阅读说明：本技术 润滑油加氢补充精制催化剂及其制备方法和应用 (Lubricating oil hydrogenation complementary refining catalyst and preparation method and application thereof ) 是由 宋君辉 甄涛 焦祖凯 金吉海 张铎 严金龙 刘丽芝 于 2019-10-09 设计创作，主要内容包括：本发明公开一种润滑油加氢补充精制催化剂的制备方法,包括如下步骤：提供包含氧化铝的含孔的催化剂载体；配制助剂溶液并对所述催化剂载体进行浸渍、干燥,得载体A；配制催化剂组成所需的Mo-Ni-P溶液和W-Ni溶液；将油相、表面活性剂和助表面活性剂加入到所述Mo-Ni-P溶液或W-Ni溶液中,搅拌,混合均匀,得油包水型微乳液；用所述微乳液浸渍所述载体A,经干燥、焙烧,得催化剂半成品；用所述W-Ni溶液或Mo-Ni-P溶液浸渍所述催化剂半成品,经干燥、焙烧,得所述润滑油加氢补充精制催化剂。该方法在提高催化剂脱硫脱氮性能的同时提高烯烃和芳烃加氢饱和能力。本发明还公开了该方法制备得到的催化剂及其应用。(The invention discloses a preparation method of a lubricating oil hydrogenation refining catalyst, which comprises the following steps: providing a pore-containing catalyst support comprising alumina; preparing an auxiliary agent solution, and impregnating and drying the catalyst carrier to obtain a carrier A; preparing Mo-Ni-P solution and W-Ni solution required by catalyst composition; adding the oil phase, the surfactant and the cosurfactant into the Mo-Ni-P solution or the W-Ni solution, stirring and uniformly mixing to obtain the water-in-oil microemulsion; dipping the carrier A by the microemulsion, drying and roasting to obtain a catalyst semi-finished product; and (3) impregnating the semi-finished product of the catalyst with the W-Ni solution or the Mo-Ni-P solution, and drying and roasting to obtain the lubricating oil hydrofining catalyst. The method improves the desulfurization and denitrification performance of the catalyst and simultaneously improves the hydrogenation saturation capacity of olefin and aromatic hydrocarbon. The invention also discloses the catalyst prepared by the method and application thereof.)

1. A preparation method of a lubricating oil hydrofinishing catalyst is characterized by comprising the following steps:

1) providing a pore-containing catalyst support comprising alumina;

2) preparing an auxiliary agent solution, and impregnating and drying the catalyst carrier to obtain a carrier A;

3) preparing Mo-Ni-P solution and W-Ni solution required by catalyst composition;

4) adding the oil phase, the surfactant and the cosurfactant into the Mo-Ni-P solution or the W-Ni solution, stirring and uniformly mixing to obtain the water-in-oil microemulsion;

5) dipping the carrier A by the microemulsion, drying and roasting to obtain a catalyst semi-finished product;

6) and impregnating the semi-finished product of the catalyst with the prepared W-Ni solution or Mo-Ni-P solution, drying and roasting to obtain the lubricating oil hydrofinishing catalyst.

2. The production method according to claim 1, wherein in step 1), the production of the pore-containing catalyst support containing alumina comprises the steps of:

mixing and rolling pseudo-boehmite, peptizing agent, extrusion aid and water, extruding into strips, forming, drying and roasting to prepare the catalyst carrier.

3. The preparation method according to claim 2, wherein the pseudoboehmite has a pore volume of > 0.95mL/g and a specific surface area of 280-330 m²(ii)/g; preferably, the peptizing agent is one or more of nitric acid, acetic acid and citric acid; preferably, the extrusion aid is one or more of sesbania powder, starch and methyl cellulose; preferably, the proportion of the pseudo-boehmite, the peptizing agent, the extrusion aid and the water is 1: (0.01-0.06): (0.01-0.04): (1.0-1.5); preferably, the drying temperature is 120-150 ℃, and the drying time is 6-10 hours; preferably, the roasting temperature is 550-800 ℃, and the roasting time is 2-6 hours.

4. The method according to claim 1, wherein, in the step 2),

the auxiliary agent solution is a metal solution capable of capturing an impregnation solution; preferably, the assistant solution is one or more of calcium nitrate, strontium nitrate and barium nitrate solution; preferably, in the aid solution, the concentration is 0.015-0.035 g/mL based on the metal oxide in the aid solution; preferably, the mass content of the auxiliary agent in the carrier A is 1-3% calculated by metal oxide in the auxiliary agent solution; preferably, the drying temperature is 120-150 ℃, and the drying time is 6-10 hours.

5. The method according to claim 1, wherein, in step 3),

in the Mo-Ni-P solution, calculated as metal oxide, MoO₃The mass ratio of NiO and P in the catalyst is 20-25%, 3.0-5.0% and 2-2.5% respectively; contains MoO in terms of metal oxide concentration₃ 0.313～0.476g/mL，NiO 0.0471～0.095g/mL，P 0.0314～0.0476g/mL；

In the W-Ni solution, in terms of metal oxide, WO₃And NiO accounts for 28-32% and 4.0-6.0% of the catalyst respectively by mass; containing WO in terms of metal oxide concentration₃ 0.484～0.607g/mL，NiO 0.069～0.114g/mL。

6. The method according to claim 1, wherein, in the step 4),

the oil phase is selected from one or a mixture of more of C4-C10 naphthenic hydrocarbon, straight-chain alkane and branched-chain alkane;

preferably, the surfactant is a nonionic surfactant;

preferably, the cosurfactant is C4-C6 alcohol;

preferably, the weight ratio of the surfactant, the cosurfactant and the oil phase is 1: 0.5-5: 1-6;

preferably, the volume ratio of the surfactant to the Mo-Ni-P solution or the W-Ni solution is 1: 4-1: 8.

7. the method according to claim 1, wherein, in step 5),

the impregnation is saturated impregnation;

preferably, the drying temperature is 120-150 ℃, and the drying time is 6-10 hours;

preferably, the roasting temperature is 400-550 ℃, and the roasting time is 2-6 hours.

8. The method according to claim 1, wherein, in step 6),

the impregnation is unsaturated impregnation;

preferably, the drying temperature is 120-150 ℃, and the drying time is 6-10 hours;

preferably, the roasting temperature is 400-550 ℃, and the roasting time is 2-6 hours.

9. The catalyst for hydrorefining of lubricating oil produced by the production process according to any one of claims 1 to 8.

10. Use of a catalyst for hydrorefining of lubricating oils prepared by the process according to any of claims 1 to 8 in the catalysis of lubricating oils prepared from base oils.

Technical Field

The invention relates to the technical field of oil refining. More particularly, relates to a lubricating oil hydrofinishing catalyst, and a preparation method and application thereof.

Background

The naphthenic base crude oil has the characteristics of high density, high viscosity, low wax content, high aromatic hydrocarbon and naphthenic hydrocarbon content, low condensation point and the like, and is commonly used for producing low-condensation lubricating oil base oil, such as transformer oil, refrigerator oil, rubber filling oil and the like. The traditional lubricant base oil production adopts a solvent process which mainly comprises the steps of solvent refining to remove non-ideal components such as aromatic hydrocarbon and the like and solvent dewaxing so as to ensure the low-temperature flow property of the base oil. At present, the technology for producing lubricating oil by a hydrogenation method is developed rapidly, and the hydrogenation method is a process method for producing lubricating oil base oil by adopting a combined process of hydrotreating, hydrocracking, hydrodewaxing or isodewaxing and hydrofining. The hydrogenation method has the advantages of high product quality, no environmental protection problem, high base oil yield and the like, and gradually replaces the traditional solvent method process.

In the hydrofining catalyst, different metal component combinations have great influence on the activity, wherein the activity sequence of the hydrodesulfurization reaction is as follows: Mo-Co > Mo-Ni > W-Co; the activity sequence of the hydrogenation dearomatization reaction is as follows: W-Ni > Mo-Co > W-Co, i.e., the Mo-Ni series active metal catalyst is beneficial to removing sulfur and nitrogen impurities, but the aromatic saturation capacity is slightly poor; the W-Ni catalyst has strong arene saturation capacity, but poor sulfur and nitrogen impurity removal performance. Therefore, sulfur, nitrogen, oxygen and other impurities in distillate oil are removed, olefin and aromatic hydrocarbon are selectively hydrogenated and saturated, and W-Mo-Ni is often used as a catalyst of an active component. There are two conventional methods for preparing W-Mo-Ni catalysts, one of which is: the preparation method has the advantages that the W-Mo-Ni solution is directly prepared, and the catalyst is prepared by impregnating a carrier, so that the defect is that the content of metal W and Mo is limited in the solution preparation process, the desulfurization and denitrification performance of the catalyst is lower than that of a Mo-Ni catalyst, and the olefin and aromatic hydrocarbon hydrogenation saturation capacity of the catalyst is also lower than that of a W-Ni catalyst, so that the enhanced impurity removal and hydrogenation saturation performance of the catalyst is influenced; the second step is as follows: respectively preparing W-Ni and Mo-Ni active metal solutions, and impregnating the W-Ni and Mo-Ni active metal solutions on a carrier for preparing the catalyst in two times, wherein the defects are that part of active metal is covered due to the two times of impregnation, the utilization rate of the active metal is reduced, and the hydrogenation activity of the catalyst is weakened.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a preparation method of a lubricating oil hydrogenation complementary refining catalyst, which is used for preparing a W-Mo-Ni catalyst with high active metal utilization rate, and improving the hydrogenation saturation capacity of olefin and aromatic hydrocarbon while improving the desulfurization and denitrification performance.

The second purpose of the invention is to provide a catalyst for hydrorefining lubricating oil.

The third purpose of the invention is to provide the application of the lubricating oil hydrofinishing catalyst.

In order to achieve the first purpose, the invention adopts the following technical scheme:

a preparation method of a lubricating oil hydrofinishing catalyst comprises the following steps:

1) providing a pore-containing catalyst support comprising alumina;

2) preparing an auxiliary agent solution, and impregnating and drying the catalyst carrier to obtain a carrier A;

3) preparing Mo-Ni-P solution and W-Ni solution required by catalyst composition;

4) adding the oil phase, the surfactant and the cosurfactant into the Mo-Ni-P solution or the W-Ni solution, stirring and uniformly mixing to obtain the water-in-oil microemulsion;

5) dipping the carrier A by the microemulsion, drying and roasting to obtain a catalyst semi-finished product;

6) and impregnating the semi-finished product of the catalyst with the prepared W-Ni solution or Mo-Ni-P solution, drying and roasting to obtain the lubricating oil hydrofinishing catalyst.

Alternatively, in step 1), the preparation of the pore-containing catalyst support comprising alumina comprises the steps of: mixing and rolling pseudo-boehmite, peptizing agent, extrusion aid and water, extruding into strips, forming, drying and roasting to prepare the catalyst carrier.

The pseudo-boehmite is produced by an aluminum sulfate method, a carbonization method and an aluminum chloride method which are commonly used in the industry at present. Optionally, the pore volume of the pseudo-boehmite is more than 0.95mL/g, and the specific surface area is 280-330 m²/g。

Optionally, the peptizing agent is one or more of nitric acid, acetic acid and citric acid, and preferably nitric acid.

Optionally, the extrusion aid is one or more of sesbania powder, starch and methyl cellulose, and sesbania powder is preferred.

Optionally, the ratio of the pseudo-boehmite, the peptizing agent, the extrusion aid and the water is 1: (0.01-0.06): (0.01-0.04): (1.0-1.5).

Optionally, in the step 1), the drying temperature is 120-150 ℃, and the drying time is 6-10 hours.

Optionally, in the step 1), the roasting temperature is 550-800 ℃, and the roasting time is 2-6 hours.

Optionally, in step 1), the catalyst carrier is cylindrical, clover-shaped or clover-shaped, preferably clover-shaped, and the carrier has the properties of pore volume of more than 0.70mL/g and specific surface area of 180-250 m²The water absorption capacity is more than 0.85 mL/g.

Optionally, in step 2), the aid solution is a metal solution capable of capturing an impregnation solution (water-in-oil microemulsion).

Optionally, in step 2), the aid solution is one or more of calcium nitrate, strontium nitrate and barium nitrate solution, and calcium nitrate is preferred.

Optionally, in the step 2), the concentration of the metal oxide in the auxiliary solution is 0.015 to 0.035 g/mL.

Optionally, in the step 2), the mass content of the auxiliary in the carrier a is 1-3% based on the metal oxide in the auxiliary solution.

Optionally, in the step 2), the drying temperature is 120-150 ℃, and the drying time is 6-10 hours.

Optionally, in the step 3), MoO is calculated by metal oxide in the Mo-Ni-P solution₃The mass ratio of NiO and P in the catalyst is 20-25%, 3.0-5.0% and 2-2.5%.

Optionally, in the step 3), the Mo-Ni-P solution contains MoO according to the concentration of the metal oxide₃ 0.313～0.476g/mL，NiO 0.0471～0.095g/mL，P 0.0314～0.0476g/mL。

Alternatively, in step 3), WO is added to the W-Ni solution in terms of metal oxide₃And NiO accounts for 28-32% and 4.0-6.0% of the catalyst by mass ratio respectively.

Optionally, in the step 3), the W-Ni solution contains WO according to the concentration of the metal oxide₃ 0.484～0.607g/mL，NiO 0.069～0.114g/mL。

In the step 3), a Mo-Ni-P solution or a W-Ni solution required by the catalyst composition is prepared according to the metal content of the Mo-Ni catalyst or the W-Ni catalyst and the water absorption of the carrier, wherein the Mo-Ni-P catalyst accounts for 30-70% of the catalyst by volume, and the W-Ni catalyst accounts for 30-70% of the catalyst by volume. The preparation method of the Mo-Ni-P solution or the W-Ni solution is a conventional preparation method for the person skilled in the art.

Optionally, in the step 4), the oil phase is selected from one or a mixture of more of C4-C10 naphthenic hydrocarbon, straight-chain alkane and branched-chain alkane.

Alternatively, in step 4), the oil phase includes but is not limited to a solvent selected from n-hexane, cyclohexane, n-heptane, isooctane, and the like.

Optionally, in step 4), the surfactant is a nonionic surfactant.

Alternatively, in step 4), the surfactant includes, but is not limited to, one selected from the group consisting of ethylene glycol octyl phenyl ether, cetyl methyl ammonium bromide, Span-80, fatty alcohol polyoxyethylene ether, polyoxyethylene glycol octyl phenyl ether, and the like.

Optionally, in the step 4), the cosurfactant is a C4-C6 alcohol.

Optionally, in step 4), the co-surfactant includes, but is not limited to, n-butanol. N-pentanol.

Optionally, the microemulsion has a particle size of less than 6nm, and the microemulsion is a homogeneous water-in-oil microemulsion.

Optionally, in step 4), the weight ratio of the surfactant, the co-surfactant and the oil phase is 1: 0.5-5: 1 to 6.

Optionally, the volume ratio of the surfactant to the Mo-Ni-P solution or the W-Ni solution is 1: 4-1: 8.

optionally, in step 5), the impregnation is saturated impregnation.

Optionally, in the step 5), the drying temperature is 120-150 ℃, and the drying time is 6-10 hours.

Optionally, in the step 5), the roasting temperature is 400-550 ℃, and the roasting time is 2-6 hours.

In the step 5), the carrier A is impregnated by the microemulsion, the volume of an impregnation solution is measured according to the volume ratio of the Mo-Ni-P catalyst and the W-Ni catalyst in the catalyst, then an oil phase, a surfactant and a cosurfactant are added into the impregnation solution to prepare the microemulsion, the volume of the microemulsion is equal to the volume of the water absorption required by the impregnated carrier, and then the carrier is subjected to saturated impregnation.

Optionally, in the step 5), the nature of the semi-finished catalyst is that the pore volume is more than 0.55mL/g, and the specific surface area is 160-230 m²Water absorption of > 0.65 mL/g.

Optionally, in step 6), the impregnation is an unsaturated impregnation. Namely, according to the volume ratio of W-Ni catalyst and Mo-Ni-P catalyst in the catalyst, 2/3-3/4 times of water absorption capacity of the semi-finished product is taken as the impregnation solution for impregnating the semi-finished product.

Optionally, in the step 6), the drying temperature is 120-150 ℃, and the drying time is 6-10 hours.

Optionally, in the step 6), the roasting temperature is 400-550 ℃, and the roasting time is 2-6 hours.

Furthermore, it should be noted that, when the oil phase, the surfactant and the co-surfactant are added to the Mo-Ni-P solution in step 4), the prepared W-Ni solution is used to impregnate the catalyst semi-finished product in step 6); when the oil phase, the surfactant and the cosurfactant are added into the W-Ni solution in the step 4), the prepared Mo-Ni-P solution is used for impregnating the catalyst semi-finished product in the corresponding step 6)

In order to achieve the second object, the invention also protects the lubricating oil hydrofinishing catalyst prepared by the preparation method of the first object.

The properties of the catalyst are as follows: pore volume is more than 0.35mL/g, and specific surface area is 150-200 m²(ii) in terms of/g. The Mo-Ni-P catalyst accounts for 30-70% of the catalyst by volume; the Mo-Ni catalyst is MoO₃20-25 wt%, NiO 3.0-5.0 wt%, and P2-2.5 wt%; the volume ratio of the W-Ni catalyst in the catalyst is 30-70%; the composition of the W-Ni catalyst is WO₃28～32wt％，NiO 4.0～6.0wt％。

In order to achieve the third purpose, the invention also protects the application of the lubricating oil hydrofinishing catalyst prepared by the preparation method of the first purpose in catalyzing the lubricating oil prepared from the raw oil.

Optionally, the feedstock oil is selected from a hydro-upgraded diesel fraction, a lube oil fraction.

In addition, in the present invention, the specific surface area, pore volume, pore diameter and pore distribution are measured by a low temperature liquid nitrogen adsorption method, unless otherwise specified.

The invention has the following beneficial effects:

the preparation method provided by the invention comprises the steps of saturating and impregnating a carrier A by adopting a water-in-oil microemulsion with a specific composition, wherein after a microemulsion impregnating solution enters a pore channel of the carrier A, due to the change of environment, an oil layer of the microemulsion is damaged and shrunk, a metal solution is adsorbed by exposed alumina, the metal solution is difficult to diffuse because the surrounding oil phase surrounds the metal solution, the metal solutions in different liquid layers are converged together along with the continuous damage and shrinkage of the oil layer to form an independent catalyst system, after drying and roasting, an organic solution is burnt, a pit is left at the position of an organic matter, and a certain space is left for a second impregnating solution; furthermore, the second-time impregnated semi-finished catalyst is impregnated in an unsaturated mode, because hydroxyl (or exposed auxiliary oxide) of exposed alumina formed after roasting exists in a pit reserved at the position of an organic matter, the hydroxyl has stronger adsorption capacity on an acidic impregnating solution Mo-Ni-P solution or a W-Ni solution, and the impregnating solution is converged at the pit to form another independent catalyst system due to competitive adsorption; therefore, the Mo-Ni catalyst system and the W-Ni catalyst system independently exist on one catalyst simultaneously by the preparation method, and compared with the existing W-Mo-Ni catalyst system, the preparation method not only increases the desulfurization and denitrification activity of the catalyst, but also improves the olefin and aromatic hydrocarbon hydrogenation saturation performance of the catalyst.

In addition, the preparation method is simple and flexible to operate, and the proportion of the two catalyst systems can be adjusted according to the different contents of sulfur, nitrogen and aromatic hydrocarbon in the raw materials and the different requirements on target products.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

Example 1

Respectively weighing the pore volume of 1.095mL/g and the specific surface area of 328m produced by the aluminum sulfate method²500g (dry basis 71%) of pseudo-boehmite per gram, 18.4g (65%) of nitric acid, 10g of sesbania powder and 694g of deionized water are added into a rolling machine to be rolled and mixed, and the mixture is dried for 10 hours at 120 ℃ after being extruded and formed, and then is roasted for 3 hours at 750 ℃ to obtain the clover-shaped catalyst carrier for standby. The carrier property is that the pore volume is 0.757mL/g, and the specific surface area is 235m2/g and the water absorption capacity is 0.90 mL/g.

90mL of calcium nitrate solution containing 0.02g/mL of calcium oxide was prepared, 100g of the above-mentioned carrier was weighed and immersed, and dried at 140 ℃ for 8 hours, and the water absorption of the calcium-containing carrier after drying was 88 mL/g.

The catalyst composition is MoO₃22 percent of NiO, 3.5 percent of NiO and 2.0 percent of P, and combining the water absorption capacity of a calcium-containing carrier to prepare a Mo-Ni-P solution for standby use, wherein MoO₃The concentration is 0.344g/mL, the NiO concentration is 0.055g/mL, and the P concentration is 0.031 g/mL;

the volume ratio of the pre-prepared catalyst Mo-Ni catalyst in the catalyst is 40%. Weighing 35.2mL of the solution, starting stirring, adding 26.5g of isooctane (density 0.6919), 5.0g of polyoxyethylene glycol octylphenyl ether (density 1.06) and 8.0g of n-amyl alcohol (density 0.82) respectively, mixing uniformly, and continuing stirring fully for 50min to obtain 88mL of water-in-oil microemulsion with the particle size less than 6 nm;

weighing 100g of the calcium-containing carrier, soaking the carrier in 88mL of microemulsion, drying at 120 ℃ for 8 hours, and roasting at 450 ℃ for 3 hours to obtain a semi-finished catalyst. The properties are as follows: the pore volume is 0.655mL/g, and the water absorption capacity is 0.67 mL/g.

The catalyst composition is WO₃32 percent of NiO, 5.5 percent of NiO, and preparing a W-Ni solution for standby by combining the water absorption of a carrier, wherein WO₃The concentration is 0.582g/mL, and the NiO concentration is 0.10 g/mL;

the volume ratio of the W-Ni catalyst in the catalyst is 60%. Weighing 52.8mL of W-Ni solution to impregnate the semi-finished product of the catalyst, drying the semi-finished product at 120 ℃ for 10 hours, and roasting the semi-finished product at 500 ℃ for 3 hours to obtain the catalyst. The catalyst properties are shown in Table 1, and the catalyst evaluation results are shown in Table 4.

Example 2

The preparation process is as in example 1, except that the pseudoboehmite produced by the aluminum sulfate method is changed into the material with the pore volume of 1.061mL/g and the specific surface area of 320m²In the case of the pseudo-boehmite produced by the carbonization method, the amount of nitric acid added was changed to 19.1g (65%) and the amount of deionized water added was changed to 712g, so that the catalyst AC of the present invention was obtained, the catalyst properties are shown in Table 1, and the catalyst evaluation results are shown in Table 4.

Example 3

The procedure is as in example 1, except that 27.3g of cyclohexane (density 0.78) is added instead of isooctane, 6.0g of fatty alcohol-polyoxyethylene ether (density 1.1) is added instead of polyoxyethylene glycol octylphenyl ether, and 10.0g of n-butanol (density 0.81) is added instead of n-pentanol, to give the catalyst AC of the invention, the properties of which are shown in Table 1, and the evaluation results of which are shown in Table 4.

Example 4

Weighing 1.095mL/g of pore volume produced by an aluminum sulfate method, 500g (dry basis 71%) of pseudo-boehmite with a specific surface area of 328m2/g, 18.4g (65%) of nitric acid, 10g of sesbania powder and 694g of deionized water, adding into a rolling machine, rolling and mixing, extruding to form strips, drying at 120 ℃ for 10 hours, and roasting at 750 ℃ for 3 hours to obtain a clover-shaped catalyst carrier for later use. The carrier has the properties of pore volume of 0.757mL/g, specific surface area of 235m2/g and water absorption capacity of 0.90 mL/g;

90mL of calcium nitrate solution containing 0.02g/mL of calcium oxide was prepared, 100g of the above-mentioned carrier was weighed and immersed, and dried at 140 ℃ for 8 hours, and the water absorption of the calcium-containing carrier after drying was 88 mL/g.

The catalyst composition is WO₃32 percent of NiO and 5.5 percent of NiO, and preparing a W-Ni solution for standby by combining with the water absorption of a calcium-containing carrier, wherein the concentration of WO3 is 0.582g/mL, and the concentration of NiO is 0.10 g/mL;

the volume ratio of the W-Ni catalyst in the catalyst is 40%. Weighing 35.2mL of the solution, starting stirring, adding 26.5g of isooctane (density 0.6919), 5.0g of polyoxyethylene glycol octylphenyl ether (density 1.06) and 8.0g of n-amyl alcohol (density 0.82) respectively, mixing uniformly, and continuing stirring fully for 50min to obtain 88mL of water-in-oil microemulsion with the particle size less than 6 nm;

weighing 100g of the calcium-containing carrier, soaking the carrier in 88mL of microemulsion, drying at 120 ℃ for 8 hours, and roasting at 450 ℃ for 3 hours to obtain a semi-finished catalyst. The properties are as follows: the pore volume is 0.643mL/g, the specific surface area is 209m2/g, and the water absorption capacity is 0.65 mL/g.

The catalyst composition is MoO₃22 percent, NiO 3.5 percent and P2.0, and combining the water absorption capacity of the carrier to prepare Mo-Ni-P solution for standby use, wherein MoO₃The concentration is 0.344g/mL, the NiO concentration is 0.055g/mL, and the P concentration is 0.031 g/mL;

the volume ratio of the pre-prepared catalyst Mo-Ni catalyst in the catalyst is 60%. Weighing 52.8mL of W-Ni solution to impregnate the semi-finished product of the catalyst, drying the semi-finished product at 120 ℃ for 10 hours, and roasting the semi-finished product at 500 ℃ for 3 hours to obtain the catalyst. The catalyst properties are shown in Table 1, and the catalyst evaluation results are shown in Table 4.

Comparative example 1

Respectively weighing the pore volume of 1.095mL/g and the specific surface area of 328m produced by the aluminum sulfate method²500g (dry basis 71%) of pseudo-boehmite per gram, 18.4g (65%) of nitric acid, 10g of sesbania powder and 694g of deionized water are added into a rolling machine to be rolled and mixed, and the mixture is dried for 10 hours at 120 ℃ after being extruded and formed, and then is roasted for 3 hours at 750 ℃ to obtain the clover-shaped catalyst carrier for standby. The carrier has the properties of pore volume of 0.757mL/g, specific surface area of 235m2/g and water absorption capacity of 0.90 mL/g;

90mL of calcium nitrate solution containing 0.02g/mL of calcium oxide was prepared, 100g of the above-mentioned carrier was weighed and immersed, and dried at 140 ℃ for 8 hours, and the water absorption of the calcium-containing carrier after drying was 88 mL/g.

Based on the average composition of the catalyst of example 1, i.e., WO₃ 20.5％，MoO₃8.0 percent of NiO, 4.8 percent of NiO and 0.7 percent of P, and combining the water absorption capacity of the carrier to prepare a W-Mo-Ni-P solution for standby use, wherein WO₃The concentration is 0.353g/mL, MoO₃The concentration is 0.138g/mL, the NiO concentration is 0.083g/mL, and the P concentration is 0.012 g/mL;

35.2mL of the above solution was measured and addedAdding 88mL of ionized water, mixing, soaking 100g of the calcium-containing carrier, drying at 120 ℃ for 8 hours, and roasting at 450 ℃ for 3 hours to obtain a semi-finished catalyst. The properties are as follows: pore volume is 0.643mL/g, specific surface area is 201m²Water absorption of 0.63 mL/g.

Weighing 52.8mL of the solution, adding deionized water to 79mL of the solution, saturating and soaking the semi-finished product of the catalyst, drying the semi-finished product at 120 ℃ for 10 hours, and roasting the semi-finished product at 500 ℃ for 3 hours to obtain a comparative catalyst. The catalyst properties are shown in Table 1, and the catalyst evaluation results are shown in Table 4.

TABLE 1 Properties of catalysts of the invention and comparative examples

The catalyst evaluation uses the diesel oil fraction of a hydro-upgrading device of a certain plant as a raw material, the properties of the raw material are shown in the following table 2, and the catalyst is used as a supplementary refining catalyst of a hydrodewaxing catalyst. The catalyst evaluation process conditions are shown in Table 3 below

TABLE 2 Properties of the feed oils

Table 3 evaluation of process conditions for catalysts of the invention

TABLE 4 catalyst evaluation results

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.