A catalytic support material and a method for preparing the same

Abstract

The application discloses a kind of catalytic carrier materials and preparation method thereof, carrier material includes aluminium oxide, carbon and hydrogen.The preparation method of catalytic carrier material includes the following steps: (1) first auxiliary agent is mixed with first solvent, and first stream is obtained;(2) first carrier, first stream is mixed uniformly, then second carrier, second auxiliary agent and second solvent are mixed uniformly, and then forming treatment is carried out, and second stream is obtained;(3) carbonization treatment is carried out to second stream in the presence of inert atmosphere;(4) the material after carbonization treatment is carried out oxidation treatment in the presence of oxygen-containing atmosphere, and carrier is obtained.The preparation method of the application is simple, easy to realize industrial production, and the carrier obtained has high strength, which can effectively improve the water resistance of the carrier.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of petroleum chemical industry, and relates to a catalytic material and a preparation method thereof, in particular to a catalyst carrier and a preparation method thereof. BACKGROUND

[0002] Generally, alumina is used as the catalyst carrier material of hydrogenation catalysts. The aluminum ions and oxygen ions in alumina form a polycrystalline structure through ionic bonds or covalent bonds. Therefore, under the action of internal and external forces, cracks will be generated along the stress action surface, thereby affecting the mechanical properties and use effect of the catalyst. For example, when processing high-oxygen-containing raw materials such as coal tar, the water contained in the raw materials and the water generated by hydrogenation deoxidization will have a significant impact on the mechanical strength of the catalyst, causing the catalyst to break, thereby affecting the activity and stability of the hydrogenation catalyst.

[0003] A common method for improving the hydrothermal stability of catalysts is to use non-alumina-based catalysts, or to modify alumina with silicon oxide, magnesium oxide, etc., or to convert small crystal grains with high activity into relatively inert large crystal grains by changing the particle size of alumina, thereby sacrificing the hydrogenation activity to improve the hydrothermal stability. For example, a silane modifier is used to perform hydrophobic modification treatment on the surface of the hydrogenation catalyst. This method covers the surface of the hydrogenation catalyst with a layer of silane modifier, thereby improving the water resistance of the hydrogenation catalyst. However, in this process, the surface area and acidity of the catalyst are reduced, which is based on sacrificing the activity of the catalyst to improve the water resistance of the catalyst, and is not a rational solution. Therefore, for the hydrogenation of these oxygen-containing raw materials, how to improve the water resistance of the catalyst while ensuring the performance of the catalyst is the goal of research in this field.

[0004] CN201810203515.X discloses a hydrophobic modified hydrogenation catalyst and a preparation method and application thereof. The preparation method comprises: providing an active component solution containing VIII group metal and / or IB group metal ammonia complex ions; impregnating and drying the TiO2-Al2O3 composite oxide carrier in the active component solution to prepare a catalyst precursor; contacting the catalyst precursor with a carrier gas carrying a silane modifier to perform hydrophobic modification treatment; and heating the catalyst precursor subjected to the hydrophobic modification treatment under a hydrogen atmosphere to prepare the hydrogenation catalyst. The present application uses multiple ammonia molecules complexed on the surface of the VIII group metal and / or IB group metal to realize spatial occupation, thereby being able to adjust the subsequent hydrophobic modification process, and obtaining a hydrogenation catalyst whose catalytic activity is not reduced due to the coverage of active sites by the silane modifier.

[0005] CN201310519826.4 discloses a kind of water-resistant catalyst for hydroxy aldehyde condensation and its preparation method and application, using water-resistant treatment solution is prepared by the following method: 1%-20% carrier precursor or catalyst precursor weight Organic siloxane derivative, such as chloropropyl triethoxysilane, is dispersed in 10 times-50 times mass percentage concentration 1%-5% alkali solution, such as guanidine, tetramethylammonium hydroxide, trimethylethylammonium hydroxide etc. Organic base or sodium hydroxide, cesium hydroxide etc. Inorganic base, stirring time 1h-8h, it is obtained.

[0006] In summary, the high water resistance of the hydrogenation catalyst disclosed in the prior art, the preparation process is more complex, and the activity of the catalyst is significantly reduced, which cannot meet the requirements of the activity and stability of the catalyst in use. SUMMARY

[0007] To overcome the shortcomings in the prior art, the present application provides a catalytic carrier material with good water resistance and a preparation method thereof. In the preparation method of the carrier material, a flexible material is added to the existing alumina-based catalytic material preparation carrier. The flexible material has multiple functional groups, which can effectively combine with alumina. At the same time, the flexibility of the material at high temperature can weaken the gasification of water, maintain the strength of the carrier and improve the water resistance of the carrier. The preparation method is simple and easy to realize industrial production.

[0008] The first aspect of the present application provides a catalytic carrier material, which comprises alumina, carbon and hydrogen. Based on the weight of the carrier material, the content of alumina is 78.2-94.6wt%, the content of carbon is 5-20wt%, and the content of H (elemental) is 0.4-1.8wt%. H exists in the form of C-H bond.

[0009] Further, in the above-mentioned catalytic carrier material, as a preferred embodiment, the pore volume of the carrier material is not less than 0.40mL / g, preferably greater than 0.50mL / g, generally 0.55-0.80mL / g.

[0010] Further, in the above-mentioned catalytic carrier material, as a preferred embodiment, the specific surface area of the carrier material is 120-260m 2 / g, preferably 150-250m 2 / g.

[0011] Further, in the above-mentioned catalytic carrier material, as a preferred embodiment, the total acid content of the carrier material is 0.2-0.6mmol / g, preferably 0.3-0.6mmol / g.

[0012] Further, in the catalytic carrier material, as a preferred embodiment, the side pressure strength of the carrier material is greater than 6 N / mm, preferably greater than 8 N / mm.

[0013] Further, in the catalytic carrier material, as a preferred embodiment, the H / C molar ratio of the carrier material is 0.95-1.3, preferably 0.95-1.25. The H in the carrier material mainly exists in the form of C-H bond, which is derived from the H retained by incomplete carbonization of the high molecular polymer.

[0014] The second aspect of the present application provides a preparation method of a catalytic carrier material, which comprises the following steps:

[0015] (1) mixing a first additive with a first solvent to obtain a first stream;

[0016] (2) mixing the first carrier and the first stream uniformly, then adding a second carrier, a second additive and a second solvent, mixing them uniformly and then performing a molding treatment to obtain a second stream;

[0017] (3) performing a carbonization treatment on the second stream in the presence of an inert atmosphere;

[0018] (4) performing an oxidation treatment on the material after the carbonization treatment in the presence of an oxygen-containing atmosphere to obtain a carrier.

[0019] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the first additive in step (1) is a polymer, and the specific first additive is selected from high molecular polymers, which can be one or more of resin, rubber, plastic and the like, preferably one or more of C5 petroleum resin, C9 petroleum resin, silicone rubber, polyethylene and polyester (PET), and further preferably C9 petroleum resin.

[0020] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the first solvent in step (1) is an organic solvent, and the organic solvent is one or more of benzene and its derivatives, cycloalkane, ketone, alcohol, chlorinated hydrocarbon, and the specific organic solvent can be one or more of benzene, toluene, xylene, cyclohexane, acetone, N-methyl pyrrolidone and trichloromethane; further, the selection of the first solvent is generally based on the selection of the appropriate solvent according to the type of the selected first additive, for example, cyclohexane can be used as the solvent when resin is selected as the first additive, toluene can be used as the solvent when rubber is selected as the first additive, and N-methyl pyrrolidone can be used as the solvent when polyester (PET) is selected as the first additive.

[0021] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the weight ratio of the first solvent to the first additive is 4:1 to 10:1, preferably 4:1 to 8:1.

[0022] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the first carrier in step (2) is at least one of alumina and silicon-containing alumina, preferably, the alumina is alumina obtained by calcining pseudoboehmite, the calcining temperature is 550 to 900°C, the calcining time is 2 to 5 hours, and the calcining is generally performed in an air atmosphere; the specific surface area of the alumina is 200 to 350 m 2 / g, preferably 220 to 330 m 2 / g, and the pore volume is 0.8 to 1.4 mL / g, preferably 0.8 to 1.2 mL / g.

[0023] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the addition ratio of the first carrier to the first stream in step (2) is 1:1.5 to 8:1, preferably 1:1.5 to 4:1, in terms of g / mL, and the mixing is uniform on a mixer, and more specifically, the mixing time can be controlled to be 10 to 60 minutes, preferably 20 to 50 minutes.

[0024] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the second carrier in step (2) is pseudoboehmite, and the pseudoboehmite can be one or more of macro-pore pseudoboehmite and small-pore pseudoboehmite, and is preferably small-pore pseudoboehmite, wherein the macro-pore pseudoboehmite has a specific surface area greater than 260 m 2 / g and a pore volume greater than 0.95 mL / g after calcining at 600°C, and the small-pore pseudoboehmite has a specific surface area greater than 300 m 2 / g and a pore volume greater than 0.50 mL / g after calcining at 600°C, and the second carrier is added in an amount of 5 to 10 wt% based on the alumina.

[0025] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the molding in step (2) is not particularly limited and can be any one of a spherical shape, a strip shape, a three-leaf clover shape, a four-leaf clover shape, etc., and the molding method can be any one of the existing molding methods in the art.

[0026] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the second solvent is an alcohol solution, specifically at least one of an ethanol solution and an ethylene glycol solution, etc., the concentration of the alcohol solution is greater than 50 wt%, preferably 50 wt% to 80 wt%, and the addition amount of the alcohol solution is 1 to 15 wt%, preferably 2 to 15 wt%, based on the addition amount of the alumina on the final carrier.

[0027] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the second additive is starch and / or cellulose; the starch can be one or more of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water caltrop starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch. The cellulose can be one or more of sesbania gum, methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose. The amount of the second additive is 3wt%-10wt% of the aluminum oxide in the final carrier material, preferably 3wt%-8wt%.

[0028] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the mixing in step (2) is not particularly limited and any existing mixing method that can achieve uniform mixing of two or more materials can be used, such as kneading, specifically, kneading on a mixer.

[0029] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the carbonization treatment temperature in step (3) is 450-600°C, and the carbonization treatment time is 2-5h; the inert gas atmosphere can be nitrogen and / or an inert gas, and the inert gas can be at least one of helium, neon, argon, krypton, and xenon.

[0030] Further, in the preparation method of the catalytic carrier material, as a preferred embodiment, the oxidation treatment temperature in step (4) is 400-500°C, and the oxidation treatment time is 0.5-1.5h. The oxygen-containing atmosphere can be oxygen, air, or a mixture of oxygen and an inert gas, and the inert gas atmosphere can be nitrogen and / or an inert gas, and the volume content of oxygen in the mixture is 15%-30%.

[0031] The application also provides a catalytic carrier material prepared by the above method.

[0032] The application further provides a hydrogenation catalyst comprising the above catalytic carrier material.

[0033] Compared with the prior art, the catalytic carrier material and the preparation method thereof have the following advantages:

[0034] 1. In the catalytic support material provided by the present invention, a network structure of CH bonds is constructed between alumina particles. During the reaction process, due to the stretching and shrinking changes of the CH bonds containing plastic materials, the impact of product volume expansion on the final catalyst is reduced, avoiding catalyst breakage, and maintaining good activity stability of the catalyst.

[0035] 2. In the method for preparing the catalyst support material provided by the present invention, a first auxiliary agent combined with alumina is added during the preparation of the support to improve the deformation performance of the material. When used to process oxygen-containing raw materials, the first auxiliary agent has variability under high temperature conditions, which can reduce the influence of water generated by hydrogenation of oxygen in the raw material or water vaporization in the raw material on the strength of the catalyst support, thereby improving the water resistance of the catalyst.

[0036] 3. In the method for preparing the catalytic support material provided by this invention, a two-step mixing method is adopted. First, the first solvent and the first auxiliary agent are mixed evenly, and then mixed with the first support, so that the first auxiliary agent is adsorbed on the first support and forms a coating, constructing a network structure with CH bonds between the alumina particles. Then, in the second step, the second auxiliary agent and the second support are added. Utilizing the multifunctional structure rich in the first auxiliary agent, and simultaneously adding the second solvent miscible with water, the second support containing the first auxiliary agent is better combined with other viscous substances, thereby improving the mechanical strength of the support.

[0037] 4. The method for preparing catalytic support material provided by the present invention eliminates the drying step, which not only simplifies the preparation process, but also allows for the control of the pore structure of the material by leaving a certain amount of moisture in the support precursor, thereby effectively increasing the content of macropores.

[0038] 5. In the method for preparing catalytic support material provided by the present invention, the first auxiliary material is fixed by carbonizing the surface of the support, which enhances the mechanical properties of the catalyst and weakens the interaction between the subsequent active metal and the support; then, shallow oxidation is performed on the surface of the support to enhance the adhesion of different materials and lay the foundation for improving the water resistance of the catalyst. Attached Figure Description

[0039] Figure 1 The infrared spectra of the samples obtained in Example 1, Comparative Example 1, and Comparative Example 3 of the present invention are shown.

[0040] Figure 2 This is a photograph of the carrier after the breakage test obtained in Example 1 of the present invention.

[0041] Figure 3 This is a photograph of the carrier after a breakage test obtained in Comparative Example 1 of the present invention. Detailed Implementation

[0042] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings and specific examples, but it should be noted that the scope of protection of the present application is not limited by these specific embodiments, but is determined by the claims.

[0043] In the context of the present specification, the pore volume, specific surface area and pore size distribution of the support are measured by low temperature nitrogen adsorption. The total acid is measured by pyridine infrared adsorption. C, H are measured by elemental analysis, and the sample infrared spectrum is measured by a Fourier transform infrared spectrometer.

[0044] The crushing test of the support is carried out in a constant temperature oil bath, using dimethyl silicone oil, heated to 200°C, after the support is saturated with water, it is added to the oil bath, and the sample added to the oil bath is counted for crushing condition by using Leica image analysis system.

[0045] In the absence of explicit indication, all percentages, parts, ratios, etc. mentioned in the present specification are based on weight.

[0046] In the context of the present specification, any two or more embodiments of the present application can be combined arbitrarily, and the technical solutions formed thereby are part of the original disclosure of the present specification and also fall within the scope of protection of the present application.

[0047] Example 1

[0048] Take 100g of C9 petroleum resin, add 400g of cyclohexane and stir to dissolve, and wait for use. Take 800g of macroporous pseudo-boehmite and place it in a calcination dish to be calcined in a high temperature furnace, with a calcination temperature of 800°C and a calcination time of 3h, to obtain calcined alumina (specific surface area 250m 2 / g, pore volume 0.95mL / g). Take 300g of calcined alumina powder and 200g of C9 petroleum resin solution, add the calcined alumina powder to a kneader, add the C9 petroleum resin solution in a spraying manner, mix for 30min, then add 40g of pseudo-boehmite (600°C specific surface area 270m 2 / g, pore volume 1.03mL / g), 9.9g of methyl cellulose, mix, then add 40g of ethanol solution (ethanol content 80wt%), mix uniformly, then take out and form into balls on a ball forming device. The formed sample is calcined in a nitrogen atmosphere, with a calcination temperature of 550°C and a calcination time of 4h. After the sample is cooled, it is lightly oxidized in an air atmosphere, with a calcination temperature of 500°C and a calcination time of 0.5h, to prepare 1.0mm microspherical support Z-1, the analysis results of which are shown in Table 1 and Figure 1 .

[0049] Example 2

[0050] Other conditions are the same as example 1, except that C9 petroleum resin is replaced by silicone rubber, cyclohexane is replaced by toluene, and the molded sample is calcined under nitrogen atmosphere, the calcination temperature is 600℃, and the calcination time is 3h. 1.0mm microsphere carrier Z-2 is prepared, and the analysis results are shown in Table 1.

[0051] Example 3

[0052] Other conditions are the same as example 1, except that the calcination temperature of macroporous pseudoboehmite is changed from 800℃ to 700℃, and the calcined alumina (specific surface area 281m 2 / g, pore volume 1.00mL / g) is obtained. 300g of the calcined alumina powder and 150g of C9 petroleum resin solution are taken, the mixing time is changed to 40min, and 50g of ethylene glycol solution (ethylene glycol content 50wt%) is added after mixing. 1.0mm microsphere carrier Z-3 is prepared, and the analysis results are shown in Table 1.

[0053] Example 4

[0054] PET 80g is weighed, and after stirring, it is dissolved in 500g of N-methyl pyrrolidone, and is ready for use. 800g of macroporous pseudoboehmite is weighed and placed in a calcination boat for calcination in a high-temperature furnace, the calcination temperature is 750℃, and the calcination time is 3h. The calcined alumina (specific surface area 273m 2 / g, pore volume 1.00mL / g) is obtained. 300g of the calcined alumina powder and 180g of polyethylene terephthalate solution are weighed, the calcined alumina powder is added to a kneader, and the polyethylene terephthalate solution is added in a spraying manner, mixed for 30min, and then 60g of pseudoboehmite (specific surface area 330m 2 / g at 600℃, pore volume 0.72mL / g), 25g of starch are added, 50g of ethylene glycol solution (ethylene glycol content 70%) is added after mixing, and the mixture is uniformly mixed and taken out to be formed into a ball on a ball forming device. The molded sample is calcined under nitrogen atmosphere, the calcination temperature is 600℃, and the calcination time is 2h. After cooling, the sample is subjected to shallow oxidation in air atmosphere, the calcination temperature is 550℃, and the calcination time is 0.5h. 1.0mm microsphere carrier Z-1 is prepared, and the analysis results are shown in Table 1.

[0055] Example 5

[0056] Other conditions are the same as example 4, except that the calcination temperature of macroporous pseudoboehmite is changed from 700℃ to 900℃, and the calcined alumina (specific surface area 205m 2 / g, pore volume is 1.03mL / g). Take 300g of calcined alumina powder and 150g of polyethylene terephthalate, change the mixing time to 50min, add 75g of propylene glycol solution (ethanol content is 50%), and prepare 1.0mm microsphere carrier Z-3. The analysis results are shown in Table 1.

[0057] Comparative Example 1

[0058] Weigh out 400g of cyclohexane solution and set aside. Weigh out 800g of macroporous boehmite, place it in a calcining dish, and calcine it in a high-temperature furnace at 800℃ for 3 hours to obtain calcined alumina (specific surface area 250m²). 2 / g, pore volume is 0.95mL / g). Weigh 300g of calcined alumina powder and 200g of cyclohexane solution. Add the calcined alumina powder to a kneader, and add the cyclohexane solution by spraying. Mix for 30min, then add 40g of boehmite (specific surface area 270m² at 600℃). 2 9.9 g of methylcellulose (with a pore volume of 1.03 mL / g) was mixed with 40 g of ethanol solution (80% ethanol content), and the mixture was then removed and spherically formed using a spheroidizing device. The spheroidized sample was calcined under a nitrogen atmosphere at 550℃ for 4 h. After cooling, the sample was lightly oxidized in air at 500℃ for 0.5 h to prepare 1.0 mm microsphere carrier F-1. The analytical results are shown in Table 1 and [Table data would be inserted here]. Figure 1 .

[0059] Comparative Example 2

[0060] Weigh 100g of C9 petroleum resin, add 400g of cyclohexane, and stir until completely dissolved. Set aside. Weigh 800g of macroporous pseudoboehmite, place it in a calcining dish, and calcine it in a high-temperature furnace at 800℃ for 3 hours to obtain calcined alumina (specific surface area 250m²). 2 / g (pore volume 0.95mL / g). Weigh 300g of calcined alumina powder and 200g of C9 petroleum resin solution. Add the calcined alumina powder to a kneader, and add the C9 petroleum resin solution by spraying. Mix for 30min, then add 40g of boehmite (specific surface area 270m² / g at 600℃, pore volume 1.03mL / g) and 9.9g of methylcellulose. Mix, then add 40g of purified water, mix thoroughly, and remove. Form the mixture into spheres using a sphere forming device. The formed samples are calcined under a nitrogen atmosphere at 550℃ for 4h. After cooling, the samples are lightly oxidized in air at 500℃ for 0.5h to prepare 1.0mm microsphere carrier F-2. The analytical results are shown in Table 1.

[0061] Comparative Example 3

[0062] Take 100 g of C9 petroleum resin, add 400 g of cyclohexane and stir to dissolve. Take 800 g of macroporous pseudo-boehmite and place in a calcination dish and calcine in a high temperature furnace at 800°C for 3 h to obtain calcined alumina (specific surface area 250 m 2 / g, pore volume 0.95 mL / g). Take 300 g of the calcined alumina powder and 200 g of the C9 petroleum resin solution, add the calcined alumina powder to a kneader, add the C9 petroleum resin solution by spraying, mix for 30 min, then add 40 g of pseudo-boehmite (600°C specific surface area 270 m2 / g, pore volume 1.03 mL / g) and 9.9 g of methyl cellulose, mix, then add 40 g of an ethanol solution (ethanol content 80%), mix uniformly, and then take out and form into spheres on a sphere forming device. The formed sample is calcined in a nitrogen atmosphere at 750°C for 4 h. A 1.0 mm microsphere carrier F-3 is prepared, and the analysis results are shown in Table 1.

[0063] Table 1 Analysis results of samples obtained in examples and comparative examples

[0064]

[0065]

[0066] As can be seen from the table and the figure, the carrier prepared in the present application has a C and H containing additive added and special preparation conditions, in the infrared characterization, 1450-1650 cm -1 is the C=C vibration peak, 800-860 cm -1 is the characteristic peak of CH of p-xylene (adjacent to 2 H), which shows that the carrier maintains good characteristics during preparation, has a larger pore volume and specific surface area, higher mechanical strength, and lower breakage rate, and is very suitable for hydrogenation reactions of oxygen-containing compounds.

Claims

1. A method for preparing a catalytic carrier material, the method comprising the following steps: (1) mixing a first additive with a first solvent to obtain a first stream; the first additive is a high molecular polymer selected from one or more of resin, rubber and plastic; the first solvent is an organic solvent; the weight ratio of the first solvent to the first additive is 4:1 to 10:1; (2) mixing the first stream with a first carrier to obtain a second stream; (3) carbonizing the second stream in the presence of an inert atmosphere; (4) oxidizing the carbonized material in the presence of an oxygen-containing atmosphere to obtain the carrier. The first additive in step (1) is one or more of C5 petroleum resin, C9 petroleum resin, silicone rubber, polyethylene and polyester. (2) mixing the first carrier, the first stream uniformly, then adding the second carrier, the second additive and the second solvent uniformly to carry out a molding treatment to obtain the second stream; wherein the first carrier is at least one of alumina and silicon-containing alumina, the specific surface area of the alumina is 200-350 m 2 / g, the pore volume is 0.8-1.4 mL / g; the second carrier is pseudoboehmite; the second solvent is an alcohol solution, the alcohol solution is at least one of an ethanol solution and a glycol solution; the second additive is starch and / or cellulose; The first additive in step (1) is C9 petroleum resin. The first solvent in step (1) is one or more of benzene and its derivatives, cycloalkane, ketone, alcohol and chlorinated hydrocarbon.

2. The method for producing a catalytic support material according to claim 1, wherein, The first solvent is one or more of benzene, toluene, xylene, cyclohexane, acetone, N-methyl pyrrolidone and trichloromethane.

3. The method of preparing a catalytic support material according to claim 1 or 2, wherein, The weight ratio of the first solvent to the first additive is 4:1 to 8:

1.

4. The method for producing a catalytic support material according to claim 1, wherein, The alumina is alumina obtained by calcining pseudo-boehmite.

5. The process for the preparation of a catalytic support material according to claim 1 or 4, wherein, The ratio of the first carrier to the first stream in step (2) is 1:1.5 to 8:1 by g / mL.

6. The method of making a catalytic support material according to claim 1, wherein, The ratio of the first carrier to the first stream in step (2) is 1:1.5 to 4:1 by g / mL.

7. The method of making a catalytic support material according to claim 1, wherein, The concentration of the alcohol solution is greater than 50 wt%.

8. The method of making a catalytic support material according to claim 1, wherein, The specific surface area of the alumina is 220 to 330 m 2 / g, and the pore volume is 0.8 to 1.2 mL / g.

9. The method of making a catalytic support material according to claim 1, wherein, The concentration of the alcohol solution is 50 wt% to 80 wt%.

10. The method of making a catalytic support material according to claim 1, wherein, The starch is one or more of green bean starch, cassava starch, sweet potato starch, sweet potato starch, potato starch, cereal starch, water chestnut starch, lotus root starch and corn starch; the cellulose is one or more of sesbania gum, methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose and phenyl cellulose.

11. The method of making a catalytic support material according to claim 1, wherein, The starch is corn starch and / or potato starch.

12. The method of making a catalytic support material according to claim 1, wherein, The carbonization temperature in step (3) is 450 to 600°C, and the carbonization time is 2 to 5 hours; the inert atmosphere is nitrogen and / or an inert gas, and the inert gas is at least one of helium, neon, argon, krypton and xenon.

13. The method of making a catalytic support material according to claim 1, wherein, The oxidation temperature in step (4) is 400 to 500°C, and the oxidation time is 0.5 to 1.5 hours.

14. The method of making a catalytic support material according to claim 1, wherein, 17. A catalytic carrier material prepared by the method of any one of claims 1 to 16.

15. The method of making a catalytic support material according to claim 1, wherein, The catalytic carrier material comprises alumina, carbon and hydrogen, wherein the content of alumina is 78.2 to 94.6 wt%, the content of carbon is 5 to 20 wt%, and the content of H (elemental) is 0.4 to 1.8 wt% based on the weight of the catalytic carrier material; wherein H exists in the form of C-H bond.

16. The method of making a catalytic support material according to claim 1, wherein, The pore volume of the carrier material is not less than 0.40 mL / g. The pore volume of the carrier material is greater than 0.50 mL / g.

18. The catalytic support material of claim 17, wherein, The pore volume of the carrier material is 0.55 to 0.80 mL / g.

19. The catalytic support material according to claim 17 or 18, wherein, The total acid content of the carrier material is 0.2 to 0.6 mmol / g.

20. The catalytic support material according to claim 17 or 18, wherein, ​ 21. The catalytic support material according to claim 17 or 18, wherein, ​ 22. The catalytic support material of claim 17 or 18, wherein, The specific surface area of the support material is between 120 and 260 m2 / g. 2 / g.

23. The catalytic support material of claim 17 or 18, wherein, The specific surface area of the support material is 150-250 m 2 / g.

24. The catalytic support material of claim 17 or 18, wherein, ​ 25. The catalytic support material of claim 17 or 18, wherein, The total acid content of the support material is 0.3 to 0.6 mmol / g.

26. The catalytic support material of claim 17 or 18, wherein, The side crush strength of the support material is greater than 6 N / mm.

27. The catalytic support material of claim 17 or 18, wherein, The side crush strength of the support material is greater than 8 N / mm.

28. The catalytic support material of claim 17 or 18, wherein, The H / C molar ratio of the support material is 0.95 to 1.

3.

29. The catalytic support material of claim 17 or 18, wherein, The H / C molar ratio of the support material is 0.95 to 1.

25.

30. A hydrogenation catalyst comprising the catalytic support material of any one of claims 17-29.

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