CN103086870A - Novel process for producing trichloro-acetic chloride - Google Patents
Novel process for producing trichloro-acetic chloride Download PDFInfo
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- CN103086870A CN103086870A CN2011103301083A CN201110330108A CN103086870A CN 103086870 A CN103086870 A CN 103086870A CN 2011103301083 A CN2011103301083 A CN 2011103301083A CN 201110330108 A CN201110330108 A CN 201110330108A CN 103086870 A CN103086870 A CN 103086870A
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Abstract
The invention relates to a method for preparing trichloro-acetic chloride by using chloroacetic acid waste liquid as a raw material, and belongs to the field of organic chemicals and preparation technology. The method comprises the following steps of (1) pumping chloroacetic acid waste liquid refined by a rectifying tower into an acylation kettle, adding a proper amount of sulphur, and passing a chlorine gas at a certain temperature for reaction, and thus mixed acid chloride is obtained after the reaction, wherein to make the chlorine gas reacted adequately, cross chloride is adopted by using a main kettle and an assistant kettle; and (2) adding the mixed acid chloride into a chlorination reaction vessel, reacting by using pyridine as a catalyst and 4-dimethylamino pyridine as a cocatalyst and passing the chlorine gas for reaction at a certain temperature, and thus trichloro-acetic chloride is formed. The novel process has wide raw material source and low production cost and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of method for preparing trichoroacetic chloride, take the Mono Chloro Acetic Acid waste liquid as raw material, belong to organic chemicals and preparing technical field.
Background technology
Trichoroacetic chloride is a kind of important Organic Chemicals, has a wide range of applications in industries such as medicine, agricultural chemicals, dyestuff, daily use chemicals, oil, fine chemistry industries.The method of synthesizing trichloroacetyl chlorine has multiple, as (1) trichoroacetic acid(TCA) at CsCl, KCl, K
2CO
3And the catalyzer such as quaternary ammonium salt carries out pyrolysis under existing.(2) trichoroacetic acid(TCA) and sulfur oxychloride, reaction under gac or DMF existence.(3) with CCl
4, CO is raw material, at catalyzer such as CuCl, AlCl
3React under existing.(4) trichoroacetic acid(TCA) under DMF exists, gets through the phosgene acidylate.But there are some problems to some extent in above-mentioned preparation method, as: pressure is higher, reacts not thorough, and toxicity is larger, separation difficulty, the problems such as contaminate environment.
Summary of the invention
The object of the invention is to, provide a kind of Mono Chloro Acetic Acid waste liquid to prepare the method for trichoroacetic chloride, to overcome the defective of prior art, production method of the present invention comprises following step:
(1) will begin rectifying in Mono Chloro Acetic Acid waste liquid importing reactor, temperature is at 100～180 ℃, at 0～3 hour, cut is discharged, sample examination moisture after 3 hours, as moisture less than 30%, cut is adopted in front sluice, continue distillation and stop distillation to instantaneous sample moisture less than 1%～3% the time, be cooled to 50 ℃, in the importing mother liquor holding tank.
(2) sequentially adjust each valve by major and minor still, adjusting temperature according to quantity of reflux is 65～75 ℃ of main stills, 50～60 ℃ of secondary stills.Boiling range is done in reaction later stage sampling, is terminal point as the height content that boils 5%～10%, and the reaction times is 10～15 hours.
(3) by major and minor each valve of adjusting, begin in a small amount logical chlorine when being warming up to 75 ℃ of 85 ℃ of main stills, secondary still, in reaction process according to the size adjustment valve of quantity of reflux, logical chlorine dose is little green with main still condenser, on secondary still, tracheae condenser pure white is best, if the content of mixing acyl chlorides (monochloro-acetyl chloride and dichloroacetyl chloride)＜3% reaction reaches terminal point, stop logical chlorine.
(4) chlorination is completed liquid and is imported distillation tower after, regulate vapor pressure.Adopt to tower top and almost stop extraction without the gold-plating timesharing.Strictly control reflux ratio in the extraction process and guarantee that vapor pressure is stable.
Technique of the present invention is simple, production cost is low, operation is continuous, the reaction yield advantages of higher, and the tail gas that produces in production process absorbs by film-falling absorption tower, has reduced environmental pollution.
Embodiment:
Example 1
Step 1: the Mono Chloro Acetic Acid waste liquid is refining
Throw Mono Chloro Acetic Acid waste liquid 3.5t, open water of condensation, salt solution, the intensification air distillation, cut is adopted into the four-hole altar or is directly released, and gets instantaneous sample during 130 ℃ of still temperature and does moisture, and moisture＜30% stops air distillation.Get instantaneous sample chemical examination moisture content after normally going out fraction 3h.Item stop distillation as moisture content＜1～3%, be cooled to 50 ℃, import mother liquor tank.
Step 2: chloride
Drop into the mother liquor 3000kg after making with extra care, sulphur 390kg sequentially adjusts each valve by major and minor still, opens water of condensation, chilled brine.If first be warmed up to when main still feeds intake first, 75 ℃ of in a small amount logical chlorine of beginning, logical chlorine dose is controlled to be about 10 lattice.When the observation condensing liquid quantity increases, (approximately logical chlorine 1h) is cooled to 70 ℃ gradually, strengthens logical chlorine dose to 20～30 lattice.Adjusting main still temperature according to quantity of reflux is 50～60 ℃ of 65～75 ℃, secondary still.If the chlorine reaction deleterious reduces logical chlorine dose to 10～15 lattice and boiling range is done in sampling, be terminal point as the height 5-10% that boils.
Step 3: chlorination
Drop into and mix acyl chlorides 3000kg, pyridine 1.8kg, 4-dimethylamino pyridine 0.15kg, by major and minor each valve of adjusting, begin in a small amount logical chlorine when being warming up to 75 ℃ of 85 ℃ of main stills, secondary still, in reaction process according to the size adjustment valve of quantity of reflux, logical chlorine dose is little green with main still condenser, on secondary still, tracheae condenser pure white is best, if the content of mixing acyl chlorides (monochloro-acetyl chloride and dichloroacetyl chloride)＜3% reaction reaches terminal point, stops logical chlorine.
Step 4: refining
After liquid importing distillation tower is completed in chlorination, close the borrow valve, the discharging jacket water (J.W.), then open steam valve, slowly heat up, when heat up early stage, vapor pressure is no more than 0.3Mpa in order to avoid liquid flooding, when the tower reactor temperature rises to 130 ℃ of left and right, vapor pressure is retained to 0.4Mpa～0.5Mpa.Adopt to tower top and almost stop extraction without the gold-plating timesharing.Strictly control reflux ratio in the extraction process and guarantee that vapor pressure is stable.Trichoroacetic chloride product purity after refining can reach 99%.
Claims (6)
1. the production method of a trichoroacetic chloride, its feature comprises the following steps:
(1) the Mono Chloro Acetic Acid waste liquid after making with extra care by rectifying tower with in vacuum suction acidylate still, adds a certain amount of sulphur, passes at a certain temperature chlorine reaction; for chlorine is fully reacted; just take, secondary tank intersects chlorination, the chlorine advanced person becomes owner of tank, the tail gas after having reacted enters secondary tank again; chlorine is after second order reaction; tail gas is substantially without free chlorine, and after reaction acquired a certain degree, boiling range was done in sampling; if height boils less than 10%, acylation reaction finishes.Tail gas enters exhaust treatment system.
(2) mixture that acyl chloride reaction is made adds the chlorination reaction still after refining, add catalyzer, at a certain temperature, logical chlorine reaction, tail gas enters secondary tank.Reaction solution reaches certain proportion, and reaction is completed, and stops logical chlorine, reduces pressure degassed, is pressed into rectifying still, and atmospheric distillation is collected 116～118 ℃ of fractions, obtains the tribromo-acetyl chlorine products.Low fraction enters the anti-still recycled of chlorination again, and the HCl tail gas of generation enters the absorption by Hydrochloric Acid system, preparation byproduct hydrochloric acid.
2. the production method of a kind of trichoroacetic chloride according to claim 1, the mode that it is characterized in that the rectifying by containing certain stage number of Mono Chloro Acetic Acid waste liquid in (1) is made with extra care, the wider model of the compositing range of Mono Chloro Acetic Acid waste liquid, can be mother liquor of chloroacetic acid, can be also the Mono Chloro Acetic Acid waste liquid that contains a certain amount of Monochloro Acetic Acid, dichloro acetic acid, Mono Chloro Acetic Acid or other material.
3. the production method of a kind of trichoroacetic chloride according to claim 1, it is characterized in that (1) is take the Mono Chloro Acetic Acid waste liquid as raw material, remove low boiling substance 130 ℃～140 ℃ rectifying, refining mother liquor of chloroacetic acid is under the effect of sulfur catalyst, pass into chlorine and carry out chloride, obtain the acyl chlorides mixture.Pyridine, 4-dimethylamino pyridine are added in the acyl chlorides mixture, pass into chlorine, make the tribromo-acetyl chlorine products after rectifying.The tail gas that produces in production process absorbs by film-falling absorption tower, has reduced environmental pollution.
4. the production method of a kind of trichoroacetic chloride as claimed in claim 1 is characterized in that in (1) that in acyl chloride reaction, temperature is 50 ℃～75 ℃, and the quality that feeds intake of sulphur is 10%～15% of Mono Chloro Acetic Acid waste liquid, and the reaction times is 7～15 hours.For chlorine is fully reacted, just taking, secondary tank intersects chloride, the chlorine advanced person becomes owner of tank, and the tail gas that has reacted enters secondary tank again; chlorine is after second order reaction, and tail gas is substantially without free chlorine, after reaction reaches certain proportion; boiling range is done in sampling, if height boils less than 10%, acylation reaction finishes.The acyl chloride reaction final product is for mixing acyl chlorides, and its major ingredient is monochloro-acetyl chloride and dichloroacetyl chloride, and wherein the massfraction of dichloroacetyl chloride is 30～80%.Tail gas enters exhaust treatment system, by the falling film absorption by-product hydrochloric acid.
5. Mono Chloro Acetic Acid waste liquid as claimed in claim 1 is produced the method for trichoroacetic chloride, it is characterized in that in chlorination reaction, temperature is 70 ℃～120 ℃, catalyzer is pyridine, quality is for mixing 0.05～0.1% of acyl chlorides, promotor is the 4-dimethylamino pyridine, and quality is for mixing 0.005～0.01% of acyl chlorides, and the reaction times is 9～12 hours.Just also taking in chlorination reaction, secondary tank intersects chlorination, if mix the content of acyl chlorides (major ingredient: monochloro-acetyl chloride and dichloroacetyl chloride)＜3% in reaction process, reaction reaches terminal point, stops logical chlorine.
6. Mono Chloro Acetic Acid waste liquid as claimed in claim 1 is produced the method for trichoroacetic chloride, it is characterized in that being that its comprehensive yield of tribromo-acetyl chlorine products made from extra care is not less than 92%, purity 99%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011103301083A CN103086870A (en) | 2011-10-27 | 2011-10-27 | Novel process for producing trichloro-acetic chloride |
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| CN2011103301083A CN103086870A (en) | 2011-10-27 | 2011-10-27 | Novel process for producing trichloro-acetic chloride |
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| CN103086870A true CN103086870A (en) | 2013-05-08 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037137A (en) * | 2015-08-27 | 2015-11-11 | 广西田东新特化工有限公司 | Method for producing chloroacetic acid |
| CN105085237A (en) * | 2015-08-27 | 2015-11-25 | 广西田东新特化工有限公司 | Method for manufacturing trichloroacetyl chloride from chlorinated materials |
| CN105503577A (en) * | 2015-12-16 | 2016-04-20 | 南京工业大学 | Chlorine resource recycling method and system in monochloroacetyl chloride chlorination reaction process |
| CN106380395A (en) * | 2016-08-18 | 2017-02-08 | 重庆华歌生物化学有限公司 | A synthetic method of trichloroacetyl chloride |
| 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 |
| CN114835575A (en) * | 2022-05-27 | 2022-08-02 | 成武县晨晖环保科技有限公司 | Method for producing chloroacetic acid mixed acid and trichloro-acetyl chloride by using residues in chloroacetyl chloride production process |
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| GB810461A (en) * | 1954-07-08 | 1959-03-18 | Monsanto Chemicals | Production of trichloroacetic acid and its functional derivatives |
| JPH03193744A (en) * | 1989-12-22 | 1991-08-23 | Daicel Chem Ind Ltd | Production of trichloroacetic acid |
| CN1562941A (en) * | 2004-03-24 | 2005-01-12 | 大庆市富杰化工有限公司 | Method for preparing trichlorideacetyl chloride from mother liquor of chloroactic acid |
| CN1752065A (en) * | 2004-09-24 | 2006-03-29 | 陈世强 | Green chemical technology for producing chloracetyl chloride |
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2011
- 2011-10-27 CN CN2011103301083A patent/CN103086870A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB810461A (en) * | 1954-07-08 | 1959-03-18 | Monsanto Chemicals | Production of trichloroacetic acid and its functional derivatives |
| JPH03193744A (en) * | 1989-12-22 | 1991-08-23 | Daicel Chem Ind Ltd | Production of trichloroacetic acid |
| JP2649422B2 (en) * | 1989-12-22 | 1997-09-03 | ダイセル化学工業株式会社 | Production method of trichloroacetic acid |
| CN1562941A (en) * | 2004-03-24 | 2005-01-12 | 大庆市富杰化工有限公司 | Method for preparing trichlorideacetyl chloride from mother liquor of chloroactic acid |
| CN1752065A (en) * | 2004-09-24 | 2006-03-29 | 陈世强 | Green chemical technology for producing chloracetyl chloride |
Non-Patent Citations (2)
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| 孙勇: "三氯乙酰氯的合成与应用", 《中国氯碱》 * |
| 杨钟恒: "氯乙酰氯的工业生产及评价", 《辽宁化工》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037137A (en) * | 2015-08-27 | 2015-11-11 | 广西田东新特化工有限公司 | Method for producing chloroacetic acid |
| CN105085237A (en) * | 2015-08-27 | 2015-11-25 | 广西田东新特化工有限公司 | Method for manufacturing trichloroacetyl chloride from chlorinated materials |
| CN105503577A (en) * | 2015-12-16 | 2016-04-20 | 南京工业大学 | Chlorine resource recycling method and system in monochloroacetyl chloride chlorination reaction process |
| CN105503577B (en) * | 2015-12-16 | 2018-03-27 | 南京工业大学 | Chlorine resource recycling method and system in monochloroacetyl chloride chlorination reaction process |
| CN106380395A (en) * | 2016-08-18 | 2017-02-08 | 重庆华歌生物化学有限公司 | A synthetic method of trichloroacetyl chloride |
| CN106380395B (en) * | 2016-08-18 | 2019-07-12 | 重庆华歌生物化学有限公司 | A kind of synthetic method of trichloro-acetic chloride |
| 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 |
| CN114835575A (en) * | 2022-05-27 | 2022-08-02 | 成武县晨晖环保科技有限公司 | Method for producing chloroacetic acid mixed acid and trichloro-acetyl chloride by using residues in chloroacetyl chloride production process |
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Application publication date: 20130508 |