CN104888766A - Hydrogenation deoxidation catalyst and preparation method thereof - Google Patents

Abstract

The invention relates to a hydrodeoxygenation catalyst, which is prepared by loading a hydrogenation active metal component on a carrier through an impregnation method, and the carrier is an ordered mesoporous carbon/silica-alumina composite material; Based on the sum of mass percentages of aluminum oxide and aluminum oxide as 100%, carbon is 10-80%, and the balance is silicon oxide and aluminum oxide, wherein the molar ratio of silicon to aluminum is 7-300; the specific surface area of the catalyst is 200-450 m ² / g, the pore volume is 0.20-0.40 cm ³ /g, and the pore diameter is 3.0-6.0 nm. The catalyst can hydrodeoxygenate and upgrade the phenolic substances in the bio-oil/water mixed system. The efficiency and selectivity of alkanes were significantly improved.

Description

A kind of hydrodeoxygenation catalyst and preparation method thereof

technical field

The invention belongs to the technical field of material preparation and catalysis, and in particular relates to a hydrodeoxygenation catalyst and a preparation method thereof, in particular to a catalyst for hydrodeoxygenation of phenolic substances in an oil/water mixed system.

Background technique

Facing the irreversible consumption of fossil fuels and the impact of the resulting greenhouse gas emissions on the environment, it is imminent to actively develop environmentally friendly renewable and clean energy. As a renewable energy source, biomass can not only replace the increasingly depleted fossil fuels, but also reduce greenhouse gas emissions. Biomass can be converted into liquid fuel - bio-oil by fast pyrolysis technology. Bio-oil is a complex mixture of different oxygenated compounds (acids, phenols, aldehydes, ketones and alcohols, etc.) and water (15-30 wt.%). Due to its high oxygen content and certain corrosiveness, it is not suitable for direct use in engines, and further hydrodeoxidation refining is required to improve the quality of bio-oil. Among them, phenolic substances account for about 30 wt.% of bio-oil, including phenol, guaiacol, etc., which are the main harmful components that affect the stability and combustion performance of bio-oil. substances removed.

Co-Mo and Ni-Mo catalysts used for hydrodesulfurization in the petrochemical industry were first used in the research of hydrodeoxygenation of bio-oil. Although the sulfided Co-Mo and Ni-Mo catalysts have good hydrodeoxygenation activity, due to the low sulfur content in bio-oil, additional sulfur needs to be supplemented in the hydrogenation process to activate the catalyst, resulting in Unnecessary impurity sulfur is introduced. Therefore, researchers have gradually shifted their research focus to non-sulfurized catalysts. Among them, noble metal catalysts exhibit high hydrodeoxygenation activity. For example, patent CN201210153043 discloses a catalyst that supports the active metal Pt on Al-SBA-15, which has high hydrodeoxygenation activity and selectivity to the bio-oil model compound phenol.

The activity of the catalyst is not only related to the active components, but also affected by the carrier. The mechanical strength and thermal stability of the support will affect the life of the catalyst. At the same time, the structure and surface properties of the support will also have an important impact on the catalytic activity and selectivity. The carriers used for bio-oil hydrogenation catalysts mainly include zeolite molecular sieves (HZSM-5 and HBeta, etc.), metal oxides (Al ₂ O ₃ , TiO ₂ , ZrO ₂ , SiO ₂ , SiO ₂ -Al ₂ O ₃ , CeO ₂ and CeO ₂ -ZrO ₂ , etc.), and activated carbon, etc. Zeolite molecular sieves have a regular pore structure and strong surface acid centers, which are beneficial to acid-catalyzed reactions, but the acidity makes the surface and pores of zeolite prone to carbon deposition, causing catalyst deactivation. Metal oxide supports also have the problem of carbon deposition. In addition, the weak acid resistance and hydrothermal stability will also destroy the structure of the metal oxide support during the hydrodeoxygenation process of bio-oil. Neutral activated carbon supports have a large specific surface area and good chemical stability, and are not prone to carbon deposition. However, due to the small pore size (usually less than 2 nm) of activated carbon materials, it is not conducive to the rapid migration of reactants in its pores. In addition, because bio-oil contains a certain amount of water, hydrodeoxygenation also produces water, so in the process of catalytic hydrogenation of bio-oil, not only gas-liquid reactions in the oil phase and gas-liquid reactions in the water phase are involved, but also There is also species transfer in oil-water systems. However, the functions of catalyst supports currently studied are relatively single, and it is difficult to meet the needs of the complex oil-water system of bio-oil. Therefore, designing a multifunctional composite support, adjusting the hydrophilicity and hydrophobicity of the catalyst support, so that the catalyst can simultaneously catalyze the reaction of the oil phase and the water phase, will greatly improve the catalytic hydrodeoxygenation efficiency of bio-oil.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art (i.e., the support function of the supported catalyst is single, it is difficult to meet the needs of the bio-oil/water system, and the catalyst pores are irregular, the pore diameter is small, etc.), and to provide a hydrogenation A deoxygenation catalyst and a preparation method thereof, the catalyst has oil/water amphiphilic dual functions, and is suitable for preparing cyclohexane through hydrodeoxygenation of phenol in a bio-oil system.

To achieve the above object, the present invention adopts the following technical solutions:

A hydrodeoxygenation catalyst, which is prepared by loading a hydrogenation active metal component on a carrier through an impregnation method, and the carrier is an ordered mesoporous carbon/silica-alumina composite material; the catalyst is made of carbon, silicon oxide and aluminum oxide The sum of the mass percentages is 100%, the carbon is 10-80%, and the balance is silicon oxide and aluminum oxide, wherein the silicon-aluminum molar ratio is 7-300; the specific surface area (BET) of the catalyst is 200-450 m ² / g, the pore volume is 0.20-0.40 cm ³ /g, and the pore diameter is 3.0-6.0 nm. By changing the mass ratio of carbon to silicon oxide and aluminum oxide, the hydrophilicity and hydrophobicity of the composite material carrier can be adjusted, and the carbon content is 10-80wt%.

Specifically, the hydrogenation active metal component is preferably palladium or nickel.

The preparation method of above-mentioned hydrodeoxygenation catalyst, it comprises the steps:

1) Dissolve the nonionic surfactant and acid catalyst in a volatile solvent. After the solution is clarified, add silicon source, aluminum source and carbon source, and stir evenly;

2) Use the mixed solution obtained in step 1) to completely evaporate the solvent by pulling, spin coating or film coating;

3) Polymerize and crosslink the product obtained in step 2) at 80-130°C for 12-36 hours;

4) Calcining the product obtained in step 3) at 450-1200°C under an inert atmosphere (to remove the surfactant and carbonize the carbon source) to obtain the carrier;

5) The hydrogenation active metal component is loaded on the carrier by impregnation method.

Preferably, the nonionic surfactants described in step 1) are C ₁₂ H ₂₅ EO ₂₃ (Brij35), C ₁₆ H ₃₃ EO ₁₀ (Brij56), C ₁₈ H ₃₇ EO ₁₀ (Brij76), EO ₁₀₆ PO One or more of ₇₀ EO ₁₀₆ (F127), EO ₂₀ PO ₇₀ EO ₂₀ (P123) and EO ₁₃₂ PO ₅₀ EO ₁₃₂ (F108).

The acid catalyst described in step 1) is one or more of formic acid, acetic acid, oxalic acid, benzoic acid, sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.

The volatile solvent described in step 1) is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, tetrahydrofuran, benzene, toluene, ether, chloroform and dichloromethane.

The silicon source described in step 1) is tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl orthosilicate, silicon tetrachloride and one or more of sodium silicate.

The aluminum source described in step 1) is one or more of aluminum isopropoxide, aluminum chloride, aluminum sulfate, aluminum nitrate and sodium aluminate.

The carbon source described in step 1) is one or more of soluble phenolic resin, urea-formaldehyde resin, furan resin, polyimide and polyacrylonitrile, with a molecular weight of 200-5000.

Step 1) The mass ratio of medium acid catalyst to silicon source is 0.2 ~ 0.004; the mass ratio of carbon source to nonionic surfactant is 0.01 ~ 1; the mass ratio of silicon source to carbon source is 1 ~ 25; the mass ratio of silicon source to aluminum source The molar ratio is 7 ~ 300.

Compared with prior art, the beneficial effect of the present invention is:

The present invention aims at the complex composition of bio-oil (that is, containing a large amount of oxygen-containing compounds, such as acids, phenols, aldehydes, ketones and alcohols, etc., and 15-30 wt.% of water), using silicon sources, aluminum sources, carbon sources and non- The multi-component assembly of ionic surfactants successfully synthesized ordered mesoporous carbon/silica-alumina composites as the carrier of bio-oil hydrodeoxygenation catalysts. The carrier not only has high specific surface area, large pore size, moderate The surface is acidic, and by changing the ratio of carbon and silica-alumina, the hydrophilicity and hydrophobicity of the carrier can be adjusted, so that the catalyst is stable at the oil-water two-phase interface, and simultaneously catalyzes the hydrogenation reaction in the oil phase and the water phase, improving the efficiency of hydrodeoxygenation .

Description of drawings

Fig. 1 is catalyst Pd/C-S-A-16 (embodiment 2), Pd/C-S-A-24 (embodiment 3), Pd/C-S-A-42 (embodiment 4), Pd/Al-SBA-15 (embodiment 5) and The small angle X-ray diffraction pattern of Pd/C (embodiment 6);

Fig. 2 is catalyst Pd/C-S-A-16 (embodiment 2), Pd/C-S-A-24 (embodiment 3), Pd/C-S-A-42 (embodiment 4), Pd/Al-SBA-15 (embodiment 5) and The large-angle X-ray diffraction pattern of Pd/C (embodiment 6);

Fig. 3 is the catalyst Pd/CSA-16 (Example 2), Pd/CSA-24 (Example 3), Pd/CSA-42 (Example 4), Pd/Al-SBA-15 (Example 5) and _N2 adsorption-desorption isotherm (A) and pore size distribution diagram (B) of Pd/C (Example 6);

Fig. 4 is the TEM photograph of the amphiphilic catalyst Pd/C-S-A-24 that embodiment 3 prepares;

Fig. 5 is the optical photograph that catalyst Pd/C-S-A-24 (embodiment 3), Pd/Al-SBA-15 (embodiment 5) and Pd/C (embodiment 6) distribute in decalin/water system;

Figure 6 is the small angle (A) and large angle (B) X-ray diffraction patterns of the amphiphilic catalyst Ni/C-S-A-24 prepared in Example 7;

Figure 7 is the _N2 adsorption-desorption isotherm (A) and pore size distribution diagram (B) of the amphiphilic catalyst Ni/CSA-24 prepared in Example 7;

Fig. 8 is a TEM photo of the amphiphilic catalyst Ni/C-S-A-24 prepared in Example 7.

Detailed ways

The technical solutions of the present invention will be further described in detail below in conjunction with the examples, but the protection scope of the present invention is not limited thereto.

The preparation of the amphiphilic catalyst of the present invention is divided into two steps, the first is the synthesis of the amphiphilic carrier (ordered mesoporous carbon/silicon aluminum oxide composite material), and then the hydrogenation active metal component is loaded on the on the carrier. The synthesis of the carrier is to add carbon source, silicon source and aluminum source in the volatile solvent dissolved with non-ionic surfactant and acid catalyst at the same time. The amphiphilic carrier is obtained by further heating, polymerizing, cross-linking, and high-temperature calcination to remove the surfactant. By changing the feed ratio of carbon source, silicon source and aluminum source, ordered mesoporous C-SiO ₂ -Al ₂ O ₃ composite supports with different carbon contents were synthesized, denoted as CSAx, where x represents C-SiO ₂ -Al The mass percentage of carbon in ₂ O ₃ composites. Unless otherwise specified, the silicon-aluminum ratio Si/Al (atom number ratio) in this application is 22. The hydrogenation active metal components were loaded onto the support by wet impregnation, the loading amount of Pd was 3%, and the loading amount of Ni was 5%.

The phenol hydrodeoxygenation reaction described in the present application is: use deionized water and equal volume of decahydronaphthalene mixed solution to simulate bio-oil oil-water two-phase system, dissolve phenol in the above solution, add the prepared catalyst, and then The mixed solution containing the catalyst was poured into a high-pressure reactor, H ₂ was introduced to reach a pressure of 5 MPa, the stirring speed was 600 r/min, and the reaction temperature was 200°C; the target product was cyclohexane.

The liquid product after catalytic hydrodeoxygenation of phenol was placed in a separatory funnel for layering, the water phase product was extracted with dichloromethane several times, and the decahydronaphthalene phase and dichloromethane extracted phase products were qualitatively analyzed by GC-MS , GC-FID quantitative analysis.

The phenol conversion (Y _phenol ) and the selectivity of the reaction product (S _i ) are defined as follows:

;

.

Embodiment 1: the preparation of resol resin

Melt 20.0 g of phenol at 40-42 °C, add 4.25 g of NaOH aqueous solution (20 wt%) and stir for 10 min, then add 35.4 g of formaldehyde aqueous solution (37 wt%) dropwise, heat up to 70-75 °C for reflux reaction for 1 h, Cool to room temperature, and adjust the pH of the solution to about 7.0 with hydrochloric acid (2 mol/l). The water was distilled under reduced pressure below 50°C, and the obtained viscous liquid was dissolved in absolute ethanol to form a solution with a concentration of 20wt%, left to stand overnight, and the precipitated NaCl was removed by centrifugation to obtain a clear ethanol solution of soluble phenolic resin. stand-by.

Example 2: Preparation of Pd/ C-S-A-16 and its evaluation on the hydrodeoxygenation activity of phenol

1) Preparation of carrier CSA-16: Dissolve 2.0 g of nonionic surfactant F127 (EO ₁₀₆ PO ₇₀ EO ₁₀₆ ) in 20.0 g of absolute ethanol at 40°C, add 2.0 g of 0.2 mol/l dilute hydrochloric acid, wait After F127 was completely dissolved, 4.16 g tetraethyl orthosilicate, 0.22 g aluminum chloride hexahydrate and 0.8 g ethanol solution of 20 wt% phenolic resole resin were added, and the stirring was continued for 2 h. Transfer the reaction solution to a Petri dish, and let it stand at room temperature to completely evaporate the solvent (about 5-10 hours). Then placed in an oven at 100 °C for further polymerization and cross-linking for 24 h. After cooling, the obtained product was scraped off from the petri dish, ground into powder, and calcined at 600 °C for 3 h under _N2 atmosphere to obtain a carbon content of 16% (calculated by TG), and a silicon-aluminum molar ratio (Si/Al) 22 mesoporous carbon/silica aluminum composite material support CSA-16.

2) Loading of Pd: Dissolve 0.05 g PdCl ₂ in absolute ethanol, then add 1.0 g of dry carrier CSA-16, stir at room temperature, after the solvent is completely evaporated, dry it in an oven at 100°C overnight, and then transfer the obtained powder Reduction in a tube furnace at 200°C for 3 h (10 vol % H ₂ /N ₂ ) to obtain a fresh catalyst 3%Pd/CSA-16.

Small-angle XRD characterization (Figure 1) shows that the catalyst has a two-dimensional hexagonal p 6 m mesoscopic structure; from large-angle XRD (Figure 2), it can be seen that PdCl ₂ is completely reduced to elemental Pd, according to the Scherrer formula, according to Pd(111) According to peak calculation, the average particle size of Pd metal particles is 4.9 nm; it is obtained from N ₂ adsorption and desorption characterization (Figure 3), the specific surface area of Pd/CSA-16 is 210 m ² /g, and the pore volume is 0.23 cm ³ /g, The pore size is 4.3nm.

3) Evaluation of Pd/CSA-16 catalytic phenol hydrodeoxygenation activity: Take 20 mL of deionized water and an equal volume of decahydronaphthalene to simulate the bio-oil-water two-phase system, dissolve 0.5 g of phenol in the above mixed solution, After adding 0.05 g of catalyst, pour it into a 100 mL batch high-pressure reactor, replace the air in the system with H ₂ , then increase the hydrogen pressure to 5 MPa, turn on the condensate water and the electric mixer (rotating speed 600 r/min), program Raise the temperature to 200°C (heating rate 100°C/h), and react for 2 h. After the reaction, the reaction kettle was lowered to room temperature, and the reacted product was collected, filtered with suction and washed to obtain the recovered catalyst. The collected liquid product was placed statically in a separatory funnel for layering, the aqueous phase product was extracted multiple times with dichloromethane, and the products of the decahydronaphthalene phase and dichloromethane extraction phase were subjected to GC-MS qualitative and GC-FID Quantitative analysis by internal standard method. As shown in Table 1, the conversion rate of phenol reached 86.4%, the selectivity of cyclohexane was 81.5%, and the by-products were cyclohexanone and cyclohexanol, the selectivities were 5.0% and 13.5%, respectively.

Example 3: Preparation of Pd/ C-S-A-24 and its evaluation on the hydrodeoxygenation activity of phenol

1) Preparation of carrier CSA-24: Dissolve 2.0 g of nonionic surfactant F127 in 20.0 g of absolute ethanol at 40°C, add 2.0 g of 0.2 mol/l dilute hydrochloric acid, after F127 is completely dissolved, add 4.16 g tetraethyl orthosilicate, 0.22 g aluminum chloride hexahydrate and 1.6 g ethanol solution of 20 wt% resole phenolic resin, and continue to stir for 2 h. Transfer the reaction solution to a Petri dish, and let it stand at room temperature to completely evaporate the solvent (about 5-10 hours). Then placed in an oven at 100 °C for further polymerization and cross-linking for 24 h. After cooling, the obtained product was scraped off from the petri dish, ground into powder, and calcined at 600°C for 3 hours under N ₂ atmosphere to obtain a carbon content of 24 wt% (calculated by TG), a silicon-aluminum molar ratio (Si/Al) 22 mesoporous carbon/silica aluminum composite material support CSA-24.

2) Pd loading: Same as in Example 2, the catalyst 3%Pd/C-S-A-24 was obtained.

XRD (Figure 1 and Figure 2) and TEM (Figure 4) show that the catalyst has a two-dimensional hexagonal p 6 m mesoscopic structure, and Pd metal particles with an average particle size of 5.0 nm are uniformly dispersed in the mesoporous channels. According to the N ₂ adsorption and desorption characterization (Figure 3), it can be seen that the specific surface area of Pd/CSA-24 is 275 m ² /g, the pore volume is 0.34 cm ³ /g, and the pore diameter is 5.1 nm. Using decahydronaphthalene and deionized water to simulate the oil/water system of bio-oil, put the catalyst in the above mixed solution, stir and let it stand, the optical photos (Figure 5) show that the catalyst Pd/CSA-24 can stably exist in the oil /water two-phase interface, indicating that the catalyst is oil-water amphiphilic.

3) Evaluation of Pd/C-S-A-24 catalytic phenol hydrodeoxygenation activity: the catalytic reaction and product analysis are the same as in Example 2. The conversion rate of phenol reached 98.0%, the selectivity of cyclohexane was 87.7%, the by-products were cyclohexanone and cyclohexanol, and the selectivities were 2.4% and 9.9%, respectively. The results are shown in Table 1.

Example 4: Preparation of Pd/ C-S-A-42 and Evaluation of Its Hydrodeoxygenation Activity to Phenol

1) Preparation of carrier CSA-42: Dissolve 3.2 g of nonionic surfactant F127 in 20.0 g of absolute ethanol at 40°C, add 2.0 g of 0.2 mol/l dilute hydrochloric acid, after F127 is completely dissolved, add 4.16 g tetraethyl orthosilicate, 0.22 g aluminum chloride hexahydrate and 10.0 g ethanol solution of 20 wt% resole phenolic resin, and continue to stir for 2 h. Transfer the reaction solution to a Petri dish, and let it stand at room temperature to completely evaporate the solvent (about 5-10 hours). Then placed in an oven at 100 °C for further polymerization and cross-linking for 24 h. After cooling, the obtained product was scraped off from the petri dish, ground into powder, and calcined at 600°C for 3 hours under _N2 atmosphere to obtain a carbon content of 42 wt% (calculated by TG), and a silicon-aluminum molar ratio (Si/Al) 22 mesoporous carbon/silicon aluminum oxide composite material support CSA-42.

2) Pd loading: Same as in Example 2, the catalyst 3%Pd/C-S-A-42 was obtained.

The characterization results are shown in Figure 1, Figure 2 and Figure 3, respectively. The results show that the catalyst has a two-dimensional hexagonal p 6 m mesoscopic structure, the average particle size of Pd metal particles is 5.8 nm, the specific surface area of Pd/CSA-42 is 340 m ² /g, and the pore volume is 0.30 cm ³ /g , with a pore size of 3.6 nm.

3) Evaluation of Pd/C-S-A-42 catalytic phenol hydrodeoxygenation activity: the catalytic reaction and product analysis are the same as in Example 2. The conversion rate of phenol was 88.1%, the selectivity of cyclohexane was 73.9%, the by-products were cyclohexanone and cyclohexanol, and the selectivities were 3.9% and 22.2%, respectively. The results are shown in Table 1.

Example 5: Preparation of Pd/ Al-SBA-15 and its evaluation on the hydrodeoxygenation activity of phenol

1) Preparation of carrier mesoporous silica aluminum Al-SBA-15: Add 3.0 g tetraethyl orthosilicate and 0.16 g AlCl ₃ 6H to 20 mL hydrochloric acid solution (pH=1.5) at 38-42 °C ₂ O (Si/Al=22/1), stirred for 4 h; dissolved 1.3 g of nonionic surfactant P123 (EO ₂₀ PO ₇₀ EO ₂₀ ) in 33 mL of dilute hydrochloric acid with pH=1.5, after the dissolution was complete, The above two solutions were mixed, kept stirring at a temperature of 38-42 ° C for 24 h, then moved the resulting white suspension to a hydrothermal kettle, aged at 100 ° C for 24 h, filtered to obtain a white solid, and washed The samples were dried at 100 °C for 8 h and calcined in a muffle furnace at 550 °C for 5 h to obtain fresh mesoporous silica-alumina Al-SBA-15.

2) The loading of Pd is the same as in Example 2 to obtain catalyst 3%Pd/Al-SBA-15.

The characterization results show that the catalyst has an ordered two-dimensional hexagonal p 6 m mesoscopic structure (Fig. 1), the average particle size of Pd metal particles is 6.4 nm (Fig. 2), and the specific surface area of Pd/CSA-42 is 494 m ² /g, pore volume 0.65 cm ³ /g, pore diameter 5.6 nm (Figure 3). Using decahydronaphthalene and deionized water to simulate the oil/water system of bio-oil, put the catalyst in the above mixed solution, stir and let it stand, the optical photos (Figure 5) show that the catalyst Pd/Al-SBA-15 is mainly distributed in the oil In the lower water phase of the water/water two-phase, it shows that the catalyst is hydrophilic.

3) Evaluation of Pd/Al-SBA-15 catalytic phenol hydrodeoxygenation activity: the catalytic reaction and product analysis are the same as in Example 2, and the results are shown in Table 1. The conversion rate of phenol was 82.0%, the selectivity of cyclohexane was 77.5%, and the selectivity of by-products cyclohexanone and cyclohexanol were 10.3% and 12.2%, respectively. Comparing the conversion rate of phenol under the action of Pd/Al-SBA-15 and Pd/C-S-A series catalysts shows that the catalyst with oil/water affinity (Pd/C-S-A) is more than the catalyst with only hydrophilicity (Pd/Al-SBA -15) Higher catalytic activity for phenol hydrodeoxygenation in oil/water system.

Example 6: Preparation of Pd/C and evaluation of its hydrodeoxygenation activity to phenol

1) Preparation of carrier mesoporous carbon: Dissolve 1.0 g of nonionic surfactant F127 in 20.0 g of absolute ethanol at 40 °C, add 5.0 g of 20 wt% ethanol solution of resole phenolic resin, and stir for 10 min to form Homogeneous transparent solution. Transfer the solution to a Petri dish and let it stand at room temperature to completely evaporate the solvent (about 5-10 hours). Then placed in an oven at 100 °C for further polymerization and cross-linking for 24 h. After cooling, the obtained product was scraped off from the petri dish, ground into powder, and calcined at 600°C for 3h under _N2 atmosphere with a heating rate of 1°C/min to obtain a mesoporous carbon material.

2) Loading of Pd: Same as in Example 2, that is, the catalyst 3%Pd/C is obtained.

The catalyst has an ordered two-dimensional hexagonal p 6 m mesoscopic structure (Figure 1), the average particle size of Pd metal particles is 6.9 nm (Figure 2), the specific surface area of Pd/C is 456 m ² /g, and the pore volume is 0.30 cm ³ /g, pore size 3.4 nm (Figure 3). Optical photographs (Fig. 5) show that Pd/C is mainly distributed in the upper oil phase of the oil/water two-phase composed of decahydronaphthalene and deionized water, indicating that the catalyst is lipophilic.

3) Pd/C catalyzed phenol hydrodeoxygenation activity evaluation: the catalytic reaction and product analysis are the same as in Example 2, the results are shown in Table 1, the conversion rate of phenol is 77.8%, the main product is cyclohexanol, and its selectivity is 91.3% , the selectivity of cyclohexanone is 5.9%, and the selectivity of cyclohexane is 2.8%. Comparing the conversion rate and product distribution of phenol under the action of Pd/C and Pd/C-S-A catalysts, it can be seen that the catalyst with oil/water affinity (Pd/C-S-A) is better than the catalyst with only lipophilicity (Pd/C) in oil/water The system has a higher conversion rate of phenol, and the presence of silica-alumina acidic support is beneficial to the deoxidation reaction of phenol.

Example 7: Preparation of Ni/C-S-A-24 and evaluation of its hydrodeoxygenation activity to phenol

1) The preparation of the carrier C-S-A-24 is the same as in Example 3.

2) Ni loading: Dissolve 0.05 gNi(NO ₃ ) ₂ ·6H ₂ O in 20ml absolute ethanol, stir well and add 0.2 g carrier. Stir at room temperature until the solvent evaporates completely, then dry in an oven at 60°C for 4 h, transfer the obtained powder to a tube furnace at 450°C for reduction for 4 h (10 vol%H ₂ /N ₂ ), and obtain 5%Ni/CSA-24 . XRD (Fig. 6) and TEM (Fig. 8) characterizations show that the catalyst has a two-dimensional hexagonal p 6 m mesoscopic structure, and Ni(NO ₃ ) ₂ is completely converted into elemental Ni. According to the Scherrer formula, according to Ni(111) According to the peak calculation, the average particle size of Ni is 6.7 nm, and the metal particles are uniformly dispersed on the mesoporous support. According to the N ₂ adsorption and desorption characterization (Figure 7), the specific surface area of Ni/CSA-24 is 220 m ² /g, the pore volume is 0.24 cm ³ /g, and the pore diameter is 4.0 nm.

3) Evaluation of Ni/CSA-24 catalytic phenol hydrodeoxygenation activity: 20 mL of deionized water and 20 ml of decahydronaphthalene were mixed to simulate a bio-oil-water two-phase system, and 0.2 g of phenol was dissolved in the above mixed solution. After adding 0.2 g of catalyst, pour it into a 100 mL batch high-pressure reactor, replace the air in the system with H ₂ , then increase the hydrogen pressure to 5 MPa, turn on the condensate water and the electric stirrer (speed 600 r/min), program Raise the temperature to 200°C (heating rate 100°C/h), and react for 5 h. After the reaction, the reaction kettle was lowered to room temperature, and the reacted product was collected, filtered with suction and washed to obtain the recovered catalyst. The collected liquid product was placed statically in a separatory funnel for layering, the aqueous phase product was extracted multiple times with dichloromethane, and the products of the decahydronaphthalene phase and dichloromethane extraction phase were subjected to GC-MS qualitative and GC-FID Quantitative analysis by internal standard method. As shown in Table 1, the conversion of phenol reached 97.3%, the selectivity of cyclohexane was 80.2%, and the selectivities of by-products cyclohexanone and cyclohexanol were 8.9% and 10.9%, respectively.

Finally, it should be noted that what is listed above are only specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and many variations are possible. Any changes within the meaning and scope equivalent to the claims of the present invention should be considered to be included in the scope of the claims.

Claims (10)

1. A hydrodeoxygenation catalyst, characterized in that, the catalyst is prepared by loading a hydrogenation active metal component on a carrier by an impregnation method, and the carrier is an ordered mesoporous carbon/silicon aluminum oxide composite material; The sum of mass percentages of silicon oxide and aluminum oxide is 100%, carbon is 10-80%, and the balance is silicon oxide and aluminum oxide, wherein the molar ratio of silicon to aluminum is 7-300; the specific surface area of the catalyst is 200-450 m ² /g, the pore volume is 0.20-0.40 cm ³ /g, and the pore diameter is 3.0-6.0 nm. 2. The hydrodeoxygenation catalyst according to claim 1, wherein the hydrogenation active metal component is palladium or nickel. 3. The preparation method of the described hydrodeoxygenation catalyst of claim 1 or 2, is characterized in that, comprises the steps: 1) Dissolve the nonionic surfactant and acid catalyst in a volatile solvent. After the solution is clarified, add silicon source, aluminum source and carbon source, and stir evenly; 2) Use the mixed solution obtained in step 1) to completely evaporate the solvent by pulling, spin coating or film coating; 3) Polymerize and crosslink the product obtained in step 2) at 80-130°C for 12-36 hours; 4) Calcining the product obtained in step 3) at 450-1200°C under an inert atmosphere to obtain the carrier; 5) The hydrogenation active metal component is loaded on the carrier by impregnation method. 4. The method for preparing a hydrodeoxygenation catalyst according to claim 3, wherein the nonionic surfactants in step 1) are C ₁₂ H ₂₅ EO ₂₃ , C ₁₆ H ₃₃ EO ₁₀ , C ₁₈ H One or more of ₃₇ EO ₁₀ , EO ₁₀₆ PO ₇₀ EO ₁₀₆ , EO ₂₀ PO ₇₀ EO ₂₀ and EO ₁₃₂ PO ₅₀ EO ₁₃₂ . 5. The method for preparing a hydrodeoxygenation catalyst according to claim 3, wherein the acid catalyst described in step 1) is one of formic acid, acetic acid, oxalic acid, benzoic acid, sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid or two or more. 6. The method for preparing a hydrodeoxygenation catalyst as claimed in claim 3, wherein the volatile solvent described in step 1) is methanol, ethanol, n-propanol, isopropanol, n-butanol, tetrahydrofuran, benzene , toluene, ether, chloroform and dichloromethane, or one or more of them. 7. The preparation method of the hydrodeoxygenation catalyst as claimed in claim 3, characterized in that, the silicon source described in step 1) is tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate , tetraisopropyl orthosilicate, tetrabutyl orthosilicate, and one or more of silicon tetrachloride or sodium silicate. 8. The method for preparing a hydrodeoxygenation catalyst according to claim 3, wherein the aluminum source described in step 1) is aluminum isopropoxide, aluminum chloride, aluminum sulfate, aluminum nitrate and sodium aluminate One or more than two. 9. The method for preparing a hydrodeoxygenation catalyst as claimed in claim 3, wherein the carbon source in step 1) is soluble phenolic resin, urea-formaldehyde resin, furan resin, polyimide and polyacrylonitrile One or two or more, the molecular weight is 200-5000. 10. The method for preparing a hydrodeoxygenation catalyst according to claim 3, wherein the mass ratio of the acid catalyst to the silicon source in step 1) is 0.2-0.004; the mass ratio of the carbon source to the nonionic surfactant is 0.01- 1. The mass ratio of the silicon source to the carbon source is 1-25; the molar ratio of the silicon source to the aluminum source is 7-300.