CN110713433A - Process for the hydrogenation of acids to alcohols - Google Patents
Process for the hydrogenation of acids to alcohols Download PDFInfo
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- CN110713433A CN110713433A CN201810835818.3A CN201810835818A CN110713433A CN 110713433 A CN110713433 A CN 110713433A CN 201810835818 A CN201810835818 A CN 201810835818A CN 110713433 A CN110713433 A CN 110713433A
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- acid
- alcohol
- catalyst
- copper
- hydrogenation
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- 239000002253 acid Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 30
- 150000001298 alcohols Chemical class 0.000 title claims description 17
- 230000008569 process Effects 0.000 title claims description 13
- 150000007513 acids Chemical class 0.000 title claims description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- 239000010949 copper Substances 0.000 claims abstract description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 claims abstract description 60
- 238000002360 preparation method Methods 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 10
- 235000011037 adipic acid Nutrition 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004566 IR spectroscopy Methods 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 229960002446 octanoic acid Drugs 0.000 claims description 5
- 150000007519 polyprotic acids Polymers 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 229940005605 valeric acid Drugs 0.000 claims description 5
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims description 4
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 20
- 239000000376 reactant Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- -1 cycloalkane carboxylic acid Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Images
Classifications
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- B01J23/72—Copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method for hydrogenating acid into alcohol, which comprises the following steps: copper-containing sheet silicate (copper phyllosilicate) is used as a catalyst, and after reduction treatment, acid is hydrogenated into alcohol in the presence of the reduced catalyst, wherein the catalyst comprises SiO carrier2And the active metal Cu. The preparation method for hydrogenating acid into alcohol not only can hydrogenate carboxylic acid into alcohol, but also can directly hydrogenate dibasic acid into dihydric alcohol and naphthenic carboxylic acid into cycloalkanol, and has the advantages of simplifying reaction steps, reducing production cost, reducing reaction pressure, improving reaction yield and the like.
Description
Technical Field
The present invention relates to a method for preparing alcohol by hydrogenating acid, especially a method for directly hydrogenating carboxylic monoacid, diacid or naphthenoid with carboxyl (-COOH) into alcohol.
Background
However, the utilization of fossil fuels causes a great deal of environmental pollution, and fossil fuels are non-renewable, and resources are increasingly scarce, so that the search for other methods for producing monohydric alcohols and dihydric alcohols is the focus of research in related industries at present.
Although it is known that monohydric and dihydric alcohols can be obtained by hydrogenation of organic acids, the conditions for hydrogenation of carboxylic acids are very severe because of the low electrophilicity of the C ═ O bonds in organic acids, for example: higher reaction temperature and higher hydrogen pressure, etc. The more common way to hydrogenate acids to alcohols is a two-step process of esterifying organic acids and then further hydrogenating the esters to alcohols.
In order to increase the yield of the hydrogenation reaction, acid hydrogenation is often carried out using a noble metal catalyst having high activity together with one or more metals, and it has been reported that a copper-based catalyst is used in the reaction, but only a hydroxyl group-containing monobasic acid is hydrogenated to an alcohol.
Disclosure of Invention
In the prior art, the reaction of hydrogenating acid into alcohol in one step is difficult, especially for carboxylic acid, the C ═ O bond in the carboxylic acid is difficult to be adsorbed by the catalyst due to low electrophilicity, so the hydrogenation condition is severe, generally, the acid is esterified first, then the ester is hydrogenated into alcohol, namely, a two-step method is needed, the reaction procedure is complex, and the noble metal catalyst used in the reaction of hydrogenating acid into alcohol in one step has high yield, but the preparation of the noble metal catalyst is complex and the production cost is high.
In addition, although there are documents using copper-based catalysts, bimetallic copper-containing catalysts are used, such as: the reaction of CuO/CoO needs to be carried out under the high pressure of 280atm to hydrogenate the adipic acid, and the reaction condition is difficult; monometallic copper-containing catalysts, such as: Cu/SiO2Currently, the method is only used for the reaction of hydrogenating hydroxyl-containing monobasic acid into dihydric alcohol, and the yield is far lower than 95%.
In view of the above, the present invention provides a method for preparing alcohol by hydrogenating acid, comprising the steps of: copper-containing sheet silicate (copper phyllosilicate) is used as a catalyst, and after reduction treatment, acid is hydrogenated into alcohol in the presence of the reduced catalyst, wherein the catalyst comprises SiO carrier2And the active metal Cu.
In a preferred embodiment, the catalyst has an I value as determined by infrared spectroscopy (IR) analysis670/I800The peak area ratio ranges from 0.05 to 0.5.
In a preferred embodiment, the catalyst has an I value as determined by infrared spectroscopy (IR) analysis670/I800The peak area ratio ranges from 0.1 to 0.37.
In a preferred embodiment, the acid comprises one or a combination selected from the group consisting of a monobasic acid, a hydroxyl-containing monobasic acid, a dibasic acid and a polybasic acid.
In a preferred embodiment, the acid comprises one or more compounds having a carboxyl group (-COOH), and the alcohol is a monohydric alcohol or a dihydric alcohol.
In a preferred embodiment, the acid comprises one or a combination selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, and 1, 4-cyclohexanedicarboxylic acid; the corresponding alcohols produced are methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, butanediol, pentanediol, hexanediol, decanediol and 1, 4-cyclohexanedimethanol, respectively.
In a preferred embodiment, the reduction treatment is carried out by pretreating the copper-containing layered silicate at 120 to 400 ℃ for 1 to 7 hours in a hydrogen atmosphere.
In a preferred embodiment, the pressure during the reaction is 50kg/cm2To 100kg/cm2。
In a preferred embodiment, the pressure during the reaction is 90kg/cm2。
Another object of the present invention is to provide a method for preparing a dibasic acid by direct hydrogenation into a diol, comprising the steps of: a process for the preparation of an acid hydrogenated to an alcohol as hereinbefore described wherein a dibasic acid is directly hydrogenated to a glycol in the presence of the reduced catalyst.
Another object of the present invention is to provide a process for directly hydrogenating a cycloalkane carboxylic acid to a cycloalkanol, which comprises the steps of: the process for producing an alcohol by hydrogenation of an acid as described above, wherein a cycloalkanecarboxylic acid is directly hydrogenated to a cycloalkanol in the presence of the reduced catalyst.
The preparation method for hydrogenating acid into alcohol has the following advantages:
1. the invention uses the copper-containing layered silicate as the catalyst, and compared with the existing noble metal catalyst, the cost is lower, the composition is simple, and the preparation is easier;
2. the preparation method adopts a one-step method to directly hydrogenate the acid into the alcohol, and the acid does not need to be esterified and then hydrogenated, so that the reaction steps are simplified, and the production cost is reduced;
3. compared with the copper-based catalyst using CuO/CoO, the reaction pressure is up to 280atm, the reaction pressure required by the preparation method is lower;
4. compared with the Cu/SiO used in the prior art2The catalyst, the copper-containing layered silicate of the invention has highly dispersed active metal copper due to the layered structure, can not only hydrogenate the unit acid, the hydroxyl-containing unit acid, the dibasic acid and the polybasic acid into alcohol, but also hydrogenate the dibasic acid directly into the dihydric alcohol and the naphthenic acid directly into the naphthenic alcohol, and meanwhile, the yield can reach more than 95 percent.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is an infrared spectrum of a catalyst used in a preferred embodiment of the present invention.
Detailed Description
The following detailed description, embodiments and technical contents of the present invention are described with reference to the drawings, however, it should be understood that these embodiments are only for the purpose of facilitating the understanding of the present invention and are not intended to limit the scope of the present invention.
The word "comprise" or "comprising" when used herein is intended to mean that it does not exclude the presence or addition of one or more other elements, steps, operations and/or elements. "A" means that the grammatical object of the object is one or more than one (i.e., at least one).
The invention provides a preparation method for hydrogenating acid into alcohol, which comprises the following steps: using a copper-containing sheet silicate (copper phyllosilicate) as a catalyst, reducing the catalyst, and hydrogenating the acid to alcohol in the presence of the reduced catalyst, wherein the catalyst comprises a carrier SiO2And the active metal Cu.
The invention also provides a preparation method for directly hydrogenating dibasic acid into dihydric alcohol, which comprises the following steps: copper-containing layered silicate (copper phyllosilicate) is used as a catalyst, and after reduction, the copper-containing layered silicate is subjected to reduction in the presence of the reduced catalystThe dibasic acid is directly hydrogenated into the dihydric alcohol, wherein the catalyst comprises a carrier SiO2And the active metal Cu.
The invention also provides a preparation method for directly hydrogenating naphthenic carboxylic acid into naphthenic alcohol, which comprises the following steps: copper-containing layered silicate (copper phyllosilicate) is used as a catalyst, and after reduction, naphthenic carboxylic acid is directly hydrogenated into alkanol in the presence of the reduced catalyst, wherein the catalyst comprises SiO carrier2And the active metal Cu.
The term "method for preparing an alcohol by hydrogenating an acid" as used herein refers to a method for preparing an alcohol by hydrogenating an acid in one step, i.e., directly preparing an alcohol by hydrogenating an acid, rather than a two-step method comprising esterifying an acid to form an ester and then hydrogenating the ester to form an alcohol.
The "acid" as used herein refers to a reactant of the preparation method of the present invention. In a preferred embodiment, the acid is, for example but not limited to: comprises one or a combination of a monobasic acid, a hydroxyl group-containing monobasic acid, a dibasic acid and a polybasic acid. In a preferred embodiment, the acid comprises one or more compounds having a carboxyl group (-COOH), i.e., the acid comprises one or more compounds having a carboxyl group. . In a preferred embodiment, the acid is, for example but not limited to: comprises one or a combination of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1, 4-cyclohexanedicarboxylic acid and other organic acids.
The term "alcohol" as used herein refers to the product of the preparation process of the present invention, which may be a monohydric alcohol, a dihydric alcohol or a polyhydric alcohol, depending on the reactants. In a preferred embodiment, in the method of the present invention for the hydrogenation of an acid to an alcohol, the reactant is a monocarboxylic acid and the product is a monohydric alcohol. In a preferred embodiment, in the method for preparing alcohol by hydrogenating acid of the present invention, the reactant is dicarboxylic acid and the product is diol. In a preferred embodiment, in the process for the hydrogenation of an acid to an alcohol of the present invention, the reactant is a naphthenic carboxylic acid and the product is a cycloalkanol. In a preferred embodiment, in the method of the present invention for preparing alcohols by hydrogenating acids, when the reactant acid is one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1, 4-cyclohexanedicarboxylic acid, the corresponding alcohol is methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, butanediol, pentanediol, hexanediol, decanediol, 1, 4-cyclohexanedimethanol, respectively.
The "catalyst" referred to herein is the use of copper-containing layered silicate (CPS), which is a good catalyst in hydrogenation. The copper-containing layered silicate forms a layered structure with highly dispersed active metal copper (Cu), while Cu0And Cu+The copper-containing phyllosilicate used in the invention has excellent catalytic performance due to the synergistic effect of the copper-containing phyllosilicate and the copper-containing phyllosilicate. And the copper and the silicon dioxide have stronger interaction, so that the catalyst has good heat resistance, and the catalyst can be prevented from being deactivated due to the agglomeration of active metals. In a preferred embodiment, the copper-containing layered silicate of the present invention has an infrared spectroscopy (IR) analysis of 670 and 800cm-1Band of (1) found experimentally670And I800The area ratio of (A) can be taken as the proportion occupied by the layered structure when I670And I800When the area ratio is too low, the layered structure of the copper-containing layered silicate is less, and the surface area of copper metal is too small, so that the reaction rate is too slow, and even catalytic reaction cannot be carried out; when I is670And I800When the area ratio is too high, it means that the layered structure of the copper-containing layered silicate is large, and the surface area of copper metal is too large, so that the activity of the catalyst becomes too high, and the reactant is excessively hydrogenated, resulting in an increase in by-products, thereby affecting the yield, and therefore it is preferable to have I670/I800The peak area ratio (ratio) ranges from 0.05 to 0.5, such as but not limited to: 0.05, 0.07, 0.1, 0.13, 0.15, 0.17, 0.2, 0.23, 0.25, 0.27, 0.3, 0.33, 0.35, 0.37, 0.4, 0.43, 0.45, 0.47, or 0.5. In a more preferred embodiment, the copper-containing layered silicate of the invention has an IR spectrum analysis of I670/I800Peak area ratioIn the range of 0.1 to 0.37, such as but not limited to: 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37.
According to the present invention, it is found that there is a correlation between the yield of the product "alcohol" and the surface area of the active metal, and therefore, the copper particles dispersed in the layered silicate are preferably copper nanoparticles.
The preparation method of the invention uses the copper-containing layered silicate as the catalyst, and the catalyst is subjected to reduction treatment after preparation and before use, and the reduction treatment comprises the following steps: the copper-containing layered silicate is reduced by exposing it to hydrogen, however, the method of reducing the catalyst is not limited in the present invention. In a preferred embodiment, the reduction treatment is carried out by pretreating the copper-containing layered silicate at 120 to 400 ℃ for 1 to 7 hours in a hydrogen atmosphere; the temperature of the reduction reaction is not limited to: 120 deg.C, 150 deg.C, 170 deg.C, 200 deg.C, 220 deg.C, 250 deg.C, 270 deg.C, 300 deg.C, 320 deg.C, 350 deg.C, 370 deg.C, or 400 deg.C; the time of the aforementioned reduction reaction is, for example, but not limited to: 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or the like.
In the preparation method of the present invention, a certain reaction pressure is required to be maintained during the hydrogenation reaction, and in a preferred embodiment, the reaction pressure may be 50 to 200kg/cm2Examples, but not limited to: 50kg/cm2、60kg/cm2、70kg/cm2、80kg/cm2、90kg/cm2、100kg/cm2、110kg/cm2、120kg/cm2、130kg/cm2、140kg/cm2、150kg/cm2、160kg/cm2、170kg/cm2、180kg/cm2、190kg/cm2Or 200kg/cm2And the like. In a more preferred embodiment, the reaction pressure of the preparation process of the present invention is 90kg/cm2。
In the preparation method of the present invention, the hydrogenation reaction has a better reaction temperature and reaction time, and in a preferred embodiment, the hydrogenation reaction is performed at a temperature of 150 ℃ to 350 ℃ for 3 to 24 hours, and the reaction temperature is, for example, but not limited to: 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, or 350 ℃, and the like, and the reaction time is, for example, but not limited to: 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 16.5 hours, 17 hours, 17.5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours, 20 hours, 20.5 hours, 21 hours, 21.5 hours, 22 hours, 22.5 hours, 23 hours, 23.5 hours, or 24 hours, etc.
With respect to the reaction pressure, temperature and time of the hydrogenation reaction, the reaction conditions may be adjusted according to the reactants and catalyst and the desired effect, and in a preferred embodiment, the hydrogenation reaction is carried out in the presence of the reduced copper-containing layered silicate with a gas pressure of 90kg/cm at 240 ℃2And reacting for 12 to 20 hours. The advantage of such hydrogenation conditions is that the reaction pressure only has to be maintained at 90kg/cm2The method can achieve the excellent effect of hydrogenating the carboxylic acid into the alcohol in one step with the yield of more than 95 percent, and overcome the defects that the reaction condition is difficult because the high-pressure reaction needs to be maintained in the conventional preparation method or the production cost is high because of a noble metal catalyst.
The following examples are intended to illustrate, but not to limit, the present invention.
PREPARATION EXAMPLE 1 preparation of copper-containing layered silicate catalyst
(1) 15g of copper nitrate and 46ml of aqueous ammonia were taken and added to 300ml of pure water.
(2) The above solution was added to 45ml of silica sol and stirred for 1 day.
(3) The solution was heated in a water bath at 80 ℃ until the pH decreased from 11 to 7.
(4) The above solution was placed in an oven at 150 ℃ and heated for 1 day, filtered and dried at 60 ℃.
(5) Finally, the copper-containing layered silicate Catalyst (CPS) is obtained by placing the copper-containing layered silicate catalyst into a high-temperature furnace and calcining the copper-containing layered silicate catalyst at 400 ℃ for 4 hours.
[ example 1]
(1) 0.3g of the copper-containing layered silicate catalyst of preparation example 1 was placed in a 1 liter autoclave and subjected to reduction treatment in a hydrogen atmosphere at 350 ℃ for 3 hours.
(2) Next, 0.6g of adipic acid as a reactant, and 180ml of 1, 4-dioxane as a solvent were charged into the autoclave.
(3) Introducing nitrogen for 3 times, introducing hydrogen for 3 times, and introducing hydrogen to increase pressure to 54kg/cm2。
(4) The temperature was raised to 240 ℃ and the pressure was maintained at 90kg/cm2The reaction was stirred for 12 hours.
(5) After completion of the reaction, the catalyst was filtered and analyzed by a gas chromatograph, and the results are shown in Table 1.
[ examples 2 to 12]
The reaction was carried out in the same manner as in example 1 except that the reactants were changed to those shown in Table 1, and the results are shown in Table 1.
TABLE 1
The results show that, as shown in example 1 of table 1, adipic acid was successfully converted into hexanediol by the preparation method of the present invention, and the product yield was as high as 95.9%, confirming that the preparation method of the present invention can be applied to the direct hydrogenation of carboxylic acids to alcohols, and that the preparation method of the present invention can be applied to the direct hydrogenation of dibasic acids to glycols, and the product yield was as high as 95% or more.
As shown in example 2 of table 1, the preparation method of the present invention successfully converts 1, 4-cyclohexanedicarboxylic acid into 1, 4-cyclohexanedimethanol with a product yield as high as 97.2%, confirming that the preparation method of the present invention can be applied to the direct hydrogenation of naphthenic carboxylic acid into cycloalkanol, and that the preparation method of the present invention can be applied to the direct hydrogenation of naphthenic dibasic acid into naphthenic diol with a product yield of more than 95%.
As shown in examples 3 to 9 of Table 1, the method of the present invention successfully converts monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid and caprylic acid into monohydric alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and octanol, respectively, and the yield of the corresponding monobasic alcohols is as high as 95.7% to 98.6%, and it is evident that the method of the present invention can directly hydrogenate monobasic acids into monohydric alcohols, and the yield of the corresponding monobasic alcohols is 95% or more.
As shown in examples 10 to 12 in table 1, the preparation method of the present invention can successfully convert dibasic acids such as succinic acid, glutaric acid, and sebacic acid into diols such as butanediol, pentanediol, and decanediol, and their corresponding diols, respectively, in addition to converting adipic acid into hexanediol, and the product yield reaches 95.1% to 97.2%, so that the preparation method of the present invention for hydrogenating acids into alcohols can directly hydrogenate dibasic acids into diols, and the product yield reaches 95% or more.
Thus, as demonstrated in examples 1 to 12, the preparation process of the present invention can hydrogenate an acid to the corresponding alcohol in one step, and the reaction pressure is maintained at only 90kg/cm2The yield of the product is as high as 95.1 percent to 98.6 percent.
[ preparation example 2]Copper silicon shell (Cu/SiO)2) Preparation of the catalyst
(1) 15g of copper nitrate was taken and added to 13ml of pure water.
(2) An aqueous solution of copper nitrate was uniformly sprayed on 16g of silica.
(3) It was placed in an oven at 60 ℃ and dried overnight.
(4) Finally, the catalyst is put into a high-temperature furnace at 400 ℃ to be calcined for 4 hours to obtain the shell-shaped copper-silicon catalyst.
Comparative example 1
The reaction was carried out in the same manner as in example 1 except that the catalyst was changed to that of preparation example 2, whereby the yield of hexanediol was 69.3%.
Comparative example 2
Except that the catalyst was changed to commercially available non-lamellar Cu/SiO2The reaction was carried out in the same manner as in example 1 except for using a catalyst (CU60/8T, Johnson Matthey corporation), whereby the yield of hexanediol was 72.8%.
Comparative example 3
Except that the catalyst is changed into a commercial noble metal Ru/Al2O3A reaction was carried out in the same manner as in example 1 except for using a catalyst (T-8403, manufactured by Clariant corporation), whereby the yield of hexanediol was 52.6%.
Comparative example 4
The reaction was carried out in the same manner as in example 1 except that the catalyst was changed to a commercially available Cu/Al/Mn multimetal Cu/Al catalyst (T-8706, manufactured by Clariant Co., Ltd.), whereby the yield of hexanediol was 76.6%.
Thus, the catalyst component used has Cu/SiO2However, the yields of the products of comparative examples 1 and 2, which do not have a layered structure, were 69.3% and 72.8%, respectively, which is much lower than the yield of 95.9% of the product of example 1 under the same reaction conditions. If the catalysts containing copper component are compared (i.e., comparative examples 1, 2, 4), the yield of the product is about 69% -77%, which is much lower than the yield of 95.9% of the product obtained in example 1 under the same reaction conditions. Furthermore, generally speaking, higher product yields would be expected using noble metal catalysts, but comparative example 3 uses a commercially available noble metal catalyst Ru/Al2O3The product yield of (a) is only 52.6%, which is much lower than the product yield of 95.9% of example 1 under the same reaction conditions. It is apparent that the yields of hydrogenation of adipic acid to hexanediol in comparative examples 1 to 4 are only 52.6% to 76.6%, which is much lower than the yield of the product of example 1 in which adipic acid is also converted, i.e. the preparation process of the present invention using a copper-containing layered silicate as a reaction catalyst, not only allows the acid to be hydrogenated to the corresponding alcohol in only one step, but also results in superior efficacy which cannot be achieved with other alternative catalysts.
[ preparation example 3]
A copper-containing layered silicate catalyst was obtained in the same manner as in preparation example 1, except that 7g of copper nitrate and 21ml of aqueous ammonia were used.
[ preparation example 4]
A copper-containing layered silicate catalyst was obtained in the same manner as in preparation example 1, except that 27g of copper nitrate and 82ml of aqueous ammonia were used.
IR spectrum measurement and analysis
For preparation examples 1 to 4, IR spectrum measurement and analysis were performed.
IR measurement: preparing 2 wt% catalyst in potassium bromide (KBr) by using a spectrum 1000 type (from Perkin Elmer company), pressing the sample into a test piece, putting the test piece into a machine for analysis, and analyzing the test piece at a wavelength of 400-4400 cm-1The obtained infrared spectrum is shown in FIG. 1.
Spectral analysis: calculation of I670And I800Peak area of (D) to obtain I670And I800The results of the area ratios of (a) to (b) are shown in Table 2.
[ examples 13 and 14]
The reaction procedure for example 13 is the same as example 1, with the only difference that: the catalyst was changed to the catalyst of preparation example 3 and the reaction time was changed to 20 hours.
The reaction procedure for example 14 is the same as example 1, with the only difference that: the catalyst was changed to the catalyst of preparation example 4.
The reaction results of examples 13 and 14 are shown in Table 2.
TABLE 2
The results show that I in FIG. 11040And I670Represents OH vibration, I, in the copper-containing layered silicate1100And I800Represents an amorphous silica band (amorphous silica SiO band), from which it can be seen that670And I800The area ratio of (a) can be used as the proportion of the layered structure in the copper-containing layered silicate catalyst.
According to the above IR spectrum analysis results, when I670/I800When the ratio is too low, it means that the layered structure is small and the surface area of the copper metal is too smallThe activity of the catalyst is too low, so that the reaction rate is too slow, and even the catalytic reaction cannot be carried out; when I is670/I800When the ratio is too high, it means that the number of layered structures is large, the surface area of copper metal is too large, resulting in too high catalyst activity, excessive hydrogenation of reactants, resulting in increase of by-products, and thus, yield is affected. Referring to the reaction results of examples 12 to 14 shown in Table 2, I670And I800Has a good effect in the range of 0.1 to 0.37.
Furthermore, from the IR spectrum, I670The specific structure of the copper-containing layered silicate catalysts of the present invention can also be demonstrated.
In summary, the preparation method for hydrogenating acid into alcohol according to the present invention has the following advantages: the invention uses the copper-containing layered silicate as the catalyst, which has lower cost, simple composition and easier preparation compared with the prior noble metal catalyst; the preparation method of the invention adopts a one-step method to directly hydrogenate the acid into alcohol, and does not need to esterify the acid and then hydrogenate the acid, thereby simplifying the reaction steps and reducing the production cost; compared with the copper-based catalyst using CuO/CoO, the reaction pressure of the preparation method is as high as 280atm, and the reaction pressure required by the preparation method is lower; compared with the Cu/SiO used in the prior art2The catalyst, the copper-containing layered silicate of the present invention has a high dispersion of the active metal copper due to its layered structure, and thus has a high surface area of the active metal copper, and is soluble in Cu+And Cu0The method has a synergistic effect, can hydrogenate the monoacid, the hydroxyl-containing monoacid, the dibasic acid and the polybasic acid into alcohol, can hydrogenate the dibasic acid into the dihydric alcohol directly, and can hydrogenate naphthenic acid into the naphthenic alcohol directly, and the yield can reach more than 95 percent.
Although the present invention has been described in detail, it should be understood that the above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the invention, i.e., the appended claims are intended to cover all such modifications and changes as fall within the true spirit and scope of the invention.
Claims (11)
1. A process for the preparation of an alcohol by hydrogenation of an acid, comprising the steps of:
using a copper-containing sheet silicate as a catalyst, reducing the catalyst, and hydrogenating the acid to alcohol in the presence of the reduced catalyst, wherein the catalyst comprises SiO as a carrier2And the active metal Cu.
2. The process for the preparation of an alcohol by hydrogenation of an acid as claimed in claim 1, wherein the catalyst has I by IR spectroscopy670/I800The peak area ratio ranges from 0.05 to 0.5.
3. The process for the preparation of an alcohol by hydrogenation of an acid as claimed in claim 2, wherein the catalyst has I by IR spectroscopy670/I800The peak area ratio ranges from 0.1 to 0.37.
4. The method of claim 2, wherein the acid comprises one or a combination of a monobasic acid, a hydroxyl group-containing monobasic acid, a dibasic acid, and a polybasic acid.
5. The method of claim 4, wherein the acid comprises one or more compounds having a carboxyl group and the alcohol is a monohydric alcohol or a dihydric alcohol.
6. The method of claim 5, wherein the acid comprises one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, and 1, 4-cyclohexanedicarboxylic acid; the corresponding alcohols produced are methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, butanediol, pentanediol, hexanediol, decanediol and 1, 4-cyclohexanedimethanol, respectively.
7. The method according to claim 4, wherein the reduction treatment comprises pretreating the copper-containing layered silicate at 120 to 400 ℃ for 1 to 7 hours in a hydrogen atmosphere.
8. The process for producing an alcohol by hydrogenation of an acid according to claim 4, wherein the pressure at the time of the reaction is 50kg/cm2To 100kg/cm2。
9. The process for producing an alcohol by hydrogenation of an acid according to claim 8, wherein the pressure during the reaction is 90kg/cm2。
10. A method for preparing dihydric alcohol by directly hydrogenating dibasic acid, which is characterized by comprising the following steps:
the process for the production of alcohols by hydrogenation of acids as claimed in any of claims 1 to 9, characterized in that the dibasic acids are directly hydrogenated to glycols in the presence of the reduced catalyst.
11. A method for preparing naphthenic carboxylic acid directly hydrogenated into naphthenic alcohol is characterized by comprising the following steps:
the production process for hydrogenating an acid into an alcohol according to any one of claims 1 to 9, wherein naphthenic carboxylic acid is directly hydrogenated into a cycloalkanol in the presence of the reduced catalyst.
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