The method of hydrotreating catalytic cracking gasoline

 

(57) Abstract:

The present invention relates to chemical technology, in particular to methods of Hydrotreating catalytic cracking gasoline, and can be used in the refining and petrochemical industries. The invention consists in the method of Hydrotreating catalytic cracking gasoline, including the splitting of the original large fractions of gasoline to light N. K. - 130-160°C and heavy fractions of 130-160°C. - K. K. followed by Hydrotreating the heavy fraction in the presence of a catalyst and a mixture of light fraction from the hydrotreated heavy fraction. The process of Hydrotreating heavy fraction is carried out at a temperature of 200-320°C., a pressure of 1.0 to 3.5 MPa, the space velocity of the feedstock 1-10 h-1in the presence of a catalyst containing 8-19% of Moo3and 2-6% of COO and/or NiO, the rest - Al2ABOUT3obtained by impregnation in two stages pre-calcined alumina carrier first with a solution of ammonium molybdate, and then a solution of nitrate of cobalt and/or Nickel nitrate with an intermediate heat treatment at a temperature of 100-200°C and a final calcination at amounts to 400-650°C. the Technical result consists in obtaining the product - components

The present invention relates to chemical technology, in particular to methods of Hydrotreating catalytic cracking gasoline, and can be used in the refining and petrochemical industries.

The main objective is realized in the process of Hydrotreating catalytic cracking gasoline (BCA), is to reduce the sulfur content in it 0,08-0,20 wt.% to the level of not more than 0.05% wt. without a noticeable decrease in its octane number. The principal reaction in the process, along with the hydrogenolysis of sulfur compounds, hydrogenation is diolefines hydrocarbons (HC) with little involvement in the transformation monoolefinic HC.

There is a method of Hydrotreating BCA in the presence aluminoborosilicate catalyst AKM, containing not less than 12.0 wt.% Moo3and not less than 4.0 wt.% Soo, the rest of the media. The main process parameters: pressure of 2 MPa, the volumetric feed rate 3-10 h-1. Reduction of the sulphur content to 0.1 wt.% (when the content of sulfur in the original gasoline 0.2 wt.%) is achieved at a temperature of 250 to 300° C, and the reduction of the sulphur content to 0.05 wt.% - at a temperature of 280-350° [Khavkin C. A., Teregulov D. H., V. L. N. etc. // Chemistry and technology of fuels and oils, 1973, No. 1, S. 22-24 Hawk or the second method is the low gidroobesserivaniya activity of the catalyst, causing the need for Hydrotreating process at high temperatures, which in turn leads to a noticeable loss of octane number of gasoline (1-2 paragraph).

Closest to the present invention to the technical essence and the achieved results is a method of Hydrotreating BCA, including a preliminary fractionation of the original gasoline light N. K. - 120° C and heavy 120° C - K. K. fractions followed by Hydrotreating the heavy fraction in the presence of a catalyst KGM-70 (TU 301-03-87-89) containing 14,0-16,0 wt.% Moo3and 2.8-4.0 wt.% NiO, the rest of the media, and the subsequent mixing of the light fraction from the hydrotreated heavy fraction. The Hydrotreating process is carried out at a temperature of 250-290° C, pressure 3 MPa, the space velocity of the feedstock 2-3 h-1[Khavkin C. A., L. Gulyaeva, A., Osipov, L. N., Kaminski, E. F. //Chemistry and technology of fuels and oils, 2001, No. 1, S. 10-13]. The disadvantage of this method is low gidroobesserivaniya activity of the catalyst, which does not allow to obtain a component of commercial gasoline (after mixing dehydroacetic faction BPC with hydrotreated fraction) with sulfur content less than 0.05 wt.% with a slight loss of octane number (not more than 0.5 points).

This technical problem is solved by dividing the BCA into fractions N. K. - 130-160° C and 130-160° C - K. K. followed by Hydrotreating of the heavy fractions of the BCA 130-160° C - K. K. at a temperature of 200-320° C, pressure of 1.0 to 3.5 MPa, the space velocity of the feedstock 1-10 h-1in the presence of a Hydrotreating catalyst containing 8-19 wt.% Moo3and 2-6 wt.% COO and/or NiO, the rest - Al2ABOUT3obtained by impregnation in two stages pre-calcined alumina carrier first with a solution of ammonium molybdate, and then a solution of nitrate of cobalt and/or Nickel nitrate with an intermediate heat treatment at a temperature of 100 to 200° C and a final calcination at amounts to 400-650° C. After mixing light dehydroacetic fraction (N. K. - 130-160° C) heavy hydrotreated fraction BCA (130-160° C - K. K.) sulfur content in the product (component commodity gasoline) is less than 0.05 wt.%, and the loss of octane number - not more than 0.5 points.

Common features of the invention and prototype are preliminary fractionation BCA on Les hard. Distinctive features of the present invention in comparison with the prototype are the following:

the selection of the BCA heavy fraction with a higher beginning of the boil (130-160° instead of 120° C), which provides for the subsequent Hydrotreating less loss of octane number, because it contains less of olefinic hydrocarbons, olefinic hydrocarbons have a high octane number, and their hydrogenation to saturated hydrocarbons is undesirable;

carrying out Hydrotreating process with the following process parameters: temperature 200-320° C, a pressure of 1.0 to 3.5 MPa, the volumetric feed rate 1-10 h-1in the presence of a catalyst containing 8-19 wt.% Moo3and 2-6 wt.% COO and/or NiO and obtained by the method of double impregnation of alumina media first with a solution of ammonium molybdate, and then a solution of nitrate of cobalt and/or Nickel nitrate with an intermediate heat treatment at a temperature of 100 to 200° C and a final calcination at amounts to 400-650° C.

The proposed set of features a method of Hydrotreating catalytic cracking gasoline corresponds, according to the authors, the condition of patentability “inventive step” nor shall private the proposed set of features leads to the solution of the above tasks. Namely, that the use of aluminoborosilicate and/or alumnirelations catalyst produced by the method of double impregnation of the alumina carrier first with a solution of ammonium molybdate, and then a solution of nitrate of cobalt and/or Nickel nitrate and containing 8-19 wt.% Moo3and 2-6 wt.% COO and/or NiO, allows to obtain a catalytic cracking gasoline with a sulfur content of not more than 0.05 wt.% and the loss of octane number of not more than 0.5 points in the preliminary BCA division into fractions N. K. - 130-160° C and 130-160° C - K. K. and Hydrotreating the heavy fraction at the following process parameters: temperature 200-320° C, a pressure of 1.0 to 3.5 MPa, the volumetric feed rate 1-10 h-1with the subsequent mixture of hydrotreated light and heavy fractions.

Comparative characterization of known and proposed methods of Hydrotreating BCA is given in table. 1.

The invention is illustrated by the following examples.

Example 1. The initial fraction of catalytic cracking gasoline (35-220° C, the sulfur content of 0.08 wt.%) separated into two fractions: lay the second fraction is subjected to Hydrotreating in the presence of the catalyst according to example 19, containing 8 wt.% Moo3and 2 wt.% Soo, the rest - Al2ABOUT3obtained by impregnation in two stages, pre-calcined at a temperature of 650° With alumina media first with a solution of ammonium molybdate, and then a solution of nitrate of cobalt with an intermediate heat treatment at a temperature of 200° C and a final calcination at 650° C. the Hydrotreating Process is conducted under the following conditions: temperature 200° C, a pressure of 1.0 MPa, the volumetric feed rate of 1.0 h-1(mode 1). Then hydrotreated heavy fraction is mixed with dehydroacetic light fraction. The sulfur content in the product mixture component commodity gasoline to 0.05 wt.%, and the loss of octane number (research method) for obtaining a component of commercial gasoline of less than 0.5 point.

Examples 2-9. Analogously to example 1, heavy fraction of BPC is subjected to Hydrotreating in the presence of catalysts obtained in examples 20 to 27, respectively, under conditions relevant to mode 1. The results of the hydrotreatment and quality of the product mixture hydrotreated heavy fraction with dehydroacetic light fraction are given in table.2.

Examples 10 (prototype). Analogously to example 1, the heavy fraction of the BCA podanie sulfur in the product mixture 0,059 wt.%, and the loss of octane number (research method) 0.6 point.

Example 11. The initial fractions of catalytic cracking gasoline (30-205° C, the sulfur content of 0.10 wt.%) separated into two fractions: a light (30-130° C) output 65 wt.%, the sulfur content of 0.05 wt.% and heavy (130-205° C) with a sulfur content of 0.20 wt.%. The heavy fraction is subjected to Hydrotreating in the presence of a catalyst obtained according to example 20 under the following conditions: temperature 250° C, a pressure of 2.0 MPa, the volumetric feed rate 3 h-1(mode 2). Then hydrotreated heavy fraction is mixed with dehydroacetic light fraction. The sulfur content in the product mixture 0,040 wt.%, and the loss of octane number (research method) less than 0.5 point.

Examples 12-13. Analogously to example 11, the heavy fraction of BPC is subjected to Hydrotreating in the presence of catalysts obtained in examples 23 and 26, respectively, under conditions relevant to mode 2. The results of the hydrotreatment and quality of the product mixture hydrotreated heavy fraction with dehydroacetic light fraction are given in table.2.

Examples 14 (prototype). Analogously to example 11, the heavy fraction of BPC is subjected to Hydrotreating in the presence of a catalyst KGM-70 in terms sootvetst) 0.8.

Example 15. The initial fractions of catalytic cracking gasoline (30-190° C, the sulfur content of 0.07 wt.%) separated into two fractions: a light (30-130° C) with the release of 60 wt.% and with a sulfur content of 0.04 wt.% and heavy (130° C-190° C) with a sulfur content of 0.11 wt.%. The heavy fraction is subjected to Hydrotreating in the presence of a catalyst obtained according to example 20, under the following conditions: temperature 320° C, a pressure of 3.5 MPa, the volumetric feed rate 10 h-1(mode 3). Then hydrotreated heavy fraction is mixed with dehydroacetic light fraction. The sulfur content in the product mixture 0,031 wt.%, and the loss of octane number (research method) 0.5 point.

Examples 16-17. Analogously to example 15, the heavy fraction of BPC is subjected to Hydrotreating in the presence of catalysts obtained in examples 23 and 26, respectively, in conditions corresponding to the mode 3. The results of the hydrotreatment and quality of the product mixture hydrotreated heavy fraction with dehydroacetic light fraction are given in table. 2.

Examples 18 (prototype). Analogously to example 15, the heavy fraction of BPC is subjected to Hydrotreating in the presence of a catalyst KGM-70 in conditions corresponding to the mode 3. The sulfur content in the product mixture being 0.036 makalanga at 650° With alumina carrier is impregnated with a solution containing 9.8 g of ammonium molybdate (NH4)6Mo7O24·4H2O. the Impregnated carrier is dried at 200° C for 6 h, and then impregnated with a solution containing 7.8 grams of cobalt nitrate With(NO3)2·6N2O, dried at 120° C for 6 h and calcined at 650° C for 4 h, the Composition of the obtained catalyst: 8 wt.% Moo3, 2 wt.% Soo and the rest - Al2ABOUT3.

Example 19-27. Analogously to example 19, by changing the composition of the active components and the temperature of the intermediate calcination media were obtained samples of the catalysts in examples 19-27, are presented in table. 3.

Presented in table. 2 data shows that the catalysts obtained in examples 19-27, in terms of the proposed method (modes 1-3) provide the product (component of commercial gasoline that meets the standards for sulfur content (less than 0.05 wt.%), whereas under similar conditions the catalyst KGM-70 used in the method of Hydrotreating the prototype shows lower activity and do not provide the required standards for sulfur content. In addition, the proposed method provides prototype in similar conditions, there is great loss of octane number.

The method of Hydrotreating catalytic cracking gasoline, including preliminary fractionation of the original gasoline on light and heavy fractions followed by Hydrotreating the heavy fraction in the presence of a catalyst and a mixture of light fraction from the hydrotreated heavy fraction, wherein the light fraction is the fractional composition of the N. K.-130-160°C, and weight fraction of 130-160°C.-K. K., and the process of Hydrotreating the heavy fraction is carried out at a temperature of 200-320°C., a pressure of 1.0 to 3.5 MPa, the space velocity of the feedstock 1-10 h-1in the presence of a catalyst containing 8-19 wt.% Moo3and 2-6 wt.% COO and/or NiO, the rest - Al2O3obtained by impregnation in two stages pre-calcined alumina carrier first with a solution of ammonium molybdate, and then a solution of nitrate of cobalt and/or Nickel nitrate with an intermediate heat treatment at a temperature of 100-200°C and a final calcination at amounts to 400-650°C.



 

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