阅读说明：本技术 一种原油制化学品组合工艺方法 (Combined process for preparing chemical products from crude oil ) 是由 靳凤英 于海斌 范景新 臧甲忠 辛利 李犇 王银斌 郭春垒 赵闯 刘凯隆 王梦迪 于 2021-09-20 设计创作，主要内容包括：本发明公开了一种原油制化学品组合工艺方法。该方法包括：原油先经加氢精制脱除S、N、金属等杂质,得到精制原油；精制原油进入原油吸附分离单元,在吸附剂的作用下吸附分离,得到原油非芳烃组分和原油芳烃组分；针对原油非芳烃组分和原油芳烃组分组成和性质的差异,分别采用不同的加工方式,原油非芳烃组分经过烯烃增产单元和汽柴油吸附分离单元最大化生产低碳烯烃,原油芳烃组分通过芳烃组分切割单元、芳烃增产单元和针状焦增产单元最大化生产低碳芳烃,并副产针状焦等产品。本发明原油直接制化学品组合工艺方法提供的方法以原油为原料最大限度地生产低碳烯烃和低碳芳烃,减少低附加值油品,从而实现石油资源高效利用。(The invention discloses a combined process method for preparing chemicals from crude oil. The method comprises the following steps: firstly, carrying out hydrofining on the crude oil to remove S, N, metal and other impurities to obtain refined crude oil; the refined crude oil enters a crude oil adsorption separation unit, and is subjected to adsorption separation under the action of an adsorbent to obtain a crude oil non-aromatic hydrocarbon component and a crude oil aromatic hydrocarbon component; aiming at the differences of the composition and properties of the crude oil non-aromatic hydrocarbon component and the crude oil aromatic hydrocarbon component, different processing modes are respectively adopted, the crude oil non-aromatic hydrocarbon component produces low-carbon olefin to the maximum extent through an olefin yield increasing unit and a gasoline and diesel oil adsorption separation unit, the crude oil aromatic hydrocarbon component produces low-carbon aromatic hydrocarbon to the maximum extent through an aromatic hydrocarbon component cutting unit, an aromatic hydrocarbon yield increasing unit and a needle coke yield increasing unit, and products such as needle coke are by-produced. The method provided by the combined process method for directly preparing chemicals from crude oil provided by the invention takes the crude oil as a raw material to produce low-carbon olefin and low-carbon aromatic hydrocarbon to the maximum extent, and reduces oil products with low added values, thereby realizing high-efficiency utilization of petroleum resources.)

1. A combined process method for preparing chemicals from crude oil is characterized by comprising the following steps:

(a) introducing crude oil and hydrogen into a crude oil hydrofining unit, and obtaining fuel gas and refined crude oil under the hydrofining condition;

(b) introducing the refined crude oil into a crude oil adsorption separation unit, and obtaining a crude oil non-aromatic hydrocarbon component and a crude oil aromatic hydrocarbon component under the action of an adsorbent;

(c) the non-aromatic components of the crude oil in the step (b) enter an olefin yield increasing unit to obtain alkene-rich gas, cracked gasoline and diesel oil, oil slurry and coke;

(d) the cracked gasoline and diesel oil in the step (c) enters a gasoline and diesel oil adsorption separation unit, and a gasoline and diesel oil non-aromatic component and a gasoline and diesel oil aromatic component are obtained under the action of a gasoline and diesel oil aromatic hydrocarbon adsorbent;

(e) returning the non-aromatic components of the gasoline and diesel oil to the olefin yield increasing unit to be used as cracking raw materials;

(f) the crude oil aromatic hydrocarbon component in the step (b) enters an aromatic hydrocarbon component cutting unit, and a I-type aromatic hydrocarbon component with the distillation range of less than or equal to 350 ℃ and a II-type aromatic hydrocarbon component with the distillation range of more than 350 ℃ are obtained through rectification cutting;

(g) the I-type aromatic hydrocarbon component with the distillation range of less than or equal to 350 ℃ in the step (f) and the gasoline and diesel oil aromatic hydrocarbon component in the step (d) enter an aromatic hydrocarbon yield increasing unit, and hydrogenation and lightening are realized in a hydrogen atmosphere to obtain fuel gas, liquefied gas, light naphtha, BTX, C9 and C10 aromatic hydrocarbon;

(h) and (f) the II-type aromatic hydrocarbon component with the distillation range of more than 350 ℃ enters a needle coke yield increasing unit to obtain alkene-rich gas, coking gasoline and diesel oil and needle coke.

2. The combined process method for preparing chemicals from crude oil according to claim 1, wherein the crude oil adsorption separation unit adopts a simulated moving bed process, the operation temperature is 30-200 ℃, and the pressure is 0.1-2.0 MPa.

3. The combined process for preparing chemicals from crude oil as claimed in claim 1, wherein: the analytic agent used by the crude oil adsorption separation unit is one or more of methylcyclohexane, toluene, ethylbenzene or xylene, or one or more of lower alcohols such as methanol, ethanol, propanol and the like.

4. The combined process for the production of chemicals from crude oil of claim i wherein the product of the crude oil adsorptive separation unit in step (b) is a non-aromatic component of crude oil having an aromatics content of no greater than 10 wt% and an aromatic component of crude oil having a non-aromatic content of no greater than 10 wt%.

5. The combined process for the production of chemicals from crude oil of claim 4 wherein the product of the crude oil adsorptive separation unit in step (b) is a non-aromatic component of crude oil having an aromatics content of no greater than 5 wt.% and an aromatic component of crude oil having a non-aromatic content of no greater than 5 wt.%.

6. The combined process for the production of chemicals from crude oil of claim 1 wherein the olefin stimulation unit is a steam cracking unit or a catalytic cracking unit.

7. The combined process method for preparing chemicals from crude oil according to claim 1, wherein the gasoline and diesel oil adsorption separation unit adopts a simulated moving bed process, the operation temperature is 30-100 ℃, and the pressure is 0.2-0.6 MPa.

8. The combined process for the production of chemicals from crude oil of claim 1 wherein in step (d) the gasoline and diesel adsorption separation unit produces non-aromatic components of gasoline and diesel having an aromatics content of no more than 5 wt% and aromatic components of gasoline and diesel having a non-aromatics content of no more than 5 wt%.

9. The combined process for preparing chemicals from crude oil as claimed in claim 1, wherein the desorbent used in the adsorption and separation unit for gasoline and diesel oil is one or more of methylcyclohexane, toluene, ethylbenzene or xylene.

Technical Field

The invention relates to crude oil processing, belongs to the technical field of petrochemical industry, and particularly relates to a combined process method for preparing chemicals from crude oil.

Background

In the last 10 years, the oil refining industry in the world is continuously carrying out structure transformation and upgrading due to the influence of adverse factors such as fierce market competition of the finished oil, descending of processing profit margin, economic uncertainty and the like. Different from the market of finished oil, the olefin and the aromatic hydrocarbon are important basic chemical raw materials, have wide application and vigorous demand. Therefore, many large projects built and proposed in the world seek to improve the refining and chemical integration level and improve the utilization rate of raw materials. However, due to the limitations of processing technology and supporting equipment, the major products of most of the current refineries are still fuels, and the conversion rate of chemicals is still limited.

US3702292 describes an integrated crude oil refinery for the production of fuels and chemicals comprising a crude distillation unit, a hydrocracking unit, a delayed coking unit, a reforming unit, an ethylene and propylene production unit (which includes a pyrolysis steam cracking unit and a pyrolysis product separation unit), a catalytic cracking unit, an aromatics product recovery unit, a butadiene recovery unit and an alkylation unit in a system associated with each other to achieve about 50% conversion of crude oil to petrochemicals and about 50% conversion of crude oil to fuels.

Cn201380006638.x provides an integrated solvent deasphalting, hydrotreating and steam pyrolysis process for direct processing of crude oil to produce olefinic and aromatic petrochemicals, i.e. solvent deasphalting of crude oil to remove impurities such as asphaltenes and metals, hydrotreating of deasphalted oil, and thermal cracking in the presence of steam to produce olefins, aromatic compounds and pyrolysis fuel oil.

CN200910162163.9 provides a combined process for processing inferior crude oil, which comprises subjecting inferior heavy oil raw material to solvent deasphalting to obtain deasphalted oil, preheating the deasphalted oil, introducing into a first reaction zone of a catalytic conversion reactor, mixing the oil gas generated by reaction, used catalyst and light raw oil, introducing into a second reaction zone for cracking reaction, hydrogen transfer reaction and isomerization reaction, and separating the reaction product into dry gas, liquefied gas, gasoline, diesel oil and catalytic wax oil after liquid-solid separation. After the catalytic wax oil is hydrogenated, the catalytic wax oil is introduced into a catalytic conversion device for further reaction to obtain a light fuel oil product. The method produces propylene and light fuel oil from inferior raw oil to the maximum extent, particularly the yield of high-octane gasoline can reach 42 percent, and the total yield of liquefied gas, gasoline and diesel oil can reach 75 percent, thereby realizing the high-efficiency utilization of petroleum resources.

CN1448483A provides a combined hydrogenation process and decarburization process, which comprises the steps of firstly carrying out mild thermal cracking on residual oil feed, then carrying out solvent deasphalting together with catalytic cracking slurry oil, and carrying out hydrogenation treatment on deasphalted oil. The method reduces the etching degree of a residual oil hydrogenation device, prolongs the service life of a hydrogenation catalyst, improves the yield and the property of a liquid product, has the total light oil yield of 80 percent, and reduces the yields of coke and cracked gas.

In summary, the conventional heavy oil processing technologies mainly include two main types: firstly, decarburization, which mainly comprises solvent deasphalting, heavy oil catalytic cracking and delayed coking; and the second is hydrogenation, which mainly comprises hydrofining and hydrotreating. The hydrogen-carbon ratio of the inferior heavy oil can be improved through the process, so that the inferior heavy oil is converted into low-boiling-point compounds, a large amount of fuel is still generated, and the high-efficiency and high-value utilization of heavy oil molecules is not realized.

Disclosure of Invention

The invention mainly aims to provide a combined process method for preparing chemicals from crude oil, which aims at overcoming the defects of the prior art, takes the crude oil as a raw material, comprises units of crude oil hydrofining, crude oil adsorption separation, olefin yield increase, aromatic hydrocarbon component cutting, aromatic hydrocarbon yield increase and the like, and finally obtains high-added-value chemical products such as low-carbon olefin, low-carbon aromatic hydrocarbon and the like through the processes of hydrofining, adsorption separation, cracking, delayed coking and the like, and simultaneously obtains C₉、C₁₀Byproducts such as aromatic hydrocarbon, needle coke and the like realize that alkene is preferred and arene is preferred.

In order to achieve the aim, the invention provides a combined process method for preparing chemicals from crude oil, which comprises the following steps:

(a) introducing crude oil and hydrogen into a crude oil hydrofining unit, and obtaining fuel gas and refined crude oil under the hydrofining condition;

(b) introducing the refined crude oil into a crude oil adsorption separation unit, and obtaining a crude oil non-aromatic hydrocarbon component and a crude oil aromatic hydrocarbon component under the action of an adsorbent;

(c) the non-aromatic components of the crude oil in the step (b) enter an olefin yield increasing unit to obtain alkene-rich gas, cracked gasoline and diesel oil, oil slurry and coke;

(d) the cracked gasoline and diesel oil in the step (c) enters a gasoline and diesel oil adsorption separation unit, and a gasoline and diesel oil non-aromatic component and a gasoline and diesel oil aromatic component are obtained under the action of a gasoline and diesel oil aromatic hydrocarbon adsorbent;

(e) returning the non-aromatic components of the gasoline and diesel oil to the olefin yield increasing unit to be used as cracking raw materials;

(f) the crude oil aromatic hydrocarbon component in the step (b) enters an aromatic hydrocarbon component cutting unit, and a I-type aromatic hydrocarbon component with the distillation range of less than or equal to 350 ℃ and a II-type aromatic hydrocarbon component with the distillation range of more than 350 ℃ are obtained through rectification cutting;

(g) the I-type aromatic hydrocarbon component with the distillation range of less than or equal to 350 ℃ in the step (f) and the gasoline and diesel oil aromatic hydrocarbon component in the step (d) enter an aromatic hydrocarbon yield increasing unit, and hydrogenation and lightening are realized in a hydrogen atmosphere to obtain fuel gas, liquefied gas, light naphtha, BTX and C₉And C₁₀Aromatic hydrocarbons;

(h) and (f) the II-type aromatic hydrocarbon component with the distillation range of more than 350 ℃ enters a needle coke yield increasing unit to obtain alkene-rich gas, coking gasoline and diesel oil and needle coke.

In the combined process method for preparing chemicals from crude oil, the crude oil adsorption separation unit preferably adopts a simulated moving bed process, the operation temperature is 30-200 ℃, and the pressure is 0.1-2.0 MPa;

in the combined process method for preparing chemicals from crude oil, the analytic reagent used by the crude oil adsorption separation unit is one or more of methyl cyclohexane, toluene, ethylbenzene or xylene, and can also be one or more of low-carbon alcohols such as methanol, ethanol, propanol and the like;

in the combined process for preparing chemicals from crude oil, the crude oil adsorption separation unit can obtain non-aromatic hydrocarbon components of crude oil with the aromatic hydrocarbon content of not more than 10 wt% and aromatic hydrocarbon components of crude oil with the non-aromatic hydrocarbon content of not more than 10 wt%, and preferably obtain non-aromatic hydrocarbon components of crude oil with the aromatic hydrocarbon content of not more than 5 wt% and aromatic hydrocarbon components of crude oil with the non-aromatic hydrocarbon content of not more than 5 wt%.

In the combined process for preparing chemicals from crude oil, the olefin yield increasing unit can be a steam cracking unit or a catalytic cracking unit.

In the combined process method for preparing chemicals from crude oil, the gasoline and diesel oil adsorption and separation unit adopts a simulated moving bed process, the operation temperature is 30-100 ℃, and the pressure is 0.2-0.6 MPa.

In the combined process method for preparing chemicals from crude oil, the gasoline and diesel oil adsorption separation unit can obtain gasoline and diesel oil non-aromatic components with the aromatic hydrocarbon content of not more than 5 wt% and gasoline and diesel oil aromatic hydrocarbon components with the non-aromatic hydrocarbon content of not more than 5 wt%.

In the combined process method for preparing chemicals from crude oil, the desorption agent used by the gasoline and diesel oil adsorption and separation unit is one or more of methylcyclohexane, toluene, ethylbenzene or xylene.

Compared with the prior art, the method has the beneficial effects that: the method can convert non-aromatic hydrocarbon components in the crude oil into low-carbon olefin to the maximum extent, convert heavy aromatic hydrocarbon components into low-carbon aromatic hydrocarbon and needle coke, reduce the yield of oil products with low additional value and the dependence on hydrogen, and realize the efficient utilization of petroleum resources of alkene and arene in preference.

Drawings

FIG. 1 is a schematic diagram of a process scheme for maximizing the production of aromatics from crude oil in a refinery.

FIG. 2 is a schematic diagram of the process for preparing chemicals from crude oil according to the present invention.

Description of the reference numerals

1 is crude oil, 2 is an atmospheric and vacuum distillation unit, 3 is a light hydrocarbon recovery unit, 4 is a kerosene hydrofining unit, 5 is a diesel hydrocracking unit, 6 is a boiling bed residual oil hydrocracking unit, 7 is C3/C4, 8 is a naphtha hydrocracking unit, 9 is a steam cracking unit, 10 is heavy naphtha, 11 is a continuous reforming unit, 12 is paraxylene/benzene, 13 is a wax oil hydrocracking unit, 14 is a solvent deasphalting unit, 15 is a lubricating oil isomerization dewaxing unit, 16 is hydrogen, 17 is a crude oil hydrofining unit, 18 is fuel gas, 19 is refined crude oil, 20 is a crude oil adsorption separation unit, 21 is a crude oil non-aromatic component, 22 is a crude oil aromatic component, 23 is an olefin yield increasing unit, 24 is a rich olefin gas, 25 is cracked gasoline diesel, 26 is oil slurry, 27 is coke, 28 is a gasoline and diesel oil adsorption separation unit, 29 is a diesel oil non-aromatic component, 30 is gasoline and diesel oil aromatic hydrocarbon component, 31 is aromatic hydrocarbon component cutting unit, 32 is I-type aromatic hydrocarbon component (less than or equal to 350 ℃), 33 is II-type aromatic hydrocarbon component (more than 350 ℃), 34 is aromatic hydrocarbon yield increasing unit, 35 is fuel gas, 36 is saturated liquefied gas and light naphtha, 37 is benzene, toluene and xylene, 38 is C₉、C₁₀Aromatic hydrocarbon 39 is a needle coke yield increasing unit, 40 is coking gasoline and diesel oil, and 41 is needle coke.

Detailed Description

The following detailed description of the embodiments and the advantages of the present invention will be made with reference to the accompanying drawings, which are provided for illustration purposes, and are not intended to limit the scope of the present invention.

Comparative example 1: process scheme for maximizing aromatic hydrocarbon production by crude oil

For the example of maximizing aromatic hydrocarbon production from crude oil in a refinery, the process flow diagram is shown in FIG. 1. The scheme mainly comprises an atmospheric and vacuum distillation unit 2, a light hydrocarbon recovery unit 3, a kerosene hydrofining unit 4, a diesel oil hydrocracking unit 5, a residual oil hydrocracking unit 6, a naphtha hydrocracking unit 8, a wax oil hydrocracking unit 13, a solvent deasphalting unit 14, a continuous reforming unit 11 and a steam cracking unit 9.

By adding the process devices such as hydrocracking and the like, heavy products such as wax oil, residual oil and the like in the crude oil refining process are converted into light products, and the hydrogen-carbon ratio is improved. The existing mature technology is utilized, and the petrochemical raw material yield is greatly improved through reconfiguration. The actual product distribution of the refinery is shown in table 1.

Example 1

By adopting the combined process method, firstly, crude oil 1 and hydrogen 16 enter a crude oil hydrofining unit 17 for hydrofining, and sulfur, nitrogen and metal impurities are removed to obtain fuel gas 18 and refined crude oil 19; introducing the refined crude oil 19 into a crude oil adsorption separation unit 20, and obtaining a crude oil non-aromatic hydrocarbon component 21 and a crude oil aromatic hydrocarbon component 22 under the action of an adsorbent; crude oil non-aromatic hydrocarbon components 21 enter an olefin yield increasing unit 23 to obtain alkene-rich gas 24, cracked gasoline and diesel oil 25, oil slurry 26 and coke 27; the cracked gasoline and diesel oil 25 enters a gasoline and diesel oil adsorption separation unit 28, and a gasoline and diesel oil non-aromatic component 29 and a gasoline and diesel oil aromatic component 30 are obtained under the action of a gasoline and diesel oil aromatic hydrocarbon adsorbent; returning the non-aromatic components 29 of the gasoline and diesel oil to the olefin yield increasing unit 23 to be used as cracking raw materials; crude oil aromatic hydrocarbon component 22 enters an aromatic hydrocarbon component cutting unit 31, and a I-type aromatic hydrocarbon component 32 with the distillation range of less than or equal to 350 ℃ and a II-type aromatic hydrocarbon component 33 with the distillation range of more than 350 ℃ are obtained through rectification cutting; the I-type aromatic hydrocarbon component 32 with the distillation range less than or equal to 350 ℃ and the gasoline and diesel oil aromatic hydrocarbon component 30 in the step (d) enter an aromatic hydrocarbon yield increasing unit 34, and hydrogenation and lightening are realized in a hydrogen atmosphere to obtain fuel gas 35, liquefied gas, light naphtha 36, BTX37 and C₉And C₁₀An aromatic hydrocarbon 38; the II-type aromatic hydrocarbon component 33 with the distillation range of more than 350 ℃ enters a needle coke yield increasing unit 39 to obtain the alkene-rich gas 24, the coking gasoline and diesel oil 40 and the needle coke 41.

The crude oil adsorption separation unit adopts a 24-column simulated moving bed process, the operation temperature is 60 ℃, the pressure is 0.2MPa, and the mass space velocity is 0.5h^-1The resolving agent is a mixture of toluene and methylcyclohexane, wherein the toluene content is 70 wt%, the operation parameters of the simulated moving bed are controlled,the aromatic hydrocarbon content of the non-aromatic hydrocarbon component of the crude oil is less than 5 wt%, and the non-aromatic hydrocarbon content of the aromatic hydrocarbon component of the crude oil is less than 5 wt%.

The gasoline and diesel oil adsorption separation unit adopts a 12-column simulated moving bed process, the operation temperature is 50 ℃, the pressure is 0.2MPa, and the mass space velocity is 0.5h^-1The analytical agent is a mixture of toluene and methylcyclohexane, wherein the toluene content is 30 wt%, and the operating parameters of the simulated moving bed are controlled, so that the aromatic hydrocarbon content of the non-aromatic components of the gasoline and diesel oil is less than 5 wt%, and the non-aromatic hydrocarbon content of the aromatic components of the gasoline and diesel oil is less than 5 wt%.

Other units may employ conventional operating conditions found in the literature. The conditions adopted in this example are as follows:

the conditions of the crude oil hydrofining unit are as follows: the average reaction temperature is 375 ℃, and the volume space velocity is 0.5h^-1The reaction hydrogen partial pressure is 16MPa, and the volume ratio of hydrogen to oil at the inlet of the reactor is 900.

The olefin yield increasing unit conditions are as follows: the reaction temperature is 620 ℃, the agent-oil ratio is 12, the water-oil ratio is 0.25, and the retention time is 2 s.

The aromatic hydrocarbon yield increasing unit conditions are as follows: the reaction temperature is 390 ℃, the hydrogen partial pressure is 5MPa, and the volume space velocity is 1.2h^-1Hydrogen to hydrocarbon volume ratio 1000.

The conditions of the needle coke yield increasing unit are as follows: the reaction temperature of the coking device is 510 ℃, and the reaction pressure is 0.15 MPa.

The properties of the starting materials used in the examples are shown in Table 2. Examples representative product schemes are shown in table 3.

TABLE 1 product distribution for process for maximizing aromatic production from crude oil

Table 2 properties of the raw materials used in the examples

Name of item	Crude oil Properties
		Density, g/cm3	0.862
Sulfur content, w%	0.15
		Acid value, mgKOH%	0.32
Nitrogen content, w%	0.16
		Paraffin, w%	54.0
Cycloalkane, w%	29.3
		Aromatic hydrocarbon, w%	16.7

Table 3 example representative product distribution

Principal product	Yield, wt.%
		Trienes as inhibitors of HIV infection	50.46
BTX	4.16
		C9, C10 aromatic hydrocarbons	1.56
Chemical product yield	56.18
		Needle coke	4.77
Coking gasoline and diesel oil	4.07

Compared with a comparative example, the combined process method for preparing the chemicals from the crude oil provided by the invention has the advantages that non-aromatic hydrocarbon components and aromatic hydrocarbon components in the crude oil are respectively fed into more suitable units for processing, so that the yield of the chemicals is increased, the non-aromatic hydrogenation loss is reduced, a large amount of aromatic hydrocarbon is prevented from being coked in an olefin yield increasing unit, a part of needle coke products are by-produced, and the yield of the oils with low added values and the dependence on hydrogen are reduced. The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the embodiments is to enable people to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the main technical scheme of the invention are covered in the protection scope of the invention.