A method of producing motor fuels and catalyst for its implementation

 

(57) Abstract:

Usage: oil refining and petrochemical industry. The inventive mixture of hydrocarbon gases C1-C7processed at elevated temperature and pressure, preferably at temperautre 400-600C and a pressure of 0.1:2.0 MPa, in the presence of a catalyst having the following composition, wt. sverhkrupnyh zeolite type pentasil a molar ratio of SiO2/ Al2O3,25:160, 20-70; manganese oxide or a mixture of zinc oxide and/or gallium, 0,05-2,5; the rest of the binder. The catalyst used in the microspheric, or ball, or pellet form or in the form of extracash, or ball, or pellet form or in the form of extrudates. The catalyst may contain as a binder silicate, while it has the following chemical composition, wt. aluminum oxide 0,5-7,5; oxide selected from the group of zinc, or manganese, or gallium, or a mixture of 0.05-2.5; sodium oxide of 0.05-0.5; silica rest. The catalyst may contain a binder alumina, while it has the following chemical composition, wt. oxide selected from the group of zinc, or manganese, or gallium, or a mixture of 0,0 is et to contain a mixture of oxides of zinc, manganese and gallium, or a mixture of oxides of zinc and gallium, or a mixture of oxides of manganese and gallium, an oxide or manganese, and zinc. A method of producing motor fuels and catalyst for its implementation allows to obtain gasoline From 200 C output 44,8:43.3% octane 88,3-87,4 and diesel 200 K. K. with the release of a 14.1-12.9% to 2 C. and 13 C. p. F.-ly, 2 tab.

The invention relates to the production of motor fuels and can be used in the refining and petrochemical industries.

A method of obtaining aromatic hydrocarbons such as benzene, toluene, xylene, at elevated temperature and pressure from the lungs2-C5hydrocarbons in the presence of a catalyst comprising a zeolite of type ZSM-5, metals II or a mixture of them with VI metals and/or I In the groups of the Periodic table in an amount up to 15 wt%. in the calculation of the zeolite and 1 to 90 wt%. the binder is alumina, silica or clay (GDR patent N 251710, 01 J 29/28, 1986).

There is also known a process for the aromatization of hydrocarbons2-C4in the presence of a catalyst containing 0.1 to 99 wt.%. binder, 0.01 to 10% wt.gallium and 0.5 to 99.99 wt.zeolite synthesized in a fluoride medium with a molar ratio of SiO2/ is closest to the proposed method to the technical essence and the achieved result is a way of flavoring hydrocarbon fraction, containing ethylene, propylene and propane, using zeolite ZSM-5 or ZSM-11, containing 0.1% wt. gallium or thorium and forming part of the porous inorganic binder, clay, metal oxides, combinations thereof, etc.

The process is conducted at temperatures up to 700aboutC and a pressure of 0.1 to 6 MPa, and the weight rate of 0.1-400 h-1(U.S. Pat. USA N 4629818, C 07 C 12/02, 1986).

The disadvantage of the above patents, including prototype is not a high yield of the target fraction.

The present invention is to increase the output of motor fuels by increasing the activity of the catalyst.

The problem is solved by the proposed method for the production of motor fuels by processing a mixture of hydrocarbon gases WITH1-C7at elevated temperatures and pressures over zeolite catalyst containing servicecommunity zeolite type pentasil with a molar ratio of SiO2/Al2O3equal 25-160 and a metal oxide, a distinctive feature of which is that the use of a catalyst containing as the metal oxide, manganese oxide or mixture of oxide of manganese with zinc oxide and/or gallium oxide and having the following with the NCA with zinc oxide and/or gallium oxide of 0.05-2.5, the Rest of the Binder

It is preferable to use a catalyst containing the silicate as a binder or alyumooksid.

By using a catalyst having as a binder silicate, it has the following chemical composition, wt. Aluminum oxide 0,5-7,5

Manganese oxide or

the mixture of oxide of manganese with

zinc oxide and/or gallium oxide 0.05-2.5 Oxide, 0.05-0.5 sodium silica Rest

When using a catalyst having as a binder alyumooksid, it has the following chemical composition, wt.

Manganese oxide or a mixture of

manganese oxide with zinc oxide and/or gallium oxide 0.05-2.5 Oxide, 0.05-0.5 sodium Oxide silicon 18,0-68,8 alumina Rest

The process is preferably carried out at a temperature of 400-600aboutC, a pressure of 0.1-2.0 MPa and a space velocity of gas 100-3000 h-1.

The catalyst may be used in microspherical or ball, or pellet form or in the form of extrudates.

The problem is solved also the catalyst for the production of motor fuels containing binder, servicecompany zeolite type pentasil with a molar ratio of SiO2/Al2O3equal 25-160, and the oxide is of organza or a mixture of manganese oxide with zinc oxide and/or gallium oxide and has the following chemical composition, wt.

Sverkhvisokimi - natural zeolite 20-70

Manganese oxide or

the mixture of oxide of manganese with

zinc oxide and/or gallium oxide of 0.05-2.5, the Rest of the Binder

The catalyst may contain a mixture of oxides of metals in all proportions

As a binder, as indicated, the catalyst may contain alyumooksid or aluminosilicate. The chemical composition of the catalyst with different binder above in the description text.

As a mixture of oxides in the catalyst composition can be used a mixture of oxides of manganese and zinc, or a mixture of oxides of manganese and gallium, or a mixture of oxides of manganese, zinc and gallium.

The essence of the method consists in the following: a mixture of hydrocarbon gases WITH1-C7pass through a layer of the above catalyst at a temperature of 400-600aboutC, a pressure of 0.1-2.0 MPa and flow rate of gas 100-3000 h-1. As hydrocarbon gases can be used oily gas, gas condensate and propane-butane fraction of petrochemical processes, the composition shown in example 1.

Below are examples of the preparation of the catalyst, and examples of the method using the proposed kataliziruyemoi characteristics:

sulfuric acid, analytical grade, GOST 7712-80;

aluminum sulfate, H, GOST 3758-75;

gallium nitrate, H, TU 6-09-04-8-74;

ammonium sulfate, X. H. GOST 3769-73;

the gallium sulfate H, TU 6-09-4736-79;

nitrate zinc, H, GOST 5106-77;

nitrate manganese, H, GOST 6203-77.

Sodium silicate (liquid glass) with silicate module 2,7 received by the inserts silicate blocks (described in the book. Davidyants A. A. Pervushkin N. And. "The production of the catalyst for cracking and high-octane silica) Chemistry, 1972, 168 S.).

P R I m e R 1. An aqueous solution of aluminum sulfate containing 20 kg/m3aluminum oxide and 70 kg/m3sulfuric acid, an aqueous solution of sodium silicate (liquid glass) concentration of NaOH 1.6 kg-EQ/m3and suspension sverkhvysokochastotnogo (ICS) zeolite type pentasil with a molar ratio of SiO2/Al2O340 in an aqueous solution of manganese nitrate containing 100 kg/m3CRS-zeolite and 5 kg/m3manganese oxide, are mixed in the mixer with the formation of a Hydrosol, which is coagulated in 7aboutC and pH 8.0 in the hydrogel pellet form in a layer of mineral oil. Then the hydrogel treated with an aqueous solution of ammonium sulfate concentration of 10 kg/m3at the 50aboutC for 18 h, washed with condensate in the spirit.

The resulting catalyst contains 30 wt. CRS-zeolite and has the following chemical composition, wt. Aluminum oxide 7.5 Oxide manganese Oxide 1.5 0.3 sodium silica Rest

The catalyst according to example experience in the processing of hydrocarbon gases WITH1-C7(NGL wide fraction of light hydrocarbons) by running the installation with a fixed catalyst bed at atmospheric pressure, a temperature of 600aboutC, space velocity of the raw material (gas) 500 h-1and duration of experience 1 h

NGL had the following composition, wt. WITH11,8;28,3; C342,7; C437,8; C56.4; C62,1; C70,9.

P R I m m e R 2. An aqueous solution of aluminum sulfate containing 1.3 kg/m3aluminum oxide and 80 kg/m3sulfuric acid, an aqueous solution of sodium silicate concentration of NaOH (1.4 kg) EQ/m3and suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O325 in an aqueous solution of gallium sulfate, containing 80 kg/m3CRS-zeolite and 0.2 kg/m3manganese oxide, are mixed in the mixer with the formation of a Hydrosol, which is coagulated at the 15aboutC and a pH of 8.3 in the hydrogel pellet form in a layer of mineral oil. Then the hydrogel formation is condensate water at 30aboutC for 24 h from sulfate ions, dried at 110aboutC and calcined at 600aboutWith the current of air.

The catalyst containing 20 wt. CRS-zeolite and has the following chemical composition, wt. Alumina Oxide 0.5 manganese Oxide sodium 0.05 0.05 silicon Oxide Rest

The catalyst was tested under the conditions of example 1, except that, the volumetric feed rate of 100 h-1.

P R I m e R 3. An aqueous solution of aluminum sulfate containing 20 kg/m3aluminum oxide and 70 kg/m3sulfuric acid, an aqueous solution of sodium silicate concentration of NaOH 1.8 kg-EQ/m3mix in the mixer and forth in example 1. After washing, the hydrogel is dispersed with suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O3160 in an aqueous solution of manganese nitrate and subjected to spray drying at 400aboutC and calcining at 600aboutWith the current of air.

The resulting catalyst contains 70 wt. CRS-zeolite and has the following chemical composition, wt. Alumina 6.5 Oxide manganese Oxide 2.5 sodium 0.5 silica Else

The catalyst was tested at a temperature of 500aboutC, a pressure of 1 MPa, the space velocity of the feedstock 2000 h-1like nitrate, a mixture of gallium, zinc and manganese.

The resulting catalyst contains 30 wt. CRS-zeolite and has the following chemical composition, wt. Aluminum oxide 7.5 Oxide, gallium Oxide 0.5 zinc Oxide 0.5 manganese Oxide 0.5 0.3 sodium silica Rest

The catalyst was tested under the conditions of example 1.

P R I m e R 5. After washing the hydrogel obtained in example 3 was dispersed with suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O3160 in an aqueous solution of gallium nitrate and manganese and is subjected to spray drying at 400aboutC and calcining at 600aboutWith the current of air.

The resulting catalyst contains 50 wt. CRS-zeolite and has the following chemical composition, wt. Alumina 6.5 2.45 gallium Oxide manganese Oxide sodium 0.05 0.5 silica Else

The catalyst was tested at a temperature of 400aboutC, a pressure of 2 MPa, the space velocity of the feedstock 3000 h-1rest in example 1.

P R I m e R 6. After washing the hydrogel obtained in example 3 was dispersed with suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O3160 in an aqueous solution of nitrates of zinc and manganese and is subjected to spray with the jam contains 70 wt. CRS-zeolite and has the following chemical composition, wt. Aluminum oxide 6.6 Oxide zinc Oxide 2.45 manganese Oxide sodium 0.05 0.5 silica Else

The catalyst was tested at a temperature of 500aboutC, a pressure of 2 MPa, the space velocity of the feedstock 3000 h-1rest in example 1.

P R I m e R 7. Suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O325 in an aqueous solution of manganese nitrate, containing 200 kg/m3CRS-zeolite and 15 kg/m3manganese oxide, is dispersed with patinirovaniem aluminum hydroxide containing 20 kg/m3aluminium oxide and 1 kg/m3nitric acid, and subjecting the hydrocarbon-ammonia formed, dried at 120aboutC and calcined at 550aboutWith the current of air.

The resulting ball catalyst contains 20 wt. CRS-zeolite and has the following chemical composition, wt. Manganese oxide 1.5 sodium Oxide 0.05 silicon Oxide 18,0 alumina Rest

The catalyst was tested under the conditions of example 1.

P R I m e R 8. Suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O340 in an aqueous solution of manganese nitrate, containing 200 kg/m3CRS-zeolite and 1 kg/m3oxide of manganese,xtruded Chervyakova form, which is dried at 150oC and calcined at 600aboutWith the current of air.

The resulting catalyst contains 50 wt. CRS-zeolite and has the following chemical composition, wt. Oxide manganese Oxide sodium 0.05 0.2 silica 46.8 alumina Rest

The catalyst was tested under the conditions of example 2.

P R I m e R 9. Suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O3160 in an aqueous solution of manganese nitrate, containing 350 kg/m3CRS-zeolite and 12.5 kg/m3manganese oxide, is dispersed with patinirovaniem aluminum hydroxide containing 40 kg/m3aluminium oxide is dried at 120aboutWith, formed into pellets and calcined at 600aboutWith 6 hours in air flow.

The resulting catalyst contains 70 wt. CRS-zeolite and has the following chemical composition, wt. Manganese oxide 2.5 Oxide sodium Oxide 0.5 silicon 68,8 alumina Rest

The catalyst was tested under the conditions of example 5.

P R I m e R 10. Suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O340 in an aqueous solution of gallium nitrate, zinc and manganese, containing 300 kg/m3CRS-zeolite and 3 kg/m3oxides of gallium, zinc and manganese, dispel the chemical composition, wt. Zinc oxide Oxide 0.5 manganese Oxide 0.5 gallium Oxide 0.5 sodium 0.2 silica 46.8 alumina Rest

The catalyst was tested under the conditions of example 1.

P R I m e R 11. Suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O375 in an aqueous solution of gallium nitrate and manganese, containing 200 kg/m3CRS-zeolite and 9.8 kg/m3gallium oxide and 0.2 kg/m3manganese oxide, is dispersed and forth in example 8.

The resulting catalyst contains 50 wt. CRS-zeolite and has the following chemical composition, wt. The 2.45 gallium oxide manganese Oxide sodium 0.05 0.2 silica 48.2 alumina Else

The catalyst was tested under the conditions of example 1.

P R I m e R 12. Suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O335 in an aqueous solution of nitrates of zinc and manganese, containing 200 kg/m3CRS-zeolite, 9,8 kg/m3zinc oxide and 0.2 kg/m3manganese oxide, is dispersed and forth in example 8.

The resulting catalyst contains 50 wt. CRS-zeolite and has the following chemical composition, wt. Zinc oxide Oxide 2.45 manganese Oxide sodium 0.05 0.2 silica 48.1 alumina Else

Catalysate is the totype.

The catalyst in the form of an extruder contains 65 wt. zeolite ZSM-5 with a molar ratio of SiO2/Al2O370 in the alumina matrix and has the following chemical composition, wt. Gallium oxide, sodium Oxide 1.0 0.1 silica 63.1 alumina Rest

The catalyst was tested under the conditions of example 1.

In table. 1 shows the composition of the catalyst and its appearance.

In table. 2 shows the process conditions and product yield.

1. A method of producing motor fuels by processing a mixture of hydrocarbon gases C1C7at elevated temperature and pressure over zeolite catalyst containing the catalyst containing servicecompany zeolite type pentasil a molar ratio of SiO2/AI2O325 160 and a metal oxide, characterized in that the use of a catalyst containing as the metal oxide, manganese oxide or mixture of oxide of manganese with zinc oxide and/or gallium oxide and having the following composition, wt.

Servicecompany zeolite 20-70

Manganese oxide or mixture of oxide of manganese with zinc oxide and/or gallium oxide of 0.05-2.5

The Rest of the binder

2. The method according to p. 1, characterized in that use it is causesa fact, using the catalyst containing the silicate as a binder and having the following chemical composition, wt.

Aluminum oxide 0,5-7,5

Manganese oxide or mixture of oxide of manganese with zinc oxide and/or gallium oxide 0.05-2.5

The sodium oxide 0,05 0,5

Silica Rest

4. The method according to PP. 1 and 2, characterized in that the use of a catalyst containing as a binder alyumooksid and having the following chemical composition, wt.

Manganese oxide or mixture of oxide of manganese with zinc oxide and/or gallium oxide 0.05-2.5

The sodium oxide 0,05 0,5

The silicon oxide 18-68,8

Alumina Rest

5. The method according to PP. 1-4, characterized in that the process is carried out at 400 to 600oC, 0.1 to 2.0 MPa and a space velocity of gas 100-3000 h-1.

6. The method according to PP. 1-5, characterized in that use in microspherical catalyst, or ball, or pellet form or in the form of extrudates.

7. The catalyst for the production of motor fuels containing binder, servicecompany zeolite type pentasil a molar ratio of SiO2/AI2O325-160 and a metal oxide, characterized in that as the oxide of the metal it contains the oxide is, the AU.

Servicecompany zeolite 20-70

Manganese oxide or mixture of oxide of manganese with zinc oxide and/or gallium oxide of 0.05-2.5

The Rest of the binder

8. The catalyst according to p. 7, characterized in that the binder contains a silicate and has the following chemical composition, wt.

Aluminum oxide 0,5-7,5

Manganese oxide or mixture of oxide of manganese with zinc oxide and/or gallium oxide of 0.05-2.5

Oxide, 0.05-0.5 sodium

Silica Rest

9. The catalyst p. 8, characterized in that it contains a mixture of oxides of manganese and zinc.

10. The catalyst PP. 8 and 9, characterized in that it contains a mixture of oxides of manganese and gallium.

11. The catalyst PP. 8 to 10, characterized in that it contains a mixture of oxides of manganese, zinc and gallium.

12. The catalyst according to p. 7, characterized in that it contains as a binder alumina and has the following chemical composition, wt.

Manganese oxide or mixture of oxide of manganese with zinc oxide and/or gallium oxide of 0.05-2.5

The sodium oxide 0,05-0,6

The silicon oxide 18,0-68,8

Alumina Rest

13. The catalyst according to p. 12, characterized in that it contains a mixture of oxides of manganese and zinc.

/P>15. The catalyst PP. 12-14, characterized in that it contains a mixture of oxides of manganese, zinc and gallium.

 

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