CN106866359A - A kind of method that PVF is prepared by 1,1- Difluoroethane cracking - Google Patents
A kind of method that PVF is prepared by 1,1- Difluoroethane cracking Download PDFInfo
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- CN106866359A CN106866359A CN201510927473.0A CN201510927473A CN106866359A CN 106866359 A CN106866359 A CN 106866359A CN 201510927473 A CN201510927473 A CN 201510927473A CN 106866359 A CN106866359 A CN 106866359A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses the method that one kind prepares PVF by 1,1- Difluoroethane cracking, it is included in the presence of acetylene, under catalyst action, 1,1- Difluoroethane obtains 1,1- Difluoroethanes through cracking.The method that the present invention is provided has the advantages that raw material conversion per pass is high, cracking reaction temperature is low, PVF impurities are few, selectivity is high.
Description
Technical field
The present invention relates to a kind of preparation method of Fluorine containing olefine, particularly it is adapted to a kind of preparation method of PVF.
Background technology
Polyfluoroethylene resin is one kind that fluorinated volume is minimum, density is minimum in fluororesin, in addition to the characteristic with general fluorine resin,
Also there is long service life, the features such as anti-flex performance is good, corrosion resistance is strong, be usually used in making erosion shield, lining, pad
Circle, shafting oil pipe coating, construction and decoration material, solar energy backboard membrane etc., tool has been widely used.
When polyfluoroethylene resin is prepared, raw material fluoride monomers need to be used.For the preparation method of fluoride monomers, Neng Gougong
The main of industry application has acetylene hydrofluorination and 1,1- Difluoroethanes (HFC-152a) cracking process.
The method for wherein preparing PVF with acetylene hydrofluorination method, Chinese patent CN101363037A is disclosed using La/ γ-Al2O3
The method that PVF is prepared for catalyst, by acetylene.Its conversion of alkyne is up to 96.0%, and PVF is selectively up to
The selectivity of 73.0%, accessory substance HFC-152a is 24.1%.Chinese patent CN102698778A discloses use
Cr2O3-La2O3/AlF3-α-Al2O3Catalyst, the method that PVF is prepared by acetylene.Its conversion of alkyne is 93.1%, PVF
Selectivity be 79.2%, the selectivity of accessory substance HFC-152a is 20.4%.The accessory substance that both approaches are not only produced
HFC-152a contents are high, and easily form carbon distribution, catalyst service life influenceed, so as to cause reaction pipeline blockage.It is solution
The defect accessory substance HFC-152a that certainly produces high, Chinese patent CN101417925A discloses a kind of acetylene in gas phase fluorination production
The method of VF, using two reactors, carries out the addition reaction of acetylene and hydrogen fluoride in reactor I, the tail gas of generation is separated
Afterwards, hydrogen fluoride enters the cycling and reutilization of reactor I, and PVF carries out product collection, and acetylene and HFC-152a then enter reactor
Reacted in II.Although the method solves the Utilizing question of accessory substance HFC-152a, improves the selectivity and product of PVF
Rate, but still do not solve due to carbon distribution problem caused by Addition on acetylene exothermic heat of reaction simultaneously.
United States Patent (USP) US5880315 discloses the method that HFC-152a cracking prepares PVF, with Zn/AlF3Or Mg/AlF3For
Catalyst, in 275 DEG C, air speed 600h-1Under the conditions of react 720h obtain PVF.The method, the conversion ratio of HFC-152a
Only 34.3% or 40%.
Therefore, still it is hopeful to be further improved the preparation method of PVF.
The content of the invention
It is an object of the invention to provide a kind of new method for preparing PVF, with raw material conversion per pass is high, cracking reaction temperature
Spend the advantages of low, PVF impurities are few, selectivity is high.
The present invention provides following technical scheme：
The method that one kind prepares PVF by 1,1- Difluoroethane cracking, methods described includes：
In the presence of acetylene, under catalyst action, 1,1- Difluoroethane obtains 1,1- Difluoroethanes through cracking；
The catalyst include major catalyst and major catalyst, wherein major catalyst be aluminium, co-catalyst be selected from lanthanum, yttrium, cerium,
One kind, two or three combination of the above, major catalyst and co-catalysis in zirconium, zinc, magnesium, nickel, cobalt, iron, manganese, tin and bismuth
The mol ratio of agent is 1:0.01~0.3；
The 1,1- Difluoroethanes are 1.0 with the mol ratio of acetylene:0.02~0.2.
The method for preparing PVF by 1,1- Difluoroethane cracking that this law is provided, a small amount of acetylene is added by toward reaction,
Exothermic heat of reaction and heat absorption is set to obtain efficient coupling, so that the conversion per pass of raw material HFC-152a is improved, and it is anti-to reduce cracking simultaneously
Answer temperature.
The mol ratio of the addition of acetylene, i.e. 1,1- Difluoroethanes and acetylene, satisfaction is smoothed out reaction.Preferably,
The 1,1- Difluoroethanes are 1.0 with the mol ratio of acetylene:0.02~0.2.It may further be preferable that 1, the 1- Difluoroethanes
It is 1.0 with the mol ratio of acetylene:0.05~0.15.
The method for preparing PVF by 1,1- Difluoroethane cracking that this law is provided, the catalyst includes major catalyst and co-catalysis
Agent.Wherein major catalyst is aluminium.
The co-catalyst be selected from lanthanum, yttrium, cerium, zirconium, zinc, magnesium, nickel, cobalt, iron, manganese, tin and bismuth in one kind, two kinds
Or three kinds of combination of the above combination of the above.Preferably, the co-catalyst is selected from the one kind in lanthanum, boron, zinc, nickel, iron, bismuth
Or two or more combinations.It may further be preferable that the co-catalyst be selected from lanthanum, zinc, nickel, iron in one or more
Combination.
The mol ratio of catalyst of the present invention, its major catalyst and co-catalyst, satisfaction is smoothed out reaction.It is preferred that
, the major catalyst is 1 with the mol ratio of co-catalyst:0.01~0.3.It may further be preferable that major catalyst with help
The mol ratio of catalyst is 1:0.04~0.25.It is even furthermore preferable that major catalyst is with the mol ratio of co-catalyst
1:0.1~0.25.Catalyst of the present invention, before for preparing PVF by 1,1- Difluoroethane cracking, preferably through
Activation process.The activating treatment method, preferably activates in accordance with the following methods：With inert gas at 200~400 DEG C dry 2~
12h, is passed through by HF and inert gas according to mol ratio 1 at 150~400 DEG C:The mixed gas of 4~10 compositions are carried out at fluorination
Reason, gradually increases the concentration of HF in mixed gas, until the final mixed gas being passed through are pure hydrogen fluoride, the fluorination treatment time is
10~24h.
The method for preparing PVF by 1,1- Difluoroethane cracking that this law is provided, reaction temperature meets makes reaction be smoothed out i.e.
Can.Preferably, the reaction temperature is 200~400 DEG C.It may further be preferable that the reaction temperature is 280~350 DEG C.
The method for preparing PVF by 1,1- Difluoroethane cracking that this law is provided, reaction pressure meets makes reaction be smoothed out i.e.
Can.Preferably, the reaction pressure is 0.1~1.0MPa.It may further be preferable that the reaction pressure is normal pressure.
The method for preparing PVF by 1,1- Difluoroethane cracking that this law is provided, feed space velocity meets makes reaction be smoothed out i.e.
Can.Preferably, the feed space velocity is 300~2000h-1.It may further be preferable that the feed space velocity is 500~1000
h-1。
Specific embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these specific implementations
Mode.One skilled in the art would recognize that all alternative present invention encompasses what is potentially included in Claims scope
Scheme, improvement project and equivalents.
Embodiment 1
It is 1: 0.1 according to Al: Fe mol ratio, weighs the Al (OH) of 78.00g3And the Fe (OH) of 10.69g3, ball
Mill blending, then, in 500 DEG C of roasting temperature treatment 6h, is obtained well mixed powder by wet mixing extrusion extrusion forming
To the presoma Fe of catalyst2O3-Al2O3.By the catalyst precursor nitrogen at a temperature of 200 DEG C dried in place 6h, then
It is passed through HF: N2It is 1: 10 mixed gas, 4h is fluorinated at 180 DEG C, is then warming up to 340 DEG C with the speed of 1 DEG C/min, by
Cumulative plus hydrogen fluoride concentration, until the later stage is passed through pure fluorination hydrofluorination 8h, obtains Dehydrofluorination catalyst.
A certain amount of above-mentioned Dehydrofluorination catalyst is fitted into reactor.By HFC-152a and acetylene according to mol ratio 1:0.20
Reactor is passed through after mixing preheating, in 300 DEG C of temperature, air speed 200h-1, reacted under normal pressure, reacted gas is through water
Wash, alkali cleaning, the hydrofluoric acid that obtains recycles, and other gases are further dried, condensation liquefaction, isolate and purify, unreacted
Continue to react in 1,1- Difluoroethane Returning reactor, the PVF isolated carries out product packaging.
During the course of the reaction, reactor tail gas are analyzed, the content of HFC-152a is 74.9% for the content of 22.5%, VF,
The content of acetylene is 2.2%.
Embodiment 2
According to Al: Fe: Ni mol ratio is 1: 0.08: 0.02, weighs the Al of 101.96g2O3, 6.39g Fe2O3、
The NiO of 1.49g, ball milling blending, then by well mixed powder by wet mixing extrusion extrusion forming, in 600 DEG C of temperature
Lower treatment 3h, obtains the presoma NiO-Fe of catalyst2O3-Al2O3.By the catalyst precursor nitrogen at a temperature of 300 DEG C
Dried in place 2h, then passes to HF: N2It is 1: 10 mixed gas, 4h is fluorinated at 180 DEG C, then with the speed of 1 DEG C/min
Rate is warming up to 340 DEG C, gradually increases hydrogen fluoride concentration, until the later stage is passed through pure fluorination hydrofluorination 8h, obtains aluminium-based catalyst.
A certain amount of above-mentioned Dehydrofluorination catalyst is fitted into reactor.By HFC-152a and acetylene according to mol ratio 1:0.02
Reactor is passed through after mixing preheating, is reacted under 350 DEG C of temperature, air speed 200h-1, normal pressure, reacted gas is through water
Wash, alkali cleaning, the hydrofluoric acid that obtains recycles, and other gases are further dried, condensation liquefaction, isolate and purify, unreacted
Continue to react in 1,1- Difluoroethane Returning reactor, the PVF isolated carries out product packaging.
During the course of the reaction, reactor tail gas are analyzed, the content of HFC-152a is 78.0% for the content of 21.3%, VF,
The content of acetylene is 0.5%.
Embodiment 3
According to Al: Zn: La mol ratio is 1: 0.15: 0.01, weighs the γ-AlF of 83.98g3, 12.21g ZnO,
The La of 3.26g2O3, ball milling blending, then by well mixed powder by wet mixing extrusion extrusion forming, in 300 DEG C of temperature
Lower calcination process 3h, obtains the presoma La of catalyst2O3-ZnO-AlF3.By the catalyst precursor nitrogen in 300 DEG C of temperature
Lower dried in place 2h, then passes to HF: N2It is 1: 4 mixed gas, 4h is fluorinated at 200 DEG C, then with the speed of 1 DEG C/min
Rate is warming up to 360 DEG C, gradually increases hydrogen fluoride concentration, until the later stage is passed through pure fluorination hydrofluorination 6h, obtains aluminium-based catalyst.
A certain amount of above-mentioned Dehydrofluorination catalyst is fitted into reactor.By HFC-152a and acetylene according to mol ratio 1:0.15
Reactor is passed through after mixing preheating, in 350 DEG C of temperature, air speed 500h-1, reacted under normal pressure, reacted gas is through water
Wash, alkali cleaning, the hydrofluoric acid that obtains recycles, and other gases are further dried, condensation liquefaction, isolate and purify, unreacted
Continue to react in 1,1- Difluoroethane Returning reactor, the PVF isolated carries out product packaging.
During the course of the reaction, reactor tail gas are analyzed, the content of HFC-152a is 67.3% for the content of 30.6%, VF,
The content of acetylene is 1.5%.
Comparative example 1
Above-mentioned Dehydrofluorination catalyst is fitted into reactor, HFC-152a is passed through, in 300 DEG C of temperature, air speed 200h-1, often
Pressure is reacted, and reacted gas is recycled through washing, alkali cleaning, the hydrofluoric acid that obtains, other gases are further dried,
Condensation liquefaction, isolate and purify, continue to react in unreacted 1,1- Difluoroethanes Returning reactor, the PVF isolated is carried out
Product packaging.
During the course of the reaction, reactor tail gas are analyzed.When reaction temperature is 300 DEG C, the content of HFC-152a in tail gas
It is that the content of 36.5%, VF is 62.8%, the content of acetylene is 0.6%.
Knowable to above example and comparative example's data, added in the reaction that PVF is prepared by 1,1- Difluoroethane cracking
Acetylene, can effectively improve the growing amount of VF.
Claims (7)
1. the method that one kind prepares PVF by 1,1- Difluoroethane cracking, it is characterised in that methods described includes：
In the presence of acetylene, under catalyst action, 1,1- Difluoroethane obtains 1,1- Difluoroethanes through cracking；
The catalyst include major catalyst and major catalyst, wherein major catalyst be aluminium, co-catalyst be selected from lanthanum, yttrium, cerium,
One kind, two or three combination of the above in zirconium, zinc, magnesium, nickel, cobalt, iron, manganese, tin and bismuth, the major catalyst with help
The mol ratio of catalyst is 1:0.01~0.3；
The 1,1- Difluoroethanes are 1.0 with the mol ratio of acetylene:0.02~0.2.
2. according to the method for preparing PVF by 1,1- Difluoroethane cracking described in claim 1, it is characterised in that 1, the 1- difluoros
Ethane is 1.0 with the mol ratio of acetylene:0.05~0.15.
3. according to the method for preparing PVF by 1,1- Difluoroethane cracking described in claim 1, it is characterised in that the co-catalyst
Selected from one or more combinations in lanthanum, boron, zinc, nickel, iron, bismuth, major catalyst is 1 with the mol ratio of co-catalyst:0.04~
0.25。
4. according to the method for preparing PVF by 1,1- Difluoroethane cracking described in claim 3, it is characterised in that the co-catalysis
Agent is selected from one or more combinations in lanthanum, zinc, nickel, iron, and major catalyst is 1 with the mol ratio of co-catalyst:0.1~
0.25。
5. according to the method for preparing PVF by 1,1- Difluoroethane cracking described in claim 1, it is characterised in that the catalyst is pressed
According to following methods activation：With inert gas at 200~400 DEG C dry 2~12h, be passed through at 150~400 DEG C by HF with it is lazy
Property gas is according to mol ratio 1:The mixed gas of 4~10 compositions carry out fluorination treatment, gradually increase the concentration of HF in mixed gas,
Until the mixed gas being finally passed through are pure hydrogen fluoride, the fluorination treatment time is 10~24h.
6. according to the method for preparing PVF by 1,1- Difluoroethane cracking described in claim 1, it is characterised in that reaction temperature is
200~400 DEG C, feed space velocity is 300~2000h-1, reaction pressure is 0.1~1.0MPa.
7. according to the method for preparing PVF by 1,1- Difluoroethane cracking described in claim 6, it is characterised in that reaction temperature is
280~350 DEG C, feed space velocity is 500~1000h-1, reaction pressure is normal pressure.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510927473.0A CN106866359B (en) | 2015-12-14 | 2015-12-14 | Method for preparing vinyl fluoride by cracking 1, 1-difluoroethane |
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| CN201510927473.0A CN106866359B (en) | 2015-12-14 | 2015-12-14 | Method for preparing vinyl fluoride by cracking 1, 1-difluoroethane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776394A (en) * | 2019-11-07 | 2020-02-11 | 上海三爱富新材料科技有限公司 | Method for preparing fluorine-containing ethylene by catalytic cracking of 2-chloro-1, 1-difluoroethane |
| CN114560750A (en) * | 2022-01-28 | 2022-05-31 | 浙江巨化技术中心有限公司 | Preparation method of 1-chloro-2, 3, 3-trifluoropropene |
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| US3726931A (en) * | 1964-09-22 | 1973-04-10 | Phillips Petroleum Co | Process of preparing fluorethylene |
| CN101417925A (en) * | 2008-12-01 | 2009-04-29 | 浙江师范大学 | Method for producing fluoroethylene by gas phase fluorination of acetylene |
| CN103920484A (en) * | 2013-01-14 | 2014-07-16 | 中化蓝天集团有限公司 | Catalyst for hydrofluorination reaction of acetylene to prepare vinyl fluoride and 1,1-difluoroethane, and preparation method and application thereof |
| CN104841413A (en) * | 2014-02-18 | 2015-08-19 | 浙江蓝天环保高科技股份有限公司 | Aluminum base catalyst for preparing vinyl fluoride from 1,1-difluoroethane, and preparation method and application thereof |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3726931A (en) * | 1964-09-22 | 1973-04-10 | Phillips Petroleum Co | Process of preparing fluorethylene |
| CN101417925A (en) * | 2008-12-01 | 2009-04-29 | 浙江师范大学 | Method for producing fluoroethylene by gas phase fluorination of acetylene |
| CN103920484A (en) * | 2013-01-14 | 2014-07-16 | 中化蓝天集团有限公司 | Catalyst for hydrofluorination reaction of acetylene to prepare vinyl fluoride and 1,1-difluoroethane, and preparation method and application thereof |
| CN104841413A (en) * | 2014-02-18 | 2015-08-19 | 浙江蓝天环保高科技股份有限公司 | Aluminum base catalyst for preparing vinyl fluoride from 1,1-difluoroethane, and preparation method and application thereof |
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| Title |
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| SIRLIBAEV, T. S. ET AL.: "Catalytic synthesis of vinyl fluoride based on 1,1-difluoroethane and acetylene", 《ZHURNAL PRIKLADNOI KHIMII》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776394A (en) * | 2019-11-07 | 2020-02-11 | 上海三爱富新材料科技有限公司 | Method for preparing fluorine-containing ethylene by catalytic cracking of 2-chloro-1, 1-difluoroethane |
| CN110776394B (en) * | 2019-11-07 | 2022-06-10 | 上海华谊三爱富新材料有限公司 | Method for preparing fluorine-containing ethylene by catalytic cracking of 2-chloro-1, 1-difluoroethane |
| CN114560750A (en) * | 2022-01-28 | 2022-05-31 | 浙江巨化技术中心有限公司 | Preparation method of 1-chloro-2, 3, 3-trifluoropropene |
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