High-activity catalyst as well as preparation method and application thereof
Synthesis of Ni12P5-CePO4 catalyst by solvothermal method has solved the problems of poor selectivity, low activity and short life of existing catalysts, and achieved efficient hydrogenation conversion and high-value utilization of dephenolized phenol oil.
Patent Information
- Application Number
- CN202510151026.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-10
- Publication Date
- 2025-05-06
AI Technical Summary
The existing catalysts used for hydrotreating dephenol phenol oil have the disadvantages of poor selectivity, low catalytic activity and short life, and it is difficult to achieve efficient and high-value utilization of dephenol phenol oil.
The Ni12P5-CePO4 catalyst was synthesized in one step by solvothermal method. By uniformly mixing the nickel source, the phosphorus source and the cerium source in an ethylene glycol solution, and then hydrothermal treatment was carried out in a hydrothermal reactor to form a highly active and highly selective catalyst.
The efficient catalytic hydrogenation conversion of dephenol phenol oil and its model oil is achieved. The catalyst shows excellent hydrogenation activity and deep hydrogenation performance, which extends the life of the catalyst.
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Figure CN119926436A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of hydrogenation catalysis, and relates to a method for preparing a catalyst and its application in catalytic hydrogenation dephenolization of phenol oil to prepare special oil products, specifically a one-step solvent thermal method for synthesizing Ni 12 The invention discloses a preparation method of P5-CePO4 catalyst and its application in catalytic hydrogenation of dephenolized phenol oil and model oil thereof. Background Art
[0002] Dephenolized phenol oil has attracted much attention as a substance with important research value. With the rapid development of industry, the coal tar processing industry is growing stronger and stronger, and dephenolized phenol oil is one of the key products in the deep processing of coal tar. Dephenolized phenol oil comes from the phenol oil fraction (170-210℃) cut during the distillation of coal tar, and dephenolized phenol oil is obtained after dephenolization. Coal tar is a by-product in the process of coal distillation, with huge output. If it is not effectively utilized, it will not only cause waste of resources, but also bring serious environmental problems. The rational development of dephenolized phenol oil has opened up an important way for the high-value utilization of coal tar, which can maximize the potential value of coal tar and conform to the current trend of sustainable development of resources. Dephenolized phenol oil contains rich aromatic compounds, which give it unique chemical properties and provide the possibility for subsequent conversion into high value-added products. Due to the complexity of the structure of dephenolized phenol oil, the dephenolized phenol oil model oil was studied first, and then the real system dephenolized phenol oil was studied. Therefore, the catalytic hydrogenation performance can be improved by modifying the carrier and its catalyst, thereby achieving the goal of high-value utilization of dephenolized phenol oil. At present, the catalyst used for dephenolized phenol oil hydroprocessing has the disadvantages of poor selectivity, low catalytic activity and short life. Therefore, the development of highly active and highly selective hydrogenation catalysts has become a key step in achieving high added value conversion of dephenolized phenol oil.
[0003] Domestic researchers have done a lot of research on catalysts for coal tar. Transition metal phosphide catalysts represented by nickel-based catalysts have good catalytic hydrogenation performance and are widely used in the catalytic hydrogenation of coal tar. In the catalytic hydrogenation process of dephenolized phenol oil and its model oil (composed of toluene, indene, naphthalene, 3-methylpyridine, benzofuran, and phenol), the modification of the catalyst can introduce acidic additives or modifiers to enhance the acidity of the catalyst. At the same time, the composite material design of the heterojunction structure can confine the growth to obtain a catalyst with smaller particle size and more open pore structure. Through the composite catalyst design strategy of cerium phosphate composite nickel phosphide,
[0004] In Ni 12 CePO4 was introduced into P5 catalyst, which can significantly improve Ni 12In addition, since CePO4 has a certain surface acidity (mainly Lewis acid), it can provide the required catalytic active centers, thereby improving the hydrogenation activity of the catalyst.
[0005] Therefore, it is necessary to develop a high-activity and high-selectivity nickel phosphide and cerium phosphate composite catalyst with a simple preparation method.
[0006] In view of this, the present invention is proposed. Summary of the invention
[0007] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art, provide a high-activity catalyst and a preparation method and application thereof, and solve the problems raised in the above-mentioned background technology.
[0008] In order to solve the above technical problems, the basic concept of the technical solution adopted by the present invention is:
[0009] In a first aspect, a method for preparing a highly active catalyst comprises the following steps:
[0010] S1. Dissolve the nickel source and phosphorus source in ethylene glycol solution and stir magnetically for 4-8 hours to form a uniform solution;
[0011] S2. Add the cerium source to the mixed solution described in step S1, and stir for 1-3 hours to form a uniform solution.
[0012] S3, transferring the mixed solution described in step S2 to the polytetrafluoroethylene liner of the hydrothermal reactor, maintaining the hydrothermal reactor at a heating temperature of 140-200° C. for 8-14 hours, then cooling, and washing the obtained product with deionized water 2-4 times;
[0013] S4, drying the product of step S3 in a vacuum oven at 60-100°C for 6-12h, and obtaining Ni 12 P5-CePO4 catalyst.
[0014] Optionally, in step S1, the nickel source is nickel chloride, nickel nitrate, or nickel sulfate; and the phosphorus source is sodium hypophosphite or sodium hydrogen phosphate.
[0015] Optionally, the cerium source in step S2 is cerium nitrate or cerium sulfate.
[0016] Cerium sulfate. The molar ratio of cerium source / nickel source is 1:(0.05, 0.1, 0.2, 0.3, 0.4).
[0017] In a second aspect, the present invention provides a high-activity catalyst prepared by the above-mentioned preparation method.
[0018] Preferably, the Ni 12The Ce / Ni molar ratio of the P5-CePO4 catalyst was 0.3 and the hydrothermal temperature was 180°C for 12 h at a heating rate of 5°C / min.
[0019] In a third aspect, the present invention provides an application of the above catalyst to the catalytic hydrogenation of dephenolized phenol oil and its model oil, and the specific application steps include:
[0020] a. Mix model oil, Ni 12 The P5-CePO4 catalyst and solvent were placed in a reactor, which was sealed and then the residual air was removed by introducing nitrogen three times and then hydrogen three times. Subsequently, the reactor was pressurized to 0.5-2.5 MPa with hydrogen at room temperature, and then the temperature was raised to the desired reaction temperature of 180-260°C and maintained at a stirring speed of 300 rpm for 30-150 min. After the experiment, the reaction system was naturally cooled to room temperature and the pressure was released. The reaction mixture was filtered to remove the catalyst, and the composition of the liquid product was analyzed by gas chromatography-mass spectrometry and gas phase analysis.
[0021] b. Remove phenol oil and Ni 12 P5-CePO4 catalyst and solvent were placed in a reactor, which was sealed and then the residual air was removed by introducing nitrogen three times and then hydrogen three times. Subsequently, the reactor was pressurized to 4 MPa with hydrogen at room temperature, and then the temperature was raised to the required reaction temperature of 220-300°C and maintained at a stirring speed of 400 rpm for 480 min. After the experiment, the reaction system was naturally cooled to room temperature and the pressure was released. The reaction mixture was filtered to remove the catalyst, and the composition of the liquid product was analyzed by gas chromatography-mass spectrometry and gas phase analysis.
[0022] In step a, the model oil is preferably prepared from six model compounds: toluene, naphthalene, benzofuran, indene, 3-methylpyridine and phenol.
[0023] Step a is preferred, the Ni 12 The amount of P5-CePO4 catalyst used is 50% of the mass of the model oil.
[0024] After adopting the above technical solution, the present invention has the following beneficial effects compared with the prior art. Of course, any product implementing the present invention does not necessarily need to achieve all the advantages described below at the same time:
[0025] The present invention uses nickel chloride, sodium hypophosphite and ethylene glycol as raw materials, and prepares Ni and NiO nanoparticles through sol-gel. 12 P5-CePO4 catalyst. Preparation of highly active Ni 12The P5-CePO4 catalyst was applied to the hydrogenation reaction of dephenolized phenol oil and its model oil, and it was found that it has excellent hydrogenation activity and deep hydrogenation performance, and can ultimately achieve efficient catalytic hydrogenation conversion of dephenolized phenol oil and its model oil.
[0026] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The drawings described below are only some embodiments. For those skilled in the art, other drawings can be obtained based on these drawings without creative work. In the drawings:
[0028] Figure 1 The Ni of different cerium / nickel molar ratios of the present invention 12 XRD image of P5-CePO4 catalyst;
[0029] Figure 2 The Ni of different cerium / nickel molar ratios of the present invention 12 SEM image of P5-CePO4 catalyst;
[0030] Figure 3 is the effect of reaction temperature on catalytic hydrogenation of model oil;
[0031] Figure 4 is the effect of reaction pressure on catalytic hydrogenation of model oil;
[0032] Figure 5 is the effect of reaction time on catalytic hydrogenation of model oil;
[0033] Figure 6 It's Ni 12 Effect of P5-CePO4 catalyst on catalytic hydrogenation of dephenolized phenol oil.
[0034] It should be noted that these drawings and textual descriptions are not intended to limit the conceptual scope of the present invention in any way, but are intended to illustrate the concept of the present invention for those skilled in the art by referring to specific embodiments. DETAILED DESCRIPTION
[0035] The present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments. The described specific embodiments are only used to explain the present invention and are not intended to limit the present invention.
[0036] Example 1: Catalyst Ni 12 The preparation of P5-CePO4 includes the following steps:
[0037] S1. First, dissolve 1.43 g of nickel chloride and 4.45 g of sodium hypophosphite in 60 mL of ethylene glycol and stir for 6 h until they are completely dissolved to form a uniform solution.
[0038] S2. Add 0.13 g of cerium nitrate to the mixed solution described in step S1 and stir for 2 h to form a uniform solution.
[0039] S3, transferring the mixed solution described in step S2 to the polytetrafluoroethylene liner of the hydrothermal reactor, maintaining the hydrothermal reactor at a heating temperature of 180° C. for 12 hours, then cooling, and washing the obtained product with deionized water three times;
[0040] S4, drying the product in step S3 in a vacuum oven at 80°C for 12h, and obtaining Ni 12 P5-CePO4 (Ce / Ni molar ratio is 0.05) catalyst.
[0041] Example 2: Catalyst Ni 12 Preparation of P5-CePO4 (Ce / Ni molar ratio of 0.1)
[0042] The preparation method is basically the same as that of Example 1, except that the Ce / Ni molar ratio is 0.1.
[0043] Example 3: Catalyst Ni 12 Preparation of P5-CePO4 (Ce / Ni molar ratio of 0.2)
[0044] The preparation method is basically the same as that of Example 1, except that the Ce / Ni molar ratio is 0.2.
[0045] Example 4: Catalyst Ni 12 Preparation of P5-CePO4 (Ce / Ni molar ratio of 0.3
[0046] The preparation method is basically the same as that of Example 1, except that the Ce / Ni molar ratio is 0.3.
[0047] Example 5: Catalyst Ni 12 Preparation of P5-CePO4 (Ce / Ni molar ratio of 0.4):
[0048] The preparation method is basically the same as that of Example 1, except that the Ce / Ni molar ratio is 0.4.
[0049] Experimental Example 1: Ni with different Ce / Ni molar ratios 12 XRD spectra of P5-CePO4 catalyst, Ni with different Ce / Ni molar ratios 12 SEM image of P5-CePO4 catalyst;
[0050] Figure 1 It's Ni 12 XRD spectra of P5 and a series of different Ce / Ni molar ratios. After hydrothermal reaction at 180℃ for 12h, Ni12 The characteristic diffraction peaks of P5 correspond to those of the standard comparison card PDF#74-1381, and are located at 29.2°, 32.7°, 35.8°, 38.4°, 41.25°, 41.63°, 41.75°, 44.42°, 46.96°, 48.96°, 54°, and 56.15°, respectively, corresponding to the (220), (310), (301), (112), (202), (231), (400), (330), (240), (312), (510), and (501) crystal planes. The diffraction peaks at 2θ of 28.9° and 31.2° belong to the (120) and (012) crystal planes of CePO4 (PDF#77-0429), respectively, indicating that the main components of the catalysts with different Ce / Ni molar ratios are Ni. 12 A mixed phase consisting of P5 and CePO4. Ni 12 The intensity of the diffraction peak of P5 (240) plane gradually weakened and began to shift when the Ce / Ni molar ratio was 0.1. This shift may be due to the change of lattice parameters caused by the introduction of CePO4.
[0051] Figure 2 Ni was characterized by SEM 12 Morphology of P5 and catalysts with different Ce / Ni molar ratios. Figure 2 As shown in af, Ni 12 The morphology of P5 catalyst ( Figure 2 a) Agglomeration of particles of uneven size. After the introduction of CePO4, the particles agglomerated to form spheres, and the spheres gradually decreased with the increase of Ce / Ni molar ratio. When the Ce / Ni molar ratio increased to 0.3 and 0.4, the particles agglomerated into spheres, but the spheres were very small, indicating that the introduction of CePO4 successfully reduced the particle size of the catalyst particles.
[0052] Experimental Example 2: Ni 12 Application of P5-CePO4 catalyst in catalytic hydrogenation of model oil
[0053] The present invention selects model oil to investigate Ni 12 The catalytic hydrogenation ability of P5-CePO4 catalyst and the optimal catalyst Ni 12 P5-CePO4 (Ce / Ni molar ratio is 0.3) was used to investigate the effects of different reaction temperatures, different reaction pressures and different reaction times on the conversion rate and product selectivity of the catalytic hydrogenation of the model oil. 12P5-CePO4 (Ce / Ni molar ratio of 0.3) was used as a catalyst for the experiment. The catalytic hydrogenation experiment was first conducted using a model oil mixed with naphthalene, indene and toluene to explore the reaction temperature conditions. The subsequent exploration of the reaction pressure and reaction time will use a model oil mixed with toluene, indene, naphthalene, 3-methylpyridine, benzofuran and phenol. The present invention uses 100 mg of model oil, 50 mg of catalyst and 20 mL of n-hexane as the reaction solvent to determine the optimal catalytic hydrogenation conditions of the model oil.
[0054] The model oil, Ni 12 P5-CePO4 (Ce / Ni molar ratio is 0.3) catalyst and solvent are placed in a reactor. After sealing, residual air is removed by passing nitrogen three times and then hydrogen three times. Subsequently, the reactor is pressurized to 0.5-2.5MPa with hydrogen at room temperature, and then the temperature is raised to the required reaction temperature of 180-260°C and maintained at a stirring speed of 300rpm for 30-150min. After the experiment, the reaction system is naturally cooled to room temperature and the pressure is released. The reaction mixture is filtered to remove the catalyst, and the liquid product composition is analyzed by gas chromatography-mass spectrometry and gas phase analysis.
[0055] Experimental Example 3: Effect of reaction temperature on catalytic hydrogenation conversion of model oil
[0056] Reaction conditions: 100 mg model oil, 50 mg catalyst, 20 mL n-hexane, 2 MPaH2, 2 h.
[0057] Reaction temperature plays an important role in the catalytic hydrogenation of model oil. Therefore, the catalyst and dosage were fixed to explore the effect of temperature on the directional catalytic hydrogenation of model oil (composed of toluene, indene, and naphthalene). Figure 3 It can be seen that as the reaction temperature increases from 180°C to 260°C, the conversion rate of the model oil increases rapidly from 45.51% to 100.00%, indicating that a moderate increase in temperature can significantly enhance the activity of the catalyst, promote the complete conversion of the model oil, and optimize the selectivity of the product. This may be due to the decrease in the activation energy of hydrogen molecules at higher temperatures, which accelerates the rate of the hydrogenation reaction. As the temperature increases, the selectivity of methylcyclohexane in the product increases from 0% to 65.93%, and the selectivity of octahydroindene increases from 0% to 23%. When the temperature is further increased to 240°C, the selectivity of tetralin decreases from 52.29% to 0%, and the products are methylcyclohexane, octahydroindene and decahydronaphthalene, indicating that at relatively high temperatures, the naphthalene hydrogenation reaction becomes more active and can be further converted into decahydronaphthalene. It not only confirms the promoting effect of temperature increase on the hydrogenation conversion of the model oil, but also highlights the importance of reaction temperature to the catalytic hydrogenation conversion process of the model oil. Therefore, 260°C was selected as the Ni 12 The optimal reaction temperature of P5-CePO4 catalyst for catalytic hydrogenation conversion of model oil.
[0058] Experimental Example 4: Effect of reaction hydrogen pressure on catalytic hydrogenation conversion of model oil
[0059] Reaction conditions: 100 mg model oil, 50 mg catalyst, 20 mL n-hexane, 260 °C, 2 h. Figure 4 The effect of hydrogen pressure on the catalytic hydrogenation performance of model oil (composed of toluene, indene, naphthalene, 3-methylpyridine, benzofuran, and phenol) during the reaction was investigated. As the initial hydrogen pressure increased from 0.5 MPa to 2.5 MPa, the conversion rate of the model oil increased rapidly from 22.51% to 100.00%, indicating that a moderate increase in the initial hydrogen pressure can significantly enhance the activity of the catalyst, promote the complete conversion of the model oil, and optimize the selectivity of the product. Under the condition of an initial hydrogen pressure of 0.5 MPa, the conversion rate of the model oil was 22.51%, and only tetralin, cyclohexanol, and 2-ethylcyclohexanol were present in the products. When the initial hydrogen pressure was increased to 1 MPa, the conversion rate of the model oil was 55.80%, and the conversion rate increased. However, in addition to tetralin, cyclohexanol, and 2-ethylcyclohexanol, decahydronaphthalene, methylcyclohexane, octahydroindene, and 3-methylpiperidine were also produced in the products. As for the products of naphthalene, the selectivity of tetralin is 22.43%, and the selectivity of decalin is 12.4%. This is because the catalytic hydrogenation performance of the catalyst for the model oil is improved with the increase of the initial hydrogen pressure. When the initial hydrogen pressure is further increased to 1.5MPa, the conversion rate of the model oil reaches 100%. The selectivity of methylcyclohexane increases from 0% to 34.1%, the selectivity of octahydroindene increases from 0% to 19.33%, the selectivity of tetralin decreases from 47.02% to 0%, and the selectivity of decalin increases from 0% to 16.76%. It shows that with the increase of the initial hydrogen pressure, the substrate is completely converted and the product selectivity increases accordingly. With the further increase of the initial hydrogen pressure to 2.5MPa, the conversion rate of the model oil is 100%. It shows that the increase of the initial hydrogen pressure can provide more active hydrogen species for the hydrogenation reaction, thereby realizing the hydrogenation of the aromatic ring. This not only confirms the effect of increasing the initial hydrogen pressure on the hydrogenation conversion of the model oil, but also highlights the importance of the initial hydrogen pressure on the catalytic hydrogenation conversion process of the model oil. 12 The optimal initial hydrogen pressure of P5-CePO4 catalyst for catalytic hydroconversion of model oil.
[0060] Experimental Example 5: Effect of reaction time on catalytic hydrogenation conversion of model oil
[0061] Reaction conditions: 100 mg model oil, 50 mg catalyst, 20 mL n-hexane, 260 °C, 1.5 MPa. Figure 5The effect of reaction time on the catalytic hydrogenation of model oil is shown. As the reaction time is extended from 0.5h to 2h, the conversion rate of the model oil increases from 67.71% to 100%. This shows that the extension of reaction time is beneficial to the catalytic hydrogenation reaction of the model oil. When the reaction time is 0.5h, the conversion rate of BPE is 67.71%, at which time all other substrates are converted, but toluene is not converted. When the reaction time is extended to 2h, the conversion rate of the model oil is significantly increased to 100%, and toluene is completely converted, and methylcyclohexane begins to appear as a hydrogenation product with a selectivity of 33.03%. This result shows that extending the reaction time helps to improve the contact efficiency between the catalyst and the substrate, thereby promoting the conversion of more toluene into methylcyclohexane. Prolonging the reaction time is beneficial to the hydrogenation reaction. Based on the conversion rate of the model oil, 2h is selected as the Ni 12 The optimal reaction time of P5-CePO4 catalyst for catalytic hydrogenation conversion of model oil.
[0062] Experimental Example 6: Ni 12 Application of P5-CePO4 catalyst in catalytic hydrogenation of dephenolized phenol oil 12 The P5-CePO4 catalyst and solvent were placed in a reactor, sealed, and the residual air was removed by passing nitrogen three times and then hydrogen three times; then, the reactor was pressurized to 4MPa with hydrogen at room temperature, and then the temperature was raised to the required reaction temperature of 220-300°C and maintained at a stirring speed of 400rpm for 480min. After the experiment, the reaction system was naturally cooled to room temperature and the pressure was released; the reaction mixture was filtered to remove the catalyst, and the liquid product composition was analyzed by gas chromatography-mass spectrometry. The present invention uses 300mg model oil, 150mg catalyst, and 20mL n-hexane as the reaction solvent to explore Ni 12 The catalytic hydrogenation conversion performance of P5-CePO4 catalyst on dephenolized phenol oil at different temperatures (220℃, 260℃, 300℃).
[0063] Experimental Example 7: Effect of reaction temperature on catalytic hydrogenation conversion of dephenolized phenol oil
[0064] Reaction conditions: 300 mg model oil, 150 mg catalyst, 20 mL n-hexane, 4 MPaH2, 6 h.
[0065] GC / MS analysis was performed on the dephenolized phenol oil before hydrogenation and the dephenolized phenol oil after hydrogenation at different temperatures. Figure 6 This is the distribution diagram of the group components of phenol oil and dephenolized phenol oil. The species detectable by GC / MS are divided into 9 groups: benzene, alkanes, indenes, naphthalenes, furans, pyridines, olefins, and phenols. Figure 6It can be seen that the distribution of group components of each product before and after hydrogenation of dephenolized phenol oil has changed significantly. With the increase of temperature, the content of benzene gradually decreased from 41.79% to 13.91%. The content of alkanes gradually increased from 31.29% to 53.73%. The content of olefins gradually increased from 0.93% to 5.97%. The content of furans decreased to 0%, the content of phenols decreased to 0%, and the content of alcohols gradually increased from 0% to 3.93%. Indenes, naphthalenes, and pyridines were converted by hydrogenation at different temperatures, and the content did not change much. From the above trend analysis, the decrease in benzene content, the increase in alkane content, and the hydrogenation conversion of indenes, naphthalenes, furans, and phenols indicate that catalytic hydrogenation promotes the lightweight utilization of dephenolized phenol oil, realizes the full utilization of dephenolized phenol oil resources and the production of high value-added products.
[0066] The present invention is not limited to the above-mentioned embodiments. Anyone should be aware that any structural changes made under the enlightenment of the present invention, and any technical solutions that are the same or similar to the present invention, fall within the protection scope of the present invention. The technology, shape, and structural parts not described in detail in the present invention are all well-known technologies.
Claims
1. A method for preparing a highly active catalyst, characterized in that: The following steps are involved: S1. Dissolve the nickel source and phosphorus source in ethylene glycol solution and stir magnetically for 4-8 hours to form a uniform solution; S2, adding the cerium source to the mixed solution described in step S1, stirring for 1-3 hours to form a uniform solution; S3, transferring the mixed solution described in step S2 to the polytetrafluoroethylene liner of the hydrothermal reactor, maintaining the hydrothermal reactor at a heating temperature of 140-200° C. for 8-14 hours, then cooling, and washing the obtained product with deionized water 2-4 times; S4, drying the product of step S3 in a vacuum oven at 60-100°C for 6h-12h, and obtaining Ni 12 P5-CePO4 catalyst.
2. The method for preparing a highly active catalyst according to claim 1, characterized in that: In step S1, the nickel source is nickel chloride, the phosphorus source is sodium hypophosphite, and the cerium source is cerium nitrate.
3. The method for preparing a highly active catalyst according to claim 2, characterized in that: The molar ratio of the cerium source / nickel source in step S2 is (0.05, 0.1, 0.2, 0.3, 0.4).
4. A highly active catalyst, characterized in that The method is prepared by the preparation method according to any one of claims 1 to 3.
5. The highly active catalyst according to claim 4, characterized in that Application in catalytic hydrogenation of dephenolized phenol oil and its model oil.
6. The use of the high-activity catalyst according to claim 5 in the catalytic hydrogenation of dephenolized phenol oil and its model oil, characterized in that: The specific application steps include: a. Mix model oil, Ni 12 P5-CePO4 catalyst and solvent were placed in a reactor, which was sealed and then the residual air was removed by introducing nitrogen three times and then hydrogen three times; then, the reactor was pressurized to 0.5-2.5MPa with hydrogen at room temperature, and then the temperature was raised to the desired reaction temperature of 180-260°C and maintained at a stirring speed of 300rpm for 30-150min. After the experiment, the reaction system was naturally cooled to room temperature and the pressure was released; the reaction mixture was filtered to remove the catalyst, and the composition of the liquid product was analyzed by gas chromatography-mass spectrometry and gas phase analysis; b. Remove phenol oil and Ni 12 P5-CePO4 catalyst and solvent were placed in a reactor, which was sealed and then the residual air was removed by introducing nitrogen three times and then hydrogen three times. Subsequently, the reactor was pressurized to 4 MPa with hydrogen at room temperature, and then the temperature was raised to the required reaction temperature of 220-300°C and maintained at a stirring speed of 400 rpm for 480 min. After the experiment, the reaction system was naturally cooled to room temperature and the pressure was released. The reaction mixture was filtered to remove the catalyst, and the composition of the liquid product was analyzed by gas chromatography-mass spectrometry and gas phase analysis.
7. The model oil according to claim 5, characterized in that The model oil is prepared from six model compounds, namely, toluene, naphthalene, benzofuran, indene, 3-methylpyridine and phenol.