阅读说明：本技术 一种渣油加氢原料的预处理方法及渣油加氢的方法 (Pretreatment method of residual oil hydrogenation raw material and residual oil hydrogenation method ) 是由 雷杰 韩海波 刘丹禾 李治 李康 陈曼桥 王文柯 樊麦跃 魏小波 于 2019-09-29 设计创作，主要内容包括：本发明涉及渣油加氢工艺技术领域,具体而言,涉及一种渣油加氢原料的预处理方法及渣油加氢方法。本发明中的渣油加氢原料的预处理方法,包括以下步骤：将经缓和加氢处理的渣油进行空化处理；所述缓和加氢处理的方法包括：将渣油原料于温度为300-350℃、压力为2-5MPa的条件下进行处理；所述空化处理的温度为90-150℃,压力为2-20MPa。本发明通过对渣油进行缓和加氢处理与空化处理,以改善渣油组分的组成结构及分布状态,得到的渣油的平均相对分子质量减小,残炭和粘度有明显的降低,而且渣油进一步进行加氢反应后轻质油收率大幅提高,焦炭收率降低。(The invention relates to the technical field of residual oil hydrogenation processes, in particular to a pretreatment method of a residual oil hydrogenation raw material and a residual oil hydrogenation method. The pretreatment method of the residual oil hydrogenation raw material comprises the following steps: subjecting the residue subjected to mild hydrotreating to cavitation treatment; the method for moderating hydrotreating comprises: treating the residual oil raw material at the temperature of 300-350 ℃ and the pressure of 2-5 MPa; the temperature of the cavitation treatment is 90-150 ℃, and the pressure is 2-20 MPa. The invention improves the composition structure and distribution state of the residual oil components by carrying out mild hydrogenation treatment and cavitation treatment on the residual oil, the average relative molecular mass of the obtained residual oil is reduced, the carbon residue and the viscosity are obviously reduced, the yield of light oil is greatly improved after the residual oil is further subjected to hydrogenation reaction, and the yield of coke is reduced.)

1. A pretreatment method of a residual oil hydrogenation raw material is characterized by comprising the following steps:

subjecting the residue subjected to mild hydrotreating to cavitation treatment;

the method for moderating hydrotreating comprises: treating the residual oil raw material at the temperature of 300-350 ℃ and the pressure of 2-5 MPa;

the temperature of the cavitation treatment is 90-150 ℃, and the pressure is 2-20 MPa.

2. The method for pretreating a residuum hydrogenation feedstock according to claim 1, characterized in that the mild hydrotreating pressure is 3-4MPa and the temperature is 320-340 ℃.

3. The process for the pretreatment of a residuum hydroprocessing feedstock according to claim 1 or 2, characterized in that the mild hydroprocessing time is from 20 to 40 min;

preferably, the time for the mild hydrotreating is from 25 to 30 min.

4. The method for pretreating a residuum hydrogenation feedstock according to claim 1, wherein the cavitation treatment temperature is 100 ℃ and 110 ℃, and the pressure is 8-10 MPa.

5. The process for pretreating a residuum hydrogenated feedstock according to claim 1, characterized in that said residuum feedstock comprises at least one of vacuum distillate oil, atmospheric residuum, and vacuum residuum.

6. The process for the pretreatment of a residuum hydroprocessed feedstock according to claim 1 wherein said residuum is preheated prior to mild hydroprocessing.

7. The method of pretreating a residuum hydrogenation feedstock according to claim 6, characterized in that the temperature of said preheating treatment is 100-120 ℃.

8. The method of pretreating a residuum hydrogenation feedstock according to claim 1, characterized in that said cavitation treatment employs an apparatus comprising at least one of a venturi-type cavitation apparatus, an orifice plate-type cavitation apparatus, and a jet pipe-type cavitation apparatus;

preferably, the cavitation treatment is performed by using a venturi-type cavitation device.

9. A method for hydrogenating residual oil is characterized by comprising the following steps: a residuum feedstock subjected to a pretreatment process as described in any of claims 1-8, followed by hydrogenation.

10. The residue hydrogenation process of claim 9, wherein the hydrogenation reaction temperature is 380-430 ℃ and the pressure is 8-10 MPa.

Technical Field

The invention relates to the technical field of residual oil hydrogenation processes, in particular to a pretreatment method of a residual oil hydrogenation raw material and a residual oil hydrogenation method.

Background

With the increasing shortage of crude oil at home and abroad and the acceleration of the heavy and inferior degree of the crude oil, the production of light oil products in a large amount in the crude oil processing process has become a long-term trend, and as an effective technical means for realizing the efficient and clean utilization of residual oil, the residual oil hydrogenation plays a very important role in increasing the yield of the light oil and improving the utilization rate of the crude oil. In order to improve the yield and quality of light oil products in the residual oil hydrogenation process to a greater extent, scholars at home and abroad carry out a great deal of research and provide a plurality of improvement methods.

Disclosure of Invention

The invention relates to a pretreatment method of a residual oil hydrogenation raw material, which comprises the following steps;

subjecting the residue subjected to mild hydrotreating to cavitation treatment;

the method for moderating hydrotreating comprises: treating the residual oil raw material at the temperature of 300-350 ℃ and the pressure of 2-5 MPa;

the temperature of the cavitation treatment is 90-150 ℃, and the pressure is 2-20 MPa.

The method combines mild hydrogenation treatment and cavitation treatment, and adopts a specific mild hydrogenation process and cavitation treatment conditions to reduce the content of asphaltene and increase the content of colloid in the residual oil, thereby greatly improving the dispersion state of the asphaltene, increasing the stability of the residual oil colloid, further deepening the hydrogenation reaction degree and improving the product distribution. The method of the invention overcomes the limitation of the prior residual oil hydrogenation raw material pretreatment technology, and can effectively improve the yield of light oil after residual oil hydrogenation treatment.

A method for hydrogenating residual oil comprises the following steps: the residual oil raw material is subjected to hydrogenation reaction after being subjected to the pretreatment method.

The yield of light oil is improved through hydrogenation reaction, and the yield of coke is reduced.

Compared with the prior art, the invention has the beneficial effects that:

the method of the invention improves the content, structure and distribution state of the residual oil components by combining the mild hydrogenation process with the cavitation treatment process. Through the mild hydrogenation reaction, the content of micromolecular components in the raw material can be improved, and then the spatial structure of asphaltene in the residual oil is destroyed through cavitation treatment, so that the association degree of asphaltene macromolecular groups is reduced, partial asphaltene is converted into colloid and smaller molecular structures, the content of asphaltene in the residual oil is reduced, the colloid content is increased, the dispersion state of the asphaltene is greatly improved, the stability of the residual oil colloid is increased, the hydrogenation reaction degree is further deepened, and the product distribution is improved. The average relative molecular mass of the residual oil obtained by the pretreatment method is reduced, the carbon residue and the viscosity are obviously reduced, the yield of light oil is greatly improved after the residual oil is further subjected to hydrogenation reaction, and the yield of coke is reduced.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. 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 commercially available.

According to one aspect of the invention, the invention relates to a process for pretreating a residuum hydrogenation feedstock, comprising the steps of:

subjecting the residue subjected to mild hydrotreating to cavitation treatment;

the method for moderating hydrotreating comprises: treating the residual oil raw material at the temperature of 300-350 ℃ and the pressure of 2-5 MPa;

the temperature of the cavitation treatment is 90-150 ℃, and the pressure is 2-20 MPa.

The pretreatment method of the residual oil hydrogenation raw material combines mild hydrogenation treatment and cavitation treatment, and the main reaction mechanism is as follows: under the extreme conditions of the cavitation process, the macromolecules and small molecules of the raw material components generate corresponding free radicals, which are then recombined. Before the vacuum residue is subjected to cavitation treatment, mild hydrogenation reaction is carried out, mainly for improving the content of small molecular components in the raw material so that more small molecular free radicals are generated in the cavitation process.

In one embodiment, the mild hydrotreating pressure is from 2 to 5MPa, and optionally 2.2MPa, 2.5MPa, 2.7MPa, 3MPa, 3.2MPa, 3.5MPa, 3.7MPa, 4MPa, 4.2MPa, 4.5MPa, or 4.7 MPa.

In one embodiment, the mild hydrotreating temperature is 300-.

In one embodiment, the temperature of the cavitation treatment is 90-150 deg.C, and optionally 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C or 145 deg.C.

In one embodiment, the pressure of the cavitation treatment is 2-20MPa, and may be selected from 2MPa, 4MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa or 19 MPa.

Preferably, the pressure of the mild hydrotreating is 3-4MPa, and the temperature is 320-340 ℃;

preferably, the time for the mild hydrotreating is from 20 to 40 min;

in one embodiment, the mild hydrotreating time is 20-40min, and optionally 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min, 35min, 36min, 37min, 38min, or 39 min.

Preferably, the time for the mild hydrotreating is from 25 to 30 min.

Preferably, the temperature of the cavitation treatment is 100-110 ℃, and the pressure is 8-10 MPa;

by further optimizing and moderating the hydrotreating conditions and the cavitation treatment conditions, the structural composition and morphological distribution of the residual oil can be better improved.

Preferably, the residue feedstock comprises at least one of vacuum distillate, atmospheric residue, and vacuum residue.

The vacuum distillate oil, the atmospheric residue oil and the vacuum residue oil have the characteristics of large molecular weight and high viscosity, the physical and chemical properties of the residue oil can be better improved by the pretreatment method, the yield of the light oil is greatly improved after further hydrogenation reaction, and the yield of coke is reduced.

Preferably, the residue is preheated prior to mild hydrotreating.

Preferably, the temperature of the preheating treatment is 100-120 ℃.

In one embodiment, the temperature of the pre-heating treatment is 100-120 ℃, and 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃ or 119 ℃ can be selected.

Preferably, the cavitation treatment employs a device comprising at least one of a venturi-type cavitation device, an orifice plate-type cavitation device, and a jet pipe-type cavitation device;

the high temperature, high pressure, micro-jet, powerful shearing force and other microcosmic high energy produced in local area when bubbles are broken in the cavitation process change the content, structure and distribution form of each component in residual oil, especially destroy the spatial structure of asphaltene in residual oil, reduce the degree of association of asphaltene macromolecular groups, lead to the conversion of partial asphaltene to colloid and smaller molecular structure, thereby lead to the reduction of residual oil asphaltene content, increase of colloid content, greatly improve the dispersion state of asphaltene, increase the stability of residual oil colloid, further deepen the hydrogenation reaction degree, and improve the product distribution.

Preferably, the cavitation treatment is performed by using a venturi-type cavitation device.

A method for hydrogenating residual oil comprises the following steps: after the residual oil raw material is subjected to the pretreatment method, hydrogenation reaction is carried out;

preferably, the temperature of the hydrogenation reaction is 380-430 ℃, and the pressure is 8-10 MPa.

In one embodiment, the temperature of the hydrogenation reaction is 380-.

In one embodiment, the hydrogenation reaction pressure is 8 to 10MPa, and optionally 8.1MPa, 8.2MPa, 8.3MPa, 8.4MPa, 8.5MPa, 8.6MPa, 8.7MPa, 8.8MPa, 8.9MPa, 9MPa, 9.1MPa, 9.2MPa, 9.3MPa, 9.4MPa, 9.5MPa, 9.6MPa, 9.7MPa, 9.8MPa or 9.9 MPa.

The invention adopts a specific mild hydrogenation process and cavitation treatment, and then carries out hydrogenation reaction, thereby improving the yield of the light oil, about 7-15 percentage points and reducing the yield of coke.

In a preferred embodiment, the resid hydroprocessmg pretreatment process comprises the steps of:

(a) preheating the residual oil at the temperature of 100-120 ℃; the residue comprises at least one of vacuum distillate oil, atmospheric residue and vacuum residue;

(b) carrying out mild hydrotreating on the preheated residual oil, wherein the pressure of the mild hydrotreating is 2-5MPa, the temperature is 300-350 ℃, and the time is 20-40 min;

(c) carrying out cavitation treatment on the residual oil subjected to mild hydrotreating, wherein the cavitation treatment temperature is 90-150 ℃, and the pressure is 8-20 MPa;

the cavitation device adopted by the cavitation treatment comprises at least one of a Venturi tube type cavitation device, a throttling hole plate type cavitation device and a jet pipe type cavitation device.

The present invention will be further explained with reference to specific examples and comparative examples.