Catalyst for naphthalene hydrogenation reaction as well as preparation method and application thereof

Abstract

The invention provides a catalyst for naphthalene hydrogenation reaction and a preparation method and application thereof. A catalyst for naphthalene hydrogenation reaction comprises a molecular sieve, a noble metal loaded on the molecular sieve and a silicon dioxide film, and the noble metal is coated with the silicon dioxide film. The invention provides a preparation method of a catalyst for naphthalene hydrogenation reaction, which comprises the following steps: 1, carrying out contact reaction on a molecular sieve, a noble metal source, a silicon source a and an alkali source a to obtain a precursor, co-molding the precursor and water, and extruding into strips to obtain a mixture A; 2, a template agent, water, a silicon source b and an alkali source b are subjected to a contact reaction, and a mixture B is obtained; and 3, carrying out a contact reaction on the mixture B and the mixture A, carrying out a crystallization reaction, washing, drying and roasting to obtain the catalyst. According to the prepared catalyst, the noble metal is distributed inside the silicon dioxide film and outside the molecular sieve, so that the metal on the outer surface of the molecular sieve is not easy to lose in the reaction process, and the service life of the catalyst is prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of catalysis, and in particular to a catalyst for naphthalene hydrogenation reaction and a preparation method and application thereof. Background Art

[0002] With people's increasing attention to environmental protection, the regulations on clean environment have become increasingly stringent in recent years. Low-sulfur, low-aromatic, high-cetane diesel has become a development trend in countries around the world. The use of catalysts in the aromatics hydrogenation reaction can reduce the aromatics content of diesel, improve the cetane number of diesel, and reduce the emission of harmful gases. Therefore, the development of new aromatics hydrogenation catalysts has attracted widespread attention. Traditional metal sulfide or oxide catalysts such as CoMo, NiMo and NiW require higher operating temperatures, and the reaction is limited by equilibrium, which cannot complete the deep hydrogenation of aromatics, and can no longer meet the reaction requirements of aromatics hydrogenation in the current industry. At present, the aromatics hydrogenation catalysts used at home and abroad are mainly based on Group VIII metals, such as Rh, Pt, Pd, W, Ni, Fe and Co. The use of precious metal catalysts can overcome the above shortcomings of traditional metal sulfide and oxide catalysts. Precious metal catalysts have high hydrogenation reaction activity under low temperature and low pressure conditions, and can achieve deep hydrogenation of aromatics under milder reaction conditions compared with sulfided catalysts. However, due to the scarcity and high price of precious metals, how to improve the activity of precious metal catalysts and how to reduce the loss of precious metals during the reaction process have always been topics of great concern in the field of catalysis. Traditional supported catalysis generally first obtains a mesoporous molecular sieve of pure silicon, and then bonds the hydroxyl groups on the surface of the mesoporous molecular sieve with heteroatoms by means of immersion, calcination, etc. The catalyst obtained by this direct impregnation method is very easy to cause the loss of metal components during the reaction because the metal is on the surface of the molecular sieve, resulting in a reduction in the service life of the catalyst and a reduction in the catalytic effect. Therefore, a catalyst with high catalytic activity and stable performance is urgently needed in the prior art. Summary of the invention

[0003] In order to solve the above problems in the prior art, the present invention provides a catalyst for naphthalene hydrogenation reaction and a preparation method and application thereof.

[0004] In a first aspect, the present invention provides a catalyst for naphthalene hydrogenation reaction, comprising a molecular sieve, a noble metal loaded on the molecular sieve, and a silicon dioxide film, wherein the silicon dioxide film covers the noble metal.

[0005] As a specific embodiment of the present invention, the mass ratio of the noble metal to the molecular sieve is less than or equal to 5%.

[0006] As a specific embodiment of the present invention, the mass ratio of the noble metal to the molecular sieve is 2% to 3%.

[0007] As a specific embodiment of the present invention, the noble metal is any one of gold, platinum or palladium.

[0008] In a second aspect, the present invention provides a method for preparing a catalyst for naphthalene hydrogenation reaction, comprising the steps of:

[0009] Step 1: The molecular sieve, the noble metal source, the silicon source a and the alkali source a are contacted and reacted to obtain a precursor, and the precursor is formed and extruded with water to obtain a mixture A;

[0010] Step 2: The template, water, silicon source b and alkali source b are contacted and reacted to obtain a mixture B;

[0011] Step 3: The mixture B is contacted with the mixture A for reaction and crystallization reaction, and a catalyst is obtained after washing, drying and calcining;

[0012] Preferably, the molecular sieve, the noble metal source, the silicon source a and the alkali source a are contacted and reacted to obtain a precursor, and the precursor is dried and put into an extruder together with water, and the mixture A is obtained after extrusion molding and drying.

[0013] Preferably, the water is deionized water.

[0014] As an embodiment of the present invention, the mass ratio of silicon source a to molecular sieve is 1:5 to 2:5; preferably, silicon source a is one or more of ethyl orthosilicate, silica sol or water glass;

[0015] As an embodiment of the present invention, the molecular sieve is MCM-41. The silicon source and alkali source used in the process of preparing the catalyst of the present invention are the same as those used in preparing the MCM-41 molecular sieve, ensuring that the skeleton structure of the silicon dioxide film and the molecular sieve itself is similar, and a silicon dioxide film can be formed on the surface of the molecular sieve.

[0016] As a specific embodiment of the present invention, in step 2, the silicon source b includes SiO2, and the alkali source b includes OH - ; SiO2, water, template and OH - The molar ratio is 1:80~160:0.1~0.7:2~7.

[0017] Preferably, the molar ratio of silicon source b, deionized water, template and alkali source b is 1:100-140:0.2-0.5:4-5.

[0018] As a specific embodiment of the present invention, the mass ratio of the noble metal source to the molecular sieve is ≤10%, preferably 2% to 8%.

[0019] As a specific embodiment of the present invention, the noble metal source is any one of a gold source, a platinum source or a palladium source.

[0020] Preferably, the gold source is one or more of gold oxide, hydroxide, sulfide, chloride and cyanide;

[0021] As a specific embodiment of the present invention, the platinum source is one or more of platinum oxide, hydroxide, sulfide, chloride, and cyanide;

[0022] As a specific embodiment of the present invention, the palladium source is one or more of palladium oxide, hydroxide, sulfide, chloride and cyanide.

[0023] As a specific embodiment of the present invention, the mass of the alkali source a is 20% to 50% of the mass of the silicon source a.

[0024] Preferably, the alkaline source a is a NaOH solution, and preferably, the concentration of the NaOH solution is less than or equal to 0.5 mol / L, preferably 0.1 mol / L to 0.15 mol / L. The NaOH solution at this concentration condition can ensure that the prepared catalyst forms a silicon dioxide film.

[0025] As a specific embodiment of the present invention, the mass of the deionized water added during the extrusion process in step 1 is 10% to 30% of the mass of the precursor.

[0026] Preferably, the mass of the deionized water added during the extrusion process in step 1 is 15% to 25% of the mass of the precursor.

[0027] As a specific embodiment of the present invention, the template agent is one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride or hexadecyltriethylammonium bromide.

[0028] Preferably, the template is hexadecyltrimethylammonium chloride.

[0029] As a specific embodiment of the present invention, the silicon source b is one or more of white carbon black, tetraethyl orthosilicate, sodium silicate or silica sol.

[0030] Preferably, the silicon source b is tetraethyl orthosilicate.

[0031] As a specific embodiment of the present invention, the alkali source b is one or more of sodium hydroxide, tetramethylammonium hydroxide or ammonia water.

[0032] Preferably, the alkaline source b is aqueous ammonia.

[0033] As a specific embodiment of the present invention, the drying temperature in step 1 is 100-150° C., preferably 120-130° C. As a specific embodiment of the present invention, the calcination temperature in step 3 is 400-600° C., and the calcination time is 2-10 hours.

[0034] As a specific embodiment of the present invention, in step three, the crystallization temperature is 110-140° C., preferably 120-130° C.; the crystallization time is 72-108 h, preferably 84-100 h.

[0035] As a specific embodiment of the present invention, the drying temperature in step three is 100-150°C, preferably 120-130°C.

[0036] In a third aspect, the present invention provides a catalyst prepared according to the preparation method of the second aspect.

[0037] As a specific embodiment of the present invention, the catalyst includes a molecular sieve, a noble metal supported on the molecular sieve, and a silicon dioxide film, wherein the silicon dioxide film covers the noble metal.

[0038] As a specific embodiment of the present invention, the noble metal is any one of gold, platinum or palladium.

[0039] In a fourth aspect, the present invention provides a use of the catalyst according to the first aspect or the third aspect in a naphthalene hydrogenation reaction.

[0040] In a fifth aspect, the present invention provides a method for naphthalene hydrogenation reaction. Naphthalene and H2 are used as raw materials and the catalyst of the first aspect or the catalyst of the third aspect is used to react in a reactor.

[0041] Compared with the prior art, the present invention has the following beneficial effects.

[0042] In the process of preparing the catalyst of the present invention, in step 1, silicon source a is hydrolyzed under the action of alkaline solution to generate a silica gel mesh with a viscous structure, and the viscous silica gel mesh bonds the molecular sieve particles to each other. After extrusion, the silica gel mesh is transformed into a silica film under high temperature conditions, covering the silanol structure on the outer surface of the molecular sieve. Since the skeleton structure of the silica film is similar to that of the molecular sieve itself, the outer surface of the molecular sieve will not be covered and blocked, and since the metal is on the outer surface of the molecular sieve, the silica film formed will have a gap at the position of the metal. At this time, a template, water, silicon source b and an alkaline source mixed solution are added for secondary crystallization, and the position of the gap is crystallized and grown to form a complete silica film, and the silica film includes metal, so that the metal exists outside the molecular sieve and inside the silica film. In practical applications, the reactants will enter the outer surface of the molecular sieve from the silica film in the form of diffusion, and these silica films make it difficult for the metal active sites to be lost during the reaction, effectively extending the life and activity of the catalyst.

[0043] The method adopts the method of directly adding the noble metal source in the molecular sieve forming stage, without the need to impregnate the molecular sieve and the metal solution, completing the forming and metal impregnation processes in one step, and the preparation method is simple and practical. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is a scanning electron microscope image of the catalyst obtained in Example 3. DETAILED DESCRIPTION

[0045] The present invention will be further described below in conjunction with specific embodiments, but they do not constitute any limitation to the present invention.

[0046] In the embodiments, the scanning electron microscope adopts the S-4700 scanning electron microscope produced by Hitachi.

[0047] Example 1

[0048] Step 1: Add 40g MCM-41 molecular sieve powder, 0.8g Au2O, 8g tetraethyl orthosilicate (TEOS) and 1.6g 0.1mol / L NaOH solution into a mortar and mix them. After mixing evenly, dry them at 100°C. Then, take 30g of the dried sample and put it into an extruder. Add 3g deionized water and stir evenly to start molding. The molded molecular sieve is dried at 100°C and recorded as mixture A.

[0049] Step 2: 4.4 g of hexadecyltrimethylammonium bromide (CTAB) and 38.9 g of deionized water were added to the reactor in sequence, stirred evenly, 5 g of tetraethylorthosilicate (TEOS) was slowly added dropwise, and finally 4.8 g of 0.1 mol / L NaOH was added to adjust the pH of the solution to 11-13. The molar ratio of the reaction mixture obtained was SiO2:H2O:template:OH - The ratio of the carbonyl compounds to the aqueous phase is 1:90:0.5:5, thus obtaining mixture B.

[0050] Step 3: Mix mixture B and mixture A and transfer them to a crystallization kettle, raise the temperature to 110°C, and crystallize at a constant temperature for 72 hours. After the crystallization is complete, wait for the temperature to drop to room temperature, separate and wash the reaction mixture, dry it at 100°C, and finally calcine it at 400°C for 3 hours to obtain the catalyst. The obtained sample was used for naphthalene hydrogenation experiment, and the results are shown in Table 1.

[0051] The hydrogenation activity of the catalyst was evaluated in a high-pressure reactor. 0.3 g of the catalyst was added to a reactor containing 50 mL of n-octane containing 5% (mass fraction) naphthalene, and hydrogen was introduced to increase the pressure and temperature. The reaction H2 pressure was 4.0 MPa, the temperature was 250°C, the stirring rate was 500 r / min, and the product was subjected to chromatographic analysis after 900 min of reaction.

[0052] Example 2

[0053] The difference from Example 1 is that:

[0054] Step 1: Change the gold source to AuCl3, the amount is 1.6g, the silicon source is changed to silica sol (silica sol JN-25, silica content is 25wt%), the amount is 12g, the amount of NaOH solution is changed to 3.6g, the amount of deionized water is changed to 6g, and the drying temperature is changed to 110℃.

[0055] Step 2: The template agent was changed to hexadecyltrimethylammonium chloride (CTAC) in an amount of 1.8 g, the amount of deionized water was changed to 20.3 g, the silicon source was changed to sodium silicate in an amount of 4 g, and the amount of NaOH was changed to 3.4 g. The molar ratio of the reaction mixture was SiO2:H2O:template agent:OH - It is 1:80:0.4:6.

[0056] Step 3: The crystallization temperature was changed to 120°C, the crystallization time was changed to 80h, the calcination temperature was changed to 450°C, and the calcination time was changed to 4h.

[0057] The obtained sample was used for naphthalene hydrogenation experiment, and the experimental conditions were the same as in Example 1. The results are shown in Table 1.

[0058] Example 3

[0059] The difference from Example 1 is that:

[0060] Step 1: Change the gold source to AuCl3, the amount used is 3.2g, the amount of TEOS to 12g, the amount of NaOH solution to 4.8g, the amount of deionized water to 7.5g, and the drying temperature to 120℃.

[0061] Step 2: The template agent was changed to hexadecyltrimethylammonium chloride (CTAC) in an amount of 1.4 g, the amount of deionized water was changed to 25.9 g, the amount of TEOS was changed to 3 g, and the alkali source was changed to ammonia water in an amount of 2.0 g. The molar ratio of the reaction mixture obtained was SiO2:H2O:template agent:OH - It is 1:100:0.3:4.

[0062] Step 3: The crystallization temperature was changed to 130°C, the crystallization time was changed to 90h, the calcination temperature was changed to 500°C, and the calcination time was changed to 5h. The SEM image of the sample is shown in Figure 1 .

[0063] The obtained sample was used for naphthalene hydrogenation experiment, and the experimental conditions were the same as in Example 1. The results are shown in Table 1.

[0064] Example 4

[0065] Step 1: Add 40g MCM-41 molecular sieve powder, 3.2g PtO, 12g TEOS and 4.8g 0.1mol / L NaOH solution into a mortar and mix them. After mixing evenly, dry them at 120°C. Then take 30g of the dried sample and put it into an extruder. Add 7.5g deionized water and stir evenly before starting to shape it. Dry the formed molecular sieve at 120°C to obtain mixture A.

[0066] Step 2: 1.4 g of hexadecyltrimethylammonium chloride (CTAC) and 25.9 g of deionized water were added to the reactor in sequence, stirred evenly, 3 g of tetraethyl orthosilicate (TEOS) was slowly added dropwise, and finally 2.0 g of ammonia water was added to adjust the pH of the solution to 11-13. The molar ratio of the reaction mixture obtained was SiO2:H2O:template:OH - The mixture B is obtained with a ratio of 1:100:0.3:4.

[0067] Step 3: Mix mixture B and mixture A and transfer them to a crystallization kettle, raise the temperature to 130°C, and crystallize at a constant temperature for 90 hours. After the crystallization is complete, wait for the temperature to drop to room temperature, separate the reaction mixture, wash it, dry it at 120°C, and finally calcine it at 500°C for 5 hours to obtain the catalyst.

[0068] The obtained sample was used for naphthalene hydrogenation experiment, and the experimental conditions were the same as in Example 1. The results are shown in Table 1.

[0069] Example 5

[0070] Step 1: Add 40g MCM-41 molecular sieve powder, 3.2g PdCl2, 12g TEOS and 4.8g 0.1mol / L NaOH solution into a mortar and mix them. After mixing evenly, dry them at 120°C. Then take 30g of the dried sample and put it into an extruder, add 7.5g deionized water, stir evenly and start molding. Dry the molded molecular sieve at 120°C to obtain mixture A.

[0071] Step 2: 1.4 g of hexadecyltrimethylammonium chloride (CTAC) and 25.9 g of deionized water were added to the reactor in sequence, stirred evenly, 3 g of tetraethyl orthosilicate (TEOS) was slowly added dropwise, and finally 2.0 g of ammonia water was added to adjust the pH of the solution to 11-13. The molar ratio of the reaction mixture obtained was SiO2:H2O:template:OH - The mixture B is obtained with a ratio of 1:100:0.3:4.

[0072] Mixture B and mixture A are mixed and transferred to a crystallization kettle, heated to 130°C, and crystallized at a constant temperature for 90 hours. After the crystallization is complete, the temperature is lowered to room temperature, the reaction mixture is separated, washed, and dried at 120°C, and finally calcined at 500°C for 5 hours to obtain the catalyst.

[0073] The obtained sample was used for naphthalene hydrogenation experiment, and the experimental conditions were the same as in Example 1. The results are shown in Table 1.

[0074] Comparative Example 1

[0075] 40g of MCM-41 molecular sieve powder and 14.2g of pseudo-boehmite (Al2O3 content is 70%) are added to a mixer and mixed. After mixing evenly, 25.8g of dilute nitric acid (HNO3 content is 6.3%) is added for kneading, and then 15.5g of deionized water is added for further kneading. The kneaded material is then put into an extruder for molding. The molded molecular sieve is dried at 120°C and then calcined at 500°C for 5h. The molded molecular sieve sample is then mixed with 3.2g of AuCl3 solution for 4h, dried at 120°C and then calcined at 500°C for 5h to obtain the catalyst.

[0076] The experimental conditions were the same as those in Example 1. The obtained sample was used for a naphthalene hydrogenation experiment under the same experimental conditions as in Example 1. The results are shown in Table 1.

[0077] Comparative Example 2

[0078] Step 1: Add 40g MCM-41 molecular sieve powder, 3.2g AuCl3, 12g TEOS and 8.4g 0.1mol / L NaOH solution into a mortar and mix them. After mixing evenly, dry them at 120°C. Then take 30g of the dried sample and put it into an extruder. Add 7.5g deionized water and stir evenly before forming. Dry the formed molecular sieve at 120°C to obtain mixture A.

[0079] Step 2: 1.4 g of hexadecyltrimethylammonium chloride (CTAC) and 25.9 g of deionized water were added to the reactor in sequence, stirred evenly, 3 g of tetraethyl orthosilicate (TEOS) was slowly added dropwise, and finally 2.0 g of ammonia water was added to adjust the pH of the solution to 11-13. The molar ratio of the reaction mixture obtained was SiO2:H2O:template:OH - The mixture B is obtained with a ratio of 1:100:0.3:4.

[0080] Step 3: Mix mixture B and mixture A and transfer them to a crystallization kettle, raise the temperature to 130°C, and crystallize at a constant temperature for 90 hours. After the crystallization is complete, wait for the temperature to drop to room temperature, separate the reaction mixture, wash it, dry it at 120°C, and finally calcine it at 500°C for 5 hours to obtain the catalyst.

[0081] The obtained sample was used for naphthalene hydrogenation experiment, and the experimental conditions were the same as in Example 1. The results are shown in Table 1.

[0082] Table 1 Naphthalene hydrogenation experimental results

[0083]

[0084]

[0085] As can be seen from Examples 1-5 and Table 1, the catalyst obtained by this method has shown excellent catalytic performance in terms of conversion rate and tetralin selectivity. The conversion rate of naphthalene can reach 99.2% and the tetralin selectivity can reach 82.3% during the reaction. In Comparative Example 1, the conventional molding method is used for loading and impregnation. First, due to the addition of adhesives during the molding process, the active sites of the conventional method in the catalyst of the same mass are relatively few. Second, due to the absence of the protection of the outer surface silicon dioxide film, the metals on the surface of these molecular sieves are very likely to be lost during the reaction, causing the catalyst activity to decrease. In Comparative Example 2, due to the addition of too much alkali in step 1, the collapse of the molecular sieve skeleton itself can be caused while the silicon source hydrolysis generates silicon dioxide film and sticky net, so the catalytic activity is very low.

[0086] Depend on Figure 1 The catalyst prepared by implementation 3 of the present invention can be clearly seen to have a silica spherical film on the outer surface and no metal compounds can be seen in the entire field of view, indicating that the precious metals are distributed inside the silica film and outside the molecular sieve, and the outer surface of the precious metals is protected by the silica film, so that the precious metals on the outer surface of the molecular sieve are not easily lost during the reaction, thereby extending the service life of the catalyst.

[0087] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A catalyst for naphthalene hydrogenation, It is characterized in that The invention comprises a molecular sieve, a noble metal loaded on the molecular sieve and a silicon dioxide film, wherein the silicon dioxide film covers the noble metal.

2. The catalyst according to claim 1, It is characterized in that The mass ratio of the noble metal to the molecular sieve is less than or equal to 5%.

3. The catalyst according to claim 2, characterized in that the mass ratio of the noble metal to the molecular sieve is 2% to 3%.

4. The catalyst according to any one of claims 1 to 3, It is characterized in that The noble metal is any one of gold, platinum or palladium.

5. A method for preparing a catalyst for naphthalene hydrogenation, It is characterized in that The steps include: Step 1: The molecular sieve, the noble metal source, the silicon source a and the alkali source a are contacted and reacted to obtain a precursor, and the precursor is formed and extruded with water to obtain a mixture A; Step 2: The template, water, silicon source b and alkali source b are contacted and reacted to obtain a mixture B; Step 3: The mixture B is contacted with the mixture A for reaction and crystallization reaction, and a catalyst is obtained after washing, drying and calcining; Preferably, the molecular sieve, the noble metal source, the silicon source a and the alkali source a are contacted and reacted to obtain a precursor, and the precursor is dried and put into an extruder together with water to form and dry to obtain a mixture A; Preferably, the water is deionized water.

6. The preparation method according to claim 5, It is characterized in that The mass ratio of the silicon source a to the molecular sieve is 1:5 to 2:5; preferably, the silicon source a is one or more of ethyl orthosilicate, silica sol or water glass; and / or the molecular sieve is MCM-41.

7. The preparation method according to claim 5 or 6, It is characterized in that The silicon source b in step 2 includes SiO 2 The alkaline source b includes OH - ; The SiO 2 , the water, the template and the OH - The molar ratio is 1:80-160:0.1-0.7:2-7; preferably 1:100-140:0.2-0.5:4-5.

8. The preparation method according to claim 7, It is characterized in that The mass ratio of the noble metal source to the molecular sieve in step 1 is ≤10%; preferably 2% to 8%; and / or, The noble metal source is any one of a gold source, a platinum source or a palladium source; preferably, the gold source is one or more of gold oxide, hydroxide, sulfide, chloride and cyanide; and / or, the platinum source is one or more of platinum oxide, hydroxide, sulfide, chloride and cyanide; and / or, the palladium source is one or more of palladium oxide, hydroxide, sulfide, chloride and cyanide; and / or, The mass of the alkali source a is 20% to 50% of the mass of the silicon source a; preferably, the alkali source a is a NaOH solution, preferably, the solubility of the NaOH solution is less than 0.5 mol / L, more preferably, the solubility of the NaOH solution is 0.1 mol / L to 0.15 mol / L; and / or, the mass of the deionized water added during the extrusion process in step 1 is 10% to 30% of the mass of the precursor, preferably 15% to 25%.

9. The preparation method according to claim 8, It is characterized in that The template agent is one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride or hexadecyltriethylammonium bromide; and / or, the silicon source b is one or more of white carbon black, tetraethyl orthosilicate, sodium silicate or silica sol; and / or, the alkali source b is one or more of sodium hydroxide, tetramethylammonium hydroxide or ammonia water.

10. The preparation method according to claim 9, It is characterized in that The drying temperature in step one is 100-150°C, preferably 120-130°C; and / or, the calcination temperature in step three is 400-600°C, and the calcination time is 2-10h; and / or, the crystallization temperature in step three is 110-140°C, preferably 120-130°C; and / or, the crystallization time in step three is 72-108h, preferably 84-100h; and / or, the drying temperature in step three is 100-150°C, preferably 120-130°C.

11. Use of the catalyst according to any one of claims 1 to 4 or the catalyst prepared according to any one of claims 5 to 10 in naphthalene hydrogenation reaction.

12. A method for hydrogenating naphthalene, It is characterized in that Naphthalene and H 2 The catalyst according to any one of claims 1 to 4 or the catalyst prepared by the method according to any one of claims 5 to 10 is used as the raw material, and the reaction is carried out in a reactor.

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