CN106925321B - One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method - Google Patents
One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method Download PDFInfo
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- CN106925321B CN106925321B CN201511032231.1A CN201511032231A CN106925321B CN 106925321 B CN106925321 B CN 106925321B CN 201511032231 A CN201511032231 A CN 201511032231A CN 106925321 B CN106925321 B CN 106925321B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 379
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 365
- 238000000034 method Methods 0.000 title claims abstract description 157
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 62
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 62
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 55
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 226
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229910000765 intermetallic Inorganic materials 0.000 claims description 102
- 239000002994 raw material Substances 0.000 claims description 92
- 239000002184 metal Substances 0.000 claims description 90
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 48
- 239000006185 dispersion Substances 0.000 claims description 43
- 239000001301 oxygen Substances 0.000 claims description 39
- 229910052760 oxygen Inorganic materials 0.000 claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000002048 multi walled nanotube Substances 0.000 claims description 34
- 229910052723 transition metal Inorganic materials 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 208000016261 weight loss Diseases 0.000 claims description 19
- 230000004580 weight loss Effects 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 150000001450 anions Chemical class 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 229910052718 tin Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 235000007164 Oryza sativa Nutrition 0.000 claims description 12
- -1 basic metal carbonates Chemical class 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 235000009566 rice Nutrition 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 9
- 150000003624 transition metals Chemical group 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 150000004696 coordination complex Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims 5
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000002186 photoelectron spectrum Methods 0.000 claims 1
- 125000004429 atom Chemical group 0.000 description 227
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 65
- 239000000203 mixture Substances 0.000 description 37
- 229910052757 nitrogen Inorganic materials 0.000 description 37
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 30
- 229910017604 nitric acid Inorganic materials 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 28
- 230000003595 spectral effect Effects 0.000 description 28
- 150000002736 metal compounds Chemical class 0.000 description 27
- 150000003839 salts Chemical class 0.000 description 25
- 125000004433 nitrogen atom Chemical group N* 0.000 description 24
- 125000004430 oxygen atom Chemical group O* 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 15
- 229910002804 graphite Inorganic materials 0.000 description 13
- 239000010439 graphite Substances 0.000 description 13
- 241000209094 Oryza Species 0.000 description 11
- 230000010355 oscillation Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 241000894007 species Species 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000004437 phosphorous atom Chemical group 0.000 description 6
- 239000005864 Sulphur Chemical group 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 4
- WGECXQBGLLYSFP-UHFFFAOYSA-N 2,3-dimethylpentane Chemical compound CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
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- 238000004458 analytical method Methods 0.000 description 4
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- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 235000014413 iron hydroxide Nutrition 0.000 description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- VCJPCEVERINRSG-UHFFFAOYSA-N 1,2,4-trimethylcyclohexane Chemical compound CC1CCC(C)C(C)C1 VCJPCEVERINRSG-UHFFFAOYSA-N 0.000 description 3
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 description 3
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
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- 239000011261 inert gas Substances 0.000 description 3
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
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- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 3
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- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 3
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- 239000010937 tungsten Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
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- ODNRTOSCFYDTKF-UHFFFAOYSA-N 1,3,5-trimethylcyclohexane Chemical compound CC1CC(C)CC(C)C1 ODNRTOSCFYDTKF-UHFFFAOYSA-N 0.000 description 2
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- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical group 0.000 description 1
- QRMPKOFEUHIBNM-UHFFFAOYSA-N p-dimethylcyclohexane Natural products CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- LTHAIAJHDPJXLG-UHFFFAOYSA-N pentan-2-ylbenzene Chemical compound CCCC(C)C1=CC=CC=C1 LTHAIAJHDPJXLG-UHFFFAOYSA-N 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 229910000385 transition metal sulfate Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/18—Carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of nano-carbon material containing metallic atom and preparation method and application, the nano-carbon material contains the O element of 0.5-10 weight %, the N element of 0.1-4 weight % and the metallic element of 1-25 weight %, in XPS, the ratio of the content of the O element determined by the peak of 529.5-530.8eV and the total amount by the XPS O element determined is 0.02-0.3, the ratio of the amount of the O element determined by the peak of 531.0-532.5eV and the amount of the O element determined by the peak of 532.6-533.5eV is 0.3-1, the ratio of the amount of the N element determined by the peak within the scope of 398.5-400.1eV and the total amount by the XPS N element determined is 0-0.5, by 403.5-406. The content for the N element that peak within the scope of 5eV determines is 0.2-1 with the ratio of the total amount by the XPS N element determined.The present invention also provides the hydrocarbon dehydrogenation reaction method of the nano-carbon material containing metallic atom as catalyst is used, this method can obtain higher feed stock conversion and selectivity of product.
Description
Technical field
The present invention relates to a kind of nano-carbon materials containing metallic atom, and the invention further relates to a kind of nano carbon materials containing metallic atom
The preparation method of material and the nano-carbon material containing metallic atom prepared by this method, the present invention further relates to a kind of pass through will be above-mentioned
Nano-carbon material containing metallic atom is roasted and the nano-carbon material containing metallic atom for preparing, and the invention further relates to bases
Application and a kind of hydrocarbon dehydrogenation reaction side of the nano-carbon material containing metallic atom of the invention as the catalyst of hydrocarbon dehydrogenation reaction
Method.
Background technique
The dehydrogenation reaction of hydrocarbons is a kind of important reaction type, such as most of low-carbon olefine is to pass through low-carbon
The dehydrogenation reaction of alkane and obtain.Whether dehydrogenation reaction participates in be divided into direct dehydrogenation reaction (that is, oxygen according to oxygen
Gas is not involved in) and oxidative dehydrogenation (that is, oxygen participation) two classes.
A plurality of types of nano-carbon materials have been demonstrated equal to the direct dehydrogenation reaction of hydrocarbons and oxidative dehydrogenation
With catalytic effect, its catalytic activity can then be improved by introducing oxygen atom and/or nitrogen-atoms in nano-carbon material.
Oxygen atom is introduced in nano-carbon material, can form hydroxyl, carbonyl, carboxyl, ester group on nano-carbon material surface
With the oxygen-containing functional groups such as acid anhydrides.
Oxygen atom can be introduced in nano-carbon material by carrying out oxidation processes realization to nano-carbon material, to increase
The content of oxygen-containing functional group in nano-carbon material.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or it is strong
Oxidizing solution (such as H2O2、KMnO4) in carry out back flow reaction, can also be assisted while back flow reaction carry out microwave heating
Or sonic oscillation, to enhance the effect of oxidation reaction.It can but carry out back flow reaction in strong acid and/or strong oxidizing solution
Can have an adverse effect to the skeleton structure of nano-carbon material, or even destroy the skeleton structure of nano-carbon material.Such as: it will receive
Rice carbon material carries out back flow reaction in nitric acid, although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface,
Nano-carbon material is easily caused to be cut off and/or obviously increase the defects of graphite network structure position, to reduce nano carbon material
The performance of material, such as thermal stability.In addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, to introduce oxygen original
The introduction volume of the period of the day from 11 p.m. to 1 a.m, oxygen atom is high to the dependence of operation condition, and fluctuation range is wider.
When introducing nitrogen-atoms in nano-carbon material, according to nitrogen-atoms, locating chemical environment is not in nano-carbon material
Together, nitrogen-atoms is usually divided into chemical nitrogen and structure nitrogen.Chemical nitrogen mainly appears in material in the form of surface functional group
Surface, such as amino or nitrosyl radical surface nitrogen-containing functional group.Structure nitrogen refer to skeleton structure into nano-carbon material with
The nitrogen-atoms of carbon atom bonding.Structure nitrogen mainly include graphite mould nitrogen (that is,), pyridine type nitrogen (that is,) and pyrrole
Cough up type nitrogen (that is,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen and
Pyrroles's type nitrogen is unsaturated nitrogen atom, while replacing carbon atom, often will cause the missing for closing on carbon atom, forms defect
Position.
Can by introduced in nano-carbon material synthesis process nitrogenous functional atmosphere (such as ammonia, nitrogen, urea,
Melamine), nitrogen is introduced into nano carbon material simultaneously in the synthesis process of nano-carbon material using high temperature and/or high pressure
In the skeleton structure of material and/or surface；It can also be by the way that nano-carbon material to be placed in nitrogenous functional atmosphere (such as ammonia, nitrogen
Gas, urea, melamine) in, nitrogen is introduced into the surface of nano-carbon material using high temperature and/or high pressure.High temperature and/or
For high pressure although can form structure nitrogen in nano-carbon material, the type of nitrogen containing species depends on reaction condition, not easily-controllable
System；Also, the different types of nitrogen containing species so generated are unevenly distributed on the surface of nano-carbon material, lead to nitrogenous nanometer
The performance of carbon material is unstable.It then can also be reacted with amine, by the way that nano-carbon material is carried out oxidation processes thus in nanometer
Carbon material surface introduces nitrogen-atoms, and the nitrogen-atoms so introduced is essentially chemical nitrogen.
Although the research of doping vario-property and its catalytic performance in relation to nano-carbon material achieves many progress, for
Some of which basic problem is not built consensus yet, is still needed to doping vario-property nano-carbon material and preparation method thereof and catalysis
Performance is furtherd investigate.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of nano-carbon material containing metallic atom, using this method
Metallic atom can not only be introduced on nano-carbon material surface, and can steadily improve heteroatomic content in nano-carbon material,
The structure of nano-carbon material itself is influenced simultaneously little.
It is another object of the present invention to provide a kind of nano-carbon materials containing metallic atom, this contains metallic atom nano-sized carbon
When material is used for the dehydrogenation reaction of hydrocarbons, higher feed stock conversion and selectivity of product can be obtained.
Another object of the present invention is to provide a kind of hydrocarbon dehydrogenation reaction method, this method can obtain higher raw material conversion
Rate and selectivity of product.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material contains C element, O element, N element and at least one metallic element, with the nano carbon material containing metallic atom
On the basis of the total amount of material and based on the element, the content of O element is 0.5-10 weight %, and the total amount of the metallic element is 1-25 weight
% is measured, the content of N element is 0.1-4 weight %, and the content of C element is 61-98.4 weight %,
This contains in metallic atom nano-carbon material, and the total content of the oxygen element determined by x-ray photoelectron spectroscopy is IO t, by
The content for the O element that peak in x-ray photoelectron spectroscopy within the scope of 529.5-530.8eV determines is IO m, IO m/IO tIn 0.02-
In the range of 0.3；
This contains in metallic atom nano-carbon material, true by the peak within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy
The amount of fixed O element is IO c, the amount of the O element determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is
IO e, IO c/IO eIn the range of 0.3-1；
This contains in metallic atom nano-carbon material, determines that this contains metallic atom nano-carbon material by x-ray photoelectron spectroscopy
In N element total amount be IN t, by the amount for the N element that the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy determines
For IN c, IN c/IN tIn the range of 0-0.5, the N that is determined by the peak within the scope of 403.5-406.5eV in x-ray photoelectron spectroscopy
The content of element is IN n, IN n/IN tIn the range of 0.2-1.
According to the second aspect of the invention, the present invention provides a kind of preparation sides of nano-carbon material containing metallic atom
Method, this method include by a kind of aqueous dispersions for being dispersed with raw material nano carbon material and at least one metallic compound in closed
It is reacted in container, at least partly the metallic element in metallic compound is transition metal element, and is at least partly metallized
Closing the anion in object is NO3 -, in reaction process, the temperature of the aqueous dispersions is maintained in the range of 80-300 DEG C.
According to the third aspect of the present invention, the present invention provides a kind of method systems by the second aspect according to the present invention
Standby nano-carbon material containing metallic atom.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material be by the nano-carbon material containing metallic atom in terms of first aspect according to the present invention or third into
Prepared by row roasting.
According to the fifth aspect of the present invention, receiving containing metallic atom the present invention provides first aspect according to the present invention
Rice carbon material, the according to the present invention nano-carbon material containing metallic atom of third aspect or according to the present invention the 4th aspect
Nano-carbon material containing metallic atom as hydrocarbon dehydrogenation reaction catalyst application.
According to the sixth aspect of the invention, the present invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, is deposited
Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with first aspect according to the present invention containing metal
Atom nano-carbon material, the according to the present invention nano-carbon material containing metallic atom in terms of third or according to the present invention the 4th
The nano-carbon material containing metallic atom of a aspect contacts.
The preparation method of the nano-carbon material according to the present invention containing metallic atom steadily can not only regulate and control and/or improve
Metallic atom and heteroatomic content in nano-carbon material, while the structure of nano-carbon material itself is influenced small.Also, according to
The nano-carbon material containing metallic atom of the preparation method of the nano-carbon material containing metallic atom of the invention, preparation has stable property
Energy.Nano-carbon material containing metallic atom according to the present invention shows good catalytic in the dehydrogenation reaction of hydrocarbons
Can, feed stock conversion and selectivity of product can be significantly improved.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing metallic atom prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo for the raw material nano carbon material that embodiment 1 uses.
Specific embodiment
In the present invention, nano-carbon material refers to that dispersed phase scale at least one dimension is less than the carbon material of 100nm.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material contains C element, O element, N element and at least one metallic element.In the present invention, "at least one" table
Show one or more.
Nano-carbon material containing metallic atom according to the present invention, on the basis of the total amount of the nano-carbon material containing metallic atom
And based on the element, the content of O element is 0.5-10 weight %, preferably 1-8 weight %, more preferably 2.5-7 weight %；N member
The content of element is 0.1-4 weight %, preferably 0.1-3.5 weight %, more preferably 0.5-2 weight %；The total amount of metallic element
For 1-25 weight %, preferably 2-12 weight %, more preferably 5-8 weight %；The content of C element is 61-98.4 weight %, excellent
It is selected as 76.5-96.9 weight %, more preferably 83-92 weight %.Wherein, the content of each element uses x-ray photoelectron spectroscopy
Method measurement.Sample before testing 150 DEG C at a temperature of dry 3 hours in helium atmosphere.
In the present invention, X-ray photoelectron spectroscopic analysis is in Thermo Scientific company equipped with Thermo
It is tested on the ESCALab250 type x-ray photoelectron spectroscopy of Avantage V5.926 software, excitaton source is monochromatization Al
K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, base vacuum when analysis test
It is 6.5 × 10-10Mbar, the peak C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage software
Upper carry out data processing carries out quantitative analysis using sensitivity factor method in analysis module.
Nano-carbon material containing metallic atom according to the present invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity
The total content for the oxygen element that sub- power spectrum determines is IO t, determined by the peak within the scope of 529.5-530.8eV in x-ray photoelectron spectroscopy
O element (that is, the oxygen atom being bonded with metallic atom) content be IO m, IO m/IO tIn the range of 0.02-0.3, preferably exist
In the range of 0.05-0.3, more preferably in the range of 0.05-0.2.Nano-carbon material containing metallic atom according to the present invention, by
The content for the O element that peak in x-ray photoelectron spectroscopy within the scope of 531.0-533.5eV determines is IO nm, IO nm/IO tIn 0.7-
In the range of 0.98, preferably in the range of 0.7-0.95, more preferably in the range of 0.8-0.95.In the present invention, indicating
When numberical range, " ×-× in the range of " it include two binary values.
In the present invention, the area of the O1s spectral peak in x-ray photoelectron spectroscopy is denoted as AO 1, O1s spectral peak is divided into two groups
The area of spectral peak (corresponding to the oxygen species being connected with metallic atom) within the scope of 529.5-530.8eV is denoted as A by peakO 2, will
The area of spectral peak (corresponding to the oxygen species not being connected with metallic atom) within the scope of 531.0-533.5eV is denoted as AO 3, wherein
IO m/IO t=AO 2/AO 1, IO nm/IO t=AO 3/AO 1。
Nano-carbon material containing metallic atom according to the present invention, by 531.0-532.5eV range in x-ray photoelectron spectroscopy
The amount for the O element (that is, C=O) that interior peak determines is IO c, by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy
The amount of determining O element (that is, C-O) is IO e, IO c/IO eIn the range of 0.3-1, preferably in the range of 0.6-1.The present invention
In, by the spectral peak in x-ray photoelectron spectroscopy within the scope of 531.0-533.5eV (corresponding to the oxygen not being connected with metallic atom
Species) be further separated into two groups of peaks, i.e., spectral peak within the scope of 531.0-532.5eV (corresponding to C=O species) and
Spectral peak (corresponding to C-O species) within the scope of 532.6-533.5eV, by the area of the spectral peak within the scope of 531.0-532.5eV
It is denoted as AO 4, the area of the spectral peak within the scope of 532.6-533.5eV is denoted as AO 5, IO c/IO e=AO 4/AO 5。
Nano-carbon material containing metallic atom according to the present invention, in the nano-carbon material containing metallic atom by X-ray light
It is true by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy on the basis of the total amount for the C element that electron spectrum determines
The content of fixed C element (that is, graphite mould carbon) can be 50-95 weight %, preferably 60-90 weight %, more preferably 65-80
Weight %；The total content of the C element determined by the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy can be 5-
50 weight %, preferably 10-40 weight %, more preferably 20-35 weight %.In the present invention, by x-ray photoelectron spectroscopy
The area A of C1s spectral peakC 1C1s spectral peak in x-ray photoelectron spectroscopy is divided into two groups of peaks, that is, existed by the total amount for determining C element
Spectral peak (corresponding to graphite mould carbon species) within the scope of 284.7-284.9eV and the spectral peak within the scope of 286.0-288.8eV
(corresponding to non-graphite type carbon species), the area of the spectral peak within the scope of 284.7-284.9eV is denoted as AC 2, will be in 286.0-
The area of spectral peak within the scope of 288.8eV is denoted as AC 3, true by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy
Content=A of fixed C elementC 2/AC 1, the C element that is determined by the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy
Total content=AC 3/AC 1。
Nano-carbon material containing metallic atom according to the present invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity
The amount for the C element that peak in sub- power spectrum within the scope of 288.6-288.8eV determines is IC c, by 286.0- in x-ray photoelectron spectroscopy
The amount for the C element that peak within the scope of 286.2eV determines is IC e, IC c/IC eIn the range of 0.5-2, preferably in the model of 0.55-1.5
In enclosing, more preferably in the range of 1-1.2.In the present invention, by x-ray photoelectron spectroscopy within the scope of 286.0-288.8eV
Spectral peak (correspond to agraphitic carbon species) be further divided into two groups of peaks, i.e., the spectral peak within the scope of 286.0-286.2eV is (right
Should be in hydroxyl and ether type carbon species) and within the scope of 288.6-288.8eV spectral peak (correspond to carboxyl, acid anhydride and ester type carbon object
Kind), the area of the spectral peak within the scope of 286.0-286.2eV is denoted as AC 4, by the spectral peak within the scope of 288.6-288.8eV
Area is denoted as AC 5, IC c/IC e=AC 5/AC 4。
Nano-carbon material containing metallic atom according to the present invention determines that this contains metallic atom and receives by x-ray photoelectron spectroscopy
The total amount of N element in rice carbon material is IN t, the N that is determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy
Element is (that is, remove graphite mould nitrogen and-NO2Nitrogen species outside type nitrogen) amount be IN c, IN c/IN tIn the range of 0-0.5, preferably
In the range of 0.01-0.3, more preferably in the range of 0.01-0.25.
Nano-carbon material containing metallic atom according to the present invention determines that this contains metallic atom and receives by x-ray photoelectron spectroscopy
The total amount of N element in rice carbon material is IN t, the N that is determined by the peak within the scope of 403.5-406.5eV in x-ray photoelectron spectroscopy
Element is (that is,-NO2Species) content be IN n, IN n/IN tIn the range of 0.2-1, preferably in the range of 0.6-1, more preferably
In the range of 0.6-0.95.
Nano-carbon material containing metallic atom according to the present invention, by 400.6-401.5eV range in x-ray photoelectron spectroscopy
Content is lower or even is free of for the N element (that is, graphite mould nitrogen) that interior peak determines.Generally, according to the present invention to contain metallic atom
In nano-carbon material, the amount of the N element determined by the peak within the scope of 400.6-401.5eV in x-ray photoelectron spectroscopy is IN g,
IN g/IN tFor not higher than 0.3, generally in the range of 0.02-0.2, preferably in the range of 0.03-0.1.
In the present invention, the total amount A of N element is determined by the area of the N1s spectral peak in x-ray photoelectron spectroscopyN 1, by X-ray
N1s spectral peak in photoelectron spectroscopy is divided into three groups of peaks, i.e., the spectral peak within the scope of 403.5-406.5eV (corresponds to-NO2Object
Kind), within the scope of spectral peak within the scope of 400.6-401.5eV (corresponding to graphite mould nitrogen species) and 398.5-400.1eV
Spectral peak (removes graphite mould nitrogen and-NO2Nitrogen species outside type nitrogen), the area of the spectral peak within the scope of 400.6-401.5eV is remembered
For AN 2, the area of the spectral peak within the scope of 398.5-400.1eV is denoted as AN 3, by the spectral peak within the scope of 403.5-406.5eV
Area be denoted as AN 4, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/AN 1, IN n/IN t=AN 4/AN 1, it is lower than 0.01 in obtained ratio
When, it is believed that such species is free of, and the content of such species is denoted as 0.
In the present invention, position combination as corresponding to the summit at the peak at each peak be can determine that, range determines by mentioned earlier
Peak refer to combination corresponding to summit can peak within that range, in the range may include a peak, also can wrap
Include more than two peaks.Such as: the peak within the scope of 531.0-532.5eV refers to that combination corresponding to summit can be in 531.0-
Whole peaks in the range of 532.5eV.
Nano-carbon material containing metallic atom according to the present invention, the metallic element, which is selected from, has catalysis to hydrocarbon dehydrogenation reaction
The metallic element of effect, such as: the metallic element can be group ia metal element, group iia metal in the periodic table of elements
The combination of one or more of element, group III A metallic element, group IVA metallic element and transition metal element.
Preferably, the nano-carbon material containing metallic atom contains at least one first metallic element and optional at least one second gold medal
Belong to element, first metallic element is selected from transition metal element, and second metallic element is selected from group ia metal element, the
Group IIA metal element, group III A metallic element and group IVA metallic element.
The content of first metallic element and the second metallic element can contain metallic atom nano-carbon material according to this
Concrete application occasion makes appropriate choice.Generally, on the basis of the total amount of metal in the nano-carbon material containing metallic atom
And based on the element, the content of first metallic element can be 2-100 weight %, and the content of second metallic element can be with
For 0-98 weight %.From the angle for further increasing catalytic activity of the nano-carbon material containing metallic atom in hydrocarbon dehydrogenation reaction
It sets out, on the basis of the total amount of metal in the nano-carbon material containing metallic atom, the content of first metallic element is preferably
2-95 weight %, more preferably 55-85 weight %, the content of second metallic element are preferably 5-98 weight %, more preferably
For 15-45 weight %.
First metallic element can in the periodic table of elements Group IIIB metallic element, group ivb metallic element,
Group VB metallic element, vib metals element, V Group IIB metallic element, group VIII metallic element, I B-group metal member
Element and group iib metallic element.The specific example of first metallic element can include but is not limited to scandium, yttrium, rare earth metal
Element (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, Jin Hexin.It is excellent
Selection of land, first metallic element are selected from group VIII metallic element, I B-group metal element, group iib metallic element, the
IIIB race metallic element and group ivb metallic element.It is highly preferred that first metallic element is selected from group VIII metal member
Element.It is further preferred that first metallic element is selected from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum.
Second metallic element be selected from group ia metal element, group iia metallic element, group III A metallic element and
Group IVA metallic element, specific example can include but is not limited to lithium, sodium, potassium, magnesium, calcium, barium, strontium, aluminium, tin and lead.It is preferred that
Ground, second metallic element are selected from group ia metal element and group iia metallic element.It is highly preferred that second metal
Element is selected from sodium, potassium, magnesium, calcium and barium.
Nano-carbon material containing metallic atom according to the present invention, in a preferred embodiment, first metal
Element is selected from iron, cobalt and nickel, and second metallic element is selected from magnesium, calcium and barium.In the preferred embodiment, with this containing gold
On the basis of the total amount of category atom nano-carbon material and based on the element, the content of first metallic element is preferably 5-95 weight
% is measured, the content of more preferably 50-70 weight %, further preferably 55-65 weight %, second metallic element are preferably
5-95 weight %, more preferably 30-50 weight %, further preferably 35-45 weight %.In another preferred embodiment
In, first metallic element is selected from ruthenium, rhodium, palladium and platinum, and second metallic element is selected from sodium and potassium.Preferably implement at this
In mode, on the basis of the total amount of the nano-carbon material containing metallic atom and based on the element, the content of first metallic element
Preferably 30-90 weight %, more preferably 60-90 weight %, further preferably 65-85 weight %, the second metal member
The content of element is preferably 10-70 weight %, more preferably 10-40 weight %, further preferably 15-35 weight %.
Nano-carbon material containing metallic atom according to the present invention can exist with common various forms, be specifically as follows but
It is not limited to carbon nanotube containing metallic atom, graphene containing metallic atom, thin layer graphite containing metallic atom, nano-sized carbon containing metallic atom
One of particle, carbon nano-fiber containing metallic atom, Nano diamond containing metallic atom and fullerene containing metallic atom or two
Kind or more combination.The carbon nanotube containing metallic atom can be single-walled carbon nanotube containing metallic atom, contain metallic atom
The combination of one or more of double-walled carbon nano-tube and multi-walled carbon nanotube containing metallic atom.It is according to the present invention to contain gold
Belong to atom nano-carbon material, preferably multi-walled carbon nanotube containing metallic atom.
Nano-carbon material containing metallic atom according to the present invention, it is preferable that the multi-walled carbon nanotube containing metallic atom
Specific surface area is 50-500m2/ g can be further improved the catalytic performance of the nano-carbon material containing metallic atom, especially in this way
The catalytic performance of catalyst as hydrocarbons dehydrogenation reaction.It is highly preferred that this contains the ratio of metallic atom multi-walled carbon nanotube
Surface area is 80-300m2/g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nanotube is 90-250m2/
g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nanotube is 120-180m2/g.In the present invention, than
Surface area is measured by nitrogen adsorption BET method.
Nano-carbon material containing metallic atom according to the present invention, the multi-walled carbon nanotube containing metallic atom is in 400-800
DEG C temperature range in weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that
In the range of 0.01-0.5, better catalytic effect, especially urging as hydrocarbons dehydrogenation reaction can be obtained in this way
When agent, better catalytic effect can be obtained.It is highly preferred that w500/w800In the range of 0.01-0.4.It is further preferred that
w500/w800In the range of 0.04-0.15.In the present invention, w800=W800- W400, w500=W500- W400, W400For at 400 DEG C
At a temperature of the mass loss rate that measures, W800For in 800 DEG C of the at a temperature of mass loss rate that measures, W500For at 500 DEG C
At a temperature of the mass loss rate that measures；The weight-loss ratio is measured in air atmosphere using thermogravimetric analyzer, tests initial temperature
It is 25 DEG C, heating rate is 10 DEG C/min；Sample is before testing in 150 DEG C of temperature and the pressure of 1 normal atmosphere in helium atmosphere
Middle drying 3 hours.
In a preferred embodiment of the invention, the nano-carbon material containing metallic atom preferably contains metal original
Sub- multi-walled carbon nanotube, which is 50-500m2/ g, preferably 80-300m2/
G, more preferably 90-250m2/ g, further preferably 120-180m2/g；Also, w500/w800It is excellent in the range of 0.01-0.5
It is selected in the range of 0.01-0.4, more preferably in the range of 0.04-0.15.
Nano-carbon material containing metallic atom according to the present invention, for oxygen atom and nitrogen-atoms outside it is other nonmetallic miscellaneous
Atom, such as sulphur atom and phosphorus atoms, content can be customary amount.Generally, nanometer containing metallic atom according to the present invention
In carbon material, the total amount of other nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) outside oxygen atom and nitrogen-atoms can be
0.5 weight % hereinafter, preferably 0.2 weight % hereinafter, more preferably 0.1 weight % hereinafter, further preferably 0.05 weight
Measure % or less.Nano-carbon material containing metallic atom according to the present invention can also contain other metals in addition to aforesaid metal elements
Atom, other metallic atoms for example can be for from the catalyst used when preparing nano-carbon material.Other gold
The content for belonging to atom is generally 2.5 weight % hereinafter, preferably 2 weight % are hereinafter, further preferably 1 weight % is hereinafter, more
Further preferably 0.5 weight % is hereinafter, particularly preferably 0.2 weight % or less.
According to the second aspect of the invention, the present invention provides a kind of preparation sides of nano-carbon material containing metallic atom
Method, this method include by a kind of aqueous dispersions for being dispersed with raw material nano carbon material and at least one metallic compound in closed
It is reacted in container, at least partly the metallic element in metallic compound is that metallic element (is by transition metal element below
The metallic compound of transition metal element is known as transistion metal compound), and the anion at least partly in metallic compound is
NO3 -It (is below NO by anion3 -Metallic compound be known as nitric acid metal salt).
According to the method for the present invention, the metallic compound can be selected from metal nitrate, metal acetate, metal carbonate
Salt, metal sulfate, basic metal carbonates, metal phosphate, metal hydroxides, metal chloride and metal complex
(such as four ammino palladium of nitric acid, palladium acetylacetonate and four ammino platinic hydroxides) are further preferably selected from metal nitrate, metal acetic acid
Salt, metal carbonate, metal complex, basic metal carbonates, metal hydroxides and metal complex.Anion is non-
NO3 -Metallic compound can be selected from metal acetate, metal carbonate, metal sulfate, basic metal carbonates, metal phosphorus
Hydrochlorate, metal hydroxides, metal chloride and metal complex are further preferably selected from metal acetate, metal carbonate
Salt, basic metal carbonates, metal hydroxides and metal complex.
According to the method for the present invention, the metallic element in the transistion metal compound is selected from transition metal element, specifically
Can in the periodic table of elements Group IIIB metallic element, group ivb metallic element, Group VB metallic element, group VIB gold
Belong to element, V Group IIB metallic element, group VIII metallic element, I B-group metal element and group iib metallic element.It is described
The specific example of metallic element in transistion metal compound can include but is not limited to scandium, yttrium, thulium (such as lanthanum,
Cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, Jin Hexin.Preferably, described
Metallic element in transistion metal compound is selected from group VIII metallic element, I B-group metal element, group iib metal member
Element, Group IIIB metallic element and group ivb metallic element.It is highly preferred that the metallic element in the transistion metal compound
Selected from group VIII metallic element.It is further preferred that metallic element in the transistion metal compound be selected from iron, ruthenium, cobalt,
Rhodium, nickel, palladium and platinum.
The transistion metal compound can be selected from transition metal nitrate, transition metal acetate, transition metal carbonic acid
Salt, transition metal sulfate, transition metal subcarbonate, transition metal phosphate, transition metal hydroxide, transition metal
Chloride and transition metal complex, further preferably transition metal nitrate, transition metal acetate, transition metal carbon
Hydrochlorate, transition metal subcarbonate, transition metal hydroxide and transition metal complex (such as four ammino palladium of nitric acid, second
Acyl acetone palladium and four ammino platinic hydroxides).
The transistion metal compound can specifically be selected from but not limited to nickel nitrate, nickel acetate, nickel sulfate, basic carbonate
Nickel, nickel chloride, nickel hydroxide, cobalt nitrate, cobalt acetate, cobaltous sulfate, basic cobaltous carbonate, cobalt chloride, cobalt hydroxide, ferric nitrate, second
Sour ferrous iron, ferric sulfate, basic carbonate iron, iron chloride, iron hydroxide, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, chlorination
Zinc, zinc hydroxide, copper nitrate, copper acetate, copper sulphate, basic copper carbonate, copper chloride, Kocide SD, lanthanum nitrate, lanthanum carbonate, chlorine
Change lanthanum, lanthanum hydroxide, cerous nitrate, cerous carbonate, cerium chloride, cerium hydroxide, nitric acid ruthenium, ruthenic chloride, hydroxide ruthenium, palladium nitrate, chlorine
Change palladium, palladium dydroxide, platinum nitrate, platinum chloride, rhodium nitrate, nitric acid ammonia palladium (such as four ammino palladium of nitric acid), radium chloride, acetylacetone,2,4-pentanedione
Palladium, butyl titanate, zirconium hydroxide, plumbi nitras, manganese nitrate and four ammino platinic hydroxides.
According to the method for the present invention, the metallic element in the nitric acid metal salt can in the periodic table of elements group ia
Metallic element, group iia metallic element, Group IIIB metallic element, group ivb metallic element, Group VB metallic element,
Group vib metallic element, V Group IIB metallic element, group VIII metallic element, I B-group metal element, group iib metal member
Element, group III A metallic element and group IVA metallic element.The specific example of metallic element in the nitric acid metal salt can be with
Including but not limited to lithium, sodium, potassium, magnesium, calcium, barium, strontium, scandium, yttrium, thulium (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium,
Chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminium, germanium and tin.
According to the method for the present invention, metallic element is the metallic compound of transition metal element and anion is NO3 -Gold
It can be identical for belonging to compound, or different.Generally, on the basis of the total amount of the metallic compound, metallic element
Content for the metallic compound of transition metal element can be 1-100 weight %, and preferably 15-75 weight %, anion is
NO3 -The content of metallic compound can be 1-100 weight %, preferably 25-75 weight %.
According to the method for the present invention, from the nano-carbon material containing metallic atom of preparation is further increased anti-as hydrocarbon dehydrogenation
The angle of catalytic activity when the catalyst answered is set out, and at least partly anion is NO3 -Metallic compound in metallic element
Preferably non-transition metal elements are more preferably selected from group ia metal element, group iia metallic element, group III A metal member
Element and group IVA metallic element are further preferably selected from group ia metal element and group iia metallic element, further excellent
Choosing is selected from sodium, potassium, magnesium, calcium and barium.At this point, metallic element is nontransition metal on the basis of the total amount of the metallic compound
Element and anion are NO3 -Metallic compound content can be 1-99 weight %, preferably 20-80 weight %, more preferably
For 25-75 weight %.
According to the method for the present invention, the dosage of the metallic compound can be according to it is contemplated that draw in raw material nano carbon material
The content and type of the oxygen element, nitrogen and the metallic element that enter are selected.It is received what is finally prepared containing metallic atom
Rice carbon material is when being used as the catalyst of hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material: the weight ratio of metallic compound exists
In the range of 1:0.01-12, the nano-carbon material containing metallic atom thus prepared is in the catalysis for being used as hydrocarbon such as butane dehydrogenation reaction
The catalytic effect further increased can be obtained when agent.It is highly preferred that raw material nano carbon material: the weight ratio of metallic compound is 1:
In the range of 0.02-10.It is further preferred that raw material nano carbon material: model of the weight ratio of metallic compound in 1:0.2-10
In enclosing.It is further preferred that raw material nano carbon material: the weight ratio of metallic compound is in the range of 1:0.2-5.
Method according to the invention it is possible to be selected according to dosage of the amount of raw material nano carbon material to water.Preferably,
Raw material nano carbon material: H2The weight ratio of O is 1:5-1000, and when within the scope of the dosage of water being in this, nano-carbon material exists
Structural form retentivity in treatment process is more preferable, such as: when raw material nano carbon material is carbon nanotube, during processing
Substantially it is not cut off.It is highly preferred that raw material nano carbon material: H2The weight ratio of O is 1:10-500.It is further preferred that former
Expect nano-carbon material: H2The weight ratio of O is 1:20-150.
According to the method for the present invention, in a preferred embodiment, the aqueous dispersions contain the first metal compound
The metallic element of object and the second metallic compound, first metallic compound is selected from iron, cobalt and nickel, second metal compound
The metallic element of object is selected from magnesium, calcium and barium, and second metallic compound is preferably nitric acid metal salt, and what is thus prepared contains metal
Atom nano-carbon material can obtain preferably catalysis reaction effect when being used as the catalyst of hydrocarbon dehydrogenation reaction.Raw material nano carbon materials
Material: the first metallic compound: the weight ratio of the second metallic compound is preferably in the range of 1:0.02-6:0.02-8, more preferably
In the range of 1:0.1-1:0.1-3.In the preferred embodiment, with the first metallic compound and the second metallic compound
Total amount on the basis of, the content of first metallic compound is preferably 1-99 weight %, more preferably 50-75 weight %, institute
The content for stating the second metallic compound is preferably 1-99 weight %, more preferably 25-50 weight %.In the preferred embodiment
In, raw material nano carbon material: H2The weight ratio of O is preferably in the range of 1:20-200, more preferably in the range of 1:40-150.
According to the method for the present invention, in another preferred embodiment, the metal member of first metallic compound
Element is selected from ruthenium, rhodium, palladium and platinum, and the metallic element of second metallic compound is selected from sodium and potassium, second metallic compound
Preferably nitric acid metal salt, the nano-carbon material containing metallic atom thus prepared can be obtained when being used as the catalyst of hydrocarbon dehydrogenation reaction
It obtains and is preferably catalyzed reaction effect.Raw material nano carbon material: the first metallic compound: the weight ratio of the second metallic compound is preferred
In the range of 1:0.01-1:0.01-1, more preferably in the range of 1:0.2-0.5:0.1-0.2.In the preferred embodiment party
In formula, on the basis of the total amount of the first metallic compound and the second metallic compound, the content of first metallic compound is excellent
It is selected as 15-98 weight %, more preferably 60-80 weight %, further preferably 65-75 weight %, second metal compound
The content of object is preferably 2-85 weight %, more preferably 20-40 weight %, further preferably 25-35 weight %.It is preferred at this
Embodiment in, raw material nano carbon material: H2The weight ratio of O is preferably in the range of 1:10-200, more preferably in 1:25-
In the range of 100.
According to the method for the present invention, the condition of the reaction is to be enough to improve oxygen atom, nitrogen in raw material nano carbon material
Subject to the content of atom and metallic atom.Preferably, in reaction process, range of the temperature of the aqueous dispersions at 80-300 DEG C
It is interior.When the temperature of the aqueous dispersions is within above range, can not only effectively improve in raw material nano carbon material
Oxygen atom, nitrogen-atoms and metal atom content, and the structural form of raw material nano carbon material will not be generated and be significantly affected.More
Preferably, in reaction process, the temperature of the aqueous dispersions is in the range of 110-240 DEG C.
According to the method for the present invention, the duration of the reaction can be selected according to the temperature of reaction, with can
It is introduced in raw material nano carbon material subject to enough oxygen atoms, nitrogen-atoms and metallic atom.Generally, the reaction continues
Time can be in the range of 0.5-96 hours, preferably in the range of 2-72 hours, more preferably in 24-72 hours ranges
It is interior.
Method according to the invention it is possible to form the aqueous dispersions using common various methods, such as can incite somebody to action
Raw material nano carbon material is dispersed in water (preferably deionized water), and the metallic compound is then added, to obtain described
Aqueous dispersions.In order to further increase the dispersion effect of raw material nano carbon material, while shortening the time of dispersion, it can be using super
Raw material nano carbon material is dispersed in water by the method for sound oscillation.The condition of the sonic oscillation can be conventional selection, generally
Ground, the frequency of the sonic oscillation can be 10-200kHz, preferably 90-140kHz；The duration of the sonic oscillation can
Think 0.1-6 hours, preferably 1-4 hours.According to the method for the present invention, the metallic compound is according to specific type, can be with
It is provided in the form of solution (preferably aqueous solution), can also be provided, be not particularly limited in the form of pure material.
According to the method for the present invention, the content of oxygen element and nitrogen does not limit especially in the raw material nano carbon material
It is fixed, it can be conventional selection.Generally, in the raw material nano carbon material content of oxygen element be not higher than 1.5 weight %, it is excellent
It is selected as further preferably being not higher than 0.3 weight % not higher than 1.2 weight %, more preferably not above 0.5 weight %；Nitrogen member
The content of element is not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably not above 0.1 weight %, into one
Step is preferably not higher than 0.05 weight %, still more preferably for not higher than 0.02 weight %.According to the method for the present invention, described
The total amount of oxygen atom and remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside nitrogen-atoms in raw material nano carbon material
It (based on the element) can be customary amount.Generally, remaining in the raw material nano carbon material in addition to oxygen element and nitrogen
The total amount (based on the element) of nonmetallic heteroatoms is not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably
Not higher than 0.1 weight %, it is further preferably not higher than 0.05 weight %.According to the method for the present invention, the raw material nano carbon
Material may contain some metallic elements according to the difference in source, such as from using when preparing raw material nano carbon material
Metallic atom in catalyst.The content (based on the element) of metallic atom is generally 2.5 weights in the raw material nano carbon material
Measure % hereinafter, preferably 1.8 weight % hereinafter, further preferably 0.5 weight % hereinafter, still more preferably be 0.1 weight
Measure % or less.
According to the method for the present invention, raw material nano carbon material can be washed before use using method commonly used in the art
It washs, to remove some impurity of raw material nano carbon material surface；It can also directly be used without washing.It is disclosed by the invention
In embodiment, raw material nano carbon material is not pre-processed using preceding.
Method according to the invention it is possible to handle the nano-carbon material of various existing forms, received to improve this
Oxygen atom, nitrogen-atoms and metal atom content in rice carbon material.The raw material nano carbon material can be but be not limited to carbon and receive
One or both of mitron, graphene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene with
On combination.The carbon nanotube can for one of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube or
Two or more combinations.Preferably, the raw material nano carbon material is carbon nanotube, more preferably multi-walled carbon nanotube.
According to the method for the present invention, in a preferred embodiment, the raw material nano carbon material is that multi wall carbon is received
Mitron, the specific surface area of the multi-walled carbon nanotube can be 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-
260m2/ g, further preferably 120-190m2/g。
When the raw material nano carbon material is multi-walled carbon nanotube, temperature of the multi-walled carbon nanotube at 400-800 DEG C
The weight-loss ratio spent in section is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It can be in 0.01-
In the range of 0.5, preferably in the range of 0.02-0.4, more preferably in the range of 0.05-0.35, further preferably exist
In the range of 0.05-0.15.
In a kind of more preferably embodiment of the invention, the raw material nano carbon material is multi-walled carbon nanotube,
The specific surface area of the multi-walled carbon nanotube is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, into
One step is preferably 120-190m2/g；Weight-loss ratio of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800,
Weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, preferably 0.02-0.4's
In range, more preferably in the range of 0.05-0.35, further preferably in the range of 0.05-0.15.
According to the method for the present invention, the reaction carries out in closed container.The reaction can self-generated pressure (that is,
Do not apply pressure additionally) under carry out, can also carry out under pressure.Preferably, it is described reaction at autogenous pressures into
Row.The closed container can be the common reactor for being able to achieve sealing and heating, such as autoclave.
It according to the method for the present invention, can also include solid matter being isolated from the mixture that reaction obtains, and will divide
The solid matter separated out is dried, to obtain the nano-carbon material containing metallic atom.
Solid matter can be isolated from the mixture that reaction obtains using common solid-liquid separating method, such as centrifugation,
Filtering and decantation one or more of combination.
The condition of the drying can be conventional selection, be can remove the volatile materials in the solid matter isolated
It is quasi-.Generally, the drying can 50-200 DEG C at a temperature of carry out, preferably 80-180 DEG C at a temperature of carry out, it is more excellent
It is carried out at a temperature of being selected in 120-160 DEG C.The duration of the drying can be selected according to dry temperature and mode.
Generally, the duration of the drying can be 0.5-48 hours, preferably 6-24 hours, more preferably 10-12 hours.Institute
Stating drying can carry out under normal pressure (that is, 1 standard atmospheric pressure), can also carry out at reduced pressure.From further increasing
The angle of dry efficiency is set out, and the drying preferably carries out at reduced pressure.
According to the method for the present invention, oxygen atom, nitrogen-atoms and the metal that can be effectively improved in raw material nano carbon material are former
Sub- content, while the structural form of raw material nano carbon material will not be generated and be significantly affected.
According to the third aspect of the present invention, the present invention provides one kind contains metal by prepared according to the methods of the invention
Atom nano-carbon material.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material is by the nano-carbon material containing metallic atom of first aspect according to the present invention or according to the present invention
Prepared by the nano-carbon material containing metallic atom of three aspects is roasted.
The roasting can carry out under normal conditions.Preferably, it is described roasting 250-500 DEG C at a temperature of carry out.
It is highly preferred that it is described roasting 300-450 DEG C at a temperature of carry out, such as 350-450 DEG C at a temperature of carry out.The roasting
Duration can be selected according to the temperature of roasting.Generally, the duration of the roasting can be 1-24 hours, excellent
It is selected as 2-12 hours, more preferably 2-4 hours.The roasting can carry out in oxygen-containing atmosphere, can also be by inert gas
It is carried out in the atmosphere of formation.The oxygen-containing atmosphere can be air atmosphere；It can also be mixed to form for oxygen with inert gas
Mixed atmosphere, in the mixed atmosphere, the content of oxygen can be 0.1-22 volume %.The inert gas may include but not
It is limited to nitrogen and/or rare gas, the rare gas can be argon gas and/or helium.It is angularly examined from convenience and cost
Consider, it is preferable that the roasting carries out in oxygen-containing atmosphere (such as air atmosphere).
Nano-carbon material containing metallic atom according to the present invention is received by prepared by method of the invention containing metallic atom
Rice carbon material has good catalytic performance, and higher catalytic activity is especially shown in hydrocarbons dehydrogenation reaction.
Nano-carbon material containing metallic atom according to the present invention is received by prepared by method of the invention containing metallic atom
Rice carbon material can be directly used as catalyst, can also be used in the form of preformed catalyst.The preformed catalyst can contain
With good grounds nano-carbon material containing metallic atom of the invention or the nano carbon material containing metallic atom prepared by method of the invention
Material and binder.The binder can be selected according to the specifically used occasion of the preformed catalyst, can satisfy
It subject to requirement, such as can be organic binder and/or inorganic binder.The organic binder can be common each
Kind polymer-type binder, the inorganic binder can be common various heat-resistant inorganic oxides, such as aluminium oxide and/or oxygen
SiClx.It is to hydrocarbon dehydrogenation reaction (such as direct dehydrogenation reaction and oxidative dehydrogenation), particularly to oxygen in the preformed catalyst
When fluidized dehydrogenation reaction has the preformed catalyst of catalytic action, the binder is preferably inorganic binder.The shaped catalyst
In agent, the content of the nano-carbon material containing metallic atom can be selected according to specifically used requirement, be not particularly limited, generally
Ground, on the basis of the total amount of the preformed catalyst, the content of the nano-carbon material containing metallic atom can be 5-95 weight
Measure %.
According to the fifth aspect of the present invention, receiving containing metallic atom the present invention provides first aspect according to the present invention
Rice carbon material, the according to the present invention nano-carbon material containing metallic atom of third aspect or according to the present invention the 4th aspect
Nano-carbon material containing metallic atom as hydrocarbon dehydrogenation reaction catalyst application.
Application according to the present invention, the nano-carbon material containing metallic atom are used directly for hydrocarbon dehydrogenation reaction, can also
To be used for hydrocarbon dehydrogenation reaction after molding.The dehydrogenation reaction can carry out in the presence of oxygen, can not also be in the presence of oxygen
It carries out.Preferably, the dehydrogenation reaction carries out in the presence of oxygen, can obtain better catalytic effect in this way.
According to the sixth aspect of the invention, the present invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, is deposited
Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with first aspect according to the present invention containing metal
Atom nano-carbon material, the according to the present invention nano-carbon material containing metallic atom in terms of third or according to the present invention the 4th
The nano-carbon material containing metallic atom of a aspect contacts.
Hydrocarbon dehydrogenation reaction method according to the present invention, the nano-carbon material containing metallic atom are used directly for connecing with hydrocarbon
Touching is used to contact with hydrocarbon after can also forming the nano-carbon material containing metallic atom.
Hydrocarbon dehydrogenation reaction method according to the present invention can carry out dehydrogenation to a plurality of types of hydrocarbon, to obtain unsaturation
Hydrocarbon, such as alkene.According to the method for the present invention particularly suitable for carrying out dehydrogenation to alkane, to obtain unsaturated hydrocarbons, such as alkene.Root
According to method of the invention, the hydrocarbon is preferably alkane, such as C2-C12Alkane.Specifically, the hydrocarbon can be but be not limited to second
Alkane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene, n-hexane, 2- methylpentane, 3- methylpent
Alkane, 2,3- dimethylbutane, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexane, 3- methyl hexane, 2- ethylpentane,
3- ethylpentane, 2,3- dimethyl pentane, 2,4- dimethyl pentane, normal octane, 2- methyl heptane, 3- methyl heptane, 4- methyl
Heptane, 2,3- dimethylhexane, 2,4- dimethylhexane, 2,5- dimethylhexane, 3- ethyl hexane, 2,2,3- trimethyl penta
Alkane, 2,3,3- trimethylpentane, 2,4,4- trimethylpentane, 2- methyl -3- ethylpentane, n -nonane, 2- methyloctane, 3- first
Base octane, 4- methyloctane, 2,3- dimethyl heptane, 2,4- dimethyl heptane, 3- ethyl heptane, 4- ethyl heptane, 2,3,4-
Trimethyl cyclohexane, 2,3,5- trimethyl cyclohexane, 2,4,5- trimethyl cyclohexane, 2,2,3- trimethyl cyclohexane, 2,2,4- trimethyl oneself
Alkane, 2,2,5- trimethyl cyclohexane, 2,3,3- trimethyl cyclohexane, 2,4,4- trimethyl cyclohexane, 2- methyl -3- ethyl hexane, 2- first
Base -4- ethyl hexane, 3- methyl -3- ethyl hexane, 3- methyl -4- ethyl hexane, 3,3- diethylpentane, 1- methyl -2- second
Butylcyclohexane, 1- methyl -3- ethyl cyclohexane, 1- methyl -4- ethyl cyclohexane, n-propyl hexamethylene, isopropyl cyclohexane, three
Hexahydrotoluene (the various isomers including trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- 3-methyl cyclohexanols
Alkane, 1,2,5- trimethyl-cyclohexane, 1,3,5- trimethyl-cyclohexane), n-decane, 2- methylnonane, 3- methylnonane, 4- methyl
Nonane, 5- methylnonane, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyl octane, 4- ethyl octane, 2,3,4- tri-
Methyl heptane, 2,3,5- trimethylheptane, 2,3,6- trimethylheptane, 2,4,5- trimethylheptane, 2,4,6- trimethylheptane,
2,2,3- trimethylheptane, 2,2,4- trimethylheptane, 2,2,5- trimethylheptane, 2,2,6- trimethylheptane, 2,3,3- tri-
Methyl heptane, 2,4,4- trimethylheptane, 2- methyl -3- ethyl heptane, 2- methyl -4- ethyl heptane, 2- methyl -5- ethyl heptan
Alkane, 3- methyl -3- ethyl heptane, 4- methyl -3- ethyl heptane, 5- methyl -3- ethyl heptane, 4- methyl -4- ethyl heptane, 4-
Propyl heptane, 3,3- diethylhexane, 3,4- diethylhexane, 2- methyl -3,3- diethylpentane, vinylbenzene, 1- phenyl third
One of alkane, 2- phenyl-propane, 1- phenyl butane, 2- phenyl butane, 1- phenyl pentane, 2- phenyl pentane and 3- phenyl pentane
Or two or more combination.It is highly preferred that the hydrocarbon be one or both of propane, normal butane, iso-butane and vinylbenzene with
On.It is further preferred that the hydrocarbon is normal butane.
Hydrocarbon dehydrogenation reaction method according to the present invention, the reaction can carry out under conditions of there are oxygen, can also be with
Under conditions of oxygen is not present.Preferably, hydrocarbon dehydrogenation reaction method according to the present invention, under conditions of there are oxygen into
Row.When method of the invention carries out under conditions of there are oxygen, the dosage of oxygen can be conventional selection.Generally, hydrocarbon
Molar ratio with oxygen can be 0.01-100:1, preferably 0.1-10:1, more preferably 0.2-5:1, most preferably 0.5-2:
1。
Hydrocarbon dehydrogenation reaction method according to the present invention, can by carrier gas by hydrocarbon and optional oxygen be sent into reactor with
The haptoreaction of nano-carbon material containing metallic atom.The carrier gas can for it is common at reaction conditions will not with reactant and instead
The gas answered product that chemical interaction occurs and will not decomposed, as nitrogen, carbon dioxide, rare gas and water steam
The combination of one or more of gas.The dosage of the carrier gas can be conventional selection.Generally, the content of carrier gas can be with
For 30-99.5 volume %, preferably 50-99 volume %, more preferably 70-98 volume %.
The temperature of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be conventional selection, to be enough to send out hydrocarbon
Subject to raw dehydrogenation reaction.Generally, the contact can 200-650 DEG C at a temperature of carry out, preferably in 300-600 DEG C of temperature
Degree is lower to carry out, more preferably 350-550 DEG C at a temperature of carry out, further preferably 400-450 DEG C at a temperature of carry out.According to
Hydrocarbon dehydrogenation reaction method of the invention, the contact can carry out in fixed bed reactors, can also be in fluidized-bed reactor
Middle progress, is not particularly limited.Preferably, the contact carries out in fixed bed reactors.Hydrocarbon dehydrogenation according to the present invention is anti-
The duration of induction method, the contact can be selected according to the temperature of contact, and such as described contact is in fixed bed reactors
When middle progress, the duration of contact can be indicated with the volume space velocity of the gas of charging.Generally, the body of the gas of charging
Product air speed can be 0.1-10000h-1, preferably 1-6000h-1, more preferably 5-5000h-1, further preferably 10-
4000h-1, such as 600-800h-1。
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, outfit of the X-ray photoelectron spectroscopic analysis in Thermo Scientific company
It is tested on the ESCALab250 type x-ray photoelectron spectroscopy for having Thermo Avantage V5.926 software, excitaton source
For monochromatization Al K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, analysis test
When base vacuum be 6.5 × 10-10Mbar, the peak C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo
Data processing is carried out on Avantage software, and quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is being surveyed
It is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere before examination.
In following embodiment and comparative example, thermogravimetric analysis carries out on TA5000 thermal analyzer, and test condition is air gas
Atmosphere, heating rate are 10 DEG C/min, and temperature range is room temperature (25 DEG C) to 1000 DEG C.Sample is before testing in 150 DEG C of temperature
It is 3 hours dry in helium atmosphere with the pressure of 1 normal atmosphere.Using the ASAP2000 type N of Micromertrics company, the U.S.2
Physical adsorption appearance measurement the specific area.Raw material nano carbon material is analyzed using the high-resolution-ration transmission electric-lens of FEI Co., U.S. production
And the microscopic appearance of the nano-carbon material containing metallic atom.
Embodiment 1-34 is for illustrating nano-carbon material containing metallic atom and preparation method thereof of the invention.
Embodiment 1
(1) using 20g as multi-walled carbon nanotube (the specific surface area 136m of raw material nano carbon material2/ g, oxygen atom content
For 0.3 weight %, nitrogen atom content is 0.02 weight %, and (phosphorus is former for remaining nonmetallic heteroatoms in addition to nitrogen-atoms and oxygen atom
Son and sulphur atom) total content be 0.01 weight %, metallic atom total content be 0.1 weight %, in 400-800 DEG C of temperature range
Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.12, is purchased from Chinese science
Chengdu organic chemistry Co., Ltd, institute) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition
It include: frequency for 140kHz, the time is 1 hour., then, it is added as the acid chloride of transistion metal compound and as nitric acid
The potassium nitrate of metal salt, to obtain aqueous dispersions, wherein press raw material nano carbon material: transistion metal compound: nitric acid metal
Salt: H2The weight ratio of O is that the ratio of 1:0.2:0.1:100 feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 110 DEG C of temperature
Under, it reacts 48 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction
Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into, in normal pressure, (1 standard is big
Air pressure, similarly hereinafter), after 12 hours dry at a temperature of 120 DEG C, nano-carbon material containing metallic atom is obtained, this contains metallic atom and receives
Composition, specific surface area and the w of rice carbon material500/w800It is listed in table 1.
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing metallic atom of preparation, and Fig. 2 is as the more of raw material
The transmission electron microscope photo of wall carbon nano tube.It can be seen that the microcosmic of the nano-carbon material containing metallic atom from Fig. 1 and Fig. 2
Form is good, and it is little to show that reaction process influences the structure of nano-carbon material.
Comparative example 1
Aqueous dispersions same as Example 1 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in
In the oil bath that temperature is 110 DEG C, back flow reaction 48 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask
After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120
At a temperature of DEG C after drying 12 hours, nano-carbon material containing metallic atom is obtained.The nano-carbon material containing metallic atom of preparation
Composition, specific surface area and w500/w800It is listed in table 1.
Comparative example 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, step (1) is prepared
Aqueous dispersions be free of nitric acid metal salt, it is, by raw material nano carbon material dispersion in deionized water, conduct is then added
The acid chloride of transistion metal compound, to obtain aqueous dispersions, wherein the mole and embodiment 1 of transistion metal compound
Middle transistion metal compound is identical with the integral molar quantity of nitric acid metal salt, the dosage and reality of raw material nano carbon material and deionized water
It is identical to apply example 1.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Comparative example 3
It will be dispersed in deionized water using the nano-carbon material containing metallic atom of method identical with comparative example 2 preparation,
It is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes: that frequency is 140kHz, and the time is 1 hour.Then, it is added
Containing the potassium nitrate as nitric acid metal salt, to obtain aqueous dispersions, wherein press raw material nano carbon material: nitric acid metal salt:
H2The weight ratio of O is that the ratio of 1:0.1:100 feeds intake.
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 110 DEG C,
It reacts 48 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction kettle,
Reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature
After the lower drying of degree 12 hours, nano-carbon material containing metallic atom is obtained, this contains the composition of metallic atom nano-carbon material, specific surface
Long-pending and w500/w800It is listed in table 1.
Comparative example 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), nitre
The corresponding potassium carbonate of sour potassium equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area with
And w500/w800It is listed in table 1.
Comparative example 5
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), nitre
The corresponding potassium hydroxide of sour potassium equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area
And w500/w800It is listed in table 1.
Embodiment 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), make
Specific surface area for the multi-walled carbon nanotube (be purchased from Shandong great Zhan nano material Co., Ltd) of raw material nano carbon material is
251m2/ g, the weight-loss ratio in 400-800 DEG C of temperature range are w800, weight-loss ratio in 400-500 DEG C of temperature range
For w500, w500/w800Be 0.33, oxygen atom content is 0.62 weight %, and nitrogen atom content is 0.01 weight %, except nitrogen-atoms and
The total content of remaining nonmetallic heteroatoms (phosphorus atoms and sulphur atom) outside oxygen atom is 0.01 weight %, metallic atom total content
For 0.08 weight %.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, it, will in step (2)
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, in self-generated pressure
Lower reaction 48 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), mistake
Cross metallic compound and nitric acid metal salt total weight it is constant under conditions of, make transistion metal compound: nitric acid metal salt rubs
You are than being 1:10.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 5
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), nitre
The manganese nitrate of sour potassium equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/
w800It is listed in table 1.
Embodiment 6
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), second
The palladium nitrate of sour palladium equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/
w800It is listed in table 1.
Embodiment 7
Using 20g as multi-walled carbon nanotube (the specific surface area 183m of raw material nano carbon material2/ g, oxygen atom content are
0.2 weight %, nitrogen atom content are 0.01 weight %, remaining nonmetallic heteroatoms (phosphorus atoms in addition to nitrogen-atoms and oxygen atom
And sulphur atom) total content be 0.04 weight %, metallic atom total content be 0.03 weight %, 400-800 DEG C of humidity province
Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.07, purchased from China
Chengdu organic chemistry Co., Ltd, the academy of sciences) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation
Condition includes: that frequency is 90kHz, and the time is 4 hours.Then, iron hydroxide and the conduct as transistion metal compound is added
The magnesium nitrate of nitric acid metal salt, to obtain aqueous dispersions, wherein press raw material nano carbon material: transistion metal compound: nitric acid
Metal salt: H2The weight ratio of O is that the ratio of 1:1:3:150 feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 240 DEG C of temperature
Under, it reacts 24 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction
Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into normal pressure, 160 DEG C
At a temperature of after dry 10 hours, obtain nano-carbon material containing metallic atom, this contains the composition of metallic atom nano-carbon material, compares table
Area and w500/w800It is listed in table 1.
Comparative example 6
Aqueous dispersions same as Example 7 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in
In the oil bath that temperature is 240 DEG C, back flow reaction 24 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask
After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 160
At a temperature of DEG C after drying 10 hours, nano-carbon material containing metallic atom is obtained.The nano-carbon material containing metallic atom of preparation
Composition, specific surface area and w500/w800It is listed in table 1.
Embodiment 8
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), make
Specific surface area for the multi-walled carbon nanotube (be purchased from Shandong great Zhan nano material Co., Ltd) of raw material nano carbon material is
103m2/ g, w500/w800Be 0.23, oxygen atom content is 1.1 weight %, and nitrogen atom content is 0.03 weight %, except nitrogen-atoms and
The total content of remaining nonmetallic heteroatoms (phosphorus atoms and sulphur atom) outside oxygen atom is 0.01 weight %, metallic atom total content
For 1.6 weight %.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 9
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, it, will in step (2)
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 260 DEG C, in self-generated pressure
Lower reaction 24 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 10
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), press
Raw material nano carbon material: transistion metal compound: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:0.02:3:150 feeds intake.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 11
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), press
Raw material nano carbon material: transistion metal compound: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:1:0.02:150 feeds intake.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 12
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre
The aluminum nitrate of sour magnesium equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/
w800It is listed in table 1.
Embodiment 13
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre
The plumbi nitras of sour magnesium equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/
w800It is listed in table 1.
Embodiment 14
Nano-carbon material containing metallic atom is prepared using method identical with implementing 7, unlike, in step (1), hydrogen-oxygen
Change iron to be replaced with copper nitrate, the mole of copper nitrate is 2 times of the mole of iron hydroxide in embodiment 7.Preparation contains metal
Composition, specific surface area and the w of atom nano-carbon material500/w800It is listed in table 1.
Embodiment 15
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), hydrogen
Iron oxide is replaced with butyl titanate, and the mole of butyl titanate is 2 times of mole of iron hydroxide in embodiment 7.Preparation
The nano-carbon material containing metallic atom composition, specific surface area and w500/w800It is listed in table 1.
Embodiment 16
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), hydrogen
The zirconium hydroxide of iron oxide equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and
w500/w800It is listed in table 1.
Embodiment 17
Nano-carbon material containing metallic atom is prepared using method same as Example 1, difference is as follows:
In step (1), in deionized water by the dispersion of raw material nano carbon material, then it is added and is used as transistion metal compound
Nickel acetate and barium nitrate as nitric acid metal salt, to obtain aqueous dispersions, wherein press raw material nano carbon material: transition
Metallic compound: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:0.1:0.1:40 feeds intake；In step (2), by what is obtained
Aqueous dispersions at a temperature of 110 DEG C, react 72 in the autoclave with polytetrafluoroethyllining lining at autogenous pressures
Hour.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Comparative example 7
Aqueous dispersions identical with embodiment 17 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in
In the oil bath that temperature is 110 DEG C, back flow reaction 72 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask
After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120
At a temperature of DEG C after drying 12 hours, nano-carbon material containing metallic atom is obtained.The nano-carbon material containing metallic atom of preparation
Composition, specific surface area and w500/w800It is listed in table 2.
Embodiment 18
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 17, unlike, in step (2),
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, in spontaneous pressure
It is reacted 72 hours under power.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is arranged in table 2
Out.
Embodiment 19
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 17, unlike, it is received as raw material
The multi-walled carbon nanotube of rice carbon material is the same as embodiment 2.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and
w500/w800It is listed in table 2.
Embodiment 20
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 17, unlike, in step (1),
By raw material nano carbon material: transistion metal compound: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:6:0.1:40 feeds intake.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 21
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 17, unlike, in step (1),
By raw material nano carbon material: transistion metal compound: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:0.1:8:40 feeds intake.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 22
Nano-carbon material containing metallic atom is prepared using method same as Example 7, difference is as follows:
In step (1), in deionized water by the dispersion of raw material nano carbon material, then it is added and is used as transistion metal compound
Four ammino platinic hydroxides and sodium nitrate as nitric acid metal salt, to obtain aqueous dispersions, wherein raw material nano carbon materials
Material: transistion metal compound: nitric acid metal salt: H2The weight ratio of O is 1:0.5:0.2:25；In step (2), the moisture that will obtain
Dispersion liquid is placed in the autoclave with polytetrafluoroethyllining lining, and at a temperature of 180 DEG C, it is small to react 24 at autogenous pressures
When.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 23
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 22, unlike, in step (1),
Multi-walled carbon nanotube as raw material nano carbon material is the same as embodiment 8.Composition, the ratio of the nano-carbon material containing metallic atom of preparation
Surface area and w500/w800It is listed in table 2.
Embodiment 24
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 22, unlike, in step (1),
Under conditions of the total weight of transistion metal compound and nitric acid metal salt remains unchanged, make transistion metal compound: nitric acid metal
The molar ratio of salt is 10:1.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800In table 2
It lists.
Embodiment 25
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 22, unlike, in step (2),
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 300 DEG C, in spontaneous pressure
It is reacted 24 hours under power.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is arranged in table 2
Out.
Embodiment 26
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 22, unlike, in step (1),
The cobalt acetate of four ammino platinic hydroxide equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface
Long-pending and w500/w800It is listed in table 2.
Embodiment 27
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 22, unlike, in step (1),
The plumbi nitras of four ammino platinic hydroxide equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface
Long-pending and w500/w800It is listed in table 2.
Embodiment 28
Nano-carbon material containing metallic atom prepared by embodiment 1 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 8
Nano-carbon material containing metallic atom prepared by comparative example 1 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 9
Nano-carbon material containing metallic atom prepared by comparative example 2 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 10
Nano-carbon material containing metallic atom prepared by comparative example 3 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 11
Nano-carbon material containing metallic atom prepared by comparative example 4 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 12
Nano-carbon material containing metallic atom prepared by comparative example 5 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 29
Nano-carbon material containing metallic atom prepared by embodiment 2 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 30
Nano-carbon material containing metallic atom prepared by embodiment 3 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 31
Nano-carbon material containing metallic atom prepared by embodiment 4 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 32
Nano-carbon material containing metallic atom prepared by embodiment 5 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 33
Nano-carbon material containing metallic atom prepared by embodiment 6 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 34
Nano-carbon material containing metallic atom prepared by embodiment 22 450 DEG C at a temperature of air atmosphere in roasting it is 2 small
When.
Embodiment 35-68 is used to illustrate application and the hydrocarbon dehydrogenation reaction side of the nano-carbon material of the invention containing metallic atom
Method.
Embodiment 35-61
Respectively using the nano-carbon material containing metallic atom of 0.2g (admission space 1.9mL) embodiment 1-27 preparation as urging
Agent is seated in universal fixed bed miniature quartz pipe reactor, and two end seal of miniature quartz pipe reactor has quartz sand,
Under the conditions of 0.1MPa and 450 DEG C, by the gas containing hydrocarbon and oxygen, (concentration of normal butane is 1.98 volume %, normal butane and oxygen
Gas molar ratio 0.5:1, surplus are nitrogen as carrier gas) it with total volume air speed is 750h-1It is passed through in reactor and is reacted, even
The composition for the reaction mixture that continuous monitoring is exported from reactor, and calculate n-butane conversion, total olefin selectivity and 1- fourth
Alkene selectivity, the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 13-19
It is reacted using method identical with embodiment 35-61, unlike, it is prepared respectively using comparative example 1-7
Nano-carbon material containing metallic atom is as catalyst.Reaction result is listed in table 3.
Comparative example 20
It is reacted using method identical with embodiment 35-61, unlike, use raw material same as Example 1
Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Comparative example 21
It is reacted using method identical with embodiment 35-61, unlike, use raw material same as Example 7
Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Embodiment 62-68
It is reacted using method identical with embodiment 35-61, unlike, contained using prepared by embodiment 28-34
Metallic atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 22-26
It is reacted using method identical with embodiment 35-61, unlike, contain gold using prepared by comparative example 8-12
Belong to atom carbon nanotube as catalyst.Reaction result is listed in table 4.
Comparative example 27
It is reacted using method identical with embodiment 35-61, unlike, catalyst is will be same as Example 1
Raw material nano carbon material 350 DEG C at a temperature of air atmosphere in roast 4 hours obtained from.Reaction result arranges in table 4
Out.
Comparative example 28
It is reacted using method identical with embodiment 35-61, unlike, catalyst is will be same as Example 7
Raw material nano carbon material 300 DEG C at a temperature of air atmosphere in roast 12 hours obtained from.Reaction result arranges in table 4
Out.
Table 3
Table 4
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (84)
1. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material contain C element, O element, N element and
At least one metallic element, on the basis of the total amount of the nano-carbon material containing metallic atom and based on the element, the content of O element is
0.5-10 weight %, the total amount of the metallic element are 1-25 weight %, and the content of N element is 0.1-4 weight %, C element
Content is 61-98.4 weight %,
This contains in metallic atom nano-carbon material, and the total content of the oxygen element determined by x-ray photoelectron spectroscopy is IO t, penetrated by X
The content for the O element that peak in photoelectron spectra within the scope of 529.5-530.8eV determines is IO m, IO m/IO t0.02-0.3's
In range；
This contains in metallic atom nano-carbon material, is determined by the peak within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy
The amount of O element is IO c, the amount of the O element determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is IO e,
IO c/IO eIn the range of 0.3-1；
This contains in metallic atom nano-carbon material, determines the N in the nano-carbon material containing metallic atom by x-ray photoelectron spectroscopy
The total amount of element is IN t, the amount of the N element determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy is
IN c, IN c/IN tIn the range of 0-0.5, the N determined by the peak within the scope of 403.5-406.5eV in x-ray photoelectron spectroscopy is first
The content of element is IN n, IN n/IN tIn the range of 0.2-1；
This is contained metallic atom nano-carbon material and is prepared using method comprising the following steps: one kind being dispersed with raw material nano carbon materials
The aqueous dispersions of material and at least one metallic compound are reacted in closed container, at least partly in metallic compound
Metallic element is transition metal element, and the anion at least partly in metallic compound is NO3 -, in reaction process, the water
The temperature of dispersion liquid is maintained in the range of 80-300 DEG C.
2. nano-carbon material containing metallic atom according to claim 1, wherein IO m/IO tIn the range of 0.05-0.3,
IO c/IO eIn the range of 0.6-1, IN c/IN tIn the range of 0.01-0.3, IN n/IN tIn the range of 0.6-1.
3. nano-carbon material containing metallic atom according to claim 2, wherein IO m/IO tIn the range of 0.05-0.2,
IN c/IN tIn the range of 0.01-0.25, IN n/IN tIn the range of 0.6-0.95.
4. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein this contains metallic atom and receives
In rice carbon material, the amount of the C element determined by the peak within the scope of 288.6-288.8eV in x-ray photoelectron spectroscopy is IC c, by X
The amount for the C element that peak in X-ray photoelectron spectroscopy X within the scope of 286.0-286.2eV determines is IC e, IC c/IC eIn the model of 0.5-2
In enclosing.
5. nano-carbon material containing metallic atom according to claim 4, wherein IC c/IC eIn the range of 0.55-1.5.
6. nano-carbon material containing metallic atom according to claim 5, wherein IC c/IC eIn the range of 1-1.2.
7. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein contain metallic atom with this
On the basis of the total amount of the C element determined in nano-carbon material by x-ray photoelectron spectroscopy, by x-ray photoelectron spectroscopy
The content for the C element that peak within the scope of 284.7-284.9eV determines is 50-95 weight %, by x-ray photoelectron spectroscopy
The content for the C element that peak within the scope of 286.0-288.8eV determines is 5-50 weight %.
8. nano-carbon material containing metallic atom according to claim 7, wherein in the nano-carbon material containing metallic atom
On the basis of the total amount of the C element determined by x-ray photoelectron spectroscopy, by 284.7-284.9eV range in x-ray photoelectron spectroscopy
The content for the C element that interior peak determines is 60-90 weight %, by within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy
The content for the C element that peak determines is 10-40 weight %.
9. nano-carbon material containing metallic atom according to claim 8, wherein in the nano-carbon material containing metallic atom
On the basis of the total amount of the C element determined by x-ray photoelectron spectroscopy, by 284.7-284.9eV range in x-ray photoelectron spectroscopy
The content for the C element that interior peak determines is 65-80 weight %, by within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy
The content for the C element that peak determines is 20-35 weight %.
10. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein former containing metal with this
On the basis of the total amount of sub- nano-carbon material and based on the element, the content of O element is 1-8 weight %, and the content of N element is 0.1-
3.5 weight %, the content of C element are 76.5-96.9 weight %, and the total amount of the metallic element is 2-12 weight %.
11. nano-carbon material containing metallic atom according to claim 10, wherein with the nano-carbon material containing metallic atom
Total amount on the basis of and based on the element, the content of O element is 2.5-7 weight %, and the content of N element is 0.5-2 weight %, C member
The content of element is 83-92 weight %, and the total amount of the metallic element is 5-8 weight %.
12. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein this contains metallic atom
Nano-carbon material contains at least one first metallic element and optional at least one second metallic element, first metal
Element is selected from transition metal element, and second metallic element is selected from group ia metal element, group iia metallic element, the
Group IIIA metallic element and group IVA metallic element.
13. nano-carbon material containing metallic atom according to claim 12, wherein first metallic element is selected from the
Group VIII metal element, I B-group metal element, group iib metallic element, Group IIIB metallic element and group ivb metal member
Element, second metallic element are selected from group ia metal element and group iia metallic element.
14. nano-carbon material containing metallic atom according to claim 13, wherein first metallic element is selected from the
Group VIII metal element, second metallic element are selected from sodium, potassium, magnesium, calcium and barium.
15. nano-carbon material containing metallic atom according to claim 14, wherein first metallic element be selected from iron,
Cobalt, nickel, ruthenium, rhodium, palladium and platinum.
16. nano-carbon material containing metallic atom according to claim 12, wherein with the nano-carbon material containing metallic atom
Total amount on the basis of and based on the element, the content of first metallic element is 2-100 weight %, second metallic element
Content is 0-98 weight %.
17. nano-carbon material containing metallic atom according to claim 16, wherein with the nano-carbon material containing metallic atom
Total amount on the basis of and based on the element, the content of first metallic element is 2-95 weight %, second metallic element
Content is 5-98 weight %.
18. nano-carbon material containing metallic atom according to claim 17, wherein with the nano-carbon material containing metallic atom
Total amount on the basis of and based on the element, the content of first metallic element is 55-85 weight %, second metallic element
Content is 15-45 weight %.
19. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein this contains metallic atom
Nano-carbon material is carbon nanotube containing metallic atom.
20. nano-carbon material containing metallic atom according to claim 19, wherein this contains metallic atom nano-carbon material and is
Multi-walled carbon nanotube containing metallic atom.
21. nano-carbon material containing metallic atom according to claim 20, wherein the multi-wall carbon nano-tube containing metallic atom
The specific surface area of pipe is 50-500m2/g。
22. nano-carbon material containing metallic atom according to claim 21, wherein the multi-wall carbon nano-tube containing metallic atom
The specific surface area of pipe is 80-300m2/g。
23. nano-carbon material containing metallic atom according to claim 22, wherein the multi-wall carbon nano-tube containing metallic atom
The specific surface area of pipe is 90-250m2/g。
24. nano-carbon material containing metallic atom according to claim 23, wherein the multi-wall carbon nano-tube containing metallic atom
The specific surface area of pipe is 120-180m2/g。
25. nano-carbon material containing metallic atom according to claim 20, wherein the multi-wall carbon nano-tube containing metallic atom
Weight-loss ratio of the pipe in 400-800 DEG C of temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500,
w500/w800In the range of 0.01-0.5, the weight-loss ratio measures in air atmosphere.
26. nano-carbon material containing metallic atom according to claim 25, wherein w500/w800In the range of 0.01-0.4
It is interior.
27. nano-carbon material containing metallic atom according to claim 26, wherein w500/w800In the range of 0.04-0.15
It is interior.
28. a kind of preparation method of the nano-carbon material described in claim 1 containing metallic atom, this method includes by a kind of dispersion
There are raw material nano carbon material and the aqueous dispersions of at least one metallic compound to be reacted in closed container, at least partly
Metallic element in metallic compound is transition metal element, and the anion at least partly in metallic compound is NO3 -, reaction
In the process, the temperature of the aqueous dispersions is maintained in the range of 80-300 DEG C.
29. according to the method for claim 28, wherein metallic element be transition metal element metallic compound and yin from
Son is NO3 -Metallic compound it is identical or different, on the basis of the total amount of the metallic compound, metallic element is transition metal
The content of the metallic compound of element is 1-100 weight %, anion NO3 -Metallic compound content be 1-100 weight
Measure %.
30. according to the method for claim 29, wherein metallic element be transition metal element metallic compound and yin from
Son is NO3 -Metallic compound it is identical or different, on the basis of the total amount of the metallic compound, metallic element is transition metal
The content of the metallic compound of element is 15-75 weight %, anion NO3 -Metallic compound content be 25-75 weight
Measure %.
31. according to the method for claim 28, wherein at least partly anion is NO3 -Metallic compound in metal
Element is non-transition metal elements.
32. according to the method for claim 31, wherein at least partly anion is NO3 -Metallic compound in metal
Element is selected from group ia metal element, group iia metallic element, group III A metallic element and group IVA metallic element.
33. according to the method for claim 32, wherein at least partly anion is NO3 -Metallic compound in metal
Element is selected from group ia metal element and group iia metallic element.
34. the method according to any one of claim 28 and 31-33, wherein with the total amount of the metallic compound
On the basis of, metallic element is non-transition metal elements and anion is NO3 -Metallic compound content be 1-99 weight %.
35. according to the method for claim 34, wherein on the basis of the total amount of the metallic compound, metallic element is
Non-transition metal elements and anion are NO3 -Metallic compound content be 20-80 weight %.
36. according to the method for claim 35, wherein on the basis of the total amount of the metallic compound, metallic element is
Non-transition metal elements and anion are NO3 -Metallic compound content be 25-75 weight %.
37. the method according to any one of claim 28-33, wherein the non-NO of anion3 -Metallic compound be selected from
Metal acetate, metal carbonate, basic metal carbonates, metal hydroxides and metal complex.
38. the method according to any one of claim 28-33, wherein raw material nano carbon material: metallic compound
Weight ratio is in the range of 1:0.01-12；
Raw material nano carbon material: H2The weight ratio of O is 1:5-1000.
39. according to the method for claim 38, wherein raw material nano carbon material: the weight ratio of metallic compound is 1:
In the range of 0.02-10；
Raw material nano carbon material: H2The weight ratio of O is 1:10-500.
40. according to the method for claim 39, wherein raw material nano carbon material: the weight ratio of metallic compound is 1:
In the range of 0.2-10；
Raw material nano carbon material: H2The weight ratio of O is 1:20-150.
41. according to the method for claim 40, wherein raw material nano carbon material: the weight ratio of metallic compound is 1:
In the range of 0.2-5.
42. the method according to any one of claim 28-33, wherein the aqueous dispersions contain the first metallization
Object and the second metallic compound are closed, the metallic element of first metallic compound is selected from iron, cobalt and nickel, second metallization
The metallic element for closing object is selected from magnesium, calcium and barium, raw material nano carbon material: the first metallic compound: the weight of the second metallic compound
Ratio is measured in the range of 1:0.02-6:0.02-8, on the basis of the total amount of the first metallic compound and the second metallic compound, institute
The content for stating the first metallic compound is 1-99 weight %, and the content of second metallic compound is 1-99 weight %, raw material
Nano-carbon material: H2The weight ratio of O is in the range of 1:20-200.
43. according to the method for claim 42, wherein raw material nano carbon material: the first metallic compound: the second metallization
The weight ratio of object is closed in the range of 1:0.1-1:0.1-3, the total amount with the first metallic compound and the second metallic compound is
Benchmark, the content of first metallic compound are 50-75 weight %, and the content of second metallic compound is 25-50 weight
Measure %, raw material nano carbon material: H2The weight ratio of O is in the range of 1:40-150.
44. the method according to any one of claim 28-33, wherein the aqueous dispersions contain the first metallization
Object and the second metallic compound are closed, the metallic element of first metallic compound is selected from ruthenium, rhodium, palladium and platinum, second gold medal
The metallic element for belonging to compound is selected from sodium and potassium, raw material nano carbon material: the first metallic compound: the weight of the second metallic compound
Ratio is measured in the range of 1:0.01-1:0.01-1, on the basis of the total amount of the first metallic compound and the second metallic compound, institute
The content for stating the first metallic compound is 15-98 weight %, and the content of second metallic compound is 2-85 weight %, raw material
Nano-carbon material: H2The weight ratio of O is in the range of 1:10-200.
45. according to the method for claim 44, wherein raw material nano carbon material: the first metallic compound: the second metallization
The weight ratio of object is closed in the range of 1:0.2-0.5:0.1-0.2, with the total of the first metallic compound and the second metallic compound
On the basis of amount, the content of first metallic compound is 60-80 weight %, and the content of second metallic compound is 20-
40 weight %, raw material nano carbon material: H2The weight ratio of O is in the range of 1:25-100.
46. according to the method for claim 45, wherein the total amount with the first metallic compound and the second metallic compound is
Benchmark, the content of first metallic compound are 65-75 weight %, and the content of second metallic compound is 25-35 weight
Measure %.
47. the method according to any one of claim 28-33, wherein in reaction process, the temperature of the aqueous dispersions
Degree is maintained in the range of 110-240 DEG C.
48. the method according to any one of claim 28-33, wherein the duration of the reaction is in 0.5-96
In the range of hour.
49. according to the method for claim 48, wherein the duration of the reaction is in the range of 2-72 hours.
50. according to the method for claim 49, wherein the duration of the reaction is in the range of 24-72 hours.
51. the method according to any one of claim 28-33, wherein in the raw material nano carbon material, O element
Content be not higher than 1.5 weight %, the content of N element is not higher than 0.5 weight %, and the total amount of metallic element is 2.5 weights
Measure % or less.
52. method according to claim 51, wherein in the raw material nano carbon material, the content of O element be not higher than
1.2 weight %, the content of N element are not higher than 0.2 weight %, and the total amount of metallic element is 1.8 weight % or less.
53. method according to claim 52, wherein in the raw material nano carbon material, the content of O element be not higher than
0.5 weight %, the total amount of metallic element are 0.5 weight % or less.
54. method according to claim 53, wherein in the raw material nano carbon material, the content of O element be not higher than
0.2 weight %, the total amount of metallic element are 0.1 weight % or less.
55. method according to claim 54, wherein in the raw material nano carbon material, the content of O element be not higher than
0.1 weight %.
56. method according to claim 55, wherein in the raw material nano carbon material, the content of O element be not higher than
0.05 weight %.
57. method according to claim 56, wherein in the raw material nano carbon material, the content of O element be not higher than
0.02 weight %.
58. the method according to any one of claim 28-33, wherein the raw material nano carbon material is carbon nanometer
Pipe.
59. method according to claim 58, wherein the raw material nano carbon material is multi-walled carbon nanotube.
60. method according to claim 59, wherein the specific surface area of the multi-walled carbon nanotube is 50-500m2/g。
61. method according to claim 60, wherein the specific surface area of the multi-walled carbon nanotube is 80-300m2/g。
62. method according to claim 61, wherein the specific surface area of the multi-walled carbon nanotube is 100-260m2/g。
63. method according to claim 62, wherein the specific surface area of the multi-walled carbon nanotube is 120-190m2/g。
64. method according to claim 59, wherein the multi-walled carbon nanotube is in 400-800 DEG C of temperature range
Weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5,
The weight-loss ratio measures in air atmosphere.
65. method according to claim 64, wherein w500/w800In the range of 0.02-0.4.
66. method according to claim 65, wherein w500/w800In the range of 0.05-0.35.
67. method according to claim 66, wherein w500/w800In the range of 0.05-0.15.
68. the method according to any one of claim 28-33, wherein this method further include obtained from reaction it is mixed
It closes in object and isolates solid matter, and the solid matter isolated is dried.
69. method according to claim 68, wherein the drying 50-200 DEG C at a temperature of carry out, the drying
Duration be 0.5-48 hours.
70. method according to claim 69, wherein the drying 80-180 DEG C at a temperature of carry out, the drying
Duration be 6-24 hours.
71. method according to claim 70, wherein the drying 120-160 DEG C at a temperature of carry out, the drying
Duration be 10-12 hours.
72. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material be will be in claim 1-27 arbitrarily
Prepared by nano-carbon material containing metallic atom described in one is roasted.
73. the nano-carbon material containing metallic atom according to claim 72, wherein temperature of the roasting at 250-500 DEG C
Degree is lower to carry out, and the duration of the roasting is 1-24 hours.
74. the nano-carbon material containing metallic atom according to claim 73, wherein temperature of the roasting at 300-450 DEG C
Degree is lower to carry out, and the duration of the roasting is 2-12 hours.
75. nano-carbon material containing metallic atom according to claim 74, wherein the duration of the roasting is 2-4
Hour.
76. appointing in nano-carbon material containing metallic atom described in any one of claim 1-27 or claim 72-75
Application of the nano-carbon material containing metallic atom as the catalyst of hydrocarbon dehydrogenation reaction described in meaning one.
77. the application according to claim 76, wherein the dehydrogenation reaction carries out in the presence of oxygen.
78. the application according to claim 76 or 77, wherein the hydrocarbon is alkane.
79. the application according to claim 78, wherein the hydrocarbon is C2-C12Alkane.
80. the application according to claim 79, wherein the hydrocarbon is normal butane.
81. a kind of hydrocarbon dehydrogenation reaction method, this method is included under conditions of existence or non-existence oxygen, in hydrocarbon dehydrogenation reaction item
Under part, by nano-carbon material containing metallic atom or claim 72-75 described in any one of hydrocarbon and claim 1-27
Any one of described in nano-carbon material containing metallic atom contact.
82. the method according to claim 81, wherein the hydrocarbon is alkane.
83. the method according to claim 82, wherein the hydrocarbon is C2-C12Alkane.
84. the method according to claim 83, wherein the hydrocarbon is normal butane.
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