CN100398205C - Catalyst for fluorination - Google Patents
Catalyst for fluorination Download PDFInfo
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- CN100398205C CN100398205C CNB2005100532004A CN200510053200A CN100398205C CN 100398205 C CN100398205 C CN 100398205C CN B2005100532004 A CNB2005100532004 A CN B2005100532004A CN 200510053200 A CN200510053200 A CN 200510053200A CN 100398205 C CN100398205 C CN 100398205C
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
To produce a catalyst having an enhanced fluorination activity in the catalyst used for a fluorination reaction using hydrogen fluoride as a fluorinating agent, and to provide a fluorination method using the catalyst. This catalyst for the fluorination reaction is characterized in that a porous support comprising calcium fluoride or magnesium fluoride is carried with an antimony halogenated substance represented by formula (1): SbFnCl(5-n) (wherein (n) represents a number of 0-5).
Description
[technical field]
The present invention relates to catalyst for fluorination and use the preparation method of the fluorinated hydrocarbons of this catalyst.
[background technology]
The halogen exchange metal fluoride catalysts is the catalyst of high efficiency in the vapor phase flaorination process.Improving this catalyst performance by increase surface area or interpolation assistant metal is the important method of carrying out so far.EP 0514923 (1998) discloses by carrying out the come to the surface method of the catalytic performance that improves chromium-based catalysts of height.In addition, EP 0502605 (1992) or J.Fluorine Chem.111 (2001) 193 and EP0801980 (1997) have reported the result who improves catalyst activity by the assistant metal that this catalyst is added Zn, Co, Ti, Ni etc.
For synthetic organofluorine compound, use antimony pentafluoride (SbF
5) handle the exemplary that the organic halogen derivative is the Swart reaction.Yet this occasion is because SbF
5Volatilization consumingly in humid air, its application is subjected to great restriction.J.C.S.Chem.Comm.1973 has put down in writing in 815 by to SbF
5Heating adds graphite and obtains new fluorination reagent.WO 98/40335 discloses by making HF and four halogenopropanes carry out the method for the synthetic HFC-245fa of gas-phase reaction, and this method is used in the active carbon and flooded SbCl
5Catalyst as process catalyst.JP 3031465 discloses the gaseous fluoridizing method in order to obtain HFC-245fa, HF and pentachloropropane to be reacted.The SbCl of this method working load on active carbon
5As process catalyst.The operability of catalyst in practicality that these antimonic salts are loaded in the carbon compares SbF
5Height, but the existing problems of stability at high temperature.Use the slaine that contains antimony as fluorination catalyst in addition in the United States Patent (USP) 5910616, but the kind of its metal is restricted.
Present inventors have found to make SbCl
5After being immersed in the porous aluminum fluoride (PAF), fluoridize the method (special Willing J P2002-334883) that obtains new fluorination catalyst by using HF.This catalyst is excellent catalytic activity to be arranged and for SbF in halogen exchange reaction
5The improved catalyst of characteristic (humidity corrosion and toxicity).SbF
5/ PAF is adapted in the organic synthesis using as the fixed bde catalyst of fluorization agent or F/Cl exchange usefulness.
Present inventors have proposed to have 60m
2Porous calcirm-fluoride (PCF) scheme (non-patent literature 1) of/g surface area (J.Fluorine Chem.116 (2002) 65-69).In addition, also proposed to have 90～200m
2The porous charomic fluoride of this high surface of/g (Porous Chromium fluoride) is scheme (patent documentation 1) (special Willing JP 2003-303078) (PCrF).
Yet these schemes consider to be still the catalyst that can not meet the demands from the viewpoint for the metal load that further makes the fluorination reaction activate.
[non-patent literature 1]
J.Fluorine Chem.116(2002)65～69
[patent documentation 1]
Special Willing JP2003-303078 number
[summary of the invention]
[problem that invention will solve]
The problem that the present invention relates to is, for the catalyst to use in the fluorination reaction of hydrogen fluoride as fluorization agent, provides a kind of fluorination process that height is fluoridized active catalyst and this catalyst of use is provided that has.
[solving the measure that problem is used]
According to the invention provides catalyst shown below and method.
(1) catalyst for fluorination is characterized in that, the antimony halide shown in the following general formula of load (1) on the porous carrier that calcirm-fluoride or magnesium fluoride constitute:
[changing 4]
SbF
nCl
5-n (1)
(in the formula, n represents 0～5 number).
(2) catalyst for fluorination is characterized in that, has 90～200m by what porous chromium oxide and hydrogen fluoride made
2Antimony halide shown in the following general formula of load (1) on the porous carrier of/g surface area.
[changing 5]
SbF
nCl
5-n (1)
(in the formula, n represents 0～5 number)
(3) catalyst described in aforementioned (1), wherein this porous carrier is to have 15～100m
2The calcirm-fluoride of/g surface area.
(4) any one described catalyst in aforementioned (1)～(3), wherein the halid content of this antimony is 1～70 weight % in the catalyst.
(5) preparation method of fluorinated hydrocarbons is characterized in that, uses hydrogen fluoride that the hydrocarbon of the halogen beyond fluorine-containing is carried out in the method for gas phase fluorination in the presence of catalyst, as this catalyst, uses any one described catalyst in aforementioned (1)～(4).
(6) aforementioned (5) described method, wherein this halogen-containing hydrocarbon is the alkene of carbon number 1～6 or the halide of alkane.
(7) aforementioned (5) described method, wherein this halogen-containing hydrocarbon is 1,1,3,3,3-pentachloropropane, 1-chloro-3,3,3-trifluoro propene, 1,3,3,3-tetrachloro propane or carrene.
(8) aforementioned (5) described method wherein uses 1,1,3,3 as this halogen-containing hydrocarbon, and the 3-pentachloropropane generates anti-form-1-chloro-3,3,3-trifluoro propene and/or cis-1-chloro-3,3,3-trifluoro propene.
(9) aforementioned (5) described method is wherein used 1-chloro-3,3 as this halogen-containing hydrocarbon, 3-trifluoro propene, generation 1,1,1,3,3-pentafluoropropane.
(10) aforementioned (5) described method wherein uses 1,1,1 as this halogen-containing hydrocarbon, and 3-tetrachloro propane generates 3,3,3-trifluoro propene and/or 1,1,1,3-tetrafluoropropane.
(11) a kind of method is characterized in that, in the presence of catalyst, use hydrogen fluoride with 1,1,3,3,3-pentachloropropane, 1-chloro-3,3,3-trifluoro propene or 1,1,1,3-tetrachloro propane carries out in the method for gas phase fluorination, as this catalyst, use the halid catalyst for fluorination of antimony shown in the following general formula of load (1) on the porous carrier that the porous aluminum fluoride constitutes:
[changing 6]
SbF
nCl
5-n (1)
(in the formula, n represents 0～5 number).
(12) aforementioned (5) described method is wherein used carrene as this halogen-containing hydrocarbon, generates difluoromethane and/or chlorofluoromethane.
[invention effect]
According to the present invention, provide and use hydrogen fluoride (HF) to make chlorine atom contained in the organohalogen compounds be transformed into the high efficiency catalyst that uses in the fluorination reaction of fluorine atom.This catalyst has high activity and at high temperature also stable, is to be suitable as the catalyst that industrial catalyst uses.
[preferred plan that carries out an invention]
Catalyst of the present invention has the structure of the antimony fluoride shown in the following formula of load (1) in porous carrier.
[changing 7]
SbF
nCl
5-n (1)
(in the formula, n represents 0～5 number)
This porous carrier is calcirm-fluoride or the porous carrier of magnesium fluoride formation or the porous carrier that is made by porous chromium oxide and hydrogen fluoride.
The porous carrier that calcirm-fluoride constitutes, its surface area does not have particular restriction, preferably 15～100m
2/ g.The porous carrier that magnesium fluoride constitutes, its surface area does not have particular restriction.
The porous carrier that porous chromium oxide and hydrogen fluoride make, its surface area is 90～200m
2/ g, 150～190m preferably
2/ g.
These porous carriers can be figure of tablet or graininess, and its average grain diameter of granular occasion does not have particular restriction, normally 0.2～5mm, 0.5～3mm preferably.
Any porous carrier can contain auxiliary element.Can enumerate metal oxide, metal chloride, other slaine etc. as auxiliary element, its kind does not have particular restriction.The content of auxiliary element is following, the 5 weight % or below the 5 weight % preferably of 30 weight % or 30 weight %.
The surface area of porous carrier is the bigger the better.This porous carrier shows the effect of the antimony fluoride stabilisation of the difficult operation of sening as an envoy to.
As porous carrier, preferably having average pore diameter is 5～120
, preferred 20～50
, porosity is the carrier of the pore structure of 0.05～0.8cc/g, preferred 0.1～0.7cc/g.
The antimony fluoride of aforementioned formula (1) expression that the present invention uses promotes composition as activity of such catalysts and works.Antimony fluoride is with respect to the ratio of porous carrier, is 1～70 weight %, 5～50 weight % preferably in catalyst.
Catalyst of the present invention can be immersed on the porous carrier with the solution state that is dissolved in the carbon tetrachloride equal solvent by making antimony fluoride, and carries out drying and prepare.
In addition, catalyst of the present invention also can make antimony chloride be immersed in the porous carrier with solution state, after the drying, hydrogen fluoride (HF) reaction is prepared the method that this antimony chloride is transformed into antimony fluoride.
Catalyst of the present invention has the high activity of fluoridizing, and can be suitable as the halogen atom that makes beyond the fluorine contained in the halogenated hydrocarbon and HF and carry out the fluoridation catalyst use of gas-phase reaction when being transformed into fluorine atom.But this occasion is if the antimony fluoride monomer though be liquid, can use with the form of fixed bed by catalyst being carried out immobilization.In addition, catalyst of the present invention is also stable under the high temperature more than 400 ℃ or 400 ℃.
When using catalyst of the present invention, for example, by making 1,1,1,3,3-pentachloropropane and HF carry out gas-phase reaction, then can be transformed into anti-form-1-chloro-3,3 expeditiously, 3-trifluoro propene or cis-1-chloro-3,3,3-trifluoro propene.At this moment, reaction temperature is 150～450 ℃, is preferably 200～300 ℃.HF and 1,1,1,3, the mol ratio of 3-pentachloropropane is 1: 1～30: 1, preferred 3: 1～20: 1, more preferably 5: 1～15: 1.
In addition, when using catalyst of the present invention, by making 1-chloro-3,3,3-trifluoro propene and HF carry out gas-phase reaction, can be transformed into 1,1,1,3 expeditiously, the 3-pentafluoropropane.At this moment, reaction temperature is 50～350 ℃, is preferably 70～120 ℃.HF and 1-chloro-3,3, the mol ratio of 3-trifluoro propene are 1: 1～30: 1, are preferably 2: 1～15: 1.
When using catalyst of the present invention, by making 1,1,1,3-tetrachloro propane and HF carry out gas-phase reaction, can be transformed into 3,3 expeditiously, 3-trifluoro propene or 1,1,1,3-tetrafluoropropane.This occasion reaction temperature is 250～450 ℃, is preferably 300～350 ℃.HF and 1,1,1, the mol ratio of 3-tetrachloro propane is 1: 1～30: 1, is preferably 5: 1～15: 1.
In addition, above-mentioned 1,1,3,3,3-pentachloropropane, 1-chloro-3,3,3-trifluoro propene or 1,1,1, in the gas-phase reaction of 3-tetrachloro propane and HF, even use the catalyst of the antimony fluoride that contains aforementioned formula (1) expression on the porous carrier of porous aluminum fluoride, also can react equally aptly as main body.As such catalyst, for example, can enumerate above-mentioned SbF
5/ PAF (special Willing JP2002-334883).
When using catalyst of the present invention, carry out gas-phase reaction, can be transformed into difluoromethane expeditiously by making carrene and HF.This occasion, HF and carrene (CH
2Cl
2) mol ratio be 1: 1～30: 1, be preferably 3: 1～10: 1.Reaction temperature is 150～450 ℃, is preferably 200～350 ℃.
When using Preparation of Catalyst fluorinated hydrocarbons of the present invention, as the halogenated hydrocarbon of this reaction raw materials can enumerate only contain chlorine, chlorine and fluorine, only brominated, bromine and fluorine, only contain the hydrocarbon of iodine, iodine and fluorine.The carbon number of hydrocarbon is 1～12, is preferably 1～6.In the halogenated hydrocarbon, this hydrocarbon can be the aliphatic hydrocarbon of carbon number 1～8 or the annular aliphatic hydrocarbon of carbon number 5～8, the aromatic hydrocarbon of carbon number 6-12.When making these halogenated hydrocarbons and HF carry out gas-phase reaction, can suitably select for use this halogenated hydrocarbon to form the reaction temperature of gas phase, in addition, also can suitably select for use and the corresponding HF/ halogenated hydrocarbon of desired fluoride mol ratio.
[embodiment]
Reach comparative example by the following examples and illustrate in greater detail the present invention, but the present invention is not subjected to the qualification of following example.
Moreover said surface area is the B.E.T surface area of habitually practising in this specification.
Embodiment 1
(in the porous charomic fluoride, contain SbF
5The catalyst S bF of structure
5The preparation of/PCrF)
At N
2(adopting PCrF, its surface area of the method preparation described in special Willing JP2003-303078 number is 187m to 10g tablet shape porous charomic fluoride (PCrF) under the ambiance
2/ g) in, slowly drip the SbCl of 10g
5Make in this wise and contain SbCl
5The PCrF tablet.
At circulation N
2Behind following 100 ℃ of these tablets of drying, use N
2Anhydrous HF (the AHF) (N of dilution
2/ AHF=1/1) to handle at 100 ℃, the concentration of the temperature that raises again and AHF uses pure AHF to handle at 200 ℃ at last.By blowing N
2Gas is removed the HF of final residual, makes catalyst A SbF
5/ PCrF.SbF
5The result that/PCrF carries out differential scanning calorimetric analysis (DSC) shows, do not have neither endothermic nor exothermic to change to about 500 ℃, promptly illustrates to be still stable up to about 500 ℃.
Embodiment 2
(use SbF
5The 1-chloro-3,3 of/PCrF catalyst, 3-trifluoro propene synthetic)
10ml is added in the reactor catalyst A, and with 1,1,1,3,3-pentachloropropane (PCPAN) (flow: the 0.15g/ branch) supply with, react at 305 ℃ with the mixture gasification back of anhydrous HF.Reaction product carries out structural confirmation with NMR after washing, soda lime drying, generated anti-form-1-chloro-3,3, and 3-trifluoro propene and cis-1-chloro-3,3,3-trifluoro propene, yield are respectively 89.8% and 9.0%.
Embodiment 3
Except using the SbCl of 5.4g
5In addition, other make catalyst B similarly to Example 1.
Embodiment 4
Among the embodiment 2, except using catalyst B alternative catalysts A, similarly react.The results are shown in table 1 described later.
Embodiment 5
Except using SbCl
53.2g in addition, other make catalyst C similarly to Example 1.
Embodiment 6
Among the embodiment 2, except using catalyst C alternative catalysts A, similarly react, the results are shown in aftermentioned table 1.
Comparative example 1
Among the embodiment 2, except using porous charomic fluoride PCrF alternative catalysts A, similarly react.The results are shown in aftermentioned table 1.
Aforesaid reaction result conclusion is shown in table 1.The catalyst that use contains antimonic salt can obtain higher yield than the catalyst that does not contain antimonic salt under lower reaction temperature.
[table 1]
Product 1: trans-CF
3CH=CHCl
Product 2: cis-CF
3CH=CHCl
Embodiment 7
(use SbF
5/ PCrF catalyst synthesizes 1,1,1,3, the 3-pentafluoropropane)
Among the embodiment 2, except the catalyst C that uses embodiment 5 expressions as catalyst, use 1-chloro-3,3 simultaneously, 3-trifluoro propene (CTFP) is as beyond the raw material halogenated hydrocarbon, other similarly react.But the reaction temperature of this moment is 270 ℃.
The result of this reaction generates trans-CF
3CH=CHF (selectivity 44.7%), CF
3CH
2CHF
2(selectivity 49.5%), cis-CF
3CH=CHCl (selectivity 6.0%).This moment, raw material was (trans-CF
3CH=CHCl) conversion ratio is 70.2%.
Embodiment 8
(use SbF
3/ PCrF catalyst synthesizes 3,3, the 3-trifluoro propene)
Among the embodiment 2, except using catalyst A as catalyst, use 1,1,1 simultaneously, 3-tetrachloro propane (TCP) is as beyond the raw material, and other similarly react.At this moment, under 320 ℃ and 340 ℃, react.
The result of this reaction generates 3,3,3-trifluoro propene (yield 64.7%) and 1,3,3,3-tetrafluoeopropene (yield 0.7%) at 320 ℃.Generate aforementioned 2 kinds of compounds at 340 ℃, yield is respectively 89.6% and 10%.
Embodiment 9
(use SbF
5/ PCrF catalyst synthesizes difluoromethane)
Except the catalyst A of using embodiment 1 to make, use carrene as beyond the raw material simultaneously, other react similarly to Example 2.
The reaction result of this moment is shown in table 2.
[table 2]
Embodiment 10
Among the embodiment 9, except using the catalyst B shown in the embodiment 3, other similarly react as catalyst.This reaction result is shown in table 3.
[table 3]
Embodiment 11
(preparation contains SbF in porous calcirm-fluoride (PCF)
5Catalyst S bF
5/ PCF)
Except use has 60m
2The tablet shape PCF 10g of/g surface area is as beyond the porous compounds, and other experimentize similarly to Example 1, make catalyst D SbF
5/ PCF.SbF
5The result that/PCF carries out differential scanning calorimetric analysis (DSC) shows, do not have neither endothermic nor exothermic to change to about 500 ℃, promptly is still stable to about 500 ℃.
Embodiment 12
(use SbF
5/ PCF catalyst synthesizes 1,1,1,3, the 3-pentafluoropropane)
Among the embodiment 7, except the catalyst D that makes as catalyst use embodiment 11, other similarly react.Reaction result is shown in table 4.
[table 4]
Product 1: trans-CF
3CH=CHF
Product 2:CF
3CH
2CF
2
Product 3: cis-CF
3CH=CHCl
Embodiment 13
(use SbF
5/ PCF catalyst synthesizes 1-chloro-3,3,3-trifluoro propene)
Among the embodiment 2, except the catalyst D alternative catalysts A that use embodiment 11 makes, other similarly react.The results are shown in table 5.
[table 5]
| No. | Reaction temperature (℃) | Product 1 yield (%) |
| 1 | 190 | 49.6 |
| 2 | 220 | 68.2 |
| 3 | 250 | 77.4 |
| 4 | 280 | 76.8 |
Product 1:CF
3CH=CHCl
Embodiment 14
(contain SbF in the preparation porous magnesium fluoride
5Catalyst S bF
5/ PM)
SbCl except the 25.8g that uses
5, use and to have 8.6m
2The magnesium fluoride 23.4g of/g surface area is as beyond the porous compounds, and other experimentize similarly to Example 1, make SbF
5/ PMgF catalyst E.SbF
5The result that/PCF carries out differential scanning calorimetric analysis (DSC) shows, do not have neither endothermic nor exothermic to change to about 500 ℃, promptly is still stable to about 500 ℃.
Embodiment 15
(use SbF
5The PMgF catalyst synthesizes 1-chloro-3,3,3-trifluoro propene)
Among the embodiment 2, except use embodiment 14 made catalyst E alternative catalysts A, other similarly reacted.The results are shown in table 6.
[table 6]
| No. | Reaction temperature (℃) | Product 1 yield (%) |
| 1 | 190 | 67.1 |
| 2 | 220 | 79.2 |
| 3 | 250 | 80.5 |
| 4 | 280 | 79.7 |
Product 1:CF
3CH=CHCl
Embodiment 16
(use SbF
5/ PMgF catalyst synthesizes 1,1,1,3, the 3-pentafluoropropane)
Among the embodiment 7, except the catalyst E that makes as catalyst use embodiment 14, other similarly react.The results are shown in table 7.
[table 7]
Product 1: trans-CF
3CH=CHF
Product 2:CF
3CH
2CF
2
Product 3: cis-CF
3CH=CHCl
Embodiment 17
(contain SbF in the preparation porous aluminum fluoride
5Catalyst S bF
5/ PAF)
Except using the SbCl of 26.7g
5, use to have 92.0m
2The porous aluminum fluoride 18.0g of/g surface area is as beyond the porous compounds, and other experimentize similarly to Example 1, make SbF
5/ PAF catalyst F.SbF
5The result that/PAF carries out differential scanning calorimetric analysis (DSC) shows, do not have neither endothermic nor exothermic to change to about 500 ℃, promptly is still stable to about 500 ℃.
Embodiment 18
(use SbF
5/ PAF catalyst synthesizes 1,1,1,3, the 3-pentafluoropropane)
Among the embodiment 7, except using catalyst F that embodiment 17 makes as the catalyst, other similarly react.The results are shown in table 8.
[table 8]
Product 1: trans-CF
3CH=CHF
Product 2:CF
3CH
2CF
2
Product 3: cis-CF
3CH=CHCl
Comparative example 2
(contain SbF in the active carbon
5Catalyst S bF
5The heat endurance of/C)
Except using active carbon (use amount and SbCl
5Identical) as beyond the porous compounds, other experimentize similarly to Example 1, make SbF
5/ C.SbF
5/ C carries out the result of differential scanning calorimetric analysis (DSC), produces big heat release, SbF from about 330 ℃
5/ C decomposes.Show SbF thus
5/ C stability at high temperature is than containing SbF in the slaine
5Catalyst S bF
5/ PCF, SbF
5/ PCrF, SbF
5/ PMgF, SbF
5/ PAF is low.
Claims (12)
1. a catalyst for fluorination is characterized in that, the antimony halide of the following general formula of load (1) expression on the porous carrier of calcirm-fluoride or magnesium fluoride formation:
SbF
nCl
5-n(1)
In the formula, n represents 0～5 number.
2. a catalyst for fluorination is characterized in that, the 90～200m that has that is being made by porous chromium oxide and hydrogen fluoride
2Antimony halide shown in the following general formula of load (1) on the porous carrier of/g surface area:
SbF
nCl
5-n(1)
In the formula, n represents 0～5 number.
3. the described catalyst of claim 1, wherein this porous carrier is to have 15～100m
2The calcirm-fluoride of/g surface area.
4. each described catalyst in the claim 1～3, wherein the halid content of this antimony is 1～70 weight % in the catalyst.
5. the preparation method of a fluorinated hydrocarbons, it is characterized in that, in the presence of catalyst, use hydrogen fluoride that halogen-containing hydrocarbon is carried out gas phase fluorination, fluorine contained in halogen-containing hydrocarbon halogen in addition is transformed in the method for fluorine atom, uses each described catalyst in claim 1～4 as this catalyst.
6. the described method of claim 5, wherein this halogen-containing hydrocarbon is the alkene of carbon number 1～6 or the halide of alkane.
7. the described method of claim 5, wherein this halogen-containing hydrocarbon is 1,1,1,3,3-pentachloropropane, 1-chloro-3,3,3-trifluoro propene, 1,1,1,3-tetrachloro propane or carrene.
8. the described method of claim 5 wherein as this halogen-containing hydrocarbon, uses 1,1,1,3, and the 3-pentachloropropane generates anti-form-1-chloro-3,3,3-trifluoro propene and/or cis-1-chloro-3,3,3-trifluoro propene.
9. the described method of claim 5 is wherein used 1-chloro-3,3 as this halogen-containing hydrocarbon, and the 3-trifluoro propene generates 1,1,1,3, the 3-pentafluoropropane.
10. the described method of claim 5 wherein as this halogen-containing hydrocarbon, uses 1,1,1, and 3-tetrachloro propane generates 3,3,3-trifluoro propene and/or 1,1,1,3-tetrafluoropropane.
11. a method is characterized in that, uses hydrogen fluoride with 1 in the presence of catalyst, 1,1,3,3-pentachloropropane, 1-chloro-3,3,3-trifluoro propene or 1,1,1,3-tetrachloro propane carries out in the method for gas phase fluorination, as this catalyst, uses the halid catalyst for fluorination of antimony shown in the following general formula of load (1) on the porous carrier that the porous aluminum fluoride constitutes:
SbF
nCl
5-n(1)
In the formula, n represents 0～5 number.
12. the described method of claim 5 is wherein used carrene as this halogen-containing hydrocarbon, generates difluoromethane and/or chlorofluoromethane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004065929A JP4257424B2 (en) | 2004-03-09 | 2004-03-09 | Catalyst for fluorination reaction |
| JP065929/04 | 2004-03-09 | ||
| JP065929/2004 | 2004-03-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1680029A CN1680029A (en) | 2005-10-12 |
| CN100398205C true CN100398205C (en) | 2008-07-02 |
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ID=35067004
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| CNB2005100532004A Expired - Fee Related CN100398205C (en) | 2004-03-09 | 2005-03-08 | Catalyst for fluorination |
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| JP (1) | JP4257424B2 (en) |
| CN (1) | CN100398205C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2041053A1 (en) * | 2006-07-07 | 2009-04-01 | E.I. Du Pont De Nemours And Company | Catalytic addition of hydrofluorocarbons to fluoroolefins |
| US8916733B2 (en) * | 2008-06-17 | 2014-12-23 | Honeywell International Inc. | Processes for hydrofluorination of 2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropane |
| CN101696149A (en) * | 2009-10-29 | 2010-04-21 | 江苏康泰氟化工有限公司 | Method for preparing 1,1,1-trifluoro-2-chloroethane |
| US9045386B2 (en) * | 2010-02-18 | 2015-06-02 | Honeywell International Inc. | Integrated process and methods of producing (E)-1-chloro-3,3,3-trifluoropropene |
| CN102199071B (en) * | 2011-04-08 | 2013-05-01 | 北京宇极科技发展有限公司 | Method for synthesizing 2,3,3,3-tetrafluoropropene |
| CN104707631A (en) | 2013-12-12 | 2015-06-17 | 西安近代化学研究所 | Chromium-free gas phase fluorination catalyst and use thereof |
| EP3847145A2 (en) * | 2018-09-07 | 2021-07-14 | The Chemours Company FC, LLC | Fluorine removal from antimony fluorohalide catalyst using chlorocarbons |
| CN112452345B (en) * | 2020-11-17 | 2023-03-21 | 西安近代化学研究所 | Catalyst for gas phase fluorination synthesis of trans-1-chloro-3, 3-trifluoropropene and synthesis method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205246A (en) * | 1998-07-16 | 1999-01-20 | 中国科学院上海有机化学研究所 | Catalyst for preparing 1,1,1-trifluoro-2-ethane chloride and its application |
| CN1282723A (en) * | 1999-07-28 | 2001-02-07 | 浙江省化工研究院 | Process for preparing 1,1,1-trichloro-2-chloroethone |
| US6350926B1 (en) * | 1996-09-03 | 2002-02-26 | Syngenta Limited | Chlorofluorohydrocarbon and process thereto |
| WO2002043861A1 (en) * | 2000-11-30 | 2002-06-06 | Union Carbide Chemicals & Plastics Technology Corporation | Novel antimony catalyst compositions |
-
2004
- 2004-03-09 JP JP2004065929A patent/JP4257424B2/en not_active Expired - Lifetime
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2005
- 2005-03-08 CN CNB2005100532004A patent/CN100398205C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6350926B1 (en) * | 1996-09-03 | 2002-02-26 | Syngenta Limited | Chlorofluorohydrocarbon and process thereto |
| CN1205246A (en) * | 1998-07-16 | 1999-01-20 | 中国科学院上海有机化学研究所 | Catalyst for preparing 1,1,1-trifluoro-2-ethane chloride and its application |
| CN1282723A (en) * | 1999-07-28 | 2001-02-07 | 浙江省化工研究院 | Process for preparing 1,1,1-trichloro-2-chloroethone |
| WO2002043861A1 (en) * | 2000-11-30 | 2002-06-06 | Union Carbide Chemicals & Plastics Technology Corporation | Novel antimony catalyst compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005254064A (en) | 2005-09-22 |
| JP4257424B2 (en) | 2009-04-22 |
| CN1680029A (en) | 2005-10-12 |
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