EP4709704A1 - Procédé d'hydrogénation directe d'acides carboxyliques en alcanes - Google Patents

Procédé d'hydrogénation directe d'acides carboxyliques en alcanes

Info

Publication number
EP4709704A1
EP4709704A1 EP24724459.3A EP24724459A EP4709704A1 EP 4709704 A1 EP4709704 A1 EP 4709704A1 EP 24724459 A EP24724459 A EP 24724459A EP 4709704 A1 EP4709704 A1 EP 4709704A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydrogenation
bar
range
ruthenium
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
EP24724459.3A
Other languages
German (de)
English (en)
Inventor
Holger Becker
Julian Dominic HABERKORN
Konrad Möbus
Mona MÜLLER
Nikolai SONNEK
Niklas ZAHN
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.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
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Filing date
Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP4709704A1 publication Critical patent/EP4709704A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
    • 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
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium

Definitions

  • the present invention relates to a process for direct hydrogenation of free fatty acids in the presence of a catalyst in order to produce linear saturated alkanes.
  • the catalyst used is a supported ruthenium catalyst.
  • Breit (ACS Catal. 2018, 8, 785-789) describes the hydrogenation of carboxylic acids using PdRe/C catalysts. Depending on the temperature, either the corresponding alcohols or alkanes are obtained. Temperatures above 160°C result in the formation of alkanes. A disadvantage of this method is the use of very expensive palladium. In addition, rhenium must also be used, which is presumably lost in the product solution during the reaction.
  • Rhenium-based catalysts have impressive selectivity resulting in alcohol as the only product (Broadbent, H. Smith; Bartley, William J., Journal of Organic Chemistry (1963), 28(9), 2347-2350). However, relatively high pressures and temperatures are necessary and the need to use rhenium makes the method commercially unattractive.
  • rhenium on titanium dioxide has been used for the hydrogenation of fatty acids to alcohols.
  • the processing of the used catalysts and the recovery of rhenium remains to be clarified.
  • the use of rhenium renders the method commercially unattractive.
  • so-called copper chromite catalysts (Adkins catalysts) are known, which are available for producing fatty alcohols from fatty acid esters by hydrogenation at high temperatures (see Shigeo Nishimura HANDBOOK OF HETEROGENEOUS CATALYTIC HYDROGENATION FOR ORGANIC SYNTHESIS, John Wiley & Sons, 2001 , page 392).
  • esters must be used, since the catalysts are not stable in the presence of free fatty acids and dissolve during the reaction.
  • chromium is used as a feedstock, which must be avoided at all costs for environmental and health reasons.
  • modified ruthenium catalysts various modified ruthenium catalysts are known in which the ruthenium is used in combination with other metals. The addition of other metals serves to increase the selectivity for alcohol formation.
  • W02014066062A1 describes the use of bimetallic ruthenium-rhenium and ruthenium-tin catalysts, and also trimetallic ruthenium-rhenium-tin catalysts for the hydrogenation of carboxylic acids.
  • the alcohols are formed selectively here.
  • Zhao et al. (Green Chem., 2019, 21 , 3059-3064) describe an example of the use of ruthenium in combination with tin on nitrogen-modified carbon support materials.
  • fatty alcohols are formed from various fats and fatty acids.
  • Rodiansono et al. (RSC Adv., 2022, 12, 13319-13329) describe the direct hydrogenation of free fatty acids using titanium dioxide-supported ruthenium catalysts which have been additionally modified with molybdenum. The catalysts exhibit moderate selectivity for the alcohol dodecanol in the hydrogenation of lauric acid at 170°C and 40 bar, and result in only low formation of alkanes.
  • Rodiansono et al. also describe the hydrogenation of lauric acid with an unmodified, titanium dioxide-supported ruthenium catalyst at 170°C, partial H2 pressure 40 bar, over a period of 7 h, which gives 65% dodecanol and only 4% dodecane (cf.
  • CN108993495A discloses a process for producing alkanes from fatty acids by hydrogenation in the presence of a ZrC ⁇ /A Ch-supported ruthenium catalyst. At 140°C and partial H2 pressure 40 bar, alkane yields above 90% are obtained.
  • the object of the present invention consisted of providing a novel method for producing linear saturated alkanes by direct hydrogenation of carboxylic acids, which avoids the disadvantages of the aforementioned methods.
  • the present invention is a.
  • alkanes are produced from fatty acids by a process comprising the following step a: a. hydrogenation of a fatty acid F in the presence of a catalyst K, wherein catalyst K is a supported ruthenium catalyst, and fatty acid F is a linear fatty acid having 4 to 24 carbon atoms, present in free form, and either TiC>2 is used as support material for catalyst K at the temperature during the hydrogenation is in the range between 180°C and 230°C, and the partial hydrogen pressure during the hydrogenation is in the range between 30 bar and 120 bar, or a carbonaceous material is used as support material for catalyst K at the temperature during the hydrogenation is in the range between 180°C and 230°C, and the partial hydrogen pressure during the hydrogenation is in the range between 30 bar and 120 bar.
  • a catalyst K is a supported ruthenium catalyst
  • fatty acid F is a linear fatty acid having 4 to 24 carbon atoms, present in free form
  • TiC>2 is used as support material for catalyst K at the temperature during the
  • the method according to the invention allows simple separation of the catalyst from the reaction mixture by means of conventional filtration methods and thus easy recycling thereof.
  • the catalyst K of the present invention is stable with respect to free fatty acids.
  • the method according to the invention affords good yields and has high selectivity for alkane products.
  • the method of the present invention does not use prohibitively expensive metals and can be carried out under relatively moderate pressure and temperature conditions.
  • the fatty acids F are free, linear carboxylic acids having a carbon chain length in the range of C4- C24. They are obtained from renewable raw materials such as coconut, palm or palm kernel oil (triglycerides) by processes known per se.
  • the triglycerides are converted to the free fatty acids and glycerol by so-called fat splitting. During splitting, animal and vegetable fats are continuously cleaved into a fatty acid fraction and glycerol. Depending on the crude fat, the fatty acid fraction comprises both saturated and unsaturated fatty acids. After purification, unsaturated fatty acids can be converted to saturated fatty acids by hydrogenation.
  • the free fatty acids can be hydrogenated directly using the method according to the invention.
  • the free fatty acids have different chain lengths, e.g. C4-C18 (butter fat), Cs-Cie (coconut oil), Cie-C (sunflower, olive, rapeseed, nut and soya oils).
  • linear, saturated alkanes having 4 to 24 carbon atoms are obtained according to the following reaction scheme:
  • the resulting alkanes are linear and usually have the same number of carbon atoms or one carbon atom less than the fatty acids used as raw material. Lower alkanes are also formed as by-products: for example, lauric acid is converted to a mixture with the main components dodecane and undecane. In addition, alkanes having a lower number of carbon atoms, such as decane, nonane, octane, etc., are also formed.
  • the resulting linear, saturated alkanes are used, for example, as additives for producing cosmetic preparations such as creams, gels, lotions, emulsions, waxes/fats or powders and ointments.
  • linear saturated alkanes having a carbon number of 4 to 24 carbon atoms are used.
  • examples of such compounds are n-nonane, n-undecane, n-tridecane or n-heptadecane.
  • linear alkanes are also used as mixtures, for example as alkane mixtures in cosmetic formulations.
  • Linear, saturated alkanes are also constituents of diesel and kerosene fuels.
  • the main constituents of diesel fuel are predominantly alkanes, cycloalkanes and aromatic hydrocarbons, each having about 9 to 22 carbon atoms per molecule and a boiling range between 170°C and 390°C.
  • Kerosene consists of a complex mixture of alkanes, cycloalkanes, aromatics and olefins. Jet A, for example, comprises almost exclusively compounds having 9 to 17 carbon atoms, with the emphasis (19.5% mass) on C12 compounds.
  • the products of the method according to the invention can be used accordingly as additives for diesel and kerosene.
  • the catalyst K used in the method according to the invention is a heterogeneous ruthenium catalyst, which is characterized in that the active ruthenium is deposited on a support.
  • Ruthenium is used as a catalyst for the hydrogenation of a large number of functional groups and aromatic rings (Morris Freifelder, Practical Catalytic Hydrogenation, Wiley and Sons 1971).
  • the reactions are carried out at 70-100°C and 60-70 bar hydrogen pressure.
  • Ruthenium is generally less sensitive to poisoning than other comparable catalysts. Examples are the hydrogenation of aniline to cyclohexylamine, substituted benzenes and pyridines to ring- hydrogenated products, carboxylic acids and hydroxycarboxylic acids to the corresponding alcohols and diols, and the reduction of ketones and aldehydes. For instance, ruthenium on activated carbon is used for the hydrogenation of sugars to the corresponding sugar alcohols.
  • the ruthenium catalysts are prepared according to known methods as described, for example, in US2014243562A1 .
  • Ruthenium catalysts are also commercially available, e.g. Evonik Noblyst®P3 series, such as Noblyst®P3060 5% Ru on activated carbon.
  • Support materials used in the catalysts according to the invention may be various powder materials.
  • moulded supports such as extrudates, tablets, spheres or other moulded bodies.
  • the ruthenium may either be applied to carbonaceous support materials or to titanium dioxide supports.
  • Activated carbon for example, may be used as carbonaceous support material. It is possible to use activated carbon from different source materials such as peat, wood, coconut, bamboo etc., which have been activated by different processes (e.g. by steam or by chemical activation using phosphoric acid, zinc chloride etc.).
  • Graphite, carbon black, carbon nanotubes, carbon fibres and carbon aerogels may also be used as suitable support materials based on carbon.
  • titanium dioxide it is possible to use titanium dioxide as support material.
  • the proportion of the mass of ruthenium in the total mass of catalyst K is in the range between 1 % and 10%.
  • the method according to the invention can be carried out, for example, as a suspension process.
  • the reaction is carried out in a stirred pressure vessel.
  • the catalyst and the fatty acid are initially charged in the reactor without solvent or dissolved in a suitable solvent and reacted with hydrogen at elevated temperature and pressure.
  • the substrate can be fully initially charged in the reactor or be added continuously or discontinuously during the reaction.
  • the reaction mixture is separated from the catalyst (for example by filtration) and optionally purified.
  • the catalyst can then be reused.
  • the method can also be carried out in continuous mode, as is well known to those skilled in the art, for example in a continuous stirred tank reactor, or in a cascade of stirred tank reactors, in loop reactors, in bubble columns, or, for example, in plug flow reactors.
  • Tubular reactors in which the catalyst is permanently installed in the form of a tubular reactor, or is used as a moving bed, are particularly suitable for the use of the catalyst as a moulded body.
  • activated carbon is used as support material for catalyst K and the temperature during the hydrogenation is in the range between 180°C and 230°C, and the partial hydrogen pressure during the hydrogenation is in the range between 30 bar and 90 bar.
  • a TiC>2-containing material is used as support material for catalyst K and the temperature during the hydrogenation is in the range between 180°C and 230°C, and the partial hydrogen pressure during the hydrogenation is in the range between 30 bar and 120 bar.
  • the carbonaceous support material used for catalyst K is activated carbon, graphite, carbon black, carbon nanotubes, carbon fibres, carbon aerogels, or a mixture of two or more of these materials.
  • a carbonaceous material is used as support material for catalyst K, and the partial hydrogen pressure during the hydrogenation is in the range between 30 bar and 90 bar.
  • the solvent used for the hydrogenation of the fatty acid F in the presence of catalyst K is an alkane having 4 to 24 carbon atoms.
  • the solvent used for the hydrogenation of a fatty acid F having XC carbon atoms in the presence of catalyst K is an alkane having XC carbon atoms, where XC is an integer from 4 to 24.
  • Methods according to this embodiment have the advantage that, after the catalyst has been removed, the reaction product can be used again as solvent for the hydrogenation.
  • the present invention further encompasses the use of a catalyst K for producing alkanes from fatty acids by hydrogenation, wherein catalyst K is a supported ruthenium catalyst, and wherein fatty acid F is a linear fatty acid having 4 to 24 carbon atoms, present in free form, and either TiC>2 is used as support material for catalyst K at the temperature during the hydrogenation is in the range between 180°C and 230°C, and the partial hydrogen pressure during the hydrogenation is in the range between 30 bar and 120 bar, or a carbonaceous material is used as support material for catalyst K at the temperature during the hydrogenation is in the range between 180°C and 230°C, and the partial hydrogen pressure during the hydrogenation is in the range between 30 bar and 120 bar.
  • a catalyst K for producing alkanes from fatty acids by hydrogenation wherein catalyst K is a supported ruthenium catalyst, and wherein fatty acid F is a linear fatty acid having 4 to 24 carbon atoms, present in free form, and either TiC>2 is used as support material for
  • the reuse of the catalyst was performed as follows: the reaction solution was separated from the catalyst by centrifuging. The catalyst was retained as completely as possible in the 100 ml pressure vessel. Thereafter, 9.6 g of dodecanoic acid was dissolved in 22.4 g of the centrifugate obtained from the preceding experiment and transferred into the pressure vessel. The rest of the process was effected as in Example 16-B.
  • Table 4 shows the results of the GC analysis of the product solutions from the recycling experiments.
  • the lauric acid was fully converted in all cases.
  • what is formed is predominantly undecane, the concentration of which rises with increasing degree of recycling.
  • the reuse of the catalyst was performed as follows: 30 ml of the product solution was centrifuged, and 11 .5 g of the centrifugate was taken for GC analysis. The catalyst remaining in the centrifuge vessel was suspended and returned to the pressure vessel. Subsequently, 11.5 g dodecanoic acid was weighed into the 100 ml pressure vessel, continuing as described in Example 17-B.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production d'alcanes saturés linéaires par hydrogénation directe d'acides gras libres ayant 4 à 24 atomes de carbone. Les acides gras libres sont hydrogénés en présence de catalyseur et d'hydrogène. Le catalyseur utilisé est un catalyseur à base de ruthénium supporté, avec utilisation soit de TiO2 soit d'un matériau carboné en tant que matériau de support pour le catalyseur.
EP24724459.3A 2023-05-11 2024-05-02 Procédé d'hydrogénation directe d'acides carboxyliques en alcanes Pending EP4709704A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23172881 2023-05-11
PCT/EP2024/062015 WO2024231202A1 (fr) 2023-05-11 2024-05-02 Procédé d'hydrogénation directe d'acides carboxyliques en alcanes

Publications (1)

Publication Number Publication Date
EP4709704A1 true EP4709704A1 (fr) 2026-03-18

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ID=86332354

Family Applications (1)

Application Number Title Priority Date Filing Date
EP24724459.3A Pending EP4709704A1 (fr) 2023-05-11 2024-05-02 Procédé d'hydrogénation directe d'acides carboxyliques en alcanes

Country Status (2)

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EP (1) EP4709704A1 (fr)
WO (1) WO2024231202A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102876350B (zh) * 2012-09-26 2015-09-09 中国科学技术大学 由Ru系催化剂催化植物油或长链脂肪酸制备高十六烷值烷烃燃料的方法及其应用
US9108895B2 (en) 2012-10-26 2015-08-18 Eastman Chemical Company Promoted ruthenium catalyst for the improved hydrogenation of carboxylic acids to the corresponding alcohols
DE102013203420A1 (de) 2013-02-28 2014-08-28 Evonik Industries Ag Hydrogenolyse von Furfurylalkohol zu 1,2-Pentandiol
CN108993495B (zh) 2018-08-01 2020-12-25 中国科学技术大学 含羰基或羟基化合物催化脱氧制备烷烃类化合物的方法

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