The method of obtaining low-sulfur diesel fuel

 

(57) Abstract:

The invention relates to methods of producing low-sulfur diesel by Hydrotreating of the feedstock and can be used in the refining industry. The Hydrotreating process is carried out in two stages with intermediate heating Gutseriev mixture using the first stage alumnirelations catalyst with a predominant pore 9 - 12 nm and in the second stage alumnirelations or aluminoborosilicate catalyst with a predominant pore 4 - 8 nm at a mass ratio of the catalysts of the first and second stage 1:2 - 6. The process is carried out at a temperature of 250 - 350oC in the first stage and 320 - 380oC in the second stage. The method allows to increase the degree of hydrodesulphurization unit feedstock and get diesel fuel with sulfur content less than 0.05 wt.% while increasing the yield of the target fraction 200 - 360oC. 1 C.p. f-crystals, 1 table.

The invention relates to methods of producing low-sulfur diesel fuel and can be used in the oil industry.

A method of obtaining low-sulfur distillate oil put the, the lines, the feed rate of the raw material 1 h-1, a pressure of 3.0 MPa, and a molar ratio of hydrogen to hydrocarbon equal to 4, in the presence of a catalytic system comprising a catalyst hydroconversion and hydrodesulphurization unit, taken in the mass ratio of 50 90 50 10, both of the catalyst used in the form of individual layers and the catalyst hydrodesulphurization unit is situated above the catalyst hydroconversion. The disadvantage of this method is the relatively low degree of hydrodesulphurization unit (ed.St. THE USSR, N 1181522, 1985).

The closest in technical essence and the achieved effect is a method of obtaining low-sulfur diesel by Hydrotreating of the feedstock at elevated temperature using three spaced from top to bottom layers of the catalyst: aluminoborosilicate, alumnirelations and aluminoborosilicate when the mass ratio of catalyst layers 0,5 1,0 4,0 4,5 5,0 8,0 subjected to preliminary solifidian elementary sulfur at a temperature of 350 - 450oC. the Process of Hydrotreating is carried out at a temperature of 320 370oC (RF patent N 1801116, 1993).

The known method has the following disadvantages: the resulting product has a relatively vysokokachestvennoj target faction 200 360oC, especially when the temperature of the process.

The invention is directed to solution of the task of improving the quality of the target product sulfur content not exceeding 0.05 wt. and his exit.

The decision of the given task mediated the new technical result consists in the selection of catalysts with different pore structure, the ratio of the catalysts for their high activity and selectivity.

Obtaining low-sulfur diesel fuel is made by Hydrotreating at elevated temperatures and pressures in the presence of hydrogen production using catalysts for hydrodesulphurization unit.

The process is carried out in two stages with intermediate heating Gutseriev mixture and in the first stage, use aluminumalloy catalyst with a predominant pore 9 12 nm, in the second stage aluminumalloy or allocability catalyst with a predominant pore 4 8 nm at a mass ratio of the catalysts of the first and second stages of 1:2 6, the process is carried out at a temperature of 250 350oC in the first stage, 320 380oC in the second stage.

Example 1. The Hydrotreating process carried out at pilot plant feed M heated each reactor. The hydrodesulphurization unit is subjected to straight-run diesel fraction, 200 360oC with a sulfur content of 1.6 wt. In the first as the reactor load 25 g alumnirelations catalyst (AMN) containing 6.1% NiO, up 15.3% MoO3, Al2O3the rest with the predominant pore 9 - 12 nm and 0.5 g of elemental sulfur. In the second reactor load of 75 g AMN catalyst containing 4.1% of NiO 15,6% MoO3, Al2O3the rest with the predominant pore 4 8 nm and 4 g of elemental sulfur. After purging the installation with nitrogen, pressure testing and replacement of nitrogen to hydrogen raises the pressure to 2.0 MPa and conduct sulfatirovnie catalysts at high temperature up to 400oC, then reduce the temperature in the first reactor to 300oC, in the second reactor to 370oC and served raw. The process hydrodesulphurization unit is carried out at a hydrogen pressure of 3.0 MPa, the space velocity of the raw material 4 h-1, the ratio of hydrogen:feedstock 300 nl/L. Determination of sulfur content in the hydrogenation product is performed on the device "Sulf U. V." method ultraviolet fluorescence. Determination of the yield of fraction 200 360oC performed according to GOST 11011-85. The sulfur content in the resulting hydrogenation product is of 0.015 wt. output faction 200 360oC 97,0 about.

Examples 2 to 4. The condition is howling and second stages. When the temperature in the first stage 250oC and in the second stage 320oC sulfur content in the hydrogenation product is 0.045 wt. the yield of 98.5 about.

The results presented in the table.

Examples 5 to 8. Loading catalysts, sulfur, nitrogen purge, pressurization, and sulfatirovnie catalysts carried out analogously to example 1, except that the second downstream reactor load of 75 g aluminoborosilicate catalyst (AKM), containing 3.9% CoO, 14.2% MoO3, Al2O3the rest of the predominant pore 4 to 8 nm. The process conditions are the same as in example 1 at different temperature stages of the process.

Examples 9 to 12. The process conditions hydrodesulphurization unit are the same as in example 1. When loading catalysts change the mass ratio of the catalysts of the first and second stage hydrodesulphurization unit.

Examples 13 to 16 (for comparison). Conditions for the Hydrotreating process analogous to example 1. In the first reactor and the second stage load AMN or AKM catalysts with a predominant pore 4 to 8 nm.

Examples 17 to 19 (for comparison). Conditions for the Hydrotreating process are the same as in example 1. In both reactor loading is in the table, it contains the indices of the known method.

Thus, the advantage of the proposed method is to increase the degree of gidroobesserivaniya, reducing sulfur content in the hydrotreated fuel while increasing the yield of the target fraction 200 360oC. for example, under comparable process conditions, but with a combination of different catalysts on the first and second stages (examples 1 and 13), the sulfur content in the product in the proposed method below 0.01 wt. while increasing the yield about 0.4. as compared with the known method (example 20) at 0.005 wt. and 3.8 about. respectively. At low process temperatures (examples 2 and 19) reducing the sulfur content is 0,027 wt. with the increase in the yield of about 0.2. and in comparison with the known method (example 21) - of 0.015 wt. and 1.8 about. respectively. Another advantage is the possibility of reducing the rigidity of the Hydrotreating process to ensure the specified quality of diesel fuel and, consequently, increase the duration of mezhregionalnogo period.

1. The method of obtaining low-sulfur diesel by Hydrotreating of the feedstock at elevated temperature and pressure in the presence of vaderotank heated Gutseriev mixture and in the first stage, use aluminumalloy catalyst with a predominant pore 9 12 nm, in the second stage aluminumalloy or allocability catalyst with a predominant pore 4 8 nm at a mass ratio of the catalysts of the first and second stage 1 2 6.

2. The method according to p. 1, wherein the Hydrotreating is carried out at a temperature in the first stage 250 350oC and 320 380oWith the second stage.

 

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FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

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