阅读说明：本技术 一种重油改质方法 (Heavy oil modification method ) 是由 韩海波 李康 雷杰 李治 于 2020-07-30 设计创作，主要内容包括：本发明公开了一种重油改质方法,涉及石油化工技术领域。重油改质方法将重油、催化剂和氢源在水力空化反应器中反应。发明人创造性地在水力空化反应器中进行重油改质的反应,可以在更低反应温度下使氢源活化,显著降低了反应能耗,且反应工艺简单易行；由于水力空化反应器的作用,使得沥青质团聚体微晶结构变得松散,有利于解决沥青质团聚的问题。(The invention discloses a heavy oil modification method, and relates to the technical field of petrochemical industry. The heavy oil upgrading process reacts heavy oil, a catalyst, and a hydrogen source in a hydrodynamic cavitation reactor. The inventor creatively carries out the heavy oil modification reaction in the hydrodynamic cavitation reactor, can activate the hydrogen source at lower reaction temperature, obviously reduces the reaction energy consumption, and has simple and easy reaction process; due to the action of the hydrodynamic cavitation reactor, the microcrystalline structure of the asphaltene aggregate becomes loose, which is beneficial to solving the problem of asphaltene aggregate.)

1. A heavy oil upgrading method is characterized by comprising the following steps: reacting heavy oil, a catalyst, and a hydrogen source in a hydrodynamic cavitation reactor.

2. A process for upgrading heavy oil according to claim 1, wherein the reaction temperature in the hydrodynamic cavitation reactor is in the range of 25-150 ℃, preferably 50-80 ℃.

3. The heavy oil upgrading process of claim 1 or 2, wherein the hydrodynamic cavitation pressure is from 5 to 18 MPa; preferably 10-18 MPa.

4. The heavy oil upgrading process of claim 1, wherein the catalyst comprises a support, a molecular sieve, and an active metal;

preferably, the mass fraction of the molecular sieve in the catalyst is 20-45%, the mass fraction of the carrier is 50-78%, and the mass fraction of the active metal is 0.5-5.0%.

5. The heavy oil upgrading method of claim 4, wherein the mass ratio of the catalyst to the heavy oil is from 0.002 to 0.1; preferably 0.003-0.01.

6. The heavy oil upgrading process of claim 4, wherein the molecular sieve is of type HZSM-5;

preferably, the silicon-aluminum ratio in the molecular sieve is 20-60, and the BJH pore size is larger than 5 nm.

7. The heavy oil upgrading method of claim 4, wherein the support is selected from at least one of alumina and silica.

8. The heavy oil upgrading process of claim 4, wherein the active metal is selected from at least one of silver, gallium, zinc, nickel, cobalt, and molybdenum.

9. The heavy oil upgrading process of claim 1, wherein the source of hydrogen is selected from at least one of methane, ethane, and propane;

preferably, the hydrogen source is methane, and the mass ratio of the methane to the heavy oil is 0.01-0.2: 1; more preferably 0.01-0.08: 1.

10. The heavy oil upgrading method of claim 1, wherein the heavy oil is selected from at least one of heavy crude oil, atmospheric resid, and vacuum resid.

Technical Field

The invention relates to the technical field of petrochemical industry, and in particular relates to a heavy oil modification method.

Background

According to statistics, the reserves of heavy crude oil in the global range account for about 70% of the total reserves of the oil, high-quality raw materials can be provided for subsequent processing through heavy oil modification, the H/C atomic ratio can be effectively improved through the heavy oil modification, the molecular weight and the asphaltene content are reduced, and the like, so that the heavy oil modified heavy crude oil has very important economic value. Therefore, the development of heavy oil upgrading technology is also a hot spot of research in the global oil refining industry.

However, the existing heavy oil upgrading technology mainly has the problems of high operation temperature, high energy consumption and low light oil yield. In addition, heavy oil upgrading has the problems of high carbon residue, complex process, easy aggregation of asphaltene and the like.

Disclosure of Invention

The invention aims to provide a heavy oil upgrading method, which aims to reduce reaction temperature and energy consumption and improve the problem of asphaltene agglomeration.

The technical problem to be solved by the invention is realized by adopting the following technical scheme.

The invention provides a heavy oil upgrading method, which comprises the following steps: reacting heavy oil, a catalyst, and a hydrogen source in a hydrodynamic cavitation reactor.

The embodiment of the invention provides a heavy oil upgrading method which has the beneficial effects that: the heavy oil catalyst and the hydrogen source are used as raw materials, the inventor creatively carries out heavy oil modification reaction in the hydrodynamic cavitation reactor, the hydrogen source can be activated at lower reaction temperature, the reaction energy consumption is obviously reduced, and the reaction process is simple and easy to implement; due to the action of the hydrodynamic cavitation reactor, the microcrystalline structure of the asphaltene aggregate becomes loose, which is beneficial to solving the problem of asphaltene aggregate.

Additionally, in the prior art, the activation temperature of hydrogen source such as methane is approximately above 700 ℃, even thousands of degrees centigrade, the inventors found that the activation temperature of hydrogen source is significantly reduced after introducing the hydrodynamic cavitation reactor, and the heavy oil upgrading reaction can be completed at very low temperature.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The following is a detailed description of a heavy oil upgrading method according to an embodiment of the present invention.

The embodiment of the invention provides a heavy oil upgrading method, which comprises the following steps: reacting heavy oil, a catalyst, and a hydrogen source in a hydrodynamic cavitation reactor. The inventor creatively carries out the heavy oil modification reaction in the hydrodynamic cavitation reactor, can activate the hydrogen source at lower reaction temperature (from the original temperature of more than 700 ℃ to 25-150 ℃), obviously reduces the reaction energy consumption, and has simple and easy reaction process; due to the action of the hydrodynamic cavitation reactor, the microcrystalline structure of the asphaltene aggregate becomes loose, which is beneficial to solving the problem of asphaltene aggregate.

Specifically, the reaction principle of heavy oil upgrading is roughly summarized as: activation of a hydrogen source, e.g. methane, to CH over a catalyst₃And H, activated CH₃And H, completing the heavy oil methylation and hydro-upgrading processes. Under the action of the cavitation reactor, high pressure of 300MPa and high temperature of 3200K can be generated within microsecond time and micrometer range when cavitation bubbles in heavy oil collapse, each cavitation bubble can be regarded as a micro-reactor, the collapse of the cavitation bubbles provides conditions for the reaction of the heavy oil and methane on a catalyst, and the purpose of obviously reducing the reaction temperature is achieved.

Specifically, the reaction in the hydrodynamic cavitation reactor can effectively improve the problem of asphaltene agglomeration, probably because extreme phenomena such as micro-jet flow and strong shearing force generated in the hydrodynamic cavitation reactor can effectively reduce the interaction force among asphaltene molecules, so that the microcrystalline structure of the asphaltene agglomeration becomes loose, the association degree of aromatic hydrocarbon compounds in the asphaltene is reduced, the particle size distribution of asphaltene micelles becomes small, and the asphaltene solid particles become disordered and loose from ordered compactness. By improving the problem of asphaltene agglomeration, the secondary processing performance of the heavy oil can be improved, and particularly the generation of coking during secondary processing of the heavy oil is reduced.

Further, the reaction temperature in the hydrodynamic cavitation reactor is 25-150 ℃, preferably 50-80 ℃; the hydraulic cavitation pressure is 5-18 MPa; preferably 10-18 MPa. The heavy oil upgrading reaction can be completed by controlling the reaction temperature and pressure within the above ranges, and the yield of light oil is also preferable.

Further, the heavy oil is selected from at least one of heavy crude oil, atmospheric residue and vacuum residue, which are common raw materials in heavy oil upgrading, and the heavy oil upgrading method in this embodiment is suitable for the above raw materials.

Further, the hydrogen source is at least one selected from methane, ethane and propane, and the above three raw materials are all suitable for the upgrading method in the embodiment of the invention, and are used as the hydrogen source to increase the H/C atomic ratio of the heavy oil in the reaction.

In a preferred embodiment of the invention, the hydrogen source is methane and the mass ratio of methane to heavy oil is 0.01-0.2: 1; more preferably 0.01-0.08: 1. The use amount of the methane is controlled within the range, so that the methane can play a good role in methylation and hydrogenation modification, and the H/C atomic ratio of the heavy oil can be effectively improved.

Further, the mass ratio of the catalyst to the heavy oil is 0.002-0.1; preferably 0.003-0.01. The catalyst comprises a carrier, a molecular sieve and an active metal; in the catalyst, the mass fraction of the molecular sieve is 20-45%, the mass fraction of the carrier is 50-78%, and the mass fraction of the active metal is 0.5-5.0%. The inventor optimizes the dosage and the composition of the catalyst so as to further improve the reaction efficiency and reduce the activation temperature of the hydrogen source.

In a preferred embodiment of the invention, the molecular sieve is of type HZSM-5; preferably, the silicon-aluminum ratio in the molecular sieve is 20-60, and the BJH pore size is larger than 5 nm. The inventor further regulates and controls the silica-alumina ratio and the BJH pore diameter in the HZSM-5 molecular sieve, and compared with other conventional molecular sieve catalysts, the catalyst can further reduce the activation temperature of methane and improve the yield of light oil.

Further, the carrier is at least one selected from alumina and silica, or an alumina-silica composite catalyst. The active metal is selected from at least one of silver, gallium, zinc, nickel, cobalt and molybdenum, all of which are suitable for the upgrading method in the embodiment of the present invention.

The features and properties of the present invention are described in further detail below with reference to examples.