Catalytic system for the hydrochlorination of acetylene and a method of producing vinyl chloride

 

(57) Abstract:

Usage: in catalytic chemistry, in particular in the method of producing catalysts for the hydrochlorination process. the inventive catalyst system contains a compound of a metal of the eighth group, preferably a compound of palladium or platinum in the amount of 1 to 200 mmol/l catalytic system additionally hydrochloride fatty amine number with the number of carbon atoms greater than 8, preferably C10-C20with a melting point above 25C, and an organic solvent selected from aliphatic, cycloaliphatic and aromatic hydrocarbons and their mixtures (volume ratio of solvent to the amine hydrochloride is 0.1 to 20). this catalytic system is used for the hydrochlorination of acetylene at a temperature of from room temperature up to 200C To produce vinyl chloride monomer for the production of polymeric materials. 2 S. and 6 C.p. f-crystals, 3 tables.

The invention relates to the catalytic hydrochlorination system based on the connection of the metal of group VIII and the method of producing vinyl chloride by hydrochlorination of acetylene using this catalytic system.

Obtaining vinyl chloride by vzaimodeistvie solid heterogeneous catalyst in the form of chloride of copper on the substrate. Currently an increasing interest in the catalytic system without the use of compounds based on mercury, which is mainly related to its high toxicity. There were developed various catalysts intended to replace existing catalysts used in the gas phase. For example, the known method hydrochlorination of acetylene in the gas phase in the presence of a fixed catalyst layer consisting of Halogens noble metal on a substrate of activated charcoal. However, until now, the lifetime of such catalysts intended for carrying out processes in the gas phase, remains very small compared to the lifetime of the catalysts based on compounds of mercury.

At the same time, in the literature some examples hydrochlorination of acetylene in liquid catalytic environment. Described is a method of obtaining vinyl halides by reacting at an elevated temperature of acetylene and molten salts halogenerator organic bases with conventional catalyst. As organic bases used aliphatic, aromatic or heterocyclic amines, and mixtures thereof. In one example vinylclub. hours of diethylamine and 100 wt. including mercury chloride, at a temperature of 220-225aboutC. there is a method of using an aqueous acid solution containing 46 wt. chloride of copper and 14-16 wt. the hydrochloride of methyl-, dimethyl - or trimethylamine. The described method of producing vinyl chloride by reacting acetylene with hydrogen chloride in the presence of a catalyst prepared by suspension in water or in an organic solvent binary system consisting of a chloride of tin, platinum chloride and palladium chloride, optionally substituted by chloride of a transition metal of variable valency. Also described is a method of producing vinyl chloride by reacting acetylene and hydrogen chloride in the presence of palladium compounds as catalysts in the solution of an aliphatic or cycloaliphatic amide at a temperature above the ambient temperature. Although the use of this method allows to expect a greater product yield, it is clear that under the reaction conditions such catalytic system will quickly disintegrate, forming a blackened products containing coal.

The aim of the invention is the development of sustainable catalytic hydrochlorination system, not the Lena in the presence of such liquid catalytic system, which is particularly active, not destroyed in the reaction conditions and, in addition, has a high selective action upon receipt of vinyl chloride, which provides a significant reduction of yield unwanted side products. Unlike systems based on compounds of mercury advantage of this catalytic system is the lack of evaporation of metal salts in the installation.

The invention relates to fluid catalytic hydrochlorination system, in particular, to hydrochloridebuy acetylene. This catalytic system comprises at least one compound of a metal of group VIII, fatty amanohashidate with a melting point above 25aboutWith and an organic solvent. To fatty amines number is any amine or mixture of amines containing a high number of carbon atoms, for example, more than 8 carbon atoms, which have a weakly or strongly branched molecular structure. It is advisable to use amines with 10-20 carbon atoms. Such weakly or strongly branched molecular structure causes free crystallization of the hydrochloride, obtained by reaction of fatty amine and hydrogen chloride, which is associated with PTSA, for example, decylamine, undecillion, dodecylamine, 3-methylcobalamin.

Good results were obtained with the use of a catalytic system comprising dodecylamine hydrochloride.

Compounds of metals of group VIII, used in catalytic systems related to the present invention, mainly select among the compounds of iron, cobalt, Nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and mixtures thereof. It is advisable to use the chlorides of the metals of group VIII, but can also be used any other connection, breaking into a chloride in the presence of hydrogen chloride in the preparation of the catalytic system. Suitable as compounds of a metal of group VIII used in the present invention, to select compounds of platinum or palladium, such as platinum chloride (II) or palladium (II) chloride, chloroplatinic or chloropalladite alkaline or alkaline earth metals, such as Na2(PtCl4), Na2(PdCl4), K2(PtCl4), K2(PdCl4), Li2(PtCl4), Li2(PdCl4), (NH4)2(PtCl4), (NH4)2(PdCl4)-hexachloroplatinate acid and its salts, such as Na2PtCl6, K2PtCl66, K2PdCl6, Li2PdCl6and so on, also Use the complexes of metals of group VIII, in which the metal has a zero valence, such as Pt(PO3)2Pd(PO3)2, (PO3)Pt(CO), etc. Can also be used a mixture of compounds of metals of group VIII.

Most commonly used compounds of metals of group VIII in the form of chloride of platinum (II) and palladium (II) chloride. The most appropriate use of such a compound of the metal of group VIII, as the palladium (II) chloride.

The nature of the solvent for the implementation of the method of the present invention, connected to its inertness with respect to the reagents in the reaction conditions, the ability to wetting fatty amanohashidate at the reaction temperature and the ability to dissolve at a temperature below its melting point. At the same time in order to preserve the security and ease of use prefer to use low volatile organic compounds. The choice of organic solvent is also due to its ability to absorb acetylene. The solvents satisfying the above criteria, choose among the aliphatic, cycloaliphatic and aromatic butylbenzyl, methylethylbenzene. To save money it is advisable to choose a solvent among the products of commercial quality, consisting of mixtures of aliphatic hydrocarbons such as solvent ISOPAR de Esso or solvent SHELLSOL K de Shell or mixtures of aromatic compounds, such as solvent SOLVESSO de Esso or solvent SHELLSOL AB de Shell.

Good results are obtained by the use of saturated aliphatic solvents such as solvent SHELLSOL K, consisting of petroleum fractions with a boiling point of about 190-250aboutC.

Other compounds considered on the basis of an assessment of their compliance with the above criteria are some heavy halogenated compounds such as halogenoalkane, halogenoalkane and other halogenated derivatives of aromatic compounds.

Most commonly used catalytic system containing dodecylmercaptan, palladium (II) chloride and aliphatic solvent, such as SHELLSOL K. This catalytic system has a high catalytic activity and selectivity in relation to vinyl chloride, which can exceed 99.9% of moreover, such a system is almost not degrade over time.

The content of the compound of metal of group VIII catalytic system, expressed in mmol per liter of solution of a catalytic system, is higher than or equal to about 1 mmol/l, mainly greater than or equal to 10 mmol/L. the content of the compound of metal of group VIII in the catalyst system is generally lower than or equal to 200 mmol/l, mainly less than or equal to about 100 mmol/L. Although not necessarily, but it is advisable that any compound of the metal of group VIII were in the catalytic system in the dissolved form. In the General case, the catalytic system is obtained by dissolving or dispersing the desired amount of compound of metal of group VIII in fatty Amina or in a mixture of fatty amine number and an organic solvent while heating this solution to a temperature exceeding the melting point of the amine hydrochloride of the fatty series, and by the subsequent saturation of this is possible, although more difficult, practically, to first saturate fatty amine or the mixture of fatty amine number and an organic solvent in the preliminary heating with the use of hydrogen chloride to form the hydrochloride fatty amine number, and then enter the compound of the metal of the VIII group in the amine hydrochloride fatty series or its mixture with an organic solvent. Normally, the amount of compound of metal of group VIII used in the catalytic system should be such that any compound of the metal of group VIII it was in the dissolved form. However, and apply such amount of the compound of metal of group VIII or a compound of such a nature that the minimum fraction which is present in the catalytic system in a dispersed solid form that does not contradict the invention.

The invention also relates to the production of vinyl chloride by hydrochlorination of acetylene in liquid catalytic system comprising at least compound of the metal of group VIII, fatty amanohashidate with a melting point above 25aboutWith and an organic solvent. The nature and ratios of the components of the catalytic system used in the implementation of the method corresponding to the ear and up to 200aboutC. At a higher temperature catalytic system tends to rapidly deteriorate. Mostly the reaction temperature corresponds to the temperature at which any fatty amanohashidate is in solution. The preferred reaction temperature, i.e. the temperature at which achieved the best performance, efficiency and sustainability of the system in a catalytic environment temperature is higher than or approximately equal to 80aboutC. the Best results were obtained when the temperature is higher than or approximately equal to 120aboutC. Mainly the reaction temperature does not exceed 180aboutC. Often use a reaction temperature lower than or approximately equal to 170aboutC. the Proposed method is mainly carried out under atmospheric pressure or under a little more pressure, not exceeding 1.5 bar, which is connected with the observance of safety measures when handling acetylene.

The proposed method of producing vinyl chloride by hydrochlorination of acetylene is carried out by interaction in any reactor of the appropriate type of gaseous reagents acetylene and hydrogen chloride and a liquid catalyst system. The proposed method usually osushestvljaem. Another way to ensure optimal exchange between the vapor and liquid phases, is to use a counter-current reactor, in particular, a reactor with a Packed column and chilled layer when the fluid flow in the opposite direction to the flow of gaseous reagents.

In accordance with the proposed method, the molar ratio between injected into the reactor hydrogen chloride and acetylene is higher than or equal to approximately 0.5. Mainly, this ratio is higher or equal to approximately 0.8. In the General case, this molar ratio is less than or equal to about 3. Good results were obtained when the molar ratio between the hydrogen chloride and acetylene introduced into the reactor of approximately 1.5 or less. Acetylene and hydrogen chloride lead in the interaction in the reactor or, mostly, are mixed before introduction into the reactor.

To increase the amount of acetylene dissolved in the liquid phase, is also allowed to enter into the reactor one acetylene in a gas where it reacts with chloride hydrogen in the liquid phase in the form of a hydrochloride, with a bold amanohashidate catalytic system will reg the A.

The invention is illustrated by the following examples. Examples 1-5 correspond to the proposed method, and example 6(S)-8(C) are shown for comparison.

P R I m e R s 1-3. The catalytic system is prepared using dodecylamine, palladium (II) chloride and solvent SHELLSOL K

The solvent SHELLSOL K is a commercial product manufactured by Shell, consisting of a mixture of hydrocarbons, mainly aliphatic series. The substance used in these examples has an initial boiling point 193aboutWith, and the final boiling point equal to 245aboutC.

Dodecylamine first mixed with different quantities of solvent SHELLSOL K, then add 4 g of palladium chloride (II) or 22.6 mmol of palladium chloride in 1 l of solution under stirring. Then, the solution of the catalytic system is saturated with gaseous hydrogen chloride.

The reaction between acetylene and hydrogen chloride is conducted as follows. In a reactor made of Pyrex (borosilicate glass) internal volume of 45 ml with double membrane, which circulates heat-transfer oil, and with a device for introducing reagents, consisting of a nozzle fused glass intended for dispersing gas in a liquid what happens to the temperature of 150aboutWith, and a gas stream containing a mixture of hydrogen chloride and acetylene with a molar ratio of HCl to C2H2equal 1,17 injected into the reactor. The gas retention time in the reactor, i.e., the ratio of the volume of the reactor and the volumetric flow of the reactants at the reaction temperature is 4.9 C. the Gaseous product leaving the reactor, analyzed by gas chromatography. The only celebrating the products of the reaction are vinyl chloride (VC) and 1-chloroprene (international champion pain relief). The results are presented in table. 1. The product yield is defined as the molar ratio between the obtained vinyl chloride and introduced into the reactor acetylene. The selectivity is calculated by the molar ratio of the obtained product VC and the amount (VC + (2 x xICPr)).

P R I m e R s 4-5. Two reaction medium prepared as described in example 1 with the use of changeable quantities of dodecylamine and solvent SHELLSOL K, but instead of palladium chloride take 15 mmol/l of chloride of platinum (II).

The reaction hydrochlorination of acetylene is carried out in the same conditions as described in examples 1-3. The results are presented in table. 2.

P R I m e R 6(C). The catalytic system is prepared as described in example 1, but without the use of organic rastvorenie 150aboutThat makes it impossible to carry out reaction hydrochlorination of acetylene in the reactor.

P R I m e R 7(C). The catalytic system is prepared as described in example 1, but without using dodecylamine in solution. The reaction hydrochlorination of acetylene takes place in the same conditions as in the examples above. The results are presented in table. 3.

P R I m e R 8(C). The catalytic system is prepared as described in example 1, but instead of dodecylamine take dimethylformamide.

The reaction hydrochlorination of acetylene is carried out in the same conditions as in the examples above. The results are presented in table. 3.

1. Catalytic system for the hydrochlorination of acetylene-containing compound of the metal of group VIII and an organic solvent, characterized in that it further comprises the amine hydrochloride fatty series, containing more than 8 carbon atoms, with a melting point above 25oAnd as the organic solvent, the solvent is selected from aliphatic, cycloaliphatic and aromatic hydrocarbons and their mixtures, when the volume ratio of solvent to the amine hydrochloride bold range of 0.1 to 20.0 and when the content of metal joining VIII gr is ia metal of group VIII it contains a compound of palladium or platinum.

3. The system under item 1, characterized in that it contains amine hydrochloride C10C20.

4. The method of producing vinyl chloride by reacting acetylene and hydrogen chloride in the presence of a liquid catalyst system containing compound of the metal of group VIII and an organic solvent, wherein the process is conducted at a temperature from room temperature up to 200oAnd ispolzuut catalytic system, optionally containing amine hydrochloride fatty series, containing more than 8 carbon atoms, with a melting point above 25oWith the use of an organic solvent selected from aliphatic, cycloaliphatic and aromatic hydrocarbons and their mixtures, when the volume ratio of solvent to the amine hydrochloride bold range of 0.1 to 20.0, and the content of the compound of metal of group VIII 1 200 mmol/l catalytic system.

5. The method according to p. 4, characterized in that the use of amine hydrochloride10WITH12.

6. The method according to p. 4, characterized in that the connection of the metal of group VIII is used as a compound of palladium or platinum.

7. The method according to p. 4, characterized in that the process is carried out at 80 - 180oC.

8.

 

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