CN103936548B - Method for producing 1,1, 2-trichloroethane by chlorination of 1, 2-dichloroethane - Google Patents
Method for producing 1,1, 2-trichloroethane by chlorination of 1, 2-dichloroethane Download PDFInfo
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 title abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 34
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000460 chlorine Substances 0.000 claims abstract description 28
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 28
- 238000000066 reactive distillation Methods 0.000 claims abstract description 28
- 239000007791 liquid phase Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000007086 side reaction Methods 0.000 claims description 104
- 238000000605 extraction Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 20
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000012808 vapor phase Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- -1 receive Chemical compound 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing 1,1, 2-trichloroethane by chlorination of 1, 2-dichloroethane, which adopts a reaction rectification integrated device mainly comprising a rectification tower and a side reactor, takes 1, 2-dichloroethane and chlorine as raw materials, directly introduces the 1, 2-dichloroethane into the side reactor, and performs chlorination reaction with the chlorine under the photocatalysis condition. And returning the reacted material in the side reactor to the rectifying tower, extracting the liquid phase material of the tower plate of the rectifying tower into the next-stage side reactor for continuous chlorination reaction, and obtaining the required product from the rectifying tower kettle. The method has the advantages of simple process flow, flexible operation, low production cost and high economic benefit; the advantages of the reactive distillation integration technology can be kept, the operating conditions of the reactor and the rectifying tower can be kept independent, the volume and the reaction amount of the reactor can be freely adjusted, the optimal matching of the reaction capacity and the separation capacity is realized, and the large-scale industrial production is favorably realized.
Description
Technical field
The invention belongs to chemical field, relate to a kind of technique of producing vinyl trichloride, specifically one take 1,2-ethylene dichloride as the technique of raw material production vinyl trichloride.
Background technology
Vinyl trichloride is a kind of important organic intermediate, can be used for production vinylidene.The method of preparation of industrialization vinyl trichloride mainly contains vinylchlorid chlorination process and 1,2-ethylene dichloride chlorination process.Vinylchlorid chlorination process is ripe, and reaction conditions is gentle; But along with international oil price Continued, vinylchlorid chlorination process production cost is higher, 1,2-ethylene dichloride chlorination process relies on its raw materials cost advantage to receive much attention.
1,2-ethylene dichloride chlorination reaction is a multistep consecutive reaction process, along with the difference of depth of chlorination, reaction can generate vinyl trichloride, 1,1,1,2-tetrachloroethane (abbreviation unsym-tetrachloroethane), 1,1,2, many chlorinated compounds such as 2-tetrachloroethane (being called for short positive tetrachloroethane), pentaline, hexachloroethane, except hexachloroethane be all hydrogen all by the final chlorizate that chlorine replaces, other many chloro-products are all intermediate products of chlorination consecutive reaction.
Patent US2174737 describes 1, 2-ethylene dichloride and chlorine photocatalytically generate 1, 1, 2-trichloroethane, report gas phase 1 in patent US2140549, 2-ethylene dichloride and chlorine by the metal chloride of melting (as iron, receive, zinc, aluminium etc.) produce 1, 1, 2-trichloroethane, patent US3919337 describes one and does not use illumination and any catalyzer, under higher temperature and pressure (120 ~ 150 DEG C, 3 ~ 5atm) by 1, 2-ethylene dichloride direct chlorination generates 1, 1, the method of 2-trichloroethane, patent CN101921167 describes a kind of multi-floating bodies and produces 1, 1, the method of 2-trichloroethane.The shortcoming of these methods is that reaction conditions is complicated above, and the selectivity of reaction is poor, many chloros by product is many, causes difficulty and the high cost of later separation.
For overcoming 1, complicated, the very difficult highly selective of reaction product of 2-ethylene dichloride chlorination obtains the shortcoming of target product, adopt reactive distillation integrated technology not only can reduce reaction process flow process, and reactant can be separated with product original position, be conducive to improving transformation efficiency and selectivity.The people such as Wu Huabing (Wu Huabing, Yuan Xiangqian, Song Hong space .1,2-ethylene dichloride reactive distillation prepares 1,1,2-trichloroethane. chemical reaction engineering and technique .2008,24 (4): 381-384) adopt reaction rectification technique, with 21,2-monochloroethane and chlorine are raw material, in reactive distillation column, prepare 1,1,2-trichloroethane, under the condition of reaction pressure 0.2MPa, temperature of reaction 110 DEG C, 1,1, the selectivity of 2-trichloroethane is maximum reaches 96%, but temperature of reaction and pressure higher.But, by the traditional way that reaction and rectifying are coupled in tower, response capacity depends on the liquid holdup on rectifying tower plates or filler, therefore plant capacity is limited by very large, only take to pressurize, improve the mode of temperature and strengthen reaction and carry out lifting gear ability, be not suitable for large-scale industrial production.
Summary of the invention
Object of the present invention is exactly for existing 1,2-ethylene dichloride chlorination production 1,1, the deficiency of 2-trichloroethane technology, provides a kind of in the reactive distillation integrating device that forms of being coupled by rectifying tower and side reaction device, by 1,2-ethylene dichloride and chlorine reaction produce the method for vinyl trichloride.
Object of the present invention can be reached by following measures:
A kind of with 1,2-ethylene dichloride is raw material production 1,1, the method of 2-trichloroethane, the method adopts the reactive distillation integrating device primarily of rectifying tower and side reaction device coupling composition, with 1,2-ethylene dichloride and chlorine are raw material, 1,2-ethylene dichloride is directly passed into the First side reaction device be coupled with rectifying tower, chlorine passes into each the side reaction device be connected with rectifying tower continuously, in First side reaction device, photocatalytically chlorination reaction occurs, the liquid phase material be obtained by reacting in side reaction device enters rectifying tower, obtains required product from rectifying tower reactor; Or when side reaction device is more than two, continues chlorination reaction by entering next stage side reaction device after the liquid phase material extraction of rectifying tower, then be back to next block column plate of extraction, obtain required product from rectifying tower reactor; Wherein, total intake of chlorine and the inlet amount mol ratio of 1,2-ethylene dichloride are 1:1.
Described rectifying tower working pressure controls at normal pressure; Temperature of reaction in each side reaction device is at 20 ~ 80 DEG C, and reaction pressure controls at normal pressure, and reaction time controls at 0.1 ~ 5h.The tower top temperature of rectifying tower is 80 ~ 90 DEG C, and tower bottom of rectifying tower temperature is 110 ~ 115 DEG C.
Temperature of reaction preferably in each side reaction device is at 50 ~ 70 DEG C.
Reaction time preferably in each side reaction device controls at 0.5 ~ 2h.
Rectifying tower is divided into reactive distillation district and stripping zone from top to bottom, and described side reaction device passes through into and out of material pipe and reactive distillation district butt coupling; Stripping zone stage number at 5 ~ 50 pieces, preferably 10 ~ 20 pieces; Reactive distillation district stage number at 1 ~ 20 piece, preferably 5 ~ 15 pieces.Between sides adjacent reactor, the reactive distillation district stage number at interval is at 1 ~ 5 piece.Chlorine passes into each the side reaction device be connected with rectifying tower by a certain percentage continuously; First side reaction device is entered after the full extraction of tower top light constituent, after chlorine generation chlorination reaction, return reactive distillation district rectifying tower first block of column plate, the full extraction of column plate liquid phase material of reactive distillation district enters each the side reaction device be attached thereto respectively and carries out chlorination reaction, returns next block column plate of reactive distillation district extraction column plate after reaction; Chlorination reaction product carries out carrying heating up in a steamer in the stripping zone of rectifying tower, and gained reaction product is by extraction at the bottom of tower.
The turnover material of side reaction device of the present invention is all connected with rectifying tower, side reaction device number of units 1 ~ 5, preferably 2 ~ 4.When side reaction device number of units is multiple stage, 1,2-ethylene dichloride directly passes into First side reaction device, and chlorine is assigned to each side reaction device by a certain percentage, and the ratio that the chlorine passing into each side reaction device accounts for total intake is 1 ~ 99%, and preferably 20 ~ 80%.
Described side reaction device adopts tank reactor, and reaction is photocatalytically carried out, and the wavelength region of light is visible ray.
The chlorizate of vinyl trichloride is rich in continuous extraction at the bottom of the tower of reaction and rectification device of the present invention.
The present invention is specifically with 1,2-ethylene dichloride is raw material production 1,1, the method of 2-trichloroethane, adopt the reactive distillation integrating device primarily of rectifying tower and side reaction device coupling composition, 1,2-ethylene dichloride directly passes into the side reaction device connected with overhead condensation liquid phase, photocatalytically chlorination reaction occurs with chlorine, in side reaction device, reacted material returns rectifying tower first block of column plate; And then whole for rectifying tower plates liquid phase material extraction is entered next stage side reaction device continuation chlorination reaction, chlorination reaction liquid is back to next block column plate of extraction column plate again, configures different side reaction device number of units according to this, obtains 1 from rectifying tower reactor, the thick product of 1,2-trichloroethane.
Advantage of the present invention is:
Side reaction device is placed in the outside of rectifying tower by the present invention, and the material in side reaction device comes from the column plate above it, enters the column plate below it, not only connect each other but also separate between side reaction device and rectifying tower after reaction.This coupled modes both can keep the advantage of reactive distillation integrated technology, and reactor operating condition and rectifying tower operational condition can be made again to keep independent simultaneously.The mode that the side reaction device that the present invention adopts is coupled with rectifying tower, by 1,2-ethylene dichloride chlorination production 1,1,2-trichloroethane, can reach high conversion, and to make in bottom product 1,1, the molar fraction of 2-trichloroethane is up to 0.98, and the molar fraction of tetrachloroethane growing amount is below 0.02, and technical process is short, operation controls flexibly, production cost is low, high financial profit, and simultaneous reactions body sum reacting weight can freely adjust, achieve the optimum matching of response capacity and separating power, be conducive to realizing large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the process flow diagram that vinyl trichloride is produced in reactive distillation coupling.
In Fig. 1, label is: 1-distillation column reactor rectification zone, 2-rectifying tower stripping zone, 3-rectifying tower overhead vapor phase pipeline, 4-rectifying tower overhead condenser, 5-rectifying column top return pipeline, the material of full condensation enters the 1st side reaction device, the hydrogen chloride gas discharging pipeline of 6-the 1st side stage reactor, 1 of 7-the 1st side reaction device, 2-ethylene dichloride feeding line, 8-the 1st side reaction device, 9-returns the liquid phase pipeline of rectifying tower from the 1st side reaction device, reaction product returns to distillation column reactor rectification zone by this pipeline, the chlorine feed pipeline of 10-the 1st side reaction device, 11-is from rectifying tower to the liquid phase feeding pipeline of the 2nd side reaction device, the hydrogen chloride gas discharging pipeline of 12-the 2nd side stage reactor, 13-the 2nd side reaction device, 14-returns the liquid phase pipeline of rectifying tower from the 2nd side reaction device, the chlorine feed pipeline of 15-the 2nd side reaction device, the hydrogen chloride gas discharging pipeline of 16-n-th side stage reactor, 17-is from rectifying tower to the liquid phase feeding pipeline of n-th side reaction device, 18-n-th side reaction device, 19-returns the liquid phase pipeline of rectifying tower from n-th side reaction device, the chlorine feed pipeline of 20-n-th side reaction device, 21-tower bottom of rectifying tower reboiler vapour phase circulation line, 22-tower bottom of rectifying tower reboiler, 23-tower bottom of rectifying tower reboiler liquid phase circulation pipeline, 24-tower bottom of rectifying tower product extraction pipeline.
Embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention is not limited to these embodiments.
Embodiment 1:
At diameter 0.8m, stage number is (reactive distillation district stage number 1 piece, stripping zone stage number 14 pieces) in the rectifying tower of 15 blocks of column plates, amasss 5m with 1 stage body
3tank reactor be connected, wherein all enter the 1st side reaction device after the condensation of overhead vapor phase material, side reaction device outlet material returns rectifying tower the 1st piece of column plate (stage number counts from the top down), and the material between rectifying tower and side reaction device passes through pump delivery.
Side reaction device is built with blue light source.1,2-ethylene dichloride is 4kmol/h to the feed flow rates of side reaction device, and chlorine is 4kmol/h to the feed flow rates of side reaction device.Temperature of reaction 80 DEG C, side reaction device pressure is 0.1MPa, and the liquid phase flow rate being returned rectifying tower by side reaction device is 65kmol/h, and each component molar mark is: 1,2-ethylene dichloride 0.908, vinyl trichloride 0.090, tetrachloroethane 0.002.Rectifying tower working pressure is 0.1MPa, and produced quantity at the bottom of tower is 4kmol/h.After reaction and rectification device is stable, rectifying tower tower top temperature 85.2 DEG C, bottom temperature 113.1 DEG C.In bottom product, the molar fraction of vinyl trichloride is that the molar fraction of 0.950,1,2-ethylene dichloride and tetrachloroethane is respectively 0.03,0.02.
Note: tetrachloroethane has two kinds of isomerss, but consider that in this technique, tetrachloroethane growing amount is considerably less, and also in product, two kinds of isomer growing amounts are suitable, therefore be referred to as tetrachloroethane, lower same.
Embodiment 2:
At diameter 0.8m, stage number is (reactive distillation district stage number 7 pieces, stripping zone stage number 8 pieces) in the rectifying tower of 15 blocks of column plates, amasss 3m with 2 stage bodies
3tank reactor be connected, between reactor, interval stage number is 5 pieces, wherein all enters the 1st side reaction device after the condensation of overhead vapor phase material, and side reaction device outlet material returns rectifying tower the 1st piece of column plate (stage number counts from the top down); Enter the 2nd reactor from the 6th piece of rectifiying plate material out, side reaction device outlet material returns rectifying tower the 7th block of column plate, and the material between rectifying tower and side reaction device passes through pump delivery.
Every platform side reaction device is built with white light source, and reaction adopts photochemical catalysis.1,2-ethylene dichloride is 4kmol/h to the feed flow rates of side reaction device, and chlorine is respectively 2.4 to the feed flow rates of the 1st, 2 side reaction device, 1.6kmol/h.Temperature of reaction 70 DEG C, each side reaction device pressure is 0.1MPa, returns the liquid phase flow rate of rectifying tower and form as table 1 by side reaction device.Rectifying tower working pressure is 0.1MPa, and produced quantity at the bottom of tower is 4kmol/h, and the full extraction of column plate liquid phase material enters the side reaction device be attached thereto.After reaction and rectification device is stable, rectifying tower tower top temperature 84.2 DEG C, bottom temperature 113.3 DEG C.In bottom product, the molar fraction of vinyl trichloride is that the molar fraction of 0.970,1,2-ethylene dichloride and tetrachloroethane is respectively 0.014,0.016.
Table 1 side reaction device outlet liquid phase flow rate and composition
Embodiment 3:
At diameter 0.8m, stage number is (reactive distillation district stage number 11 pieces, stripping zone stage number 19 pieces) in the rectifying tower of 30 blocks of column plates, amasss 3m with 3 stage bodies
3tank reactor be connected, between reactor, interval stage number is 4 pieces, wherein all enters the 1st side reaction device after the condensation of overhead vapor phase material, and side reaction device outlet material returns rectifying tower the 1st piece of column plate (stage number counts from the top down); Enter the 2nd reactor from the 5th piece of rectifiying plate material out, side reaction device outlet material returns rectifying tower the 6th block of column plate; Enter the 3rd reactor from the 10th piece of rectifiying plate material out, side reaction device outlet material returns rectifying tower the 11st block of column plate, and the material between rectifying tower and side reaction device passes through pump delivery.
Every platform side reaction device is built with yellow light sources, and reaction adopts photochemical catalysis.1,2-ethylene dichloride is 3kmol/h to the feed flow rates of side reaction device, chlorine is respectively 1.8 to the feed flow rates of each side reaction device, 0.9,0.3kmol/h.Temperature of reaction 60 DEG C, each side reaction device pressure is 0.1MPa, returns the liquid phase flow rate of rectifying tower and form as table 2 by side reaction device.Rectifying tower working pressure is 0.1MPa, and produced quantity at the bottom of tower is 3kmol/h, and the full extraction of column plate liquid phase material enters the side reaction device be attached thereto.After reaction and rectification device is stable, rectifying tower tower top temperature 83.9 DEG C, bottom temperature 113.5 DEG C.In bottom product, the molar fraction of vinyl trichloride is that the molar fraction of 0.980,1,2-ethylene dichloride and tetrachloroethane is respectively 0.009,0.011.
Table 2 side reaction device outlet liquid phase flow rate and composition
Embodiment 4:
At diameter 0.8m, stage number is (reactive distillation district stage number 13 pieces, stripping zone stage number 17 pieces) in the rectifying tower of 30 blocks of column plates, amasss 2m with 5 stage bodies
3tank reactor be connected, between reactor, interval stage number is 2 pieces, wherein all enters the 1st side reaction device after the condensation of overhead vapor phase material, and side reaction device outlet material returns rectifying tower the 1st piece of column plate (stage number counts from the top down); Enter the 2nd reactor from the 3rd piece of rectifiying plate material out, side reaction device outlet material returns rectifying tower the 4th block of column plate; By that analogy, between sides adjacent reactor, the stage number at interval is 2, and the turnover material be connected with side reaction device is adjacent tray on rectifying tower.Material between rectifying tower and side reaction device passes through pump delivery.
Every platform side reaction device is built with blue light source, and reaction adopts photochemical catalysis.1,2-ethylene dichloride is 4kmol/h to the feed flow rates of side reaction device, and chlorine is 0.8kmol/h to the feed flow rates of each side reaction device.Temperature of reaction 80 DEG C, each side reaction device pressure is 0.1MPa, returns the liquid phase flow rate of rectifying tower and form as table 4 by side reaction device.Rectifying tower working pressure is 0.1MPa, and produced quantity at the bottom of tower is 4kmol/h, and the full extraction of column plate liquid phase material enters the side reaction device be attached thereto.After reaction and rectification device is stable, rectifying tower tower top temperature 83.7 DEG C, bottom temperature 113.2 DEG C.In bottom product, the molar fraction of vinyl trichloride is that the molar fraction that 0.965,1,2-ethylene dichloride and tetrachloroethane are is 0.019,0.016.
Table 3 side reaction device outlet liquid phase flow rate and composition
Claims (9)
1. one kind with 1,2-ethylene dichloride is raw material production 1,1, the method of 2-trichloroethane, it is characterized in that the method adopts the reactive distillation integrating device primarily of rectifying tower and side reaction device coupling composition, with 1,2-ethylene dichloride and chlorine are raw material, 1,2-ethylene dichloride is directly passed into the First side reaction device be coupled with rectifying tower, chlorine passes into each the side reaction device be connected with rectifying tower continuously, in First side reaction device, photocatalytically chlorination reaction occurs, the liquid phase material be obtained by reacting enters rectifying tower, obtains required product from rectifying tower reactor; Or when side reaction device is more than two, continues chlorination reaction by entering next stage side reaction device after the liquid phase material extraction of rectifying tower, then be back to next block column plate of extraction, obtain required product from rectifying tower reactor; Wherein, total intake of chlorine and the inlet amount mol ratio of 1,2-ethylene dichloride are 1:1; Side reaction device number of units 1 ~ 5, described rectifying tower is divided into reactive distillation district and stripping zone from top to bottom, reactive distillation district passes through into and out of material pipe and each side reaction device butt coupling, stripping zone stage number is at 5 ~ 50 pieces, reactive distillation district stage number is at 1 ~ 20 piece, between sides adjacent reactor, the reactive distillation district stage number at interval is at 1 ~ 5 piece, described rectifying tower working pressure controls at normal pressure, temperature of reaction in each side reaction device is at 20 ~ 80 DEG C, reaction pressure controls at normal pressure, and reaction time controls at 0.1 ~ 5h.
2. method according to claim 1, is characterized in that side reaction device number of units 2 ~ 4.
3. method according to claim 2, is characterized in that when side reaction device number of units is multiple stage, and the ratio that the chlorine passing into each side reaction device accounts for total intake is 1 ~ 99%.
4. method according to claim 3, the ratio that the chlorine that it is characterized in that passing into each side reaction device accounts for total intake is 20 ~ 80%.
5. method according to claim 1, is characterized in that temperature of reaction in each described side reaction device is at 50 ~ 70 DEG C.
6. method according to claim 1, is characterized in that the reaction time in each described side reaction device controls at 0.5 ~ 2h.
7. method according to claim 1, is characterized in that described stripping zone stage number is at 10 ~ 20 pieces.
8. method according to claim 1, is characterized in that described reactive distillation district stage number is at 5 ~ 15 pieces.
9. method according to claim 1, First side reaction device is entered after it is characterized in that the full extraction of tower top light constituent, after chlorine generation chlorination reaction, return first block, distillation column reactor rectification zone column plate, the full extraction of column plate liquid phase material of reactive distillation district enters each the side reaction device be attached thereto respectively and carries out chlorination reaction, returns next block column plate of reactive distillation district extraction column plate after reaction; Chlorination reaction product carries out carrying heating up in a steamer in the stripping zone of rectifying tower, and gained reaction product is by extraction at the bottom of tower.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5315052A (en) * | 1993-04-29 | 1994-05-24 | Ppg Industries, Inc. | Concurrent production of trichloroethane isomers |
| CN1762935A (en) * | 2005-09-22 | 2006-04-26 | 上海氯碱化工股份有限公司 | Method and device for preparing 1,1,2-trichloroethane |
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| US5315052A (en) * | 1993-04-29 | 1994-05-24 | Ppg Industries, Inc. | Concurrent production of trichloroethane isomers |
| CN1762935A (en) * | 2005-09-22 | 2006-04-26 | 上海氯碱化工股份有限公司 | Method and device for preparing 1,1,2-trichloroethane |
Non-Patent Citations (1)
| Title |
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| 1,2-二氯乙烷反应精馏制备1,1,2-三氯乙烷;吴化冰等;《化学反应工程与工艺》;20080831;第24卷(第4期);第381-384页 * |
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