CN105964260A - Preparation method for metal catalyst and preparation method for carbon nano tube prepared by metal catalyst - Google Patents
Preparation method for metal catalyst and preparation method for carbon nano tube prepared by metal catalyst Download PDFInfo
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- CN105964260A CN105964260A CN201610326095.5A CN201610326095A CN105964260A CN 105964260 A CN105964260 A CN 105964260A CN 201610326095 A CN201610326095 A CN 201610326095A CN 105964260 A CN105964260 A CN 105964260A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 137
- 239000002184 metal Substances 0.000 title claims abstract description 137
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 25
- 239000003054 catalyst Substances 0.000 title abstract description 12
- 239000002041 carbon nanotube Substances 0.000 title abstract description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 title abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 54
- 239000013078 crystal Substances 0.000 claims abstract description 45
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 40
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003863 metallic catalyst Substances 0.000 claims description 76
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 28
- 150000001455 metallic ions Chemical class 0.000 claims description 20
- -1 manganese, lanthanide Chemical class 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 238000011017 operating method Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 claims 2
- 239000010931 gold Substances 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 28
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 24
- 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 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000012530 fluid Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- B01J23/74—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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method for a metal catalyst. The preparation method comprises the following operation steps: step I, providing a metal salt solution, wherein carrier metal ions and active metal ions with a carbon nano tube preparation catalysis effect are dissolved in the metal salt solution; step II, separating out the active metal ions and the carrier metal ions in the metal salt solution in a crystalline state, thereby obtaining a compound metal crystal; and step III, calcining the compound metal crystal to obtain the metal catalyst. Meanwhile, the invention further discloses a method for preparing a carbon nano tube by the metal catalyst prepared by the preparation method for the metal catalyst. The preparation method is used for preparing the metal catalyst which is high in crystallinity and is consistent in structure; and the preparation method is simple and practical, is low in cost and is more suitable for preparing the carbon nano tube with high crystallinity in a large scale.
Description
Technical field
The present invention relates to preparation method and the preparation side of CNT thereof of a kind of CNT metallic catalyst
Method.
Background technology
From 1991 the end of the year Japanese scholars Lijimat be found that the CNT being made up of carbon atom, due to its tie
The particularity of structure, CNT shows the many and diverse property of other carbonaceous materials, application
In Novel electronic devices or new function material field.Therefore the discovery of CNT and the synthesis of maroscopic quantity thereof,
Due to the purposes that it is potential, cause the very big concern of international chemistry, physics and material educational circles immediately.Close at present
The method becoming CNT has varied, and the synthesis of maroscopic quantity uses arc process and catalytic cracking solution mostly,
But synthesis thick product in be usually associated with miscellaneous shape carbon more or less, as be similar to activated carbon miscellaneous shape carbon and
Containing five-membered ring, the little granule of carbon nanometer of heptatomic ring and graphite fractionlet etc. and metal impurities, owing to association is miscellaneous
The existence of matter, makes the application of CNT and research characterize and run into the biggest difficulty, this in order to further investigate
Material, the purification of CNT is the most necessary, but the carbon nano tube surface structure after final purification is all
Have damage in various degree, make follow-up application greatly be hindered, as electric conductivity, heat conductivility,
Wearability etc. is the most restricted.The purity of CNT is used by its preparation process to a great extent
Metallic catalyst determines, if just synthesize consistent the urging of high-crystallinity structure when preparing metallic catalyst
Agent, reduces the defect of metallic catalyst, and follow-up CNT of preparing is also beneficial to find preparation technology, system
For going out highly purified carbon nanotube product, direct application is also beneficial to carbon with market or purity requirements at the higher level and receives
The purification again of mitron, urges it would therefore be highly desirable to invent the metal that a kind of applicable magnanimity prepares high-purity carbon nano tube
Agent preparation method.
The preparation method of the existing metallic catalyst for preparing CNT includes: 1, by carrier metal
Salt and activity component metal salt are dissolved separately in solvent, by adding precipitant, make carrier metal and activity
Component metals complexation, forms many metal salt precipitate；2, by the mixed precipitation solution in step one, at high temperature
Calcination, obtains catalyst granules；Above method all fails the active metal components in metallic catalyst and load
Body composition is sufficiently mixed, and the CNT using this metallic catalyst to prepare is easily formed impurity, it is difficult to formed big
Large-scale production.
Summary of the invention
There is impurity for the metallic catalyst being currently used for CNT many, the CNT defect caused and
Problem prepared by magnanimity, the invention provides a kind of preparation method preparing CNT metallic catalyst and
The preparation method of its CNT, is used for the metallic catalyst preparing high-crystallinity, structure is consistent, and this system
Preparation Method is simple and practical, low cost, be more suitable for large-scale and prepare CNT.
It is as follows that the present invention solves the technical scheme that above-mentioned technical problem used:
There is provided a kind of metallic catalyst preparation method, including following operating procedure:
Step one: a kind of metal salt solution is provided, described metal salt solution is dissolved with carrier metal ion and
Active metallic ion；
Step 2: metal salt solution regulation pH value is 7～11, active metallic ion and carrier metal ion in
Crystalline state separates out, and obtains composition metal crystal；
Step 3: composition metal crystal obtains degree of crystallinity metallic catalyst through calcining.
Further, described carrier metal ion includes one or more in transition metal and lanthanide series metal
Combination.
Further, described active metallic ion include ferrum, cobalt, nickel, yttrium, molybdenum, copper, platinum, palladium, vanadium,
One or more combinations in niobium, tungsten, chromium, iridium and titanium.
Further, it is characterised in that described carrier metal ion include copper, zinc, magnesium, aluminum, molybdenum, manganese,
In lanthanide series metal one or more combination, described active metallic ion include the one in ferrum, cobalt, nickel or
Multiple combination.
Further, the mol ratio of the active metallic ion in described metal salt solution and carrier metal ion is
0.5～5:0.5～4.
Further, in described step 2, described precipitant is ammonia, adds in described metal salt solution
Ammonia, regulation pH value is 7～11, stands, obtains metallic catalyst crystal；
Further, in described step 2, described precipitant is organic solvent, in described metal salt solution
Adding organic solvent, regulation pH value is 7～11, stands, obtains metallic catalyst crystal；Described organic molten
Agent includes normal hexane, toluene, n-propane.
Further, the process that stands keeps 1～12h, and during standing, the crystallization temperature of holding metal salt solution is
-80 DEG C～30 DEG C.
Further, in described step 3, calcining heat is 300 DEG C～650 DEG C.
The preparation method of a kind of CNT, described CNT is prepared by metallic catalyst, and described metal is urged
Agent is prepared by above-mentioned metallic catalyst preparation method.
Active metal and carrier metal are dissolved in solvent by the present invention with the form of ion, are formed homogeneous molten
Liquid dispersion, makes active metallic ion and carrier metal ion analyse with crystal form by adding precipitant
Going out, this composition metal crystal is the presoma of metallic catalyst, and by metallic crystal calcining, sieving obtains metal
Catalyst, through excess syndrome, when being carried out the preparation of extensive CNT by this metallic catalyst, the carbon obtained
Nanotube length can reach more than 200 microns, the G/D peak of Raman than more than 1, thermal weight loss more than 600 DEG C,
Uniform diameter, degree of graphitization are high.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the CNT that existing metallic catalyst prepares；
Fig. 2 is the SEM figure of the CNT that the metallic catalyst that the present invention provides prepares；
Fig. 3 is the thermogravimetric analysis figure of the CNT that the metallic catalyst that the present invention provides prepares；
Fig. 4 is the Raman figure of the CNT that the metallic catalyst that the present invention provides prepares.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, with
Lower combination drawings and Examples, are further elaborated to the present invention.Should be appreciated that described herein
Specific embodiment only in order to explain the present invention, be not intended to limit the present invention.
The invention discloses a kind of metallic catalyst preparation method, including following operating procedure:
Step one: a kind of metal salt solution is provided, described metal salt solution is dissolved with carrier metal ion and
There is CNT and prepare the active metallic ion of catalytic action；
Step 2: in metal salt solution add precipitant, regulation pH value be 7～11, active metallic ion and
Carrier metal ion is that crystalline state separates out, and obtains composition metal crystal；
Step 3: composition metal crystal obtains metallic catalyst through calcining.
The present invention relates to use the preparation side of presoma of the metallic catalyst that crystallization mode carries out CNT
Method, weighs active metal salt and is dissolved in solvent, treat that active metal salt all dissolves, and filters, obtains activity
Metal salt solution；Weigh carrier metal salt equally to be dissolved in solvent, treat that carrier metal salt all dissolves, mistake
Filter, obtains carrier metal saline solution；The two mixing is i.e. obtained mixed salt solution described in step one；
Another embodiment of the invention is: be sequentially added into active metal salt and carrier metal salt in same solvent
Dissolve, filter, obtain mixed salt solution described in step one.
The solvent that this metal salt solution uses is deionized water, and described deionized water is i.e. without other metal ion
Water, can avoid introducing foreign ion in the solution and produce impurity nucleus when crystal separates out, affect crystal matter
Amount and precipitation rate；
Active metallic ion and the mol ratio of carrier metal ion in further preferred described metal salt solution are
0.5～5:0.5～4.
Make active metallic ion and carrier metal ion with crystalline substance by adding the method such as precipitant or reduction temperature
The form of body structure separates out, and is filtrated to get composition metal crystal, it should be noted that this composition metal crystal
Structure according to use precipitant difference can form different crystal structures, with ammonia disclosed by the invention be
Example, obtains metallic catalyst crystal.
This composition metal crystal is the presoma of metallic catalyst, by making metal exist with crystal form, from
And ensure that the uniformity in the high-crystallinity of this metal catalysts precursors and microstructure, thus effectively carry
Its catalysis activity in prepared by CNT high, improves the carbon nanotube mass of preparation；By composition metal
Crystal is calcined, and sieves and obtains metallic catalyst, and this metallic catalyst is O composite metallic oxide catalyst.
In the present invention, the kind for carrier metal ion is not particularly limited, described carrier metal
Ion includes one or more combinations in transition metal and lanthanide series metal.One as the present invention is preferred
Embodiment, described carrier metal ion includes the transition metal such as copper, zinc, magnesium, aluminum, molybdenum, manganese, with
And one or more combinations in lanthanide series metal.
Described active metallic ion i.e. CNT can be prepared produce catalytic action active metal from
Sub-form, described active metallic ion include active metallic ion include ferrum, cobalt, nickel, yttrium, molybdenum, copper,
One or more combinations in platinum, palladium, vanadium, niobium, tungsten, chromium, iridium and titanium.One as the present invention is excellent
The embodiment of choosing, described active metallic ion includes one or more combinations in ferrum, cobalt, nickel.
As the present invention one preferred embodiment, in described step 2, in described metal salt solution
Adding ammonia, regulation pH value is 7～11, stands, and composition metal crystal separates out.When carrier metal and activity
When metal is dissolved in deionized water with ionic forms, in solution, add ammonia, carrier metal ion and work
Property metal ion respectively with OH-Ion forms precipitation, separates out with crystal habit, high-temperature calcination, is crystallized
Degree metallic catalyst.
NH in described ammonia3·H2The amount of the material of O and the electric charge sum of metal cation in metal salt solution
Ratio is 1～5:1.
As another preferred embodiment of the present invention, in described step 2, at described metal salt solution
Middle addition organic solvent, regulation pH value is 7～11, stands, and composition metal crystal separates out；Described organic molten
Agent and the immiscible Organic substance of water, including normal hexane, toluene, n-propane, by described metal salt solution
Adding described organic solvent, organic solvent includes having the group of coordination, group and metal with metal ion
Active metallic ion and carrier metal ion complex in saline solution form composition metal complex crystal, thus
Promote that metal ion is carried out toward the direction that crystal separates out.
It should be noted that addition ammonia and organic solvent are only the preferred embodiment of the present invention, promote institute
The mode stating the precipitation of composition metal crystal is the most multiple, as reduced temperature etc., all should be included in the guarantor of the present invention
Within the scope of protecting.
, need to make to form nucleus in metal salt solution through still aging process when crystal separates out simultaneously
The initial nucleus granule continued growth separated out, the process that stands keeps 1～12h, keeps metal salt solution during standing
Crystallization temperature be-80 DEG C～30 DEG C, crystallization temperature is the lowest, active metallic ion and carrier metal ion molten
Xie Du reduces the most accordingly, therefore stands process required time with the reduction of the crystallization temperature residing for metal salt solution
Shortening, when crystallization temperature is higher than 25 DEG C, the time of repose needed for composition metal crystal growth is long, unfavorable
In improving production efficiency；
Being calcined by the metallic crystal obtained, calcining heat is 300 DEG C～650 DEG C, removes in metallic crystal
Water of crystallization and easy pyrolysis component, obtain the metal oxide catalyst of brownish black granule or powder；
The invention also discloses a kind of CNT, described CNT uses metallic catalyst as above
The metallic catalyst that preparation method prepares, is prepared especially by fluidized-bed chemical vapor deposition method,
Comprise the following steps:
Step one: put into metallic catalyst in fluid unit, be passed through nitrogen and protect, heat up, treat
Temperature reaches 460～800 DEG C and keeps constant, is passed through hydrogen and reduces metallic catalyst, and the recovery time is
25～50min, stop after having reduced being passed through hydrogen；
Step 2: being passed through carbon-source gas and react in fluid bed, the response time is 40～140min, stops
Stop-pass enters carbon-source gas, and fluid bed is cooled to room temperature under nitrogen protection, obtains granular carbon nano tube and slightly produces
Product, carry out test and characterize the CNT obtained.
It is experimentally confirmed, is fluidized by the highly crystallineization metallic catalyst using the inventive method to obtain
Bed vapour deposition process prepares CNT, and the CNT obtained is in many aspects performance excellence, and such as carbon is received
The uniform diameter of mitron, degree of graphitization are high, configuration state stable and consistent etc..
By the following examples the present invention is further detailed.
Embodiment 1
The present embodiment, for the preparation method of metallic catalyst disclosed by the invention and CNT thereof is described, wraps
Include following steps.
Step one: preparing metal saline solution: weigh active metal salt nickel nitrate and be dissolved in deionized water, treat
Nickel nitrate all dissolves, and is filtrated to get nickel nitrate solution；Weigh carrier metal salt aluminum nitrate equally to be dissolved in
In ionized water, treat that aluminum nitrate all dissolves, be filtrated to get aluminum nitrate solution；By nickel nitrate solution and aluminum nitrate
Solution is mixed to get metal salt solution, and in described metal salt solution, the mol ratio of nickel nitrate and aluminum nitrate is 2:1；
Step 2: adding ammonia in metal salt solution, regulation pH value is 10, activity in metal salt solution
Metal ion and carrier metal ion are that crystalline state separates out, and crystallization process keeps ambient temperature to be 25 DEG C, knot
The brilliant time is 12h, obtains metallic crystal；
Step 3: metallic crystal puts in Muffle furnace and calcines, and calcining heat is 400 DEG C, and calcination time is 3h,
Obtain the metallic catalyst of brownish black through calcining, 100～200 mesh sieves crossed by metallic catalyst；
Step 4: put into 1g metallic catalyst in fluid unit, be passed through nitrogen and protect, heat up,
Treat that temperature reaches 750 DEG C and keeps constant, be passed through hydrogen and metallic catalyst is reduced, VH2:VN2=2:8,
Recovery time is 30min, stops being passed through hydrogen after having reduced；
Step 5: be passed through carbon source methane and react in fluid bed, VCH4:VN2=4:6, the response time is 60
Min, stops being passed through carbon source methane, and fluid bed is cooled to room temperature under nitrogen protection, obtains graininess carbon nanometer
Manage thick product.
Embodiment 2
The present embodiment is for illustrating the preparation method of metallic catalyst disclosed by the invention and CNT thereof, originally
Embodiment major part step is same as in Example 1, and concrete difference is:
In step one: preparing metal saline solution: weigh active metal salt nickel nitrate and be dissolved in deionized water,
Treat that nickel nitrate all dissolves, be filtrated to get nickel nitrate solution；Weigh carrier metal salt aluminum nitrate equally to be dissolved in
In deionized water, treat that aluminum nitrate all dissolves, be filtrated to get aluminum nitrate solution；By nickel nitrate solution and nitric acid
Aluminum solutions is mixed to get metal salt solution, and in described metal salt solution, the mol ratio of nickel nitrate and aluminum nitrate is 1:
2；
In step 3: composition metal crystal puts in Muffle furnace and calcines, and calcining heat is 500 DEG C, calcination time
For 3h, obtaining the metallic catalyst of brownish black through calcining, 100～200 mesh sieves crossed by metallic catalyst.
Embodiment 3
The present embodiment is for illustrating the preparation method of metallic catalyst disclosed by the invention and CNT thereof, originally
Embodiment major part step is same as in Example 1, and concrete difference is:
In step one: preparing metal saline solution: weigh active metal salt nickel nitrate and be dissolved in deionized water,
Treat that nickel nitrate all dissolves, be filtrated to get nickel nitrate solution；Weigh carrier metal salt aluminum nitrate equally to be dissolved in
In deionized water, treat that aluminum nitrate all dissolves, be filtrated to get aluminum nitrate solution；By nickel nitrate solution and nitric acid
Aluminum solutions is mixed to get metal salt solution, and in described metal salt solution, the mol ratio of nickel nitrate and aluminum nitrate is 2.5:
1；
In step 2: adding ammonia in metal salt solution, regulation pH value is 10, lives in metal salt solution
Property metal ion and carrier metal ion be crystalline state separate out, crystallization process keep ambient temperature be 0 DEG C, knot
The brilliant time is 8h, obtains composition metal crystal；
In step 3: composition metal crystal puts in Muffle furnace and calcines, and calcining heat is 550 DEG C, calcination time
For 3h, obtaining the metallic catalyst of brownish black through calcining, 100～200 mesh sieves crossed by metallic catalyst.
Embodiment 4
The present embodiment is for illustrating the preparation method of metallic catalyst disclosed by the invention and CNT thereof, originally
Embodiment major part step is same as in Example 1, and concrete difference is:
Step one: preparing metal saline solution: weigh active metal salt nickel nitrate and be dissolved in deionized water, treat
Nickel nitrate all dissolves, and is filtrated to get nickel nitrate solution；Weigh carrier metal salt aluminum nitrate equally to be dissolved in
In ionized water, treat that aluminum nitrate all dissolves, be filtrated to get aluminum nitrate solution；By nickel nitrate solution and aluminum nitrate
Solution is mixed to get metal salt solution, and in described metal salt solution, the mol ratio of nickel nitrate and aluminum nitrate is 3:2；
Step 2: adding ammonia in metal salt solution, regulation pH value is 10, activity in metal salt solution
Metal ion and carrier metal ion are that crystalline state separates out, and crystallization process keeps ambient temperature to be-30 DEG C, knot
The brilliant time is 5h, obtains composition metal crystal；
Step 3: composition metal crystal puts in Muffle furnace and calcines, and calcining heat is 450 DEG C, and calcination time is
3h, obtains the metallic catalyst of brownish black through calcining, and 100～200 mesh sieves crossed by metallic catalyst.
Embodiment 5
The present embodiment is for illustrating the preparation method of metallic catalyst disclosed by the invention and CNT thereof, originally
Embodiment major part step is same as in Example 1, and concrete difference is:
Step one: preparing metal saline solution: weigh active metal salt nickel nitrate and be dissolved in deionized water, treat
Nickel nitrate all dissolves, and is filtrated to get nickel nitrate solution；Weigh carrier metal salt aluminum nitrate equally to be dissolved in
In ionized water, treat that aluminum nitrate all dissolves, be filtrated to get aluminum nitrate solution；By nickel nitrate solution and aluminum nitrate
Solution is mixed to get metal salt solution, and in described metal salt solution, the mol ratio of nickel nitrate and aluminum nitrate is 4:3；
Step 2: adding ammonia in metal salt solution, regulation pH value is 10, activity in metal salt solution
Metal ion and carrier metal ion are that crystalline state separates out, and crystallization process keeps ambient temperature to be-50 DEG C, knot
The brilliant time is 3h, obtains composition metal crystal；
Step 3: composition metal crystal puts in Muffle furnace and calcines, and calcining heat is 650 DEG C, and calcination time is
3h, obtains the metallic catalyst of brownish black through calcining, and 100～200 mesh sieves crossed by metallic catalyst.
Embodiment 6
The present embodiment is for illustrating the preparation method of metallic catalyst disclosed by the invention and CNT thereof, originally
Embodiment major part step is same as in Example 1, and concrete difference is:
Step one: preparing metal saline solution: weigh active metal salt nickel nitrate and be dissolved in deionized water, treat
Nickel nitrate all dissolves, and is filtrated to get nickel nitrate solution；Weigh carrier metal salt aluminum nitrate equally to be dissolved in
In ionized water, treat that aluminum nitrate all dissolves, be filtrated to get aluminum nitrate solution；By nickel nitrate solution and aluminum nitrate
Solution is mixed to get metal salt solution, and in described metal salt solution, the mol ratio of nickel nitrate and aluminum nitrate is 1.5:
1；
Step 2: adding ammonia in metal salt solution, regulation pH value is 10, activity in metal salt solution
Metal ion and carrier metal ion are that crystalline state separates out, and crystallization process keeps ambient temperature to be-80 DEG C, knot
The brilliant time is 1h, obtains composition metal crystal；
Step 3: composition metal crystal puts in Muffle furnace and calcines, and calcining heat is 600 DEG C, and calcination time is
3h, obtains the metallic catalyst of brownish black through calcining, and 100～200 mesh sieves crossed by metallic catalyst.
Comparative example 1
This comparative example is used for comparative illustration metallic catalyst disclosed by the invention and the preparation side of CNT thereof
Method, comprises the following steps:
Step one: a kind of amorphous metallic catalyst is provided；
Step 2: put into 1g metallic catalyst in fluid unit, be passed through nitrogen and protect, heat up,
Treat that temperature reaches 750 DEG C and keeps constant, be passed through hydrogen and metallic catalyst is reduced, VH2:VN2=2:8,
Recovery time is 30min, stops being passed through hydrogen after having reduced；
Step 3: be passed through carbon source methane and react in fluid bed, VCH4:VN2=4:6, the response time is 60
Min, stops being passed through carbon source methane, and fluid bed is cooled to room temperature under nitrogen protection, obtains graininess carbon nanometer
Manage thick product.
Performance test
It is existing amorphous metallic catalyst system that the above-mentioned CNT prepared is divided into two classes, a class
Standby CNT, another kind of for using the CNT that in the present invention prepared by the metallic catalyst of high-crystallinity,
Two class CNTs are carried out electron-microscope scanning, and (scanning electron microscope, sweeps to obtain SEM figure
Retouch ultramicroscope) as depicted in figs. 1 and 2, comparison diagram 1 and Fig. 2 is it can be seen that use in the present invention
The metallic catalyst of high-crystallinity prepares that CNT is longer at caliber, cleanliness factor is high, it is possible to reach 200
More than Wei meter；In Fig. 2, the present invention obtains the diameter Distribution narrow range of CNT, uniform diameter simultaneously, keeps away
Exempt to occur such as the distortion of CNT and bending in Fig. 1.
As it is shown on figure 3, the thermogravimetric analysis figure of the CNT prepared for the present invention；As seen from the figure, carbon
Nanotube starts weightlessness close to 500 DEG C when, and its heat decomposition temperature is 622.46 DEG C, 700 DEG C time
Time weightlessness terminates.
As shown in Figure 4, the Raman figure of the CNT prepared for the present invention；G peak and D peak in figure
Ratio is more than 1, illustrates that this CNT degree of graphitization is high, and structure is consistent.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (10)
1. a metallic catalyst preparation method, it is characterised in that include following operating procedure:
Step one: a kind of metal salt solution is provided, described metal salt solution is dissolved with carrier metal ion and
There is CNT and prepare the active metallic ion of catalytic action；
Step 2: in metal salt solution add precipitant, regulation pH value be 7～11, active metallic ion and
Carrier metal ion is that crystalline state separates out, and obtains composition metal crystal；
Step 3: composition metal crystal obtains the metallic catalyst of high-crystallinity through calcining.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described load
Body metal ion includes one or more combinations in transition metal and lanthanide series metal.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described work
Property metal ion includes ferrum, cobalt, nickel, yttrium, molybdenum, copper, platinum, palladium, vanadium, niobium, tungsten, chromium, iridium and titanium
In one or more combination.
4. according to a kind of metallic catalyst preparation method described in Claims 2 or 3, it is characterised in that institute
State one or more combinations that carrier metal ion includes in copper, zinc, magnesium, aluminum, molybdenum, manganese, lanthanide series metal,
Described active metallic ion includes one or more combinations in ferrum, cobalt, nickel.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described gold
The mol ratio belonging to the active metallic ion in saline solution and carrier metal ion is 0.5～5:0.5～4.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described step
In rapid two, described precipitant is ammonia, adds ammonia in described metal salt solution, and regulation pH value is 7～11,
Standing, composition metal crystal separates out；NH in described ammonia3·H2The amount of the material of O and gold in metal salt solution
The ratio of the electric charge sum belonging to cation is 0.5～5:0.5～4.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described step
In rapid two, described precipitant is organic solvent, adds organic solvent, regulate PH in described metal salt solution
Value is 7～11, stands, and composition metal crystal separates out；Described organic solvent include normal hexane, toluene, positive third
Alkane.
8. according to a kind of metallic catalyst preparation method described in claim 6 or 7, it is characterised in that quiet
Process of putting keeps 1～12h, and the crystallization temperature keeping metal salt solution during standing is-80 DEG C～30 DEG C.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described step
In rapid three, calcining heat is 300 DEG C～650 DEG C.
10. the preparation method of a CNT, it is characterised in that described CNT is by metallic catalyst
Preparing, described metallic catalyst is by the metallic catalyst preparation method described in any one in claim 1～9
Prepare.
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| CN115672335A (en) * | 2022-11-10 | 2023-02-03 | 无锡碳谷科技有限公司 | Preparation method of iron-nickel-aluminum ternary nano catalyst |
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