RU2448153C1 - Hydrocracking method of heavy oil raw material using vortex reactor - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: invention refers to the method implemented in vortex reactor with volume of 1-20 litres, through which processed raw material is passed together with hydrogen of 0.1 to 0.8 wt % of weight of initial raw material at excess pressure of 0.01-0.5 MPa and temperature of 380-450°C, rotor speed of vortex reactor of 2000 to 10 000 rpm and power of rotor drive of 30 kW to 5 MW.

EFFECT: increasing the output of light distillate fractions and obtaining only commercial products: diesel fractions and tar oil - raw material for bitumen production at considerable simplicity of method and high process technological effectiveness.

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Description

The present invention relates to the field of oil refining, in particular to the process of hydrocracking of heavy petroleum feedstocks, and can be used in the directed processing of heavy and bituminous oils, as well as oil residues, for example, residues from atmospheric and vacuum distillation of oils, including fuel oil, tar, and oil refinery waste - oil sludge.

Due to the huge reserves of heavy and bituminous oil, the problem of their processing with high depth into distillate fuels is becoming increasingly important. Existing refining processes are characterized by huge capital investments. Heavy and bituminous oils, as well as oil residues (vacuum gas oils, fuel oils, semi-tars and tars), in contrast to light oil products (gasolines and diesel fuels), are characterized by a higher molecular weight, a different group, fractional composition and a low hydrogen content. The bulk of heteroatomic components are concentrated in heavy petroleum feedstocks, almost all resins and asphaltenes, therefore its average molecular weight is 3-5 times higher than that of distillate petroleum products. It should also be noted that diesel fractions contain the minimum amount of hydrogen among the distillates, which determines the maximum possible yield of distillates from heavy petroleum feedstock, provided that it is diesel fractions.

A known method of cracking heavy oil products, which consists in preparing a homogeneous mixture of heavy oil residues (TNO) and specially dried and subjected to mechanochemical processing in a vibratory mill finely ground sapropelite (particle size 20-30 μm), followed by thermocracking the resulting mixture at 390-420 ° C and 0.2-5 MPa and the separation of cracking products, moreover, the mechanochemical treatment is carried out in an inert medium under a pressure of 0.05 atm, the vibrating mill operates on a line with a vibrating screen, and the continuous supply of components to Addressing lead screw feeder at a controlled feed rate. As oil sapropelite, oil shale, saproximite, boghead, kennel are used. A thermal cracking unit for heavy oil residues in the presence of an organomineral catalyst, in addition to a feed mixer, a feed mixture heating furnace with a reaction chamber, includes disintegrators, remote reactors, a separator, and an atmospheric column for the separation of thermal cracking products.

(See RF Patents 2178446 and 2178447, BI No. 2 (II), 2002)

However, this method has several disadvantages, such as the complicated hardware design of the process, the need for thorough drying and very fine grinding of sapropelite, the use of sapropelite of one genetic type (carbonate), heating of raw materials in a tube furnace with its inevitable coking, the need to carry out the process in an inert atmosphere, including vibration grinding of sapropelite, the presence of remote reactors operating under high pressure, the need to use water vapor to isolate from the reaction products ganomineralnogo spent catalyst.

There is also a method of cracking heavy oil residues at temperatures above 400 ° C, including preheating the feedstock to a cracking temperature, the cracking being carried out in the presence of thermally or catalytically active hydrogen donor additives selected from the group: ordinary or enriched shales of various genetic types (carbonate , aluminosilicate, aluminosilicate-carbonate, silicate), the mineral part of shales, zeolite-containing catalysts, a mixture of ordinary slate and zeolite-containing aluminosilicate ka alizatorov at atmospheric pressure within a temperature range of 400-430 ° C, when the content of these additives 8-12 wt.%, while the duration of the process, providing complete stripping of light distillate products.

(RF patent 2288940 dated 2005.07.20, MPK С10G 47/22.)

A known method of cracking TNO in a mixture with a catalytic additive by mixing oil residues with natural zeolite containing 5-20% alumina, grinding it to a particle size of not more than 100 μm, dispersing it with an oil residue and thermocracking the mixture at a temperature of 390-450 ° C, a pressure of 0.2-5 MPa and a space velocity of 1-6 h ^-1 . Zeolite may contain up to 7% iron oxides. The catalyst is introduced into the feedstock in an amount of 1-10%.

(See RF Patent 2179570 dated 2000.12.25, IPC C10G 1/05.)

These processes require the preparation of raw materials, the use of a consumable catalyst, the control of many parameters, and have low reproducibility of the results.

A known method of processing heavy oil residues by treating them with an ozone-containing gas to absorb ozone in an amount of preferably 0.05-0.5 wt.% Followed by thermal cracking of the resulting product at a temperature of preferably 400-430 ° C, pressure 0.5-3.0 MPa and bulk velocity of the raw materials in the thermal reactor 1-2 h ^-1 . The yield of light oil products is about 70% with coke formation of 0.2-0.25%.

(See RF Patent No. 2184761, CL C10G 27/14, C10G 9/00 from 2001.07.18.)

However, this method does not allow to regulate the production of gas oil (diesel) fractions, it requires the use of ozone in sufficiently large amounts of 0.05-0.5%, and the fact that industrial ozone generators with such a capacity are not produced makes this method not applicable in industry.

Closest to the proposed one is the electrochemical method of cracking petroleum feedstock by exposing it to an electric field with a voltage source of 10-100 kV of both alternating and direct current, which is applied to the hydrocarbon feed vapor by an electric field, passing the vapor through the field.

(See RF Application No. 94013148 dated 1994.04.14, IPC C10G 15/12.)

The disadvantage of this method is the relatively low yield of light distillate fractions and the presence of unused waste.

The objective of the invention is to increase the yield of light distillate fractions and obtain only marketable products: diesel fractions and tar - raw materials for the production of bitumen - with significant simplicity of the method and high processability.

The technical result is achieved by the fact that the hydrocracking of heavy crude oil - heavy and bituminous oil, including heavy oil residues, is carried out in a vortex reactor with a volume of 1-20 liters at an overpressure of 0.01-0.5 MPa and a temperature of 380-450 ° C, through the vortex reactor passes the processed raw materials together with hydrogen in an amount of from 0.1 to 0.8 wt.% of the feedstock. Figure 1 shows one of the possible schemes of the vortex reactor, which includes a housing 1, consisting of two conical half-shells 2 and 3, equipped with means (fittings) for supplying raw materials 4 and removal of reaction products 5. In the housing 1 is installed a rotor 6, which is a a shaft with a conical ribbing mounted for rotation inside the housing 1. These elements form a vortex chamber 7 in the housing 1. View AA allows you to imagine the location of the ribs of the shaft, forming a conical surface during rotation.

The rotor speed is in the range from 2000 to 10000 revolutions per minute, the rotor drive power can vary from 30 kW to 5 MW. The process begins, and avalanche develops in the reaction vortex chamber 7, in which there are pulsed effects on the feedstock in a vortex field. Along with the feedstock, hydrogen is also supplied in an amount of from 0.1 to 0.8 wt.% Of the feedstock mass; as a result, the cracking processes are supplemented by hydrogenation processes. Special preliminary preparation of raw materials is not required.

The present invention allows to significantly simplify the hardware design of the hydrocracking process in comparison with the known hydrocracking methods and increase the depth of processing of heavy oil residues, up to 90 wt.%, To obtain only marketable products: diesel fraction and tar. Using this technology, it is possible to process not only fuel oils and tars, but oil sludges with a mechanical impurity content of up to 5 wt.%, Cracking gases are less than 1 wt.%.

The proposed non-waste hydrocracking method allows, within certain limits, to vary the ratio between the obtained diesel fractions and the obtained tar.

The influence of the main technological parameters on the hydrocracking process

Technological parameters affecting the process of hydrocracking reactions are the pressure, temperature, rotor speed, drive power and residence time in the reaction vortex chamber.

An increase in temperature leads to an increase in the yield of distillate (light) oil products and, to a certain limit, a decrease in the viscosity of the hydrocracking residue, but at the same time, the density of the residue increases.

The same applies to increasing the residence time in the reaction chamber, which is achieved by reducing the feed rate of the feedstock or by reducing the selection of the hydrocracking residue - tar.

The change in pressure in the reaction vortex chamber, which is controlled by a pressure valve when the liquid phase exits the vortex reactor, also affects the space velocity and the conversion process as a whole.

To organize the optimal course of hydrocracking reactions of petroleum feedstocks in the vortex reaction chamber, the structure and flow rate are regulated by feeding the feedstock and selecting the hydrocracking products. The supply of raw materials to the vortex reaction chamber, as a rule, is carried out after preliminary heating of the raw materials to 360-380 ° C of a direct heating furnace or in indirect heat exchangers of the raw materials with a coolant.

Hydrocracking reactions take place in the vortex reaction chamber under the influence of vortex pulsed influences in the presence of hydrogen, as a result of which the feedstock is enriched with distillate fractions, which evaporate in the vaporizer when the cracker is removed from the vortex reactor.

Subsequently, diesel fractions are either shipped in the form of automobile or marine fuels, or subjected to further processing — rectification, hydrotreating to higher requirements for sulfur content in automotive fuels, etc., and the residue in the form of tar is used as raw material for the production of road or building bitumen.

Example 1

The processed raw materials are fuel oil M 100, manufactured by OJSC Salavatnefteorgsintez.

Characteristics of the feedstock of fuel oil M100:

Specific gravity at 20 ° C 0.985 g / cm ³ Fractional composition of fuel oil M 100: - The beginning of the boil 365 ° C - NK-160 ° C 0% - 160-360 ° C 0% - 360-500 ° C 55% - 500 ° and above 45% Sulfur content 2.9% Solids content 0.5 wt.%

The feedstock is heated in a steam heat exchanger to a temperature of 90 ° C, the feed pump feeds into the cracking coil of the cracking furnace, passing through which the feedstock is heated from flue gases to 380 ° C, and then it is fed together with hydrogen 0.2 wt.% By weight of the feedstock into a vortex reaction chamber, where, under the influence of pulsed vortex effects, cracking and hydrogenation reactions of the feedstock occur, as a result of which diesel fractions and cracked residue are separated in de tar, which is removed from the bottom of the evaporator separately. The pressure in the reaction chamber is supported by 0.1 MPa by a pressure valve installed on the outlet line of the processed raw materials enriched with distillate, the residence time of the raw materials in the reaction chamber is 5 seconds, the rotor speed is 3100 rpm. The evaporated vapor-liquid mixture is cooled in a heat exchanger. The resulting product is condensed, analyzes of the obtained distillate oil product are carried out - diesel fraction 160-360 ° C and tar.

Material balance of processing:

Received: Fuel oil M 100 99.8% Hydrogen 0.2% Received: - diesel fraction 160-360 ° C 62% - tar 500 ° and above 37% - gas + losses one% Total: one hundred%

The characteristic of the obtained diesel fraction:

Specific gravity at 20 ° C 0.852 g / cm ³ Sulfur content 0.2%

Example 2

The processed raw materials are fuel oil M 100, produced by Gazprom Dobycha Astrakhan LLC.

Experimental conditions: temperature 390 ° C, pressure in the reaction chamber 0.3 MPa, rotor speed of 3500 rpm, hydrogen supply 0.5 wt.%, Residence time of the raw material in the reactor 3 seconds.

Characteristics of the feedstock of fuel oil M 100:

Specific gravity at 20 ° C 0.933 g / cm ³ Fractional composition of fuel oil M 100: - The beginning of the boil 350 ° C - NK-160 ° C 0% - 160-360 ° C 5% - 360-500 ° C 95% Sulfur content 3.2% Solids content 0.02 wt.%

Material balance of processing:

Received: Fuel oil M 100 99.5% Hydrogen 0.5% Received: - diesel fraction 160-360 ° C 85% - tar 500 ° and above fourteen% - gas + losses one% Total: one hundred%

The characteristic of the obtained diesel fraction:

Specific gravity at 20 ° C 0.832 g / cm ³ Sulfur content 0.15%

Example 3

The processed raw materials are fuel oil M 40, produced by OJSC Novoshakhtinsky Oil Product Plant.

The conditions of the experiment: temperature 410 ° C, pressure in the reaction chamber 0.5 MPa, rotor speed of 3700 rpm, hydrogen feed 0.8 wt.%, The residence time of the raw material in the reactor is 4 seconds.

Characteristics of the feedstock of fuel oil M 40:

Specific gravity at 20 ° C 0.934 g / cm ³ Fractional composition of fuel oil M 40: - The beginning of the boil 360 ° C - NK-160 ° C 0% - 160-360 ° C 5% - 360-500 ° C 65% - 500 ° C and above thirty% Sulfur content 2.0% Solids content 0.2 wt.%

Material balance of processing:

Received: Fuel oil M 40 99.2% Hydrogen 0.8% Received: - diesel fraction 160-360 ° C 80% - tar 500 ° and above 19% - gas + losses one% Total: one hundred%

The characteristic of the obtained diesel fraction:

Specific gravity at 20 ° C 0.835 g / cm ³ Sulfur content 0.12%

Example 4

The processed raw materials are bituminous oil, the Russkoye field.

Experimental conditions: temperature: 420 ° C, pressure in the reaction chamber 0.5 MPa, rotor speed of 3900 rpm, hydrogen feed 0.1 wt.%, Residence time of the raw material in the reactor 5 seconds.

Characteristics of the feedstock - bituminous oil of the Russkoye field:

Specific gravity at 20 ° C 0.940 g / cm ³ Fractional composition of bituminous oil: - The beginning of the boil 260 ° C - NK-160 ° C 0% - 160-360 ° C 28% - 360-500 ° C 40% - 500 ° C and above 32% Sulfur content 0.4% Solids content 0.8 wt.%

Material balance of processing:

Received: Oil 99.9% Hydrogen 0.1% Received: - diesel fraction 160-360 ° C 90% - tar 500 ° and above 9% - gas + losses one% Total: one hundred%

The characteristic of the obtained diesel fraction:

Specific gravity at 20 ° C 0.825 g / cm ³ Sulfur content 0.10%

As follows from the examples, the claimed method is a good and reliable solution to the problem with the achievement of a technical result.

An analysis of the known solutions did not allow us to identify a set of features that coincide with the proposed ones, which allows us to conclude that the proposed solution meets the “Novelty” criterion.

The described examples allow us to conclude that the criterion "Technical applicability".

Analysis of the known solutions did not allow to identify the totality of the distinguishing features that provide the claimed technical result, which allows us to conclude that the proposed solution meets the criterion of "Inventive step".

Claims (1)

Hydrocracking method for heavy petroleum feedstocks, including heavy petroleum residues, characterized in that the process is conducted in a vortex reactor of 1-20 l volume, through which the feedstock is passed together with hydrogen from 0.1 to 0.8 wt.% Based on the weight of the feedstock an excess pressure of 0.01-0.5 MPa, a temperature of 380-450 ° C, with a rotational speed of the vortex reactor rotor from 2000 to 10000 rpm and a rotor drive power of 30 kW to 5 MW.

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