CN109293470A - A kind of process of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction - Google Patents

A kind of process of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction Download PDF

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CN109293470A
CN109293470A CN201811134107.XA CN201811134107A CN109293470A CN 109293470 A CN109293470 A CN 109293470A CN 201811134107 A CN201811134107 A CN 201811134107A CN 109293470 A CN109293470 A CN 109293470A
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acetylene
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catalytic pyrolysis
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CN109293470B (en
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韩文锋
周胜兰
李西良
刘兵
唐浩东
李瑛�
刘化章
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0252—Nitrogen containing compounds with a metal-nitrogen link, e.g. metal amides, metal guanidides
    • 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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Abstract

The invention discloses the processes of a kind of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterized in that filling nitrating C catalyst or pattern of fusion catalyst in fixed bed reactors, HCFC-142b and acetylene are passed through in fixed bed reactors together to be reacted, raw material of the HCl that HCFC-142b catalytic pyrolysis generates as acetylene hydrochlorination, reaction generate vinylidene and vinyl chloride.The features such as catalyst has the function of while being catalyzed HCFC-142b cracking and acetylene hydrochlorination in process provided by the invention, and stability is good, and preparation process is simple.Compared with existing HCFC-142b cracks VDF technique processed, greatly reduce reaction temperature, the energy is saved, and it is passed through the byproduct hydrogen chloride that HCFC-142b is cracked to form by acetylene and is changed into vinyl chloride, the expense that industrial HCFC-142b cracks VDF processing hydrogen chloride processed is greatly saved, and turn waste into wealth, it is also more environmentally-friendly to prepare vinyl chloride production method ratio with traditional acetylene method mercury catalysis.

Description

A kind of process of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction
Technical field
The present invention relates to the processes of a kind of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction.
Background technique
Vinylidene is important one of the monomer of fluorine chemical industry, mainly for the production of Kynoar and fluorubber.It is poly- Vinylidene is a kind of high comprehensive performance, widely used thermoplastic engineering plastic, is mainly used for chemical industry equipment, electronics electricity The fields such as gas, piezoelectric material, lithium battery and building coating.The fluorubber that vinylidene, hexafluoropropene, tetrafluoroethene are copolymerized Become modern industry especially high-tech because of its outstanding heat-resisting quantity, oil resistivity, solvent resistance and physical and mechanical property to lead Indispensable and substitution basic material in domain.
Vinyl chloride is a kind of widely used chemical raw material, mainly to manufacture homopolymer and the copolymerization of polyvinyl chloride Object is the important source material of plastics industry, can also make refrigerant etc..The commercial synthesis method of vinyl chloride monomer mainly has acetylene at present Hydrogen chloride method and process for oxychlorination of ethylene.
Currently, HCFC-142b(1- chlorine-1,1-difluoroethane) industrially most common method is blank pipe cracking to dehydrochlorination Method, the reaction temperature of blank pipe cracking process is high, and energy consumption is high, and cracking tube service life is short, and a large amount of hydrogen chloride generated are formed Higher Environmental costs.Catalytic pyrolysis can be such that the reaction activity of HCFC-142b dehydrochlorination significantly reduces, so as to drop Low reaction temperatures reduce energy consumption.Same catalytic pyrolysis can inhibit the generation of side reaction to be conducive to improve the selection of product Property.Catalytic cracking catalyst mainly active charcoal, metal oxide and metal fluoride.In United States Patent (USP) US3444251 HCFC-142b is with 60 ~ 100 h of air speed-1, in 420 DEG C by the catalyst layer in tubular reactor, catalyst is with standby ZnCl2 The α aluminium of dipping and aluminum fluoride etc. can obtain the VDF of different yields.MeCClF is mentioned in United States Patent (USP) US27747993, MeCCl2F or CH2ClCHF2By being catalyzed MgF2Copper pipe, be heated to 630 ~ 660 DEG C, 5 ~ 30s of time of contact, can be obtained 96% ~ 98% VDF. HCFC-142b is reacted by the ferric flouride being loaded on active carbon in 300 DEG C with certain flow rate in German patent DE 1625568, HCFC-142b conversion ratio is 93%, and VDF/ fluorine vinyl chloride is about 99:1 in product.Although catalytic pyrolysis has many advantages, such as but same There is the stability of its disadvantage, especially catalyst and service life difference is causes catalytic pyrolysis cannot industrialized main cause.Specially Sharp CN201611237027 and CN201710034557 discloses nitrating C catalyst and Ba base catalyst, reached high income, Step is few, is easy to industrialized purpose.
Currently, the mercury catalyst that acetylene hydrochlorination method uses faces more and more environmental protection pressures.Therefore, more and more notes Meaning power focuses in the exploitation of non-mercury catalyst.Therefore, Au catalyst and other noble metal carrier catalysts, base metal are urged Agent etc. is gradually taken seriously.Patent CN201710218261 and CN201810022904, which are disclosed, utilizes nitrogen-doped carbon catalyst The method of catalyzing acetylene hydrogen chloride.
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 HCFC-142b catalysis The process of cracking and acetylene hydrochlorination coupling reaction, solution HCFC-142b production energy consumption is big, hydrogen chloride product processing trouble The problem of.
A kind of process of the HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterised in that Filling nitrating C catalyst or pattern of fusion catalyst, HCFC-142b and nitrogen are passed through with certain proportion in fixed bed reactors It is reacted in fixed bed reactors, is passed through acetylene, HCFC-142b and acetylene integral molar quantity and nitrogen mole after reacting 2-12h Than for 1:1, reaction generates vinylidene and vinyl chloride, the HCl that wherein HCFC-142b catalytic pyrolysis generates is as acetylene hydrochlorination Raw material, while in two reaction process of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination, heat absorption and heat release are complementary, a side The effective use of by-product HCl is realized in face, and the coupling of reaction heat may be implemented in next, to realize effective use and the energy of material Optimization.
A kind of process of the HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterised in that Reaction temperature is 220 ~ 400 DEG C, and total air speed of HCFC-142b and acetylene is 50h ~ 1200h-1, the charging mole of acetylene and R142b Than for 1:1 ~ 4.
A kind of process of the HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterised in that Nitrating C catalyst is to load nitrogenous compound using active carbon as carrier；In the nitrating C catalyst, nitrogenous compound and work Property charcoal mass ratio be 0.5 ~ 2:1.
A kind of process of the HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterised in that Nitrating C catalyst the preparation method comprises the following steps: by washing and drying after active carbon pickling, be placed in flask, add nitrogenous compound and anhydrous Ethyl alcohol is stirred at reflux, then is dried, in a nitrogen atmosphere calcination activation.
A kind of process of the HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterised in that The specific preparation step of nitrating C catalyst are as follows: take active carbon to carry out pickling, pickling time is 2 ~ 6h, and the pickling solution is salt One or more of the aqueous solution of acid, sulfuric acid or nitric acid mixed solution, sour mass concentration are 10 ~ 30%, will be active after pickling Charcoal is placed in 80 ~ 110 DEG C of dryings, and drying time is 10 ~ for 24 hours, the active carbon after drying process is spare as carrier；By nitrogenous chemical combination Object and ethyl alcohol are added in the active carbon after above-mentioned pickling drying, and the mass ratio of the nitrogenous compound and active carbon is 0.5 ~ 2:1, It is stirred at reflux 4 ~ 10h under water bath condition, then evaporates ethyl alcohol, after re-dry, lives under nitrogen protection in 200 ~ 800 DEG C Change, activation time is 2 ~ 12h, obtains nitrating C catalyst.
A kind of process of the HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterised in that Pattern of fusion catalyst the preparation method comprises the following steps: by PVDF, barium salt and nitrogenous compound mechanical lapping mix after, be added DMF it is sufficiently molten Solution is mixed and dried, and is roasted in a nitrogen atmosphere to get the pattern of fusion catalyst；The barium salt is acetylacetone barium or acetic acid Barium.
A kind of process of the HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterised in that Maturing temperature is 300 ~ 700 DEG C, and calcining time is 2 ~ 6h.
A kind of process of the HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterised in that The nitrogenous compound is melamine or urea, preferably melamine.
Compared with prior art, the invention has the following beneficial effects:
(1) catalyst has while being catalyzed the work of HCFC-142b cracking and acetylene hydrochlorination in process provided by the invention With, and the features such as stability is good, and preparation process is simple.Compared with existing HCFC-142b cracks VDF technique processed, substantially reduce Reaction temperature, has saved the energy, and be passed through the byproduct hydrogen chloride that HCFC-142b is cracked to form by acetylene and be changed into chloroethene Alkene is greatly saved industrial HCFC-142b and cracks the expense of VDF processing hydrogen chloride processed, and turns waste into wealth, with traditional acetylene method mercury It is also more environmentally-friendly that catalysis prepares vinyl chloride production method ratio.It is anti-to carry out the two on same catalyst simultaneously in same reactor It answers, equipment cost more low energy consumption decreases.
(2) mechanism of HCFC-142b cracking and acetylene hydrochlorination reaction is as follows:
CH3CClF2 → CH2=CF2 + HCl；
CH≡CH + HCl → CH2=CHCl；
Reaction temperature can be reduced to 300 DEG C or so from 600 ~ 700 DEG C to HCFC-142b cracking reaction under the action of catalyst.And root According to thermodynamics of reactions, at 350 DEG C, HCFC-142b cracking reaction 93.13 kJ/mol of heat absorption, and the corresponding heat release of acetylene hydrochlorination 93.17 kJ/mol.Therefore, two reactions can be coupled, on the one hand by-product HCl can be efficiently used, secondly The coupling of reaction heat may be implemented, to realize the effective use of material and energy-optimised.
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.
In following example 1 ~ 6, the processing step of the absorbent charcoal carrier are as follows: be with mass concentration by cocoanut active charcoal 20% aqueous solution of nitric acid is cleaned after impregnating 2h, and then in 110 DEG C of dry 12h, the cocoanut active charcoal after drying process is as carrier It is spare.
Embodiment 1
Cocoanut active charcoal after taking 5g melamine and 10g to be dried is put into flask, and the anhydrous second of 80mL is added in flask Alcohol, solvent, (is evaporated) by water-bath reflux 6h after dry under conditions of 60 DEG C, 500 r/min, leads to nitrogen gas in 600 DEG C of high temperature 5h is activated under atmosphere, nitrating C catalyst is made.The chloro- 1,1- Difluoroethane gas of 1- is passed through equipped with the nitrating C catalyst In fixed bed reactors, reaction temperature is 250 DEG C, is passed through acetylene, the charging of 1- chlorine-1,1-difluoroethane and acetylene after reacting 4h Molar ratio is 2:1, and total air speed of 1- chlorine-1,1-difluoroethane and acetylene is 180h-1.Reaction obtains as a result, chloro- 1, the 1- difluoro of 1- The conversion ratio of ethane is 20%, conversion of alkyne 25%, and the selectivity of vinylidene is up to 90% or more, the selectivity of vinyl chloride 100%。
Embodiment 2
Cocoanut active charcoal after taking 10g melamine and 10g to be dried is put into flask, and the anhydrous second of 80mL is added in flask Alcohol, water-bath reflux 6h under conditions of 60 DEG C, 500 r/min after dry, activate 5h in the case where 650 DEG C of high temperature lead to nitrogen atmosphere, make Obtain nitrating C catalyst.The chloro- 1,1- Difluoroethane gas of 1- is passed through the fixed bed reactors equipped with the nitrating C catalyst In, reaction temperature is 250 DEG C, is passed through acetylene after reacting 4h, and the raw materials components mole ratio of 1- chlorine-1,1-difluoroethane and acetylene is 3:1, Total air speed of the chloro- 1,1- Difluoroethane of 1- and acetylene is 180h-1.Reaction obtains the conversion ratio as a result, 1- chlorine-1,1-difluoroethane It is 15%, conversion of alkyne 30%, the selectivity of vinylidene is up to 90% or more, the selectivity 100% of vinyl chloride.
Embodiment 3
Cocoanut active charcoal after taking 20g melamine and 10g to be dried is put into flask, and the anhydrous second of 80mL is added in flask Alcohol, water-bath reflux 6h under conditions of 60 DEG C, 500 r/min after dry, activate 4h in the case where 700 DEG C of high temperature lead to nitrogen atmosphere, make Obtain nitrating C catalyst.The chloro- 1,1- Difluoroethane gas of 1- is passed through the fixed bed reactors equipped with the nitrating C catalyst In, reaction temperature is 250 DEG C, is passed through acetylene after reacting 4h, and the raw materials components mole ratio of 1- chlorine-1,1-difluoroethane and acetylene is 3:1, Total air speed of the chloro- 1,1- Difluoroethane of 1- and acetylene is 180h-1.Reaction obtains the conversion ratio as a result, 1- chlorine-1,1-difluoroethane It is 30%, conversion of alkyne 45%, the selectivity of vinylidene is up to 90% or more, the selectivity 100% of vinyl chloride.
Embodiment 4
Cocoanut active charcoal after taking 20g melamine and 10g to be dried is put into flask, and the anhydrous second of 80mL is added in flask Alcohol, water-bath reflux 6h under conditions of 60 DEG C, 500 r/min after dry, activate 4h in the case where 700 DEG C of high temperature lead to nitrogen atmosphere, make Obtain nitrating C catalyst.The chloro- 1,1- Difluoroethane gas of 1- is passed through the fixed bed reactors equipped with the nitrating C catalyst In, reaction temperature is 280 DEG C, is passed through acetylene after reacting 4h, and total air speed of 1- chlorine-1,1-difluoroethane and acetylene is 180h-1.Instead It should obtain as a result, the conversion ratio of 1- chlorine-1,1-difluoroethane is 40%, the selectivity of conversion of alkyne 40%, vinylidene reaches 90% or more, the selectivity 100% of vinyl chloride.
Embodiment 5
Cocoanut active charcoal after taking 20g melamine and 10g to be dried is put into flask, and the anhydrous second of 80mL is added in flask Alcohol, water-bath reflux 6h under conditions of 60 DEG C, 500 r/min after dry, activate 4h in the case where 700 DEG C of high temperature lead to nitrogen atmosphere, make Obtain nitrating C catalyst.The chloro- 1,1- Difluoroethane gas of 1- is passed through the fixed bed reactors equipped with the nitrating C catalyst In, reaction temperature is 350 DEG C, is passed through acetylene after reacting 4h, and the raw materials components mole ratio of 1- chlorine-1,1-difluoroethane and acetylene is 2:1, Total air speed of the chloro- 1,1- Difluoroethane of 1- and acetylene is 180h-1.Reaction obtains the conversion ratio as a result, 1- chlorine-1,1-difluoroethane It is 60%, conversion of alkyne 60%, the selectivity of vinylidene is up to 90% or more, the selectivity 100% of vinyl chloride.
Embodiment 6
Cocoanut active charcoal after taking 20g melamine and 10g to be dried is put into flask, and the anhydrous second of 80mL is added in flask Alcohol, water-bath reflux 6h under conditions of 60 DEG C, 500 r/min after dry, activate 4h in the case where 700 DEG C of high temperature lead to nitrogen atmosphere, make Obtain nitrating C catalyst.The chloro- 1,1- Difluoroethane gas of 1- is passed through the fixed bed reactors equipped with the nitrating C catalyst In, reaction temperature is 350 DEG C, is passed through acetylene after reacting 4h, and the raw materials components mole ratio of 1- chlorine-1,1-difluoroethane and acetylene is 2.5: Total air speed of 1,1- chlorine-1,1-difluoroethane and acetylene is 600h-1.Reaction obtains the conversion as a result, 1- chlorine-1,1-difluoroethane Rate is 40%, conversion of alkyne 40%, and the selectivity of vinylidene is up to 90% or more, the selectivity 100% of vinyl chloride.
Embodiment 7
10.2g barium acetate is taken, 2.56g PVDF, 3.6g melamine carries out mechanical lapping, 15mL DMF is added after grinding sufficiently, It is sufficiently stirred, 400 DEG C of roasting 4h are washed and are centrifuged with dilute hydrochloric acid immersion ultrasound 2h after taking-up in a nitrogen atmosphere after drying, dry Obtain pattern of fusion catalyst.The chloro- 1,1- Difluoroethane gas of 1- is passed through the fixed bed reactors equipped with the pattern of fusion catalyst In, reaction temperature is 350 DEG C, is passed through acetylene after reacting 4h, and the raw materials components mole ratio of 1- chlorine-1,1-difluoroethane and acetylene is 3:1, Total air speed of the chloro- 1,1- Difluoroethane of 1- and acetylene is 180h-1.Reaction obtains the conversion ratio as a result, 1- chlorine-1,1-difluoroethane It is 20%, conversion of alkyne 15%, the selectivity of vinylidene is up to 99% or more, the selectivity 100% of vinyl chloride.
Embodiment 8
10.2g barium acetate is taken, 2.56g PVDF, 3.6g melamine carries out mechanical lapping, 15mL DMF is added after grinding sufficiently, It is sufficiently stirred, 400 DEG C of roasting 2h are washed and are centrifuged with dilute hydrochloric acid immersion ultrasound 2h after taking-up in a nitrogen atmosphere after drying, dry Obtain pattern of fusion catalyst.The chloro- 1,1- Difluoroethane gas of 1- is passed through the fixed bed reactors equipped with the pattern of fusion catalyst In, reaction temperature is 350 DEG C, is passed through acetylene after reacting 4h, and the raw materials components mole ratio of 1- chlorine-1,1-difluoroethane and acetylene is 1:1, Total air speed of the chloro- 1,1- Difluoroethane of 1- and acetylene is 180h-1.Reaction obtains the conversion ratio as a result, 1- chlorine-1,1-difluoroethane It is 20%, conversion of alkyne 15%, the selectivity of vinylidene is up to 99% or more, the selectivity 100% of vinyl chloride.
Embodiment 9
10.2g barium acetate is taken, 2.56g PVDF carries out mechanical lapping, and 15mL DMF is added after grinding sufficiently, is sufficiently stirred, dries 400 DEG C of roasting 2h are washed and are centrifuged with dilute hydrochloric acid immersion ultrasound 2h after taking-up in a nitrogen atmosphere afterwards, dry that pattern of fusion is catalyzed Agent.1- chlorine-1,1-difluoroethane gas is passed through in the fixed bed reactors equipped with the pattern of fusion catalyst, reaction temperature is 350 DEG C, acetylene is passed through after reacting 4h, and the raw materials components mole ratio of 1- chlorine-1,1-difluoroethane and acetylene is 2:1, chloro- 1, the 1- difluoro of 1- Total air speed of ethane and acetylene is 180h-1.Reaction obtains as a result, the conversion ratio of 1- chlorine-1,1-difluoroethane is 50%, and acetylene is not Reaction, the selectivity of vinylidene is up to 95% or more.
Embodiment 10
10.2g barium acetate is taken, 2.56g PVDF, 2.4g melamine carries out mechanical lapping, 15mL DMF is added after grinding sufficiently, It is sufficiently stirred, 400 DEG C of roasting 2h are washed and are centrifuged with dilute hydrochloric acid immersion ultrasound 2h after taking-up in a nitrogen atmosphere after drying, dry Obtain pattern of fusion catalyst.The chloro- 1,1- Difluoroethane gas of 1- is passed through the fixed bed reactors equipped with the pattern of fusion catalyst In, reaction temperature is 350 DEG C, is passed through acetylene after reacting 4h, and the raw materials components mole ratio of 1- chlorine-1,1-difluoroethane and acetylene is 2:1, Total air speed of the chloro- 1,1- Difluoroethane of 1- and acetylene is 180h-1.Reaction obtains the conversion ratio as a result, 1- chlorine-1,1-difluoroethane It is 20%, conversion of alkyne 15%, the selectivity of vinylidene is up to 95% or more, the selectivity 100% of vinyl chloride.
Embodiment 11
10.2g barium acetate is taken, 2.56g PVDF, 1.2g melamine carries out mechanical lapping, 15mL DMF is added after grinding sufficiently, It is sufficiently stirred, 400 DEG C of roasting 2h are washed and are centrifuged with dilute hydrochloric acid immersion ultrasound 2h after taking-up in a nitrogen atmosphere after drying, dry Obtain pattern of fusion catalyst.The chloro- 1,1- Difluoroethane gas of 1- is passed through the fixed bed reactors equipped with the pattern of fusion catalyst In, reaction temperature is 350 DEG C, is passed through acetylene after reacting 4h, and the raw materials components mole ratio of 1- chlorine-1,1-difluoroethane and acetylene is 3:1, Total air speed of the chloro- 1,1- Difluoroethane of 1- and acetylene is 180h-1.Reaction obtains the conversion ratio as a result, 1- chlorine-1,1-difluoroethane It is 25%, conversion of alkyne 35%, the selectivity of vinylidene is up to 90% or more, the selectivity 100% of vinyl chloride.
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 (7)

1. a kind of process of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction, it is characterised in that fixed bed is anti- Answer filling nitrating C catalyst or pattern of fusion catalyst in device, HCFC-142b and acetylene be passed through in fixed bed reactors together into Row reaction, raw material of the HCl that HCFC-142b catalytic pyrolysis generates as acetylene hydrochlorination, reaction generate vinylidene and chloroethene Alkene.
2. the process of a kind of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction according to claim 1, It is characterized in that reaction temperature is 220 ~ 400 DEG C, total air speed of HCFC-142b and acetylene is 50h ~ 1200h-1, acetylene and R142b Raw materials components mole ratio be 1:1 ~ 4.
3. the process of a kind of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction according to claim 1, It is characterized in that nitrating C catalyst is to load nitrogenous compound using active carbon as carrier；It is nitrogenous in the nitrating C catalyst The mass ratio of compound and active carbon is 0.5 ~ 2:1.
4. the process of a kind of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction according to claim 1, It is characterized in that nitrating C catalyst the preparation method comprises the following steps: by washing and drying after active carbon pickling, be placed in flask, add nitrogen Object and absolute ethyl alcohol and stirring reflux are closed, then is dried, in a nitrogen atmosphere calcination activation.
5. the process of a kind of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction according to claim 1, It is characterized in that pattern of fusion catalyst the preparation method comprises the following steps: by PVDF, barium salt and nitrogenous compound mechanical lapping mix after, be added DMF, which sufficiently dissolves, to be mixed and dried, and is roasted in a nitrogen atmosphere to get the pattern of fusion catalyst；The barium salt is acetylacetone,2,4-pentanedione Barium or barium acetate.
6. the process of a kind of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction according to claim 5, It is characterized in that maturing temperature is 300 ~ 700 DEG C, calcining time is 2 ~ 6h.
7. the technique side of a kind of HCFC-142b catalytic pyrolysis and acetylene hydrochlorination coupling reaction according to claim 4 or 5 Method, it is characterised in that the nitrogenous compound is melamine or urea, preferably melamine.
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