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INVENTION
Russian Federation Patent RU2051138

METHOD FOR PRODUCING MOTOR FUELS AND CATALYST FOR CARRYING OUT

METHOD FOR PRODUCING MOTOR FUELS AND CATALYST FOR CARRYING OUT

Name of the inventor: Melnikov VB .; Vershinin VI .; Sorokina TV
The name of the patentee: Melnikov Vyacheslav Borisovich; Gorokhovsky Victor A.; Viktor Ivanovich Rodionov
Address for correspondence:
Starting date of the patent: 1993.12.27

Use: oil refining and petrochemical industry. The inventive mixture is C 1 -C 7 hydrocarbon gases, is processed at elevated temperature and pressure, preferably at a temperautre 400-600 ° C and a pressure of 0.1 2.0 MPa, in the presence of a catalyst having the following composition. sverhkremnezemny pentasil-type zeolite with a molar ratio SiO 2 / Al 2O 3 of 25: 160, 20-70; manganese oxide or a mixture of zinc oxide and / or gallium, 0.05-2.5; binder else. The catalyst used in the microsphere, or a ball, or tablet form, or as ekstrucheskoy, or a ball, or tablet form, or as extrudates. The catalyst can comprise silica-alumina as a binder, wherein it has the following chemical composition, by weight. alumina, 0.5-7.5; oxide selected from the group consisting of manganese or zinc, or gallium or mixtures thereof 0.05-2.5; 0.05-0.5 sodium oxide; silicon oxide rest. The catalyst may contain alumina as a binder, wherein it has the following chemical composition, by weight. oxide selected from the group consisting of manganese or zinc, or gallium or mixtures thereof 0.05-2.5; 0.05-0.5 sodium oxide; silica 18,0-68,8; alumina rest. The mixture of oxides as the catalyst may comprise a mixture of zinc oxide, gallium and manganese, or a mixture of zinc oxide and gallium, or a mixture of manganese and gallium oxides, or zinc and manganese oxides. A method of producing motor fuels and catalyst for its implementation provides a gasoline 200 ° C in a yield of 44.8: 43.3% and 88,3-87,4 octane and diesel 200 ° kk with output 14,1-12,9%

DESCRIPTION OF THE INVENTION

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

A method of producing aromatic hydrocarbons such as benzene, toluene, xylene, at elevated temperature and pressure of the light C 2 -C 5 hydrocarbons in the presence of a catalyst comprising a zeolite of type ZSM-5, II B metals or mixtures of metals and VI / in group I or the Periodic system in an amount up to 15% by weight. based on the zeolite and 1 to 90% by weight. alumina binder, silica or clay (the GDR patent N 251710, B 01 J 29/28, 1986).

Known process and aromatization of hydrocarbons of C 2 -C 4 in the presence of a catalyst comprising 0.1 99% by weight. binder, 0.01 to 10% and 0.5 99.99 mas.galliya mas.tseolita synthesized in a fluoride medium with a molar ratio SiO 2 / Al 2 O 3 equal to 12, 1000. The zeolite containing from 0.02 to 15% by weight .ftora (EP N 351312, B 01 J 29/28, 1989).

The closest to the method proposed in technical essence and attainable result is a method for aromatizing a hydrocarbon fraction containing ethylene, propane and propylene, using zeolite ZSM-5 or ZSM-11 containing 0.1% by weight. thorium and gallium or a part of a porous inorganic binder clay, metallic oxides, combinations thereof, and others.

The process is conducted at temperatures up to 700 ° C and a pressure of 0.1-6 MPa, and a weight space velocity of 0.1-400 h -1 (US Pat. N 4629818, C 07 C 12/02, 1986 YG).

A disadvantage of the above patents, including the prototype is not sufficiently high yield of the desired fractions.

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

The problem is solved by the proposed method for producing motor fuels by processing the mixture of hydrocarbon gases C 1 -C 7 at elevated temperatures and pressures on the zeolite catalyst comprising pentasil type zeolite sverhvysokokremnezemisty molar ratio SiO 2 / Al 2 O 3 equal to 25-160 and metal oxide , the distinguishing feature of which is that the catalyst containing manganese oxide as a metal oxide or a mixture of manganese oxide with zinc oxide and / or gallium oxide and having the following composition.

  • Sverhvysokokremne- terrestrial zeolite 20-70
  • Manganese oxide or the mixture of manganese oxide with zinc oxide and / or gallium oxide 0.05-2.5
  • binder Other

Preferably, the catalyst containing the aluminosilicate as binder or alyumooksid.

Thus, using a catalyst having a silica-alumina as a binder, it has the following chemical composition, by weight. Alumina 0.5-7.5

  • Manganese oxide or the mixture of manganese oxide with zinc oxide and / or sodium oxide, gallium oxide, 0.05-2.5 0.05-0.5
  • Silica rest

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

Manganese oxide or a mixture of

manganese oxide with zinc oxide and / or sodium oxide, gallium oxide 0.05-2.5 0.05-0.5 silica alumina rest 18,0-68,8

The process is preferably conducted at a temperature of 400-600 C and a pressure of 0.1-2.0 MPa and a volumetric gas hourly space velocity of 100-3000 h -1.

The catalyst can be used as a microsphere or a ball, or tablet form, or as extrudates.

The problem is solved and a catalyst for the production of motor fuels containing binder sverhvysokokremnezemny pentasil type zeolite having a molar ratio SiO 2 / Al 2 O 3 equal to 25-160, and a metal oxide, the stability of which is distinctive in that as metal oxide it manganese oxide contains manganese oxide or a mixture of zinc oxide and / or gallium oxide and has the following chemical composition by weight.

  • Sverhvysokokremne- terrestrial zeolite 20-70
  • Manganese oxide or the mixture of manganese oxide with zinc oxide and / or gallium oxide 0.05-2.5
  • binder Other

The catalyst may comprise a mixture of said metal oxide in any proportions

As a binder, as indicated, the catalyst may contain alyumooksid or aluminosilicate. The chemical composition of the catalyst with various binders is given above in the specification.

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

The inventive method is as follows: a mixture of gaseous hydrocarbons C 1 -C 7 passed through the above catalyst layer at a temperature of 400-600 C and pressure of 0.1-2.0 MPa and gas hourly space velocity of 100-3000 h -1. As the hydrocarbon gases can be used wet gas condensate gas or propane-butane fraction petrochemical processes, its composition is given in Example 1.

The following are examples of the preparation of the catalyst, and as examples of the method of using the present catalyst.

In the following examples, reagents having the following characteristics were used in the preparation of the catalyst:

  • sulfuric acid, analytical grade, GOST 7712-80;
  • aluminum sulfate, B, GOST 3758-75;
  • gallium nitrate, B, TU 6-09-04-8-74;
  • ammonium sulfate, reagent grade GOST 3769-73;
  • gallium sulfate B, TU 6-09-4736-79;
  • zinc nitrate, B, GOST 5106-77;
  • manganese nitrate, B, GOST 6203-77.

Sodium silicate (water glass) with a silicate module received 2.7 splicing silicate lump (described in the book. Davidyants AA Pervushkin NI "cracking catalyst manufacturing and high-silica gels", M. Chemistry, 1972 168 )..

Example 1. Aluminum sulfate aqueous solution containing 20 kg / m 3, aluminum oxide, and 70 kg / m 3 of sulfuric acid, an aqueous sodium silicate solution (waterglass) NaOH at a concentration of 1.6 kg-eq / m3 and sverhvysokokremnezemnogo suspension (ICS) type zeolite pentasil with a molar ratio SiO 2 / Al 2 O 3 of 40 in an aqueous solution of manganese nitrate, containing 100 kg / m 3 CRS zeolite and 5 kg / m 3 manganese oxide are mixed in a mixer to form a hydrosol which coagulate at 7 ° C and pH 8.0 to form a hydrogel layer ballpoint mineral oil. Hydrogel is then treated with an aqueous solution of ammonium sulfate concentration of 10 kg / m 3at 50 ° C for 18 hours, washed with condensate water at 50 ° C for 18 hours from sulphate ions, dried at 150 ° C and calcined at 550 C. flowing air.

The resulting catalyst contains 30 wt. CRS and zeolite has the following chemical composition, by weight. Alumina 7.5 manganese oxide 1.5 sodium oxide 0.3 Silica rest

The catalyst was tested in the example of processing of hydrocarbon gases C 1-C7 (NGL wide fraction of light hydrocarbons) to flow unit with a fixed bed of catalyst at atmospheric pressure and a temperature of 600 ° C, WHSV of feed (for gas) of 500 h -1, and 1 hour duration of the experiment.

NGL had the following composition. From 1 1.8; C 2 8.3; With 3 42.7; With 4 37.8; With 5 6.4; C 6 2.1; From 7 to 0.9.

Example 2. Aluminum sulfate aqueous solution containing 1.3 kg / m 3, aluminum oxide, and 80 kg / m 3 of sulfuric acid, an aqueous solution of NaOH at a concentration of 1.4 kg of sodium silicate-eq / m 3 and SIS-suspension type pentasil zeolite having a molar ratio of SiO 2 / Al 2 O 3 25 gallium sulfate aqueous solution containing 80 kg / m 3 CRS-zeolite and 0.2 kg / m 3 manganese oxide are mixed in a mixer to form a hydrosol which coagulate at 15 ° C and pH 8 3 in the hydrogel layer to form a ball of mineral oil. Hydrogel is then treated with an aqueous solution of ammonium sulfate concentration of 5 kg / m 3at 30 ° C for 24 hours, washed with condensate water at 30 ° C for 24 hours from sulphate ions, dried at 110 ° C and calcined at 600 ° C flowing air.

The resulting catalyst contains 20 wt. CRS and zeolite has the following chemical composition, by weight. Alumina 0.5 Manganese oxide 0.05 Sodium Oxide 0.05 Silica rest

The catalyst was tested under the conditions of Example 1, but, the volume hourly space velocity of 100 h -1.

Example 3. Aluminum sulfate aqueous solution containing 20 kg / m 3, aluminum oxide, and 70 kg / m 3 of sulfuric acid, the concentration of the aqueous sodium silicate solution by NaOH 1,8 kg-eq / m3 is mixed in a mixer and then in Example 1. After washing, the hydrogel CRS dispersed slurry pentasil type zeolite having a molar ratio SiO 2 / Al 2 O 3 160 in the manganese nitrate aqueous solution and spray dried at 400 ° C and calcination at 600 ° C in flowing air.

The resulting microspheroidal catalyst contains 70 wt. CRS and zeolite has the following chemical composition, by weight. Alumina 6.5 manganese oxide 2.5 sodium oxide 0.5 Silica rest

The catalyst was tested at a temperature of 500 ° C, a pressure of 1 MPa, feed space velocity 2000 h -1, the rest of Example 1.

Example 4. The catalyst prepared in Example 1. Only manganese nitrate instead of a mixture of gallium nitrate, zinc and manganese.

The resulting catalyst contains 30 wt. CRS and zeolite has the following chemical composition, by weight. Alumina 7.5 Gallium Oxide Zinc Oxide 0.5 0.5 0.5 Manganese oxide sodium oxide 0.3 Silica rest

The catalyst was tested under the conditions of Example 1.

Example 5. After washing, the hydrogel obtained in Example 3 was dispersed slurry CRS-type zeolite of pentasil with a molar ratio SiO 2 / Al 2 O 3 160 to an aqueous solution of gallium nitrate and manganese and spray dried at 400 ° C and calcination at 600 ° C flowing air.

The resulting microspheroidal catalyst contains 50 wt. CRS and zeolite has the following chemical composition, by weight. Alumina Oxide 6.5 2.45 Ga 0.05 Mn oxide sodium oxide 0.5 Silica rest

The catalyst was tested at a temperature of 400 ° C, a pressure of 2 MPa, feed space velocity of 3000 hr -1, the rest of Example 1.

Example 6. After washing, the hydrogel obtained in Example 3 was dispersed slurry CRS-type zeolite of pentasil with a molar ratio SiO 2 / Al 2 O 3 160 to an aqueous solution of zinc nitrate and manganese and spray dried at 400 ° C and calcination at 600 ° C flowing air.

The resulting microspheroidal catalyst contains 70 wt. CRS and zeolite has the following chemical composition, by weight. Alumina 6.6 Zinc oxide manganese oxide 2.45 0.05 sodium oxide 0.5 Silica rest

The catalyst was tested at a temperature of 500 ° C, a pressure of 2 MPa, feed space velocity of 3000 hr -1, the rest of Example 1.

Example 7. The suspension CRS-type zeolite of pentasil with a molar ratio SiO 2 / Al 2 O 3 25 aqueous solution of manganese nitrate, containing 200 kg / m 3 CRS zeolite and 15 kg / m 3 manganese oxide dispersed peptized aluminum hydroxide containing 20 kg / m 3 of aluminum oxide and 1 kg / m 3 with nitric acid, and subjected to ammonium-forming hydrocarbon, dried at 120 ° C and calcined at 550 ° C in flowing air.

Ball resulting catalyst contains 20 wt. CRS and zeolite has the following chemical composition, by weight. Manganese oxide 1.5 Sodium Oxide 0.05 Silica Alumina 18.0 Other

The catalyst was tested under the conditions of Example 1.

Example 8. The suspension CRS-type zeolite of pentasil with a molar ratio SiO 2 / Al 2 O 3 of 40 in an aqueous solution of manganese nitrate, containing 200 kg / m 3 CRS-zeolite, and 1 kg / m 3 manganese oxide dispersed peptized aluminum hydroxide containing 20 kg / m 3, aluminum oxide, and the obtained extrudate chervyachkovoy form which was dried at 150 o C and calcined at 600 ° C in flowing air.

The resulting catalyst contains 50 wt. CRS and zeolite has the following chemical composition, by weight. Manganese oxide 0.05 sodium oxide 0.2 Silica Alumina 46.8 Other

The catalyst was tested under the conditions of Example 2.

Example 9. CRS suspension pentasil type zeolite having a molar ratio SiO 2 / Al 2 O 3 160 a manganese nitrate aqueous solution containing 350 kg / m 3 CRS zeolite and 12.5 kg / m 3 manganese oxide dispersed peptized aluminum hydroxide containing 40 kg / m 3, aluminum oxide, dried at 120 ° C, formed into tablets and calcined at 600 ° C for 6 hours in flowing air.

The resulting catalyst contains 70 wt. CRS and zeolite has the following chemical composition, by weight. Manganese oxide 2.5 sodium oxide 0.5 Silica Alumina 68.8 Other

The catalyst was tested under the conditions of Example 5.

Example 10. The suspension CRS-type zeolite of pentasil with a molar ratio SiO 2 / Al 2 O 3 of 40 in an aqueous solution of gallium nitrate, zinc and manganese containing 300 kg / m 3 CRS zeolite and 3 kg / m 3, gallium oxide, zinc and manganese, dispersed further in example 8.

The resulting catalyst contains 50 wt. CRS and zeolite has the following chemical composition, by weight. Zinc oxide manganese oxide 0.5 0.5 0.5 gallium oxide sodium oxide 0.2 Silica Alumina 46.8 Other

The catalyst was tested under the conditions of Example 1.

Example 11. CRS suspension pentasil type zeolite having a molar ratio SiO 2 / Al 2 O 3 of 75 in an aqueous solution of gallium nitrate and manganese containing 200 kg / m 3 CRS-zeolite and 9.8 kg / m 3, gallium oxide and 0.2 kg / m 3 manganese oxide dispersed further in example 8.

The resulting catalyst contains 50 wt. CRS and zeolite has the following chemical composition, by weight. Gallium Oxide Manganese Oxide 2.45 0.05 sodium oxide 0.2 Silica Alumina 48.2 Other

The catalyst was tested under the conditions of Example 1.

Example 12. CRS suspension pentasil type zeolite having a molar ratio SiO 2 / Al 2 O 3 of 35 in an aqueous solution of zinc nitrate and manganese containing 200 kg / m 3 CRS-zeolite, 9.8 kg / m3 of zinc oxide and 0.2 kg / m 3 manganese oxide dispersed further in example 8.

The resulting catalyst contains 50 wt. CRS and zeolite has the following chemical composition, by weight. Zinc oxide manganese oxide 2.45 0.05 sodium oxide 0.2 Silica Alumina 48.1 Other

The catalyst was tested under the conditions of Example 1.

Example 13 (for comparison). The catalyst is prepared according to prior art.

The resultant catalyst in the form of an extruder contains 65 wt. zeolite ZSM-5 having a molar ratio SiO 2 / Al 2 O 3 alumina binder at 70 and has the following chemical composition, by weight. Gallium oxide 1.0 sodium oxide 0.1 Silica Alumina 63.1 Other

The catalyst was tested under the conditions of Example 1.

Table. 1 shows the composition and form of the catalyst.

Table. 2 shows the process conditions and product yield.

CLAIM

1. A method of producing motor fuels by processing the mixture C 1 C 7 hydrocarbon gases at elevated temperature and pressure on the zeolite catalyst comprising a catalyst containing sverhvysokokremnezemny pentasil-type zeolite with a molar ratio SiO 2 / AI 2 O March 25 160 and a metal oxide, wherein that a catalyst containing manganese oxide as a metal oxide or manganese oxide mixed with zinc oxide and / or gallium oxide and having the following composition.

  • Sverhvysokokremnezemny zeolite 20-70
  • Manganese oxide or the mixture of manganese oxide with zinc oxide and / or gallium oxide 0.05-2.5
  • binder Other

2. A method according to claim 1, characterized in that the catalyst containing the aluminosilicate as binder or alyumooksid.

3. The method of claim. 1 and 2, characterized in that the catalyst containing the aluminosilicate as binder and having the following mechanical composition, wt.

  • Alumina 0.5-7.5
  • Manganese oxide or the mixture of manganese oxide with zinc oxide and / or gallium oxide 0.05 2.5
  • Sodium Oxide 0.05 0.5
  • Silica rest

4. The method of claim. 1 and 2, characterized in that the catalyst contains as binder alyumooksid and having the following chemical composition, by weight.

  • Manganese oxide or the mixture of manganese oxide with zinc oxide and / or gallium oxide 0.05 2.5
  • Sodium Oxide 0.05 0.5
  • Silica 18-68,8
  • Alumina Other

5. The method of claim. 1-4, wherein the process is carried out at 400-600 o C, 0.1 MPa and 2.0 volumetric gas hourly space velocity of 100-3000 h -1.

6. The method of claim. 1-5, wherein the catalyst is used in the microsphere, or a ball, or tablet form, or as extrudates.

7. A catalyst for producing motor fuels containing binder sverhvysokokremnezemny pentasil-type zeolite with a molar ratio SiO 2 / AI 2 O 3, 25-160 and a metal oxide, characterized in that as metal oxide it contains a mixture of manganese oxide or manganese oxide with zinc and / or gallium oxide with the following component, in weight.

  • Sverhvysokokremnezemny zeolite 20-70
  • Manganese oxide or the mixture of manganese oxide with zinc oxide and / or gallium oxide 0.05-2.5
  • binder Other

8. The catalyst according to claim 7, characterized in that it contains as binder and aluminosilicate has a chemical composition, by weight.

  • Alumina 0.5-7.5
  • Manganese oxide or the mixture of manganese oxide with zinc oxide and / or gallium oxide 0.05-2.5
  • Sodium Oxide 0.05-0.5
  • Silica rest

9. The catalyst according to claim. 8, characterized in that it comprises a mixture of zinc and manganese oxides.

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

11. The catalyst of claim. On August 10, characterized in that it contains a mixture of oxides of manganese, zinc and gallium.

12. The catalyst according to claim 7, characterized in that as binder it contains aluminum oxide and has the following chemical composition, by weight.

  • Manganese oxide or the mixture of manganese oxide with zinc oxide and / or gallium oxide 0.05-2.5
  • Sodium Oxide 0.05-0.6
  • Silica 18,0-68,8
  • Alumina Other

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

14. The catalyst of claim. 12 and 13, characterized in that it contains a mixture of oxides of manganese and gallium.

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

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Publication date 07.04.2007gg