WO2017093473A1 - Réaction de condensation de guerbet - Google Patents

Réaction de condensation de guerbet Download PDF

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Publication number
WO2017093473A1
WO2017093473A1 PCT/EP2016/079565 EP2016079565W WO2017093473A1 WO 2017093473 A1 WO2017093473 A1 WO 2017093473A1 EP 2016079565 W EP2016079565 W EP 2016079565W WO 2017093473 A1 WO2017093473 A1 WO 2017093473A1
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alcohol
copper
guerbet
reaction
group
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PCT/EP2016/079565
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English (en)
Inventor
An Verberckmoes
Pascal van der Voort
Willinton Yesid HERNÁNDEZ
Kevin DE VLIEGER
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Universiteit Gent
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Publication of WO2017093473A1 publication Critical patent/WO2017093473A1/fr

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    • 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
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy

Definitions

  • This invention concerns a process for the preparation of a Guerbet alcohol.
  • This invention concerns a catalyst suitable for the preparation of a Guerbet alcohol.
  • the Guerbet reaction is an organic condensation reaction, whereby a primary or secondary alcohol with a methylene group adjacent to the hydroxylated carbon atom is condensed with the same alcohol (self-condensation) or with another alcohol (cross-condensation), with the release of water. This reaction requires a catalyst and elevated temperatures.
  • the alcohols derived from this reaction are called Guerbet alcohols.
  • the Guerbet reaction Due to the specific branching pattern of the product alcohols, the Guerbet reaction has many interesting applications. In comparison to their linear isomers, branched-chain Guerbet alcohols have extremely low melting points and excellent fluidity. Because of the increasing availability of bio-based alcohol feedstock, this reaction is of growing importance and interest in terms of renewable value chains for the chemical and biof uel industry.
  • the invention comprises a process for the preparation of a Guerbet alcohol.
  • the process comprises the steps of: (a) providing at least one alcohol, wherein said at least one alcohol has a carbon atom bearing at least one hydrogen atom adjacent to the hydroxyl group;
  • the hydrotalcite is a compound of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • M 2+ is selected from the group comprising Mg, Ni, Zn, Cu, Co, Fe, Pd, Pt, and Ru ; preferably Mg, Ni and Cu ;
  • M 3+ is selected from the group comprising Al, Cr, Mn, Co, Fe, and Ga; preferably Al;
  • M 2+ and/or M 3+ ions are isomorphously substituted by M + or M 4+ , wherein M 4+ is selected from the group comprising Ge, Sn, and Pb.
  • the Cu:Ni molar ratio in the copper-nickel catalyst is at least 0.1 :9.9 and at most 6.0:4.0, preferably at least 0.2:9.8 and at most 5.0:5.0, preferably at least
  • the copper-nickel catalyst comprised in a hydrotalcite is subjected to a thermal treatment prior to step (b).
  • the copper-nickel catalyst is present in an amount of 0.05 to 5.0% by weight, based on the weight of said at least one alcohol.
  • the alkaline catalyst is present in an amount of 0.5 to 5.0% by weight, based on the weight of said at least one alcohol, and wherein the alkaline catalyst is selected from the group comprising alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates and alkali earth metal carbonates, alkali metal phosphates, alkaline earth metal oxides, zeolites, alkyl amines or mixtures thereof.
  • the at least one alcohol is a C 2 -C 36 alcohol, preferably a C 6 - C 24 alcohol, more preferably a C 8 -Ci 8 alcohol.
  • the at least one alcohol comprises at least one aliphatic diol, preferably selected from the group comprising: 1 ,3-propanediol, 1 ,4-butanediol, 1 ,2- butanediol, 1 ,3-butanediol, 2,3-butanediol, 2, 2-dimethyl-1 ,3-propanediol, and 1 ,5-pentanediol.
  • step (a) at least one second alcohol is provided in step (a) methanol, an aldehyde, and/or a ketone is provided.
  • step (d) is performed at a temperature of 170 to 280 °C and at a pressure of 1 to 50 bars.
  • step (d) is performed after pre-reduction of the copper-nickel catalyst comprised in a hydrotalcite.
  • the copper-nickel catalyst comprised in a hydrotalcite is recovered and used for a subsequent process according to the first aspect of the invention.
  • the present invention relates to a Guerbet alcohol obtainable by the process according to the first aspect.
  • Preferred embodiments for the first aspect of the invention are also preferred embodiments for the second aspect of the invention.
  • the present invention relates to a Guerbet alcohol.
  • Preferred embodiments for the first or second aspect of the invention are also preferred embodiments for the third aspect of the invention.
  • the present invention relates to the use of a copper-nickel catalyst comprised in a hydrotalcite to prepare a Guerbet alcohol.
  • Preferred embodiments for the first, second, or third aspect of the invention are also preferred embodiments for the third aspect of the invention.
  • the present invention relates to a copper-nickel catalyst comprised in a hydrotalcite.
  • a copper-nickel catalyst comprised in a hydrotalcite.
  • the copper-nickel catalyst is comprised in a hydrotalcite of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • n is an integer selected from 1 or 2;
  • M 2+ is selected from the group comprising Mg, Ni, Zn, Cu, Co, Fe, Pd Pt, and Ru; preferably Mg, Ni and Cu;
  • M 3+ is selected from the group comprising Al, Cr, Mn, Co, Fe, and Ga; preferably Al;
  • M 2+ and/or M 3+ ions are isomorphously substituted by M + or M 4+ , wherein M 4+ is selected from the group comprising Ge, Sn, and Pb.
  • the present invention relates to a process for preparing a copper- nickel catalyst comprised in a hydrotalcite.
  • Preferred embodiments for the first, second, third, fourth, or fifth aspect of the invention are also preferred embodiments for the sixth aspect of the invention.
  • the process for preparing a copper-nickel catalyst comprised in a hydrotalcite preferably comprises the step of adding a solution (A) comprising metal salts to a solution (B) comprising precipitating agents, thereby obtaining solids.
  • FIG. 1 illustrates the water-removal configurations described in Example 5.
  • the rectangular frame corresponds to the thermally insulated part of the Dean-Stark configuration, while (10) refers to the molecular sieve.
  • FIG. 2 illustrates a product obtained from a 1 :1 molar ratio of n-C8-OH and n-C18-OH as reacted in example 20.
  • FIG. 3 illustrates the Guerbet product from example 22 from the self-condensation of isostearyl alcohol.
  • FIG. 4 illustrates a chromatogram of the products obtained in example 26. Two C16 Guerbet (GB) products have been formed.
  • FIG. 5 illustrates Guerbet products obtained from the cross-condensation of stearyl alcohol with hexanol, octanol, decanol or dodecanol in a 1 :1 molar ratio.
  • the terms "one or more” or “at least one”, such as one or more or at least one member(s) of a group of members, is clear per se, by means of further exemplification, the term encompasses inter alia a reference to any one of said members, or to any two or more of said members, such as, e.g., any >3, >4, >5, >6 or >7 etc. of said members, and up to all said members.
  • the present invention relates to a process for the preparation of a Guerbet alcohol.
  • the process comprises the steps of: (a) providing at least one alcohol, wherein said at least one alcohol has a carbon atom bearing at least one hydrogen atom adjacent to the hydroxyl group;
  • the at least one alcohol may be any alcohol that is suitable to undergo a Guerbet reaction.
  • the at least one alcohol may be linear or branched.
  • the at least one alcohol may be saturated or unsaturated.
  • the at least one alcohol may comprise substitutions.
  • the at least one alcohol is a C 2 -C 3 6 alcohol, preferably a C 6 -C 2 4 alcohol, more preferably a C 8 -Ci 8 alcohol.
  • the at least one alcohol is selected from the group comprising: 1 -octanol, n-stearyl alcohol, isostearyl alcohol, citronellol, n- hexanol, and n-decanol.
  • the at least one alcohol is preferably a bio-based alcohol.
  • the at least one alcohol may comprise cellulose.
  • the at least one alcohol is derived from a natural source.
  • the at least one alcohol is a fatty acid, preferably a fatty acid derived from a natural source.
  • the natural source is palm oil, algal oil, canola oil, castor bean oil, coconut oil, corn oil, cotton oil, fish oil, flaxseed oil, hempseed oil, jatropha oil, lard, mustard seed oil, nut oil, olive oil, palm kernel oil, peanut oil, rapeseed oil, safflower seed oil, soybean oil, sunflower oil, tall oil, tallow, or yellow grease.
  • the at least one alcohol comprises at least one aliphatic diol, preferably a biomass-derived aliphatic diol.
  • biomass-derived aliphatic diols may be selected from the group comprising: 1 ,3-propanediol, 1 ,4-butanediol, 1 ,2-butanediol, 1 ,3- butanediol, 2,3-butanediol, 2,2-dimethyl-1 ,3-propanediol, and 1 ,5-pentanediol.
  • the at least one alcohol comprises an alcohol as described in US20150148569, hereby incorporated in its entirety by reference.
  • a second alcohol is provided and mixed in step (c), wherein the second alcohol is different from the at least one alcohol.
  • the second alcohol is a Ci-C 3 6 alcohol, preferably a C 6 -C 2 4 alcohol, more preferably a C 8 -Ci 8 alcohol.
  • the second alcohol is an aliphatic diol, preferably a biomass-derived aliphatic diol.
  • biomass-derived aliphatic diols may be selected from the group comprising: 1 ,3- propanediol, 1 ,4-butanediol, 1 ,2-butanediol, 1 ,3-butanediol, 2,3-butanediol, 2, 2-dimethyl-1 ,3- propanediol, and 1 ,5-pentanediol.
  • a second alcohol is provided and mixed in step (c), wherein the second alcohol is different from the at least one alcohol, and wherein the at least one alcohol and the second alcohol are selected from the group comprising: C 6 alcohol, C 8 alcohol, Ci o alcohol, Ci2 alcohol, C M alcohol, Ci 6 alcohol, Ci 8 alcohol, C 20 alcohol, C 22 alcohol, C 24 alcohol, and C 26 alcohol.
  • a second alcohol is provided and mixed in step (c), wherein the second alcohol is different from the at least one alcohol, and wherein the at least one alcohol and the second alcohol are selected from the group comprising: C 6 alcohol, C 8 alcohol, Ci o alcohol, and C 12 alcohol.
  • the at least one alcohol is a C 6 alcohol and the second alcohol is selected from the group comprising: C 8 alcohol, Ci o alcohol, and Ci 2 alcohol.
  • the at least one alcohol is a C 8 alcohol and the second alcohol is selected from the group comprising: C 6 alcohol, Ci o alcohol, and Ci 2 alcohol.
  • the at least one alcohol is a C 10 alcohol and the second alcohol is selected from the group comprising: C 6 alcohol, C 8 alcohol, and Ci 2 alcohol. In some embodiments, the at least one alcohol is a C 12 alcohol and the second alcohol is selected from the group comprising: C 6 alcohol, C 8 alcohol, and Ci o alcohol.
  • a second alcohol is provided and mixed in step (c), wherein the second alcohol is different from the at least one alcohol, and wherein the at least one alcohol and the second alcohol are selected from the group comprising: C 14 alcohol, C 16 alcohol, Ci 8 alcohol, C 20 alcohol, C 22 alcohol, C 24 alcohol, and C 26 alcohol.
  • the reaction temperature is at least 200* ⁇ and at most 280 * ⁇ .
  • step (a) a second alcohol is provided and mixed in step (c), wherein the second alcohol is different from the at least one alcohol, the at least one alcohol is selected from the group comprising: C 6 alcohol, C 8 alcohol, C 10 alcohol, and C 12 alcohol; and the second alcohol is selected from the group comprising: C alcohol, Ci 6 alcohol, Ci 8 alcohol, C 20 alcohol, C 22 alcohol, C 24 alcohol, and C 26 alcohol.
  • the resulting Guerbet alcohol may be solid, and the catalyst may be recovered by a hotfilter.
  • the at least one alcohol and the second alcohol are selected from the group comprising: 1 -octanol, n-stearyl alcohol, isostearyl alcohol, citronellol, n-hexanol, and n- decanol.
  • an aldehyde and/or a ketone is provided and mixed in step (c).
  • Preferred aldehydes and/or ketones are biomass-derived aldehydes and/or ketones.
  • the aldehyde and/or ketone is selected from the group comprising: hydroxylmethylfurfural, furfural, 2-ethylhexanal, decanal, dodecanal, tridecanal, isobutyraldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and C 3 -C 6 methyl ketones (such as acetone, butan-2-one, pentan-2-one, or hexan-2-one), or a combination thereof.
  • the hydrotalcite is a compound of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • n is an integer selected from 1 or 2;
  • M 2+ is selected from the group comprising Mg, Ni, Zn, Cu, Co, Fe, Pd Pt, and Ru; preferably Mg, Ni and Cu; preferably wherein M 2+ comprises all three of Mg, Ni and Cu;
  • M 3+ is selected from the group comprising Al, Cr, Mn, Co, Fe, and Ga; preferably Al;
  • M 2+ and/or M 3+ ions are isomorphously substituted by M + or M 4+ ions, preferably wherein M 4+ is selected from the group comprising Ge, Sn, and Pb.
  • the hydrotalcite is a compound of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • n is an integer selected from 1 or 2;
  • M 2+ is selected from the group comprising Mg, Ni and Cu; preferably wherein M 2+ comprises all three of Mg, Ni and Cu;
  • M 3+ is selected from the group comprising Al, Cr, Mn, Co, Fe, and Ga; preferably Al;
  • M 2+ and/or M 3+ ions are isomorphously substituted by M + or
  • M 4+ ions preferably wherein M 4+ is selected from the group comprising Ge, Sn, and Pb.
  • the hydrotalcite is a compound of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • n is an integer selected from 1 or 2;
  • M 2+ is selected from the group comprising Mg, Ni, Zn, Cu, Co, Fe, Pd Pt, and Ru; preferably
  • Mg, Ni and Cu preferably wherein M 2+ comprises all three of Mg, Ni and Cu;
  • M 3+ is Al
  • M 2+ and/or M 3+ ions are isomorphously substituted by M + or
  • M 4+ ions preferably wherein M 4+ is selected from the group comprising Ge, Sn, and Pb.
  • the hydrotalcite is a compound of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • n 2;
  • M 2+ is selected from the group comprising Mg, Ni, Zn, Cu, Co, Fe, Pd Pt, and Ru; preferably Mg, Ni and Cu; preferably wherein M 2+ comprises all three of Mg, Ni and Cu; M 3+ is selected from the group comprising Al, Cr, Mn, Co, Fe, and Ga; preferably Al;
  • A is C0 3 2" ;
  • M 2+ and/or M 3+ ions are isomorphously substituted by M + or M 4+ ions, preferably wherein M 4+ is selected from the group comprising Ge, Sn, and Pb.
  • the hydrotalcite is a compound of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • n is an integer selected from 1 or 2;
  • M 2+ is selected from the group comprising Mg, Ni and Cu; preferably wherein M 2+ comprises all three of Mg, Ni and Cu;
  • M 3+ is Al
  • M 2+ and/or M 3+ ions are isomorphously substituted by M + or
  • M 4+ ions preferably wherein M 4+ is selected from the group comprising Ge, Sn, and Pb.
  • the hydrotalcite is a compound of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • n 2;
  • M 2+ is selected from the group comprising Mg, Ni and Cu; preferably wherein M 2+ comprises all three of Mg, Ni and Cu;
  • M 3+ is selected from the group comprising Al, Cr, Mn, Co, Fe, and Ga; preferably Al;
  • A is C0 3 2" ;
  • M 2+ and/or M 3+ ions are isomorphously substituted by M + or M 4+ ions, preferably wherein M 4+ is selected from the group comprising Ge, Sn, and Pb.
  • the hydrotalcite is a compound of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • n 2;
  • M 2+ is selected from the group comprising Mg, Ni, Zn, Cu, Co, Fe, Pd Pt, and Ru; preferably Mg, Ni and Cu; preferably wherein M 2+ comprises all three of Mg, Ni and Cu;
  • A is C0 3 2" ;
  • the hydrotalcite is a compound of formula (I)
  • x is selected from 0.1 to 0.33;
  • n is an integer selected from 1 , 2, 3, 4 or 5;
  • n 2;
  • M 2+ is selected from the group comprising Mg, Ni and Cu; preferably wherein M 2+ comprises all three of Mg, Ni and Cu;
  • M 3+ is Al
  • A is C0 3 2" ;
  • M 2+ and/or M 3+ ions are isomorphously substituted by M + or M 4+ ions, preferably wherein M 4+ is selected from the group comprising Ge, Sn, and Pb.
  • the hydrotalcite has an M 2+ :M 3+ ratio of at least 2:1 ; preferably the hydrotalcite has an M 2+ :M 3+ ratio of at least 2:1 to at most 4:1 , for example about 3:1 .
  • M 2+ is selected from the group comprising Mg, Ni and Cu, preferably wherein M 2+ comprises all three of Mg, Ni and Cu; and the hydrotalcite has an M 2+ :M 3+ ratio of at least 2:1 ; preferably the hydrotalcite has an M 2+ :M 3+ ratio of at least 2:1 to at most 4:1 , for example about 3:1 .
  • M 3+ is Al, and the hydrotalcite has an M 2+ :M 3+ ratio of at least 2:1 ; preferably the hydrotalcite has an M 2+ :M 3+ ratio of at least 2:1 to at most 4:1 , for example about 3:1 .
  • M 2+ is selected from the group comprising Mg, Ni and Cu, preferably wherein M 2+ comprises all three of Mg, Ni and Cu; M 3+ is Al, and the hydrotalcite has an M 2+ :M 3+ ratio of at least 2:1 ; preferably the hydrotalcite has an M 2+ :M 3+ ratio of at least 2:1 to at most 4:1 , for example about 3:1 .
  • the copper-nickel catalyst comprises nickel in an atomic percent from 0.5% to 40% based on the total mole of metals present in said copper-nickel catalyst; more preferably an atomic percent of 0.5% to 20%; the most preferably an atomic percent of 0.5% to 10%; for example from 1 .5% to 10%; for example from 2.0% to 9.0%; for example from 2.5% to 7.5%.
  • the copper-nickel catalyst comprises copper in an atomic percent from 0.5% to 40% based on the total mole of metals present in said copper-nickel catalyst, more preferably an atomic percent of 0.5% to 20%; the most preferably an atomic percent of 0.5% to 10%; for example from 1 .5% to 10%; for example from 2.0% to 9.0%; for example from 2.5% to 7.5%.
  • the copper-nickel catalyst comprises magnesium in an atomic percent from 20% to 90% based on the total mole of metals present in said copper- nickel catalyst; preferably an atomic percent from 30% to 85%; preferably an atomic percent from 40% to 80%; for example from 50% to 75%; for example from 60% to 70%; for example about 65%.
  • the copper-nickel catalyst comprised in a hydrotalcite is subjected to a thermal treatment prior to step (b).
  • the copper-nickel catalyst is present in an amount of 0.05 to 5.0% by weight, based on the weight of said at least one alcohol, more preferably in an amount of 0.05 to 2.5% by weight; most preferably in an amount of 0.05 to 1 .0% by weight.
  • the Cu:Ni molar ratio in the copper-nickel catalyst is at least 0.1 :9.9 and at most 6.0:4.0, preferably at least 0.2:9.8 and at most 5.0:5.0, preferably at least 0.4:9.6 and at most 4.0:6.0, preferably at least 0.5:9.5 and at most 3.0:7.0, preferably at least 0.6:9.4 and at most 2.5:7.5, preferably at least 0.8:9.2 and at most 2.0:8.0, preferably at least 0.9:9.1 and at most 1 .5:8.5, preferably about 1 .0:9.0.
  • the Cu:Ni molar ratio in the copper-nickel catalyst is at most 2.0:8.0. In some preferred embodiments, the Cu:Ni molar ratio in the copper-nickel catalyst is at most 1 .5:8.5, preferably at most 1 .4:8.6, preferably at most 1 .3:8.7, preferably at most 1 .2:8.8, preferably at most 1 .1 :8.9, preferably about 1 .0:9.0.
  • the Cu:Ni molar ratio in the copper-nickel catalyst is at least 0.1 :9.9 and at most 1 .5:8.5, preferably at least 0.2:9.8 and at most 1 .4:8.6, preferably at least 0.4:9.6 and at most 1 .3:8.7, preferably at least 0.6:9.4 and at most 1 .2:8.8, preferably at least 0.8:9.2 and at most 1 .1 :8.9, preferably about 1 .0:9.0.
  • the Cu:Ni molar ratio in the copper-nickel catalyst is at most 1 .5:8.5, preferably at most 1 .4:8.6, preferably at most 1 .3:8.7, preferably at most 1 .2:8.8, preferably at most 1 .1 :8.9, preferably about 1 .0:9.0; and the copper-nickel catalyst comprises magnesium in an atomic percent from 20% to 90% based on the total mole of metals present in said copper-nickel catalyst; preferably an atomic percent from 30% to 85%.
  • the Cu:Ni molar ratio in the copper-nickel catalyst is at most 1 .5:8.5, preferably at most 1 .4:8.6, preferably at most 1 .3:8.7, preferably at most 1 .2:8.8, preferably at most 1 .1 :8.9, preferably about 1 .0:9.0; and the copper-nickel catalyst comprises magnesium in an atomic percent from 40% to 80%; for example from 50% to 75%; for example from 60% to 70%; for example about 65%.
  • the Cu:Ni molar ratio in the copper-nickel catalyst is at least 0.1 :9.9 and at most 1 .5:8.5, preferably at least 0.2:9.8 and at most 1 .4:8.6, preferably at least 0.4:9.6 and at most 1 .3:8.7, preferably at least 0.6:9.4 and at most 1 .2:8.8, preferably at least 0.8:9.2 and at most 1 .1 :8.9, preferably about 1 .0:9.0; and the copper-nickel catalyst comprises magnesium in an atomic percent from 20% to 90% based on the total mole of metals present in said copper-nickel catalyst; preferably an atomic percent from 30% to 85%.
  • the Cu:Ni molar ratio in the copper-nickel catalyst is at least 0.1 :9.9 and at most 1 .5:8.5, preferably at least 0.2:9.8 and at most 1 .4:8.6, preferably at least 0.4:9.6 and at most 1 .3:8.7, preferably at least 0.6:9.4 and at most 1 .2:8.8, preferably at least 0.8:9.2 and at most 1 .1 :8.9, preferably about 1 .0:9.0; and the copper-nickel catalyst comprises magnesium in an atomic percent from 40% to 80%; for example from 50% to 75%; for example from 60% to 70%; for example about 65%.
  • the alkaline catalyst is selected from the group comprising alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates and alkali earth metal carbonates, alkali metal phosphates, alkaline earth metal oxides, zeolites, alkyl amines or mixtures thereof.
  • the alkaline catalyst is selected from alkali metal hydroxides and alkaline earth metal hydroxides.
  • the alkaline catalyst is selected from the group comprising KOH, K phosphates, K carbonates, and 3-ethylamine.
  • the alkaline catalyst is KOH.
  • the alkaline catalyst is present in an amount of 0.5 to 5.0% by weight, based on the weight of said at least one alcohol; more preferably in an amount of 1 .0 to 4.0% by weight, more preferably in an amount of 1 .5 to 3.0% by weight.
  • the process according to the first aspect of the invention further comprises the step (e) of removing the water formed in step (d).
  • this step is performed by a Dean-Stark apparatus.
  • step (d) is performed at a temperature of 170 to 280 q C. In some preferred embodiments, step (d) is performed at a pressure of 1 to 50 bars. In some preferred embodiments, step (d) is performed at a temperature of 170 to 280* and at a pressure of 1 to 50 bars. In some preferred embodiments, step (d) is performed under inert atmosphere, preferably selected from the group comprising: N 2 , He, and Ar. In some preferred embodiments, step (d) is performed from 30 min up to 48 hours.
  • step (d) is performed after pre-reduction of the copper-nickel catalyst comprised in a hydrotalcite.
  • the pre-reduction may for example be performed in a high-pressure reaction system.
  • the catalyst may be suspended in alcohol, for example 1 - octanol and then transferred to the high-pressure reaction system.
  • the headspace may be purged several times, for example with N 2 .
  • the activation process may be performed at 240 Q C, during 6 h, under autogenously pressurized conditions (approx. 6 bars overpressure).
  • the high-pressure reaction system may then be cooled at room temperature, slowly degassed and finally, the activated catalyst may be transferred (still moistened by the 1 -octanol) to the atmospheric pressure reaction system in order to perform the Guerbet condensation reaction.
  • the copper- nickel catalyst comprised in a hydrotalcite is recovered after the process according to the first aspect, and then used for subsequent process according to the first aspect, or preferred embodiments thereof.
  • the copper-nickel catalyst comprised in a hydrotalcite is used in at least 2 subsequent processes according to the first aspect, or preferred embodiments thereof, for example in at least 3 subsequent processes, for example in at least 4 subsequent processes.
  • subsequent processes refers to processes that were performed after each other, without treatment of the catalyst, such as regeneration of the catalyst, between the processes.
  • the present invention relates to a Guerbet alcohol obtainable by the process according to the first aspect.
  • Preferred embodiments for the first aspect of the invention are also preferred embodiments for the second aspect of the invention.
  • the present invention relates to a Guerbet alcohol.
  • Preferred embodiments for the first aspect of the invention are also preferred embodiments for the third aspect of the invention.
  • the present invention relates to a Guerbet alcohol selected from the list comprising:
  • the Guerbet alcohol is selected from the list comprising: (A), (B), and (IC). In some embodiments, the Guerbet alcohol is selected from the list comprising: (A), (B), and (D). In some embodiments, the Guerbet alcohol is selected from the list comprising: (A), (C), and (D). In some embodiments, the Guerbet alcohol is selected from the list comprising: (B), (D), and (D).
  • the Guerbet alcohol is selected from the list comprising: (A) and (B). In some embodiments, the Guerbet alcohol is selected from the list comprising: (A) and (C). In some embodiments, the Guerbet alcohol is selected from the list comprising: (A) and (D). In some embodiments, the Guerbet alcohol is selected from the list comprising: (B) and (C). In some embodiments, the Guerbet alcohol is selected from the list comprising: (B) and (D). In some embodiments, the Guerbet alcohol is selected from the list comprising: (C) and (D).
  • the Guerbet alcohol is (A). In some embodiments, the Guerbet alcohol is (B). In some embodiments, the Guerbet alcohol is (C). In some embodiments, the Guerbet alcohol is (D).
  • the Guerbet alcohol has a viscosity of at most 100 Pa.s, wherein the viscosity is measured at 25 °C using Brookfield Viscometer according to the ASTM D 4889 standard.
  • the melting point is at least 40 ⁇ ⁇ and at most 50 ⁇ ⁇ , preferably at least 40 ⁇ ⁇ and at most 50 ⁇ ⁇ , preferably at least 41 °C and at most 49 ⁇ ⁇ , preferably at least 42 °C and at most 48 ⁇ ⁇ , preferably at least 43 °C and at most 47 ⁇ ⁇ .
  • the melt temperature is preferably measured using an IA9000 series Digital Melting Point Apparatus from Electrothermal to measure the capillary melting point.
  • the chemical structure of the Guerbet alcohol can be distinguished by using different analytical techniques, such as: mass spectrometry, 1 H and 13C NMR, elemental analysis (CHN), among others.
  • the present invention relates to the use of a copper-nickel catalyst comprised in a hydrotalcite to prepare a Guerbet alcohol.
  • Preferred embodiments for the first, second, or third aspect of the invention are also preferred embodiments for the fourth aspect of the invention.
  • the present invention relates to a copper-nickel catalyst comprised in a hydrotalcite.
  • Preferred embodiments for the first, second, third, or fourth aspect of the invention are also preferred embodiments for the fifth aspect of the invention. More particularly, preferred embodiments for the copper-nickel catalyst comprised in a hydrotalcite as described above for the process according to the first aspect are also preferred embodiments for the copper-nickel catalyst comprised in a hydrotalcite according to the fifth aspect.
  • the present invention relates to a process for preparing a copper- nickel catalyst comprised in a hydrotalcite.
  • Preferred embodiments for the first, second, third, fourth, or fifth aspect of the invention are also preferred embodiments for the sixth aspect of the invention.
  • the hydrotalcite is preferably prepared by co-precipitation under high supersaturation conditions, as reported elsewhere (J. Catal., 225, 2004, 316-326).
  • the process for preparing a copper-nickel catalyst comprised in a hydrotalcite preferably comprises the step of adding a solution (A) comprising metal salts to a solution (B) comprising precipitating agents, thereby obtaining solids.
  • solution (A) comprises from at least 0.2 M to at most 5 M metal salts, preferably from at least 0.5 M to at most 2.5 M, more preferably from at least 0.5 M to at most 1 .5 M.
  • Metal salts of solution (A) are preferably selected from metal nitrates, chlorides or sulphates; preferably metal nitrates.
  • solution (A) comprises from at least 0.2 M to at most 5 M metal nitrates, preferably from at least 0.5 M to at most 2.5 M, more preferably from at least 0.5 M to at most 1 .5 M.
  • the metal salts comprise Ni and Cu, and optionally comprise Mg and/or Al.
  • the metal nitrates comprise Ni and Cu, and optionally comprise Mg and/or Al.
  • the Cu:Ni molar ratio used in solution (A) is at least 0.1 :9.9 and at most 6.0:4.0; preferably at least 0.2:9.8 and at most 5.0:5.0; preferably at least 0.4:9.6 and at most 4.0:6.0; preferably at least 0.5:9.5 and at most 3.0:7.0; preferably at least 0.6:9.4 and at most 2.5:7.5; preferably at least 0.8:9.2 and at most 2.0:8.0; preferably at least 0.9:9.1 and at most 1 .5:8.5, preferably about 1 .0:9.0.
  • solution (B) comprises NaOH and/or Na 2 C0 3 .
  • solution (B) comprises from at least 1 .5 M to at most 5.5 M NaOH, preferably from at least 2.0 M to at most 3.0 M.
  • solution (B) comprises from at least 0.05 M to at most 1 .5 M Na 2 C0 3 , preferably from at least 0.15 M to at most 0.5 M.
  • solution (B) comprises from at least 1 .5 M to at most 5.5 M NaOH and from at least 0.05 M to at most 1 .5 M Na 2 C0 3 , preferably from at least 2.0 M to at most 3.0 M NaOH and from at least 0.15 M to at most 0.5 M Na 2 C0 3 .
  • solution (B) comprises KOH or NH 4 OH instead of NaOH, preferably at the concentrations as described above.
  • solution (B) comprises K 2 C0 3 instead of Na 2 C0 3 , preferably at the concentrations as described above.
  • solution B is kept in an ultrasonic bath during addition of solution (A).
  • An ultrasonic bath frequency of 20-400 kHz is used, preferably of 20-50 kHz.
  • the addition in ultrasonic bath is preferably performed at room temperature, or at elevated temperature.
  • Other agitation methods may comprise mechanical or magnetic stirring, or shaking.
  • an ageing step may be applied at room temperature or at elevated temperature (e.g. reflux at 50-80°C).
  • Other treatments that may be applied after addition are hydrothermal or microwave treatments.
  • the obtained solids are washed, for example by centrifugation or filtration.
  • the obtained solids are dried, for example using the following temperature profile: in 0.5-5 O/min to 100-120 ⁇ and keep at this temperature for 4-24 hrs.
  • the obtained solids are calcined, for example using the following temperature profile: in 0.5-3°C/min to 375-600 ⁇ ⁇ , preferably to 450-550 ⁇ ⁇ , and keep at this calcination temperature for 4-16 hrs.
  • the process for preparing a copper-nickel catalyst comprised in a hydrotalcite may comprise co-precipitation at low saturation conditions, sol-gel-synthesis, combustion synthesis, or an induced hydrolysis method.
  • a solution (A) containing the desired amount of 1 M solution of metal nitrates is mixed thoroughly to make a homogeneous solution. Then, solution (A) is added dropwise on a solution (B) containing precipitating agents. During the addition, solution (B) may be kept in ultrasonic bath, at room temperature. The obtained solids can be washed by centrifugation, and dried in an air oven. All materials may be calcined in air, in order to obtain the respective mixed oxides.
  • the present invention relates to a process for the preparation of a Guerbet acid, comprising the steps of:
  • the Guerbet alcohol is selected from the list comprising: (A) a C26-Guerbet alcohol resulting from the cross-condensation of 1 -octanol and n-stearyl alcohol, (B) a C36- Guerbet alcohol resulting from the self-condensation of isostearyl alcohol, (C) a C20-Guerbet alcohol resulting from the self-condensation of citronellol, (D) a C20-Guerbet alcohol resulting from the cross-condensation of n-hexanol and n-decanol, or any one of the specific combinations as described above.
  • the hydrotalcite was prepared by co-precipitation under high supersaturation conditions, as reported elsewhere (J. Catal., 225, 2004, 316-326).
  • a solution (A) containing the desired amount of 1 M solution of metal nitrates (Ni and/or Cu, Mg and Al, where the M(II)/AI molar ratio was 3.0, the (Cu+Ni)/(Cu+Ni+Mg+AI) ratio was 0.1 and the Mg/(Cu+Ni+Mg+AI) was 0.65) were mixed thoroughly to make a homogeneous solution.
  • solution (A) was added dropwise on a solution (B) containing the precipitating agents (i.e., NaOH and Na 2 C0 3 ; 2.2 M NaOH and 0.15 M Na 2 C0 3 ).
  • solution (B) was kept in ultrasonic bath, at room temperature.
  • the obtained solids were washed by centrifugation (until nitrates and sodium were totally absent in the washing liquids), and dried in an air oven at 100 °C for at least 12 h. All materials were calcined at 500 °C (with a heating rate of 2 Q C/min) for 4 h in air, in order to obtain the respective mixed oxides.
  • the calcined materials had the following formula:
  • Nio .2 Cuo. 6 Mg 5.2 AI 2 C>9 Ni(2.5)Cu(7.5);
  • Nio.4Cuo. 4 Mg 5.2 AI 2 C>9 Ni(5.0)Cu(5.0);
  • Nio.6Cuo .2 Mg 5.2 AI 2 C>9 Ni(7.5)Cu(2.5);
  • Nio.72Cuo.o8Mg 5.2 AI 2 C>9 Ni(9.0)Cu(1 .0).
  • the copper-nickel supported catalysts were synthesized by a wet impregnation method, ensuring a copper/nickel molar ratio of 2.5/7.5 and a total loading of copper and nickel metals in the whole catalyst of 12 wt%.
  • the appropriated amounts of Ni(N0 3 ) 2 .6H 2 0 and Cu(N0 3 ).3H 2 0 salts were dissolved in 150 mL of distilled water, in order to impregnate 4 g of support.
  • the desired support ⁇ - ⁇ 2 0 3 or MgO
  • was added to the cationic solution was kept under vigorous stirring during 2 h, at room temperature. Afterwards, the excess of solvent was removed at low pressure at 50 Q C, until having a totally dried solid.
  • the material was calcined in presence of air at 500 Q C, during 4h.
  • the temperature was elevated under N 2 flow (rate of 50 to 60 mL/min) up to the boiling point of the alcohol (195 9 C).
  • the time when the reaction mixture reached 190 to 200 QC (reflux) was designed as the point of initiation of the reaction.
  • the highest temperature allowed for the reaction to be conducted was 225 Q C.
  • the reaction was terminated after 8 hours.
  • the liquid reaction mixture was cooled and centrifuged to remove the copper- nickel catalyst and the precipitated soap-type products (potassium carboxylates).
  • the composition of the final reaction mixture was analysed by GC, as follow: 83.4% 2-hexyl-1 - decanol; 5.3% C16-non-Guerbet; 5.3% C24-products; 2.1 % 1 -octanol.
  • a purity of the final target product (2-hexyl-1 -decanol (C16-Guerbet alcohol)) was calculated considering the losses in the mass balance during the reaction (due to the formation of carboxylic salts and 1 -octanol evaporation) and subtracting the un reacted 1 -octanol. This value is a good agreement with the purity of the Cl 6-Guerbet estimated after distillation of the final reaction mixture.
  • Example 2 The reaction was carried out under the same conditions as described in Example 1 except that 0.4 g of a copper-nickel catalyst supported on alumina (the copper/nickel molar ratio was 2.5/7.5 and the total content of copper and nickel metal in the whole catalyst was 12% by weight) was used instead of copper-nickel catalyst comprised in a hydrotalcite. Conversion, selectivity, yields, and purity after 6 hours reaction are presented in Table 1 .
  • Example 2 The reaction was carried out under the same conditions as described in Example 1 except that 0.4 g of a copper-nickel catalyst supported on MgO (the copper/nickel molar ratio was 2.5/7.5 and the total content of copper and nickel metal in the whole catalyst was 12% by weight) was used instead of copper-nickel catalyst comprised in a hydrotalcite. Conversion, selectivity, yields, and purity after 6 hours reaction are presented in Table 1 .
  • the reaction was carried out under the same conditions as described in Example 1 except that the copper-nickel catalyst comprised in a hydrotalcite was pre-reduced just before to proceed with the condensation of 1 -octanol.
  • the pre-reduction process was performed in a high- pressure reaction system (PARR reactor, 160 imL stainless-steel vessel), as follow: typically, 0.4 g of catalyst were suspended in 100 g of 1 -octanol and then, transferred to the PARR reactor. After closing the reactor, the headspace was purged several times with N 2 .
  • the activation process was performed at 240 Q C, during 6 h, under autogenously pressurized conditions (approx. 6 bars overpressure).
  • the reactor was then cooled at room temperature, slowly degassed and finally, the activated catalyst was transferred (still moistened by the 1 - octanol) to the atmospheric pressure reaction system in order to perform the condensation reaction.
  • the composition of the final reaction mixture was characterized as follow: 87.3% 2- hexyl-1 -decanol; 3.8% C16-non-Guerbet alcohol products; 6.8% C24-products; 2.1 % 1 - octanol.
  • the pre-reduction of the copper-nickel catalyst decreases the concentration of C16- non-Guerbet alcohol products in the final reaction product in around 2%. Conversion, selectivity, yields, and purity after 6 hours reaction are presented in Table 2.
  • the reaction was carried out under the same conditions as described in Example 1 except that the composition of the copper-nickel catalyst comprised in a hydrotalcite carrier was modified (the Cu/Ni molar ratio was 1 .0/9.0; the total content of copper and nickel metals in the whole catalyst was kept at 13% by weight).
  • the composition of the final reaction mixture was characterized as follow: 94.5% 2-hexyl-1 -decanol; 1 .1 % C16-non-Guerbet alcohol products; 4.4% 1 -octanol.
  • the increment in the Ni-to-Cu ratio highly favoured the selectivity of the process and the pre-reduction step can be avoided. Conversion, selectivity, yields, purity after 6 hours reaction are presented in Table 2.
  • Example 3 The reaction was carried out under the same conditions as described in Example 1 .
  • the copper-nickel catalyst comprised in a hydrotalcite was removed by centrifugation and re-used as such up to 3 times (the recovered catalyst was mixed 40g of new 1 -octanol and 0.6 g of new granular potassium hydroxide). Conversion, selectivity and yields after 6 hours reaction are presented in Table 3.
  • Table 3 the re-use of the copper-nickel catalyst (example 4) promoted the selectivity of the process compared to example 1 .
  • Example 4 The reaction was carried out under the same conditions as described in Example 4 (catalyst recovery and reuse) except that 0.4 g of a copper-nickel catalyst supported on an alumina (the copper/nickel molar ratio was 2.5/7.5 and the total content of copper and nickel metal in the whole catalyst was 12% by weight) was used instead of copper-nickel catalyst comprised in a hydrotalcite. Conversion, selectivity, yields, and purity after 6 hours reaction are presented in Table 3.
  • Example 3 The reaction was carried out under the same conditions as described in Example 3 (catalyst recovery and reuse) except that 0.4 g of a copper-nickel catalyst supported on MgO (the copper/nickel molar ratio was 2.5/7.5 and the total content of copper and nickel metal in the whole catalyst was 12% by weight) was used instead of copper-nickel catalyst comprised in a hydrotalcite. Conversion, selectivity and yields after 6 hours reaction are presented in Table 3. In analogy to the comparative example 6, the copper-nickel catalyst supported on MgO shown a good stability during the first re-use, being it as good as the fresh catalyst (Table 1 , comparative example 4).
  • the effect of the copper/nickel molar ratio in the structure of the copper-nickel catalysts comprised in a hydrotalcite carrier was evaluated, going from the single Ni or Cu catalysts to the bimetallic ones.
  • the different Ni/Cu molar ratios analysed were selected as follow: 10/0; 2.5/7.5; 5.0/5.0; 7.5/2.5 and 0/10.
  • the reaction was carried out under the same conditions as described in Example 1 , using the five different copper-nickel catalysts described before. Conversion, selectivity, yields and purity after 6 hours reaction are presented in Table 5.
  • the increment in the content of Ni in the structure of the catalysts has a positive influence in the selectivity of the process, favouring the production of the target C16-Guerbet alcohol.
  • the presence of Cu is also important in order to keep a high conversion of the starting alcohol, which suggests a synergistic interaction between the copper and nickel during the catalytic reaction.
  • the copper is preferably involved in the first dehydrogenation step of the 1 -octanol, driving at the same time the generation of reduced nickel species, and then the reduced nickel can promote the final hydrogenation of the aldol condensation products.
  • the reaction was carried out under the same conditions as described in Example 1 except that the concentration of the copper-nickel catalyst comprised in a hydrotalcite carrier was 0.5 wt% instead of 1 .0 wt%. Conversion, selectivity, yields and purity are presented in Table 6 after 10 h reaction. Although the copper-nickel catalyst-to-KOH ratio is the same as presented in example 8, a lower yield to the C16-Guerbet alcohol and reaction rate were observed. Thus, 10 h reaction were needed in order to achieve the steady state conversion.
  • the reaction was carried out under the same conditions as described in Example 1 except that the vessel was charged with 40 g of a mixture of 1 -octanol :1 -decanol 50%:50% by weight.
  • the composition of the final reaction mixture was characterized as follow: 1 .3% 1 -octanol; 1 .0% 1 - decanol; 23.8% C16-Guerbet; 1 .2% C16-non-Guerbet; 44.9% C18-Guerbet; 2.2% C18-non- Guerbet; 20.7% C20-Guerbet; 1 .0% C20-non-Guerbet; 3.8% trimer-type molecules.
  • the selectivity and stability of the copper-nickel catalyst was as good as shown in Example 1 , achieving a total yield to Guerbet products of 89.4%.
  • the reaction was carried out in the same vessel as used in Example 1 except that 40 g of stearyl alcohol was used as starting alcohol.
  • On top of the reactor an open glass tube with quartz wool is placed.
  • the alcohol was first melted and then, after reaching 240 Q C, the base and then the copper-nickel catalyst were added. After this point, the reaction was performed during 2 to 12.5 hours. The water produced during the condensation was released through the top of the five-necked flask, where quartz wool was placed in order to avoid the losses of alcohol.
  • the final reaction product is hot-filtered at 120 Q C. This process allows the recovery of the final reaction product, while the catalyst and the biggest part of the soap-type products formed (Potassium stearate) remains on the glass filter.
  • the composition of the final reaction mixture (after 12.5 hours) was characterized by HT-GC-FID as follow: 2.0% stearyl alcohol; 70.4% dimers (C36- Guerbet product and C36-aldehydes); 20.5% trimers (C54) and 7.3% tetramers (C72).
  • the composition of the reaction mixtures after 12 hours and 24 hours at 240* ⁇ was characterized by HT-GC-FID and is given in Table 9.
  • the reaction was carried out as in Example 12 using 40 g of n-stearyl alcohol as starting alcohol and with an amount of 0.1 g of the copper-nickel catalyst (0.25 wt%) and 0.3 g of potassium hydroxide (0.75 wt%), except that a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 was used (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%).
  • the composition of the reaction mixtures after 12 hours and 24 hours at 240* ⁇ was characterized by HT-GC-FID and is given in Table 10.
  • Example 14 The reaction was carried out as in Example 13 using 40 g of n-stearyl alcohol as starting alcohol and 0.3 g of potassium hydroxide (0.75 wt%) and using a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), but with varying amounts of the copper-nickel catalyst, being 1 wt%, 0.5 wt% or 0.25 wt%.
  • the composition of the reaction mixtures after 12 hours at 240 * ⁇ was characterized by HT-GC-FID and is given in Table 1 1 .
  • Example 13 The reaction was carried out as in Example 13 using 40 g of n-stearyl alcohol as starting alcohol and 0.3 g of potassium hydroxide (0.75 wt%) and 0.1 g of a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), but applying vacuum (800 mbar) instead of working at atmospheric pressure.
  • vacuum 800 mbar
  • composition of the reaction mixture after 12 hours at 240* ⁇ was characterized by HT-GC- FID and is given in Table 13.
  • the reaction was carried out as in Example 13 using 40 g of n-stearyl alcohol as starting alcohol and 0.3 g of potassium hydroxide (0.75 wt%) and 0.1 g of a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), but with molecular sieve instead of quart wool in the glass vessel on top of the reactor.
  • the composition of the reaction mixture after 12 hours at 240* ⁇ was characterized by HT-GC- FID and is given in Table 14.
  • the reaction was carried out as in Example 13 using 40 g of n-stearyl alcohol as starting alcohol and 0.3 g of potassium hydroxide (0.75 wt%) and 0.1 g of copper-nickel catalyst a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), but at 250 ⁇ ⁇ instead of 240 ⁇ ⁇ for 12 hours.
  • composition of the reaction mixture after 12 hours at 250* ⁇ was characterized by HT-GC- FID and is given in Table 15.
  • the reaction was carried out as in Example 13 using 40 g of n-stearyl alcohol as starting alcohol and with 0.1 g of a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), but with varying amounts of potassium hydroxide, being 0.3 g (0.75 wt%), 0.4 g (1 .0 wt%) or 0.5 g (1 .25 wt%).
  • the reaction was carried out as in Example 13 using 40 g of n-stearyl alcohol as starting alcohol and using 0.5 g potassium hydroxide and 0.1 g of a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), but with re-use of the catalyst (up to 2 times) (the recovered catalyst was mixed with 40 g of new molten n-stearyl alcohol and 0.5 g of new granular potassium hydroxide).
  • composition of the reaction mixtures after 12 hours at 240* ⁇ was characterized by HT- GC-FID and is given in Table 17.
  • the reaction was carried out in the same vessel as used in Example 1 (for the self- condensation of 1 -octanol) except that a 1 :1 molar ratio of a middle-range alcohol (1 -octanol, C8-OH) and a long-range alcohol (n-stearyl alcohol, n-C18-OH) was used (respectively 15.0 g C8-OH and 31 .1 g C18-OH).
  • 0.82 g of potassium hydroxide is used providing a ratio of total moles of alcohols to moles of KOH of 15.8.
  • 0.2 g of a copper-nickel catalyst was used with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), and nitrogen flow is added in the head space.
  • Reaction time was 12 hours and the reaction was performed at 225 q C.
  • a creamy product was obtained (see FIG. 2), with a melting point of 38-44 ⁇ 0.
  • This Guerbet alcohol product is expected to be a mixture of C16-Guerbet, C26-Guerbet and C36 Guerbet.
  • FIG. 2 illustrates a product obtained from a 1 :1 molar ratio of n-C8-OH and n-C18-OH as reacted in example 20.
  • the reaction was carried out in the same vessel as used in Example 1 but the vessel was charged with 40 g of isostearyl alcohol (iso-C18-OH).
  • the reaction conditions used were: 0.25 wt% of a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), 1 .25 wt% potassium hydroxide.
  • Reaction time was 12 hours and the reaction was performed at 240 °C. A gel-type product was obtained (see FIG.
  • FIG. 3 illustrates the Guerbet product from example 22 from the self-condensation of isostearyl alcohol.
  • the reaction was carried out in the same vessel as used in Example 1 but the vessel was charged with 40 g of citronellol (C20-alcohol) (a-citronellol: 0,35 %, ⁇ -citronellol: 97,35%).
  • the reaction conditions used were: 1 wt% copper-nickel catalyst (the Cu/Ni molar ratio was 1 .0/9.0), 3 wt% potassium hydroxide.
  • Reaction time was 1 hour 15 min and the reaction was performed at 250 * ⁇ .
  • the composition of the reaction mixtures was analysed by GC and is shown in Table 18. A new Guerbet alcohol, the C20-Guerbet alcohol resulting from the self- condensation of citronellol, was formed.
  • reaction was carried out as in example 23, except that the reaction temperature was elevated to 260 °C.
  • the reaction was carried out as in example 23, except that 1 wt% of a copper-nickel catalyst with Cu/Ni molar ratio of 2.5/7.5 was used.
  • the composition of the reaction mixtures was analysed by GC and is shown in Table 18. A new Guerbet alcohol, the C20-Guerbet alcohol resulting from the self-condensation of citronellol, was formed.
  • the reaction was carried out in the same vessel as used in Example 1 but the vessel was charged with 40 g of a 1 :1 molar ratio n-hexanol and n-decanol.
  • the Dean-Stark configuration was filled with 50:50 molar ratio n-hexanol :n-decanol mixture
  • the reaction conditions used were: 1 wt% copper-nickel catalyst (the Cu/Ni molar ratio was 2.5/7.5), 3 wt% potassium hydroxide. Reaction time was 6 hour and the reaction was performed at 255 * ⁇ .
  • the GC data are shown in Table 19 and 19b.
  • FIG. 4 A GC chromatogram is shown in FIG. 4.
  • FIG. 4 illustrates a chromatogram of the products obtained in example 26. Two C16 Guerbet (GB) products have been formed.
  • the reaction was carried out in the same vessel as used in Example 26, except that the catalyst used was 1 wt% of a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%).
  • the GC data of example 27 are shown in Table 19 and 19b.
  • Cross coupling reactions were performed using 1 :1 molar ratio combinations of the starting alcohol C6-OH with C8-OH, C10-OH or C12-OH.
  • the reaction conditions used were: 1 wt% of a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), 3 wt% potassium hydroxide.
  • the reaction was performed at 225 ⁇ ⁇ , 240 ⁇ ⁇ or 250 ⁇ ⁇ .
  • the data obtained for the cross-condensation of C6-OH with C8-OH at 225 ⁇ ⁇ are given in Table 20.
  • Cross coupling reactions were performed using 1 :1 molar ratio combinations of the starting alcohol C8-OH with C10-OH or C12-OH.
  • the reaction conditions used were: 1 wt% a copper- nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), 3 wt% potassium hydroxide.
  • Reaction time was 2 and 4 hours and the reaction was performed at 225 °C, 240 °C or 250 °C.
  • Cross coupling reactions were performed using 1 :1 molar ratio combinations of the starting alcohol C10-OH with C12-OH.
  • the reaction conditions used were: 1 wt% copper-nickel catalyst a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), 3 wt% potassium hydroxide.
  • Reaction time was 2 and 4 hours and the reaction was performed at 225°C, 240°C or 250 ⁇ ⁇ .
  • Self-condensation reaction was performed using C22-OH (actually mixture C18:C20:C22).
  • Standard conditions for the C22 self-condensation were a reaction temperature of 240 * ⁇ ; 0,25 wt% of a copper-nickel catalyst with Cu/Ni molar ratio of 1 .0/9.0 (the theoretical molar ratio of moles (Cu+Ni) to total moles of metals (Cu+Ni+Mg+AI) was 13% and the molar ratio of moles Mg to total moles of metals was 65%), and 1 ,25 wt% KOH.

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Abstract

L'invention concerne un procédé de préparation d'un alcool de Guerbet, comprenant les étapes de: (a) fourniture d'au moins un alcool, le(s)dit(s) alcool(s) comprenant un atome de carbone portant au moins un atome d'hydrogène adjacent au groupe hydroxyle; (b) fourniture d'une composition catalytique, ladite composition catalytique comprenant un catalyseur alcalin et un catalyseur cuivre-nickel compris dans une hydrotalcite; (c) mélange de l'alcool a) avec une composition catalytique (b), ce qui permet d'obtenir un mélange; et d) chauffage dudit mélange; ce qui permet d'obtenir un alcool de Guerbet.
PCT/EP2016/079565 2015-12-02 2016-12-02 Réaction de condensation de guerbet WO2017093473A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107983328A (zh) * 2017-12-07 2018-05-04 中国科学院山西煤炭化学研究所 一种醇醇缩合反应的催化剂及其制备方法和应用
CN114558581A (zh) * 2022-03-08 2022-05-31 中国科学院青岛生物能源与过程研究所 一种Cu/Cr基催化剂及其制备方法和用于制备1,2-戊二醇的用途
WO2023187226A1 (fr) 2022-04-02 2023-10-05 Biosynthis Procede de preparation d'un melange volatil d'alcanes et de composition cosmetique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0089569A1 (fr) * 1982-03-18 1983-09-28 Kao Corporation Procédé de préparation d'alcools de Guerbet
WO1994014700A1 (fr) * 1992-12-21 1994-07-07 Amoco Corporation Procede de preparation de gaz synthetique a l'aide de catalyseurs contenant du nickel
WO1999003779A1 (fr) * 1997-07-21 1999-01-28 Bp Amoco Corporation Procede de reformage d'hydrocarbures et catalyseur et precurseur de catalyseur associes
WO2009112856A1 (fr) * 2008-03-12 2009-09-17 Johnson Matthey Plc Préparation de matières de désulfuration
US20150148569A1 (en) 2012-06-29 2015-05-28 Abengoa Bioenergia Nuevas Technolgias, S.A. Method for obtaining high alcohols
EP2913319A1 (fr) * 2014-02-28 2015-09-02 Arkema France Synthèse d'alcools de Guerbet

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0089569A1 (fr) * 1982-03-18 1983-09-28 Kao Corporation Procédé de préparation d'alcools de Guerbet
WO1994014700A1 (fr) * 1992-12-21 1994-07-07 Amoco Corporation Procede de preparation de gaz synthetique a l'aide de catalyseurs contenant du nickel
WO1999003779A1 (fr) * 1997-07-21 1999-01-28 Bp Amoco Corporation Procede de reformage d'hydrocarbures et catalyseur et precurseur de catalyseur associes
WO2009112856A1 (fr) * 2008-03-12 2009-09-17 Johnson Matthey Plc Préparation de matières de désulfuration
US20150148569A1 (en) 2012-06-29 2015-05-28 Abengoa Bioenergia Nuevas Technolgias, S.A. Method for obtaining high alcohols
EP2913319A1 (fr) * 2014-02-28 2015-09-02 Arkema France Synthèse d'alcools de Guerbet

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. CATAL., vol. 225, 2004, pages 316 - 326

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107983328A (zh) * 2017-12-07 2018-05-04 中国科学院山西煤炭化学研究所 一种醇醇缩合反应的催化剂及其制备方法和应用
CN114558581A (zh) * 2022-03-08 2022-05-31 中国科学院青岛生物能源与过程研究所 一种Cu/Cr基催化剂及其制备方法和用于制备1,2-戊二醇的用途
WO2023187226A1 (fr) 2022-04-02 2023-10-05 Biosynthis Procede de preparation d'un melange volatil d'alcanes et de composition cosmetique
FR3135395A1 (fr) 2022-04-02 2023-11-17 Biosynthis Procede de preparation d’un melange volatil d’alcanes et de composition cosmetique

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