CN114835575A - Method for producing chloroacetic acid mixed acid and trichloro-acetyl chloride by using residues in chloroacetyl chloride production process - Google Patents
Method for producing chloroacetic acid mixed acid and trichloro-acetyl chloride by using residues in chloroacetyl chloride production process Download PDFInfo
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- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229940106681 chloroacetic acid Drugs 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 title claims abstract description 20
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 title claims abstract description 18
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 title abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000460 chlorine Substances 0.000 claims abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 235000019614 sour taste Nutrition 0.000 claims abstract description 4
- 235000019640 taste Nutrition 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 238000005660 chlorination reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000498 cooling water Substances 0.000 claims description 3
- 230000020169 heat generation Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 14
- 150000008064 anhydrides Chemical class 0.000 description 9
- 239000003814 drug Substances 0.000 description 8
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 238000005485 electric heating Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- RQHMQURGSQBBJY-UHFFFAOYSA-N (2,2-dichloroacetyl) 2,2-dichloroacetate Chemical compound ClC(Cl)C(=O)OC(=O)C(Cl)Cl RQHMQURGSQBBJY-UHFFFAOYSA-N 0.000 description 1
- PNVPNXKRAUBJGW-UHFFFAOYSA-N (2-chloroacetyl) 2-chloroacetate Chemical compound ClCC(=O)OC(=O)CCl PNVPNXKRAUBJGW-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
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- TURHTASYUMWZCC-UHFFFAOYSA-N Olaquindox [BAN:INN] Chemical compound C1=CC=C2N([O-])C(C)=C(C(=O)NCCO)[N+](=O)C2=C1 TURHTASYUMWZCC-UHFFFAOYSA-N 0.000 description 1
- 208000007107 Stomach Ulcer Diseases 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000012443 analytical study Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- -1 azo disperse red Chemical compound 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 208000015114 central nervous system disease Diseases 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical class NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 201000005917 gastric ulcer Diseases 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- HSPSCWZIJWKZKD-UHFFFAOYSA-N n-chloroacetamide Chemical compound CC(=O)NCl HSPSCWZIJWKZKD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229950010210 olaquindox Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 229960002957 praziquantel Drugs 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 201000004409 schistosomiasis Diseases 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/64—Separation; Purification; Stabilisation; Use of additives
-
- 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
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing chloroacetic acid mixed acid and trichloro-acetyl chloride by utilizing residues in a production process of chloroacetyl chloride, belonging to the technical field of chemical industry. In the method, the chloroacetic acid chloride is introduced with chlorine under the condition of taking sulfur as a catalyst in the production process of chloroacetic chloride, the residue is black tar-like solid at normal temperature, has fluidity above 80 ℃, and has sharp sour taste and rotten apple taste. The invention analyzes and determines the substance components and the content of the residues in the production process of the chloroacetyl chloride, and obtains the chloroacetic acid mixed acid which has lower moisture content and can be directly used through quantitative hydrolysis. The invention takes the residues in the production process of the chloracetyl chloride as raw materials to produce the chloracetic acid mixed acid and the trichloro-acetyl chloride, thereby not only solving the problem of environmental pollution caused by waste, but also utilizing the waste and reducing the cost of manufacturing products.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for producing chloroacetic acid mixed acid and trichloroacetyl chloride by using residues in a production process of chloroacetyl chloride.
Background
Chloroacetyl chloride is an important organic intermediate, and has high reaction activity, so that the chloroacetyl chloride serving as an acylating agent has higher superiority in the yield and quality of a synthetic product than other acylating methods, and is widely used for the synthesis of pesticides, medicines, dyes, auxiliaries, extraction solvents, refrigerants, fire extinguishing agents, lubricating oil additives, military toxic gases and the like.
In the field of pesticides, chloroacetyl chloride is mainly used for synthesizing dithio-and monothio-phosphate esters as insecticides and acaricides, and chloroacetamides as herbicides. In medicine, chloroacetyl chloride can be used for synthesizing medicaments for treating gastric ulcer, cardiovascular diseases, anticancer medicaments, central nervous system diseases, antibiotic medicaments and the like. In addition, chloroacetyl chloride is also used for preparing schistosomiasis killing praziquantel medicaments, preparing platelet active anti-agent tetrahydrofuran medicaments, other medicaments, medicinal intermediates and the like.
In the aspect of dyes, the method can be used for synthesizing N-chloroacetamide intermediates, synthesizing neutral brilliant blue GL dyes, special dyes for polyester fibers, azo disperse red and the like.
In the aspect of food and feed additives, chloroacetyl chloride is mainly used for synthesizing various amino acids and can also be used for producing the growth promoter olaquindox for livestock and poultry.
In other aspects, chloroacetyl chloride can be used as a catalyst for polymerization, a stabilizer and modifier for polymers, a surface treatment agent, a surface coating for preventing metal materials from splashing during fusion welding, a lubricating oil additive, a bleaching agent, a metal complexing agent, a surfactant, and the like.
In the industrial production of chloroacetyl chloride, chloroacetic acid is generally introduced with chlorine gas in the presence of sulfur as a catalyst. The method has the advantages of high product purity, less investment, simple operation and easy mastering, so the process is generally applied at present. The defect is that the residue is about 5 percent of the yield, and the residue is not researched and solved so far, and the fundamental reason is that whether available substances exist in the residue or not is unknown. Chloroacetyl chloride generates residue in the production process, is black tar-like solid at normal temperature, has fluidity above 80 ℃, and has pungent sour taste and rotten apple taste. Generally, the treatment is difficult, and the treatment cost is high only by neutralizing the waste liquor with strong alkali and then burning the waste liquor. The chloroacetyl chloride has large market demand and large yield, the annual domestic yield of the chloroacetyl chloride is about 10 ten thousand tons, and residues in the production process are about 5 percent, namely about 5000 tons every year. The residues are treated as hazardous wastes before, and the treatment cost is too high.
Disclosure of Invention
In order to solve the above problems, after an analytical study, it was confirmed that the main component of the residue was a mixed acid anhydride, which accounted for about 90% of the total amount of the residue, and the composition in which various chloroacetic acids were distributed was analyzed, i.e., the monochloroacetic acid content was 94%, dichloroacetic acid was about 5%, and trichloroacetic acid was about 0.5%. About 5 percent of the mixed anhydride accounts for about 90 percent of the total amount, and about 5 percent of the mixed anhydride is carbonized substance and chloracetyl chloride accounts for about 5 percent.
Based on the resolved composition being a mixed acid, we speculate that the mixed anhydride in the residue includes: monochloroacetic anhydride, dichloroacetic anhydride, mixed anhydrides of monochloroacetic acid and dichloroacetic acid, mixed anhydrides of monochloroacetic acid and trichloroacetic acid, and other low-content mixed anhydrides. Since the mixed anhydride is not a pure substance, the mixed anhydride is not directly used after extraction, only the mixed anhydride is decomposed into various chloroacetic acid mixtures, and the chloroacetic acid mixtures can only be used as raw materials for producing trichloroacetyl chloride or trichloroacetic acid.
The extraction of the mixed acid anhydride adopts organic solvent extraction, and in principle, the solvent capable of dissolving the mixed acid anhydride can be used as the solvent for extraction, but the solvent capable of reacting with the acid anhydride can not be used, such as alcohol solvents such as methanol, ethanol and the like. Therefore, the solvent can be selected from ethyl acetate, benzene, toluene, xylene, chloroform, dichloroethane, etc. It is recommended not to use aromatic solvents, which are more toxic.
The mixed acid anhydride is hydrolyzed by adding water after being extracted, the mixed acid anhydride is converted into mixed acid, the hydrolysis is more thorough when the water amount is larger in principle, but actually, the mixed acid with large water content is not beneficial to production and use, and the mixed acid cannot be directly used as a raw material for producing trichloroacetic acid and trichloroacetyl chloride due to too much water content, and the raw material use requirement for producing the trichloroacetic acid and the trichloroacetyl chloride can be met only after the water content is less than 0.5% by dehydration.
The patent describes that mixed acid anhydride is hydrolyzed quantitatively, the water content of the obtained mixed acid is less than 0.5%, and meanwhile, in the hydrolysis process, the hydrolysis temperature is controlled to be not lower than 60 ℃, so that the situation that the hydrolysis reaction cannot be completely initiated at low temperature and an instant explosion reaction is possibly generated to generate potential safety hazards is prevented.
In the treatment of the reaction residue, chloroacetyl chloride of about 5% is hydrolyzed together, which is advantageous in terms of treatment cost.
The invention discloses a method for producing chloroacetic acid mixed acid by using residues in a chloroacetyl chloride production process, which is characterized in that in the chloroacetyl chloride production process, chloroacetic acid is introduced with chlorine under the condition of taking sulfur as a catalyst, the residues are black tar-like solids at normal temperature, have fluidity above 80 ℃, and have sharp sour taste and rotten apple taste.
In some preferred embodiments of the present invention, the following steps are included:
s01, taking the residue, dissolving the residue in a solvent, and filtering to obtain a filtrate;
s02, adding water into the filtrate to perform hydrolysis reaction;
s03, distilling off the solvent.
In some preferred embodiments of the present invention, in S01, the solvent is one or more of ethyl acetate, toluene, or chloroform.
In some preferred embodiments of the invention, in S01, the dissolving step is performed in a flask, the ratio of the residue to the solvent being 300 g: 700 and 800 g.
In some preferred embodiments of the present invention, in S01, the dissolving step is performed in a reaction kettle, and the ratio of the residue to the solvent is 1800 kg: 4000 and 5000 kg.
In some preferred embodiments of the present invention, the dissolving is performed by heating to 50-80 ℃ in S01.
In some preferred embodiments of the present invention, in S02, the filtrate is heated to not less than 60 ℃, and then water is added to perform the hydrolysis reaction.
The second aspect of the invention discloses a method for preparing trichloroacetyl chloride by using chloroacetic acid mixed acid produced by the method of the first aspect, which comprises the following steps:
s11, adding the mixed chloroacetic acid and sulfur into a reaction kettle, heating, and introducing chlorine gas until all the chlorine gas is dissolved;
s12, heating, and stopping chlorine introduction until the color of the reflux liquid turns yellow;
s13, cooling, adding pyridine, heating, introducing chlorine again until the chlorination reaction liquid does not absorb chlorine any more, and stopping introducing chlorine;
and S14, continuously heating to drive out free chlorine in the reaction liquid, then cooling, and transferring the chlorination liquid to a rectification system for rectification to obtain the trichloroacetyl chloride.
In some preferred embodiments of the invention, the weight ratio of the mixed chloroacetic acid, sulfur and pyridine is 2000: (350-370):(6-8).
In some preferred embodiments of the present invention, in S11, the temperature is raised to 48-55 c,
in some preferred embodiments of the present invention, in S12, the temperature is raised to 65-75 ℃.
In some preferred embodiments of the present invention, in S13, the temperature is reduced to 38-45 ℃.
In some preferred embodiments of the present invention, in S13, the temperature is raised to 60 ℃ to 65 ℃.
In some preferred embodiments of the present invention, in S14, the temperature is reduced to 35 ℃ to 40 ℃.
In some preferred embodiments of the invention, temperature control of the temperature increase and decrease is performed by switching condenser cooling water, switching and jacket steam or reaction heat generation.
The beneficial technical effects of the invention are as follows:
(1) the invention analyzes and determines the substance components and the content of the residues in the production process of the chloroacetyl chloride, and obtains the chloroacetic acid mixed acid which has lower moisture content and can be directly used through quantitative hydrolysis.
(2) The invention takes the residues in the production process of the chloracetyl chloride as raw materials to produce the chloracetic acid mixed acid and the trichloro-acetyl chloride, thereby not only solving the problem of environmental pollution caused by waste, but also utilizing the waste and reducing the cost of manufacturing products.
(3) In the invention, the hydrolysis temperature of the residue in the solvent is not lower than 60 ℃, when the hydrolysis temperature is lower than 60 ℃, the reaction speed is slow, more materials are easy to drop, more unreacted materials are accumulated in the reaction kettle, once the temperature in the kettle exceeds 60 ℃, the reaction can be instantly generated, and the reaction heat can not be instantly transferred to cause explosion.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The slow temperature rise is that the temperature rise speed is lower than 5 ℃/min.
Unless otherwise specified, the examples and comparative examples are parallel tests with the same components, component contents, preparation steps, preparation parameters.
Example 1
A2000 ml four-necked flask was equipped with an electric stirrer, a thermometer, and a reflux condenser. 300g of chloroacetyl chloride production residue was weighed into a four-necked flask, and 750 g of ethyl acetate solvent was added. Heating with electric heating jacket under stirring, slowly heating to 50 deg.C, filtering while hot, removing insoluble impurities, and collecting filtrate.
The filtrate was put into a 2000ml four-necked reaction flask again, equipped with an electric stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and 28.5 g of water was weighed into the constant pressure dropping funnel. Under the condition of continuously stirring, heating by using an electric heating sleeve, slowly heating to 60 ℃, then slowly dropwise adding water in a constant-pressure dropping funnel into a reaction bottle for hydrolysis reaction, wherein the reaction is finished after about 1 hour.
Changing the reaction device into a distillation device, slowly heating to evaporate the ethyl acetate solvent under continuous stirring, changing into reduced pressure distillation when the solvent is not removed at 100 ℃, gradually increasing the vacuum degree according to the distillation amount until the vacuum degree reaches-0.095 MPa and the distillation is not removed at 100 ℃. The bottom material of the recovery kettle is mixed with 313 g of chloroacetic acid.
Example 2
A2000 ml four-neck flask was equipped with an electric stirrer, a thermometer and a reflux condenser, and 300g of chloroacetyl chloride production residue was weighed and put into the flask, and 750 g of toluene solvent was put into the flask. Heating with electric heating jacket under stirring, slowly heating to 80 deg.C, filtering while hot, removing insoluble impurities, and collecting filtrate.
The filtrate was put into a 2000ml four-necked reaction flask again, equipped with an electric stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and 28.5 g of water was weighed into the constant pressure dropping funnel. Continuously stirring, heating by an electric heating sleeve, slowly heating to 60 ℃, slowly dripping water in a constant-pressure dropping funnel into a reaction bottle for hydrolysis reaction, wherein the reaction is finished after about 1 hour.
Changing the reaction device into a distillation device, slowly heating to evaporate the solvent toluene under continuous stirring, changing into reduced pressure distillation when the solvent is not substantially discharged at 120 ℃, gradually increasing the vacuum degree according to the size of the discharged distillation amount until the vacuum degree reaches-0.095 MPa and the distillation separation is not discharged at 120 ℃. The still bottoms were combined with 314 g of chloroacetic acid.
Example 3
A2000 ml four-neck flask was equipped with an electric stirrer, a thermometer and a reflux condenser, and 400 g of a chloroacetyl chloride-producing residue was weighed and put into the flask, and 1000 g of a chloroform solvent was put into the flask. Heating with electric heating jacket under stirring, slowly heating to 50 deg.C, filtering while hot, removing insoluble impurities, and collecting filtrate.
The filtrate was put into a 2000ml four-necked reaction flask again, equipped with an electric stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel, and 38.0 g of water was weighed into the constant pressure dropping funnel. Continuously stirring, heating by an electric heating sleeve, slowly heating to 60 ℃, slowly dripping water in a constant-pressure dropping funnel into a reaction flask for hydrolysis reaction, and taking about 1 hour to finish the reaction.
Changing the reaction device into a distillation device, slowly heating to evaporate the chloroform solvent under continuous stirring, changing into reduced pressure distillation when the solvent is not removed at 100 ℃, gradually increasing the vacuum degree according to the distillation amount until the vacuum degree reaches-0.095 MPa and the distillation is not removed at 100 ℃. The bottom material of the recovery kettle is mixed with 422 g of chloroacetic acid.
Example 4
6300L enamel reactor, 1800kg chloroacetyl chloride residue and 4500 kg dichloroethane solvent. Continuously stirring, opening jacket, steam heating, slowly heating to 50 deg.C, press-filtering while it is hot, removing insoluble impurities, and feeding the filtrate into hydrolysis kettle.
And (3) slowly heating the filtrate to 60 ℃ by using steam under the condition of continuous stirring, and then slowly dropwise adding 170 kg of water in a metering tank to perform hydrolysis reaction for about 2 hours to complete the reaction.
The solvent was removed by distillation under atmospheric and reduced pressure. The hydrolyzed reaction liquid is heated by steam in a distillation still under normal pressure and continuously stirred to slowly raise the temperature, the dichloroethane solvent is evaporated, reduced pressure distillation is changed when the solvent is not substantially removed at 120 ℃, and the vacuum degree is gradually increased according to the size of the distillation amount until the vacuum degree reaches-0.095 MPa and the distillation is not removed when the temperature is 120 ℃. After the dichloroethane in the kettle is completely removed, the jacket is opened to circulate water while keeping the vacuum state in the kettle and continuously stirring, the temperature of the kettle is reduced to 80 ℃, then the vacuum is removed until the interior of the kettle is in a normal pressure state, and the stirring is stopped. The mixture is barreled and weighed, and the mixed chloroacetic acid of kettle bottom materials is recovered by 1880 kg.
Example 5
2000 kg of the mixed chloroacetic acid produced in example 4 and 360 kg of sulfur were charged into a 3000L enamel chlorination reactor. And opening a cooling water and tail gas absorption system of the condenser, continuously stirring, opening a jacket for steam heating, slowly heating to 50 ℃, and introducing chlorine gas until the chlorine gas is completely dissolved. And simultaneously, closing the jacket for heating, naturally heating the chlorination reaction to 70 ℃, introducing chlorine until the color of the reflux liquid becomes yellow, and stopping introducing chlorine. Cooling to 40 ℃, adding 7 kg of pyridine, then heating to above 60 ℃, introducing chlorine again until the chlorination reaction liquid does not absorb chlorine any more, stopping introducing chlorine, continuously heating to drive out free chlorine in the reaction liquid, then cooling to below 40 ℃, and then transferring the chlorination liquid to a rectification system for rectification to obtain 105 kg of the former remaining part with the content of 93.5 percent, thus obtaining 3662 kg of trichloroacetyl chloride with the content of 99.45 percent and the yield of 95 percent.
Wherein, the gas chromatography detection condition of trichloroacetyl chloride is as follows:
the column SE-30 was maintained at 80 ℃ for 3 minutes and then heated to 180 ℃ at 15 ℃/min for 10 minutes.
The sample inlet is 250 ℃, the detector is 250 ℃, and the front column pressure is 0.06 MPa.
Sample introduction amount: 2 microliter. And (6) directly carrying out sample injection detection.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A method for producing chloroacetic acid mixed acid by utilizing residues in a chloroacetyl chloride production process is characterized in that in the chloroacetyl chloride production process, chlorine is introduced into chloroacetic acid under the condition that sulfur is used as a catalyst, the residues are black tar-like solids at normal temperature, have fluidity above 80 ℃, and have pungent sour taste and rotten apple taste.
2. The method of claim 1, comprising the steps of:
s01, taking the residue, dissolving the residue in a solvent, and filtering to obtain a filtrate;
s02, adding water into the filtrate to perform hydrolysis reaction;
s03, distilling off the solvent.
3. The method according to claim 1 or 2, wherein in S01, the solvent is one or more of ethyl acetate, toluene or chloroform.
4. The process according to any one of claims 1 to 3, wherein in S01, the dissolution step is carried out in a flask, the ratio of the residue to the solvent being 300 g: 700- & lt800 g-;
and/or, in S01, performing a dissolving step in a reaction kettle, the ratio of the residue to the solvent being 1800 kg: 4000 and 5000 kg.
5. The method according to any one of claims 1 to 4, wherein the dissolving is carried out by heating to 50 to 80 ℃ in S01.
6. The method according to any one of claims 1 to 5, wherein in S02, the filtrate is heated to not less than 60 ℃, and then water is added to perform the hydrolysis reaction.
7. A method for preparing trichloroacetyl chloride using chloroacetic acid mixed acid produced according to any of claims 1 to 5, comprising the steps of:
s11, adding the mixed chloroacetic acid and sulfur into a reaction kettle, heating, and introducing chlorine gas until all the chlorine gas is dissolved;
s12, heating, and stopping chlorine introduction until the color of the reflux liquid turns yellow;
s13, cooling, adding pyridine, heating, introducing chlorine again until the chlorination reaction liquid does not absorb chlorine any more, and stopping introducing chlorine;
and S14, continuously heating to drive out free chlorine in the reaction liquid, then cooling, and transferring the chlorination liquid to a rectification system for rectification to obtain the trichloroacetyl chloride.
8. The method for preparing trichloroacetyl chloride from chloroacetic acid mixed acid according to claim 7, wherein the weight ratio of the mixed chloroacetic acid, sulfur and pyridine is 2000: (350-370):(6-8).
9. The method for preparing trichloroacetyl chloride from chloroacetic acid mixed acid according to claim 7 or 8, wherein in S11, the temperature is raised to 48-55 ℃;
and/or, in S12, heating to 65-75 ℃;
and/or, in S13, cooling to 38-45 ℃;
and/or, in S13, heating to 60-65 ℃;
and/or, in S14, cooling to 35-40 ℃.
10. The method for preparing trichloroacetyl chloride from chloroacetic acid mixed acid as claimed in claim 7, wherein the temperature control of raising and lowering temperature is performed by switching condenser cooling water, switching and jacket steam or reaction heat generation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103086870A (en) * | 2011-10-27 | 2013-05-08 | 山西三维丰海化工有限公司 | Novel process for producing trichloro-acetic chloride |
| CN105152914A (en) * | 2015-09-23 | 2015-12-16 | 山东谦诚工贸科技有限公司 | Production technology of trichloroacetyl chloride |
| CN105348074A (en) * | 2015-12-05 | 2016-02-24 | 山东谦诚工贸科技有限公司 | Production method of trichloroacetyl chloride |
| CN107827728A (en) * | 2017-11-23 | 2018-03-23 | 山东民基化工有限公司 | Based on the processing method for reclaiming chloroacetic monoxone heavy constituent |
| CN110372498A (en) * | 2019-06-27 | 2019-10-25 | 成武县晨晖环保科技有限公司 | A kind of recycling and reusing method of chloracetyl chloride rectification residue |
| CN112830875A (en) * | 2021-01-07 | 2021-05-25 | 宁夏清禾科技服务有限公司 | Method and system for recycling acid wastewater and rectification residual liquid in trichloro-acetic chloride production process |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086870A (en) * | 2011-10-27 | 2013-05-08 | 山西三维丰海化工有限公司 | Novel process for producing trichloro-acetic chloride |
| CN105152914A (en) * | 2015-09-23 | 2015-12-16 | 山东谦诚工贸科技有限公司 | Production technology of trichloroacetyl chloride |
| CN105348074A (en) * | 2015-12-05 | 2016-02-24 | 山东谦诚工贸科技有限公司 | Production method of trichloroacetyl chloride |
| CN107827728A (en) * | 2017-11-23 | 2018-03-23 | 山东民基化工有限公司 | Based on the processing method for reclaiming chloroacetic monoxone heavy constituent |
| CN110372498A (en) * | 2019-06-27 | 2019-10-25 | 成武县晨晖环保科技有限公司 | A kind of recycling and reusing method of chloracetyl chloride rectification residue |
| CN112830875A (en) * | 2021-01-07 | 2021-05-25 | 宁夏清禾科技服务有限公司 | Method and system for recycling acid wastewater and rectification residual liquid in trichloro-acetic chloride production process |
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