CN102816045A - Method for synthesizing chloromethane by tail gas generated during chloroacetic acid production - Google Patents
Method for synthesizing chloromethane by tail gas generated during chloroacetic acid production Download PDFInfo
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Abstract
The invention relates to a method for synthesizing chloromethane by tail gas generated during chloroacetic acid production. Firstly, the tail gas which is generated during chloroacetic acid production and contains hydrogen chloride is enabled to sequentially pass through a hydrochloric acid gas washing device, an acetic acid gas washing device and an adsorption device which contains solid adsorbents to be subjected to a purification treatment, then the tail gas is premixed with methanol to obtain a mixture, and the mixture is fed to a synthesis reactor to generate the chloromethane under the action of catalysts. The gas after the reaction is respectively subjected to washing, alkaline washing and concentrated sulfuric acid drying to obtain a high purity chloromethane product. The method for synthesizing the chloromethane by the tail gas generated during chloroacetic acid production has the advantages that the equipment investment is small, the operation is simple, the efficiency is high, raw materials are easy to obtain, and the like.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid.
Background technology
Methyl chloride is a kind of important organic synthesis intermediate, and the methyl chloride product is gone into the ripening stage in developed country, the domestic important development stage that is in.The present main application of monochloro methane is to produce methyl chlorosilane; Methyl atmosphere silane is the monomer of synthesizing organo-silicon material; Be widely used in industries such as building, weaving, electronics, electrical equipment, machinery, traffic, chemical industry, medical treatment, food, Aeronautics and Astronautics; Because current industry and social development, in for some time from now on, still be zooming trend as the methane chloride production and the trade of methyl atmosphere silane main raw material.The industrial production of methyl chloride mainly is to be the production technique of raw material with methyl alcohol and hydrogenchloride; The hydrogenchloride that the hydrogenchloride that the hydrogen chloride gas that is adopted needs synthesis method to produce perhaps obtains through concentrated hydrochloric acid high temperature deep analysis is raw material, and is general higher to the purity requirement of hydrogen chloride gas.The hydrogenchloride of organic chloride building-up process by-product, owing to contain more organic impurity, also not appearing in the newspapers is used for the synthetic of methyl chloride.
China most production of chloroacetic acid enterprise all adopts the acetate chlorination, and the composition of producing tail gas is mainly hydrogenchloride.All be to absorb the generation by-product hydrochloric acid through water to carry out the low price sale at present,, limited its use, unsalable phenomenon usually occurs, influenced the further expansion of production of chloroacetic acid scale because the amount of by-product is very big, and wherein contains organic impurity.If it is directly carried out scene digestion, further produce high value-added product, will help the Mono Chloro Acetic Acid industrial expansion, also help eliminating the environmental pollution hidden danger that the existence by excessive hydrochloric acid causes simultaneously.
It is catalyzer that the production processes of chloroacetic acid of China all adopts SULPHUR POWDER; The hydrogen chloride tail gas of by-product generally contains catalyzer SULPHUR POWDER and impurity such as Acetyl Chloride 98Min., chloroacetyl chloride and sulfocompound; The quality that influence methyl chloride building-up reactions and product is understood in bringing into of these materials, therefore must before reaction, purify this tail gas.
Summary of the invention
The present invention provides a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid for solving the problem in the present technology, to remove the impurity in the production of chloroacetic acid tail gas, uses it for the synthetic of methyl chloride.
The present invention adopts following technical scheme to be achieved:
A kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid of the present invention, it may further comprise the steps:
A. from the tail gas that contains hydrogenchloride in the production processes of chloroacetic acid; At first getting into compressor compresses gas; Get into the bottom of acetic acid washing tower then, in the acetic acid washing tower, contain the tail gas and the acetum counter current contact of hydrogenchloride, to absorb the material that is dissolved in acetic acid in the gas.
B. the gas that come out in acetic acid washing tower top in said step a, the bottom of entering hydrochloric acid washing tower, gas and hydrochloric acid soln counter current contact in the hydrochloric acid washing tower are to absorb water-soluble material in the gas.
C. the gas that come out in hydrochloric acid washing tower top in said step b gets into gas adsorbing device, contains the sulfur-containing impurities in the tail gas of hydrogenchloride with absorption, and gas is carried out deep purifying.
D. the methanol gas among the said step c after cleaned gas and the heating after the pre-mixing, gets into the synthetic methyl chloride of chemical reaction takes place in the reactor drum that contains liquid-phase catalyst in mixing tank.
E. said steps d is carried out condensing reflux by the methyl chloride gas that contains that reactor drum comes out through reflux condensate device; Get into water wash column subsequently; Get into soda-wash tower again; Get into first step sulfuric acid tower, second stage sulfuric acid tower, third stage sulfuric acid tower afterwards successively, methyl chloride gas is carried out depickling, dehydration and purifying treatment after, obtain highly purified methyl chloride gas.
F. the methyl chloride gas that said step e obtains gets into water cooler again and cools off with condensation and obtain the methyl chloride liquid product behind compressor, gets into the storage of liquid methyl chloride storage tank.
Preferably, described a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid, the described pressure that behind compressor, contains hydrogen chloride tail gas of step a is brought up to 0.3-0.8MPa.The described acetic acid scrubber tower of step a is two sections packing towers, and service temperature is 15 ℃ ~ 40 ℃.
Preferably, described a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid, the described hydrochloric acid washing tower of step b is two sections packing towers, service temperature is 15 ℃ ~ 40 ℃.
Preferably, described a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid, the solid adsorbent in the described gas adsorbing device of step c is one or more in aluminum oxide, molecular sieve, gac, the silica gel.
Preferably, described a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid, the described reactor drum of steps d is a glass lined reaction vessel, and temperature of reaction is 130 ~ 160 ℃, and working pressure is 0.1 ~ 0.5MPa.The described liquid-phase catalyst of steps d is 50% ~ 85% zinc chloride and/or 5% ~ 10% nickel chloride aqueous solution.
Preferably, described a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid, the used alkali absorption liquid of the described soda-wash tower of step e is 10% ~ 60% aqueous sodium hydroxide solution.The used sour absorption liquid of the described third stage sulfuric acid tower of step e is 93% or the above vitriol oil.
Further preferred, described a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid is characterized in that it specifically may further comprise the steps:
A. from the tail gas that contains hydrogenchloride in the production processes of chloroacetic acid; At first get into compressor gas is compressed to 0.5MPa; Get into the bottom of acetic acid washing tower then, in the acetic acid washing tower, contain the tail gas and the acetum counter current contact of hydrogenchloride, to absorb the material that is dissolved in acetic acid in the gas.The service temperature of acetic acid washing tower is 30 ℃.The tail gas that contains hydrogenchloride is discharged from the washing tower top after the acetic acid washing, squeezes into circulation device by pump again after acetic acid is discharged from the bottom and recycles.
B. the gas that comes out from a step acetic acid scrubber tower top, the bottom of entering hydrochloric acid washing tower, gas and hydrochloric acid soln counter current contact in the hydrochloric acid washing tower are to absorb water-soluble material in the gas.The service temperature of hydrochloric acid washing tower is 30 ℃.The tail gas that contains hydrogenchloride is discharged from the washing tower top behind the salt acid elution, squeezes into circulation device by pump again after hydrochloric acid is discharged from the bottom and recycles.
C. the gas that comes out from b step hydrochloric acid washing tower top gets into gas adsorbing device, contains the sulfur-containing impurities in the tail gas of hydrogenchloride with absorption, and gas is carried out deep purifying.Gas adsorbing device inside is filled with molecular sieve and aluminum oxide.
D. the methanol gas after cleaned gas and the heating gets in the reactor drum of the aqueous solution liquid-phase catalyst that contains 60% zinc chloride and 10% nickelous chloride the synthetic methyl chloride of chemical reaction takes place in mixing tank after the pre-mixing among the step c.The service temperature of reactor drum is 150 ℃, and working pressure is 0.3MPa.
E. said steps d is carried out condensing reflux by the methyl chloride gas that contains that reactor drum comes out through reflux condensate device; Get into water wash column subsequently; Get into soda-wash tower then; Get into first step sulfuric acid tower, second stage sulfuric acid tower, third stage sulfuric acid tower more successively, methyl chloride gas is carried out depickling, dehydration and purifying treatment after, obtain highly purified methyl chloride gas.The used alkali absorption liquid of soda-wash tower is 50% aqueous sodium hydroxide solution.The used sour absorption liquid of sulfuric acid tower is 95% the vitriol oil, and the sulfuric acid absorption liquid that comes out from third stage sulfuric acid tower gets into second stage sulfuric acid tower, and the sulfuric acid absorption liquid that sulfuric acid tower comes out from the second stage gets into second stage sulfuric acid tower.
F. to 0.7MPa, the entering water cooler cools off with condensation and obtains the methyl chloride liquid product methyl chloride gas that said step e obtains through compressor compresses, gets into the storage of liquid methyl chloride storage tank at last.
The present invention compared with prior art has following significant advantage:
1. equipment is operated under normal pressure, invests for a short time, and equipment is simple, and technical process is short.
2. quiet run and control easily, simple to operate, expense is low.
3. the product separation is simple, thorough, and the product after separating can recycle.
4. the production process environmental pollution is little.
5. treated hydrogen chloride tail gas purity is high, quality is good, and the hydrogenchloride after the processing can be used for the synthetic methyl chloride technology of methyl alcohol hydrogenchloride.
In a word, the present invention have that technology is simple, facility investment is little, simple to operate, good stability, the characteristics of control easily.Utilize this technology can make the acquisition high value utilization in the methyl chloride of synthetic high added value is synthetic of the low hydrogen chloride tail gas of poor quality in the Mono Chloro Acetic Acid technology, purity.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method.
Each part description among the figure:
1, production processes of chloroacetic acid contains hydrogen chloride tail gas; 2, compressor; 3 acetic acid washing towers; 4, hydrochloric acid washing tower; 5, gas adsorbing device; Methyl alcohol behind 6 heating and gasifyings; 7, mixing tank; 8, reactor drum; 9, reflux condensate device; 10, water wash column; 11, soda-wash tower; 12, first step sulfuric acid tower; 13, second stage sulfuric acid tower; 14, third stage sulfuric acid tower; 15, compressor; 16, cooler condenser; 17, methyl chloride storage tank.
Embodiment
Below in conjunction with accompanying drawing the present invention is done further detailed description.
A. from the tail gas that contains hydrogenchloride in the production processes of chloroacetic acid 1; At first get into compressor 2 gas is compressed to 0.3MPa; Get into the bottom of acetic acid washing tower 3 then; The tail gas 1 and acetum counter current contact that in acetic acid washing tower 3, contain hydrogenchloride are to absorb the material that is dissolved in acetic acid in the gas.The service temperature of acetic acid washing tower 3 is 15 ℃.The tail gas 1 that contains hydrogenchloride is discharged from the washing tower top after the acetic acid washing, squeezes into circulation device by pump again after acetic acid is discharged from the bottom and recycles.
B. the gas that comes out from a step acetic acid scrubber tower 3 tops, the bottom of entering hydrochloric acid washing tower 4, gas and hydrochloric acid soln counter current contact in hydrochloric acid washing tower 4 are to absorb water-soluble material in the gas.The service temperature of hydrochloric acid washing tower 4 is 15 ℃.The tail gas 1 that contains hydrogenchloride is discharged from the washing tower top behind the salt acid elution, squeezes into circulation device by pump again after hydrochloric acid is discharged from the bottom and recycles.
C. the gas that comes out from b step hydrochloric acid washing tower 4 tops gets into gas adsorbing device 5, contains the sulfur-containing impurities in the tail gas 1 of hydrogenchloride with absorption, and gas is carried out deep purifying.Gas adsorbing device 5 inside are filled with gac and silica gel.
D. the methanol gas 6 after cleaned gas and the heating after the pre-mixing, gets into the synthetic methyl chloride of chemical reaction takes place in the reactor drum 8 that contains 50% zinc chloride and 10% nickel chloride aqueous solution liquid-phase catalyst in mixing tank 7 among the step c.The service temperature of reactor drum 8 is 130 ℃, and working pressure is 0.1MPa.
E. said steps d is carried out condensing reflux by the methyl chloride gas that contains that reactor drum 8 comes out through reflux condensate device 9; Get into water wash column 10 subsequently; Get into soda-wash tower 11 then; Get into first step sulfuric acid tower 12, second stage sulfuric acid tower 13, third stage sulfuric acid tower 14 more successively, methyl chloride gas is carried out depickling, dehydration and purifying treatment after, obtain highly purified methyl chloride gas.Soda-wash tower 11 used alkali absorption liquids are 10% aqueous sodium hydroxide solution.Sulfuric acid tower 14 used sour absorption liquids are 93% the vitriol oil, and the sulfuric acid absorption liquid that comes out from third stage sulfuric acid tower 14 gets into second stage sulfuric acid tower 13, and the sulfuric acid absorption liquid that sulfuric acid tower 13 comes out from the second stage gets into second stage sulfuric acid tower 12.
F. the methyl chloride gas that said step e obtains is after compressor 15 is compressed to 0.7MPa, and entering water cooler 16 cools off with condensation and obtains the methyl chloride liquid product, gets into 17 storages of liquid methyl chloride storage tank at last.
Embodiment 2
A. from the tail gas that contains hydrogenchloride in the production processes of chloroacetic acid 1; At first get into compressor 2 gas is compressed to 0.5MPa; Get into the bottom of acetic acid washing tower 3 then; The tail gas 1 and acetum counter current contact that in acetic acid washing tower 3, contain hydrogenchloride are to absorb the material that is dissolved in acetic acid in the gas.The service temperature of acetic acid washing tower 3 is 30 ℃.The tail gas 1 that contains hydrogenchloride is discharged from the washing tower top after the acetic acid washing, squeezes into circulation device by pump again after acetic acid is discharged from the bottom and recycles.
B. the gas that comes out from a step acetic acid scrubber tower 3 tops, the bottom of entering hydrochloric acid washing tower 4, gas and hydrochloric acid soln counter current contact in hydrochloric acid washing tower 4 are to absorb water-soluble material in the gas.The service temperature of hydrochloric acid washing tower 4 is 30 ℃.The tail gas 1 that contains hydrogenchloride is discharged from the washing tower top behind the salt acid elution, squeezes into circulation device by pump again after hydrochloric acid is discharged from the bottom and recycles.
C. the gas that comes out from b step hydrochloric acid washing tower 4 tops gets into gas adsorbing device 5, contains the sulfur-containing impurities in the tail gas 1 of hydrogenchloride with absorption, and gas is carried out deep purifying.Gas adsorbing device 5 inside are filled with molecular sieve and aluminum oxide.
D. the methanol gas 6 after cleaned gas and the heating gets in the reactor drum 8 of the aqueous solution liquid-phase catalyst that contains 60% zinc chloride and 10% nickelous chloride the synthetic methyl chloride of chemical reaction takes place in mixing tank 7 after the pre-mixing among the step c.The service temperature of reactor drum 8 is 150 ℃, and working pressure is 0.3MPa.
E. said steps d is carried out condensing reflux by the methyl chloride gas that contains that reactor drum 8 comes out through reflux condensate device 9; Get into water wash column 10 subsequently; Get into soda-wash tower 11 then; Get into first step sulfuric acid tower 12, second stage sulfuric acid tower 13, third stage sulfuric acid tower 14 more successively, methyl chloride gas is carried out depickling, dehydration and purifying treatment after, obtain highly purified methyl chloride gas.Soda-wash tower 11 used alkali absorption liquids are 50% aqueous sodium hydroxide solution.Sulfuric acid tower 14 used sour absorption liquids are 95% the vitriol oil, and the sulfuric acid absorption liquid that comes out from third stage sulfuric acid tower 14 gets into second stage sulfuric acid tower 13, and the sulfuric acid absorption liquid that sulfuric acid tower 13 comes out from the second stage gets into second stage sulfuric acid tower 12.
F. the methyl chloride gas that said step e obtains is after compressor 15 is compressed to 0.7MPa, and entering water cooler 16 cools off with condensation and obtains the methyl chloride liquid product, gets into 17 storages of liquid methyl chloride storage tank at last.
A. from the tail gas that contains hydrogenchloride in the production processes of chloroacetic acid 1; At first get into compressor 2 gas is compressed to 0.8MPa; Get into the bottom of acetic acid washing tower 3 then; The tail gas 1 and acetum counter current contact that in acetic acid washing tower 3, contain hydrogenchloride are to absorb the material that is dissolved in acetic acid in the gas.The service temperature of acetic acid washing tower 3 is 40 ℃.The tail gas 1 that contains hydrogenchloride is discharged from the washing tower top after the acetic acid washing, squeezes into circulation device by pump again after acetic acid is discharged from the bottom and recycles.
B. the gas that comes out from a step acetic acid scrubber tower 3 tops, the bottom of entering hydrochloric acid washing tower 4, gas and hydrochloric acid soln counter current contact in hydrochloric acid washing tower 4 are to absorb water-soluble material in the gas.The service temperature of hydrochloric acid washing tower 4 is 40 ℃.The tail gas 1 that contains hydrogenchloride is discharged from the washing tower top behind the salt acid elution, squeezes into circulation device by pump again after hydrochloric acid is discharged from the bottom and recycles.
C. the gas that comes out from b step hydrochloric acid washing tower 4 tops gets into gas adsorbing device 5, contains the sulfur-containing impurities in the tail gas 1 of hydrogenchloride with absorption, and gas is carried out deep purifying.Gas adsorbing device 5 inside are filled with gac.
D. the methanol gas 6 after cleaned gas and the heating after the pre-mixing, gets into the synthetic methyl chloride of chemical reaction takes place in the reactor drum 8 that contains 85% solder(ing)acid liquid-phase catalyst in mixing tank 7 among the step c.The service temperature of reactor drum 8 is 140 ℃, and working pressure is 0.5MPa.
E. said steps d is carried out condensing reflux by the methyl chloride gas that contains that reactor drum 8 comes out through reflux condensate device 9; Get into water wash column 10 subsequently; Get into soda-wash tower 11 then; Get into first step sulfuric acid tower 12, second stage sulfuric acid tower 13, third stage sulfuric acid tower 14 more successively, methyl chloride gas is carried out depickling, dehydration and purifying treatment after, obtain highly purified methyl chloride gas.Soda-wash tower 11 used alkali absorption liquids are 60% aqueous sodium hydroxide solution.Sulfuric acid tower 14 used sour absorption liquids are 98% the vitriol oil, and the sulfuric acid absorption liquid that comes out from third stage sulfuric acid tower 14 gets into second stage sulfuric acid tower 13, and the sulfuric acid absorption liquid that sulfuric acid tower 13 comes out from the second stage gets into second stage sulfuric acid tower 12.
F. the methyl chloride gas that said step e obtains is after compressor 15 is compressed to 0.7MPa, and entering water cooler 16 cools off with condensation and obtains the methyl chloride liquid product, gets into 17 storages of liquid methyl chloride storage tank at last.
Claims (10)
1. method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid is characterized in that it may further comprise the steps:
A. from the tail gas that contains hydrogenchloride in the production processes of chloroacetic acid (1); At first getting into compressor (2) compresses gas; Get into the bottom of acetic acid washing tower (3) then; The tail gas (1) and acetum counter current contact that in acetic acid washing tower (3), contain hydrogenchloride are to absorb the material that is dissolved in acetic acid in the gas;
B. the gas that come out in acetic acid washing tower (3) top in said step a, the bottom of entering hydrochloric acid washing tower (4), gas and hydrochloric acid soln counter current contact in hydrochloric acid washing tower (4) are to absorb water-soluble material in the gas;
C. the gas that come out in hydrochloric acid washing tower (4) top in said step b gets into gas adsorbing device (5), contains the sulfur-containing impurities in the tail gas (1) of hydrogenchloride with absorption, and gas is carried out deep purifying;
D. the methanol gas (6) among the said step c after cleaned gas and the heating after the pre-mixing, gets into the middle chemical reaction that takes place of the reactor drum (8) that contains liquid-phase catalyst and synthesizes methyl chloride in mixing tank (7);
E. said steps d is carried out condensing reflux by the methyl chloride gas that contains that reactor drum (8) comes out through reflux condensate device (9); Get into water wash column (10) subsequently; Get into soda-wash tower (11) again; Get into first step sulfuric acid tower (12), second stage sulfuric acid tower (13), third stage sulfuric acid tower (14) afterwards successively, methyl chloride gas is carried out depickling, dehydration and purifying treatment after, obtain highly purified methyl chloride gas;
F. the methyl chloride gas that said step e obtains gets into water cooler (16) again and cools off with condensation and obtain the methyl chloride liquid product behind compressor (15), gets into liquid methyl chloride storage tank (17) storage.
2. a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid as claimed in claim 1 is characterized in that the described pressure that behind compressor, contains hydrogen chloride tail gas (1) of step a brings up to 0.3-0.8MPa.
3. a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid as claimed in claim 1 is characterized in that the described acetic acid scrubber tower of step a (3) is two sections packing towers, and service temperature is 15 ℃ ~ 40 ℃.
4. a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid as claimed in claim 1 is characterized in that the described hydrochloric acid washing tower of step b (4) is two sections packing towers, and service temperature is 15 ℃ ~ 40 ℃.
5. a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid as claimed in claim 1 is characterized in that solid adsorbent in the described gas adsorbing device of step c (5) is one or more in aluminum oxide, molecular sieve, gac, the silica gel.
6. a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid as claimed in claim 1 is characterized in that the described reactor drum of steps d (8) is a glass lined reaction vessel, and temperature of reaction is 130 ~ 160 ℃, and working pressure is 0.1 ~ 0.5MPa.
7. a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid as claimed in claim 1 is characterized in that the described liquid-phase catalyst of steps d is 50% ~ 85% zinc chloride and/or 5% ~ 10% nickel chloride aqueous solution.
8. a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid as claimed in claim 1 is characterized in that the used alkali absorption liquid of the described soda-wash tower of step e (11) is 10% ~ 60% aqueous sodium hydroxide solution.
9. a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid as claimed in claim 1 is characterized in that the used sour absorption liquid of the described third stage sulfuric acid tower of step e (14) is 93% or the above vitriol oil.
10. a kind of method of utilizing the synthetic methyl chloride of tail gas in the production of chloroacetic acid as claimed in claim 1 is characterized in that it specifically may further comprise the steps:
A. from the tail gas that contains hydrogenchloride in the production processes of chloroacetic acid (1); At first get into compressor (2) gas is compressed to 0.5MPa; Get into the bottom of acetic acid washing tower (3) then; The tail gas (1) and acetum counter current contact that in acetic acid washing tower (3), contain hydrogenchloride are to absorb the material that is dissolved in acetic acid in the gas.The service temperature of acetic acid washing tower (3) is 30 ℃.The tail gas (1) that contains hydrogenchloride is discharged from the washing tower top after the acetic acid washing, squeezes into circulation device by pump again after acetic acid is discharged from the bottom and recycles.
B. the gas that comes out from a step acetic acid scrubber tower (3) top, the bottom of entering hydrochloric acid washing tower (4), gas and hydrochloric acid soln counter current contact in hydrochloric acid washing tower (4) are to absorb water-soluble material in the gas.The service temperature of hydrochloric acid washing tower (4) is 30 ℃.The tail gas (1) that contains hydrogenchloride is discharged from the washing tower top behind the salt acid elution, squeezes into circulation device by pump again after hydrochloric acid is discharged from the bottom and recycles.
C. the gas that comes out from b step hydrochloric acid washing tower (4) top gets into gas adsorbing device (5), contains the sulfur-containing impurities in the tail gas (1) of hydrogenchloride with absorption, and gas is carried out deep purifying.Gas adsorbing device (5) inside is filled with molecular sieve and aluminum oxide.
D. the methanol gas (6) after cleaned gas and the heating gets into and in the reactor drum (8) of the aqueous solution liquid-phase catalyst that contains 60% zinc chloride and 10% nickelous chloride chemical reaction takes place and synthesize methyl chloride in mixing tank (7) after the pre-mixing among the step c.The service temperature of reactor drum (8) is 150 ℃, and working pressure is 0.3MPa.
E. said steps d is carried out condensing reflux by the methyl chloride gas that contains that reactor drum (8) comes out through reflux condensate device (9); Get into water wash column (10) subsequently; Get into soda-wash tower (11) then; Get into first step sulfuric acid tower (12), second stage sulfuric acid tower (13), third stage sulfuric acid tower (14) more successively, methyl chloride gas is carried out depickling, dehydration and purifying treatment after, obtain highly purified methyl chloride gas.The used alkali absorption liquid of soda-wash tower (11) is 50% aqueous sodium hydroxide solution.The used sour absorption liquid of sulfuric acid tower (14) is 95% the vitriol oil; The sulfuric acid absorption liquid that comes out from third stage sulfuric acid tower (14) gets into second stage sulfuric acid tower (13), and the sulfuric acid absorption liquid that the sulfuric acid tower from the second stage (13) comes out gets into second stage sulfuric acid tower (12).
F. the methyl chloride gas that said step e obtains is after compressor (15) is compressed to 0.7MPa, and entering water cooler (16) cools off with condensation and obtains the methyl chloride liquid product, gets into liquid methyl chloride storage tank (17) storage at last.
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| CN105129734A (en) * | 2015-07-28 | 2015-12-09 | 江苏同泰化工有限公司 | Method for recovering available substances in chloroacetic acid production tail gas |
| CN107827080A (en) * | 2017-11-16 | 2018-03-23 | 新疆中泰新鑫化工科技股份有限公司 | The cleansing and recycling method of containing benezene hydrogen chloride gas |
| CN108409526A (en) * | 2018-03-09 | 2018-08-17 | 中国化学赛鼎宁波工程有限公司 | A kind of monochloro methane production energy-saving system and method |
| CN109503312A (en) * | 2019-01-15 | 2019-03-22 | 浙江迪邦化工有限公司 | A kind of technique of the by-product hydrogen chloride continuous production chloroethanes using chlorobenzene production |
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| CN111875471A (en) * | 2020-07-28 | 2020-11-03 | 华陆工程科技有限责任公司 | Methyl chloride synthesis process for cyclic dehydration of catalyst |
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| CN105129734A (en) * | 2015-07-28 | 2015-12-09 | 江苏同泰化工有限公司 | Method for recovering available substances in chloroacetic acid production tail gas |
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| CN109503312B (en) * | 2019-01-15 | 2021-08-10 | 浙江迪邦化工有限公司 | Process for continuously producing chloroethane by using byproduct hydrogen chloride produced in chlorobenzene production |
| CN110922995A (en) * | 2019-11-20 | 2020-03-27 | 新奥生物质能(天津)有限公司 | Biomass high-temperature pyrolysis gas treatment method and treatment system |
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| CN111875471B (en) * | 2020-07-28 | 2023-08-29 | 华陆工程科技有限责任公司 | Catalyst circulation dehydration chloromethane synthesis process |
| CN112010770A (en) * | 2020-09-07 | 2020-12-01 | 河北东华舰化工有限公司 | Novel production method of glycine ethyl ester hydrochloride |
| CN114835086A (en) * | 2022-05-07 | 2022-08-02 | 南通星球石墨股份有限公司 | Hydrogen chloride gas purification technology |
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