Hydrocarbon feedstock pyrolysis catalyst, method for preparation thereof, and a method of hydrocarbon feedstock pyrolysis into lower olefins

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

 

The invention relates to the production of lower olefins and can be used in the chemical and petrochemical industry, in particular to a method for producing catalysts for the pyrolysis of hydrocarbons and method for catalytic pyrolysis of hydrocarbons in order to obtain lower olefins With2-C4.

Industrial process of obtaining lower olefins With2-C4is 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 is low and the output of the lower olefins 42-46 % and very hard process conditions.

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-C4and reduce the formation of by-products - polycondensating aromatic hydrocarbons and coke deposits.

Known catalyst and method of production, where the preparation of a carrier for catalyst for pyrolysis of 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 doba is kami, with the subsequent molding and calcination of the catalyst at 1150° C (A. C. SU N 1292825, B 01 J 37/04, 1985). In a further catalyst was prepared by impregnation of the support 12 wt.% In2O3+4 wt.% K2O. the Yield of lower olefins With2-C4on the thus obtained catalyst is at 63.5-64 wt.% from straight-run gasoline fraction 28-180° C; ethylene - 41,3-of 41.7 wt.%, propylene -17,6 to 18.5 wt.%.

The disadvantages of this method are 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 In2O3.

A method of obtaining a catalyst of Fe2O-K2O-MgO (A. C. SU N 1825525, C 10 G 11/10, 1990), adopted for the prototype. Catalyst Fe2O-K2O-MgO obtained by coprecipitation of Fe (III) and Mg (II) from solutions of nitrate salts with a solution of caustic potash.

The disadvantages of the catalyst and method of its production, taken as a prototype, is a multi-stage and complexity of the preparation of the catalyst by coprecipitation method.

A method of obtaining lower olefins by thermal decomposition of gasoline in prisutstviuyuschih catalyst at a temperature 250-390° C (A. C. SU N 1191456, C 10 G 11/02, 1984).

The disadvantage of this method is the low yield of ethylene and propylene.

A method of obtaining lower olefins from a hydrocarbon feedstock in the presence of a catalyst of Fe2O-K2O-MgO 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 number, occupying 10-70 vol.% reactor (A. C. SU N 1825525, C 10 G 11/10, 1990).

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.

The closest to the essence of the technical solutions of lower olefins from a hydrocarbon feedstock in the presence of a catalyst is way 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, Jafarov F.G. Catalytic pyrolysis of hydrocarbons // Catalysis in the chemical and petrochemical industries. - 2001. No. 2. - S. 13-18.). The output of the lower olefins With2-C4from straight run, gasoline is a, NGL and n-butane on vanadium-potassium catalyst comprises 58.9; 62,4 and 63.2 wt.% respectively.

The disadvantages of this method are the complexity of preparation and the high cost of the catalyst and not a high yield of lower olefins With2-C3.

The objective of the invention is the obtaining of an active and selective catalyst for the pyrolysis of hydrocarbons and increase the yield of lower olefins With2-C3catalytic pyrolysis of hydrocarbons: straight-run gasoline and propane-butane fraction.

The technical result is achieved by the fact that the proposed catalyst was prepared by dry mixing the starting components: compounds II A group of the Periodic system of the elements or mixtures thereof, aluminum compounds and a hardening additive compounds of boron, phosphorus, or mixtures thereof, followed by mechanochemical processing them in a vibrating mill for 0.1 to 72 hours, by forming the catalyst mass, drying at a temperature of 100-110° C for 0.1 to 24 hours and the catalyst formed during the heat treatment at 600-1100° C for 0.1 to 48 hours

Under the action of mechanical and high-temperature treatments of a mixture of compounds II A group of the Periodic system of elements (Ca, Mg, Sr, and others) or their mixtures and compounds of aluminum are formed cements composition: MeO· n Al2O3where MeO - metal oxide gr II A is PI of the periodic system of elements, n = 1,0-6,0, which under normal conditions are obtained when 1200-1500° C. Preliminary mechanical activation of a mixture of the starting components can significantly reduce the temperature of annealing required for the formation of cements. In the IR spectra of the obtained catalysts are observed absorption band at 420-460, 750-850 and 550-700 cm-1characteristic of cements.

The modifying additive in the catalyst introduced by impregnation of cement corresponding salts of magnesium, strontium, copper, zinc, indium, chromium, manganese or mixtures thereof in the amount of 1.0 -15,0 wt.%, followed by drying at 100-110° C for 0.1 to 24 hours, and calcining at a temperature of 800-1000° C for 4-24 hours

The invention is illustrated by the following examples.

Example 1. of 10.50 g of Mg(NO3)2·6 H2O mixed with 9,825 g pseudoboehmite AlO(OH), 0.14 g H3PO4and subjected to mechanochemical treatment in a vibrating mill for 24 hours and Then the resulting powder was molded, dried 2 h at 110° C, calcined in air for 8 h at 750° C and 4 h at 1050-1100° C.

The resulting cement has a composition of MgO · n Al2O3where n = 2.

The resulting catalyst has a composition, wt.%:

MgO-16,3;

Al2O3-82,7;

P2O5of-1.0.

Example 2. 1,300 g of Mg(OH)2mixed with 13,919 g Al(OH)3, 0,177 g H3BO3and put Mahaneh the chemical processing in a vibrating mill for 48 hours Then the resulting powder was molded, dried 2 h at 110° C, calcined in air for 4 h at 800° C, 2 h at 950° C and 4 h at 1100-1150° C.

The resulting cement has a composition of MgO n Al2O3where n=4.

The resulting catalyst has a composition, wt.%:

MgO-8,9;

Al2O3-90,1;

B2O3of-1.0.

Example 3. 2,848 g CA(Oh)2mixed with 27,648 g AlO(OH), 0,362 g H3PO4, 0,464 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 72 hours and Then the resulting powder was molded, dried 4 h at 110° C, calcined in air for 4 h at 750° C and 8 h at 1050-1100° C.

The resulting cement has a composition CaO · n Al2O3where n = 6.

The resulting catalyst has a composition, wt.%:

CaO-8,2;

Al2O3-89,8;

P2O5-1,0;

B2O3of-1.0.

Example 4. 2,387 g Mg(OH)2mixed with 12,771 g Al(OH)3, of 0.182 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 72 hours and Then the resulting powder was molded, dried 2 h at 110° C, calcined in air for 4 h at 800° C, 8 h at 1100-1150° C.

The resulting cement has a composition of MgO · n Al2O3where n = 2.

Then the obtained cement impregnated put 1,348 grams Cr(NO3)3·9H2O. For this 1,348 grams Cr(NO3)3·9H2O dissolved in 10 ml distilleria the Noi water, impregnation of the cement obtained with a solution of chromium nitrate is carried out at 40-50° C and stirring for 3-4 hours, after which the catalyst was dried at 100-110° C for 6-8 h and calcined in air for 8 h at 600° C and 6 h at 1000-1050° C.

The resulting catalyst has a composition, wt.%:

MgO-15,9;

Al2O3-80,6;

Cr2O3-2,5;

B2O3of-1.0.

Example 5. 1,65 g MgO is mixed with 8,35 g Al2O3, 0,146 g H3PO4and subjected to mechanochemical treatment in a vibrating mill for 72 hours and Then the resulting powder was molded, dried 2 h at 110° C, calcined in air for 4 h at 800° C, 4 h at 1050-1100° C.

The resulting cement has a composition of MgO · n Al2O3where n=2.

Then the obtained cement impregnated put 2,769 grams Cr(NO3)3·9H2O. For this 2,769 grams Cr(NO3)3·9 H2O dissolved in 15 ml of distilled water, the impregnated cement obtained with a solution of chromium nitrate is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 8 h at 800° C and 4 h at 1000-1050° C.

The resulting catalyst has a composition, wt.%:

MgO-15,5;

Al2O3-78,5;

Cr2O3-5,0;

P2O5of-1.0.

Example 6. 10,496 g of Mg(NO3)2· 6 H2O mix the with 28,80 g pseudoboehmite AlO(OH), 0,776 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 12 hours and Then the resulting powder was molded, dried 2 h at 100° C, calcined in air for 4 h at 750° C and 24 h at 1050-1100° C.

The resulting cement has a composition of MgO · n Al2O3where n = 6.

Then the obtained cement impregnated put 7,398 grams Cr(NO3)3·9H2O. For this 7,398 grams Cr(NO3)3·9 H2O was dissolved in 20 ml of distilled water, the impregnated cement obtained with a solution of chromium nitrate is carried out at 40-50° and With stirring for 3-4 hours, after which the catalyst was dried at 100-110° C for 8 h and calcined in air for 4 h at 600° C and 8 h at 950-1000° C.

The resulting catalyst has a composition, wt.%:

MgO-5,9;

Al2O3-87,1;

Cr2O3-5,0;

B2O3-2,0.

Example 7. 2,387 g Mg(OH)2mixed with 12,771 g Al(OH)3, 0,179 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 12 hours and Then the resulting powder was molded, dried 2 h at 110° C, calcined in air for 8 h at 800° C, 24 h at 1100-1150° C.

The resulting cement has a composition of MgO · n Al2O3where n = 2.

Then the obtained cement impregnated put 5,850 grams Cr(NO3)3·9H2O. For this 5,850 grams Cr(NO3)3·9 2O was dissolved in 20 ml of distilled water, the impregnated cement obtained with a solution of chromium nitrate is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 8 h at 800° C and 8 h at 1000-1050° C.

The resulting catalyst has a composition, wt.%:

MgO-14.5cm;

Al2O3-74,5;

Cr2O3-10,0;

B2O3of-1.0.

Example 8. 2,387 g Mg(OH)2mixed with 12,771 g Al(OH)3, 0,139 g H3PO4and subjected to mechanochemical treatment in a vibrating mill for 48 hours and Then the resulting powder was molded, dried 4 h at 100° C, calcined in air for 4 h at 800° C and 24 h at 1100-1150° C.

The resulting cement has a composition of MgO · n Al2O3where n = 2.

Then the obtained cement impregnated put 9,293 grams Cr(NO3)3·9H2O. For this 9,293 grams Cr(NO3)3·9 H2O was dissolved in 20 ml of distilled water, the impregnated cement obtained with a solution of chromium nitrate is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 6 h at 800° C and 4 h at 1100-1150° C.

The resulting catalyst has a composition, wt.%:

MgO-13,9;

Al2O3-70,4;

Cr2O3-14,9;

P2O5-0,8.

When is EP 9. 2,387 g Mg(OH)2mixed with 12,771 g Al(OH)3,0,101 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 24 hours and Then the resulting powder was molded, dried 2 h at 100° C, calcined in air for 6 h at 600° C, 24 h at 1050-1100° C.

The resulting cement has a composition of MgO · n Al2O3where n = 2.

Then the obtained cement impregnated put 1,459 g MnSO4· 5 H2O. For this 1,459 g MnSO4· 5 H2O dissolved in 15 ml of distilled water, the impregnated cement obtained by a solution of sulphate of manganese is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 8 h and calcined in air for 8 h at 600° C and 12 h at 1000-1050° C.

The resulting catalyst has a composition, wt.%:

MgO-15,5;

Al2O3-78,6;

MnO2-4,9;

B2O3of-1.0.

Example 10. 2,387 g Mg(OH)2mixed with 9.60 g AlO(OH), 0,196 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 24 hours

Then the resulting powder was molded, dried 2 h at 100° C, calcined in air for 6 h at 600° C, 24 h at 1050-1100° C.

The resulting cement has a composition of MgO · n Al2O3where n = 2.

Then the obtained cement impregnated put 3,058 g MnSO4· 5 H2O. For this 3,058 g MnSO4· 5 H2O was dissolved in 20 ml of distilled water, the impregnated cement obtained by a solution of sulphate of manganese is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 8 h and calcined in air for 8 h at 600° C and 8 h at 1000-1050° C.

The resulting catalyst has a composition, wt.%:

MgO-15,0;

Al2O3-74,0;

MnO2-10,0;

B2O3of-1.0.

Example 11. 2,387 g Mg(OH)2mixed with 9.60 g AlO(OH), 0,208 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 48 hours and Then the resulting powder was molded, dried for 8 h at 100° C, calcined in air for 6 h at 600° C, 24 h at 1050-1100° C.

The resulting cement has a composition of MgO · n Al2O3where n = 2.

Then the obtained cement impregnated put 4,g MnSO4·5H2O. this shows 4,861 g MnSO4· 5 H2O was dissolved in 20 ml of distilled water, the impregnated cement obtained by a solution of sulphate of manganese is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 4 h at 600° C and 8 h at 950-1000° C.

The resulting catalyst has a composition, wt.%:

MgO-14,0;

Al2O3-70,0;

MnO2-15,0;

B2O3of-1.0.

Example 12. 2,963 g Ca(OH)2) the t 9.60 g AlO(OH), 0,208 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 48 hours and Then the resulting powder was molded, dried 4 h at 100° C, calcined in air for 8 h at 600° C, 24 h at 1050-1100° C.

The resulting cement has a composition CaO · n Al2O3where n = 2.

Then the obtained cement impregnated put 1,620 g MnSO4·5H2O. For this 1,620 g MnSO4· 5 H2O was dissolved in 20 ml of distilled water, the impregnated cement obtained by a solution of sulphate of manganese is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 4 h at 800° C.

Then the obtained cement impregnated put 3,075 grams Cr(NO3)3·9H2O. For this 3,075 grams Cr(NO3)3· 9 H2O was dissolved in 20 ml of distilled water, the impregnated cement obtained with a solution of chromium nitrate is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 4 h at 800° C and 8 h at 1050-1100° C.

The resulting catalyst has a composition, wt.%:

CaO-19,2;

Al2O3-69,8;

MnO2-5,0;

Cr2O3-5,0;

B2O3of-1.0.

Example 13. 2,963 g Ca(OH)2mixed with 9.60 g AlO(OH), 0,208 g H3BO3and will overhaul mechanochemical treatment in a vibrating mill for 24 hours Then the resulting powder was molded, dried 4 h at 100° C, calcined in air for 8 h at 600° C, 24 h at 1050-1100° C.

The resulting cement has a composition CaO · n Al2O3where n = 2.

Then the obtained cement impregnated put 1,416 g In(NO3)3· 3H2O. For this 1,416 g In(NO3)3· 3 H2O dissolved in 10 ml of distilled water, the impregnated cement obtained by the solution of nitrates India is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 4 h at 800° C and 8 h at 950-1000° C.

The resulting catalyst has a composition, wt.%:

CaO-20,3;

Al2O3-73,7;

In2O3-5,0;

B2O3of-1.0.

Example 14. 2,963 g Ca(OH)2mixed with 9.60 g AlO(OH), 0,208 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 48 hours and Then the resulting powder was molded, dried 4 h at 100° C, calcined in air for 8 h at 600° C, 24 h at 1050-1100° C.

The resulting cement has a composition CaO · n Al2O3where n = 2.

Then the obtained cement impregnated put 1,213 g Zn(NO3)2· 6H2O. For this 1,213 g Zn(NO3)2· 6 H2O dissolved in 10 ml of distilled water, the impregnated cement obtained solution sarnaki the CSOs manganese is carried out at 40-50° C and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 4 h at 800° C.

Then the obtained cement impregnated put 0,672 g of Cu(NO3)2· 3H2O. For this 0,672 g of Cu(NO3)2· 3 H2O dissolved in 10 ml of distilled water, the impregnated cement obtained with a solution of chromium nitrate is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 4 h at 800° C and 8 h at 1050-1100° C.

The resulting catalyst has a composition, wt.%:

CaO-20,3;

Al2O3-73,7;

ZnO-3,0;

CuO-2,0;

B2O3of-1.0.

Example 15. 8,46 g Sr(NO3)2mixed with 9.60 g of pseudoboehmite AlO(OH), 0.21 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 24 hours and Then the resulting powder was molded, dried 2 h at 110° C, calcined in air for 8 h at 750° C and 4 h at 1050-1100° C.

The resulting cement has a composition of SrO · n Al2O3where n = 2.

The resulting catalyst has a composition, wt.%:

SrO-33,3;

Al2O3-65,7;

B2O3of-1.0.

Example 16. Alumomagnesium the catalyst was prepared as in example 2.

The resulting cement has a composition of MgO · n Al2O3where n = 4.

Then on the received price is UNT by impregnation put 3,338 g of Mg(NO 3)2· 6H2O. To do this, 3,g Mg(NO3)2· 6H2O dissolved in 15 ml of distilled water, the impregnated cement obtained by the solution of nitrates of magnesium is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 4 h at 600° C and 8 h at 950-1000° C.

The resulting catalyst has a composition, wt.%:

MgO-8,5;

Al2O3-85,5;

MgO-5,0;

B2O3of-1.0.

Example 17. Alumomagnesium the catalyst was prepared as in example 2.

The resulting cement has a composition of MgO · n Al2O3where n = 4.

Then the obtained cement impregnated cause of 5.92 g Cr(NO3)3· 9H2O. To do this, of 5.92 g Cr(NO3)3· 9H2O was dissolved in 20 ml of distilled water, the impregnated cement obtained with a solution of chromium nitrate is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 4 h at 600° C and 8 h at 950-1000° C.

The resulting catalyst has a composition, wt.%:

MgO-8,0;

Al2O3-81,0;

Cr2O3-10,0;

B2O3of-1.0.

Example 18. Alumomagnesium the catalyst was prepared as in example 2.

The resulting cement has a composition of MgO · n Al2O3where n = 4.

Then the obtained cement impregnated put 1,476 g MnSO4· 5H2O. For this 1,476 g MnSO4· 5H2O dissolved in 10 ml of distilled water, the impregnated cement obtained by a solution of sulphate of manganese is carried out at 40-50° and stirring for 2-3 hours, after which the catalyst was dried at 100-110° C for 12 h and calcined in air for 4 h at 600° C and 8 h at 950-1000° C.

The resulting catalyst has a composition, wt.%:

MgO-8,5;

Al2O3-85,5;

MnO2-5,0;

B2O3of-1.0.

The resulting catalysts have in the processes of pyrolysis straight-run gasoline fraction 28-185° and propane-butane fraction (LPG) in a laboratory setup flow-type fixed bed of the catalyst at a temperature of 780-850° C, flow rate of feed 2-4 h-1the mass ratio of hydrocarbon : water vapor = 1 : 0.5 to 1.0.

Shown in tables 1-2, examples clarify the invention without limiting it.

As can be seen from the table. 1-2 samples of catalysts based cements have high activity and selectivity in the formation of lower olefins With2-C4from straight-run gasoline fraction and a propane-butane fraction and not inferior to the prototype.

Thus, the proposed catalysts, obtained by dry-mixing the original com is onenew: compounds II A group of the Periodic system of the elements or mixtures thereof, aluminum compounds and a hardening additive compounds of boron, phosphorus, or mixtures thereof, followed by mechanochemical processing in a vibrating mill and modified at least one metal oxide from the group of magnesium, strontium, copper, zinc, indium, chromium, manganese or their mixture in an amount of 1.0 to 15.0 wt.%, stable at high temperatures 1000-1200° and above are active and selective catalysts in the formation of lower olefins With2-C4from straight-run gasoline and propane-butane fraction.

The proposed method for the preparation of the catalyst allows to considerably simplify the technology of preparation of the catalyst in comparison with the existing methods due to the exclusion stage coprecipitation from solutions of salts, there are no waste water and emissions.

The method of obtaining lower olefins With2-C4catalytic pyrolysis of hydrocarbons: straight-run gasoline fraction 25-185° and propane-butane fraction in the presence of catalysts, obtained by dry-mixing the starting components: compounds II A group of the Periodic system of the elements or mixtures thereof, aluminum compounds and a hardening additive compounds of boron, phosphorus, or mixtures thereof, followed by mechanochemical processing in a vibrating mill and modified at least one oxide of a metal from groups: the magician is s, strontium, copper, zinc, indium, chromium, manganese or mixtures thereof in the amount of 1.0 to 15.0 wt.%, allows great output and selectivity to obtain lower olefins With2-C4than in the presence of a catalyst of the prototype.

Table 1

The results of the pyrolysis of straight-run gasoline fraction 28-195°

various catalysts
Example

catalyst

No.
Tp,

°
Vabout,

h-1
H2Oh,

%

wt.
The output of alkenes With2-C4, wt.%Arena, wt.%
With2H4With3H6With4H6With2-C4
1800

820
2

3
80

80
32,2

34,8
21,0

18,3
4,9

5,0
61,5

62,2
6,0

5,6
2800

820
2

2
80

80
32,0

36,4
19,7

17,6
4,1

a 4.9
60,1

61,3
6,4

7,0
3800

820
2

80

80
31,5

34,8
20,9

18,6
5,2

of 5.4
61,5

62,6
5,5

6,7
4780

800

820
2

2

3
70

80

80
29,5

32,2

35,6
22,0

20,4

19,3
3,7

4,1

4,6
60,3

61,6

63,0
5,0

5,3

5,5
5800

820

800

820
2

2

3

3
80

80

70

70
33,2

36,1

32,7

35,3
20,7

18,4

18,1

17,6
4,9

4,9

4,9

5,0
62,0

63,1

60,1

62,5
4,0

5,1

6,4

5,3
6780

800

820
2

2

2
80

80

80
29,9

32,1

35,1
21,1

19,3

18,4
4,2

5,4

6,0
58,8

60,2

61,4
5,4

4,8

of 5.4
7800

820

800
2

2

3
70

70

70
33,8

36,8

34,2
20,4

18,9

17,9
5,3

5,4

5,5
62,8

63,9

61,6
3,4

4,5

3,1
8 780

800

820
3

3

3
70

70

70
28,5

32,0

33,5
20,8

19,6

the 17.3
4,7

6,3

5,5
58,4

60,8

62,6
7,6

8,0

8,2
9780

800

820
2

2

2
80

80

80
27,2

31,8

35,2
20,7

19,7

18,4
4,2

4,5

5,3
58,6

61,7

62,8
4,5

5,0

5,9

Example

catalyst

No.
Tp,

°
Vabout,

h-1
H2Oh,

%

wt.
The output of alkenes With2-C4, wt.%Arena, wt.%
With2H4With3H6With4H6With2-C4
10800

820
2

2
80

80
With2H4With3H6 With4H6With2-C48,2

8,4
11800

820

820
2

2

3
80

80

80
33,4

35,2

32,1
18,1

17,6

17,1
4,2

4,5

4,5
60,8

61,1

60,6
7,4

8,0

8,2
12800

820
2

2
80

80
32,0

34,2
18,5

of 17.5
6,2

6,0
60,2

61,2
5,1

5,9
13800

820
2

2
80

80
33,6

35,6
19,0

18,1
4,4

6,5
60,9

62,3
5,5

of 5.4
14780

800

820
2

2

2
80

80

80
30,0

32,1

35,7
18,7

17,6br>
16,4
6,1

6,0

of 5.4
58,6

59,8

61,6
4,0

4,2

4,6
Prototype79037033,016,86,0of 58.910,7
Table 2

The results of the pyrolysis of propane-butane fraction (LPG) on various

the catalysts
Example

catalyst

No.
Tp,

°
Vabout,

h-1
H2O,

%

wt.
Conversion,

%
The output of alkenes With2-C4, wt.%Arena, wt.

%
With2H4With3H6With2-C4
1800

820

840
2,5

2,5

3,0
70

70

70
80

84

89
35,3

37,1

38,9
17,6

16,4

15,7
54,9

56,1

58,3
0,6

1,2

1,5
2800

820

840
2,5

2,5

2,5
80

80

80
84

88

92
34,8

36,6

of 37.8
17,6

16,7

16,2
53,3

55,1

of 57.5
0,5

0,8

1,2
3820

840
2,0

2,0
100

100
87

96
35,9

to 38.3
16,9

the 15.6
54,7

55,3
0,8

1,4
5820

840
2,5

2,5
70

70
86

95
37,5

of 40.3
18,7

17,8
59,2

61,3
0,5

0,9
15820

840
2,0

2,0
80

80
87

96
36,9

42,6
18,3

15,8
58,1

60,8
0,9

1,3
16820

840
2,5

2,5
80

80
83

87
36,9

38,7
17,2

16,6
58,5

59,2
0,8

1,2
17820

840
2,5

2,5
70

70
87

96
37,9

41,7
17,8

17,4
59,4

62,8
0,6

1,1
18820

840
2,5

2,5
70

70
86

95
36,8

39,9
18,8

17,9
57,3

61,7
0,7

0,9
Prototype:

raw material: NGL

n-butane
800

800
3,0

3,0
70

50
37,6

40,8
16,5

of 17.5
62,4

63,2
6,8

2,7

1. The catalyst for the pyrolysis of hydrocarbons to lower olefins, characterized in that it is a formed during the heat treatment cements patterns MeO·nAl2O3where MeO - oxide II And group of the Periodic system of the elements or mixtures thereof, and n is a number from 1.0 to 6.0, contains the modifying component is applied to the cement impregnated 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 a mixture thereof 10,0-40,0

The modifying component 1,0-15,0

The oxide of boron, phosphorus, or mixtures thereof 0,5-5,0

Alumina rest

2. The method of preparation of the catalyst according to claim 1, characterized in that the catalyst was prepared by dry mixing of the compounds II And the Periodic system of the elements or mixtures thereof, aluminum compounds and a hardening additive compounds of boron, phosphorus, or mixtures thereof, followed by mechanochemical processing in a vibrating mill for 0.1 to 72 hours, by forming the catalyst mass, drying and calcining 0.1 to 48 h at 600-1200°s, followed by impregnation of the obtained cement modifier component: the corresponding salts is magnesium, strontium, copper, zinc, indium, chromium, manganese or mixtures thereof in the amount of 1.0 to 15.0 wt.%, followed by drying and calcining at a temperature of 800-1000°C for 4-24 hours

3. Way catalytic pyrolysis of hydrocarbons to lower olefins With2-C4, characterized in that the pyrolysis process is carried out at 600-850°C, space velocity of the hydrocarbon feedstock 2-4 h-1the mass ratio of hydrocarbon : water vapor=1:0.5 to 1 on the catalyst according to claim 1, as well as hydrocarbons using straight-run gasoline fraction 25-195°With or propane-butane fraction.



 

Same patents:

The invention relates to the production of lower olefins and can be used in the chemical and petrochemical industry, in particular to a method for producing catalysts for the pyrolysis of hydrocarbons and method of pyrolysis of hydrocarbon feedstocks to obtain lower olefins WITH2-C4

The invention relates to the field of pyrolysis of hydrocarbons

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

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides reforming catalyst containing Pt and Re on oxide carrier, in particular Al2O3, wherein content of Na, Fe, and Ti oxides are limited to 5 (Na2O), 20 (Fe2O3), and 2000 ppm (TiO2) and Pt is present in catalyst in reduced metallic state and in the form of platinum chloride at Pt/PtCl2 molar ratio between 9:1 and 1:1. Contents of components, wt %: Pt 0.13-0.29, PtCl2 0.18-0.04, Re 0.26-0.56, and Al2O3 99.43-99.11. Preparation of catalyst comprises impregnation of alumina with common solution containing H2PtCl6, NH4ReO4, AcOH, and HCl followed by drying and calcination involving simultaneous reduction of 50-90% platinum within the temperature range 150-550оС, while temperature was raised from 160 to 280оС during 30-60 min, these calcination conditions resulting in creation of reductive atmosphere owing to fast decomposition of ammonium acetate formed during preparation of indicated common solution.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 3 ex

FIELD: hydrocarbon conversion catalysts.

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4 cl, 1 tbl, 8 ex

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8 cl, 1 dwg, 11 ex

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EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.

40 cl, 2 tbl, 19 ex

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