CN105461509A - Liquid-phase production method for difluorotrichloroethane - Google Patents
Liquid-phase production method for difluorotrichloroethane Download PDFInfo
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- CN105461509A CN105461509A CN201510865162.6A CN201510865162A CN105461509A CN 105461509 A CN105461509 A CN 105461509A CN 201510865162 A CN201510865162 A CN 201510865162A CN 105461509 A CN105461509 A CN 105461509A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/357—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by dehydrogenation
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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Abstract
The invention discloses a liquid-phase production method for difluorotrichloroethane and belongs to the field of difluorotrichloroethane production. According to the method, dichloroethane is taken as a raw material, dichloroethylene is generated under the catalytic action of a catalyst, dichloro-vinylamine is generated under the action of ammonium hydroxide and manganese dioxide, after a sodium hydroxide solution and hydrochloric acid are added and soaking and mixing are performed, equal amount of hydrofluoric acid is added twice, a mixture has reaction at certain temperature and pressure, difluorotrichloroethane is prepared through leaving to stand and pumping filtration, and the problems of high probability of falling of fluorine, substitution by chlorine atoms, more complicated by-products and separation difficulties are solved. The liquid-phase production method for difluorotrichloroethane has the benefits as follows: the production process is simple, a few by-products are obtained and easy to separate, and secondary environmental pollution is avoided; the product yield is high and higher than 96%, and the cost of the method is lower than that of other methods by more than 5%.
Description
Technical field
The present invention relates to a kind of method of liquid phase production difluorotrichloroethane, belong to difluorotrichloroethane production field.
Background technology
Ethane is second member in alkane homologous series, is the hydrocarbon the most simply containing C-C.All molecules in ethane by covalent bonds, usually in the writing of molecule in order to show two C(carbon atoms) between only have a chemical bond, writing CH3-CH3.Aliphatic hydrocarbon unique in the alkane that it is made up of two carbon atoms.The content of ethane in some Sweet natural gas is 5% ~ 10%, is only second to methane; And be present in oil with dissolved state.Freon 113 is colourless volatile liquid at normal temperatures and pressures.Stable chemical nature, to metal non-corrosiveness.There is ether taste.Do not burn at normal temperatures, burning-point is 680 DEG C, but burning is very weak.Water-soluble hardly, be dissolved in alcohol, ether and most of organic solvent, to lipid favorable solubility, that chlorotrifluoroethylene manufactures Dare intermediate, also be the main raw material of trichoroacetic acid(TCA) product, have purposes widely, there is very large demand in market, but because it is comparatively large to depletion of the ozone layer, be limited to use.Therefore work out and work out the replacement of a kind of material on this basis, there is good development prospect.At present about the research of difluorotrichloroethane have not been reported, the production generally about these materials is all use vapor phase process, and vapor phase process often adopts the oxide compound of potassium halide and ferric oxide-rare earth metal to be catalyzer.But vapor phase process investment of production is large, temperature of reaction is higher, the fluorine of the carbon atom fluoridized easily is come off, is replaced by chlorine atom, and there is the comparatively complicated and separation difficulty of by product, complex technical process, pollutes large, and long reaction time, energy consumption be high, the problem that yields poorly.So it is simple to work out a kind of technique, by product is few and separation is simple, and the difluorotrichloroethane production method that output is high, has great importance and social value.
Summary of the invention
Technical problem to be solved by this invention: large for vapor phase process investment of production, temperature of reaction is higher, the fluorine of the carbon atom fluoridized easily is come off, replaced by chlorine atom, cause by product comparatively complicated and separation difficulty, long reaction time, energy consumption is high, yield poorly, heavy-polluted drawback, providing a kind of is raw material with ethylene dichloride, by under the katalysis of catalyzer, generate Ethylene Dichloride, Ethylene Dichloride amine is generated under the effect of oxyammonia and Manganse Dioxide, after adding sodium hydroxide solution and the mixing of salt acid soak, add for twice with measuring hydrofluoric acid, react under certain temperature and pressure, standing suction filtration obtains the liquid phase production method of difluorotrichloroethane, reach solution fluorine easily to come off, replaced by chlorine atom, the comparatively complicated and object of separation difficulty of by product.Production process of the present invention is simple, energy consumption is low, and products obtained therefrom output is high.
For achieving the above object, the production line of difluorotrichloroethane of the present invention is:
For solving the problems of the technologies described above, the present invention adopts technical scheme as described below to be:
(1) get 30 ~ 40mL ethylene dichloride and put into reaction vessel, respectively to adding 15 ~ 20mL tin tetrafluoride and 16 ~ 20g iron(ic) chloride in container, control temperature is 30 ~ 45 DEG C, rotating speed is 100 ~ 200r/min, be uniformly mixed, drip 10 ~ 20mL tin tetrachloride wherein, after dropwising with the speed of 2 ~ 3/s while stirring, insulation reaction 1 ~ 2h, obtains Ethylene Dichloride for subsequent use;
(2) in the three-necked flask with agitator, dropping funnel and escape pipe, 10 ~ 20g sodium hydroxide is loaded, add 15 ~ 20mL butanols simultaneously, stir 10 ~ 15min, to be mixed complete after, from dropping funnel instillation 20 ~ 30mL butanols and 10 ~ 15mL hydrogen peroxide, rate of addition is set as 1 ~ 2/s, be the mixing of 30 ~ 35 DEG C of magnetic agitation in temperature, with absolute ethanol washing 3 ~ 4 times after filtering, be cooled to-10 DEG C, suction filtration also with anhydrous diethyl ether washing 2 ~ 3 times, obtains oxyammonia;
(3) oxyammonia of above-mentioned gained is added in Ethylene Dichloride for subsequent use, add-on and Ethylene Dichloride mass ratio are 1:3, it is 40 ~ 50 DEG C in temperature, stir 30 ~ 40min, to be mixed complete after, add 7 ~ 9g Manganse Dioxide wherein, stirring reaction 50 ~ 60min, then filtered while hot, pours into filtrate in cold water and is cooled to room temperature, obtains Ethylene Dichloride amine;
(4) in the Ethylene Dichloride amine of above-mentioned gained, adding 10 ~ 20mL massfraction is 30 ~ 40% sodium hydroxide solutions, soak 1 ~ 2h, 60 ~ 70 DEG C of stirring reaction 30 ~ 40min are warming up to the speed program of 5 DEG C/min, after question response completes, add 20 ~ 30mL acetic acid wherein, be cooled to 50 ~ 60 DEG C, stir 30 ~ 50min, obtain Ethylene Dichloride diamines;
(5) the Ethylene Dichloride diamines of above-mentioned gained is put into there-necked flask, add the hydrochloric acid that 10 ~ 20mL massfraction is 30 ~ 35% wherein, be uniformly mixed, again respectively to wherein adding 5 ~ 7g magnesium oxide and 10 ~ 20mL ammoniacal liquor, be 500 ~ 700r/min at rotating speed, temperature is under 40 ~ 50 DEG C of conditions, mixes, be placed in frozen water 3 ~ 5min, obtain trichlorine quadrol;
(6) the trichlorine quadrol of above-mentioned gained is added in reactor, in reactor, drip 10 ~ 20mL hydrofluoric acid with the speed of 2 ~ 3/s, controlling temperature in reactor is 200 ~ 300 DEG C, and pressure is 1 ~ 3MPa, reaction 1 ~ 2h, obtain trichloro-monofluoro ethamine, then add 10 ~ 20mL hydrofluoric acid, keep condition in reactor constant, reaction 3 ~ 4h, after question response completes, leave standstill suction filtration, obtain difluorotrichloroethane.
The present invention is compared with additive method, and Advantageous Effects is:
(1) production process of the present invention is simple, and gained by product is few and separation is easy, to environment non-secondary pollution;
(2) products obtained therefrom output is high, reaches more than 96%, and cost is lower than additive method more than 5%.
Embodiment
First get 30 ~ 40mL ethylene dichloride and put into reaction vessel, respectively to adding 15 ~ 20mL tin tetrafluoride and 16 ~ 20g iron(ic) chloride in container, control temperature is 30 ~ 45 DEG C, rotating speed is 100 ~ 200r/min, be uniformly mixed, drip 10 ~ 20mL tin tetrachloride wherein, after dropwising with the speed of 2 ~ 3/s while stirring, insulation reaction 1 ~ 2h, obtains Ethylene Dichloride for subsequent use; Then in the three-necked flask with agitator, dropping funnel and escape pipe, 10 ~ 20g sodium hydroxide is loaded, add 15 ~ 20mL butanols simultaneously, stir 10 ~ 15min, to be mixed complete after, from dropping funnel instillation 20 ~ 30mL butanols and 10 ~ 15mL hydrogen peroxide, rate of addition is set as 1 ~ 2/s, be the mixing of 30 ~ 35 DEG C of magnetic agitation in temperature, with absolute ethanol washing 3 ~ 4 times after filtering, be cooled to-10 DEG C, suction filtration also with anhydrous diethyl ether washing 2 ~ 3 times, obtains oxyammonia; The oxyammonia of above-mentioned gained is added in Ethylene Dichloride for subsequent use, add-on and Ethylene Dichloride mass ratio are 1:3, it is 40 ~ 50 DEG C in temperature, stir 30 ~ 40min, to be mixed complete after, add 7 ~ 9g Manganse Dioxide wherein, stirring reaction 50 ~ 60min, then filtered while hot, pours into filtrate in cold water and is cooled to room temperature, obtains Ethylene Dichloride amine; In the Ethylene Dichloride amine of above-mentioned gained, add 10 ~ 20mL massfraction is 30 ~ 40% sodium hydroxide solutions, soak 1 ~ 2h, 60 ~ 70 DEG C of stirring reaction 30 ~ 40min are warming up to the speed program of 5 DEG C/min, after question response completes, add 20 ~ 30mL acetic acid wherein, be cooled to 50 ~ 60 DEG C, stir 30 ~ 50min, obtain Ethylene Dichloride diamines; Again the Ethylene Dichloride diamines of above-mentioned gained is put into there-necked flask, add the hydrochloric acid that 10 ~ 20mL massfraction is 30 ~ 35% wherein, be uniformly mixed, again respectively to wherein adding 5 ~ 7g magnesium oxide and 10 ~ 20mL ammoniacal liquor, be 500 ~ 700r/min at rotating speed, temperature is under 40 ~ 50 DEG C of conditions, mixes, be placed in frozen water 3 ~ 5min, obtain trichlorine quadrol; Finally the trichlorine quadrol of above-mentioned gained is added in reactor, in reactor, drip 10 ~ 20mL hydrofluoric acid with the speed of 2 ~ 3/s, controlling temperature in reactor is 200 ~ 300 DEG C, and pressure is 1 ~ 3MPa, reaction 1 ~ 2h, obtain trichloro-monofluoro ethamine, then add 10 ~ 20mL hydrofluoric acid, keep condition in reactor constant, reaction 3 ~ 4h, after question response completes, leave standstill suction filtration, obtain difluorotrichloroethane.
Example 1
First get 30mL ethylene dichloride and put into reaction vessel, respectively to adding 15mL tin tetrafluoride and 16g iron(ic) chloride in container, control temperature is 30 DEG C, rotating speed is 100r/min, be uniformly mixed, drip 10mL tin tetrachloride wherein, after dropwising with the speed of 2/s while stirring, insulation reaction 1h, obtains Ethylene Dichloride for subsequent use; Then in the three-necked flask with agitator, dropping funnel and escape pipe, 10g sodium hydroxide is loaded, add 15mL butanols simultaneously, stir 10min, to be mixed complete after, from dropping funnel instillation 20mL butanols and 10mL hydrogen peroxide, rate of addition is set as 1/s, be the mixing of 30 DEG C of magnetic agitation in temperature, with absolute ethanol washing 3 times after filtering, be cooled to-10 DEG C, suction filtration also washs 2 times with anhydrous diethyl ether, obtains oxyammonia; The oxyammonia of above-mentioned gained is added in Ethylene Dichloride for subsequent use, add-on and Ethylene Dichloride mass ratio are 1:3, it is 40 DEG C in temperature, stir 30min, to be mixed complete after, add 7g Manganse Dioxide wherein, stirring reaction 50min, then filtered while hot, pours into filtrate in cold water and is cooled to room temperature, obtains Ethylene Dichloride amine; In the Ethylene Dichloride amine of above-mentioned gained, add 10mL massfraction is 30% sodium hydroxide solution, soaks 1h, is warming up to 60 DEG C of stirring reaction 30min with the speed program of 5 DEG C/min, after question response completes, add 20mL acetic acid wherein, be cooled to 50 DEG C, stir 30min, obtain Ethylene Dichloride diamines; Again the Ethylene Dichloride diamines of above-mentioned gained is put into there-necked flask, add the hydrochloric acid that 10mL massfraction is 30% wherein, be uniformly mixed, again respectively to wherein adding 5g magnesium oxide and 10mL ammoniacal liquor, be 500r/min at rotating speed, temperature is under 40 DEG C of conditions, mixes, be placed in frozen water 3min, obtain trichlorine quadrol; Finally the trichlorine quadrol of above-mentioned gained is added in reactor, in reactor, drip 10mL hydrofluoric acid with the speed of 2/s, controlling temperature in reactor is 200 DEG C, and pressure is 1MPa, reaction 1h, obtain trichloro-monofluoro ethamine, then add 10mL hydrofluoric acid, keep condition in reactor constant, reaction 3h, after question response completes, leave standstill suction filtration, obtain difluorotrichloroethane.Production process of the present invention is simple, and gained by product is few and separation is easy, to environment non-secondary pollution; Products obtained therefrom output is high, reaches 96.3%, and cost is lower than additive method 5.2%.
Example 2
First get 35mL ethylene dichloride and put into reaction vessel, respectively to adding 18mL tin tetrafluoride and 18g iron(ic) chloride in container, control temperature is 37 DEG C, rotating speed is 150r/min, be uniformly mixed, drip 15mL tin tetrachloride wherein, after dropwising with the speed of 3/s while stirring, insulation reaction 1.5h, obtains Ethylene Dichloride for subsequent use; Then in the three-necked flask with agitator, dropping funnel and escape pipe, 15g sodium hydroxide is loaded, add 17mL butanols simultaneously, stir 13min, to be mixed complete after, from dropping funnel instillation 25mL butanols and 12mL hydrogen peroxide, rate of addition is set as 2/s, be the mixing of 33 DEG C of magnetic agitation in temperature, with absolute ethanol washing 3 times after filtering, be cooled to-10 DEG C, suction filtration also washs 2 times with anhydrous diethyl ether, obtains oxyammonia; The oxyammonia of above-mentioned gained is added in Ethylene Dichloride for subsequent use, add-on and Ethylene Dichloride mass ratio are 1:3, it is 45 DEG C in temperature, stir 35min, to be mixed complete after, add 8g Manganse Dioxide wherein, stirring reaction 55min, then filtered while hot, pours into filtrate in cold water and is cooled to room temperature, obtains Ethylene Dichloride amine; In the Ethylene Dichloride amine of above-mentioned gained, add 15mL massfraction is 35% sodium hydroxide solution, soaks 1.5h, is warming up to 65 DEG C of stirring reaction 35min with the speed program of 5 DEG C/min, after question response completes, add 25mL acetic acid wherein, be cooled to 55 DEG C, stir 40min, obtain Ethylene Dichloride diamines; Again the Ethylene Dichloride diamines of above-mentioned gained is put into there-necked flask, add the hydrochloric acid that 15mL massfraction is 33% wherein, be uniformly mixed, again respectively to wherein adding 6g magnesium oxide and 15mL ammoniacal liquor, be 600r/min at rotating speed, temperature is under 45 DEG C of conditions, mixes, be placed in frozen water 4min, obtain trichlorine quadrol; Finally the trichlorine quadrol of above-mentioned gained is added in reactor, in reactor, drip 15mL hydrofluoric acid with the speed of 3/s, controlling temperature in reactor is 250 DEG C, and pressure is 2MPa, reaction 1.5h, obtain trichloro-monofluoro ethamine, then add 15mL hydrofluoric acid, keep condition in reactor constant, reaction 3.5h, after question response completes, leave standstill suction filtration, obtain difluorotrichloroethane.Production process of the present invention is simple, and gained by product is few and separation is easy, to environment non-secondary pollution; Products obtained therefrom output is high, reaches 97.1%, and cost is lower than additive method 5.7%.
Example 3
First get 40mL ethylene dichloride and put into reaction vessel, respectively to adding 20mL tin tetrafluoride and 20g iron(ic) chloride in container, control temperature is 45 DEG C, rotating speed is 200r/min, be uniformly mixed, drip 20mL tin tetrachloride wherein, after dropwising with the speed of 3/s while stirring, insulation reaction 2h, obtains Ethylene Dichloride for subsequent use; Then in the three-necked flask with agitator, dropping funnel and escape pipe, 20g sodium hydroxide is loaded, add 20mL butanols simultaneously, stir 15min, to be mixed complete after, from dropping funnel instillation 30mL butanols and 15mL hydrogen peroxide, rate of addition is set as 2/s, be the mixing of 35 DEG C of magnetic agitation in temperature, with absolute ethanol washing 4 times after filtering, be cooled to-10 DEG C, suction filtration also washs 3 times with anhydrous diethyl ether, obtains oxyammonia; The oxyammonia of above-mentioned gained is added in Ethylene Dichloride for subsequent use, add-on and Ethylene Dichloride mass ratio are 1:3, it is 50 DEG C in temperature, stir 40min, to be mixed complete after, add 9g Manganse Dioxide wherein, stirring reaction 60min, then filtered while hot, pours into filtrate in cold water and is cooled to room temperature, obtains Ethylene Dichloride amine; In the Ethylene Dichloride amine of above-mentioned gained, add 20mL massfraction is 40% sodium hydroxide solution, soaks 2h, is warming up to 70 DEG C of stirring reaction 40min with the speed program of 5 DEG C/min, after question response completes, add 30mL acetic acid wherein, be cooled to 60 DEG C, stir 50min, obtain Ethylene Dichloride diamines; Again the Ethylene Dichloride diamines of above-mentioned gained is put into there-necked flask, add the hydrochloric acid that 20mL massfraction is 35% wherein, be uniformly mixed, again respectively to wherein adding 7g magnesium oxide and 20mL ammoniacal liquor, be 700r/min at rotating speed, temperature is under 50 DEG C of conditions, mixes, be placed in frozen water 5min, obtain trichlorine quadrol; Finally the trichlorine quadrol of above-mentioned gained is added in reactor, in reactor, drip 20mL hydrofluoric acid with the speed of 3/s, controlling temperature in reactor is 300 DEG C, and pressure is 3MPa, reaction 2h, obtain trichloro-monofluoro ethamine, then add 20mL hydrofluoric acid, keep condition in reactor constant, reaction 4h, after question response completes, leave standstill suction filtration, obtain difluorotrichloroethane.Production process of the present invention is simple, and gained by product is few and separation is easy, to environment non-secondary pollution; Products obtained therefrom output is high, reaches 98.0%, and cost is lower than additive method 6.1%.
Claims (1)
1. a method for liquid phase production difluorotrichloroethane, is characterized in that concrete preparation process is:
(1) get 30 ~ 40mL ethylene dichloride and put into reaction vessel, respectively to adding 15 ~ 20mL tin tetrafluoride and 16 ~ 20g iron(ic) chloride in container, control temperature is 30 ~ 45 DEG C, rotating speed is 100 ~ 200r/min, be uniformly mixed, drip 10 ~ 20mL tin tetrachloride wherein, after dropwising with the speed of 2 ~ 3/s while stirring, insulation reaction 1 ~ 2h, obtains Ethylene Dichloride for subsequent use;
(2) in the three-necked flask with agitator, dropping funnel and escape pipe, 10 ~ 20g sodium hydroxide is loaded, add 15 ~ 20mL butanols simultaneously, stir 10 ~ 15min, to be mixed complete after, from dropping funnel instillation 20 ~ 30mL butanols and 10 ~ 15mL hydrogen peroxide, rate of addition is set as 1 ~ 2/s, be the mixing of 30 ~ 35 DEG C of magnetic agitation in temperature, with absolute ethanol washing 3 ~ 4 times after filtering, be cooled to-10 DEG C, suction filtration also with anhydrous diethyl ether washing 2 ~ 3 times, obtains oxyammonia;
(3) oxyammonia of above-mentioned gained is added in Ethylene Dichloride for subsequent use, add-on and Ethylene Dichloride mass ratio are 1:3, it is 40 ~ 50 DEG C in temperature, stir 30 ~ 40min, to be mixed complete after, add 7 ~ 9g Manganse Dioxide wherein, stirring reaction 50 ~ 60min, then filtered while hot, pours into filtrate in cold water and is cooled to room temperature, obtains Ethylene Dichloride amine;
(4) in the Ethylene Dichloride amine of above-mentioned gained, adding 10 ~ 20mL massfraction is 30 ~ 40% sodium hydroxide solutions, soak 1 ~ 2h, 60 ~ 70 DEG C of stirring reaction 30 ~ 40min are warming up to the speed program of 5 DEG C/min, after question response completes, add 20 ~ 30mL acetic acid wherein, be cooled to 50 ~ 60 DEG C, stir 30 ~ 50min, obtain Ethylene Dichloride diamines;
(5) the Ethylene Dichloride diamines of above-mentioned gained is put into there-necked flask, add the hydrochloric acid that 10 ~ 20mL massfraction is 30 ~ 35% wherein, be uniformly mixed, again respectively to wherein adding 5 ~ 7g magnesium oxide and 10 ~ 20mL ammoniacal liquor, be 500 ~ 700r/min at rotating speed, temperature is under 40 ~ 50 DEG C of conditions, mixes, be placed in frozen water 3 ~ 5min, obtain trichlorine quadrol;
(6) the trichlorine quadrol of above-mentioned gained is added in reactor, in reactor, drip 10 ~ 20mL hydrofluoric acid with the speed of 2 ~ 3/s, controlling temperature in reactor is 200 ~ 300 DEG C, and pressure is 1 ~ 3MPa, reaction 1 ~ 2h, obtain trichloro-monofluoro ethamine, then add 10 ~ 20mL hydrofluoric acid, keep condition in reactor constant, reaction 3 ~ 4h, after question response completes, leave standstill suction filtration, obtain difluorotrichloroethane.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113816825A (en) * | 2021-09-18 | 2021-12-21 | 南通宝凯药业有限公司 | Method for synthesizing 1, 1-difluoro-2, 2-dichloroethane by using R142b hazardous waste |
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CN101460436A (en) * | 2006-06-21 | 2009-06-17 | 阿克马法国公司 | Procede de fabrication du pentafluoroethane |
CN101514139A (en) * | 2009-03-31 | 2009-08-26 | 上海氯碱化工股份有限公司 | Method for preparing vinyl chloride using dichloroethane as raw material |
CN102746150A (en) * | 2012-07-30 | 2012-10-24 | 内蒙古奥特普氟化学新材料开发有限公司 | Method for preparing ethyl difluorobromoacetate with high-boiling-point substances from difluoromonochlorethane process |
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GB791792A (en) * | 1955-04-05 | 1958-03-12 | Ethyl Corp | A dehydrochlorination process |
CN86101742A (en) * | 1985-03-20 | 1986-09-17 | 阿托化学公司 | Continuous cracking 1, the method for 2-ethylene dichloride |
CN101460436A (en) * | 2006-06-21 | 2009-06-17 | 阿克马法国公司 | Procede de fabrication du pentafluoroethane |
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CN113816825A (en) * | 2021-09-18 | 2021-12-21 | 南通宝凯药业有限公司 | Method for synthesizing 1, 1-difluoro-2, 2-dichloroethane by using R142b hazardous waste |
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