CN1153160A - Production process of 1, 1, 1, 2-tetrafluoroethane - Google Patents
Production process of 1, 1, 1, 2-tetrafluoroethane Download PDFInfo
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- CN1153160A CN1153160A CN 95119421 CN95119421A CN1153160A CN 1153160 A CN1153160 A CN 1153160A CN 95119421 CN95119421 CN 95119421 CN 95119421 A CN95119421 A CN 95119421A CN 1153160 A CN1153160 A CN 1153160A
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- tetrafluoroethane
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 title abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 20
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 241000282326 Felis catus Species 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229960003750 ethyl chloride Drugs 0.000 claims description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 239000000047 product Substances 0.000 abstract description 16
- 239000006227 byproduct Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 229910016569 AlF 3 Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004334 fluoridation Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- -1 methyl chlorofluoride Chemical compound 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a production process of 1, 1, 1, 2-tetrafluoroethane, which aims to solve the process problems that the byproduct of the second reaction is reduced, the heat accumulated in the first step of reaction is timely evacuated, and the main product and the byproduct are not separately separated. The product at the outlet of the second reactor is recycled to the first reactor, and the components in the product are separated in sections by using a rectifying separation tower instead of separating each component separately. Thus, the method can reduce equipment, save investment, reduce energy consumption, simplify operation, stabilize reaction and improve product yield.
Description
The present invention is a kind of 1,1,1, and the production technique of 2-Tetrafluoroethane relates to a kind of by trieline and hydrogen fluoride gas phase catalytic reaction preparation 1,1, the 1-trifluoro-chloroethane, after make 1,1, the further gas phase catalytic fluorination of 1-trifluoro-chloroethane produces 1,1,1, the technology of 2-Tetrafluoroethane.
1,1,1,2-Tetrafluoroethane (hereinafter referred to as " R-134a ") is a kind of cooling agent to atmospheric ozone safety, the recommended surrogate that substitutes the methyl chlorofluoride that is widely used as cooling agent.R-134a can be from the preparation of multiple halohydrocarbon, and main have zellon and a trieline (TCE hereinafter referred to as), and the former will be through three step catalyzed reactions, comprising catalytic hydrogenation, need to use expensive platinum metal catalysts, its cost is improved, by product HCl growing amount is big in addition.Therefore under the contrast, be that raw material only needs the two-step catalysis fluoridation with TCE, catalyzer is inexpensive, and the growing amount of by product HCl is lower by 1/3 than the former, is the method that the method for raw material production R-134a becomes many companies first-selection with TCE.But this method difficulty is big: the fluoridation of first TCE is thermopositive reaction, and the heat of accumulating of beds is difficult for taking out of, makes reaction restive; It two is 1,1, generate in the fluoridation of 1-trifluoro-chloroethane (R-133a hereinafter referred to as) with R-134a and form 1 of azeotropic mixture, 1-difluoro vinylchlorid (R-1122 hereinafter referred to as) is comprised in the reaction mixture, and it is difficult separating R-134a in the mix products of reaction.Japan's publication 72105/1973 has been reported a kind of and has been made R-133a by TCE and HF reaction, in gas phase, R-133a is fluoridized then and make R-134a with HF, this method has been used three reactors, two refining plants and a separator, and the equipment complexity costs an arm and a leg.Chinese patent 93109641.3 has been reported the production method of a kind of R-134a, and this method is TCE and HF reaction generation R-133a in first reactor; R-133a and HF reaction generates R-134a in second reactor.The product of first and second reactors is imported first distillation tower, at the recovered overhead HCl of first distillation tower cut; Tower still material is imported second column obtain R-134a.The advantage of this method is to have reduced reactor, compares with the former and has reduced distilation steps.But still have bigger weakness: the heat that the by product R-1122 of second reactor can not get further fluoridizing with first reactor can not in time be taken away, and the independent separation of major and minor product has increased distillation tower and energy consumption in addition.
The objective of the invention is to overcome disadvantages of background technology, design a kind of by product that can reduce the reaction of second step, in time evacuate the heat of accumulating of the first step reaction, major and minor product is the production technique of independent isolating R-134a not.
Design of the present invention: in order to realize above-mentioned purpose, for reducing by second reactor byproducts and taking away first heat that reacts, adopt the second reactor outlet product to be recycled to first reactor, make the by product R-1122 in second reaction further be reacted generation R-133a, and second reactor product can be used as diluent gas, reaction heat is taken away, made reacting balance.Adopt a rectifying separation tower that each component in the product is carried out segmentation and separate, and each component is not separated separately.Comprise R-133a, R-134a, HCl, HF and TCE etc. according to first reactor product, utilize these component boiling point difference bigger, the needs according to reaction are divided into three boiling range sections with these components:
| The boiling range section | The low section of boiling (15～-90 ℃) | In the section of boiling (0～30 ℃) | The high section of boiling (＞50 ℃) |
| Name of material | ??HCl??R-134a | ????HF??R-133a | ??TCE |
| Normal boiling point, ℃ | ??-85.8??-26.5 | ????19??6.5 | ???86 |
| Content, % | ??20～40 | ????0～60 | ???＜1 |
According to basic, normal, high three boiling range sections, with a rectifying separation tower, 4 side lines (in the section of boiling) and tower still 2 (the high section of boiling) taking-up from cat head 5 (low the section of boiling), tower respectively.
The production technique of R-134a of the present invention, it may further comprise the steps:
A, in first reactor 1, make the mixture of TCE and HF and fluorination catalyst contact reacts generate R-133a.
B, in second reactor 7, the mixture of R-133a and HF is contacted with fluorination catalyst generates R-134a.
C, with the product of steps A 3 sending into from the rectifying separation tower, R-133a and HF take out with liquid phase 4 side lines from rectifying tower, send into second reactor 7 with volume pump 6, R-134a, HCl distillate from cat head 5, send into recovery system based on the tower bottoms of TCE from tower still 2.
D, the product of step B is all sent into first reactor 1, material begins circulation, stops to add HF to first reactor 1, adjusts the amount that TCE adds first reactor 1 by the transformation efficiency of R-133a, and HF adds from second reactor 7.
After E, the circulation of step D material, isolate R-134a and HCl, reclaim R-134a through washing from cat head 5.
For the first step reaction, the mol ratio of TCE and HF can change in a big way, and preferably 1: 4～6, temperature of reaction is 250～350 ℃, and preferred temperature range is 250～280 ℃, and be 1～30sec duration of contact, and reaction pressure is 0.1～1MPa.
In the reaction of second step, the mol ratio of R-133a and HF is 1: 8～12.Temperature of reaction is 300～450 ℃, is preferably between 350～400 ℃.Be 1～30sec duration of contact, and reaction pressure is 0.1～1MPa, and common second reactor pressure is a little more than first reactor.
Catalyzer used in the present invention is for loading on active A lF
3On Cr
3+, Co
2+, Ni
2+, Zn
2+, Mg
2+In the fluorochemical of element, wherein the content of Cr (in metal) is 0.5%～10%, and other element is 1/2～1/10 of a Cr content.Carrier A lF
3Crystalline phase composition, specific surface area and activity of such catalysts be funtcional relationship, general γ-phase content should 〉=70%, specific surface area 〉=40m
2/ g.The major cause of catalyst deactivation is the crystal transition of carrier, *-diffraction analysis shows γ-AlF
3Since 450 ℃ crystal transition takes place, formation α-AlF
3Along with α-AlF
3The increase of phase, activity of such catalysts reduces gradually, and therefore, strict control reaction temperature is crucial to keeping catalyst activity for a long time.Another characteristics of this catalyzer are that same catalyzer can be used in the two-step reaction.
Advantage of the present invention: adopt single tower that middle material is separated with product, minimizing equipment is reduced investment outlay, and cuts down the consumption of energy, and simplifies the operation; Adopted reverse circulation technology, made easily to form azeotropic R-1122 and change into R-133a, and the reaction heat of taking away first reactor 1 makes reacting balance, raising product yield with R-134a.
Description of drawings of the present invention is as follows:
Accompanying drawing 1 is the technological process of production figure of R-134a.In conjunction with the accompanying drawings 1 the explanation R-134a the technological process of production: HF and TCE enter first reactor 1 through pipeline 10, reaction is after pipeline 11 enters in the tower of rectifying separation tower 3, through separating R-133a and H F 4 pipeline 12 and pipeline 13 from tower respectively, enter second reactor 7 through volume pump 6 and pipeline 14, reaction is after pipeline 8,10 returns first reactor 1; Isolating HCl and R-134a discharge through cat head 5; Isolating TCE enters recovery system from tower still 2 and reclaims use behind pipeline 9, circulation back HF enters second reactor 7 from pipeline 14.After washing, alkali cleaning, drying, obtain the storage of R-134a crude product from cat head 5 isolated HCl and R-134a.
Embodiment:
By accompanying drawing 1 flow implementation: catalyzer is for being carried on high-specific surface area AlF
3On Cr
3+, Zn
2+, Mg
2+In fluorochemical, content (by metal) is respectively 4.2%, 1.3%, 0.5%.Reactor is made with the pure nickel pipe, with salt bath or oil bath heating.Establish 4 sampling point A, B, C, D in position as shown in the figure, the gas sample is formed with the gas Chromatographic Determination organic gas after washing, alkali cleaning drying, with chlorine, content of fluoride ion in chlorion, the fluoride ion selective electrode potential measurement washing lotion, calculate each sampling point HCl and HF content.
The reaction conditions of embodiment (1～4) and the results are shown in following table
| Embodiment | Temperature of reaction ℃ | Charge ratio mol/mol | Sampling point | Material is formed mol% | |||||||
| One is anti- | Two is anti- | HF/ TCE | ????HF/ ??R-133a | ?R- ?134a | ?R- ?133a | ??HF | ??HCl | R- 1122 | Other | ||
| 1 | ? 260 ??｜ ?300 | ??330 ???｜ ??380 | ????4∶1 | ????10∶1 | ?A | ?21.38 | ?5.79 | ?2.13 | ?69.05 | ?0.047 | ?1.65 |
| ?B | ?1.95 | ?8.67 | ?82.27 | ?6.84 | ?0.020 | ?0.27 | |||||
| ?C | ?0.42 | ?7.98 | ?90.83 | ?0.69 | ?0.018 | ?0.08 | |||||
| ?D | ?3.25 | ?6.93 | ?87.09 | ?2.52 | ?0.089 | ?0.21 | |||||
| ??2 | ? ?260 ???｜ ??300 | ??330 ???｜ ??380 | ????5∶1 | ????11∶1 | ?A | ?22.13 | ?5.95 | ?2.45 | ?67.46 | ?0.043 | ?2.01 |
| ?B | ?1.87 | ?8.97 | ?82.53 | ?6.42 | ?0.012 | ?0.15 | |||||
| ?C | ?0.37 | ?8.94 | ?89.64 | ?0.96 | ?0.016 | ?0.09 | |||||
| ?D | ?2.91 | ?6.73 | ?87.57 | ?2.49 | ?0.071 | ?0.30 | |||||
| ??3 | ? ?260 ???｜ ??300 | ??330 ???｜ ??380 | ????5.5∶1 | ????11.5∶1 | ?A | ?19.87 | ?7.06 | ?2.76 | ?69.17 | ?0.031 | ?1.14 |
| ?B | ?1.96 | ?8.79 | ?82.15 | ?6.97 | ?0.015 | ?0.13 | |||||
| ?C | ?0.39 | ?8.92 | ?89.61 | ?0.91 | ?0.019 | ?0.17 | |||||
| ?D | ?2.78 | ?6.94 | ?86.50 | ?3.41 | ?0.066 | ?0.37 | |||||
| ??4 | ? ?260 ???｜ ??300 | ??330 ???｜ ??380 | ????6∶1 | ????12∶1 | ?A | ?21.22 | ?7.11 | ?1.97 | ?69.48 | ?0.056 | ?0.22 |
| ?B | ?2.02 | ?8.91 | ?81.46 | ?7.54 | ?0.018 | ?0.07 | |||||
| ?C | ?0.31 | ?9.13 | ?89.64 | ?0.86 | ?0.020 | ?0.06 | |||||
| ?D | ?2.44 | ?6.60 | ?88.65 | ?2.26 | ?0.098 | ?0.05 | |||||
Claims (1)
1, a kind of 1,1,1, the production technique of 2-Tetrafluoroethane, it may further comprise the steps:
A, in first reactor (1), make trieline and hydrofluoric mixture and fluorination catalyst contact reacts generate 1,1, the 1-trifluoro-chloroethane;
B, in second reactor (7), make 1,1,1-trifluoro-chloroethane and hydrofluoric mixture contact with fluorination catalyst and generate 1,1,1, the 2-Tetrafluoroethane;
C, (3) of product from the rectifying separation tower of steps A are sent into, 1,1,1-trifluoro-chloroethane and hydrogen fluoride take out with liquid phase (4) side line from rectifying tower, send into second reactor (7), 1 with volume pump (6), 1,1,2-Tetrafluoroethane, hydrogenchloride distillate from cat head (5), send into recovery system based on the tower bottoms of trieline from tower still (2);
D, the product of step B is all sent into first reactor (1), material begins circulation, stops to add hydrogen fluoride to first reactor (1), by 1,1, the transformation efficiency of 1-trifluoro-chloroethane is adjusted the amount that trieline adds first reactor (1), and hydrogen fluoride adds from second reactor (7);
After E, the circulation of step D material, isolate 1,1,1 from cat head (5), 2-Tetrafluoroethane and hydrogenchloride reclaim 1,1,1 through washing, the 2-Tetrafluoroethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95119421A CN1045200C (en) | 1995-12-27 | 1995-12-27 | Process for producing 1,1,1, 2-tetrafluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95119421A CN1045200C (en) | 1995-12-27 | 1995-12-27 | Process for producing 1,1,1, 2-tetrafluoroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1153160A true CN1153160A (en) | 1997-07-02 |
| CN1045200C CN1045200C (en) | 1999-09-22 |
Family
ID=5082013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95119421A Expired - Lifetime CN1045200C (en) | 1995-12-27 | 1995-12-27 | Process for producing 1,1,1, 2-tetrafluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1045200C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117305B (en) * | 2007-04-11 | 2010-07-28 | 西安近代化学研究所 | Method for preparing 1,1,1,2-tetrafluoro thane |
| CN104892353A (en) * | 2015-06-02 | 2015-09-09 | 江苏三美化工有限公司 | Method for increasing conversion ratio of 1,1,1,2-tetrafluoroethane prepared by gas phase fluorination |
| CN107266285A (en) * | 2017-06-09 | 2017-10-20 | 浙江三美化工股份有限公司 | A kind of method that trichloro ethylene prepares HFC-134a |
| CN107759501A (en) * | 2017-12-07 | 2018-03-06 | 查都（上海）科技有限公司 | A kind of device for producing DMDS coproduction dimethyltrisulfide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07100671B2 (en) * | 1990-03-13 | 1995-11-01 | ダイキン工業株式会社 | Method for producing 1,1,1,2-tetrafluoroethane |
| TW227550B (en) * | 1992-08-05 | 1994-08-01 | Showa Denko Kk |
-
1995
- 1995-12-27 CN CN95119421A patent/CN1045200C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117305B (en) * | 2007-04-11 | 2010-07-28 | 西安近代化学研究所 | Method for preparing 1,1,1,2-tetrafluoro thane |
| CN104892353A (en) * | 2015-06-02 | 2015-09-09 | 江苏三美化工有限公司 | Method for increasing conversion ratio of 1,1,1,2-tetrafluoroethane prepared by gas phase fluorination |
| CN107266285A (en) * | 2017-06-09 | 2017-10-20 | 浙江三美化工股份有限公司 | A kind of method that trichloro ethylene prepares HFC-134a |
| CN107759501A (en) * | 2017-12-07 | 2018-03-06 | 查都（上海）科技有限公司 | A kind of device for producing DMDS coproduction dimethyltrisulfide |
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| Publication number | Publication date |
|---|---|
| CN1045200C (en) | 1999-09-22 |
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Assignee: Sinochem Taicang Environmental Protection Chemical Co., Ltd. Assignor: Sinochem Modern Environmental Protection Chemicals (Xi'an) Co., Ltd. Contract record no.: 2012320010044 Denomination of invention: Process for the preparation of 1.1.1.2- tetrafluoroethylene Granted publication date: 19990922 License type: Exclusive License Open date: 19970702 Record date: 20120322 |
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