TW201236758A - Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene - Google Patents

Abstract

Catalytic system consisting essentially of at least one ionic liquid comprising at least one non-protonated cation and at least one anion selected from chloride and methanesulfonate and its use in the hydrochlorination reaction of acetylene with hydrogen chloride.

Description

201236758 VI. Description of the Invention: [Technical Field] The present invention relates to a catalytic system which is particularly useful in a process for producing vinyl chloride by hydrochlorination of acetylene. The invention also relates to such a method. [Prior Art] The production of vinyl chloride by the reaction between acetylene and hydrogen chloride is usually carried out in the gas phase in a fixed bed reactor in the presence of a heterogeneous solid catalyst loaded with mercuric chloride. . Catalytic systems with reduced or no mercury compounds are currently of increasing interest primarily due to toxicity. A number of different catalysts have been developed to replace the catalysts in current gas phase processes. For example, the uncensored patent application 52/1 36 1 04 describes a process for the hydrochlorination of acetylene in the presence of a fixed catalytic bed consisting of a noble metal halide deposited on activated carbon in the gas phase. However, to date, the lifetime of such alternative catalysts intended for use in gas phase processes is still much shorter than the lifetime of mercury based catalysts. In addition, there are some examples in the literature for the hydrochlorination of acetylene in the presence of a liquid catalytic medium. German Patent 709.000 describes a process for preparing vinyl halides by contacting acetylene with a hydrohalide salt melt of an organic city containing a standard catalyst at elevated temperatures. Aliphatic, aromatic or heterocyclic amines -5 - 201236758 and mixtures thereof are considered as organic domains. The inventor's certificate SU 23 7 1 1 6 describes the use of a cuprous chloride containing ^wt°/〇 and a hydrochloride of from 1 4 wt% to 16 wt% of a methylamine, amine or trimethylamine. Aqueous acid solution. European Patent Application No. -0 340 4 1 6 discloses the production of ethylene by reacting acetylene with hydrogen chloride in a solvent consisting of an aliphatic or alicyclic guanamine as a catalyst at a high temperature. method. Although it allows for high yields, however, this has some significant drawbacks: it has been shown to gradually degrade the catalyst system under reaction conditions to form a black product with a carbonaceous appearance. Furthermore, in the presence of hydrogen chloride, the decylamine is converted to a salt which typically has a melting point well above room temperature. For example, N-methylpyrrolidine is only a liquid above 80 °C. In fact, this can cause serious implementation problems associated with blockage of the catalyst medium at the coldest point of the facility during reactor shutdown. Thus, the entire reaction and also the line in which the reaction medium flows must be continuously maintained at the temperature at which the hydrochloride salt melts. These different problems have been solved by the hydrochlorination reaction system described in the European patent applications EP 0 5 1 9 5 4 8 - A 1 and EP 0 843 - A1, which systems comprise at least one Group VIII gold And an amine hydrochloride (having a melting point lower than or equal to 25 ° C, a fatty amine hydrochloride containing more than 8 carbon atoms (the melting point of 25 ° C) and selected from aliphatic, alicyclic a family of aromatic hydrocarbons and an organic solvent thereof. However, the catalysts described therein are r 4 6 dimethyl groups in the chamber chlorine preparation method Above 5 2 5 seems to be subordinate): or higher than the mixed system,

S -6- 201236758 Especially the system in which the Group VIII metal compound is platinum (II) chloride or palladium chloride (II), when considering the productivity of producing vinyl chloride from the hydrochlorination of acetylene and the flood season The stability aspects they make are not fully satisfactory when they enable performance. WO 200 8/778 68 discloses a catalyzed hydrochlorination reaction system comprising at least one amine hydrochloride and at least one Group VIII metal compound selected from the group consisting of: a uranium (IV) A mixture of a compound with tin chloride (ruthenium), a mixture of a platinum (II) compound and triphenylphosphine oxide, and a mixture of a palladium (II) compound and triphenylphosphine. The catalytic system exhibits an improved productivity compared to the system described in the European patent applications EP-A 0519548 and EP-A 0525843. Finally, patent application CN 101*716528 discloses a catalytic system for the production of vinyl chloride by hydrochlorination of acetylene, the catalytic system comprising ions having chlorine, bromine, hexafluorophosphate or tetrafluorophosphate as an anion Imidazole-based ionic liquids and one or more of the chlorides of gold, uranium, palladium, tin, mercury, copper or cerium. The above catalytic system exhibits the disadvantage of requiring an amine hydrochloride or an ionic liquid and at least one metal compound, which increases the cost of the catalytic system. Problems associated with passivation of metals can also occur in such catalytic systems. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a catalytic system, in particular with hydrochlorination of 201236758 and more particularly for the hydrochlorination of acetylene, which is as simple and inexpensive as possible, it does not Problems associated with passivation of metal are encountered and very good performance is allowed. Another object of the present invention is to provide a process for the synthesis of vinyl chloride by hydrochlorination of acetylene in the presence of such a catalytic system which does not degrade under the reaction conditions and which enables a very good orientation towards vinyl chloride. Productivity. Unlike mercury compound-based systems, the catalytic system according to the present invention has the advantage of having no toxicity problems associated with such compounds and avoiding evaporation of metal salts in the facility. The present invention therefore relates to a catalytic system, and more particularly to a catalytic system for the hydrochlorination of acetylene, as defined in the scope of the patent application. The preferred embodiment of the catalytic system according to the present invention is set forth in the scope of the patent application, which is incorporated herein by reference. Another aspect of the invention relates to the hydrochlorination of acetylene in the presence of a catalytic system as defined in the scope of the patent application and the scope of the patent application of the patent application. A method of reacting vinyl chloride. The catalytic system according to the invention consists essentially of at least one ionic liquid comprising at least one non-protonated cation and at least one anion selected from the group consisting of chloride and mesylate. The expression "consisting essentially of" is understood in this specification to mean a catalytic system according to the invention in addition to at least one ionic liquid as defined.

S-8-201236758 may also include one or more additional components (preferably in small amounts) that have no effect on the catalytic properties of the catalytic system; in other words, the reaction during the reaction using the catalytic system No catalysis. Among the one or more additional components, one or more ionic liquids other than the one or more ionic liquids defined above may be mentioned, for example, they are added to lower the viscosity of the catalytic system. Preferably, the catalytic system according to the invention does not comprise any metal. Preferably, the catalytic system according to the invention consists of at least one ionic liquid comprising at least one non-protonated cation and at least one anion selected from the group consisting of chloride and mesylate. The expression "consisting of" is understood in this specification to mean that the catalytic system consists solely of at least one ionic liquid as defined above. Ionic liquids are mainly salts in a liquid state, while ordinary liquids (such as water and gasoline) are mainly composed of electrically neutral molecules. Ionic liquids are advantageously composed of ions. It is generally believed that any salt that melts without decomposition will generally produce an ionic liquid. However, many salts melt at high temperatures, much higher than those used in catalytic processes. For the purposes of the present invention, the term ionic liquid shall mean a system which is liquid at the temperatures used in the process using the catalytic system. For the purposes of the present invention, a preferred ionic liquid system is at a temperature of 150 ° C or lower, more preferably at 100 ° C or lower, more preferably at 80 ° C or lower. Those that are liquid at the temperature. Most preferred is an ionic liquid that is in a liquid state at room temperature or even below room temperature. Further, the preferred ionic liquid -9-201236758 is one which has a very low vapor pressure and a very low flammability and exhibits good electrical conductivity. The ionic liquid which advantageously acts as a reaction medium is preferably selected such that it is substantially inert to the materials participating in the reaction and preferably has solvent capabilities for the products and intermediates formed in the reaction. The expression "at least one ionic liquid" in this specification is understood to mean one or more than one ionic liquid. Preferably, the catalytic system consists essentially of an ionic liquid as defined above. In the remainder of the text, the expression "in singular or plural" is used to mean one or more than one ionic liquid, unless otherwise stated. The ionic liquid according to the invention comprises at least one non-protonated cation and at least An anion selected from the group consisting of chloride and mesylate. In the present specification, the expression "at least one non-protonated cation" is understood to mean one or more than one. non-protonated cation. Preferably, the The ionic liquid includes an unprotonated cation. In the remainder of the text, the expression "a non-protonated cation" used in the singular or plural form is understood to mean one or more than one non-protonated cation unless otherwise stated. As used herein, the term aprotonated cation, for the purposes of the present invention, shall mean a cation that does not carry one or more free hydrogen atoms at one or more of the atoms to which the positive charge of the cation is assigned. The non-protonated cation is selected from

-10- S 201236758 - quaternary ammonium cation, which may be represented by the general formula [nrH'r]4, a phosphonium cation, which may be represented by the general formula [NR'rUT, - a cation comprising a five or six membered heterocyclic ring, the heterocyclic ring There is at least one nitrogen atom, advantageously one or two nitrogen ions. Preferred cations comprising a five or six membered heterocyclic ring - having the oxime cation of formula (I) R3 R4

a pyridinium cation having the formula (II), and

Pyrrolidine cation having the general formula (III)

Wherein the group R and R1 to R9 may each independently of each other be a hydrogen, optionally substituted saturated or unsaturated group (preferably -11 - 201236758 is a randomly substituted saturated or unsaturated Ci-) a C^-institutional group and ig is preferably a optionally substituted saturated or unsaturated C^-Cm-house group), wherein the carbon chain is interrupted by an oxygen atom, optionally substituted, saturated or unsaturated. The C2-Cualkyl group, or the optionally substituted C6_C|2 aryl group, is agglomerated, provided that the group carried by one or more atoms to which the positive charge of the cation is carried is not hydrogen. Preferably, the non-protonated cation is selected from the group consisting of quaternary ammonium cations, iron cations, imidazolium cations, pyridyl cations, and pyrrolidine cations. More preferably, the non-protonated cation is selected from the group consisting of phosphonium cations, imidazolium cations, pyridyl cations, and pyrrolidine cations. Most preferably, the non-protonated cation is selected from the group consisting of scaly cations and imidazole cations. Catalytic systems in which the non-protonated cations are selected from the group consisting of scaly cations and pyrrolidine cations are novel and give good results within the framework of the present invention. Examples of quaternary ammonium cations are tributylmethylammonium, butyltrimethylammonium, octyltrimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, methyltrioctylammonium '2-hydroxyl Ethyltrimethylammonium and diethylmethyl(2-methoxyanthrylethyl)ammonium. Examples of scale cations are triisobutylmethyl scale, tributylmethyl scale, ethyltributyl scale, tetrabutyl scale, tetraoctyl scale, tributyltetradecyl scale, trihexyltetradecyl scale, and Benzyl triphenyl scales. Examples of imidazole cations are 1,3 dimethylimidazole, 1 ·ethyl-:3- -12- 201236758 methyl imidazole, 1-butyl-3-methylimidazole, 1-pentyl- 3-methyl imiline, 1-hexyl-3-methylimidazole, 1-mercapto-3-methylimidazolium, 1-dodecyl-3-methylimidazole, 丨-tetradecane 3-methylimidazolium, 1-hexadecyl-3-methylimidazole, i-(2-hydroxyethyl)-3-methylimidazolium, 1-allyl-3-methyl Imidazole key, 丨_benzyl-3_methylimidazole key, 丨_phenylpropyl-3-methylimidazole key, i,3-diethylimidazole key, 1-butyl-3-ethylidazole key , 1-methyl-3-propylimidazole, 1-methyl-3-octyl imidazole, 1-methyl-3-octadecyl imidazole, i,3-dibutyl-2-methyl Imidazolium, 1,3 -dimercapto-2-methylimidazole, 1-(2-hydroxyethyl)-3-methylimidazole, 1-ethyl-2,3-dimethylimidazole , 1-propyl-2,3-dimethylimidazole, 1-butyl-2,3-dimethylimidazole, 1-butyl-3,4-dimethylimidazole, b-hexyl-2 , 3-dimethylimidazole, 1-hexadecyl-2,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1,3, 4-trimethylimidazolium, 1-butyl-3-ethylimidazolium, 1,3-dibutylimidazole, 1-methyl-3-octyl imidazole, 1-butyl-3,4 , 5-trimethylidazole key and 1,3,4,5-tetramethylimidazole key. Examples of pyridine gun cations are 1-methylpyridine gun, 1-ethylpyridine gun, 1-propylpyridine key, 1-butylpyridine key, 1-hexylpyridinium, 1-octylpyridinium, 1,2 - dimethylpyridine, 2-ethyl-1.methylpyridine, ?-butyl-2-methylpyridine, 1-butyl-3-methylpyridine, 1-butyl-4 -methylpyridine, 1-hexyl-3-methylpyridine, 1-hexyl-4-methylpyridine, 1-butyl-2-ethylpyridinium, 1-butyl-3-ethylpyridine Key, 4-methyl-1 -octylpyridine, 1-butyl-2-ethyl-6-methylpyridine, 2-ethyl-1,6-dimethylpyridine, 1-butyl -3,4-Dimethylpyridine key and 1-butyl-3,5-dimethylpyridine gun. -13- 201236758 Examples of pyrrolidine gun cations are 1,1 dimethylpyrrolidine key ' 1 _ethyl-1-methylpyrrolidine key, 1-ethyl-3-methylpyrrolidine key, 1- Butyl-I-methylpyrrolidine, 1-hexyl-1-methylpyrrolidine gun, 1-octyl-1-methylpyrrolidinium, 1-butyl-1-ethylpyrrolidine and 1 -Methyl-1 -propylpyrrolol iron. The expression "at least one anion" in this specification is to be understood to mean one or more than one anion. Preferably, the ionic liquid comprises an anion. In the remainder of the text, the expression "anion" used in the singular or plural is understood to mean one or more than one anion unless otherwise stated. The at least one anion is selected from the group consisting of chloride and mesylate. The catalytic system according to the invention consists essentially of at least one ionic liquid comprising at least one non-protonated cation and at least one anion selected from the group consisting of chloride ions and mesylate, wherein for non-protonated cations and for anions The preferred items are listed above. Preferably, the ionic liquid system is selected from the group consisting of: quaternary ammonium chlorides, quaternary ammonium methanesulfonates, chlorinated scales, methanesulfonic acid scales, imidazolium chloride, methanesulfonic acid Imidazole gun, pyridine chloride, pyridinium sulfonate, chlorinated pyrrolidine key and pyrrolidine mesylate. Wherein the ionic liquid system is selected from the group consisting of quaternary ammonium methanesulfonate, chlorinated money, methanesulfonic acid scale, imidazole mesylate, pyridinium mesylate, pyrrolidine chloride, and pyrrolidine mesylate. Novel and within the framework of the present invention - 14

S 201236758 gives good results. More preferably, the ionic liquid system is selected from the group consisting of: chlorinated scale, iron methanesulfonate, imidazolium chloride, imidazolium mesylate, pyridinium chloride, pyridinium methanesulfonate, pyrrolidine chloride and a Sulfonic acid pyrrolidine key. More preferably, the ionic liquid system is selected from the group consisting of chlorinated scales, methanesulfonic acid scales, imidazolium chloride, and imidazolium methanesulfonate. The catalytic system in which the ionic liquid system is selected from the group consisting of chlorinated scales and imidazolium methanesulfonate is novel and gives good results within the framework of the present invention. Particularly preferred ionic liquid systems are those used in the working examples below, namely 1-butyl-3-methylimidazolium chloride, triethyltetradecyl chloride, 1-ethyl methanesulfonate. 3-methylimidazole gun, 1-methyl-3-octyl imidazolium chloride, 1-ethyl-3-methylimidazole chloride, and 1-benzyl-3-methylimidazole chloride. The catalytic system in which the ionic liquid system chlorinates trihexyltetradecyl sulphate or methanesulfonic acid 1-ethyl-3-methylimidazole is novel and gives good results within the framework of the present invention. Wherein the ionic liquid system is selected from the group consisting of 1-methyl-3-octyl imidazolium chloride, 1-ethyl-3-methylimidazole chloride, and 1-benzyl-3-methylimidazolium This is also the case with the system. Particularly preferred ionic liquid systems are commercially available, for example, from Liquid Electrolyte Technology (Iolitec GmbH) or from BASF SE. Methods for making suitable ionic liquids are known to those of ordinary skill and are therefore not necessarily described in detail herein. -15- 201236758 The catalyst system according to the invention can be used in the liquid phase or deposited on a bulk carrier such as vermiculite alumina, belite, cordierite, mullite or activated carbon (only a few suitable carriers are listed) On the material), up to the pore volume of the support and the limit of available surface area. The carrier may have any shape for such carrier materials including, but not limited to, honeycombs as well as extrudates or the like. When the catalytic system is used in the liquid phase, it can be diluted with an organic solvent. The choice of the nature of the organic solvent to be included in the catalytic system according to the invention then depends inter alia on the requirement that it is inert with respect to the reactants under the reaction conditions, that it is easily mixed or not easily mixed with the ionic liquid; It is desirable to form a medium with the ionic liquid that has a viscosity that is lower than the viscosity of the ionic liquid alone. Preferably, however, the ionic liquid itself acts as a solvent so that no additional solvent is necessary. The catalytic system according to the invention can be used for any reaction to alkynes, ie a compound in which two carbons are linked by a triple bond. In such alkynes, mention may be made of acetylene, propyne (also known as methyl acetylene). ), dimethyl dimethyl acetylate, 1,4-butene diol, together with propyne compounds. The reaction can be nitrogen halogenation, in particular hydrochlorination (with hydrogen chloride), hydroiodination (with hydrogen iodide), hydrofluorination (with hydrogen fluoride), or hydrobromination (with bromine) Hydrogenation), or reaction with phosphoric acid. The catalytic system according to the invention is particularly useful for the hydrochlorination of acetylene. In the present invention, the term "acetylene" is understood to mean acetylene or contains

-16- S 201236758 A mixture of alkynes which may contain, in addition to acetylene, other components, such as ethylene or other unsaturated hydrocarbons, which may be by-products of acetylene synthesis. The source of such mixtures of different unsaturated compounds may be mixtures of any source, as they may be obtained during the known synthetic methods for acetylene. Mixtures containing less than 50% acetylene can be used. Preferably, however, the term "acetylene" means a mixture comprising at least 90% acetylene and more preferably 100% acetylene. Acetylene is primarily produced by partial combustion of methane or as a by-product of ethylene vapor from hydrocarbon cracking. Another method for the manufacture of acetylene is the hydrolysis of carbonized fishing.

CaC〗 + 2H2O - ► Ca(OH)2 + C2H2 This requires an extremely high temperature of about 2000 ° C, making it necessary to use an electric furnace or the like. The mixture comprising acetylene and ethylene can be used as it is, i.e. without the need to separate the components 'because the reactivity of acetylene compared to ethylene enables the hydrochlorination of acetylene to first separate the vinyl chloride obtained and subsequently use ethylene. get on. The ethylene can be chlorinated to produce 1,2-dichloroethane' for use in a combined process for the manufacture of vinyl chloride monomer. Pyrolysis of 1,2-dichloroethane can produce hydrogen chloride for this first reaction with acetylene. Accordingly, the present invention also relates to a process for the production of vinyl chloride in the presence of a catalytic system according to the invention by the reaction of acetylene with hydrogen chloride (hydrochlorination)" as defined above for the catalytic system according to the invention Definitions and preferences apply to a process for the manufacture of vinyl chloride according to the invention. -17- 201236758 The process according to the invention can advantageously be carried out at temperatures ranging from room temperature to 22 °C. At higher temperatures, the catalytic system has a tendency to degrade. The preferred reaction temperature, i.e., the best compromise between providing productivity, yield, and stability of the catalytic medium, is greater than or equal to about 40 °C. At a temperature greater than or equal to about 50 ° C, more preferably at a temperature greater than or equal to about 80 ° C, and most preferably at most temperatures equal to or greater than about 120 ° C. good result. Preferably, the reaction temperature does not exceed about 200 °C. The reaction temperature of about 40 ° C to about 200 ° C is the most particularly good. In some cases, a reaction temperature of not more than 1 70 ° C proves to be advantageous. The process according to the invention is advantageously carried out at ambient pressure or at a higher pressure compatible with the safety regulations for the treatment of acetylene. Usually, the pressure will not exceed 5 MPa, and preferably it will not exceed the partial pressure of acetylene of 2.5 Mpa. The process for the preparation of vinyl chloride by hydrochlorination of acetylene in accordance with the present invention is advantageously carried out by contacting gaseous reactants (acetylene and hydrogen chloride) with the catalytic system in any suitable reactor. The process according to the invention can be carried out conventionally in any apparatus which promotes gas-liquid exchange, such as a plate column, an overflow enthalpy column or an overflow non-filling column. Another embodiment of the process which enables good material exchange between the gas phase and the liquid phase comprises the use of a countercurrent reactor which can be optionally sprayed into a bed type, the liquid catalytic system flowing through the gas stream against the reactants. Filling things. In the process according to the invention, hydrogen chloride and B are added to the reactor

S -18- 201236758 The molar ratio of the alkyne is advantageously greater than or equal to a ratio greater than or equal to about 〇. It is advantageous to 3. 5。 The amount of less than or equal to about 1.5. Good results have been obtained when hydrogen chloride and acetylene are from about 〇. Acetylene and hydrogen chloride can be mixed prior to entering the reactor in the reactor. In order to increase the B method dissolved in the liquid phase, only acetylene is reacted in the process with hydrogen in the liquid phase. Hydrogen chloride can be used in any form pure or dissolved in the solvent to be extracted, followed by drying of an intermediate. The catalytic system according to the invention is advantageously used in the manufacture of vinyl chloride. The present invention therefore also relates to the production of vinyl chloride in accordance with the present catalytic hydrogenation to produce a simple and inexpensive catalyst compared to conventional catalytic systems, without encountering a passivation rate with the metal, Selectivity and therefore also improved properties and characterized by long-term stability The catalytic system according to the invention additionally has a height of about 0.5. Preferably, the molar ratio is less than or equal to about 2% to about 3 molar ratios of hydrogen chloride and hexagram molar ratio, or preferably in the amount of acetylene. It is possible to introduce into the reactor using a gaseous form, the presence of a chlorinated form in the form of a chloride: a diluted gaseous, for example an insoluble amine, which is operational. The use of the catalytic system according to the invention for acetylene can be used. In contrast, the advantages of the catalytic system according to the present invention are problems with the catalytic system. It also allows for very good conversion productivity. The use of mercury compounds is avoided and does not have the advantage of toxicity problems associated with these compounds. The following examples are intended to illustrate the invention, but are not intended to limit the scope thereof. The examples indicated by the letter C are comparative examples and the other examples describe the catalytic system according to the present invention. General procedure for working examples: 30 ml of a catalytic system consisting mainly of the corresponding ionic liquid used in the received form is added to a Pyrex reactor with an internal volume of 45 ml, 'the reactor is equipped with heat A double clamp that circulates the oil therein and a device for introducing the reactants, consisting of a sintered glass nozzle, which is intended to ensure the dispersion of the gas in the liquid medium. The reactor was maintained at a temperature of 150 °C. The reactants acetylene and HCl were introduced at a molar ratio of 1:1.2 in an amount of 10 Nl/h and 12 Nl/h (measured at 0 ° C and atmospheric pressure). The conversion of acetylene was analyzed for the effluent leaving the reactor. The selectivity was 100% in all experiments, i.e., no by-products were present except for the desired product, vinyl chloride. Therefore, the productivity can be directly calculated from the conversion ratio of acetylene. The following are summarized in the ionic liquid system tested and indicated in the table of the catalytic system tested: IL1 1-butyl-3-methylimidazolium chloride IL2 trihexyltetradecyl sulphate IL3 methane sulfonate Acid 1-ethyl-3-methylimidazole

-20- S 201236758 IL4 1-methyl-3-octyl imidazolium chloride IL5 1-ethyl-3-methylimidium chloride IL6 Chlorinated 1-benzyl-3·methylimidazole key IL7 1 -ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) quinone imine IL8 butyl trimethylammonium bis(trifluoromethylsulfonyl) quinone imine IL9 butyl-4-methylpyridine Key di(trifluoromethylsulfonyl) quinone imine IL10 trifluoromethanesulfonate 1-ethyl-3-methylimidazole key IL1 1 tetrachloroferric (III) acid 1-butyl-3-methylimidazole Key IL12 tetrafluoroethylsulfonic acid 1-ethyl-3-methylimidazole key IL 13 toluenesulfonic acid triisobutylmethyl scale IL14 trifluoromethanesulfonic acid 1-methyl-3-octyl imidazole key IL15 trihexyl ten Tetraalkyl iron bis(trifluoromethylsulfonyl) quinone imine IL1 6 1-butyl-1-methylpyrrolidine bis(trifluoromethylsulfonyl) quinone imine IL17 1-ethyl- 2,3-Dimethylimidazolium iron (trifluoromethylsulfonyl) quinone imine The results of these experiments are given in the table below and / or shown in Figure 1, which shows acetylene conversion (%) changes with time (X-axis shows time in hours)" The number of the immediately adjacent curve corresponds to the instance No.-21 - 201236758 Table 1 - Examples 1 to 17 Example No. Ionic Liquid Results 1 IL1 Figure 1 2 IL2 Figure 1 3 IL3 Figure 1 4 IL4 Figure 1 5 IL5 Figure 1 6 IL6 Figure 1 7C IL7 No Transformation 8C IL8 No Transformation 9C IL9 No transformation 1 0C IL 1 0 No transformation 1 1 C IL1 1 No transformation 1 2C IL 1 2 No transformation 1 3C IL 1 3 No transformation 1 4C IL 1 4 No transformation 1 5C IL 1 5 No transformation 1 6C IL 1 6 No conversion 1 7C IL 1 7 No conversion The results of these experiments showed that very good results were obtained with the catalytic systems according to Examples 1 to 6 and no conversion was observed for the catalytic systems according to Comparative Examples 7 to 17. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the results of the experiments of Examples 1 to 6.

-22- S

Claims (1)

201236758 VII. Patent application scope: 1. A method for producing vinyl chloride by reacting acetylene with hydrogen chloride in the presence of a catalytic system, the catalytic system consisting essentially of at least one ionic liquid, the ionic liquid comprising at least one An unprotonated cation and at least one anion selected from the group consisting of chloride and mesylate. 2. The method of claim 1, wherein the non-protonated cation is selected from the group consisting of a quaternary ammonium cation, a phosphonium cation, and a cation comprising a five or six membered heterocyclic ring having at least one nitrogen atom. 3. The method of claim 2, wherein the five or six member heterocycle has one or two nitrogen atoms. 4. The method of claim 1, wherein the non-protonated cation is selected from the group consisting of quaternary ammonium cations, iron cations, imidazolium cations, pyridyl cations, and pyrrolidine cations. 5. The method of claim 1, wherein the non-protonated cation is selected from the group consisting of a scaly cation and a pyrrolidine cation. 6. The method of claim 1, wherein the ionic liquid system is selected from the group consisting of: quaternary ammonium chloride, quaternary ammonium methanesulfonate, chlorinated scale, methanesulfonic acid scale, imidazolium chloride, mesylate imidazole , pyridine chloride _, pyridinium mesylate, chlorinated pyrrolidine key and pyrrolidine mesylate gun. 7. The method of claim 1, wherein the ionic liquid system is selected from the group consisting of chlorinated scales and imidazolium methanesulfonate. 8. The method of claim 7, wherein the ionic liquid system is selected from the group consisting of trihexyltetradecyl chloride or 1-ethyl-3-methylimidazolium methanesulfonate. -23- 201236758 9. The method of claim 6, wherein the ionic liquid system is selected from the group consisting of 1-methyl-3-octyl imidazolium chloride, 1-ethyl-3-methylimidazolium chloride And a 1-benzyl-3-methylimidazolium chloride. The method of claim 1, wherein the reaction is carried out at a temperature ranging from room temperature to 220 °C. 11. A catalytic system consisting essentially of at least one ionic liquid. The ionic liquid comprises at least one non-protonated cation and at least one anion selected from the group consisting of chloride and mesylate, wherein the non-protonated cation is selected from the group consisting of squamous cations And a pyrrolidine cation. 1 2. A catalytic system consisting essentially of at least one ionic liquid, the ionic liquid comprising at least one non-protonated cation and at least one anion selected from the group consisting of chloride and mesylate, wherein the ionic liquid system is selected from the group consisting of methyl sulfonate Acid quaternary ammonium, chlorinated scale, methanesulfonic acid scale, mesylate imidazole, mesylate pyridine, chloropyrrolidine and pyrrolidine mesylate. The catalytic system of claim 12, wherein the ionic liquid system is selected from the group consisting of chlorinated scales and imidazolium mesylate. The method of claim 13, wherein the ionic liquid is selected from the group consisting of trihexyltetradecyl chloride or a 1-ethyl-3-methylimidazole gun. a catalytic system consisting essentially of at least one ionic liquid, the ionic liquid comprising at least one non-protonated cation and at least one chloride anion, wherein the ionic liquid system is selected from the group consisting of 1-methyl-3-octyl chloride Imidazole key, 1-ethyl-3-methylimidazole chloride, and 1-benzyl-3-methylimidazole chloride. -24- S