阅读说明：本技术 一种原油制化学品的组合工艺方法 (Combined process for preparing chemical products from crude oil ) 是由 范景新 于海斌 臧甲忠 郭春垒 王春雷 靳凤英 李滨 辛利 刘凯隆 宫毓鹏 王静 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的组合工艺方法,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,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加氢精制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, which 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 a crude oil non-aromatic hydrocarbon component and a crude oil aromatic hydrocarbon component are obtained under the action of an adsorbent; 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 hydrofining 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 invention takes the crude oil as the raw material to produce the low-carbon olefin and the low-carbon aromatic hydrocarbon to the maximum extent, and reduces the oil products with low added values, thereby realizing the 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 enter an olefin yield increasing unit to undergo cracking reaction to obtain alkene-rich gas, cracked gasoline and diesel oil, tar and coke;

(d) the cracked gasoline and diesel oil in the step (c) enters a gasoline and diesel oil hydrofining unit, and fuel gas, saturated liquefied gas, light naphtha and refined gasoline and diesel oil are obtained in a hydrogen atmosphere;

(e) returning the fuel gas, the saturated liquefied gas and the light naphtha to an 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 refined gasoline and diesel oil in the step (d) enter an aromatic hydrocarbon yield increasing unit to realize hydrogenation and lightening in a hydrogen atmosphere to obtain fuel gas, saturated liquefied gas, light naphtha, BTX and C₉And C₁₀Aromatic hydrocarbons;

(h) returning the fuel gas, the saturated liquefied gas and the light naphtha to an olefin yield increasing unit to be used as cracking raw materials;

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

2. The combined process according to claim 1, characterized in that: 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 according to claim 1, characterized in that: the analytic agent used by the crude oil adsorption separation unit is one or more of methylcyclohexane, toluene, ethylbenzene and xylene, or one or more of methanol, ethanol and propanol.

4. The combined process according to claim 1, characterized in that: and b) adsorbing and separating to obtain crude oil non-aromatic hydrocarbon components with the aromatic hydrocarbon content of not more than 10 wt% and crude oil aromatic hydrocarbon components with the non-aromatic hydrocarbon content of not more than 10 wt%.

5. The combined process according to claim 1, characterized in that: and b) adsorbing and separating to obtain crude oil non-aromatic hydrocarbon components with the aromatic hydrocarbon content not more than 5 wt% and crude oil aromatic hydrocarbon components with the non-aromatic hydrocarbon content not more than 5 wt%.

6. The combined process according to claim 1, characterized in that: the olefin yield increasing unit is a steam cracking unit or a catalytic cracking unit.

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 inventionThe main purpose of the method is to provide a combined process method for preparing chemical products from crude oil, which 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 enter an olefin yield increasing unit to undergo cracking reaction to obtain alkene-rich gas, cracked gasoline and diesel oil, tar and coke;

(d) the cracked gasoline and diesel oil in the step (c) enters a gasoline and diesel oil hydrofining unit, and fuel gas, saturated liquefied gas, light naphtha and refined gasoline and diesel oil are obtained in a hydrogen atmosphere;

(e) returning the fuel gas, the saturated liquefied gas and the light naphtha to an 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 refined gasoline and diesel oil in the step (d) enter an aromatic hydrocarbon yield increasing unit to realize hydrogenation and lightening in a hydrogen atmosphere to obtain fuel gas, saturated liquefied gas, light naphtha, BTX and C₉And C₁₀Aromatic hydrocarbons;

(h) returning the fuel gas, the saturated liquefied gas and the light naphtha obtained in the step (g) to an olefin yield increasing unit to be used as cracking raw materials;

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

In the technical scheme, 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 above technical scheme, the analytic agent used in the crude oil adsorption separation unit is one or more of methylcyclohexane, toluene, ethylbenzene or xylene, and may also be one or more of lower alcohols such as methanol, ethanol, propanol, and the like.

In step b), the crude oil adsorption separation unit preferably obtains crude oil non-aromatic components with aromatic content not more than 10 wt% and crude oil aromatic components with non-aromatic content not more than 10 wt%, more preferably obtains crude oil non-aromatic components with aromatic content not more than 5 wt% and crude oil aromatic components with non-aromatic content not more than 5 wt%.

The olefin stimulation unit is preferably a steam cracking unit or a catalytic cracking unit.

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 'preferably alkene, preferably arene'.

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 oil 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 stoneNaphtha, 11 is a continuous reforming unit, 12 is paraxylene, 13 is a wax oil hydrocracking unit, 14 is a solvent deasphalting unit, and 15 is a lubricating oil isodewaxing 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 hydrocarbon component, 22 is a crude oil aromatic hydrocarbon component, 23 is an olefin yield increasing unit, 24 is a rich olefin gas, 25 is cracked gasoline and diesel oil, 26 is tar, 27 is coke, 28 is a gasoline and diesel oil hydrofining unit, 29 is fuel gas, 30 is saturated liquefied gas, 31 is light naphtha, 32 is refined gasoline and diesel oil, 33 is an aromatic hydrocarbon component cutting unit, 34 is a type I aromatic hydrocarbon component (less than or equal to 350 ℃), 35 is a type II aromatic hydrocarbon component (greater than 350 ℃), 36 is an aromatic hydrocarbon yield increasing unit, 37 is benzene, toluene and xylene, and 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 examples are intended to illustrate the practice and advantageous effects of the present invention, but are not to be construed as limiting 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. 2. 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 product distribution is shown in table 1.

Example 1

The combined process for preparing chemicals from crude oil includes such steps as adding crude oil 1 and hydrogen 16 to the hydrorefining unit 17Hydrogen refining, removing sulfur, nitrogen and metal impurities to obtain fuel gas 18 and refined crude oil 19; introducing the refined crude oil 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 components enter an olefin yield increasing unit 23 to obtain alkene-rich gas 24, cracked gasoline and diesel oil 25, tar 26 and coke 27; the cracked gasoline and diesel oil 25 enters a gasoline and diesel oil hydrofining unit 28, and under the hydrogen atmosphere, fuel gas 29, saturated liquefied gas 30, light naphtha 31 and refined gasoline and diesel oil 32 are obtained; fuel gas 29, saturated liquefied gas 30 and light naphtha 31 obtained by the gasoline and diesel hydrofining unit 28 return to the olefin yield increasing unit 23 to be used as cracking raw materials; crude oil aromatic hydrocarbon component 32 enters an aromatic hydrocarbon component cutting unit 33, and a I-type aromatic hydrocarbon component 34 with the distillation range of less than or equal to 350 ℃ and a II-type aromatic hydrocarbon component 35 with the distillation range of more than 350 ℃ are obtained through rectification cutting; the I-type aromatic hydrocarbon component 34 with the distillation range less than or equal to 350 ℃ and the refined gasoline and diesel oil 32 in the step (d) enter an aromatic hydrocarbon yield increasing unit 36, and hydrogenation and lightening are realized in a hydrogen atmosphere to obtain fuel gas 29, saturated liquefied gas 30, BTX 37 and C₉And C₁₀An aromatic hydrocarbon 38; the fuel gas 29, the saturated liquefied gas 30 and the light naphtha 31 obtained by the aromatic hydrocarbon yield increasing unit 36 also return to the catalytic cracking unit to be used as cracking raw materials; the II-type aromatic hydrocarbon component 34 with the distillation range of more than 350 ℃ and tar enter a needle coke yield increasing unit 39 to obtain alkene-rich gas, coking gasoline and diesel oil 40 and 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 analytical agent is a mixture of toluene and methylcyclohexane, wherein the toluene content is 70 wt%, and the operating parameters of the simulated moving bed are controlled, so that the aromatic hydrocarbon content of the non-aromatic hydrocarbon component of the obtained crude oil is less than 5 wt%, and the non-aromatic hydrocarbon content of the aromatic hydrocarbon component of the obtained crude 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 crude oil hydrofining conditions 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 catalytic cracking 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 gasoline and diesel hydrorefining unit conditions are as follows: the hydrogen partial pressure of the reaction is 7MPa, the average reaction temperature is 330 ℃, and the space velocity of the reaction volume is 2.5h^-1The volume ratio of hydrogen to oil is 800V/V.

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

Principal product	Yield, wt.%
		Para-xylene	21.7
Pure benzene	4.85
		Polypropylene	2.2
Chemical light oil	8.15
		95# national V gasoline	12.75
92# national V gasoline	10.3
		GuoV diesel oil	8.05
Aviation kerosene	18.55
		Commercial liquefied gas	3.25
Lubricating oil base oil	2.7
		Heavy aromatic hydrocarbons	0.65
Sulfur	2.6
		Chemical product yield	42

Table 2 properties of the raw materials used in the examples

Table 3 example representative product distribution

Principal product	Yield, wt.%
		Trienes as inhibitors of HIV infection	51.13
BTX	4.25
		C9, C10 aromatic hydrocarbons	1.61
Chemical product yield	56.99
		Needle coke	5.71
Coking gasoline and diesel oil	5.00

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.