CN103450010B - Method for preparing cyclohexanecarboxylic acid - Google Patents
Method for preparing cyclohexanecarboxylic acid Download PDFInfo
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- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 26
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 69
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005554 pickling Methods 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 38
- 230000035484 reaction time Effects 0.000 claims description 27
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 25
- 235000010234 sodium benzoate Nutrition 0.000 claims description 25
- 239000004299 sodium benzoate Substances 0.000 claims description 25
- 230000004048 modification Effects 0.000 claims description 23
- 238000012986 modification Methods 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229940050390 benzoate Drugs 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 11
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000010235 potassium benzoate Nutrition 0.000 claims description 9
- 239000004300 potassium benzoate Substances 0.000 claims description 9
- 229940103091 potassium benzoate Drugs 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000001020 rhythmical effect Effects 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 239000005711 Benzoic acid Substances 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RSPWPAYFBOWLKA-UHFFFAOYSA-N cyclohexane;formic acid Chemical compound OC=O.C1CCCCC1 RSPWPAYFBOWLKA-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002547 new drug Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- LAOOXBLMIJHMFO-UHFFFAOYSA-N 1-[2-(diethylamino)ethylamino]-4-methylthioxanthen-9-one;hydron;chloride Chemical compound Cl.S1C2=CC=CC=C2C(=O)C2=C1C(C)=CC=C2NCCN(CC)CC LAOOXBLMIJHMFO-UHFFFAOYSA-N 0.000 description 1
- FSVJFNAIGNNGKK-UHFFFAOYSA-N 2-[cyclohexyl(oxo)methyl]-3,6,7,11b-tetrahydro-1H-pyrazino[2,1-a]isoquinolin-4-one Chemical compound C1C(C2=CC=CC=C2CC2)N2C(=O)CN1C(=O)C1CCCCC1 FSVJFNAIGNNGKK-UHFFFAOYSA-N 0.000 description 1
- ZKTFZNPTAJIXMK-UHFFFAOYSA-N 2-cyclohexylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1CCCCC1 ZKTFZNPTAJIXMK-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- OELFLUMRDSZNSF-BRWVUGGUSA-N nateglinide Chemical compound C1C[C@@H](C(C)C)CC[C@@H]1C(=O)N[C@@H](C(O)=O)CC1=CC=CC=C1 OELFLUMRDSZNSF-BRWVUGGUSA-N 0.000 description 1
- 229960000698 nateglinide Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960002957 praziquantel Drugs 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001843 schistosomicidal effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing cyclohexanecarboxylic acid, and belongs to the field of synthesis of fine chemicals. The method is characterized by comprising the following steps: pouring a benzoate water solution into a reaction kettle filled with a selective hydrogenation catalyst from a material storage tank to carry out hydrogenation reaction; directly feeding the product to a pickling tower after hydrogenation reaction, wherein the upper oil is cyclohexanecarboxylic acid. By adopting the method, cyclohexanecarboxylic acid with a high additional value is produced by using benzoate; the used catalyst has ultrahigh selectivity and high hydrogenation activity. The method not only is simple to operate and can carry out intermittent reaction and continuous reaction, but also has good economic benefits and an industrial application prospect.
Description
Technical field
The invention belongs to catalyst preparation field, relate to a kind of method preparing hexahydrobenzoic acid.
Background technology
Hexahydrobenzoic acid is a kind of important organic synthesis intermediate, itself time good light curing agent, the synthesis of schistosomicide new drug praziquantel can also be used for the treatment of.Its derivative is the intermediate of production for treating diabetes new drug nateglinide as trans-4-sec.-propyl heptanaphthenic acid methyl esters, therefore prepares the status that hexahydrobenzoic acid occupation ratio in organic synthesis is more important.Preparing hexahydrobenzoic acid by phenylformic acid selec-tive hydrogenation is more difficult at typical condition, even if with the palladium/carbon catalyst of high hydrogenation activity, its transformation efficiency is also difficult to reach 100%, prepares in hexahydrobenzoic acid process with benzoic acid hydrogenation, not only the easy hydrogenation and removing of benzoic carboxyl.And due to catalyst stability and reclaim problem be all difficult to industrialization.
Along with the continuous increase of the consumption of hexahydrobenzoic acid, preparation high purity hexahydrobenzoic acid becomes more and more important.Most important for development active good, good stability, catalyzer of being easy to reclaim in aqueous phase.Raney's nickel not only has higher high active of hydrogenation catalysis in water, and itself has the separation that magnetic is of value to product.Therefore, be well suited for aqueous phase and prepare hexahydrobenzoic acid.Following known technology, all comes with some shortcomings:
Now conventional selective hydrogenation catalyst is palladium/carbon catalyst, phenylformic acid selective hydrogenation reaction is at temperature 160-170oC, carry out in tank reactor under pressure 1.2-1.4MPa condition, because palladium/carbon catalyst is fine catalyst, with reaction raw materials and product separation more difficult.For reclaiming precious metal palladium, palladium/carbon catalyst is needed thoroughly to be separated with other materials of reaction system, therefore reactant phenylformic acid is needed thoroughly to react completely, to reduce subsequent processing steps, but when reactant and palladium/carbon catalyst Long contact time can increase side reaction, the yield of cyclohexylbenzoic acid is significantly reduced.
Document Reactive Polymers, 18(1992) 1 report adopt organic supported method prepare platinum-organic carrier catalyzer, benzoic acid can be carried out stone literary composition outstanding person and generate hexahydrobenzene formic acid, and transformation efficiency is close to 100%, but there is separation and the problem of recovery in this catalyzer, and the poor stability of catalyzer, easy in inactivation.
Chinese patent, publication number: CN1406921A, introduce a kind of method of phenylformic acid selec-tive hydrogenation hexahydrobenzene formic acid, it adopts fixed-bed reactor, but the activity of catalyzer is low, and low conversion rate is poor to target product selectivity, and the later separation of product is comparatively difficult.
Chinese patent, publication number: CN1406666A, introduces a kind of catalyzer of preparation of hexahydrobenzoic acid by hydrogenation of benzoic acid, and this catalyzer take acidic alumina as carrier, with VI B or VIII race's metal for active ingredient.Use it for the reaction of fixed bed benzoic acid hydrogenation, the hexahydrobenzene formic acid yield not only that its process produces is low, and the purity of hexahydrobenzene formic acid is low.
Summary of the invention
The invention provides a kind of method preparing hexahydrobenzoic acid.For the purpose of resource rational utilization benzoate, more drawback is there is for phenylformic acid, as poor catalyst stability, it is more difficult to reclaim, environmental pollution is serious, the problems such as hexahydrobenzoic acid productive rate is low, are organically combined by constant voltage reaction, pickling and rectifying and realize benzoate recycling, change into the chemical hexahydrobenzoic acid of high added value.In addition, benzoate is raw material by the present invention, avoids the generation of side reaction during selec-tive hydrogenation, improves the productive rate of target product.Invention increases the transformation efficiency of reaction and the selectivity of hexahydrobenzoic acid, simultaneously the extending catalyst life-span, obtain the highly purified hexahydrobenzoic acid of high added value.
Technical scheme of the present invention is as follows:
Benzoate raw material in the present invention comprise Sodium Benzoate, potassium benzoate, phenylformic acid and sodium hydroxide reaction product, phenylformic acid with or potassium hydroxide reaction product in one or two or more kinds mix as raw material.
The Raney's nickel catalyst that the catalyzer that in the present invention, selec-tive hydrogenation uses is modification.The Main Function of Raney's nickel catalyst carries out benzoate aromatic ring hydrotreated lube base oil.First Raney's nickel catalyst carries out dealumination reaction, increases its activity.Dealuminzation condition is: temperature of reaction 70 DEG C, reaction times 2h, aqueous sodium hydroxide solution concentration 30%, and the mass ratio of aqueous sodium hydroxide solution and Raney's nickel catalyst is 4-10:1.The consisting of of Raney's nickel catalyst after dealuminzation: nickel content is 65 ~ 80%, and molybdenum content is 5 ~ 10%, and aluminium content is 10 ~ 25%.
The method is that the constant voltage reactor that just the benzoate aqueous solution is equipped with selective hydrogenation catalyst by raw material storage tank injection carries out hydrogenation reaction.Reaction conditions is: the concentration of hydrogenation reaction temperature 160 ~ 240 DEG C, hydrogen pressure 2 ~ 6MPa, reaction times 6 ~ 10h, benzoate is 10 ~ 40%, and the mass ratio of benzoate and catalyzer is 100:1 ~ 5.After hydrogenation reaction, product directly enters pickling tower acid and washes, and acid used is the vitriol oil or concentrated hydrochloric acid.Obtaining upper strata oily hexahydrobenzoic acid after pickling goes rectifying tower rectifying to obtain high purity hexahydrobenzoic acid, lower floor's brine waste decontaminated water process.
The yield of hexahydrobenzoic acid is obtained more than 95% by method production of the present invention.
Constant voltage reactor of the present invention, pickling tower, rectifying adopt interval or the mode of operate continuously, flexible operation, easy.
The present invention adopts the benzoate aqueous solution to be raw material, and with the Raney's nickel of modification for hydrogenation catalyst, in constant voltage reactor, carry out hydrogenation reaction, after hydrogenation reaction, product directly enters pickling tower, and upper strata oily hexahydrobenzoic acid obtains high purity hexahydrobenzoic acid through rectifying.The present invention's benzoate produces the high hexahydrobenzoic acid of added value; The catalyzer used has very high selectivity and higher hydrogenation activity.This method not only has simple to operate, can single still rhythmic reaction, again can multi-floating bodies successive reaction, and has good economic benefit and prospects for commercial application.
Accompanying drawing explanation
Accompanying drawing is process flow diagram of the present invention.
In figure: 1 raw material storage tank; 2 constant voltage hydrogenation stills; 3 pickling towers; 4 rectifying tower.
Embodiment
Specific embodiments of the invention are described in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1: Raney's nickel catalyst carries out dealumination reaction, dealuminzation condition is: the mass ratio of temperature of reaction 70 DEG C, reaction times 2h, aqueous sodium hydroxide solution concentration 30%, aqueous sodium hydroxide solution and Raney's nickel catalyst is 4:1.Following table 1 is shown in that Raney's nickel catalyst carries out the composition of dealumination reaction
Embodiment 2: Raney's nickel catalyst carries out dealumination reaction, dealuminzation condition is: the mass ratio of temperature of reaction 70 DEG C, reaction times 2h, aqueous sodium hydroxide solution concentration 30%, aqueous sodium hydroxide solution and Raney's nickel catalyst is 7:1.Following table 1 is shown in that Raney's nickel catalyst carries out the composition of dealumination reaction
Embodiment 3: Raney's nickel catalyst carries out dealumination reaction, dealuminzation condition is: the mass ratio of temperature of reaction 70 DEG C, reaction times 2h, aqueous sodium hydroxide solution concentration 30%, aqueous sodium hydroxide solution and Raney's nickel catalyst is 10:1.Following table 1 is shown in that Raney's nickel catalyst carries out the composition of dealumination reaction.
Nickel content/% molybdenum content/% aluminium content/%
Embodiment 4: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, Sodium Benzoate is 10%, and the mass ratio of Sodium Benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 5: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, Sodium Benzoate is 20%, and the mass ratio of Sodium Benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 6: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, Sodium Benzoate is 40%, and the mass ratio of Sodium Benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 7: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, Sodium Benzoate is 40%, and the mass ratio of Sodium Benzoate and catalyzer is 100:1.Following table 2 is shown in reaction result.
Embodiment 8: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, Sodium Benzoate is 40%, and the mass ratio of Sodium Benzoate and catalyzer is 100:5.Following table 2 is shown in reaction result.
Embodiment 9: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, potassium benzoate is 40%, and the mass ratio of potassium benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 10: with the Raney's nickel catalyst of embodiment 1 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, potassium benzoate is 40%, and the mass ratio of potassium benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 11: with the Raney's nickel catalyst of embodiment 2 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, potassium benzoate is 40%, and the mass ratio of potassium benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 12: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, benzoic concentration are 40%, and the mol ratio of phenylformic acid and sodium hydroxide is 0.8, the mass ratio of phenylformic acid and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 13: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, benzoic concentration are 40%, and the mol ratio of phenylformic acid and sodium hydroxide is 1.2, the mass ratio of phenylformic acid and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 14: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, benzoic concentration are 40%, and the mol ratio of phenylformic acid and potassium hydroxide is 0.8, the mass ratio of phenylformic acid and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 15: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 8h, benzoic concentration are 40%, and the mol ratio of phenylformic acid and potassium hydroxide is 1.2, the mass ratio of phenylformic acid and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 16: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 160 DEG C, hydrogen pressure 5MPa, reaction times 8h, Sodium Benzoate is 40%, and the mass ratio of Sodium Benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 17: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 240 DEG C, hydrogen pressure 5MPa, reaction times 8h, Sodium Benzoate is 40%, and the mass ratio of Sodium Benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 18: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 2MPa, reaction times 8h, Sodium Benzoate is 40%, and the mass ratio of Sodium Benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 19: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 4MPa, reaction times 8h, Sodium Benzoate is 40%, and the mass ratio of Sodium Benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 20: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 6h, Sodium Benzoate is 40%, and the mass ratio of Sodium Benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
Embodiment 21: with the Raney's nickel catalyst of embodiment 3 modification for selective hydrogenation catalyst in constant voltage reactor.Reaction conditions is: the concentration of hydrogenation reaction temperature 180 DEG C, hydrogen pressure 5MPa, reaction times 10h, Sodium Benzoate is 40%, and the mass ratio of Sodium Benzoate and catalyzer is 100:3.Following table 2 is shown in reaction result.
As shown in Table 2, along with concentration of benzoic acid increases, transformation efficiency reduces, but constant to the selectivity of hexahydrobenzoic acid; Along with the increase of temperature of reaction, transformation efficiency increases, but declines to the selectivity of hexahydrobenzoic acid; Along with the prolongation in reaction times, transformation efficiency increases, but substantially constant to the selectivity of hexahydrobenzoic acid; Along with the increase of reaction pressure, transformation efficiency increases, but substantially constant to the selectivity of hexahydrobenzoic acid; Potassium benzoate selec-tive hydrogenation easier than Sodium Benzoate, and when reaction solution is alkalescence, speed of reaction is faster, and selectivity is better.
Embodiment 22: the enterprising line stabilization experiment on the basis of embodiment 6, following table 3 is shown in 5 circulating reaction results.
5 circulation experiment results as shown in Table 3, show that the Raney's nickel catalyst of modification has good selec-tive hydrogenation active, and show satisfactory stability.
Claims (8)
1. prepare the method for hexahydrobenzoic acid for one kind, it is characterized in that: the benzoate aqueous solution injects the constant voltage reactor that selective hydrogenation catalyst is housed and carries out hydrogenation reaction, after hydrogenation reaction, product directly enters pickling tower, upper strata oily hexahydrobenzoic acid goes rectifying tower rectifying to obtain high purity hexahydrobenzoic acid, lower floor's brine waste decontaminated water process; Selec-tive hydrogenation catalyst for refining is the Raney's nickel catalyst of modification, and it consists of: nickel content is 65 ~ 80%, and molybdenum content is 5 ~ 10%, and aluminium content is 10 ~ 25%.
2. method according to claim 1, is further characterized in that: benzoate comprises Sodium Benzoate, potassium benzoate.
3. method according to claim 2, is further characterized in that: the concentration of benzoate is 10 ~ 40%, and the mass ratio of benzoate and catalyzer is 100:1 ~ 5.
4. the method according to claim 1,2 or 3, is further characterized in that: the Raney's nickel catalyst of described modification, obtains in the following ways: first carry out dealumination reaction, increases its activity; Dealuminzation condition is: temperature of reaction 70 DEG C, reaction times 2h, aqueous sodium hydroxide solution concentration 30%, and the mass ratio of aqueous sodium hydroxide solution and Raney's nickel catalyst is 4-10:1.
5. the method according to claim 1,2 or 3, is further characterized in that: hydrogenation reaction temperature 160 ~ 240 DEG C, hydrogen pressure 2 ~ 6MPa, reaction times 6 ~ 10h.
6. method according to claim 4, is further characterized in that: hydrogenation reaction temperature 160 ~ 240 DEG C, hydrogen pressure 2 ~ 6MPa, reaction times 6 ~ 10h.
7. method according to claim 5, is further characterized in that: adopt single still rhythmic reaction or multi-floating bodies successive reaction.
8. method according to claim 6, is further characterized in that: adopt single still rhythmic reaction or multi-floating bodies successive reaction.
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| CN105251482A (en) * | 2015-10-14 | 2016-01-20 | 南京大学连云港高新技术研究院 | Ruthenium palladium/carbon catalyst of cyclohexanecarboxylic acid synthesized through benzoic acid hydrogenation and preparation method and application thereof |
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| CN111217695A (en) * | 2020-02-21 | 2020-06-02 | 内蒙古世杰化工有限公司 | Method for continuously synthesizing cyclohexanecarboxylic acid |
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| US3326972A (en) * | 1962-05-26 | 1967-06-20 | Basf Ag | Preparation of trans-hexahydro-terephthalic acid by hydrogenation of a terephthalic acid salt in the presence of a cis-hexahydro terephthalic acid salt |
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