CN102295518B - Method for preparing pentachloroethane by liquid phase chlorination of vinylidene chloride - Google Patents
Method for preparing pentachloroethane by liquid phase chlorination of vinylidene chloride Download PDFInfo
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- CN102295518B CN102295518B CN 201110122875 CN201110122875A CN102295518B CN 102295518 B CN102295518 B CN 102295518B CN 201110122875 CN201110122875 CN 201110122875 CN 201110122875 A CN201110122875 A CN 201110122875A CN 102295518 B CN102295518 B CN 102295518B
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Abstract
The invention provides a method for preparing pentachloroethane by liquid phase chlorination of vinylidene chloride. The method comprises the following steps: putting vinylidene chloride into a reactor and adding metal halides comprising one or combination, serving as a catalyst A, of more than two of ferric chloride, aluminum chloride, cobalt chloride, copper chloride, calcium chloride, manganese chloride, chromic chloride, barium chloride, cesium chloride and antimony chloride, introducing nitrogen under the conditions of mixing and stirring, carrying out intermittent reaction at the temperature of 20-less than 85 DEG C at normal pressure so as to prepare tetrachlorethane; adding one or combination, serving as a catalyst B, of more than two of metal halides, introducing pressure chlorine under the conditions of mixing and stirring, carrying out intermittent reaction at the temperature of 85-130 DGE C at normal pressure so as to prepare a pentachloroethane crude product; and directlycarrying out water alkali washing and rectification on the crude product so as to prepare a pentachloroethane finished product. According to the invention, the problem that the costs of raw materialsin the original production are relatively high is fundamentally solved because vinylidene chloride is used as the raw material; and simultaneously, a novel, high-quality and inexpensive method is provided for preparation of pentachloroethane, and the method is simple, is easy to operate and is suitable for industrial production in large batch, and the purity and yield of the product are high.
Description
Technical field
The present invention relates to a kind of preparation method of pentaline, particularly a kind of method for preparing pentaline with the vinylidene chloride liquid phase chlorination.
Background technology
Because pentaline is a kind of main organochlorine product, it is the main raw material of producing zellon (PCE) and cooling agent pentafluoride ethane (HFC125), and zellon has industrial use widely, be mainly used in dry cleaning fabric and metal degreasing, with the chloride halogenated alkane of conventional refrigerants by a series of international standards limit or forbidding, but it can be used as not chloride fluoric ether substitute and uses, also can make cooling agent difluoro one chlorine (HCFC-123), pentafluoride ethane HFC125, the intermediate of HFC134a uses, therefore, the demand of zellon (PCE) heightens, and as the main raw material of producing zellon, the market potential of pentaline is bigger, and the patent of simultaneously relevant substitute refrigerants is also arisen at the historic moment.
It is that raw material is produced that traditional pentaline production technique all adopts with the trieline, but the high deficiency in economic performance of its production cost.
What still adopted number of patent application CN200810024583.6 " a kind of preparation method of pentafluoride ethane " but it is to be raw material with the trieline, generate pentaline then, enter gas phase fluorination by pentaline again and make pentafluoride ethane, so its raw material of this method, production cost still are higher.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of vinylidene chloride liquid phase chlorination to prepare the method for pentaline, this method technology is simple, and raw material is inexpensive, and the transformation efficiency height, selectivity is good, and purity of products height, quality are good, be fit to industrialized mass, greatly reduce production cost.
The present invention addresses the above problem the technical scheme that adopts: the vinylidene chloride liquid phase chlorination prepares the method for pentaline, may further comprise the steps:
1) with highly purified 1,1-Ethylene Dichloride (VDC) is called vinylidene chloride in the following text and is made raw material, put into reactor, and add metal halide by weight percentage and comprise iron(ic) chloride, aluminum chloride, cobalt chloride, cupric chloride, calcium chloride, Manganous chloride tetrahydrate, chromium chloride, bariumchloride, cesium chloride, catalyst A is made in the combination of one or more in the antimony chloride, and main ingredient iron(ic) chloride, aluminum chloride is 70～100%, remaining is to pass to pressure chlorine again under 0～30% mixing is stirred, and vinylidene chloride: chlorine adds reactor by 1: 1.0～1.5 mol ratio, 20 ℃～less than 85 ℃ normal pressure under intermittent reaction 15～20 hours, be made into tetrachloroethane by addition reaction, reaction equation is: Cl
2C=CH
2+ Cl
2→ Cl
3C-CH
2Cl, and through heat exchanger cooling to room temperature;
2), add metal halide again in the tetrachloroethane that above-mentioned reaction is made and comprise iron(ic) chloride, aluminum chloride, cobalt chloride, cupric chloride, calcium chloride, Manganous chloride tetrahydrate, chromium chloride, bariumchloride, cesium chloride, catalyst B is made in the combination of one or more in the antimony chloride, and main ingredient iron(ic) chloride, the weight percent of aluminum chloride is 70～100%, remaining is 0～30%, mix to stir and feed pressure chlorine down again, and tetrachloroethane and chlorine add reactor by 1: 1.0～1.5 mol ratio, intermittent reaction is 20～24 hours under 85 ℃～130 ℃ normal pressures, nucleophilic substitution reaction is made into the crude product of pentaline, and reaction equation is: Cl
3C-CH
2Cl+Cl
2→ Cl
3C-CHCl
2+ HCl, and through heat exchanger cooling to room temperature;
3), the chlorated liquid that more above-mentioned reaction made directly carries out scale and washes, and is made into the pentaline finished product 130 ℃ of temperature as rectification process.
Compared with prior art, the invention has the advantages that: adopted inexpensive vinylidene chloride to make raw material, fundamentally solved the higher difficult problem of raw materials cost in original production, and this method technology is simple, only need twice catalyzer of transposing and just can make the pentaline crude product through twice chlorination, wash with rectification process through scale again and make the pentaline finished product, its method is simple, easy to operate, for the preparation pentaline provides a kind of cheap and good-quality novel method, and the product purity that this method is made is up to more than 99%, recovery rate is up to more than 97%, the material use efficiency height.
Description of drawings
Accompanying drawing: process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are described in further detail.
Addition reaction general formula: Cl
2C=CH
2+ Cl
2→ Cl
3C-CH
2Cl
Nucleophilic substitution reaction formula: Cl
3C-CH
2Cl+Cl
2→ Cl
3C-CHCl
2+ HCl
Embodiment 1
In the four-hole boiling flask of 250ml, install chlorine access tube, reflux condensing tube, thermometer and electric blender respectively, add highly purified vinylidene chloride liquid 147ml (180 gram) in from charging opening to flask, and the adding weight percent is 80% iron(ic) chloride, 20% cesium chloride, with the composite 0.9 gram catalyst A of 150～250 purpose solid powder, under agitation from the chlorine access tube, pass to 2～3 kilograms per centimeter
2Pressure chlorine, and the mol ratio of vinylidene chloride and chlorine is 1: 1.1～1.4, reacting initial temperature is at 20～25 ℃, progressively be warmed up to 70 ℃～80 ℃, every chlorated liquid that once makes with regard to detection through reaction in two hours, when the content of vinylidene chloride less than 1% the time, be the fs reaction terminating, 15.5 hours reaction times, and through heat exchanger cooling to room temperature, add weight percent then and be 75% aluminum chloride, 25% cesium chloride, be mixed into the catalyst B of 1 gram with 150～250 purpose solid powder, reacting by heating liquid also is warmed up to 80～90 ℃, continue logical chlorine, the mol ratio of tetrachloroethane and chlorine is 1: 1.2～1.5, and temperature progressively rises to 114～116 ℃, every chlorated liquid that once makes with regard to detection through reaction in two hours, when the content of tetrachloroethane is lower than 0.4～0.6%, be the subordinate phase reaction terminating, the reaction times is at 21 hours, and through heat exchanger cooling to room temperature, be after 1% sodium hydroxide scale is washed neutrality through over-richness directly with the chlorated liquid that makes again, handle through 130 ℃ smart gold-plating that to obtain purity be 99% pentaline 364.2 grams, based on vinylidene chloride, the recovery rate of pentaline is 97.01% again.
Embodiment 2
In the four-hole boiling flask of 1000ml, install chlorine access tube, reflux condensing tube, thermometer and electric blender respectively, add liquid vinylidene chloride liquid 590ml (700 gram) in from charging opening to flask, and the adding weight percent is 75% iron(ic) chloride, 15% antimony chloride, 10% cesium chloride, with the composite 3.6 gram catalyst A of 150～250 purpose solid powder, under agitation from the chlorine access tube, pass to 2～3 kilograms per centimeter
2Pressure chlorine, and the mol ratio of vinylidene chloride and chlorine is 1: 1.1～1.4, reacting initial temperature is at 20～25 ℃, progressively be warmed up to 65 ℃～75 ℃, every chlorated liquid that once makes with regard to detection through reaction in two hours, when the content of vinylidene chloride less than 1% the time, be the fs reaction terminating, reaction times was at 17 hours, arrive room temperature through heat exchanger cooling, adding weight percent then is 70% aluminum chloride, 15% antimony chloride, 15% cesium chloride, be mixed into the catalyst B of 3.6 grams with 150～250 purpose solid powder, reacting by heating liquid also is warmed up to 84～86 ℃, continue logical chlorine, and the mol ratio of tetrachloroethane and chlorine is 1: 1.2～1.5, and temperature progressively rises to 115～125 ℃, every chlorated liquid that once makes that just detected through two hours of reaction times, when the content of tetrachloroethane is lower than 0.4～0.6%, be the subordinate phase reaction terminating, the reaction times arrived room temperature at 20.5 hours through heat exchanger cooling, be after 1% sodium hydroxide scale is washed neutrality through over-richness directly with the chlorated liquid that makes, handle through 130 ℃ smart gold-plating that to obtain purity be 99.4% pentaline 1433.8 grams, based on vinylidene chloride, the recovery rate of pentaline is 98.2% again.
Embodiment 3
At 10 meters
3Drop into 7000 kilograms of liquid vinylidene chlorides in the chlorination reactor, the adding weight percent is 75% iron(ic) chloride, 25% cesium chloride, with the composite 35 kilograms of catalyst A of 150～250 purpose solid powder, under agitation passes to 2～3 kilograms per centimeter from the chlorine access tube
2Pressure chlorine, and the mol ratio of vinylidene chloride and chlorine is 1: 1.1～1.4, reacting initial temperature is at 20～25 ℃, progressively be warmed up to 75 ℃～less than 85 ℃, every chlorated liquid that once makes that just detected through two hours of reaction times, when the content of vinylidene chloride less than 1% the time, be the fs reaction terminating, 20 hours reaction times, arrive room temperature through heat exchanger cooling, add weight percent then and be 80% aluminum chloride, 10% antimony chloride, 10% cesium chloride, be mixed into 35 kilograms catalyst B with 150～250 purpose solid powder, reacting by heating liquid also is warmed up to 87～93 ℃, continue logical chlorine, the mol ratio of tetrachloroethane and chlorine is 1: 1.2～1.5, and temperature progressively rises to 112～118 ℃, every chlorated liquid that once makes with regard to detection through reaction in two hours, when the content of tetrachloroethane is lower than 0.4～0.6%, be the subordinate phase reaction terminating, in 24 hours reaction times, arrive room temperature through heat exchanger cooling, be after 1% sodium hydroxide scale is washed neutrality through over-richness directly with the chlorated liquid that makes, handle through 130 ℃ smart gold-plating that to obtain purity be 14293 kilograms of 99.5% pentalines, based on vinylidene chloride, the recovery rate of pentaline is 97.9% again.
Claims (4)
1. a vinylidene chloride liquid phase chlorination prepares the method for pentaline, it is characterized in that may further comprise the steps:
1) with highly purified 1,1-Ethylene Dichloride (VDC) is called vinylidene chloride in the following text and is made raw material, put into reactor, and add metal halide by weight percentage and comprise iron(ic) chloride, aluminum chloride, cobalt chloride, cupric chloride, calcium chloride, Manganous chloride tetrahydrate, chromium chloride, bariumchloride, cesium chloride, catalyst A is made in the combination of one or more in the antimony chloride, and main ingredient iron(ic) chloride, aluminum chloride is 70～100%, all the other components are to pass to pressure chlorine again under 0～30% mixing is stirred, and vinylidene chloride: chlorine adds reactor by 1: 1.0～1.5 mol ratio, 20 ℃～less than 85 ℃ normal pressure under intermittent reaction 15～20 hours, be made into tetrachloroethane by addition reaction, reaction equation is: Cl
2C=CH
2+ Cl
2→ Cl
3C-CH
2Cl, and through heat exchanger cooling to room temperature;
2), in the tetrachloroethane that above-mentioned reaction makes, add metal halide by weight percentage again and comprise iron(ic) chloride, aluminum chloride, cobalt chloride, cupric chloride, calcium chloride, Manganous chloride tetrahydrate, chromium chloride, bariumchloride, cesium chloride, catalyst B is made in the combination of one or more in the antimony chloride, and main ingredient iron(ic) chloride, aluminum chloride is 70～100%, all the other components are 0～30%, mix to stir and feed pressure chlorine down again, and tetrachloroethane and chlorine add reactor by 1: 1.0～1.5 mol ratio, intermittent reaction is 20～24 hours under 85 ℃～130 ℃ normal pressures, nucleophilic substitution reaction is made into the crude product of pentaline, and reaction equation is: Cl
3C-CH
2Cl+Cl
2→ Cl
3C-CHCl
2+ HCl, and through heat exchanger cooling to room temperature;
3), the chlorated liquid that more above-mentioned reaction made directly carries out scale and washes, and is made into the pentaline finished product 130 ℃ of temperature as rectification process.
2. vinylidene chloride liquid phase chlorination according to claim 1 prepares the method for pentaline, it is characterized in that making catalyst A by 10～25% combinations of weight percent iron(ic) chloride 75～80%, cesium chloride or by iron(ic) chloride 75～80%, antimony chloride 10～15%, cesium chloride 10～25% combinations, made up or made up and made catalyst B by aluminum chloride 70～80%, antimony chloride 10～15%, cesium chloride 10～15% by aluminum chloride 75～80%, cesium chloride 10～25%, each catalyst A, B all mix with 150～250 purpose solid powder.
3. vinylidene chloride liquid phase chlorination according to claim 1 prepares the method for pentaline, and the pressure that it is characterized in that described pressure chlorine is 2 kilograms per centimeter
2～3 kilograms per centimeter
2
4. vinylidene chloride liquid phase chlorination according to claim 1 prepares the method for pentaline, and the crude product that it is characterized in that described pentaline is that 1% sodium hydroxide scale is washed neutrality through concentration directly.
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| CN108546228B (en) * | 2018-05-25 | 2021-09-07 | 宁夏凯力特新能源科技发展有限公司 | Method for directly producing pentachloroethane by reacting acetylene with chlorine |
| CN109796298A (en) * | 2018-12-29 | 2019-05-24 | 南通东港化工有限公司 | A kind of carbon trichloride synthesis technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775491A (en) * | 1967-08-30 | 1973-11-27 | Central Glass Co Ltd | Processes for producing polychlorinated ethanes and polychlorinated ethylenes |
| US5696309A (en) * | 1995-04-17 | 1997-12-09 | Laroche Industries, Inc. | Purification of halogenated carbon compounds |
| 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 |
-
2011
- 2011-05-10 CN CN 201110122875 patent/CN102295518B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775491A (en) * | 1967-08-30 | 1973-11-27 | Central Glass Co Ltd | Processes for producing polychlorinated ethanes and polychlorinated ethylenes |
| US5696309A (en) * | 1995-04-17 | 1997-12-09 | Laroche Industries, Inc. | Purification of halogenated carbon compounds |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 《化工百科全书》编辑委员会.氯代烃-模具.《化工百科全书》.1996,第11卷(第1版), * |
| 乙炔联产三氯乙烯、四氯乙烯的探索;蔡培英;《氯碱工业》;19850829(第4期);第29-33页 * |
| 蔡培英.乙炔联产三氯乙烯、四氯乙烯的探索.《氯碱工业》.1985,(第4期),第29-33页. |
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Effective date of registration: 20160111 Address after: 331200 new salt chemical industry park, Zhangshu City, Jiangxi Province Patentee after: Jiangxi Guohong Chemical Co., Ltd. Address before: 315012, room 24, 29 lane, Baiyang Poplar Street, Haishu District, Zhejiang, Ningbo, 607 Patentee before: Huang Zhiqiang |