EA025978B1 - Process for the hydrohalogenation of an alkyne and for the manufacture of vinyl chloride by hydrochlorination of acetylene - Google Patents

Abstract

Process for the hydrohalogenation of an alkyne and for manufacturing vinyl chloride by hydrochlorination of acetylene in the presence of a catalytic system comprising at least one ionic liquid comprising at least one non-protonated cation, according to which said process is carried out in apparatus made from or covered with materials which are resistant to halogenated acids and more particularly HCl, in dissociated form.

Description

The invention relates to a method for the hydrohalogenation of alkyne and for the production of vinyl chloride by hydrochlorination of acetylene.

The production of vinyl chloride by the reaction of acetylene and hydrogen chloride is usually carried out in the gas phase, in a fixed-bed reactor in the presence of a heterogeneous solid mercury chloride-based catalyst on a support. Basically, due to the cause of toxicity, there is currently increasing interest in catalytic systems with a reduced mercury content or no mercury compounds at all.

Various catalysts have been developed to replace existing catalysts in a gas phase process.

For example, Japanese Unexamined Patent Application 52/136104 describes a process for hydrochlorinating acetylene in a gas phase in the presence of a fixed catalyst bed consisting of noble metal halides supported on activated carbon. However, to date, the service life of such alternative catalysts designed for gas phase processes is much shorter than the service life of catalysts based on mercury compounds.

In addition, there are a number of examples in the literature of acetylene hydrochlorination in the presence of a liquid catalyst medium.

German patent 709000 describes a process for producing vinyl halides by contacting acetylene at high temperatures with a melt of the hydrohalogen salt of organic bases containing a standard catalyst. Aliphatic, aromatic or heterocyclic amines and mixtures thereof are organic bases.

Copyright 8I 237116 describes the use of an aqueous acid solution containing 46 vol.% Copper chloride and from 14 to 16 vol.% Methylamine, dimethylamine or trimethylamine hydrochloride.

European patent EP-A-0340416 discloses a process for producing vinyl chloride by reacting acetylene with hydrogen chloride in the presence of palladium compounds as a catalyst, in a solvent consisting of aliphatic or cycloaliphatic amides, at a temperature above room temperature. Despite the fact that this provides high yields, this process, however, has a number of significant drawbacks: it turned out that under the reaction conditions the liquid catalytic system gradually decomposes, forming blackish carbon-type products. In addition, in the presence of hydrogen chloride, the amide is converted to hydrochloride, the melting point of which is usually much higher than room temperature. Ν-methylpyrrolidone hydrochloride, for example, is a liquid only above 80 ° C. In practice, this can cause serious problems during execution, problems associated with agglomeration of the catalytic medium during reactor shutdown or line blocking at the coldest point of the installation. The entire reactor and also the lines in which the reaction medium flows must constantly maintain a temperature above the melting point of the hydrochloride.

These various problems seemed to be solved thanks to the catalytic hydrochlorination system described in European patents EP 0519548-A1 and EP 0525843-A1, which include at least one compound of a Group VIII metal and any amine hydrochloride whose melting point is less than or equal to 25 ° C, or a fatty amine hydrochloride of more than 8 carbon atoms, the melting point of which is above 25 ° C and an organic solvent selected from aliphatic, cycloaliphatic or aromatic hydrocarbons or mixtures thereof. Nevertheless, the catalytic systems described therein, especially those in which the group VIII metal compound is platinum chloride (P) or palladium chloride (P), are not completely satisfactory provided that they are introduced to increase the performance of vinyl chloride by hydrochlorination acetylene and to prolong thermal stability.

\ νϋ 2008/77868 describes a catalytic hydrochlorination system comprising at least one amine hydrochloride and at least one group VIII metal compound selected from the group formed by a mixture of platinum compound (II) with tin chloride (II), a mixture of platinum compound (II ) with triphenylphosphine oxide and a mixture of palladium (P) compound with triphenylphosphine. These catalytic systems have improved performance compared to the systems described in European patents EP 0519548-A1 and EP 0525843-A1.

Finally, patent CN 101716528 (with reference to the inventor Ζ1ιίνοη§ Yi) describes catalytic systems for the production of vinyl chloride by hydrochlorinating acetylene containing imidazole (which is an unprotonated cation) based on an ionic liquid with chloride, bromide, hexafluorophosphate and tetrafluorophosphate and tetrafluorophosphate and one or more chloride of gold, platinum, palladium, tin, mercury, copper or rhodium.

The latter catalyst system, as it turned out, leads to an increase in selectivity and an increase in the degrees of conversion, at least when used in laboratory devices made of chemically inert materials (like glass or pyrex). In this regard, the publication of Sgeei Sies., 2011, 13, 1495, in which и1ιίνοη§ Wu was one of the authors, accurately describes a glass reactor without any mention of corrosion problems. In fact, glass was not chosen to solve the problems of corrosion, but it is a widespread material used mainly for laboratory equipment.

However, the applicant noted that, unexpectedly, materials used in industrial equipment processing processes in the aforementioned patents using amine hydrochloride quickly and strongly corrode if the imidazole above contains a hydrochlorinated medium. And after some verification, the applicant noted that this problem could also extend to ionic liquids containing at least one non-protonated cation and HC1.

Then the applicant unexpectedly discovered that when using materials that are resistant to the dissociation of HC1 (i.e., HC1 dissociates into active protons and chlorine anions), this problem almost disappears. This is very surprising, because there is no water in the reaction medium (while the dissociation of HC1, as is known, occurs due to the presence of water) and since in the aforementioned hydrochlorination processes using amine hydrochloride, the presence of HC1 does not appear to lead to corrosion problems. In fact, similar problems occur with all halogen acids, not only with hydrogen chloride, but also with hydrogen iodide, hydrogen fluoride and hydrogen bromide. Such acids can be used to hydrogenate alkynes, i.e. compounds in which two carbon atoms are linked together by a triple bond. Among such alkynes, acetylene, propine, which is also called methylacetylene, dimethylacetylene dicarboxylate, 1,4-butanediol, as well as propargyl compounds can be distinguished.

The presented invention relates to a method for the hydrohalogenation of alkyne (preferably acetylene) in the presence of a catalytic system containing at least one ionic liquid containing at least one non-protonated cation, due to which the said method is at least partially carried out in a device made completely or coated with materials that are resistant to HC1 in dissociated form and which are selected from metals, polymers, ceramics, refractory materials, (processed) graphite and enamel.

A preferred embodiment of the invention relates to a method for the production of vinyl chloride by hydrochlorination of acetylene in the presence of a catalytic system containing at least one ionic liquid containing at least one non-protonated cation, whereby this method is at least partially carried out in a device made completely or coated with materials that are resistant to HC1 in dissociated form and which are selected from metals, polymers, ceramics, refractory materials s (treated) graphite and enamel.

The term “at least partially” is understood to mean that at least a part of the device where the reaction proceeds and which comes into contact with the reaction medium is made of said corrosion resistant materials.

The term resistant to halogen acids (HC1) in dissociated form means that the corresponding materials can be used for the part of the device during the normal life (several years, usually at least 10 years) without the need for replacement or repair.

As used herein, the term acetylene is understood to mean acetylene or mixtures containing acetylene, which, together with acetylene, may contain other components, such as ethylene or other unsaturated hydrocarbons, which may be by-products of acetylene synthesis. The source of such mixtures of various unsaturated compounds can be any known source of reaction mixtures, since they can be obtained in the process of known methods for the synthesis of acetylene. Mixtures containing less than 50% acetylene can be used. Preferably, however, the term acetylene refers to mixtures containing at least 90% acetylene, and more preferably 100% acetylene.

Acetylene is mainly produced by the partial combustion of methane or appears as a by-product in the ethylene stream in the cracking of hydrocarbons.

Another method for producing acetylene is the hydrolysis of calcium carbide.

CaC ₂ + 2H ₂ O.Ca (OH) ₂ + C ₂ H ₂ , which requires very high temperatures, approximately 2000 ° C, which necessitates the use of electric furnaces or the like.

Mixtures containing acetylene and ethylene can be used directly as such, without the need for separation of the components, because the reactivity of acetylene, as well as ethylene, allows you to first carry out the hydrochlorination of acetylene with the release of vinyl chloride obtained by using ethylene. This ethylene can be chlorinated to produce

1.2- Dichloroethane for a joint process for the production of vinyl chloride monomer. Pyrolysis

1.2-dichloroethane can lead to the formation of hydrogen chloride for the first reaction with acetylene. The hydrochlorination reaction in accordance with the invention is preferably carried out at a temperature range from room temperature to 220 ° C. At high temperatures, the catalyst system is prone to decomposition. The preferred reaction temperature, that is, the one at which there will be the best correspondence between productivity, yield and stability, is 40 ° C. The best results are obtained at temperatures above or equal to 50 ° C, and more preferably 2,025,978, at temperatures above or equal to 80 ° C, and even more preferably at temperatures above or equal to 120 ° C. The main thing is that the reaction temperature does not exceed 200 ° C. A reaction temperature of from 40 to 200 ° C. is most preferred. In some cases, a reaction temperature of 170 ° C. has proven to be more advantageous.

The hydrochlorination reaction in accordance with the invention is preferably carried out at atmospheric pressure or at elevated pressures compatible with safety in the handling of acetylene. Typically, the pressure does not exceed 5 MPa, preferably should not exceed 2.5 MPa, the partial pressure of acetylene.

The hydrochlorination of acetylene in accordance with the invention is preferably carried out by bringing gaseous reactants — acetylene and hydrogen chloride — into contact with the catalyst system in any suitable reactor.

The hydrochlorination reaction in accordance with the invention can be carried out in the usual way in any gas-liquid exchange equipment, such as a plate column, a flooded packed column or a flooded non-packed column. Another variant of the method, providing a good metabolism between the liquid and gas phases, consists in using a countercurrent reactor, in some cases with a filter bed, the liquid catalytic system flows through the filter bed in countercurrent with a gaseous stream of reactants.

In the method according to the invention, the molar ratio of hydrogen chloride to acetylene introduced into the reactor is preferably greater than or equal to about 0.5. Preferably, this ratio is greater than or equal to about 0.8. Advantageously, this molar ratio is less than or equal to about 3. Preferably, the molar ratio of hydrogen chloride to acetylene introduced into the reactor is less than or equal to 1.5.

Ionic liquids are, in principle, salts in the liquid state, while ordinary liquids, such as, for example, water or gasoline, mainly consist of electronically neutral molecules. Ionic liquids are mainly composed of ions.

In general, it can be concluded that any salt that melts without decomposition will usually be an ionic liquid at the outlet. Many salts, however, melt at high temperatures, significantly higher than the temperatures used in catalytic processes. For the purposes of the present invention, the term ionic liquid should refer to a system that is a liquid at the temperature used in the process in which this catalyst system is used.

The most preferred ionic liquids of the present invention are liquids at temperatures of 150 ° C or less, more preferably a temperature of 100 ° C or less, or even more preferably a temperature of 80 ° C. Most preferred are ionic liquids that are in a liquid state at room temperature or even lower. In addition, those ionic liquids that have a very low vapor pressure or very low flammability, and which show good electrical conductivity, are preferred.

Ionic liquids, which predominantly function as a reaction medium, have mainly solubility for the products and intermediates formed in the reaction.

In the present description, the expression at least one ionic liquid refers to one or more than one ionic liquid.

Advantageously, the catalyst system comprises essentially one ionic liquid, as defined above.

Further in the text, the expression ionic liquid, used in the singular or plural, should be understood as one or more than one ionic liquid, unless otherwise indicated.

In the present description, the expression at least one unprotonated cation refers to one or more than one unprotonated cation.

Advantageously, the ionic liquid includes one non-protonated cation.

Further in the text, the expression unprotonated cation, used in the singular or plural, should be understood as one or more than one unprotonated cation, unless otherwise indicated.

The term unprotonated cations, used here to implement the present invention, should be understood as cations that do not carry free hydrogen atom (s) per atom (s) that have a positive charge of the cation.

Mostly, non-protonated cations are selected from quaternary ammonium cations, which can be represented by the general formula [ΝΚ ¹ Κ ² Κ ³ Κ] ⁺ , phosphonite cations, which can be represented by the general formula [RK ¹ K ² K ³ K] ⁺ , and cations, including 5- or 6-membered heterocycles that have at least one nitrogen atom, preferably one or two nitrogen atoms.

Preferably cations consisting of 5- or 6-membered heterocycles are

- 3 025978 cations of imidazole of the general formula (I)

pyridine cations of the general formula (II) pyrrolidine cations of the general formula (III)

where the radicals K and P'-P ⁹ can be independent of each other under the condition that the radical transferred via the atom (s) to which a positively charged cation is attached is not hydrogen, and each hydrogen in some cases is replaced by saturated or unsaturated C1-C18 alkyl group (preferably, in some cases, substitution with a saturated or unsaturated C'-C ₁₆ alkyl group, and more preferably in some cases, substitution with a saturated or unsaturated C ₁ -C ₁₄ alkyl group), and in some cases, is replaced by on yschennuyu or unsaturated C ₂ -C ₁₈ alkyl group with a carbon chain which terminates due to hydrogen, in some cases, substituted by C ₆ -C ₁₂ alkyl group.

The predominantly unprotonated cation is selected from quaternary ammonium cations, phosphonite cations, imidazole cations, pyridine cations or pyrrolidine cations.

More preferably, the unprotonated cation is selected from phosphonite cations, imidazole cations, pyridine cations and pyrrolidine cations.

More preferably, the unprotonated cation is selected from phosphonite cations and imidazole cations.

Examples of quaternary ammonium cations are tributyl methyl ammonium, butyl trimethyl ammonium, octyl trimethyl ammonium, tetramethyl ammonium, tetraethyl ammonium, tetrabutyl ammonium, 2-hydroxyethyl trimethyl ammonium and diethyl methyl (2-methoxyethyl) ammonium.

Examples of phosphonite cations are triisobutylmethylphosphonite, tributylmethylphosphonite, ethyl tributylphosphonite, tetrabutylphosphonite, tetraoctylphosphonite, tributyltetradecylphosphonite, trihexyltetradecylphosphonite and benzyl.

Examples of imidazole cations are 1,3-dimethylimidazole, 1-ethyl-3-methylimidazole,

1-butyl-3-methylimidazole, 1-pentyl-3-methylimidazole, 1-hexyl-3-methylimidazole, 1-decyl-3-methylimidazole, 1-dodecyl-3-methylimidazole, 1-tetradecyl-3-methylimidazole, 1- hexadecyl-3-methylimidazole, 1- (2-hydroxyethyl) -3-methylimidazole, 1-allyl-3-methylimidazole, 1-benzyl-3-methylimidazole, 1-phenylpropyl-3-methylimidazole, 1,3-diethylimidazole, 1- butyl-3-ethylimidazole, 1-methyl-3-propylimidazole, 1-methyl-3-octylimidazole, 1-methyl-3-decylimidazole, 1,3-dibutyl-2-methylimidazole, 1,3-didecyl-2methylimidazole, 1 - (2-hydroxyethyl) -3-methylimidazole, dimethylimidazole, 1-butyl-2,3-dimethylimidazole dimethylimide dazole, 1-hexadecyl-2,3-dimethylimidazole, 1,2,3-trimethylimidazole, 1,3,4-trimethylimidazole, 1-butyl-3-ethylimidazole, 1,3-dibutylimidazole, 1-methyl-3-octylimidazole, 1-butyl-3,4,5trimethylimidazole and 1,3,4,5-tetramethylimidazole.

Examples of pyridine cations are 1-methylpyridine, 1-ethylpyridine, 1-propylpyridine, 1-butylpyridine, 1-hexylpyridine, 1-octylpyridine, 1,2-dimethylpyridine, 2-ethyl-1-methylpyridine, 1-butyl-2-methylpyridine, 1-butyl-3-methylpyridine, 1-butyl-4-methylpyridine, 1-hexyl-3-methylpyridine, 1-hexyl-4-methylpyridine, 1-butyl-2-ethylpyridine, 1-butyl-3-ethylpyridine, 4- methyl-1-octylpyridine, 1-butyl-2-ethyl-6-methylpyridine, 2-ethyl-1,6-dimethylpyridine, 1-butyl-3,4-dimethylpyridine and 1-butyl3,5-dimethylpyridine.

Examples of pyrrolidine cations are 1,1-dimethylpyrrolidine, 1-ethyl-1-methylpyrrolidine, 1-ethyl-3-methylpyrrolidine, 1-butyl-1-methylpyrrolidine, 1-hexyl-1-methylpyrrolidine, 1-octyl-1methylpyrrolidine, 1- butyl-1-ethylpyrrolidine and 1-methyl-1-propylpyrrolidine.

In the present description, the expression at least one anion refers to at least one or more than one anion.

Advantageously, the ionic liquid comprises one anion.

ethyl-2,3-dimethylimidazole, 1-butyl-3,4-dimethylimidazole,

1-propyl-2.31-hexyl-2,3-4,025978

Further in the text, the expression anion, used in the singular or plural, should be understood as one or more than one anion, unless otherwise indicated.

In principle, all anions can be used as anions. The anion [Υ] is mainly selected from the group consisting of halides and halogen-containing anions, the so-called pseudohalides of the formula C1-, Br-, BP ₄ -, PP ₆ -, A1 ₂ C1 ₄ -, A1 ₂ C1 ₇ , PeCl ₄ -, BC1 ₄ -, ЗСС1 ₄ -, ЗПР ₆ -, ΆδΡ ₆ -, ΖηΟ1 ₃ -, ЗпС1 ₃ -, СР3ЗО3-, (СРз80з) 2Н-, СР3СО2-, СС13СО2-, СЫ-, ЗСЫ- and ОСЫ-;

the group consisting of sulfates, sulfites and sulfonates of the general formula ZO ₄₂ -, NZO ₄ -, ZO ₃₂ -, NZO3-, YuOZOz-, K ^and ZOz-;

a group consisting of phosphates of the general formula PO ₄₃ -, NPO ₄₂ -, H ₂ PO ₄ -, K ^a PO42-, NK ^a PO4-, K ^a K ^b PO4-; a group consisting of phosphonates and phosphinates of the general formula K ^a HPO3-, K ^a K ^b PO2-, K ^a K ^b PO3-; the group consisting of phosphonates of the general formula RO ₃₃ -, HPO ₃₂ -, H ₂ PO ₃ -, K ^and RO32-, K ^and NRO3-,

K ^a K ^b RO ₃ -;

a group consisting of phosphonites and phosphinates of the general formula K ^a K ^b PO2-, K ^a HOB2-, K ^a K ^b PO-, K ^a NRO-;

, K ^a HBO3-, K ^a BO3 of the group consisting of carboxylic acids of the general formula K ^a COO-; a group consisting of borates of the general formula BO33-, HBO32-, H2BO3-, K ^a K ^b BO3 of a group consisting of boronates of the general formula K ^a BO22-, K ^a K ^b BO-; a group consisting of carbonates and carboxylic esters of the general formula HCO3-, CO ₃₂ -. K ^a SOz-;

the group consisting of silicates and silicic acid esters of the general formula 3ίΟ ₄₄ -, НЗУ ₄₃ Н28Ю42-, Н3З1О4-, К ^а ЗЮ4з-, К ^a К ^b ЗЮ42-, К ^a К ^b KСО4-, НК ^а ЗЮ42-, Н2К ^and ЗЫ4 -, IPTN Z1O4-;

a group consisting of alkylsilanes and salts of arylsilanes of the general formula K ^a Z1O ₃₃

K ^a K ^b Sz2-,

K ^and K ^{L K} SiO, R ^and K ^{L K} SiO _3, K ^and K ^L K ^with SiO _2, K ^{L and} K SW '3-, Z1O2-, ZYU32-;

a group consisting of carboximides, bis (sulfonyl) imides and sulfonyl imides of the general formula

a group consisting of alkoxides and aryloxides of the general formula K ^a O—; and a group consisting of complex metal ions, such as Fe (CI) ₆₃ -, Fe (CI) ₆₄ -, ΜηΟ ₄ -, Fe (CO) ₄ -, and where the radicals K ^a , K ^b , K ^{c are} each independent from each other, C'gC'A-alkyl. C ₂ -C ₁₈ -alkyl carbon chain, which can be broken by one or more phosphorus, oxygen and / or sulfur atoms and / or one or more substituted imino groups, C ₆ -C ₁₂ aryl, C ₅ -C ₁₂ - cycloalkyl or a 5- or 6-membered phosphorus, oxygen, nitrogen and / or sulfur containing heterocycle or two of them together, in the form of an unsaturated, saturated or aromatic ring that can be broken by one or more phosphorus, oxygen and / or sulfur and / or one or more substituted imino groups, where each radical may be substituted Shchen via functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen heteroatoms and / or heterocycles.

The preference is given to K ^a , K ^b and K ^c , each of which, independently of each other, is hydrogen, methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl ,

2- (n-butoxycarbonyl) ethyl and chlorine.

The anion (s) are preferably selected from the following: chlorine, bromine, iodine, triflate (trifluoromethanesulfonate), tosylate, tetrafluoroethyl sulfonate, bis trifluoromethyl sulfonylimide, tetrachloroferrate, tetrafluoroborate, tetrafluorophosphate, hexafluorophosphate.

Methods for creating suitable ionic liquids are known to those skilled in the art, and therefore, a detailed description is not necessary here.

The catalyst system of the present invention may be used in the liquid phase, or it may be supported on a solid support such as silicon, aluminum, aluminum silicate, cordierite, mullite or activated carbon (only some of the suitable materials are named) to a limiting volume pores and accessible surface of the carrier. The carrier may be of any shape known for such materials, including, but not limited to, honeycombs and extrudates, or the like.

When it is used in the liquid phase, the catalytic system can be dissolved using organic solvents. According to the invention, the choice of the nature of the organic solvents then incorporated into the catalyst system especially depends on the requirement that it be inert with respect to the reactants under the reaction conditions, that it mixes or not with the ionic liquid, and it is desirable that it forms a medium with an ionic liquid whose viscosity is lower than the viscosity of an ionic liquid alone.

Preferably, however, the ionic liquid acts as a solvent so that no further solvent is used.

- 5,025978

In a first preferred embodiment of the invention, the catalyst system consists mainly of at least one ionic liquid containing at least one unprotonated cation and at least one anion selected from chlorine and methanesulfonate.

Under the expression consists mainly of the fact that in the present description, in addition, at least one ionic liquid is defined, the catalytic system in accordance with the invention may contain additional component (s), mainly in small quantities, which do not affect the catalytic properties catalytic system; in other words, do not have a catalytic effect on the reaction during which the catalytic system is used. Among such additional component (s) may be ionic liquid (s), different from that which was originally determined, introduced, for example, to reduce the viscosity of the catalytic system.

The catalyst system in accordance with the first embodiment of the invention contains mainly at least one ionic liquid containing at least one non-protonated cation and at least one anion selected from chlorine and methanesulfonate with the preferences listed above for non-protonated cations.

Preferred is an ionic liquid selected from quaternary ammonium chloride, quaternary ammonium methane sulfonate, phosphonite chloride, phosphonite methanesulfonate, imidazole chloride, imidazole methanesulfonate, pyridine chloride, pyridine methanesulfonate, pyrrolidine chloride and pyrrolidine methane sulfonate.

Most preferred is an ionic liquid selected from phosphonite chloride, phosphonite methanesulfonate, imidazole chloride, imidazole methanesulfonate, pyridine chloride, pyridine methanesulfonate, pyrrolidine chloride and pyrrolidine methanesulfonate.

Most preferred is an ionic liquid selected from phosphonite chloride, phosphonite methanesulfonate, imidazole chloride, imidazole methanesulfonate.

Particularly preferred is an ionic liquid selected from 1-butyl-3-methylimidazole chloride, trihexyltetradecylphosphonite chloride, 1-ethyl-3-methylimidazole methanesulfonate, 1-methyl3-octylimidazole chloride, 1-ethyl-3-methylimidazole chloride and 3-chloride 1 methylimidazole.

Particularly preferred is an ionic liquid from commercially available from 1 ° C CbH or from ΒΑ8Ρ 8E.

In a second preferred embodiment of the invention, the catalytic system comprises:

a) at least one Ν-alkylated imidazole and / or the corresponding imidazole;

b) in some cases, at least one compound of at least one metal.

By the expression “contains” it is to be understood in the present description that in addition to at least one Ν-alkylated imidazole and / or the corresponding imidazole and, in some cases, at least one compound of at least one metal, the catalyst system in accordance with the invention may contain an additional component ( s) having an effect on the catalytic properties of the catalytic system or not contain them. Among such additional component (s) may be ionic liquid (s), different from that which was originally determined, introduced, for example, to reduce the viscosity of the catalytic system.

The preferred catalyst system in accordance with the invention, containing mainly:

a) at least one Ν-alkylated imidazole and / or the corresponding imidazole;

b) in some cases, at least one compound of at least one metal.

By expression contains mainly should be understood the same as that defined for the first embodiment of the invention.

The term “at least one Ν-alkylated imidazole and / or the corresponding imidazole” means one or more than one Ν-alkylated imidazole and / or the corresponding imidazole.

A preferred catalyst system in a second embodiment of the invention comprising one Ν-alkylated imidazole and / or the corresponding imidazole.

Hereinafter, the expression Ν-alkylated imidazole and / or the corresponding imidazole used in the singular or plural is to be understood as one or more than one Ν-alkylated imidazole and / or the corresponding imidazole, unless otherwise indicated.

Ν-Alkylated imidazole in accordance with the second embodiment of the invention is defined by formula (I) below

where the radicals K ¹ , K ² , K ³ and K ⁴ can, independently of one another, be hydrogen radicals or, in some cases, can be substituted by a saturated or unsaturated C ₁ -C ₁₈ alkyl group

- 6,025,978 (preferably C ^ C ₁₄ , more preferably C1-C12, most preferably C ₁ -C ₁₀ and especially most preferably C ₁ -C ₈ ).

Examples of Ν-alkylated imidazole are 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-pentylimidazole, 1-hexylimidazole, 1-heptylimidazole, 1-octylimidazole, 1-nonylimide-imidazole 2-octylimidazole, 1-ethyl-2-methylimidazole, 1-butyl-2methylimidazole, 1-hexyl-2-methylimidazole and 1-decyl-2-methylimidazole.

Preferably, the Ν-alkylated imidazole is selected from 1-methylimidazole, 1-ethylimidazole, 1-butylimidazole, 1-hexylimidazole, 1-octylimidazole, 1-decylimidazole, 1-methyl-2-octylimidazole, 1-ethyl-2-methylimidylazole -2-methylimidazole, 1-hexyl-2-methylimidazole and 1-decyl-2methylimidazole.

More preferably, the Ν-alkylated imidazole is selected from 1-methylimidazole, 1-ethylimidazole and 1-butylimidazole. Even more preferably, Ν-alkylated imidazole is commercially available from Λΐάπαίι.

Methods for creating soluble alkylated imidazoles are known to those skilled in the art and, therefore, detailed description is not necessary here.

The catalyst system in accordance with the second embodiment of the invention contains, as a component b) in some cases, at least one compound of at least one metal.

The expression of at least one compound of at least one metal, used here, means one metal compound or one metal, as well as mixtures of various compounds of similar metals, or mixtures of compounds of various metals or compounds containing two metals, as defined above, t .e. the catalytic system in accordance with the second embodiment of the invention may contain more than one metal or metal compounds, as defined above.

Preferably, the catalyst system comprises one compound of at least one metal, and more preferably one compound of one metal.

The expression compound and metal, used in the singular or plural, should be understood as one or more than one compound and one or more than one metal, unless otherwise indicated.

The expression contains in some cases at least one compound, it should be understood that such a compound is or is absent in the catalyst system.

According to a first subvariant, a catalyst system according to a second embodiment of the invention advantageously comprises compound a) i.e. at least one Ν-alkylated imidazole and / or the corresponding imidazole. In other words, the catalyst system advantageously does not contain component b) of at least one compound of at least one metal.

In accordance with the second subvariant, the catalytic system contains mainly:

a) at least one Ν-alkylated imidazole and / or the corresponding imidazole;

b) at least one compound of at least one metal.

In a second embodiment of the invention, the metal may be any metal. The metal is mainly selected from Ρά, Ρΐ, Au, Nd, Ki, Οδ, Ki, KB and 1g. Mostly the metal is selected from Ρά, Ρΐ, Au, Nd, Ki and Οδ.

The catalytic system in accordance with a second embodiment of the invention therefore comprises advantageously:

a) at least one Ν-alkylated imidazole and / or the corresponding imidazole;

b) at least one compound of at least one metal selected from Ρά, Ρΐ, Au, Nd, Ki and Οδ.

Although good results were obtained when the metal was selected from those mentioned above, very good results were obtained when the metal was selected from Ρά, Ρΐ, Au and Οδ, especially good results were obtained when the metal was selected from Ρά, Ρΐ and Au and even more particularly good results were obtained when the metal was selected from Ρά and Ki. The most interesting results were obtained when Ρά was chosen as the metal.

Mostly Ρΐ (ΐν) or Ρΐ (ΙΙ) or Ρά (ΙΙ) compounds that can be converted to the chlorides of the metals mentioned during the preparation of the catalytic system in accordance with this invention. Thus, chlorides, nitrates, acetates, carbonates or oxides of platinum (III), platinum (11) or palladium (11) can be used. Chlorides and acetates of these metals are nonetheless preferred.

Among the chlorine-containing compounds of platinum (III), platinum chloride (III) and hexachloroplatinic acid or its salts can be noted, for example, Να ₂ ΡΐΟ ₆ , Ι < ₂ ΡΚΤ ·, or ΕΤΡΚΤ · ,.

Among the chlorine-containing compounds of platinum (II), platinum chloride (11) and the salt of platinum-hydrochloric acid of alkali metals or alkaline earth metals, such as, for example, ΝαΤΡίίΤ-Τ Κ ₂ (ΡΐΟ ₄ ) and (ΝΗ ₄ ), can be noted ₂ (ΡΐΟ ₄ ).

- 7 025978

Among the chlorine-containing compounds of palladium (P), palladium chloride (P) and chloropalladite of alkali metals or alkaline-earth metals, such as, for example, 2α2 (ΡάΟ1. ₄ ), can be noted. K ₂ (RICE1 ₄ ) and (ΝΗ ₄ ) ₂ (ΡΗΟ1 ₄ ).

Particularly preferred are ΡΐΟ1 ₄ , ΡΐΟ1 ₂ , PbC1 ₂ and palladium acetate (11) selected from platinum (1U), platinum (11) and palladium (11), respectively. ΡΐΟ1 ₂ , ΡάΟ1 ₂ and palladium acetate (11) are more preferred.

Among the compounds of Au, Au ³ 'are preferred, and compounds, as is the case with Ρά and Ρΐ, these compounds can be converted into the chlorides being preferred. AuCl ₃ most preferred.

The corresponding compounds Ki and Oz with their valency 3 can be converted to acid chlorides or chlorides, are themselves particularly preferred. KiC1 ₃ and OzC1 _3, respectively, are more preferable.

Among suitable Nd compounds, NdCl ₁ can be noted.

The content of metal compounds in the catalytic system in accordance with the second subvariant, expressed in millimoles per liter of Ν-alkylated imidazole and / or the corresponding imidazole, is advantageously greater than or equal to from about 1 mmol / L and less than or equal to about 1000 mmol / L. The content of metal compounds in the catalyst system in accordance with the second embodiment of the invention is advantageously greater than or equal to about 1 mmol / L, preferably greater than or equal to about 5 mmol / L, and particularly preferably greater than or equal to about 10 mmol / L. The content of metal compounds in the catalyst system is preferably less than or equal to about 1000 mmol / L, preferably less than or equal to about 800 mmol / L, particularly preferably less than or equal to about 600 mmol / L, most particularly preferably less than or equal to about 500 mmol / l and even more particularly preferably less than or equal to approximately 400 mmol / l. Although not necessary, however, it is desirable that all metal compounds included in the catalyst system are in dissolved form.

In general, the catalytic system according to the second subvariant is created by dissolving or dispersing the desired amount of the metal compound in the рован-alkylated imidazole and / or the corresponding imidazole and then saturating the solution with hydrogen chloride. However, it is also possible to first saturate the Ν-alkylated imidazole and / or the corresponding imidazole with hydrogen chloride, and then introduce the metal compound into the Ν-alkylated imidazole and / or the corresponding imidazole. Typically, the amount of the metal compound is used such that in the catalytic system the entire metal compound is in dissolved form. However, it is also possible to use a metal compound in such an amount or such a nature that at least one fraction of this compound is in the form of a solid dispersion in the catalyst system, without prejudice to the invention.

In a second preferred embodiment of the invention, the catalyst system comprises a mixture of:

a) at least one compound of at least one metal, one of which is selected from palladium, platinum and osmium; and

b) at least one ionic liquid containing at least one unprotonated cation and at least one anion;

the mixture is selected from the group of mixtures containing, when the metal is palladium, palladium acetate (11) and 1-butyl-3-methylimidazole chloride or 1-ethyl-3-methylimidazole chloride, palladium chloride (11), copper chloride and 1-butyl chloride -3-methylimidazole, palladium chloride (11), copper chloride and 1-butyl-3-methylimidazole chloride, palladium chloride (11) and 1-ethyl-3-methylimidazole chloride, 1-methyl-3-octylimidazole chloride, 1-benzyl- chloride 3-methylimidazole, trihexyltetradecylphosphonium chloride or bis (trifluoromethylsulfonyl) 1-butyl-4-methylpyridine, palladium chloride (11), palladium acetate (11) and is (trifluoromethylsulfonyl) 1-butyl-4-methylimide when the metal is platinum, platinum chloride (11) and 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole tetrachloroferrate, 1-ethyl-3methylimidazole chloride, methanesulfonate -ethyl-3-methylimidazole, 1-ethyl-3-methylimidazole tetrafluoroethylsulfonate, 1-methyl-3-octylimidazole chloride, 1-methyl-3-octylimidazole triflate or trihexyltetradecylphosphonium chloride, platinum (1U) methyl ethyl triflate or triflate bis (trifluoromethylsulfonyl) imide trihexyltetradecylphosphonium, potassium hexachloroplatinate (1U) and t iflat 1-ethyl-3-methylimidazole; and when the metal is osmium, osmium (111) chloride and 1-butyl-3methylimidazole chloride, 1-ethyl-3-methylimidazole tetrafluoroethylsulfonate, 1-methyl-3-octylimidazole chloride or trihexyltetradecylphosphonium chloride.

The expression contains defined above.

Preferably, the catalytic system according to the third embodiment of the invention comprises mainly at least one compound of at least one metal and at least one ionic liquid as defined above.

The expression contains mainly and at least one compound of at least one metal, also defined above, for the first and second embodiments of the invention.

- 8 025978

The catalyst system in accordance with the third embodiment of the invention contains as components a) at least one compound of at least one metal selected from platinum, palladium and osmium.

In the description of the third embodiment, the expression of at least one compound of at least one metal includes one metal compound or one metal, as well as mixtures of various compounds of similar metals, or mixtures of compounds of various metals or compounds containing two metals, as defined hereinabove , i.e. the catalyst system may contain more than one metal or metal compounds, as defined above.

In the description of the third embodiment of the invention, the expression one metal, which is selected from palladium, platinum and osmium, it should be understood that one of the metals is palladium, platinum or osmium.

The expression compound and metal, used in the singular or plural, should be understood as one or more than one compound and one or more than one metal, unless otherwise indicated.

According to a first subvariant of the third embodiment, the catalyst system comprises a mixture a) and b) selected from the group of mixtures containing palladium acetate (11) and 1-butyl-3-methylimidazole chloride or 1-ethyl-3-methylimidazole chloride, chloride palladium (11), copper chloride and 1-butyl-3-methylimidazole chloride, palladium chloride (11), copper chloride and 1-butyl-3methylimidazole chloride, palladium chloride (11) and 1-ethyl-3-methylimidazole chloride, chloride 1 methyl 3-octylimidazole, 1-benzyl-3-methylimidazole chloride, trihexyltetradecylphosphonium chloride or bis ( riftormetilsulfonil) 1-butyl-4-methylpyridine, palladium chloride (11), palladium acetate (11) and bis (trifluoromethylsulfonyl) 1-butyl-4-metilimida.

According to a second subvariant of the third embodiment, the catalyst system comprises a mixture a) and b) selected from the group of mixtures containing platinum (II) chloride and 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole tetrachloroferrate, 1-ethyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole methanesulfonate, 1-ethyl-3methylimidazole tetrafluoroethylsulfonate, 1-methyl-3-octylimidazole chloride, 1-methyl-3-octylimidazole triflate or trihexylphosphonium chloride 1-ethyl-3-methylimidazole triflate or bis ( riftormetilsulfonil) imide trigeksiltetradetsilfosfoniya, hexachloroplatinate (1U) and potassium triflate etil3-1-methylimidazole.

According to a third subvariant of the third embodiment, the catalyst system comprises a mixture a) and b) selected from the group of mixtures containing osmium (111) chloride and 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole tetrafluoroethyl sulfonate, 1-methyl3-octylimidazole chloride or trihexyltetradecylphosphonium chloride.

However, good results were obtained with the catalytic system in accordance with the third sub-variant of the third embodiment of the invention, very good results were obtained with the catalytic system in accordance with the first and second sub-variants, and particularly good results were obtained with the catalytic system in accordance with the first sub-variant. .

The amount of the compound of at least one metal selected from palladium, platinum or osmium in the catalyst system according to the third embodiment of the invention is expressed in millimoles per liter of ionic liquid, preferably greater than or equal to 1 mmol / l and less than or equal to 1000 mmol / l. The content of the compound, as defined above, is preferably greater than or equal to 1 mmol / L, preferably greater than or equal to 5 mmol / L, and particularly preferably greater than or equal to 10 mmol / L. The content of the compound as defined above is preferably less than or equal to 1000 mmol / L and preferably less than or equal to 900 mmol / L.

The content of the palladium, platinum or osmium compound in the catalyst system according to the third embodiment of the invention, expressed in millimoles per liter of ionic liquid, is preferably greater than or equal to 1 mmol / L and less than or equal to 1000 mmol / L. The content of the compound, as defined above, is preferably greater than or equal to 1 mmol / L, preferably greater than or equal to 5 mmol / L, and particularly preferably greater than or equal to 10 mmol / L. The content of the compound as defined above is preferably less than or equal to 1000 mmol / L, preferably less than or equal to 500 mmol / L, particularly preferably less than or equal to 200 mmol / L, even more preferably less than or equal to 100 mmol / L and most preferably less or equal to 50 mmol / l.

Although not necessary, however, it is desirable that all metal compounds included in the catalyst system are in dissolved form.

In general, a catalyst system in accordance with a third embodiment of the invention is created by dissolving or dispersing a desired amount of a metal compound in an ionic liquid and then saturating the solution with hydrogen chloride. However, it is also possible to first saturate the ionic liquid with hydrogen chloride, and then introduce the metal compound into the ionic liquid. Typically, the amount of the metal compound is used such that in the catalytic system the entire metal compound is in dissolved form. However, it is also possible to use a compound

- 9,025,978 metal in such an amount or of such a nature that at least one fraction of this compound is in the catalyst system in the form of a solid dispersion, without prejudice to the invention.

According to a fourth embodiment of the invention, the catalytic system is approved and described in the patent application ί '.' Ν 101716528 (the contents of which are incorporated by reference into the present invention), i.e. a catalytic system containing an imidazole-based ionic liquid with chloride, bromide, hexafluorophosphate or tetrafluorophosphate ion as the anion and chloride of gold, platinum, palladium, tin, mercury, copper or rhodium.

As explained above, the method in accordance with the invention is at least partially carried out on a device made or coated with materials resistant to HC1 in a dissociated form: from metals, polymers, ceramics, refractory materials, graphitized materials and enamel.

Not based on theory, the applicant believes that, although the method of the invention is mainly carried out in the absence of water, the reaction medium, however, is highly polar (ionic), which increases the dissociation of HC1 into active protons and chlorine anions, leading to increased corrosion of materials such like stainless steel.

Therefore, as appropriate materials that can be used in the framework of the invention, one can note both metallic and non-metallic materials.

These materials can be used in bulk or as a coating, but they must all be resistant to dissociated HC1.

Among the metal materials we can mention tantalum and tantalum alloys, zirconium and zirconium alloys, titanium and titanium alloys, platinum and platinum group metals, silver and silver-gold-palladium alloy with a minimum of 30% gold, gold and gold-silver alloys and gold-platinum alloys, molybdenum and molybdenum alloys, nickel-molybdenum alloys, nickel-chromium-molybdenum alloys, nickel-copper alloys, copper alloys (silicon bronze), copper alloys with tantalum and copper with niobium, tin and antimony alloys containing 5% antimony, tin alloys with nickel , niobium and nio alloys tions with tantalum.

Among the metals of the platinum group, rhodium, iridium, ruthenium and osmium can be noted.

Among metallic materials, gold and tantalum are preferred. Tantalum, platinum and niobium give good results even up to 150 ° C, the temperature at which zirconium, gold and Τί-Ρά alloys strongly corrode. Especially tantalum and tantalum-based alloys (containing tantalum of more than 50%) are most preferred in the framework of the present invention.

Specific HC1-resistant alloys can also be used: Grade 7 titanium, NACHePou V TatLu, alloy 400, stainless steel class 904L and super austenitic stainless steel or Na1e11ou S'TatPu.

Among non-metallic materials, high-density polyethylene, fluoroplastic-based elastomers, polypropylene-based thermoplastics, fluoropolymers (for example, polytetrafluoroethylene: PTFE; copolymer of fully fluorinated propylene and ethylene: FEP; perfluoroalkoxy copolymer: PFA MFA; polychlorofluorofluoridethene; polyvinyl fluoride: PVF; polyethylene tetrafluoroethylene: PETFE; polyethylene chlorotrifluoroethylene: PEHTFE), ABS (acrylonitrile-butanediene-styrene) copolymers, acrylonitrile (40%) - vinyl alcohol (60%) copoly ep, polysulfones, polyphenylene polymers (PFP), for example polyphenylene sulfides and polyphenyl sulfones, vitreous resins based on polyester resin, phenolic resins, furan resins, epoxy resins and vinyl ester resins, alumina and corundum ceramics, ceramic materials based on hafnium carbide and titanium nitride, refractory materials based on silicon carbide, on silicon, on high silicon aluminosilicates, on zirconium silicates, on zirconium oxides and on sillimanite e (Α1 ₂ Ο ₃ -δίΟ ₂ ), coatings based on epoxy resins, on Bakaryeya, VtaiFye on the basis of phenol-formaldehyde resin and 18o1-thai, acid-resistant cements based on silicates, phenol-formaldehyde resins and mixtures of sulfides with quartz sand, self-curing phenol-based form-resistant cements resins mixed with graphite; furfuryl alcohol resins mixed with carbon; and polyester resins mixed with quartz. In the case of cements, the substrate must be protected by an additional sheet of plastic. Graphite, impregnated graphite (impregnated with polytetrafluoroethylene or phenolic resin), carbon, glass, quartz, enamel, porcelain, ceramics, stone and acid-resistant bricks may also be suitable as non-metallic materials. Silicon carbide, alumina and (impregnated) graphite give good results.

Among the polymers / resins that can be used, the following specific polymers / resins can also be noted: HVSL (chlorinated polyvinyl alcohol), Betakaye 470, Batoi ΧΡ 45, DCPD (dicyclopentadiene), ebonite and EPDM.

Enamel is mainly used as a material for coating steel.

Among the polymers, these are most suitable, including polyolefins such as high density polyethylene (HDPE), ultra high molecular weight PE (UVMPE) and polypropylene (PP) and, in particular, based on thermoplastics, fluoropolymers, sulfur-containing polymers such as polysulfones or polysulfides, especially aromatic polymers of this type, and graphite, and impregnated graphite.

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Among the thermoplastics based on fluoropolymers, the most suitable are polyvinylidene fluoride, polytetrafluoroethylene, perfluoroalkoxyalkane, copolymers of ethylene and tetrafluoroethylene, copolymers of tetrafluoroethylene, perfluoromethyl vinyl ether and copolymers of tetrafluoroethylene and hexafluoropropylene.

These polymers can be used in the solid state or with reinforcing elements (steel, spiral reinforcement, for example, GRP).

Among the polymers / resins that can be used, PEEK (polyester ether ketone) and fluorinated polymers are preferred, preferred at high temperature (usually about 100 ° C). Fluorinated polymers such as PTFE, FEP, PFA-MFA (manufactured under the ΗΎΤΈΟΝ brand), ETFE and ECTFE (like the previous one, manufactured under the NATEK brand.) Give good results. At lower application temperatures, the following specific polymers give good results: PP (or polypropylene) homopolymer and CPVS (chlorinated PVA).

Among the coatings based on resins, the most advantageous are those based on epoxy resins or phenolic resins. Plastic coatings can be applied, for example, to steel or SAP (glass reinforced polyester).

Depending on the operating conditions and type of device, preferred materials for coating or manufacturing a device for carrying out the method of the invention are graphite, impregnated graphite with polytetrafluoroethylene or phenolic resin, enamel, tantalum, gold, fluoropolymers, polyolefins or metal alloys.

For some specific elements, such as a heat exchanger and pumps, graphite, whether it is impregnated or not, is particularly suitable. For heat exchangers that promote heating or evaporation of the liquid in the process, graphite impregnated with polytetrafluoroethylene is particularly suitable.

Enamel, tantalum, gold and perforated polymers are well suited for coatings or the manufacture of devices operating at elevated temperatures.

Polyolefins, fluoropolymers and metal alloys are well suited for coatings or the manufacture of devices operating at low temperatures.

Especially enamelled steel (sometimes called vitrified steel) has proven to work well within the scope of the present invention. This is in fact a cheaper solution than steel with perforated polymers and enamel shows better adhesion to steel than perforated polymers.

Therefore, it is preferable that the method for carrying out the invention at least partially is carried out in a device made of enameled steel, i.e. at least one part of the device used in the method for carrying out the invention is made of enameled steel.

In this regard, the enamels that were described in \ UO 2009/043796 (the contents of which are incorporated by reference in the present application) are preferred.

These enamels contain silicon, oxygen and calcium, and preferably potassium and titanium, and also most preferably have a low calcium content; and / or high potassium content; and / or low titanium content.

The examples below are intended to illustrate the invention without limiting its scope.

The general course of the experiment, used as examples.

The hydrochlorination reaction was carried out in a glass reactor equipped with a sintered glass disk in the lower part to obtain a good distribution of gaseous reagents consisting of acetylene and hydrochloric acid.

Thermal control of the system was carried out using double walls of the reactor and thermal control of oil to maintain the desired temperature, controlled by a thermal valve placed directly on the reactor.

The gaseous flow rate was 5 l / h for C ₂ H ₂ and 6 l / h for HC1. The residence time calculated for an empty reactor (loaded only with ionic liquid) at 150 ° C and atmospheric pressure was 3.2 s.

Small samples of materials to be evaluated were immersed in the medium and analyzed.

Samples of stainless steel (HC) 316 b remain almost unchanged when exposed to butylmethylimidazole chloride (CBMI) after 7 hours at 150 ° C, but in the presence of the indicated imidazole, HC1 and C ₂ H ₂ (hydrochlorination medium), destructive corrosion was noted after half an hour. The same applies to zirconium and silver, the latter even completely dissolved in the medium.

On the other hand, after 544 hours with a similar reaction medium (imidazole, HC1 and C ₂ H ₂ ), the enameled steel remained unchanged. ΗΥΤΈΟΝ® (0.0%), PEEK (0.0%), ECTFE (-0.3%) and PTFE (0.0%) also remained or did not change significantly under similar conditions after 216 hours; ETFE (0.0%) after 186 hours; FEP (0.0%) after 139.5 hours; graphite impregnated with PTFE (0.0%) after 210 hours and with phenolic resin (0.0%) after 161 hours; aluminum (0.0%) after 210 hours; niobium (-0.6%) after 164 hours; tantalum (0.0%) after 11 025978 after 142 hours; platinum (-0.1%) after 158.5 hours and silicon carbide (0.0%) after 180.5 hours, the numbers in () indicate a change in weight after the indicated exposure period.

None of the homopolymers and HPS were tested under similar conditions, but at a lower temperature (90 ° C), and they turned out to look good and showed a slight change in weight after 186 hours (respectively -0.2% and + 0.1%) .

Other polymers, which were also tested, remained in the same state with the following results:

Jehakape 470 at 150 ° C / 118 h (+ 0.7%);

Kega 8P 30 at 100 ° C / 40.5 h (-0.2%);

SouMit 883 at 90 ° C / 187 h (+ 0.9%);

U1CO 2190 at 90 ° C / 162 h (+ 0.9%);

HB2 at 100 ° C / 163.5 h (0%) HC276 at 90 ° C / 163.5 h (0%).

In addition, some of the above materials unexpectedly increased the degree of conversion compared with the degree of conversion obtained in a glass reactor, namely PTFE, impregnated graphite with PTFE or with phenolic resin and tantalum.

Claims (12)

CLAIM 1. The method of hydrohalogenation of alkyne in the presence of a catalytic system containing at least one ionic liquid containing at least one non-protonated cation, characterized in that the method is at least partially carried out in a device made or coated with materials that are resistant to halogen acids in dissociated form and which are selected from PTFE (polytetrafluoroethylene), graphite impregnated with PTFE or phenolic resin, or tantalum. 2. The method according to the preceding paragraph, in which the alkyne is acetylene and the halogen acid is HC1. 3. The method according to the preceding paragraph, in which the hydrochlorination reaction is carried out at a temperature in the range from room temperature to 220 ° C. 4. The method according to any one of the preceding paragraphs, in which the unprotonated cation is selected from quaternary ammonium cations, phosphinium cations, imidazolium cations, pyridinium cations and pyrrolidinium cations. 5. The method according to any one of the preceding paragraphs, in which the ionic liquid acts as a solvent in such a way that does not use an additional solvent. 6. The method according to any one of the preceding paragraphs, in which the catalytic system consists mainly of at least one ionic liquid containing at least one unprotonated cation and at least one anion selected from chloride or methanesulfonate. 7. The method according to the preceding paragraph, in which the ionic liquid is selected from phosphonium chloride, phosphonium methanesulfonate, imidazolium chloride, imidazolium methanesulfonate. 8. The method according to the preceding paragraph, in which the ionic liquid is selected from 1-butyl-3-methylimidazole chloride, trihexyltetradecylphosphonite chloride, 1-ethyl-3methylimidazole methanesulfonate, 1-methyl-3-octylimidazole chloride, 1-ethyl-3-methylimidazole chloride -3-methylimidazole. 9. The method according to any one of claims 1 to 5, in which the catalytic system comprises: a) at least one Ν-alkylated imidazole and / or the corresponding imidazole; b) optionally at least one compound of at least one metal. 10. The method according to the preceding paragraph, in which the Ν-alkylated imidazole is represented by the formula (I) k ^! where the radicals K ¹ , K ² , K ³ and K ⁴ may, independently of one another, be hydrogen or optionally substituted saturated or unsaturated C ₁ -C ₁₈ (preferably C ₁ -C ₁₄ , more preferably C ₁ -C ₁₂ , most preferably a C ₁ -C ₁₀ and especially most preferably a C ₁ -C ₈ ) alkyl group. 11. The method according to the preceding paragraph, in which the Ν-alkylated imidazole is selected from 1-methylimidazole, 1-ethylimidazole and 1-butylimidazole. 12. The method according to any one of claims 1 to 5, in which the catalytic system comprises an imidazole-based ionic liquid with chloride, bromide, hexafluorophosphate or tetrafluorophosphate ion as an anion and one or more chloride of gold, platinum, palladium, tin, mercury, copper or rhodium.