The catalyst for the oxidation of sulfur compounds
(57) Abstract:The invention relates to the production of heterogeneous catalysts for liquid-phase oxidation of sulfur compounds (sulfur dioxides, verouderde, mercaptans) and can be used for purification of gas emissions and wastewater, energy, refining, petrochemical, chemical and pulp and paper industries.Proposed heterogeneous catalyst for the oxidation of sulfur compounds containing active ingredient and a carrier - high-pressure polyethylene, characterized in that as component contains the oxide of antimony (III) and pyrite cinder, in the following catalyst components (mass fraction, %):
pyrite cinder - 33 - 37
the oxide of antimony (III) - 4 - 6
polyethylene - the rest. table 1. The invention relates to the production of heterogeneous catalysts for liquid-phase oxidation of sulfur compounds (sulfur dioxide, hydrogen sulfide, mercaptans) and can be used for gas cleaning and wastewater, energy, refining, petrochemical, chemical and pulp and paper industries.Known heterogeneous ka is kind and organic sulfur compounds  the Main disadvantage of this catalyst is unsatisfactory, the depth of oxidation of hydrogen sulfide and organic sulfur compounds to sulfur dioxide. Sulfur dioxide is hard to recover highly toxic component. The cleaning gas from the sulfur dioxide is in itself no less a problem than purification from hydrogen sulfide and serverance.The closest in technical essence and the achieved effect to the present invention is a catalyst for the oxidation of sulfur compounds, containing as an active ingredient the active sludge (35 of 50) and medium - high density polyethylene (or polypropylene, polystyrene) 
The specified catalyst-prototype differs relatively little activity in the process of liquid-phase oxidation of sulfur dioxide, and also has significantly less activity in the oxidation of hydrogen sulfide and mercaptans in comparison with the proposed catalyst.The aim of the invention is to increase the catalyst activity.This goal is achieved by the fact that the catalyst for the oxidation of sulfur compounds (sulfur dioxide, hydrogen sulfide, mercaptans) contains as active ingredients pyrite cinder and oxide of antimony (III) and medium - high-pressure polyethylene in the following ratio, wt.Pyrite cinder 33 37
The oxide of antimony (III) 4 6
Polyethylene is the quiet inserted into the mass media of high-pressure polyethylene. Instead of activated sludge is used a mixture of oxides of metals of variable valence pyrite cinder and oxide of antimony (III).The proposed catalyst in comparison with the known has a higher total activity, but most significantly the activity of the catalyst is increased in the process of liquid-phase oxidation of sulfur dioxide. Using a specified catalyst for the oxidation of sulfur compounds is carried out in the liquid phase and flows mainly to thiosulfate or sulfates, depending on the oxidation conditions.Testing the activity of the catalyst in the process of absorption and catalytic gas cleaning and SO2was carried out in the reactor of continuous operation when the film mode of the process. Absorbent, which used water, was fed into the reactor from above, the gas backflow from the bottom. For experiments we used synthetic gas mixture containing sulphur dioxide 2000 - 2500 mg/m3and volume concentration of oxygen of 10% which roughly corresponds to their content in the flue gases of thermal power plants operating on brown coal. Sulfur dioxide was supplied from a cylinder, and the reduction of oxygen was carried out by dilution of the gas mixture with nitrogen.
Therefore, additional controlled plant's effluent liquid-phase oxidation of SO2for completeness turning it into an H2SO4. The testing results show that using the proposed catalyst absorbed water SO2oxidized to sulfuric acid of not less than 96 99% versus 5 to 10% in the control experiment without catalyst.Experiments to determine the activity of the catalyst in the process of liquid-phase oxidation of hydrogen sulfide and mercaptans oxygen was carried out on real wastewater of pulp and paper production secondary condensates residue of black school is the Odile in reactor periodic action with the following parameters: temperature 60oC; pressure 0.3 MPa; oxidation time 3 min; feed rate of air 10 20 h-1; the mass ratio of the catalyst waste water 1 5. The air in the reactor was carried out from the bottom using a special dispersant, provide good mass transfer.The catalyst activity was evaluated according to the degree of oxidation of hydrogen sulfide and methylmercaptan in waste water, for this was determined by the concentration of H2S and mercaptan in the original and oxidized wastewater. The definition of H2S and mercaptan was carried out potentiometrically by GOST 22985-88.High catalytic activity of the proposed catalyst is observed at the specified mixing ratio of the active basis of the catalyst pyrite cinder and oxide of antimony (III), especially activity in the process of liquid-phase oxidation of sulfur dioxide.In addition, it is important that the mass fraction of the carrier in the catalyst was in the range of 57 to 65% Decrease in the mass fraction of the carrier of polyethylene in the composition of the catalyst is less than 57% leads to decrease in mechanical strength of the granules of the catalyst, and the increase in the mass fraction of the media more than 65% decrease in catalyst activity.Example 1. Cat is Aut as follows. Mixing of the components and forming pellets of the catalyst is carried out at an industrial unit for the granulation of polyethylene with a minimum load of mixer 60 kg, so the components of the catalyst are taken in the following quantities, kg: pyrite cinder 19,8; oxide of antimony (III) 2,4; polyethylene 37,8. Active the basis of the oxides of metals of variable valency after a preliminary dry mixing and grinding them in a ball mill for 8 hours mixed with the carrier of the high-pressure polyethylene (LDPE) at a temperature of 120 130oC for 20 to 30 minutes Duration of mixing depends on the composition of the catalyst. After mixing the resulting mass is fed into a screw extruder, where with the help of special nozzles is formed in the form of pellets or rings required shape and size. For studies were made of the samples of the catalyst in the form of spherical granules with a diameter of 4 to 6 mmExample 2. The catalyst composition, wt.Pyrite cinder 33
The oxide of antimony (III) 6
manufactured according to the technology described in example 1.Example 3. The catalyst composition, wt.Pyrite cinder 37
The oxide of antimony (III) 4
manufactured by BR>The oxide of antimony (III) 6
manufactured according to the technology described in example 1.The catalysts obtained in examples 1 to 4, and the catalyst-the prototype was tested for activity in the processes of liquid-phase oxidation of SO2H2S and mercaptan according to the methods described above, as well as stability within 200 hours the Results are given in the table.Experiments to determine the activity of the samples showed that the introduction of the catalyst components in the ratio of examples 1 to 4, i.e. in the ratio provided by the invention allows to obtain highly active catalysts with high mechanical strength and stability. The proposed catalyst is substantially outweighed by the activity known.The efficiency of absorption and catalytic gas cleaning and SO2in the presence of the proposed catalyst is 96 to 97% compared to 41.5% for the catalyst of the prototype. The proposed activity of the catalyst in relation to the oxidation of hydrogen sulfide is 98 to 99% and methylmercaptan 95 96% compared with 76.8% and 62.7 percent, respectively, for the prototype. The greatest increase in activity was noted in the oxidation dioxide is N 5 8 content components, lying outside the bounds provided by the invention. The composition of the sample and the test results of their activity and stability are also presented in the table.Analysis of the results allows us to conclude that the ratio of the mass fraction of pyrite cinder to the mass fraction of oxide of antimony (III) must be within 1 (6 8,2). The change of this ratio of components in the direction of increasing the share of pyrite cinder (sample 5), and in the direction of increasing the share Sb2O3(sample 6), leads to a reduction in the overall activity of the catalyst.The decrease in the mass fraction of the carrier in the catalyst below 57% (sample 7: the content of the carrier 55%), while maintaining the required ratio of the metal oxides in the composition of the active bases leads to an abrupt drop in the mechanical strength of the obtained sample. This entails rapid destruction of the catalyst in the catalytic reaction conditions and, therefore, reduction of service life. The increase in the mass fraction of the carrier above 65% (sample 8: the content of the carrier 66), while maintaining the desired ratio of metal oxides in the composition of the active framework entails a reduction in the overall activity of the catalyst.The results of the tests about the ora is the best.The use of the catalyst in the industry will improve the efficiency of wastewater treatment and gas emissions, reduce the size of technological devices, to carry out the cleaning process in more mild conditions. All this makes it possible to reduce capital and operating costs during the implementation of the cleaning process using this catalyst. The catalyst for the oxidation of sulfur compounds containing active component on the carrier of the high-pressure polyethylene, characterized in that as the active component contains the oxide of antimony (III) and pyrite cinder at the following content, wt.share
Pyrite cinder 33 37
The oxide of antimony (III) 4 6
SUBSTANCE: invention relates to a homogeneous catalyst based on tetra-4-(4'-carboxyphenylsulphanium)-5-cobalt nitrophtalocyanine(II) of tetrasodium salt of formula .
EFFECT: invention allows to produce a compound having a high catalytic activity in the oxidation of sodium diethyldithiocarbamate.
4 dwg, 1 tbl, 2 ex
SUBSTANCE: nanotubular materials crystallising in the system of K2O-TiO2-X-H2O (X=NiO, MgO, Al2O3, Cr2O3, CO2O3, Fe2O3) are characterized by the fact that in their composition up to 10% of ions Ti4+ is replaced by doping two- or trivalent metal. The method of synthesis of nanotubular materials is characterized by the fact that the synthesis of the samples is carried out by hydrothermal treatment of a pre-prepared mixture of hydroxide in KOH solution, to produce the initial mixtures of hydroxides, a solution of titanyl chloride synthesised by reaction of TiCl4 with chilled distilled water, is mixed with aqueous solutions of salts of finished elements in a predetermined ratio, and then the precipitation of hydroxides is produced by adding NH4OH to the aqueous solution mixture at pH=9-9.5 followed by washing with distilled water, drying at 70-90°C and mechanical crushing, then the crushed precipitate is mixed with 10 M KOH solution and subjected to a hydrothermal treatment at 170-180°C for, at least, 24 hours, after which the resulting product is washed with distilled water.
EFFECT: invention makes it possible to synthesise potassium-titanate nanotubes with an average outer diameter of 5 to 12 nm.
2 cl, 5 dwg, 2 ex
SUBSTANCE: method of growing diamond single-crystals doped with nitrogen and phosphorus at high pressures of 5.5-6.0 GPa and temperatures of 1600-1750°C is carried out on the seed crystal, which is pre-pressed into a substrate of cesium chloride and separated from the source of carbon, nitrogen, and phosphorus with the metal-solvent, which is used as an alloy of iron, aluminium, and carbon. Between the source of carbon, nitrogen, and phosphorus and the seed crystal, a temperature difference of 20-50°C is created. The alloy of iron, aluminium, and carbon in the metal-solvent is taken with the following component ratio, wt %: iron 92.5-95.0; aluminium 2.5-0.5; carbon 5.0-4.0. The mixture of the source of carbon, nitrogen, and phosphorus is taken with the following component ratio, wt %: carbon (graphite) 95.0-97.0; phosphorus 5.0-3.0; adsorbed nitrogen 0.001±0.0005. Heating is carried out up to the initial temperature in a zone of growth at 100-250°C higher the melting temperature of the alloy of the metal-solvent, the exposure is produced at this temperature for 50 to 150 h. The mass flow rate of crystal growth is more than 2 mg/h. The technical result consists in the controlled doping the diamond single- crystal grown on the seed with impurities of phosphorus and nitrogen in the conditions of influence of high pressure and temperature.
EFFECT: resulting large diamond single-crystals contain a nitrogen admixture in the concentration of 0,1-17,8 parts per million of carbon atoms and phosphorus in a concentration of 0,5-5 parts per million of carbon atoms.
2 dwg, 3 ex
SUBSTANCE: urea-containing solution (13) is produced in the section (10) of synthesis, the solution is purified in the section (14) of extraction, and an aqueous solution (15) containing mostly urea and water, which is produced from the above-mentioned section of the extraction is subjected to the concentration process. Herewith the concentration process includes a separation step through an elective membrane.
EFFECT: improvement of the current urea production process.
9 cl, 1 dwg
SUBSTANCE: anti-photobleaching additive is polyester-modified polysiloxane, methyl ether of polyethylene glycol, or polyoxyethylenesorbitan. The anti-photobleaching additive is selected to reduce photobleaching while maintaining the photocatalytic activity of the composition to at least 90%. In the photocatalytic composition, the said additive is present in a series of 1-35 vol.%. The photobleaching index (AL) of the said composition is less than 6. A photocatalytic coating, a building panel, and a method for applying a photocatalytic composition are also described.
EFFECT: obtaining a composition with reduced photobleaching and with the stored photocatalytic activity.
25 cl, 10 dwg, 3 tbl, 6 ex
SUBSTANCE: method involves transporting the polymer to a polymer storage container along a supply line using a carrier medium. The container is a container for the seed layer for the gas phase polymerization process. Then, at least a portion of the polymer in the container is recirculated by means of recovering the polymer from the container and supplying the recovered polymer to said supply line. Recycling is carried out simultaneously with transportation. During the transportation and recycling, cooling the polymer to a temperature not exceeding 50°C is provided.
EFFECT: expanding the range of technological tools.
14 cl, 3 dwg
SUBSTANCE: claimed invention relates to catalysts of hydration, method of their production and use for hydration such as selective hydration of acetylene admixtures in non-purified olefinic and diolefiniuc flows. Described is a selective catalyst of hydration for selective hydration of acetylene admixtures in non-purified olefinic and diolefinic flows, containing only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, applied on carrier, which is alumunium oxide with the following physical characteristics: BET surface area from 30 to approximately 100 m2/g, total volume of pores on nitrogen from 0.4 to approximately 0.9 cm3/g and the average pore diameter from approximately 110 to 450 Å , where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Described are the method of catalyst production, which includes impregnation of carrier represented by aluminium oxide and having the aforesaid physical characteristics, with soluble salts of only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, from one or more solutions, obtaining impregnated carrier, where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Also described is the method of selective hydration of acetylene compounds, which includes contact of original raw material containing acetylene compounds and other unsaturated compounds, with the described above catalyst.
EFFECT: increased degree of 1,3-butadien extraction with full or nearly full conversion of C4-acetylenes.
25 cl, 1 dwg, 1 tbl, 2 ex
SUBSTANCE: description is given of a catalyst for converting ammonia to nitrogen (II) oxide with a block cellular structure, with the shape of a rectangular prism or oblique prism with obliquity of 0-45°, coefficient of thermal expansion in the interval 10-7-10-5 K-1 in the temperature range of 900°C, based on mixed oxides with general formula: xMe1O·yMe2O·(1-x-y)(2MgO·(2-z)Al2O3·(5+z)SiO2), where: x=0.03-0.25; y=0.01-0.1; z=0-2, Me1 - is an active component; Me2 - is a structural promoter. Described also is a method of catalytic conversion of ammonia, which involves passing a reaction gaseous mixture, containing ammonia and an oxygen containing gas, through a two-stage catalyst system, made using different methods, including in a set with trapping platinoid gauze and/or inert packing. The proposed catalyst is used in the second stage.
EFFECT: catalyst has high activity, selectivity and resistance to thermo-cycles when used in a two-stage system.
6 cl, 3 tbl, 13 ex
SUBSTANCE: invention relates to regeneration of spent metal-containing catalysts for organic synthesis. Described is a method of regenerating metal oxide industrial catalysts for organic synthesis, comprising a support with oxides of Cu and Bi or Cu, Ni and Cr, the method involving treatment of the spent catalyst with salicylalaniline solution in dimethyl formamide with concentration between 0.1 and 0.5 mol, filtration of the solution of the complex compound, which is adsorbed directly on the cleaned support which is silica gel or zeolite obtained after filtration, and the obtained adsorbent undergoes thermal decomposition on the surface of the support at temperature 150-200°C.
EFFECT: described catalyst regeneration method enables multiple regenerations, lowers power consumption of the regeneration process while simplifying the process and without aggressive and toxic media.
SUBSTANCE: invention relates to a method of producing a photocatalyst based on bismuthate of an alkali-earth metal and to a method for photocatalytic treatment of water from organic contaminants. Method of producing a photocatalyst involves dissolving bismuth nitrate and alkali-earth metal nitrate in a solvent, wherein solvent is an aqueous solution of polyatomic alcohol, containing at least five carbon atoms, with subsequent annealing of precursor at 550-650 °C to produce nanoparticles of amorphous bismuthate of alkali-earth metal of non-stoichiometric composition with degree of oxidation not equal to two. Prior to annealing, precursor is evaporated until formation of an organic matrix with uniform distribution of bismuth and alkali-earth metal atoms. Then a crystal lattice of photocatalyst is formed at 650-750 °C. When purifying water from organic contaminants using photocatalyst, weight ratio of purified water to weight of photocatalyst is selected from interval of 1000/1-1600/1, and irradiation with visible light of water with organic pollutants is carried out for 3-4 hours.
EFFECT: method enables to obtain particles of bismuthate of alkali-earth metal with an inhomogeneous composition, in form of a heterostructure of bismuth oxide, coated with bismuthate of alkali-earth metal of stoichiometric composition with degree of oxidation of calcium, equal to two, without defects in crystal lattice with low specific surface area without pores, as well as reduced consumption of photocatalyst during water treatment due to reduction of average particle size of photocatalyst and broader functional capabilities.
4 cl, 2 tbl, 59 ex
SUBSTANCE: method of producing a photocatalyst based on alkaline earth metal bismuthate is to dissolve a mixture of bismuth nitrate Bi(NO3)3 and inorganic salt of alkaline earth metal Me, followed by standing of the products of their hydrolysis to form particles with bismuth ions evenly distributed by their volume and unevenly distributed alkaline earth ions and removal of excess moisture from the hydrolysis products, heating the produced particles to form particles as a heterostructure from amorphous by structure and stoichiometric by composition alkaline earth metal bismuthate and amorphous by structure and stoichiometric by composition bismuth oxide Bi2O3 followed by their crystallization. Herewith as inorganic salt of alkaline earth metal Me, alkaline earth metal oxalate MeC2O4 is taken, before dissolving alkaline earth metal oxalate MeC2O4 is purified from the adsorbed compounds and mixed with bismuth nitrate Bi(NO3)3, maturation of the products of their hydrolysis leads to the formation of particles of alkaline earth metal oxalate MeC2O4 impregnated with ions Bi(OH)2+, with evenly distributed bismuth ions and unevenly distributed alkaline earth metal ions, removal of excess moisture from the products of hydrolysis leads to the formation of precursor-particles in the form of heterostructures with the central part of alkaline earth metal oxalate MeC2O4impregnated with ions Bi(OH)2+ and the outer shell of bismuth hydroxonitrate Bi(OH)(NO3)2, heating the precursor-particles is carried out at two stages to form alkaline earth metal carbonate MeCO3impregnated with ions Bi(OH)2+, in the central part of each particle in the first stage and up to the formation of amorphous particles in the form of heterostructures with a central area of amorphous by structure and stechiometric by composition alkaline earth metal bismutite and the surface layer of the amorphous by structure and stechiometric by composition bismuth oxide Bi2O3 at the second stage, crystallization leads to the formation of particles of the photocatalyst in the form of heterostructures with the central area of crystalline by structure and stechiometric by composition alkaline earth metal bismutite and the surface layer of crystalline by structure and stechiometric by composition bismuth oxide Bi2O3. For mixing, the components are taken in the following ratio, wt %: alkaline earth metal oxalate MeC2O4 4.49-3.63, bismuth nitrate Bi(NO3)3 95.51-96.37, dissolution is carried out in distilled water with the following ratio of components, wt %: mixture of alkaline earth metal oxalate powders MeC2O4 and bismuth nitrate Bi(NO3)3 5.00-15.00, distilled water 95.00-85.00, heating of precursor-particles at the first stage is carried out up to 520°C with a heating rate of 0.5-1.0°C/min, at the second stage - up to 810°C with a heating rate of 1.0-2.0°C/min, the crystallization is carried out at a temperature of 750-825°C.
EFFECT: increasing the lifetime of the catalytic properties of the photocatalyst.
1 tbl, 20 ex