Method of refining gasoline

 

(57) Abstract:

Usage: oil refining and petrochemical industry. The inventive improvement of gasoline is carried out at elevated temperature and pressure, preferably at 200 to 400C., a pressure of 0.1 to 1 MPa, at aluminosilicate zeolite catalyst containing 0.5 to 5 wt. sverkhvysokochastotnogo zeolite type pentasil a molar ratio of silicon oxide to aluminum oxide, 25 to 90, amorphous silica-alumina basis. The used catalyst has a chemical composition, wt. 0.5 to 7.5 aluminum oxide; 0,05 0,5 sodium oxide; the remaining silicon oxide, or 0.5 7.5 aluminum oxide; 0.05 to 2.5 zinc oxide; 0,05 0,5 sodium oxide; the remaining silicon oxide, or 0.5 7.5 aluminum oxide; 0,05 2,5 gallium oxide; 0,05 0,5 sodium oxide; the rest of the silicon oxide. 1 C. p. F.-ly, 1 table.

The invention relates to catalytic reforming, in particular the elevation of gasoline over zeolite catalysts, and can be used in the refining and petrochemical industries.

There is a method of refining of gasoline produced in thermal cracking in the presence of a catalyst containing 9-29 wt. SWE basis. The resultant catalysate at 480aboutWith, the duration of the experience 1 h, the mass feed rate of the raw material 4,4-6,7 h-175 wt. when the octane number of 76.4-79,6.

(Lewinter M. E. and other Beautification gasoline, thermal cracking at high zeolite catalyst. Oil refining and petrochemistry", N 3, 1991, S. 7-9).

The present invention is to develop a catalytic method for the refining of gasoline, allowing to increase the output of refined gasoline and its octane number.

The problem is solved by the proposed method of refining gasoline on zeolite-containing catalyst containing sverhkrupnyh zeolite in an amorphous aluminosilicate based at elevated temperature and pressure, the distinctive feature of which is that the use of aluminosilicate zeolite-containing catalyst containing 0.5-5 wt. sverkhvysokochastotnogo zeolite type pentasil a molar ratio of SiO2/Al2O3equal 25-90, amorphous silica-alumina base, and the catalyst has the following chemical composition (wt. ) aluminium oxide 0,5-7,5; oxide, 0.05-0.5 sodium; silica rest, or aluminum oxide, 0.5 to 7.5% zinc oxide 0 silica rest.

The process is preferably carried out at 200-400aboutC, a pressure of 0.1-1 MPa and space velocity of the raw material of 0.5-2.5 h-1.

The invention consists in the following.

Raw naphtha or gasoline, thermal cracking is passed through a fixed catalyst bed through conduit installation. The process is conducted at 200-400aboutC, a pressure of 0.1-1 MPa, the space velocity of the raw material of 0.5-2.5 h-1.

Characteristics of the raw materials used are presented in the examples.

Below are examples of the preparation of the catalyst, and the results of its tests in the proposed method of refining gasoline (see data table).

As can be seen from the data presented, the proposed method allows to increase the output of refined gasoline to 2-21,2 wt. with a simultaneous increase in the octane number of gasoline 3.5 and 8.6.

P R I m e R 1. An aqueous solution of aluminum sulfate containing 20 kg/m3Al2O3and 70 kg/m3H2SO4, an aqueous solution of sodium silicate (liquid glass) concentration of NaOH 1.6 kg-EQ/m3and suspension sverkhvysokochastotnogo (ICS) zeolite type pentasil a molar ratio of SiO2/Al2O340, containing 100 kg/m< 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 water at 50aboutC for 20 h from sulfate ions, dried at 150aboutC and calcined at 550aboutC for 12 h in air flow.

The catalyst containing 2 wt. CRS-zeolite and has the following chemical composition, wt. aluminum oxide 6.0 sodium oxide 0.1 silica rest (up to 100)

P R I m m e R 2. An aqueous solution of aluminum sulfate containing 20 kg/m3Al2O3and 70 kg/m3H2SO4, an aqueous solution of sodium silicate concentration of NaOH 1.6 kg-EQ/m3and suspension CRS-zeolite type pentasil a molar ratio of SiO2/Al2O340 in an aqueous solution of aluminum sulfate containing 100 kg/m3CRS-zeolite and 5 kg/m3Al2O3are mixed in the mixer. Further according to the example 1.

The catalyst containing 2 wt. CRS-zeolite and has the following chemical composition, wt. aluminum oxide 6.1 oxide sodium 0.1 silica else

P R I m e R 3. The catalyst was prepared as in example 1. After activation of ammonium sulfate hydrogel treated with an aqueous solution of aluminum sulfate concentration 2 the hydrated catalyst containing 2 wt. CRS-zeolite and has the following chemical composition, wt. aluminum oxide 7.5 sodium oxide 0.1 silica else.

P R I m e R 4. The catalyst was prepared as in example 1. After washing the condensate water, the hydrogel is subjected to spray drying at 400aboutC and calcining at 600aboutWith 12 hours in an environment of steam-air mixture containing up to about 40. steams. The catalyst has the microspheric form. The catalyst containing 2 wt. CRS-zeolite and has a chemical composition of example 1.

P R I m e R 5. An aqueous solution of aluminum sulfate containing 20 kg/m3aluminum oxide and 70 kg/m3sulfuric acid and an aqueous solution of sodium silicate concentration of NaOH 1.6 kg-EQ/m3mix in the mixer and forth in example 1. After washing, the hydrogel is dispersed with SPCS-zeolite type pentasil with a molar ratio of SiO2/Al2O340 and subjected to spray drying under the conditions of example 4. The catalyst containing 2 wt. CRS-zeolite and has a chemical composition of example 1.

P R I m e R 6. The catalyst was prepared as in example 5. After dispersion with SPCS-zeolite and timke on the filter press receive the extrudate Chervyakova form, which is dried at 150aboutC and calcined at 600and m e R 7. The catalyst was prepared as in example 6. After the filter press, the hydrogel is dried at 150aboutC. and Then formed into pellets and calcined at 600aboutAt 6 a.m. the catalyst containing 2 wt. CRS-zeolite and has a chemical composition of example 1.

P R I m e R 8. An aqueous solution of aluminum sulfate containing 2 kg/m3Al2O3and 90 kg/m3H2SO4, an aqueous solution of sodium silicate concentration of NaOH 1.8 kg-EQ/m3and suspension CRS-zeolite with a molar ratio of SiO2/Al2O325, contains 10 kg/m3CRS-zeolite are mixed in the mixer with the formation of a Hydrosol, which is coagulated in 5aboutC and a pH of 8.4 in the hydrogel pellet form in a layer of mineral oil. Then the hydrogel treated with an aqueous solution of ammonium nitrate concentration of 5 kg/m3when 30aboutC for 36 h, washed with condensate water at 30aboutC for 18 h from nitrate ions, dried at 120aboutC and calcined at 500aboutC for 24 h in air flow.

The resulting catalyst contains 0.5 wt. CRS-zeolite and has the following chemical composition, wt. alumina oxide 0.5 sodium 0.05 silicon oxide rest.

P R I m e R 9. An aqueous solution of aluminum sulfate containing 25 kg/the aOH 1.4 kg-EQ./m3and suspension CRS-zeolite with a molar ratio of SiO2/Al2O390 containing 150 kg/m3CRS-zeolite are mixed in the mixer with the formation of a Hydrosol, which coagulated at 20aboutC and pH 7.8 in the hydrogel pellet form in a layer of mineral oil. Then the hydrogel treated with an aqueous solution of ammonium chloride concentration of 20 kg/m3at 60aboutC for 12 h, washed with condensate water at 60aboutC for 8 h from the chloride ions, dried at 190aboutC and calcined at 600aboutC for 6 h in air flow.

The catalyst containing 5 wt. CRS-zeolite and 95 wt. amorphous aluminosilicate framework, having the following chemical composition, wt. aluminum oxide 7.5 oxide sodium oxide 0.5 silica rest.

P R I m e R 10 (for comparison). The catalyst prepared according to the prototype 1.

The catalyst containing 10 wt. CRS-zeolite with a molar ratio of SiO2/Al2O330 and 90 wt. amorphous aluminosilicate framework, having the following chemical composition, wt. aluminum oxide 6 oxide sodium oxide 0.2 silica rest.

The catalysts according to examples 1-10 were tested in the process of refining gasoline running on installing the raw 1H-1and duration of experience 0.5 hours

Straight-run gasoline had the following characteristics: Density, g/cm30,71

Limits boiling GOST,aboutWith 35-190 sulfur Content, wt. 0,1 Octane number (m m) 50,4

Group hydrocarbon composition, wt. Unsaturated 4 Paraffin-naphthenic 87 Aromatic 9

P R I m e R s 11-12. The catalyst of examples 1 and 10 respectively were similar to the catalysts of examples 1-9 at 200aboutC and space velocity of the feedstock 0.5 h-1.

P R I m e R s 13-14. The catalysts of examples 1 and 10 respectively were similar to the catalysts of examples 1-9 400aboutC and space velocity of the raw materials 2.5 h-1.

P R I m e R s 15-16. The catalysts of examples 1 and 10 respectively were similar to the catalysts of examples 1-9 at a pressure of 1 MPa, a temperature of 350aboutC, space velocity of the raw material 1 h-1and duration of experience 0.5 hours

P R I m e R s 17-26. The catalysts according to examples 1-10 respectively were in the process of refining gasoline, thermal cracking at atmospheric pressure, a temperature of 350aboutC, space velocity of the raw material 1 h-1and duration of experience 0.5 hours

Gasoline Ter is SUP>about
With 60-180 sulfur Content, wt. 0,3 Octane number (m m) 62,7

Group hydrocarbon composition, wt. Unsaturated 38 Paraffin-naphthene Aromatic 51 11

P R I m e R s 27-28. The catalysts of examples 1 and 10 respectively were similar to the catalysts of examples 17-26 at 200aboutC and space velocity of the feedstock 0.5 h-1.

P R I m e R s 29-30. The catalysts of examples 1 and 10 respectively were similar to the catalysts of examples 17-26 at 400aboutC and space velocity of the raw materials 2.5 h-1.

P R I m e R s 31-32. The catalysts of examples 1 and 10 respectively were similar to the catalysts of examples 15-23 at a pressure of 1 MPa.

P R I m e R 33. The catalyst was prepared as in example 1. After activation of ammonium sulfate hydrogel treated with an aqueous solution of zinc sulfate concentration of 2 kg/m3at the 50aboutC for 6 h and further according to the example 1.

The catalyst containing 2 wt. CRS-zeolite and has the following chemical composition, wt. aluminum oxide 6.0 zinc oxide, sodium oxide 1.0 0.1 silica else

P R I m e R 34. An aqueous solution of aluminum sulfate containing 2 kg/m3aluminum oxide and 90 kg/m3sulfuric acid, aqueous solution SILM 25 in an aqueous solution of zinc sulfate, containing 10 kg/m3CRS-zeolite and 1 kg/m3zinc oxide is mixed in the mixer. Further according to the example 8.

The resulting catalyst contains 0.5 wt. CRS-zeolite and has the following chemical composition, wt. alumina oxide 0.5 zinc oxide sodium 0.05 0.05 silicon oxide rest

P R I m e R 35. An aqueous solution of aluminum sulfate and zinc, containing 25 kg/m3aluminum oxide, 8,3 kg/m3zinc oxide and 50 kg/m3of sulfuric acid. Further according to the example 9.

The catalyst containing 5 wt. CRS-zeolite and has the following chemical composition, wt. aluminum oxide 7.5 zinc oxide 2,5 oxide sodium oxide 0.5 silica rest

P R I m e R 36. The catalyst was prepared as in example 33. After washing, the hydrogel is subjected to spray drying at 400aboutC and calcining at 600aboutWith in the air. The resulting catalyst has a microspherical form and contains 2 wt. CRS-zeolite and has a chemical composition of example 33.

P R I m e R 37. The catalyst was prepared as in examples 33. After dispersion and spin on filter press receive the extrudate Chervyakova form under the conditions of example 6. The catalyst containing 2 wt. CRS-zeolite and has a chemical composition of example 33.

Katal the Catalyst according to example 33 was tested under the conditions of examples 11-12.

P R I m e R 39. The catalyst according to example 33 was tested under the conditions of examples 13-14.

P R I m e R 40. The catalyst according to example 33 was tested under the conditions of examples 15-16.

P R I m e R s 41-45. The catalysts according to examples 33 to 37, respectively, experienced at the test conditions of the catalysts of examples 17-26.

P R I m e R 46. The catalyst according to example 33 was tested under the conditions of examples 27-28.

P R I m e R 47. The catalyst according to example 33 was tested under the conditions of examples 29-30.

P R I m e R 48. The catalyst according to example 33 was tested under the conditions of examples 31-32.

P R I m e R 49. 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 1.6 kg-EQ/m3and suspension CRS-zeolite type pentasil with a molar ratio of SiO2/Al2O340 in an aqueous solution of gallium nitrate containing 10 kg/m3CRS-zeolite and 6 kg/m3gallium oxide is mixed in the mixer. Further according to the example 1.

The catalyst containing 2 wt. CRS-zeolite and has the following chemical composition, wt. aluminum oxide 6,0 gallium oxide 1,2-oxide sodium 0.1 silica else

P R I m e R 50. Water RA is/m3of sulfuric acid. Further according to the example 9. The catalyst containing 5 wt. CRS-zeolite and has the following chemical composition, wt. alumina oxide gallium 7.5 2.5 oxide sodium oxide 0.5 silica rest.

P R I m e R 51. The catalyst was prepared as in example 7. After activation of ammonium sulfate hydrogel treated with an aqueous solution of gallium sulfate concentration of 1 kg/m3when 30aboutC for 6 h and further in example 8.

The resulting catalyst contains 0.5 wt. CRS-zeolite and has the following chemical composition, wt. alumina oxide 0.5 gallium oxide sodium 0.05 0.05 silicon oxide rest.

P R I m e R 52. The catalyst was prepared as in example 49. After washing, the hydrogel is subjected to spray drying at 400aboutC and calcining at 600aboutWith in the air. The resulting catalyst has a microspheric form, contains 2 wt. CRS-zeolite and has a chemical composition of example 49.

P R I m e R 53. The catalyst was prepared under the conditions of example 49. After dispersion and spin on filter press receive the extrudate Chervyakova form under the conditions of example 6. The catalyst containing 2 wt. CRS-zeolite and has a chemical composition of example 49.

Catalysts for approx the example 49 was tested under the conditions of examples 11-12.

P R I m e R 55. The catalyst according to example 49 was tested under the conditions of examples 13-14.

P R I m e R 56. The catalyst according to example 49 was tested under the conditions of examples 15-16.

P R I m e R s 57-61. The catalysts obtained in examples 49-53, respectively, experienced at the test conditions of the catalysts of examples 17-26.

P R I m e R 62. The catalyst according to example 49 was tested under the conditions of examples 27-28.

P R I m e R 63. The catalyst according to example 49 was tested under the conditions of examples 29-30.

P R I m e R 64. The catalyst according to example 49 was tested under the conditions of examples 31-32.

1. METHOD of REFINING GASOLINE by contact with a catalyst containing servicecompany zeolite in an amorphous aluminosilicate based at elevated temperature and pressure, characterized in that the use of a catalyst containing as sverkhkriticheskogo zeolite zeolite type pentasil a molar ratio of SiO2/ Al2O325 90, in the amount of 0.5 to 5.0 wt. and having a chemical composition, wt.

Aluminum oxide is 0.5 to 7.5

The sodium oxide 0,05 0,5

Silica Rest

or catalyst containing the zeolite zeolite type pentasil a molar ratio of SiO"ptx2">

Aluminum oxide is 0.5 to 7.5

Zinc oxide 0,05 2,5

The sodium oxide 0,05 0,5

Silica Rest

or catalyst containing the zeolite zeolite type pentasil a molar ratio of SiO2/ Al2O325 90, optionally containing gallium oxide and having a chemical composition, wt.

Aluminum oxide is 0.5 to 7.5

The gallium oxide 0.05-2.5

The sodium oxide 0,05 0,5

Silica Rest

2. The method according to p. 1, wherein the process is carried out at a temperature of 200 400oC, a pressure of 0.1 to 1.0 MPa, the space velocity of the raw material of 0.5 to 2.5 h-1.

 

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