Methods of regenerating aromatization catalysts

FIELD: chemistry.

SUBSTANCE: invention discloses and describes methods for treating or regenerating spent catalysts containing a transition metal and a catalyst substrate, reforming methods, and a regenerated catalyst produced by the said methods. The method for treating the spent catalyst comprises: (1) contacting the spent catalyst with a halogen-containing stream containing chlorine and fluorine to produce a halogenated spent catalyst. The halogen-containing stream contains less than 100 ppm weight of the oxygen-containing compounds; (2) contacting the halogenated spent catalyst with a purge stream containing essentially inert gas; and (3) contacting the halogenated spent catalyst with a coke-removal gas stream containing oxygen; where the stream of coke oven gas contains less than 50 ppm weight of the halogenated compounds after step (2). Another method of treating the catalyst comprises: (i) bringing the spent catalyst into contact with a halogen-containing stream containing chlorine and fluorine to produce a halogenated spent catalyst; and (ii) bringing the halogenated spent catalyst into contact with a coke oven gas stream containing oxygen after step (i). In the halogenation step, fluorine and chlorine can be used together, or fluorine and chlorine can be used sequentially. The reforming method comprises: (a) bringing the hydrocarbon feed into contact with the aromatization catalyst under reforming conditions in the reactor system to produce an aromatic product; (b) carrying out step (a) for a period of time sufficient to form a spent aromatization catalyst; (c) bringing the spent aromatization catalyst into contact with a halogen-containing stream containing chlorine and fluorine to produce a halogenated spent catalyst; and (d) bringing the halogenated spent catalyst into contact with a coke oven gas stream containing oxygen.

EFFECT: spent catalyst, which was initially halogenated, has a significantly lower start-up temperature than the spent catalyst, which was first subjected to the coke removal, demonstrating the unexpected advantage of carrying out the halogenation step prior to the carbon annealing step, the advantage is maintained, when halogens are added sequentially prior to the coke removal step.

39 cl, 4 tbl, 63 ex

 



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a fluidised-bed reactor and a method of catalytic hydrogenation in the reactor. The fluidised-bed reactor comprises a reactor shell, vertical to the ground, a phase separator located within the top part of the shell, an internal circulation zone, located under the phase separator. The internal circulation zone comprises a cylinder, a tapered diffusion section and a guide support. Both the cylinder and the tapered diffusion section at the bottom of the cylinder are located inside the reactor shell, the guide support is fitted on the shell inner wall at the bottom of the tapered diffusion section. The guide support is an annular protrusion of the reactor inner wall.

EFFECT: invention provides effective hydrogenation resulting in a high quality product, and stable operation of the reactor.

26 cl, 2 dwg, 4 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining engine fuel in interval of petrol boiling by benzole alkylation. Invention deals with method of obtaining hydrocarbon product in interval of petrol boiling, which has concentration of benzole not more than 1 vol.% and regulated temperature of evaporation, from raw material, which consists of reforming product, with concentration of benzole at least 20 wt %, which includes reforming product alkylation in reactor of alkylation in presence of zeolite catalyst MWW at least in two immobile catalytic layers in mode of single passing in liquid phase by alkylation agent.

EFFECT: high level of benzole and olefin conversion.

10 cl, 10 dwg, 15 tbl, 14 ex

FIELD: oil and gas industry.

SUBSTANCE: as an additive to increase the processing depth of hydrocarbon-containing raw materials, in thermocatalytic processes there used is organic salt having the following formula: M(OOC-R)n, or M(SOC-R)n, or M(SSC-R)n, where R means alkyl, aryl, isoalkyl, tert-alkyl, alkylaryl, possibly containing hydroxylic, keto-, amino-, carboxylic, thiocarbamic groups, n 1-3, and M means transition metal from the elements of the Mendeleyev's Classification Table. Also, invention refers to the method for increasing the processing depth of hydrocarbon-containing raw materials, in which the above additive is used.

EFFECT: use of the described invention allows increasing the processing depth of hydrocarbon-containing raw materials in thermocatalytic processes.

14 cl, 8 ex, 12 tbl

FIELD: oil and gas industry.

SUBSTANCE: catalytic reforming system described below includes the following: raw material stream including naphtha and at least one compound containing manganese, which is chosen from the group consisting of manganese cyclopentadienyl tricarbonyl, manganese methylcyclopentadienyl tricarbonyl, manganese dimethylcyclopentadienyl tricarbonyl, manganese trimethylcyclopentadienyl tricarbonyl, manganese tetramethylcyclopentadienyl tricarbonyl, manganese pentamethylcyclopentadienyl tricarbonyl, manganese ethylcyclopentadienyl tricarbonyl, manganese diethylcyclopentadienyl tricarbonyl, manganese propylcyclopentadienyl tricarbonyl, manganese isopropylcyclopentadienyl tricarbonyl, manganese tert- butylcyclopentadienyl tricarbonyl, manganese octylcyclopentadienyl tricarbonyl, manganese dodecyclopentadienyl tricarbonyl, manganese ethylmethylcyclopentadienyl tricarbonyl and manganese indenyl tricarbonyl; and catalyst; at that, catalyst of reforming plant includes the following: substrate; precious metal on substrate; and deposit of free particles of manganese on catalyst, which are formed during decomposition at least of one manganese containing compound which is described above. Method for increasing octane number of mixture of reforming product produced with catalytic reforming plant at oil refinery having the stream of raw product of reforming plant is described; the above method includes the following: addition of catalyst to raw product stream of reforming plant; the above catalyst contains oxidised manganese; as a result, octane number of mixture of the produced reforming product increases relative to octane number of mixture of produced reforming product obtained at oil refinery without any addition of catalyst containing the oxidised manganese; at that, oxidised manganese catalyst is obtained from group of manganese tricarbonyls which are specified above.

EFFECT: increasing catalyst service life or increasing octane number of reforming product stream.

19 cl

The invention relates to systems for producing high-octane gasoline low-octane reforming of gasoline fractions

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of regenerating a catalyst, according to which content of sulphur in a ruthenium- or ruthenium compound-containing catalyst, which is contaminated with sulphur in form of sulphur compounds, is reduced by directed treatment with a gas stream containing a hydrogen halide, particularly hydrogen chloride, which is carried out in non-oxidative conditions, optionally at high temperature. Described is a method for catalysed gas-phase oxidation of hydrogen chloride with oxygen based on ruthenium or ruthenium compounds, wherein after reducing catalytic activity to a given value, the catalyst is regenerated according to the method described above.

EFFECT: content of sulphur in the catalyst can be reduced such that activity of the treated catalyst increases to a level which is typical for a similar ruthenium- or ruthenium compound-containing catalyst which is not deactivated with sulphur in form of sulphur compounds.

12 cl, 7 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of activating a catalyst for producing fluorine-containing hydrocarbons via gas-phase hydrofluorination of halohydrocarbons. The catalyst contains chromium (III) oxide and an aluminium (III) compound, whose content ranges from 2 to 15 wt % in terms of Al2O3, and additionally contains a metal compound, where the metal Me is selected from either iron or nickel or cobalt or zinc or copper or magnesium any mixture in amount of 0.1-1.5 wt % in terms of oxides. The activation process is carried in four steps: a) drying the catalyst in a current of nitrogen at temperature 100-200°C and atmospheric pressure; b) treating the catalyst with difluorochloromethane (R-22) at temperature 300-370°C and atmospheric pressure; c) treating the catalyst with a mixture of hydrogen fluoride and nitrogen at temperature 340-370°C and atmospheric pressure, while gradually increasing hydrogen fluoride concentration in the mixture with nitrogen to 100 mol %; d) treating the catalyst with hydrogen fluoride at temperature 340-370° and pressure of up to 0.4 MPa.

EFFECT: cutting overall duration of activation, avoiding overheating in the catalyst grain, preserving catalyst activity and high efficiency of the process of producing fluorine-containing hydrocarbons.

1 cl, 6 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: method includes leaching the obtained cinder with a chloride solution, which contains an oxidant or a mixture of oxidants, to extract platinum and/or palladium from the leaching solution. Oxidising roasting of the catalyst is carried out at 500-800°C. Leaching is carried out with saturated aluminium chloride solution in an apparatus with a fixed bed of the product being leached, followed by extraction of platinum and/or palladium from the leaching solution by sorption on an anion-exchange resin.

EFFECT: method improves effectiveness of treating deactivated catalysts and simplifies the process scheme.

6 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for manufacturing a regenerated Fischer-Tropsch synthesis catalyst by regenerating a used catalyst which was previously used in a Fischer-Tropsch synthesis reaction. A method comprises a steaming step of bringing the spent catalyst into contact with a mixed gas comprising 1 to 30% by volume of steam and an inert gas at a pressure of atmospheric pressure to 5 MPa and a temperature of 150 to 350°C. The above spent catalyst being a spent catalyst in which cobalt and/or ruthenium is supported on a carrier comprising silica with an average pore diameter measured by a nitrogen adsorption method of 4 to 25 nm, and of which activity represented by an initial carbon monoxide conversion is 40 to 95%, based on the activity of a corresponding unused catalyst. The invention also relates to a method for producing hydrocarbons using a regenerated FT synthesis catalyst produced by the method.

EFFECT: regenerated FT synthesis catalysts having high activity and high chain propagation probability can be obtained.

5 cl, 1 tbl, 14 ex

FIELD: metallurgy.

SUBSTANCE: method includes catalyst dilution in chlorhydric acid with palladium chloride and other metals solutions obtainment. Then three-staged treatment of solutions by sodium hydroxide with fibrillated cellulose fibres available in solution as sorbent is performed, composite materials being obtained at each stage consisting of cellulose fibres with metal insoluble compounds particles immobilised by them, at each stage composite materials are extracted by pressure flotation method.

EFFECT: simplifying process, increasing degree of palladium regeneration, utilisation of copper and aluminium and process performance in continuous mode.

5 cl, 1 dwg, 1 ex

FIELD: metallurgy.

SUBSTANCE: method involves roasting of a catalyst, leaching of a roasted product in acid medium and introduction to the obtained pulp of reagents to improve filtration. Then, non-soluble residue is separated from the solution by filtration and metals of platinum group and rhenium are extracted from the solution. Prior to filtration the pulp is treated with water solution of flocculant of cationic type based on polyacrylamide. The obtained reaction mixture is exposed without mixing till solid and liquid phases are separated. Then, clarified part of the solution is separated by decantation and paper pulp in the form of paper wastes in the quantity of 10-20 kg/m3 of the pulp is added to thickened pulp and mixed, and filtration is performed.

EFFECT: improving efficiency of separation of non-soluble residue from the solution; reducing costs for filtration materials.

1 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of regenerating a catalyst, according to which content of sulphur in a ruthenium- or ruthenium compound-containing catalyst, which is contaminated with sulphur in form of sulphur compounds, is reduced by directed treatment with a gas stream containing a hydrogen halide, particularly hydrogen chloride, which is carried out in non-oxidative conditions, optionally at high temperature. Described is a method for catalysed gas-phase oxidation of hydrogen chloride with oxygen based on ruthenium or ruthenium compounds, wherein after reducing catalytic activity to a given value, the catalyst is regenerated according to the method described above.

EFFECT: content of sulphur in the catalyst can be reduced such that activity of the treated catalyst increases to a level which is typical for a similar ruthenium- or ruthenium compound-containing catalyst which is not deactivated with sulphur in form of sulphur compounds.

12 cl, 7 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: described is purifying from disperse particles material, used for filter-catalyst for purification from disperse particles, and filter-catalyst is located on the way of flow of exhaust gases of internal combustion engine, catching disperse particles in exhaust gases, which are formed in internal combustion engine, and burning precipitated disperse particles in order to be regenerated, and purifying from disperse particles material includes: oxide, containing cerium (Ce), possessing ability to accumulate-release oxygen; and at least one metal (Me), selected from group, consisting of zirconium (zr), yttrium (Y), lanthanum (La), praseodymium (Pr), strontium (Sr), nioubium (Nb) and neodymium (Nd), and ratio of content of (Ce:Me) cerium to metal constitutes from 6:4 to 9:1 in units of atomic ratio, and degree of crystallinity (CR), represented by the following formula (1), lies within the range 36-60%: Degree of crystallinity (CR)=I/I0× 100(%) (1), where I represents intensity of X-ray diffraction peak with respect to plane (111) of phase CeO2 in purifying from disperse particles material, and I0 stands for intensity of X-ray diffraction peak with respect to plane (111) of phase CeO2 after roasting material, which purifies from disperse particles, in the air at 1000°C. Described is filter-catalyst for purification from disperse particles, which is located on the way of flow of exhaust gases of internal combustion engine, catching disperse particles in exhaust gases, which are formed in internal combustion engine, and burning precipitated disperse particles in order to be regenerated, and filter-catalyst includes: filter-carrier, made from porous ceramics with continuous small pores; and layer of catalyst, formed on the wall of filter-carrier, and catalyst layer contains: 25-100 g/l of mixture of described above purifying from disperse particles material and noble metal; and 0.25-1.0 g/l of noble metal, counted per unit of volume of filter-carrier. Described is method of regeneration of described above filter-catalyst, including control of internal temperature of filter-catalyst at the level from 350°C to 800°C, thus ensuring burning and removal of disperse particles, precipitated on filter-catalyst.

EFFECT: obtaining efficient material, purifying from disperse particles.

10 cl, 4 tbl, 7 dwg, 24 ex

FIELD: process engineering.

SUBSTANCE: invention relates to production of automotive catalysts, particularly, to their recovery. Method or recovery comprises thermal decomposition of pyrocarbon, dissolution of platinoids by the mix of hydrochloric acid and nitric acid, or 30%- hydrogen peroxide in closed cycle. Note here that dissolution process is analysed for completeness of platinoids extraction while excess nitric acid and hydrogen peroxide are removed by reducing agents. To extract platinoids, acid solution is subjected to ionic flotation extraction by cationic surfactants. Then, extract with platinoid precursors is separated from acid solution containing cerium and aluminium ions to evaporate extractant. Platinoid precursors are dissolved in water to produce micellar solution, added is hydrazine hydrate to reduce platinoids in alkaline medium to metal nanoparticles on mixing by ultrasound. Dispersion is centrifuged to drain aqueous solution and rinse centrate by alcohol to proceed with centrifugation to obtain nanopowder of platinoids. Acid solution containing ions of cerium and aluminium is neutralised by potassium hydroxide to pH=8-9. Potash soap of higher carbonic acids is added to separate cerium and aluminium soaps. The latter are dissolved in micellar aqueous solution of sodium dodecylsulphate to make the mix of cerium and aluminium hydroxides and centrifuge obtained dispersion. Precipitate of cerium and aluminium hydroxides are rinsed by water to be centrifuged again so that precipitate is separated and air dried. Then, said precipitate is calcined at 400°C to obtain nanopowders CeO2 and γ-Al2O3 and CeO2.

EFFECT: new catalysts produced with no extra treatment.

5 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of regenerating a catalyst layer and a method of producing acrolein and/or acrylic acid via heterogeneously catalysed partial gas-phase oxidation of propylene. The method of regenerating a catalyst layer which is deactivated during heterogeneously catalysed partial dehydrogenation of a hydrocarbon involves passing a regenerating gas through a layer of deactivated catalyst for a period of time t, said gas being at high temperature and containing molecular oxygen and an inert gas but not containing a hydrocarbon, under the condition that during the regeneration process total content GA of carbon oxides in the regenerating gas passed through the catalyst layer at the outlet of the catalyst layer within a period of time t at least periodically exceeds total content GE of carbon oxides in the regenerating gas passed through the catalyst layer at the inlet of the catalyst layer, wherein the corresponding content values are expressed as a percentage of the volume (vol. %) of the regenerating gas and wherein the difference ΔG=GA-GE before the end of the regeneration process passes through a maximum ΔGmax, where: a) 0.2 vol. % ≤ ΔGmax≤ to 5 vol. %, and b) content of molecular oxygen in the regenerating gas to be passed through the catalyst layer expressed in vol. % of the regenerating gas, for a period of time t before the end of the regeneration process, is increased at least thrice, wherein the increase in content of molecular oxygen each time is at least 2 vol. %. In the method of producing acrolein and/or acrylic acid, the catalyst layer is regenerated using the disclosed regeneration method from time to time.

EFFECT: susceptibility of the regenerated catalyst layer to deactivation is not different from susceptibility of a freshly loaded catalyst to deactivation.

22 cl, 3 tbl, 4 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for cleaning exhaust gases, a method of regenerating such a catalyst, as well as a device and a method of cleaning exhaust gases using the said catalyst. The invention describes a catalyst for cleaning exhaust gases where a noble metal is attached to a metal oxide support. In an oxidative atmosphere, the noble metal on the surface of the support is in a high oxidation state and the noble metal is bonded to the cation of the support though an oxygen atom on the surface of the support with formation of a surface oxide layer. In a reductive atmosphere, the noble metal on the surface of the support is metallic state and the amount of noble metal open on the surface of the support, measured through CO chemisorption, is equal to or greater than 10 at % of the total amount of noble metal attached to the support. Described is a method of regenerating a catalyst for cleaning exhaust gases in which the above described catalyst for cleaning exhaust gases undergoes oxidative treatment by heating in an oxidative atmosphere which contains oxygen, and reduction treatment. Described also are devices for cleaning exhaust gases (versions) and a method of cleaning exhaust gases, involving cleaning exhaust gases by bringing the exhaust gases into contact with the above described catalyst.

EFFECT: prevention of reduction of catalyst activity.

18 cl, 11 tbl, 46 ex, 10 dwg

FIELD: metallurgy.

SUBSTANCE: invention refers to particles of metal oxide carrier of catalyst, method of such particle obtainment, waste gas treatment catalyst including metal oxide catalyst, and method of waste gas treatment catalyst recovery. Invention describes particle of metal oxide catalyst carrier, consisting of central part and external shell part, where both central and external shell parts include first metal oxide and second metal oxide, central part and external shell part differ in composition, molar fraction of first metal oxide is higher in central part than in external shell part, molar fraction of second metal oxide is higher in external shell part than in central part, and first metal oxide is aluminium or zirconium oxide while second metal oxide is selected out of group including neodymium, praseodymium, lanthanum, scandium and yttrium oxides. Invention describes waste gas treatment catalyst including the claimed particle of metal oxide carrier and platinum applied onto the particle of metal oxide catalyst carrier. Invention describes method of waste gas treatment catalyst recovery involving waste gas treatment catalyst heating at 500°C or higher in oxidation medium including oxygen. Also invention describes method of obtaining particle of metal oxide catalyst carrier, consisting of central part and external shell part, where both parts include first metal oxide and second metal oxide, central part and external shell part differ in composition. Method involves obtainment of material solution including at least colloid particles of first metal oxide and metal salts of second metal oxide, where first metal oxide is aluminium or zirconium oxide, second metal oxide is selected out of group including neodymium, praseodymium, lanthanum, scandium and yttrium oxides; achievement of solution pH close to isoelectric point of colloid particles of first metal oxide so as to coagulate colloid particles of the first metal oxide; solution pH increase so as to cause precipitation of colloid particles of the second metal oxide from metal salts and coagulate colloid particles of the second metal oxide around coagulated colloid particles of the first metal oxide, where isoelectric point of colloid particles of the second metal oxide is higher than isoelectric point of colloid particles of the first metal oxide; and coagulated product drying and calcination.

EFFECT: increased specific area of waste gas treatment catalyst surface, increased degree of platinum particle recovery.

10 cl, 19 ex, 2 tbl, 3 dwg

FIELD: noble metal hydrometallurgy.

SUBSTANCE: invention relates to method for acid leaching of platinum method from secondary raw materials, in particular from ceramic support coated with platinum metal film. Target metals are leached with mixture of hydrochloric acid and alkali hypochlorite at mass ratio of OCl-/HCL = 0.22-0.25 and redox potential of 1350-1420 mV.

EFFECT: decreased leaching temperature, reduced cost, improved platinum metal yield.

2 ex

FIELD: separation of palladium from waste mangani-palladium catalyst and cleaning of palladium.

SUBSTANCE: palladium-containing concentrate is treated with aqua regia solution and palladium is deposited in form of chloropalladate by means of treatment with aqua regia solution with solid ammonium chloride, pulp thus obtained is settled, cooled and filtered; sediment is treated with saturated hydrochloric acid solution of ammonium chloride. Then sediment thus treated is dissolved in water and solution is filtered and neutralized; pallarium is restored to metal by means of hydrochloric acid hydrazine at pH≥2 or formic acid solution at pH≥6; solution is filtered and metallic palladium is washed and dried at 90-100°C. Prior to treatment, mangani-palladium catalyst with aqua regia, it is dissolved in concentrated hydrochloric acid; solution is neutralized by asmmonia to pH=6-7 and treated with formic acid at flow rate no less than 1 l of HCOOH per kg of mangani-palladium catalyst; then mangani-palladium concentrate is filtered, washed and dried at 90-100ºC.

EFFECT: enhanced purity of metallic palladium at minimum losses of catalyst at all stages of chemical treatment.

4 ex

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