CN109867585A - A kind of chloropropene prepares epichlorohydrin reaction process waste gas processing method - Google Patents

A kind of chloropropene prepares epichlorohydrin reaction process waste gas processing method Download PDF

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Publication number
CN109867585A
CN109867585A CN201711249722.0A CN201711249722A CN109867585A CN 109867585 A CN109867585 A CN 109867585A CN 201711249722 A CN201711249722 A CN 201711249722A CN 109867585 A CN109867585 A CN 109867585A
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China
Prior art keywords
tower
absorption tower
chloropropene
reaction
epoxychloropropane
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CN201711249722.0A
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Chinese (zh)
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高爽
张毅
吕迎
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CN201711249722.0A priority Critical patent/CN109867585A/en
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Abstract

A kind of chloropropene provided by the invention prepares epichlorohydrin reaction process waste gas processing method, and reaction unit is made of reaction end gas surge tank, absorption tower, tower bottom heat exchanger, overhead condenser, top gaseous phase surge tank;To using reaction control phase transfer catalyst, hydrogen peroxide to carry out the exhaust gas progress condensed absorbent processing that chloro propylene epoxidation reaction prepares the generation of epoxychloropropane process for oxidant, the chloropropene recycled in exhaust gas reaches discharge standard.

Description

A kind of chloropropene prepares epichlorohydrin reaction process waste gas processing method
Technical field
The invention belongs to petrochemical industries, and in particular to a kind of chloropropene is prepared at epichlorohydrin reaction process waste gas Reason method.
Background technique
Epoxychloropropane (Epichlorohydrin, ECH) is a kind of important basic chemical industry raw material, mainly for the production of Epoxy resin, chlorohydrin rubber, glycerol and surfactant, medicine, pesticide, coating, ion exchange resin, plasticizer etc. are a variety of Product, industrial process mainly have chlorohydrination and allyl acetate-allyl alcohol method.
In recent years, reaction control phase transfer catalyst achieves more progress during epoxidation reaction of olefines, this is urged Agent is widely used in the alkene such as propylene, chloropropene, butylene, isobutene, styrene, 1- octene, cyclohexene, cyclo-octene, 1- laurylene In hydrocarbon ring oxidation reaction [Li Jun, invigorating, Xi Zuwei reaction control phase transfer catalyst progress of research catalysis journal, 2010, 31 (8): 895~911.].Especially with reaction control phase transfer catalyst, using hydrogen peroxide as oxidant, in inert gas air pressure Under the conditions of carry out preparing epichlorohydrin by chloropropene epoxidation, which has that whole set process is simple, low energy consumption, reaction item The feature that part is mild, the three wastes are few is suitable for epoxychloropropane industrial production.The technology waste gas is in subsequent technique treatment process Method there is no mature treatment process, propose to solve this technical problem a kind of to using hydrogen peroxide as oxygen source, reaction control Catalyzed By Phase-transfer Catalyst chloro propylene epoxidation reaction processed generates the treatment process and method of exhaust gas.
Summary of the invention
The purpose of the present invention is to provide a kind of chloropropenes to prepare epichlorohydrin reaction process waste gas processing method, the party Method is to be catalyzed preparing epichlorohydrin by chloropropene epoxidation as oxygen source, reaction control phase transfer catalyst using hydrogen peroxide to react The tail gas generated in journey enters the chloropropene in absorption tower in condensed absorbent tail gas by reaction end gas surge tank, reduces tail gas In content of organics.Chloro propylene epoxidation, which is catalyzed, as oxygen source, reaction control phase transfer catalyst using hydrogen peroxide prepares epoxy The tail gas generated in chloropropane reaction process contains nitrogen, chloropropene and oxygen, and tail gas direct emission will cause chloropropene loss And pollution is generated to atmosphere, need to solve chloropropene loss in order to which production technology is environmentally protective and pollution is generated to atmosphere, therefore The present invention provides a kind of chloropropene and prepares epoxychloropropane process waste gas processing method.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows:
Ring is prepared to using reaction control phase transfer catalyst, hydrogen peroxide to carry out chloro propylene epoxidation reaction for oxidant The exhaust gas that oxygen chloropropane process generates carries out condensed absorbent processing, recycles the chloropropene in exhaust gas.A kind of chloropropene prepares epoxy Chloropropane reaction process waste gas processing method, it is characterised in that: reaction unit include reaction end gas surge tank V1, absorption tower T1, Tower bottom heat exchanger E1, overhead condenser E2, top gaseous phase surge tank V2, prepare epoxychloropropane mistake to chloro propylene epoxidation reaction The exhaust gas that journey generates, exhaust gas enter the absorption tower lower part T1 by reaction end gas surge tank V1, and absorption tower T1 tower reactor inserts ring in advance Oxygen chloropropane, absorption tower T1 tower bottom are equipped with epoxychloropropane outflux, the epoxychloropropane warp of epoxychloropropane outflux outflow It is back to the absorption tower lower part T1 again after heat exchanger E1 heat exchange, epoxychloropropane is formed by tower bottom heat exchanger E1 and absorption tower T1 Rectification section is sent in extraction after low-temperature circulating absorbs chloropropene, and absorption tower T1 tower top is equipped with overhead condenser E2 and keeps deep cooling, condensation The condensed condensate liquid of device E2 is back to the absorption tower top T1 after entering top gaseous phase surge tank V2, and condenser gas phase is by emptying Exhaust pipe discharge, recycles the chloropropene in exhaust gas.
Chloropropene generates giving up containing nitrogen, chloropropene and oxygen after preparing the emptying condensation of epoxychloropropane process gas phase Gas, the exhaust gas are that hydrogen peroxide is used to be catalyzed chloro propylene epoxidation reaction for oxidant, reaction control phase transfer catalyst The exhaust gas of epoxychloropropane process generation is prepared, generation contains nitrogen after chloropropene prepares the emptying condensation of epoxychloropropane process gas phase Gas, chloropropene and oxygen.
Reaction end gas is connected with reaction end gas surge tank V1 entrance, reaction end gas surge tank V1 outlet with absorption tower T1 under Portion's entrance is connected, and absorption tower T1 outlet at bottom is connected with tower bottom heat exchanger E1 entrance, tower bottom heat exchanger E1 centre exit and absorption Tower T1 middle and lower part entrance is connected, and tower bottom heat exchanger E1 top exit is extraction absorbing liquid, and absorption tower T1 top exit and tower top are cold Condenser E2 entrance is connected, and the outlet overhead condenser E2 is connected with top gaseous phase surge tank V2 top entry, top gaseous phase surge tank V2 outlet at bottom is connected with the absorption tower middle and upper part T1 entrance, and top gaseous phase surge tank V2 top exit is equipped with emptying end gas pipeline.
Tower bottom heat exchanger E1 temperature range: -5~25 DEG C;Overhead condenser E2 temperature range: -5~-20 DEG C.
Absorption tower T1 pressure limit are as follows: 0~500kPa, in tower reactor epoxychloropropane charging quantity be tower reactor volume 30~ 75%.
A kind of chloropropene provided by the invention prepares epichlorohydrin reaction process waste gas processing method, solves with peroxide Change hydrogen is oxygen source, reaction control phase transfer catalyst catalysis preparing epichlorohydrin by chloropropene epoxidation process is crossed generation exhaust gas and asked Topic, the technological operation is simple, technical security is reliable, organic matter extrusion rate is high in exhaust gas, is widely portable to alkene epoxidation system In standby epoxide waste gas treatment process.
Detailed description of the invention
Fig. 1 is generation waste-gas treatment process flow schematic diagram in preparing epichlorohydrin by chloropropene epoxidation reaction process.
Wherein: V1 is reaction end gas surge tank, V2 is top gaseous phase surge tank, T1 is absorption tower, E1 be tower bottom heat exchanger, E2 is overhead condenser.
Specific embodiment
As shown in Figure 1, technique of the invention is by reaction end gas surge tank V1, absorption tower T1, tower bottom heat exchanger E1, tower top Condenser E2, top gaseous phase surge tank V2 composition.
Concrete technology implementation process are as follows:
The tail gas that reaction process generates enters the absorption tower lower part T1 by reaction end gas surge tank V1, and absorption tower T1 tower reactor is pre- Epoxychloropropane is first inserted, absorption tower T1 tower bottom is equipped with epoxychloropropane outflux, the epoxy of epoxychloropropane outflux outflow Chloropropane is back to the absorption tower lower part T1 again after heat exchanger E1 heat exchange, and epoxychloropropane is by tower bottom heat exchanger E1 and absorbs Tower T1 forms extraction after low-temperature circulating absorbs chloropropene and send rectification section, and absorption tower T1 tower top is equipped with overhead condenser E2 and keeps deep Cold, the condensed condensate liquid of condenser E2 is back to the absorption tower top T1, condenser gas phase after entering top gaseous phase surge tank V2 By emptying end gas discharge of pipes, the chloropropene in exhaust gas is recycled.Below by specific embodiment to the present invention done into One step explanation.
Embodiment 1
It is 10 DEG C that tower bottom heat exchanger E1 temperature, which is arranged,;
It is -15 DEG C that overhead condenser E2 heat exchange temperature, which is arranged,;
T1 pressure limit in absorption tower is set are as follows: 100kPa,
It is the 50% of tower reactor volume that epoxychloropropane charging quantity in the T1 tower reactor of absorption tower, which is arranged,.
It is anti-as oxygen source, reaction control phase transfer catalyst catalysis preparing epichlorohydrin by chloropropene epoxidation using hydrogen peroxide Answering process to generate exhaust-gas treatment the results are shown in Table 1, it is seen that organic matter is significantly less in the exhaust gas after the process, reduces The content of chloropropene in exhaust gas.
1. preparing epichlorohydrin by chloropropene epoxidation technology waste gas processing result of table
Embodiment 2
It is 0 DEG C that tower bottom heat exchanger E1 temperature, which is arranged,;
It is -20 DEG C that overhead condenser E2 heat exchange temperature, which is arranged,;
T1 pressure limit in absorption tower is set are as follows: 500kPa,
It is the 65% of tower reactor volume that epoxychloropropane charging quantity in the T1 tower reactor of absorption tower, which is arranged,.
It is anti-as oxygen source, reaction control phase transfer catalyst catalysis preparing epichlorohydrin by chloropropene epoxidation using hydrogen peroxide Answering process to generate exhaust-gas treatment the results are shown in Table 2, it is seen that organic matter is significantly less in the exhaust gas after the process, reduces The content of chloropropene in exhaust gas.
2. preparing epichlorohydrin by chloropropene epoxidation technology waste gas processing result of table
Embodiment 3
It is 15 DEG C that tower bottom heat exchanger E1 temperature, which is arranged,;
It is -10 DEG C that overhead condenser E2 heat exchange temperature, which is arranged,;
T1 pressure limit in absorption tower is set are as follows: 300kPa,
It is the 45% of tower reactor volume that epoxychloropropane charging quantity in the T1 tower reactor of absorption tower, which is arranged,.
It is anti-as oxygen source, reaction control phase transfer catalyst catalysis preparing epichlorohydrin by chloropropene epoxidation using hydrogen peroxide Answering process to generate exhaust-gas treatment the results are shown in Table 3, it is seen that organic matter is significantly less in the exhaust gas after the process, reduces The content of chloropropene in exhaust gas.
3. preparing epichlorohydrin by chloropropene epoxidation technology waste gas processing result of table

Claims (5)

1. a kind of chloropropene prepares epichlorohydrin reaction process waste gas processing method, it is characterised in that: reaction unit includes anti- Tail gas buffer (V1), absorption tower (T1), tower bottom heat exchanger (E1), overhead condenser (E2), top gaseous phase surge tank (V2) are answered, The exhaust gas of epoxychloropropane process generation is prepared to chloro propylene epoxidation reaction, exhaust gas enters by reaction end gas surge tank (V1) The lower part absorption tower (T1), absorption tower (T1) tower reactor insert epoxychloropropane in advance, and absorption tower (T1) tower bottom is equipped with epoxychloropropane The epoxychloropropane of outflux, the outflow of epoxychloropropane outflux is back to absorption tower (T1) after heat exchanger (E1) heat exchange again Lower part, epoxychloropropane form extraction after low-temperature circulating absorbs chloropropene by tower bottom heat exchanger (E1) and absorption tower (T1) and send essence Workshop section is evaporated, absorption tower (T1) tower top is equipped with overhead condenser (E2) and keeps deep cooling, and the condensed condensate liquid of condenser (E2) enters The top absorption tower (T1) is back to after top gaseous phase surge tank (V2), condenser gas phase passes through emptying end gas discharge of pipes, recycling Chloropropene in exhaust gas.
2. according to the method described in claim 1, it is characterized by:
The exhaust gas is that hydrogen peroxide is used to be catalyzed chloro propylene epoxidation reaction for oxidant, reaction control phase transfer catalyst The exhaust gas of epoxychloropropane process generation is prepared, generation contains nitrogen after chloropropene prepares the emptying condensation of epoxychloropropane process gas phase Gas, chloropropene and oxygen.
3. according to the method described in claim 1, it is characterized by:
Reaction end gas is connected with reaction end gas surge tank (V1) entrance, in reaction end gas surge tank (V1) outlet and absorption tower (T1) Lower entrances are connected, and absorption tower (T1) outlet at bottom is connected with tower bottom heat exchanger (E1) entrance, go out in the middle part of tower bottom heat exchanger (E1) Mouth is connected with the middle and lower part absorption tower (T1) entrance, and tower bottom heat exchanger (E1) top exit is extraction absorbing liquid, the top absorption tower (T1) Portion outlet is connected with overhead condenser (E2) entrance, overhead condenser (E2) outlet and top gaseous phase surge tank (V2) top entry It is connected, top gaseous phase surge tank (V2) outlet at bottom is connected with the middle and upper part absorption tower (T1) entrance, top gaseous phase surge tank (V2) Top exit is equipped with emptying end gas pipeline.
4. according to the method described in claim 1, it is characterized by:
Tower bottom heat exchanger (E1) temperature range: -5~25 DEG C;Overhead condenser (E2) temperature range: -5~-20 DEG C.
5. according to the method described in claim 1, it is characterized by:
Absorption tower (T1) pressure limit are as follows: 0~500kPa, in tower reactor epoxychloropropane charging quantity be tower reactor volume 30~ 75%.
CN201711249722.0A 2017-12-01 2017-12-01 A kind of chloropropene prepares epichlorohydrin reaction process waste gas processing method Pending CN109867585A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115138185A (en) * 2022-07-30 2022-10-04 武汉凯比思电力设备有限公司 Device and method for treating and recycling waste gas in epichlorohydrin production process

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CN1962028A (en) * 2006-10-26 2007-05-16 清华大学 Method for reclaiming methylene chloride from waste gas
US20120238782A1 (en) * 2009-11-17 2012-09-20 Masahiro Kinoshita Methods for producing allyl chloride and dichlorohydrin
CN101870709A (en) * 2010-06-25 2010-10-27 天津大学 Method for refining and reclaiming chloromethane from organic silicon production process
CN202116344U (en) * 2011-06-10 2012-01-18 山东聊城鲁西化工第六化肥有限公司 Device for comprehensively treating production waste water of methane chloride
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CN104844416A (en) * 2015-03-26 2015-08-19 南京师范大学 Method for multistage extracting and absorpting dichloromethane and monochloroacetone in MCPa synthetic tail gas
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115138185A (en) * 2022-07-30 2022-10-04 武汉凯比思电力设备有限公司 Device and method for treating and recycling waste gas in epichlorohydrin production process
CN115138185B (en) * 2022-07-30 2023-12-05 武汉凯比思电力设备有限公司 Device and method for treating and recycling waste gas in epichlorohydrin production process

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