RU2284344C1 - Petroleum feedstock hydrogenation processing method - Google Patents

Abstract

FIELD: petroleum processing.

SUBSTANCE: blend composed of vacuum distillate and distilled fraction of secondary destruction processes is subjected to hydrogenation processing at elevated temperature and pressure in presence of catalyst, said secondary destruction process fraction containing sulfur up to 1% and being taken in amount 2 to 25% based on total weight of feedstock, while vacuum distillate boils up to 560°C. More particularly, secondary destruction process fraction is catalytic cracking, visbreaking, or retarded coking gas oil fraction. Process is carried out at 340-415°C, pressure 4-10 MPa, and feedstock supply volume flow rate 0.5-2.0 h-1.

EFFECT: improved purification degree of residue and enabled involvement of heavy vacuum distillate.

2 cl, 3 ex

Description

The invention relates to the field of oil refining, specifically to a method for the hydrogenation processing of petroleum feeds.

A known method of light hydrocracking of sulfur vacuum distillates, which allows to obtain 35-40% of diesel fuel and 2-4% of gasoline distillate. The hydrocracking process is carried out in the presence of a catalyst at a pressure of 5.5 MPa, a volumetric feed rate of 0.59-0.68 h ^-1 , a temperature of 385-420 ° C and a hydrogen-containing gas circulation ratio of 1000-1300 nm ³ / m ³ . The total degree of conversion is 40-45 wt.% For raw materials, while there remains an unconverted residue (55-60 wt.%), Which, due to the low sulfur content (about 0.1 wt.%), Can be used as a refined raw material for catalytic cracking.

The resulting diesel distillate containing 0.04-0.05 wt.% Sulfur can be used directly as commercial diesel fuel or serve as a component of the latter. ("Oil Refining and Petrochemicals", 1999, No. 11, p. 28.)

The disadvantage of this method is the complex catalytic system, which involves the use of a three-stage loading of catalysts (successively hydrotreating, hydrogenation and hydrocracking), as well as the inability to process vacuum distillates with a boiling end exceeding 520-525 ° C, which complicates the involvement of heavier vacuum distillates (with an end boiling up to 560 ° C).

Closest to the claimed is a method of hydrogenation processing of a mixture of vacuum distillate (fractions 350-500 ° C) and a wide gas oil fraction of delayed tar coking in an amount of 35 wt.% On raw materials with a sulfur content of 1.6 wt.%.

Hydrogenation processing is carried out in two stages: at the first stage at a temperature of 390 ° C and a volumetric feed rate of 2.5 h ^-1 , in the second stage at a temperature of 400 ° C and a volumetric feed rate of 2.5 h ^-1 , at a ratio hydrogen-containing gas / feed - 1000 nm ³ / m ³ at a pressure of 5 MPa in the presence of a nickel-molybdenum catalyst on alumina (stage I) and a nickel-molybdenum catalyst on a zeolite catalyst (stage II). 63 wt.% Of the diesel fraction of 150-370 ° C with a sulfur content of 0.04 wt.% Of the diesel fuel component and 30 wt.% Of the residue with a sulfur content of 0.15 wt.%, Which can be used as a boiler fuel. (RF patent No. 2205200, 2003, example 3.)

The disadvantage of this method is the inability to process vacuum distillates with a boiling end above 500 ° C, which significantly reduces the involvement in the processing of heavy vacuum distillates (with a boiling end up to 560 ° C). Among the shortcomings should also include an insufficiently deep degree of purification of the residue from sulfur (0.15 wt.%), Which leads to the fact that it can be used as a component of boiler fuel, and only after additional preparation - as a raw material for catalytic cracking.

The objective of the invention is to develop a method for the hydrogenation processing of petroleum feedstocks, which allows the processing of heavy vacuum distillates with a boiling end up to 560 ° C, while obtaining low-sulfur diesel distillates, and at the same time improve the quality of the unconverted residue that can be used as catalytic cracking feedstock without additional training.

To solve this problem, we propose a method for the hydrogenation processing of petroleum feedstock, which is a mixture of a vacuum distillate and a distillate fraction of secondary destructive processes, at elevated temperature and pressure in the presence of a catalyst, which differs in that they use a distillate fraction of secondary destructive processes with a sulfur content of up to 1 wt. % in an amount of 2-25 wt.% for raw materials.

Moreover, vacuum distillate with a boiling end up to 560 ° C is used as a raw material, and gas oil fractions of catalytic cracking, visbreaking, delayed coking, boiling inside the temperature range 180-530 ° C are used as the distillate fraction of the secondary destructive processes.

Hydrogenation processing is carried out at a pressure of 4-10 MPa, a temperature of 340-415 ° C, a volumetric feed rate of 0.5-2.0 h ^-1 .

It should be noted that the distillate fraction of the secondary destructive processes with a sulfur content of up to 1 wt.% Is a "hydrogen donor", the addition of which to the vacuum distillate with a boiling end up to 560 ° C promotes the appearance of atomic hydrogen in the reaction system. This intensifies the required catalytic reactions, allows to achieve a deepening of the desulfurization reactions and destruction of the feedstock without increasing the pressure above 10 MPa. If the sulfur content is above 1 wt.% In the distillate fraction of the secondary destructive processes, atomic hydrogen will participate in the binding of the "excess" sulfur of this fraction without participating in the reactions of the desired direction.

The use of a distillate fraction of secondary destructive processes as a "hydrogen donor" in an amount of less than 2 wt.% Is not enough to intensify the process of hydrogenation processing of a heavier vacuum distillate, and in an amount of more than 25 wt.% It is not economically feasible.

The hydrogenation process is carried out in the presence of catalysts (a system consisting of one or two sequentially located catalysts).

The inventive method allows to obtain diesel distillate with a yield of 10-45 wt.% With a sulfur content of 0.01-0.02 wt.%, Which can be used as a component of diesel fuel, as well as a refined residue with a yield of 47-80 wt.% With a content sulfur 0.02-0.06 wt.%, which is a high quality raw material for the catalytic cracking process.

The following are specific examples of the implementation of the proposed method.

Example 1

A mixture of vacuum distillate of West Siberian oil (fraction 350-560 ° C) in an amount of 75 wt.%, Characterized by the following indicators:

density at 20 ° С - 926 kg / m ³ ;

sulfur content - 1.7 wt.%;

nitrogen content - 0.2 wt.%;

vanadium content - 0.55 g / t;

nickel content - 0.26 g / t;

boils up to 360 ° С - 3 vol.%

and the gas oil fraction of catalytic cracking in an amount of 25 wt.%, characterized by the following indicators:

boiling limits - 200-350 ° C;

density at 20 ° C - 890 kg / m ³ ;

sulfur content - 0.3 wt.%

subjected to hydrogenation processing at a pressure of 10 MPa, a temperature of 390 ° C, a volumetric feed rate of 2.0 h ^-1 , a hydrogen-containing gas / feed ratio of 1500 vol / vol. in the presence of a zeolite-containing aluminum-nickel-molybdenum catalyst.

The result is 4 wt.% Gasoline distillate, 45 wt.% Diesel distillate (fraction 180-350 ° C) with a sulfur content of 0.01 wt.%, Which can serve as a component of commercial diesel fuel, and 47 wt.% Ennobled residue boiling above 350 ° C and characterized by a sulfur content of 0.02 wt.%, which is a high-quality raw material for the catalytic cracking process (density at 20 ° C - 920 kg / m ³ , nitrogen content - less than 0.05 wt.%, vanadium content - 0.10 g / t, nickel content - 0.10 g / t).

Example 2

A mixture of vacuum distillate of sulfuric Tatar oils (fraction 350-540 ° C) in an amount of 90 wt.%, Characterized by the following indicators:

density at 20 ° С - 924 kg / m ³ ;

sulfur content - 2.4 wt.%;

nitrogen content - 0.3 wt.%;

vanadium content - 0.7 g / t;

nickel content - 0.4 g / t;

boils up to 360 ° С - 4 vol.%

and a gas oil fraction of viscous cracking in an amount of 10 wt.%, characterized by the following indicators:

boiling limits - 165-400 ° C;

density at 20 ° C - 870 kg / m ³ ;

sulfur content - 1.0 wt.%

subjected to hydrogenation processing at a pressure of 6 MPa in two stages: in the first stage at a temperature of 340 ° C and a volumetric feed rate of 1.5 h ^-1 ; in the second stage at a temperature of 400 ° C and a volumetric feed rate of 1.5 h ^-1 (the ratio of hydrogen-containing gas / feed is 1000 vol./about.) in the presence of an aluminum-cobalt-molybdenum catalyst (stage I) and a zeolite-containing aluminum nickel-molybdenum catalyst (stage II).

The result is 3 wt.% Gasoline distillate, 10 wt.% Diesel distillate (fraction 160-360 ° C) with a sulfur content of 0.02 wt.%, Which can serve as a component of commercial diesel fuel, and 80 wt.% Ennobled residue boiling above 360 ° C and characterized by a sulfur content of 0.06 wt.%, which is a high-quality raw material for the catalytic cracking process (density at 20 ° C - 918 kg / m ³ , nitrogen content - 0.10 wt.%, vanadium content - 0.15 g / t, nickel content - 0.12 g / t).

Example 3

A mixture of vacuum distillate of West Siberian oil (fraction 350-530 ° C) in an amount of 98 wt.%, Characterized by the following indicators:

density at 20 ° С - 922 kg / m ³ ;

sulfur content - 1.5 wt.%;

nitrogen content - 0.15 wt.%;

vanadium content - 0.45 g / t;

nickel content - 0.21 g / t;

boils up to 360 ° С - 5 vol.%

and the gas oil fraction of delayed coking in an amount of 2 wt.%, characterized by the following indicators:

boiling limits - 350-500 ° C;

density at 20 ° C - 980 kg / m ³ ;

sulfur content - 0.9 wt.%

subjected to hydrogenation processing at a pressure of 4 MPa, a temperature of 415 ° C, a volumetric feed rate of 0.5 h ^-1 , the ratio of hydrogen-containing gas / raw material 1200 vol./about. in the presence of a zeolite-containing aluminum-nickel-molybdenum catalyst.

The result is 2 wt.% Gasoline distillate, 45 wt.% Diesel distillate (fraction 160-360 ° C) with a sulfur content of 0.02 wt.%, Which can serve as a component of commercial diesel fuel, and 53 wt.% Ennobled residue boiling above 360 ° C and characterized by a sulfur content of 0.06 wt.%, which is a high-quality raw material for the catalytic cracking process (density at 20 ° C - 917 kg / m ³ , nitrogen content - less than 0.14 wt.%, vanadium content - 0.11 g / t, nickel content - 0.10 g / t).

Claims (3)

1. The method of hydrogenation processing of petroleum feedstock, which is a mixture of a vacuum distillate and a distillate fraction of secondary destructive processes, at elevated temperature and pressure in the presence of a catalyst, characterized in that the distillate fraction of secondary destructive processes with a sulfur content of up to 1 wt.% In an amount of 2 -25 wt.% On raw materials. 2. The method according to claim 1, characterized in that vacuum distillate with a boiling end up to 560 ° C is used as a raw material, and gas oil fractions of catalytic cracking, visbreaking, delayed coking are used as a distillate fraction of secondary destructive processes. 3. The method according to claims 1 and 2, characterized in that the hydrogenation processing is carried out at a pressure of 4-10 MPa, a temperature of 340-415 ° C, a volumetric feed rate of 0.5-2.0 h ^-1 .