A polycyclic aromatic hydrocarbon hydrogenation catalyst, a preparation method and application thereof

Abstract

The application discloses a polycyclic aromatic hydrocarbon hydrogenation catalyst and a preparation method and application thereof. The catalyst comprises a carrier and an active metal component, wherein the active metal component comprises at least one metal element selected from a La system, a group IB or a group VIB; and the carrier is characterized by electron paramagnetic resonance (EPR) technology and peaks in the range of g=1.94-2.06. The catalyst is used in polycyclic aromatic hydrocarbon hydrogenation reaction, especially naphthalene and naphthalene series hydrogenation reaction, and has the characteristics of high conversion rate and high selectivity of target products.

Description

Technical Field

[0001] This invention relates to the field of polycyclic aromatic hydrocarbon hydrogenation, and more specifically to a polycyclic aromatic hydrocarbon hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] Polycyclic aromatic hydrocarbons (PAHs) are important byproducts in petroleum refining and chemical processes, such as light cycle oil from fluidized bed catalytic cracking, pyrolysis fuel from naphtha cracking, and heavy aromatics from xylene plants. Traditionally, these PAHs are used as fuel blending components or directly for energy production. However, with the increasing scarcity of fossil fuels and the globalization of carbon emission standards, effectively utilizing aromatic resources within PAHs has become a research topic related to sustainable energy development and environmental protection. Therefore, finding more efficient and environmentally friendly ways to utilize aromatic resources within PAHs is urgent. Converting PAHs into high-value-added benzene, toluene, and xylene through hydrocracking is a promising route. Converting PAHs into monocyclic aromatic hydrocarbons such as tetrahydronaphthalene and its naphthalene derivatives is a crucial step in PAH utilization. This reaction often involves loading metal species before use, as the metal component is the main functional species for hydrogenation. Therefore, the utilization rate of the metal component directly affects the conversion rate and yield of the catalyst in the hydrogenation reaction.

[0003] CN102838438A discloses a method for hydrogenating naphthalene to tetrahydronaphthalene. The hydrogenation catalyst used in this method has the following composition by weight: ZSM-5 molecular sieve content of 10.0%–80.0%, alkali metal content of 0.1%–10.0%, nickel oxide content of 10.0%–80.0%, molybdenum trioxide content of 0.5%–5.0%, with the balance being silicon dioxide. The method employs a fixed-bed reactor, and the catalyst undergoes pre-sulfurization treatment. Under suitable hydrogenation reaction conditions, tetrahydronaphthalene is obtained.

[0004] CN108059581A discloses a method for preparing tetrahydronaphthalene by hydrogenation of naphthalene. The method obtains tetrahydronaphthalene product by using a two-stage hydrogenation reactor.

[0005] CN105749984A discloses a method for preparing a naphthalene hydrogenation catalyst, wherein the catalyst is composed of a support, a group VB metal sulfide, and a passivation oil.

[0006] In summary, current research on polycyclic aromatic hydrocarbon hydrogenation catalysts focuses primarily on their conversion rate and stability, but the yield of the target product still needs further improvement. Summary of the Invention

[0007] To address the issue of insufficient yield of target products in the hydrogenation reaction of polycyclic aromatic hydrocarbons (PAHs) using existing catalysts, this invention provides a novel PAH hydrogenation catalyst, its preparation method, and its applications. The catalyst of this invention, when used in the hydrogenation reaction of PAHs, especially naphthalene and naphthalene derivatives, exhibits high conversion rates and high selectivity for target products.

[0008] The first aspect of this invention provides a polycyclic aromatic hydrocarbon hydrogenation catalyst, comprising:

[0009] a) Carrier;

[0010] b) An active metal component, wherein the active metal component comprises at least one metal element selected from the La series, Group IB or Group VIB;

[0011] The carrier was characterized by electron paramagnetic resonance (EPR) technology, and showed peaks in the range of g = 1.94-2.06.

[0012] Furthermore, the catalyst, characterized by X-ray photoelectron spectroscopy, exhibits a reduction degree of the active metal component of 15% or higher, preferably 20% to 65%. The reduction degree of the active metal component refers to the reduction of the metal from its valence state inherent in the active metal itself within the catalyst to a lower valence state.

[0013] Furthermore, the carrier is selected from non-acidic or weakly acidic carriers, preferably from at least one of titanium oxide, zinc oxide, zirconium oxide, cerium oxide, and iron oxide, and more preferably from titanium oxide and / or zinc oxide.

[0014] Furthermore, the active metal component is selected from at least one of La, Ce, Cu, Cr, Mo, and W, preferably Ce and / or Mo.

[0015] Furthermore, based on the weight of the catalyst, the content of the metal component, calculated as an element, is 0.01% to 20%, preferably 0.1% to 5%; the content of the support is 80% to 99.99%, preferably 95% to 99.9%.

[0016] Furthermore, the carrier is a porous carrier treated with a reducing solution.

[0017] A second aspect of the present invention provides a method for preparing the above-mentioned polycyclic aromatic hydrocarbon hydrogenation catalyst, comprising:

[0018] (1) The porous carrier material is dried to obtain carrier precursor I;

[0019] (2) After treating the carrier precursor I in a reducing solution and drying it, the carrier II is obtained;

[0020] (3) Prepare a metal salt solution, load it onto the support II obtained in step (2), dry and calcine to obtain the catalyst.

[0021] Furthermore, the porous carrier material is selected from acid-free or weakly acidic carrier materials, preferably from at least one of titanium oxide, zinc oxide, zirconium oxide, cerium oxide, and iron oxide, and more preferably from titanium oxide and / or zinc oxide.

[0022] Furthermore, the drying temperature in step (1) is 70-120°C, preferably 90-110°C, and the drying time is 2-10 hours, preferably 5-8 hours.

[0023] Further, the reducing solution in step (2) can be at least one of NaBH4 or KBH4 aqueous solution, preferably NaBH4 aqueous solution.

[0024] Further, the molar concentration of the reducing solution is 0.2–5 mol / L, preferably 0.5–2 mol / L, and the treatment conditions in the reducing solution are: a treatment temperature of 25–100℃, preferably 40–90℃, a treatment time of 1–18 h, preferably 5–10 h, and a mass ratio of carrier to reducing solution of 1:5–1:20, preferably 1:10–1:15.

[0025] Furthermore, the drying temperature in step (2) is 70-120°C, preferably 90-110°C, and the drying time is 2-10 hours, preferably 5-8 hours.

[0026] Furthermore, the carrier II was characterized by electron paramagnetic resonance (EPR) technology, and showed peaks in the range of g = 1.94-2.06.

[0027] Furthermore, in step (3), the method of loading the metal component in the metal salt solution onto the carrier can be by impregnation, precipitation or physical kneading, preferably impregnation.

[0028] Further, in step (3), the metal salt solution may be selected from at least one of the nitrates, chlorides, acetates or other soluble salts of an active metal (selected from at least one of the metals of the La series, Group IB or Group VIB).

[0029] Furthermore, in step (3), the drying temperature is 70-120°C, preferably 90-110°C, and the drying time is 2-10 hours, preferably 5-8 hours.

[0030] Further, in step (3), the calcination atmosphere of the catalyst is air, the calcination temperature is 300-700℃, preferably 400-550℃, and the calcination time is 1-10h, preferably 2-6h.

[0031] A third aspect of the present invention provides the application of the above-mentioned catalyst in the hydrogenation reaction of polycyclic aromatic hydrocarbons.

[0032] Further, the reaction conditions are as follows: reaction temperature of 100–550 °C, reaction pressure of 1.0–5.0 MPa, hydrogen-to-hydrogen volume ratio of 1–8, and feed weight hourly space velocity of 0.5–20 h⁻¹. -1 .

[0033] Furthermore, the polycyclic aromatic hydrocarbon is preferably naphthalene or naphthalene derivatives, and the target product is tetrahydronaphthalene.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] 1. Metal components are crucial active components in polycyclic aromatic hydrocarbon (PAH) hydrogenation catalysts. The loading state of the metal component and its interaction with the support surface are closely related, directly affecting its properties and catalytic performance in the reaction. Reduction treatment is a vital step in activating the metal component; the degree of reduction determines the utilization rate and catalytic efficiency of the metal component in the catalyst. To improve catalyst activation, industrial processes often modify the metal components in existing catalysts through steps such as pre-sulfurization to achieve a more reactive state. This pretreatment often increases catalyst production costs, complicates processes, and frequently leads to environmental issues.

[0036] The inventors of this invention discovered that the utilization rate of metal components in the hydrogenation reaction of polycyclic aromatic hydrocarbons (PAHs) is related to the activity and selectivity of the catalyst. However, in conventionally prepared catalysts, metal components are often not fully reduced, and a large amount of metal components still exist in the reaction system in a highly oxidized state. This invention, by preferentially treating the support in the reducing agent, can generate oxygen vacancies on its surface. These defect sites cause oxygen atoms in the metal clusters to deviate from their original positions during subsequent metal loading and calcination, resulting in microstructural distortion. This elongates the metal-oxygen bonds, making them easier to break during subsequent reduction, thus facilitating the reduction of metal components. This surpasses the reducibility of conventionally prepared catalysts, further increasing the number of active sites actually participating in the reaction in the catalyst, and improving the conversion and yield of PAH hydrogenation, especially the preparation of tetrahydronaphthalene from naphthalene and naphthalene derivatives.

[0037] 2. The preparation method provided by this invention is simple to operate, economical and feasible, does not require the introduction of additional elements into the target catalyst system, and is easy to apply industrially.

[0038] 3. The polycyclic aromatic hydrocarbon hydrogenation catalyst provided by this invention is used in the hydrogenation reaction of polycyclic aromatic hydrocarbons and has the characteristics of high utilization rate of metal components, high conversion rate of reactants and high yield of target product. Detailed Implementation

[0039] The technical solution of the present invention will be further illustrated below with reference to the embodiments, but it is not limited to the following embodiments.

[0040] In this invention, the catalyst is reduced in a hydrogen atmosphere at a reduction temperature of 400–500°C for 1–4 hours, and then XPS analysis is performed.

[0041] In this invention, the X-ray photoelectron spectroscopy (XPS) instrument used is a PerkinElmer PHI 5000C ESCA model, with an emission source of Mg Kα (hν = 1253.6 eV), an operating voltage of 14 kV, and an operating current of 20 mA. In this invention, the degree of reduction of the metal element is calculated quantitatively from the peak area after peak separation in the XPS spectrum.

[0042] In this invention, electron paramagnetic resonance (EPR) was performed using an EMX-8 / 2.7 instrument from Bruker GmbH, Germany. The sample was placed at room temperature for measurement, with a frequency of 9.88 GHz and a microwave power of 2.0 mW.

[0043]

Example 1

[0044] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 1 mol / L NaBH4 aqueous solution at 50 °C for 6 hours, filter and dry to obtain support B1. EPR characterization shows that support B1 has a peak in the range of g = 1.94-2.06.

[0045] An equal volume of ammonium molybdate solution and support B1 were impregnated and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air. Catalyst C1 with a Mo content of 2% (wt) was obtained. EPR characterization showed that catalyst C1 eluted in the range of g = 1.94-2.06. After reducing catalyst C1 at 450℃ for 3 h, the reduction of Mo was determined by XPS. The reduction of Mo after peak separation is shown in Table 1.

[0046] Three grams of catalyst C1 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0047]

Example 2

[0048] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 2 mol / L NaBH4 aqueous solution at 80 °C for 6 hours, filter and dry to obtain support B2. EPR characterization shows that support B2 has a peak in the range of g = 1.94-2.06.

[0049] After impregnating ammonium molybdate solution and support B2 in equal volumes, the mixture was dried at 100℃ for 7 h and then calcined at 500℃ for 2 h in air atmosphere to obtain catalyst C2 with a Mo content of 2% (wt). EPR characterization showed that catalyst C2 eluted in the range of g = 1.94-2.06. Catalyst C2 was reduced at 450℃ for 3 h, and the reduction of Mo was determined by XPS. The reduction of Mo after peak separation is shown in Table 1.

[0050] Three grams of catalyst C2 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0051]

Example 3

[0052] Take 10 g of zinc oxide support, dry the support at 100 °C for 7 hours to obtain support A3. Treat support A3 in 120 g of 1 mol / L NaBH4 aqueous solution at 50 °C for 6 hours, filter and dry to obtain support B3. EPR characterization shows that support B3 has a peak in the range of g = 1.94-2.06.

[0053] An equal volume of ammonium molybdate solution and support B3 were impregnated and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air atmosphere. Catalyst C3 with a Mo content of 2% (wt) was obtained. EPR characterization showed peaks in the range of g = 1.94-2.06. Catalyst C3 was reduced at 450℃ for 3 h, and the reduction of Mo was determined by XPS. The reduction of Mo after peak separation is shown in Table 1.

[0054] Three grams of catalyst C3 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0055]

Example 4

[0056] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 1 mol / L NaBH4 aqueous solution at 50 °C for 6 hours, filter and dry to obtain support B1. EPR characterization shows that support B1 has a peak in the range of g = 1.94-2.06.

[0057] After impregnating the catalyst with an equal volume of cerium nitrate solution and support B1, the catalyst was dried at 100℃ for 7 h and then calcined at 500℃ for 2 h in air. Catalyst C4 with a Ce content of 2% (wt) was obtained. EPR characterization showed that catalyst C4 eluted in the range of g = 1.94-2.06. Catalyst C4 was reduced at 450℃ for 3 h, and the reduction of Ce was determined by XPS. The reduction of Ce after peak separation is shown in Table 1.

[0058] Three grams of catalyst C4 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0059]

Example 5

[0060] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 2 mol / L NaBH4 aqueous solution at 80 °C for 6 hours, filter and dry to obtain support B5. EPR characterization shows that support B5 has a peak in the range of g = 1.94-2.06.

[0061] Equal volumes of cerium nitrate solution and support B5 were impregnated and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air atmosphere. Catalyst C5 with a Ce content of 2% (wt) was obtained. EPR characterization showed that catalyst C5 eluted in the range of g = 1.94-2.06. After reducing catalyst C5 at 450℃ for 3 h, XPS was used to determine the reduction of Ce. The reduction of Ce after peak separation is shown in Table 1.

[0062] Three grams of catalyst C5 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0063]

Example 6

[0064] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 1 mol / L NaBH4 aqueous solution at 50 °C for 6 hours, filter and dry to obtain support B1. EPR characterization shows that support B1 has a peak in the range of g = 1.94-2.06.

[0065] After impregnating the catalyst with an equal volume of ammonium molybdate solution and support B1, the catalyst was dried at 100℃ for 7 h and then calcined at 500℃ for 2 h in air. Catalyst C6 with a Mo content of 3% (wt) was obtained. EPR characterization showed that catalyst C6 eluted in the range of g = 1.94-2.06. Catalyst C6 was reduced at 450℃ for 3 h, and the reduction of Mo was determined by XPS. The reduction of Mo after peak separation is shown in Table 1.

[0066] Three grams of catalyst C6 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0067]

Example 7

[0068] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 1 mol / L NaBH4 aqueous solution at 50 °C for 6 hours, filter and dry to obtain support B1. EPR characterization shows that support B1 has a peak in the range of g = 1.94-2.06.

[0069] Equal volumes of copper nitrate solution and support B1 were impregnated and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air atmosphere. Catalyst C7 with a Cu content of 2% (wt) was obtained. EPR characterization showed peaks in the range of g = 1.94-2.06. Catalyst C7 was reduced at 450℃ for 3 h, and the reduction of Cu was determined by XPS. The reduction of Cu after peak separation is shown in Table 1.

[0070] Three grams of catalyst C7 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0071]

Example 8

[0072] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 5 mol / L NaBH4 aqueous solution at 95 °C for 15 hours, filter and dry to obtain support B8. EPR characterization shows that support B8 has a peak in the range of g = 1.94-2.06.

[0073] An equal volume of ammonium molybdate solution and support B8 were impregnated and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air atmosphere. Catalyst C8 with a Mo content of 2% (wt) was obtained. EPR characterization showed that catalyst C8 eluted in the range of g = 1.94-2.06. After reducing catalyst C8 at 450℃ for 3 h, XPS was used to determine the reduction of Mo. The reduction of Mo after peak separation is shown in Table 1.

[0074] Three grams of catalyst C8 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0075]

Example 9

[0076] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 0.2 mol / L NaBH4 aqueous solution at 25 °C for 1 hour, filter and dry to obtain support B9. EPR characterization shows that support B9 has a peak in the range of g = 1.94-2.06.

[0077] After impregnating ammonium molybdate solution and support B9 in equal volumes, the mixture was dried at 100℃ for 7 h and then calcined at 500℃ for 2 h in air atmosphere to obtain catalyst C9 with a Mo content of 2% (wt). EPR characterization showed that catalyst C9 eluted in the range of g = 1.94-2.06. Catalyst C9 was reduced at 450℃ for 3 h, and the reduction of Mo was determined by XPS. The reduction of Mo after peak separation is shown in Table 1.

[0078] Three grams of catalyst C9 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0079]

Example 10

[0080] Take 10 g of zirconia support, dry the support at 100 °C for 7 hours to obtain support A10, treat support A10 in 120 g of 1 mol / L NaBH4 aqueous solution at 50 °C for 6 hours, filter and dry to obtain support B10, characterize support B10 by EPR, and show peaks in the range of g = 1.94-2.06.

[0081] An equal volume of ammonium molybdate solution and support B10 were impregnated and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air atmosphere. Catalyst C10 with a Mo content of 2% (wt) was obtained. EPR characterization showed peaks in the range of g = 1.94-2.06. Catalyst C10 was reduced at 450℃ for 3 h, and the reduction of Mo was determined by XPS. The reduction of Mo after peak separation is shown in Table 1.

[0082] Three grams of catalyst C10 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0083]

Example 11

[0084] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 1 mol / L NaBH4 aqueous solution at 50 °C for 6 hours, filter and dry to obtain support B1. EPR characterization shows that support B1 has a peak in the range of g = 1.94-2.06.

[0085] Lanthanum nitrate solution and support B1 were impregnated in equal volumes and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air atmosphere. Catalyst C11 with a La content of 2% (wt) was obtained. EPR characterization showed that catalyst C11 eluted in the range of g = 1.94-2.06. Catalyst C11 was reduced at 450℃ for 3 h, and the reduction of La was determined by XPS. The La reduction results after peak separation are shown in Table 1.

[0086] Three grams of catalyst C11 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0087]

Example 12

[0088] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 1 mol / L NaBH4 aqueous solution at 50 °C for 6 hours, filter and dry to obtain support B1. EPR characterization shows that support B1 has a peak in the range of g = 1.94-2.06.

[0089] An equal volume of ammonium molybdate solution and support B1 were impregnated and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air atmosphere. Catalyst C12 with a Mo content of 20% (wt) was obtained. EPR characterization showed peaks in the range of g = 1.94-2.06. Catalyst C12 was reduced at 450℃ for 3 h, and the reduction of Mo was determined by XPS. The reduction of Mo after peak separation is shown in Table 1.

[0090] Three grams of catalyst C12 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0091]

Example 13

[0092] Take 10 g of titanium dioxide support, dry the support at 100 °C for 7 hours to obtain support A1. Treat support A1 in 120 g of 1 mol / L NaBH4 aqueous solution at 80 °C for 4 hours, filter and dry to obtain support B13. Characterize support B13 by EPR, and it shows a peak in the range of g = 1.94-2.06.

[0093] An equal volume of ammonium molybdate solution and support B13 were impregnated and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air. Catalyst C13 with a Mo content of 2% (wt) was obtained. EPR characterization showed peaks for catalyst C13 in the range of g = 1.94-2.06. After reducing catalyst C13 at 400℃ for 2 h, the reduction of Mo was determined by XPS. The reduction of Mo after peak separation is shown in Table 1.

[0094] Three grams of catalyst C13 were placed in a reactor, and hydrogen gas was introduced for reduction at 400°C for 2 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0095] Comparative Example 1

[0096] Take 10 g of titanium dioxide support and dry the support at 100 °C for 7 hours to obtain support A1. EPR characterization of support DA1 did not find any peaks in the range of g = 1.94-2.06.

[0097] An equal volume of ammonium molybdate solution and support A1 were impregnated and dried at 100℃ for 7 h, followed by calcination at 500℃ for 2 h in air atmosphere. Catalyst D-C1 with a Mo content of 2% (wt) was obtained. EPR characterization of catalyst D-C1 showed no peaks in the g = 1.94-2.06 range. Catalyst D-C1 was reduced at 450℃ for 3 h, and the reduction of Mo was determined by XPS. The reduction of Mo after peak separation is shown in Table 1.

[0098] Three grams of catalyst D-C1 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and naphthalene-containing materials were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0099] Comparative Example 2

[0100] Take 10 g of titanium oxide support and dry it at 100 °C for 7 hours to obtain support A1. EPR characterization of support A1 showed no peaks in the range of g = 1.94-2.06.

[0101] After impregnating the catalyst D-C2 with an equal volume of cerium nitrate solution and support A1, the catalyst was dried at 100℃ for 7 h and then calcined at 500℃ for 2 h in air atmosphere. Catalyst D-C2 with a Ce content of 2% (wt) was obtained. Catalyst D-C2 was reduced at 450℃ for 3 h, and the reduction of Ce was determined by XPS. The reduction of Ce after peak separation is shown in Table 1.

[0102] Three grams of catalyst D-C2 were placed in a reactor, and hydrogen gas was introduced for reduction at 450°C for 3 hours. The temperature was then lowered to 365°C, and hydrogen gas and a naphthalene-containing material were introduced to investigate the activity. The reaction conditions were as follows: total weight hourly space velocity (WHSV) of 8 h⁻¹. -1 The reaction temperature was 365℃, the reaction pressure was 4.0MPa, the hydrogen-to-hydrocarbon molar ratio was 5.0, and the reaction raw material was a 5% (wt) naphthalene n-hexane solution. The reaction performance is shown in Table 1.

[0103] Table 1

[0104]

[0105] *The reduction treatment conditions refer to the concentration x mol / L, treatment temperature y℃, and treatment time zh of the NaBH4 solution when treating the carrier. These are expressed in the form of x / y / z in the table.

[0106] Except for Example 13, the degree of reducibility of the metal element was calculated by peak separation of the XPS spectrum measured after the corresponding sample was reduced at 450°C for 3 hours.

[0107] ***In this embodiment, the degree of reducibility of the metal element is calculated by peak separation of the XPS spectrum measured after the corresponding sample is reduced at 400℃ for 2 hours.

[0108] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. The application of a polycyclic aromatic hydrocarbon hydrogenation catalyst in the hydrogenation reaction of polycyclic aromatic hydrocarbons, wherein, The polycyclic aromatic hydrocarbon hydrogenation catalyst comprises: a) Carrier, b) An active metal component, wherein the active metal component is selected from at least one of La, Ce, Cu, Cr, Mo, and W; The carrier is a porous carrier treated with a reducing solution, and is characterized by electron paramagnetic resonance (EPR) technology, showing peaks in the range of g = 1.94-2.

06. The catalyst, characterized by X-ray photoelectron spectroscopy, exhibits a reduction degree of 20%–65% for the active metal component. The polycyclic aromatic hydrocarbons are naphthalene and naphthalene derivatives.

2. The application according to claim 1, characterized in that, The carrier is selected from non-acidic or weakly acidic carriers.

3. The application according to claim 2, characterized in that, The carrier is selected from at least one of titanium oxide, zinc oxide, zirconium oxide, cerium oxide, and iron oxide.

4. The application according to claim 3, characterized in that, The carrier is titanium oxide and / or zinc oxide.

5. The application according to claim 1, characterized in that, The active metal component is selected from Ce and / or Mo.

6. The application according to claim 1, characterized in that, Based on the weight of the catalyst, the content of the metal component, calculated by element, is 0.01% to 20%, and the content of the support is 80% to 99.99%.

7. The application according to claim 6, characterized in that, Based on the weight of the catalyst, the content of the metal component, calculated as an element, is 0.1% to 5%, and the content of the support is 95% to 99.9%.

8. The application according to any one of claims 1-7, characterized in that, The preparation method of the polycyclic aromatic hydrocarbon hydrogenation catalyst includes: (1) The porous carrier material is dried to obtain carrier precursor I; (2) After treating the carrier precursor I in a reducing solution and drying it, the carrier II is obtained; (3) Prepare a metal salt solution, load it onto the support II obtained in step (2), dry and calcine to obtain the catalyst.

9. The application according to claim 8, characterized in that, In step (2), the reducing solution used to treat the carrier precursor I is at least one of the aqueous solutions of NaBH4 or KBH4.

10. The application according to claim 9, characterized in that, The reducing solution used to treat the carrier precursor I in step (2) is an aqueous solution of NaBH4.

11. The application according to claim 8, characterized in that, In step (2), the molar concentration of the reducing solution is 0.5~2 mol / L.

12. The application according to claim 8, characterized in that, In step (2), the mass ratio of carrier precursor I to reducing solution is 1:10 to 1:

15.

13. The application according to claim 8, characterized in that, In step (2), the treatment conditions in the reducing solution are: treatment temperature of 40~90°C and treatment time of 5~10h.

14. The application according to claim 8, characterized in that, In step (3), the metal salt solution is selected from at least one of the nitrate, chloride, and acetate salts of active metals.

15. The application according to claim 8, characterized in that, In step (3), the catalyst is roasted in air, the roasting temperature is 300~700°C, and the roasting time is 1~10h.

16. The application according to claim 8, characterized in that, In step (3), the catalyst is roasted in air, the roasting temperature is 400~550°C, and the roasting time is 2~6h.

17. The application according to claim 1, characterized in that, The reaction conditions are as follows: reaction temperature 100-550 °C, reaction pressure 1.0-5.0 MPa, hydrogen-to-hydrocarbon molar ratio 1-8, and feed weight hourly space velocity 0.5-20 h⁻¹. -1 .

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