CN114011418A - Preparation method of methane cracking catalyst - Google Patents
Preparation method of methane cracking catalyst Download PDFInfo
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- CN114011418A CN114011418A CN202111479259.5A CN202111479259A CN114011418A CN 114011418 A CN114011418 A CN 114011418A CN 202111479259 A CN202111479259 A CN 202111479259A CN 114011418 A CN114011418 A CN 114011418A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000005336 cracking Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 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 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 239000002904 solvent Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000001354 calcination Methods 0.000 claims 2
- 238000005470 impregnation Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 43
- 239000007789 gas Substances 0.000 description 43
- 239000002041 carbon nanotube Substances 0.000 description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 238000010926 purge Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000002079 double walled nanotube Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
-
- B01J35/40—
-
- 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
- C01B2202/34—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
Abstract
The invention discloses a preparation method of a methane cracking catalyst, which comprises the following steps: (1) drying the carrier at the temperature of 100-120 ℃ for 1-5h, and then placing the carrier in a dryer to cool to room temperature; (2) dropwise adding a metal salt solution into the carrier obtained in the step (1) while stirring, standing at room temperature for 1-4h after dropwise adding is finished, and drying at 80-120 ℃ for 8-15 h; (3) grinding until no obvious block is formed after drying is finished, then roasting at the temperature of 400-800 ℃ for 4-8h, cooling to room temperature, and grinding again to obtain powder, namely the methane cracking catalyst; the dosage of the metal salt solution is equal to the product of the saturated adsorption capacity of the carrier and the mass of the carrier. The method for preparing the methane cracking catalyst by using the isometric impregnation method has the advantages that no redundant liquid is generated in the preparation process, all active substances are completely adsorbed on the surface of the carrier, and the loading capacity of the active components can be well controlled.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a methane cracking catalyst.
Background
Carbon Nanotubes (CNTs) are a tubular material composed of carbon (graphitic layers) and have a diameter measured in the nanometer scale (equivalent to 1m parts per billion or ten-thousandths of the thickness of human hair). The graphite layers look much like rolled up sheets, a continuous full hexagonal grid with carbon molecules at the vertices of the hexagons. Carbon nanotubes can be classified into various structures according to their length, thickness, helicity, and number of layers, such as single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), and multi-walled carbon nanotubes (MWCNTs), which are classified according to the number of layers. The diameter of the SWCNT is 0.5-several nanometers, and the diameter of the MWNT is 5-100 nm; the length is typically hundreds of nanometers to hundreds of micrometers. The carbon nano tube has good mechanical property, the tensile strength of the CNTs reaches 50-200 GPa, which is 100 times of that of steel, the density of the CNTs is only one sixth of that of the steel, and the CNTs are at least one order of magnitude higher than that of the conventional graphite fiber; its elastic modulus can reach 1TPa, which is equivalent to that of diamond, about 5 times that of steel. The carbon nano tube has good heat conduction performance and can synthesize anisotropic heat conduction materials. Carbon nanotubes have unique properties and are widely used in the industries of electronics, hydrogen storage, sensors, catalyst carriers, wave-absorbing materials, sewage treatment and the like.
At present, the preparation method of the carbon nano tube mainly comprises an arc discharge method, a chemical vapor deposition method, a laser evaporation method and the like, wherein the arc discharge method and the laser evaporation method are not suitable for industrial production due to more energy required; the Chemical Vapor Deposition (CVD) method is suitable for industrial production because the carbon source reduces the cracking reaction temperature under the action of the catalyst. Currently, carbon sources prepared by the CNT mainly comprise methane, ethane, ethylene, acetylene, propylene, propane, methanol, ethanol and the like. The quality of the catalyst plays a crucial role throughout the CVD reaction. The preparation method of the catalyst used in the industrial production process of the CNT mainly adopts an impregnation method and a coprecipitation method. The impregnation method is mainly characterized in that the carrier is impregnated in a metal solution, and after the carrier reaches adsorption balance, the carrier is taken out to be dried and roasted; this method has a significant disadvantage in that the amount of active ingredient loaded cannot be controlled, and is also called an excess impregnation method. The coprecipitation method also needs to carry out reaction for several hours at 80-120 ℃ in the process of preparing the catalyst, and then the reaction is carried out through the processes of filtering, cleaning for many times, drying, roasting and the like, so that a large amount of water is wasted and waste liquid is generated in the whole preparation process.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a methane cracking catalyst. The method for preparing the methane cracking catalyst by using the isometric impregnation method has the advantages that no redundant liquid is generated in the preparation process, all active substances are completely adsorbed on the surface of the carrier, and the loading capacity of the active components can be well controlled.
The technical scheme of the invention is as follows:
a method for preparing a methane cracking catalyst, the method comprising the steps of:
(1) drying the carrier at the temperature of 100-120 ℃ for 1-5h, and then placing the carrier in a dryer to cool to room temperature;
(2) dropwise adding a metal salt solution into the carrier obtained in the step (1) while stirring, standing at room temperature for 1-4h after dropwise adding is finished, and drying at 80-120 ℃ for 8-15 h; the purpose of standing is mainly to make the metal salt solution better contact with the carrier and enter pores on the surface of the carrier.
(3) Grinding until no obvious block is formed after drying is finished, then roasting at the temperature of 400-800 ℃ for 4-8h, cooling to room temperature, and grinding again to obtain powder, namely the methane cracking catalyst;
the dosage of the metal salt solution is equal to the product of the saturated adsorption capacity of the carrier and the mass of the carrier.
Preferably, in step (1), the carrier is commercial SiO2、γ-Al2O3、TiO2One or more of MgO; the particle size D50 of the carrier is 5-10 μm.
The method for measuring the saturated adsorption capacity of the carrier comprises the following steps: taking a certain amount of carrier, drying the carrier at the temperature of 100-120 ℃ for 1-5h, placing the carrier in a dryer, cooling to room temperature, accurately weighing a proper amount of carrier, dropwise adding deionized water into the carrier by using an acid burette, and stirring simultaneously in the dropwise adding process until the deionized water just soaks the carrier;
in the formula: v is the volume of deionized water used for titrating the carrier, mL; m is the mass of the support, g.
The method for judging that the deionized water just infiltrates the carrier comprises the following steps: all carriers were water kneaded together to form a dough and no "sand" sound was heard during stirring.
Preferably, in the step (2), the volume of the metal solution is the product of the saturated adsorption capacity of the carrier and the mass of the carrier.
In the step (2), the metal salt is a mixture of trivalent metal salt and divalent metal salt, and the molar ratio of the trivalent metal salt to the divalent metal salt is 1 (4-20); the trivalent metal salt is one or more of ferric nitrate, ferric acetate, ferric chloride, molybdenum nitrate and molybdenum chloride; the divalent metal salt is one or more of nickel nitrate, nickel acetate, nickel chloride, cobalt nitrate, cobalt acetate, cobalt chloride, copper nitrate, copper acetate, copper chloride, manganese nitrate, manganese acetate, manganese chloride and molybdenum acetate;
the stirring mode is grinding and stirring.
In the step (2), the concentration of the metal salt solution is 1-5 mol/L; the solvent of the metal salt solution is deionized water or a mixed solvent of the deionized water and methanol and/or ethanol, wherein the volume ratio of the alcohol to the deionized water is 0-1: 1.
Preferably, in the step (3), the roasting gas atmosphere is flowing air, and the roasting temperature rise rate is 5 ℃/min.
The particle size of the methane cracking catalyst is 38-74 mu m.
A methane cracking catalyst prepared by the preparation method.
Method for evaluating catalyst performance:
weighing 0.1-2.0g of catalyst powder, filling the catalyst powder into a methane cracking device, and introducing N2The airtightness of the apparatus was checked. General formula (N)2And removing residual air in the device for 10min-30 min. Then introducing cracking reaction raw material gas (CH)4:H2Volume ratio of 10:1-4), and detecting by gas chromatographInitial concentration of raw material gas (when the same gradual rising or gradual falling trend does not exist in 4 continuous test results and the relative standard deviation is less than 10%, the initial concentration test is finished, and the next stage can be entered); then N is introduced2Purging for 10-30min, heating to 600 deg.C, introducing reducing gas (N)2:H2The volume ratio is 1-10:1) to carry out reduction reaction on the catalyst, and the reaction time is 10-120 min. After the reaction is finished, N is introduced2Purging until no H is detected2Until now, the reaction gas (CH) is finally introduced4:H2The volume ratio is 10:1-4) to carry out methane cracking reaction. The tail gas is divided into two parts in the cracking reaction process, wherein one part enters a micro gas chromatograph for gas component detection, and the other part is emptied; after the reaction is completed, at N2The temperature was lowered to room temperature under protection and the carbon product was taken out and weighed and packed into sample bags for subsequent handling.
In the formula: m is1The total mass g of carbon, quartz wool and the catalyst after the methane cracking reaction is finished; m is2Is the catalyst mass, g; m is3The mass of the quartz wool before the start of the reaction, g.
In the formula: m is4The mass g of methane entering a reactor after the start of a methane cracking reaction; m is5The mass g of methane discharged from the outlet end of the reactor after the start of the methane cracking reaction.
In the formula: m is4The mass g of methane entering a reactor after the start of a methane cracking reaction; m is5After the methane cracking reaction is startedMass g of methane discharged from the outlet end of the reactor; m is6Carbon yield, g.
The beneficial technical effects of the invention are as follows:
the method does not need heating, filtering, cleaning and other processes before drying and roasting, does not generate waste liquid, reduces environmental pollution, only needs to be carried out at normal temperature, and has short catalyst preparation time.
The invention optimizes the proportion of active metal elements in the catalyst, so that the pipe diameter of the carbon nano-tube obtained by methane cracking is concentrated between 30 and 45nm, and the pipe length is more than 1 mu m; the cracking conversion rate of the catalyst to methane is reduced by less than or equal to 5 percent within 7 hours.
The metal salt solution is completely impregnated in the carrier by an isometric impregnation method, so that the loading capacity of the active component is ensured to be consistent with the theoretical calculation, and the prepared catalyst has high conversion rate of methane, which can reach more than 50%; the catalyst has high selectivity of preparing the carbon nano tube by methane, which is close to 100%; the carbon yield of the catalyst can reach 64g at mostc/gcat。
Drawings
FIG. 1 is a TEM image of carbon nanotubes prepared by the catalyst obtained in example 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
A method for preparing a methane cracking catalyst, the method comprising the steps of:
(1) mixing SiO2As a carrier, drying the carrier in an oven at 110 ℃ for 4h, then taking out the carrier and placing the carrier in a dryer to cool to room temperature;
(2) weighing 3g of SiO2Placing the mixture into a ceramic crucible, dropwise adding deionized water into a carrier by using an acid burette, stirring the mixture during the dropwise adding process until the deionized water just infiltrates the carrier, and measuring the saturated adsorption capacity to be 3.4 mL/g;
(3) weighing 19.1g Ni (NO)3)2·6H2O and 3.0g Fe (NO)3)3·9H2O, and deionized waterMixed and prepared into 51mL of metal salt aqueous solution.
(4) Dropwise adding a metal salt solution into 15.0g of the carrier obtained in the step (1) while stirring, standing at room temperature for 2h after dropwise adding is finished, and drying at 80 ℃ for 10 h; the standing purpose is mainly to ensure that the metal salt solution is better contacted with the carrier and enters pores on the surface of the carrier;
(5) grinding until no obvious block exists after drying is finished, then heating to 500 ℃ at the rate of 5 ℃/min, roasting for 4h, cooling to room temperature, and grinding again until the particle size is 45-74 mu m, namely the methane cracking catalyst;
0.5g of the catalyst powder prepared in this example was weighed out and charged in a methane cracker, and N was passed through2The airtightness of the apparatus was checked. General formula (N)2Removing residual air in the device for 20min, and introducing cracking reaction raw material gas (CH)4:H2The volume ratio is 10:1), and detecting the initial concentration of the raw material gas by a gas chromatograph (until 4 continuous test results do not have the same gradual rising or gradual falling trend and the relative standard deviation is less than 10%, the initial concentration test is finished, and the next stage can be entered); then N is introduced2Purging for 20min, heating to 600 deg.C, introducing reducing gas (N) when the temperature is reached2:H2The volume ratio is 1:1) and the catalyst is subjected to reduction reaction for 120 min. After the reaction is finished, N is introduced2Purging until no H is detected2Until now, the reaction gas (CH) is finally introduced4:H2The volume ratio is 10:1) and methane cracking reaction is carried out for 12 h. The tail gas is divided into two parts in the cracking reaction process, wherein one part enters a micro gas chromatograph for gas component detection, and the other part is emptied. After the reaction is completed, at N2Reducing the temperature to room temperature under protection, taking out the carbon product, weighing, and obtaining the carbon nanotube with the methane conversion rate of 40.1 percent and the carbon nanotube yield of 15.4gc/gcatThe selectivity of the carbon nanotubes was 99.7%.
Example 2
A method for preparing a methane cracking catalyst, the method comprising the steps of:
(1) mixing gamma-Al2O3As a carrier, drying the carrier in an oven at 120 ℃ for 1h, then taking out the carrier and placing the carrier in a dryer to cool to room temperature;
(2) weighing 3g of gamma-Al2O3Placing the mixture into a ceramic crucible, dropwise adding deionized water into a carrier by using an acid burette, stirring the mixture during the dropwise adding process until the deionized water just infiltrates the carrier, and measuring the saturated adsorption capacity to be 1.5 mL/g;
(3) weighing 19.9g Ni (NO)3)2·6H2O and 6.9g Fe (NO)3)3·9H2O was mixed with a mixed solution of deionized water and ethanol (ethanol: deionized water ═ 1:1) to prepare 22.5mL of an aqueous metal salt solution.
(4) Dropwise adding a metal salt solution into 15.0g of the carrier obtained in the step (1) while stirring, standing at room temperature for 1h after dropwise adding is finished, and drying at 80 ℃ for 12 h; the standing purpose is mainly to ensure that the metal salt solution is better contacted with the carrier and enters pores on the surface of the carrier;
(5) grinding until no obvious block exists after drying is finished, then heating to 600 ℃ at the rate of 5 ℃/min, roasting for 5h, cooling to room temperature, and grinding again until the particle size is 38-45 mu m, namely the methane cracking catalyst;
0.5g of the catalyst powder prepared in this example was weighed out and charged in a methane cracker, and N was passed through2The airtightness of the apparatus was checked. General formula (N)2Removing residual air in the device for 30min, and introducing cracking reaction raw material gas (CH)4:H2The volume ratio is 10:1), and detecting the initial concentration of the raw material gas by a gas chromatograph (until 4 continuous test results do not have the same gradual rising or gradual falling trend and the relative standard deviation is less than 10%, the initial concentration test is finished, and the next stage can be entered); then N is introduced2Purging for 30min, heating to 600 deg.C, introducing reducing gas (N)2:H2The volume ratio is 1:1) and the catalyst is subjected to reduction reaction for 24 h. After the reaction is finished, N is introduced2Purging until no H is detected2Until now, the reaction gas (CH) is finally introduced4:H2Volume ratio of 10:1) for methane crackingAnd (4) performing solution reaction. The tail gas is divided into two parts in the cracking reaction process, wherein one part enters a micro gas chromatograph for gas component detection, and the other part is emptied. After the reaction is completed, at N2Reducing the temperature to room temperature under protection, taking out the carbon product, weighing, and obtaining the carbon nanotube with the methane conversion rate of 50.1 percent and the carbon nanotube yield of 64gc/gcatThe selectivity of the carbon nanotubes was 99.8%.
The TEM image of the obtained carbon nanotube is shown in FIG. 1, and it can be seen from FIG. 1 that the prepared carbon nanotube has good tube diameter uniformity, which is concentrated between 30-45 nm.
Example 3
A method for preparing a methane cracking catalyst, the method comprising the steps of:
(1) mixing gamma-Al2O3As a carrier, drying the carrier in an oven at 120 ℃ for 1h, then taking out the carrier and placing the carrier in a dryer to cool to room temperature;
(2) weighing 3g of gamma-Al2O3Placing the mixture into a ceramic crucible, dropwise adding deionized water into a carrier by using an acid burette, stirring the mixture during the dropwise adding process until the deionized water just infiltrates the carrier, and measuring the saturated adsorption capacity to be 1.5 mL/g;
(3) weighing 19g Ni (NO)3)2·6H2O、0.8g Cu(NO3)2·3H2O and 6.5gFe (NO)3)3·9H2O was mixed with deionized water to prepare 22.5mL of an aqueous solution of the metal salt.
(4) Dropwise adding a metal salt solution into the carrier obtained in the step (1) while stirring, standing at room temperature for 4h after dropwise adding is finished, and drying at 120 ℃ for 8 h; the standing purpose is mainly to ensure that the metal salt solution is better contacted with the carrier and enters pores on the surface of the carrier;
(5) grinding until no obvious block exists after drying is finished, then heating to 800 ℃ at the rate of 5 ℃/min, roasting for 5h, cooling to room temperature, and grinding again until the particle size is 38-45 mu m, namely the methane cracking catalyst;
0.5g of the catalyst powder obtained in this example was weighed out and charged in a methane cracker, and N was passed through2The airtightness of the apparatus was checked. General formula (N)2Removing residual air in the device for 10min, and introducing cracking reaction raw material gas (CH)4:H2The volume ratio is 10:4), and detecting the initial concentration of the raw material gas by a gas chromatograph (until 4 continuous test results do not have the same gradual rising or gradual falling trend and the relative standard deviation is less than 10%, the initial concentration test is finished, and the next stage can be entered); then N is introduced2Purging for 10min, heating to 600 deg.C, introducing reducing gas (N) when the temperature is reached2:H2The volume ratio is 8:1) and the reduction reaction is carried out on the catalyst, and the reaction time is 16 h. After the reaction is finished, N is introduced2Purging until no H is detected2Until now, the reaction gas (CH) is finally introduced4:H2The volume ratio is 10:4) to carry out methane cracking reaction. The tail gas is divided into two parts in the cracking reaction process, wherein one part enters a micro gas chromatograph for gas component detection, and the other part is emptied. After the reaction is completed, at N2Reducing the temperature to room temperature under protection, taking out the carbon product, weighing, and obtaining the carbon nanotube with the methane conversion rate of 20.1 percent and the carbon nanotube yield of 5gc/gcatThe selectivity of the carbon nanotubes was 99.5%.
Example 4
A method for preparing a methane cracking catalyst, the method comprising the steps of:
(1) mixing SiO2As a carrier, drying the carrier in an oven at 100 ℃ for 5 hours, then taking out the carrier, and placing the carrier in a dryer to cool to room temperature;
(2) weighing 3g of SiO2Placing the mixture into a ceramic crucible, dropwise adding deionized water into a carrier by using an acid burette, stirring the mixture during the dropwise adding process until the deionized water just infiltrates the carrier, and measuring the saturated adsorption capacity to be 3.4 mL/g;
(3) weighing 19.2g Ni (NO)3)2·6H2O、1.6g Cu(NO3)2·3H2O and 1.5gFe (NO)3)3·9H2O was mixed with a mixed solution of deionized water and ethanol (ethanol: deionized water ═ 1:5) to prepare 51mL of an aqueous metal salt solution.
(4) Dropwise adding a metal salt solution into 15.0g of the carrier obtained in the step (1) while stirring, standing at room temperature for 4h after dropwise adding is finished, and drying at 80 ℃ for 10 h; the standing purpose is mainly to ensure that the metal salt solution is better contacted with the carrier and enters pores on the surface of the carrier;
(5) grinding until no obvious block exists after drying is finished, then heating to 600 ℃ at the rate of 5 ℃/min, roasting for 4h, cooling to room temperature, and grinding again until the particle size is 38-45 mu m, namely the methane cracking catalyst;
0.5g of the catalyst powder prepared in this example was weighed out and charged in a methane cracker, and N was passed through2The airtightness of the apparatus was checked. General formula (N)2Removing residual air in the device for 20min, and introducing cracking reaction raw material gas (CH)4:H2The volume ratio is 10:2), and detecting the initial concentration of the raw material gas by a gas chromatograph (until 4 continuous test results do not have the same gradual rising or gradual falling trend and the relative standard deviation is less than 10%, the initial concentration test is finished, and the next stage can be entered); then N is introduced2Purging for 20min, heating to 600 deg.C, introducing reducing gas (N) when the temperature is reached2:H2The volume ratio is 8:1) and the catalyst is subjected to reduction reaction for 10 min. After the reaction is finished, N is introduced2Purging until no H is detected2Until now, the reaction gas (CH) is finally introduced4:H2The volume ratio is 10:2) to carry out methane cracking reaction for 8 h. The tail gas is divided into two parts in the cracking reaction process, wherein one part enters a micro gas chromatograph for gas component detection, and the other part is emptied. After the reaction is completed, at N2The temperature is reduced to room temperature under protection, the carbon product is taken out and weighed, the methane conversion rate is 30.1 percent, and the yield of the carbon nano tube is 10.7gc/gcatThe selectivity of the carbon nanotubes was 99.6%.
Comparative example 1
A method for preparing a methane cracking catalyst, the method comprising the steps of:
(1) mixing gamma-Al2O3As a support, after drying in an oven at 110 ℃ for 1h, it was subsequently removedCooling to room temperature in a drier;
(2) weighing 19.9g Ni (NO)3)2·6H2O and 6.9g Fe (NO)3)3·9H2And O, mixing with deionized water, and preparing into a 60mL metal salt aqueous solution.
(3) Pouring a metal salt solution into 15.0g of the carrier obtained in the step (1), stirring while pouring, standing at room temperature for 1h after stirring uniformly, filtering to remove excess water, washing without deionized water, and then drying at 80 ℃ for 12 h; the standing purpose is mainly to ensure that the metal salt solution is better contacted with the carrier and enters pores on the surface of the carrier;
(4) grinding until no obvious block exists after drying is finished, then heating to 600 ℃ at the rate of 5 ℃/min, roasting for 5h, cooling to room temperature, and grinding again until the particle size is 38-45 mu m, namely the methane cracking catalyst;
0.5g of the catalyst powder prepared in this example was weighed out and charged in a methane cracker, and N was passed through2The airtightness of the apparatus was checked. General formula (N)2Removing residual air in the device for 30min, and introducing cracking reaction raw material gas (CH)4:H2The volume ratio is 10:1), and detecting the initial concentration of the raw material gas by a gas chromatograph (until 4 continuous test results do not have the same gradual rising or gradual falling trend and the relative standard deviation is less than 10%, the initial concentration test is finished, and the next stage can be entered); then N is introduced2Purging for 30min, heating to 600 deg.C, introducing reducing gas (N)2:H2The volume ratio is 1:1) and the catalyst is subjected to reduction reaction for 7 h. After the reaction is finished, N is introduced2Purging until no H is detected2Until now, the reaction gas (CH) is finally introduced4:H2The volume ratio is 10:1) to carry out methane cracking reaction. The tail gas is divided into two parts in the cracking reaction process, wherein one part enters a micro gas chromatograph for gas component detection, and the other part is emptied. After the reaction is completed, at N2Reducing the temperature to room temperature under protection, taking out the carbon product, weighing, and obtaining the carbon nanotube with the methane conversion rate of 12.1 percent and the carbon nanotube yield of 8.8gc/gcatCarbon nanotubeThe selectivity of (A) was 99.4%.
Claims (9)
1. A preparation method of a methane cracking catalyst is characterized by comprising the following steps:
(1) drying the carrier at the temperature of 100-120 ℃ for 1-5h, and then placing the carrier in a dryer to cool to room temperature;
(2) dropwise adding a metal salt solution into the carrier obtained in the step (1) while stirring, standing at room temperature for 1-4h after dropwise adding is finished, and drying at 80-120 ℃ for 8-15 h;
(3) grinding until no obvious block is formed after drying is finished, then roasting at the temperature of 400-800 ℃ for 4-8h, cooling to room temperature, and grinding again to obtain powder, namely the methane cracking catalyst;
the dosage of the metal salt solution is equal to the product of the saturated adsorption capacity of the carrier and the mass of the carrier.
2. The production method according to claim 1, wherein in the step (1), the carrier is commercial SiO2、γ-Al2O3、TiO2One or more of MgO; the particle size D50 of the carrier is 5-10 μm.
3. The method according to claim 1, wherein the saturated adsorption amount of the carrier is measured by: taking a certain amount of carrier, drying the carrier at the temperature of 100-120 ℃ for 1-5h, placing the carrier in a dryer, cooling to room temperature, accurately weighing a proper amount of carrier, dropwise adding deionized water into the carrier by using an acid burette, and stirring simultaneously in the dropwise adding process until the deionized water just soaks the carrier;
saturated adsorption capacity of carrier
In the formula: v is the volume of deionized water used for titrating the carrier, mL; m is the mass of the support, g.
4. The production method according to claim 1, wherein in the step (2), the volume of the metal solution is a product of a saturated adsorption amount of the carrier and a mass of the carrier.
5. The preparation method according to claim 1, wherein in the step (2), the metal salt is a mixture of trivalent metal salt and divalent metal salt, and the molar ratio of the trivalent metal salt to the divalent metal salt is 1 (4-20); the trivalent metal salt is one or more of ferric nitrate, ferric acetate, ferric chloride, molybdenum nitrate and molybdenum chloride; the divalent metal salt is one or more of nickel nitrate, nickel acetate, nickel chloride, cobalt nitrate, cobalt acetate, cobalt chloride, copper nitrate, copper acetate, copper chloride, manganese nitrate, manganese acetate, manganese chloride and molybdenum acetate;
the stirring mode is grinding and stirring.
6. The production method according to claim 1, wherein in the step (2), the concentration of the metal salt solution is 1 to 5 mol/L; the solvent of the metal salt solution is deionized water or a mixed solvent of the deionized water and methanol and/or ethanol, wherein the volume ratio of the alcohol to the deionized water is 0-1: 1.
7. The production method according to claim 1, wherein in the step (3), the atmosphere of the gas for calcination is flowing air, and the temperature rise rate for calcination is 5 ℃/min.
8. The production method according to claim 1, wherein the particle size of the methane cracking catalyst is 38 to 74 μm.
9. A methane cracking catalyst obtained by the production method according to any one of claims 1 to 8.
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