CN107970919A - Modified carbon nano tube material - Google Patents
Modified carbon nano tube material Download PDFInfo
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- CN107970919A CN107970919A CN201610918530.3A CN201610918530A CN107970919A CN 107970919 A CN107970919 A CN 107970919A CN 201610918530 A CN201610918530 A CN 201610918530A CN 107970919 A CN107970919 A CN 107970919A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000002086 nanomaterial Substances 0.000 claims abstract description 16
- 239000011232 storage material Substances 0.000 claims abstract description 13
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000010306 acid treatment Methods 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002048 multi walled nanotube Substances 0.000 claims description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- SBVSDAFTZIVQEI-UHFFFAOYSA-N 2,3,4,4a,4b,5,6,7,8,8a,9,9a-dodecahydro-1h-carbazole Chemical compound C1CCCC2C3CCCCC3NC21 SBVSDAFTZIVQEI-UHFFFAOYSA-N 0.000 claims description 2
- KVSWZGISCXEZGZ-UHFFFAOYSA-N C(C)C1=CC=CC=2C3=CC=CC=C3NC12.[N] Chemical compound C(C)C1=CC=CC=2C3=CC=CC=C3NC12.[N] KVSWZGISCXEZGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 235000013847 iso-butane Nutrition 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 241000143432 Daldinia concentrica Species 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000002134 carbon nanofiber Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 229910021392 nanocarbon Inorganic materials 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000002604 ultrasonography Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- -1 carbon nanomaterials;Modified carbon nano tube Chemical class 0.000 abstract description 2
- 238000004939 coking Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 94
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 239000002041 carbon nanotube Substances 0.000 description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 description 23
- 229910052697 platinum Inorganic materials 0.000 description 23
- 239000012298 atmosphere Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 21
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 20
- 238000011084 recovery Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 238000006555 catalytic reaction Methods 0.000 description 19
- 238000001816 cooling Methods 0.000 description 19
- 238000003860 storage Methods 0.000 description 19
- 238000012545 processing Methods 0.000 description 17
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000001802 infusion Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002079 double walled nanotube Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/36—Rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/48—Silver or gold
- C07C2523/52—Gold
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Inorganic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of modified carbon nano tube material, Preparation method and use, including following content：Modified carbon nano tube material is made of (a) 0.1~5 part of active component and (b) 95~99.9 parts of carbon nanomaterials；Modified carbon nano tube material carries out carbon nanomaterial strong acid treatment by (1), and (2) introduce active component to prepare with ultrasound in a manner of impregnating or precipitate.The modified carbon nano tube material being prepared can solve the problems, such as that activity component load quantity existing for this current material preparation method is smaller, scattered bad, this material is when for dehydrogenating low-carbon alkane or organic liquid hydrogen storage material dehydrogenation reaction, catalyst have Pt dispersion degrees are high, carrier is no acidic, reaction process substantially without coking, the advantages of activity is high and stability is high.
Description
Technical field
The present invention discloses a kind of modified carbon nano tube material, this carbon nanomaterial can be used for dehydrogenating low-carbon alkane, organic liquid
Hydrogen storage material dehydrogenation and other dehydrogenation reactions.
Background technology
Carbon nanomaterial has high aspect ratio, big specific surface area, outstanding chemically and thermally stability, high machinery
Intensity and good electric conductivity, have very tempting prospect in heterogeneous catalysis as catalyst carrier.So far, it is many
Metal or metal oxide, such as Pt, Au, Ru, Pd, RuO4It is loaded on carbon nanomaterial, is urged so as to form support type
Agent, they show good catalytic performance in catalytic field.
The method of carbon nanotube loaded metal has very much, since carbon nanotubes is by modified, can exist on surface a large amount of
Oxygen-containing functional group, these oxygen-containing functional groups are easily combined with metal ion, then with different reduction steps with regard to that can obtain
The carbon nano tube compound material of carried metal.Main method has：Ion-exchange, infusion process, microemulsion method, hydro-thermal method etc..
Ion-exchange, is swapped by means of the ion in the ion and weak solution in Solid-state Ion-exchange agent, with reach extraction or
The purpose of some ions in solution is removed, is a kind of unit operation for belonging to mass transfer separation process.Prepared with ion-exchange
Catalyst good dispersion degree, activity is high, is particularly suitable for preparing low content, the noble metal catalyst of high usage and acid-base catalysis
Agent.Infusion process is a kind of simple, easy method, and the load in many documents to metal all adopts this method, and manufactures solid
One of method of catalyst, will one or more of active components method on carrier is supported on by impregnated carrier.Typically
Contacted with carrier with the aqueous solution of metallic salt, metal salt solution is adsorbed or is stored in carrier capillary, removed superfluous
Solution, then through drying, calcining and activation be made catalyst.Infusion process dosage is few, and utilization rate is high, and this point is to precious metal catalyst
Agent is extremely important, can prepare the less particle of particle diameter, but particle size disunity, and due to metal load mainly according to
By physical action, its load capacity is smaller, and scattered bad, and to improve such case, people are improved based on this situation.
CN1559686 report it is a kind of by orientated deposition carbon nano tube surface loaded metal platinum new method, by every
Containing 0.1~10g carbon nanotubes, 1~100g surfactants, 0.05~10g platinum (with metal salt in the polyalcohol mixed liquor of 1L
In platiniferous gauge), the chloride and surfactant of carbon nanotubes and platinum are reacted in polyalcohol, realize nano platinum particle
Deposited in the directed chemical of carbon nano tube surface, solve metallic particles and this problem of itself reuniting occurs；The load factor of platinum is high,
It is evenly distributed；The nano platinum particle layer of densification can be obtained under higher load factor (more than 50%), its particle size is averaged
For 5nm, and Size Distribution is very narrow.This catalyst shows preferable performance in methanol oxidation.
CN101683624 discloses dispersed metallic catalyst grain in a kind of control carbon nanotube cavity or outside wall surface
The method of son.It is included in dispersed metal particle in carbon nanotubes lumen, and in carbon nanotubes outside wall surface carrying metal particles two
Part, realizes and metallic is expeditiously filled in carbon nanotubes lumen and optionally in opening carbon nanotubes outside wall surface
Carrying metal particles.Comprise the following steps that：1) pretreatment of carbon nanotubes：Carbon nanometer is submerged using the concentrated nitric acid of 60-68wt%
Pipe, when 120-140 DEG C of processing 10-15 is small, filters, washs, drying, obtains spare carbon pipe；2) A. is in carbon nanotubes lumen
Fill metallic：Spare carbon pipe is stirred with concentration for 0.01-1mg/ml metal salt solutions at room temperature, metal salt solution
Ratio with carbon pipe is 50-300ml/g, when ultrasound 2-6 is small at 20-40 DEG C after, to dry, mixing speed is magnetic agitation at room temperature
20-80g/min, when the time is 20-50 small；Temperature programming is dried in an oven, and Temperature Programmed Processes refer to from room temperature with 0.5-3
DEG C/heating rate of min rises to 110 DEG C and keeps the temperature 6-12h, obtain the carbon nanotubes filled with metal salt；In a hydrogen atmosphere
When 300-500 DEG C of reductase 12-5 is small, obtain filling the carbon pipe of metallic in tube chamber；Or B. is born in carbon nanotubes outside wall surface
Carry metallic：After spare carbon pipe and organic solvent are sufficiently mixed, the mass ratio of organic solvent and carbon pipe is 10-30；20-40
After when ultrasound 2-6 is small at DEG C, addition concentration is 2-20mg/ml metal salt solutions, adds the aqueous slkali of pH=8-12, spare charcoal
The ratio of pipe and metal salt solution is 300-10mg/ml, the ratio of aqueous slkali and spare carbon pipe is 30-5ml/g, is heated with stirring to
Do, mixing speed 50-100g/min, 70-110 DEG C of heating-up temperature, it is dry in baking oven, from room temperature to 100-150 DEG C of guarantor
Warm 8-18h, in a hydrogen atmosphere when 300-500 DEG C of reductase 12-5 is small, finally obtains in carbon nanotubes outside wall surface carried metal grain
The sample of son.
CN201110144034.4 discloses one kind chemical combination such as dispersed metal and metal oxide in carbon nanotubes lumen
The effective ways of thing, this method are particularly suitable for carbon nanotubes of the internal diameter for 1-20nm or so, including single wall, double-walled and multi wall
Carbon nanotubes.Specifically, this method relates to the use of the relatively low metallic compound of boiling point, after gasifying under certain temperature, is passed through
The metal oxygen of carbon nanotubes lumen confinement is obtained into the carbon nanotubes lumen vacuumized, and using solid support methods such as control hydrolysis
Compound nano-particle, then obtain metal nanoparticle through gas phase or liquid-phase reduction.This method has simple, easily operated and control
The characteristics of processed.
Above-mentioned patent achieves certain achievement preparing carbon nanotube loaded connection metal, but is reinforced metal
Load, preparation process all introduce organic matter, and for some chemical reactions, organic matter may pollute product, thus
Limit the application range of these method for preparing catalyst.
The content of the invention
The technical problems to be solved by the invention are that activity component load quantity existing for existing preparation method is smaller, disperse not
The problem of good, using the material of this method preparation when for dehydrogenating low-carbon alkane or organic liquid hydrogen storage material dehydrogenation reaction,
Catalyst have Pt dispersion degrees are high, carrier is no acidic, reaction process substantially without coking, the advantages of activity is high and stability is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of modified carbon nano tube material, in terms of parts by weight, including following components：
(a) 0.1~5 part of active component；
(b) 95~99.9 parts of carbon nanomaterials；
Component (a) is selected from selected from least one of the VIIth B races of the periodic table of elements or the VIIIth race's element metal or its alloy.
In above-mentioned technical proposal, it is preferred that component (a) is selected from the VIIth B races of the periodic table of elements or the VIIIth race's element
A kind of metal or its alloy.
In above-mentioned technical proposal, it is preferred that component (b) is selected from single-walled carbon nanotube (SCNT) and multi-walled carbon nanotube
(MCNT) one kind in.
In above-mentioned technical proposal, it is preferred that active component is mainly distributed on the inner wall of carbon nanomaterial.
In above-mentioned technical proposal, it is preferred that the preparation method of modified carbon nano tube material, comprises the following steps：
(1) strong acid treatment is carried out to carbon nanomaterial；
(2) to introduce active component in a manner of impregnating or precipitate in the form of ultrasonic wave added.
In above-mentioned technical proposal, it is preferred that carry out strong acid treatment to carbon nanomaterial, be to be immersed in carbon nanomaterial by force
Mixture is formed in acid solution, this mixture is heated at 60-100 DEG C, heating time 4-8h, is filtered afterwards, is washed with water straight
To solution into neutrality.
In above-mentioned technical proposal, it is preferred that active component is introduced in a manner of impregnating or precipitate, is to put carbon nanomaterial
Enter the solution of active component, and be ultrasonically treated.
In above-mentioned technical proposal, in step (2) except through ultrasonic wave added processing, can also by microwave treatment etc. other
Mode realizes the function of auxiliary.
In above-mentioned technical proposal, it is preferred that the carbon nanomaterial being prepared can be used for dehydrogenating low-carbon alkane, organic liquid
Hydrogen storage material dehydrogenation and other dehydrogenation reactions.
A kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene, uses propane and/or iso-butane as raw material, in reaction temperature
520~620 DEG C, 0~0.4MPa of reaction pressure of degree, 0.1~8.0h of alkane mass space velocity-1, H2O/CnH2n+2Volume ratio is 1~18
Under the conditions of, raw material and above-mentioned catalyst haptoreaction generation propylene and/or isobutene.
A kind of method of organic liquid hydrogen storage material dehydrogenation, reaction condition are as follows：Reaction pressure is 0~1MPa, temperature is
200~450 DEG C, mass space velocity be 0.1~10h-1；Organic liquid hydrogen storage material is catalyzed with claim 1~6 any one of them
Agent haptoreaction produces hydrogen and corresponding aromatic hydrocarbons.
In above-mentioned technical proposal, it is preferred that organic liquid hydrogen storage material is selected from hexahydrotoluene, hexamethylene, naphthane, ten
At least one of hydrogen naphthalene, perhydro nitrogen ethyl carbazole and perhydro carbazole.
In above-mentioned technical proposal, it is preferred that the reaction condition before catalyst reaction is as follows：Reduction temperature is 300-500 DEG C,
It is preferred that 400-500 DEG C, hydrogen flow rate is 100-500mL/min, preferably 200-400mL/min in reduction process, and the recovery time is
2-8h, preferably 3-6h.
For these reasons, peculiar property of the present invention according to carbon nanotubes, using the infusion process of ultrasonic wave added by activity
Component is imported in carbon material endoporus, on the one hand can increase activity component load quantity, on the other hand can fix active component, final to obtain
The dehydrogenation good to active high stability.
Below by embodiment, the present invention is further elaborated, but the invention is not restricted to following embodiments.
Embodiment
【Embodiment 1】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 8h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
To investigate the stability of catalyst, X2 and X100 is defined, the conversion ratio of raw material when respectively reacting 2h and 100h.
【Embodiment 2】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.124mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 8h, and the dry 8h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 3】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 1.244mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 8h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 4】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 2.448mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 8h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 5】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 2h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 6】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 4h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 7】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 6h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 8】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 2h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 6h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 9】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 4h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 6h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 10】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 6h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 6h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 11】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The palladium chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 6h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 12】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The chlorogold solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, ultrasonic 6h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Embodiment 13】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The chlorination rhenium solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, microwave 6h, and the dry 4h at 120 DEG C, finally puts it into afterwards
4h is roasted at 350 DEG C in the Muffle furnace of He atmosphere, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Comparative example 1】
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g
SCNT is added in this solution, and stirring, room temperature places 2h, afterwards the dry 4h at 120 DEG C, finally puts it into the Muffle of He atmosphere
4h is roasted at 350 DEG C in stove, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Comparative example 2】
The platinum acid chloride solution that 0.124mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g
SCNT is added in this solution, and stirring, room temperature places 2h, afterwards the dry 4h at 120 DEG C, finally puts it into the Muffle of He atmosphere
4h is roasted at 350 DEG C in stove, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Comparative example 3】
The platinum acid chloride solution that 1.224mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g
SCNT is added in this solution, and stirring, room temperature places 2h, afterwards the dry 4h at 120 DEG C, finally puts it into the Muffle of He atmosphere
4h is roasted at 350 DEG C in stove, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Comparative example 4】
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g
SCNT is added in this solution, and stirring, room temperature places 2h, ultrasonic 8h, and the dry 4h at 120 DEG C, finally puts it into He atmosphere afterwards
4h is roasted at 350 DEG C in the Muffle furnace enclosed, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Comparative example 5】
2g single-walled carbon nanotubes (SCNT) are weighed, are added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, it
After filter, be washed with water until solution into neutrality, by obtained SCNT in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
SCNT afterwards is added in this solution, and stirring, room temperature places 2h, and the dry 4h at 120 DEG C, finally puts it into He atmosphere afterwards
4h is roasted at 350 DEG C in Muffle furnace, obtains catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
【Comparative example 6】
2g aluminium oxide is weighed, is added in the salpeter solution of 50ml 68%, 8h is heated at 80 DEG C, filters, be washed with water afterwards
Wash until solution is into neutrality, by obtained aluminium oxide in 120 DEG C of dry 6h, the SCNT after being handled.
The platinum acid chloride solution that 0.622mL concentration is 16.14mL/L is taken, 1.378mL water is added and is configured to solution, by 2g processing
Aluminium oxide afterwards is added in this solution, and stirring, room temperature places 2h, and the dry 4h at 120 DEG C, finally puts it into He atmosphere afterwards
Muffle furnace in 350 DEG C roast 4h, obtain catalyst.
Obtained catalysis material tabletting is ground, the part that granularity is 20-40 mesh is chosen, takes 0.1 gram to consolidate in isotherm formula
Evaluated in fixed bed differential reactor, evaluate preceding hydrogen reducing, reducing condition is as follows：Pressure normal pressure, 350 DEG C of temperature, hydrogen
Throughput is 20mL/min, recovery time 4h, and cooling evaluation, appreciation condition are as follows afterwards：Reaction pressure normal pressure, temperature 320
DEG C, air speed 2h-1, the representative raw material of organic liquid hydrogen storage is used as using hexahydrotoluene.The result is shown in table 1.
Table 1
【Embodiment 14~19】
The catalyst that embodiment 1 is prepared is used for the performance evaluation in dehydrogenating low-carbon alkane producing light olefins, as a result
It is shown in Table 2.
Table 2
【Embodiment 20~26】
The catalyst that embodiment 1 is prepared is used for the performance evaluation of organic liquid hydrogen storage material dehydrogenation reaction, as a result
It is shown in Table 3.
Table 3
Claims (10)
1. a kind of modified carbon nano tube material, in terms of parts by weight, including following components：
(a) 0.1~5 part of active component；
(b) 95~99.9 parts of carbon nanomaterials；
Active component (a) is selected from least one of the VIIth B races of the periodic table of elements or the VIIIth race's element metal or its alloy.
2. modified carbon nano tube material according to claim 1, it is characterised in that carbon nanomaterial is selected from single-walled carbon nanotube
(SCNT), at least one of multi-walled carbon nanotube (MCNT), carbon nano-fiber and Nano carbon balls.
3. modified carbon nano tube material according to claim 2, it is characterised in that carbon nanomaterial is selected from single-walled carbon nanotube
(SCNT) and/or multi-walled carbon nanotube (MCNT).
4. modified carbon nano tube material according to claim 1, it is characterised in that active component is mainly distributed on carbon nanometer material
The inner wall of material.
5. the preparation method of Claims 1 to 4 any one of them modified carbon nano tube material, comprises the following steps：
(1) strong acid treatment is carried out to carbon nanomaterial；
(2) to introduce active component in a manner of impregnating or precipitate in the form of ultrasonic wave added.
6. the preparation method of modified carbon nano tube material according to claim 5, it is characterised in that impregnate carbon nanomaterial
Mixture is formed in strong acid solution, heats this mixture at 60-100 DEG C, heating time 4-8h, filtration washing solution afterwards
To neutrality.
7. any one of the claim 1-3 modified carbon nano tube materials are used for dehydrogenating low-carbon alkane, organic liquid hydrogen storage material takes off
The purposes of hydrogen and other dehydrogenation reactions.
8. a kind of method that dehydrogenating low-carbon alkane prepares low-carbon alkene, uses propane and/or iso-butane as raw material, in reaction temperature
520~620 DEG C, 0~0.4MPa of reaction pressure, 0.1~8.0h of alkane mass space velocity-1, H2O/CnH2n+2Volume ratio is 1~18
Under part, any one of raw material and claims 1 to 3 the modified carbon nano tube material reaction generation propylene and/or isobutene.
9. a kind of method of organic liquid hydrogen storage material dehydrogenation, reaction condition are as follows：Reaction pressure is 0~1MPa, temperature 200
~450 DEG C, mass space velocity be 0.1~10h-1；Organic liquid hydrogen storage material is received with any one of claim 1~6 carbon modified
Rice material reaction produces hydrogen and corresponding aromatic hydrocarbons.
10. the method for organic liquid hydrogen storage material dehydrogenation according to claim 9, it is characterised in that organic liquid hydrogen storage material
Material is selected from least one of hexahydrotoluene hexamethylene, naphthane, decahydronaphthalene, perhydro nitrogen ethyl carbazole and perhydro carbazole.
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