CN102730673A - Apparatus and method for continuously preparing thin-layer grapheme or hybrid combining thin-layer grapheme with thin-walled carbon nanotube - Google Patents
Apparatus and method for continuously preparing thin-layer grapheme or hybrid combining thin-layer grapheme with thin-walled carbon nanotube Download PDFInfo
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Abstract
The invention discloses an apparatus for continuously preparing thin-layer grapheme or a hybrid combining the thin-layer grapheme with thin-walled carbon nanotube and a preparation method of the thin-layer grapheme or the hybrid combining the thin-layer grapheme with the thin-walled carbon nanotube by utilizing the apparatus, which belongs to the field of multiphase flow reactor technology and carbon nanomaterial preparation. The apparatus provided by the invention comprises a downer, a riser and a heating system wrapped on the outside of the riser for heating up. According to the method, the heating system is started; reaction gas and a template are led through the entrance of a gas-solid mixture of the downer to grow thin-layer grapheme, or the reaction gas and a catalyst are led to grow hybrid of thin-layer grapheme and thin-walled carbon nanotube; and then the reaction gas is led through the a gas inlet of the riser; all gas-solid mixture moves forward, passes through a member area, gets out of the riser and enters a subsequent gas-solid separation section and a cooling and storage section. The apparatus provided by the invention has the advantages of simplicity in structure and low cost of equipment. The method provided by the invention has low environmental pollution and the obtained product has high quality.
Description
Technical field
The invention belongs to polyphasic flow reactor technology and carbon nanomaterial preparation field, be specifically related to a kind ofly prepare the device of thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid and utilize this device to prepare the method for thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid.
Background technology
Thin layer Graphene (1-10 layer) or thin layer Graphene and thin wall carbon nano-tube (1-3 wall; Diameter is mostly between 0.6 ~ 4 nm; Length can reach hundreds of micron even tens of centimetres) hybrid; Have good electrical conductivity, thermal conductivity, mechanical property and huge specific surface area, can be widely used in fields such as high molecular enhancing, electro-conductive material, field emmision material, suction ripple or electromagnetic shielding material, support of the catalyst, nanometer circuit, electrochemical energy storage.The preparation method of the hybrid of typical thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube is a chemical Vapor deposition process, promptly uses metal-free template, or metallic catalyzer; Under 400 ~ 1400 ℃; Through carbon source (like hydro carbons, alcohols, CO; Ethers, or ketone etc.) decomposition and deposition and get.
At present; The process of preparation thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid is mainly carried out in fixed-bed reactor or the mobile up fluidized-bed reactor of gas-solid, because template or catalyzer overstand in reactor drum are prone to produce 10 layers of multi-layer graphenes (>); The thick multi-walled carbon nano-tubes of diameter (the wall number>5); And the impurity such as metal nanoparticle that coat of decolorizing carbon, carbon, so the purge process of product is complicated, with high costs.Utilize the thin layer Graphene that the reactor drum of drum-type can depositing large-area, but can't prepare the hybrid of itself and thin wall carbon nano-tube.Large-area thin layer Graphene is mainly used in fields such as nanometer circuit or electrically conducting transparent demonstration simultaneously, but thin layer Graphene preparation cost is high, and output is very little, can not satisfy the application demand in these two fields; And the application of aspects such as electrochemical energy storage and support of the catalyst inconvenient (pile up easily, and cause specific surface area to reduce).Preparation thin wall carbon nano-tube and thin layer Graphene are assembled into its hybrid then, usually need utilize the functional group on the graphene oxide to carry out organic assembling, but need remove these functional groups during subsequent applications, and purifying is with high costs.Because technical defective and bottleneck, cause the absolute yield of hybrid of present international thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube very low, cost an arm and a leg, seriously limited its applied research and commercialization.
Summary of the invention
In order to overcome above-mentioned shortcoming, the present invention proposes a kind of device for preparing thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid, the structure of this device is following:
(1) descending bed 1: the import 11 of descending bed gas-solid mixture is arranged on the top of descending bed 1; The outlet 12 of descending bed gas-solid mixture is arranged in the bottom of descending bed 1;
(2) riser tubes 2: the outlet 23 of riser tube gas-solid mixture is arranged on riser tube 2 tops; Riser tube 2 inner side-walls are member district 22; In riser tube 2 bottoms pyramidal structure 25 is arranged; Riser tube gas feed 21 is to remove a plurality of symmetric nozzle in the pyramidal structure 25 shared extra-regional zones along riser tube 2 bottoms;
(3) described descending bed 1 is inserted in the described riser tube 2; It is riser tube 2 and descending bed 1 heating that heating system 24 is wrapped in riser tube 2 outsides; The outlet 12 of descending bed gas-solid mixture is adjacent with the upper end of the pyramidal structure 25 in the riser tube 2; The sectional area of descending bed 1 is 1 ~ 10 times of riser tube 2 sectional areas.
It is following that the another kind that the present invention proposes prepares the apparatus structure of thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid:
(1) descending bed 1: the import 11 of descending bed gas-solid mixture is arranged on the top of descending bed 1; The outlet 12 of the descending bed gas-solid mixture that is arranged on riser tube gas feed 21 1 sides is arranged in the bottom of descending bed 1;
(2) riser tubes 2: riser tube 2 inner side-walls are member district 22; A vertical partition plate 26 that is positioned at riser tube 2 middle parts; Described vertical partition plate 26 is divided into riser tube 2 in two the equal zones of volume that only communicate at the top; Riser tube gas feed 21 is for being arranged on a plurality of nozzles of vertical partition plate 26 1 sides; The outlet 23 of riser tube gas-solid mixture is for being arranged on a plurality of nozzles of vertical partition plate 26 opposite sides;
(3) described descending bed 1 is inserted in the described riser tube 2; It is riser tube 2 and descending bed 1 heating that heating system 24 is wrapped in riser tube 2 outsides; The sectional area of descending bed 1 is 1 ~ 10 times of riser tube 2 sectional areas.
A kind ofly utilize above-mentioned first kind of device for preparing thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid to prepare the method for thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid, comprise the steps:
(1) opens heating system 24, descending bed 1 is heated to 300 ~ 1400 ℃ with riser tube 2, and keep heated condition;
(2) import 11 from descending bed gas-solid mixture feeds reactant gases and template, thin layer graphene; Or feed reactant gases and catalyzer, thin layer graphene and thin wall carbon nano-tube hybrid from the import 11 of descending bed gas-solid mixture; Gas that is generated and template, thin layer Graphene or gas and catalyzer, thin layer Graphene come out from the outlet 12 of descending bed gas-solid mixture with the thin wall carbon nano-tube hybrid, get into the bottom of riser tube 2;
(3) the riser tube gas feed 21 from riser tube 2 feeds reactant gases; Make the gas composition that is arranged in riser tube gas feed 21 near zones in the riser tube 2, hydrogen is identical with the ratio of carbon source with the hydrogen at import 11 places of descending bed gas-solid mixture with the volume ratio of carbon source; All gas-solid mixture moves upward, and through member district 22, goes out riser tube 2 from the outlet 23 of riser tube gas-solid mixture, gets into the gas solid separation workshop section and cooling, storage workshop section of postorder;
Repeating step (1) is to step (3), and thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid are produced in serialization.
A kind ofly utilize above-mentioned second kind of device for preparing thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid to prepare the method for thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid, comprise the steps:
(1) opens heating system 24, descending bed 1 is heated to 300 ~ 1400 ℃ with riser tube 2, and keep heated condition;
(2) import 11 from descending bed 1 gas-solid mixture feeds reactant gases and template, thin layer graphene; Or feed reactant gases and catalyzer, thin layer graphene and thin wall carbon nano-tube hybrid from the import 11 of descending bed gas-solid mixture; Gas that is generated and template, thin layer Graphene or gas and catalyzer, thin layer Graphene come out from the outlet 12 of the descending bed gas-solid mixture of descending bed 1 with the thin wall carbon nano-tube hybrid, get into the bottom of riser tube 2;
(3) feed reactant gases from riser tube gas feed 21; Make the gas composition that is arranged in riser tube gas feed 21 near zones in the riser tube 2, hydrogen is identical with the ratio of carbon source with the hydrogen at import 11 places of the descending bed gas-solid mixture of descending bed 1 with the volume ratio of carbon source; All gas-solid mixture moves upward; Through member district 22; To the top of riser tube 2, move downward after walking around vertical partition plate 26, through the member district 22 of opposite side; Outlet 23 by the riser tube gas-solid mixture goes out riser tube 2, the gas solid separation workshop section of entering postorder and cooling, storage workshop section;
Repeating step (1) can be continuously produced thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid to step (3).
The template of described thin layer graphene is metal-free mineral compound; Like in aluminium sesquioxide, silicon oxide, zirconium white, Natural manganese dioxide, zinc oxide, Si-Al molecular sieve, Al-Mg-O type hydrotalcite, the silit one or more; Particle diameter is 20nm ~ 500 μ m, and tap density is 200 ~ 1800 kg/m
3
The catalyzer of described thin layer graphene and thin wall carbon nano-tube hybrid is the nano metal loaded catalyst; Said activity of such catalysts component is one or more in iron, nickel, the cobalt; Auxiliary agent is one or more in molybdenum, tungsten, manganese, vanadium, the copper; Carrier is one or more in aluminium sesquioxide, silicon oxide, zirconium white, Natural manganese dioxide, Si-Al molecular sieve, the Al-Mg-O type hydrotalcite; The mass ratio of active ingredient in catalyzer is 0.1% ~ 10%, and the mass ratio of auxiliary agent in catalyzer is 0 ~ 10%, and the ratio of carrier in catalyzer is 90% ~ 99.9%; Granularity is 20 nm ~ 500 μ m, and tap density is 200 ~ 1800 kg/m
3
Described reactant gases refers to the mixture of carbon source or carbon source and hydrogen and/or rare gas element; Carbon source refers to that molecular weight is not more than the compound of 150 carbon elements, as includes but not limited to CO, C1 ~ C9 hydro carbons, alcohols, ethers, ketone etc.; When preparing nitrogenous thin layer Graphene or nitrogenous thin layer Graphene and nitrogenous thin wall carbon nano-tube hybrid; Then in above-mentioned reactant gases, add the small amount of nitrogen compounds; As include but not limited to ammonia, aliphatic amide (like methylamine) or aromatic amine (like aniline or pyridine etc.); If the mixture of described reactant gases carbon source and hydrogen and/or rare gas element, then the volume ratio of the mixture of carbon source and hydrogen and/or rare gas element is 1:1 ~ 1:200; The volume ratio of carbon source and nitrogenous compound is 100:1 ~ 20:1; Described rare gas element is one or more in helium, argon gas, the nitrogen;
Operating gas velocity in the descending bed 1 is 0.1 ~ 2m/s, and the operating gas velocity in the riser tube 2 is 1 ~ 20m/s, and the carbon source air speed is 0.2 ~ 800g/gcat/h.
Beneficial effect of the present invention is:
(1) descending bed and the shared heating system of riser reactor, simple in structure, equipment manufacturing cost is low; Also very easy aspect the reactor drum installation support of reality, easy handling;
(2) import of supplementary carbon source is provided in the riser tube; Key conditions such as the temperature that can make the hybrid growth that is suitable for thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube in the riser tube and gas concentration keep stablizing, thereby make the thin layer Graphene of acquisition or thin layer Graphene higher than existing reactors with the purity of the hybrid of thin wall carbon nano-tube;
(3) utilize method of the present invention, both can use very little template, make the graphene film that size is merely 20 ~ 50nm, supply in the electrochemical energy storage process, to use with the other materials compound tense; Also can use bigger template, preparation size is the graphene film of big (500 μ m), supplies the compound use of polymer; Simultaneously, can pass through more catalyst changeout and processing condition (like temperature, gas speed etc.) easily, prepare the Graphene of the different numbers of plies and the hybrid of the carbon nanotube of different wall numbers, and the mass ratio of accurately controlling two types of materials in the hybrid; Simultaneously, can also directly synthesize nitrogenous Graphene or nitrogenous carbon nanotube through regulating carbon source or nitrogenous source, applied widely;
(4) descending bed is lacked (being merely several seconds) with the total reaction time in the riser tube, makes on the catalyzer the very little metal grain preferred growth thin layer Graphene or the hybrid of thin layer Graphene and thin wall carbon nano-tube; Most of catalyzer coalescence that also is not able to do in time just is moved out of reaction zone, and the multi-walled carbon nano-tubes that therefore generates reduces with the ratio of the metal nanoparticle of carbon coating significantly;
(5) high cycle speed in the riser tube, solid (support of the catalyst or template, and thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid) is with gas flow; During through the member district, because member has occupied certain reaction device space, causing here, gas speed increases; Make solid and member produce the intensive rubbing effect; Cause the thin layer Graphene to separate, or the thin layer Graphene separates with the thin wall carbon nano-tube hybrid with template, be easy to purifying with support of the catalyst; Particularly effectively separation chemistry character is more stable than SWCN; But density is greater than the multi-walled carbon nano-tubes of SWCN and the metal nanoparticle of carbon coating; Purifying products is handled (mainly to be comprised: remove catalyzer or template carrier with acid; Remove decolorizing carbon and multi-walled carbon nano-tubes etc. with thermal oxidation method or hydrothermal treatment consists method) step simplify, cost reduces by 60 ~ 85%; Simultaneously practice thrift sour consumption significantly, alleviated environmental pollution.
Above-mentioned complex art advantage makes and produces 99.9% even the cost of the product of the hybrid of more highly purified thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube in the present technique, than 5 ~ 50 times of prior art reductions.
Description of drawings
Fig. 1: a figure is when the bottom of riser tube configuration pyramidal structure, apparatus structure of the present invention and schematic flow sheet; B figure is the nozzle orientation synoptic diagram of a figure shown device;
Fig. 2: a figure is when the bottom of riser tube configuration vertical partition plate, apparatus structure of the present invention and schematic flow sheet; B figure is the nozzle orientation synoptic diagram of a figure shown device.
Embodiment
Below in conjunction with accompanying drawing and concrete embodiment the present invention is done further detailed explanation:
As shown in Figure 1, the preparation thin layer Graphene that the present invention proposes or the apparatus structure of thin layer Graphene and thin wall carbon nano-tube hybrid are following:
(1) descending bed 1: the import 11 of descending bed gas-solid mixture is arranged on the top of descending bed 1; The outlet 12 of descending bed gas-solid mixture is arranged in the bottom of descending bed 1;
(2) riser tubes 2: the outlet 23 of riser tube gas-solid mixture is arranged on riser tube 2 tops; Riser tube 2 inner side-walls are member district 22; In riser tube 2 bottoms pyramidal structure 25 is arranged; Riser tube gas feed 21 is to remove a plurality of symmetric nozzle in the pyramidal structure 25 shared extra-regional zones along riser tube 2 bottoms;
(3) described descending bed 1 is inserted in the described riser tube 2; It is riser tube 2 and descending bed 1 heating that heating system 24 is wrapped in riser tube 2 outsides; The outlet 12 of descending bed gas-solid mixture is adjacent with the upper end of the pyramidal structure 25 in the riser tube 2; The sectional area of descending bed 1 is 1 ~ 10 times of riser tube 2 sectional areas.
Use device as shown in Figure 1 to prepare the method for thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid, comprise the steps:
(1) opens heating system 24, descending bed 1 is heated to 300 ~ 1400 ℃ with riser tube 2, and keep heated condition;
(2) import 11 from descending bed gas-solid mixture feeds reactant gases and template, thin layer graphene; Or feed reactant gases and catalyzer, thin layer graphene and thin wall carbon nano-tube hybrid from the import 11 of descending bed gas-solid mixture; Gas that is generated and template, thin layer Graphene or gas and catalyzer, thin layer Graphene come out from the outlet 12 of descending bed gas-solid mixture with the thin wall carbon nano-tube hybrid, get into the bottom of riser tube 2;
(3) the riser tube gas feed 21 from riser tube 2 feeds reactant gases; Make the gas composition that is arranged in riser tube gas feed 21 near zones in the riser tube 2, hydrogen is identical with the ratio of carbon source with the hydrogen at import 11 places of descending bed gas-solid mixture with the volume ratio of carbon source; All gas-solid mixture moves upward, and through member district 22, goes out riser tube 2 from the outlet 23 of riser tube gas-solid mixture, gets into the gas solid separation workshop section and cooling, storage workshop section of postorder.
Repeating step (1) can be continuously produced thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid to step (3).
As shown in Figure 2, the another kind of structure of the preparation thin layer Graphene that the present invention proposes or the device of thin layer Graphene and thin wall carbon nano-tube hybrid is following:
(1) descending bed 1: the import 11 of descending bed gas-solid mixture is arranged on the top of descending bed 1; The outlet 12 of the descending bed gas-solid mixture that is arranged on riser tube gas feed 21 1 sides is arranged in the bottom of descending bed 1;
(2) riser tubes 2: riser tube 2 inner side-walls are member district 22; A vertical partition plate 26 that is positioned at riser tube 2 middle parts; Described vertical partition plate 26 is divided into riser tube 2 in two the equal zones of volume that only communicate at the top; Riser tube gas feed 21 is for being arranged on a plurality of nozzles of vertical partition plate 26 1 sides; The outlet 23 of riser tube gas-solid mixture is for being arranged on a plurality of nozzles of vertical partition plate 26 opposite sides;
(3) described descending bed 1 is inserted in the described riser tube 2; It is riser tube 2 and descending bed 1 heating that heating system 24 is wrapped in riser tube 2 outsides; The sectional area of descending bed 1 is 1 ~ 10 times of riser tube 2 sectional areas.
Use device as shown in Figure 2 to prepare the method for thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid, comprise the steps:
(1) opens heating system 24, descending bed 1 is heated to 300 ~ 1400 ℃ with riser tube 2, and keep heated condition;
(2) import 11 from descending bed 1 gas-solid mixture feeds reactant gases and template, thin layer graphene; Or feed reactant gases and catalyzer, thin layer graphene and thin wall carbon nano-tube hybrid from the import 11 of descending bed gas-solid mixture; Gas that is generated and template, thin layer Graphene or gas and catalyzer, thin layer Graphene come out from the outlet 12 of the descending bed gas-solid mixture of descending bed 1 with the thin wall carbon nano-tube hybrid, get into the bottom of riser tube 2;
(3) feed reactant gases from riser tube gas feed 21; Make the gas composition that is arranged in riser tube gas feed 21 near zones in the riser tube 2, hydrogen is identical with the ratio of carbon source with the hydrogen at import 11 places of the descending bed gas-solid mixture of descending bed 1 with the volume ratio of carbon source; All gas-solid mixture moves upward; Through member district 22; To the top of riser tube 2, move downward after walking around vertical partition plate 26, through the member district 22 of opposite side; Outlet 23 by the riser tube gas-solid mixture goes out riser tube 2, the gas solid separation workshop section of entering postorder and cooling, storage workshop section.
Repeating step (1) can be continuously produced thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid to step (3).
Use reaction unit as shown in Figure 1, wherein descending bed 1 is 3:1 with the ratio of the sectional area of riser tube 2, and (the Fe mass ratio is 1.2%, and all the other are MgO, and particle diameter is 100 microns, and tap density is 1600 kg/m to use the Fe/MgO catalyzer
3), reactant gases is the gas mixture (methane: hydrogen: argon: the volume ratio of nitrogen is 2:7:300:100) of methane, hydrogen, argon gas and nitrogen, the total air speed of carbon source is 300 g/gcat/h; Reactant gases and catalyzer are fed descending bed 1, are the hybrid of generation single-layer graphene and SWCN under the condition of 0.1m/s at 800 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures from descending bed gas-solid mixture get into the bottom of riser tube 2, replenish methane through riser tube gas feed 21, make methane: the volume ratio of hydrogen still keeps 2:7; At 800 ℃, gas speed is under the condition of 1 ~ 1.5m/s, through member district 22, goes out riser tube 2 from the outlet 23 of riser tube gas-solid mixture.Products obtained therefrom contains the metal nanoparticle that 33% single-layer graphene (carbon back) and 65% SWCN, 0.2% decolorizing carbon, 1% carbon coat, and 0.8% diameter is the multi-walled carbon nano-tubes of 5 ~ 9 nm.
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 1.2:1 with the ratio of the sectional area of riser tube 2, uses Ni/Mo/SiO
2(the Ni mass ratio is 1% to catalyzer, and the Mo mass ratio is 0.5%, and all the other are SiO
2, particle diameter is 400 microns, tap density is 500 kg/m
3), reactant gases is the gas mixture (acetylene: ethene: the volume ratio of hydrogen is 2:2:4) of acetylene, ethene, hydrogen, the total air speed of carbon source is 20g/gcat/h; Reactant gases and catalyzer are fed descending bed 1, are the hybrid of generation Graphene and carbon nanotube under the condition of 2m/s at 450 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures of descending bed gas-solid mixture get into the bottom of riser tubes 2; Replenish acetylene and ethene through riser tube gas feed 21; Make acetylene: ethene: the volume ratio of hydrogen still keeps 2:2:4, is under the condition of 3 ~ 4 m/s at 450 ℃, gas speed, through the member district 22 of riser tube gas feed 21 ends; Arrive riser tube 2 tops; Behind vertical partition plate 26 tops, move downward, pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, go out riser tube 2 from the outlet 23 of riser tube gas-solid mixture.Products obtained therefrom contains the metal nanoparticle of 28% single-layer graphene, 36% SWCN (carbon back), 32.6% double-walled carbon nano-tube, 0.4 % decolorizing carbon, the coating of 0.5% carbon, and 0.5% diameter is the multi-walled carbon nano-tubes of 5 ~ 10 nm.
Embodiment 3
Use reaction unit as shown in Figure 1, wherein descending bed 1 is 4:1 with the ratio of the sectional area of riser tube 2, Fe/V/Al
2O
3(the Fe mass ratio is 1% to catalyzer, and the V mass ratio is 0.2%, and all the other are Al
2O
3, particle diameter is 500 nm, tap density is 500 kg/m
3), reactant gases is the gas mixture (ethanol: methyl alcohol: the volume ratio of hydrogen is 2:0.5:500) of ethanol, methyl alcohol, hydrogen, the total air speed of carbon source is 50 g/gcat/h; Reactant gases and catalyzer are fed descending bed 1, and at 900 ℃, gas speed is for generating thin wall carbon nano-tube under the condition of 1m/s; When the outlet 12 effusive gas-solid mixtures of descending bed gas-solid mixture get into the bottom of riser tubes 2; Riser tube gas feed 21 through riser tube 2 replenishes ethanol and methyl alcohol; Make acetylene: ethene: the volume ratio of hydrogen still keeps 2:0.5:500; At 900 ℃, gas speed is under 16 ~ 18 m/s, and through member district 22, the outlet 23 from the riser tube gas-solid mixture goes out riser tube then.Products obtained therefrom contains the metal nanoparticle of 36% SWCN (carbon back), 26% double-walled carbon nano-tube, 37% 3-5 layer graphene, 0.2% decolorizing carbon, the coating of 0.1% carbon, and 0.1% diameter is the multi-walled carbon nano-tubes of 5 ~ 12 nm.
Embodiment 4
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 9:1 with the ratio of the sectional area of riser tube 2, and (the Fe mass ratio is 1% to use Fe/W/ Si-Al molecular sieve catalyzer; The W mass ratio is 10%; All the other are Si-Al molecular sieve, and particle diameter is 70 microns, and tap density is 800 kg/m
3), reactant gases is the gas mixture (volume ratio of argon is 2:0.1:400 for hexanaphthene, pyridine) of hexanaphthene, pyridine and argon gas, the total air speed of carbon source is 800g/gcat/h; Reactant gases and catalyzer are fed descending bed 1, generate thin wall carbon nano-tube under the condition of 0.2m/s at 950 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures from descending bed gas-solid mixture get into the bottom of riser tube 2; Riser tube gas feed 21 complementary ring hexanes through riser tube 2; Make hexanaphthene: the volume ratio of pyridine still keeps 2:0.1, is under the condition of 18 ~ 20 m/s at 950 ℃, gas speed, through the member district 22 of riser tube gas feed 21 ends; Arrive riser tube 2 tops; Behind vertical partition plate 26 tops, move downward, pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.Products obtained therefrom contains the metal nanoparticle of 90.2% SWCN (carbon back), 6% single-layer graphene, 1% decolorizing carbon, the coating of 2% carbon, and 0.8% diameter is the multi-walled carbon nano-tubes of 5 ~ 12 nm.
Embodiment 5
Use reaction unit as shown in Figure 1, wherein descending bed 1 is 5:1 with the ratio of the sectional area of riser tube 2, uses Fe/Co/Zr
2O
3(the Fe mass ratio is 9% to catalyzer, and the Co mass ratio is 1%, and all the other are Zr
2O
3, particle diameter is 200 nm, tap density is 220 kg/m
3), reactant gases is the gas mixture (YLENE: hydrogen: the volume ratio of helium is 2:1:1) of YLENE, hydrogen and helium, the total air speed of carbon source is 20g/gcat/h; Reactant gases and catalyzer are fed descending bed 1, are the hybrid of generation Graphene and carbon nanotube under the condition of 0.2m/s at 750 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures of descending bed gas-solid mixture get into the bottom of riser tubes 2; Riser tube gas feed 21 through riser tube 2 replenishes YLENE; Make YLENE: the volume ratio of hydrogen still keeps 2:1; At 750 ℃, gas speed is under 5 ~ 6 m/s, and through member district 22, the outlet 23 from the riser tube gas-solid mixture goes out riser tube then.Products obtained therefrom contains the metal nanoparticle of 77% double-walled carbon nano-tube (carbon back), 21.98% 2 ~ 4 layer graphene, 1% decolorizing carbon, the coating of 0.02% carbon.
Embodiment 6
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 3:1 with the ratio of the sectional area of riser tube 2, uses Fe/Mn/SiO
2(the Fe mass ratio is 0.5% to catalyzer, and the Mn mass ratio is 0.2%, and all the other are SiO
2, particle diameter is 20 microns, tap density is 1020 kg/m
3), reactant gases is the gas mixture (propylene: MTBE: hydrogen: the volume ratio of argon is 2:0.1:4:0.5) of propylene, MTBE, hydrogen and argon gas, the total air speed of carbon source is 800 g/gcat/h; Reactant gases and catalyzer are fed descending bed 1, are the hybrid of generation Graphene and carbon nanotube under the condition of 0.3m/s at 600 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures of descending bed gas-solid mixture get into the bottom of riser tubes 2; Riser tube gas feed 21 through riser tube 2 replenishes propylene, MTBE; Make propylene: MTBE: the volume ratio of hydrogen still keeps 2:0.1:4, is under the condition of 3 ~ 4 m/s at 600 ℃, gas speed, through the member district 22 of riser tube gas feed 21 ends; Arrive riser tube 2 tops; Behind vertical partition plate 26 tops, move downward, pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.Products obtained therefrom contains the metal nanoparticle of 6.7% double-walled carbon nano-tube (carbon back), 34% 3 wall carbon nano tube, 34 % single-layer graphenes, 24 % double-layer graphite alkene, 0.8% decolorizing carbon, the coating of 0.5% carbon.
Embodiment 7
Use reaction unit as shown in Figure 1, wherein descending bed 1 is 1:1 with the ratio of the sectional area of riser tube 2, and (the Co mass ratio is 0.5%, and the Cu mass ratio is 0.2%, and all the other are MgO, and particle diameter is 20 nm, and tap density is 200 kg/m to use the Co/Cu/MgO catalyzer
3), reactant gases is the gas mixture (methane: hydrogen: the volume ratio of argon is 2:150:50) of methane, hydrogen and argon gas, the total air speed of carbon source is 30 g/gcat/h; Reactant gases and catalyzer are fed descending bed 1, are the hybrid that generates Graphene and carbon nanotube under the condition of 1.8 m/s at 850 ℃, gas speed.When the outlet 12 effusive gas-solid mixtures from descending bed gas-solid mixture get into the bottom of riser tube 2; Replenish methane through riser tube gas feed 21; Make methane: the volume ratio of hydrogen still keeps 2:150; At 850 ℃, gas speed is under 2 ~ 3 m/s, and through member district 22, the outlet 23 from the riser tube gas-solid mixture goes out riser tube then.Products obtained therefrom contains the metal nanoparticle of 50% SWCN (carbon back), 49.5 %, 3 layer graphenes, 0.2% decolorizing carbon, the coating of 0.3% carbon.
Embodiment 8
Use reaction unit as shown in Figure 2; Wherein descending bed 1 is 2:1 with the ratio of the sectional area of riser tube 2; (the Co mass ratio is 0.1%, and the Mo mass ratio is 0.05%, and all the other are Al-Mg-O hydrotalcite type catalyzer to use Co/Mo/Al-Mg-O hydrotalcite type catalyzer; Particle diameter is 80 microns, and tap density is 720 kg/m
3), reactant gases is the gas mixture (methane: ammonia: hydrogen: the volume ratio of argon is 2:0.02:2:3) of methane, ammonia, hydrogen and argon gas, the total air speed of carbon source is 120 g/gcat/h; Reactant gases and catalyzer are fed descending bed 1, are the hybrid of generation Graphene and carbon nanotube under the condition of 2m/s at 760 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures of descending bed gas-solid mixture get into the bottom of riser tubes 2; Replenish methane and ammonia through riser tube gas feed 21; Make methane: ammonia: the volume ratio of hydrogen still keeps 2:0.02:2, is under the condition of 9 ~ 10 m/s at 760 ℃, gas speed, through the member district 22 of riser tube gas feed 21 ends; Arrive riser tube 2 tops; Behind vertical partition plate 26 tops, move downward, pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.Products obtained therefrom contains the metal nanoparticle of 90% SWCN (carbon back), 8% double-walled carbon nano-tube, 1.8% double-layer graphite alkene, 0.1% decolorizing carbon, the coating of 0.1% carbon, and the nitrogen content in the above-mentioned hybrid is 0.5%.
Embodiment 9
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 2:1 with the ratio of the sectional area of riser tube 2, uses Fe/Ni/SiO
2(Fe content is 0.1% to catalyzer, and Ni content is 0.1%, and all the other are SiO
2, particle diameter is 20 nm, tap density is 220 kg/m
3), reactant gases uses the gas mixture (methane: hydrogen: the volume ratio of helium is 2:5:30) of methane, hydrogen and helium, and the total air speed of carbon source is 0.2 g/gcat/h; Reactant gases and catalyzer are fed descending bed 1, are the hybrid that generates Graphene and carbon nanotube under the condition of 1.8 m/s at 880 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures of descending bed gas-solid mixture get into the bottom of riser tubes 2; Replenish methane through riser tube gas feed 21, make methane: the volume ratio of hydrogen still keeps 2:5, at 880 ℃; Gas speed is under the condition of 8 ~ 10m/s; Through the member district 22 of riser tube gas feed 21 ends, arrive riser tube 2 tops, behind vertical partition plate 26 tops, move downward; Pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.Products obtained therefrom contains the metal nanoparticle of 70% SWCN (carbon back), 20% double-walled carbon nano-tube, 9.8% single-layer graphene, 0.1% decolorizing carbon, the coating of 0.1% carbon.
Embodiment 10
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 4:1 with the ratio of the sectional area of riser tube 2, uses ZrO
2(particle diameter is 20 μ m to template, and tap density is 1800 kg/m
3), reactant gases is the gas mixture (methane: hydrogen: the volume ratio of argon is 1:100:100) of methane, hydrogen and argon gas, the total air speed of carbon source is 20 g/gcat/h; Reactant gases and template are fed descending bed 1, generate Graphene under the condition of 0.25m/s at 1400 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures from descending bed gas-solid mixture get into the bottom of riser tube 2; Replenish methane through riser tube gas feed 21, make the volume ratio of methane and hydrogen still keep 1:100, at 1400 ℃; Gas speed is under the condition of 4.5 ~ 6 m/s; Through the member district 22 of riser tube gas feed 21 ends, arrive riser tube 2 tops, behind vertical partition plate 26 tops, move downward; Pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.Products obtained therefrom contains 70% double-layer graphite alkene (carbon back), 18% 3 layer graphenes, 7% 4-10 layer graphene, 5% decolorizing carbon.
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 2:1 with the ratio of the sectional area of riser tube 2, and (particle diameter is 60 nm, and tap density is 200 kg/m to use Al-Mg-O hydrotalcite type template
3), reactant gases is the gas mixture (methane: the volume ratio of hydrogen is 2:2) of methane, hydrogen, the total air speed of carbon source is 60 g/gcat/h.Reactant gases and template are fed descending bed 1, generate Graphene under the condition of 2m/s at 600 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures from descending bed gas-solid mixture get into the bottom of riser tube 2; Replenish methane through riser tube gas feed 21; Making the volume ratio of methane and hydrogen still keep 2:2, is under the condition of 9 ~ 10m/s at 600 ℃, gas speed, through the member district 22 of riser tube gas feed 21 ends; Arrive riser tube 2 tops; Behind vertical partition plate 26 tops, move downward, pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.Products obtained therefrom contains 70% 3 layer graphenes (carbon back), 28% 4 layer graphenes, 1.5% 5-10 layer graphene, 0.5% decolorizing carbon.
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 2:1 with the ratio of the sectional area of riser tube 2, and (particle diameter is 200 nm, and tap density is 420 kg/m to use the Si-Al molecular sieve template
3), reactant gases is the gas mixture (ethanol: the helium volume ratio is 2:2) of ethanol and helium, the total air speed of carbon source is 0.2 g/gcat/h; Reactant gases and template are fed descending bed 1, generate Graphene under the condition of 2m/s at 300 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures of descending bed gas-solid mixture get into the bottom of riser tubes 2; Replenish ethanol through riser tube gas feed 21; Making the volume ratio of ethanol and helium still keep 2:2, is under the condition of 9 ~ 10m/s at 300 ℃, gas speed, through the member district 22 of riser tube gas feed 21 ends; Arrive riser tube 2 tops; Behind vertical partition plate 26 tops, move downward, pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.The gained carbon products contains 40% double-layer graphite alkene (carbon back), 48% 3 layer graphenes, 11.9% 4-10 layer graphene, 0.1% decolorizing carbon.
Embodiment 13
Use reaction unit as shown in Figure 1, wherein descending bed 1 is 4:1 with the ratio of the sectional area of riser tube 2, and (particle diameter is 150 microns, and tap density is 820 kg/m to use the MgO template
3), reactant gases is the gas mixture (methane: aniline: acetone: hydrogen: the volume ratio of helium is 2:0.1:0.3:6:2) of methane, aniline, acetone, hydrogen and helium, the total air speed of carbon source is 300 g/gcat/h; Reactant gases and template are fed descending bed 1, are to generate Graphene under the condition of 0.5 m/s at 900 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures of descending bed gas-solid mixture get into the bottom of riser tubes 2; Replenish methane, aniline, acetone through riser tube gas feed 21; Make methane: aniline: acetone: the volume ratio of hydrogen still keeps 2:0.1:0.3:6; At 900 ℃, gas speed is under 8 ~ 10 m/s, and through member district 22, the outlet 23 from the riser tube gas-solid mixture goes out riser tube then.Products obtained therefrom contains the Graphene, 0.4% of 16.6% single-layer graphene (carbon back), 80% double-layer graphite alkene, 3% 3-10 layer>10 layers Graphene.Nitrogen content in the above-mentioned Graphene is 0.6 %.
Embodiment 14
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 5:1 with the ratio of the sectional area of riser tube 2, uses MgO and Al
2O
3(MgO is 30% to mixed templates, and all the other are Al
2O
3, particle diameter is 500 microns, tap density is 520 kg/m
3), reactant gases is the gas mixture (benzene: hydrogen: the volume ratio of helium is 2:4:4) of benzene, hydrogen and helium, the total air speed of carbon source is 800 g/gcat/h; Reactant gases and template are fed descending bed 1, generate Graphene under the condition of 0.2m/s at 350 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures from descending bed gas-solid mixture get into the bottom of riser tube 2; Replenish benzene through riser tube gas feed 21; Making the volume ratio of benzene and hydrogen still keep 2:4, is under the condition of 5 ~ 6 m/s at 350 ℃, gas speed, through the member district 22 of riser tube gas feed 21 ends; Arrive riser tube 2 tops; Behind vertical partition plate 26 tops, move downward, pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.Products obtained therefrom contains 56.4% single-layer graphene (carbon back), 22.4% double-layer graphite alkene, 21% 3 layer graphenes, 0.2% decolorizing carbon.
Embodiment 15
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 4:1 with the ratio of the sectional area of riser tube 2, and (MgO is 90%, and all the other are ZnO, and particle diameter is 1 micron, and tap density is 820 kg/m to use MgO and ZnO mixed templates
3), reactant gases is the gas mixture (ethane: hydrogen: the volume ratio of helium is 2:8:4) of ethane, hydrogen and helium, the total air speed of carbon source is 1g/gcat/h.Reactant gases and template are fed descending bed 1, generate Graphene under the condition of 0.5m/s at 550 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures from descending bed gas-solid mixture get into the bottom of riser tube 2; Replenish ethane through riser tube gas feed 21; Making the volume ratio of ethane and hydrogen still keep 2:8, is under the condition of 9 ~ 10 m/s at 550 ℃, gas speed, through the member district 22 of riser tube gas feed 21 ends; Arrive riser tube 2 tops; Behind vertical partition plate 26 tops, move downward, pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.Products obtained therefrom contains 26.6% single-layer graphene (carbon back), 52.2% double-layer graphite alkene, 21% 3 layer graphenes, 0.2% decolorizing carbon.
Embodiment 16
Use reaction unit as shown in Figure 2, wherein descending bed 1 is 4:1 with the ratio of the sectional area of riser tube 2, and (MgO is 1%, and all the other are silit, and particle diameter is 100 microns, and tap density is 642 kg/m to use MgO and silit mixed templates
3), reactant gases is the gas mixture (propane: methylamine: hydrogen: the volume ratio of nitrogen is 2:0.02:8:4) of propane, methylamine, hydrogen and nitrogen, the total air speed of carbon source is 3g/gcat/h; Reactant gases and template are fed descending bed 1, are generation thin layer Graphene under the condition of 0.3m/s at 520 ℃, gas speed; When the outlet 12 effusive gas-solid mixtures from descending bed gas-solid mixture get into the bottom of riser tube 2; Replenish propane and methylamine through riser tube gas feed 21; Making the volume ratio of propane, methylamine and hydrogen still keep 2:0.02:8, is under the condition of 5 ~ 6 m/s at 520 ℃, gas speed, through the member district 22 of riser tube gas feed 21 ends; Arrive riser tube 2 tops; Behind vertical partition plate 26 tops, move downward, pass through the member district 22 of outlet 23 ends of riser tube gas-solid mixture again, the outlet 23 from the riser tube gas-solid mixture goes out riser tube 2 then.Products obtained therefrom contains 96.6% single-layer graphene (carbon back), 2.2% double-layer graphite alkene, 1% three layer graphenes, 0.2% decolorizing carbon.Nitrogen content in the above-mentioned Graphene is 1.2%.
Claims (10)
1. device for preparing thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid is characterized in that described apparatus structure is following:
(1) descending bed (1): the import (11) of descending bed gas-solid mixture is arranged on the top of descending bed (1); The outlet (12) of descending bed gas-solid mixture is arranged in the bottom of descending bed (1);
(2) riser tubes (2): the outlet (23) of riser tube gas-solid mixture is arranged on riser tube (2) top; Riser tube (2) inner side-wall is member district (22); In riser tube (2) bottom pyramidal structure (25) is arranged; Riser tube gas feed (21) is to remove a plurality of symmetric nozzle in the shared extra-regional zone of pyramidal structure (25) along riser tube (2) bottom;
(3) described descending bed (1) is inserted in the described riser tube (2); Heating system (24) is wrapped in riser tube (2) outside and is riser tube (2) and descending bed (1) heating; The outlet (12) of descending bed gas-solid mixture is adjacent with the upper end of the pyramidal structure (25) in the riser tube (2).
2. device for preparing thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid is characterized in that described apparatus structure is following:
(1) descending bed (1): the import (11) of descending bed gas-solid mixture is arranged on the top of descending bed (1); The outlet (12) of the descending bed gas-solid mixture that is arranged on riser tube gas feed (21) one sides is arranged in the bottom of descending bed (1);
(2) riser tubes (2): riser tube (2) inner side-wall is member district (22); A vertical partition plate (26) that is positioned at riser tube (2) middle part; Described vertical partition plate (26) is divided into riser tube (2) in two the equal zones of volume that only communicate at the top; Riser tube gas feed (21) is for being arranged on a plurality of nozzles of vertical partition plate (26) one sides; The outlet of riser tube gas-solid mixture (23) is for being arranged on a plurality of nozzles of vertical partition plate (26) opposite side;
(3) described descending bed (1) is inserted in the described riser tube (2); Heating system (24) is wrapped in riser tube (2) outside and is riser tube (2) and descending bed (1) heating.
3. the device of preparation thin layer Graphene according to claim 1 and 2 or thin layer Graphene and thin wall carbon nano-tube hybrid is characterized in that, the sectional area of descending bed (1) is 1 ~ 10 times of riser tube (2) sectional area.
4. a method of utilizing the described device of claim 1 to prepare thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid comprises the steps:
(1) opens heating system (24), descending bed (1) and riser tube (2) are heated to 300 ~ 1400 ℃, and keep heated condition;
(2) import (11) from descending bed gas-solid mixture feeds reactant gases and template, thin layer graphene; Or feed reactant gases and catalyzer, thin layer graphene and thin wall carbon nano-tube hybrid from the import (11) of descending bed gas-solid mixture; Gas that is generated and template, thin layer Graphene or gas and catalyzer, thin layer Graphene come out from the outlet (12) of descending bed gas-solid mixture with the thin wall carbon nano-tube hybrid, get into the bottom of riser tube (2);
(3) the riser tube gas feed (21) from riser tube (2) feeds reactant gases; Make the gas composition that is arranged in riser tube gas feed (21) near zone in the riser tube (2), the hydrogen that the import (11) of the volume ratio of hydrogen and carbon source and descending bed gas-solid mixture is located is identical with the ratio of carbon source; All gas-solid mixture moves upward, and through member district (22), goes out riser tube (2) from the outlet (23) of riser tube gas-solid mixture, gets into the gas solid separation workshop section and cooling, storage workshop section of postorder;
Repeating step (1) is to step (3), and thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid are produced in serialization.
5. a method of utilizing the described device of claim 2 to prepare thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid comprises the steps:
(1) opens heating system (24), descending bed (1) and riser tube (2) are heated to 300 ~ 1400 ℃, and keep heated condition;
(2) import (11) from descending bed (1) gas-solid mixture feeds reactant gases and template, thin layer graphene; Or feed reactant gases and catalyzer, thin layer graphene and thin wall carbon nano-tube hybrid from the import (11) of descending bed gas-solid mixture; Gas that is generated and template, thin layer Graphene or gas and catalyzer, thin layer Graphene come out from the outlet (12) of the descending bed gas-solid mixture of descending bed (1) with the thin wall carbon nano-tube hybrid, get into the bottom of riser tube (2);
(3) feed reactant gases from riser tube gas feed (21); Make the gas composition that is arranged in riser tube gas feed (21) near zone in the riser tube (2), the hydrogen that the import (11) of the descending bed gas-solid mixture of the volume ratio of hydrogen and carbon source and descending bed (1) is located is identical with the ratio of carbon source; All gas-solid mixture moves upward; Through member district (22); To the top of riser tube (2), move downward after walking around vertical partition plate (26), through the member district (22) of opposite side; Outlet (23) by the riser tube gas-solid mixture goes out riser tube (2), the gas solid separation workshop section of entering postorder and cooling, storage workshop section;
Repeating step (1) can be continuously produced thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid to step (3).
6. according to claim 4 or the 5 described methods that prepare thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid; It is characterized in that; The template of described thin layer graphene is one or more in aluminium sesquioxide, silicon oxide, zirconium white, Natural manganese dioxide, zinc oxide, Si-Al molecular sieve, Al-Mg-O type hydrotalcite, the silit; Particle diameter is 20nm ~ 500 μ m, and tap density is 200 ~ 1800 kg/m
3
7. according to claim 4 or the 5 described methods that prepare thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid; It is characterized in that the catalyzer of described thin layer graphene and thin wall carbon nano-tube hybrid is the nano metal loaded catalyst; Said activity of such catalysts component is one or more in iron, nickel, the cobalt; Auxiliary agent is one or more in molybdenum, tungsten, manganese, vanadium, the copper; Carrier is one or more in aluminium sesquioxide, silicon oxide, zirconium white, Natural manganese dioxide, Si-Al molecular sieve, the Al-Mg-O type hydrotalcite; The mass ratio of active ingredient in catalyzer is 0.1% ~ 10%, and the mass ratio of auxiliary agent in catalyzer is 0 ~ 10%, and the ratio of carrier in catalyzer is 90% ~ 99.9%; Granularity is 20 nm ~ 500 μ m, and tap density is 200 ~ 1800kg/m
3
8. according to claim 4 or the 5 described methods that prepare thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid, it is characterized in that described reactant gases is the mixture of carbon source or carbon source and hydrogen and/or rare gas element; Carbon source refers to that molecular weight is not more than the compound of 150 carbon elements; Described rare gas element is one or more in helium, argon gas, the nitrogen; When described reactant gases was the mixture of carbon source and hydrogen and/or rare gas element, the volume ratio of the mixture of carbon source and hydrogen and/or rare gas element was 1:1 ~ 1:200.
9. according to claim 4 or the 5 described methods that prepare thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid; It is characterized in that; When preparing nitrogenous thin layer Graphene or nitrogenous thin layer Graphene and nitrogenous carbon nano-tube hybridization body; In reactant gases, add ammonia, aliphatic amide or aromatic amine, and the volume ratio of carbon source and ammonia, aliphatic amide or aromatic amine is 100:1 ~ 20:1.
10. according to claim 4 or the 5 described methods that prepare thin layer Graphene or thin layer Graphene and thin wall carbon nano-tube hybrid; It is characterized in that; Operating gas velocity in the descending bed (1) is 0.1 ~ 2m/s; Operating gas velocity in the riser tube (2) is 1 ~ 20m/s, and the carbon source air speed is 0.2 ~ 800g/gcat/h.
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