WO2016026132A1 - Process for oxidation of alcohols - Google Patents

Process for oxidation of alcohols Download PDF

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Publication number
WO2016026132A1
WO2016026132A1 PCT/CN2014/084984 CN2014084984W WO2016026132A1 WO 2016026132 A1 WO2016026132 A1 WO 2016026132A1 CN 2014084984 W CN2014084984 W CN 2014084984W WO 2016026132 A1 WO2016026132 A1 WO 2016026132A1
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Prior art keywords
catalyst
group
formula
alcohol
gold
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PCT/CN2014/084984
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French (fr)
Inventor
Wenjuan ZHOU
Wenhao FANG
Floryan De Campo
Pascal Metivier
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Rhodia Operations
Centre National De La Recherche Scientifique
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Priority to PCT/CN2014/084984 priority Critical patent/WO2016026132A1/en
Publication of WO2016026132A1 publication Critical patent/WO2016026132A1/en

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    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J37/0201—Impregnation
    • 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
    • B01J37/12—Oxidising
    • 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
    • B01J37/16—Reducing
    • 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
    • B01J37/32—Freeze drying, i.e. lyophilisation
    • 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
    • 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
    • C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion

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 /-butyl peroxide in the presence of palladium catalyst.
  • 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
  • R represents a saturated or unsaturated, linear, branched or cyclic C3-C50 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 [Catalyst (C)] selected from a group consisting of: (i) a gold- containing catalyst [Catalyst (C1 )]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second element selected from tin, bismuth, selenium, tellurium and antimony.
  • a catalyst selected from a group consisting of: (i) a gold- containing catalyst [Catalyst (C1 )]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second
  • peroxide oxidant a base compound and the selected Catalyst (C) 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.
  • 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.
  • 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
  • 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*, -CH 3 , -CH 2 CH 3 , -COOH, -CONH 2 and -COOR 3 , wherein R 3 represents an alkyl or aryl group.
  • the R 2 group on an individual molecule can be hydrogen, methyl or mixtures thereof.
  • 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).
  • process of the present invention is an ethoxylated fatty alcohol 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 [Catalyst (C)] selected from a group consisting of: (i) a gold- containing catalyst [Catalyst (C1 )]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second element selected from tin, bismuth, selenium, tellurium and antimony.
  • a catalyst selected from a group consisting of: (i) a gold- containing catalyst [Catalyst (C1 )]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second
  • 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
  • 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) mentions can be made for a group consisting of lauric acid
  • amides based on chain fractions or mixtures of these fatty acid monoethanolamides preferably coconut fatty acid monoethanolamide.
  • the invention provides a process for producing compounds of formula (V)
  • oxidation is performed in a liquid phase using a peroxide as oxidant and in the presence of a base compound and a catalyst [Catalyst (C)] selected from a group consisting of: (i) a gold- containing catalyst [Catalyst (C1 )]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second element selected from tin, bismuth, selenium, tellurium and antimony.
  • a catalyst selected from a group consisting of: (i) a gold- containing catalyst [Catalyst (C1 )]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second
  • 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.
  • 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
  • hydroperoxides such as hydrogen peroxide, te -butyl hydroperoxide, and cumenehydroperoxide
  • diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and the like
  • ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, and the like.
  • 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 te -butyl hydroperoxide, of which hydrogen peroxide is further preferred.
  • 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 upper amount 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 molequivalent, 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 "pure gold catalyst” means that the Catalyst (C1) contains gold as the sole noble metal
  • the “mixed gold catalyst” means that the Catalyst (C1) contains gold and at least one metal typically selected from: (1) transition metals including palladium, platinum, ruthenium, rhodium, osmium, iridium, iron, nickel, cobalt, copper, and lanthanum; (2) main group metals including bismuth and tin; and (3) alkaline earth metals including strontium and barium.
  • Catalyst (C1) contains gold and at least one other transition metal selected from a group consisting of palladium, platinum and copper.
  • the preferred gold/transition metal ratio is between 1 :1 to 20:1 , more preferably between 3:1 to 10:1.
  • Catalyst (C1) contains gold and at least one other main group metal selected from bismuth and tin, more preferably bismuth.
  • the preferred gold/main group metal ratio is between 1 :1 to 20:1 , more preferably between 3:1 to 10:1.
  • Catalyst (C1 ) contains gold, at least one other main group metal selected from bismuth and tin, and at least one alkaline earth metal selected from strontium and barium. In this
  • the amount of alkaline earth metal used is generally between 0.5 wt% and 75 wt% of gold, while the amount of main group metal is generally between 0.5 wt% and 75 wt% of gold.
  • the gold particles contained in the Catalyst (C1 ) have an
  • average particles size in the nanometer range preferably from 1 to 50 nm and more preferably from 2 to 10 nm.
  • the particle size can be measured, e.g., by transmission electron microscopy or light scattering methods known in the art.
  • Catalyst (C2) used in the process of the invention preferably contains a first element selected from palladium and platinum and a second element selected from a group consisting of tin, copper and bismuth, of which copper and bismuth are further preferred.
  • Catalyst (C2) is in the range of 1 :100 to 1 :1 , more preferably in the range of 1 :100 to 1 :2.
  • Catalyst (C2) further contains a third element
  • the amount of the third element used is between 1 % and 100% by mole of the first element in Catalyst (C2).
  • Catalyst (C) is a heterogeneous catalyst.
  • the metal(s) of Catalyst (C) is applied to a support.
  • Preferred supports are activated carbon and oxide supports.
  • Exemplary oxide supports include titanium dioxide, zinc oxide, magnesium oxide, cerium dioxide and aluminium oxide, among which zinc oxide, magnesium oxide, and aluminium oxide are particularly preferred.
  • Such supported Catalyst (C) can be produced by known methods such as adsorption, deposition-precipitation, or incipient wetness impregnation approach.
  • the supported Catalyst (C) may comprise 0.5 to 10 wt% of noble metal, preferably 1 to 5 wt% of noble metal, based on the total weight of the supported catalyst.
  • 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 selected Catalyst (C) 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 selected Catalyst (C).
  • 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 selected Catalyst (C); or by mixing the peroxide, the alcohol, the base compound and the selected Catalyst (C) in advance to prepare a mixed reagent.

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  • Engineering & Computer Science (AREA)
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Abstract

Provided is a process of oxidizing an alcohol of formula ROH (I), wherein R represents a saturated or unsaturated, linear, branched or cyclic C3-C50 hydrocarbon group which is optionally substituted with a heteroatom, characterized in that the oxidation is performed in a liquid phase using a peroxide as oxidant and in the presence of a base compound and a catalyst [Catalyst (C) ] selected from a group consisting of: (i) a gold-containing catalyst [Catalyst (C1) ]; and (ii) a noble metal catalyst [Catalyst (C2) ] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second element selected from tin, bismuth, selenium, tellurium and antimony.

Description

Description
Process for Oxidation of Alcohols
Technical Field
[0001] This invention relates to a process for oxidation of alcohols using peroxide as oxidant and in the presence of a noble metal catalyst.
Background Art
[0002] Direct oxidation of fatty alcohols in the presence of noble metal catalyst(s) is known in the art and draws considerable interest, because this type of reaction has the potential to generate numerous fatty acid end-products with wide industrial uses, particularly in detergent and cosmetics applications.
[0003] For example, many publications described that 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.
[0004] To circumvent this high temperature problem, many later-published
patents for this process chose to oxidize ether alcohols using oxygen or oxygen-containing gas in the presence of a noble metal catalyst (in most cases palladium or platinum), which generally allows a lower reaction temperature (e.g. 20-95°C). See, for example, the description in US 3342858 (ALLIED CHEMICAL CORPORATION) 9/19/1967 , US 4214101 A (KAO SOAP CO., LTD) 6/22/1980 , DE 3135946 A (BAYER AG) 3/24/1983 , EP 0304763 A (HENKEL KGAA) 3/1/1989 , US 5292940 A (HENKEL KGAA) 3/7/1991 , JP 2903187 B (KAWAKEN FINE
CHEMICALS CO. LTD) 8/1 1/1992 , US 5463114 A (HENKEL KGAA) 10/26/1995 , US 8093414 B (CLARIANT INTERNATIONAL LTD)
2/21/2008 , US 2010056735 A (CLARIANT FINANCE BVI LTD)
10/23/2008 , US 20110144385 A (CLARIANT INTERNATIONAL LTD.) 2/11/2010 , CN 101357333 B (CHINA RESEARCH INSTITUTE OF DAILY CHEMICAL INDUSTRY) 2/4/2009 , US 20120296115 A (KAO CORP) 7/14/2011 , JP 2011184379 A (KAO CORP) 9/22/2011 , JP 2011184380 A (KAO CORP) 9/22/2011 , JP 2012149046 A (KAO CORP) 8/9/2012 , JP 2012149047 A (KAO CORP) 8/9/2012 , JP 2013067564 A (KAO CORP) 4/18/2013 and JP 2013151469 A (KAO CORP) 7/4/2013 . However, such gas-liquid reaction has its inherent problems, such as gas diffusion limitation, insufficient mass transfer at the gas-liquid interface, and the need of additional equipment such as gas compressors. In particular, if the oxygen or oxygen-containing gas is to pass into a relatively concentrated aqueous solution of the ether alcohol reactant in the presence of the catalysts, the viscosity of the reaction mixture would increase greatly as the conversion increases, causing a significant drop of reaction rate with time, as explained in US 4214101 A . Another disadvantage of oxidation with air is that the waste gas stream entrains ether alcohol in accordance with its vapor pressure and thus causes a certain degree of environmental pollution.
[0005] As an alternative approach, EP 0018681 B (SHELL INTERNATIONALE RESEARCH) 4/17/1980 and 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 /-butyl peroxide in the presence of palladium catalyst.
Nevertheless, according to the examples listed in EP 0039111A , the desirable effect of heterogeneous palladium catalyst relies on the combined use with a te -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 te -butyl alcohol is known as an instable solvent and not easy to handle in large quantity.
[0006] Recently, 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).
[0007] There is thus a need to provide a better process for oxidizing alcohols, in particular fatty alcohols and the like, to obtain their corresponding carboxylic acid with a high yield while avoiding the prior art problems discussed above.
Summary of invention
[0008] The present invention relates to a process of oxidizing an alcohol of
formula
OH (I),
wherein R represents a saturated or unsaturated, linear, branched or cyclic C3-C50 hydrocarbon group which is optionally substituted with a heteroatom, notably for the production of its corresponding carbonyl compounds,
characterized in that the oxidation is performed in a liquid phase using a peroxide as oxidant and in the presence of a base compound and a catalyst [Catalyst (C)] selected from a group consisting of: (i) a gold- containing catalyst [Catalyst (C1 )]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second element selected from tin, bismuth, selenium, tellurium and antimony.
[0009] As discovered by the present inventors, the special combination of
peroxide oxidant, a base compound and the selected Catalyst (C) as above detailed can effectively facilitate the desired oxidation of an alcohol of formula (I). Advantageously, 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. Notably, the process of the present invention is particularly suited to the detergent range alkoxyalkanols and fatty acid monoethanolamide.
[0010] The "alcohol" as used herein includes primary alcohols and secondary alcohols. Notably, 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.
[001 1] Throughout the description and the claims, the term "comprising one" should be understood as being synonymous with the term "comprising at least one" unless otherwise specified, and the term "between" should be understood as being inclusive of the limits. Moreover, unless otherwise indicated in the description and the claims, the values at the limits are included in the ranges of values which are given.
[0012] For the purpose of the present invention, the term "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.
[0013] In one preferred embodiment, the alcohol subjected to oxidation according to the process of the present invention is an ethoxylated fatty alcohol of formula (II)
R (OCH2CHR2)nOCH2CH2OH (II)
wherein: R1 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; R2 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.
[0014] For the purpose of the present invention, the term "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,
[0015] R1 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 R1 is given to methyl, butyl and lauryl, of which lauryl is further preferred. The R1 group can be an alkyl group substituted with any substituent which does not interfere with the oxidation of the hydroxyl group. For example, R1 in formula (II) may be an alkyl group substituted with at least one substituent selected from a group consisting of -OR*, -CH3, -CH2CH3, -COOH, -CONH2 and -COOR3, wherein R3 represents an alkyl or aryl group.
[0016] In formula (II), the R2 group on an individual molecule can be hydrogen, methyl or mixtures thereof. Accordingly, 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. Commercially, 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.
[0017] Preferably, n is an integer of from 4 to 12, more preferably from 4 to 9 in the individual molecule of formula (II).
[0018] In particular, when the alcohol subjected to oxidation according to the
process of the present invention is an ethoxylated fatty alcohol of formula (II), the invention provides a process for producing compounds of formula (III)
Ri(OCH2CHR2)nOCH2COOB (III)
with B being a cation and R1, R2 and n having the same meaning given above, and/or of the corresponding protonated carboxylic acids by oxidizing one or more ethoxylated fatty alcohols of formula (II),
characterized in that the oxidation is performed in a liquid phase using a peroxide as oxidant and in the presence of a base compound and a catalyst [Catalyst (C)] selected from a group consisting of: (i) a gold- containing catalyst [Catalyst (C1 )]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second element selected from tin, bismuth, selenium, tellurium and antimony.
[0019] Preferably, 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.
[0020] During the oxidation reaction in the basic medium, firstly the alkali metal salts (B=Li, Na, K, Rb, Cs) of formula (III) are formed. To produce 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.
[0021] In another preferred embodiment, the fatty alcohol subjected to oxidation according to the process of the present invention is a fatty acid
monoethanolamide of formula (IV)
Figure imgf000007_0001
wherein 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.
[0022] In the preferred fatty acid monoethanolamides according to the process of the present invention, 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.
[0023] 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. Here, it is also possible to use amides based on chain fractions or mixtures of these fatty acid monoethanolamides, preferably coconut fatty acid monoethanolamide.
[0024] In particular, when the alcohol subjected to oxidation according to the process of the present invention is a fatty acid monoethanolamide of formula (IV), the invention provides a process for producing compounds of formula (V)
Figure imgf000008_0001
with B and R' having the same meaning given above, and/or of the corresponding protonated acylglycine acids by oxidizing one or more fatty acid monoethanolamides of formula (IV),
characterized in that the oxidation is performed in a liquid phase using a peroxide as oxidant and in the presence of a base compound and a catalyst [Catalyst (C)] selected from a group consisting of: (i) a gold- containing catalyst [Catalyst (C1 )]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second element selected from tin, bismuth, selenium, tellurium and antimony.
[0025] During the oxidation reaction in the basic medium, firstly the alkali metal salts (B=Li, Na, K, Rb, Cs) of formula (V) are formed. To produce 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.
[0026] Alternatively, in yet another embodiment, 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.
[0027] 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. [0028] 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, te -butyl hydroperoxide, and cumenehydroperoxide; 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 te -butyl hydroperoxide, of which hydrogen peroxide is further preferred.
[0029] As hydrogen peroxide, hydrogen peroxide solution may be used. Typically, the concentration of the hydrogen peroxide solution used is 5 to 60 wt%, preferably 8 to 45 wt% and more preferably 30 to 40 wt%.
[0030] The upper amount 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 molequivalent, preferably 0.5 mol to 10 mol equivalent, more preferably 2 mol to 8 mol equivalent of the alcohol reactant.
[0031] The process of the invention is preferably carried out in water.
[0032] As gold-containing Catalyst (C1) used in the process of the invention, pure gold catalyst or mixed gold catalyst containing further metals may be used. As used herein, the "pure gold catalyst" means that the Catalyst (C1) contains gold as the sole noble metal, and the "mixed gold catalyst" means that the Catalyst (C1) contains gold and at least one metal typically selected from: (1) transition metals including palladium, platinum, ruthenium, rhodium, osmium, iridium, iron, nickel, cobalt, copper, and lanthanum; (2) main group metals including bismuth and tin; and (3) alkaline earth metals including strontium and barium.
[0033] In one preferred form, Catalyst (C1) contains gold and at least one other transition metal selected from a group consisting of palladium, platinum and copper. The preferred gold/transition metal ratio is between 1 :1 to 20:1 , more preferably between 3:1 to 10:1.
[0034] In another preferred form, Catalyst (C1) contains gold and at least one other main group metal selected from bismuth and tin, more preferably bismuth. The preferred gold/main group metal ratio is between 1 :1 to 20:1 , more preferably between 3:1 to 10:1. [0035] In yet another preferred form, Catalyst (C1 ) contains gold, at least one other main group metal selected from bismuth and tin, and at least one alkaline earth metal selected from strontium and barium. In this
embodiment, the amount of alkaline earth metal used is generally between 0.5 wt% and 75 wt% of gold, while the amount of main group metal is generally between 0.5 wt% and 75 wt% of gold.
[0036] Preferably, the gold particles contained in the Catalyst (C1 ) have an
average particles size in the nanometer range, preferably from 1 to 50 nm and more preferably from 2 to 10 nm. The particle size can be measured, e.g., by transmission electron microscopy or light scattering methods known in the art.
[0037] As Catalyst (C2) used in the process of the invention, it preferably contains a first element selected from palladium and platinum and a second element selected from a group consisting of tin, copper and bismuth, of which copper and bismuth are further preferred.
[0038] The preferred molar ratio of the second element to the first element in
Catalyst (C2) is in the range of 1 :100 to 1 :1 , more preferably in the range of 1 :100 to 1 :2.
[0039] In one preferred form, Catalyst (C2) further contains a third element
selected from strontium and barium. Generally, the amount of the third element used is between 1 % and 100% by mole of the first element in Catalyst (C2).
[0040] Preferably, Catalyst (C) is a heterogeneous catalyst.
[0041] Further preferably, the metal(s) of Catalyst (C) is applied to a support.
Preferred supports are activated carbon and oxide supports. Exemplary oxide supports include titanium dioxide, zinc oxide, magnesium oxide, cerium dioxide and aluminium oxide, among which zinc oxide, magnesium oxide, and aluminium oxide are particularly preferred. Such supported Catalyst (C) can be produced by known methods such as adsorption, deposition-precipitation, or incipient wetness impregnation approach.
[0042] The supported Catalyst (C) may comprise 0.5 to 10 wt% of noble metal, preferably 1 to 5 wt% of noble metal, based on the total weight of the supported catalyst. [0043] 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.
[0044] 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. Optionally, a uniform pH value is maintained throughout the reaction by adding a base in a given range.
[0045] When an alcohol is to be subjected to oxidation according to the process of the invention, the reaction can be allowed to proceed by successively adding the peroxide oxidant and the selected Catalyst (C) 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 selected Catalyst (C). Alternatively, 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 selected Catalyst (C); or by mixing the peroxide, the alcohol, the base compound and the selected Catalyst (C) in advance to prepare a mixed reagent.
Description of embodiments
[0046] The following examples are provided to illustrate preferred embodiments of the invention and are not intended to restrict the scope thereof. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.
Examples
[0047] Example 1
Method for Oxidizing Ethoxylated Fatty Alcohol using Gold Catalyst (C1)
[0048] 20 g of 20 wt% polyoxyethylene lauryl ether (Mw = 494.7, 7EO, AEO 7 obtained from Sasol) aqueous solution was mixed with 355.6 mg of NaOH and 367.6 mg of a gold catalyst (1 wt% by weight of gold on aluminium oxide, particle size of 3.2nm, obtained from Johnson Matthey Pic) in a three necked-flask equipped with magnetic stirrer and cooling condenser and pump injector, giving a NaOH/alcohol molar ratio of 1.1 and an alcohol/metal molar ratio of 432 in the mixture. The mixture was then stirred at 80°C for 5 min. Then, 3.66 g of 35 wt% hydrogen peroxide solution (, H2O2 alcohol = 4 mol/mol) was dropwise added into the heated mixture during a period of 10 hours. The end products in the reactor were analyzed and quantified by H NMR and 3C NMR, which found that 95 % of polyoxyethylene lauryl ether was converted with a 89.7% selectivity to sodium polyoxyethylene lauryl ether carboxylate.
[0049] Example 2
Method for Oxidizing Fatty Acid Ethanolamide using Gold Catalyst (C1) 7.96 g aqueous solution containing 12.7 wt% lauric acid ethanolamide (Mw = 243.2) and 12.7 wt% sodium N-lauroylglycine (Mw = 279.2) was mixed with 355.6 mg of NaOH and a gold catalyst (1wt% by weight of gold on aluminium oxide, particle size of 3.2nm, obtained from Johnson Matthey Pic) in a three necked-flask equipped with magnetic stirrer and cooling condenser and pump injector, giving a NaOH/alcohol molar ratio of 1.1 and an alcohol/metal molar ratio of 432 in the mixture. The mixture was then stirred at 80°C for 5 min. Then, 5.86 g of 35 wt% hydrogen peroxide solution (H2O2 alcohol = 6.4 mol/mol) was dropwise added into the heated mixture during a period of 10 hours. The end products in the reactor were analyzed and quantified by H NMR and 3C NMR, which found that 92.1 % of lauric acid ethanolamide was converted with a 70% selectivity to sodium lauryl glycinate.
[0050] Example 3
Method for Oxidizing Ethoxylated Fatty Alcohol using Mixed Catalyst (C2)
[0051] Gold and copper nanoparticles were adsorbed on nanoparticulate cerium oxide using the following procedure: 350 ml_ aqueous solution of gold (III) chloride trihydrate (0.082 g, HAuCI4-3H2O, Mw = 393.83, Au > 49.0%) and copper (II) chloride dihydrate (0.0055 g, CuCl2-2H2O, Mw = 170.48, CuCI2- 2H2O > 99%) in deionized water was added to 20 ml_ aqueous solution of 2.0 g cerium oxide in deionized water. The resulting slurry was
continuously stirred vigorously for 1 hour at room temperature. To this, 5ml_ aqueous solution of sodium borohydride (0.13 g, Mw = 37.83, NaBH4 > 98%) in deionized water was dropwise added. The Au-Cu/CeO2 solid thus produced was filtered and washed with several litres of deionized water until no traces of chlorides were detected by the AgNO3 test, and then freeze-dried under vacuum for 24 hours. The dried Au-Cu/CeO2 solid was analyzed by chemical analysis and transition electronic microscopy (TEM), to determine the content and size of gold and copper nanoparticles on the CeO2 support (1 wt% Au and 0.1 wt% Cu on the CeO2 support). Subsequently, 367.6 mg of the Au-Cu/CeO2 solid thus produced was mixed with 355.6 mg of NaOH in 20 g of 20 wt% polyoxyethylene lauryl ether (Mw = 494.7, 7EO, AEO 7 obtained from Sasol) aqueous solution, in a three necked-flask equipped with a magnetic stirrer, a cooling condenser and a pump injector, giving a NaOH/alcohol molar ratio of 1.1 and an alcohol/metal molar ratio of 432 in the mixture. The mixture was then stirred at 80°C for 5 min. Then, 2.93 g of hydrogen peroxide solution (35 wt. %, H2O2 alcohol = 6.4 mol/mol) was dropwise added into the heated mixture during a period of 10 hours. The end products in the reactor were analyzed and quantified by H NMR and 3C NMR, which found that 90 % of polyoxyethylene lauryl ether was converted with a 85.5% selectivity to sodium polyoxyethylene lauryl ether carboxylate.

Claims

A process of oxidizing an alcohol of formula
OH (I),
wherein R represents a saturated or unsaturated, linear, branched or cyclic C3-C50 hydrocarbon group which is optionally substituted with a heteroatom, characterized in that the oxidation is performed in a liquid phase using a peroxide as oxidant and in the presence of a base compound and a catalyst [Catalyst (C)] selected from a group consisting of: (i) a gold-containing catalyst [Catalyst (C1)]; and (ii) a noble metal catalyst [Catalyst (C2)] containing a first element selected from palladium, platinum, ruthenium, rhodium, osmium, and iridium and a second element selected from tin, bismuth, selenium, tellurium and antimony.
The process of claim 1 , for the production of the corresponding carbonyl compounds of the alcohol.
The process of claim 1 or 2, wherein the alcohol is an ethoxylated fatty alcohol of formula (II)
Ri(OCH2CHR2)nOCH2CH2OH (II)
wherein: R1 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; R2 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.
The process of claim 3, wherein R1 is selected from a group consisting of methyl, butyl and lauryl.
The process of claim 3, wherein R1 is an alkyl group substituted with at least one substituent selected from a group consisting of -OR3, -CH3, -CH2CH3, - COOH, -CONH2 and -COOR3, wherein R3 represents an alkyl or aryl group. The process of any of the claims 3-5, for producing compounds of formula (III)
R (OCH2CHR2)nOCH2COOB (III)
with B being a cation, and/or of the corresponding protonated carboxylic acids by oxidizing one or more ethoxylated fatty alcohols of formula (II).
7. The process of claim 6, further comprising reacting the compounds of formula (III) with acids.
8. The process of claim 1 or 2, wherein the alcohol is a fatty acid
monoethanolamide of formula (IV)
Figure imgf000015_0001
wherein 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.
9. The process of claim 8, wherein the fatty acid monoethanolamide of formula (IV) is lauric acid monoethanolamide.
10. The process of claim 8 or 9, for producing compounds of formula (V)
Figure imgf000015_0002
with B being a cation, and/or of the corresponding protonated acylglycine acids by oxidizing one or more fatty acid monoethanolamides of formula (IV).
11. The process of any one of the preceding claims, wherein the base compound is selected hydroxides of formula BOH, wherein B is an alkali metal cation selected from a group consisting of Li, Na, K, Rb and Cs.
12. The process of any one of the preceding claims, wherein the peroxide is
selected from the group consisting of hydrogen peroxide and te -butyl hydroperoxide.
13. The process of any one of the preceding claims, using a Catalyst (C1)
containing gold as the sole noble metal.
14. The process of any one of the preceding claims, using a Catalyst (C1)
containing gold and at least one metal typically selected from: (1) transition metals including palladium, platinum, ruthenium, rhodium, osmium, iridium, iron, nickel, cobalt, copper, and lanthanum; (2) main group metals including bismuth and tin; and (3) alkaline earth metals including strontium and barium.
15. The process of any one of the preceding claims, using a Catalyst (C1 ) containing gold and at least one other transition metal selected from a group consisting of palladium, platinum and copper.
16. The process of any one of the preceding claims, using a Catalyst (C2)
containing a first element selected from palladium and platinum and a second element selected from a group consisting of tin, copper and bismuth.
17. The process of claim 16, wherein the second element is copper or bismuth.
18. The process of any one of the preceding claims, wherein the Catalyst (C) is applied to a support selected from activated carbon and oxide supports.
19. The process of claim 18, wherein the support is an oxide support selected from zinc oxide, magnesium oxide, cerium dioxide and aluminium oxide.
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CN116099532A (en) * 2021-11-10 2023-05-12 广州米奇化工有限公司 Supported platinum ruthenium-based catalyst, preparation method thereof and preparation method of alcohol ether carboxylic acid
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