CN115709061B - Preparation method and application of porous boron-molybdenum doped silicon-based material - Google Patents
Preparation method and application of porous boron-molybdenum doped silicon-based material Download PDFInfo
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- 239000002210 silicon-based material Substances 0.000 title claims abstract description 44
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 50
- 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 50
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims abstract description 38
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- 239000011733 molybdenum Substances 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000005530 etching Methods 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 230000003068 static effect Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 241000269350 Anura Species 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 238000006462 rearrangement reaction Methods 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000003763 carbonization Methods 0.000 abstract description 6
- 238000006237 Beckmann rearrangement reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 13
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 10
- 238000007605 air drying Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000006675 Beckmann reaction Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HYBIIGFUKKOJJM-UHFFFAOYSA-N cyclohexanone;hydroxylamine Chemical compound ON.O=C1CCCCC1 HYBIIGFUKKOJJM-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of catalysts for caprolactam production, and discloses a preparation method of a porous boron-molybdenum doped silicon-based material, which comprises the following steps: 1) Stirring and mixing an industrial molecular sieve, a carbon source and water uniformly, and drying, roasting and carbonizing, acid etching, washing and drying to obtain a porous carbon material; 2) Uniformly stirring and mixing the porous carbon material, the molybdenum source, the boron source, the silicon source, the ammonia water and the deionized water, carrying out static crystallization, drying, and roasting in an oxygen-enriched atmosphere to obtain the Kong Pengmu doped silicon-based material. According to the invention, through the steps of carbonization, acid etching, oxygen-enriched roasting and the like, the pore channel structure of the original molecular sieve is reserved, and molybdenum and boron elements are doped simultaneously when the molecular sieve framework is reduced, so that the catalytic performance of the porous boron-molybdenum doped silicon-based material in the cyclohexanone oxime liquid-phase Beckmann rearrangement reaction is improved.
Description
Technical Field
The invention belongs to the technical field of catalysts for caprolactam production, and relates to a preparation method and application of a porous boron-molybdenum doped silicon-based material.
Background
Caprolactam is an important organic chemical raw material, which mainly produces polyamide-6 fibers, polyamide resins and films by polymerization. The caprolactam production process mainly comprises the following steps: cyclohexanone-hydroxylamine, toluene, cyclohexane photonitrosation and cyclohexanone ammoximation. The method has the advantages of simple process flow, mild reaction conditions, high reactant conversion rate, high selectivity and the like, and the cyclohexanone oxime liquid-phase Beckmann rearrangement (cyclohexanone ammoximation method) is the main process for producing caprolactam. The concentrated sulfuric acid catalyst has strong corrosiveness and a large amount of low-value ammonium sulfate products as byproducts in the catalytic reaction process, and is a technical problem which needs to be overcome urgently. Therefore, the development of green catalytic research for producing caprolactam by rearrangement without ammonium sulfate is of great significance.
Molecular sieves including MCM-41, TS-1, SBA-15, HY, USY, beta, SAPO and the like have the advantages of excellent pore canal shape selectivity, excellent specific surface property, easy separation from products, reusability and the like, and are currently used for catalyzing the rearrangement of cyclohexanone oxime liquid phase to prepare caprolactam. However, the molecular sieve has the defects in catalyzing the cyclohexanone oxime liquid-phase rearrangement reaction: (1) lower catalytic efficiency; (2) the catalytic reaction temperature is higher; (3) the molecular sieve preparation process is too complex. Therefore, in order to overcome the defects of the molecular sieve in catalyzing the cyclohexanone oxime liquid-phase rearrangement reaction, the molecular sieve catalyst needs to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of a porous boron-molybdenum doped silicon-based material, which not only maintains the pore channel structure of an original molecular sieve, but also simultaneously dopes molybdenum and boron elements when a molecular sieve framework is reduced through the steps of carbonization, acid etching, oxygen-enriched roasting and the like, thereby improving the catalytic performance of the porous boron-molybdenum doped silicon-based material in a cyclohexanone oxime liquid-phase Beckmann rearrangement reaction.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of a porous boron-molybdenum doped silicon-based material, which comprises the following steps:
1) Stirring and mixing an industrial molecular sieve, a carbon source and water uniformly, and drying, roasting and carbonizing, acid etching, washing and drying to obtain a porous carbon material;
2) Uniformly stirring and mixing the porous carbon material, the molybdenum source, the boron source, the silicon source, the ammonia water and the deionized water, carrying out static crystallization, drying, and roasting in an oxygen-enriched atmosphere to obtain the Kong Pengmu doped silicon-based material.
Preferably, the industrial molecular sieve is selected from one of Beta-type, HY-type, SAPO-type or USY-type molecular sieves.
Preferably, the carbon source is selected from one or more of starch, wheat flour, corn flour, glucose or sucrose.
Preferably, the specific steps of roasting and carbonizing are as follows: roasting the dried sample at 350-850 ℃ for 6-24 h under the nitrogen atmosphere, wherein the temperature rising rate during roasting is 1-20 ℃/min.
Preferably, the specific steps of the acid etching are as follows: NH is added to 4 F/HF, water and the roasted carbonized sample are mixed and stirred for 12-48 hours at the temperature of 10-40 ℃, then the sample is washed by deionized water until the washing liquid is neutral, and then the porous carbon material is prepared by drying.
Preferably, the molybdenum source is selected from one or more of molybdic acid, ammonium molybdate, sodium molybdate.
Preferably, the boron source is selected from one of boric acid, ammonium borate, sodium borate or potassium borate.
Preferably, the silicon source is selected from one of alkaline silica sol, silica microsphere, orthosilicic acid, gamma-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, ethyl orthosilicate 28, ethyl orthosilicate 40 or white carbon black.
Preferably, the specific steps of roasting in the oxygen-enriched atmosphere are as follows: roasting the dried sample at 350-950 ℃ for 6-72 h under the oxygen-enriched atmosphere condition, wherein the temperature rising rate during roasting is 1-20 ℃/min, and the porous boron-molybdenum doped silicon-based material is obtained.
The invention also provides application of the porous boron-molybdenum doped silicon-based material in the reaction for producing caprolactam by liquid phase rearrangement, which is characterized in that the porous boron-molybdenum doped silicon-based material and cyclohexanone oxime are added into a reactor according to the mass ratio of 1-100:10, and react for 60-360 min at 50-130 ℃.
Compared with the prior art, the invention has the beneficial effects that:
according to the schematic diagram of the preparation of the catalyst shown in FIG. 1, a carbon source is filled in a molecular sieve pore canal, a baked carbon material is reserved in the molecular sieve pore canal, then a molecular sieve framework is removed through acid etching, so that a porous carbon material is prepared, the shape of the porous carbon material reserves the pore canal structure of the molecular sieve, then elements such as molybdenum, boron and silicon are filled around the porous carbon material, the molecular sieve framework is reduced through static crystallization, meanwhile, molybdenum and boron elements are doped in the molecular sieve framework, and finally, the carbon material is removed through oxygen-enriched baking, so that the porous boron-molybdenum doped silicon-based material is obtained.
The porous boron-molybdenum doped silicon-based material prepared by the invention effectively improves the catalytic performance in the cyclohexanone oxime liquid-phase Beckmann rearrangement reaction, the highest cyclohexanone conversion rate can reach 83.1%, and the highest caprolactam selectivity can reach 99.5%.
Drawings
FIG. 1 is a schematic diagram of the preparation principle of the porous boron-molybdenum doped silicon-based material.
Detailed Description
The following examples are illustrative of the present invention and are not intended to limit the scope of the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. The test methods in the following examples are conventional methods unless otherwise specified.
Example 1
(1) Preparation of porous carbon Material
Firstly, 50g of Beta molecular sieve, 100g of starch and 200g of deionized water are weighed and placed in a reaction vessel, and the mixture is fully stirred for 1h at 20 ℃. Then, the mixture was dried in a forced air drying oven at a temperature of 100℃for 12 hours. Subsequently, the dried sample was baked under the following specific baking conditions: and (3) in a muffle furnace in a nitrogen atmosphere, heating to 550 ℃ at a heating rate of 15 ℃/min, and roasting for 10h. Next, 50 to 50gNH 4 And (3) performing sealed mixing stirring on the F/HF mixed solution, 30g of water and 50g of roasted sample at 20 ℃ for 12 hours, washing the sample by using a large amount of deionized water until the washing solution is neutral, and then drying at 100 ℃ to obtain the porous carbon material.
(2) Preparation of porous boron-molybdenum doped silicon-based material
Firstly, 25g of porous carbon material, 30g of molybdic acid, 30g of boric acid, 30g of alkaline silica sol, 20g of ammonia water (concentration 28%) and 300g of deionized water are weighed, placed in a beaker, mechanically stirred at 20 ℃ for 60min at 800rpm, and statically crystallized. Then, the above mixture was placed in a forced air drying oven and dried at 100℃for 3 hours. And then roasting the dried sample under the oxygen-enriched atmosphere condition, heating to 550 ℃ at a heating rate of 20 ℃/min, and roasting for 24 hours to finally prepare the porous boron-molybdenum doped silicon-based material.
(3) Catalytic caprolactam reaction
20g of porous boron-molybdenum doped silicon-based material and 5g of cyclohexanone oxime are mixed and placed into a reactor, reacted for 180min at 130 ℃, and subjected to centrifugal separation to obtain liquid phase mixed solution, and gas chromatography analysis is carried out. The results are shown in Table 1.
Example two
(1) Preparation of porous carbon Material
Firstly, 50g of HY molecular sieve, 100g of wheat flour and 200g of deionized water are weighed and placed in a reaction vessel, and fully stirred for 1h at 20 ℃. Then, the mixture was dried in a forced air drying oven at a temperature of 100℃for 12 hours. Subsequently, the dried sample was baked under the following specific baking conditions: and (3) in a muffle furnace in a nitrogen atmosphere, heating to 550 ℃ at a heating rate of 15 ℃/min, and roasting for 10h. Next, 60 to 60gNH 4 And (3) performing sealed mixing stirring on the F/HF mixed solution, 30g of water and 50g of roasted sample at 20 ℃ for 12 hours, washing the sample by using a large amount of deionized water until the washing solution is neutral, and then drying at 100 ℃ to obtain the porous carbon material.
(2) Preparation of porous boron-molybdenum doped silicon-based material
First, 18g of a porous carbon material, 20g of ammonium molybdate, 40g of boric acid, 30g of tetraethyl orthosilicate 28, 10g of ammonia water (concentration 28%) and 350g of deionized water were weighed and placed in a beaker, and mechanically stirred at 40 ℃ for 40min at 1000rpm, and statically crystallized. Then, the above mixture was placed in a forced air drying oven and dried at 100℃for 6 hours. And then roasting the dried sample under the oxygen-enriched atmosphere condition, heating to 850 ℃ at the heating rate of 10 ℃/min, and roasting for 36 hours to finally prepare the porous boron-molybdenum doped silicon-based material.
(3) Catalytic caprolactam reaction
24g of porous boron-molybdenum doped silicon-based material and 8g of cyclohexanone oxime are mixed and placed into a reactor, reacted for 180min at 130 ℃, and subjected to centrifugal separation to obtain liquid phase mixed solution, and gas chromatography analysis is carried out. The results are shown in Table 1.
Example III
(1) Preparation of porous carbon Material
Firstly, 50g of SAPO molecular sieve, 100g of wheat flour and 500g of deionized water are weighed and placed in a reaction vessel, and the mixture is fully stirred for 1h at 20 ℃. Then, the mixture is placed at the temperature ofDrying in a forced air drying oven at 100deg.C for 12 hr. Subsequently, the dried sample was baked under the following specific baking conditions: and (3) in a muffle furnace in a nitrogen atmosphere, heating to 550 ℃ at a heating rate of 15 ℃/min, and roasting for 10h. Next, 60 to 60gNH 4 And (3) performing sealed mixing stirring on the F/HF mixed solution, 30g of water and 50g of roasted sample at 20 ℃ for 12 hours, washing the sample by using a large amount of deionized water until the washing solution is neutral, and then drying at 100 ℃ to obtain the porous carbon material.
(2) Preparation of porous boron-molybdenum doped silicon-based material
First, 20g of a porous carbon material, 20g of sodium molybdate, 40g of boric acid, 30g of tetraethyl orthosilicate 40, 18g of ammonia water (concentration 28%) and 380g of deionized water were weighed and placed in a beaker, and mechanically stirred at 40 ℃ for 90min at 1000rpm, and statically crystallized. Then, the above mixture was placed in a forced air drying oven and dried at 100℃for 6 hours. And then roasting the dried sample under the oxygen-enriched atmosphere condition, heating to 850 ℃ at the heating rate of 10 ℃/min, and roasting for 36 hours to finally prepare the porous boron-molybdenum doped silicon-based material.
(3) Catalytic caprolactam reaction
24g of porous boron-molybdenum doped silicon-based material and 8g of cyclohexanone oxime are mixed and placed into a reactor, reacted for 180min at 130 ℃, and subjected to centrifugal separation to obtain liquid phase mixed solution, and gas chromatography analysis is carried out. The results are shown in Table 1.
Example IV
(1) Preparation of porous carbon Material
Firstly, 50g of USY molecular sieve, 100g of glucose and 500g of deionized water are weighed and placed in a reaction vessel, and fully stirred for 1h at 20 ℃. Then, the mixture was dried in a forced air drying oven at a temperature of 100℃for 12 hours. Subsequently, the dried sample was baked under the following specific baking conditions: and (3) in a muffle furnace in a nitrogen atmosphere, heating to 550 ℃ at a heating rate of 15 ℃/min, and roasting for 10h. Next, 60 to 60gNH 4 And (3) performing sealed mixing stirring on the F/HF mixed solution, 30g of water and 50g of roasted sample at 20 ℃ for 12 hours, washing the sample by using a large amount of deionized water until the washing solution is neutral, and then drying at 100 ℃ to obtain the porous carbon material.
(2) Preparation of porous boron-molybdenum doped silicon-based material
Firstly, 20g of porous carbon material, 20g of molybdic acid, 40g of boric acid, 30g of orthosilicic acid, 18g of ammonia water (28%) and 250g of deionized water are weighed, placed in a beaker, mechanically stirred at 40 ℃ and 1000rpm for 90min, and statically crystallized. Then, the above mixture was placed in a forced air drying oven and dried at 100℃for 6 hours. And then roasting the dried sample under the oxygen-enriched atmosphere condition, heating to 850 ℃ at the heating rate of 10 ℃/min, and roasting for 36 hours to finally prepare the porous boron-molybdenum doped silicon-based material.
(3) Catalytic caprolactam reaction
24g of porous boron-molybdenum doped silicon-based material and 8g of cyclohexanone oxime are mixed and placed into a reactor, reacted for 180min at 130 ℃, and subjected to centrifugal separation to obtain liquid phase mixed solution, and gas chromatography analysis is carried out. The results are shown in Table 1.
Comparative example 1
50g of Beta molecular sieve, 20g of molybdic acid, 40g of boric acid and 30g of orthosilicic acid are weighed and placed in a beaker, and fully stirred for 1h at 20 ℃. The mixture is placed in a blast drying oven and dried for 6 hours at 100 ℃. And then roasting the dried sample under the oxygen-enriched atmosphere condition, heating to 550 ℃ at a heating rate of 15 ℃/min, and roasting for 10 hours to finally prepare the molecular sieve A.
20g of molecular sieve A and 8g of cyclohexanone oxime are mixed and placed into a reactor, reacted for 180min at 130 ℃, and subjected to centrifugal separation to obtain liquid phase mixed solution, and gas chromatography analysis is carried out. The results are shown in Table 1.
Comparative example 2
50g of Beta molecular sieve, 100g of starch, 200g of deionized water, 30g of molybdic acid and 30g of boric acid are weighed, placed in a reaction vessel and fully stirred for 1h at 20 ℃. Then, the above mixture was placed in a forced air drying oven and dried at 100℃for 3 hours. And then roasting the dried sample under the oxygen-enriched atmosphere condition, heating to 550 ℃ at a heating rate of 15 ℃/min, and roasting for 10 hours to finally prepare the molecular sieve B.
24g of molecular sieve B and 5g of cyclohexanone oxime are mixed and placed into a reactor, reacted for 180min at 130 ℃, and subjected to centrifugal separation to obtain liquid phase mixed solution, and gas chromatography analysis is carried out. The results are shown in Table 1.
Comparative example 3
This comparative example is substantially the same as example 1 except that a molecular sieve C is obtained without adding a molybdenum source in the second step of preparing the porous boron molybdenum doped silicon-based material.
24g of molecular sieve C and 5g of cyclohexanone oxime are mixed and placed into a reactor, reacted for 180min at 130 ℃, and subjected to centrifugal separation to obtain liquid phase mixed solution, and gas chromatography analysis is carried out. The results are shown in Table 1.
Comparative example 4
This comparative example is substantially the same as example 1 except that a boron source is not added in the second step of preparing the porous boron molybdenum doped silicon-based material to obtain molecular sieve D.
24g of molecular sieve D and 5g of cyclohexanone oxime are mixed and placed into a reactor, reacted for 180min at 130 ℃, and subjected to centrifugal separation to obtain liquid phase mixed solution, and gas chromatography analysis is carried out. The results are shown in Table 1.
Comparative example 5
This comparative example is substantially the same as example 1 except that a silicon source is not added in the second step of preparing a porous boron molybdenum doped silicon-based material to obtain molecular sieve E.
24g of molecular sieve E and 5g of cyclohexanone oxime are mixed and placed into a reactor, reacted for 180min at 130 ℃, and subjected to centrifugal separation to obtain liquid phase mixed solution, and gas chromatography analysis is carried out. The results are shown in Table 1.
TABLE 1 catalytic Effect of the catalysts of examples 1-4 and comparative examples 1-5
| Examples | Cyclohexanone conversion (%) | Caprolactam Selectivity (%) |
| Example 1 | 83.1 | 99.0 |
| Example 2 | 78.2 | 99.5 |
| Example 3 | 79.1 | 99.2 |
| Example 4 | 78.7 | 99.1 |
| Comparative example 1 | 63.1 | 99.2 |
| Comparative example 2 | 60.3 | 99.0 |
| Comparative example 3 | 62.7 | 99.1 |
| Comparative example 4 | 44.4 | 99.3 |
| Comparative example 5 | 37.9 | 98.9 |
As can be seen from table 1, in comparative example 1, molybdenum and boron are directly doped in the molecular sieve, while in the process of statically crystallizing and reducing the molecular sieve framework, the cyclohexanone conversion rate of the catalyst obtained by doping molybdenum and boron in example 1 of the invention is greatly improved, and therefore, the doping in the crystallization process can improve the doping amount of the elements, thereby being beneficial to improving the conversion rate. Compared with the carbon material of comparative example 2, the carbon material is added and carbonized in the doping process of the molecular sieve molybdenum and boron, in all the embodiments 1 to 4 of the invention, the molecular sieve pore canal is reserved through carbonization of the carbon material, the molecular sieve framework is removed through acid etching, and then the molecular sieve framework is reduced through static crystallization, so that the cyclohexanone conversion rate of the obtained catalyst is greatly improved, and the catalyst obtained through carbonization is better than that obtained through carbonization after carbonization. Compared with the comparative example 3 in which only boron element is doped and the comparative example 4 in which only molybdenum element is added, the comparative example 5 in which silicon element is absent when the molecular sieve framework is reduced, and the catalysts obtained by adding boron, molybdenum and silicon elements simultaneously in the examples 1 to 4 of the invention have better catalytic performance. In addition, different molecular sieves are selected in the embodiment 1-4 of the invention, the pore canal structure of the corresponding molecular sieve is still maintained after the molecular sieve framework is reduced, and compared with the embodiment 2-4 which adopts HY, SAPO and USY type molecular sieves, the embodiment 1 of the invention adopts Beta type molecular sieves, and the pore canal structure has excellent shape selective catalytic performance in the cyclohexanone oxime Beckmann reaction.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and other embodiments can be easily made by those skilled in the art through substitution or modification according to the technical disclosure in the present specification, so that all changes and modifications made in the principle of the present invention shall be included in the scope of the present invention.
Claims (9)
1. The preparation method of the porous boron molybdenum doped silicon-based material is characterized by comprising the following steps of:
1) Stirring and mixing an industrial molecular sieve, a carbon source and water uniformly, and drying, roasting and carbonizing, acid etching, washing and drying to obtain a porous carbon material; the industrial molecular sieve is selected from one of Beta type, HY type, SAPO type or USY type molecular sieves;
2) Uniformly stirring and mixing the porous carbon material, the molybdenum source, the boron source, the silicon source, the ammonia water and the deionized water, carrying out static crystallization, drying, and roasting in an oxygen-enriched atmosphere to obtain the Kong Pengmu doped silicon-based material.
2. The method for preparing a porous boron molybdenum doped silicon based material according to claim 1, wherein the carbon source is one or more selected from starch, wheat flour, corn flour, glucose and sucrose.
3. The method for preparing the porous boron molybdenum doped silicon-based material according to claim 1, wherein the specific steps of roasting and carbonizing are as follows: and roasting the dried sample at 350-850 ℃ for 6-24 hours under the nitrogen atmosphere, wherein the temperature rising rate during roasting is 1-20 ℃/min.
4. The method for preparing the porous boron molybdenum doped silicon-based material according to claim 1, wherein the specific steps of the acid etching are as follows: NH is added to 4 F/HF, water and the roasted and carbonized sample are mixed and stirred for 12-48 hours at the temperature of 10-40 ℃, then the sample is washed by deionized water until the washing liquid is neutral, and then the porous carbon material is prepared by drying.
5. The method for preparing a porous boron molybdenum doped silicon based material according to claim 1, wherein said molybdenum source is selected from one or more of molybdic acid, ammonium molybdate, sodium molybdate.
6. The method for preparing a porous boron molybdenum doped silicon based material according to claim 1, wherein said boron source is selected from one of boric acid, ammonium borate, sodium borate or potassium borate.
7. The method for preparing a porous boron molybdenum doped silicon based material according to claim 1, wherein the silicon source is selected from one of alkaline silica sol, silica microsphere, orthosilicic acid, gamma-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, ethyl orthosilicate 28, ethyl orthosilicate 40 or white carbon black.
8. The preparation method of the porous boron molybdenum doped silicon-based material according to claim 1, wherein the specific steps of roasting in the oxygen-enriched atmosphere are as follows: and (3) roasting the dried sample at 350-950 ℃ for 6-72 h under the oxygen-enriched atmosphere condition, wherein the temperature rising rate during roasting is 1-20 ℃/min, and the porous boron-molybdenum doped silicon-based material is obtained.
9. The application of the porous boron-molybdenum doped silicon-based material prepared by the preparation method of the porous boron-molybdenum doped silicon-based material according to any one of claims 1-8 in a liquid phase rearrangement reaction for producing caprolactam, wherein the porous boron-molybdenum doped silicon-based material and cyclohexanone oxime are added into a reactor according to a mass ratio of 1-100:10, and react for 60-360 min at 50-130 ℃.
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