CN112745949B

Movatterモバイル変換

Info

Publication number: CN112745949B
Application number: CN201911053864.9A
Authority: CN
Inventors: 杨清河; 贾燕子; 牛传峰; 孙淑玲; 胡大为; 戴立顺; 王振; 任亮; 户安鹏
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2022-06-28
Anticipated expiration: 2039-10-31
Also published as: CN112745949A

Abstract

The invention relates to the field of hydrocarbon oil processing, and discloses a method and a system for combined processing of deoiled asphalt, which comprises the following steps: (11) carrying out solvent deasphalting treatment on heavy raw oil; (12) carrying out hydrogenation reaction on the deasphalted oil, and introducing liquid phase effluent into a DCC unit for reaction; (2) carrying out hydrogenation saturation on the aromatic-rich distillate oil containing LCO and/or HCO and then fractionating; (3) mixing the deoiled asphalt and the aromatic hydrocarbon-containing material flow with hydrogen and then carrying out hydrogenation reaction; (4) fractionating the liquid phase product; (51) reacting the second light component to yield at least one product selected from the group consisting of a gasoline component, a diesel component, and a BTX feedstock component; and (52) reacting the second heavy components to yield at least one product selected from the group consisting of coker gasoline, coker diesel, coker gas oil, and low sulfur petroleum coke; or the second heavy component as a low sulfur marine fuel oil component. The treatment process provided by the invention can realize high-value DOA utilization.

Description

Translated fromChinese

一种联合加工脱油沥青和富芳馏分油的方法和系统A method and system for combined processing of deoiled pitch and aromatic-rich distillate

技术领域technical field

本发明涉及烃油加工领域，具体涉及一种联合加工脱油沥青和富芳馏分油的方法和一种联合加工脱油沥青和富芳馏分油的系统。The invention relates to the field of hydrocarbon oil processing, in particular to a method for combined processing of deoiled asphalt and aromatic-rich distillate oil and a system for combined processing of de-oiled asphalt and aromatic-rich distillate oil.

背景技术Background technique

渣油高效转化是炼油企业的核心。而固定床渣油加氢是渣油高效转化的关键技术，具有产品质量好、工艺成熟等特点。Efficient conversion of residual oil is the core of oil refining enterprises. The hydrogenation of fixed-bed residue oil is the key technology for the efficient conversion of residue oil, which has the characteristics of good product quality and mature technology.

但渣油中高含量的沥青质和金属是固定床渣油加氢装置运转周期的制约因素。However, the high content of asphaltenes and metals in the residual oil is the limiting factor for the operation cycle of the fixed-bed residual oil hydrotreating unit.

为解决这一难题，中石化石油化工科学研究院开发的渣油溶剂脱沥青(脱金属)-加氢处理-催化裂化组合工艺技术(SHF)是从低价值减压渣油中最大限度生产车用清洁燃料并延长运转周期的创新技术，但由于脱油沥青质(DOA)软化点高，难于输送和利用，限制了SHF技术的推广。To solve this problem, the combined process technology of residual solvent deasphalting (demetallization)-hydroprocessing-catalytic cracking (SHF) developed by Sinopec Petrochemical Research Institute is to maximize the production of automotive products from low-value vacuum residues. The innovative technology of cleaning fuel and prolonging the operation cycle, but due to the high softening point of deoiled asphaltene (DOA), it is difficult to transport and utilize, which limits the promotion of SHF technology.

向化工转型的渣油加氢-催化裂解(DCC)多产丙烯的新组合工艺，也是受限于渣油中的沥青质和金属的影响，加氢渣油氢含量低，渣油加氢的运转周期短，DCC丙烯收率低，影响组合技术的经济效益。The new combined process of residual oil hydrogenation-catalytic cracking (DCC) to produce more propylene in the chemical industry is also limited by the influence of asphaltenes and metals in the residual oil. The operation period is short and the DCC propylene yield is low, which affects the economic benefits of the combined technology.

另外，2020年开始要实行硫质量分数≯0.5％的低硫船燃新标准和硫质量分数≯3.0％的低硫石油焦标准，如何低成本生产低硫船燃(低硫石油焦) 技术也是目前急需解决的问题。In addition, starting from 2020, a new standard for low-sulfur marine fuel with a sulfur mass fraction of ≯ 0.5% and a low-sulfur petroleum coke standard with a sulfur mass fraction of ≯ 3.0% will be implemented. How to produce low-sulfur marine fuel (low-sulfur petroleum coke) technology at low cost problems that need to be solved urgently.

因此，将DOA转化成低硫船燃或生产低硫石油焦的原料是迫切需要解决的技术难题。Therefore, converting DOA into low-sulfur fuel for ships or producing low-sulfur petroleum coke is an urgent technical problem to be solved.

发明内容SUMMARY OF THE INVENTION

本发明的目的是为了克服现有技术无法高价值利用DOA的弊端。The purpose of the present invention is to overcome the disadvantage that the prior art cannot utilize DOA with high value.

为了实现上述目的，本发明的第一方面提供一种联合加工脱油沥青和富芳馏分油的方法，该方法包括：In order to achieve the above object, a first aspect of the present invention provides a method for combined processing of deoiled pitch and aromatic-rich distillate oil, the method comprising:

(11)将重质原料油引入至溶剂脱沥青单元中进行溶剂脱沥青处理，得到脱油沥青和脱沥青油；(11) introducing heavy feedstock oil into a solvent deasphalting unit for solvent deasphalting treatment to obtain deoiled asphalt and deasphalted oil;

(12)将所述脱沥青油引入至第一加氢单元中进行加氢反应，并将所述第一加氢单元中获得的液相流出物引入至DCC单元进行反应，得到丙烯、 LCO、HCO和油浆，其中，所述第一加氢单元为固定床加氢单元；(12) The deasphalted oil is introduced into the first hydrogenation unit for hydrogenation reaction, and the liquid-phase effluent obtained in the first hydrogenation unit is introduced into the DCC unit for reaction to obtain propylene, LCO, HCO and oil slurry, wherein, the first hydrogenation unit is a fixed bed hydrogenation unit;

(2)将含有来自所述DCC单元的LCO和/或HCO的富芳馏分油引入至第二加氢单元中进行加氢饱和后分馏以获得第一轻组分和第一重组分，所述第一轻组分和所述第一重组分的切割点为100-250℃，所述第一重组分中的芳烃含量为大于等于20质量％；(2) introducing an aromatic-rich distillate containing LCO and/or HCO from the DCC unit into a second hydrogenation unit for hydrosaturation and post-fractionation to obtain a first light component and a first heavy component, the The cutting point of the first light component and the first heavy component is 100-250° C., and the aromatic hydrocarbon content in the first heavy component is greater than or equal to 20% by mass;

(3)将所述脱油沥青和含有所述第一重组分的含芳烃物流引入至溶氢单元中与氢气混合，并将混合后的物料引入至第三加氢单元中进行加氢反应，其中，所述第三加氢单元中含有富矿前驱体材料和/或加氢催化剂，所述第三加氢单元为液相加氢反应单元，所述富矿前驱体材料为能够吸附选自 V、Ni、Fe、Ca和Mg中的至少一种金属的材料，所述脱油沥青和所述含芳烃物流的用量比使得由该脱油沥青和含芳烃物流形成的混合原料在不高于400℃时呈液态；(3) introducing the deoiled pitch and the aromatic-containing stream containing the first heavy component into a hydrogen dissolving unit to be mixed with hydrogen, and introducing the mixed material into a third hydrogenation unit for hydrogenation reaction, Wherein, the third hydrogenation unit contains a rich ore precursor material and/or a hydrogenation catalyst, the third hydrogenation unit is a liquid phase hydrogenation reaction unit, and the rich ore precursor material is capable of adsorbing selected from V, The material of at least one metal among Ni, Fe, Ca and Mg, the amount ratio of the deoiled asphalt and the aromatics-containing stream is such that the mixed feed formed from the deoiled asphalt and the aromatics-containing stream has a temperature not higher than 400°C liquid;

(4)将来自所述第三加氢单元的液相产物进行分馏，得到第二轻组分和第二重组分，其中，所述第二轻组分和所述第二重组分的切割点为 240～450℃；(4) fractional distillation of the liquid phase product from the third hydrogenation unit to obtain a second light component and a second heavy component, wherein the cutting point of the second light component and the second heavy component 240～450℃;

(51)将所述第二轻组分引入至第四反应单元中进行反应以得到选自汽油组分、柴油组分和BTX原料组分中的至少一种产物，或者将所述第二轻组分循环回所述DCC单元中，其中，所述第四反应单元选自加氢裂化单元、催化裂化单元和柴油加氢提质单元中的至少一种；以及(51) introducing the second light component into the fourth reaction unit for reaction to obtain at least one product selected from the gasoline component, the diesel component and the BTX feedstock component, or the second light component The components are recycled back to the DCC unit, wherein the fourth reaction unit is selected from at least one of a hydrocracking unit, a catalytic cracking unit, and a diesel hydroupgrading unit; and

(52)将所述第二重组分引入至延迟焦化单元中进行反应以得到选自焦化汽油、焦化柴油、焦化蜡油和低硫石油焦中的至少一种产物；或者将所述第二重组分作为低硫船用燃料油组分。(52) introducing the second heavy component into a delayed coking unit for reaction to obtain at least one product selected from coker gasoline, coking diesel oil, coking wax oil and low-sulfur petroleum coke; or recombining the second As a component of low-sulfur marine fuel oil.

本发明的第二方面提供一种联合加工脱油沥青和富芳馏分油的系统，该系统中包括：A second aspect of the present invention provides a system for combined processing of deoiled pitch and aromatic-rich distillate, comprising:

溶剂脱沥青单元，该溶剂脱沥青单元用于将重质原料油在其中进行溶剂脱沥青处理，得到脱油沥青和脱沥青油；A solvent deasphalting unit, the solvent deasphalting unit is used for solvent deasphalting treatment of heavy feedstock oil therein to obtain deoiled asphalt and deasphalted oil;

第一加氢单元，该第一加氢单元与所述溶剂脱沥青单元保持流体连通，且该第一加氢单元为固定床加氢单元，用于将来自所述溶剂脱沥青单元的脱沥青油在其中进行加氢反应；a first hydrogenation unit in fluid communication with the solvent deasphalting unit and which is a fixed bed hydrogenation unit for deasphalting the solvent from the solvent deasphalting unit The oil is hydrogenated therein;

DCC单元，该DCC单元与所述第一加氢单元保持流体连通，用于将所述第一加氢单元中获得的液相流出物在其中进行反应以得到丙烯、LCO、 HCO和油浆；A DCC unit in fluid communication with the first hydrogenation unit for reacting therein a liquid phase effluent obtained in the first hydrogenation unit to obtain propylene, LCO, HCO and an oil slurry;

第二加氢单元，该第二加氢单元与所述DCC单元保持流体连通，用于将含有来自所述DCC单元的LCO和/或HCO的富芳馏分油在其中进行加氢饱和和分馏以得到第一轻组分和第一重组分；A second hydrogenation unit in fluid communication with the DCC unit for hydrosaturating and fractionating therein an aromatic-rich distillate containing LCO and/or HCO from the DCC unit to obtaining the first light component and the first heavy component;

溶氢单元，该溶氢单元与所述第二加氢单元保持流体连通，用于将来自所述溶剂脱沥青单元的脱油沥青和含有来自所述第二加氢单元的第一重组分的含芳烃物流在其中与氢气混合；a hydrogen dissolving unit in fluid communication with the second hydrogenation unit for dissolving the deoiled bitumen from the solvent deasphalting unit and the wherein the aromatics-containing stream is mixed with hydrogen;

第三加氢单元，该第三加氢单元为液相加氢反应单元且与所述溶氢单元保持流体连通，用于将所述溶氢单元的混合物料在其中进行加氢反应；a third hydrogenation unit, the third hydrogenation unit is a liquid-phase hydrogenation reaction unit and is in fluid communication with the hydrogen-dissolving unit, and is used for performing hydrogenation reaction in the mixed material of the hydrogen-dissolving unit;

分离单元，该分离单元与所述第三加氢单元和所述DCC单元分别保持流体连通，用于将来自所述第三加氢单元的液相产物在其中进行分馏，以及能够将该分离单元中所得的第二轻组分循环回所述DCC单元中；a separation unit in fluid communication with the third hydrogenation unit and the DCC unit, respectively, for fractionating liquid phase products from the third hydrogenation unit therein, and capable of the separation unit The second light component obtained in is recycled back to the DCC unit;

第四反应单元，该第四反应单元与所述分离单元保持流体连通，用于将由所述分离单元中获得的第二轻组分在其中进行反应，所述第四反应单元选自加氢裂化单元、催化裂化单元和柴油加氢提质单元中的至少一种；a fourth reaction unit in fluid communication with the separation unit for reacting therein the second light components obtained from the separation unit, the fourth reaction unit being selected from hydrocracking at least one of a unit, a catalytic cracking unit, and a diesel hydroupgrading unit;

延迟焦化单元，该延迟焦化单元与所述分离单元保持流体连通，用于将来自所述分离单元的第二重组分在其中进行反应以得到选自焦化汽油、焦化柴油、焦化蜡油和低硫石油焦中的至少一种产物；a delayed coking unit in fluid communication with the separation unit for reacting therein a second heavy component from the separation unit to obtain a coker selected from the group consisting of coker gasoline, coker diesel, coker wax oil, and low sulfur at least one product of petroleum coke;

出口，该出口与所述分离单元保持流体连通，用于将来自所述分离单元的第二重组分作为低硫船用燃料油组分引出系统。An outlet in fluid communication with the separation unit for withdrawing the second heavier component from the separation unit out of the system as a low sulfur marine fuel oil component.

本发明特别适用于常渣与减渣的加氢转化，尤其适用于高金属、高残炭、高稠环物质、高氮含量的劣质渣油加氢转化。The present invention is especially suitable for the hydroconversion of normal residue and reduced residue, and is especially suitable for the hydroconversion of inferior residue oil with high metal content, high carbon residue, high condensed ring substance and high nitrogen content.

本发明将脱油沥青(DOA)进行加氢处理的工艺方法，使得重油高效转化并能够生产汽油、BTX原料，以及能够灵活生产低硫船燃和低硫石油焦的系统和方法。The process method for hydrotreating deoiled asphalt (DOA) in the present invention enables the efficient conversion of heavy oil and the production of gasoline and BTX raw materials, as well as the system and method for flexible production of low-sulfur ship fuel and low-sulfur petroleum coke.

附图说明Description of drawings

图1是本发明的一种优选的具体实施方式的联合加工脱油沥青和富芳馏分油的工艺流程图。FIG. 1 is a process flow diagram of the combined processing of deoiled pitch and aromatic-rich distillate oil according to a preferred embodiment of the present invention.

附图标记说明Description of reference numerals

1 重油原料 2 溶剂脱沥青单元1Heavy oil feedstock 2 Solvent deasphalting unit

3 脱沥青油 4 脱油沥青3Deasphalted oil 4 Deoiled asphalt

5 芳烃化合物 6 混合原料5Aromatic compounds 6 Mixed raw materials

7 第三加氢单元 8 第二轻组分7Third Hydrogenation Unit 8 Second Lights

9 第二重组分 10 第四反应单元9 Secondheavy component 10 Fourth reaction unit

11 延迟焦化单元 12 BTX原料组分11Delayed coking unit 12 BTX feedstock components

13 汽油组分 14 柴油组分13Gasoline components 14 Diesel components

15 焦化汽油 16 焦化柴油15Coker gasoline 16 Coker diesel

17 焦化蜡油 18 低硫石油焦17 Cokingwax oil 18 Low sulfur petroleum coke

19 分离单元 20 富芳馏分油19Separation unit 20 Aromatic distillate

21 第二加氢单元 22 第一重组分21Second Hydrogenation Unit 22 First Heavy Component

23 油浆 24 第一加氢单元23Oil Slurry 24 First Hydrogenation Unit

25 DCC单元 26 丙烯25DCC unit 26 Propylene

27 LCO 28 HCO27 LCO 28 HCO

29 溶氢单元29 Hydrogen Dissolved Unit

具体实施方式Detailed ways

在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints of ranges and any values disclosed herein are not limited to the precise ranges or values, which are to be understood to encompass values proximate to those ranges or values. For ranges of values, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein.

如前所述，本发明的第一方面提供了一种联合加工脱油沥青和富芳馏分油的方法，该方法包括：As previously mentioned, a first aspect of the present invention provides a method for combined processing of deoiled pitch and aromatic-rich distillate, the method comprising:

优选地，所述脱油沥青和所述含芳烃物流的用量比使得由该脱油沥青和含芳烃物流形成的混合原料在不高于280℃时呈液态；进一步优选所述脱油沥青和所述含芳烃物流的用量比使得由该脱油沥青和含芳烃物流形成的混合原料在不高于100℃时呈液态。Preferably, the amount ratio of the deoiled asphalt and the aromatics-containing stream is such that the mixed feedstock formed from the deoiled asphalt and the aromatics-containing stream is in a liquid state at a temperature not higher than 280°C; further preferably, the deoiled asphalt and the aromatics-containing stream are in a liquid state. The amount ratio of the aromatics-containing stream is such that the mixed feed formed from the deoiled asphalt and the aromatics-containing stream is liquid at a temperature not higher than 100°C.

在将所述第二轻组分循环回所述DCC单元中时，优选循环比为1～30质量％。When recycling the second light component back to the DCC unit, the recycling ratio is preferably 1 to 30% by mass.

本发明优选所述第二加氢单元中进行的加氢饱和反应为部分加氢饱和，特别优选所述第一轻组分和所述第一重组分的切割点为180℃。In the present invention, it is preferred that the hydrosaturation reaction carried out in the second hydrogenation unit is partial hydrosaturation, and it is particularly preferred that the cutting point of the first light component and the first heavy component is 180°C.

优选情况下，在本发明的溶氢单元中的操作条件包括：氢气的送入量与所述脱油沥青和所述含芳烃物流形成的混合原料的体积比(即氢油体积比) 为30-200，更优选为50-150，溶氢单元操作温度为300-450℃，压力为 2-20MPa。Preferably, the operating conditions in the hydrogen dissolving unit of the present invention include: the volume ratio of the amount of hydrogen fed to the mixed feedstock formed by the deoiled asphalt and the aromatic-containing stream (ie, the volume ratio of hydrogen to oil) is 30. -200, more preferably 50-150, the operating temperature of the hydrogen dissolving unit is 300-450°C, and the pressure is 2-20MPa.

根据本发明的方法，溶氢单元中与氢气混合后获得的混合后的物料能够以向上流动的方式进入第三加氢单元，也可以以向下流动的方式进入第三加氢单元。优选地，溶氢单元中与氢气混合后获得的混合后的物料以向上流动的方式进入第三加氢单元这样在反应过程中，溶解并分散在油料中的氢气基本不会聚集形成大的气泡并逸出，从而能够为加氢反应提供足够的氢源，获得更好的加氢处理效果，并进一步降低催化剂结焦趋势，使催化剂保持较高的催化活性，进一步延长催化剂的使用寿命和装置的稳定运行周期。According to the method of the present invention, the mixed material obtained by mixing with hydrogen in the hydrogen dissolving unit can enter the third hydrogenation unit in an upward flow mode, or can enter the third hydrogenation unit in a downward flow mode. Preferably, the mixed material obtained by mixing with hydrogen in the hydrogen dissolving unit enters the third hydrogenation unit in an upward flow manner, so that during the reaction process, the hydrogen dissolved and dispersed in the oil will not aggregate to form large bubbles. and escape, so as to provide sufficient hydrogen source for the hydrogenation reaction, obtain better hydrotreating effect, and further reduce the tendency of catalyst coking, keep the catalyst high catalytic activity, and further prolong the service life of the catalyst and the equipment’s performance. stable operation cycle.

所述第一轻组分优选进入催化裂化单元生产低碳烯烃。本发明对第一轻组分进入催化裂化单元生产低碳烯烃的具体操作条件没有特别的限制。The first light component preferably enters a catalytic cracking unit to produce light olefins. The present invention has no particular limitation on the specific operating conditions for the first light components to enter the catalytic cracking unit to produce light olefins.

特别优选地，所述第二轻组分和所述第二重组分的切割点为350℃。Particularly preferably, the cutting point of the second light component and the second heavy component is 350°C.

优选地，在步骤(3)中，所述脱油沥青和所述含芳烃物流的用量比使得由该脱油沥青和含芳烃物流形成的混合原料的100℃粘度不大于 400mm²/s，更优选不大于200mm²/s，进一步优选不大于100mm²/s。Preferably, in step (3), the amount ratio of the deoiled asphalt and the aromatics-containing stream is such that the 100°C viscosity of the mixed feedstock formed from the deoiled asphalt and the aromatics-containing stream is not greater than 400 mm² /s, more It is preferably not more than 200 mm² /s, more preferably not more than 100 mm² /s.

优选情况下，在步骤(3)中，所述含芳烃物流中还含有芳烃化合物和/ 或芳烃油，所述芳烃油选自FGO(催化重馏出油)、乙烯焦油、煤焦油、焦化柴油和焦化蜡油中的至少一种。Preferably, in step (3), the aromatic-containing stream also contains aromatic compounds and/or aromatic oil, and the aromatic oil is selected from FGO (catalytic heavy distillate oil), ethylene tar, coal tar, coker diesel oil and at least one of coker wax oil.

优选地，所述芳烃化合物选自苯、甲苯、二甲苯、萘、甲基萘、多支链萘及双环以上芳烃中的一种或几种，优选为环数不超过三环的多环芳烃或它们的混合物。特别优选情况下，所述芳烃化合物选自苯、甲苯、二甲苯、萘、由至少一种C_1-6的烷基取代的萘、三环以上芳烃中的至少一种。Preferably, the aromatic hydrocarbon compound is selected from one or more of benzene, toluene, xylene, naphthalene, methyl naphthalene, multi-branched naphthalene and aromatic hydrocarbons with more than two rings, preferably polycyclic aromatic hydrocarbons with no more than three rings or their mixtures. Particularly preferably, the aromatic hydrocarbon compound is selected from at least one of benzene, toluene, xylene, naphthalene, naphthalene substituted by at least one C_1-6 alkyl group, and aromatic hydrocarbons with three or more rings.

更优选地，所述富芳馏分油中的芳烃含量大于等于20质量％，优选大于等于25质量％，特别优选大于等于40质量％。More preferably, the aromatic hydrocarbon content in the aromatic-rich distillate oil is greater than or equal to 20% by mass, preferably greater than or equal to 25% by mass, particularly preferably greater than or equal to 40% by mass.

优选地，在所述溶剂脱沥青单元中，所述脱油沥青的收率质量分数不大于50％，更优选不大于40％，进一步优选不大于30％。Preferably, in the solvent deasphalting unit, the yield mass fraction of the deoiled asphalt is not more than 50%, more preferably not more than 40%, further preferably not more than 30%.

根据一种优选的具体实施方式，在步骤(3)中，所述脱油沥青与所述含芳烃物流的用量质量比为1:10至50:10，更优选为2:10至30:10；进一步优选为3:10至15:10。According to a preferred embodiment, in step (3), the amount-to-mass ratio of the deoiled asphalt to the aromatic-containing stream is 1:10 to 50:10, more preferably 2:10 to 30:10 ; further preferably 3:10 to 15:10.

优选地，本发明的该方法还包括：将步骤(52)中获得的所述焦化柴油和/或所述焦化蜡油循环回所述第二加氢单元中进行加氢饱和。Preferably, the method of the present invention further comprises: recycling the coking diesel oil and/or the coking wax oil obtained in step (52) back to the second hydrogenation unit for hydrosaturation.

优选情况下，在步骤(12)中，所述第一加氢单元的操作条件包括：反应温度为280～400℃，反应压力为6.0～14.0MPa，氢油体积比为600～1200，液时体积空速为0.3～2.0h^-1。Preferably, in step (12), the operating conditions of the first hydrogenation unit include: the reaction temperature is 280-400°C, the reaction pressure is 6.0-14.0MPa, the volume ratio of hydrogen to oil is 600-1200, the liquid hour The volumetric space velocity is 0.3 to 2.0 h^-1 .

优选地，在步骤(12)中，所述第一加氢单元中装填有至少两种加氢催化剂。更优选地，在步骤(12)中，所述加氢催化剂为能够催化选自加氢脱金属反应、加氢脱硫反应和加氢脱残炭反应中的至少一种反应的催化剂。所述加氢催化剂一般都是以多孔耐熔无机氧化物如氧化铝为载体；特别优选情况下，在步骤(12)中，所述加氢催化剂中含有作为载体的氧化铝和作为活性组分元素的第VIB族和/或VIII族金属元素，且该加氢催化剂中任选还含有选自P、Si、F和B中的至少一种助剂元素。在所述加氢催化剂中，所述第VIB族和VIII族金属元素例如可以为W、Mo、Co、Ni等。并且，在所述加氢催化剂中，所述活性组分可以为上述活性组分元素的氧化物和/或硫化物。Preferably, in step (12), the first hydrogenation unit is loaded with at least two hydrogenation catalysts. More preferably, in step (12), the hydrogenation catalyst is a catalyst capable of catalyzing at least one reaction selected from the group consisting of hydrodemetallization reaction, hydrodesulfurization reaction and hydrodecarbon residue reaction. The hydrogenation catalysts are generally supported by porous refractory inorganic oxides such as alumina; particularly preferably, in step (12), the hydrogenation catalysts contain alumina as a support and as an active component The element is a metal element of Group VIB and/or Group VIII, and the hydrogenation catalyst optionally further contains at least one auxiliary element selected from the group consisting of P, Si, F and B. In the hydrogenation catalyst, the metal elements of Group VIB and Group VIII may be, for example, W, Mo, Co, Ni, and the like. And, in the hydrogenation catalyst, the active component may be oxides and/or sulfides of the above-mentioned active component elements.

以下提供本发明的第一加氢单元中的优选的具体实施方式：Preferred embodiments in the first hydrogenation unit of the present invention are provided below:

有氢存在的脱沥青油(DAO)的第一加氢单元的条件通常如下：DAO 的加氢处理技术为固定床加氢处理技术。以目前工业上较成熟固定床重、渣油加氢技术为例，所述反应器或反应床层至少包括两种加氢催化剂，采用的重渣油加氢催化剂是指具有重、渣油加氢脱金属、加氢脱硫、加氢脱氮和加氢脱残炭等功能的组合催化剂。这些催化剂一般都是以多孔耐熔无机氧化物如氧化铝为载体，第ⅥB族和/或Ⅷ族金属如W、Mo、Co、Ni等的氧化物或硫化物为活性组分，选择性地加入其它各种助剂如P、Si、F、B等元素的催化剂，例如由石油化工科学研究院研发的RDM、RCS系列重、渣油加氢脱金属催化剂和脱硫催化剂。目前在固定床渣油加氢技术中，经常是多种催化剂配套使用，其中有加氢脱金属催化剂、加氢脱硫催化剂、加氢脱氮催化剂，装填顺序一般是使原料油依次与加氢脱金属、加氢脱硫、加氢脱氮催化剂接触，有时也可根据情况，少装一种或两种催化剂，例如只装填加氢脱金属催化剂和加氢脱硫催化剂，而不装加氢脱氮催化剂。当然也有将这几种催化剂混合装填的技术。The conditions of the first hydrotreating unit of deasphalted oil (DAO) in the presence of hydrogen are generally as follows: The hydrotreating technology of DAO is a fixed bed hydrotreating technology. Taking the current industrially mature fixed-bed heavy-residue hydrogenation technology as an example, the reactor or the reaction bed layer includes at least two hydrogenation catalysts, and the heavy-residue hydrogenation catalyst used refers to the hydrogenation catalyst with heavy and residual oil. Combined catalyst with functions such as hydrodemetallization, hydrodesulfurization, hydrodenitrogenation and hydrodecarbon residue. These catalysts are generally supported by porous refractory inorganic oxides such as alumina, and oxides or sulfides of Group VIB and/or Group VIII metals such as W, Mo, Co, Ni, etc. as active components, optionally Catalysts with other additives such as P, Si, F, B and other elements added, such as RDM, RCS series heavy and residual oil hydrodemetallization catalysts and desulfurization catalysts developed by the Research Institute of Petrochemical Engineering. At present, in the fixed-bed residue hydrogenation technology, various catalysts are often used together, including hydrodemetallization catalysts, hydrodesulfurization catalysts, and hydrodenitrogenation catalysts. Metal, hydrodesulfurization, hydrodenitrogenation catalyst contact, and sometimes one or two catalysts can be omitted according to the situation, for example, only the hydrodemetallization catalyst and the hydrodesulfurization catalyst are loaded, but the hydrodenitrogenation catalyst is not installed. . Of course, there are also techniques for mixing and packing these catalysts.

优选地，在步骤(2)中，所述第二加氢单元为固定床反应器、移动床反应器和沸腾床反应器中的至少一种反应器。Preferably, in step (2), the second hydrogenation unit is at least one of a fixed bed reactor, a moving bed reactor and an ebullated bed reactor.

优选情况下，所述第二加氢单元中的操作条件包括：反应温度为 200-420℃，反应压力为2-18MPa，液时体积空速为0.3-10h^-1，氢油体积比 50-5000；更优选地，所述第二加氢单元中的操作条件包括：反应温度为 220-400℃，反应压力为2-15MPa，液时体积空速为0.3-5h^-1，氢油体积比为 50-4000。Preferably, the operating conditions in the second hydrogenation unit include: the reaction temperature is 200-420°C, the reaction pressure is 2-18MPa, the liquid hourly volumetric space velocity is 0.3-10h^-1 , and the volume ratio of hydrogen to oil is 50- 5000; more preferably, the operating conditions in the second hydrogenation unit include: the reaction temperature is 220-400°C, the reaction pressure is 2-15MPa, the liquid hourly volumetric space velocity is 0.3-5h^-1 , and the volume ratio of hydrogen to oil is 220-400°C. 50-4000.

以下提供本发明的第二加氢单元中的优选的具体实施方式：Preferred embodiments in the second hydrogenation unit of the present invention are provided below:

有氢存在的富芳馏分油的部分加氢饱和的条件通常如下：富芳馏分油的部分加氢饱和技术为固定床/沸腾床/移动床加氢处理技术。以目前工业上较成熟固定床柴油或蜡油加氢技术为例，所述反应器或反应床层至少包括一种加氢精制催化剂。富芳馏分油的部分加氢饱和中应用的加氢精制催化剂优选具有良好且适中的加氢饱和活性，以避免四氢萘类结构进一步饱和为供氢能力较低的十氢萘或环烷烃结构。这些催化剂一般都是以多孔耐熔无机氧化物如氧化铝为载体，第ⅥB族和/或Ⅷ族金属如W、Mo、Co、Ni等的氧化物为活性组分，选择性地加入其它各种助剂如P、Si、F、B等元素的催化剂，例如由石油化工科学研究院研发的RS系列预处理催化剂就属于这类催化剂。RS系列催化剂是一种NiMo催化剂。The conditions for partial hydrosaturation of aromatic-rich distillates in the presence of hydrogen are generally as follows: The partial hydrosaturation technology of aromatic-rich distillates is fixed bed/ebullated bed/moving bed hydrotreating technology. Taking the current industrially mature fixed-bed diesel or wax oil hydrogenation technology as an example, the reactor or reaction bed layer includes at least one hydrotreating catalyst. The hydrofinishing catalyst used in the partial hydrosaturation of aromatic-rich distillates preferably has good and moderate hydrosaturation activity to avoid further saturation of tetralin-like structures into decalin or naphthenic structures with lower hydrogen-donating capacity . These catalysts are generally supported by porous refractory inorganic oxides such as alumina, oxides of Group VIB and/or Group VIII metals such as W, Mo, Co, Ni, etc. as active components, and other Catalysts of various additives such as P, Si, F, B and other elements, such as the RS series pretreatment catalysts developed by the Research Institute of Petrochemical Engineering, belong to this category of catalysts. The RS series catalyst is a NiMo catalyst.

本发明优选所述第三加氢单元为渣油液相加氢反应器。In the present invention, preferably, the third hydrogenation unit is a residual oil liquid-phase hydrogenation reactor.

优选情况下，在步骤(3)中，所述第三加氢单元中的操作条件包括：反应温度260～500℃，反应压力为2.0～20.0MPa，循环油与所述第三加氢单元入口原料油的体积比例为0.1:1至15:1，液时体积空速为0.1～1.5h^-1。液时体积空速和反应压力可以根据待处理物料的特性和要求的转化率及精制深度进行选择的。本发明由脱油沥青和含芳烃物流形成的混合原料与氢气混合后可以从第三加氢单元的反应器的顶部进入，自上向下下行穿过催化剂床层；也可以从第三加氢单元的反应器的底部进入，自下向上上行穿过催化剂床层。Preferably, in step (3), the operating conditions in the third hydrogenation unit include: a reaction temperature of 260 to 500° C., a reaction pressure of 2.0 to 20.0 MPa, the circulating oil and the inlet of the third hydrogenation unit. The volume ratio of the raw oil is 0.1:1 to 15:1, and the liquid hourly volume space velocity is 0.1 to 1.5h^-1 . The liquid hourly volume space velocity and reaction pressure can be selected according to the characteristics of the material to be treated and the required conversion rate and refining depth. The mixed raw material formed by the deoiled asphalt and the stream containing aromatic hydrocarbons in the present invention can enter from the top of the reactor of the third hydrogenation unit after being mixed with hydrogen, and pass through the catalyst bed from top to bottom; The bottom of the reactor of the unit enters and goes up through the catalyst bed from bottom to top.

优选地，在步骤(3)中，所述富矿前驱体材料中含有载体和负载在所述载体上的活性组分元素，所述载体选自氢氧化铝、氧化铝和氧化硅中的至少一种，所述活性组分元素选自第VIB族和VIII族金属元素中的至少一种。更优选地，所述富矿前驱体材料中的活性组分为选自第VIB族和VIII族金属元素的氧化物和/或硫化物。Preferably, in step (3), the rich ore precursor material contains a carrier and an active component element supported on the carrier, and the carrier is selected from at least one of aluminum hydroxide, aluminum oxide and silicon oxide The active component element is selected from at least one of the metal elements of Group VIB and Group VIII. More preferably, the active components in the rich ore precursor material are oxides and/or sulfides of metal elements selected from Group VIB and Group VIII.

优选情况下，在步骤(3)中，所述富矿前驱体材料的灼减不低于3质量％，比表面积不低于80m²/g，吸水率不低于0.9。所述灼减是指富矿前驱体材料在600℃/2h焙烧处理后减少的质量占焙烧前质量的百分比例；所述吸水率是指富矿前驱体材料室温(例如25℃)下浸泡水中半小时增加的质量占浸泡前质量的百分比例。Preferably, in step (3), the ignition reduction of the rich ore precursor material is not less than 3% by mass, the specific surface area is not less than 80 m² /g, and the water absorption rate is not less than 0.9. The ignition loss refers to the percentage of the mass of the rich ore precursor material after the roasting treatment at 600°C/2h to the mass before roasting; the water absorption rate refers to the rich ore precursor material immersed in water for half an hour at room temperature (for example, 25°C). The increased mass as a percentage of the mass before soaking.

根据一种优选的具体实施方式，在步骤(3)中，按照反应物流方向，所述第三加氢单元中依次装填有第一富矿前驱体材料和第二富矿前驱体材料，且所述第二富矿前驱体材料的灼减大于等于所述第一富矿前驱体材料的灼减。According to a preferred specific embodiment, in step (3), according to the flow direction of the reactants, the third hydrogenation unit is sequentially filled with the first rich ore precursor material and the second rich ore precursor material, and the third hydrogenation unit is filled with the first rich ore precursor material and the second rich ore precursor material in sequence, and the The ignition reduction of the second rich ore precursor material is greater than or equal to the ignition reduction of the first rich ore precursor material.

根据前述优选的具体实施方式，进一步优选地，所述第一富矿前驱体材料的灼减为3-15质量％，以及所述第二富矿前驱体材料的灼减为不小于15 质量％。According to the aforementioned preferred embodiments, further preferably, the ignition reduction of the first rich ore precursor material is 3-15 mass %, and the ignition reduction of the second rich ore precursor material is not less than 15 mass %.

根据前述优选的具体实施方式，进一步优选地，所述第一富矿前驱体材料与所述第二富矿前驱体材料的装填体积比为5:95至95:5。According to the aforementioned preferred embodiment, further preferably, the packing volume ratio of the first rich ore precursor material to the second rich ore precursor material is 5:95 to 95:5.

本发明所述的加氢催化剂可以为不同催化剂的级配组合，优选加氢催化剂至少能够催化加氢脱金属反应和加氢脱硫反应。The hydrogenation catalyst of the present invention can be a gradation combination of different catalysts, preferably the hydrogenation catalyst can at least catalyze the hydrodemetallization reaction and the hydrodesulfurization reaction.

本发明对能够催化加氢脱金属反应、加氢脱硫反应、加氢脱沥青反应和加氢脱残炭反应的催化剂的具体种类没有特别的限定，可以采用本领域内常规应用的能够催化上述反应的催化剂。The present invention does not specifically limit the specific types of catalysts capable of catalyzing the hydrodemetallization reaction, hydrodesulfurization reaction, hydrodeasphalting reaction and hydrodecarbon residue reaction, and the catalysts commonly used in the field can be used to catalyze the above reactions. catalyst.

本发明的所述加氢催化剂例如可以为以多孔耐熔无机氧化物为载体，第 VIB族和/或VIII族金属的氧化物或硫化物为活性组分，选择性地加入助剂的催化剂。The hydrogenation catalyst of the present invention can be, for example, a catalyst with a porous refractory inorganic oxide as a carrier, oxides or sulfides of Group VIB and/or Group VIII metals as active components, and optionally with additives.

优选情况下，本发明的第三加氢单元在长周期运行后(例如持续运行 2000h后)，富矿前驱体材料能够转变为富钒材料，富钒材料中的钒含量不小于10质量％；特别优选情况下，所述富矿前驱体材料转变为V含量20质量％以上的富钒材料，能够直接炼制高价值的V₂O₅。Preferably, after the third hydrogenation unit of the present invention runs for a long period of time (for example, after continuous operation for 2000 hours), the rich ore precursor material can be converted into a vanadium-rich material, and the vanadium content in the vanadium-rich material is not less than 10% by mass; Preferably, the rich ore precursor material is converted into a vanadium-rich material with a V content of more than 20 mass %, which can directly refine high-value V₂ O₅ .

以下提供本发明的第三加氢单元中的优选的具体实施方式：Preferred specific embodiments in the third hydrogenation unit of the present invention are provided below:

本发明的所述第三加氢单元中涉及的原料加氢处理技术为液相加氢处理技术，所述反应器或反应床层至少包括一种富矿前驱体材料和/或一种加氢催化剂，富矿前驱体材料主要由两部分组成：一是吸附油中含钒有机化合物能力强的载体，二是具有加氢活性功能的活性组分。所述载体主要由氧化硅、氢氧化铝或氢氧化铝/氧化铝混合物挤条成型、干燥得到，表面富含丰富的 -OH，对油中含钒有机化合物有强的吸附能力，600℃焙烧2h，其灼减不低于5质量％。活性组分主要采用第VIB族和/或VIII族金属如W、Mo、Co、 Ni等的氧化物或硫化物。The raw material hydrotreating technology involved in the third hydrogenation unit of the present invention is a liquid-phase hydrotreating technology, and the reactor or reaction bed at least includes a rich ore precursor material and/or a hydrogenation catalyst , the rich ore precursor material is mainly composed of two parts: one is a carrier with strong ability to adsorb vanadium-containing organic compounds in oil, and the other is an active component with hydrogenation activity. The carrier is mainly obtained by extrusion molding and drying of silicon oxide, aluminum hydroxide or aluminum hydroxide/alumina mixture. The surface is rich in -OH, and has strong adsorption capacity for vanadium-containing organic compounds in oil. It is roasted at 600 °C. 2h, the reduction on ignition is not less than 5% by mass. The active components are mainly oxides or sulfides of Group VIB and/or Group VIII metals such as W, Mo, Co, Ni and the like.

前述优选的具体实施方式中涉及的加氢催化剂一般为重渣油加氢催化剂，重渣油加氢催化剂是指具有重、渣油加氢脱金属、加氢脱硫和加氢脱残炭等功能的组合催化剂。这些催化剂一般都是以多孔耐熔无机氧化物如氧化铝为载体，第VIB族和/或VIII族金属如W、Mo、Co、Ni等的氧化物或硫化物为活性组分，选择性地加入其它各种助剂如P、Si、F、B等元素的催化剂，例如由石油化工科学研究院研发的RDM、RCS系列重、渣油加氢脱金属催化剂和脱硫催化剂。目前在液相加氢处理技术中，经常是多种催化剂配套使用。本发明中优选有富矿前驱体材料、加氢脱金属脱硫催化剂、加氢脱硫催化剂，装填顺序一般是使原料依次与富矿前驱体材料、加氢脱金属脱硫、加氢脱硫催化剂接触，有时也可根据情况，少装一种或两种催化剂，例如只装填富矿前驱体材料和加氢脱硫催化剂，而不装加氢脱金属脱硫催化剂。当然也有将这几种催化剂混合装填的技术。The hydrogenation catalyst involved in the aforementioned preferred embodiment is generally a heavy residue oil hydrogenation catalyst. combination catalyst. These catalysts are generally supported by porous refractory inorganic oxides such as alumina, and oxides or sulfides of Group VIB and/or Group VIII metals such as W, Mo, Co, Ni, etc. as active components, selectively Catalysts with other additives such as P, Si, F, B and other elements added, such as RDM, RCS series heavy and residual oil hydrodemetallization catalysts and desulfurization catalysts developed by the Research Institute of Petrochemical Engineering. At present, in the liquid phase hydroprocessing technology, a variety of catalysts are often used together. In the present invention, there are preferably rich ore precursor materials, hydrodemetallization desulfurization catalysts, and hydrodesulfurization catalysts. Depending on the situation, one or two catalysts are less loaded, for example, only the rich ore precursor material and the hydrodesulfurization catalyst are loaded without the hydrodemetallization desulfurization catalyst. Of course, there are also techniques for mixing and packing these catalysts.

优选地，在步骤(51)中，所述第四反应单元为加氢裂化单元，且所述加氢裂化单元中的操作条件包括：反应温度为360～420℃，反应压力为 10.0～18.0MPa，氢油体积比为600～2000，液时体积空速为1.0～3.0h^-1。Preferably, in step (51), the fourth reaction unit is a hydrocracking unit, and the operating conditions in the hydrocracking unit include: the reaction temperature is 360-420° C., and the reaction pressure is 10.0-18.0 MPa , the volume ratio of hydrogen to oil is 600-2000, and the liquid hourly volume space velocity is 1.0-3.0h^-1 .

优选地，所述加氢裂化单元中装填有至少一种加氢处理催化剂和至少一种加氢裂化催化剂。Preferably, the hydrocracking unit is loaded with at least one hydrotreating catalyst and at least one hydrocracking catalyst.

优选地，所述加氢裂化单元为固定床加氢裂化单元。Preferably, the hydrocracking unit is a fixed bed hydrocracking unit.

以下提供本发明的第四反应单元中的优选的具体实施方式：Preferred specific embodiments in the fourth reaction unit of the present invention are provided below:

在步骤(51)中，将所述第二轻组分引入至第四反应单元中进行反应，采用的加氢裂化技术为固定床加氢裂化技术。以目前工业上较成熟固定床蜡油加氢裂化技术为例，所述反应器或反应床层至少包括两种加氢裂化催化剂，一种是预处理催化剂，一种是加氢裂化催化剂。由于经液相加氢处理技术后又经分馏得到的物料中金属含量、硫、氮含量及残炭值都较高，因此预处理催化剂优选具有很强的脱金属活性和很好的脱硫、脱氮活性，以保证后面的加氢裂化催化剂的活性。加氢裂化催化剂优选具有很好的加氢裂化活性和高VGO转化与HDS活性。这些催化剂一般都是以多孔耐熔无机氧化物如氧化铝或分子筛为载体，第ⅥB族和/或Ⅷ族金属如W、Mo、Co、Ni等的氧化物为活性组分，选择性地加入其它各种助剂如P、Si、F、B等元素的催化剂，例如由石油化工科学研究院研发的RS系列预处理催化剂和RHC系列加氢裂化催化剂就属于这类催化剂。RS系列催化剂是一种NiW催化剂， RHC系列催化剂是一种NiMo分子筛催化剂。In step (51), the second light component is introduced into the fourth reaction unit for reaction, and the adopted hydrocracking technology is fixed bed hydrocracking technology. Taking the current industrially mature fixed-bed wax oil hydrocracking technology as an example, the reactor or reaction bed includes at least two hydrocracking catalysts, one is a pretreatment catalyst and the other is a hydrocracking catalyst. Due to the high metal content, sulfur, nitrogen content and carbon residue value in the material obtained by liquid phase hydrotreating technology and fractional distillation, the pretreatment catalyst preferably has strong demetallization activity and good desulfurization, desulfurization and desulfurization. Nitrogen activity to ensure the activity of the subsequent hydrocracking catalyst. The hydrocracking catalyst preferably has very good hydrocracking activity and high VGO conversion and HDS activity. These catalysts are generally based on porous refractory inorganic oxides such as alumina or molecular sieves as supports, and oxides of Group VIB and/or Group VIII metals such as W, Mo, Co, Ni, etc. as active components. Catalysts with various other additives such as P, Si, F, B and other elements, such as RS series pretreatment catalysts and RHC series hydrocracking catalysts developed by the Research Institute of Petrochemical Sciences, belong to this category of catalysts. The RS series catalyst is a NiW catalyst, and the RHC series catalyst is a NiMo molecular sieve catalyst.

优选情况下，在步骤(51)中，所述第四反应单元为催化裂化单元，且所述催化裂化单元为流化催化裂化(FCC)单元。Preferably, in step (51), the fourth reaction unit is a catalytic cracking unit, and the catalytic cracking unit is a fluid catalytic cracking (FCC) unit.

优选地，第二轻组分催化裂化中采用的第二轻组分催化裂化技术为流化床催化裂化(FCC)技术，优选采用石油化工科学研究院开发的LTAG技术，主要生产汽油馏分和液化气。Preferably, the second light component catalytic cracking technology used in the second light component catalytic cracking is a fluidized bed catalytic cracking (FCC) technology, preferably LTAG technology developed by the Research Institute of Petrochemical Engineering, mainly to produce gasoline fractions and liquefaction gas.

优选地，所述流化催化裂化单元中的操作条件包括：反应温度为 500～600℃，剂油比为3～12，停留时间为0.6～6s。Preferably, the operating conditions in the fluidized catalytic cracking unit include: the reaction temperature is 500-600°C, the agent-oil ratio is 3-12, and the residence time is 0.6-6s.

在没有特别说明的情况下，本发明所述剂油比均表示剂油质量比。Unless otherwise specified, the agent-oil ratios in the present invention all refer to the agent-oil mass ratio.

优选情况下，在步骤(51)中，所述第四反应单元为柴油加氢提质单元，且所述柴油加氢提质单元中的操作条件包括：反应温度为330～420℃，反应压力为5.0～18.0MPa，氢油体积比为500～2000，液时体积空速为0.3～3.0h^-1。Preferably, in step (51), the fourth reaction unit is a diesel hydroupgrading unit, and the operating conditions in the diesel hydroupgrading unit include: the reaction temperature is 330-420° C., the reaction pressure is It is 5.0～18.0MPa, the volume ratio of hydrogen to oil is 500～2000, and the liquid hourly volume space velocity is 0.3～3.0h^-1 .

优选地，所述柴油加氢提质单元中装填有至少一种柴油加氢提质催化剂。Preferably, the diesel hydro-upgrading unit is loaded with at least one diesel hydro-upgrading catalyst.

本发明的所述柴油加氢提质催化剂例如可以为石油化工科学研究院研发的RS系列预处理催化剂和RHC-100系列柴油加氢裂化催化剂。The diesel hydro-upgrading catalyst of the present invention can be, for example, RS series pretreatment catalysts and RHC-100 series diesel hydrocracking catalysts developed by the Research Institute of Petrochemical Industry.

优选情况下，在步骤(52)中，将所述第二重组分引入至延迟焦化单元中进行反应以得到选自焦化汽油、焦化柴油、焦化蜡油和低硫石油焦中的至少一种产物，且所述至延迟焦化单元中的操作条件包括：反应温度为 440～520℃，停留时间为0.1～4h。Preferably, in step (52), the second heavy component is introduced into a delayed coking unit for reaction to obtain at least one product selected from coker gasoline, coker diesel, coker wax oil and low sulfur petroleum coke , and the operating conditions in the delayed coking unit include: the reaction temperature is 440-520° C., and the residence time is 0.1-4 h.

优选地，在步骤(52)中，所述第二重组分的硫含量不大于1.8质量％，将所述第二重组分引入至延迟焦化单元中进行反应以得到低硫石油焦，更优选所述低硫石油焦的硫含量不大于3质量％。Preferably, in step (52), the sulfur content of the second heavy component is not greater than 1.8% by mass, and the second heavy component is introduced into a delayed coking unit for reaction to obtain low-sulfur petroleum coke, more preferably the The sulfur content of the low-sulfur petroleum coke is not more than 3% by mass.

优选情况下，在步骤(52)中，将所述第二重组分作为低硫船用燃料油组分，且所述低硫船用燃料油组分中的硫含量不大于0.5质量％。Preferably, in step (52), the second heavy component is used as a low-sulfur marine fuel oil component, and the sulfur content in the low-sulfur marine fuel oil component is not more than 0.5% by mass.

优选情况下，将所述DCC单元中获得的油浆循环回所述溶剂脱沥青单元中与所述重质原料油一起进行溶剂脱沥青处理。Preferably, the oil slurry obtained in the DCC unit is recycled back to the solvent deasphalting unit for solvent deasphalting together with the heavy feedstock oil.

本发明对所述溶剂脱沥青处理的具体操作没有特别的限制，可以采用本领域内常规的溶剂脱沥青工艺进行。本发明的实例中示例性地列举了溶剂脱沥青工艺的操作参数，本领域技术人员不应理解为对本发明的限制。The present invention has no particular limitation on the specific operation of the solvent deasphalting treatment, which can be carried out by using a conventional solvent deasphalting process in the art. The operating parameters of the solvent deasphalting process are exemplified in the examples of the present invention, which should not be construed as a limitation of the present invention by those skilled in the art.

本发明适用于常渣与减渣的加氢转化，尤其适用于高金属、高残炭、高稠环物质的劣质渣油加氢转化。The invention is suitable for the hydroconversion of normal slag and reduced slag, and is especially suitable for the hydroconversion of inferior residue oil with high metal, high residual carbon and high condensed ring substances.

如前所述，本发明的第二方面提供了一种联合加工脱油沥青和富芳馏分油的系统，该系统中包括：As previously mentioned, a second aspect of the present invention provides a system for the combined processing of deoiled pitch and aromatic-rich distillates, the system comprising:

第一加氢单元，该第一加氢单元与所述溶剂脱沥青单元保持流体连通，且该第一加氢单元为固定床加氢单元，用于将来自所述溶剂脱沥青单元的脱沥青油在其中进行加氢反应；a first hydrogenation unit in fluid communication with the solvent deasphalting unit and which is a fixed bed hydrogenation unit for deasphalting the solvent from the solvent deasphalting unit The oil undergoes a hydrogenation reaction in it;

优选地，所述延迟焦化单元与所述溶氢单元保持流体连通，用于将来自所述延迟焦化单元的所述焦化柴油和/或所述焦化蜡油循环回所述第二加氢单元中。Preferably, the delayed coking unit is in fluid communication with the hydrogen dissolution unit for recycling the coker diesel and/or the coker wax oil from the delayed coking unit back to the second hydroprocessing unit .

根据一种优选的具体实施方式，在本发明的系统中，所述第四反应单元为加氢裂化单元。According to a preferred embodiment, in the system of the present invention, the fourth reaction unit is a hydrocracking unit.

根据另一种优选的具体实施方式，在本发明的系统中，所述第四反应单元为催化裂化单元，且所述催化裂化单元为流化催化裂化单元。According to another preferred embodiment, in the system of the present invention, the fourth reaction unit is a catalytic cracking unit, and the catalytic cracking unit is a fluid catalytic cracking unit.

根据另一种优选的具体实施方式，在本发明的系统中，所述第第四反应单元为柴油加氢提质单元。According to another preferred embodiment, in the system of the present invention, the fourth reaction unit is a diesel hydro-upgrading unit.

以下结合图1对本发明的联合加工脱油沥青和富芳馏分油的方法进行进一步详细说明。The method for combined processing of deoiled asphalt and aromatic-rich distillate oil of the present invention will be described in further detail below with reference to FIG. 1 .

如图1所示，重油原料1进入溶剂脱沥青单元2中进行溶剂脱沥青处理后得到脱油沥青4和脱沥青油3；将所述脱沥青油3引入至第一加氢单元24 中进行加氢反应，并将所述第一加氢单元24中获得的液相流出物引入至 DCC单元25中进行反应，得到丙烯26、LCO27、HCO28和油浆23；将含有来自所述DCC单元25的LCO27和/或HCO28的富芳馏分油20引入至第二加氢单元21中进行加氢饱和后分馏以获得第一重组分22和第一轻组分；将脱油沥青4和含有所述第一重组分22的含芳烃物流一起形成混合原料6 并引入至溶氢单元29中与氢气混合，并将混合后的物料引入至第三加氢单元7中进行加氢反应，所述含芳烃物流中优选还含有来自外界的芳烃化合物 5，其中，所述第三加氢单元7中含有富矿前驱体材料和能够催化选自加氢脱金属反应、加氢脱硫反应、加氢脱沥青反应和加氢脱残炭反应中的至少一种反应的加氢催化剂；来自所述第三加氢单元7的液相产物进入分离单元19 中进行分馏，得到第二轻组分8和第二重组分9；将所述第二轻组分8引入至第四反应单元10中进行反应以得到选自汽油组分13、BTX原料组分12、柴油组分14中的至少一种产物，或者将所述第二轻组分8循环回所述DCC 单元25中；以及将所述第二重组分9引入至延迟焦化单元11中进行反应以得到选自焦化汽油15、焦化柴油16、焦化蜡油17和低硫石油焦18中的至少一种产物；或者将所述第二重组分9作为低硫船用燃料油组分。As shown in FIG. 1 , the heavy oil raw material 1 enters thesolvent deasphalting unit 2 for solvent deasphalting treatment to obtaindeoiled asphalt 4 anddeasphalted oil 3; thedeasphalted oil 3 is introduced into thefirst hydrogenation unit 24 for processing. Hydrogenation reaction, and the liquid phase effluent obtained in thefirst hydrogenation unit 24 is introduced into theDCC unit 25 for reaction to obtainpropylene 26, LCO27, HCO28 andoil slurry 23; The aromatic-rich distillate 20 of LCO27 and/or HCO28 is introduced into thesecond hydrogenation unit 21 for hydrosaturation and post-fractionation to obtain the firstheavy component 22 and the first light component; The aromatics-containing streams of the firstheavy component 22 together form amixed feedstock 6 and are introduced into thehydrogen dissolving unit 29 to be mixed with hydrogen, and the mixed material is introduced into thethird hydrogenation unit 7 for hydrogenation. The stream preferably also contains aromatic compounds 5 from the outside, wherein thethird hydrogenation unit 7 contains rich ore precursor materials and can catalyze a reaction selected from the group consisting of hydrodemetallization reaction, hydrodesulfurization reaction, hydrodeasphalting reaction and Hydrogenation catalyst for at least one reaction in the hydrogenation and decarbonization reaction; the liquid-phase product from thethird hydrogenation unit 7 enters theseparation unit 19 for fractionation to obtain the secondlight component 8 and the secondheavy component 9; introducing the secondlight component 8 into thefourth reaction unit 10 for reaction to obtain at least one product selected from thegasoline component 13, theBTX feedstock component 12, and thediesel component 14, or The secondlight component 8 is recycled back to theDCC unit 25; and the secondheavy component 9 is introduced into the delayedcoking unit 11 for reaction to obtain a coker selected from the group consisting ofcoker gasoline 15,coker diesel 16, andcoker wax oil 17 and at least one product of low-sulfur petroleum coke 18; or use the secondheavy component 9 as a low-sulfur marine fuel oil component.

本发明的技术使得重油高效转化并能够生产汽油、BTX原料，以及能够灵活生产低硫船燃和低硫石油焦。The technology of the present invention enables efficient conversion of heavy oil and enables the production of gasoline, BTX feedstock, and the flexible production of low-sulfur marine fuel and low-sulfur petroleum coke.

与现有技术相比，优选情况下，本发明由于采用了渣油加氢、加氢裂化或催化裂化等工艺的有机联合，不但使低价值的DOA转化成符合环保要求的低硫船燃组分和低硫石油焦原料，而且实现了重质石油资源的高效、环保和综合利用。Compared with the prior art, preferably, the present invention adopts the organic combination of residual oil hydrogenation, hydrocracking or catalytic cracking, etc., which not only converts low-value DOA into a low-sulfur ship-fuel group that meets environmental protection requirements. and low-sulfur petroleum coke raw materials, and realize the efficient, environmental protection and comprehensive utilization of heavy petroleum resources.

另外，本发明提供的技术能够使得DOA在渣油液相加氢反应器中高效转化并能够生产汽油馏分、BTX原料，以及能够提供生产低硫船燃和低硫焦产品的原料。In addition, the technology provided by the present invention enables the efficient conversion of DOA in the residual liquid phase hydrogenation reactor and the production of gasoline fractions, BTX feedstocks, and feedstocks for the production of low-sulfur marine fuel and low-sulfur coke products.

以下将通过实例对本发明进行详细描述。在没有特别说明的情况下，以下实例均采用图1所示的工艺流程进行。以及，在没有特别说明的情况下，以下实例具有如下共同特征：The present invention will be described in detail below by way of examples. Unless otherwise specified, the following examples are all carried out using the process flow shown in FIG. 1 . And, unless otherwise specified, the following examples have the following common features:

在没有特别说明的情况下，以下实例中表4的结果为装置持续运行100h 中，每25h取样检测获得的结果的平均值。Unless otherwise specified, the results in Table 4 in the following examples are the average values of the results obtained by sampling and testing every 25 hours during the continuous operation of the device for 100 hours.

脱沥青油在第一加氢单元中进行的加氢反应在中型固定床渣油加氢处理装置上进行，按照物流方向，第一加氢单元中依次装填RG-30B、RDM-202、 RCS-31催化剂，各催化剂之间的装填比为：RG-30B:RDM-202:RCS-31＝6： 40：44(V/V)。第一加氢单元的操作条件为：反应温度为350℃，反应压力为10MPa，液时体积空速为1.2h^-1，氢油体积比为800：1。The hydrogenation reaction of the deasphalted oil in the first hydrogenation unit is carried out on a medium-sized fixed bed residual oil hydrotreating unit. 31 catalysts, the loading ratio between the catalysts is: RG-30B:RDM-202:RCS-31=6:40:44 (V/V). The operating conditions of the first hydrogenation unit are: the reaction temperature is 350°C, the reaction pressure is 10MPa, the liquid hourly volume space velocity is 1.2h^-1 , and the volume ratio of hydrogen to oil is 800:1.

DCC单元的操作条件为：反应温度为580℃，剂油比为6，停留时间为 3s。The operating conditions of the DCC unit were: the reaction temperature was 580 °C, the agent-oil ratio was 6, and the residence time was 3 s.

富芳馏分油部分加氢饱和实验在中型固定床柴油加氢处理装置上进行试验，反应器总体积为200mL。在以下实例中，富芳馏分油部分加氢饱和使用的加氢催化剂和材料是由石油化工科学研究院研发的RS-2100系列加氢催化剂。The partial hydrogenation and saturation experiment of aromatic-rich distillate oil was carried out on a medium-sized fixed-bed diesel hydrotreating unit with a total reactor volume of 200 mL. In the following examples, the hydrogenation catalysts and materials used in the partial hydrogenation saturation of the aromatic-rich distillate are RS-2100 series hydrogenation catalysts developed by the Research Institute of Petrochemical Engineering.

将第二加氢单元中的部分加氢饱和得到的液相物流进行分馏，得到切割点为180℃的第一轻组分和第一重组分。The liquid phase stream obtained from the partial hydrogenation saturation in the second hydrogenation unit is fractionated to obtain the first light component and the first heavy component with a cut point of 180°C.

第一重组分和DOA引入至溶氢单元中与氢气混合，获得混合原料，混合原料的加氢反应在中型重油液相加氢处理装置上进行试验，反应器总体积为200mL。在以下实例中。第三加氢单元中使用的加氢催化剂和材料是由石油化工科学研究院研发的RG-30B保护催化剂、富矿前驱体材料1、富矿前驱体材料2、RDM-33B渣油脱金属脱硫过渡催化剂、RCS-31脱硫催化剂。按照物流方向，催化剂装填的顺序为加氢保护催化剂、富矿前驱体材料1、富矿前驱体材料2、加氢脱金属脱硫催化剂、加氢脱硫催化剂。第三加氢单元中，各催化剂之间的装填比为：RG-30B:富矿前驱体材料1、富矿前驱体材料2：RDM-33B:RCS-31＝6：30：30：14：20(V/V)。The first heavy component and DOA were introduced into the hydrogen dissolving unit and mixed with hydrogen to obtain mixed raw materials. The hydrogenation reaction of the mixed raw materials was tested on a medium-sized heavy oil liquid-phase hydrotreating device with a total reactor volume of 200 mL. in the following example. The hydrogenation catalysts and materials used in the third hydrogenation unit are RG-30B protective catalyst, rich ore precursor material 1, richore precursor material 2, RDM-33B residue demetallization and desulfurization transition catalyst developed by the Research Institute of Petrochemical Engineering , RCS-31 desulfurization catalyst. According to the flow direction, the catalyst loading sequence is hydrogenation protection catalyst, rich ore precursor material 1, richore precursor material 2, hydrodemetallization desulfurization catalyst, and hydrodesulfurization catalyst. In the third hydrogenation unit, the loading ratio between the catalysts is: RG-30B: rich ore precursor material 1, rich ore precursor material 2: RDM-33B: RCS-31=6:30:30:14:20 ( V/V).

第四反应单元为固定床加氢裂化装置，所用的催化剂为石油化工科学研究院研发的RS-2100精制催化剂、RHC-131加氢裂化催化剂。各催化剂之间的装填比为：RS-2100:RHC-131＝40：60(V/V)。固定床加氢裂化装置的操作条件为：精制段反应温度为370℃，裂化段反应温度为385℃，反应压力为10MPa，液时体积空速为2.0h^-1，氢油体积比为：1200：1。The fourth reaction unit is a fixed bed hydrocracking unit, and the catalysts used are RS-2100 refining catalyst and RHC-131 hydrocracking catalyst developed by the Research Institute of Petrochemical Engineering. The loading ratio between the catalysts was: RS-2100:RHC-131=40:60 (V/V). The operating conditions of the fixed bed hydrocracking unit are: the reaction temperature in the refining section is 370°C, the reaction temperature in the cracking section is 385°C, the reaction pressure is 10MPa, the liquid hourly volume space velocity is 2.0h^-1 , and the volume ratio of hydrogen to oil is: 1200 :1.

实施例AExample A

富矿前驱体材料1制备：选取中石化催化剂有限公司长岭分公司生产的 RPB110拟薄水铝石2000g，其中1000g在550℃下处理2h，得到约700g氧化铝，将约700g氧化铝和另外1000g拟薄水铝石充分混合，之后加入40g 田菁粉和20g柠檬酸，并加入2200g去离子水，混捏并挤条成型，在300℃下干燥3h，得到约1730g载体，加入2100mL含Mo和Ni的溶液进行饱和浸渍，溶液中Mo含量以MoO₃质量计为5.5％，Ni含量以NiO质量计为1.5％，浸渍半小时，之后在180℃下处理4h，得到富矿前驱体材料1，性质如表7 中所示。Preparation of rich ore precursor material 1: Select 2000 g of RPB110 pseudo-boehmite produced by Sinopec Catalyst Co., Ltd. Changling Branch, of which 1000 g is treated at 550 ° C for 2 hours to obtain about 700 g of alumina, and about 700 g of alumina and another 1000 g of pseudo-boehmite are obtained. The boehmite was thoroughly mixed, then 40g of saffron powder and 20g of citric acid were added, and 2200g of deionized water was added, kneaded and extruded into strips, dried at 300°C for 3h to obtain about 1730g of carrier, and 2100mL of Mo and Ni were added. The solution was saturated and impregnated, the Mo content in the solution was 5.5% by mass_of MoO3, and the content of Ni was 1.5% by mass of NiO, immersed for half an hour, and then treated at 180 ° C for 4 hours to obtain rich ore precursor material 1, the properties are shown in the table shown in 7.

富矿前驱体材料2制备：选取中石化催化剂有限公司长岭分公司生产的 RPB110拟薄水铝石2000g，加入30g田菁粉和30g柠檬酸，并加入2400g 去离子水，混捏并挤条成型，在120℃下干燥5h，得到约2040g载体，加入 2200mL含Mo和Ni的溶液进行饱和浸渍，溶液中Mo含量以MoO₃质量计为7.5％，Ni含量以NiO质量计为1.7％，浸渍半小时，之后在200℃下处理3h，得到富矿前驱体材料2，性质如表7中所示。Preparation of rich ore precursor material 2: Select 2000g of RPB110 pseudo-boehmite produced by Changling Branch of Sinopec Catalyst Co., Ltd., add 30g of cyanine powder and 30g of citric acid, and add 2400g of deionized water, knead and extrude into strips. Dry at 120 °C for₅ h to obtain about 2040 g of carrier, add 2200 mL of a solution containing Mo and Ni for saturated impregnation. After that, it was treated at 200° C. for 3 h to obtain richore precursor material 2, and the properties are shown in Table 7.

富矿前驱体材料3制备：选取市售的氧化硅2000g，加入30g田菁粉和 30g氢氧化钠，并加入2400g去离子水，混捏并挤条成型，在120℃下干燥 5h，得到载体，加入2200mL含Mo和Ni的溶液进行饱和浸渍，溶液中Mo 含量以MoO₃重量计为4.5％，Ni含量以NiO重量计为1.0％，浸渍半小时，之后在200℃下处理3h，得到富矿前驱体材料3，性质如表7中所示。Preparation of rich ore precursor material 3: Select 2000g of commercially available silicon oxide, add 30g of succulent powder and 30g of sodium hydroxide, and add 2400g of deionized water, knead and extrude into strips, dry at 120 ° C for 5 hours to obtain a carrier, add 2200 mL of a solution containing Mo and Ni was saturated and impregnated, the Mo content in the solution was 4.5% by weight_of MoO3, and the content of Ni was 1.0% by weight of NiO, immersed for half an hour, and then treated at 200 °C for 3h to obtain richore precursors Material 3, the properties are shown in Table 7.

实施例BExample B

以一种减压渣油为原料进行溶剂脱沥青，所用溶剂为丁烷含量为70量％以上的烃类混合物，在120℃下，溶剂：减压渣油＝3：1(质量比)的条件下进行溶剂脱沥青，DAO质量收率70％，DOA质量收率30％。A kind of vacuum residue oil is used as raw material to carry out solvent deasphalting, and the solvent used is a hydrocarbon mixture with a butane content of more than 70% by weight, and at 120° C., solvent: vacuum residue oil=3:1 (mass ratio) The solvent deasphalting was carried out under the conditions, the mass yield of DAO was 70%, and the mass yield of DOA was 30%.

所得DAO和DOA的性质见表1。The properties of the resulting DAO and DOA are shown in Table 1.

实施例1Example 1

本实施例采用的DAO和DOA均来自实施例B。The DAO and DOA used in this example are from Example B.

DAO经第一加氢单元中进行加氢反应后的液相产品性质见表1；液相产品进入DCC单元进行反应，得到LCO1和HCO1。The properties of the liquid-phase product after the hydrogenation reaction of DAO in the first hydrogenation unit is shown in Table 1; the liquid-phase product enters the DCC unit for reaction to obtain LCO1 and HCO1.

LCO1在第二加氢单元中进行加氢饱和后分馏以获得第一轻组分1和第一重组分1，第二加氢单元加氢的操作条件为：反应温度为290℃，反应压力为4MPa，液时体积空速为1h^-1，氢油体积比为800：1。LCO1和第一重组分1性质如表2所示。The LCO1 is subjected to hydrogenation and saturation in the second hydrogenation unit and then fractionated to obtain the first light component 1 and the first heavy component 1. The operating conditions for the hydrogenation of the second hydrogenation unit are: the reaction temperature is 290 °C, and the reaction pressure is 4MPa, the liquid hourly volume space velocity is 1h^-1 , and the volume ratio of hydrogen to oil is 800:1. The properties of LCO1 and the first heavy component 1 are shown in Table 2.

DOA与第一重组分1按照质量比1:10混合，混合原料的性质见表3。DOA is mixed with the first heavy component 1 in a mass ratio of 1:10, and the properties of the mixed raw materials are shown in Table 3.

DOA和第一重组分1进入溶氢单元中与氢气混合，获得的混合物料(其中的氢含量见表3中)在第三加氢单元的操作条件为：反应温度为360℃，反应压力为10MPa，液时体积空速为0.3h^-1，循环油：第三加氢单元入口原料油体积比例0.5:1。混合原料加氢后产品性质见表4。DOA and the first heavy component 1 enter the hydrogen-dissolving unit to be mixed with hydrogen, and the obtained mixed material (wherein the hydrogen content is shown in Table 3) operates under the conditions of the third hydrogenation unit: the reaction temperature is 360° C., and the reaction pressure is 10MPa, the liquid hourly volume space velocity is 0.3h^-1 , and the volume ratio of circulating oil: feedstock oil at the inlet of the third hydrogenation unit is 0.5:1. The properties of the products after hydrogenation of the mixed raw materials are shown in Table 4.

分馏第三加氢单元处理得到的液相产品，大于等于350℃第二重组分性质见表5。Table 5 shows the properties of the liquid-phase product obtained by the treatment of the third hydrogenation unit of fractional distillation, and the properties of the second heavy component at or above 350°C.

小于350℃第二轻组分在第四反应单元进行试验，得到加氢裂化产品，性质见表6。The second light fraction less than 350°C is tested in the fourth reaction unit to obtain a hydrocracking product whose properties are shown in Table 6.

实施例2Example 2

DAO经第一加氢单元中进行加氢反应后的液相产品性质见表1；液相产品进入DCC单元进行反应，得到LCO2和HCO2。The properties of the liquid-phase product after the hydrogenation reaction of DAO in the first hydrogenation unit is shown in Table 1; the liquid-phase product enters the DCC unit for reaction to obtain LCO2 and HCO2.

HCO2在第二加氢单元中进行加氢饱和后分馏以获得第一轻组分2和第一重组分2，第二加氢单元加氢操作条件为：反应温度为330℃，反应压力为6MPa，液时体积空速为1h^-1，氢油体积比为800：1。HCO2和第一重组分2性质如表2所示。The HCO2 is subjected to hydrogenation and saturation in the second hydrogenation unit and then fractionated to obtain thefirst light component 2 and the firstheavy component 2. The hydrogenation operation conditions of the second hydrogenation unit are as follows: the reaction temperature is 330°C, and the reaction pressure is 6MPa , the liquid hourly volume space velocity is 1h^-1 , and the volume ratio of hydrogen to oil is 800:1. The properties of HCO2 and the firstheavy component 2 are shown in Table 2.

DOA与第一重组分2按照质量比5:10混合，混合原料的性质见表3。DOA is mixed with the firstheavy component 2 according to the mass ratio of 5:10, and the properties of the mixed raw materials are shown in Table 3.

DOA和第一重组分2进入溶氢单元中与氢气混合，获得的混合物料(其中的氢含量见表3中)在第三加氢单元的操作条件为：反应温度为380℃，反应压力为8MPa，液时体积空速为0.3h^-1，循环油：第三加氢单元入口原料油体积比例0.5:1。混合原料加氢后产品性质见表4。DOA and the firstheavy component 2 enter the hydrogen-dissolving unit to be mixed with hydrogen, and the obtained mixed material (the hydrogen content therein is shown in Table 3) is operated in the third hydrogenation unit under the following conditions: the reaction temperature is 380° C., and the reaction pressure is 8MPa, the liquid hourly volume space velocity is 0.3h^-1 , and the volume ratio of circulating oil: feedstock oil at the inlet of the third hydrogenation unit is 0.5:1. The properties of the products after hydrogenation of the mixed raw materials are shown in Table 4.

实施例3Example 3

DAO经第一加氢单元中进行加氢反应后的液相产品性质见表1；液相产品进入DCC单元(操作条件同实施例1中)进行反应，得到LCO1和HCO1。The properties of the liquid-phase product after the hydrogenation reaction of DAO in the first hydrogenation unit is shown in Table 1; the liquid-phase product enters the DCC unit (operating conditions are the same as in Example 1) and reacts to obtain LCO1 and HCO1.

LCO1在第二加氢单元中进行加氢饱和后分馏以获得第一轻组分3和第一重组分3，第二加氢单元加氢操作条件为：反应温度为320℃，反应压力为6MPa，液时体积空速为1h^-1，氢油体积比为800：1。LCO1和第一重组分3性质如表2所示。The LCO1 is subjected to hydrogenation and saturation in the second hydrogenation unit and then fractionated to obtain thefirst light component 3 and the firstheavy component 3. The hydrogenation operating conditions of the second hydrogenation unit are: the reaction temperature is 320°C, and the reaction pressure is 6MPa , the liquid hourly volume space velocity is 1h^-1 , and the volume ratio of hydrogen to oil is 800:1. The properties of LCO1 and the firstheavy component 3 are shown in Table 2.

DOA与第一重组分3按照质量比10:10混合，混合原料的性质见表3。DOA is mixed with the firstheavy component 3 according to the mass ratio of 10:10, and the properties of the mixed raw materials are shown in Table 3.

DOA和第一重组分3进入溶氢单元中与氢气混合，获得的混合物料(其中的氢含量见表3中)在第三加氢单元的操作条件为：反应温度为370℃，反应压力为8MPa，液时体积空速为0.3h^-1，循环油：第三加氢单元入口原料油体积比例0.5:1。混合原料加氢后产品性质见表4。DOA and the firstheavy component 3 enter the hydrogen-dissolving unit to be mixed with hydrogen, and the obtained mixed material (wherein the hydrogen content is shown in Table 3) operates in the third hydrogenation unit as follows: the reaction temperature is 370° C., and the reaction pressure is 8MPa, the liquid hourly volume space velocity is 0.3h^-1 , and the volume ratio of circulating oil: feedstock oil at the inlet of the third hydrogenation unit is 0.5:1. The properties of the products after hydrogenation of the mixed raw materials are shown in Table 4.

将该第二重组分在反应温度为500℃停留时间为0.5小时下进行焦化反应，得到石油焦(收率31质量％)，硫含量为2.7质量％。The second heavy component was subjected to a coking reaction at a reaction temperature of 500° C. and a residence time of 0.5 hours to obtain petroleum coke (yield 31% by mass) with a sulfur content of 2.7% by mass.

实施例4Example 4

本实施例采用的富芳馏分油为来自国内某煤焦化装置的煤焦油(性质见表1)和LCO1，LCO1与煤焦油的质量比为1:1，富芳馏分油在第二加氢单元中进行加氢饱和后分馏以获得第一轻组分4和第一重组分4，第二加氢单元加氢操作条件为：反应温度为300℃，反应压力为10MPa，液时体积空速为0.8h^-1，氢油体积比为800：1。富芳馏分油和第一重组分4的性质如表2 所示。The aromatic-rich distillate oil used in this example is coal tar (see Table 1 for properties) and LCO1 from a domestic coal coking unit. The mass ratio of LCO1 and coal tar is 1:1. The aromatic-rich distillate oil is used in the second hydrogenation unit. Carry out hydrogenation and saturation and fractional distillation to obtain thefirst light component 4 and the firstheavy component 4. The hydrogenation operating conditions of the second hydrogenation unit are: the reaction temperature is 300 ° C, the reaction pressure is 10 MPa, and the liquid hourly volume space velocity is 0.8h^-1 , the volume ratio of hydrogen to oil is 800:1. The properties of the aromatic-rich distillate and the firstheavy fraction 4 are shown in Table 2.

DOA与第一重组分4按照质量比15:10混合，混合原料的性质见表3。DOA is mixed with the firstheavy component 4 according to the mass ratio of 15:10, and the properties of the mixed raw materials are shown in Table 3.

DOA和第一重组分4进入溶氢单元中与氢气混合，获得的混合物料(其中的氢含量见表3中)在第三加氢单元的操作条件为：反应温度为350℃，反应压力为12MPa，液时体积空速为0.3h^-1，循环油：第三加氢单元入口原料油体积比例0.5:1。混合原料加氢后产品性质见表4。DOA and the firstheavy component 4 enter the hydrogen-dissolving unit to be mixed with hydrogen, and the obtained mixed material (wherein the hydrogen content is shown in Table 3) operates under the conditions of the third hydrogenation unit: the reaction temperature is 350° C., and the reaction pressure is 12MPa, the liquid hourly volume space velocity is 0.3h^-1 , and the volume ratio of circulating oil: feedstock oil at the inlet of the third hydrogenation unit is 0.5:1. The properties of the products after hydrogenation of the mixed raw materials are shown in Table 4.

实施例5Example 5

采用与实施例3相似的方法进行，所不同的是：Use a method similar to Example 3, except:

本实施例中，第三加氢单元的加氢处理的温度为395℃。In this embodiment, the temperature of the hydroprocessing of the third hydrogenation unit is 395°C.

其余条件与实施例3中相同。The remaining conditions are the same as in Example 3.

混合原料加氢后产品性质见表4。The properties of the products after hydrogenation of the mixed raw materials are shown in Table 4.

实施例6Example 6

催化剂装填和加氢处理的操作条件同实施例4。The operating conditions for catalyst packing and hydrotreating are the same as in Example 4.

与实施例4相同的混合原料经第三加氢单元加氢处理后，每过30天，反应温度提3℃，加氢试验共计运行360天后停止运转。After the mixed raw material same as Example 4 was hydrotreated by the third hydrogenation unit, the reaction temperature was increased by 3°C every 30 days, and the hydrogenation test was stopped after running for a total of 360 days.

初始装到反应器的富矿前驱体材料1和富矿前驱体材料2，反应后变成富V材料1和富钒材料2，经焙烧分析其V含量分别为69质量％和60质量％，是提炼高价值V₂O₅的高品质材料。The rich ore precursor material 1 and the richore precursor material 2 initially loaded into the reactor become V-rich material 1 and vanadium-rich material 2 after the reaction, and their V content is 69% by mass and 60% by mass respectively after roasting analysis._High quality material of high value_V2O5 .

实施例7Example 7

将实施例3中的小于350℃第二轻组分在小型催化裂化固定流化床试验装置进行催化裂化试验，所用催化剂为中石化催化剂有限公司长岭分公司生产的催化裂化催化剂MLC-500，反应温度为540℃，剂油比为6，停留时间为3s。The second light component less than 350 ° C in Example 3 was subjected to a catalytic cracking test in a small catalytic cracking fixed fluidized bed test device, and the catalyst used was the catalytic cracking catalyst MLC-500 produced by the Changling Branch of Sinopec Catalyst Co., Ltd., the reaction The temperature was 540°C, the agent-oil ratio was 6, and the residence time was 3s.

结果，产品汽油质量收率为40％，汽油RON辛烷值为93。As a result, the product gasoline mass yield was 40%, and the gasoline RON octane number was 93.

实施例8Example 8

采用与实施例1相似的工艺，不同之处在于，本实施例中将所得第二重组分引入至延迟焦化单元中进行反应，得到焦化汽油、焦化柴油和焦化蜡油。A process similar to that of Example 1 is adopted, except that in this example, the obtained second heavy component is introduced into a delayed coking unit for reaction to obtain coker gasoline, coker diesel oil and coker wax oil.

延迟焦化单元的操作条件为：反应温度为510℃，停留时间为0.6h。The operating conditions of the delayed coking unit were as follows: the reaction temperature was 510°C and the residence time was 0.6h.

焦化柴油的硫含量0.26质量％，凝点-11℃，十六烷值48。The sulfur content of the coking diesel is 0.26% by mass, the freezing point is -11°C, and the cetane number is 48.

焦化蜡油的硫含量1.12质量％，凝点32℃。The sulfur content of the coking wax oil was 1.12% by mass, and the freezing point was 32°C.

焦化汽油的收率为14.7％，硫含量0.10质量％，MON为61.8。The yield of coker gasoline was 14.7%, the sulfur content was 0.10% by mass, and the MON was 61.8.

并将焦化柴油和焦化蜡油循环回第二加氢单元和所述LCO1混合，以进行加氢饱和后分馏以获得切割点为180℃的第一轻组分8和第一重组分8，反应工艺条件同实施例1。混合焦化柴油、焦化蜡油以及LCO1的油料的性质和第一重组分8的性质如表2所示。The coking diesel oil and coking wax oil are recycled back to the second hydrogenation unit and mixed with the LCO1 to carry out hydrosaturation and post-fractionation to obtain thefirst light component 8 and the firstheavy component 8 with a cut point of 180 ° C, and the reaction Process conditions are the same as in Example 1. The properties of the oil mixed with coker diesel oil, coker wax oil and LCO1 and the properties of the firstheavy component 8 are shown in Table 2.

DOA来自实施例B，与第一重组分8按照质量比1:10混合，混合原料的性质见表3。DOA comes from Example B and is mixed with the firstheavy component 8 in a mass ratio of 1:10. The properties of the mixed raw materials are shown in Table 3.

DOA和第一重组分8进入溶氢单元中与氢气混合，获得的混合物料(其中的氢含量见表3中)在第三加氢单元的操作条件为：反应温度为360℃，反应压力为8MPa，液时体积空速为0.3h^-1，氢油体积比为800：1。混合原料加氢后产品性质见表4。DOA and the firstheavy component 8 enter the hydrogen-dissolving unit to be mixed with hydrogen, and the obtained mixed material (wherein the hydrogen content is shown in Table 3) operates in the third hydrogenation unit as follows: the reaction temperature is 360° C., and the reaction pressure is 8MPa, the liquid hourly volume space velocity is 0.3h^-1 , and the volume ratio of hydrogen to oil is 800:1. The properties of the products after hydrogenation of the mixed raw materials are shown in Table 4.

实施例9Example 9

将实施例1所得小于350℃第二轻组分在柴油加氢改质装置上进行试验，得到柴油组分。The second light component less than 350°C obtained in Example 1 was tested on a diesel hydro-upgrading device to obtain a diesel component.

柴油加氢改质装置的操作条件为：反应温度为360℃，反应压力为 12MPa，氢油体积比为1000，液时体积空速为1.0h^-1。The operating conditions of the diesel hydrogenation-upgrading device are as follows: the reaction temperature is 360°C, the reaction pressure is 12MPa, the hydrogen-oil volume ratio is 1000, and the liquid-hour volume space velocity is 1.0h^-1 .

结果：所得柴油组分性质为硫含量5ppm，凝点-33℃，十六烷值53。Result: The properties of the obtained diesel components are: sulfur content of 5ppm, freezing point of -33°C, and cetane number of 53.

实施例10Example 10

采用与实施例1相似的工艺进行，所不同的是，本实施例中的第三加氢单元中的催化剂装填情况如下：The process is similar to that of Example 1, except that the catalyst loading in the third hydrogenation unit in this example is as follows:

按照物流方向，催化剂装填的顺序为加氢保护催化剂、富矿前驱体材料 1、加氢脱金属脱硫催化剂、加氢脱硫催化剂。第三加氢单元中，各催化剂之间的装填比为：RG-30B:富矿前驱体材料1：RDM-33B:RCS-31＝6：60： 14：20(V/V)。According to the flow direction, the order of catalyst loading is hydrogenation protection catalyst, rich ore precursor material 1, hydrodemetallization desulfurization catalyst, and hydrodesulfurization catalyst. In the third hydrogenation unit, the loading ratio between the catalysts is: RG-30B: rich ore precursor material 1: RDM-33B: RCS-31=6:60:14:20 (V/V).

实施例11Example 11

按照物流方向，催化剂装填的顺序为加氢保护催化剂、富矿前驱体材料 2、富矿前驱体材料1、加氢脱金属脱硫催化剂、加氢脱硫催化剂。第三加氢单元中，各催化剂之间的装填比为：RG-30B:富矿前驱体材料2：富矿前驱体材料1：RDM-33B：RCS-31＝6：30：30：14：20(V/V)。According to the flow direction, the catalyst loading sequence is hydrogenation protection catalyst, richore precursor material 2, rich ore precursor material 1, hydrodemetallization desulfurization catalyst, and hydrodesulfurization catalyst. In the third hydrogenation unit, the loading ratio between the catalysts is: RG-30B: rich ore precursor material 2: rich ore precursor material 1: RDM-33B: RCS-31=6:30:30:14:20 ( V/V).

实施例12Example 12

按照物流方向，催化剂装填的顺序为：加氢保护催化剂、加氢脱金属脱硫催化剂、加氢脱硫催化剂。各催化剂之间的装填比为：RG-30B： RDM-33B:RCS-31＝15:40:45(V/V)。According to the flow direction, the order of catalyst loading is: hydroprotection catalyst, hydrodemetallization desulfurization catalyst, and hydrodesulfurization catalyst. The loading ratio between the catalysts was: RG-30B: RDM-33B: RCS-31=15:40:45 (V/V).

实施例13Example 13

按照物流方向，催化剂装填的顺序：加氢保护催化剂、富矿前驱体材料 3、加氢脱金属脱硫催化剂、加氢脱硫催化剂。各催化剂之间的装填比为： RG-30B:富矿前驱体材料3：RDM-33B:RCS-31＝10：40：25：35(V/V)。According to the flow direction, the order of catalyst loading: hydrogenation protection catalyst, richore precursor material 3, hydrodemetallization desulfurization catalyst, hydrodesulfurization catalyst. The loading ratio between the catalysts is: RG-30B: rich ore precursor material 3: RDM-33B: RCS-31=10:40:25:35 (V/V).

对比例1Comparative Example 1

催化剂与装置与实施例1相似。所不同的是：The catalyst and apparatus were similar to Example 1. The difference is:

本对比例中富芳馏分油QY(芳烃含量为20质量％)不经过部分加氢饱和处理装置，而直接与DOA混合。DOA与QY以质量比1:10混合，混合原料的性质见表3。In this comparative example, the aromatic-rich distillate QY (aromatics content of 20% by mass) was directly mixed with DOA without going through a partial hydrosaturation treatment device. DOA and QY were mixed in a mass ratio of 1:10, and the properties of the mixed raw materials were shown in Table 3.

混合原料进入溶氢单元中与氢气混合，获得的混合原料(其中的氢含量见表3中)经第三加氢单元加氢处理后，产品性质见表4。The mixed raw material enters the hydrogen dissolving unit and is mixed with hydrogen, and the obtained mixed raw material (the hydrogen content thereof is shown in Table 3) is hydrotreated by the third hydrogenation unit, and the product properties are shown in Table 4.

分馏第三加氢单元加氢处理得到的液相产品，大于等于350℃第二重组分性质见表5。The liquid phase product obtained by the hydroprocessing of the third hydrogenation unit of fractional distillation, the properties of the second heavy component at or above 350°C are shown in Table 5.

小于350℃第二轻组分在第四反应单元上进行试验，得到加氢裂化产品，性质见表6。The second light component less than 350°C is tested on the fourth reaction unit to obtain a hydrocracking product whose properties are shown in Table 6.

对比例2Comparative Example 2

本对比例中富芳馏分油QY不经过部分加氢饱和处理装置，而直接与 DOA混合。DOA与QY以质量比2:10混合，混合原料的性质见表3。In this comparative example, the aromatic-rich distillate QY is directly mixed with DOA without passing through the partial hydrosaturation treatment unit. DOA and QY were mixed in a mass ratio of 2:10, and the properties of the mixed raw materials were shown in Table 3.

对比例3Comparative Example 3

对比例3中富芳馏分油QY不经过部分加氢饱和处理装置，而直接与DOA混合。DOA与QY以质量比3:10混合，因混合原料中有大量固体(100℃下)，故无法进行下一步试验。In Comparative Example 3, the aromatic-rich distillate QY was directly mixed with DOA without passing through the partial hydrosaturation treatment unit. DOA and QY were mixed at a mass ratio of 3:10, and the next test could not be carried out due to a large amount of solids (at 100°C) in the mixed raw materials.

表1：DOA、DAO及第一加氢单元加氢处理后液相产品等的性质Table 1: Properties of DOA, DAO and liquid phase products after hydrotreating in the first hydroprocessing unit, etc.

项目projectDOADOADAODAO第一加氢单元加氢处理后液相产品Liquid phase product after hydrotreating of the first hydrotreating unit密度(20℃)，g/cm3Density (20℃), g/cm31153.61153.6981.1981.1939.1939.1残炭，质量％Residual carbon, mass %53.553.510.410.45.15.1硫含量，质量％Sulfur content, mass %7.27.24.54.50.390.39氮含量，质量％Nitrogen content, mass %0.680.680.390.390.210.21(Ni+V),μg/g(Ni+V), μg/g39039039396.86.8

表2：富芳馏分油加氢前后性质Table 2: Properties of aromatic-rich distillates before and after hydrogenation

表3：混合原料性质Table 3: Properties of mixed raw materials

表3(续表)：混合原料性质Table 3 (continued): Properties of mixed raw materials

实施例8Example 8对比例1Comparative Example 1对比例2Comparative Example 2种类typeDOA：第一重组分8DOA: Thefirst component 8DOA：QYDOA: QYDOA：QYDOA: QY质量比mass ratio1:101:101:101:102:102:1020℃状态20℃ state液态liquid液态liquid液态liquidC7不溶物，质量％C7 insoluble matter, mass%3.43.43.53.54.64.6残炭，质量％Residual carbon, mass %4.74.74.94.95.95.9硫，质量％Sulfur, mass %1.331.331.351.352.012.01粘度(100℃),(mm2/s)Viscosity(100℃),(mm2/s)2.92.92.92.93.03.0Ni+V,(μg/g)Ni+V, (μg/g)36.236.235.635.650.150.1溶氢后氢含量，质量％Hydrogen content after dissolving hydrogen, mass%0.150.150.140.140.150.15

表4：混合原料加氢处理后产品性质Table 4: Product properties after hydrotreating of mixed feedstocks

项目projectC7不溶物,质量％C7 insoluble matter, mass%残炭,质量％Residual carbon, mass %硫,质量％Sulfur, mass %粘度(100℃),mm2/sViscosity(100℃),mm2/sNi+V,(μg/g)Ni+V, (μg/g)实施例1Example 10.490.492.32.30.190.191.71.78.08.0实施例2Example 20.510.515.15.10.380.382.92.919.319.3实施例3Example 32.492.499.399.390.540.5410.110.126.426.4实施例4Example 43.903.9011.5011.500.690.6912.412.439.539.5实施例5Example 52.432.439.059.050.520.529.89.825.925.9实施例8Example 80.510.512.42.40.210.211.91.98.58.5实施例10Example 100.490.492.52.50.200.201.81.88.08.0实施例11Example 110.510.512.52.50.220.221.91.98.38.3实施例12Example 120.550.552.92.90.290.292.22.28.98.9实施例13Example 130.530.532.72.70.250.252.02.08.98.9对比例1Comparative Example 12.182.183.43.40.560.562.32.312.712.7对比例2Comparative Example 22.422.424.64.60.640.645.45.425.625.6

表5：第二重组分性质Table 5: Properties of the second component

表6：加氢裂化产品性质Table 6: Hydrocracking product properties

项目project密度(20℃)，g/cm3Density (20℃), g/cm3RONRON硫含量，μg/gSulfur content, μg/g实施例1Example 10.720.72＞92>92＜10<10实施例2Example 20.720.72＞92>92＜10<10实施例3Example 30.720.72＞92>92＜10<10实施例4Example 40.720.72＞92>92＜10<10实施例8Example 80.720.72＞92>92＜10<10实施例10Example 100.720.72＞92>92＜10<10实施例11Example 110.720.72＞92>92＜10<10实施例12Example 120.720.72＞92>92＜10<10实施例13Example 130.720.72＞92>92＜10<10对比例1Comparative Example 1>0.72>0.72<92<921313对比例2Comparative Example 2>0.72>0.72<92<921212

表7：富矿前驱体材料性质Table 7: Material properties of bonanza precursors

灼减，质量％Ignition reduction, mass %比表面积，m2/gSpecific surface area, m2/g吸水率，g/gWater absorption, g/g富矿前驱体材料1Bonanza Precursor Material 113.513.52632631.081.08富矿前驱体材料2Bonanza Precursor Material 229.929.92792791.221.22富矿前驱体材料3Bonanza Precursor Material 320.520.599991.051.05

由上述结果可以看出，本发明的技术能够从DOA得到优质的生产低硫船燃或低硫焦产品原料。It can be seen from the above results that the technology of the present invention can obtain high-quality raw materials for producing low-sulfur ship fuel or low-sulfur coke products from DOA.

并且，本发明的技术能够得到优质的和符合国V标准的汽油产品。Moreover, the technology of the present invention can obtain high-quality gasoline products that meet the National V standard.

以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described above in detail, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, a variety of simple modifications can be made to the technical solutions of the present invention, including combining various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the content disclosed in the present invention. All belong to the protection scope of the present invention.