CN1680029A - Catalyst for fluorination - Google Patents

Catalyst for fluorination Download PDF

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Publication number
CN1680029A
CN1680029A CNA2005100532004A CN200510053200A CN1680029A CN 1680029 A CN1680029 A CN 1680029A CN A2005100532004 A CNA2005100532004 A CN A2005100532004A CN 200510053200 A CN200510053200 A CN 200510053200A CN 1680029 A CN1680029 A CN 1680029A
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catalyzer
fluoride
sbf
catalyst
halogen
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CN100398205C (en
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权恒道
杨会娥
田村正则
关屋章
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National Institute of Advanced Industrial Science and Technology AIST
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National Institute of Advanced Industrial Science and Technology AIST
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • 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

Catalyst for fluorination
[technical field]
The present invention relates to catalyst for fluorination and use the preparation method of the fluorinated hydrocarbons of this catalyzer.
[background technology]
The halogen exchange metal fluoride catalysts is the catalyzer 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), reported the result who improves catalyst activity by the assistant metal that this catalyzer 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 damp atmosphere, its application is subjected to great restriction.J.C.S.Chem.Comm., put down in writing in 1973,815 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 gac and flooded SbCl 5Catalyzer as process catalyst.The gaseous fluoridizing method that JP 3,031 465 discloses in order to obtain HFC-245fa, HF and pentachloropropane to be reacted.The SbCl of this method working load on gac 5As process catalyst.The operability of catalyzer in practicality that these antimonic salts are loaded in the carbon compares SbF 5Height, but the existing problems of stability at high temperature.Use stibiated metal-salt 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 JP2002-334883) that obtains new fluorination catalyst by using HF.This catalyzer is excellent catalytic activity to be arranged and for SbF in halogen exchange reaction 5The improved catalyzer of characteristic (humidity corrosion and toxicity).SbF 5/ PAF is adapted in the organic synthesis using as the fixed bed catalyst of fluorizating agent or F/Cl exchange usefulness.
Present inventors have proposed to have 60m 2Porous Calcium Fluoride (Fluorspan) (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 chromium fluoride of this high surface area of/g (Porous Chromium fluoride) is scheme (patent documentation 1) (special Willing JP 2003-303078) (PCrF).
Yet these schemes consider to be still the catalyzer that can not meet the demands from the viewpoint for the metal load that further makes the fluoridation sensitization.
[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 catalyzer to use in the fluoridation of hydrogen fluoride as fluorizating agent, provides a kind of fluorination process that height is fluoridized active catalyzer and this catalyzer of use is provided that has.
[solving the measure that problem is used]
According to the invention provides catalyzer shown below and method.
(1) catalyst for fluorination is characterized in that, the antimony halogenide shown in the following general formula of load (1) on the porous support that Calcium Fluoride (Fluorspan) 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 chromic oxide and hydrogen fluoride made 2Antimony halogenide shown in the following general formula of load (1) on the porous support of/g surface-area.
[changing 5]
SbF nCl 5-n?????????????????????????????????(1)
(in the formula, n represents 0～5 number)
(3) catalyzer described in aforementioned (1), wherein this porous support is to have 15～100m 2The Calcium Fluoride (Fluorspan) of/g surface-area.
(4) any one described catalyzer in aforementioned (1)～(3), wherein the halid content of this antimony is 1～70 weight % in the catalyzer.
(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 catalyzer, as this catalyzer, uses any one described catalyzer in aforementioned (1)～(4).
(6) aforementioned (5) described method, wherein this halogen-containing hydrocarbon is the alkene of carbonatoms 1～6 or the halogenide 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 methylene dichloride.
(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 catalyzer, 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 catalyzer, use the halid catalyst for fluorination of antimony shown in the following general formula of load (1) on the porous support 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 methylene dichloride as this halogen-containing hydrocarbon, generates methylene fluoride 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 catalyzer that uses in the fluoridation of fluorine atom.This catalyzer has high reactivity and at high temperature also stable, is to be suitable as the catalyzer that commercial catalysts uses.
[preferred plan that carries out an invention]
Catalyzer of the present invention has the structure of the antimony fluoride shown in the following formula of load (1) in porous support.
[changing 7]
SbF nCl 5-n????????????????(1)
(in the formula, n represents 0～5 number)
This porous support is Calcium Fluoride (Fluorspan) or the porous support of magnesium fluoride formation or the porous support that is made by porous chromic oxide and hydrogen fluoride.
The porous support that Calcium Fluoride (Fluorspan) constitutes, its surface-area does not have particular restriction, preferably 15～100m 2/ g.The porous support that magnesium fluoride constitutes, its surface-area does not have particular restriction.
The porous support that porous chromic oxide and hydrogen fluoride make, its surface-area is 90～200m 2/ g, 150～190m preferably 2/ g.
These porous supports can be figure of tablet or particulate state, and its median size of granular occasion does not have particular restriction, normally 0.2～5mm, 0.5～3mm preferably.
Any porous support can contain ancillary component.Can enumerate metal oxide, metal chloride, other metal-salt etc. as ancillary component, its kind does not have particular restriction.The content of ancillary component is following, the 5 weight % or below the 5 weight % preferably of 30 weight % or 30 weight %.
The surface-area of porous support is the bigger the better.This porous support shows the effect of the antimony fluoride stabilization of the difficult operation of sening as an envoy to.
As porous support, preferably having average pore diameter is that 5～120 , preferred 20～50 , porosity are the carrier of the pore structure of 0.05～0.8cc/g, preferred 0.1～0.7cc/g.
The antimonic fluoride of aforementioned formula (1) expression that the present invention uses promotes composition as activity of such catalysts and works.Antimonic fluoride is with respect to the ratio of porous support, is 1～70 weight %, 5～50 weight % preferably in catalyzer.
Catalyzer of the present invention can be immersed on the porous support with the solution state that is dissolved in the tetracol phenixin equal solvent by making antimonic fluoride, and carries out drying and prepare.
In addition, catalyzer of the present invention also can make antimony chloride be immersed in the porous support with solution state, after the drying, hydrogen fluoride (HF) reaction is prepared the method that this antimony chloride is transformed into antimonic fluoride.
Catalyzer 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 halon 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 monomeric words of antimonic fluoride though be liquid, can be used with the form of fixed bed by catalyzer being carried out immobilization.In addition, catalyzer of the present invention is also stable under the high temperature more than 400 ℃ or 400 ℃.
When using catalyzer 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, temperature of reaction 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 catalyzer 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, temperature of reaction 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 catalyzer 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 temperature of reaction 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 catalyzer of the antimonic fluoride that contains aforementioned formula (1) expression on the porous support of porous aluminum fluoride, also can react equally aptly as main body.As such catalyzer, for example, can enumerate above-mentioned SbF 5/ PAF (special Willing JP2002-334883).
When using catalyzer of the present invention, carry out gas-phase reaction, can be transformed into methylene fluoride expeditiously by making methylene dichloride and HF.This occasion, HF and methylene dichloride (CH 2Cl 2) mol ratio be 1: 1～30: 1, be preferably 3: 1～10: 1.Temperature of reaction is 150～450 ℃, is preferably 200～350 ℃.
When using Preparation of Catalyst fluorinated hydrocarbons of the present invention, as the halon 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 carbonatoms of hydrocarbon is 1～12, is preferably 1～6.In the halon, this hydrocarbon can be the aliphatic hydrocarbon of carbonatoms 1～8 or the annular aliphatic hydrocarbon of carbonatoms 5～8, the aromatic hydrocarbons of carbonatoms 6-12.When making these halons and HF carry out gas-phase reaction, can suitably select for use this halon to form the temperature of reaction of gas phase, in addition, also can suitably select for use and the corresponding HF/ halon of desired fluorochemical 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 sheets.
Embodiment 1
(in the porous chromium 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 chromium 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) handle at 100 ℃, the concentration of elevated temperature and AHF uses pure AHF to handle at 200 ℃ at last again.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 up to about 500.C is still stable.
Embodiment 2
(use SbF 5The 1-chloro-3,3 of/PCrF catalyzer, 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.Resultant of reaction 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 catalyzer C similarly to Example 1.
Embodiment 6
Among the embodiment 2, except using catalyzer C alternative catalysts A, similarly react, the results are shown in aftermentioned table 1.
Comparative example 1
Among the embodiment 2, except using porous chromium 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 catalyzer that use contains antimonic salt can obtain higher yield than the catalyzer that does not contain antimonic salt under lower temperature of reaction.
[table 1]
Sequence number SbF in the catalyzer 5(wt％) Temperature of reaction (℃) Yield (%)
Resultant 1 Resultant 2
Embodiment 2 ????50 ????305 ????89.8 ????9.0
Embodiment 4 ????35 ????305 ????330 ????45.3 ????80.0 ????6.4 ????11.3
Embodiment 6 ????20 ????305 ????330 ????50.0 ????74.6 ????7.1 ????10.6
Comparative example 1 ????0 ????320 ????340 ????34.5 ????56.1 ????6.9 ????5.6
Resultant 1: trans-CF 3CH=CHCl
Resultant 2: cis-CF 3CH=CHCl
Embodiment 7
(use SbF 5/ PCrF catalyzer synthesizes 1,1,1,3, the 3-pentafluoropropane)
Among the embodiment 2, except the catalyzer C that uses embodiment 5 expressions as catalyzer, use 1-chloro-3,3 simultaneously, 3-trifluoro propene (CTFP) is as beyond the raw material halon, other similarly react.But the temperature of reaction 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) transformation efficiency is 70.2%.
Embodiment 8
(use SbF 3/ PCrF catalyzer synthesizes 3,3, the 3-trifluoro propene)
Among the embodiment 2, except using catalyst A as catalyzer, 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 catalyzer synthesizes methylene fluoride)
Except the catalyst A of using embodiment 1 to make, use methylene dichloride 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]
Temperature of reaction (℃) Yield (%)
????CH 2F 2 ???CH 2C1F
????250 ????15.8 ????20.5
????275 ????68.6 ????12.9
????300 ????70.4 ????13.4
????330 ????68.6 ????14.6
????360 ????68.5 ????15.4
Embodiment 10
Among the embodiment 9, except using the catalyst B shown in the embodiment 3, other similarly react as catalyzer.This reaction result is shown in table 3.
[table 3]
Temperature of reaction (℃) Yield (%)
????CH 2F 2 ????CH 2ClF
????250 ????34.6 ????19.8
????276 ????48.1 ????15.4
????304 ????45.0 ????16.6
????334 ????44.5 ????17.6
????360 ????44.2 ????18.2
Embodiment 11
(preparation contains SbF in porous Calcium Fluoride (Fluorspan) (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 catalyzer 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 catalyzer synthesizes 1,1,1,3, the 3-pentafluoropropane)
Among the embodiment 7, except the catalyzer D that makes as catalyzer use embodiment 11, other similarly react.Reaction result is shown in table 4.
[table 4]
????No. Temperature of reaction (℃) Transformation efficiency % The selectivity .% of resultant
Resultant 1 Resultant 2 Resultant 3
????1 ????80 ????40.7 ????31.4 ????61.2 ????7.4
????2 ????100 ????47.6 ????13.3 ????80.7 ????6.0
????3 ????125 ????32.3 ????10.5 ????81.1 ????8.4
????4 ????145 ????41.8 ????13.8 ????79.7 ????6.5
Resultant 1: trans-CF 3CH=CHF
Resultant 2:CF 3CH 2CF 2
Resultant 3: cis-CF 3CH=CHCl
Embodiment 13
(use SbF 5/ PCF catalyzer synthesizes 1-chloro-3,3,3-trifluoro propene)
Among the embodiment 2, except the catalyzer D alternative catalysts A that use embodiment 11 makes, other similarly react.The results are shown in table 5.
[table 5]
????No. Temperature of reaction (℃) Resultant 1 yield (%)
????1 ????190 ????49.6
????2 ????220 ????68.2
????3 ????250 ????77.4
????4 ????280 ????76.8
Resultant 1:CF 3CH=CHCl
Embodiment 14
(contain SbF in the preparation porous magnesium fluoride 5Catalyst S bF 5/ PMgF)
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 catalyzer 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 catalyzer synthesizes 1-chloro-3,3,3-trifluoro propene)
Among the embodiment 2, except use embodiment 14 made catalyzer E alternative catalysts A, other similarly reacted.The results are shown in table 6.
[table 6]
????No. Temperature of reaction (℃) Resultant 1 yield (%)
????1 ????190 ????67.1
????2 ????220 ????79.2
????3 ????250 ????80.5
????4 ????280 ????79.7
Resultant 1:CF 3CH=CHCl
Embodiment 16
(use SbF 5/ PMgF catalyzer synthesizes 1,1,1,3, the 3-pentafluoropropane)
Among the embodiment 7, except the catalyzer E that makes as catalyzer use embodiment 14, other similarly react.The results are shown in table 7.
[table 7]
????No. Temperature of reaction (℃) Transformation efficiency % The selectivity .% of resultant
Resultant 1 Resultant 2 Resultant 3
????1 ????80 ????46.1 ????19.2 ????74.8 ????6.0
????2 ????100 ????58.7 ????11.8 ????83.8 ????4.4
????3 ????120 ????63.2 ????10.1 ????86.5 ????3.4
Resultant 1: trans-CF 3CH=CHF
Resultant 2:CF 3CH 2CF 2
Resultant 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 catalyzer 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 catalyzer synthesizes 1,1,1,3, the 3-pentafluoropropane)
Among the embodiment 7, except using catalyzer F that embodiment 17 makes as the catalyzer, other similarly react.The results are shown in table 8.
[table 8]
?????No. Temperature of reaction (℃) Transformation efficiency % The selectivity .% of resultant
Resultant 1 Resultant 2 Resultant 3
????1 ????300 ????42.5 ???39.6 ????45.1 ????15.1
????2 ????350 ????72.5 ???60.8 ????31.0 ????4.5
Resultant 1: trans-CF 3CH=CHF
Resultant 2:CF 3CH 2CF 2
Resultant 3: cis-CF 3CH=CHCl
Comparative example 2
(contain SbF in the gac 5Catalyst S bF 5The thermostability of/C)
Except using gac (usage quantity 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 metal-salt 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 halogenide of the following general formula of load (1) expression on the porous support of Calcium Fluoride (Fluorspan) or magnesium fluoride formation:
[changing 1]
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 chromic oxide and hydrogen fluoride 2Antimony halogenide shown in the following general formula of load (1) on the porous support of/g surface-area:
[changing 2]
SbF nCl 5-n???????????????????????????????(1)
(in the formula, n represents 0～5 number).
3. the described catalyzer of claim 1, wherein this porous support is to have 15～100m 2The Calcium Fluoride (Fluorspan) of/g surface-area.
4. each described catalyzer in the claim 1～3, wherein the halid content of this antimony is 1～70 weight % in the catalyzer.
5. the preparation method of a fluorinated hydrocarbons is characterized in that, in the presence of catalyzer, uses hydrogen fluoride that the hydrocarbon of the halogen beyond fluorine-containing is carried out in the method for gas phase fluorination, uses each described catalyzer in the claim 1～4 as this catalyzer.
6. the described method of claim 5, wherein this halogen-containing hydrocarbon is the alkene of carbonatoms 1～6 or the halogenide 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 methylene dichloride.
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 catalyzer, 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 catalyzer, uses the halid catalyst for fluorination of antimony shown in the following general formula of load (1) on the porous support that the porous aluminum fluoride constitutes:
[changing 3]
SbF nCl 5-n????????????????????????????(1)
(in the formula, n represents 0～5 number).
12. the described method of claim 5 is wherein used methylene dichloride as this halogen-containing hydrocarbon, generates methylene fluoride and/or chlorofluoromethane.
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