CN107661761A - The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material - Google Patents
The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material Download PDFInfo
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- CN107661761A CN107661761A CN201610602403.2A CN201610602403A CN107661761A CN 107661761 A CN107661761 A CN 107661761A CN 201610602403 A CN201610602403 A CN 201610602403A CN 107661761 A CN107661761 A CN 107661761A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 339
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 339
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 57
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- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 53
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims description 131
- 238000002360 preparation method Methods 0.000 title claims description 79
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 60
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- 238000001228 spectrum Methods 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000002808 molecular sieve Substances 0.000 claims description 47
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- 238000003786 synthesis reaction Methods 0.000 claims description 4
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- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 2
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 14
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
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- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- HFXKQSZZZPGLKQ-UHFFFAOYSA-N cyclopentamine Chemical compound CNC(C)CC1CCCC1 HFXKQSZZZPGLKQ-UHFFFAOYSA-N 0.000 description 1
- 229960003263 cyclopentamine Drugs 0.000 description 1
- 125000004856 decahydroquinolinyl group Chemical class N1(CCCC2CCCCC12)* 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HDHOHQHZKXFKOS-UHFFFAOYSA-N ethylbenzene;hydrogen peroxide Chemical compound OO.CCC1=CC=CC=C1 HDHOHQHZKXFKOS-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical class CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical class C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-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 class CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229950002366 nafoxidine Drugs 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Chemical group C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- SDPBQTFSSSPDBS-UHFFFAOYSA-N pentan-1-amine;hydrate Chemical compound [OH-].CCCCC[NH3+] SDPBQTFSSSPDBS-UHFFFAOYSA-N 0.000 description 1
- LTHAIAJHDPJXLG-UHFFFAOYSA-N pentan-2-ylbenzene Chemical class CCCC(C)C1=CC=CC=C1 LTHAIAJHDPJXLG-UHFFFAOYSA-N 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-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
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 description 1
- GDRLAWYXAIXEGC-UHFFFAOYSA-N propan-2-amine;hydrate Chemical compound O.CC(C)N GDRLAWYXAIXEGC-UHFFFAOYSA-N 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 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
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- BGXXXYLRPIRDHJ-UHFFFAOYSA-N tetraethylmethane Chemical class CCC(CC)(CC)CC BGXXXYLRPIRDHJ-UHFFFAOYSA-N 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 group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 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
- 229960001124 trientine Drugs 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JXPOLSKBTUYKJB-UHFFFAOYSA-N xi-2,3-Dimethylhexane Chemical class CCCC(C)C(C)C JXPOLSKBTUYKJB-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of nano-carbon material formed body, the formed body contains nano-carbon material and for by the heat-resistant inorganic oxide of the nano-carbon material molding bonded, the nano-carbon material to contain O elements and optional N element.According to the nano-carbon material formed body of the present invention using heat-resistant inorganic oxide as binding agent by nano-carbon material molding bonded, not only there is higher crushing strength, and there is higher porosity, the catalyst for being adapted as catalyst, particularly hydrocarbon dehydrogenation reaction uses.
Description
Technical field
The present invention relates to nano-carbon material field shaping technique, in particular it relates to which a kind of nano-carbon material is molded
Body and preparation method thereof, the invention further relates to the application of catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction,
The invention further relates to a kind of hydrocarbon dehydrogenation reaction method using the nano-carbon material formed body as catalyst.
Background technology
The dehydrogenation reaction of hydrocarbons is a kind of important reaction type, such as most of low-carbon olefine is to pass through low-carbon
The dehydrogenation reaction of alkane and obtain.Whether dehydrogenation reaction participates in that direct dehydrogenation reaction (that is, oxygen can be divided into according to oxygen
Gas is not involved in) and oxidative dehydrogenation (that is, oxygen participates in) two classes.
Polytype nano-carbon material has been demonstrated equal to the direct dehydrogenation reaction of hydrocarbons and oxidative dehydrogenation
With catalytic effect.
Hydrocarbon oxidative dehydrogenation process using nano-carbon material as catalyst, need to be by nano-sized carbon as used fixed bed reaction technique
Material is molded, and formed body needs the requirement for meeting following two aspects：(1) there is certain intensity, to avoid in course of reaction
Middle formed body occurs to crush, and on the one hand broken the fine grained formed or powder can cause beds pressure drop to raise, so as to carry
High production run cost, increase the danger of production；On the other hand if the broken fine grained formed or powder are by reaction product band
Go out, catalyst loss and product can be caused to separate and complicate；(2) there is certain porosity, to improve the ratio table of formed body
Area so that the nano-carbon material in formed body can be contacted more fully with reaction mass.
As an example for being molded nano-carbon material, researcher attempts CNT (CNT) being supported on SiC bubbles
The surface of foam, form CNT/SiC foams.Although CNT can preferably be anchored on SiC foam surface, CNT load capacity compared with
It is low, it is typically only capable to reach 0.5-4 weight %.
Therefore, how nano-carbon material is shaped in wide in range nano-carbon material content range still with higher
The formed body of intensity is still a technical problem urgently to be resolved hurrily.
The content of the invention
It is an object of the invention to provide a kind of nano-carbon material formed body and preparation method thereof, nano-carbon material shaping
Body not only has higher intensity, and the content of nano-carbon material can be adjusted in wider scope.
According to an aspect of the present invention, the invention provides a kind of nano-carbon material formed body, the formed body, which contains, to be received
Rice carbon material and for the heat-resistant inorganic oxide of the nano-carbon material molding bonded, the nano-carbon material to be contained into O
Element and optional N element
According to the second aspect of the invention, the invention provides a kind of nano-carbon material formed body, the formed body to contain
Nano-carbon material and for by the heat-resistant inorganic oxide of the nano-carbon material molding bonded；
The nano-carbon material is made using the method comprised the following steps：By one kind be dispersed with raw material nano carbon material with
And the aqueous dispersions of at least one modifying agent are reacted in closed container, in course of reaction, the temperature of the aqueous dispersions
It is maintained in the range of 80-250 DEG C, the modifying agent is peroxide, or is peroxide and HNO3。
According to the third aspect of the present invention, should the invention provides a kind of preparation method of nano-carbon material formed body
Method include nano-carbon material is mixed with binding agent source, obtained mixture is molded, obtains article shaped, by it is described into
Type thing is dried and is optionally calcined, and the binding agent source is selected from heat-resistant inorganic oxide and/or heat-resistant inorganic oxide
Precursor, the nano-carbon material is not surface treated nano-carbon material and/or surface treated nano-carbon material,
Determine that the surface treated nano-carbon material contains O elements and optional N element by x-ray photoelectron power spectrum.
According to the fourth aspect of the present invention, the invention provides a kind of method system as described in third aspect of the present invention
Standby nano-carbon material formed body.
According to the fifth aspect of the present invention, the invention provides a kind of forming method of nano-carbon material, this method bag
Include in closed container, nano-carbon material is subjected to hydro-thermal process in a kind of aqueous dispersions, the slurry that hydro-thermal process is obtained
Shaping, obtains article shaped, the article shaped is dried and is optionally calcined, and the aqueous dispersions contain binding agent source,
The binding agent source is selected from the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, and the nano-carbon material is not
Surface treated nano-carbon material and/or surface treated nano-carbon material, the warp is determined by x-ray photoelectron power spectrum
The nano-carbon material of surface treatment contains O elements and optional N element.
According to the sixth aspect of the invention, the invention provides as the method preparation described in the 5th aspect of the present invention
Nano-carbon material formed body.
According to the seventh aspect of the present invention, the invention provides according to the present invention nano-carbon material formed body as hydrocarbon
The application of the catalyst of dehydrogenation reaction.
According to the eighth aspect of the present invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, deposits
Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with the present invention the on one side, second aspect,
Nano-carbon material formed body contact described in 4th aspect or the 6th aspect.
Nano-carbon material is glued using heat-resistant inorganic oxide as binding agent according to the nano-carbon material formed body of the present invention
Form type, not only there is higher crushing strength, and there is higher porosity, be adapted as catalyst, particularly hydrocarbon
The catalyst of dehydrogenation reaction uses.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.In the present invention, nano-carbon material refers to disperse
The phase yardstick at least one-dimensional carbon material less than 100nm.In the present invention, when representing number range, " ×-× in the range of "
Including two binary values.In the present invention, " at least one " represents one or more kinds of.
According to the first aspect of the invention, the invention provides a kind of nano-carbon material formed body, the formed body to contain
Nano-carbon material and the binding agent by the nano-carbon material molding bonded.
According to the nano-carbon material formed body of the present invention, the nano-carbon material contains O elements and optional N element
(hereinafter, otherwise referred to as nano-carbon material containing hetero atom).
The content of O elements and optional N element can be according to the source of the nano-carbon material in the nano-carbon material
Selected, can also be selected with the concrete application occasion of the nano-carbon material formed body.Usually, with the nano-sized carbon
On the basis of the total amount of material and in terms of element, the contents of O elements can be 2-15 weight %, preferably 5-12 weight %, more excellent
Elect 7-11 weight % as；The content of N element can be 0-5 weight %, and preferably 0.1-5 weight %, more preferably 1.5-4.5 are heavy
Measure %.
In the present invention, the content of each element is determined using X-ray photoelectron spectroscopy.Sample is before testing at 150 DEG C
At a temperature of in helium atmosphere dry 3 hours.Wherein, X-ray photoelectron spectroscopic analysis are in Thermo Scientific companies
Equipped with being tested on the ESCALab250 type x-ray photoelectron spectroscopies of Thermo AvantageV5.926 softwares, excite
Source is monochromatization Al K α X ray, and energy 1486.6eV, power 150W, penetrating energy used in narrow scan be 30eV, and analysis is surveyed
Base vacuum during examination is 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, in Thermo
Data processing is carried out on Avantage softwares, quantitative analysis is carried out using sensitivity factor method in analysis module.
According to the formed body of one side of the invention, in the nano-carbon material, by x-ray photoelectron power spectrum
The amount for the O elements that peak in the range of 531.0-532.5eV determines is IO c, by 532.6-533.5eV models in x-ray photoelectron power spectrum
The amount for the O elements that peak in enclosing determines is IO e, IO c/IO eIn the range of 0.1-1.
In the present invention, by the area A of the O1s spectral peaks in x-ray photoelectron power spectrumO 1The total amount of O elements is determined, by X ray
O1s spectral peaks in photoelectron spectroscopy are divided into two groups of peaks, i.e., the spectral peak (corresponding to C=O species) in the range of 531.0-532.5eV
And the spectral peak (corresponding to C-O species) in the range of 532.6-533.5eV, by the spectral peak in the range of 531.0-532.5eV
Area be designated as AO 2, the area of the spectral peak in the range of 532.6-533.5eV is designated as AO 3, IO c/IO e=AO 2/AO 3。
According to the formed body of one side of the invention, on the basis of the total amount of C element in the nano-carbon material, by X
The content for the C element that peak in X-ray photoelectron spectroscopy X in the range of 284.7-284.9eV determines can be 60-95 weight %, excellent
Elect 70-92 weight % as；The total content of the C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum
Can be 5-40 weight %, preferably 8-30 weight %.
In the present invention, by the area A of the C1s spectral peaks in x-ray photoelectron power spectrumC 1The total amount of C element is determined, by X ray
C1s spectral peaks in photoelectron spectroscopy are divided into two groups of peaks, i.e., the spectral peak in the range of 284.7-284.9eV (corresponds to graphite mould carbon
Species) and spectral peak (corresponding to non-graphite type carbon species) in the range of 286.0-288.8eV, will be in 284.7-284.9eV
In the range of the area of spectral peak be designated as AC 2, the area of the spectral peak in the range of 286.0-288.8eV is designated as AC 3, by X ray light
Content=the A for the C element that peak in electron spectrum in the range of 284.7-284.9eV determinesC 2/AC 1, by x-ray photoelectron power spectrum
Total content=the A for the C element that peak in the range of middle 286.0-288.8eV determinesC 3/AC 1。
According to the formed body of one side of the invention, in the range of 288.6-288.8eV in x-ray photoelectron power spectrum
The amount for the C element that peak determines is IC c, the C element that is determined by the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum
Measure as IC e, IC c/IC eCan be in the range of 0.1-2.
In the present invention, the spectral peak in x-ray photoelectron power spectrum in the range of 286.0-288.8eV (is corresponded into non-graphite
Carbon species) be further divided into two groups of peaks, i.e., the spectral peak in the range of 286.0-286.2eV (corresponds to hydroxyl and ether type carbon thing
Kind) and spectral peak (corresponding to carboxyl, acid anhydride and ester type carbon species) in the range of 288.6-288.8eV, will be in 286.0-
The area of spectral peak in the range of 286.2eV is designated as AC 4, the area of the spectral 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 formed body of one side of the invention, the nano-carbon material can contain N element, can also be free of N
Element.In a kind of embodiment (embodiment hereinafter is referred to as into first embodiment), N members in the nano-carbon material
The content of element is less than 0.1 weight %.In another embodiment (embodiment hereinafter is referred to as into second embodiment)
In, the content of N element is more than 0.1 weight % in the nano-carbon material.
In the first embodiment, on the basis of the total amount of the nano-carbon material and in terms of element, the content of O elements can
Think 6-12 weight %, preferably 7-11 weight %；The content of C element can be 88-94 weight %, preferably 89-93 weights
Measure %.
In the first embodiment, in the nano-carbon material, by 531.0-532.5eV models in x-ray photoelectron power spectrum
The amount for the O elements (that is, C=O) that peak in enclosing determines is IO c, in the range of 532.6-533.5eV in x-ray photoelectron power spectrum
The amount for the O elements (that is, C-O) that peak determines is IO e, IO c/IO eIt is preferred that in the range of 0.3-0.95, more preferably 0.5-0.7's
In the range of.
In the first embodiment, on the basis of the total amount of C element in nano-carbon material, by x-ray photoelectron power spectrum
The content for the C element that peak in the range of 284.7-284.9eV determines can be 75-98 weight %, preferably 85-95 weight %；
The total content of the C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum can be 2-25 weights
Measure %, preferably 5-15 weight %.
In the first embodiment, in the nano-carbon material, by 288.6-288.8eV models in x-ray photoelectron power spectrum
The amount for the C element that peak in enclosing determines is IC c, the C that is determined by the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum
The amount of element is IC e, IC c/IC eCan be in the range of 0.3-1.8, preferably in the range of 0.5-1.5, more preferably in 0.8-1
In the range of.
In this second embodiment, on the basis of the total amount of nano-carbon material and in terms of element, the content of O elements can be
4-20 weight %, preferably 7-15 weight %, more preferably 8-10 weight %；The content of N element can be 0.1-5 weight %,
Preferably 0.4-4.8 weight %, more preferably 1.5-4.5 weight %；The content of C element can be 75-95.9 weight %, preferably
For 80.2-92.6 weight %, more preferably 85.5-90.5 weight %.
In this second embodiment, in the nano-carbon material, by 531.0-532.5eV in x-ray photoelectron power spectrum
In the range of the amount of O elements that determines of peak be IO c, determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum
The amounts of O elements be IO e, IO c/IO eCan be in the range of 0.1-1, preferably in the range of 0.2-0.8, more preferably in 0.4-
In the range of 0.7.
In this second embodiment, with the total amount of the C element determined in the nano-carbon material by x-ray photoelectron power spectrum
On the basis of, the content of the C element determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum can be 60-90
Weight %, preferably 60-85 weight %, more preferably 70-80 weight %；By 286.0-288.8eV in x-ray photoelectron power spectrum
In the range of the total content of C element that determines of peak can be 10-40 weight %, preferably 15-40 weight %, more preferably 20-
30 weight %.
In this second embodiment, in the nano-carbon material, by 288.6-288.8eV in x-ray photoelectron power spectrum
In the range of the amount of C element that determines of peak be IC c, determined by the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum
The amount of C element be IC e, IC c/IC eCan be in the range of 0.1-0.8, preferably in the range of 0.25-0.6.
In this second embodiment, the total amount that the N element in nano-carbon material is determined by x-ray photoelectron power spectrum is IN t,
The amount of the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum is IN c, IN c/IN tCan be
In the range of 0.05-0.5, preferably in the range of 0.1-0.4.In the range of 403.5-406.5eV in x-ray photoelectron power spectrum
The amount of N element that determines of peak be IN n, IN n/IN tCan be in the range of 0.5-0.95, preferably in the range of 0.6-0.8.
In this second embodiment, in nano-carbon material, by 400.6-401.5eV scopes in x-ray photoelectron power spectrum
The N element content of interior peak determination is relatively low not to be contained even.Usually, by 400.6-401.5eV scopes in x-ray photoelectron power spectrum
The amount for the N element that interior peak determines is IN g, IN g/IN tFor not higher than 0.3, typically in the range of 0-0.25, preferably in 0.02-
In the range of 0.2.
In the present invention, the total amount A of N element is determined by the area of the N1s spectral peaks in x-ray photoelectron power spectrumN 1, by X ray
N1s spectral peaks in photoelectron spectroscopy are divided into three groups of peaks, i.e., the spectral peak in the range of 403.5-406.5eV (corresponds to-NO2Thing
Kind), in the range of the spectral peak (corresponding to graphite mould nitrogen species) in the range of 400.6-401.5eV and 398.5-400.1eV
Spectral peak (removes graphite mould nitrogen and-NO2Nitrogen species outside type nitrogen), the area of the spectral peak in the range of 400.6-401.5eV is remembered
For AN 2, the area of the spectral peak in the range of 398.5-400.1eV is designated as AN 3, by the spectral peak in the range of 403.5-406.5eV
Area be designated as AN 4, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/AN 1, IN n/IN t=AN 4/AN 1, obtained ratio be 0.01 with
When lower, it is believed that be designated as 0 without such species, and by the content of such species.
In the present invention, the position at each peak can determine that as the combination corresponding to the summit at the peak, and scope determines by mentioned earlier
The peak combination that refers to corresponding to summit can be within that range peak, a peak can be included within the range, can also be wrapped
Include more than two peaks.Such as：Peak in the range of 398.5-400.1eV refers to that the combination corresponding to summit can be in 398.5-
Whole peaks in the range of 400.1eV.
According to the nano-carbon material formed body of the present invention, the nano-carbon material can by it is common it is various in the form of exist,
Be specifically as follows but be not limited to CNT, graphene, thin layer graphite, nano carbon particle, carbon nano-fiber, Nano diamond and
Combination more than one or both of fullerene.The CNT can be single-walled carbon nanotube, double-walled carbon nano-tube and
Combination more than one or both of multi-walled carbon nanotube.According to nano-carbon material formed body, the nano-carbon material is preferred
For multi-walled carbon nanotube.
According to the nano-carbon material formed body of the present invention, the specific surface area of the multi-walled carbon nanotube is preferably 50-
500m2/ g, the catalytic performance of the formed body so can be further improved, especially as the catalyst of hydrocarbons dehydrogenation reaction
Catalytic performance.The specific surface area of the multi-walled carbon nanotube is more preferably 90-280m2/ g, more preferably 100-180m2/
g.In the present invention, the specific surface area is determined by nitrogen adsorption BET method.
According to the nano-carbon material formed body of the present invention, the multi-walled carbon nanotube is in 400-800 DEG C of temperature range
Weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that in 0.01-0.5 model
In enclosing, more preferable catalytic effect can be so obtained, during catalyst particularly as hydrocarbons dehydrogenation reaction, can be obtained more
Good catalytic effect.w500/w800More preferably in the range of 0.02-0.4, further preferably in the range of 0.1-0.25.This
In invention, w800=W800- W400, w500=W500- W400, W400For the mass loss rate determined at a temperature of 400 DEG C, W800For
The mass loss rate determined at a temperature of 800 DEG C, W500For the mass loss rate determined at a temperature of 500 DEG C；The weightlessness
Rate is determined using thermogravimetric analyzer in air atmosphere, and test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample exists
Depress in 150 DEG C of temperature and 1 normal atmosphere before test and dried 3 hours in helium atmosphere.
According to the nano-carbon material formed body of the present invention, in the nano-carbon material, its outside oxygen atom and nitrogen-atoms
Its nonmetallic heteroatoms, such as sulphur atom and phosphorus atoms, its content can be customary amount.Usually, according to the nanometer of the present invention
Carbon material formed body, in the nano-carbon material, other nonmetallic heteroatoms outside oxygen atom and nitrogen-atoms (such as sulphur atom and
Phosphorus atoms) total amount can be below 0.5 weight %, preferably below 0.2 weight %, more preferably below 0.1 weight %, enter
One step is preferably below 0.05 weight %.According to the nano-carbon material formed body of the present invention, in the nano-carbon material, except selected from
Outside aforesaid metal elements, other metallic atoms can also be contained, other metallic atoms for example can be to be received from preparation
The catalyst used during rice carbon material.The content of other metallic atoms is generally below 2.5 weight %, preferably 2 weights
Below % is measured, is still more preferably below 0.5 weight %, particularly preferably 0.2 weight more preferably below 1 weight %
Measure below %.
According to the nano-carbon material formed body of the present invention, also contain and be used for the heat-resisting of the nano-carbon material molding bonded
Inorganic oxide.In the present invention, term " heat-resistant inorganic oxide " refers to that under oxygen or oxygen-containing atmosphere decomposition temperature is not less than
300 DEG C (such as：Decomposition temperature be 300-1000 DEG C) inorganic oxygen-containing compound.
The heat-resistant inorganic oxide is preferably more than one or both of aluminum oxide, silica and titanium oxide.One
In individual example, the heat-resistant inorganic oxide is aluminum oxide, and it is higher to be molded physical efficiency acquisition according to the nano-carbon material of the example
Feed stock conversion.
In a preferred embodiment, at least part heat-resistant inorganic oxide is silica, according to the preferable reality
The nano-carbon material formed body of mode is applied in the catalyst as hydrocarbon dehydrogenation reaction, can be in feed stock conversion and selectivity of product
Between obtain preferably balance.It is described on the basis of the total amount of the heat-resistant inorganic oxide in the preferred embodiment
The content of silica can be 10-100 weight %, more preferably preferably 20-99 weight %, 50-99 weight %, silicon
Outside the content of heat-resistant inorganic oxide can be 0-90 weight %, preferably 1-80 weight %, more preferably 1-50 weight
Measure %.In the preferred embodiment, the instantiation of the heat-resistant inorganic oxide outside silicon can be included but not
It is limited to aluminum oxide and/or titanium oxide.As an example of the preferred embodiment, the heat resistant inorganic oxygen outside silicon
Compound is titanium oxide.
According to the nano-carbon material formed body of the present invention, the content of the nano-carbon material can become in wider scope
It is dynamic, still such that the nano-carbon material formed body has higher intensity.Usually, with the nano-carbon material formed body
On the basis of total amount, the content of the nano-carbon material can be 6-94 weight %, preferably 8-92 weight %, more preferably 10-
90 weight %, more preferably 20-90 weight %, it is still more preferably 40-90 weight %, particularly preferably 70-90 weight
% is measured, the content of the heat-resistant inorganic oxide can be 6-94 weight %, preferably 8-92 weight %, more preferably 10-90
Weight %, more preferably 10-80 weight %, it is still more preferably 10-60 weight %, particularly preferably 10-30 weight
Measure %.The composition of formed body can use x-ray fluorescence spectrometry.In embodiment disclosed by the invention, by the gauge that feeds intake
The composition of the composition and the formed body using x-ray fluorescence spectrometry of obtained formed body is basically identical, and error is 5%
Within.
According to the second aspect of the invention, the invention provides a kind of nano-carbon material formed body, the formed body to contain
Nano-carbon material and for by the heat-resistant inorganic oxide of the nano-carbon material molding bonded.
According to the formed body described in second aspect of the present invention, the nano-carbon material is using the method comprised the following steps
It is made：A kind of aqueous dispersions for being dispersed with raw material nano carbon material and at least one modifying agent are carried out instead in closed container
Should, in course of reaction, the temperature of the aqueous dispersions is in the range of 80-250 DEG C.
The modifying agent is peroxide, or is peroxide and HNO3。
The peroxide refers to the compound for containing-O-O- keys in molecular structure.Specifically, the peroxide can be with
Selected from the organic peroxide shown in hydrogen peroxide and Formulas I,
In Formulas I, R1And R2It each is selected from H, C4-C12Alkyl, C6-C12Aryl, C7-C12Aralkyl and
And R1And R2It is asynchronously H, R3For C4-C12Straight or branched alkyl or C6-C12Aryl.
In the present invention, C4-C12The instantiation of alkyl include but is not limited to normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, neopentyl, isopentyl, tertiary pentyl, hexyl (the various isomers for including hexyl), cyclohexyl, octyl group are (including pungent
The various isomers of base), nonyl (the various isomers for including nonyl), decyl (the various isomers for including decyl), hendecane
Base (the various isomers for including undecyl) and dodecyl (the various isomers for including dodecyl).
In the present invention, C6-C12The instantiation of aryl include but is not limited to phenyl, naphthyl, aminomethyl phenyl and ethylo benzene
Base.
In the present invention, C7-C12The instantiation of aralkyl including but is not limited to phenyl methyl, phenylethyl, phenyl just
Propyl group, phenyl normal-butyl, phenyl t-butyl, propyloxy phenyl base, phenyl n-pentyl and phenyl normal-butyl.
The instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, TBHP, peroxidating
Hydrogen isopropylbenzene, hydrogen peroxide ethylbenzene, cyclohexyl hydroperoxide, cumyl peroxide, dibenzoyl peroxide, the uncle of peroxidating two
Butyl and dilauroyl peroxide.
The modifying agent can contain HNO3, HNO can also be free of3.In one embodiment, the modifying agent was
The embodiment (is referred to as embodiment A) by oxide below.In a kind of embodiment being more highly preferred to, the modifying agent is
Peroxide and HNO3(embodiment is referred to as embodiment B below), it is molded according to the nano-carbon material of the embodiment
Body can obtain higher catalytic activity in the catalyst as hydrocarbon dehydrogenation reaction.
In embodiment A, although in the presence of peroxide, raw material nano carbon material is subjected to hydro-thermal process
Catalytic activity during catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction is improved, it is preferred that being carried out to reaction condition
Optimize further to improve catalytic activity of the nano-carbon material formed body in hydrocarbon dehydrogenation reaction.
In embodiment A, raw material nano carbon material：The weight ratio of peroxide is preferably 1：In the range of 0.5-50,
More preferably 1：In the range of 1.5-40.
In embodiment A, raw material nano carbon material：H2O weight ratio is preferably 1：In the range of 2-50, in the use of water
When amount is within the scope of being somebody's turn to do, structural form retentivity of the nano-carbon material in processing procedure is more preferable, such as：Raw material nano carbon
When material is CNT, it will not be cut off substantially in processing procedure.Raw material nano carbon material：H2O weight ratio is more preferably
1：In the range of 5-40, further preferably 1：In the range of 10-30.Furthermore it is also possible to the species pair according to peroxide
The dosage of water is adjusted, and is defined so that the peroxide can be dispersed in water.
In embodiment B, by by HNO3With peroxide combination using nano-carbon material formed body can be significantly improved
Catalytic activity in hydrocarbon dehydrogenation reaction.In embodiment B, raw material nano carbon material：HNO3：The weight of peroxide is than excellent
Elect 1 as：0.01-20：0.01-20, the nano-carbon material containing hetero atom thus prepared is in the catalyst as hydrocarbon dehydrogenation reaction
More preferable catalytic effect can be obtained.Raw material nano carbon material：HNO3：The weight ratio more preferably 1 of peroxide：0.05-10：
0.02-10, more preferably 1：0.2-6：0.5-3.
In embodiment B, raw material nano carbon material：H2O weight ratio preferably 1：2-500, it is in the dosage of water
When within the scope of being somebody's turn to do, structural form retentivity of the nano-carbon material in processing procedure is more preferable, such as：Raw material nano carbon material is
During CNT, it will not be cut off substantially in processing procedure.Raw material nano carbon material：H2O weight ratio more preferably 1：15-
400.The dosage of water can also be adjusted according to the species of peroxide so that the peroxide can be dispersed in water for
It is accurate.Furthermore it is also possible to according to HNO3Dosage the dosage of water is adjusted, usually, HNO in aqueous dispersions3Mass concentration
Preferably not higher than 50 weight %, more preferably not above 40 weight %, more preferably not higher than 30 weight %, more enter one
Step is preferably not higher than 25 weight %.
According to the formed body described in second aspect of the present invention, it is preferable that in course of reaction, the temperature of the aqueous dispersions
In the range of 80-250 DEG C.When the temperature of the aqueous dispersions is within above range, original can not only be effectively improved
Expect the oxygen atom and nitrogen atom content in nano-carbon material, and the structural form of raw material nano carbon material will not be produced obvious
Influence.It is highly preferred that in course of reaction, the temperature of the aqueous dispersions is in the range of 110-200 DEG C.The reaction continues
Time can be selected according to the temperature of reaction.Usually, the duration of the reaction can be in the model of 0.5-96 hours
In enclosing, preferably in the range of 2-72 hours, more preferably in the range of 8-36 hours.
According to the formed body described in second aspect of the present invention, the moisture can be formed using conventional various methods
Dispersion liquid, for example, can by raw material nano carbon material in water (be preferably deionized water), then add the peroxide and
Optional HNO3It is well mixed, so as to obtain the aqueous dispersions.In order to further improve the scattered effect of raw material nano carbon material
Fruit, while shorten the scattered time, the method for sonic oscillation can be used to be dispersed in water raw material nano carbon material.It is described super
The condition of sound oscillation can be conventional selection, and usually, the frequency of the sonic oscillation can be 10-100kHz, the ultrasound
The duration of vibration can be 0.1-6 hours, preferably 0.5-2 hours.HNO3Typically provide in form of an aqueous solutions, it is described
Peroxide can in form of an aqueous solutions be provided, can also provided in the form of pure material according to specific species.
According to the formed body described in second aspect of the present invention, oxygen element and nitrogen in the raw material nano carbon material
Content is not particularly limited, and can be conventional selection.Usually, the content of oxygen element is not high in the raw material nano carbon material
In 1.5 weight %, preferably not higher than 0.5 weight %, more preferably not above 0.3 weight %；The content of nitrogen is not high
In 0.2 weight %, preferably not higher than 0.1 weight %, more preferably not above 0.05 weight %, more preferably it is not higher than
0.02 weight %.Remaining nonmetallic heteroatoms (such as phosphorus atoms in the raw material nano carbon material outside oxygen atom and nitrogen-atoms
And sulphur atom) total amount (in terms of element) can be customary amount.Usually, in the raw material nano carbon material except oxygen element and
The total amount (in terms of element) of remaining nonmetallic heteroatoms outside nitrogen is not higher than 0.5 weight %, preferably not higher than 0.2 weight
Measure %, more preferably not above 0.1 weight %, more preferably not higher than 0.05 weight %.The raw material nano carbon material
According to the difference in source, some metallic elements may be contained, such as the catalysis used during from preparing raw material nano-carbon material
Metallic atom in agent.In the raw material nano carbon material content of metallic atom be generally (in terms of element) 2.5 weight % with
Under, preferably below 1.8 weight %, more preferably below 0.5 weight %.
According to the formed body described in second aspect of the present invention, raw material nano carbon material can use this area before use
Conventional method is pre-processed (as washed), to remove some impurity of raw material nano carbon material surface；Can also be without
Pretreatment, directly use.In preparation example disclosed by the invention, raw material nano carbon material is not pre-processed using preceding.
According to the formed body described in second aspect of the present invention, the raw material nano carbon material can be but be not limited to carbon and receive
One or both of mitron, graphene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene with
On combination.The CNT can be single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube in one kind or
Two or more combinations.Preferably, the raw material nano carbon material is CNT, more preferably multi-walled carbon nanotube.
According to the formed body described in second aspect of the present invention, in a preferred embodiment, the raw material nano
Carbon material is multi-walled carbon nanotube, and the specific surface area of the multi-walled carbon nanotube can be 50-500m2/ g, preferably 80-
300m2/ g, more preferably 100-260m2/ g, more preferably 120-190m2/g。
When the raw material nano carbon material is multi-walled carbon nanotube, temperature of the multi-walled carbon nanotube at 400-800 DEG C
The weight-loss ratio spent in section is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800Can be in 0.01-
In the range of 0.5, preferably in the range of 0.02-0.4.
According to the formed body described in second aspect of the present invention, the reaction is carried out in closed container.The reaction can
To be carried out under self-generated pressure (that is, not applying pressure additionally), can also carry out under pressure.Preferably, it is described anti-
It should carry out at autogenous pressures.The closed container can be the common reactor that can realize sealing and heating, as high pressure is anti-
Answer kettle.
According to the formed body described in second aspect of the present invention, isolated in the mixture that can also include obtaining from reaction
It is dried after solid matter, so as to obtain nano-carbon material.It can use what conventional solid-liquid separating method obtained from reaction
Solid matter is isolated in mixture, such as combination more than one or both of centrifugation, filtering and decantation.The bar of the drying
Part can be conventional selection, be defined by that can remove the volatile materials in the solid matter isolated.Usually, the drying can
To be carried out at a temperature of 50-400 DEG C, carried out preferably at a temperature of 80-180 DEG C.The duration of the drying can root
Selected according to dry temperature and mode.Usually, the duration of the drying can be no more than 48 hours, be preferably
4-24 hours, more preferably 6-12 hours.The drying can be carried out under normal pressure (that is, 1 standard atmospheric pressure), can also subtracted
Carried out under conditions of pressure.From the further angle for improving dry efficiency, the drying is preferably entered at reduced pressure
OK.Also spray drying etc. is without by solid matter is isolated in mixture the step of can be used, drying now can be
Carried out at a temperature of 120-400 DEG C, carry out preferably at a temperature of 150-350 DEG C, more preferably enter at a temperature of 180-300 DEG C
OK, the duration of the drying can be selected according to dry degree, be such as no more than 0.5 hour, preferably no more than
0.2 hour, more preferably less than 0.1 hour.
According to the formed body described in second aspect of the present invention, also contain and be used for the nano-carbon material molding bonded
Heat-resistant inorganic oxide.The species and its content of the heat-resistant inorganic oxide with it is heat-resisting described in one side of the invention
The species and content of inorganic oxide are identical, are no longer described in detail herein.
Nano-carbon material formed body according to one side of the invention and second aspect can have as needed
There is variously-shaped such as spherical, bar shaped.
There is nano-carbon material formed body according to one side of the invention and second aspect higher resisting to break
Broken intensity.Usually, can be more than 4N/mm according to the radial direction crushing strength of the nano-carbon material formed body of the present invention, typically
For more than 5N/mm.Specifically, the footpath of the nano-carbon material formed body according to one side of the invention and second aspect
It is 5-25N/mm, preferably 6-25N/mm, more preferably 10-25N/mm to crushing strength.In the present invention, radial direction crushing strength is pressed
According to《Petrochemical Engineering Analysis method》In RIPP 25-90 described in (Science Press, the nineteen ninety first edition, Yang Cui are waited and compiled surely)
Defined method measure.
Nano-carbon material formed body according to one side of the invention and second aspect has higher hole
Rate.Usually, according to the present invention nano-carbon material formed body porosity can be more than 5%, it might even be possible to for 10% with
On, such as can be in the range of 5-50%, preferably in the range of 10-30%, more preferably in the range of 12-25%.This
In invention, porosity refers to all interstitial space volume sums and the body of the nano-carbon material formed body in nano-carbon material formed body
Long-pending ratio, the porosity of the nano-carbon material formed body is referred to as, is expressed as a percentage, using mercury injection method (with reference to text
Offer《Graphite porosity of porous material study on determination method》,《Lubrication and sealing》, 2010,35 (10)：99-101) method determines.
According to the third aspect of the present invention, should the invention provides a kind of preparation method of nano-carbon material formed body
Method include nano-carbon material is mixed with binding agent source, obtained mixture is molded, obtains article shaped, by it is described into
Type thing is dried and is optionally calcined.
Method according to third aspect of the present invention, the binding agent source are selected from heat-resistant inorganic oxide and/or resistance to
The precursor of hot inorganic oxide.The heat-resistant inorganic oxide be preferably one kind in aluminum oxide, silica and titanium oxide or
It is two or more.In an example, the heat-resistant inorganic oxide is aluminum oxide, according to the nano-carbon material formed body of the example
Higher feed stock conversion can be obtained.
In a preferred embodiment, at least part heat-resistant inorganic oxide is silica, according to the preferable reality
Nano-carbon material formed body prepared by the mode of applying can select in the catalyst as hydrocarbon dehydrogenation reaction in feed stock conversion and product
Preferably balance is obtained between selecting property.In the preferred embodiment, on the basis of the total amount of the heat-resistant inorganic oxide,
The content of the silica can be 10-100 weight %, more preferably preferably 20-99 weight %, 50-99 weight %, deoxygenation
The content of heat-resistant inorganic oxide outside SiClx can be 0-90 weight %, preferably 1-80 weight %, more preferably 1-50
Weight %.In the preferred embodiment, the instantiation of the heat-resistant inorganic oxide outside silicon can include but
It is not limited to aluminum oxide and/or titanium oxide.As an example of the preferred embodiment, the heat resistant inorganic outside silicon
Oxide is titanium oxide.
The heat-resistant inorganic oxide can by it is common it is various in the form of provide, such as (such as Ludox, titanium is molten with colloidal sol
Glue, Alumina gel) form provide.The precursor of the heat-resistant inorganic oxide can be according to expected heat-resistant inorganic oxide
Species is selected.
For example, when the heat-resistant inorganic oxide is aluminum oxide, the precursor of the heat-resistant inorganic oxide can be
The material of aluminum oxide can be transformed into, the material of aluminum oxide can be such as formed by hydrolysis-condensation reaction and/or roasting, for example, it is organic
Aluminium salt and inorganic aluminate, its instantiation can include but is not limited to hydrated alumina (such as boehmite), aluminium hydroxide, sulphur
Sour aluminium, sodium metaaluminate, aluminium chloride, aluminum nitrate and C1-C10Organic aluminium salt (such as aluminium isopropoxide, isobutanol aluminum, three isopropoxies
Aluminium, three tert-butoxy aluminium and isooctanol aluminium) one or both of more than.
For another example when the heat-resistant inorganic oxide is silica, the precursor of the heat-resistant inorganic oxide can be with
For the material of silica can be transformed into, the material of silica can be such as formed by hydrolysis-condensation reaction and/or roasting, its is specific
Example can include but is not limited to the organo-silicon compound that hydrolysis-condensation reaction can occur.It is described that hydrolysis-condensation reaction can occur
Organo-silicon compound can be the common various materials that silica can be formed by hydrolysis-condensation reaction.As an example,
The organo-silicon compound that hydrolysis-condensation reaction can occur can be more than one or both of compound shown in Formula II：
In Formula II, R4、R5、R6And R7Respectively C1-C4Alkyl.The C1-C4Alkyl include C1-C4Straight chained alkyl
And C3-C4Branched alkyl, its instantiation can include but is not limited to：It is methyl, ethyl, n-propyl, isopropyl, normal-butyl, secondary
Butyl, isobutyl group and the tert-butyl group.Preferably, organic silicon source is selected from methyl silicate, tetraethyl orthosilicate, positive silicic acid positive third
Ester, positive isopropyl silicate and positive silicic acid N-butyl.
In another example when the heat-resistant inorganic oxide is titanium oxide, the precursor of the heat-resistant inorganic oxide can be with
For organic titanate and/or inorganic titanium salt, its instantiation can include but is not limited to TiCl4、Ti(SO4)2、TiOCl2, hydrogen-oxygen
Change titanium, nitric acid titanium salt, phosphoric acid titanium salt, fatty alcohol titanium and organic titanate (such as tetraisopropyl titanate, the n-propyl of metatitanic acid four, metatitanic acid
One or more in four butyl esters and tetraethyl titanate) in one or more.
Method according to third aspect of the present invention, in one embodiment, the binding agent source are selected from heat-resisting
Inorganic oxide, such as the heat-resistant inorganic oxide provided with solation.In this embodiment, by nano-carbon material with gluing
It is molded after knot agent source is well mixed.In another embodiment, at least part binding agent source is heat resistant inorganic oxygen
The precursor of compound.In this embodiment, after nano-carbon material is mixed with binding agent source, entered according to the species in binding agent source
Row processing, is transformed into heat-resistant inorganic oxide by the precursor of the heat-resistant inorganic oxide in binding agent source.
Method according to third aspect of the present invention, the mixture preferably also contain at least one inorganic agent, institute
It is alkali or HNO to state inorganic agent3, the nano-carbon material formed body finally prepared so can be further improved anti-as hydrocarbon dehydrogenation
The catalytic activity during catalyst answered.The alkali can be organic base and/or inorganic base.The inorganic base can be ammonia, sun from
Son is the alkali of alkali metal and cation is more than one or both of alkali of alkaline-earth metal.The organic base can be urea,
It is more than one or both of amine, hydramine and quaternary ammonium base.
The quaternary ammonium base can be various organic level Four ammonium alkali, and the amine can be various NH3In at least one hydrogen quilt
The compound formed after alkyl (being preferably alkyl) substitution, the hydramine can be various NH3In at least one hydrogen by containing hydroxyl
The compound formed after alkyl (being preferably alkyl) substitution of base.Specifically, the quaternary ammonium base can be the quaternary ammonium shown in formula III
Alkali,
In formula III, R8、R9、R10And R11It is identical or different, respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and
C3-C4Branched alkyl, such as：R8、R9、R10And R11Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding
Base, isobutyl group or the tert-butyl group.
The amine can be the aliphatic amine and general formula R that formula IV represents15(NH2)2One kind in the material of expression or two
More than kind,
In formula IV, R12、R13And R14Respectively H, C1-C6Alkyl or C6-C12Aryl, and R12、R13And R14When different
For H.In the present invention, C1-C6The instantiation of alkyl can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, just
Butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl and n-hexyl.In the present invention, C6-C12
The instantiation of aryl include but is not limited to phenyl, naphthyl, aminomethyl phenyl and ethylphenyl.
General formula R15(NH2)2In, R15Can be C1-C6Alkylidene or C6-C12Arlydene.In the present invention, C1-C6's
Alkylidene includes C1-C6Straight-chain alkyl-sub and C3-C6Branched alkylidene, its instantiation can include but is not limited to：Methylene
Base, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, isobutylidene, the sub- tert-butyl group, sub- n-pentyl and sub- n-hexyl.This
In invention, C6-C12The instantiation of arlydene include but is not limited to phenylene and naphthylene.
The hydramine can be the aliphatic hydramine that Formula V represents,
In Formula V, R16、R17And R18Respectively-R19OH or hydrogen, and R16、R17And R18In it is at least one be-R19OH, R19
For C1-C4Alkylidene.In the present invention, C1-C4Alkylidene include C1-C4Straight-chain alkyl-sub and C3-C4Branched alkylidene,
Its instantiation can include but is not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, isobutylidene
With the sub- tert-butyl group.
The instantiation of the alkali can include but is not limited to ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate,
Potassium carbonate, barium hydroxide, urea, hydrazine, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, n-propylamine, two positive third
Amine, Tri-n-Propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl
Amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, iso-amylamine, di-iso-amylamine, three isoamyls
Amine, tertiary amylamine, n-hexylamine, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane base amine, dodecyl amine, dimethyl
Base amine, n-tridecane base amine, n-tetradecane base amine, n-pentadecane base amine, n-hexadecyl amine, triethanolamine, triisopropanolamine,
Diethanol amine, two n-propanolamines, three n-propanolamines, two n-butanol amine, three n-butanol amine, dodecyl-dimethyl amine, the tetradecane
It is base dimethyl amine, hexadecyldimethyl benzyl ammonium amine, ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, substituted or unsubstituted
Pyrroles, substituted or unsubstituted nafoxidine, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substitution or
Unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted EEDQ, take
Generation or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinolin, substitution or unsubstituted
Pyrimidine, aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-toluidine, m-toluidine, right
Methylaniline, 23 dimethyl aniline, 2,4- dimethylanilines, 2,5- dimethylanilines, 2,6- dimethylanilines, 3,4- diformazans
Base aniline, 3,5- dimethylanilines, 2,4,6- trimethylanilines, o ethyl aniline, N- butylanilines, 2,6- diethylanilines,
Cyclohexylamine, cyclopentamine, hexamethylenetetramine, diethylenetriamine, triethylene tetramine, TMAH, tetraethyl hydroxide
Ammonium, TPAOH (including its various isomers, such as four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), four fourths
Base ammonium hydroxide (including its various isomers, such as 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group hydrogen-oxygens
Change ammonium and tetra-tert ammonium hydroxide) and one or both of four pentyl ammonium hydroxide (including its various isomers) more than.
Preferably, the alkali is organic base, so can further improve the nano-carbon material formed body conduct finally prepared
The catalytic activity of the catalyst of hydrocarbon dehydrogenation reaction.It is highly preferred that the alkali is synthesis of titanium silicon molecular sieve template, such as formula III
Shown quaternary ammonium base, the nano-carbon material formed body thus prepared have higher crushing strength, and as hydrocarbon dehydrogenation
The catalytic activity further improved is shown during the catalyst of reaction.
The dosage of the inorganic agent can be selected according to the dosage in binding agent source.Usually, inorganic agent glues with described
The mol ratio for tying agent source is 0.05-20：1, preferably 0.1-18：1, the binding agent source is in terms of oxide.In a kind of embodiment party
In formula, inorganic agent and the mol ratio in the binding agent source are 0.1-2：1, the binding agent source is in terms of oxide.Another real
Apply in mode, inorganic agent and the mol ratio in the binding agent source are 0.2-18：1, the binding agent source is in terms of oxide.
Method according to third aspect of the present invention, various decentralized media can be used by nano-carbon material and bonding
Agent source and optional alkali are well mixed.Preferably, the decentralized medium is water.The dosage of the decentralized medium is with can be by nanometer
Carbon material, binding agent source and optional alkali are well mixed to be defined.As an example, when the decentralized medium is water, water
Mol ratio with the binding agent source can be 5-150：1, preferably 10-80：1, the binding agent source is in terms of oxide.
The present inventor has found that molecular sieve preparation solution generally contains caused by molecular sieve preparation process in research process
There are the required binding agent source of the present invention and alkali, while also contain water, above-mentioned molecular sieve preparation solution is mixed with nano-carbon material
One of water, binding agent source and alkali, both or three are alternatively supplemented afterwards, nano-carbon material can not only be molded, and are made
Standby nano-carbon material also shows higher crushing strength, while still shows preferable catalytic activity, also real in addition
Recycling of the system with molecular sieve for preparing for process waste is showed.
The molecular sieve preparation solution can be the common various required binding agent sources of the present invention and optional of providing
The molecular sieve preparation solution of alkali.Preferably, the molecular sieve preparation solution is the crystallization mother liquor and siliceous molecular sieve of siliceous molecular sieve
Reset mixed liquor more than one or both of modified mother liquor.The siliceous molecular sieve can be silica zeolite, containing miscellaneous original
It is more than one or both of sub- si molecular sieves (such as HTS) and Si-Al molecular sieve.The crystallization mother liquor refers to passing through
When hydrothermal crystallizing prepares molecular sieve, the mixture obtained to hydrothermal crystallizing carries out the liquid that separation of solid and liquid obtains, i.e., brilliant from hydro-thermal
Change and the liquid mixture remained after the molecular sieve to be formed is isolated in obtained mixture, also referred to as synthesis mother liquid, filtering waste liquid
Or filter raw liquid.The rearrangement modified mother liquor refers to when preparing modified molecular screen by hydrothermal modification rearrangement, to hydrothermal modification
The mixture obtained after rearrangement carries out the liquid that separation of solid and liquid obtains, i.e., is isolated in the mixture for resetting to obtain from hydrothermal modification
The liquid mixture remained after molecular sieve, mother liquor, modified mother liquor are also referred to as reset, filtering waste liquid, modified filtering waste liquid is reset, changes
Property filter raw liquid or reset filter raw liquid.The crystallization mother liquor and rearrangement solution can be mixed directly with nano-carbon material, according to need
It can also be concentrated or be mixed after being diluted with nano-carbon material, so that the dosage in binding agent source, alkali and water can be caused
It can meet to require, proportion requirement as previously described is defined.
It is highly preferred that the siliceous molecular sieve preparation solution is the crystallization mother liquor (crystallization of such as silica zeolite of si molecular sieves
Mother liquor), crystallization mother liquor (crystallization mother liquor of such as HTS), the crystallization mother liquor of Si-Al molecular sieve of the si molecular sieves containing hetero atom
One or both of with the modification rearrangement solution (rearrangement solution of such as silica zeolite and HTS) of above-mentioned siliceous molecular sieve
Mixed liquor above.
The concrete composition of the crystallization mother liquor and rearrangement solution is not particularly limited, as long as binding agent source and optional can be provided
Alkali.As an example, in the crystallization mother liquor of siliceous molecular sieve, with SiO2The content of the element silicon of meter is generally
0.05-10 weight %, preferably 0.1-5 weight %, more preferably 1-4 weight %；The content of alkali is generally 0.05-15 weights
Measure %, more preferably preferably 0.1-15 weight %, 1.5-14 weight %.As another example, the rearrangement of HTS
In liquid, with SiO2The content of the element silicon of meter is generally 0.01-10 weight %, preferably 0.02-5 weight %, more preferably
0.5-2 weight %；With TiO2The content of the titanium elements of meter is generally 0.0001-0.2 weight %, preferably 0.001-0.1 weights
Measure %, more preferably 0.01-0.08 weight %；The content of alkali is generally 0.01-10 weight %, preferably 0.05-5 weight %,
More preferably 1-4 weight %.As there is an example, in the crystallization mother liquor of Si-Al molecular sieve, with SiO2The element silicon of meter contains
Amount is generally 0.05-10 weight %, more preferably preferably 0.1-8 weight %, 1-4 weight %；With Al2O3The aluminium element of meter
Content is generally 0.01-5 weight %, preferably 0.05-2 weight %, more preferably 0.1-0.5 weight %, and the content of alkali is general
For 0.05-15 weight %, preferably 0.1-14 weight %, more preferably 8-13 weight %.
Method according to third aspect of the present invention, when using molecular sieve preparation solution, the inorganic agent is preferably
Alkali.
Method according to third aspect of the present invention, in a preferred embodiment, by the mixture
Before being molded, the mixture is subjected to hydro-thermal process (that is, mixture hydro-thermal process obtained is molded), such energy
Further improve catalytic activity during catalyst of the nano-carbon material formed body finally prepared as hydrocarbon dehydrogenation reaction.It is excellent at this
In the embodiment of choosing, nano-carbon material, binding agent source and optional alkali can be dispersed in water, aqueous dispersions are carried out
Hydro-thermal process.
In the preferred embodiment, the condition of hydro-thermal process is not particularly limited, as long as enter in closed environment
Row high-temperature process.Specifically, the temperature of the hydro-thermal process can be 100-200 DEG C, preferably 120-180 DEG C.It is described
The time of hydro-thermal process can be selected according to the temperature for carrying out hydro-thermal process, typically can be 0.5-24 hours, be preferably
6-12 hours.The hydro-thermal process can carry out (that is, in hydrothermal treatment process, not applying pressure additionally at autogenous pressures
Power), it can also be carried out under conditions of pressure is additionally applied.Preferably, the hydro-thermal process is carried out at autogenous pressures.
Method according to third aspect of the present invention, the dosage in binding agent source can be according to expected nano-carbon material
The content of binding agent is selected in formed body.Usually, the dosage in the binding agent source causes in the formed body that finally prepares,
The content of nano-carbon material can be more than 5 weight % (such as more than 6 weight %), preferably more than 10 weight %, more preferably
More than 50 weight %, it is still more preferably more than 70 weight %, still more preferably more preferably more than 60 weight %
For more than 75 weight %, particularly preferably more than 80 weight %, the content of the nano-carbon material is generally below 95 weight %,
Preferably below 94 weight %, more preferably below 90 weight %.In an example, with the nano-carbon material formed body
On the basis of total amount, the content of the nano-carbon material can be 5-95 weight %, preferably 6-94 weight %, more preferably 8-92
Weight %, more preferably 10-90 weight %, it is still more preferably 20-90 weight %, particularly preferably 40-90 weight
% is measured, particularly preferably 70-90 weight %, the content of the heat-resistant inorganic oxide can be 5-95 weight %, be preferably
6-94 weight %, more preferably 8-92 weight %, more preferably 10-90 weight %, it is still more preferably 10-80 weights
%, particularly preferably 10-60 weight % are measured, particularly preferably 10-30 weight %.When carrying out hydro-thermal process before the forming, i.e.,
Make under relatively low binder content, can also obtain higher intensity.Usually, when carrying out hydro-thermal process before the forming, with institute
On the basis of the total amount for stating formed body, the content of the nano-carbon material is preferably 75-95 weight %, and more preferably 85-95 is heavy
% is measured, the content of the heat-resistant inorganic oxide is preferably 5-25 weight %, more preferably 5-15 weight %.
Method according to third aspect of the present invention, conventional method can be used to contain nano-carbon material and bonding
The mixture in agent source is molded, and obtains article shaped., can be by way of mediating and/or extruding by institute as an example
State mixture shaping.The article shaped can have common variously-shaped such as spherical, bar shaped.
Method according to third aspect of the present invention, the article shaped can be dried under normal conditions,
To remove the volatile materials in the article shaped.Usually, the drying can be carried out at a temperature of 50-200 DEG C, preferably
Carry out at a temperature of 80-180 DEG C, carried out more preferably at a temperature of 120-180 DEG C.The duration of the drying can root
Selected according to dry temperature, typically can be preferably 3-24 hours, more preferably 5-15 hours no more than 48 hours.
It is able to can also be calcined without roasting through dry article shaped.The present invention does not have for the condition of roasting yet
It is particularly limited to, can carries out under normal conditions.Usually, the roasting can 300-800 DEG C, preferably not higher than
Carried out at a temperature of 650 DEG C.The roasting can be carried out in oxygen-containing atmosphere (such as air, oxygen), can also be non-oxygenous
Carried out in atmosphere (such as nitrogen, group 0 element gas).When the roasting is carried out in oxygen-containing atmosphere, the roasting is preferably in 300-
Carry out at a temperature of 500 DEG C, more preferably carried out at a temperature of not higher than 450 DEG C.Enter in the roasting in non-oxygen-containing atmosphere
During row, the roasting is more preferably carried out preferably at 400-800 DEG C at a temperature of the temperature not higher than 750 DEG C.The roasting
Duration can be 1-12 hours, preferably 2-4 hours.
Method according to third aspect of the present invention, the nano-carbon material in various sources can be handled, can
Think not surface treated nano-carbon material, or surface treated nano-carbon material.In the present invention, penetrated using X
Photoelectron Spectroscopy detects to the surface of nano-carbon material, if removing C in nano-carbon material surface-element after testing
The total content of element outside element is below 2 weight %, then the nano-carbon material is considered as into not surface treated nano carbon material
Material, conversely, the nano-carbon material then is considered as into surface treated nano-carbon material.
In one embodiment, the nano-carbon material is not surface treated nano-carbon material.In the embodiment party
In formula, before the mixture is molded, the mixture is preferably subjected to hydro-thermal process in closed container, so not
It is only capable of significantly improving the intensity of the formed body finally prepared, and the catalytic performance of the formed body finally prepared can be obviously improved.
It is highly preferred that the binding agent source and optional alkali source come from molecular sieve preparation solution, by receiving for non-modified surface treatment
Rice carbon material carries out hydro-thermal process in molecular sieve preparation solution can further improve the formed body finally prepared in hydrocarbon dehydrogenation reaction
In catalytic performance.In this embodiment, the nano-carbon material can by it is common it is various in the form of exist, be specifically as follows
But it is not limited in CNT, graphene, thin layer graphite, nano carbon particle, carbon nano-fiber, Nano diamond and fullerene
One or more kinds of combinations.The CNT can be single-walled carbon nanotube, double-walled carbon nano-tube and multi-wall carbon nano-tube
Combination more than one or both of pipe, preferably multi-walled carbon nanotube.The specific surface area of the multi-walled carbon nanotube can be with
For 50-500m2/ g, preferably 80-300m2/ g, more preferably 90-250m2/g.The multi-walled carbon nanotube is at 400-800 DEG C
Weight-loss ratio in temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that
In the range of 0.01-0.5.As an example, described without surface treating nano carbon material can be second side of the invention
Raw material nano carbon material in formed body described in face.
In another embodiment, the nano-carbon material is surface treated nano-carbon material, by X ray photoelectricity
Sub- power spectrum determines that the surface treated nano-carbon material contains O elements and optional N element.
Specifically, the surface treated nano-carbon material can be in the present invention one side formed body
Nano-carbon material in second aspect formed body of nano-carbon material and/or the present invention.
According to the fourth aspect of the present invention, the invention provides a kind of method system as described in third aspect of the present invention
Standby nano-carbon material formed body.
Nano-carbon material formed body according to the 4th aspect of the present invention has higher crushing strength.Typically
Ground, the radial direction crushing strength according to the nano-carbon material formed body of the present invention can be more than 4N/mm, generally more than 5N/mm.
Specifically, the radial direction crushing strength of the nano-carbon material formed body according to one side of the invention and second aspect is
5-25N/mm, preferably 6-25N/mm, more preferably 10-25N/mm.According to the nano carbon material described in the 4th aspect of the present invention
Material formed body has higher porosity.Usually, the nano-carbon material formed body according to the 4th aspect of the present invention
Porosity can be more than 5%, it might even be possible to it is more than 10%, such as can be in the range of 5-50%, preferably in 10-30%
In the range of, more preferably in the range of 12-25%.
According to the fifth aspect of the present invention, the invention provides a kind of forming method of nano-carbon material, this method bag
Include and nano-carbon material is subjected to hydro-thermal process in a kind of aqueous dispersions, the sizing material forming that hydro-thermal process is obtained, be molded
Thing, the article shaped is dried and is optionally calcined, the aqueous dispersions contain binding agent source, the binding agent source choosing
From the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide.The binding agent source and third aspect of the present invention institute
It is identical to state the species in binding agent source, is no longer described in detail herein.
According to the method described in the 5th aspect of the present invention, the nano-carbon material in various sources can be handled, can
Think not surface treated nano-carbon material, or surface treated nano-carbon material.The nano-carbon material tool
Body can be the nano-carbon material described in third aspect of the present invention methods described, no longer be described in detail herein.
According to the method described in the 5th aspect of the present invention, the aqueous dispersions preferably also contain at least one inorganic agent,
The inorganic agent is selected from alkali, acid and peroxide.It so can further improve the anti-of the nano-carbon material formed body that finally prepares
Breaking strength, while when can also further improve catalyst of the nano-carbon material formed body finally prepared as hydrocarbon dehydrogenation reaction
Catalytic activity.Particularly when the nano-carbon material is not surface treated nano-carbon material, it can significantly improve final
The crushing strength and catalytic performance of the nano-carbon material formed body of preparation.
The alkali is identical with the species of alkali and dosage that are related in third aspect of the present invention methods described, herein no longer
It is described in detail.The peroxide can be the peroxide described in second aspect of the present invention, no longer be described in detail herein.
According to the method described in the 5th aspect of the present invention, in one embodiment, the inorganic agent is alkali, HNO3Or
Person's peroxide.The alkali is preferably organic base, more preferably synthesis of titanium silicon molecular sieve template, the season as shown in formula III
Ammonium alkali.
In a kind of embodiment being more highly preferred to, the inorganic agent is alkali and peroxide, so can further be improved
The intensity of the formed body finally prepared and the catalytic performance in hydrocarbon dehydrogenation reaction.In the embodiment that this is more highly preferred to,
The mol ratio of alkali and peroxide is preferably 1：1-20, more preferably 1：4-18.The alkali is preferably organic base, is more preferably closed
Into HTS template, the quaternary ammonium base as shown in formula III.
In the embodiment that another kind is more highly preferred to, the inorganic agent is peroxide and HNO3.With first using peroxide
Compound and HNO3With nano-carbon material progress hydro-thermal process compared with aftershaping, in peroxide and HNO3In the presence of, by nanometer
Carbon material carries out hydro-thermal process aftershaping together with binding agent source, can be in lower peroxide and HNO3Dosage under, improve
The intensity of the formed body finally prepared and the catalytic performance in hydrocarbon dehydrogenation reaction.In the embodiment that this is more highly preferred to,
Peroxide and HNO3Mol ratio be 1：1-6, preferably 1：2-4.
According to the method described in the 5th aspect of the present invention, the dosage of the inorganic agent can be entered according to the amount in binding agent source
The appropriate selection of row.Preferably, the inorganic agent and the mol ratio in the binding agent source can be 0.1-20：1, preferably 0.4-
18：1, the binding agent source is in terms of oxide.
According to the method described in the 5th aspect of the present invention, when using molecular sieve preparation solution, the inorganic agent is preferably
Alkali and/or peroxide.
According to the method described in the 5th aspect of the present invention, the dosage of water with can by nano-carbon material and binding agent source and
Optional alkali is well mixed to be defined.Usually, water and the mol ratio in the binding agent source can be 5-150：1, preferably 10-
80：1, the binding agent source is in terms of oxide.
According to the method described in the 5th aspect of the present invention, the dosage in the binding agent source can be according to formed body expection group
Into being selected.Usually, the dosage in the binding agent source make it that in the formed body that finally prepares that the content of nano-carbon material can
Think more than 5 weight % (such as more than 6 weight %), preferably 10 weight %, more preferably more than 50 weight %, further preferably
It is still more preferably more than 70 weight % for more than 60 weight %, is still more preferably more than 75 weight %, particularly preferably
For more than 80 weight %, the content of the nano-carbon material is generally below 95 weight %, more excellent preferably below 94 weight %
Elect as below 90 weight %.In an example, on the basis of the total amount of the nano-carbon material formed body, the nano carbon material
The content of material can be 5-95 weight % (such as 6-94 weight %), more preferably preferably 8-92 weight %, 10-90 weight %,
More preferably 20-90 weight %, it is still more preferably 40-90 weight %, particularly preferably 70-90 weight %, it is described
The content of heat-resistant inorganic oxide can be 5-95 weight % (such as 6-94 weight %), preferably 8-92 weight %, be more preferably
10-90 weight %, more preferably 10-80 weight %, it is still more preferably 10-60 weight %, particularly preferably 10-30
Weight %.Nano-carbon material formed body prepared by method described according to the fifth aspect of the present invention, glued even in relatively low
Tie under agent content, can also obtain higher intensity.Usually, on the basis of the total amount of the formed body, the nano-carbon material
Content be preferably 75-95 weight %, more preferably 85-95 weight %, the content of the heat-resistant inorganic oxide is preferably 5-
25 weight %, more preferably 5-15 weight %.
According to the method described in the 5th aspect of the present invention, the condition of hydro-thermal process is not particularly limited, as long as close
High-temperature process is carried out in closed loop border.Specifically, the temperature of the hydro-thermal process can be 100-200 DEG C, preferably 120-
180℃.The time of the hydro-thermal process can be selected according to the temperature for carrying out hydro-thermal process, typically can be that 0.5-24 is small
When, preferably 6-12 hours.The hydro-thermal process can be carried out (that is, in hydrothermal treatment process, not additionally at autogenous pressures
Apply pressure), it can also be carried out under conditions of pressure is additionally applied.Preferably, the hydro-thermal process is entered at autogenous pressures
OK.
According to the method described in the 5th aspect of the present invention, the shaping, the drying of article shaped and optionally it is calcined
Method and condition are identical with the description in the method described in third aspect of the present invention, are no longer described in detail herein.
The sixth aspect of the invention, prepared the invention provides a kind of method as described in the 5th aspect of the present invention
Nano-carbon material formed body.
Nano-carbon material formed body according to the 6th aspect of the present invention has higher crushing strength.Typically
Ground, the radial direction crushing strength of the nano-carbon material formed body according to the 6th aspect of the present invention can be more than 4N/mm, very
Extremely can be more than 5N/mm.The radial direction crushing strength according to《Petrochemical Engineering Analysis method》(Science Press, nineteen ninety
One edition, Yang Cui surely wait compile) described in RIPP 25-90 specified in method measure.According to the 6th aspect of the present invention
Nano-carbon material formed body has higher porosity.Usually, the nano-carbon material according to the 6th aspect of the present invention
The porosity of formed body can be more than 5%, it might even be possible to it is more than 10%, such as can be in the range of 5-50%, preferably
In the range of 10-30%, more preferably in the range of 12-20%.
According to the seventh aspect of the present invention, the invention provides according to the present invention the on one side, second aspect, the
Application of the nano-carbon material formed body as the catalyst of hydrocarbon dehydrogenation reaction described in four aspects and the 6th aspect.It is described de-
Hydrogen reaction can be carried out in the presence of oxygen, can not also be carried out in the presence of oxygen.Preferably, the dehydrogenation reaction is in oxygen
In the presence of carry out, can so obtain more preferable catalytic effect.The species of the hydrocarbon and the actual conditions of dehydrogenation reaction will be under
Text is described in detail, and is no longer described in detail herein.
According to the eighth aspect of the present invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, deposits
Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with the present invention the on one side, second aspect,
Nano-carbon material formed body contact described in 4th aspect and the 6th aspect.According to the nano-carbon material formed body of the present invention
It can use directly as catalyst, be used after can also crushing according to specific needs as catalyst.
Dehydrogenation can be carried out to polytype hydrocarbon according to the hydrocarbon dehydrogenation reaction method of the present invention, so as to obtain unsaturation
Hydrocarbon, such as alkene.The method according to the invention to alkane particularly suitable for carrying out dehydrogenation, so as to obtain alkene.The hydrocarbon is preferably alkane
Hydrocarbon, such as C2-C12Alkane.Specifically, the hydrocarbon can be but be not limited to ethane, propane, normal butane, iso-butane, pentane, different
Pentane, neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl ring
Pentane, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- bis-
Methylpentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethyl oneself
Alkane, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethyls penta
Alkane, 2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes,
2,4- dimethyl heptanes, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5-
Trimethyl cyclohexane, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyls oneself
Alkane, 2,4,4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3-
Methyl -4- ethyl hexanes, 3,3- diethylpentanes, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- first
(including trimethyl-cyclohexane is various for base -4- ethyl cyclohexanes, n-propyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane
Isomers, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- trimethyl-cyclohexanes, 1,2,5- trimethyl-cyclohexanes, 1,3,5- front threes
Butylcyclohexane), n-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane,
2,4- dimethyl octane, 3- ethyls octane, 4- ethyls octane, 2,3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6-
Trimethylheptane, 2,4,5- trimethylheptanes, 2,4,6- trimethylheptanes, 2,2,3- trimethylheptanes, 2,2,4- trimethyls heptan
Alkane, 2,2,5- trimethylheptanes, 2,2,6- trimethylheptanes, 2,3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- first
Base -3- ethyl heptanes, 2- methyl -4- ethyl heptanes, 2- methyl -5- ethyl heptanes, 3- methyl -3- ethyl heptanes, 4- methyl -3-
Ethyl heptane, 5- methyl -3- ethyl heptanes, 4- methyl -4- ethyl heptanes, 4- propyl group heptane, 3,3- diethylhexanes, 3,4- bis-
Ethyl hexane, 2- methyl -3,3- diethylpentanes, vinylbenzene, 1- phenyl-propanes, 2- phenyl-propanes, 1- phenyl butanes, 2- phenyl
Combination more than one or both of butane, 1- phenyl pentanes, 2- phenyl pentanes and 3- phenyl pentanes.
The hydrocarbon is more preferably more than one or both of propane, normal butane, iso-butane and vinylbenzene, further preferably
For normal butane.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the reaction can be carried out under conditions of it oxygen be present, can also
Carried out under conditions of in the absence of oxygen.It is preferred that carried out under conditions of it oxygen be present.When being carried out under conditions of oxygen being present,
The dosage of oxygen can be conventional selection.Usually, the mol ratio of hydrocarbon and oxygen can be 0.01-100：1, preferably 0.1-
10：1, more preferably 0.2-5：1, most preferably 0.5-2：1.
According to the hydrocarbon dehydrogenation reaction method of the present invention, can by carrier gas by hydrocarbon and optional oxygen be sent into reactor with
The haptoreaction of nano-carbon material containing hetero atom.The carrier gas can be it is conventional at reaction conditions will not be with reactant and reaction
Chemical interaction and the gas that will not be decomposed occur for product, such as nitrogen, carbon dioxide, rare gas and vapor
One or both of more than combination.The dosage of the carrier gas can be conventional selection.Usually, the content of carrier gas can be with
30-99.5 volume %, preferably 50-99 volumes %, more preferably 70-98 volumes %.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the temperature of the contact can be conventional selection, to be enough to send out hydrocarbon
Raw dehydrogenation reaction is defined.Usually, the contact can be carried out at a temperature of 200-650 DEG C, preferably in 300-600 DEG C of temperature
Degree is lower to be carried out, and is carried out more preferably at a temperature of 350-550 DEG C, further preferably in 400-450 DEG C of temperature when such as hydrocarbon being butane
Degree is lower to be carried out.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the contact is carried out preferably in fixed bed reactors.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the duration of the contact can be selected according to the temperature of contact
Select, when such as described contact is carried out in fixed bed reactors, the duration of contact can be represented with the weight (hourly) space velocity (WHSV) of charging.
Usually, the weight (hourly) space velocity (WHSV) of feed gas can be 1-50000h-1, preferably 10-20000h-1, more preferably 50-10000h-1, more preferably 100-8000h-1, such as 2500-4500h-1。
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following preparation example, X-ray photoelectron spectroscopic analysis are in Thermo Scientific companies equipped with Thermo
Tested on the ESCALab250 type x-ray photoelectron spectroscopies of AvantageV5.926 softwares, excitaton source is monochromatization Al
K α X ray, energy 1486.6eV, power 150W, the penetrating base vacuum that can be 30eV, analyze during test used in narrow scan
For 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage softwares
Upper carry out data processing, quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is before testing at 150 DEG C
Temperature and 1 normal atmosphere are depressed to be dried 3 hours in helium atmosphere.
In following preparation example, thermogravimetric analysis is carried out on TA5000 thermal analyzers, and test condition is air atmosphere, heating speed
It is room temperature (25 DEG C) to 1000 DEG C to spend for 10 DEG C/min, temperature range.Sample is big in 150 DEG C of temperature and 1 standard before testing
Dried 3 hours in helium atmosphere under air pressure.Using the ASAP2000 types N of Micromertrics companies of the U.S.2Physical adsorption appearance
Measurement the specific area.
The property of multi-walled carbon nanotube in following preparation example as raw material nano carbon material is listed in table 1 below.
Table 1
In following examples and comparative example, the content of silicon, titanium and aluminium element in crystallization mother liquor and rearrangement solution and alkali
Content is using Perkin-Elmer 3300DV types sensing coupled plasma (ICP) spectroanalysis instrument measure.
In following examples and comparative example, radial direction crushing strength according to《Petrochemical Engineering Analysis method》(Science Press,
The nineteen ninety first edition, Yang Cui surely wait compile) described in RIPP 25-90 specified in method measure；Porosity refers to nano-carbon material
The ratio of all interstitial space volume sums and the volume of the nano-carbon material formed body, is referred to as the nanometer in formed body
The porosity of carbon material formed body, is expressed as a percentage, using mercury injection method (reference literature《Graphite porosity of porous material determines
Technique study》,《Lubrication and sealing》, 2010,35 (10)：99-101) method determines.
Preparation example 1-25 is used to prepare nano-carbon material containing hetero atom.
Preparation example 1
(1) (it is purchased from Chinese Academy of Sciences's Chengdu organic chemistry using 20g as the multi-walled carbon nanotube A of raw material nano carbon material
Co., Ltd) it is scattered in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition includes：Frequency is
40kHz, time are 0.5 hour.Then hydrogen peroxide is added, is well mixed, so as to obtain aqueous dispersions.Wherein, hydrogen peroxide
There is provided in the form of 30 weight % hydrogen peroxide, by raw material nano carbon material：Hydrogen peroxide：H2O weight ratio is 1：5：25 ratio
Example feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 150 DEG C of temperature
Under, react 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened
Kettle, reactant mixture is filtered and washed, and collect solid matter.By the solid matter being collected into, in normal pressure, (1 standard is big
Air pressure, similarly hereinafter), dry 6 hours at a temperature of 120 DEG C, obtain nano-carbon material containing hetero atom, its composition, specific surface area and
w500/w800Listed in table 2.
Preparation example 2
It is equipped with being placed in the identical aqueous dispersions of preparation example 1 in the three-necked flask of condenser pipe, the three-necked flask is placed in
Temperature is back flow reaction 24 hours under normal pressure in 150 DEG C of oil bath.After reaction terminates, treat that the temperature in three-necked flask is down to
After room temperature, reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120
Dried 6 hours at a temperature of DEG C, obtain nano-carbon material containing hetero atom.
Preparation example 3
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 1, unlike, in step (1), as
Raw material nano carbon material is multi-walled carbon nanotube B.
Preparation example 4
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 1, unlike, in step (2), will
To aqueous dispersions be placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 110 DEG C, at autogenous pressures
Reaction 24 hours.
Preparation example 5
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 1, unlike, in step (1), raw material
Nano-carbon material：Hydrogen peroxide：H2O weight ratio is 1：0.5：25.
Preparation example 6
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 1, unlike, in step (1), peroxide
Change hydrogen to be replaced with the TBHP of equimolar amounts.
Preparation example 7
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 1, unlike, in step (1), peroxide
Change hydrogen to be replaced with the cumyl peroxide of equimolar amounts.
Preparation example 8
(1) (it is purchased from Chinese Academy of Sciences's Chengdu organic chemistry using 20g as the multi-walled carbon nanotube C of raw material nano carbon material
Co., Ltd) it is scattered in deionized water, it is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes：Frequency is
60kHz, time are 1 hour.Then add hydrogen peroxide to be well mixed, so as to obtain aqueous dispersions.Wherein, hydrogen peroxide and 40
The form of the weight % aqueous solution provides, by raw material nano carbon material：Hydrogen peroxide：H2O weight ratio is 1：1.5：10 ratio
Feed intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 200 DEG C of temperature
Under, react 8 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened
Kettle, reactant mixture is filtered, and collect solid matter.By the solid matter being collected at a temperature of normal pressure, 140 DEG C
Dry 6 hours, obtain nano-carbon material containing hetero atom, its composition, specific surface area and w500/w800Listed in table 2.
Preparation example 9
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 8, unlike, in step (2), will
To aqueous dispersions be placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 240 DEG C, at autogenous pressures
Reaction 8 hours.
Preparation example 10
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 8, unlike, in step (1), as
Raw material nano carbon material is multi-walled carbon nanotube D (being purchased from Shandong great Zhan nano materials Co., Ltd).
Preparation example 11
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 8, unlike, in step (1), by original
Expect nano-carbon material：Hydrogen peroxide：H2O weight ratio is 1：0.8：10 ratio feeds intake.
Preparation example 12
(1) (it is purchased from Chinese Academy of Sciences's Chengdu organic chemistry using 20g as the multi-walled carbon nanotube E of raw material nano carbon material
Co., Ltd) it is scattered in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition includes：Frequency is
14kHz, time are 0.5 hour.Then add hydrogen peroxide to be well mixed, so as to obtain aqueous dispersions.Wherein, hydrogen peroxide with
The form of the 35 weight % aqueous solution provides, by raw material nano carbon material：Hydrogen peroxide：H2O weight ratio is 1：7.5：30 ratio
Example feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 170 DEG C of temperature
Under, react 36 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened
Kettle, reactant mixture is filtered and washed, and collect solid matter.By the solid matter being collected into normal pressure, 120 DEG C
At a temperature of dry 12 hours after, obtain nano-carbon material containing hetero atom, its composition, specific surface area and w500/w800Arranged in table 2
Go out.
Preparation example 13
(1) it is scattered in deionized water using 20g as the multi-walled carbon nanotube A of raw material nano carbon material, it is dispersed in ultrasound
Carried out under oscillating condition, sonic oscillation condition includes：Frequency is 14kHz, and the time is 0.5 hour.Then HNO is added3And peroxide
Change hydrogen to be well mixed, so as to obtain aqueous dispersions.Wherein, HNO3It is water-soluble with 50 weight % and 30 weight % respectively with hydrogen peroxide
The form of liquid provides, by raw material nano carbon material：HNO3：Hydrogen peroxide：H2O weight ratio is 1：0.2：0.5：50 ratio is thrown
Material.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 110 DEG C of temperature
Under, react 36 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened
Kettle, reactant mixture is filtered and washed, and collect solid matter.By the solid matter being collected into, in normal pressure, (1 standard is big
Air pressure, similarly hereinafter), after drying 12 hours at a temperature of 120 DEG C, obtain nano-carbon material containing hetero atom, its composition, specific surface area with
And w500/w800Listed in table 3.
Preparation example 14
It is equipped with being placed in the identical aqueous dispersions of preparation example 13 in the three-necked flask of condenser pipe, the three-necked flask is placed in
In 110 DEG C of oil bath, back flow reaction 36 hours at ambient pressure.After reaction terminates, after the temperature in three-necked flask is down to room temperature,
Reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature
After being dried 6 hours under degree, nano-carbon material containing hetero atom is obtained.
Preparation example 15
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 13, unlike, in step (1), make
That for raw material nano carbon material is multi-walled carbon nanotube B.
Preparation example 16
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 13, unlike, will in step (2)
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in self-generated pressure
Lower reaction 36 hours.
Preparation example 17
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 13, unlike, in step (1), press
Raw material nano carbon material：HNO3：Hydrogen peroxide：H2O weight ratio is 1：5：0.02：15 ratio feeds intake.
Preparation example 18
It is scattered in deionized water using 20g as the multi-walled carbon nanotube C of raw material nano carbon material, it is dispersed in sonic oscillation
Under the conditions of carry out, sonic oscillation condition includes：Frequency is 90kHz, and the time is 2 hours.Then HNO is added3Mixed with hydrogen peroxide
Close uniformly, so as to obtain aqueous dispersions, wherein, HNO3With hydrogen peroxide respectively with 40 weight % and the shape of the 30 weight % aqueous solution
Formula provides, by raw material nano carbon material：HNO3：Hydrogen peroxide：H2O weight ratio is 1：2：1：100 ratio feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 180 DEG C of temperature
Under, react 12 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened
Kettle, reactant mixture is filtered and washed, and collect solid matter.By the solid matter being collected into normal pressure, 140 DEG C
At a temperature of dry 8 hours after, obtain nano-carbon material containing hetero atom, its composition, specific surface area and w500/w800Arranged in table 3
Go out.
Preparation example 19
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 18, unlike, in step (1), make
That for raw material nano carbon material is multi-walled carbon nanotube D.
Preparation example 20
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 18, unlike, will in step (2)
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 250 DEG C, in self-generated pressure
Lower reaction 12 hours.
Preparation example 21
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 18, unlike, in step (1), press
Raw material nano carbon material：HNO3：Hydrogen peroxide：H2O weight ratio is 1：3：2：400 ratio feeds intake.
Preparation example 22
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 18, unlike, in step (1), mistake
Hydrogen oxide is replaced with the TBHP of equimolar amounts.
Preparation example 23
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 18, unlike, in step (1), mistake
Hydrogen oxide is replaced with the cumyl peroxide of equimolar amounts.
Preparation example 24
It is equipped with being placed in the identical aqueous dispersions of preparation example 23 in the three-necked flask of condenser pipe, the three-necked flask is placed in
In 150 DEG C of oil bath, back flow reaction 24 hours at ambient pressure.After reaction terminates, after the temperature in three-necked flask is down to room temperature,
Reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature
After being dried 6 hours under degree, nano-carbon material containing hetero atom is obtained.
Preparation example 25
(1) it is scattered in deionized water using 20g as the multi-walled carbon nanotube E of raw material nano carbon material, it is dispersed in ultrasound
Carried out under oscillating condition, sonic oscillation condition includes：Frequency is 14kHz, and the time is 0.5 hour.Then HNO is added3And peroxide
Change hydrogen to be well mixed, so as to obtain aqueous dispersions, wherein, HNO3It is water-soluble with 45 weight % and 35 weight % respectively with hydrogen peroxide
The form of liquid provides, by raw material nano carbon material：HNO3：Hydrogen peroxide：H2O weight ratio is 1：6：3：200 ratio feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 150 DEG C of temperature
Under, react 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened
Kettle, reactant mixture is filtered and washed, and collect solid matter.By the solid matter being collected into normal pressure, 120 DEG C
At a temperature of dry 12 hours after, obtain nano-carbon material containing hetero atom, its composition, specific surface area and w500/w800Arranged in table 3
Go out.
Embodiment 1-82 is used to illustrate according to nano-carbon material formed body of the present invention and preparation method thereof.
It is related to following binding agent source in embodiment 1-82.
Ludox：Purchased from Zhejiang Province Yuda Chemical Co., Ltd, dioxide-containing silica is 25 weight %
Tetraethyl orthosilicate：Purchased from Zhangjiagang new Asia Chemical Co., Ltd. (numbering TES)
Alumina gel：Purchased from Shandong, Chile reaches chemical inc, and alumina content is 12 weight %
Aluminium isopropoxide：Purchased from Beijing Deco Dao Jin Science and Technology Ltd.s (numbering IPOA)
Titanium oxide：Purchased from Shandong Origine Nanomaterial Engineering Co., Ltd., particle diameter 5-10nm
Tetraethyl titanate：Purchased from Jin Yu chemical industry Co., Ltd of Shouguang City (numbering TET)
(1) crystallization mother liquor of HTS
Method according to US4410501 embodiments 1 prepares titanium-silicon molecular sieve TS-1, and collects crystallization mother liquor.Concrete operations
Process is：
455g tetraethyl orthosilicates are placed in equipped with agitating device and for without CO2In the reactor of atmosphere, Ran Houxian
The TPAOH aqueous solution of 15g tetraethyl titanates and 800g concentration for 25 weight % is added afterwards., will after stirring 1 hour
Temperature is increased to 80~90 DEG C, continues stirring 5 hours.Then deionized water is added into reaction solution, until the totality of reaction solution
Product is 1.5L.Then, reaction solution is transferred to and be equipped with the autoclave of agitating device, the hydro-thermal under 175 DEG C, self-generated pressure
After crystallization 10 days, obtained reactant mixture is filtered, crystallization mother liquor is collected, by the solid being filtrated to get in 550 DEG C of air gas
It is calcined 6 hours in atmosphere, so as to obtain titanium-silicon molecular sieve TS-1.
After testing, on the basis of the total amount of crystallization mother liquor, with SiO2The content of the element silicon of meter is 1.2 weight %, with TiO2
The content of the titanium elements of meter is 0.04 weight %, and the content of TPAOH is 3.1 weight %.The crystallization mother liquor is concentrated
(concentrate numbering be TS-A) on the basis of the total amount of concentrate, with SiO2The content of the element silicon of meter is 3.6 weight %, with
TiO2The content of the titanium elements of meter is 0.12 weight %, and the content of TPAOH is 9.3 weight %.
(2) crystallization mother liquor of HTS
Method according to US4410501 embodiments 2 prepares titanium-silicon molecular sieve TS-1, and collects crystallization mother liquor.Concrete operations
Process is：
150g tetraethyl titanates are slowly added dropwise in 2.5L distilled water and hydrolyzed under agitation, obtain a white gum
Suspension, this suspension is then cooled to 5 DEG C；Then it is 30% by the 1.8L mass concentrations for having cooled to 5 DEG C in advance
Aqueous hydrogen peroxide solution is incorporated in wherein, and is kept for 2 hours at 5 DEG C under conditions of intermittent stirring, and it is molten to obtain an orange clarification
Liquid；Then the TPAOH aqueous solution that the 2.4L mass concentrations for having cooled to 5 DEG C in advance are 25% is added to orange
In settled solution, after 1 hour, 500g SiO are added2The Ludox that content is 40% carefully mixes, and obtained mixture is in normal temperature
Left overnight；Most after 70-80 DEG C of heating stirring 6 hours.Obtained mixture is transferred to the high pressure for being equipped with agitating device
In reactor, hydrothermal crystallizing filtered obtained reactant mixture after 10 days under 175 DEG C, self-generated pressure, and it is female to collect crystallization
Liquid, the solid phase being filtrated to get is calcined 6 hours in 550 DEG C of air atmospheres, confirmed through X-ray diffraction analysis, obtain titanium silicon point
Son sieve TS-1.
After testing, on the basis of the total amount of crystallization mother liquor, with SiO2The content of the element silicon of meter is 2.8 weight %, with TiO2
The content of the titanium elements of meter is 0.04 weight %, and the content of TPAOH is 1.6 weight %.The crystallization mother liquor is concentrated
(concentrate numbering be TS-B) on the basis of the total amount of concentrate, with SiO2The content of the element silicon of meter is 7 weight %, with
TiO2The content of the titanium elements of meter is 0.1 weight %, and the content of TPAOH is 4 weight %.
(3) crystallization mother liquor of HTS
According to J.Chem.Soc.Chem.Commun., the method described in 1992,589-590 prepares HTS
Ti-Beta, crystallization mother liquor is collected during separation of solid and liquid.Specifically preparation process is：
At room temperature, tetraethyl titanate and amorphous silica gel Aerosil 200 are added to tetraethyl hydrogen-oxygen under agitation
Change in ammonium (TEAOH) aqueous solution, then add appropriate aluminum nitrate, the glue mole composition now formed is A12O3：TiO2：
SiO2：H2O：TEAOH=1：12：388：6000：108, the glue of formation is transferred to the autoclave with polytetrafluoroethyllining lining
Middle carry out dynamic crystallization, crystallization temperature are 130 DEG C, mixing speed 60rpm, crystallization time 3d.After cooling, consolidate what is obtained
Liquid mixture is centrifuged, and obtains solid and crystallization mother liquor (numbering TS-C).The solid isolated is washed with water to pH=9
Left and right, 80 DEG C of dry 5h, the lower 580 DEG C of roastings 5h of air atmosphere, so as to obtain HTS Ti-Beta.
After testing, on the basis of the total amount of crystallization mother liquor, with SiO2The content of the element silicon of meter is 3.4 weight %, with TiO2
The content of the titanium elements of meter is 0.3 weight %, and the content of tetraethyl ammonium hydroxide is 13.1 weight %.
(4) rearrangement solution of HTS
Method according to the embodiment 9 of China's application 99126289.1 obtains the rearrangement solution of HTS, specific to prepare
Process is：
According to TS-1 molecular sieves (gram)：Tetraethyl ammonium hydroxide (mole)：Water (mole)=100：0.25：60 ratio is mixed
Close uniformly, mixture is placed in stainless steel sealing reactor, constant temperature is placed 3 days under 175 DEG C and self-generated pressure.Cool down release
Afterwards, filtered, gained filtrate is the rearrangement solution of HTS.
After testing, on the basis of the total amount of rearrangement solution, with SiO2The content of the element silicon of meter is 1.1 weight %, with TiO2Meter
The contents of titanium elements be 0.02 weight %, the content of TPAOH is 3.6 weight %.Rearrangement solution is concentrated into (concentration
Liquid numbering is TS-D) extremely on the basis of the total amount of rearrangement solution, with SiO2The content of the element silicon of meter is 4.4 weight %, with TiO2Meter
The contents of titanium elements be 0.08 weight %, the content of TPAOH is 14.4 weight %.
(5) crystallization mother liquor of Si-Al molecular sieve
With reference to the method for US4410501 embodiments 1 sial is prepared using silicon source aluminium isopropoxide replacement titanium source tetraethyl titanate
Molecular sieve, and collect crystallization mother liquor.Specific operation process is：
Without CO2Atmosphere under, 455g tetraethyl orthosilicates are positioned in heatproof glass container, with stirring add 15g
Aluminium isopropoxide, be subsequently added into by 800g mass concentrations be 25% the TPAOH aqueous solution, mix 4h after, in 80-90
DEG C heating stirring drives ethanol out of after 5 hours completely.Then 1.5L is added water to, obtained mixture is transferred to outfit stirring
In the autoclave of device, hydrothermal crystallizing 10 days under 175 DEG C, self-generated pressure, obtained reactant mixture is filtered, collected
Crystallization mother liquor.
After testing, on the basis of the total amount of crystallization mother liquor (being AS-F by crystallization mother liquor numbering), with SiO2The element silicon of meter
Content be 2.3 weight %, with Al2O3The content of the aluminium element of meter is 0.14 weight %, and the content of TPAOH is
12.5 weight %.By crystallization mother liquor concentration (concentrate numbering is AS-E) extremely on the basis of the total amount of concentrate, with concentrate
Total amount on the basis of, with SiO2The content of the element silicon of meter is 8.28 weight %, with Al2O3The content of the aluminium element of meter is 0.504
Weight %, the content of TPAOH is 45 weight %.
Embodiment 1-49
The condition provided according to table 4, nano-carbon material is molded respectively using following methods.
Nano-carbon material is well mixed with binding agent source under environment temperature (25 DEG C) respectively, mixture feeding will be obtained
After being dried and be optionally calcined in strip mould, obtain nano-carbon material formed body and (randomly select part formed body to enter
Row polishing, obtain the batten that length is 3-5mm and be used to determine crushing strength and porosity, as a result listed in table 4), will be surplus
Sieved after remaining formed body is broken, obtain graininess formed body, its mean particle size (particle diameter) is listed in table 4.
Table 4
1：The dosage of nano-carbon material is 10g2：TPAOH3：Tetraethyl ammonium hydroxide4：In terms of oxide
5：The species and dosage of the inorganic agent additionally added outside contained inorganic agent in binding agent source
Embodiment 50-78
Using following methods, nano-carbon material is molded by the condition provided according to table 5 respectively：
Nano-carbon material is mixed with binding agent source and optional inorganic agent respectively, is then placed in obtained mixture
In sealing autoclave with polytetrafluoroethyllining lining, hydro-thermal process is carried out under self-generated pressure.Treat in autoclave
Temperature be down to environment temperature after, open reactor, obtained slurries be sent into strip mould and are dried and optionally
After roasting, obtain nano-carbon material formed body and (randomly select part formed body to be polished, obtain the batten that length is 3-5mm
For determining crushing strength and porosity, as a result listed in table 5), by remaining formed body it is broken after sieved, obtain
Granular formed body, its mean particle size are listed in table 5.
Embodiment 79
Difference with embodiment 50 is, nano-carbon material is well mixed with binding agent source in environment temperature (25 DEG C)
Afterwards, without hydro-thermal process, but directly it is molded.
Embodiment 80
Difference with embodiment 50 is, the mixture in nano-carbon material and binding agent source is placed in three-necked flask,
With carrying out back flow reaction, time and the water in embodiment 50 of back flow reaction at a temperature of the hydro-thermal process temperature identical of embodiment 50
Heat treatment time is identical, and the mixture that back flow reaction is obtained is sent into mould.
Embodiment 81
Difference with embodiment 51 is, nano-carbon material is well mixed with binding agent source in environment temperature (25 DEG C)
Afterwards, without hydro-thermal process, but directly it is molded.
Embodiment 82
Difference with embodiment 51 is, the mixture in nano-carbon material and binding agent source is placed in three-necked flask,
With carrying out back flow reaction, time and the water in embodiment 51 of back flow reaction at a temperature of the hydro-thermal process temperature identical of embodiment 51
Heat treatment time is identical, and the mixture that back flow reaction is obtained is sent into mould.
Table 5
1：The dosage of nano-carbon material is 10g2：TPAOH3：In terms of oxide
4：The species and dosage of the inorganic agent additionally added outside contained inorganic agent in binding agent source
Testing example 1-82
The catalytic performance of the catalyst prepared using following methods successively testing example 1-82.
The graininess formed body respectively prepared by 0.2g embodiments 1-82 is micro- in universal fixed bed as Catalyst packing
In type quartz tube reactor, the end seal of miniature quartz pipe reactor two has quartz sand, will under the conditions of 0MPa (gauge pressure) and 450 DEG C
(concentration of normal butane is 1.98 volume %, normal butane and oxygen molar ratio 0.5 to gas containing normal butane and oxygen：1, surplus
For the nitrogen as carrier gas) with 3500h-1Weight (hourly) space velocity (WHSV) be passed through in reactor and reacted, continuous monitoring is defeated from reactor
The composition of the reactant mixture gone out, and calculate n-butane conversion and total olefin selectivity, the result of reaction 3 hours and 24 hours
Listed in table 6.
Test comparison example 1-5
Using the catalytic for testing multi-walled carbon nanotube A, B, C, D and E successively with testing example 1-82 identicals method
Energy.
Table 6
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.It is further to note that described in above-mentioned embodiment
Each particular technique feature, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention no longer separately illustrate to various combinations of possible ways.In addition, a variety of implementations of the present invention
It can also be combined between mode, as long as it without prejudice to the thought of the present invention, it is public that it should equally be considered as institute of the invention
The content opened.
Claims (40)
1. a kind of nano-carbon material formed body, the formed body contains nano-carbon material and for the nano-carbon material to be bonded
The heat-resistant inorganic oxide of shaping, the nano-carbon material contain O elements and optional N element.
2. formed body according to claim 1, wherein, on the basis of the total amount of the nano-carbon material and in terms of element, O
The content of element is 2-15 weight %, more preferably preferably 5-12 weight %, 7-11 weight %；The content of N element is 0-5 weights
Measure %, more preferably preferably 0.1-5 weight %, 1.5-4.5 weight %.
3. formed body according to claim 1 or 2, wherein, in the nano-carbon material, by x-ray photoelectron power spectrum
The amount for the O elements that peak in the range of 531.0-532.5eV determines is IO c, by 532.6-533.5eV models in x-ray photoelectron power spectrum
The amount for the O elements that peak in enclosing determines is IO e, IO c/IO eIn the range of 0.1-1.
4. according to the formed body described in any one in claim 1-3, wherein, by 288.6- in x-ray photoelectron power spectrum
The amount for the C element that peak in the range of 288.8eV determines is IC c, in the range of 286.0-286.2eV in x-ray photoelectron power spectrum
The amount for the C element that peak determines is IC e, IC c/IC eIn the range of 0.1-2.
5. formed body according to claim 1, wherein, the content of N element is less than 0.1 weight in the nano-carbon material
% is measured, on the basis of the total amount of the nano-carbon material and in terms of element, the content of O elements is 6-12 weight %, preferably 7-
11 weight %；The content of C element is 88-94 weight %, preferably 89-93 weight %；
In the nano-carbon material, the O elements that are determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum
Measure as IO c, the amount of the O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum is IO e, IO c/IO eIt is excellent
It is selected in the range of 0.3-0.95, more preferably in the range of 0.5-0.7；
The amount of the C element determined by the peak in the range of 288.6-288.8eV in x-ray photoelectron power spectrum is IC c, by X ray photoelectricity
The amount for the C element that peak in sub- power spectrum in the range of 286.0-286.2eV determines is IC e, IC c/IC eIt is preferred that in 0.3-1.8 scope
It is interior, preferably in the range of 0.5-1.5, more preferably in the range of 0.8-1.
6. formed body according to claim 1, wherein, on the basis of the total amount of the nano-carbon material and in terms of element, O
The content of element is 4-20 weight %, more preferably preferably 7-15 weight %, 8-10 weight %；The content of N element is 0.1-5
Weight %, preferably 0.4-4.8 weight %, more preferably 1.5-4.5 weight %；The content of C element is 75-95.9 weight %,
Preferably 80.2-92.6 weight %, more preferably 85.5-90.5 weight %；
In the nano-carbon material, the O elements that are determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum
Measure as IO c, the amount of the O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum is IO e, IO c/IO e
In the range of 0.1-1, preferably in the range of 0.2-0.8, more preferably in the range of 0.4-0.7；
In the nano-carbon material, determine that the total amount of the N element in the nano-carbon material is I by x-ray photoelectron power spectrumN t,
The amount of the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum is IN c, IN c/IN tIn 0.05-
In the range of 0.5, preferably in the range of 0.1-0.4；By the peak in the range of 403.5-406.5eV in x-ray photoelectron power spectrum
The amount of the N element of determination is IN n, IN n/IN tIn the range of 0.5-0.95, preferably in the range of 0.6-0.8.
7. formed body according to claim 6, wherein, in the nano-carbon material, by x-ray photoelectron power spectrum
The amount for the C element that peak in the range of 288.6-288.8eV determines is IC c, by 286.0-286.2eV models in x-ray photoelectron power spectrum
The amount for the C element that peak in enclosing determines is IC e, IC c/IC eIn the range of 0.1-0.8, preferably in the range of 0.25-0.6.
8. the formed body according to claim 6 or 7, wherein, determined by x-ray photoelectron power spectrum in the nano-carbon material
The total amount of N element be IN t, the amount of the N element determined by the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum is
IN g, IN g/IN tFor not higher than 0.3, preferably in the range of 0-0.25, more preferably in the range of 0.02-0.2.
9. according to the formed body described in any one in claim 1-8, wherein, with the nano-carbon material by X ray light
It is true by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum on the basis of the total amount for the C element that electron spectrum determines
The content of fixed C element is 60-95 weight %, preferably 70-92 weight %；By 286.0- in x-ray photoelectron power spectrum
The total content for the C element that peak in the range of 288.8eV determines is 5-40 weight %, preferably 8-30 weight %.
10. according to the formed body described in any one in claim 1-9, wherein, the nano-carbon material is CNT, excellent
Elect multi-walled carbon nanotube as；
Preferably, the specific surface area of the multi-walled carbon nanotube is in 50-500m2In the range of/g, preferably in 90-280m2/ g model
In enclosing, more preferably in 100-180m2In the range of/g；
Preferably, weight-loss ratio of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800, at 400-500 DEG C
Weight-loss ratio in temperature range is w500, w500/w800It is more excellent preferably in the range of 0.02-0.3 in the range of 0.01-0.5
It is selected in the range of 0.1-0.25, the weight-loss ratio determines in air atmosphere.
11. a kind of nano-carbon material formed body, the formed body contains nano-carbon material and for the nano-carbon material to be glued
Form the heat-resistant inorganic oxide of type；
The nano-carbon material is made using the method comprised the following steps：One kind is dispersed with raw material nano carbon material and extremely
A kind of few aqueous dispersions of modifying agent are reacted in closed container, and in course of reaction, the temperature of the aqueous dispersions is kept
In the range of 80-250 DEG C, the modifying agent is peroxide, or is peroxide and HNO3。
12. formed body according to claim 11, wherein, the modifying agent is peroxide, raw material nano carbon material：Cross
The weight ratio of oxide is 1：In the range of 0.5-50, preferably 1：In the range of 1.5-40.
13. formed body according to claim 12, wherein, raw material nano carbon material：H2O weight ratio is 1：2-50 model
In enclosing, preferably 1：In the range of 5-40, more preferably 1：In the range of 10-30.
14. formed body according to claim 11, wherein, the modifying agent is peroxide and HNO3, raw material nano carbon materials
Material：HNO3：The weight ratio of peroxide is 1：0.01-20：0.01-20, preferably 1：0.05-10：0.02-10, more preferably
1：0.2-6：0.5-3.
15. formed body according to claim 14, wherein, raw material nano carbon material：H2O weight ratio is 1：2-500, it is excellent
Elect 1 as：15-400.
16. according to the formed body described in any one in claim 11-15, wherein, the peroxide is selected from hydrogen peroxide
With the organic peroxide shown in Formulas I,
In Formulas I, R1And R2It each is selected from H, C4-C12Alkyl, C6-C12Aryl, C7-C12Aralkyl andAnd R1
And R2It is asynchronously H, R3For C4-C12Straight or branched alkyl or C6-C12Aryl.
17. according to the formed body described in any one in claim 11-16, wherein, in course of reaction, the aqueous dispersions
Temperature is maintained in the range of 110-200 DEG C；
Preferably, the duration of the reaction is more excellent preferably in the range of 2-72 hours in the range of 0.5-96 hours
It is selected in the range of 8-36 hours.
18. according to the formed body described in any one in claim 11-17, wherein, in the raw material nano carbon material, N members
The content of element is not higher than 0.2 weight %, preferably not higher than 0.02 weight %；The content of O elements is not higher than 1.5 weights
Measure %, preferably not higher than 0.3 weight %；The total amount of metallic element is below 2.5 weight %, preferably below 0.5 weight %.
19. according to the formed body described in any one in claim 11-18, wherein, the raw material nano carbon material is received for carbon
Mitron；Preferably, the raw material nano carbon material is multi-walled carbon nanotube；
Preferably, the specific surface area of the multi-walled carbon nanotube is 50-500m2/ g, preferably 120-190m2/g；
Preferably, total weight loss rate of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800, at 400-500 DEG C
Temperature range in total weight loss rate be w500, w500/w800In the range of 0.01-0.5, preferably in the range of 0.02-0.4,
The weight-loss ratio determines in air atmosphere.
20. according to the formed body described in any one in claim 11-19, wherein, methods described also includes obtaining from reaction
Mixture in isolate solid matter, and the solid matter isolated is dried；
Preferably, the drying is carried out at a temperature of 50-400 DEG C, is carried out preferably at a temperature of 80-180 DEG C；The drying
Duration be preferably 4-24 hours, more preferably 6-12 hours no more than 48 hours.
21. according to the formed body described in any one in claim 1-20, wherein, on the basis of the total amount of the formed body,
The content of the nano-carbon material is 6-94 weight %, more preferably preferably 10-90 weight %, 40-90 weight %, further
Preferably 70-90 weight %, the content of the heat-resistant inorganic oxide are 6-94 weight %, preferably 10-90 weight %, more excellent
Elect 10-60 weight %, more preferably 10-30 weight % as.
22. according to the formed body described in any one in claim 1-21, wherein, the heat-resistant inorganic oxide is oxidation
It is more than one or both of aluminium, silica and titanium oxide；
Preferably, the heat-resistant inorganic oxide contains silica；
It is highly preferred that on the basis of the total amount of the heat-resistant inorganic oxide, the content of the silica is 10-100 weight %,
Preferably 20-99 weight %, more preferably 50-99 weight %.
23. a kind of preparation method of nano-carbon material formed body, this method includes mixing nano-carbon material with binding agent source, will
Obtained mixture is molded, and obtains article shaped, and the article shaped is dried and is optionally calcined, the binding agent
Source is selected from the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, and the nano-carbon material is non-surface treated
Nano-carbon material and/or surface treated nano-carbon material, determined by x-ray photoelectron power spectrum described surface treated
Nano-carbon material contains O elements and optional N element.
24. according to the method for claim 23, wherein, the mixture also contains at least one inorganic agent, the processing
Agent is alkali or HNO3；
Preferably, the alkali is selected from organic base, is preferably selected from quaternary ammonium base, aliphatic amine and aliphatic hydramine, is more preferably selected from closing
Into HTS template, the quaternary ammonium base shown in formula III is further preferably selected from,
In formula III, R8、R9、R10And R11It is identical or different, respectively C1-C4Alkyl；
Inorganic agent and the mol ratio in the binding agent source are 0.05-20：1, preferably 0.1-18：1, the binding agent source is to aoxidize
Thing meter.
25. the method according to claim 23 or 24, wherein, before the mixture is molded, this method also includes will
The mixture carries out hydro-thermal process.
26. according to the method for claim 25, wherein, the hydro-thermal process is at 100-200 DEG C, preferably 120-180 DEG C
At a temperature of carry out, the duration of the hydro-thermal process is 0.5-24 hours, preferably 6-12 hours.
27. according to the method described in any one in claim 23-26, wherein, at least part binding agent source, at least partly may be used
The alkali and at least part water of choosing come from molecular sieve preparation solution, and the molecular sieve preparation solution is the crystallization mother liquor of siliceous molecular sieve
With the mixed liquor reset more than one or both of modified mother liquor of siliceous molecular sieve；
Preferably, the molecular sieve preparation solution is the crystallization mother liquor of silica zeolite and/or resets modification liquid, HTS
One or both of crystallization mother liquor and/or rearrangement modification liquid of crystallization mother liquor and/or rearrangement modification liquid and Si-Al molecular sieve
Mixed liquor above.
28. a kind of forming method of nano-carbon material, this method are included in closed container, by nano-carbon material in a kind of moisture
Hydro-thermal process is carried out in dispersion liquid, the sizing material forming that hydro-thermal process is obtained, obtains article shaped, by the article shaped be dried with
And optional roasting, the aqueous dispersions contain binding agent source, the binding agent source is selected from heat-resistant inorganic oxide and/or heat-resisting
The precursor of inorganic oxide, the nano-carbon material are not surface treated nano-carbon material and/or surface treated
Nano-carbon material, determine that the surface treated nano-carbon material contains O elements and optional by x-ray photoelectron power spectrum
N element.
29. forming method according to claim 28, wherein, the aqueous dispersions also contain at least one inorganic agent, institute
State inorganic agent and be selected from alkali, HNO3And peroxide；
Preferably, the alkali is organic base；
It is highly preferred that the alkali is selected from quaternary ammonium base, aliphatic amine and aliphatic hydramine；
It is further preferred that the alkali is selected from synthesis of titanium silicon molecular sieve template, still more preferably selected from shown in formula III
Quaternary ammonium base,
In formula III, R8、R9、R10And R11It is identical or different, respectively C1-C4Alkyl；
Preferably, the peroxide is selected from hydrogen peroxide and the organic peroxide shown in Formulas I,
In Formulas I, R1And R2It each is selected from H, C4-C12Alkyl, C6-C12Aryl, C7-C12Aralkyl andAnd R1
And R2It is asynchronously H, R3For C4-C12Straight or branched alkyl or C6-C12Aryl；
The peroxide is preferably selected from hydrogen peroxide, TBHP and cumyl peroxide.
30. forming method according to claim 29, wherein, the inorganic agent is alkali and peroxide, alkali and peroxidating
The mol ratio of thing is preferably 1：1-20, more preferably 1：4-18；Or
The inorganic agent is peroxide and HNO3, peroxide and HNO3Mol ratio be 1：1-6, preferably 1：2-4.
31. the method according to claim 29 or 30, wherein, inorganic agent and the mol ratio in the binding agent source are 0.1-
20：1, preferably 0.4-18：1, the binding agent source is in terms of oxide.
32. according to the method described in any one in claim 29-31, wherein, at least part binding agent source, at least partly may be used
The alkali and at least part water of choosing come from molecular sieve preparation solution, and the molecular sieve preparation solution is the crystallization mother liquor of siliceous molecular sieve
With the mixed liquor reset more than one or both of modified mother liquor of siliceous molecular sieve；
Preferably, the molecular sieve preparation solution is the crystallization mother liquor of silica zeolite and/or resets modification liquid, HTS
One or both of crystallization mother liquor and/or rearrangement modification liquid of crystallization mother liquor and/or rearrangement modification liquid and Si-Al molecular sieve
Mixed liquor above.
33. according to the method described in any one in claim 23-32, wherein, the heat-resistant inorganic oxide be aluminum oxide,
It is more than one or both of silica and titanium oxide；
Preferably, the heat-resistant inorganic oxide contains silica；
It is highly preferred that on the basis of the total amount of the heat-resistant inorganic oxide, the content of the silica is 10-100 weight %,
Preferably 20-99 weight %, more preferably 50-99 weight %.
34. according to the method described in any one in claim 23-33, wherein, the dosage in the binding agent source causes finally
In the formed body of preparation, the content of nano-carbon material is 5-95 weight %, and preferably 6-94 weight %, more preferably 75-95 are heavy
% is measured, more preferably 85-95 weight %, the content of the heat-resistant inorganic oxide is 5-95 weight %, preferably 6-94
Weight %, more preferably 5-25 weight %, more preferably 5-15 weight %.
35. according to the method described in any one in claim 23-34, wherein, the surface treated nano-carbon material
For the nano-carbon material described in any one in claim 2-10 and 11-20.
36. according to the method described in any one in claim 23-35, wherein, the drying is at a temperature of 50-200 DEG C
Carry out, carried out preferably at a temperature of 120-180 DEG C；The duration of the drying is no more than 48 hours, preferably 3-24
Hour, more preferably 5-15 hours；
The roasting is carried out at a temperature of 300-800 DEG C, is carried out preferably at a temperature of 450-650 DEG C, the roasting is held
The continuous time is 1-12 hours, preferably 2-4 hours.
37. nano-carbon material formed body prepared by a kind of method in 23-36 as claim described in any one.
38. catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction in claim 1-22 and 37 described in any one
Application, the hydrocarbon is preferably alkane, more preferably C2-C12Alkane, more preferably normal butane.
39. a kind of hydrocarbon dehydrogenation reaction method, this method is included under conditions of existence or non-existence oxygen, in hydrocarbon dehydrogenation reaction bar
Under part, hydrocarbon is contacted with the nano-carbon material formed body described in any one in claim 1-22 and 37.
40. according to the method for claim 39, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably
Normal butane.
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| CN101014412A (en) * | 2004-07-16 | 2007-08-08 | 那诺克有限公司 | Catalyst comprising nanocarbon structures for the production of unsaturated hydrocarbons |
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| CN104667916A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Method for preparing catalytic wet oxidation catalyst |
| CN105195132A (en) * | 2014-05-26 | 2015-12-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Catalyst for diisobutylene selective dehydrogenation aromatization-based preparation of p-xylene, preparation method of catalyst and p-xylene preparation method |
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| CN101014412A (en) * | 2004-07-16 | 2007-08-08 | 那诺克有限公司 | Catalyst comprising nanocarbon structures for the production of unsaturated hydrocarbons |
| CN101704504A (en) * | 2009-12-03 | 2010-05-12 | 中国科学院宁波材料技术与工程研究所 | In-situ synthesis method for nano tin dioxide/carbon nano tube composite material |
| CN104667916A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Method for preparing catalytic wet oxidation catalyst |
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