CN118106019A - Dual-function catalyst and preparation method and application thereof - Google Patents
Dual-function catalyst and preparation method and application thereof Download PDFInfo
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- 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
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- tetrahydrodicyclopentadiene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000523 sample Substances 0.000 claims description 19
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical group [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 18
- 238000011068 loading method Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- XILWPJQFJFHOSI-UHFFFAOYSA-L dichloropalladium;dihydrate Chemical compound O.O.[Cl-].[Cl-].[Pd+2] XILWPJQFJFHOSI-UHFFFAOYSA-L 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- LPSXSORODABQKT-FIRGSJFUSA-N exo-trimethylenenorbornane Chemical compound C([C@@H]1C2)C[C@@H]2[C@@H]2[C@H]1CCC2 LPSXSORODABQKT-FIRGSJFUSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- 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
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.
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