CN103569993A - Catalyst and method for producing nanometer carbon and hydrogen - Google Patents
Catalyst and method for producing nanometer carbon and hydrogen Download PDFInfo
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- CN103569993A CN103569993A CN201210252175.2A CN201210252175A CN103569993A CN 103569993 A CN103569993 A CN 103569993A CN 201210252175 A CN201210252175 A CN 201210252175A CN 103569993 A CN103569993 A CN 103569993A
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- sized carbon
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Abstract
The present invention provides a method for producing nanometer carbon and hydrogen. The method comprises: adopting a hydrocarbon as a raw material, carrying out catalysis cracking on the hydrocarbon at a temperature of 500-850 DEG C under a pressure of 0-1 MPa to obtain a nanometer carbon crude product and hydrogen, calcining the nanometer carbon crude product for 0.8-1.5 h at a temperature of 250-400 DEG C, refluxing for 2-5 h in concentrated hydrochloric acid, collecting the solid, and drying to obtain the pure nanometer carbon. With the catalyst and the method for producing nanometer carbon and hydrogen through hydrocarbon cracking, the amorphous carbon precursor or the by-product can be eliminated, and the raw materials containing carbon dioxide, oxygen, water and other gases can be adopted to perform production; and the raw material purity requirement is reduced, and the production cost is substantially reduced.
Description
Technical field
The present invention relates to a kind of Catalyst And Method of producing nano-sized carbon and hydrogen, relate in particular to and a kind ofly take hydrocarbon and carry out cracking, the Catalyst And Method of production nano-sized carbon and hydrogen as raw material.
Background technology
Rudimentary hydrocarbon polymer (hydrocarbon) is cracked into into carbon and hydrogen, it is thermo-negative reaction, if want, by single step reaction, reach high transformation efficiency, just need higher temperature of reaction, but, because higher decomposition reaction temperature is decomposed lower hydrocarbon polymer, bring speed of response to improve, just cause in solid catalyst surface and generate a large amount of solid knot carbon.This solid knot carbon the inside is except some functional nano-sized carbon, and beyond carbon nanofiber, it also contains amorphous carbon byproduct.The generation of decolorizing carbon will cause reacting with metal catalyst, and the surface that produces a kind of inert metal carbide covering catalyst, reduce the catalytic activity of catalyzer, reduce the speed of response of decomposing hydrogen and carbon nano-sized carbon, reduce the switching speed of hydrocarbon polymer.Therefore, traditional manufacture method is with highly purified hydro carbons, to be raw material as far as possible.
In recent years, the exhaustion of the fossil resources such as oil worry, sun power, wind energy and biomass energy become noticeable substitute energy, and combustion of hydrogen does not discharge the carbonic acid gas that causes Greenhouse effect, so cause people's very big concern as a kind of clean energy.Biogas is a kind of renewable energy source, and main component is lower hydrocarbon methane, and utilizing biogas to replace petrochemical complex hydrocarbon product is raw material, and cracking, for nano-sized carbon and hydrogen, can solve the pressure that oil shortage brings.But, as described above, the method for existing cracking lower hydrocarbon production nano-sized carbon, must highly purified hydrocarbon feed, the increase of the needs of the purification apparatus of hydrocarbon polymer and running cost is become to the obstruction of industrialization, as the removal of carbonic acid gas in biogas needs PSA or membrane separation plant.
Summary of the invention
The problems referred to above for utilizing hydrocarbon pyrolysis production nano-sized carbon and hydrogen to exist, the invention provides a kind of new production nano-sized carbon and the Catalyst And Method of hydrogen, have reduced hydrocarbon feed purity requirement, thereby have reduced the production cost of nano-sized carbon and hydrogen.
The method of production nano-sized carbon provided by the invention and hydrogen, step comprises: take hydrocarbon as raw material, under 0 ~ 1MPa pressure, 500 ~ 850 ℃ of temperature condition, catalytic cracking hydrocarbon obtains nano-sized carbon crude product and hydrogen, by nano-sized carbon crude product, at 250 ~ 400 ℃ of calcining 0.8 ~ 1.5h, the 2 ~ 5h that then refluxes in concentrated hydrochloric acid, collects solid, dry, obtain pure nano-sized carbon.
Preferably, the method for described production nano-sized carbon and hydrogen, by nano-sized carbon crude product 300 ℃ of calcinings, then 100 ℃ of backflows in concentrated hydrochloric acid.
Wherein, described raw material can be at present known can cracking production nano-sized carbon and any hydrocarbon of hydrogen, be preferably any one or a few in the hydrocarbon of C1 ~ C5, or contain in C1 ~ C5 hydrocarbon any one mixed gas, as methane, ethane, propane, butane, ethene, propylene, any one or a few in divinyl, pentane or the mixed gas that contains above-mentioned any hydrocarbon.
According to a kind of preferred embodiment of the method for production nano-sized carbon of the present invention and hydrogen, described raw material is biogas.More preferably, in described biogas, can contain any one or a few in carbonic acid gas, carbon monoxide, nitrogen, water, oxygen.
According to the more preferred embodiment of the method for production nano-sized carbon of the present invention and hydrogen, in described biogas, contain the carbonic acid gas that volume content is 0.05%-35%, contain water and/or carbon monoxide and/or oxygen and/or nitrogen that volume content is 0.05%-10%.
In the method for production nano-sized carbon of the present invention and hydrogen, the active metal of described cracking hydrocarbon used catalyst is preferably any one or a few the mixture in iron, nickel, cobalt.Wherein, described catalyzer can also comprise the second metal, and the second metal is selected from mendeleev periodic table of elements IBHe VIII family metal, as copper, gold and silver, ruthenium, rhodium, palladium, osmium, iridium, platinum.
Described catalyzer also comprises carrier, and described carrier is selected from magnesium oxide, aluminum oxide, silicon oxide, more preferably magnesium oxide.
Preferably, described method for preparing catalyst is: in reaction solvent, and M (NO
3)
x, metal compound and organic carboxyl acid be at 40 ~ 55 ℃ of reaction 0.5 ~ 2h, then removes solvent; At 8 ± 0.5h, be interiorly warming up to 600 ± 5 ℃ by solid sintering from 100 ± 5 ℃, then with hydrogen reducing, obtain described metal M-oxide catalyst, M (NO
3)
xbe selected from Ni (NO
3)
2, Co (NO
3)
2, or Fe (NO
3)
3; Metal compound is selected from Mg (NO
3)
2, Al (NO
3)
3, SiO
2, Al
2o
3.
In the another kind of preferred embodiment of the present invention, described method for preparing catalyst is: in reaction solvent, and M (NO
3)
x, M
2(NO
3)
ymetal compound and organic carboxyl acid, at 40 ~ 55 ℃ of reaction 0.5 ~ 2h, are then removed solvent; At 8 ± 0.5h, be interiorly warming up to 600 ± 5 ℃ by solid sintering from 100 ± 5 ℃, then with hydrogen reducing, obtain described metal M-M
2oxide catalyst, M
2(NO
3)
yit is the second metal nitrate.
Wherein, described reaction solvent is preferably methyl alcohol, ethanol, water, propyl alcohol, methylene dichloride or the mixture of solvent arbitrarily wherein.
Second object of the present invention is to provide a kind of catalyzer for above-mentioned production nano-sized carbon and hydrogen method, and described catalyzer comprises active metal, carrier, and described carrier is selected from silicon oxide, magnesium oxide, aluminum oxide; Described active metal is selected from nickel, iron, cobalt.
In described catalyzer, active metal weight percentage is preferably 30 ~ 80%, and more preferably 30% ~ 70%, as 40%, 45%, 50%, 60%, 65%.
Described method for preparing catalyst is preferably as follows: in reaction solvent, and M (NO
3)
x, metal compound and organic carboxyl acid be at 40 ~ 55 ℃ of reaction 0.5 ~ 2h, then removes solvent; At 8 ± 0.5h, be interiorly warming up to 600 ± 5 ℃ by solid sintering from 100 ± 5 ℃, then with hydrogen reducing, obtain described metal M-oxide catalyst, M (NO
3)
xbe selected from Ni (NO
3)
2, Co (NO
3)
2, or Fe (NO
3)
3; Metal compound is selected from Mg (NO
3)
2, Al (NO
3)
3, SiO
2, Al
2o
3.
In a kind of preferred embodiment of catalyzer of the present invention, also comprise the second metal, the second metal is selected from mendeleev periodic table of elements VIII HuoIB family metal, such as copper, gold and silver, ruthenium, rhodium, palladium, osmium, iridium, platinum.
In catalyzer of the present invention, described the second active metal and above-mentioned active metal weight ratio are preferably 1:3 ~ 10, and 1:5 ~ 8 more preferably, as 1:6,1:7.
Described method for preparing catalyst is preferably as follows: in reaction solvent, and M (NO
3)
x, M
2(NO
3)
ymetal compound and organic carboxyl acid, at 40 ~ 55 ℃ of reaction 0.5 ~ 2h, are then removed solvent; At 8 ± 0.5h, be interiorly warming up to 600 ± 5 ℃ by solid sintering from 100 ± 5 ℃, then with hydrogen reducing, obtain described metal M-M
2oxide catalyst, M
2(NO
3)
yit is the second metal nitrate.
Wherein, described organic carboxyl acid is preferably citric acid.
Third aspect of the present invention is to provide a kind of preparation method of described catalyzer, in reaction solvent, and M (NO
3)
x, metal compound and organic carboxyl acid be at 40 ~ 55 ℃ of reaction 0.5 ~ 2h, then removes solvent; At 8 ± 0.5h, be interiorly warming up to 600 ± 5 ℃ by solid sintering from 100 ± 5 ℃, then with hydrogen reducing, obtain described metal M-oxide catalyst, M (NO
3)
xbe selected from Ni (NO
3)
2, Co (NO
3)
2, or Fe (NO
3)
3; Metal compound is selected from Mg (NO
3)
2, Al (NO
3)
3, SiO
2, Al
2o
3.
The 4th aspect of the present invention is to provide the preparation method of another kind of catalyzer, in reaction solvent, and M (NO
3)
x, M
2(NO
3)
ymetal compound and organic carboxyl acid, at 40 ~ 55 ℃ of reaction 0.5 ~ 2h, are then removed solvent; At 8 ± 0.5h, be interiorly warming up to 600 ± 5 ℃ by solid sintering from 100 ± 5 ℃, then with hydrogen reducing, obtain described metal M-M
2oxide catalyst, M
2(NO
3)
yit is the second metal nitrate.
Cracking hydrocarbon provided by the invention is prepared catalyzer and the method for nano-sized carbon, has highly selective, without hydrocarbon is separated with other impurity, directly uses biogas can produce for raw material, greatly reduces the cost of cracking hydrocarbon production nano-sized carbon and hydrogen.
Embodiment
embodiment 1
step 1, the preparation of catalyzer
Ni (NO
3)
26H
2o 15g adds methyl alcohol 500mL, stirring and dissolving, then add Mg (NO
3)
26H
2o 20g, citric acid 20g, deionized water 200mL, 50 ℃ of heated and stirred 1 hour, remove methyl alcohol and water major part with Rotary Evaporators.By solid in air 100 ℃ start to be sintered to 600 ℃, amount to 8 hours, then within 5 hours, obtain metallic nickel magnesia catalyst with hydrogen reducing, wherein, Ni weight content 50%.
step 2, scission reaction
Silica fiber is put at the silica tube middle part of 1 inch of internal diameter, the catalyzer 2g preparing is above placed on silica fiber, hydrogen 100sccm flow velocity, 500 ℃ of furnace temperatures, carry out restore 3 hours of catalyzer, then nitrogen enters reaction tubes with 100sccm flow velocity portion, at same temperature, rinses, and the upper demonstration of GC does not have other gaseous constituents except nitrogen.
Biogas: main component is methane, wherein also contains 35% carbonic acid gas, 10% oxygen, 4% carbon monoxide, 10% water, 0.5% nitrogen.
Biogas flow velocity 50sccm, the mixed gas of nitrogen flow rate 100sccm flows into this reaction silica tube, at 500 ~ 850 ℃ of temperature, carry out scission reaction, reaction terminating after 2 hours, is as cold as room temperature under nitrogen circulation, and CNT (carbon nano-tube) is taken out, tem analysis the structure of nano-sized carbon, the about 2nm of nanometer caliber, the number of plies is 2 layers, accounts for overall 90%.
The crude product obtaining is burnt 1 hour in 300 ℃ of air, then reflux 3 hours with 100 ℃ of concentrated hydrochloric acid aqueous solutions.Filter, repeatedly several times, dry 10 hours of 100 ℃ of the products that obtain, obtain the nano-sized carbon of sterling in same operation.
embodiment 2
step 1, the preparation of catalyzer
Co (NO
3)
26H
2o 15g adds propyl alcohol 500mL, stirring and dissolving, then add Mg (NO
3)
26H
2o 20g, oxalic acid 13g, deionized water 200mL, 55 ℃ of heated and stirred 1.8 hours, remove methyl alcohol and water major part with Rotary Evaporators.By solid in air 100 ℃ start to be sintered to 600 ℃, amount to 8 hours, then within 5 hours, obtain cobalt metal magnesia catalyst, Co weight content 50% with hydrogen reducing.
step 2, scission reaction
Silica fiber is put at the silica tube middle part of 1 inch of internal diameter, the catalyzer 2g preparing is above placed on silica fiber, hydrogen 100sccm flow velocity, 500 ℃ of furnace temperatures, carry out restore 3 hours of catalyzer, then nitrogen enters reaction tubes with 100sccm flow velocity portion, at same temperature, rinses, and the upper demonstration of GC does not have other gaseous constituents except nitrogen.
Biogas: main component is methane, wherein also contains 5% carbonic acid gas, 1% oxygen, 5% carbon monoxide, 3% water.
Biogas flow velocity 50sccm, the mixed gas of nitrogen flow rate 100sccm flows into this reaction silica tube, at 500 ~ 850 ℃ of temperature, carry out scission reaction, reaction terminating after 2.5 hours, is as cold as room temperature under nitrogen circulation, and CNT (carbon nano-tube) is taken out, tem analysis the structure of nano-sized carbon, the about 2nm of nanometer caliber, the number of plies is 2 layers, accounts for overall 90%.
The crude product obtaining is burnt 1 hour in 280 ℃ of air, then reflux 3 hours with 100 ℃ of concentrated hydrochloric acid aqueous solutions.Filter, repeatedly several times, dry 10 hours of 100 ℃ of the products that obtain, obtain the nano-sized carbon of sterling in same operation.
embodiment 3
step 1, the preparation of catalyzer
Fe (NO
3)
39H
2o 20g adds propyl alcohol 500mL, stirring and dissolving, then add Mg (NO
3)
26H
2o 20g, citric acid 20g, deionized water 200mL, 47 ℃ of heated and stirred 1 hour, remove methyl alcohol and water major part with Rotary Evaporators.By solid in air 100 ℃ start to be sintered to 600 ℃, amount to 8 hours, then within 5 hours, obtain metallic iron magnesia catalyst, Fe weight content 50% with hydrogen reducing.
step 2, scission reaction
Silica fiber is put at the silica tube middle part of 1 inch of internal diameter, the catalyzer 2g preparing is above placed on silica fiber, hydrogen 100sccm flow velocity, 500 ℃ of furnace temperatures, carry out restore 3 hours of catalyzer, then nitrogen enters reaction tubes with 100sccm flow velocity portion, at same temperature, rinses, and the upper demonstration of GC does not have other gaseous constituents except nitrogen.
Biogas: main component is methane, wherein also contains 20% carbonic acid gas, 0.5% oxygen, 2% carbon monoxide, 10% water, 3% nitrogen.
Biogas flow velocity 50sccm, the mixed gas of nitrogen flow rate 100sccm flows into this reaction silica tube, at 500 ~ 850 ℃ of temperature, carry out scission reaction, reaction terminating after 2.5 hours, is as cold as room temperature under nitrogen circulation, and CNT (carbon nano-tube) is taken out, tem analysis the structure of nano-sized carbon, the about 2nm of nanometer caliber, the number of plies is 2 layers, accounts for overall 90%.
The crude product obtaining is burnt 1 hour in 360 ℃ of air, then reflux 3 hours with 100 ℃ of concentrated hydrochloric acid aqueous solutions.Filter, repeatedly several times, dry 10 hours of 100 ℃ of the products that obtain, obtain the nano-sized carbon of sterling in same operation.
embodiment 4
Silica fiber is put at the silica tube middle part of 1 inch of internal diameter, in embodiment 1, the catalyzer 2g of preparation is placed on silica fiber, hydrogen 100sccm flow velocity, 500 ℃ of furnace temperatures, carry out restore 3 hours of catalyzer, then nitrogen enters reaction tubes with 100sccm flow velocity portion, at same temperature, rinses, and the upper demonstration of GC does not have other gaseous constituents except nitrogen.
Butylene flow velocity 50sccm, the mixed gas of nitrogen flow rate 100sccm flows into this reaction silica tube, at 500 ~ 850 ℃ of temperature, carry out scission reaction, reaction terminating after 2 hours, is as cold as room temperature under nitrogen circulation, and CNT (carbon nano-tube) is taken out, tem analysis the structure of nano-sized carbon, the about 2nm of nanometer caliber, the number of plies is 2 layers, accounts for overall 90%.
The crude product obtaining is burnt 1 hour in 300 ℃ of air, then reflux 3 hours with 100 ℃ of concentrated hydrochloric acid aqueous solutions.Filter, repeatedly several times, dry 10 hours of 100 ℃ of the products that obtain, obtain the nano-sized carbon of sterling in same operation.
embodiment 5
step 1: the preparation of catalyzer:
5 grams of cupric nitrates add in 50 ml deionized water, then add Mg (NO3) 26H2O 100g, 100 ℃ of heated and stirred 1 hour, with Rotary Evaporators, methyl alcohol and water major part are removed.By solid in air 100 ℃ start to be sintered to 600 ℃, amount to 8 hours, then within 5 hours, obtain 15 grams of metallic copper magnesium oxide (about cupric 10%) catalyzer with hydrogen reducing.By Ni (NO
3)
26H
2o 15g adds methyl alcohol 500mL, stirring and dissolving, then add metallic copper magnesium oxide 5g, citric acid 20g, the deionized water 200mL of above-mentioned preparation, and 50 ℃ of heated and stirred 1 hour, remove methyl alcohol and water major part with Rotary Evaporators.By solid in air 100 ℃ start to be sintered to 600 ℃, amount to 8 hours, then within 5 hours, obtain metallic copper-metallic nickel-magnesia catalyst (copper/nickel ratio is about 1/6) with hydrogen reducing, weight metal is 40%.
step 2, scission reaction
Silica fiber is put at the silica tube middle part of 1 inch of internal diameter, the catalyzer 2g preparing is above placed on silica fiber, hydrogen 100sccm flow velocity, 500 ℃ of furnace temperatures, carry out restore 3 hours of catalyzer, then nitrogen enters reaction tubes with 100sccm flow velocity portion, at same temperature, rinses, and the upper demonstration of GC does not have other gaseous constituents except nitrogen.
Biogas: main component is methane, wherein also contains 35% carbonic acid gas, 10% oxygen, 4% carbon monoxide, 10% water, 0.5% nitrogen.
Biogas flow velocity 50sccm, the mixed gas of nitrogen flow rate 100sccm flows into this reaction silica tube, at 500 ~ 850 ℃ of temperature, carry out scission reaction, reaction terminating after 2 hours, is as cold as room temperature under nitrogen circulation, and CNT (carbon nano-tube) is taken out, tem analysis the structure of nano-sized carbon, the about 2nm of nanometer caliber, the number of plies is 2 layers, accounts for overall 90%.
Found through experiments, the nickel magnesia catalyst after the second metallic copper adds demonstrates has advantages of long catalytic life.
The Catalyst And Method of cracking hydrocarbon production nano-sized carbon provided by the invention and hydrogen, can eliminate decolorizing carbon presoma or by product, and the raw material that can use gases such as containing carbonic acid gas, oxygen G&W to exist is produced.Final solid product turns out to be pure nano-sized carbon with analyses such as X-ray diffraction and Raman spectrums.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (10)
1. a method of producing nano-sized carbon and hydrogen, it is characterized in that, take hydrocarbon as raw material, under 0 ~ 1MPa pressure, 500 ~ 850 ℃ of temperature condition, catalytic cracking hydrocarbon obtains nano-sized carbon crude product and hydrogen, and nano-sized carbon crude product is calcined to 0.8 ~ 1.5h at 250 ~ 400 ℃, then 2 ~ 5h refluxes in concentrated hydrochloric acid, collect solid, dry, obtain pure nano-sized carbon.
2. the method for production nano-sized carbon according to claim 1 and hydrogen, is characterized in that, any one or a few in the hydrocarbon that described raw material is C1 ~ C5, or contain in C1 ~ C5 hydrocarbon any one mixed gas.
3. the method for production nano-sized carbon according to claim 2 and hydrogen, is characterized in that, described raw material is methane, ethane, propane, butane, ethene, propylene, divinyl, pentane or the mixed gas that contains above-mentioned any hydrocarbon.
4. the method for production nano-sized carbon according to claim 1 and hydrogen, is characterized in that, the active metal of described cracking hydrocarbon used catalyst is any one or a few the mixture in iron, nickel, cobalt.
5. the method for production nano-sized carbon according to claim 4 and hydrogen, is characterized in that, described catalyzer also comprises carrier, and described carrier is selected from any one or a few mixture of magnesium oxide, aluminum oxide, silicon oxide.
6. for cracking hydrocarbon, prepare a catalyzer for nano-sized carbon and hydrogen, it is characterized in that, described catalyzer comprises active metal and carrier, and described active metal is selected from any one or a few in Ni, Co, Fe.
7. catalyzer according to claim 6, is characterized in that, the weight percent of described active metal catalyst is 30 ~ 80%.
8. catalyzer according to claim 6, is characterized in that, also comprises the second metal in described catalyzer.
9. a method of preparing catalyzer claimed in claim 7, is characterized in that, the preparation process of described catalyzer comprises:
In reaction solvent, M (NO
3)
x, metal compound and organic carboxyl acid be at 40 ~ 55 ℃ of reaction 0.5 ~ 2h, then removes solvent; At 8 ± 0.5h, be interiorly warming up to 600 ± 5 ℃ by solid sintering from 100 ± 5 ℃, then with hydrogen reducing, obtain described metal M-oxide catalyst, M (NO
3)
xbe selected from Ni (NO
3)
2, Co (NO
3)
2, or Fe (NO
3)
3; Metal compound is selected from Mg (NO
3)
2, Al (NO
3)
3, SiO
2, Al
2o
3.
10. method according to claim 9, is characterized in that, the preparation process of described catalyzer comprises: in reaction solvent, and M (NO
3)
x, M
2(NO
3)
ymetal compound and organic carboxyl acid, at 40 ~ 55 ℃ of reaction 0.5 ~ 2h, are then removed solvent; At 8 ± 0.5h, be interiorly warming up to 600 ± 5 ℃ by solid sintering from 100 ± 5 ℃, then with hydrogen reducing, obtain described metal M-M
2oxide catalyst, M
2(NO
3)
yit is the second metal nitrate.
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|---|---|---|---|
| CN201210252175.2A CN103569993A (en) | 2012-07-20 | 2012-07-20 | Catalyst and method for producing nanometer carbon and hydrogen |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210252175.2A CN103569993A (en) | 2012-07-20 | 2012-07-20 | Catalyst and method for producing nanometer carbon and hydrogen |
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| Publication Number | Publication Date |
|---|---|
| CN103569993A true CN103569993A (en) | 2014-02-12 |
Family
ID=50042804
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| CN201210252175.2A Pending CN103569993A (en) | 2012-07-20 | 2012-07-20 | Catalyst and method for producing nanometer carbon and hydrogen |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108584871A (en) * | 2018-05-08 | 2018-09-28 | 黎晟 | The technique and system of carbon nanomaterial and hydrogen are recycled from the organic waste of city |
| CN113896183A (en) * | 2021-10-22 | 2022-01-07 | 北京化工大学 | Method for growing carbon nano material by solar drive |
-
2012
- 2012-07-20 CN CN201210252175.2A patent/CN103569993A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108584871A (en) * | 2018-05-08 | 2018-09-28 | 黎晟 | The technique and system of carbon nanomaterial and hydrogen are recycled from the organic waste of city |
| CN113896183A (en) * | 2021-10-22 | 2022-01-07 | 北京化工大学 | Method for growing carbon nano material by solar drive |
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