The method of obtaining romagnuolo catalyst for gas-phase fluorination of kalogeropoulou

 

(57) Abstract:



 

Same patents:

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to production of olefin or diolefin hydrocarbons via dehydrogenation of corresponding paraffinic C3-C5-hydrocarbons carried out in presence of catalyst comprising chromium oxide and alkali metal deposited on composite material including alumina and aluminum wherein percentage of pores larger than 0.1 μm is 10.0-88.5% based on the total volume of open pores equal to 0.10-0.88 cm3/g. Preparation of catalyst involves treatment of carrier with chromium compound solution and solution of modifying metal, preferably sodium or sodium and cerium. Carrier is prepared by from product resulting from thermochemical activation of amorphous hydrargillite depicted by formula Al2O3·nH2O, where 0.25<n<2.0, added to homogenous mass in amount 1.0 to 99.0% using, as additional material, powdered aluminum metal, which is partly oxidized in hydrothermal treatment and calcination stages. Hydrocarbon dehydrogenation process in presence of the above-defined catalyst is also described.

EFFECT: increased activity and selectivity of catalyst.

3 cl, 2 dwg, 4 tbl, 7 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention concerns catalysts for dehydrogenation of C2-C5-alkanes into corresponding olefin hydrocarbons. Alumina-supported catalyst of invention contains 10-20% chromium oxide, 1-2% alkali metal compound, 0.5-2% zirconium oxide, and 0.03-2% promoter oxide selected from zinc, copper, and iron. Precursor of alumina support is aluminum oxide hydrate of formula Al2O3·nH2O, where n varies from 0.3 to 1.5.

EFFECT: increased mechanical strength and stability in paraffin dehydrogenation process.

9 cl, 1 dwg, 3 tbl, 7 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention relates to methods for preparing carbon monoxide-conversion catalysts used in production of hydrogen, nitrogen-hydrogen mixture, and other hydrogen-containing gases. According to first option, active catalyst component, i.e. iron compound, is precipitated from solution with precipitation reagent, whereupon precipitate is separated from mother liquor and washed to form catalyst mass, which is molded and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. According to second option, iron compound is first mixed with promoting additives and cations of promoting additives are precipitated jointly with iron cations, resulting precipitate is separated from mother liquor, washed and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. As iron compound in the first and second options, ferrous and ferric sulfates and, as precipitation reagent, carbonate salts or corresponding hydroxides are utilized. Promoting additives are selected from Cu, Mn, and Al or, in the second option, their mixture.

EFFECT: reduced content of sulfur in finished catalyst at the same catalyst activity.

3 cl, 1 tbl, 12 ex

FIELD: technical chemistry; catalyst carriers for various heterogeneous processes in chemical industry.

SUBSTANCE: proposed carrier has metal base made from chromium and aluminum alloy and/or metallic chromium and coat made from chromium of aluminum oxides or oxides of chromium, aluminum, rare-earth elements or mixture of them. Method of preparation of carrier includes forming of metal powder containing aluminum and other powder-like components and calcination of carrier at solid phase sintering point; used as additional component of metal powder is powder-like chromium; mixture thus obtained is subjected to mechanical activation and is placed in mold accessible for water vapor, after which it is subjected to hydro-thermal treatment and molded product is withdrawn from mold, dried and calcined at respective temperature; then additional layer of aluminum and rare-earth elements oxides or mixture of solutions and suspensions is applied on calcined product followed by drying and calcination.

EFFECT: increased specific surface; enhanced heat resistance of carrier.

8 cl, 1 tbl, 5 ex

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention describes a catalyst for dehydrogenation of (C2-C5)-hydrocarbons that comprises aluminum, chrome oxides, compound of modifying metal, alkaline and/or alkaline-earth metal. Catalyst comprises additionally silicon and/or boron compounds and as a modifying agent the proposed catalyst comprises at least one compound chosen from the following group: zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin. The catalyst is formed in the process of thermal treatment of aluminum compound of the formula Al2O3. n H2O wherein n = 0.3-1.5 and in common with compounds of abovementioned elements and shows the following composition, wt.-% (as measure for oxide): chrome oxide as measured for Cr2O3, 12-23; compound of a modifying metal from the group: Zr, Ti, Ga, Co, Sn, Mo and Mn, 0.1-1.5; silicon and/or boron compound, 0.1-10.0; alkaline and/or alkaline-earth metal compound, 0.5-3.5, and aluminum oxide, the balance. Catalyst shows the specific surface value 50-150 m2/g, the pore volume value 0.15-0.4 cm3/g and particles size 40-200 mcm. Also, invention describes a method for preparing this catalyst. Invention provides preparing the catalyst showing the enhanced strength and catalytic activity.

EFFECT: improved and valuable properties of catalyst.

12 cl, 2 tbl

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to a method of preparing catalysts for dehydrogenation of paraffin hydrocarbons into corresponding olefin hydrocarbons. Method comprises impregnating thermochemically activated hydroargillite with chromium. alkali metal, titanium, and hafnium compound solutions, drying, and calcination at 700-800°C. Catalyst is molded during thermoactivation of hydrated thermochemically activated hydroargillite together with chromium, zirconium, alkali metal compounds and titanium, zirconium, and hafnium oxides. Catalyst contains (on conversion to oxides): 10-20% chromium (as Cr2O3), 0.5-3,5% alkali metal, and 0.05-5% sum of zirconium, hafnium, and titanium oxides, with balancing amount of alumina obtained from thermochemically activated hydroargillite as precursor, provided that oxide ratio Ti/Zr/Hf is (0.001-0.05):1:(0.01-0.3).

EFFECT: increased mechanical strength of catalyst, catalytic activity, selectivity, stability, reduced coking, and reduced yield of catalyst and yield of olefins.

5 cl, 1 tbl, 6 ex

FIELD: petrochemical processes catalysts.

SUBSTANCE: invention relates to production of catalysts used in hydrocarbon feed processing and can be, in particular, used in the hydrodealkylation of toluene and benzene-toluene-xylene fraction isolated from pyrocondensate resulting from hydrocarbon pyrolysis. Alumina-supported catalyst contains 16-20% chromium oxide, 0.3-1.5% sodium oxide, 0.5-3.0 boron oxide. Preparation of alumina comprises adding fine aluminum hydroxide powder to aluminum hydroxide in the form of "wet cake" in amount 15-50% of the weight of "wet cake" in presence of organic acid. As a result, process of hydrodealkylation of real feed material (industrial benzene-toluene-xylene fraction) is stabilized under conditions of temperature gradient throughout the catalyst bed, while high catalytic activity and selectivity are preserved. Simultaneously, coking resistance of the catalyst is enhanced, porous structure thereof shows improvement (increased percentage of wide pores), mechanical strength is increased, and specific surface optimized.

EFFECT: enlarged assortment of high-efficiency hydrodealkylation catalysts.

2 dwg, 4 tbl, 6 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to methods of preparing alumino-chromium catalysts and their compositions for dehydrogenation of С2-С5-paraffin hydrocarbons into corresponding olefins. A method for preparing above-said alumino-chromium catalyst and catalyst prepared by this method are disclosed. Method comprises providing saturated solution of water-soluble chromium and aluminum salts, heating solution to 80-90°C, precipitating alumino-chromium hydroxide by passing ammonia gas through saturated solution until pH 9.5-10 is attained, drying resulting slurry of hydroxides at 100-120°C and subsequent calcination of dry powder for 5 h at temperature not higher than 550°C. Starting components are taken in such amounts as to ensure, after calcination, contents of chromium oxide 10-30% (the rest: aluminum oxide). Chromium oxide is composed of chromium(VI) and chromium(III) oxides, wherein proportion of chromium(VI) oxide in chromium oxide mixture is at least 20 wt %.

EFFECT: simplified catalyst preparation procedure and increased activity and selectivity of catalyst in paraffin hydrocarbon dehydrogenation process.

4 cl, 2 ex

FIELD: isomerization and disproportionation catalysts.

SUBSTANCE: invention relates to crystalline α-chromium oxide, chromium-containing catalytic compositions, methods for preparation thereof, and to a process of fluorine distribution in hydrocarbon and/or halogenated hydrocarbon in presence of indicated catalytic compositions. Claimed crystalline α-chromium oxide, wherein about 0.05 to about 6 atomic % chromium in the lattice of α-chromium oxide is substituted by trivalent cobalt (Co+3) atoms is via coprecipitation of solid substance by introducing ammonium hydroxide, this method being supplemented by introducing an excess of ammonium nitrate into precipitated mixture before dehydration step and calcination step at 375 to 1000°C in presence of oxygen. Chromium-containing catalytic compositions containing crystalline cobalt-substituted α-chromium oxide as chromium-containing component optionally treated with fluorination agent are also claimed. Composition preparation procedure comprises: (a) coprecipitation of solid substance by introducing ammonium hydroxide into aqueous solution of soluble cobalt salt and soluble trivalent chromium salt, wherein solution contains at least three moles nitrate per mole chromium and has concentration of cobalt from about 0.05 to about 6 mol % based on total content of cobalt and chromium in solution, followed by introducing into solution at least three moles ammonium per mole chromium; (b) collecting coprecipitated solid substance obtained in step (a); (c) drying collected solid substance; and (d) calcination of dried solid substance at 375 to 1000°C in presence of oxygen.

EFFECT: increased activity of catalytic composition in above-indicated processes.

15 cl, 8 dwg, 13 ex

FIELD: isomerization and disproportionation catalysts.

SUBSTANCE: invention relates to crystalline α-chromium oxide, chromium-containing catalytic compositions, method for preparation thereof, and to a process of fluorine distribution in hydrocarbon and/or halogenated hydrocarbon in presence of indicated catalytic compositions. In claimed α-chromium oxide, about 0.05 to about 2 atomic % chromium in the lattice of α-chromium oxide is substituted by nickel atoms and, optionally, further chromium atoms in the lattice are substituted by trivalent cobalt atoms, the total amount of nickel and trivalent cobalt atoms in the α-chromium oxide lattice not exceeding 6 atomic %. Claimed α-chromium oxide is prepared via coprecipitation of solid substance by introducing ammonium hydroxide, this method being supplemented by introducing an excess of ammonium nitrate into precipitated mixture before dehydration step and calcination step at 375 to 1000°C in presence of oxygen. Chromium-containing catalytic compositions containing crystalline nickel-substituted α-chromium oxide as chromium-containing component optionally treated with fluorination agent are also claimed. Composition preparation procedure comprises: (a) coprecipitation of solid substance by introducing ammonium hydroxide into aqueous solution of soluble bivalent nickel salt, soluble trivalent chromium salt, and optionally soluble bi- or trivalent cobalt salt, wherein solution contains at least three moles nitrate per mole chromium and has concentration of nickel from about 0.05 to about 2 mol % based on total content of nickel, chromium, and cobalt (if present) in solution and total concentration of nickel and cobalt (if present) not higher than 6 mol % on the same basis; (b) collecting coprecipitated solid substance obtained in step (a); (c) drying collected solid substance; and (d) calcination of dried solid substance at 375 to 1000°C in presence of oxygen.

EFFECT: increased activity of catalytic composition in above-indicated processes.

15 cl, 8 dwg, 13 ex

FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.

EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.

1 dwg, 1 tbl, 12 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.

EFFECT: increased catalyst activity.

5 cl, 2 tbl, 6 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention relates to methods for preparing carbon monoxide-conversion catalysts used in production of hydrogen, nitrogen-hydrogen mixture, and other hydrogen-containing gases. According to first option, active catalyst component, i.e. iron compound, is precipitated from solution with precipitation reagent, whereupon precipitate is separated from mother liquor and washed to form catalyst mass, which is molded and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. According to second option, iron compound is first mixed with promoting additives and cations of promoting additives are precipitated jointly with iron cations, resulting precipitate is separated from mother liquor, washed and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. As iron compound in the first and second options, ferrous and ferric sulfates and, as precipitation reagent, carbonate salts or corresponding hydroxides are utilized. Promoting additives are selected from Cu, Mn, and Al or, in the second option, their mixture.

EFFECT: reduced content of sulfur in finished catalyst at the same catalyst activity.

3 cl, 1 tbl, 12 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention, in particular, relates to catalyst based on synthetic mesoporous crystalline materials and provides hydrocarbon conversion catalyst composed of: group VIII metal/SO42-/ZrO2-EOx, where E represents element of the group III or IV of Mendeleev's periodic table, x = 1.5 or 2, content of SO42- is 0.1 to 10% by weight, ZrO2/EOx molar ratio is 1:(0.1-1.0), which has porous crystalline structure with specific surface 300-800 m2/g and summary pore volume 0.3-0.8 cm3/g. Preparation method comprises precipitation of zirconium compounds, in particular zirconium hydroxide or zirconyl, under hydrothermal conditions in presence of surfactant to form mesoporous phase, which is stabilized with stabilizing agents: group III and IV elements. When stabilization is achieved, if necessary, acidity is adjusted and group VIII metal is added.

EFFECT: increased specific surface area and heat resistance at simplified technology.

9 cl, 2 dwg, 2 tbl, 6 ex

FIELD: chemical industry; methods of production of zirconium oxides

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of obtaining of zirconium oxide for production of the catalytic agents used, for example, in the reactions of the organic synthesis. The invention presents the method of obtaining of zirconium oxide for production of the catalytic agents, which includes the operations of dissolution of the zirconium salt in water, treatment of the solution with the alkaline reactant, settling of the metals hydroxides, filtration, separation of the mother-liquor from the settlings, the settlings water flushing, its drying, calcination and granulation and-or granulation by molding. At that dissolution of the source zirconium chloride and-or zirconium oxychloride is conducted in the sodium chloride solution with concentration of 200-250 g/dc3 till reaching of the concentration of zirconium of 20-120 g/dc3. Settling of zirconium oxyhydrate is conducted by the adding the initial chloride solution in the solution of the sodium hydroxide with concentration of 20-80 g/dm3 up to reaching the suspension pH equilibrium value - 5-8. Then the suspension is filtered up to the zirconium oxyhydrate pasta residual humidity of 40-80 %. The mother chloride solution is separated from the settlings of zirconium oxyhydrate and again use it for dissolution of the next batch of zirconium chloride and-or zirconium oxychloride. The settlings of zirconium oxyhydrate are subjected to drying at 80-100°C within 2-6 hours, then the dry settlings are suspended in the water at the ratio of liquid to solid L:S = (5-10 :1, the suspension is filtered, the sediment on the filter is flushed by water, the chlorides are wash off up to the residual concentration of ions of chlorine in the flush waters of 0.1-0.5 g/dm3, divided into 2 parts, one of which in amount of 60-80 % is subjected to drying and calcinations at the temperatures of 300-600°C, and other part in amount of 20-40 % is mixed with the calcined part of the settlings and subjected to granulation by extrusion at simultaneous heating and dehydration of the damp mixture of zirconium oxide and zirconium oxyhydrate with production of the target product. The technical result of the invention is improvement of quality of the produced zirconium oxide for production of the catalytic agents due to provision of the opportunity to use ZrO2 for the subsequent production of the various catalytic agents of the wide range of application and thereby improving the consumer properties of the produced production.

EFFECT: the invention ensures improvement of the quality of the produced zirconium oxide for production of the catalytic agents with improved consumer properties.

1 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+1-xAl+3x(OH)2]x+[An-x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.

EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

FIELD: chemical industry; materials and the methods for the catalyst carrier manufacture.

SUBSTANCE: the invention is pertaining to the new mixed oxides produced from ceric oxide and zirconium oxide, which can used as the catalyzers or the catalyzers carriers for purification of the combustion engine exhaust gases. The mixed oxide possesses the polyphase cubical form of the crystallization and oxygenous capacity of at least 260/ micromoles of O2 /g of the sample and the speed of the oxygen extraction of more than 1.0 mg-O2/m2-minute, which are measured after combustion within 4 hours at the temperature of 1000°C. The invention also presents the substrate with the cover containing the indicated mixed oxide. The method of production of the polycrystallic particles of the indicated mixed ceric-zirconium oxide includes the following stages: i) production of the solution of the mixed salt which are containing, at least, one salt of cerium and, at least, one salt of zirconium in the concentration, sufficient for formation of the polycrystallic particles of the corresponding dry product on the basis of the mixed oxide. At that the indicated particles have the cerium-oxide component and zirconium-oxide component, in which these components are distributed inside the subcrystalline structure of the particles in such a manner, that each crystallite in the particle consists of a set of the adjacent one to another domains, in which the atomic ratios of Ce:Zr which are inherited by the adjacent to each other domains, are characterized by the degree of the non-uniformity with respect to each other and determined by means of the method of the X-ray dissipation the small angles and expressed by the normalized intensity of the dissipation I(Q) within the limits from approximately 47 up to approximately 119 at vector of dissipation Q, equal to 0.10 A-1; ii) treatment of the solution of the mixed salt produced in compliance with the stage (i),with the help of the base with formation of sediment; iii) treatment of the sediment produced in compliance with the stage (ii),using the oxidative agent in amount, sufficient for oxidizing Ce+3 up to Ce+4; iv) washing and drying of the residue produced in compliance with the stage (iii); and v) calcination of the dry sediment produced in compliance with the stage (iv),as the result there are produced polycrystallic particles of the oxide of ceric and zirconium in the form of the mixed oxide with the above indicated characteristics. The technical result is the produced mixed oxide possesses both the high oxygenous capacitance, and the heightened speed of the oxygen return in the conditions of the high temperatures.

EFFECT: the invention ensures production of the mixed oxide manufactured from ceric oxide and zirconium oxide and possessing the high oxygenous capacitance and the heightened speed of the oxygen return in the conditions of the high temperatures.

68 cl, 21 ex, 2 dwg

FIELD: production of catalytic compositions.

SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.

EFFECT: enhanced efficiency.

29 cl, 8 ex

FIELD: redox reaction catalysts.

SUBSTANCE: invention relates to methods for preparing vanadium-titanium oxide catalysts for redox reactions, e.g. for industrial processes of production of phthalic anhydride via oxidation of o-xylene, selective reduction nitrogen oxides, and detoxification of organochlorine compounds. Method of invention comprises following stages: providing titanyl sulfate solution; adding ammonia and then vanadium peroxide solution to titanyl sulfate solution or adding to the same vanadyl sulfate or oxalate and then ammonia solution; optionally ageing suspension resulting after mixing of solutions; filtration; and calcinations at 450°C.

EFFECT: increased heat resistance of active chlorobenzene oxidation catalyst and reduced catalyst preparation time (10-12 h instead 72 h as in a known method).

1 tbl, 3 ex

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