Method of producing catalyst of hydrodeoxygenation of aliphatic oxygen-containing compounds

FIELD: chemistry.

SUBSTANCE: method of producing a catalyst for the hydrodeoxygenation of aliphatic oxygen-containing compounds to n-alkanes containing, as an active component, nickel phosphide on the surface γ-Al2O3, includes the impregnation of the carrier granules with a nickel compound, followed by reduction of the catalyst precursor, and treatment with a phosphorus-containing compound in the liquid phase by the method of temperature-programmed reducing phosphidation, characterized in that, in preparing the catalyst, an aqueous solution of nickel citrate and citric acid molar ratio of citric acid: Ni equal to 2, the resulting sample of the nickel-containing precursor catalyst prec preliminarily reduced in a hydrogen flow at a temperature not higher than 400°C, and treatment with the phosphorus-containing compound is carried out in the liquid phase by the method of temperature-programmed phosphidation with a phosphorus-organic compound solution, preferably with a solution of triphenylphosphine in n-decane, in a stream of hydrogen at a temperature of 250-380°C for 1-4 hours.

EFFECT: high activity and selectivity of the catalyst in the hydrodeoxygenation reaction of methyl palmitate to form n-hexadecane and n-pentadecane.

2 tbl, 4 ex

 



 

Same patents:

FIELD: chemistry.

SUBSTANCE: method of producing liquid hydrocarbon mixtures is carried out via hydroconversion of lignocellulose biomass in a solvent medium in the presence of a dispersed catalyst precursor. The method includes drying the biomass; grinding the biomass; preparing a paste from the ground biomass, solvent and dispersed catalyst precursor; hydroconversion of the prepared paste; separating the obtained products in a system of separators; the method is characterised by that the solvent used is an organic solvent having viscosity of 0.5-2.5 Pa·s at 60-90°C, which contains 2-5.5 wt % sulphur and 5-25 wt % polycyclic aromatic hydrocarbons and/or derivatives thereof, and grinding of the biomass and preparation of said paste is carried out via dispersion with mechanical activation of the biomass in a solvent medium containing a catalyst precursor, wherein the prepared paste is first heated in an inert atmosphere to temperature of 330-380°C and pressure of 0.2-0.5 MPa until removal of the basic amount of oxygen in the biomass in the form of CO, CO2 and H2O, followed by hydroconversion.

EFFECT: high output of liquid products of hydroconversion of the biomass, higher conversion of the biomass and simpler process.

10 cl, 10 tbl, 2 dwg, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of processing tall oil resin. The method of processing tall oil resin, which contains sterol alcohols, and, possibly, wood alcohols of fatty acids and resin acids, the source of which is tall oil, is characterised by the fact that, at least, a part of the fatty acids and resin acids is released from sterol ethers and ethers of wood alcohols and converted into lower alkyl ethers; alkyl ethers, obtained in he said way, are extracted by evaporation from resin, then condensed, with the further hydration of the obtained condensate. The product, obtained by the claimed method and the application of the method for fuel production are also claimed.

EFFECT: application of tall oil resin, which usually represents a waste product, for obtaining fuel or a fuel component.

17 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining olefins, including a) steam cracking of an ethane-including raw material in the zone of cracking and under conditions of cracking with obtaining a flow discharged from the zone of cracking, which includes, at least, olefins and hydrogen; b) conversion of the oxygenated raw material in the zone of conversion of oxygenate to olefins in the presence of a catalyst with obtaining a flow, consisting of, at least, olefins and hydrogen, discharged from the oxygenate-to-olefins (OTO) flow; c) combination of, at least, a part of the flow, discharged from the zone of cracking and a part of the flow, discharged from the OTO zone with obtaining a combined output flow; and d) separation of hydrogen from the combined output flow, with the formation of, at least, a part of the oxygenated raw material due to the supply of hydrogen, obtained at stage d), and the raw material, containing carbon oxide and/or carbon dioxide, into the zone of oxygenates synthesis and obtaining oxygenates. The invention also relates to a combined system for the claimed method realisation.

EFFECT: claimed invention makes it possible to obtain target products by the improved combined method of ethane cracking and OTO technology.

8 cl, 1 dwg, 5 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the catalytic conversion of a renewable raw material - products of the biomass fermentation (ethanol, fusel alcohols) and their mixtures with vegetable oil into an alkane-aromatic fraction C3-C11+, which can be used for obtaining fuel components. The method of obtaining alkane and aromatic hydrocarbons from the products of the biomass processing for obtaining the hydrocarbon fuel components includes passing the products of the biomass processing through a layer of a preliminarily regenerated zeolite ZSM-based catalyst, containing Pd and Zn, in an inert atmosphere at an increased temperature. The method is characterised by the fact that as the catalyst used is the Pd-Zn/ZSM/Al2O3 catalyst of the general formula of 0.6 wt % Pd-1 Zn/Al2O3/ZSM, with the products of the biomass processing, which contain a mixture of organic fermentation products or fusel alcohols, being passed through the catalyst layer at a temperature of 280-500°C and volume rate of 0.3-6 h-1.

EFFECT: extension of the raw material base and method for obtaining alkane and aromatic hydrocarbons.

5 cl, 6 tbl, 26 ex

FIELD: chemistry.

SUBSTANCE: described is catalyst for single-stage manufacturing of components for jet and Diesel fuels from oil and fat raw material, containing platinum or palladium, fixed on the surface of porous carrier, represented by borate-containing aluminium oxide, with the following component ratio, wt %: Pt or Pd 0,10-0.50; B2O3 5-25; Al2O3 - the remaining part. Catalyst can be prepared by granulation of mixture of aluminium oxide hydrate of pseudoboehmite structure with orthoboric acid with the following drying of granules at 120°C and annealing at 550-700°C for 16 h. Granules are soaked with solutions of hexachloroplatinic acid or palladium chloride, subjected to drying at 120°C and annealing at 500°C. Method of single-stage manufacturing of components for jet and Diesel fuels with improved low-temperature properties from oil and fat raw material in presence of claimed catalyst includes passing mixture of hydrogen and oil and fat raw material through immobile layer of catalyst at temperature 380°C, pressure 4.0 MPa, mass rate of raw material supply 1 h-1 and with volume ratio hydrogen:raw material, equal 1300.

EFFECT: increased efficiency of single-stage manufacturing of components for jet and Diesel fuels with improved low-temperature properties from oil and fat raw material due to simplification of catalyst composition, method of its preparation and reduction of catalyst cost.

3 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing pyrolysis oil. A method of producing biomass-derived pyrolysis oil (38) with low metal content includes steps of: filtering a biomass-derived pyrolysis oil (12) with a high-throughput filter unit (20) having throughput of 10 l/m2/h or higher to form biomass-derived pyrolysis oil (22) with low content of solid substances; filtering the biomass-derived pyrolysis oil (22) with low content of solid substances with a fine filter (28) having a pore diameter of 50 mcm or less to form biomass-derived pyrolysis oil (30) with very low content of solid substances; and contacting the biomass-derived pyrolysis oil (30) with very low content of solid substances with an ion-exchange resin to remove metal ions and form biomass-derived pyrolysis oil (38) with low metal content. A version of the method is also disclosed.

EFFECT: total metal content is reduced to concentration of 100 ppm or less.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: method includes producing synthesis gas, converting the synthesis gas into methanol, producing a concentrate of aromatic hydrocarbons and water from the methanol in the presence of a catalyst, separating the water, blowing off hydrocarbon residues from the water, separating the formed concentrate of aromatic hydrocarbons and a hydrogen-containing gas, which is at least partially used when producing synthesis gas, to change the ratio H2:CO=1.8-2.3:1 therein. The production of aromatic hydrocarbons from methanol in the presence of a catalyst is carried out in two series-connected aromatic hydrocarbon synthesis reactors - a first low-temperature isothermic aromatic and aliphatic hydrocarbon synthesis reactor and a second high-temperature adiabatic reactor for synthesis of aromatic and aliphatic hydrocarbons from the aliphatic hydrocarbons formed in the first reactor and subsequent stabilisation in a unit for stabilising the concentrate of aromatic hydrocarbons. At least part of the hydrogen-containing gas is fed into a synthesis gas production unit and used to obtain synthesis gas using an autothermal reforming technique with a pre-reforming or non-catalytic partial oxidation unit using oxygen or oxygen-air mixtures as the oxidising agent to change the ratio according to the relationship (m.f.H2-m.f.CO2)/(m.f.CO+m.f.CO2)≥2, where m.f. is the molar fraction of a component in synthesis gas. The invention also relates to an apparatus.

EFFECT: high efficiency of producing concentrates of aromatic hydrocarbons.

12 cl, 2 dwg, 1 ex

FIELD: oil and gas industry.

SUBSTANCE: invention relates to a method for obtaining hydrocarbon products, which involves the following stages: (a) provision of synthesis gas containing hydrogen, carbon monoxide and carbon dioxide; (b) reaction of conversion of synthesis gas to an oxygenate mixture containing methanol and dimethyl ester, in presence of one or more catalysts, which simultaneously catalyse the reaction of conversion of hydrogen and carbon monoxide to oxygenates, at pressure of at least 4 MPa; (c) extraction from stage (b) of an oxygenate mixture containing quantities of methanol, dimethyl ester, carbon dioxide and water together with non-reacted synthesis gas, introduction of the whole amount of the oxygenate mixture without any additional treatment to a stage of catalytic conversion of oxygenates (d); (d) reaction of oxygenate mixture in presence of a catalyst, which is active in conversion of oxygenates to higher hydrocarbons; (e) extraction of the outlet flow from stage (d) and separation of the outlet flow into tail gas containing carbon dioxide occurring from synthesis gas and carbon dioxide formed at stage (b), liquid hydrocarbon phase containing the higher hydrocarbons obtained at stage (d) and liquid water phase where the pressure used at stages (c)-(e) is mainly the same as that used at stage (b); besides, some part of tail gas obtained at stage (e) is recirculated to stage (d), and the rest part of tail gas is discharged.

EFFECT: this method is a method in which there is no recirculation of non-reacted synthesis gas to a synthesis stage of oxygenates and without any cooling of a conversion reaction of dimethyl ester to higher hydrocarbons.

6 cl, 2 ex, 1 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: claimed invention relates to liquid fuel compositions. Invention deals with liquid fuel composition, containing, at least, one fuel component and from 0.1%(vil.) to 99.5% (vol.) of fraction of distillation of component, which contains, at least, one C4+ compound, derived from water-soluble oxygenated hydrocarbon. Method includes supply of water and water-soluble oxygenated hydrocarbon, including C1+O1+ hydrocarbon, in water liquid phase and/or vapour phase; supply of H2; carrying out catalytic reaction in liquid and/or vapour phase between oxygenated hydrocarbon and H2 in presence of deoxygenation catalyst at temperature of deoxygenation and pressure of deoxygenation to obtain oxygenate, which contains C1+O1-3 hydrocarbon in reaction flow; and carrying put catalytic reaction in liquid and/or vapour phase for oxygenate in presence of condensation catalyst at temperature of condensation and pressure of condensation to obtain C4+ compound, where C4+ compound includes representative, selected from the group, consisting of C4+ alcohol, C4+ ketone, C4+ alkane, C4+ alkene, C5+ cycloalkane, C5+ cycloalkene, aryl, condensed aryl and their mixture. Invention also relates to petrol composition, Diesel fuel composition, kerosene composition and methods of obtaining thereof.

EFFECT: improved characteristics of fuel composition, containing component, obtained from biomass.

9 cl, 19 dwg, 14 tbl, 59 ex

FIELD: chemistry.

SUBSTANCE: method includes stage of contact of pyrolysis oil, produced from biomass, with first catalyst of oxygen removal in presence of hydrogen under first, preliminarily set conditions of hydropurification with formation of first effluent stream of pyrolysis oil with low oxygen content. First catalyst of oxygen removal contains neutral catalytic carrier, nickel, cobalt and molybdenum. First catalyst of oxygen removal contains nickel in quantity from 0.1 to 1.5 wt % in terms of oxide. Version of method is also claimed.

EFFECT: extension of assortment of oxygen removal methods.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a novel method of producing a phosphorus-containing catalyst, which includes the following steps: (a) depositing a phosphorus-containing compound on a zeolite, (b) calcining the modified zeolite, (c) treating the calcined zeolite obtained at step (b) with an aqueous solution or water to remove part, particularly at least 50 wt %, preferably at least 70 wt %, especially preferably 80-95 wt %, of phosphorus-containing components and optionally performing further calcination, (d) mixing the material obtained at step (c) with binder, (e) moulding the binder-zeolite mixture obtained at step (d), and (f) calcining the moulded material obtained at step (e), where the zeolite has a silicon to aluminium ratio ranging from 50 to 250. The invention also relates to a catalyst obtained using said method and use thereof in a method of producing lower olefins from methanol, dimethyl ether and/or mixtures thereof.

EFFECT: obtained catalyst has improved stability and provides higher conversion of the raw material.

20 cl, 1 dwg, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a hydrotreatment catalyst. Described is a method of producing a hydrotreatment catalyst which involves the following steps: a) at least one step for saturating a dried and/or annealed catalyst precursor containing at least one group VIII element and/or at least one group VIB element and an amorphous support using an impregnating solution consisting of at least one phosphorus-containing compound dissolved in at least one polar solvent with relative permittivity higher than 20; b) a step for maturation of said saturated catalyst precursor obtained at step a); wherein said maturation step is carried out at atmospheric pressure, at temperature ranging from ambient temperature to 60°C for maturation period of 12 to 340 hours; c) a step for drying without a subsequent step for annealing said catalyst precursor obtained at step b), wherein the drying step c) is carried out in a drying oven at atmospheric or low pressure and at temperature 50-200°C. Described is use of the catalyst obtained using the described method to carry out hydrofining and hydroconversion of hydrocarbon material.

EFFECT: high catalyst activity.

14 cl, 8 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention refers to methylmercaptane synthesis prepared from aluminium oxide, alkali metal wolframate and at least one of ammonium salt containing sulphur or nitrogen with catalyst pH in water suspension 10% being 5.0 - 9.7. The method of methylmercaptanes preparation from methanol and hydrogen sulfide using said catalyst is described also.

EFFECT: enhancing of catalyst activity and selectivity particularly at low hydrogen sulfide/methanol ratios.

6 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst of selective hydrodesulphurisation of olefin-containing hydrocarbon raw material. Said catalyst consists of compounds of metals Co or Ni, Mo and Na or K, applied on carrier. Claimed catalyst contains bimetal complex compound of metals Co or Ni, Mo and Na or K, carboxylic acid, containing, at least, one carboxyl group and 1-20 carbon atoms; it has specific surface 180-350 m2/g, volume of pores 0.3-1.1 cm3/g, average pore diameter 5.5-11.0 nm. Invention relates to method of preparing claimed catalyst, as well as to process of selective hydrodesulphurisation with its application.

EFFECT: claimed catalyst makes it possible to obtain petrol with ultralow content of sulphur and preservation of value of its octane number at initial level.

14 cl, 3 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a catalyst for deep hydrofining of oil fractions. The present method includes impregnating an aluminium oxide support with a solution of compounds of metals of groups VIII and VI with pH of the impregnating solution of 1.5-5.0, vacuum treatment of the support before contact thereof with the impregnating solution, using impregnation at high temperature. The starting compounds used for preparing the impregnating solution are sodium salts Mo and one of modifiers X selected from the group (B, P, Si, V, Zn, Ge, Sn), which are soluble in water in molar ratio Mo/X=12/1, after which the solution is passed through a column with a cationite in H+ form and Co or Ni acetate is added to said solution.

EFFECT: disclosed method enables to obtain catalysts having high activity and selectivity with respect to hydrodesulfurisation, hydrodenitrogenation and hydrogenation of olefins and aromatic compounds.

2 cl, 5 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: method includes preparation of carrier by thermal processing at 500°C, application of alcohol film-generating solution by method of stretching at rate 100 mm/min, drying at 60°C for 1 h and annealing at 750°C for 4 h. Film-generating solution is applied on fibreglass carrier by method of soaking with further drying at 60°C for 1 h and annealing at 600-750°C for 1 h. Catalyst, which is obtained in form of cloth, is cut at output in accordance with reactor shape and packed in layers at angle of 20-30°, with formation of honeycomb structure, with the following component ratio in film-generating solution, wt %: Ce(NO3)3·6H2O - from 6.0 to 12.0, SnCl4·5H2O - from 16.6 to 22.3, C6H4OHCOOH - from 9.1 to 10.0, 96%-by weight C2H5OH - the remaining part.

EFFECT: method makes it possible to obtain catalysts, characterised by high permeability of gas mixture flow.

2 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining a catalyst for the selective catalytic reduction of NOx in a flue gas, containing an alkali metal, with the application of ammonia as the reducing agent, with the catalyst containing a surface with catalytically active centres of Bronsted or Lewis acids, with the surface being, at least, partially covered with a coating, containing, at least, one metal oxide, and the said method includes the supply of a carrier, impregnation of the carrier with the first water solution, containing a vanadium component, drying and calcination of the impregnated carrier, covering the impregnated carrier with the second water suspension, containing, at least, one oxide of a basic metal, representing MgO, and drying and calcination of the coated carrier for the second time.

EFFECT: obtaining the catalyst with an improved resistance to poisoning with alkali metals.

7 cl, 6 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the field of chemistry and chemical technology, and namely, to processes of processing a gaseous hydrocarbon raw material and obtaining technical hydrogen for chemical, metallurgical, automobile, aircraft and other fields of industry, scientific research, precision engineering, instrument-making, synthesis of materials for microelectronics, initial raw material for hydrogen power engineering and power for fuel cells, etc. by the method of steam catalytic conversion of hydrocarbons (methane). Claimed is a catalyst of the steam conversion of hydrocarbons of the following composition (vol %): nickel oxide - 10-70; zircon oxide - 30-90; to 10 vol % powder of carbonyl nickel and/or to 10 vol % of nichrome powder of grade PC20H80. Claimed is a method of obtaining the catalyst, in the presence of which, fractions 30-100 mcm are separated from nickel NiO oxides powder and zircon Zr2O, respectively, mixed in a specified volume ratio, powder of carbonyl nickel and/or nichrome powder of grade PC20H80 is added, then subjected to conglomeration, with the realisation of plasma spraying of the obtained mixture on a preliminarily prepared surface, grounded with metal nickel and/or nichrome powder.

EFFECT: increase of the efficiency and reliability of the catalyst and the increase of the process selectivity.

2 cl, 5 ex

FIELD: engines and pumps.

SUBSTANCE: invention relates to a manufacturing method of a honeycomb ceramic unit for a catalytic neutraliser of exhaust gases, according to which to the ceramic unit from the main material there applied is a binding layer containing sodium silicate Na2O(SiO2)n or potassium silicate K2O(SiO2)n, or their mixture, above which there formed is at least one substrate layer for application of a catalyst, which contains a nanodispersed oxide of aluminium hydroxide (boehmite); for that purpose, a suspension layer is applied onto the second workpiece, which contains nanodispersed oxide of aluminium hydroxide; the workpiece with the applied suspension layer is dried; after that, the workpiece of the honeycomb ceramic unit with the applied substrate material is roasted, and therefore, a honeycomb ceramic unit for a catalytic neutraliser of exhaust gases is obtained. In addition, an application method of substrate onto the honeycomb ceramic unit for the catalytic neutraliser of exhaust gases, which applies this technology, is proposed.

EFFECT: improvement of passage of a gas flow through pores and channels of a substrate; increase and optimisation of a catalytic neutralisation process of substances in exhaust gases of diesel engines.

17 cl, 24 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention refers to a catalyst for hydrocarbon material hydroprocessing. The presented catalyst comprises an amorphous alumina-based carrier, phosphorus, at least one dialkyl(C1-C4)succinate, acetic acid and a functional group with a hydrogenation/dehydrogenation ability containing at least one group VIB element and at least one group VIII element specified in cobalt and/or nickel. The Raman spectrum of the above catalyst has characteristic bands of at least one Keggin heteropolyanionwithin the range of 990 and/or 974 cm-1, characteristic bands of said succinate and a principal characteristic band of acetic acid within 896 cm-1. The invention also refers to a method for producing this catalyst and to the catalyst produced by this method, as well as to a method for hydrocarbon material hydroprocessing in the presence of this catalyst.

EFFECT: presented catalyst possesses overactivity shown in hydroprocessing by the synergetic action of a combination of acetic acid and dimethylsuccinate.

24 cl, 2 dwg, 5 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: problem is solved by using graphite oxide functionalised by ethylene amide as a carrier. The described method for preparing a palladium-containing hydrogenation catalyst by coating a carbon nanomaterial with a bivalent palladium salt (PdCl2) followed by reducing to zero-valent palladium by sodium borane in the hydrogen medium, differs by the fact that the used carbon nanomaterial is graphite oxide modified by ethylene amide and prepared by boiling a graphite oxide suspension in butanol-1 in the presence of excessive ethylene amine. The palladium content in the catalyst makes 4.8-5 wt %. The catalyst is stable in the standard environment and keeps being active at long air storage, as well as maintains its activity after repeated hydrogenation cycles involving no regeneration.

EFFECT: creating the palladium-containing hydrogenation catalyst, wherein the palladium particles have a nanometre size and are uniformly distributed over the carrier surface.

2 cl, 3 ex

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