Composite carrier-supported metal catalyst, its preparation method and use

Abstract

The application discloses a composite carrier loaded metal catalyst, a preparation method and application thereof, and belongs to the field of catalysts. The catalyst is prepared by using Ni as an active component, using one or more of alkali metals and metals in the IB-VIB side group of the fifth period as an auxiliary agent, and using an alumina-multistage pore molecular sieve as a composite carrier. The catalyst prepared by using the method disclosed by the application is applied to the preparation of tetrahydrodicyclopentadiene by dicyclopentadiene hydrogenation, and the conversion rate of dicyclopentadiene, the selectivity of tetrahydrodicyclopentadiene and the reaction stability can be improved.

Description

TECHNICAL FIELD

[0001] The present application relates to a composite carrier supported metal catalyst, its preparation method and application, and belongs to the field of catalyst preparation. BACKGROUND

[0002] Dicyclopentadiene mainly exists in the carbon 5 component of petroleum cracking, is rich in source, and is mainly used for producing petroleum resin. Dicyclopentadiene can be prepared into tetrahydrodicyclopentadiene by hydrogenation, and the hanging type tetrahydrodicyclopentadiene is the main component (more than 98.5%) of high energy density rocket fuel (JP-10).

[0003] Tetrahydrodicyclopentadiene can be produced by the method of dicyclopentadiene hydrogenation. In order to solve the problem of short service life of nickel catalyst, Chinese patent CN101406839 discloses a catalyst, the mass percentage composition of which is Ni: 1%~10%; Rh: 0.05%~0.5%; Y: 0.05%~0.5%; the balance is γ-Al2O3, and Ni, Rh and Y exist in the form of elements or element oxides. CN100509717 discloses a method for preparing tetrahydrodicyclopentadiene by using Ni, Pd catalyst to catalyze dicyclopentadiene hydrogenation. In order to reduce the cost of catalyst, researchers have developed catalysts without noble metals. For example, patent CN103877982 discloses a supported Ni-based catalyst for continuous hydrogenation of DCPD (dicyclopentadiene), the composition of the supported catalyst includes nickel oxide, copper oxide, basic metal oxide, transition metal oxide and γ-alumina carrier, and dicyclopentadiene is continuously hydrogenated on the catalyst to prepare tetrahydrodicyclopentadiene. SUMMARY

[0004] The present application provides a nickel-based catalyst for preparing tetrahydrodicyclopentadiene by hydrogenation of dicyclopentadiene. The catalyst prepared by the method disclosed in the present application is applied to the preparation of tetrahydrodicyclopentadiene by hydrogenation of dicyclopentadiene, which can improve the conversion rate of dicyclopentadiene, the selectivity and reaction stability of tetrahydrodicyclopentadiene.

[0005] The catalyst uses Ni as the active component, one or more of alkali metals and metals in the IB-VIB side group of the fifth period as the promoter, and alumina-multistage pore molecular sieve as the composite carrier.

[0006] According to one aspect of the present application, a composite carrier supported metal catalyst is provided, which comprises an alumina-multistage pore molecular sieve composite carrier, a promoter supported on the surface of the alumina-multistage pore molecular sieve composite carrier, and a Ni active component supported on the surface of the alumina-multistage pore molecular sieve composite carrier.

[0007] The promoter is selected from alkali metals and metals in the IB-VIB side group of the fifth period.

[0008] the alkali metal is selected from at least one of Li, Na, K, Rb, Cs, Fr;

[0009] the metal of the fifth period IB-VIB subgroup is selected from at least one of Ag, Cd, Y, Zr, Nb, Mo;

[0010] in the composite carrier supported metal catalyst, the mass of the Ni active component is 0.1-30wt% of the mass of the alumina-multistage pore molecular sieve composite carrier;

[0011] Optionally, in the composite carrier supported metal catalyst, the mass of the Ni active component is any value or a range value between any two values of 0.1wt%, 0.5wt%, 1wt%, 5wt%, 10wt%, 20wt%, 30wt% of the mass of the alumina-multistage pore molecular sieve composite carrier.

[0012] in the composite carrier supported metal catalyst, the mass of the alkali metal in the additive is 0.1-2wt% of the mass of the alumina-multistage pore molecular sieve composite carrier;

[0013] Optionally, in the composite carrier supported metal catalyst, the mass of the alkali metal in the additive is any value or a range value between any two values of 0.1wt%, 0.5wt%, 1wt%, 2wt% of the mass of the alumina-multistage pore molecular sieve composite carrier.

[0014] in the composite carrier supported metal catalyst, the mass of the metal of the fifth period IB-VIB subgroup in the additive is 0.1-5wt% of the mass of the alumina-multistage pore molecular sieve composite carrier.

[0015] Optionally, in the composite carrier supported metal catalyst, the mass of the metal of the fifth period IB-VIB subgroup in the additive is any value or a range value between any two values of 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt% of the mass of the alumina-multistage pore molecular sieve composite carrier.

[0016] in the alumina-multistage pore molecular sieve composite carrier, the mass ratio of the alumina and the multistage pore molecular sieve is 95:5-5:95;

[0017] Optionally, in the alumina-multistage pore molecular sieve composite carrier, the mass ratio of the alumina and the multistage pore molecular sieve is any value or a range value between any two values of 95:5, 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, 10:90, 5:95.

[0018] a range value between any two of them.

[0019] the multistage pore molecular sieve has mesopore and micropore;

[0020] the multistage pore molecular sieve is selected from at least one of ZSM-5, ZSM-11, Y, Beta, ZSM-35, ZSM-22.

[0021] According to another aspect of the present application, a preparation method of the composite carrier loaded metal catalyst is provided, comprising the following steps:

[0022] 1) dispersing the multistage pore molecular sieve in an aqueous solution containing an aluminum source, adding an alkali solution, drying to obtain the composite carrier of alumina-multistage pore molecular sieve;

[0023] 2) mixing the composite carrier of alumina-multistage pore molecular sieve obtained in 1) with a solution containing a metal source of IB-VIB group in the fifth period, drying I, calcining I to obtain a catalyst precursor;

[0024] 3) impregnating the catalyst precursor obtained in 2) in a solution containing a nickel source and an alkali metal source, drying II, calcining II to obtain the composite carrier loaded metal catalyst.

[0025] the molecular sieve is selected from at least one of ZSM-5, ZSM-11, Y, Beta, ZSM-35, ZSM-22;

[0026] the aluminum source is selected from at least one of alumina, aluminum sulfate,

[0027] in the aqueous solution containing the aluminum source, the concentration of the aluminum source is 1-50wt%, calculated based on the aluminum element in the aluminum source;

[0028] Optionally, in the aqueous solution containing the aluminum source, the concentration of the aluminum source is any value or a range value between any two of 1wt%, 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%.

[0029] the solid-liquid ratio of dispersing the multistage pore molecular sieve in the aqueous solution containing the aluminum source is 1:1-50;

[0030] Optionally, the solid-liquid ratio of dispersing the multistage pore molecular sieve in the aqueous solution containing the aluminum source is any value or a range value between any two of 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50.

[0031] the alkali solution is selected from at least one of sodium hydroxide solution, potassium hydroxide;

[0032] The concentration of the alkali solution is 0.4-0.8M;

[0033] Optionally, the concentration of the alkali solution is any value or a range value between any two values of 0.4M, 0.5M, 0.6M, 0.7M, 0.8M.

[0034] The solid-liquid ratio of the multi-level pore molecular sieve to the alkali solution is 1:1-50;

[0035] Optionally, the solid-liquid ratio of the multi-level pore molecular sieve to the alkali solution is any value or a range value between any two values of 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50.

[0036] The temperature of the alkali solution when added is 20-80℃;

[0037] Optionally, the temperature of the alkali solution when added is any value or a range value between any two values of 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃.

[0038] The temperature of the drying is 120℃;

[0039] The time of the drying is 12h;

[0040] The fifth period IB-VIB sub-group metal source is selected from at least one of silver nitrate, cadmium nitrate, niobium oxalate, ammonium heptamolybdate, and zirconyl nitrate;

[0041] In the solution with the fifth period IB-VIB sub-group metal source, the concentration of the fifth period IB-VIB sub-group metal source is 0.05-2.5wt%, calculated based on the mass of the fifth period IB-VIB sub-group metal element in the fifth period IB-VIB sub-group metal source;

[0042] Optionally, in the solution with the fifth period IB-VIB sub-group metal source, the concentration of the fifth period IB-VIB sub-group metal source is any value or a range value between any two values of 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%.

[0043] The temperature of the drying I is 120℃;

[0044] The time of the drying I is 12h;

[0045] The temperature of the calcination I is 350-600℃;

[0046] Optionally, the temperature of the calcination I is any value or a range value between any two values of 350℃, 400℃, 450℃, 500℃, 550℃, 600℃.

[0047] The time of the calcination I is 1-10.

[0048] Optionally, the time of the calcination I is any value or a range value between any two values of 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h.

[0049] The nickel source is selected from at least one of nickel nitrate, nickel acetate, nickel chloride;

[0050] The alkali metal source is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide;

[0051] The impregnation is equal volume impregnation;

[0052] The temperature of the drying II is 120℃;

[0053] The time of the drying II is 12h;

[0054] The temperature of the calcination II is 350-600℃;

[0055] Optionally, the temperature of the calcination II is any value or a range value between any two values of 350℃, 400℃, 450℃, 500℃, 550℃, 600℃.

[0056] The time of the calcination II is 1-10.

[0057] Optionally, the time of the calcination II is any value or a range value between any two values of 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h.

[0058] Specifically, the catalyst preparation comprises the following steps:

[0059] 1) dispersing the hierarchical pore molecular sieve in an aluminum-containing liquid medium, then adding a base solution into the above medium and stirring to precipitate aluminum therein, filtering, washing, drying and calcining the precipitate to obtain an Al2O3-hierarchical pore molecular sieve as a composite carrier.

[0060] 2) adding the above composite carrier into a solution of a metal of the fifth period IB-VIB transition group, stirring and adding a base solution, then filtering, washing, drying and calcining to obtain a catalyst precursor.

[0061] 3) simultaneously impregnating nickel and alkali metal on the above catalyst precursor by equal volume impregnation, drying and calcining to obtain the catalyst.

[0062] According to another aspect of the present application, a method for preparing tetrahydrodicyclopentadiene by hydrogenating dicyclopentadiene is provided, comprising the following steps:

[0063] in a reactor, a material containing hydrogen and a reactant is introduced and reacted with a catalyst to obtain a product containing tetrahydrodicyclopentadiene;

[0064] wherein the catalyst is selected from the composite support loaded metal catalyst as described above or the composite support loaded metal catalyst prepared by the method as described above.

[0065] the reactant is selected from bridged dicyclopentadiene and / or hanging dicyclopentadiene;

[0066] the molar ratio of the hydrogen to the reactant is 5-80;

[0067] Optionally, the molar ratio of the hydrogen to the reactant is any value or a range value between any two values selected from 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80.

[0068] the space velocity of the reactant is 0.1-10 h -1 ;

[0069] Optionally, the space velocity of the reactant is any value or a range value between any two values selected from 0.1 h -1 , 0.5 h -1 , 1 h -1 , 2 h -1 , 3 h -1 , 4 h -1 , 5 h -1 , 6 h -1 , 7 h -1 , 8 h -1 , 9 h -1 , 10 h -1 .

[0070] the temperature of the reaction is 60-160℃;

[0071] DD220942I-DL

[0072] Optionally, the temperature of the reaction is any value or a range value between any two values selected from 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃.

[0073] the pressure of the reaction is 1-4 MPa.

[0074] Optionally, the pressure of the reaction is any value or a range value between any two values selected from 1 MPa, 2 MPa, 3 MPa, 4 MPa.

[0075] the reactor is a tubular fixed bed reactor.

[0076] The catalyst is reduced;

[0077] The reducing atmosphere is a hydrogen atmosphere;

[0078] The reducing temperature is 350-500°C;

[0079] Optionally, the reducing temperature is any value of 350°C, 400°C, 450°C, 500°C or a range value between any two of them.

[0080] The reducing time is 3-10h.

[0081] Optionally, the reducing time is any value of 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or a range value between any two of them.

[0082] The reaction can use a solvent;

[0083] The solvent is selected from at least one of n-hexane, cyclohexane, methylcyclohexane, n-heptane, dicyclopentadiene.

[0084] The concentration of dicyclopentadiene is 10-50wt%.

[0085] The beneficial effects that can be produced by the present application include:

[0086] The catalyst provided by the present application or the catalyst prepared by the method provided by the present application is applied to the hydrogenation of dicyclopentadiene to tetrahydrodicyclopentadiene, which can improve the conversion rate of dicyclopentadiene, the selectivity and reaction stability of tetrahydrodicyclopentadiene. DETAILED DESCRIPTION

[0087] The present application will be described in detail below in conjunction with examples, but the present application is not limited to these examples.

[0088] In the examples of the present application, the raw materials are purchased through commercial channels unless otherwise specified.

[0089] In the examples of the present application, the conversion rate and selectivity are calculated as follows:

[0090] The conversion rate of dicyclopentadiene = (1-mass of dicyclopentadiene in product / mass of dicyclopentadiene in raw material) x 100%.

[0091] The selectivity of tetrahydrodicyclopentadiene = (moles of tetrahydrodicyclopentadiene in product / (moles of cyclohexyl carboxylate in raw material-moles of cyclohexyl carboxylate in product)) x 100%.

[0092] Example 1

[0093] 83.33 g of hydrated alumina and 40 g of ZSM-5 molecular sieve were dispersed in 200 ml of water at 60°C. 200 ml of 0.6 M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 500°C for 3 hours to obtain a composite support. The obtained composite support was dispersed with 7.87 g of silver nitrate in 200 ml of water at 60°C. 200 ml of 0.6 M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 500°C for 3 hours to obtain a catalyst precursor. 93.39 g of nickel nitrate and 0.57 g of sodium hydroxide were impregnated onto the above catalyst precursor using an equal-volume impregnation method. After drying, the precursor was calcined at 500°C for 3 hours to obtain catalyst A.

[0094] 30g of catalyst A was loaded into a tubular fixed-bed reactor. Hydrogen gas was introduced into the reactor, and the reactor temperature was raised to 400℃ and maintained for 6 hours to reduce the catalyst. The reactor temperature was then lowered to 100℃, and the reactor pressure was increased to 2.0 MPa. A 20% dicyclopentadiene solution in hexane was then introduced into the reactor at a dicyclopentadiene space velocity of 2.0 h⁻¹. -1 The molar ratio of hydrogen to dicyclopentadiene was 30. The dicyclopentadiene and hydrogen reacted with a catalyst to obtain tetrahydrodicyclopentadiene as the product. The generated tetrahydrodicyclopentadiene was collected, and the composition of the collected material was analyzed using gas chromatography. After the reaction was carried out continuously for 1000 hours, the conversion rate of the reactants was 99.8%, and the selectivity for tetrahydrodicyclopentadiene was 99.5%.

[0095] Example 2

[0096] 234.9 g of aluminum sulfate and 30 g of ZSM-11 molecular sieve were dispersed in 200 ml of water at 40°C. 200 ml of 0.6 M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 350°C for 10 hours to obtain a composite support. The obtained composite support was dispersed with 4.22 g of cadmium nitrate in 200 ml of water at 40°C. 200 ml of 0.6 M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 350°C for 10 hours to obtain a catalyst precursor. 62.26 g of nickel nitrate and 0.29 g of lithium hydroxide were impregnated onto the above catalyst precursor using an equal-volume impregnation method. After drying, the precursor was calcined at 350°C for 10 hours to obtain catalyst B.

[0097] 30g of catalyst B was loaded into a tubular fixed-bed reactor. Hydrogen gas was introduced into the reactor, and the reactor temperature was raised to 350℃ and maintained for 3 hours to reduce the catalyst. The reactor temperature was then lowered to 60℃, and the reactor pressure was increased to 4.0 MPa. A 30% dicyclopentadiene solution in hexane was then introduced into the reactor at a dicyclopentadiene space velocity of 0.5 h⁻¹. -1 The molar ratio of hydrogen to dicyclopentadiene was 20. The dicyclopentadiene and hydrogen reacted with a catalyst to obtain tetrahydrodicyclopentadiene. The generated tetrahydrodicyclopentadiene was collected, and the composition of the collected material was analyzed using gas chromatography. After the reaction was carried out continuously for 1000 hours, the conversion rate of the reactants was 99.7%, and the selectivity for tetrahydrodicyclopentadiene was 99.6%.

[0098] Example 3

[0099] 131.9 g of hydrated alumina and 5 g of ZSM-5 molecular sieve were dispersed in 200 ml of water at 20°C. 200 ml of 0.6 M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 600°C for 5 hours to obtain a composite support. The obtained composite support was dispersed with 9.78 g of niobium oxalate in 200 ml of water at 20°C. 200 ml of 0.6 M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 600°C for 5 hours to obtain a catalyst precursor. 31.13 g of nickel nitrate and 1.15 g of sodium hydroxide were impregnated onto the above catalyst precursor using an equal-volume impregnation method. After drying, the precursor was calcined at 600°C for 5 hours to obtain catalyst C.

[0100] 30g of catalyst C was loaded into a tubular fixed-bed reactor. Hydrogen gas was introduced into the reactor, and the reactor temperature was raised to 500℃ and maintained for 10 hours to reduce the catalyst. The reactor temperature was then lowered to 140℃, and the reactor pressure was increased to 3.0 MPa. A 50% solution of dicyclopentadiene in methylcyclohexane was then introduced into the reactor at a dicyclopentadiene space velocity of 0.1 h⁻¹. -1 The molar ratio of hydrogen to dicyclopentadiene was 60. The dicyclopentadiene and hydrogen reacted with a catalyst to obtain tetrahydrodicyclopentadiene as the product. The generated tetrahydrodicyclopentadiene was collected, and the composition of the collected material was analyzed using gas chromatography. After the reaction was carried out continuously for 1000 hours, the conversion rate of the reactants was 99.8%, and the selectivity for tetrahydrodicyclopentadiene was 99.5%.

[0101] Example 4

[0102] Example 1

[0103] Example 2 -1 Example 3

[0104] Example 4

[0105] Example 5

[0106] 30g of catalyst E was loaded into a tubular fixed-bed reactor. Hydrogen gas was introduced into the reactor, and the reactor temperature was raised to 400℃ and maintained for 5 hours to reduce the catalyst. The reactor temperature was then lowered to 120℃, and the reactor pressure was increased to 1.0 MPa. A 40% dicyclopentadiene solution in cyclohexane was then introduced into the reactor at a dicyclopentadiene space velocity of 1.0 h⁻¹. -1 The molar ratio of hydrogen to dicyclopentadiene was 50. The dicyclopentadiene and hydrogen reacted with a catalyst to obtain tetrahydrodicyclopentadiene as the product. The generated tetrahydrodicyclopentadiene was collected, and the composition of the collected material was analyzed using gas chromatography. After the reaction was carried out continuously for 1000 hours, the conversion rate of the reactants was 99.6%, and the selectivity for tetrahydrodicyclopentadiene was 99.6%.

[0107] Example 6

[0108] 134.23 g of aluminum sulfate and 60 g of Y molecular sieve were dispersed in 200 ml of water at 60 °C. 200 ml of 0.6 M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 500 °C for 6 hours to obtain a composite support. The obtained composite support was dispersed with 1.27 g of zirconium oxynitrate in 200 ml of water at 60 °C. 200 ml of 0.6 M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 500 °C for 6 hours to obtain a catalyst precursor. 46.69 g of nickel nitrate and 0.35 g of potassium hydroxide were impregnated onto the above catalyst precursor using an equal-volume impregnation method. After drying, the precursor was calcined at 500 °C for 6 hours to obtain catalyst F.

[0109] 30g of catalyst F was loaded into a tubular fixed-bed reactor. Hydrogen gas was introduced into the reactor, and the reactor temperature was raised to 400℃ and maintained for 5 hours to reduce the catalyst. The reactor temperature was then lowered to 80℃, and the reactor pressure was increased to 1.0 MPa. A 40% dicyclopentadiene solution in cyclohexane was then introduced into the reactor at a dicyclopentadiene space velocity of 1.0 h⁻¹. -1 The molar ratio of hydrogen to dicyclopentadiene was 50. The dicyclopentadiene and hydrogen reacted with a catalyst to obtain tetrahydrodicyclopentadiene as the product. The generated tetrahydrodicyclopentadiene was collected, and the composition of the collected material was analyzed using gas chromatography. After the reaction was carried out continuously for 1000 hours, the conversion rate of the reactants was 99.4%, and the selectivity for tetrahydrodicyclopentadiene was 99.5%.

[0110] Example 7

[0111] A mixture of 69.44 g of hydrous alumina and 50 g of Beta molecular sieve was dispersed in 200 ml of water at 50°C, and 200 ml of 0.6 M sodium hydroxide solution was added dropwise thereto while stirring. After stirring for 1 hour, it was filtered, washed, dried, and calcined at 550°C for 8 h to obtain a composite support. The obtained composite support was dispersed in 200 ml of water at 50°C, and 2.53 g of zirconyl nitrate and 6.13 g of ammonium heptamolybdate were added dropwise thereto while stirring. After stirring for 1 hour, it was filtered, washed, dried, and calcined at 550°C for 8 h to obtain a catalyst precursor. 93.39 g of nickel nitrate and 0.29 g of sodium hydroxide were impregnated on the above catalyst precursor by the equal volume impregnation method. After drying, it was calcined at 550°C for 8 h to obtain a catalyst G.

[0112] A mixture of 30 g of catalyst G was charged into a tubular fixed bed reactor, hydrogen was passed into the reactor, the temperature of the reactor was raised to 450°C, and the catalyst was reduced for 6 hours. Then the temperature of the reactor was lowered to 100°C, and the pressure of the reactor was raised to 2.0 MPa, and then 20% of dicyclopentadiene in n-heptane was passed into the reactor, the dicyclopentadiene space velocity was 10.0 h -1 , the molar ratio of hydrogen to dicyclopentadiene was 80, and the product obtained by reacting dicyclopentadiene with hydrogen over the catalyst was tetrahydrodicyclopentadiene. The generated tetrahydrodicyclopentadiene was collected, and the composition of the collected material was analyzed using a gas chromatograph. After the reaction was continuously carried out for 1000 hours, the conversion of the reactant was 99.5%, and the selectivity of tetrahydrodicyclopentadiene was 99.6%.

[0113] Example 8

[0114] A mixture of 111.11 g of hydrous alumina and 20 g of ZSM-5 molecular sieve was dispersed in 200 ml of water at 60°C, and 200 ml of 0.6 M sodium hydroxide solution was added dropwise thereto while stirring. After stirring for 1 hour, it was filtered, washed, dried, and calcined at 550°C for 8 h to obtain a composite support. The obtained composite support was dispersed in 200 ml of water at 60°C, and 3.26 g of niobium oxalate and 3.06 g of ammonium heptamolybdate were added dropwise thereto while stirring. After stirring for 1 hour, it was filtered, washed, dried, and calcined at 550°C for 8 h to obtain a catalyst precursor. 62.26 g of nickel nitrate and 0.06 g of sodium hydroxide were impregnated on the above catalyst precursor by the equal volume impregnation method. After drying, it was calcined at 550°C for 8 h to obtain a catalyst G.

[0115] 30g of catalyst G was loaded into a tubular fixed-bed reactor. Hydrogen gas was introduced into the reactor, and the reactor temperature was raised to 450℃ and maintained for 6 hours to reduce the catalyst. The reactor temperature was then lowered to 90℃, and the reactor pressure was increased to 2.0 MPa. A 20% dicyclopentadiene solution in n-heptane was then introduced into the reactor, with a dicyclopentadiene space velocity of 2.0 h⁻¹. -1 The molar ratio of hydrogen to dicyclopentadiene was 60. The dicyclopentadiene and hydrogen reacted with a catalyst to obtain tetrahydrodicyclopentadiene. The generated tetrahydrodicyclopentadiene was collected, and the composition of the collected material was analyzed using gas chromatography. After the reaction was carried out continuously for 1000 hours, the conversion rate of the reactants was 99.7%, and the selectivity for tetrahydrodicyclopentadiene was 99.5%.

[0116] Comparative Example 1

[0117] 138.89 g of hydrated alumina was dispersed in 200 ml of water at 60 °C. 200 ml of 0.6 M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 500 °C for 3 hours to obtain an alumina support. 93.39 g of nickel nitrate and 0.57 g of sodium hydroxide were impregnated onto the support using an equal-volume impregnation method. After drying, the mixture was calcined at 500 °C for 3 hours to obtain catalyst P.

[0118] 30g of catalyst P was loaded into a tubular fixed-bed reactor. Hydrogen gas was introduced into the reactor, and the reactor temperature was raised to 450℃ and maintained for 6 hours to reduce the catalyst. The reactor temperature was then lowered to 90℃, and the reactor pressure was increased to 2.0 MPa. A 20% dicyclopentadiene solution in n-heptane was then introduced into the reactor, with a dicyclopentadiene space velocity of 2.0 h⁻¹. -1 The molar ratio of hydrogen to dicyclopentadiene was 60. The dicyclopentadiene and hydrogen reacted with a catalyst to obtain tetrahydrodicyclopentadiene. The generated tetrahydrodicyclopentadiene was collected, and the composition of the collected material was analyzed using gas chromatography. After the reaction was carried out continuously for 1000 hours, the conversion rate of the reactants was 85.2%, and the selectivity for tetrahydrodicyclopentadiene was 95.6%.

[0119] Comparative Example 2

[0120] 100g of ZSM-5 molecular sieve support and 7.87g of silver nitrate were dispersed in 200ml of water at 60℃. 200ml of 0.6M sodium hydroxide solution was added dropwise while stirring. After stirring for 1 hour, the mixture was filtered, washed, dried, and calcined at 500℃ for 3 hours to obtain the catalyst precursor. 93.39g of nickel nitrate and 0.57g of sodium hydroxide were impregnated onto the catalyst precursor using an equal-volume impregnation method. After drying, the precursor was calcined at 500℃ for 3 hours to obtain catalyst Q.

[0121] The 30 g catalyst Q was loaded into a tubular fixed bed reactor, hydrogen was passed into the reactor, the reactor temperature was raised to 400℃ and maintained for 6 hours to reduce the catalyst. Then the reactor temperature was lowered to 100℃, the reactor pressure was raised to 2.0 MPa, then a 20% solution of dicyclopentadiene in n-hexane was passed into the reactor, the dicyclopentadiene space velocity was 2.0 h-1, the molar ratio of hydrogen to dicyclopentadiene was 30, and the dicyclopentadiene reacted with hydrogen over the catalyst to obtain tetrahydrodicyclopentadiene product. The generated tetrahydrodicyclopentadiene was collected and the composition of the collected material was analyzed using a gas chromatograph. After the reaction was continuously carried out for 1000 hours, the conversion of the reactants was 90.6% and the selectivity of tetrahydrodicyclopentadiene was 96.4%. -1 , the molar ratio of hydrogen to dicyclopentadiene was 30, and the dicyclopentadiene reacted with hydrogen over the catalyst to obtain tetrahydrodicyclopentadiene product. The generated tetrahydrodicyclopentadiene was collected and the composition of the collected material was analyzed using a gas chromatograph. After the reaction was continuously carried out for 1000 hours, the conversion of the reactants was 90.6% and the selectivity of tetrahydrodicyclopentadiene was 96.4%.

[0122] From the comparison of Example 1 and Comparative Example 1 and Comparative Example 2, it can be seen that the catalysts in Comparative Example 1 and Comparative Example 2 were not prepared using the method described in the present application. Although the loading of the active component nickel was the same as in Example DD220942I-DL1, under the same reaction conditions, the conversion and selectivity of the reactions catalyzed by the catalysts in Comparative Example 1 and Comparative Example 2 were lower than in Example 1.

[0123] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the preferred embodiments are disclosed above, they are not intended to limit the present application. Any skilled person in the art can make minor changes or modifications to the disclosed technical content without departing from the scope of the technical solution, which are equivalent to equivalent embodiments and belong to the scope of the technical solution.

Claims

1. A composite supported metal catalyst for the hydrogenation of dicyclopentadiene to tetrahydrodicyclopentadiene, characterized in that, The composite support for the metal catalyst includes an alumina-hierarchical porous molecular sieve composite support, an additive supported on the surface of the alumina-hierarchical porous molecular sieve composite support, and a Ni active component supported on the surface of the alumina-hierarchical porous molecular sieve composite support. The additives are selected from alkali metals and fifth-period IB-VIB subgroup metals; The alkali metal is selected from at least one of Li, Na, K, Rb, Cs, and Fr; The fifth-period IB-VIB subgroup metal is selected from at least one of Ag, Cd, Y, Zr, Nb, and Mo; In the composite support-supported metal catalyst, the mass of the Ni active component is 0.1~30 wt% of the mass of the alumina-hierarchical porous molecular sieve composite support; In the composite support for the metal catalyst, the mass of the alkali metal in the promoter is 0.1~2 wt% of the mass of the alumina-hierarchical porous molecular sieve composite support. In the composite support-supported metal catalyst, the mass of the fifth-period IB-VIB group metal in the promoter is 0.1~5 wt% of the mass of the alumina-hierarchical porous molecular sieve composite support; The multi-level porous molecular sieve has mesopores and micropores; The hierarchical porous molecules are screened from at least one of ZSM-5, ZSM-11, Y, Beta, ZSM-35, and ZSM-22; The preparation method of the composite support-supported metal catalyst includes the following steps: 1) Molecular sieves are dispersed in an aqueous solution containing an aluminum source, an alkaline solution is added, and the mixture is dried to obtain the alumina-multi-level porous molecular sieve composite carrier; 2) The alumina-hierarchical porous molecular sieve composite support obtained in 1) is mixed with a solution containing a fifth-period IB-VIB subgroup metal source, dried I, and calcined I to obtain a catalyst precursor; 3) The catalyst precursor obtained in 2) is impregnated in a solution containing a nickel source and an alkali metal source, dried (II) and calcined (II) to obtain the composite support-supported metal catalyst.

2. The composite supported metal catalyst for the hydrogenation of dicyclopentadiene to tetrahydrodicyclopentadiene according to claim 1, characterized in that, In the alumina-multi-level porous molecular sieve composite carrier, the mass ratio of alumina to multi-level porous molecular sieve is 95:5 to 5:

95.

3. The composite supported metal catalyst for the hydrogenation of dicyclopentadiene to tetrahydrodicyclopentadiene according to claim 1, characterized in that, In the method for preparing the catalyst: The molecules are screened from at least one of ZSM-5, ZSM-11, Y, Beta, ZSM-35, and ZSM-22; The aluminum source is selected from at least one of alumina and aluminum sulfate; In the aqueous solution containing the aluminum source, the concentration of the aluminum source is 1~50 wt%, calculated based on the aluminum element in the aluminum source; The multi-level porous molecular sieve is dispersed in an aqueous solution containing an aluminum source at a solid-liquid ratio of 1:1 to 50. The alkaline solution is selected from at least one of sodium hydroxide solution and potassium hydroxide solution; The concentration of the alkaline solution is 0.4~0.8M; The solid-liquid ratio of the multi-level porous molecular sieve to the alkaline solution is 1:1~50; The alkaline solution is added at a temperature of 20~80℃.

4. The composite supported metal catalyst for the hydrogenation of dicyclopentadiene to tetrahydrodicyclopentadiene according to claim 1, characterized in that, In the method for preparing the catalyst: The fifth-period IB-VIB subgroup metal source is selected from at least one of silver nitrate, cadmium nitrate, niobium oxalate, ammonium heptamolybdate, and zirconium oxynitrate. In the solution containing a fifth-period IB-VIB subgroup metal source, the concentration of the fifth-period IB-VIB subgroup metal source is 0.05~2.5wt%, based on the mass of the fifth-period IB-VIB subgroup metal element in the fifth-period IB-VIB subgroup metal source; The temperature of the calcination I is 350~600℃; The roasting time for the first stage is 1 to 10 hours.

5. The composite supported metal catalyst for the hydrogenation of dicyclopentadiene to tetrahydrodicyclopentadiene according to claim 1, characterized in that, In the method for preparing the catalyst: The nickel source is selected from at least one of nickel nitrate, nickel acetate, and nickel chloride; The alkali metal source is selected from at least one of sodium hydroxide, potassium hydroxide, and lithium hydroxide; The impregnation is an equal-volume impregnation; The temperature of calcination II is 350~600℃; The roasting time for the second stage is 1 to 10 hours.

6. A method for hydrogenating dicyclopentadiene to tetrahydrodicyclopentadiene, characterized in that, Includes the following steps: In a reactor, a material containing hydrogen and reactants is introduced and reacted with a catalyst to obtain a product containing tetrahydrodicyclopentadiene. The catalyst is selected from the composite supported metal catalyst according to any one of claims 1 to 5.

7. The method according to claim 6, characterized in that, The reactants are selected from bridged dicyclopentadiene and / or hanging dicyclopentadiene; The molar ratio of hydrogen to the reactants is 5-80; The space velocity of the reactants is 0.1~10 h⁻¹. -1 ; The reaction temperature is 60~160℃; The reaction is carried out at a pressure of 1-4 MPa.

8. The method according to claim 6, characterized in that, The reaction uses a solvent; The solvent is selected from at least one of n-hexane, cyclohexane, methylcyclohexane, and n-heptane.

9. The method according to claim 6, characterized in that, The reactor is a tubular fixed-bed reactor; The catalyst is reduced; The reducing atmosphere is a hydrogen atmosphere; The reduction temperature is 350~500℃; The restoration time is 3 to 10 hours.