Molecular sieve catalyst, its preparation method and application

Abstract

The application discloses a molecular sieve catalyst and a preparation method and application thereof. The catalyst comprises a first component, a second component, a hydrogen type molecular sieve and a carrier; the first component is selected from Pt single substance and / or Pd single substance; the second component is Ru single substance; and the hydrogen type molecular sieve is selected from at least one of FAU, BEA, MOR and MTW. The catalyst provided by the application is applied to catalyzing the reaction of bridging tetrahydrodicyclopentadiene isomerization into hanging tetrahydrodicyclopentadiene, and the stability of the catalyst can be remarkably prolonged. Under the reaction conditions provided by the application, the conversion rate of bridging tetrahydrocyclopentadiene can reach more than 99 %, and the selectivity of hanging tetrahydrodicyclopentadiene is close to 100 %. The catalyst is continuously used in a fixed bed reactor for 8000 hours, and no deactivation phenomenon is found.

Description

Technical Field

[0001] This application relates to a molecular sieve catalyst, its preparation method and application, and belongs to the field of catalyst materials. Background Technology

[0002] Exo-THDCPD is a high-energy-density liquid fuel. It is characterized by high calorific value, high density, and low freezing point, and is a major component of missile / rocket propellant JP-10.

[0003] Bridged tetrahydrodicyclopentadiene can be prepared by isomerization of bridging tetrahydrodicyclopentadiene. Currently, reported catalysts for the isomerization of bridging tetrahydrodicyclopentadiene include concentrated sulfuric acid, AlCl3, molecular sieves, and supported metal molecular sieves. Among these, AlCl3 catalysts have the advantages of mild reaction conditions, high conversion rate, and high selectivity, making them the currently widely used catalysts. However, the difficulty in separating AlCl3 catalysts from the products leads to large catalyst consumption, making reuse impossible and product purification difficult. Therefore, molecular sieve-based catalysts represent a development direction to replace current AlCl3 catalysts. Bridged tetrahydrodicyclopentadiene readily undergoes polymerization on molecular sieve catalysts, generating carbon deposits and causing rapid catalyst deactivation. Although reports indicate that using platinum or palladium-supported molecular sieve catalysts, in the presence of hydrogen, can delay carbon formation and extend catalyst lifetime, the problem of slow deactivation still exists. How to further improve catalyst stability is a problem that needs to be solved. Summary of the Invention

[0004] To improve the stability of bridged tetrahydrodicyclopentadiene hydroisomerization catalysts for the preparation of hanging tetrahydrodicyclopentadiene, this application provides a supported molecular sieve catalyst. The first component is one or both of Pt and Pd, the second component is Ru, and the third component is a hydrogen-form molecular sieve with 12-membered ring pores and an oxide support. The catalyst provided in this application can inhibit carbon deposition and extend catalyst lifetime. In a fixed-bed reactor, the catalyst lifetime can reach over 8000 hours.

[0005] According to one aspect of this application, a molecular sieve catalyst is provided, comprising a first component, a second component, a hydrogen-form molecular sieve, and a support;

[0006] The first component is selected from elemental Pt and / or elemental Pd;

[0007] The second component is elemental Ru;

[0008] The hydrogen-type molecular sieve is a macroporous molecular sieve with twelve-membered ring pores.

[0009] The hydrogen-form molecules are selected from at least one of FAU, BEA, MOR, and MTW. For example, Y-type, USY-type, and mordenite.

[0010] The carrier is selected from at least one of alumina, silicon oxide, and zirconium oxide.

[0011] In the molecular sieve catalyst

[0012] The mass of the first component is 0.1 to 3 wt% of the mass of the hydrogen-form molecular sieve;

[0013] Optionally, the mass of the first component is any value or a range between 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, and 3 wt% of the mass of the hydrogen-type molecular sieve.

[0014] The mass of the second component is 0.05 to 1 wt% of the mass of the hydrogen-form molecular sieve;

[0015] Optionally, the mass of the second component is any value or a range between any two of 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, and 1wt% of the mass of the hydrogen-type molecular sieve.

[0016] The mass ratio of the hydrogen-type molecular sieve to the support is 10:90 to 70:30.

[0017] According to another aspect of this application, a method for preparing the above-mentioned molecular sieve catalyst is provided, comprising the following steps:

[0018] 1) The hydrogen-type molecular sieve is impregnated in an aqueous solution containing the first component source and the second component source, dried (I) and calcined (I) to obtain the catalyst precursor;

[0019] 2) The catalyst precursor obtained in 1) is mixed with the support and inorganic acid, dried (II) and calcined (II) to obtain the molecular sieve catalyst.

[0020] The first component source is selected from at least one of chloroplatinic acid, platinum nitrate, platinum chloride, ammonium chloroplatinate, palladium chloride, and palladium nitrate;

[0021] The second component source is selected from ruthenium chloride and / or ruthenium nitrate;

[0022] The solid-liquid ratio of the hydrogen-form molecular sieve to the aqueous solution containing the first component source and the second component source is 0.5:1 to 1:2.

[0023] Optionally, the solid-liquid ratio of the hydrogen-type molecular sieve to the aqueous solution containing the first component source and the second component source is any value among 0.5:1, 0.5:2, 1:1, 1:2, or any range between the two.

[0024] The temperature of the drying process I is 80–120°C;

[0025] Optionally, the temperature of the drying I is any value among 80°C, 90°C, 100°C, 110°C, and 120°C, or a range between any two.

[0026] The drying time for step I is 8–24 hours;

[0027] Optionally, the drying time I is any value among 8h, 12h, 18h, and 24h, or a range between any two.

[0028] The temperature of the calcination I is 350–600°C;

[0029] Optionally, the temperature of the calcination I is any value among 350°C, 400°C, 450°C, 500°C, 550°C, and 600°C, or a range between any two.

[0030] The roasting time for the first stage is 2 to 8 hours.

[0031] Optionally, the roasting time I is any value among 2h, 3h, 4h, 5h, 6h, 7h, and 8h, or a range between any two.

[0032] The inorganic acid is selected from hydrochloric acid and / or nitric acid;

[0033] The ratio of the catalyst precursor to the inorganic acid is 0.5 to 2:1;

[0034] Optionally, the ratio of the catalyst precursor to the inorganic acid is any value from 0.5:1, 1:1, 1.5:1, 2:1, or any range between the two.

[0035] The temperature of the drying II process is 80–120°C;

[0036] Optionally, the temperature of the drying II is any value among 80°C, 90°C, 100°C, 110°C, and 120°C, or a range between any two.

[0037] The drying time for step II is 8–24 hours;

[0038] Optionally, the drying time II is any value among 8h, 12h, 18h, and 24h, or a range between any two.

[0039] The temperature of the second calcination is 350–600°C;

[0040] Optionally, the temperature of the calcination II is any value among 350°C, 400°C, 450°C, 500°C, 550°C, and 600°C, or a range between any two.

[0041] The roasting time for the second stage is 2 to 8 hours.

[0042] Optionally, the roasting time II is any value among 2h, 3h, 4h, 5h, 6h, 7h, and 8h, or a range between any two.

[0043] 2) After being mixed evenly, the mixture is extruded.

[0044] According to another aspect of this application, a method for producing hanging tetrahydrodicyclopentadiene via bridging tetrahydrodicyclopentadiene hydroisomerization is provided, comprising the following steps:

[0045] In a reactor, a raw material containing hydrogen gas and a bridged tetrahydrodicyclopentadiene solution is introduced and reacted with a catalyst to obtain a product containing a bridged tetrahydrodicyclopentadiene.

[0046] The catalyst is selected from the molecular sieve catalysts described above or the molecular sieve catalysts prepared by the preparation method described above.

[0047] The space velocity of the raw material is 0.1 to 4 h⁻¹. -1 ;

[0048] Optionally, the space velocity of the raw material is 0.1 h⁻¹. -1 0.5h -1 1h -1 2h -1 3h -1 4h -1 Any value in the range or any value between the two.

[0049] The molar ratio of hydrogen gas to tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is (10-600):1;

[0050] Optionally, the molar ratio of hydrogen to tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is any value from 10:1, 15:1, 50:1, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, or any range between the two.

[0051] The solvent of the bridged tetrahydrodicyclopentadiene solution is selected from at least one of n-hexane, cyclohexane, methylcyclohexane, and n-heptane;

[0052] The molar ratio of the solvent to the tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is (1-30):1;

[0053] Optionally, the molar ratio of the solvent to the tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is any value from 1:1, 5:1, 10:1, 20:1, 30:1, or any range between the two.

[0054] The reaction temperature is 50–300°C;

[0055] Optionally, the temperature of the reaction is any value or a range between 50°C, 100°C, 150°C, 200°C, 250°C, and 300°C.

[0056] The reaction pressure is 0.1–5 MPa.

[0057] Optionally, the pressure of the reaction is any value among 0.1 MPa, 0.5 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, and 5 MPa, or a range between any two.

[0058] The catalyst is reduced;

[0059] The reducing atmosphere is a hydrogen atmosphere;

[0060] The reduction temperature is 300–500°C;

[0061] Optionally, the reduction temperature is any value among 300℃, 350℃, 400℃, 450℃, and 500℃, or a range between any two.

[0062] The reduction time is 2 to 6 hours.

[0063] Optionally, the restoration time is any value among 2h, 3h, 4h, 5h, and 6h, or a range between any two.

[0064] The reactor is selected from a fixed-bed reactor or a batch reactor.

[0065] The beneficial effects that this application can produce include:

[0066] The catalyst provided in this application, when applied to the catalytic isomerization of bridged tetrahydrodicyclopentadiene to hanging tetrahydrodicyclopentadiene, can significantly extend catalyst stability. Under the reaction conditions provided in this application, the conversion rate of bridged tetrahydrodicyclopentadiene can reach over 99%, and the selectivity of hanging tetrahydrodicyclopentadiene is close to 100%. No deactivation was observed in the catalyst after continuous use in a fixed-bed reactor for 8000 hours. Detailed Implementation

[0067] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments. Unless otherwise specified, the raw materials used in the embodiments of the present application are all purchased through commercial channels.

[0068] Example 1

[0069] 1.26 g of chloroplatinic acid, 0.60 g of palladium chloride dihydrate, and 0.93 g of ruthenium chloride trihydrate were dissolved in 60 g of water. The solution was then impregnated onto 60 g of HUSY molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 500 °C for 4 hours. The sample was then mixed with 40 g of alumina and 20 g of nitric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 500 °C for 4 hours to obtain catalyst A. The loading amounts of the catalyst metals on the molecules are listed in Table 1.

[0070] 50g of catalyst A was loaded into a fixed-bed reactor. Hydrogen gas was introduced and the reactor temperature was raised to 300℃ and maintained for 6 hours. The temperature was then lowered to 150℃ and the pressure to 0.1MPa. A hexane solution of bridged tetrahydrodicyclopentadiene was introduced into the reactor, maintaining a space velocity of 2.0 h⁻¹ for the bridged dicyclopentadiene. -1 The molar ratio of hydrogen to n-hexane to bridged dicyclopentadiene was 100:5:1. The reaction products were analyzed by gas chromatography, and the conversion rate and selectivity are listed in Table 2.

[0071] Example 2

[0072] 1.68 g of palladium chloride dihydrate and 0.72 g of ruthenium chloride trihydrate were dissolved in 50 g of water. The solution was then impregnated onto 70 g of HUSY molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 300 °C for 6 hours. The sample was then mixed with 30 g of alumina and 20 g of nitric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 300 °C for 6 hours to obtain catalyst B. The metal loadings on the catalyst molecules are listed in Table 1.

[0073] 50g of catalyst B was loaded into a fixed-bed reactor. Hydrogen gas was introduced and the reactor temperature was raised to 500℃ and maintained for 3 hours. The temperature was then lowered to 200℃ and the pressure to 4.0 MPa. A hexane solution of bridged tetrahydrodicyclopentadiene was introduced into the reactor, maintaining a space velocity of 4.0 h⁻¹ for the bridged dicyclopentadiene. -1 The molar ratio of hydrogen to n-hexane to bridged dicyclopentadiene was 10:25:1. The reaction products were analyzed by gas chromatography, and the conversion and selectivity are listed in Table 2.

[0074] Example 3

[0075] 0.32 g of chloroplatinic acid, 0.06 g of palladium chloride dihydrate, and 0.26 g of ruthenium chloride trihydrate were dissolved in 60 g of water. The solution was then impregnated onto 10 g of HUSY molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 400 °C for 8 hours. The sample was then mixed with 90 g of silica and 20 g of hydrochloric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 400 °C for 8 hours to obtain catalyst C. The metal loadings on the catalyst molecules are listed in Table 1.

[0076] Example 4

[0077] 0.32 g of chloroplatinic acid, 0.30 g of palladium chloride dihydrate, and 0.23 g of ruthenium chloride trihydrate were dissolved in 70 g of water. The solution was then impregnated onto 30 g of HUSY molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 300 °C for 6 hours. The sample was then mixed with 70 g of alumina and 20 g of nitric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 300 °C for 6 hours to obtain catalyst D. The metal loadings on the catalyst molecules are listed in Table 2.

[0078] Example 5

[0079] 0.63 g of chloroplatinic acid, 1.80 g of palladium chloride dihydrate, and 1.24 g of ruthenium chloride trihydrate were dissolved in 80 g of water. The solution was then impregnated onto 60 g of HUSY molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 400 °C for 5 hours. The sample was then mixed with 40 g of silica and 20 g of hydrochloric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 400 °C for 5 hours to obtain catalyst E. The loading amounts of the catalyst metals on the molecules are listed in Table 1.

[0080] 50g of catalyst E was loaded into a fixed-bed reactor. Hydrogen gas was introduced and the reactor temperature was raised to 400℃ and maintained for 4 hours. The temperature was then lowered to 50℃ and the pressure to 3.0 MPa. A heptane solution of bridged tetrahydrodicyclopentadiene was introduced into the reactor, maintaining a space velocity of 0.1 h⁻¹ for the bridged dicyclopentadiene. -1 The molar ratio of hydrogen to n-heptane to bridged dicyclopentadiene was 600:1:1. The reaction products were analyzed by gas chromatography, and the conversion and selectivity are listed in Table 2.

[0081] Example 6

[0082] 3.15 g of chloroplatinic acid, 0.20 g of palladium chloride dihydrate, and 0.52 g of ruthenium chloride trihydrate were dissolved in 70 g of water. The solution was then impregnated onto 50 g of HUSY molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 350 °C for 8 hours. The sample was then mixed with 50 g of zirconium oxide and 20 g of nitric acid. After homogenization, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 350 °C for 8 hours to obtain catalyst F. The loading amounts of the catalyst metals on the molecules are listed in Table 1.

[0083] Example 7

[0084] 1.26 g of chloroplatinic acid, 0.40 g of palladium chloride dihydrate, and 1.03 g of ruthenium chloride trihydrate were dissolved in 90 g of water. The solution was then impregnated onto 40 g of HBeta molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 500 °C for 5 hours. The sample was then mixed with 50 g of alumina and 20 g of nitric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 500 °C for 5 hours to obtain catalyst G. The loading amounts of the catalyst metals on the molecules are listed in Table 1.

[0085] 50 g of catalyst G was loaded into a fixed-bed reactor. Hydrogen gas was introduced and the reactor temperature was raised to 450 °C and maintained for 4 hours. The temperature was then lowered to 250 °C and the pressure to 0.1 MPa. A methylcyclohexane solution of bridged tetrahydrodicyclopentadiene was introduced into the reactor, maintaining a space velocity of 1.0 h⁻¹ for the bridged dicyclopentadiene. -1 The molar ratio of hydrogen to methylcyclohexane to bridged dicyclopentadiene was 50:30:1. The reaction products were analyzed by gas chromatography, and the conversion and selectivity are listed in Table 2.

[0086] Example 8

[0087] 0.64 g of palladium chloride dihydrate and 0.25 g of ruthenium chloride trihydrate were dissolved in 120 g of water. The solution was then impregnated onto 20 g of HBeta molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 450 °C for 4 hours. The sample was then mixed with 80 g of alumina and 20 g of nitric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 450 °C for 4 hours to obtain catalyst H. The metal loadings on the catalyst molecules are listed in Table 1.

[0088] Example 9

[0089] 0.50 g of chloroplatinic acid, 0.48 g of palladium chloride dihydrate, and 0.70 g of ruthenium chloride trihydrate were dissolved in 100 g of water. The solution was then impregnated onto 30 g of HBeta molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 550 °C for 6 hours. The sample was then mixed with 70 g of silica and 20 g of hydrochloric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 550 °C for 6 hours to obtain catalyst I. The metal loading amounts on the catalyst molecules are listed in Table 1.

[0090] Example 10

[0091] 1.68 g of chloroplatinic acid and 0.62 g of ruthenium chloride trihydrate were dissolved in 40 g of water. The solution was then impregnated onto 40 g of HBeta molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 500 °C for 2 hours. The sample was then mixed with 60 g of silica and 20 g of nitric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 500 °C for 2 hours to obtain catalyst J. The metal loadings on the catalyst molecules are listed in Table 1.

[0092] Example 11

[0093] 1.18 g of chloroplatinic acid, 0.32 g of palladium chloride dihydrate, and 0.62 g of ruthenium chloride trihydrate were dissolved in 40 g of water. The solution was then impregnated onto 40 g of HZSM-12 molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 500 °C for 3 hours. The sample was then mixed with 60 g of silica and 20 g of nitric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 500 °C for 3 hours to obtain catalyst K. The metal loadings on the catalyst molecules are listed in Table 1.

[0094] 50g of catalyst K was loaded into a fixed-bed reactor. Hydrogen gas was introduced and the reactor temperature was raised to 400℃ and maintained for 4 hours. The temperature was then lowered to 180℃ and the pressure to 0.1MPa. A hexane solution of bridged tetrahydrodicyclopentadiene was introduced into the reactor, maintaining a space velocity of 1.0 h⁻¹ for the bridged dicyclopentadiene. -1 The molar ratio of hydrogen to n-hexane to bridged dicyclopentadiene was 150:10:1. The reaction products were analyzed by gas chromatography, and the conversion and selectivity are listed in Table 2.

[0095] Example 12

[0096] 0.32 g of chloroplatinic acid, 1.80 g of palladium chloride dihydrate, and 0.65 g of ruthenium chloride trihydrate were dissolved in 80 g of water. The solution was then impregnated onto 50 g of HMOR molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 400 °C for 6 hours. The sample was then mixed with 50 g of alumina and 20 g of nitric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 400 °C for 6 hours to obtain catalyst L. The metal loadings on the catalyst molecules are listed in Table 1.

[0097] 50 g of catalyst L was loaded into a fixed-bed reactor. Hydrogen gas was introduced and the reactor temperature was raised to 400 °C and maintained for 5 hours. The temperature was then lowered to 150 °C and the pressure to 5.0 MPa. A cyclohexane solution of bridged tetrahydrodicyclopentadiene was introduced into the reactor, maintaining a space velocity of 1.0 h⁻¹ for the bridged dicyclopentadiene. -1 The molar ratio of hydrogen to cyclohexane to bridged dicyclopentadiene was 80:2:1. The reaction products were analyzed by gas chromatography, and the conversion and selectivity are listed in Table 2.

[0098] Comparative Example 1

[0099] 1.26 g of chloroplatinic acid and 0.60 g of palladium chloride dihydrate were dissolved in 60 g of water. The solution was then impregnated onto 60 g of HUSY molecular sieve using an equal-volume impregnation method. The impregnated sample was dried at 120 °C for 12 hours and then calcined at 500 °C for 4 hours. The sample was then mixed with 40 g of alumina and 20 g of nitric acid. After thorough mixing, the mixture was extruded, dried at 120 °C for 12 hours, and calcined at 500 °C for 4 hours to obtain catalyst M. The metal loadings on the catalyst molecules are listed in Table 1.

[0100] 50 g of catalyst M was loaded into a fixed-bed reactor. Hydrogen gas was introduced and the reactor temperature was raised to 300 °C and maintained for 6 hours. The temperature was then lowered to 150 °C and the pressure to 0.1 MPa. A hexane solution of bridged tetrahydrodicyclopentadiene was introduced into the reactor, maintaining a space velocity of 2.0 h⁻¹ for the bridged dicyclopentadiene. -1 The molar ratio of hydrogen to n-hexane to bridged dicyclopentadiene was 100:5:1. The reaction products were analyzed by gas chromatography, and the conversion rate and selectivity are listed in Table 2.

[0101] Table 1. Metal loading on molecular sieves in catalysts of Examples 1-12 and Comparative Example 1

[0102]

[0103] Table 2 Results of the bridged tetrahydrodicyclopentadiene hydroisomerization reaction

[0104]

[0105] As can be seen from the table, without using catalyst M prepared by the method disclosed in this application, the conversion rate of the reaction decreased significantly to 64.3% after 8000 hours of reaction, and the selectivity of the target product, tetrahydrodicyclopentadiene, also decreased.

[0106] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. The application of a molecular sieve catalyst in the hydroisomerization of bridged tetrahydrodicyclopentadiene to pedilicate tetrahydrodicyclopentadiene, characterized in that, The catalyst comprises a first component, a second component, a hydrogen-form molecular sieve, and a support; The first component is selected from elemental Pt and / or elemental Pd; The second component is elemental Ru; The hydrogen form molecules are selected from at least one of FAU, BEA, MOR, and MTW.

2. The application according to claim 1, characterized in that, The carrier is selected from at least one of alumina, silicon oxide, and zirconium oxide.

3. The application according to claim 1, characterized in that, In the molecular sieve catalyst The mass of the first component is 0.1~3 wt% of the mass of the hydrogen-form molecular sieve; The mass of the second component is 0.05~1wt% of the mass of the hydrogen-form molecular sieve; The mass ratio of the hydrogen-type molecular sieve to the support is 10:90 to 70:

30.

4. A method for preparing the molecular sieve catalyst as described in any one of claims 1 to 3, characterized in that, Includes the following steps: 1) The hydrogen-type molecular sieve is impregnated in an aqueous solution containing the first component source and the second component source, dried (I) and calcined (I) to obtain the catalyst precursor; 2) The catalyst precursor obtained in 1) is mixed with the support and inorganic acid, dried (II) and calcined (II) to obtain the molecular sieve catalyst.

5. The preparation method according to claim 4, characterized in that, The first component source is selected from at least one of chloroplatinic acid, platinum nitrate, platinum chloride, ammonium chloroplatinate, palladium chloride, and palladium nitrate; The second component source is selected from ruthenium chloride and / or ruthenium nitrate; The solid-liquid ratio of the hydrogen-form molecular sieve to the aqueous solution containing the first component source and the second component source is 0.5:1 to 1:

2. The temperature of the drying process I is 100~120℃; The drying time for step I is 8~24 hours; The temperature of the calcination I is 350~600℃; The roasting time for step I is 2 to 8 hours.

6. The preparation method according to claim 4, characterized in that, The inorganic acid is selected from hydrochloric acid and / or nitric acid; The ratio of the catalyst precursor to the inorganic acid is 0.5 to 2:1; The temperature of the drying II process is 100~120℃; The drying time for step II is 8-24 hours; The temperature of the second calcination is 350~600℃; The roasting time for the second stage is 2 to 8 hours.

7. A method for producing hanging tetrahydrodicyclopentadiene via bridging-type hydroisomerization of tetrahydrodicyclopentadiene, characterized in that, Includes the following steps: In a reactor, a raw material containing hydrogen gas and a bridged tetrahydrodicyclopentadiene solution is introduced and reacted with a catalyst to obtain a product containing a bridged tetrahydrodicyclopentadiene. The catalyst is selected from the molecular sieve catalyst described in any one of claims 1 to 3 or the molecular sieve catalyst prepared by the preparation method described in any one of claims 4 to 6.

8. The method according to claim 7, characterized in that, The space velocity of the raw material is 0.1~4h. -1 ; The molar ratio of hydrogen gas to bridged tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is (10~600):1; The solvent of the bridged tetrahydrodicyclopentadiene solution is selected from at least one of n-hexane, cyclohexane, methylcyclohexane, and n-heptane; The molar ratio of the solvent to the bridged tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is (1~30):1; The reaction temperature is 50~300℃; The reaction pressure is 0.1~5 MPa.

9. The method according to claim 7, characterized in that, The catalyst is reduced; The reducing atmosphere is a hydrogen atmosphere; The reduction temperature is 300~500℃; The restoration time is 2 to 6 hours.

10. The method according to claim 7, characterized in that, The reactor is selected from a fixed-bed reactor or a batch reactor.

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