CN100427207C - Catalyst for gas phase process of producing 1,1 difluoroethane - Google Patents
Catalyst for gas phase process of producing 1,1 difluoroethane Download PDFInfo
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- CN100427207C CN100427207C CNB2005100446969A CN200510044696A CN100427207C CN 100427207 C CN100427207 C CN 100427207C CN B2005100446969 A CNB2005100446969 A CN B2005100446969A CN 200510044696 A CN200510044696 A CN 200510044696A CN 100427207 C CN100427207 C CN 100427207C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 16
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 230000008569 process Effects 0.000 title abstract description 6
- 229940051271 1,1-difluoroethane Drugs 0.000 title abstract 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims description 30
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012808 vapor phase Substances 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 19
- 239000000428 dust Substances 0.000 description 18
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 150000008282 halocarbons Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012974 tin catalyst Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 235000014121 butter Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- -1 tin halide Chemical class 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The catalyst for preparing 1, 1-difluoroethane includes Cr element and one or two other metal elements of Co, Mn, Zn, Fe, Mg, Al and Ni in the molar ratio of 1 to 0.001-0.6, as well as F element and O element. The Cr base catalyst has less environmental pollution, high activity, high stability, long service life, no tendency of polymerizing 1, 1-difluoroethane, great contact area, fast reaction, high space time yield and easy regeneration. When the reaction is controlled in 150-200 deg.c, the reaction pressure has no influence on the variety of the reaction products, and the reaction products have less side products. The catalyst is prepared through a simple co-precipitation process.
Description
Technical field
The present invention relates to vapor phase method and produce 1, the catalyst of 1-Difluoroethane.
Background technology
1, the 1-Difluoroethane, common name HFC-152a in the world at present, it is a kind of broad-spectrum fluorinated organic compound, can be used as cold-producing medium, spray is the raw material of producing fluoroplastics, especially its destruction ozone latent energy value (ODP) is 0, and global warming potential (GWP) is 0.02, just more and more is subjected to people's attention as the substitute of CFC.1, the conventional production method of 1-Difluoroethane is to utilize vinyl chloride to produce for raw material, and also useful employing acetylene is that raw material is produced.
Be that the method that raw material is produced all adopts liquid phase method production with vinyl chloride in the disclosed patent documentation.Adopting liquid phase method to produce the Difluoroethane catalyst system therefor in the patent 97192750 is " a kind ofly to contain the catalyst system of at least a tin catalyst that is selected from tin halide, tin oxyhalogenation thing and organotin and be selected from alkali halide at least and formula CX
1X
2X
3X
4The compound of saturated halogenated hydrocarbon, X wherein
1--X
4In at least a be chlorine, remaining X
1--X
4Respectively be selected from hydrogen, fluorine, bromine and C
(Y)Z
(2Y+1), wherein Z is the group that is selected from hydrogen, fluorine, chlorine and bromine, Y is the integer of 1-6, wherein saturated halogenated hydrocarbon in liquid phase mixture weight content less than 55%; Contain the described alkali halide of 0.001-2 mole with respect to every mole of described tin catalyst in the wherein said catalyst system; The mol ratio of wherein said saturated halogenated hydrocarbon and described tin catalyst is 0.001-5." wherein preferably tin halide is a butter of tin.In other the open patent of invention and the explanation of patent application, all adopting butter of tin is major catalyst, and different is that co-catalyst is selected saturated halogenated hydrocarbon or phenolic compound or organophosphorus compound for use.This tin class catalyst has the conversion ratio height, the advantage that the byproduct of production is few.But the environmental pollution of this tin class catalyst is serious, catalyst weak point in service life, 1, and the 1-Difluoroethane is easily polymerization in preparation process, produces oily mater and causes catalysqt deactivation.
Summary of the invention
Technical problem to be solved by this invention provides a kind of vapor phase method that is used for and produces 1, the catalyst of 1-Difluoroethane, and the catalytic activity height, long service life, environmental pollution is little, can not make 1, and the 1-Difluoroethane produces polymerism.
The present invention is used for vapor phase method and produces 1, the catalyst of 1-Difluoroethane, it is characterized in that comprising chromium element, other Metal Substrate and fluorine, oxygen element, other Metal Substrate is one or both elements among Co, Mn, Zn, Fe, Mg, Al, the Ni, and the mol ratio of chromium element and other metallic elements is 1: 0.001～0.6.
When other Metal Substrate was made up of two kinds of elements, the mol ratio in the Metal Substrate between two kinds of metallic elements was 0.1～20: 1.
Below enumerate several preferred catalyst and form (chromium and metallic element):
1, be made up of two kinds of metallic elements of Cr, Co, the mol ratio between them is 1: 0.2.
2, be made up of Cr, Co, three kinds of metallic elements of Fe, the mol ratio between them is 1: 0.2: 0.1.
3, be made up of Cr, Zn, three kinds of metallic elements of Fe, the mol ratio between them is 1: 0.1: 0.15.
4, be made up of Cr, Co, three kinds of metallic elements of Al, the mol ratio between them is 1: 0.2: 0.1.
5, be made up of Cr, Zn, three kinds of metallic elements of Al, the mol ratio between them is 1: 0.1: 0.2.
Preparation of catalysts is carried out in two steps, and the one, the preparation of oxide catalyst (catalyst precarsor), the 2nd, the preparation of fluoride catalysts must be through fluoridizing (being that catalyst precarsor is fluoridized) before catalyst uses.
I. the preparation of oxide catalyst.The preparation method is that the employing trivalent chromium is a main active component; the soluble-salt (nitrate, sulfate, chloride etc.) of chromic salts and other Metal Substrate adds precipitating reagent at normal temperatures; from corresponding salt, be settled out its hydroxide; and keep between solution PH=7-10; at 100 ℃ of-150 ℃ of low temperature dryings, 300 ℃-400 ℃ are carried out roasting under inert gas shielding.
The catalyst of roasting, compression moulding is measured indexs such as its specific area, pore volume, intensity.
II. the preparation of fluoride catalysts.The oxide catalyst of moulding is packed in the nickel pipe of φ 26*2.9, at inert gas N
2Protection feed down hydrogen fluoride gas and fluoridize, until be measured to the nickel pipe into and out of the hydrogen fluoride content at the mouth of pipe place when identical catalyst fluoridize and finish.
From the preparation method as can be seen, comprise chromium element, other metallic element and fluorine, oxygen element in the catalyst of the present invention.
Vapor phase method 1, the reaction principle of the production method of 1-Difluoroethane is:
CH
2＝CHCl+2HF→C
2H
4F
2+HCI
Reaction temperature is controlled at 150 ℃-200 ℃, reaction condition HF: vinyl chloride=2-4: 1 (mol ratio).
Catalyst of the present invention is a chromium-based catalysts, it is less to the pollution of environment, and catalyst activity is higher, good stability, the catalyst long service life, continous way production is adopted in operating process, and operating process is convenient, and is simple, toxic and side effect is little, and this catalyst can not make 1, and the 1-dichloroethanes produces polymerism, does not have oily mater in the production process and produces.The chromium-based catalysts contact area is big, and course of reaction is fast, the space-time yield height, and reaction temperature is controlled at 150 ℃-200 ℃, and reaction pressure can not influence the kind of reaction product, and the byproduct kind is less in the product, and this catalyst activation regeneration is easily.Method for preparing catalyst of the present invention is simple, adopts the coprecipitation preparation, the simple easy operating of technology.
Description of drawings
Fig. 1 is vinyl chloride and hydrogen fluoride reaction, the relation in Difluoroethane productive rate and reaction time.
The specific embodiment
Embodiment one: catalyst is formed: Cr: Co=1: 0.2 (following examples are the mol ratio of each element)
The Preparation of catalysts process:
Take by weighing the chromic salts of 1mol soluble in water accurately, the cobalt salt of 0.2mol (salt can be nitrate, sulfate or chloride) is dissolved in water, and water is pure water.(precipitating reagent can be NaOH, KOH or NH to add alkaline solution again
4OH solution), keep between the PH=7-10.Filter, dry, carry out low-temperature bake in 330 ℃ of-380 ℃ of scopes at 100 ℃.Feed inert gas N in the roasting process
2, the raw material extrusion modling after the roasting can make oxide catalyst.Each component in the oxide catalyst mainly is that the form with oxide exists.
After oxide catalyst prepares, get the 100ml oxide catalyst and pack in the nickel pipe of φ 26*2.9, at inert gas N
2Protection feed down hydrogen fluoride gas and fluoridize; the hydrogen fluoride amount that measures turnover mouth of pipe place to be checked stops logical protection gas when identical, feeds vinyl chloride, and the vinyl chloride flow is 100ml/min; reaction temperature is controlled at 150 ℃-200 ℃, reaction condition HF: vinyl chloride=2-4: 1 (mol ratio).
The catalyst index is:
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (dust) | Most probable radius (dust) |
| 0.37 | 128.5 | 20.62 | 10.75 |
Embodiment two:
Catalyst is formed: Cr: Mg=1: 0.1
The catalyst index is:
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (dust) | Most probable radius (dust) |
| 0.24 | 137.5 | 15.26 | 7.32 |
Embodiment three: Cr: Co: Fe=1: 0.2: 0.1
The catalyst index is:
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (dust) | Most probable radius (dust) |
| 0.32 | 197.6 | 18.34 | 12.17 |
Embodiment four: Cr: Co: Al=1: 0.2: 0.1
The catalyst index is:
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (dust) | Most probable radius (dust) |
| 0.27 | 204 | 20.24 | 7.63 |
Embodiment five: Cr: Zn: Al=1: 0.1: 0.2
The catalyst index is:
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (dust) | Most probable radius (dust) |
| 0.15 | 143.2 | 17.64 | 7.65 |
Embodiment six: Cr: Mg: Al=1: 0.2: 0.1
The catalyst index is:
| Pore volume (ml/g) | Specific area (m2/g) | Average pore radius (dust) | Most probable radius (dust) |
| 0.24 | 204.7 | 15.34 | 7.62 |
Embodiment seven: Cr: Mg: Fe=1: 0.1: 0.5
The catalyst index is:
| Pore volume (ml/g) | Specific area (m2/g) | Average pore radius (dust) | Most probable radius (dust) |
| 0.3 | 124 | 17.35 | 7.29 |
Embodiment eight: Cr: Zn: Fe=1: 0.1: 0.15
The catalyst index is:
| Pore volume (ml/g) | Specific area (m2/g) | Average pore radius (dust) | Most probable radius (dust) |
| 0.32 | 256 | 17.3 | 20.03 |
Embodiment nine: Cr: Al=1: 0.6
| Pore volume (ml/g) | Specific area (m2/g) | Average pore radius (dust) | Most probable radius (dust) |
| 0.29 | 182 | 12.30 | 15.02 |
Embodiment ten: Cr: Mn: Fe=1: 0.01: 0.1
Embodiment 11: Cr: Mn: Al=1: 0.4: 0.02
Embodiment 12: Cr: Fe=1: 0.001
Embodiment 13: Cr: Ni: Fe=1: 0.01: 0.01
The comparison of catalyst activity
| Reaction temperature ℃ | HF: vinyl chloride | Content of vinylchloride % in the product | R152a productive rate % | |
| Embodiment one | 150-200 | 2-4∶1 | 46.272 | 44.253 |
| Embodiment two | 150-200 | 2-4∶1 | 52.681 | 40.769 |
| Embodiment three | 150-200 | 2-4∶1 | 22.501 | 69.583 |
| Embodiment four | 150-200 | 2-4∶1 | 17.656 | 73.728 |
| Embodiment five | 150-200 | 2-4∶1 | 21.989 | 70.775 |
| Embodiment six | 150-200 | 2-4∶1 | 49.669 | 42.275 |
| Embodiment seven | 150-200 | 2-4∶1 | 50.514 | 40.592 |
| Embodiment eight | 150-200 | 2-4∶1 | 18.950 | 72.379 |
The catalyst life test:
Pick out the highest embodiment of conversion ratio four and carry out biometrics from selected sample, experimental condition is 150 ℃-200 ℃, HF: vinyl chloride=2-3: test in the scope of 1 (mol ratio).About 700 hours, catalyst is lived again.
Claims (5)
1, a kind of vapor phase method that is used for produces 1, the catalyst of 1 one Difluoroethanes, it is characterized in that comprising metallic element and fluorine, oxygen element, described metallic element is made up of Cr, Co and Fe or Cr, Co and Al or Cr, Zn and Fe or Cr, Zn and three kinds of elements of Al, the mol ratio of chromium element and other two kinds of metallic elements is 1: 0.001～0.6 in three kinds of metallic elements, and the mol ratio between other two kinds of metallic elements is 0.1～20: 1.
2, catalyst according to claim 1 is characterized in that described metallic element is made up of Cr, Co, three kinds of metallic elements of Fe, and the mol ratio between them is 1: 0.2: 0.1.
3, catalyst according to claim 1 is characterized in that described metallic element is made up of Cr, Zn, three kinds of metallic elements of Fe, and the mol ratio between them is 1: 0.1: 0.15.
4, catalyst according to claim 1 is characterized in that described metallic element is made up of Cr, Co, three kinds of metallic elements of Al, and the mol ratio between them is 1: 0.2: 0.1.
5, catalyst according to claim 1 is characterized in that described metallic element is made up of Cr, Zn, three kinds of metallic elements of Al, and the mol ratio between them is 1: 0.1: 0.2.
Priority Applications (1)
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|---|---|---|---|
| CNB2005100446969A CN100427207C (en) | 2005-09-12 | 2005-09-12 | Catalyst for gas phase process of producing 1,1 difluoroethane |
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|---|---|---|---|
| CNB2005100446969A CN100427207C (en) | 2005-09-12 | 2005-09-12 | Catalyst for gas phase process of producing 1,1 difluoroethane |
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| CN100427207C true CN100427207C (en) | 2008-10-22 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105344365A (en) * | 2015-11-23 | 2016-02-24 | 山东东岳化工有限公司 | Method for preparing fluorinated catalyst by homogeneous precipitation method |
| CN105344349B (en) * | 2015-11-23 | 2017-12-22 | 山东东岳化工有限公司 | A kind of solid fluorinated catalyst and preparation method thereof |
| CN110615728B (en) * | 2019-09-24 | 2022-10-21 | 浙江三美化工股份有限公司 | Preparation method of monofluoroethane |
| GB202100874D0 (en) | 2021-01-22 | 2021-03-10 | Mexichem Fluor Sa De Cv | Process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547483A (en) * | 1983-06-29 | 1985-10-15 | Hoechst Aktiengesellschaft | Catalysts for fluorination and/or dismutation reactions on halogenated hydrocarbons, and a process for their preparation |
| CN1064628A (en) * | 1991-03-07 | 1992-09-23 | 帝国化学工业公司 | The Catalysts and its preparation method that is used for fluorination reaction |
| US5523500A (en) * | 1991-12-09 | 1996-06-04 | D'elf Atochem S.A. | Mass catalysts based on chromium and nickel oxides and their application to the fluorination of halogenated hydrocarbons |
| WO2004007410A1 (en) * | 2002-07-10 | 2004-01-22 | Srf Limited | A process for the production of difluoromethane |
-
2005
- 2005-09-12 CN CNB2005100446969A patent/CN100427207C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547483A (en) * | 1983-06-29 | 1985-10-15 | Hoechst Aktiengesellschaft | Catalysts for fluorination and/or dismutation reactions on halogenated hydrocarbons, and a process for their preparation |
| CN1064628A (en) * | 1991-03-07 | 1992-09-23 | 帝国化学工业公司 | The Catalysts and its preparation method that is used for fluorination reaction |
| US5523500A (en) * | 1991-12-09 | 1996-06-04 | D'elf Atochem S.A. | Mass catalysts based on chromium and nickel oxides and their application to the fluorination of halogenated hydrocarbons |
| WO2004007410A1 (en) * | 2002-07-10 | 2004-01-22 | Srf Limited | A process for the production of difluoromethane |
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