CN1680251A - Synthesis of chloroacetic acid - Google Patents

Synthesis of chloroacetic acid Download PDF

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CN1680251A
CN1680251A CN 200510012347 CN200510012347A CN1680251A CN 1680251 A CN1680251 A CN 1680251A CN 200510012347 CN200510012347 CN 200510012347 CN 200510012347 A CN200510012347 A CN 200510012347A CN 1680251 A CN1680251 A CN 1680251A
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acetic acid
acid
aceticanhydride
synthesis
gac
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CN1296340C (en
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李福祥
吴岚
吕志平
薛建伟
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Taiyuan University of Technology
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Taiyuan University of Technology
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Abstract

Synthesis of chloroacetic acid is characterized by taking acetic anhydride as catalyst, and taking SO42-/MxOy or SO42-/MxOy-C, S2O82-/MxOy or S2O82-/MxOy-C as auxiliary catalyst. It adopts acetic acid chlorine gas chlorinating method. MxOy can be ZrO2, or TiO2, or Fe2O3, or Cr2O3, or MnO2, or Sn2O3, or WO3, or MoO3, or can be mixture of them. It achieves higher reacting speed, shorter reacting time, and less content of by-products.

Description

A kind of method for synthesizing chloroacetic acid
One, technical field:
A kind of method for synthesizing chloroacetic acid of the present invention belongs to organic synthesis and catalytic science field.
Two, background technology:
Mono Chloro Acetic Acid is a kind of important organic chemical industry's intermediate, it no longer is the fine chemical product of traditional definition, in recent years world's aggregate consumption is more than 600,000 tons, the aggregate consumption of China is the important source material of synthetic dyestuff, agricultural chemicals, medicine, spices, oil field chemical, papermaking chemical product, textile auxiliary agent, tensio-active agent etc. also more than 100,000 tons.Now, chloroacetic industrial process mainly contains two kinds: the one, and the trieline hydrolysis method, another kind is the acetate chlorination process.The former can obtain high-purity chloro acetate, but raw material consumption is big, and operation is long, the cost height; Latter's synthesis technique is simple, invests for a short time, and raw material is inexpensive, be easy to get, but the control reaction is difficult, is difficult for producing high-purity product.Adopt the latter at present in the world mostly, China's Mono Chloro Acetic Acid also adopts this method.Acetate is the same with other carboxylic acid, and its α-hydrogen atom activity is relatively poor, is difficult for direct chlorination, and the essential catalytic chlorination that adopts adopted sulphur, phosphorus or phosphorus trichloride to make catalyzer in the past, but often contains catalyst residue such as sulphur in the product, influences quality product.Generally adopt the catalyzer of aceticanhydride at present abroad as acetate chlorination process synthesis of chloroacetic acid, simultaneously for fast reaction speed, reduce the growing amount of by-product dichloroacetic acid, also add some other promotors, as sulfuric acid, chlorsulfonic acid and manganous acetate, dichloro acetic acid inhibitor such as chromium acetate, but it is residual that these promotors also have in product, residual in order to reduce, occurred the beginning of the nineties with the gac is promotor, this composite catalyst of forming with gac and aceticanhydride, the generation probability of dichloro acetic acid has been reduced to some extent, and product yield also can improve greatly.But use gac to do the generation that promotor can not fundamentally suppress dichloro acetic acid separately, speed of response is yet slower, because the chlorination reaction of acetic acid is an acid catalyzed reaction, only under suitable acid catalysis effect, could fundamentally improve the selectivity and the speed of response of reaction.
Three, summary of the invention
Its purpose of a kind of method for synthesizing chloroacetic acid of the present invention is, for the selectivity and the speed of response of fundamentally raising reaction, thereby discloses a kind of mechanism according to the acetic acid chlorination reaction, is raw material with acetic acid and chlorine, is Primary Catalysts with the aceticanhydride, solid super-strong acid SO 4 2-/ M xO yAnd S 2O 8 2-/ M xO yOr SO 4 2-/ M xO y+ gac and S 2O 8 2-/ M xO y+ gac is a promotor, the technical scheme of catalysis acetic acid chlorination reaction synthesis of chloroacetic acid.
A kind of method for synthesizing chloroacetic acid of the present invention is characterized in that: being a kind of mechanism according to the acetic acid chlorination reaction, is raw material with acetic acid and chlorine, is Primary Catalysts with the aceticanhydride, solid super-strong acid SO 4 2-/ M xO yAnd S 2O 8 2-/ M xO yOr SO 4 2-/ M xO y+ gac and S 2O 8 2-/ M xO y+ gac is a promotor, catalysis acetic acid chlorination reaction synthesis of chloroacetic acid.
Above-mentioned a kind of method for synthesizing chloroacetic acid is characterized in that: with the aceticanhydride catalyzer, and solid super-strong acid SO 4 2-/ M xO yOr SO 4 2-/ M xO y+ gac, solid super-strong acid S 2O 8 2-/ M xO yOr S 2O 8 2-/ M xO y+ gac is a promotor, makes acetic acid and chlorine carry out the chlorination reaction synthesis of chloroacetic acid under 90～130 ℃, and reaction can be carried out in the batch reactor, also can carry out in flow reactor.
Above-mentioned a kind of synthesis of chloroacetic acid method is characterized in that M xO yCan be ZrO 2, TiO 2, Fe 2O 3, Cr 2O 3, MnO 2, Sn 2O 3, WO 3, MoO 3Or their several mixtures, ZrO 2, TiO 2, Fe 2O 3, Cr 2O 3, MnO 2, Sn 2O 3, WO 3Or MoO 3At M xO yIn ratio be 0～100%.
Above-mentioned a kind of synthesis of chloroacetic acid method is characterized in that acetic acid: aceticanhydride: SO 4 2-/ M xO y=100: 3～15: 0.5～5; Acetic acid: aceticanhydride: gac: SO 4 2-/ M xO y=100: 3～15: 1～10: 0.5～5; Acetic acid: aceticanhydride: S 2O 8 2-/ M xO y=100: 3～15: 0.1～3; Acetic acid: aceticanhydride: gac: S 2O 8 2-/ M xO y=100: 3～15: 1～10: 0.1～3.
Above-mentioned a kind of synthesis of chloroacetic acid method is characterized in that acetic acid: aceticanhydride: SO 4 2-/ M xO y=100: 7～11: 1～2; Acetic acid: aceticanhydride: gac: SO 4 2-/ M xO y=100: 7～11: 5～8: 1～3; Acetic acid: aceticanhydride: S 2O 8 2-/ M xO y=100: 7～11: 0.6～1.5; Acetic acid: aceticanhydride: gac: S 2O 8 2-/ M xO y=100: 7～11: 3～5: 0.8～2 is better.
Above-mentioned a kind of synthesis of chloroacetic acid method is characterized in that using solid super-strong acid S 2O 8 2-/ M xO yFor promotor better.
Above-mentioned a kind of synthesis of chloroacetic acid method is characterized in that being reflected at and carries out under 100～110 ℃ better;
Above-mentioned a kind of synthesis of chloroacetic acid method is characterized in that employed solid super-strong acid SO 4 2-/ M xO yWith S 2O 8 2-/ M xO yHandle at 450～650 ℃ roasting temperatures.
Advantage of the present invention has been to use solid super-strong acid SO 4 2-/ M xO y, S 2O 8 2-/ M xO y, SO 4 2-/ M xO y+ gac or S 2O 8 2-/ M xO yBehind+gac the promotor, the speed and the selectivity of acetic acid chlorination reaction improve greatly, under the top condition when acetic acid conversion reaches 98%, the content of dichloro acetic acid is less than 1.7% in the reaction solution, and be reduced to 6～8 hours by original 15～24 hours between inverse time in rhythmic reaction, therefore miniaturization and the serialization for this technology full scale plant provides condition.
Four, description of drawings:
Fig. 1 is solid super-strong acid SO 4 2-/ 1.5%Cr/Fe 2O 3XRD figure at 550 ℃ of following roasting samples;
Fig. 2 is solid super-strong acid S 2O 8 2-/ 1.5%Cr/0.5%Sn/Fe 2O 3XRD figure at 500 ℃ of following roasting samples.
Five, embodiment:
Embodiment one:
In homemade 50ml hard glass chlorination reactor, add 25ml Glacial acetic acid and 2.5ml aceticanhydride, and add solid super-strong acid SO 4 2-/ 1.5%Cr/Fe 2O 3Promotor 0.2g, at 100 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable of chlorine, and afterreaction finished in 6 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 95.3%, dichloro acetic acid 3.0%, acetate 1.7%.
Embodiment two:
In above-mentioned chlorination reactor, add 25ml Glacial acetic acid and 2.5ml aceticanhydride, and add solid super-strong acid SO 4 2-/ 0.5%Mn/Fe 2O 3Promotor 0.4g, at 115 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable of chlorine, and afterreaction finished in 6 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 93.4%, dichloro acetic acid 3.8%, acetate 2.8%.
Embodiment three:
In above-mentioned chlorination reactor, add 25ml Glacial acetic acid and 3.0ml aceticanhydride, and add solid super-strong acid SO 4 2-/ 2.0%Sn/Fe 2O 3Promotor 0.3g, gac 1.5g, at 105 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable of chlorine, and afterreaction finished in 6 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 96%, dichloro acetic acid 3.2%, acetate 0.8%.
Embodiment four:
In above-mentioned chlorination reactor, add 25ml Glacial acetic acid and 3.0ml aceticanhydride, and add solid super-strong acid SO 4 2-/ Fe 2O 3Promotor 0.3g, gac 1.5g, at 105 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable of chlorine, and afterreaction finished in 6 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 94.7%, dichloro acetic acid 3.5%, acetate 1.8%.
Embodiment five:
In above-mentioned chlorination reactor, add 25ml Glacial acetic acid and 2.5ml aceticanhydride, and add solid super-strong acid SO 4 2-/ 1.5%V/Fe 2O 3Promotor 0.6g, gac 1.5g, at 120 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable of chlorine, and afterreaction finished in 6 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 94.6%, dichloro acetic acid 4.2%, acetate 1.2%.
Embodiment six:
In above-mentioned chlorination reactor, add 25ml Glacial acetic acid and 2.5ml aceticanhydride, and add solid super-strong acid S 2O 8 2-/ 1.5%Cr/0.5%Sn/Fe 2O 3Promotor 0.3g, at 105 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable, and afterreaction finished in 5 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 96.2%, dichloro acetic acid 1.6%, acetate 2.2%.
Embodiment seven:
In above-mentioned chlorination reactor, add 25ml Glacial acetic acid and 2.5ml aceticanhydride, and add solid super-strong acid S 2O 8 2-/ Fe 2O 3Promotor 0.3g, at 105 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable, and afterreaction finished in 5 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 96.0%, dichloro acetic acid 1.7%, acetate 2.3%.
Embodiment eight:
In above-mentioned chlorination reactor, add 25ml Glacial acetic acid and 3.0ml aceticanhydride, and add solid super-strong acid S 2O 8 2-/ 1.5%W/Fe 2O 3Promotor 0.2g, at 115 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable of chlorine, and afterreaction finished in 5 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 95.5%, dichloro acetic acid 2.9%, acetate 1.6%.
Embodiment nine:
In above-mentioned chlorination reactor, add 25ml Glacial acetic acid and 2.0ml aceticanhydride, and add solid super-strong acid S 2O 8 2-/ 2.0%Mo/1.5%Zr/Fe 2O 3Promotor 0.3g, gac 1.5g, at 105 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable of chlorine, and afterreaction finished in 6 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 93.3%, dichloro acetic acid 3.8%, acetate 2.9%.
Embodiment ten:
In above-mentioned chlorination reactor, add 25ml Glacial acetic acid and 2.5ml aceticanhydride, and add solid super-strong acid S 2O 8 2-/ 1.5%Ti/Fe 2O 3Promotor 0.4g, gac 1.0g, at 125 ℃ of following logical chlorine reactions, the logical chlorine speed of control is with little excessive being advisable of chlorine, and afterreaction finished in 6 hours, the consisting of of assaying reaction liquid: Mono Chloro Acetic Acid 94.6%, dichloro acetic acid 3.2%, acetate 2.2%.

Claims (7)

1, a kind of method for synthesizing chloroacetic acid is characterized in that: with acetic acid and chlorine is raw material, and aceticanhydride is a catalyzer, solid super-strong acid SO 4 2-/ M xO yOr SO 4 2-/ M xO y+ gac, solid super-strong acid S 2O 8 2-/ M xO yOr S 2O 8 2-/ M xO y+ gac is a promotor, makes acetic acid and chlorine carry out the chlorination reaction synthesis of chloroacetic acid under 90～130 ℃, is reflected at batch reactor or carries out in flow reactor.
2, according to the described a kind of synthesis of chloroacetic acid method of claim 1, it is characterized in that described M xO yBe ZrO 2, TiO 2, Fe 2O 3, Cr 2O 3, MnO 2, Sn 2O 3, WO 3Or MoO 3And their several mixtures, ZrO 2, TiO 2, Fe 2O 3, Cr 2O 3, MnO 2, Sn 2O 3, WO 3Or MoO 3At M xO yIn ratio be 0～100%.
3, according to the described a kind of synthesis of chloroacetic acid method of claim 1, it is characterized in that described acetic acid: aceticanhydride: SO 4 2-/ M xO y=100: 3～15: 0.5～5; Acetic acid: aceticanhydride: gac: SO 4 2-/ M xO y=100: 3～15: 1～10: 0.5～5; Acetic acid: aceticanhydride: S 2O 8 2-/ M xO y=100: 3～15: 0.1～3; Acetic acid: aceticanhydride: gac: S 2O 8 2-/ M xO y=100: 3～15: 1～10: 0.1～3.
4, according to the described a kind of synthesis of chloroacetic acid method of claim 1, it is characterized in that described acetic acid: aceticanhydride: SO 4 2-/ M xO y=100: 7～11: 1～2; Acetic acid: aceticanhydride: gac: SO 4 2-/ M xO y=100: 7～11: 5～8: 1～3; Acetic acid: aceticanhydride: S 2O 8 2-/ M xO y=100: 7～11: 0.6～1.5; Acetic acid: aceticanhydride: gac: S 2O 8 2-/ M xO y=100: 7～11: 3～5: 0.8～2.
5, according to the described a kind of synthesis of chloroacetic acid method of claim 1, it is characterized in that preferentially using solid super-strong acid S 2O 8 2-/ M xO yBe promotor.
6,, it is characterized in that described acetic acid and chlorine carry out chlorination reaction and carries out under 100～110 ℃ according to the described a kind of synthesis of chloroacetic acid method of claim 1.
7, according to the described a kind of synthesis of chloroacetic acid method of claim 1, it is characterized in that employed solid super-strong acid SO 4 2-/ M xO yWith S 2O 8 2-/ M xO yHandle at 450～650 ℃ roasting temperatures.
CNB2005100123479A 2005-01-29 2005-01-29 Synthesis of chloroacetic acid Expired - Fee Related CN1296340C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101948377A (en) * 2010-08-25 2011-01-19 江苏索普（集团）有限公司 Method for preparing chloroacetic acid
CN103357426A (en) * 2013-07-15 2013-10-23 江苏索普（集团）有限公司 Preparation method of solid strong acid and catalysis prompting function thereof in process of preparing chloroacetic acid by using acetic anhydride catalysis method
CN108640828A (en) * 2018-08-17 2018-10-12 山东民基化工有限公司 Chloroacetic technique and its device are prepared using micro passage reaction catalytic chlorination

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3152174A (en) * 1960-04-21 1964-10-06 Dow Chemical Co Manufacture of monochloroacetic acid
CN1382680A (en) * 2001-04-26 2002-12-04 山东新华医药集团淄博东风化工有限责任公司 Process for preparing chloracetic acid

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101948377A (en) * 2010-08-25 2011-01-19 江苏索普（集团）有限公司 Method for preparing chloroacetic acid
CN103357426A (en) * 2013-07-15 2013-10-23 江苏索普（集团）有限公司 Preparation method of solid strong acid and catalysis prompting function thereof in process of preparing chloroacetic acid by using acetic anhydride catalysis method
CN108640828A (en) * 2018-08-17 2018-10-12 山东民基化工有限公司 Chloroacetic technique and its device are prepared using micro passage reaction catalytic chlorination
CN108640828B (en) * 2018-08-17 2023-10-03 山东民基新材料科技有限公司 Process and device for preparing chloroacetic acid by catalytic chlorination of microchannel reactor

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