RU2297439C1 - Method of producing fuel distillates and fuel oil - Google Patents

Abstract

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: method resides in preliminarily mixing starting feedstock with (i) liquid hydrogen-donor additive having 4-10% active hydrogen and taken in amount 0.5-1.0% of the weight of feedstock and (ii) coke scavenger taken in amount 0.5-5%, after which resulting three-component mixture is dispersed and activated. Thermal hydrocracking of the mixture is conducted at elevated temperature and pressure. Coke scavenger is withdrawn out of the process together with residual products.

EFFECT: increased yield of desired products and reduced coking on equipment walls due to the presence of hydrogen-donor additive and coke scavenger.

7 cl, 1 tbl, 5 ex

Description

This invention relates to the production of fuel distillates, in particular gasoline and diesel fuel, and can be used in the refining industry.

The tasks of the oil refining industry at the present stage are unsolvable without the widespread introduction of secondary processes for processing residual oil raw materials containing an increased amount of metals, primarily vanadium and nickel, such as fuel oils, tars and heavy oils (Malta).

One of the widely used ways of solving this problem abroad is the process of thermal hydrocracking of residual crude oil.

A known method of producing fuel distillates by thermal hydrocracking of a mixture containing residual petroleum feed and coal in an amount of 2-10% by weight of the residual petroleum feed at elevated temperature and pressure, followed by isolation of the desired products. The main feature of the claimed invention is the use of sapropelite as coal, as well as the use as a raw material of a mixture additionally containing a liquid gasification product of sapropelite in an amount of 2-10% by weight of the residual oil feed and a fraction with boiling point> 370 ° C, isolated from hydrocracking products and recyclable in an amount of 20-40% by weight of the residual crude oil (RU 2009166, C10G 47/22, 03/15/1994).

The disadvantage of this method is cumbersome, and most importantly, its environmental harmfulness, because it is accompanied by the formation of a large amount of unused semicoke containing toxic components and capable of spontaneous combustion during storage, as well as fusa mixture of liquid shale gasification products containing toxic phenols.

Closer to the claimed invention in essence and the achieved result is a method for producing fuel distillates and boiler fuel by processing residual raw materials (tar) by mixing the raw material with a liquid additive-activator (hydrogen donor) - a fraction of shale oil with a boiling range of 200-400 ° C, obtained gasification of shale with an active hydrogen content of at least 10 wt.%. The process of thermal conversion is carried out at a temperature in the reactor of 410-450 ° C, a pressure of 2.5-5 MPa, a space velocity of 1.0-3.0 h ^-1 . Before thermoconversion, the mixture is subjected to mechanical activation and the influence of a magnetic vortex field in the respective devices. The mechanical activation of the mixture is carried out in dispersants, and the magnetic vortex field treatment is carried out by passing a medium flow through ferromagnetic particles, for example, through rotating ferromagnetic needles. Needles rotate in the working area of the apparatus at a temperature of 80-150 ° C, where a mixture of tar and shale oil enters (RU 2198199, С10G 9/00, 02/10/2003).

The disadvantage of this method is the formation of a significant amount of coke both on the surface of the process equipment and in the composition of the target products.

The aim of this invention is to increase the yield of target products and reduce the formation of coke to a minimum.

This goal is achieved by the method of producing fuel distillates and boiler fuel in the process of thermal hydrocracking at elevated temperature and pressure by introducing into the feedstock a liquid donor-hydrogen additive - activator followed by preliminary heating to a temperature of 410-430 ° C, adding coke scavenger taken in an amount 0.5-5 wt.%. In this case, the hydrogen donor additive is preferably taken in an amount of 0.5-10 wt.% On the feedstock and contains from 4 to 10 wt.% Active hydrogen. Moreover, the coke scavenger is introduced into the process with the beginning of the formation of the target products, i.e. when entering the mode, and is derived from the remainder of the raw material, not subjected to destruction.

As the raw material, you can use any heavy oil raw materials, such as fuel oil, tar, heavy oil, etc.

As a coke scavenger, natural or synthetic zeolites, bentonite clays, kieselguhr, alumina, various silicates, aluminosilicates, etc. can be used.

The process is preferably carried out at a temperature of 410-490 ° C, a pressure of 3-10 MPa and a space velocity of 1.0-3.0 h ^-1 .

Hydrogen donors of alkylbenzene, mixtures of alkylbenzenes, alkylbenzene-containing hydrocarbon mixtures, as well as tetrahydroquinoline, tetrahydrophenanthrene, tetrahydroanthracene, octahydropyrene, tetralin and other hydroaromatic compounds can be used as a hydrogen donor additive. It is preferable to use a fraction with a boiling point of 200-400 ° C, obtained by pyrolysis of oil, coal or shale raw materials, as well as hydrotreated oil fraction with so Kip. 340-420 ° C obtained in the process of thermal hydrocracking.

It is advisable to mix the feedstock with a hydrogen donor additive in an ejector-type transonic mixer at a temperature of 70-90 ° C and a pressure of 0.5-1 MPa to activate the feed mixture.

If necessary, an emergency or scheduled shutdown of the process when its temperature is lower than necessary in the products obtained, to prevent the formation of coke, you can enter the above coke scavengers in the same quantities.

The coke scavenger is best mixed first with a portion of the feedstock in a weight ratio of 1: 2-1: 4 in a mechanical mixer at a temperature of 50-150 ° C, and then added to the previously obtained mixture of the feedstock with a hydrogen donor additive for subsequent dispersion and activation into transonic mixer.

Comparison of the claimed solutions with the prototype and other technical solutions in this technical field allows us to conclude that the claimed solutions meet the criteria of "novelty" and "inventive step".

Target fuel distillates in the separation of thermal hydrocracking products in accordance with the invention are fuel fractions:

gasoline, boiling up to 180 ° С, diesel, boiling up within 180-360 ° С, as well as fuel oil with low viscosity (conditional viscosity - not higher than 8 degrees at 80 ° С).

Such fuel fractions are the main products in the implementation of the process in accordance with the invention. Fuel fractions can easily be processed into high quality commercial fuel components, i.e. The invention allows to obtain a result that does not follow with obviousness from the prior art.

The claimed method is as follows.

The process of thermal hydrogenation of heavy raw materials is carried out in a flow unit with a reactor volume of 6 l or in an industrial unit with a reactor volume of 10 m ³ or more. Thermal hydrogenation conditions: temperature 410-490 ° C, pressure 3-10 MPa, space velocity 1.0-3.0 h ^-1 . The amount of donor-hydrogen additive is 0.5-10.0% based on the raw material, the hydrogen content in it is from 4 to 10 wt.%. The amount of coke scavenger is 0.5-5 wt.% Based on raw materials. After the start of the thermal hydrogenation process, to achieve stable operation of the process and equipment with the formation of target products from a two-component raw material mixture, a coke scavenger is gradually added; while increasing the temperature of the raw materials at the outlet of the tubular furnace of the installation. For up to 90 days, the process of thermal hydrocracking is carried out at a temperature of 410-430 ° C only in the presence of a donor-hydrogen additive, the amount of which is maintained in the above limit (0.5-10%). Only after stabilization of the regime, coke scavenger is introduced into the feedstock in addition to the hydrogen donor additive and at the same time the process temperature is maintained at 410-490 ° С.

During the process, gas and liquid products are removed, and solid components are separated. Liquid products of the process n.a. - 420 ° C are hydrotreated and distilled into fractions with boiling point. up to 180 ° С, 180-340 (360) ° С, gas oil fraction with b.p. 340-420 ° C, as well as a component of fuel oil with so kip. above 340 (360) ° С. The obtained fraction 340-420 ° C is used as a donor-hydrogen additive.

Examples of the invention

The advantages of the invention are illustrated by the following examples.

As the residual crude oil in the above examples 1, 2, 4, 5 use tar, which has the following characteristic: density 984 kg / m ³ , elemental composition, wt.%: C 86.8; H 10.86; S 1.5; N 0.3 (oxygen and impurities by difference - up to 100.0), viscosity 28.0 cSt, coking ability 10.0 wt.%, Asphaltenes 9.3 wt.%, Boil up to 500 ° C 24.5 wt.% contains vanadium 180 g / t, nickel 90 g / t, and in example 3 fuel oil grade M 100.

Example 1

The initial mixture is prepared by mixing tar with bentonite clay, taken in an amount of 3 wt.% For raw materials. Then, the resulting mixture is added to a mixture of feedstock with a hydrogen donor – hydrogenated gas oil fraction of 340–420 ° C, taken in an amount of 7 wt.% And containing 7%, prepared previously in a transonic mixer at a temperature of 80 ° C and a pressure of 0.7 MPa. active hydrogen. Mixing is carried out in a heated stirrer at a temperature of 90 ° C, a pressure of 1 MPa, for 2.5 hours, and then a three-phase mixture is passed through a dispersant and a transonic mixer.

Thermal hydrocracking is carried out under a pressure of 10 MPa, a temperature of 410 ° C, and a space velocity of 3 h ^-1 . After the temperature reaches 410 ° C, a coke scavenger is introduced into the feedstock. Upon reaching the stability of the operational parameters of the process of thermal hydrocracking, the process is conducted in the presence of both additives (solid and liquid). Liquid products are distilled into fractions with so Kip. up to 180 ° С (gasoline), 180-340 (360) ° С (diesel), 340-420 ° С (gas oil) and the remainder with the boiling point. above 420 ° C. Process indicators are given in the table.

Example 2

The initial mixture is prepared by mixing tar and kieselguhr in a mass ratio of 2: 1 in a mechanical mixer at 100 ° C. Then the resulting mixture is added to a mixture of feedstock with a donor-hydrogen additive - a fraction of 200-400 ° C obtained by coal pyrolysis containing 4 wt.% Active hydrogen, prepared previously in a transonic mixer at a temperature of 80 ° C and a pressure of 0.7 MPa .

Thermal hydrocracking is carried out at a temperature of 425 ° C, a pressure of 3 MPa and a space velocity of 1 h ^-1 .

Liquid products are distilled into fractions with so Kip. up to 180 ° С (gasoline), 180-360 ° С (diesel) and the remainder with boiling point. above 360 ° C. Process indicators are given in the table.

Example 3

The initial mixture is prepared by mixing fuel oil brand M 100 with clinoptilolite in a mass ratio of 4: 1 in a mechanical mixer at 150 ° C. Then, the resulting mixture is added to a mixture of feedstock with a donor-hydrogen additive - a fraction of 200-400 ° C obtained by shale pyrolysis containing 9.9 wt.% Active hydrogen, prepared previously in a transonic mixer at a temperature of 90 ° C and a pressure of 1 MPa.

Thermal hydrocracking is carried out at a temperature of 430 ° C, a pressure of 5 MPa and a space velocity of 2 h ^-1 .

Liquid products are distilled into fractions with so Kip. up to 180 ° С (gasoline), 180-360 ° С (diesel) and the remainder with boiling point. above 360 ° C. Process indicators are given in the table.

Example 4

The initial mixture is prepared by mixing tar with zeolite NaHY in a mass ratio of 4: 1 in a mechanical mixer at 150 ° C. Then, the resulting mixture is added to a mixture of feedstock with a donor-hydrogen additive - a fraction of 200-400 ° C obtained by shale pyrolysis containing 6 wt.% Active hydrogen, prepared previously in a transonic mixer at a temperature of 90 ° C and a pressure of 1 MPa.

Thermal hydrocracking is carried out at a temperature of 490 ° C, a pressure of 7 MPa and a space velocity of 2 h ^-1 .

Liquid products are distilled into fractions with so Kip. up to 180 ° С (gasoline), 180-360 ° С (diesel) and the remainder with boiling point. above 360 ° C. Process indicators are given in the table.

Example 5

The initial mixture is prepared by mixing tar with aluminosilicate in a mass ratio of 3: 1 in a mechanical mixer at 150 ° C. Then, the resulting mixture is added to a mixture of feedstock with a donor-hydrogen additive - a fraction of 200-400 ° C obtained by pyrolysis of an oil residue containing 6.5 wt.% Active hydrogen, prepared previously in a transonic mixer at a temperature of 90 ° C and a pressure of 1 MPa .

Thermal hydrocracking is carried out at a temperature of 450 ° C, a pressure of 4 MPa and a space velocity of 1 h ^-1 .

Liquid products are distilled into fractions with so Kip. up to 180 ° С (gasoline), 180-360 ° С (diesel) and the remainder with boiling point. above 360 ° C. Process indicators are given in the table.

Analysis of the data shows that the claimed method allows the process to obtain high yields of distillate fractions and boiler fuel of excellent quality with a minimum coke content both in the obtained fractions and on the walls of the equipment.

Examples of the thermal hydrocracking process No. p / p Raw materials, process conditions, yield of target products and coke Examples one 2 3 four 5 one Feedstock, wt.% 90 92 95 96 99 2 Hydrogen donor 10 8 5 four one additive, wt.% including active hydrogen, wt.% 7 four 9.9 6 6.5 3 Process conditions Temperature ° C 410 425 430 490 450 Pressure, MPa 10 3 5 7 four Volumetric speed, h ^-1 3 one 2 2 one four The yield of products, wt.% Calculated on raw materials with hydrogen-donor additive Gas 4,5 5,6 5.2 7.8 7.0 Water 0.7 0.65 0.7 0.75 0.9 Fraction N.K. - 180 ° C 9.0 12.0 12.8 13.5 11.6 Fraction 180-340 (360) ° С 26.0 38.5 35.6 37,2 35.3 Fraction 340-420 ° C 10.0 - - - - Fuel oil (residue) with boiling point> 360 (420) ° С 49.0 42.35 44.7 39.27 43.9 Coke (total amount deposited on coke scavenger, on walls and in fractions obtained) 0.8 0.9 1,0 1.48 1.3

Claims (7)

1. A method of producing fuel distillates by thermal hydrocracking of residual oil at elevated temperatures and pressures in the presence of a hydrogen donor additive and the isolation of the target products, characterized in that they use a hydrogen donor additive with an active hydrogen content of 4 to 10% from the moment of release the process to the mode with the beginning of obtaining stable target products, it is conducted in the presence of a coke scavenger taken in an amount of 0.5-5 wt.% on the feedstock and at the temperature of the raw material mixture exit the furnace agreva to 490 ° C. 2. The method according to claim 1, characterized in that use a hydrogen-donor additive in an amount of 0.5-10 wt.% On the feedstock. 3. The method according to claim 1 or 2, characterized in that as a raw material for producing a hydrogen-donor additive, a pyrolysis fraction of oil, coal or shale raw materials boiling in the range of 200-400 ° C or a hydrotreated oil fraction with a boiling point of 340 is used -420 ° C. 4. The method according to claim 1 or 2, characterized in that as a coke scavenger, natural or synthetic zeolites, bentonite clays, kieselguhr, aluminum oxide are used. 5. The method according to any one of claim 1 or 2, characterized in that the heavy oil residue and the hydrogen donor additive are mixed and dispersed in mechanical and transonic mixers at a temperature of 70-90 ° C and a pressure of 0.5-1 MPa. 6. The method according to any one of claim 1 or 2, characterized in that the coke scavenger is pre-mixed in a mechanical mixer at a temperature of 50-150 ° C with an oil residue in a mass ratio of 1: 2-1: 4, followed by addition to the previously obtained mixture heavy oil residue with a hydrogen-donor additive and dispersion and activation of a three-component mixture in a transonic mixer. 7. The method according to any one of claims 1 and 2, characterized in that the process is carried out at a temperature of 410-490 ° C, a pressure of 3-10 MPa and a space velocity of 1.0-3.0 h ^-1 .