CN100352797C - Novel process for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation - Google Patents
Novel process for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation Download PDFInfo
- Publication number
- CN100352797C CN100352797C CNB2005100171928A CN200510017192A CN100352797C CN 100352797 C CN100352797 C CN 100352797C CN B2005100171928 A CNB2005100171928 A CN B2005100171928A CN 200510017192 A CN200510017192 A CN 200510017192A CN 100352797 C CN100352797 C CN 100352797C
- Authority
- CN
- China
- Prior art keywords
- acid
- reaction
- reactor
- hydrogenation
- hexahydrobenzoic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 title claims abstract description 105
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 26
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010948 rhodium Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 238000003760 magnetic stirring Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000010926 purge Methods 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 11
- 235000011089 carbon dioxide Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 229910052709 silver Inorganic materials 0.000 description 14
- 239000004332 silver Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- -1 titanium dioxide metal oxide Chemical class 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a novel process for synthesizing cyclohexyl methanoic acid by benzoic acid hydrogenation. Under the conditions with a load type transitional metal rhodium catalyst, supercritical carbon dioxide and the cyclohexyl methanoic acid, without solvents and mild reaction condition, the benzoic acid contacts with hydrogen gas to generate circulation catalytic reaction; after the catalytic reaction is over, the benzoic acid carries out extraction by utilizing the dissolubility of the cyclohexyl methanoic acid in the supercritical carbon dioxide, and the catalyst and the product are separated. The present invention has the advantages of mild reaction condition, clean reaction process, no side product and waste generation, and high quality cyclohexyl methanoic acid yield; the present invention avoids large amounts of organic solvents and subsequent separation processes caused by the use of additive agents.
Description
Technical field
The invention relates to the method for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation, be specially: under condition of no solvent, the method for load type rhodium catalyst catalysis synthesizing cyclohexyl formic acid by benzoic acid hydrogenation in supercritical co and the hexahydrobenzoic acid
Background technology
Hexahydrobenzoic acid and derivative thereof are the important Organic Chemicals and the intermediate of synthetic drugs, have suitable application prospects.Hexahydrobenzoic acid can be used for light curing agent 184, that is: 1-hydroxy-cyclohexyl phenyl ketone is synthetic; Simultaneously also be the finings of solubilizing agent, oil of ultraviolet light polymerization initiator and non-flavescence light trigger, vulcanized rubber efficiently and medicine intermediate etc.Hexahydrobenzoic acid can make from the phenylformic acid shortening, and benzoic acid hydrogenation is the important step that the SNIA technology prepares caprolactam technology, and traditional benzoic acid hydrogenation technology is catalyzer with Pd/C.The benzoic acid hydrogenation technology of present industrial employing has: the phenylformic acid catalytic hydrogenation reaction in (1) solvent (methyl alcohol, higher alcohols kind solvent, acids solvent, alkaline solution etc.): this method exists by product many, shortcomings such as separated from solvent reclaims difficulty, and product yield is low.(2) molten state phenylformic acid catalytic hydrogenation reaction: phenylformic acid can be realized hydrogenation reaction rapidly, completely in molten state, loaded down with trivial details separation, recycling step in the time of can avoiding with an organic solvent, but reaction needs comparatively carry out under the exacting terms at comparatively high temps and vigorous stirring etc.(3) phenylformic acid is at the aqueous phase catalytic hydrogenation reaction: phenylformic acid and hexahydrobenzoic acid generation decarboxylation side reaction generate CO and CO
2, the CO of generation causes poisoning of catalyst.(CN1343651A) proposed by add Ni-based promotor to reactive system, with CO and the H that impels reaction to generate in the recently relevant patent
2Reaction is converted into methane, eliminates the influence of CO to the Pd/C catalyzer, improves active.But the adding of Ni-based auxiliary agent has brought operations such as additional separation to reaction process.Recently in disclosed Chinese patent CN1406921A in 2003, adopt fixed-bed reactor utilize alumina load platinum catalysis benzoic acid hydrogenation prepare hexahydrobenzoic acid work simplification catalyzer and product separating step, at temperature of reaction 160-220 ℃, hydrogen pressure 0.5-4.0MPa obtains the yield of hexahydrobenzoic acid about 70% under the air speed 0.1-15 hour condition.Up to the present, the industrial catalyzer that uses of para Toluic Acid's hydrogenation preparing hexahydrobenzoic acid often is the Pd/C catalyzer, and hydrogenation reaction, is carried out in tank reactor under the 1.2-1.4MPa condition at 160-200 ℃.This technological reaction temperature height, complex procedures, and catalyzer and product duration of contact longly cause secondary reaction to increase to cause reaction preference to descend.
Summary of the invention
The present invention is directed to the problem that exists in the existing benzoic acid hydrogenation reaction process, developed under mild conditions (temperature of reaction 20-80 ℃,) green synthesis method of organic solvent-free, product can separate by supercritical carbon dioxide extraction with catalyzer, obtain high-quality, the hexahydrobenzoic acid of high yield.
The purpose of the inventive method is that to utilize be the loaded catalyst catalysis of active constituent efficiently with the rhodium, at no any solvent, uses synthesizing cyclohexyl formic acid by benzoic acid hydrogenation under low temperature, the low pressure; Can also take the benzoic acid hydrogenation method in the carbon dioxide reaction medium to prepare hexahydrobenzoic acid at low temperatures; Can also make solvent, under low temperature, low pressure condition, use synthesizing cyclohexyl formic acid by benzoic acid hydrogenation with hexahydrobenzoic acid; And with supercritical co product is carried out extracting and separating and obtain high-quality, the hexahydrobenzoic acid of high yield.
Characteristics of the present invention: not with an organic solvent, additive under the mild reaction conditions of promotor, is made synthetic high yield purpose product hexahydrobenzoic acid in the cleaning activity system of reaction medium at supercritical co, solvent-free and hexahydrobenzoic acid.
The condition and the step of the method for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation provided by the invention are as follows:
A. the benzoic acid hydrogenation method under the condition of no solvent:
(1), the composition proportion of reactant is: the molar ratio of reactant phenylformic acid and catalyzer is: 500: 1;
In autoclave, add the phenylformic acid of proportional quantity and rhodium catalyst or be the loading type Rh/C of active constituent, Rh/Al with the rhodium
2O
3, Rh/SiO
2, Rh/TiO
2Catalyzer a kind of;
Then autoclave is tightened the air of at room temperature using in the nitrogen pipeline purging emptying reaction system;
(2), reactor is heated to 20-80 ℃, suitable temperature is 20-50 ℃; Charging into hydrogen in reactor is 1-10MPa to the required pressure of reaction, opens magnetic stirring apparatus then, and the reaction times is 2-6 hour; After reaction finished, product separated with catalyzer through carbon dioxide abstraction.Also can separate through natural subsidence or filtration.
B. the method for A can also adopt the benzoic acid hydrogenation in the carbon dioxide reaction medium to prepare hexahydrobenzoic acid as mentioned above, it is characterized in that:
In step (2), reactor is heated to 20-80 ℃, and suitable temperature is 20-50 ℃, charging into hydrogen in reactor is 1-10MPa to the required pressure of reaction, charge into carbonic acid gas then, (8-16MPa) open magnetic stirring apparatus then, the reaction times is 2-6 hour.
C. the method for A can also adopt that benzoic acid hydrogenation prepares hexahydrobenzoic acid in the hexahydrobenzoic acid as mentioned above, it is characterized in that: in step (1), add phenylformic acid, rhodium catalyst and the hexahydrobenzoic acid of proportional quantity in autoclave, the benzoic mol ratio of hexahydrobenzoic acid and reactant is 5: 1～1: 1; Then autoclave is tightened and at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system.
Aforesaid extraction and the separation method that carries out product with supercritical co is: aforesaid A, B and C, after finishing, reaction make the temperature of reactor remain on 30-60 ℃, in reactor, charge into carbonic acid gas continuously, extracting pressure is 10-15MPa, the carbonic acid gas flow velocity is 5mL/Min, obtains product.The purity of products therefrom is greater than 99.5%.
The support of the catalyst of method is as mentioned above: aluminium sesquioxide, activated carbon, silicon-dioxide, titanium dioxide metal oxide carrier.
The reaction product that method of the present invention obtains takes after acetone diluted that gas-chromatography, chromatography-mass spectroscopy are online to be analyzed and qualitative.
The present invention compares as the traditional method of Pd/C catalysis benzoic acid hydrogenation in and the organic solvent following with dewatered melted type with existing reaction process has the reaction conditions gentleness, advantages such as product purity height and reaction process cleaning.Temperature of reaction has dropped to 20-50 ℃ from 120-200 ℃, does not add any organic solvent and additive, and reaction process does not generate any by product.(as Comparative Examples 1-5.)
Embodiment
Further by the following Examples, the present invention will be described.
Embodiment 1
(1), in the 50mL autoclave, add the 1g phenylformic acid (SILVER REAGENT, homemade) of proportional quantity, the 0.05g rhodium catalyst is tightened autoclave then and is at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 30 ℃ of temperature, charging into hydrogen in reactor is 2MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; Reaction is carried out separating with product through natural subsidence or filtration after finishing, and the hexahydrobenzoic acid yield that obtains is 24.57%.
Embodiment 2
(1), in the 50mL autoclave, add the 1g phenylformic acid (SILVER REAGENT, homemade) of proportional quantity, the 0.05g rhodium catalyst is tightened autoclave then and is at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 20 ℃ of temperature, charging into hydrogen in reactor is 4 MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; The hexahydrobenzoic acid yield that obtains through carbon dioxide abstraction is 99.38%.
Embodiment 3
(1), in the 50mL autoclave, add the 1g phenylformic acid (SILVER REAGENT, homemade) of proportional quantity, the 0.05g rhodium catalyst is tightened autoclave then and is at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 30 ℃ of temperature, charging into hydrogen in reactor is 6MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finished, the hexahydrobenzoic acid yield that obtains through carbon dioxide abstraction was 99.56%.
Embodiment 4
(1), in the 50mL autoclave, add the 1g phenylformic acid (SILVER REAGENT, homemade) of proportional quantity, the rhodium catalyst of 0.05g is tightened autoclave then and is at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 50 ℃ of temperature, charging into hydrogen in reactor is 2MPa to the required pressure of reaction, charging into carbonic acid gas then is 8MPa to reacting required pressure, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finished, the hexahydrobenzoic acid yield that obtains through carbon dioxide abstraction was 39.55%.
Embodiment 5
(1), in the 50mL autoclave, add the 1g phenylformic acid (SILVER REAGENT, homemade) of proportional quantity, the rhodium catalyst of 0.05g is tightened autoclave then and is at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 80 ℃ of temperature, charging into hydrogen in reactor is 4MPa to the required pressure of reaction, charging into carbonic acid gas then is 8MPa to reacting required pressure, opens magnetic stirring apparatus then, the reaction times is 3 hours; Reaction is carried out separating with product through natural subsidence or filtration after finishing, and the hexahydrobenzoic acid yield that obtains is 60.78%.
Embodiment 6
(1), in the 50mL autoclave, add the 1g phenylformic acid (SILVER REAGENT, homemade) of proportional quantity, the rhodium catalyst of 0.05g is tightened autoclave then and is at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 40 ℃ of temperature, charging into hydrogen in reactor is 6MPa to the required pressure of reaction, charging into carbonic acid gas then is 9MPa to reacting required pressure, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finished, the hexahydrobenzoic acid yield that obtains through carbon dioxide abstraction was 70.76%.
Embodiment 7
(1), in the 50mL autoclave, add the 1g phenylformic acid (SILVER REAGENT, homemade) of proportional quantity, the rhodium catalyst of 0.05g is tightened autoclave then and is at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 40 ℃ of temperature, charging into hydrogen in reactor is 10MPa to the required pressure of reaction, charging into carbonic acid gas then is 10MPa to reacting required pressure, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finished, the hexahydrobenzoic acid yield that obtains through carbon dioxide abstraction was 99.10%.
Embodiment 8
(1), in autoclave, add the 1g phenylformic acid (SILVER REAGENT, homemade) of proportional quantity, the rhodium catalyst of 0.05g and 3g hexahydrobenzoic acid are tightened autoclave then and are at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 30 ℃ of temperature, charging into hydrogen in reactor is 2MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finished, the hexahydrobenzoic acid yield that obtains through carbon dioxide abstraction was 80.3%.
Embodiment 9
(1), in autoclave, add the 1g phenylformic acid (SILVER REAGENT, homemade) of proportional quantity, the rhodium catalyst of 0.05g and 1g hexahydrobenzoic acid are tightened autoclave then and are at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 30 ℃ of temperature, charging into hydrogen in reactor is 2MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; The hexahydrobenzoic acid yield that obtains through carbon dioxide abstraction is 96.4%.
Comparative Examples 1
(1), adding mol ratio in the 50mL autoclave is 500: 1 reactant phenylformic acid (SILVER REAGENT, homemade) and Pd/C catalyzer; Add the 10mL deionized water then; Then autoclave is tightened and at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 125 ℃ of temperature, charging into hydrogen in reactor is 1.6MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finishes, cooling, catalyzer separates with product through natural subsidence or filtration, and the hexahydrobenzoic acid yield that obtains is 96.20%.
Comparative Examples 2
(1), adding mol ratio in the 50mL autoclave is 500: 1 reactant phenylformic acid (SILVER REAGENT, homemade) and Pd/C catalyzer; Then autoclave is tightened and at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 140 ℃ of temperature, charging into hydrogen in reactor is 4MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finishes, cooling, catalyzer separates with product through natural subsidence or filtration, and the hexahydrobenzoic acid yield that obtains is 61.65%.
Comparative Examples 3
(1), adding mol ratio in the 50mL autoclave is 500: 1 reactant phenylformic acid (SILVER REAGENT, homemade) and Pd/C catalyzer; Then autoclave is tightened and at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 50 ℃ of temperature, charging into hydrogen in reactor is 4MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finishes, cooling, catalyzer separates with reaction mixture through natural subsidence or filtration, does not have the product hexahydrobenzoic acid by analysis and generates.
Comparative Examples 4
(1), adding mol ratio in the 50mL autoclave is 500: 1 reactant phenylformic acid (SILVER REAGENT, homemade) and Pt/Al
2O
3Catalyzer; Then autoclave is tightened and at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 200 ℃ of temperature, charging into hydrogen in reactor is 1.0MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finishes, cooling, catalyzer separates with product through natural subsidence or filtration, and the hexahydrobenzoic acid yield that obtains is 73.0%.
Comparative Examples 5 of the present invention
(1), adding mol ratio in the 50mL autoclave is 500: 1 reactant phenylformic acid (SILVER REAGENT, homemade) and Ph/C catalyzer; Then autoclave is tightened and at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system;
(2), after reactor is heated to 30 ℃ of temperature, charging into hydrogen in reactor is 6MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 3 hours; After reaction finished, the hexahydrobenzoic acid yield that obtains through carbon dioxide abstraction was 99.56%.
Claims (6)
1, a kind of method of synthesizing cyclohexyl formic acid by benzoic acid hydrogenation, its step and condition are as follows:
(1), the composition proportion of reactant is: the mol ratio of reactant phenylformic acid and catalyzer is 500: 1;
In autoclave, add the phenylformic acid of proportional quantity and be the loading type Rh/C of active constituent, Rh/Al with the rhodium
2O
3, Rh/SiO
2, Rh/TiO
2Catalyzer a kind of;
Then autoclave is tightened and at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system; With
(2), reactor is heated to 20-80 ℃, charging into hydrogen in reactor is 1-10MPa to the required pressure of reaction, opens magnetic stirring apparatus then, the reaction times is 2-6 hour; After reaction finishes, separate with product and obtain hexahydrobenzoic acid, also can carry out separating and obtain hexahydrobenzoic acid through natural subsidence or filtration with product through carbon dioxide abstraction.
2. the method for a synthesizing cyclohexyl formic acid by benzoic acid hydrogenation as claimed in claim 1 is characterized in that, and is described in step (2), and the suitable temperature of reactor heating is 20-50 ℃.
3, a kind of method of synthesizing cyclohexyl formic acid by benzoic acid hydrogenation as claimed in claim 2 is characterized in that:
In step (2), after reactor was heated to 30-50 ℃ of temperature, charging into hydrogen in reactor was 1-10MPa to the required pressure of reaction, and charging into carbonic acid gas then is 8-16MPa, opens magnetic stirring apparatus then, and the reaction times is 2-6 hour; After reaction finishes, obtain hexahydrobenzoic acid through carbon dioxide abstraction.
4, a kind of method as the described synthesizing cyclohexyl formic acid by benzoic acid hydrogenation of any one claim of claim 1-3, it is characterized in that, aforesaid in step (1), the phenylformic acid, rhodium catalyst and the hexahydrobenzoic acid that in autoclave, add proportional quantity, the benzoic mol ratio of hexahydrobenzoic acid and reactant is 5: 1～1: 1, then autoclave is tightened and at room temperature used the nitrogen pipeline purging, the air in the emptying reaction system.
5, as the method for the described synthesizing cyclohexyl formic acid by benzoic acid hydrogenation of any one claim of claim 1-3, it is characterized in that, describedly obtain the hexahydrobenzoic acid method through carbon dioxide abstraction and be: after reaction finishes, make the temperature of reactor remain on 30-60 ℃, in reactor, charge into carbonic acid gas continuously, extracting pressure is 10-15MPa, obtains hexahydrobenzoic acid.
6. the method for a synthesizing cyclohexyl formic acid by benzoic acid hydrogenation as claimed in claim 4, it is characterized in that: describedly obtain the hexahydrobenzoic acid method through carbon dioxide abstraction and be: after reaction finishes, make the temperature of reactor remain on 30-60 ℃, in reactor, charge into carbonic acid gas continuously, extracting pressure is 10-15MPa, obtains hexahydrobenzoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100171928A CN100352797C (en) | 2005-10-17 | 2005-10-17 | Novel process for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100171928A CN100352797C (en) | 2005-10-17 | 2005-10-17 | Novel process for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1749234A CN1749234A (en) | 2006-03-22 |
| CN100352797C true CN100352797C (en) | 2007-12-05 |
Family
ID=36604913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100171928A Expired - Fee Related CN100352797C (en) | 2005-10-17 | 2005-10-17 | Novel process for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100352797C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6524693B2 (en) * | 2014-02-26 | 2019-06-05 | 三菱ケミカル株式会社 | Process for producing alicyclic polyvalent carboxylic acid |
| CN109694321B (en) * | 2017-10-24 | 2021-09-14 | 中国石油化工股份有限公司 | Method for preparing high-purity cyclohexanecarboxylic acid |
| CN114632511A (en) * | 2020-12-15 | 2022-06-17 | 中国科学院大连化学物理研究所 | Catalyst for hydrogenation reaction of benzoic acid compounds and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406921A (en) * | 2001-08-29 | 2003-04-02 | 中国石油化工股份有限公司 | Selective hydrogenation for preparing hexabydrobenzoic acid from benzoic acid |
-
2005
- 2005-10-17 CN CNB2005100171928A patent/CN100352797C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406921A (en) * | 2001-08-29 | 2003-04-02 | 中国石油化工股份有限公司 | Selective hydrogenation for preparing hexabydrobenzoic acid from benzoic acid |
Non-Patent Citations (1)
| Title |
|---|
| 浙江化工 余中林，余卫国，1.3，苯甲酸催化加氢合成环己基甲酸的研究 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1749234A (en) | 2006-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3235804B1 (en) | Method for purifying 1,5-pentanediamine | |
| EP2913319B1 (en) | Synthesis of guerbet alcohols | |
| CN113024350B (en) | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound | |
| EP1630155B1 (en) | Hydrogenation of methylenedianiline | |
| CN106496017B (en) | Catalytic hydrogenation continuous production device and production method | |
| CN102099320A (en) | Process for obtaining neopentyl glycol by cracking high boilers occurring in the production process | |
| CN100352797C (en) | Novel process for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation | |
| CN110386856B (en) | Method for preparing 1, 3-propylene glycol by hydration and hydrogenation of acrolein | |
| US8664444B2 (en) | Method for producing primary aliphatic amines from aldehydes | |
| CN111215138A (en) | catalyst, preparation method and application of catalyst in preparation of β -isophorone | |
| CN114276533A (en) | Method and device for continuously preparing polyether amine | |
| US20150252015A1 (en) | Method for synthesising 2,5-di(hydroxymethyl)furan and 2,5-di(hydroxymethyl)tetrahydrofuran by selective hydrogenation of furan-2,5-dialdehyde | |
| CN102471189B (en) | Method for producing low-odor n-butane | |
| CN111215079B (en) | Method for preparing alcohol by hydrogenation of aldehydes by adopting nickel-based heterogeneous catalyst | |
| CN101497561A (en) | Hydroformylation process | |
| CN100337753C (en) | Method for reproducing catalyst by supercritical fluid | |
| US20090054702A1 (en) | Hydrogenation process | |
| CN101798272A (en) | Method for synthesizing para aminophenylmethylether by catalytic hydrogenation of paranitroanisole | |
| CN104844449A (en) | Benzoic acid based anhydrous and solvent-free method for preparing heptanaphthenic acid | |
| CN114522737A (en) | Method for preparing 3-acetoxy propanol with high selectivity | |
| CN111217750B (en) | Preparation method of caprolactam | |
| CN103272579A (en) | Catalyst for oriented synthesis of isobutanol by synthesis gas as well as preparation method and application of catalyst | |
| CN103842322A (en) | Method for preparing a mixture of alcohols | |
| CN113735688A (en) | Recycling method of waste liquid of butanol device | |
| CN102336737B (en) | Method for catalytically reducing alkyl-substituted benzocrown ether with Pichler ruthenium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHEJIANG TAIZHOU QINGQUAN MEDICAL + CHEMICAL CO., Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20090403 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090403 Address after: No. 3, South City Road, Chengguan Town, Xianju County, Zhejiang, Taizhou Patentee after: Zhejiang Taizhou Qingquan Medical & Chemical Co., Ltd. Address before: No. 5625 Renmin Street, Jilin, Changchun Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Jiangsu Qingquan Chemical Co., Ltd. Assignor: Zhejiang Taizhou Qingquan Medical & Chemical Co., Ltd. Contract record no.: 2010330002268 Denomination of invention: Novel process for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation Granted publication date: 20071205 License type: Exclusive License Open date: 20060322 Record date: 20101221 |
|
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU QINGQUAN CHEMICAL CO., LTD. Free format text: FORMER OWNER: ZHEJIANG TAIZHOU QINGQUAN MEDICAL + CHEMICAL CO., LTD. Effective date: 20140822 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 317300 TAIZHOU, ZHEJIANG PROVINCE TO: 222455 YANCHENG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20140822 Address after: 222455 Jiangsu Province, Yancheng City Binhai County Binhuai town head Zeng village coastal chemical industry park Patentee after: JIANGSU QINGQUAN CHEMICAL CO., LTD. Address before: 317300, No. 3, South City Road, Chengguan Town, Xianju County, Taizhou, Zhejiang Patentee before: Zhejiang Taizhou Qingquan Medical & Chemical Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071205 Termination date: 20171017 |