CN113801014A - Preparation process of phenylacetic acid - Google Patents
Preparation process of phenylacetic acid Download PDFInfo
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- CN113801014A CN113801014A CN202110870467.1A CN202110870467A CN113801014A CN 113801014 A CN113801014 A CN 113801014A CN 202110870467 A CN202110870467 A CN 202110870467A CN 113801014 A CN113801014 A CN 113801014A
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- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229960003424 phenylacetic acid Drugs 0.000 title claims abstract description 43
- 239000003279 phenylacetic acid Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 230000006315 carbonylation Effects 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229940073608 benzyl chloride Drugs 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- BASMANVIUSSIIM-UHFFFAOYSA-N 1-chloro-2-(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1Cl BASMANVIUSSIIM-UHFFFAOYSA-N 0.000 claims description 3
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 16
- 230000007062 hydrolysis Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 108091006629 SLC13A2 Proteins 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JAUFWTSSYRTLLB-UHFFFAOYSA-N (2-phenylacetyl) 2-phenylacetate Chemical compound C=1C=CC=CC=1CC(=O)OC(=O)CC1=CC=CC=C1 JAUFWTSSYRTLLB-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DULCUDSUACXJJC-UHFFFAOYSA-N Ethyl phenylacetate Chemical compound CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 1
- ITIONVBQFUNVJV-UHFFFAOYSA-N Etomidoline Chemical compound C12=CC=CC=C2C(=O)N(CC)C1NC(C=C1)=CC=C1OCCN1CCCCC1 ITIONVBQFUNVJV-UHFFFAOYSA-N 0.000 description 1
- 229910004721 HSiCl3 Inorganic materials 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- KRMDCWKBEZIMAB-UHFFFAOYSA-N amitriptyline Chemical compound C1CC2=CC=CC=C2C(=CCCN(C)C)C2=CC=CC=C21 KRMDCWKBEZIMAB-UHFFFAOYSA-N 0.000 description 1
- 229960000836 amitriptyline Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BULOCEWDRJUMEL-UHFFFAOYSA-N benzene formaldehyde Chemical compound C=O.C1=CC=CC=C1.C=O BULOCEWDRJUMEL-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001037 epileptic effect Effects 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- DDBREPKUVSBGFI-UHFFFAOYSA-N phenobarbital Chemical compound C=1C=CC=CC=1C1(CC)C(=O)NC(=O)NC1=O DDBREPKUVSBGFI-UHFFFAOYSA-N 0.000 description 1
- 229960002695 phenobarbital Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 230000001624 sedative effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940006198 sodium phenylacetate Drugs 0.000 description 1
- OWMHBKYAOYHOQK-UHFFFAOYSA-N sodium;methanidylbenzene Chemical compound [Na+].[CH2-]C1=CC=CC=C1 OWMHBKYAOYHOQK-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a phenylacetic acid preparation process, which comprises the following steps: (S1) adding water, raw materials, solvent and catalyst into a premixing tank for premixing; (S2) introducing carbon monoxide into the reaction tower, transferring the mixed liquid (S1) into the reaction tower, carrying out carbonylation synthesis reaction, and separating unreacted carbon monoxide from the materials in the reaction tower through a gas-liquid separation device; (S3) carrying out water-oil separation on the reaction liquid obtained in the step (S2) to respectively obtain a water phase and an oil phase, wherein the oil phase mainly contains a solvent and a catalyst and returns to (S1); (S4) transferring the water phase to a crystallization kettle, adding hydrochloric acid for acidification, cooling the reaction material to 15-20 ℃ after acidification, and crystallizing and separating out phenylacetic acid; (S5) centrifuging and washing the crystallized product obtained in the step (S4) to obtain a wet product of phenylacetic acid; (S6) drying the wet phenylacetic acid product obtained in the step (S5) by a fluidized bed to obtain the phenylacetic acid product. The scheme can recover the reaction catalyst, reduce the cost and reduce the discharge of three wastes.
Description
Technical Field
The invention relates to a phenylacetic acid synthesis technology, in particular to a phenylacetic acid preparation process.
Background
Phenylacetic acid is an important fine chemical intermediate for medicines, spices and the like, and belongs to the field of fine chemical engineering. In the medical aspect, the phenylacetic acid is mainly used for producing penicillin, and is also used for preparing sedative anti-depression drug amitriptyline, epileptic drug phenobarbital and the like. In the industrial aspect, phenylacetic acid is commonly used for preparing high-performance curing agents for engineering plastics, fluorescent whitening agents, developers for fuel and photosensitive materials, and the like. In addition, phenylacetic acid is edible spice which is allowed to be used in China, and is mainly used for producing foods, detergents, cleaning agents, cosmetics, tobaccos and beverages.
The synthesis method of phenylacetic acid is dozens of methods, and some methods have no great practical significance because the price of main raw materials is higher or close to that of phenylacetic acid products, such as a acetophenone method, a benzyl alcohol method, a phenylacetic acid ethyl ester hydrolysis method, a benzaldehyde method, a trichloroethylene hydrolysis method and the like. The production process which is industrially adopted or has industrial value mainly comprises the following steps: benzyl cyanide hydrolysis, CO carbonylation, benzene-acetic anhydride, ethyl benzene oxidation, benzyl sodium, benzene-formaldehyde carbonylation, phenylacetamide hydrolysis (Vigregore de), benzyl chloride-CO 2 electrolysis, and industrial production mainly comprises benzyl cyanide hydrolysis and CO carbonylation.
After 2000 years, there are dozens of phenylacetic acid manufacturers in China, and most of the phenylacetonitrile hydrolysis methods are adopted, wherein carbonylation process routes are adopted by German resource fine chemical plants in Taixing city, silver electrochemical limited company in Jining, SulIi chemical plants in Heilongjiang, Shijiazhuang chemical plants and the like. The technology of the hydrolysis method of the phenylacetonitrile falls behind, the production cost is high, the pollution of three wastes is serious, the product quality is poor, the use of downstream products is influenced due to the existence of toxic cyanide, and the method is eliminated by developed countries. In order to replace the benzyl cyanide hydrolysis method, some domestic enterprises simulate foreign technologies and successfully develop the process route of the carbonylation method. However, the traditional carbonylation method must add a cocatalyst (such as ferroferric oxide and the like) and a phase transfer catalyst (such as quaternary ammonium salt and the like), catalytic metals must be prepared again after each batch of reaction, so that production equipment is more, a process route is long, the scale of a device is small, and with the reduction of the raw material cost of the phenylacetonitrile hydrolysis method and the enlargement of the scale of the device, the carbonylation method gradually loses the cost advantage in the competition of the phenylacetonitrile hydrolysis method and finally becomes dull. With the successive shut-down or production change of only a few domestic carbonylation industrial devices, the hydrolysis of phenylacetonitrile has been the pattern for a whole day in the phenylacetic acid industry. Because of the monopoly advantage of the raw materials of a few enterprises, the benzyl cyanide hydrolysis method gradually forms oligopolism, but serious three-waste pollution still can not be treated, and the quality and the application field of the product are limited.
The carbonylation method is adopted for industrially producing the phenylacetic acid products in foreign Germany, Japan, Italy and other countries. At the end of the last ninety th century, a plurality of domestic scientific research institutions research the carbonylation process, and a plurality of benzyl chloride carbonylation industrial devices are successively built. The key point of the method lies in the selection and recovery of the catalyst, the catalyst mainly adopted in China is cobalt carbonyl, and the cobalt catalyst has a plurality of defects, such as: the catalyst is difficult to recover, the catalyst is easy to be poisoned and inactivated, the production cost is high, and the like, and the working procedures of producing the phenylacetic acid by the domestic carbonylation method process technology are shut down or transferred.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a phenylacetic acid preparation process, which realizes the recycling of a catalyst, and has the advantages of easily available raw materials, mild reaction conditions, high yield, automatic, continuous and stable operation, large production scale, high product quality, environmental friendliness and no pollution.
In order to achieve the purpose, the invention provides a phenylacetic acid preparation process, which comprises the following steps: (S1) adding water, raw materials, solvent and catalyst into a premixing tank for premixing; wherein, the raw material comprises 50 percent of sodium hydroxide as a raw material A and one of benzyl chloride, p-chlorobenzyl chloride or o-chlorobenzyl chloride as a raw material B; solvent C is one of benzene, toluene or xylene, and the ratio of water: raw material A: raw material B: catalyst: the mass ratio of the solvent C is 5.0-6.5: 1-2: 0.8-1.2: 0.15-0.5: 3-4.5. (ii) a Introducing carbon monoxide into the reaction tower (S2), transferring the mixed solution of (S1) into the reaction tower, and carrying out carbonylation synthesis reaction, wherein the chemical reaction formula of the reaction raw material is benzyl chloride is C6H5CH2Cl+2Na0H+CO→C6H5CH2C00Na+NaC1+H20, separating unreacted carbon monoxide from the materials in the reaction tower through a gas-liquid separation device; (S3) carrying out water-oil separation on the reaction liquid obtained in the step (S2) to respectively obtain a water phase and an oil phase; (S4) transferring the water phase to a crystallization kettle, adding hydrochloric acid for acidification, wherein the acidification reaction formula is C6H5CH2C00Na+HC1→C6H5CH2C00H + NaC1, cooling the reaction material to 15-20 ℃ after acidification, and crystallizing and separating out phenylacetic acid; (S5) centrifuging and washing the crystallized product obtained in the step (S4) to obtain a wet product of phenylacetic acid; (S6) drying the wet phenylacetic acid product obtained in the step (S5) by a fluidized bed to obtain the phenylacetic acid product.
Further, the solvent of the step (S1) is toluene, water: raw material A: raw material B: catalyst: the mass ratio of the solvent C is 5.7:1.3:1.0:0.3:3.7, and the oil phase obtained in the step (S3): the oil phase, including the solvent and catalyst, is returned (S1).
Further, after filtering the centrifugal washing mother liquor generated in the step (S5), collecting fine microcrystalline phenylacetic acid precipitate suspension, and returning the collected fine microcrystalline phenylacetic acid precipitate suspension to the crystallization kettle for recrystallization.
Further, adding 50% sodium hydroxide solution into the clear liquid obtained after the centrifugal washing mother liquor is filtered, carrying out acid-base neutralization until the pH value is 10, transferring the clear liquid to a saline water storage tank, transferring the clear liquid to MVR (mechanical vapor recompression) for evaporation and concentration to obtain a sodium chloride crystal mixed liquid, and carrying out centrifugal washing to obtain a sodium chloride byproduct.
Further, the evaporation condensed water of the MVR enters an evaporation condensing tank for storage, and the condensed water in the evaporation condensing tank is adsorbed and purified by resin and then is used as washing reuse water, water for a steam generator and make-up water for a circulating water system in the production process.
Further, the carbon monoxide separated by the liquid separation device in the step (S2) and the pressure-regulating exhaust gas of the reaction tower are returned to the carbonylation reaction tower through a pipeline for recycling.
Further, in the carbonylation synthesis reaction of the step (S2), the reaction conditions are 70 to 75 ℃, 2MPa, and the reaction time is about 80 to 90 min.
Further, the chemical formula of the catalyst in the step (S1) is:
the invention has the beneficial effects that: compared with a hydrolysis method of phenylacetonitrile, the method has completely different raw materials and process routes, avoids highly toxic raw materials and highly toxic intermediate products, and solves the problem that waste salt and waste water are difficult to treat. Compared with the traditional carbonylation method, the catalyst of the traditional carbonylation method cannot be recycled, and needs to be precipitated, separated and prepared again; the traditional carbonylation method usually selects a soluble alcohol solvent, and can not realize 'water and oil' phase separation, so that the solvent, unreacted benzyl chloride and brine are very complicated to treat, the product quality and the brine quality are poor, the production scale is small, the cost is high, and the market competition advantage is lacked.
Drawings
FIG. 1 is a process flow diagram of a phenylacetic acid production process of the present invention.
FIG. 2 is a chemical formula of the catalyst in the present invention.
Detailed Description
As shown in fig. 1 and 2, the invention provides a phenylacetic acid preparation process, which comprises the following steps:
example one
(S1) preheating a premixing tank to 70-75 ℃, adding water into the premixing tank, and premixing the raw material A, the raw material B, the catalyst and the solvent C in a mass ratio of 5.7:1.3:1.0:0.3: 3.7; the raw material includes a raw material a which is a 50% sodium hydroxide solution, a raw material B which is one of benzyl chloride, p-chlorobenzyl chloride and o-chlorobenzyl chloride, in this embodiment, benzyl chloride is preferred, a solvent C which is one of benzene, toluene or xylene is preferred, and in this embodiment, toluene is preferred as the solvent.
(S2) introducing carbon monoxide into the reaction tower, transferring the mixed liquid (S1) into the reaction tower, stirring and uniformly mixing, carrying out carbonylation synthesis reaction, reacting at 70-75 ℃ under 2MPa for about 80-90 min, separating unreacted CO from the materials through a gas-liquid separation device after the reaction is finished, and returning the separated CO gas phase and the pressure-regulating exhaust gas of the reaction tower to the carbonylation reaction tower through a pipeline for recycling.
(S3) carrying out water-oil separation on the reaction liquid obtained in the step (S2) to respectively obtain a water phase and an oil phase; and (3) transferring the oil phase into a standing tank, standing for natural layering, extracting 10% of the volume of the upper layer of the oil phase in the standing tank, transferring into a toluene tower, and transferring the rest into a recovery tank. Condensing the toluene distilled out of the toluene tower at 120 ℃ under normal pressure, and then sending the condensed toluene into a solvent recovery tank, wherein the toluene in the recovery tank is used for recovering and adding the toluene into the premixing tank in the step (S1); and transferring the residual tower bottom liquid after the toluene tower distillation to a batch tower process to refine and distill the benzyl alcohol byproduct.
Wherein, the batch tower procedure comprises a first batch tower and a second batch tower, the bottom liquid of the tower firstly transfers to the first batch tower, the benzyl chloride is rectified at 145 ℃ and minus 0.098MPa, and the benzyl chloride transfers to a recovery tank; the bottom liquid of the first batch tower is transferred to a second batch tower, and the benzyl alcohol byproduct is rectified at 150 ℃ and-0.098 MPa.
(S4) transferring the water phase to a crystallization kettle, adding excessive 31% hydrochloric acid for acidification, acidifying sodium phenylacetate into phenylacetic acid and simultaneously producing sodium chloride as a byproduct, cooling the reaction material to 15-20 ℃ after acidification, and crystallizing and separating out the phenylacetic acid;
(S5) centrifugal washing is carried out on the crystallized product obtained in the step (S4) to obtain a wet product of phenylacetic acid. (S5), filtering the generated centrifugal washing mother liquor, collecting fine microcrystalline phenylacetic acid precipitate suspension, and returning the fine microcrystalline phenylacetic acid precipitate suspension to the crystallization kettle for recrystallization. And (3) centrifugally washing the clear liquid obtained after the mother liquor is filtered, adding 50% of sodium hydroxide solution to perform acid-base neutralization until the pH value is 10, transferring to a saline water storage tank, transferring to MVR (mechanical vapor recompression) to perform evaporation concentration to obtain a sodium chloride crystal mixed solution, and centrifugally washing to obtain a sodium chloride byproduct.
The evaporation condensed water of MVR enters an evaporation condensing tank for storage, and the condensed water in the evaporation condensing tank is adsorbed and purified by resin and then is used as washing reuse water, water for a steam generator and make-up water for a circulating water system in the production process.
(S6) drying the wet phenylacetic acid product obtained in the step (S5) by airflow at 60 ℃ through a fluidized bed to obtain the phenylacetic acid product.
Example two
Different from the first embodiment, the water, the raw material A, the raw material B, the catalyst and the solvent C are premixed in a mass ratio of 5.: 1: 0.8: 0.15: 3.
EXAMPLE III
Different from the first embodiment, the water, the raw material A, the raw material B, the catalyst and the solvent C are premixed in a mass ratio of 6.5.: 2: 1.2: 0.5: 4.5.
the preparation method of the catalyst comprises the following steps: (1) copolymer (II) and Os (SPh3)4 were mixed in THF, followed by addition of hexane to obtain a coagulated mixture, wherein the reaction volume ratio was: copolymer (II): os (SPh3) 4: THF: hexane 10: 1: 3: 4.
reaction proportion: copolymer (II): os (SPh3) 4: THF: hexane 10: 1: 3: 4
Wherein x is 70-75, y is 6, z is 3-5, and w is 16-18. Preferably, x is 71, y is 8, z is 4, and w is 17.
(2) Filtering the mixture, washing the filtrate with 99.5% n-hexane having a molar ratio of 4 times that of the copolymer (II), and drying the filtrate;
(3) crosslinking the filtrate at 120 ℃ for 2 hours in a solvent-free state;
(4) refiltering, the filtrate was washed with 2 times the molar amount of copolymer (II) in 99.5% THF and then dried;
(5) adding HSiCl3 with the concentration of 99.5% of copolymer (II) of 1.5 times the mol number of the filtrate treated in the step (4), and reacting in a mixed solvent of toluene with the concentration of 99.5% of copolymer (II) of 3 times the mol number of the copolymer (II) and triethylamine with the concentration of 99.5% of copolymer (II) of 2.6 times the mol number of the copolymer (II);
(6) after filtration, the filtrate was washed with 1.5-fold molar amount of copolymer (II) in 99.5% THF, and then dried to obtain the objective product.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (8)
1. A preparation process of phenylacetic acid is characterized by comprising the following steps:
(S1) adding water, raw materials, solvent and catalyst into a premixing tank for premixing;
wherein, the raw material comprises 50 percent of sodium hydroxide as a raw material A and one of benzyl chloride, p-chlorobenzyl chloride or o-chlorobenzyl chloride as a raw material B; solvent C is one of benzene, toluene or xylene, and the ratio of water: raw material A: raw material B: catalyst: the mass ratio of the solvent C is 5.0-6.5: 1-2: 0.8-1.2: 0.15-0.5: 3-4.5.
(S2) introducing carbon monoxide into the reaction tower, transferring the mixed liquid (S1) into the reaction tower, carrying out carbonylation synthesis reaction, and separating unreacted carbon monoxide from the materials in the reaction tower through a gas-liquid separation device;
(S3) carrying out water-oil separation on the reaction liquid obtained in the step (S2) to respectively obtain a water phase and an oil phase, wherein the oil phase mainly contains a solvent and a catalyst and returns to (S1);
(S4) transferring the water phase to a crystallization kettle, adding hydrochloric acid for acidification, cooling the reaction material to 15-20 ℃ after acidification, and crystallizing and separating out phenylacetic acid;
(S5) centrifuging and washing the crystallized product obtained in the step (S4) to obtain a wet product of phenylacetic acid;
(S6) drying the wet phenylacetic acid product obtained in the step (S5) by a fluidized bed to obtain the phenylacetic acid product.
2. The process according to claim 1, wherein: the solvent of the step (S1) is toluene, water: raw material A: raw material B: catalyst: the mass ratio of the solvent C is 5.7:1.3:1.0:0.3: 3.7.
3. The process according to claim 1, wherein: and (4) filtering the centrifugal washing mother liquor generated in the step (S5), collecting fine microcrystalline phenylacetic acid precipitate suspension, and returning the fine microcrystalline phenylacetic acid precipitate suspension to the crystallization kettle for recrystallization.
4. The process according to claim 3, wherein: and adding 50% sodium hydroxide solution into the clear liquid obtained after the centrifugal washing mother liquor is filtered, carrying out acid-base neutralization until the pH value is 10, transferring to a saline water storage tank, transferring to MVR (mechanical vapor recompression) for evaporation and concentration to obtain a sodium chloride crystal mixed solution, and carrying out centrifugal washing to obtain a sodium chloride byproduct.
5. The process according to claim 4, wherein: the evaporation condensate water of the MVR enters an evaporation condensate tank for storage, and the condensate water of the evaporation condensate tank is adsorbed and purified by resin and then is used as washing reuse water, water for a steam generator and make-up water for a circulating water system in the production process.
6. The process according to claim 1, wherein: and (S2) returning the carbon monoxide separated by the liquid separation device in the step (S2) and the pressure-regulating exhaust gas of the reaction tower to the carbonylation reaction tower for recycling through a pipeline.
7. The process according to claim 1, wherein: in the carbonylation synthesis reaction of the step (S2), the reaction condition is 70-75 ℃, the reaction pressure is 2MPa, and the reaction time is about 80-90 min.
8. The process according to claim 1, wherein: the chemical formula of the catalyst in the step (S1) is:
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107698433A (en) * | 2017-09-12 | 2018-02-16 | 潍坊滨海石油化工有限公司 | The preparation method of phenylacetic acid |
| CN108997106A (en) * | 2018-07-30 | 2018-12-14 | 麻城市天恒商贸有限公司 | The preparation method of phenylacetic acid |
| CN109438215A (en) * | 2018-11-12 | 2019-03-08 | 西南化工研究设计院有限公司 | A kind of method of carbonylation synthesis phenylacetic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698433A (en) * | 2017-09-12 | 2018-02-16 | 潍坊滨海石油化工有限公司 | The preparation method of phenylacetic acid |
| CN108997106A (en) * | 2018-07-30 | 2018-12-14 | 麻城市天恒商贸有限公司 | The preparation method of phenylacetic acid |
| CN109438215A (en) * | 2018-11-12 | 2019-03-08 | 西南化工研究设计院有限公司 | A kind of method of carbonylation synthesis phenylacetic acid |
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