CN118106019A - Dual-function catalyst and preparation method and application thereof - Google Patents

Dual-function catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN118106019A
CN118106019A CN202211519915.4A CN202211519915A CN118106019A CN 118106019 A CN118106019 A CN 118106019A CN 202211519915 A CN202211519915 A CN 202211519915A CN 118106019 A CN118106019 A CN 118106019A
Authority
CN
China
Prior art keywords
catalyst
hydrogen
tetrahydrodicyclopentadiene
component
molecular sieve
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211519915.4A
Other languages
Chinese (zh)
Inventor
张大治
黄声骏
邹明明
焦雨桐
丁辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202211519915.4A priority Critical patent/CN118106019A/en
Publication of CN118106019A publication Critical patent/CN118106019A/en
Pending legal-status Critical Current

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The application discloses a bifunctional catalyst and a preparation method and application thereof. Comprises a first component, a second component, a hydrogen molecular sieve and a carrier; the first component is selected from Pt simple substance and/or Pd simple substance; the second component is Nb simple substance; the hydrogen form molecular sieve is selected from at least one of FAU, BEA, MOR, MTW. The catalyst provided by the application has good activity at low temperature, can enable the hydroisomerization reaction of bridge-type tetrahydrodicyclopentadiene to be carried out at a lower temperature (20-60 ℃) so as to achieve the purposes of inhibiting the formation of carbon deposit and improving the stability of the catalyst.

Description

Dual-function catalyst and preparation method and application thereof
Technical Field
The application relates to a bifunctional catalyst, a preparation method and application thereof, and belongs to the field of catalyst materials.
Background
The pendant tetrahydrodicyclopentadiene (exo-THDCPD) is a high energy density liquid fuel. The hanging tetrahydrodicyclopentadiene has the characteristics of high heat value, high density, low solidifying point and the like, and is the main component of the missile/rocket propellant JP-10.
The pendant tetrahydrodicyclopentadiene can be prepared by bridge tetrahydrodicyclopentadiene isomerization. The isomerization reaction of bridged tetrahydrodicyclopentadiene initially uses a concentrated sulfuric acid catalyst, which was a lewis acidic AlCl 3 catalyst developed from the last 70 th century due to its strong corrosiveness. The AlCl 3 catalyst has the advantages of mild reaction conditions, high conversion rate and high selectivity, and is the catalyst mainly used at present. However, because AlCl 3 catalyst is difficult to separate from the product, the catalyst cannot be reused due to large dosage, and the product is difficult to refine.
In order to solve the above-mentioned shortcomings of AlCl 3 catalyst, in recent years, research reports that an acidic molecular sieve catalyst can be used for catalyzing isomerization of bridge-type tetrahydrodicyclopentadiene to prepare the pendent tetrahydrodicyclopentadiene. CN100572347 reports a method for preparing hanging tetrahydrodicyclopentadiene by loading nickel, platinum, palladium or rhodium catalysts on an HY or HBeta molecular sieve. However, when using acidic molecular sieve catalysts, higher reaction temperatures (120-300 ℃) are generally required. Under the condition, reactants are easy to polymerize on the catalyst to generate carbon deposit, so that the catalyst is deactivated quickly, and the catalyst is deactivated quickly even under the hydrogen condition in the presence of hydrogen. Therefore, the development of a high-stability bridge-type tetrahydrodicyclopentadiene hydroisomerization preparation method for the hanging-type tetrahydrodicyclopentadiene catalyst is a problem to be solved urgently.
Disclosure of Invention
In order to improve the stability of a catalyst for preparing the hanging-type tetrahydrodicyclopentadiene through the hydroisomerization of bridge-type tetrahydrodicyclopentadiene, the application provides the Nb-additive molecular sieve-added supported noble metal Pt/Pd catalyst, and the acid property and the hydrogenation performance of the catalyst are improved through adding the additive. The main reason for the rapid deactivation rate of the bridge tetrahydrodicyclopentadiene hydroisomerization catalyst is that the rate of carbon deposition during the reaction is relatively rapid. The rate of carbon formation is in turn related to the reaction temperature. The reaction temperature is favorable for the occurrence of polymerization reaction, so that the generation rate of carbon deposition is accelerated, and the catalyst is deactivated rapidly. Aiming at the above factors, the catalyst provided by the application has good activity and stability at low temperature, and can enable the hydroisomerization reaction of bridge-type tetrahydrodicyclopentadiene to be carried out at a lower temperature (20-60 ℃), thereby achieving the purposes of inhibiting the formation of carbon deposit and improving the stability of the catalyst.
According to one aspect of the present application, there is provided a dual function catalyst comprising a first component, a second component, a hydrogen form molecular sieve, and a support;
the first component is selected from Pt simple substance and/or Pd simple substance;
The second component is Nb simple substance;
The hydrogen type molecular sieve is a macroporous molecular sieve with twelve-membered ring openings;
the hydrogen-type molecular sieve is selected from at least one of FAU, BEA, MOR, MTW. Such as form Y, USY, mordenite, and the like.
The carrier is at least one selected from alumina, silica and zirconia.
In the case of the double-function catalyst,
The mass of the first component is 0.1-2 wt% of the mass of the hydrogen type molecular sieve;
Alternatively, the mass of the first component is any value or range between any two of 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt% of the mass of the hydrogen form molecular sieve.
The mass of the second component is 0.05-0.5wt% of the mass of the hydrogen type molecular sieve;
Alternatively, the mass of the second component is any value or range of values between any two of 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt% of the mass of the hydrogen form molecular sieve.
The mass ratio of the hydrogen type molecular sieve to the carrier is 20: 80-60: 40.
According to another aspect of the present application, there is provided a method for preparing the above-mentioned bifunctional catalyst, comprising the steps of:
1) Immersing hydrogen molecular sieve in water solution containing a first component source and a second component source, drying I, roasting I to obtain a catalyst precursor;
2) Mixing the catalyst precursor obtained in the step 1) with a carrier and an inorganic acid, drying II, and roasting II to obtain the bifunctional catalyst.
The first component source is at least one of chloroplatinic acid, platinum nitrate, platinum chloride, ammonium chloroplatinate, palladium chloride and palladium nitrate;
The second component source is selected from ammonium niobium oxalate;
The solid-to-liquid ratio of the hydrogen molecular sieve to the aqueous solution containing the first component source and the second component source is 0.5:1 to 1:3, a step of;
optionally, the solid to liquid ratio of the hydrogen molecular sieve to the aqueous solution containing the first component source and the second component source is 0.5: 1. 0.5: 2. 0.5: 3. 1: 1. 1: 2. 1:3 or a range value between any two.
The temperature of the drying I is 80-140 ℃;
optionally, the temperature of the drying I is any value or a range of values between any two of 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃.
The time for drying the I is 10-30 h;
optionally, the time of drying I is any value or a range of values between any two of 10h, 20h, 30 h.
The temperature of the roasting I is 300-600 ℃;
optionally, the temperature of the calcination I is any value or a range of values between any two of 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃.
The roasting time of the catalyst I is 3-6 hours.
Optionally, the time of roasting I is any value or a range of values between any two of 3h, 4h, 5h and 6 h.
The inorganic acid is selected from hydrochloric acid and/or nitric acid;
the dosage ratio of the catalyst precursor to the inorganic acid is 0.5-3: 1, a step of;
alternatively, the ratio of the catalyst precursor to the inorganic acid is 0.5: 1. 1: 1. 1.5: 1. 2: 1. 2.5: 1.3: 1 or a range value between any two.
The temperature of the drying II is 80-140 ℃;
optionally, the temperature of the drying II is any value or a range of values between any two of 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃.
The time for drying II is 10-30 h;
Optionally, the time of drying II is any value or a range of values between any two of 10h, 20h, 30 h.
The temperature of the roasting II is 300-600 ℃;
Optionally, the temperature of the roasting II is any value or a range of values between any two of 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃.
The roasting time of II is 3-6 h.
Optionally, the time of roasting II is any value or a range of values between any two of 3h, 4h, 5h and 6 h.
2) And (3) uniformly mixing and extruding.
According to another aspect of the present application, there is provided a method for producing exo-tetrahydrodicyclopentadiene by hydroisomerization of bridge-type tetrahydrodicyclopentadiene, comprising the steps of:
Introducing raw materials containing hydrogen and bridge type tetrahydrodicyclopentadiene solution into a reactor, and carrying out contact reaction on the raw materials and a catalyst to obtain a product containing the pendant tetrahydrodicyclopentadiene;
wherein the catalyst is selected from the bifunctional catalyst or the bifunctional catalyst prepared by the preparation method.
The airspeed of the raw material is 0.1-5 h -1;
Alternatively, the space velocity of the feedstock is any value or range of values between any two of 0.1h -1、0.5h-1、1h-1、2h-1、3h-1、4h-1、5h-1.
The molar ratio of the hydrogen to the formula tetrahydrodicyclopentadiene in the bridge tetrahydrodicyclopentadiene solution is (20-500): 1, a step of;
Optionally, the molar ratio of the hydrogen to the formula tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is 20: 1. 50: 1. 100: 1. 200: 1. 300: 1. 400: 1. 500:1 or a range value between any two.
The solvent of the bridged tetrahydrodicyclopentadiene solution is at least one selected from n-hexane, cyclohexane, methylcyclohexane and n-heptane;
the molar ratio of the solvent to the formula tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is (1-20): 1, a step of;
Optionally, the molar ratio of the solvent to the tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is 1: 1. 5: 1. 10: 1. 20:1 or a range value between any two.
The temperature of the reaction is 20-60 ℃;
alternatively, the temperature of the reaction is any value or a range of values between any two of 20 ℃, 30 ℃,40 ℃, 50 ℃,60 ℃.
The pressure of the reaction is 0.1-3 MPa.
Alternatively, the pressure of the reaction is any value or range of values between any two of 0.1MPa, 0.5MPa, 1MPa, 2MPa, 3 MPa.
The catalyst is reduced;
The reducing atmosphere is hydrogen atmosphere;
alternatively, the temperature of the reduction is any value or a range of values between any two of 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃.
The reduction time is 2-6 h.
Optionally, the time of the reduction is any value or range of values between any two of 2h, 3h, 4h, 5h, 6 h.
The reactor is selected from a fixed bed reactor or a kettle reactor.
The application has the beneficial effects that:
The catalyst provided by the application is applied to the reaction of preparing the hanging-type tetrahydrodicyclopentadiene by catalyzing the isomerization of the bridge-type tetrahydrodicyclopentadiene, and has obvious low-temperature reaction activity and selectivity. Under the condition that the reaction temperature is 20 ℃, the conversion rate of the reaction can reach more than 98 percent, and the selectivity of the hanging tetrahydrodicyclopentadiene is close to 100 percent. The catalyst was used continuously in a fixed bed reactor for 2000 hours without deactivation.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples. Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Example 1
0.12G of chloroplatinic acid, 0.60g of palladium chloride dihydrate and 0.10g of ammonium niobium oxalate are dissolved in 60g of water, and the solution is impregnated on 60g of hydrogen type FUA structure molecular sieve by an isovolumetric impregnation method. The impregnated sample was dried at 120℃for 12 hours and then calcined at 400℃for 4 hours. Then mixing the sample with 40g of silicon dioxide and 20g of nitric acid, extruding, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 4 hours to obtain the catalyst A. The loading of the catalyst metal on the molecule is listed in table 1.
50G of catalyst A were charged into a fixed bed reactor. Hydrogen was introduced and the reactor temperature was raised to 300 ℃ for 6 hours. Then the temperature was reduced to 30℃and the pressure 0.1MPa. Introducing a cyclohexane solution of bridge type tetrahydrodicyclopentadiene into a reactor, and keeping the space velocity of the bridge type dicyclopentadiene at 0.5h -1, and hydrogen: cyclohexane: the molar ratio of the bridge dicyclopentadiene is 20:15:1. the reaction products were analyzed by gas chromatography, and the conversion and selectivity of the reaction are shown in Table 1.
Example 2
0.42G of chloroplatinic acid and 0.13g of ammonium niobium oxalate were dissolved in 40g of water, and the solution was impregnated on 40g of hydrogen form FUA structure molecular sieve by an isovolumetric impregnation method. The impregnated sample was dried at 120℃for 12 hours and then calcined at 500℃for 3 hours. Then mixing the sample with 60g of alumina and 20g of nitric acid, extruding, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 3 hours to obtain the catalyst B. The loading of the catalyst metal on the molecule is listed in table 1.
50G of catalyst B were charged into a fixed bed reactor. Hydrogen was introduced and the reactor temperature was raised to 400 ℃ for 4 hours. The temperature was then reduced to 20℃and the pressure 0.1MPa. Introducing n-hexane solution of bridge type tetrahydrodicyclopentadiene into a reactor, and keeping the space velocity of the bridge type dicyclopentadiene to be 2.0h -1, and hydrogen: n-hexane: the molar ratio of the bridge dicyclopentadiene is 100:3:1. the reaction products were analyzed by gas chromatography, and the conversion and selectivity of the reaction are shown in Table 1.
Example 3
0.50G of palladium chloride dihydrate and 0.33g of niobium oxalate were dissolved in 80g of water, and the solution was impregnated onto 50g of hydrogen BEA structure molecular sieve by an isovolumetric impregnation method. The impregnated sample was dried at 120℃for 12 hours and then calcined at 600℃for 3 hours. Then mixing the sample with 50g of silicon dioxide and 20g of hydrochloric acid, extruding, drying at 120 ℃ for 12 hours, and roasting at 600 ℃ for 3 hours to obtain the catalyst C. The loading of the catalyst metal on the molecule is listed in table 1.
50G of catalyst C were charged into a fixed bed reactor. Hydrogen was introduced and the reactor temperature was raised to 500 ℃ for 2 hours. The temperature was then reduced to 60℃and the pressure 2.0MPa. Introducing n-hexane solution of bridge type tetrahydrodicyclopentadiene into a reactor, and keeping the space velocity of the bridge type dicyclopentadiene to be 1.0h -1, and hydrogen: n-hexane: the molar ratio of the bridge dicyclopentadiene is 150:4:1. the reaction products were analyzed by gas chromatography, and the conversion and selectivity of the reaction are shown in Table 1.
Example 4
0.63G of chloroplatinic acid and 0.39g of ammonium niobium oxalate were dissolved in 120g of water, and the solution was impregnated in an equal volume on 30g of a hydrogen form BEA structure molecular sieve. The impregnated sample was dried at 120℃for 12 hours and then calcined at 300℃for 6 hours. Then mixing the sample with 70g of zirconium dioxide and 20g of nitric acid, extruding, drying at 120 ℃ for 12 hours and roasting at 300 ℃ for 6 hours to obtain the catalyst D. The loading of the catalyst metal on the molecule is listed in table 1.
50G of catalyst D were charged into a fixed bed reactor. Hydrogen was introduced and the reactor temperature was raised to 450 ℃ for 3 hours. The temperature was then reduced to 40℃and the pressure 0.5MPa. Introducing n-heptane solution of bridge type tetrahydrodicyclopentadiene into a reactor, and keeping the space velocity of the bridge type dicyclopentadiene to be 1.5h -1, and hydrogen: n-heptane: the molar ratio of the bridge dicyclopentadiene is 300:10:1. the reaction products were analyzed by gas chromatography, and the conversion and selectivity of the reaction are shown in Table 1.
Example 5
0.63G of chloroplatinic acid and 0.29g of ammonium niobium oxalate were dissolved in 50g of water, and the solution was impregnated onto 30g of a molecular sieve of the MOR structure in hydrogen form by an isovolumetric impregnation method. The impregnated sample was dried at 120℃for 12 hours and then calcined at 500℃for 6 hours. Then mixing the sample with 70g of silicon dioxide and 20g of hydrochloric acid, extruding, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 6 hours to obtain the catalyst E. The loading of the catalyst metal on the molecule is listed in table 1.
50G of catalyst E were charged into a fixed bed reactor. Hydrogen was introduced and the reactor temperature was raised to 400 ℃ for 4 hours. The temperature was then reduced to 30℃and the pressure 1.0MPa. Introducing n-heptane solution of bridge type tetrahydrodicyclopentadiene into a reactor, and keeping the space velocity of the bridge type dicyclopentadiene to be 1.0h -1, and hydrogen: n-heptane: the molar ratio of the bridge dicyclopentadiene is 100:5:1. the reaction products were analyzed by gas chromatography, and the conversion and selectivity of the reaction are shown in Table 1.
Example 6
1.60G of palladium chloride dihydrate and 0.65g of ammonium niobium oxalate were dissolved in 90g of water, and the solution was impregnated on 40g of hydrogen form MTW structure molecular sieve by an equal volume impregnation method. The impregnated sample was dried at 120℃for 12 hours and then calcined at 450℃for 4 hours. Then mixing the sample with 60g of silicon dioxide and 20g of nitric acid, extruding, drying at 120 ℃ for 12 hours, and roasting at 450 ℃ for 4 hours to obtain the catalyst F. The loading of the catalyst metal on the molecule is listed in table 1.
50G of catalyst F are charged into a fixed bed reactor. Hydrogen was introduced and the reactor temperature was raised to 350 ℃ for 5 hours. Then the temperature was reduced to 30℃and the pressure 0.1MPa. Introducing methylcyclohexane solution of bridge tetrahydrodicyclopentadiene into a reactor, and keeping the space velocity of the bridge dicyclopentadiene at 5.0h -1, and hydrogen: methylcyclohexane: the molar ratio of the bridge dicyclopentadiene is 80:2:1. the reaction products were analyzed by gas chromatography, and the conversion and selectivity of the reaction are shown in Table 1.
Example 7
1.00G of chloroplatinic acid, 016g of palladium chloride dihydrate and 0.39g of ammonium niobium oxalate were dissolved in 60g of water, and the solution was impregnated on 40g of hydrogen type FUA structure molecular sieve by an isovolumetric impregnation method. The impregnated sample was dried at 120℃for 12 hours and then calcined at 500℃for 3 hours. Then mixing the sample with 60G of alumina and 20G of nitric acid, extruding, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 3 hours to obtain the catalyst G. The loading of the catalyst metal on the molecule is listed in table 1.
50G of catalyst G were charged into a fixed bed reactor. Hydrogen was introduced and the reactor temperature was raised to 400 ℃ for 4 hours. The temperature was then reduced to 20℃and the pressure 0.1MPa. Introducing methylcyclohexane solution of bridge tetrahydrodicyclopentadiene into a reactor, and keeping the space velocity of the bridge dicyclopentadiene at 1.0h -1, and hydrogen: methylcyclohexane: the molar ratio of the bridge dicyclopentadiene is 50:10:1. the reaction products were analyzed by gas chromatography, and the conversion and selectivity of the reaction are shown in Table 1.
Example 8
0.63G of chloroplatinic acid, 0.20g of palladium chloride dihydrate and 0.20g of ammonium niobium oxalate were dissolved in 70g of water, and the solution was impregnated onto 20g of molecular sieve of hydrogen form MOR structure by an isovolumetric impregnation method. The impregnated sample was dried at 120℃for 12 hours and then calcined at 400℃for 6 hours. Then mixing the sample with 80g of alumina and 20g of nitric acid, extruding, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ for 6 hours to obtain the catalyst H. The loading of the catalyst metal on the molecule is listed in table 1.
50G of catalyst H are charged into a fixed bed reactor. Hydrogen was introduced and the reactor temperature was raised to 400 ℃ for 5 hours. The temperature was then reduced to 20℃and the pressure 0.1MPa. Introducing n-hexane solution of bridge type tetrahydrodicyclopentadiene into a reactor, and keeping the space velocity of the bridge type dicyclopentadiene to be 1.0h -1, and hydrogen: n-hexane: the molar ratio of the bridge dicyclopentadiene is 500:20:1. the reaction products were analyzed by gas chromatography, and the conversion and selectivity of the reaction are shown in Table 1.
Comparative example 1
0.42G of chloroplatinic acid was dissolved in 60g of water, and the solution was impregnated on 40g of hydrogen form FUA structure molecular sieve by an isovolumetric impregnation method. The impregnated sample was dried at 120℃for 12 hours and then calcined at 500℃for 3 hours. Then mixing the sample with 60g of alumina and 20g of nitric acid, extruding, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 3 hours to obtain the catalyst P. The loading of the catalyst metal on the molecule is listed in table 1.
50G of catalyst P are charged into a fixed bed reactor. Hydrogen was introduced and the reactor temperature was raised to 400 ℃ for 4 hours. The temperature was then reduced to 20℃and the pressure 0.1MPa. Introducing n-hexane solution of bridge type tetrahydrodicyclopentadiene into a reactor, and keeping the space velocity of the bridge type dicyclopentadiene to be 2.0h -1, and hydrogen: n-hexane: the molar ratio of the bridge dicyclopentadiene is 100:3:1. the reaction products were analyzed by gas chromatography, and the conversion and selectivity of the reaction are shown in Table 1.
As shown in the results in Table 1, the catalyst provided by the application has good low-temperature isomerization conversion rate, selectivity and stability of the bridged tetrahydrodicyclopentadiene. The catalyst without the addition agent of the application in the comparative example has low conversion rate in low-temperature reaction and poor stability.
TABLE 1 Supports of metals on molecular sieves and hydroisomerization reaction results in the catalysts of examples 1 to 8 and comparative example 1
DD220655I-DL
The catalyst prepared by the method can reach more than 99% of conversion rate and selectivity of the hanging type tetrahydrodicyclopentadiene in the bridge type tetrahydrodicyclopentadiene hydroisomerization reaction, and the conversion rate and the selectivity of the reaction are not obviously changed after 2000 hours of reaction. The catalyst prepared in comparative example 1 had a conversion of only 57.8% and a selectivity of less than 99% under the same reaction conditions, and the conversion and selectivity were significantly reduced after 2000 hours of reaction.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (10)

1. A bifunctional catalyst, characterized in that,
Comprises a first component, a second component, a hydrogen molecular sieve and a carrier;
the first component is selected from Pt simple substance and/or Pd simple substance;
The second component is Nb simple substance;
the hydrogen-type molecular sieve is selected from at least one of FAU, BEA, MOR, MTW.
2. A bifunctional catalyst as claimed in claim 1, wherein,
The carrier is at least one selected from alumina, silica and zirconia.
3. A bifunctional catalyst as claimed in claim 1, wherein,
In the case of the double-function catalyst,
The mass of the first component is 0.1-2 wt% of the mass of the hydrogen type molecular sieve;
the mass of the second component is 0.05-0.5wt% of the mass of the hydrogen type molecular sieve;
the mass ratio of the hydrogen type molecular sieve to the carrier is 20: 80-60: 40.
4. A process for preparing a bifunctional catalyst as claimed in any one of claims 1 to 3, wherein,
The method comprises the following steps:
1) Immersing hydrogen molecular sieve in water solution containing a first component source and a second component source, drying I, roasting I to obtain a catalyst precursor;
2) Mixing the catalyst precursor obtained in the step 1) with a carrier and an inorganic acid, drying II, and roasting II to obtain the bifunctional catalyst.
5. The method according to claim 4, wherein,
The first component source is at least one of chloroplatinic acid, platinum nitrate, platinum chloride, ammonium chloroplatinate, palladium chloride and palladium nitrate;
The second component source is selected from ammonium niobium oxalate;
The solid-to-liquid ratio of the hydrogen molecular sieve to the aqueous solution containing the first component source and the second component source is 0.5:1 to 1:3, a step of;
The temperature of the drying I is 80-140 ℃;
the time for drying the I is 10-30 h;
the temperature of the roasting I is 300-600 ℃;
The roasting time of the catalyst I is 3-6 hours.
6. The method according to claim 4, wherein,
The inorganic acid is selected from hydrochloric acid and/or nitric acid;
the dosage ratio of the catalyst precursor to the inorganic acid is 0.5-3: 1, a step of;
The temperature of the drying II is 80-140 ℃;
The time for drying II is 10-30 h;
the temperature of the roasting II is 300-600 ℃;
The roasting time of II is 3-6 h.
7. A method for producing hanging type tetrahydrodicyclopentadiene through hydroisomerization of bridge type tetrahydrodicyclopentadiene is characterized in that,
The method comprises the following steps:
Introducing raw materials containing hydrogen and bridge type tetrahydrodicyclopentadiene solution into a reactor, and carrying out contact reaction on the raw materials and a catalyst to obtain a product containing the pendant tetrahydrodicyclopentadiene;
Wherein the catalyst is selected from the group consisting of the bifunctional catalyst of any one of claims 1 to 3 or the bifunctional catalyst prepared by the preparation method of any one of claims 4 to 6.
8. The method of claim 7, wherein the step of determining the position of the probe is performed,
The airspeed of the raw material is 0.1-5 h -1;
The molar ratio of the hydrogen to the formula tetrahydrodicyclopentadiene in the bridge tetrahydrodicyclopentadiene solution is (20-500): 1, a step of;
the solvent of the bridged tetrahydrodicyclopentadiene solution is at least one selected from n-hexane, cyclohexane, methylcyclohexane and n-heptane;
the molar ratio of the solvent to the formula tetrahydrodicyclopentadiene in the bridged tetrahydrodicyclopentadiene solution is (1-20): 1, a step of;
The temperature of the reaction is 20-60 ℃;
the pressure of the reaction is 0.1-3 MPa.
9. The method of claim 7, wherein the catalyst is reduced;
The reducing atmosphere is hydrogen atmosphere;
The temperature of the reduction is 300-500 ℃;
The reduction time is 2-6 h.
10. The method of claim 7, wherein the reactor is selected from a fixed bed reactor or a tank reactor.
CN202211519915.4A 2022-11-30 2022-11-30 Dual-function catalyst and preparation method and application thereof Pending CN118106019A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211519915.4A CN118106019A (en) 2022-11-30 2022-11-30 Dual-function catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211519915.4A CN118106019A (en) 2022-11-30 2022-11-30 Dual-function catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN118106019A true CN118106019A (en) 2024-05-31

Family

ID=91211204

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211519915.4A Pending CN118106019A (en) 2022-11-30 2022-11-30 Dual-function catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN118106019A (en)

Similar Documents

Publication Publication Date Title
US5364998A (en) Process for the selective hydrogenation of hydrocarbons
JPS6156139A (en) Manufacture of alcohol from carboxylic acid ester by hydrogenolysis under presence of catalyst containing nickel and tin, germanium or lead
NZ210651A (en) Palladium/rhenium catalyst and preparation of tetrahydrofuran and 1,4-butanediol
US4088603A (en) Catalyst activation process
CN114524715B (en) Directional hydrogenation method for carbonyl compound
US4006165A (en) Process for converting maleic anhydride to γ-butyrolactone
JPS63255253A (en) Production of amines
EP0277562B1 (en) Hydrogenation of citric acid and substituted citric acids to 3-substituted tetrahydrofuran, 3- and 4-substituted butyrolactones and mixtures thereof
US3948805A (en) Catalysts for converting maleic anhydride to alpha-butyrolactone
CN114433100B (en) Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation
CN111499603A (en) Method for preparing furfuryl alcohol by catalytic conversion of furfural
CN118106019A (en) Dual-function catalyst and preparation method and application thereof
CN112934251A (en) Bifunctional catalyst for catalyzing n-heptane hydroisomerization and preparation method thereof
CN112934254A (en) Bifunctional catalyst for catalyzing n-heptane conversion and preparation method thereof
US3994928A (en) Process for the production of γ-butyrolactone
CN113372303B (en) Method for preparing tetrahydrofuran dimethanol dialkyl ether
CN118106015A (en) Molecular sieve catalyst and preparation method and application thereof
CN113457724A (en) Bifunctional catalyst for preparing toluene and co-producing diphenylmethane by directly converting synthesis gas and benzene, and preparation method and application thereof
CN107952439B (en) Catalyst for catalyzing methanol carbonylation, preparation method thereof, and method for preparing acetic acid and methyl acetate by methanol carbonylation
CN107531595B (en) Method for producing 1, 4-butanediol and tetrahydrofuran from furan
CN111939967A (en) Catalyst for synthesizing exo-tetrahydrodicyclopentadiene and preparation method and application method thereof
CN118106023A (en) Composite carrier supported metal catalyst and preparation method and application thereof
KR20120035760A (en) PALLADIUM-ALUMINA COMPLEX CATALYST FOR PRODUCTION OF γ-BUTYROLACTONE BY HYDROGENATION OF SUCCINIC ACID, PREPARATION METHOD THEREOF AND PRODUCTION METHOD FOR γ-BUTYROLACTONE BY HYDROGENATION OF SUCCINIC ACID USING SAID CATALYST
CN112973790B (en) Zirconium-based alkylation catalyst and preparation method and application thereof
CN114656442B (en) Method for preparing caprolactone from 5-hydroxymethyl furoic acid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination