Catalyst of pyrolysis of propane-butane hydrocarbon material in lowest olefins and method of obtaining it

FIELD: chemistry.

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)

Table

The output of the olefins in the pyrolysis CBE by the claimed invention.
ExamplesT°pyrolysis maximum yield of ethyleneτ contact, secondsOutput* mol.% ethylene**, propylene***
166027-2898**
263019-2070**
363010-1160**
45906-750**
55603,9034-35**
65803,2033**
75903,2597**
8 5904,1029**
95905,5032**
105907,6042**
1159010,2050**
1259013,0066**
1359019,0083**
145600,03817,6***
156300,03819,0***
167000,03818,1***
* 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.



 

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