EP3990424A1 - Process for the preparation of a fatty aldehyde - Google Patents

Process for the preparation of a fatty aldehyde

Info

Publication number
EP3990424A1
EP3990424A1 EP20734048.0A EP20734048A EP3990424A1 EP 3990424 A1 EP3990424 A1 EP 3990424A1 EP 20734048 A EP20734048 A EP 20734048A EP 3990424 A1 EP3990424 A1 EP 3990424A1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
process according
catalyst
fatty
contacting
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.)
Withdrawn
Application number
EP20734048.0A
Other languages
German (de)
French (fr)
Inventor
Jens Johannsen
Thomas WALUGA
Georg Fieg
Francesca Meyer
Niels KOPETZ
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.)
Technische Universitaet Hamburg TUHH
Original Assignee
Technische Universitaet Hamburg TUHH
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
Priority claimed from LU101281A external-priority patent/LU101281B1/en
Application filed by Technische Universitaet Hamburg TUHH filed Critical Technische Universitaet Hamburg TUHH
Publication of EP3990424A1 publication Critical patent/EP3990424A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6409—Fatty acids
    • C12P7/6418—Fatty acids by hydrolysis of fatty acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y301/00—Hydrolases acting on ester bonds (3.1)
    • C12Y301/01—Carboxylic ester hydrolases (3.1.1)
    • C12Y301/01003—Triacylglycerol lipase (3.1.1.3)

Definitions

  • the present invention relates to a process for the preparation of a fatty aldehyde, which process avoids the use of fossil resources and/or harsh reaction conditions, as well as the use of the obtained fatty aldehyde as e.g. a flavoring agent or fragrance .
  • Short-chain fatty al dehydes are usually prepared by hydroformylation .
  • the alkenes used as starting material in the hydroformylation reaction are typically obtained on the basis of crude oil.
  • ra ther high temperatures and very high pressures are applied in the hydroformylation reaction.
  • Long-chain fatty aldehydes are primarily obtained by dehydration of fatty alcohols. Also this process is typically characterized by the use of fossil start ing materials and rather harsh reaction conditions.
  • EP 37149 describes a method for the preparation of aldehydes by dehydrogenation of monovalent primary alcohols in the gas phase by means of a copper-containing catalyst. For example, passing a gaseous mixture comprising octanol-1 and hydrogen over a Cu/MgO catalyst for a period of four weeks at a temperature of 265 to 330°C results in an octanol conversion of 58%.
  • a gaseous mixture comprising octanol-1 and hydrogen over a Cu/MgO catalyst for a period of four weeks at a temperature of 265 to 330°C results in an octanol conversion of 58%.
  • the corresponding use of an Ag/Na20 catalyst is de scribed in SU 789491, and US 4,304,943 describes the conver sion of alkyl and aryl hydroxy compounds to aldehydes in the presence of hydrogen using a MnO/NiO/MgO catalyst.
  • US 2,128,908 relates to a process for preparing short chain aliphatic aldehydes by oxidizing C3- and C4- alkanes. For instance, a mixture of propane and butane is oxi dized at 425 to 460°C to yield the desired aldehyde (20%) as well as formaldehyde (15%), methanol (19%) and carboxylic ac ids (11%) .
  • the present invention relates to a process for the preparation of a fatty aldehyde which comprises
  • a solid zerovalent metal catalyst allows the synthe sis of a fatty aldehyde with a high selectivity in a simple method without the use of excessive reaction temperatures or pressures.
  • the fatty acid used as starting material in the process according to the invention can suitably be pro vided on the basis of natural, renewable resources. Thus, the use of fossil resources can be reduced or even avoided.
  • the zerovalent metal catalyst is in the form of solid parti cles, i.e. is a solid catalyst. It can be an unsupported (bulk) catalyst or can comprise a support material on or in which the zerovalent metal is present.
  • the zerovalent metal catalyst is a bulk catalyst, i.e. the cata lyst is unsupported and essentially consists of or consists of the zerovalent metal.
  • the oxidation state of the metal is ze ro .
  • the solid particles of the zerovalent metal catalyst have a specific surface area of 0.0001 to 1080 m 2 /g, preferably 0.0003 to 1 m 2 /g, more prefera bly 0.005 to 0.002 m 2 /g or 0.0005 to 0.02 m 2 /g, even more pref erably 0.001 to 0.01 m 2 /g.
  • the specific surface area can suita bly be determined by imaging procedures.
  • the average particle size of the solid particles size is deter mined via microscopy and on the basis of this parameter the surface area of the particles is calculated assuming a spheri cal shape of each particle. It has been found that a zerovalent metal catalyst having such a specific surface area is particularly suitable for the efficient and selective con version of fatty acids into fatty aldehydes.
  • the solid particles have an average particle size of 70 nm to 3000 pm, preferably 5 to 2500 pm, such as 5 to 20 pm or 50 to 150 pm or 500 to 2500 pm, as de termined by imaging procedures, such as microscopy, resulting in a number-based average.
  • the metal of the zerovalent metal catalyst can suitably have a standard electrode potential of less than 1.40 V, preferably less than 1.20 V, more preferably less than 0.80 V.
  • the metal can be selected from the group consisting of Fe, Cu, Ag, Hg, Au, Pt and Sn and combinations thereof, and preferably is Fe or Cu or Ag and more preferably is Fe . In one embodiment the iron is present in the form of iron filings.
  • catalysts having a rather high specif ic surface area suitably comprise a more noble metal, such as silver.
  • catalysts having a rather low specific surface area suitably comprise a less noble metal, such as iron .
  • the fatty acid which is provided in step (a) of the process according to the invention and which is to be reduced to the corresponding aldehyde, can typically comprise an aliphatic carboxylic acid having 1 to 32 carbon atoms, preferably 4 to 28, more preferably 6 to 18 carbon atoms.
  • the fatty acid can be saturated or unsaturated and can be branched or unbranched.
  • the fatty acid is unbranched.
  • the fat ty acid provided in step (a) is a saturated fatty acid and the metal of the zerovalent metal catalyst used in step (b) is Fe or Cu, preferably Fe .
  • the catalayst used in step (b) is a bulk catalyst.
  • step (a) The selective reduction of the fatty acid to yield the corre sponding aldehyde does generally not depend on the source of the fatty acid.
  • synthetic fatty acids as well as fatty acids obtained from natural products or renewable starting ma terials, like vegetable oils or other natural fatty acid es ters, can be provided in step (a) .
  • the fatty acid provided in step (a) is obtained from natural sources such as renewable starting materials.
  • the fatty acid is provided by
  • the enzymatic catalyst is suitably a hydrolase, preferably a hydrolase of subclass EC 3.1 such as subclass 3.1.1 like 3.1.1.1 and 3.1.1.3, more preferably an esterase like a li pase, such as e.g. lipase B Candida antarctica.
  • the fatty acid ester provided in step (al) can be both a synthetic fatty acid ester or a natural fatty acid ester, such as a veg etable oil.
  • the fatty acid ester provided in step (al) is preferably natural fatty acid ester, such as a vegetable oil.
  • step (b) the contacting is typically effected at a ratio of the zerovalent metal catalyst relative to the fatty acid of 8.0 ⁇ 10 5 to 3.1 ⁇ 10 3 m 2 of catalyst per mmol of fatty acid, preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 3 m 2 of catalyst per mmol of fatty acid, and more preferably 2.0 ⁇ 10 4 to 5.0 ⁇ 10 4 m 2 of catalyst per mmol of fatty acid. It has been found that such a ratio of zerovalent metal catalyst to fatty acid is particu larly suitable for the efficient and selective conversion of fatty acids into fatty aldehydes.
  • step (b) the contacting is effected at a temperature of 80 to 800°C, pref erably 80 to 250°C, more preferably 85 to 250°C, most prefera bly 90 to 220°C, such as about 90°C or 180 to 220°C; and/or at a pressure of 100 to 1200 mbar, preferably 100 to 300 mbar or about 1000 mbar; and/or for a time of 3 to 180 min, preferably 15 to 120 min, more preferably 20 to 90 min, most preferably 30 to 70 min.
  • the reducing performance of the metal catalyst can be effected by other conditions as well.
  • the presence of oxy gen or water can result in an undesired redox reaction between the metal catalyst and oxygen and/or water so that the amount of metal catalyst available for the reduction the fatty acid becomes too low.
  • the contacting in step (b) is suitably effected at a concentration of water of less than 10 wt.-%, preferably less than 2 wt.-%, more preferably 0 to less than 1 wt.-%, relative to the total weight of the reaction mixture of step (b) .
  • the contacting in step (b) is suitably effected at a concentration of oxygen of less than 20 wt.-%, preferably less than 19 wt.-%, more preferably 0 to 1 wt.-%, such as 0 to 0.1 or 0 to 0.01 wt.-%, relative to the total weight of the reaction mixture of step (b) .
  • step (b) can be carried without the presence of hydrogen and it is preferred that the contact ing in step (b) is effected at a concentration of hydrogen of about 0 wt.-%.
  • the reduction in step (b) can be carried out in the presence of an alcohol, such as a fatty alcohol like hexanol.
  • the weight ratio between such an alcohol and the fat ty acid provided in step (a) can range from e.g. 1:10 to 10:1, such as 1:5 to 5:1 or 1:2 to 2:1 and can in particular be about 1:1. It has been found that the presence of an alcohol can increase the conversion of the fatty acid to the fatty al dehyde. Without wishing to be bound by a particular theory, it is assumed that the alcohol may result in a certain regenera tion of the metal catalyst, e.g. by reducing iron oxide formed during step (b) to zerovalent iron again.
  • the aldehyde obtained in step (b) preferably comprises 1 to 32 carbon atoms, and more preferably comprises hexanal, octanal, decanal, dodecanal or mixtures thereof.
  • Such aldehydes are valuable products which can in particular be used as a flavor ing agent, fragrance or as an intermediate product for the production of plastifiers, lubricating agents, polymers of pharmaceuticals .
  • the container containing the solid phase com prising dodecanoic acid was equipped with a heating unit and a distilling connecting tube which was held at 18°C. A pressure of 100 mbar was applied. The temperature of the distillation receiver and the gas phase of the distilling connecting unit was monitored and water was completely removed from the dodecanoic acid by distillation at a temperature of about 60 °C .
  • Iron particles having a particle size of about 500 to 2500 pm and a specific surface area of about 14.7 cm 2 /g.
  • Iron particles having a particle size of about 90 pm and a specific surface area of about 8.44 ⁇ 10 3 cm 2 /g.
  • Iron particles having a particle size of about 70 nm and a specific surface area of about 1.08 ⁇ 10 7 cm 2 /g.
  • Copper particles having a particle size of about 9 pm and a specific surface area of about 7.41 ⁇ 10 4 cm 2 /g.
  • reaction mixtures were also analyzed via gas chromatography using a PerkinElmer Clarus 500 apparatus equipped with flame ionization detector and a SUPELCO SLB-5ms capillary column having dimensions of 30 mm x 0.25 mm x 0.25 pm. Nitrogen was used as mobile phase.
  • the temperature was kept at 60°C for 6 minutes and subsequently raised to 210°C at a rate of 12°C/min. Then the temperature was kept at 210°C for 1.5 minutes.
  • the reaction mixtures showed a peak at about 6.9 min indicative for hexanal with no peak at about 9.5 min which would be indicative for hexanol .

Abstract

The present invention relates to a process for the preparation of a fatty aldehyde which process comprises (a) providing a fatty acid, and (b) contacting the fatty acid with a zerovalent metal catalyst to reduce the fatty acid to the fatty aldehyde, wherein the zerovalent metal catalyst is in the form of solid particles.

Description

Process for the preparation of a fatty aldehyde
The present invention relates to a process for the preparation of a fatty aldehyde, which process avoids the use of fossil resources and/or harsh reaction conditions, as well as the use of the obtained fatty aldehyde as e.g. a flavoring agent or fragrance .
There are currently two main methods for the synthesis of al dehydes, in particular fatty aldehydes. Short-chain fatty al dehydes are usually prepared by hydroformylation . The alkenes used as starting material in the hydroformylation reaction are typically obtained on the basis of crude oil. In general, ra ther high temperatures and very high pressures are applied in the hydroformylation reaction. Long-chain fatty aldehydes are primarily obtained by dehydration of fatty alcohols. Also this process is typically characterized by the use of fossil start ing materials and rather harsh reaction conditions.
For instance, EP 37149 describes a method for the preparation of aldehydes by dehydrogenation of monovalent primary alcohols in the gas phase by means of a copper-containing catalyst. For example, passing a gaseous mixture comprising octanol-1 and hydrogen over a Cu/MgO catalyst for a period of four weeks at a temperature of 265 to 330°C results in an octanol conversion of 58%. The corresponding use of an Ag/Na20 catalyst is de scribed in SU 789491, and US 4,304,943 describes the conver sion of alkyl and aryl hydroxy compounds to aldehydes in the presence of hydrogen using a MnO/NiO/MgO catalyst.
Furthermore, US 2,128,908 relates to a process for preparing short chain aliphatic aldehydes by oxidizing C3- and C4- alkanes. For instance, a mixture of propane and butane is oxi dized at 425 to 460°C to yield the desired aldehyde (20%) as well as formaldehyde (15%), methanol (19%) and carboxylic ac ids (11%) .
Alternative methods for the preparation of aldehydes, such as the extraction of aldehydes from natural products, are typi cally characterized by a very low yield. For example, Palma et al . (J. Agric. Food Chem. 1999, 47, 5044) report on the super critical fluid extraction of white grape seeds resulting in a an average yield of 10.6% for the first fraction which inter alia comprises aliphatic aldehydes in addition to fatty acids and sterols. Moreover, Chouchi et al . describe the desorption of bigarade peel oil from a polar adsorbent by supercritical CO2 yielding a residue fraction comprising 0.22% of n-heptanal .
Hence, there is still a need for a further process for the preparation of fatty aldehydes. In particular, it would be de sirable to provide a process for the synthesis of fatty alde hydes which process allows the use of renewable starting mate rials and, thereby, reducing or avoiding the use of fossil re sources. Moreover, the process should allow the use of mild reaction conditions so that rather high temperatures and/or pressures can be avoided. In addition, the fatty aldehyde should be obtainable with a high selectivity.
It has surprisingly been found that the above problems are solved by the process defined below and in the appended claims .
Accordingly, in a first aspect the present invention relates to a process for the preparation of a fatty aldehyde which comprises
(a) providing a fatty acid, and (b) contacting the fatty acid with a zerovalent metal cata lyst to reduce the fatty acid to the fatty aldehyde, wherein the zerovalent metal catalyst is in the form of solid particles.
It has surprisingly been found that the contacting of a fatty acid with a solid zerovalent metal catalyst allows the synthe sis of a fatty aldehyde with a high selectivity in a simple method without the use of excessive reaction temperatures or pressures. Moreover, the fatty acid used as starting material in the process according to the invention can suitably be pro vided on the basis of natural, renewable resources. Thus, the use of fossil resources can be reduced or even avoided.
The zerovalent metal catalyst is in the form of solid parti cles, i.e. is a solid catalyst. It can be an unsupported (bulk) catalyst or can comprise a support material on or in which the zerovalent metal is present. Preferably, the zerovalent metal catalyst is a bulk catalyst, i.e. the cata lyst is unsupported and essentially consists of or consists of the zerovalent metal. The oxidation state of the metal is ze ro .
Moreover, it is preferred that the solid particles of the zerovalent metal catalyst have a specific surface area of 0.0001 to 1080 m2/g, preferably 0.0003 to 1 m2/g, more prefera bly 0.005 to 0.002 m2/g or 0.0005 to 0.02 m2/g, even more pref erably 0.001 to 0.01 m2/g. The specific surface area can suita bly be determined by imaging procedures. In particular, the average particle size of the solid particles size is deter mined via microscopy and on the basis of this parameter the surface area of the particles is calculated assuming a spheri cal shape of each particle. It has been found that a zerovalent metal catalyst having such a specific surface area is particularly suitable for the efficient and selective con version of fatty acids into fatty aldehydes.
It is also preferred that the solid particles have an average particle size of 70 nm to 3000 pm, preferably 5 to 2500 pm, such as 5 to 20 pm or 50 to 150 pm or 500 to 2500 pm, as de termined by imaging procedures, such as microscopy, resulting in a number-based average.
The metal of the zerovalent metal catalyst can suitably have a standard electrode potential of less than 1.40 V, preferably less than 1.20 V, more preferably less than 0.80 V. As used herein, the term "standard electrode potential" refers to the standard potential E° at a temperature of 25°C, a pressure of 1 atm and an effective ion concentration of 1 mol/L, with the metal in its zerovalent state as reductant and the metal cati on in its monovalent (oxidation state = +1), divalent (oxida tion state = +2) or trivalent (oxidation state = +3), prefera bly the metal cation in its divalent form, as oxidant. The metal can be selected from the group consisting of Fe, Cu, Ag, Hg, Au, Pt and Sn and combinations thereof, and preferably is Fe or Cu or Ag and more preferably is Fe . In one embodiment the iron is present in the form of iron filings.
Without wishing to be bound to a particular theory, it is be lieved that the higher the specific surface area of the cata lyst is, the higher the tendency for formation of the corre sponding alcohol instead of the desired aldehyde is. The for mation of alcohol is probably due to the further reduction of the intermediate aldehyde. Thus, the specific surface area of the catalyst is believed to have an effect on the selectivity of the catalyst. Hence, catalysts having a rather high specif ic surface area suitably comprise a more noble metal, such as silver. In contrast, catalysts having a rather low specific surface area suitably comprise a less noble metal, such as iron .
The fatty acid, which is provided in step (a) of the process according to the invention and which is to be reduced to the corresponding aldehyde, can typically comprise an aliphatic carboxylic acid having 1 to 32 carbon atoms, preferably 4 to 28, more preferably 6 to 18 carbon atoms. Moreover, the fatty acid can be saturated or unsaturated and can be branched or unbranched. Preferably, the fatty acid is unbranched.
According to a preferred embodiment of the invention, the fat ty acid provided in step (a) is a saturated fatty acid and the metal of the zerovalent metal catalyst used in step (b) is Fe or Cu, preferably Fe . Moreover, it is preferred in this embod iment that the catalayst used in step (b) is a bulk catalyst.
The selective reduction of the fatty acid to yield the corre sponding aldehyde does generally not depend on the source of the fatty acid. Thus, synthetic fatty acids as well as fatty acids obtained from natural products or renewable starting ma terials, like vegetable oils or other natural fatty acid es ters, can be provided in step (a) . Preferably, the fatty acid provided in step (a) is obtained from natural sources such as renewable starting materials. In particular, it is preferred that in step (a) the fatty acid is provided by
(al) providing a fatty acid ester, and
(a2) contacting the fatty acid ester with an enzymatic catalyst to hydrolize the fatty acid ester to the fatty acid.
The enzymatic catalyst is suitably a hydrolase, preferably a hydrolase of subclass EC 3.1 such as subclass 3.1.1 like 3.1.1.1 and 3.1.1.3, more preferably an esterase like a li pase, such as e.g. lipase B Candida antarctica.
Moreover, it is known that synthetic fatty esters, such as ethyl esters, on the one hand and natural fatty acid esters on the basis of triglyceride, such as vegetable oils, on the oth er hand show a very similar hydrolization behavior. Hence, the fatty acid ester provided in step (al) can be both a synthetic fatty acid ester or a natural fatty acid ester, such as a veg etable oil. However, due the general demand for the use of natural starting materials, the fatty acid ester provided in step (al) is preferably natural fatty acid ester, such as a vegetable oil.
In step (b) , the contacting is typically effected at a ratio of the zerovalent metal catalyst relative to the fatty acid of 8.0 · 105 to 3.1 · 103 m2 of catalyst per mmol of fatty acid, preferably 1.0 · 104 to 1.0 · 103 m2 of catalyst per mmol of fatty acid, and more preferably 2.0 · 104 to 5.0 · 104 m2 of catalyst per mmol of fatty acid. It has been found that such a ratio of zerovalent metal catalyst to fatty acid is particu larly suitable for the efficient and selective conversion of fatty acids into fatty aldehydes.
Moreover, it is preferred - with a view to avoid the undesired formation of the corresponding alcohols - that in step (b) the contacting is effected at a temperature of 80 to 800°C, pref erably 80 to 250°C, more preferably 85 to 250°C, most prefera bly 90 to 220°C, such as about 90°C or 180 to 220°C; and/or at a pressure of 100 to 1200 mbar, preferably 100 to 300 mbar or about 1000 mbar; and/or for a time of 3 to 180 min, preferably 15 to 120 min, more preferably 20 to 90 min, most preferably 30 to 70 min. The reducing performance of the metal catalyst can be effected by other conditions as well. For example, the presence of oxy gen or water can result in an undesired redox reaction between the metal catalyst and oxygen and/or water so that the amount of metal catalyst available for the reduction the fatty acid becomes too low. Hence, the contacting in step (b) is suitably effected at a concentration of water of less than 10 wt.-%, preferably less than 2 wt.-%, more preferably 0 to less than 1 wt.-%, relative to the total weight of the reaction mixture of step (b) . Furthermore, the contacting in step (b) is suitably effected at a concentration of oxygen of less than 20 wt.-%, preferably less than 19 wt.-%, more preferably 0 to 1 wt.-%, such as 0 to 0.1 or 0 to 0.01 wt.-%, relative to the total weight of the reaction mixture of step (b) .
In addition, the reduction in step (b) can be carried without the presence of hydrogen and it is preferred that the contact ing in step (b) is effected at a concentration of hydrogen of about 0 wt.-%.
Furthermore, the reduction in step (b) can be carried out in the presence of an alcohol, such as a fatty alcohol like hexanol. The weight ratio between such an alcohol and the fat ty acid provided in step (a) can range from e.g. 1:10 to 10:1, such as 1:5 to 5:1 or 1:2 to 2:1 and can in particular be about 1:1. It has been found that the presence of an alcohol can increase the conversion of the fatty acid to the fatty al dehyde. Without wishing to be bound by a particular theory, it is assumed that the alcohol may result in a certain regenera tion of the metal catalyst, e.g. by reducing iron oxide formed during step (b) to zerovalent iron again.
The aldehyde obtained in step (b) preferably comprises 1 to 32 carbon atoms, and more preferably comprises hexanal, octanal, decanal, dodecanal or mixtures thereof. Such aldehydes are valuable products which can in particular be used as a flavor ing agent, fragrance or as an intermediate product for the production of plastifiers, lubricating agents, polymers of pharmaceuticals .
The invention disclosed herein is exemplified by the following examples which should not be construed to limit the scope of the disclosure.
Examples
Example 1: Preparation of dodecanal
A mixture of 250 mL of ethyl dodecanoat, 250 mL of water and 5g of Novozym 435 (a lipase B acrylic resin from Candida ant- arctica) was stirred at 40°C for 24 hours. Then the mixture was cooled to 0°C for 8 hours. The liquid phase was separated by decantation. The container containing the solid phase com prising dodecanoic acid was equipped with a heating unit and a distilling connecting tube which was held at 18°C. A pressure of 100 mbar was applied. The temperature of the distillation receiver and the gas phase of the distilling connecting unit was monitored and water was completely removed from the dodecanoic acid by distillation at a temperature of about 60 °C .
Subsequently, 200 g of iron filings having a particle size of about 500 to 2500 pm and a specific surface area of about 14.7 cm2/g were added to the dodecanoic acid. The system was rinsed with nitrogen three times and then a nitrogen pressure of 200 mbar was applied. The reaction mixture was heated to a temper ature of 200 to 230°C for 35 min. Then the pressure was re duced in intervals of 5 mbar to yield dodecanal in the distil lation receiver which dodecanal was identified via gas chroma tography using a PerkinElmer Clarus 500 apparatus equipped with flame ionization detector and a SUPELCO SLB-5ms capillary column having dimensions of 30 mm x 0.25 mm x 0.25 pm. Nitro gen was used as mobile phase. For the detection of dodecanal, the temperature was kept at 60°C for 6 minutes and subsequent ly raised to 200°C at a rate of 12°C/min. Then the temperature was kept at 200°C for 7 minutes.
Example 2: Preparation of hexanal
2 mL (16 mmol) of hexanoic acid were contacted at 90°C for 60 min with the following bulk catalysts A to D. The amount of the bulk catalysts is indicated in Table 1 below. The contact ing was performed at ambient pressure under air atmosphere.
Catalyst A:
Iron particles (iron filings) having a particle size of about 500 to 2500 pm and a specific surface area of about 14.7 cm2/g.
Catalyst B:
Iron particles (iron powder) having a particle size of about 90 pm and a specific surface area of about 8.44 · 103 cm2/g.
Catalyst C:
Iron particles (iron powder) having a particle size of about 70 nm and a specific surface area of about 1.08 · 107 cm2/g.
Catalyst D:
Copper particles having a particle size of about 9 pm and a specific surface area of about 7.41 · 104 cm2/g.
The resulting reaction mixtures were subjected to a Fehling analysis. A blue color was indicative for the presence of al dehydes, i.e. the formation of hexanal. Table 1 :
+/-: moderate blue Fehling analysis
+: significant blue Fehling analysis
++ : intensive blue Fehling analysis
+++ : very intensive blue Fehling analysis
Some of the resulting reaction mixtures were also analyzed via gas chromatography using a PerkinElmer Clarus 500 apparatus equipped with flame ionization detector and a SUPELCO SLB-5ms capillary column having dimensions of 30 mm x 0.25 mm x 0.25 pm. Nitrogen was used as mobile phase. For the detection of hexanal, the temperature was kept at 60°C for 6 minutes and subsequently raised to 210°C at a rate of 12°C/min. Then the temperature was kept at 210°C for 1.5 minutes. The reaction mixtures showed a peak at about 6.9 min indicative for hexanal with no peak at about 9.5 min which would be indicative for hexanol .
Example 3: Preparation of hexanal
3 mL (24 mmol) of hexanoic acid were contacted with 0.669 g of silver catalyst having a total surface of 1.27 cm2 and heated with a Bunsen burner for about 3 minutes. Subsequently, the reaction mixture was subjected to Fehling analysis which was positive indicating the presence of hexanal .

Claims

Claims
1. Process for the preparation of a fatty aldehyde comprising
(a) providing a fatty acid, and
(b) contacting the fatty acid with a zerovalent metal catalyst to reduce the fatty acid to the fatty al dehyde, wherein the zerovalent metal catalyst is in the form of solid particles.
2. Process according to claim 1, wherein the zerovalent metal catalyst is a bulk catalyst.
3. Process according to claim 1 or 2, wherein the solid par ticles have a specific surface area of 0.0001 to 1080 m2/g, preferably 0.0003 to 1 m2/g, more preferably 0.0005 to 0.02 m2/g, even more preferably 0.001 to 0.01 m2/g.
4. Process according to claims 1 to 3, wherein the solid par ticles have an average particle size of 70 nm to 3000 pm, preferably 5 to 2500 pm, such as 5 to 20 pm or 50 to 150 pm or 500 to 2500 pm.
5. Process according to any one of claims 1 to 4, wherein the metal of the zerovalent metal catalyst has a standard electrode potential of less than 1.40 V, preferably less than 1.20 V, more preferably less than 0.80 V.
6. Process according to claim 5, wherein the metal is select ed from the group consisting of Fe, Cu, Ag, Hg, Au, Pt and
Sn and combinations thereof, and preferably is Fe or Cu and more preferably is Fe .
7. Process according to any one of claims 1 to 6, wherein the fatty acid comprises an aliphatic carboxylic acid having 1 to 32 carbon atoms, preferably 4 to 28, more preferably 6 to 18 carbon atoms.
8. Process according to any one of claims 1 to 7, wherein the fatty acid is saturated or unsaturated and preferably is unbranched .
9. Process according to any one of claims 1 to 8, wherein the metal of the zerovalent metal catalyst is Fe or Cu and the fatty acid is saturated.
10. Process according to any one of claims 1 to 9, wherein in step (b) the contacting is effected at a ratio of the zerovalent metal catalyst relative to the fatty acid of 8.0 · 105 to 3.1 · 103 m2 of catalyst per mmol of fatty acid, preferably 1.0 · 104 to 1.0 · 103 m2 of catalyst per mmol of fatty acid, and more preferably 2.0 · 104 to
5.0 · 104 m2 of catalyst per mmol of fatty acid.
11. Process according to any one of claims 1 to 10, wherein in step (b) the contacting is effected at a temperature of 80 to 800°C, preferably 80 to 250°C, more preferably 85 to 250°C, most preferably 90 to 220°C, such as about 90°C or 180 to 220°C; and/or at a pressure of 100 to 1200 mbar, preferably 100 to 300 mbar or about 1000 mbar; and/or for a time of 3 to 180 min, preferably 15 to 120 min, more preferably 20 to 90 min, most preferably 30 to 70 min.
12. Process according to any one of claims 1 to 11, wherein in step (b) the contacting is effected at a concentration of water of less than 10 wt.-%, preferably less than 2 wt.-%, more preferably 0 to less than 1 wt.-%.
13. Process according to any one of claims 1 to 12, wherein in step (b) the contacting is effected at a concentration of oxygen of less than 20 wt.-%, preferably less than 19 wt . - %, more preferably 0 to 1 wt.-%, such as 0 to 0.1 or 0 to 0.01 wt . -% .
14. Process according to any one of claims 1 to 13, wherein in step (b) the contacting is effected at a concentration of hydrogen of about 0 wt.-%.
15. Process according to any one of claims 1 to 14, wherein in step (a) the fatty acid is provided by
(al) providing a fatty acid ester, and
(a2) contacting the fatty acid ester with an enzymatic catalyst to hydrolyze the fatty acid ester to the fatty acid.
16. Process according to claim 15, wherein the enzymatic cata lyst is a hydrolase, preferably a hydrolase of subclass EC 3.1 such as subclass 3.1.1 like 3.1.1.1 and 3.1.1.3, more preferably an esterase like a lipase, such as e.g. lipase B Candida antarctica.
17. Process according to any one of claims 1 to 16, wherein the fatty aldehyde obtained in step (b) comprises 1 to 32 carbon atoms, and preferably comprises hexanal, octanal, decanal, dodecanal or mixtures thereof.
18. Use of a fatty aldehyde obtained by a process according to any one of claims 1 to 17 as a flavoring agent, fragrance or as an intermediate product for the production of plastifiers, lubricating agents, polymers of pharmaceuti- cals.
EP20734048.0A 2019-06-28 2020-06-25 Process for the preparation of a fatty aldehyde Withdrawn EP3990424A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP19183426 2019-06-28
LU101281A LU101281B1 (en) 2019-06-28 2019-06-28 Process for the preparation of a fatty aldehyde
PCT/EP2020/067934 WO2020260523A1 (en) 2019-06-28 2020-06-25 Process for the preparation of a fatty aldehyde

Publications (1)

Publication Number Publication Date
EP3990424A1 true EP3990424A1 (en) 2022-05-04

Family

ID=71111449

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20734048.0A Withdrawn EP3990424A1 (en) 2019-06-28 2020-06-25 Process for the preparation of a fatty aldehyde

Country Status (2)

Country Link
EP (1) EP3990424A1 (en)
WO (1) WO2020260523A1 (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2128908A (en) 1934-09-18 1938-09-06 Celanese Corp Preparation of oxygenated compounds
SU789491A1 (en) 1978-07-05 1980-12-23 Московский Ордена Трудового Красного Знамени Институт Тонкой Химической Технологии Им. М.В.Ломоносова Method of preparing isovaleric aldehyde
US4304943A (en) 1979-08-08 1981-12-08 Phillips Petroleum Company Conversion of alkyl and aryl hydroxy compounds producing aldehyde, alcohol and ketone using manganese oxide/nickel oxide/magnesium oxide catalysts
NL8001878A (en) 1980-03-29 1981-11-02 Stamicarbon PROCESS FOR THE PREPARATION OF ALDEHYDES.
JP3812101B2 (en) * 1997-11-17 2006-08-23 三菱化学株式会社 Method for producing aldehydes and / or alcohols
US20070179082A1 (en) * 2006-01-30 2007-08-02 The Procter & Gamble Company Dryer-added fabric care articles

Also Published As

Publication number Publication date
WO2020260523A1 (en) 2020-12-30

Similar Documents

Publication Publication Date Title
EP2006389A2 (en) Method for production of condensed polyunsaturated fatty acid oil
Van den Hark et al. Hydrogenation of fatty acid methyl esters to fatty alcohols at supercritical conditions
Rieke et al. Fatty methyl ester hydrogenation to fatty alcohol part II: process issues
Hermans et al. Solvent‐and metal‐free ketonization of fatty acid methyl esters and triacylglycerols with nitrous oxide
CN105452431A (en) Process for the selective hydrogenation of vegetable oils
JPH10502115A (en) Unsaturated fatty substances with improved low-temperature behavior
CN104640833A (en) Process for preparing a carboxylic acid from a diol or from an epoxide by oxidative cleavage
WO2020260523A1 (en) Process for the preparation of a fatty aldehyde
TW200813229A (en) Method for the regeneration of lipase
LU101281B1 (en) Process for the preparation of a fatty aldehyde
EP1588999B1 (en) Process for producing hydroxy fatty acids from palm oil
EP3237369B1 (en) Improved process for the selective hydrogenation of vegetable oils
JP5334462B2 (en) Production method of fatty acid ester
Frankel et al. Catalytic carboxylation of fats. Carboxy acids and esters from monounsaturates
CA2055960A1 (en) Fatty ester hydrogenation
Martinelli et al. Castor oil hydrogenation by a catalytic hydrogen transfer system using limonene as hydrogen donor
Hark et al. Hydrogenation of fatty acid methyl esters to fatty alcohols at supercritical conditions
CA2329040A1 (en) Method for producing hexanediol
KR102456004B1 (en) Downstream processing of fatty alcohol compositions produced by recombinant host cells
WO2017066901A1 (en) Process for oxidation of alcohols
JP2004512839A (en) Method for isolating 12-hydroxystearic acid
van de Scheur et al. The effect of free fatty acid on the reactivity of copper‐based catalysts for the hydrogenolysis of fatty acid methyl esters
JP4531461B2 (en) Process for producing monounsaturated fatty acids
CN107570085A (en) A kind of phenolic hydroxyl group fatty acid emulsifier and preparation method and application
CA3028249C (en) Process for the selective hydrogenation of vegetable oils using egg-shell type catalysts

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: 20220125

AK Designated contracting states

Kind code of ref document: A1

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 MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20220817