CN112264019B - Synthetic carbon nanotube catalyst taking waste gypsum as carrier, and preparation method and application thereof - Google Patents
Synthetic carbon nanotube catalyst taking waste gypsum as carrier, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a synthetic carbon nano tube catalyst taking waste gypsum as a carrier, a preparation method and application thereof. The preparation method comprises the steps of preparing a granular carrier from waste phosphogypsum, carbon nanotubes and a forming agent through the processes of crushing, proportioning, granulating, forming, calcining at low temperature, and the like, immersing the granular carrier in an active component precursor composite solution, and drying and calcining at low temperature to prepare the synthetic carbon nanotube catalyst. The catalyst for synthesizing the carbon nano tube not only can realize the resource utilization of industrial waste phosphogypsum, but also can carry out incomplete catalytic oxidation on toluene which is an organic pollutant at low temperature to synthesize the carbon nano tube.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a synthetic carbon nanotube catalyst taking waste gypsum as a carrier, and a preparation method and application thereof.
Background
Phosphogypsum is solid waste discharged during the production of phosphate fertilizer and phosphoric acid, and about 4.5-5 tons of phosphogypsum is produced per 1 ton of phosphoric acid. Phosphogypsum main component CaSO 4 ·2H 2 O, and also contains a small amount of phosphoric acid, silicon, magnesium, iron, aluminum, organic impurities, and the like. The phosphogypsum resource utilization condition is not satisfactory both in China and abroad. The utilization rate of phosphogypsum in developed countries such as japan, korea and germany is relatively high. The utilization rate of phosphogypsum in other undeveloped countries is relatively low, and direct discharge (disposal) is the main factor. The disposal mode occupies a large amount of farmland and land, and has a certain influence on the environment besides consuming money in the construction and maintenance of a storage yard. In China, phosphogypsum is unreasonable to be utilized, so that a large amount of resources are wasted, and the phosphogypsum is mainly used for building material products, soil amendments, cement retarders and other aspects with low additional output values. Patent CN201910457646.5 discloses a method for preparing micro-nano calcium carbonate and ammonium sulfate by using waste phosphogypsum, which comprises sequentially adding cationic surfactant and ammonium bicarbonate into phosphogypsum dispersion, suction-filtering the mixed solution, and filteringDrying the upper layer solid to obtain calcium carbonate; and finally concentrating and crystallizing the filtrate to obtain the ammonium sulfate. Patent CN201910174925.0 discloses a camptothectic acid crop nutrient soil prepared by using waste phosphogypsum and edible fungus culture medium, which is prepared by mixing peat soil, sandy soil, phosphogypsum, waste edible fungus culture medium, compound fertilizer and Chinese medicine residues. The organic components of the waste edible fungus culture medium and the pH value of phosphogypsum are utilized to adjust the pH value of the nutrient soil and increase the organic matters, so that the pollution is reduced, the environment is protected, and the waste is recycled. Patent CN201710873171.9 discloses a method for obtaining reinforced and toughened phosphogypsum by screening, adding reinforced and toughened materials, aging, drying and desulfurizing waste phosphogypsum. Patent CN201010143052.6 discloses a method for producing cement retarder from waste phosphogypsum, which comprises the following steps: (1) adding a modifier and a quality improver into phosphogypsum, and mixing; (2) crushing the mixture by a crusher; (3) stacking and aging the crushed mixture; (4) drying the aged mixture; (5) kneading and compacting the dried mixture; (6) granulating with a granulator. The above patent can prepare the waste phosphogypsum into products such as calcium carbonate, nutrient soil, toughened phosphogypsum and the like, and solves the problem of comprehensive utilization of solid waste phosphogypsum, but the economic added value of the final product is lower. Therefore, the disposal of industrial waste phosphogypsum is not only needed to solve the problem of solid waste, but also considered to improve the economic value of large-scale utilization.
Meanwhile, with the rapid development of the industry in China, the problem of air pollution is increasingly serious, and the industrial waste gas treatment technology is more and more widely focused. Toluene is an important raw material in the field of organic chemical production, and is used as a solvent and a high-octane gasoline additive in a large quantity. Toluene is a typical Volatile Organic Compound (VOCs) and has acute toxicity, reproductive toxicity, mutagenic and other hazards, and direct discharge of toluene can cause serious harm to human health and the environment. The thermal catalytic oxidation method is an effective method for treating high-concentration toluene industrially at present, and has the advantages of low catalytic temperature, high activity, small environmental pollution and the like. The catalyst is the core of the thermal catalytic oxidation technology. Conventional catalysts include noble metal catalysts and goldBelongs to an oxide catalyst. The noble metal catalyst has good initial catalytic activity, but has the defects of high price, easy poisoning, easy sintering at high temperature and the like. Metal oxide catalysts, although inexpensive, tend to have poor catalytic activity. The development of efficient, inexpensive catalysts has therefore become one of the focus of research for the thermocatalytic oxidation of toluene. Patent CN201510560923.7 discloses an iron ion exchange titanium ion pillared montmorillonite catalyst for thermocatalytically oxidizing toluene with sodium-based montmorillonite, iron salt, titanium salt as raw materials. It can effectively catalyze and oxidize high-concentration toluene and is used for removing high-concentration toluene at 375 deg.C>1000mL/m 3 ) The toluene removal rate of the catalyst reaches more than 90 percent. Patent CN201811440916.3 discloses a molecular sieve catalyst for preparing toluene by thermal catalytic oxidation, which uses potassium permanganate and manganese nitrate as metal element sources of the catalyst and uses molecular sieve as a load, and has the advantages of high catalytic activity, simple preparation method, low cost and the like, wherein the conversion rate of toluene with low concentration (200 ppm) reaches more than 90% at 255 ℃. The patent has low price and high catalytic activity, but the toluene is completely catalyzed and oxidized, and the product has no economic value. Therefore, it is also a waste of resources for the disposal of toluene.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a synthetic carbon nano tube catalyst using waste gypsum as a carrier, and the invention also aims to provide a preparation method and application of the synthetic carbon nano tube catalyst
The aim of the invention can be achieved by the following technical scheme:
a catalyst for synthesizing carbon nanotubes by taking waste gypsum as a carrier is characterized in that: the catalyst takes carbon nano tubes and waste phosphogypsum discharged during industrial phosphoric acid preparation as carriers and nickel-copper composite oxide as a catalytic active component; wherein, abandonment phosphogypsum: carbon nanotubes: and (3) a forming agent: the mass ratio of the catalytic active components is 90-98: 1 to 5: 3-8: 1 to 10.
Among the above catalysts: waste phosphogypsum: carbon nanotubes: and (3) a forming agent: the mass ratio of the catalytic active components is 93-94: 1-2: 5: 5-10, and the mass ratio of nickel oxide to copper oxide is 1-5: 1 to 5.
Among the above catalysts: the carbon nano tube is a multi-wall carbon nano tube, and the tube diameter of the nano tube is 20-50nm.
Among the above catalysts: the forming agent is ethylene glycol dimethacrylate.
The catalyst is as follows: the nickel oxide precursor is nickel chloride hexahydrate, and the copper oxide precursor is copper chloride dihydrate.
The preparation method of the synthetic carbon nano tube catalyst comprises the following steps:
(1) Preparation of particulate support
Respectively crushing and sieving waste phosphogypsum and multi-wall carbon nanotube powder, uniformly mixing, adding a forming agent for granulating, adding the granulated pug into a die for pressurizing, maintaining pressure, preparing spherical particle blanks, and calcining in an atmosphere furnace under the atmosphere of carbon monoxide to obtain a granular carrier;
(2) Preparation of active component precursor composite solution
Deionized water and phosphoric acid are respectively added into nickel chloride hexahydrate and copper chloride dihydrate, and the mixture is stirred until the solution is clear and transparent; adding the nickel chloride solution into the copper chloride solution, mixing and stirring uniformly until the solution is clear and transparent, and obtaining an active component precursor composite solution;
(3) Catalyst preparation
And (3) immersing the granular carrier prepared in the step (1) in the active component precursor composite solution prepared in the step (2), placing in an oven, preserving heat for 24 hours at 90 ℃ for drying, and then placing in an atmosphere furnace, introducing carbon monoxide atmosphere for secondary calcination to obtain the granular synthetic carbon nanotube catalyst.
The preparation method comprises the following steps: the pressurizing pressure in the step (1) is 5-6 MPa, and the pressure maintaining time is 3min.
The preparation method comprises the following steps: the calcining temperature in the step (1) is 400-500 ℃, and the heat preservation time is 4-6 h.
The preparation method comprises the following steps: the secondary calcination temperature in the step (3) is 400-500 ℃, and the heat preservation time is 4-6 h.
The technical scheme of the invention is as follows: the catalyst is applied to the aspect of preparing the carbon nano tube; as preferable: the catalyst is used for catalyzing toluene to synthesize the carbon nano tube.
The invention has the beneficial effects that:
in view of the problems of large amount of industrial waste phosphogypsum in China, lack of advanced safety treatment and high added value recycling technology, the invention creatively provides a method for preparing a granular carrier by utilizing waste phosphogypsum and multi-wall carbon nano tubes, and the method uses nickel-copper composite oxide as an active component to prepare a catalyst to incompletely catalyze and oxidize toluene to generate the carbon nano tubes. The method solves the disposal problem of toluene waste gas and large-batch waste phosphogypsum fundamentally, and realizes the high added value recycling of the toluene waste gas and the large-batch waste phosphogypsum. The main basis is: the main component of the waste phosphogypsum is calcium sulfate with rich hydroxyl groups on the surface, has certain catalysis assisting performance, and can be used as seed crystals of carbon nanotube products by doping a small amount of multi-wall carbon nanotubes to promote the conversion of toluene to the carbon nanotubes. After the active component nickel-copper composite oxide is loaded, the granular synthetic carbon nano tube catalyst can be prepared, and toluene pollution can be effectively solved. The successful application of the invention not only can thoroughly solve the problem of safe disposal of waste phosphogypsum, but also can solve the problems of toluene pollution and carbon nano tube scale production as a catalyst for synthesizing the carbon nano tube, thereby bringing great economic, environmental and social benefits.
The synthetic carbon nanotube catalyst prepared by the invention thoroughly and effectively solves the secondary pollution and high added value recycling of waste phosphogypsum. Meanwhile, toluene is used as a carbon source, and the multi-wall carbon nano tube is prepared by carrying out a carbon nano tube synthesis reaction under the action of a catalyst, so that the problems of toluene environmental pollution and multi-wall carbon nano tube mass production can be solved. The catalyst for synthesizing the carbon nano tube has high conversion rate of the carbon nano tube at low temperature, simple preparation process and wide market application prospect.
Detailed Description
The invention is further illustrated below with reference to examples, but the scope of the invention is not limited thereto:
example 1:
(1) Crushing of raw materials
Respectively crushing waste phosphogypsum and multi-wall carbon nanotubes by a ball mill, and homogenizing by a 100-target standard sieve for standby;
(2) Proportioning and granulating
93.000g of waste phosphogypsum powder and 2.000g of multi-wall carbon nano tube powder are weighed and uniformly stirred, and then 5.000g of ethylene glycol dimethacrylate is weighed and mixed with the powder for grinding and granulating;
(3) Shaping and calcining
Weighing 5.000g of granulated pug, adding the pug into a die, pressurizing to 5MPa, maintaining the pressure for 3min, taking out a sample, repeating blank molding for 20 times to obtain spherical granular blank 20 blocks, placing the spherical granular blank into an atmosphere furnace, introducing carbon monoxide atmosphere, and calcining at 400 ℃ for 4h to obtain a granular carrier;
(4) Preparation of active component precursor composite solution
12.726g of nickel chloride hexahydrate is weighed, 50.904g of deionized water is added, 6.363g of concentrated phosphoric acid is added dropwise, and stirring is carried out until the solution is clear and transparent; then 2.143g of copper chloride dihydrate is weighed, 8.572g of deionized water is added, 1.072g of concentrated phosphoric acid is added dropwise, and stirring is carried out until the solution is clear and transparent; adding the nickel chloride solution into the copper chloride solution, mixing and stirring uniformly until the solution is clear and transparent, and obtaining the active component precursor composite solution.
(5) Catalyst preparation
And (3) dipping the granular carrier prepared in the step (3) into the active component precursor composite solution prepared in the step (4), placing the solution in an oven, preserving heat for 24 hours at 90 ℃, drying the solution, placing the solution in an atmosphere furnace, introducing carbon monoxide atmosphere, preserving heat for 4 hours at 400 ℃, and obtaining the granular synthetic carbon nanotube catalyst, wherein the mass percent of nickel oxide is 4%, and the mass percent of copper oxide is 1%.
(6) Catalyst Activity test
10g of a synthetic carbon nanotube catalyst was charged into a catalyst performance evaluation reaction apparatus, and a reaction gas was introduced to evaluate the activity. The concentration of each gas is: n (N) 2 (1000mL/min)；H 2 O (50 mL/min); toluene (toluene)(1 mL/min). 200mg of carbon nano tubes can be grown on the surface of the catalyst per minute on average at 350 ℃, and the conversion rate of the carbon nano tubes reaches 25.2 percent.
(7) Application range: the synthesized carbon nanotube catalyst prepared by the method is suitable for catalyzing toluene to synthesize carbon nanotubes.
Example 2:
(1) Crushing of raw materials
Respectively crushing waste phosphogypsum and multi-wall carbon nanotubes by a ball mill, and homogenizing by a 100-target standard sieve for standby;
(2) Proportioning and granulating
94.000g of waste phosphogypsum powder and 1.000g of multi-wall carbon nano tube powder are weighed and uniformly stirred, and then 5.000g of ethylene glycol dimethacrylate is weighed and mixed with the powder for grinding and granulating;
(3) Shaping and calcining
Weighing 5.000g of granulated pug, adding the pug into a die, pressurizing to 6MPa, maintaining the pressure for 3min, taking out a sample, repeating blank molding for 20 times to obtain spherical granular blank 20 blocks, placing the spherical granular blank into an atmosphere furnace, introducing carbon monoxide atmosphere, and calcining at 500 ℃ for 6h to obtain a granular carrier;
(4) Preparation of active component precursor composite solution
15.908g of nickel chloride hexahydrate is weighed, 63.632g of deionized water is added, 7.954g of concentrated phosphoric acid is added dropwise, and stirring is carried out until the solution is clear and transparent; then weighing 10.717g of copper chloride dihydrate, adding 42.868g of deionized water, dropwise adding 5.359g of concentrated phosphoric acid, and stirring until the solution is clear and transparent; adding the nickel chloride solution into the copper chloride solution, mixing and stirring uniformly until the solution is clear and transparent, and obtaining the active component precursor composite solution.
(5) Catalyst preparation
And (3) dipping the granular carrier prepared in the step (3) into the active component precursor composite solution prepared in the step (4), placing the solution in an oven, preserving heat for 24 hours at 90 ℃, drying the solution, placing the solution in an atmosphere furnace, introducing carbon monoxide atmosphere, preserving heat for 6 hours at 500 ℃, and obtaining the granular synthetic carbon nanotube catalyst, wherein the nickel oxide accounts for 5% by mass and the copper oxide accounts for 5% by mass.
(6) Catalyst Activity test
10g of a synthetic carbon nanotube catalyst was charged into a catalyst performance evaluation reaction apparatus, and a reaction gas was introduced to evaluate the activity. The concentration of each gas is: n (N) 2 (1000mL/min)；H 2 O (50 mL/min); toluene (1 mL/min). 235mg of carbon nano tubes can grow on the surface of the catalyst at 350 ℃ in average per minute, and the conversion rate of the carbon nano tubes reaches 29.6 percent.
(7) Application range: the synthesized carbon nanotube catalyst prepared by the method is suitable for catalyzing toluene to synthesize carbon nanotubes.
Comparative example 1
(1) Crushing of raw materials
Respectively crushing waste phosphogypsum and multi-wall carbon nanotubes by a ball mill, and homogenizing by a 100-target standard sieve for standby;
(2) Proportioning and granulating
94.000g of waste phosphogypsum powder and 1.000g of multi-wall carbon nano tube powder are weighed and uniformly stirred, and then 5.000g of ethylene glycol dimethacrylate is weighed and mixed with the powder for grinding and granulating;
(3) Shaping and calcining
Weighing 5.000g of granulated pug, adding the pug into a die, pressurizing to 6MPa, maintaining the pressure for 3min, taking out a sample, repeating blank molding for 20 times to obtain spherical granular blank 20 blocks, placing the spherical granular blank into an atmosphere furnace, introducing carbon monoxide atmosphere, and calcining at 500 ℃ for 6h to obtain a granular carrier;
(4) Catalyst Activity test
10g of the particulate carrier was charged into a catalyst performance evaluation reaction apparatus, and a reaction gas was introduced to evaluate the activity. The concentration of each gas is: n (N) 2 (1000mL/min)；H 2 O (50 mL/min); toluene (1 mL/min). Carbon nanotubes are not generated on the surface of the carrier at the temperature of 200-500 ℃.
(5) Contrast effect: in contrast to example 2, the synthesized carbon nanotube catalyst has no catalytically active component, which does not catalyze the synthesis of carbon nanotubes.
Comparative example 2
(1) Crushing of raw materials
Crushing waste phosphogypsum by a ball mill, and sieving the crushed phosphogypsum by a 100-target standard sieve for homogenization for standby;
(2) Proportioning and granulating
95.000g of waste phosphogypsum powder is weighed, 5.000g of ethylene glycol dimethacrylate is weighed and mixed with the powder for grinding and granulating;
(3) Shaping and calcining
Weighing 5.000g of granulated pug, adding the pug into a die, pressurizing to 6MPa, maintaining the pressure for 3min, taking out a sample, repeating blank molding for 20 times to obtain spherical granular blank 20 blocks, placing the spherical granular blank into an atmosphere furnace, introducing carbon monoxide atmosphere, and calcining at 500 ℃ for 6h to obtain a granular carrier;
(4) Preparation of active component precursor composite solution
15.908g of nickel chloride hexahydrate is weighed, 63.632g of deionized water is added, 7.954g of concentrated phosphoric acid is added dropwise, and stirring is carried out until the solution is clear and transparent; then weighing 10.717g of copper chloride dihydrate, adding 42.868g of deionized water, dropwise adding 5.359g of concentrated phosphoric acid, and stirring until the solution is clear and transparent; adding the nickel chloride solution into the copper chloride solution, mixing and stirring uniformly until the solution is clear and transparent, and obtaining the active component precursor composite solution.
(5) Catalyst preparation
And (3) dipping the granular carrier prepared in the step (3) into the active component precursor composite solution prepared in the step (4), placing the solution in an oven, preserving heat for 24 hours at 90 ℃, drying the solution, placing the solution in an atmosphere furnace, introducing carbon monoxide atmosphere, preserving heat for 6 hours at 500 ℃, and obtaining the granular synthetic carbon nanotube catalyst, wherein the nickel oxide accounts for 5% by mass and the copper oxide accounts for 5% by mass.
(6) Catalyst Activity test
10g of a synthetic carbon nanotube catalyst was charged into a catalyst performance evaluation reaction apparatus, and a reaction gas was introduced to evaluate the activity. The concentration of each gas is: n (N) 2 (1000mL/min)；H 2 O (50 mL/min); toluene (1 mL/min). 28mg of carbon nano tubes can grow on the surface of the catalyst at 350 ℃ on average per minute, and the conversion rate of the carbon nano tubes is only 3.5 percent.
(7) Contrast effect: compared with the example 2, the catalyst for synthesizing the carbon nano tube has no multi-wall carbon nano tube as seed crystal, and the conversion rate of the catalytic synthesis of the carbon nano tube is obviously reduced.
Comparative example 3
(1) Crushing of raw materials
Respectively crushing waste phosphogypsum and multi-wall carbon nanotubes by a ball mill, and homogenizing by a 100-target standard sieve for standby;
(2) Proportioning and granulating
93.000g of waste phosphogypsum powder and 2.000g of multi-wall carbon nano tube powder are weighed and uniformly stirred, and then 5.000g of polyvinyl alcohol solution with mass fraction of 7% is weighed and mixed with the powder for grinding and granulating;
(3) Shaping and calcining
Weighing 5.000g of granulated pug, adding the pug into a die, pressurizing to 5MPa, maintaining the pressure for 3min, taking out a sample, repeating the blank molding for 20 times to obtain 20 spherical granular blank blocks, and calcining the spherical granular blank blocks in a muffle furnace at 400 ℃ for 4 hours to obtain a granular carrier;
(4) Preparation of active component precursor composite solution
12.726g of nickel chloride hexahydrate is weighed, 50.904g of deionized water is added, 6.363g of concentrated phosphoric acid is added dropwise, and stirring is carried out until the solution is clear and transparent; then 2.143g of copper chloride dihydrate is weighed, 8.572g of deionized water is added, 1.072g of concentrated phosphoric acid is added dropwise, and stirring is carried out until the solution is clear and transparent; adding the nickel chloride solution into the copper chloride solution, mixing and stirring uniformly until the solution is clear and transparent, and obtaining the active component precursor composite solution.
(5) Catalyst preparation
And (3) dipping the granular carrier prepared in the step (3) into the active component precursor composite solution prepared in the step (4), placing the solution in an oven, preserving heat for 24 hours at 90 ℃, drying, and placing the solution in a muffle furnace, preserving heat for 4 hours at 400 ℃ to obtain the granular synthetic carbon nanotube catalyst, wherein the nickel oxide accounts for 4% by mass and the copper oxide accounts for 1% by mass.
(6) Catalyst Activity test
10g of synthetic carbon nano tube catalyst is taken and put into a catalyst performance evaluation reaction device, and reaction gas is introducedActivity evaluation was performed. The concentration of each gas is: n (N) 2 (1000mL/min)；H 2 O (50 mL/min); toluene (1 mL/min). Carbon nanotubes are not generated on the surface of the carrier at the temperature of 200-500 ℃.
(7) Contrast effect: in comparison with example 1, when the synthetic carbon nanotube catalyst was prepared, it was not catalytically synthesized carbon nanotube activity after the molding agent and the firing atmosphere were changed.
Claims (7)
1. A preparation method of a catalyst for synthesizing carbon nanotubes by taking waste gypsum as a carrier is characterized by comprising the following steps of: the catalyst takes multi-wall carbon nano tubes and waste phosphogypsum discharged during industrial phosphoric acid preparation as carriers and nickel-copper composite oxide as a catalytic active component; wherein, abandonment phosphogypsum: multiwall carbon nanotubes: and (3) a forming agent: the mass ratio of the catalytic active components is 90-98: 1 to 5: 3-8: 1 to 10; the method comprises the following steps:
(1) Preparation of particulate support
Respectively crushing and sieving waste phosphogypsum and multi-wall carbon nanotube powder, uniformly mixing, adding a forming agent for granulating, adding the granulated pug into a die for pressurizing, maintaining pressure, preparing spherical particle blanks, and calcining in an atmosphere furnace under the atmosphere of carbon monoxide to obtain a granular carrier; the forming agent is ethylene glycol dimethacrylate;
(2) Preparation of active component precursor composite solution
Deionized water and phosphoric acid are respectively added into nickel chloride hexahydrate and copper chloride dihydrate, and the mixture is stirred until the solution is clear and transparent; adding the nickel chloride solution into the copper chloride solution, mixing and stirring uniformly until the solution is clear and transparent, and obtaining an active component precursor composite solution;
(3) Catalyst preparation
And (3) immersing the granular carrier prepared in the step (1) in the active component precursor composite solution prepared in the step (2), placing in an oven, preserving heat for 24 hours at 90 ℃ for drying, and then placing in an atmosphere furnace, introducing carbon monoxide atmosphere for secondary calcination to obtain the granular synthetic carbon nanotube catalyst.
2. The method of manufacturing according to claim 1, characterized in that: waste phosphogypsum: multiwall carbon nanotubes: and (3) a forming agent: the mass ratio of the catalytic active components is 93-94: 1-2: 5: 5-10, and the mass ratio of nickel oxide to copper oxide is 1-5: 1 to 5.
3. The method of manufacturing according to claim 1, characterized in that: the pipe diameter of the multi-wall carbon nano-tube is 20-50nm.
4. The method of manufacturing according to claim 1, characterized in that: the pressurizing pressure in the step (1) is 5-6 MPa, and the pressure maintaining time is 3min.
5. The method of manufacturing according to claim 1, characterized in that: the calcining temperature in the step (1) is 400-500 ℃, and the heat preservation time is 4-6 h.
6. The method of manufacturing according to claim 1, characterized in that: the secondary calcination temperature in the step (3) is 400-500 ℃, and the heat preservation time is 4-6 h.
7. The use of the catalyst for synthesizing carbon nanotubes by using waste gypsum as a carrier, which is prepared by the method of claim 1, as a catalyst for synthesizing carbon nanotubes by using toluene.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006231172A (en) * | 2005-02-23 | 2006-09-07 | National Institute Of Advanced Industrial & Technology | Manufacturing method of catalyst particles for manufacturing nanocarbon material and catalyst particles for manufacturing nanocarbon material |
| JP2006231198A (en) * | 2005-02-24 | 2006-09-07 | Mitsubishi Heavy Ind Ltd | Catalyst for producing nanocarbon material, its production method and apparatus for producing nanocarbon material |
| WO2008020826A2 (en) * | 2005-07-25 | 2008-02-21 | Nanodynamics Inc. | Combustion process for producing carbon nanotubes |
| JP2012082077A (en) * | 2010-10-06 | 2012-04-26 | Kawaken Fine Chem Co Ltd | Multilayer carbon nanotube aggregate and method for producing the same |
| CN105238497A (en) * | 2015-09-28 | 2016-01-13 | 昆明理工大学 | Method for preparing oxygen carrier by using phosphogypsum, and applications of carrier |
| CN111036264A (en) * | 2019-12-11 | 2020-04-21 | 太原理工大学 | Preparation method of coal-based carbon nanotube catalyst for efficiently catalyzing and oxidizing toluene |
| CN111138167A (en) * | 2019-12-31 | 2020-05-12 | 南京环福新材料科技有限公司 | Ceramic catalyst taking red mud waste residue as carrier and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4584142B2 (en) * | 2003-02-14 | 2010-11-17 | 茂夫 丸山 | Method for forming catalytic metal fine particles for production of single-walled carbon nanotubes |
| US8895105B2 (en) * | 2011-06-13 | 2014-11-25 | University Of Dayton | Receptor-catalyst growth process for carbon nanotubes |
-
2020
- 2020-11-16 CN CN202011279462.3A patent/CN112264019B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006231172A (en) * | 2005-02-23 | 2006-09-07 | National Institute Of Advanced Industrial & Technology | Manufacturing method of catalyst particles for manufacturing nanocarbon material and catalyst particles for manufacturing nanocarbon material |
| JP2006231198A (en) * | 2005-02-24 | 2006-09-07 | Mitsubishi Heavy Ind Ltd | Catalyst for producing nanocarbon material, its production method and apparatus for producing nanocarbon material |
| WO2008020826A2 (en) * | 2005-07-25 | 2008-02-21 | Nanodynamics Inc. | Combustion process for producing carbon nanotubes |
| JP2012082077A (en) * | 2010-10-06 | 2012-04-26 | Kawaken Fine Chem Co Ltd | Multilayer carbon nanotube aggregate and method for producing the same |
| CN105238497A (en) * | 2015-09-28 | 2016-01-13 | 昆明理工大学 | Method for preparing oxygen carrier by using phosphogypsum, and applications of carrier |
| CN111036264A (en) * | 2019-12-11 | 2020-04-21 | 太原理工大学 | Preparation method of coal-based carbon nanotube catalyst for efficiently catalyzing and oxidizing toluene |
| CN111138167A (en) * | 2019-12-31 | 2020-05-12 | 南京环福新材料科技有限公司 | Ceramic catalyst taking red mud waste residue as carrier and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 化学工业部科学技术情报研究所.《化工产品手册 有机化工原料 上册》.化学工业出版社,1985,322-324. * |
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