WO2010146117A2 - Procédé d'hydrogénation de glycérine en 1,2-propanediol, avec désulfuration par hydrogénation sur lit sacrificiel - Google Patents

Procédé d'hydrogénation de glycérine en 1,2-propanediol, avec désulfuration par hydrogénation sur lit sacrificiel Download PDF

Info

Publication number
WO2010146117A2
WO2010146117A2 PCT/EP2010/058543 EP2010058543W WO2010146117A2 WO 2010146117 A2 WO2010146117 A2 WO 2010146117A2 EP 2010058543 W EP2010058543 W EP 2010058543W WO 2010146117 A2 WO2010146117 A2 WO 2010146117A2
Authority
WO
WIPO (PCT)
Prior art keywords
glycerol
catalyst
process according
hydrogenation
stream
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.)
Ceased
Application number
PCT/EP2010/058543
Other languages
German (de)
English (en)
Other versions
WO2010146117A3 (fr
Inventor
Roman Prochazka
Stephan Maurer
Oliver Bey
Jochen Steiner
Jochem Henkelmann
Gerhard Theis
Peter Wahl
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 WO2010146117A2 publication Critical patent/WO2010146117A2/fr
Publication of WO2010146117A3 publication Critical patent/WO2010146117A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C07C29/90—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound using hydrogen only

Definitions

  • the present invention relates to a process for the preparation of 1,2-propanediol from glycerol comprising at least the steps (A) providing a glycerol stream G1, (B) desulfurizing the glycerol stream G1 from step (A) by hydrogenation with hydrogen at a pressure of 50 - 300 bar in the presence of a catalyst to obtain a glycerol stream G2, and (C) hydrogenation of the glycerol stream G2 from step (B) with hydrogen in the presence of a catalyst to obtain 1, 2-propanediol.
  • WO 2007/099161 A1 discloses a process for the preparation of 1, 2-propanediol from glycerol-containing streams by reduction with hydrogen in the presence of a copper-containing, heterogeneous catalyst at a temperature of 100 to 320 0 C and a pressure of 100 to 325 bar.
  • the glycerol used in the hydrogenation can be subjected to catalytic desulfurization before the hydrogenation.
  • the reactant stream is hydrogenated in the presence of a catalyst with hydrogen, wherein this takes place at a temperature of 40 to 200 0 C and a pressure of 1 to 40 bar.
  • DE 541 362 discloses a process for the hydrogenation of polyoxy compounds, for example glycerol or carbohydrates, at a pressure of 10 to 60 atmospheres or higher pressures such. B. 200 atmospheres or 1000 atmospheres, and a temperature of 200 to 240 0 C. DE 541 362 does not disclose a process for the production of 1, 2-propanediol from glycerol, in which the crude glycerol is first subjected to desulfurization.
  • DE 524 101 discloses a process for the reduction of polyhydric alcohols.
  • copper, silver, zinc or nickel catalysts from ethyl glycol or of glycerol Propylengly- col and n-propyl alcohol can be obtained at a temperature of 250-260 0 C in the presence of hydrogenation catalysts.
  • DE 524 101 does not disclose a process for the preparation of 1,2-propanediol from glycerol, in which the crude glycerol is first subjected to desulfurization.
  • DE 43 02 464 A1 discloses a process for the preparation of 1, 2-propanediol by hydrogenation of glycerol in the presence of a heterogeneous catalyst at a pressure of 20 to 300 bar and a temperature of 150 to 320 0 C.
  • a heterogeneous catalyst at a pressure of 20 to 300 bar and a temperature of 150 to 320 0 C.
  • the use of glycerol-containing streams, which originate from the production of biodiesel and processes for pretreatment of these educt streams are not disclosed in DE 43 02 464 A1.
  • EP 0 523 015 discloses a process for the catalytic hydrogenation of glycerol for the preparation of 1, 2-propanediol and 1, 2-ethanediol in the presence of a Co / Zn catalyst.
  • the starting compound used is an aqueous solution of glycerol having a glycerol content of 20 to 60% by weight.
  • WO 2005/095536 discloses a process for the preparation of propylene glycol from glycerol, wherein the glycerol-containing stream having a water content of less than 50 wt .-% at a temperature of 150 to 250 0 C and a pressure of 1 to 25 bar catalytically hydrogenated becomes.
  • the object of the present invention is to provide a process for the preparation of 1,2-propanediol from glycerol, which is distinguished by a particularly long service life of the hydrogenation catalyst used. Furthermore, the activity of the catalyst should be particularly high.
  • the process according to the invention is intended to remove catalyst poisons present in the educt stream in order to increase the service life of the catalyst in the hydrogenation of glycerol to 1,2-propanediol. Furthermore, 1,2-propanediol should be obtainable in high yield and purity by the process according to the invention.
  • step (B) desulfurization of the glycerol stream G1 from step (A) by hydrogenation with hydrogen at a pressure of 50 - 300 bar in the presence of a catalyst to obtain a Glycerinstrom G2, and
  • step (C) Hydrogenation of the glycerol stream G2 from step (B) with hydrogen in the presence of a catalyst to obtain 1, 2-propanediol.
  • Step (A) of the method according to the invention comprises providing a glycerin stream G1.
  • step (A) all the glycerol streams G1 known to the person skilled in the art can be used in step (A), for example comprising those obtainable from industrial processes.
  • the glycerol streams G1 which can be used according to the invention should have purities which are suitable for the process according to the invention.
  • glycerol streams G1 from the treatment of oil and / or fat-containing starting materials for example, from the soap, fatty acid and fatty acid ester production, etc., are used.
  • glycerol-containing streams which are industrially available and have purities suitable for the process according to the invention can be used.
  • corresponding glycerol-containing streams are used in the processing of oil and / or fat-containing starting materials, e.g. As in the production of soap, or in the production of fatty acids and fatty acid esters, etc. obtained.
  • the glycerol-containing stream preferably provided in step (A) is preferably a glycerol-containing stream obtained in the preparation of the higher fatty acid alkyl esters by transesterification of the fatty acid triglycerides, especially in the production of "biodiesel"
  • biodiesel means a mixture of fatty acid alkyl esters obtainable from biogenic oil and / or fat-containing starting materials which can be used as fuel in diesel engines.
  • Oils and fats are generally solid, semi-solid or liquid fatty acid triglycerides, particularly from vegetable or animal sources, which in the chemical sense essentially comprise glycerol esters of the higher fatty acids.
  • Suitable higher fatty acids are, for example, the saturated or mono- or polyunsaturated fatty acids, which preferably have 8 to 40, particularly preferably 12 to 30, carbon atoms.
  • n-nonanoic acid n-decanoic acid, n-undecanoic acid, n-tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, nonadecanoic acid, peanutic acid, behenic acid, lignoic acid, cerotic acid, melissic acid, palmitinoleic acid, oleic acid, linoleic acid, linolenic acid, stearic acid , Elaostearic acid, etc.
  • Vegetable fats and oils are based essentially on fatty acids having an even number of carbon atoms, while animal fats and oils may also comprise fatty acids having an odd number of carbon atoms in the free form or bound as triglyceride esters.
  • the unsaturated fatty acids found in vegetable fats and oils are in the cis configuration, while animal unsaturated fatty acids are often in the trans configuration.
  • glycerol-containing stream in step (A) may be used to provide the glycerol-containing stream in step (A).
  • These can be shares of other ingredients, eg. Free fatty acids.
  • the proportion of free fatty acids is generally from 0 to 50 wt .-%, preferably 0.1 to 20 wt .-%.
  • free fatty acids may be removed before or after the transesterification of the fatty acid triglycerides. Salts of these fatty acids, eg.
  • the alkali metal salts may be previously converted to the free acid by reaction with a strong acid, e.g. B. with HCl. The isolation of the free fatty acids takes place z.
  • Suitable fats and oils which are suitable for providing the glycerol-containing stream according to step (A) of the process according to the invention are generally fatty and / or oleaginous constituents which, after being obtained from the corresponding biogenic starting materials, are initially other purposes, eg. For example, have been used for technical purposes or for food production, and therefore may be chemically modified or unmodified or may contain additional ingredients. These can be at least partially removed.
  • fats and the oils which are suitable for providing the glycerol-containing stream in step (A) are fatty or oleaginous components which, after their recovery from the corresponding biogenic starting materials, have not yet been used for other purposes, e.g. , For example, for technical purposes or for food production have been used, and thus contain only components derived from the starting materials or related to the extraction of the starting materials.
  • Other constituents than fatty acid triglycerides and optionally free fatty acids may optionally be at least partially separated from the starting materials by transesterification before step (A) of the process according to the invention.
  • the fats or oils used or unused may be freed of undesirable components such as lecithins, carbohydrates, proteins, oil sludge, water, etc.
  • Vegetable oils and fats are those which are generally derived from vegetable source materials such as seeds, roots, leaves or other suitable plant parts.
  • Animal fats or oils are predominantly derived from animal feedstocks such as animal organs, tissues or other body parts or body fluids such as milk.
  • Industrial oils and fats are those obtained in particular from animal or vegetable raw materials and for technical purposes.
  • the used or unused, unrefined or purified oils and / or fats come especially from soap base, brown fat, yellow fat, industrial tallow, industrial lard, frying oil, animal fat, edible tallow, unrefined vegetable oils, unpurified animal oils or mixtures thereof ,
  • “soap base material” is understood to mean by-products which are obtained in the processing of vegetable oils, in particular in edible oil refineries, for example based on soybean, rapeseed or sunflower oil.
  • "Seefeng round cloth” has a proportion of about 50 up to 80% by weight of free fatty acids.
  • “Brown fat” is understood according to the invention as a waste product containing animal fat, which has a content of free fatty acids 15 to 40 wt .-%.
  • “Yellow fat” comprises about 5 to 15 wt .-% of free fatty acids.
  • “Industrial tallow” and “industrial lard” are understood according to the invention as animal fats, which are produced for industrial purposes and obtained after drying or wet-melting process, for. B. from slaughterhouse waste. Industrial tallow is added according to the acid number, i. H. the content of free fatty acids, evaluated, the z. B. 1 to 20 wt .-% is.
  • the "animal fats” include the fat-containing waste products obtained in the use of poultry, livestock, pigs, fish and marine mammals as a solid residue.
  • the stream containing glycerol provided in step (A) of the process according to the invention is preferably obtained from unpurified vegetable oils as starting material.
  • This can be based on liquid or of the solid compositions obtained from vegetable starting materials, for.
  • Such unrefined vegetable oils may also be vegetable oils obtained by extraction.
  • the proportion of free fatty acids in the unrefined vegetable fats and oils is z. B. 0 to 20 wt .-%.
  • the vegetable oils Before the vegetable oils are supplied to the transesterification, the vegetable oils can be subjected to one or more treatment steps.
  • purified vegetable oils eg. As raffinates or semiraffinates of the above-mentioned vegetable oils can be used as starting materials.
  • rapeseed oil selected from the group consisting of rapeseed oil, palm oil, soybean oil, sunflower oil, corn oil, cottonseed oil, palm kernel oil, coconut fat and mixtures thereof
  • rapeseed oil or a mixture containing rapeseed oil particular preference is given to rapeseed oil or a mixture containing rapeseed oil.
  • Tiered oils or fats are selected from the group consisting of milk fat, wool fat, beef tallow, pork fat, fish oils, Tran, etc., and mixtures thereof.
  • the production of the glycerol-comprising stream for step (A) of the process according to the invention particularly preferably comprises the following steps:
  • Step a1)
  • provision of a starting mixture containing biogenic fats and / or oils according to step a1) comprises at least one purification step.
  • the fat and / or oil-containing starting mixture may be at least be subjected to a purification process suitable for fats and oils, such as clarification, filtration, treatment with bleaching earth or working up with acids or bases, for the separation of impurities such as proteins, phosphatides and sludges. Also possible is a combination of the mentioned methods.
  • At least one d-Cg monoalcohol is preferably used for the transesterification of the fatty acid triglycerides.
  • the use of methanol or ethanol is particularly preferred.
  • the transesterification of the fatty acid triglycerides can be carried out by acidic or preferably basic catalysis. Suitable acids are, for. For example, mineral acids such as HCl, H 2 SO 4 or H 3 PO 4 . At least one base is preferably used as the catalyst.
  • Preferred bases are alkali metal hydroxides such as NaOH, KOH, alkaline earth metal hydroxides such as Ca (OH) 2 , alkali metal and alkaline earth metal d-Ce alkoxides such as NaOCH 3 , KOCH 3 , Na (OCH 2 CH 2 ) and Ca (OCH 2 CH 2 ) 2 and mixtures thereof.
  • NaOH, KOH or NaOCH 3 are particularly preferably used.
  • the amount of the base used is generally in the range of 0.1 to 10 wt%, preferably 0.2 to 5 wt%, based on the amount of the fatty acid triglycerides used.
  • the base is preferably used in the form of an aqueous or an alcoholic, more preferably an alcoholic, solution.
  • a solution of NaOCH 3 in methanol is preferably used for the transesterification.
  • the transesterification is preferably carried out at a temperature of 20 to 150 0 C, more preferably 30 to 95 0 C.
  • the transesterification takes place in conventional apparatus known to those skilled in the art, preferably continuously, more preferably in a column.
  • a high-boiling phase enriched with the basic catalyst, with unreacted monoalcohol and glycerol, which is formed in the transesterification, and a low-boiling phase, which is enriched with the transesterification product, is generally obtained in this case. If the transesterification product still contains triglycerides which have not been transesterified, these may be separated or subjected to a further transesterification stage.
  • the mixture obtained from the transesterification is then preferably fed to a drying unit in order to remove residual amounts of water. After drying lies the preferred desired end product "biodiesel" in purified form, and can be used directly.
  • the optionally present free fatty acids are preferably esterified with the same d-Cg monoalcohol which is used for the transesterification of the fatty acid triglycerides.
  • the esterification of the free fatty acids can take place before, during or after the transesterification of the fatty acid triglycerides. In a preferred embodiment, the esterification of the free fatty acids takes place before the transesterification of the fatty acid triglycerides.
  • the esterification of the free fatty acids can be carried out by basic or preferably acid catalysis. Suitable acids are the above-mentioned mineral acids, such as HCl, H 2 SO 4 or H 3 PO 4 , para-toluene-sulfonic acid, etc.
  • the esterification is preferably carried out at a temperature of 20 to 95 0 C, especially 40 to 80 0 C.
  • the esterification takes place in customary and known to the expert devices, such as a column.
  • the esterification mixture is separated to obtain at least one biodiesel-enriched fraction and at least one glycerol-enriched fraction.
  • This separation is preferably carried out by the conventional distillation methods known to those skilled in the art. Suitable distillation apparatuses are those mentioned above.
  • the at least one glycerol-enriched fraction obtained in step a3) may optionally be subjected to at least one work-up step.
  • the removal of undesirable components such as salts and components that adversely affect the catalytic hydrogenation or the removal of water or, if present, the organic solvent.
  • the glycerol stream G1 used in step (A) optionally contains water.
  • the glycerol stream G1 preferably has a water content of less than 30% by weight, more preferably less than 20% by weight, for example 8 to 12% by weight, in particular 10% by weight. Methods for determining the water content are known in the art, for example Karl Fischer titration.
  • the use of a glycerol stream G1 having a water content in the range of less than 30 wt .-%, preferably less than 20 wt .-%, allows the production of 1, 2-propanediol with high yields and high selectivity in the temperature and pressure range of the method according to the invention (step (C)).
  • glycerol streams G1 which are essentially not anhydrous, in particular of streams which have a higher water content than glycerol monohydrate, but according to the invention is also possible with high yields and high selectivity.
  • a water content in the range of 3 to 30 wt .-% may be advantageous for the rheological properties during the hydrogenation.
  • a glycerol stream G1 is used in step (A) of the process according to the invention, which has a water content of 3 to 30 wt .-%, preferably 5 to 20 wt .-%, each based on the total current G1, for example to lower the viscosity of the reaction mixture during hydrogenation.
  • the glycerol stream G1 can generally contain at least one further, preferably a glycerol-miscible, and therefore also water-miscible, organic solvent instead of or in combination with water.
  • the glycerol stream G1 used in step (A) of the process according to the invention generally has a total solvent content of less than 20% by weight, preferably less than 15% by weight, very preferably less than 10% by weight and in particular preferably less than 5% by weight, in each case based on the total glycerol flow G1.
  • the proportion of the organic solvent is preferably less than 50% by weight, more preferably less than 20% by weight, in each case on the total amount of solvent.
  • Suitable glycerol-miscible organic solvents are C 1 -C 4 -alcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, polyols, and mono- and dialkyl ethers thereof, cyclic ethers For example, dioxane and tetrahydrofuran, etc.
  • Other suitable solvents are aromatic hydrocarbons, for example benzene, toluene or the xylene.
  • Preferred organic solvents are CrC 4 -AlkOhOIe, preferably methanol and / or ethanol, and mixtures thereof with water.
  • a particularly preferred glycerol stream G1 used in step (A) of the process according to the invention contains no organic solvents, ie in the glycerol stream G1 used according to the invention the content of organic solvents is more preferably less than 4% by weight, preferably less as 2% by weight, more preferably less than 1% by weight.
  • Analytical methods for determining the content of organic solvents are known to the person skilled in the art, for example gas chromatography GC or high performance liquid chromatography to HPLC.
  • the glycerol stream G1 provided in step (A) of the process according to the invention generally has a sulfur content of 0.1 to 20 ppm, preferably 0.1 to 5 ppm.
  • the said amount of sulfur is preferably present in sulfur-containing compounds, for example as organic sulfur-containing compounds, for example sulfur-containing amino acids such as cysteine and / or methionine, or as inorganic sulfur-containing compounds, for example sulfates or sulfides.
  • the glycerol stream G1 provided in step (A) of the process according to the invention may, in addition to sulfur, optionally contain further substances as impurity, for example inorganic salts, for example NaCl, KCl. These are for example in amounts of 0 to 5 wt .-%, based on the current G1, before.
  • impurity for example inorganic salts, for example NaCl, KCl.
  • the glycerol stream G1 is first fed to at least one work-up step.
  • This pretreatment step (s) includes, for example, at least one purification step to remove unwanted components. Further, this pretreatment step (s) also includes lowering the level of water and / or, if present, organic solvents, for example, to achieve the preferred levels specified above. Depending on the origin of the glycerol stream G1, this may contain, in addition to the sulfur-containing compounds, inorganic salts as undesired components. These can be removed from the glycerol stream G1, for example by appropriate work-up steps, for example thermal work-up, for example with a Sambay evaporator.
  • the stream G1 is treated by distillation to obtain a stream G1 which contains substantially no inorganic salts.
  • Further pretreatment steps to which the glycerol stream G1 may be subjected are, for example, distillation, adsorption, ion exchange, membrane separation, crystallization or extraction, or a combination of two or more of these methods, to obtain a glycerol stream G1 satisfying the requirements of the present invention Method corresponds. These methods are known to the person skilled in the art and are described, for example, in WO 2007/099161 A1.
  • the glycerol stream G1 preferably used according to the invention may also contain acidic compounds.
  • a measure of the content of acidic compounds is the Versei- number, which can be determined by methods known in the art.
  • the glycerol stream G1 used in step (A) of the process according to the invention has a saponification number of 0.1 to 10 mg KOH / g, preferably 0.1 to 5 mg KOH / g, particularly preferably 0.1 to 3 mg KOH / g , on.
  • Step (B) of the process according to the invention comprises the desulfurization of the glycerol stream G1 from step (A) by hydrogenation with hydrogen at a pressure of 50 to 300 bar in the presence of a catalyst in order to obtain a glycerol stream G2.
  • the desulfurization according to step (B) of the process according to the invention serves to lower the content of sulfur-containing compounds.
  • the reduction of the sulfur content is advantageous because the catalyst used in the hydrogenation to 1, 2-propanediol is damaged by the presence of sulfur, and thus has a limited activity.
  • the separation of sulfur from the reactant stream thus contributes to increasing the activity and the service life of the hydrogenation catalyst.
  • Suitable catalysts which can be used in step (B) of the process according to the invention generally comprise metal components known to the person skilled in the art, which are selected, for example, from groups 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table of the Elements ( new IUPAC nominee).
  • the present invention relates to the process according to the invention, wherein in step (B) a catalyst is used comprising at least one metal component selected from the groups 6, 7, 8, 9, 10, 11 and / or 12 of the Periodic Table of the Elements (new IUPAC nomenclature).
  • the metals present in the catalyst used in step (B) of the process according to the invention are selected from the group consisting of Mo, Ni, Cu, Ag, Zn and mixtures thereof.
  • the catalyst in step (B) can be used in oxidized, reduced form or in the form of a mixture comprising oxidized and reduced fractions.
  • the active element of the catalyst according to step (B) can be used on a support material or unsupported.
  • Suitable support materials are for example selected from the group consisting of activated carbon, graphite, carbon black, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , SiC, silicates, zeolites, clay-like earth, z. B. bentonite, and mixtures thereof.
  • the application of the at least one metal component and optionally further components to the support material can be carried out by methods known to the person skilled in the art, for example by co-precipitation or impregnation.
  • the catalyst used in step (B) of the process according to the invention can generally be used in any form known to those skilled in the art, for example as spheres, rings, cylinders, cuboids and / or other geometric bodies.
  • Unsupported catalysts may be formed by shaping processes known to those skilled in the art, e.g. Extrusion, tableting, etc.
  • the shape of the supported catalysts of step (B) is generally dictated by the shape of the support material.
  • a copper-containing catalyst is used in step (B) of the process according to the invention. This may be supported or not supported.
  • the catalyst can be used in the form of a uniform composition, as impregnated catalyst, coated catalyst or precipitated catalyst.
  • a large number of copper-containing catalysts which may additionally contain at least one further element from groups 1 to 15 of the periodic table and lanthanides (new IUPAC nomenclature) are suitable for step (B) of the process according to the invention.
  • Particularly preferred further elements are selected from the group consisting of Ca, Mg, Al, La, Ti, Zr, Cr, Mo, W, Mn, Ni, Co, Zn and mixtures thereof.
  • a skeletal catalyst or a metal sponge catalyst is used in step (B) of the process according to the invention, for example, known as "Raney catalysts.”
  • Raney catalysts include, in particular, Raney copper and copper-containing metal alloys in the form of a Raney catalyst.
  • Raney catalysts containing at least 95%, more preferably at least 99%, copper as the metal component are preferred. Processes for the preparation of Raney catalysts are known to the person skilled in the art and are described, for example, in DE-A-43 35 360, DE-A-43 45 265, DE-A-44 46 907 and EP-A-842-699.
  • Preferred catalysts which can be used in step (B) of the process according to the invention include the following metals or combinations of metals in oxidic form, reduced form (elementary form) or a combination thereof. Metals which are stable in more than one oxidation state can be used as a whole in an oxidation state or in a combination of different oxidation states.
  • silica quartz
  • porcelain magnesium oxide
  • tin oxide silicon carbide
  • TiC> 2 rutile and / or anatase
  • ZrC> 2 Al 2 O 3
  • aluminum silicate Steatite (magnesium silicate), zirconium silicate, cersilicate or mixtures thereof.
  • Particularly preferred support materials are alumina and silica.
  • Silica materials of different origin or production process for example pyrogenically or wet-chemically produced silica, such as silica gels, aerogels or precipitated silica, can be used as silica support material for the catalyst used in step (B) of the process according to the invention be used.
  • a catalyst in step (B) of the process according to the invention a catalyst can be used which comprises copper in oxidic form and optionally additionally in elemental form.
  • the catalyst used in step (B) of the process according to the invention preferably contains at least 23% by weight, particularly preferably at least 35% by weight, of copper in oxidic and / or elemental form, based on the total weight of the catalyst.
  • a catalyst is used in step (B) of the process according to the invention, preferably containing, in addition to copper, another metal selected from the group consisting of Al, La, W, Mo, Ti, Zr and mixtures thereof, more preferably in oxidic Shape.
  • composition of the catalyst according to step (B) of the process according to the invention is generally such that the proportion of copper oxide in the range of 40 to 90 wt .-%, the content of the oxides of La, W, Mo, Ti and / or Zr in the range of 0 to 50 wt .-% and the content of alumina up to 50 wt .-%, each based on the total weight of the catalyst.
  • the total mass of said metal oxides is at least 80 wt .-% of the catalyst, the missing wt .-% of materials that do not fall under the above-mentioned oxidic compounds, for example, elemental copper in an amount of up to 15 wt .-% ,
  • a catalyst is used in step (B) of the process according to the invention comprising an oxidic material containing
  • alumina in an amount of 15 ⁇ y ⁇ 35% by weight, preferably 20 ⁇ y ⁇ 30% by weight, and (c) at least one of the oxides of La, W, Mo, Ti or Zr, preferably of La and / or W, in an amount of 3 ⁇ z ⁇ 20% by weight, preferably 3 ⁇ z ⁇ 15% by weight , in each case based on the total weight of the oxidic material after calcination, wherein 80 ⁇ x + y + z ⁇ 100 wt .-%, preferably 95 ⁇ x + y + z ⁇ 100 wt .-% applies.
  • a catalyst is used in step (B), which corresponds to the following general formula CuOm (Al 2 Os) n (La 2 O 3 ) O, where
  • m 0.55 to 0.85 preferably 0.60 to 0.75, particularly preferably 0.60 to 0.70, n 0.15 to 0.30, preferably 0.18 to 0.28, particularly preferably 0, 20 to 0.25 and 0.01 to 0.10, preferably 0.02 to 0.08, particularly preferably 0.03 to 0.06
  • the catalyst used is preferably reduced in situ by treatment with hydrogen. This is preferably done under the conditions that are also present in step (B).
  • the catalyst which is preferably used in step (B) can generally be arranged in the reactor in a manner known per se in the art, for example as a fixed bed.
  • Step (B) of the process according to the invention can generally be carried out in any reactor known to the person skilled in the art for carrying out such a reaction, for example a shaft reactor which can be operated in trickle or bottom mode.
  • a shaft reactor which can be operated in trickle or bottom mode.
  • the desulfurization according to step (B) of the process according to the invention is carried out at a pressure of 50 to 200 bar, preferably 100 to 250 bar, particularly preferably 150 to 220 bar.
  • the desulfurization according to step (B) of the process according to the invention is carried out at a temperature of 100 to 300 ° C., preferably 120 to 250 ° C., particularly preferably 160 to 220 ° C.
  • the desulfurization by hydrogenation according to step (B) of the process according to the invention is carried out in the presence of hydrogen as a reducing agent.
  • the hydrogen used according to the invention generally has a purity of> 99.8% by volume, preferably 99.9% by volume, particularly preferably ⁇ 99.95% by volume.
  • the weight ratio of glycerol stream G1 to hydrogen in step (B) of the process according to the invention is 40,000: 1 to 1,000: 1, preferably 38,000: 1 to 5,000: 1, more preferably 37,000: 1 to 15,000: 1, very particularly preferably 36,000: 1 to 25,000: 1, more preferably 35,000: 1 to 30,000: 1.
  • Step (B) of the process according to the invention can be carried out continuously or batchwise, preferably continuously.
  • a glycerol stream G2 is obtained which differs from glycerol stream G1 by a reduced sulfur content.
  • the sulfur-containing compounds are preferably removed from the stream G1 by being bound to the catalyst used by reductive chemisorption.
  • step (B) of the process according to the invention the glycerol contained in glycerol stream G1 is at least partially reduced to 1,2-propanediol.
  • step (B) The glycerol stream G2 obtained in step (B) is converted in a preferred embodiment directly into step (C) of the process according to the invention.
  • steps (B) and (C) are carried out in a reactor so that the stream obtained in step (B) is transferred directly to step (C).
  • steps (B) and (C) are carried out in at least two spatially separate reactors.
  • Step (C) of the process according to the invention comprises the hydrogenation of the glycerol stream G2 from step (B) with hydrogen in the presence of a catalyst in order to obtain 1,2-propanediol.
  • Methods for the hydrogenation of glycerol-containing streams are known per se to those skilled in the art.
  • the hydrogenation step (C) being preceded by a desulfurization step (B) according to the invention, it is possible to separate sulfur-containing compounds which would act as catalyst poisons in step (C), so that the catalyst used in step (C) produces a longer life and higher activity.
  • step (C) of the process according to the invention it is generally possible to use all catalysts which have been mentioned with regard to step (B). Therefore, what has been said about the catalyst used in step (B) also applies correspondingly to step (C).
  • step (C) of the process according to the invention a catalyst is used comprising an oxidic material containing
  • a catalyst is used in step (C), which corresponds to the following general formula CuOm (Al 2 Os) n (La 2 O 3 ) O, where
  • m 0.55 to 0.85 preferably 0.60 to 0.75, particularly preferably 0.60 to 0.70, n 0.15 to 0.30, preferably 0.18 to 0.28, particularly preferably 0, 20 to 0.25 and 0.01 to 0.10, preferably 0.02 to 0.08, particularly preferably 0.03 to 0.06
  • the catalysts used in step (C) of the process according to the invention can, for. B. in a fixed bed or as a suspension.
  • the hydrogenation may, for. B. in the trickle bed, in the upflow mode or in the liquid phase.
  • the catalysts are preferably in finely divided form, for. As a powder used.
  • the catalysts are preferably used as moldings, for. In the form of pressed cylinders, tablets, lozenges, strands, rings, stars or extrudates, for example solid extrudates, polylobal extrudates, hollow extrudates and honeycombs.
  • Excess hydrogen is preferably recycled, so that it is preferably possible to separate off a portion of the hydrogen so as to discharge inert materials.
  • step (C) of the process according to the invention a reactor or a plurality of reactors arranged in series or in parallel.
  • the temperature in the hydrogenation in step (C) of the process according to the invention is generally from 100 to 325 0 C, preferably 150 to 300 C °, particularly preferably 175 to 250 0 C.
  • Step (C) of the process according to the invention is generally carried out at a pressure of 100 to 325 bar, preferably 140 to 250 bar.
  • the present invention also relates to the process according to the invention, wherein the hydrogenation in step (C) is carried out at a temperature of 100 to 325 0 C and a pressure of 100 to 325 bar.
  • the molar ratio of hydrogens to glycerol in step (C) is preferably 2: 1 to 500: 1, more preferably 3: 1 to 100: 1.
  • the catalyst space velocity in the continuous procedure is preferably 0.1 to 1, particularly preferably 0.2 to 0.6 and very particularly preferably 0.3 to 0.6, kg of glycerol to be hydrogenated per kg of catalyst per hour.
  • the hydrogenation according to step (C) of the process according to the invention is generally carried out up to a conversion with respect to glycerol of at least 90%, preferably at least 95%.
  • the selectivity with respect to 1,2-propanediol is according to According to the invention, preferably at least 85%, particularly preferably at least 90%, very particularly preferably at least 95%.
  • the hydrogenation is preferably carried out continuously.
  • the product obtained after step (C) of the process according to the invention contains essentially 1,2-propanediol.
  • Further constituents are, if appropriate, inter alia methanol, ethanol, n-propanol, isopropanol, 1,3-propanediol, glycerol, ethylene glycol and / or water.
  • the product obtained after the hydrogenation according to step (C) can be worked up by methods known to the person skilled in the art, for example thermal treatment, preferably distillation, adsorption, ion exchange, membrane separation, crystallization or extraction or a combination of two or more of these processes, wherein distillative workup is preferred.
  • thermal treatment preferably distillation, adsorption, ion exchange, membrane separation, crystallization or extraction or a combination of two or more of these processes, wherein distillative workup is preferred.
  • distillation processes known to those skilled in the art can be used.
  • Suitable devices for the workup by distillation are also known to the person skilled in the art.
  • the glycerol separated off in the work-up of the product from step (C) of the process according to the invention can in a preferred embodiment be recycled to the hydrogenation stage.
  • Carrier gas helium
  • a fluid circulation reactor is used for the glycerol hydrogenation.
  • a catalyst containing Cu, La and Al are filled in oxidic form.
  • the catalyst is reduced in situ with hydrogen.
  • the reactor is followed by a second reactor (control reactor), which is filled under identical operating conditions with the same catalyst.
  • this reactor corresponds to the reactor in which, according to step (C), the glycerol stream G2 is reduced to 1,2-propanediol.
  • the catalyst in the second reactor is also assayed for traces of sulfur after 8000 hours to determine the efficiency of the first reactor.
  • the reactor effluent is collected and analyzed.
  • the catalyst is removed in portions and analyzed for sulfur content. Based on the measured data, a sulfur profile is created over the catalyst bed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de 1,2-propanediol à partir de glycérine, comportant au moins les étapes consistant (A) à préparer un flux de glycérine G1, (B) à désulfurer le flux de glycérine G1 de l'étape (A) par hydrogénation avec de l'hydrogène à une pression comprise entre 50 et 300 bars en présence d'un catalyseur pour obtenir un flux de glycérine G2, et (C) à hydrogéner le flux de glycérine G2 de l'étape (B) avec de l'hydrogène en présence d'un catalyseur pour obtenir du 1,2-propanediol.
PCT/EP2010/058543 2009-06-19 2010-06-17 Procédé d'hydrogénation de glycérine en 1,2-propanediol, avec désulfuration par hydrogénation sur lit sacrificiel Ceased WO2010146117A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09163198 2009-06-19
EP09163198.6 2009-06-19

Publications (2)

Publication Number Publication Date
WO2010146117A2 true WO2010146117A2 (fr) 2010-12-23
WO2010146117A3 WO2010146117A3 (fr) 2011-06-23

Family

ID=43067160

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/058543 Ceased WO2010146117A2 (fr) 2009-06-19 2010-06-17 Procédé d'hydrogénation de glycérine en 1,2-propanediol, avec désulfuration par hydrogénation sur lit sacrificiel

Country Status (1)

Country Link
WO (1) WO2010146117A2 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007099161A1 (fr) * 2006-03-03 2007-09-07 Basf Se Procédé de synthèse du 1,2-propanediol
CN101848884B (zh) * 2007-08-31 2013-05-01 巴斯夫欧洲公司 通过在至少三个连续的反应器中将甘油氢化制备1,2-丙二醇的方法

Also Published As

Publication number Publication date
WO2010146117A3 (fr) 2011-06-23

Similar Documents

Publication Publication Date Title
JP4278910B2 (ja) エステルの製造法
EP2200960B1 (fr) Procédé de production de propane-1,2-diol par hydrogénation à basse pression de glycérine
EP2097367B1 (fr) Procédé de fabrication d'esters alkyliques d'acides gras et d'acroléine à partir de triglycérides
EP0198243B1 (fr) Procédé de préparation d'esters alkyliques d'acides carboxyliques en particulier d'esters alkyliques d'acides gras
EP2432756B1 (fr) Procédé de production d'alcools gras par hydrogénation de triglycérides d'acide gras en présence d'un catalyseur hétérogène contenant du cuivre
EP2200958B1 (fr) Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans une cascade de réacteurs à deux étages
WO2009027501A2 (fr) Procédé de production de propane-1,2-diol par hydrogénation de glycérine dans au moins trois réacteurs montés en série
EP0610742A1 (fr) Procédé d'obtention de tocophérols et de stérols à partir de sources naturelles
EP2358851B1 (fr) Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras
DE3719790A1 (de) Herstellung von langkettigen polyolen aus nachwachsenden rohstoffen
EP2635544A1 (fr) Procédé de production d'un phénylcyclohexane
WO2009133066A1 (fr) Procédé d'hydrogénolyse de polyols
WO2017093308A1 (fr) Isomérisation de mdach
DE4217839B4 (de) Verfahren zur Herstellung von entschwefelten Fetten und Ölen oder Fettsäureestern und Verfahren zur Herstellung von Alkoholen unter Verwendung der entschwefelten Fette und Öle oder Fettsäureester
EP1132385B1 (fr) Procédé de production d'acétate d' alfa-tocophérol par condensation de diesters de triméthylhydroquinone avec l' isophytol
WO2010146117A2 (fr) Procédé d'hydrogénation de glycérine en 1,2-propanediol, avec désulfuration par hydrogénation sur lit sacrificiel
DE19810440C1 (de) Verfahren zur Herstellung von ungesättigten Fettalkoholen aus Lauricölen
EP2415738B1 (fr) Procédé de fabrication d'alcanes saturés linéaires à partir d'alcools primaires
EP0285835A2 (fr) Procédé d'hydrogénation directe de graisse de beurre
EP0902006B1 (fr) Oléines stables à l'oxydation
DE102014113197A1 (de) Verfahren und Anlage zur Herstellung von Fettalkoholen
EP1889825A1 (fr) Procédé pour la synthèse du 1,2-propanediol
DE102008008389A1 (de) Methylcyclopentylester
WO1999025674A1 (fr) Alcools gras insatures de noix de coco et de noix de palme
DE102011012177A1 (de) Verfahren zum Gewinnen von Fettalkoholen aus Abfallfetten oder Abfallölen

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10725708

Country of ref document: EP

Kind code of ref document: A2

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10725708

Country of ref document: EP

Kind code of ref document: A2