阅读说明：本技术 一种渣油加氢保护剂载体、催化剂及其制备方法 (Residual oil hydrogenation protective agent carrier, catalyst and preparation method thereof ) 是由 隋宝宽 季洪海 彭冲 吕振辉 于 2019-04-17 设计创作，主要内容包括：本发明公开了一种渣油加氢保护剂载体、催化剂及其制备方法。所述载体为改性氧化铝基载体,所述改性氧化铝基载体含有改性元素、第一加氢活性金属组分；所述改性氧化铝基载体包括主体改性氧化铝和棒状改性氧化铝,所述的主体改性氧化铝为具有微米级孔道的氧化铝,其中至少部分棒状改性氧化铝分布在主体改性氧化铝的外表面和孔直径D为5-10μm的微米级孔道中；所述改性元素为钒,所述第一加氢活性金属组分为钼。采用本发明加氢保护剂载体制备的催化剂具有大分子扩散性能好、容杂质能力强、沥青质转化率高等特性,特别适用于渣油加氢处理工艺中。(The invention discloses a residual oil hydrogenation protective agent carrier, a catalyst and a preparation method thereof. The carrier is a modified alumina-based carrier, and the modified alumina-based carrier contains a modified element and a first hydrogenation active metal component; the modified alumina-based carrier comprises main body modified alumina and rodlike modified alumina, wherein the main body modified alumina is alumina with micron-sized pore channels, and at least part of rodlike modified alumina is distributed on the outer surface of the main body modified alumina and the micron-sized pore channels with the pore diameter D of 5-10 mu m; the modified element is vanadium, and the first hydrogenation active metal component is molybdenum. The catalyst prepared by the hydrogenation protective agent carrier has the characteristics of good macromolecule diffusion performance, strong impurity-containing capacity, high asphaltene conversion rate and the like, and is particularly suitable for a residual oil hydrotreating process.)

1. A residual oil hydrogenation protective agent carrier is characterized in that: the carrier is a modified alumina-based carrier, and the modified alumina-based carrier contains a modified element and a first hydrogenation active metal component; the modified alumina-based carrier comprises main body modified alumina and rodlike modified alumina, wherein the main body modified alumina is alumina with micron-sized pore channels, and at least part of rodlike modified alumina is distributed on the outer surface of the main body modified alumina and the micron-sized pore channels with the pore diameter D of 5-10 mu m; the modified element is vanadium, and the first hydrogenation active metal component is molybdenum.

2. The carrier of claim 1, wherein: the total content of the modified elements is 0.1 to 1 percent, preferably 0.2 to 0.6 percent in terms of oxide, based on the weight of the residual oil hydrogenation protective agent carrier; the content of the first hydrogenation active metal component is 0.2-1.5 percent of molybdenum calculated by oxide, and preferably 0.5-1.0 percent.

3. The carrier of claim 1, wherein: the rodlike modified alumina is basically distributed on the outer surface of the main body modified alumina and in the micron-sized pore channels.

4. The carrier of claim 1, wherein: the length of the rod-shaped modified alumina in the micron-sized pore channel is mainly 0.3D-0.9D; the length of the outer surface rod-shaped modified alumina is mainly 3-8 μm.

5. The carrier of claim 1, wherein: the diameter of the rod-shaped modified alumina is 100-300 nm.

6. The carrier of claim 1, wherein: at least one end of at least part of the rod-shaped modified alumina is attached to the micron-sized pore channel wall of the main body modified alumina, preferably at least one end of at least part of the rod-shaped modified alumina is combined on the micron-sized pore channel wall and is integrated with the main body modified alumina, and further preferably at least one end of the rod-shaped modified alumina in the micron-sized pore channel is combined on the micron-sized pore channel wall and is integrated with the main body modified alumina.

7. The carrier of claim 1, wherein: one end of at least part of the rod-shaped modified alumina is attached to the outer surface of the main modified alumina, preferably one end of at least part of the rod-shaped modified alumina is combined with the outer surface of the main modified alumina, and the other end of the rod-shaped modified alumina extends outwards and is integrated with the main modified alumina, and further preferably, one end of the rod-shaped modified alumina on the outer surface of the main modified alumina is combined with the outer surface of the main modified alumina, and the other end of the rod-shaped modified alumina extends outwards and is integrated with the main modified alumina.

8. The carrier of claim 1, wherein: the coverage rate of the rod-shaped modified alumina in the micron-sized pore channel of the main body modified alumina is 70-95%, and the coverage rate of the rod-shaped modified alumina on the outer surface of the main body modified alumina is 70-95%.

9. The carrier of claim 1, wherein: the specific surface area of the carrier is 150-300m²(iv)/g, pore volume of 0.8-1.9mL/g, crush strength of 9-18N/mm.

10. The carrier of claim 1, wherein: the pores formed by the rod-shaped modified alumina in the carrier in a disordered and staggered manner are concentrated between 100-800 nm.

11. The carrier of claim 1, wherein: the pore distribution of the carrier is as follows: the pore volume occupied by the pores with the pore diameter of less than 10nm is less than 15 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 15-35nm is 20-45 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-800nm is 25-45 percent of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 1000nm is 10-25 percent of the total pore volume, preferably 10-20 percent.

12. A process for preparing a residual hydro-protectant carrier according to any of claims 1-11, comprising:

(1) dipping a physical pore-enlarging agent in a solution containing a modification element, kneading, molding, drying and roasting the dipped physical pore-enlarging agent, pseudo-boehmite and a first hydrogenation active metal component source to obtain an intermediate;

(2) and (2) immersing the intermediate obtained in the step (1) into an ammonium bicarbonate solution, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain the residual oil hydrogenation protective agent carrier.

13. The method of claim 12, wherein: the physical pore-enlarging agent in the step (1) is one or more of activated carbon and sawdust, the particle size of the physical pore-enlarging agent is 5-10 mu m, and the addition amount of the physical pore-enlarging agent is 20-35 wt% of the weight of the intermediate.

14. The method of claim 12, wherein: the solution containing the modification element in the step (1) is a vanadium-containing acid solution or salt solution, preferably a vanadium-containing salt solution, and the vanadium-containing salt solution is one or more of ammonium vanadate and ammonium metavanadate; the first hydrogenation active metal component source is one or more of ammonium molybdate and ammonium paramolybdate.

15. The method of claim 12, wherein: the drying temperature in the step (1) is 80-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 650-750 ℃, and the roasting time is 4-6 hours.

16. The method of claim 12, wherein: the mass ratio of the using amount of the ammonium bicarbonate solution in the step (2) to the intermediate obtained in the step (1) is 4:1-10:1, and the mass concentration of the ammonium bicarbonate solution is 15% -25%.

17. The method of claim 12, wherein: and (2) performing sealing pretreatment before sealing heat treatment, wherein the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is lower than that before the pretreatment by at least 3 ℃/min, preferably at least 5 ℃/min.

18. The method of claim 12, wherein: the drying temperature in the step (2) is 160 ℃ and the drying time is 6-10 hours, the roasting temperature is 600 ℃ and 750 ℃ and the roasting time is 4-6 hours.

19. A residual oil hydrogenation protection catalyst, which comprises a residual oil hydrogenation protection agent carrier and a second hydrogenation active metal component, wherein the second hydrogenation active metal component is molybdenum and nickel, and the residual oil hydrogenation protection agent carrier adopts the residual oil hydrogenation protection agent carrier in any one of claims 1 to 11.

20. The catalyst of claim 19, wherein: the total content of molybdenum and nickel in the hydrogenation active metal components is 5wt% -15wt% based on the weight of the residual oil hydrogenation protection catalyst, wherein the weight ratio of molybdenum and nickel introduced by the second hydrogenation active metal component calculated by oxides is as follows: 3.0:1-5.0:1.

Technical Field

The invention relates to the field of catalyst carrier preparation, in particular to a residual oil hydrogenation protective agent carrier, a residual oil hydrogenation protective agent catalyst and a preparation method thereof.

Background

Currently, hydrotreating is still the most important means for producing high quality, environmentally friendly petroleum products. The core of the hydrotreating technology is the catalyst, and for hydrotreating heavy components of petroleum (such as VGO, especially residual oil), the size of the pore diameter and the pore volume of the catalyst directly influence the exertion of the activity of the catalyst.

The residual oil hydrogenation protecting catalyst has the main function of eliminating iron, calcium, nickel, vanadium and other matters from residual oil. The carrier material used by the existing residual oil hydrogenation protection catalyst is generally macroporous alumina and modified products thereof. The common preparation method of the macroporous alumina comprises the following steps: physical pore-forming method and high-temperature roasting method.

CN1120971A discloses a preparation method of an alumina carrier with a bimodal pore structure. The method uniformly mixes two or more than two pseudo-boehmite dry glue prepared by different raw material route methods, and then carries out peptization, molding, drying and roasting treatment to obtain the alumina with the specific surface area of 100-200 m-²The pore volume is 0.7-1.6mL/g, the double-peak pores are respectively concentrated in the areas of 3.5-35nm and more than 100nm, wherein the pore volume occupied by the pores with the diameter of more than 100nm is 10% -56% of the total pore volume. However, the content of pores with the diameter of over 1000nm is low, which is not beneficial to the precipitation and removal of iron, calcium, nickel, vanadium and other substances in the residual oil, and the asphaltene conversion capability is to be improved.

CN106622307A discloses a hydrogenation protective agent, a preparation method and an application thereof, the protective agent contains an active metal component and a modified hydrogenation catalyst carrier, the modified hydrogenation catalyst carrier is prepared by the following method, the method comprises the following steps: the carrier subjected to the hydrothermal treatment is repeatedly impregnated and dried in sequence, and the dried product obtained at the last time is calcined. The protective agent can obtain a comprehensive metal removal effect in the application of heavy oil hydrotreating, and the hydrogenation protective agent is not easy to form carbon deposition, but the asphaltene conversion capability of the catalyst needs to be improved.

CN106622262A discloses a hydrogenation protective agent and a preparation method and application thereof, the protective agent contains an active metal component and a modified hydrogenation catalyst carrier, the modified hydrogenation catalyst carrier comprises a carrier and a metal auxiliary and an acid auxiliary loaded on the carrier, the metal auxiliary and the acid auxiliary are distributed on the carrier in a layered manner, the shell layer is the metal auxiliary, the core layer is the acid auxiliary, the metal auxiliary is a group IA metal component and/or a group IIA metal component, and the acid auxiliary is at least one component selected from F, P and B. The hydrogenation protective agent can obtain a comprehensive metal removal effect in the application of heavy oil hydrogenation treatment, and the hydrogenation protective agent is not easy to form carbon deposition, but has a complex preparation process, poor pore passage connectivity and low asphaltene conversion capability.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a residual oil hydrogenation protective agent carrier, a residual oil hydrogenation protective agent catalyst and a preparation method thereof. The catalyst prepared by the hydrogenation protective agent carrier has the characteristics of good macromolecule diffusion performance, strong impurity-containing capacity, high asphaltene conversion rate and the like, and is particularly suitable for residual oil hydrotreating process.

The invention provides a residual oil hydrogenation protective agent carrier in a first aspect, wherein the carrier is a modified alumina-based carrier, and the modified alumina-based carrier contains a modified element and a first hydrogenation active metal component; the modified alumina-based carrier comprises main body modified alumina and rodlike modified alumina, wherein the main body modified alumina is alumina with micron-sized pore channels, and at least part of rodlike modified alumina is distributed on the outer surface of the main body modified alumina and the micron-sized pore channels with the pore diameter D of 5-10 mu m; the modified element is vanadium, and the first hydrogenation active metal component is molybdenum.

The micron-sized pore canal in the invention refers to a micron-sized pore canal with the pore diameter D of 5-10 μm.

The total content of the modified elements is 0.1 to 1 percent, preferably 0.2 to 0.6 percent in terms of oxide, based on the weight of the residual oil hydrogenation protective agent carrier; the content of the first hydrogenation active metal component is 0.2-1.5 percent of molybdenum calculated by oxide, and preferably 0.5-1.0 percent.

In the modified alumina-based carrier, the rodlike modified alumina is basically distributed on the outer surface of the main modified alumina and in the micron-sized pore channels. The rod-shaped modified alumina distributed on the outer surface of the main body modified alumina and in the micron-sized pore channels accounts for more than 95 percent of the total weight of all the rod-shaped alumina, and preferably more than 97 percent.

In the modified alumina-based carrier, the length of the rod-shaped modified alumina in the micron-sized pore channel is mainly 0.3D-0.9D (which is 0.3-0.9 time of the diameter of the micron-sized pore channel), namely the length of more than 85 percent of the rod-shaped alumina in the micropore is 0.3D-0.9D by weight; the length of the rod-shaped modified alumina on the outer surface is mainly 3-8 μm, namely, the length of more than 85 percent of the rod-shaped modified alumina on the outer surface is 3-8 μm.

The diameter of the rod-shaped modified alumina is 100-300 nm.

Wherein, in the micron-sized pore canal of the main body modified alumina, the rod-shaped modified alumina is distributed in a disordered and mutually staggered state.

Wherein at least one end of at least part of the rod-shaped modified alumina is attached to the micron-sized pore channel wall of the main body modified alumina, and preferably at least one end of at least part of the rod-shaped modified alumina is bonded to the micron-sized pore channel wall and is integrated with the main body modified alumina. Further preferably, at least one end of the rod-like modified alumina in the micron-sized pore channel is bonded to the wall of the micron-sized pore channel, and is integrated with the main body of the modified alumina.

Wherein the rod-like modified alumina is distributed in a disordered and mutually staggered state on the outer surface of the main body modified alumina.

Wherein one end of at least part of the rod-shaped modified alumina is attached to the outer surface of the main modified alumina, and preferably, one end of at least part of the rod-shaped modified alumina is combined with the outer surface of the main modified alumina, and the other end of the rod-shaped modified alumina extends outwards and is integrated with the main modified alumina. Further preferably, one end of the rod-shaped modified alumina on the outer surface of the body modified alumina is bonded to the outer surface of the body modified alumina, and the other end thereof protrudes outward and is integrated with the body.

In the modified alumina-based carrier, the coverage rate of the rod-shaped modified alumina in the micron-sized pore canal of the main body modified alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface of the inner surface of the micron-sized pore canal of the main body modified alumina, which is occupied by the rod-shaped modified alumina, in the inner surface of the micron-sized pore canal of the main body modified alumina. The coverage rate of the rod-shaped modified alumina on the outer surface of the main body modified alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface occupied by the rod-shaped modified alumina on the outer surface of the main body modified alumina.

The residual oil hydrogenation protective agent carrier has the following properties: the specific surface area is 150-300m²(iv) g, pore volume of 0.8-1.9mL/g, crush strength of 9-18N/mm.

The residual oil hydrogenation protective agent carrier of the invention is characterized in that the pores formed by the disordered mutual interlacing of the rod-shaped modified alumina are concentrated between 100 and 800 nm.

The pore distribution of the residual oil hydrogenation protective agent carrier is as follows: the pore volume occupied by the pores with the pore diameter of less than 10nm is less than 15 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 15-35nm is 20-45 percent of the total pore volume, the pore volume occupied by the pores with the pore diameter of 100-800nm is 25-45 percent of the total pore volume, and the pore volume occupied by the pores with the pore diameter of more than 1000nm is 10-25 percent of the total pore volume, preferably 10-20 percent.

The second aspect of the invention provides a preparation method of a residual oil hydrogenation protective agent carrier, which comprises the following steps:

(1) dipping a physical pore-enlarging agent in a solution containing a modification element, kneading, molding, drying and roasting the dipped physical pore-enlarging agent, pseudo-boehmite and a first hydrogenation active metal component source to obtain an intermediate;

(2) and (2) immersing the intermediate obtained in the step (1) into an ammonium bicarbonate solution, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain the residual oil hydrogenation protective agent carrier.

In the method, the physical pore-expanding agent in the step (1) can be one or more of activated carbon and wood chips, the particle size of the physical pore-expanding agent is about 5-10 mu m, and the addition amount of the physical pore-expanding agent is 20-35 wt% of the weight of the intermediate. The solution containing the modification element is a vanadium-containing acid solution or salt solution, preferably a vanadium-containing salt solution, and the vanadium-containing salt solution is one or more of ammonium vanadate and ammonium metavanadate. The first hydrogenation active metal component source is one or more of ammonium molybdate and ammonium paramolybdate.

In the method of the present invention, the pseudoboehmite described in the step (1) may be a pseudoboehmite prepared by any method, for example, prepared by a precipitation method, an aluminum alkoxide hydrolysis method, an inorganic salt sol-gel method, a hydrothermal method, a vapor deposition method, and the like.

In the method, the kneading molding in the step (1) is carried out by adopting a conventional method in the field, and a proper amount of conventional molding aids, such as one or more of peptizing agents, extrusion aids and the like, can be added according to needs in the molding process. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like; the extrusion aid is sesbania powder.

In the method, the drying temperature in the step (1) is 80-160 ℃, and the drying time is 6-10 hours. The roasting temperature is 650-750 ℃, and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere. The intermediate may be in the form of a conventional alumina support, such as a sphere, having a particle size of typically 0.5-8.0mm, such as a bar, clover, etc., having a diameter of about 0.2-3.0mm and a length of about 0.5-8.0 mm.

In the method, the mass ratio of the using amount of the ammonium bicarbonate solution in the step (2) to the intermediate obtained in the step (1) is 4:1-10:1, and the mass concentration of the ammonium bicarbonate solution is 15-25%.

In the method of the invention, the sealing heat treatment temperature in the step (2) is 120-.

In the method of the invention, the step (2) is preferably carried out before the sealing heat treatment, the sealing pretreatment is carried out, the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is at least 3 ℃/min, preferably at least 5 ℃/min lower than that before the pretreatment.

In the method of the invention, the drying temperature in the step (2) is 160 ℃ for 6-10 hours, the roasting temperature is 600 ℃ for 750 ℃ for 4-6 hours.

In a third aspect, the invention provides a hydrogenation protection catalyst, which comprises the residual oil hydrogenation protective agent carrier and a second hydrogenation active metal component, wherein the second hydrogenation active metal component is molybdenum and nickel.

The residual oil hydrogenation protection catalyst takes the weight of the residual oil hydrogenation protection catalyst as a reference, and the total content of the hydrogenation active metal components, namely molybdenum and nickel, is 5-15 wt%. Wherein the weight ratio of molybdenum to nickel in the second hydrogenation active metal component calculated by oxide is as follows: 3.0:1-5.0:1.

The fourth aspect of the present invention provides a preparation method of the above hydrogenation protection catalyst, which comprises: and (3) dipping the solution containing the second hydrogenation active metal component into a residual oil hydrogenation protective agent carrier, drying and roasting to obtain the hydrogenation protection catalyst.

The solution containing the second active metal component source is an acid solution, an aqueous solution or an ammonia solution containing molybdenum and nickel. Wherein the content of molybdenum is 5.0-17.5g/100mL calculated by metal oxide, and the content of nickel is 1.5-5.0g/100mL calculated by metal oxide.

The impregnation may be carried out by a conventional impregnation method, and may be carried out by an unsaturated impregnation method, a saturated impregnation method, or the like, and a saturated impregnation method is preferably used. The drying temperature is 100-160 ℃, the drying time is 6-10 hours, the roasting temperature is 450-650 ℃, and the roasting time is 4-6 hours.

The residual oil hydrogenation protection catalyst of the invention can also contain one or more auxiliary agents, such as fluorine, boron, silicon and the like. The weight content of the auxiliary agent in the catalyst is less than 10.0 percent, preferably 0.1 to 10.0 percent in terms of oxide.

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

1. the hydrogenation protective agent carrier of the invention fully utilizes the micron-scale pore canal of the intermediate, the rod-shaped modified alumina grows in the micron-scale pore canal, and the rod-shaped modified alumina is distributed in a disordered and staggered manner, so that on one hand, the penetrability of the micron-scale pore canal is maintained, the specific surface area of the hydrogenation protective agent carrier is improved, the mechanical strength is enhanced, on the other hand, the gas generated during the roasting of the physical pore-enlarging agent plays a certain hole-enlarging role on the nanometer-scale pore canal, the penetrability and the uniformity of the nanometer-scale pore canal are further promoted, and the diffusion capacity of reactant molecules is improved. Therefore, the hydrogenation protective agent carrier of the invention overcomes the problem that the large aperture, the specific surface area and the mechanical strength are not compatible caused by adopting a physical pore-expanding agent.

2. In the process of preparing the hydrogenation protective agent carrier, the hydrogenation protective agent carrier is pretreated at a certain temperature before sealing heat treatment, the pretreatment condition is relatively mild, and NH is slowly formed on the outer surface of an intermediate in the sealed and hydrothermal mixed atmosphere of carbon dioxide and ammonia gas₄Al(OH)₂CO₃Crystal nuclei, raising the reaction temperature NH during the post-heat treatment₄Al(OH)₂CO₃The crystal nucleus continues to grow evenly to make rod-shaped NH₄Al(OH)₂CO₃Having uniform diameter and length while increasing rod-like NH₄Al(OH)₂CO₃Coverage on the outer surface of the intermediate body and the inner surface of the micron-sized pore channel. NH (NH)₄Al(OH)₂CO₃The gases such as ammonia gas and carbon dioxide generated during thermal decomposition play a good role in expanding the pore of the carrier intermediate again, so that the penetration and uniformity of the carrier pore are further promoted, and the diffusion capability of reactant molecules is improved.

3. According to the invention, a vanadium modified substance is loaded into a physical pore-expanding agent, and the properties of the micron-sized pore channel and the rod-shaped modified alumina in the micron-sized pore channel are modulated by the corresponding modified substance during roasting; meanwhile, part of the active metal component molybdenum is doped into the carrier during carrier forming, the active metal component is secondarily dispersed on the surface of the carrier in the later hydrothermal treatment process, the other part of the active metal component molybdenum and nickel adopts an impregnation mode to impregnate the modified alumina-based carrier, and the components are mutually cooperated, so that the action of the active metal and the carrier is effectively adjusted, and the metal capacity and asphaltene conversion capacity at the macropore of the catalyst are improved.

Drawings

FIG. 1 is an SEM image of a residue hydro-protecting agent carrier obtained in example 1;

wherein the reference numbers are as follows: 1-main body modified alumina, 2-rod-shaped modified alumina and 3-micron pore canal.

Detailed Description

The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples. In the present invention, wt% is a mass fraction and v% is a volume fraction.

Application N₂Physical adsorption-desorption characterization of the pore structures of the catalyst carriers and catalysts of the examples and comparative examples, the specific operations are as follows: adopting ASAP-2420 type N₂And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter below 50nm is obtained according to a BJH model.

Mercury pressing method: the pore diameter distribution of the carrier and the catalyst of the examples and the comparative examples is characterized by applying a mercury porosimeter, and the specific operation is as follows: and characterizing the distribution of sample holes by using an American microphone AutoPore9500 full-automatic mercury porosimeter. The samples were dried, weighed into an dilatometer, degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and filled with mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm^-1The distribution ratio of pore diameter of 100nm or more is measured by mercury intrusion method.

A scanning electron microscope is used for representing the microstructures of the catalyst and the catalyst carrier, and the specific operation is as follows: a JSM-7500F scanning electron microscope is adopted to represent the microstructure of the catalyst and the catalyst carrier, the accelerating voltage is 5KV, the accelerating current is 20 muA, and the working distance is 8 mm.