Catalyst for oxidation of sulfur compounds
(57) Abstract:The invention relates to the production of heterogeneous catalysts for liquid-phase oxidation of sulfur compounds, in particular sulfidogenic solutions, natural and waste water, and can be used in power, metallurgical, gas, refining, petrochemical and pulp and paper industries. The essence of the invention lies in the fact that the proposed active, stable, mechanically strong heterogeneous catalyst for oxidation of sulfidogenic solutions having a solids containing microsphere, chromium oxide, and optionally a polymeric binder, in a ratio of components, wt.%: microsphere 10-15, chromium oxide 3-5, the polymeric binder is rest. 3 table. The invention relates to the production of heterogeneous catalysts for liquid-phase oxidation of sulfur compounds, in particular sulfidogenic solutions, natural and waste water, and can be used in power, metallurgical, gas, refining, petrochemical and pulp and paper industries.Known electrochemical oxidation sulfidogenic obrazovanie hydrogen ions and, therefore, sulfuric acid occurs at the anode.The disadvantage of this process are the high cost of electricity, a limited amount of oxidizable solution and the absence of impurities in the oxidized solution.Closest to the invention on the achieved result and the technical nature of is use in the oxidation sulfidogenic solutions as a catalyst of activated carbon modified with Nickel, silver or platinum (UK Application N 1602218, B 10 D 53/36, published. 30.04.77).The disadvantage of this process is the low mechanical strength of the activated carbon in the process of liquid-phase oxidation in the conditions of the bubbling regime and the high sensitivity of the activated carbon to mechanical impurities.The gradual destruction of the active carbon will be accompanied by loss of modifying components, which are expensive metals and as a consequence the decrease of catalytic activity and stability of the catalyst.Clogged pores mechanical impurities will lead to blocking of active sites and deactivation of the active carbon and a catalyst and a sorbent.To resolve the above shortcomings, the oxidation sulfidogenic solutions proposed active, stable, mechanically robust, does not require filtering of impurities oxidized solutions of the heterogeneous catalyst containing microsphere, chromium oxide, and optionally a polymeric binder, wt.the microsphere 10-15
the chromium oxide 3-5
the rest of the binder polymer
The microsphere is part of the fly ash of thermal power stations and represents the gas aluminosilicates with a smooth external surface. The main components of the microspheres are steklovata, mullite, quartz, hematite, magnetite, an oxide of calcium. The composition of the microspheres include, wt.Al2O323,8
SiO2the rest of it.Example 1. The microsphere fly ash feed coal took the place of discharge of ash pulp in shlakozalivnyye with a specific gravity <1 t/m3dried in air at room temperature and then in an oven at 105oC to a residual moisture content of 7-/BR>Fe3O46,24
kept in chromic acid at room temperature and periodic stirring for 2 h, and then dried to a residual moisture content of 3-7 wt. and progulivali in a muffle oven at 350-400oC, then added to the polymer binder and molded spherical catalyst pellet. As the polymer binder used high-pressure polyethylene.Similarly produced catalysts containing chromium oxide and the microsphere in different mass ratio, mixing the respective components of the catalyst.Example 2. 500 ml sulfanilamide of structure solution 1000 mg/l sulfite ions were oxidized in the presence of 20 g of the catalyst prepared according to example 1.The catalyst was loaded into a glass reactor with recurring action dispergating plate at the bottom of the reactor to air. The air was applied from the block through the gearbox, the dosage was carried out using a rheometer at the exit of the reactor. Otdelochnye gases passed through the system sinks control the sulfur dioxide.Salpicaduras the solutions were oxidized in static mode PRA.Evaluation of catalytic activity of the prepared catalyst composition of example 1 was carried out in comparison with activated carbon modified with Nickel (prototype).The residual concentration of the sulfite ions and the concentration of sulfate ions in the oxidized solution was determined by conventional methods (Lurie Y. Y. A. Rybnikov I. Chemical analysis of industrial wastewater. Chemistry, 1974). Data on the catalytic activity of the catalysts are presented in table. 1.Example 3. 500 ml sulfanilamide solution containing 1,000 mg/l sulfite ions were oxidized in the presence of 20 g of the catalyst prepared according to example 1. The oxidation of the sulfite ions were carried out in static mode, at room temperature, atmospheric pressure, when the air flow of 10 l per 1 l of oxidized solution at the time of oxidation 1, 3, 5, 7, 10, 15, 25, 30, 40, 60, 80 minutes of the Received data with a known catalyst are presented in table. 2.Example 4. In this example determined the duration of the work proposed and the known catalysts. As oxidizable solution used the drains of getsomevalue with the content of the sulfite ions 300 mg/l and the concentration of mechanical impurities (ash) up to 2 g/l Effluent oxidized ID of chrome 3
the rest of the binder polymer
The catalyst was loaded into the reactor in example 2. Oxidation sulfidogenic wastewater was carried out at room temperature, atmospheric pressure, air flow of 10 l per 1 l of oxidized solution for 30 min, then the solution was decanted and analyzed for the residual content of the sulfite ions and the presence of sulfate ions. In this mode, the catalyst has worked for 40 hours Analysis of the presence of sulfite ions and sulfate ions were carried out in each 10-m experience.Comparative data for the determination of catalytic activity of the proposed catalyst in comparison with the known are given in table. 3.When used as a catalyst carrier activated carbon is mainly the adsorption of sulfate ions. After 6 hours of catalyst on active coal catalyst must partly be replaced because there is a saturation of the pores of the carrier, sulfite, sulfate ions, pores become clogged with ash and catalyst practically deactivated.Mechanical destruction of the granules of catalyst on charcoal when working in conditions of fluidized bed starts already after 3 h of operation catalyst. After 40 h of operation of the catalyst is enhanced by the above, and from data presented in the table, the claimed catalyst composition has a sufficiently high mechanical strength at the operating conditions of the fluidized bed, is not clogged with ash and superior to the catalyst-the prototype for catalytic activity in the oxidation of solutions containing sulfite ion and mechanical impurities.High catalytic activity of the proposed catalyst is achieved due to the significant dispersion caused active component and oxides of metals of variable valence, within the framework of the microspheres provided by the structure of the microspheres. Catalyst for oxidation of sulfur compounds containing active component on the carrier, characterized in that the active ingredient it contains chromium oxide as a carrier microsphere fly ash of thermal power stations and optionally a polymeric binder in the following ratio, wt.Microsphere fly ash of thermal power plants 10 15
The chromium oxide 3 5
The Rest of the binder polymer
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
FIELD: production of hydrorefining catalyst.
SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.
EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.
10 cl, 8 ex, 4 dwg
SUBSTANCE: proposed catalyst contains a complex of catalytically active oxides, including oxides of rubidium, cerium, chrome, magnesium, iron, bismuth, molylbdenum and at least, one of nickel or nickel with cobalt. The ratio of components is presented by the following general formula: RbaCebCrcMgdAeFefBigMo12Ox, where A is Ni or a combination of Ni and Co, a approximately ranges from 0.01 to 1, b approximately ranges from 0.01 to 3, c approximately ranges from 0.01 to 2, d approximately ranges from 0.01 to 7, e approximately ranges from 0.01 to 10, f approximately ranges from 0.01 to 4, g approximately ranges from 0.01 to 4, and x is a number, defined by valency of other present elements. "b"+"c" is greater than g. The catalyst does not contain manganese, noble metal or vanadium. The carrier is chosen from a group comprising silica gel, aluminium oxide, zirconium oxide, titanium oxide or their mixture. The catalyst is used for oxidative ammonolysis of olefin, chosen from a group containing isobutylene or their mixture, with formation of acrylonitrile, metacrylontrile and their mixture, respectively.
EFFECT: high activity of the catalyst.
19 cl, 1 tbl, 16 ex
SUBSTANCE: described is a catalyst for oxidising methanol to formaldehyde which contains catalyst Fe2(MoO4)3/MoO3 mixtures in which the atomic ratio Mo/Fe ranges from 1.5 to 5, and a compound of cerium, molybdenum and oxygen in amount ranging from 0.1 to 10 wt % with respect to pure cerium. Described is a multilayer catalyst layer formed using the above described catalyst. Described is a method of preparing a catalyst, involving a) mixing a suspension obtained through precipitation of a Fe2(MoO4)3/MoO3 mixture in which the ratio Mo/Fe ranges from 1.5 to 5, from a solution of a soluble iron (III) salt mixed with a solution of a molybdate of an alkali metal or ammonia with an aqueous suspension obtained from reacting hot molybdenum trioxide and cerium (III) carbonate in atomic ratio Mo/Ce ranging from 1.5 to 2.1 until generation of CO2 stops, b) dilution, precipitation, filtration an washing the residue converted to a suspension after that by stirring before mixing with a suspension of the product of reacting molybdenum trioxide with cerium carbonate, c) formation of a dry mixture or paste thereof in form of granules and d) calcination thereof at temperature ranging from 450 to 600°C. A method is described for oxidising methanol using the above described catalyst.
EFFECT: increased stability of the catalyst layer.
15 cl, 2 tbl, 5 ex
SUBSTANCE: invention relates to a method of preparing a catalyst for oxidising methanol to formaldehyde and its use in formaldehyde synthesis methods. Described is a method of preparing a catalyst for oxidising methanol to formaldehyde, which contains a Fe2(MoO4)3/MoO3 mixture in which atomic ratio Mo/Fe ranges from 1.5 to 5. The method involves reacting powdered iron and molybdenum trioxide in ratio Mo/Fe ranging from 1.5 to 5 in an aqueous suspension at temperature ranging from 20 to 100°C and then optional simultaneous oxidation of the mixture with an oxidising agent in an amount equal to or greater than the amount required for oxidising iron (II) to iron (III) and for oxidising molybdenum to molybdenum (VI). Describe is the obtained catalyst and a formaldehyde synthesis method through methanol oxidation using the said catalyst.
EFFECT: simple technique.
9 cl, 2 tbl, 3 ex
SUBSTANCE: invention relates to a crust catalyst specifically designed for oxidising methanol to formaldehyde, a method of preparing the said catalyst and use of a catalyst for oxidising methanol to formaldehyde. A catalyst is described, which contains at least one coating layer on an inert, preferably essentially non-porous carrier, where the said coating layer, before removal of organic components b) and c), contains (a) oxides or precursor molybdenum and iron compounds transformed to corresponding oxides, where molar ratio Mo:Fe ranges from 1:1 to 5:1, and, if necessary, other metal or metal oxide compounds or precursor compounds transformed to corresponding oxides, (b) at least one organic binder material, preferably an aqueous dispersion of copolymers selected from vinylacetate/vinylaurate, vinylacetate/ethylene, vinylacetate/acrylate, vinylacetate/maleate, styrene/acrylate or mixtures thereof, and (c) at least one other component selected from a group consisting of SiO2 sol or its precursor, Al2O3 sol or its precursor, ZrO2 sol or its precursor, TiO2 sol or its precursor, liquid glass, MgO, cement, monomers, oligomers or polymers of silanes, alkoxysilanes, aryloxysilanes, acryloxysilanes, aminosilanes, siloxanes or silanols. Described also is a method of preparing the catalyst and its preferred use in the method with a fixed bed catalyst.
EFFECT: obtaining an active, selective and wear-resistant catalyst.
35 cl, 4 ex,1 dwg
SUBSTANCE: invention relates to the field of catalysis and can be applied as a catalyst in the process of thermolysis of heavy crude and fuel-oil residuals; the method describes the iron oxide catalysts used for thermolysis of heavy crude hydrocarbons which allows to increase the output of light fractions without application of steam and hydrogen; the above catalyst represents the microspheric magnetic product substracted from flue dust received in the process of burning of powdered brown and black coal with the fraction within the range of 0.05-0.4 mm 80-90 % consisting of the iron oxide (silicon oxide, aluminium, calcium, magnesium, natrium, kalium, manganese, sulphur make up the rest of the composition) therein the iron oxide is constituted by two iron-containing phases: 13.0- 34.5 % of the mass - ferromagnetic spinel and 35.0-63.0 % - hematite.
EFFECT: catalyst with advanced activity in the process of heavy crude hydrocarbons cracking.
1 cl, 2 tbl, 5 ex
SUBSTANCE: invention relates to a method of producing a catalyst for oxidising methanol to formaldehyde and can be used in production of formaldehyde and urea-formaldehyde resin. The method of producing a catalyst for oxidising methanol to formaldehyde involves reaction of an iron-containing component with molybdenum trioxide with subsequent moulding of granules, drying and calcination, wherein the iron-containing component used is iron oxide, and the reaction is carried out in a mill with impact-shear action and power density 10-200 W/g and weight ratio MoO3:Fe2O3=(80-40):(20-60).
EFFECT: use of the invention increases specific surface area by 51-84%, mechanical strength by 60-68%, and cuts the number of process operations twofold.
1 cl, 1 tbl, 3 ex