CN106278805A - A kind of preparation method of vinylidene chloride monomer - Google Patents
A kind of preparation method of vinylidene chloride monomer Download PDFInfo
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- CN106278805A CN106278805A CN201610684935.5A CN201610684935A CN106278805A CN 106278805 A CN106278805 A CN 106278805A CN 201610684935 A CN201610684935 A CN 201610684935A CN 106278805 A CN106278805 A CN 106278805A
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- vinylidene chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only 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
- 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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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention discloses the preparation method of a kind of vinylidene chloride monomer, it is under catalyst existence condition, and chloromethanes, dichloromethane and oxygen reaction prepare vinylidene chloride monomer, and its reaction equation is: CH3Cl+CH2Cl2+1/2O2→C2H2Cl2+HCl+H2O；Described chloromethanes, dichloromethane sum are (0.5～10) with the mol ratio of oxygen: 1, and chloromethanes, dichloromethane mol ratio are (0.5～2): 1, and the reaction temperature of described reaction is 450～700 DEG C, and reaction pressure is 1～10atm.Raw material sources of the present invention are extensive, use single carbon atom raw material one step to generate double carbon vinylidene chloride monomer, and production cost is low, and three waste discharge is few, is a kind of vinylidene chloride monomer new technique for synthesizing, is suitable to popularization and application.
Description
Technical field
The present invention relates to the preparation method of a kind of vinylidene chloride monomer, be specifically related to a kind of employing chloromethanes and dichloromethane
Oxidative coupling prepares the method for vinylidene chloride monomer.
Background technology
Vinylidene chloride (CH2CCl2) it is a kind of important polymerization monomer, mainly for the production of vinylidene chloride-vinyl chloride, inclined chlorine
Ethylene-propylene nitrile and vinylidene chloride-acrylic acid esters co-polymer, product is widely used in national economy every field.Chloroethene partially
Alkene has multiple production method, by raw material route can be divided into vinyl chloride chloridising, vinyl chloride hydrogen chloride method, 1,2-dichloroethanes chlorination
Method and ethane chlorination method.
(1) vinyl chloride chloridising: this method is catalyst, reaction temperature 35～45 DEG C at iron chloride, and vinyl chloride is anti-with chlorine
Vinyl trichloride should be generated, then generate vinylidene chloride through alkaline hydrolysis saponification.This method is carried out in 1,1,2-trichloroethane
Chlorination reaction, chlorine and olefine reaction speed are than very fast.This technical process is simple, technology maturation, small investment, but conversion ratio is the highest,
Production cost is high, and the three wastes are many.Current domestic vinylidene chloride factory uses this technique substantially, and western developed country is the most no longer adopted
With.
(2) vinyl chloride hydrogen chloride method: this technique vinyl chloride and hydrogen chloride addition under catalyst aluminum chloride, iron chloride effect
Generating 1,1-dichloroethanes, 480 DEG C of high-temp chlorinations 1,1-dichloroethanes obtains vinylidene chloride and 1，1，1-trichloroethane, 510 DEG C
Pintsch process 1，1，1-trichloroethane obtains vinylidene chloride, this method coproduction trichloro ethylene.This method because of use thermal cracking dehydrochlorination, three
Useless few, in addition to a small amount of high-boiling components, basic no waste is discharged.This method technological process is long, and equipment is many, and the process development cycle is long, investment
Greatly.It is reported, The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, has this process unit.
(3) 1,2-dichloroethanes chloridising: 1,2-dichloroethanes and chlorine carry out halogenating reaction, generates 1,1,2-tri-chloroethene
Alkane, then obtain vinylidene chloride with alkali liquor removing hydrogen chloride.Vinylidene chloride technique processed and chlorine is reacted further by 1,1,2-trichloroethane
Ethylene chlorination method is similar.It is reported, reaction temperature is 115～120 DEG C, and reaction pressure is 0.1～0.5MPa, and liquid phase reacts,
Without catalyst, this technique is relatively simple, invests less, but reaction condition is the harshest, and three waste discharge is many.The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, and
Glass plate industrial group of Pittsburgh, BASF Aktiengesellschaft, Solvay of France, rising sun Dow Chemical Company of Japan, Wu Yu chemistry
Industrial group has this type of process unit.
(4) ethane chlorination method: this technique use ethane be raw material, when 426 DEG C chlorination become containing vinylidene chloride, hydrogen chloride,
Vinyl chloride, ethyl chloride, 1,1-dichloroethanes and the mixture of methyl chloroform, with rectificating method by above-mentioned product separately.Owing to adopting
Doing raw material with cheap ethane, cost is relatively low.Whole technique is in addition to a small amount of high-boiling components need to make burning disposal, and other products all obtain
Make full use of, almost without other three waste discharges, but long flow path, equipment is many, and investment is big, so far there are no this type of process unit
Report.
Above, although vinylidene chloride has a multiple production method, but its core basic simlarity, it is all with containing carbon number 2
Organic substance based on raw material, generate trichloroethane (1，1，1-trichloroethane or vinyl trichloride), then remove chlorination
Hydrogen is produced.Trichloroethane is converted into vinylidene chloride and has Pintsch process 1,1,1-trichloroethane method, alkaline hydrolysis 1,1,2-tri-chloroethene
Alkane method and 1,1,2-trichloroethane gas phase catalysis dehydrochlorination.First two method has been used for Large Scale Industrial Process, and technology is very
Maturation, later approach is still in conceptual phase.
1,1,2-trichloroethane gas phase catalysis dehydrochlorination is prepared the catalyst research of vinylidene chloride and has been delivered many patents
And paper.Such as Japan Patent (examined patent publication 56-53527 publication) (the flat second-101029 of publication number), United States Patent (USP) (USP
4816609) etc..British patent 2008117A describes in the presence of catalyst caesium halide, vinyl trichloride gas phase dechlorination
Change hydrogen reaction and prepare the process of vinylidene chloride.United States Patent (USP) 4144192 and 4225519 describes in catalyst cesium nitrate effect
Lower 1,1,2-trichloroethane dehydrochlorination reaction process.United States Patent (USP) 380762 discloses and utilizes chlorine (fluorine) to change potassium/rubidium/caesium gas phase
Dehydrochlorination process.Although vinyl trichloride gas phase catalysis dehydrochlorination has zero emission advantage, but catalyst is researched and developed
Investment cost is big, and the construction cycle is long, the most not yet realizes industrialization.
In sum, in figure 5 it can be seen that different vinylidene chloride preparation methods all use has the carbide acetylene of double carbon, stone
Based on oil ethylene or ethane, raw material prepares vinylidene chloride.Accordingly, consult domestic and international data of literatures, look for and whether have it
Its raw material process route prepares vinylidene chloride.The Japan Patent (JPH05262682) of an expired inefficacy has been found through retrieval
Outside relating to, other does not finds pertinent literature.This Japan Patent " preparation method of a kind of halocarbon hydride " proposes at catalyst
With under oxygen existence condition, halomethane and oxygen generation coupling reaction, preparing carbon number is 2 and above halocarbon hydride.Should
Patent used catalyst is the first component with alkali metal compound, with the first subgroup in the periodic table of elements, the second subgroup, the 5th
In subgroup, the 6th subgroup, the 7th subgroup, the 8th race, the 3rd main group, the 4th main group and the 5th main group in metallic compound one
Plant or several as second component.It should be noted that this patent used catalyst component does not comprise that to have oxidative coupling anti-
Should active alkaline-earth metal and rare earth element；Meanwhile, this patent proposes to prepare carbon number with halomethane for raw material is 2 and above halogen
Change hydrocarbons, but whether the clearest and the most definite product comprises vinylidene chloride, does not lists experimental product title in patent working case
And data.
Novelty of the present invention proposes a kind of employing chloromethanes, dichloromethane and oxygen direct reaction under catalyst action
The method preparing vinylidene chloride monomer.The method has been abandoned to prepare inclined chlorine containing raw material based on the Organic substance that carbon number is 2 completely
Ethylene, makes synthesis vinylidene chloride monomer raw material sources scope more extensive, and cost is lower, and process three waste discharge is few, is a kind of
Brand-new vinylidene chloride monomer synthesis technique.
Summary of the invention
The present invention provides a kind of methane chloride with single carbon directly to prepare the new side of vinylidene chloride monomer for raw materials for production
Method, compared with existing technology method, this method raw material sources are more extensive, it is possible to obtain inclined chlorine under lower production costs
Vinyl monomer.
For achieving the above object, the technical solution used in the present invention is:
The preparation method of a kind of vinylidene chloride monomer, under catalyst existence condition, chloromethanes, dichloromethane are anti-with oxygen
Should prepare vinylidene chloride monomer, described catalyst has oxidative dehydrogenation activity；
Gaseous state dichloromethane, chloromethanes and oxygen reaction, use catalyst that unstripped gas carries out activation preparation in the reaction
Obtaining vinylidene chloride monomer, its reaction equation is:
CH3Cl+CH2Cl2+1/2O2→C2H2Cl2+HCl+H2O (1)
Its possible reaction mechanism is:
O2→2O· (2)
2CH3Cl+O·→2CH2Cl·+H2O (3)
2CH2Cl2+O·→2CHCl2·+H2O (4)
CH2Cl·+CHCl2·→C2H2Cl2+HCl (5)
The possible reaction mechanism of its side reaction is:
2CH2Cl·→C2H3Cl+HCl (6)
2CHCl2·→C2HCl3+HCl (7)
According to reaction mechanism, it is the committed step that reaction occurs that oxygen fully activates as active oxygen species (O), from experiment
From the point of view of result, increase oxygen blending ratio, liter high reaction temperature, reduction feed gas flow rates are useful to improving feed stock conversion, but can not
Reduce vinylidene chloride selectivity with degree, produce vinyl chloride, trichloro ethylene, and a small amount of dichloroethanes, trichloroethane, tetrachloro
The by-products such as ethane.Therefore, select suitable catalyst and reaction condition, vinylidene chloride monomer can be obtained by high yield.
The active component of described catalyst is selected from alkaline-earth metal and compound, the rare earth metal with oxidative dehydrogenation activity
And one or more in compound；If alkaline-earth metal is magnesium, calcium, strontium and barium, and rare earth metal is lanthanum, cerium, neodymium and samarium,
These metallic compounds are with oxide, chloride, sulfide, phosphide, carbide, nitride, complex, organic metal salt etc.
Form plays catalytic action.
The auxiliary agent of catalyst of the present invention is main selected from transition metal and compound, alkali metal and compound thereof, the 3rd and four
One or more in race's metal and compound thereof, described transition metal be titanium, vanadium, copper, zirconium, molybdenum, zinc, chromium, tungsten, ferrum, cobalt,
Nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, silver, cadmium and gold；Described alkali metal is lithium, sodium, potassium, rubidium and caesium, the 3rd and four main groups
Metal is aluminum, gallium, germanium, stannum and lead.
Catalyst carrier of the present invention is selected from activated alumina, silicon dioxide, sieve and silica-sesquioxide, zeolite molecular sieve, titanium dioxide
One or more in titanium, zirconium oxide.Additionally, catalyst activity component, auxiliary agent comprise transition metal, alkaline-earth metal, rare earth
The compound of metal self also can be as catalyst carrier.Catalyst can be prepared by multiple preparation method, such as the sedimentation method, leaching
Stain method, heat melting method, the molten method of leaching, ion exchange, mechanical mixing, sol-gal process etc..
In the present invention, reaction temperature is 450～700 DEG C, and reaction pressure is 1～10atm, chloromethanes, dichloromethane it
And be (0.5～10) with the mol ratio of oxygen: 1, chloromethanes, dichloromethane mol ratio are (0.5～2): 1.
Compared with existing vinylidene chloride monomer preparation technology, innovative point of the present invention is as follows:
Use chloromethanes and dichloromethane oxidative coupling to prepare vinylidene chloride monomer, open one and new prepare inclined chloroethene
Alkene monomer raw material process route；Single carbon methane chloride is used to prepare the vinylidene chloride of double carbon as the direct step of raw materials for production,
Carbon Organic substances double with existing use prepare vinylidene chloride technique and are clearly distinguished from.And present invention process flow process is short, equipment is few, investment
Less, substantially without three wastes product withdraw, be suitable to popularization and application.
Accompanying drawing explanation
Fig. 1 technological process of production of the present invention schematic diagram
Detailed description of the invention
For being more clearly understood from the object of the invention, technical scheme and beneficial effect, below in conjunction with specific embodiment to this
Bright it is described further, but protection scope of the present invention is not limited in the examples below.
Seeing Fig. 1, the technological process of production of the present invention is: it is anti-that chloromethanes, dichloromethane and oxygen enter equipped with catalyst 2
Answer in device 1 and react；Chilling tower 3 is entered, through washing alkali cleaning dechlorinationization after chilling tower is lowered the temperature from reactor 1 product out
Hydrogen, condensation enters rectifying column 4 and carries out refrigerated separation of pressurizeing, gas phase chloromethanes, circulating oxygen reuse after removing water, liquid is the most partially
Vinyl chloride product (comprise dichloromethane, vinyl chloride, trichloro ethylene and the most undecomposed dichloroethanes completely, trichloroethane,
Sym-tetrachloroethane), as required, liquid is separated further, available pure vinylidene chloride monomer and other by-product.
According to the difference of used catalyst catalytic performance, the present invention is reactor used is fixed bed, fluid bed or movement
Bed.
Embodiment 1
It is that 1:1:1 mixes by chloromethanes, dichloromethane (heating and gasifying) and oxygen according to mol ratio, is passed through and does not loads
In the reactor of catalyst, at 600 DEG C, reacting under 1atm, product carries out component analysis after washing alkali cleaning.Chloromethane
Conversion ratio of alkane is 0.2%, and conversion ratio of dichloromethane is 0.6%, vinylidene chloride, vinyl chloride, trichloro ethylene selectivity
It respectively is 7%, 0.0%, 11%.
Embodiment 2
The precursor compound of barium is made solution according to a certain ratio, with Si-Al molecular sieve as carrier, uses infusion process
Prepare catalyst；Chloromethanes, dichloromethane (heating and gasifying) and oxygen are that 1:1:1 mixes according to mol ratio, are passed through filling
In the reactor of above-mentioned catalyst, at 600 DEG C, reacting under 1atm, product carries out component analysis after washing alkali cleaning,
Conversion ratio of chloromethanes is 38%, and conversion ratio of dichloromethane is 46%, and vinylidene chloride, vinyl chloride, trichloro ethylene select
Property respectively is 18%, 3%, 12%.
Embodiment 3
The precursor compound of barium, tungsten is made solution according to a certain ratio, with Si-Al molecular sieve as carrier, uses dipping
Legal system obtains catalyst, and chloromethanes, dichloromethane (heating and gasifying) and oxygen are that 2:1:1 mixes according to mol ratio, are passed through dress
Filling out in the reactor stating catalyst, at 600 DEG C, react under 1atm, product carries out composition after washing alkali cleaning and divides
Analysis.Conversion ratio of chloromethanes is 53%, and conversion ratio of dichloromethane is 74%, and vinylidene chloride, vinyl chloride, trichloro ethylene select
Selecting property respectively is 41%, 20%, 9%.
Embodiment 4
Barium, tungsten, the precursor compound of caesium are made solution according to a certain ratio, with Si-Al molecular sieve as carrier, uses
Infusion process prepares catalyst, and chloromethanes, dichloromethane (heating and gasifying) and oxygen are that 1:2:1 mixes according to mol ratio, logical
Entering in the reactor loading above-mentioned catalyst, at 600 DEG C, react under 1atm, product becomes after washing alkali cleaning
Analyze.Conversion ratio of chloromethanes is 72%, and conversion ratio of dichloromethane is 65%, vinylidene chloride, vinyl chloride, three chloroethenes
Alkene selectivity respectively is 48%, 12%, 13%.
Embodiment 5
Barium, tungsten, the precursor compound of caesium are made solution according to a certain ratio, with Si-Al molecular sieve as carrier, uses
Infusion process prepares catalyst, and chloromethanes, dichloromethane (heating and gasifying) and oxygen are that 5:5:1 mixes according to mol ratio, logical
Entering in the reactor loading above-mentioned catalyst, at 700 DEG C, react under 1atm, product becomes after washing alkali cleaning
Analyze.Conversion ratio of chloromethanes is 43%, and conversion ratio of dichloromethane is 66%, vinylidene chloride, vinyl chloride, three chloroethenes
Alkene selectivity respectively is 26%, 13%, 40%.
Embodiment 6
Lanthanum, strontium, the precursor compound of sodium are made solution according to a certain ratio, with titanium dioxide as carrier, uses leaching
Stain legal system obtains catalyst, and chloromethanes, dichloromethane (heating and gasifying) and oxygen are that 0.25:0.25:1 mixes according to mol ratio
Closing, be passed through in the reactor loading above-mentioned catalyst, at 500 DEG C, react under 1atm, product is laggard through washing alkali cleaning
Row component analysis.Conversion ratio of chloromethanes is 65%, and conversion ratio of dichloromethane is 77%, vinylidene chloride, vinyl chloride, three
Vinyl chloride selectivity respectively is 25%, 24%, 18%.
Embodiment 7
Calcium, molybdenum, stannum, the precursor compound of potassium are made solution according to a certain ratio, with silicon dioxide as carrier, uses
Infusion process prepares catalyst, and chloromethanes, dichloromethane (heating and gasifying) and oxygen are that 2:2:1 mixes according to mol ratio, logical
Entering in the reactor loading above-mentioned catalyst, at 450 DEG C, react under 10atm, product becomes after washing alkali cleaning
Analyzing, conversion ratio of chloromethanes is 38%, and conversion ratio of dichloromethane is 43%, vinylidene chloride, vinyl chloride, three chloroethenes
Alkene selectivity respectively is 22%, 19%, 10%.
Embodiment 8
Barium, nickel, chromium, the precursor compound of caesium are made solution according to a certain ratio, with silicon dioxide as carrier, uses
Infusion process prepares catalyst, and chloromethanes, dichloromethane (heating and gasifying) and oxygen are that 2:2:1 mixes according to mol ratio, logical
Entering in the reactor loading above-mentioned catalyst, at 550 DEG C, react under 1atm, product becomes after washing alkali cleaning
Analyze.Conversion ratio of chloromethanes is 67%, and conversion ratio of dichloromethane is 72%, vinylidene chloride, vinyl chloride, three chloroethenes
Alkene selectivity respectively is 55%, 18%, 15%.
As can be seen from the above embodiments, the inventive method can be prepared inclined chloroethene by chloromethanes and dichloromethane oxidative coupling
Alkene monomer, simultaneously by-product vinyl chloride and trichloro ethylene.
Claims (9)
1. the preparation method of a vinylidene chloride monomer, it is characterised in that: under catalyst existence condition, chloromethanes, dichloromethane
Alkane and oxygen reaction prepare vinylidene chloride monomer, and described catalyst has oxidative dehydrogenation activity, the active component of described catalyst
One or more in the alkaline-earth metal with oxidative dehydrogenation activity and compound, rare earth metal and compound thereof.
The preparation method of a kind of vinylidene chloride monomer the most according to claim 1, it is characterised in that there is oxidation de-described in:
The alkaline-earth metal of hydrogen activity is magnesium, calcium, strontium and barium, and rare earth metal is lanthanum, cerium, neodymium and samarium.
The preparation method of a kind of vinylidene chloride monomer the most according to claim 1, it is characterised in that: helping of described catalyst
Agent is selected from one in main group metal and compound thereof of transition metal and compound, alkali metal and compound thereof, the 3rd and four
Or it is several.
The preparation method of a kind of vinylidene chloride monomer the most according to claim 3, it is characterised in that: described transition metal is
Titanium, vanadium, copper, zirconium, molybdenum, zinc, chromium, tungsten, ferrum, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, silver, cadmium and gold；Described alkali metal
For lithium, sodium, potassium, rubidium and caesium；3rd and four main group metals are aluminum, gallium, germanium, stannum and lead.
5. according to the preparation method of a kind of vinylidene chloride monomer described in claim 1 or 3, it is characterised in that: described compound
Including oxide, chloride, sulfide, phosphide, carbide, nitride, complex and organic metal salt.
The preparation method of a kind of vinylidene chloride monomer the most according to claim 1, it is characterised in that: the load of described catalyst
Body one or several in activated alumina, silicon dioxide, sieve and silica-sesquioxide, zeolite molecular sieve, titanium dioxide, zirconium oxide
Kind.
The preparation method of a kind of vinylidene chloride monomer the most according to claim 1, it is characterised in that: described chloromethanes, two
Chloromethanes sum is (0.5～10) with the mol ratio of oxygen: 1, and chloromethanes, dichloromethane mol ratio are (0.5～2): 1.
The preparation method of a kind of vinylidene chloride monomer the most according to claim 1, it is characterised in that: the reaction of described reaction
Temperature is 450～700 DEG C.
The preparation method of a kind of vinylidene chloride monomer the most according to claim 1, it is characterised in that: the reaction of described reaction
Pressure is 1～10atm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573209A (en) * | 2017-08-16 | 2018-01-12 | 宜宾天原集团股份有限公司 | A kind of preparation method of VCM |
| WO2022189513A1 (en) | 2021-03-11 | 2022-09-15 | Lonza Ltd | Methods of detecting peroxo compounds in samples |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144192A (en) * | 1977-11-18 | 1979-03-13 | Ppg Industries, Inc. | Dehydrochlorination catalyst |
| JPH05262682A (en) * | 1992-03-23 | 1993-10-12 | Tosoh Corp | Production of halogenated hydrocarbon compound |
-
2016
- 2016-08-18 CN CN201610684935.5A patent/CN106278805B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144192A (en) * | 1977-11-18 | 1979-03-13 | Ppg Industries, Inc. | Dehydrochlorination catalyst |
| JPH05262682A (en) * | 1992-03-23 | 1993-10-12 | Tosoh Corp | Production of halogenated hydrocarbon compound |
Non-Patent Citations (1)
| Title |
|---|
| VAIBHAV GAIKWAD, ET AL.,: "Reaction of dichloromethane under non-oxidative conditions in a dielectric barrier discharge reactor and characterisation of the resultant polymer", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573209A (en) * | 2017-08-16 | 2018-01-12 | 宜宾天原集团股份有限公司 | A kind of preparation method of VCM |
| WO2022189513A1 (en) | 2021-03-11 | 2022-09-15 | Lonza Ltd | Methods of detecting peroxo compounds in samples |
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