CN109627142A - A kind of processing method and processing system producing tetrachloro-ethylene by-product tail gas - Google Patents
A kind of processing method and processing system producing tetrachloro-ethylene by-product tail gas Download PDFInfo
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- CN109627142A CN109627142A CN201811516512.8A CN201811516512A CN109627142A CN 109627142 A CN109627142 A CN 109627142A CN 201811516512 A CN201811516512 A CN 201811516512A CN 109627142 A CN109627142 A CN 109627142A
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- ethylene
- tetrachloro
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
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Abstract
The present invention provides a kind of processing method and processing system for producing tetrachloro-ethylene by-product tail gas.Processing method of the present invention is compressed, is condensed comprising steps of producing tetrachloro-ethylene by-product tail gas, and liquid carbon tetrachloride and gaseous mixture are obtained；Gained carbon tetrachloride can continue to participate in and prepare tetrachloro-ethylene；Gained gaseous mixture carries out thermal chlorination with monochloro methane as raw material and reacts, while gained byproduct hydrogen chloride can be used as raw material and be sent to hydrochlorination system.The method of the present invention step is brief, does not need too low condensation temperature, cost is relatively low；The recycling of by-product reduces the consumption of raw material, reduces production cost；It solves the problems, such as the processing of a large amount of hydrogen chloride generated in tetrachloro-ethylene production process, reduces the discharge of the three wastes, while so that tail gas is fully used, improve economic value and environmental benefit.
Description
Technical field
The present invention relates to a kind of processing methods and processing system for producing tetrachloro-ethylene by-product tail gas, belong at process tail gas
Reason field.
Background technique
Methane chloride (including monochloro methane, methylene chloride, chloroform and carbon tetrachloride) and being important of tetrachloro-ethylene
Work raw material.Domestic existing tetrachloro-ethylene production mainly uses C1~C3 hydro carbons thermal chlorination technique, meeting in this art production process
A large amount of tail gas are generated, contain a large amount of hydrogen chloride gas, a small amount of chlorine and carbon tetrachloride in tail gas.These tail gas usually by with
It is and limited to the demand of hydrochloric acid in the market in the dilute hydrochloric acid of preparation low value, often because of the unsalable influence device of hydrochloric acid
Operating load.
Therefore, the reasonable processing and application of above-mentioned tail gas, turns waste into wealth to tail gas, reduces environmental pressure, improves economic valence
Value has great influence.Chinese patent literature CN103816768A discloses a kind of from production chloromethanes or tetrachloro-ethylene tail gas
Recycle the method and system of hydrogen chloride.This method uses methane chloride mixture as solvent, and chlorination is removed in solvent absorption tail gas
Other substances outside hydrogen are to get hydrogen chloride；The system includes absorption tower, circulator and cooler；Solvent is cooling through cooler
Enter absorption tower afterwards, contacted with the tail gas of production chloromethanes or the containing hydrogen chloride of tetrachloro-ethylene, chlorination is removed in solvent absorption tail gas
Other substances outside hydrogen and removal system under the action of circulator.The invention can be to the chlorine in tail gas using distinctive solvent
Change hydrogen and carry out highly selective separation, but this method step is relatively complicated, also, when solvent and tail gas contact required temperature compared with
It is low, it is related to cooler, deep freezer, heat exchanger etc., needs to consume a large amount of hot and cold coal, higher cost.For another example, Chinese patent
Document CN204981132U discloses a kind of system of process for producing tetrachloro-ethylene by-product tail gas, including pressure charging system, cooling capacity are returned
Receive device, cryogenic separator, rectifying column and evaporator.The patent equally uses cryogenic separator, and required temperature is lower, needs to disappear
A large amount of hot and cold coal, higher cost are consumed, and step is also relatively complicated.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provide a kind of processing method for producing tetrachloro-ethylene by-product tail gas and
Processing system.The method of the present invention step is brief, does not need too low condensation temperature, cost is relatively low；Produce tetrachloro-ethylene by-product tail
Gas can continue to participate in through overcompression and condensation, gained carbon tetrachloride and prepare tetrachloro-ethylene；As raw material heat occurs for gained gaseous mixture
Chlorination reaction produces methane polychloride, while gained byproduct hydrogen chloride can be used as raw material and be sent to hydrochlorination system；Above-mentioned pair
The recycling of product reduces the consumption of raw material, reduces production cost；Solve generated in tetrachloro-ethylene production process it is big
Measure hydrogen chloride processing problem, reduce the discharge of the three wastes, while so that tail gas is fully used, improve economic value and
Environmental benefit.
Technical scheme is as follows:
A kind of processing method producing tetrachloro-ethylene by-product tail gas, comprising steps of production tetrachloro-ethylene by-product tail gas is through pressing
Contracting, condensation, obtain liquid carbon tetrachloride and gaseous mixture；Then gaseous mixture is reacted as raw material with monochloro methane progress thermal chlorination.
According to the present invention, produce includes following main component: hydrogen chloride 79-82%wt, chlorine in tetrachloro-ethylene by-product tail gas
Gas and carbon tetrachloride 9-11%wt.
Preferred according to the present invention, the compression is will to produce tetrachloro-ethylene by-product tail gas compression to 0.5~1.5MPa；It is excellent
Choosing, the compression is will to produce tetrachloro-ethylene by-product tail gas compression to 0.5~1.2MPa.
Preferred according to the present invention, the condensation is by compressed tail gas condensing to -30 DEG C~0 DEG C；Preferably, described
Condensation is by compressed tail gas condensing to -15 DEG C~-5 DEG C.
According to the present invention, in the gaseous mixture include following main component: the hydrogen chloride of 80.3%~86%wt and
The chlorine of 10.2%~14%wt.
According to the present invention, the compression, condensation are carried out by the prior art.
According to the present invention, gaseous mixture reacts with monochloro methane progress thermal chlorination as raw material and refers to: the chlorine in gaseous mixture
It is reacted with monochloro methane progress thermal chlorination and prepares methane polychloride, the hydrogen chloride in gaseous mixture is not involved in reaction, and generates chlorine simultaneously
Change hydrogen by-product；The methane polychloride includes: methylene chloride, chloroform, carbon tetrachloride.The thermal chlorination reaction condition can be by existing
Technology carries out.
It is preferred according to the present invention, the thermal chlorination reaction comprising steps of gaseous mixture is preheated prior to 70-90 DEG C, then in
390-410 DEG C, carry out thermal chlorination with monochloro methane under 0.5-0.7MPa and react.
Preferred according to the present invention, gained liquid carbon tetrachloride can be repeated for the preparation of tetrachloro-ethylene after condensing.
Preferred according to the present invention, gaseous mixture gained hydrogen chloride after thermal chlorination is reacted can be used as raw material through condensation and carry out hydrogen
Chlorination reaction；The condensation temperature is -30 DEG C~-10 DEG C.The hydrochlorination can be reacting for hydrogen chloride and methanol.
According to the present invention, a kind of processing system producing tetrachloro-ethylene by-product tail gas, comprising: compressibility, condenser system,
Carbon tetrachloride storage tank and thermal chlorination reaction system；The compressibility, condenser system, carbon tetrachloride storage tank pass through pipeline sequentially phase
Even；The condenser system is also connected with thermal chlorination system by pipeline.
Preferred according to the present invention, the carbon tetrachloride storage tank is connected by circulator with tetrachloro-ethylene production system,
Tetrachloro-ethylene production system is connected by pipeline with compressibility.
Preferred according to the present invention, the thermal chlorination reaction system includes preheater and hot aluminum slag, the preheating
Device is connected with hot aluminum slag, and preheater is connected with condenser system；The hot aluminum slag connects hydrogen by condensing unit
Chlorination system.
According to the present invention, the compressibility, condenser system, carbon tetrachloride storage tank, thermal chlorination reaction system, circulation dress
Set, tetrachloro-ethylene production system, condensing unit, hydrochlorination system can be by the prior art, connection side of the present invention
Formula can be by the prior art.
The workflow of present system: production tetrachloro-ethylene by-product tail gas obtains liquid through compressibility, condenser system
Carbon tetrachloride and gaseous mixture；Liquid carbon tetrachloride enters carbon tetrachloride storage tank, can go successively to tetrachloro-ethylene by circulator
Production system, which continues to participate in, prepares tetrachloro-ethylene；Gaseous mixture enters preheater preheating as raw material, reacts subsequently into thermal chlorination
Device carries out thermal chlorination with monochloro methane and reacts；The hydrogen chloride obtained after thermal chlorination reaction can be used as raw material after condensing unit condenses
It participates in reacting into hydrochlorination system.
Technical characterstic of the invention and the utility model has the advantages that
1, present invention production tetrachloro-ethylene by-product tail gas is more advantageous to tetrachloro in tail gas using first compressing the method condensed afterwards
Change the separation of carbon and hydrogen chloride and chlorine；The carbon tetrachloride in tail gas is condensed, too low condensation temperature is not needed, cost is relatively low,
And the good separating effect of carbon tetrachloride and gaseous mixture.Gained liquid carbon tetrachloride continues to participate in four chloroethenes of preparation after condensing
Alkene；As raw material thermal chlorination reaction production methane polychloride occurs for gained gaseous mixture, while gained byproduct hydrogen chloride can be used as original
Material is sent to hydrochlorination system.Step of the present invention is simple, and the recycling of above-mentioned by-product reduces the consumption of reaction raw materials,
Production cost greatly reduces；It solves the problems, such as the processing of a large amount of hydrogen chloride generated in tetrachloro-ethylene production process, reduces
The discharge of the three wastes, while so that tail gas is fully used, improves economic value and environmental benefit.
2, the present invention avoids the secondary pollution of environment without using organic solvent etc.；The harshnesses such as too low temperature are not needed
Condition, required condition are easily achieved, and cost is relatively low；Production tetrachloro-ethylene by-product tail gas is fully used, and turns waste into wealth, after
Continuous thermal chlorination byproduct of reaction is fully utilized, and is reduced and is prepared tetrachloro-ethylene reaction, thermal chlorination reaction, hydrogen chloride
The cost of reaction etc., substantially increases economic value and environmental benefit.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the processing system of present invention production tetrachloro-ethylene by-product tail gas；
Wherein, W1 is production tetrachloro-ethylene by-product tail gas, and W2 is monochloro methane, and 1 is compressibility, and 2 be condenser system, 3
It is tetrachloro-ethylene production system for carbon tetrachloride storage tank, 4,5 be preheater, and 6 be hot aluminum slag, and 7 be hydrochlorination system
System.
Specific embodiment
Below by specific embodiment and in conjunction with attached drawing, the present invention is described further, but not limited to this.
Embodiment 1
A kind of processing system producing tetrachloro-ethylene by-product tail gas, as shown in Figure 1, comprising: compressibility 1, condenser system
2, (including preheater 5 and hot aluminum slag 6, preheater 5 and thermal chlorination are anti-for carbon tetrachloride storage tank 3 and thermal chlorination reaction system
Device 6 is answered to be sequentially connected)；The compressibility 1, condenser system 2, carbon tetrachloride storage tank 3 are sequentially connected by pipeline, carbon tetrachloride
Storage tank 3 is connected by circulator with tetrachloro-ethylene production system 4, and tetrachloro-ethylene production system 4 passes through pipeline and compressibility 1
It is connected；The condenser system 2 is also connected with preheater 5 by pipeline；The hot aluminum slag 6 connects hydrogen chlorine by condensing unit
Change reaction system 7.
The compressibility 1, condenser system 2, carbon tetrachloride storage tank 3, thermal chlorination reaction system, circulator, four chloroethenes
Alkene production system 4, condensing unit, hydrochlorination system 7 press the prior art, and connection type of the present invention can be by existing
Technology.
Embodiment 2
Using the method for processing system process for producing tetrachloro-ethylene by-product tail gas described in embodiment 1, produced from tetrachloro-ethylene
It include main component: hydrogen chloride 80.3%wt, chlorine and carbon tetrachloride in the production tetrachloro-ethylene by-product tail gas that system 4 comes out
10.2%wt.
Production tetrachloro-ethylene by-product tail gas W1 enters compressibility 1, is compressed to 1.0MPa, cold subsequently into condenser system 2
Solidifying temperature is -10 DEG C；Liquid carbon tetrachloride and gaseous mixture are obtained after condensation (carbon tetrachloride content is 1wt% in mixed gas)；
Liquid carbon tetrachloride enters carbon tetrachloride storage tank 3, returns to tetrachloro-ethylene production system 4 by circulator and continues to participate in preparation four
Vinyl chloride；Gained gaseous mixture main component after condensation are as follows: 85.3%wt hydrogen chloride and 13.6%wt chlorine, gaseous mixture enter preheating
Device 5 is heated to 80 DEG C, and subsequently into hot aluminum slag 6, the chlorine and W2 monochloro methane in gaseous mixture are in reaction temperature 398
DEG C, carry out thermal chlorination reaction under pressure 0.61MPa and prepare methane polychloride；Gained hydrogen chloride gas after thermal chlorination reaction, through being subcooled
Solidifying device is condensed to -15 DEG C, into hydrochlorination system 7, participates in hydrochlorination as raw material.
Embodiment 3
Using the method for processing system process for producing tetrachloro-ethylene by-product tail gas described in embodiment 1, produced from tetrachloro-ethylene
It include main component: hydrogen chloride 80.3%wt, chlorine and carbon tetrachloride in the production tetrachloro-ethylene by-product tail gas that system 4 comes out
10.2%wt.
Production tetrachloro-ethylene by-product tail gas W1 enters compressibility 1, is compressed to 1.2MPa, cold subsequently into condenser system 2
Solidifying temperature is -5 DEG C；Liquid carbon tetrachloride and gaseous mixture are obtained after condensation (carbon tetrachloride content is 1.6wt% in mixed gas)；
Liquid carbon tetrachloride enters carbon tetrachloride storage tank 3, returns to tetrachloro-ethylene production system 4 by circulator and continues to participate in preparation four
Vinyl chloride；Gained gaseous mixture main component after condensation are as follows: 84.8%wt hydrogen chloride and 13.4%wt chlorine, gaseous mixture enter preheating
Device 5 is heated to 80 DEG C, and subsequently into hot aluminum slag 6, the chlorine and W2 monochloro methane in gaseous mixture are in reaction temperature 398
DEG C, carry out thermal chlorination reaction under pressure 0.61MPa and prepare methane polychloride；Gained hydrogen chloride gas after thermal chlorination reaction, through being subcooled
Solidifying device is condensed to -15 DEG C, into hydrochlorination system 7, participates in hydrochlorination as raw material.
Embodiment 4
Using the method for processing system process for producing tetrachloro-ethylene by-product tail gas described in embodiment 1, produced from tetrachloro-ethylene
It include main component: hydrogen chloride 80.3%wt, chlorine and carbon tetrachloride in the production tetrachloro-ethylene by-product tail gas that system 4 comes out
10.2%wt.
Production tetrachloro-ethylene by-product tail gas W1 enters compressibility 1, is compressed to 0.5MPa, cold subsequently into condenser system 2
Solidifying temperature is 0 DEG C；Liquid carbon tetrachloride and gaseous mixture are obtained after condensation (carbon tetrachloride content is 2wt% in mixed gas)；Liquid
Body carbon tetrachloride enters carbon tetrachloride storage tank 3, returns to tetrachloro-ethylene production system 4 by circulator and continues to participate in and prepares tetrachloro
Ethylene；Gained gaseous mixture main component after condensation are as follows: 84.3%wt hydrogen chloride and 12.9%wt chlorine, gaseous mixture enter preheater
5 are heated to 80 DEG C, subsequently into hot aluminum slag 6, chlorine and W2 monochloro methane in gaseous mixture in 398 DEG C of reaction temperature,
Thermal chlorination reaction is carried out under pressure 0.61MPa prepares methane polychloride；Gained hydrogen chloride gas, fills by condensation after thermal chlorination reaction
Condensation is set to -15 DEG C, into hydrochlorination system 7, participates in hydrochlorination as raw material.
Comparative example 1
Using the method for processing system process for producing tetrachloro-ethylene by-product tail gas described in embodiment 1, as described in Example 2,
Except that: production tetrachloro-ethylene by-product tail gas W1 enters compressibility 1, is compressed to 0.3MPa, other steps and condition with
Embodiment 2 is consistent.
Carbon tetrachloride content is 3wt% in gained gaseous mixture after condensing.From there through the comparison with embodiment 2, this hair
Bright pressure limit is conducive to the separation of carbon tetrachloride Yu hydrogen chloride, chlorine.
Comparative example 2
Using the method for processing system process for producing tetrachloro-ethylene by-product tail gas described in embodiment 1, as described in Example 2,
Except that: by compressed tail gas condensing to 10 DEG C, other steps and condition and embodiment 2 are unanimously.
Carbon tetrachloride content is 2.4% in gained gaseous mixture after condensing.From there through the comparison with embodiment 2, this hair
Bright suitable, mild condensation temperature is conducive to the separation of carbon tetrachloride Yu hydrogen chloride, chlorine, and does not need too low temperature,
Save the cost.
Claims (9)
1. a kind of processing method for producing tetrachloro-ethylene by-product tail gas, comprising steps of production tetrachloro-ethylene by-product tail gas through compression,
Condensation, obtains liquid carbon tetrachloride and gaseous mixture；Then gaseous mixture is reacted as raw material with monochloro methane progress thermal chlorination.
2. according to claim 1 produce tetrachloro-ethylene by-product tail gas processing method, which is characterized in that it is described compression be by
Tetrachloro-ethylene by-product tail gas compression is produced to 0.5~1.5MPa；Preferably, the compression is will to produce tetrachloro-ethylene by-product tail gas
It is compressed to 0.5~1.2MPa.
3. according to claim 1 produce tetrachloro-ethylene by-product tail gas processing method, which is characterized in that it is described condensation be by
Compressed tail gas condensing is to -30 DEG C~0 DEG C；Preferably, the condensation is by compressed tail gas condensing to -15 DEG C~-5
℃。
4. producing the processing method of tetrachloro-ethylene by-product tail gas according to claim 1, which is characterized in that the thermal chlorination is anti-
It answers comprising steps of prior to 70-90 DEG C preheating of gaseous mixture, then carries out heat with monochloro methane under 390-410 DEG C, 0.5-0.7MPa
Chlorination reaction.
5. producing the processing method of tetrachloro-ethylene by-product tail gas according to claim 1, which is characterized in that the gained after condensing
Liquid carbon tetrachloride can be repeated for the preparation of tetrachloro-ethylene.
6. producing the processing method of tetrachloro-ethylene by-product tail gas according to claim 1, which is characterized in that gaseous mixture is through hot chlorine
Hydrogen chloride obtained by changing after reacting can be used as raw material through condensation and carry out hydrochlorination.
7. producing the processing system of tetrachloro-ethylene by-product tail gas used in the processing method as described in claim 1-6, comprising: compression system
System, condenser system, carbon tetrachloride storage tank and thermal chlorination reaction system；The compressibility, condenser system, carbon tetrachloride storage tank are logical
Piping is sequentially connected；The condenser system is also connected with thermal chlorination system by pipeline.
8. producing the processing system of tetrachloro-ethylene by-product tail gas according to claim 7, which is characterized in that the carbon tetrachloride
Storage tank is connected by circulator with tetrachloro-ethylene production system, and tetrachloro-ethylene production system passes through pipeline and compressibility phase
Even.
9. producing the processing system of tetrachloro-ethylene by-product tail gas according to claim 7, which is characterized in that the thermal chlorination is anti-
Answering system includes preheater and hot aluminum slag, and the preheater is connected with hot aluminum slag, preheater and condenser system
It is connected；The hot aluminum slag connects hydrochlorination system by condensing unit.
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| CN201811516512.8A CN109627142B (en) | 2018-12-12 | 2018-12-12 | Treatment method and treatment system for byproduct tail gas in tetrachloroethylene production |
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| CN201811516512.8A CN109627142B (en) | 2018-12-12 | 2018-12-12 | Treatment method and treatment system for byproduct tail gas in tetrachloroethylene production |
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| CN109627142B (en) | 2021-10-22 |
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