The catalyst for the pyrolysis of hydrocarbons and method thereof

 

The invention relates to the field of pyrolysis of hydrocarbons. The described catalyst having the following phase composition, wt.%: the sum of the oxides of vanadium - 1,5-6,0, vanadium bronze - 0.5 to 1.0, the boron oxide is 0.5 to 3.0, quartz - 5,0-10,5, mullite - 6,0-14,5, cristobalite - 1,1-3,5, corundum - rest. Described is a method of obtaining such a catalyst, comprising mixing dry ingredients for the preparation of the carrier with the dry components of the active component of the catalyst, followed by molding, drying and annealing step. Technical result: the catalyst bears a high degree of selectivity, stability and service life when used in pyrolysis processes. 2 S. and 2 C.p. f-crystals, 2 tab.

The invention relates to the petrochemical industry, and more particularly, to a catalyst for the pyrolysis of hydrocarbons, and to a method for producing such a catalyst.

As shown in several studies, the most active in the pyrolysis of hydrocarbons are catalysts, as an active component which are vanadium compounds. A significant role is played by the porosity, specific surface area and mechanical strength of the carrier. The dependence of the activity, selectives what these indicators in absolute value, the better performance characteristics of catalysts.

The pyrolysis catalysts consisting of compounds of vanadium on the pumice, silicon oxides or zirconium is described in U.S. patent 5866745, CL 585-653 [1]. However, the catalysts, which are vanadium compounds on the pumice, silica, or Zirconia, have insufficient stability. It defines a limited service life of the catalyst.

Known catalyst based pyrovanadate potassium deposited on pumice, differs slightly long life, but its lack of selectivity.with. The USSR 219593, CL 10 G 11/02) [2].

The output products of pyrolysis in the presence of other known catalyst on the basis of potassium Vanadate caused by synthetic corundum media, based on the ethylene reaches 33,6%, the total yield of ethylene and propylene is 50,6% (C. A. Adelson and other "Chemistry and technology of fuels oils", 1980, 7, S. 19-22) [3].

However, in the products of pyrolysis in the presence of this catalyst is celebrated significant coke formation. In addition, significant quantities of methane is formed, there is not enough high selectivity of the catalyst [3] .

Known catalyst pyrolysis, containing as the active status is 01 J 23/22) [4]. This catalyst containing crystallites of a pyramidal shape, layering on each other with the formation of islet clusters, high mechanical strength and activity. However, due to the uneven distribution of the active component on the surface of the carrier, the catalyst does not have sufficient stability. When it is used in the pyrolysis process occurs high hydraulic resistance in the layer, leading to the destruction of the catalyst particles. In hard hydrodynamic conditions, the active component of the catalyst is gradually washed out of the reaction streams, and the catalyst irreversibly loses activity. Its durability is insufficient.

The present invention therefore was to create a catalyst pyrolysis with enhanced activity, strength and stability, as well as extended life.

The objective is formulated, in accordance with the present invention is solved by a catalyst for the pyrolysis of hydrocarbons, characterized in that as the active component it contains the sum of the oxides of vanadium to a valence of from 2 to 7, vanadium bronze and boron oxide in the following ratio ingredientsin Bora 0,5 - 3,0 Corundum - the Rest of the Proposed catalyst has a high degree of dispersion of the crystallites of the active component, having a hexagonal shape, which is the most durable of all types of crystallites.

The content of the active component in the above relation provides a good grip it with the media, which significantly increases the service life of such a catalyst with high activity and stability.

The catalyst, in accordance with the present invention, according to rentgenofazovogo analysis contains vanadium bronze, representing a combination of such compounds, as KAlSiO8To4V10About27, K2V8O21To3VO4, KV6O15To0,33V2O5, AlVO4minor amounts of other derivative polyvanadate acids, and oxides of vanadium II-V. This provides not only strengthening, but also reduce the porosity of the catalyst, which ultimately lead to increase its selectivity in pyrolysis processes, and increase service life. In addition, this catalyst is significantly cheaper known [4].

Another object of the present invention is a method of obtaining such a catalyst Pirna synthetic corundum by mixing with the carrier and subsequent evaporation of excess aqueous solution of the active component - of Vanadate, potassium and barium oxide of a given composition.with. The USSR 1011236, CL 01 J 23/22) [4].

The method in [4] does not allow to obtain the catalyst, in accordance with the present invention.

Thus, another objective of the present invention was to provide a method for obtaining the above-mentioned catalyst pyrolysis of hydrocarbons.

The objective is formulated, in accordance with the present invention, is solved by the method of obtaining the above-mentioned catalyst for pyrolysis of hydrocarbons, characterized in that the dry ingredients the basis for media - alumina and kaolin, mixed with the dry components to obtain the active component is potassium hydroxide, perioxide vanadium, boric acid and a temporary link - carboxymethylcellulose obtained catalyst mass is molded, dried and calcined in the temperature range 550-1500oIn manual mode using at least three heating stages, with increasing temperature in each stage is not more than 200oC.

The proposed method for the preparation of the catalyst according to the present invention assures high strength, active and stable catalyst having uvelicheniya catalyst, in accordance with the present invention allows to reduce the energy consumption for the process of preparation of the catalyst.

Optimal results are achieved when the ratio of corundum:kaolin to obtain the media is kept in the range of 2.56,0:1.

Optimal results are achieved when the catalyst was calcined exposure at each stage of heating at least one hour.

Example 1 For the preparation of a catalyst mass is mixed 77,14 g of corundum with 12,86 g of kaolin (mass ratio of alumina: kaolin is 6:1), 6,65 g perioxide vanadium, 0,41 g of potassium hydroxide, 5.31g boric acid and 8 g of carboxymethyl cellulose 20% humidity. The resulting mass is mixed, molded in the form of cuttings passing through the extruder, dried at a temperature of ~ 100oWith up to 6% residual moisture. Molded catalyst is finally dried at 120oC and calcined in three stages, starting with 650oWith increasing temperature calcination at 200oAnd age for at least one hour at each stage. Phase composition and properties of the catalyst are given in table.1.

Example 2
The catalyst prepared in accordance with example 1 using 69,64 g of corundum, 27,86 g of kaolin (mass ratio of alumina: it is llulose 20% humidity. After molding and drying, the catalyst was calcined in four stages, starting with a temperature of 500oWith increasing temperature calcination at 150oWith and exposure for 1.5 hours at each step. Phase composition and properties of the catalyst are given in table. 1.

Example 3
The catalyst prepared in accordance with example 1 using 80,57 g of corundum, 27,86 g of kaolin (mass ratio of alumina:kaolin is 2.9: 1) 4.4 g of perioxide vanadium, 0.26 g of potassium hydroxide, of 2.46 g of boric acid and 8.0 g of carboxymethyl cellulose 20% humidity. After molding and drying, the catalyst was calcined in five stages, starting with a temperature of 650oWith increase of the temperature of calcination on the 100oWith the first stage, 150o- On the second and third stages and 170oWith in subsequent stages. Phase composition and properties of the catalyst are given in table. 1.

Example 4
The catalyst prepared in accordance with example 3, using 77,45 g of corundum, 30,95 g of kaolin at a mass ratio of alumina:kaolin, equal to 6: 1, the remaining components of the catalyst used in the same quantities as in example 3. The calcining of the prepared catalyst is carried out in four stages, starting with 600oWith increasing temperature the measures 5
The catalyst prepared in accordance with example 1, except that the calcination of the prepared catalyst is carried out in four stages aged for 1.5 hours and the temperature increase of the calcination 180oSince at each step. Phase composition and properties of the catalyst are given in table.1.

Example 6
The catalyst prepared in accordance with example 1, except that the calcination of the prepared catalyst is carried out in five steps of calcination, starting with 550oWith increase of the temperature of calcination on the 100oWith the first stage, 150o- On the second, and 200oWith - in subsequent stages. Excerpt proklinaemogo catalyst in each stage is 1.0 hour.

Example 7
As the catalyst of comparison used is described in [4], with composition, wt.%: the potassium Vanadate - 6; barium oxide - 30, synthetic corundum - rest.

As can be seen from the data presented in table.1 the catalyst, in accordance with the present invention, has a lower specific surface area, low porosity and high crushing strength, which is extremely important for the operation of catalysts in pyrolysis processes.

Examples 8-14
The catalysts according to examples 1-7 were tested in odinakovaya steam - 70-75 wt. % and the pressure in the reaction zone is 0.7 to 0.9 MPa. The raw material used straight-run gasoline with density d4200,702 g/cm3the next fractional composition:
TemperatureoC -% vol. distillation
NC 42,0 -
70,0 - 10
109,0 - 50
160,0 - 90
QC 170,0 -
The chemical composition of gasoline, wt.%:
N. paraffin - 32,5
ISO-paraffins - 27,4
Naphthenic - 34,1
Aromatic hydrocarbons - 6,0
The results of pyrolysis gasoline in the presence of catalysts according to examples 1-7 are shown in table.2.

As can be seen from the data presented in table.2, the catalyst, in accordance with the present invention is superior to known [4] for selectivity ~ 1.5 times, meregenerasikan cycle 2 times and the service life of ~ 1.5 times.

The present invention can be used on any oil and gas production associated with the catalytic pyrolysis, as when upgrading existing installations of pyrolysis, and the creation of new industries.

The catalyst may be manufactured in a production environment using existing equipment without significant capital investments.


Claims

1. The catalyst feast is este active component the amount of vanadium oxides with a valency of from 2 to 7, vanadium bronze and boron oxide in the following ratio of ingredients, wt.%:
Quartz - 5,0-10,5
Mullite - 6,0-14,5
The cristobalite - 1,1-3,5
The sum of the oxides of vanadium - 1,5-6,0
Vanadium bronze - 0,5-1,0
The boron oxide - 0,5-3,0
Corundum - Rest
2. The method of producing catalyst for pyrolysis of hydrocarbons under item 1, characterized in that the dry ingredients the basis for media - alumina and kaolin is mixed with the dry components to obtain the active component is potassium hydroxide, perioxide vanadium, boric acid and a temporary link - carboxymethylcellulose obtained catalyst mass is molded, dried and calcined in the temperature range 550-1500oIn manual mode, using at least three stages of heating and temperature increase at each step is not more than 200oC.

3. The method of producing catalyst p. 2, characterized in that the mass ratio of alumina : kaolin to obtain the media is kept in the range of 2.56,0:1.

4. The method of producing catalyst according to p. 2, characterized in that the catalyst calcined exposure at each stage of heating at least one hour.

 

Same patents:

The invention relates to the field of production of commodity fuel and chemical products and semi-products of the processing of natural oil shale with the aim of obtaining products of organic synthesis, shale resin semi-coking and motor fuels, similar to the results obtained from crude oil, namely gasoline /1 Rudin M,, Serebryannikov N. D

The invention relates to catalysts for pyrolysis of hydrocarbons and can be used to produce unsaturated hydrocarbons, which is the raw material for the production of polymers, rubbers and so on

The invention relates to the field of processing oils and tars with a high content of metals and coke by high temperature contact with a granular or powdered broad porous adsorbent contact

The invention relates to the field of synthesis carriers for catalysts for conversion of hydrocarbons, for example catalysts for pyrolysis
The invention relates to the production of catalysts for ammonia synthesis and can be used in the nitrogen industry
The invention relates to the field of chemistry, and in particular to methods of preparation of catalysts for the conversion of light hydrocarbons to high octane motor fuel components

The invention relates to catalysts, catalyst carrier, process for their preparation and methods of purification of exhaust gases from the NOxincluding flue gases of thermal power plants, exhaust gases of cars, as well as in the production of nitric acid

The invention relates to a method for producing an activated catalyst composition in which a catalytic composition comprising a noble metal of group VIII and a compound of aluminum with hydrocarbon substituents on aluminiumoxide carrier containing up to 20 wt.% other components selected from the group comprising silicon dioxide, magnesium oxide, titanium oxide and zirconium oxide, activated by contact with hydrogen-containing gas at a temperature above 500oWith provided that at least when present in the catalytic composition, the compound of aluminum with a hydrocarbon Deputy is not a halide of aluminum compounds with hydrocarbon Deputy, you must activate the catalytic composition by contact with the halogen compound, either before or during the stage of activation

The invention relates to catalysts for the reductive alkylation of 4-aminodiphenylamine acetone and hydrogen to N-isopropyl-N-phenyl-p-phenylenediamine (diafana OP, IPPD) and methods for their preparation

The invention relates to catalytic chemistry, in particular to methods of preparation of oxide catalysts, and may find application in the chemical industry

The invention relates to the field of preparation of microspherical alumina carriers for catalysts

The invention relates to a method of producing methylformate used as an intermediate product when receiving the organic acid is formic, acetic, propionic and their esters, as well as formamido, and to a method of preparation of the catalyst to obtain methylformate

The invention relates to a method of manufacturing a catalyst with a catalytically active mass on the body of the carrier by thermal spraying, and the catalyst produced in this way
The invention relates to the production of catalysts for production of polyether polyols

The invention relates to the field of oil refining, in particular, to a method of preparation of the catalyst intended for use in the Hydrotreating of petroleum fractions

The invention relates to methods of producing catalysts for industrial flue gases from sulfur compounds, in particular for the oxidation of hydrogen sulfide and organic sulfur compounds to sulfur dioxide contained in the tail gas of the Claus process
The invention relates to methods for Nickel-alumina-chromium catalysts used for hydrogenation processes, gas purification, for processes mahanirvana carbon oxides
Up!