CN111470985A - Synthetic method of aminoanisole compound - Google Patents
Synthetic method of aminoanisole compound Download PDFInfo
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- CN111470985A CN111470985A CN201910063322.3A CN201910063322A CN111470985A CN 111470985 A CN111470985 A CN 111470985A CN 201910063322 A CN201910063322 A CN 201910063322A CN 111470985 A CN111470985 A CN 111470985A
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- Prior art keywords
- alkali metal
- nickel
- composite material
- carbon
- catalyst
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- -1 aminoanisole compound Chemical class 0.000 title claims abstract description 37
- 238000010189 synthetic method Methods 0.000 title claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 137
- 239000002114 nanocomposite Substances 0.000 claims abstract description 96
- 239000000463 material Substances 0.000 claims abstract description 93
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 72
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 67
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 51
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 238000006722 reduction reaction Methods 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- POIOOCHMXHKUHV-UHFFFAOYSA-N [nitro-[nitro(phenyl)methoxy]methyl]benzene Chemical class C=1C=CC=CC=1C([N+](=O)[O-])OC([N+]([O-])=O)C1=CC=CC=C1 POIOOCHMXHKUHV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract 5
- 239000011148 porous material Substances 0.000 claims description 33
- 238000009826 distribution Methods 0.000 claims description 25
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 239000013335 mesoporous material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- WGYFINWERLNPHR-UHFFFAOYSA-N 3-nitroanisole Chemical compound COC1=CC=CC([N+]([O-])=O)=C1 WGYFINWERLNPHR-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- CFBYEGUGFPZCNF-UHFFFAOYSA-N 2-nitroanisole Chemical compound COC1=CC=CC=C1[N+]([O-])=O CFBYEGUGFPZCNF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- RTZOGYCMIMOVHU-UHFFFAOYSA-N 4-methoxy-2-methyl-1-nitrobenzene Chemical compound COC1=CC=C([N+]([O-])=O)C(C)=C1 RTZOGYCMIMOVHU-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052730 francium Inorganic materials 0.000 claims description 3
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 88
- 238000010438 heat treatment Methods 0.000 description 39
- 239000010410 layer Substances 0.000 description 32
- 238000002360 preparation method Methods 0.000 description 29
- 239000000047 product Substances 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 239000002131 composite material Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 229910052573 porcelain Inorganic materials 0.000 description 14
- 239000000376 reactant Substances 0.000 description 14
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000012456 homogeneous solution Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 10
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 150000002815 nickel Chemical class 0.000 description 7
- 229940078494 nickel acetate Drugs 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- PRLDILURXJMICQ-UHFFFAOYSA-N 4-[(4-aminophenyl)methoxymethyl]aniline Chemical compound C1=CC(N)=CC=C1COCC1=CC=C(N)C=C1 PRLDILURXJMICQ-UHFFFAOYSA-N 0.000 description 3
- GMPKIPWJBDOURN-UHFFFAOYSA-N Methoxyamine Chemical compound CON GMPKIPWJBDOURN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- NOXMVNQTYSBCJC-UHFFFAOYSA-N CC(C=C(COCC(C=C1)=CC(C)=C1N)C=C1)=C1N Chemical compound CC(C=C(COCC(C=C1)=CC(C)=C1N)C=C1)=C1N NOXMVNQTYSBCJC-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- QDWGWHMTZIAPOE-UHFFFAOYSA-N [N+](=O)([O-])C1=CC=C(C=C1C)COCC=1C=C(C(=CC=1)[N+](=O)[O-])C Chemical compound [N+](=O)([O-])C1=CC=C(C=C1C)COCC=1C=C(C(=CC=1)[N+](=O)[O-])C QDWGWHMTZIAPOE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 150000005323 carbonate salts Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- GOJFAKBEASOYNM-UHFFFAOYSA-N 2-(2-aminophenoxy)aniline Chemical class NC1=CC=CC=C1OC1=CC=CC=C1N GOJFAKBEASOYNM-UHFFFAOYSA-N 0.000 description 1
- PHQAPVZFVVIONO-UHFFFAOYSA-N COC1=CC=CC=C1C(=O)C=CN Chemical compound COC1=CC=CC=C1C(=O)C=CN PHQAPVZFVVIONO-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method 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
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention provides a synthetic method of an amino anisole compound, which comprises the following steps: the carbon-coated nickel nano composite material containing alkali metal is used as a catalyst to catalyze the nitrobenzyl ether compounds to carry out hydrogenation reduction reaction in the hydrogen atmosphere; the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkali metal and oxygen, and the inner core is nickel nano particles. The method adopts the carbon-coated nickel-containing nano composite material containing alkali metal as the catalyst, the carbon material and the nickel nano particles act synergistically to produce a good catalytic effect, the alkali metal of the shell layer further synergistically improves the catalytic performance of the material, and the catalyst is used for hydrogenation reduction synthesis of an amino phenyl ether compound from a nitrobenzyl ether compound, and has excellent activity, selectivity and safety.
Description
Technical Field
The invention relates to the field of catalysis, and particularly relates to a synthesis method of an amino anisole compound.
Background
The amino-phenyl ether compound can be widely applied to dye industry, medicine industry and perfume intermediates. The traditional industrial production method is a chemical reduction method, and the nitro-anisole is usually prepared by reducing nitro-anisole by iron powder or sodium sulfide. The method has simple process, but has the defects of heavy three-waste pollution, high cost, poor quality and the like. Compared with a chemical reduction method, the catalytic hydrogenation reduction method has the advantages of good product quality, high yield, simple process and the like, is concerned, and is an environment-friendly green process.
At present, the catalyst for catalyzing hydrogenation reaction of nitrobenzyl ether mainly takes noble metal catalysts such as platinum (Pt), palladium (Pd) and rhodium (Rh) as the main catalyst. The Pt and Pd noble metal catalysts have the advantages of high catalytic activity, mild reaction conditions and the like, but the noble metal catalysts have high price and cost, and the loss of noble metals has great harm to the environment, so the application of the noble metal catalysts in industrial production is limited. Non-noble metal catalysts, such as nickel, also have a series of problems in practical production application, such as easy agglomeration in the preparation process, easy elution in the catalytic hydrogenation process, poor stability, great potential safety hazard, and the like.
From the above, it is known that the development of a hydrogenation reduction catalyst which is stable in air and has excellent catalytic performance for the hydrogenation reduction of nitroanisole to synthesize the aminoacrylanisole is a problem to be solved in the art.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention provides a method for synthesizing an amino benzyl ether compound, which adopts a carbon-coated nickel-containing nano composite material containing alkali metal as a catalyst, wherein the nano composite material is in a core-shell structure formed by coating nickel nano particles with a graphitized carbon layer containing alkali metal and oxygen, a carbon material and the nickel nano particles act synergistically to generate a good catalytic effect, the alkali metal of the shell layer further synergistically improves the catalytic performance of the material, and the carbon-coated nano composite material is used for synthesizing the amino benzyl ether compound by hydrogenation reduction of the nitro benzyl ether compound and has excellent activity, selectivity and safety.
The invention provides a synthetic method of an amino anisole compound, which comprises the following steps:
the carbon-coated nickel nano composite material containing alkali metal is used as a catalyst to catalyze the nitrobenzyl ether compounds to carry out hydrogenation reduction reaction in the hydrogen atmosphere;
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkali metal and oxygen, and the inner core is nickel nano particles.
According to an embodiment of the present invention, the nitrobenzyl ethers further comprise a substituent on the benzene ring, wherein the substituent is selected from C1-20One or more of alkyl, cycloalkyl and aryl.
According to an embodiment of the present invention, wherein the nitroanisole compound is selected from one or more of o-nitroanisole, p-nitroanisole, m-nitroanisole and 3-methyl-4-nitroanisole.
According to an embodiment of the present invention, the catalyst accounts for 1% to 50%, preferably 5% to 30% of the weight of the nitrobenzyl ethers.
According to one embodiment of the present invention, wherein the temperature of the hydrogenation reduction reaction is 50 ℃ to 120 ℃.
According to one embodiment of the present invention, wherein the pressure of the hydrogen gas is 0.5 to 2 MPa.
According to an embodiment of the present invention, the nitrobenzyl ethers and the catalyst are mixed in a solvent, and then subjected to a hydrogenation reduction reaction, wherein the solvent is one or more selected from alcohols, ethers, alkanes and water.
According to one embodiment of the present invention, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak. Optionally, the nanocomposite is a mesoporous material having two or more mesopore distribution peaks. Optionally, the nanocomposite material has a mesopore distribution peak in a pore size range of 2nm to 7nm and a pore size range of 8nm to 20nm, respectively. Optionally, wherein the mesopore material has a proportion of mesopore volume of more than 50%, preferably more than 80%, of the total pore volume.
According to an embodiment of the present invention, wherein the alkali metal content is 0.1 at% to 3 at%, preferably 0.2 at% to 3 at%, in atomic percent; the carbon content is 80 at% to 95 at%, preferably 84 at% to 92 at%; the nickel content is 0.1 at% to 10 at%, preferably 1 at% to 8 at%; the oxygen content is 1 at% to 15 at%, preferably 5 at% to 12 at%.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
According to one embodiment of the present invention, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
According to an embodiment of the present invention, the particle size of the core-shell structure is 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
According to an embodiment of the invention, wherein the alkali metal is selected from one or more of lithium (L i), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr).
The invention has the beneficial effects that:
the invention provides a synthesis method of an amino anisole compound, which uses a carbon-coated nickel nano composite material containing alkali metal as a catalyst to carry out hydrogenation reduction on a nitroanisole compound, and because the catalyst material contains a graphitized carbon layer/metal core-shell structure, no pore channel or defect which can enable reactants to approach the center of nickel exists, the nickel material of an inner core is very stable, does not self-ignite, is resistant to acid corrosion and low in danger, and is suitable for storage and transportation, thereby ensuring the use safety of the composite material. The catalyst material disclosed by the invention is very stable, free of spontaneous combustion, resistant to oxidation and acid corrosion, low in risk and suitable for storage and transportation, so that the safety of the synthetic process of the amino anisole compound is ensured.
The carbon-coated nickel nanocomposite containing alkali metal shows good repeatability, high activity and high selectivity in the reaction of catalytically reducing nitrobenzyl ether compounds into amino-phenyl-ether compounds, and the nickel coated in the graphitized carbon layer has a penetration effect, so that the electronic state of the alkali metal loaded on the surface of the graphitized carbon layer is influenced, and a synergistic effect is exerted, so that the nanocomposite has good catalytic performance; in addition, the nano composite material has stronger magnetism, and can be conveniently used for separating a catalyst by utilizing the magnetism or used for processes such as a magnetic stabilization bed and the like.
Drawings
FIG. 1 is a TEM image of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIG. 2 is an XRD pattern of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIGS. 3a and 3b show N of the alkali metal-containing carbon-nickel-coated nanocomposite prepared in preparation example 1, respectively2Adsorption-desorption isotherms and BJH pore size distribution curves;
FIG. 4 is a TEM image of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
FIG. 5 is an XRD pattern of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
FIGS. 6a and 6b respectively show N of the alkali metal-containing carbon-nickel-coated nanocomposite prepared in preparation example 22Adsorption-desorption isotherm and BJH pore size distribution curveA wire;
FIG. 7 is a TEM image of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 3;
FIG. 8 is an XRD pattern of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 3;
fig. 9 shows the BJH pore size distribution curve of the alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 3.
Detailed Description
The present invention is described in further detail below by way of specific embodiments in conjunction with the attached drawings, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and do not limit the invention in any way.
In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the examples but also the endpoints of each numerical range in the specification, and ranges in which any combination of the numerical points is disclosed or recited should be considered as ranges of the present invention.
Any terms not directly defined herein should be understood to have meanings associated with them as commonly understood in the art of the present invention. The following terms as used throughout this specification should be understood to have the following meanings unless otherwise indicated.
Term(s) for
The term "alkyl" is defined herein as a straight or branched chain alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and the like.
The term "cycloalkyl" is defined herein as an alkyl group connected by single bonds and constituting a ring, such as cyclohexyl.
The term "aryl" is defined herein as a functional group or substituent derived from a simple aromatic ring, such as benzyl.
The term "nitrobenzyl ether compounds" refers to compounds wherein at least one hydrogen atom on the phenyl ring is substituted with a nitro group and the other hydrogen atoms are substituted with a methoxy group, and includes nitrobenzyl ethers wherein the phenyl ring has no substituents other than methoxy and nitro groups, and nitrobenzyl ethers wherein at least one of the other hydrogen atoms on the phenyl ring is substituted with a group other than methoxy and nitro groups.
The term "graphitized carbon layer" means a carbon structure in which a layered structure is clearly observed under a high-resolution transmission electron microscope, not an amorphous structure, and the interlayer distance is 0.34 nm. The nano composite material formed after the graphitized carbon layer is coated with the nickel nano particles is spherical or quasi-spherical.
The term "mesoporous" is defined as a pore having a pore diameter in the range of 2 to 50 nm. Pores with a pore size of less than 2nm are defined as micropores and pores with a pore size of more than 50nm are defined as macropores.
The term "mesoporous material" is defined as a porous material comprising a mesoporous channel structure.
The terms "alkali metal" and "oxygen" in the "graphitized carbon layer containing alkali metal and oxygen" refer to alkali metal elements and oxygen elements, wherein the "alkali metal content" of the nanocomposite refers to the content of the alkali metal elements, and the "oxygen content" refers to the content of the oxygen elements, and specifically means that the alkali metal elements and the oxygen elements exist in various forms in the graphitized carbon layer formed in the preparation process of the carbon-coated nanocomposite, the "alkali metal content" is the total content of all forms of alkali metal elements, and the "oxygen content" is the total content of all forms of oxygen elements. The "alkali metal content" and "oxygen content" were determined by XPS method.
The term "mesopore distribution peak" refers to a mesopore distribution peak on a pore distribution curve calculated from a desorption curve according to the Barrett-Joyner-Halenda (BJH) method.
The term "TOF" is defined herein as the amount of a reactant converted per unit time by a single active metal atom, and TOF measures the rate at which a catalyst catalyzes a reaction and indicates the intrinsic activity of the catalyst.
Reagents, instruments and tests
Unless otherwise specified, the reagents used in the present invention are all in analytical grade and are commercially available, for example from Sigma Aldrich (Sigma-Aldrich).
The XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are Cu target, K α ray (the wavelength lambda is 0.154nm), tube voltage is 40kV, tube current is 200mA, and scanning speed is 10 degrees (2 theta)/min.
The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100(HRTEM) (Nippon electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200 kV.
The X-ray photoelectron spectrum analyzer (XPS) is an ESCA L ab220i-X L type electron spectrum analyzer which is produced by VG scientific company and is provided with Avantage V5.926 software, the X-ray photoelectron spectrum analyzer has the analysis and test conditions that an excitation source is monochromized A1K α X-rays, the power is 330W, and the basic vacuum is 3 × 10 during analysis and test-9mbar. In addition. The electron binding energy was corrected for the C1s peak (284.6eV), and the late peak processing software was XPSPEAK.
BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
In the invention, after the average particle size of the carbon-coated nickel nano particles is subjected to peak splitting by an XRD (X-ray diffraction) pattern, the average particle size is determined by a Sherle formula: d ═ k γ/(Bcos θ) was calculated. Wherein k is Scherrer constant, k is 0.89; b is half-height width; theta is the diffraction angle, unit radian; gamma is the x-ray wavelength, 0.154054 nm.
The invention provides a synthetic method of an amino anisole compound, which comprises the following steps: the carbon-coated nickel nano composite material containing alkali metal is used as a catalyst to catalyze the nitrobenzyl ether compounds to carry out hydrogenation reduction reaction in the hydrogen atmosphere; the chemical reaction equation is exemplified as follows,
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkali metal and oxygen, and the inner core is nickel nano particles.
In some embodiments, the nitrobenzophenone compound further contains a substituent on the benzene ring, and the substituent R is selected from C1-20The above substitution may be mono-substitution or poly-substitution, such as p-nitroanisole, m-nitroanisole or 3-methyl-4-nitroanisole.
In some embodiments, the catalyst accounts for 1% to 50%, preferably 5% to 30% of the mass of the nitrobenzyl ethers.
In some embodiments, the temperature in which the hydrogenation reduction reaction is carried out is generally in the range of 50 ℃ to 120 ℃.
In some embodiments, the pressure of the hydrogen gas therein is generally in the range of 0.5MPa to 2 MPa.
In some embodiments, the nitrobenzyl ethers are mixed with the catalyst in a solvent selected from one or more of alcohols, ethers, alkanes and water, such as ethanol, tetrahydrofuran, cyclohexane, and the like, followed by a hydrogenation reduction reaction.
According to one embodiment of the present invention, the nanocomposite of the present invention is a composite material composed of a "graphitized carbon layer containing an alkali metal and oxygen", a "nickel nanoparticle that is tightly coated with (not in contact with) the graphitized carbon layer", and a "nickel nanoparticle that can be in contact with and confined to the outside". The carbon material has catalytic activity, and the nickel coated in the graphitized carbon layer has penetration effect, so that the electronic state of the alkali metal loaded on the surface of the graphitized carbon layer is influenced, and the synergistic effect is exerted, so that the nano composite material has better catalytic performance.
In some embodiments, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak. That is, the nano composite material has at least one mesoporous distribution peak on a pore distribution curve obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method. As known to those skilled in the art, mesoporous materials generally have large specific surface areas and relatively regular channel structures, so that the mesoporous materials can play better roles in separation, adsorption and catalytic reactions of macromolecules and can be used as microreactors for limited-domain catalysis. The nano composite material has rich mesoporous structure, so that the nano composite material has higher mass transfer efficiency and more excellent catalytic performance.
In some embodiments, the batch-produced composite has two distribution peaks in the mesoporous range; if a plurality of batches of the composite material are mixed, more distribution peaks can be obtained in the mesoporous range. When the nano composite material has the multilevel mesoporous structure with different aperture ranges, the nano composite material can show more unique performance, and the applicable application range of the multilevel mesoporous structure is wider.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous structure has one mesoporous distribution peak in mesoporous ranges of 2nm to 5nm and 6nm to 15nm, respectively.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous structure has one mesoporous distribution peak in mesoporous ranges of 2nm to 7nm and 8nm to 20nm, respectively.
In some embodiments, the proportion of mesopore volume in the composite material to the total pore volume is greater than 50%, preferably greater than 80%, according to the nanocomposite material of the present invention. In some embodiments, the proportion of mesopore volume to the total pore volume is greater than 90%, and even 100%.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous volume thereof may be 0.05cm3/g～1.25cm3Per g, also may be 0.10cm3/g～0.30cm3/g。
The nanocomposites according to the invention, in some embodiments, have specific surface areas generally greater than 140m2/g, may be greater than 200m2/g。
The nanocomposites according to the invention, which are not pyrophoric in air, can be stored in air.
According to the nanocomposite of the invention, in some embodiments, the carbon layer of the composite is doped with an oxygen element and not with a nitrogen element.
According to the nanocomposite material of the invention, in some embodiments, the carbon layer of the composite material is doped with only oxygen, and is not doped with other elements than hydrogen and oxygen.
In some embodiments, wherein the alkali metal content is from 0.1 at% to 3 at%, preferably from 0.2 at% to 3 at%, as measured by XPS; the carbon content is 80 at% to 95 at%, preferably 84 at% to 92 at%; the nickel content is 0.1 at% to 10 at%, preferably 1 at% to 8 at%; the oxygen content is 1 at% to 15 at%, preferably 5 at% to 12 at%.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
According to the nanocomposite material of the present invention, the graphitized carbon layer is doped with oxygen. The oxygen content can be adjusted by additionally introducing an oxygen-containing compound, such as a polyol, during the manufacturing process. The catalytic performance of the graphitized carbon layer can be adjusted by adjusting the oxygen content in the nano composite material, so that the graphitized carbon layer is suitable for catalyzing different reactions. In some embodiments, the oxygen content in the nanocomposite is less than 15.0%, preferably 5% to 12%, by mass.
According to one embodiment of the present invention, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
According to an embodiment of the present invention, the particle size of the core-shell structure is 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
According to an embodiment of the invention, wherein the alkali metal is selected from one or more of lithium (L i), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr).
The invention also provides a preparation method of the nano composite material, which comprises the following steps:
putting nickel salt and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution;
removing the solvent in the homogeneous solution to obtain a precursor;
carrying out primary pyrolysis on the precursor in an inert atmosphere or a reducing atmosphere;
contacting the product after the primary pyrolysis with the solution containing alkali metal, and then drying;
and (3) placing the dried product in an inert atmosphere for secondary pyrolysis to obtain the carbon-coated nickel-containing nano composite material containing alkali metal.
Specifically, the precursor is a water-soluble mixture, which means that nickel salt and polybasic organic carboxylic acid are dissolved into a homogeneous solution in a solvent such as water and/or ethanol, and then the solvent is directly removed to obtain the nickel-containing precursor. The solvent may be removed by evaporation, and the temperature and process of evaporation of the solvent may be by any available art, for example, spray drying at 80 ℃ to 120 ℃ or drying in an oven.
In some embodiments, wherein the nickel salt is selected from one or more of an organic acid salt, a carbonate salt, and a basic carbonate salt of nickel, the organic acid salt of nickel is preferably an organic carboxylate salt of nickel that is free of heteroatoms, more preferably an acetate salt of the nickel that is free of heteroatoms, wherein the heteroatoms refer to metal atoms other than the nickel.
In some embodiments, wherein the poly-organic carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid (EDTA), and dipicolinic acid. Wherein the mass ratio of the nickel salt to the polybasic organic carboxylic acid is 1: 0.1-10, preferably 1: 0.5-5, and more preferably 1: 0.8-3.
In some embodiments, the method further comprises mixing the nickel salt, the polybasic organic carboxylic acid and other organic compounds except the nickel salt and the polybasic organic carboxylic acid in a solvent such as water, ethanol and the like to form a homogeneous solution, and then removing the solvent to obtain the water-soluble mixture containing nickel. Such other organic compounds include, but are not limited to, organic polyols. In some embodiments, the mass ratio of the nickel salt, the polybasic organic carboxylic acid and the other organic compound is 1: 0.5-10: 0-10, preferably 1: 1-3: 0-3.
In some embodiments, wherein the primary pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-30 ℃/min, preferably 1-10 ℃/min; the temperature of the constant temperature section is 400-800 ℃, and preferably 500-800 ℃; the constant temperature time is 20min to 600min, preferably 30min to 300 min; the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of an inert gas and hydrogen, for example, a small amount of hydrogen is doped in the inert atmosphere.
In some embodiments, the alkali metal-containing solution is an alkali metal salt and/or base-containing solution, such as a potassium bicarbonate solution, a potassium hydroxide solution, a sodium carbonate solution, and the like. The mass ratio of the alkali metal salt and/or alkali to the product after primary pyrolysis is 1: 2-100, preferably 1: 2-50, and more preferably 1: 2-20. When the amount of alkali metal-containing salt or alkali is excessive, the core-shell structure of carbon-coated nickel is easily destroyed in the secondary pyrolysis process, and the nickel in the core is exposed to air and spontaneously ignited.
In some embodiments, wherein the secondary pyrolysis comprises: under the inert atmosphere, heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-10 ℃/min, preferably 2.5-10 ℃/min; the temperature of the constant temperature section is 80-500 ℃, and preferably 100-400 ℃; the constant temperature time is 20 min-600 min; the inert atmosphere is nitrogen or argon.
The carbon-coated nickel nanocomposite is prepared by the method, a method of pyrolyzing a metal-organic framework compound (MOF) serving as a precursor is not adopted, the method needs to prepare a crystalline solid Material (MOF) with a periodic structure in a solvent at high temperature and high pressure, the condition for preparing MOFs is strict, the needed ligand is expensive, and the mass production is difficult; in addition, the composite material prepared by the method has imprecise cladding on the metal particles, and is remarkably different from the nano composite material in structure. The alkali metal contained in the shell layer of the core-shell structure in the nano composite material can generate a synergistic effect with the core nickel nano particles, so that the catalytic performance is more excellent. The method for preparing the nano composite material is convenient for adjusting the oxygen content in the graphitized carbon layer in the preparation process, thereby conveniently adjusting the electronic characteristics of the nano composite material so as to be suitable for catalyzing different reactions.
The present invention is described in further detail below by way of specific embodiments in conjunction with the attached drawings, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and do not limit the invention in any way.
Preparation example 1
(1) Weighing 10g of nickel acetate and 10g of citric acid, adding the nickel acetate and the citric acid into a beaker containing 30m L of deionized water, stirring the mixture at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating the homogeneous solution to dryness to obtain a solid precursor.
(2) And (2) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) And (3) weighing 2g of the material obtained in the step (2), adding 4ml of aqueous solution containing 0.1538 potassium bicarbonate, stirring for 24 hours at room temperature, and drying to obtain the carbon-coated transition nickel material containing potassium.
(4) And (3) placing the material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100m L/min, heating to 400 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite containing potassium.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content was 84.9 at%, the nickel content was 6.34 at%, the oxygen content was 8.36 at%, and the potassium content was 0.4 at%.
The atomic percentages of the respective elements in the material measured by XPS are shown in table 1, and the TEM image of the material is shown in fig. 1, and it can be seen that the material contains a carbon-coated nickel structured nanocomposite. The XRD pattern of this material is shown in fig. 2, and it can be seen that the diffraction pattern of this material includes diffraction peaks (2 θ angle 25.9 °) of graphite carbon and diffraction peaks (2 θ angles 44.5 °, 51.7 ° and 76.4 °) of face-centered cubic (fcc) Ni. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 5.2nm by the scherrer equation.
The BET test shows that the specific surface area of the composite material is 151m2Per g, pore volume 0.365cm3Per g, wherein>The mesoporous volume of 2nm is 0.365cm3(ii) in terms of/g, representing 100% of the total pore volume. FIG. 3a shows N of the composite material2An adsorption-desorption isotherm is shown in fig. 3b, which is a BJH pore size distribution curve of the composite material, and it can be seen that the composite material has two mesopore distribution peaks at 3.77nm and 12.19 nm.
Preparation example 2
(1) 10g of nickel acetate and 20g of citric acid were weighed into a beaker containing 50m L of deionized water, stirred at 80 ℃ to obtain a homogeneous solution, and continuously heated and evaporated to dryness to obtain a solid precursor.
(2) And (2) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 150m L/min, heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) Weighing 2g of the material obtained in the step (2), adding 15M of L1M KOH aqueous solution, stirring at room temperature for 24h, filtering, and finally drying at 120 ℃ to obtain the potassium-containing carbon-coated nickel material.
(4) And (3) placing the dried material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 50m L/min, heating to 200 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite containing potassium.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: 91.55 at% of carbon, 1.86 at% of nickel, 6.41 at% of oxygen and 0.18 at% of potassium.
The TEM image of the nanocomposite is shown in fig. 4, and it can be seen that a graphitized carbon layer is wrapped on the outer layer of the nickel nanoparticle to form a complete core-shell structure. The X-ray diffraction pattern of the nanocomposite material was as shown in fig. 5, in which diffraction peaks corresponding to carbon (2 θ angle of 25.9 °) and fcc Ni (2 θ angles of 44.5 °, 51.7 ° and 76.4 °) were present, and the average particle diameter of the carbon-coated nickel nanoparticles was 31.3nm as calculated from the scherrer equation.
The BET test shows that the specific surface area of the material is 168m2Per g, pore volume 0.342cm3Per g, wherein>Pore volume of 0.32cm at 2nm3(ii) in terms of/g, 93.6% of the total pore volume. FIGS. 6a and 6b show N of the nanocomposite, respectively2According to the adsorption-desorption isotherm and the BJH pore size distribution curve, two mesoporous distribution peaks exist at 3.38nm and 8.94nm of the composite material.
Preparation example 3
(1) Weighing 10g of nickel acetate and 10g of terephthalic acid, adding the nickel acetate and the terephthalic acid into 30m L deionized water, stirring at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a precursor.
(2) And (2) placing the precursor in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen at a flow rate of 100m L/min, heating to 650 ℃ at a speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the material containing the carbon-coated nickel.
(3) 2g of the material obtained in step (2) were weighed, 4m of L aqueous solution containing 0.2765g of sodium carbonate was added, and the mixture was immersed at room temperature for 24 hours, and then the product was dried at 120 ℃.
(4) And (3) placing the material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 50m L/min, heating to 200 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nano composite material containing sodium.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content was 82.27 at%, the nickel content was 4.34 at%, the oxygen content was 11.69 at%, and the sodium content was 1.7 at%.
The TEM image of the nanocomposite is shown in fig. 7, which shows that the outer layer of the nickel nanoparticle is coated with a graphitized carbon layer to form a complete core-shell structure. The X-ray diffraction pattern of this nanocomposite material is shown in FIG. 8, and there are diffraction peaks (2. theta. angle of 25.9 ℃) corresponding to carbon and fcc Ni (2. theta. angle of 44.5 °, 51.7 ° and 76.4 °) in the X-ray diffraction pattern of this material. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 27.6nm by the scherrer equation.
The BET test shows that the specific surface area of the material is 164m2Per g, pore volume 0.33cm3Per g, wherein>Pore volume of 0.33cm at 2nm3(ii) in terms of/g, representing 100% of the total pore volume. Fig. 9 shows the BJH pore size distribution curve of the material, and it can be seen that there are two mesopore distribution peaks at 4.01nm and 18.9nm in the material.
Comparative preparation example 1
(1) Weighing 10g of nickel acetate and 10g of citric acid, adding the nickel acetate and the citric acid into a beaker containing 30m L of deionized water, stirring the mixture at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating the homogeneous solution to dryness to obtain a solid precursor.
(2) And (2) placing the solid obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content was 88.26 at%, the nickel content was 5.4 at%, and the oxygen content was 6.36 at%.
Comparative preparation example 2
The same as preparation example 1, except that 1.5g of potassium bicarbonate was added in step (3), and the carbon-coated nickel composite material containing potassium was obtained by impregnation and baking at 400 ℃ and was flammable in air.
Example 1
The composite material obtained in preparation example 1 is used as a catalyst for a reaction of hydrogenation of a nitrobenzyl ether compound to prepare a target product, namely an amino phenyl ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 1.99g of p-nitroanisole and 100m of L ethanol into a reaction kettle, introducing H2After 3 times of replacement, the reaction kettle is charged with H2And (3) controlling the pressure in the reaction kettle to be 2MPa, stirring and heating, heating to the preset reaction temperature of 50 ℃, stopping heating after reacting for 3 hours, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product, namely, p-anisidine to perform chromatographic analysis. The reactant conversion and the target product selectivity were calculated by the following formulas:
conversion-amount of reacted reaction mass/amount of added reaction × 100%
The selectivity is × 100% based on the mass of the target product/mass of the reaction product
After analysis, the conversion rate of the p-nitroanisole is 100 percent, and the selectivity of the p-anisidine is 99.0 percent.
When the reaction proceeded for 300s, a sample was taken and subjected to chromatography to calculate the conversion of the reactant, according to the formula TOF ═ amount of reacted reactant species)/(amount of catalytically active metal speciesAmount 300s) gave a catalyst TOF of 9.66 × 10-3s-1。
Example 2
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.49g of p-nitroanisole and 50m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 0.5MPa, stirring and heating, heating to a preset reaction temperature of 120 deg.C, continuously reacting for 0.5 hr, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle and taking out the product to make chromatographic analysis of amino methyl ether, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain p-nitroanisole conversion rate of 100%, p-aminophenylmethylether selectivity of 99.2% and TOF of 9.42 × 10-3s-1。
Example 3
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.49g of p-nitroanisole and 30m L of cyclohexane into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 80 ℃, the heating is stopped after the reaction is continued for 1 hour, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product is taken out, the chromatographic analysis is carried out on the amino methyl ether, the conversion rate of the reactant, the selectivity of the product and the TOF are respectively calculated by the formula shown in the example 1, the conversion rate of the p-nitroanisole is 100 percent, the selectivity of the p-aminophenylmethylether is 99.5 percent-3s-1。
Example 4
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
0.1g of the nanocomposite, 0.34g of p-nitroanisole and 30m LAdding ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 100 ℃, the heating is stopped after the reaction lasts for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product is taken out, the chromatographic analysis is carried out on the amino methyl ether, the conversion rate of the reactant, the selectivity of the product and the TOF are respectively calculated by the formula shown in the example 1, the conversion rate of the p-nitroanisole is 100 percent, the selectivity of the p-aminophenylmethylether is 99.1 percent-3s-1。
Example 5
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.34g of o-nitroanisole and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 100 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product anthranilic ether is taken out for chromatographic analysis, the conversion rate of the reactant, the product selectivity and TOF are respectively calculated by the formula shown in the example 1, the conversion rate of the o-nitroanisole is 100 percent, the selectivity of the anthranilic ether is 99.6 percent, and the TOF is 9.20 × 10-3s-1。
Example 6
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.34g of m-nitroanisole and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2And (3) controlling the pressure in the reaction kettle to be 1MPa, stirring and heating, heating to the preset reaction temperature of 100 ℃, stopping heating after continuously reacting for 2 hours, reducing the temperature to room temperature, discharging pressure, opening the reaction kettle, and taking out the product of the m-anisidine for chromatographic analysis. The reactant conversion, the product selectivity and the TOF were respectively calculated by the formulas shown in example 1,the conversion rate of the obtained m-nitroanisole is 100 percent, the selectivity of the m-anisidine is 99.3 percent, and the TOF is 9.97 × 10-3s-1。
Example 7
The nano composite material prepared in preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.33g of 3-methyl-4-nitrobenzyl ether and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 100 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product 3-methyl-4-aminobenzyl ether is taken out for chromatographic analysis, the conversion rate of the reactant, the product selectivity and TOF are respectively calculated by the formula shown in example 1, the conversion rate of the 3-methyl-4-nitrobenzyl ether is 100 percent, the selectivity of the 3-methyl-4-aminobenzyl ether is 99.4 percent, and the TOF is 8.24 × 10-3s-1。
Example 8
The nano composite material prepared in preparation example 2 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.2g of nano composite material, 0.69g of p-nitroanisole and 50m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1.5MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 80 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product para-anisidine is taken out for chromatographic analysis, the conversion rate of the reactant, the product selectivity and TOF are respectively calculated by the formula shown in the example 1, the conversion rate of the para-anisidine is 100 percent, the selectivity of the para-anisidine is 99.1 percent, and the TOF is 8.81 × 10-3s-1。
Example 9
The nano composite material prepared in preparation example 3 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.2g of nano composite material, 0.69g of p-nitroanisole and 50m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1.5MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 80 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product para-anisidine is taken out for chromatographic analysis, the conversion rate of the reactant, the product selectivity and TOF are respectively calculated by the formula shown in the example 1, the conversion rate of the para-anisidine is 100 percent, the selectivity of the para-anisidine is 99.2 percent, and the TOF is 9.16 × 10-3s-1。
Comparative example
The nano composite material prepared in comparative preparation example 1 is used as a catalyst for the hydrogenation reduction reaction of the nitrobenzophenone ether compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 1.99g of p-nitroanisole and 100m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 2MPa, stirring and heating, heating to 50 deg.C, continuously making reaction for 3 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product p-anisidine and making chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain p-nitroanisole conversion rate of 100%, p-anisidine selectivity of 98.7% and TOF of 5.26 × 10-3s-1。
It can be seen from the above examples and comparative examples that the nanocomposite of the present invention has a good catalytic effect when used as a catalyst for catalyzing a catalytic hydrogenation reaction of nitrobenzyl ether compounds, and compared with a catalyst containing no alkali metal, the nanocomposite containing carbon coated nickel containing alkali metal not only enables the catalytic reaction to have a high conversion rate and a high product selectivity, but also has a higher catalytic reaction rate and a better catalytic performance.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (12)
1. A synthetic method of an amino anisole compound comprises the following steps:
the carbon-coated nickel nano composite material containing alkali metal is used as a catalyst to catalyze the nitrobenzyl ether compounds to carry out hydrogenation reduction reaction in the hydrogen atmosphere;
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkali metal and oxygen, and the inner core is nickel nano particles.
2. The synthesis method according to claim 1, wherein the phenyl ring of the nitrobenzyl ether compound further comprises a substituent selected from C1-20One or more of alkyl, cycloalkyl and aryl.
3. The synthesis method according to claim 1, wherein the nitroanisole compound is selected from one or more of o-nitroanisole, p-nitroanisole, m-nitroanisole and 3-methyl-4-nitroanisole.
4. The synthesis process according to claim 1, wherein the catalyst accounts for 1-50%, preferably 5-30% of the weight of the nitrobenzethers.
5. The synthesis process of claim 1, wherein the temperature of the hydrogenation reduction reaction is from 50 ℃ to 120 ℃.
6. The synthesis process according to claim 1, wherein the pressure of the hydrogen is between 0.5MPa and 2 MPa.
7. The synthesis method according to claim 1, wherein the nitrobenzyl ethers are mixed with the catalyst in a solvent and then subjected to a hydrogenation reduction reaction, wherein the solvent is selected from one or more of alcohols, ethers, alkanes and water.
8. The synthesis method according to any one of claims 1 to 7, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak.
9. The method of synthesizing as defined in claim 8 wherein the nanocomposite is a mesoporous material having two or more mesopore distribution peaks.
10. The method of synthesis according to claim 8, wherein the mesoporous material has a proportion of mesopore volume of more than 50%, preferably more than 80%, of the total pore volume.
11. The method of claim 1, wherein the alkali metal is present at 0.1 at% to 3 at%, the carbon is present at 80 at% to 95 at%, the nickel is present at 0.1 at% to 10 at%, and the oxygen is present at 1 at% to 15 at%, in terms of atomic percentage.
12. The synthesis method of any one of claims 1-11, wherein the alkali metal is selected from one or more of lithium, sodium, potassium, rubidium, cesium, and francium.
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| CN113735722A (en) * | 2021-09-26 | 2021-12-03 | 武汉炼化工程设计有限责任公司 | Preparation process of N-methyl-p-anisidine |
| CN113893858A (en) * | 2021-08-31 | 2022-01-07 | 浙江工业大学 | Application of catalyst in synthesis of 4,4 '-diaminodiphenyl ether from 4,4' -dinitrodiphenyl ether |
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| CN1439456A (en) * | 2003-04-08 | 2003-09-03 | 天津大学 | Catalyst for producing melaphenylene from m-dinitrobenze by liquid phase hydrogenation and preparation thereof |
| CN105032424A (en) * | 2015-06-05 | 2015-11-11 | 中国科学院化学研究所 | Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst |
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| CN1439456A (en) * | 2003-04-08 | 2003-09-03 | 天津大学 | Catalyst for producing melaphenylene from m-dinitrobenze by liquid phase hydrogenation and preparation thereof |
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| CN113893858A (en) * | 2021-08-31 | 2022-01-07 | 浙江工业大学 | Application of catalyst in synthesis of 4,4 '-diaminodiphenyl ether from 4,4' -dinitrodiphenyl ether |
| CN113893858B (en) * | 2021-08-31 | 2024-03-26 | 浙江工业大学 | Application of catalyst in synthesis of 4,4 '-diaminodiphenyl ether from 4,4' -dinitrodiphenyl ether |
| CN113735722A (en) * | 2021-09-26 | 2021-12-03 | 武汉炼化工程设计有限责任公司 | Preparation process of N-methyl-p-anisidine |
| CN113735722B (en) * | 2021-09-26 | 2023-05-16 | 武汉炼化工程设计有限责任公司 | Preparation process of N-methyl-para-aminoanisole |
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