CN107661769B - Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method - Google Patents
Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method Download PDFInfo
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- CN107661769B CN107661769B CN201610603361.4A CN201610603361A CN107661769B CN 107661769 B CN107661769 B CN 107661769B CN 201610603361 A CN201610603361 A CN 201610603361A CN 107661769 B CN107661769 B CN 107661769B
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 325
- 239000000463 material Substances 0.000 title claims abstract description 269
- 238000000034 method Methods 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 72
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 56
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 54
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 44
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 42
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000011230 binding agent Substances 0.000 claims abstract description 62
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 55
- 239000006185 dispersion Substances 0.000 claims abstract description 50
- 150000007530 organic bases Chemical class 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 57
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 57
- 239000002808 molecular sieve Substances 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 238000000026 X-ray photoelectron spectrum Methods 0.000 claims description 39
- 238000002425 crystallisation Methods 0.000 claims description 39
- 230000008025 crystallization Effects 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 38
- 238000010335 hydrothermal treatment Methods 0.000 claims description 36
- -1 aliphatic amines Chemical class 0.000 claims description 32
- 239000002048 multi walled nanotube Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002585 base Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 238000000465 moulding Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 19
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 19
- 230000008707 rearrangement Effects 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 230000004580 weight loss Effects 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000001412 amines Chemical group 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 241000764238 Isis Species 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 230000002045 lasting effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000007767 bonding agent Substances 0.000 abstract 1
- 125000005842 heteroatom Chemical group 0.000 description 33
- 239000012452 mother liquor Substances 0.000 description 33
- 239000010703 silicon Substances 0.000 description 23
- 229910052710 silicon Inorganic materials 0.000 description 23
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 16
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 10
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 101710154778 Thymidylate synthase 1 Proteins 0.000 description 6
- 150000001722 carbon compounds Chemical class 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 238000005216 hydrothermal crystallization Methods 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 238000000926 separation method Methods 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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 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
- ODGLTLJZCVNPBU-UHFFFAOYSA-N 2,3,5-trimethylhexane Chemical compound CC(C)CC(C)C(C)C ODGLTLJZCVNPBU-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
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000002079 double walled nanotube Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910003472 fullerene Inorganic materials 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- PLZDDPSCZHRBOY-UHFFFAOYSA-N inaktives 3-Methyl-nonan Natural products CCCCCCC(C)CC PLZDDPSCZHRBOY-UHFFFAOYSA-N 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000002113 nanodiamond Substances 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- DQTVJLHNWPRPPH-UHFFFAOYSA-N 1,2,3-trimethylcyclohexane Chemical compound CC1CCCC(C)C1C DQTVJLHNWPRPPH-UHFFFAOYSA-N 0.000 description 2
- ODNRTOSCFYDTKF-UHFFFAOYSA-N 1,3,5-trimethylcyclohexane Chemical compound CC1CC(C)CC(C)C1 ODNRTOSCFYDTKF-UHFFFAOYSA-N 0.000 description 2
- CYISMTMRBPPERU-UHFFFAOYSA-N 1-Aethyl-4-methyl-cyclohexan Natural products CCC1CCC(C)CC1 CYISMTMRBPPERU-UHFFFAOYSA-N 0.000 description 2
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- XARGIVYWQPXRTC-UHFFFAOYSA-N 1-ethyl-2-methylcyclohexane Chemical compound CCC1CCCCC1C XARGIVYWQPXRTC-UHFFFAOYSA-N 0.000 description 2
- RUTNOQHQISEBGT-UHFFFAOYSA-N 2,3,4-trimethylhexane Chemical compound CCC(C)C(C)C(C)C RUTNOQHQISEBGT-UHFFFAOYSA-N 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- WBRFDUJXCLCKPX-UHFFFAOYSA-N 2,3-dimethylheptane Chemical compound CCCCC(C)C(C)C WBRFDUJXCLCKPX-UHFFFAOYSA-N 0.000 description 2
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical compound CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 2
- HDGQICNBXPAKLR-UHFFFAOYSA-N 2,4-dimethylhexane Chemical compound CCC(C)CC(C)C HDGQICNBXPAKLR-UHFFFAOYSA-N 0.000 description 2
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- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical compound CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
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- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
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- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 2
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 2
- DUPUVYJQZSLSJB-UHFFFAOYSA-N 3-ethyl-2-methylpentane Chemical compound CCC(CC)C(C)C DUPUVYJQZSLSJB-UHFFFAOYSA-N 0.000 description 2
- CYWROHZCELEGSE-UHFFFAOYSA-N 3-ethyl-3-methylhexane Chemical compound CCCC(C)(CC)CC CYWROHZCELEGSE-UHFFFAOYSA-N 0.000 description 2
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- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- SEEOMASXHIJCDV-UHFFFAOYSA-N 3-methyloctane Chemical compound CCCCCC(C)CC SEEOMASXHIJCDV-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
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- DOGIHOCMZJUJNR-UHFFFAOYSA-N 4-methyloctane Chemical compound CCCCC(C)CCC DOGIHOCMZJUJNR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N iso-quinoline Natural products C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 125000002183 isoquinolinyl group Chemical class C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- QRMPKOFEUHIBNM-UHFFFAOYSA-N p-dimethylcyclohexane Natural products CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 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
- 239000012071 phase Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- CPOUUWYFNYIYLQ-UHFFFAOYSA-M tetra(propan-2-yl)azanium;hydroxide Chemical compound [OH-].CC(C)[N+](C(C)C)(C(C)C)C(C)C CPOUUWYFNYIYLQ-UHFFFAOYSA-M 0.000 description 1
- LBUJPTNKIBCYBY-UHFFFAOYSA-N tetrahydroquinoline Natural products C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 1
- 125000000147 tetrahydroquinolinyl group Chemical class N1(CCCC2=CC=CC=C12)* 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- JVOPCCBEQRRLOJ-UHFFFAOYSA-M tetrapentylazanium;hydroxide Chemical compound [OH-].CCCCC[N+](CCCCC)(CCCCC)CCCCC JVOPCCBEQRRLOJ-UHFFFAOYSA-M 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/40—
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
Abstract
A nano carbon material forming body, a preparation method and application thereof, a forming method of the nano carbon material and a hydrocarbon dehydrogenation reaction method. The invention discloses a nano carbon material forming body, which contains a nano carbon material and a heat-resistant inorganic oxide for bonding and forming the nano carbon material, wherein the content of the nano carbon material is 6-94 wt%, the content of a bonding agent is 6-94 wt%, and the nano carbon material is prepared by adopting a method comprising the following steps: reacting an aqueous dispersion solution in which a raw material nanocarbon material is dispersed in a closed container, wherein the aqueous dispersion solution contains or does not contain an organic base, the organic base is amine and/or quaternary ammonium base, and the temperature of the aqueous dispersion solution is kept within the range of 80-220 ℃ during the reaction. The nano carbon material formed body of the invention uses the heat-resistant inorganic oxide as a binder to bond and form the nano carbon material, has high crushing strength and high porosity, and is suitable for being used as a catalyst, in particular a catalyst for dehydrogenation reaction of hydrocarbon.
Description
Technical Field
The invention relates to the technical field of nano carbon material forming, in particular to a nano carbon material forming body and a preparation method thereof, and also relates to application of the nano carbon material forming body as a catalyst for hydrocarbon dehydrogenation reaction.
Background
Dehydrogenation of hydrocarbons is an important type of reaction, for example, most lower alkenes are obtained by dehydrogenation of lower alkanes. Dehydrogenation reactions can be classified into two types, direct dehydrogenation reactions (i.e., oxygen does not participate) and oxidative dehydrogenation reactions (i.e., oxygen does participate), depending on whether oxygen participates.
Various types of nanocarbon materials have been demonstrated to have catalytic effects on both direct dehydrogenation reactions and oxidative dehydrogenation reactions of hydrocarbon materials.
In the hydrocarbon oxidative dehydrogenation process using the nano-carbon material as the catalyst, for example, a fixed bed reaction process is adopted, the nano-carbon material needs to be molded, and the molded body needs to meet the following two requirements: (1) the catalyst has certain strength to avoid the molded body from being crushed in the reaction process, and on one hand, the pressure drop of a catalyst bed layer is increased due to fine particles or powder formed by crushing, so that the production and operation cost is increased, and the production danger is increased; on the other hand, the fine particles or powder formed by crushing can cause catalyst loss and product separation complication if the fine particles or powder is carried out by reaction products; (2) the nano carbon material has certain porosity to improve the specific surface area of the formed body, so that the nano carbon material in the formed body can be more fully contacted with reaction materials.
As an example of shaping nanocarbon materials, researchers have attempted to load Carbon Nanotubes (CNTs) on the surface of SiC foams to form CNT/SiC foams. Although CNTs anchor well to the surface of the SiC foam, the loading of CNTs is low, typically reaching only 0.5-4 wt%.
Therefore, how to form the nanocarbon material into a formed body with high strength in a wide nanocarbon material content range still remains a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a nano carbon material forming body and a preparation method thereof, wherein the nano carbon material forming body not only has higher strength, but also can adjust the content of a nano carbon material in a wider range.
According to one aspect of the present invention, there is provided a nanocarbon material molded body comprising a nanocarbon material and a heat-resistant inorganic oxide for binding and molding the nanocarbon material, wherein the nanocarbon material is contained in an amount of 6 to 94% by weight and the binder is contained in an amount of 6 to 94% by weight, based on the total amount of the molded body;
the nano carbon material is prepared by adopting a method comprising the following steps: reacting an aqueous dispersion in which a raw material nanocarbon material is dispersed in a closed container, wherein the aqueous dispersion contains or does not contain an organic base, the organic base is amine and/or quaternary ammonium base, and the temperature of the aqueous dispersion is kept within the range of 80-220 ℃ during the reaction.
According to a second aspect of the present invention, there is provided a nanocarbon material molded body comprising a nanocarbon material and a heat-resistant inorganic oxide for binding and molding the nanocarbon material, wherein the nanocarbon material is contained in an amount of 6 to 94% by weight and the binder is contained in an amount of 6 to 94% by weight, based on the total amount of the molded body, and the nanocarbon material contains an O element and optionally an N element.
According to a third aspect of the present invention, there is provided a method for producing a nanocarbon material molded body, comprising mixing a nanocarbon material with a binder source, molding the obtained mixture to obtain a molded body, drying and optionally firing the molded body, the binder source being selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, the nanocarbon material being a nanocarbon material which has not been surface-treated and/or a surface-treated nanocarbon material, the surface-treated nanocarbon material containing an O element and optionally an N element as determined by X-ray photoelectron spectroscopy.
According to a fourth aspect of the present invention, there is provided a nanocarbon material molded body produced by the method according to the third aspect of the present invention.
According to a fifth aspect of the present invention, the present invention provides use of the nanocarbon material shaped body according to the present invention as a catalyst for dehydrogenation reaction of hydrocarbons.
According to a sixth aspect of the present invention, there is provided a hydrocarbon dehydrogenation reaction method comprising contacting a hydrocarbon with the nanocarbon material shaped body according to the first, second or fourth aspect of the present invention under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen.
The nano carbon material formed body of the invention uses the heat-resistant inorganic oxide as a binder to bond and form the nano carbon material, has high crushing strength and high porosity, and is suitable for being used as a catalyst, in particular a catalyst for dehydrogenation reaction of hydrocarbon.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the invention, the nano carbon material refers to a carbon material with at least one dimension of a disperse phase dimension less than 100 nm. In the present invention, "in the range of x to x" includes two boundary values when a numerical range is expressed. In the present invention, "at least one" means one or two or more.
According to a first aspect of the present invention, there is provided a nanocarbon material molded body containing a nanocarbon material (hereinafter, the nanocarbon material is sometimes also referred to as a heteroatom-containing nanocarbon material) and a heat-resistant inorganic oxide for binding molding the nanocarbon material.
According to the molded body of the first aspect of the present invention, the nanocarbon material is produced by a method comprising: reacting an aqueous dispersion in which a raw material nanocarbon material is dispersed in a closed container, wherein the aqueous dispersion contains or does not contain an organic base, the organic base is amine and/or quaternary ammonium base, and the temperature of the aqueous dispersion is kept within the range of 80-220 ℃ during the reaction.
The dispersion medium in the aqueous dispersion may be water or an aqueous solution containing at least one organic base.
In the case where the dispersion medium of the aqueous dispersion is water, the raw material nanocarbon material: h2The weight ratio of O is preferably in the range of 1: 2-200, more preferably in the range of 1: in the range of 5 to 100, further preferably in the range of 1: in the range of 10 to 50, particularly preferably in the range of 1: 15-25. The amount of water used may be adjusted depending on the type of the organic base so that the organic base can be uniformly dispersed in water.
When the dispersion medium of the aqueous dispersion contains water and an organic base dissolved in water, the catalytic performance of the nanocarbon material molded body in the hydrocarbon dehydrogenation reaction process can be further improved. From the viewpoint of further improving the catalytic performance when the nanocarbon material molded body is used as a catalyst for a hydrocarbon dehydrogenation reaction, the raw nanocarbon material: the weight ratio of the organic base is preferably in the range of 1: in the range of 0.05 to 20, more preferably in the range of 1: 0.1 to 8, and more preferably 0.5 to 5.
The organic base is selected from amines and quaternary ammonium bases. The quaternary ammonium base may specifically be a compound of formula I:
in the formula I, R1、R2、R3And R4Each may be C1-C20Alkyl (including C)1-C20Straight chain alkyl of (2) and C3-C20Branched alkyl of) or C6-C12Aryl group of (1). Said C is1-C20Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, methyl,One or more of ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, and n-eicosyl. Said C is6-C12Specific examples of the aryl group of (a) may include, but are not limited to, phenyl, naphthyl, methylphenyl and ethylphenyl. Preferably, R1、R2、R3And R4Each is C1-C10Alkyl (including C)1-C10Straight chain alkyl of (2) and C3-C10Branched alkyl groups of (a). Further preferably, R1、R2、R3And R4Each is C1-C6Alkyl (including C)1-C6Straight chain alkyl of (2) and C3-C6Branched alkyl groups of (a).
The amine refers to a substance in which one, two or three hydrogens in an ammonia molecule are replaced with an organic group, which may be bonded to a nitrogen atom to form a cyclic structure. The organic group may be a substituted (e.g., hydroxyl-substituted) or unsubstituted aliphatic hydrocarbon group and/or a substituted (e.g., hydroxyl-substituted) or unsubstituted aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be one or two or more of a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated aliphatic chain hydrocarbon group, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated aliphatic chain hydrocarbon group, a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated alicyclic hydrocarbon group, and a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated alicyclic hydrocarbon group. Specifically, the amine may be one or two or more of a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated aliphatic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated aliphatic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated alicyclic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated alicyclic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted heterocyclic amine, and a substituted (e.g., hydroxyl-substituted) or unsubstituted arylamine.
The unsaturated aliphatic amine refers to an aliphatic chain amine having an unsaturated group in a molecular structure, and the unsaturated group is preferably an alkenyl group (i.e., -C ═ C —). The number of the unsaturated group and the amino group may be one or two or more, respectively, and is not particularly limited.
Specific examples of the organic base according to the method of the present invention may include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, sec-butylamine, diisobutylamine, triisobutylamine, tert-butylamine, n-pentylamine, di-n-pentylamine, tri-n-pentylamine, neopentylamine, isoamylamine, diisopentylamine, triisopentylamine, tert-pentylamine, n-hexylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecyldimethylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, monoethanolamine, triethanolamine, triisopropanolamine, diethanolamine, di-n-propanolamine, tri-n-propanolamine, di-n-butanolamine, tri-n-butanolamine, di-n-pentanolamine, di-n, Dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, ethylenediamine, propylenediamine, butylenediamine, pentyldiamine, hexyldiamine, substituted or unsubstituted pyrrole, substituted or unsubstituted tetrahydropyrrole, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted quinoline, substituted or unsubstituted dihydroquinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinoline, substituted or unsubstituted pyrimidine, aniline, diphenylamine, benzidine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-toluidine, m-toluidine, p-toluidine, 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5-dimethylaniline, p-toluidine, p-tolu, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-trimethylaniline, o-ethylaniline, N-butylaniline, 2, 6-diethylaniline, cyclohexylamine, cyclopentylamine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (including various isomers thereof, such as tetra-N-propylammonium hydroxide and tetraisopropylammonium hydroxide), tetrabutylammonium hydroxide (including various isomers thereof, such as tetra-N-butylammonium hydroxide, tetra-sec-butylammonium hydroxide, tetra-isobutylammonium hydroxide and tetra-tert-butylammonium hydroxide), and tetrapentylammonium hydroxide (including various isomers thereof).
The amine is preferably a compound of formula II, a compound of formula III, and a general formula R12(NH2)2One or more of the substances shown,
in the formula II, R5、R6And R7Are each H, C1-C6Alkyl or C6-C12And R is an aryl group of5、R6And R7Not H at the same time. In the present invention, C1-C6Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl and n-hexyl. In the present invention, C6-C12Specific examples of aryl groups of (a) include, but are not limited to, phenyl, naphthyl, methylphenyl, and ethylphenyl.
In the formula III, R8、R9And R10Each is-R11OH or hydrogen, and R8、R9And R10At least one of which is-R11OH，R11Is C1-C4An alkylene group of (a). In the present invention, C1-C4Alkylene of (A) includes C1-C4Linear alkylene of (A) and (C)3-C4Specific examples thereof may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutyleneAnd a tert-butylene group.
General formula R12(NH2)2In, R12Can be C1-C6Alkylene or C6-C12An arylene group of (a). In the present invention, C1-C6Alkylene of (A) includes C1-C6Linear alkylene of (A) and (C)3-C6Specific examples thereof may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, and n-hexylene. In the present invention, C6-C12Specific examples of the arylene group of (a) include, but are not limited to, phenylene and naphthylene.
Preferably, the organic base is selected from quaternary ammonium bases.
The temperature of the aqueous dispersion during the reaction is preferably in the range of 80 to 220 ℃. When the temperature of the aqueous dispersion is within the above range, the content of oxygen atoms and/or nitrogen atoms in the raw material nanocarbon material can be effectively increased, and the structural morphology of the raw material nanocarbon material is not significantly affected. The temperature of the aqueous dispersion during the reaction is more preferably in the range of 140-180 ℃.
The duration of the reaction may be selected according to the temperature of the reaction, based on the ability to introduce a sufficient amount of oxygen and/or nitrogen atoms into the raw nanocarbon material. In general, the duration of the reaction may be in the range of 0.5 to 96 hours, preferably in the range of 2 to 72 hours, more preferably in the range of 20 to 50 hours.
The shaped body according to the first aspect of the present invention may be formed into the aqueous dispersion by various methods commonly used, for example, the raw nanocarbon material may be dispersed in water (preferably deionized water), and then the organic base may be optionally added to obtain the aqueous dispersion. In order to further improve the dispersion effect of the raw material nano carbon material and shorten the dispersion time, the raw material nano carbon material can be dispersed in water by adopting an ultrasonic oscillation method. The conditions of the ultrasonic oscillation may be conventionally selected, and in general, the frequency of the ultrasonic oscillation may be 10 to 100kHz, preferably 40 to 80kHz, and the duration of the ultrasonic oscillation may be 0.1 to 6 hours, preferably 0.5 to 2 hours. According to the process of the present invention, the organic base is preferably provided in the form of a solution (preferably an aqueous solution).
According to the molded body of the first aspect of the present invention, the content of the oxygen element and the nitrogen element in the raw material nanocarbon material is not particularly limited and may be selected conventionally. Generally, the content of the O element in the raw material nanocarbon material is not more than 1.2% by weight, preferably not more than 0.5% by weight; the content of the N element is less than 0.1 wt%, preferably not more than 0.08 wt%, more preferably not more than 0.05 wt%. The total amount (in terms of elements) of the non-metallic hetero atoms (such as phosphorus atoms and sulfur atoms) other than oxygen atoms and nitrogen atoms in the raw material nanocarbon material may be a conventional amount. Generally, the total amount of the non-metallic hetero atoms other than the oxygen atom and the nitrogen atom in the raw material nanocarbon material is not more than 0.5% by weight, preferably not more than 0.2% by weight, more preferably not more than 0.1% by weight, and further preferably not more than 0.05% by weight. The raw material nanocarbon material may further contain some metal elements depending on the source, for example, metal elements derived from a catalyst used in the preparation of the raw material nanocarbon material. The content (in terms of element) of the metal element in the raw nanocarbon material is generally 2.5 wt% or less, preferably 2 wt% or less, more preferably 1 wt% or less, and still more preferably 0.5 wt% or less.
According to the molded body of the first aspect of the present invention, the raw material nanocarbon material may be pretreated (e.g., washed) by a method commonly used in the art before use to remove some impurities on the surface of the raw material nanocarbon material; or may be used without pretreatment. In the preparation examples disclosed in the present invention, the raw material nanocarbon material was not pretreated before use.
According to the molded body of the first aspect of the present invention, the raw nanocarbon material may be, but is not limited to, one or a combination of two or more of carbon nanotubes, graphene, nanodiamonds, thin-layer graphites, nanocarbon particles, nanocarbon fibers, and fullerenes. The carbon nanotube can be one or the combination of more than two of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube. Preferably, the raw material nanocarbon material is a carbon nanotube, more preferably a multiwall carbon nanotube.
In a preferred embodiment of the molded body according to the first aspect of the present invention, the raw nanocarbon material is a multi-walled carbon nanotube, and the specific surface area of the multi-walled carbon nanotube may be 50 to 500m2A/g, preferably from 80 to 300m2(ii)/g, more preferably 100-260m2(ii)/g, more preferably 120-190m2/g。
When the raw material nano carbon material is the multi-walled carbon nanotube, the weight loss rate of the multi-walled carbon nanotube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800May be in the range of 0.01 to 0.5, preferably in the range of 0.02 to 0.4.
According to the molded article of the first aspect of the present invention, the reaction is carried out in a closed vessel. The reaction may be carried out under autogenous pressure (i.e., without additional application of pressure) or under pressurized conditions. Preferably, the reaction is carried out under autogenous pressure. The closed container can be a common reactor capable of realizing sealing and heating, such as a high-pressure reaction kettle.
The molded body according to the first aspect of the present invention may further comprise a step of separating solid matter from the mixture obtained by the reaction and then drying the separated solid matter to obtain a nanocarbon material. The solid matter can be separated from the mixture obtained by the reaction by a conventional solid-liquid separation method such as one or a combination of two or more of centrifugation, filtration and decantation. The drying conditions may be chosen conventionally, so as to be able to remove volatile substances from the separated solid material. In general, the drying may be carried out at a temperature of from 50 to 400 ℃, preferably from 80 to 180 ℃. The duration of the drying may be selected according to the temperature and manner of drying. Generally, the duration of the drying may be no more than 48 hours, preferably 4 to 24 hours, more preferably 6 to 12 hours. The drying may be performed under normal pressure (i.e., 1 atm), or under reduced pressure. From the viewpoint of further improving the efficiency of drying, the drying is preferably performed under reduced pressure. Spray drying or the like can also be employed without a step of separating solid substances from the mixture, in which case the drying can be carried out at a temperature of 120-400 ℃, preferably at a temperature of 150-350 ℃, more preferably at a temperature of 180-300 ℃, and the duration of the drying can be selected according to the degree of drying, such as not more than 0.5 hour, preferably not more than 0.2 hour, more preferably not more than 0.1 hour.
The nanocarbon material molded body according to the present invention further contains a heat-resistant inorganic oxide for binding and molding the nanocarbon material. In the present invention, the term "heat-resistant inorganic oxide" means an inorganic oxygen-containing compound having a decomposition temperature of not less than 300 ℃ under an oxygen or oxygen-containing atmosphere (e.g., a decomposition temperature of 300-1000 ℃).
The heat-resistant inorganic oxide is preferably one or more of alumina, silica and titania. In one example, the heat-resistant inorganic oxide is alumina, and the nanocarbon material molding according to this example can achieve a higher conversion rate of raw materials.
In a preferred embodiment, at least a portion of the refractory inorganic oxide is silica, and the nanocarbon material shaped body according to this preferred embodiment can achieve a better balance between feedstock conversion and product selectivity when used as a catalyst for a hydrocarbon dehydrogenation reaction. In the preferred embodiment, the content of the silicon oxide may be 10 to 100% by weight, preferably 20 to 99% by weight, and more preferably 50 to 99% by weight, based on the total amount of the heat-resistant inorganic oxides, and the content of the heat-resistant inorganic oxides other than silicon oxide may be 0 to 90% by weight, preferably 1 to 80% by weight, and more preferably 1 to 50% by weight. In the preferred embodiment, specific examples of the heat-resistant inorganic oxide other than silicon oxide may include, but are not limited to, aluminum oxide and/or titanium oxide. As an example of the preferred embodiment, the heat-resistant inorganic oxide other than silicon oxide is titanium oxide.
According to the nanocarbon material molded body of the present invention, the content of the nanocarbon material can be varied in a wide range, and still the nanocarbon material molded body has high strength. In general, the content of the nanocarbon material may be 6 to 94% by weight, preferably 8 to 92% by weight, more preferably 10 to 90% by weight, still more preferably 20 to 90% by weight, still more preferably 40 to 90% by weight, and particularly preferably 65 to 90% by weight, and the content of the heat-resistant inorganic oxide may be 6 to 94% by weight, preferably 8 to 92% by weight, more preferably 10 to 90% by weight, still more preferably 10 to 80% by weight, still more preferably 10 to 60% by weight, and particularly preferably 10 to 35% by weight, based on the total amount of the nanocarbon material molded body. The composition of the shaped bodies can be determined by X-ray fluorescence spectroscopy. In the examples disclosed in the present invention, the composition of the molded article calculated from the charged amount was substantially the same as the composition of the molded article measured by X-ray fluorescence spectrometry with an error of within 5%.
According to a second aspect of the present invention, there is provided a nanocarbon material molded body containing a nanocarbon material and a heat-resistant inorganic oxide for binding and molding the nanocarbon material.
According to the nanocarbon material molded body of the present invention, the nanocarbon material contains an O element and optionally an N element (hereinafter, sometimes referred to as a heteroatom-containing nanocarbon material).
The contents of the O element and the optional N element in the nano carbon material can be selected according to the source of the nano carbon material and can also be selected according to the specific application occasion of the nano carbon material forming body. In general, the content of the O element may be 0.5 to 6 wt%, the content of the N element may be 0 to 2 wt%, and the content of the C element may be 92 to 99.5 wt% based on the total amount of the nanocarbon material and in terms of elements.
In the invention, the content of each element is measured by adopting an X-ray photoelectron spectroscopy. The samples were dried at a temperature of 150 ℃ for 3 hours in a helium atmosphere before testing. Wherein the X-ray photoelectron spectroscopy is performed by Thermo ScientificThe test is carried out on an ESCALB 250 type X-ray photoelectron spectrometer equipped with Thermo Avantage V5.926 software, an excitation source is monochromatized Al K α X-ray, the energy is 1486.6eV, the power is 150W, the transmission energy used by narrow scanning is 30eV, and the basic vacuum during the analysis test is 6.5X 10-10mbar, electron binding energy was corrected for the C1s peak (284.0eV) of elemental carbon, data processed on Thermo Avantage software, and quantified in the analytical module using the sensitivity factor method.
In one embodiment, when the content of the N element in the nanocarbon material is less than 0.1 wt%, the content of O may be 0.5 to 5.8 wt%, preferably 3 to 5.5 wt%, more preferably 4.5 to 5.5 wt%, based on the total amount of the nanocarbon material and calculated as the element; the content of the element C may be 94.2 to 99.5% by weight, preferably 94.5 to 97% by weight, more preferably 94.5 to 95.5% by weight.
In a more preferred embodiment, the nanocarbon material preferably contains an element N, which can further improve catalytic performance as a catalyst for a hydrocarbon dehydrogenation reaction. More preferably, the content of the O element may be 1.3 to 6 wt%, preferably 2 to 6 wt%, more preferably 4 to 6 wt%, calculated as element, based on the total amount of the nanocarbon material; the content of the N element may be 0.2 to 1.8% by weight, preferably 0.5 to 1.8% by weight, more preferably 1 to 1.5% by weight; the content of the element C may be 92.2 to 98.5% by weight, preferably 92.2 to 97.5% by weight, more preferably 92.5 to 95% by weight.
According to the molded body of the second aspect of the present invention, in the nanocarbon material, the amount of the O element (i.e., C ═ O) determined by the peak in the X-ray photoelectron spectrum in the range of 531.0 to 532.5eV is IO cThe amount of O element (i.e., CO) determined from a peak in the range of 532.6 to 533.5eV in the X-ray photoelectron spectrum is IO e，IO c/IO eMay be in the range of 0.1-0.8. When the content of N element in the nanocarbon material is less than 0.1 wt%, IO c/IO ePreferably in the range of 0.1 to 0.7, more preferably in the range of 0.4 to 0.7, and further preferably in the range of 0.55 to 0.65Inside the enclosure. When the content of N element in the nanocarbon material is 0.1 wt% or more, IO c/IO ePreferably in the range of 0.1 to 0.9, more preferably in the range of 0.35 to 0.85, and further preferably in the range of 0.5 to 0.8.
In the present invention, the area A of the peak of O1s spectrum in the X-ray photoelectron spectrumO 1Determining the total amount of O element, dividing the peak of O1s in X-ray photoelectron spectrum into two groups, namely the peak in 531.0-532.5eV (corresponding to C ═ O species) and the peak in 532.6-533.5eV (corresponding to C-O species), and recording the area of the peak in 531.0-532.5eV as AO 2The area of the peak in the range of 532.6 to 533.5eV is designated as AO 3，IO c/IO e＝AO 2/AO 3。
According to the molded article of the second aspect of the present invention, the content of the C element in the nanocarbon material, which is determined by a peak in the range of 284.7 to 284.9eV in the X-ray photoelectron spectrum, may be 20% by weight or more, preferably 40% by weight or more, more preferably 50% by weight or more, and further preferably 70% by weight or more, based on the total amount of the C element determined by the X-ray photoelectron spectrum. The content of the C element determined from a peak in the range of 284.7-284.9eV in the X-ray photoelectron spectrum may be 95% by weight or less, preferably 90% by weight or less. The total content of the C element determined from a peak in the range of 286.0-288.8eV in the X-ray photoelectron spectrum may be 5% by weight or more, preferably 10% by weight or more. The total content of the C element determined from a peak in the range of 286.0 to 288.8eV in the X-ray photoelectron spectrum may be 80% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less, further preferably 30% by weight or less.
In the present invention, the area A of the peak of C1s spectrum in the X-ray photoelectron spectrumC 1The total amount of C element was determined, and the peak of C1s in the X-ray photoelectron spectrum was divided into two groups, i.e., a peak in the range of 284.7-284.9eV (corresponding to a graphitic carbon species) and a peak in the range of 286.0-288.8eV (corresponding to a non-graphitic carbon species)Type carbon species), the area of the spectral peak in the range of 284.7-284.9eV is designated as AC 2The area of a peak in the range of 286.0-288.8eV is designated as AC 3The content of C element determined from a peak in the range of 284.7-284.9eV in X-ray photoelectron spectrum (A)C 2/AC 1Total content of C element determined from peak in range of 286.0-288.8eV in X-ray photoelectron spectrumC 3/AC 1。
According to the molded article of the second aspect of the present invention, the amount of C element in the nanocarbon material, which is determined by a peak in the range of 288.6-288.8eV in an X-ray photoelectron spectrum, is IC cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is IC e，IC c/IC eGenerally in the range of 0.1 to 1.
When the content of N element in the nanocarbon material is less than 0.1 wt%, IC c/IC ePreferably in the range of 0.1 to 0.9, more preferably in the range of 0.3 to 0.9, still more preferably in the range of 0.35 to 0.8, and still more preferably in the range of 0.5 to 0.7. When the content of N element in the nanocarbon material is 0.1 wt% or more, IC c/IC ePreferably in the range of 0.1 to 0.98, preferably in the range of 0.3 to 0.98, more preferably in the range of 0.45 to 0.6.
In the present invention, peaks in the X-ray photoelectron spectrum in the range of 286.0-288.8eV (corresponding to non-graphitic carbon species) are further divided into two groups of peaks, i.e., peaks in the range of 286.0-286.2eV (corresponding to hydroxyl and ether-type carbon species) and peaks in the range of 288.6-288.8eV (corresponding to carboxyl, anhydride and ester-type carbon species), and the area of the peaks in the range of 286.0-286.2eV is designated as AC 4The area of a peak in the range of 288.6-288.8eV is designated as AC 5，IC c/IC e＝AC 5/AC 4。
According to the second aspect of the inventionIn the molded article according to the aspect, when the nanocarbon material further contains N element, the total amount of N element in the nanocarbon material is I as determined by X-ray photoelectron spectroscopyN tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is IN c，IN c/IN tMay be in the range of 0.7 to 1, preferably in the range of 0.8 to 0.95. The N element content determined by the peak in the range of 400.6-401.5eV in the X-ray photoelectron spectrum is low or even free. Generally, the amount of N element determined by a peak in the range of 400.6 to 401.5eV in the X-ray photoelectron spectrum is IN g，IN g/IN tIs not higher than 0.35, and is generally in the range of 0.05 to 0.2.
In the present invention, the total amount A of N element is determined from the area of the peak of N1s in the X-ray photoelectron spectrumN 1The peaks in the X-ray photoelectron spectrum of N1s were divided into two groups, i.e., a peak in the range of 400.6 to 401.5eV (corresponding to a graphite-type nitrogen species) and a peak in the range of 398.5 to 400.1eV (a nitrogen species other than graphite-type nitrogen), the respective areas of the two groups were determined, and the area of the peak in the range of 400.6 to 401.5eV was designated as AN 2The area of the peak in the range of 398.5-400.1eV is designated as AN 3，IN c/IN t＝AN 3/AN 1，IN g/IN t＝AN 2/AN 1When the obtained ratio is 0.01 or less, the species is considered to be absent, and the content of the species is noted as 0.
In the present invention, the position of each peak is determined by the binding energy corresponding to the peak top of the peak, and the peak determined by the above-mentioned range refers to a peak having the binding energy corresponding to the peak top within the range, and may include one peak or two or more peaks within the range. For example: the peak in the range of 398.5-400.1eV means all peaks having a binding energy in the range of 398.5-400.1eV corresponding to the peak top.
According to the nanocarbon material molded body of the present invention, the nanocarbon material may exist in various forms, and specifically, but not limited to, one or a combination of two or more of carbon nanotubes, graphene, thin graphite, nanocarbon particles, nanocarbon fibers, nanodiamonds, and fullerenes. The carbon nanotube can be one or the combination of more than two of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube. According to the nanocarbon material molded body, the nanocarbon material is preferably a multiwalled carbon nanotube.
According to the nanocarbon material molded body of the present invention, the specific surface area of the multi-walled carbon nanotube is preferably 50 to 500m2In this way, the catalytic properties of the shaped bodies, in particular as catalysts for the dehydrogenation of hydrocarbon materials, can be further improved. The specific surface area of the multi-wall carbon nano-tube is more preferably 80-300m2(ii)/g, more preferably 100-2/g, more preferably 130-2(ii) in terms of/g. In the present invention, the specific surface area is measured by a nitrogen adsorption BET method.
According to the nano carbon material forming body, the weight loss rate of the multi-wall carbon nano tube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800Preferably in the range of 0.01 to 0.5, which enables better catalytic performance, particularly when used as a catalyst for dehydrogenation of hydrocarbons. w is a500/w800More preferably in the range of 0.02 to 0.4, still more preferably in the range of 0.05 to 0.15. In the present invention, w800＝W800－W400，w500＝W500－W400，W400The mass loss rate, W, measured at a temperature of 400 deg.C800The mass loss rate, W, measured at a temperature of 800 deg.C500Is the mass loss rate determined at a temperature of 500 ℃; the weight loss rate is measured in an air atmosphere by adopting a thermogravimetric analyzer, the test starting temperature is 25 ℃, and the heating rate is 10 ℃/min; the samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing.
According to the nanocarbon material molded body of the present invention, the content of non-metallic hetero atoms other than oxygen atoms and nitrogen atoms, such as sulfur atoms and phosphorus atoms, in the nanocarbon material may be a conventional content. Generally, according to the nanocarbon material molded body of the present invention, the total amount of non-metallic hetero atoms (such as sulfur atoms and phosphorus atoms) other than oxygen atoms and nitrogen atoms in the nanocarbon material may be 0.5% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less, and further preferably 0.05% by weight or less. According to the nanocarbon material molded body of the present invention, the nanocarbon material may contain other metal atoms in addition to the metal elements selected from the group consisting of the metal elements, and the other metal atoms may be derived from a catalyst used in the production of the nanocarbon material, for example. The content of the other metal atom is generally 2.5% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight or less, and particularly preferably 0.2% by weight or less.
The molded article according to the second aspect of the present invention further contains a heat-resistant inorganic oxide for binding and molding the nanocarbon material. The kind and content of the refractory inorganic oxide are the same as those of the refractory inorganic oxide described in the first aspect of the present invention, and are not described in detail herein.
The nanocarbon material molded body according to the first and second aspects of the present invention may have various shapes such as a spherical shape and a strip shape as needed.
The nanocarbon material molded body according to the first and second aspects of the present invention has high crushing strength. Generally, the nanocarbon material shaped body according to the invention may have a radial crush strength of 4N/mm or more, typically 5N/mm or more. Specifically, the nanocarbon material shaped body according to the first and second aspects of the present invention has a radial crush strength of 5 to 25N/mm, preferably 6 to 25N/mm, and more preferably 10 to 25N/mm. In the present invention, the radial crush strength was measured by a method specified in RIPP 25-90 described in "analytical methods for petrochemical industry" (first edition, 1990, ed., Yankee edition, and edited by Yankee corporation).
The nanocarbon material molded body according to the first and second aspects of the present invention has a high porosity. Generally, the porosity of the nanocarbon material shaped body according to the invention may be 5% or more, even 10% or more, for example, may be in the range of 5 to 50%, preferably in the range of 10 to 30%, more preferably in the range of 12 to 25%. In the present invention, the porosity is a ratio of a sum of volumes of all pore spaces in the nanocarbon material molded body to a volume of the nanocarbon material molded body, and may be also referred to as a porosity of the nanocarbon material molded body, and is measured by a mercury intrusion method (see document "research on porosity of graphite porous material", "lubrication and sealing", "2010, 35 (10): 99-101) in percentage).
According to a third aspect of the present invention, there is provided a method for producing a nanocarbon material shaped body, comprising mixing a nanocarbon material with a binder source, shaping the obtained mixture to obtain a shaped body, drying and optionally firing the shaped body.
According to the method of the third aspect of the invention, the binder source is selected from the group consisting of refractory inorganic oxides and/or precursors of refractory inorganic oxides. The heat-resistant inorganic oxide is preferably one or more of alumina, silica and titania. In one example, the heat-resistant inorganic oxide is alumina, and the nanocarbon material molding according to this example can achieve a higher conversion rate of raw materials.
In a preferred embodiment, at least a portion of the refractory inorganic oxide is silica, and the nanocarbon material shaped body prepared according to this preferred embodiment can achieve a better balance between feedstock conversion and product selectivity when used as a catalyst for a hydrocarbon dehydrogenation reaction. In the preferred embodiment, the content of the silicon oxide may be 10 to 100% by weight, preferably 20 to 99% by weight, and more preferably 50 to 99% by weight, based on the total amount of the heat-resistant inorganic oxides, and the content of the heat-resistant inorganic oxides other than silicon oxide may be 0 to 90% by weight, preferably 1 to 80% by weight, and more preferably 1 to 50% by weight. In the preferred embodiment, specific examples of the heat-resistant inorganic oxide other than silicon oxide may include, but are not limited to, aluminum oxide and/or titanium oxide. As an example of the preferred embodiment, the heat-resistant inorganic oxide other than silicon oxide is titanium oxide.
The refractory inorganic oxide may be provided in various forms as is common, for example, in the form of a sol (e.g., silica sol, titanium sol, aluminum sol). The precursor of the heat-resistant inorganic oxide may be selected according to the kind of the intended heat-resistant inorganic oxide.
For example, when the refractory inorganic oxide is alumina, the precursor of the refractory inorganic oxide may be a substance capable of being converted into alumina, such as a substance capable of forming alumina by hydrolytic condensation reaction and/or calcination, for example, organic aluminum salts and inorganic aluminum salts, specific examples of which may include, but are not limited to, hydrated alumina (such as pseudo-boehmite), aluminum hydroxide, aluminum sulfate, sodium metaaluminate, aluminum chloride, aluminum nitrate and C1-C10And one or more of organic aluminum salts (e.g., aluminum isopropoxide, aluminum isobutoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, and aluminum isooctanolate) of (a).
For another example, when the heat-resistant inorganic oxide is silicon oxide, the precursor of the heat-resistant inorganic oxide may be a substance that can be converted into silicon oxide, such as a substance that can form silicon oxide by a hydrolytic condensation reaction and/or firing, and specific examples thereof may include, but are not limited to, organosilicon compounds that can undergo a hydrolytic condensation reaction. The organosilicon compound capable of undergoing a hydrolytic condensation reaction may be any of various conventional substances capable of forming silicon oxide by a hydrolytic condensation reaction. As an example, the organosilicon compound capable of undergoing hydrolytic condensation reaction may be one or more than two of the compounds represented by formula IV:
in the formula IV, R13、R14、R15And R16Each is C1-C4Alkyl group of (1). Said C is1-C4Alkyl of (2) includes C1-C4Straight chain alkyl of (2) and C3-C4Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. Preferably, the organic silicon source is selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, isopropyl orthosilicate, and n-butyl orthosilicate.
For another example, when the heat-resistant inorganic oxide is titanium oxide, the precursor of the heat-resistant inorganic oxide may be an organic titanate and/or an inorganic titanium salt, and specific examples thereof may include, but are not limited to, TiCl4、Ti(SO4)2、TiOCl2One or more of titanium hydroxide, titanium nitrate, titanium phosphate, titanium alkoxide, and organic titanate (e.g., one or more of tetraisopropyl titanate, tetra-n-propyl titanate, tetrabutyl titanate, and tetraethyl titanate).
In an embodiment of the method according to the third aspect of the invention, the binder source is selected from refractory inorganic oxides, such as refractory inorganic oxides provided in the form of a sol. In this embodiment, the nanocarbon material and the binder source may be uniformly mixed and then molded. In another embodiment, at least a portion of the binder source is a precursor to a refractory inorganic oxide. In this embodiment, after mixing the nanocarbon material with the binder source, treatment is performed according to the kind of the binder source to convert the precursor of the heat-resistant inorganic oxide in the binder source into the heat-resistant inorganic oxide.
According to the method of the third aspect of the present invention, the mixture preferably further contains at least one base, which can further improve the catalytic activity of the finally prepared nanocarbon material shaped body when used as a catalyst for a dehydrogenation reaction of hydrocarbons. The base may be an organic base and/or an inorganic base. The inorganic base may be one or more of ammonia, an alkali whose cation is an alkali metal, and an alkali whose cation is an alkaline earth metal. The organic alkali can be one or more than two of urea, amine, alcohol amine and quaternary ammonium alkali. The organic base may be selected from the organic bases described in the first aspect of the invention and will not be described in detail herein.
Preferably, the base is an organic base, which can further improve the catalytic activity of the finally prepared nanocarbon material molding as a catalyst for dehydrogenation reaction of hydrocarbon. More preferably, the base is a template agent for synthesizing the titanium silicalite molecular sieve, such as quaternary ammonium base shown in formula I, so that the prepared nano carbon material formed body has higher crushing strength and shows further improved catalytic activity when being used as a catalyst for hydrocarbon dehydrogenation reaction.
The amount of the base may be selected according to the amount of the binder source. Generally, the molar ratio of the base to the binder source may be from 0.1 to 10: 1, preferably 0.15 to 5: 1, the binder source is calculated by oxide.
According to the method of the third aspect of the present invention, the nanocarbon material may be uniformly mixed with the binder source and optionally the alkali using various dispersion media. Preferably, the dispersion medium is water. The amount of the dispersion medium is such that the nanocarbon material, the binder source and optionally the alkali can be mixed uniformly. As an example, when the dispersion medium is water, the molar ratio of water to the binder source may be 5 to 200: 1, preferably 10 to 150: 1, the binder source is calculated by oxide.
The inventor of the present invention finds in the research process that the molecular sieve preparation solution generated in the molecular sieve preparation process usually contains the binder source and the alkali required in the present invention, and also contains water, and after the molecular sieve preparation solution is mixed with the nanocarbon material, one, two or three of the water, the binder source and the alkali are optionally supplemented, so that not only can the nanocarbon material be molded, but also the prepared nanocarbon material shows higher crushing resistance strength, and simultaneously still shows better catalytic activity, and in addition, the reuse of the waste liquid in the molecular sieve preparation process is realized.
The molecular sieve preparation solution can be any common molecular sieve preparation solution capable of providing the binder source and optional base required by the invention. Preferably, the molecular sieve preparation liquid is a mixed liquid of one or more of a crystallization mother liquid of a silicon-containing molecular sieve and a rearrangement modified mother liquid of the silicon-containing molecular sieve. The silicon-containing molecular sieve can be one or more than two of an all-silicon molecular sieve, a silicon molecular sieve containing heteroatom (such as titanium-silicon molecular sieve) and a silicon-aluminum molecular sieve. The crystallization mother liquor refers to a liquid obtained by performing solid-liquid separation on a mixture obtained by hydrothermal crystallization when a molecular sieve is prepared by hydrothermal crystallization, namely a liquid mixture remaining after a formed molecular sieve is separated from the mixture obtained by hydrothermal crystallization, and is also called as synthesis mother liquor, filtered waste liquor or filtered stock liquor. The rearrangement modified mother liquor refers to a liquid obtained by performing solid-liquid separation on a mixture obtained after hydrothermal modification rearrangement when the modified molecular sieve is prepared by hydrothermal modification rearrangement, namely a liquid mixture remaining after the molecular sieve is separated from the mixture obtained by hydrothermal modification rearrangement, and is also called as rearrangement mother liquor, modified mother liquor, rearrangement filtration waste liquor, modified filtration raw liquor or rearrangement filtration raw liquor. The crystallization mother liquor and the rearrangement liquor can be directly mixed with the nano-carbon material, and can also be mixed with the nano-carbon material after being concentrated or diluted according to the needs, so that the dosage of the binder source, the alkali and the water can meet the requirements, for example, the proportion requirements are met.
More preferably, the solution for preparing the silicon-containing molecular sieve is one or more of a crystallization mother liquor of the silicon molecular sieve (e.g. a crystallization mother liquor of the all-silicon molecular sieve), a crystallization mother liquor of the heteroatom-containing molecular sieve (e.g. a crystallization mother liquor of the titanium-silicon molecular sieve), a crystallization mother liquor of the silicon-aluminum molecular sieve, and a modified heavy liquid discharge of the silicon-containing molecular sieve (e.g. a heavy liquid discharge of the all-silicon molecular sieve and the titanium-silicon molecular sieve).
The specific composition of the crystallization mother liquor and the heavy liquor is not particularly limited, so long as a binder source and, optionally, a base are provided. As an example, in the crystallization mother liquor of the silicon-containing molecular sieve, SiO is used2The content of elemental silicon is generally 0.05 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 1 to 4% by weight; the content of the base is generally 0.05 to 15% by weight, preferably 0.1 to 15% by weight, more preferably 1.5 to 14% by weight. As another example, in heavy liquid discharge of titanium silicalite, SiO is used2The content of the silicon element is generally 0.01 to 10% by weight, and preferably0.02 to 5 wt%, more preferably 0.5 to 2 wt%; with TiO2The content of titanium element is generally 0.0001 to 0.2% by weight, preferably 0.001 to 0.1% by weight, more preferably 0.01 to 0.08% by weight; the content of the base is generally 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 1 to 4% by weight. As an example, in the crystallization mother liquor of the silicon-aluminum molecular sieve, SiO is used2The content of elemental silicon is generally 0.05 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 1 to 4% by weight; with Al2O3The content of the aluminum element is generally 0.01 to 5% by weight, preferably 0.05 to 2% by weight, and more preferably 0.1 to 0.5% by weight, and the content of the alkali is generally 0.05 to 15% by weight, preferably 0.1 to 14% by weight, and more preferably 8 to 13% by weight.
According to the method of the third aspect of the present invention, in a preferred embodiment, the mixture is subjected to hydrothermal treatment (i.e., the mixture obtained by the hydrothermal treatment is subjected to molding) before the mixture is subjected to molding, which can further improve the catalytic activity of the finally produced nanocarbon material molded body when used as a catalyst for a dehydrogenation reaction of hydrocarbons. In this preferred embodiment, the nanocarbon material, the binder source and optionally the base may be dispersed in water and the aqueous dispersion subjected to a hydrothermal treatment.
In this preferred embodiment, the conditions of the hydrothermal treatment are not particularly limited, and the hydrothermal treatment may be performed at a high temperature in a closed environment. Specifically, the temperature of the hydrothermal treatment may be 100-. The time for the hydrothermal treatment may be selected depending on the temperature at which the hydrothermal treatment is carried out, and may be generally 0.5 to 24 hours, preferably 6 to 12 hours. The hydrothermal treatment may be performed under autogenous pressure (i.e., no additional pressure is applied during the hydrothermal treatment), or may be performed under additional applied pressure. Preferably, the hydrothermal treatment is carried out under autogenous pressure.
According to the method of the third aspect of the present invention, the amount of the binder source may be selected according to the content of the binder in the desired nanocarbon material shaped body. Generally, the binder source is used in an amount such that the nanocarbon material content in the finally produced molded article may be 5 wt% or more (e.g., 6 wt% or more), preferably 10 wt% or more, more preferably 50 wt% or more, further preferably 60 wt% or more, further preferably 70 wt% or more, further preferably 75 wt% or more, and particularly preferably 80 wt% or more, and the nanocarbon material content is generally 95 wt% or less, preferably 94 wt% or less, and more preferably 90 wt% or less. In one example, the nanocarbon material may be contained in an amount of 5 to 95% by weight, preferably 6 to 94% by weight, more preferably 8 to 92% by weight, still more preferably 10 to 90% by weight, still more preferably 20 to 90% by weight, particularly preferably 40 to 90% by weight, and still more preferably 70 to 90% by weight, based on the total amount of the nanocarbon material molded body, and the heat-resistant inorganic oxide may be contained in an amount of 5 to 95% by weight, preferably 6 to 94% by weight, more preferably 8 to 92% by weight, still more preferably 10 to 90% by weight, still more preferably 10 to 80% by weight, particularly preferably 10 to 60% by weight, and still more preferably 10 to 30% by weight. When subjected to hydrothermal treatment prior to molding, higher strength can be obtained even at a lower binder content. Generally, when the hydrothermal treatment is performed before the molding, the content of the nanocarbon material is preferably 75 to 95% by weight, more preferably 80 to 95% by weight, and the content of the heat-resistant inorganic oxide is preferably 5 to 25% by weight, more preferably 5 to 20% by weight, based on the total amount of the molded body.
According to the method of the third aspect of the present invention, the mixture containing the nanocarbon material and the binder source may be shaped by a conventional method to obtain a shaped article. As an example, the mixture may be shaped by kneading and/or extrusion. The molding may have various shapes such as a spherical shape and a strip shape.
According to the method of the third aspect of the present invention, the shaped product may be dried under conventional conditions to remove volatile substances from the shaped product. Generally, the drying may be carried out at a temperature of from 50 to 200 deg.C, preferably at a temperature of from 80 to 180 deg.C, more preferably at a temperature of from 120 to 180 deg.C. The duration of the drying may be selected depending on the temperature of the drying, and may be generally not more than 48 hours, preferably 3 to 24 hours, more preferably 5 to 15 hours.
The dried shaped product may be calcined or not. The conditions for the calcination in the present invention are not particularly limited, and the calcination may be carried out under conventional conditions. Generally, the calcination may be carried out at a temperature of 300-800 deg.C, preferably no higher than 650 deg.C. The calcination may be performed in an oxygen-containing atmosphere (e.g., air, oxygen) or in an oxygen-free atmosphere (e.g., nitrogen, a group zero gas). When the calcination is carried out in an oxygen-containing atmosphere, the calcination is preferably carried out at a temperature of 300-500 deg.C, more preferably at a temperature of not higher than 450 deg.C. When the calcination is carried out in an oxygen-free atmosphere, the calcination is preferably carried out at a temperature of 400-800 deg.C, more preferably at a temperature of not higher than 750 deg.C. The duration of the calcination may be from 1 to 12 hours, preferably from 2 to 4 hours.
According to the method of the third aspect of the present invention, nanocarbon materials of various sources can be treated, and the nanocarbon materials can be non-surface-treated nanocarbon materials or surface-treated nanocarbon materials. In the present invention, the surface of the nanocarbon material is detected by X-ray photoelectron spectroscopy, and if the total content of elements other than C in the surface elements of the nanocarbon material detected is 2 wt% or less, the nanocarbon material is regarded as a nanocarbon material without surface treatment, whereas the nanocarbon material is regarded as a nanocarbon material with surface treatment.
In one embodiment, the nanocarbon material is a nanocarbon material that has not been surface treated. In this embodiment, before the mixture is formed, the mixture is preferably subjected to hydrothermal treatment in a closed container, so that not only the strength of the finally prepared formed body can be remarkably improved, but also the catalytic performance of the finally prepared formed body can be remarkably improved. More preferably, the binder source and the optional alkali source are from a molecular sieve preparation solution, and the nano carbon material without modified surface treatment is subjected to hydrothermal treatment in the molecular sieve preparation solutionThe catalytic performance of the finally prepared shaped body in the dehydrogenation reaction of hydrocarbon can be further improved. In this embodiment, the nanocarbon material may exist in various forms, and specifically, may be, but not limited to, one or a combination of two or more of carbon nanotubes, graphene, thin graphite, nanocarbon particles, nanocarbon fibers, nanodiamonds, and fullerenes. The carbon nanotube can be one or the combination of more than two of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube, and is preferably a multi-walled carbon nanotube. The specific surface area of the multi-walled carbon nanotube can be 50-500m2A/g, preferably from 80 to 300m2A/g, more preferably 90 to 250m2(ii) in terms of/g. The weight loss rate of the multi-walled carbon nano-tube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800Preferably in the range of 0.01-0.5. As an example, the nanocarbon material without surface treatment may be a raw nanocarbon material in the molded body according to the second aspect of the invention.
In another embodiment, the nanocarbon material is a surface treated nanocarbon material, which contains an element O, and optionally an element N, as determined by X-ray photoelectron spectroscopy.
Specifically, the surface-treated nanocarbon material may be a nanocarbon material in the molded body according to the first aspect of the present invention and/or a nanocarbon material in the molded body according to the second aspect of the present invention.
According to a fourth aspect of the present invention, there is provided a nanocarbon material molded body produced by the method according to the third aspect of the present invention.
The nanocarbon material molded body according to the fourth aspect of the present invention has high crushing strength. Generally, the nanocarbon material shaped body according to the invention may have a radial crush strength of 4N/mm or more, typically 5N/mm or more. Specifically, the nanocarbon material shaped body according to the first and second aspects of the present invention has a radial crush strength of 5 to 25N/mm, preferably 6 to 25N/mm, and more preferably 10 to 25N/mm. The nanocarbon material molded body according to the fourth aspect of the present invention has a high porosity. Generally, the porosity of the nanocarbon material shaped body according to the fourth aspect of the present invention may be 5% or more, or even 10% or more, for example, may be in the range of 5 to 50%, preferably in the range of 10 to 30%, and more preferably in the range of 12 to 25%.
According to a fifth aspect of the present invention, there is provided a use of the nanocarbon material shaped body according to the first, second or fourth aspect of the present invention as a catalyst for dehydrogenation reaction of hydrocarbon. The dehydrogenation reaction may be carried out in the presence or absence of oxygen. Preferably, the dehydrogenation reaction is carried out in the presence of oxygen, which results in a better catalytic effect. The type of hydrocarbon and the specific conditions of the dehydrogenation reaction will be described in detail below and will not be described in detail here.
According to a sixth aspect of the present invention, there is provided a hydrocarbon dehydrogenation reaction method comprising contacting a hydrocarbon with the nanocarbon material shaped body according to the first, second or fourth aspect of the present invention under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen. The nanocarbon material molded body according to the present invention can be used as it is as a catalyst, or can be used as a catalyst after being crushed as needed.
The hydrocarbon dehydrogenation reaction process according to the present invention can dehydrogenate various types of hydrocarbons to obtain unsaturated hydrocarbons such as olefins. The process according to the invention is particularly suitable for dehydrogenating alkanes, thereby obtaining alkenes. The hydrocarbon is preferably an alkane, such as C2-C12Of (a) an alkane. Specifically, the hydrocarbon may be, but is not limited to, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2, 3-dimethylbutane, cyclohexane, methylcyclopentane, n-heptane, 2-methylhexane, 3-methylhexane, 2-ethylpentane, 3-ethylpentane, 2, 3-dimethylpentane, 2, 4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,3-dimethylhexane, 2, 4-dimethylhexane, 2, 5-dimethylhexane, 3-ethylhexane, 2, 3-trimethylpentane, 2,3, 3-trimethylpentane, 2,4, 4-trimethylpentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2, 3-dimethylheptane, 2, 4-dimethylheptane, 3-ethylheptane, 4-ethylheptane, 2,3, 4-trimethylhexane, 2,3, 5-trimethylhexane, 2,4, 5-trimethylhexane, 2, 3-trimethylhexane, 2, 4-trimethylhexane, 2, 5-trimethylhexane, 2,3, 3-trimethylhexane, 2,4, 4-trimethylhexane, 2-methyl-3-ethylhexane, 2-methyl-4-ethylhexane, 3-methyl-3-ethylhexane, 3-methyl-4-ethylhexane, 3, 3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, i-propylcyclohexane, trimethylcyclohexane (including various isomers of trimethylcyclohexane, such as 1,2, 3-trimethylcyclohexane, 1,2, 4-trimethylcyclohexane, 1,2, 5-trimethylcyclohexane, 1,3, 5-trimethylcyclohexane), N-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2, 3-dimethyloctane, 2, 4-dimethyloctane, 3-ethyloctane, 4-ethyloctane, 2,3, 4-trimethylheptane, 2,3, 5-trimethylheptane, 2,3, 6-trimethylheptane, 2,4, 5-trimethylheptane, 2,4, 6-trimethylheptane, 2, 3-trimethylheptane, 2, 4-trimethylheptane, 2, 5-trimethylheptane, 2, 6-trimethylheptane, 2,3, 3-trimethylheptane, 2,4, 4-trimethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 2-methyl-5-ethylheptane, 3-methyl-3-ethylheptane, 4-methyl-3-ethylheptane, 5-methyl-3-ethylheptane, 4-methyl-4-ethylheptane, 4-propylheptane, 3-diethylhexane, 3, 4-diethylhexane, 2-methyl-3, 3-diethylpentane, phenylethane, 1-phenylpropane, 2-phenylpropane, 1-phenylbutane, 2-phenylbutane, 1-phenylpentane, 2-phenylpentane and 3-phenylpentane.
The hydrocarbon is more preferably one or two or more of propane, n-butane, isobutane and phenylethane, and further preferably n-butane.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the reaction may be carried out in the presence or absence of oxygen. Preferably in the presence of oxygen. When carried out in the presence of oxygen, the amount of oxygen may be conventionally selected. Generally, the molar ratio of hydrocarbon to oxygen may be from 0.01 to 100: 1, preferably 0.1 to 10: 1, more preferably 0.2 to 5: 1, most preferably 0.5-2: 1.
according to the hydrocarbon dehydrogenation reaction method, the hydrocarbon and optional oxygen can be fed into the reactor by the carrier gas to contact and react with the heteroatom-containing nano carbon material. The carrier gas may be a commonly used gas that does not chemically interact with the reactants and the reaction product under the reaction conditions and does not undergo decomposition, such as one or a combination of two or more of nitrogen, carbon dioxide, a noble gas, and water vapor. The amount of carrier gas may be conventionally selected. Generally, the carrier gas may be present in an amount of 30 to 99.5% by volume, preferably 50 to 99% by volume, more preferably 70 to 98% by volume.
In the process for the dehydrogenation of hydrocarbons according to the present invention, the temperature of the contacting may be conventionally selected to be sufficient for the dehydrogenation of hydrocarbons to take place. Generally, the contacting may be carried out at a temperature of 200-650 ℃, preferably at a temperature of 300-600 ℃, more preferably at a temperature of 350-550 ℃, even more preferably at a temperature of 400-450 ℃ when the hydrocarbon is butane.
According to the process for the dehydrogenation of hydrocarbons according to the present invention, the contacting is preferably carried out in a fixed bed reactor.
According to the hydrocarbon dehydrogenation process of the present invention, the duration of the contacting can be selected according to the contacting temperature, such as the duration of the contacting can be expressed in terms of the weight hourly space velocity of the feed when the contacting is carried out in a fixed bed reactor. In general, the weight hourly space velocity of the feed gas may be in the range of from 1 to 50000h-1Preferably 10 to 20000h-1More preferably 50 to 10000h-1More preferably 100--1E.g. 2000-4000h-1。
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following preparations, X-ray photoelectron spectroscopy was carried out on an ESCALab model 250X-ray photoelectron spectrometer equipped with ThermoAvantage V5.926 software, manufactured by Thermo Scientific, with an excitation source of monochromated AlK α X-rays, an energy of 1486.6eV, a power of 150W, a transmission energy for narrow scanning of 30eV, and a base vacuum of 6.5X 10 during analytical testing-10mbar, electron binding energy was corrected for the C1s peak (284.0eV) of elemental carbon, data processed on Thermo Avantage software, and quantified in the analytical module using the sensitivity factor method. The samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing.
In the following preparation examples, thermogravimetric analysis was carried out on a TA5000 thermal analyzer under air atmosphere at a temperature rise rate of 10 ℃/min and at a temperature range of room temperature (25 ℃) to 1000 ℃. The samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing. The method adopts ASAP2000 type N of Micromertrics corporation in America2The physical adsorption apparatus measures the specific surface area.
The properties of the multi-walled carbon nanotubes as the raw nanocarbon material in the following preparation examples are listed in table 1 below.
TABLE 1
In the following examples and comparative examples, the contents of silicon, titanium and aluminum elements and the alkali content in the crystallization mother liquor and the heavy liquid were measured by a Perkin-Elmer 3300DV type Inductively Coupled Plasma (ICP) spectrometer.
In the following examples and comparative examples, the radial crush strength was measured according to the method specified in RIPP 25-90 described in "analytical methods for petrochemical industry" (edited by scientific Press, first edition 1990, Yankee, et al); the porosity is a ratio of a sum of volumes of all pore spaces in the nanocarbon material molded body to a volume of the nanocarbon material molded body, and may be also referred to as a porosity of the nanocarbon material molded body, and is measured by a mercury intrusion method (refer to "research on porosity of graphite porous material", lubrication and sealing ", 2010, 35 (10): 99-101) in percentage).
Preparation examples 1 to 23 were used to prepare heteroatom-containing nanocarbon materials.
Preparation example 1
(1) 20g of multiwall carbon nanotube A (purchased from Kyowa organic chemistry, Ltd., China academy of sciences) as a raw material nanocarbon material was dispersed in 300g of deionized water to obtain an aqueous dispersion, wherein the dispersion was performed under ultrasonic oscillation conditions including: the frequency was 40kHz and the time was 2 hours.
(2) The obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at 140 ℃ under autogenous pressure for 48 hours. After the reaction is finished, after the temperature in the high-pressure reaction kettle is reduced to room temperature, the reaction kettle is opened, the reaction mixture is filtered and washed, and solid substances are collected. Drying the collected solid substance at normal pressure (1 atm, the same below) and 120 deg.C for 12 hr to obtain heteroatom-containing nano carbon material with composition, specific surface area and w500/w800Listed in table 2.
Preparation example 2
The same aqueous dispersion as in preparation example 1 was placed in a three-necked flask equipped with a condenser tube, and the three-necked flask was placed in an oil bath at a temperature of 140 ℃ and reacted under reflux at normal pressure for 48 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at normal pressure and 120 ℃ for 6 hours to obtain the heteroatom-containing nano carbon material.
Preparation example 3
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that in step (1), the nanocarbon material was a multiwall carbon nanotube B.
Preparation example 4
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 1, except that, in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at a temperature of 90 ℃ under autogenous pressure for 48 hours.
Preparation example 5
(1) 20g of multiwall carbon nanotube C (purchased from medley organic chemistry, ltd, academy of china) as a raw nanocarbon material was dispersed in 500g of deionized water to obtain an aqueous dispersion, wherein the dispersion was performed under ultrasonic oscillation conditions including: the frequency was 80kHz and the time was 0.5 hour.
(2) The obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at 180 ℃ under autogenous pressure for 24 hours. After the reaction is finished, after the temperature in the high-pressure reaction kettle is reduced to room temperature, the reaction kettle is opened, the reaction mixture is filtered and washed, and solid substances are collected. And drying the collected solid substance at the temperature of 120 ℃ for 12 hours under normal pressure to obtain the heteroatom-containing nano carbon material.
Preparation example 6
The same aqueous dispersion as in preparation example 5 was placed in a three-necked flask equipped with a condenser tube, and the three-necked flask was placed in an oil bath at a temperature of 100 ℃ and reacted under reflux at normal pressure for 24 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at normal pressure and 120 ℃ for 6 hours to obtain the heteroatom-containing nano carbon material.
Preparation example 7
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 5, except that, in step (1), the nanocarbon material was a multiwall carbon nanotube D.
Preparation example 8
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 5, except that, in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at a temperature of 210 ℃ under autogenous pressure for 24 hours.
Preparation example 9
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that, in step (1), after dispersing a raw nanocarbon material in deionized water, tetrapropylammonium hydroxide (provided in the form of a 25 wt% aqueous solution) was added, wherein, as the raw nanocarbon material: the weight ratio of tetrapropylammonium hydroxide is 1: the feed was dosed at a ratio of 0.75.
Preparation example 10
The same aqueous dispersion as in preparation example 9 was placed in a three-necked flask equipped with a condenser, the three-necked flask was placed in an oil bath at a temperature of 140 ℃ and reacted under reflux at normal pressure for 48 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at normal pressure and 120 ℃ for 6 hours to obtain the heteroatom-containing nano carbon material.
Preparation example 11
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 9, except that in step (1), tetrapropylammonium hydroxide was replaced with an equimolar amount of n-propylamine.
Preparation example 12
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 9, except that in step (1), tetrapropylammonium hydroxide was replaced with an equimolar amount of pyridine.
Preparation example 13
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 9, except that in step (1), tetrapropylammonium hydroxide was replaced with an equimolar amount of cyclohexylamine.
Preparation example 14
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 9, except that in step (1), tetrapropylammonium hydroxide was replaced with an equimolar amount of diethanolamine.
Preparation example 15
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 9, except that in the step (1), tetrapropylammonium hydroxide was replaced with diethylenetriamine having a molar amount of 0.3 times that of tetrapropylammonium hydroxide.
Preparation example 16
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 9, except that, in step (1), the raw nanocarbon material was the multiwall carbon nanotube B.
Preparation example 17
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 9, except that, in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at a temperature of 80 ℃ under autogenous pressure for 48 hours.
Preparation example 18
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 9, except that, in step (1), the carbon material was prepared as follows: the weight ratio of tetrapropylammonium hydroxide is 1: the feed was dosed at a ratio of 0.4.
Preparation example 19
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 5, except that, in step (1), after the raw nanocarbon material was dispersed in deionized water, tetraethylammonium hydroxide (provided in the form of a 20 wt% aqueous dispersion) was added to obtain an aqueous dispersion, wherein, as the raw nanocarbon material: the weight ratio of tetraethyl ammonium hydroxide is 1: 5 in proportion.
Preparation example 20
The same aqueous dispersion as in preparation example 19 was placed in a three-necked flask equipped with a condenser tube, and the three-necked flask was placed in an oil bath at a temperature of 180 ℃ and reacted under reflux at normal pressure for 24 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at normal pressure and 120 ℃ for 6 hours to obtain the heteroatom-containing nano carbon material.
Preparation example 21
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 19, except that, in step (1), the raw nanocarbon material was the multiwalled carbon nanotube D.
Preparation example 22
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 19, except that, in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at a temperature of 200 ℃ under autogenous pressure for 48 hours.
Preparation example 23
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 19, except that, in the step (1), the raw nanocarbon material: the weight ratio of tetraethyl ammonium hydroxide is 1: 8 in the proportion.
Examples 1 to 82 are for illustrating the nanocarbon material molded bodies and the method of preparing the same according to the present invention.
Examples 1-82 refer to the following binder sources.
Silica sol: purchased from Zhejiang Yuda chemical Co., Ltd, and the content of silica was 25% by weight
Tetraethyl orthosilicate: from Zhang Jiagang Xinya chemical Co Ltd (TES number)
Aluminum sol: purchased from Shandong Chilida chemical Co., Ltd., and having an alumina content of 12% by weight
Aluminum isopropoxide: purchased from Beijing Germany island gold technologies Co Ltd (number IPOA)
Titanium oxide: purchased from Shandong Zhengyuan nanometer materials engineering Co., Ltd, and has a particle diameter of 5-10nm
Tetraethyl titanate: from Jinyu chemical Limited liability company (TET)
(1) Crystallization mother liquor of titanium silicon molecular sieve
Titanium silicalite TS-1 was prepared according to the method of US4410501, example 1, and the crystallization mother liquor was collected. The specific operation process is as follows:
455g of tetraethylorthosilicate were placed in a reactor equipped with a stirring device and free of CO2In the reactor under the atmosphere, 15g of tetraethyl titanate and 800g of 25% strength by weight aqueous tetrapropylammonium hydroxide solution were then added. Stirring for 1 hourAnd then, raising the temperature to 80-90 ℃, and continuing stirring for 5 hours. Deionized water was then added to the reaction solution until the total volume of the reaction solution was 1.5L. And then, transferring the reaction liquid into a high-pressure reaction kettle with a stirring device, carrying out hydrothermal crystallization at 175 ℃ under autogenous pressure for 10 days, filtering the obtained reaction mixture, collecting crystallization mother liquor, and roasting the filtered solid in air atmosphere at 550 ℃ for 6 hours to obtain the titanium silicalite TS-1.
Through detection, the total amount of the crystallization mother liquor is taken as a reference, and SiO is taken2The content of silicon element was 1.2% by weight in terms of TiO2The content of titanium element was 0.04% by weight, and the content of tetrapropylammonium hydroxide was 3.1% by weight. Concentrating the crystallization mother liquor (the concentrated liquor is numbered TS-A) to the total amount of the crystallization mother liquor as the reference, and taking SiO as the reference2The content of silicon element was 2.4 wt.% in terms of TiO2The content of titanium element was 0.08% by weight, and the content of tetrapropylammonium hydroxide was 6.2% by weight.
(2) Crystallization mother liquor of titanium silicon molecular sieve
The titanium silicalite TS-1 was prepared according to the method of US4410501, example 2, and the crystallization mother liquor was collected. The specific operation process is as follows:
150g tetraethyl titanate was slowly added dropwise to 2.5L distilled water and hydrolyzed under stirring to give a white colloidal suspension which was then cooled to 5 ℃; then 1.8L of 30% by mass aqueous hydrogen peroxide which had been cooled to 5 ℃ in advance was added thereto and kept at 5 ℃ for 2 hours with intermittent stirring to give an orange clear solution; then 2.4L of 25% strength by mass aqueous tetrapropylammonium hydroxide solution which had previously been cooled to 5 ℃ were added to the orange clear solution, and after 1 hour 500g of SiO were added2Carefully mixing silica sol with the content of 40%, and standing the obtained mixture at normal temperature overnight; finally, the mixture is heated and stirred for 6 hours at 70-80 ℃. Transferring the obtained mixture into a high-pressure reaction kettle equipped with a stirring device, performing hydrothermal crystallization at 175 deg.C under autogenous pressure for 10 days, filtering the obtained reaction mixture, collecting crystallization mother liquor (TS-B), and calcining the filtered solid phase at 550 deg.C in air atmosphere for 6 daysAnd when the reaction solution is small, the titanium silicalite TS-1 is obtained by the verification of X-ray diffraction analysis.
Through detection, the total amount of the crystallization mother liquor is taken as a reference, and SiO is taken2The content of silicon element was 2.8 wt.% in terms of TiO2The content of titanium element was 0.04% by weight, and the content of tetrapropylammonium hydroxide was 1.6% by weight.
(3) Crystallization mother liquor of titanium silicon molecular sieve
The Ti-Beta molecular sieve was prepared as described in J.chem.Soc.chem.Commun, 1992, 589-590 and the crystallization mother liquor was collected during the solid-liquid separation. The preparation process comprises the following steps:
tetraethyl titanate and amorphous silica gel Aerosil 200 were added to an aqueous tetraethylammonium hydroxide (TEAOH) solution with stirring at room temperature, followed by the addition of a suitable amount of aluminum nitrate, the molar composition of the gel formed being A12O3：TiO2：SiO2：H2O: TEAOH ═ 1: 12: 388: 6000: 108, transferring the formed glue solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining for dynamic crystallization, wherein the crystallization temperature is 130 ℃, the stirring speed is 60rpm, and the crystallization time is 3 d. After cooling, the solid-liquid mixture obtained was centrifuged to obtain a solid and a crystallization mother liquor (numbered TS-C). And washing the separated solid with water until the pH value is about 9, drying at 80 ℃ for 5h, and roasting at 580 ℃ in an air atmosphere for 5h to obtain the titanium silicalite Ti-Beta.
Through detection, the total amount of the crystallization mother liquor is taken as a reference, and SiO is taken2The content of silicon element was 3.4 wt% in terms of TiO2The content of titanium element was 0.3% by weight, and the content of tetraethylammonium hydroxide was 13.1% by weight.
(4) Rearrangement liquid of titanium-silicon molecular sieve
The method of embodiment 9 of the chinese application 99126289.1 is used to obtain the heavy liquid discharge of the titanium silicalite molecular sieve, and the specific preparation process is as follows:
according to TS-1 molecular sieve (g): tetraethylammonium hydroxide (mol): water (mole) ═ 100: 0.25: 60, placing the mixture into a stainless steel sealed reaction kettle, and placing the mixture for 3 days at a constant temperature of 175 ℃ and an autogenous pressure. Cooling, releasing pressure, and filtering to obtain filtrate, i.e. the heavy discharge liquid of the titanium-silicon molecular sieve.
Through detection, the total amount of the heavy discharge liquid is taken as a reference, and SiO is taken2The content of silicon element was 1.1% by weight in terms of TiO2The content of titanium element was 0.02% by weight, and the content of tetrapropylammonium hydroxide was 3.6% by weight. Concentrating the rearranged solution (the concentrated solution is numbered TS-D) to SiO based on the total amount of the rearranged solution2The content of silicon element was 2.2 wt.% in terms of TiO2The content of titanium element was 0.04% by weight, and the content of tetrapropylammonium hydroxide was 7.3% by weight.
(5) Crystallization mother liquor of silicon-aluminum molecular sieve
Referring to US4410501, example 1, a silicon aluminum molecular sieve is prepared using aluminum isopropoxide as an aluminum source instead of tetraethyl titanate as a titanium source, and the crystallization mother liquor is collected. The specific operation process is as follows:
in the absence of CO2In a heat-resistant glass vessel, 455g of tetraethyl silicate was placed in the vessel, 15g of aluminum isopropoxide was added with stirring, 800g of an aqueous 25% tetrapropylammonium hydroxide solution was added, the mixture was mixed for 4 hours, and the mixture was heated at 80 to 90 ℃ and stirred for 5 hours, thereby completely removing ethanol. Then, water was added to 1.5L, the resulting mixture was transferred to a high-pressure reaction vessel equipped with a stirring device, and subjected to hydrothermal crystallization at 175 ℃ under autogenous pressure for 10 days, and the resulting reaction mixture was filtered to collect a crystallization mother liquor (No. AS-E).
Through detection, the total amount of the crystallization mother liquor is taken as a reference, and SiO is taken2The content of silicon element calculated as Al was 2.3 wt%2O3The content of aluminum element was 0.14% by weight, and the content of tetrapropylammonium hydroxide was 12.5% by weight.
Examples 1 to 49
The nanocarbon materials were molded by the following methods, respectively, under the conditions given in table 3.
The nanocarbon material was mixed with a binder source at ambient temperature (25 ℃) respectively, the resulting mixture was dried in a strip mold and optionally calcined to obtain nanocarbon material moldings (a portion of the moldings was randomly selected and ground to obtain a sample band of 3-5mm in length for measuring crushing strength and porosity, the results are listed in table 3), and the remaining moldings were crushed and sieved to obtain granular moldings, the average particle size (particle size for short) of which is listed in table 3.
TABLE 3
1: the amount of the nanocarbon material is 10g2: calculated by oxide3: tetrapropylammonium hydroxide
4: the kind and amount of the treating agent added in addition to the treating agent contained in the binder source
Examples 49 to 76
The following methods were used to shape the nanocarbon materials according to the conditions given in table 4, respectively:
mixing the nano carbon material with a binder source and an optional treating agent respectively, then placing the obtained mixture into a sealed high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment under autogenous pressure. After the temperature in the high-pressure reaction kettle is reduced to the ambient temperature, the reaction kettle is opened, the obtained slurry is sent into a strip-shaped mold to be dried and optionally roasted to obtain a nano-carbon material forming body (a part of the forming body is randomly selected to be ground to obtain a sample strip with the length of 3-5mm for measuring the crushing resistance strength and the porosity, the result is listed in table 4), the rest forming body is crushed and then screened to obtain a granular forming body, and the average particle size of the granular forming body is listed in table 4.
Examples 77, 79 and 81
Example 77 differs from example 50 in that the nanocarbon material and the binder source were uniformly mixed at ambient temperature (25 ℃) and then molded without hydrothermal treatment.
Example 79 differs from example 51 in that the nanocarbon material and the binder source were uniformly mixed at ambient temperature (25 ℃ C.) and then molded without hydrothermal treatment.
Example 81 differs from example 52 in that the nanocarbon material and the binder source were uniformly mixed at ambient temperature (25 ℃ C.) and then molded without hydrothermal treatment.
Examples 78, 80 and 82
Example 78 differs from example 50 in that a mixture of a nanocarbon material and a binder source was placed in a three-necked flask, a reflux reaction was carried out at the same temperature as the hydrothermal treatment temperature in example 50 for the same time as the hydrothermal treatment in example 50, and the mixture obtained by the reflux reaction was fed into a mold.
Example 80 differs from example 51 in that a mixture of a nanocarbon material and a binder source was placed in a three-necked flask, a reflux reaction was carried out at the same temperature as the hydrothermal treatment temperature in example 51 for the same time as the hydrothermal treatment in example 51, and the mixture obtained by the reflux reaction was fed into a mold.
Example 82 is different from example 52 in that a mixture of a nanocarbon material and a binder source was placed in a three-necked flask, a reflux reaction was carried out at the same temperature as the hydrothermal treatment temperature in example 52 for the same time as the hydrothermal treatment in example 52, and the mixture obtained by the reflux reaction was fed into a mold.
TABLE 4
1: the amount of the nanocarbon material is 10g2: calculated by oxide3: tetrapropylammonium hydroxide4: tetramethylammonium hydroxide 5: tetraethyl ammonium hydroxide
6: the kind and amount of the treating agent added in addition to the treating agent contained in the binder source
Test examples 1 to 82
The catalysts prepared in examples 1-82 were tested for catalytic performance in the following order.
0.2g of each of the granular molded bodies prepared in examples 1 to 82 was packed as a catalyst in a general-purpose fixed bed micro quartz tube reactor each having quartz sand sealed at both ends, and a gas containing n-butane and oxygen (n-butane concentration of 1.98% by volume, n-butane/oxygen molar ratio of 0.5: 1, and the balance nitrogen as a carrier gas) was charged at 0MPa (gauge pressure) and 450 ℃ for 3000 hours-1The reaction was carried out by passing into the reactor at a weight hourly space velocity of (g), continuously monitoring the composition of the reaction mixture output from the reactor, and calculating the n-butane conversion and the total olefin selectivity, the results of the reaction for 3 hours and 24 hours being shown in table 5.
Testing of comparative examples 1-4
The catalytic performance of multi-walled carbon nanotubes A, B, C and D were tested in turn using the same method as in test examples 1-82.
TABLE 5
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (90)
1. A nanocarbon material molded body comprising a nanocarbon material and a heat-resistant inorganic oxide for bonding and molding the nanocarbon material, wherein the nanocarbon material is contained in an amount of 6 to 94% by weight and the binder is contained in an amount of 6 to 94% by weight, based on the total amount of the molded body;
the nano carbon material is prepared by adopting a method comprising the following steps: reacting an aqueous dispersion in which a raw material nanocarbon material is dispersed in a closed container, wherein the aqueous dispersion contains or does not contain an organic base, the organic base is amine and/or quaternary ammonium base, and the temperature of the aqueous dispersion is kept within the range of 80-220 ℃ during the reaction;
the preparation method of the nano carbon material forming body comprises the steps of mixing a nano carbon material with a binder source, forming the obtained mixture to obtain a formed body, drying and optionally roasting the formed body, wherein the mixture optionally contains at least one alkali selected from organic alkali; the binder source is selected from heat-resistant inorganic oxide and/or precursor of the heat-resistant inorganic oxide, at least part of the binder source, at least part of optional alkali and at least part of water come from a molecular sieve preparation liquid, the molecular sieve preparation liquid is a mixed liquid of one or more than two of crystallization mother liquid and/or rearrangement modification liquid of a titanium-silicon molecular sieve and crystallization mother liquid and/or rearrangement modification liquid of a silicon-aluminum molecular sieve,
wherein before the mixture is formed, the method further comprises the step of carrying out hydrothermal treatment on the mixture, wherein the hydrothermal treatment is carried out at the temperature of 100-200 ℃, and the duration of the hydrothermal treatment is 0.5-24 hours.
2. The molded body according to claim 1, wherein the polymer is a copolymer,wherein, in the aqueous dispersion, the raw material nano carbon material: h2The weight ratio of O is 1: 2-200.
3. The molded body according to claim 2, wherein in the aqueous dispersion, the raw material nanocarbon material: h2The weight ratio of O is 1: in the range of 5-100.
4. The molded body according to claim 3, wherein in the aqueous dispersion, the ratio of the raw nanocarbon material: h2The weight ratio of O is 1: in the range of 10-50.
5. The shaped body according to claim 1, wherein the aqueous dispersion comprises at least one organic base, the starting nanocarbon material: the weight ratio of the organic base is 1: 0.05-20.
6. The molded body according to claim 5, wherein in the aqueous dispersion, the ratio of the raw nanocarbon material: the weight ratio of the organic base is 1: in the range of 0.1-8.
7. The molded body according to claim 6, wherein in the aqueous dispersion, the ratio of the raw nanocarbon material: the weight ratio of the organic base is in the range of 0.5-5.
8. Shaped body according to any one of claims 5 to 7, wherein the organic base in the aqueous dispersion is selected from the group consisting of compounds of formula I, compounds of formula II, compounds of formula III and compounds of the general formula R12(NH2)2A substance represented by R12Is C1-C6Alkylene or C6-C12An arylene group of (a) to (b),
in the formula I, R1、R2、R3And R4Each of which isIs C1-C20Alkyl or C6-C12Aryl of (a);
in the formula II, R5、R6And R7Are each H, C1-C6Alkyl or C6-C12And R is an aryl group of5、R6And R7Not H at the same time;
in the formula III, R8、R9And R10Each is-R11OH, hydrogen or C1-C6And R is alkyl of8、R9And R10At least one of which is-R11OH，R11Is C1-C4An alkylene group of (a).
9. The shaped body as claimed in any of claims 1 to 7, wherein the temperature of the aqueous dispersion is kept in the range of 140-180 ℃ during the reaction.
10. The shaped body according to claim 9, wherein the duration of the reaction is in the range of 0.5 to 96 hours.
11. The shaped body according to claim 10, wherein the duration of the reaction is in the range of 2 to 72 hours.
12. The shaped body according to claim 11, wherein the duration of the reaction is in the range of 20 to 50 hours.
13. The molded body according to any one of claims 1 to 7, wherein the raw nanocarbon material contains N in an amount of not more than 0.2 wt%, O in an amount of not more than 1.5 wt%, and a total amount of metal elements is not more than 2.5 wt%.
14. The molded body according to claim 13, wherein the raw nanocarbon material contains not more than 0.02% by weight of an N element, not more than 0.3% by weight of an O element, and not more than 2.5% by weight of a total amount of metal elements.
15. The molded body according to any one of claims 1 to 7, wherein the raw nanocarbon material is a carbon nanotube.
16. The shaped body according to claim 15, wherein the raw nanocarbon material is multi-walled carbon nanotubes.
17. The shaped body according to claim 16, wherein the multi-walled carbon nanotubes have a specific surface area of 50-500m2/g。
18. The shaped body as claimed in claim 17, wherein the multi-walled carbon nanotubes have a specific surface area of 120-190m2/g。
19. The shaped body as claimed in claim 16, wherein the total weight loss of the multiwalled carbon nanotubes in the temperature interval of 400-800 ℃ is w800The total weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800The weight loss ratio is measured in an air atmosphere in the range of 0.01 to 0.5.
20. The shaped body of claim 19, wherein w is500/w800In the range of 0.02-0.4.
21. The molded body according to any one of claims 1 to 7, wherein the method for producing the nanocarbon material further comprises separating a solid substance from the mixture obtained by the reaction, and drying the separated solid substance.
22. The shaped body according to claim 21, wherein the drying is carried out at a temperature of 50-400 ℃ and the duration of the drying is not more than 48 hours.
23. Shaped body according to claim 22, wherein the drying is carried out at a temperature of 80-180 ℃ and the duration of the drying is 4-24 hours.
24. The shaped body according to claim 23, wherein the duration of drying is from 6 to 12 hours.
25. A nanocarbon material molded body containing a nanocarbon material and a heat-resistant inorganic oxide for bonding and molding the nanocarbon material, the nanocarbon material being contained in an amount of 6 to 94% by weight and the binder being contained in an amount of 6 to 94% by weight, based on the total amount of the molded body, the nanocarbon material containing an O element and optionally an N element;
the nano carbon material is prepared by adopting a method comprising the following steps: reacting an aqueous dispersion solution in which a raw material nano carbon material is dispersed in a closed container, wherein the aqueous dispersion solution contains or does not contain an organic base, the organic base is amine and/or quaternary ammonium base, the temperature of the aqueous dispersion solution is kept within the range of 80-220 ℃ in the reaction process, and the duration of the reaction is 2-96 hours;
the preparation method of the nano carbon material forming body comprises the steps of mixing a nano carbon material with a binder source, forming the obtained mixture to obtain a formed body, drying and optionally roasting the formed body, wherein the mixture optionally contains at least one alkali selected from organic alkali; the binder source is selected from heat-resistant inorganic oxide and/or precursor of the heat-resistant inorganic oxide, at least part of the binder source, at least part of optional alkali and at least part of water come from a molecular sieve preparation liquid, the molecular sieve preparation liquid is a mixed liquid of one or more than two of crystallization mother liquid and/or rearrangement modification liquid of a titanium-silicon molecular sieve and crystallization mother liquid and/or rearrangement modification liquid of a silicon-aluminum molecular sieve,
wherein before the mixture is formed, the method further comprises the step of carrying out hydrothermal treatment on the mixture, wherein the hydrothermal treatment is carried out at the temperature of 100-200 ℃, and the duration of the hydrothermal treatment is 0.5-24 hours.
26. The molded body according to claim 25, wherein the content of the O element is 0.5 to 6% by weight, the content of the N element is 0 to 2% by weight, and the content of the C element is 92 to 99.5% by weight, in terms of elements, based on the total amount of the nanocarbon material.
27. The molded body according to claim 25, wherein the nanocarbon material contains N in an amount of less than 0.1 wt%, and the content of O in the nanocarbon material is 0.5 to 5.8 wt% and the content of C in the nanocarbon material is 94.2 to 99.5 wt%, based on the total amount of the nanocarbon material and calculated as elements.
28. The molded body according to claim 27, wherein the nanocarbon material contains an element N in an amount of less than 0.1 wt%, an element O in an amount of 3 to 5.5 wt% and an element C in an amount of 94.5 to 97 wt% based on the total amount of the nanocarbon material and calculated as the element.
29. The molded body according to claim 28, wherein the nanocarbon material contains N in an amount of less than 0.1 wt%, and the content of O in the nanocarbon material is 4.5 to 5.5 wt% and the content of C in the nanocarbon material is 94.5 to 95.5 wt%, based on the total amount of the nanocarbon material and calculated as elements.
30. The shaped body according to claim 27, wherein the amount of O element in the nanocarbon material determined by a peak in the range of 531.0 to 532.5eV in an X-ray photoelectron spectrum is IO cThe amount of O element determined from a peak in the range of 532.6 to 533.5eV in the X-ray photoelectron spectrum is IO e，IO c/IO eIn the range of 0.1-0.7;
in the nanocarbon material, the amount of C element determined by a peak in the range of 288.6-288.8eV in an X-ray photoelectron spectrum is IC cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is IC e，IC c/IC eIn the range of 0.1-0.9.
31. The shaped body of claim 30, wherein IO c/IO eIn the range of 0.4-0.7, IC c/IC eIn the range of 0.3-0.9.
32. The shaped body of claim 31, wherein IO c/IO eIn the range of 0.55-0.65, IC c/IC eIn the range of 0.35-0.8.
33. The shaped body of claim 32, wherein IC c/IC eIn the range of 0.5-0.7.
34. The molded body according to claim 25, wherein the content of the O element is 1.3 to 6% by weight, the content of the N element is 0.2 to 1.8% by weight, and the content of the C element is 92.2 to 98.5% by weight, based on the total amount of the nanocarbon material and calculated as elements.
35. The molded body according to claim 34, wherein the content of the O element is 2 to 6% by weight, the content of the N element is 0.5 to 1.8% by weight, and the content of the C element is 92.2 to 97.5% by weight, in terms of elements, based on the total amount of the nanocarbon material.
36. The molded body according to claim 35, wherein the content of the O element is 4 to 6% by weight, the content of the N element is 1 to 1.5% by weight, and the content of the C element is 92.5 to 95% by weight, in terms of elements, based on the total amount of the nanocarbon material.
37. The shaped body according to any one of claims 34 to 36, wherein the amount of O element in the nanocarbon material, determined by a peak in the range of 531.0 to 532.5eV in X-ray photoelectron spectroscopy, is IO cThe amount of O element determined from a peak in the range of 532.6 to 533.5eV in the X-ray photoelectron spectrum is IO e，IO c/IO eIn the range of 0.1-0.9;
in the nanocarbon material, the amount of C element determined by a peak in the range of 288.6-288.8eV in an X-ray photoelectron spectrum is IC cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is IC e，IC c/IC eIn the range of 0.1-0.98.
38. The shaped body of claim 37, wherein IO c/IO eIn the range of 0.35-0.85, IC c/IC eIn the range of 0.3-0.98.
39. The shaped body of claim 38, wherein IO c/IO eIn the range of 0.5-0.8, IC c/IC eIn the range of 0.45-0.6.
40. The shaped body according to any one of claims 25, 26 and 34 to 36, wherein the total amount of N elements in the nanocarbon material is I as determined by X-ray photoelectron spectroscopyN tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is IN c，IN c/IN tIn the range of 0.7-1.
41. The shaped body of claim 40, wherein IN c/IN tIn the range of 0.8-0.95.
42. The molded body according to any one of claims 25 to 36, wherein the nanocarbon material has a content of a C element determined by a peak in a range of 284.7 to 284.9eV in an X-ray photoelectron spectrum of 20% by weight or more and a content of a C element determined by a peak in a range of 284.7 to 284.9eV in an X-ray photoelectron spectrum of 95% by weight or less, based on the total amount of the C element determined by the X-ray photoelectron spectrum.
43. The molded body according to claim 42, wherein the nanocarbon material has a C element content determined from a peak in the range of 284.7-284.9eV in an X-ray photoelectron spectrum of 40% by weight or more and a C element content determined from a peak in the range of 284.7-284.9eV in an X-ray photoelectron spectrum of 90% by weight or less, based on the total amount of the C element determined by the X-ray photoelectron spectrum.
44. The molded body according to claim 43, wherein the nanocarbon material contains 50% by weight or more of C element determined from a peak in the range of 284.7 to 284.9eV in an X-ray photoelectron spectrum, based on the total amount of C element determined by the X-ray photoelectron spectrum.
45. The molded body according to claim 44, wherein the nanocarbon material contains 70% by weight or more of C element determined from a peak in the range of 284.7-284.9eV in an X-ray photoelectron spectrum, based on the total amount of C element determined by the X-ray photoelectron spectrum.
46. The shaped body according to any one of claims 1-7 and 25-36, wherein the nanocarbon material is a carbon nanotube.
47. The shaped body according to claim 46, wherein the nanocarbon material is a multiwall carbon nanotube.
48. The shaped body according to claim 47, wherein the multi-walled carbon nanotubes have a specific surface area of 50 to 500m2In the range of/g.
49. The shaped body according to claim 48, wherein the multi-walled carbon nanotubes have a specific surface area of 80 to 300m2In the range of/g.
50. The shaped body as claimed in claim 49, wherein the specific surface area of the multi-walled carbon nanotubes is in the range of 130-180m2In the range of/g.
51. The shaped body as claimed in claim 47, wherein the weight loss rate of the multi-walled carbon nanotubes in the temperature interval of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800The weight loss ratio is measured in an air atmosphere in the range of 0.01 to 0.5.
52. The shaped body of claim 51, wherein w is500/w800In the range of 0.02-0.3.
53. The shaped body of claim 52, wherein w is500/w800In the range of 0.05-0.15.
54. The shaped body according to any one of claims 1 to 7 and 25 to 36, wherein the nanocarbon material is contained in an amount of 10 to 90% by weight and the heat-resistant inorganic oxide is contained in an amount of 10 to 90% by weight, based on the total amount of the shaped body.
55. The shaped body according to claim 54, wherein the nanocarbon material is present in an amount of 40-90 wt.% and the heat-resistant inorganic oxide is present in an amount of 10-60 wt.%, based on the total amount of the shaped body.
56. The shaped body according to claim 55, wherein the nanocarbon material is contained in an amount of 65 to 90% by weight and the heat-resistant inorganic oxide is contained in an amount of 10 to 35% by weight, based on the total amount of the shaped body.
57. The shaped body according to any one of claims 1 to 7 and 25 to 36, wherein the heat-resistant inorganic oxide is one or two or more of alumina, silica and titania.
58. The shaped body of claim 57, wherein the heat-resistant inorganic oxide comprises silicon oxide.
59. The shaped body according to claim 58, wherein the silicon oxide is contained in an amount of 10 to 100% by weight, based on the total amount of the heat-resistant inorganic oxide.
60. The shaped body according to claim 59, wherein the silicon oxide is present in an amount of 20 to 99% by weight, based on the total amount of the heat-resistant inorganic oxide.
61. The shaped body according to claim 60, wherein the silicon oxide is contained in an amount of 50 to 99% by weight, based on the total amount of the heat-resistant inorganic oxide.
62. A method for preparing a nano carbon material forming body comprises the steps of mixing a nano carbon material with a binder source, forming the obtained mixture to obtain a forming body, drying and optionally roasting the forming body, wherein the binder source is selected from a heat-resistant inorganic oxide and/or a precursor of the heat-resistant inorganic oxide, at least part of the binder source, at least part of optional alkali and at least part of water come from a molecular sieve preparation liquid, the molecular sieve preparation liquid is one or a mixture of more than two of a crystallization mother liquid and/or a rearrangement modification liquid of a titanium-silicon molecular sieve and a crystallization mother liquid and/or a rearrangement modification liquid of a silicon-aluminum molecular sieve, before forming the mixture, the method further comprises the step of carrying out hydrothermal treatment on the mixture, the hydrothermal treatment is carried out at the temperature of 100-180 ℃, the duration time of the hydrothermal treatment is 0.5-24 hours,
the nanocarbon material is a nanocarbon material without surface treatment and a nanocarbon material with surface treatment, or the nanocarbon material is a nanocarbon material with surface treatment, which contains an O element and optionally an N element as determined by X-ray photoelectron spectroscopy, wherein the nanocarbon material with surface treatment is the nanocarbon material described in any one of claims 1 to 53.
63. The method of claim 62, wherein the mixture further comprises at least one base.
64. A process as claimed in claim 63, in which the base is selected from organic bases.
65. The method of claim 64, wherein the organic base is selected from the group consisting of quaternary ammonium bases, aliphatic amines, and aliphatic alcohol amines.
66. The method of claim 65, wherein the organic base is selected from templating agents for synthesizing titanium silicalite molecular sieves.
67. A process according to claim 66, wherein the organic base is selected from compounds of formula I:
in the formula I, R1、R2、R3And R4Each is C1-C20Alkyl or C6-C12Aryl group of (1).
68. The method of any of claims 63-67, wherein the molar ratio of the base to the binder source is from 0.1 to 10: 1, the binder source is calculated by oxide.
69. The method of claim 68, wherein the molar ratio of the base to the binder source is 0.15-5: 1, the binder source is calculated by oxide.
70. The method as claimed in claim 62, wherein the hydrothermal treatment is carried out at a temperature of 120-180 ℃ and the duration of the hydrothermal treatment is 6-12 hours.
71. The method of any of claims 62-67 and 70, wherein the refractory inorganic oxide is one or more of alumina, silica and titania.
72. The method of claim 71, wherein the refractory inorganic oxide comprises silicon oxide.
73. The method as claimed in claim 72, wherein the silicon oxide is present in an amount of 10-100 wt% based on the total amount of the refractory inorganic oxide.
74. The method as claimed in claim 73, wherein the silicon oxide is present in an amount of 20-99 wt% based on the total amount of the refractory inorganic oxide.
75. A method as claimed in claim 74, wherein the silica is present in an amount of 50-99% by weight, based on the total amount of refractory inorganic oxide.
76. The method as claimed in any one of claims 62 to 67 and 70, wherein the binder source is used in an amount such that the nanocarbon material content in the finally prepared shaped body is 5-95 wt% and the refractory inorganic oxide content is 5-95 wt%.
77. A method as claimed in claim 76, in which the binder source is used in an amount such that the nanocarbon material content in the finally produced shaped body is in the range of 75-95% by weight and the refractory inorganic oxide content is in the range of 5-25% by weight.
78. A method as claimed in claim 77, wherein the binder source is used in an amount such that the nanocarbon material content in the finally produced shaped body is 80-95 wt% and the refractory inorganic oxide content is 5-20 wt%.
79. The method of any one of claims 62-67 and 70, wherein said drying is performed at a temperature of 50-200 ℃, said drying lasting no more than 48 hours;
the calcination is carried out at a temperature of 300-800 ℃ and the duration of the calcination is 1-12 hours.
80. The method as claimed in claim 79, wherein the drying is carried out at a temperature of 120-180 ℃; the duration of the drying is 3-24 hours;
the duration of the calcination is 2-4 hours.
81. The method of claim 80, wherein the duration of drying is 5-15 hours.
82. A nanocarbon material molded body produced by the method of any one of claims 62 to 81.
83. Use of a nanocarbon material shaped body as claimed in any one of claims 1 to 61 and 82 as a catalyst for dehydrogenation reactions of hydrocarbons.
84. The use of claim 83, wherein the hydrocarbon is an alkane.
85. The use of claim 84, wherein the hydrocarbon is C2-C12Of (a) an alkane.
86. The use according to claim 85, wherein the hydrocarbon is n-butane.
87. A hydrocarbon dehydrogenation reaction process comprising contacting a hydrocarbon with the nanocarbon material shaped body of any one of claims 1 to 61 and 82 under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen.
88. The method of claim 87, wherein the hydrocarbon is an alkane.
89. The method of claim 88, wherein the hydrocarbon is C2-C12Of (a) an alkane.
90. The method of claim 89, wherein the hydrocarbon is n-butane.
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