阅读说明：本技术 一种加氢催化剂的开工方法 (Startup method of hydrogenation catalyst ) 是由 高玉兰 方向晨 徐黎明 佟佳 杨涛 王继锋 于 2019-10-29 设计创作，主要内容包括：本发明公开了一种加氢催化剂的开工方法,包括以下步骤：(l)将加氢催化剂载体,与硫代钼酸盐和/或硫代钨酸盐溶液、镍盐和/或钴盐溶液分别混合,干燥,得到中间态加氢催化剂；(2)将硫化剂与步骤(1)得到的中间态加氢催化剂混合均匀,然后进行热处理,降温后,加入含磷物质；(3)将步骤(2)所得物料干燥,得到预硫化催化剂；(4)将步骤(3)预硫化催化剂装入反应器,进行湿法活化开工。该方法解决了由于催化剂初始活性温度过高所带来的反应器氢脆的安全性问题,也改进催化剂器外预硫化过程、预硫化催化剂开工活化方法,提高催化剂的初始活化温度的同时,提高催化剂活性。(The invention discloses a startup method of a hydrogenation catalyst, which comprises the following steps: (l) Respectively mixing a hydrogenation catalyst carrier with a thiomolybdate and/or thiotungstate solution and a nickel salt and/or cobalt salt solution, and drying to obtain an intermediate hydrogenation catalyst; (2) uniformly mixing a vulcanizing agent and the intermediate hydrogenation catalyst obtained in the step (1), then carrying out heat treatment, cooling, and adding a phosphorus-containing substance; (3) drying the material obtained in the step (2) to obtain a pre-vulcanized catalyst; (4) and (4) loading the presulfurized catalyst in the step (3) into a reactor, and performing wet activation and start-up. The method solves the safety problem of hydrogen embrittlement of the reactor caused by overhigh initial activity temperature of the catalyst, improves the ex-situ presulfurization process of the catalyst and the start-up activation method of the presulfurized catalyst, and improves the initial activation temperature of the catalyst and the activity of the catalyst at the same time.)

1. A start-up method of a hydrogenation catalyst comprises the following steps:

(l) Respectively mixing a hydrogenation catalyst carrier with a thiomolybdate and/or thiotungstate solution and a nickel salt and/or cobalt salt solution, and drying to obtain an intermediate hydrogenation catalyst;

(2) uniformly mixing a vulcanizing agent and the intermediate hydrogenation catalyst obtained in the step (1), then carrying out heat treatment, cooling, and adding a phosphorus-containing substance;

(3) drying the material obtained in the step (2) to obtain a pre-vulcanized catalyst;

(4) and (4) loading the presulfurized catalyst in the step (3) into a hydrogenation device, and performing wet activation and start-up.

2. The method of claim 1, wherein: in the step (1), the hydrogenation catalyst carrier is firstly mixed with a thiomolybdate solution and/or a thiotungstate solution, dried, then mixed with a nickel salt solution and/or a cobalt salt solution, and dried to obtain an intermediate hydrogenation catalyst; or mixing the hydrogenation catalyst carrier with a nickel salt solution and/or a cobalt salt solution, drying, mixing with a thiomolybdate solution and/or a thiotungstate solution, and drying to obtain the intermediate hydrogenation catalyst.

3. The method of claim 2, wherein: in the step (1), the drying conditions of the hydrogenation catalyst carrier after being mixed with the thiomolybdate solution and/or the thiotungstate solution are as follows: drying for 1-6 h at 30-250 ℃; the drying conditions of the hydrogenation catalyst carrier after being mixed with the nickel salt solution and/or the cobalt salt solution are as follows: drying for 1-6 h at 50-130 ℃.

4. The process according to claim 1, characterized in that the mass concentration of the thiomolybdate and/or thiotungstate solution in step (1) is 0.5-50%, preferably 3-25%; the mass concentration of the nickel salt solution and/or the cobalt salt solution is 0.2-200%, preferably 1.5-8%.

5. The method according to claim 1, wherein the intermediate hydrogenation catalyst in step (1) contains hydrogenation active metals in a total mass content of 5wt% to 50 wt%; preferably, Mo and/or W accounts for 10-30% of the total mass content of the intermediate hydrogenation catalyst, and Ni and/or Co accounts for 0.5-8% of the total mass content of the intermediate hydrogenation catalyst.

6. The method according to claim 1, wherein the vulcanizing agent of step (2) is one or more of elemental sulfur and/or a sulfur-containing compound.

7. The method according to claim 1, wherein the sulfiding agent in step (2) is used in an amount of 5% to 120%, preferably 5% to 50%, of the theoretical sulfur requirement of the intermediate hydrogenation catalyst.

8. The method of claim 1, wherein a vulcanization aid is added in step (2); the vulcanizing assistant is preferably one or more of hydrocarbon oil and organic carboxylic ester; the hydrocarbon oil is preferably one or more of gasoline, kerosene, diesel oil, lamp oil, white oil, industrial soybean oil, lubricating oil base oil, straight-run and reduced-pressure heavy distillate oil; the organic carboxylic acid ester is preferably an organic carboxylic acid ester containing 6 to 60 carbon atoms, and more preferably one or more of fatty glyceride, animal oil, rapeseed oil, peanut oil, soybean oil and cottonseed oil.

9. A process according to claim 8, wherein the sulfiding aid is present in an amount of from 0.1% to 30%, preferably from 1% to 25%, by weight of the intermediate hydrogenation catalyst.

10. The method according to claim 1, wherein the temperature of the heat treatment in the step (2) is 70-500 ℃, preferably 120-270 ℃, and the heat treatment time is 10-480 min, preferably 15-240 min.

11. The method according to claim 1, wherein in the step (2), the temperature is reduced to 20-70 ℃, and then the phosphorus-containing substance is added.

12. The method of claim 1, wherein the phosphorus-containing material of step (2) is selected from one or more of phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, phosphate esters, phosphorus pentoxide, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphonic acid, phosphinic acid, phosphonate esters, adenosine triphosphate; preferably one or more of phosphoric acid, ammonium dihydrogen phosphate and ammonium phosphate.

13. The process according to claim 1, wherein in step (2), the phosphorus-containing substance is used in an amount of 0.1% to 50%, preferably 0.4% to 50%, by weight of the intermediate hydrogenation catalyst.

14. The method of claim 1, wherein in step (2), the phosphorus-containing substance is added together with an auxiliary agent, and the auxiliary agent is at least one of alcohols and hydrocarbon oil.

15. The method according to claim 1, wherein the drying conditions in step (3) are: drying for 0.5-5 h at 60-130 ℃.

16. The process of claim 1, wherein one or more of an organic acid, an organic nitrogen is introduced as a modifier before, after, or simultaneously with step (3).

17. The process according to claim 16, wherein the modifier loading is from 0.5% to 20%, preferably from 2.0% to 10% by weight of the intermediate hydrogenation catalyst.

18. The method according to claim 1, wherein the specific method of the wet activation start-up in step (4) comprises: the temperature of the reactor is raised to 50-180 ℃, preferably to 90-140 ℃ at the temperature raising speed of 1-50 ℃/h, preferably 10-30 ℃/h; introducing the starting oil, introducing hydrogen to boost pressure at the speed of 0.1-10 MPa/h, preferably 1-2 MPa/h to 2-8 MPa, preferably 3-5 MPa, at the temperature of 270-400 ℃, preferably 300-330 ℃, and keeping the temperature for 1-8 h, preferably 1-3 h.

Technical Field

The invention discloses a startup method of a hydrogenation catalyst, in particular to a startup method of a vulcanization type hydrogenation catalyst.

Background

In recent years, the crude oil deterioration tendency is increasingly obvious, the requirement of each country for clean fuel is increasingly increased, the hydrogenation process is taken as one of the most effective means for producing the clean fuel, and the high-efficiency hydrogenation catalyst becomes the technical key of the hydrogenation process. The active metal of the conventional hydrogenation catalyst is in an oxidation state, and the material which really plays an active role in actual use is in a vulcanization state, so the material needs to be vulcanized in a reactor before use. The conventional catalyst is presulfurized in a reactor, special equipment is needed, the production cost is increased, the vulcanization process is easy to cause pollution, and the required start-up time is longer.

In view of this problem, in recent years, ex-situ prevulcanization techniques have been developed. The external presulfurization technology mainly comprises two technologies of sulfur-carrying type external presulfurization technology and complete type external presulfurization technology. In the application of the sulfur-carrying type ex-situ presulfurization technology, because of the hydrogen brittleness requirement of the material of the reactor, the initial reaction temperature of the ex-situ presulfurization catalyst needs to be increased, and the activation also needs to be carried out in a reaction device; after the catalyst is fully presulfurized by the full ex-situ presulfurization technology, the catalyst can generate violent oxidation reaction (or referred to as a reverse sulfuration reaction) in air or oxygen-containing atmosphere, and can generate spontaneous combustion or explosion and other violent reactions when the catalyst is serious, and the prepared fully ex-situ presulfurization catalyst has safety problems of spontaneous combustion or explosion and the like in the processes of storing, transporting and filling a reaction device if the catalyst is not passivated and protected. In order to ensure the safety of catalyst storage, transportation and filling, a passivation process needs to be added in the pre-vulcanization process, and the equipment requirement is high and the operation condition is harsh, so that the overall catalyst pre-vulcanization cost is higher.

CN103769169A discloses a preparation method of a sulfidation type hydrotreating catalyst, which comprises mixing a carrier and thiomolybdate, drying, adding an adhesive, extruding into strips, molding, drying under the protection of inert gas, and calcining to obtain the sulfidation type hydrotreating catalyst.

CN101618330B discloses a preparation method of a sulfidation type catalyst, which comprises loading a metal sulfide precursor on a carrier by an impregnation method, adding a third component, reacting the third component with the metal sulfide precursor in pores of the carrier, and uniformly depositing metal sulfides in the pores, thereby preparing the sulfidation type catalyst.

The presulfurization method of CN102284299A hydrogenation catalyst, make the mixture of vulcanizing agent, hydrogen and inert gas introduce into catalyst, sulfurize under the hydrogen, this method has increased the preparation cost of the presulfurization catalyst because of introducing hydrogen and its course.

CN102041051A discloses a start-up method of a vulcanized hydrogenation catalyst, which comprises the steps of impregnating and loading vulcanizing agents such as sodium sulfide, ammonium sulfide and the like, loading the vulcanized catalyst into a reactor, heating and activating under hydrogen, and then starting hydrogenation reaction through raw oil. The method has complex process and high catalyst preparation cost.

The prior ex-situ presulfurization technology is used for treatment, the vulcanization process is still not very ideal, and the activity of the catalyst is influenced. Therefore, the ex-situ presulfiding method needs further improvement to improve the catalyst activity.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a startup method of a hydrogenation catalyst, and aims to solve the safety problem of hydrogen brittleness of a reactor caused by overhigh initial activity temperature of the catalyst. The invention also aims to improve the ex-situ presulfurization process of the catalyst and the start-up activation method of the presulfurized catalyst, and improve the activity of the catalyst while improving the initial activation temperature of the catalyst.

The start-up method of the hydrogenation catalyst comprises the following steps:

(l) Respectively mixing a hydrogenation catalyst carrier with a thiomolybdate and/or thiotungstate solution and a nickel salt and/or cobalt salt solution, and drying to obtain an intermediate hydrogenation catalyst;

(2) uniformly mixing a vulcanizing agent and the intermediate hydrogenation catalyst obtained in the step (1), then carrying out heat treatment, cooling, and adding a phosphorus-containing substance;

(3) drying the material obtained in the step (2) to obtain a pre-vulcanized catalyst;

(4) and (4) loading the presulfurized catalyst in the step (3) into a reactor, and performing wet activation and start-up.

In the step (1), the hydrogenation catalyst carrier may be at least one of a hydrofining catalyst carrier, a hydrocracking catalyst carrier, a hydro-upgrading catalyst carrier and a hydrotreating catalyst carrier, and may be used for hydrogenation of light distillate oil (such as gasoline, kerosene and diesel oil), hydrogenation of heavy distillate oil (such as wax oil), and hydrogenation of heavy oil (such as residual oil). The hydrogenation catalyst carrier is an inorganic refractory oxide, and mainly comprises alumina. The hydrogenation catalyst support can be prepared by a conventional method in the field.

In the step (1), the hydrogenation catalyst carrier may further include an auxiliary component, wherein the auxiliary is one or more selected from Si, B, Ti, Zr, and the like.

In the step (1), the hydrogenation catalyst carrier is firstly mixed with a thiomolybdate solution and/or a thiotungstate solution, dried, then mixed with a nickel salt solution and/or a cobalt salt solution, and dried to obtain an intermediate hydrogenation catalyst; or the hydrogenation catalyst carrier is mixed with a nickel salt solution and/or a cobalt salt solution, dried, mixed with a thiomolybdate solution and/or a thiotungstate solution, and dried to obtain the intermediate hydrogenation catalyst.

The drying conditions of the hydrogenated catalyst carrier mixed with the thiomolybdate solution and/or the thiotungstate solution in the step (1) are as follows: drying for 1-6 h at 30-250 ℃; the drying conditions of the hydrogenation catalyst carrier after being mixed with the nickel salt solution and/or the cobalt salt solution are as follows: drying for 1-6 h at 50-130 ℃.

The thiomolybdate in the step (1) may be one or more of ammonium thiomolybdate, potassium thiomolybdate, sodium thiomolybdate and the like, and is preferably ammonium thiomolybdate. The thiomolybdate is preferably one or more of tetrathiomolybdate and alkyl substituted thiomolybdate. The thiotungstate can be one or more of ammonium thiotungstate, potassium thiotungstate, sodium thiotungstate and the like, and preferably is ammonium thiotungstate. The thiotungstate is preferably one or more of tetrathiotungstate and alkyl substituted thiotungstate. The nickel salt and/or cobalt salt is selected from one or more of nitrate, carbonate, basic carbonate, acetate and chloride.

The mass concentration of the thiomolybdate and/or thiotungstate solution in the step (1) is 0.5-50%, preferably 3-25%; the mass concentration of the nickel salt solution and/or the cobalt salt solution is 0.2-200%, preferably 1.5-8%.

The total content of hydrogenation active metals in the intermediate hydrogenation catalyst in the step (1) is 5-50 wt%. Wherein, Mo and/or W accounts for 10-30% of the total mass content of the intermediate hydrogenation catalyst, and Ni and/or Co accounts for 0.5-8% of the total mass content of the intermediate hydrogenation catalyst.

The vulcanizing agent in step (2) may be a sulfur-containing substance conventional in the art, and may be one or more of elemental sulfur and/or a sulfur-containing compound. Inexpensive elemental sulfur (i.e., sulfur) is preferred. The sulfur-containing compound may be at least one of an inorganic sulfur-containing compound and an organic sulfur-containing compound, the inorganic sulfur-containing compound may be at least one of carbon disulfide and ammonium sulfide, and the organic sulfur-containing compound may be at least one of a mono-sulfur compound and a multi-sulfur compound, such as one or more of dimethyl disulfide, tert-butyl polysulfide, tert-nonyl polysulfide, thiourea, SZ-54 (commercial product), thiols (such as n-butyl thiol, ethyl thiol), thiophenol, thioether, sulfolane, dimethyl sulfoxide, and the like. The dosage of the vulcanizing agent is generally 5 to 120 percent, preferably 5 to 50 percent of the theoretical sulfur demand of the intermediate hydrogenation catalyst. The theoretical sulfur demand of the catalyst is that active metal components contained in the catalyst are completely converted into sulfide (Co)₉S₈、MoS₂、Ni₃S₂、WS₂) The amount of sulfur is needed.

In the step (2), in order to mix the vulcanizing agent and the intermediate hydrogenation catalyst uniformly, other proper amount of vulcanizing assistant, such as organic solvent commonly used in the field, can be added. The vulcanizing assistant may be one or more of hydrocarbon oil and organic carboxylic ester, the hydrocarbon oil is one or more of gasoline, kerosene, diesel oil, lamp oil, white oil, industrial soybean oil, lubricating oil base oil, straight run and reduced pressure heavy distillate oil, and the like, and the hydrocarbon oil obtained by secondary processing, such as the hydrocarbon oil obtained by catalytic cracking, thermal cracking and other processes, is preferred. The organic carboxylic ester can be organic carboxylic ester containing 6-60 carbon atoms, preferably one or more of fatty glyceride, animal oil, rapeseed oil, peanut oil, soybean oil, cottonseed oil, etc. The dosage of the vulcanization assistant is 0.1-30%, preferably 1-25% of the weight of the hydrogenation catalyst of the intermediate hydrogenation catalyst.

In the method, the temperature of the heat treatment in the step (2) is generally 70-500 ℃, preferably 120-270 ℃, and the heat treatment time is generally 10-480 min, preferably 15-240 min.

In the method, in the step (2), the temperature is reduced to 20-70 ℃, and then the phosphorus-containing substance is added.

In the process of the present invention, in step (2), the phosphorus-containing substance may be added separately, preferably together with the auxiliary agent, and the auxiliary agent functions to promote more uniform dispersion of the phosphorus-containing substance in the catalyst. The auxiliary agent can be at least one of alcohols and hydrocarbon oil; the alcohol auxiliary agent is at least one of ethanol, propanol, glycol, glycerol and the like; the hydrocarbon oil is one or more of gasoline, kerosene, diesel oil, lamp oil, white oil, industrial soybean oil, lubricating oil base oil and heavy distillate oil of straight run and pressure reduction. The addition amount of the auxiliary agent is 1-30% of the weight of the intermediate hydrogenation catalyst.

In the method of the present invention, the phosphorus-containing substance in step (2) may be a phosphorus-containing substance conventional in the art, and may be selected from phosphorus-containing compounds, specifically, one or more of phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, phosphate esters, phosphorus pentoxide, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphonic acid, phosphinic acid, phosphonate esters, adenosine triphosphate, and the like, preferably one or more of phosphoric acid, ammonium dihydrogen phosphate, and ammonium phosphate. The dosage of the phosphorus-containing substance is 0.1-50%, preferably 0.4-50% of the weight of the intermediate hydrogenation catalyst.

In the method of the present invention, the drying conditions in step (3) are: drying for 0.5-5 h at 60-130 ℃.

In the process of the present invention, one or more of organic acids, organic nitrogen and the like may be introduced as a modifier before, after or simultaneously with step (3) as necessary for adjusting the properties of the catalyst. The loading amount of the modifier is 0.5-20% of the weight of the intermediate hydrogenation catalyst in the step (1), and preferably 2.0-10%. After introduction of organic acids, organic nitrogen, and the like, a suitable drying treatment may be employed. The organic acid and the organic nitrogen may be those conventionally used in the preparation of hydrogenation catalysts. For example, the organic acid may be at least one of citric acid, malic acid, lactic acid, sorbic acid, gluconic acid, tartaric acid, succinic acid, benzoic acid, acetic acid, and oxalic acid, and the organic nitrogen may be at least one of organic amine, amino acid, urea, amide, protein, aniline, and quaternary ammonium salt.

In the method of the present invention, the specific method for the wet activation start-up in the step (4) includes: the temperature of the reactor is raised to 50-180 ℃, preferably to 90-140 ℃ at the temperature raising speed of 1-50 ℃/h, preferably 10-30 ℃/h; introducing the starting oil, introducing hydrogen to boost pressure at the speed of 0.1-10 MPa/h, preferably 1-2 MPa/h to 2-8 MPa, preferably 3-5 MPa, at the temperature of 270-400 ℃, preferably 300-330 ℃, and keeping the temperature for 1-8 h, preferably 1-3 h.

The starting oil is conventional in the field, and if gasoline hydrogenation reaction is performed, gasoline is introduced (see table 2), kerosene is introduced (see table 3) and if diesel hydrogenation reaction is performed, diesel is introduced (see table 4).

Compared with the prior art, the invention has the following advantages:

(1) compared with the conventional sulfur-carrying catalyst, the start-up time of the catalyst is further reduced;

(2) the method firstly prepares the intermediate hydrogenation catalyst, then contacts with a vulcanizing agent for heat treatment, and then adds a phosphorus-containing substance to finally obtain the pre-vulcanized catalyst, which is beneficial to forming metal sulfur phosphide in a specific state, so that the initial reaction temperature of start-up activation can be further improved, the start-up operation requirement of the hydrogenation reactor is met, the safety of the hydrogenation reactor is improved, and the better vulcanization degree and higher catalyst activity of the ex-situ pre-vulcanized catalyst are promoted; in the vulcanization process, the phosphorus-containing substance is added after the heat treatment, so that the original pore structure of the catalyst is prevented from being damaged in the preparation process of the intermediate catalyst, and the reaction activity of the catalyst is further influenced.

Detailed Description

The following is a selection of the prior art hydrogenation catalyst for the ex-situ presulfiding treatment to further illustrate the process and effect of the method of the present invention, but not to limit the scope of the invention, and the main material properties referred to in the examples are as follows. The main materials referred to in the examples and comparative examples are shown in tables 1 to 4.

In the present invention, the unspecified percentages are mass fractions unless the skilled person considers that they are not in accordance with the common general knowledge in the art.

Table 1 main properties of industrial soybean oil

Consists of the following components:
		palmitic acid,% of	7.5
Oleic acid, content of	28.5
		Stearic acid, based on	4.1
Linoleic acid%	57.9
		Linolenic acid content%	2.0
Acid value (KOH) mg. g-1	4.0
		Water and volatile matter%	0.20
Insoluble impurities,% of	0.10

TABLE 2 Main Properties of gasoline

Item	Gasoline (gasoline)
		Density (20 ℃ C.)/g-cm-3	0.7363
Distillation range/. degree.C
		IBP/10%	28/57
30%/50%	95/136
		70%/90%	169/207
95%/EBP	221/229

TABLE 3 essential Properties of kerosene

Item	Kerosene oil
		Density (20 ℃ C.)/g-cm-3	0.8092
Distillation range/. degree.C
		IBP/10%	170/183
30%/50%	193/203
		70%/90%	215/233
95%/EBP	240/251
		Viscosity (20 ℃ C.)/mm2·s-1	1.916
Flash point (off)/deg.C	51
		Freezing point/. degree.C	<-60
Smoke point/mm	25
		Arene, v%	5.6

TABLE 4 Main Properties of Diesel

Item	Straight-run diesel oil
		Density (20 ℃ C.)/g-cm-3	0.8223
Distillation range/. degree.C
		IBP/10%	263/278
30%/50%	288/293
		70%/90%	305/322
95%/EBP	327/354
		Viscosity (20 ℃ C.)/mm2·s-1	8.321
Flash point/. degree.C	125
		Cetane index	51.7

Example 1

(1) 100g of pseudo-boehmite (commercial product or self-product), 2.5g of sesbania powder, 5g of citric acid, 30mL of deionized water, 5mL of nitric acid (the concentration is 30wt percent) and 15mL of silica gel (containing 15wt percent of silicon) are uniformly mixed, extruded into strips, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. Preparing tetrathiomolybdate solution (containing 27% of molybdenum oxide), mixing with the silicon-containing alumina carrier, and drying at 115 ℃ for 3 h. Then mixing with prepared nickel nitrate solution (containing nickel oxide 8%), drying at 75 deg.C for 3.5h, and preparing intermediate hydrogenation catalyst.

(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the using amount of which is 15% of the theoretical sulfur demand of the intermediate hydrogenation catalyst) and a vulcanizing assistant (a mixture of industrial soybean oil and diesel oil, the weight ratio of which is 2:1 and is shown in table 1 and 4, and the using amount of which is 25% of the weight of the intermediate hydrogenation catalyst) to obtain a pre-vulcanized raw material; uniformly mixing the pre-vulcanized raw material with an intermediate hydrogenation catalyst; heat treatment is carried out for 1h at the temperature of 160 ℃; cooling to 60 ℃, then adding 16mL of phosphoric acid (the amount of phosphoric acid (the content is 85%) accounting for 1.9% of the weight of the intermediate hydrogenation catalyst and 15mL of deionized water, uniformly mixing), mixing with 30mL of ethanol, and uniformly mixing;

(3) and (3) treating the material obtained in the step (2) at 120 ℃ for 2h to obtain the pre-vulcanized catalyst 1.

(4) Loading the presulfurized catalyst in the step (3) into a hydrogenation device, and starting up the hydrogenation device under the following conditions: the temperature of the reactor is raised to 140 ℃ at the temperature raising speed of 25 ℃/h, the straight-run diesel oil shown in the table 4 is introduced, then, the hydrogen is introduced for pressure raising, the pressure is raised to 4MPa at the pressure raising speed of 2MPa/h, and the temperature is raised to 300 ℃ and kept constant for 2 h.

Example 2

(1) 100g of pseudo-boehmite (commercial product or self-product), 5g of sesbania powder, 5g of citric acid, 30mL of deionized water, 5mL of nitric acid (the concentration is 30wt percent) and 15mL of silica gel (containing 15wt percent of silicon) are uniformly mixed, extruded into strips and molded, and roasted for 3 hours at 500 ℃ to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. Then mixing with prepared nickel nitrate solution (containing nickel oxide 10%), drying at 110 deg.C for 3h, and preparing intermediate hydrogenation catalyst.

(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 25 percent of the theoretical sulfur demand of the intermediate state catalyst) and a vulcanizing aid (a mixture of industrial rapeseed oil and diesel oil in a weight ratio of 1:2 to obtain a pre-vulcanized raw material, uniformly mixing the pre-vulcanized raw material and the intermediate state hydrogenation catalyst, carrying out heat treatment for 3.5 hours at 225 ℃, reducing the temperature to 60 ℃, adding 35g of diammonium hydrogen phosphate (the dosage of which is 50 percent of the weight of the intermediate state hydrogenation catalyst), and uniformly mixing.

(3) And (3) treating the material obtained in the step (2) at 100 ℃ for 2h, then loading citric acid, introducing the material containing 5% of citric acid by weight of the intermediate hydrogenation catalyst, and then treating at 140 ℃ for 6h to obtain the pre-vulcanized catalyst 2.

(4) Loading the presulfurized catalyst in the step (3) into a hydrogenation device, and starting up the hydrogenation device under the following conditions: the temperature of the reactor is raised to 90 ℃ at the temperature raising speed of 10 ℃/h, the straight-run diesel oil shown in the table 4 is introduced, then, the hydrogen is introduced for pressure raising, the pressure is raised to 5MPa at the pressure raising speed of 1.2MPa/h, and the temperature is raised to 305 ℃ and kept constant for 3 h.

Example 3

(1) 100g of pseudo-boehmite (commercial product or self-product) roasted at 600 ℃, 5g of sesbania powder, 5g of citric acid, 30m of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and formed, and the mixture is roasted at 500 ℃ for 3 hours to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. Then mixing with prepared cobalt nitrate solution (containing cobalt oxide 10%), drying at 100 deg.C for 2.5h, and preparing intermediate hydrogenation catalyst.

(2) Uniformly mixing a vulcanizing agent (elemental sulfur, the dosage of which is 35 percent of the theoretical sulfur demand of the intermediate hydrogenation catalyst) and a vulcanizing aid (a mixture of industrial rapeseed oil and diesel oil in a weight ratio of 1:2 to obtain a pre-vulcanized raw material, uniformly mixing the pre-vulcanized raw material and the intermediate hydrogenation catalyst, carrying out heat treatment for 3.5 hours at 205 ℃, reducing the temperature to 60 ℃, adding 25g of diammonium hydrogen phosphate (the dosage of which is 50 percent of the dosage of the intermediate hydrogenation catalyst and adding 35mL of deionized water), and uniformly mixing.

(3) And (3) treating the material obtained in the step (2) at 100 ℃ for 3h, then loading citric acid, introducing the material containing 5% of citric acid by weight of the intermediate hydrogenation catalyst, and then treating at 140 ℃ for 6h to obtain a pre-vulcanized catalyst 3.

(4) Loading the presulfurized catalyst in the step (3) into a hydrogenation device, and starting up the hydrogenation device under the following conditions: the temperature of the reactor was raised to 130 ℃ at a temperature rise rate of 10 ℃/h, the straight-run diesel oil shown in Table 4 was introduced, then, hydrogen was introduced to increase the pressure, the pressure was increased to 4.5MPa at a pressure rise rate of 1.5MPa/h, and the temperature was raised to 315 ℃ and maintained for 1.5 h.

Example 4

(1) 150g of pseudo-boehmite (commercial product or self-product), 2.5g of sesbania powder, 5g of citric acid, 30m of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and molded, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. Then mixing with prepared nickel nitrate solution (containing nickel oxide 10%), drying at 55 deg.C for 6h, and preparing intermediate hydrogenation catalyst.

(2) Uniformly mixing a vulcanizing agent (SZ-54, 12g, the dosage of which is 30 percent of the theoretical sulfur demand of the intermediate catalyst) and a vulcanizing additive (a mixture of industrial soybean oil and gasoline in a weight ratio of 2:1, the dosage of which is 9 percent of the weight of the intermediate hydrogenation catalyst) to obtain a pre-vulcanized raw material; uniformly mixing the pre-vulcanized raw material with an intermediate hydrogenation catalyst; heat treatment is carried out for 3 hours at the temperature of 150 ℃; cooling to 40 ℃, and then adding 19g of adenosine triphosphate (the dosage of which accounts for 19 percent of the dosage of the intermediate hydrogenation catalyst) and uniformly mixing;

(3) and (3) treating the material obtained in the step (2) at 100 ℃ for 3h, then loading citric acid, introducing the material containing 5% of citric acid by weight of the intermediate hydrogenation catalyst, and then treating at 130 ℃ for 6h to obtain a pre-vulcanized catalyst 4.

(4) Loading the presulfurized catalyst in the step (3) into a hydrogenation device, and starting up the hydrogenation device under the following conditions: the temperature of the reactor is raised to 150 ℃ at the temperature raising speed of 15 ℃/h, the straight-run diesel oil shown in the table 4 is introduced, then, the hydrogen is introduced for pressure raising, the pressure is raised to 7.5MPa at the pressure raising speed of 1.5MPa/h, and the temperature is raised to 325 ℃ and the constant temperature is kept for 1.5 h.

Comparative example 1

Comparative catalyst A was obtained by following the procedure of example 1 except that phosphoric acid and ethanol were not added in step (2).

Comparative example 2

Comparative catalyst B was obtained by following the procedure of example 2 except that diammonium hydrogen phosphate was not added in step (2).

Comparative example 3

(1) 150g of pseudo-boehmite (commercial product or self-product), 2.5g of sesbania powder, 5g of citric acid, 30mL of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and molded, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. Then mixing with prepared nickel nitrate solution (containing nickel oxide 10%), drying at 55 deg.C for 6h, and preparing intermediate hydrogenation catalyst. Adding diammonium hydrogen phosphate into the intermediate hydrogenation catalyst to obtain a hydrogenation catalyst to be pre-vulcanized, wherein the phosphorus content in the hydrogenation catalyst to be pre-vulcanized is 6 wt%;

(2) uniformly mixing a vulcanizing agent (SZ-54, 12g, the dosage of which is 30 percent of the theoretical sulfur demand of the intermediate catalyst) and a vulcanizing additive (a mixture of industrial soybean oil and gasoline in a weight ratio of 2:1, the dosage of which is 9 percent of the weight of the intermediate hydrogenation catalyst) to obtain a pre-vulcanized raw material; uniformly mixing a presulfurized raw material with 115g of the hydrogenation catalyst to be presulfurized obtained in the step (1); heat treatment is carried out for 3 hours at the temperature of 150 ℃;

(3) and (3) loading citric acid on the material obtained in the step (2), introducing the material containing 5% of citric acid by weight of the intermediate hydrogenation catalyst, and then treating at 130 ℃ for 6 hours to obtain a comparative catalyst C.

(4) Loading the presulfurized catalyst in the step (3) into a hydrogenation device, and starting up the hydrogenation device under the following conditions: the temperature of the reactor is raised to 150 ℃ at the temperature raising speed of 15 ℃/h, the straight-run diesel oil shown in the table 4 is introduced, then, the hydrogen is introduced for pressure raising, the pressure is raised to 7.5MPa at the pressure raising speed of 1.5MPa/h, and the temperature is raised to 325 ℃ and the constant temperature is kept for 1.5 h.

Comparative example 4

(1) 150g of pseudo-boehmite (commercial product or self-product), 2.5g of sesbania powder, 5g of citric acid, 30m of deionized water, 5mL of nitric acid (30%) and 15mL of silica gel (containing 15%) are uniformly mixed, extruded into strips and molded, and roasted at 550 ℃ for 4 hours to prepare the silicon-containing alumina carrier. And preparing an ammonium thiomolybdate solution (containing 30% of molybdenum oxide), mixing the ammonium thiomolybdate solution with the silicon-containing alumina carrier, and drying the mixture for 3 hours at 115 ℃. And mixing the mixed solution with a prepared nickel nitrate solution containing 10 percent of nickel oxide), wherein the nickel nitrate solution contains diammonium hydrogen phosphate, and drying the mixture for 6 hours at the temperature of 55 ℃ to prepare the intermediate catalyst.

(2) Uniformly mixing a vulcanizing agent (SZ-54, 12g, the dosage of which is 30 percent of the theoretical sulfur demand of the intermediate catalyst) and a vulcanizing additive (a mixture of industrial soybean oil and gasoline in a weight ratio of 2:1, the dosage of which is 9 percent of the weight of the intermediate hydrogenation catalyst) to obtain a pre-vulcanized raw material; uniformly mixing a pre-vulcanized raw material and the intermediate catalyst obtained in the step (1); heat treatment is carried out for 3 hours at the temperature of 150 ℃;

(3) and (3) loading citric acid on the material obtained in the step (2), introducing the material containing 5% of citric acid by weight of the intermediate hydrogenation catalyst, and then treating at 130 ℃ for 6 hours to obtain a comparative catalyst D.

(4) Loading the presulfurized catalyst in the step (3) into a hydrogenation device, and starting up the hydrogenation device under the following conditions: the temperature of the reactor is raised to 150 ℃ at the temperature raising speed of 15 ℃/h, the straight-run diesel oil shown in the table 4 is introduced, then, the hydrogen is introduced for pressure raising, the pressure is raised to 7.5MPa at the pressure raising speed of 1.5MPa/h, and the temperature is raised to 325 ℃ and the constant temperature is kept for 1.5 h.

Example 5

The ex-situ presulfurization catalysts obtained in examples 1 to 4 and the catalysts obtained in comparative examples 1 to 4 were subjected to evaluation tests. The initial activation temperatures of the various ex-situ presulfided catalysts (initial activation temperatures are based on the significant release of water in the presence of hydrogen) were compared, along with the relative activities after activation.

The initial activation temperature test method comprises the following steps: under the condition of 0.2MPa (gauge pressure) and hydrogen gas existence, the temperature is gradually raised, and the temperature of water obviously collected from the material at the outlet of the device is the initial activation temperature.

The relative activity evaluation conditions were: mixed diesel oil is used as raw oil (Table 5), the reaction pressure is 6.0MPa, the volume ratio of hydrogen to oil is 350:1, and the volume airspeed is 2.5h^-1The reaction temperature was 345 ℃. Based on the activity of catalyst A (100).

TABLE 6 Primary Properties of the feedstocks

Item	Data of
		Density (20 ℃), kg/m3	853.3
Distillation range, deg.C
		IBP/10%	217/277
30%/50%	296/309
		70%/90%	327/356
95%/EBP	369/375
		S，μg/g	15150
N，μg/g	118
		Cetane number	59.0
Bromine number, gBr/100g	4.5

TABLE 7 initial activation temperature comparison of catalysts

Catalyst numbering	1	2	3	4	A	B	C	D
									Initial activation temperature,. degree.C	237	285	196	230	127	124	102	109

TABLE 8 comparison of hydrogenation activity of catalysts

Catalyst numbering	1	2	3	4	A	B	C	D
									Desulfurization rate%	136	126	134	129	100	107	108	114

From the above results, it can be seen that the ex-situ presulfided catalyst obtained by the method of the present invention has a higher initial activation temperature (which is advantageous to match the operating conditions of the hydrogenation reactor), and a higher catalytic performance.