CN101402546B - Method for preparing dichloro-trifluoro-ethane - Google Patents
Method for preparing dichloro-trifluoro-ethane Download PDFInfo
- Publication number
- CN101402546B CN101402546B CN2008101597512A CN200810159751A CN101402546B CN 101402546 B CN101402546 B CN 101402546B CN 2008101597512 A CN2008101597512 A CN 2008101597512A CN 200810159751 A CN200810159751 A CN 200810159751A CN 101402546 B CN101402546 B CN 101402546B
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- CN
- China
- Prior art keywords
- zellon
- dichlorotrifluoroethane
- reaction
- catalyzer
- fixed
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 17
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000002309 gasification Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 2
- KLZDCUBZWUSEGO-UHFFFAOYSA-N CC.F.F.F.F.F Chemical compound CC.F.F.F.F.F KLZDCUBZWUSEGO-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing dichlorotrifluoroethane, and belongs to the technical field of fluoroethane. In essence, tetracarp and fluorine hydride are taken as raw materials, and the dichlorotrifluoroethane is prepared by gas-phase catalysis method. The method comprises a step that mixed gases undergo contact reaction in a fixed bed reactor filled with a catalyst. The method is characterized in that the reaction temperature is between 250 and 300 DEG C; the reaction pressure is between 1.0 and 1.2 MPa; the mol ratio of the tetracarp to the fluorine hydride is 1 to between 5 and 10; and the contacting time is between 8 and 12 seconds. The method has the advantages of easily obtained raw materials, high yield of products, and suitability for industrialized production on a large scale.
Description
Technical field
The invention belongs to the fluorinated ethanic technical field; Be specifically related to the method for making of a kind of dichlorotrifluoroethane (R123), the R123 main application that the present invention makes is to substitute F-11 and F-113 sanitising agent, whipping agent and the refrigeration agent etc. as central air-conditioning or centrifugal refrigerating machines.
Background technology
In the prior art, the preparation of R123 generally adopts trieline as raw material, and production technology is ripe.For example: publication number is that all to disclose a kind of trieline that adopts be the method for making of feedstock production dichlorotrifluoroethane to the Chinese patent of CN1205246A, CN1282723A.
But the trieline raw material supply is nervous, and purchase cost is higher.In recent years; Development along with the zellon production technique; Its manufacturing cost significantly reduces, and market is surging day by day to the demand of pentafluoride ethane (R125) and dichlorotrifluoroethane (R123) simultaneously, and therefore production R125 and R123 come into one's own gradually on same set of production equipment.
Through retrieval, do not find with the zellon to be the document of feedstock production dichlorotrifluoroethane.
Summary of the invention
The purpose of this invention is to provide a kind of is that raw material adopts gas-phase catalysis to prepare the method for dichlorotrifluoroethane (R123) with zellon and hydrogen fluoride, and this method is a main raw material owing to having adopted zellon, and raw material is easy to get, cost is low, and feed stock conversion is high.
The following technical scheme of the concrete employing of the present invention:
A kind of method for making of dichlorotrifluoroethane; Be raw material with zellon and hydrogen fluoride in essence, gas-phase catalysis prepares dichlorotrifluoroethane, comprises that mixed gas is being equipped with the fixed-bed reactor contact reacts step of catalyzer; It is characterized in that temperature of reaction is 250-300 ℃; Reaction pressure 1.0～1.2Mpa; Zellon and hydrogen fluoride mol ratio are 1:5-10, duration of contact 8～12s.
Said catalyzer is dipping CrCl
3γ-AlF
3
The applicant finds, feeds the reactive behavior that a small amount of chlorine can improve catalyzer, catalyzer long service life (generally greater than 1000 hours) in the reaction process.Therefore, also need continue in reactor drum, to feed chlorine in the reaction process, chlorine feeding amount is the 0.001-0.01 of zellon amount of substance.
The method for making of described dichlorotrifluoroethane is characterized in that, comprises the steps:
1) zellon and hydrofluoric gasification;
2) mix intensification;
3) contact reacts in fixed-bed reactor;
4) washing, alkali cleaning;
5) rectifying.
Among the present invention, gasification, mixing heat up and washing, alkali cleaning, the rectifying of bullion all are pre-treatment and refining means that the technician uses always in the present technique field, and it is not an emphasis of the present invention, does not do being described in detail at this.
Reaction equation of the present invention is: C
2Cl
4+ 3HF → C
2HCl
2F
3+ 2HCl ↑
The fixed-bed reactor that the present invention adopts are calandria type fixed bed reactors made from nickel-base alloy, and the tube side of reactor drum loads a certain amount of catalyzer; Shell side adopts fused salt to circulate as heat-conducting fluid, to replenish and to remove reaction heat.
Technology of the present invention is simple, and product yield is high, is easy to realize large-scale industrial production.This technology has advantages such as three-waste pollution is few, easy control of reaction system, and catalyst life is long simultaneously.
Feed stock conversion of the present invention is high, and through applicant's checking, the zellon total conversion rate is greater than 98%, and the R123 selectivity is greater than 90%.
Embodiment
Embodiment:
1) proportioning raw materials and reaction parameter, as shown in table 1:
Table 1 proportioning raw materials and reaction parameter table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Zellon and hydrogen fluoride mol ratio | 1：5 | 1：7 | 1：10 |
| Chlorine and zellon mol ratio | 0.001 | 0.005 | 0.01 |
| Temperature of reaction, ℃ | 250 | 270 | 300 |
| Reaction pressure, Mpa | 1.0 | 1.1 | 1.2 |
| Duration of contact, s | 8 | 10 | 12 |
2) preparation process: comprise zellon and hydrofluoric gasification; Mix and heat up; Contact reacts in fixed-bed reactor; Washing, alkali cleaning; Rectifying.Catalyzer adopts dipping CrCl
3γ-AlF
3
Claims (2)
1. the method for making of a dichlorotrifluoroethane; With zellon and hydrogen fluoride is raw material; Gas-phase catalysis prepares dichlorotrifluoroethane, comprises that mixed gas in that the fixed-bed reactor contact reacts step of catalyzer is housed, is characterized in that; The fixed-bed reactor that adopt are calandria type fixed bed reactors made from nickel-base alloy, and the tube side of reactor drum loads a certain amount of catalyzer; Shell side adopts fused salt to circulate as heat-conducting fluid, to replenish and to remove reaction heat; Said catalyzer is dipping CrCl
3γ-AlF
3Continue in the reaction process in reactor drum, to feed chlorine, chlorine feeding amount is the 0.001-0.01 of zellon amount of substance; Reaction process condition is following:
1.. temperature of reaction ℃ 250～300
2.. reaction pressure Mpa 1.0～1.20
3.. zellon: hydrogen fluoride mol is than 1: 5～10
4.. second 8～12 duration of contact.
2. the method for making of dichlorotrifluoroethane according to claim 1 is characterized in that, comprises the steps:
1) zellon and hydrofluoric gasification;
2) mix intensification;
3) contact reacts in fixed-bed reactor;
4) washing, alkali cleaning;
5) rectifying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101597512A CN101402546B (en) | 2008-11-13 | 2008-11-13 | Method for preparing dichloro-trifluoro-ethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101597512A CN101402546B (en) | 2008-11-13 | 2008-11-13 | Method for preparing dichloro-trifluoro-ethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101402546A CN101402546A (en) | 2009-04-08 |
| CN101402546B true CN101402546B (en) | 2012-02-29 |
Family
ID=40536732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101597512A Active CN101402546B (en) | 2008-11-13 | 2008-11-13 | Method for preparing dichloro-trifluoro-ethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101402546B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014117014A2 (en) * | 2013-01-25 | 2014-07-31 | Trane International Inc. | Refrigerant additives and compositions |
| CN112341311A (en) * | 2020-11-06 | 2021-02-09 | 江苏蓝色星球环保科技股份有限公司 | Preparation method of 1,1, 2-trifluoro-2-chloroethylene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4967023A (en) * | 1987-03-09 | 1990-10-30 | Ausimont S.P.A. | Process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination in the presence of catalysts |
| CN1048700A (en) * | 1989-07-12 | 1991-01-23 | 奥西蒙特公司 | Preparation 1,2-two chloro-1,1, the method for 2-Halothane |
| US5262574A (en) * | 1987-03-09 | 1993-11-16 | Ausimont S.P.A. | Process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination in the presence of catalysts |
| US5276224A (en) * | 1987-03-09 | 1994-01-04 | Ausimont S.P.A. | Process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination in the presence of catalysts |
| CN1097188A (en) * | 1993-07-05 | 1995-01-11 | 浙江省化工研究院 | 1,1, the improvement method for making of 1-three fluoro-2-monochloroethane |
-
2008
- 2008-11-13 CN CN2008101597512A patent/CN101402546B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4967023A (en) * | 1987-03-09 | 1990-10-30 | Ausimont S.P.A. | Process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination in the presence of catalysts |
| US5262574A (en) * | 1987-03-09 | 1993-11-16 | Ausimont S.P.A. | Process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination in the presence of catalysts |
| US5276224A (en) * | 1987-03-09 | 1994-01-04 | Ausimont S.P.A. | Process for preparing 1,1,1-trifluoro-2,2-dichloroethane by hydrofluorination in the presence of catalysts |
| CN1048700A (en) * | 1989-07-12 | 1991-01-23 | 奥西蒙特公司 | Preparation 1,2-two chloro-1,1, the method for 2-Halothane |
| CN1097188A (en) * | 1993-07-05 | 1995-01-11 | 浙江省化工研究院 | 1,1, the improvement method for making of 1-three fluoro-2-monochloroethane |
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| Publication number | Publication date |
|---|---|
| CN101402546A (en) | 2009-04-08 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of dichlorotrifluoroethane Effective date of registration: 20220622 Granted publication date: 20120229 Pledgee: Shandong Zhoucun Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG HUAAN NEW MATERIAL Co.,Ltd. Registration number: Y2022980008503 |
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Granted publication date: 20120229 Pledgee: Shandong Zhoucun Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG HUAAN NEW MATERIAL Co.,Ltd. Registration number: Y2022980008503 |
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| PC01 | Cancellation of the registration of the contract for pledge of patent right |