A heavy oil processing method and system

Abstract

The present invention discloses a heavy oil processing method and system. The method comprises: a. a first heavy oil raw material is mixed with hydrogen and enters a first reaction zone for reaction, the product after the reaction enters a first separation zone, the liquid product obtained by the first hot low-pressure separator and the liquid product obtained by the first cold low-pressure separator are both entered into a flash tower for fractionation to obtain light components and heavy components; b. a second heavy oil raw material is mixed with hydrogen and enters a second reaction zone for reaction, the product after the reaction enters a second separation zone, the liquid product obtained by the second hot low-pressure separator, the liquid product obtained by the second cold low-pressure separator and the light component obtained by the flash tower in step a are all entered into a normal pressure fractionation tower for fractionation to obtain hydrogenated naphtha, hydrogenated diesel and hydrogenated heavy oil. The method and system can realize low-cost production of low-sulfur marine fuel oil.

Description

Technical Field

[0001] The invention belongs to the technical field of heavy oil processing, and in particular relates to a heavy oil processing method and system. Background Art

[0002] As global environmental regulations become increasingly stringent, the market demand for clean, light oil products such as gasoline and diesel is increasing, while the demand for clean, low-sulfur marine fuel oil is also increasing rapidly. The International Maritime Organization (IMO) convention stipulates that from January 2020, when ships are sailing in general areas at sea, the sulfur content of the marine fuel oil used will be reduced from the current no more than 3.5% to no more than 0.5%; when sailing in emission control areas, the sulfur content of the fuel oil used on board should not exceed 0.1%.

[0003] More stringent environmental standards for sulfur content and strong control of emission areas will have a huge impact on the fuel oil market, which is currently dominated by high-sulfur residual marine fuel oil, and will also bring huge challenges and opportunities to suppliers. In order to meet the requirements of the new standards, a large number of high-sulfur marine fuel oils will be replaced by low-sulfur residual or distillate marine fuel oils in the future. As the world's crude oil resources gradually become inferior and heavier, how to efficiently, economically and flexibly use the existing inferior heavy oil hydroprocessing technology to produce clean marine fuel oil has become an urgent problem for refineries and suppliers to solve.

[0004] At present, the main technologies for hydrotreating inferior heavy oil include fixed bed, fluidized bed, suspended bed and moving bed. Compared with other heavy oil hydrotreating technologies, fixed bed residue oil hydrotreating technology has the characteristics of mature process, easy operation and low investment, and can achieve efficient conversion and utilization of heavy oil, accounting for about 3 / 4 of the total residue oil hydrotreating processing capacity. The main purpose of fixed bed residue oil hydrotreating technology is to remove impurities such as sulfur, nitrogen, and metals from residue oil raw materials through the hydrotreating process, reduce the residual carbon value, provide feed for catalytic cracking units, and meet the market demand for light oil products such as gasoline and diesel. However, with the increasing market demand for low-sulfur marine fuel oil, existing fixed bed residue oil hydrotreating units often have to take into account the production tasks of catalytic cracking raw materials and low-sulfur residual marine fuel oil at the same time.

[0005] Due to the relatively stringent technical indicators of the feed properties of the catalytic cracking unit, the existing fixed-bed residue oil hydrogenation catalyst and its system and process technology directly produce low-sulfur residual marine fuel oil, which has problems such as insufficient hydrodesulfurization selectivity, excessive properties of hydrogenated products, and high production costs (high hydrogen consumption). For the existing fixed-bed residue oil hydrogenation unit in the refinery, although it can directly produce low-sulfur residual marine fuel oil with a sulfur content of less than 0.5% by optimizing the catalyst grading and adjusting the operating conditions of the unit, the purpose of reducing the cost of producing low-sulfur marine fuel oil by the unit is achieved. However, there is still insufficient hydrodesulfurization selectivity of the catalyst and its system, and it is difficult to simultaneously take into account the production needs of low-sulfur residual marine fuel and catalytic cracking raw materials.

[0006] CN10274690A discloses a method for preparing marine fuel oil, in which a heavy oil component is subjected to visbreaking and fractionation to obtain a blending component for marine fuel. This method can reduce the production cost of marine fuel oil. However, visbreaking generally has a low conversion rate, insufficient reaction depth, and the sulfur content of the produced product is still very high, which cannot directly meet the index requirements of marine fuel oil. On the other hand, the light oil products with high added value are reduced, which is not conducive to maximizing the economic benefits of the device.

[0007] CN19705909A discloses a method for producing marine fuel oil by hydrogenation of coal tar, wherein coal tar is introduced into a slurry bed hydrogenation reactor for hydrogenation treatment, and then fractionated to obtain a blending component of marine fuel oil. This method can produce qualified blending components of marine fuel oil, but the current slurry bed process technology is not mature enough, and the processing capacity of the device is insufficient to meet the huge market demand for marine fuel oil.

[0008] CN110205160A discloses a process for preparing marine fuel oil by desolidification and hydrogenation of catalytic cracking oil slurry. The method comprises: hydrogenating the desolidified oil slurry under the action of a catalyst having nickel oxide and molybdenum oxide as active components and aluminum oxide as a carrier to obtain hydrogenated oil slurry, and then mixing it with marine fuel components to obtain marine fuel oil. The method can produce marine fuel oil blending components based on low hydrogen consumption, but still uses conventional hydroprocessing catalysts, which have the problems of low desulfurization capacity and low blending ratio. Summary of the invention

[0009] In view of the shortcomings of the prior art, the present invention provides a heavy oil processing method and system. The method and system can enable different reaction series of the heavy oil hydroprocessing unit to adjust the hydrogenation products economically and flexibly according to market demand, which can not only realize the low-cost production of low-sulfur marine fuel oil, but also can more flexibly adjust and optimize the light / heavy clean hydrogenation product structure of the refinery, meet market demand, and improve the economic benefits of the refinery.

[0010] The first aspect of the present invention provides a heavy oil processing system, comprising two series of residue oil hydrogenation process devices, namely a first series of devices and a second series of devices, wherein the first series of devices comprises a first reaction zone and a first separation zone, the first separation zone comprises a first hot high-pressure separator, a first hot low-pressure separator, a first cold high-pressure separator and a first cold low-pressure separator and a flash tower, the second series of devices comprises a second reaction zone and a second separation zone, the second separation zone comprises a second hot high-pressure separator, a second hot low-pressure separator, a second cold high-pressure separator and a second cold low-pressure separator and an atmospheric distillation tower; the liquid phase outlet of the first hot low-pressure separator and the liquid phase outlet of the first cold low-pressure separator are connected to the inlet of the flash tower, and the light component outlet of the flash tower, the liquid phase outlet of the second hot low-pressure separator and the liquid phase outlet of the second cold low-pressure separator are connected to the inlet of the atmospheric distillation tower.

[0011] Furthermore, the first reaction zone is preferably a fixed bed reactor; and the second reaction zone is preferably a fixed bed reactor.

[0012] The second aspect of the present invention provides a heavy oil processing method, which adopts the above-mentioned heavy oil processing system, that is, two series of residual oil hydrogenation process devices, and the process includes:

[0013] a. The first heavy oil feedstock is mixed with hydrogen and enters the first reaction zone for reaction. The reaction product enters the first separation zone. The liquid product obtained from the first hot low-pressure separator and the liquid product obtained from the first cold low-pressure separator enter the flash tower for fractionation to obtain light components and heavy components.

[0014] b. The second heavy oil feedstock is mixed with hydrogen and enters the second reaction zone for reaction. The reaction product enters the second separation zone. The liquid product obtained from the second hot low-pressure separator, the liquid product obtained from the second cold low-pressure separator, and the light component obtained from the flash tower in step a all enter the atmospheric distillation tower for fractionation to obtain hydrogenated naphtha, hydrogenated diesel and hydrogenated heavy oil.

[0015] Furthermore, in the heavy oil processing method, step a includes: the first hot high-pressure separator in the first separation zone performs gas-liquid two-phase separation, the obtained gas phase product enters the first cold high-pressure separator, and the obtained liquid phase product enters the first hot low-pressure separator for gas-liquid separation; the gas phase product obtained after separation by the first hot low-pressure separator and the liquid phase product obtained by separation by the first cold high-pressure separator enter the first cold low-pressure separator for gas-liquid separation, and the liquid phase product obtained by the first hot low-pressure separator and the liquid phase product obtained by the first cold low-pressure separator both enter the flash tower for fractionation to obtain light components and heavy components. The gas phase separated by the first cold high-pressure separator is used as circulating hydrogen after operations such as dehydrogenation, and is mixed with part of the new hydrogen and enters the first reaction zone as a hydrogen raw material. The gas phase separated by the first cold low-pressure separator is sent to a purification device or incorporated into a low-fraction gas pipeline network after operations such as dehydrogenation.

[0016] Furthermore, in the heavy oil processing method, step b includes: the second hot high-pressure separator in the second separation zone performs gas-liquid two-phase separation, the obtained gas phase product enters the second cold high-pressure separator, the obtained liquid phase product enters the second hot low-pressure separator for gas-liquid separation, the gas phase product obtained after separation by the second hot low-pressure separator and the liquid phase product obtained by separation by the second cold high-pressure separator enter the second cold low-pressure separator for gas-liquid separation, the liquid phase product obtained by the second hot low-pressure separator, the liquid phase product obtained by the second cold low-pressure separator and the light component obtained by the flash tower in step a all enter the atmospheric distillation tower for fractionation to obtain hydrogenated naphtha, hydrogenated diesel and hydrogenated heavy oil. The gas phase separated by the second cold high-pressure separator is used as circulating hydrogen after dehydrogenation and other operations, and is mixed with part of the new hydrogen and enters the second reaction zone as a hydrogen raw material. The gas phase separated by the second cold low-pressure separator is sent to a purification device or incorporated into a low-fraction gas pipeline network after dehydrogenation and other operations.

[0017] Furthermore, the cutting point between the light component and the heavy component obtained in step a is 260°C to 400°C, preferably 280°C to 380°C. The heavy component obtained in step a is used as low-sulfur marine fuel oil (sulfur content is less than 0.5% by mass) or a blending component. The initial boiling point of the hydrogenated heavy oil in step b is 330°C to 370°C, preferably 340°C to 360°C, and is used as low-sulfur marine fuel oil (sulfur content is less than 0.5% by mass) or a blending component.

[0018] Furthermore, the first heavy oil feedstock and the second heavy oil feedstock can be independently selected from at least one of atmospheric residue and vacuum residue, and the heavy oil feedstock can also contain one or more of catalytic diesel, coker wax oil, deasphalted oil, and heavy distillate oil. In the heavy oil feedstock, the sulfur content is not higher than 5.0% by mass, and can be 2.0% to 4.0%; the Conradson carbon residue is not higher than 18%, and can be 9% to 14%; the total content of heavy metal nickel and vanadium is not higher than 200 μg / g, and can be 40 to 120 μg / g; the total nitrogen content is not higher than 0.80%, and can be 0.25% to 0.70%.

[0019] Furthermore, the first reaction zone adopts a fixed bed residue oil hydrogenation process. The fixed bed residue oil hydrogenation process adopts at least one hydrogenation reactor, more preferably multiple hydrogenation reactors are arranged in series, and most preferably three to five hydrogenation reactors are arranged.

[0020] Furthermore, the first reaction zone is loaded with a hydrogenation protection catalyst, a hydrodemetallization catalyst and a hydrodesulfurization catalyst. Among them, based on the total loading volume of the catalyst in the first reaction zone, the hydrogenation protection catalyst accounts for 5% to 30% of the total loading volume, preferably 10% to 25%; the hydrodemetallization catalyst accounts for 10% to 55% of the total loading volume, preferably 20% to 45%; the hydrodesulfurization catalyst accounts for 30% to 85% of the total loading volume, preferably 30% to 65%. After the hydrodesulfurization catalyst, a hydrodenitrogenation catalyst can also be selectively loaded, and its loading volume accounts for less than 20% of the total loading volume, preferably 5% to 15%. The first reaction zone can be loaded in a conventional grading order, and the loading order is generally to make the feedstock oil contact with the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst, and the hydrodenitrogenation catalyst in turn. The hydroprotection catalyst, hydrodemetallization catalyst, hydrodesulfurization catalyst and hydrodenitrogenation catalyst can adopt catalysts with corresponding functions commonly used in the art, such as CEN, FZC, ZTN and ZTS series residue hydrotreating catalysts produced by the Catalyst Branch of Sinopec.

[0021] Furthermore, the operating conditions of the first reaction zone in step a are as follows: hydrogen partial pressure of 5MPa to 35MPa, reaction temperature of 300°C to 420°C, and volumetric space velocity of the first heavy oil raw material liquid of 0.1h -1 ~5.0h -1 , the total hydrogen-to-oil volume ratio is 100-5000; preferably, the hydrogen partial pressure is 13MPa-20MPa, the reaction temperature is 330℃-410℃, and the volumetric space velocity of the first heavy oil raw material liquid is 0.15h -1 ~2.0h -1 , the total hydrogen-to-oil volume ratio is 300-3000.

[0022] Furthermore, the second reaction zone adopts a fixed bed residue oil hydrogenation process. The fixed bed residue oil hydrogenation process adopts at least one hydrogenation reactor, more preferably multiple hydrogenation reactors are arranged in series, and most preferably three to five hydrogenation reactors are arranged.

[0023] Furthermore, the second reaction zone includes a hydrogenation protection catalyst, a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodenitrogenation catalyst. Wherein, based on the total loading volume of the catalyst in the second reaction zone, the hydrogenation protection catalyst accounts for 5% to 30% of the total loading volume, preferably 10% to 25%; the hydrodemetallization catalyst accounts for 10% to 55% of the total loading volume, preferably 20% to 50%; the hydrodesulfurization catalyst accounts for 20% to 65% of the total loading volume, preferably 30% to 45%; the hydrodenitrogenation catalyst accounts for 10% to 40% of the total loading volume, preferably 15% to 35%. The second reaction zone can be loaded in a conventional grading order, and the loading order is generally to contact the feedstock oil with the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the residual oil hydrodenitrogenation catalyst in turn. The hydroprotection catalyst, hydrodemetallization catalyst, hydrodesulfurization catalyst, and residue hydrodenitrogenation catalyst can adopt catalysts with corresponding functions commonly used in the art, such as CEN, FZC, ZTN, and ZTS series residue hydrotreating catalysts produced by the Catalyst Branch of Sinopec.

[0024] Furthermore, the operating conditions of the second reaction zone in step b are as follows: hydrogen partial pressure of 5MPa to 35MPa, reaction temperature of 300°C to 420°C, volumetric space velocity of the second heavy oil raw material liquid of 0.1h -1 ~5.0h -1 , the total hydrogen-to-oil volume ratio is 100-5000; preferably, the hydrogen partial pressure is 13MPa-20MPa, the reaction temperature is 330℃-410℃, and the volumetric space velocity of the second heavy oil raw material liquid is 0.15h -1 ~2.0h -1 , the total hydrogen-to-oil volume ratio is 300-3000.

[0025] Furthermore, the hydrodesulfurization catalyst in the first reaction zone and / or the second reaction zone is preferably a hydrodesulfurization catalyst A. The hydrodesulfurization catalyst A comprises: a carrier, a molybdenum element and a Group VIII metal element, wherein the molybdenum element is at least partially present in the catalyst in the form of carbonyl molybdenum, and the Group VIII metal element is present in the catalyst in the form of a Group VIII metal porphyrin compound.

[0026] Furthermore, in the hydrodesulfurization catalyst A, based on the weight of the carrier, the content of the Group VIII metal in terms of oxide is 0.5% to 8.0%, preferably 1.0% to 6.0%, and the content of molybdenum in terms of oxide is 5.0% to 25.0%, preferably 8.0% to 20.0%.

[0027] Furthermore, in the hydrodesulfurization catalyst A, at least part of the molybdenum element exists in the catalyst in the form of carbonyl molybdenum, and the molybdenum in the form of carbonyl molybdenum accounts for more than 40% of the total molybdenum, preferably 50% to 90%, calculated as molybdenum atoms.

[0028] Furthermore, in the hydrodesulfurization catalyst A, the molybdenum element exists in the catalyst in the form of carbonyl molybdenum and molybdenum oxide, and the ratio of carbonyl molybdenum to molybdenum oxide is 4:6 to 9.5:0.5, preferably 7:3 to 9:1, calculated on the basis of molybdenum atoms.

[0029] Furthermore, in the hydrodesulfurization catalyst A, the Group VIII metal is selected from at least one of nickel and cobalt, and the Group VIII metal porphyrin compound is preferably selected from at least one of protoporphyrin nickel, protoporphyrin cobalt, tetraphenylporphyrin nickel, tetraphenylporphyrin cobalt, tetramethoxyphenylporphyrin nickel, and tetramethoxyphenylporphyrin cobalt.

[0030] Furthermore, in the hydrodesulfurization catalyst A, the carrier may be at least one of alumina, silicon oxide, molecular sieve, activated carbon, titanium aluminum, titanium silicon, etc., preferably alumina.

[0031] Furthermore, the properties of the hydrodesulfurization catalyst A are as follows: the specific surface area is 50 to 300 m 2 / g, preferably 100-240m 2 / g, and the pore volume is 0.4-1.3 mL / g, preferably 0.5-1.0 mL / g.

[0032] Furthermore, the hydrodesulfurization catalyst A is a molded body, and its shape can be the shape commonly used for fixed bed hydrogenation catalysts, such as strip, clover, four-leaf clover, sphere, cylinder, etc., and its particle size is 2-10 mm, preferably 2.5-8.0 mm.

[0033] Furthermore, the preparation method of the hydrodesulfurization catalyst A comprises:

[0034] (1) preparing a catalyst intermediate containing carbonyl molybdenum;

[0035] (2) impregnating the catalyst intermediate obtained in step (1) with an organic impregnation solution containing a Group VIII metal porphyrin compound, removing the organic solvent, and obtaining the hydrodesulfurization catalyst A.

[0036] Furthermore, in the preparation method of the hydrodesulfurization catalyst A, the step (1) of preparing the catalyst intermediate containing carbonyl molybdenum can first prepare a carrier-loaded MoO 3 The catalyst intermediate is then MoO 3 At least part of it is converted into molybdenum carbonyl to prepare a catalyst intermediate containing molybdenum carbonyl.

[0037] Furthermore, in the preparation method of the hydrodesulfurization catalyst A, the preparation carrier loaded with MoO 3 The catalyst intermediate can be prepared by conventional methods such as coprecipitation, impregnation, kneading, etc., preferably by impregnation, the process is as follows: impregnating a molybdenum-containing solution on a carrier, drying and calcining to obtain a carrier-loaded MoO 3 The catalyst intermediate. Wherein, the carrier can be prepared by commercial products or according to the method disclosed in the prior art. In the molybdenum-containing solution, the solute includes at least one of ammonium molybdate, molybdenum heteropolyacid salts, etc. The impregnation method can be equal volume impregnation or supersaturated impregnation, preferably equal volume impregnation. The drying conditions are as follows: the drying temperature is 80-180°C, and the drying time is 2-6h; the calcination conditions are as follows: the calcination temperature is 400-600°C, and the calcination time is 2-5h. The carrier loads MoO 3 The catalyst intermediate is a molded body, which can be molded by conventional methods, such as extrusion molding, etc. During the molding process, conventional molding aids, such as peptizers, additives, etc., can be added.

[0038] Furthermore, in the preparation method of the hydrodesulfurization catalyst A, the preparation process of the catalyst intermediate containing carbonyl molybdenum is as follows: the carrier loads MoO 3 The catalyst intermediate is mixed with an organic solvent I, a first catalyst and an ether gas to cause a first reaction, and then carbon monoxide is introduced into the reaction system to cause a second reaction. After drying, a catalyst intermediate containing carbonyl molybdenum is obtained. The organic solvent I can be at least one of carbon tetrachloride, trichloropropane, chloroform, perchloroethylene and trichloroethylene. The first catalyst can be at least one of pentacarbonyl iron, tetracarbonyl nickel and octacarbonyl dicobalt. The organic solvent I and the loaded MoO 3 The mass ratio of the catalyst intermediate is 1:1-5:1, preferably 2:1-4:1. 3The mass ratio of the catalyst intermediate is 1:10-1:50, preferably 1:20-1:40. The reaction conditions of the first reaction are as follows: the reaction pressure is 1.0-10.0MPa, preferably 3.0-6.0MPa, the reaction temperature is 150-300°C, preferably 180-250°C, and the reaction time is 1.0-10.0h, preferably 3.0-6.0h. The ether gas can be one or a mixture of diethyl ether and methyl ether. The amount of ether gas introduced is to maintain the pressure required for the first reaction. The reaction conditions of the second reaction are as follows: the reaction pressure is 5.0-20.0MPa, preferably 8.0-14.0MPa, the reaction temperature is 50-150°C, preferably 70-120°C, and the reaction time is 1.0-10.0h, preferably 3.0-6.0h. The carbon monoxide partial pressure accounts for more than 50% of the reaction pressure, preferably 60%-80%. The drying conditions are as follows: drying temperature is 90-150°C, and drying time is 1-4h.

[0039] Furthermore, in the preparation method of the hydrodesulfurization catalyst A, the preparation method of the organic impregnation liquid containing the Group VIII metal porphyrin compound in step (2) is: the Group VIII metal porphyrin compound is dissolved in an organic solvent II. The organic solvent II can be at least one of toluene, benzene, xylene, decahydronaphthalene, and tetrahydronaphthalene. The Group VIII metal compound comes from soluble salts, such as at least one of nitrates, citrates, monohydrogen phosphates, and dihydrogen phosphates. In the organic impregnation liquid containing the Group VIII metal porphyrin compound, the concentration of the Group VIII metal porphyrin compound is 100g / L-300g / L. The impregnation can be performed by an equal volume impregnation method, an unsaturated impregnation method, etc. The removal of the organic solvent generally requires that the organic solvent be removed under the condition that the Group VIII metal porphyrin compound is not decomposed, specifically, the temperature is 90-150°C and the time is 1-4h. The removal of the organic solvent is preferably performed under reduced pressure.

[0040] Furthermore, the sulfur content of the low-sulfur marine fuel oil does not exceed 0.5% by mass.

[0041] Compared with the prior art, the present invention has the following advantages:

[0042] (1) The heavy oil processing method of the present invention adjusts and optimizes the process flow of the first series of devices and the second series of devices, so that the heavy components (sulfur content by mass is less than 0.5%) in the flash tower of the first series of devices are preferably 280°C to 380°C; the hydrogenated heavy oil (sulfur content by mass is less than 0.5%) in the atmospheric distillation tower of the second series of devices is preferably 340°C to 360°C, both of which can be used as low-sulfur marine fuel oil, thereby achieving the purpose of maximizing the production of low-sulfur marine fuel oil.

[0043] (2) In the heavy oil processing method of the present invention, the hydrodesulfurization catalyst used in the first reaction zone and / or the second reaction zone is preferably a hydrodesulfurization catalyst A, wherein the active component is mainly present in the catalyst in the form of carbonyl molybdenum and Group VIII metal porphyrin compounds, which not only improves the existence state of the active component on the carrier, but also improves the interaction between the active component and the carrier. After the hydrodesulfurization catalyst A is sulfurized, it can produce a Ni(Co)-Mo-S active phase with high selective hydrodesulfurization activity and low aromatic hydrogenation saturation activity, thereby facilitating the selective hydrodesulfurization reaction process, reducing the hydrogenation saturation reaction process of condensed aromatics, etc., having the characteristics of low hydrogen consumption, etc., while reducing the production cost of low-sulfur marine fuel oil, it can also achieve the purpose of maximizing the production of low-sulfur marine fuel oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 It is a schematic diagram of the heavy oil processing method of the present invention.

[0045] Description of reference numerals:

[0046] 11 is the first heavy oil feedstock; 12 is hydrogen; 13 is the first reaction zone; 14 is the first hot high-pressure separator; 15 is the first hot low-pressure separator; 16 is the first cold high-pressure separator; 17 is the first cold low-pressure separator; 18 is the flash tower; 19 is the liquid product obtained from the first hot low-pressure separator; 110 is the liquid product obtained from the first cold low-pressure separator; 111 is the flash light component; 112 is the flash heavy component; 113 is the gas product obtained from the first hot low-pressure separator; 114 is the gas product obtained from the first cold high-pressure separator; 115 is the gas product obtained from the first cold low-pressure separator;

[0047] 21 is the second heavy oil feedstock; 22 is hydrogen; 23 is the second reaction zone; 24 is the second hot high-pressure separator; 25 is the second hot low-pressure separator; 26 is the second cold high-pressure separator; 27 is the second cold high-pressure separator; 28 is the atmospheric distillation tower; 29 is the liquid product obtained from the second hot low-pressure separator; 210 is the liquid product obtained from the second cold low-pressure separator; 211 is hydrogenated naphtha; 212 is hydrogenated diesel; 213 is hydrogenated heavy oil; 214 is the gaseous product obtained from the second hot low-pressure separator; 215 is the gaseous product obtained from the second cold high-pressure separator; 216 is the gaseous product obtained from the second cold low-pressure separator. DETAILED DESCRIPTION

[0048] In the present invention, the following is combined Figure 1 The heavy oil processing method of the present invention is described in detail.

[0049] The process flow of heavy oil processing of the present invention (see Figure 1 )include:

[0050] a. The first heavy oil feedstock 11 is mixed with hydrogen 12 and enters the first reaction zone 13 for reaction. The product after the reaction enters the first hot high-pressure separator 14 of the first separation zone for gas-liquid two-phase separation. The obtained gas phase product enters the first cold high-pressure separator 16, and the obtained liquid phase product enters the first hot low-pressure separator 15 for gas-liquid separation; the gas phase product 113 obtained after separation in the first hot low-pressure separator 15 and the liquid phase product obtained after separation in the first cold high-pressure separator 16 enter the first cold low-pressure separator 17 for gas-liquid separation, and the liquid phase product 19 obtained by the first hot low-pressure separator 15 and the liquid phase product 110 obtained by the first cold low-pressure separator enter the flash tower 18 to obtain a light component 111 and a heavy component 112; the gas phase 114 separated by the first cold high-pressure separator is used as circulating hydrogen after being subjected to operations such as dehydrogenation, and is mixed with part of the new hydrogen and enters the second reaction zone as the hydrogen feedstock 12; the gas phase 115 separated by the first cold low-pressure separator is sent to a purification device or incorporated into a low-fraction gas pipeline network after being subjected to operations such as dehydrogenation.

[0051] b. The second heavy oil feedstock 21 is mixed with hydrogen 22 and enters the second reaction zone 23 for reaction. The product after the reaction enters the second hot high-pressure separator 24 of the second separation zone for gas-liquid two-phase separation. The obtained gas phase product enters the second cold high-pressure separator 26. The obtained liquid phase product enters the second hot low-pressure separator 25 for gas-liquid separation. The gas phase product 214 obtained after separation in the second hot low-pressure separator 25 and the liquid phase product obtained by separation of the second cold high-pressure separator 26 enter the second cold low-pressure separator 27 for gas-liquid separation. The liquid product 29, the liquid product 210 obtained by the second cold low-pressure separator 27 and the light component 111 obtained by the flash tower in step a enter the atmospheric distillation tower 28 to obtain hydrogenated naphtha 211, hydrogenated diesel 212 and hydrogenated heavy oil 213; the gas phase 215 separated by the second cold high-pressure separator is used as circulating hydrogen after being subjected to operations such as dehydrogenation, and is mixed with part of the new hydrogen and enters the second reaction zone as hydrogen feedstock 22; the gas phase 216 separated by the second cold low-pressure separator is sent to a purification device or incorporated into a low-pressure gas pipeline network after being subjected to operations such as dehydrogenation.

[0052] The heavy component 112 obtained in step a is used as low-sulfur marine fuel oil (sulfur content is less than 0.5% by mass). The hydrogenated heavy oil 213 in step b can also be used as low-sulfur marine fuel oil (sulfur content is less than 0.5% by mass) and can also be used as catalytic cracking feed.

[0053] The method of the present invention is first described in detail below with reference to embodiments.

[0054] In the present invention, XPS is measured on a MultiLab 2000 X-ray photoelectron spectrometer, and the operating conditions are: light source: Al Kα, E b = 1486.6 eV, and the peak shift caused by charging is corrected by the position of the Al 2p peak of the reference catalyst carrier (C1s, 285.0 eV). In the present invention, the ratio of Mo to Group VIII atoms on the surface of the sulfided catalyst is measured by the XPS method.

[0055] In the present invention, the specific surface area and pore volume are measured by using ASAP2405 physical adsorption instrument, and the measurement method is as follows: After the sample is treated, the liquid N 2 The specific surface area was calculated by BET method, and the pore volume and pore distribution were calculated by BJH method.

[0056] Example 1

[0057] Weigh 1000.0g of alumina dry powder, add 20.0g of citric acid and 15.0g of sesbania powder, mix well, add 800.0g of aqueous solution containing 2.0% nitric acid, roll for 15.0min, and squeeze out strips with a clover plate with a diameter of 2.0mm. Dry at 120℃ for 4.0h and calcine at 600℃ for 3.0h. The calcined carrier is recorded as S-0.

[0058] Weigh 49.0g of ammonium heptamolybdate and 30.0g of 25wt% ammonia water to make 180mL of aqueous solution, the solution is recorded as MQ-1. Use 180mL of MQ-1 to impregnate 200g of S-0, dry at 150℃ for 3.0h, and then calcine at 400℃ for 2.0h to obtain carrier-loaded MoO 3 The catalyst intermediate is denoted as MA-1.

[0059] Weigh 50g MA-1, 150g carbon tetrachloride, and 2.0g iron pentacarbonyl, add them into a 500mL autoclave, introduce ether gas, maintain the pressure at 4.0MPa, and the temperature at 200°C, and react for 5h. Then lower the temperature to 90°C, introduce carbon monoxide, raise the pressure to 12.0MPa, and react for 5h. Take out the catalyst, dry it at 120°C for 2h, and obtain a catalyst intermediate containing carbonyl molybdenum, which is recorded as MT-1.

[0060] Weigh 8.3 g of nickel tetraphenylporphyrin and dissolve it in 50.0 mL of toluene. The obtained solution is recorded as BQ-1. MT-1 is impregnated with BQ-1 and evaporated at 120° C. under reduced pressure for 4.0 h. The obtained catalyst is recorded as TC-1.

[0061] Take 10.0g TC-1 and put it into a tubular reactor to pre-sulfurize the catalyst. The sulfiding liquid is 4.0% by mass of CS 2The cyclohexane solution was introduced at a flow rate of 30.0 mL / h for the sulfiding liquid, the hydrogen pressure was 3.0 MPa, the hydrogen flow rate was 120 mL / min, and the reaction was divided into two temperature stages. The first stage started from 120°C, the heating rate was 1.0°C / min, and the temperature was kept constant for 6.0 hours after reaching 160°C; the second stage started from 160°C, the heating rate was 2.0°C / min, and the temperature was kept constant for 2.0 hours after reaching 280°C, and the sulfidation was completed. The catalyst obtained after sulfidation was recorded as SC-1.

[0062] Example 2

[0063] Carrier S-0, carrier loaded with MoO 3 The preparation process of the catalyst intermediate MA-1 and the catalyst intermediate MT-1 containing carbonyl molybdenum is the same as that in Example 1.

[0064] Weigh 8.3 g of tetraphenylporphyrin cobalt and dissolve it in 50.0 mL of toluene. The obtained solution is recorded as BQ-2. MT-1 is impregnated with BQ-2 and evaporated at 120° C. under reduced pressure for 4.0 h. The obtained catalyst is recorded as TC-2.

[0065] Take 10.0g TC-2 and put it into a tubular reactor to pre-sulfurize the catalyst. The sulfiding liquid is 4.0% by mass of CS 2 The cyclohexane solution was introduced at a flow rate of 30.0 mL / h for the sulfiding liquid, the pressure of hydrogen was 3.0 MPa, the flow rate of hydrogen was 120 mL / min, and the reaction was divided into two temperature stages. The first stage started from 120°C, the heating rate was 1.0°C / min, and the temperature was kept constant for 6.0 hours after reaching 160°C; the second stage started from 160°C, the heating rate was 2.0°C / min, and the temperature was kept constant for 2.0 hours after reaching 280°C, and the sulfidation was completed. The catalyst obtained after sulfidation was recorded as SC-2.

[0066] Example 3

[0067] Carrier S-0, carrier loaded with MoO 3 The preparation process of the catalyst intermediate MA-1 is the same as that in Example 1.

[0068] Weigh 50g MA-1, 150g carbon tetrachloride, and 2.0g iron pentacarbonyl, add them into a 500mL autoclave, introduce methyl ether gas, maintain the pressure at 4.0MPa, and the temperature at 200°C, and react for 5h. Then lower the temperature to 90°C, introduce carbon monoxide, raise the pressure to 12.0MPa, and react for 5h. Take out the catalyst, dry it at 120°C for 2h, and obtain a catalyst intermediate containing carbonyl molybdenum, which is recorded as MT-2.

[0069] Weigh 6.4 g of protoporphyrin nickel and dissolve it in 50.0 mL of toluene. The obtained solution is recorded as BQ-3. MT-2 is impregnated with BQ-3 and evaporated at 120°C under reduced pressure for 4.0 h. The obtained catalyst is recorded as TC-3.

[0070] Take 10.0g TC-3 and put it into a tubular reactor to pre-sulfurize the catalyst. The sulfiding liquid is 4.0% by mass of CS 2 The cyclohexane solution was introduced at a flow rate of 30.0 mL / h for the sulfiding liquid, a hydrogen pressure of 3.0 MPa, a hydrogen flow rate of 120 mL / min, and the reaction was divided into two temperature stages. The first stage started at 120°C, with a heating rate of 1.0°C / min, and kept at a constant temperature for 6.0 h after reaching 160°C; the second stage started at 160°C, with a heating rate of 2.0°C / min, and kept at a constant temperature for 2.0 h after reaching 280°C, and the sulfidation was completed. The catalyst obtained after sulfidation was recorded as SC-3.

[0071] Example 4

[0072] Carrier S-0, carrier loaded with MoO 3 The preparation process of the catalyst intermediate MA-1 is the same as that of Example 1. The preparation process of the catalyst intermediate MT-2 containing carbonyl molybdenum is the same as that of Example 3.

[0073] Weigh 10.0 g of tetramethoxyphenylporphyrin cobalt and dissolve it in 50.0 mL of toluene. The obtained solution is recorded as BQ-4. MT-2 is impregnated with BQ-4 and evaporated at 120° C. under reduced pressure for 4.0 h. The obtained catalyst is recorded as TC-4.

[0074] Take 10.0g TC-4 and put it into a tubular reactor to pre-sulfurize the catalyst. The sulfiding liquid is 4.0% by mass of CS 2 The cyclohexane solution was introduced at a flow rate of 30.0 mL / h for the sulfiding liquid, a hydrogen pressure of 3.0 MPa, a hydrogen flow rate of 120 mL / min, and the reaction was divided into two temperature stages. The first stage started at 120°C, with a heating rate of 1.0°C / min, and kept at a constant temperature for 6.0 h after reaching 160°C; the second stage started at 160°C, with a heating rate of 2.0°C / min, and kept at a constant temperature for 2.0 h after heating to 280°C, and the sulfidation was completed. The catalyst obtained after sulfidation was recorded as SC-4.

[0075] Example 5

[0076] Carrier S-0, carrier loaded with MoO 3 The preparation of the catalyst intermediate MA-1 and the catalyst intermediate MT-1 containing carbonyl molybdenum is the same as in Example 1.

[0077] Weigh 3.5 g of nickel nitrate hexahydrate and dissolve it in 50.0 mL of water. The resulting solution is recorded as BQ-5. MT-1 is impregnated with BQ-5 and evaporated at 120° C. under reduced pressure for 4.0 h. The resulting catalyst is recorded as TC-5.

[0078] Take 10.0g TC-5 and put it into a tubular reactor to pre-sulfurize the catalyst. The sulfiding liquid is 4.0% CS 2 The cyclohexane solution was introduced at a flow rate of 30.0 mL / h for the sulfiding liquid, a hydrogen pressure of 3.0 MPa, a hydrogen flow rate of 120 mL / min, and the reaction was divided into two temperature stages. The first stage started at 120°C, with a heating rate of 1.0°C / min, and kept at a constant temperature for 6.0 h after reaching 160°C; the second stage started at 160°C, with a heating rate of 2.0°C / min, and kept at a constant temperature for 2.0 h after heating to 280°C, and the sulfidation was completed. The catalyst obtained after sulfidation was recorded as SC-5.

[0079] Example 6

[0080] Carrier S-0, carrier loaded with MoO 3 The preparation of catalyst intermediate MA-1 and solution BQ-6 is the same as in Example 1.

[0081] MA-1 was impregnated with BQ-6 and evaporated under reduced pressure at 120°C for 4.0 h. The obtained catalyst was named TC-6.

[0082] Take 10.0g TC-6 and put it into a tubular reactor to pre-sulfurize the catalyst. The sulfiding liquid is 4.0% by mass of CS 2 The cyclohexane solution was introduced at a flow rate of 30.0 mL / h for the sulfiding liquid, a hydrogen pressure of 3.0 MPa, a hydrogen flow rate of 120 mL / min, and the reaction was divided into two temperature stages. The first stage started at 120°C, with a heating rate of 1.0°C / min, and kept at a constant temperature for 6.0 h after reaching 160°C; the second stage started at 160°C, with a heating rate of 2.0°C / min, and kept at a constant temperature for 2.0 h after reaching 280°C, and the sulfidation was completed. The catalyst obtained after sulfidation was recorded as SC-6.

[0083] Example 7

[0084] This example introduces the preparation of a conventional nickel-molybdenum-alumina catalyst.

[0085] Carrier S-0, carrier loaded with MoO 3 The preparation of catalyst intermediate MA-1 is the same as in Example 1, and the preparation of solution BQ-7 is the same as in Example 5.

[0086] 50.0 g of MA-1 was impregnated with solution BQ-7 and dried at 150°C. The obtained catalyst was designated as TC-7.

[0087] Take 10.0g TC-7 and put it into a tubular reactor to pre-sulfurize the catalyst. The sulfiding liquid is 4.0% by mass of CS 2 The cyclohexane solution was introduced at a flow rate of 30.0 mL / h for the sulfiding liquid, a hydrogen pressure of 3.0 MPa, a hydrogen flow rate of 120 mL / min, and the reaction was divided into two temperature stages. The first stage started at 120°C, with a heating rate of 1.0°C / min, and kept at a constant temperature for 6.0 h after reaching 160°C; the second stage started at 160°C, with a heating rate of 2.0°C / min, and kept at a constant temperature for 2.0 h after reaching 280°C, and the sulfidation was completed. The catalyst obtained after sulfidation was recorded as SC-7.

[0088] The catalysts TC-1, TC-2, TC-3, TC-4, TC-5, TC-6 and TC-7 obtained in the above examples were characterized by XPS to obtain the ratio of carbonyl molybdenum to total molybdenum in terms of molybdenum atoms, and the results are shown in Table 1. The sulfided catalysts obtained in the above examples were characterized by XPS, and the ratio of Mo to Group VIII atoms on their surfaces is shown in Table 2. The compositions and properties of the catalysts TC-1, TC-2, TC-3, TC-4, TC-5, TC-6 and TC-7 obtained in the above examples are shown in Table 3.

[0089] Table 1 XPS characterization results of catalysts obtained in various examples

[0090] Example No. Carbonyl molybdenum proportion, % (based on molybdenum atoms) 1 83 2 79 3 85 4 82 5 82 6 0 7 0

[0091] Table 2 Ratio of Mo to Group VIII atoms on the surface of sulfided catalysts obtained in various examples

[0092] Example No. Mo / Co(Ni) atomic ratio 1 6.2 2 6.5 3 6.4 4 6.3 5 7.2 6 8.5 7 10.4

[0093] Table 3 Composition and properties of the catalysts obtained in each embodiment

[0094]

[0095] Embodiment 8-14

[0096] Using fixed bed technology, according to the process flow of the present invention Figure 1The order of loading the catalysts in the first reaction zone and the second reaction zone is to make the raw oil contact with the hydrogenation protection catalyst, the hydrogenation demetallization catalyst, the hydrogenation desulfurization catalyst, and the hydrogenation denitrification catalyst in sequence; wherein the hydrogenation protection catalyst is FZC-103D, the hydrogenation demetallization catalyst is FZC-204A, the hydrogenation denitrification agent is FZC-41A, and the hydrogenation desulfurization catalyst examples 8-14 are respectively selected from the catalysts TC-1, TC-2, TC-3, TC-4, TC-5, TC-6, and TC-7 prepared according to the above examples. The raw oil is atmospheric residue (properties are shown in Table 4). The properties of the catalysts are shown in Table 5.

[0097] The first reaction zone is filled with a hydrogenation protection catalyst, a hydrodemetallization catalyst and a hydrodesulfurization catalyst, and the volume ratio of the hydrogenation protection catalyst, the hydrodemetallization catalyst and the hydrodesulfurization catalyst is 2.0:2.0:6.0. The second reaction zone is filled with a hydrogenation protection catalyst, a hydrodemetallization catalyst, a hydrodesulfurization catalyst and a hydrodenitrogenation catalyst, and the volume ratio of the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst is 2.0:2.0:3.0:3.0.

[0098] Sulfiding of the catalysts in the first and second reaction zones: 2 A sulfiding liquid with a sulfiding agent content of 5.0% and a low nitrogen distillate oil with a nitrogen content of not more than 150 μg / g is introduced into the first reaction zone and the second reaction zone at a rate of 0.5 g / h per gram of catalyst, and hydrogen is introduced into the first reaction zone and the second reaction zone at a rate of 0.3 L / hr per gram of catalyst, and the hydrogen pressure is controlled to be 17.0 MPa. The first reaction zone and the second reaction zone are first heated to 230°C at a rate of 5.0°C / hr, and kept at this temperature for 12 hours, then heated to 280°C at a rate of 5.0°C / hr, and kept at this temperature for 8 hours, and then heated to 310°C at a rate of 2.5°C / hr, and kept at this temperature for 4 hours, and the sulfiding is completed. After the sulfiding is completed, the residual oil feedstock is cut into the device for normal operation.

[0099] Normal production conditions are: the first reaction zone is: reaction temperature 375℃, reaction pressure 17.0MPa, hydrogen oil volume ratio 600:1, liquid hourly volume space velocity 0.2h -1 The second reaction zone is: reaction temperature 375 ° C, reaction pressure 17.0 MPa, hydrogen oil volume ratio 600:1, liquid hourly volume space velocity 0.20h -1 .

[0100] After the reaction stabilized, the properties of the oil produced by hydrogenation in the first reaction zone and the oil produced by hydrogenation in the second reaction zone in Examples 8-14 are shown in Table 6.

[0101] In Examples 8-11, the heavy components of the fraction not lower than 280°C obtained in the first reaction zone are directly used as marine fuel oil 1, and the hydrogenated heavy oil of the fraction not lower than 340°C obtained in the second reaction zone is directly used as marine fuel oil 2. In Examples 12-14, the heavy components of the fraction not lower than 280°C obtained in the first reaction zone are used as blending raw material 1 of marine fuel oil, and the hydrogenated heavy oil of the fraction not lower than 340°C obtained in the second reaction zone is used as blending raw material 2 of marine fuel oil.

[0102] The properties of marine fuel oil 1 and marine fuel oil 2 in Examples 8-14 are shown in Table 7, wherein marine fuel oil 1 and marine fuel oil 2 in Examples 12-14 refer to blending raw material 1 and blending raw material 2 of marine fuel oil, respectively.

[0103] Table 4 Raw oil properties

[0104]

[0105]

[0106] Table 5 Properties of fixed bed residue hydrotreating catalyst

[0107] Catalyst brand FZC-103D FZC-204A FZC-41A Function Protecting the catalyst Demetallization catalyst Denitrification catalyst Particle size, mm 3-10 2-8 2-8 Particle shape Four impeller Bar Bar <![CDATA[Strength, N.mm -1 > 10 18 26 <![CDATA[Specific surface area, m 2 / g]]> 82 169 228 composition Mo-Ni Mo-Ni Mo-Ni Carrier <![CDATA[Al 2 THE 3 ]]> <![CDATA[Al 2 THE 3 ]]> <![CDATA[Al 2 THE 3 ]]>

[0108] Table 6 Evaluation results of Examples 8-14

[0109]

[0110] Table 7 Properties of marine fuel oils used in Examples 8-14

[0111]

[0112] As can be seen from Table 6, the selective hydrodesulfurization catalyst A used in Example 8, Example 9, Example 10, and Example 11 exhibits better hydrodesulfurization performance, and the hydrogenation saturation performance of condensed aromatics is significantly reduced. The hydrodesulfurization catalyst A and the catalyst grading scheme adopted in the first reaction zone thereof exhibit better selectivity in the hydrodesulfurization reaction process, while the hydrogenation saturation reaction process of condensed aromatics is reduced, and the hydrogen consumption in the hydrogenation reaction process is also correspondingly low, which effectively reduces the catalyst cost and production cost of producing low-sulfur marine fuel oil, and achieves the purpose of low-cost production of low-sulfur marine fuel oil.

[0113] As can be seen from Table 7, the heavy component of the fraction not less than 280°C obtained in the first reaction zone in Examples 8, 9, 10 and 11 can be used as marine fuel oil 1, and the hydrogenated heavy oil of the fraction not less than 340°C obtained in the second reaction zone can also be directly used as marine fuel oil 2, both of which are very good low-sulfur marine fuel oils. The purpose of producing low-sulfur marine fuel oil in maximum quantity is achieved through the optimization and adjustment of the process flow.

Claims

1. A heavy oil processing method, the heavy oil processing system used includes two series of residue oil hydrogenation process devices, namely a first series of devices and a second series of devices, wherein the first series of devices includes a first reaction zone and a first separation zone, the first separation zone includes a first hot high-pressure separator, a first hot low-pressure separator, a first cold high-pressure separator and a first cold low-pressure separator and a flash tower, the second series of devices includes a second reaction zone and a second separation zone, the second separation zone includes a second hot high-pressure separator, a second hot low-pressure separator, a second cold high-pressure separator and a second cold low-pressure separator and an atmospheric distillation tower; the first hot low-pressure separator liquid phase outlet and the first cold low-pressure separator liquid phase outlet are connected to the flash tower inlet, and the flash tower light component outlet, the second hot low-pressure separator liquid phase outlet and the second cold low-pressure separator liquid phase outlet are connected to the atmospheric distillation tower inlet; the method comprises: a. The first heavy oil feedstock is mixed with hydrogen and enters the first reaction zone for reaction. The reaction product enters the first separation zone. The liquid product obtained from the first hot low-pressure separator and the liquid product obtained from the first cold low-pressure separator enter the flash tower for fractionation to obtain light components and heavy components. b. The second heavy oil feedstock is mixed with hydrogen and enters the second reaction zone for reaction. The product after the reaction enters the second separation zone. The liquid product obtained from the second hot low-pressure separator, the liquid product obtained from the second cold low-pressure separator and the light component obtained from the flash tower in step a are all entered into the atmospheric pressure fractionation tower for fractionation to obtain hydrogenated naphtha, hydrogenated diesel and hydrogenated heavy oil; The hydrodesulfurization catalyst in the first reaction zone and / or the second reaction zone is a hydrodesulfurization catalyst A, comprising: a carrier, a molybdenum element and a Group VIII metal element, wherein the molybdenum element is at least partially present in the catalyst in the form of carbonyl molybdenum, and the Group VIII metal element is present in the catalyst in the form of a Group VIII metal porphyrin compound; In the hydrodesulfurization catalyst A, based on the weight of the carrier, the content of the Group VIII metal in terms of oxide is 0.5% to 8.0%, and the content of molybdenum in terms of oxide is 5.0% to 25.0%; In the hydrodesulfurization catalyst A, at least part of the molybdenum element is present in the catalyst in the form of carbonyl molybdenum, and the molybdenum present in the form of carbonyl molybdenum accounts for more than 40% of the total molybdenum, calculated as molybdenum atoms; In the hydrodesulfurization catalyst A, the molybdenum element exists in the catalyst in the form of carbonyl molybdenum and molybdenum oxide, and the ratio of carbonyl molybdenum to molybdenum oxide is 4:6-9.5:0.5 in terms of molybdenum atoms; The properties of the hydrodesulfurization catalyst A are as follows: the specific surface area is 50-300m 2 / g, and the pore volume is 0.4~1.3mL / g.

2. The processing method according to claim 1, characterized in that: The cutting point between the light component and the heavy component obtained in step a is 260°C to 400°C; the initial distillation point of the hydrogenated heavy oil in step b is 330°C to 370°C.

3. The processing method according to claim 2, characterized in that: The cutting point between the light component and the heavy component obtained in step a is 280°C to 380°C; the initial distillation point of the hydrogenated heavy oil in step b is 340°C to 360°C.

4. The processing method according to claim 2, characterized in that: The heavy component obtained in step a is used as low-sulfur marine fuel oil or its blending component; the hydrogenated heavy oil in step b is used as low-sulfur marine fuel oil or its blending component.

5. The processing method according to claim 1, characterized in that: The first heavy oil feedstock and the second heavy oil feedstock are each independently selected from at least one of atmospheric residue oil and vacuum residue oil; in the heavy oil feedstock, the sulfur content is not higher than 5.0%, the Conradson carbon residue is not higher than 18%, the total content of heavy metal nickel and vanadium is not higher than 200 μg / g, and the total nitrogen content is not higher than 0.80%, calculated by mass content.

6. The processing method according to claim 1, characterized in that: The first reaction zone and the second reaction zone adopt a fixed bed residue oil hydrogenation process.

7. The processing method according to claim 1 or 6, characterized in that: Based on the total loading volume of the catalyst in the first reaction zone, the hydrogenation protection catalyst accounts for 5% to 30% of the total loading volume; the hydrogenation demetallization catalyst accounts for 10% to 55% of the total loading volume; the hydrogenation desulfurization catalyst accounts for 30% to 85% of the total loading volume; after the hydrogenation desulfurization catalyst, a hydrogenation denitrification catalyst is selectively loaded, and its loading volume accounts for less than 20% of the total loading volume.

8. The processing method according to claim 7, characterized in that: Based on the total loading volume of the catalyst in the first reaction zone, the hydrogenation protection catalyst accounts for 10% to 25% of the total loading volume; the hydrogenation demetallization catalyst accounts for 20% to 45% of the total loading volume; the hydrogenation desulfurization catalyst accounts for 30% to 65% of the total loading volume; after the hydrogenation desulfurization catalyst, the hydrogenation denitrification catalyst is selectively loaded, and its loading volume accounts for 5% to 15% of the total loading volume.

9. The processing method according to claim 1, characterized in that: The operating conditions of the first reaction zone are as follows: hydrogen partial pressure of 5MPa~35MPa, reaction temperature of 300℃~420℃, volumetric space velocity of the first heavy oil raw material liquid of 0.1h -1 ~5.0h -1 , the total hydrogen-to-oil volume ratio is 100~5000.

10. The processing method according to claim 9, characterized in that: The operating conditions of the first reaction zone are as follows: hydrogen partial pressure of 13MPa~20MPa, reaction temperature of 330℃~410℃, volumetric space velocity of the first heavy oil raw material liquid of 0.15h -1 ~2.0h -1 , the total hydrogen-to-oil volume ratio is 300~3000.

11. The processing method according to claim 1 or 6, characterized in that: Based on the total loading volume of the catalyst in the second reaction zone, the hydroprotection catalyst accounts for 5% to 30% of the total loading volume; the hydrodemetallization catalyst accounts for 10% to 55% of the total loading volume; the hydrodesulfurization catalyst accounts for 20% to 65% of the total loading volume, and the hydrodenitrogenation catalyst accounts for 10% to 40% of the total loading volume.

12. The processing method according to claim 11, characterized in that: Based on the total loading volume of the catalyst in the second reaction zone, the hydrogenation protection catalyst accounts for 10% to 25% of the total loading volume; the hydrogenation demetallization catalyst accounts for 20% to 50% of the total loading volume; the hydrogenation desulfurization catalyst accounts for 30% to 45% of the total loading volume, and the hydrogenation denitrification catalyst accounts for 15% to 35% of the total loading volume.

13. The processing method according to claim 1, characterized in that: The operating conditions of the second reaction zone are as follows: hydrogen partial pressure of 5MPa~35MPa, reaction temperature of 300℃~420℃, volumetric space velocity of the second heavy oil raw material liquid of 0.1h -1 ~5.0h -1 , the total hydrogen-to-oil volume ratio is 100~5000.

14. The processing method according to claim 13, characterized in that: The operating conditions of the second reaction zone are as follows: hydrogen partial pressure of 13MPa~20MPa, reaction temperature of 330℃~410℃, volumetric space velocity of the second heavy oil raw material liquid of 0.15h -1 ~2.0h -1 , the total hydrogen-to-oil volume ratio is 300~3000.

15. The processing method according to claim 1, characterized in that: In the hydrodesulfurization catalyst A, based on the weight of the carrier, the content of the Group VIII metal in terms of oxide is 1.0% to 6.0%, and the content of molybdenum in terms of oxide is 8.0% to 20.0%.

16. The processing method according to claim 1, characterized in that: In the hydrodesulfurization catalyst A, at least part of the molybdenum element exists in the catalyst in the form of carbonyl molybdenum, and the molybdenum existing in the form of carbonyl molybdenum accounts for 50% to 90% of the total molybdenum, calculated as molybdenum atoms.

17. The processing method according to claim 1, characterized in that: In the hydrodesulfurization catalyst A, the molybdenum element exists in the catalyst in the form of carbonyl molybdenum and molybdenum oxide, and the ratio of carbonyl molybdenum to molybdenum oxide is 7:3-9:1 based on molybdenum atoms.

18. The processing method according to claim 1, characterized in that: In the hydrodesulfurization catalyst A, the Group VIII metal is selected from at least one of nickel and cobalt, and the Group VIII metal porphyrin compound is selected from at least one of protoporphyrin nickel, protoporphyrin cobalt, tetraphenylporphyrin nickel, tetraphenylporphyrin cobalt, tetramethoxyphenylporphyrin nickel, and tetramethoxyphenylporphyrin cobalt.

19. The processing method according to claim 1, characterized in that: In the hydrodesulfurization catalyst A, the carrier is at least one of alumina, silicon oxide, molecular sieve, activated carbon, titanium aluminum, and titanium silicon.

20. The processing method according to claim 19, characterized in that: In the hydrodesulfurization catalyst A, the carrier is alumina.

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