Industrial grade bifunctional catalyst, its preparation method and application

Abstract

The present application relates to a kind of industrial grade bifunctional catalyst and its preparation method and its application.The bifunctional catalyst is mainly composed of Y type molecular sieve, alumina binder and group VIII metal, and the preparation process includes mixing Y type molecular sieve with aluminum binder, then adding rice husk powder and mixing uniformly, then adding nitric acid, then preparing into shape, then further treating by pressurized hydrothermal calcination, then loading metal and reducing.The bifunctional catalyst can be used for bridge type tetrahydrodicyclopentadiene isomerization reaction.The preparation method of the catalyst in the present application is simple, easy to enlarge, pollution-free, has the effect of catalyst hole expansion, the prepared catalyst has abundant pore volume, high activity and good mechanical strength, is an industrial grade shaped catalyst, and is suitable for industrial application.

Description

Technical Field

[0001] This invention relates to the technical field of hydrocarbon isomerization, specifically to a catalyst for the isomerization of bridged tetrahydrodicyclopentadiene to prepare hanging tetrahydrodicyclopentadiene, and its preparation and application. Background Technology

[0002] Tetrahydrodicyclopentadiene (Exo-THDCPD) is a polycyclic hydrocarbon compound with the molecular formula C10H16. It has a high density (0.94 g / cm³). -3 With advantages such as low freezing point (<-79℃), high volumetric calorific value (39.4MJ / L), and low toxicity, it is a liquid fuel with excellent comprehensive performance. It can be used alone or as a solvent to blend with other fuels. It has been widely studied and applied in the field of aviation fuel. For example, the US military's JP-9 fuel is a blend of tetrahydrodicyclopentadiene, methylcyclohexane, and fully hydrogenated norbornene dimer, while more than 98.5% of JP-10 fuel is tetrahydrodicyclopentadiene.

[0003] The typical Exo-THDCPD preparation process involves a two-step conversion: first, dicyclopentadiene (DCPD) is hydrogenated to prepare bridged tetrahydrodicyclopentadiene (Endo-THDCPD), and then isomerized to Exo-THDCPD. The hydrogenation process is relatively mature and can be completed using common supported hydrogenation catalysts or Raney nickel catalysts. However, in industrial applications, the isomerization process still requires highly toxic and polluting AlCl3 as a catalyst and is carried out intermittently. Continuous industrial production has not yet been achieved. As described in patent CN102924216B, the hydrogenation conversion process can operate continuously for up to 2000 hours, but the isomerization conversion process still requires AlCl3 as a catalyst. This results in low Exo-THDCPD yield, high cost, and severe pollution during the production process, limiting its large-scale application. Furthermore, although some studies have used molecular sieves as isomerization catalysts to replace AlCl3, such as the patent CN 101786936B which uses Y, Beta, mordenite, Al-MCM-41, Al-MCM-48, and Al-SBA-15 as isomerization catalysts, these studies only examined the conversion rate of the feedstock and the yield of the product. They did not address catalyst lifetime or the feasibility of scaled-up continuous production, thus lacking practical application capability. Simultaneously, in the process of molecular sieve-catalyzed Exo-THDCPD isomerization, the tendency of molecular sieves to coke is the main cause of molecular sieve deactivation. Therefore, appropriately treating the molecular sieve to improve its anti-coking ability will help improve the activity and stability of the catalyst. In addition, when molecular sieve catalysts are used industrially, they require shaping treatment to ensure good mechanical properties to meet the requirements of long-term catalyst operation, while simultaneously preserving the catalytic activity and stability of the molecular sieve to the greatest extent possible. Summary of the Invention

[0004] This invention addresses the problem of catalyst deactivation due to coking in existing molecular sieve catalysts during the isomerization of bridged tetrahydrodicyclopentadiene to hanging tetrahydrodicyclopentadiene. It provides a bifunctional catalyst suitable for industrial application and its preparation method, and applies it to this isomerization reaction process.

[0005] In a first aspect, the present invention provides a bifunctional catalyst, which mainly comprises a Y-type molecular sieve, an alumina binder, and a group VIII metal. Based on the total mass of the catalyst (100%), the content of the Y-type molecular sieve is 50%-95%, the content of the alumina binder is 5%-50%, and the content of the group VIII metal is 0.1-20%.

[0006] Secondly, the present invention provides a method for preparing a bifunctional catalyst, comprising:

[0007] (1) Mix Y-type molecular sieve with aluminum binder and optional Tianqing powder, add nitric acid solution and stir evenly, extrude to form a shaped molecular sieve, and dry it;

[0008] (2) Molecular sieve formed by hydrothermal calcination at 450-650℃ and 0-0.5MPa steam atmosphere;

[0009] (3) Optionally, when there is tanqing powder, the steam atmosphere is switched to an air atmosphere to continue calcining the shaped molecular sieve to remove the tanqing powder.

[0010] (4) Optionally, the shaped molecular sieve is subjected to ammonium exchange treatment to reduce the sodium content in the molecular sieve;

[0011] (5) Metal loading of shaped molecular sieves is carried out using group VIII metal precursors, followed by drying, calcination, and reduction under a reducing atmosphere to obtain shaped bifunctional catalysts.

[0012] Thirdly, the present invention provides a method for isomerizing bridged tetrahydrodicyclopentadiene into hanging tetrahydrodicyclopentadiene, comprising: isomerizing bridged tetrahydrodicyclopentadiene into hanging tetrahydrodicyclopentadiene in the presence of the bifunctional catalyst described in the present invention.

[0013] This invention shapes powdered molecular sieves to achieve a certain strength (≥10 N / mm) to meet industrial application requirements. Simultaneously, the shaped molecular sieves undergo high-temperature steam pressure calcination, which expands the pores, thereby enhancing molecular diffusion, inhibiting the aggregation of coking precursors on the catalyst, and reducing the rate of catalyst coking and deactivation. Further metal impregnation of the catalyst yields a bifunctional catalyst. This catalyst features high metal dispersion and a significant effect in inhibiting catalyst coking and deactivation, and can be used in the industrial isomerization process of bridged tetrahydrodicyclopentadiene. Detailed Implementation

[0014] A bifunctional catalyst, comprising mainly a Y-type molecular sieve, an alumina binder, and a Group VIII metal, wherein, based on 100% of the total catalyst mass, the content of the Y-type molecular sieve is 50%-95%, preferably 70%-90%; the content of the alumina binder is 5%-50%, preferably 10%-30%; and the content of the Group VIII metal is 0.1-20%, preferably 0.2-10%.

[0015] In a preferred embodiment, the total pore volume of the bifunctional catalyst is determined to be 0.20-0.80 cm³ by the BET method. 3 / g, preferably 0.30-0.50cm 3 / g; mesopore volume is 0.02-0.30cm³ 3 / g, preferably 0.15-0.25cm 3 / g.

[0016] The Y-type molecule is screened from at least one of HY, USY, REHY, SSY, and NTY, with REHY, HY, and USY being preferred.

[0017] The metal is derived from at least one of Group VIII, preferably one or more of Pt, Pd, Ru, Rh and Ni. When the metal is selected from noble metals such as Pd, Pt, Ru and Rh, the metal content is preferably 0.1-1.0%, more preferably 0.2-0.5%. When the metal is a non-noble metal such as Ni, the metal content is 1.0-20%, more preferably 5-10%.

[0018] A method for preparing a bifunctional catalyst, comprising:

[0019] (1) Mix Y-type molecular sieve with aluminum binder and optional Tianqing powder, add nitric acid solution and stir evenly, extrude to form a shaped molecular sieve, and dry it;

[0020] (2) The shaped molecular sieve is subjected to hydrothermal calcination at 450-650℃ and 0-0.5MPa steam atmosphere;

[0021] (3) Optionally, when there is tanqing powder, the steam atmosphere is switched to an air atmosphere to continue calcining the shaped molecular sieve to remove the tanqing powder.

[0022] (4) Optionally, the shaped molecular sieve is subjected to ammonium exchange treatment to reduce the sodium content in the molecular sieve;

[0023] (5) Metal loading of shaped molecular sieves is carried out using group VIII metal precursors, followed by drying, calcination, and reduction under a reducing atmosphere to obtain shaped bifunctional catalysts.

[0024] According to the method of the present invention, in step (1), the content of Y-type molecular sieve is 50%-95%, preferably 70%-90%, by mass percentage of the mixture; the dry solid content of aluminum binder is 5%-50%, preferably 10%-30%; and the content of Tianqing powder is 0%-5%, preferably 1%-4%. The aluminum binder mainly includes, but is not limited to, aluminum sol, boehmite, Al2O3, etc. The drying temperature in step (1) is 100-200℃.

[0025] According to the method of the present invention, in step (2), the hydrothermal calcination temperature is 450-650℃, preferably 500-600℃, the treatment pressure is 0-0.5MPa, preferably 0.1-0.3MPa, and the treatment time is 1-6h, preferably 2-4h, so as to realize the function of expanding the molecular sieve pores, increasing the mesopore volume, and enhancing the diffusion of materials.

[0026] According to the method of the present invention, in step (3), when there is field rind powder, the field rind powder is removed by calcining in air atmosphere for 1-3 hours.

[0027] According to the method of the present invention, in step (4), the Y-type molecular sieve undergoes ammonium exchange to reduce its sodium content (calculated as sodium oxide) to below 1.0 wt%, preferably below 0.5 wt%, and more preferably below 0.2 wt%. The ammonium exchange method is as follows: the molecular sieve is added to an ammonium salt aqueous solution, stirred thoroughly, then filtered and washed, and the above process is repeated to meet the Na2O content requirements.

[0028] According to the method of the present invention, in step (5), the method for loading the shaped molecular sieve with metal can be a conventional method, such as the equal volume impregnation method, the excess volume impregnation method, etc., preferably the excess volume impregnation method, more preferably the impregnation liquid volume is 1-5 times excess. In some specific embodiments, the metal-loaded molecular sieve catalyst can be prepared as follows: an excess metal precursor solution is prepared according to the metal loading amount, and then impregnated on the molecular sieve, and left to stand at room temperature for more than 6 hours, accompanied by intermittent stirring; then dried at 80-100°C for more than 10 hours, and then calcined at 450-550°C for 2-5 hours in an air atmosphere; the calcined catalyst is reduced in a reducing atmosphere such as hydrogen at 400-550°C for 2-5 hours to obtain the activated catalyst. This application does not have strict limitations on the metal precursor used, which can be selected from the soluble salts of the corresponding metal, including but not limited to nitrates, sulfates and chlorides.

[0029] The industrial-grade bifunctional catalyst described in this invention can be applied to the isomerization of bridged tetrahydrodicyclopentadiene to hanging tetrahydrodicyclopentadiene, and can be used in both batch and continuous reaction processes.

[0030] A method for isomerizing bridged tetrahydrodicyclopentadiene to hanging tetrahydrodicyclopentadiene includes: isomerizing bridged tetrahydrodicyclopentadiene to hanging tetrahydrodicyclopentadiene in the presence of the industrial-grade bifunctional catalyst described in this invention.

[0031] In a preferred embodiment, the reaction temperature is 100-180°C, preferably 130-170°C.

[0032] In a preferred embodiment, the reaction pressure is 0.1-3.0 MPa, preferably 0.5-1.0 MPa; and the mass hourly space velocity is 0.2-5 h⁻¹. -1 Preferred time: 0.5-2 hours -1 The hydrogen / liquid volume ratio is 100-3200 Nm. 3 / m 3 Preferred capacity: 600-1200 Nm 3 / m 3 More preferably, the reaction is carried out in a hydrogen atmosphere, where the reaction pressure is the hydrogen pressure.

[0033] According to the present invention, the bridged tetrahydrodicyclopentadiene, which is used as a raw material for the isomerization reaction, can be commercially available or prepared in accordance with various methods disclosed in the prior art.

[0034] In a preferred embodiment, the bridged tetrahydrodicyclopentadiene is mixed with a solvent before the reaction to obtain a mixture with a mass concentration of 10-80 wt%, preferably 30-60 wt%, of the bridged tetrahydrodicyclopentadiene, and then the reaction is carried out.

[0035] More preferably, the solvent is a hydrocarbon or halogenated hydrocarbon solvent with a boiling point of 40-300℃, such as cyclohexane, methylcyclohexane, dichloromethane, etc., preferably C6-C. 10 Hydrocarbons, more preferably selected from cyclohexane, methylcyclohexane, tetrahydrodicyclopentadiene, or combinations thereof.

[0036] In a preferred embodiment, the method of the present invention is carried out using a fixed-bed reactor. In this embodiment, bridged tetrahydrodicyclopentadiene and the reaction solvent are uniformly premixed in a feed tank, and then pumped to the upper end of the fixed-bed reactor to pass through the bifunctional catalyst reaction bed together with hydrogen gas. The reaction products flow out from the lower end of the fixed bed.

[0037] In a particularly preferred embodiment, the method of the present invention includes: first, mixing bridge-type tetrahydrodicyclopentadiene with a reaction solvent until homogeneous, then pumping the mixture from the top to the bottom of a fixed-bed reactor; the isomerization reaction temperature is 100-180°C; the reaction pressure of the entire fixed-bed reactor is 0.1-3.0 MPa; and the mass hourly space velocity is 0.2-5 h⁻¹. -1 The hydrogen / liquid volume ratio is 100-3200 Nm. 3 / m 3 .

[0038] The following examples further illustrate specific implementations of the present invention.

[0039] In the following examples, the bridged tetrahydrodicyclopentadiene was purchased from Beijing Innocare Technology Co., Ltd., with a purity >99%, olefin content <1%, total sulfur content <100ppm, and total nitrogen content <100ppm.

[0040] Unless otherwise stated, all reagents used in the following examples and comparative examples are commercially available products of analytical purity.

[0041] Among them, HY, USY, REHY, SSY, and NTY molecular sieves were purchased from Sinopec Catalyst Branch.

[0042] The method for evaluating metal dispersion is the CO pulse adsorption method.

[0043] The method for evaluating the mechanical strength of molecular sieves is the determination of the crushing strength of strip-shaped catalysts (Q / SH 3360306-2020).

[0044] Examples 1-5

[0045] 80g of different Y-type molecular sieves, 20g of dry aluminum sol, and 4g of Tianqing powder were uniformly mixed, and then acidified with nitric acid solution. After that, the mixture was extruded and shaped, dried at 120℃ for 12h, and then calcined at 550℃ and 0.3MPa steam for 2h. After that, the atmosphere was switched to air and calcined for another 1h to remove the Tianqing powder, thus obtaining the shaped molecular sieve.

[0046] Subsequently, ammonium exchange can be selectively performed on the shaped molecular sieve. The method is as follows: add molecular sieve, NH4Cl and water into a container in a mass ratio of 1:0.4:10, stir at 60℃ and 500 rpm for 1 hour. After stirring, filter out the NH4Cl aqueous solution, rinse the molecular sieve with deionized water, and then repeat the above process to ensure that Na2O is less than 0.2%.

[0047] Then, metal Pt was impregnated with tetraamine platinum chloride as the precursor, with a loading of 0.3%. The excess volume impregnation method was adopted (1g of catalyst corresponds to 2.5g of precursor solution, with an excess of 1.5 times). The impregnation was carried out by continuous stirring at 50℃ for 6h, followed by drying at 80℃, calcination at 450℃ for 3h, and hydrogen reduction at 400℃ for 3h, thus obtaining different Y-type industrial-grade bifunctional catalysts.

[0048] The bifunctional catalyst was used for the isomerization of bridged tetrahydrodicyclopentadiene to prepare hanging tetrahydrodicyclopentadiene. The reaction was carried out in a fixed-bed reactor using a methylcyclohexane solution containing 50 wt% bridged tetrahydrodicyclopentadiene as feedstock. The reaction temperature was 150 °C, the reaction pressure was 0.5 MPa H2, and the mass hourly space velocity (WHSV) was 1 h⁻¹. -1 With a hydrogen-to-hydrogen volume ratio of 1000, the effluent from the fixed-bed reactor was sampled and analyzed by gas chromatography after 50 h of reaction. The reactant conversion rate and product selectivity were calculated using the area normalization method. The results are shown in Table 1.

[0049] Comparative Example 1

[0050] Instead of hydrothermal calcination of the catalyst precursor after REHY extrusion, it was directly calcined at 550°C in air for 3 hours to obtain a shaped molecular sieve. Then, metal Pt was directly loaded according to the method in Example 1, with a loading amount of 0.3%. The results are shown in Table 1.

[0051] Table 1. Influence of Y-type molecular sieve type

[0052]

[0053] Examples 6-9

[0054] A certain amount of REHY molecular sieve and 20g of dry alumina sol were mixed evenly with Tianqing powder at 4% of the total mass. Catalysts with different molecular sieve contents were then prepared according to the process in Example 1, and their mechanical strength and catalytic activity were evaluated. The results are shown in Table 2.

[0055] Table 2 Effect of Molecular Sieve Content

[0056]

[0057]

[0058] Examples 10-12

[0059] The REHY shaped molecular sieve, after water roasting at 550℃, 0.3MPa, and 2h as described in Example 1, underwent ammonium exchange. The Na₂O content after exchange was controlled, and then metals were impregnated or reduced according to the process described in Example 1 to obtain catalysts with different Na₂O contents. Their catalytic activity was then evaluated. The results are shown in Table 3.

[0060] Table 3 Effect of Na₂O content

[0061]

[0062] Examples 13-21

[0063] The formed REHY molecular sieve prepared in Example 1 was subjected to hydrothermal calcination under different conditions. Subsequently, the formed REHY molecular sieve after high-temperature hydrothermal calcination was subjected to ammonium exchange, metal impregnation, reduction, etc., according to the method described in Example 1. BET analysis was performed to examine the changes in its pore structure, and the activity of the catalyst was further evaluated (samples were taken for analysis after 50 h of reaction). The results are shown in Table 4.

[0064] Table 4. Effects of hydrothermal roasting treatment conditions

[0065]

[0066]

[0067] Examples 22-28

[0068] The REHY shaped molecular sieve (Na2O < 0.2%) prepared in Example 1 was impregnated with a tetraamine-platinum chloride metal precursor at a loading of 0%, 0.1%, 0.3%, or 0.5%. When using the excess volume impregnation method, the process in Example 1 was followed. In addition, for a loading of 0.3%, an equal volume impregnation method was also used. The process included: impregnation at room temperature for 6 hours with intermittent stirring, followed by drying at 80°C, calcination at 450°C for 3 hours, and hydrogen reduction at 400°C for 3 hours, thus obtaining the Pt-based bifunctional catalyst prepared by equal volume impregnation.

[0069] The REHY shaped molecular sieve (Na2O < 0.2%) prepared in Example 1 was impregnated with nickel nitrate as the metal precursor, with a loading of 1.0%, 5.0%, or 10%. The excess impregnation method as described in Example 1 was used. After impregnation, the sieve was dried at 80°C, calcined at 450°C for 3 hours, and reduced with hydrogen at 500°C for 3 hours to obtain Ni-based bifunctional catalysts with different loadings.

[0070] The catalysts prepared above were subjected to metal dispersion analysis by CO pulse adsorption (CO-TPD) and then used for the isomerization reaction of bridged tetrahydrodicyclopentadiene to investigate their catalytic performance (samples were taken after 50 h of reaction). The results are shown in Table 5.

[0071] Table 5. Effects of active metals and impregnation methods

[0072]

[0073]

[0074] Examples 29-31

[0075] The industrial-grade 0.3% Pt / REHY bifunctional catalyst prepared in Example 2 was reacted and analyzed according to the reaction conditions in Example 2, but the reaction temperatures were adjusted to 120℃ and 180℃ respectively. The results are shown in Table 6.

[0076] Table 6 Effect of different reaction temperatures

[0077]

[0078] Examples 32-34

[0079] The industrial-grade 0.3% Pt / REHY bifunctional catalyst prepared in Example 2 was reacted and analyzed according to the reaction conditions in Example 2, but the reaction pressures were adjusted to 0.2 MPa and 1.0 MPa, respectively. The results are shown in Table 7.

[0080] Table 7 Effect of different reaction pressures

[0081]

[0082]

[0083] Examples 35-37

[0084] The industrial-grade 0.3% Pt / REHY bifunctional catalyst prepared in Example 2 was reacted and analyzed according to the reaction conditions in Example 2, but the mass space velocity was adjusted to 0.5 h⁻¹. -1 and 2.0h -1 The results are shown in Table 8.

[0085] Table 8. Effect of different mass air velocities

[0086]

[0087] Examples 38-40

[0088] The industrial-grade 0.3% Pt / REHY bifunctional catalyst prepared in Example 2 was reacted and analyzed according to the reaction conditions in Example 2, but the hydrogen liquid volume ratio was adjusted to 500 and 1500, respectively. The results are shown in Table 9.

[0089] Table 9. Effect of different hydrogen liquid volume ratios

[0090]

[0091] Examples 41-44

[0092] The industrial-grade 0.3% Pt / REHY bifunctional catalyst prepared in Example 2 was reacted and analyzed according to the reaction conditions in Example 2, but the solvent and feed concentrations were adjusted. The results are shown in Table 10.

[0093] Table 10 Effect of different reaction solvents and reactant concentrations

[0094]

[0095] Example 45

[0096] The industrial-grade 0.3% Pt / REHY bifunctional catalyst prepared in Example 2 was reacted and analyzed according to the reaction conditions in Example 2, but the reaction time was extended to 200 h, and samples were taken for analysis every 50 h to examine the stability of the prepared catalyst. The results are shown in Table 11.

[0097] Table 11

[0098]

Claims

1. A method for isomerizing bridged tetrahydrodicyclopentadiene to hanging tetrahydrodicyclopentadiene, comprising: In the presence of a bifunctional catalyst, bridged tetrahydrodicyclopentadiene is isomerized to hanging tetrahydrodicyclopentadiene. The bifunctional catalyst comprises a Y-type molecular sieve, an alumina binder, and a Group VIII metal. Based on 100% of the total catalyst mass, the content of the Y-type molecular sieve is 60%-90%, and the content of the alumina binder is 5%-30%. The Y-type molecular sieve is selected from at least one of HY, USY, and REHY. The Group VIII metal is selected from one or more of Pt, Pd, Ru, Rh, and Ni. When the metal is selected from noble metals such as Pd, Pt, Ru, and Rh, the metal content is 0.2-0.5%; when the metal is Ni, the metal content is 5-10%. The total pore volume of the bifunctional catalyst is 0.30-0.50 cm³. 3 / g, mesopore volume is 0.15-0.25 cm³ 3 / g, the preparation method of the bifunctional catalyst includes: (1) Mix Y-type molecular sieve with aluminum binder and Tianqing powder, add nitric acid solution and stir evenly, extrude to form a shaped molecular sieve, and dry it; (2) The formed molecular sieve is subjected to hydrothermal calcination at 500-600℃ and 0.1-0.3MPa steam atmosphere for 1-4 hours; (3) Switch the water vapor atmosphere to an air atmosphere and continue calcining the formed molecular sieve to remove the spore powder; (4) The shaped molecular sieve is subjected to ammonium exchange treatment to reduce the sodium content in the molecular sieve to below 0.2 wt%; (5) Metal loading of the shaped molecular sieve is carried out using a precursor solution of a group VIII metal, followed by drying, calcination, and reduction under a reducing atmosphere to obtain the shaped bifunctional catalyst.

2. The method according to claim 1, wherein, The content of Y-type molecular sieve is 70%-80%, and the content of alumina binder is 10%-30%.

3. The method according to claim 1, wherein the aluminum binder is selected from aluminum sol, boehmite, and Al2O3.

4. The method according to claim 1, wherein in step (5), the shaped molecular sieve is loaded with metal by excess volume impregnation, and the volume of the impregnation liquid is 1-5 times excess.

5. The method according to claim 1, wherein, The isomerization reaction temperature is 120-180℃, the reaction pressure is 0.1-1.0 MPa, and the mass hourly space velocity (HHSV) is 0.2-5 h⁻¹. -1 The hydrogen / liquid volume ratio is 100-3200 Nm 3 / m 3 .

6. The method according to claim 1, wherein, The isomerization reaction temperature is 130-170℃, the reaction pressure is 0.2-0.5 MPa, and the mass hourly space velocity is 0.5-2 h⁻¹. -1 The hydrogen / liquid volume ratio is 500-1500 Nm. 3 / m 3 .

7. The method according to claim 1, wherein, Before the reaction, the bridged tetrahydrodicyclopentadiene was mixed with a solvent to obtain a mixture with a mass concentration of 10-80 wt% of the bridged tetrahydrodicyclopentadiene.

8. The method according to claim 1, wherein, Before the reaction, the bridged tetrahydrodicyclopentadiene was mixed with a solvent to obtain a mixture with a mass concentration of 30-60 wt% of the bridged tetrahydrodicyclopentadiene.

9. The method according to claim 7 or 8, wherein, The solvent is a hydrocarbon or halogenated hydrocarbon solvent with a boiling point of 40-300℃.

10. The method according to claim 7 or 8, wherein, The solvent is selected from cyclohexane, methylcyclohexane, tetrahydrodicyclopentadiene, or a combination thereof.

11. The method according to claim 1, wherein, Bridged tetrahydrodicyclopentadiene and reaction solvent are uniformly premixed in a feed tank and then pumped to the top of a fixed-bed reactor, passing through a bifunctional catalyst reaction bed together with hydrogen. The reaction products flow out from the bottom of the fixed bed.

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