CN101696147B - Method for preparing 1,1,1-trifluoro-2-chloroethane - Google Patents
Method for preparing 1,1,1-trifluoro-2-chloroethane Download PDFInfo
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- CN101696147B CN101696147B CN 200910185097 CN200910185097A CN101696147B CN 101696147 B CN101696147 B CN 101696147B CN 200910185097 CN200910185097 CN 200910185097 CN 200910185097 A CN200910185097 A CN 200910185097A CN 101696147 B CN101696147 B CN 101696147B
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- tetrachloroethane
- hydrogen fluoride
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Abstract
The invention discloses a method for preparing 1,1,1-trifluoro-2-chloroethane (HCFC-133a) from anhydrous hydrogen fluoride and mixed materials of 1,1,2,2-tetrachloroethane and 1,1,1,2-tetrachloroethane, wherein the anhydrous hydrogen fluoride and the mixed materials of the 1,1,2,2-tetrachloroethane and the 1,1,1,2-tetrachloroethane react to produce HCFC-133a under the action of a catalyst SbC15. In the method, trichloroethylene with higher price is not used, but the mixed materials of the 1,1,2,2-tetrachloroethane and the 1,1,1,2-tetrachloroethane, the price of which is only 5,000-6,000 yuan/ton, is adopted, other used raw materials and catalysts are same as raw materials used in a trichloroethylene synthesizing method, the preparation process requirements are similar, the preparation costs are equal and the obtained products are same, therefore, estimated by actual tests, the cost for producing each ton of HCFC-133a finished products can be directly lowered by 3,000-3,500 yuan.
Description
Technical field
The present invention relates to the preparation method of 1,1,1-trifluoro-2-chloroethane.
Background technology
The trade name of 1,1,1-trifluoro-2-chloroethane is HCFC-133a, is the intermediate of preparation environment friendly refrigerating fluid HFC-134a (chemical name is 1,1,1-, three fluoro-2-fluoroethanes), also can prepare trifluoroethanol, HCFC-123 etc.The preparation method of HCFC-133a is existing numerous report at home and abroad, and in published numerous synthetic routes, only two synthetic routes take trieline or zellon as raw material have industrial value.Wherein, the synthetic route take trieline as raw material has advantages of that reactions steps is brief, by product is few, and this synthetic route is better than the synthetic route take zellon as raw material.At present, in the producer that forms 1,1,1-trifluoro-2-chloroethane suitability for industrialized production, most synthetic routes that adopt take trieline as raw material.Britain ICI company built became to beat the world to overlap kiloton commerical test device in 1991.After this, du pont company, French atropic company, Daikin company, Italian Ao Simengte company, German Hoechst AG etc. set up 5000 ton/years of-10000 ton/years of industrial installations in succession.In above each company, except E.I.Du Pont Company because adopting the synthetic route take zellon as raw material with the other products coproduction, all the other all adopt the synthetic route take trieline as raw material.Because the range of application of trieline is wide, the huge market demand, this raw material is very nervous, holds at high price, and present market value is about 9000 yuan/tons.The high price of trieline is the major cause that directly affects environment friendly refrigerating fluid HFC-134a wide popularization and application, and the production cost that reduces environment friendly refrigerating fluid HFC-134a is that those skilled in the art thirst for the technical barrier that solves for a long time.Wherein low-cost synthetic 1,1,1-trifluoro-2-chloroethane is crucial, and the applicant is by long-term test and exploration, found and utilized sym.-tetrachloroethane, 1,1,1,2-tetrachloroethane or their mixture are raw material synthetic 1, the method of 1,1-trifluoro-2-chloroethane, this class synthetic method energy decrease 1, the preparation cost of 1,1-trifluoro-2-chloroethane is through measuring and calculating, produce per tonly 1,1, the 1-trifluoro-2-chloroethane can reduce by 3000 yuan～3500 yuan.
Summary of the invention
The object of the present invention is to provide a kind of mixture with sym.-tetrachloroethane and unsym.-tetraehloroethane and anhydrous hydrogen fluoride to prepare the method for 1,1,1-trifluoro-2-chloroethane (HCFC-133a).
Synthetic chemistry equation of the present invention is:
The present invention is raw materials used as follows:
1. sym.-tetrachloroethane;
2. unsym.-tetraehloroethane;
3. anhydrous hydrogen fluoride;
4. catalyst S bCl
5
5. chlorine;
1. sym.-tetrachloroethane is commercial commodity, the production and marketing of the outstanding scholar's chemical industry in Shanghai company limited;
Its physico-chemical property:
GB numbering: 61556
CAS number: 79-34-5
Chinese: sym.-tetrachloroethane
English name: 1,1,2,2-tetrachloroethane; Acetylene tetrachloride
Another name: acetylene tetrachloride; Symmetric tetrachloroethane
Molecular formula: C
2H
2C1
4CHCl
2CHCl
2
Molecular weight: 167.86
Vapour pressure: 1.33kPa (32 ℃)
Fusing point :-43.8 ℃
Boiling point: 146.4 ℃
Solvability: be slightly soluble in water, be dissolved in ethanol, ether etc.
Density: relative density (water=1) 1.60g/ml
Outward appearance and proterties: colourless heavy liquid has the smell of chloroform sample, stable in properties
Structural formula is:
2. unsym.-tetraehloroethane is commercial commodity, and Beijing gold is real opens the production and marketing of sincere chemical industry company limited;
Its physico-chemical property:
GB numbering: 61556
CAS number: 79-34-5
Chinese: unsym.-tetraehloroethane
English name: Tetrachloroethane
Another name: unsym-tetrachloroethane; Unsym.-tetrachloroethane
Molecular formula: C
2H
2Cl
4Cl
3CCH
2Cl
Molecular weight: 167.85
Vapour pressure: 0.80kPa (25 ℃)
Fusing point :-68.1 ℃
Boiling point: 138.2 ℃
Solvability: water insoluble, be dissolved in ethanol, ether etc.
Density: relative density (water=1) 1.60
Outward appearance and proterties: colourless, the liquid like the smell of chloroform, stable in properties arranged
Structural formula is:
3. anhydrous hydrogen fluoride is strong acid, is commercial product.
4. catalyst S bCl
5, be commercial product.
5. chlorine Cl
2It also is commercial product.
The method of 1,1,1-trifluoro-2-chloroethane (HCFC-133a) is as follows:
Add first the catalyzer antimony pentachloride in autoclave, add anhydrous hydrogen fluoride again, the add-on of anhydrous hydrogen fluoride is 1.2～1.8 times of antimony pentachloride molar weight, slowly be warmed up to 80 ℃～90 ℃ while adding, then will be by 1,1,2,2-tetrachloroethane and 1,1, the mixture (liquid) that 1,2-tetrachloroethane forms and anhydrous hydrogen fluoride (gas) add continuously by 1: 3～1: 6 mol ratio, and wherein 1,1,2,2-tetrachloroethane and 1,1, the mixture of 1,2-tetrachloroethane add-on hourly is 1/10th of antimony pentachloride quality, 1,1,2,2-tetrachloroethane and 1,1,1, in the mixture of 2-tetrachloroethane, 1,1,2, the content of 2-tetrachloroethane is 1%～99%, controls the discharging speed of reaction product by the air outlet valve of control reactor, guarantees that the interior pressure of reactor is between 0.8～1.0Mpa, pass into chlorine after reaction is carried out 5～8 hours in reactor, the amount that per hour passes into chlorine is 0.1%～0.3% of antimony pentachloride quality; The gained reaction product is for containing hydrogen fluoride, chlorine, the mixed gas of hydrogenchloride and HCFC-133a, this product passes through first water-cooled to 20 ℃～30 ℃, carry out deep cooling with subzero 15 ℃ salt solution again, then passing into the alkali cleaning still that has sodium hydroxide solution carries out alkali cleaning and gets HCFC-133a gas, this gas obtains purity at the HCFC-133a finished product more than 99.6% through the separation column fractionation again through molecular sieve drying, and fractionation pressure is 0.7Mpa～1.5Mpa, the still temperature of separation column is 60 ℃～90 ℃, the top temperature of separation column is 30 ℃～50 ℃, with 1,1,2,2-tetrachloroethane and 1,1,1, the mixture of 2-tetrachloroethane calculates, and its comprehensive yield is 92%～96%.
In preparation method of the present invention, the mixture of sym.-tetrachloroethane and unsym.-tetraehloroethane and anhydrous hydrogen fluoride are at catalyst S bCl
5Lower HCFC-133a, the catalyst S bCl of generating of effect
5Begin to add the fashionable antimony pentachloride that is in reaction, when passing into anhydrous hydrogen fluoride, then form SbF
2Cl
3, along with the carrying out of reaction, thereby can making antimony in the catalyzer be converted into three valence states, a large amount of muriates that produce in the reaction lose activity, keep active for making catalyzer, need in reaction, pass into a certain amount of chlorine.
In whole reaction, 1,1,2,2-tetrachloroethane and 1,1, the control of the intake of the mixture of 1,2-tetrachloroethane, anhydrous hydrogen fluoride, chlorine is extremely important, and 1,1,2,2-tetrachloroethane and 1,1, the mixture intake of 1,2-tetrachloroethane is crossed the selectivity that conference reduces reaction, otherwise has then reduced the production efficiency of reaction; The intake of anhydrous hydrogen fluoride is excessive to keep the high fluorine content of catalyzer, the generation of inhibition side reaction, but has reduced equally the production efficiency of reaction, otherwise, the incidence of side reaction is increased; The excessive generation that can increase equally side reaction of chlorine intake, on the contrary then can not effectively keep the activity of catalyzer.So the adding of each amount has strict control in the reaction, so just can reach best production effect.
Because the present invention does not use the higher trieline of price, adopt 1,1,2,2-tetrachloroethane and 1,1, the mixture of 1,2-tetrachloroethane, its price only have 5000～6000 yuan/tons, used other raw material (anhydrous hydrogen fluoride), chlorine and catalyzer (antimony pentachloride) all with the trieline synthesis method in raw materials used identical, preparation technology requires similar, and preparation cost is suitable, and products therefrom is identical, through the actual tests measuring and calculating, produce HCFC-133a finished product per ton and can directly reduce by 3000～3500 yuan of costs.
Embodiment
The below sets forth the inventive method with specific examples, but content of the present invention is not limited to following embodiment fully.
Embodiment 1
In the autoclave of 1500ml, add the 450g antimony pentachloride, add the 36.12g anhydrous hydrogen fluoride by the reactor bottom again, the add-on that is anhydrous hydrogen fluoride is 1.2 times of antimony pentachloride molar weight, slowly heat up while adding, temperature is controlled at 80 ℃～90 ℃ after adding anhydrous hydrogen fluoride, then by the per hour amount adding 1 of 45g, 1,2,2-tetrachloroethane and 1,1, the mixture of 1,2-tetrachloroethane adds anhydrous hydrogen fluoride simultaneously, the add-on of anhydrous hydrogen fluoride is 1,1,2,2-tetrachloroethane and 1,1,3 times of molar masss of 1,2-tetrachloroethane mixture, namely quality is 16.07g/ hour, by regulating discharging speed reacting kettle inner pressure is controlled between 0.8～1.0Mpa, reaction is carried out beginning after 5 hours to pass into chlorine in reactor, and logical chlorine dose is per hour 0.45g/ hour, and the gained reaction product is for containing hydrogen fluoride, chlorine, the mixed gas of hydrogenchloride and HCFC-133a, this product passes through first water-cooled to 20 ℃～30 ℃, carry out deep cooling with subzero 15 ℃ salt solution again, then pass into the alkali cleaning still that has sodium hydroxide solution and carry out alkali cleaning and get HCFC-133a gas, this gas is through molecular sieve drying, obtain purity at the HCFC-133a finished product more than 99.6% through the separation column fractionation again, fractionation pressure is 0.7Mpa～1.5Mpa, and fractionation tower reactor temperature is 60 ℃～90 ℃, and fractionation cat head temperature is 30 ℃～50 ℃, with 1,1,2,2-tetrachloroethane and 1,1, the mixture of 1,2-tetrachloroethane calculates, and its comprehensive yield is 92.3%.
Embodiment 2
In the autoclave of 1500ml, add the 450g antimony pentachloride, add the 54.18g anhydrous hydrogen fluoride by the reactor bottom again, the add-on that is anhydrous hydrogen fluoride is 1.8 times of antimony pentachloride molar weight, slowly heat up while adding, temperature is controlled at 80 ℃～90 ℃ after adding anhydrous hydrogen fluoride, then by the per hour amount adding 1 of 45g, 1,2,2-tetrachloroethane and 1,1, the mixture of 1,2-tetrachloroethane adds anhydrous hydrogen fluoride simultaneously, the add-on of anhydrous hydrogen fluoride is 1,1,2,2-tetrachloroethane and 1,1,6 times of molar masss of 1,2-tetrachloroethane mixture, namely quality is 32.14g/ hour, by regulating discharging speed reacting kettle inner pressure is controlled between 0.8～1.0Mpa, reaction is carried out beginning after 6 hours to pass into chlorine in reactor, and logical chlorine dose is per hour 0.45g/ hour, and the gained reaction product is for containing hydrogen fluoride, chlorine, the mixed gas of hydrogenchloride and HCFC-133a, this product passes through first water-cooled to 20 ℃～30 ℃, carry out deep cooling with subzero 15 ℃ salt solution again, then pass into the alkali cleaning still that has sodium hydroxide solution and carry out alkali cleaning and get HCFC-133a gas, this gas is through molecular sieve drying, obtain purity at the HCFC-133a finished product more than 99.6% through the separation column fractionation again, fractionation pressure is 0.7Mpa～1.5Mpa, and the still temperature of separation column is 60 ℃～90 ℃, and the top temperature of separation column is 30 ℃～50 ℃, with 1,1,2,2-tetrachloroethane and 1,1, the mixture of 1,2-tetrachloroethane calculates, and its comprehensive yield is 96%.
Embodiment 3
In the autoclave of 1500ml, add the 450g antimony pentachloride, add the 36.12g anhydrous hydrogen fluoride by the reactor bottom again, the add-on that is anhydrous hydrogen fluoride is 1.4 times of antimony pentachloride molar weight, slowly heat up while adding, temperature is controlled at 80 ℃～90 ℃ after adding anhydrous hydrogen fluoride, then by the per hour amount adding 1 of 45g, 1,2,2-tetrachloroethane and 1,1, the mixture of 1,2-tetrachloroethane adds anhydrous hydrogen fluoride simultaneously, the add-on of anhydrous hydrogen fluoride is 1,1,2,2-tetrachloroethane and 1,1,5 times of molar masss of 1,2-tetrachloroethane mixture, namely quality is 26.79g/ hour, by regulating discharging speed reacting kettle inner pressure is controlled between 0.8～1.0Mpa, reaction is carried out beginning after 5 hours to pass into chlorine in reactor, and logical chlorine dose is per hour 0.45g/ hour, and the gained reaction product is for containing hydrogen fluoride, chlorine, the mixed gas of hydrogenchloride and HCFC-133a, this product passes through first water-cooled to 20 ℃～30 ℃, carry out deep cooling with subzero 15 ℃ salt solution again, then pass into the alkali cleaning still that has sodium hydroxide solution and carry out alkali cleaning and get HCFC-133a gas, this gas is through molecular sieve drying, obtain purity at the HCFC-133a finished product more than 99.6% through the separation column fractionation again, fractionation pressure is 0.7Mpa～1.5Mpa, and the still temperature of separation column is 60 ℃～90 ℃, and the top temperature of separation column is 30 ℃～50 ℃, with 1,1,2,2-tetrachloroethane and 1,1, the mixture of 1,2-tetrachloroethane calculates, and its comprehensive yield is 94.7%.
Claims (1)
1. one kind with 1,2,2-tetrachloroethane and 1,1, mixture and the anhydrous hydrogen fluoride of 1,2-tetrachloroethane prepare 1,1, the method of 1-trifluoro-2-chloroethane, it is characterized in that: add first the catalyzer antimony pentachloride in autoclave, add anhydrous hydrogen fluoride again, the add-on of anhydrous hydrogen fluoride is 1.2～1.8 times of antimony pentachloride molar weight, slowly be warmed up to 80 ℃～90 ℃ while adding, then will be by 1,1,2,2-tetrachloroethane and 1, the mixture that 1,1,2-tetrachloroethane forms and anhydrous hydrogen fluoride add continuously by 1: 3～1: 6 mol ratio, wherein 1,1,2,2-tetrachloroethane and 1,1, the mixture of 1,2-tetrachloroethane add-on hourly is 1/10th of antimony pentachloride quality, 1,1,2,2-tetrachloroethane and 1,1,1, in the mixture of 2-tetrachloroethane, 1,1,2, the content of 2-tetrachloroethane is 1%～99%, controls the discharging speed of reaction product by the air outlet valve of control reactor, guarantees that the interior pressure of reactor is between 0.8～1.0Mpa, pass into chlorine after reaction is carried out 5～8 hours in reactor, the amount that per hour passes into chlorine is 0.1%～0.3% of antimony pentachloride quality; The gained reaction product is for containing hydrogen fluoride, chlorine, the mixed gas of hydrogenchloride and HCFC-133a, this product passes through first water-cooled to 20 ℃～30 ℃, carry out deep cooling with subzero 15 ℃ salt solution again, then passing into the alkali cleaning still that has sodium hydroxide solution carries out alkali cleaning and gets HCFC-133a gas, this gas obtains purity at the HCFC-133a finished product more than 99.6% through the separation column fractionation again through molecular sieve drying, and fractionation pressure is 0.7Mpa～1.5Mpa, the still temperature of separation column is 60 ℃～90 ℃, the top temperature of separation column is 30 ℃～50 ℃, with 1,1,2,2-tetrachloroethane and 1,1,1, the mixture of 2-tetrachloroethane calculates, and its comprehensive yield is 92%～96%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075709A (en) * | 1992-02-24 | 1993-09-01 | 中国科学院上海有机化学研究所 | 1,1, the preparation technology of 1-three fluoro-2-monochloroethane |
| CN1958542A (en) * | 2006-08-16 | 2007-05-09 | 江苏康泰氟化工有限公司 | Method for preparing 1,1,1 trifluo - 2 ethyl chloride |
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2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075709A (en) * | 1992-02-24 | 1993-09-01 | 中国科学院上海有机化学研究所 | 1,1, the preparation technology of 1-three fluoro-2-monochloroethane |
| CN1958542A (en) * | 2006-08-16 | 2007-05-09 | 江苏康泰氟化工有限公司 | Method for preparing 1,1,1 trifluo - 2 ethyl chloride |
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