CN111321001A

CN111321001A - Startup method of hydrotreating catalyst

Info

Publication number: CN111321001A
Application number: CN201811522347.7A
Authority: CN
Inventors: 杨占林; 王会刚; 姜虹; 吕振辉; 彭绍忠; 王继锋; 王平; 温德荣
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2018-12-13
Filing date: 2018-12-13
Publication date: 2020-06-23
Anticipated expiration: 2038-12-13
Also published as: CN111321001B

Abstract

The invention discloses a startup method of a hydrotreating catalyst, which specifically comprises the following steps: (1) introducing start-up diesel into a vulcanized hydrotreating catalyst bed layer to wet a vulcanized hydrotreating catalyst, wherein the start-up diesel contains phosphorus-containing organic matters; (2) after the start-up diesel penetrates through the catalyst bed, increasing the temperature of the reactor to 300-400 ℃ and processing for 10-120 min; (3) and (5) switching raw oil to produce qualified products. The start-up method can shorten the time of start-up initial stage, quickly increase the content of monocyclic aromatic hydrocarbon and quickly and obviously improve the property of hydrogenated oil.

Description

Startup method of hydrotreating catalyst

Technical Field

The invention relates to a startup method of a hydrotreating catalyst, in particular to a startup method of a hydrotreating catalyst, which shortens the time used in the initial startup period and quickly improves the content of monocyclic aromatic hydrocarbon.

Background

In the next 20 years, oil remains the world's leading primary energy source, and the world's oil demand will continue to steadily increase, with asia-pacific regions being the most active, with the increase accounting for approximately 70% of the world's total increase. The global refining technology has developed over 150 years to form a complete refining technology system, and various crude oil processing technical schemes can be provided for 662 refineries in the world at present. In recent years, around the topics of energy conservation, environmental protection, low carbon emission, economic benefit improvement, sustainable development realization and the like, great progress is made in key technical fields of coal-to-oil technology, deep processing of heavy oil (residual oil), clean fuel production, oiling combination, production of alternative fuels and lubricating oil base oil and the like all over the world.

Before the nineties of the last century, most of crude oil processed by refineries in China belongs to low-sulfur paraffin-based or intermediate-base crude oil, and is relatively suitable for FCC processing, and factors such as high price of gasoline and liquefied gas, low requirement on quality of gasoline and diesel oil, high quality of diesel oil and low price of diesel oil and the like cause rapid development of FCC technology in China, become a main means for lightening heavy oil of oil refining enterprises, and are also important sources of economic benefits. Along with the improvement of FCC technology, the requirement of high yield of light products is met, and in addition, the slag mixing ratio is increased year by year, so that the contradiction between the production structure of gasoline and diesel oil and the market demand in China is aggravated, and the quality of diesel oil is greatly reduced. One third of finished diesel oil in China is FCC diesel oil with poor quality, which is characterized by low cetane number, high density and high aromatic hydrocarbon content of the diesel oil and is the biggest obstacle to producing clean diesel oil.

In order to meet the requirement of upgrading product quality, the hydrogenation pretreatment technology for catalytic cracking raw materials is widely applied, and the total processing capacity of domestic residual oil and wax oil hydrotreating is estimated to reach over 5000 ten thousand tons/year, the total quantity of diesel oil as a byproduct of residual oil hydrogenation and wax oil hydrogenation reaches 400-500 ten thousand tons/year, and the diesel oil has poor properties (the sulfur content is 400-800 mug/g, the cetane number is 40-45, and the density is 0.86-0.89 g/cm)³) It is further hydrogenated since it is already a product at higher pressureThe difficulty of desulfurization and cetane number increase is high.

The naphthenic base crude oil becomes an opportunity raw material due to lower price, almost all enterprises for refining foreign crude oil are processing the naphthenic base crude oil, and the proven reserves and the exploitation amount of marine oil in China are increased year by year. Due to the particularity of the naphthenic base crude oil, the straight-run diesel oil mainly comprises naphthenic hydrocarbon and aromatic hydrocarbon, has high density and low cetane number, and has poor quality of coking diesel oil and catalytic diesel oil, so that the difficulty of producing diesel oil products meeting the national IV index requirements is further increased.

The technology for producing clean diesel oil is mainly hydrogenation technology, and the hydrogenation technology widely used at home at present mainly comprises the following steps: hydrofining, MCI, RICH, FHI, MPHC, MHUG, etc. With the deterioration of diesel raw materials and the upgrading of diesel product quality, the deep hydrogenation modification of diesel becomes a necessary trend.

At present, domestic environmental protection laws and regulations require the production of clean diesel oil products. The inferior diesel oil with high processing difficulty can not be directly used for producing the diesel oil product meeting the specification requirement by using a common processing method.

In order to realize low-cost quality upgrading of the high-aromatic-hydrocarbon catalytic diesel oil, the poor-quality catalytic diesel oil can be partially converted into clean gasoline blending components with high added values by a high-aromatic-hydrocarbon-content catalytic diesel oil hydro-conversion technology (FD 2G). The existing catalyst usually has higher HDN and aromatic hydrocarbon saturation performance at the same time, so that the aromatic hydrocarbon saturation at a pre-refining section is too deep, and the following problems are caused: 1. the hydrogenation activity is higher, and the time for entering normal production in the initial start-up stage is longer; 2. influences the octane number of the gasoline product or further improves the BTX content.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a startup method of a hydrotreating catalyst, which can shorten the time for the initial startup, quickly increase the content of monocyclic aromatic hydrocarbon, and quickly and obviously improve the property of hydrogenated oil.

The invention relates to a startup method of a hydrotreating catalyst, which specifically comprises the following steps:

(1) introducing start-up diesel into a vulcanized hydrotreating catalyst bed layer to wet a vulcanized hydrotreating catalyst, wherein the start-up diesel contains phosphorus-containing organic matters;

(2) after the start-up diesel penetrates through the catalyst bed, increasing the temperature of the reactor to 300-400 ℃ and processing for 10-120 min;

(3) and (5) switching raw oil to produce qualified products.

In the method, the hydrotreating catalyst bed layer can be directly filled with an oxidation catalyst, a sulfur-carrying catalyst or a completely-vulcanized catalyst; when the oxidation catalyst and the sulfur-carrying catalyst are filled, the oxidation catalyst and the sulfur-carrying catalyst need to be presulfided or further processed to be converted into the sulfided catalyst.

In the method, the temperature is controlled not to be higher than 100 ℃ in the wetting process, and the temperature of the reactor is increased to 300-400 ℃ at the temperature rising speed of 2-30 ℃/h.

In the method, the processes of the step (1) and the step (2) can be repeated for 2-5 times, and then the raw oil is switched to produce qualified products. In the repeated process, the addition amount of the phosphorus-containing organic matter in the last time in the step (1) is preferably 120-200% of the addition amount of the phosphorus-containing organic matter in the last time, and the treatment temperature in the step (2) is increased by 5-20 ℃ in the last time compared with the previous time.

In the method, the hydrotreating catalyst contains VIB-group and VIII-group metal components. Wherein the VIB group active metal is W and/or Mo, the VIII group active metal is Ni and/or Co, and the active metals in the final hydrotreating catalyst are generally as follows by weight: the content of VIB group metal oxide is 9% -50%, and the content of VIII group metal oxide is 1% -15%. The catalyst carrier is one or more of porous refractory oxide such as alumina, silica-alumina, alumina with silica-alumina dispersed therein, silica-coated alumina, magnesia, zirconia, boria, titania, molecular sieve, etc. According to the use requirement of the catalyst, a proper auxiliary agent can be added, such as one or more of fluorine, phosphorus, zinc, copper and the like.

In the method, the vulcanization process of the catalyst is divided into dry vulcanization and wet vulcanization, and different vulcanization methods can be selected according to different technological process requirements. Commonly used vulcanizing agents are chemical agents which react to generate hydrogen sulfide, such as carbon disulfide, dimethyldisulfide, SulfrZol 54, butanethiol, DMSO, etc.

In the method, the low-nitrogen oil is not required to be introduced in the vulcanizing process by a dry method, and besides the chemical agent, the vulcanizing agent can also select hydrogen sulfide gas which can be compressed by a new hydrogen compressor. In the dry-process vulcanization process, the constant temperature time and the constant temperature are different through two constant temperature processes according to different properties of the catalyst. The temperature is controlled to be 200-260 ℃ in the first stage of constant temperature, the constant temperature time is controlled to be 2-24 hours, and the temperature is controlled to be 340-400 ℃ in the second stage of constant temperature, and the constant temperature time is controlled to be 2-24 hours.

In the method, in the wet-process vulcanization process, through three stages of constant temperature processes, the constant temperature time and the constant temperature are different according to different properties of the catalyst. The temperature is controlled to be 190-250 ℃ during the first-stage constant temperature, the constant temperature time is controlled to be 2-24 hours, the temperature is controlled to be 270-310 ℃ during the second-stage constant temperature, the constant temperature time is controlled to be 1-12 hours, the temperature is controlled to be 320-380 ℃ during the third-stage constant temperature, and the constant temperature time is controlled to be 2-24 hours.

In the method, the start diesel is generally hydrogenated straight-run diesel, the density is less than 0.83g/cm3, the nitrogen content is less than 10ppm, the water content is less than 100ppm, and the final distillation point is not more than 370 ℃.

In the method, the boiling point of the phosphorus-containing organic substance is higher than 300 ℃, phosphate ester and phosphite ester are preferred, and the number of carbon atoms in the organic substance is preferably 2-70, and more preferably 10-50. 2-ethylhexyl diphenyl phosphate, 2-ethylhexyl mono-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, diphenyl monoisooctyl phosphite, diphenyl monoisodecyl phosphite, monobenzenediisodecyl phosphite, tris (nonylphenyl) phosphite.

In the method, the addition amount of the phosphorus-containing organic matters in the start-up diesel oil is 0.1-10 wt%, the addition amount of the first passivation operation of dry vulcanization is preferably 0.3-3%, and the addition amount of the first passivation operation of wet vulcanization is preferably 0.5-5%.

In the method, the hydrogen pressure in the processes of the step (1) and the step (2) is 2.0MPa to 20.0MPa, and the oil inlet amount of the start-up diesel oil is 0.5 to 5.0h^-1And the hydrogen-oil ratio is 200-2000, and the content of hydrogen sulfide in the circulating hydrogen is maintained to be more than 0.05 v% in the process.

By the treatment method, the Ni (Co) -Mo (W) -S active phase on the catalyst interacts with the phosphorus-containing precursor, so that higher hydrogenation activity and selectivity inhibition are inhibited, the problem of over-deep saturation of aromatic hydrocarbon at the preliminary refining stage in the initial reaction stage is solved, and more monocyclic aromatic hydrocarbon is contained in the target product.

Detailed Description

The Mo and Ni catalyst CAT is prepared by the method of patent CN200810010260.1 example 1, and the characteristics of the catalyst are shown in Table 1.

Table 1 key properties of the oxidation state catalyst prepared

The main properties of the start-up diesel are shown in Table 2.

TABLE 2 Start-up diesel key properties

The detailed procedures of the present invention will be further described below by way of examples, but the present invention should not be construed as being limited to these examples, and the percentages are by weight unless otherwise specified.

Example 1

This example describes the preparation of a sulfided catalyst by dry sulfiding and wet sulfiding with an oxidized catalyst, CAT.

The specific dry-method vulcanization process is introduced by taking the first-stage constant temperature of 230 ℃ and the second-stage constant temperature of 360 ℃:

(1) the catalyst is heated by circulating hydrogen with a certain flow, and when the temperature of the reactor inlet reaches 190-210 ℃ and the temperature of all the beds reaches 190-200 ℃, DMDS can be introduced for vulcanization.

(2) After introducing the vulcanizing agent, the temperature of the inlet of the reactor is increased at the speed of 2-4 ℃/h, and the temperature of any point in the bed layer of the reactor is not allowed to exceed 230 ℃ until no hydrogen sulfide is detected at the outlet of the reactor. Otherwise, the finishing reactor inlet temperature should be maintained and the carbon disulfide addition reduced until the temperature is controlled.

（3）H₂And (3) after S penetrates through the reactor, adjusting the addition amount of carbon disulfide to ensure that the content of H2S in the circulating gas at the outlet of the reactor is 0.1 percent (v) to 0.5 percent (v), continuously increasing the inlet temperature of the reactor to 230 ℃, and keeping the temperature at 230 ℃ for 8 hours.

(4) After the 230 ℃ constant-temperature vulcanization is finished, the inlet temperature of the reactor is increased to 290 ℃ at the speed of 3-5 ℃/H, and H is added₂Increasing the S content to 0.5-1.0% (v) if the H content of the reactor effluent is₂If the S content is less than 0.5% (v), the temperature rise is stopped.

(5) When the inlet temperature of the reactor reaches 290 ℃, the temperature is raised at a speed of not more than 5-7 ℃/h, and the inlet temperature of the reactor is raised to 360 ℃ smoothly. While raising the temperature to 360 ℃, continuously injecting carbon disulfide and keeping H of reactor effluent₂S content not less than 0.5% (v) if H₂When the S content is lower than 0.5 percent (v), the temperature is stopped, and the temperature is increased after the requirement is met.

(6) When the reactor inlet temperature is 360 ℃, recycling H of hydrogen₂Increasing the S concentration to 1.0-2.0% (v), maintaining the reactor inlet temperature at 360 deg.C for 8H, and adding H at the reactor inlet and outlet₂The S concentration is the same, and the vulcanization process is finished. And (4) carrying out cooling operation to ensure that the temperature of the vulcanized catalyst is not higher than 100 ℃. The obtained catalyst in a sulfided state is named CATG.

The specific process of the wet-process vulcanization is described by the first-stage constant temperature of 230 ℃, the second-stage constant temperature of 290 ℃ and the third-stage constant temperature of 360 ℃:

(1) the finishing reactor inlet temperature was controlled at 160 ℃.

(2) Introducing low-nitrogen oil into the reaction system, wherein the initial oil inlet amount is 30% of the design load, and after the adsorption heat release temperature wave passes through the catalyst bed layer, increasing the oil inlet amount to 80% of the design load to establish low-nitrogen oil circulation.

(3) The inlet temperature of the refining reactor is stably raised to 190 ℃ at the speed of not more than 20 ℃/h, and then the DMDS is injected into the reaction system. The amount of the sulfiding agent to be added is determined in accordance with the relevant process conditions such as operating pressure, circulating hydrogen flow rate, reaction temperature, etc.

(4) After the vulcanizing agent is injected into the reaction system, the inlet temperature of the refining reactor can be stably raised to 230 ℃ at the speed of not more than 10 ℃/h, and the constant-temperature vulcanization is carried out for 8 h. During the constant temperature period, the concentration of hydrogen sulfide in the circulating hydrogen should be maintained at 0.1-0.5 v%.

(5) And after the constant-temperature vulcanization at 230 ℃, adjusting the injection rate of the vulcanizing agent to enable the concentration of the hydrogen sulfide in the circulating hydrogen to reach 0.5-1.0 v%. Then, the inlet temperature of the refining reactor is stably raised to 290 ℃ at the speed of not more than 8 ℃/h, and the temperature is kept constant for 4 h. In the temperature raising process, if the concentration of the hydrogen sulfide is less than 0.5v%, the temperature raising is stopped, and the injection rate of the vulcanizing agent is increased until the concentration of the hydrogen sulfide meets the requirement.

(6) After the constant temperature of 290 ℃, the inlet temperature of the refining reactor is smoothly raised to 360 ℃ at the speed of not more than 5 ℃/h. And simultaneously adjusting the injection rate of the vulcanizing agent to ensure that the concentration of the hydrogen sulfide in the circulating hydrogen reaches 1.0-1.5 v%, and keeping the temperature for 8 h. When the vulcanization process is finished, the temperature is reduced to ensure that the temperature of the vulcanized catalyst is not higher than 100 ℃. The sulfided catalyst obtained was designated CATL.

Example 2

This example describes the passivation of the catalyst CATG in the sulfided state.

Adding the monobenzenediisodecyl phosphite into start-up diesel to ensure that the content of the monobenzenediisodecyl phosphite is 0.6 percent. Maintaining hydrogen partial pressure of 8.0MPa and feeding amount of 2.0h at 100 deg.C or below^-1Hydrogen-to-oil ratio of 800, H in circulating hydrogen₂The S content is not less than 0.2 v%. The first passivation treatment, using the start diesel oil to wet CATG, after the start diesel oil penetrates the catalyst bed layer, raising the temperature to 330 ℃ at the temperature raising speed of 20 ℃/hour, stopping the start diesel oil, reacting for 60min, and then cooling to below 100 ℃. Passivating again to increase the content of the monobenzene diisodecyl phosphite to 1.0 percent by weight in the start diesel oilRepeating the steps, wherein the treatment temperature is 340 ℃; and passivating for the third time to improve the content of the monobenzylisodecyl phosphite in the start diesel to 1.5%, repeating the steps, wherein the treatment temperature is 350 ℃, and the obtained sample is recorded as CATG-1.

Example 3

This example describes the passivation of a catalyst CATL in the sulfided state.

2-ethylhexyl phosphate mono-2-ethylhexyl ester was added to the start diesel fuel to a level of 1.0%. Maintaining hydrogen partial pressure of 8.0MPa and feeding amount of 1.5h at 100 deg.C or below^-1Hydrogen-to-oil ratio of 800, H in circulating hydrogen₂The S content is not less than 0.2 v%. The first passivation treatment, the CATL is wetted by the start diesel, when the start diesel penetrates the catalyst bed, the temperature is raised to 350 ℃ at the temperature rising speed of 20 ℃/hour, the start diesel is stopped, and after the reaction is carried out for 60min, the temperature is reduced to below 100 ℃. Passivating again to increase the content of the 2-ethylhexyl phosphate in the start diesel oil to 2.0 percent, repeating the steps, wherein the treatment temperature is 360 ℃, and the obtained sample is marked as CATL-1

Example 4

This comparative example describes the passivation of the catalyst CATG in the sulfided state.

Adding the monobenzenediisodecyl phosphite into start-up diesel to make the content of the monobenzenediisodecyl phosphite be 3.1%. Maintaining hydrogen partial pressure of 8.0MPa and feeding amount of 2.0h at 100 deg.C or below^-1Hydrogen-to-oil ratio of 800, H in circulating hydrogen₂The S content is not less than 0.2 v%. The startup diesel oil is used for wetting CATG, when the startup diesel oil penetrates through a catalyst bed layer, the temperature is raised to 340 ℃ at the temperature rise speed of 20 ℃/hour, the startup diesel oil is stopped to be fed, after the reaction is carried out for 60min, the temperature is reduced to below 100 ℃, and the obtained sample is marked as CATG-2.

Comparative example 1

The catalyst CATG in the sulfided state prepared in example 1 was used as a comparative example.

TABLE 3 physicochemical Properties of the catalyst

Catalyst and process for preparing same	CATG	CATL	CATG-1	CATL-1	CATG-2
						Carbon content%	0.2	2.8	4.3	3.9	4.9
Content of phosphorus%	1.32	1.30	1.83	1.99	1.92

The carbon content analysis method comprises the following steps: the X-ray diffraction result shows that the organic matter on the catalyst carrier has been carbonized, the high temperature combustion method is adopted to determine the carbon content of the sample, and the carbon is combusted in the high purity oxygen atmosphere to generate CO₂，CO₂And (4) conveying the gas into a chromatogram, and detecting and analyzing the gas by a thermal conductivity cell to calculate the carbon content of the sample.

The phosphorus content analysis method comprises the following steps: after a sample is dissolved by sodium hydroxide, the acidity of the solution is adjusted, phosphorus in the solution reacts with a proper amount of ammonium vanadate and ammonium molybdate in a 0.8M nitric acid solution to generate a yellow complex of phospho-vanadium-molybdenum heteropoly acid, and the phosphorus is subjected to colorimetric determination according to the yellow complex.

Example 4

This example is an activity evaluation experiment of a catalyst.

Catalyst activity evaluation experiments were performed on a 50ml small scale hydrogenation unit. The evaluation conditions of the catalyst are that the total reaction pressure is 8.0MPa, and the volume space velocity is 1.9h^-1Hydrogen-oil ratio of 800: 1, the reaction temperature is 380 ℃. Properties of the raw oil for the activity evaluation test are shown in Table 2.

The results of activity evaluation of the catalysts of examples and comparative examples are shown in tables 4 and 5. The data in the table show that the startup process is carried out by adopting the method, the hydrodenitrogenation activity of the catalyst is slightly lower than that of a CATG catalyst, and the total monocyclic aromatic hydrocarbon content is obviously higher than that of a comparative catalyst when the startup process is carried out by adopting the method in the invention from the viewpoint of the total monocyclic aromatic hydrocarbon content of the generated oil, which proves that the startup process is more suitable for the catalytic diesel hydrotreating process of FD2G technology, can more quickly lead the catalyst to reach a stable state, and is beneficial to improving the octane number of gasoline products.

TABLE 4 Properties of the feed oils

Raw oil	Catalytic diesel fuel
		Density (20 ℃ C.), g.cm^-3	0.9415
Distillation range, deg.C
		IBP/10%	209/239
90%/EBP	283/338
		S，%	3152
N，µg·g^-1	579
		Alkane,% of	18.9
Total naphthenes,% of	13.2
		Total aromatic hydrocarbons,%	67.9
Total monocyclic aromatic hydrocarbons,%)	24.7

TABLE 5 evaluation results of catalyst activity in 300-hour operation

Catalyst and process for preparing same	CATG	CATG-1	CATL-1	CATG-2
					Relative denitrification activity,%	109	105	108	100
Relative desulfurization activity of%	107	104	108	100
					Alkane,% of	25.6	23.5	23.0	23.1
Total naphthenes,% of	21.7	18.2	17.9	18.6
					Total aromatic hydrocarbons,%	52.7	58.3	59.1	58.3
Total monocyclic aromatic hydrocarbons,%)	29.7	34.2	34.8	32.3

Claims

1. A startup method of a hydrotreating catalyst is characterized by comprising the following steps: the method specifically comprises the following steps:

(3) and (5) switching raw oil to produce qualified products.

2. The method of claim 1, wherein: the hydrotreating catalyst bed layer is directly filled with an oxidation type catalyst, a sulfur-carrying type catalyst or a completely-vulcanized type catalyst; when the oxidation catalyst and the sulfur-carrying catalyst are filled, the catalyst needs to be presulfurized to be converted into a sulfided catalyst.

3. The method of claim 1, wherein: the temperature of the wetting process in the step (1) is controlled to be not higher than 100 ℃; and (2) increasing the temperature of the reactor to 300-400 ℃ at a temperature rise speed of 2-30 ℃/h.

4. The method of claim 1, wherein: the processes of the step (1) and the step (2) can be repeated for 2-5 times, and then the raw oil is switched to produce qualified products.

5. The method of claim 4, wherein: in the repeated process, the addition amount of the phosphorus-containing organic matter in the last time in the step (1) is preferably 120-200% of the addition amount of the phosphorus-containing organic matter in the last time, and the treatment temperature in the step (2) is increased by 5-20 ℃ in the last time compared with the previous time.

6. The method of claim 1, wherein: the hydrotreating catalyst contains VIB group and VIII group metal components, wherein the VIB group active metal is W and/or Mo, the VIII group active metal is Ni and/or Co, and the final hydrotreating catalyst comprises the following active metals in terms of oxide weight: the content of VIB group metal oxide is 9% -50%, and the content of VIII group metal oxide is 1% -15%.

7. The method of claim 1, wherein: the hydrotreating catalyst contains a carrier, and the carrier is one or more of alumina, silica-alumina, magnesia, zirconia, boron oxide, titania and a molecular sieve.

8. The method of claim 1, wherein: the hydrotreating catalyst is added with proper auxiliary agents, and the auxiliary agents are one or more of fluorine, phosphorus, zinc and copper.

9. The method of claim 2, wherein: the vulcanization process of the catalyst is divided into dry vulcanization and wet vulcanization, and the vulcanizing agent is carbon disulfide, dimethyl disulfide, SulfrZol 54, butyl mercaptan or DMSO.

10. The method of claim 9, wherein: low-nitrogen oil is not required to be introduced in the dry-method vulcanization process, and the process is carried out through two constant temperature processes, wherein the temperature is controlled to be 200-260 ℃ in the first constant temperature process, the constant temperature time is controlled to be 2-24 hours, the temperature is controlled to be 340-400 ℃ in the second constant temperature process, and the constant temperature time is controlled to be 2-24 hours.

11. The method of claim 9, wherein: in the wet vulcanization process, three sections of constant temperature processes are carried out, wherein the temperature is controlled to be 190-250 ℃ in the first section of constant temperature, the constant temperature time is controlled to be 2-24 hours, the temperature is controlled to be 270-310 ℃ in the second section of constant temperature, the constant temperature time is controlled to be 1-12 hours, the temperature is controlled to be 320-380 ℃ in the third section of constant temperature, and the constant temperature time is controlled to be 2-24 hours.

12. The method of claim 1, wherein: the start diesel oil is hydrogenated straight-run diesel oil, the density is less than 0.83g/cm3, the nitrogen content is less than 10ppm, the water content is less than 100ppm, and the final distillation point is not more than 370 ℃.

13. The method of claim 9, wherein: the phosphorus-containing organic matter is phosphate and phosphite ester, the boiling point is higher than 300 ℃, and the number of carbon atoms in the organic matter is preferably 2-70.

14. The method of claim 1, wherein: the phosphorus-containing organic matter is one or more of 2-ethylhexyl diphenyl phosphate, 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, 2-ethylhexyl diphenyl phosphate, diphenyl-isooctyl phosphite, diphenyl-isodecyl phosphite, diphenyl-diisodecyl phosphite and tris (nonylphenyl) phosphite.

15. The method of claim 1, wherein: the addition amount of the phosphorus-containing organic matters in the start diesel oil is 0.1-10 wt%, the addition amount of the first passivation operation of dry vulcanization is 0.3-3%, and the addition amount of the first passivation operation of wet vulcanization is 0.5-5%.

16. The method of claim 1, wherein: the hydrogen pressure in the processes of the step (1) and the step (2) is 2.0 MPa-20.0 MPa, and the oil inlet amount of start-up diesel oil is 0.5-5.0 h^-1And the hydrogen-oil ratio is 200-2000, and the content of hydrogen sulfide in the circulating hydrogen is maintained to be more than 0.05 v% in the process.