EP4673492A2 - Oxyde d'éthylène respectueux de l'environnement, oxyde de propylène et produits en aval - Google Patents

Oxyde d'éthylène respectueux de l'environnement, oxyde de propylène et produits en aval

Info

Publication number
EP4673492A2
EP4673492A2 EP24707865.2A EP24707865A EP4673492A2 EP 4673492 A2 EP4673492 A2 EP 4673492A2 EP 24707865 A EP24707865 A EP 24707865A EP 4673492 A2 EP4673492 A2 EP 4673492A2
Authority
EP
European Patent Office
Prior art keywords
hydrogen
alkoxylated
ethylene oxide
polyethylenimine
ethanolamines
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24707865.2A
Other languages
German (de)
English (en)
Inventor
Stephan Hueffer
Marco Krueger
Thomas Weiss
Ralf Widmaier
Christian Koenig
Juergen Tropsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP4673492A2 publication Critical patent/EP4673492A2/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis
    • C01C1/0405—Preparation of ammonia by synthesis from N2 and H2 in presence of a catalyst
    • C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor

Definitions

  • the present invention relates to a process for preparing ethylene oxide or propylene oxide comprising the following steps:
  • step (c) converting the methanol from step (ab) to ethene and/or propene
  • step (d) reacting the ethene and/or propene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and/or propylene oxide
  • the carbon dioxide in step (b) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass
  • the hydrogen in step (b) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least in part from non-fossil resources; a process for preparing ethanolamines, wherein said process comprises steps (b), (c) and (d) of the process for preparing ethylene oxide or propylene oxide additionally the following steps:
  • step (e) converting the ammonia from step (a) with ethylene oxide from step (d) to ethanolamines in one or more steps, wherein the hydrogen in step (a) and/or step (b) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources; a process for preparing polyethylenimine, wherein said process comprises steps (a),
  • step (f) separating monoethanolamine from the ethanolamines obtained in step (e);
  • step (g) converting monoethanolamine from step (f) to ethylenimine, preferably by a catalytic gas-phase synthesis, and
  • step (h) polymerizing the ethylenimine obtained in step (g) to polyethylenimine, wherein the hydrogen in step (a) and/or step (b) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources; a process for preparing alkoxylated compounds comprising i) 20 wt-% to ⁇ 100 wt-% of ethylene oxide units and/or propylene oxide units, ii) 0 wt-% to 30 wt-% of at least one alkylene oxide unit different from ethylene oxide and propylene oxide units, iii) >0 wt-% to 80 wt-% of at least one starter unit having Zerewitinoff active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%, comprising steps (b), (c) and (d) of the
  • step (eO) reacting the ethylene oxide and/or propylene oxide obtained in step (d) and optionally the at least one alkylene oxide different from ethylene oxide and propylene oxide with the at least one starter unit having Zerewitinoff active hydrogen atoms in one or more steps to form the alkoxylated compound
  • the carbon dioxide in step (b) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass; a process for making alkoxylated di-, oligo- and polyamines or alkoxylated polyethyl- enimine (any of it alone or together “compound”), wherein said process comprises steps (a), (b), (c) and (d) of the process according the process for preparing ethanolamines and additionally the following step: e1 ) converting the ethylene oxide and/or propylene oxide from step (d) and optionally the at least one alkylene oxide different from ethylene oxide and propy
  • step (i) alkoxylating the polyethyleneimine from step (g) with the ethylene oxide and/or propylene oxide, and optionally further ingredients such as other alkylene oxides and/or lactones, to obtain alkoxylated polyethyleneimines, wherein the hydrogen in steps (a) and (b) having a molar share of deuterium ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy, wherein preferably step (g) is carried out in gas phase or in liquid phase; a process for making surfactant, such surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or is produced with hydrogen, wherein said process comprises the following steps:
  • step (b) reacting hydrogen with carbon oxides, preferably carbon dioxide to form methanol, (c) and (d) converting the methanol from step (b) to ethylene and further with oxygen to ethylene oxide,
  • step (e) converting the ammonia from step (a) with ethylene oxide from step (d) to ethanolamines in one or more steps
  • step (f) separating monoethanolamine, diethanolamine and triethanolamine from ethanolamines obtained in step (e),
  • step (gO) converting any of the products from step a), b), c), d), and e) in at least one known process step to a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen, to obtain a surfactant comprising less deuterium based on total hydrogen content compared to the chemical identical surfactant obtained from fossil-based sources only, wherein the hydrogen in steps (a) and (b) having a molar share of deuterium ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy; polyethylenimines, ethanolamines, alkoxylated compounds, surfactants, alkoxy
  • the present invention relates to a process for preparing polyethylenimine in good yields having a low product carbon footprint (PCF), based at least in part on energy generated from non-fossil resources, a process for preparing ethanolamines in good yields having a low product carbon footprint (PCF), based at least in part on energy generated from non-fossil resources, polyethylenimine and ethanolamines obtained by the inventive processes, preferably having a low product carbon footprint (PCT), the polyethylenimine being particularly stable when used in carbon capturing and the use of the inventive polyethylenimine and the inventive ethanolamines as CO2 absorbent in CO2 capturing processes.
  • PCF product carbon footprint
  • PCT low product carbon footprint
  • CO2 equivalents are abbreviated with "CO2e”.
  • Scope 1 are direct CO2e emissions resulting from production processes in the plants that are owned or controlled by the reporting company. They arise from e.g.,
  • Scope 2 are indirect CO2e emissions resulting from the generation of purchased energy such as electricity, steam, heat and cooling available via e.g. grid-connections and used as utilities by the company’s plants.
  • Scope 3 upstream CO2e emissions are the sum of all indirect emissions resulting e.g., from the use of purchased raw materials from other suppliers including indirect emissions from transport up to the cradle of generation and extraction of fuels consumed by all product-processing plants in the complete value chain. It is important to note, that this can encompass the emissions of much more than one company since the total emissions of e.g. purchased raw materials up to the cradle must be included. This sum of indirect emissions are also called backpack emissions.
  • Scope 3 downstream CO2e emissions include the indirect greenhouse gas emissions within the company’s value chain related to sold goods and services and emitted after they leave the company’s ownership or control. This includes e.g. additional transportation and transformation related emissions up to the final disposal waste-related emissions at the final product’s end-of-life.
  • the “material carbon” in the polymer product is considered as the only add-on CO2 emissions for the scope 3 downstream (end of life “grave”) emissions; all other e.g. transportation and use-related emissions in the products customer and consumer use phase are out of scope.
  • the product carbon footprint sums up the total greenhouse gas (GHG) emissions generated by a product over the different stages of its life cycle.
  • GHG greenhouse gas
  • a cradle-to-gate (partial) PCF considers all the processes from extraction of resources through manufacturing of precursors and the making of the final product itself up to the point where it leaves the company gate (all product related direct GHG emissions, including removals, from Scopes 1 , 2 and 3 upstream).
  • a cradle-to-grave PCF covers the complete life cycle of the product, including the emissions from the use phase and end- of-life of the product (all product related direct GHG emissions, including removals, from Scopes 1 , 2 and 3 upstream and downstream).
  • Fig. 1 the system boundary definition according to the GHG Protocol are shown.
  • PCF in this application refers to cradle-to-gate PCF.
  • total cradle-to-gate PCF is meant the total PCF of the corresponding alkoxylated compound from cradle to gate.
  • total cradle-to-gate PCF is meant the total PCF of the corresponding compound from cradle to gate.
  • the total cradle-to-grave PCF of the alkoxylated compounds according to the definition mentioned above is given, i.e. the “material carbon” in the polymer product is considered as the only add-on CO2 emissions for the scope 3 downstream (end of life “grave”) emissions; all other e.g. transportation and use-related emissions in the products customer and consumer use phase are out of scope.
  • PCF Product Carbon Footprint
  • PCF Product Carbon Footprint
  • US2022/0107618 A1 , US2022/0108327 A1 and US2022/0108326 A1 relate to computer-implemented methods for determining the carbon footprint of a product in production processes in a production plant, in particular of a product in interconnected production processes.
  • the Product Carbon Footprint helps to identify, analyze and, with the right measures, reduce or (ideally) completely avoid the climate-relevant impacts arising in the form of greenhouse gas emissions.
  • the biodegradability of the alkoxylated compounds according to the present invention is determined based on the currently valid OECD guidelines.
  • Inherent biodegradable A classification of chemicals for which there is unequivocal evidence of biodegradation (primary or ultimate) in any test of biodegradability.
  • Disappearance time 50 (DT50): The time within which the initial concentration of the test substance is reduced by 50 percent.
  • alkoxylated compounds according to the present invention are generally tested regarding their ready biodegradability according to OECD 301 B.
  • Test No. 301 Ready Biodegradability (https://www.oecd-ilibrary.org/environment/test- no-301-ready-biodegradability_9789264070349-en)
  • This Test Guideline describes six methods that permit the screening of chemicals for ready biodegradability in an aerobic aqueous medium.
  • the methods are: the DOC Die- Away (301 A), the CO2 Evolution (Modified Sturm Test) (301 B), the MITI (I) (Ministry of International Trade and Industry, Japan) (301C), the Closed Bottle (301 D), the Modified OECD Screening (301 E) and the Manometric Respirometry (301 F).
  • a solution, or suspension, of the test substance, well determined/described, in a mineral medium is inoculated and incubated under aerobic conditions in the dark or in diffuse light.
  • the running parallel blanks with inoculum but without test substance permits to determined the endogenous activity of the inoculum.
  • a reference compound aniline, sodium acetate or sodium benzoate
  • the test lasts for 28 days. At least two flasks or vessels containing the test substance plus inoculum, and at least two flasks or vessels containing inoculum only should be used; single vessels are sufficient for the reference compound.
  • degradation is followed by the determination of parameters such as DOC, CO2 production and oxygen uptake.
  • the pass levels for ready biodegradability are 70% removal of DOC and 60% of ThOD or ThCO2 production for respirometric methods. These pass values have to be reached in a 10-d window within the 28-d period of the test.
  • the ethylene glycol and propylene glycol part (i.e. the alkylene oxide units) in alkox- ylated compounds has an important impact on the product carbon footprint of the alkoxylated compounds.
  • alkoxylated compounds ethylene glycol and/or propylene glycol based compounds
  • the ethylene oxide and/or the propylene oxide employed in the synthesis of the alkoxylated compounds are prepared by the specific process of the present invention.
  • ethylene oxide and propylene oxide are versatile starting materials for numerous downstream products like the polyethylenimines, ethanolamines, alkoxylated compounds, surfactants, alkoxylated di-, oligo- and polyamines, and alkoxylated polyethyl- enimine.
  • PEI Polyethylenimine
  • a versatile polymer that can be used for various purposes such as, but not limited to detergents, adhesives, water treatment agents and cosmetics. Furthermore, PEI is used in paper manufacture as well as in flocculating processes or as a raw material in the field of biotechnology.
  • Ethanolamines are flammable, corrosive, colorless, viscous liquids that are produced by the reaction between ammonia and ethylene oxide (EO).
  • EO ethylene oxide
  • ethanolamines are a key ingredient in a number of important product formulations such as cosmetics and personal hygiene applications, agricultural products, wood-preservation chemicals, soaps and detergents, gas treatments. They can also be used in the production of nonionic detergents, emulsifiers, and soaps, as well as in emulsion paints, polishes, and cleansers.
  • MEA, DEA, or TEA depends on whether an ammonia molecule reacts with one, two, or three ethylene oxide molecules and the product ratio can be adjusted by the raw material feed composition and processing conditions.
  • MEA, DEA and TEA can be separated after synthesis e.g. by distillation in order to manufacture high purity chemical materials with order of magnitude 99% purity, as required for the application use.
  • PEI as well as MEA, DEA and/or TEA are useful as capturing agent for carbon dioxide (CO2).
  • CO2 carbon dioxide
  • the amino groups in PEI react with the CO2, thereby binding and removing it from a relevant emission gas source or even ambient air.
  • the bound CO2 can be desorbed in order to concentrate the carbon dioxide allowing for certain re-use of the PEI, MEA, DEA and/or TEA.
  • inherent capturing efficiency losses over time could be compensated with fresh material and optimization of the overall CO2 capturing performance by product and process innovation is ongoing work in progress . Since according to scientists gigatonnes amounts per annum of CO2 must be removed from the atmosphere in order to achieve the climate goals there is a high demand for these adsorber materials.
  • Ammonia is a key precursor in the preparation of MEA, which is in turn a key precursor in the preparation of El and PEI. Since the development of the Haber-Bosch process for the preparation of ammonia, the vast majority of ammonia is manufactured by the direct synthesis from hydrogen and nitrogen in the presence of a catalyst, especially an iron-containing catalyst. In modern processes, a significant amount of the hydrogen is provided by steam reforming, thus, from natural gas.
  • US 6,495,609 B1 concerns the carbon dioxide recovery in an ethylene to ethylene oxide production process.
  • a method for recovering carbon dioxide from an ethylene oxide production process is disclosed, wherein the recovered carbon dioxide is used as a carbon source from ethanol synthesis. The carbon dioxide is used to produce a syngas stream and the syngas stream is then used to produce methanol.
  • GB 2,464,691 A concerns the manufacture of methanol from agricultural by-product cellulosic/lignitic material. It is disclosed that the cellulosic/lignitic by-product that remains after the cropping of agricultural products is converted to carbon dioxide by calorific oxidation and in another section of the synthesis factory, hydrogen gas is produced by electrolysis. The hydrogen gas is then reacted with the carbon dioxide to make methanol.
  • the ethanolamines and polyethylenimine should be especially useful for carbon capturing.
  • the polyethylenimine and ethanolamines should not be based on starting materials based on biomass feedstocks or biomass balanced feedstocks.
  • carbon oxides like CO and CO2 are not considered as biomass feedstocks.
  • Biomass balance and biomass balanced feedstocks are for example described in https://www.basf.com/global/documents/en/sustainability/we-produce-safely-and-effi- ciently/resources-and-ecosystems/BASFs_biomass-balance-approach.pdf
  • the object is solved by a process for preparing polyethylenimine, wherein said process comprises the following steps:
  • step (c) converting the methanol from step (b) to ethylene
  • step (d) reacting ethylene from step (c) with oxygen to form ethylene oxide
  • step (e) converting the ammonia from step (a) with ethylene oxide from step (d) to ethanolamines in one or more steps
  • step (f) separating monoethanolamine from the ethanolamines obtained in step (e);
  • step (g) converting monoethanolamine from step (f) to ethylenimine, preferably by a catalytic gas-phase synthesis, and
  • step (h) polymerizing ethylenimine obtained in step (g) to polyethylenimine, wherein the hydrogen in step (a) and/or step (b) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources.
  • the process of the present invention is not based on starting materials based on biomass feedstocks or biomass balanced feedstocks.
  • the unique Verbund system of the applicant creates efficient value chains that extend from basic chemicals all the way to consumer products. This makes it possible to gather reliable data about greenhouse gas (GHG) emissions generated by a product in and beyond the company-owned Verbund, especially generated by polyethylenimine and ethanolamines and upstream compounds in the preparation process of both, over the different stages of its life cycle, especially from cradle-to-gate (scopes 1 , 2 and 3 upstream).
  • GSG greenhouse gas
  • the process for preparing polyethylenimine is energy demanding and many of steps (a) to (h) of the process for preparing polyethylenimine can be carried out by a number of alternative methods.
  • the inventors found a process for the preparation of polyethylenimine, wherein each step is optimized or at least prepared for obtaining polyethylenimine having a low carbon footprint.
  • Ethylenimine (aziridine) is for example produced industrially from monoethanolamine via two commercial routes.
  • the catalytic gas-phase dehydration process requires an oxide catalyst and very high temperatures (350 - 450 °C) to effect the dehydration and 3-ring closure.
  • monoethanolamine is converted to its sulfate ester, which undergoes base-induced sulfate elimination under relatively mild conditions.
  • Older methods entailed amination of 1 ,2-dichloroethane and cyclization of 2-chloroethylamine.
  • polyethylenimine having an especially low PCF is obtained based on ethylenimine prepared by a catalytic gas-phase synthesis, whereby the hydrogen used for the preparation of ammonia and methanol, i.e. the starting materials for the preparation of ammonia and ethylene oxide being the raw materials for ethanolamines including monoethanolamine required for synthesis of ethylenimine and polyethylenimine, is obtained at least in part by water splitting, preferably electrolysis, based on electrical power generated at least in part from non-fossil resources.
  • the product carbon footprint sums up the total greenhouse gas (GHG) emissions generated by a product over the different stages of its life cycle.
  • a cradle-to-gate product carbon footprint sums up the total greenhouse gas (GHG) emissions generated by a product over scopes 1 , 2 and scope 3 upstream as prescribed in the “TfS guideline” mentioned above and as shown with the relevant boundary conditions in Fig 1 .
  • PCF in this application refers to cradle-to-gate PCF.
  • total cradle-to-gate PCF is meant the total PCF of the corresponding compound from cradle to gate.
  • One highly relevant factor determining the PCF is besides the input ratio and the backpack emissions of the starting materials used as well as the input ratio and the backpack emissions of the energy needed in every production step of a specific product.
  • the process of the present invention for preparing ethanolamines and the process for preparing polyethylenimine in all steps (a) to (h) and the step of generating hydrogen energy in form of heating energy (e.g. steam) and/or electrical power is used as contributors in the PCF.
  • heating energy e.g. steam
  • step (a) to (h) and the step of generating hydrogen of the process of the present invention energy in form of heating energy (e.g. steam) and/or electrical power is used.
  • the energy (electrical power) used for generating the hydrogen which is used in steps (a) and/or (b) preferably the energy used for generating the hydrogen which is used in steps (a) and/or (b) and the energy used in one or more of steps (a) to (h) is generated at least in part from non-fossil resources.
  • step (g) are highly energy demanding steps in the process for preparing polyethylenimine, but also steps (c) and (b) as well as steps (a) and (f).
  • Polyethylenimine - as well as ethanolamines - having a particularly low total cradle-to-gate product carbon footprint are therefore only achieved, if the energy used at least in step (c), and preferably at least in steps (c) and (b), more preferably at least in steps (c), (b), (a) and (f) (in addition to the step of generating the hydrogen and step (g)) is generated at least in part from non-fossil resources.
  • the measure of using at least in part energy generated from non-fossil resources is not sufficient for obtaining a particularly low cradle- to-gate PCF of polyethylenimine. Additionally, the yield of every process step and thus minimal waste generation is a strong lever. One further important factor is especially the conversion of monoethanolamine to ethylenimine, by a catalytic gas-phase synthesis as claimed in step (g) of the process of the present invention.
  • non-fossil resources means especially for the process for preparing polyethylenimine and for the process for preparing ethanolamines and in a further embodiment of the invention for all inventive processes, that part of the energy can still be produced from fossil fuels, preferably from natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of energy produced than combustion of coal.
  • the portion of energy produced from fossil fuels should be as low as possible in the process of the present invention, preferably ⁇ 50%, preferably ⁇ 30%, most preferably ⁇ 20%, further most preferably ⁇ 10%.
  • the energy is generated exclusively from non-fossil resources.
  • At least part of the energy used in the process of the present invention is utilized from excess energy generated in other exothermic chemical processes than the process steps of the present invention (typical examples: acrylic acid, formaldehyde or ethylene oxide production), for example in a chemical “Verbund” production setup distributing the excess energy e.g. as steam to endothermic process consumers.
  • Excess steam can substitute steam generated by fossil fuels and be allocated as CO2e credits to the exothermic process source thereby closing the CC>2-balance as described in the “TfS PCF guideline”.
  • Such a Verbund plant is preferably supplied with additional energy generated from non-fossil resources.
  • At least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required energy input used in the process of the present invention is generated from non-fossil resources.
  • the energy is generated at least in part from non-fossil resources selected from solar energy (thermal, photovoltaic and concentrated solar power), wind power, hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste energy sources, nuclear energy and mixtures thereof.
  • non-fossil resources selected from solar energy (thermal, photovoltaic and concentrated solar power), wind power, hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste energy sources, nuclear energy and mixtures thereof.
  • the energy is generated at least in part from non-fossil resources selected from renewable resources, preferably selected from solar energy (thermal, photovoltaic and concentrated solar power), wind power, hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste and mixtures thereof.
  • renewable resources preferably selected from solar energy (thermal, photovoltaic and concentrated solar power), wind power, hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste and mixtures thereof.
  • the greenhouse gas (GHG) emissions generated by polyethylenimine over scopes 1 , 2 and scope 3 upstream (cra- dle-to-gate), i.e. the total cradle-to-gate product carbon footprint (PCF) of polyethylenimine is preferably reduced by > 50% compared to the product carbon footprint of typically prepared polyethylenimine.
  • typically or conventionally prepared polyethylenimine preferably has the meaning that hydrogen and syngas is provided by steam reforming of natural gas and the conversion of monoethanolamine to ethylenimine in step (g) of the present invention is carried out by the liquid-phase process, whereby pre- dominatly no non-fossil energy is used in said conventional process.
  • the polyethylenimine obtained in step (h) having a total cradle-to-gate product carbon footprint of generally ⁇ 8.0 kg CC>2e/kg polyethylenimine, preferably ⁇ 7.0 kg CO2e/kg polyethylenimine, more preferably ⁇ 6 kg CO2e/kg polyethylenimine, further more preferably ⁇ 5 kg CO2e/kg polyethylenimine, most preferably ⁇ 4.0 kg CO2e/kg polyethylenimine, further most preferably ⁇ 3.0 kg CO2e/kg polyethylenimine, even further most preferably ⁇ 2.0 kg CC>2e/kg polyethylenimine, very most preferably ⁇ 1 .5 kg CO2e/kg polyethylenimine.
  • the greenhouse gas (GHG) emissions generated by polyethylenimine according to the process of the present invention over scopes 1 , 2 and scope 3 upstream (cradle-to-gate) are generally ⁇ 8.0 kg CO2e/kg polyethylenimine, preferably ⁇ 7.0 kg CC>2e/kg polyethylenimine, more preferably ⁇ 6 kg CO2e/kg polyethylenimine, further more preferably ⁇ 5 kg CO2e/kg polyethylenimine, most preferably ⁇ 4.0 kg CC>2e/kg polyethylenimine, further most preferably ⁇ 3.0 kg CO2e/kg polyethylenimine, even further most preferably ⁇ 2.0 kg CO2e/kg polyethylenimine, very most preferably ⁇ 1.5 kg CC>2e/kg polyethylenimine.
  • the product carbon footprint given in kgCO2e/kg product relates to the active product (100% product).
  • the active product 100% product.
  • aqueous PEI aqueous PEI is prepared, only the active product without water and other impurities counts for the total cradle-to-gate product carbon footprint.
  • the present invention further relates to polyethylenimine obtainable by the process for preparing polyethylenimine according to the present invention.
  • the carbon source for the production of ethanolamines and polyethyleneimine, namely in step (b) (production of methanol) are carbon oxides, preferably carbon dioxide.
  • the by-product spectrum of ammonia and methanol employed in the process for the preparation of ethanolamines and polyethylenimine according to the present invention is different from the by-product spectrum of ammonia and methanol obtained by conventional processes (i.e. using synthesis gas “syngas,” which is a combination of varying amounts of H2, CO, and CO2 frequently derived from gasified coal or natural gas).
  • synthesis gas “syngas,” which is a combination of varying amounts of H2, CO, and CO2 frequently derived from gasified coal or natural gas i.e. using synthesis gas “syngas,” which is a combination of varying amounts of H2, CO, and CO2 frequently derived from gasified coal or natural gas.
  • conventionally obtained methanol generally comprises more methylformiate, acetone and higher alcohols (> C3)
  • conventionally obtained ammonia generally comprises more sulfur compounds and unsaturated hydrocarbon impurities than methanol and ammonia obtained by the process according to the present invention.
  • the polyethylenimine obtained by the process of the present invention is further characterized by a different ratio of primary, secondary and tertiary amino groups compared with polyethylenimine obtained by conventional processes.
  • the share of secondary amino groups is increased at the expense of the share of primary amino groups in the polyethylenimine prepared according to the present invention.
  • Said ratio of primary, secondary and tertiary amino groups in the inventive polyethylenimine is beneficial for the stability of the polyethylenimine during carbon capturing (primary amino groups generally decompose faster under the conditions that occur during cyclic exposure at for example up to 110 °C during the CO2 desorption phase than secondary amino groups).
  • the present invention further relates to polyethylenimine having a total cradle-to-gate product carbon footprint of ⁇ 8.0 kg CO2e/kg polyethylenimine, preferably ⁇ 7.0 kg CC>2e/kg polyethylenimine, more preferably ⁇ 6 kg CO2e/kg polyethylenimine, further more preferably ⁇ 5 kg CO2e/kg polyethylenimine, most preferably ⁇ 4.0 kg CO2e/kg polyethylenimine, further most preferably ⁇ 3.0 kg CO2e/kg polyethylenimine, even further most preferably ⁇ 2.0 kg CO2e/kg polyethylenimine, very most preferably ⁇ 1 .5 kg CC>2e/kg polyethylenimine.
  • the present application teaches all necessary steps for obtaining polyethylenimine having the specific total cradle-to-gate product carbon footprint mentioned.
  • a number of carbon labels, which indicate the PCF of a given product, are known.
  • the world's first carbon label, the Carbon Reduction Label shows the carbon footprint embodied in a product and was first introduced in the UK in 2006 by the Carbon Trust.
  • the guideline: ’’ The Product Carbon Footprint Guideline for the Chemical Industry” launched by TfS (Together for Sustainability), Version 2.0, November 2022) (TfS guideline) used as basis for the calculation of the total cradle-to-gate PCF in this application is “open source”, i.e. available to everyone.
  • the specific product carbon footprint of pol- yethylenimine prepared by different processes and using raw materials and energy sources available at specific locations can therefore be calculated by a person skilled in the art, and the polyethylenimine prepared by different processes with differentiated material and energy input can be clearly distinguished by different cradle-to-gate product carbon footprints.
  • the ammonia obtained in step (a) having a total cradle-to-gate product carbon footprint of generally ⁇ 0.6 kg CO2e/kg ammonia, preferably ⁇ 0.4 kg CO2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia.
  • GFG greenhouse gas
  • the greenhouse gas (GHG) emissions generated by ammonia according to the process of the present invention over scopes 1 , 2 and scope 3 upstream (cradle-to-gate) are generally ⁇ 0.6 kg CO2e/kg ammonia, preferably ⁇ 0.4 kg CO2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia.
  • the present invention further relates to ammonia having a total cradle-to-gate product carbon footprint of ⁇ 0.6 kg CO2e/kg ammonia, preferably ⁇ 0.4 kg CO2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia.
  • the present application teaches all necessary steps for obtaining ammonia having the specific total cradle-to-gate product carbon footprint mentioned.
  • the ethylene oxide obtained in step (d) having a total cradle-to-gate product carbon footprint of generally ⁇ 1 .2 kg CC>2e/kg ethylene oxide, preferably ⁇ 0.8 kg CO2e/kg ethylene oxide, more preferably ⁇ 0.6 kg CO2e/kg ethylene oxide.
  • the greenhouse gas (GHG) emissions generated by ethylene oxide according to the process of the present invention over scopes 1 , 2 and scope 3 upstream (cradle-to-gate) are generally ⁇ 1 .2 kg CC>2e/kg ethylene oxide, preferably ⁇ 0.8 kg CO2e/kg ethylene oxide, more preferably ⁇ 0.6 kg CC>2e/kg ethylene oxide.
  • the present invention further relates to ethylene oxide having a total cradle-to-gate product carbon footprint of ⁇ 1 .2 kg CO2e/kg ethylene oxide, preferably ⁇ 0.8 kg CC>2e/kg ethylene oxide, more preferably ⁇ 0.6 kg CO2e/kg ethylene oxide.
  • the present application teaches all necessary steps for obtaining ethylene oxide having the specific total cradle-to-gate product carbon footprint mentioned.
  • the ethanolamines obtained in step (e) having a total cradle-to-gate product carbon footprint of generally ⁇ 1 .6 kg CO2e/kg ethanolamines, preferably of ⁇ 1 .2 kg CO2e/kg ethanolamines, more preferably of ⁇ 0.9 kg CO2e/kg ethanolamines.
  • the greenhouse gas (GHG) emissions generated by ethanolamine according to the process of the present invention over scopes 1 , 2 and scope 3 upstream (cradle-to-gate) are generally ⁇ 1 .6 kg CO2e/kg ethanolamines, preferably of ⁇ 1.2 kg CO2e/kg ethanolamines, more preferably of ⁇ 0.9 kg CO2e/kg ethanolamines.
  • the present invention further relates to ethanolamines having a total cradle-to-gate product carbon footprint of ⁇ 1 .6 kg CO2e/kg ethanolamines, preferably of ⁇ 1 .2 kg CC>2e/kg ethanolamines, more preferably of ⁇ 0.9 kg CO2e/kg ethanolamines.
  • the present application teaches all necessary steps for obtaining ethanolamine having the specific total cradle-to-gate product carbon footprint mentioned.
  • the ethyl- enimine obtained in step (g) having a total cradle-to-gate product carbon footprint of generally ⁇ 7.5 kg CO2e/kg ethylenimine, more preferably ⁇ 6.5 kg CO2e/kg ethyl- enimine, most preferably 4.5 kg CO2e/kg ethylenimine.
  • the greenhouse gas (GHG) emissions generated by ethylenimine according to the process of the present invention over scopes 1 , 2 and scope 3 upstream (cradle-to-gate) are preferably ⁇ 7.5 kg CC>2e/kg ethylenimine, more preferably ⁇ 6.5 kg CO2e/kg ethylenimine, most preferably 4.5 kg CO2e/kg ethylenimine.
  • the present invention further relates to ethylenimine having a total cradle-to-gate product carbon footprint of ⁇ 7.5 kg CO2e/kg ethylenimine, more preferably ⁇ 6.5 kg CC>2e/kg ethylenimine, most preferably 4.5 kg CO2e/kg ethylenimine.
  • the present application teaches all necessary steps for obtaining ethylenimine having the specific total cradle-to-gate product carbon footprint mentioned.
  • the present invention preferably relates to a process for preparing polyethylenimine, wherein said process comprises the following steps:
  • step (a) reacting hydrogen with nitrogen to form ammonia, wherein the ammonia obtained in step (a) preferably having a total cradle-to-gate product carbon footprint of ⁇ 0.6 kg CC>2e/kg ammonia, preferably ⁇ 0.4 kg CO2e/kg ammonia, more preferably ⁇ 0.15 kg CC>2e/kg ammonia,
  • step (c) converting the methanol from step (b) to ethylene
  • step (d) reacting ethylene from step (c) with oxygen to form ethylene oxide, wherein the ethylene oxide obtained in step (e) having a total cradle-to-gate product carbon footprint of ⁇ 1 .2 kg CO2e/kg ethylene oxide, preferably ⁇ 0.8 kg CO2e/kg ethylene oxide, more preferably ⁇ 0.6 kg CO2e/kg ethylene oxide,
  • step (e) converting the ammonia from step (a) with ethylene oxide from step (d) to ethanolamines in one or more steps, wherein the ethanolamines obtained in step (e) preferably having a total cradle-to-gate product carbon footprint of ⁇ 1.6 kg CC>2e/kg ethanolamines, preferably of ⁇ 1 .2 kg CO2e/kg ethanolamines, more preferably of ⁇ 0.9 kg CO2e/kg ethanolamines,
  • step (f) separating monoethanolamine from the ethanolamines obtained in step (e);
  • step (g) converting monoethanolamine from step (f) to ethylenimine, by a catalytic gasphase synthesis, wherein the ethylenimine obtained in step (g) preferably having a total cradle-to-gate product carbon footprint of ⁇ 7.5 kg CO2e/kg ethylenimine, more preferably ⁇ 6.5 kg CO2e/kg ethylenimine, most preferably 4.5 kg CO2e/kg ethylenimine, and
  • step (h) polymerizing ethylenimine obtained in step (g) to polyethylenimine, wherein the polyethylenimine obtained in step (i) preferably having a total cradle-to-gate product carbon footprint of ⁇ 8.0 kg CO2e/kg polyethylenimine, preferably ⁇ 7.0 kg CC>2e/kg polyethylenimine, more preferably ⁇ 6 kg CO2e/kg polyethylenimine, further more preferably ⁇ 5 kg CO2e/kg polyethylenimine, most preferably ⁇ 4.0 kg CC>2e/kg polyethylenimine, further most preferably ⁇ 3.0 kg CO2e/kg polyethylenimine, even further most preferably ⁇ 2.0 kg CO2e/kg polyethylenimine, very most preferably ⁇ 1 .5 kg CO2e/kg polyethylenimine, wherein the hydrogen in step (a) and/or step (b) is obtained at least in part by water splitting, preferably by electro
  • the ammonia obtained in step (a) having a total cradle-to-gate product carbon footprint of ⁇ 0.6 kg CO2e/kg ammonia, preferably ⁇ 0.4 kg CO2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia.
  • step (a) having a total cradle-to-gate product carbon footprint of ⁇ 0.6 kg CO2e/kg ammonia, preferably ⁇ 0.4 kg CO2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia and the ethanolamines obtained in step (e) having a total cradle-to-gate product carbon footprint of ⁇ 1 .6 kg CO2e/kg ethanolamines, preferably of ⁇ 1 .2 kg CO2e/kg ethanolamines, more preferably of ⁇ 0.9 kg CO2e/kg ethanolamines.
  • step (a) having a total cradle-to-gate product carbon footprint of ⁇ 0.4 kg CC>2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia
  • the ethanolamines obtained in step (e) having a total cradle-to-gate product carbon footprint of ⁇ 1 .6 kg CC>2e/kg ethanolamines, preferably of ⁇ 1 .2 kg CO2e/kg ethanolamines, more preferably of ⁇ 0.9 kg CC>2e/kg ethanolamines
  • the ethylenimine obtained in step (g) having a total cradle-to-gate product carbon footprint of ⁇ 7.5 kg CO2e/kg ethylenimine, more preferably ⁇ 6.5 kg CO2e/kg ethylenimine, most preferably 4.5 kg CO2e/kg ethylenimine and the polyethylenimine obtained
  • the present invention further relates to a process for preparing ethanolamines, wherein said process comprises the following steps: (a) reacting hydrogen with nitrogen to form ammonia, wherein the ammonia obtained in step (b) preferably having a total cradle-to-gate product carbon footprint of ⁇ 0.4 kg CC>2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia,
  • step (c) converting the methanol from step (b) to ethylene
  • step (d) reacting ethylene from step (c) with oxygen to form ethylene oxide, wherein the ethylene oxide obtained in step (d) preferably having a total cradle-to-gate product carbon footprint of ⁇ 1 .2 kg CO2e/kg ethylene oxide, preferably ⁇ 0.8 kg CC>2e/kg ethylene oxide, more preferably ⁇ 0.6 kg CO2e/kg ethylene oxide,
  • step (e) converting the ammonia from step (a) with ethylene oxide from step (d) to ethanolamines in one or more steps, wherein the ethanolamines obtained in step (f) preferably having a total cradle-to-gate product carbon footprint of ⁇ 1.6 kg CC>2e/kg ethanolamines, preferably of ⁇ 1 .2 kg CO2e/kg ethanolamines, more preferably of ⁇ 0.9 kg CO2e/kg ethanolamines, wherein the hydrogen in step (a) and/or step (b) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources, the hydrogen in step (a) and/or step (b) preferably having a total cradle-to-gate product carbon footprint of ⁇ 5 kg CC>2e/kg hydrogen, preferably ⁇ 4.6 kg CO2e/kg hydrogen, more preferably ⁇ 3.5 kg CC>2e/
  • the ethylene oxide obtained in step (d) having a total cradle-to-gate product carbon footprint of ⁇ 1.2 kg CO2e/kg ethylene oxide, more preferably ⁇ 0.8 kg CO2e/kg ethylene oxide, most preferably ⁇ 0.8 kg CC>2e/kg ethylene oxide.
  • the ammonia obtained in step (a) having a total cradle-to-gate product carbon footprint of ⁇ 0.4 kg CO2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia.
  • the ammonia obtained in step (a) having a total cradle-to-gate product carbon footprint of ⁇ 0.4 kg CO2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia, and the ethylene oxide obtained in step (d) having a total cradle-to-gate product carbon footprint of ⁇ 1 .2 kg CO2e/kg ethylene oxide, preferably ⁇ 0.8 kg CO2e/kg ethylene oxide, more preferably ⁇ 0.6 kg CO2e/kg ethylene oxide.
  • the ammonia obtained in step (a) having a total cradle-to-gate product carbon footprint of ⁇ 0.4 kg CO2e/kg ammonia, more preferably ⁇ 0.15 kg CO2e/kg ammonia
  • the ethylene oxide obtained in step (d) having a total cradle-to-gate product carbon footprint of ⁇ 1 .2 kg CO2e/kg ethylene oxide, preferably ⁇ 0.8 kg CO2e/kg ethylene oxide, more preferably ⁇ 0.6 kg CO2e/kg ethylene oxide
  • the ethanolamines obtained in step (e) having a total cradle-to-gate product carbon footprint of ⁇ 1.6 kg CO2e/kg ethanolamines, preferably of ⁇ 1 .2 kg CC>2e/kg ethanolamines, more preferably of ⁇ 0.9 kg CO2e/kg ethanolamines.
  • the greenhouse gas (GHG) emissions generated by ethanolamines over scopes 1 , 2 and scope 3 upstream cra- dle-to-gate
  • the total cradle-to-gate product carbon footprint (PCF) of ethanolamines is preferably reduced by > 50% compared to the product carbon footprint of typically prepared ethanolamines.
  • typically or conventionally prepared ethanolamines preferably has the meaning that hydrogen and syngas is provided by steam reforming of natural gas.
  • the present invention further relates to ethanolamines obtainable by the process for preparing ethanolamines according to the present invention.
  • the total cradle-to-gate product carbon footprint of ethanolamines obtainable by the process according to the present invention is mentioned above.
  • the process for preparing polyethylenimine comprises steps (a) to (h) and the generation of hydrogen as mentioned above:
  • Preparation (generation) of hydrogen The hydrogen in step (a) and/or step (b), preferably in step (a) and (b) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources:
  • This step concerns the provision of hydrogen at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources.
  • water splitting means that part of the hydrogen can still be produced by other processes, generally by steam reforming of natural gas and/or other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification, preferably by steam reforming of natural gas and/or other light hydrocarbons.
  • the portion of hydrogen in steps (a) and/or (b) produced by other methods than by water splitting should be as low as possible.
  • step (a) of the process of the present invention ⁇ 50%, preferably ⁇ 30%, most preferably ⁇ 20%, further most preferably ⁇ 10% of the hydrogen is produced by other methods than by water splitting.
  • the hydrogen in step (a) is produced exclusively by water splitting, preferably by electrolysis.
  • step (b) of the process of the present invention ⁇ 50%, preferably ⁇ 30%, most preferably ⁇ 20%, further most preferably ⁇ 10% of the hydrogen is produced by other methods than by water splitting.
  • the hydrogen in step (b) is produced exclusively by water splitting, preferably by electrolysis.
  • steps (a) and (b) of the process of the present invention ⁇ 50%, preferably ⁇ 30%, most preferably ⁇ 20%, further most preferably ⁇ 10% of the hydrogen is produced by other methods than by water splitting.
  • the hydrogen in step (a) is produced exclusively by water splitting, preferably by electrolysis.
  • the hydrogen in step (a) and/or step (b) preferably having a total cradle-to- gate product carbon footprint of ⁇ 5 kg CO2e/kg hydrogen, preferably ⁇ 4.6 kg CO2e/kg hydrogen, more preferably ⁇ 3.5 kg CO2e/kg hydrogen, most preferably ⁇ 2.5 kg CC>2e/kg hydrogen, further most preferably ⁇ 2 kg CO2e/kg hydrogen, more preferably, the hydrogen in step (a) and step (b) having a total cradle-to-gate product carbon footprint of ⁇ 5 kg CC>2e/kg hydrogen, preferably ⁇ 4.6 kg CO2e/kg hydrogen, more preferably ⁇ 3.5 kg CC>2e/kg hydrogen, most preferably ⁇ 2.5 kg CO2e/kg hydrogen, further most preferably ⁇ 2 kg CO2e/kg hydrogen.
  • Alkoxylated compounds like polyalkylene glycols and compounds comprising alkylene glycol groups are used in various industrial fields and have high performance when used, for example, in home care products, cosmetic products, pharmaceutical products, food sector, building materials, lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids, agrochemicals like pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and polyurethane) applications.
  • lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids,
  • polyalkylene glycols are aliphatic polyethers which are generated by the ring-opening polymerization (ROP) of epoxide monomers, especially ethylene oxide (EO), propylene oxide (PO), and, to a lesser extent, butylene oxide (BO).
  • ROP ring-opening polymerization
  • EO ethylene oxide
  • PO propylene oxide
  • BO butylene oxide
  • the characteristic properties of polyether-based materials are due to their unique backbone, in particular its high flexibility leading to low glass transitions below -60 °C, and its hydrophilicity due to the C-O-C bond.
  • Poly(ethylene glycol) (or polyethylene glycol) is the gold standard biocompatible polymer for pharmaceutical, cosmetic, and medical applications and is used for an extremely wide range of products ranging from skin care products to tablet formulations, and food additives.
  • Higher molecular weight polymers of EO are commonly called poly(ethylene) oxide (PEO) or sometimes poly(oxyethylene) (POE), whereas polymers with molecular weights below 30 000 g/mol are referred to as poly(ethylene glycol) (PEG).
  • PEO poly(ethylene) oxide
  • POE poly(oxyethylene)
  • PEG poly(ethylene glycol)
  • the abbreviation mPEG designates a monomethyl-ether terminated PEG with a single terminal hydroxyl group that can be further functionalized for block copolymer synthesis or bioconjugation with PEG, commonly called “PEGylation.
  • Polypropylene oxide) (PPO), often designated polypropylene glycol) (or polypropylene glycol) (PPG) for lower molecular weights, is commonly produced by the ROP of PO.
  • PPO polypropylene glycol
  • PPG polypropylene glycol
  • PPO is not water-soluble at room temperature.
  • PPGs are soluble in aqueous solution at low temperature.
  • the base-initiated polymerization of PO in industry mostly relies on potassium hydroxide and alcohols as initiators. Since a major fraction of PO is used for the preparation of star polymers, so-called polyether-polyols, multifunctional initiators, such as glycerol, pentaerythritol, or sorbitol are often used.
  • PPO based star polyether polyols play a key role in the synthesis of polyurethane flexible foams due to their chain flexibility, i.e., low glass transition and their amorphous nature.
  • PPG is used for lubricants, antifoaming agents, softeners, rheology modifiers, poly(urethane) applications, and nonionic surfactants, often in combination with PEG (e.g. as block copolymers).
  • the 1 ,2-butylene oxide monomer In contrast to EO and PO the 1 ,2-butylene oxide monomer (BO), has to be produced in a two-step industrial process and cannot be obtained by direct oxidation of the respective alkene.
  • the synthesis relies on the oxidation of butadiene to vinyloxirane and subsequent hydrogenation.
  • the properties of poly(butylene oxide) (or polybutylene glycol) (PBO) resemble PPO, however, as expected, it is more hydrophobic.
  • the high hydrophobicity of PBO is advantageous for several applications, for instance for polyurethanes that have to be stable toward water or hot water vapor. Small amounts of PBO added to lubricants can serve to improve their properties.
  • BO is used as a comonomer to modify the properties of other polyethers, i.e., to increase their apolar and amorphous structure.
  • the increased hydrophobicity of PBO is an advantage for surfactants combining PEO and PBO blocks.
  • polyalkylene glycol polyethylene glycol
  • polypropylene glycol polypropylene glycol
  • polybutylene glycol are used for the respective polymers or polymer blocks of any molecular weight.
  • a solution for said dilemma i.e. to provide alkoxylated compounds having a low cradle to grave (i.e. including scope 3 downstream*) product carbon footprint (PCF) and generally at the same time a good biodegradability.
  • the “material carbon” in the polymer product is considered as the only add-on CO2 emissions for the end of life “grave” emissions; all other e.g. transportation and use-related emissions in the products customer and consumer use phase are out of scope.
  • the object is achieved by a process for preparing alkoxylated compounds comprising i) 20 wt-% to ⁇ 100 wt-% , preferably 30 wt-% to ⁇ 99.3 wt-% of ethylene oxide units and/or propylene oxide units, ii) 0 wt-% to 30 wt-%, preferably 0.5 wt-% to 20 wt-% of at least one alkylene oxide unit different from ethylene oxide and propylene oxide units, iii) >0 wt-% to 80 wt-%, preferably 0.2 wt-% to 70 wt-% of at least one starter unit having Zerewitinoff active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%, comprising the following steps:
  • step (b) reacting hydrogen with carbon dioxide to form methanol, (c) converting the methanol from step (b) to ethene and/or propene,
  • step (d) reacting the ethene and/or propene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and/or propylene oxide, and
  • step (eO) reacting the ethylene oxide and/or propylene oxide obtained in step (d) and optionally the at least one alkylene oxide different from ethylene oxide and propylene oxide with the at least one starter unit having Zerewitinoff active hydrogen atoms in one or more steps to form the alkoxylated compound
  • the carbon dioxide in step (b) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example fermentation processes from waste or biomass, preferably, wherein the hydrogen in step (b) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least in part from non-fossil resources.
  • alkoxylated compounds obtainable by the process according to the present invention and by alkoxylated compounds having a total cradle- to-grave product carbon footprint of generally ⁇ 8.88*C - 0.253*E + 1 ,33*P - 0.940, preferably ⁇ 8.38*C - 0.330*E + 1 ,12*P - 0.829, more preferably ⁇ 7.89*C - 0.406*E + 0.898*P - 0.718, most preferably ⁇ 7.40*C - 0.483*E + 0.681 *P - 0.606, further most preferably ⁇ 6.90*C - 0.560*E + 0.464*P - 0.495, further most preferably ⁇ 6.48*C - 0.489*E + 0.239*P - 0.436, further most preferably ⁇ 6.06*C - 0.418*E - 0.014*P - 0.377, further most preferably ⁇ 5.64*C
  • inventive alkoxylated compounds preferably satisfying the biodegradability requirements set forth in OECD 301 B.
  • the object is further achieved by the use of the inventive alkoxylated compounds in home care products, cosmetic products, pharmaceutical products, food sector, building materials, lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids, agrochemicals like pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and poly(urethane) applications.
  • lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids, agrochemicals like pesticides, textile and leather auxiliaries, bioprocessing, fuel performance
  • step (b) reacting hydrogen with carbon dioxide to form methanol, (c) converting the methanol from step (b) to ethene and/or propene,
  • step (d) reacting the ethene and/or propene from step (c) with oxygen or an oxidizing agent to form ethylene oxide and/or propylene oxide, wherein the carbon dioxide in step (b) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example fermentation processes from waste or biomass, and/or wherein the hydrogen in step (b) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least in part from non-fossil resources.
  • the present invention further relates to ethylene oxide obtained in step (d) having a total cradle-to-gate product carbon footprint of ⁇ 1 .7 kg CO2e/kg ethylene oxide, preferably ⁇ 1 .6 kg CC>2e/kg ethylene oxide, more preferably ⁇ 1 .5 kg CO2e/kg ethylene oxide, further more preferably ⁇ 1 .4 kg CO2e/kg ethylene oxide, most preferably ⁇ 1 .3 kg CC>2e/kg ethylene oxide, further most preferably ⁇ 1 .2 kg CO2e/kg ethylene oxide, further most preferably ⁇ 1.1 kg CO2e/kg ethylene oxide, even further most preferably ⁇ 1 .0 kg CC>2e/kg ethylene oxide, even further most preferably ⁇ 0.9 kg CO2e/kg ethylene oxide, even further most preferably ⁇ 0.8 kg CO2e/kg ethylene oxide, even further most preferably ⁇ 0.7 kg CO2e/kg ethylene oxide, even further most preferably ⁇
  • steps (b), (c) and (d) of the present invention is not based on starting materials based on biomass feedstocks or biomass balanced feedstocks.
  • the IUPAC name of the term ethylene oxide used in the present application is oxirane (C2H4O). Propylene oxide is in the meaning of the present application 1 ,2-propylene oxide.
  • the IUPAC name of the term propylene oxide used in the present application is 2- methyloxirane (CsHeO).
  • An alternative name is 1 ,2-epoxypropane.
  • An ethylene oxide unit is the reacted form of ethylene oxide in the alkoxylated compound
  • a propylene oxide unit is the reacted form of propylene oxide in the alkoxylated compound
  • an alkylene oxide unit is the reacted form of alkylene oxide in the alkoxylated compound.
  • alkoxylated compound covers alkoxylated compounds composed of at least one ethylene oxide unit and/or propylene oxide unit and at least one starter unit having Zerewitinoff active hydrogen atoms.
  • a "monomer unit” means the reacted form of a monomer substance in a polymer (for the identification of the monomeric unit(s) in the chemical structure of the polymer the mechanism of polymer formation may, for instance, be taken into consideration).
  • a “sequence” is a continuous string of monomer units within the molecule that are covalently bonded to one another and are uninterrupted by units other than monomer units. This continuous string of monomer units can possibly follow any network within the polymer structure.
  • “Other reactant” refers to a molecule that can be linked to one or more sequences of monomer units but which cannot be regarded as a monomer under the relevant reaction conditions used for the polymer formation process.
  • the relevant PCFs of alkoxylated compounds and upstream compounds in its preparation were calculated based on the following Guideline: “The Product Carbon Footprint Guideline for the Chemical Industry” launched by TfS (Together for Sustainability), Version 2.0, November 2022 (https://www.tfs-initiative.com/) (in the following: “TfS guideline”).
  • the Guideline is “Audit-ready”, ISO-compliant, and accepted by the GHG Protocol and further “Open source”, useful for global industries using chemical materials.
  • the unique Verbund system of the applicant creates efficient value chains that extend from basic chemicals all the way to consumer products. This makes it possible to gather reliable data about greenhouse gas (GHG) emissions generated by a product in and beyond the company-owned Verbund, especially generated by alkoxylated compounds and upstream compounds in its preparation process, over the different stages of its life cycle, from cradle-to-gate (scopes 1 , 2 and 3 upstream) as well as from cra- dle-to-grave* (scopes 1 , 2 and 3 upstream and downstream).
  • GOG greenhouse gas
  • the “material carbon” in the polymer product is considered as the only add-on CO2 emissions for the end of life “grave” emissions; all other e.g. transportation and use-related emissions in the products customer and consumer use phase are out of scope.
  • the process for preparing alkoxylated compounds is energy demanding and many of steps (b) to (eO) of the process for preparing the alkoxylated compounds can be carried out by a number of alternative methods.
  • the inventors found a process for the preparation of alkoxylated compounds, wherein each step is optimized or at least prepared for obtaining alkoxylated compounds having a low carbon footprint.
  • methanol preparation step (b) a reaction of hydrogen with carbon dioxide, wherein the carbon dioxide is at least in part, preferably completely captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from fermentation processes from waste or biomass.
  • chlorohydrin process (CHPO; a multi-step process that proceeds via addition of hypochlorous acid to propylene to form a chlorohydrin intermediate, which is subsequently dehydrochlorinated to the epoxide), oxidation of propylene with an organic peroxide including tert-butyl hydroperoxide and ethylbenzene hydroperoxide (MTBE PO process:
  • the by-products include t-butyl alcohol (TBA) for making methyl tert-butyl ethyl (MTBE);
  • SMPO process The by-products include ethylbenzene for styrene production); cumene hydroperoxide process (CHP; use of cumene hydroperoxide (CHP) for the epoxidation of propylene; CHP is obtained by oxidation of cumene with air; on giving up oxygen to propylene
  • alkoxylated compounds having an especially low PCF are obtained when the hydrogen used in step (b) for the preparation of methanol is obtained at least in part by water splitting, preferably electrolysis, based on electrical power generated at least in part from non-fossil resources.
  • the present invention further relates to a process for preparing ethylene oxide or propylene oxide as mentioned above.
  • Steps (b), (c) and (d) in the inventive process for preparing ethylene oxide or propylene oxide are the same as steps (b), (c) and (d) in the inventive process for preparing the alkoxylated compounds, and the definitions of process steps (b), (c) and (d) above and below apply to both processes.
  • steps (b), (c) and (d) above and below apply to both processes.
  • (d) and (eO) energy in form of heating energy and/or electrical power is used, and the energy used is generated at least in part from non-fossil resources.
  • steps (b) to (eO) energy in form of heating energy and/or electrical power is used, and the energy used in steps (b) to (eO) is generated at least in part from non-fossil resources.
  • step (b) energy in form of heating energy and/or electrical power is used, and the energy used is generated at least in part from non-fossil resources.
  • step (b) to step (d) energy in form of heating energy and/or electrical power is used, and the energy used in steps (b) to (d) is generated at least in part from non-fossil resources.
  • non-fossil resources in the process for preparing ethylene oxide and propylene oxide and alkoxylated compounds means that part of the energy can still be produced from fossil fuels, preferably from natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of energy produced than combustion of coal.
  • the portion of energy produced from fossil fuels should be as low as possible, preferably ⁇ 50%, more preferably ⁇ 30%, most preferably ⁇ 20%, further most preferably ⁇ 10% of the energy in step (b), preferably in step (b) and in one or two further of steps (c), (d) and (eO), more preferably in all steps (b) to (eO) is generated from fossil resources.
  • step (b) preferably at least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required energy input used in step (b), preferably in step (b) and in one or two further of steps (c), (d) and (eO), more preferably in all steps (b) to (eO) is generated from non-fossil resources.
  • step (b) the energy in step (b), preferably in step (b) and in one or two further of steps (c), (d) and (eO), more preferably in all steps (b) to (eO) is generated exclusively from non-fossil resources.
  • step (b) the energy in step (b), preferably in step (b) and in one or both further of steps (c) and (d), more preferably in all steps (b) to (eO) is generated exclusively from non-fossil resources.
  • At least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required energy input used in the process of the present invention is generated from non-fossil resources.
  • At least part of the energy used in the process of the present invention is utilized from excess energy generated in other exothermic chemical processes than the process steps of the present invention (typical examples: acrylic acid, formaldehyde or ethylene oxide production), for example in a chemical “Verbund” production setup distributing the excess energy e.g. as steam to endothermic process consumers.
  • Excess steam can substitute steam generated by fossil fuels and be allocated as CO2e credits to the exothermic process source thereby closing the CC>2-balance as described in the “TfS PCF guideline”.
  • Such a Verbund plant is preferably supplied with additional energy generated from non-fossil resources.
  • the energy is generated at least in part from non-fossil resources selected from renewable resources, preferably selected from solar energy (thermal, photovoltaic and concentrated solar power), wind power, hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste and mixtures thereof.
  • renewable resources preferably selected from solar energy (thermal, photovoltaic and concentrated solar power), wind power, hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste and mixtures thereof.
  • alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine, alkoxylated polyethylenimine and surfactants of the present invention are known as such and widely used today or were just recently disclosed as further detailed hereinafter, and thus are known to a person of skill in the art.
  • the petrochemical steam reforming process has its negative impacts with regard to its carbon footprint including the consumption of a lot of fossil-based natural resources and energy.
  • US 2011/136097 relates to a method for determining origins of food products, more specifically for determining the geographic and/or biological origin of food products containing alcohols or sugars by using the specific isotope ratios of fer example sugars from different plants, which is influenced by climate conditions and the area of origin as isotopic “fingerprint” of the specific plants.
  • the deuterium content taken advantage of in the present invention is not the natural “fingerprint”, but the finding that the deuterium content of hydrogen obtained by electrolysis of water is lower than the naturally occurring deuterium content of hydrogen. Further, not the geographic area of origin is determined, but the preparation process of the hydrogen.
  • US 6,495,609 concerns a method for recovering carbon dioxide from an ethylene oxide production process and using the recovered carbon dioxide as a carbon source for methanol synthesis.
  • the hydrogen used in the process of US 6,495,609 is present in syngas, such as natural gas or refinery off-gas.
  • GB 2 464 691 A relates to the manufacture of methanol from agricultural by-product cellulosic/lignitic material.
  • the cellulosic/lignitic by-product that remains after the cropping of agricultural products is converted to carbon dioxide by calorific oxidation.
  • hydrogen gas is produced by electrolysis which is then reacted with carbon dioxide to make methanol.
  • WO 2016/149507 A1 relates to the oxidative coupling of methane for obtaining a high number of different products.
  • Claim 217 for example discloses a method for producing oxalate compounds.
  • US 7,119,231 B2 relates to a process for preparing alkanolamines by reacting ammonia with alkylene oxide in a reaction space in the presence of a catalyst to give monoalkanolamine or dialkanolamine or trialkanolamine or a mixture of two or three of these compounds.
  • a catalyst to give monoalkanolamine or dialkanolamine or trialkanolamine or a mixture of two or three of these compounds.
  • FR 2 851 564 A1 concerns a process for preparation of ethylene oxide and ethanolamines. As in FR 2 851 564 A1 does not contain any hint to the presence of deuterium in the hydrogen-comprising compounds or the use of non-fossil energies.
  • US 2008/0283411 A1 relates to a method for converting a carbon source and a hydrogen source into hydrocarbons. It is mentioned that the method and the device are useful to produce a fossil fuel alternative energy source, store renewable energy, sequester carbon dioxide from the atmosphere, counteract global warming, and store carbon dioxide in a liquid fuel.
  • WO 2015/102985 A1 relates to a process for the preparation of ethanolamines comprising reacting a water-ammonia solution with ethylene oxide.
  • WO 2015/102985 A1 concerning the preparation of hydrogen by electrolysis, the use of renewable energies and the presence of deuterium in the hydrogen-containing compounds disclosed in WO 2015/102985 A1 .
  • DE 195 34 493 A1 relates to a process for the preparation of aziridines in the presence of fine-particle shell catalysts.
  • the aziridine is prepared by dehydration of alkanolamine in the presence of said catalysts.
  • neither an electrolysis of water for the preparation of hydrogen nor the deuterium content of the hydrogen-containing compounds mentioned in DE 195 34 493 A1 nor the use of renewable energies is mentioned in DE 195 34 493 A1.
  • This object is also achieved by use of the molar share of deuterium in hydrogen bound in the inventive compounds based on hydrogen for tracing the origin, especially the energetic origin, of the hydrogen bound in those inventive compounds based on hydrogen; a process for tracing the origin, especially the energetic origin, of hydrogen bound in downstream compounds based on hydrogen by determining the molar share of deuterium in the hydrogen bound in said inventive compounds is also part of the invention.
  • Methods for determination of the molar share of deuterium in hydrogen and in downstream compounds based on hydrogen are known to a person skilled in the art and include mass spectrometry and NMR technologies.
  • the object is achieved by alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine using a process leading to non-fossil based ethyleneoxide and/or propylene oxide, preferably ethylene oxide, which is then used to produce the inventive compounds using known means, wherein the molar share of deuterium is lower than in products made using ethylene oxide (EO) and/or propylene oxide (PO), preferably EO from fossil-based sources only.
  • EO ethylene oxide
  • PO propylene oxide
  • the deuterium content is preferably lower in the products using non-fossil-based-EO and/or PO, preferably EO compared to products using only fossil-based-EO and/or PO, preferably EO by at least 10, more preferably at least 20, even more preferably at least 30, even more preferably at least 50, such as more than 60, 70, 80 or even 90 percent, such percentage being based on the total hydrogen content of units stemming from EO and/or PO, preferably EO having reacted to the compounds of the invention.
  • the object is achieved by a process for making alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine, wherein said process comprises the following steps:
  • (aO) providing hydrogen with a molar share of deuterium ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy,
  • step (a) reacting the hydrogen from step (aO) with nitrogen to form ammonia
  • step (b) reacting the hydrogen from step (aO) with carbon oxides, preferably carbon dioxide to form methanol,
  • step (c) converting the methanol from step (c) to ethylene and/or propylene, preferably ethylene and (d) further, preferably with oxygen or an oxidizing agent, to ethylene oxide and/or propylene oxide, preferably ethylene oxide,
  • step (e1 ) converting the ethylene oxide and/or propylene oxide, preferably ethylene oxide, from step (d) to alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine in one or more steps using known methods.
  • the object is achieved by a process for making alkoxylated polyethylenimine, wherein said process comprises the following steps:
  • (aO) providing hydrogen with a molar share of deuterium ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy,
  • step (a) reacting the hydrogen from step (aO) with nitrogen to form ammonia
  • step (b) reacting the hydrogen from step (aO) with carbon oxides, preferably carbon dioxide to form methanol,
  • step (c) converting the methanol from step (c) to ethylene and/or propylene, preferably ethylene and (d) further, preferably with oxygen, to ethylene oxide and/or propylene oxide, preferably ethylene oxide,
  • step (e) converting the ammonia from step (b) with ethylene oxide from step (d) to ethanolamines in one or more steps
  • step (f) separating monoethanolamine from ethanolamines obtained in step (e),
  • step (h) polymerizing ethylenimine from step (g) to polyethylenimine
  • step (i) alkoxylating the polyethyleneimine from step (g) with the ethylene oxide and/or propylene oxide, preferably ethylene oxide, and optionally further ingredients such as other alkylene oxides and/or lactones, to obtain alkoxylated polyethyleneimines. Further, it is important that the origin of the hydrogen and downstream compounds obtained by clean energy can be tracked in a reliable way.
  • This object is also achieved by use of the molar share of deuterium in hydrogen and downstream compounds based on hydrogen for tracing the origin, especially the energetic origin, of the hydrogen and downstream compounds based on hydrogen, wherein the compounds are preferably alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine, and a process for tracing the origin, especially the energetic origin, of hydrogen and downstream compounds based on hydrogen by determining the molar share of deuterium in hydrogen and said downstream compounds based on hydrogen, wherein the compounds are preferably alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine.
  • a further environmental benefit of the environmentally friendly alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine according to the present invention is their use in carbon capturing processes, since the alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine according to the present invention are produced using as little fossil-based energy as possible, ideally no fossil-based energy, at least with respect to the content derived from EO and/or PO, preferably EO, and do therefore only add as little as possible, ideally nothing, to CO2 emission.
  • the invention of course will be even more environmentally friendly if also for other ingredients, such as the amines, environmentally friendly processes will be employed.
  • the invention encompasses also such even more environmentally friendly products, wherein the amines employed and also further optional ingredients, such as the before mentioned other alkyleneoxides and lactones, are sourced from or made from renewable or even better non-fossil-based sources. Such sources are known already to date.
  • a further embodiment of the present invention is therefore the use of the alkoxylated di- , oligo- and polyamines and alkoxylated polyethylenimine according to the present invention as liquid or solid CO2 absorbents in CO2 capturing processes.
  • the object further encompasses an environmentally friendly process for making the same, that process using as little fossil-based energy as possible, ideally no fossilbased energy, thus such process therefore only adding as little as possible, ideally nothing, to CO2 emission;
  • a further object is the use of the molar share of deuterium in hydrogen and thus in such surfactants based on hydrogen comprise at least one structural units derived from ethylene oxide, methanol, ammonia, ethanolamine, or are produced with hydrogen for tracing the origin, especially the energetic origin, of the hydrogen and thus tracing of such surfactants based on hydrogen, comprising at least one structural units derived from ethylene oxide, methanol, ammonia, ethanolamine, or are produced with hydrogen.
  • the object is achieved by the inventive surfactants comprising at least one structural units derived from ethylene oxide, methanol, ammonia, ethanolamine, or are produced with hydrogen when using a process comprising the steps of producing hydrogen from non-fossil based sources, optionally producing in a further step methanol, ammonia, ethanolamine or ethene or ethylene oxide, of which - or a combination thereof in various order - is then used to produce the inventive surfactants using known means, wherein the molar share of deuterium is lower than in products made using hydrogen, methanol, ammonia, ethanolamine or ethene or ethylene oxide (each of them individually as “starting material” and at least two of them as “starting materials”) from fossil-based sources only.
  • the deuterium content is preferably lower in the products using non-fossil-based-starting material(s) compared to products using only fossil- based-material by at least 10, more preferably at least 20, even more preferably at least 30, even more preferably at least 50, such as more than 60, 70, 80 or even 90 percent, such percentage being based on the total hydrogen content of units stemming from starting material(s) having reacted to the compounds of the invention.
  • the object is achieved by a process for making surfactant comprising at least one structural units derived from ethylene oxide, methanol, ammonia, ethanolamine, or are produced with hydrogen, wherein said process comprises the following steps:
  • (aO) providing hydrogen with a molar share of deuterium ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy,
  • step (a) reacting the hydrogen from step (aO) with nitrogen to form ammonia
  • step (b) reacting the hydrogen from step (aO) with carbon oxides, preferably carbon dioxide to form methanol,
  • step (c) converting the methanol from step (b) to ethylene and (d) further, preferably with oxygen, to ethylene oxide,
  • step (e) converting the ammonia from step (a) with ethylene oxide from step (d) to ethanolamines in one or more steps
  • step (f) separating monoethanolamine, diethanolamine and triethanolamine from ethanolamines obtained in step (e),
  • step a (gO) converting any of the products from step a), b), c), d), and e) in at least one known process step to a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or hydrogen, to obtain a surfactant comprising less deuterium based on total hydrogen content compared to the chemical identical surfactant obtained from fossil-based sources only.
  • a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, ethanolamine, or hydrogen
  • the present invention further relates to a method for tracing surfactants back to its origin, especially also the energetic origin, and to non-fossil based lives is also part of this invention by using the molar share of deuterium in hydrogen and thus in the inventive surfactants based on such hydrogen.
  • a further environmental benefit of the environmentally friendly surfactants according to the present invention is their use in carbon capturing processes, since the surfactants according to the present invention are produced using as little fossil-based energy as possible, ideally no fossil-based energy, at least with respect to the content derived from hydrogen and carbon (via carbon dioxide or carbon monoxide from non-fossil b- based sources) and - optionally - via methanol, ammonia, ethanolamine or ethene or ethylene oxide prepared using such hydrogen from non-fossil based sources, and do therefore only add as little as possible, ideally nothing, to CO2 emission.
  • the invention of course will be even more environmentally friendly if also for other ingredients needed to prepare the surfactants such as alcohols, fatty acids etc, environmentally friendly processes will be employed and - more preferably - such ingredients are also derived from non-fossil-based sources.
  • the invention encompasses also such even more environmentally friendly products, wherein the other ingredients employed for the preparation of the final surfactants are sourced from and/or made from renewable or even better non-fossil-based sources.
  • sources are known already to date for at least some of those other ingredients, such as methanol and higher alcohols, fatty acids, fatty alcohols etc.
  • a further embodiment of the present invention is the use of the surfactants according to the present invention as liquid or solid CO2 absorbents in CO2 capturing processes.
  • a further embodiment of the present invention is the use of the surfactants according to the present invention as in compositions, products or formulations, wherein such compositions, products or formulations are those as currently known for the use of the conventionally produced surfactants of the same - besides the difference in deuterium content - chemically identical surfactants.
  • ppm based on the total hydrogen content
  • mol-ppm content of deuterium based on the total hydrogen content (in hydrogen or in the compounds discussed, respectively).
  • deuterium content of hydrogen and downstream compounds based on hydrogen is given in the present application in atom-ppm based on the total molar hydrogen content (total atoms of protium 1 H and deuterium 2 H).
  • deuterium content and “molar share of deuterium” are used synonymously throughout the application.
  • a kinetic isotope effect is the change in the reaction rate of a chemical reaction when one of the atoms in the reactants is replaced by one of its isotopes.
  • it is the ratio of rate constants ki. I kn for the reactions involving the light (ki) and the heavy (kn) isotopically substituted reactants (isotopologues).
  • This change in reaction rate is a quantum mechanical effect that primarily results from heavier isotopologues having lower vibrational frequencies compared to their lighter counterparts. In most cases, this implies a greater energetic input needed for heavier isotopologues to reach the transition state, and consequently a slower reaction rate.
  • Isotopic rate changes are most pronounced when the relative mass change is greatest, since the effect is related to vibrational frequencies of the affected bonds. For instance, changing a hydrogen atom (H) to its isotope deuterium (D) represents a 100 % increase in mass, whereas in replacing 12 C with 13 C, the mass increases by only 8 percent.
  • the rate of a reaction involving a C-H bond is typically 6-10 times faster than the corresponding C-D bond, whereas a 12 C reaction is only 4 percent faster than the corresponding 13 C reaction.
  • a primary kinetic isotope effect may be found when a bond to the isotope atom is being formed or broken.
  • a secondary kinetic isotope effect is observed when no bond to the isotope atom in the reactant is broken or formed. Secondary kinetic isotope effects tend to be much smaller than primary kinetic isotope effects; however, secondary deuterium isotope effects can be as large as 1.4 per deuterium atom.
  • the processes for making alkoxylated di-, oligo- and polyamines, alkoxylated polyethyl- enimine, alkoxylated polyethylenimine and surfactants of according to the present invention comprise the provision of hydrogen with a molar share of deuterium below 90 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy (sometimes described as step (aO) in the description of the present invention).
  • the electrical power is generated at least in part from non-fossil resources.
  • the term “at least in part” means that part of the electrical power can still be produced from fossil fuels, preferably from natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of electrical energy produced than combustion of coal.
  • the portion of electrical energy produced from fossil fuels should be as low as possible, preferably ⁇ 50%, preferably ⁇ 30%, most preferably ⁇ 20%, further most preferably ⁇ 10%.
  • the electrical power is generated exclusively from non-fossil resources.
  • the electrical power is generated at least in part from wind power, solar energy (thermal, photovoltaic and concentrated solar power), hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, ambient or industrial heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste energy sources or nuclear energy (fission).
  • solar energy thermo, photovoltaic and concentrated solar power
  • hydroelectricity titanium power, wave power, hydroelectric dams, In-river-hydrokinetics
  • geothermal energy ambient or industrial heat captured by heat pumps
  • bioenergy biofuel, biomass
  • nuclear energy nuclear energy
  • the electrical power is generated at least in part from renewable resources, preferably from wind power, solar energy (thermal, photovoltaic and concentrated solar power), hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, ambient heat captured by heat pumps, bioenergy (biofuel, biomass), or the renewable part of waste.
  • renewable resources preferably from wind power, solar energy (thermal, photovoltaic and concentrated solar power), hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, ambient heat captured by heat pumps, bioenergy (biofuel, biomass), or the renewable part of waste.
  • aO alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine and surfactants: (aO) providing hydrogen with a molar share of deuterium ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy.
  • the definitions regarding the molar share of deuterium generally apply to all embodiments of the processes for making alkoxylated di-, oligo- and polyamines or alkoxylated polyethylenimine, alkoxylated polyethylenimine and surfactants. Specific embodiments regarding specific processes are mentioned above and below.
  • the definitions regarding the electrolysis based on energy, especially electrical power generated at least in part from non-fossil energy also generally apply to all embodiments of the processes for making alkoxylated di-, oligo- and polyamines or alkoxylated polyethylenimine, alkoxylated polyethylenimine and surfactants. However, said definitions also apply to the other inventive processes for preparing ethylene oxide or propylene oxide, ethanolamines, polyethylenimine and alkoxylated compounds. Specific embodiments regarding specific processes are mentioned above and below.
  • Steps (b), (c) and (d) in the inventive process for preparing ethylene oxide or propylene oxide are generally the same as steps (b), (c) and (d) in the inventive process for preparing the ethanolamines, polyethylenimine, alkoxylated compounds, alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine, and surfactants, and the definitions of process steps (b), (c) and (d) above and below apply to all processes.
  • steps (b), (c) and (d) in the inventive processes for preparing ethylene oxide or propylene oxide, ethanolamines, polyethylenimine, alkoxylated compounds, alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine and surfactants are mentioned below, as well as specific embodiments of the further steps for preparing the ethanolamines, polyethylenimine, alkoxylated compounds, alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine, and surfactants.
  • Steps (a), (b), (c), (d) and (e) in the inventive process for preparing ethanolamines are generally the same as steps (a), (b), (c), (d) and (e) in the inventive process for preparing polyethylenimine, alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine and surfactants, and the definitions of process steps (a), (b), (c), (d) and (e) above and below apply to all processes mentioned in this paragraph.
  • steps (a), (b), (c), (d) and (e) in the inventive processes for preparing for preparing polyethylenimine, alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine, and surfactants are mentioned below, as well as specific embodiments of the further steps for preparing polyethylenimine, alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine, and surfactants.
  • Steps (a), (b), (c), (d), (e), (f) and (g) in the inventive process for preparing polyethylenimine are generally the same as steps (a), (b), (c), (d), (e), (f) and (g) in the inventive process for preparing alkoxylated polyethylenimine and surfactants, and the definitions of process steps (a), (b), (c), (d), (e), (f) and (g) above and below apply to all processes mentioned in this paragraph.
  • steps (a), (b), (c), (d), (e), (f) and (g) in the inventive processes for preparing for preparing polyethylenimine, alkoxylated polyethylenimine and surfactants are mentioned below, as well as specific embodiments of the further steps for preparing polyethylenimine, alkoxylated polyethylenimine and surfactants.
  • Steps (a), (b), (c), (d), (e), (f), (g) and (h) in the inventive process for preparing polyethylenimine are generally the same as steps (a), (b), (c), (d), (e), (f), (g) and (h) in the inventive process for preparing alkoxylated polyethylenimine, and the definitions of process steps (a), (b), (c), (d), (e), (f), (g) and (h) above and below apply to all processes mentioned in this paragraph.
  • steps (a), (b), (c), (d), (e), (f), (g) and (h) in the inventive processes for preparing for preparing polyethylenimine and alkoxylated polyethylenimine are mentioned below, as well as specific embodiments of the further steps for preparing alkoxylated polyethylenimine.
  • the energy (electrical power) from non-fossil resources used in the process according to the invention can be generated at least in part by nuclear energy.
  • the nuclear energy can be obtained by fission.
  • Fission occurs when a neutron enters a larger atomic nucleus, forcing it to excite and spilt into two smaller atoms —also known as fission products. Additional neutrons are also released that can initiate a chain reaction. When each atom splits, a tremendous amount of energy is released. Uranium and plutonium isotopes are most commonly used for fission reactions in nuclear power reactors because they are easy to initiate and control. The energy released by fission in these reactors heats water into steam. The steam is used to spin a turbine to produce carbon-free electricity.
  • the electrical power from non-fossil resources used in water electrolysis according to the invention is preferably generated from wind power, solar energy, biomass, hydropower and geothermal energy.
  • the energy (electrical power) used in the process according to the invention is generated at least in part from wind power.
  • Wind power can be used to run wind turbines.
  • Modern utility-scale wind turbines range from around 600 kW to 9 MW of rated power.
  • the power available from the wind is a function of the cube of the wind speed, so as wind speed increases, power output increases up to the maximum output for the particular turbine.
  • Areas where winds are stronger and more constant, such as offshore and high- altitude sites, are preferred locations for wind farms.
  • the energy (electrical power) used in the process according to the invention is generated at least in part from solar power, particularly preferred from photovoltaic systems.
  • a photovoltaic system converts light into electrical direct current (DC) by taking advantage of the photoelectric effect.
  • Concentrated solar power (CSP) systems use lenses or mirrors and tracking systems to focus a large area of sunlight into a small beam. CSP-Stirling currently has by far the highest efficiency among all solar energy technologies.
  • the energy (electrical power) used in the process according to the invention is generated at least in part from hydropower.
  • hydropower There are many forms of hydropower.
  • hydroelectric power comes from constructing large hydroelectric dams and reservoirs.
  • Small hydro systems are hydroelectric power installations that typically produce up to 50 MW of power. They are often used on small rivers or as a low-impact development on larger rivers.
  • Run-of-the-river hydroelectricity plants derive energy from rivers without the creation of a large reservoir.
  • the water is typically conveyed along the side of the river valley (using channels, pipes and/or tunnels) until it is high above the valley floor, whereupon it can be allowed to fall through a penstock to drive a turbine.
  • Wave power which captures the energy of ocean surface waves
  • tidal power converting the energy of tides
  • the energy (electrical power) used in the process according to the invention is generated at least in part from geothermal energy.
  • Geothermal energy is the heat that comes from the sub-surface of the earth. It is contained in the rocks and fluids beneath the earth’s crust and can be found as far down to the earth’s hot molten rock, magma.
  • To produce power from geothermal energy wells are dug a mile deep into underground reservoirs to access the steam and hot water there, which can then be used to drive turbines connected to electricity generators.
  • geothermal power plants dry steam, flash and binary.
  • Dry steam is the oldest form of geothermal technology and takes steam out of the ground and uses it to directly drive a turbine. Flash plants use high-pressure hot water into cool, low-pressure water whilst binary plants pass hot water through a secondary liquid with a lower boiling point, which turns to vapor to drive the turbine.
  • the energy (electrical power) used in the process according to the invention is generated at least in part from biomass.
  • Biomass is biological material derived from living, or recently living organisms. It most often refers to plants or plant-derived materials which are specifically called lignocellulosic biomass.
  • biomass can either be used directly via combustion to produce heat (e.g. heat from fermentation processes) or electricity, or indirectly after converting it to various forms of biofuel and gas. Conversion of biomass to biofuel can be achieved by different methods which are broadly classified into: thermal, chemical, and biochemical methods.
  • Industrial biomass can be grown from numerous types of plants, including miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, bamboo, and a variety of tree species, ranging from eucalyptus to oil palm (palm oil). Plant energy is produced by crops specifically grown for use as fuel that offer high biomass output per hectare with low input energy. The grain can be used for liquid transportation fuels while the straw can be burned to produce heat or electricity. Biomass can be converted to other usable forms of energy such as methane gas or transportation fuels such as ethanol and biodiesel.
  • Crops such as corn and sugarcane, can be fermented to produce the transportation fuel, ethanol.
  • Biodiesel another transportation fuel, can be produced from left-over food products such as vegetable oils and animal fats.
  • Biopower technologies convert renewable biomass fuels into heat and electricity using processes like those used with fossil fuels. There are three ways to harvest the energy stored in biomass to produce biopower: burning, bacterial decay, and conversion to a gas or liquid fuel. Biopower can offset the need for carbon fuels burned in power plants, thus lowering the carbon intensity of electricity generation. Unlike some forms of intermittent renewable energy, biopower can increase the flexibility of electricity generation and enhance the reliability of the electric grid.
  • the hydrogen may generally be obtained by any process known in the art.
  • Hydrogen can be produced using a number of different processes. Thermochemical processes use heat and chemical reactions to release hydrogen from organic materials, such as fossil fuels and biomass, or from materials like water. Water (H2O) can also be split into hydrogen (H2) and oxygen (O2) using electrolysis or solar energy. Microorganisms such as bacteria and algae can produce hydrogen through biological processes. Said processes are known in the art (see for example https://en.wikipedia.org/wiki/Hydro- gen_production and https://www.energy.gov/eere/fuelcells/hydrogen-production-pro- Deads).
  • the hydrogen in step (a) and/or (b) is obtained using energy (especially electrical power) generated at least in part from non-fossil resources.
  • the hydrogen in step (a) and/or (b) in the inventive processes for preparing ethylene oxide or propylene oxide, ethanolamines, polyethylenimine and alkox- ylated compounds is obtained at least in part by water splitting, preferably by electrolysis. Most preferably, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources.
  • step (a) and/or (b) produced by other methods than by water splitting should be as low as possible.
  • step (a) and/or (b) of the inventive processes for preparing ethylene oxide or propylene oxide ethanolamines, polyethylenimine and alkoxylated compounds ⁇ 50%, preferably ⁇ 30%, most preferably ⁇ 20%, further most preferably ⁇ 10% of the hydrogen is produced by other methods than by water splitting.
  • the hydrogen in step (a) is produced exclusively by water splitting, preferably by electrolysis.
  • the hydrogen in step (a) and/or (b) of the inventive processes for preparing ethylene oxide or propylene oxide, ethanolamines, polyethylenimine and alkoxylated compounds having a total cradle-to-gate product carbon footprint of ⁇ 5 kg CO2e/kg hydrogen, preferably ⁇ 4.6 kg CO2e/kg hydrogen, more preferably ⁇ 3.5 kg CO2e/kg hydrogen, most preferably ⁇ 2.5 kg CO2e/kg hydrogen, further most preferably ⁇ 2 kg CC>2e/kg hydrogen.
  • the hydrogen in step (a) and/or (b) in the inventive processes for preparing alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine and surfactants is obtained by electrolysis based on electrical power generated at least in part from non-fossil energy,
  • Hydrogen can be defined according to the energy sources for its production, and often a color code is used to categorize hydrogen. For example, hydrogen produced using renewable energy might be referred to as renewable hydrogen or green hydrogen. Hydrogen produced from coal may be called brown hydrogen, and hydrogen produced from natural gas or petroleum might be referred to as grey hydrogen. Brown or grey hydrogen production combined with carbon capture and storage/sequestration might be referred to as blue hydrogen. Hydrogen produced with nuclear energy may be called pink hydrogen or clean hydrogen.
  • the hydrogen used in steps (a) and/or (b) in the process of the present invention which is not obtained by water splitting, preferably by electrolysis, using energy generated at least in part from non-fossil resources, may generally be obtained by any process known in the art using any suitable energy, i.e. said hydrogen may be of any color mentioned above.
  • the hydrogen which is not obtained by water splitting, preferably by electrolysis, using energy generated at least in part from non- fossil resources is blue hydrogen obtained by steam methane reforming (SMR) with carbon capture and storage (CCS), i.e. a process used to produce hydrogen gas from natural gas while capturing and storing the resulting carbon dioxide emissions.
  • SMR steam methane reforming
  • CCS carbon capture and storage
  • the hydrogen used in steps (a) and/or (b) in the process of the present invention which is obtained by water splitting, preferably by electrolysis, but using energy generated from fossil resources, may generally obtained by using any energy generated from fossil resources known in the art.
  • a preferred fossil resource is natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of energy produced than combustion of fer example coal.
  • the portion of energy produced from fossil fuels should be as low as possible in the process of the present invention.
  • the hydrogen in steps (a) and/or (b) is obtained by water splitting, preferably by electrolysis, the energy is fully generated from non-fossil resources.
  • Water splitting preferably the electrolysis of water, is an environmentally friendly method for production of hydrogen because it uses renewable H2O and produces only pure oxygen as by-product.
  • the water splitting can generally performed by known processes like electrolysis; photocatalytic water splitting, also called photoelectrochemical (PEC) water splitting; chemically assisted electrolysis, e.g.
  • CAWE carbon/hydrocarbon assisted water electrolysis
  • radiolysis ultrasound
  • thermolysis especially via solar energy, e.g involving using solar concentrators to directly collect solar energy to heat water
  • pyrolysis on biomass nuclear-assisted thermolysis, e.g in a high-tempera- ture gas-cooled reactor (HTGR); thermochemical cycle combining solely heat sources (thermo) with chemical reactions to split water into its hydrogen and oxygen components, e.g the sulfur-iodine cycle (S-l cycle); ferrosilicon method; photobiological water splitting and mixtures thereof.
  • HTGR high-tempera- ture gas-cooled reactor
  • S-l cycle sulfur-iodine cycle
  • ferrosilicon method photobiological water splitting and mixtures thereof.
  • any water source can be used in the water splitting.
  • the water splitting in the inventive processes for preparing ethylene oxide or propylene oxide, ethanolamines, polyethylenimine and alkoxylated compounds is performed by electrolysis and/or photocatalytic water splitting, more preferably by electrolysis.
  • photocatalytic hydrogen is produced from water using sunlight and one or more photocatalysts, in general specialized semiconductors called photoelectrochemical materials, which use light energy to directly dissociate water molecules into hydrogen and oxygen.
  • the photocatalysts (semiconductor materials) used in the photocatalytic (PEC) process are similar to those used in photovoltaic solar electricity generation, but for photocatalytic (PEC) applications the photocatalyst (semiconductor) is generally immersed in a water-based electrolyte, where sunlight energizes the water-splitting process.
  • PEC reactors can for example be constructed in panel form (similar to photovoltaic panels) as electrode systems or as slurry-based particle systems.
  • the most preferred water electrolysis generally utilizes as electrical power direct current (DC) at least in part from non-fossil energy resources. It is now observed as a key observation of the present application, especially the invention concerning alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine and surfactants, that by the electrolysis of water, the deuterium atom content of the hydrogen is lower than in the hydrogen generated petrochemically, for example as contained in fossil-based synthesis gas, i.e.
  • ⁇ 100 ppm preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content.
  • the deuterium atom content in electrolytically produced hydrogen may be as low as 10 ppm.
  • the remaining deuterium is mainly present in the form of D-H rather than D2.
  • alkaline water electrolysis Hydrogen production by alkaline water electrolysis is a well-established technology up to the megawatt range for a commercial level.
  • KOH/NaOH alkaline solution
  • OH- hydroxyl ions
  • the produced H2 emanates from the cathode surface in gaseous form and the hydroxyl ions (OH-) migrate under the influence of the electrical field between anode and cathode through the porous diaphragm to the anode, where they are discharged to half a molecule of oxygen (O2) and one molecule of water (H2O).
  • Alkaline electrolysis operates at lower temperatures such as 30-100°C, preferably 30 - 80°C, with alkaline aqueous solution (KOH/NaOH) as the electrolyte, the concentration of the electrolyte being about 20% to 30 %.
  • the diaphragm in the center (middle) of the electrolysis cell separates the cathode and anode and also separates the produced gases from their respective electrodes, avoiding the mixing of the produced gases.
  • alkaline electrolysis has negative aspects such as limited current densities (below 400 mA/cm 2 ), low operating pressure and low energy efficiency.
  • hydrogen is provided by polymer electrolyte membrane water electrolysis.
  • Variants of polymer electrolyte membrane water electrolysis are proton exchange membrane water electrolysis (PEMWE, PEM water electrolysis) and anion exchange membrane water electrolysis (AEMWE, AEM water electrolysis).
  • PEM water electrolysis technology is similar to the PEM fuel cell technology, where solid polysulfonated membranes (Nation®, fumapem®) are used as an electrolyte (proton conductor). These proton exchange membranes have many advantages such as low gas permeability, high proton conductivity (0.1 ⁇ 0.02 S cm -1 ), low thickness (20- 300 pm), and allow high-pressure operation. In terms of sustainability and environmental impact, PEM water electrolysis is one of the most favorable methods for conversion of renewable energy to highly pure hydrogen. PEM water electrolysis has great advantages such as compact design, high current density (above 2 A cm -2 ), high efficiency, fast response, operation at low temperatures (20-90°C) and production of ul- trapure hydrogen.
  • the state-of-the-art electrocatalysts for PEM water electrolysis are highly active noble metals such as Pt/Pd for the hydrogen evolution reaction (HER) at the cathode and lrO2/ uO2 for the oxygen evolution reaction (OER) at the anode.
  • PEM water electrolysis One of the largest advantages of PEM water electrolysis is its ability to operate at high current densities. This can result in reduced operational costs, especially for systems coupled with very dynamic energy sources such as wind and solar power, where sudden spikes in energy output would otherwise result in uncaptured energy.
  • the polymer electrolyte allows the PEM water electrolyzer to operate with a very thin membrane (ca. 100-200 pm) while still allowing high operation pressure, resulting in low ohmic losses, primarily caused by the conduction of protons across the membrane (0.1 S/cm), and a compressed hydrogen output.
  • the PEM water electrolyzer utilizes a solid polymer electrolyte (SPE) to conduct protons from the anode to the cathode while insulating the electrodes electrically.
  • SPE solid polymer electrolyte
  • the enthalpy required for the formation of water is 285.9 kJ/mol.
  • One portion of the required energy for a sustained electrolysis reaction is supplied by thermal energy and the remainder is supplied through electrical energy.
  • the half reaction taking place on the anode side of a PEM water electrolyzer is commonly referred to as the Oxygen Evolution Reaction (OER).
  • OER Oxygen Evolution Reaction
  • the liquid water reactant is supplied to a catalyst where it is oxidized to oxygen, protons and electrons.
  • the half reaction taking place on the cathode side of a PEM water electrolyzer is commonly referred to as the Hydrogen Evolution Reaction (HER).
  • HER Hydrogen Evolution Reaction
  • the protons that have moved through the membrane are reduced to gaseous hydrogen.
  • PEMs can be made from either pure polymer membranes or from composite membranes, where other materials are embedded in a polymer matrix.
  • One of the most common and commercially available PEM materials is the fluoropolymer PFSA (e.g. National®, a DuPont product). While Nation® is an ionomer with a perfluorinated backbone like Teflon, there are many other structural motifs used to make ionomers for pro- ton-exchange membranes. Many use polyaromatic polymers, while others use partially fluorinated polymers.
  • A V x p / (J/2F x 60 x M H 2O)
  • V (mL min 1 ) is the water mass flow in the anode
  • F is the Faraday constant
  • J electrolysis current (A)
  • p is the density of water (g mL 1 )
  • MH2O (g mob 1 ) is the molar weight of water.
  • a stoichiometric number A of 10 means that 10 times the amount of fresh water than can be theoretically consumed by electrolysis at the given electrolysis current is supplied to the anode.
  • deuterium in the evolving hydrogen gas can easily be depleted by a factor of from 2 to 5 with regard to feed water in polymer electrolyte membrane water electrolysis.
  • the electrolysis conditions water flow, current density
  • even higher depletion factors are possible.
  • the average deuterium content of water is about 150 ppm, based on the total hydrogen content
  • hydrogen provided in step (a) of the inventive process may have a deuterium content of from 30 to 75 ppm, based on the total hydrogen content, or even lower.
  • the AEM water electrolysis technology adopts low-cost catalytic materials, as in alkaline electrolysis, and a solid polymer electrolyte architecture, as in PEM electrolysis technology.
  • the membrane used in this type of electrolysis is a polymeric membrane, containing quaternary ammonium salts. It is relatively inexpensive and has low interaction with atmospheric CO2.
  • HER hydrogen evolution reaction
  • catalysts based on Ni- Mo alloyed materials are suitable.
  • oxygen evolution reaction (OER) catalysts high activity of transition metal mixed oxides are suitable.
  • Specific examples are CuxCo3_xO4, NiCo2O4:Fe and Ni-Fe alloys on Ni foam supports, for example the PGM-free catalysts (Ni-Fe, Ni-Mo, Ni/(CeO2-La2O3)/C and CuxCo3_xO4).
  • Liquid electrolyte Pure water feeds generally result in poor current densities while 1 % K2CO3 or dilute KOH solutions give good results. A good electrolysis performance is achieved with a 1% K2CO3 electrolyte. It is therefore preferable that the water electrolyte comprises 0.1 to 2 wt% K2CO3 or KOH.
  • SOE solid oxide electrolysis
  • SOEC solid oxide electrolysis cell feeds water into the cathode and the water undergoes water reduction reaction (WRR), which converts water into hydrogen gas and oxide ions. This hydrogen gas is later brought to purification modules to separate hydrogen gas from the remaining water. Then, the oxide ions migrate from cathode to anode and they release electrons to external circuit to become oxygen gas via oxygen evolution reaction (OER).
  • OER oxygen evolution reaction
  • the operating temperatures for SOFCs are from 800 to 1 ,000 °C, because high temperatures are required to thermally activate the migration of oxide ions and to facilitate electrochemical reactions on both electrodes. As a result, the overall efficiency is improved.
  • the SOEC is for example described in K. Kamlung- sua et al., FUEL CELLS 20, 2020, No. 6, 644-649.
  • the electrolysis for obtaining hydrogen is a water electrolysis, more preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.
  • the electrolysis for obtaining hydrogen is a solid oxide water electrolysis (SOE).
  • SOE solid oxide water electrolysis
  • deuterium in the evolving hydrogen gas can be depleted with regard to feed water in water electrolysis, e.g. polymer electrolyte membrane water electrolysis.
  • the depletion factor is depending on the electrolysis conditions (water flow, current density).
  • hydrogen provided in step (a) of the inventive process has a molar share of deuterium (deuterium content) of ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, or even lower.
  • any water source can be used in the preferred water electrolysis in step (a).
  • the hydrogen prepared in step (a) has a molar share of deuterium (deuterium content) below ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, it is preferable to use water having a molar share of deuterium (deuterium content) below 160 ppm, based on the total hydrogen content.
  • VSMOW Vienna Standard Mean Ocean Water
  • H2O pure water
  • VSMOW serves as a reference standard for comparing hydrogen and oxygen isotope ratios, mostly in water samples.
  • Very pure, distilled VSMOW water is also used for making high accuracy measurement of water’s physical properties and for defining laboratory standards since it is considered to be representative of “average ocean water”, in effect representing the water content of Earth.
  • the isotopic composition of VSMOW water is specified as ratios of the molar abundance of the rare isotope in question divided by that of its most common isotope and is expressed as parts per million (ppm). For instance 16 O (the most common isotope of oxygen with eight protons and eight neutrons) is roughly 2,632 times more prevalent in sea water than is 17 O (with an additional neutron).
  • the isotopic ratios of VSMOW water are defined as follows:
  • the water in step (a) has an average deuterium content of 1 ppm (super light water to 156 ppm, based on the total hydrogen content, most preferably 2 ppm to 150 ppm, based on the total hydrogen content.
  • Processes for the depletion of deuterium in water are known by a person skilled in the art. However, said processes are generally energy consuming electrolysis processes as e.g. described in CN103848399A.
  • deuterium depleted water obtained from the following resources:
  • a byproduct of “heavy water” (D2O) production (heavy water has applications in organic chemistry, drug development, and nuclear reactors); (deuterium content about 10-120 ppm)
  • Pole water and antarctic glacier water (deuterium content about 90-150 ppm)
  • Low salinity sea water e.g. close to river mouths, desalinated sea water or brackish water and waste water treatment effluent water; (deuterium content about 130 - 155 ppm)
  • Step (a) concerns reacting hydrogen with nitrogen to form ammonia.
  • the hydrogen is obtained in the inventive processes for preparing ethylene oxide or propylene oxide, ethanolamines, polyethylenimine and alkoxylated compounds at least in part by water splitting, preferably by electrolysis, using energy generated at least in part from nonfossil resources. Suitable and preferred processes for generating the hydrogen in step (a) are mentioned above.
  • the hydrogen is obtained in the inventive processes for preparing alkoxylated di-, oligo- and polyamines, alkoxylated polyethylenimine and surfactants by electrolysis based on electrical power generated at least in part from non-fossil energy.
  • step (a) preferably follows the Haber-Bosch process.
  • Fused-iron catalysts are derived from iron oxides, of which there are three possibilities: Fe2Os, FesO4, and Fei- O, which are known as hematite, magnetite, and wustite, respectively.
  • these iron catalysts will be multipromoted with promoters such as K2O, BaO, KOH, CaO, MgO and AI2O3 are present in small quantities of a few weight percentage.
  • Supported metallic catalysts are catalysts made up of a metallic catalyst material, normally ruthenium or cobalt for the ammonia synthesis reaction, present on the surface of a support material, normally activated carbon or a metal oxide. Commonly the weight percentage of the metallic catalyst is around 2-10%.
  • catalysts which may be used are nickel, and nitride catalyst systems or electride, hydride, nitride, oxynitride hydride promoted Ru, Fe, Co, and Ni catalysts.
  • the catalysts mentioned above can be used for both conventional centralized large- scale Haber-Bosch ammonia synthesis plants and distributed small-scale ammonia production via the same process.
  • step (a) is performed at a pressure in the range of from 50 to 350 bar (abs), preferably 150 to 300 bar (abs).
  • step (a) is performed at a temperature in the range of from 300 to 600 °C, preferably 400 to 500 °C.
  • step (a) ammonia is formed.
  • the deuterium content is even lower than corresponding to the distribution obtained by classical petrochemical routes.
  • Step (b) concerns reacting hydrogen with carbon oxides, preferably carbon dioxide to form methanol.
  • carbon oxides preferably carbon dioxide
  • Step (b) concerns reacting hydrogen with carbon oxides, preferably carbon dioxide to form methanol.
  • the hydrogen is obtained at least in part by water splitting, preferably by electrolysis, using energy generated at least in part from non-fossil resources. Suitable and preferred processes for generating the hydrogen in step (b) are mentioned above.
  • step (b) generally comprises reacting hydrogen with carbon dioxide to form methanol.
  • step (b) preferably concerns reacting hydrogen having a molar share of deuterium ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy (e.g. from step (aO) in the process described in the description) with carbon oxides, preferably carbon dioxide to form methanol.
  • non-fossil energy e.g. from step (aO) in the process described in the description
  • Suitable carbon oxides are carbon monoxide, carbon dioxide or mixtures of both, wherein carbon dioxide is preferred.
  • the carbon dioxide in step (b) is fully or at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass.
  • alkoxylated compounds and ethylene oxide or propylene oxide, respectively are provided having a low cradle to grave (i.e. including scope 3 downstream (for details: see above)) product carbon footprint (PCF) and the alkoxylated compounds generally having at the same time a good biodegradability.
  • the term “at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass” means that part of the carbon dioxide can still be obtained from other sources.
  • carbon dioxide is obtained tech- nically by burning coke with excess air or as a by-product of lime burning and subsequent purification and natural gas sources (mineral water) are also used for extraction.
  • the portion of carbon dioxide obtained from other sources than from capturing from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass should be as low as possible in the process of the present invention, preferably ⁇ 50%, preferably ⁇ 30%, most preferably ⁇ 20%, further most preferably ⁇ 10%.
  • the carbon dioxide is exclusively obtained from capturing from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass.
  • At least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required carbon dioxide used in step (a) in the process of the present invention is captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass.
  • step (b) By performing step (b) according to the embodiment of the inventive process for preparing ethylene oxide or propylene oxide and the embodiment of the inventive process for preparing alkoxylated compounds, wherein it is mandatory that the carbon dioxide in step (b) is fully or at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass, methanol is formed, CH3OH, by reacting carbon dioxide which is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from fermentation processes from waste or biomass with hydrogen.
  • the low-pressure synthesis is generally carried out at pressures between 50 and 100 bar.
  • the temperature is generally 220 to 300°C.
  • a catalyst generally a catalyst based on Cu, Zn and AI2O3 (e.g. CuO/ZnO/AhOs) is used.
  • the low-pressure synthesis is the most preferred synthesis for the preparation of methanol from carbon monoxide or from mixtures of carbon monoxide and carbon dioxide.
  • the medium-pressure-synthesis is generally carried out at pressures between 100 and 250 bar.
  • the temperature is generally up to 300°C.
  • catalysts generally a catalyst based on Zn/C ⁇ Os or Zn-Cu catalysts are used.
  • High-pressure synthesis The high-pressure-synthesis is generally carried out at pressures between 250 and 350 bar.
  • the temperature is generally 320 to 380°C.
  • a catalyst based on zinc-chromium oxide is used. This process is less preferred for the production of methanol from carbon monoxide or from mixtures of carbon monoxide and carbon dioxide.
  • methanol is prepared by reacting hydrogen in case of ethanolamines, polyethylenimine, ammonia, ethylene oxide, propylene oxide, alkoxylated compounds hydrogen obtained at least in part by water splitting, preferably by electrolysis, using energy generated at least in part from nonfossil resources and in case of alkoylated di-, oligo- and polyamines, alkoxyl
  • the carbon dioxide that is provided in step (b) is fully or at least in part captured from industrial flue gases or from air, preferably ambient air, or - in case of ethanolamines, polyethylenimine, ammonia, ethylene oxide, propylene oxide, alkoxylated compounds - from ocean water or other natural waters. All available capture technologies may be used. An overview of commercial CO2 capturing technologies is given in Koytsoumoa et aL, The Journal of Supercritical Fluids, Volume 132, February 2018, Pages 3-16 and NexantECA, Carbon Capture and Sequestration (CCS) Technologies, TECH 2022S7, Christopher Ho, Caleb Chong, Alexander Zoelle, October 2022. CO2 capturing from ocean water and other natural waters is for example described in https://arpa-e.en- ergy.gov/technologies/exploratory-topics/direct-ocean-capture.
  • CO2 is most cost-effective at point sources, such as large carbon-based energy facilities, industries with major CO2 emissions (e.g. cement production, ammonia synthesis, steel making), natural gas processing, synthetic fuel plants and fossil fuelbased hydrogen production plants. Extracting CO2 from air is possible, although the lower concentration of CO2 in air compared to combustion sources complicates the engineering and makes the process therefore more expensive.
  • the carbon dioxide that is provided in step (b) is fully or at least in part captured from industrial flue gases.
  • the main industrial sources of CO2 are power plants based on burning of fossil fuels, oil refineries, biogas sweetening (e.g. fermentation) as well as the production of chemicals.
  • Relevant chemical production processes are e.g. naphtha cracking for C1-C4 olefins and Ce aromatics as well as downstream chemicals such as especially ammonia (based on steam reformed natural gas) and other CC>2-intensive products.
  • industrial paper, food, cement, mineral and iron and steel production can be named as examples.
  • CO2 is removed after combustion of the fossil fuel — this is the scheme that would apply to fossil-fuel power plants.
  • CO2 is captured from flue gases at power stations or other point sources.
  • Absorption, or carbon scrubbing with amines is the dominant capture technology. It is the only carbon capture technology so far that has been used industrially.
  • Suitable post carbon capture methods are for example absorption (chemical, physical), adsorption (chemical, physical), membrane processes, biological and cryogenic processes.
  • Pre-conversion capture means capturing CO2 generated as an undesired co-product of an intermediate reaction of a conversion process.
  • Some examples include the production of ammonia and coal gasification in power plants.
  • CO2 that is co-produced with hydrogen during steam reforming must be removed before the ammonia synthesis can take place - absorption in monoethanolamine (MEA) and/or diethanolamine (DEA) is commonly used for these purposes.
  • MEA monoethanolamine
  • DEA diethanolamine
  • CO2 in an integrated gasification combined cycle (IGCC) power plant, CO2 must be separated from hydrogen. This is typically achieved using physical solvents such as selexol and rectisol. Note that, when applied in power plants, pre-conversion capture is also referred to as precombustion capture.
  • Oxy-fuel combustion technology involves the combustion of carbonaceous fuel in a stream of pure oxygen instead of air. Since the oxidant (O2) is free of other components in the air (such as nitrogen), the CO2 concentration in the flue gas will be very high, while the water vapor content can be easily removed.
  • O2 oxidant
  • CO2 adsorbs to a MOF (Metal-organic framework) through physisorption or chemisorption based on the porosity and selectivity of the MOF leaving behind a CO2 poor gas stream.
  • MOF Metal-organic framework
  • the CO2 is then stripped off the MOF using temperature swing adsorption (TSA) or pressure swing adsorption (PSA) so the MOF can be reused.
  • TSA temperature swing adsorption
  • PSA pressure swing adsorption
  • the carbon dioxide that is provided in step (b) is fully or at least in part captured from air, preferably ambient air.
  • Direct air capture is a process of capturing carbon dioxide (CO2) directly from the ambient air and generating a concentrated stream of CO2 for sequestration or utilization or production of carbon-neutral fuel.
  • CO2 removal is achieved when ambient air makes contact with chemical media, typically an aqueous alkaline solvent or sorbents.
  • chemical media typically an aqueous alkaline solvent or sorbents.
  • energy namely heat
  • Sorbents for the Direct Capture of CO2 from Ambient Air describes major types of sorbents designed to capture CO2 from ambient air categorized by the sorption mechanism: physisorption, chemisorption, and moisture-swing sorption.
  • Dilute CO2 can be efficiently separated using an anionic exchange polymer resin called Marathon MSA, which absorbs air CO2 when dry, and releases it when exposed to moisture. A large part of the energy for the process is supplied by the latent heat of phase change of water.
  • Other substances which can be used are metal-organic frameworks (or MOF's).
  • Membrane separation of CO2 rely on semi-permeable membranes.
  • the carbon dioxide that is provided in step (b) is fully or at least in part captured from oceanwater and other natural waters (direct ocean capture (DOC)).
  • DOC is one of the main pathways in terms of carbon dioxide removal (CDR).
  • CDR carbon dioxide removal
  • DOC technologies with non-biological concepts are for example electrochemical ocean capture (EOC), mineralization, ocean alkalinity enhancement (OAE), etc. There is a clearly visible attention towards the EOC.
  • BPMED bipolar membrane electrodialysis
  • E-CEM electrolytic cation exchange module
  • EHL electrochemical hydrogen looping
  • the ethanolamines in a mixture or each of monoethanolamine, diethanolamine and triethanolamine, preferably in a mixture of monoethanolamine (MEA) and diethanolamine (DEA), and/or the polyethylenimine according to the present invention are employed in a process for capturing CO2.
  • the inventive ethanolamines in a mixture or each of monoethanolamine, diethanolamine and triethanolamine and the polyethylenimine do only add as little as possible, in a preferred embodiment nothing, to a CO2 emission and do therefore as little as possible, preferably not, contribute to a CO2 emission themselves, i.e.
  • the cradle-to-gate PCF values of the inventive polyethylenimine and of the inventive ethanolamines are as low as possible, whereby specific cradle-to gate PCF values are mentioned above.
  • the present invention therefore relates to the use of the ethanolamines, selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, preferably in a mixture of monoethanolamine (MEA) and diethanolamine (DEA), or the polyethylenimine according to the present invention as (liquid and/or solid) CO2 absorbents in CO2 capturing processes.
  • the ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, preferably in a mixture of monoethanolamine (MEA) and diethanolamine (DEA), or the polyethylenimine according to the present invention as (liquid and/or solid) CO2 absorbents in CO2 capturing processes.
  • step (b) the carbon oxides, preferably carbon dioxide, and hydrogen are reacted to form methanol.
  • Process conditions for the hydrogenation of carbon oxides, preferably carbon dioxide, are known perse.
  • Different process approaches are being developed for the synthesis of methanol by hydrogenation of CO2: (1 ) heterogeneous catalysis, (2), homogeneous catalysis, (3) electrochemical, and (4) photocatalysis (see R. Guil-Lopez, Materials 2019, 12, 3902; doi:10.3390/ma12233902).
  • the synthesis of methanol by hydrogenation of carbon dioxide is performed in the presence of a heterogeneous catalyst.
  • the methanol production is carried out in a synthesis converter, e.g. a fixed- bed, catalytic reactor.
  • the average temperature inside the reactor is generally in the range of 150 to 300°C.
  • the average pressure inside the reactor is generally in the range of 50 to 150 bar (abs.).
  • step (b) methanol is formed, CH3OH, by reacting carbon oxides, preferably carbon dioxide, with hydrogen obtained at least in part by water splitting, preferably by electrolysis, using energy generated at least in part from non-fossil resources.
  • methanol is formed, CH3OH, by reacting carbon oxides, preferably carbon dioxide, with the hydrogen having a molar share of deuterium ⁇ 100 ppm, preferably in the range of from 10 to ⁇ 95 ppm, more preferably in the range of from 10 to ⁇ 90 ppm, most preferably in the range of from 10 to ⁇ 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy (e.g. from step (aO) in the process described in the description).
  • the deuterium content is even lower than corresponding to the distribution obtained by classical petrochemical routes.
  • step (c) methanol from step (b) is converted
  • inventive process for preparing ethylene oxide or propylene oxide in the inventive process for preparing alkoxylated compounds and in the inventive process for making alkoxylated di-, oligo- and polyamines or alkoxylated polyethyl- enimine - to ethene and/or propene, preferably in the inventive process for making alkoxylated di-, oligo- and polyamines or alkoxylated polyethylenimine - to ethene.
  • the ethene and/or propene in step (c) are obtained by a methanol-to-olefin process (MTO-process).
  • MTO-process methanol-to-olefin process
  • the methanol-to-olefin (MTO) process is a process in which olefins (especially ethene and propene) are produced from methanol.
  • the MTO process is generally known by a person skilled in the art.
  • An example for an MTO process is generally described in the following:
  • the process can be divided into three main steps.
  • methanol is fed into a reactor, preferably a fluidized bed reactor.
  • a catalyst is used to produce a gas that is particularly rich in ethylene and propylene.
  • the percentage yield of ethylene and propylene is determined, among other things, by the choice of catalyst and the control of the temperature and pressure in the reactor, as known by a person skilled in the art. For example: In order to achieve the highest possible yield of ethylene, the reactor is operated at a preferred temperature between 300 and 600 °C and a preferred pressure between 0.1 and 0.3 MPa. More general temperature and pressure ranges are given below.
  • the gas stream leaving the reactor generally contains light olefins (generally ethene, propene, butadiene and butene) as well as carbon monoxide (CO) and carbon dioxide (CO2).
  • the gas stream exiting the reactor is cooled down, preferably to about 95-115 °C. This is preferably done by quenching. This also generally removes water and dust from the gas stream. Possibly formed dimethyl ether and methanol remaining in the gas stream is returned to the reactor.
  • the individual gas fractions are fractionated. This is generally analogous to the fractionation during production via the route with steam crackers as known in the art.
  • the MTO process is generally an acid catalyzed reaction.
  • Preferred catalysts are zeolites like zeolites containing silica and alumina (e.g. ZSM-5) and silicon alumina phosphate zeolit-catalysts (SAPO) (e.g. SAPO-34).
  • SAPO silicon alumina phosphate zeolit-catalysts
  • This reaction is generally carried out at temperatures of from 300-600 °C.
  • the pressure is generally 0.1 -0.3 MPa.
  • the process is preferably carried out in a fluidized catalytic reactor (fluidized bed reactor).
  • the molar ratio propylene to ethylene can be adjusted by choosing appropriate process conditions, and may vary from 0.77 in the ethylene production mode and 1.33 in the propylene production mode.
  • Examples for commercial MTO technology licensors are UOP (e.g. UOP Advanced MTO process), Energy Technology Co. Ltd. (DMTO process) and Sinopec (SMTO process).
  • Steps (c) and (d) are generally known as CO2 to olefins via Methanol-to-olefin pathway (CO2MTO). The specific conditions of each step are mentioned above.
  • a preferred step (c) in the inventive process for preparing for preparing ethanolamines and in the inventive process for preparing polyethylenimine and also preferably in the inventive process for making alkoxylated di-, oligo- and polyamines or alkoxylated polyethylenimine is mentioned below:
  • step (c) methanol from step (b) is converted to ethylene.
  • the ethylene in step (c) is obtained by a methanol-to-olefin process (MTO- process).
  • MTO- process methanol-to-olefin process
  • the MTO process is an acid catalyzed reaction.
  • Preferred catalysts are zeolithes like zeolithes containing silica and alumina (e.g. ZSM-5) and silicon alumina phosphate ze- olith-catalysts (SAPO) (e.g. SAPO-34).
  • SAPO silicon alumina phosphate ze- olith-catalysts
  • This reaction is generally carried out at temperatures of from 300-600 °C.
  • the pressure is generally 0.1 -0.3 MPa.
  • the process is preferably carried out in a fluidized catalytic reactor.
  • the ratio propylene to ethylene can be adjusted by choosing appropriate process conditions, and may vary from 0.77 in the ethylene production mode and 1 .33 in the propylene production mode.
  • UOP e.g. UOP Advanced MTO process
  • DMTO process Energy Technology Co. Ltd.
  • SMTO process Sinopec
  • steps (b) and (c) are generally known as CO2 to olefins via Methanol-to-ole- fins pathway (CO2MTO). The specific conditions of each step are mentioned above.
  • step (d) ethene and/or propene from step (c) is/are reacted with oxygen or an oxidizing agent to form ethylene oxide and/or propylene oxide.
  • ethylene oxide can be prepared by any process known in the art.
  • the ethylene oxide in step (d) is obtained by oxidation of ethene (direct oxidation process).
  • the direct oxidation process is preferably performed in gas-phase, for example with oxygen or air, generally in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.
  • the direct oxidation process of ethene is generally performed at a temperature of from 230 to 270°C.
  • the pressure is preferably in the range of from 10 to 30 bar.
  • the direct oxidation process of ethene in step (d) is performed by gas-phase selective ethene oxidation that is typically performed in fixed-bed tubular reactors with supported Ag/ AI2O3 catalysts at 230-270 °C and 10-30 bar.
  • Preferred catalysts for the process in direct oxidation process of ethene in step (d) are silver-based catalysts like supported Re/Cs/Ag/AhOs catalysts that operate preferably in excess C2H4/O2; or alkaline-metal (Na, Cs)-promoted supported Ag/AI 2 O 3 catalysts that operate preferably in excess O2/C2H4.
  • the supported Re/Cs/Ag/AhOs system may additionally comprise oxides of Mo and/or S as promoters.
  • C2H4CI2 may also be added to deposit Cl on the catalyst, which acts as a promoter.
  • a preferred step (d) in the inventive process for preparing for preparing ethanolamines and in the inventive process for preparing polyethylenimine and also preferably in the inventive process for making alkoxylated di-, oligo- and polyamines or alkoxylated poly- ethylenimine is mentioned below:
  • step (d) ethylene from step (c) is reacted with oxygen to form ethylene oxide.
  • the ethylene oxide in step (d) is obtained by oxidation of ethylene (direct oxidation process).
  • the direct oxidation process is preferably performed in gas-phase, for example with oxygen or air, in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.
  • the step (d) is generally performed at a temperature of from 230 to 270°C.
  • the pressure is preferably in the range of from 10 to 30 bar.
  • step (d) is performed by gas-phase selective ethylene oxidation that is typically performed in fixed-bed tubular reactors with supported Ag/ AI2O3 catalysts at 230-270 °C and 10-30 bar.
  • Preferred catalysts for the process in step (d) are silver-based catalysts like supported Re/Cs/Ag/AhOs catalysts that operate preferably in excess C2H4/O2; or alkaline-metal (Na, Cs)-promoted supported Ag/AhOs catalysts that operate preferably in excess O2/C2H4.
  • the supported Re/Cs/Ag/AhOs system may additionally comprise oxides of Mo and/or S as promoters.
  • C2H4CI2 may also be added to deposit Cl on the catalyst, which acts as a promoter.
  • propylene oxide can be prepared by any process known in the art. Suitable processes for the preparation of propylene oxide are mentioned above.
  • propylene oxide in step (d) is obtained by oxidation of propene with hydrogen peroxide as an oxidizing agent, generally in the presence of a catalyst, preferably a zeolite catalyst, more preferably in the presence of Titansilikalit-1 (TS-1 ) (HPPO process).
  • a catalyst preferably a zeolite catalyst, more preferably in the presence of Titansilikalit-1 (TS-1 ) (HPPO process).
  • the HPPO process is generally carried out at temperatures below 90°C and pressures below 35 bar.
  • the process may be carried out in single or multi reactors system, e.g. in a tubular reactor, e.g. in a fixed bed or trickle bed.
  • HPPO process as well as other industrially relevant processes are for example described in M. Di Serio at aL, Ind. Eng. Chem. Res. 2013, 52, 1168-1178.
  • the hydrogen peroxide used as an oxidizing agent in the HPPO process which is preferably carried out for the preparation of propylene oxide according to the present invention may be obtained by any known process.
  • the hydrogen peroxide is obtained by an anthraquinone process (NexantECA study publication by Jia Lin and Adam Chan, Propylene Oxide, TECH 2022-3, December 2022).
  • the anthraquinone process is based on the catalytic hydrogenation of anthraquinone to anthrahydroquinone with hydrogen over a catalyst, e.g. a palladium catalyst. Subsequently, the anthraquinone is reformed in a re-oxidation with oxygen, for example pure oxygen or atmospheric oxygen, under elimination of hydrogen peroxide.
  • a catalyst e.g. a palladium catalyst.
  • the process steps in the anthraquinone process run under mild reaction conditions (generally a pressure below 1 MPa, i.e. 10 bar, generally a temperature below 100 °C) and preferably continuously.
  • the solubility can be adapted via the alkyl substituents and the solvent composition.
  • alkylated derivatives such as 2-ethyl-, 2-tert-butyl- or 2-amyl anthraquinone are employed.
  • nonpolar substances such as C9-/C10-alkyl benzene mixtures are part of the of the working solution.
  • Polar substances such as tris-(2-ethylhexyl)-phosphate, diisobutylcarbinol, tetra butylurea or urea or methyl cyclohexyl acetate take over this task for the hydroquinone.
  • the preparation of hydrogen peroxide is for example described in Anjali A. Ingle et aL, Environmental Science and Pollution Research (2022) 29:86468-86484 (anthraquinone process) , in Shu Hu et al., ACS AppL Energy Mater. 2019, 2, 11 , 7972-7979 (electrochemical synthesis of hydrogen peroxide from oxygen and water) and in NexantECA study publication by Sandrine Romand, Hydrogen Peroxide, TECH 2019- 8, September 2019.
  • propylene oxide in step (d) is obtained by oxidation of propene with hydrogen peroxide as an oxidizing agent, preferably in a HPPO process.
  • the present invention therefore relates to a process for preparing propylene oxide comprising the following steps:
  • step (c) converting the methanol from step (a) to propene
  • step (d) reacting the propene from step (b) with an oxidizing agent to form propylene oxide, wherein the carbon dioxide in step (b) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass, and/or the hydrogen in step (b) of the process of the present invention is preferably obtained at least in part by water splitting, preferably by electrolysis.
  • the by-product of the water splitting, preferably electrolysis is pure oxygen, which is usually released into the environment without further use; and wherein the propylene oxide in step (d) is therefore obtained by oxidation of propene with hydrogen peroxide as an oxidizing agent, preferably in a HPPO process, wherein the hydrogen peroxide is preferably obtained by an anthraquinone process.
  • the present invention therefore relates to a process for preparing propylene oxide comprising the following steps:
  • step (f) converting the methanol from step (a) to propene
  • step (g) reacting the propene from step (b) with an oxidizing agent to form propylene oxide, wherein the carbon dioxide in step (b) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass, and wherein the propylene oxide in step (d) is therefore obtained by oxidation of propene with hydrogen peroxide as an oxidizing agent, preferably in a HPPO process, wherein the hydrogen peroxide is preferably obtained by an anthraquinone process.
  • the hydrogen in step (b) of the process of the present invention is preferably obtained at least in part by water splitting, preferably by electrolysis.
  • the by-product of the water splitting, preferably electrolysis is pure oxygen, which is usually released into the environment without further use.
  • the oxygen in step (d) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least in part from non-fossil resources.
  • the oxygen in step (d) mentioned above is the oxygen which may be employed in the preparation of ethylene oxide, preferably by direct oxidation as well as the oxygen employed in the preparation of the oxidizing agent employed in the preparation of propylene oxide.
  • the oxidizing agent is preferably hydrogen peroxide, more preferably hydrogen peroxide prepared by the anthraquinone process.
  • the ethylene oxide obtained in step (d) of the inventive process preferably having a total cradle-to-gate product carbon footprint of ⁇ 1 .7 kg CO2e/kg ethylene oxide, preferably ⁇ 1 .6 kg CC>2e/kg ethylene oxide, more preferably ⁇ 1 .5 kg CO2e/kg ethylene oxide, further more preferably ⁇ 1 .4 kg CO2e/kg ethylene oxide, most preferably ⁇ 1 .3 kg CC>2e/kg ethylene oxide, further most preferably ⁇ 1 .2 kg CO2e/kg ethylene oxide, further most preferably ⁇ 1.1 kg CO2e/kg ethylene oxide, even further most preferably ⁇ 1 .0 kg CC>2e/kg ethylene oxide, even further most preferably ⁇ 0.9 kg CO2e/kg ethylene oxide, even further most preferably ⁇ 0.8 kg CO2e/kg ethylene oxide, even further most preferably ⁇ 0.7 kg CO2e/kg ethylene oxide, even further most preferably ⁇
  • the present invention therefore further relates to ethylene oxide obtained in the process according to the present invention as well as to ethylene oxide having a total cra- dle-to-gate product carbon footprint of ⁇ 1 .7 kg CO2e/kg ethylene oxide, preferably ⁇ 1 .6 kg CC>2e/kg ethylene oxide, more preferably ⁇ 1 .5 kg CO2e/kg ethylene oxide, further more preferably ⁇ 1 .4 kg CO2e/kg ethylene oxide, most preferably ⁇ 1 .3 kg CC>2e/kg ethylene oxide, further most preferably ⁇ 1 .2 kg CO2e/kg ethylene oxide, further most preferably ⁇ 1.1 kg CO2e/kg ethylene oxide, even further most preferably ⁇ 1 .0 kg CC>2e/kg ethylene oxide, even further most preferably ⁇ 0.9 kg CO2e/kg ethylene oxide, even further most preferably ⁇ 0.8 kg CO2e/kg ethylene oxide, even further most preferably ⁇ 0.7 kg CO2e/
  • the propylene oxide obtained in step (d) of the inventive process preferably having a total cradle-to-gate product carbon footprint of ⁇ 3.4 kg CO2e/kg propylene oxide, preferably ⁇ 3.3 kg CC>2e/kg propylene oxide, more preferably ⁇ 3.2 kg CO2e/kg propylene oxide, further more preferably ⁇ 3.1 kg CO2e/kg propylene oxide, most preferably ⁇ 3.0 kg CC>2e/kg propylene oxide, further most preferably ⁇ 2.9 kg CO2e/kg propylene oxide, even further most preferably ⁇ 2.8 kg CO2e/kg propylene oxide, even further most preferably ⁇ 2.7 kg CC>2e/kg propylene oxide, even further most preferably ⁇ 2.6 kg CC>2e/kg propylene oxide, even further most preferably ⁇ 2.5 kg CO2e/kg propylene oxide, even further most preferably ⁇ 2.4 kg CO2e/kg propylene oxide, even further most preferably ⁇
  • the present invention therefore further relates to propylene oxide obtained in the process according to the present invention as well as to propylene oxide having a total cradle-to-gate product carbon footprint of ⁇ 3.4 kg CO2e/kg propylene oxide, preferably ⁇ 3.3 kg CC>2e/kg propylene oxide, more preferably ⁇ 3.2 kg CO2e/kg propylene oxide, further more preferably ⁇ 3.1 kg CO2e/kg propylene oxide, most preferably ⁇ 3.0 kg CC>2e/kg propylene oxide, further most preferably ⁇ 2.9 kg CO2e/kg propylene oxide, even further most preferably ⁇ 2.8 kg CO2e/kg propylene oxide, even further most preferably ⁇ 2.7 kg CC>2e/kg propylene oxide, even further most preferably ⁇ 2.6 kg CC>2e/kg propylene oxide, even further most preferably ⁇ 2.5 kg CO2e/kg propylene oxide, even further most preferably ⁇ 2.4 kg CO2e/kg prop
  • step (b) production of methanol
  • step (b) production of methanol
  • the by-product spectrum of methanol employed in the process for the preparation of ethylene oxide and propylene oxide according to the present invention is different from the by-product spectrum of methanol obtained by conventional processes (i.e. using synthesis gas “syngas,” which is a combination of varying amounts of H2, CO, and CO2 frequently derived from gasified coal or natural gas).
  • synthesis gas “syngas,” which is a combination of varying amounts of H2, CO, and CO2 frequently derived from gasified coal or natural gas synthesis gas “syngas,” which is a combination of varying amounts of H2, CO, and CO2 frequently derived from gasified coal or natural gas.
  • conventionally obtained methanol generally comprises more methylformiate, acetone and higher alcohols (> C3) than methanol obtained by the process according to the present invention.
  • the by-product spectrum of ethene and propene manufactured by cracking of fossil-based hydrocarbon raw materials such as naphtha or natural gas used in conventionally obtained ethylene oxide and propylene oxide is even more different than the ethylene oxide and propylene oxide obtained by the CO2 to olefins via Methanol-to-olefins pathway (CO2MTO) according to the present invention for example due to the highly undesired sulfur components present especially in naphtha.
  • CO2MTO Methanol-to-olefins pathway
  • the different by-product spectrum of methanol respectively ethene and propene is also reflected in the downstream products, e.g. in the ethylene oxide and propylene oxide and in the alkoxylated compounds obtained according to the invention.
  • step (e) ammonia from step (a) is converted with ethylene oxide from step (d) to ethanolamines, selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof in one or more steps.
  • the reaction product obtained in step (e) generally comprises monoethanolamine, diethanolamine and triethanolamine.
  • step (e) is preferably performed in the presence of water, generally in a closed-cycle process with only minor fresh-water feed.
  • water generally in a closed-cycle process with only minor fresh-water feed.
  • Anhydrous processes preferably employ a fixed-bed catalyst, for example an organic ion-exchange resin or thermally more stable acidic inorganic clays or zeolites.
  • the reaction takes place in an aqueous phase, and the reactor pressure is usually sufficiently large to prevent vaporization of ammonia and ethylene oxide at the reaction temperature.
  • Ammonia concentrations in water are preferably between 50 and 100%.
  • the reaction pressure in the aqueous phase reaction is generally up to 160 bar, preferably 90 to 130 bar (abs).
  • the reaction temperature in the aqueous phase reaction is generally up to 150 °C, preferably 40 to 130°C.
  • Unconsumed ammonia and water are generally separated from the products in a distillation line downstream of the reactor and are recycled.
  • Product distribution of the three ethanolamines can be controlled by appropriate choice of the ammonia : ethylene oxide ratio.
  • the above reaction may be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia, for obtaining monoethanolamine, usually a work-up by distillation is required to remove diethanolamine and triethanolamine.
  • monoethanolamine, diethanolamine and triethanolamine may each be separated from the ethanolamines which are generally obtained as mixtures of monoethanolamine, diethanolamine and triethanolamine in steps (a) to (e) of the process according to the present invention by distillation (see step (f)).
  • a separation of monoethanolamine may not be necessary.
  • carbon capturing for example, a mixture of monoethanolamine and diethanolamine may be employed and only trieth- anoamine has to be separated, generally by distillation.
  • Ethanolamines are a family of chemicals that work as ingredients in personal care products, cleaning products and industrial applications.
  • ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof according to the present invention are for example:
  • Ethanolamines like MEA and especially TEA work as ingredients in personal care products and cosmetics.
  • ethanolamines help remove dirt and oil on skin by dissolving grease and blending other important ingredients.
  • ethanolamines do not impart a strong odor, they are commonly ingredients in products like hair dye.
  • Ethanolamines like MEA help adjust the pH of a product to keep it from degrading when stored in a container so it will last longer.
  • Ethanolamines such as MEA are common ingredients in cleaning products like floor and tile cleaners, as well as laundry detergents.
  • DEA is a common ingredient in industrial cleaning products, such as engine degreasers and industrial strength detergents, due to its ability to break down oil and grease.
  • MEA acts as a plasticizing agent to help make plastic become pliable and soft.
  • Chemical manufacturing plants use MEA to remove carbon dioxide from ammonia gas in the production of synthetic ammonia.
  • DEA is used in agrochemicals to make pesticides, where it helps increase a pesticide’s ability to dissolve in water.
  • DEA works as an emulsifier to help ingredients mix and help keep other materials from corroding.
  • MEA and DEA also can be used in industrial applications, such as chemical manufacturing and gas treating. In gas treating processes for refineries and natural gas streams, MEA and DEA help remove contaminants from gasoline.
  • TEA is used in agrochemicals, to help pesticides disperse into crops, which then helps repel insects from the crops.
  • TEA helps separate oil from water and other substances.
  • cement additives TEA helps advance setting and/or hardening of cement. It is also a corrosion inhibitor in steel and zinc materials used in building and construction.
  • step (eO) In the preparation of the inventive alkoxylated compounds, step (eO) generally is carried out subsequent to step (d) mentioned above.
  • step (eO) the ethylene oxide and/or propylene oxide obtained in step (d) and optionally the at least one alkylene oxide different from ethylene oxide and propylene oxide is reacted with the at least one starter unit having Zerewitinoff active hydrogen atoms in one or more steps to form the alkoxylated compound.
  • the alkoxylated compound prepared in the process of the present invention comprises i) 20 wt-% to ⁇ 100 wt-%, preferably 30 wt-% to ⁇ 99.3 wt-% of ethylene oxide units and/or propylene oxide units, ii) 0 wt-% to 30 wt-%, preferably 0.5 wt-% to 20 wt -% of at least one alkylene oxide unit different from ethylene oxide and propylene oxide units, iii) >0 wt-% to 80 wt-%, preferably 0.2 wt-% to 70 wt -% of at least one starter unit having Zerewitinoff active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%.
  • Ethylene oxide units and/or propylene oxide units Ethylene oxide units and/or propylene oxide units:
  • the alkoxylated compound according to the present invention comprises ethylene oxide units (EO), propylene oxide units (PO) or both.
  • EO and PO can be present in various weight ratios.
  • the alkoxylated compound has an EO:PO weight ratio of from 100:0 to 0:100, 90:10 to 10:90, 25:75 to 75:25, 25:75 to 85:15, 50:50 to 85:15, 55:45 to 80:20, or 60:40 to 75:25, or any range between the lowest and highest of these values.
  • the alkoxylated compound according to the present invention may comprise at least one alkylene oxide unit different from ethylene oxide and propylene oxide units.
  • alkylene oxide units different from ethylene oxide and propylene oxide units are based on 1 ,2-butylene oxide, 2,3-butylene oxide, styrene oxide, 1 ,3-propylene oxide or tetrahydrofuran, preferably 1 ,2-butylene oxide or 2,3-butylene oxide, more preferably 1 ,2-butylene oxide (BuO).
  • the alkoxylated compound prepared in the process of the present invention comprises 0 wt-% of alkylene oxide units different from ethylene oxide and propylene oxide units.
  • the alkylene oxide units may be present in the alkoxylated compound in form of exclusively one type of alkylene oxide units, i.e. exclusively ethylene oxide units or exclusively propylene oxide units, for example in the case of polymeric alkylene oxide units in the form of homopolymers, or in form of two or more different alkylene oxide units, e.g. ethylene oxide units and propylene oxide units in the ratios mentioned above, or ethylene oxide units and/or propylene oxide units and 1 ,2-butylene oxide units.
  • polymeric alkylene oxide units in the form of random copolymers or block copolymers.
  • the polymer is EO capped. In other embodiments, the polymer is PO capped. Such capping may be referred to as a small block, e.g. a small block of EO which acts as the cap. If the polymer is capped, it may be referred to in the art as a block copolymer. In certain embodiments, the polymer is a block PAG. Such block PAGs can comprise blocks of all EO or PO, blocks of random EO/PO monomers with at least two blocks being of different EO/PO ratios, or a combination of all EO or PO blocks and random EO/PO blocks.
  • Preferred ethylene oxide units and/or propylene oxide units according to the present invention are characterized by the following formulae: ia) lb) ic) wherein n, m, n’ and m’ are each independently 1 to 500, preferably 1 to 100, more preferably 2 to 50; and the groups n' and in formula (Ic) are arranged in the form of two or more, preferably 2 or 3 blocks and/or randomly.
  • the total number average molecular weight of the ethylene oxide units is in the range of 88 to 22000 Da, preferably 88 to 4400 Da, more preferably 88 to 2200 Da and the total number average molecular weight of the propylene oxide units is in the range of 116 to 29000 Da, preferably 116 to 5800 Da, more preferably 116 to 2900 Da.
  • the average molecular weight of the ethylene oxide units and/or propylene oxide units may be calculated based on its monomeric structure.
  • Zerewitinoff active hydrogen is reactive as determined by the Zerewitinoff method as described in the Analyst 1963, 88, 782-790.
  • the quantitative determination of active hydrogens in a chemical substance by means of adding methylmagnesium iodide in pentyl ether to the solution of substrate and quantitatively measuring the volume of gaseous methane evolved is generally known as the Zerewitinoff determination.
  • the starter units having Zerewitinoff active hydrogen atoms are selected from the group consisting of water, at least one of mono-, di- or polyfunctional alcohols, mono, di- or polyfunctional amines and mono-, di- or polyfunctional thio compounds. More preferred starter units are water, mono-, di- or polyfunctional alcohols and/or mono-, di- or polyfunctional amines.
  • the starter units preferably contain from 1 to 100, more preferably in the from 2 to 50, most preferably 2 or 8, further most preferably 2 or 3 Zerewitinoff active hydrogen atoms.
  • polyethyleneimines as starter units, preferred polyethylene imine starter units having an amine number of 3 to 30 mmol/g, preferably 5 to 25 mmol/g, more preferably 10 to 22 mmol/g.
  • the amine number refers to the proportion of amine present in an element.
  • the amine number is determined according to DIN 53176 (edition 2000-12).
  • Suitable mono-, di- or polyfunctional alcohols include monools, diols, triols, tetrols or higher alcohols, which may also be referred to in the art as polyols.
  • the alcohol is a monool.
  • Suitable monools include Ci- to C20 alcohols, for example n-butanol, iso-butanol, 2-ethyl hexanol, 2-propyl heptanol, butyl glycol, butyl diethyleneglycol, butyl triethyleneglycol, butyl propyleneglycol, butyl dipropyleneglycol, butyl tripropyleneglycol, methyl diglycol, methyl triglycol, methyldipropyleneglycol, methyldipropyleneglycol, methanol, ethanol, hexanol, iso-nonanol, decanol, 2-butyloctanol, oleyl alcohol, octadecanol (C alcohol) (e.g.
  • stearyl alcohol isononadecanol, C12 alcohol, C13 alcohol, C14 alcohol, C15 alcohol, C16 alcohol, C17 alcohol, 2- ethylhexanol, 2-propylheptanol, 2-butyloctanol, 2-pentylnonanol, 2-hexyldecanol, and mixtures of said alcohols like C13-C15 alcohol, C12-C18 alcohol, C16-C18 alcohol, or C12- C14 alcohol.
  • the alcohol is a diol.
  • Suitable diols include ethyleneglycol, 1 ,2-propylene glycol, 1 ,2-hexanediol, diethyleneglycol, triethyleneglycol, dipropyleneglycol, and tripropyleneglycol.
  • the alcohol is a polyol.
  • suitable polyols include glycerol, trimethylolpropane, and pentaerithritol.
  • amines can be used to form the alkoxylated compound.
  • suitable amines include monoamines, diamines, triamines or higher amines, which may also be referred to in the art as polyamines.
  • suitable amines include alkanolamines, ethylene diamines, diethylene triamines, and polyethylenimines.
  • polyethylenimine in the context of the present invention does not only refer to polyethylenimine homopolymers but also to polyalkyleneimines containing NH-CH2- CH2-NH structural elements together with other alkylene diamine structural elements, for example NH-CH2-CH2-CH2-NH structural elements, NH-CH2-CH(CH3)-NH structural elements, NH-(CH2)4-NH structural elements, NH-(CH2)6-NH structural elements or (NH-(CH2)8-NH structural elements but the NH-CH2-CH2-NH structural elements being in the majority with respect to the molar share.
  • Preferred polyethylenimines contain NH-CH2-CH2-NH structural elements being in the majority with respect to the molar share, for example amounting to 60 mol-% or more, more preferably amounting to at least 70 mol-%, referring to all alkyleneimine structural elements.
  • polyethylenimine refers to those polyalkylene imines that bear one or zero alkyleneimine structural element per molecule that is different from NH-CH2-CH2-NH.
  • the “polyethylenimine” in the context of the present invention is linear or branched. The degree of the branching may be determined by a skilled person according to practical application by 13C NMR.
  • Polyalkyleneimines including polyethyleneimines, can be characterised by their degree of branching (DB).
  • DB degree of branching
  • the degree of branching DB is defined therein as
  • T is the average number of terminally bound monomeric units (primary amino groups)
  • Z is the average number of branching monomeric units (tertiary amino groups)
  • L is the average number of linearly bound monomeric units (secondary amino groups).
  • T, Z, and L can be determined via 13C-NMR in D2O.
  • the degree of branching DB of the polyalkyleneimines, especially polyethyleneimines, according to the present invention is preferably in the range of 55 to 95%, preferably in the range from 57 to 90% and more preferably in the range from 60 to 80%.
  • the polyalkyleneimine, preferably polyethyleneimine, employed in the reaction mixture may desirably have a weight average molecular weight (MW) or from 300 to 20,000, for instance from 300 to 15,000, suitably from 300 to 10,000, more suitably from 300 to 5000, preferably from 500 to 1500, more preferably from 500 to 1000 g/mol.
  • the weight average molecular weight (Mw) can be determined by gel permeation chromatography (GPC), with hexafluoroisopropanol and 0,05w% ammoniumacetate as eluent and narrowly distributed polyethylene glycol standards as stationary phase.
  • the alkoxylation can generally be carried out in three ways: (i) anionic (base-initiated) polymerization, (ii) acid initiated polymerization, and (iii) by coordination polymerization.
  • the anionic polymerization of epoxides represents the “classical” technique for the synthesis of the respective polymers/compounds comprising ethylene oxide and/or propylene oxide units.
  • the anionic polymerization is usually carried out by catalytic addition of ethylene oxide and/or propylene oxide and optionally at least one alkylene oxide different from ethylene oxide and propylene oxide, onto at least one starter unit having Zerewitinoff active hydrogen atoms.
  • metal compounds preferably alkali metal (especially sodium, potassium, or cesium) compounds with high nucleophilicity can be employed.
  • alkali metal hydroxides especially sodium, potassium, or cesium
  • alkali metal salts especially sodium, potassium, or cesium
  • alkali metal hydrides especially sodium, potassium, or cesium
  • potassium hydroxide having the greatest significance in practice (see for example US 6156720 A).
  • a further suitable class of catalyst are multimetal cyanide compounds, preferably double metal cyanide compounds, especially zinc hexacyanometalates. These catalysts are frequently also referred to as DMC catalysts.
  • the polyether alcohols prepared using multimetal cyanide compounds feature a very low content of unsaturated constituents.
  • a further advantage in the use of multimetal cyanide compounds as catalysts consists in the distinctly increased space-time yield in the addition of the alkylene oxides.
  • the alkoxylation in the presence of DMC catalysts is for example described in DD 203 735, DD 203 734, WO 97/29146, WO 98/03571 , WO 00/14143, WO 99/44739 and US 2008/0161509 A1.
  • Solvents employed for the anionic polymerization of epoxides are generally polar and aprotic; therefore, tetrahydrofuran (THF), dioxane, dimethyl sulfoxide (DMSO), and hexamethylphosphoramide (HMPA) are often used. Furthermore, polymerization in the bulk monomer is possible and is the preferred process.
  • Alkoxides with sodium, potassium, or cesium counterions in THF or other polar, aprotic solvents represent popular initiator systems.
  • complexing agents such as crown ethers suitable for the respective cation can strongly accelerate the anionic polymerization of epoxides.
  • the temperatures during the alkoxylation are usually between 80 and 200°C, preferably 90 to 180°C.
  • the alkoxylated compounds of the present invention can be prepared either in a batch- wise, semibatchwise or in a continuous process.
  • the catalyst and the at least one starter are initially charged while epoxide (ethylene or propylene oxide) is added during the reaction course.
  • epoxide ethylene or propylene oxide
  • the alkoxylated polyethylenimines of the present invention can be obtained by alkoxylation of polyethylenimine via a process commonly known in the art.
  • the alkoxylation of polyethyleneimines using ethylene oxide, propylene oxide and butylene oxide is for example described in Houben-Weyl, Methoden der organischen Chemie, 4. Ed., Vol.14/2, p.440 ff. (1963) and Vol. E 20, p.1367 f. (1987).
  • the alkoxylated polyethylenimine of the present invention may be obtained as for example described in US5445765 and DE-A 2227546.
  • the at least one starter unit is a mono-, di- or polyfunctional alcohol
  • the alcohol alkoxide components (alkoxlated alcohols) obtained can be converted into alkyl ether sulfate salts by sulfating them in a manner known per se using sulfuric acid or sulfuric acid derivatives to give acid alkyl ether sulfate salts (see for example US 2008/0207939 A1 ).
  • Sulfation reactions of alcohols have already been described, for example in US 3,462,525, US 3,420,875 and US 3,524,864. Details on carrying out this reaction are also given in “Ullmann’s Encyclopedia of Industrial Chemistry”, 5th edition, Vol. A25 (1994), pages 779-783 and in the literature references given there.
  • sulfuric acid itself is used for the esterification, expediently use is generally made of from 75 to 100% strength by weight, preferably from 85 to 98% strength by weight, acid (termed “concentrated sulfuric acid” or “monohydrate”.
  • the esterification can be formed in a solvent or diluent if it is wanted for control of the reaction, for example heat development.
  • the alcoholic reactant is introduced first and the sulfation reagent is added gradually with continuous mixing.
  • the sulfation reagent and the alcohol alkoxide component are generally used in a molar ratio of from 1 :1 to 1 :1.5, preferably from 1 :1 to 1 :1.2. Smaller amounts of sulfation reagent can be advantageous if mixtures of alcohol alkoxylates are used.
  • the esterification is usually carried out at temperatures of from 25 to 85° C, preferably in the range from 45 to 75° C. If appropriate it can be expedient to carry out the esterification in a low-boiling, water-immiscible solvent and diluent at its boiling point, the water being formed in the esterification being distilled off azeotropically.
  • sulfuric acid of the concentration stated above
  • sulfur trioxide sulfur trioxide complexes
  • solutions of sulfur trioxide in sulfuric acid (“oleum”) chlorosulfonic acid
  • sulfuryl chloride sulfuryl chloride
  • the reaction can also be carried out advantageously in a falling-film reactor in countercurrent or cocurrent flow, if appropriate also continuously.
  • the batches, after the esterification, are neutralized by adding alkali and, if appropriate after removing excess alkali metal sulfate and any solvent present, are worked up.
  • chlorosulfonic acid is used as sulfating reagent
  • the corresponding alcohol alkoxide component is charged into a stirred apparatus under inert conditions. Under vigorous stirring, a corresponding amount of chlorosulfonic acid is added dropwise.
  • the molar ratio between alcohol component and chlorosulfonic acid is generally from 0.5:1 to 1 :0.5, preferably the ratio is from 0.75:1 to 1 :0.75.
  • the molar ratio of alcohol alkoxide component to chlorosulfonic acid is 1 :1.
  • the reaction batch is adjusted to a slightly alkaline pH using sodium hydroxide solution.
  • the alkoxylated compounds obtained in step (eO) are characterized by a low cradle to grave product carbon footprint (see the explanation above) compared with the same alkoxylated compounds obtained in conventional processes (i.e. without CO2 to olefins via Methanol-to-olefin pathway (CO2MTO), without carbon capturing etc.).
  • CO2MTO Methanol-to-olefin pathway
  • the present invention therefore solves the dilemma mentioned above, and provides alkoxylated compounds having a low cradle to grave (i.e. including scope 3 downstream (see the explanation above)) product carbon footprint and generally at the same time a good biodegradability.
  • the “material carbon” in the polymer product is considered as the only add-on CO2 emissions for the end of life “grave” emissions; all other e.g. transportation and use-related emissions in the products customer and consumer use phase are out of scope.
  • the 3 scenarios i), ii) or iii) are as follows: i) Fossil conventional: Ethylene oxide and/or propylene oxide are not prepared via steps b) and c) but instead fossil based ethene and/or propene obtained e.g. by Naphtha cracking is directly used in step d).
  • steps d) and e) are carried out on the basis of fossil energy (comparative example);
  • the carbon dioxide used in step b) is; additionally the hydrogen in step (b) is obtained by electrolysis based on electrical power generated from non-fossil resources, step c) and d) are based on CO2MTO (CO2 to olefins via Methanol-to-olefins pathway); hydrogen from SMR with CCS (carbon capturing and storage) is only used for preparing the oxidizing agent (hydrogen peroxide) required for preparing propylene oxide via HPPO in step d) iii) Best-case according to the present invention: All steps b) to d) as well as the production of hydrogen and oxygen are carried out predominantly on the basis of non-fossil energy.
  • the present invention therefore relates to alkoxylated compounds, having a total cra- dle-to-grave (see the explanation above) product carbon footprint of generally ⁇ 8.88*C - 0.253*E + 1 ,33*P - 0.940, preferably ⁇ 8.38*C - 0.330*E + 1 ,12*P - 0.829, more preferably ⁇ 7.89*C - 0.406*E + 0.898*P - 0.718, most preferably ⁇ 7.40*C - 0.483*E + 0.681 *P - 0.606, further most preferably ⁇ 6.90*C - 0.560*E + 0.464*P - 0.495, further most preferably ⁇ 6.48*C - 0.489*E + 0.239*P - 0.436, further most preferably ⁇ 6.06*C
  • the weight fraction of alkylene oxide units different from ethylene oxide and propylene oxide units is 0 wt-%.
  • P PO-content in the alkoxylated compound [mass-ratio].
  • the present invention further relates to alkoxylated compounds obtainable by the process of the present invention.
  • said alkoxylated compounds having a cradle- to-grave (see the explanation above) product carbon footprint of generally ⁇ 8.88*C - 0.253*E + 1 ,33*P - 0.940, preferably ⁇ 8.38*C - 0.330*E + 1 ,12*P - 0.829, more preferably ⁇ 7.89*C - 0.406*E + 0.898*P - 0.718, most preferably ⁇ 7.40*C - 0.483*E + 0.681 *P - 0.606, further most preferably ⁇ 6.90*C - 0.560*E + 0.464*P - 0.495, further most preferably ⁇ 6.48*C - 0.489*E + 0.239*P - 0.436, further most preferably ⁇ 6.06*C
  • the alkoxylated compounds according to the present invention satisfy the biodegradability requirements set forth in OECD 301 B (as mentioned above).
  • the alkoxylated compounds of the present invention comprising i) 20 wt-% to ⁇ 100 wt-%, preferably 30 wt-% to 99.3 wt-% of ethylene oxide units and/or propylene oxide units, ii) 0 wt-% to 30 wt-%, preferably 0.5 wt-% to 20 wt-% of at least one alkylene oxide unit different from ethylene oxide and propylene oxide units, iii) >0 wt-% to 80 wt-%, 0.2 wt-% to 70 wt-% of at least one starter unit having Zere- witinoff active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%, wherein the ethylene oxide units and/or propylene oxide units, the alkylene oxide unit different from ethylene oxide and propylene oxide units and the starter unit having Zerewitinoff active hydrogen atoms are defined above
  • the alkoxylated compounds of the present invention comprising an EO:PO weight ratio of from 100:1 to 0:100, 90:10 to 10:90, 25:75 to 75:25, 25:75 to 85:15, 50:50 to 85:15, 55:45 to 80:20, or 60:40 to 75:25, or any range between the lowest and highest of these values.
  • the ethylene oxide units and/or propylene oxide units, the alkylene oxide unit different from ethylene oxide and propylene oxide units and the starter unit having Zerewitinoff active hydrogen atoms are defined above.
  • inventive alkoxylated compounds generally having a number average molecular weight of 100 to 50000 Da, preferably 200 to 30000Da, more preferably 300 to 20000 Da, determined by GPC in THF with PEG standard.
  • alkoxylated compounds of the present invention have a wide range of applications across various industries. Some of the applications are:
  • Lubricants The alkoxylated compounds can be used as lubricants in various industries such as automotive, aerospace, and industrial machinery. They offer excellent lubrication properties, high thermal stability, and resistance to oxidation.
  • Personal care products The alkoxylated compounds can be used in formulations of personal care products such as lotions, creams, and shampoos. They provide for example moisturizing and conditioning properties to the skin and hair.
  • the alkoxylated products can be used as surfactants in laundry detergents, hard surface cleaner, and rinse aids. They provide excellent wetting, cleaning, and emulsifying properties
  • the alkoxylated compounds can be used as excipients in the pharmaceutical industry to improve drug solubility, stability, and bioavailability. They are also used in formulations of ointments, creams, and gels.
  • the alkoxylated compounds can be used in the textile industry as softeners and anti-static agents. They can improve the texture and feel of fabrics and reduce static electricity.
  • Food industry The alkoxylated compounds can be used in the food industry as emulsifiers, thickeners, and stabilizers. They can be used in the production of ice cream, dairy products, and baked goods.
  • the alkoxylated compounds can be used as hydraulic fluids, oil breakers and heat transfer fluids in the oil and gas industry. They offer for example excellent lubrication properties and high thermal stability.
  • the alkoxylated compounds can be used as adjuvants in the agriculture industry for example to improve the effectiveness of herbicides and pesticides.
  • the alkoxylated compounds can be used as reaction media, surfactants, and dispersants in the chemical industry. They can be used in the production of polymers, resins, and coatings.
  • the alkoxylated compounds can be used in the construction industry as additives in cement, concrete, and plaster to improve for example their workability, strength, and durability.
  • the alkoxylated compounds can be used as starting materials for the production of fer example polyurethane foams, adhesives, and coatings. They can act as chain extenders and cross-linking agents in the polymerization process.
  • the alkoxylated compounds can be as coolants and lubricants in metalworking processes such as cutting, grinding, and drilling. They offer for example excellent thermal stability, low volatility, and high lubricity.
  • the alkoxylated compounds can be used as heat transfer fluids in electronic cooling systems. They offer for example high thermal conductivity, low viscosity, and compatibility with various materials.
  • the alkoxylated compounds can be used as additives in fuels and lubricants, for example fuel performance packages, to improve their performance and reduce emissions. They can also be used as heat transfer fluids in solar and geothermal energy systems.
  • the alkoxylated compounds can be used as flocculants and coagulants in water treatment processes. They can help removing suspended particles and impurities from water.
  • the alkoxylated compounds can be used as binders and thickeners in the formulation of adhesives and sealants. They can provide improved adhesion, flexibility, and moisture resistance.
  • the present invention therefore further relates to the use of the inventive alkoxylated compounds in any one of the applications mentioned above.
  • the present invention therefore further relates to the use of the alkoxylated compounds according to the present invention or obtained by a process according to the present invention in home care products, cosmetic products, pharmaceutical products, food sector, building materials, lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids, agrochemicals like pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and polyurethane) applications, and home care products, cosmetic products, pharmaceutical products, products in food sector, building materials, lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents,
  • Step (f) comprises separating monoethanolamine from ethanolamines obtained in step (e).
  • reaction step (e) may be controlled by the stoichiometric ratio of the reactants ethylene oxide and ammonia, for obtaining monoethanolamine, usually separation is required to remove diethanolamine and triethanolamine.
  • Said work-up is generally known in the art and is usually performed by distillation, preferably at reduced pressure, e.g. vacuum distillation.
  • step (g) monoethanolamine from step (f) is converted to ethylenimine (aziridine), preferably by a catalytic gas-phase-synthesis.
  • One object of the present invention is the provision of environmentally friendly polyeth- ylenimine. It was surprisingly found by the inventors that the greenhouse gas (GHG) emissions generated by a conversion of monoethanolamine to ethylenimine by a catalytic gas-phase-synthesis is significantly lower than the GHG emissions generated by a conversion of monoethanolamine to ethylenimine by other processes.
  • the PCF of ethylenimine obtained by a catalytic gas-phase-synthesis and consequently polyethylenimine is therefore significantly lower than the PCF of ethylenimine and polyethylenimine obtained by other processes (in the case that only step (g) is different in the process for preparing ethylenimine and polyethylenimine).
  • step (g) of the process of the present invention by using the monothanolamine from step (f), i.e. based on hydrogen obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources.
  • Suitable processes for the preparation of ethylenimine from monoethanolamine are generally known in the art.
  • Suitable catalytic gas-phase-processes for the preparation of ethylenimine from monoethanolamine are generally known in the art, see e.g. US 4,841 ,061 for suitable examples of catalyst compositions and US 4,966,980 for the respective ethylenimine gasphase process conditions.
  • ethylenimine is prepared by dehydration of monoethanolamine at temperatures of generally 350 to 450 °C, generally at reduced pressure of 30 to 500 mbar(abs).
  • the process is generally carried out in the presence of a catalyst with weak basic and acidic sites, which is for example based on Si-Cs-P or Si-Rb-P.
  • a catalyst with weak basic and acidic sites which is for example based on Si-Cs-P or Si-Rb-P.
  • An overview of this production technology and optimal catalyst composition with high yield (e.g. up to 80 mol%), selectivity and activity is found in Applied Catalysis A: General 221 (2001) 209- 217; Acid-base catalysis: On the example of ethylenimine production; Hideaki Tsuneki; Nippon Shokubai Co. Ltd., Functions and Materials Research Laboratory, Suita 564- 8512, Japan.
  • the process is susceptible to catalyst deactivation by coking and sintering as well as loss of active components due to the high processing temperature despite low contact times.
  • a catalyst regeneration cycle with e.g. trimethylphosphate-treatment can be employed as described in Applied Catalysis A: General 331 (2007) 95-99; Deactivation and regeneration of ethylenimine production catalyst; Hideaki Tsuneki, Kimio Ariyoshi; Nippon Shokubai Co. Ltd., Functions and Materials Research Laboratory, Suita 564-8512, Japan.
  • Other examples of suitable catalyst preparation methods include regeneration methods are described in WO 2015090084 and CN 104475144.
  • the catalytic gas phase dehydration process is usually carried out in the gas phase in a flow tube reactor, preferably in a fixed-bed flow tube reactor.
  • a fluidized bed reactor for the dehydration of monoethanolamine can be used for more efficient catalytic contact and heat transfer.
  • the product mixture obtained is usually separated by quenching followed by multistage distillation giving high purity ethylenimine, and unreacted monoethanolamine is fed back into the reactor.
  • the liquid phase ethylenimine process can be generally carried out in batch or continuous mode usually with very high yields of 85 - 90 mol% giving high purity ethylenimine after distillation with excellent properties required e.g. for high molecular weight poly- ethylenimines and other derivatives.
  • step (h) ethylenimine from step (g) is polymerized to polyethylenimine.
  • Suitable processes for the preparation of polyethylenimine by polymerization of ethylenimine are known by a person skilled in the art.
  • Polyethylenimine is preferably prepared by cationic ring opening polymerization of ethylenimine in the presence of Broensted acids, Lewis acids, haloalkanes or carbon dioxide. Examples are given in US 2,182,306 and US 3,203,910 as well as US 2001/0039318.
  • the polymerization may be carried out for example in a batch process in which water and 1 ,2-dichloroethane as catalyst are placed in a reaction vessel, the mixture is heated to a temperature of from 70 to 100°C and ethylenimine is continuously added with stirring of the reaction mixture.
  • the polyethylenimines obtained are generally branched or hyperbranched polyethyl- enimines.
  • the polyethylenimine obtained has preferably a weight average molecular weight M w in the range of from 500 to 2,000,000 g/mol, preferably in the range of from 500 to 100,000 g/mol.
  • the degree of branching of the polyethylenimines is preferably in the range of from 0.45 to 0.75, more preferably 0.5 to 0.7, most preferably 0.55 to 0.7, determined by 13 C NMR spectroscopy in D2O.
  • the degree of branching is calculated as (Z7 + 7) / (Z7 + T+ L).
  • D refers to the dendritic (or tertiary) amin groups
  • L (linear) refers to the secondary amino groups
  • environmentally friendly ethanolamines selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof, polyethylenimine, ethylenimine, ethylene oxide and ammonia and an environmentally friendly process for making the same, wherein said process uses as little fossil energy as possible, are provided.
  • the inventive polyethylenimine is characterized by a low molar share of deuterium, which is ⁇ 110 ppm, preferably in the range of from 10 to ⁇ 105 ppm, more preferably in the range of from 10 to ⁇ 95 ppm, most preferably in the range of from 10 to ⁇ 92 ppm, based on the total hydrogen content.
  • the present invention further relates to polyethylenimine, wherein the molar share of deuterium is ⁇ 110 ppm, preferably in the range of from 10 to ⁇ 105 ppm, more preferably in the range of from 10 to ⁇ 95 ppm, most preferably in the range of from 10 to ⁇ 92 ppm, based on the total hydrogen content.
  • Said polyethylenimines are preferably prepared by a process comprising at least step (a) according to the present invention. More preferably, said polyethylenimines are prepared by the process of the present invention comprising steps (a) to (h).
  • the polyethylenimines according to the present invention are characterized by a low deuterium molar share. They display a deuterium share different from petrochemically made polymers and ethanolamine made by a petrochemical process, i.e. based on fossil energy.
  • One further key feature of the ethanolamines, selected from monoethanolamine, diethanolamine, triethanolamine and mixtures thereof and the polyethylenimine of the present invention is a low deuterium molar share.
  • Said low deuterium molar share is mainly introduced by the hydrogen employed in the process according to the present invention. Therefore, also the ammonia, prepared by reacting said hydrogen with nitrogen is characterized by a low deuterium molar share.
  • the polyethyleneimine is further reacted with at least ethylene oxide and/or propylene oxide, preferably at least ethylene oxide obtained from step (d) in the known alkoxylation reaction to obtain the ethoxylated and/or propolylated, preferably ethoxylated polyethyleneimine.
  • ethylene oxide and/or propylene oxide preferably at least ethylene oxide obtained from step (d) in the known alkoxylation reaction.
  • propolylated preferably ethoxylated polyethyleneimine.
  • Steps (i) and (e1) are the same type of process; instep (i) an PEI is alkoxylated, whereas in step (e2) a di-, olido, polyamine or a PEI are alkoxylated.
  • the processes are otherwesie the same.
  • alkylene oxides When other alkylene oxides are employed for the alkoxylation reaction, other typical alkoxylated polyetheyleneimines are obtained; typical alkylene oxides known for such use are butylene oxide (especially n-butylene oxide, nBuO) and higher alkoylene oxides. Usually used is nBuO.
  • Sokalan® PG617 from BASF, which is a polyethylene imine which is alkoxylated with typically about 7 EO and 5 PO in a block structure of PEI-1 OEO-7PO
  • Sokalan® HP20 also from BASF, which is a polyethylene imine being ethoxylated typically with about 20 EO- units per NH, with the polyethylene imine having a molecular weight being reported to be about 600 or 800 g/mol, depending on the source.
  • Sokalan®-products Sokalan® PG617 and Sokalan® HP20 and all similar products using polyethyleneimine and using EO for alkoxylation - and optionally further ingredients such as the mentioned lactones and other alkylene oxides besides EO - can be obtained in the known manner, but such products having a much lower content of fossil-based share based on the molar weight of those products.
  • alkoxylated PEI-products can be found for example in EP 2 014 753 A1 , EP 2 925 848 B1 ; further, alkoxylated PEI and alkoxylated di/oligo/polyamines - sometimes comprising further alkylene oxides and/or lactones (typically included within the alkoxylation reaction or as separate “polylactone-blocks” or insertions of single lactone or not more than two or perhaps three lactones into an alkylene oxide chain with such alkylene oxide chain being derived from EO only or from EO and other alkylene oxides with such more than one alkylene oxide being in any form such as random, block arrangement, depending on the process steps) - can be also found in WO2021/165468 A, WO2021/165493, WO2022/136408 A, WO2022/136409 A, W02023/021104 A, W02023/021105 A, W0202
  • said environmentally friendly prepared compounds i.e. alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine are characterized by a specifically low deuterium molar share.
  • hydrogen obtained by electrolysis is preferably obtained by using non-fossil energy sources. It is expected that the electrification (power generation) of fossil sources will be fully replaced by the generation of power by non-fossil resources in the near future.
  • the inventors therefore found a way for tracing the origin of hydrogen and downstream products of hydrogen, preferably alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine, via the deuterium molar share of said compounds.
  • These downstream products based on hydrogen, such hydrogen obtained by electrolysis, and hydrogen itself can be distinguished by its deuterium molar share from the chemically in principle identical compounds prepared by processes based on fossil energy, i.e. made by petrochemical processes.
  • the present invention therefore relates to the use of the molar share of deuterium in hydrogen and downstream compounds based on hydrogen for tracing the origin, especially the energetic origin, of the hydrogen and downstream compounds based on hydrogen, wherein the compounds are preferably alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine.
  • the present invention further relates to a process for tracing the origin, especially the energetic origin, of hydrogen and downstream compounds based on hydrogen by determining the molar share of deuterium in hydrogen and said downstream compounds based on hydrogen, wherein the compounds are preferably alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine.
  • Downstream products based on hydrogen are generally products prepared by using hydrogen, preferably alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine.
  • the preparation of the downstream products as well as other downstream products based on hydrogen are known in the art.
  • the origin is in the meaning of the present invention the preparation method of the hydrogen employed, especially electrolysis and/or the energetic origin, i.e. non-fossil energy sources.
  • electrolysis i.e. electrolysis
  • energetic origin i.e. non-fossil energy sources.
  • hydrogen made by electrolysis is in this case hydrogen of non-fossil origin. Examples for non-fossil power sources are mentioned above.
  • the inventive process for tracing the origin, especially the energetic origin, of hydrogen and downstream compounds mentioned above may be employed as a single tracing (tracking) method or in combination with further tracing (tracking) methods.
  • Suitable deuterium molar shares of the compounds based on hydrogen, especially alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine, and the hydrogen itself obtained based on hydrogen made by electrolysis, especially obtained by the process of the present invention, are mentioned in the present application.
  • Inventive compounds accessible with the present invention encompasses any and all such alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimines; such compounds are well-known, i.e. the alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine as accessible with this present invention, and especially those as detailed herein before, and more specifically as those disclosed in the following disclosures of the prior art, such as very preferably those as disclosed by their structure and/or their process to produce as disclosed in EP 2 014 753 A1 , EP 2 925 848 B1 , WO2021/165468 A, WO2021/165493, WO2022/136408 A, WO2022/136409 A, W02023/021104 A, W02023/021105 A, W02023/021103 A, W02023/021101 A, WO2022/136389 A, and WO2023/117494 A, EP36652
  • multifunctional polyethylene imines for example BASF’s Sokalan® HP20 and Sokalan PG617 which are both preferred structures of an inventive compound
  • multifunctional diamines for example BASF’s Sokalan® HP96, which is a preferred structure of an inventive compound.
  • Such multifunctional polyethylene imines - which are inventive compounds according to this present invention - are typically ethoxylated polyethylene imines with a weightaverage molecular weight Mw in the range from 3000 to 250000, preferably 5000 to 200000, more preferably 8000 to 100000, more preferably 8000 to 50000, more preferably 10000 to 30000, and most preferably 10000 to 20000 g/mol.
  • Suitable multifunctional polyethylene imines have 80 wt. % to 99 wt. %, preferably 85 wt. % to 99 wt. %, more preferably 90 wt. % to 98 wt. %, most preferably 93 wt. % to 97 wt. % or 94 wt. % to 96 wt. % ethylene oxide side chains, based on the total weight of the materials.
  • Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell.
  • Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight Mw in the range of 500 to 5000 g/mol.
  • ethoxylated polymer Preferably employed is a molecular weight from 500 to 1000 g/mol, even more preferred is a Mw of 600 to 800 g/mol.
  • the ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.
  • EO ethylene oxide
  • the invention encompasses this also multifunctional diamines which are typically ethoxylated C2 to C12 alkylene diamines, preferably hexamethylene diamine, which may be further quaternized and/or optionally sulfated.
  • Typical multifunctional diamines have a weight-average molecular weight Mw in the range from 2000 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g/mol.
  • ethoxylated hexamethylene diamine, furthermore quaternized and sulfated is a preferred compound, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.
  • EO ethylene oxide
  • All of the before mentioned compounds are encompassed by this present invention when produced using the present invention by replacing at least one element of the prior art process/starting material with an element of the present invention, e.g. replacing the standard fossil-based PEI, EO and/or PO, amine etc with the PEI and/or the EO and/or PO and/or Amine as producible or preferably produced with a process of this present invention.
  • the stae of the art compounds can be replaced partially or completely with inventive compounds having the same or closely similar chemical structures but being produced using at least one element of the present invention, e.g. replacing the standard fossil-based PEI, EO and/or PO and/or amine etc. with the PEI and/or the EO and/or PO and/or Amine as producible or preferably produced with a process of this present invention.
  • step (gO) any of the products from step a), b), c), d), and/or e) are converted in at least one known process step to a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen, to obtain a surfactant comprising less deuterium based on total hydrogen content compared to the chemical identical surfactant obtained from fossil-based sources only.
  • a surfactant comprising at least one structural unit derived from ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen
  • the inventors therefore found a way for tracing the origin of hydrogen and downstream products of hydrogen, preferably the inventive surfactants via the deuterium molar share of said compounds.
  • These downstream products, i.e. surfactants as detailed herein, based on hydrogen, such hydrogen obtained by electrolysis, and hydrogen itself can be distinguished by its deuterium molar share from the chemically in principle identical compounds prepared by processes based on fossil energy, i.e. made by petrochemical processes.
  • the present invention therefore relates to the use of the molar share of deuterium in hydrogen and downstream compounds based on hydrogen for tracing the origin, especially the energetic origin, of the hydrogen and downstream compounds based on hydrogen, wherein the compounds are preferably surfactants as detailed herein.
  • the inventive process for tracing the origin, especially the energetic origin, of hydrogen and downstream compounds mentioned above may be employed as a single tracing (tracking) method or in combination with further tracing (tracking) methods.
  • Such surfactants are structurally known. Many of them are listed in the following sections; those specifically listed and known to be producible with the use of at least one of ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen, are specifically encompassed by this present invention.
  • the process of the present invention can be used to produce any of the following surfactants listed in the following chapters, provided that for such synthesis route at least one of ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen, is used for the process to produce such surfactant.
  • Surfactants producible with the present invention are in principle any provided that for such synthesis route at least one of ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen, is used for the process to produce such surfactant.
  • such surfactants are being disclosed in any of the following disclosures US 2019/390142, W02020/264077, W02020/005476, W02023017061 A1 , WO 03/042262, publications numbers 800542 and 800500, WO 99/05242, U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1
  • Surfactants comprise non-ionic, anionic and amphoteric surfactants which are defined in more detail in the following:
  • Non-ionic cleaning surfactants means surfactants that contain neither positively nor negatively charged functional groups. In contrast to anionic and cationic surfactants, non-ionic surfactants do not ionize in solution.
  • the non-ionic surfactant is selected from compounds of the general formulae (NIS1a) and (NIS1 b): ( 1b)
  • NIS1a The variables of the general formulae (NIS1a) and (N IS1 b) are defined as follows:
  • R1 is selected from C1-C23 alkyl and C2-C23 alkenyl, wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched; examples are n-C7H 15, n-C8H 17, n-C9H 19, n- C11 H23, n-C13H27, n-C15H31 , n-C17H35, i-C9H19, i-C12H25.
  • R2 is selected from H, C1-C20 alkyl and C2-C20 alkenyl, wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched.
  • R3 and R4 each independently selected from C1-C16 alkyl, wherein alkyl is linear (straightchain; n-) or branched; examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpro- pyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl, isodecyl.
  • R5 is selected from H and C1-C18 alkyl, wherein alkyl is linear (straight-chain; n-) or branched.
  • the integers of the general formulae (NIS1 a) and (NIS1 b) are defined as follows: m is in the range of zero to 200, preferably 1-80, more preferably 3-20; n and o, each independently in the range of zero to 100; n preferably is in the range of 1 to 10, more preferably 1 to 6; o preferably is in the range of 1 to 50, more preferably 4 to 25.
  • the sum of m, n and o is at least one, preferably the sum of m, n and o is in the range of 5 to 100, more preferably in the range of from 9 to 50.
  • the non-ionic surfactants of the general formulae (NIS1 a) and (NIS1 b) may be of any structure, is it block or random structure, and is not limited to the displayed sequence of formulae (NIS1a) and (NIS1 b).
  • NIS1a alkyl polyethyleneglycol ether
  • N IS1 b alkylphenol polyethyleneglycol ether
  • the compound is of general formula (NIS1a) with R1 being n- C13H27, R2 and R5 being H, m being 3-20, n and o being 0.
  • the compound is of general formula (NIS1a) with R1 being linear or branched C10 alkyl, R2 and R5 being H, m being 3-14, n and o being 0.
  • the non-ionic cleaning surfactant is selected from compounds of general formula (NIS1 a), wherein the non-ionic cleaning surfactants is characterized in R1 being n-C15H31 , R2 and R5 being H, m being 9-80, n and o being 0, or the cleaning surfactant is characterized in R1 being n-C17 H35, R2 and R5 being H, m being 9-80, n and o being 0.
  • n in both non-ionic cleaning surfactants is 25-80, preferably m is either 25 or 80.
  • Said NIS may be called NIS1 a1 herein.
  • the non-ionic cleaning surfactant is selected from general formula (NIS1 a), wherein m is in the range of 3 to 11 , preferably not more than 10, more preferably not more than 7; n and o being 0, R1 being linear C9-C17 alkyl, R2 and R5 being H.
  • the non-ionic cleaning surfactant is selected from compounds of general formula (NIS1a), wherein said non-ionic cleaning surfactants is characterized in R1 being n-C12H25, R2 and R5 being H, m being 3-30, preferably 7, n and o being 0, or the cleaning surfactant is characterized in R1 being n-C14H29, R2 and R5 being H, m being 3-30, preferably 7, n and o being 0. Said NIS may be called NIS1 a2 herein.
  • Said NIS may be called NIS1 a3 herein.
  • NIS may be called NIS1 a4 herein.
  • NIS may be called NIS1 a5 herein.
  • the non-ionic cleaning surfactant is according to general formula (NIS1 a) with R1 being C3 to C18 linear alkyl, R2 being H, R3 and R4, each independently selected from
  • n or o being 2-25, or
  • R5 is H.
  • R5 is selected from methyl, butyl, benzyl and t-butyl.
  • Said NIS may be called NIS1a6 herein.
  • the compound is according to general formula (NIS1a) with R2 being H, m being 10-50, R3 being linear or branched C8-C12 alkyl, n being 1 or 2 with 1 being preferred, o being 0 or 1 and R5 being H.
  • the compound is according to general formula (NIS1a) with R2 being H, m being 10-50, R3 being linear or branched C8-C12 alkyl, n being 1 or 2 with 1 being preferred, o being 0 or 1 and R5 being H.
  • NIS1a general formula (NIS1a) with R2 being H, m being 10-50, R3 being linear or branched C8-C12 alkyl, n being 1 or 2 with 1 being preferred, o being 0 or 1 and R5 being H.
  • the non-ionic cleaning surfactant is selected from compounds according to formula (NIS1a) with R1 being n-C8 alkyl, R2 being H, R3 being branched C11 alkyl, R5 being H, m being 22, n being 1 and o being 0. Said NIS may be called NIS1a7 herein.
  • the non-ionic cleaning surfactant is selected from compounds according to formula (NIS1a) with R1 being n-C8 alkyl, R2 being H, R3 being branched C11 alkyl, R5 being H, m being 19, n being 1 and o being 0. Said NIS may be called NIS1a8 herein.
  • the non-ionic cleaning surfactant is selected from compounds according to formula (NIS1 a) with R1 being n-C8 alkyl, R2 being H, R3 being n-C8-C10 alkyl, R5 being H, m being 40, n being 1 and o being 0.
  • NIS may be called NIS1 a9 herein.
  • the non-ionic cleaning surfactant selected from compounds according to formula (NIS1 a) with R1 being n-C8 alkyl, R2 being H, R3 being methyl, R4 being n-C10 alkyl, R5 being H, m being 22, n being 1 and o being 1.
  • NIS may be called NIS1a10 herein.
  • the non-ionic cleaning surfactant is selected from compounds of the general formula (NIS2), which might be called alkyl-polyglycosides (APG) herein:
  • R1 in general formula (NIS2) is selected from C1-C17 alkyl and C2-C17 alkenyl, wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched; examples are n-C7H15, n-C9H19, n-C11 H23, n-C13H27, n-C15H31 , n-C17H35, i-C9H19, i-C12H25.
  • R2 in general formula (NIS2) is selected from H, C1-C17 alkyl and C2-C17 alkenyl, wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched.
  • G1 in general formula (NIS2) is selected from monosaccharides with 4 to 6 carbon atoms, such as glucose and xylose.
  • NIS2 The integer w of the general formula (NIS2) is in the range of from 1.1 to 4, w being an average number.
  • NIS2 is caprylyl glucoside, which is a compound according to formulas (NIS2) wherein R1 is n-C6H13, R2 is H, G1 is glucose and w is about 1 .
  • NIS2 is lauryl glucoside, which is a compound according to formulas (NIS2) wherein R1 is n-C10H21 , R2 is H, G1 is glucose and w is about 1.
  • non-ionic cleaning surfactant selected from compounds of general formula (NIS3):
  • NIS3 The variables of the general formula (NIS3) are defined as follows:
  • AO is selected from ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and mixtures thereof.
  • R6 is selected from 05-017 alkyl and 05-017 alkenyl, wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched.
  • R7 is selected from H, C1-C18-alkyl, wherein alkyl is linear (straight-chain; n-) or branched.
  • the integer y of the general formula (N IS3) is a number in the range of 1 to 70, preferably 7 to 15.
  • the non-ionic cleaning surfactant is NIS4 which includes sorbitan esters (NIS4a) and/or ethoxylated (NIS4b) or propoxylated (NIS4c) sorbitan esters.
  • NIS4 sorbitan esters
  • NIS4b ethoxylated
  • NIS4c propoxylated sorbitan esters.
  • SPAN sorbitan esters
  • TWEEN propoxylated
  • the one non-ionic cleaning surfactant NIS5 is selected from alkox- ylated mono- or di-alkylamines (NIS5a), fatty acid monoethanolamides (FAMA, NIS5b), fatty acid diethanolamides (FADA, NIS5c), ethoxylated fatty acid monoethanolamides (EFAM, NIS5d), propoxylated fatty acid monoethanolamides (PFAM, NIS5e), polyhydroxy alkyl fatty acid amides (NIS5f), or N-acyl N-alkyl derivatives of glucosamine (NIS5g) such as glucamides (GA), fatty acid glucamide (FAGA) and combinations thereof.
  • NIS5a alkox- ylated mono- or di-alkylamines
  • FAMA fatty acid monoethanolamides
  • FADA fatty acid diethanolamides
  • EFAM ethoxylated fatty acid monoethanolamides
  • PFAM propoxylated
  • Anionic cleaning surfactant means surfactants with a negatively charged ionic group.
  • Anionic surfactants include, but are not limited to, surface-active compounds that contain a hydrophobic group and at least one water-solubilizing anionic group, usually selected from sulfates, sulfonate, and carboxylates to form a water-soluble compound.
  • the anionic cleaning surfactant is selected from compounds of general formulae (AS 1a) or (AS 1 b):
  • R1 is selected from C1-C23-alkyl (such as 1-, 2-, 3-, 4- C1-C23-alkyl) and C2-C23- alkenyl, wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched, and wherein 2-, 3-, or 4-alkyl; examples are n-C7H 15, n-C9H19, n-C11 H23, n-C13H27, n- C15H31 , n-C17H35, i-C9H19, i-C12H25.
  • C1-C23-alkyl such as 1-, 2-, 3-, 4- C1-C23-alkyl
  • C2-C23- alkenyl wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched, and wherein 2-, 3-, or 4-alkyl; examples are n-C7H 15, n-C9H19, n
  • R2 is selected from H, C1-C20-alkyl and C2-C20-alkenyl, wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched.
  • R is selected from linear (straightchain; n-) or branched C1-C8-alkyl and C1-C4 hydroxyalkyl.
  • Compounds might be called (fatty) alcohol/alkyl (ethoxy/ether) sulfates [(F)A €S] when A- is -SO3-, (fatty) alcohol/alkyl (ethoxy/ether) carboxylate [(F)A €C] when A- is -RCOO-.
  • M+ is selected from H and salt forming cations.
  • Salt forming cations may be monovalent or multivalent; hence M+ equals 1/v Mv+. Examples include but are not limited to sodium, potassium, magnesium, calcium, ammonium, and the ammonium salt of mono-, di, and triethanolamine.
  • m is in the range of zero to 200, preferably 1-80, more preferably 3-20; n and o, each independently in the range of zero to 100; n preferably is in the range of 1 to 10, more preferably 1 to 6; o preferably is in the range of 1 to 50, more preferably 4 to 25.
  • the sum of m, n and o is in the range of 0 to 100. In one embodiment, the sum of m, n and o is 0. In another embodiment the sum of m, n and o is at least one, preferably the sum of m, n and o is in the range of 9 to 50.
  • Anionic cleaning surfactants of the general formulae (AS1a) and (AS1 b) may be of any structure, block copolymers or random copolymers.
  • the anionic cleaning surfactant according to formula (AS1a) is a compound, wherein R1 is n-C11 H23, R2 is H, A- is -SO3-, m, n and o being 0. M+ preferably is Na+.
  • Such compounds may be called sodium lauryl sulfate.
  • the anionic cleaning surfactants according to formula (AS1a) is a compound, wherein AS1 a is characterized by R1 is n-C11 H23, R2 is H, A- is -SO3-, m, n and o being 0; M+ preferably is Na+ or AS1a is characterized by R1 is n-C18H37, R2 is H, A- is -SO3-, m, n and o being 0; M+ preferably is Na+.
  • AS1 a1 is characterized by R1 is n-C11 H23, R2 is H, A- is -SO3-, m, n and o being 0; M+ preferably is Na+.
  • AS1 a1 is characterized by R1 is n-C11 H23, R2 is H, A- is -SO3-, m, n and o being 0; M+ preferably is Na+.
  • AS1 a1 is characterized by R1 is
  • the anionic cleaning surfactant according to formula (AS1a) is a compound, wherein R1 is n-C11 H23, R2 is selected from H, A- is -SO3-, m being 2-5, preferably 3, and n and o being 0. M+ preferably is Na+.
  • Such compounds, herein, may be called laurylether sulfates (LES) or sodium laurylether sulfates (SLES) or AS1a2.
  • anionic cleaning surfactants include salts (M+) of C12-C18 sulfo fatty acid alkyl esters (such as C12-C18 sulfo fatty acid methyl esters), C10-C18-alkylaryl- sulfonic acids (such as n-C10-C18-alkylbenzene sulfonic acids) and C10-C18 alkyl alkoxy carboxylates.
  • M+ in all cases is selected from salt forming cations.
  • Salt forming cations may be monovalent or multivalent; hence M+ equals 1/v Mv+. Examples include but are not limited to sodium, potassium, magnesium, calcium, ammonium, and the ammonium salt of mono- , di, and triethanolamine.
  • the anionic cleaning surfactant is selected from compounds of general formula (AS1 a), wherein said anionic surfactant is characterized in R1 being C11 , R2 being H, m being 2, n and o being 0, A- being -SO3-, M+ being Na+ or the surfactant is characterized in R1 being C13, R2 being H, m being 2, n and o being 0, A- being - SO3-, M+ being Na+.
  • AS may be called AS1a3 herein.
  • the anionic cleaning surfactant selected from compounds of general formulae (AS2a) or (AS2b): wherein R1 in formula (AS2a) is linear or branched C10-C13 alkyl; M+ being preferably Na+. wherein R1 in formula (AS2b) is linear or branched C10-C13 alkyl; n being 1 or 2; M+ being preferably Na+.
  • BABS branched alkylbenzene sulfonates
  • LAS linear alkylbenzene sulfonates
  • the anionic cleaning surfactant is selected from compounds of general formula (AS2a), wherein said anionic cleaning surfactant is characterized in R1 being n-C10H21 , and another surfactant is characterized in R1 being n-C13H27.
  • Said two anionic cleaning surfactants may be sodium salts and may be called AS2a herein.
  • the compound according to formula (AS2b) is a compound, wherein R1 is n-C14H29 to n-C17H35, preferably R1 is n-C12H29 to n-C15H31 .
  • Said compounds may be called alpha-olefin sulfonates (AOS) herein.
  • AOS are a mixture of alkene sulfonates (60-65%) and hydroxyalkane sulfonates (35-40%).
  • the anionic cleaning surfactant is selected from compounds of general formula (AS3), which might be called N-acyl amino acid surfactants:
  • R6 is selected from linear (straight-chain; n-) or branched C6-C22-alkyl and linear (straightchain; n-) or branched C6-C22-alkenyl such as oleyl.
  • R7 is selected from H and C1-C4-alkyL
  • R8 is selected from H, methyl, -(CH2)3NHC(NH)NH2, -CH2C(O)NH2, -CH2C(O)OH, - (CH2)2C(O)NH2, -(CH2)2C(O)OH, (imidazole-4-yl)-methyl, -CH(CH3)C2H5, - CH2CH(CH3)2, -(CH2)4NH2, benzyl, hydroxymethyl, -CH(OH)CH3, (indole-3-yl)-me- thyl, (4-hydroxy-phenyl)-methyl, isopropyl, -(CH2)2SCH3, and -CH2SH.
  • R9 is selected from -COOX and -CH2SO3X, wherein X is selected from Li+, Na+ and K+.
  • AS3 is selected from mono- and di-carboxylate salts (e.g., sodium, potassium, ammonium and ammonium salt of mono-, di, and triethanolamine) of N-acyl- ated glutamic acid, for example, sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, disodium cocoyl glutamate, disodium stearoyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate, and potassium myristoyl glutamate; the carboxylate salts (e.g., sodium, potassium, ammonium and ammonium salt of mono-, di, and triethanolamine) of N-acylated alanine, for example, sodium cocoyl alaninate, and triethanolamine lauroyl alaninate; the carboxylate salts (e.g., sodium, potassium, ammonium and ammonium salt of mono-
  • the anionic cleaning surfactant is selected from the group of soaps (AS4).
  • AS4 are selected from salts (M+) of saturated and unsaturated C12-C 18 fatty acids (AS4a), such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, (hydrated) erucic acid.
  • M+ is selected from salt forming cations. Salt forming cations may be monovalent or multivalent; hence M+ equals 1/v Mv+.
  • Examples include but are not limited to sodium, potassium, magnesium, calcium, ammonium, and the ammonium salt of mono-, di, and triethanolamine.
  • AS4 are salts (M+) of sulfates, sulfonates or carboxylates derived from natural fatty acids (AS4b) such as tallow (mainly C14-C18), coconut oil (mainly C12- C14), palm kernel oil (mainly C8-C18), olive oil (mainly C16-C18) or canola oil (mainly C18).
  • anionic surfactants comprise sulfates, sulfonates or carboxylates of lauric acid and/or myristic acid and/or palmitic acid and/or stearic acid and/or oleic acid and/or linoleic acid in different amounts, depending on the natural fatty acids from which the soaps are derived.
  • the anionic cleaning surfactant is selected from sulfonated fatty acid methyl ester according to formula (AS5): wherein
  • R1 is either fatty acid C6 to C16 or -CH2COOH and M+ is preferably Na+.
  • AS5 is fatty acid methyl ester sulfonate (MES).
  • MES in one embodiment, are derived from natural fatty acids such as tallow (mainly C14-C18), coconut oil (mainly C12-C14), palm kernel oil (mainly C8-C18), olive oil (mainly C16-C18) or canola oil (mainly C18).
  • MES may be called AS5a herein.
  • AS5a is C12-C18 fatty acid methyl ester sulfonate.
  • AS5a is coco methyl ester sulfonate.
  • the anionic cleaning surfactants are monoesters sulfosuccinic acid (may be called AS5b herein) or diesters of sulfosuccinic acid (may be called AS5c herein).
  • Amphoteric cleaning surfactants means those surfactants, depending on pH, which can be either cationic, zwitterionic or anionic.
  • amphoteric cleaning surfactant is selected from compounds of the general formula (AMS1), which might be called modified amino acids (proteinogenic as well as non-proteinogenic):
  • AMS1 The variables in general formula (AMS1) are defined as follows: R8 is selected from H, C1-C4 alkyl, C2-C4 alkenyl, wherein alkyl and/or are linear (straightchain; n-) or branched.
  • R9 is selected from C1-C22- alkyl, C2-C22- alkenyl, C10-C22 alkylcarbonyl, and C10- C22 alkenylcarbonyl.
  • R10 is selected from H, methyl, -(CH2)3NHC(NH)NH2, -CH2C(O)NH2, -CH2C(O)OH, - (CH2)2C(O)NH2, -(CH2)2C(O)OH, (imidazole-4-yl)-methyl, -CH(CH3)C2H5, - CH2CH(CH3)2, -(CH2)4NH2, benzyl, hydroxymethyl, -CH(OH)CH3, (indole-3-yl)-me- thyl, (4-hydroxy-phenyl)-methyl, isopropyl, -(CH2)2SCH3, and -CH2SH.
  • Rx is selected from H and C1-C4-alkyL
  • amphoteric cleaning surfactant selected from compounds of general formulae (AMS2a), (AMS2b), or (AMS2c), which might be called betaines and/or sulfobetaines (AMS2):
  • AMS2a The variables in general formulae (AMS2a), (AMS2b) and (AMS2c) are defined as follows:
  • R11 is selected from linear (straight-chain; n-) or branched C7-C22 alkyl and linear (straightchain; n-) or branched C7-C22 alkenyl.
  • R12 are each independently selected from linear (straight-chain; n-) C1-C4 alkyl.
  • R13 is selected from C1-C5 alkyl and hydroxy C1-C5 alkyl; for example 2-hydroxypropyL is selected from carboxylate and sulfonate.
  • AMS2a The integer r in general formulae (AMS2a), (AMS2b), and (AMS2c) is in the range of 2 to 6.
  • AMS2b is cocoamidopropyl betaine.
  • amphoteric cleaning surfactant selected from compounds of general formula (AMS3), which might be called alkyl-amphocarboxylates:
  • R11 is selected from C7-C22 alkyl and C7-C22 alkenyl, wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched, preferably linear.
  • R15 is selected from H and -CH2C(O)O-.
  • AMS3 The integer r in general formula (AMS3) is in the range of 2 to 6.
  • the alkyl-amphocarboxylate is selected from sodium cocoampho- acetate, sodium lauroamphoacetate, sodium capryloamphoacetate, disodium cocoam- phodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroam- phodipropionate, disodium caprylamphodipropionate, and disodium capryloamphodi- propionate.
  • amphoteric cleaning surfactant is selected from compounds of general formula (AMS4), which might be called amine oxides (AO):
  • AMS4 The variables in general formula (AMS4) are defined as follows:
  • R16 is selected from C8-C18 alkyl, hydroxy C8-C18 alkyl, acylamidopropoyl and C8-C18 alkyl phenyl group; wherein alkyl and/or alkenyl are linear (straight-chain; n-) or branched.
  • R17 is selected from C2-C3 alkylene, hydroxy C2-C3 alkylene, and mixtures thereof.
  • each residue can be independently selected from C1-C3 alkyl and hydroxy C1-C3;
  • R15 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • the integer x in general formula (AMS4) is in the range of 0 to 5, preferably from 0 to 3, most preferably 0.
  • the amine oxide selected from C10-C18 alkyl dimethyl amine oxides and C8-C18 alkoxy ethyl di hydroxyethyl amine oxides.
  • examples of such materials include dimethyloctyl amine oxide, diethyldecyl amine oxide, bis-(2-hydroxyethyl)dodecyl amine oxide, dimethyldodecylamine oxide, dipropyltetradecyl amine oxide, methylethylhexadecyl amine oxide, dodecylamidopropyl dimethyl amine oxide, cetyl dimethyl amine oxide, stearyl dimethyl amine oxide, tallow dimethyl amine oxide and dimethyl-2- hydroxyoctadecyl amine oxide.
  • the amine oxide is cocamidylpropyl dimethylaminoxide, which is sometimes also called cocamidopropylamine oxide.
  • inventive surfactants as disclosed and defined herein are the same as known in the art; such uses of and the products /formulations/compositions comprising such inventive surfactants are especially those, respectively, being disclosed in any of the following disclosures US 2019/390142, WC2020/264077, WC2020/005476, WC2023017061 A1 , WO 03/042262, publications numbers 800542 and 800500 WO 99/05242, U.S. Patent Nos.
  • the surfactants can be replaced partially or completely with inventive surfactants when having the same or closely similar chemical structures but being produced using at least one element of the present invention, e.g. replacing the standard fossil-based ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, and/or hydrogen, with ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, and/or hydrogen, as producible or preferably produced with a process of this present invention.
  • the “inventive compound(s)” and “compound(s) of the invention” are specifically alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine or specifically surfactants, the “inventive compound(s)” and “compound(s) of the invention” are characterized accordingly. Otherwise, the “inventive compound(s)” and “compound(s) of the invention” cover alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine as well as specifically surfactants.
  • inventive compound(s) encompasses one, two, three, four or more inventive compound(s) as a mixture.
  • inventive compound(s) as directly obtained from the inventive process can be used advantageously in cleaning compositions.
  • They may be used as at least one inventive compound, or mixtures of more than one inventive compound.
  • any of the surfactants being mentioned in this section and the sections thereafter, on uses and compositions and cleaning additives etc., and producible with the use of ethylene oxide, methanol, ammonia, monoethanolamine, diethanolamine and triethanolamine, or hydrogen and thus with the use of at least one element of this present invention, can be partially or fully replaced with an inventive surfactant of the same chemical structure but being produced with the use of this present invention.
  • the inventive compound(s) can be added to cleaning compositions.
  • inventive compound(s) are present in general in said formulations at a concentration of from about 0.1 % to about 50%, preferably from about 0,25% to 15%, more preferably from about 0.5% to about 10%, and even more preferably from about 0.5% to about 5%, and most preferably in amounts of up to 3%, each in weight % in relation to the total weight of such composition/product, optionally further comprising from about 1 % to about 70% by weight of a surfactant system, wherein - specifically - for a liquid hand dishwashing or spray detergent cleaning composition such composition comprising from 0.1 % to 50%, preferably from 1 % to 35%, more preferably from 3% to 30%, by weight of the total composition, of a surfactant system, and such surfactant system preferably comprising from 60% to 90%, more preferably from 70% to 80% by weight of the surfactant system of an anionic surfactant.
  • an inventive surfactant can of course be
  • inventive compound ⁇ obtained by a process of the invention as detailed before, in fabric and home care products, in particular cleaning compositions for improved oily and fatty stain removal, removal of solid dirt such as clay, prevention of greying of fabric surfaces, and/or anti-scale agents, wherein the cleaning composition is preferably a laundry detergent formulation and/or a dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.
  • Another subject-matter of the present invention is, therefore, also a cleaning composition, fabric and home care product, industrial and institutional cleaning product, prefera- bly in laundry detergents, in cleaning compositions and/or in fabric and home care products, each comprising at least one inventive compound(s) obtained by a process of the invention.
  • a further subject-matter of the present invention is a fabric and home care product, cleaning composition, industrial and institutional cleaning product, preferably a laundry detergent, a cleaning composition and/or a fabric and home care product, each containing at least one inventive compound obtained by a process of the invention.
  • it is a cleaning composition and/or fabric and home care product and/or industrial and institutional cleaning product, comprising at least one inventive compound obtained by a process of the invention.
  • a cleaning composition for improved cleaning performance especially improved primary washing, preferably a laundry detergent formulation and/or a manual dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.
  • the cleaning composition of the present invention is a liquid or solid laundry detergent composition, preferably a liquid laundry detergent composition.
  • the cleaning composition of the present invention is a liquid or solid (e.g. powder or tab/unit dose) detergent composition for manual or automatic dish wash, preferably a liquid manual dish wash detergent composition.
  • a liquid or solid detergent composition for manual or automatic dish wash preferably a liquid manual dish wash detergent composition.
  • Such compositions are known to a person of skill in the art.
  • the cleaning composition of the present invention is a hard surface cleaning composition that may be used for cleaning various surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass.
  • a hard surface cleaning composition that may be used for cleaning various surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass.
  • a detergent formulation for washing dishes and cutlery i.e. a “hand dish detergent”.
  • a spray cleaner which is typically to be sprayed on a hard surface and then wiped away thereby removing soil and grease etc.
  • the inventive compound(s) obtained by a process of the invention is a component of a cleaning compositions or fabric and home care product, preferably a laundry cleaning composition, a laundry care product or laundry treatment product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant.
  • the cleaning composition comprises (besides at least one inventive compound obtained by a process of the invention) additionally at least one enzyme, preferably selected from one or more option- ally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicore- ductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme being selected from lipases.
  • at least one enzyme preferably selected from one or more option- ally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pect
  • the cleaning compositions of the present invention comprising at least one inventive compound obtained by a process of the invention and optionally further comprising at least one surfactant or a surfactant system - as detailed before - are those for improved cleaning performance within laundry and manual dish wash applications, even more specifically, for improved cleaning performance (such actions as detailed before) such as those on fabrics and dishware, and may additionally comprise at least one enzyme selected from the list consisting of optionally further comprising at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably
  • inventive compound(s) obtained by a process of the invention may be utilized in cleaning compositions comprising a surfactant system comprising C10-C15 alkyl benzene sulfonates (LAS) as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.
  • LAS alkyl benzene sulfonates
  • inventive compound(s) obtained by a process of the invention may be utilized in cleaning compositions or fabric and home care product, preferably a laundry cleaning composition, a laundry care product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising C12-C18 alkyl ethoxylate surfactants with 5-10 ethoxy-units as the primary surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants, or mixtures thereof.
  • cleaning compositions or fabric and home care product preferably a laundry cleaning composition, a laundry care product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising C12-C18 alkyl ethoxylate surfactants with 5-10 ethoxy-units as the primary surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants, or mixtures thereof.
  • the inventive compound(s) obtained by a process of the invention may be utilized in the cleaning compositions or fabric and home care product, preferably a laundry cleaning composition, a laundry care product or laundry treatment product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising C8-C18 linear or branched alkyl ethersulfates with 1-5 ethoxy-units as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.
  • the inventive compound(s) obtained by a process of the invention is a component of a cleaning composition, such as preferably a laundry or a dish wash formulation, more preferably a liquid laundry or manual dish wash formulation, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant.
  • a cleaning composition such as preferably a laundry or a dish wash formulation, more preferably a liquid laundry or manual dish wash formulation, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant.
  • this invention also encompasses a composition comprising at least one inventive compound obtained by a process of the invention, further comprises an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.
  • an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.
  • this invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising inventive compound(s) obtained by a process of the invention in the amounts detailed before as described herein before, such composition further comprising 4,4’-dichoro 2-hydroxydi- phenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition.
  • this invention also encompasses a composition, specifically a cleaning composition, more preferably a cleaning composition in liquid, solid or semisolid form, preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation or solid automatic dish washing formulation, more preferably a laundry detergent formulation, comprising inventive compound(s) obtained by a process of the invention and in the amounts as detailed before, such composition being preferably a detergent composition, such composition further comprising an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.
  • a cleaning composition more preferably a cleaning composition in liquid, solid or semisolid form, preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation or solid automatic dish washing formulation, more preferably a laundry detergent formulation, comprising inventive compound(s) obtained by a process
  • this invention also encompasses a method of preserving an aqueous composition against microbial contamination or growth, such composition, specifically a cleaning composition, more preferably a cleaning composition in liquid, solid or semi-solid form, preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation or solid automatic dish washing formulation, more preferably a laundry detergent formulation, comprising inventive compound(s) obtained by a process of the invention and in the amounts detailed before, such composition being preferably a deter- gent composition, such method comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents as disclosed hereinafter, such antimicrobial agent preferably being 2-phenoxyethanoL
  • this invention also encompasses a method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising inventive compound(s) obtained by a process of the invention in the amounts detailed before, such composition further comprising 4,4’-dichoro 2-hydroxydi- phenylether.
  • a cleaning composition more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising inventive compound(s) obtained by a process of the invention in the amounts detailed before, such composition further comprising 4,4’-dichoro 2-hydroxydi- phenylether.
  • cleaning composition includes compositions and formulations designed for cleaning soiled material.
  • Such compositions include but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein.
  • compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation.
  • the cleaning compositions may have a form selected from liquid, powder, single-phase or multi-phase unit dose, pouch, tablet, gel, paste, bar, or flake.
  • the cleaning compositions of the invention comprise a surfactant system in an amount sufficient to provide desired cleaning properties.
  • the cleaning composition comprises, by weight of the composition, from about 1 % to about 70% of a surfactant system.
  • the liquid cleaning composition comprises, by weight of the composition, from about 2% to about 60% of the surfactant system.
  • the cleaning composition comprises, by weight of the composition, from about 5% to about 30% of the surfactant system.
  • such composition comprises preferably from from 60% to 90%, more preferably from 70% to 80% by weight of the surfactant system, more preferably of an anionic surfactant.
  • the surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, am- pholytic surfactants, and mixtures thereof.
  • a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
  • compositions or products of the present invention as detailed herein before comprising at least one inventive alkoxylated amino acid esters and/or their salts obtained by a process of the invention and in the amounts as specified in the previous paragraph, optionally further comprising at least one surfactant or a surfactant system in amounts from about 1 % to about 70% by weight of the composition or product, are preferably those for primary cleaning (i.e.
  • stains removal of stains
  • laundry applications may additionally comprise at least one enzyme selected from lipases, hydrolases, amylases, proteases, cellulases, man- nanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types.
  • at least one enzyme selected from lipases, hydrolases, amylases, proteases, cellulases, man- nanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types.
  • cleaning composition includes compositions and formulations and products designed for cleaning soiled material. Such compositions, formulations and products include those designed for cleaning soiled material or soiled surfaces of any kind.
  • compositions for “industrial and institutional cleaning” includes such cleaning compositions being designed for use in industrial and institutional cleaning, such as those for use of cleaning soiled material or surfaces of any kind, such as hard surface cleaners for surfaces of any kind, including tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, lacquered surfaces.
  • compositions for Fabric and Home Care include cleaning compositions including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein.
  • Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation, preferably during the wash cycle of the laundering or dish washing operation.
  • the cleaning compositions of the invention may be in any form, namely, in the form of a liquid; a solid such as a powder, granules, agglomerate, paste, tablet, pouches, bar, gel; an emulsion; types delivered in dual- or multi-compartment containers; singlephase or multi-phase unit dose; a spray or foam detergent; premoistened wipes (i.e., the cleaning composition in combination with a nonwoven material such as that discussed in US 6,121 ,165, Mackey, et al.); dry wipes (i.e., the cleaning composition in combination with a nonwoven materials, such as that discussed in US 5,980,931 , Fowler, et al.) activated with water by a user or consumer; and other homogeneous, non-homogeneous or single-phase or multiphase cleaning product forms.
  • liquid cleaning compositions of the present invention preferably have a viscosity of from 50 to 10000 mPa*s; liquid manual dish wash cleaning compositions (also liquid manual “dish wash compositions”) have a viscosity of preferably from 100 to 10000 mPa*s, more preferably from 200 to 5000 mPa*s and most preferably from 500 to 3000 mPa*s at 20 1/s and 20°C; liquid laundry cleaning compositions have a viscosity of preferably from 50 to 3000 mPa*s, more preferably from 100 to 1500 mPa*s and most preferably from 200 to 1000 mPa*s at 20 1/s and 20°C.
  • the cleaning compositions and formulations of the invention may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as “adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before.
  • adjunct cleaning additives also abbreviated herein as “adjuncts”
  • Suitable adjunct cleaning additives include builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, and perfumes.
  • dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating
  • Liquid cleaning compositions additionally may comprise - and preferably do comprise at least one of - rheology control/modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.
  • Solid compositions additionally may comprise - and preferably do comprise at least one of - fillers, bleaches, bleach activators and catalytic materials.
  • the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above.
  • the surfactant system may be composed from one surfactant or from a combination of surfactants selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
  • a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
  • the cleaning compositions of the invention typically comprise a surfactant system in an amount sufficient to provide desired cleaning properties.
  • the liquid cleaning compositions of the present invention may have any suitable pH- value.
  • the pH of the composition is adjusted to between 4 and 14. More preferably the composition has a pH of from 6 to 13, even more preferably from 6 to 10, most preferably from 7 to 9.
  • the pH of the composition can be adjusted using pH modifying ingredients known in the art and is measured as a 10% product concentration in demineralized water at 25°C.
  • NaOH may be used and the actual weight% of NaOH may be varied and trimmed up to the desired pH such as pH 8.0.
  • a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.
  • cleaning compositions their ingredients including (adjunct) cleaning additives, their general compositions and more specific compositions are known, as for example illustrated in WO 2022/136409 and WO 2022/136408, wherein in any of the before prior art documents the inventive compound, i.e. any of the alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine (wherein any of the before may optionally include also other alkylene oxide(s) and7or lactone(s) in the alkylene oxide chain(s)) or any of the surfactants as detailed herein, within the general compositions and also each individualized specific cleaning composition disclosed in the beforementioned publications may be replaced partially or completely by the respective inventive compound prepared using the present invention.
  • inventive compound i.e. any of the alkoxylated di-, oligo- and polyamines and alkoxylated polyethylenimine (wherein any of the before may optionally include also other alkylene oxide(s) and7or lactone(
  • the content of the inventive compound being present in said formulations is the same concentration as used in the referenced prior art document and the products and formulations therein; such concentration - in case of surfactants - typically being from 0,05 to 50 wt.%, preferably up to 40 wt. %, more preferably 0.1 to 30 weight%, even more preferably at a concentration of 0.5 to 20 weight%, and any number in between as lower and as upper range, so that any range possibly being made up within the broadest range can be also selected as specific range.
  • Liquid cleaning compositions additionally may comprise - and preferably do comprise at least one of - rheology control/modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.
  • Solid compositions additionally may comprise - and preferably do comprise at least one of - fillers, bleaches, bleach activators and catalytic materials.
  • a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
  • the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above and below in more detail.
  • the surfactant system may be composed from one surfactant or from a combination of surfactants selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
  • a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.
  • the cleaning compositions of the invention preferably comprise a surfactant system in an amount sufficient to provide desired cleaning properties.
  • the surfactant system may comprise a detersive surfactant selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.
  • the surfactants mentioned as cleaning additives may be conventional surfactants produced from other means than this present invention, or may be partially or fully made according to this present invention.
  • “Laundry composition” may be any composition, formulation or product which is intended for use in laundry including laundry care, laundry cleaning etc.; hence this term will be used in the following denoting any composition, formulation or product.
  • Nonlimiting examples of anionic surfactants - which may be employed also in combinations of more than one surfactant - useful herein include C9-C20 linear alkylbenzenesulfonates (LAS), C10-C20 primary, branched chain and random alkyl sulfates (AS); C10-C 18 secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) wherein x is from 1 to 30; C10-C18 alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99
  • suitable anionic surfactants are alkali metal and ammonium salts of C8-C12-al kyl sulfates, of C12-C18-fatty alcohol ether sulfates, of C12-C18-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-C12-alkylphe- nols (ethoxylation: 3 to 50 mol of ethylene oxide/mol), of 012-018-alkylsulfonic acids, of 012-C18 sulfo fatty acid alkyl esters, for example of 012-018 sulfo fatty acid methyl esters, of C10-C18-alkylarylsulfonic acids, preferably of n-C10-C18-alkylbenzene sulfonic acids, of 010-C18 alkyl alkoxy carboxylates and of soaps such as for example C8-C24-carboxylic acids.
  • Preference is given to the following
  • the alkoxylation group of both types of alkoxylated alkyl sulfates is an ethoxylation group and an average ethoxylation degree of any of the alkoxylated alkyl sulfates is 1 to 5, preferably 1 to 3.
  • anionic surfactants are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10-C18 alkylsulfates.
  • Cleaning compositions may also contain non-ionic surfactants - which may be employed also in combinations of more than one other surfactant.
  • Non-limiting examples of non-ionic surfactants - which may be employed also in combinations of more than one other surfactant - include: C8-C18 alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF; C14-C22 mid-chain branched alkyl alkox- ylates, BAEx, wherein x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as discussed in U.S.
  • C8-C18 alkyl ethoxylates such as, NEODOL® non-ionic surfactants from Shell
  • ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF
  • non-ionic surfactants are in particular alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glu- camides).
  • Examples of (additional) amphoteric surfactants are so-called amine oxides.
  • Cleaning compositions may also contain amphoteric surfactants - which may be employed also in combinations of more than one other surfactant.
  • Non-limiting examples of amphoteric surfactants - which may be employed also in combinations of more than one other surfactant - include: water-soluble amine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. See WO 01/32816, US 4,681 ,704, and US 4,133,779. Suitable surfactants include thus so-called amine oxides, such as lauryl dimethyl amine oxide (“laura- mine oxide”).
  • amphoteric surfactants are amine oxides.
  • Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amido propyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides and especially coco dimethyl amino oxides.
  • Amine oxides may have a linear or mid-branched alkyl moiety.
  • Formulations according to the invention can comprise one or more alkali carriers.
  • the laundry formulation or composition according to the invention comprises additionally at least one enzyme.
  • Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types.
  • composition according to the present invention comprises additionally at least one enzyme.
  • the at least one enzyme is a detergent enzyme.
  • the enzyme is classified as an oxidoreductase (EC 1), a transferase (EC 2), a hydrolase (EC 3), a lyase (EC 4), an isomerase (EC 5), or a ligase (EC 6) (the EC-numbering is according to Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology including its supplements published 1993-1999).
  • the enzyme is a hydrolase (EC 3).
  • the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullula- nases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, DNase, phosphodiesterases, phytases, carbohydrases, galactanases, xanthanases, xyloglucanases, oxidoreductase, perhydrolase
  • the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the foregoing types.
  • the enzyme is a protease, preferably, a serine protease, more preferably, a subtilisin protease.
  • Such enzyme(s) can be incorporated into the composition at levels sufficient to provide an effective amount for achieving a beneficial effect, preferably for primary washing effects and/or secondary washing effects, like antigreying or antipilling effects (e.g., in case of cellulases).
  • the enzyme is present in the composition at levels from about 0.00001 % to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001 % to about 1 %, or even more preferably from about 0.001 % to about 0.5% enzyme protein by weight of the composition.
  • the enzyme-containing composition further comprises an enzyme stabilizing system.
  • the enzyme-containing composition described herein comprises from about 0.001 % to about 10%, from about 0.005% to about 8%, or from about 0.01 % to about 6%, by weight of the composition, of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme.
  • the enzyme stabilizing system comprises at least one compound selected from the group consisting of polyols (preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2-propanediol, or sorbitol), salts (preferably, CaCI2, MgCI2, or NaCI), short chain (preferably, C1-C6) carboxylic acids (preferably, formic acid, formate (preferably, sodium formate), acetic acid, acetate, or lactate), borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • polyols preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2-propanediol, or sorbitol
  • salts preferably, CaCI
  • the enzyme stabilizing system comprises a combination of at least two of the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids and preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • boronic acids preferably, 4-formyl phenylboronic acid (4-FP
  • protease inhibitors may be added, preferably selected from borate, boric acid, boronic acids (preferably, 4-FPBA), peptide aldehydes (preferably, peptide aldehydes like Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde hydrosulfite adducts.
  • Compositions according to the invention may comprise one or more bleaching agent (bleaches).
  • Preferred bleaches are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term “persulfate” in each case includes the salt of the peracid H2SO5 and also the peroxodisulfate.
  • the alkali metal salts can in each case also be alkali metal hydrogen carbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulfate.
  • the dialkali metal salts are preferred in each case.
  • Formulations according to the invention can comprise one or more bleach catalysts.
  • Formulations according to the invention can comprise one or more bleach activators.
  • Formulations according to the invention can comprise one or more corrosion inhibitors, such compounds for example being N-(2-carboxyethyl)-N-dodecyl-beta-alaninate (also named N-lauryl-beta-iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium).
  • corrosion inhibitors such compounds for example being N-(2-carboxyethyl)-N-dodecyl-beta-alaninate (also named N-lauryl-beta-iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium).
  • Formulations according to the invention may also comprise further cleaning polymers and/or soil release polymers.
  • the additional cleaning polymers may include, without limitation, “multifunctional polyethylene imines” (for example BASF’s Sokalan® HP20) and/or “multifunctional diamines” (for example BASF’s Sokalan® HP96).
  • Such multifunctional polyethylene imines are typically ethoxylated polyethylene imines with a weight-average molecular weight Mw in the range from 3000 to 250000, preferably 5000 to 200000, more preferably 8000 to 100000, more preferably 8000 to 50000, more preferably 10000 to 30000, and most preferably 10000 to 20000 g/mol.
  • Suitable multifunctional polyethylene imines have 80 wt. % to 99 wt. %, preferably 85 wt. % to 99 wt.
  • Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell.
  • Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight Mw in the range of 500 to 5000 g/mol.
  • Mw weight-average molecular weight
  • Preferably employed is a molecular weight from 500 to 1000 g/mol, even more preferred is a Mw of 600 to 800 g/mol.
  • the ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.
  • EO ethylene oxide
  • Suitable multifunctional diamines are typically ethoxylated C2 to C12 alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated.
  • Typical multifunctional diamines have a weight-average molecular weight Mw in the range from 2000 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g/mol.
  • ethoxylated hexamethylene diamine may be employed, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.
  • EO ethylene oxide
  • the cleaning compositions may contain at least one multifunctional polyethylene imine and/or at least one multifunctional diamine to improve the cleaning performance, such as preferably improve the stain removal ability, especially the primary detergency of particulate stains on polyester fabrics of laundry detergents.
  • the multifunctional polyethylene imines or multifunctional diamines or mixtures thereof according to the descriptions above may be added to the laundry detergents and cleaning compositions in amounts of generally from 0.05 to 15 wt. %, preferably from 0.1 to 10 wt. % and more preferably from 0.25 to 5 wt. % and even as low as up to 2 wt.%, based on the particular overall composition, including other components and water and/or solvents.
  • one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one inventive compound and (ii) at least one compound selected from multifunctional polyethylene imines and multifunctional diamines and mixtures thereof.
  • the ratio of the at least one inventive compound and (ii) the at least one compound selected from multifunctional polyethylene imines and multifunctional diamines and mixtures thereof is from 10:1 to 1 :10, preferably from 5:1 to 1 :5 and more preferably from 3:1 to 1 :3.
  • Cleaning compositions, fabric and home care products and specifically the laundry formulations comprising the inventive compound may also comprise at least one antimicrobial agent (named also “preservative”).
  • An antimicrobial agent is a chemical compound that kills microorganisms or inhibits their growth or reproduction.
  • Microorganisms can be bacteria, yeasts or molds.
  • a preservative is an antimicrobial agent which may be added to aqueous products and compositions to maintain the original performance, characteristics and integrity of the products and compositions by killing contaminating microorganisms or inhibiting their growth.
  • composition/formulation may contain one or more antimicrobial agents and/or preservatives as listed in patent WO2021/115912 A1 (“Formulations comprising a hydro- phobically modified polyethyleneimine and one or more enzymes”) on pages 35 to 39.
  • Formulations according to the invention may also comprise water and/or additional organic solvents, e.g., ethanol or propylene glycol.
  • Further optional ingredients may be but are not limited to viscosity modifiers, cationic surfactants, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, and dye transfer inhibiting agents.
  • Another aspect of the present invention is also a dish wash composition, comprising at least one inventive compound(s) as described above.
  • an aspect of the present invention is also the use of the inventive compound(s) as described above, in dish wash applications, such as manual or automated dish wash applications.
  • Dish wash compositions according to the invention can be in the form of a liquid, semiliquid, cream, lotion, gel, or solid composition, solid embodiments encompassing, for example, powders and tablets.
  • Liquid compositions are typically preferred for manual dish wash applications, whereas solid formulations and pouch formulations (where the pouches may contain also solids in addition to liquid ingredients) are typically preferred for automated dish washing compositions; however, in some areas of the world also liquid automated dish wash compositions are used and are thus of course also encompassed by the term “dish wash composition”.
  • the dish wash compositions are intended for direct or indirect application onto dishware and metal and glass surfaces, such as drinking and other glasses, beakers, dish and cooking ware like pots and pans, and cutlery such as forks, spoons, knives and the like.
  • the inventive method of cleaning dishware, metal and/or glass surfaces comprises the step of applying the dish wash cleaning composition, preferably in liquid form, onto the surface, either directly or by means of a cleaning implement, i.e., in neat form.
  • the composition is applied directly onto the surface to be treated and/or onto a cleaning device or implement such as a dish cloth, a sponge or a dish brush and the like without undergoing major dilution (immediately) prior to the application.
  • the cleaning device or implement is preferably wet before or after the composition is delivered to it.
  • the composition can also be applied in diluted form.
  • the composition is formulated to provide superior grease cleaning (degreasing) properties, long-lasting suds and/or improved viscosity control at decreased temperature exposures; preferably at least two, more preferably all three properties are present in the inventive dish wash composition.
  • Optional - preferably present - further benefits of the inventive manual dish wash composition include soil removal, shine, and/or hand care; more preferably at least two and most preferably all three further benefits are present in the inventive dish wash composition.
  • the inventive compound(s) is one component of a manual dish wash formulation that additionally comprises at least one surfactant, preferably at least one anionic surfactant.
  • the inventive compound(s) is one component of a manual dish wash formulation that additionally comprises at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric surfactants and/or zwitterionic surfactants.
  • the manual dish wash formulations contain at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or mixtures thereof, to aid in the foaming, detergency, and/or mildness of the detergent composition.
  • Dish wash compositions according to the invention may comprise at least one hydrotrope in an effective amount, to ensure the compatibility of the liquid manual dish wash detergent compositions with water.
  • Dish wash compositions according to the invention may comprise at least one organic solvent.
  • the dish wash compositions herein may further comprise from 30 wt% to 90 wt% of an aqueous liquid carrier, comprising water, in which the other essential and optional ingredients are dissolved, dispersed or suspended. More preferably the compositions of the present invention comprise from 45 wt% to 85 wt%, even more preferably from 60 wt% to 80 wt% of the aqueous liquid carrier.
  • the aqueous liquid carrier may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature (25 °C) and which may also serve some other function besides that of an inert filler.
  • Dish wash compositions according to the invention may comprise at least one electrolyte.
  • Manual dish wash formulations comprising the inventive compound(s) may also comprise at least one antimicrobial agent.
  • the antimicrobial agent may be added to the inventive hand dish wash composition in a concentration of 0.0001 wt% to 10 wt% relative to the total weight of composition.
  • the formulation contains 2-phenoxyethanol in a concentration of 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt% and/or 4,4’-dichloro 2-hydroxydiphenyl ether in a concentration of 0.001 wt% to 1 wt%, more preferably 0.002 wt% to 0.6 wt% (in all cases relative to the total weight of the composition).
  • Further additional ingredients are such as but not limited to conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, emollients, humectants, skin rejuvenating actives, carboxylic acids, scrubbing particles, bleach and bleach activators, perfumes, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, antibacterial agents, pH adjusters including NaOH and alkanolamines such as mono-ethanolamines and buffering means.
  • the present invention further relates to:
  • the invention is further illustrated by examples.
  • Example 1 Preparation of Ethanolamines (MEA/DEA/TEA) Ethanolamines have been prepared as described in US 5,880,058 example 17. Both raw materials ammonia and ethylene oxide were fed into the reactor in the composition, ratio and conditions as defined in the mentioned patent example and the source and combination of both feed materials were varied using the following raw material grades:
  • Example 1d was conducted with a mixed feed of ethylene oxide and ammonia (composition wt-% of the non-fossil I fossil starting materials shown in table 1)
  • the raw MEA/DEA/TEA mixtures obtained in examples 1 a), 1 b), 1 c), 1d) and C1e) were subjected to purification by vacuum distillation. Due to the big differences in boiling temperatures (MEA ⁇ 170°C, DEA ⁇ 270°C, TEA ⁇ 335°C) the separation of MEA is achieved with high purity >99.5% in a standard distillation setup. Light boiling fractions (i.a. water and small amounts of residual ammonia and EO) as well as high boiling substances (i.a. DEA, TEA and oligomer sump sludge) were disposed.
  • Light boiling fractions i.a. water and small amounts of residual ammonia and EO
  • high boiling substances i.a. DEA, TEA and oligomer sump sludge
  • the purified MEA samples have been converted to crude ethylenimine by catalytic gasphase dehydration as outlined in US 9,920,008 B2 example 2.
  • the process was run continuously with freshly prepared catalyst by feeding and contacting MEA with the catalyst bed with conditions as defined in the mentioned patent example and the source of MEA feed material was varied using the purified MEA as described in example 1 above.
  • the reaction gas was quenched by absorption with water and sampled/ana- lyzed after 8 hours and again after 1000 hours of continuous runtime. In table 3 the results are shown.
  • Example 3 Preparation of polyethylenimine
  • the crude ethylenimine raw material feed obtained in examples 2a), 2b) and C2e) was subjected to continuous purification by vacuum distillation as described in CN 112457230A example 4. Separation of ethylenimine was achieved with high purity > 99.5% in the described distillation setup with 4 stages with conditions as defined in the mentioned patent example.
  • Light boiling fractions i.a. acetaldehyde, ethylamine
  • high boiling substances i.a. water, acetonitrile, piperazine and oligomer sump sludge
  • Samples of pure El product condensed from the final column 4 head were taken under steady state conditions.
  • the purified El samples have been converted to polyethylenimine by aqueous ringopening polymerization as described in the following section and the PEI product was analyzed as shown below.
  • a stirred double-jacketed reactor vessel equipped with a vertical reflux intensive condenser (cooled with chilled water) was flushed with nitrogen to completely displace air. Then 100 g deinonized water, 17 g ethylenediamine and 6 g carbon dioxide were charged and the reactor was heated to 85°C while stirring. Thereafter, heating was stopped and while dosing 240 g of purified ethylenimine (El) within 6 hours the reactor temperature and pressure was held constant with automated temperature control (90 +-2°C) thereby continuously removing the heat of reaction via jacket cooling with cold water. After a post reaction time of 3 hours the reactor content was heated to 120°C.
  • El purified ethylenimine
  • the yield of polyethyleneimine in the polymerization step, expressed in molar conversion of El is almost quantitative (close to 100%) due to the controlled reaction in diluted aqueous solution with sufficient starter in a practically closed system as well as the provided post-reaction time.
  • Losses of volatile organic carbon (VOC) to the reactor offgas system are minimized by appropriate condenser design operated with chilled water so that only traces need to be scrubbed and removed/disposed. This is state-of-the art for PEI manufacturing especially since residual El in the PEI product usually must be minimized to non-detectable levels for product safety reasons.
  • the share of secondary amino groups is increased at the expense of the share of primary amino groups in the inventive polyethylenimine compared with the conventionally prepared polyethylenimine.
  • Said ratio of primary, secondary and tertiary amino groups in the inventive polyethylenimine is beneficial for the stability of the polyethylenimine during carbon capturing and thus improves the lifetime of the polymer (primary amino groups generally decompose faster under the conditions that occur during cyclic exposure at for example up to 110°C during the CO2 desorption phase than secondary amino groups).
  • Example 4 Determination of the total cradle-to-gate product carbon footprint (PCF) of mono-, di and triethanolamine and polyethylenimine
  • the process for preparing polyethylenimine comprises the following steps:
  • step (c) converting the methanol from step (b) to ethylene
  • step (d) reacting ethylene from step (c) with oxygen to form ethylene oxide
  • step (e) converting the ammonia from step (a) with ethylene oxide from step (d) to ethanolamines in one or more steps
  • step (f) separating monoethanolamine from the ethanolamines obtained in step (e);
  • step (g) converting monoethanolamine from step (f) to ethylenimine, by a catalytic gasphase synthesis
  • step (h) polymerizing ethylenimine obtained in step (g) to polyethylenimine, wherein the hydrogen in step (a) and/or step (b) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources.
  • the total cradle-to-gate PCF data were determined based on the TfS Guideline* as follows:
  • Raw Materials e.g. kg raw material/kg step product (for all major raw materials)
  • Waste Generation e.g. waste material output in kg waste/kg step product and the effective carbon content in wt-%, for example as total organic carbon (TOC) in waste water (for all C-containing waste materials)
  • TOC total organic carbon

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Polyethers (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Epoxy Compounds (AREA)

Abstract

La présente invention concerne un procédé de préparation d'oxyde d'éthylène ou d'oxyde de propylène comprenant (b) la réaction d'hydrogène avec des oxydes de carbone pour former du méthanol, (c) la conversion du méthanol de l'étape (b) en éthène et/ou propène, (d) la réaction de l'éthène et/ou du propène de l'étape (c) avec de l'oxygène ou un agent oxydant pour former de l'oxyde d'éthylène et/ou de l'oxyde de propylène, le dioxyde de carbone dans l'étape (b) étant au moins en partie capturé à partir de gaz de combustion industriels ou d'air ou d'eau océanique ou d'autres eaux naturelles ou obtenu à partir de processus biologiques, par exemple à partir de processus de fermentation à partir de déchets ou de biomasse, et/ou l'hydrogène dans l'étape (b) étant obtenu au moins en partie par dissociation de l'eau, la dissociation de l'eau utilisant de préférence l'énergie générée au moins en partie à partir de ressources non fossiles ; un procédé de préparation d'éthanolamines, un procédé de préparation de composés alcoxylés, un procédé de fabrication de diamines, d'oligoamines et de polyamines alcoxylées ou de polyéthylèneimine alcoxylée, un procédé de fabrication de polyéthylèneimine alcoxylée, un procédé de fabrication de tensioactif, chaque procédé étant basé sur ledit procédé de préparation d'oxyde d'éthylène ou d'oxyde de propylène ; les polyéthylèneimines, les éthanolamines, les composés alcoxylés, les tensioactifs, les diamines, oligoamines et polyamines alcoxylées, et les polyéthylèneimines alcoxylées pouvant être obtenues par les procédés susmentionnés ; l'utilisation des polyéthylèneimines, des éthanolamines, des composés alcoxylés, des tensioactifs, des diamines, oligoamines et polyamines alcoxylées, et des polyéthylèneimines alcoxylées ; une composition étant un détergent de nettoyage, une composition de nettoyage ou un tissu et un produit d'entretien ménager, contenant au moins des diamines, oligoamines et polyamines alcoxylées ou de la polyéthylèneimine alcoxylée, ou un tensioactif ; les polyéthylèneimines, les éthanolamines, les tensioactifs alcoxylés, les diamines, oligoamines et polyamines alcoxylées, et les polyéthylèneimines alcoxylées avec une quantité réduite de teneur en hydrogène à base de fossiles ayant ainsi un berceau réduit global pour déclencher une empreinte carbone de produit.
EP24707865.2A 2023-03-02 2024-03-04 Oxyde d'éthylène respectueux de l'environnement, oxyde de propylène et produits en aval Pending EP4673492A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP23159730 2023-03-02
EP23175778 2023-05-26
EP23207077 2023-10-31
EP23207078 2023-10-31
PCT/EP2024/055617 WO2024180261A2 (fr) 2023-03-02 2024-03-04 Oxyde d'éthylène respectueux de l'environnement, oxyde de propylène et produits en aval

Publications (1)

Publication Number Publication Date
EP4673492A2 true EP4673492A2 (fr) 2026-01-07

Family

ID=90059675

Family Applications (1)

Application Number Title Priority Date Filing Date
EP24707865.2A Pending EP4673492A2 (fr) 2023-03-02 2024-03-04 Oxyde d'éthylène respectueux de l'environnement, oxyde de propylène et produits en aval

Country Status (4)

Country Link
EP (1) EP4673492A2 (fr)
JP (1) JP2026509789A (fr)
CN (1) CN121079338A (fr)
WO (1) WO2024180261A2 (fr)

Family Cites Families (89)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2182306A (en) 1935-05-10 1939-12-05 Ig Farbenindustrie Ag Polymerization of ethylene imines
US3203910A (en) 1962-04-13 1965-08-31 Dow Chemical Co Polymerization of alkylenimines
DE1302658B (fr) 1963-07-05
US3420875A (en) 1966-08-02 1969-01-07 Colgate Palmolive Co Olefin sulfonates
US3524864A (en) 1966-09-14 1970-08-18 Colgate Palmolive Co Sultone isomerization process
US3462525A (en) 1966-09-15 1969-08-19 Colgate Palmolive Co Dental compositions comprising long-chain olefin sulfonates
DE2227546C3 (de) 1972-06-07 1979-04-05 Basf Ag, 6700 Ludwigshafen Verwendung von oxalkylierten PoIyalkylenpolyaminen zur SchneUentwässening von Rohölen
US4133779A (en) 1975-01-06 1979-01-09 The Procter & Gamble Company Detergent composition containing semi-polar nonionic detergent and alkaline earth metal anionic detergent
DD203735A1 (de) 1981-12-24 1983-11-02 Adw Ddr Verfahren zur kontinuierlichen herstellung von polyetheralkoholen
DD203734A1 (de) 1981-12-24 1983-11-02 Adw Ddr Verfahren zur herstellung lebender polyetheralkohol-staemme
US4483779A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions comprising polyglycoside and polyethoxylate surfactants and anionic fluorescer
US4483780A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
DE3229216A1 (de) 1982-08-05 1984-02-09 Basf Ag, 6700 Ludwigshafen Verfahren zur reinigung von rohen polyether-polyolen
US4681704A (en) 1984-03-19 1987-07-21 The Procter & Gamble Company Detergent composition containing semi-polar nonionic detergent alkaline earth metal anionic detergent and amino alkylbetaine detergent
EP0230776B1 (fr) 1985-12-27 1991-03-06 Nippon Shokubai Kagaku Kogyo Co., Ltd Procédé pour la production des amines cycliques
US4966980A (en) 1987-03-12 1990-10-30 Nippon Shokubai Kagaku Kogyo Co. Ltd. Process for producing aziridines
WO1992006152A1 (fr) 1990-09-28 1992-04-16 The Procter & Gamble Company Amides de l'acide gras de polyhydroxy dans des compositions detergentes contenant un agent antisalissures
DE4136661A1 (de) 1991-11-07 1993-05-13 Basf Ag Erdoelemulsionsspalter
DE69409463T2 (de) 1993-11-02 1998-07-30 Nippon Catalytic Chem Ind Verfahren zur Herstellung von Alkanolamin, Katalysator für dieses Verfahren und Verfahren zur Herstellung des Katalysators
US5576282A (en) 1995-09-11 1996-11-19 The Procter & Gamble Company Color-safe bleach boosters, compositions and laundry methods employing same
DE19534493A1 (de) 1995-09-18 1997-03-20 Basf Ag Verfahren zur Herstellung feinteiliger Schalenkatalysatoren und ihre Verwendung bei der Synthese von Aziridinen
US5739075A (en) 1995-10-06 1998-04-14 Shell Oil Company Process for preparing ethylene oxide catalysts
US5777177A (en) 1996-02-07 1998-07-07 Arco Chemical Technology, L.P. Preparation of double metal cyanide-catalyzed polyols by continuous addition of starter
EG21623A (en) 1996-04-16 2001-12-31 Procter & Gamble Mid-chain branced surfactants
PH11997056158B1 (en) 1996-04-16 2001-10-15 Procter & Gamble Mid-chain branched primary alkyl sulphates as surfactants
EG22088A (en) 1996-04-16 2002-07-31 Procter & Gamble Alkoxylated sulfates
MA24137A1 (fr) 1996-04-16 1997-12-31 Procter & Gamble Fabrication d'agents de surface ramifies .
US5689012A (en) 1996-07-18 1997-11-18 Arco Chemical Technology, L.P. Continuous preparation of low unsaturation polyoxyalkylene polyether polyols with continuous additon of starter
AU733203B2 (en) 1996-10-25 2001-05-10 Procter & Gamble Company, The Cleansing products
US6093856A (en) 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
WO1998039405A1 (fr) 1997-03-07 1998-09-11 The Procter & Gamble Company Compositions de blanchiment contenant un catalyseur de blanchiment metallique et des activateurs de blanchiment et/ou des acides percarboxyliques organiques
PH11998001775B1 (en) 1997-07-21 2004-02-11 Procter & Gamble Improved alkyl aryl sulfonate surfactants
EP1002029B1 (fr) 1997-07-21 2003-05-14 The Procter & Gamble Company Tensio-actifs ameliores d'alkylbenzenesulfonate
DE69814870T2 (de) 1997-07-21 2004-05-06 The Procter & Gamble Company, Cincinnati Reinigungsmittelzusammensetzungen mit kristallinitätsstörenden tensiden
CN1270628A (zh) 1997-07-31 2000-10-18 普罗克特和甘保尔公司 湿状清洁制品
US6482994B2 (en) 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
DE19809539A1 (de) 1998-03-05 1999-09-09 Basf Ag Verfahren zur Herstellung von Doppelmetallcyanidkatalysatoren
US6156720A (en) 1998-06-23 2000-12-05 Basf Aktiengesellschaft Propoxylated/ethoxylated polyalkyleneimine dispersants
DE19840587A1 (de) 1998-09-05 2000-03-09 Basf Ag Katalysatoren zur Herstellung von Polyetherolen durch ringöffnende Polymerisation von Alkylenoxiden
WO2001032815A1 (fr) 1999-10-29 2001-05-10 The Procter & Gamble Company Compositions detergentes de blanchissage avec entretien des textiles
WO2001042408A2 (fr) 1999-12-08 2001-06-14 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
US6451961B2 (en) * 2000-02-03 2002-09-17 Nippon Shokubai Co Ltd Ethylenimine polymer, aqueous solution of ethylenimine polymer, production process for the same and purifying process therefor
JP4493152B2 (ja) 2000-04-10 2010-06-30 株式会社日本触媒 エチレンイミン重合体水溶液の製造方法
DE10028636A1 (de) 2000-06-09 2001-12-13 Basf Ag Verfahren zur Herstellung von Alkanolaminen
US6495609B1 (en) * 2000-11-03 2002-12-17 Exxonmobil Chemical Patents Inc. Carbon dioxide recovery in an ethylene to ethylene oxide production process
DE10156135A1 (de) 2001-11-16 2003-06-05 Basf Ag Pfropfpolymerisate mit Stickstoffheterocyclen enthaltenden Seitenketten
FR2851564A1 (fr) 2003-02-24 2004-08-27 Bp Lavera Snc Procede de fabrication combinee d'oxyde d'ethylene et d'ethanolamine(s)
DE10320635A1 (de) 2003-05-08 2004-11-18 Basf Ag Verfahren zur Herstellung von Propylenoxid
DE10322784A1 (de) 2003-05-19 2004-12-09 Basf Ag Verfahren zur Herstellung von Polyetherolen
DE10324998A1 (de) 2003-06-03 2004-12-23 Basf Ag Herstellung von Polyetheralkoholen unter Verwendung der DMC-Katalyse
DE102004007152A1 (de) 2004-02-12 2005-08-25 Basf Ag Alkylethersulfate
DE102005041142A1 (de) 2005-08-30 2007-03-01 Basf Ag Verfahren zur Herstellung von Polyetheralkoholen
KR20100031500A (ko) 2007-05-04 2010-03-22 프린시플 에너지 솔루션스, 인코포레이티드 탄소원과 수소원으로부터 탄화수소 제조
EP2014753A1 (fr) 2007-07-11 2009-01-14 The Procter and Gamble Company Composition nettoyante liquide
US9005979B2 (en) 2008-05-15 2015-04-14 Ivan Smajlovic Method for determining origin of alcohol or sugar containing products
GB2464691A (en) * 2008-10-22 2010-04-28 Christopher Denham Wall Manufacture of methanol from agricultural by-product cellulosic/lignitic material
DE102009043616A1 (de) * 2009-09-29 2011-03-31 Bayer Materialscience Ag Verfahren zur Herstellung von aminogruppenhaltigen Polyolen
CA2779260A1 (fr) * 2009-11-10 2011-05-19 Shell Internationale Research Maatschappij B.V. Procede de production d'oxyde d'ethylene
BR112012011078A2 (pt) * 2009-11-10 2016-07-05 Shell Int Research processo para produção de olefinas
US9035105B2 (en) * 2012-07-20 2015-05-19 Bayer Materialscience Llc Process for the in situ production of polyether polyols based on renewable materials and their use in the production of flexible polyurethane foams
CN103664831A (zh) * 2012-09-14 2014-03-26 中国科学院上海高等研究院 生产烯烃衍生物的系统及方法
ES2744246T3 (es) 2012-11-28 2020-02-24 Ecolab Usa Inc Estabilización de espuma con etoxilatos de polietilenimina
CN103848399B (zh) 2012-11-28 2015-09-02 柯香文 一种轻水制取超轻水的方法及设备
CN103816927B (zh) 2013-12-18 2015-12-30 西安近代化学研究所 一种用于合成乙撑亚胺的催化剂、制备方法及应用
US9120720B2 (en) 2013-12-30 2015-09-01 Scientific Design Company, Inc. Process for making ethanolamines
AU2015213022B9 (en) 2014-01-28 2018-05-24 Basf Se The use of alkoxylated polyethylene glycols in lubricating oil compositions
CN104475144B (zh) 2014-11-28 2017-02-01 西安近代化学研究所 一种氨基醇类化合物分子内脱水用催化剂的原位再生方法
WO2016149507A1 (fr) 2015-03-17 2016-09-22 Siluria Technologies, Inc. Procédés et systèmes de couplage oxydatif du méthane
WO2018146005A1 (fr) 2017-02-13 2018-08-16 Basf Se Procédé de fabrication d'une polyalkylènimine alcoxylée
WO2019030230A1 (fr) 2017-08-08 2019-02-14 Byk-Chemie Gmbh Composé à fonction amine
US11326129B2 (en) 2018-06-26 2022-05-10 The Procter & Gamble Company Fabric care compositions that include a graft copolymer and related methods
BR112021003603A2 (pt) 2018-08-27 2021-05-18 Basf Se uso de polímeros, e, método para remover sujeira sensível a tensoativo ou enzima de têxteis.
WO2020264077A1 (fr) 2019-06-28 2020-12-30 The Procter & Gamble Company Composition nettoyante
WO2021115912A1 (fr) 2019-12-09 2021-06-17 Basf Se Formulations comprenant une polyéthylèneimine modifiée de manière hydrophobe et une ou plusieurs enzymes
MX2022010150A (es) 2020-02-21 2022-09-12 Basf Se Polialquileniminas alcoxiladas o poliaminas alcoxiladas con biodegradabilidad mejorada.
US12223513B2 (en) 2020-10-05 2025-02-11 Basf Se Method for determining the carbon footprint of a product in production processes of a production plant
CN112457230B (zh) 2020-11-13 2022-08-19 西安近代化学研究所 一种乙烯亚胺的分离提纯方法
JP2024507319A (ja) 2020-12-23 2024-02-19 ビーエーエスエフ ソシエタス・ヨーロピア 新規なアルコキシル化ポリアルキレンイミン又はアルコキシル化ポリアミン
WO2022136389A1 (fr) 2020-12-23 2022-06-30 Basf Se Polyamines alcoxylées amphiphiles et leurs utilisations
US20240132668A1 (en) 2020-12-23 2024-04-25 Basf Se Amphiphilic alkoxylated polyalkylene imines or alkoxylated polyamines
CA3228918A1 (fr) 2021-08-10 2023-02-16 Nippon Shokubai Co., Ltd. Compose a teneur en oxyde de polyalkylene
US20250136740A1 (en) 2021-08-12 2025-05-01 Basf Se Biodegradable graft polymers for dye transfer inhibition
US20250122337A1 (en) 2021-08-19 2025-04-17 Basf Se Modified alkoxylated polyalkylene imines and modified alkoxylated polyamines obtainable by a process comprising the steps a) to d)
US20240360280A1 (en) 2021-08-19 2024-10-31 Basf Se Modified alkoxylated polyalkylene imines or modified alkoxylated polyamines
WO2023021101A1 (fr) 2021-08-19 2023-02-23 Basf Se Polyalkylène-imines alcoxylées modifiées
JP2024531330A (ja) 2021-08-19 2024-08-29 ビーエーエスエフ ソシエタス・ヨーロピア 修飾アルコキシル化オリゴアルキレンイミン及び修飾アルコキシル化オリゴアミン
CN118202030A (zh) 2021-10-13 2024-06-14 巴斯夫欧洲公司 包含聚合物的组合物、聚合物及其用途
WO2023117494A1 (fr) 2021-12-20 2023-06-29 Basf Se Polymères de polypropylène imine (ppi), leur préparation, leurs utilisations et compositions comprenant de tels ppi

Also Published As

Publication number Publication date
WO2024180261A2 (fr) 2024-09-06
CN121079338A (zh) 2025-12-05
JP2026509789A (ja) 2026-03-25
WO2024180261A3 (fr) 2024-10-17

Similar Documents

Publication Publication Date Title
WO2023213713A1 (fr) Procédé de fabrication d'éthanolamines, de polyéthylèneimine et d'ammoniac à base d'énergie non fossile
US8859259B2 (en) Surfactant and cleaning compositions comprising microbially produced branched fatty alcohols
US20120172281A1 (en) Detergent compositions comprising microbially produced fatty alcohols and derivatives thereof
KR101714967B1 (ko) 신규한 메틸로모나스 속(Methylomonas sp.) 균주 및 이의 용도
Aresta et al. Carbon recycling through CO2-conversion for stepping toward a cyclic-C economy. A perspective
JP2017534731A (ja) ソイルリリースポリマーを含有する洗濯用洗剤
Sarkar et al. Green hydrogen and platform chemicals production from acidogenic conversion of brewery spent grains co-fermented with cheese whey wastewater: adding value to acidogenic CO 2
Aresta et al. Merging the Green-H2 production with Carbon Recycling for stepping towards the Carbon Cyclic Economy
JP2009155611A (ja) 液体洗浄剤組成物
US20250296902A1 (en) Synthetic methanol having low deuterium content from non-fossil resources
WO2024180261A2 (fr) Oxyde d'éthylène respectueux de l'environnement, oxyde de propylène et produits en aval
EP4695321A1 (fr) Acétate de vinyle à faible teneur en deutérium
CN100547015C (zh) 氨基改性亲水硅油的制备方法
Aresta et al. Large scale utilization of carbon dioxide: from its reaction with energy rich chemicals to (Co)-processing with water to afford energy rich products. Opportunities and barriers
US20240199983A1 (en) Fabric serum composition
EP4556456A1 (fr) Procédé de fabrication d'éthylène glycols et d'éthoxylates basés sur l'énergie non-fosil
Aresta et al. Artificial carbon sinks: utilization of carbon dioxide for the synthesis of chemicals and technological applications.
WO2022219134A1 (fr) Composition pour le lavage de la vaisselle à la main
CN109529906A (zh) 一种合成1,1,2,3,3,3-六氟丙基甲醚的催化剂及其制备方法
KR101042488B1 (ko) 친환경 및 무독성 저수조 세정액
WO2022219105A1 (fr) Détergent pour lave-vaisselle
Senda et al. Role of the Heteroatoms in the Complex Metal Hydride Reduction of 2-t-Butyl-1, 3-dioxan-5-one and 3-Oxoquinolizidine: Comparison of Their Reactivity and Stereochemistry with Those of the Corresponding Carbocyclic Compounds.
WO2022219101A1 (fr) Composition solide
EP4549621A1 (fr) Procédé de fabrication d'amines à partir d'alcools à l'aide d'hydrogène à faible teneur en deutérium produit à l'aide d'énergie non-fossil
Abidin et al. Valorization of CO2 emissions into ethanol by an innovative process

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20251002

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR