WO2017066901A1 - Procédé d'oxydation d'alcools - Google Patents

Procédé d'oxydation d'alcools Download PDF

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Publication number
WO2017066901A1
WO2017066901A1 PCT/CN2015/092157 CN2015092157W WO2017066901A1 WO 2017066901 A1 WO2017066901 A1 WO 2017066901A1 CN 2015092157 W CN2015092157 W CN 2015092157W WO 2017066901 A1 WO2017066901 A1 WO 2017066901A1
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WIPO (PCT)
Prior art keywords
metal
formula
gold
alcohol
palladium
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PCT/CN2015/092157
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English (en)
Inventor
Armin T. Liebens
Wenjuan ZHOU
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Rhodia Operations
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Priority to PCT/CN2015/092157 priority Critical patent/WO2017066901A1/fr
Publication of WO2017066901A1 publication Critical patent/WO2017066901A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups

Definitions

  • This invention relates to a process for oxidation of alcohols using peroxide as oxidant and in the presence of a noble metal catalyst.
  • ether carboxylic acids and/or their salts may be produced by oxidation of their corresponding ether alcohols, usually with the help of a noble metal catalyst.
  • These publications include JP 50-96516 (KAO CORPORATION) 7/31/1975, which discloses a process for preparing carboxylic acid salts by liquid phase dehydrogenative oxidation of ether alcohols in the presence of a palladium or platinum catalyst. Disadvantageously, this process needed a high reaction temperature of 100-270°C, which can easily degrade the ether link in the desired product.
  • EP 0018681 B SHELL INTERNATIONALE RESEARCH 4/17/1980
  • EP 0039111 A SHELL INTERNATIONALE RESEARCH 4/13/1981 described an essentially liquid-phase reaction to oxidize alkoxyalkanol to its corresponding carboxylic acid, using hydrogen peroxide or t-butyl peroxide in the presence of palladium catalyst.
  • the desirable effect of heterogeneous palladium catalyst relies on the combined use with a tert-butyl alcohol solvent, otherwise the reaction mixture solidified halfway through the reaction and the ether alcohol was only half converted. This particular solvent dependence of this process is disadvantageous, especially considering that tert-butyl alcohol is known as an instable solvent and not easy to handle in large quantity.
  • CN 101905158 B (CHINA RESEARCH INSTITUTE OF DAILY CHEMICAL INDUSTRY) 12/8/2010 proposed a modified liquid-phase reaction to oxidize alkoxyalkanol, using hydrogen peroxide as oxidant and a carbon-supported palladium catalyst containing at least one main group metal of Sn or Bi. While this modification on catalyst has avoided the solidification problem of the reaction mixture, the final yield of the desired ether carboxylic acid is fairly low (roughly 50% or lower according to the Examples) .
  • the present invention relates to a process of oxidizing an alcohol of formula
  • R represents a saturated or unsaturated, linear, branched or cyclic C 3 -C 50 hydrocarbon group which is optionally substituted with a heteroatom, notably for the production of its corresponding carbonyl compounds
  • oxidation is performed in a liquid phase using a peroxide as oxidant and in the presence of a base compound and a catalyst comprising at least: (i) gold metal, (ii) platinum metal and/or palladium metal, the gold metal/ (platinum metal and/or palladium metal) molar ratio is comprised between 2: 1 and 50: 1 with the exclusion of 3: 1, 10: 1 and 20: 1, and (iii) a CeO 2 , TiO 2 and/or carbon support.
  • the special combination of peroxide oxidant, a base compound and the catalyst as above detailed can effectively facilitate the desired oxidation of an alcohol of formula (I) .
  • said special combination makes it possible to perform the desired alcohol oxidation reaction in a liquid phase and thus avoids most problems encountered by gas-liquid phase operations, meanwhile providing an extremely mild, low temperature process. Furthermore, it minimizes degradation products, waste organic solvents or hardly-recyclable catalysts, and provides high conversion of the alcohol reactant and oxidant, with high selectivity and yield of the end product.
  • the catalyst mentioned above show excellent catalytic performance over any other noble metal catalyst applied to a support.
  • the catalyst could be recycled for more times than normal noble metal without loss of catalytic activity.
  • the process of the present invention is particularly suited to the detergent range alkoxyalkanols and fatty acid monoethanolamide.
  • the “alcohol” as used herein includes primary alcohols and secondary alcohols.
  • the reaction encompassed in the "process of oxidizing an alcohol” in the present invention includes a process of obtaining carboxylic acid from a primary alcohol, a process of obtaining aldehyde from a primary alcohol, and a process of obtaining ketone from a secondary alcohol.
  • hydrocarbon group refers to a group which contains carbon and hydrogen bonds.
  • a hydrocarbon group may be linear, branched, or cyclic, and may contain a heteroatom such as oxygen, nitrogen, sulfur, halogen, etc.
  • the alcohol subjected to oxidation according to the process of the present invention is an ethoxylated fatty alcohol of formula (II)
  • R 1 represents an alkyl radical having 1 to 22 carbon atoms or a monounsaturated or polyunsaturated linear or branched alkenyl radical having 2 to 22 carbon atoms, optionally comprising at least a substituent and/or a heteroatom such as N or O;
  • R 2 represents a hydrogen atom or a methyl group or a mixture thereof in the individual molecule; and n has an average number between 2 and 20.
  • alkyl refers to saturated aliphatic groups, including linear, branched and/or cyclic groups; the term “alkyenyl” refers to unsaturated aliphatic groups having at least one double bond, including linear, branched and/or cyclic groups having at least one double bond,
  • R 1 in formula (II) preferably represents an alkyl group having from 3 to 22, more preferably from 8 to 20 and most preferably from 10 to 16 carbon atoms. Particular preference for R 1 is given to methyl, butyl and lauryl, of which lauryl is further preferred.
  • the R 1 group can be an alkyl group substituted with any substituent which does not interfere with the oxidation of the hydroxyl group.
  • R 1 in formula (II) may be an alkyl group substituted with at least one substituent selected from a group consisting of ⁇ OR 3 , ⁇ CH 3 , ⁇ CH 2 CH 3 , -COOH, -CONH 2 and -COOR 3 , wherein R 3 represents an alkyl or aryl group.
  • exemplary ethoxylated fatty alcohol of formula (II) may be selected from a group consisting of straight ethoxylates, straight propoxylates and mixed ethoxylatepropoxylate, all being detergent range ethoxylate alcohols.
  • detergent range ethoxylate alcohols are available with an average of 3, 7, 9 and 12 ethoxylate units per molecule. Preparation of these detergent range ethoxylate alcohols are well known in the art.
  • n is an integer of from 4 to 12, more preferably from 4 to 9 in the individual molecule of formula (II) .
  • the invention provides a process for producing compounds of formula (III)
  • oxidation is performed in a liquid phase using a peroxide as oxidant and in the presence of a base compound and a catalyst comprising at least: (i) gold metal, (ii) platinum metal and/or palladium metal, the gold metal/ (platinum metal and/or palladium metal) molar ratio is comprised between 2: 1 and 50: 1 with the exclusion of 3: 1, 10: 1 and 20: 1, and (iii) a CeO 2 , TiO 2 and/or carbon support.
  • the counterion B is an alkali metal cation selected from a group consisting of Li, Na, K, Rb and Cs, of which Na and K are particularly preferred.
  • the free ether carboxylic acids i.e. protonated carboxylic acids of compounds of formula (III)
  • the resulting alkali metal salts of formula (III) are reacted with acids.
  • Preferred acids are hydrochloric acid and sulphuric acid.
  • the fatty alcohol subjected to oxidation according to the process of the present invention is a fatty acid monoethanolamide of formula (IV)
  • R’ represents a saturated, linear or branched alkyl radical having from 1 to 21 carbon atoms or a monounsaturated or polyunsaturated linear or branched alkenyl radical having from 2 to 21 carbon atoms.
  • R’ is a saturated linear or branched alkyl radical having from 7 to 17 carbon atoms or a monounsaturated or polyunsaturated linear or branched alkenyl radical having from 7 to 17 carbon atoms, and is more preferably a saturated linear alkyl radical having from 9 to 14 carbon atoms.
  • fatty acid monoethanolamide of formula (IV) As preferred examples of fatty acid monoethanolamide of formula (IV) , mentions can be made for a group consisting of lauric acid monoethanolamide, myristic acid monoethanolamide, caprylic acid monoethanolamide, capric acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide and isostearic acid monoethanolamide, among which lauric acid monoethanolamide is particularly preferred.
  • the invention provides a process for producing compounds of formula (V)
  • the free ether acylglycine acids i.e. protonated carboxylic acids of compounds of formula (V)
  • the resulting alkali metal salts of formula (V) are reacted with acids.
  • Preferred acids are hydrochloric acid and sulphuric acid.
  • the alcohol subjected to oxidation according to the process of the present invention is selected from a group consisting of hexanol, octanol, 1-decanol, 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, 1-octadecenol and mixtures thereof.
  • the base compound used in the process of the present invention may be selected from carbonates, hydroxides and oxides, and is preferably selected from hydroxides of formula BOH with B as defined above.
  • the peroxide used in the process of the present invention is not particularly limited, and may be selected from a group consisting of: hydroperoxides, such as hydrogen peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide; diacyl peroxides, such as benzoyl peroxide, lauroyl peroxide, and the like; and ketone peroxides, such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, and the like. Particular preference is given to hydrogen peroxide and tert-butyl hydroperoxide, of which hydrogen peroxide is further preferred.
  • hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide
  • diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and the like
  • ketone peroxides such as
  • hydrogen peroxide solution may be used.
  • concentration of the hydrogen peroxide solution used is 5 to 60 wt. %, preferably 8 to 45 wt. % and more preferably 30 to 40 wt. %.
  • the upperamount of use of peroxide in the process of the invention is not particularly limited.
  • a typical amount of use of peroxide is 0.1 mol to 15 mol equivalent, preferably 0.5 mol to 10 mol equivalent, more preferably 2 mol to 8 mol equivalent of the alcohol reactant.
  • the process of the invention is preferably carried out in water.
  • the gold metal, platinum metal and/or palladium metal contained in catalyst used in the process of the invention are particularly pure metal.
  • the gold particles used to produce the catalyst have an average particles size in the nanometer range, preferablyfrom 1 to 50 nm and more preferably from 2 to 10 nm.
  • the platinum metal and/or palladium metal used to produce the catalyst have an average particles size in the nanometer range, preferablyfrom 0.1 to 30 nm and more preferably from 0.5 to 10 nm.
  • the bimetallic Au-Pt and/or Au-Pd nonaparticles in the catalyst have average particles size in nanometer range, preferably from 0.1 to 15 nm.
  • the particle size can be measured, e.g., by transmission electron microscopy or light scattering methods known in the art.
  • the catalyst above mentioned is a heterogeneous catalyst.
  • the metal (s) of catalyst is applied to a support.
  • Said supports are CeO 2 , TiO 2 and/or carbon supports.
  • Such supported catalyst can be produced by known methods such as adsorption, deposition-precipitation, or incipientwetness impregnation approach.
  • the support particles may have a specific surface area comprises between 5 to 1300 m 2 /g.
  • surface area of CeO 2 ranges from 10 to 250 m 2 /g.
  • surface area of TiO 2 ranges from 10-1000 m 2 /g.
  • surface area of carbon ranges from 150-1200 m 2 /g.
  • the supported catalyst may comprise 0.5 to 10 wt. % of gold metal and platinum metal and/or palladium metal, preferably 1 to 5 wt. % of gold metal and platinum metal and/or palladium metal, based on the total weight of the supported catalyst.
  • the gold metal/ (platinum metal and/or palladium metal) molar ratio is comprised between 2: 1 and 9.9: 1.
  • the gold metal/ (platinum metal and/or palladium metal) molar ratio is comprised between 10.1: 1 and 19.9: 1.
  • the gold metal/ (platinum metal and/or palladium metal) molar ratio is comprised between 20.1: 1 and 50: 1.
  • the gold metal/ (platinum metal and/or palladium metal) molar ratio is comprised between 3.5: 1 and 9.5: 1, more preferably comprised between 4: 1 and 9: 1, particularly comprised between 4: 1 and 8: 1, specifically equal to 4, 5, 6, 7 or 8 or any possible range comprised between these values.
  • At least part of the supported catalyst used in the process of the invention may be recycled. More preferably, all the supported catalyst is recycled to a fresh reaction solution.
  • the recycled catalyst may be directly reused after physical separation from reaction solution.
  • the oxidation reaction according to the process of the invention is usually carried out at a temperature between 30°C and 100°C, preferably between 40°C and 90°C.
  • the reaction pressure is generally atmospheric pressure, although higher pressure is also possible.
  • the reaction time is generally between 1 hour and 20 hours, preferably between 5 hours and 15 hours.
  • the pH value in the liquid phase at the start of the oxidation reaction is preferably set between 9 and 15, more preferably between 10 and 14.
  • a uniform pH value is maintained throughout the reaction by adding a base in a given range.
  • the reaction can be allowed to proceed by successively adding the peroxide oxidant and the catalyst to a solution containing the alcohol and the base compound, or by successively adding the peroxide and the base compound to a mixture containing the fatty alcohol and the catalyst.
  • the reaction can also be allowed to proceed conveniently by successively adding the peroxide oxidant to a mixture containing the alcohol, the base compound and the catalyst; or by mixing the peroxide, the alcohol, the base compound and the catalyst in advance to prepare a mixed reagent.
  • This comparative example is performed in the same way of Example 1.
  • the molar ratio of different catalysts to alcohol is same.
  • 1%Au/Al 2 O 3 , 1%Au/TiO 2 and 1%Au/ZnO are from Stream.
  • 5%Pt/C, 5%Ru/C, 5%Ru-Bi/C and 5%Pt-Bi/C are from Johnson Matthey.
  • the rest catalysts are prepared as follows.
  • the Au/CeO 2 solid thus produced was filtered and washed with several liters of deionized water until no traces of chlorides were detected by the AgNO 3 test, and then freeze-dried under vacuum for 24 hours.
  • the dried Au/CeO 2 solid was analysed by chemical analysis and transition electronic microscopy (TEM) , to determine the content and size of gold nanoparticles on the CeO 2 support (Au: 0.95 wt. %) on the CeO 2 support.
  • TEM transition electronic microscopy
  • the Pt/TiO 2 solid thus produced was filtered and washed with several liters of deionized water until no traces of chlorides were detected by the AgNO 3 test, and then freeze-dried under vacuum for 24 hours.
  • the dried Pt/TiO 2 solid was analyzed by chemical analysis and transition electronic microscopy (TEM) , to determine the content and size of gold and platinum nanoparticles on the TiO 2 support (Pt: 0.98 wt. %) on the TiO 2 support.
  • TEM transition electronic microscopy
  • the Pt/CeO 2 solid thus produced was filtered and washed with several liters of deionized water until no traces of chlorides were detected by the AgNO 3 test, and then freeze-dried under vacuum for 24 hours.
  • the dried Pt/CeO 2 solid was analyzed by chemical analysis and transition electronic microscopy (TEM) , to determine the content and size of platinum nanoparticles on the CeO 2 support (Pt: 1wt. %) on the CeO 2 support.
  • TEM transition electronic microscopy
  • Catalyst AECA6 yield % TON AECA6 1%Au/Al 2 O 3 81 346 1%Au/TiO 2 80 321 1%Au/ZnO 74 225 0.95%Au/CeO 2 52 249 1%Pt/CeO 2 3.0 60 5%Pt/C 14 235 0.98Pt/TiO 2 56.4 349 5%Pt-Bi/C 67.9 290 1%Au0.1%Pd/CeO 2 74.7 319 0.9%Au0.1%Pt/CeO 2 77 367 1.1%Au0.11%Pt/TiO 2 89 350 5%Ru/C 3.4 14 5%Ru-Bi/C 4.0 15
  • This comparative example is performed in the same way of Example 1.
  • the molar ratio of different catalysts to alcohol is same.
  • This comparative example relates to catalytic recyclability test. It shows catalyst of the present invention could be recycled for more times than other noble metals without loss of catalytic activity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

La présente invention concerne un procédé d'oxydation d'un alcool de formule ROH (I), dans laquelle R représente un groupe hydrocarboné saturé ou insaturé, linéaire, ramifié ou cyclique en C3-C50, qui est éventuellement substitué par un hétéroatome, caractérisé en ce que l'oxydation est effectuée dans une phase liquide à l'aide d'un peroxyde utilisé comme oxydant et en présence d'un composé basique et d'un catalyseur comprenant au moins : (i) de l'or métal, (ii) du platine métal et/ou du palladium métal, et (iii) un support à base de CeO2, de TiO2 et/ou de carbone.
PCT/CN2015/092157 2015-10-19 2015-10-19 Procédé d'oxydation d'alcools WO2017066901A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113173863A (zh) * 2021-03-16 2021-07-27 张家港格瑞特化学有限公司 一种脂肪酰基氨基酸的制备方法
CN114899422A (zh) * 2022-04-26 2022-08-12 湘潭大学 一种负载型双金属催化剂及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5801276A (en) * 1996-08-16 1998-09-01 Bayer Aktiengesellschaft Process for the preparation of hydroxypivalic acid
WO2007087048A1 (fr) * 2006-01-25 2007-08-02 Lyondell Chemical Technology, L.P. Procédé d'oxydation d'une oléfine
WO2015103350A1 (fr) * 2013-12-31 2015-07-09 Bp Corporation North America Inc. Procédé d'oxydation pour la préparation d'acides carboxyliques purifiés

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5801276A (en) * 1996-08-16 1998-09-01 Bayer Aktiengesellschaft Process for the preparation of hydroxypivalic acid
WO2007087048A1 (fr) * 2006-01-25 2007-08-02 Lyondell Chemical Technology, L.P. Procédé d'oxydation d'une oléfine
WO2015103350A1 (fr) * 2013-12-31 2015-07-09 Bp Corporation North America Inc. Procédé d'oxydation pour la préparation d'acides carboxyliques purifiés

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113173863A (zh) * 2021-03-16 2021-07-27 张家港格瑞特化学有限公司 一种脂肪酰基氨基酸的制备方法
CN114899422A (zh) * 2022-04-26 2022-08-12 湘潭大学 一种负载型双金属催化剂及其制备方法和应用
CN114899422B (zh) * 2022-04-26 2024-04-05 湘潭大学 一种负载型双金属催化剂及其制备方法和应用

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