CN103269796A - Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene - Google Patents
Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene Download PDFInfo
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- CN103269796A CN103269796A CN2011800624438A CN201180062443A CN103269796A CN 103269796 A CN103269796 A CN 103269796A CN 2011800624438 A CN2011800624438 A CN 2011800624438A CN 201180062443 A CN201180062443 A CN 201180062443A CN 103269796 A CN103269796 A CN 103269796A
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- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
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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
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/825—Osmium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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- B01J2531/828—Platinum
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Abstract
Catalytic system comprising a mixture of a) at least one compound of at least one metal one of which being chosen from palladium, platinum and osmium; and b) at least one ionic liquid comprising at least one non-protonated cation and at least one anion, the mixture being chosen from a selected group of mixtures.
Description
The present invention relates to a kind of catalysis system, this catalysis system is a kind of useful especially for the method for making vinyl chloride by the hydrochlorination of acetylene.The invention still further relates to this method.
Carry out normally in gas phase, in a kind of fixed bed reactors, when existing based on a kind of heterogeneous solid catalyst that is loaded with mercury chloride by the manufacturing of the reaction between acetylene and hydrogen chloride vinyl chloride.Mainly be because toxicity, at present to mercury content with minimizing or the catalysis system of compound containing mercury is more and more not interested.
Develop multiple different catalyst, be intended to replace the catalyst in the present gas phase process.
When for example, uncensored Japanese patent application 52/136104 has been described a kind of fixed catalytic bed existence of being made up of the noble metal halide that is deposited on the active carbon in gas phase acetylene is carried out the method for hydrochlorinate.Yet up to now, this type of is intended to alternative life of catalyst for gas phase process and still is significantly shorter than life of catalyst based on mercury compound.
In addition, there are some in the presence of a kind of liquid catalyst medium, acetylene to be carried out the example of hydrochlorinate in the document.
Deutsche Bundespatent 709.000 has been described a kind of method for preparing vinyl halide by the hydrohalide salt melt that at high temperature makes acetylene contact the organic base that contains a kind of standard catalyst.Amine of aliphatic, aromatic or heterocycle and composition thereof is considered as organic base.
Inventor's certificate SU237116 has described the stannous chloride that uses a kind of 46wt% of containing and from the aqueous peracid solution of the hydrochloride of a kind of methylamine, dimethylamine or the trimethylamine of 14wt% to 16wt%.
European patent application book EP-A-0340416 has disclosed and a kind ofly acetylene and hydrogen chloride reacted in the solvent of being made up of aliphatic or alicyclic acid amides when palladium compound exists as catalyst and has prepared the method for vinyl chloride being higher than under the temperature of environment temperature.Though its allow to obtain high output, yet this method also has some significant disadvantages: it has shown, and this liquid catalyst system degenerates gradually under reaction condition, thereby forms the black product with carbonaceous outward appearance.In addition, in the presence of hydrogen chloride, acid amides is converted into a kind of hydrochloride, and its fusing point is normally far above environment temperature.For example, N-crassitude keto hydrochloride only is only liquid at 80 ° more than the C.In fact, this may cause serious implementation issue, the reunion of these problems and reactor down periods catalytic media or on the coldest point of facility the obstruction of pipeline relevant.So the pipeline that whole reactor and the medium that responds flow therein must remain on the temperature that is higher than the hydrochloride fusing point constantly.
Because the hydrochlorination system of in European patent application EP 0519548-A1 and EP0525843-A1, describing, as if these different problems are resolved, and these systems comprise at least a group VIII metallic compound and or a kind of amine hydrochlorate (its fusing point is less than or equal to 25 ° of C) or a kind of a kind of organic solvent that comprises the fatty amine hydrochloride (its fusing point is higher than 25 ° of C) more than 8 carbon atoms and be selected from aliphatic, alicyclic and aromatic hydro carbons and composition thereof.However, described antigravity system wherein, especially wherein the group VIII metallic compound is the system of platinum chloride (II) or palladium bichloride (II), when consider aspect the productivity ratio of being produced vinyl chloride by the hydrochlorination of acetylene and long-term stable aspect they make it possible to realize performance the time, be not to be entirely satisfactory.
WO2008/77868 has disclosed a kind of hydrochlorination system of catalysis, comprise at least a amine hydrochlorate and at least a group VIII metallic compound, this metallic compound is selected from down group, and this group comprises: the compound of the compound of a kind of platinum (IV) and the mixture of stannic chloride (II), a kind of platinum (II) and the mixture of triphenylphosphine oxide and the compound of a kind of palladium (II) and the mixture of triphenylphosphine.These catalysis systems show with European patent application EP-A0519548 and EP-A0525843 in the system described compare a kind of improved productivity ratio.Above-mentioned catalysis system shows the shortcoming that requires a kind of amine hydrochlorate to combine with very specific metallic compound.
At last, patent application CN101716528 has disclosed the catalysis system that is used for producing by the hydrochlorination of acetylene vinyl chloride, this catalysis system comprise have chlorine, the ion of bromine, hexafluoro-phosphate radical or tetrafluoro phosphate radical as anion based in the chloride of the ionic liquid of imidazoles and gold, platinum, palladium, tin, mercury, copper or rhodium one or more.Above-mentioned catalysis system is at conversion ratio, be entirely satisfactory still failing aspect the productivity ratio selectively and thus.
Therefore, an object of the present invention is to provide a kind of catalysis system, specifically be for hydrochlorination and more specifically be used for the hydrochlorination of acetylene, this catalysis system is simple as far as possible and cheap, permission conversion ratio, selective and therefore also have productivity ratio aspect extraordinary performance is arranged, and it shows better than original system.Another object of the present invention is a kind of method that the hydrochlorination synthesizing chloroethylene of acetylene is provided in the presence of this catalysis system, and this catalysis system is not degraded under reaction condition and enabled to realize extraordinary productivity ratio towards vinyl chloride.Unlike the system based on mercury compound, the advantage that catalysis system according to the present invention has is not have the toxicity problem relevant with these compounds, and has avoided the evaporation of slaine in facility.
Therefore the present invention relates to a kind of catalysis system, a kind of catalysis system of the hydrochlorination for acetylene more specifically, as defined in claim 7.
According to the preferred embodiment of catalysis system of the present invention in the claim that is subordinated to claim 7 and hereinafter propose in the more detailed description.
Another aspect of the present invention relate to as claim 1 and be subordinated in the claim of claim 1 and in the explanation of more describing in detail hereinafter defined a kind of catalysis system in the presence of make a kind of method of vinyl chloride by the hydrochlorination of acetylene.
The catalysis system of Shi Yonging comprises a kind of mixture of the following in the method according to the invention
A) at least a compound of at least a metal that one of is selected from palladium, platinum and the osmium; And
B) comprise the cation of at least a non-protonization and at least a ionic liquid of at least a anion;
This mixture is selected from the group of following mixture, comprises
When this metal is palladium,
Palladium (II) and 1-butyl-3-methyl imidazolitm chloride or 1-ethyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), copper chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), stannous chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II) and 1-ethyl-3-methyl imidazolitm chloride, 1-methyl-3-octyl group imidazolitm chloride, 1-benzyl-3-methyl imidazolitm chloride or three hexyls, four decyl phosphonium chlorides,
Palladium bichloride (II), palladium (II) and butyl trimethyl ammonium two (trifluoromethyl sulfonyl) imidization thing;
When this metal is platinum,
Platinum chloride (II) and 1-butyl-3-methyl imidazolitm chloride, 1-butyl-3-methyl tetrachloro ferric acid imidazoles, 1-ethyl-3-methyl imidazolitm chloride, 1-ethyl-3-methylmethane sulfonic acid imidazoles, 1-ethyl-3-methyl tetrafluoro ethylsulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride, 1-methyl-3-octyl group TFMS imidazoles or three hexyls, four decyl phosphonium chlorides
Platinum chloride (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles or three hexyl Si Gui Ji Phosphonium two (trifluoromethyl sulfonyl) imidization things;
The sour potassium of chlordene platinum (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles; And
When this metal is osmium,
Osmium chloride (III) and 1-butyl-3-methyl imidazolitm chloride, 1-ethyl-3-methyl tetrafluoro ethylsulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride or three hexyls, four decyl phosphonium chlorides.
Statement " comprising " is interpreted as in this manual referring to except at least a compound of at least a metal and as at least a ionic liquid of above definition, can also comprises that according to catalysis system of the present invention catalysis characteristics to this catalysis system is with or without one or more other components of influence.In this one or more other component, can mention one or more ionic liquids a kind of or different kinds of ions liquid except this of above definition, they are influential and/or allow the viscosity of this catalysis system to reduce to catalysis characteristics.
Preferably, mainly formed by at least a compound of at least a metal and the mixture of at least a ionic liquid as defined above according to catalysis system of the present invention.
Statement " mainly by ... form " be interpreted as in this manual referring to except at least a compound and at least a ionic liquid of at least a metal, can also comprise the catalysis characteristics of this catalysis system one or more other components of influence (preferably with a small amount of) not according to catalysis system of the present invention; In other words, in the course of reaction of using this catalysis system, this reaction there is not catalytic action.In this one or more other component, can mention one or more ionic liquids a kind of or different kinds of ions liquid except this of above definition, for example they are added to reduce the viscosity of this catalysis system.
More preferably, catalysis system according to the present invention by as defined above, at least a compound of at least a metal and the mixture of at least a ionic liquid form.Statement " by ... form " be interpreted as in this manual referring to this catalysis system only by at least a compound of at least a metal with as the mixture of at least a ionic liquid of above definition form.
At least a compound that catalysis system according to the present invention comprises at least a metal that one of is selected from palladium, platinum and the osmium as component a).
In this manual, as used herein, statement " at least a compound of at least a metal " comprises the compound of the mixture of different compounds of a kind of single metallic compound of metal and metal of the same race or different metal or comprises the mixture of compound of two kinds of metals of above definition, namely, can comprise more than a kind of metal as defined above (correspondingly, metallic compound) according to catalysis system of the present invention.
In this manual, statement one of " be selected from palladium, platinum and the osmium a kind of metal " is interpreted as referring to that a kind of in this metal is palladium, platinum or osmium.
At the remainder of this paper, the statement of using with odd number or plural form " compound " and " metal " are interpreted as representing a kind of accordingly or more than a kind of compound and a kind of or more than a kind of metal, except as otherwise noted.
Catalysis system according to the present invention comprises that at least a ionic liquid is as components b).
Ionic liquid mainly is the salt that is in liquid condition, and common liq (for example as water and gasoline) mainly is to be made of electroneutral molecule.Ionic liquid advantageously is made of ion.
Can think any fusion generally and Undec salt will produce a kind of ionic liquid usually.Yet many salt at high temperature melt, far above the temperature of using in catalysis process.For the purposes of the present invention, the term ionic liquid should refer to a kind of a kind of system of liquid of being under the employed temperature in using the method for this catalysis system.
For the purposes of the present invention, preferred ionic liquid be under 150 ° of C or the lower temperature, more preferably 100 ° of C or lower, more preferably under 80 ° of C or lower temperature, be those of liquid.Most preferably in room temperature or even be in the ionic liquid of liquid condition when being lower than room temperature.In addition, preferred ionic liquid is to have low-down vapour pressure and low-down combustibility and show those of good electrical conductivity.
Advantageously the ionic liquid that works as reaction medium preferably is selected as making it that the material that participates in this reaction roughly is inertia and preferably has the solvent ability for the product and the intermediate that form in this reaction.
In this manual, statement " at least a ionic liquid " is interpreted as referring to a kind of or more than a kind of ionic liquid.
Preferably, this catalysis system comprises a kind of mixture of ionic liquid as defined above.
At the remainder of this paper, the statement of using with odd number or plural form " ionic liquid " is interpreted as representing a kind of or more than a kind of ionic liquid, except as otherwise noted.
Ionic liquid according to the present invention comprises cation and at least a anion of at least a non-protonization.
In this manual, statement " cation of at least a non-protonization " is interpreted as referring to a kind of or more than a kind of cation of non-protonization.
Preferably, this ionic liquid comprises a kind of cation of non-protonization.
At the remainder of this paper, the statement of using with odd number or plural form " cation of non-protonization " is interpreted as representing a kind of or more than a kind of cation of non-protonization, except as otherwise noted.
As used herein, the cation of non-protonization of term should refer to not carry the cation of one or more free hydrogen atoms for the purposes of the present invention on the assigned one or more atoms of this cationic positive charge.
In this manual, statement " at least a anion " is interpreted as referring to a kind of or more than a kind of anion.
Preferably, this ionic liquid comprises a kind of anion.
At the remainder of this paper, the statement of using with odd number or plural form " anion " is interpreted as representing a kind of or more than a kind of anion, except as otherwise noted.
Catalysis system according to the present invention comprises a kind of mixture of the following
A) at least a compound of at least a metal that one of is selected from palladium, platinum and the osmium; And
B) comprise the cation of at least a non-protonization and at least a ionic liquid of at least a anion;
This mixture is selected from the group of following mixture, comprising:
When this metal is palladium,
Palladium (II) and 1-ethyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), stannous chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II) and 1-methyl-3-octyl group imidazolitm chloride, 1-benzyl-3-methyl imidazolitm chloride or three hexyls, four decyl phosphonium chlorides,
Palladium bichloride (II), palladium (II) and butyl trimethyl ammonium two (trifluoromethyl sulfonyl) imidization thing;
When this metal is platinum,
Platinum chloride (II) and 1-butyl-3-methyl imidazolitm chloride, 1-butyl-3-methyl tetrachloro ferric acid imidazoles, 1-ethyl-3-methyl imidazolitm chloride, 1-ethyl-3-methylmethane sulfonic acid imidazoles, 1-ethyl-3-methyl tetrafluoro ethylsulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride, 1-methyl-3-octyl group TFMS imidazoles or three hexyls, four decyl phosphonium chlorides
Platinum chloride (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles or three hexyl Si Gui Ji Phosphonium two (trifluoromethyl sulfonyl) imidization things;
The sour potassium of chlordene platinum (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles; And
When this metal is osmium,
Osmium chloride (III) and 1-butyl-3-methyl imidazolitm chloride, 1-ethyl-3-methyl tetrafluoro ethylsulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride or three hexyls, four decyl phosphonium chlorides.
According to first embodiment, catalysis system according to the present invention comprise a kind of a) and b) mixture, this mixture is selected from the group of following mixture, comprises
Palladium (II) and 1-ethyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), stannous chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II) and 1-methyl-3-octyl group imidazolitm chloride, 1-benzyl-3-methyl imidazolitm chloride or three hexyls, four decyl phosphonium chlorides,
Palladium bichloride (II), palladium (II) and butyl trimethyl ammonium two (trifluoromethyl sulfonyl) imidization thing.
According to second embodiment, this catalysis system comprise a kind of a) and b) mixture, this mixture is selected from the group of following mixture, comprises
Platinum chloride (II) and 1-butyl-3-methyl imidazolitm chloride, 1-butyl-3-methyl tetrachloro ferric acid imidazoles, 1-ethyl-3-methyl imidazolitm chloride, 1-ethyl-3-methylmethane sulfonic acid imidazoles, 1-ethyl-3-methyl tetrafluoro ethylsulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride, 1-methyl-3-octyl group TFMS imidazoles or three hexyls, four decyl phosphonium chlorides
Platinum chloride (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles or three hexyl Si Gui Ji Phosphonium two (trifluoromethyl sulfonyl) imidization things;
The sour potassium of chlordene platinum (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles.
According to the 3rd embodiment, this catalysis system comprise a kind of a) and b) mixture, this mixture is selected from the group of following mixture, comprises
Osmium chloride (III) and 1-butyl-3-methyl imidazolitm chloride, 1-ethyl-3-methyl tetrafluoro ethylsulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride or three hexyls, four decyl phosphonium chlorides.
Though use the catalysis system according to three embodiments of the present invention to obtain good result, but use according to first and obtained extraordinary result according to the catalysis system of second embodiment, and use the catalysis system according to first embodiment (namely comprising chlorination and/or acetic acid Pd (II)) to obtain good especially result.
The content of the compound of at least a metal that one of is selected from palladium, platinum or the osmium in catalysis system according to the present invention reaches advantageously more than or equal to 1mmol/l with the mM numerical table that whenever lifts away from sub-liquid and is less than or equal to 1000mmol/l.The content of compound is advantageously more than or equal to 1mmol/l as defined above, is preferably greater than or equals 5mmol/l, and be preferably greater than especially or equal 10mmol/l.The content of compound advantageously is less than or equal to 1000mmol/l and preferably is less than or equal to 900mmol/l as defined above.
The content of the compound of palladium, platinum or osmium in catalysis system according to the present invention reaches advantageously more than or equal to 1mmol/l with the mM numerical table that whenever lifts away from sub-liquid and is less than or equal to 1000mmol/l.The content of compound is advantageously more than or equal to 1mmol/l as defined above, is preferably greater than or equals 5mmol/l, and be preferably greater than especially or equal 10mmol/l.The content of compound advantageously is less than or equal to 1000mmol/l as defined above, preferably be less than or equal to 500mmol/l, especially preferably be less than or equal to 200mmol/l, more especially preferably be less than or equal to 100mmol/l, and especially the most preferably be less than or equal to 50mmol/l.
Though be not enforceable, yet all metallic compounds that preferably comprise in this catalysis system all are the forms that is in dissolving.
The catalyst according to the invention system can be used to liquid phase or be deposited over solid carrier such as silica, aluminium oxide, cimita, cordierite, mullite or active carbon (only listing several suitable carriers materials) on, up to the pore volume of carrier and the limiting value of useable surface area.This carrier can have Any shape for the examples of such carriers material, include but not limited to cellular thing and extrudate or analog.
When this catalysis system uses, it can be used a kind of organic solvent diluting in liquid phase.So be included in according to the selection of the character of the organic solvent in the catalysis system of the present invention and especially depend on following requirement: it under reaction condition for reactant be inertia, it mixes easily with ionic liquid; And depend on following hope: it and this ionic liquid form a kind of medium, the viscosity the when viscosity of this medium is lower than this ionic liquid individualism.
Yet preferably, this ionic liquid self serves as a kind of solvent, thereby makes that other solvent needn't be arranged.
In general, catalysis system according to the present invention is by with the dissolving of the metallic compound of desirable amount or be dispersed in the ionic liquid and make with hydrogen chloride then that this solution is saturated to be prepared when using in hydrochlorination with hydrogen chloride.Yet, also might be at first that this ionic liquid is saturated with hydrogen chloride, then this metallic compound is introduced in this ionic liquid afterwards.Usually, the amount of employed metallic compound is to make in catalysis system whole metallic compounds all be in the form of dissolving.Yet, also might use a kind of metallic compound, its value or the character that has make at least a portion of this compound be present in this catalysis system with the form of dispersed solids, and not unfavorable to the present invention.
Can be for any reaction at alkynes according to catalysis system of the present invention, that is, two carbon pass through the compounds that a triple bond connects.In this type of alkynes, can mention acetylene, propine (being also referred to as allylene), dimethyl butyn, 1,4-butylene glycol, together with the propine compounds.This reaction can be hydrohalogenation, particularly hydrochlorinate effect (carrying out with hydrogen chloride), hydrogen iodination (carrying out with hydrogen iodide), hydrofluorination (carrying out with hydrogen fluoride) or hydrobromination (carrying out with hydrogen bromide), or the reaction of carrying out with phosphoric acid.
Catalysis system according to the present invention is useful especially for the hydrochlorinate effect of acetylene.
In the present invention, it is acetylene or the mixture that comprises acetylene that term " acetylene " is interpreted as, and these mixtures can also comprise other components except acetylene, and for example ethene or other unsaturated hydro carbons, these hydro carbons can be the synthetic accessory substances of acetylene.The source of this type of mixture of different unsaturated compounds can be the mixture in any source, can obtain in the process of the known synthetic method that is used for acetylene as them.Can use and comprise the mixture that is less than 50% acetylene.Yet preferably, term " acetylene " refers to comprise at least 90% acetylene and the more preferably mixture of 100% acetylene.
Acetylene mainly is that the partial combustion by methane is made or as occurring from the accessory substance in the ethene steam of hydrocarbon cracking.
Another kind of method for the manufacture of acetylene is the hydrolysis of calcium carbide
CaC
2+2H
2O→Ca(OH)
2+C
2H
2
This requires the extremely high temperature of about 2000 ° of C, must use electric furnace or analog thereby make.
The mixture that comprises acetylene and ethene can directly in statu quo use, that is, need not component is separated, because the reactivity that acetylene is compared with ethene makes the hydrochlorinate effect of acetylene can at first separate the vinyl chloride that obtains and uses ethene subsequently and carry out.Can be with this ethylene chlorination producing 1,2-dichloroethanes, thus be used for a kind of integrated processes of making VCM.The pyrolysis of 1,2-dichloroethanes can produce hydrogen chloride, this first reaction that is used for carrying out with acetylene.
Therefore, the invention still further relates to a kind of for the reaction (hydrochlorinate effect) by acetylene and hydrogen chloride according to the method for making vinyl chloride in the presence of a kind of catalysis system of the present invention.
More than be applicable to the method for vinyl chloride constructed in accordance for the defined definition of catalysis system according to the present invention and preference.
The method according to this invention advantageously can be carried out under the temperature in the scope of room temperature to 220 ° C.Under higher temperature, this catalysis system has a kind of trend of degraded.Preferred reaction temperature that is to say best trading off between the stability that productivity ratio, output and catalytic media are provided, and is more than or equal to about 40 ° of C.Under the temperature more than or equal to about 50 ° of C, more particularly preferably be more than or equal to the temperature of about 80 ° of C under and particularly preferably be most and under the temperature more than or equal to about 120 ° of C, obtained best result.Preferably, this reaction temperature is no more than 200 ° of C.About 40 ° of C are the most particularly preferred to the reaction temperature of about 200 ° of C.In some cases, the reaction temperature that is no more than 170 ° of C proves favourable.
The method according to this invention is advantageously carried out under environmental pressure or the more high pressure compatible with the security legislation that is used for handling acetylene.Usually, this pressure will be no more than 5MPa, and preferably it will be no more than the dividing potential drop of the acetylene of 2.5Mpa.
Advantageously by being contacted with this catalysis system, gaseous reactant (acetylene and hydrogen chloride) undertaken in any suitable reactor according to the method for the preparing vinyl chloride by hydrochlorination by acetylene of the present invention.
The method according to this invention can be routinely be carried out in the equipment of any promotion solution-air exchange, and this equipment is for example plate tower, overflow-type packed column or the non-packed column of overflow-type.The another one of this method can make the embodiment that good mass exchange is arranged between gas phase and the liquid phase comprise the use counter-current reactor, the packed bed type of optionally spraying, the liquid catalyst system reverse in reactant air-flow and flow through this filler.
In the method according to the invention, the mol ratio of the hydrogen chloride in the adding reactor and acetylene is advantageously more than or equal to about 0.5.Preferably, this ratio is more than or equal to about 0.8.Advantageously, this mol ratio is less than or equal to about 3.Preferably, the hydrogen chloride in the adding reactor and the mol ratio of acetylene are to be less than or equal to about 1.5.
When hydrogen chloride and acetylene are when using to about 3 the mol ratio from about 0.5, obtained good result.
Acetylene can contact in reactor with hydrogen chloride, perhaps preferably mixes before introducing reactor.
In order to increase the amount that is dissolved in the acetylene in the liquid phase, also might use a kind of method, only acetylene is introduced in the reactor with gaseous form in the method, it reacts with the hydrogen chloride that exists with the form of hydrochloride in liquid phase in this reactor.The chlorination Hydrogen Energy is introduced in any form: the gaseous state of dilution, pure or be dissolved in the solvent that remains to be extracted, a kind of insoluble amine for example carries out the drying process of an intermediate after advantageously.
Advantageously can be in the method according to the invention for the manufacture of vinyl chloride according to catalysis system of the present invention.
Therefore the invention still further relates to according to catalysis system of the present invention and be used for the catalytic hydrochlorinate work of acetylene in order to make the purposes of vinyl chloride.
Catalysis system according to the present invention provides at conversion ratio, selectively and therefore also have and be better than the extraordinary performance of the catalysis system of prior art aspect the improved productivity ratio, and it is characterized by long-term stability.Avoid the use mercury compound, had the advantage of the toxicity problem relevant with these compounds according to catalysis system of the present invention in addition.
Following example is intended to illustrate the present invention, but is not intended to limit its scope.The example of representing with letter C has been comparison example and other case descriptions according to catalysis system of the present invention.
General program in order to working example:
It is sending in the Simon Rex reactor of 45ml that the corresponding solution of the catalysis system that 30ml is comprised as described below and prepare adds an inner volume, this reactor be equipped with heat transmit a dual chuck of oil circulation therein and be used for introducing reactant, by the device that a sintered glass nozzle constitutes, this nozzle is intended to guarantee the dispersion of gas in liquid medium.This reactor is remained under the temperature of 150 ° of C.
Reactant acetylene and HCl are introduced with the amount (measuring under 0 ° of C and atmospheric pressure) of 10Nl/h and 12Nl/h with the mol ratio of 1:1.2.
Pointed metallic compound is dissolved in as the form that receives with needed amount and in the ionic liquid that uses.Except indicating in addition, the amount of metal is the ionic liquid of 22.6mmol/l.
The effluent that leaves this reactor is analyzed with regard to the conversion ratio of acetylene.In all experiments, selectively be 100%, that is, except desirable product vinyl chloride, do not have accessory substance.Therefore, can directly calculate productivity ratio by the conversion ratio of acetylene.
The ionic liquid of testing and indicating in the table of having summed up the catalysis system of testing is the following:
IL11-butyl-3-methyl imidazolitm chloride
IL21-butyl-3-methyl tetrachloro ferric acid imidazoles
IL31-ethyl-3-methyl imidazolitm chloride
IL41-ethyl-3-methylimidazole two (trifluoromethyl sulfonyl) imidization thing
IL51-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles
IL61-ethyl-3-methylmethane sulfonic acid imidazoles
IL71-ethyl-3-methyl tetrafluoro ethylsulfonic acid imidazoles
IL81-cetyl-3-methyl imidazolitm chloride
IL91-benzyl-3-methyl imidazolitm chloride
IL101-ethyl-2,3-methylimidazole two (trifluoromethyl sulfonyl) imidization thing
IL111-methyl-3-octyl group imidazolitm chloride
IL121-methyl-3-octyl group TFMS imidazoles
IL13 three hexyls four decyl phosphonium chlorides
IL14 three hexyl Si Gui Ji Phosphonium two (trifluoromethyl sulfonyl) imidization things
IL15 triisobutyl methyl Jia Ben phosphonium sulfonates
IL17 butyl trimethyl ammonium two (trifluoromethyl sulfonyl) imidization thing
IL161-butyl-4-picoline two (trifluoromethyl sulfonyl) imidization thing
IL181-butyl-1-methylpyrrole two (trifluoromethyl sulfonyl) imidization thing
These result of experiment provide in following table and/or show in Fig. 1 to 4, these figure demonstrated conversion of alkyne (%) over time (the x axle show in hour time).The numbering of next-door neighbour's curve is corresponding to the numbering of example.
Table 1-example 1 to 29C-comprises the catalysis system of the mixture of a kind of ionic liquid and a kind of palladium compound
#: the Pd of 22.6mmol/l and the Cu of 820mmol/l, the while is at the IL1 that located to add 15ml in 252 hours of example 2
$: the Cu of 820mmol/l
§: the Cu of 67.8mmol/l
﹠amp;: the amount of metal increases to 67.8mmol/l by 22.6 in experimentation
*: every kind of metal 22.6mmol/l
These result of experiment show, use the better result of catalysis system who has obtained the factually routine 4C to 7C of beguine according to example 1,2 or 3 catalysis system.
They also show, use according to example 9,10,17 and 19 catalysis system and have obtained extraordinary conversion ratio.
In addition, seen in table 1, according to the catalysis system of example 11C to 16C, 18C, 20C, 23C to 27C and 29C show on the dissolubility problem and therefore can not further use.
At last, result of experiment shows, uses the catalysis system according to example 21 and 28 to obtain good conversion ratio, and namely this conversion ratio is lower than the conversion ratio that use obtains according to example 1,2,3,9,10,17 and 19 catalysis system.
Table 2-example 30 to 48C-comprises the catalysis system of the mixture of a kind of ionic liquid and a kind of platinum compounds
Example number | Ionic liquid | Metallic compound | The |
30 * | IL1 | PtCl 2 | Fig. 2 |
31C $ | IL1 | PtCl 4 | Fig. 2 and Fig. 3 |
32C $ | IL1 | K 2PtCl 6 | Fig. 2 and Fig. 3 |
33 | IL2 | PtCl 2 | Fig. 3 |
34 & | IL3 | PtCl 2 | Fig. 3 |
35C | IL4 | PtCl 2 | Soluble |
36C | IL5 | PtCl 2 | Soluble |
37 | IL6 | PtCl 2 | Fig. 3 |
38 & | IL7 | PtCl 2 | Fig. 2 |
39C | IL10 | PtCl 2 | Soluble |
40 § | IL11 | PtCl 2 | Fig. 3 |
41 | IL12 | PtCl 2 | Fig. 2 |
42 & | IL13 | PtCl 2 | Fig. 2 |
43C | IL14 | PtCl 2 | Soluble |
44C | IL14 | K 2PtCl 6 | Soluble |
45C | IL15 | PtCl 2 | Soluble |
46C | IL16 | PtCl 2 | Soluble |
47C | IL17 | PtCl 2 | Soluble |
48C | IL18 | PtCl 2 | Soluble |
49 | IL14 | PtCl 4 | Solvable |
50 | IL5 | PtCl 4 | Solvable |
51 | IL5 | K 2PtCl 6 | Solvable |
*: the Pt of 67.8mmol/l
$: the amount of metal increases to 67.8mmol/l by 22.6 in experimentation
﹠amp; : the amount of metal increases to 90.4mmol/l by 22.6 in experimentation
The Pt of §: 67.2mmol/l
These result of experiment show, use according to example 30,33,34,37,38,40,41 and 42 catalysis system and have obtained the beguine better result of catalysis system of routine 31C and 32C factually.
In addition, seen in table 2, according to the catalysis system of example 35C, 36C, 39C, 43C, 44C, 45C, 46C, 47C and 48C show on the dissolubility problem and therefore can not further use, and be soluble according to example 49,50 and 51 catalysis system.
Table 3-example 52 to 60C-comprises the catalysis system of the mixture of a kind of ionic liquid and a kind of osmium compound
Example number | Ionic liquid | Metallic compound | The |
52 | IL1 | OsCl 3 | Fig. 4 |
53C | IL5 | OsCl 3 | Soluble |
54C | IL6 | OsCl 3 | Soluble |
55 | IL7 | OsCl 3 | Fig. 4 |
56 | IL11 | OsCl 3 | Fig. 4 |
57C | IL12 | OsCl 3 | Soluble |
58 | IL13 | OsCl 3 | Fig. 4 |
59C | IL15 | OsCl 3 | Soluble |
60C | IL17 | OsCl 3 | Soluble |
These result of experiment show, use according to example 52,55,56 and 58 catalysis system and have obtained extraordinary conversion ratio.
In addition, seen in table 3, according to the catalysis system of example 53C, 54C, 57C, 59C and 60C show on the dissolubility problem and therefore can not further use.
Claims (10)
1. make the method for vinyl chloride in the presence of catalysis system by the reaction of acetylene and hydrogen chloride, described catalysis system comprises the mixture of following material
A) at least a compound of at least a metal that one of is selected from palladium, platinum and the osmium; And
B) comprise the cation of at least a non-protonization and at least a ionic liquid of at least a anion;
Described mixture is selected from the group of following mixture, and the group of described mixture comprises
When described metal is palladium,
Palladium (II) and 1-butyl-3-methyl imidazolitm chloride or 1-ethyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), copper chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), stannous chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II) and 1-ethyl-3-methyl imidazolitm chloride, 1-methyl-3-octyl group imidazolitm chloride, 1-benzyl-3-methyl imidazolitm chloride or three hexyls, four decyl phosphonium chlorides,
Palladium bichloride (II), palladium (II) and butyl trimethyl ammonium two (trifyl) imidization thing;
When described metal is platinum,
Platinum chloride (II) and 1-butyl-3-methyl imidazolitm chloride, 1-butyl-3-methyl tetrachloro ferric acid imidazoles, 1-ethyl-3-methyl imidazolitm chloride, 1-ethyl-3-methylmethanesulfonate imidazoles, 1-ethyl-3-methyl tetrafluoro ethyl sulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride, 1-methyl-3-octyl group TFMS imidazoles or three hexyls, four decyl phosphonium chlorides
Platinum chloride (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles or three hexyl Si Gui Ji Phosphonium two (trifyl) imidization things;
The sour potassium of chlordene platinum (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles; With
When described metal is osmium,
Osmium chloride (III) and 1-butyl-3-methyl imidazolitm chloride, 1-ethyl-3-methyl tetrafluoro ethyl sulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride or three hexyls, four decyl phosphonium chlorides.
2. method according to claim 1, wherein said mixture is selected from the group of following mixture, and the group of described mixture comprises
Palladium (II) and 1-butyl-3-methyl imidazolitm chloride or 1-ethyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), copper chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), stannous chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II) and 1-ethyl-3-methyl imidazolitm chloride, 1-methyl-3-octyl group imidazolitm chloride, 1-benzyl-3-methyl imidazolitm chloride or three hexyls, four decyl phosphonium chlorides,
Palladium bichloride (II), palladium (II) and butyl trimethyl ammonium two (trifyl) imidization thing.
3. method according to claim 1, wherein said mixture is selected from the group of following mixture, and the group of described mixture comprises
Platinum chloride (II) and 1-butyl-3-methyl imidazolitm chloride, 1-butyl-3-methyl tetrachloro ferric acid imidazoles, 1-ethyl-3-methyl imidazolitm chloride, 1-ethyl-3-methylmethanesulfonate imidazoles, 1-ethyl-3-methyl tetrafluoro ethyl sulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride, 1-methyl-3-octyl group TFMS imidazoles or three hexyls, four decyl phosphonium chlorides
Platinum chloride (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles or three hexyl Si Gui Ji Phosphonium two (trifyl) imidization things;
The sour potassium of chlordene platinum (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles.
4. method according to claim 1, wherein said mixture is selected from the group of following mixture, and the group of described mixture comprises
Osmium chloride (III) and 1-butyl-3-methyl imidazolitm chloride, 1-ethyl-3-methyl tetrafluoro ethyl sulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride or three hexyls, four decyl phosphonium chlorides.
5. catalysis system according to claim 1, wherein the content that a) reaches with the mM numerical table that whenever lifts away from sub-liquid is more than or equal to 1mmol/l and is less than or equal to 1000mmol/l.
6. method according to claim 1, wherein said reaction is to carry out under the temperature of environment temperature to 220 ° C.
7. catalysis system, it comprises the mixture of following material
A) at least a compound of at least a metal that one of is selected from palladium, platinum and the osmium; And
B) comprise the cation of at least a non-protonization and at least a ionic liquid of at least a anion;
Described mixture is selected from the group of following mixture, and the group of described mixture comprises
When this metal is palladium,
Palladium (II) and 1-ethyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), stannous chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II) and 1-methyl-3-octyl group imidazolitm chloride, 1-benzyl-3-methyl imidazolitm chloride or three hexyls, four decyl phosphonium chlorides,
Palladium bichloride (II), palladium (II) and butyl trimethyl ammonium two (trifyl) imidization thing;
When described metal is platinum,
Platinum chloride (II) and 1-butyl-3-methyl imidazolitm chloride, 1-butyl-3-methyl tetrachloro ferric acid imidazoles, 1-ethyl-3-methyl imidazolitm chloride, 1-ethyl-3-methylmethanesulfonate imidazoles, 1-ethyl-3-methyl tetrafluoro ethyl sulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride, 1-methyl-3-octyl group TFMS imidazoles or three hexyls, four decyl phosphonium chlorides
Platinum chloride (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles or three hexyl Si Gui Ji Phosphonium two (trifyl) imidization things;
The sour potassium of chlordene platinum (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles; With
When this metal is osmium,
Osmium chloride (III) and 1-butyl-3-methyl imidazolitm chloride, 1-ethyl-3-methyl tetrafluoro ethyl sulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride or three hexyls, four decyl phosphonium chlorides.
8. catalysis system according to claim 7, wherein said mixture is selected from the group of following mixture, and the group of described mixture comprises
Palladium (II) and 1-ethyl-3-methyl imidazolitm chloride,
Palladium bichloride (II), stannous chloride and 1-butyl-3-methyl imidazolitm chloride,
Palladium bichloride (II) and 1-methyl-3-octyl group imidazolitm chloride, 1-benzyl-3-methyl imidazolitm chloride or three hexyls, four decyl phosphonium chlorides,
Palladium bichloride (II), palladium (II) and butyl trimethyl ammonium two (trifyl) imidization thing.
9. catalysis system according to claim 7, wherein said mixture is selected from the group of following mixture, and the group of described mixture comprises
Platinum chloride (II) and 1-butyl-3-methyl imidazolitm chloride, 1-butyl-3-methyl tetrachloro ferric acid imidazoles, 1-ethyl-3-methyl imidazolitm chloride, 1-ethyl-3-methylmethanesulfonate imidazoles, 1-ethyl-3-methyl tetrafluoro ethyl sulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride, 1-methyl-3-octyl group TFMS imidazoles or three hexyls, four decyl phosphonium chlorides
Platinum chloride (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles or three hexyl Si Gui Ji Phosphonium two (trifyl) imidization things;
The sour potassium of chlordene platinum (IV) and 1-ethyl-3-methyl trifluoro methanesulfonic acid imidazoles.
10. catalysis system according to claim 7, wherein said mixture is selected from the group of following mixture, and the group of described mixture comprises: osmium chloride (III) and 1-butyl-3-methyl imidazolitm chloride, 1-ethyl-3-methyl tetrafluoro ethylsulfonic acid imidazoles, 1-methyl-3-octyl group imidazolitm chloride or three hexyls, four decyl phosphonium chlorides.
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CN104109076A (en) * | 2014-06-30 | 2014-10-22 | 浙江大学 | Method for preparing vinyl chloride by hydrochlorinating acetylene through using quaternary phosphonium long-chain ionic liquid as medium |
CN105148989A (en) * | 2015-07-28 | 2015-12-16 | 浙江工业大学 | Porous solid material supported ionic liquid-gold catalyst, as well as preparation and application thereof |
CN106397108A (en) * | 2015-07-31 | 2017-02-15 | 天津大学 | Application of catalyst used for preparation of vinyl chloride to catalysis of one-step preparation of vinyl chloride from dichloroethane and acetylene |
WO2018049820A1 (en) * | 2016-09-18 | 2018-03-22 | 天津大学 | Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination |
CN115715280A (en) * | 2018-10-23 | 2023-02-24 | 科莱恩国际有限公司 | Selective hydrogenation process and catalyst |
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EA029427B1 (en) * | 2012-12-19 | 2018-03-30 | Солвей Са | Process for the hydrohalogenation of an unsaturated hydrocarbon |
EP3103786A1 (en) * | 2015-06-08 | 2016-12-14 | Hexion Research Belgium SA | Process for the production of higher carboxylic acid vinyl esters |
CN107715919B (en) * | 2017-09-29 | 2020-10-09 | 浙江工业大学 | Load type [ PdSClx]x-Catalyst, preparation thereof and application of catalyst in vinyl chloride synthesis |
CN107715915B (en) * | 2017-09-29 | 2020-07-28 | 浙江工业大学 | Sulfide ionic liquid complexed palladium catalyst and preparation method and application thereof |
CN112156809A (en) * | 2020-10-20 | 2021-01-01 | 西安凯立新材料股份有限公司 | Ionic liquid modified activated carbon loaded gold catalyst and application thereof in catalyzing acetylene hydrochlorination |
CN113549116B (en) * | 2021-08-18 | 2022-11-08 | 河北美邦工程科技股份有限公司 | Preparation method and application of metal chelating imidazole catalyst |
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DE709000C (en) | 1936-03-01 | 1941-08-02 | Chem Fab Von Heyden Akt Ges | Process for the preparation of vinyl halides |
JPS52136104A (en) | 1976-05-08 | 1977-11-14 | Denki Kagaku Kogyo Kk | Preparation of vinyl chloride |
DE3824634A1 (en) | 1988-04-30 | 1989-11-09 | Huels Chemische Werke Ag | METHOD FOR PRODUCING VINYL CHLORIDE BY REACTIVATING ACETYLENE WITH HYDROCHLORINE |
BE1004983A3 (en) | 1991-06-20 | 1993-03-09 | Solvay | CATALYST SYSTEM AND METHOD hydrochlorination CHLORIDE PRODUCTION START IN VINYL CHLORIDE ACETYLENE AND HYDROGEN IN THE PRESENCE OF THIS SYSTEM CATALYST. |
BE1004984A3 (en) | 1991-06-20 | 1993-03-09 | Solvay | CATALYST SYSTEM AND METHOD hydrochlorination CHLORIDE PRODUCTION START IN VINYL CHLORIDE ACETYLENE AND HYDROGEN IN THE PRESENCE OF THIS SYSTEM CATALYST. |
FR2910350B1 (en) | 2006-12-22 | 2009-01-30 | Solvay | CATALYTIC HYDROCHLORIZATION SYSTEM AND PROCESS FOR PRODUCING VINYL CHLORIDE FROM ACETYLENE AND HYDROGEN CHLORIDE IN THE PRESENCE OF THIS CATALYTIC SYSTEM |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104109076A (en) * | 2014-06-30 | 2014-10-22 | 浙江大学 | Method for preparing vinyl chloride by hydrochlorinating acetylene through using quaternary phosphonium long-chain ionic liquid as medium |
CN105148989A (en) * | 2015-07-28 | 2015-12-16 | 浙江工业大学 | Porous solid material supported ionic liquid-gold catalyst, as well as preparation and application thereof |
CN106397108A (en) * | 2015-07-31 | 2017-02-15 | 天津大学 | Application of catalyst used for preparation of vinyl chloride to catalysis of one-step preparation of vinyl chloride from dichloroethane and acetylene |
CN106397108B (en) * | 2015-07-31 | 2018-07-10 | 天津大学 | The catalyst for preparing vinyl chloride prepares the purposes of vinyl chloride in catalysis dichloroethanes and acetylene one-step method |
WO2018049820A1 (en) * | 2016-09-18 | 2018-03-22 | 天津大学 | Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination |
CN115715280A (en) * | 2018-10-23 | 2023-02-24 | 科莱恩国际有限公司 | Selective hydrogenation process and catalyst |
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