CN117138798A - Composite material of carbon-coated nickel-palladium alloy nano particles, and preparation method and application thereof - Google Patents
Composite material of carbon-coated nickel-palladium alloy nano particles, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117138798A CN117138798A CN202310602919.7A CN202310602919A CN117138798A CN 117138798 A CN117138798 A CN 117138798A CN 202310602919 A CN202310602919 A CN 202310602919A CN 117138798 A CN117138798 A CN 117138798A
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- Prior art keywords
- composite material
- palladium
- nickel
- sulfur
- carbon
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- Pending
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- 239000002131 composite material Substances 0.000 title claims abstract description 135
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 35
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001252 Pd alloy Inorganic materials 0.000 title claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 60
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 132
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 72
- 229910052717 sulfur Inorganic materials 0.000 claims description 66
- 239000011593 sulfur Substances 0.000 claims description 65
- 229910052763 palladium Inorganic materials 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 42
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 42
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000002923 metal particle Substances 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 35
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 231100000572 poisoning Toxicity 0.000 description 10
- 230000000607 poisoning effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002082 metal nanoparticle Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 6
- 229960002303 citric acid monohydrate Drugs 0.000 description 6
- 238000005695 dehalogenation reaction Methods 0.000 description 6
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 6
- 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 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- -1 hydroxy, carboxyl Chemical group 0.000 description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 4
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
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- 239000003112 inhibitor Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- 239000005711 Benzoic acid Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
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- 230000005540 biological transmission Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 2
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- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ZPWNCSAEXUDWTN-UHFFFAOYSA-N 1-nitro-2-phenylsulfanylbenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1SC1=CC=CC=C1 ZPWNCSAEXUDWTN-UHFFFAOYSA-N 0.000 description 1
- BVHNGWRPAFKGFP-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenyl)sulfonylbenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 BVHNGWRPAFKGFP-UHFFFAOYSA-N 0.000 description 1
- ONJRTQUWKRDCTA-UHFFFAOYSA-N 2h-thiochromene Chemical compound C1=CC=C2C=CCSC2=C1 ONJRTQUWKRDCTA-UHFFFAOYSA-N 0.000 description 1
- AXBVSRMHOPMXBA-UHFFFAOYSA-N 4-nitrothiophenol Chemical compound [O-][N+](=O)C1=CC=C(S)C=C1 AXBVSRMHOPMXBA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 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
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- 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
- C07C209/365—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 by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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Abstract
The invention relates to a composite material of carbon-coated nickel-palladium alloy nano particles, a preparation method and application thereof, wherein the composite material comprises a core-shell structure with a shell layer and a core, the shell layer is a graphitized carbon layer, and the core is the nickel-palladium alloy nano particles. The composite material has intrinsic safety, can avoid the problems of agglomeration, inactivation and loss of metal particles, and has higher catalytic activity than the carbon-coated nickel nanoparticle composite material in hydrogenation reaction.
Description
Technical Field
The invention relates to a composite material of carbon-coated nickel-palladium alloy nano particles, a preparation method and application thereof.
Background
The metal particles have long history and wide application as active components of the catalyst. In the field of catalytic hydrogenation, palladium is generally more catalytically active than nickel, as in hydrodechlorination reactions, palladium is generally recognized as the most catalytically active.
Agglomeration of metal particles is one of the main causes of catalyst deactivation, and the smaller the particle diameter of the metal particles, the higher the catalytic activity, but the larger the surface energy, the more easy the agglomeration deactivation. Even when the particle size is reduced to a certain degree, the potential safety hazard is brought, for example, nano-grade nickel and palladium can be spontaneously burned in the air. Metal poisoning is another major cause of catalyst deactivation, and both the hydrogenation feedstock, such as hydrogen, and the reaction substrate may contain sulfur, which is a common poison for nickel and palladium, which is more readily poisoned by sulfur than nickel.
There are many documents reporting composite materials with graphitized carbon coated nickel nanoparticles core-shell structure, the core-shell structure is generally nickel nanoparticles coated by graphene layers with the thickness of less than 10nm, and the composite materials have both the stability of the carbon nano materials and the high activity of the nickel nano particles when being used for catalytic hydrogenation reaction. CN114425341 a disclosed earlier the sulfur poisoning resistance of graphene-coated nickel nanoparticles, and tight coating of graphitized carbon layers was one of the key factors in its ability to resist sulfur poisoning. However, it is difficult to manufacture a composite material of graphitized carbon coated palladium, and although the prior art discloses a large amount of graphitized carbon coated nickel nanomaterial, the graphitized carbon coated palladium is relatively rare in literature, and a simple and effective graphitized carbon coated palladium manufacturing method is still lacking in the prior art. Therefore, how to use the advantage of high palladium catalytic activity and overcome the weakness of easy coalescence and poisoning deactivation is a technical problem which is not well solved in the prior art.
Methods for improving the reaction selectivity can be broadly divided into two types, one of which is realized by changing the properties of the catalyst during the catalyst manufacturing process; the other is achieved during the reaction by controlling the reaction conditions or adding selective regulators. A large number of references to reaction selectivity are directed to metal or metal oxide catalyzed reactions, and there are rarely references to modulating the selectivity of a carbon coated metal material catalyzed reaction.
Halogenated aromatic amines are important organic intermediates, halogenated nitroaromatics catalytic hydrogenation is the most important synthesis method, and palladium and nickel are metals commonly used for halogenated nitroaromatics catalytic hydrogenation. The most important problem of catalytic hydrogenation of halogenated nitroaromatics is the ease with which dehalogenation reactions occur. The prior art focuses on the atomic economy of the reaction; however, even if only a small amount of dehalogenation reaction occurs, the hydrogen halide produced can still cause catalyst halogen poisoning and metal loss, resulting in a decrease in catalyst performance, and thus improvements are still necessary.
The catalytic hydrogenation of halogenated nitroaromatics is a complex reaction process, and the reaction mechanism is different due to different catalytic systems. One of the main approaches to the prior art solution to the dehalogenation problem is to add dehalogenation inhibitors during the reaction. Dehalogenation inhibitors are generally nitrogen-, sulfur-, phosphorus-containing compounds that block part of the highly active sites by binding these heteroatoms to the metal surface, thereby inhibiting the dehalogenation reaction. The disadvantage is that these heteroatoms have a strong action with the metal surface and can easily form chemisorption bonds or react directly with active centers, so that the type and the amount of the heteroatoms are critical, and incorrect selection can cause serious degradation of the catalyst performance and even loss of the catalytic capability. The prior art generally only adds dechlorination inhibitors at the time of reaction, and these toxic compounds are often present in the reaction product components, which are difficult to completely remove.
Disclosure of Invention
The invention aims at providing a carbon-coated metal palladium catalytic material with higher catalytic hydrogenation activity, more stable performance and stronger sulfur poisoning resistance. It is a second object of the present invention to provide the use of the catalytic material described above for the sulfur-containing production of a hydrogenation feedstock. A third object of the present invention is to provide the use of the catalytic material described above in the hydrogenation of nitro compounds. A fourth object of the present invention is to provide the use of the catalytic material described above in the selective hydrogenation of halogenated nitroaromatic hydrocarbons. The fifth object of the present invention is to overcome the disadvantage of the toxic auxiliary being mixed into the hydrogenation product based on the fourth object.
In order to achieve the above purpose, the present invention provides the following technical solutions.
1. The composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer, and the inner core is nickel-palladium alloy nano particles; in the composite material, the mass ratio of nickel to palladium is 3:1-100:1; based on the mass of the composite material, the total mass fraction of nickel and palladium is 1-80%.
2. A composite material according to the foregoing; wherein the mass ratio of nickel to palladium is 4:1-100:1.
3. A composite material according to any of the preceding; wherein, based on the composite material, the total mass fraction of nickel and palladium is 30-80%, preferably 50-78%.
4. A composite material according to any of the preceding; wherein the composite material is a mesoporous and/or macroporous material, and the volume of the mesopores and macropores accounts for more than 50% of the total pore volume.
5. A composite material according to any of the preceding; wherein, the particle diameter of the nickel-palladium alloy nano particles is 1nm to 50nm, preferably 2nm to 25nm, more preferably 3nm to 15nm.
6. A composite material according to any of the preceding; wherein the graphitized carbon layer has a thickness of 0.5nm to 10nm, preferably 0.5nm to 5nm, more preferably 1nm to 5nm.
7. A composite material according to any of the preceding; in the XRD spectrum of the composite material, 2 theta has only one diffraction peak within the range of 40.1-44.5 degrees.
8. A preparation method of a composite material of carbon-coated nickel-palladium alloy nano particles comprises the following steps:
s1, mixing a nickel source, a palladium source and a multi-element organic carboxylic acid in the presence of a first solvent to obtain a precursor solution, and then removing the first solvent to obtain a precursor;
s2, pyrolyzing the precursor in inert gas.
9. According to the preparation method; wherein the first solvent is water and/or ethanol, preferably water.
10. A method according to any of the foregoing; wherein the nickel source is one or more of nickel acetate, basic nickel carbonate and nickel carbonate.
11. A method according to any of the foregoing; wherein the palladium source is glacial acetic acid solution of palladium acetate.
12. A method according to any of the foregoing; wherein the organic polycarboxylic acid is one or more of citric acid, ascorbic acid, ethylenediamine tetraacetic acid, 2, 5-pyridine dicarboxylic acid, malic acid, tartaric acid, benzoic acid and terephthalic acid.
13. A method according to any of the foregoing; wherein, the mass ratio of the nickel source to the palladium source is 3:1-100:1, preferably 4:1-100:1, more preferably 4:1-9:1 based on metal elements.
14. A method according to any of the foregoing; wherein the molar ratio of the nickel source and the palladium source to the organic polycarboxylic acid is 0.1:1-3:1, preferably 0.3:1-1.5:1, wherein the nickel source and the palladium source are calculated by the total molar amount of metal elements.
15. A method according to any of the foregoing; wherein in S2, the pyrolysis temperature is 550-650 ℃.
16. A method according to any of the foregoing; wherein an acid treatment step after S2 is included.
17. A composite material of carbon-coated nickel-palladium alloy nano particles; wherein the composite material of 1 and a sulfur-containing compound supported thereon.
18. A composite material according to 17; wherein the sulfur-containing compound is thiourea.
19. A composite material according to 17 or 18; wherein the mass fraction of the sulfur element in the elemental analysis is 0.5% -5%.
20. A preparation method of a composite material of carbon-coated nickel-palladium alloy nano particles comprises the following steps: comprising the step of supporting a sulfur-containing compound on the composite material of 1.
21. The preparation method is as described in 20; wherein the sulfur-containing compound is thiourea.
22. The preparation method according to 20 or 21; wherein the sulfur-containing compound is used in an amount of 0.01 to 20 in terms of sulfur element relative to 1mol of palladium element in the composite material of 1.
23.8-16.
24.20-22.
25. The use of any of the foregoing composite materials as a hydrogenation catalyst in the presence of sulfur in a catalytic hydrogenation system.
26. Application according to 25; wherein the hydrogen and/or the hydrogenation substrate contains sulfur.
27. The use of a composite material of any of the foregoing in the catalytic hydrogenation of nitro groups in organic compounds.
28. A method of selectively hydrogenating nitro groups in a halogenated nitroaromatic hydrocarbon comprising: under the condition of liquid phase catalytic hydrogenation, hydrogen and halogenated nitroarene are contacted with a catalyst in the presence of a sulfur-containing compound to carry out liquid phase catalytic hydrogenation reaction; the catalyst is the composite material of any one of 1 to 7 and 23; the sulfur-containing compound is thiocyanate and/or thiourea, and the mass ratio of the sulfur-containing compound to halogenated nitroaromatic hydrocarbon is 1: 100-1: 10000.
29. the method according to 28, wherein the mass ratio of the sulfur-containing compound to the halogenated nitroaromatic hydrocarbon is 1: 100-1: 150.
30. a method of selectively hydrogenating nitro groups in a halogenated nitroaromatic hydrocarbon comprising: under the condition of liquid phase catalytic hydrogenation, hydrogen and halogenated nitroaromatic hydrocarbon are contacted with a catalyst to carry out liquid phase catalytic hydrogenation reaction; the catalyst is the composite material of any one of 17 to 19 and 24.
Compared with the prior art, the invention has the following beneficial technical effects.
The invention utilizes the graphitization promoting capability of the carbon and combines the specific complexation and the reduction capability of the multi-element organic carboxylic acid to realize the coating of the palladium metal into the carbon by a simple method and has tighter coating, thereby obtaining the composite material of the carbon-coated nickel-palladium alloy nano particles. The composite material has the stability of the nano carbon material and the catalysis characteristic of palladium metal nano particles. In particular, the composite material has intrinsic safety, has no problems of agglomeration, inactivation and loss of metal particles in theory, and shows higher catalytic activity than the carbon-coated nickel nanoparticle composite material in hydrogenation reaction.
The invention can also conveniently modulate the catalytic property of the composite material, thereby being applicable to different purposes, in particular to selectively hydrogenating the nitro in the organic compound. Specifically, the high-selectivity hydrogenation of the nitro group in the organic compound can be realized no matter the sulfur-containing compound is added in the reaction process or the sulfur-containing compound is loaded on the surface of the composite material in advance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a spherical aberration-free electron microscope image of the composite material prepared according to preparation example 3.
Fig. 2 is an XRD pattern of the composite material prepared according to preparation example 3.
FIG. 3 is an XPS broad spectrum of a composite material prepared according to preparation example 4.
Detailed Description
The invention is described in detail below in connection with the embodiments, but it should be noted that the scope of the invention is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present invention, anything other than those explicitly stated, but not mentioned, is directly applicable to what is known in the art without any change. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or description of the present invention, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is known or described in this invention and should be interpreted as specifically disclosed and described herein unless the combination is clearly unreasonable by those skilled in the art. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the embodiments but also the end points of each numerical range in the specification, and any combination of these numerical points should be considered as the disclosed or described range of the present invention, unless specifically indicated otherwise.
Technical and scientific terms used in the present invention are defined to have their meanings, and are not defined to have their ordinary meanings in the art.
The term "graphitized carbon layer" means that a lamellar carbon structure, not an amorphous structure, is clearly observed under high resolution transmission electron microscopy, and the interlayer spacing is about 0.34nm.
The term "alloy" refers to a mixture of different metallic elements.
The term "mesoporous" is defined as pores having a pore diameter in the range of 2nm to 50nm. Pores with a pore diameter of less than 2nm are defined as micropores and pores with a pore diameter of greater than 50nm are defined as macropores.
The term "acid treatment" refers to an operation of acid washing the product formed after the pyrolysis step at a temperature near boiling when preparing a composite of carbon-coated nickel-palladium alloy nanoparticles.
The term "inert gas" is defined as a gas that does not contribute appreciably to the catalytic hydrogenation performance of the composite.
The term "soluble" means soluble in a solvent at the time of use.
The symbol "PPMw" represents weight percent.
The term "optional" means that there may be or may not be, such as a and optionally B, meaning "there is a and no B" or "there are a and B at the same time".
The first aspect of the invention provides a composite material of carbon-coated nickel-palladium alloy nano particles, which comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer, and the inner core is nickel-palladium alloy nano particles; in the composite material, the mass ratio of nickel to palladium is 3:1-100:1; based on the mass of the composite material, the total mass fraction of nickel and palladium is 1-80%.
The composite material according to the first aspect, which consists of nickel, palladium, carbon and oxygen. It should be understood that the composite material of the present invention is mainly composed of zero-valent nickel, palladium and carbon, and that since the carbon source in the synthetic raw material contains oxygen, it is inevitable that a small amount of oxygen is incorporated into the surface carbon of the composite material; the surface of the composite material stored in the air can absorb oxygen, a small amount or a trace amount of nickel and palladium can exist in an oxidation state, and impurities in the synthetic raw materials can contain a small amount or a trace amount of other elements, but the factors have no obvious influence on the performance of the composite material; the present invention recognizes that it is not necessary to specify these.
The composite material according to the first aspect, wherein the mass ratio of nickel to palladium is 3:1 to 100:1, preferably 4:1 to 100:1; if relatively higher catalytic hydrogenation activity is required, the mass ratio of nickel to palladium can be further controlled between 4:1 and 9:1. Within the above ratio range, only diffraction peaks of fcc NiPd alloy exist in the XRD spectrum of the composite material; and the characteristic peaks of the simple substance palladium appear when the content of the palladium is higher, and the simple substance palladium is difficult to be tightly coated by carbon and does not have the capability of resisting coalescence and poisoning deactivation.
The composite material according to the first aspect has a total mass fraction of nickel and palladium of 1% to 80%, preferably 30% to 80%, more preferably 50% to 78%, based on the composite material. The present invention has found that doping nickel with about 1% palladium significantly improves the catalytic hydrogenation capacity of the composite. In some preparation examples of the invention, the total mass fraction of nickel-palladium in the composite material can still reach about 75% even if subjected to acid treatment.
The composite material according to the first aspect, which is composed of the core-shell structure and a small amount of carbon matrix.
The composite material according to the first aspect, which is a mesoporous and/or macroporous material, the mesopore and macropore volumes accounting for more than 50% of the total pore volume. In some embodiments, the composite material has a mesoporous structure or a mesoporous and macroporous structure. The pore structure is a macroscopic property of the catalytic material, as is well known in the art.
The composite material according to the first aspect, having a specific surface area of 50m 2 /g～500m 2 /g, preferably 100m 2 /g～300m 2 /g。
According to the composite material of the first aspect, the particle size of the nickel-palladium alloy nano particles is 1nm to 50nm, generally 2nm to 25nm, and preferably 3nm to 15nm under the observation of a transmission electron microscope. In some preparation examples, the nickel-palladium alloy nanoparticles have a relatively narrow particle size distribution, substantially between 4nm and 10 nm.
According to the composite material of the first aspect, the graphitized carbon layer has a thickness of 0.5nm to 10nm, preferably 0.5nm to 5nm, typically between 1nm and 5nm, under observation by a transmission electron microscope.
The composite material according to the first aspect, the core-shell structure is spherical or spheroid.
According to the composite material of the first aspect, the XRD patterns of some preparation examples have only one diffraction peak in the range of 40.1-44.5 degrees.
In a second aspect the invention provides another composite of carbon-coated nickel-palladium alloy nanoparticles comprising the composite of the first aspect and a sulfur-containing compound supported thereon.
The composite material according to the second aspect, which consists of the composite material of the first aspect and the sulfur-containing compound supported thereon.
The composite material according to the second aspect, the molecular weight of the sulfur-containing compound is generally less than 200. The sulfur-containing compound may be either an organic sulfur compound or an inorganic sulfur compound; in the organic sulfur compound, the carbon-sulfur bond may be a double bond or a single bond. The sulfur-containing compound is preferably thiourea.
The mass fraction of sulphur may be from 0.1% to 10%, preferably from 0.5% to 5%, more preferably from 0.8% to 1.8%, based on the composite material of the second aspect.
A third aspect of the present invention provides a method of preparing the composite material of the first aspect, comprising:
s1, mixing a nickel source, a palladium source and a multi-element organic carboxylic acid in the presence of a first solvent to obtain a precursor solution, and then removing the first solvent to obtain a precursor;
s2, pyrolyzing the precursor in inert gas.
According to the preparation method of the third aspect, the first solvent is water and/or ethanol, preferably water.
According to the preparation method of the third aspect, the nickel source is a soluble nickel salt, and can be one or more of nickel acetate, basic nickel carbonate and nickel carbonate.
According to the preparation method of the third aspect, the palladium source is preferably a palladium-containing solution, and may be a palladium acetate solution, preferably a palladium acetate glacial acetic acid solution.
According to the production method of the third aspect, the organic polycarboxylic acid is preferably a polycarboxylic acid having hydroxyl groups in the molecule at the same time. The organic polycarboxylic acid may be one or more of citric acid, ascorbic acid, ethylenediamine tetraacetic acid, 2, 5-pyridinedicarboxylic acid, tartaric acid, benzoic acid or terephthalic acid, preferably citric acid.
According to the preparation method of the third aspect, the mass ratio of the nickel source to the palladium source is 3:1-100:1, preferably 4:1-100:1, and more preferably 4:1-9:1, calculated as metal elements.
According to the production method of the third aspect, in S1, the molar ratio of the nickel source and the palladium source to the organic polycarboxylic acid is 0.1:1 to 3:1, preferably 0.3:1 to 1.5:1, wherein the nickel source and the palladium source are calculated on the total molar amount of the metal elements.
According to the production method of the third aspect, in S1, the precursor solution may be produced as follows: adding a nickel source, a palladium source and a carbon source into water and/or alcohol, stirring for 8-16 h at 40-100 ℃, preferably stirring for 10-12 h at 50-90 ℃; wherein the palladium source is provided as a palladium acetate solution containing 0.5g to 1.1g palladium dissolved in 100mL glacial acetic acid and the nickel source is provided as nickel acetate (which may or may not contain water of crystallization).
According to the production method of the third aspect, in S1, the first solvent in the precursor solution is preferably removed by direct evaporation, and for example, the first solvent in the precursor solution may be evaporated to dryness on a rotary evaporator and/or dried in an oven.
According to the preparation method of the third aspect, in S2, the pyrolysis temperature is 500-800 ℃, preferably 500-700 ℃, more preferably 550-650 ℃; and/or pyrolysis time is 1h to 4h, preferably 1.5h to 3h; and/or the heating rate is 1 ℃/min to 10 ℃/min, preferably 2 ℃/min to 5 ℃/min.
According to the production method of the third aspect, in S2, the inert gas may be nitrogen, argon or helium.
The production method according to the third aspect, further comprising an optional acid treatment step after S2. The kind, amount and treatment time of the acid used for the acid treatment are not limited in the present invention, and may be selected by those skilled in the art based on prior knowledge and/or simple experiments. Acid treatment, such as hydrochloric acid or sulfuric acid, is typically carried out using a strong non-oxidizing acid. In some preparation examples of the invention, hydrochloric acid is used, the concentration is generally 0.5mol/L to 2mol/L, the temperature can be 60 ℃ to 100 ℃, the boiling is generally close to boiling, and the time can be 3 hours to 24 hours, and is generally 3 hours to 10 hours.
The preparation method according to the third aspect further comprises post-treatment steps of the product, such as filtration, washing, drying, etc.
In a fourth aspect the present invention provides a method of preparing a composite material of the second aspect, comprising the step of supporting a sulphur-containing compound on the composite material of the first aspect.
According to the production method of the fourth aspect, the manner of loading the sulfur-containing compound is not particularly limited, and the sulfur-containing compound may be loaded on the composite material of the first aspect in any known manner by those skilled in the art. In a preferred manner, the composite material of the first aspect is first dispersed in a second solvent, and the sulfur-containing compound is dissolved in a third solvent to form a solution; then mixing the two liquids; in order to make the contact between the two materials be full and uniform, mechanical stirring and mixing can be adopted, and ultrasonic mixing can also be adopted; or combining the two, firstly carrying out ultrasonic mixing, and then carrying out mechanical stirring mixing. The general load time is 12-24 h. In some embodiments, the sulfur-containing compound is thiourea, in which case the solvent is preferably water. In some preparation examples, the ultrasonic time is 0.5-3 h, the mechanical stirring time is 2-24 h, and the loading temperature is 25-90 ℃.
According to the production method of the fourth aspect, the kind and amount of the sulfur-containing compound may vary widely. The present inventors have found that the selectivity of the catalytic hydrogenation reaction can be significantly affected by treating the composite material of the first aspect with a sulfur-containing compound, and that the skilled person can experimentally select the appropriate sulfur-containing compound and determine its amount according to the actual needs. However, the influence of different small molecular sulfur-containing compounds on the composite material is different, for example, the selectivity of the catalyst for the hydrogenation reaction of the halogenated nitrobenzene can reach 100% when thiourea is selected.
According to the production method of the fourth aspect, the sulfur-containing compound can be supported by an impregnation method. For higher selectivity, the sulfur-containing compound may be used in an amount of 0.01 to 20, preferably 0.3 to 5, in terms of sulfur element, relative to 1mol of palladium element in the composite material of the first aspect.
According to the preparation method of the fourth aspect, the second solvent is water and/or an alcohol solvent, preferably water.
According to the preparation method of the fourth aspect, the third solvent is water and/or an alcohol solvent, preferably water.
The preparation method according to the fourth aspect further comprises post-treatment steps of the product, such as filtration, washing, drying, etc.
In a fifth aspect, the present invention provides a composite of carbon-coated nickel-palladium alloy nanoparticles prepared by the preparation method of any one of the preceding aspects.
In a sixth aspect the invention provides the use of the composite material of any of the preceding aspects as a hydrogenation catalyst in the presence of sulphur in a catalytic hydrogenation system.
According to the use of the sixth aspect, the hydrogen and/or the hydrogenation substrate contains sulphur. The preparation of hydrogen from fossil fuels is a main mode for obtaining industrial hydrogen in the petrochemical field, and the raw materials inevitably generate sulfur-containing compounds in the hydrogen production process, and although the Pressure Swing Adsorption (PSA) technology can enable the purity of the hydrogen to reach more than 99.9%, the sulfur-containing compounds still exist in the hydrogen; some substrates are inherently sulfur-containing, such as thiochromene and the like; sulfur-containing impurities may also be present in the reaction substrate, and the effect of these sulfur-containing compounds on the hydrogenation catalyst is still not negligible. The present invention has found that even when the composite material of the present invention is treated with thiourea of high concentration and high toxicity, it still has high catalytic hydrogenation activity, so that it is of particular advantage when it is used as a hydrogenation catalyst in these sulfur-containing catalytic hydrogenation systems.
According to the use of the sixth aspect, the hydrogenation substrate contains one or more functional groups selected from the group consisting of nitro groups, carbon-carbon double bonds, carbon-carbon triple bonds, ketone groups, aldehyde groups and aromatic rings. The hydrogenation of the above functional groups with carbon-coated nickel nanoparticle composites has been achieved in the prior art, and the composites of the present invention have higher catalytic hydrogenation activity than carbon-coated nickel nanoparticle composites, and thus the above functional groups contained in organic compounds can be similarly catalytically hydrogenated.
A seventh aspect of the invention provides the use of the composite material of the first, second or fifth aspect for the catalytic hydrogenation of nitro groups in organic compounds.
According to a seventh aspect of the use, the organic compound is a thio-nitroarene.
According to a seventh aspect of the use, the nitroaromatic hydrocarbon has a structure as shown in formula (I):
wherein X is selected from one or more of sulfur and sulfonyl, R1 is selected from one or more of hydrogen, C1-C6 alkyl, C1-C3 halohydrocarbyl, C1-C3 hydroxyhydrocarbyl, mercapto, aryl and arylthio, R2 is selected from one or more of hydrogen, C1-C6 alkyl, hydroxy, carboxyl, halogen, amino, mercapto, aryl, arylthio and nitro, and the aryl is unsubstituted or substituted with one or more of the following groups: nitro, C1-C6 hydrocarbyl, hydroxy, carboxyl, halogen, amino or amino. Typical thio-nitroarenes are 4-nitroanisole sulfide, 2-nitrodiphenyl sulfide, 4-nitrothiophenol, 3 '-dinitrodiphenyl sulfone and 4,4' -dinitrodiphenyl sulfone. The prior art has realized that the hydrogenation of the above-mentioned compounds with carbon-coated nickel nanoparticle composites, the composite of the present invention has higher catalytic hydrogenation activity than carbon-coated nickel nanoparticle composites, and thus can also perform catalytic hydrogenation of the above-mentioned organic compounds.
In an eighth aspect, the invention provides a process for selectively hydrogenating nitro groups in a halogenated nitroaromatic hydrocarbon comprising: under the condition of liquid phase catalytic hydrogenation, hydrogen and halogenated nitroarene are contacted with a catalyst in the presence of a sulfur-containing compound to carry out liquid phase catalytic hydrogenation reaction; the catalyst is the composite material of the first aspect of the invention; the sulfur-containing compound is thiocyanate and/or thiourea, and the mass ratio of the sulfur-containing compound to halogenated nitroaromatic hydrocarbon is 1: 100-1: 10000.
the present invention has found that the selectivity of the catalytic hydrogenation reaction can be significantly affected by the addition of the sulfur-containing compound, and those skilled in the art can experimentally select the appropriate sulfur-containing compound and determine the amount thereof according to actual needs. According to the method of the eighth aspect, the molecular weight of the sulfur-containing compound is generally 200 or less, and the operation is more convenient; the general dosage range is wider, so that the control is easier. However, the influence of different small molecular sulfur compounds on the reaction selectivity is different, for example, for preparing chloroaniline by selective hydrogenation of chloronitrobenzene, the selectivity of sodium sulfide is only 70-80%, the selectivity of thiocyanate is above 98%, and the selectivity of thiourea is 100%.
The method according to the eighth aspect, the thiocyanate is typically potassium thiocyanate and/or sodium thiocyanate.
According to the method of the eighth aspect, the mass ratio of the sulfur-containing compound to the halogenated nitroaromatic hydrocarbon is preferably 1: 100-1: 150.
according to the method of the eighth aspect, the mass ratio of the catalyst to halogenated nitroaromatic hydrocarbon is 1:1 to 1:15, preferably 1:1 to 1:7.
according to the method of the eighth aspect, the conditions for liquid phase catalytic hydrogenation are: the temperature is 20-100 ℃, preferably 40-60 ℃; and/or the hydrogen pressure is 0.5MPa to 4MPa, preferably 0.8MPa to 2MPa.
According to the method of the eighth aspect, the liquid phase hydrogenation reaction uses a solvent selected from one or more of isopropanol, ethanol, acetone and water, preferably isopropanol and/or water, more preferably isopropanol to water in a volume ratio of 10:1 to 5: 1.
According to the method of the eighth aspect, the halogenated nitroarene is chloronitrobenzene, preferably m-chloronitrobenzene or p-chloronitrobenzene.
In a ninth aspect, the invention provides another method for selectively hydrogenating nitro groups in a halogenated nitroaromatic hydrocarbon, comprising: under the condition of liquid phase catalytic hydrogenation, hydrogen and halogenated nitroaromatic hydrocarbon are contacted with a catalyst to carry out liquid phase catalytic hydrogenation reaction; the catalyst is the composite material of the second aspect of the invention.
According to the method of the ninth aspect, the mass ratio of the catalyst to halogenated nitroaromatic hydrocarbon is 1:1 to 1:15, preferably 1:1 to 1:7.
according to the method of the ninth aspect, the conditions for liquid phase catalytic hydrogenation are: the temperature is 20-100 ℃, preferably 40-60 ℃; and/or the hydrogen pressure is 0.5MPa to 4MPa, preferably 0.8MPa to 2MPa.
According to the method of the ninth aspect, the liquid phase hydrogenation reaction uses a solvent selected from one or more of isopropanol, ethanol, acetone and water, preferably isopropanol and/or water.
According to the method of the ninth aspect, the halogenated nitroarene is chloronitrobenzene, preferably m-chloronitrobenzene or p-chloronitrobenzene.
Analysis and characterization
The distribution of each element in the material was characterized by means of a spherical aberration electron microscope (STEM). The type of the adopted spherical aberration electron microscope is JEM-ARM200F (Japanese electronics Co., ltd.) and the test conditions are as follows: the acceleration voltage was 200kV.
Information such as the composition of the material, the structure or morphology of atoms or molecules within the material, and the like is obtained by XRD. The XRD diffractometer used was an X-ray diffractometer of model X' Pert Pro from Nalytical, pa, netherlands, under the following test conditions: cu target, K alpha ray, tube voltage of 40kV, tube current of 40mA,2 theta scanning range of 5 DEG to 80 deg.
The elements of the material surface were detected by X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source was monochromatized A1K alpha X-rays with a power of 330W and a base vacuum of 3X 10-9mbar at the analytical test.
The specific surface area and pore size distribution of the material were determined by the Brunauer-Emmett-Taller method (BET, quantachrome AS-6B type analyzer).
The content test of carbon, hydrogen, oxygen, nitrogen and sulfur elements is carried out on a Elementar Vario EL Cube element analyzer, and the specific operation method is as follows: the sample is weighed about 5mg in a tin cup, put into an automatic sample feeding disc, enter a combustion tube through a ball valve for combustion, and have a combustion temperature of 1000 ℃ (for eliminating atmospheric interference during sample feeding, helium purging is adopted), and C, H, N, S in the sample is respectively converted into carbon dioxide, water, nitrogen and sulfur dioxide. And separating the mixed gas by a chromatographic column, and finally detecting by a thermal conductivity cell. When oxygen element is measured, the sample is cracked in a high-temperature cracking tube filled with carbon powder, oxygen in the sample is converted into carbon monoxide, carrier gas carries the cracked product into a series scrubber to remove acid gas and water vapor, and finally the obtained product enters an infrared detector for detection.
The content of nickel and palladium elements is measured by adopting an inductively coupled plasma emission spectrometry (ICP-OES), and the specific method is as follows: (1) nitrolysis: 10mg of catalyst sample is measured and placed in a flask, 16mL of fresh aqua regia is added, a magnetic stirrer is added, the flask is placed in an oil bath, the temperature of 120 ℃ is condensed and refluxed for 12 hours, after cooling to room temperature, a glass syringe is used for sucking the solution, a disposable filter head with the aperture of 0.22 mu m is used for filtering, the filtrate is added into a 500mL volumetric flask, and ultrapure water is added for volume fixing. (2) content test: 10mL of the solution after nitrolysis and volume fixation is taken, and an instrument Agilent 5110 is adopted for metal content test.
Unless otherwise specified, all reagents used in the present invention are analytically pure and commercially available.
Preparation examples 1 to 4 are given to illustrate the composite material of the present invention and the preparation method thereof
Preparation example 1
1) 0.040g of palladium acetate was weighed and 3mL of glacial acetic acid was measured. Added to 170mL of deionized water and dissolved with stirring at 50 ℃. The mass ratio of the nickel source to the palladium source is 100:1 (calculated by metal elements), the molar ratio of the total molar quantity of nickel and palladium to the complexing agent is 1:1, weighing citric acid monohydrate and nickel acetate tetrahydrate, adding the citric acid monohydrate and the nickel acetate tetrahydrate into the solutions, stirring at 70 ℃ to obtain a homogeneous solution, continuously heating and evaporating to dryness, and grinding the solid to obtain a precursor.
2) And (3) placing the precursor obtained in the step (1) in a porcelain boat, placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen, heating to 600 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature under the nitrogen atmosphere to obtain a pyrolysis product.
3) And (3) adding the pyrolysis product obtained in the step (2) into 200mL of 1mol/L HCl solution, stirring at 90 ℃ and refluxing for 4 hours, carrying out suction filtration on the solution, washing with deionized water to be neutral, and then drying the powder in a 100 ℃ oven for 2 hours to obtain the carbon-coated nickel-palladium nanocomposite.
Preparation example 2
The procedure of preparation 1 was followed except that in step 1), 0.657g of palladium acetate was weighed and 35mL of glacial acetic acid was taken. Added to 170mL of deionized water and dissolved with stirring at 50 ℃. The mass ratio of the nickel source to the palladium source is 17:3 (calculated by metal elements), the molar ratio of the total molar quantity of nickel and palladium to the complexing agent is 1:1, weighing citric acid monohydrate and nickel acetate tetrahydrate, adding the citric acid monohydrate and the nickel acetate tetrahydrate into the solutions, stirring at 70 ℃ to obtain a homogeneous solution, continuously heating and evaporating to dryness, grinding the solid to obtain a precursor, and obtaining the carbon-coated nickel-palladium nanocomposite material by the rest of the precursor, which is the same as that of preparation example 1.
Preparation example 3
The procedure of preparation 1 was followed except that in step 1), 0.943g of palladium acetate was weighed and 60mL of glacial acetic acid was measured. Added to 170mL of deionized water and dissolved with stirring at 50 ℃. The mass ratio of the nickel source to the palladium source is 4:1 (calculated by metal elements), the molar ratio of the total molar quantity of nickel and palladium to the complexing agent is 1:1, weighing citric acid monohydrate and nickel acetate tetrahydrate, adding the citric acid monohydrate and the nickel acetate tetrahydrate into the solutions, stirring at 70 ℃ to obtain a homogeneous solution, continuously heating and evaporating to dryness, grinding the solid to obtain a precursor, and obtaining the carbon-coated nickel-palladium nanocomposite material by the rest of the precursor, which is the same as that of preparation example 1.
Preparation example 4
This preparation example is used to illustrate a sulfur-containing carbon-coated nickel-palladium nanocomposite.
Weighing 0.5g of the composite material obtained according to the method of preparation example 3, adding the composite material into 10mL of deionized water, and carrying out ultrasonic treatment for 1h to uniformly disperse the nano material; weighing 0.036g of thiourea, adding the thiourea into 10mL of deionized water, and performing ultrasonic treatment for 1h to completely dissolve the thiourea; mixing the two liquids, performing ultrasonic treatment for 1h, mechanically stirring for 12h at a rotating speed of 800rpm, performing suction filtration, washing with deionized water for 5 times, and performing freeze drying to obtain the sulfur-containing carbon-coated nickel-palladium nanocomposite, wherein the mass percent of sulfur element is 1.67% as measured by elemental analysis, and the specific surface area of the material is 145.0m as measured by BET 2 /g。
Examples 1 to 3 illustrate the method of synthesizing p-chloroaniline by catalytic selective hydrogenation of p-chloronitrobenzene using the composite material of the present invention as a catalyst
100mg of the carbon-coated nickel-palladium nano catalytic material prepared according to the preparation methods 1-3, 315mg of p-chloronitrobenzene, 2.4mg of thiourea, 27mL of isopropanol and 3mL of water are respectively added into a reaction kettle, and H is introduced 2 After the reaction kettle is replaced for 4 times, stirring and heating at low pressure, heating to the preset reaction temperature of 60 ℃, and then introducing H again 2 The pressure in the reaction kettle is 1.0MPa, the reaction is continued until the pressure is unchanged for 10 minutes, the reaction kettle is cooled to room temperature and then discharged, and the reaction kettle is opened to take out the product for chromatographic analysis. Reactant conversion and target product selectivity were calculated by the following formula:
conversion = mass of reacted reactant/amount of reactant added x 100%
Selectivity = target product mass/reaction product mass x 100%
The duration from the reaction of example 1 to the 10 minutes of pressure without change was 180 minutes, and after analysis of the product, p-chloronitrobenzene conversion was 100% and p-chloroaniline selectivity was 100%.
Example 2 the reaction time to 10 minutes pressure was 77 minutes and the product was analyzed to give 100% p-chloronitrobenzene conversion and 100% p-chloroaniline selectivity.
Example 3 the duration of the reaction to 10 minutes of pressure unchanged was 50 minutes and after analysis of the product, p-chloronitrobenzene conversion was 100% and p-chloroaniline selectivity was 100%.
Example 4
The procedure of example 3 was followed, except that thiourea was replaced with potassium thiocyanate, and the other was the same as in example 3, to catalyze the hydrogenation of p-chloronitrobenzene under the same conditions, with a conversion of 100% and a selectivity to p-chloroaniline of 98.84%.
Example 5
The procedure of example 1 was followed, except that thiourea was not added, the rest was the same as in example 1, and p-chloronitrobenzene was hydrogenated under the same conditions, with a p-chloronitrobenzene conversion of 100%, p-chloroaniline selectivity of 65.5% and the rest aniline.
Example 6
The procedure of example 3 was followed, except that the catalyst was a composite material of preparation example 4 in an amount of 100mg, thiourea was not added, p-nitrochlorobenzene was 157.5mg, and the rest was the same as in example 3, and p-chloronitrobenzene was hydrogenated under the same conditions, with a p-chloronitrobenzene conversion of 100% and a p-chloroaniline selectivity of 100%.
Comparative example 1
The same procedure as in example 1 was followed except that the catalyst was replaced with a commercial palladium carbon catalyst (10 wt% Pd, 55% aqueous) and the catalytic hydrogenation reaction was carried out under the same conditions as in example 1, whereby the conversion of p-chloronitrobenzene was 0%. It can be seen that the conventional supported Pd catalyst completely loses catalytic activity in the presence of sulfur-containing toxicants and does not have the capability of resisting sulfur poisoning.
Comparative example 2
The procedure of example 1 was followed, except that the catalyst was replaced with a commercial palladium-carbon catalyst (10% by weight Pd, water content: 55%) and thiourea was not added, and the other was the same as in example 1, except that p-chloronitrobenzene was hydrogenated under the same conditions, the conversion of p-chloronitrobenzene was 100%, and the p-chloroaniline content in the product was approximately 0. It can be seen that the selectivity of the conventional supported Pd catalyst to p-chloroaniline is poor.
TABLE 1 mass fractions of Nickel and Palladium and Nickel Palladium mass ratio in the composite Material of the invention
As can be seen from Table 1, the metal content of the composite materials of preparation examples 1 to 3 was about 75%, i.e., the metal content of the composite material of the present invention was very high, although the acid washing was performed and the mass ratio of nickel to palladium was varied in a wide range.
As can be seen from the pictures of the spherical aberration electron microscope in fig. 1, in the composite material prepared according to preparation example 3, the metal nano-particles are formed by mixing nickel element and palladium element, and other preparation examples of the invention also have the same characteristics, namely, the metal nano-particles in the composite material of the invention are nickel-palladium alloy; other preparation examples of the present invention also have the same features. As can be seen from the upper left corner picture in fig. 1, the metal nanoparticle has a particle diameter of 2 nm-25 nm, the graphitized carbon layer has a thickness of 1 nm-5 nm, and the carbon-coated nickel-palladium nanoparticle core-shell structure is spherical or spheroidic; other preparation examples of the present invention also have the same features.
As can be seen from the XRD patterns of FIG. 2, the composite material prepared according to preparation example 3 has only diffraction peaks of fcc NiPd alloy, and has no diffraction peaks of elemental nickel and elemental palladium, and other preparation examples of the present invention also have the same characteristics, namely, the metal nanoparticles in the composite material of the present invention are nickel-palladium alloys.
As can be seen from fig. 3, the surface layer of the composite material prepared according to preparation example 4 has carbon, oxygen, nickel, palladium, sulfur and nitrogen elements.
From example 5, it is clear that about 35% of the chlorine can be removed despite the incorporation of very small amounts of palladium in the metal nanoparticles, indicating a significant increase in the catalytic hydrogenation capacity of the composite, whereas the metal nanoparticles are essentially free of hydrodechlorination capacity only of elemental nickel.
As is clear from comparative example 2, the commercial palladium-carbon catalyst has high hydrogenation activity, and almost all of the chlorine is removed when catalyzing the hydrogenation of p-chloronitrobenzene. As is evident from comparative example 1, the commercial palladium on carbon catalyst does not have sulfur poisoning resistance and is rendered inactive by the addition of about 80PPMw of sulfide.
From examples 1 to 4, it is known that when a small amount of sulfide is added into the reaction system, the composite material of the invention has good sulfur poisoning resistance, maintains high catalytic activity in catalyzing p-chloronitrobenzene hydrogenation, and has high selective catalytic hydrogenation capability; the composite material of the invention can catalyze the hydrogenation of halogenated nitroaromatic hydrocarbon with high activity and high selectivity to prepare halogenated aromatic amine.
From example 6, it is known that even if the composite material is treated with high concentration of sulfide in the process of manufacturing the composite material, the composite material still has high activity catalytic hydrogenation capability, which indicates that the composite material has extremely strong sulfur poisoning resistance, and the treated composite material can catalyze p-chloronitrobenzene to selectively hydrogenate to manufacture p-chloroaniline with high selectivity without adding sulfide into a reaction system; the composite material treated by the sulfide can directly catalyze the halogenated nitroaromatic hydrocarbon to hydrogenate to prepare the halogenated aromatic amine with high activity and high selectivity, and toxic substances are prevented from being mixed into hydrogenation products.
Claims (19)
1. The composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer, and the inner core is nickel-palladium alloy nano particles; in the composite material, the mass ratio of nickel to palladium is 3:1-100:1; based on the mass of the composite material, the total mass fraction of nickel and palladium is 1-80%.
2. A composite material according to claim 1; the composite material is characterized in that the mass ratio of nickel to palladium is 4:1-100:1; based on the mass of the composite material, the total mass fraction of nickel and palladium is 50-78%.
3. A composite material according to claim 1; the method is characterized in that the particle size of the nickel-palladium alloy nano particles is 1 nm-50 nm.
4. A composite material according to claim 3; the method is characterized in that the particle size of the nickel-palladium alloy nano particles is 2 nm-25 nm.
5. A composite material according to claim 1; the graphitized carbon layer is characterized in that the thickness of the graphitized carbon layer is 0.5 nm-5 nm.
6. A preparation method of a composite material of carbon-coated nickel-palladium alloy nano particles comprises the following steps:
s1, mixing a nickel source, a palladium source and a multi-element organic carboxylic acid in the presence of a first solvent to obtain a precursor solution, and then removing the first solvent to obtain a precursor;
s2, pyrolyzing the precursor in inert gas.
7. The process of claim 6, wherein the first solvent is water and/or ethanol.
8. The method of claim 6, wherein the palladium source is a glacial acetic acid solution of palladium acetate.
9. The method according to claim 6, wherein the mass ratio of the nickel source to the palladium source is 3:1 to 100:1 in terms of metal element.
10. The process according to claim 6, wherein in S2, the pyrolysis temperature is 550℃to 650 ℃.
11. The process according to claim 6, comprising an acid treatment step after S2.
12. A composite of carbon-coated nickel-palladium alloy nanoparticles comprising the composite of claim 1 and thiourea supported thereon.
13. The composite material according to claim 12, wherein the mass fraction of elemental sulfur is 0.5% to 5%.
14. A preparation method of a composite material of carbon-coated nickel-palladium alloy nano particles comprises the following steps: comprising the step of loading thiourea on the composite of claim 1.
15. The production method according to claim 14, wherein the thiourea is used in an amount of 0.01 to 20 in terms of elemental sulfur, relative to 1mol of the palladium element in the composite material according to claim 1.
16. Use of the composite material according to claim 1 or 12 as a hydrogenation catalyst in the sulfur-containing catalytic hydrogenation system.
17. Use of the composite material according to claim 1 or 12 for the catalytic hydrogenation of nitro groups in organic compounds.
18. A method of selectively hydrogenating nitro groups in a halogenated nitroaromatic hydrocarbon comprising: under the condition of liquid phase catalytic hydrogenation, hydrogen and halogenated nitroarene are contacted with a catalyst in the presence of a sulfur-containing compound to carry out liquid phase catalytic hydrogenation reaction; the catalyst is the composite material of claim 1; the sulfur-containing compound is thiocyanate and/or thiourea, and the mass ratio of the sulfur-containing compound to halogenated nitroaromatic hydrocarbon is 1: 100-1: 10000.
19. a method of selectively hydrogenating nitro groups in a halogenated nitroaromatic hydrocarbon comprising: under the condition of liquid phase catalytic hydrogenation, hydrogen and halogenated nitroaromatic hydrocarbon are contacted with a catalyst to carry out liquid phase catalytic hydrogenation reaction; the catalyst is the composite material of claim 12.
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