CN110721681A - Catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, preparation method and application - Google Patents

Catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, preparation method and application Download PDF

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CN110721681A
CN110721681A CN201911100180.XA CN201911100180A CN110721681A CN 110721681 A CN110721681 A CN 110721681A CN 201911100180 A CN201911100180 A CN 201911100180A CN 110721681 A CN110721681 A CN 110721681A
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mass
precursor
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程杰
张炳亮
张力
万克柔
林涛
高明明
赵茁然
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Kaili Catalyst New Materials Co Ltd
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Abstract

The invention discloses a catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, which comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, metal M1 and metal M2, wherein in the catalyst, the mass percent of Pd is 0.05-1%, the mass percent of metal M1 is 0.01-2%, and the mass percent of metal M2 is 0.05-3%; the metal M1 is Sn, Mn, Ce or Zn, and the metal M2 isK, Na, Ag or Ga. In addition, the invention also provides a method for preparing the catalyst and application thereof. The catalyst comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The Pd, the metal M1 and the metal M2 can keep high catalytic activity and cyclopentene selectivity in a long-time reaction process.

Description

Catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, preparation method and application
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, and a preparation method and application thereof.
Background
The cracked C5 fraction contained only about 4% cyclopentene, which in industry mainly originated from the cracking of dicyclopentadiene and the selective hydrogenation of cyclopentadiene. With the continuous increase of the production capacity of ethylene from liquid hydrocarbons and the perfection of the separation technology of C5, the production of dicyclopentadiene will also increase. Therefore, the development of dicyclopentadiene downstream high value-added products has positive significance for improving the economic benefits of enterprises.
Cyclopentadiene prepared by cracking dicyclopentadiene is subjected to selective hydrogenation to prepare cyclopentene, and due to the specific structure of the cyclopentene, downstream products of the cyclopentadiene are high-value-added fine chemical products, can be used as high-value-added medical intermediates for producing cyclopentanol, bromocyclopentane and the like, and are also main raw materials of polycycloolefin high-molecular polymers.
The catalyst used for hydrogenation of cyclopentadiene to prepare cyclopentene in the prior art is not satisfactory in terms of catalyst activity, life and selectivity. Therefore, there is a need to develop a better catalyst for hydrogenation of cyclopentadiene to produce cyclopentene.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, a preparation method and an application thereof, aiming at the defects of the prior art. The catalyst comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3Pd, metal M1 and metal M2, the catalyst being capable ofCan maintain high catalytic activity and cyclopentene selectivity in long-term reaction, and the cyclopentadiene conversion rate and the cyclopentene selectivity are both over 88%.
In order to solve the technical problems, the invention adopts the technical scheme that: a catalyst for preparing cyclopentene by cyclopentadiene hydrogenation is characterized by comprising a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, metal M1 and metal M2, wherein in the catalyst, the mass percent of Pd is 0.05-1%, the mass percent of metal M1 is 0.01-2%, and the mass percent of metal M2 is 0.05-3%; the metal M1 is Sn, Mn, Ce or Zn, and the metal M2 is K, Na, Ag or Ga; the gamma-Al2O3The particle diameter of (A) is 1.5 mm-2 mm.
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation is characterized in that the mass percentage of Pd is 0.1-0.5%, the mass percentage of metal M1 is 0.1-0.5%, and the mass percentage of metal M2 is 0.1-0.5%.
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation is characterized in that the mass percent of Pd is 0.3%, the mass percent of metal M1 is 0.2%, and the mass percent of metal M2 is 0.2%.
In addition, the invention also provides a method for preparing the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, which is characterized by comprising the following steps:
step one, gamma-Al is added2O3Activating for 1-3 h at 150-250 ℃ to obtain activated gamma-Al2O3：
Step two, spraying soluble salt solution of metal M1 on the activated gamma-Al2O3On or after activation of gamma-Al2O3Soaking in soluble salt solution of metal M1 to obtain gamma-Al loaded with metal M12O3(ii) a The metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent, and the organic solvent is absolute ethyl alcohol and methylAlcohol or isopropanol, wherein the metal M1 soluble salt is stannous chloride dihydrate, manganese nitrate, cerium nitrate or zinc nitrate;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Firstly, drying for 1-4 h at 50-150 ℃, and then roasting for 1-4 h at 350-550 ℃ to obtain a precursor A;
step four, loading Pd and metal M2 on the precursor A in the step three by a one-step loading method or a step-by-step loading method to obtain a precursor C;
the one-step loading method comprises the steps of spraying a mixed solution of a Pd precursor, a metal M2 soluble compound, water and an organic solvent on the precursor A obtained in the third step to obtain a precursor C, or comprises the steps of dipping the precursor A obtained in the third step into a mixed solution of the Pd precursor, the metal M2 soluble compound, the water and the organic solvent, and filtering to obtain the precursor C;
the step-by-step load method comprises a first step load and a second step load, wherein the first step load comprises: putting the precursor A in the step three into a Pd precursor solution for dipping and filtering to obtain a precursor B; or spraying a Pd precursor solution on the precursor A obtained in the third step to obtain a precursor B; the Pd precursor solution is a mixed solution of a Pd precursor, water and an organic solvent;
the second-step load includes: placing the precursor B in a soluble compound solution of metal M2 for dipping and filtering to obtain a precursor C; or comprises the following steps: spraying a soluble compound solution of metal M2 on the precursor B to obtain a precursor C; the metal M2 soluble compound solution is a mixed solution of a metal M2 soluble compound, water and an organic solvent;
the Pd precursor is sodium chloropalladate, palladium nitrate or chloropalladic acid, the metal M2 soluble compound is potassium hydroxide, sodium hydroxide, silver nitrate or gallium nitrate, and the organic solvent is absolute ethyl alcohol, methanol or isopropanol;
step five, drying the precursor C obtained in the step four for 1 to 4 hours at the temperature of between 100 and 150 ℃, and then roasting the precursor C for 1 to 4 hours at the temperature of between 350 and 550 ℃ to obtain a roasted precursor C;
and step six, reducing the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation.
The method is characterized in that the spraying temperature in the second step is 50-70 ℃, and the spraying speed is 0.5-3 mL/s;
the volume of the soluble salt solution of the metal M1 used for spraying in the second step is gamma-Al after activation2O30.8-1.2 times of mass, the unit of volume is mL, the unit of mass is g, and the mass of water in the metal M1 soluble salt solution used for spraying is 1.5-3 times of the mass of the organic solvent.
The method is characterized in that the dipping temperature in the second step is 40-60 ℃, the dipping time is 8-12 h, and the dipping mode is standing dipping;
the volume of the soluble salt solution of the metal M1 used for impregnation in the second step is gamma-Al after activation2O33 to 5 times of the mass, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the metal M1 soluble salt solution used for impregnation is 3 to 5 times of the mass of the organic solvent.
The method is characterized in that the spraying temperature in the fourth step is 50-70 ℃, and the spraying speed is 0.5-3 mL/s;
in the fourth step, the volume of the mixed solution used for spraying is 0.8-1.2 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the mixed solution used for spraying is 1.5-3 times of the mass of the organic solvent;
in the fourth step, the volume of the Pd precursor solution used for spraying is 0.8-1.2 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the Pd precursor solution used for spraying is 1.5-3 times of the mass of the organic solvent;
in the fourth step, the volume of the soluble compound solution of the metal M2 used for spraying is 0.8-1.2 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the soluble compound solution of the metal M2 used for spraying is 1.5-3 times of the mass of the organic solvent.
The method is characterized in that the dipping temperature in the fourth step is 20-40 ℃, the dipping time is 2-6 h, and the dipping mode is stirring dipping;
in the fourth step, the volume of the mixed solution used for dipping is 4-6 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the mixed solution used for dipping is 4-6 times of the mass of the organic solvent;
in the fourth step, the volume of the Pd precursor solution used for dipping is 4-6 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the Pd precursor solution used for dipping is 4-6 times of the mass of the organic solvent;
in the fourth step, the volume of the soluble compound solution of the metal M2 used for impregnation is 4-6 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the soluble compound solution of the metal M2 used for impregnation is 4-6 times of the mass of the organic solvent.
The method is characterized in that the reduction in the sixth step is temperature programmed reduction, the temperature rate of the temperature programmed reduction is 2-5 ℃/min, the temperature of the reduction is 300-550 ℃, and the time of the reduction is 2-4 h.
Furthermore, the invention also provides a method for preparing cyclopentene by catalyzing cyclopentadiene hydrogenation by using the catalyst, which is characterized by comprising the following steps:
adding hydrogen and cyclopentadiene solution into a fixed bed continuous reactor provided with a catalyst bed layer for reaction under the condition of oil bath at 30-80 ℃ to obtain cyclopentene; the flow rate of the hydrogen is 80 mL/min-120 mL/min, the cyclopentadiene solution is a mixed solution of cyclopentadiene and toluene, and the volume of the toluene in the cyclopentadiene solution is 3 times-5 times of that of the cyclopentadiene; the mass of the catalyst filled in the catalyst bed layer is 0.03-3% of that of the cyclopentadiene.
Compared with the prior art, the invention has the following advantages:
1. in the catalyst, the metal M1 is Sn, Mn, Ce or Zn, and the metal M1 occupies an active site, so that the excessive activity of a single Pd particle cluster is inhibited, the carbon deposition on the surface of catalyst particles is avoided, the carbon deposition resistance of the catalyst and the overall activity of the catalyst are improved, the service life of the catalyst is prolonged, the selectivity of cyclopentene is improved, and the conversion rate of cyclopentadiene and the selectivity of cyclopentene both exceed 88%.
2. In the catalyst, the metal M2 is K, Na, Ag or Ga, and the metal M2 is used for controlling the distribution of Pd particle clusters and the size of the particle clusters, so that the service life of the catalyst is prolonged, and the selectivity of cyclopentene is improved.
3. In the preparation method, the metal M1 is introduced by a spraying method or an immersion method, and the Pd and the metal M2 are introduced by a one-step loading method or a step-by-step loading method, so that the gamma-Al carrier of the Pd, the metal M1 and the metal M2 can be used for preparing the gamma-Al2O3The surface is uniformly dispersed, and the active component Pd is utilized to the maximum extent.
4. The application method of the invention adopts toluene to dissolve cyclopentadiene, which can solve the problem of feeding of a raw material pump, and simultaneously, toluene can effectively inhibit cyclopentadiene from polymerizing to generate dicyclopentadiene, promote the reaction to proceed towards the direction of cyclopentadiene hydrogenation to generate cyclopentene, and reduce the occurrence of side reactions.
5. The method has the advantages of simple process, easy operation, low production cost and easy mass production.
The technical solution of the present invention is further described in detail with reference to the following examples.
Detailed Description
Example 1
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.3%, the mass percent of metal M1 is 0.2%, and the mass percent of metal M2 is 0.2%; the metal M1 is Sn, and the metal M2 is K; the gamma-Al2O3The particle diameter of (A) is 1.8 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 200 deg.C for 2 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one2O3Placing in the pan body of a sugar-coating machine, starting the rotary switch and the heating switch of the sugar-coating machine, and activating the activated gamma-Al rotating in the pan body at the temperature of 60 DEG C2O3Spraying metal M1 soluble salt solution, and rotating for 30min to obtain gamma-Al loaded with metal M12O3(ii) a The volume of the soluble salt solution of the metal M1 is gamma-Al after activation2O31 time of mass, the unit of volume is mL, and the unit of mass is g; the spraying rate is 2 mL/s;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent; in the metal M1 soluble salt solution, the mass of water is 2 times of that of the organic solvent; the metal M1 soluble salt is SnCl2·2H2O, wherein the organic solvent is absolute ethyl alcohol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 2h at 100 ℃, and then roasting for 2h at 500 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a one-step spraying load method, and specifically comprising the following steps:
mixing a metal M2 soluble compound, sodium chloropalladate, water and an organic solvent to obtain a mixed solution; in the mixed solution, the mass of water is 2 times of that of the organic solvent, and the soluble compound of the metal M2 is potassium hydroxide; the organic solvent is absolute ethyl alcohol;
placing the precursor A in the step three in a pan body of a sugar coating machine, starting a rotary switch and a heating switch of the sugar coating machine, spraying the mixed solution on the precursor A rotating in the pan body at the temperature of 60 ℃, and continuing to rotate for 30min after the spraying is finished to obtain a precursor C; the volume of the mixed solution is 1 time of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the spraying rate is 2 mL/s;
step five, drying the precursor C obtained in the step four at 120 ℃ for 2h, and then roasting at 500 ℃ for 2h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 3 ℃/min, the reduction temperature is 400 ℃, and the heat preservation time at 400 ℃ is 3 h.
Example 2
This example is the same as example 1, except that,
in the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, the mass percentage of the metal M1 is 0.4%; the gamma-Al2O3Has a particle diameter of 1.5 mm.
Example 3
This example is the same as example 1, except that,
in the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, the mass percentage of Pd is 0.5%; the gamma-Al2O3Has a particle diameter of 2.0 mm.
Example 4
This example is the same as example 1, except that,
in the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, the mass percentage of the metal M2 is 0.4%.
Example 5
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.1%, the mass percent of metal M1 is 0.5%, and the mass percent of metal M2 is 0.1%; the metal M1 is Sn, and the metal M2 is K; the gamma-Al2O3The particle diameter of (A) is 1.8 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 150 deg.C for 3 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one2O3Placing in the pan body of a sugar-coating machine, starting the rotary switch and the heating switch of the sugar-coating machine, and activating the activated gamma-Al rotating in the pan body at 50 deg.C2O3Spraying metal M1 soluble salt solution, and rotating for 30min to obtain gamma-Al loaded with metal M12O3(ii) a The volume of the soluble salt solution of the metal M1 is gamma-Al after activation2O31.2 times of the mass, the unit of the volume is mL, and the unit of the mass is g; the spraying rate is 0.5 mL/s;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent, and in the metal M1 soluble salt solution, the mass of water is 1.5 times that of the organic solvent; the metal M1 soluble salt is SnCl2·2H2O, wherein the organic solvent is absolute ethyl alcohol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 4h at 50 ℃, and then roasting for 4h at 350 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a one-step spraying load method, and specifically comprising the following steps:
mixing a soluble compound of metal M2, palladium nitrate, water and an organic solvent to obtain a mixed solution; in the mixed solution, the mass of water is 1.5 times of that of the organic solvent, and the soluble compound of the metal M2 is potassium hydroxide; the organic solvent is methanol;
placing the precursor A in the step three in a pan body of a sugar coating machine, starting a rotary switch and a heating switch of the sugar coating machine, spraying the mixed solution on the precursor A rotating in the pan body at the temperature of 50 ℃, and continuing to rotate for 30min after the spraying is finished to obtain a precursor C; the volume of the mixed solution is 1.2 times of the mass of the precursor A in the third step, the unit of the volume is mL, and the unit of the mass is g; the spraying rate is 3 mL/s;
step five, drying the precursor C obtained in the step four at 100 ℃ for 4h, and then roasting at 550 ℃ for 1h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 3 ℃/min, the reduction temperature is 400 ℃, and the heat preservation time at 400 ℃ is 3 h.
Example 6
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.5%, the mass percent of metal M1 is 0.1%, and the mass percent of metal M2 is 0.5%; the metal M1 is Sn, and the metal M2 is K; the gamma-Al2O3The particle diameter of (A) is 1.5 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 250 deg.C for 1 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one2O3Placing in the pan body of a sugar-coating machine, starting the rotary switch and the heating switch of the sugar-coating machine, and rotating the activated gamma-Al in the pan body at 70 deg.C2O3Spraying metal M1 soluble salt solution, and rotating for 30min to obtain gamma-Al loaded with metal M12O3(ii) a The volume of the soluble salt solution of the metal M1 is gamma-Al after activation2O30.8 times of the mass, the unit of the volume is mL, and the unit of the mass is g; the spraying rate is 3 mL/s;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent, and the mass of the water in the metal M1 soluble salt solution is the mass of the organic solvent3 times the amount; the metal M1 soluble salt is SnCl2·2H2O; the organic solvent is absolute ethyl alcohol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 1h at 150 ℃, and then roasting for 1h at 550 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a one-step spraying load method, and specifically comprising the following steps:
mixing a soluble compound of metal M2, chloropalladite, water and an organic solvent to obtain a mixed solution; in the mixed solution, the mass of water is 3 times of that of the organic solvent, and the soluble compound of the metal M2 is potassium hydroxide; the organic solvent is isopropanol;
placing the precursor A in the step three in a pan body of a sugar coating machine, starting a rotary switch and a heating switch of the sugar coating machine, spraying the mixed solution on the precursor A rotating in the pan body at the temperature of 70 ℃, and continuing to rotate for 30min after the spraying is finished to obtain a precursor C; the volume of the mixed solution is 0.8 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the spraying rate is 0.5 mL/s;
step five, drying the precursor C obtained in the step four at 150 ℃ for 1h, and then roasting at 350 ℃ for 4h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 3 ℃/min, the reduction temperature is 400 ℃, and the heat preservation time at 400 ℃ is 3 h.
Example 7
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, metal M1 and metal M2, wherein in the catalyst, the mass percent of Pd is 0.05%, the mass percent of metal M1 is 2.0%, and the mass percent of metal M2 is 0.05%; the metal M1 is Sn, and the metal M2 is K; the gamma-Al2O3The particle diameter of (2.0 mm);
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 150 deg.C for 3 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one at the temperature of 50 DEG C2O3Soaking in a metal M1 soluble salt solution for 10h, and filtering to obtain a precursor A; the impregnation is standing impregnation; the volume of the metal M1 soluble salt solution is gamma-Al after activation2O34 times of the mass; the unit of volume is mL, and the unit of mass is g;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent; in the metal M1 soluble salt solution, the mass of water is 4 times of that of the organic solvent; the metal M1 soluble salt is SnCl2·2H2O, wherein the organic solvent is absolute ethyl alcohol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 2h at 100 ℃, and then roasting for 2h at 500 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a one-step impregnation loading method, and specifically comprising the following steps:
mixing a metal M2 soluble compound, sodium chloropalladate, water and an organic solvent to obtain a mixed solution; in the mixed solution, the mass of water is 5 times of that of the organic solvent, and the soluble compound of the metal M2 is potassium hydroxide; the organic solvent is absolute ethyl alcohol;
placing the precursor A in the step three into the mixed solution to be soaked for 4 hours at the temperature of 30 ℃, and filtering to obtain a precursor C; the impregnation is stirring impregnation; the volume of the mixed solution is 5 times of the mass of the precursor A; the unit of volume is mL, and the unit of mass is g;
step five, drying the precursor C obtained in the step four at 100 ℃ for 4h, and then roasting at 550 ℃ for 1h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 2 ℃/min, the reduction temperature is 300 ℃, and the heat preservation time at 300 ℃ is 4 h.
Example 8
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, metal M1 and metal M2, wherein in the catalyst, the mass percent of Pd is 1.0%, the mass percent of metal M1 is 0.01%, and the mass percent of metal M2 is 3%; the metal M1 is Sn, and the metal M2 is K; the gamma-Al2O3The particle diameter of (A) is 1.8 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 250 deg.C for 1 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one at the temperature of 40 DEG C2O3Soaking in a metal M1 soluble salt solution for 12h, and filtering to obtain a precursor A; the impregnation is standing impregnation; the volume of the metal M1 soluble salt solution is gamma-Al after activation2O35 times of the mass; the unit of volume is mL, and the unit of mass is g;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent; in the metal M1 soluble salt solution, the mass of water is 5 times of that of the organic solvent; the metal M1 soluble salt is SnCl2·2H2O, wherein the organic solvent is absolute ethyl alcohol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 4h at 50 ℃, and then roasting for 4h at 350 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a one-step impregnation loading method, and specifically comprising the following steps:
mixing a soluble compound of metal M2, palladium nitrate, water and an organic solvent to obtain a mixed solution; in the mixed solution, the mass of water is 4 times of that of the organic solvent, the soluble compound of the metal M2 is potassium hydroxide, and the organic solvent is methanol;
placing the precursor A in the step three into the mixed solution to be soaked for 6 hours at the temperature of 20 ℃, and filtering to obtain a precursor C; the impregnation is stirring impregnation; the volume of the mixed solution is 4 times of the mass of the precursor A; the unit of volume is mL, and the unit of mass is g;
step five, drying the precursor C obtained in the step four at 120 ℃ for 2h, and then roasting at 500 ℃ for 2h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 5 ℃/min, the reduction temperature is 550 ℃, and the heat preservation time at 300 ℃ is 2 h.
Example 9
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.3%, the mass percent of metal M1 is 0.2%, and the mass percent of metal M2 is 0.2%; the metal M1 is Mn, and the metal M2 is Na; the gamma-Al2O3The particle diameter of (A) is 1.8 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 200 deg.C for 2 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one at the temperature of 60 DEG C2O3Soaking in metal M1 soluble salt solution for 8 hr, and filtering to obtainPrecursor A; the impregnation is standing impregnation; the volume of the metal M1 soluble salt solution is gamma-Al after activation2O33 times of the mass; the unit of volume is mL, and the unit of mass is g;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent; in the metal M1 soluble salt solution, the mass of water is 3 times of that of the organic solvent; the metal M1 soluble salt is manganese nitrate, and the organic solvent is absolute ethyl alcohol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 1h at 150 ℃, and then roasting for 1h at 550 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a one-step impregnation loading method, and specifically comprising the following steps:
mixing a soluble compound of metal M2, chloropalladite, water and an organic solvent to obtain a mixed solution; in the mixed solution, the mass of water is 6 times of that of the organic solvent, the soluble compound of the metal M2 is sodium hydroxide, and the organic solvent is isopropanol;
placing the precursor A in the step three into the mixed solution for soaking for 2 hours at the temperature of 40 ℃, and filtering to obtain a precursor C; the impregnation is stirring impregnation; the volume of the mixed solution is 6 times of the mass of the precursor A; the unit of volume is mL, and the unit of mass is g;
step five, drying the precursor C obtained in the step four at 150 ℃ for 1h, and then roasting at 350 ℃ for 4h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 5 ℃/min, the reduction temperature is 550 ℃, and the heat preservation time at 550 ℃ is 2 h.
Example 10
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3Pd on,The catalyst comprises a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.1%, the mass percent of the metal M1 is 0.5%, and the mass percent of the metal M2 is 0.1%; the metal M1 is Mn, and the metal M2 is Na; the gamma-Al2O3The particle diameter of (A) is 1.8 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 250 deg.C for 1 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one2O3Placing in the pan body of a sugar-coating machine, starting the rotary switch and the heating switch of the sugar-coating machine, and activating the activated gamma-Al rotating in the pan body at the temperature of 60 DEG C2O3Spraying metal M1 soluble salt solution, and rotating for 30min to obtain gamma-Al loaded with metal M12O3(ii) a The volume of the soluble salt solution of the metal M1 is gamma-Al after activation2O31 time of mass, the unit of volume is mL, and the unit of mass is g; the spraying rate is 2 mL/s;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent; in the metal M1 soluble salt solution, the mass of water is 2 times of that of the organic solvent; the metal M1 soluble salt is manganese nitrate, and the organic solvent is methanol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 2h at 100 ℃, and then roasting for 2h at 500 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a step-by-step impregnation loading method, and specifically comprising the following steps:
soaking the precursor A in a sodium chloropalladate solution for 5 hours at the temperature of 30 ℃, filtering to obtain a retentate, namely a precursor B, soaking the precursor B in a soluble compound solution of metal M2 for 4 hours at the temperature of 30 ℃, and filtering to obtain a precursor C;
the volume of the sodium chloropalladate solution is 4 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the sodium chloropalladate solution is a mixed solution of chloropalladate, water and an organic solvent, wherein the mass of the water is 4 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol;
the volume of the soluble compound solution of the metal M2 is 4 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the metal M2 soluble compound solution is a mixed solution of a metal M2 soluble compound, water and an organic solvent, wherein the metal M2 soluble compound is sodium hydroxide, the mass of the water is 4 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol;
the impregnation is stirring impregnation;
step five, drying the precursor C obtained in the step four at 120 ℃ for 2h, and then roasting at 500 ℃ for 2h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 2 ℃/min, the reduction temperature is 300 ℃, and the heat preservation time at 300 ℃ is 4 h.
Example 11
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.5%, the mass percent of metal M1 is 0.1%, and the mass percent of metal M2 is 0.5%; the metal M1 is Mn, and the metal M2 is Na; the gamma-Al2O3The particle diameter of (A) is 1.8 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 200 deg.C for 2 hr to obtain activated gamma-Al2O3；
Step two, activating the activated product obtained in the step oneγ-Al2O3Placing in the pan body of a sugar-coating machine, starting the rotary switch and the heating switch of the sugar-coating machine, and activating the activated gamma-Al rotating in the pan body at 50 deg.C2O3Spraying metal M1 soluble salt solution, and rotating for 30min to obtain gamma-Al loaded with metal M12O3(ii) a The volume of the soluble salt solution of the metal M1 is gamma-Al after activation2O31.2 times of the mass, the unit of the volume is mL, and the unit of the mass is g; the spraying rate is 0.5 mL/s;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent, and in the metal M1 soluble salt solution, the mass of water is 1.5 times that of the organic solvent; the metal M1 soluble salt is manganese nitrate, and the organic solvent is isopropanol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 4h at 50 ℃, and then roasting for 4h at 350 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a spraying-dipping load method, and specifically comprising the following steps:
placing the precursor A in the step three in a pan body of a sugar coating machine, starting a rotary switch and a heating switch of the sugar coating machine, spraying a sodium chloropalladate solution on the precursor A rotating in the pan body at the temperature of 50 ℃, continuing to rotate for 30min after the spraying to obtain a precursor B, then placing the precursor B in a metal M2 soluble compound solution, soaking for 6h at the temperature of 20 ℃, and filtering to obtain a precursor C;
the volume of the sodium chloropalladate solution is 1 time of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the spraying rate is 2 mL/s; the sodium chloropalladate solution is a mixed solution of chloropalladate, water and an organic solvent, wherein the mass of the water is 3 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol;
the volume of the metal M2 soluble compound solution is 6 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the impregnation is stirring impregnation; the metal M2 soluble compound solution is a mixed solution of a metal M2 soluble compound, water and an organic solvent, wherein the metal M2 soluble compound is sodium hydroxide, the mass of the water is 5 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol;
step five, drying the precursor C obtained in the step four at 100 ℃ for 4h, and then roasting at 550 ℃ for 1h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 2 ℃/min, the reduction temperature is 300 ℃, and the heat preservation time at 300 ℃ is 4 h.
Example 12
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.3%, the mass percent of metal M1 is 0.2%, and the mass percent of metal M2 is 0.2%; the metal M1 is Ce, and the metal M2 is Ag; the gamma-Al2O3The particle diameter of (A) is 1.5 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 150 deg.C for 3 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one2O3Placing in the pan body of a sugar-coating machine, starting the rotary switch and the heating switch of the sugar-coating machine, and rotating the activated gamma-Al in the pan body at 70 deg.C2O3Spraying metal M1 soluble salt solution, and rotating for 30min to obtain gamma-Al loaded with metal M12O3(ii) a The volume of the soluble salt solution of the metal M1 is gamma-Al after activation2O30.8 times of the mass, the unit of the volume is mL, and the unit of the mass is g; the spraying rate is 3 mL/s;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent, and in the metal M1 soluble salt solution, the mass of water is 3 times of that of the organic solvent; the metal M1 soluble salt is cerous nitrate; the organic solvent is isopropanol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 1h at 150 ℃, and then roasting for 1h at 550 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a dipping-spraying load method, and specifically comprising the following steps:
placing the precursor A obtained in the third step into a sodium chloropalladate solution for soaking for 2 hours at 40 ℃, filtering to obtain a trapped substance, namely a precursor B, placing the precursor B into a pan body of a sugar-coating machine, starting a rotary switch and a heating switch of the sugar-coating machine, spraying a metal M2 soluble compound solution on the precursor rotating in the pan body at the temperature of 50 ℃, and continuing to rotate for 30 minutes after the spraying is finished to obtain a precursor C; the spraying rate is 2 mL/s;
the volume of the sodium chloropalladate solution is 6 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the sodium chloropalladate solution is a mixed solution of sodium chloropalladate, water and an organic solvent, wherein the mass of the water is 6 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol; the impregnation is stirring impregnation;
the volume of the soluble compound solution of the metal M2 is 1 time of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the metal M2 soluble compound solution is a mixed solution of a metal M2 soluble compound, water and an organic solvent, wherein the metal M2 soluble compound is silver nitrate, the mass of the water is 2 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol;
step five, drying the precursor C obtained in the step four at 150 ℃ for 1h, and then roasting at 350 ℃ for 4h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 2 ℃/min, the reduction temperature is 300 ℃, and the heat preservation time at 300 ℃ is 4 h.
Example 13
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.1%, the mass percent of metal M1 is 0.5%, and the mass percent of metal M2 is 0.1%; the metal M1 is Ce, and the metal M2 is Ag; the gamma-Al2O3The particle diameter of (A) is 1.5 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 250 deg.C for 1 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one at the temperature of 60 DEG C2O3Soaking in a metal M1 soluble salt solution for 8h, and filtering to obtain a precursor A; the impregnation is standing impregnation; the volume of the metal M1 soluble salt solution is gamma-Al after activation2O33 times of the mass; the unit of volume is mL, and the unit of mass is g;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent; in the metal M1 soluble salt solution, the mass of water is 3 times of that of the organic solvent; the metal M1 soluble salt is cerous nitrate, and the organic solvent is methanol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 1h at 150 ℃, and then roasting for 1h at 550 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a spraying-dipping load method, and specifically comprising the following steps:
placing the precursor A in the step three in a pan body of a sugar coating machine, starting a rotary switch and a heating switch of the sugar coating machine, spraying a sodium chloropalladate solution on the precursor A rotating in the pan body at the temperature of 70 ℃, continuing to rotate for 30min after the spraying to obtain a precursor B, then placing the precursor B in a metal M2 soluble compound solution, soaking for 4h at the temperature of 40 ℃, and filtering to obtain a precursor C;
the volume of the sodium chloropalladate solution is 0.8 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the spraying rate is 3 mL/s; the sodium chloropalladate solution is a mixed solution of sodium chloropalladate, water and an organic solvent, wherein the mass of the water is 2 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol;
the volume of the soluble compound solution of the metal M2 is 5 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the impregnation is stirring impregnation; the metal M2 soluble compound solution is a mixed solution of a metal M2 soluble compound, water and an organic solvent, wherein the metal M2 soluble compound is silver nitrate, the mass of the water is 6 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol;
step five, drying the precursor C obtained in the step four at 150 ℃ for 1h, and then roasting at 350 ℃ for 4h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 2 ℃/min, the reduction temperature is 300 ℃, and the heat preservation time at 300 ℃ is 4 h.
Example 14
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.5%, the mass percent of metal M1 is 0.1%, and the mass percent of metal M2 is 0.5%; the metal M1 is Ce, and the metal M2 is Ag; the gamma-Al2O3The particle diameter of (2.0 mm);
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 200 deg.C for 2 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one at the temperature of 50 DEG C2O3Soaking in a metal M1 soluble salt solution for 10h, and filtering to obtain a precursor A; the impregnation is standing impregnation; the volume of the metal M1 soluble salt solution is gamma-Al after activation2O34 times of the mass; the unit of volume is mL, and the unit of mass is g;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent; in the metal M1 soluble salt solution, the mass of water is 4 times of that of the organic solvent; the metal M1 soluble salt is cerium nitrate, and the organic solvent is isopropanol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 2h at 100 ℃, and then roasting for 2h at 500 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a dipping-spraying load method, and specifically comprising the following steps:
placing the precursor A obtained in the third step into a chloropalladic acid solution for soaking for 6 hours at the temperature of 30 ℃, filtering to obtain a trapped substance, namely a precursor B, placing the precursor B into a pan body of a sugar coating machine, starting a rotary switch and a heating switch of the sugar coating machine, spraying a metal M2 soluble compound solution on the precursor B rotating in the pan body at the temperature of 70 ℃, and continuing to rotate for 30 minutes after the spraying is finished to obtain a precursor C; the spraying rate is 0.5 mL/s;
the volume of the chloropalladate solution is 5 times of the mass of the precursor A, the unit of the volume is mLML, and the unit of the mass is g; the chloropalladite solution is a mixed solution of chloropalladite, water and an organic solvent, wherein the mass of the water is 5 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol; the impregnation is stirring impregnation;
the volume of the soluble compound solution of the metal M2 is 0.8 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the metal M2 soluble compound solution is a mixed solution of a metal M2 soluble compound, water and an organic solvent, wherein the metal M2 soluble compound is silver nitrate, the mass of the water is 1.5 times that of the organic solvent, and the organic solvent is absolute ethyl alcohol;
step five, drying the precursor C obtained in the step four at 100 ℃ for 4h, and then roasting at 550 ℃ for 1h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 2 ℃/min, the reduction temperature is 300 ℃, and the heat preservation time at 300 ℃ is 4 h.
Example 15
The catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, a metal M1 and a metal M2, wherein in the catalyst, the mass percent of Pd is 0.3%, the mass percent of metal M1 is 0.2%, and the mass percent of metal M2 is 0.2%; the metal M1 is Zn, and the metal M2 is Ga; the gamma-Al2O3The particle diameter of (A) is 1.8 mm;
the preparation method of the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation comprises the following steps:
step one, gamma-Al is added2O3Activating at 150 deg.C for 3 hr to obtain activated gamma-Al2O3；
Step two, activating the activated gamma-Al in the step one at the temperature of 40 DEG C2O3Soaking in a metal M1 soluble salt solution for 12h, and filtering to obtain a precursor A; the impregnation is standing impregnation; the volume of the metal M1 soluble salt solution is gamma-Al after activation2O35 times of the mass; the unit of volume is mL, and the unit of mass is g;
the metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent; in the metal M1 soluble salt solution, the mass of water is 5 times of that of the organic solvent; the metal M1 soluble salt is zinc nitrate, and the organic solvent is isopropanol;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Drying for 4h at 50 ℃, and then roasting for 4h at 350 ℃ to obtain a precursor A;
step four, obtaining a precursor C by a step-by-step spraying load method, and specifically comprising the following steps:
placing the precursor A in the step three in a pan body of a sugar coating machine, starting a rotary switch and a heating switch of the sugar coating machine, spraying a palladium nitrate solution to the precursor A rotating in the pan body at the temperature of 60 ℃, continuing to rotate for 30min after spraying to obtain a precursor B, spraying a metal M2 soluble compound solution to the precursor B rotating in the pan body at the same temperature, and continuing to rotate for 30min after spraying to obtain a precursor C; the spraying speed is 0.5 m/s;
the volume of the palladium nitrate solution is 1.2 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; the palladium nitrate solution is a mixed solution of palladium nitrate, water and an organic solvent, wherein the mass of the water is 1.5 times that of the organic solvent, and the organic solvent is methanol;
the volume of the soluble compound solution of the metal M2 is 1.2 times of the mass of the precursor A, the unit of the volume is mL, and the unit of the mass is g; in the metal M2 soluble compound solution, the metal M2 soluble compound is gallium nitrate, the mass of water is 2 times of that of an organic solvent, and the organic solvent is methanol;
step five, drying the precursor C obtained in the step four at 120 ℃ for 2h, and then roasting at 500 ℃ for 2h to obtain a roasted precursor C;
and step six, performing temperature programmed reduction on the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, wherein the temperature programmed reduction rate is 5 ℃/min, the reduction temperature is 550 ℃, and the heat preservation time at 550 ℃ is 2 h.
Example 16
The method for preparing cyclopentene by hydrogenating cyclopentadiene of the embodiment comprises the following steps:
step one, heating a fixed bed continuous reactor provided with a catalyst bed layer to 50 ℃ by adopting an oil bath, keeping the temperature, and introducing hydrogen into the fixed bed continuous reactor at the flow rate of 100 mL/min;
step two, adding cyclopentadiene solution into the fixed bed continuous reactor, reacting the cyclopentadiene solution entering the fixed bed continuous reactor through the catalyst bed layer to obtain cyclopentene, sampling the product, and determining by gas chromatography-mass spectrometry, wherein the determination result is shown in table 1; the cyclopentadiene solution is a mixed solution of cyclopentadiene and toluene, and the volume of the toluene in the mixed solution of cyclopentadiene and toluene is 4 times of that of cyclopentadiene; the reaction pressure was normal pressure.
The catalysts of examples 1 to 15 were used to prepare cyclopentene by hydrogenation of cyclopentadiene by the above method, and the mass of the catalyst was 0.03% of that of cyclopentadiene, and the results are shown in Table 1.
TABLE 1 reaction results of catalytic cyclopentadiene hydrogenation to cyclopentene
Figure BDA0002269613970000221
Figure BDA0002269613970000231
Table 1 shows that in the reaction of preparing cyclopentene by hydrogenation of cyclopentadiene with the catalyst of the present invention, the conversion rate of raw material cyclopentadiene is over 88%, the selectivity of the product cyclopentene is over 88%, and the yield of byproduct cyclopentane is below 2.2%, which indicates that the catalyst of the present invention can effectively promote the generation of cyclopentene, and the accumulated operation time of the catalyst is over 300h, which indicates that the catalyst of the present invention has long service life and can meet the requirement of industrial production. The catalyst of the invention can keep high catalytic activity and cyclopentene selectivity in a long-term reaction process.
Example 17
The method for preparing cyclopentene by hydrogenating cyclopentadiene of the embodiment comprises the following steps:
step one, heating a fixed bed continuous reactor provided with a catalyst bed layer to 30 ℃ by adopting an oil bath, keeping the temperature, and introducing hydrogen into the fixed bed continuous reactor at the flow rate of 80 mL/min;
step two, adding cyclopentadiene solution into the fixed bed continuous reactor, reacting the cyclopentadiene solution entering the fixed bed continuous reactor through the catalyst bed layer to obtain cyclopentene, sampling the product, and determining by gas chromatography-mass spectrometry, wherein the determination result is shown in table 1; the cyclopentadiene solution is a mixed solution of cyclopentadiene and toluene, and the volume of the toluene in the mixed solution of cyclopentadiene and toluene is 3 times of that of cyclopentadiene; the reaction pressure was normal pressure.
The catalysts of the embodiments 1 to 15 are used for catalyzing cyclopentadiene hydrogenation to prepare cyclopentene by the method, and the mass of the catalyst is 3% of that of cyclopentadiene.
In the reaction for preparing cyclopentene by catalyzing cyclopentadiene hydrogenation by using the catalyst, the conversion rate of raw material cyclopentadiene is over 88%, the selectivity of the product cyclopentene is over 87.6%, and the yield of byproduct cyclopentane is below 2.3%, which shows that the catalyst can effectively promote the generation of cyclopentene, the accumulated operation time of the catalyst is over 300h, and shows that the catalyst has long service life and can meet the requirement of industrial production.
Example 18
The method for preparing cyclopentene by hydrogenating cyclopentadiene of the embodiment comprises the following steps:
step one, heating a fixed bed continuous reactor provided with a catalyst bed layer to 80 ℃ by adopting an oil bath, keeping the temperature, and introducing hydrogen into the fixed bed continuous reactor at the flow rate of 120 mL/min;
step two, adding cyclopentadiene solution into the fixed bed continuous reactor, reacting the cyclopentadiene solution entering the fixed bed continuous reactor through the catalyst bed layer to obtain cyclopentene, sampling the product, and determining by gas chromatography-mass spectrometry, wherein the determination result is shown in table 1; the cyclopentadiene solution is a mixed solution of cyclopentadiene and toluene, and the volume of the toluene in the mixed solution of cyclopentadiene and toluene is 5 times of that of cyclopentadiene; the reaction pressure was normal pressure.
The catalysts of the embodiments 1 to 15 are used for catalyzing cyclopentadiene hydrogenation to prepare cyclopentene by the method, and the mass of the catalyst is 0.1 percent of that of the cyclopentadiene.
In the reaction for preparing cyclopentene by catalyzing cyclopentadiene hydrogenation by using the catalyst, the conversion rate of raw material cyclopentadiene is over 88 percent, the selectivity of the product cyclopentene is over 88 percent, and the yield of byproduct cyclopentane is below 2.21 percent, which shows that the catalyst can effectively promote the generation of cyclopentene, the accumulated operation time of the catalyst is over 300h, and shows that the catalyst has long service life and can meet the requirement of industrial production.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (10)

1. A catalyst for preparing cyclopentene by cyclopentadiene hydrogenation is characterized by comprising a carrier gamma-Al2O3gamma-Al supported on the carrier2O3The catalyst comprises Pd, metal M1 and metal M2, wherein in the catalyst, the mass percent of Pd is 0.05-1%, the mass percent of metal M1 is 0.01-2%, and the mass percent of metal M2 is 0.05-3%; the metal M1 is Sn, Mn, Ce or Zn, and the metal M2 is K, Na, Ag or Ga; the gamma-Al2O3The particle diameter of (A) is 1.5 mm-2 mm.
2. The catalyst for preparing cyclopentene through cyclopentadiene hydrogenation according to claim 1, wherein the mass percent of Pd is 0.1-0.5%, the mass percent of metal M1 is 0.1-0.5%, and the mass percent of metal M2 is 0.1-0.5%.
3. The catalyst for preparing cyclopentene through cyclopentadiene hydrogenation according to claim 1, wherein the mass percent of Pd is 0.3%, the mass percent of metal M1 is 0.2%, and the mass percent of metal M2 is 0.2%.
4. A method for preparing the catalyst for cyclopentadiene hydrogenation to cyclopentene according to claim 1, comprising the steps of:
step one, gamma-Al is added2O3Activating for 1-3 h at 150-250 ℃ to obtain activated gamma-Al2O3：
Step two, spraying soluble salt solution of metal M1 on the activated gamma-Al2O3On or after activation of gamma-Al2O3Soaking in soluble salt solution of metal M1 to obtain gamma-Al loaded with metal M12O3(ii) a The metal M1 soluble salt solution is a mixed solution of metal M1 soluble salt, water and an organic solvent, the organic solvent is absolute ethyl alcohol, methanol or isopropanol, and the metal M1 soluble salt is stannous chloride dihydrate, manganese nitrate, cerium nitrate or zinc nitrate;
step three, loading the gamma-Al loaded with the metal M1 in the step two2O3Firstly, drying for 1-4 h at 50-150 ℃, and then roasting for 1-4 h at 350-550 ℃ to obtain a precursor A;
step four, loading Pd and metal M2 on the precursor A in the step three by a one-step loading method or a step-by-step loading method to obtain a precursor C;
the one-step loading method comprises the steps of spraying a mixed solution of a Pd precursor, a metal M2 soluble compound, water and an organic solvent on the precursor A obtained in the third step to obtain a precursor C, or comprises the steps of dipping the precursor A obtained in the third step into a mixed solution of the Pd precursor, the metal M2 soluble compound, the water and the organic solvent, and filtering to obtain the precursor C;
the step-by-step load method comprises a first step load and a second step load, wherein the first step load comprises: putting the precursor A in the step three into a Pd precursor solution for dipping and filtering to obtain a precursor B; or spraying a Pd precursor solution on the precursor A obtained in the third step to obtain a precursor B; the Pd precursor solution is a mixed solution of a Pd precursor, water and an organic solvent;
the second-step load includes: placing the precursor B in a soluble compound solution of metal M2 for dipping and filtering to obtain a precursor C; or comprises the following steps: spraying a soluble compound solution of metal M2 on the precursor B to obtain a precursor C; the metal M2 soluble compound solution is a mixed solution of a metal M2 soluble compound, water and an organic solvent;
the Pd precursor is sodium chloropalladate, palladium nitrate or chloropalladic acid, the metal M2 soluble compound is potassium hydroxide, sodium hydroxide, silver nitrate or gallium nitrate, and the organic solvent is absolute ethyl alcohol, methanol or isopropanol;
step five, drying the precursor C obtained in the step four for 1 to 4 hours at the temperature of between 100 and 150 ℃, and then roasting the precursor C for 1 to 4 hours at the temperature of between 350 and 550 ℃ to obtain a roasted precursor C;
and step six, reducing the roasted precursor C in the step five by using hydrogen to obtain the catalyst for preparing cyclopentene by cyclopentadiene hydrogenation.
5. The method according to claim 4, wherein the temperature of spraying in the second step is 50 ℃ to 70 ℃, and the spraying rate is 0.5mL/s to 3 mL/s;
the volume of the soluble salt solution of the metal M1 used for spraying in the second step is gamma-Al after activation2O30.8-1.2 times of mass, the unit of volume is mL, the unit of mass is g, and the mass of water in the metal M1 soluble salt solution used for spraying is 1.5-3 times of the mass of the organic solvent.
6. The method according to claim 4, wherein the temperature of the impregnation in the second step is 40-60 ℃, the time of the impregnation is 8-12 h, and the impregnation mode is static impregnation;
the volume of the soluble salt solution of the metal M1 used for impregnation in the second step is gamma-Al after activation2O33 to 5 times of the mass, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the metal M1 soluble salt solution used for impregnation is 3 to 5 times of the mass of the organic solvent.
7. The method according to claim 4, wherein the temperature of the spraying in the fourth step is 50 ℃ to 70 ℃ and the speed of the spraying is 0.5mL/s to 3 mL/s;
in the fourth step, the volume of the mixed solution used for spraying is 0.8-1.2 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the mixed solution used for spraying is 1.5-3 times of the mass of the organic solvent;
in the fourth step, the volume of the Pd precursor solution used for spraying is 0.8-1.2 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the Pd precursor solution used for spraying is 1.5-3 times of the mass of the organic solvent;
in the fourth step, the volume of the soluble compound solution of the metal M2 used for spraying is 0.8-1.2 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the soluble compound solution of the metal M2 used for spraying is 1.5-3 times of the mass of the organic solvent.
8. The method according to claim 7, wherein the dipping temperature in the fourth step is 20-40 ℃, the dipping time is 2-6 h, and the dipping mode is stirring dipping;
in the fourth step, the volume of the mixed solution used for dipping is 4-6 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the mixed solution used for dipping is 4-6 times of the mass of the organic solvent;
in the fourth step, the volume of the Pd precursor solution used for dipping is 4-6 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the Pd precursor solution used for dipping is 4-6 times of the mass of the organic solvent;
in the fourth step, the volume of the soluble compound solution of the metal M2 used for impregnation is 4-6 times of the mass of the precursor A, the unit of the volume is mL, the unit of the mass is g, and the mass of water in the soluble compound solution of the metal M2 used for impregnation is 4-6 times of the mass of the organic solvent.
9. The method according to claim 4, wherein the reduction in the sixth step is temperature programmed reduction, the temperature rate of the temperature programmed reduction is 2 ℃/min to 5 ℃/min, the temperature of the reduction is 300 ℃ to 550 ℃, and the time of the reduction is 2h to 4 h.
10. A method for preparing cyclopentene by hydrogenation of cyclopentadiene using the catalyst according to claim 1, comprising:
adding hydrogen and cyclopentadiene solution into a fixed bed continuous reactor provided with a catalyst bed layer for reaction under the condition of oil bath at 30-80 ℃ to obtain cyclopentene; the flow rate of the hydrogen is 80 mL/min-120 mL/min, the cyclopentadiene solution is a mixed solution of cyclopentadiene and toluene, and the volume of the toluene in the cyclopentadiene solution is 3 times-5 times of that of the cyclopentadiene; the mass of the catalyst filled in the catalyst bed layer is 0.03-3% of that of the cyclopentadiene.
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