CN103450010A - Method for preparing cyclohexanecarboxylic acid - Google Patents
Method for preparing cyclohexanecarboxylic acid Download PDFInfo
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- CN103450010A CN103450010A CN2013103822395A CN201310382239A CN103450010A CN 103450010 A CN103450010 A CN 103450010A CN 2013103822395 A CN2013103822395 A CN 2013103822395A CN 201310382239 A CN201310382239 A CN 201310382239A CN 103450010 A CN103450010 A CN 103450010A
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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 the catalyst preparation field, relate to a kind of method for preparing hexahydrobenzoic acid.
Background technology
Hexahydrobenzoic acid is a kind of important organic synthesis intermediate, itself the time good light curing agent, can also be used for the treatment of the synthetic of schistosomicide new drug praziquantel.Its derivative is the intermediate of production for treating diabetes new drug nateglinide as trans-4-sec.-propyl heptanaphthenic acid methyl esters, and therefore prepare hexahydrobenzoic acid occupies important status in organic synthesis.Select the standby hexahydrobenzoic acid of Hydrogenation by phenylformic acid is more difficult under usual conditions, even if the palladium/carbon catalyst with high hydrogenation activity, its transformation efficiency also is difficult to reach 100%, with benzoic acid hydrogenation, prepares in the hexahydrobenzoic acid process, not only the easy hydrogenation and removing of benzoic carboxyl.And because catalyst stability and recovery problem all are difficult to industrialization.
Along with the continuous increase of the consumption of hexahydrobenzoic acid, preparation high purity hexahydrobenzoic acid becomes more and more important.For development in water active good, good stability, to be easy to the catalyzer that reclaims most important.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 water and prepare hexahydrobenzoic acid.Following known technology all comes with some shortcomings:
Selective hydrogenation catalyst commonly used is palladium/carbon catalyst now, the phenylformic acid selective hydrogenation reaction is at temperature 160-170oC, under pressure 1.2-1.4MPa condition, in tank reactor, carry out, because palladium/carbon catalyst is fine catalyst, more difficult with reaction raw materials and product separation.For reclaiming precious metal palladium, palladium/carbon catalyst thoroughly need to be separated with other materials of reaction system, therefore the reactant phenylformic acid thoroughly need to be reacted completely, to reduce subsequent processing steps, can increase side reaction but work as reactant and palladium/carbon catalyst Long contact time, make the benzoic yield decrease of cyclohexyl.
Document Reactive Polymers, 18(1992) 1 reported that the organic supported method of employing prepares platinum-organic carrier catalyzer, can carry out benzoic acid stone literary composition outstanding person and generate hexahydrobenzene formic acid, and transformation efficiency approaches 100%, but this catalyzer exists and separates and the recovery problem, and the poor stability of catalyzer, easily inactivation.
Chinese patent, publication number: CN1406921A, introduce a kind of method that phenylformic acid is selected Hydrogenation hexahydrobenzene formic acid, and it adopts fixed-bed reactor, but the activity of catalyzer is low, low conversion rate, and poor to target product selectivity, the later separation of product is difficulty comparatively.
Chinese patent, publication number: CN1406666A, introduce a kind of catalyzer of preparation of hexahydrobenzoic acid by hydrogenation of benzoic acid, and this catalyzer be take acidic alumina as carrier, and take VI B or VIII family metal is 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 for preparing hexahydrobenzoic acid.Take the resource rational utilization benzoate as purpose, there is more drawback for phenylformic acid, as poor catalyst stability, it is more difficult to reclaim, environmental pollution is serious, the problems such as the hexahydrobenzoic acid productive rate is low, organically combine and realize the benzoate recycling by constant voltage reaction, pickling and rectifying, changes into the chemical hexahydrobenzoic acid of high added value.In addition, the present invention is raw material by benzoate, and the generation of side reaction while having avoided selecting hydrogenation has improved the productive rate of target product.The present invention has improved the transformation efficiency of reaction and the selectivity of hexahydrobenzoic acid, simultaneously the extending catalyst life-span, obtains 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 the potassium hydroxide reaction product in one or two or more kinds mix as raw material.
The Raney's nickel catalyst that the catalyzer of selecting hydrogenation to use in the present invention is modification.The Main Function of Raney's nickel catalyst is that to carry out benzoate aromatic ring hydrogenation saturated.At first Raney's nickel catalyst carries out dealumination reaction, increases its activity.The dealuminzation condition is: 70 ℃ of temperature of reaction, and reaction times 2h, aqueous sodium hydroxide solution concentration 30%, 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 the raw material storage tank injection carries out hydrogenation reaction.Reaction conditions is: the concentration of 160～240 ℃ of hydrogenation reaction temperature, 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 the pickling tower acid and washes, and acid used is the vitriol oil or concentrated hydrochloric acid.Obtain upper strata oily hexahydrobenzoic acid after pickling and go rectifying tower rectifying to obtain the high purity hexahydrobenzoic acid, lower floor's brine waste decontaminated water is processed.
Obtain the yield of hexahydrobenzoic acid more than 95% by method production of the present invention.
Constant voltage reactor of the present invention, pickling tower, rectifying adopt intermittently or the mode of operate continuously, flexible operation, easy.
It is raw material that the present invention adopts the benzoate aqueous solution, and the Raney's nickel of modification of take is hydrogenation catalyst, carries out hydrogenation reaction in the constant voltage reactor, and after hydrogenation reaction, product directly enters the pickling tower, and upper strata oily hexahydrobenzoic acid obtains the high purity hexahydrobenzoic acid through rectifying.The present invention produces the high hexahydrobenzoic acid of added value with benzoate; The catalyzer used has superelevation selectivity and higher hydrogenation activity.This method not only has simple to operate, can single still rhythmic reaction, again can many stills series connection successive reactions, and there is good economic benefit and prospects for commercial application.
The 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
Describe specific embodiments of the invention in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1: Raney's nickel catalyst carries out dealumination reaction, and the dealuminzation condition is: the mass ratio of 70 ℃ of temperature of reaction, 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, and the dealuminzation condition is: the mass ratio of 70 ℃ of temperature of reaction, 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, and the dealuminzation condition is: the mass ratio of 70 ℃ of temperature of reaction, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 1 modification.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 2 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 160 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 240 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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: take Raney's nickel catalyst selective hydrogenation catalyst in the constant voltage reactor of embodiment 3 modifications.Reaction conditions is: the concentration of 180 ℃ of hydrogenation reaction temperature, 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 the selectivity of hexahydrobenzoic acid is descended; 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 is more easily selected hydrogenation 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 the circulating reaction result 5 times.
5 circulation experiment results, show that the Raney's nickel catalyst of modification has good selection hydrogenation activity, and show satisfactory stability as shown in Table 3.
Claims (8)
1. a method for preparing hexahydrobenzoic acid, 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 the pickling tower, upper strata oily hexahydrobenzoic acid goes rectifying tower rectifying to obtain the high purity hexahydrobenzoic acid, and lower floor's brine waste decontaminated water is processed; Select the Raney's nickel catalyst that Hydrobon catalyst is modification, 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 that Sodium Benzoate, potassium benzoate, phenylformic acid and sodium hydroxide reaction product, phenylformic acid mix with one or two or more kinds in the potassium hydroxide reaction product; The mol ratio of phenylformic acid and sodium hydroxide or potassium hydroxide is 0.8～1.2.
3. method according to claim 2, be further characterized in that: the concentration of benzoate is 10～40%, the mass ratio of benzoate and catalyzer is 100:1～5.
4. according to claim 1,2 or 3 described methods, be further characterized in that: the Raney's nickel catalyst of described modification obtains in the following ways: at first carry out dealumination reaction, increase its activity; The dealuminzation condition is: 70 ℃ of temperature of reaction, and reaction times 2h, aqueous sodium hydroxide solution concentration 30%, the mass ratio of aqueous sodium hydroxide solution and Raney's nickel catalyst is 4-10:1.
5. according to claim 1,2 or 3 described methods, be further characterized in that: 160～240 ℃ of hydrogenation reaction temperature, hydrogen pressure 2～6MPa, reaction times 6～10h.
6. method according to claim 4, be further characterized in that: 160～240 ℃ of hydrogenation reaction temperature, hydrogen pressure 2～6MPa, reaction times 6～10h.
7. method according to claim 5, be further characterized in that: adopt single still rhythmic reaction or many stills series connection successive reaction.
8. method according to claim 6, be further characterized in that: adopt single still rhythmic reaction or many stills series connection successive reaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107365251A (en) * | 2017-08-17 | 2017-11-21 | 浙江今晖新材料股份有限公司 | A kind of preparation method of hexahydrobenzoid acid |
| 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 |
| CN103086878A (en) * | 2013-01-14 | 2013-05-08 | 浙江大学 | Preparation method of cyclohexyl compound by aromatic compound catalytic hydrogenation |
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2013
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Patent Citations (2)
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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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| 韦振雷: "雷尼镍催化剂活性简易测定及改性方法", 《木薯精细化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107365251A (en) * | 2017-08-17 | 2017-11-21 | 浙江今晖新材料股份有限公司 | A kind of preparation method of hexahydrobenzoid acid |
| 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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Effective date of registration: 20221107 Address after: No. 1-2-15, Technical Innovation Building, No. 2, East Section of Shihua North Road, Pengzhou, Chengdu, Sichuan, 611939 Patentee after: Chengdu Dayan Technology Industry Development Co.,Ltd. Address before: 116024 No. 2 Ling Road, Liaoning, Dalian Patentee before: DALIAN University OF TECHNOLOGY |