CN105801346B - A kind of method that tetrachloro-ethylene and carbon trichloride are recycled in the heavy constituent waste liquid produced from tetrachloro-ethylene device - Google Patents
A kind of method that tetrachloro-ethylene and carbon trichloride are recycled in the heavy constituent waste liquid produced from tetrachloro-ethylene device Download PDFInfo
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- CN105801346B CN105801346B CN201410842332.4A CN201410842332A CN105801346B CN 105801346 B CN105801346 B CN 105801346B CN 201410842332 A CN201410842332 A CN 201410842332A CN 105801346 B CN105801346 B CN 105801346B
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Abstract
The present invention relates to a kind of method that tetrachloro-ethylene and carbon trichloride are recycled in heavy constituent waste liquid produced from tetrachloro-ethylene device, comprise the following steps：(1) the heavy constituent waste liquid for producing tetrachloro-ethylene device is sent into heavy constituent rectifying column and carries out rectifying, (2) the condensed rear portion of component that heavy constituent rectifying column tower top obtains sends back to heavy constituent rectifier column reflux, another part sends back to tetrachloro-ethylene device of refining unit and is refined, and obtains tetrachloro-ethylene product；(3) component that heavy constituent rectifying tower bottom obtains is sent into carbon trichloride rectifying column and carries out rectifying, and (4) carbon trichloride rectifying column tower top component is condensed, crushes, and obtains carbon trichloride product.The present invention is avoided in removal process, pipeline and the susceptible to plugging problem of equipment by accurately controlling heavy constituent rectifying column and carbon trichloride rectifying column tower top column bottom temperature；The heavy constituent waste liquid that tetrachloro-ethylene device produces is difficult to resolve certainly by effective solve, the problems such as discharge smell is big.
Description
Technical field
A kind of processing method of the heavy constituent waste liquid produced the present invention relates to tetrachloro-ethylene device, more particularly to it is a kind of from four
The method that tetrachloro-ethylene and carbon trichloride are recycled in the heavy constituent waste liquid that TOWER OUTLET IN VINYL CHLORIDE UNIT produces, belongs to chemical technology field.
Background technology
More than 300,000 tons/year, tetrachloro-ethylene device can give birth to domestic existing tetrachloro-ethylene device capbility in process of production
Into the mixture waste liquid containing gas chromatographies such as carbon tetrachloride, tetrachloro-ethylene, carbon trichloride, hexachlorobutadiene, hexachloro-benzenes, these
Organic matter is mostly heavy constituent (said mixture waste liquid is referred to as heavy constituent waste liquid below).Heavy constituent discharging of waste liquid smell is big,
Complex treatment process and not environmentally, contains more application and is worth very high tetrachloro-ethylene and carbon trichloride in heavy constituent waste liquid；Mesh
Before, most domestic producer all without tetrachloro-ethylene and carbon trichloride in heavy constituent is recycled well, mostly after simple process directly
Run in and put or burn, not only to environmental concerns, but also cause the waste of tetrachloro-ethylene and carbon trichloride, it is uneconomical.Therefore,
Need to provide a kind of production technology for recycling tetrachloro-ethylene heavy constituent.
Tetrachloro-ethylene and carbon trichloride are recycled from heavy constituent waste liquid, domestic also no producer has what is completely handled at present
Technique.In removal process, pipeline and equipment easily block, and the difficult control of technological parameter, the continuous production operation of device is difficult to ensure.
The content of the invention
In view of the deficiencies of the prior art, it is big to solve the heavy constituent liquid waste processing difficulty that produces in tetrachloro-ethylene production process
Problem, the present invention provide the side that tetrachloro-ethylene and carbon trichloride are recycled in a kind of heavy constituent waste liquid produced from tetrachloro-ethylene device
Method.
Technical scheme is as follows：
A kind of method that tetrachloro-ethylene and carbon trichloride are recycled in the heavy constituent waste liquid produced from tetrachloro-ethylene device, including
The following steps：
(1) the heavy constituent waste liquid for producing tetrachloro-ethylene device is sent into heavy constituent rectifying column and carries out rectifying, controls tower top temperature
122~130 DEG C of degree, 190~200 DEG C of column bottom temperature, 0.001~0.01MPa of tower reactor pressure；
(2) the condensed rear portion of component that heavy constituent rectifying column tower top obtains sends back to heavy constituent rectifier column reflux, returns
Than being 0.4~0.6, another part sends back to tetrachloro-ethylene device of refining unit and is refined stream, obtains tetrachloro-ethylene product；
(3) component that heavy constituent rectifying tower bottom obtains is sent into carbon trichloride rectifying column and carries out rectifying, controls tower top temperature
186 DEG C~190 DEG C, 195 DEG C~205 DEG C of column bottom temperature, 0.05~0.1MPa of tower reactor pressure；
(4) carbon trichloride rectifying column tower top component is condensed, crushes, and obtains carbon trichloride product.
, according to the invention it is preferred to, main group of the heavy constituent waste liquid that the tetrachloro-ethylene device described in step (1) produces
Divide as follows：Carbon tetrachloride 0.58~1.86%, tetrachloro-ethylene 47.52~48.52%, pentachloroethane 0.04~0.16%, chlordene
Ethane 18.84~20.62%, hexachlorobutadiene 28.58~34.1%.
, according to the invention it is preferred to, the reflux ratio described in step (2) is 0.5, and the temperature of the condensation is 30~50
℃。
, according to the invention it is preferred to, the temperature condensed described in step (4) is 120~150 DEG C.
, according to the invention it is preferred to, further included in step (4) and carbon trichloride rectifying tower bottom component is subjected to burning disposal
Step.
According to the present invention, the component that heavy constituent rectifying column tower top obtains is mainly the light components such as carbon tetrachloride, tetrachloro-ethylene,
Carbon trichloride rectifying tower bottom component is mainly the heavy constituents such as hexachlorobutadiene, hexachloro-benzene, carbon trichloride rectifying column tower top component
Predominantly carbon trichloride gas, condensed, crushing obtain carbon trichloride product；It is 99.8% to recycle obtained tetrachloro-ethylene purity
More than, the rate of recovery is up to more than 95%；It is more than 98% to recycle obtained carbon trichloride purity, and the rate of recovery is up to more than 85%.
Tetrachloro-ethylene device of the present invention is tetrachloro-ethylene production process, technique mistake well known to those skilled in the art
Journey, wherein, the condensed obtained another part component of heavy constituent rectifying column tower top sends back to tetrachloro-ethylene device essence in step (2)
Unit processed, which carries out refined process, to be carried out by the prior art.
The principle of the present invention：
The principle of the present invention is that each component is separated and recovered by rectifying, and the first step is returned by the method for rectifying first
Receive tetrachloro-ethylene and carbon tetrachloride, this step are mainly controlled, it is necessary to pay attention to tower by controlling bottom temperature and reflux ratio
The composition of kettle heavy constituent, it is ensured that the content of tower reactor hexachlorobutadiene is within proper range, if tower reactor hexachlorobutadiene contains
Amount is too low, then can block tower reactor and follow-up process pipe；Then carbon trichloride, this step master are recycled by the method for rectifying again
Control tower reactor, tower top temperature, it is impossible to which excessive and too low, excessive carbon trichloride purity is not high, too low then easy blocking.Therefore,
The main technological operation point of the present invention is exactly tower reactor, tower top temperature, by accurately controlling, is avoided in removal process, pipeline and is set
Standby susceptible to plugging problem.
The available this area conventional equipment of device therefor of the present invention, heavy constituent rectifying column and carbon trichloride rectifying column space bit
To put as far as possible closely, heat exchanger used in the carbon trichloride condensation that carbon trichloride rectifying column tower top obtains can use U-tube heat exchanger,
Carbon trichloride rectifying column tower top can be fixed on.
Beneficial effects of the present invention are as follows：
1st, method of the present invention by the heavy constituent waste liquid that tetrachloro-ethylene device produces by rectifying, recycles four chloroethene therein
Alkene and carbon trichloride, then by the processing of the heavy constituent such as hexachlorobutadiene, hexachloro-benzene castoff burning.Effectively solve tetrachloro
The heavy constituent waste liquid that ethylene unit produces is difficult to resolve certainly, the problems such as discharge smell is big, and tetrachloro-ethylene and carbon trichloride are recycled
It is cost-effective using more economical.
2nd, the present invention avoids recycling by accurately controlling heavy constituent rectifying column and carbon trichloride rectifying column tower top column bottom temperature
During, pipeline and the susceptible to plugging problem of equipment.
Embodiment
Below by specific embodiment, the invention will be further described.
Device therefor is this area conventional equipment in embodiment, commercial products.
Embodiment 1
The main composition for the heavy constituent waste liquid that the present embodiment tetrachloro-ethylene device produces：Carbon tetrachloride 1.86%, four chloroethenes
Alkene 48%, pentachloroethane：0.16%th, carbon trichloride 20.62%, hexachlorobutadiene 29.35%.
A kind of method that tetrachloro-ethylene and carbon trichloride are recycled in the heavy constituent waste liquid produced from tetrachloro-ethylene device, including
The following steps：
(1) the heavy constituent waste liquid for producing tetrachloro-ethylene device enters heavy constituent rectifying column, controls heavy constituent rectifying tower
192.6 DEG C, tower bottom pressure 0.003MPa of bottom temperature, 123.8 DEG C of tower top temperature；
(2) component that heavy constituent rectifying column tower top obtains sends back to heavy constituent rectifying column through 42 DEG C of condensation rear portions and returns
Stream, regurgitant volume 0.5m3/ h, reflux ratio 0.5, another part send back to tetrachloro-ethylene device of refining unit and are refined, and obtain tetrachloro
Ethylene product；
(3) component that heavy constituent rectifying tower bottom obtains is sent into carbon trichloride rectifying column and carries out rectifying, controls carbon trichloride
198.8 DEG C, tower bottom pressure 0.06MPa of rectifying column column bottom temperature, 188.1 DEG C of tower top temperature；
(4) carbon trichloride rectifying column tower top component obtains carbon trichloride product through 143 DEG C of condensations, crushing；Carbon trichloride rectifying
Tower bottom of towe component is sent into incinerator and carries out burning disposal.
The tetrachloro-ethylene purity that the present embodiment obtains is 99.9%, and for the rate of recovery up to 96%, carbon trichloride purity is 98.5%,
The rate of recovery 87%.
Embodiment 2
The main composition for the heavy constituent waste liquid that the present embodiment tetrachloro-ethylene device produces：Carbon tetrachloride 0.58%, four chloroethenes
Alkene 47.52%, pentachloroethane 0.04%, carbon trichloride 18.84%, hexachlorobutadiene 33.01%.
A kind of method that tetrachloro-ethylene and carbon trichloride are recycled in the heavy constituent waste liquid produced from tetrachloro-ethylene device, including
The following steps：
(1) the heavy constituent waste liquid for producing tetrachloro-ethylene device enters heavy constituent rectifying column, controls heavy constituent rectifying tower
195.2 DEG C, tower bottom pressure 0.005MPa of bottom temperature, 124.9 DEG C of tower top temperature；
(2) component that heavy constituent rectifying column tower top obtains sends back to heavy constituent rectifying column through 45.8 DEG C of condensation rear portions and returns
Stream, regurgitant volume 0.49m3/ h, reflux ratio 0.48, another part send back to tetrachloro-ethylene device of refining unit and are refined, and obtain four
Vinyl chloride product；
(3) component that heavy constituent rectifying tower bottom obtains is sent into carbon trichloride rectifying column and carries out rectifying, controls carbon trichloride
196.5 DEG C, tower bottom pressure 0.05MPa of rectifying column column bottom temperature, 187.0 DEG C of tower top temperature；
(4) carbon trichloride rectifying column tower top component obtains carbon trichloride product through 138 DEG C of condensations, crushing；Carbon trichloride rectifying
Tower bottom of towe component is sent into incinerator and carries out burning disposal.
The tetrachloro-ethylene purity that the present embodiment obtains is 99.89%, and the rate of recovery is up to 96.8%, carbon trichloride purity
98.1%, the rate of recovery 86.7%.
Embodiment 3
The main composition for the heavy constituent waste liquid that the present embodiment tetrachloro-ethylene device produces：Carbon tetrachloride 1.75%, four chloroethenes
Alkene 48.52%, pentachloroethane 0.12%, carbon trichloride 19.58%, hexachlorobutadiene 30.02%.
A kind of method that tetrachloro-ethylene and carbon trichloride are recycled in the heavy constituent waste liquid produced from tetrachloro-ethylene device, including
The following steps：
(1) the heavy constituent waste liquid for producing tetrachloro-ethylene device enters heavy constituent rectifying column, controls heavy constituent rectifying tower
197.3 DEG C, tower bottom pressure 0.007MPa of bottom temperature, 127.1 DEG C of tower top temperature；
(2) component that heavy constituent rectifying column tower top obtains sends back to heavy constituent rectifying column through 36.9 DEG C of condensation rear portions and returns
Stream, regurgitant volume 0.52m3/ h, reflux ratio 0.52, another part send back to former tetrachloro-ethylene device of refining unit and are refined, obtained
Tetrachloro-ethylene product；
(3) component that heavy constituent rectifying tower bottom obtains is sent into carbon trichloride rectifying column and carries out rectifying, controls carbon trichloride
202.9 DEG C, tower bottom pressure 0.068MPa of rectifying column column bottom temperature, 189.2 DEG C of tower top temperature；
(4) carbon trichloride rectifying column tower top component obtains carbon trichloride product through 147 DEG C of condensations, crushing；Carbon trichloride rectifying
Tower bottom of towe component is sent into incinerator and carries out burning disposal.
The tetrachloro-ethylene purity that the present embodiment obtains is 99.93%, and the rate of recovery is up to 95.8%, carbon trichloride purity
98.2%, the rate of recovery 86.4%.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail in good embodiment, it will be understood by those of ordinary skill in the art that, can be to the skill of the present invention
Art scheme technical scheme is modified or replaced equivalently, without departing from the objective and scope of technical solution of the present invention, it should all cover from this
Among the right of invention.
Claims (5)
1. the method for tetrachloro-ethylene and carbon trichloride is recycled in a kind of heavy constituent waste liquid produced from tetrachloro-ethylene device, including under
Row step：
（1）The heavy constituent waste liquid that tetrachloro-ethylene device is produced is sent into heavy constituent rectifying column and carries out rectifying, controls tower top temperature 122
~ 130 DEG C, 190 ~ 200 DEG C of column bottom temperature, 0.001 ~ 0.01 MPa of tower reactor pressure；
The key component for the heavy constituent waste liquid that the tetrachloro-ethylene device produces is as follows：Carbon tetrachloride 0.58 ~ 1.86%, tetrachloro
Ethene 47.52 ~ 48.52%, pentachloroethane 0.04 ~ 0.16%, carbon trichloride 18.84 ~ 20.62%, hexachlorobutadiene 28.58 ~
34.1%；
（2）The condensed rear portion of component that heavy constituent rectifying column tower top obtains sends back to heavy constituent rectifier column reflux, reflux ratio
For 0.4 ~ 0.6, another part sends back to tetrachloro-ethylene device of refining unit and is refined, and obtains tetrachloro-ethylene product；
（3）The component that heavy constituent rectifying tower bottom obtains is sent into carbon trichloride rectifying column and carries out rectifying, controls 186 DEG C of tower top temperature
~ 190 DEG C, 195 DEG C ~ 205 DEG C of column bottom temperature, 0.05 ~ 0.1MPa of tower reactor pressure；
（4）Carbon trichloride rectifying column tower top component is condensed, crushes, and obtains carbon trichloride product.
2. recycle tetrachloro-ethylene and hexachloroethanc in the heavy constituent waste liquid according to claim 1 produced from tetrachloro-ethylene device
The method of alkane, it is characterised in that step（2）Described in reflux ratio be 0.5.
3. recycle tetrachloro-ethylene and hexachloroethanc in the heavy constituent waste liquid according to claim 1 produced from tetrachloro-ethylene device
The method of alkane, it is characterised in that step（2）Described in the temperature that condenses be 30 ~ 50 DEG C.
4. recycle tetrachloro-ethylene and hexachloroethanc in the heavy constituent waste liquid according to claim 1 produced from tetrachloro-ethylene device
The method of alkane, it is characterised in that step（4）Described in the temperature that condenses be 120 ~ 150 DEG C.
5. recycle tetrachloro-ethylene and hexachloroethanc in the heavy constituent waste liquid according to claim 1 produced from tetrachloro-ethylene device
The method of alkane, it is characterised in that step（4）In further include by carbon trichloride rectifying tower bottom component carry out burning disposal step.
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| CN201410842332.4A CN105801346B (en) | 2014-12-30 | 2014-12-30 | A kind of method that tetrachloro-ethylene and carbon trichloride are recycled in the heavy constituent waste liquid produced from tetrachloro-ethylene device |
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| CN201410842332.4A CN105801346B (en) | 2014-12-30 | 2014-12-30 | A kind of method that tetrachloro-ethylene and carbon trichloride are recycled in the heavy constituent waste liquid produced from tetrachloro-ethylene device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106187676B (en) * | 2016-08-19 | 2018-09-11 | 泸州鑫福化工有限公司 | The recovery method of distillation residual liquid in a kind of production of tetrachloro-ethylene |
| CN107056580B (en) * | 2017-05-05 | 2020-10-30 | 乐山师范学院 | Method for preparing perchloroethane and perchlorobutane by ionization |
| CN110540486B (en) * | 2018-05-29 | 2023-06-09 | 乳源东阳光氟有限公司 | Separation system and separation method for byproduct high-boiling-point substances in tetrachloroethylene production |
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| US2725412A (en) * | 1954-06-14 | 1955-11-29 | Ethyl Corp | Chlorination of 1, 1-dichloroethane |
| CN103086839A (en) * | 2012-12-20 | 2013-05-08 | 山东东岳氟硅材料有限公司 | Production process for production of tetrachloroethylene and coproduction of hexachloroethane by using methane chloride residual liquid |
| CN103787823A (en) * | 2014-02-28 | 2014-05-14 | 重庆海洲化学品有限公司 | Method for recovering organic chloride from rectification residues of methane chloride or/and tetrachloroethylene |
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2014
- 2014-12-30 CN CN201410842332.4A patent/CN105801346B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2725412A (en) * | 1954-06-14 | 1955-11-29 | Ethyl Corp | Chlorination of 1, 1-dichloroethane |
| CN103086839A (en) * | 2012-12-20 | 2013-05-08 | 山东东岳氟硅材料有限公司 | Production process for production of tetrachloroethylene and coproduction of hexachloroethane by using methane chloride residual liquid |
| CN103787823A (en) * | 2014-02-28 | 2014-05-14 | 重庆海洲化学品有限公司 | Method for recovering organic chloride from rectification residues of methane chloride or/and tetrachloroethylene |
Non-Patent Citations (3)
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| 四氯乙烯的生产和应用;张艳梅等;《中国氯碱》;20060625(第06期);9-13 * |
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