CN1041804C - Catalyst for fluoreation of halogenated hydrocarbon - Google Patents
Catalyst for fluoreation of halogenated hydrocarbon Download PDFInfo
- Publication number
- CN1041804C CN1041804C CN95115476A CN95115476A CN1041804C CN 1041804 C CN1041804 C CN 1041804C CN 95115476 A CN95115476 A CN 95115476A CN 95115476 A CN95115476 A CN 95115476A CN 1041804 C CN1041804 C CN 1041804C
- Authority
- CN
- China
- Prior art keywords
- alf
- gamma
- catalyst
- content
- carrier
- 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.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- 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
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
Abstract
The present invention relates to a fluorate catalyst of fluorate halogenated hydrocarbon, the purpose of which is to solve the problems of low activated phase content, small specific areas, small hole volume, etc. of the existing carrier AlF3. anhydrous fluorine hydride which comprises SiO2 and is used for gamma-Al2O3, a mixture of nitrogen, and pure anhydrous fluorine hydride are fluorinated at the temperature of 150 to 300 DEG C, SiO2 used as a hole forming agent is removed, the specific area of a manufactured active AlF3 carrier is greater than or equal to>=40m<2>g<-1>, the hole volume is greater than or equal to 0.18 mlg<-1>, the average hole diameter is less than 90A, the content of gamma-AlF3 is greater than or equal to 50%, the content of AlF3 is greater than or equal to 90%, and the average crystal size is less than 150A. The activated AlF3 chromium, cobalt and magnesium carrying catalyst which uses trichloroethylene as a raw material to be fluorinated and synthesized into an R-134a reaction through an R-133a intermediate and two steps of gas phases uses the same catalyst, and the present invention has the advantages of high selectivity, high durability and high activity.
Description
The present invention relates to a fluorination catalyst, which is mainly used for gas-phase fluorination reaction of halogenated hydrocarbon and hydrogen fluoride.
It is known that the fluorination catalyst used for the synthesis of 1, 1, 1, 2-tetrafluoroethane (R-134 a for short) by reacting trichloroethylene (TCE for short) with hydrogen fluoride in the gas phase is Cr2O3／Al2O3. Experiments prove that the direct fluorination of trichloroethylene in gas phase by using catalysts such as chromium fluoride and oxide can only obtain 134a with a yield of 3%, and moreover, the activity of the catalyst is rapidly reduced, so that the catalyst needs to be regenerated and replaced frequently, which is obviously not beneficial to industrial production.
EP295,885A 1 reports a process for preparing R-134a, the catalyst being commercial γ -Al2O3Is a carrier (the specific surface area is more than 100 m)2g-1) After being dipped with active metal compound, the mixture is put into a reaction tube to be dried and fluorinated. In the reaction tube with HF fluorided gamma-Al2O3All converted to AlF3。
U.S. Pat. No. 5, 4,861,744 reports a process for the preparation of 1, 1, 1-trifluoro-2-chloroethane (R-133 a for short) by catalytic fluorination of trichloroethylene with hydrogen fluoride in the gas phase, the catalyst also being activated Alumina (e.g. Alumina A-201, bulk density 0.53 g ml)-1Specific surface area 325m2g-1Impregnating active component, drying and fluorinating.
Also reported in US4, 922, 037 are gamma-Al2O3Or activated carbon as a carrier, and preparing the fluoride catalyst by a similar method.
In summary, most of the reported preparations of R-133a and R-134a to dateThe catalyst is prepared by taking active alumina as a carrier, impregnating active components, drying and fluorinating. This procedure has significant disadvantages: (1) al (Al)2O3Conversion to AlF3The reaction of (a) produces a large amount of water, causing the loss of the loaded soluble active ingredient; (2) the importance of temperature control during fluorination is not emphasized. Too high fluorination temperatures are prone to AlF3Crystal phase transformation and grain growth, which reduces the activity of the catalyst.
EP0408005A1 reports on AlF3A method for preparing a catalyst used as a carrier. AlF used3The specific surface area is only 26m2g-1The exact crystalline phase and composition of the carrier is not disclosed. It carries a single trivalent chromium compound (CrCl)3·6H2O), no other co-catalyst is added, which makes it difficult to ensure optimal selectivity and stable catalytic activity of the catalyst.
AlF as a support for fluorination catalysts has been demonstrated3The crystal phase composition and specific surface area of the supported catalyst are closely related to the activity of the catalyst, generally, when the gamma content of the carrier is higher and the specific surface area is larger, the supported catalyst has higher catalytic activity, and α -AlF3The activity of (2) is very low. By conventional gas phase fluorination of Al2O3Preparation of AlF3In time, AlF is caused by the local high temperature formed by the strongly exothermic reaction3The specific surface area is greatly reduced, and the content of gamma-crystalline phase and amorphous phase is also largeThe amplitude is reduced.
The invention aims to overcome the defects of the background technology and designs gamma-AlF3The fluorination catalyst has high content, large specific surface area, large pore volume and uniformly distributed active components on the carrier.
The conception of the invention is as follows: in order to achieve the purpose, the catalyst prepared by the traditional method cannot be realized, and the existing method for expanding the specific surface area and the pore volume of the carrier is to add pore-forming agents such as carbon black, paraffin, polyvinyl alcohol and the like. When burned, the generated gas is removed to produce the pore canal. However, these pore formers must be reacted at elevated temperatures above 500 ℃. For gamma-AlF3Crystal form, which can generate grain growth and gamma-AlF under the high-temperature condition3Conversion to α -AlF3And with a significant reduction in specific surface area.
Another method for preparing high surface area catalysts is to precipitate the components required for the catalyst homogeneously from an aqueous solution. However, AlF prepared by this method3Is powdery, has low mechanical strength after being formed and has no application value.
In order to obtain gamma-AlF with high specific surface area, large pore volume and high content3First, fluorinate Al at the temperature of 150-2O3Meanwhile, the pore-forming agent is also removed by fluorination, thus breaking the traditional method for removing the pore-forming agent by high-temperature burning. Selecting SiO2SiO is used as pore-forming agent2The chain structure and the characteristic of easily reacting with HF to form volatile fluorinated silicon compound, once fluorinated and removed, a continuous pore channel structure is left, thereby increasing the specific surface area and the pore volume, and being superior to the existing AlF preparation method3Has high specific surface area, large pore volume and high mechanical strength.
The fluorination catalyst of fluorinated halogenated hydrocarbon is characterized by containing SiO23 to 20 percent of gamma-Al2O3The mixed gas of anhydrous hydrogen fluoride and nitrogen and pure anhydrous HF are subjected to gas phase fluorination at the temperature of 150-300 ℃ to expel SiO used as a pore-forming agent2To obtain active AlF3The specific surface area of the carrier is more than or equal to 40m2g-1Pore volume is more than or equal to 0.18mlg-1gamma-AlF with average pore diameter less than 903The content of (A) is more than or equal to 50 percent, AlF3The content is more than or equal to 90 percent. The average grain size is less than or equal to 150. The chloride of chromium, cobalt and magnesium is loaded by an impregnation method, and the mass ratio of metal ions is as follows: 1-10: 1: 0.1, curing with nitrogen or air at 120-350 ℃, and then activating with a mixture of hydrogen fluoride and nitrogen at 180-350 ℃.
Compared with the prior art, the invention has the following advantages:
(1) carrier AlF3Has large specific surface area, large pore volume and proper pore size distribution.
(2) The carrier is gamma-AlF3And no crystal phase transformation and grain growth occur in the reaction process.
(3)γ-AlF3Loaded with active component Cr3+、Co2+、Mg2+The prepared catalyst enables the fluorination reaction to be carried out at lower temperature, and has optimal selectivity and lasting catalytic activity.
(4) The fluoride catalyst can be used in the fluorine-chlorine exchange reaction of various halogenated hydrocarbons.
Example (b):
1. 145.4 g of Al (OH)3Reacting with excessive NaOH to obtain sodium metaaluminate solution, adding Na2SiO310.2 g of water glass, into which a precipitant CO is introduced2Filtering, washing, forming, drying and roasting to obtain the SiO-containing material25% of gamma-Al2O3. The product was prepared at 150 ℃ in the following volume ratios: HF: N2Fluorinating the mixture for 4h in a ratio of 1: 4, gradually increasing the HF concentration to pure HF for 8h, then heating to 200 ℃ for fluorinating for 3h to obtain AlF3The carrier is loaded with chromium, cobalt and magnesium metal ions by an impregnation method in the mass ratio of: 5: 1: 0.1, i.e. 5% Cr3+、1％Co2+And 0.1% Mg2+. In a nickel tube reactor, at 120 ℃ and N2Gas flow (50ml min)-1) After 12h treatment, the temperature is further 1 ℃ for min-1Raising the temperature rise rate to 350 ℃, curing for 6h at constant temperature, wherein the volume ratio of the cured catalyst at 180 ℃ is as follows: HF: N2After 4h of activation of the mixture of = 1: 1, it was changed to pure HF and then at 1 ℃ for min-1Raising the temperature to 350 ℃ at a speed rate, and activating for 10h to prepare the fluorination catalyst.
Carrier AlF3And (3) characterization: determination of AlF on carrier by BET low-temperature nitrogen adsorption method3Has a specific surface area of 57m2g-1Pore volume of 0.25 ml g-1Average pore diameter of 40.
gamma-AlF content of 70% in the crystal phase of the support, determined by X-ray powder diffraction3，AlF3The content is 90 percent, and the average grain size is 98.
The reaction of the fluoride catalyst prepared above for synthesizing R-134a is as follows:
reaction (1) was carried out with 30ml of catalyst at 260 ℃ in the following volume ratios: TCE HF = 1: 6, contact time 3.4S, conversion of TCE 98%, selectivity to R-133a 99%. The conversion of TCE was 100% and the selectivity was 99% at 280 ℃ under the same conditions. The fluorination catalyst described above was used in reaction (2), i.e. the same fluorination catalyst was used in both reactions, when the volume ratios were: r-133 a: HF = 1: 10, and the contact time is 16.4S, the conversion of R-133a is 32%, and the selectivity to R-134a is 99%; when the contact time is 8.2S, the conversion is 25% and the selectivity is 99%; when the contact time is 5.3S, the conversion rate is 23 percent, the selectivity is 99 percent, and after the reaction is carried out for 1000 hours, the crystal phase of the carrier is still gamma-AlF3And the average crystal grain size is 101A.
2. With reference to example 1, except that SiO-containing particles were obtained210% of gamma-Al2O3AlF obtained by fluorination3A carrier having a specific surface area of 50m2g-1Pore volume of 0.23 ml g-1Average pore diameter of 52 DEG and containing gamma-AlF387% of AlF3The content is 95%, average grain sizeThe size is 105. The loaded active components still contain: cr (chromium) component3+5％、Co2+1％、Mg2+0．1％。
Reaction (1) with 30ml of fluorination catalyst at 260 ℃, volume ratio: TCE: HF = 1: 6, contact time 3.4S, conversion of TCE 96%, and selectivity to R-133a 99%. The reaction conversion was 100% and the selectivity was 99% at 280 ℃ under the same conditions. The catalyst is used in the reaction (2), and when the volume ratio is as follows: r-133 a: HF = 1: 10, contact time 16.4S, conversion of R-133aThe rate is 30% and the selectivity is 99%; when the contact time is 8.2S, the conversion rate is 23 percent, and the selectivity is 99 percent; at a contact time of 5.3S, the conversion was 21% and the selectivity was 99%. After 1000h reaction, the carrier AlF3Still dominated by the gamma phase, the average grain size is still 105. ANGSTROM.
3. Reference example 1 was made, except that SiO-containing films were obtained215% of gamma AlF3The carrier obtained by fluorination had a specific surface area of 42m2g-1Pore volume 0.20 ml g-1Average pore diameter of 73 ℃ and containing gamma-AlF3100％、AlF3The content of (B) is 100%. The average crystal size was 110. ANG.
Reaction (1) with 30ml of fluorination catalyst at 260 ℃, volume ratio: TCE: HF = 1: 6, contact time 3.4S, conversion of TCE 94%, and selectivity to R-133a 99%. The reaction was carried out at 280 ℃ under the same conditions, the conversion of TCE was 98% and the selectivity to R-133a was 99%. The catalyst is used in the reaction (2), and when the volume ratio is as follows: r-133 a: HF = 1: 10, with a contact time of 16.4S, a conversion of R-133a of 27% and a selectivity to R-134a of 99%. When the contact time is 8.2S, the conversion is 22% and the selectivity is 99%; at a contact time of 5.3S, the conversion was 19% and the selectivity was 99%.
4. The method is implemented by referring to example 1, except that the mass ratio of the supported chromium, cobalt and magnesium is as follows: 2: 1: 0.1, i.e. 2% Cr3+、1％Co2+、0．1％Mg2+。
Reaction (1) was carried out with 30ml of fluorination catalyst at 260 ℃ in the following volume ratios: TCE: HF = 1: 6, contact time 3.4S, conversion of TCE 90%, selectivity to R-133a 99%, reaction at 280 ℃ under the same conditions, conversion 95%, selectivity 99%. The above catalyst was used in reaction (2) at a volume ratio of R-133 a: HF = 1: 10, a contact time of 16.4S, a conversion of R-133a of 25%, and a selectivity of 99%; when the contact time is 8.2S, the conversion is 17% and the selectivity is 99%; at a contact time of 5.3S, the conversion was 13% and the selectivity was 99%.
5. The method is implemented by referring to example 1, except that the mass ratio of the supported chromium ions, the supported cobalt ions and the supported magnesium ions is as follows: 10: 1: 0.1, i.e. 10% Cr3+、1％Co2+、0．1％Mg2+。
Reaction (1) with 30ml of catalyst at 260 ℃, volume ratio: TCE: HF = 1: 6, contact time 3.4S, conversion of TCE 98%, selectivity to R-133a 99%, reaction at 280 ℃ under the same conditions, conversion 100%, selectivity 99%. The fluorination catalyst is used in the reaction (2), when the volume ratio is: r-133 a: HF = 1: 10, contact time is 16.4S, conversion of R-133a is 32%, selectivity is 99%; at a contact time of 8.2S, the conversion was 26% and the selectivity was 99%, and at a contact time of 5.3S, the conversion was 24% and the selectivity was 99%.
Claims (5)
1. A fluorination catalyst for fluorinating halogenated hydrocarbon is characterized in that SiO-containing23% -20% of gamma-Al2O3With a mixture of anhydrous hydrogen fluoride and nitrogen and pure anhydrous hydrogen fluoride, fluorinating at the temperature of 150-2To prepare the active aluminum fluoride carrier with the specific surface area of more than or equal to 40m2g-1Pore volume is more than or equal to 0.18ml g-1gamma-AlF with average pore diameter less than 903The content of (A) is more than or equal to 50 percent, AlF3The content is more than or equal to 90 percent, and the average grain size is less than or equal to 150. Chromium, cobalt and magnesium are loaded by adopting an impregnation method, and the mass ratio is as follows: 1-10: 1: 0.1 in a nitrogen flow at 350 ℃ under 120-Curing, and activating by using a mixture of hydrogen fluoride and nitrogen and pure hydrogen fluoride at the temperature of 350 ℃ at 180 ℃ to obtain the fluorination catalyst.
2. Fluorination catalyst according to claim 1, characterized in that it is prepared using a SiO-containing catalyst25% of gamma-AlF3Is subjected to gas phase fluorination with a mixture of anhydrous hydrogen fluoride and nitrogen and pure anhydrous hydrogen fluoride at the temperature of 150 ℃ and 200 ℃ to prepare the active aluminum fluoride carrier with the specific surface area of 57m2g-1Pore volume 0.25 ml g-1Average pore diameter of 40. gamma. -AlF3Content 70% AlF3The content is 90 percent, the average grain size is 98A, and the mass ratio of the active components chromium, cobalt and magnesium loaded on the carrier is as follows: 5: 1: 0.1.
3. Fluorination catalyst according to claim 1, characterized in that it is prepared using a SiO-containing catalyst210% of gamma-Al2O3Fluorinating with a mixture of anhydrous hydrogen fluoride and nitrogen and pure anhydrous hydrogen fluoride at the temperature of 150-200 ℃ to prepare an active aluminum fluoride carrier with the specific surface area of 50m2g-1Pore volume 0.23 ml g-1An average pore diameter of 52 DEG, gamma-AlF3Content of 87% AlF3Is 95%, the average grain size is 105. ang. and the carrier AlF3The mass ratio of the loaded chromium, the loaded cobalt andthe loaded magnesium is as follows: 5: 1: 0.1.
4. Fluorination catalyst according to claim 1, characterized in that it is prepared using a SiO-containing catalyst215% of gamma-Al2O3The mixture of the active aluminum fluoride and the nitrogen and the pure anhydrous hydrogen fluoride are fluorinated at the temperature of 200-300 ℃ to prepare the active aluminum fluoride carrier with the specific surface area of 42m2g-1Pore volume 0.20 ml g-1An average pore diameter of 73. gamma. -AlF3Content of 100% AlF3The content of (A) is 100% and the average crystal grain size is 110. ANG.
5. The same fluorination catalyst as in claims 1-4 is used in a two-step reaction for the synthesis of 1, 1, 1-trifluoro-2-chloroethane and 1, 1, 1, 2-tetrafluoroethane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95115476A CN1041804C (en) | 1995-09-13 | 1995-09-13 | Catalyst for fluoreation of halogenated hydrocarbon |
| PCT/CN1996/000061 WO1997010053A1 (en) | 1995-09-13 | 1996-08-09 | Catalyst for fluorinating halohydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95115476A CN1041804C (en) | 1995-09-13 | 1995-09-13 | Catalyst for fluoreation of halogenated hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1145275A CN1145275A (en) | 1997-03-19 |
| CN1041804C true CN1041804C (en) | 1999-01-27 |
Family
ID=5080516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95115476A Expired - Lifetime CN1041804C (en) | 1995-09-13 | 1995-09-13 | Catalyst for fluoreation of halogenated hydrocarbon |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1041804C (en) |
| WO (1) | WO1997010053A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981813A (en) * | 1996-05-22 | 1999-11-09 | Ausimont S.P.A. | Fluorination process of halogenated organic compounds |
| IT1291758B1 (en) * | 1997-05-22 | 1999-01-21 | Ausimont Spa | PROCESS FOR THE PREPARATION OF ALUMINUM FLUORIDE |
| IT1303073B1 (en) * | 1998-05-07 | 2000-10-23 | Ausimont Spa | PROCESS FOR THE PREPARATION OF ALUMINUM FLUORIDE |
| GB0507139D0 (en) | 2005-04-08 | 2005-05-18 | Ineos Fluor Holdings Ltd | Catalyst |
| CN1911512B (en) * | 2005-07-07 | 2011-12-07 | 独立行政法人产业技术综合研究所 | Fluorination catalysts, method for their preparation, and method for producing fluorinated compounds using the catalysts |
| CN106256429B (en) * | 2015-06-18 | 2020-02-11 | 中化近代环保化工(西安)有限公司 | Aluminum fluoride catalyst with high specific surface area and application thereof |
| CN105597795B (en) * | 2015-11-06 | 2018-04-17 | 西安近代化学研究所 | A kind of preparation method of nanometer of Naluminum fluoride base catalyst |
| CN106861714B (en) * | 2017-02-09 | 2019-08-27 | 西安近代化学研究所 | A kind of catalyst of hydrogen chloride conversion preparing chlorine gas |
| CN106861707B (en) * | 2017-02-09 | 2019-08-27 | 西安近代化学研究所 | A kind of preparation method of preparing chlorine by oxidizing hydrogen chloride catalyst |
| CN106964402A (en) * | 2017-04-14 | 2017-07-21 | 张玲 | A kind of preparation method for being fluorinated hydrogen activation catalyst |
| CN107597096B (en) * | 2017-08-22 | 2018-12-04 | 乳源东阳光氟有限公司 | It is a kind of using aluminium oxide as chromium-based catalysts of carrier and preparation method thereof |
| CN108273556B (en) * | 2018-01-31 | 2020-07-21 | 中国民航大学 | Preparation method of fluorine/chlorine exchange catalyst based on MOF |
| CN113856707A (en) * | 2021-09-18 | 2021-12-31 | 深圳市东有新材料科技有限公司 | Hollow nano aluminum fluoride ball with high catalytic efficiency and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107751A (en) * | 1985-11-15 | 1987-05-20 | 阿托化学公司 | Method by dichloro tetrafluoro ethane and the synthetic chloropentafluoroethane of hydrofluoric acid |
| EP0408005A1 (en) * | 1989-07-12 | 1991-01-16 | AUSIMONT S.p.A. | Process for preparing 1,1,1,2-tetrafluoroethane |
-
1995
- 1995-09-13 CN CN95115476A patent/CN1041804C/en not_active Expired - Lifetime
-
1996
- 1996-08-09 WO PCT/CN1996/000061 patent/WO1997010053A1/en active Search and Examination
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107751A (en) * | 1985-11-15 | 1987-05-20 | 阿托化学公司 | Method by dichloro tetrafluoro ethane and the synthetic chloropentafluoroethane of hydrofluoric acid |
| EP0408005A1 (en) * | 1989-07-12 | 1991-01-16 | AUSIMONT S.p.A. | Process for preparing 1,1,1,2-tetrafluoroethane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1145275A (en) | 1997-03-19 |
| WO1997010053A1 (en) | 1997-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1041804C (en) | Catalyst for fluoreation of halogenated hydrocarbon | |
| KR100351211B1 (en) | Chromium-based fluorinated catalyst, preparation method of the catalyst and fluorination method using the catalyst | |
| EP0958265B1 (en) | The catalytic manufacture of pentafluoropropenes | |
| KR950006521B1 (en) | Process for the preparation of 1,1,1,2-tetra fluoroethane | |
| US5569795A (en) | Fluorination catalyst and fluorination process | |
| EP0510771B1 (en) | Process for the preparation of an extruded silica-based catalyst of catalyst precursor | |
| AU662185B2 (en) | Mass catalysts based on chromium and nickel oxides and their application to the fluorination of halogenated hydrocarbons | |
| EP1440939A1 (en) | Method for the preparation of amorphous metal fluorides | |
| JPH0348632A (en) | Preparation of 1,1,1,2-tetra- fluoroethane | |
| US7592287B2 (en) | Method for the preparation of high surface area metal fluorides | |
| US5300711A (en) | Process for the manufacture of 2,2-dichloro-1,1,1-trifluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane and pentafluoroethane | |
| US3978145A (en) | Use of hexagonal chromium (111) oxide hydroxide catalyst in fluorination process | |
| EP0879790B1 (en) | Process for the preparation of aluminum fluoride | |
| JP4338822B2 (en) | Method for producing aluminum fluoride | |
| CN1408476A (en) | High active long-acting fluorating catalyst and its producing method | |
| JP3310666B2 (en) | Method for synthesizing metal oxide having high specific surface area and high porosity, obtained oxide, and catalyst containing the oxide | |
| CN1068244C (en) | Chromium-based fluorination catalyst, production method thereof, and fluorination method | |
| CN1037095C (en) | Process for fluorinating hydrocarbon | |
| JPH0838904A (en) | Chromium-based fluorination catalyst, its production and fluorinating method | |
| JP2000053413A (en) | Highly heat-resistant mesoporous silica and its production | |
| JPH04227066A (en) | Garoalmino silicate latalyst and its usage in aromatization of 2-7 c hydrocarbon | |
| US5494877A (en) | Chromium-based fluorination catalyst containing gallium and production method thereof | |
| JP2000070713A (en) | Catalyst for fluorination of halogenated organic compound | |
| JP3582798B2 (en) | Fluorination catalyst and fluorination method | |
| JP5026628B2 (en) | NOVEL ALUMINA, METHOD FOR PREPARATION THEREOF AND CATALYST, ITS USE AS CATALYST SUPPORT OR ADSORBENT |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JINZHU MODERN CHEMICAL CO., LTD., XI AN Free format text: FORMER OWNER: XI AN INST. OF MODERN CHEMISTRY Effective date: 20020604 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20020604 Address after: Jinghe Industrial Park in Shaanxi Province, Xi'an economic and Technological Development Zone Patentee after: Jinzhu Modern Chemical Co., Ltd., Xi'an Address before: Box eighteen, Xi'an, Shaanxi, China Patentee before: Xi'an Inst. of Modern Chemistry |
|
| C56 | Change in the name or address of the patentee |
Owner name: CHIAN CHEMICAL MODERN ENVIRONMENTAL PROTECTION CHE Free format text: FORMER NAME OR ADDRESS: JINZHU MODERN CHEMICAL CO., LTD., XI AN |
|
| CP03 | Change of name, title or address |
Address after: Jinghe Industrial Park 710201 Shaanxi Province, Xi'an economic and Technological Development Zone Patentee after: Sinochem Modern Environmental Protection Chemicals (Xi'an) Co., Ltd. Address before: Jinghe Industrial Park 710201 Shaanxi Province, Xi'an economic and Technological Development Zone Patentee before: Jinzhu Modern Chemical Co., Ltd., Xi'an |
|
| CX01 | Expiry of patent term |
Granted publication date: 19990127 |
|
| EXPY | Termination of patent right or utility model |