CN115301261B - Nickel-loaded boron-doped silicon carbide and preparation method thereof, and aniline preparation method - Google Patents
Nickel-loaded boron-doped silicon carbide and preparation method thereof, and aniline preparation method Download PDFInfo
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- CN115301261B CN115301261B CN202210725440.8A CN202210725440A CN115301261B CN 115301261 B CN115301261 B CN 115301261B CN 202210725440 A CN202210725440 A CN 202210725440A CN 115301261 B CN115301261 B CN 115301261B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 218
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 116
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 100
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052796 boron Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 74
- 239000000047 product Substances 0.000 claims description 52
- 239000013067 intermediate product Substances 0.000 claims description 42
- 238000006722 reduction reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 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 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-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
- 238000002791 soaking Methods 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- UTHULKKJYXJZLV-UHFFFAOYSA-N (3-aminophenoxy)boronic acid Chemical compound NC1=CC=CC(OB(O)O)=C1 UTHULKKJYXJZLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- JBXYCUKPDAAYAS-UHFFFAOYSA-N methanol;trifluoroborane Chemical compound OC.FB(F)F JBXYCUKPDAAYAS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229920003257 polycarbosilane Polymers 0.000 claims description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- -1 trialkylborane Chemical compound 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 63
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 22
- 238000011068 loading method Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000002829 reductive effect Effects 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 238000011049 filling Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000009489 vacuum treatment Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysis, and discloses nickel-loaded boron-doped silicon carbide, a preparation method thereof and a preparation method of aniline. Nickel-loaded boron-doped silicon carbide with SiC-B x For loading nickel on the carrier, the loading of nickel on the boron doped silicon carbide loaded with nickel is 1-30%, siC-B x X in (2) is any value between 0.01 and 0.5. The nickel-loaded boron-doped silicon carbide provided by the invention can reduce the cost of the nitrobenzene selective hydrogenation catalyst while guaranteeing the catalytic activity.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to nickel-loaded boron-doped silicon carbide, a preparation method thereof and a preparation method of aniline.
Background
Catalytic reduction of aromatic nitro compounds is an important reaction in the chemical industry, and the product aniline is one of the most important amine substances, and is mainly used for dyes, medicines and resins. Most anilines are obtained by reduction of nitrobenzene. Common methods for reducing nitrobenzene include an iron powder reduction method, a hydrazine hydrate reduction method, a sodium sulfide reduction method and the like, but the methods are not suitable for mass production and are eliminated due to the fact that production equipment for realizing the methods is huge, serious three-waste pollution is caused in the production process, and the problems of high production cost and the like exist.
In recent years, siO 2 、TiO 2 、Y-Al 2 O 3 And carbon materials and the like are used as carriers to load noble metals such as Pt, pd, au and the like as a nitrobenzene hydrogenation catalyst, so that the catalyst is widely studied. The nitrobenzene hydrogenation catalyst loaded with noble metal has high reaction activity, but simultaneously has the realistic problem of overhigh cost. Therefore, researchers pay attention to the direction of the non-noble metal nitrobenzene hydrogenation catalyst, but because the non-noble metal nitrobenzene hydrogenation catalyst has low activity and poor tolerance, the metal load is high, the cost of the non-noble metal nitrobenzene hydrogenation catalyst is increased, and the wide application of the non-noble metal nitrobenzene hydrogenation catalyst in the preparation process of aniline is limited. As in one document, the nitrobenzene hydrogenation catalyst is Co-ZrO2/SBA-15, with Co loading levels of up to 2-40wt%.
Therefore, there is a need for nickel-loaded boron-doped silicon carbide, a preparation method thereof and a preparation method of aniline, which reduce the cost of nitrobenzene hydrogenation catalyst, optimize the preparation method of aniline, reduce the pollution generated in the aniline production process, and reduce the equipment requirements in the aniline production process.
Disclosure of Invention
In order to solve the problems, the invention provides the nickel-loaded boron-doped silicon carbide, which is loaded with a small amount of nickel, so that the cost of the nitrobenzene selective hydrogenation catalyst is reduced while the catalytic activity is ensured.
The boron doped silicon carbide loaded with nickel is prepared by SiC-B x The nickel is supported on a carrier, the nickel is supported on the nickel-supported boron-doped silicon carbide at a loading amount of 1-30%, and the SiC-B is x X in (2) is any value between 0.01 and 0.5.
The invention also provides a preparation method of the nickel-loaded boron-doped silicon carbide, and the nickel-loaded boron-doped silicon carbide prepared by the method has lower cost and is beneficial to optimizing the preparation method of aniline.
The preparation method of the nickel-loaded boron-doped silicon carbide comprises the following steps:
s1: adding SiC-B into a first reaction vessel x Mixing with dispersant, water and nickel salt to form mixed solution, and charging 2MPa H 2 Reacting for 1-3h at 100-200 ℃ to obtain an intermediate product;
s2: the intermediate product is reduced by hydrogen-nitrogen mixed gas for 1-3 hours in a tube furnace at 450-600 ℃ to obtain the boron doped silicon carbide loaded with nickel,
wherein the SiC-B x X in the formula is any value between 0.01 and 0.5,
the dispersing agent is selected from one or more of polyvinylpyrrolidone and polyvinylpyrrolidone,
the nickel salt is selected from one or more of nickel nitrate hexahydrate, nickel sulfate, nickel acetate tetrahydrate and nickel chloride hexahydrate.
Optionally, the preparation method of the nickel-loaded boron-doped silicon carbide comprises post-treatment after the step S2: the boron doped silicon carbide loaded with nickel is passivated for 1h under the protection of inert gas at room temperature.
Optionally, in step S1, the reaction temperature is 150 ℃ and the reaction time period is 2 hours.
Optionally, the preparation method of the nickel-loaded boron doped silicon carbide comprises the following intermediate treatment after the step S1 and before the step S2: the intermediate product is cooled, filtered, dried in vacuo and ground. In the step S2, the reduction reaction temperature is 450 ℃, and the reduction reaction time is 1h.
Optionally, the SiC-B x The preparation method comprises the following steps:
s01: dissolving a carbon source in a first solvent, adding a silicon source, metal salt and boride to obtain a mixed solution, reacting the mixed solution at 150-200 ℃ for 2-7 hours to obtain a first product, standing, and removing supernatant of the first product to obtain a precipitate;
s02: placing the precipitate in an inert atmosphere, and performing carbothermic reduction reaction at 1000-1500 ℃ for 3-30h to obtain a second product;
s03: placing the second product in air, and calcining at 500-900 ℃ for 2-8h to obtain a third product;
s04: soaking the third product in a mixture of hydrochloric acid and hydrofluoric acid in a volume ratio of 1:1-5 for 12-48h to obtain the SiC-B x ，
Wherein the molar ratio of the carbon source to the silicon source in the mixed solution of S01 is 0.1:1-20, and the molar ratio of the silicon source to the metal salt is 0.5:1-5, the molar ratio of the silicon source to the boride is 0.01:0.5-7.
Optionally, the carbon source is selected from one or more of sucrose, biomass polystyrene sulfonic acid resin and graphite, the silicon source is selected from one or more of silica sol, water glass and polycarbosilane, the metal salt is selected from one or more of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride, and the boride is selected from one or more of boric acid, borax, sodium borohydride, 3-aminophenylboric acid, trialkylborane, boron trifluoride-methanol and ammonia borane.
The invention also provides a preparation method of the aniline, and the aniline prepared by the method can reduce pollution generated in the aniline production process and reduce the requirement on equipment in the aniline production process.
The preparation method of the aniline comprises the following steps:
preparing nickel-loaded boron-doped silicon carbide;
adding nitrobenzene, a second solvent and the boron doped silicon carbide loaded with nickel into a second reaction vessel, introducing reducing agent hydrogen, heating, carrying out reduction reaction to obtain the aniline,
wherein the volume ratio of the nitrobenzene to the solvent is 0.1-1:5-20, the mol ratio of the nitrobenzene to the nickel-loaded boron doped silicon carbide is 1-10:0.04-0.6,
after the hydrogen is filled, the pressure value of the second container is 0.5-6MPa, the reduction reaction temperature is 20-100 ℃, and the reduction reaction time is 2-8h.
Alternatively, the reduction reaction temperature is 90 ℃ and the reduction reaction time is 5 hours.
Optionally, the second solvent is one or more of methanol, ethanol, acetonitrile or N, N-dimethylformamide.
The nickel-loaded boron-doped silicon carbide has low nickel content and high activity, reduces the cost of the non-noble metal nitrobenzene hydrogenation catalyst, is beneficial to wide application in aniline production, reduces pollution in aniline production process, and reduces the requirement on equipment in aniline production process.
Drawings
FIG. 1 is a flow chart of a preparation method of nickel-loaded boron-doped silicon carbide;
FIG. 2 is a flow chart of the aniline preparation method provided by the invention;
FIG. 3 shows the invention for SiC/B with different boron doping levels x An XRD pattern of (x=0.01, 0.05, 0.1, 0.5);
FIG. 4 is SiC/B x EDS plot of (x=0.01, 0.05, 0.1, 0.5).
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a detailed description of specific embodiments thereof will be presented in connection with the accompanying drawings, but should not be construed as limiting the scope of the invention.
Non-metallic element doping, such as boron (B), fluorine (F), sulfur (S), nitrogen (N), has been attracting attention as a method capable of affecting the reactivity, and has an effect of adjusting the electronic structure, morphology, and physicochemical properties of the carrier. 1. The preparation of a nitrogen (N) -doped mesoporous carbon material loaded with palladium (Pd) in the literature achieves high dispersion of Pd nanoparticles (Journal of the American Chemical Society,2012,134 (41): 16987-16990). The B-doped graphene of another document is able to significantly increase the charge transfer efficiency, facilitating the progress of the electrocatalytic reaction (Journal of Materials Chemistry A,2018, 6:2176-2183.). In view of the advantages of non-metallic element doping, in order to solve the problems of low catalyst reaction activity, high metal loading and high catalyst cost in the research of catalysts for preparing aniline and the problems of high equipment requirements and a large amount of three wastes in the reaction caused by the reaction for preparing aniline, the invention relates to a catalyst for preparing aniline by using boron doped silicon carbide (SiC-B x ) The catalyst is loaded with a small amount of nickel, so that the activity of the nickel-loaded boron doped silicon carbide serving as the catalyst in the aniline preparation reaction by nitrobenzene selective hydrogenation is improved, and meanwhile, the cost of the catalyst is reduced, so that the catalyst is beneficial to benzeneOptimization of the amine preparation method reduces pollution generated in the preparation method and reduces the requirement of the preparation method on equipment.
The nickel-loaded boron-doped silicon carbide is formed by loading transition metal nickel serving as an active component on the boron-doped silicon carbide, and the cost of the catalyst can be reduced because raw materials used in the preparation process of the nickel-loaded boron-doped silicon carbide are easy to obtain and low in price.
A nickel-loaded boron-doped silicon carbide, which is prepared by SiC-B x For loading nickel on the carrier, the loading of nickel on the nickel-loaded boron-doped silicon carbide is 1-30%, and the SiC-B x X in (2) is any value between 0.01 and 0.5. Compared with the existing nitrobenzene hydrogenation catalyst which is Co-ZrO2/SBA-15 and has the cobalt loading of 2-40wt%, the nickel-loaded boron-doped silicon carbide provided by the invention has the nickel content of 1-30%, the loading is reduced by 25% -50%, the price of nickel is lower than the price of cobalt, the catalytic hydrogenation activity is ensured, the cost of the catalyst is reduced, the wide application in the aniline preparation process is facilitated, and the aniline preparation method is optimized.
Referring to fig. 1, a method for preparing nickel-loaded boron doped silicon carbide includes the following steps:
s1: adding SiC-B into a first reaction vessel x Mixing with dispersant, water and nickel salt to form mixed solution, sealing the first reaction container, flushing gas and filling 2MPa H 2 Reacting for 1-3h at 100-200 ℃ to obtain an intermediate product;
s2: the intermediate product is reduced by hydrogen-nitrogen mixed gas for 1-3 hours in a tube furnace at the temperature of 450-600 ℃ to obtain the boron doped silicon carbide loaded with nickel,
wherein, siC-B x X in the formula is any value between 0.01 and 0.5,
the dispersing agent is selected from one or more of polyvinylpyrrolidone and polyvinylpyrrolidone,
the nickel salt is selected from one or more of nickel nitrate hexahydrate, nickel sulfate, nickel acetate tetrahydrate and nickel chloride hexahydrate,
the polyvinylpyrrolidone and the polyacrylamide are water-soluble polymers, and are mainly used for dispersing metals in the preparation process of the catalyst. PVP belongs to a nonionic solvent, and PAM belongs to an ionic solvent.
First to H 2 The gas washing is carried out, so that the impurities in the gas can be reduced, and the occurrence of side reactions is reduced.
Intermediate NiO/SiC-B in step S2 x Reduced to form nickel-loaded boron-doped silicon carbide Ni/SiC-B x 。
The nickel content of the nickel-loaded boron-doped silicon carbide prepared by the method is 1-30 percent, compared with Co-ZrO in the prior art 2 The loading of Co on SBA-15 is 2-40wt%, the metal loading is reduced by 25% -50%, and the price of nickel is lower than that of cobalt, so that the cost of the nitrobenzene selective hydrogenation catalyst is obviously reduced while the catalytic activity of the nitrobenzene selective hydrogenation catalyst is ensured.
Content of reacted Nickel salt and reacted SiC-B x When the mass ratio of the substances is 1.56, the nickel loading capacity of the prepared nickel-loaded boron-doped silicon carbide reaches 30 percent.
Content of reacted Nickel salt and reacted SiC-B x When the mass ratio of the substances is 0.1, the nickel loading amount in the prepared nickel-loaded boron-doped silicon carbide reaches 2 percent.
In one embodiment, the preparation method of the nickel-loaded boron-doped silicon carbide comprises the post-treatment after the step S2: the boron doped silicon carbide loaded with nickel is passivated for 1h under the protection of inert gas at room temperature.
Due to reduced Ni/SiC-B x The catalyst is unstable and can be exposed to air in the process of transferring to the reaction kettle, so that Ni/SiC-B x Oxidizing the surface of the catalyst; in addition, due to reduced Ni/SiC-B x The metal nickel loaded on the catalyst has high activity, high surface hydrogen concentration and easy spark generation when exposed to air. Therefore, the protective layer is formed on the surface of the catalyst by passivation with an inert gas at room temperature, preventing the above situation from occurring.
In one embodiment, in S1, the reaction temperature is 150℃and the reaction time period is 2 hours.
In one embodiment, the intermediate processing after step S1 and before step S2 is included: the intermediate product was cooled, filtered, dried in vacuo and ground.
The reduction temperature of the intermediate product in S2 is 450 ℃, and the reduction time is 1h.
The tube furnace has fast heat transfer and higher heat efficiency, the reaction time is shorter, and under other conditions, the time of the reduction reaction can be prolonged according to the heat transfer efficiency of the reaction vessel.
The intermediate product comprises cooling, suction filtration, vacuum drying and grinding processes of the intermediate product, preferably naturally cooling to room temperature, and drying overnight in a vacuum oven before entering the tube furnace. The suction filtration process is to remove the dispersant and unreacted nickel from the intermediate product. The grinding process is to make the reaction contact fully, increase the reaction efficiency and shorten the reaction time.
In one embodiment, siC-B x The preparation method comprises the following steps:
s01: dissolving a carbon source in a first solvent, adding a silicon source, metal salt and boride to obtain a mixed solution, reacting the mixed solution at 150-200 ℃ for 2-7 hours to obtain a first product, standing, and removing supernatant of the first product to obtain a precipitate;
s02: placing the precipitate in an inert atmosphere, and performing carbothermic reduction reaction at 1000-1500 ℃ for 3-30h to obtain a second product;
s03: placing the second product in air, and calcining at 500-900 ℃ for 2-8h to obtain a third product;
s04: soaking the third product in a mixture of hydrochloric acid and hydrofluoric acid in a volume ratio of 1:1-5 for 12-48h to obtain SiC-B x ，
Wherein the molar ratio of the carbon source to the silicon source in the mixed solution in the step S01 is 0.1:1-20, and the molar ratio of the silicon source to the metal salt is 0.5:1-5, the molar ratio of the silicon source to the boride is 0.01:0.5-7.
The chemical property of the silicon carbide is very stable, and boron doping is difficult to realize by an impregnation method or a coprecipitation method, so that the silicon carbide is doped in the process of preparing the silicon carbide by an in-situ doping method.
Optionally, the third product is soaked with a 1:3 volume ratio of hydrochloric acid and hydrofluoric acid mixture for 12-48h.
Optionally, the carbon source is selected from one or more of sucrose, biomass, polystyrene sulfonic acid resin and graphite, and different carbon sources may affect SiC-B x Specific surface area of the support, pore distribution and yield. The silicon source is selected from one or more of silica sol, water glass and polycarbosilane, and different silicon sources can influence the specific surface area and pore distribution of SiC. The metal salt is selected from one or more of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride, and the boride is selected from one or more of boric acid, borax sodium borohydride, 3-aminophenylboric acid, trialkylborane, boron trifluoride-methanol and ammonia borane. The first solvent is an aqueous solvent, preferably water.
The present invention also provides a method for preparing aniline, referring to fig. 2, the method for preparing aniline includes:
preparing nickel-loaded boron-doped silicon carbide;
adding nitrobenzene, a second solvent and boron doped silicon carbide loaded with nickel into a second reaction vessel, introducing reducing agent hydrogen, heating, carrying out reduction reaction to obtain aniline,
wherein the volume ratio of nitrobenzene to the second solvent is 0.1-1:5-20, the mol ratio of nitrobenzene to nickel-loaded boron doped silicon carbide is 1-10:0.04-0.06,
after hydrogen is filled, the pressure in the second container is 0.5-6MPa, the reduction reaction temperature is 20-100 ℃, and the reduction reaction time is 2-8h.
In the preparation method of the aniline, the reaction route for preparing the aniline by the nitrobenzene selective hydrogenation is as follows:
and (3) performing selective hydrogenation on nitrobenzene to generate aniline and water, performing solid-liquid separation on a reaction product in the second reaction container after the reaction is finished, separating out a solid phase as a catalyst, and performing drying treatment on the catalyst for recycling.
Alternatively, the reduction reaction temperature is 90 ℃ and the reduction reaction time is 5 hours. Under the conditions of the reaction temperature and the reaction duration, the conversion rate of nitrobenzene and the selectivity of directional hydrogenation are the best in the process of preparing aniline by catalytic hydrogenation of nitrobenzene.
Optionally, the second solvent is a polar solvent, which may be selected from a polar protic solvent such as methanol, ethanol, isopropanol, acetic acid, or water, and may be selected from a polar aprotic solvent such as acetonitrile, acetone, or N, N-dimethylformamide.
The nickel-loaded boron-doped silicon carbide, the preparation method thereof and the preparation method of aniline are further described below by specific examples.
Example 1-example 4 preparation of SiC-B with varying boron doping levels x 。
Example 1
Firstly, 14.23g of sucrose is dissolved in 100ml of water, 0.22g of nickel nitrate, 12.47g of silica sol and 0.0386g of boric acid are added and mixed uniformly, the mixture is reacted for 4 hours at 180 ℃ in a hydrothermal reaction kettle to obtain a first product, the first product is stood, supernatant fluid of the first product is removed to obtain a precipitate, and the precipitate is dried; placing the precipitate into a tubular high-temperature furnace, introducing argon, programming to be heated to 1450 ℃, reacting at constant temperature for 8 hours to obtain a second product, and naturally cooling the second product in an argon atmosphere; calcining the obtained second product in the air at 700 ℃ for 3 hours to obtain a third product; soaking the third product in mixed acid of hydrochloric acid and hydrofluoric acid in the volume ratio of 1:3 for 24h, washing, filtering and drying to obtain SiC-B 0.01 。
Example 2
Firstly, 14.23g of sucrose is dissolved in 100ml of water, 0.22g of nickel nitrate, 12.47g of silica sol and 0.193g of boric acid are added and mixed uniformly, the mixture reacts for 4 hours at 180 ℃ in a hydrothermal reaction kettle to obtain a first product, the first product is stood, supernatant fluid of the first product is removed to obtain a precipitate, and the precipitate is dried; placing the precipitate into a tubular high-temperature furnace, introducing argon, programming to be heated to 1450 ℃, reacting at constant temperature for 8 hours to obtain a second product, and naturally cooling the second product in an argon atmosphere; the second product is obtained at 700 DEG CCalcining in air for 3h to obtain a third product; soaking the third product in mixed acid of hydrochloric acid and hydrofluoric acid in the volume ratio of 1:3 for 24h, washing, filtering and drying to obtain SiC-B 0.05 。
Example 3
Firstly, 14.23g of sucrose is dissolved in 100ml of water, 0.22g of nickel nitrate, 12.47g of silica sol and 0.386g of boric acid are added and mixed uniformly, the mixture is reacted for 4 hours at 180 ℃ in a hydrothermal reaction kettle to obtain a first product, the first product is stood, supernatant fluid of the first product is removed to obtain a precipitate, and the precipitate is dried; placing the precipitate into a tubular high-temperature furnace, introducing argon, programming to be heated to 1450 ℃, reacting at constant temperature for 8 hours to obtain a second product, and naturally cooling the second product in an argon atmosphere; calcining the obtained second product in the air at 700 ℃ for 3 hours to obtain a third product; soaking the third product in mixed acid of hydrochloric acid and hydrofluoric acid in the volume ratio of 1:3 for 24h, washing, filtering and drying to obtain SiC-B 0.1 。
Example 4
Firstly, 14.23g of sucrose is dissolved in 100ml of water, 0.22g of nickel nitrate, 12.47g of silica sol and 1.93g of boric acid are added and mixed uniformly, the mixture is reacted for 4 hours at 180 ℃ in a hydrothermal reaction kettle to obtain a first product, the first product is stood, the supernatant of the first product is removed to obtain a precipitate, and the precipitate is dried; placing the precipitate into a tubular high-temperature furnace, introducing argon, programming to be heated to 1450 ℃, reacting at constant temperature for 8 hours to obtain a second product, and naturally cooling the second product in an argon atmosphere; calcining the obtained second product in the air at 700 ℃ for 3 hours to obtain a third product; soaking the third product in mixed acid of hydrochloric acid and hydrofluoric acid in the volume ratio of 1:3 for 24h, washing, filtering and drying to obtain SiC-B 0.5 。
Example 5
(1) Preparation of catalyst 5% Ni/SiC
600mg PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 ·6H 2 O, finally 190mg of SiC support was added to form a suspension. Transferring the suspension to a micro reaction kettle, sealing the micro reaction kettle, flushing gas for three times, and filling 2MPa H 2 The reaction was carried out at 150℃for 2h. The solution in the micro reaction kettle is reduced toAnd (3) carrying out suction filtration and vacuum drying after room temperature to obtain an intermediate product of the catalyst of 5% Ni/SiC, and grinding the intermediate product.
Weighing 50mg of the ground intermediate product, placing the intermediate product into a tube furnace, carrying out vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas, reducing the intermediate product at the temperature of 450 ℃ for 1h, and passivating the intermediate product for 1h under the protection of room temperature argon gas to obtain the catalyst 5% Ni/SiC.
(2) Aniline is prepared by nitrobenzene catalytic hydrogenation, 1mmol of nitrobenzene is added into a 50mL sealed micro reaction kettle, 10mL of solvent ethanol is added, 50mg of reduced catalyst 5% Ni/SiC is added, hydrogen is flushed in the reaction kettle for 3 times, hydrogen is filled again, the reaction pressure is maintained to be 1MPa, the reaction is carried out for 5 hours at 90 ℃, after the reaction is finished, the solid-liquid phase is separated by suction filtration, the solid phase is recovered, namely the catalyst 5% Ni/SiC is recovered, and the liquid phase is subjected to gas chromatography.
Example 6
(1) Preparation of catalyst 5% Ni/SiC-B 0.01
600mg PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 ·6H 2 O, finally add 190mg of SiC-B 0.01 The carrier forms a suspension. Transferring the suspension to a micro reaction kettle, sealing the micro reaction kettle, flushing gas for three times, and filling 2MPa H 2 The reaction was carried out at 150℃for 2h. After the solution in the micro reaction kettle is cooled to room temperature, carrying out suction filtration and vacuum drying to obtain the catalyst 5% Ni/SiC-B 0.01 Is milled.
Weighing 50mg of the ground intermediate product, placing the intermediate product into a tube furnace, performing vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas, reducing the intermediate product at 450 ℃ for 1h, and passivating the intermediate product at room temperature under the protection of argon for 1h to obtain the catalyst 5% Ni/SiC-B 0.01 。
(2) Catalytic hydrogenation of nitrobenzene to prepare aniline
1mmol of nitrobenzene, 10mL of ethanol as solvent and 50mg of 5% of Ni/SiC-B as catalyst after reduction are added into a 50mL sealed micro-reactor 0.01 The reaction kettle is washed with hydrogen for 3 times, and is filled with hydrogen again, and the reaction pressure is maintained to beAfter the reaction is finished, the reaction product is subjected to suction filtration to separate solid phase and liquid phase, and the solid phase is recovered, namely the catalyst 5% Ni/SiC-B 0.01 And (3) performing gas chromatography on the liquid phase reaction liquid.
Example 7
(1) Preparation of catalyst 5% Ni/SiC-B 0.05 600mg PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 6 water, finally 190mg of SiC-B are added 0.05 The carrier forms a suspension. Transferring the suspension to a micro reaction kettle, sealing the micro reaction kettle, flushing gas for three times, and filling 2MPa H 2 The reaction was carried out at 150℃for 2h. And (3) after the solution is cooled to room temperature, carrying out suction filtration, vacuum drying and grinding to complete the first step of catalyst preparation.
Weighing 50mg of the ground intermediate product, placing the intermediate product into a tube furnace, performing vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas, reducing the intermediate product at 450 ℃ for 1h, and passivating the intermediate product at room temperature under the protection of argon for 1h to obtain the catalyst 5% Ni/SiC-B 0.05 。
(2) Catalytic hydrogenation of nitrobenzene to prepare aniline
1mmol of nitrobenzene, 10mL of ethanol as solvent, 50mg of reduced catalyst 5% Ni/SiC-B were added to a 50mL sealed microreactor 0.05 Washing the reaction kettle with hydrogen for 3 times, filling hydrogen again, maintaining the reaction pressure at 1MPa and reacting at 90 ℃ for 5 hours, filtering the reaction product after the reaction is finished to separate solid phase from liquid phase, and recovering the solid phase, namely the catalyst 5% Ni/SiC-B 0.05 The liquid phase is subjected to gas chromatography.
Example 8
(1) Preparation of catalyst 5% Ni/SiC-B 0.1 600mg PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 6 water, finally 190mg of SiC-B are added 0.1 The carrier forms a suspension. Transferring the suspension to a micro reaction kettle, sealing the micro reaction kettle, flushing gas for three times, and filling 2MPa H 2 The reaction was carried out at 150℃for 2h. After the solution in the micro reaction kettle is cooled to room temperature, carrying out suction filtration and vacuum drying to obtain the catalyst 5% Ni/SiC-B 0.1 Intermediate of (2)And (3) grinding the intermediate product.
Weighing 50mg of the ground intermediate product, placing the intermediate product into a tube furnace, performing vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas, reducing the intermediate product at 450 ℃ for 1h, and passivating the intermediate product at room temperature under the protection of argon for 1h to obtain the catalyst 5% Ni/SiC-B 0.1 。
(2) Catalytic hydrogenation of nitrobenzene to prepare aniline
1mmol of nitrobenzene, 10mL of ethanol as solvent, 50mg of reduced catalyst 5% Ni/SiC-B were added to a 50mL sealed microreactor 0.1 Washing the reaction kettle with hydrogen for 3 times, filling hydrogen again, maintaining the reaction pressure at 1MPa and reacting at 90 ℃ for 5 hours, filtering the reaction product to separate solid phase from liquid phase after the reaction, and recovering the solid phase, namely the catalyst 5% Ni/SiC-B 0.1 The liquid phase is subjected to gas chromatography.
Example 9
(1) Preparation of catalyst 5% Ni/SiC-B 0.5
600mg PVP was weighed out and dissolved in 18mL of deionized water, and 1.7mL of Ni (NO) was added at a concentration of 30mg/mL 3 ·6H 2 O, finally add 190mg of SiC-B 0.5 The carrier forms a suspension. Transferring the suspension to a micro reaction kettle, sealing the micro reaction kettle, flushing gas for three times, and filling 2MPa H 2 The reaction was carried out at 150℃for 2h. After the solution in the micro reaction kettle is cooled to room temperature, carrying out suction filtration and vacuum drying to obtain the catalyst 5% Ni/SiC-B 0.5 Is milled.
Weighing 50mg of the ground intermediate product, placing the intermediate product into a tube furnace, carrying out vacuum treatment in the tube furnace, reducing the intermediate product in the atmosphere of hydrogen-nitrogen mixed gas, reducing the intermediate product at the temperature of 450 ℃ for 1h, and passivating the intermediate product for 1h under the protection of argon at room temperature to obtain the catalyst 5% Ni/SiC-B 0.5 。
(2) Catalytic hydrogenation of nitrobenzene to prepare aniline
1mmol of nitrobenzene, 10mL of ethanol as solvent, 50mg of reduced catalyst 5% Ni/SiC-B were added to a 50mL sealed microreactor 0.5 The hydrogen in the reaction kettle is washed for 3 times, and is filled again with hydrogen to maintain the reverse reactionThe reaction is carried out for 5 hours at the temperature of 90 ℃ under the pressure of 1MPa, after the reaction is finished, the reaction product is filtered by suction to separate solid phase and liquid phase, and the solid phase is recovered, namely the catalyst 5 percent Ni/SiC-B 0.5 The liquid phase is subjected to gas chromatography.
In the preparation of 200mg of 5% nickel loaded SiC-Bx in examples 5-9, 600mg of PVP can be replaced with 700mg of Polyacrylamide (PAM), niCl 2 ·6H 2 O as Ni (NO) 3 ·6H 2 Substitutes for O, H 2 O:Ni(NO) 3 ·6H 2 O volume ratio is 18.3:1.7, H 2 O:NiCl 2 ·6H 2 O is 18.7:1.3, H 2 O:Ni(NO) 3 Or NiCl 2 ·6H 2 The total amount of O and water was 20ml.
SiC-B prepared in examples 1 to 4 x See fig. 3 and 4 for experimental results. FIG. 3 left shows SiC-B x XRD pattern of (C) and the right graph represents SiC-B x (111) The graphs of the partial amplification spectra of the crystal planes, labeled a through e in order from bottom to top in the left and right figures, represent SiC-B of x=0, 0.01, 0.05, 0.1, 0.5 x A spectrogram. In the XRD spectrum, 35.7 degrees, 60.0 degrees and 71.8 degrees are three major peaks of SiC, and the angles of the three major peaks are not obviously shifted by B doping, so that the crystal form structure of the SiC is not influenced by the B doping. FIG. 3 right is a diagram of pure SiC (111) and SiC-B x (111) An enlarged view of the crystal face, pure SiC (111) 2θ was 35.7 °. When X is 0.01, 0.05, 0.1, 0.5 SiC-B x The (111) plane 2 theta direction is slightly offset by about 0.01 deg. -0.05 deg..
The position of the peak in fig. 4 represents one element, the area of the peak represents the amount of the element, and the mass fractions of the four elements of carbon (C), silicon (Si), boron (B) and oxygen (O) and the position of the peak representing the element are shown in the upper left corner of fig. 4, and it can be seen from fig. 4 that B was successfully doped into the silicon carbide crystal.
The results of the catalytic hydrogenation of nitrobenzene to aniline in examples 5-9 are shown in Table 1
List one
It can be seen from table one that the doping of the boron atom (B) has a remarkable effect on improving the catalytic effect of the nickel-loaded boron-doped silicon carbide, and the doping of B successfully improves the catalytic performance, wherein the activity of the nickel-loaded boron-doped silicon carbide increases, the catalytic efficiency increases, and the selectivity of directional hydrogenation increases with the increase of the doping amount of the boron atom. Sp of boron atom 2 The hybridization mode changes the charge density distribution of the catalyst, and simultaneously provides an empty orbit to receive electrons, and the p orbit in the occupied state can transfer electrons to the surface of silicon carbide to adsorb nitrobenzene. The conversion and selectivity of nickel-loaded boron-doped silicon carbide catalysts loaded with different amounts of nickel are shown in table two:
as can be seen from table two, the higher the content of nickel supported, the higher the conversion of the nickel-supported boron doped silicon carbide catalyst, with the same doping amount of boron; under the condition that the doping amount of boron is the same, the content of the supported nickel is different, and the selectivity of the nickel-supported boron doped silicon carbide catalyst is not obviously changed and is maintained at a higher level.
The nickel-loaded boron-doped silicon carbide prepared in examples 5-9 has nickel loading of 5%, better catalytic activity and directional hydrogenation selectivity, and particularly the nickel-loaded boron-doped silicon carbide prepared in example 9 has excellent catalytic activity, the nitrobenzene conversion rate reaches 100%, and the selectivity reaches 100%. Therefore, the nickel-loaded boron-doped silicon carbide with higher catalytic activity can be generated under the condition of loading a small amount of nickel, and meanwhile, the cost of the nickel-loaded boron-doped silicon carbide is reduced due to the low price and small loading amount of nickel, so that the nickel-loaded boron-doped silicon carbide can be widely applied to the preparation of aniline.
In the reaction process of preparing aniline by catalytic hydrogenation of nitrobenzene catalyzed by nickel-loaded boron-doped silicon carbide, aniline and water are produced in the reaction process of hydrogen and nitrobenzene, other substances are not produced, pollution produced in the aniline production process in the prior art is reduced, and the wide application of the preparation method of the nickel-loaded boron-doped silicon carbide catalytic aniline is facilitated.
Example 10 includes example 10A, example 10B, example 10C, example 10D, and example 10E, wherein example 10A is the same as example 9, example 10B, example 10C, example 10D, example 10E, and example 10A are substantially the same, except that the catalyst is 5% Ni/SiC-B 0.5 The time for nitrobenzene hydrogenation reaction is reduced.
The results of the catalytic hydrogenation of nitrobenzene to aniline in examples 10A-10E are shown in Table III
Watch III
| Catalyst | Time (h) | Conversion (%) | Selectivity (%) | |
| Example 10A | 5％Ni/SiC-B 0.5 | 5 | 99.9 | 99.9 |
| Example 10B | 5％Ni/SiC-B 0.5 | 4 | 78.1 | 96.2 |
| Example 10C | 5％Ni/SiC-B 0.5 | 3 | 60.1 | 97.1 |
| Example 10D | 5％Ni/SiC-B 0.5 | 2 | 56.2 | 99.9 |
| Example 10E | 5％Ni/SiC-B 0.5 | 1 | 23.2 | 99.9 |
The third table shows that under the same carrier condition, transition metal is used as the active component of the reaction, the difference of the reaction performance of preparing aniline by nitrobenzene catalytic hydrogenation has a close relationship with the time, and the conversion rate of nitrobenzene is reduced along with the reduction of the reaction duration of nickel-loaded boron doped silicon carbide and nitrobenzene hydrogenation.
Claims (9)
1. A nickel-loaded boron-doped silicon carbide, characterized in that the nickel-loaded boron-doped silicon carbide is in the form of SiC-B x The nickel is supported by a carrier, the nickel is supported by 1 to 30 percent of the boron doped silicon carbide,the SiC-B x X in the formula (I) is any value between 0.01 and 0.5;
the SiC-B x The preparation method comprises the following steps:
s01: dissolving a carbon source in a first solvent, adding a silicon source, metal salt and boride to obtain a mixed solution, reacting the mixed solution at 150-200 ℃ for 2-7-h to obtain a first product, standing, and removing supernatant of the first product to obtain a precipitate;
s02: placing the precipitate in an inert atmosphere, and performing carbothermic reduction reaction at 1000-1500 ℃ for 3-30h to obtain a second product;
s03: placing the second product in air, and calcining at 500-900 ℃ for 2-8h to obtain a third product;
s04: soaking the third product in a mixture of hydrochloric acid and hydrofluoric acid in a volume ratio of 1:1-5 for 12-48h to obtain the SiC-B x ；
Wherein the molar ratio of the carbon source to the silicon source in the mixed solution of S01 is 0.1:1-20, and the molar ratio of the silicon source to the metal salt is 0.5:1-5, wherein the molar ratio of the silicon source to the boride is 0.01:0.5-7, and the metal salt is selected from one or more of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride.
2. The nickel-loaded boron-doped silicon carbide of claim 1, wherein the carbon source is selected from one or more of sucrose, biomass, polystyrene sulfonic acid resin, and graphite, the silicon source is selected from one or more of silica sol, water glass, and polycarbosilane, and the boride is selected from one or more of boric acid, borax, sodium borohydride, 3-aminophenylboric acid, trialkylborane, boron trifluoride-methanol, ammonia borane.
3. A method of preparing nickel-loaded boron-doped silicon carbide according to claim 1 or 2, comprising the steps of:
s1: adding the SiC-B into a first reaction vessel x Mixing with dispersant, water and nickel salt to form mixed solution, and charging 2 MPaH 2 At 100-20Reacting at 0 ℃ for 1-3h to obtain an intermediate product;
s2: carrying out reduction reaction on the intermediate product in a tube furnace at 450-600 ℃ by using a hydrogen-nitrogen mixed gas for 1-3h to obtain the nickel-loaded boron-doped silicon carbide;
wherein the SiC-B x X in the formula (I) is any value between 0.01 and 0.5;
the dispersing agent is polyvinylpyrrolidone;
the nickel salt is selected from one or more of nickel nitrate hexahydrate, nickel sulfate, nickel acetate tetrahydrate and nickel chloride hexahydrate.
4. The method for preparing nickel-loaded boron-doped silicon carbide according to claim 3, comprising post-treatment after step S2: the nickel-loaded boron-doped silicon carbide was passivated at room temperature under inert gas blanket gas 1h.
5. The method of preparing nickel-supported boron-doped silicon carbide according to claim 3, wherein in step S1, the reaction temperature is 150 ℃ and the reaction time period is 2h.
6. The method for preparing nickel-supported boron-doped silicon carbide according to claim 3,
the method comprises the following intermediate processing steps of step S1 and step S2: cooling, filtering, vacuum drying and grinding the intermediate product;
the reduction reaction temperature of the intermediate product in the step S2 is 450 ℃, and the reduction reaction time is 1h.
7. The preparation method of the aniline is characterized by comprising the following steps of:
a, preparing the nickel-loaded boron-doped silicon carbide according to claim 1 or 2;
adding nitrobenzene, a second solvent and the nickel-loaded boron doped silicon carbide into a second reaction container, introducing a reducing agent hydrogen, heating, and performing a reduction reaction to obtain aniline;
wherein the volume ratio of the nitrobenzene to the second solvent is 0.1-1:5-20, and the molar ratio of the nitrobenzene to the nickel-loaded boron-doped silicon carbide is 1-10:0.04-0.06;
after the hydrogen is filled, the pressure in the second reaction container is 0.5-6MPa, the reduction reaction temperature is 20-100 ℃, and the reduction reaction time is 2-8h.
8. The method for producing aniline according to claim 7, wherein the reduction reaction temperature is 90℃and the reduction reaction time is 5 hours.
9. The method for producing aniline according to claim 7, wherein the second solvent is one or more of methanol, ethanol, acetonitrile, and N, N-dimethylformamide.
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