CN101353289A - Method for extracting trans-dichloroethylene from low-boiling residue of ethinyltrichloride production by gas-phase catalytic process - Google Patents
Method for extracting trans-dichloroethylene from low-boiling residue of ethinyltrichloride production by gas-phase catalytic process Download PDFInfo
- Publication number
- CN101353289A CN101353289A CNA2008102124198A CN200810212419A CN101353289A CN 101353289 A CN101353289 A CN 101353289A CN A2008102124198 A CNA2008102124198 A CN A2008102124198A CN 200810212419 A CN200810212419 A CN 200810212419A CN 101353289 A CN101353289 A CN 101353289A
- Authority
- CN
- China
- Prior art keywords
- dichloroethylene
- low
- trans
- boiling
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for extracting trans-dichloroethylene from low-boiling-point materials which are used for producing trichloroethylene by the gas phase catalysis. The method is characterized in that the low-boiling-point materials which are used for producing the trichloroethylene by the gas phase catalysis is deacidified, dehydrated and sent in a distilling kettle for distilling, and the trans-dichloroethylene is collected at the temperature of 47-49 DEG C. A trans-dichloroethylene product with the purity being more than 99% can be obtained by the method of the invention. The method utilizes wastes and reduces environmental pollution.
Description
Technical field
The present invention relates to the production technical field of hydrochloric ether, particularly relate to a kind of method of from the low-boiling-point substance of gas-phase catalysis production trieline, extracting trans-dichloroethylene.
Background technology
All the time, trieline and zellon are had characteristics such as hypotoxicity, volatile and stable performance with it and are used as organic solvent best on the state internal solvent market and low-temperature extraction agent and are extensive use of.But, that comes recently studies show that, a large amount of uses of trieline, zellon can increase global greenhouse effect, and therefore, environment-friendly type organic solvent, the low-temperature extraction agent of seeking a kind of alternative trieline and zellon is present solvent market problem anxious to be solved.
Trans-dichloroethylene, its chemical name are the 1.2-Ethylene Dichloride, and structural formula is CH
2=CCl
2, be a kind of monomer, normal temperature is down for having the colourless liquid of special odor, fusing point-122.5 ℃, 47.67 ℃ of boiling points, relative density 1.25 dissolves in multiple organic solvent, has characteristics such as volatile, stable performance.Compared to trieline, zellon, its solubleness in water is bigger, and toxicity is lower, is a kind of novel environment-friendly type organic solvent, low-temperature extraction agent and clean-out system.
Contain trans-dichloroethylene in the low-boiling-point substance of gas phase catalysis dehydrochlorination method production trieline, but all the time, this low-boiling-point substance directly is used as waste discharge, this not only causes environmental pollution, also causes energy dissipation simultaneously.
Summary of the invention
Purpose of the present invention just is to overcome the defective of above-mentioned prior art, a kind of method of extracting trans-dichloroethylene from the low-boiling-point substance of gas-phase catalysis production trieline is provided, this method not only can obtain the higher Ethylene Dichloride product of purity, simultaneously realize utilization of waste material again, reduced environmental pollution.
The present invention is achieved through the following technical solutions:
A kind of method of from the low-boiling-point substance of gas-phase catalysis production trieline, extracting trans-dichloroethylene, it is characterized in that: the low-boiling-point substance deacidification of at first gas-phase catalysis being produced trieline, dehydration, after send into still kettle distillation, the trans-dichloroethylene under gathering 47 ℃～49 ℃;
Above-mentioned deacidification is to carry out in the deacidification still, and used acid scavenger is an aqueous sodium carbonate;
Above-mentioned dehydration is to carry out in water trap, and to water content≤70ppm, used dewatering agent is Calcium Chloride Powder Anhydrous, anhydrous sodium sulphate, silica gel or salt of wormwood;
Above-mentioned still kettle height is 20～30 meters;
Also can gather the cis Ethylene Dichloride under vinylidene chloride under 31 ℃～32 ℃ and 61 ℃～65 ℃, return still kettle then and continue distillation;
The trans-dichloroethylene of above-mentioned collection is in CO 2 medium, and under 1-1.5 the normal atmosphere, 46 ℃～49 ℃ state of temperatures separate down purifies;
The trans-dichloroethylene of above-mentioned collection adds the MEHQ of 0.1%～0.5% oxybutylene or 0.02%～0.05% or 0.04%～0.05% epoxy chloropropane by its weight;
Mixing solutions under when distillation, directly gathering 47 ℃～65 ℃, and then trans-dichloroethylene is extracted in secondary rectifying in still kettle.
Can obtain purity at the trans-dichloroethylene product more than 99% by method of the present invention.The present invention has realized utilization of waste material, has reduced environmental pollution.
Embodiment
1. calcium carbide hydrolysis
This operation production principle is as follows:
CaC
2+2H
2O→C
2H
2+Ca(OH)
2
Reinforced: after the calcium carbide that fragmentation is good installs to suspension bucket, through hertz oscilltor in producer.In the producer, calcium carbide is met water generation hydrolysis reaction and is generated acetylene gas, overflow from the producer top, and through the acetylene cleanser, positive water seal, a cooling tower part is to water-ring pump, and a part is to gas holder.Institute's liberated heat adds producer continuously by means of NaClO waste water and cooling tower waste water and tap water in the reaction, and at 86 ± 2 ℃, the shoddye slurry flows out from upflow tube with the control generator temperature, and dense slag slurry and impurity thereof are regularly discharged by the deslagging post.Peace and quiet: through cooled acetylene gas, pressurize by water-ring pump, after steam separator is removed most of water, entering peace and quiet tower and the hypochlorous acid that contains available chlorine 0.08～0.12% receives solution and contacts, make impurity oxygen such as hydrogen sulfide in the thick acetylene gas, phosphuret-(t)ed hydrogen change into phosphoric acid, sulfuric acid etc., enter neutralizing tower again, liquid caustic soda neutralisation of sulphuric acid with 10～15% and phosphoric acid form soluble salt (sodium sulfate, sodium phosphate) and remove.
2. acetylene chlorination
This operation production principle is as follows:
C
2H
2+Cl
2→C
2H
2Cl
4
Through cooling de-watering, with the further dehydration or dewater of molecular sieve transformation adsorption dry technology, make acetylene water yield control≤50ppm from the acetylene of acetylene preparation section again with the vitriol oil.After the decompression vaporization, enter Chlorine Buffer Vessel from liquid chlorine storage tank liquid chlorine, mix in the tetrachloroethane mother liquor again with acetylene after drying dewaters again, import the chlorination tower by the bottom, the tetrachloroethane that generates is from the continuous extraction of cat head, enter thick tetrachloroethane jar after the cooling of chlorination complete condenser, tail gas is through water jet pump suction tail tank.
Thick tetrachloroethane metering back adds the tetrachloroethane tower, and cat head production (1.1.2-trichloroethane) removes tetrachloroethane top flow container, and tower bottoms (1.1.2-trichloroethane), is sent to and takes off the HCl reaction process after recycle stock mixes from the side line extraction.
3. tetrachloroethane takes off Cl
2The HCl process
This operation production principle is as follows:
C
2H
2Cl
4→C
2H
2Cl
2+Cl
2
C
2H
2Cl
4→C
2HCl
3+HCl
Come together in smart tetrachloroethane jar and get material, interchanger and reactant gases heat exchange are sent in metering, are preheated to 100～140 ℃ and enter smart tetrachloroethane vaporizer, and smart tetrachloroethane vaporizer heats with middle pressure steam.Smart tetrachloroethane gas after the heating removes smart tetrachloroethane preheater, with after the heat-conducting oil heating to 300 ℃ by taking off the HCl reactor, 210～290 ℃ of temperature of reaction, keep tetrachloroethane transformation efficiency 〉=90%, reaction institute heat requirement is supplied with by thermal barrier thermal oil (thermal oil adopts electrically heated or heat-conducting oil heating boiler).Reactant gases is sent to separation circuit after the heat exchanger cooling.
4. product separation and HCl refined unit
After coming the gaseous mixture of autoreactor to enter Analytic Tower, rise rapidly when resolving the beginning of cat head temperature, show when existing a large amount of HCl gases generate, observe the backflow visor of Analytic Tower, when refluxing, proof HCl growing amount is strengthening, and regulates the vacuum tightness variable valve and sets vacuum tightness, makes Analytic Tower top vacuum degree be ± 1kPa.Separate out HCl from resolving cat head, HCl is cooled to-20 ℃ with-35 ℃ of chilled brines, remove hydrochloric ethers such as TCE through trap, adsorption tower, the Analytic Tower tower bottoms continuously flows into the still flow container, and the low tower that boils is sent in metering then, and low-boiling-point substance distillates from cat head.When low boiling mixture content in the low liquid of top of the tower that boils greater than 30% the time, low-boiling-point substance is sent to low-boiling-point substance top flow container.Low-boiling-point substance is sent to the Ethylene Dichloride rectifying tower continuously, to reclaim the Ethylene Dichloride material in the low-boiling-point substance.
The low tower bottoms that boils continuously flows into the trieline tower with the trieline charge pump, control reflux ratio and make cat head trieline content greater than 99.9%, extraction three, zellon send finished product accumulating packaging process.
The trieline tower bottoms contains three, zellon and tetrachloroethane.When still flow container liquid level reaches 2/3 when above, start middle runnings tower and zellon tower, the trieline that contains a small amount of zellon returns smart tetrachloroethane jar from middle fraction overhead extraction, unreacted tetrachloroethane is from the extraction of zellon tower still, and circulation is back to the tetrachloroethane jar.
5. Ethylene Dichloride is refining
The low-boiling-point substance overhead product (low-boiling-point substance that promptly contains trans-dichloroethylene) of sending into low-boiling-point substance top flow container is deacidified at the deacidification still with aqueous sodium carbonate earlier, generally to PH between 5～7, in water trap, use Calcium Chloride Powder Anhydrous again, anhydrous sodium sulphate, silica gel or salt of wormwood dehydration, to water content≤70ppm, send into the still kettle distillation then, gather the vinylidene chloride under 31 ℃～32 ℃ respectively, cis Ethylene Dichloride under the cis Ethylene Dichloride under trans-dichloroethylene under 47 ℃～49 ℃ and 61 ℃～65 ℃, the vinylidene chloride under wherein 31 ℃～32 ℃ and 61 ℃～65 ℃ continues to return still kettle and continues distillation.Above-mentioned still kettle height is 20～30 meters, selects preferably more than 25 meters, and purpose is the interval range that increases sampling, is beneficial to the dna purity high product, generally can obtain the product of purity 99%.
The trans-dichloroethylene of above-mentioned collection also can be in CO 2 medium, and under 1-1.5 the normal atmosphere, 46 ℃～49 ℃ state of temperatures separate down purifies, and acquisition purity reaches the product more than 99%, packs in nitrogen then.
In order to increase the stability of trans-dichloroethylene, usually need to add some stablizers, add the MEHQ of 0.1%～0.5% oxybutylene or 0.02%～0.05% or 0.04%～0.05% epoxy chloropropane as weight according to trans-dichloroethylene in packing.
Perhaps will send into the low-boiling-point substance overhead product (low-boiling-point substance that promptly contains trans-dichloroethylene) of low-boiling-point substance top flow container and collect, and then handle with aforesaid method.
Or temperature is increased to 47 ℃-65 ℃, and after being extracted together, trans-dichloroethylene and cis Ethylene Dichloride send into still kettle rectifying again, and trans-dichloroethylene is extracted in secondary rectifying.
6. low-boiling-point substance recovery process
Be sent to the low-boiling-point substance recovery tower continuously from the low cat head distilled liquid that boils, the still liquid of removing behind the impurity such as HCl, Ethylene Dichloride is delivered to Analytic Tower still flow container.Low-boiling-point substance recovery tower overhead product trieline (content 〉=70%) is delivered to the packing post, reclaim liquid from low-boiling-point substance, the sampling of acetylene chlorating mother liquor, each rectifying tower reboiler and send the chlorocarbon vaporizer, after underpressure distillation, the material in the chlorocarbon complete condenser is sent to thick tetrachloroethane jar respectively and resolves the tower bottoms jar according to forming.
Come out from the Ethylene Dichloride rectifying tower, wherein underproof mixed solution enters still kettle rectifying once more, and at the bottom of the still kettle part liquid enters the high boiling material basin after squeezing into condenser condenses.
Claims (8)
1. method of from gas-phase catalysis is produced the low-boiling-point substance of trieline, extracting trans-dichloroethylene, it is characterized in that: the low-boiling-point substance deacidification of at first gas-phase catalysis being produced trieline, dehydration, after send into still kettle distillation, the trans-dichloroethylene under gathering 47 ℃～49 ℃.
2. according to the described method of extracting trans-dichloroethylene from the low-boiling-point substance of gas-phase catalysis production trieline of claim 1, it is characterized in that: above-mentioned deacidification is to carry out in the deacidification still, and used acid scavenger is an aqueous sodium carbonate.
3. according to the described method of from the low-boiling-point substance of gas-phase catalysis production trieline, extracting trans-dichloroethylene of claim 1, it is characterized in that: above-mentioned dehydration is to carry out in water trap, to water content≤70ppm, used dewatering agent is Calcium Chloride Powder Anhydrous, anhydrous sodium sulphate, silica gel or salt of wormwood.
4. according to the described method of extracting trans-dichloroethylene from the low-boiling-point substance of gas-phase catalysis production trieline of claim 1, it is characterized in that: above-mentioned still kettle height is 20～30 meters.
5. according to the described method of from the low-boiling-point substance of gas-phase catalysis production trieline, extracting trans-dichloroethylene of claim 1, it is characterized in that: also can gather the cis Ethylene Dichloride under vinylidene chloride under 31 ℃～32 ℃ and 61 ℃～65 ℃, return still kettle then and continue distillation.
6. according to the described method of from the low-boiling-point substance of gas-phase catalysis production trieline, extracting trans-dichloroethylene of claim 1, it is characterized in that: the trans-dichloroethylene of above-mentioned collection is in CO 2 medium, 1-1.5 under the individual normal atmosphere, 46 ℃～49 ℃ state of temperatures separate down purifies.
7. according to the described method of extracting trans-dichloroethylene from gas-phase catalysis is produced the low-boiling-point substance of trieline of claim 1, it is characterized in that: the trans-dichloroethylene of above-mentioned collection adds the MEHQ of 0.1%～0.5% oxybutylene or 0.02%～0.05% or 0.04%～0.05% epoxy chloropropane by its weight.
8. according to the described method of from the low-boiling-point substance of gas-phase catalysis production trieline, extracting trans-dichloroethylene of claim 1, it is characterized in that: the mixing solutions under when distillation, directly gathering 47 ℃～65 ℃, and then trans-dichloroethylene is extracted in secondary rectifying in still kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102124198A CN101353289B (en) | 2008-08-19 | 2008-08-19 | Method for extracting trans-dichloroethylene from low-boiling residue of ethinyltrichloride production by gas-phase catalytic process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102124198A CN101353289B (en) | 2008-08-19 | 2008-08-19 | Method for extracting trans-dichloroethylene from low-boiling residue of ethinyltrichloride production by gas-phase catalytic process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101353289A true CN101353289A (en) | 2009-01-28 |
| CN101353289B CN101353289B (en) | 2010-09-29 |
Family
ID=40306343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102124198A Active CN101353289B (en) | 2008-08-19 | 2008-08-19 | Method for extracting trans-dichloroethylene from low-boiling residue of ethinyltrichloride production by gas-phase catalytic process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101353289B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891583A (en) * | 2010-07-20 | 2010-11-24 | 阿拉善达康三四氯乙烯有限公司 | Method for co-production of trichloroethylene and tetrachloroethylene by gas phase catalysis method |
| CN102079687A (en) * | 2010-12-17 | 2011-06-01 | 山东新龙集团聚氯乙烯有限公司 | Recycling method of residual liquor in production of trichloroethylene |
| CN102267868A (en) * | 2010-06-01 | 2011-12-07 | 滨化集团股份有限公司 | Industrial production apparatus for trichloroethylene |
| CN102775269A (en) * | 2012-07-13 | 2012-11-14 | 中国石油集团东北炼化工程有限公司葫芦岛设计院 | Trichloroethylene gas phase catalysis production method |
| CN105859511A (en) * | 2016-05-24 | 2016-08-17 | 芜湖融汇化工有限公司 | Separation device and method of TCE by-product low-boiling-point substance |
| CN106946649A (en) * | 2017-02-24 | 2017-07-14 | 芜湖融汇化工有限公司 | Material deacidification device in trichloro ethylene system |
| CN108299153A (en) * | 2018-04-09 | 2018-07-20 | 浙江巨化技术中心有限公司 | A kind of preparation method of trans- 1,2- dichloroethylene |
| CN110054546A (en) * | 2019-03-18 | 2019-07-26 | 浙江师范大学 | A kind of production technology of trans- 1,2- dichloroethylene |
| CN112961026A (en) * | 2021-02-08 | 2021-06-15 | 宁夏普瑞化工有限公司 | Acetylene purification linkage control type trans-1, 2-dichloroethylene preparation system |
-
2008
- 2008-08-19 CN CN2008102124198A patent/CN101353289B/en active Active
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267868A (en) * | 2010-06-01 | 2011-12-07 | 滨化集团股份有限公司 | Industrial production apparatus for trichloroethylene |
| CN102267868B (en) * | 2010-06-01 | 2013-06-19 | 滨化集团股份有限公司 | Industrial production apparatus for trichloroethylene |
| CN101891583A (en) * | 2010-07-20 | 2010-11-24 | 阿拉善达康三四氯乙烯有限公司 | Method for co-production of trichloroethylene and tetrachloroethylene by gas phase catalysis method |
| CN102079687A (en) * | 2010-12-17 | 2011-06-01 | 山东新龙集团聚氯乙烯有限公司 | Recycling method of residual liquor in production of trichloroethylene |
| CN102079687B (en) * | 2010-12-17 | 2013-05-01 | 山东新龙集团聚氯乙烯有限公司 | Recycling method of residual liquor in production of trichloroethylene |
| CN102775269A (en) * | 2012-07-13 | 2012-11-14 | 中国石油集团东北炼化工程有限公司葫芦岛设计院 | Trichloroethylene gas phase catalysis production method |
| CN105859511A (en) * | 2016-05-24 | 2016-08-17 | 芜湖融汇化工有限公司 | Separation device and method of TCE by-product low-boiling-point substance |
| CN105859511B (en) * | 2016-05-24 | 2019-01-04 | 芜湖融汇化工有限公司 | The separator and separation method of TCE by-product low-boiling-point substance |
| CN106946649A (en) * | 2017-02-24 | 2017-07-14 | 芜湖融汇化工有限公司 | Material deacidification device in trichloro ethylene system |
| CN108299153A (en) * | 2018-04-09 | 2018-07-20 | 浙江巨化技术中心有限公司 | A kind of preparation method of trans- 1,2- dichloroethylene |
| CN110054546A (en) * | 2019-03-18 | 2019-07-26 | 浙江师范大学 | A kind of production technology of trans- 1,2- dichloroethylene |
| CN110054546B (en) * | 2019-03-18 | 2021-10-15 | 浙江师范大学 | Production process of trans-1, 2-dichloroethylene |
| CN112961026A (en) * | 2021-02-08 | 2021-06-15 | 宁夏普瑞化工有限公司 | Acetylene purification linkage control type trans-1, 2-dichloroethylene preparation system |
| CN112961026B (en) * | 2021-02-08 | 2023-01-06 | 宁夏普瑞化工有限公司 | Acetylene purification linkage control type trans-1, 2-dichloroethylene preparation system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101353289B (en) | 2010-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101353289B (en) | Method for extracting trans-dichloroethylene from low-boiling residue of ethinyltrichloride production by gas-phase catalytic process | |
| CN102145912B (en) | Process for preparing calcium chloride solution by utilizing ammonia soda filtration mother liquor | |
| CN106748632B (en) | A kind of clean preparation method synthesizing chloromethanes | |
| CN102936198B (en) | Produce the method for vinyl acetate | |
| CN101747298B (en) | Process for preparing high-purity diketene | |
| CN1830934A (en) | Method for producing dimethyl ether using methanol as raw material | |
| CN106699808A (en) | Acidolysis and solvent recycling process and device for producing glyphosate by using glycine method | |
| CN103588615B (en) | Device and technology for recovery of tetrachloroethylene | |
| CN110698320B (en) | Continuous recovery device and continuous recovery process for glyphosate hydrolyzed gas phase | |
| CN108409526B (en) | Methane chloride energy-saving production system and method | |
| CN103342642B (en) | Process for continuously producing dimethyl adipate through reaction-rectification method | |
| CN114163333B (en) | Method for synthesizing methyl ethyl carbonate in one step | |
| CN112279762A (en) | Technological method for synthesizing ethyl methyl oxalate through heterogeneous catalysis ester exchange | |
| CN111592506A (en) | Epichlorohydrin separation process | |
| CN101244970A (en) | Apparatus and technique for producing ethylene with ethyl alcohol | |
| CN109748791B (en) | Energy-saving method for producing dimethyl adipate | |
| CN102304048B (en) | Method and equipment for refining high-purity diethyl carbonate | |
| CN112142599B (en) | Low energy consumption, green carbonate product production method and system | |
| CN101747176A (en) | Method for preparation of trifluoro acetyl chloride with trifluoroethane chlorinated mixture | |
| CN1807381A (en) | Crotonaldehyde production process | |
| CN101357880A (en) | Technique and system for preparing dichloropropanol by autocatalysis reaction of glycerine and hydrogen chloride | |
| CN214088355U (en) | EC/DMC/EMC joint production system | |
| CN101254906B (en) | Method and device for vacuum nitric acid gas recovering during preparation of nitric acid | |
| CN1515528A (en) | Pressure synthesis and refining process of methane chloride | |
| CN102040479B (en) | System for preparing dichloropropanol by autocatalytic reaction of glycerol and hydrogen chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |