RU2699226C1 - Method of hydrogenation refining of residual oil stock - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: invention relates to oil refining. Invention relates to a method for hydrogenation refining of residual oil stock on stationary layers of catalysts, involving the following stages: hydrodemetallisation of petroleum feedstock, subsequent hydrogenation desulphurisation and rectification of the obtained hydrogenated product with separation of distillate fractions and residue, returning a portion of the recovered gas-oil distillate fraction for mixing with the feedstock. Hydrodemetallisation stage is carried out in two parallel located alternating reactors, loaded with a catalyst system, which is layers arranged in a sequence starting from the distribution device of the pre-reactor: 1st layer is an inert ceramic material with a free volume fraction of not less than 55 %, 2nd layer – alumina nickel-molybdenum catalyst with specific surface area of not less than 100 m²/g, containing not less than 60 % of total porous pore volume with diameter of 17–25 nm and more than 5% of total porous pore volume with diameter of more than 50 nm, 3rd layer – alumina nickel-molybdenum catalyst with specific surface area of not less than 150 m²/g, containing not less than 40% of total porous pore volume of diameter of 10–17 nm, with ratio of layers of 20:(30÷35):( 45÷50) % of volume, with duration of operation cycle of each foreactor from 3,000 to 4,000 hours. Further, a hydrodeodisation step is carried out in a reactor loaded with an alumino-nickel-molybdenum-tungsten catalyst, a modified phosphorus, with specific surface area of not less than 200 m²/g, containing not less than 40% of total porous volume of pore with diameter of 5–10 nm. Subsequent step of hydrogenation desulphurisation is carried out in a reactor loaded with alumo-cobalt-molybdenum-tungsten catalyst, modified with phosphorus, with specific surface area of not less than 250 m²/g, containing not less than 60% of total porous pore volume with diameter of 3–8 nm. 50–80 wt% is directed to mixing with the raw material obtained after fractionation of gas-oil distillate fraction, remaining portion of gas-oil distillate fraction is removed as component of marine fuel or is supplied for mixing with rectification fraction, and the rectification fraction or the rectification fraction in the mixture with the rest of the gas-oil distillate fraction is separated as residual marine fuel with sulfur content of not more than 0.5 wt%.

EFFECT: obtaining marine fuel with sulfur content less than ½ wt% corresponding to RMG180 and RME180 (GOST 32510-2013).

4 cl, 1 dwg, 3 ex

Description

The invention relates to the field of oil refining, specifically to a method for the hydrogenation refinement of residual crude oil to produce marine fuel.

A known method of processing oil residues, including the stages of hydrogenation refinement of oil residues and separation of the obtained hydrogenate into distillate (fuel fractions) and an unconverted residue, characterized in that the obtained unconverted residue is subjected to delayed coking, producing coking distillates and coke, after which the coking distillates are further mixed distillates of the hydrogenation refinement stage and straight-run diesel distillates and are subjected to joint hydro cleaning at the following ratio, wt. %: coking distillates 35-80, hydrogenation refinement distillates 15-40, straight-run diesel distillates 5-25.

The method allows to obtain low-sulfur petroleum coke, gasoline fraction, diesel fraction and residual fraction (> 360 ° C) containing 0.1-0.3% of the mass. sulfur, which can be used as a component of catalytic cracking feedstock or as a component of low-sulfur boiler fuel.

(Patent RU 2309974, November 10, 2007)

The disadvantage of this method is the complexity of the technological scheme, the predominant production of motor fuel components in the absence of the possibility of producing significant quantities of low-sulfur boiler fuel, as well as marine fuel components.

A known method of processing oil residues, designed for hydrogenation refinement of heavy hydrocarbons and separation of the obtained hydrogenate into distillate and unconverted residue. The method is based on the LC-Fining liquid conversion process (hydrocracking) with a residue conversion level of up to 80% and higher. As raw materials, fuel oils, tars, heavy oils from tar sands, shale oils, coal extracts, etc. can be used.

(M. Beccari; U. Romano Encyclopaedia of hydrocarbons. Vol. II, Refining and petrochemicals. The Hydroconversion of Residues. - ENI: Istituto della Enciclopedia italiana, 2006 - P. 309-323).

With a conversion of 65% vol. get products with sulfur content in them: in the gasoline fraction - 0.01% of the mass., in the diesel fraction - 0.11% of the mass., in the fraction of heavy gas oil - 0.53% of the mass., unconverted residue - 1.6% of the mass .

The disadvantage of this method is the high residual sulfur content in the resulting distillates. To obtain commercial low-sulfur motor and residual fuels that meet the requirements of modern standards, their additional hydrofining is required.

A known method of processing residual petroleum feedstock with a high content of metals and asphaltenes, characterized in that the two-stage hydrofining process is carried out in a reactor with a fixed or boiling catalyst bed under process operating conditions (temperature 320-450 ° C, bulk feed rate 0.2-3 , 0 h ^-1 , the ratio of hydrogen / raw materials - 350-1200 nl / l) at low pressure (4.0-13.0 MPa). At the first stage, hydrodemetallization and hydrocracking of heavy oil hydrocarbon asphaltenes are carried out using a nickel-molybdenum-titanium-containing catalyst, and at the second stage, using a cobalt-molybdenum-titanium-containing catalyst, hydrodesulfurization.

(RF patent 2339680, 11/27/2008)

The disadvantage of this method is the inability to directly obtain commercial low-sulfur motor and boiler fuels that meet the requirements of modern environmental standards, and the method does not provide for the receipt of components of marine fuel.

Closest to the claimed invention is a two-stage method of hydroprocessing of heavy residual crude oil containing asphaltenes, sulfur-containing and metal impurities. The first stage is hydrodemetallization of heavy petroleum feedstock using a hydrodemetallization catalyst under hydrodemetallization conditions, the second stage is the hydrodesulfurization of a stream from the first stage on a hydrodesulfurization catalyst under hydrodesulfurization conditions.

(US Pat. No. 6,306,287 B1, Oct. 23, 2001).

In accordance with the invention, the hydrodemetallization step involves the presence of one or more hydrodemetallization zones with a fixed catalyst bed. The hydrodemetallization zones are preceded by at least two protective zones with fixed catalyst beds.

Protection zones are arranged sequentially and are used cyclically.

The hydrogenate after the hydrodesulfurization stage is subjected to atmospheric distillation with the release of fuel distillate fractions and unconverted residue. The selected gas oil fraction (170-350 ° C) is recycled in an amount of 5.0-25.0% of the mass. for raw materials to the feed line in front of the first protective zone.

The unconverted residue is used as a catalytic cracking feed. It is possible to recycle the products of catalytic cracking - light or heavy gas oil of each separately or their mixture into the feed line in front of the first protective zone.

Simultaneously with oil residues, straight-run gas oil (fraction 150-370 ° C) in the amount of 0.5-80.0% of the mass is also possible to enter the feed line before the first protective zone. on raw materials.

The considered method of processing heavy hydrocarbon raw materials solves the problem of converting highly viscous heavy oil residues non-transported through oil pipelines containing a large amount (100-1500 ppm) of heavy metals (nickel and vanadium), asphaltenes and sulfur compounds into a stable easily transported hydrocarbon-containing product with a low content of metals, asphaltenes and sulfur.

The disadvantages of the method are:

1) the lack of the possibility of direct production of low-sulfur motor and residual fuels, including marine, meeting the requirements of modern standards;

2) the complexity of the technological scheme in terms of switching protective zones;

The objective of the present invention is to develop a method for the hydrogenation refinement of residual oil raw materials with a high content of sulfur, nitrogen and metal impurities, providing residual marine fuel with a sulfur content of less than 0.5 wt%, corresponding to RME180 and RMG 180 fuels GOST 32510-2013.

To solve this problem, we propose a method for the hydrogenation refinement of residual oil feedstock on stationary catalyst beds, which includes the stages of hydrodemetallization of oil feedstock, subsequent hydrodeazotization and hydrogenation desulfurization, distillation of the obtained hydrogenate with separation of the distillate fractions and residue, and the return of some of the extracted gas oil-oil distillate to the distillate mixture.

The method is characterized in that the hydrodemetallization stage is carried out in two parallel alternately working forreactors loaded with a catalytic system that consists of layers arranged in sequence starting from the forreactor switchgear: 1st layer - inert ceramic material, 2nd and 3rd the layers are aluminum-nickel-molybdenum catalysts, with a layer ratio of 20, respectively: (30 - 35): (45 - 50)% of the volume, with a cycle time of each forreactor from 3000 to 4000 hours.

Then, after the hydrodemetallization step, the hydrodetriding step is additionally carried out in a reactor loaded with aluminum-nickel-molybdenum-tungsten catalyst.

The subsequent stage of hydrogenation desulfurization is carried out in a reactor loaded with aluminum-cobalt-molybdenum-tungsten catalyst.

50.0-80.0% of the mass of the recovered gas oil distillate fraction obtained after rectification of the hydrogenated product is returned to mixing with the feedstock, the remainder of the gas oil distillate fraction is removed as a component of diesel fuel or sent for mixing with the rectification residue.

In this case, the distillation residue or the distillation residue in a mixture with the remaining part of the gas oil distillate fraction is isolated as residual marine fuel with a sulfur content of not more than 0.5% of the mass.

As the residual crude oil, the residues of atmospheric distillation of oil with a sulfur content of not more than 4 wt%, heavy metals - nickel and vanadium - not more than 300 mg / kg are used.

The 1st layer of the catalytic system of the forreactors of the demetallization stage is an inert ceramic material with a free volume fraction of at least 55%, characterized by a high filtering ability with respect to mechanical impurities.

2nd layer - aluminum-nickel-molybdenum catalyst with a specific surface area of at least 100 m ² / g, containing at least 60% of the total porous pore volume with a diameter of 17-25 nm and more than 5% of the total porous pore volume with a diameter of more than 50 nm and is characterized by high absorption capacity heavy metals, cracking of asphaltenes and reduction of coking properties of residual oil.

3rd layer - aluminum-nickel-molybdenum catalyst with a specific surface area of at least 150 m ² / g, containing at least 40% of the total porous pore volume with a diameter of 10-17 nm and is characterized by the ability to absorb metals and low desulfurization activity.

The catalyst for the hydrodeazotization step is a phosphorus modified aluminum-nickel-molybdenum tungsten catalyst with a specific surface area of at least 200 m ² / g, containing at least 40% of the total porous pore volume with a diameter of 5-10 nm and is characterized by increased hydrogenating activity with respect to organic nitrogen compounds.

The catalyst for the hydrogenation desulfurization stage is a phosphorus-modified alumina-cobalmolybdenum-tungsten catalyst with a specific surface area of at least 250 m ² / g, containing at least 60% of the total porous pore volume with a diameter of 3-8 nm and is characterized by high hydrodesulfurization activity.

The process of hydrodemetallization is carried out at a pressure of 12-20 MPa, a temperature of 360-420 ° C, a volumetric feed rate of 0.5-2.0 h ^-1 and a ratio of hydrogen-containing gas (SHG) / feedstock 500-2000 nm ³ / m ³ .

The processes of hydrodeazotization and hydrogenation desulfurization are carried out at a pressure of 10-18 MPa, a temperature of 350-410 ° C, a volumetric feed rate of 0.3-1.5 h ^-1 and a hydrogen-containing gas / feed ratio of 500-2000 nm ³ / m ³ .

The above operations provide deep demetallization, de-nitriding and desulfurization of the original residual crude oil. The sulfur content in the distillation residue does not exceed 0.5 wt%, which allows it to be used as low-sulfur residual marine fuel of the RME180 and RMG180 brands (GOST 32510-2013).

The proposed method is implemented as shown in FIG. 1 scheme, which includes the positions of the main devices and flows:

1. Forreactor 1 stage hydrodemetallization

2. Forreactor 2 stages of hydrodemetallization

3. The reactor 3 stages of hydrodeazotization

4. The reactor 4 stages of hydrogenation desulfurization

5. Distillation column

I. Residual Petroleum

II. Demetallized flow

III. De-nitrated stream

IV. Hydrogenate

V. Gasoline distillate fraction

VI. Gas oil distillate fraction

VII. Rectification residue

Viii. Part of the gas oil fraction sent for mixing with raw materials

IX. Part of the gas oil fraction withdrawn from the installation

X. Part of the gas oil fraction, sent for mixing with the remainder of the distillation

Xi. Hydrogen gas

Residual oil feedstock I and hydrogen-containing gas XI enter one of the forreactors 1 or 2, where demetallization and deasphalting reactions occur.

Next, the demetallized stream P is sent to the reactor 3 stages of deazotization, where, together with the deazotization reaction, reactions of desulfurization, demetallization, deasphalting proceed. The de-nitrated stream III from the reactor 3 is sent to the reactor 4 of the hydrogenation desulfurization stage, where the desulfurization reaction proceeds actively. The obtained hydrogenate IV is subjected to distillation in a distillation column 5, from which the following products are removed: gasoline V, gas oil VI distillate fractions, and residue VII. The gasoline distillate fraction is a catalytic reforming feedstock.

Part of the gas oil distillate fraction VIII is sent for mixing with raw material I. The remaining part of the gas oil distillate fraction GC is removed from the plant as a component of diesel fuel or the remaining part of the gas oil distillate fraction X is sent for mixing with the remainder of rectification VII. The distillation residue VII or the distillation residue VII in a mixture with the portion remaining from the recirculation of the gas oil distillate fraction X is a low-sulfur residual marine fuel.

The method is illustrated by the following examples (see diagram shown in Fig.)

Example 1

High-sulfur oil fuel oil is subjected to hydrogenation refinement (sulfur content - 4.0 wt%, heavy metals - nickel and vanadium - 300 mg / kg, kinematic viscosity at 100 ° С - 104.7 mm ² / s).

Each of the two forrectors is loaded with a catalytic system consisting of layers arranged in sequence, starting from the switchgear: the 1st layer is an inert ceramic material, the 2nd and 3rd layers are aluminum-nickel-molybdenum catalysts with a layer ratio,% of volume: 20: 35:45.

Hydrodemetallization is carried out alternately in the forreactors.

The duration of the work cycle of each of the forreactors is 3000 hours.

First, feed the feed to the forreactor 1.

At the end of the operating cycle of the forreactor 1, it is turned off, the feed is supplied to the forreactor 2, in the forreactor 1, the catalytic system is replaced.

The process of hydrodemetallization is carried out at a pressure of 20 MPa, a temperature of 420 ° C, a volumetric feed rate of 0.5 h ^-1 , a ratio of VSG / raw material of 2000 nm ³ / m ³ .

Inert ceramic material with a free volume fraction of 65% is used as the first layer of the catalytic system of the forreactor.

As the second layer of the catalytic system of the forreactor, an aluminum-nickel-molybdenum catalyst (NiO — 3.5% by mass; MoO ₃ — 10.0% by mass) with a specific surface area of 100 m ² / g, containing 70% of the total pore volume of the pore with a diameter of 17 was used -25 nm and 15% of the total porous pore volume with a diameter of more than 50 nm.

As the 3rd layer of the forreactor-alumina-nickel-molybdenum catalyst system (NiO - 3.2% by mass; MoO ₃ - 18.0% by mass) with a specific surface area of 150 m ² / g, containing 40% of the total porous pore volume with a diameter of 10-17 nm.

The demetallized stream is sent to the reactor 3 of the stage of hydrodeazotization, where a stationary layer of phosphorus-modified aluminum-nickel-molybdenum-tungsten catalyst is loaded (NiO - 3.0% by mass; MoO ₃ - 11.6% by mass; WO ₃ - 4.5% by mass; P ₂ O ₅ - 3.5% wt.) With a specific surface area of 270 m ² / g, containing 55% of the total porous pore volume with a diameter of 5-10 nm.

Then, the de-nitrated stream enters the reactor 4 of the hydrogenation desulfurization stage, where a stationary layer of phosphorus-modified alumina-cobalt-molybdenum-tungsten catalyst is loaded (CoO - 3.0 wt%; MoO ₃ - 10.5 wt%; WO ₃ - 4.5 wt%; P ₂ O ₅ - 3.2% wt.) With a specific surface area of 280 m ² / g, containing 70% of the total porous pore volume with a diameter of 3-8 nm.

The processes of hydrodeazotization and hydrogenation desulfurization are carried out at a pressure of 18 MPa, a temperature of 410 ° C, a volumetric feed rate of 0.3 h ^-1 and a ratio of VSG / raw material of 2000 nm ³ / m ³ .

The obtained hydrogenate is subjected to distillation, in which the following products are removed: gasoline distillate fraction NK-180 ⁰ С (feedstock for catalytic reforming), gas oil distillate fraction boiling in the temperature range 180-350 ⁰ С, residue boiling off at a temperature above 350 ⁰ С.

80% of the mass. from the separated gas oil distillate fraction is directed to mixing with the raw material, the remainder of the gas oil distillate fraction is sent to mixing with the distillation residue.

The output of the distillation residue in a mixture with a part of the gas oil distillate fraction - residual marine fuel is 75% of the mass. on raw materials. The sulfur content in it is not more than 0.5% by mass, the kinematic viscosity at 50 ⁰ C is not more than 151 mm ² / s, the total content of metals (nickel and vanadium) is 45 mg / kg, which corresponds to RMG marine fuel 180 (GOST 32510-2013).

Example 2

Sublimated fuel oil is subjected to hydrogenation refinement (sulfur content - 2.0 wt%, heavy metals - nickel and vanadium - 80 mg / kg, kinematic viscosity at 100 ° C - 34.3 mm ² / s).

Hydrodemetallization is carried out alternately in the forreactors.

Each of the two forrectors is loaded with a catalytic system consisting of layers arranged in sequence, starting from the switchgear: the 1st layer is an inert ceramic material, the 2nd and 3rd layers are aluminum-nickel-molybdenum catalysts with a layer ratio,% of volume: 20: 30:50.

Hydrodemetallization is carried out alternately in the forreactors.

The duration of the work cycle of each of the forreactors is 4000 hours.

First, feed the feed to the forreactor 2.

At the end of the operating cycle of the forreactor 2, it is turned off, the feed is carried out in the forreactor 1, in the forreactor 2 the catalytic system is replaced.

The process of hydrodemetallization is carried out at a pressure of 12 MPa, a temperature of 360 ° C, a volumetric feed rate of -2.0 h ^-1 , a ratio of VSG / feed is 500 nm ³ / m ³ .

Inert ceramic material with a free volume fraction of 55% is used as the first layer of the catalytic system of the forreactor.

As the second layer of the catalytic system, an aluminum-nickel-molybdenum catalyst (NiO — 3.5% by mass; MoO ₃ — 10.0% by mass) with a specific surface area of 120 m ² / g, containing 60% of the total porous pore volume with a 17- 25 nm and 5% of the total porous pore volume with a diameter of more than 50 nm.

As the third layer of the catalytic system, an aluminum-nickel-molybdenum catalyst (NiO - 3.2% by mass; MoO ₃ - 18.0% by mass) with a specific surface area of 160 m ² / g, containing 40% of the total porous pore volume with a diameter of 10 -17 nm.

The demetallized stream is sent to the reactor 3 of the stage of hydrodeazotization, where a stationary layer of phosphorus-modified aluminum-nickel-molybdenum-tungsten catalyst is loaded (NiO - 3.0% by mass; MoO ₃ - 11.6% by mass; WO ₃ - 4.5% by mass; P ₂ O ₅ - 3.5% wt.) With a specific surface area of 200 m ² / g, containing 40% of the total porous pore volume with a diameter of 5-10 nm.

Then, the de-nitrated stream enters the reactor 4 of the hydrogenation desulfurization stage, where a stationary layer of phosphorus-modified alumina-cobalt-molybdenum-tungsten catalyst is loaded (CoO - 3.0 wt%; MoO ₃ - 10.5 wt%; WO ₃ - 4.5 wt%; P ₂ O ₅ - 3.2% wt.) With a specific surface area of 250 m ² / g, containing 60% of the total porous pore volume with a diameter of 3-8 nm.

The process of hydrodeazotization and hydrogenation desulfurization is carried out at a pressure of 10 MPa, a temperature of 350 ° C, a volumetric feed rate of 1.5 h ^-1 and a ratio of VSG / raw material of 500 nm ³ / m ³ .

The obtained hydrogenate is subjected to distillation, in which the following products are removed: gasoline distillate fraction NK - 180 ⁰ С (feedstock for catalytic reforming), gas oil distillate fraction boiling in the temperature range 180-350 ⁰ С, residue boiling off at a temperature above 350 ⁰ С.

50% of the mass of the separated gas oil distillate fraction is sent to mixing with the feed. The remainder of the gas oil distillate fraction is withdrawn as a component of diesel fuel.

The output of the distillation residue - residual marine fuel is 82% of the mass. on raw materials. The sulfur content in it is not more than 0.2% by weight, the kinematic viscosity at 50 ⁰ C is not more than 165 mm ² / s, the total content of metals (nickel and vanadium) is 12 mg / kg, which corresponds to RME marine fuel 180 (GOST 32510-2013).

Example 3

Sulfur oil fuel oil is subjected to hydrogenation upgrading (sulfur content - 3.1% by mass, heavy metals - nickel and vanadium - 162 mg / kg, kinematic viscosity at 100 ° C - 52.1 mm ² / s).

Hydrodemetallization is carried out alternately in the forreactors.

Each of the two forrectors is loaded with a catalytic system consisting of layers arranged in sequence, starting from the switchgear: the 1st layer is an inert ceramic material, the 2nd and 3rd layers are aluminum-nickel-molybdenum catalysts with a layer ratio,% of volume: 20: 33:47.

First, feed the feed to the forreactor 1.

The duration of the work cycle of each of the forreactors is 3500 hours.

At the end of the operating cycle of the forreactor 1, it is turned off, the feed is carried out in the forreactor 2, in the forreactor 1, the catalytic system is replaced

The process of hydrodemetallization is carried out at a pressure of 15 MPa, a temperature of 390 ° C, a volumetric feed rate of 1.0 h ^-1 , a ratio of VSG / raw material of 1000 nm ³ / m ³ .

Inert ceramic material with a free volume fraction of 60% is used as the first layer of the catalytic system of the forreactor.

As the second layer of the catalytic system, an aluminum-nickel-molybdenum catalyst (NiO — 3.5 wt%; MoO ₃ — 10.0 wt%) with a specific surface area of 110 m ² / g, containing 65% of the total porous pore volume with a 17- 25 nm and 10% of the total porous pore volume with a diameter of more than 50 nm.

As the third layer of the catalytic system, an aluminum-nickel-molybdenum catalyst (NiO - 3.2% by mass; MoO ₃ - 18.0% by mass) with a specific surface of 155 m ² / g, containing 40% of the total porous pore volume with a diameter of 10 -17 nm.

The demetallized stream is sent to the reactor 3 stages of hydrodetriding, where a stationary layer of phosphorus-modified aluminum-nickel-molybdenum-tungsten catalyst is loaded (NiO - 3.0% by mass; MoO ₃ - 11.6% by mass; WO ₃ - 4.5% by mass; P ₂ O ₅ - 3.5% wt.) With a specific surface area of 250 m ² / g, containing 50% of the total porous pore volume with a diameter of 5-10 nm.

Next, the de-nitrated stream enters the reactor 4 stages of hydrogenation desulfurization, where a stationary layer of phosphorus-modified alumina-cobalt-molybdenum-tungsten catalyst is loaded (CoO - 3.0% by mass; MoO ₃ - 10.5% by mass; WO ₃ - 4.5% by mass; P ₂ About ₅ - 3.2% wt.) With a specific surface area of 265 m ² / g, containing 65% of the total porous pore volume with a diameter of 3-8 nm.

The process of hydrodeazotization and hydrogenation desulfurization is carried out at a pressure of 13 MPa, a temperature of 380 ° C, a volumetric feed rate of 1.0 h ^-1 and a ratio of VSG / feed 1000 nm ³ / m ³ .

The obtained hydrogenate is subjected to distillation, in which the following products are removed: gasoline distillate fraction NK - 180 ⁰ С (feedstock for catalytic reforming), gas oil distillate fraction boiling in the temperature range 180-350 ⁰ С, residue boiling off at a temperature above 350 ⁰ С.

65% of the mass. from the separated gas oil distillate fraction is directed to mixing with the raw material, the remainder of the gas oil distillate fraction is sent to mixing with the distillation residue.

The output of the distillation residue in a mixture with part of the gas oil distillate fraction of the residual marine fuel is 70% of the mass. on raw materials. The sulfur content in it is not more than 0.1% by weight, the kinematic viscosity at 50 ⁰ C is not more than 150 mm ² / s, the total content of metals (nickel and vanadium) is 25 mg / kg, which corresponds to RMG marine fuel 180 (GOST 32510-2013).

Thus, the proposed method for the hydrogenation refinement of residual oil feedstocks successfully solves the problem of processing high-viscosity atmospheric oil residues (fuel oil) to produce a series of valuable low-sulfur products: components of motor fuels and low-sulfur residual marine fuel. At the same time, raw materials with a high sulfur content (up to 4% by weight) and heavy metals - nickel and vanadium (up to 300 mg / kg) can be involved in processing.

The proposed method is environmentally attractive, because the production scheme of the basic component of low-sulfur residual marine fuel does not use complex technological processes (deasphalting, catalytic cracking, coking).

Claims (4)

1. The method of hydrogenation refinement of residual petroleum feedstock on stationary catalyst beds, comprising the steps of: hydrodemetallization of petroleum feedstock, subsequent hydrogenation desulfurization and distillation of the obtained hydrogenate with separation of the distillate fractions and residue, returning a portion of the recovered gas oil distillate fraction to mix with the raw material hydrodemetallization is carried out in two parallel alternately working forreactors loaded with kata a lytic system consisting of layers arranged in a sequence starting from the forreactor switchgear: the 1st layer is an inert ceramic material with a free volume fraction of at least 55%, the 2nd layer is an aluminum-nickel-molybdenum catalyst with a specific surface area of at least 100 m ² / g, containing not less than 60% of the total porous pore volume with a diameter of 17-25 nm and more than 5% of the total porous pore volume with a diameter of more than 50 nm, the third layer is an aluminum-nickel-molybdenum catalyst with a specific surface area of at least 150 m ² / g, containing at least 40% vol its pore volume pore diameter of 10-17 nm, at a ratio of 20 layers, respectively: (30 ÷ 35) :( 45 ÷ 50) volume%, with a cycle time of each forreaktora from 3000 to 4000 hours; further, a hydrodetasisation step is carried out in a reactor loaded with an aluminum-nickel-molybdenum-tungsten phosphorus modified catalyst with a specific surface area of at least 200 m ² / g containing at least 40% of the total porous pore volume with a diameter of 5-10 nm; the subsequent stage of hydrogenation desulfurization is carried out in a reactor loaded with phosphorus-modified alumina-cobalt-molybdenum tungsten catalyst with a specific surface area of at least 250 m ² / g containing at least 60% of the total porous pore volume with a diameter of 3-8 nm; while mixing with raw materials direct 50-80% of the mass. obtained after distillation of the gas oil distillate fraction, the remaining part of the gas oil distillate fraction is removed as a component of diesel fuel or sent for mixing with the distillation residue, and the distillation residue or rectification residue in a mixture with the remaining part of the gas oil distillate fraction is isolated as residual marine fuel with a sulfur content of not more than 0 5% of the mass. 2. The method according to p. 1, characterized in that the residual oil is used in the residues of atmospheric distillation of oil with a sulfur content of not more than 4 wt%, heavy metals - nickel and vanadium - not more than 300 mg / kg 3. The method according to p. 1, characterized in that the hydrodemetallization process is carried out at a pressure of 12-20 MPa, a temperature of 360-420 ° C, a volumetric feed rate of 0.5-2.0 h ^-1 and a hydrogen-containing gas / feed ratio of 500 -2000 nm ³ / m ³ . 4. The method according to p. 1, characterized in that the process of hydrodeazotization and hydrogenation desulfurization is carried out at a pressure of 10-18 MPa, a temperature of 350-410 ° C, a volumetric feed rate of 0.3-1.5 h ^-1 and a ratio of hydrogen-containing gas / feedstock 500-2000 nm ³ / m ³ .

Images