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 25°C, 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 200°C 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 KThe 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.
FIELD: supported catalysts.
SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.
EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.
5 cl, 9 ex
FIELD: alternative fuel production and catalysts.
SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.
EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.
6 cl, 2 tbl, 16 ex
FIELD: exhaust gas neutralization catalysts.
SUBSTANCE: catalyst contains at least one zeolite and additionally at least one oxide carrier selected from alumina, silica, titanium dioxide, and aluminum silicate, and also at least one precious metal selected from platinum, palladium, rhodium, and iridium. The latter are characterized by average oxidation degree below +2.5, average number of metal ligands more than 3, and average number of oxygen ligands less than 3, whereas precious metal atoms are present on zeolites and oxide carriers in the form of crystallites with average particle size 1-6 nm. Catalyst is prepared on an solid cellular element, for which oxide carriers and zeolites are first separately impregnated with precious metal precursors and then calcined in yet wet state by blowing them into gaseous combustion gases at 500-1000°C for 0.1 to 10 sec. Thereafter, common coating dispersion is processed, which is further used to coat solid cellular element. Coating is then dried, calcined, and reduced.
EFFECT: increased catalytic activity, prolonged lifetime of catalyst, and lowered minimum working temperature at which carbon monoxide and hydrocarbons start being catalytically converted.
10 cl, 8 tbl, 11 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention relates to catalytic methods of isomerizing n-butane into isobutane and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-butane into isobutane utilizing above-defined catalyst is also described.
EFFECT: lowered butane isomerization process temperature and pressure and increased productivity of catalyst.
13 cl, 1 tbl, 24 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention relates to catalytic methods of isomerizing n-paraffins and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-paraffins utilizing above-defined catalyst is also described.
EFFECT: lowered isomerization process temperature and pressure and increased productivity of catalyst.
17 cl, 3 tbl, 25 ex
FIELD: petrochemical processes and catalysts.
SUBSTANCE: invention provides catalyst composed of heteropolyacid: phosphorotungstic acid and/or phosphoromolybdenic acid, at least one precious metal deposited on essentially inert inorganic amorphous or crystalline carrier selected from group including titanium dioxide, zirconium dioxide, aluminum oxide, and silicon carbide, which catalyst retains characteristic structure of heteropolyacid confirmed by oscillation frequencies of the order 985 and 1008 cm-1 recorded with the aid of laser combination scattering spectroscopy and which has specific surface area larger than 15 m2/g, from which surface area in pores 15 Å in diameter is excluded. Method of converting hydrocarbon feedstock containing C4-C24-paraffins in presence of above-defined catalyst is likewise described.
EFFECT: increased catalyst selectivity and enhanced hydrocarbon feedstock conversion.
5 cl, 7 tbl, 7 ex
FIELD: catalyst preparation methods.
SUBSTANCE: invention, in particular, relates to catalyst based on synthetic mesoporous crystalline materials and provides hydrocarbon conversion catalyst composed of: group VIII metal/SO4 2-/ZrO2-EOx, where E represents element of the group III or IV of Mendeleev's periodic table, x = 1.5 or 2, content of SO4 2- is 0.1 to 10% by weight, ZrO2/EOx molar ratio is 1:(0.1-1.0), which has porous crystalline structure with specific surface 300-800 m2/g and summary pore volume 0.3-0.8 cm3/g. Preparation method comprises precipitation of zirconium compounds, in particular zirconium hydroxide or zirconyl, under hydrothermal conditions in presence of surfactant to form mesoporous phase, which is stabilized with stabilizing agents: group III and IV elements. When stabilization is achieved, if necessary, acidity is adjusted and group VIII metal is added.
EFFECT: increased specific surface area and heat resistance at simplified technology.
9 cl, 2 dwg, 2 tbl, 6 ex
FIELD: petrochemical processes.
SUBSTANCE: invention relates to hydrogenation of acetylene hydrocarbons in olefin-rich gas mixtures on heterogeneous catalysts. Hydrogen and olefin containing stream with admixtures of acetylene hydrocarbons is passed through catalyst bed, which is composed of (a) geometrically structured system including fibers of high-silica fibrous carrier characterized by presence in IR specter of hydroxyl group absorption band having wavelength υ=3620-3650 cm-1 and half-width 65-75 cm-1, having specific surface SAr=0.5-30 m2/g as measured by BET method from thermal desorption of argon, surface area SNa=5-150 m2/g as measured by alkali titration method, at ratio SNa/SAr=5-50; and (b) active element. Active element is made in the form of charged either metallic or bimetallic clusters characterized in diffuse-reflection UV-Vis specter by specific bands in region 34000-42000 cm-1 and ratio of (i) integral intensiveness of the band related to charged either metallic or bimetallic clusters to (ii) integral intensiveness of the band related, respectively, either to metallic or bimetallic particles is at least 1.0.
EFFECT: increased activity and selectivity of process at high ethylene/acetylene ratios.
5 cl, 1 dwg, 3 tbl
FIELD: fuel combustion catalysts.
SUBSTANCE: invention provides catalyst containing active aluminum oxide, magnesium oxide, at least one platinum-group precious metal, and also at least one material capable of accumulating nitrogen oxides, said magnesium oxide forming homogenous mixed oxide with aluminum oxide in concentration ranging form about 1 to about 40 wt % based on total weight of mixed oxide. The use of catalyst is also disclosed.
EFFECT: increased heat resistance of catalyst and accelerated conversion of nitrogen oxides.
24 cl, 14 dwg, 3 tbl, 8 ex
FIELD: hydrocarbon conversion processes and catalysts.
SUBSTANCE: invention, in particular, relates to selectively upgrading paraffin feedstock via isomerization. Catalyst comprises support and sulfated oxide or hydroxide of at least one of the elements of group IVB deposited thereon; a first component selected from group consisting of consisting of lutetium, ytterbium, thulium, erbium, holmium, and combinations thereof; and a second component comprising at least one platinum-group metal component. Catalyst preparation process comprises sulfating oxide or hydroxide of at least one of the elements of group IVB to form sulfated support; depositing the first component onto prepared support; and further depositing the second component. Invention also relates to hydrocarbon conversion process in presence of above-defined catalyst.
EFFECT: improved catalyst characteristics and stability in naphta isomerization process to increase content of isoparaffins.
13 cl, 2 dwg, 1 tbl