CN1275691C - Preparation method of catalyst used for producing carbon nano pipe - Google Patents
Preparation method of catalyst used for producing carbon nano pipe Download PDFInfo
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- CN1275691C CN1275691C CN 200410015667 CN200410015667A CN1275691C CN 1275691 C CN1275691 C CN 1275691C CN 200410015667 CN200410015667 CN 200410015667 CN 200410015667 A CN200410015667 A CN 200410015667A CN 1275691 C CN1275691 C CN 1275691C
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- Prior art keywords
- cobalt
- water soluble
- soluble salt
- solution
- calcium carbonate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 11
- 229910052799 carbon Inorganic materials 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 28
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000084 colloidal system Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- -1 transition metal salt Chemical class 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 229910017052 cobalt Inorganic materials 0.000 claims description 28
- 239000010941 cobalt Substances 0.000 claims description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 28
- 238000013019 agitation Methods 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000011833 salt mixture Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract 3
- 238000007654 immersion Methods 0.000 abstract 2
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 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 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 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 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing a catalyst in use for producing carbon nanometer tubes. Nanometer calcium carbonate is used as a carrier to prepare the catalyst. The present invention has two schemes of an immersion method and a precipitation method. In the immersion method, transition metal salt is dissolved into deionized water; the nanometer calcium carbonate is dissolved into the transition metal salt solution in a suspension way; the nanometer calcium carbonate solution is baked and milled to prepare the catalyst. In the precipitation method, the transition metal salt is dissolved into deionized water, and a macromolecular dispersing agent is added; the nanometer calcium carbonate power is dissolved into the solution in a suspension way; dilute ammonia water is added drop by drop until the pH value of a colloid is equal to 8 to 10; the nanometer calcium carbonate solution is baked and milled to prepare the catalyst. The method for preparing a catalyst in use for producing carbon nanometer tubes has the advantages of simple technique, easy implementation and convenient purification by one step. The catalyst made by the present invention is used for producing the carbon nanometer tubes. Cheap carbon sources, such as acetylene, etc., can be used to prepare large numbers of high quality carbon nanometer tubes under low temperature.
Description
Technical field
The present invention relates to be used to produce the Preparation of catalysts method of CNT, being specifically related to the nano-calcium carbonate is the Preparation of catalysts method of carrier.
Background technology
CNT is to be curled into tubulose by graphite linings, and each is reined in by half richness that face carbon ball forms end to end, similar graphite, and the electronics that existence can move freely in the carbon valence link of CNT, CNT has many tempting material behaviors.Among all preparation methods, chemical vapour deposition technique (CVD) is considered to the method for tool Commercial Prospect, and its essential catalyst carrier also emerges in an endless stream, and adopts nano-calcium carbonate as catalyst carrier here first, realizes the production of high-quality multi-walled carbon nano-tubes.
Summary of the invention
The purpose of this invention is to provide that a kind of what produce that CNT uses is the Preparation of catalysts method of carrier with the nano-calcium carbonate.
What the present invention proposed is the method for preparing catalyst of carrier with the nano-calcium carbonate, and two kinds of technical solutions are arranged.
Scheme 1 is an infusion process, and this method specifically may further comprise the steps:
1) water soluble salt of iron, cobalt or nickel or the water soluble salt mixture of iron and cobalt or the water soluble salt mixture of nickel and cobalt are dissolved in the deionized water, making its concentration is 2～10wt%, magnetic agitation 15～30min;
2) with nano-calcium carbonate calcium powder and above-mentioned solution by weight 3.5～15: 100 outstanding being dissolved in the solution, behind magnetic agitation 30～60min solution is heated to 60～80 ℃, stir and evaporate most of water;
3) be put in the baking oven in 120～150 ℃ of oven dry, being milled into then that powder promptly makes with the nano-calcium carbonate is the catalyst of carrier.
In the water soluble salt mixture of above-mentioned iron and cobalt, the molar ratio range of iron and cobalt is 1: 4 to 4: 1, and in the water soluble salt mixture of nickel and cobalt, the molar ratio range of nickel and cobalt is 1: 4 to 4: 1, and the particle diameter of Paris white is generally at 50～100nm.
Scheme 2 is precipitation method, and this method specifically may further comprise the steps:
1) water soluble salt of iron, cobalt or nickel or the water soluble salt mixture of iron and cobalt or the water soluble salt mixture of nickel and cobalt are dissolved in the deionized water, making its concentration is 2～10wt%, add macromolecule dispersing agent under the magnetic agitation, the consumption of macromolecule dispersing agent is 0.5～2% of a metal salt solution weight, again magnetic agitation 15～30min;
2) nano-calcium carbonate calcium powder and above-mentioned solution outstandingly are dissolved in the solution magnetic agitation 15～30min by weight 3.5～15: 100;
3) be that 4～12% weak aqua ammonia dropwise adds in the above-mentioned suspension that is stirring with weight percent concentration, treat pH value to 8～10 o'clock of colloid, stop to add ammoniacal liquor, continue to stir 30～60min;
4) solution is heated to 60～80 ℃, stir evaporate most of water after, be put in the baking oven in 120～150 ℃ of oven dry, being milled into then that powder promptly makes with the nano-calcium carbonate is the catalyst of carrier.
In the water soluble salt mixture of above-mentioned iron and cobalt, the molar ratio range of iron and cobalt is 1: 4 to 4: 1, and in the water soluble salt mixture of nickel and cobalt, the molar ratio range of nickel and cobalt is 1: 4 to 4: 1, and the particle diameter of Paris white is generally at 50～100nm.
Said macromolecule dispersing agent can adopt: polyethylene glycol-200, polyethylene glycol-2000 or polyvinyl alcohol;
The present invention has the following advantages:
1. easy, the easy enforcement of technology of preparation catalyst.
2. prepared catalyst performance is good, can be with cheap carbon source such as acetylene, and (650 ℃) at a lower temperature prepare the highly purified CNT of high-quality.
3. the application of nano-calcium carbonate carrier makes that the particle of catalyst is more tiny.
4. nano-calcium carbonate is made carrier, can use one step of diluted acid to purify during purification.
Description of drawings
Fig. 1 is the transmission electron microscope photo with the CNT of Catalyst Production of the present invention
The specific embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
Cobalt nitrate and ferric nitrate are dissolved in the deionized water, concentration is 4wt%, wherein, the mol ratio of cobalt nitrate and ferric nitrate is 1: 1, behind the magnetic agitation 15min with nano-calcium carbonate calcium powder and above-mentioned solution by weight 3.5: 100 outstanding being dissolved in the solution, magnetic agitation 30min is heated to solution 80 ℃ of stirrings then and evaporates most of water, be put in the baking oven in 130 ℃ of oven dry, be milled into powder then and promptly make catalyst.
Embodiment 2
Cobalt nitrate and nickel nitrate are dissolved in the deionized water, concentration is 3wt%, wherein, the mol ratio of cobalt nitrate and nickel nitrate is 4: 1, is dissolved in the solution magnetic agitation 30min with nano-calcium carbonate calcium powder and above-mentioned solution are outstanding by weight 5: 100 behind the magnetic agitation 15min, then solution is heated to 70 ℃ of stirrings and evaporates most of water, ultrasonic shake do after, be put in the baking oven in 120 ℃ of oven dry, be milled into powder then and promptly make catalyst.
Embodiment 3
In the cobalt nitrate deionized water, concentration is 2wt%, add polyethylene glycol-200 under the magnetic agitation, its consumption is 2% of a metal salt solution weight, magnetic agitation 15min again, with nano-calcium carbonate calcium powder and above-mentioned solution by weight 7: 100 outstanding being dissolved in the solution, magnetic agitation 15min is that the 5wt% weak aqua ammonia dropwise adds in the above-mentioned suspension that is stirring with concentration, treats that the pH value of colloid approximates at 8 o'clock, stop to add ammoniacal liquor, continue to stir 30min, solution is heated to 80 ℃ then, after stirring evaporates most of water, be put in the baking oven in 130 ℃ of oven dry, be milled into powder then and promptly make catalyst.
Embodiment 4
Cobalt nitrate and ferric nitrate are dissolved in the deionized water, concentration is 3.5wt%, wherein, the mol ratio of cobalt nitrate and ferric nitrate is 4: 1, add polyethylene glycol-200 under the magnetic agitation, its consumption is 1% of a metal salt solution weight, magnetic agitation 15min again, with nano-calcium carbonate calcium powder and above-mentioned solution by weight 3: 100 outstanding being dissolved in the solution, magnetic agitation 15min is that the 4wt% weak aqua ammonia dropwise adds in the above-mentioned suspension that is stirring with concentration, treats that the pH value of colloid approximates at 10 o'clock, stop to add ammoniacal liquor, continue to stir 30min, solution is heated to 80 ℃ then, after stirring evaporates most of water, be put in the baking oven in 130 ℃ of oven dry, be milled into powder then and promptly make catalyst.
The catalyst that the present invention makes is put into quartz boat, in the tubular type quartz ampoule 750 ℃, catalytic pyrolysis acetylene gas (100ml/min) 20 minutes, products obtained therefrom is exactly a multi-walled carbon nano-tubes, and the transmission electron microscope photo of product is seen shown in Figure 1.
Claims (5)
1. be used to produce the Preparation of catalysts method of CNT, it is characterized in that may further comprise the steps:
1) water soluble salt of iron, cobalt or nickel or the water soluble salt mixture of iron and cobalt or the water soluble salt mixture of nickel and cobalt are dissolved in the deionized water, making its concentration is 2～10wt%, magnetic agitation 15～30min;
2) with nano-calcium carbonate calcium powder and above-mentioned solution by weight 3.5～15: 100 outstanding being dissolved in the solution, behind magnetic agitation 30～60min solution is heated to 60～80 ℃, stir and evaporate most of water;
3) be put in the baking oven in 120～150 ℃ of oven dry, being milled into then that powder promptly makes with the nano-calcium carbonate is the catalyst of carrier.
2. by the described Preparation of catalysts method of claim 1, it is characterized in that in the water soluble salt mixture of said iron and cobalt, the mol ratio of iron and cobalt is 1: 4～4: 1, in the water soluble salt mixture of nickel and cobalt, the molar ratio range of nickel and cobalt is 1: 4～4: 1.
3. be used to produce the Preparation of catalysts method of CNT, it is characterized in that may further comprise the steps:
1) water soluble salt of iron, cobalt or nickel or the water soluble salt mixture of iron and cobalt or the water soluble salt mixture of nickel and cobalt are dissolved in the deionized water, making its concentration is 2～10wt%, add macromolecule dispersing agent under the magnetic agitation, the consumption of macromolecule dispersing agent is 0.5～2% of a metal salt solution weight, again magnetic agitation 15～30min;
2) nano-calcium carbonate calcium powder and above-mentioned solution outstandingly are dissolved in the solution magnetic agitation 15～30min by weight 3.5～15: 100;
3) be that 4～12% weak aqua ammonia dropwise adds in the above-mentioned suspension that is stirring with weight percent concentration, treat pH value to 8～10 o'clock of colloid, stop to add ammoniacal liquor, continue to stir 30～60min;
4) solution is heated to 60～80 ℃, stir evaporate most of water after, be put in the baking oven in 120～150 ℃ of oven dry, being milled into then that powder promptly makes with the nano-calcium carbonate is the catalyst of carrier.
4. by the described Preparation of catalysts method of claim 3, it is characterized in that in the water soluble salt mixture of said iron and cobalt, the mol ratio of iron and cobalt is 1: 4～4: 1, in the water soluble salt mixture of nickel and cobalt, the molar ratio range of nickel and cobalt is 1: 4～4: 1.
5. by the described Preparation of catalysts method of claim 3, it is characterized in that said macromolecule dispersing agent is polyethylene glycol-200, polyethylene glycol-2000 or polyvinyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410015667 CN1275691C (en) | 2004-01-01 | 2004-01-01 | Preparation method of catalyst used for producing carbon nano pipe |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410015667 CN1275691C (en) | 2004-01-01 | 2004-01-01 | Preparation method of catalyst used for producing carbon nano pipe |
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| Publication Number | Publication Date |
|---|---|
| CN1555922A CN1555922A (en) | 2004-12-22 |
| CN1275691C true CN1275691C (en) | 2006-09-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200410015667 Expired - Fee Related CN1275691C (en) | 2004-01-01 | 2004-01-01 | Preparation method of catalyst used for producing carbon nano pipe |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531362B (en) * | 2009-04-17 | 2010-11-10 | 北京化工大学 | Method for one-step growth of carbon nanotube by taking carbon composite as catalyst |
| WO2013137825A1 (en) * | 2012-03-12 | 2013-09-19 | Nanyang Technological University | Methods of preparing catalysts for the chirally selective synthesis of single-walled carbon nanotubes |
| KR101446116B1 (en) * | 2012-09-18 | 2014-10-06 | 한화케미칼 주식회사 | Metal catalyst for producing carbon nanotubes and method for preparing carbon nanotubes using thereof |
| CN104437582A (en) * | 2014-11-03 | 2015-03-25 | 江南大学 | Preparation method of oil-fat hydrogenation nano catalyst |
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