Catalyst of pyrolysis of propane-butane hydrocarbon material in lowest olefins and method of obtaining it
SUBSTANCE: catalyst of pyrolysis of propane-butane hydrocarbon material with the formation of the ethylene and the propylene, which presents itself directly on the surface of the reactor of the ceramic catalytic film covering with a mass of 50-70 g/m2, having the gross weight-composition, moll %: mixture ZnO and CdO - 20÷30, SiO2 - 20÷40, P2O5 40÷50 with heterogeneous chemical compound through the thickness of the coating. Also another method of obtaining the catalyst is described. It is obtained by processing the surface of the reactor by aqueous solutions or suspensions of the compounds of zinc, cadmium, silicon and phosphorus or their mixtures - ashes-gel method, drying of the coating at 80-100°C and heat processing at 200-400°C for the formation the ceramic catalytic film coating.
EFFECT: obtaining active and selective catalyst for pyrolysis of propane-butane hydrocarbon material without the formation of coke with a high output of ethylene and a low output of propylene.
2 cl, 1 tbl
The invention relates to the production of lower olefins by the pyrolysis of hydrocarbons and can be used in the chemical and petrochemical industry, in particular to a method for producing catalysts for the pyrolysis of propane-butane hydrocarbons and a method of catalytic pyrolysis in order to obtain lower olefins With2-C3.
Industrial method of obtaining lower olefins With2-C3is thermal pyrolysis of different types of hydrocarbons, which is carried out at a temperature of 780-850°C. the Disadvantages of the process of thermal pyrolysis of hydrocarbons are very hard process conditions temperature, low yield of lower olefins (42-46%) and education in a significant amount of coke ("sakakawea" reactors), and in this regard, systematic stop production in order to remove coke.
The process of pyrolysis of hydrocarbons in the presence of a catalyst in comparison with thermal process allows to carry out the pyrolysis in milder conditions, to significantly improve the yield of lower olefins With2-C3and reduce the formation of by-products - polycondensating aromatic hydrocarbons and coke deposits.
Known catalyst and method thereof, where the preparation of a carrier for catalyst p is rolisa hydrocarbons lead by mixing the ceramic material, consisting of kaolin, clay, quartz, pegmatite, with burnable fosforsoderzhashchie of 0.5-1.0 wt.% the boron phosphate and 10-15 wt.% dolomite additives, with the subsequent formation and calcination of the catalyst at 1150° (A.S. SU # 1292825, 01J 37/04, 1985). In a further catalyst was prepared by impregnation of the carrier composition: 12% by weight In2About3+ 4 wt.% K2O. the Yield of lower olefins C2-C4on the thus obtained catalyst is at 63.5-64 wt.% from straight-run gasoline fraction 28-180°, ethylene 41,3-of 41.7 wt.%, propylene and 17.6 to 18.5 wt.%.
The disadvantage of this method is the complexity of making the catalyst carrier with the use of a large number of natural components (clay, kaolin, quartz, dolomite, pegmatite), which greatly complicates the play in the preparation of the carrier a stable composition with constant physico-chemical properties and high content in catalysts to 12 wt.% expensive modifier In2O3and the formation of coke.
A method of obtaining a catalyst of Fe2O-K2O-MgO (A.S. SU # 1825525, 10G 11/10, 1990) and method for producing lower olefins from a hydrocarbon feedstock in the presence of a catalyst at a temperature of 650-750°C, the mass ratio of straight-run gasoline: water vapor equal to 0.5:1.0, and when the catalyst loading compact layer at the entrance to the reactor in amounts which, occupying 10-70 vol.% the reactor.
The disadvantage of this method of producing olefinic hydrocarbons from hydrocarbon feedstock is not a high yield of lower olefins With2-C4from straight-run gasoline, as well as a multi-stage and complexity of the preparation of the catalyst and the formation of coke.
A method of obtaining lower olefins by thermal decomposition of gasoline in the presence of magnesium-containing catalyst at a temperature 250-390° (A.S. SU # 1191456, 10G 11/02, 1984). The disadvantage of this method is the low yield of ethylene and propylene and the formation of coke.
There is a method of catalytic pyrolysis of hydrocarbons: gasoline, wide fraction of light hydrocarbons (NGL) and n-butane on vanadium-potassium catalyst at 800-810°C, flow rate of feed of 2.5-3.2 h-1and the water vapor content of 50-70 wt.% (S. p. black, Mukhina T.N., At the S.E., Omelichkina G., Adelson SV, Zografou F.G. Catalytic pyrolysis of hydrocarbons // Catalysis in the chemical and petrochemical industries. - 2001 - No. 2 - S-18). The output of the lower olefins With2-C4from straight-run gasoline, LPG and n-butane on vanadium-potassium catalyst comprises 58.9; 62,4 and 63.2 wt.% respectively.
The disadvantage of this method is the complexity of preparation and high cost ka is alistor and not a high yield of lower olefins With 2-C3and also the formation of coke.
The closest to the essence of the technical solution is the way (SU # 2247599, 01J 21/04, 21/10, 23/02, 23/16, 37/04, 37/08, 10G 11/04, 2005) pyrolysis of hydrocarbons in the presence of a catalyst comprising a formed during the heat treatment cements structures MeO·nAl2About3where MeO - oxide II And group of the Periodic system of the elements or mixtures thereof, a n is a number from 1.0 to 6.0, containing the modifying component selected from at least one metal oxide is magnesium, strontium, copper, zinc, indium, chromium, manganese, or mixtures thereof, hardening additive is an oxide of boron or phosphorus, or a mixture thereof and has the following composition in terms of oxide, wt.%: oxide MeO or their mixtures - 10,0-40,0, the modifying component is 1.0 to 5.0, an oxide of boron, phosphorus, or a mixture thereof is 0.5-5.0, aluminum oxide - rest.
The disadvantage of this method is the complexity of the preparation of the catalyst, the low output of individual olefins With2-C4and the formation of coke.
The objective of the invention is obtaining active and highly selective catalyst for the pyrolysis of hydrocarbons, the increase in the yield of lower olefins With2-C3catalytic pyrolysis of hydrocarbons, in particular propane-butane feedstock (CBE) and preventing the formation of coke.
The technical result of dostigao is the, the proposed catalyst is obtained directly on the surface of the reactor for pyrolysis CBE by processing the surface of the reactor at room temperature for one hour consecutively three different composition of aqueous solutions or suspensions of compounds of zinc, cadmium, silicon and phosphorus, or mixtures thereof ("Sol-gel" method), drying each layer at 80-100°C for 1-2 hours, and the catalyst of gross composition (mol.%) P2About540-50, ZnO/CdO(mix)20-30, SiO240-20 and weighing 50-70 g/m2surface of the reactor is formed during heat treatment at 200 to 400°C for 3-4 hours.
The use of differing composition of the aqueous solutions and suspensions ensures the formation of the catalyst in the form of dense cohesion associated with the surface of the reactor "ceramic" film distribution components on the film thickness in the following order (from the surface of the reactor): ZnO, CdO, SiO2and R2About5everywhere.
The proposed catalyst is tested in a laboratory setup flow type in the pyrolysis process CBE* (* Technical product composition (mol.%): propane 76,2%, butane 17,5%, ethane 4.1% and methane 2,3%). The pyrolysis reactor made of quartz, was filled with metal shavings industrial reactor pyrolysis CBE to ethylene and propylene. After applying the catalysate the RA on the surface of metal shavings on the claimed invention, pyrolysis CBE at a temperature 530-660°accompanied by the formation of ethylene with yields up to 98% and propylene to 19%, coke is formed.
An additional significant feature of the invention is to increase the yield of ethylene with increasing contact time. In the absence of catalyst the inverse dependence that involves the cracking of hydrocarbons with the formation of coke.
The claimed invention is illustrated in examples 1-16, clarifying the invention, without limiting it (see table)
The output of the olefins in the pyrolysis CBE by the claimed invention.
|Examples||T°pyrolysis maximum yield of ethylene||τ contact, seconds||Output* mol.% ethylene**, propylene***|
|* Coke is not formed|
Thus, the proposed method of pyrolysis CBE to ethylene is more effective compared to prototype solutions.
1. The catalyst for the pyrolysis of propane-butane hydrocarbons with the formation of ethylene and propylene, characterized in that it is a is formed directly on the surface of the ceramic reactor catalytic coating weight 50-70 g/m2having the gross composition, mol.%: a mixture of ZnO and CdO 20÷30, SiO220÷40, P2About540÷50 with heterogeneous chemical composition as the coating thickness.
2. The method of preparation of the catalyst according to claim 1, characterized in that the catalyst is obtained by way of the processing surface of the reactor aqueous solutions or suspensions of zinc compounds, cadmium, silicon and phosphorus, or mixtures thereof - the Sol-gel method, drying the coating at 80 to 100°and heat treatment at 200 to 400°for the formation of ceramic catalytic film coating.
FIELD: petrochemical process catalysts.
SUBSTANCE: catalyst constitutes cements formed during heat treatment and depicted by general formula MeO·nAl2O3, where Me is at least one group IIA element and n is number from 1.0 to 6.0, containing modifying component selected from at least one oxide of magnesium, strontium, copper, zinc, indium, chromium, manganese, and strengthening additive: boron and/or phosphorus oxide. The following proportions of components are used, wt %: MeO 10.0-40.0, modifying component 1.0-5.0, boron and/or phosphorus oxide 0.5-5.0, and alumina - the balance. Catalyst is prepared by dry mixing of one group IIA element compounds, aluminum compounds, and strengthening additive followed by mechanochemical treatment on vibromill, molding of catalyst paste, drying, and calcination at 600-1200°C. Modifying additive is incorporated into catalyst by impregnation and succeeding calcination. Method of pyrolysis of hydrocarbon feedstock producing C2-C4-olefins is also described.
EFFECT: increased yield of lower olefins.
3 cl, 2 tbl, 18 ex
FIELD: technological processes.
SUBSTANCE: subject of invention is method of catalytically active lamellar silicates production with single or multiple layers, in particular, clays with interlaminar struts from A1 and/or Ti, for purification of spent gases. At that at the stage of interlaminar struts formation, metal solution is added into lamellar silicate and the received mixture at the stage of drying/calcination is heated with formation of struts supporting intermediate layer out of metal atoms. After that catalytically active salt of transition metal is added in the dry form to the received dry substance. Finally the prepared dry mixture is heated up to the temperature of higher than 300°C, as a result catalytically active transition metal atoms are introduced into immediate layer, and at the same time dry mixture calcination takes place. As metal solution, solutions of aluminium, titanium, iron, copper and chrome are used. As catalytically active salt of metal, in particular, nitrate or sulphate of copper, titanium or lanthanum are used.
EFFECT: method allows to relatively quickly obtain catalytically active lamellar silicates without exhausts.
15 cl, 1 ex, 1 tbl, 1 dwg
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: method of improving selectivity of highly selective epoxidation catalyst on support containing silver in amount at most 0.19 g per 1 m2 of the support surface area comprises bringing catalyst or catalyst precursor containing silver in cationic form into contact with oxygen-containing raw material at catalyst temperature above 250°C over a period of time more than 150 h, after which catalyst temperature is lowered to at most 250°C. Olefin epoxidation process comprises bringing above-described supported catalyst or catalyst precursor into contact with oxygen-containing raw material at catalyst temperature above 250°C over a period of time more than 150 h, after which catalyst temperature is lowered to at most 250°C and catalyst is brought into contact with raw material containing olefin and oxygen.
EFFECT: increased selectivity of catalyst.
12 cl, 3 tbl, 12 ex
FIELD: carbon materials.
SUBSTANCE: invention relates to porous carbon materials and, more specifically, to carbon catalyst supports and sorbents. Preparation of catalyst support is accomplished by mixing carbon material with gaseous hydrocarbons at 750-1200°C until mass of carbon material increases by 2-2.5 times, after which resulting compacted material is oxidized, said initial carbon material being preliminarily demetallized carbon nanofibers.
EFFECT: increased sorption capacity of material.
1 tbl, 6 ex
FIELD: carbon materials.
SUBSTANCE: invention relates to porous carbon materials and, more specifically, to carbon catalyst supports and sorbents. Preparation of catalyst support is accomplished by treating carbon black with hydrocarbon gas at heating and stirring until mass of carbon material increases by 2-2.5 times, after which resulting compacted material is oxidized, said hydrocarbon gas being gas originated from liquid hydrocarbon electrocracking and said treatment being carried out at 400-650°C.
EFFECT: simplified technology.
1 tbl, 6 ex
FIELD: petroleum processing catalysts.
SUBSTANCE: catalyst containing platinum, rhenium, antimony, and chlorine on alumina are prepared by impregnation of carrier with aqueous solution of compounds of indicated elements, antimony being deposited as first or second component. Once antimony or platinum-antimony combination, or rhenium-antimony combination deposited, catalyst is dried at 130°C and then calcined in air flow at 500°C. Reduction of catalyst is performed at 300-600°C and pressure 0.1-4.0 MPa for 4 to 49 h. After deposition of antimony or two elements (platinum-antimony or rhenium-antimony) and drying-calcination procedures, second and third or only third element are deposited followed by drying and calcination. Final reduction of catalyst is accomplished in pilot plant reactor within circulating hydrogen medium at pressure 0.3-4.0 MPa and temperature up to 600°C for a period of time 12 to 48 h.
EFFECT: enhanced aromatization and isomerization activities of catalyst and also its stability.
2 cl, 1 tbl, 8 ex
FIELD: exhaust gas afterburning means.
SUBSTANCE: invention relates to catalytic neutralizer for treating internal combustion engine exhausted gases. Proposed catalyst is composed of catalytically active coating on inert ceramic or metallic honeycomb structure, wherein coating contains at least one platinum group metal selected from series including platinum, palladium, rhodium, and iridium on fine-grain supporting oxide material, said supporting oxide material representing essentially nonporous silica-based material including aggregates of essentially spherical primary particles 7 to 60 nm in diameter, while pH of 4% water dispersion of indicated material is below 6.
EFFECT: increased catalyst activity and imparted sufficient resistance to aggressive sulfur-containing components.
27 cl, 2 dwg, 7 tbl, 6 ex
FIELD: petroleum processing and catalysts.
SUBSTANCE: invention relates to catalyst for steam cracking of hydrocarbons, which catalyst contains KMgPO4 as catalyst component. Catalyst is prepared by dissolving KMgPO4 precursor in water and impregnating a support with resulting aqueous solution of KMgPO4 precursor or mixing KMgPO4 powder or its precursor with a metal oxide followed by caking resulting mixture. Described is also a light olefin production involving steam cracking of hydrocarbons.
EFFECT: increased yield of olefins, reduced amount of coke deposited on catalyst, and stabilized catalyst activity.
21 cl, 4 tbl, 14 cl
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention provides copper and silica-based catalyst containing 22.5-53.0% copper. Catalyst is prepared by reductive thermal decomposition of copper silicate in hydrogen flow at 380-450°C. catalyst is used in dihydroxyalkane production processes carried out at 180-200°C.
EFFECT: increased activity and selectivity of catalyst.
3 cl, 1 tbl, 8 ex
FIELD: gas treatment processes and catalysts.
SUBSTANCE: invention relates to catalyst for selectively oxidizing hydrogen sulfide to sulfur in industrial gases containing 0.5-3.0 vol % hydrogen sulfide and can be used at enterprises of gas-processing, petrochemical, and other industrial fields, in particular to treat Claus process emission gases, low sulfur natural and associated gases, chemical and associated petroleum gases, and chemical plant outbursts. Catalyst for selective oxidation of hydrogen sulfide into elementary sulfur comprises iron oxide and modifying agent, said modifying agent containing oxygen-containing phosphorus compounds. Catalyst is formed in heat treatment of α-iron oxide and orthophosphoric acid and is composed of F2O3, 83-89%, and P2O5, 11-17%. Catalyst preparation method comprises mixing oxygen-containing iron compounds with modifying agent compounds, extrusion, drying, and heat treatment. α-Iron oxide used as oxygen-containing iron compound is characterized by specific surface below 10 m2/g, while 95% of α-iron oxide have particle size less than 40 μm. Orthophosphoric acid is added to α-iron oxide, resulting mixture is stirred, dried, and subjected to treatment at 300-700°C. Hydrogen sulfide is selectively oxidized to elemental sulfur via passage of gas mixture over above-defined catalyst at 200-300°C followed by separation of resultant sulfur, O2/H2S ratio in oxidation process ranging from 0.6 to 1.0 and volume flow rate of gas mixture varying between 900 and 6000 h-1.
EFFECT: increased yield of elemental sulfur.
9 cl, 5 tbl, 9 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: group of inventions relates to conversion of hydrocarbons using micro-mesoporous-structure catalysts. A hydrocarbon conversion process is provided involving bringing hydrocarbon raw material, under hydrocarbon conversion conditions, into contact with micro-mesoporous-structure catalyst containing microporous crystalline zeolite-structure silicates composed of T2O3(10-1000)SiO2, wherein T represents elements selected from group III p-elements and group IV-VIII d-elements, and mixture thereof, micro-mesoporous structure being characterized by micropore fraction between 0.03 and 0.40 and mesopore fraction between 0.60 and 0.97. Catalyst is prepared by suspending microporous zeolite-structure crystalline silicates having above composition in alkali solution with hydroxide ion concentration 0.2-1.5 mole/L until residual content of zeolite phase in suspension 3 to 40% is achieved. Thereafter, cationic surfactant in the form of quaternary alkylammonium of general formula CnH2n+1(CH3)3NAn (where n=12-18, An is Cl, Br, HSO4 -) is added to resulting silicate solution suspension and then acid is added formation of gel with pH 7.5-9.0. Gel is then subjected to hydrothermal treatment at 100-150°C at atmospheric pressure or in autoclave during 10 to 72 h to produce finished product.
EFFECT: enlarged assortment of hydrocarbons and increased selectivity of formation thereof.
16 cl, 2 dwg, 2 tbl
SUBSTANCE: invention relates to the catalyst for synthesising the 2- and 4-picolines, method for its producing and the method for producing the 2- and 4-picolines. The catalyst which can be used in synthesis of 2- and 4-picolines containing the heteropolyacid from the group containing the silicon tungsten acid, phosphorus tungsten acid and the vanadium tungsten acid applied upon the silica gel substrate with the particles size of 6-14 mesh, is described. The method for producing the catalyst is also described, which includes the dissolution of heteropolyacid in distilled water, stirring the obtained mixture with the needed amount of the silica gel to obtain the suspension; mixing the suspension till even impregnation, air drying the suspension at 200-250°C up to 1.5 hour; following heating the suspension at 300 to 400°C within 0.5 to 1.5 hours and cooling the obtained product till the room temperature in the exiccator to obtain the needed catalyst. The method for producing the of 2- and 4-picolines is described which includes the interaction of acetaldehyde and ammonium hydrate at heating in presence of the said catalyst.
EFFECT: stable highly selective and active catalyst is available.
14 cl, 3 ex