Catalytic system for heterogeneous reactions

FIELD: heterogeneous catalysts.

SUBSTANCE: catalytic system comprises (i) high-silica fibrous carrier characterized by 29Si MNR spectrum, in which lines with chemical shifts -100±3 ppm (line Q3) and -110±3 ppm (line Q4) are present at ratio of integral intensities Q3/Q4 from 0.7 to 1.2; IR spectrum, in which absorption bands of hydroxyl groups with wave number ν=3620-3650 cm-1 and half-width 65-75 cm-1 are present; which carrier has specific surface SAr=0.5-30 m2/g as measured by BET method from thermal desorption of argon, surface area SNa=10-250 m2/g as measured by alkali titration method, at SNa/SAr ratio 5 to 30; and (ii) at least one active element. The system represents geometrically structured one constituted by microfibers with diameter 5-20 μm and additionally has active centers characterized in IR spectra of adsorbed ammonia by presence of an absorption band with wave numbers ν=1410-1440 cm-1.

EFFECT: increased catalytic activity, resistance to deactivation, and selectivity.

3 cl, 7 ex

 

The invention relates to the field of chemical industry, new catalysts that can be used, in particular, in the processes of recycling of chlorinated organic wastes, the cleanup of gaseous and liquid emissions from toxic organochlorine impurities in the oxidation of sulfur dioxide to the trioxide, in the production of sulfuric acid or sulfur-containing cleaning industrial gas emissions, in the process of obtaining valuable monomer is vinyl chloride from ethylene dichloride, in the processes of production from methane and natural gas such valuable products, such as methyl chloride, vinylchloride, light olefins, the process of the purification of exhaust gases of diesel engines, in deep oxidation of toxic organic impurities and in other processes.

Known catalyst for heterogeneous reactions, containing at least one catalytically active element and vysokoglinozemistyj media, characterized by the presence of the NMR spectrum29Si lines with the chemical shift of -100±3 ppm (line Q3and -110±3 ppm (line Q4) when the ratio of the integral intensities of the lines of Q3/Q4from 0.7 to 1.2, in the infrared spectrum absorption band of hydroxyl groups with wave number 3620-3650 cm-1and the width of 65-75 cm-1having a specific surface area measured by the BET method on a heat desorb the AI argon S Ar= 0.5 to 30 m2/g, the magnitude of the surface, measured by the method of alkaline titration SNa= 10-250 m2/g at a ratio of SNa/SAr= 5-30 (RF Patent No. 2160156, IPC 6 B 01 J 21/08, priority from 28,12 .1999, published 10.12.2000,).

The disadvantages of the known catalysts are relatively low activity, decontamination aggressive reaction media, as well as low selectivity transformations in a number of reactions.

The authors sought to develop a catalytic system for heterogeneous reactions with a higher activity and resistance to deactivation and increased selectivity.

The problem is solved in that the catalytic system for heterogeneous reactions involving vysokoglinozemistyj fibrous media, characterized by the presence of the NMR spectrum29Si lines with the chemical shift of -100±3 ppm (line Q3and -110±3 ppm (line Q4) when the ratio of the integral intensities of the lines of Q3/Q40.7-1.2, infrared absorption band of hydroxyl groups with wave number ν = 3620-3650 cm-1and the width of 65-75 cm-1having a specific surface area measured by the BET method by thermal desorption of argon, SAr= 0.5 to 30 m2/g and the magnitude of the surface, measured by the method of alkaline titration, SNa= 10-250 m2/g / n and the ratio of S Na/SAr= 5-30, and at least one active element is a geometrically structured system of microfibers with a diameter of 5-20 μm, has an additional active centers, which are characterized in the IR spectra of adsorbed ammonia in the presence of absorption bands with wave numbers in the range ν = 1410-1440 cm-1. Additionally, the active component of the catalyst system selected from the group comprising platinum, palladium, rhodium, iridium, silver, zirconium, chromium, cobalt, Nickel, manganese, copper, tin, gold, titanium, aluminum, iron, molybdenum, and/or their oxides and/or their salts, and microfiber are structured as either non-woven or extruded material such as wool or felt, or threads with a diameter of 0.5 to 5 mm, or woven from the threads of the material with the weave type : sateen, canvas, Agur with a cell diameter of 0.5 to 5 mm

The technical effect of the invention is greater selectivity in providing a higher yield of the target products of heterogeneous reactions, for example, in the recycling processes of organochlorine wastes, treatment of gaseous and liquid emissions from toxic organochlorine impurities in the oxidation of sulfur dioxide to the trioxide, sulphuric acid production and purification of sulfur-containing industrial gas emissions, in the process of obtaining valuable monomer - vinyl is lorida of dichloroethane, in the processes of production from methane and natural gas products such as methyl chloride, vinylchloride, light olefins, and others.

Catalytic system for heterogeneous reactions contains a carrier and an active element and represents a geometrically structured system of microfibers. Microbiology catalytic system can be structured in the form of a woven, non-woven or extruded material. The active component of the catalyst system is at least one element selected from the group comprising platinum, palladium, rhodium, iridium, silver, zirconium, chromium, cobalt, Nickel, manganese, copper, tin, gold, titanium, aluminum, iron, molybdenum, and/or their oxides and/or their salts, the IR spectrum of the ammonia adsorbed on the catalyst, characterized by the presence of characteristic absorption bands with wave numbers in the range ν = 1410-1440 cm-1.

The presence of characteristic bands in the range ν = 1410-1440 cm-1indicates the specific acidic properties of the proposed catalyst for heterogeneous reactions. The specified properties of the catalyst can be formed in the preparation of the catalyst in a variety of ways, for example, by introducing into its constituent atoms of aluminum as described in well-known scientific and technical literature (R.G.Rouxhet, R.E.Sempels//J.Chem.Soc.Farad.Trans.l. - v.70, 1974, pp.2021-202).

Example 1

Produce the receipt of vinyl chloride from ethylene dichloride, for which the pair of dichloroethane is passed through the catalytic system. The catalytic system, structured in the form of a woven material, contains vysokoglinozemistyj fibrous media with the diameter of the microfibers of about 5-10 μm, and the active component (platinum), and in the preparation of the system is modified by introducing atoms of aluminum so that the IR spectra of adsorbed ammonia had characteristic bands in the range ν = 1410-1440 cm-1. In the temperature range of 400-550°and space velocity of the reaction mixture 10-20 thousand hours-1achieved selectivity of the conversion of dichloroethane to vinyl chloride at the level of 94-98% conversion dichloroethane about 80%. The only byproduct is acetylene, other substances are not detected just at the threshold of sensitivity analysis not higher than 1 ppm. Coking and resinification catalyst system is not observed. Conducting the experiment under these conditions for 60 hours shows no decrease in activity and selectivity of the catalyst. The results indicate a high activity, selectivity and resistance to deactivation of the claimed invention.

Example 2

Produce utilization of dichloroethane, to which the pair dichloro the Tana mixed with air (volume concentration of dichloroethane is 0.1-3.5%) and passed through a catalytic system. The catalytic system, structured in the form of a woven material, contains vysokoglinozemistyj fiberglass media with the diameter of the microfibers of about 10 μm and an active component (platinum), and in the preparation of the system is modified so that the IR spectra of adsorbed ammonia had characteristic bands in the range ν = 1410-1440 cm-1. In the temperature range 400-500°and space velocity of the reaction mixture 16-18 thousand hours-1achieved complete conversion of dichloroethane in hydrogen chloride, water vapor and carbon dioxide. Other oxidation products (products of incomplete oxidation, elemental chlorine, phosgene, dioxin) not detected just at the threshold of sensitivity analysis not higher than 1 ppm. That indicates a high activity and selectivity of the proposed catalytic system. Conducting the experiment under these conditions for 6 hours shows no decrease in activity and selectivity of the catalytic system, which indicates its high stability. Using the same unmodified catalyst (not with these bands in the IR spectra of adsorbed ammonia) leads to the formation of significant quantities of unwanted by-products (vinyl chloride WITH). The use of other known catalysts also led the it to the formation of undesirable side products, in addition, they are strong deactivation in these conditions.

Example 3

The oxidation of sulfur dioxide is carried out in a laboratory isothermal reactor, passing the mixture containing 10% (vol.) SO2and 10% O2(the rest is nitrogen) through the catalytic system. The catalytic system contains glass fiber media with the diameter of the microfibers of about 10 μm (structured in the form of a woven material) and active component (platinum) and modified so that the IR spectra of adsorbed ammonia had characteristic bands in the range ν = 1410-1440 cm-1. At 300°and flow rate of the source gas mixture 4000 h-1achieved conversion of sulfur dioxide to 61-71%. In similar conditions, the method using a known platinum catalyst provides conversion of no higher than 10-15%, the method using a vanadium catalyst is less than 1-2%.

Example 4

Chlorination is subjected to natural gas containing at least 96% methane. To do this, natural gas is mixed with elemental chlorine in a volume ratio of 2:1 and at a temperature of 400°and atmospheric pressure is passed through a catalytic system containing the active ingredient (platinum) and woven fiberglass carrier with the diameter of the microfibers of about 10 μm, and the IR spectra of adsorbed ammonia have ha Acterna bands in the range of ν = 1410-1440 cm-1. There is a complete conversion of chlorine, methane conversion is ˜38%. The main product of chlorination is methyl chloride, the selectivity of the conversion of methane into methyl chloride is 96%. The selectivity of the formation of unwanted methylene chloride does not exceed 1%, polychlorinated hydrocarbons not more than 4%, while undesirable chloroform, carbon tetrachloride, phosgene, carbon monoxide and dioxins in the products of the reaction are absent completely.

Example 5

Same as in example 4, but the process is conducted at a temperature of 450-500°and the ratio of natural gas/chlorine 1:1. The conversion of chlorine - 100%, methane is about 80%. Observe the formation of light olefins (ethylene, propylene) with selectivity up to 70%, and vinyl chloride with selectivity up to 15%. When increasing the ratio of natural gas/chlorine to a value of 4:1 conversion of methane is reduced to ˜25%, while the selectivity of the formation of olefins reaches almost 100%. The use of other known catalysts to provide the specified valuable products (olefins, vinyl chloride).

Example 6

Chlorination on this catalytic system is subjected to propane, the process is carried out at 160°C, atmospheric pressure and at an initial ratio of propane/chlorine/inert gas is 1:1:1. Achieved conversion of propane to 55%, while the sat is aktivnosti education monochloropropane reaches 80%. With increasing the reaction temperature above 350°With monochloropropane turn to propylene with a selectivity close to 100%. The use of other known catalysts do not provide the specified securities products (monochloropropane, propylene).

Example 7

Produce cleaning exhaust gases of diesel engines, passing the exhaust through the catalytic system. The catalytic system contains glass fiber media (structured in the form of a woven material) and active component (platinum) and modified so that the IR spectra of adsorbed ammonia had characteristic bands in the range ν = 1410-1440 cm-1. In the temperature range 300-600°and bulk velocities 20000-200000 h-1achieved conversion of hydrocarbons WITH greater than 90%, the degree of reduction of nitrogen oxides - up to 70%. In similar conditions, the method using a known platinum catalyst provides conversion of nitrogen oxides no higher than 30-40%.

Example 8

Produce clean exhaust air painting plants from toxic vapors of organic solvents, passing the emissions through the catalyst bed. The catalytic system contains glass fiber media with the diameter of the microfibers 15 μm (structured in the form of extruded material) and active component (platinum) is modified to the IR spectra of adsorbed ammonia had characteristic bands in the range ν = 1410-1440 cm-1. In the temperature range varying between 250 and 600°achieved full conversion of toxic organic contaminants into harmless substances (water vapor, carbon dioxide). In similar conditions, the method using a known platinum catalyst provides conversion of impurities not exceeding 95-97%.

1. Catalytic system for heterogeneous reactions involving vysokoglinozemistyj fibrous media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (line Q3and -110±3 ppm (line Q4) when the ratio of the integral intensities of the lines of Q3/Q40,7-1,2, in the infrared spectrum absorption band of hydroxyl groups with wave number ν=3620-3650 cm-1and the width of 65-75 cm-1having a specific surface area measured by the BET method by thermal desorption of argon, SAr=0.5 to 30 m2/g, the magnitude of the surface, measured by the method of alkaline titration, SNa=10-250 m2/g with respect to SNa/SAr=5-30, and at least one active element, characterized in that it is a geometrically structured system of microfibers with a diameter of 5-20 μm and has an additional active centers, which are characterized by the IR spectrum of the Oh adsorbed ammonia by the presence of absorption bands with wave numbers in the range ν = 1410-1440 cm-1.

2. The catalytic system according to claim 1, characterized in that the active element selected from the group comprising platinum, palladium, rhodium, iridium, silver, zirconium, chromium, cobalt, Nickel, manganese, copper, tin, gold, titanium, aluminum, iron, molybdenum and/or their oxides and/or their salts.

3. The catalytic system according to claim 1, characterized in that the fibers are structured as either non-woven or extruded material such as wool or felt or threads with a diameter of 0.5 to 5 mm, or woven from the threads of the material with the weave type : sateen, canvas, Agur with a cell diameter of 0.5 to 5 mm



 

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2 cl, 5 tbl, 6 ex

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10 cl, 5 ex

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13 cl, 2 tbl, 17 ex

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3 cl, 4 ex

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