CN107573209A - A kind of preparation method of VCM - Google Patents
A kind of preparation method of VCM Download PDFInfo
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- CN107573209A CN107573209A CN201710704201.3A CN201710704201A CN107573209A CN 107573209 A CN107573209 A CN 107573209A CN 201710704201 A CN201710704201 A CN 201710704201A CN 107573209 A CN107573209 A CN 107573209A
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Abstract
The invention discloses a kind of preparation method of VCM, and it is under the catalyst existence condition with oxidative coupling of methane activity, and VCM is made in methane, dichloromethane and oxygen reaction, and its reaction equation is：CH4+CH2Cl2+1/2O2→C2H3Cl+H2O+HCl；The methane is 1 with dichloromethane sum and the mol ratio of oxygen: (0.2~2), methane are 1 with dichloromethane mol ratio: (0.5~2)；The reaction temperature of the reaction is 500~800 DEG C, and reaction pressure is 1~10atm.The inventive method raw material sources are extensive, cheap, and reaction condition is gentle, are a kind of new technologies of VCM synthesis, suitable for popularization and application.
Description
Technical field
The present invention relates to a kind of preparation method of VCM, and in particular to a kind of methane, the coupling of dichloromethane oxygenation
The method that reaction prepares VCM.
Background technology
Vinyl chloride (CH2CHCl it is) a kind of monomer important applied to macromolecule chemical industry, it is industrial a large amount of poly- as production
Vinyl chloride (PVC).At present, industrially the method for production VCM mainly has two kinds of process routes of acetylene method and ethylene process.
Acetylene method reacts under mercury catalyst (mercury chloride is carried on activated carbon) effect and closed using acetylene and hydrogen chloride as raw material
Into VCM, polymerization of vinyl choride monomer obtains PVC.This method technological process is simple, and conversion of alkyne is higher than 98%, chloroethene
Alkene is selectively higher than 99%, is to realize industrialized PVC production methods earliest.But this method mainly has two shortcomings, first, needing
To use the mercury catalyst of pollution environment；Second, for producing, there is highly energy-consuming in the calcium carbide of acetylene and high pollution is asked in process of production
Topic.
Ethylene process obtains VCM using ethene direct chlorination reaction generation dichloroethanes, dichloroethanes thermal cracking,
Polymerization of vinyl choride monomer obtains PVC.This method has the advantages of process units scale is big, cost is low, monomer purity is high.With generation
Boundary's petroleum resources are petered out, and oil ethene legal system PVC process routes are also begun to by the increasingly increased puzzlement of cost of material.
For this situation, the side using resourceful natural gas and shale gas principal component methane as Material synthesis vinyl chloride
Method is actively studied.United States Patent (USP) US4804797 report reaction temperature more than 1000 DEG C, without catalyst under conditions of
Allow methane and chlorine reaction, product of the generation rich in acetylene and hydrogen chloride, next under the conditions of existing for catalyst, allow acetylene
With the preparation method of hydrogen chloride synthesis vinyl chloride.But this method reaction temperature is high, energy consumption is big；Other acetylene and hydrogen chloride
Synthesis vinyl chloride thereof process (i.e. acetylene method) can not still avoid mercury pollution problem.
United States Patent (USP) US4737594 describes a kind of method using natural gas as initiation material synthesis vinyl chloride thereof, its feature
It by natural gas direct chlorination is chloromethanes to be, or first synthesizing methanol is then converted to chloromethanes.Then chloromethanes is made be condensed instead
Should, gained condensation product carries out oxi-chlorination, and last oxychlorination product dehydrochlorination obtains vinyl chloride.From the content of the patent
See, its core reaction is still the condensation of the oxi-chlorination of ethene, the only chloromethanes that ethylene source is prepared in natural gas
Reaction, rather than the naphtha in conventional petroleum industry or light hydrocarbon cracking reaction.
Japan Patent JPH05262682 provides one kind under the conditions of existing for catalyst, by halomethane and oxygen reaction
Carbon number is prepared as 2 and the method for the halogenation hydrocarbons of the above.Halomethane includes fluoride, chloride, bromide and iodide,
Carbon number is 2 and the halogenation hydrocarbons of the above include halogenated alkane and alkenyl halide.Its core is with alkali metal or alkali metal
Chloride, nitrate, sulfate and formates, acetate, benzene sulfonate etc. prepare catalyst for main active component, anti-
It is 450~800 DEG C (preferably 500~700 DEG C) to answer temperature, and reaction pressure is normal pressure~30atm (preferably normal pressure~10atm), instead
The catalyst quality statement (g.ml/min) flowed through between seasonable with feed gas flow rates is 0.001~10 (preferably 0.005~5) condition
Lower reaction, but product distribution results are not handed over clearly.
Inventor applies for a patent CN201410770187 the last stages and provided a kind of prepares VCM by chloromethanes
Method, on this basis, the present invention propose that one kind under with oxidative coupling of methane active catalyst existence condition, uses
The method that methane and dichloromethane oxidative coupling reaction prepare VCM, this method raw material sources are extensive, cheap, instead
Mild condition is answered, is a kind of new technology of VCM synthesis, suitable for popularization and application.
The content of the invention
It is an object of the invention to provide a kind of new method that VCM is prepared using methane, dichloromethane as raw material,
This method raw material sources are extensive, cheap, and can obtain higher reaction conversion ratio and vinyl chloride selectivity.
To achieve these goals, the technical solution adopted by the present invention is as follows：
Under the catalyst existence condition with oxidative coupling of methane activity, methane, dichloromethane and oxygen reaction
VCM is made, its reaction equation is：
CH4+CH2Cl2+1/2O2→C2H3Cl+H2O+HCl
The methane is 1 with dichloromethane sum and the mol ratio of oxygen: (0.2~2), methane and dichloromethane mol ratio
For 1: (0.5~2)；The reaction temperature of the reaction is 500~800 DEG C, and reaction pressure is 1~10atm.
The present invention reacts the possible reaction mechanism of main reaction：
O2→2O· (1)
2CH4+O·→2CH3·+H2O (2)
2CH2Cl2+O·→2CHCl2·+H2O (3)
CH3·+CHCl2·→C2H3Cl+HCl (4)
Process byproduct mainly includes ethene, chloromethanes, chloroform and trichloro ethylene, and chloromethanes and chloroform may
Come from itself disproportionated reaction of raw material dichloromethane, ethene and trichloro ethylene its possible reaction mechanism are：
2CH3·+O·→C2H4+H2O (5)
2CHCl2·→C2HCl3+HCl (6)
According to reaction mechanism, from suitable catalyst and reaction condition, the conversion ratio and chloroethene of reaction raw materials can be improved
Alkene selectivity.
In this reaction mechanism, oxygen effective activation is that active oxygen atom (O) is the important step that reaction triggers, from tool
There is oxidative coupling of methane active catalyst to be activated oxygen molecule, such as alkaline-earth metal (magnesium, calcium, strontium and barium) and
Its oxide catalyst, transition metal (scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver,
Tungsten, iridium, platinum and gold) and its oxide catalyst, or the group of alkaline-earth metal and its oxide and transition-metals and their oxides
Compound, different according to raw material proportioning and residence time, these catalyst play between being 500~800 DEG C in reaction temperature
Catalytic action.
Secondly, active oxygen atom (O) captures the hydrogen atom generation methyl (CH in methane molecule3), capture dichloromethane
Hydrogen atom generation dichloromethyl (CHCl in alkane molecule2), in the process, by adding appropriate auxiliary agent, such as alkali metal
Element (lithium, sodium, potassium, rubidium and caesium) and its compound, rare earth element (lanthanum, cerium, neodymium and samarium) and its compound, or by selecting to close
Suitable catalyst carrier, adjust the reaction of methane molecule and dichloromethane molecule in the adsorption strength and oxygen atom of catalyst surface
Activity, so as to control the activation method of methane molecule and dichloromethane molecule, make a large amount of methyl (CH in system be present3) and two
Chloromethyl (CHCl2·)。
Finally, methyl (CH3) and dichloromethyl (CHCl2) coupling generation dichloroethanes molecule.In this reaction temperature
Under (500~800 DEG C), dichloroethanes molecule sloughs rapidly a chlorination hydrogen molecule generation vinyl chloride.
According to above-mentioned analysis, following technical scheme is proposed to realize the purpose of the present invention.
The active component of catalyst is the alkaline-earth metal with Catalyst for Oxidative Coupling of Methane reactivity in the present invention
(magnesium, calcium, strontium and barium) and its oxide, transition metal (scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium,
Rhodium, palladium, silver, tungsten, iridium, platinum and gold) and its oxide, or the group of alkaline-earth metal and its oxide and transition-metals and their oxides
Compound；The auxiliary agent of catalyst is alkali metal (lithium, sodium, potassium, rubidium and caesium) and rare earth element (lanthanum, cerium, neodymium and samarium) and its changed
One or more in compound.Catalyst carrier be selected from activated alumina, sieve and silica-sesquioxide, silica gel and silicon-aluminium-phosphorous oxides,
Magnesia, titanium dioxide or Ca-Ti ore type metal composite oxide.Catalyst can be prepared with a variety of preparation methods, such as machinery
Mixing method, the precipitation method, infusion process, heat melting method, the molten method of leaching, ion-exchange, sol-gal process etc..
Compared with existing vinyl chloride preparation technology, main advantages of the present invention are as follows：
(1) compared with carbide acetylene method synthesis vinyl chloride thereof technique, the calcium carbide using highly energy-consuming, high pollution can be avoided former
Material, is advantageous to save, lowers consumption, emission reduction；It can avoid using mercury catalyst, once and for all solves mercury pollution problem and mercury resource is withered
Mercury-free caused by exhausting can use problem.The present invention meets global green, environmental protection, the theory of sustainable development very much.
(2), can be with use cost cheap methane and dichloromethane compared with balancing process for oxychlorination synthesis vinyl chloride thereof technique
Alkane is raw material, avoids the ethylene raw that use cost is higher, helps to alleviate the present situation of petroleum resources growing tension, reduces chloroethene
The production cost of alkene.
(3) raw material resources wide material sources of the present invention, as shown in figure 1, methane can be by natural gas, shale gas, coal bed gas, natural
The resource containing methane component such as gas hydrate is produced, and dichloromethane can be obtained by methane chlorination process, and raw material sources have
Very high flexibility.The present invention is raw materials used, during in particular from cheap natural gas or shale gas, can be greatly reduced
The production cost of vinyl chloride.Therefore, the present invention is for natural gas or the resourceful Middle East of shale gas, the great temptation of north America region
Power.
Brief description of the drawings
Fig. 1 is raw material sources schematic diagram of the present invention；
Fig. 2 is the technological process of production schematic diagram of the present invention.
Embodiment
In order to which the purpose of the present invention, technical scheme and beneficial effect is more clearly understood, with reference to specific embodiment
The present invention is described further, but protection scope of the present invention is not limited in the examples below.
Referring to Fig. 2, the technological process of production of the invention is：Methane, dichloromethane and oxygen enter anti-equipped with catalyst 2
Answer and reacted in device 1；The product come out from reactor 1 enters after chilling tower 3 cools removes hydrogen chloride through washing alkali cleaning, and condensation removes
Pressurization refrigerated separation is carried out into rectifying column 4, gas-phase product is mainly the complete methane of unreacted and byproduct ethylene, liquid after water
Phase product is mainly vinyl chloride product (containing accessory substance chloromethanes, chloroform and trichloro ethylene), and as needed, liquid phase is produced
Thing further separates, and can obtain VCM and other accessory substances.
According to the difference of used catalyst catalytic performance, the reactor used present invention is fixed bed or fluid bed.
Embodiment 1
After the predecessor of the manganese of certain mass, tungsten, cerium and sodium is dissolved in water, add silica gel stir after drying,
Catalyst is made in roasting.It is 1 in molar ratio by methane, dichloromethane (gas phase) and oxygen:1:Reactor is passed through after 0.4 mixing
In, reaction temperature is 800 DEG C, and reaction pressure is normal pressure, and reaction effluent washing alkali cleaning is carried out after being removed water except de-chlorine hydride, condensation
Constituent analysis, methane and dichloromethane conversion ratio calculate according to Carbon balance before and after reaction, and vinyl chloride selectively uses carbonaceous products
Normalization calculates.Methane conversion per pass is 38%, and for dichloromethane conversion ratio up to 80%, vinyl chloride is selectively about 30%.
Embodiment 2
After the predecessor of the manganese of certain mass, tungsten, cerium and sodium is dissolved in water, add silica gel stir after drying,
Catalyst is made in roasting.It is 1 in molar ratio by methane, dichloromethane (gas phase) and oxygen:1:It is passed through after 1 mixing in reactor,
Reaction temperature is 700 DEG C, and reaction pressure is normal pressure, reaction effluent washing alkali cleaning except carried out after de-chlorine hydride, condensation water removal into
Analysis, methane and dichloromethane conversion ratio are calculated according to Carbon balance before and after reaction, and vinyl chloride is selectively returned using carbonaceous products
One changes calculating.Methane conversion per pass is up to 35%, and dichloromethane conversion ratio is 60%, vinyl chloride selectively about 50%.
Embodiment 3
After the predecessor of the manganese of certain mass, tungsten, cerium and sodium is dissolved in water, add silica gel stir after drying,
Catalyst is made in roasting.It is 1 in molar ratio by methane, dichloromethane (gas phase) and oxygen:1:It is passed through after 2 mixing in reactor,
Reaction temperature is 600 DEG C, and reaction pressure is normal pressure, reaction effluent washing alkali cleaning except carried out after de-chlorine hydride, condensation water removal into
Analysis, methane and dichloromethane conversion ratio are calculated according to Carbon balance before and after reaction, and vinyl chloride is selectively returned using carbonaceous products
One changes calculating.Methane conversion per pass is 32%, and dichloromethane conversion ratio is 43%, and vinyl chloride selectivity is up to 60%.
Embodiment 4
After the predecessor of the manganese of certain mass, tungsten, cerium and sodium is dissolved in water, add silica gel stir after drying,
Catalyst is made in roasting.It is 1 in molar ratio by methane, dichloromethane (gas phase) and oxygen:2:It is passed through after 6 mixing in reactor,
Reaction temperature be 500 DEG C, reaction pressure 10atm, reaction effluent washing alkali cleaning except de-chlorine hydride, condensation water removal after carry out into
Analysis, methane and dichloromethane conversion ratio are calculated according to Carbon balance before and after reaction, and vinyl chloride is selectively returned using carbonaceous products
One changes calculating.Methane conversion per pass is up to 10%, and dichloromethane conversion ratio is 35%, vinyl chloride selectively about 25%.
As can be seen from the above embodiments, the inventive method can be by methane, dichloromethane oxidative coupling one-step synthesis chloroethene
Alkene monomer.
Claims (8)
- A kind of 1. preparation method of VCM, it is characterised in that：Under catalyst existence condition, methane, dichloromethane with VCM is made in oxygen reaction, and the catalyst has oxidative coupling of methane activity, the catalyst activity component Selected from alkaline-earth metal and its oxide, transition-metals and their oxides or alkaline-earth metal and its oxide and transition metal and its oxygen The composition of compound, the auxiliary agent of the catalyst are the one or more in alkali metal, rare earth element and its compound.
- A kind of 2. preparation method of VCM according to claim 1, it is characterised in that：It is described that there is methane oxidation Coupling reaction activity alkali earth metal for magnesium, calcium, strontium, barium, transition metal be scandium, titanium, vanadium, chromium, manganese, iron, cobalt, Nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tungsten, iridium, platinum and gold.
- A kind of 3. preparation method of VCM according to claim 1, it is characterised in that：The alkali metal is Lithium, sodium, potassium, rubidium and caesium, the rare earth element are lanthanum, cerium, praseodymium, neodymium and samarium.
- A kind of 4. preparation method of VCM according to claim 1, it is characterised in that：The catalyst carrier choosing From activated alumina, sieve and silica-sesquioxide, silica gel and silicon-aluminium-phosphorous oxides, magnesia, titanium dioxide or the compound gold of Ca-Ti ore type Belong to oxide.
- A kind of 5. preparation method of VCM according to claim 1, it is characterised in that：The methane and dichloromethane Alkane sum and the mol ratio of oxygen are 1: (0.2~2), methane are 1 with dichloromethane mol ratio: (0.5~2).
- A kind of 6. preparation method of VCM according to claim 1, it is characterised in that：The reaction temperature of the reaction Spend for 500~800 DEG C.
- A kind of 7. preparation method of VCM according to claim 1, it is characterised in that：The reaction pressure of the reaction Power is 1~10atm.
- A kind of 8. preparation method of VCM according to claim 1, it is characterised in that：The phase of the reaction is Gas phase.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106278777A (en) * | 2016-08-18 | 2017-01-04 | 宜宾天原集团股份有限公司 | A kind of method preparing ethylene and Vinyl Chloride Monomer |
| CN106278805A (en) * | 2016-08-18 | 2017-01-04 | 宜宾天原集团股份有限公司 | A kind of preparation method of vinylidene chloride monomer |
| CN106316781A (en) * | 2016-08-18 | 2017-01-11 | 宜宾天原集团股份有限公司 | Method for preparing trichloroethylene from dichloromethane |
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- 2017-08-16 CN CN201710704201.3A patent/CN107573209A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278777A (en) * | 2016-08-18 | 2017-01-04 | 宜宾天原集团股份有限公司 | A kind of method preparing ethylene and Vinyl Chloride Monomer |
| CN106278805A (en) * | 2016-08-18 | 2017-01-04 | 宜宾天原集团股份有限公司 | A kind of preparation method of vinylidene chloride monomer |
| CN106316781A (en) * | 2016-08-18 | 2017-01-11 | 宜宾天原集团股份有限公司 | Method for preparing trichloroethylene from dichloromethane |
Non-Patent Citations (1)
| Title |
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| 刘慧娟等: "甲烷氯化物催化偶联合成氯乙烯单体新技术", 《四川化工》 * |
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