CN118079994A - Nitrogen-containing catalyst, preparation method thereof and application thereof in cyclohexane dehydrogenation preparation of benzene - Google Patents
Nitrogen-containing catalyst, preparation method thereof and application thereof in cyclohexane dehydrogenation preparation of benzene Download PDFInfo
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 75
- 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 75
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000004767 nitrides Chemical class 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 13
- 238000005121 nitriding Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000003657 tungsten Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052680 mordenite Inorganic materials 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical group Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910000323 aluminium silicate Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a nitrogen-containing catalyst, a preparation method thereof and application thereof in preparing benzene by cyclohexane dehydrogenation, wherein the nitrogen-containing catalyst comprises a hierarchical pore molecular sieve and nitride loaded on the surface of the hierarchical pore molecular sieve; the nitride is selected from WN. The catalyst provided by the application can be applied to cyclohexane dehydrogenation reaction to prepare benzene and improve the conversion rate of cyclohexane and the selectivity of the generated benzene. The preparation method of the catalyst provided by the application is stable, controllable and good in reproducibility. The method for preparing benzene by cyclohexane dehydrogenation reaction provided by the application adopts the catalyst provided by the application, has high reaction speed and high yield, and can be applied to large-scale production.
Description
Technical Field
The application relates to a nitrogen-containing catalyst, a preparation method thereof and application thereof in preparing benzene by dehydrogenating cyclohexane, belonging to the field of chemical industry.
Background
Cyclohexane is an important chemical raw material and intermediate, has wide application, is used for solvents and adhesives in about 20 percent, is used for organic synthesis in 80 percent, and is mainly used for producing products such as cyclohexanol, cyclohexanone, adipic acid, caprolactam and the like.
The dehydrogenation of the organic hydrogen carrier adopts a supported industrial reforming catalyst which takes gamma-Al 2O3 as a carrier and Pt as an active component, and the catalyst has the defects of high price, easy coking, carbon deposition and the like. Raney nickel or other non-noble metal catalysts are also useful. In operating units, bimetallic or multimetal catalysts are often employed, with multimetal components as cocatalysts to improve catalyst performance. In existing catalysts, ni, ir, pd and Pt are often used as the active components of dehydrogenation catalysts. Wherein Pt has high activity on naphthene dehydrogenation due to high activation capacity on C-H bond. The higher the dispersity of the metal, the higher the activity of the catalyst under the same content of active component. However, the use of noble metals for the catalyst is difficult and expensive. The active component determines the quality of the catalyst performance.
In recent years, the nitride has attracted attention, has similar catalytic performance to noble metals, has similar d-charge characteristics below the fermi level, is low in price and excellent in sulfur poisoning resistance compared with the noble metals, and has wide application prospect in the field of catalysts.
Disclosure of Invention
The metal nitride is loaded on the multi-stage pore molecular sieve, the cost is low, the preparation method is simple, and the dispersity of the nitride on the multi-stage pore molecular sieve is good. The catalyst is applied to the reaction of preparing benzene by dehydrogenating cyclohexane, and has good catalyst activity, high cyclohexane conversion rate and benzene selectivity and good stability.
According to one aspect of the present application, there is provided a nitrogen-containing catalyst for the dehydrogenation of cyclohexane to benzene, capable of improving the conversion rate of cyclohexane and the selectivity of benzene; comprises a hierarchical pore molecular sieve and nitride loaded on the surface of the hierarchical pore molecular sieve;
The nitride is selected from WN.
According to another aspect of the present application, there is provided a method for preparing the above nitrogen-containing catalyst for cyclohexane dehydrogenation to benzene, comprising the steps of:
(1) Performing alkali treatment and ammonium ion exchange treatment on the initial molecular sieve to obtain a multi-stage pore molecular sieve;
(2) Immersing the multi-stage pore molecular sieve obtained in the step (1) in a solution containing a tungsten source to obtain a catalyst precursor, drying III, and calcining III to obtain a multi-stage pore molecular sieve loaded with WO 3;
(3) And (3) nitriding the multistage pore molecular sieve loaded with WO 3 obtained in the step (2) in an ammonia atmosphere to obtain the nitrogen-containing catalyst.
The alkali treatment comprises:
treating the initial molecular sieve with alkali liquor, drying the initial molecular sieve I, and calcining the initial molecular sieve I to obtain an alkali treated initial molecular sieve;
The initial molecular sieve is selected from a silicon-aluminum molecular sieve;
The silicon-aluminum molecular sieve is selected from mordenite molecular sieve and/or ZSM-5 molecular sieve;
The temperature of the alkali liquor treatment is 65-90 ℃;
Alternatively, the alkali liquor treatment temperature is any value or a range of values between any two of 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃.
The alkali liquor treatment time is 0.5-1.5 h;
Alternatively, the lye treatment time is any value or range of values between any two of 0.5h, 0.75h, 1h, 1.25h, 1.5 h.
The alkali liquor is selected from NaOH solution and/or KOH solution;
The solid-to-liquid ratio of the molecular sieve to the alkali liquor is 1: (10-30) g/ml;
optionally, the solid-to-liquid ratio of the molecular sieve to the alkali liquor is 1:10g/ml, 1:20g/ml, 1: any value in 30g/ml or a range of values between any two.
The concentration of the alkali liquor is 0.1-0.3 mol/L;
alternatively, the concentration of the lye is any value selected from the group consisting of 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, or a range between any two.
The temperature of the drying I is 80-130 ℃;
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 ℃.
The time for drying the I is 8-24 hours;
Optionally, the drying I is performed for a time of any value or range between any two values of 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24 h.
The temperature of the calcination I is 450-650 ℃;
optionally, the temperature of calcination I is any value or range of values between any two of 450 ℃,500 ℃, 550 ℃, 600 ℃, 650 ℃.
The time of calcining the material I is 1-6 h.
Optionally, the time of calcining I is any value or range of values between any two of 1h, 2h, 3h, 4h, 5h, 6 h.
The ammonium ion exchange treatment includes:
Performing ammonium ion exchange on the obtained initial molecular sieve subjected to alkali treatment in an ammonium salt solution, drying II, and calcining II to obtain the hierarchical pore molecular sieve;
The temperature of the ammonium ion exchange is 65-90 ℃;
Alternatively, the temperature of the ammonium ion exchange treatment is any value or a range of values between any two of 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃.
The time of the ammonium ion exchange is 4-8 hours;
optionally, the time of the ammonium ion exchange treatment is any value or a range of values between any two of 4h, 5h, 6h, 7h, 8h.
The ammonium salt is NH 4NO3;
The concentration of the ammonium salt solution is 0.4-1.2 mol/L;
Optionally, the concentration of the ammonium salt solution is any value or a range of values between any two of 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2 mol/L.
The solid-to-liquid ratio of the molecular sieve to the ammonium salt solution is 1: (10-30) g/ml;
optionally, the solid-to-liquid ratio of the molecular sieve to the ammonium salt solution is 1:10g/ml, 1:20g/ml, 1: any value in 30g/ml or a range of values between any two.
The temperature of the drying II is 80-130 ℃;
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 ℃.
The time for drying II is 8-24 hours;
optionally, the time of drying II is any value or a range of values between any two of 8h, 12h, 16h, 20h, 24 h.
The temperature of the calcination II is 450-650 ℃;
Optionally, the temperature of the calcination II is any value or a range of values between any two of 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃.
The time of calcining II is 1-6 h;
optionally, the time of calcination II is selected from any value or range of values between any two of 1h, 2h, 3h, 4h, 5h, 6h.
The hierarchical pore molecular sieve is crushed and sieved;
The particle size of the hierarchical pore molecular sieve obtained after crushing and sieving treatment is 16-32 meshes.
Optionally, the particle size of the hierarchical pore molecular sieve obtained after crushing and sieving treatment is any value or range value between any two of 16 meshes, 18 meshes, 20 meshes, 22 meshes, 24 meshes, 26 meshes, 28 meshes, 30 meshes and 32 meshes.
The tungsten source is selected from tungsten hexachloride and/or ammonium metatungstate;
The solid-to-liquid ratio of the hierarchical pore molecular sieve to the solution containing tungsten salt is 1: (0.6-0.8) g/ml;
Optionally, the solid-to-liquid ratio of the hierarchical pore molecular sieve to the solution containing tungsten salt is 1:0.6g/ml, 1:0.7g/ml, 1: any value or range of values between any two of 0.8 g/ml.
The temperature of the drying III is 80-130 ℃;
Optionally, the temperature of the drying III is any value or a range of values between any two of 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃.
The time for drying III is 6-24 hours;
Optionally, the time of drying III is any value or a range of values between any two of 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24 h.
The temperature of the calcination III is 450-650 ℃;
Optionally, the temperature of the calcination III is any value or a range of values between any two of 450 ℃, 470 ℃, 490 ℃, 510 ℃, 530 ℃, 550 ℃, 570 ℃, 590 ℃, 610 ℃, 630 ℃, 650 ℃.
The time of calcining III is 1-6 h;
optionally, the time of calcining III is any value or range of values between any two of 1h, 2h, 3h, 4h, 5h, 6 h.
In the multistage pore molecular sieve loaded with WO 3, the mass ratio of the WO 3 to the multistage pore molecular sieve is (1-3): 100.
Optionally, in the multi-stage pore molecular sieve loaded with WO 3, the mass ratio of WO 3 to the multi-stage pore molecular sieve is 1: 100. 2: 100. 3:100 or a range of values therebetween.
The temperature of the nitriding treatment is 650-750 ℃;
optionally, the temperature of the nitriding treatment is any value or a range of values between any two of 650 ℃, 700 ℃, 750 ℃.
The nitriding treatment time is 0.5-4 h;
Optionally, the nitriding treatment is performed for a time of any value or a range of values between any two of 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4 h.
The temperature rising rate of the nitriding treatment is 4-10 ℃/min.
Optionally, the temperature rise rate of the nitriding treatment is any value or a range of values between any two of 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min.
The method comprises the following steps: and (3) placing the calcined mixture into an open type tubular furnace, and heating to obtain the catalyst WN/multi-level pore molecular sieve under the condition of introducing a nitrogen source.
The impregnation is an isovolumetric impregnation; the method comprises the following steps: dissolving tungsten salt in a certain amount of deionized water, pouring the deionized water into a hierarchical pore molecular sieve, stirring the mixture by using a glass plate, standing the mixture at normal temperature, drying the mixture by using an oven, and calcining the mixture.
According to another aspect of the present application, there is provided a process for preparing benzene by dehydrogenation of cyclohexane,
The method comprises the following steps:
Introducing a raw material containing hydrogen and cyclohexane into a reactor, contacting with a catalyst, and reacting to obtain a benzene-containing product;
wherein the catalyst is selected from the nitrogen-containing catalyst for preparing benzene by cyclohexane dehydrogenation or the nitrogen-containing catalyst for preparing benzene by cyclohexane dehydrogenation prepared by the preparation method.
The temperature of the reaction is 280-340 ℃;
alternatively, the temperature of the reaction is any value or range of values between any two of 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃.
The reaction time is 2-3 h;
Alternatively, the reaction time is any value or range of values between any two of 2h, 2.5h, 3 h.
The pressure of the reaction is 0.1-0.4 MPa.
Alternatively, the pressure of the reaction is any value or range of values between any two of 0.1MPa, 0.2MPa, 0.3MPa, 0.4 MPa.
Among the raw materials, the raw materials are mixed,
The flow rate of the hydrogen is 5-10 ml/min;
Optionally, the flow rate of the hydrogen is any value or range of values between any two of 5ml/min, 6ml/min, 7ml/min, 8ml/min, 9ml/min, 10 ml/min.
The mass airspeed of the cyclohexane is 2-4 h -1.
Optionally, the mass space velocity of the cyclohexane is any value or a range of values between any two of 2h -1、3h-1、4h-1.
The reactor is a fixed bed reactor.
The application has the beneficial effects that:
1) The catalyst provided by the application can be applied to cyclohexane dehydrogenation reaction to prepare benzene and improve the conversion rate of cyclohexane and the selectivity of the generated benzene.
2) The preparation method of the catalyst provided by the application is stable, controllable and good in reproducibility.
3) The method for preparing benzene by cyclohexane dehydrogenation reaction provided by the application adopts the catalyst provided by the application, has high reaction speed and high yield, and can be applied to large-scale production.
Drawings
Fig. 1 is an X-ray powder diffraction pattern of the WN mixture in catalyst 1 #.
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.
Wherein the gas chromatograph is 7890B type gas chromatograph of Agilent company.
Example 1
Preparation of the catalyst
Taking the number 1 in tables 1-3 as an example, maintaining the solution temperature at 65 ℃, treating a mordenite molecular sieve (silicon-aluminum atomic ratio is 12.5) with a solution of NaOH with the concentration of 0.3mol/L for 1.5 hours, washing to be neutral, drying at 100 ℃ for 12 hours, and calcining at 550 ℃ for 3 hours to obtain a Na-type hierarchical pore molecular sieve material; maintaining the temperature of the solution at 80 ℃, carrying out ammonium ion exchange on NH 4NO3 solution with the concentration of 0.8mol/L for the Na-type hierarchical pore molecular sieve material with the solid-to-liquid ratio (g/ml) of 1:20 for 6 hours, drying at 100 ℃ for 12 hours after washing, and calcining at 550 ℃ for 3 hours to obtain a hydrogen-type hierarchical pore molecular sieve material; crushing and sieving the mixture into a 20-mesh material to prepare a hierarchical pore molecular sieve material; dissolving ammonium metatungstate in deionized water, pouring a hierarchical pore molecular sieve material, stirring with a glass plate (the mass ratio of the synthesized WO 3 to the hierarchical pore molecular sieve is 2:100, the solid-to-liquid ratio of the hierarchical pore molecular sieve material to the tungsten salt solution is 1:0.7 g/ml), standing at normal temperature for 6h, drying in a 100 ℃ oven for 6h, and calcining at 500 ℃ for 4h. And (3) placing the calcined mixture into an open type tubular furnace, heating to 700 ℃ under the condition of introducing ammonia gas, heating at a heating rate ranging from 4 ℃/min, and heating at the temperature for 3 hours to obtain the catalyst WN/hierarchical pore molecular sieve material which is denoted as catalyst 1 #.
The kinds, amounts and reaction parameters of the respective raw materials were adjusted as follows to obtain a series of catalysts having the numbers 2 to 28, which were designated as catalysts 2 # to 28 #, as shown in the following table 1:
TABLE 1
TABLE 2
TABLE 3 Table 3
The following are listed in tables 1 to 3 above:
The ZSM-5 molecular sieve (Z) has a silicon-aluminum ratio of 25;
the mordenite molecular sieve (S) has a silicon-aluminum ratio of 30;
Solid-to-liquid ratio: solid-to-liquid ratio of molecular sieve to lye (solid-to-liquid ratio 1), solid-to-liquid ratio of hierarchical pore molecular sieve to NH 4NO3 solution (solid-to-liquid ratio 2).
Tungsten salt: tungsten hexachloride (W1, dissolved in ethanol), ammonium metatungstate (W2, dissolved in deionized water).
XRD characterization
The diffraction peak of the WN mixture in the catalyst 1 # is consistent with the characteristic peak of the WN mixture (shown in figure 1) by adopting a Miniflex 600 type X-ray diffractometer and a Cu target to diffract the powder of the catalyst 1 #.
Characterization by gas chromatography
The composition of the acetaldehyde condensation reaction product was analyzed using Agilent 7890B gas chromatography (FID detector, HP-5 capillary column).
Example 2
The catalyst is used for preparing benzene by cyclohexane dehydrogenation.
Catalysts 1 # to 28 prepared in examples 1 to 3, catalyst 28 #, are used for preparing benzene by cyclohexane dehydrogenation, and the raw materials are contacted with the catalyst in the reactor and react for 3 hours under the condition of 310 ℃ and the pressure of 0.2Mpa to obtain a product containing benzene; the mass space velocity was 3h -1,H2 and the flow rate was 8ml/min. The raw materials are introduced into a fixed bed reactor loaded with 3g of the catalyst, and the dehydrogenation reaction is carried out to prepare benzene.
After the reaction is stable, the reaction raw materials and the products are analyzed by gas online chromatography. The reaction results are shown in Table 4.
TABLE 4 Table 4
It can be seen from the table that the prepared catalyst is applied to the reaction, and the catalytic reaction conversion rate and the selectivity are high.
Example 3
The catalyst 1 # prepared in tables 1 to 3 was used for the dehydrogenation reaction of cyclohexane to prepare benzene, the reaction parameters were changed, and after the reaction was stabilized, the reaction raw materials and the products were analyzed by gas online chromatography. The reaction results are shown in Table 5.
TABLE 5
It can be seen from the table that the reaction temperature has a large influence on the reaction conversion.
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 (9)
1. A nitrogen-containing catalyst for preparing benzene by cyclohexane dehydrogenation is characterized in that,
Comprises a hierarchical pore molecular sieve and nitride loaded on the surface of the hierarchical pore molecular sieve;
The nitride is selected from WN.
2. A process for preparing a nitrogen-containing catalyst for the dehydrogenation of cyclohexane to benzene, as claimed in claim 1,
The method comprises the following steps:
(1) Performing alkali treatment and ammonium ion exchange treatment on the initial molecular sieve to obtain a multi-stage pore molecular sieve;
(2) Immersing the multi-stage pore molecular sieve obtained in the step (1) in a solution containing a tungsten source to obtain a catalyst precursor, drying III, and calcining III to obtain a multi-stage pore molecular sieve loaded with WO 3;
(3) And (3) nitriding the multistage pore molecular sieve loaded with WO 3 obtained in the step (2) in an ammonia atmosphere to obtain the nitrogen-containing catalyst.
3. The method according to claim 2, wherein,
The alkali treatment comprises:
treating the initial molecular sieve with alkali liquor, drying the initial molecular sieve I, and calcining the initial molecular sieve I to obtain an alkali treated initial molecular sieve;
preferably, the initial molecular sieve is selected from the group consisting of a silica-alumina molecular sieve;
preferably, the aluminosilicate molecular sieve is selected from mordenite molecular sieves and/or ZSM-5 molecular sieves;
Preferably, the alkali liquor treatment temperature is 65-90 ℃;
Preferably, the alkali liquor treatment time is 0.5-1.5 h;
preferably, the lye is selected from NaOH solution and/or KOH solution;
preferably, the solid-to-liquid ratio of the molecular sieve to the lye is 1: (10-30) g/ml;
preferably, the concentration of the alkali liquor is 0.1-0.3 mol/L;
preferably, the temperature of the drying I is 80-130 ℃;
Preferably, the time for drying the I is 8-24 hours;
Preferably, the temperature of the calcination I is 450-650 ℃;
preferably, the calcination time of the catalyst I is 1 to 6 hours.
4. The method according to claim 2, wherein,
The ammonium ion exchange treatment includes:
Performing ammonium ion exchange on the obtained initial molecular sieve subjected to alkali treatment in an ammonium salt solution, drying II, and calcining II to obtain the hierarchical pore molecular sieve;
Preferably, the temperature of the ammonium ion exchange is 65-90 ℃;
preferably, the time of the ammonium ion exchange is 4-8 hours;
Preferably, the ammonium salt is NH 4NO3;
preferably, the concentration of the ammonium salt solution is 0.4-1.2 mol/L;
Preferably, the solid-to-liquid ratio of the molecular sieve to the ammonium salt solution is 1: (10-30) g/ml;
preferably, the temperature of the drying II is 80-130 ℃;
preferably, the time of drying II is 8-24 hours;
Preferably, the temperature of the calcination II is 450-650 ℃;
preferably, the time of calcination II is 1-6 h;
preferably, the hierarchical pore molecular sieve is crushed and sieved;
preferably, the particle size of the hierarchical pore molecular sieve obtained after crushing and sieving treatment is 16-32 meshes.
5. The method according to claim 2, wherein,
The tungsten source is selected from tungsten hexachloride and/or ammonium metatungstate;
The solid-to-liquid ratio of the hierarchical pore molecular sieve to the solution containing tungsten salt is 1: (0.6-0.8) g/ml;
Preferably, the temperature of the drying III is 80-130 ℃;
Preferably, the time for drying III is 6-24 hours;
Preferably, the temperature of the calcination III is 450-650 ℃;
Preferably, the time of calcining III is 1-6 h;
Preferably, in the multi-stage pore molecular sieve loaded with WO 3, the mass ratio of WO 3 to the multi-stage pore molecular sieve is (1-3): 100.
6. The method according to claim 2, wherein,
The temperature of the nitriding treatment is 650-750 ℃;
preferably, the nitriding treatment is carried out for 0.5-4 hours;
preferably, the temperature rising rate of the nitriding treatment is 4-10 ℃/min.
7. A method for preparing benzene by cyclohexane dehydrogenation reaction is characterized in that,
The method comprises the following steps:
Introducing a raw material containing hydrogen and cyclohexane into a reactor, contacting with a catalyst, and reacting to obtain a benzene-containing product;
Wherein the catalyst is selected from the nitrogen-containing catalyst for the dehydrogenation of cyclohexane to benzene according to claim 1 or the nitrogen-containing catalyst for the dehydrogenation of cyclohexane to benzene prepared by the preparation method according to any one of claims 2 to 6.
8. The method of claim 7, wherein the step of determining the position of the probe is performed,
The temperature of the reaction is 280-340 ℃;
The reaction time is 2-3 h;
The pressure of the reaction is 0.1-0.4 MPa.
9. The method of claim 7, wherein the step of determining the position of the probe is performed,
Among the raw materials, the raw materials are mixed,
The flow rate of the hydrogen is 5-10 ml/min;
The mass airspeed of the cyclohexane is 2-4 h -1.
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