CN102145883B - Directly-prepared ultrahigh-purity carbon nanotube and preparation method thereof - Google Patents
Directly-prepared ultrahigh-purity carbon nanotube and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a directly-prepared ultrahigh-purity carbon nanotube and a preparation method thereof, belonging to the technical field of carbon nanotubes. Under the condition that purification is not required, the purity of the carbon nanotube is greater than 99.7 weight percent, the tube diameter is between 0.8 nanometer and 30 nanometers, the specific surface area is between 200 m<2>/g and 500 m<2>/g, the agglomeration density is between 30 kg/m<3> and 150 kg/m<3> and the agglomeration particle size is between 20 microns and 150 microns. A method for directly preparing the ultrahigh-purity carbon nanotube by adopting a chemical vapor deposition method comprises the following steps of: dispersing catalyst crystal grains generated with a liquid phase method onto the surface of an inert carrier, drying and baking; cracking hydrocarbon with 1-6 carbon atoms in a fluidized bed reactor to generate a carbon nanotube; and separating the inert carrier from the generated carbon nanotube at a higher air speed. The carbon nanotube obtained with the method has the purity between 99.7 percent and 99.9 percent, and has the advantages of high carbon nanotube quality, no need of removing impurities by acid treatment, low cost and easiness for amplification and preparation.
Description
Technical field
The invention belongs to the carbon nanotube preparation technology field, particularly ultra-high purity carbon nanotube of a kind of direct preparation and preparation method thereof.
Background technology
Carbon nanotube is a kind of seamless tubular shaped material that is curled into by Sp2 hydridization carbon, because structural pipe wall sealing, there is not outstanding key, with and huge length-to-diameter ratio, the electroconductibility of carbon nanotube, thermal conductivity, physical strength etc. are the maximum of present known materials, study its preparation and application and have important academic significance and application prospect.
Through nearly 20 years development, chemical Vapor deposition process becomes the topmost method for preparing carbon nanotube.Its principle is: (mainly be iron with metallic catalyst, cobalt, the nickel even load is on porous support or Si substrate), under comparatively high temps (500-1200 ℃), the cracking carbon source is (as hydro carbons, carbonaceous organic material or CO etc.), (comprise fixed bed, moving-bed at reactor, fluidized-bed etc.) pass through the structure of control catalyzer in, can generate carbon nanotube by highly selective with optimal preparation technology (comprising temperature, pressure, air speed and carbon source ratio etc.).Substantially realized controllable diameter (single, double-walled and Duo Bi) at present, stacking states controlled (the heap type that looses, and orthogonal array or horizontal array), but and batch preparations (multi-walled carbon nano-tubes output can reach 1-15kg/h).
But the purity of the carbon nanotube that obtains is mostly at 90-95%, and the highest purity only is 99.5% also, can not be directly used in some fields high to the carbon material purity requirement.Such as, the fields such as conductive agent of rubber tyre field of compounding and lithium ion battery require metallic impurity＜0.3% in institute's carbon dope to reach less than 10-50ppm respectively.Because metallic impurity bring out the free radical reaction in the rubber, make tire aging (intensity variation), the serious accident that may bring out the motor vehicle of running at high speed under the high temperature.And the metallic impurity in the lithium ion battery can cause lithium ion to be moved out and generate larger-size dendrite gradually, damage barrier film, cause battery short circuit etc.Obviously the direct technology of preparing of carbon current nanotube far can not satisfy this requirement.Adopt acid treatment or high temperature evaporation to remove the method for metallic impurity, though carbon nano pipe purity can be increased to 99.9%, cost significantly increases, and produces a large amount of spent acid (contaminate environment).And through after these processing, carbon nanotube easily lumps, and is difficult for disperseing, and has increased the difficulty of using.
Summary of the invention
At the deficiency of catalyzer and technology of preparing in the carbon current nanotube preparation process, the present invention proposes that a kind of can directly to prepare structure bulk, easily disperses the preparation of highly purified carbon nanotube.
The invention provides a kind of ultra-high purity carbon nanotube of direct preparation, do not need the purity of carbon nanotube under the condition of purifying more than or equal to 99.7wt%, its caliber scope is 0.8-30nm, and specific surface area is 200-500m
2/ g; Its poly-group density is 30-150kg/m
3, poly-footpath is the 20-150 micron.Described ultra-high purity refers to that purity is greater than more than or equal to 99.7wt%.
The present invention also provides a kind of direct preparation method of ultra-high purity carbon nanotube, and this method comprises the steps:
(1) support of the catalyst is first under air atmosphere, at 700-950 ℃ of following roasting 4-8 hour, cool off standby then;
(2) mixture of preparation catalyzer and inert support:
The catalyzer that uses, its active constituent is at least a among Fe, Co or the Ni, its auxiliary agent is at least a among Mo, Mg, V or the Mn, its carrier is aluminium sesquioxide mutually, wherein the content of active constituent is the 20-30% of total catalyst weight, the content of auxiliary agent accounts for the 5-40% of total catalyst weight, and all the other are the carrier phase;
This catalyzer is prepared by liquid-phase precipitation method, post precipitation in liquid phase, the eigenstate before dry is the mono-dispersed nano particle, its size distribution is 1-5nm, wherein less than the component of 1nm greater than 30%, less than the component of 3nm greater than 75%;
Described Preparation of catalysts method, the reagent that uses has: Fe, the nitrate of Co or Ni, at least a in hydrochloride or the vitriol, the ammonium molybdate of auxiliary agent Mo, ammonium vanadate, at least a in the nitrate of Mn and Mg, (described alkaline precipitating agent comprises volatile salt to alkaline precipitating agent, urea, ammoniacal liquor etc.), and precipitation generates the reagent aluminum nitrate of carrier phase, form by described catalyzer, be dissolved in the deionized water simultaneously with showing acid reagent, be made into the solution of 0.1-1Mol/L, in addition, be dissolved in the reagent that shows alkalescence in the deionized water simultaneously, be made into corresponding solution than acidic solution concentration high 0.5%, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, all the time control solution temperature at 60-90 ℃, after the Preparation of Catalyst time reaches 5 hours, inert support to be poured in the above-mentioned solution, add-on control is 17-30Pas in the soup compound viscosity that makes formation;
Wherein, described inert support, composition are SiO
2Or ZrO
2Particle diameter is the 200-600 micron; Tap density is 800-1500kg/m
3, the sphericity of carrier is greater than 75%;
It is air-dry this soup compound to be placed on the sieve of filter cloth normal temperature;
With dried pressed powder under air atmosphere 300-900 ℃ following roasting 2-4 hour, cooling back is standby;
(3) mixture with catalyzer and inert support is put in fluidized-bed reactor, at first reduces 0.5-1 hour down at 600 ℃ with the nitrogen that contains 5-50% hydrogen, then gas is switched to C
1-C
6The mixed gas of hydrocarbon (wherein olefin(e) centent is at 30-50%, and remaining gas is to form arbitrarily) and nitrogen or argon gas, wherein, described C
1-C
6The volume ratio of hydrocarbon and nitrogen or argon gas is 3: 2, and total air speed of control hydro carbons is 100-500g/gcat/h, reacts 2-4 hour down at 550-750 ℃, generates carbon nanotube;
(4) gas is switched to contain 3-10%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.3-0.8m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally;
(5) collect the carbon nanotube fly out from the fluidized-bed top, be cooled to normal temperature after, obtain the ultra-high purity carbon nanotube.
The present invention compared with former technology, had following advantage and usefulness:
(1) component is only stressed in original catalyst technology preparation, does not pay close attention to the degree of scatter of catalyzer crystal grain.Method of the present invention can guarantee that the active utilization ratio of preparation-obtained catalyzer crystal grain is than the original 3-5 of raising times.
(2) original catalyst technology also can obtain nano level catalyzer crystal grain, but its monodisperse status easily reunites, and the material footpath is too little, is difficult for carrying out mobile reaction (easily taken away by air-flow and lose), so can't adopt big gas speed and air speed operation.And method of the present invention had both guaranteed again it to be sticked to the monodisperse status of catalyzer on other inert particles, had guaranteed to carry out with fluidized-bed reactor the gas-operated of big flux, and preparation carbon nanotube space-time yield is than higher.The gas consumption cost of unit time reduces by 50% than original.
(3) the present invention adopts the air-dry method of normal temperature to carry out the seasoning of catalyzer, compares than the dehydrating and drying method of original (mostly adopting 100-110 ℃), has both guaranteed that catalyzer crystal grain do not assemble, and has reduced energy consumption again.
(4) compared with former many catalyzer, catalyzer of the present invention is suitable for the cracking of hydrocarbon mixture, and not only raw materials cost is low, and carbon nano-tube is effective.
(5) the original the highest carbon nanotube product that can directly obtain 99.4-99.5% of carbon nanotube preparation technology, but its poly-group density is greater than 300kg/m
3, major part presents the lump shape.Be difficult for carrying out laggard worker (comprise pulverizing, disperse).And the catalyzer dispersion technology among the present invention not only makes carbon nano pipe purity greater than 99.7% (reaching as high as 99.9%), and poly-group density is less than 150kg/m
3, carbon nanotube carries out laggard worker easily, and makes the cost of post-treatment reduce by 50%.
Compare with original carbon nanotube product, product of the present invention can be directly used in rubber combined field.After portioned product of the present invention (purity is greater than 99.9%) diluted through conventional dispersion agent, removal of impurities more just can be directly used in the lithium ion battery field.
Beneficial effect of the present invention is: have carbon nanotube quality height, do not need the acid treatment removal of impurities, cost is low, easily amplifies the advantage of preparation.
The method of utilizing chemical Vapor deposition process directly to prepare the ultra-high purity carbon nanotube provided by the invention.This method comprises that the catalyzer crystal grain that liquid phase method is generated is dispersed in the inert support surface, carries out drying and roasting again.Cracking C in fluidized-bed reactor then
1-C
6Hydrocarbon generate carbon nanotube.The last bigger gas speed of recycling makes the carbon nanotube separation of inert support and generation.The carbon nano pipe purity that utilizes this method directly to prepare is 99.7-99.9%, has carbon nanotube quality height, does not need the acid treatment removal of impurities, and cost is low, easily amplifies the advantage of preparation.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
Use nitrate, ammonium molybdate and volatile salt and the urea of Fe and aluminium, be made into the acidic solution of 0.1Mol/L and the basic solution of 0.105Mol/L, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, all the time control control solution temperature is at 60 ℃, after 5 hours acid-base precipitations obtain containing the liquid of catalyzer, be added in 700 ℃ of roasting SiO after 3 hours
2(particle diameter is 600 microns to inert support, and sphericity is 80, and tap density is 800kg/m
3), the viscosity that makes soup compound is 17Pas.After the oven dry of above-mentioned soup compound normal temperature, and after 4 hours, obtain containing 20wt%Fe, the Fe/Mo/Al of 35wt%Mo 400 ℃ of roastings
2O
3Catalyzer, its catalyzer crystal grain are approximately 1-5nm (wherein the component of 1nm is 35%, is 80% less than the component of 3nm).This catalyzer is packed in the fluidized-bed reactor, the catalyzer for preparing and the mixture of inert support is put in fluidized-bed reactor, at first with the nitrogen that contains 5% hydrogen 600 ℃ of reduction 0.5 hour down.Then gas is switched to 60%C
1-C
3The mixed gas of hydrocarbon (total content that wherein requires ethene and propylene is 50%, and remaining gas is to form arbitrarily) and 40% nitrogen, total air speed of control hydro carbons is that 100g/gcat/h reacted 4 hours down at 550 ℃.Gas switched to contain 3%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.8m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally.Collection is from the carbon nanotube that the fluidized-bed top flies out, be cooled to normal temperature after, obtain carbon nanotube product.Being characterized as of carbon nanotube product: purity is greater than 99.7%, and its caliber scope is 8-20nm, and specific surface area is 250m
2/ g; Poly-group density is 100kg/m
3, poly-footpath is 20 microns.
Embodiment 2
Use nitrate, ammonium molybdate and volatile salt and urea and the ammoniacal liquor of Co and aluminium, be made into the acidic solution of 1Mol/L and the basic solution of 1.05Mol/L, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, controls solution temperature all the time at 90 ℃, after 5 hours acid-base precipitations obtain containing the liquid of catalyzer.Be added in 900 ℃ of roasting ZrO after 3 hours
2(particle diameter is 500 microns to inert support, and sphericity is 76, and tap density is 1500kg/m
3), the viscosity that makes soup compound is 30Pas.After the oven dry of above-mentioned soup compound normal temperature, and after 3 hours, obtain containing 30wt%Co, the Co/Mo/Al of 40wt%Mo 600 ℃ of roastings
2O
3Catalyzer, its catalyzer crystal grain are approximately 1-5nm (wherein the component less than 1nm is 30%, is 70% less than the component of 3nm).This catalyzer is packed in the fluidized-bed reactor, the catalyzer for preparing and the mixture of inert support is put in fluidized-bed reactor, at first with the nitrogen that contains 50% hydrogen 600 ℃ of reduction 0.5 hour down.Then gas is switched to 60%C
1-C
4The mixed gas of hydrocarbon (total content that wherein requires ethene, propylene and butylene is 30%, and remaining gas is to form arbitrarily) and 40% argon gas, total air speed of control hydro carbons is that 500g/gcat/h reacted 3 hours down at 750 ℃.Gas switched to contain 10%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.3m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally.Collection is from the carbon nanotube that the fluidized-bed top flies out, be cooled to normal temperature after, obtain carbon nanotube product.Being characterized as of carbon nanotube product: purity is greater than 99.9%, and its caliber scope is 0.8-10nm, and specific surface area is 500m
2/ g; Poly-group density is 30kg/m
3, poly-footpath is 120 microns.
Embodiment 3
The hydrochloride that uses Ni with, the nitrate of manganese and aluminium, urea and ammoniacal liquor, be made into the acidic solution of 0.5Mol/L and the basic solution of 0.525Mol/L, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, all the time control solution temperature at 80 ℃, after 5 hours acid-base precipitations obtain containing the liquid of catalyzer.Be added in 800 ℃ of roasting ZrO after 4 hours
2(particle diameter is 200 microns to inert support, and sphericity is 90, and tap density is 1200kg/m
3), the viscosity that makes soup compound is 20Pas.After the oven dry of above-mentioned soup compound normal temperature, and after 4 hours, obtain containing 25wt%Ni, the Ni/Mn/Al of 10wt%Mn 900 ℃ of roastings
2O
3Catalyzer, its catalyzer crystal grain are approximately 1-5nm (wherein the component less than 1nm is 40%, is 77% less than the component of 3nm).This catalyzer is packed in the fluidized-bed reactor, the catalyzer for preparing and the mixture of inert support is put in fluidized-bed reactor, at first with the nitrogen that contains 20% hydrogen 600 ℃ of reduction 1 hour down.Then gas is switched to 60%C
4-C
6The mixed gas of hydrocarbon (wherein the total content of butylene and amylene is 50%, and remaining gas is to form arbitrarily) and 40% argon gas, total air speed of control hydro carbons is that 200g/gcat/h reacted 4 hours down at 650 ℃.Gas switched to contain 5%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.5m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally.Collection is from the carbon nanotube that the fluidized-bed top flies out, be cooled to normal temperature after, obtain carbon nanotube product.Being characterized as of carbon nanotube product: purity is greater than 99.8%, and its caliber scope is 3-20nm, and specific surface area is 430m
2/ g; Poly-group density is 130kg/m
3, poly-footpath is 80 microns.
Embodiment 4
Use Fe and Ni vitriol and, the nitrate of manganese and aluminium, urea and volatile salt, be made into the acidic solution of 0.3Mol/L and the basic solution of 0.315Mol/L, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, all the time control 75 ℃ of solution temperatures, after 5 hours acid-base precipitations obtain containing the liquid of catalyzer.Be added in 700 ℃ of roasting SiO after 4 hours
2(particle diameter is 200 microns to inert support, and sphericity is 85, and tap density is 1000kg/m
3), the viscosity that makes soup compound is 25Pas.After the oven dry of above-mentioned soup compound normal temperature, and after 4 hours, obtain containing 25wt%Fe, 1wt%Ni, the Fe/Ni/Mn/Al of 5wt%Mn 800 ℃ of roastings
2O
3Catalyzer, its catalyzer crystal grain are approximately 1-5nm (wherein the component less than 1nm is 32%, is 78% less than the component of 3nm).This catalyzer is packed in the fluidized-bed reactor, the catalyzer for preparing and the mixture of inert support is put in fluidized-bed reactor, at first with the nitrogen that contains 8% hydrogen 500 ℃ of reduction 0.6 hour down.Then gas is switched to 60%C
2-C
5The mixed gas of hydrocarbon (therein ethylene, propylene, the total content of butylene and amylene are 50%, remaining gas is to form arbitrarily) and 40% nitrogen, total air speed of control hydro carbons are 400g/gcat/h 650 ℃ of reactions 3 hours down.Gas switched to contain 4%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.5m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally.Collection is from the carbon nanotube that the fluidized-bed top flies out, be cooled to normal temperature after, obtain carbon nanotube product.Being characterized as of carbon nanotube product: purity is 99.9%, and its caliber scope is 5-15nm, and specific surface area is 230m
2/ g; Poly-group density is 60kg/m
3, poly-footpath is 150 microns.
Embodiment 5
Use Fe and Co vitriol and, the nitrate of aluminium, ammonium molybdate, urea and volatile salt, be made into the acidic solution of 0.4Mol/L and the basic solution of 0.42Mol/L, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, controls solution temperature all the time at 65 ℃, after 5 hours acid-base precipitations obtain containing the liquid of catalyzer.Be added in 950 ℃ of roasting ZrO after 5 hours
2(particle diameter is 300 microns to inert support, and sphericity is 80, and tap density is 1400kg/m
3), the viscosity that makes soup compound is 28Pas.After the oven dry of above-mentioned soup compound normal temperature, and after 4 hours, obtain containing 15wt%Fe, 5wt%Co, the Fe/Co/Mo/Al of 7wt%Mo 860 ℃ of roastings
2O
3Catalyzer, its catalyzer crystal grain are approximately 1-5nm (wherein the component less than 1nm is 40%, is 86% less than the component of 3nm).This catalyzer is packed in the fluidized-bed reactor, the catalyzer for preparing and the mixture of inert support is put in fluidized-bed reactor, at first with the nitrogen that contains 30% hydrogen 600 ℃ of reduction 1 hour down.Then gas is switched to 60%C
2The mixed gas of hydrocarbon (therein ethylene content is 50%, and all the other are ethane) and 40% argon gas, total air speed of control hydro carbons are that 300g/gcat/h reacted 4 hours down at 600 ℃.Gas switched to contain 6%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.4m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally.Collection is from the carbon nanotube that the fluidized-bed top flies out, be cooled to normal temperature after, obtain carbon nanotube product.Being characterized as of carbon nanotube product: purity is 99.85%, and its caliber scope is 1-15nm, and specific surface area is 450m
2/ g; Poly-group density is 80kg/m
3, poly-footpath is 120 microns.
Embodiment 6
Use nitrate, ammonium vanadate and volatile salt and urea and the ammoniacal liquor of Co and aluminium, be made into the acidic solution of 0.8Mol/L and the basic solution of 0.84Mol/L, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, controls solution temperature all the time at 80 ℃, after 5 hours acid-base precipitations obtain containing the liquid of catalyzer.Be added in 800 ℃ of roasting ZrO after 8 hours
2(particle diameter is 500 microns to inert support, and sphericity is 80, and tap density is 1200kg/m
3), the viscosity that makes soup compound is 20Pas.After the oven dry of above-mentioned soup compound normal temperature, and after 2 hours, obtain containing 20wt%Co, the Co/V/Al of 8wt%V 300 ℃ of roastings
2O
3Catalyzer, its catalyzer crystal grain are approximately 1-5nm (wherein the component less than 1nm is 35%, is 78% less than the component of 3nm).This catalyzer is packed in the fluidized-bed reactor, the catalyzer for preparing and the mixture of inert support is put in fluidized-bed reactor, at first with the nitrogen that contains 40% hydrogen 600 ℃ of reduction 1 hour down.Then gas is switched to 60%C
2-C
4The mixed gas of hydrocarbon (total content of therein ethylene, propylene and butylene is 45%, and remaining gas is to form arbitrarily) and 40% nitrogen, total air speed of control hydro carbons is that 400g/gcat/h reacted 3 hours down at 680 ℃.Gas switched to contain 7%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.6m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally.Collection is from the carbon nanotube that the fluidized-bed top flies out, be cooled to normal temperature after, obtain carbon nanotube product.Being characterized as of carbon nanotube product: purity is greater than 99.87%, and its caliber scope is 0.8-7nm, and specific surface area is 490m
2/ g; Poly-group density is 60kg/m
3, poly-footpath is 140 microns.
Embodiment 7
Use the vitriol of Fe and Co, the nitrate of magnesium and aluminium, ammonium molybdate, urea and volatile salt, be made into the acidic solution of 0.7Mol/L and the basic solution of 0.735Mol/L, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, all the time control solution temperature at 60 ℃, after 5 hours acid-base precipitations obtain containing the liquid of catalyzer.Be added in 850 ℃ of roasting ZrO after 4 hours
2(particle diameter is 200 microns to inert support, and sphericity is 86, and tap density is 1300kg/m
3), the viscosity that makes soup compound is 22Pas.After the oven dry of above-mentioned soup compound normal temperature, and after 4 hours, obtain containing 5wt%Fe, 25wt%Co, 7wt%Mo, the Fe/Co/Mo/Mg/Al of 8wt%Mg 800 ℃ of roastings
2O
3Catalyzer, its catalyzer crystal grain are approximately 1-5nm (wherein the component less than 1nm is 30%, is 75% less than the component of 3nm).This catalyzer is packed in the fluidized-bed reactor, the catalyzer for preparing and the mixture of inert support is put in fluidized-bed reactor, at first with the nitrogen that contains 25% hydrogen 580 ℃ of reduction 1 hour down.Then gas is switched to 60%C
3The mixed gas of hydrocarbon (wherein propylene content is 45%, and all the other are propane) and 40% argon gas, total air speed of control hydro carbons are that 500g/gcat/h reacted 4 hours down at 700 ℃.Gas switched to contain 10%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.6m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally.Collection is from the carbon nanotube that the fluidized-bed top flies out, be cooled to normal temperature after, obtain carbon nanotube product.Being characterized as of carbon nanotube product: purity is 99.88%, and its caliber scope is 0.8-20nm, and specific surface area is 480m
2/ g; Poly-group density is 40kg/m
3, poly-footpath is 130 microns.
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (4)
1. direct ultra-high purity carbon nanotube of preparation, it is characterized in that: do not need the purity of carbon nanotube under the condition of purifying more than or equal to 99.7wt%, its caliber scope is 0.8-30nm, and specific surface area is 200-500 m
2/ g; Its poly-group density is 30-150 kg/m
3, poly-footpath is the 20-150 micron;
Described ultra-high purity preparation method of carbon nano-tube comprises the steps:
⑴ under air atmosphere, at 700-950 ℃ of following roasting 4-8 hour, cool off standby then catalyzer inert support elder generation;
⑵ prepare the mixture of catalyzer and inert support:
The catalyzer that uses, its active constituent is at least a among Fe, Co or the Ni, its auxiliary agent is at least a among Mo, Mg, V or the Mn, its carrier is aluminium sesquioxide mutually, wherein the content of active constituent is the 20-30% of total catalyst weight, the content of auxiliary agent accounts for the 5-40% of total catalyst weight, and all the other are the carrier phase;
This catalyzer is prepared by liquid-phase precipitation method, the reagent that uses has: Fe, the nitrate of Co or Ni, at least a in hydrochloride or the vitriol, the ammonium molybdate of auxiliary agent Mo, ammonium vanadate, at least a in the nitrate of Mn and Mg, alkaline precipitating agent, and the reagent aluminum nitrate of precipitation generation carrier phase, form by described catalyzer, be dissolved in the deionized water simultaneously with showing acid reagent, be made into the solution of 0.1-1Mol/L, in addition, the reagent that shows alkalescence is dissolved in the deionized water simultaneously, is made into the solution than acidic solution concentration high 0.5%, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, all the time control solution temperature at 60-90 ℃, after the Preparation of Catalyst time reaches 5 hours, inert support to be poured in the above-mentioned solution, add-on control is 17-30Pas in the soup compound viscosity that makes formation;
It is air-dry this soup compound to be placed on the sieve of filter cloth normal temperature;
With dried pressed powder under air atmosphere 300-900 ℃ following roasting 2-4 hour, cooling back is standby;
⑶ be put in fluidized-bed reactor with the mixture of catalyzer and inert support, at first reduced 0.5-1 hour down at 600 ℃ with the nitrogen that contains 5-50% hydrogen, then gas switched to C
1-C
6The mixed gas of hydrocarbon and nitrogen or argon gas, wherein, described C
1-C
6The volume ratio of hydrocarbon and nitrogen or argon gas is 3:2, and total air speed of control hydro carbons is 100-500 g/gcat/h, reacts 2-4 hour down at 550-750 ℃, generates carbon nanotube;
⑷ switch to gas and contain 3-10%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.3-0.8m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally;
⑸ collect the carbon nanotube fly out from the fluidized-bed top, be cooled to normal temperature after, obtain the ultra-high purity carbon nanotube;
Described inert support, composition are SiO
2Or ZrO
2Particle diameter is the 200-600 micron; Tap density is 800-1500 kg/m
3, the sphericity of carrier is greater than 75%;
Described alkaline precipitating agent is at least a in volatile salt, urea, the ammoniacal liquor etc.
2. the direct preparation method of a ultra-high purity carbon nanotube, it is characterized in that: this method comprises the steps:
⑴ under air atmosphere, at 700-950 ℃ of following roasting 4-8 hour, cool off standby then catalyzer inert support elder generation;
⑵ prepare the mixture of catalyzer and inert support:
The catalyzer that uses, its active constituent is at least a among Fe, Co or the Ni, its auxiliary agent is at least a among Mo, Mg, V or the Mn, its carrier is aluminium sesquioxide mutually, wherein the content of active constituent is the 20-30% of total catalyst weight, the content of auxiliary agent accounts for the 5-40% of total catalyst weight, and all the other are the carrier phase;
This catalyzer is prepared by liquid-phase precipitation method, the reagent that uses has: Fe, the nitrate of Co or Ni, at least a in hydrochloride or the vitriol, the ammonium molybdate of auxiliary agent Mo, ammonium vanadate, at least a in the nitrate of Mn and Mg, alkaline precipitating agent, and the reagent aluminum nitrate of precipitation generation carrier phase, form by described catalyzer, be dissolved in the deionized water simultaneously with showing acid reagent, be made into the solution of 0.1-1Mol/L, in addition, the reagent that shows alkalescence is dissolved in the deionized water simultaneously, is made into the solution than acidic solution concentration high 0.5%, above-mentioned two kinds of solution are adopted the method that drips with the volume ratio, splash into one and fill deionized water in advance, and start in the container that stirs in advance, the volume of deionized water is 30% of acidic solution and basic solution cumulative volume in the described container, all the time control solution temperature at 60-90 ℃, after the Preparation of Catalyst time reaches 5 hours, inert support to be poured in the above-mentioned solution, add-on control is 17-30Pas in the soup compound viscosity that makes formation;
It is air-dry this soup compound to be placed on the sieve of filter cloth normal temperature;
With dried pressed powder under air atmosphere 300-900 ℃ following roasting 2-4 hour, cooling back is standby;
⑶ be put in fluidized-bed reactor with the mixture of catalyzer and inert support, at first reduced 0.5-1 hour down at 600 ℃ with the nitrogen that contains 5-50% hydrogen, then gas switched to C
1-C
6The mixed gas of hydrocarbon and nitrogen or argon gas, wherein, described C
1-C
6The volume ratio of hydrocarbon and nitrogen or argon gas is 3:2, and total air speed of control hydro carbons is 100-500 g/gcat/h, reacts 2-4 hour down at 550-750 ℃, generates carbon nanotube;
⑷ switch to gas and contain 3-10%CO
2Nitrogen, the gas speed of control in the fluidized-bed is 0.3-0.8m/s, and the carbon nanotube of generation is separated with inert carrier particle, and lowers the temperature naturally;
⑸ collect the carbon nanotube fly out from the fluidized-bed top, be cooled to normal temperature after, obtain the ultra-high purity carbon nanotube;
Described inert support, composition are SiO
2Or ZrO
2Particle diameter is the 200-600 micron; Tap density is 800-1500 kg/m
3, the sphericity of carrier is greater than 75%;
Described alkaline precipitating agent is at least a in volatile salt, urea, the ammoniacal liquor etc.
3. method according to claim 2, it is characterized in that: described catalyzer post precipitation in liquid phase, dry preceding eigenstate is the mono-dispersed nano particle, its size distribution is 1-5nm, wherein less than the component of 1nm greater than 30%, less than the component of 3nm greater than 75%.
4. method according to claim 2 is characterized in that: described C
1-C
6In the hydrocarbon, olefin(e) centent is at 30-50%, and remaining gas is to form arbitrarily.
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| KR101508101B1 (en) * | 2013-09-30 | 2015-04-07 | 주식회사 엘지화학 | Carbon nanotubes having high specific surface area and Process for preparing same |
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| CN113371694A (en) * | 2021-07-16 | 2021-09-10 | 中国石油化工股份有限公司 | Method and device for preparing carbon nano tube and hydrogen |
| CN114618516B (en) * | 2022-03-17 | 2023-06-02 | 无锡东恒新能源科技有限公司 | Synthesis method of microspherical catalyst |
| CN114749184A (en) * | 2022-04-19 | 2022-07-15 | 深圳烯湾科技有限公司 | Metal carrier catalyst, preparation method and application thereof |
| CN115074092B (en) * | 2022-05-09 | 2023-06-13 | 清华大学 | Nitrogen-containing sulfur-containing carbon nano tube and preparation method and application thereof |
| CN115041180A (en) * | 2022-06-24 | 2022-09-13 | 深圳烯湾科技有限公司 | Carbon nanotube catalyst, preparation method thereof and carbon nanotube fluidized bed preparation process |
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