CN107126965A

CN107126965A - High activity tungsten-based catalyst

Info

Publication number: CN107126965A
Application number: CN201710253918.0A
Authority: CN
Inventors: 权恒道; 张呈平; 张小玲; 庆飞要
Original assignee: BEIJING YUJI TECHNOLOGY DEVELOPMENT Co; Beijing Institute of Technology BIT
Current assignee: Quanzhou Yuji New Material Technology Co.,Ltd.; Beijing Institute of Technology BIT
Priority date: 2017-04-18
Filing date: 2017-04-18
Publication date: 2017-09-05
Anticipated expiration: 2037-04-18
Also published as: CN107126965B

Abstract

The present invention discloses " high activity tungsten-based catalyst ", belongs to the field of chemical synthesis.High activity tungsten-based catalyst of the present invention is made up of tungsten ion and auxiliary agent, and the weight/mass percentage composition of tungsten ion and auxiliary agent is followed successively by 60%~100% and 0~40%.The precursor consumption fluorine gas or tungsten hexafluoride theoretical amount that the fluorine gas or tungsten hexafluoride total amount that the present invention is passed through in activation stage are equal to tungsten ion consume fluorine gas or tungsten hexafluoride theoretical amount plus metallic element auxiliary agent, tungsten ion is reduced into state of the control in trivalent, tetravalence or pentavalent as far as possible because sexavalence tungsten is easily lost in, therefore when calculating fluorine gas consumption.The tungsten-based catalyst temperature in use of the present invention is high, catalytic activity is high, service life is long, is mainly used in gas phase catalysis alkenyl halide generation exchange chloride for fluoride under high temperature and prepares Fluorine containing olefine.

Description

High activity tungsten-based catalyst

Technical field

The present invention relates to a kind of tungsten-based catalyst, occur fluoro- chlorine more particularly, to gas phase catalysis alkenyl halide under high temperature and hand over Change reaction and prepare Fluorine containing olefine.

Background technology

In order to fulfil the Montreal Agreement for the ozone layer that is intended to preserve our planet, the hydrogen of zero odp value has been released in countries in the world Fluorohydrocarbon (HFCs) and HF hydrocarbon (HFOs), so as to eliminate CFC (CFCs) and hydrogen fluorochlorohydrocarbon that ODP values are not zero (HCFCs).At present, HFCs and HFOs have been widely used as refrigerant, cleaning agent, foaming agent, extinguishing chemical, etching agent etc..

At present, industrial production HFCs or HFOs uses the fluoro- chlorine exchange reaction of gas phase catalysis of halogenated organic matters mostly Method, the method has the advantages that technique is simple, is easy to continuous large-scale production, safe operation.Urged in the gas phase of halogenated organic matters It is fluoro- chlorine exchange catalysts to change played the role of a nucleus in fluoro- chlorine exchange reaction.At present, common fluoro- chlorine exchange catalysts are chromium Base catalyst, its main active component is chromium.

Du pont company reports the element modified chromium-based catalysts of Al in patent US4465786, for being catalyzed system Standby trifluoro propene.

It is that raw material exists that du pont company reports monochloromonofluoromethane with tetrafluoropropene in patent US20100051853 Reacted under aluminum halide effect and obtain 1- chloro- 2,2,3,3,3- pentafluoropropanes (HCFC-235cb), then HCFC-235cb exists Cr₂O₃In the presence of occur dehydrofluorination and obtain E/Z-1- chloro- 2,3,3,3- tetrafluoropropenes (E/Z-HCFC-1224yd), finally Under the element modified chromium-based catalysts effects of Zn with hydrogen fluoride the fluoro- chlorine exchange reaction of gas phase occurs for E/Z-HCFC-1224yd, obtains To E/Z-1,1,1,2,3- pentafluoropropene (E/Z-HFC-1225ye), trans and cis-configuration content is respectively 95%, 5%.

The chromium-based catalysts that Imperial Chemical Industries of Britain report the modification of Zn elements in patent US5763704 are used Difluoromethane (HFC-32) is prepared in catalysis.

Imperial Chemical Industries of Britain report the chromium that Zn elements and Ni elements are modified jointly in patent US5763707 Base catalyst, which is used to be catalyzed, prepares HFC-125.

French Ai Erfu Atochem (FR) Cedex 22, 94091 Paris La Defense, France reports chromium-based catalysts catalysis HCO-1233za in patent US5811603 Prepare 1- chloro-3,3,3 ,-trifluoropropenes (HCFO-1233zd), 1,3,3,3- tetrafluoropropenes (HFO-1234ze) and 1,1,1,3,3- Pentafluoropropane (HFC-245fa).

French Ai Erfu Atochem (FR) Cedex 22, 94091 Paris La Defense, France reports what Al elements and Ni elements were modified jointly in patent US6184172 Chromium-based catalysts are used to be catalyzed 1- chloro- 3, and 3,3- HFC-143as (HCFC-133a) prepare 1,1,1,3- HFC-134a (HFC- 134a)。

Daikin company reports a kind of specific surface area S=170~300m in patent US6300531²/ g chromium base Catalyst, occurs fluoro- chlorine exchange reaction synthesis HFC-134a, it can also be used to be catalyzed four chloroethenes for being catalyzed 1,1,1- trichloroethanes Alkene occurs exchange chloride for fluoride and obtains pentafluoroethane (HFC-125).

Daikin company reports chromium-based catalysts catalysis 2- chloro- 3,3,3- trifluoros in patent US20130217928 Propylene (HCFO-1233xf) occurs the fluoro- chlorine exchange reaction of gas phase with HF and obtains 2,3,3,3- tetrafluoropropenes (HFO-1234yf).

Japanese Central glass companies report chromium-based catalysts in patent US5905174 to be used to be catalyzed pentachloro- third Ketone prepares the fluoro- 3,3- dichloroacetones of 1,1,1- tri-.

Nippon Zeon Co., Ltd. and Central Glass CO., Ltd. report a kind of fluoro- chlorine exchange in patent CN1192995C and urged Agent, using infusion process by Cr (NO₃)₃It is carried on activated carbon, obtains, at 330 DEG C, use through drying, roasting, hydrogen fluoride activation In catalysis cyclo-CF₂CF₂CF₂CCl=CCl occurs fluoro- chlorine exchange reaction with hydrogen fluoride and prepares cyclo-CF₂CF₂CF₂CF= CCl, its catalytic activity is very low, and conversion ratio is only 26%, and selectivity is 91%.

Chinese Co., Ltd of Jinzhu Modern Chemical Co., Ltd., Xi'an is reported in patent CN1408476 in Mn, Co or Zn A kind of another element in element, and Mg or Ni, totally two kinds of element modified chromium-based catalysts be used to be catalyzed trichloro ethylene, Through intermediate HCFC-133a, occurs the fluoro- chlorine exchange reaction synthesis HFC-134a of two step gas phases.

Chinese Sinochem Modern Environmental Protection Chemicals (Xi'an) Co., Ltd. reports rare earth element in patent CN102580767A Modified chromium-based catalysts, which are used to being catalyzed HCFC-133a and HF the generation fluoro- exchange reaction of gas phase, synthesizes HFC-134a.

Chinese Xi'an Inst. of Modern Chemistry reports cobalt and magnesium-modified chrome catalysts in patent CN1145275, carries Body is aluminum fluoride, for being catalyzed trichloro ethylene, through intermediate HCFC-133a, occurs the fluoro- chlorine exchange reaction synthesis of two step gas phases HFC-134a。

Chromium-based catalysts once caused grinding for countries in the world scientist due to the advantage that its raw material is easy to get, activity is higher Study carefully interest.But going deep into research, it has been found that, chrome catalysts still have that temperature in use is low, catalytic activity is low, use Short life, the defect for being difficult to recycling, and more importantly chromium has toxicity, can be special to artificial into great damage It is not that high valence chrome has strong carcinogenicity.Research thinks that Cr VI is higher than trivalent chromium toxicity 100 times, and be easily absorbed by the body and Accumulation in vivo, the speed that it is metabolized and is eliminated is slow.Under certain condition, trivalent chromium and Cr VI can be converted mutually.Six Valency chromium can cause the mankind to suffer from respiratory cancer by confirmation.Cr VI once absorbed by intracellular ubiquitous reducing agent and It is metabolized, then the cell of the digestive system of the mankind can then form the cancer of the DNA damage of chromium promotion.Cr VI is by the World Health Organization IARC (IARC) is classified as " human carcinogen ".

The content of the invention

To be solved by this invention is the non-chromium-based catalysts that always search for of people as fluoro- chlorine exchange catalysts.Hair A kind of bright safety and environmental protection of catalyst offer is harmless, catalytic activity is high, non-chrome catalysts-tungsten-based catalyst of service life length. This invention has milestone effect in the fluoro- chlorine exchange reaction of gas phase catalysis in terms of finding non-chromium-based catalysts.

Another technical problem to be solved by this invention is to provide a kind of preparation side of above-mentioned high activity tungsten-based catalyst Method.

The present invention provides a kind of high activity tungsten-based catalyst, and the high activity tungsten-based catalyst is by tungsten ion and auxiliary agent group The one or several kinds in trivalent tungsten ion, tetravalence tungsten ion, pentavalent tungsten ion into, tungsten ion, auxiliary agent be Al, Mg, Ni, Co, Ti、Zr、V、Fe、Zn、In、Cu、Ag、Cd、Hg、Ga、Sn、Pb、Mn、Ba、Re、Sc、Sr、Ru、Nb、Ta、Ca、Ce、Sb、Tl、Hf At least one of or it is several, and tungsten ion and auxiliary agent quality percentage composition be 60%~100% and 0%~40%.

The precursor of wherein tungsten ion is at least one in tungsten simple substance, three two tungsten of oxidation, tungsten dioxide or tungsten pentoxide Kind or it is several, the precursor of auxiliary agent be in the oxide of corresponding additive, hydroxide, nitrate, acetate or carbonate extremely Few one or several kinds.

The preferred tungsten simple substance of precursor of tungsten ion of the present invention.

The preferred manganese of auxiliary agent or scandium of the present invention, the preferred manganese nitrate of precursor or scandium nitrate or nitric acid rhenium of the auxiliary agent.

The weight/mass percentage composition of tungsten ion and assistant metal element is 80%~95% and 5~20%.

The preferred tungsten simple substance of precursor and the mixture of manganese nitrate of the high activity tungsten-based catalyst of the present invention, wherein, tungsten ion Mass percent with manganese element is 90% and 10%.

The preferred tungsten simple substance of precursor and the mixture of scandium nitrate of the high activity tungsten-based catalyst of the present invention, wherein, tungsten ion Mass percent with scandium element is 90% and 10%.

The preferred tungsten simple substance of precursor and the mixture of nitric acid rhenium of the high activity tungsten-based catalyst of the present invention, wherein, tungsten ion Mass percent composition with rhenium element is 90% and 10%.

High activity tungsten-based catalyst of the present invention is prepared by the following procedure method and obtained：

(1) according to the mass percent of tungsten ion and auxiliary agent, the precursor of the precursor of tungsten ion and auxiliary agent is well mixed, pressed Type is made, catalyst precarsor is obtained；

(2) catalyst precarsor for obtaining step (1), carries out roasting 6~15 in 300 DEG C~500 DEG C under nitrogen atmosphere Hour；

(3) product of roasting for obtaining step (2), in 600 DEG C~800 DEG C, is first vacuumized, then in confined conditions, Activated 6~15 hours in fluorine gas, high activity tungsten-based catalyst is made, the precursor that the total amount that the fluorine gas is passed through is equal to tungsten ion disappears Consume fluorine gas theoretical amount and consume fluorine gas theoretical amount summation plus metallic element auxiliary agent；The precursor consumption fluorine gas theoretical amount of the tungsten ion The fluorine gas theoretical amount consumed for needed for tungsten ion in the precursor more than tungsten ion is reduced into tungsten trifluoride, and less than before tungsten ion Tungsten ion is reduced into the fluorine gas theoretical amount of consumption needed for five tungsten fluorides in body.

Or the product of roasting for obtaining step (2), it is in confined conditions, living in tungsten hexafluoride in 600 DEG C~800 DEG C Change 6~15 hours, high activity tungsten-based catalyst is made, the total amount that the tungsten hexafluoride is passed through is equal to the precursor consumption six of tungsten ion Tungsten fluoride theoretical amount consumes tungsten hexafluoride theoretical amount summation plus metallic element auxiliary agent；The precursor consumption of the tungsten ion is lithium The tungsten hexafluoride theoretical amount that tungsten theoretical amount is consumed for needed for tungsten ion in the precursor more than tungsten ion is reduced into tungsten trifluoride, and it is small Tungsten ion is reduced into the tungsten hexafluoride theoretical amount consumed needed for five tungsten fluorides in the precursor of tungsten ion.

Tungsten hexafluoride of the present invention can be prepared by following methods：

(1) in 20 DEG C~150 DEG C of temperature, tungsten simple substance reacts with fluorine gas and obtains tungsten hexafluoride；

(2) or in 300 DEG C~450 DEG C of temperature, tungstic acid reacts with fluorine gas and obtains tungsten hexafluoride and oxygen.

The precursor of the tungsten ion of the present invention is tungsten simple substance, three aoxidize in two tungsten, tungsten dioxide or tungsten pentoxide extremely Few one or several kinds, the precursor of auxiliary agent be in the oxide of metal, hydroxide, nitrate, acetate or carbonate extremely Few one or several kinds.

The precursor of the tungsten ion is tungsten simple substance, and the fluorine gas throughput is more than or equal to tungsten element material consumption fluorine gas reason Stoichiometric and 3/2 times of the ratio of the amount of tungsten element material, and less than or equal to 5/2 times, residual fluorine is carried out using dry soda lime Absorb, high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is three two tungsten of oxidation, and the fluorine gas throughput is to disappear more than or equal to three two tungsten materials of oxidation 3 times of the ratio of fluorine gas theoretical amount and the amount of three two tungsten materials of oxidation is consumed, and less than or equal to 5 times, residual fluorine uses dry alkali Lime is absorbed, and high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is tungsten dioxide, and the fluorine gas throughput is the precursor consumption fluorine more than or equal to tungsten ion 2 times of the ratio of gas theoretical amount and the amount of tungsten dioxide material, and less than or equal to 5/2 times, residual fluorine uses dry soda lime Absorbed, high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is tungsten pentoxide, and the fluorine gas throughput is the precursor consumption more than or equal to tungsten ion The ratio of fluorine gas theoretical amount and the amount of tungsten pentoxide material is 5 times, and residual fluorine is absorbed using dry soda lime, is made Obtain high activity tungsten-based catalyst；

The precursor of the tungsten ion is tungsten simple substance, and the tungsten hexafluoride throughput is the precursor consumption more than or equal to tungsten ion 1 times of the ratio of tungsten hexafluoride theoretical amount and the amount of tungsten element material, and less than or equal to 5 times, remaining tungsten hexafluoride uses drying Soda lime is absorbed, and high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is three two tungsten of oxidation, and the tungsten hexafluoride throughput is the precursor more than or equal to tungsten ion 2 times of the ratio of tungsten hexafluoride theoretical amount and the amount of three two tungsten materials of oxidation is consumed, and less than or equal to 10 times, remaining tungsten hexafluoride makes Absorbed with dry soda lime, high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is tungsten dioxide, and the tungsten hexafluoride throughput disappears for the precursor more than or equal to tungsten ion 2 times of the ratio of tungsten hexafluoride theoretical amount and the amount of tungsten dioxide material is consumed, and less than or equal to 5 times, remaining tungsten hexafluoride uses dry Dry soda lime is absorbed, and high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is tungsten pentoxide, and the tungsten hexafluoride throughput is the precursor more than or equal to tungsten ion 10 times of the ratio of tungsten hexafluoride theoretical amount and the amount of tungsten pentoxide material is consumed, remaining tungsten hexafluoride uses dry soda lime Absorbed, high activity tungsten-based catalyst is made.

High activity tungsten-based catalyst of the present invention, the preferred tungsten simple substance of precursor of tungsten ion, the precursor of the auxiliary agent is excellent Selecting the compound containing manganese, scandium or rhenium, the weight/mass percentage composition of tungsten ion and assistant metal element is followed successively by 80%~95% and 5~ 20%.

The preferred manganese nitrate of precursor, scandium nitrate or the nitric acid rhenium of the auxiliary agent.

The preferred tungsten simple substance of precursor and the mixture of nitric acid rhenium of the high activity tungsten-based catalyst of the present invention, wherein, tungsten ion Mass percent with rhenium element is 90% and 10%.

The high activity tungsten-based catalyst is prepared by the following procedure method and obtained：

(1) according to the mass percent of tungsten ion and auxiliary agent, the precursor of tungsten ion and auxiliary agent is well mixed, is pressed into Type, obtains catalyst precarsor；

The precursor of high activity tungsten-based catalyst of the present invention selects tungsten simple substance, the preferred manganese of auxiliary agent, scandium or rhenium, and the precursor of auxiliary agent is excellent Select oxide, hydroxide, nitrate, acetate or the carbonate of corresponding additive.

Fluoro- chlorine exchange reaction preparation occurs above-mentioned high activity tungsten-based catalyst for gas phase catalysis alkenyl halide under the high temperature conditions Application in Fluorine containing olefine.

The alkenyl halide is cyclo-CF₂CF₂CF₂CCl=CCl, prepares cyclo-CF₂CF₂CF₂CF=CCl；

Or the alkenyl halide is 2- chloro-3,3,3 ,-trifluoropropenes (being abbreviated as HCFO-1233xf), prepares 2,3,3,3- Tetrafluoropropene (is abbreviated as HFO-1234yf)；

Or the alkenyl halide is E/Z-1- chloro- 2,3,3,3- tetrafluoropropenes prepare E/Z-1,2,3,3,3- five fluorine third Alkene (is abbreviated as E/Z-HFO-1225ye)；

Or the alkenyl halide is E-1- chloro-3,3,3 ,-trifluoropropenes, prepares E/Z-1,3,3,3- tetrafluoropropenes (are write a Chinese character in simplified form For E/Z-HFO-1234ze)；

Or the alkenyl halide is Z-1- chloro-3,3,3 ,-trifluoropropenes, prepares E/Z-HFO-1234ze.

The precursor consumption fluorine gas theoretical amount that the fluorine gas total amount or tungsten hexafluoride that the present invention is passed through are equal to tungsten adds metallic element Auxiliary agent consumes the theoretical amount of fluorine gas or tungsten hexafluoride, because tungsten hexafluoride is easily lost in, therefore is calculating fluorine gas or tungsten hexafluoride Tungsten ion is reduced into state of the control in trivalent, tetravalence or pentavalent as far as possible during consumption.

The present invention prepares catalyst using blending method, is constituted according to the percentage of tungsten ion and auxiliary agent, before tungsten ion The precursor of body and auxiliary agent is mixed well mixed, compressing, catalyst precarsor is made, when precursor is through high-temperature roasting, before auxiliary agent Body (hydroxide, nitrate, acetate or carbonate) occurs pyrolysis and obtains the oxide of auxiliary agent, and the precursor base of tungsten ion Do not react, still exist in original valent state form in sheet；When precursor enters the activation rank of fluorine gas or tungsten hexafluoride Section, detailed process is as follows：

(1) when the precursor of tungsten ion is tungsten simple substance, the ratio between amount of material of fluorine gas and tungsten ion can be controlled, to realize tungsten Ion Quantitative yield works as F into the fluoride of tungsten₂/ W=3/2 (mol ratio), occurs following react：2W+3F₂→2WF₃；Work as F₂/W =5/2 (mol ratio), occurs following react：2W+5F₂→2WF₅；The fluorine gas of tungsten ion consumption is controlled (to be deducted from fluorine gas total amount The fluorine gas amount of metallic element auxiliary agent consumption) it is more than or equal to 3/2 with the ratio between the amount of tungsten simple substance, and less than or equal to 5/2；

(2) when the precursor of tungsten ion is three two tungsten of oxidation, the ratio between amount of material of fluorine gas and tungsten ion can be controlled, comes real Existing tungsten ion Quantitative yield works as F into the fluoride of tungsten₂/W₂O₃=3/2 (mol ratio), occurs following react：W₂O₃+3F₂→2WF₃ +3O₂；Work as F₂/W₂O₃=5 (mol ratios), occur following react：W₂O₃+5F₂→2WF₅+3O₂；Control the fluorine gas of tungsten ion consumption The ratio between (the fluorine gas amount that the consumption of metallic element auxiliary agent is deducted from fluorine gas total amount) and the amounts of three two tungsten materials of oxidation are more than or equal to 3, And less than or equal to 5；

(3) when the precursor of tungsten ion is tungsten dioxide, the ratio between amount of material of fluorine gas and tungsten ion can be controlled, to realize Tungsten ion Quantitative yield works as F into the fluoride of tungsten₂/WO₂=2 (mol ratios), occur following react：WO₂+2F₂→2WF₄+O₂；When F₂/WO₂=5/2 (mol ratio), occurs following react：2WO₂+5F₂→2WF₅+2O₂；The fluorine gas of tungsten ion consumption is controlled (from fluorine gas The fluorine gas amount of metallic element auxiliary agent consumption is deducted in total amount) it is more than or equal to 2 with the ratio between the amount of tungsten dioxide material, and be less than or equal to 5/2；

(4) when the precursor of tungsten ion is tungsten pentoxide, the ratio between amount of material of fluorine gas and tungsten ion can be controlled, comes real Existing tungsten ion Quantitative yield works as F into the fluoride of tungsten₂/W₂O₅=5 (mol ratios), occur following react：W₂O₅+5F₂→2WF₅+ 5O₂；Control fluorine gas (the fluorine gas amount that the consumption of metallic element auxiliary agent is deducted from fluorine gas total amount) and five oxidations two of tungsten ion consumption The ratio between amount of tungsten material is equal to 5.

(5) when the precursor of tungsten ion is tungsten simple substance, the ratio between amount of material of tungsten hexafluoride and tungsten ion can be controlled, comes real Existing tungsten ion Quantitative yield works as WF into the fluoride of tungsten₆/ W=1 (mol ratio), occurs following react：W+WF₆→2WF₃；When WF₆/ W=5 (mol ratio), occurs following react：W+5WF₆→6WF₅；The tungsten hexafluoride of tungsten ion consumption is controlled (from tungsten hexafluoride The tungsten hexafluoride amount of metallic element auxiliary agent consumption is deducted in total amount) it is more than or equal to 1 with the ratio between the amount of tungsten simple substance, and less than or equal to 5；

(6) when the precursor of tungsten ion is three two tungsten of oxidation, the ratio between amount of material of tungsten hexafluoride and tungsten ion can be controlled, To realize that tungsten ion Quantitative yield, into the fluoride of tungsten, works as WF₆/W₂O₃=2 (mol ratios), occur following react：W₂O₃+2WF₆→ 4WF₃+3/2O₂；Work as WF₆/W₂O₃=10 (mol ratios), occur following react：W₂O₃+10WF₆→12WF₅+3/2O₂；Control tungsten from Tungsten hexafluoride (the tungsten hexafluoride amount that the consumption of metallic element auxiliary agent is deducted from tungsten hexafluoride total amount) and three oxidations two of son consumption The ratio between amount of tungsten is more than or equal to 2, and less than or equal to 10；

(7) when the precursor of tungsten ion is tungsten dioxide, the ratio between amount of material of tungsten hexafluoride and tungsten ion can be controlled, is come Realize that tungsten ion Quantitative yield, into the fluoride of tungsten, works as WF₆/WO₂=2 (mol ratios), occur following react：WO₂+2WF₆→3WF₄ +O₂；Work as WF₆/WO₂=5/2 (mol ratio), occurs following react：WO₂+5WF₆→6WF₅+O₂；Control the hexafluoro of tungsten ion consumption Change the ratio between amount of tungsten (the tungsten hexafluoride amount that the consumption of metallic element auxiliary agent is deducted from tungsten hexafluoride total amount) and tungsten dioxide material More than or equal to 2, and less than or equal to 5；

(8) when the precursor of tungsten ion is tungsten pentoxide, the ratio between amount of material of tungsten hexafluoride and tungsten ion can be controlled, To realize that tungsten ion Quantitative yield, into the fluoride of tungsten, works as WF₆/W₂O₅=5 (mol ratios), occur following react：W₂O₅+10WF₆ →12WF₅+5/2O₂；The tungsten hexafluoride of tungsten ion consumption is controlled (to deduct the consumption of metallic element auxiliary agent from tungsten hexafluoride total amount Tungsten hexafluoride amount) it is equal to 10 with the ratio between the amount of tungsten pentoxide material.

In above-mentioned fluorine gas or the activation stage of tungsten hexafluoride, the tungsten of lower valency can be converted into the tungsten ion of high-valence state, Trivalent tungsten ion, tetravalence tungsten ion, pentavalent tungsten ion and sexavalence tungsten ion are such as converted into by zero-valent state, because sexavalence tungsten ion holds It is easy to run off, therefore, it can control F₂Or the consumption of tungsten hexafluoride, it is trivalent tungsten ion, tetravalence by low price chromium ion Quantitative yield Tungsten ion or pentavalent tungsten ion.Due to a large amount of presence of trivalent tungsten ion, tetravalence tungsten ion or pentavalent tungsten ion, tungsten base is caused to be urged Agent has strong catalytic activity, along with other metallic elements are as auxiliary agent, enhances the stability of tungsten-based catalyst.Entirely Effect sees that not only temperature in use is high for the tungsten-based catalyst prepared by such scheme, and catalytic activity is high, service life It is long.

The high activity tungsten-based catalyst of the present invention is applied to high temperature gas phase catalysis alkenyl halide and occurs fluoro- chlorine exchange reaction system Standby Fluorine containing olefine.Wherein, starting halo alkene can contain fluorine atom, can also not contain fluorine atom, but must contain and remove Fluorine atom and the one or several kinds in outer other halogen atoms such as chlorine atom or bromine atoms or iodine atom.For example：cyclo- CF₂CF₂CF₂CCl=CCl gas phase catalytic fluorinations prepare cyclo-CF₂CF₂CF₂(the letter of CF=CCl, 2- chloro-3,3,3 ,-trifluoropropene It is written as HCFO-1233xf) gas phase catalytic fluorination 2,3,3,3- tetrafluoropropenes (being abbreviated as HFO-1234yf) of preparation, E/Z-1- is chloro- 2,3,3,3- tetrafluoropropenes (being abbreviated as E/Z-HCFO-1224yd) gas phase catalytic fluorination prepares E/Z-1,2,3,3,3- pentafluoropropenes (being abbreviated as E/Z-HFO-1225ye), E-1- chloro-3,3,3 ,-trifluoropropenes gas phase catalytic fluorination prepares E/Z-1,3,3,3- tetrafluoros Propylene (is abbreviated as E/Z-HFO-1234ze), and Z-1- chloro-3,3,3 ,-trifluoropropenes gas phase catalytic fluorination prepares E/Z-HFO- 1234ze etc..

The present invention compared with prior art, has the advantage that as follows：

(1) so far, sufficient information not yet determines whether that suction, oral or skin touch tungsten or tungsten his thing meeting Cause the generation of human cancer.U.S. sanitary and crowd service department (the Department of Health and Human Services, DHHS), IARC (the International Agency for Research on Cancer, IARC) or Environmental Protection Agency (the Environmental Protection Agency, U.S.EPA) is all still Tungsten is not classified as with carcinogenicity.Therefore, compared with chromium-based catalysts, tungsten-based catalyst has safe and environment-friendly, harmless spy Point.

(2) tungsten-based catalyst is when by tungsten hexafluoride or fluorine gas activation, and the precursor of tungsten ion can be with fluorine gas or tungsten hexafluoride The one or several kinds in tungsten trifluoride, tetrafluoride tungsten or five tungsten fluorides are generated, cause tungsten-based catalyst that there is stronger catalysis to live Property, and tungsten-based catalyst is modified by metallic element, substantially increase the stability of tungsten-based catalyst.

(3) tungsten-based catalyst of the invention is applied to the fluoro- chlorine exchange reaction system of gas phase catalysis alkenyl halide generation under high temperature Standby Fluorine containing olefine, temperature in use is up to 450 DEG C, hence it is evident that more much higher than 330 DEG C of the prior art.

Embodiment

Below by embodiment, the present invention is described in more detail, but is not limited to given example.

Analytical instrument：Shimadzu GC-2010, chromatographic column is DB-VRX capillary column (i.d.0.32mm； length 30m；J&W Scientific Inc.).

GC analysis methods：Reaction product takes gaseous sample to carry out GC analyses after washing, alkali cleaning and drying.Detector temperature 250 DEG C of degree, 250 DEG C of temperature of vaporization chamber, 40 DEG C of post initial temperature is kept for 10 minutes, and 15 DEG C/min is warming up to 230 DEG C, is kept for 8 minutes.

The preparation method of tungsten hexafluoride：In 20 DEG C~150 DEG C of temperature, tungsten simple substance reacts with fluorine gas obtains lithium Tungsten；Or in 300 DEG C~450 DEG C of temperature, tungstic acid reacts with fluorine gas and obtains tungsten hexafluoride and oxygen.

Embodiment 1

It is 90% and 10% according to the percentage composition of tungsten ion and manganese element, tungsten simple substance is uniformly mixed with manganese nitrate, Compression molding, is made catalyst precarsor, and catalyst precarsor 10mL is loaded into 1/2 inch of internal diameter, long 30cm Monel material Tubular reactor, is passed through nitrogen and is calcined 8 hours at 450 DEG C, and nitrogen air speed is 200h^-1, it is cooled to 300 DEG C, it is then that tubular type is anti- Answer device closed, first vacuumize, then pass to fluorine gas, fluorine gas throughput be more than or equal to tungsten element material consumption fluorine gas theoretical amount with 3/2 times of the ratio of the amount of tungsten element material, and less than or equal to 5/2 times, activate 12 hours, residual fluorine uses dry soda lime Absorbed, purged 2 hours with nitrogen, tungsten-based catalyst is made.

Embodiment 2

The preparation technology of catalyst is substantially the same manner as Example 1, except that the percentage group of tungsten ion and manganese element As 100% and 0.

Embodiment 3

The preparation technology of catalyst is substantially the same manner as Example 1, except that the percentage group of tungsten ion and manganese element As 80% and 20%.

Embodiment 4

The preparation technology of catalyst is substantially the same manner as Example 1, except that the percentage group of tungsten ion and manganese element As 70% and 30%.

Embodiment 5

The preparation technology of catalyst is substantially the same manner as Example 1, except that the percentage group of tungsten ion and manganese element As 60% and 40%.

Embodiment 6

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to aluminum nitrate, tungsten ion and The percentage composition of aluminium element is 90% and 10%.

Embodiment 7

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to magnesium nitrate, tungsten ion and The percentage composition of magnesium elements is 90% and 10%.

Embodiment 8

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nickel nitrate, tungsten ion and The percentage composition of nickel element is 90% and 10%.

Embodiment 9

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to cobalt nitrate, tungsten ion and The percentage composition of cobalt element is 90% and 10%.

Embodiment 10

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to Titanium Nitrate, tungsten ion and The percentage composition of titanium elements is 90% and 10%.

Embodiment 11

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to zirconium nitrate, tungsten ion and The percentage composition of zr element is 90% and 10%.

Embodiment 12

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid vanadium acyl, tungsten ion Percentage composition with v element is 90% and 10%.

Embodiment 13

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to ferric nitrate, tungsten ion and The percentage composition of ferro element is 90% and 10%.

Embodiment 14

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to zinc nitrate, tungsten ion and The percentage composition of Zn-ef ficiency is 90% and 10%.

Embodiment 15

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to indium nitrate, tungsten ion and The percentage composition of phosphide element is 90% and 10%.

Embodiment 16

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to copper nitrate, tungsten ion and The percentage composition of copper is 90% and 10%.

Embodiment 17

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to silver nitrate, tungsten ion and The percentage composition of silver element is 90% and 10%.

Embodiment 18

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to cadmium nitrate, tungsten ion and The percentage composition of cadmium element is 90% and 10%.

Embodiment 19

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to mercuric nitrate, tungsten ion and The percentage composition of mercury element is 90% and 10%.

Embodiment 20

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to gallium nitrate, tungsten ion and The percentage composition of gallium element is 90% and 10%.

Embodiment 21

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid tin, tungsten ion and The percentage composition of tin element is 90% and 10%.

Embodiment 22

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to plumbi nitras, tungsten ion and The percentage composition of lead element is 90% and 10%.

Embodiment 23

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to strontium nitrate, tungsten ion and The percentage composition of strontium element is 90% and 10%.

Embodiment 24

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to barium nitrate, tungsten ion and The percentage composition of barium element is 90% and 10%.

Embodiment 25

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid rhenium, tungsten ion and The percentage composition of rhenium element is 90% and 10%.

Embodiment 26

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to scandium nitrate, tungsten ion and The percentage composition of scandium element is 90% and 10%.

Embodiment 27

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid ruthenium, tungsten ion and The percentage composition of ruthenium element is 90% and 10%.

Embodiment 28

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid niobium, tungsten ion and The percentage composition of niobium element is 90% and 10%.

Embodiment 29

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid tantalum acyl, tungsten ion Percentage composition with tantalum element is 90% and 10%.

Embodiment 30

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to calcium nitrate, tungsten ion and The percentage composition of calcium constituent is 90% and 10%.

Embodiment 31

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to cerous nitrate, tungsten ion and The percentage composition of Ce elements is 90% and 10%.

Embodiment 32

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to nitric acid antimony, tungsten ion and The percentage composition of antimony element is 90% and 10%.

Embodiment 33

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to thallium nitrate, tungsten ion and The percentage composition of thallium element is 90% and 10%.

Embodiment 34

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to hafnium nitrate, tungsten ion and The percentage composition of hafnium element is 90% and 10%.

Embodiment 35

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to manganese oxide, tungsten ion and The percentage composition of manganese element is 90% and 10%.

Embodiment 36

The preparation technology of catalyst is substantially the same manner as Example 1, except that manganese nitrate is changed to manganous hydroxide, tungsten ion Percentage composition with manganese element is 90% and 10%.

Embodiment 37

The preparation technology of catalyst is substantially the same manner as Example 1, except that tungsten simple substance is changed to the tungsten of three oxidation two, tungsten from The percentage composition of son and nickel element is 90% and 10%, and fluorine gas throughput is more than or equal to three two tungsten material consumption fluorine gas of oxidation 3 times of the ratio of theoretical amount and the amount of three two tungsten materials of oxidation, and less than or equal to 5 times, residual fluorine is entered using dry soda lime Row absorbs, and high activity tungsten-based catalyst is made.

Embodiment 38

The preparation technology of catalyst is substantially the same manner as Example 1, except that tungsten simple substance is changed to tungsten dioxide, tungsten ion Percentage composition with nickel element is 90% and 10%, and fluorine gas throughput is theoretical more than or equal to the precursor consumption fluorine gas of tungsten ion 2 times of the ratio of amount and the amount of tungsten dioxide material, and less than or equal to 5/2 times, residual fluorine is inhaled using dry soda lime Receive, high activity tungsten-based catalyst is made.

Embodiment 39

The preparation technology of catalyst is substantially the same manner as Example 1, except that tungsten simple substance is changed to tungsten pentoxide, tungsten from The percentage composition of sub and nickel element is 90% and 10%, and fluorine gas throughput is the precursor consumption fluorine gas reason more than or equal to tungsten ion The ratio of the amount of stoichiometric and tungsten pentoxide material is 5 times, and residual fluorine is absorbed using dry soda lime, is made high and lives Property tungsten-based catalyst.

Embodiment 40

The preparation technology of catalyst is substantially the same manner as Example 1, except that activation atmosphere fluorine gas is changed to tungsten hexafluoride, The ratio between amount of tungsten hexafluoride and tungsten element material is more than or equal to 1, and less than or equal to 5, remaining tungsten hexafluoride is absorbed using water, High activity tungsten-based catalyst is made.

Application examples 1

Fluoro- chlorine exchange catalysts prepared by embodiment 1, the reaction for following synthesis series fluorosurfactants alkene：

After reaction 20 hours, after reaction product removes HF through washing, alkali cleaning, constituted with GC analyzing organic substances, as a result such as the institute of table 1 Show.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 1

Fluorine containing olefine selectively refers to the ratio of target product, and generation E-HFO-1225ye, Z-HFO- are referred to for reaction (3) 1225ye selective summation, the selectivity for referring to generation E-HFO-1234ze, Z-HFO-1234ze for reaction (4) and (5) is total With, other reaction be simple target product selectivity.

Application examples 2

Catalyst prepared by embodiment 2 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 2.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 2

Application examples 3

Catalyst prepared by embodiment 3 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 3.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 3

Application examples 4

Catalyst prepared by embodiment 4 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 4.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 4

Application examples 5

Catalyst prepared by embodiment 5 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 5.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 5

Application examples 6

Catalyst prepared by embodiment 6 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 6.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 6

Application examples 7

Catalyst prepared by embodiment 7 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 7.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 7

Application examples 8

Catalyst prepared by embodiment 8 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 8.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 8

Application examples 9

Catalyst prepared by embodiment 9 is used for the reaction for synthesizing series fluorosurfactants alkene, and application conditions and application examples 1 are basic It is identical, as a result as shown in table 9.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 9

Application examples 10

Catalyst prepared by embodiment 10 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 10.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 10

Application examples 11

Catalyst prepared by embodiment 11 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 11.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 11

Application examples 12

Catalyst prepared by embodiment 12 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 12.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 12

Application examples 13

Catalyst prepared by embodiment 13 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 13.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 13

Application examples 14

Catalyst prepared by embodiment 14 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 14.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 14

Application examples 15

Catalyst prepared by embodiment 15 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in Table 15.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 15

Application examples 16

Catalyst prepared by embodiment 16 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 16.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 16

Application examples 17

Catalyst prepared by embodiment 17 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 17.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 17

Application examples 18

Catalyst prepared by embodiment 18 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 18.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 18

Application examples 19

Catalyst prepared by embodiment 19 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 19.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 19

Application examples 20

Catalyst prepared by embodiment 20 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 20.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 20

Application examples 21

Catalyst prepared by embodiment 21 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 21.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 21

Application examples 22

Catalyst prepared by embodiment 22 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 22.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 22

Application examples 23

Catalyst prepared by embodiment 23 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 23.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 23

Application examples 24

Catalyst prepared by embodiment 24 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 24.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 24

Application examples 25

Catalyst prepared by embodiment 25 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in Table 25.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 25

Application examples 26

Catalyst prepared by embodiment 26 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 26.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 26

Application examples 27

Catalyst prepared by embodiment 27 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 27.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 27

Application examples 28

Catalyst prepared by embodiment 28 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 28.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 28

Application examples 29

Catalyst prepared by embodiment 29 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 29.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 29

Application examples 30

Catalyst prepared by embodiment 30 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 30.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 30

Application examples 31

Catalyst prepared by embodiment 31 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 31.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 31

Application examples 32

Catalyst prepared by embodiment 32 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 32.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 32

Application examples 33

Catalyst prepared by embodiment 33 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 33.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 33

Application examples 34

Catalyst prepared by embodiment 34 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 34.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 34

Application examples 35

Catalyst prepared by embodiment 35 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 35.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 35

Application examples 36

Catalyst prepared by embodiment 36 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 36.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 36

Application examples 37

Catalyst prepared by embodiment 37 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 37.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 37

Application examples 38

Catalyst prepared by embodiment 38 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 38.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 38

Application examples 39

Catalyst prepared by embodiment 39 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 39.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 39

Application examples 40

Catalyst prepared by embodiment 40 is used for the reaction for synthesizing series fluorosurfactants alkene, application conditions and the base of application examples 1 This is identical, as a result as shown in table 40.Catalyst is continuously run 1000 hours, and its catalytic activity is basically unchanged.

Table 40

Claims

1. a kind of high activity tungsten-based catalyst, the high activity tungsten-based catalyst is made up of tungsten ion and auxiliary agent, tungsten ion is three Combination in valency tungsten ion, tetravalence tungsten ion, pentavalent tungsten ion, auxiliary agent be Al, Mg, Ni, Co, Ti, Zr, V, Fe, Zn, In, Cu, At least one of Ag, Cd, Hg, Ga, Sn, Pb, Mn, Ba, Re, Sc, Sr, Ru, Nb, Ta, Ca, Ce, Sb, Tl, Hf or several, and The quality percentage composition of tungsten ion and auxiliary agent is 60%~100% and 0~40%, and the preparation method of the catalyst is as follows：

(1) according to the mass percent of tungsten ion and auxiliary agent, the precursor of tungsten ion and auxiliary agent is well mixed, it is compressing, obtain To catalyst precarsor；

(2) catalyst precarsor for obtaining step (1), carries out roasting 6~15 hours in 300 DEG C~500 DEG C under nitrogen atmosphere；

(3) product of roasting for obtaining step (2), in 600 DEG C~800 DEG C, is first vacuumized, then in confined conditions, fluorine gas Middle activation 6~15 hours, is made high activity tungsten-based catalyst, and the total amount that the fluorine gas is passed through is equal to the precursor consumption fluorine of tungsten ion Gas theoretical amount consumes fluorine gas theoretical amount summation plus metallic element auxiliary agent；The precursor consumption fluorine gas theoretical amount of the tungsten ion is big Tungsten ion is reduced into the fluorine gas theoretical amount consumed needed for tungsten trifluoride in the precursor of tungsten ion, and less than in the precursor of tungsten ion Tungsten ion is reduced into the fluorine gas theoretical amount of consumption needed for five tungsten fluorides；

Or the product of roasting for obtaining step (2), in 600 DEG C~800 DEG C, first vacuumize, then in confined conditions, hexafluoro Change in tungsten and activate 6~15 hours, high activity tungsten-based catalyst is made, the total amount that the tungsten hexafluoride is passed through is equal to before tungsten ion Body consumption tungsten hexafluoride theoretical amount consumes tungsten hexafluoride theoretical amount summation plus metallic element auxiliary agent；The precursor of the tungsten ion disappears The tungsten hexafluoride reason that consumption tungsten hexafluoride theoretical amount is consumed for needed for tungsten ion in the precursor more than tungsten ion is reduced into tungsten trifluoride Stoichiometric, and the tungsten hexafluoride theoretical amount consumed needed for five tungsten fluorides is reduced into less than tungsten ion in the precursor of tungsten ion.

2. high activity tungsten-based catalyst according to claim 1, the precursor of the tungsten ion is tungsten simple substance, three oxidations two At least one of tungsten, tungsten dioxide or tungsten pentoxide are several, and the precursor of auxiliary agent is the oxide of metal, hydroxide At least one of thing, nitrate, acetate or carbonate are several.

3. the high activity tungsten-based catalyst according to claim 2, the precursor of the tungsten ion is tungsten simple substance, and the fluorine gas leads to Tolerance is 3/2 times of the ratio that fluorine gas theoretical amount and the amount of tungsten element material are consumed more than or equal to tungsten element material, and is less than or equal to 5/2 times, residual fluorine is absorbed using dry soda lime, and high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is three two tungsten of oxidation, and the fluorine gas throughput is more than or equal to three two tungsten material consumption fluorine of oxidation 3 times of the ratio of gas theoretical amount and the amount of three two tungsten materials of oxidation, and less than or equal to 5 times, residual fluorine uses dry soda lime Absorbed, high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is tungsten dioxide, and the fluorine gas throughput is the precursor consumption fluorine gas reason more than or equal to tungsten ion Stoichiometric and 2 times of the ratio of the amount of tungsten dioxide material, and less than or equal to 5/2 times, residual fluorine is carried out using dry soda lime Absorb, high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is tungsten pentoxide, and the fluorine gas throughput is the precursor consumption fluorine gas more than or equal to tungsten ion The ratio of theoretical amount and the amount of tungsten pentoxide material is 5 times, and residual fluorine is absorbed using dry soda lime, and height is made Active tungsten-based catalyst；

The precursor of the tungsten ion is tungsten simple substance, and the tungsten hexafluoride throughput is the precursor consumption hexafluoro more than or equal to tungsten ion Change 1 times of the ratio of tungsten theoretical amount and the amount of tungsten element material, and less than or equal to 5 times, remaining tungsten hexafluoride uses dry alkali stone Ash is absorbed, and high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is three two tungsten of oxidation, and the tungsten hexafluoride throughput is the precursor consumption more than or equal to tungsten ion 2 times of the ratio of tungsten hexafluoride theoretical amount and the amount of three two tungsten materials of oxidation, and less than or equal to 10 times, remaining tungsten hexafluoride uses dry Dry soda lime is absorbed, and high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is tungsten dioxide, and the tungsten hexafluoride throughput is the precursor consumption six more than or equal to tungsten ion 2 times of the ratio of tungsten fluoride theoretical amount and the amount of tungsten dioxide material, and less than or equal to 5 times, remaining tungsten hexafluoride uses drying Soda lime is absorbed, and high activity tungsten-based catalyst is made；

The precursor of the tungsten ion is tungsten pentoxide, and the tungsten hexafluoride throughput is the precursor consumption more than or equal to tungsten ion 10 times of the ratio of tungsten hexafluoride theoretical amount and the amount of tungsten pentoxide material, remaining tungsten hexafluoride is carried out using dry soda lime Absorb, high activity tungsten-based catalyst is made.

4. high activity tungsten-based catalyst according to claim 2, the precursor of the tungsten ion is tungsten simple substance, the auxiliary agent Precursor is the compound containing manganese, scandium or rhenium, the weight/mass percentage composition of tungsten ion and assistant metal element for 80%~95% and 5~ 20%.

5. high price chromium-based catalysts according to claim 4, the precursor of the auxiliary agent is manganese nitrate, scandium nitrate or nitric acid Rhenium.

6. high activity tungsten-based catalyst according to claim 5, the precursor of the high activity tungsten-based catalyst is tungsten simple substance With the mixture of manganese nitrate, wherein, the mass percent of tungsten ion and manganese element composition is 90% and 10%；Or

The precursor of described tungsten-based catalyst is the mixture of ammonium paratungstate and scandium nitrate, wherein, the matter of tungsten ion and scandium element It is 90% and 10% to measure percentage composition；Or

The precursor of described tungsten-based catalyst is the mixture of ammonium paratungstate and nitric acid rhenium, wherein, the matter of tungsten ion and rhenium element It is 90% and 10% to measure percentage composition.

7. the preparation method of any described high activity catalyst with base of molybdenum of claim 1-6, using the following steps：

(A) according to the mass percent of tungsten ion and auxiliary agent, the precursor of tungsten ion and auxiliary agent is well mixed, it is compressing, obtain To catalyst precarsor；

(B) catalyst precarsor for obtaining step (A), carries out roasting 6~15 hours in 300 DEG C~500 DEG C under nitrogen atmosphere；

(C) product of roasting for obtaining step (B), in 600 DEG C~800 DEG C, is first vacuumized, then in confined conditions, fluorine gas Middle activation 6~15 hours, is made high activity tungsten-based catalyst, and the total amount that the fluorine gas is passed through is equal to the precursor consumption fluorine of tungsten ion Gas theoretical amount consumes fluorine gas theoretical amount summation plus metallic element auxiliary agent；The precursor consumption fluorine gas theoretical amount of the tungsten ion is big Tungsten ion is reduced into the fluorine gas theoretical amount consumed needed for tungsten trifluoride in the precursor of tungsten ion, and less than in the precursor of tungsten ion Tungsten ion is reduced into the fluorine gas theoretical amount of consumption needed for five tungsten fluorides.

Or the product of roasting for obtaining step (B), in 600 DEG C~800 DEG C, in confined conditions, in tungsten hexafluoride activate 6~ 15 hours, high activity tungsten-based catalyst is made, the precursor consumption that the total amount that the tungsten hexafluoride is passed through is equal to tungsten ion is lithium Tungsten theoretical amount consumes tungsten hexafluoride theoretical amount summation plus metallic element auxiliary agent；The precursor consumption tungsten hexafluoride reason of the tungsten ion The tungsten hexafluoride theoretical amount that stoichiometric is consumed for needed for tungsten ion in the precursor more than tungsten ion is reduced into tungsten trifluoride, and less than tungsten Tungsten ion is reduced into the tungsten hexafluoride theoretical amount of consumption needed for five tungsten fluorides in the precursor of ion.

8. preparation method according to claim 7, the tungsten hexafluoride can be prepared by following methods：

1) in 20 DEG C~150 DEG C of temperature, tungsten simple substance reacts with fluorine gas and obtains tungsten hexafluoride；

2) or in 300 DEG C~450 DEG C of temperature, tungstic acid reacts with fluorine gas and obtains tungsten hexafluoride and oxygen.

9. fluoro- chlorine exchange reaction preparation occurs any tungsten-based catalysts of claim 1-6 for gas phase catalysis alkenyl halide at high temperature Application in Fluorine containing olefine.

10. application according to claim 9, the alkenyl halide is ring-CF₂CF₂CF₂CCl=CCl, prepare ring- CF₂CF₂CF₂CF=CCl；

Or the alkenyl halide is 2- chloro-3,3,3 ,-trifluoropropenes, prepares 2,3,3,3- tetrafluoropropenes；

Or the alkenyl halide is E/Z-1- chloro- 2,3,3,3- tetrafluoropropenes prepare E/Z-1,2,3,3,3- pentafluoropropenes；

Or the alkenyl halide is E-1- chloro-3,3,3 ,-trifluoropropenes, prepares E/Z-1,3,3,3- tetrafluoropropenes；

Or the alkenyl halide is Z-1- chloro-3,3,3 ,-trifluoropropenes, prepares E/Z-1,3,3,3- tetrafluoropropenes.