CN109180420A - A kind of preparation method of 1,1- difluoroethylene - Google Patents
A kind of preparation method of 1,1- difluoroethylene Download PDFInfo
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- CN109180420A CN109180420A CN201811134073.4A CN201811134073A CN109180420A CN 109180420 A CN109180420 A CN 109180420A CN 201811134073 A CN201811134073 A CN 201811134073A CN 109180420 A CN109180420 A CN 109180420A
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- vinylidene fluoride
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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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
Abstract
The invention discloses one kind 1, the preparation method of 1- difluoroethylene, the following steps are included: composite catalyst is packed into tubular reactor, with 1, the fluoro- 1- chloroethanes of 1- bis- or 1, the fluoro- 2- chloroethanes of 1- bis- are that raw material is passed through in the tubular reactor, carry out gas phase catalysis cracking reaction, vinylidene fluoride is made；The composite catalyst is that the composite catalyst is metal composite fluoride.The method provided by the invention for preparing vinylidene fluoride has reaction temperature low, selectivity of product height, the features such as high income, catalyst reproducibility is strong, preparation process condition is mild, easy to operate.
Description
Technical field
The present invention relates to a kind of preparation methods of 1,1- difluoroethylene.
Background technique
Under 1,1- bis- fluoro- 1- chloroethanes (HCFC-142b or R142b) room temperature be colourless gas, slightly fragranced and easily
It is dissolved in oil, is insoluble in water.HCFC-142b is a kind of important organic intermediate, is applied in every field such as refrigerant, hair
Infusion etc., but it is monomer for producing Kynoar (PVDF), vinylidene fluoride (VDF) that its is main.To being at present
Only, the production scale of vinylidene is only second to tetrafluoroethene in fluorochemical monomer, and is widely used in every field.1,1- difluoro
Ethylene (also referred to as vinylidene) is one of important species of Fluorine containing olefine, mainly for the production of polyvinylidene fluoride resin, fluorubber
And fluorinated copolymer such as biasfluoroethylene-hexafluoropropylene, vinylidene-vinylidene, vinylidene-tetrafluoroethene-hexafluoro third
Alkene etc..In addition the fluorubber that vinylidene and hexafluoropropene, tetrafluoroethene are copolymerized is because of its outstanding heat-resisting quantity, oil resistant
Property, solvent resistance and physical and mechanical property and become indispensable in modern industry especially high-tech sector and substitution basis
One of material.And HCFC-142 is the by-product for producing HCFC-142b and generating, industrially without application value, if can incite somebody to action
Its resource utilization can substantially reduce production cost and offal treatment cost.
The production method of vinylidene is divided by raw material, mainly there is the cracking preparation by the dehydrogenation of C2 halogenated hydrocarbons, defluorinate, dechlorination
Method, the copyrolysis preparation method and C3~C5 deep pyrolytic preparation method of C1 halogenated hydrocarbons.There is C2:HCFC-142b on raw material
(1,1- bis- fluoro- 1- chloroethanes and 1, the fluoro- 2- chloroethanes of 1- bis-), R152a (1,1- Difluoroethane), VDC (1,1- bis- chloroethene
Alkene), R132b (1,2- bis- chlorine-1,1-difluoroethane Difluoroethane) etc.；C1:R22 (the fluoro- 1- chloromethanes of 1-), R12(methylene chloride), R13
(the chloro- fluoroform of 1-) etc..Divide from preparation method, there is catalytic pyrolysis, thermal cracking, dilution cracking and promotor cracking.
Reaction for HCFC-142b dehydrochlorination, due in HCFC-142b molecule in conjunction with the same carbon atom two
A fluorine atom enhances C-Cl key so that HCFC-142b dehydrochlorination in the absence of catalyst must thermal cracking at high temperature, so
And reacted under high temperature and be easy to cause side reaction and disproportionated reaction, to influence the selectivity and yield of the reaction.Due to thermal cracking
With high income, control condition is few, simple operation and other advantages, and HCFC-142b thermal cracking and diluent, promotor cracking are industry
The main method of upper production VDF.But the method for thermal cracking needs to be reacted at high temperature so that industrialized production as described above
Energy consumption is very high, and Pintsch process is easy to generate clogged with soot pipeline.
Problems existing for HCFC-142b Pintsch process can be solved by the approach of catalytic pyrolysis.Catalytic pyrolysis can
So that the reaction activity of HCFC-142b dehydrochlorination significantly reduces, so as to reduce reaction temperature and reduce energy consumption.Equally
Catalytic pyrolysis can inhibit the generation of side reaction to be conducive to improve the selectivity of product.So catalytic pyrolysis is many due to its
Advantage becomes the focus on research direction of HCFC-142b dehydrochlorination.Using compound in Chinese patent CN201710034557.0
At 250 ~ 550 DEG C of reaction temperature, 90% or more VDF selectivity can be obtained as catalyst in type.Patent CN106588563A with
Ba based compound is major catalyst and to add transition metal etc. be that co-catalyst obtains different HCFC-142b conversion ratios and VDF choosing
Selecting property.It uses HCFC-142b with 60 ~ 100v/vh of air speed in United States Patent (USP) US3444251, passes through tubular reactor in 420 DEG C
Interior catalyst layer, catalyst are with standby ZnCl2The α aluminium of dipping and aluminum fluoride etc. can obtain the VDF of different yields.United States Patent (USP)
MeCClF is mentioned in US27747993, MeCCl2F or CH2ClCHF2By being catalyzed MgF2Copper pipe, be heated to 630 ~ 660oC connects
5 ~ 30s of time is touched, 96% ~ 98% VDF can be obtained.HCFC-142b is by being loaded on active carbon in German patent DE 1625568
Ferric flouride, in 300oC is reacted with certain flow rate, and HCFC-142b conversion ratio is 93%, and VDF/ fluorine vinyl chloride is about 99 in product:
1。
HCl is the Main By product that HCFC-142b and HCFC-142 cracking reaction generates, and the HCl of high concentration is catalyst
The severe challenge that faces of service life.Through frequently with metal chloride, metal fluoride, metal in the HCl atmosphere of highly corrosive
The compound of the highly corrosion resistants such as oxide, the metal salt of active carbon (AC) and dipping on the activated carbon is as catalyst.Catalysis
Although cracking has many advantages, such as but equally has the stability of its disadvantage, especially catalyst and service life difference is to lead to catalytic pyrolysis
It cannot industrialized main cause.Therefore need to develop that a kind of service life is high, stability is good, resistance to HCl and HF corrosion and can answer
Use catalyst system catalytic pyrolysis HCFC-142b and HCFC-142 the selectivity dehydrochlorination of industrialized production.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide a kind of vinylidene fluorides
Preparation method, the preparation method is simple, stability is good, vinylidene fluoride selectivity is high and method and step is simple and is easy to work
Industry.
The preparation method of a kind of vinylidene fluoride, it is characterised in that composite catalyst is packed into pipe reaction
In device, with the fluoro- 1- chloroethanes of 1,1- bis- or 1, the fluoro- 2- chloroethanes of 1- bis- is that raw material is passed through in the tubular reactor, carries out gas
Vinylidene fluoride is made in phase catalytic cracking reaction；The composite catalyst is metal composite fluoride.
The preparation method of a kind of vinylidene fluoride, it is characterised in that the metal in metal composite fluoride was
Cross metal, alkaline-earth metal or lanthanide series metal, transition metal Fe, Co, Cr, Zr or Zn, alkaline-earth metal Mg, Ca, Sr or Ba, lanthanum
Be metal be La, Ce or Sm.
A kind of preparation method of vinylidene fluoride, it is characterised in that the metal in the metal composite fluoride
For at least two in Fe, Co, Cr, Zr, Zn, Mg, Ca, Sr, Ba, La, Ce, Sm, it is with metallic element total moles percentage composition
The molar content of 100% meter, any one metal is no more than 75%.
The preparation method of a kind of vinylidene fluoride, it is characterised in that 1,1- bis- fluoro- 1- chloroethanes or 1,1- bis-
Fluoro- 2- chloroethanes uses N2It is passed through in tubular reactor and is reacted after being diluted, N2With the fluoro- 1- chloroethanes of 1,1- bis- or 1,
The volume ratio that feeds intake of the fluoro- 2- chloroethanes of 1- bis- is 1~9:1.
The preparation method of a kind of vinylidene fluoride, it is characterised in that the temperature of gas phase catalysis cracking reaction is
250 ~ 550 DEG C, reaction pressure is normal pressure, 1,1- bis- fluoro- 1- chloroethanes or 1, the Feed space velocities 20 of the fluoro- 2- chloroethanes of 1- bis-~
6000 h-1。
The preparation method of a kind of vinylidene fluoride, it is characterised in that tubular reactor is nickel tube.
The preparation method of a kind of vinylidene fluoride, it is characterised in that the preparation method of composite catalyst includes
The precipitation method and solid-phase sequencing；
The precipitation method preparation process is as follows:
The soluble salt of (1) at least two metal is added in container and is added water, and solid NH is added after being mixed evenly4F shape
At precipitating, continues to stir 2h or more, obtain precipitating mixed liquor；
(2) composite catalyst is made through drying, roasting in precipitating mixed liquor filtering obtained by step (1), filter residue；
The solid-phase sequencing preparation process is as follows:
After the carbonate or hydroxide ground and mixed of S1: at least two metals are uniform, (NH is added4)2SiF6Continue grinding at least
0.5h obtains milled mixtures；
S2: the composite catalyst is made through drying, roasting 5h in milled mixtures obtained by step S1.
The preparation method of a kind of vinylidene fluoride, it is characterised in that filter residue, solid-phase sequencing in the precipitation method
In milled mixtures are dry, roasting condition is identical, specifically: at 100-120 DEG C after at least dry 10h, at 400 ~ 600 DEG C
Lower roasting at least 4h.The preparation method of a kind of vinylidene fluoride, it is characterised in that according to claim 1 one
The preparation method of kind vinylidene fluoride, it is characterised in that composite catalyst is packed into before tubular reactor, first in drying
At least 2h is dried in case at 110 DEG C.
The preparation method of a kind of vinylidene fluoride, it is characterised in that specific step is as follows: by answering after drying
Mould assembly Catalyst packing enters in tubular reactor and is passed through N2, by the temperature of composite catalyst bed with the heating of 5 DEG C/min
Rate rises to 200 DEG C from room temperature, in N2In the case that flow is constant, then it is passed through 1, the fluoro- 1- chloroethanes of 1- bis- or 1, the fluoro- 2- of 1- bis-
Chloroethanes handle 2 h, then by the temperature of composite catalyst bed with the heating rate of 5 DEG C/min rise to 250 ~ 550 DEG C into
Row catalysis reaction, generates vinylidene fluoride.
By using the above method, compared with the conventional method, beneficial effects of the present invention are as follows:
1) present invention uses the fluoro- 1- chloroethanes of 1,1- bis- or 1, and the fluoro- 2- chloroethanes of 1- bis- is raw material, and raw material is cheap and easy to get, cost
Low, the present invention translates into added value height, environmental-friendly fluorochemical monomer using it as raw material, and catalytic pyrolysis route belongs to
Environmentally protective process route, it is environmentally protective, Social benefit and economic benefit is significant, wherein with 1, the fluoro- 2- chloroethanes of 1- bis-
(HCFC-142) it not only can be salvaged for raw material, can more reduce production and processing cost；
2) method provided by the invention for preparing vinylidene, using cheap composite metallic catalyst as catalyst, at
This is lower, prepares simple and effective and environmentally protective；
3) method provided by the invention for preparing vinylidene overcomes that prior art energy consumption is high, carbon distribution is serious, continuous production
The disadvantages of time is short, has reached that high income, step are few, are easy to industrialized purpose.The present invention passes through the selection of reactant and anti-
The production of the vinylidene of high-purity may be implemented in the control for answering condition.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1:
Two kinds of each 0.01mol of transition metal nitrate are taken to be added in container and 100mL water is added first.After being mixed evenly
0.04-0.06mol solid NH is added4F needed for F(is capable of forming precipitating by two kinds of metals-Calculate) precipitating is formed, and continue to stir
It is filtered after 2h.By the solid obtained after filtering in 110 DEG C of dry 12h, and 4h is roasted at 500 DEG C and obtains transition metal fluorine
The composite catalyst of compound.
Then the obtained composite catalyst catalysis fluoro- 1- chloroethanes of 1,1- bis- is taken off into HCl and prepares vinylidene.Reaction is
It is carried out in plug flow reactor, the reaction tube of plug flow reactor uses internal diameter 20mm, and length is 800mm's
Ni pipe, composite catalyst are packed into plug flow reactor, are placed in heat temperature raising in heating furnace, are warming up to 350 DEG C
It is reacted.Reaction pressure is normal pressure.
Before reaction, it is being passed through N2(air speed 1000h-1) in the case where, by composite catalyst bed temperature from room temperature
200 DEG C of 2 h of drying are risen to the heating rate of 5 DEG C/min, after then rising to 400 DEG C of 2 h of processing with the heating rate of 5 DEG C/min
It is cooled to 200 DEG C.In N2In the case that flow is constant, being passed through HCFC-142b(air speed is 600h-1) reprocessing 2 h of catalyst.So
Stop being passed through HCFC-142b afterwards, and temperature is risen to 350 DEG C of reaction temperature.Then HCFC-142b and N are passed through2Gaseous mixture into
(total air speed is 1200 h to promoting the circulation of qi phase catalytic reaction-1, HCFC-142b and N2Input material volume ratio 1:1).The tail gas generated is reacted through urgency
Vinylidene is obtained after cold, alkali cleaning, washing, drying, compression, rectification and purification.It is counted on the basis of the consumption of HCFC-142b
It calculates, obtains the conversion ratio and selectivity such as the following table 1 of partial catalyst:
Table 1
Embodiment 2
Two kinds of each 0.01mol of alkaline earth nitrate are taken to be added in container and 100mL water is added first.After being mixed evenly
0.04mol solid NH is added4F forms precipitating, and continues to be filtered after stirring 2h.By the solid obtained after filtering at 110 DEG C
Dry 12h, and roast 4h at 500 DEG C and obtain the composite catalyst of alkali earth metal fluoride.
Then the obtained composite catalyst catalysis fluoro- 1- chloroethanes of 1,1- bis- is taken off into HCl and prepares vinylidene.Reaction is
It is carried out in plug flow reactor, the reaction tube of plug flow reactor uses internal diameter 20mm, and length is 800mm's
Ni pipe, composite catalyst are packed into plug flow reactor, are placed in heat temperature raising in heating furnace, are warming up to 350 DEG C
It is reacted.Reaction pressure is normal pressure.
Before reaction, it is being passed through N2(air speed 1000h-1) in the case where, by composite catalyst bed temperature from room temperature
200 DEG C of 2 h of drying are risen to the heating rate of 5 DEG C/min, after then rising to 400 DEG C of 2 h of processing with the heating rate of 5 DEG C/min
It is cooled to 200 DEG C.In N2In the case that flow is constant, being passed through HCFC-142b(air speed is 600h-1) reprocessing 2 h of catalyst.So
Stop being passed through HCFC-142b afterwards, and temperature is risen to 350 DEG C of reaction temperature.Then HCFC-142b and N are passed through2Mixing
Gas carries out gas phase catalytic reaction, and (total air speed is 1200 h-1, HCFC-142b and N2Input material volume ratio 1:1).React the tail gas generated
Vinylidene is obtained after chilling, alkali cleaning, washing, drying, compression, rectification and purification.On the basis of the consumption of HCFC-142b
It calculates, obtains the conversion ratio and selectivity such as the following table 2 of partial catalyst:
Table 2
Embodiment 3
It takes two kinds of each 0.01mol of alkaline earth metal hydroxide to be added in grinding first, 0.02mol is added after being mixed evenly
(NH4)2SiF6, and continue after grinding at least 0.5h, by obtained solid in 110 DEG C of dry 12h, and 4h is roasted at 500 DEG C and is obtained
To the composite catalyst of alkali earth metal fluoride.
Then the obtained composite catalyst catalysis fluoro- 1- chloroethanes of 1,1- bis- is taken off into HCl and prepares vinylidene.Reaction is
It is carried out in plug flow reactor, the reaction tube of plug flow reactor uses internal diameter 20mm, and length is 800mm's
Ni pipe, composite catalyst are packed into plug flow reactor, are placed in heat temperature raising in heating furnace, are warming up to 350 DEG C
It is reacted.Reaction pressure is normal pressure.
Before reaction, it is being passed through N2(air speed 1000h-1) in the case where, by composite catalyst bed temperature from room temperature
200 DEG C of 2 h of drying are risen to the heating rate of 5 DEG C/min, after then rising to 400 DEG C of 2 h of processing with the heating rate of 5 DEG C/min
It is cooled to 200 DEG C.In N2In the case that flow is constant, being passed through HCFC-142b(air speed is 600h-1) reprocessing 2 h of catalyst.So
Stop being passed through HCFC-142b afterwards, and temperature is risen to 350 DEG C of reaction temperature.Then HCFC-142b and N are passed through2Gaseous mixture into
(total air speed is 1200 h to promoting the circulation of qi phase catalytic reaction-1, HCFC-142b and N2Input material volume ratio 1:1).The tail gas generated is reacted through urgency
Vinylidene is obtained after cold, alkali cleaning, washing, drying, compression, rectification and purification.It is counted on the basis of the consumption of HCFC-142b
It calculates, catalytic activity and VDF selectivity are substantially consistent in case study on implementation 2, but solid-phase sequencing has compared to the precipitation method
The SiF that processing prepares the waste water generated in catalyst process and roasting generates is not needed4The advantages that can recycling.
Embodiment 4
By the composite catalyst catalytic pyrolysis 1 in case study on implementation 3, the fluoro- 2- chloroethanes of 1- bis- takes off HCl and prepares vinylidene.
Reaction is carried out in plug flow reactor, and the reaction tube of plug flow reactor uses internal diameter
20mm, the Ni that length is 800mm are managed, and composite catalyst is packed into plug flow reactor, is placed in heating furnace and is added
Heat heating, is warming up to 400 DEG C and is reacted.Reaction pressure is normal pressure.
Before reaction, it is being passed through N2(air speed 1000h-1) in the case where, by composite catalyst bed temperature from room temperature
200 DEG C of 2 h of drying are risen to the heating rate of 5 DEG C/min, after then rising to 400 DEG C of 2 h of processing with the heating rate of 5 DEG C/min
It is cooled to 200 DEG C.In N2In the case that flow is constant, being passed through HCFC-142b(air speed is 600h-1) reprocessing 2 h of catalyst.So
Stop being passed through HCFC-142b afterwards, and temperature is risen to 400 DEG C of reaction temperature.Then HCFC-142b and N are passed through2Gaseous mixture into
(total air speed is 1200 h to promoting the circulation of qi phase catalytic reaction-1, HCFC-142b and N2Input material volume ratio 1:1).The tail gas generated is reacted through urgency
Vinylidene is obtained after cold, alkali cleaning, washing, drying, compression, rectification and purification.It is calculated on the basis of the consumption of HCFC-142,
Obtain the conversion ratio and selectivity such as the following table 3 of partial catalyst:
Table 3
Embodiment 5
Lanthanide metal nitrate lanthanum nitrate and each 0.01mol of cerous nitrate is taken to be added in container and 100mL water is added first.Mixing
It is stirring evenly and then adding into 0.06mol solid NH4F forms precipitating, and continues to be filtered after stirring 2h.Consolidate what is obtained after filtering
Body roasts 4h at 500 DEG C and obtains the composite catalyst of lanthanide series metal fluoride in 110 DEG C of dry 12h.
Then the obtained composite catalyst catalysis fluoro- 1- chloroethanes of 1,1- bis- is taken off into HCl and prepares vinylidene.Reaction is
It is carried out in plug flow reactor, the reaction tube of plug flow reactor uses internal diameter 20mm, and length is 800mm's
Ni pipe, composite catalyst are packed into plug flow reactor, are placed in heat temperature raising in heating furnace, are warming up to 350 DEG C
It is reacted.Reaction pressure is normal pressure.
Before reaction, it is being passed through N2(air speed 1000h-1) in the case where, by composite catalyst bed temperature from room temperature
200 DEG C of 2 h of drying are risen to the heating rate of 5 DEG C/min, after then rising to 400 DEG C of 2 h of processing with the heating rate of 5 DEG C/min
It is cooled to 200 DEG C.In N2In the case that flow is constant, being passed through HCFC-142b(air speed is 600h-1) reprocessing 2 h of catalyst.So
Stop being passed through HCFC-142b afterwards, and temperature is risen to 350 DEG C of reaction temperature.Then HCFC-142b and N are passed through2Gaseous mixture into
(total air speed is 1200 h to promoting the circulation of qi phase catalytic reaction-1, HCFC-142b and N2Input material volume ratio 1:1).The tail gas generated is reacted through urgency
Vinylidene is obtained after cold, alkali cleaning, washing, drying, compression, rectification and purification.
It is calculated on the basis of the consumption of HCFC-142b, LaCeF6HCFC-142b conversion ratio be 65%, VDF choosing
Selecting property reaches 80%.
Embodiment 6
A kind of lanthanide metal nitrate cerous nitrate and a kind of each 0.01mol of alkaline earth nitrate barium nitrate is taken to be added to appearance first
In device and 100mL water is added.0.05mol solid NH is added after being mixed evenly4F forms precipitating, and it is laggard to continue stirring 2h
Row filtering.By the solid obtained after filtering in 110 DEG C of dry 12h, and 4h is roasted at 500 DEG C and obtains lanthanide series metal-alkaline earth gold
Belong to the composite catalyst of fluoride.
Then the obtained composite catalyst catalysis fluoro- 1- chloroethanes of 1,1- bis- is taken off into HCl and prepares vinylidene.Reaction is
It is carried out in plug flow reactor, the reaction tube of plug flow reactor uses internal diameter 20mm, and length is 800mm's
Ni pipe, composite catalyst are packed into plug flow reactor, are placed in heat temperature raising in heating furnace, are warming up to 350 DEG C
It is reacted.Reaction pressure is normal pressure.
Before reaction, it is being passed through N2(air speed 1000h-1) in the case where, by composite catalyst bed temperature from room temperature
200 DEG C of 2 h of drying are risen to the heating rate of 5 DEG C/min, after then rising to 400 DEG C of 2 h of processing with the heating rate of 5 DEG C/min
It is cooled to 200 DEG C.In N2In the case that flow is constant, being passed through HCFC-142b(air speed is 600h-1) reprocessing 2 h of catalyst.So
Stop being passed through HCFC-142b afterwards, and temperature is risen to 350 DEG C of reaction temperature.Then HCFC-142b and N are passed through2Gaseous mixture into
(total air speed is 1200 h to promoting the circulation of qi phase catalytic reaction-1, HCFC-142b and N2Input material volume ratio 1:1).The tail gas generated is reacted through urgency
Vinylidene is obtained after cold, alkali cleaning, washing, drying, compression, rectification and purification.
It is calculated on the basis of the consumption of HCFC-142b, BaCeF5HCFC-142b conversion ratio be 60%, VDF choosing
Selecting property reaches 86%.
Embodiment 7
Take two kinds of alkaline earth nitrates (cerous nitrate and barium nitrate) and a kind of transition metal nitrate zinc nitrate each first
0.01mol is added in container and 100mL water is added.0.06-0.08mol solid NH is added after being mixed evenly4F(presses three
F needed for kind metal is capable of forming precipitating-Calculate) precipitating is formed, and continue to be filtered after stirring 2h.Consolidate what is obtained after filtering
Body roasts 4h at 500 DEG C and obtains the composite catalyst of earth metal-transition metal fluoride in 110 DEG C of dry 12h.
Then the obtained composite catalyst catalysis fluoro- 1- chloroethanes of 1,1- bis- is taken off into HCl and prepares vinylidene.Reaction is
It is carried out in plug flow reactor, the reaction tube of plug flow reactor uses internal diameter 20mm, and length is 800mm's
Ni pipe, composite catalyst are packed into plug flow reactor, are placed in heat temperature raising in heating furnace, are warming up to 350 DEG C
It is reacted.Reaction pressure is normal pressure.
Before reaction, it is being passed through N2(air speed 1000h-1) in the case where, by composite catalyst bed temperature from room temperature
200 DEG C of 2 h of drying are risen to the heating rate of 5 DEG C/min, after then rising to 400 DEG C of 2 h of processing with the heating rate of 5 DEG C/min
It is cooled to 200 DEG C.In N2In the case that flow is constant, being passed through HCFC-142b(air speed is 600h-1) reprocessing 2 h of catalyst.So
Stop being passed through HCFC-142b afterwards, and temperature is risen to 350 DEG C of reaction temperature.Then HCFC-142b and N are passed through2Gaseous mixture into
(total air speed is 1200 h to promoting the circulation of qi phase catalytic reaction-1, HCFC-142b and N2Input material volume ratio 1:1).The tail gas generated is reacted through urgency
Vinylidene is obtained after cold, alkali cleaning, washing, drying, compression, rectification and purification.
It is calculated on the basis of the consumption of HCFC-142b, BaSrZnF6The conversion ratio of HCFC-142b be 50%, VDF
Selectivity reaches 95%.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated, protection scope of the present invention is also only in those skilled in the art's root
According to present inventive concept it is conceivable that equivalent technologies mean.
Claims (10)
1. a kind of preparation method of vinylidene fluoride, it is characterised in that composite catalyst is packed into tubular reactor, with
1,1- bis- fluoro- 1- chloroethanes or 1, the fluoro- 2- chloroethanes of 1- bis- are that raw material is passed through in the tubular reactor, carry out gas phase catalysis and split
Solution reaction, is made vinylidene fluoride；The composite catalyst is metal composite fluoride.
2. a kind of preparation method of vinylidene fluoride according to claim 1, it is characterised in that metal composite fluoride
In metal be transition metal, alkaline-earth metal or lanthanide series metal, transition metal Fe, Co, Cr, Zr or Zn, alkaline-earth metal Mg,
Ca, Sr or Ba, lanthanide series metal La, Ce or Sm.
3. a kind of preparation method of vinylidene fluoride according to claim 2, it is characterised in that the metal composite fluorine
Metal in compound is at least two in Fe, Co, Cr, Zr, Zn, Mg, Ca, Sr, Ba, La, Ce, Sm, is always rubbed with metallic element
Your percentage composition is 100% meter, and the molar content of any one metal is no more than 75%.
4. a kind of preparation method of vinylidene fluoride according to claim 1, it is characterised in that 1,1- bis- fluoro- 1- chloroethene
Alkane or the fluoro- 2- chloroethanes of 1,1- bis- use N2It is passed through in tubular reactor and is reacted after being diluted, N2With the fluoro- 1- of 1,1- bis-
The volume ratio that feeds intake of chloroethanes or the fluoro- 2- chloroethanes of 1,1- bis- is 1~9:1.
5. a kind of preparation method of vinylidene fluoride according to claim 1, it is characterised in that gas phase catalysis cracking is anti-
The temperature answered is 250 ~ 550 DEG C, and reaction pressure is normal pressure, 1,1- bis- fluoro- 1- chloroethanes or 1, the charging of the fluoro- 2- chloroethanes of 1- bis-
20~6000 h of air speed-1。
6. a kind of preparation method of vinylidene fluoride according to claim 1, it is characterised in that tubular reactor is nickel
Pipe.
7. a kind of preparation method of vinylidene fluoride according to claim 1, it is characterised in that composite catalyst
Preparation method includes the precipitation method and solid-phase sequencing；
The precipitation method preparation process is as follows:
The soluble salt of (1) at least two metal is added in container and is added water, and solid NH is added after being mixed evenly4F is formed
Precipitating continues to stir 2h or more, obtains precipitating mixed liquor；
(2) composite catalyst is made through drying, roasting in precipitating mixed liquor filtering obtained by step (1), filter residue；
The solid-phase sequencing preparation process is as follows:
After the carbonate or hydroxide ground and mixed of S1: at least two metals are uniform, (NH is added4)2SiF6Continue grinding at least
0.5h obtains milled mixtures；
S2: the composite catalyst is made through drying, roasting 5h in milled mixtures obtained by step S1.
8. a kind of preparation method of vinylidene fluoride according to claim 7, it is characterised in that filter residue in the precipitation method,
Milled mixtures in solid-phase sequencing are dry, roasting condition is identical, specifically: at 100-120 DEG C after at least dry 10h,
At least 4h is roasted at 400 ~ 600 DEG C.
9. a kind of preparation method of vinylidene fluoride according to claim 1, it is characterised in that institute according to claim 1
The preparation method for a kind of vinylidene fluoride stated, it is characterised in that composite catalyst is packed into before tubular reactor, first
At least 2h is dried at 110 DEG C in drying box.
10. a kind of preparation method of vinylidene fluoride according to claim 9, it is characterised in that specific step is as follows:
Composite catalyst after drying is packed into tubular reactor and is passed through N2, by the temperature of composite catalyst bed with 5
DEG C/heating rate of min rises to 200 DEG C from room temperature, in N2In the case that flow is constant, then it is passed through 1, the fluoro- 1- chloroethanes of 1- bis-
Or 1, the fluoro- 2- chloroethanes of 1- bis- handles 2 h, then by the temperature of composite catalyst bed with the heating rate liter of 5 DEG C/min
Catalysis reaction is carried out to 250 ~ 550 DEG C, generates vinylidene fluoride.
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| CN111905779A (en) * | 2020-08-27 | 2020-11-10 | 浙江工业大学 | Multi-metal fluoride compound catalyst and preparation method and application thereof |
| CN112062651A (en) * | 2020-08-19 | 2020-12-11 | 浙江巨化技术中心有限公司 | Synthetic method of 1,1-difluoro-2-iodoethylene |
| CN113649032A (en) * | 2021-08-18 | 2021-11-16 | 金华永和氟化工有限公司 | Vinylidene fluoride catalyst and preparation method thereof |
| CN113893868A (en) * | 2021-10-29 | 2022-01-07 | 山东东岳化工有限公司 | Lanthanum-based catalyst for preparing 1, 1-difluoroethylene by catalytic cracking of 1, 1-difluoro-1-chloroethane and preparation method thereof |
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| CN113649032A (en) * | 2021-08-18 | 2021-11-16 | 金华永和氟化工有限公司 | Vinylidene fluoride catalyst and preparation method thereof |
| CN113649032B (en) * | 2021-08-18 | 2024-02-27 | 金华永和氟化工有限公司 | Vinylidene fluoride catalyst and preparation method thereof |
| CN113893868B (en) * | 2021-10-29 | 2023-06-23 | 山东东岳化工有限公司 | Lanthanum-based catalyst for preparing 1, 1-difluoroethylene by catalytic pyrolysis of 1, 1-difluoro-1-chloroethane and preparation method thereof |
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