CN105348074A - Production method of trichloroacetyl chloride - Google Patents
Production method of trichloroacetyl chloride Download PDFInfo
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- CN105348074A CN105348074A CN201510899930.XA CN201510899930A CN105348074A CN 105348074 A CN105348074 A CN 105348074A CN 201510899930 A CN201510899930 A CN 201510899930A CN 105348074 A CN105348074 A CN 105348074A
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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
- C07C51/58—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
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Abstract
The invention relates to a production method of trichloroacetyl chloride and belongs to the technical field of organic chemicals and preparation. Chloroacetic acid waste liquor serves as a raw material. The production method includes the following steps that firstly, the chloroacetic acid waste liquor refined through a rectifying tower is pumped into an acylation kettle in a vacuum mode, a certain amount of sulfur is added, chlorine gas is introduced for reaction at a certain temperature, positive and vice tank crossed acylation is adopted in order to make chlorine gas fully react, and mixed acyl chloride is generated through reaction; secondly, the mixed acyl chloride is added into a chlorination reaction kettle, chlorine gas is introduced for reaction at a certain temperature with pyridine as a catalyst and 4-dimethylamino pyridine as a catalyst promoter, and trichloroacetyl chloride is generated. The raw materials are wide in source, production cost is low, and the production method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of method preparing trichoroacetic chloride, be raw material with chloroacetic acid waste liquid, 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) carries out pyrolysis under the catalyzer such as CsCl, KCl, K2CO3 and quaternary ammonium salt exists.(2) trichoroacetic acid(TCA) and sulfur oxychloride, reaction under gac or DMF exist.(3) with CCl4, CO for raw material, catalyzer as CuCl, AlCl3 etc. exist under react.(4) trichoroacetic acid(TCA) is under DMF exists, and obtains through phosgene acidylate.But there are some problems to some extent in above-mentioned preparation method, as: pressure is higher, and reaction is not thorough, and toxicity is comparatively large, separation difficulty, the problems such as contaminate environment.
Summary of the invention
The object of the invention is to, provide a kind of chloroacetic acid waste liquid to prepare the method for trichoroacetic chloride, to overcome the defect of prior art, production method of the present invention, comprises following step:
(1) chloroacetic acid waste liquid is imported in reactor start rectifying, temperature is at 100 ~ 180 DEG C, at 0 ~ 3 hour, cut is discharged, and sample examination moisture after 3 hours, as moisture is less than 30%, cut is adopted in front sluice, continue distillation and stop distillation when instantaneous sample moisture is less than 1% ~ 3%, be cooled to 50 DEG C, import in mother liquor holding tank.
(2) adjusting each valve by major and minor still order, is main still 65 ~ 75 DEG C, secondary still 50 ~ 60 DEG C according to quantity of reflux adjustment temperature.Boiling range is done in the sampling of reaction later stage, and as the height content that boils is terminal 5% ~ 10%, the reaction times is 10 ~ 15 hours.
(3) each valve is adjusted by major and minor, logical chlorine is in a small amount started when being warming up to main still 85 DEG C, secondary still 75 DEG C, according to the size adjustment valve of quantity of reflux in reaction process, logical chlorine dose is micro-green with main still condenser, on secondary still, tracheae condenser pure white is best, if the content < 3% of mixing acyl chlorides (monochloro-acetyl chloride and dichloroacetyl chloride), reaction reaches terminal, stops logical chlorine.
(4), after chlorination being completed liquid importing distillation tower, vapor pressure is regulated.Adopt to tower top almost without gold-plating timesharing stopping extraction.Strict control reflux ratio in extraction process also guarantees that vapor pressure is stablized.
Present invention process is simple, production cost is low, operation is continuous, reaction yield advantages of higher, and the tail gas produced in production process is absorbed by film-falling absorption tower, decreases environmental pollution.
Embodiment:
Example 1
Step one: chloroacetic acid waste liquid is refining throws chloroacetic acid waste liquid 3.5t, and open water of condensation, salt solution, intensification air distillation, cut is adopted into four mouthfuls of altars or directly released, and gets instantaneous sample and do moisture during still temperature 130 DEG C, and moisture < 30% stops air distillation.Instantaneous sample chemical examination moisture content is got after normally going out fraction 3h.As moisture content < 1 ~ 3% stops distillation, be cooled to 50 DEG C, import mother liquor tank.
Step 2: chloride
Drop into the mother liquor 3000kg after refining, sulphur 390kg, adjust each valve by major and minor still order, open water of condensation, chilled brine.If main still is first warmed up to when feeding intake first, 75 DEG C start logical chlorine in a small amount, and logical chlorine dose controls to be about 10 lattice.Observe (about logical chlorine 1h) when condensing liquid quantity increases and be cooled to 70 DEG C gradually, strengthen logical chlorine dose to 20 ~ 30 lattice.Adjusting main still temperature according to quantity of reflux is 65 ~ 75 DEG C, secondary still 50 ~ 60 DEG C.If chlorine reaction deleterious, reduce logical chlorine dose to 10 ~ 15 lattice and boiling range is done in sampling, as the height 5-10% that boils is terminal.
Step 3: chlorination
Drop into mixing acyl chlorides 3000kg, pyridine 1.8kg, 4-dimethylamino pyridine 0.15kg, adjust each valve by major and minor, start logical chlorine in a small amount when being warming up to main still 85 DEG C, secondary still 75 DEG C, according to the size adjustment valve of quantity of reflux in reaction process, logical chlorine dose is micro-green with main still condenser, on secondary still, tracheae condenser pure white is best, if the content < 3% of mixing acyl chlorides (monochloro-acetyl chloride and dichloroacetyl chloride), reaction reaches terminal, stops logical chlorine.
Step 4: refining
After chlorination being completed liquid importing distillation tower, close borrow valve, discharge jacket water (J.W.), then open steam valve, slowly heat up, when early stage heats up, vapor pressure is no more than 0.3Mpa in order to avoid liquid flooding, when bottom temperature rises to about 130 DEG C, vapor pressure is retained to 0.4Mpa ~ 0.5Mpa.Adopt to tower top almost without gold-plating timesharing stopping extraction.Strict control reflux ratio in extraction process also guarantees that vapor pressure is stablized.Trichoroacetic chloride product purity after refining can reach 99%.
Claims (6)
1. a production method for trichoroacetic chloride, its feature comprises the following steps:
(1) by the chloroacetic acid waste liquid vacuum suction acylation kettle after being refined by rectifying tower, add a certain amount of sulphur, pass into chlorine reaction at a certain temperature; fully react for making chlorine; take just, secondary tank intersect chlorination, chlorine advanced person becomes owner of tank, and 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 acquires a certain degree, boiling range is done in sampling; if height boils be less than 10%, acylation reaction terminates.Tail gas enters exhaust treatment system.
(2) mixture obtained for acyl chloride reaction is added chlorinating container after refining, add catalyzer, at a certain temperature, logical chlorine reaction, tail gas enters secondary tank.Reaction solution reaches certain proportion, and reaction completes, and stops logical chlorine, reduces pressure degassed, and press-in rectifying still, atmospheric distillation collects 116 ~ 118 DEG C of fractions, obtains tribromo-acetyl chlorine products.Low fraction enters the anti-still recycled of chlorination again, and the HCl tail gas of generation enters absorption by Hydrochloric Acid system, preparation byproduct hydrochloric acid.
2. the production method of a kind of trichoroacetic chloride according to claim 1, it is characterized in that in (1), chloroacetic acid waste liquid is refined by the mode of the rectifying containing certain stage number, the wider model of compositing range of chloroacetic acid waste liquid, can be mother liquor of chloroacetic acid, also can be the chloroacetic acid waste liquid containing 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) take chloroacetic acid waste liquid as raw material, at 130 DEG C ~ 140 DEG C rectifying removing low boiling substances, refining mother liquor of chloroacetic acid is under the effect of sulfur catalyst, pass into chlorine and carry out chloride, obtain acyl chlorides mixture.Pyridine, 4-dimethylamino pyridine are added in acyl chlorides mixture, passes into chlorine, obtained tribromo-acetyl chlorine products after rectifying.The tail gas produced in production process is absorbed by film-falling absorption tower, decreases environmental pollution.
4. the production method of a kind of trichoroacetic chloride as claimed in claim 1, to it is characterized in that in (1) in acyl chloride reaction, temperature is 50 DEG C ~ 75 DEG C, and the quality that feeds intake of sulphur is 10% ~ 15% of chloroacetic acid waste liquid, and the reaction times is 7 ~ 15 hours.For making chlorine fully react, just taking, secondary tank intersects chloride, chlorine advanced person becomes owner of tank, and the tail gas reacted enters secondary tank again; chlorine after second order reaction, tail gas substantially without free chlorine, after reaction reaches certain proportion; boiling range is done in sampling, if height boils be less than 10%, acylation reaction terminates.Acyl chloride reaction final product is 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 falling film absorption by-product hydrochloric acid.
5. the production method of a kind of trichoroacetic chloride as claimed in claim 1, it is characterized in that in chlorination reaction, temperature is 70 DEG C ~ 120 DEG C, catalyzer is pyridine, quality is 0.05 ~ 0.1% of mixing acyl chlorides, promotor is 4-dimethylamino pyridine, and quality is 0.005 ~ 0.01% of mixing acyl chlorides, and the reaction times is 9 ~ 12 hours.Also just taking in chlorination reaction, secondary tank intersects chlorination, if mix the content < 3% of acyl chlorides (major ingredient: monochloro-acetyl chloride and dichloroacetyl chloride) in reaction process, then reaction reaches terminal, stops logical chlorine.
6. the production method of a kind of trichoroacetic chloride as claimed in claim 1, it is characterized in that its comprehensive yield of tribromo-acetyl chlorine products being to refine is not less than 92%, purity can reach 99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510899930.XA CN105348074A (en) | 2015-12-05 | 2015-12-05 | Production method of trichloroacetyl chloride |
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| CN201510899930.XA CN105348074A (en) | 2015-12-05 | 2015-12-05 | Production method of trichloroacetyl chloride |
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| CN105348074A true CN105348074A (en) | 2016-02-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2015
- 2015-12-05 CN CN201510899930.XA patent/CN105348074A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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