Catalytic system for producing vinyl chloride and a method of producing vinyl chloride

 

(57) Abstract:

Use: petrochemical industry, in particular the production of catalysts for the hydrochlorination of acetylene and obtaining vinyl chloride. The inventive catalyst system contains a compound of the metal of group VII and amanohashidate with sterically hindered spatial structure and a melting point lower than or equal to 25oC, containing from 8 to 30 carbon atoms formulas

< / BR>
where R1, R2- hydrogen atoms or identical or different alkyl or aryl group; R3is an alkyl or aryl group. The content of the compound of metal of group VIII 1-200 mmol per 1 l of amanohashidate. As compounds of group VIII system preferably contains a compound of palladium or platinum, preferably palladium chloride, or chloride of platinum. The product is vinyl chloride. Reagent 1: acetylene. Reagent 2: hydrogen chloride. Reaction conditions: 80 - 200oC, the molar ratio of hydrogen chloride : acetylene (0.5 to 3) : 1. 2 C. and 10 C.p. f-crystals. 6 table.

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 is Orada usually carried out in the gas phase, in the reactor with a fixed bed in the presence of a 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, in the application for Japanese patent 52/136104, no previous expertise, the described 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. So far, however, 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. In the application for a German patent 709.000 describes a method for vinyl halides by reacting at an elevated temperature of acetylene and molten salts halogenerator alifaticheskie, aromatic or heterocyclic amines, and mixtures thereof. In example 1, the vinyl chloride is produced by dispersion of hydrogen chloride and acetylene in a mixture containing about 350.h pyridine, about 350. h diethylamine and about 100.h mercury chloride, at a temperature of 220-225oC. ed.St. SU-237116 described method using aqueous acid solution containing 46 weight. chloride of copper and 14-16 weight. the hydrochloride of methyl-, dimetrio of trimethylamine. In the patent application EP-A-0340416 disclosed a method of producing vinyl chloride by reacting acetylene and hydrogen chloride in the presence of compounds based on palladium as catalyst under solvent-based aliphatic or cycloaliphatic amide, at a temperature above the ambient temperature. Although the use of this method allows to expect the best results, it has some significant drawbacks: it is obvious that in the conditions of the reaction liquid catalytic system quickly collapses, forming a blackened products containing coal. Moreover, in the presence of hydrogen chloride amine is converted into the hydrochloride, melting point which is mostly much higher than the ambient temperature. The hydrochloride of N-methylpyrrolidone, for example, is avidinii this procedure, the problems associated with the increase of mass in the catalytic environment during reactor shutdown, or clogging of the canal system in the most chilled places of installation. Any reactor, and the canal system, which circulates the reaction medium,would need to have a constant temperature higher than the melting point of the hydrochloride.

Thus the aim of the invention is to develop a catalytic hydrochlorination system that does not contain mercury compounds, sustainable and does not cause the above problems, being in a liquid state at ambient temperatures. The next aim of the invention is to develop a method of producing vinyl chloride by hydrochlorination of acetylene using this catalytic system, which is not destroyed in the reaction conditions and, in addition, allows to obtain vinegared, having a selective action than 99.9% of what contributes to a significant reduction in the number of unwanted by-products. Unlike systems based on compounds of mercury advantage of the catalytic system corresponding to the invention,is the lack of evaporation of metal salts in the installation.

The invention relates lytic system contains, at least the compound based on a metal of group VIII and amanohashidate, melting point that is less than or equal to 25oC.

Amanohashidate with a melting point lower than or equal to 25oC are, in particular, amanohashidate with a pronounced spatial configuration and have the following General formula:

< / BR>
In accordance with this formula, R1and R2are hydrogen atoms or alkyl or aryl groups, identical or different; R3is an alkyl or aryl group. In certain cases R1and R3form a common loop by linking their carbon atoms, for example, by 5 or 6 carbon atoms which may be substituted by alkyl groups. Mainly R1, R2and R3are alkyl groups.

An alkyl group formed of a linear or branched carbon chain, in certain cases it may be substituted by one or more aryl groups. Aryl group formed by any aromatic radical, in some cases substituted by one or more alkyl groups.

The total number of carbon atoms in this compound is in meom connection does not exceed 30 atoms. Mainly the maximum number of carbon atoms equal to 24.

Amanohashidate formed by one or more amanohashidate, including any mixture of clorhidrato several amines, for example, several isomeric compounds. This mixture of clorhidrato several amines are used, in particular, because of its availability or lower cost compared to pure substances. An example of such a connection is amanohashidate containing a mixture of various substances corresponding to the formula (1), which is produced by reacting hydrogen chloride and such commercial products as primary amines tertiary Akilov INE 81-R and RIMENE JM-T de Rohm and Haas Co., consisting of mixtures of isomeric amines, respectively, of C12-C14 and C18-C22. In some cases, it may be useful arbitrary mixing clorhidrato different amines due to formation of an electric mixture of these substances having a melting temperature below the melting temperature of the individual substances.

Good results were obtained when using a catalyst system containing amanohashidate tertiary alkyl (R1, R2and R3formed alkyl groups), consisting of 10-25 atoms coal is the train using amanohashidate, in which R1and R2are hydrogen atoms and R3is an alkyl or aryl group, for example, the hydrochloride of polyisopropylene hydrochloride and the polyethylene-phenethylamine. Such amines with a pronounced spatial configuration can be obtained, for example, from the corresponding amines with dialkylammonium aromatic nucleus, for example, for the above substances are used, respectively benzylamine and 2-phenylethylamine, and to protect the amine derivative conduct the reaction using the anhydride of carboxylic acid, typically, the alkylation of aromatic cores obtained amide, and, finally, the alkaline hydrolysis of the amide derivative.

Compounds based on metals of group VIII, used in catalytic systems, according to the invention, generally selected from compounds of iron, cobalt, Nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum or mixtures thereof. Mostly use the chlorides of the metals of group VIII, but can also be used any other connection, in turn chloride in the presence of hydrogen chloride in the preparation of the catalytic system. Mainly compound of the metal of group VIII, used according to the whether the palladium (II) chloride, chloroplatinic or chloropalladite alkali metals or alkaline-earth metals, for example, Na2, PtCl4, Na2PdCl4, K2PtCl4, K2PdCl4, Li2PtCl4, Li2PdCl4, (NH4)2PtCl4and (NH4)2PdCl4platinochloride acid or its salts, for example, Na2PtCl6, K2PtCl6, Li2PtCl6, the compounds of palladium in which the palladium has a high valence, such as Na2PdCl6, K2PdCl6, Li2PdCl6and so on, also Used complex compounds of metals of group VIII, in which the metal has a zero valence, such as complex compounds of Pt(RF3)2Pd(RF3)2, (RF3)Pt(Co), etc.

Can also be used mixtures of metals of group VIII.

Mostly use such compounds of metals of group VIII, such as, in particular, chloride platinum (II) and palladium (II) chloride. If the catalytic system contains amanohashidate tertiary alkyl (R1, R2and R3formed alkyl groups), mainly used, in particular, chloride platinum (II) from compounds of metals of group VIII. If the catalytic system contains amino is uppy mostly use the palladium (II) chloride.

Often prefer to use a catalytic system containing amanohashidate tertiary alkyl, e.g., derived from a primary amine tertiary alkyl PRIMENE 81-R and chloride platinum (II). The selectivity of action of such catalytic systems for the synthesis of vinyl chloride is more than 99.9% moreover, such a system almost does not degrade over time.

The content of the compound of metal of group VIII catalytic system, expressed in millimoles per 1l of amanohashidate, mainly greater than or equal to about 1 mmol per 1 l of, but tend to be higher than or equal to 10 mmol/L. the content of the compound of metal of group VIII in the system in General less than or equal to about 200 mmol/l, but mostly lower than or equal to 100 mmol/L. Though not necessarily, but preferably, the compound of the metal of group VIII were in the catalytic system, in the dissolved form.

The invention also relates to a method for producing vinyl chloride by hydrochlorination of acetylene using a catalytic system comprising at least compound of the metal of group VIII and amanohashidate with a melting point lower than or equal to 25oC. Properties and relation of constituents analyzed the ENES above.

In accordance with the invention, the above-described catalytic system is used in the liquid phase. It can also be located on a solid substrate in the form of silicon, alumina or activated carbon, without exceeding the total pore volume of the substrate. Mainly catalytic system is used in the liquid phase. However, the viscosity of the liquid at the temperature of the reaction often reduces the effectiveness of the exchange of substances between the gas phase containing the reagents and the liquid phase in which the reaction occurs hydrochlorination. So it is mainly catalytic system is diluted with an organic solvent. The choice of organic solvent used in accordance with the invention, due, in particular, the necessity of its inert nature with respect to the reagents in the reaction conditions, compatibility with amanohashidate and preferably the ability to form this hydrochloride environment, the viscosity of which is lower than the viscosity of the medium formed by hydrochloride. At the same time in order to comply with safety measures and ease of use I prefer the use of low volatile organic solvents. The choice of organic solvent is also influenced his is up among aliphatic, cycloaliphatic and aromatic hydrocarbons and their mixtures, for example, waxes, C7-C15 and alkyl benzenes, in particular, these include xylenes, propylbenzene, butylbenzene, methylethylbenzene. To save money the right solvent mainly selected from commercial products included in mixtures of aliphatic hydrocarbons such as solvent 1SOPAR de ESSO or solvent SHELLSOL de Shell or mixtures of aromatic compounds, such as solvent SOLVESSO de Esso or solvent SHELLSOL AB de Shell.

Good results are obtained with the use of saturated aliphatic solvents such as solvent SHELLSOL K, consisting of petroleum fractions having a boiling point of from 190 to 250oC.

Other solvents corresponding to the above criteria, are some heavy halogenated compounds such as halogenated alkanes, halogenated benzenes and other halogenated derivatives of aromatic compounds.

When the catalytic system is used in the liquid phase and diluted with an organic solvent, the mass ratio of the solvent and amanohashidate in General greater than or equal to 0.01. Mostly it korekushon it is less than or equal to 3. Most often it is below or equal to 2.

In accordance with the invention the reaction is carried out at ambient temperatures up to 220oC. At a higher temperature catalytic system is quickly destroyed. The preferred reaction temperature, i.e. the temperature at which the highest degree of productivity, performance and stability of the catalytic system, above or equal to approximately 80oC.

The best results were obtained when the temperature is higher than or equal to approximately 120oC. Mainly the reaction temperature does not exceed approximately 200oC. the reaction Temperature below or equal to approximately 170oC is the most preferred. In accordance with the invention the reaction is carried out under atmospheric pressure or under slightly greater pressure in observance of security measures in the treatment of acetylene, i.e., without exceeding pressure equal to 1.5 bar.

In accordance with the invention, a method of producing vinyl chloride by hydrochlorination of acetylene is realized by means of interaction in any suitable reactor gaseous reagents acetylene and hydrogen chloride with a catalytic system.

When the catalytic system is on solid the appropriate substrate, it is advisable to replace the mercury catalysts in existing facilities containing a reactor with a fixed bed.

In accordance with the invention the molar ratio between the hydrogen chloride and acetylene introduced into the system, in General greater 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 have been 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 PLU increase the amount dissolved in the liquid phase acetylene is also possible to introduce into the reactor one acetylene in a gas, where he will react to the presence of liquid phase hydrogen chloride in the form of a hydrochloride, with amanohashidate catalytic system will be regenerated by contact with a liquid containing amine and hydrogen chloride and circulating outside of the reactor.

In the General case, the catalytic system obtained when dissolving or dispersing the desired amount of compound of metal of group VIII in Amina or in a mixture of an amine and an organic solvent, and then by further saturation of the hydrogen chloride, contributing to the formation of amanohashidate. However, equally possible to first saturate amine or a mixture of an amine and an organic solvent hydrogen chloride before receiving amanohashidate, and then enter the compound of the metal of group VIII in amanohashidate or in a mixture of an amine with an organic solvent. Normally, the amount of compound of metal of group VIII corresponds to the fact that any use of a compound of the metal of group VIII in the catalyst system is dissolved. For information, the solubility of platinum chloride (II) in a mixture of about equal. parts of amanohashidate PRIMENE 81-R and solvent SHELLSOL exceeds 1 mol/L. However, you can use the m state, that does not contradict the invention.

The invention is illustrated by the following examples. Examples 1-5, 7, 13-15 and 18-27 comply with the proposed method of the invention. Examples 6/C/, 8/C/- - 12/C/, 16/With/ 17/S/ is shown for comparison.

Examples 1-6/C/. The catalytic system obtained on the basis of amine PRIMENE 81-R, palladium chloride, and optionally solvent SHELLSOLK. Amine PRIMENE 81-R is a primary amine tertiary alkyl, released Rohm and Haas. It is considered the mixture of amines, the number of carbon atoms in which from 12 to 14. The solvent SHELLSOLK, released Shell, consists of a mixture of hydrocarbons, mainly aliphatic series. The initial boiling point of the solvent described in these examples, equal to 193oC and the final boiling point -245oC.

Amine PRIMENE 81-R is first mixed with different volumes of solvent SHELLSOLK, then 4 g of palladium chloride (II) or 22.6 mmol enter without stirring in 1 liter of solution. The catalytic system is prepared by saturating a solution of gaseous hydrogen chloride.

The reaction between acetylene and hydrogen chloride is as follows.

In a reactor made of Pyrex with an internal volume of 45 ml with double shell in kinnego glass for dispersing gas in a liquid phase, inject 30 ml of a solution consisting of amine PRIMENE 81-R, palladium (II) chloride and, if necessary, solvent SHELLSOLK.

The solution is heated at a temperature of 150oC, and the gas stream comprising a mixture of hydrogen chloride and acetylene with a molar ratio of Hcl/C2H2equal 1,17 injected into the reactor. In accordance with the conditions of the test 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 2.5 to 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 (srg).

The results are presented in table.1. The amount of vinyl chloride expressed in g/h and g/l catalyst system. The selectivity of its action is defined as the molar ratio between the product of VC and the sum of (VC + (2 x srg)).

Examples 7 12/C/. Different catalytic systems prepared in the same manner as described in example 4 (the weight quantity of the amine PRIMENE 81-R and solvent SHELLSOLK identical), but the palladium chloride is substituted by an identical molar concentration of 22.6 mmol/l) chloride platinum (II) chloride copper (I) chloride copper (II) chloride, zinc (II), conditions, described in examples 2-6, except for the time of the presence of equal 4,95 C.

The results are presented in table.2.

Examples 13 17/C/. Different catalytic systems receive the same manner as described in examples 4 or 7, using the same weight amounts of amine and solvent SHELLSOLK, but the amine PRIMENE 81-R replaces other compounds containing nitrogen. Amine PRIMENE JM-T, used in example 13, is a mixture of primary amines tertiary alkyl of C18-C22, released Rohm and Haas.

The reaction hydrochlorination of acetylene is carried out at the same temperature and, subject to the same ratios of reagents indicated in examples 4 and 7. In examples 13-16/C/ the time is 4.9 C; for test 17/C/ it is 2.5 s;

The results are presented in table.3.

Examples 18-21. Different catalytic systems prepared in the same manner as described in example 7 (the weight amount of amine PRIMENE 81-R and solvent SHELLSOLK identical), but with the change in the number of chloride of platinum (II). The reaction hydrochlorination of acetylene is carried out in the same conditions as described in example 7.

The results are presented in table.4. Output is defined as the molar ratio of p is mu described in example 20 used in the experimental reactor with the same principle as the reactor described in examples 1-21, but consisting of one column of Pyrex height of 2 m and a diameter of 2.54 cm and provided with annular nozzles type Rash. In the reactor pour 500 ml of the catalyst solution. The reaction hydrochlorination of acetylene is carried out in the same conditions, i.e. at the same temperature and, subject to the same ratios of reagents, as in the previous examples, but using a different time.

The results are presented in table.5.

Example 26. Different catalytic systems prepared by the method described in example 20, but the solvent SHELLSOLK replace solvent SOLVESSO 150. The solvent SOLVESSO 150, released ESSO, consists of a mixture of hydrocarbons, mainly aromatic series (alkyl benzenes), having initial boiling point 188oC and a final boiling point 208oC. the Reaction hydrochlorination of acetylene is carried out in the same conditions as in example 20.

The results are presented in table.6.

Example 27. The catalytic system is prepared by impregnating 50 ml alumina, previously dried for 24 hours at a temperature of 250oC, PR is and gaseous hydrogen chloride through the impregnated alumina, placed in the reactor. The used alumina is an alumina RLKC GS 2078/3 de KALI CHEMIE. It has the following characteristics: diameter 3 to 4 mm; specific surface WET 179 m/g; pore volume of 0.53 ml/g; specific gravity of 0.71 g/ml; the amount of water absorption of 0.59 ml/g Using a reactor similar to the reactor described in examples 1-21, but having an inner volume of 70 ml Reactor is heated at a temperature of 200oC and injected into a gas stream containing a mixture of hydrogen chloride and acetylene with a molar ratio of HCl/C2H2equal 1,17. The gas retention time corresponds to 7.5 C. the Amount of vinyl chloride is equal to 32.2 g/h per 1 g used platinum. The selectivity of the reaction is 99,71%

1. Catalytic system for producing vinyl chloride by hydrochloridebuy acetylene-containing compound of the metal of group VIII, characterized in that it further comprises amanohashidate with sterically hindered spatial structure and a melting point lower than or equal to 25oC, containing from 8 to 30 carbon atoms, formulas

< / BR>
where R1and R2hydrogen atoms or identical or different alkyl or aryl groups;

R3alkyl or Ari the rata.

2. The system under item 1, characterized in that compounds of group VIII it contains a compound of palladium or platinum.

3. The system under item 1, characterized in that it contains amanohashidate formula

< / BR>
where R1, R2, R3alkyl.

4. The system under item 2, characterized in that compounds of palladium or platinum it contains a palladium (II) chloride or platinum chloride (II).

5. The system under item 1, characterized in that it contains hydrochloride tertiary alkylamine and chloride platinum (II).

6. The method of producing vinyl chloride by reacting acetylene and hydrogen chloride at an elevated temperature in the presence of a catalytic system containing a compound of the metal of group VIII, characterized in that the use of the catalytic system, optionally containing amanohashidate with sterically hindered spatial structure and a melting point lower than or equal to 25oC, containing from 8 to 30 carbon atoms, formulas

< / BR>
where R1and R2hydrogen atoms or identical or equal to alkyl or aryl group;

R3alkyl or aryl group,

when the content of the compound of metal of group VIII 1 200 mmol per 1 liter of ispolzuut the palladium (II) chloride or platinum chloride (II).

8. The method according to PP. 6 and 7, characterized in that the use of the catalytic system, deposited on a solid support.

9. The method according to p. 6, characterized in that the use of the catalytic system in the liquid phase.

10. The method according to p. 9, characterized in that the use of the catalytic system, the diluted high-boiling organic solvent selected from aliphatic, cycloaliphatic and aromatic hydrocarbons or their mixtures at a mass ratio of the specified solvent and amanohashidate equal to (0.01 to 5):1.

11. The method according to PP. 6 to 10, characterized in that the process is conducted at 80 - 200oC.

12. The method according to PP. 6 to 11, characterized in that the process is conducted at a molar ratio of hydrogen chloride and acetylene, is equal to (0.5 to 3):1.

 

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