CN113087611A - Synthesis process of p-tert-butyl benzoic acid - Google Patents
Synthesis process of p-tert-butyl benzoic acid Download PDFInfo
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- CN113087611A CN113087611A CN202110399857.5A CN202110399857A CN113087611A CN 113087611 A CN113087611 A CN 113087611A CN 202110399857 A CN202110399857 A CN 202110399857A CN 113087611 A CN113087611 A CN 113087611A
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- benzoic acid
- butyl benzoic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis process of p-tert-butyl benzoic acid, which comprises the following steps: step one, preparing a load type composite catalyst; secondly, adding the supported composite catalyst obtained in the first step and p-tert-butyl toluene into a reaction kettle, and introducing oxygen to obtain a crude product of p-tert-butyl benzoic acid; step three, cooling and crystallizing the p-tert-butyl benzoic acid crude product obtained in the step two, centrifuging and spin-drying, and washing with p-tert-butyl toluene to obtain a centrifugal crude product; and step four, adding the crude tert-butyl benzoic acid obtained in the step three into toluene, heating to dissolve, adding activated carbon and diatomite for decoloring, and then cooling, crystallizing and centrifuging to obtain a refined p-tert-butyl benzoic acid. The invention has the beneficial effects that: the invention adopts the crude product to obtain a high-quality product through simple water washing, and improves the oxidation conversion rate.
Description
Technical Field
The invention relates to the field of preparation of p-tert-butyl benzoic acid, and more particularly relates to a synthesis process of p-tert-butyl benzoic acid.
Background
The demand for production of p-tert-butylbenzoic acid product has increased year by year, and the prior art has attempted to obtain a pure product by controlling the bromine and water content, with a low acetic acid content in the medium, with recycle of the catalyst, resulting in a simplified process, and with a reduced bromine content, which also reduces the corrosion of acetic acid. However, the color of the product obtained by the method is not good, the amount of acetic acid is controlled, but the recycling of the catalyst is not facilitated, and the corrosion problem still exists.
At present, the problems of equipment corrosion and complex post-treatment caused by the existence of bromide are urgently needed to be solved.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides a synthesis process of p-tert-butyl benzoic acid.
The purpose of the invention is realized by the following technical scheme.
The synthesis process of p-tert-butyl benzoic acid includes the following steps:
step one, preparing a load type composite catalyst;
adding the supported composite catalyst obtained in the step one and p-tert-butyl toluene into a reaction kettle, and introducing oxygen to obtain a crude product of p-tert-butyl benzoic acid;
step three, cooling, crystallizing and centrifugally drying the p-tert-butyl benzoic acid crude product obtained in the step two, and washing with p-tert-butyl toluene to obtain a centrifugal crude product;
step four, adding the crude tert-butyl benzoic acid obtained in the step three into toluene, heating to dissolve, adding activated carbon and diatomite for decoloring, and then cooling, crystallizing and centrifuging to obtain a refined p-tert-butyl benzoic acid;
and step five, washing the refined p-tert-butyl benzoic acid obtained in the step four with water, then washing with toluene, centrifuging and drying to obtain a finished p-tert-butyl benzoic acid product.
Preferably, the supported composite catalyst in step one comprises a titanium zeolite and a supported catalyst, which are also co-pelletized or co-extruded prior to use.
Preferably, according to any of the above schemes, the preparation method of the supported catalyst comprises the following steps:
firstly, drying silica gel at 160 ℃ for 2h, and removing adsorbed moisture and volatile substances for later use;
secondly, preparing a mixed solution of cobalt acetate and sodium bromide according to a molar ratio of 1: 3 by using deionized water, adding the silica gel under the stirring condition to form sol, and enabling the silica gel to be just capable of being equally immersed with the mixed solution of cobalt acetate and sodium bromide; standing and aging the sol for 24h at room temperature, drying the sol at 160 ℃, activating the sol for 5h at 290 ℃, and finally activating the sol for 6h at 500 ℃ to prepare the supported composite catalyst.
Preferably, in any of the above schemes, the temperature in the reaction kettle in the second step is 150 ℃, and the reaction time is 36 h.
Preferably, the amount of the supported composite catalyst added is 0.1-1.0% of the weight of the p-tert-butyltoluene.
Preferably according to any of the above embodiments, the silica gel has a surface area of 30 to 550m2/g。
Preferably, according to any of the above embodiments, the silica gel has a pore volume of 0.5 to 3.0 ml/g.
Preferably, in any of the above embodiments, the silica gel has an average particle diameter of 0.5 to 300. mu.m.
The invention has the beneficial effects that:
the p-tert-butyl benzoic acid is prepared by a high-temperature and high-pressure method by using acetic acid as a solvent and cobalt acetate as a catalyst; the invention takes the p-tert-butyl toluene as the raw material and the solvent at the same time, and adds the composite catalyst, and the normal pressure oxidation method reduces the production cost;
by applying the self-made supported composite catalyst, reagents such as acetic acid, bromide and the like are not used, so that the problems of corrosion caused by the reagents and complex post-treatment can be solved;
the self-made supported composite catalyst has high activity, easy separation, repeated use, low production cost, environmental protection and safe production;
the invention uses toluene for pouring and washing, which can greatly reduce the chroma;
the invention adopts p-tert-butyl toluene to wash and oxidize the crude product, can greatly improve the recycling times of the mother solution, can recycle 60-80 times at most, and improves the oxidation conversion rate.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
The synthesis process of p-tert-butyl benzoic acid includes the following steps:
step one, obtaining a supported composite catalyst; the preparation method of the supported catalyst comprises the following steps:
firstly, drying silica gel at 160 ℃ for 2h, and removing adsorbed moisture and volatile substances for later use;
preferably, the silica gel has a surface area of 30 to 550m2A more preferred silica gel has a surface area of from 50 to 500m2(iv) g, most preferably the surface area of the silica gel is 100-400m2/g；
The pore volume of the silica gel is from 0.5 to 3.0ml/g, more preferably the pore volume of the silica gel is from 0.5 to 2.5ml/g, most preferably the pore volume of the silica gel is from 0.8 to 2.0 ml/g;
the average particle size of the silica gel is 0.5 to 300. mu.m. The average particle size of the silica gel is more preferably 1 to 200. mu.m, and most preferably the average particle size of the silica gel is 10 to 100. mu.m.
Secondly, preparing a mixed solution of cobalt acetate and sodium bromide according to a molar ratio of 1: 3 by using deionized water, adding the silica gel under the stirring condition to form sol, and enabling the silica gel to be just capable of being equally immersed with the mixed solution of cobalt acetate and sodium bromide; standing and aging the sol for 24h at room temperature, drying the sol at 160 ℃, activating the sol for 5h at 290 ℃, and finally activating the sol for 6h at 500 ℃ to prepare the supported composite catalyst.
Secondly, adding the supported composite catalyst obtained in the first step and p-tert-butyl toluene into a reaction kettle, wherein the addition amount of the supported composite catalyst is 0.1-1.0% of the weight of the p-tert-butyl toluene, introducing oxygen, and performing oxidation reaction to obtain a crude p-tert-butyl benzoic acid;
and in the second step, oxidation reaction is carried out in the reaction kettle, the reaction temperature is 150 ℃, and the reaction time is 36 hours.
The supported composite catalyst in the step two comprises titanium zeolite and a supported catalyst, and the titanium zeolite and the supported catalyst are also subjected to co-granulation or co-extrusion molding before use; the titanium zeolite is titanium silicalite, and the titanium zeolite is TS-1.
Step three, cooling, crystallizing and centrifugally drying the p-tert-butyl benzoic acid crude product obtained in the step two, and washing with p-tert-butyl toluene to obtain a centrifugal crude product, wherein the p-tert-butyl benzoic acid is crystallized by adopting a continuous cooling or gradient cooling mode;
and step four, adding the crude tert-butyl benzoic acid obtained in the step three into toluene, heating to dissolve, adding activated carbon and diatomite for decoloring, and then cooling, crystallizing and centrifuging to obtain a refined p-tert-butyl benzoic acid.
And step five, washing the refined p-tert-butyl benzoic acid obtained in the step four with water, then washing with toluene, centrifuging and drying to obtain a finished p-tert-butyl benzoic acid product.
Example 1
1. Preparing a supported composite catalyst: firstly, drying the silica gel at 160 ℃ for 2h, and removing adsorbed moisture and volatile substances for later use; secondly, preparing a mixed solution of cobalt acetate and sodium bromide according to a molar ratio of 1: 3 by using deionized water, adding the silica gel under the stirring condition to form sol, and enabling the silica gel to be just capable of being equally immersed with the mixed solution of cobalt acetate and sodium bromide; standing and aging the sol for 24h at room temperature, drying the sol at 160 ℃, activating the sol for 5h at 290 ℃, and finally activating the sol for 6h at 500 ℃ to prepare the supported composite catalyst.
2. Synthesis of p-tert-butylbenzoic acid: adding p-tert-butyl toluene, titanium zeolite and a supported catalyst into a reaction kettle, introducing a gas mixture containing 90% of oxygen and other inert gases, and reacting at the temperature of 150 ℃ for 36 hours to obtain a crude product of p-tert-butyl benzoic acid.
3. Obtaining a p-tert-butyl benzoic acid finished product: cooling and crystallizing the crude p-tert-butylbenzoic acid, centrifugally drying, washing with p-tert-butyltoluene to obtain a centrifugal crude product, adding the crude p-tert-butylbenzoic acid into toluene, heating to dissolve, adding activated carbon and diatomite to decolor, cooling, crystallizing and centrifuging to obtain a refined p-tert-butylbenzoic acid product, washing the refined p-tert-butylbenzoic acid product with water, rinsing with toluene, centrifuging and drying to obtain a finished p-tert-butylbenzoic acid product.
The finished product of the p-tert-butyl benzoic acid prepared by the method is white crystal, has no mechanical impurities, has a melting point range of 165.5-167.5 ℃, an acid value of 314-316mgKOH/g, a purity of 99.2 percent by HPLC detection, a water content of 0.05 percent and a toluene content of 0.07 percent.
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (8)
1. The synthesis process of the p-tert-butyl benzoic acid is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing a load type composite catalyst;
adding the supported composite catalyst obtained in the step one and p-tert-butyl toluene into a reaction kettle, and introducing oxygen to obtain a crude product of p-tert-butyl benzoic acid;
step three, cooling, crystallizing and centrifugally drying the p-tert-butyl benzoic acid crude product obtained in the step two, and washing with p-tert-butyl toluene to obtain a centrifugal crude product;
step four, adding the crude tert-butyl benzoic acid obtained in the step three into toluene, heating to dissolve, adding activated carbon and diatomite for decoloring, and then cooling, crystallizing and centrifuging to obtain a refined p-tert-butyl benzoic acid;
and step five, washing the refined p-tert-butyl benzoic acid obtained in the step four with water, then washing with toluene, centrifuging and drying to obtain a finished p-tert-butyl benzoic acid product.
2. The process according to claim 1, wherein the synthesis of p-tert-butylbenzoic acid comprises the steps of: the supported composite catalyst in the first step comprises titanium zeolite and a supported catalyst, and the titanium zeolite and the supported catalyst are also co-granulated or co-extruded and molded before use.
3. The process according to claim 2, wherein the synthesis of p-tert-butylbenzoic acid comprises the steps of: the preparation method of the supported catalyst comprises the following steps:
firstly, drying silica gel at 160 ℃ for 2h, and removing adsorbed moisture and volatile substances for later use;
secondly, preparing a mixed solution of cobalt acetate and sodium bromide according to a molar ratio of 1: 3 by using deionized water, adding the silica gel under the stirring condition to form sol, and enabling the silica gel to be just capable of being equally immersed with the mixed solution of cobalt acetate and sodium bromide; standing and aging the sol for 24h at room temperature, drying the sol at 160 ℃, activating the sol for 5h at 290 ℃, and finally activating the sol for 6h at 500 ℃ to prepare the supported composite catalyst.
4. The process according to claim 3, wherein the synthesis of p-tert-butylbenzoic acid comprises the steps of: and in the second step, the temperature in the reaction kettle is 150 ℃, and the reaction time is 36 h.
5. The process according to any one of claims 1 to 4, wherein: the addition amount of the supported composite catalyst is 0.1-1.0% of the weight of the p-tert-butyl toluene.
6. The process according to claim 5, wherein the synthesis of p-tert-butylbenzoic acid comprises the steps of: the surface area of the silica gel is 30-550m2/g。
7. The process according to claim 5, wherein the synthesis of p-tert-butylbenzoic acid comprises the steps of: the pore volume of the silica gel is 0.5-3.0 ml/g.
8. The process according to claim 5, wherein the synthesis of p-tert-butylbenzoic acid comprises the steps of: the average particle size of the silica gel is 0.5-300 μm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3128147A1 (en) * | 1981-07-16 | 1983-01-27 | Dynamit Nobel Ag, 5210 Troisdorf | METHOD FOR PRODUCING AROMATIC MONOCARBONIC ACIDS |
| CN1571777A (en) * | 2001-10-19 | 2005-01-26 | 阿克奥化学技术有限公司 | Direct epoxidation process using a mixed catalyst system |
| CN1620443A (en) * | 2001-11-29 | 2005-05-25 | 阿克奥化学技术有限公司 | Direct epoxidation process using a mixed catalyst system pretreated with a bromide containing agent |
| CN101648866A (en) * | 2009-09-18 | 2010-02-17 | 刘忠春 | Preparation technology of p-tert-butyl benzoic acid |
| CN102617335A (en) * | 2012-03-16 | 2012-08-01 | 宿迁科思化学有限公司 | Process for synthesizing p-tert-butylbenzoic acid |
| CN103274928A (en) * | 2013-04-24 | 2013-09-04 | 菏泽远东强亚化工科技有限公司 | Production method of p-tert-butyl benzoic acid |
-
2021
- 2021-04-14 CN CN202110399857.5A patent/CN113087611A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3128147A1 (en) * | 1981-07-16 | 1983-01-27 | Dynamit Nobel Ag, 5210 Troisdorf | METHOD FOR PRODUCING AROMATIC MONOCARBONIC ACIDS |
| CN1571777A (en) * | 2001-10-19 | 2005-01-26 | 阿克奥化学技术有限公司 | Direct epoxidation process using a mixed catalyst system |
| CN1620443A (en) * | 2001-11-29 | 2005-05-25 | 阿克奥化学技术有限公司 | Direct epoxidation process using a mixed catalyst system pretreated with a bromide containing agent |
| CN101648866A (en) * | 2009-09-18 | 2010-02-17 | 刘忠春 | Preparation technology of p-tert-butyl benzoic acid |
| CN102617335A (en) * | 2012-03-16 | 2012-08-01 | 宿迁科思化学有限公司 | Process for synthesizing p-tert-butylbenzoic acid |
| CN103274928A (en) * | 2013-04-24 | 2013-09-04 | 菏泽远东强亚化工科技有限公司 | Production method of p-tert-butyl benzoic acid |
Non-Patent Citations (1)
| Title |
|---|
| 王基铭: "《石油化工技术进展》", 30 April 2002, 中国石化出版社 * |
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