CN116651461A - Preparation method and application of novel superfine array carbon tube catalyst - Google Patents
Preparation method and application of novel superfine array carbon tube catalyst Download PDFInfo
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- CN116651461A CN116651461A CN202310504388.8A CN202310504388A CN116651461A CN 116651461 A CN116651461 A CN 116651461A CN 202310504388 A CN202310504388 A CN 202310504388A CN 116651461 A CN116651461 A CN 116651461A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 90
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 10
- 239000000872 buffer Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 159000000003 magnesium salts Chemical class 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- 229910000275 saponite Inorganic materials 0.000 claims description 6
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 4
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910013500 M-O—Si Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/34—Length
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
Abstract
The invention discloses a preparation method and application of a novel superfine array carbon tube catalyst, and relates to the technical field of superfine carbon nanotube catalysts. The preparation method of the novel superfine array carbon tube catalyst disclosed by the invention comprises the following steps: slowly dripping the auxiliary agent salt solution into the active component salt solution, and uniformly mixing; cage-type silsesquioxane/soapstone prepared by adopting a hydrothermal synthesis method is used as a catalyst carrier; adding the mixed auxiliary agent into a catalyst carrier, adding deionized water, carrying out ultrasonic mixing uniformly, crystallizing under the condition of high-temperature heating, drying and roasting to obtain the catalyst; also discloses a preparation method of the cage-type silsesquioxane/soapstone and application thereof in preparing the carbon nano tube. The novel superfine array carbon tube catalyst provided by the invention can obviously improve the yield and quality of carbon nanotubes and solve the macro preparation problem of superfine carbon nanotubes; and the structural parameters of the core metal and the carrier of the catalyst can be accurately regulated and controlled, so that the prepared carbon nano tube has the advantages of high purity, good uniformity of tube diameter and the like.
Description
Technical Field
The invention belongs to the technical field of ultrafine carbon nanotube catalysts, and particularly relates to a carbon nanotube catalyst with an ultrafine array structure of diameter tubes, a preparation method thereof and application thereof in preparation of carbon nanotubes.
Background
Since carbon nanotubes were found by humans, their excellent properties have been widely studied, greatly promoting the development of science and technology. The carbon nano tube is also called as a Baki tube, can be regarded as a tubular structure formed by regular hexagons as a basic unit after the graphene is curled, has the length of several micrometers to tens of micrometers, is radial but is nano-scale, is a one-dimensional quantum material, and has unique physical structure and chemical property. The superfine carbon nano tube has a tube diameter of 2-9 nm, and has remarkable high mechanical strength, heat conductivity and electric conductivity, and the superfine carbon nano tube has great application value in the aspects of composite materials, biological materials, electronic elements and the like.
The superfine carbon nanotube has the characteristics of high light absorption, wide spectrum response and the like, is a photoelectric detection material with great prospect, has extremely high aspect ratio, high mechanical strength, toughness, conductivity and elasticity, can reach 100 times of steel in theoretical strength, has the density of only one sixth of steel, is acid and alkali resistant, is basically not oxidized below 700 ℃ in air, and has good thermal stability and chemical stability. Currently, a method for preparing ultrafine carbon nanotubes is mainly a chemical vapor deposition method (CVD method) in which a gas containing a carbon source is decomposed on the surface of a catalyst and induced to form a carbon nanotube structure on one side of the catalyst. The CVD method has the advantages of low cost, large yield, convenient control of test conditions and the like, and is the method most suitable for large-scale industrial production at present. However, the main influencing factors in the process of preparing the superfine carbon nano tube by the CVD method are catalysts, carbon sources, temperature conditions and the like, and transition metals such as iron, cobalt, nickel and the like are most commonly used as active components, but the catalysts are easy to gather at high temperature and lose active sites, so that the conversion rate is low, the defects of the crystal structure of the carbon nano tube are more, the tube diameter distribution is uneven, the bending deformation is easy, and the graphitization degree is low.
And the superfine carbon nano tube has not been applied in production and living, but can not show the value prospect in production and living, the main reason is that the macro preparation problem of the superfine carbon nano tube with consistent structure and single conductive property can not be solved, and the current superfine carbon nano tube production basically belongs to laboratory preparation or production line small quantity preparation.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a novel catalyst of a carbon nano tube with an ultra-fine array structure of a diameter tube, and the prepared catalyst can obviously improve the yield and quality of the carbon nano tube so as to solve the macro preparation problem of the ultra-fine carbon nano tube; and the structural parameters of the core metal and the carrier of the catalyst can be accurately regulated and controlled, so that the prepared carbon nano tube has the advantages of high purity, good uniformity of tube diameter and the like.
In order to achieve the purpose of the invention, the invention provides a preparation method of a novel superfine array carbon tube catalyst, which specifically comprises the following steps:
(1) Preparing an auxiliary agent salt solution and an active component salt solution, slowly dropwise adding the auxiliary agent salt solution into the active component salt solution, and uniformly stirring to obtain a mixed solution A.
(2) Cage-type silsesquioxane/soapstone prepared by adopting a hydrothermal synthesis method is used as a catalyst carrier.
(3) Adding the mixed solution A into a catalyst carrier to uniformly mix the mixed solution A and the catalyst carrier, transferring the catalyst carrier and the mixed solution A into a high-pressure reactor, heating at a high temperature to crystallize the catalyst carrier and the mixed solution A, placing the obtained product into a baking oven to be dried at 100 ℃, and transferring the product into a muffle furnace to be baked to obtain the novel catalyst.
Preferably, the mass ratio of the mixed solution A to the catalyst carrier is (1-1.5): 1.
further, the auxiliary agent salt solution is any one or more of ammonium bicarbonate, ammonium molybdate, ammonium bisulfate, ammonium nitrate or ammonia water, and the concentration of the auxiliary agent salt solution is 0.1-0.8 mol/L;
the active component salt solution is one or more of ferric sulfate, ferric chloride, ferric nitrate, cobalt sulfate, cobalt chloride, cobalt nitrate, nickel sulfate, nickel chloride or nickel nitrate, and the concentration of the active component salt solution is 0.1-0.7 mol/L;
the mass ratio of the auxiliary agent salt solution to the active component salt solution is (1-3): 1.
further, the catalyst carrier in the step (3) is cage-type silsesquioxane/soapstone with the particle size of 60-100 meshes. The catalyst carrier cage-type silsesquioxane/soapstone with the particle size range is mainly used in the invention, because when the catalyst reacts in a fluidized bed, the catalyst is suspended in the reactor, the catalyst cannot be suspended due to the too large particle size and falls to the bottom of the reactor, and the catalyst is concentrated at the top of the reactor even blown into a vent pipeline by carrier gas due to the too small particle size.
Furthermore, the high-pressure reactor is provided with a gas release valve, and gas in the high-pressure reactor is released when the high-pressure reactor is heated to a certain pressure, so that the crystallization process is accelerated.
Further, in the crystallization process, the heating temperature is 700 ℃, and the reaction time is 1-2 h. Preferably, the invention adopts high heating rate in the crystallization process, so that the temperature is quickly raised to 700 ℃ within 8min, thereby ensuring that the inside of the high-pressure reactor is heated unevenly, aggravating the solution reaction and ensuring that the ion exchange is more sufficient.
Further, in the roasting process, the roasting temperature is 550-600 ℃, and the roasting time is 5-12 h.
Further, the preparation method of the cage type silsesquioxane/soapstone comprises the following steps:
s1, adding water glass and cage-type silsesquioxane into a buffer solution, and uniformly stirring to obtain a mixed solution B;
s2, adding a proper amount of magnesium-aluminum composite salt into deionized water, and stirring uniformly by ultrasonic to obtain a solution C.
S3, slowly dripping the solution C into the mixed solution B under magnetic stirring to obtain white emulsion, transferring the white emulsion into a high-pressure reaction kettle, keeping the temperature at 90 ℃, and stirring for 5 hours to obtain a product.
S4, washing the product with deionized water, then carrying out centrifugal separation to obtain a cage-type silsesquioxane/soapstone colloid, and drying at 90-110 ℃ for 12-24 hours to obtain a cage-type silsesquioxane/soapstone solid.
The catalyst carrier cage type silsesquioxane used in the inventionAlkyl/saponite is a special structure in which saponite and cage silsesquioxane are incorporated. The soapstone belongs to one of smectite layered silicate minerals, and is 2:1 (TOT) type trioctahedral phyllosilicate clay mineral, the structure of soapstone is very special, each layer is composed of two silicon oxygen tetrahedra sandwiching a magnesium oxygen octahedron, and an ideal soapstone molecular formula can be expressed as N Z+ x/z Mg 6 Si 8-x Al x O 20 (OH) 4 ·nH 2 O, the top oxygen of the tetrahedron is directed toward the center of the structural layer and shared with the octahedron, thereby joining the three sheets together. Polyhedral silsesquioxane is used as an organic-inorganic hybrid material, and the Si-O-Si structure in the compound structure has good thermal stability and thermal oxygen stability, and can be combined with most substances in application due to the structural specificity. 1) Capable of grafting one or more reactive groups or atoms; 2) The non-reactive organic functional groups can be designed to be different groups depending on the nature of the less polymer; 3) Other compounds containing N, P, S or metal atoms can be grafted.
The three-dimensional structure of the cage-type silsesquioxane molecule contains a large amount of organic end groups, the cage-type silsesquioxane is matched with soapstone to increase the reactivity, the multiport active site of the silsesquioxane can be coordinated and combined with metal atoms to form an organic/inorganic compound of metal, the catalytic activity of the supported catalyst can be improved by supporting the metal atoms, and the M-O-Si structure is formed by bonding with the active center of the metal atoms. The combination of soapstone and cage-type silsesquioxane improves the compatibility of different phases, increases the regularity and controllability of a molecular structure, and the terminal group contains a plurality of active reaction sites, so that the structure is more diversified and the application is wider.
Further, the buffer solution is deionized water or alkali liquor with the pH value of 8-10. Preferably, the alkaline solution with the pH value of 8-10 is prepared by adopting a molar ratio of 1.5:1 NaOH and NaHCO 3 Adding into deionized water, and mixing uniformly by ultrasonic.
Further, the cage type silsesquioxane is any one or more of cage type octavinyl silsesquioxane, cage type octaisobutyl silsesquioxane and cage type octaphenyl silsesquioxane.
Further, in the step S1, the molar ratio of the water glass to the cage-type silsesquioxane is (1.0 to 1.2): (0.02-0.06).
Further, in the step S2, the magnesium-aluminum composite salt includes a magnesium salt and an aluminum salt, the magnesium salt is a soluble magnesium salt, and the aluminum salt is at least a soluble aluminum salt.
Further, the soluble magnesium salt is any one of magnesium nitrate and magnesium chloride; the soluble aluminum salt is any one of aluminum nitrate and aluminum chloride.
Further, in the step S3, the molar ratio of the silicon, magnesium and aluminum elements in the white emulsion is (0.5-2): 1: (0.5-1). That is, the water glass, the cage type silsesquioxane and the magnesium aluminum composite salt in the invention are prepared by solution configuration according to n (Si): n (Al) = (0.5-2): 0.5-1): 1 to obtain the subsequent white emulsion.
The novel superfine array carbon tube catalyst can be applied to the preparation of carbon nanotubes, and the preparation method of the carbon nanotubes comprises the following steps:
heating a reactor to 670-700 ℃, adding a novel superfine array carbon tube catalyst, uniformly introducing raw material gas and carrier gas, then introducing reducing gas, and taking out a product after the reaction is completed to obtain black fluffy solid; and purifying, pickling and washing the product to obtain the carbon nanotube.
Preferably, the reaction time is 1h. Because the yield of the carbon nanotubes does not change with the extension of the reaction time.
Further, the raw material gas contains a carbon source, and is any one or more of acetone, methane, ethane, ethylene, acetylene, butane, butene, methanol, ethanol or propylene;
the carrier gas is any one or more of helium, argon or nitrogen.
Further, in the reaction process, the air flow rate of the carrier gas is 100-200L/min; the volume ratio of the carrier gas to the reducing gas to the raw material gas is 2:1:1. the reducing gas includes, but is not limited to, hydrogen.
The invention has the following beneficial effects:
1. the invention adopts the prepared superfine array carbon tube novel catalyst, prepares the metal-based nano material containing the organic ligand by a Chemical Vapor Deposition (CVD) method, and is easy to realize the controllable synthesis of the catalyst and the mass production of the carbon nanotubes.
2. The novel superfine array carbon tube catalyst is used for solving the defects of the existing superfine carbon nanotube preparation process, solving the defects of low yield, high ash content, thick tube diameter and uneven distribution, and realizing the superfine carbon tube preparation process with high quality and high yield.
3. The invention combines cage-type silsesquioxane with laponite, can graft a plurality of reactive groups or atoms, improves the compatibility of different phases, increases the regularity and controllability of a molecular structure, and ensures that the terminal group contains a plurality of active reaction sites, so that the structure is more diversified and the application is wider. The catalyst mentioned in the patent combines the silsesquioxane with the synthetic soapstone, utilizes the special structure of the soapstone and the cage-shaped silsesquioxane synthesized by the hydrothermal method, can be grafted with a plurality of reactive groups or atoms, is connected with a plurality of active reaction sites, combines more active metals, and greatly improves the catalyst yield.
4. The high-pressure reactor is provided with the air release valve, so that the air release valve releases pressure in the reaction process, and the reaction process is increased, thereby being beneficial to the crystallization process; and the heating rate can be increased, so that the heating is uneven, the solution is boiled and rolled, and the carrier and the active components are contacted more fully, so that the ion exchange is more complete.
5. The preparation process of the superfine array carbon tube novel catalyst is controllable and convenient to implement, the sources of raw materials are wide, the post-treatment and instrument maintenance of the carbon tube are simpler and more convenient, and the mass production of the carbon nanotubes can be realized.
6. The superfine array carbon tube novel catalyst prepared by the invention has adjustable carrier performance and size, active components are uniformly distributed on the carrier, the active components cannot be decomposed or sintered after high-temperature treatment, the diameter of the produced carbon nano tube is distributed at 6nm, and the tube diameter is uniformly distributed. The Raman spectrum test result shows that the carbon nano tube has fewer defects and high graphitization degree.
7. The carbon nano tube prepared by adopting the novel superfine array carbon tube catalyst has an orderly array structure, the tube length is 5-70 um, the diameter is 2-7 nm, and the number of layers is 1-20; the conductivity of the powder is 7000-18000S/m; the light-sensitive fluorescent material has good response performance to light with the wavelength of 500-1900 nm at room temperature and in an atmospheric environment, and the response at the wavelength of 700nm can reach 67.2mA/W; the crystallinity is 70-85%, and the yield is 28-42 times.
Drawings
FIG. 1 is a scanning electron microscope image of a carbon nanotube according to example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of the carbon nanotube of example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the carbon nanotube of comparative example 1 of the present invention;
FIG. 4 is a transmission electron microscope image of the carbon nanotube of comparative example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of a carbon nanotube according to example 2 of the present invention;
FIG. 6 is a transmission electron microscope image of a carbon nanotube of example 2 of the present invention;
FIG. 7 is a Raman spectrum of the chemical structure of the carbon nanotube of example 1 of the present invention;
FIG. 8 is a flow chart of the preparation of cage silsesquioxane/saponite solids according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The carbon nanotube yield in the present invention means a ratio of the mass of carbon produced to the mass of the catalyst.
The ultra-fine array carbon tube novel catalyst and the carbon nanotubes prepared by the same according to the present invention will be described with reference to specific examples.
Example 1
As shown in fig. 8, the catalyst carrier is prepared as follows:
sequentially adding sodium silicate, octavinyl silsesquioxane, aluminum chloride and magnesium chloride into 500mL of deionized water, stirring uniformly, and ultrasonically mixing uniformly to obtain a mixed solution, wherein the concentrations of the four substances are 1.2moL/L, 0.02moL/L, 0.5moL/L and 0.8moL/L respectively. The mixed solution was transferred to a high pressure reactor, kept at 90℃for 5 hours with stirring. The product was washed 4 times with deionized water, centrifuged to give a silsesquioxane/soapstone colloid, and dried at 90 ℃ for 16 hours to give a silsesquioxane/soapstone solid.
The preparation method of the catalyst comprises the following steps:
uniformly stirring ferric nitrate and aluminum nitrate in 100mL of water to prepare an active component solution with the concentration of 0.5moL/L of each of the ferric nitrate and the aluminum nitrate, wherein the mass ratio is 1:1.2 ammonium molybdate tetrahydrate and ammonium bicarbonate are mixed and stirred uniformly in 100mL of deionized water to prepare an auxiliary component solution with molybdenum content of 0.3 moL/L. Then, the auxiliary agent solution is quickly dripped into the active component solution to form a mixed solution, and the mass ratio is 1:1 and the catalyst carrier are mixed and stirred uniformly to form a suspension.
The suspension was transferred to a high pressure reactor placed in a 1cm thick aluminum skin (for promoting ion exchange reactions and recording the weight loss of the aluminum skin after the end of the re-reaction), evaporated for 1h to give the product, and the water content of the evaporated product was recorded. In the evaporation process (i.e. crystallization process), a gas leakage device of the high-pressure reactor is opened, so that the whole evaporation process keeps a certain pressure in the high-pressure equipment until the solution in the high-pressure equipment is completely changed into gas to be discharged, and the whole crystallization process is completed.
And then the product is put in a baking oven at 100 ℃ for 12 hours to obtain a catalyst precursor, and then the precursor is put in a muffle furnace for baking at 550 ℃ for 5 hours to prepare the carbon nanotube catalyst.
Preparation of carbon nanotubes:
placing 1g of the prepared carbon nano tube catalyst in an experimental fluidized bed at 700 ℃, uniformly introducing a mixed gas of propylene and nitrogen, wherein the flow rate of the mixed gas is 180L/min, the flow rate of carrier gas nitrogen is 120L/min, the flow rate of raw material gas propylene is 60L/min, and V propylene: v nitrogen = 1: and introducing reducing gas hydrogen after 2 minutes, wherein the flow is 60L/min. After the reaction for 1h, stopping introducing propylene and hydrogen, and cooling under the protection of 10L/min nitrogen to obtain the carbon nano tube. The detection shows that the yield of the carbon nano tube is 32 times, the conductivity is 8500S/m, the diameter of the carbon nano tube is 6-8 nm, the ash value is 6%, and the catalyst is qualified.
As shown in fig. 1, the carbon nanotubes prepared in example 1 were ordered into an ultrafine carbon nanotube array and the grown carbon nanotubes were dense, as a result of the surface microscopic morphology observed by a scanning electron microscope (model S-4800, hitachi electronics, japan).
As shown in FIG. 2, the diameter and the number of layers of the carbon nanotubes obtained in example 1 were observed by a transmission electron microscope (model Hitachi HT7700, hitachi electronics, japan), and the diameter of the obtained carbon nanotubes was 6 to 8nm, which was smaller than that of the carbon nanotubes on the market.
As shown in fig. 7, the chemical structure of the carbon nanotube prepared in example 1, which is characterized by raman spectroscopy, is shown in fig. 7 to have few defects and high graphitization degree.
Comparative example 1
The preparation method of the catalyst carrier comprises the following steps:
sequentially adding sodium silicate, aluminum chloride and magnesium chloride into 500mL of deionized water, and uniformly stirring to obtain a mixed solution, wherein the concentrations of the three substances are 1.4moL/L, 0.5moL/L and 0.8moL/L respectively. The mixed solution was transferred to a high pressure reactor, kept at 90℃for 5 hours with stirring. The product was washed with deionized water for 4 times, centrifuged to obtain a colloid of ploidy soapstone, and dried at 90℃for 16 hours to obtain a soapstone solid.
The preparation method of the catalyst comprises the following steps:
uniformly stirring ferric nitrate and aluminum nitrate in 100mL of water to prepare an active component solution with the concentration of 0.5moL/L of each of the ferric nitrate and the aluminum nitrate, wherein the mass ratio is 1:1.2 ammonium molybdate tetrahydrate and ammonium bicarbonate are mixed and stirred uniformly in 100mL of deionized water to prepare an auxiliary component solution with molybdenum content of 0.3 moL/L. Then, the auxiliary agent solution is quickly dripped into the active component solution to form a mixed solution, and the mass ratio is 1:1 and the catalyst carrier are mixed and stirred uniformly to form a suspension.
The suspension was transferred to a high pressure reactor placed in a 1cm thick aluminum skin (for promoting ion exchange reactions and recording the weight loss of the aluminum skin after the end of the re-reaction), evaporated for 1h to give the product, and the water content of the evaporated product was recorded. In the evaporation process (i.e. crystallization process), a gas leakage device of the high-pressure reactor is opened, so that the whole evaporation process keeps a certain pressure in the high-pressure equipment until the solution in the high-pressure equipment is completely changed into gas to be discharged, and the whole crystallization process is completed.
And then the product is put in a baking oven at 100 ℃ for 12 hours to obtain a catalyst precursor, and then the precursor is put in a muffle furnace for baking at 550 ℃ for 5 hours to prepare the carbon nanotube catalyst.
Preparation of carbon nanotubes:
placing 1g of the prepared carbon nano tube catalyst in an experimental fluidized bed at 700 ℃, uniformly introducing a mixed gas of propylene and nitrogen, wherein the flow rate of the mixed gas is 180L/min, and the velocity of the V propylene is as follows: v nitrogen = 1:2, stopping introducing propylene after reacting for 1h, and cooling under the protection of 10L/min nitrogen to obtain the carbon nano tube. Through detection, the yield of the carbon nano tube is 28 times, the conductivity is 6000S/m, the diameter of the carbon nano tube is 14-18 nm, the ash value is 10%, and the quality of the carbon nano tube is poor compared with that of the example 1.
As shown in FIG. 3, the carbon nanotube prepared in comparative example 1 has a surface microstructure observed by a scanning electron microscope (model S-4800, hitachi electron, japan), and the carbon nanotube has poor order and is disordered in orientation.
As shown in FIG. 4, the diameter and the number of layers of the carbon nanotube obtained in comparative example 1 were observed by a transmission electron microscope (model Hitachi HT7700, hitachi electronics, japan), and the diameter of the obtained carbon nanotube was 14 to 18nm, which is coarser than that in example 1.
Example 2
As shown in FIG. 8, 500mL of buffer (NaOH and NaHCO) mixed by adding sodium hydroxide and sodium bicarbonate to water was prepared 3 The molar ratio of (2) is 1.5:1, pH of buffer is 8), and the molar ratio of the buffer to the buffer is 1.2:0.02 water glass and octavinylsilsesquioxane, noted as solution a. Adding aluminum nitrate and magnesium nitrate into 200mL of deionized water, marking as a solution B, slowly adding the solution B into the solution A, and uniformly stirring to obtain a mixed solution, wherein the molar ratio of Si, al and Mg in the mixed solution is 1.4:0.5:0.8. The mixed solution was transferred to a high pressure reactor, kept at 90℃for 5 hours with stirring. The product was washed 4 times with deionized water and dried at 90 ℃ for 16 hours to give a cage silsesquioxane/saponite solid.
Uniformly stirring ferric nitrate and aluminum nitrate in 100mL of water to prepare an active component solution with the concentration of 0.5moL/L of each of the ferric nitrate and the aluminum nitrate, wherein the mass ratio is 1:1.2 ammonium molybdate tetrahydrate and ammonium bicarbonate are mixed and stirred uniformly in 100mL of deionized water to prepare an auxiliary component solution with molybdenum content of 0.2 moL/L. The auxiliary agent solution is quickly dripped into the active component solution to form a mixed solution, and the mass ratio is 1:1 and the catalyst carrier are mixed and stirred uniformly to form a suspension.
The suspension was transferred to a high pressure reactor placed in a 1cm thick aluminum skin (for promoting ion exchange reactions and recording the weight loss of the aluminum skin after the end of the re-reaction), evaporated for 1h to give the product, and the water content of the evaporated product was recorded. In the evaporation process (i.e. crystallization process), a gas leakage device of the high-pressure reactor is opened, so that the whole evaporation process keeps a certain pressure in the high-pressure equipment until the solution in the high-pressure equipment is completely changed into gas to be discharged, and the whole crystallization process is completed.
And then the product is put in a baking oven at 100 ℃ for 12 hours to obtain a catalyst precursor, and then the precursor is put in a muffle furnace for roasting at 500 ℃ for 5 hours to prepare the carbon nanotube catalyst.
Preparation of carbon nanotubes:
placing 1g of the prepared carbon nanotube catalyst in an experimental fluidized bed at 700 ℃, uniformly introducing a mixed gas of propylene and nitrogen, wherein the flow rate of the mixed gas is 180L/min, the flow rate of carrier gas nitrogen is 120L/min, the flow rate of raw material gas propylene is 60L/min, and V propylene: v nitrogen = 1:2, stopping introducing propylene after reacting for 1h, and cooling under the protection of 10L/min nitrogen to obtain the carbon nano tube. The detection shows that the yield of the carbon nano tube is 35 times, the conductivity is 9500S/m, the diameter of the carbon nano tube is 2-5 nm, the ash value is 4%, and the catalyst is qualified.
As shown in fig. 5, the carbon nanotubes prepared in example 1 were ordered into an ultrafine carbon nanotube array and the grown carbon nanotubes were dense, as a result of the surface microscopic morphology observed by a scanning electron microscope (model S-4800, hitachi electronics, japan).
As shown in fig. 6, the diameter and the number of layers of the carbon nanotube obtained in example 1 were observed by a transmission electron microscope (model Hitachi HT7700, hitachi electronics, japan), and the diameter of the obtained carbon nanotube was 2 to 5nm, which is finer than that of the carbon nanotube of example 1.
Example 3
500mL of buffer (NaOH and NaHCO) mixed by adding sodium hydroxide and sodium bicarbonate to water was prepared 3 The molar ratio of (2) is 1.5:1, pH of buffer is 8), and the molar ratio of the buffer to the buffer is 1.2:0.02 water glass and octavinylsilsesquioxane, noted as solution a. Adding aluminum nitrate and magnesium nitrate into 200mL of deionized water, marking as a solution B, slowly adding the solution B into the solution A, and uniformly stirring to obtain a mixed solution, wherein the molar ratio of Si, al and Mg in the mixed solution is 1.5:1:1. The mixed solution was transferred to a high pressure reactor, kept at 90℃for 5 hours with stirring. The product was washed 4 times with deionized water and dried at 90 ℃ for 16 hours to give a cage silsesquioxane/saponite solid.
Iron nitrate and aluminum nitrate are uniformly stirred in 100mL of water to prepare an active component solution with the concentration of iron and aluminum of 1moL/L, and the mass ratio is 1:1.2, uniformly mixing and stirring ammonium molybdate tetrahydrate and ammonium bicarbonate in 100mL of deionized water to prepare an auxiliary component solution with molybdenum content of 0.2moL/L, rapidly dripping the auxiliary component solution into an active component solution to form a mixed solution, and mixing the components according to the mass ratio of 1:1 and the catalyst carrier are mixed and stirred uniformly to form a suspension. The suspension was transferred to a high pressure reactor placed in a 1cm thick aluminum skin (for promoting ion exchange reactions and recording the weight loss of the aluminum skin after the end of the re-reaction), evaporated for 1h to give the product, and the water content of the evaporated product was recorded. In the evaporation process (i.e. crystallization process), a gas leakage device of the high-pressure reactor is opened, so that the whole evaporation process keeps a certain pressure in the high-pressure equipment until the solution in the high-pressure equipment is completely changed into gas to be discharged, and the whole crystallization process is completed.
And then the product is put in a baking oven at 100 ℃ for 12 hours to obtain a catalyst precursor, and then the precursor is put in a muffle furnace for roasting at 500 ℃ for 5 hours to prepare the carbon nanotube catalyst.
Preparation of carbon nanotubes:
placing 1g of the prepared superfine array carbon tube novel catalyst in an experimental fluidized bed at 700 ℃, uniformly introducing a mixed gas of propylene and nitrogen, wherein the flow rate of the mixed gas is 180L/min, the flow rate of carrier gas nitrogen is 120L/min, the flow rate of raw material gas propylene is 60L/min, and V propylene: v nitrogen = 1:2, stopping introducing propylene after reacting for 1h, and cooling under the protection of 10L/min nitrogen to obtain the carbon nano tube. The detection shows that the yield of the carbon nano tube is 36 times, the conductivity is 9000S/m, the diameter of the carbon nano tube is 2-5 nm, the ash value is 5%, and the catalyst is qualified.
This example 3, comparative example 2, is an increase in the concentration of the active component solution, a slight increase in the yield of carbon nanotubes, a slight increase in ash values, and no change in other quality parameters.
From the experimental procedures and the detection results of examples 1 to 3 and comparative example 1 above, the following conclusions can be drawn:
(1) Example 1 and comparative example 1 mainly compare the difference between the addition of cage-like silsesquioxane during the preparation of the catalyst, and compare the difference between the addition and the non-addition of cage-like silsesquioxane, and find the advantages of better morphology, finer tube diameter, lower ash content and higher resistivity of the carbon nanotubes produced after the addition.
(2) Example 2 is different from example 1 in that carbon nanotubes of more excellent quality can be further obtained by optimizing experimental conditions, controlling the pH of the solution, and optimizing experimental procedures.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (10)
1. The preparation method of the novel superfine array carbon tube catalyst is characterized by comprising the following steps of:
(1) Preparing an auxiliary agent salt solution and an active component salt solution, slowly dropwise adding the auxiliary agent salt solution into the active component salt solution, and uniformly stirring to obtain a solution A;
(2) Cage-type silsesquioxane/soapstone prepared by adopting a hydrothermal synthesis method is used as a catalyst carrier;
(3) Adding the solution A into a catalyst carrier to uniformly mix the solution A and the catalyst carrier, then placing the mixed solution into a high-pressure reactor, quickly heating to 700 ℃, crystallizing, drying and roasting at the temperature to obtain the novel catalyst.
2. The preparation method of the superfine array carbon tube novel catalyst according to claim 1, wherein the auxiliary agent salt solution is any one or more of ammonium bicarbonate, ammonium molybdate, ammonium bisulfate, ammonium nitrate or ammonia water, and the concentration of the auxiliary agent salt solution is 0.1-0.8 mol/L;
the active component salt solution is one or more of ferric sulfate, ferric chloride, ferric nitrate, cobalt sulfate, cobalt chloride, cobalt nitrate, nickel sulfate, nickel chloride or nickel nitrate, and the concentration of the active component salt solution is 0.1-0.7 mol/L.
3. The method for preparing a novel ultrafine array carbon tube catalyst according to claim 1, wherein in the step (3), the catalyst carrier is cage-type silsesquioxane/saponite with a particle size of 60-100 meshes;
and a gas release valve is arranged on the high-pressure reaction kettle.
4. The method for preparing the superfine array carbon tube novel catalyst according to claim 1, wherein the preparation method of the cage type silsesquioxane/soapstone is as follows:
s1, adding water glass and cage-type silsesquioxane into a buffer solution, and uniformly stirring to obtain a mixed solution B;
s2, adding a proper amount of magnesium-aluminum composite salt into deionized water, and uniformly stirring by ultrasonic to obtain a solution C;
s3, slowly dripping the solution C into the mixed solution B under magnetic stirring to obtain white emulsion, transferring the white emulsion into a high-pressure reaction kettle, keeping the temperature at 90 ℃, and stirring for 5 hours to obtain a product;
s4, washing the product with deionized water, then carrying out centrifugal separation to obtain a cage-type silsesquioxane/soapstone colloid, and drying at 90 ℃ for 16 hours to obtain a cage-type silsesquioxane/soapstone solid.
5. The method for preparing a novel ultrafine array carbon tube catalyst according to claim 4, wherein the buffer is deionized water or alkali solution with a pH value of 8-10.
6. The method for preparing a novel ultrafine array carbon-tube catalyst as defined in claim 4, wherein in the step S2, the magnesium-aluminum composite salt comprises magnesium salt and aluminum salt, the magnesium salt is soluble magnesium salt, and the aluminum salt is soluble aluminum salt.
7. The method for preparing a novel ultrafine array carbon tube catalyst according to claim 4, wherein in the step S3, the molar ratio of silicon, magnesium and aluminum elements in the white emulsion is (0.5-2): 1: (0.5-1).
8. A novel ultrafine array carbon-tube catalyst prepared by the method for preparing a novel ultrafine array carbon-tube catalyst according to any one of claims 1 to 7.
9. The use of the superfine array carbon tube novel catalyst as claimed in claim 8 in the preparation of carbon nanotubes, wherein the preparation method of the carbon nanotubes comprises the following steps:
heating a reactor to 670-700 ℃, adding a novel superfine array carbon tube catalyst, uniformly introducing raw material gas and carrier gas, then introducing reducing gas, and taking out a product after the reaction is completed to obtain black fluffy solid; and purifying, pickling and washing the product to obtain the carbon nanotube.
10. The use of the ultrafine array carbon-tube novel catalyst according to claim 9 for preparing carbon nanotubes, wherein the raw material gas contains a carbon source and is any one or more of acetone, methane, ethane, ethylene, acetylene, butane, butene, methanol, ethanol or propylene;
the carrier gas is any one or more of helium, argon or nitrogen.
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