CN107570160A - A kind of medical stone is method for preparing catalyst, catalyst and the application that carrier is used for CNT production - Google Patents
A kind of medical stone is method for preparing catalyst, catalyst and the application that carrier is used for CNT production Download PDFInfo
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Abstract
It is method for preparing catalyst, catalyst and the application that carrier is used for CNT production the invention discloses a kind of medical stone, is related to materialogy field.Preparation method is：(1) carbon nanometer pipe catalytic element is formed nanomorphic distribution on medical stone surface, obtain catalyst precursor；(2) catalyst precursor that step (1) obtains obtains the catalyst for CNT production after high-temperature calcination, crushing, gradation sizing, packaging.10~1000 ㎡ of gained specific surface area of catalyst/g.This method raw material is cheap, and technique is simple, and catalyst granules form is controllable, and catalytic elements are evenly distributed, and green.
Description
Technical field
The present invention relates to materialogy field, and in particular to a kind of preparation method of catalyst, catalyst and application.
Background technology
CNT is the important materials formed by carbon, and basic structural unit is carbon atom with sp2 hybrid form shapes
Into carbene hexatomic ring, its mechanics, electricity and chemical property are excellent, are widely used.
At present, it is exactly catalytic pyrolysis and the carbon member by carbon containing organic gas to prepare one of main method of above-mentioned material
The deposition growing of element, this method yield is high, and preparation condition is controllable, is had an optimistic view of by people.Carbon containing organic gas catalytic pyrolysis chemical gaseous phase
In sedimentation, catalyst is mostly important factor, is widely studied.Patent CN02100709.8 passes through coprecipitation, height
Pressure hydro-thermal reaction, high-temperature calcination prepare CNT Fe-series catalyst；Patent CN03117874.X is prepared for iron by complexometry
It is carbon nano-tube catalyst containing rare earth element.Above-mentioned patent has all been successfully prepared out the catalyst of CNT, but catalyst
Preparation process is all employed containing the presoma that the soluble-salts such as magnesium, aluminium, silicon, rare earth element are carrier, and raw material valency is expensive, technique is multiple
It is miscellaneous, cost is high, particle shape is uncontrollable, and catalytic elements because long-time technological operation and slow solvent evaporation easily formed state of aggregation
Skewness caused by and, and it is useless to produce the waste liquid of the pollution environment such as a large amount of chloride ion-containings, nitrate anion, sulfate radical, dust etc.
Gurry.
The content of the invention
The technical problems to be solved by the invention are the above-mentioned deficiencies for prior art, there is provided a kind of cost is cheap, work
The organic carbon vapor phase growth cracking that is used for that skill is simple and environmentally-friendly, catalyst granules form is controllable, catalytic elements are evenly distributed is deposited as
The preparation method and catalyst of the catalyst of CNT and application.
The technical problems to be solved by the invention are realized by following technical scheme, and the present invention provides a kind of wheat
Meal stone is the method for preparing catalyst that carrier is used for CNT production, is characterized in, this method comprises the following steps：(1) make
Carbon nanometer pipe catalytic element forms nanomorphic distribution on medical stone surface, obtains catalyst precursor；(2) step (1) obtains
Catalyst precursor after high-temperature calcination, crushing, gradation sizing, packaging i.e. obtain for CNT production catalysis
Agent.10~1000 ㎡ of gained specific surface area of catalyst/g.
Step (1) can be specially：Medical stone powder adds water to be made into medical stone powder suspension, adds carbon nanotubes catalysis member
The solution or suspension of the material of element, carbon nanotubes catalytic elements are prepared by a kind of in ion-exchange or infusion process
Mixture, said mixture is spray-dried, filtering, press filtration, more than one or both of rotary process removes solvent, obtains
Catalytic elements nanomorphic is distributed in the catalyst precursor on medical stone surface.
Step (1) can also be specially：Medical stone powder adds water to be made into medical stone powder suspension, adds carbon nanotubes catalysis
Precipitating reagent and dispersant are added while the solution or suspension of the material of element, passes through coprecipitation, hydro-thermal method, collosol and gel
A kind of mixture for preparing carbon nanotubes catalytic elements in method, said mixture is spray-dried, filtering, press filtration, centrifugation
Solvent more than one or both of process is removed, before obtaining the catalyst that catalytic elements nanomorphic is distributed on medical stone surface
Drive body.The precipitating reagent is in soluble hydroxide, soluble carbonate salt or bicarbonate, soluble ammonium salt, ammonia, urea
It is one or more kinds of；The dispersant is sodium metaphosphate, sodium alkyl benzene sulfonate, polyvinyl alcohol, polyethylene glycol oxide, polyoxy second
It is one or more kinds of in alkene-three sections of polyoxypropylene polyoxyethylene type copolymer, polyvinylpyrrolidone；The precipitating reagent is used
Measure as the 50%-150% of carbon nanometer pipe catalytic element theory mole, preferably 80%-120%；Dispersant dosage is that system is total
The 0.1%-10% of quality, preferably 0.25%-5%.
Step (1) can be specially again：Medical stone powder adds water to be made into medical stone powder suspension, adds carbon nanotubes catalysis
Complexing agent and dispersant are added while the solution or suspension of the material of element, preparing carbon nanotubes by complexometry is catalyzed
The mixture of element, said mixture is spray-dried, filtering, press filtration, more than one or both of rotary process remove it is molten
Agent, obtain the catalyst precursor that catalytic elements nanomorphic is distributed on medical stone surface.
The complexing agent is the one or two or more kinds in citric acid, tartaric acid, glycine, the amine tetraacethyl of second two；It is described
Dispersant is sodium metaphosphate, sodium alkyl benzene sulfonate, polyvinyl alcohol, polyethylene glycol oxide, polyoxyethylene-poly-oxypropylene polyoxyethylene
It is one or more kinds of in type three sections of copolymers, polyvinylpyrrolidones；Amount of complex is catalytic elements theoretical molar amount
20%-300%, preferably 50%-200%；Dispersant dosage is the 0.1%-10% of system gross mass, preferably
0.25%-5%.
In above step, the medical stone powder suspension solid content is 1%~60%；The carbon nanometer pipe catalytic element is
It is more than one or both of iron, cobalt, nickel, chromium, molybdenum, tungsten, the materials of the carbon nanotubes catalytic elements refer to containing iron, cobalt,
It is nickel, chromium, the oxide of molybdenum or tungsten, hydroxide, chloride, cyanide, fluoride, nitrate, sulfate, silicate, organic
More than one or both of hydrochlorate, chromate, molybdate, tungstates compound or their compound；It is described carbon containing to receive
In the solution or suspension of the material of mitron catalytic elements, the Solute mass concentration or solid content of above-claimed cpd or compound are
0.5%-95%；The temperature of the high-temperature calcination is 300 DEG C -1200 DEG C, and calcination time is 1-24 hours；The spray drying,
Spray dryer is one kind in drying machine with centrifugal spray, Pressuresprayingdrier or two/tri- fluid spray dryers, and spraying is dry
The temperature of dry machine is 120 DEG C -400 DEG C；The catalyst precursor particle size range 50-1000 microns.
Preferably, the medical stone powder suspension solid content is 5%~40%；The thing of the carbon nanotubes catalytic elements
In the solution or suspension of matter, the Solute mass concentration or solid content of the compound or compound are 2%-50%；The spray
Mist is dried, and the temperature of spray dryer is 200 DEG C -300 DEG C.
The present invention also provides the catalyst for being used for CNT and producing prepared according to the above method.
In addition, the present invention also provides application of the above-mentioned catalyst in CNT is prepared, it is characterised in that：By catalyst
It is placed in high-temperature service, is passed through the mixed gas containing seven carbon and following organic gas and inert gas and reducibility gas,
Controlling temperature, mixed gas air speed is controlled in 0.1h-1-100h-1, and CNT crude product is prepared at 500 DEG C -1200 DEG C,
By separating-purifying, CNT is made；Wherein high-temperature service is in roller kilns, rotary furnace, fixed bed, moving bed or fluid bed
One kind.
The particle diameter of above-mentioned medical stone powder is 1 μm~2000 μm, preferably 10 μm~1000 μm.
Beneficial effect
Compared with prior art, carrier of the present invention using medical stone as carbon nano-tube catalyst, catalyst form is controllable,
Avoid catalytic elements because long-time technological operation and slow solvent evaporate to form state of aggregation and caused by uneven distribution, and
Thus the problem of producing waste liquid, dust the like waste pollution environment, its technique is simple and environmentally-friendly, is easy to commercial introduction, is urged using this
Agent can efficiently prepare CNT, 30~50 times up to catalyst quality of gained carbon nanotube mass..
Brief description of the drawings
Fig. 1 is the catalyst electromicroscopic photograph of embodiment 1；
Fig. 2 is CNT stereoscan photograph obtained by the catalyst of embodiment 1；
Fig. 3 is CNT stereoscan photograph obtained by the catalyst of embodiment 5；
Fig. 4 is CNT stereoscan photograph obtained by the catalyst of embodiment 6；
Fig. 5 is CNT high power transmission electron microscope photo obtained by the catalyst of embodiment 7；
Fig. 6 is CNT high power transmission electron microscope photo obtained by the catalyst of embodiment 9；
Fig. 7 is CNT high power transmission electron microscope photo obtained by the catalyst of embodiment 10.
Embodiment
Concrete technical scheme of the invention described further below, in order to which those skilled in the art is further understood that
The present invention, without forming the limitation to its right.
Embodiment 1
Medical stone powder adds water to be made into the suspension of solid content 20%, adds the iron nitrate aqueous solution of mass fraction 30%, quality point
Several 30% sodium hydroxides are water-soluble and the neopelex solution of mass fraction 5% presses 60 DEG C of ion-exchange, ion exchange
The mixed liquor that iron-containing catalyst precursor is made in 4h is reacted, is calculated using medical stone suspension quality as 100%, iron nitrate solution matter
Measure as 10%, sodium hydroxide solution 1%, neopelex solution is 0.5%；Mixed liquor is added to centrifugal spray dryer
In dry machine, it is spray-dried at a temperature of 240 DEG C, the cyclone separator and sack cleaner collection catalyst of drying machine with centrifugal spray
Precursor, catalyst precursor particle diameter 60-150 microns, after by rotary furnace in 450 DEG C of temperature lower calcinations 3 hours, obtain particle diameter
The catalyst granules of 50-120 microns, specific surface area 90m2/g.
Catalyst apply when, above-mentioned catalyst is placed in fixed bed, temperature control at 600-800 DEG C, be passed through methane and
Argon gas volume ratio 1：4 mixed gas, air speed 0.5h-1, CNT is obtained after separating-purifying.
Fig. 1 is that catalyst electromicroscopic photograph is made in the present embodiment, it can be seen that prepared by method provided by the invention
Catalyst distribution is uniform.
Embodiment 2
Medical stone powder adds water to be made into the suspension of solid content 5%, adds the cobalt chloride solution of mass fraction 10%, mass fraction
15% ammonium carbonate solution and the sodium phosphate aqueous solution of mass fraction 5% press 40 DEG C of infusion process method, and cobalt-containing catalyst is made in dipping 3h
The mixed liquor of precursor, calculated using medical stone suspension quality as 100%, the quality of cobalt chloride solution is medical stone suspension
30%, sal volatile 20%, sodium radio-phosphate,P-32 solution 10%；Mixed liquor is added in Pressuresprayingdrier, in 280 DEG C of temperature
Degree is lower to be spray-dried, the cyclone separator and sack cleaner collection catalyst precursor of drying machine with centrifugal spray, before catalyst
Body particle diameter 80-200 microns, after by rotary furnace in 400 DEG C of temperature lower calcinations 2 hours, obtain particle diameter 60-150 microns, compare table
Area 60m2/g catalyst granules.
When catalyst is applied, above-mentioned catalyst is placed in fixed bed, temperature control is passed through ethene, nitrogen at 650-850 DEG C
Gas, hydrogen volume are than 2：7：1 mixed gas, air speed 10h-1, CNT is obtained after separating-purifying.
Embodiment 3
Medical stone powder adds water to be made into the suspension of solid content 30%, adds the iron nitrate aqueous solution of mass fraction 20%, quality point
Several 5% ammonium molybdate aqueous solutions, the ammonium carbonate solution of mass fraction 20% and the ammonium acetate aqueous solution of mass fraction 10%, with medical stone
Suspension quality is 100% calculating, and the quality of iron nitrate solution is the 50% of medical stone suspension, ammonium molybdate solution 5%, carbon
Acid ammonium solution is 50%, sodium radio-phosphate,P-32 solution 10%；After being well mixed by coprecipitation, 30 DEG C~50 DEG C, reaction 2h, which is made, to be contained
The mixed liquor of iron, molybdenum catalyst precursor, mixed liquor are added in twin-fluid spray dryer, are sprayed at a temperature of 220 DEG C dry
It is dry, the cyclone separator and sack cleaner collection catalyst precursor of twin-fluid spray dryer, catalyst precursor particle diameter
70-40 microns, after by rotary furnace in 400 DEG C of temperature lower calcinations 2 hours, obtain 50~110 microns of particle diameter, specific surface area
100m2/g catalyst granules.
When catalyst is applied, above-mentioned catalyst is placed in fixed bed, temperature control is passed through propane, nitrogen at 700-900 DEG C
Gas, hydrogen volume are than 30：65：5 mixed gas, air speed 80h-1, CNT is obtained after separating-purifying.
Embodiment 4
Medical stone powder adds water to be made into the suspension of solid content 40%, adds the nickel nitrate aqueous solution of mass fraction 40%, quality point
Several 10% ammonium tungstate aqueous solutions, 20% sodium hydroxide and 5% neopelex, using medical stone suspension quality as
100% calculates, and the quality of nickel nitrate solution is the 60% of medical stone suspension, ammonium tungstate solution 5%, and sodium hydroxide solution is
80%, neopelex solution is 5%；After being well mixed by high pressure hydro-thermal method, 0.26MPa~1.6MPa, 120 DEG C~
200 DEG C, the mixed liquor of nickeliferous tungsten catalyst precursor is made in reaction 2h, and the percentage of above material is that mass percent is dense
Degree, mixed liquor is added in pressure flame filter press, and by rotary furnace in 400 DEG C of temperature lower calcinations 2 hours, grain is obtained after crushing
Footpath 50-110 microns, specific surface area 180m2/g catalyst granules.
When catalyst is applied, above-mentioned catalyst is placed in fixed bed, temperature control is passed through acetylene, argon at 650-850 DEG C
Gas, hydrogen volume are than 20：75：5 mixed gas, air speed 40h-1, CNT is obtained after separating-purifying.
Embodiment 5
Medical stone powder adds water to be made into the suspension of solid content 50%, adds the iron nitrate aqueous solution of mass fraction 10%, quality point
Several 20% sodium hydrate aqueous solutions, the aqueous solution of urea of mass fraction 5% and mass fraction 5% PULLRONIC F68-polyoxy
Three sections of aqueous copolymers solutions of ethylene type, calculated using medical stone suspension quality as 100%, the quality of iron nitrate solution is medical stone
The 40% of suspension, sodium hydroxide solution 20%, urea liquid 5%, polyoxyethylene-poly-oxypropylene polyoxyethylene three are embedding
Section copolymer solution is 5%；After being well mixed by sol-gal process, 0.48MPa~1.6MPa, 150 DEG C~200 DEG C, 3h is reacted
The mixed liquor of iron-containing catalyst precursor is made, mixed liquor is added to centrifugal filtration, by roller furnace in 400 DEG C of temperature lower calcinations
2 hours, obtain particle diameter 50-110 microns, specific surface area 200m2/g catalyst granules.
Catalyst apply when, above-mentioned catalyst is placed in fixed bed, temperature control at 700-1000 DEG C, be passed through methane and
Argon gas volume ratio is 4：6 mixed gas, air speed 60h-1, CNT is obtained after separating-purifying.
Embodiment 6
Medical stone powder adds water to be made into the suspension of solid content 10%, adds the cobalt nitrate aqueous solution of mass fraction 30%, quality point
Several 5% ammonium molybdate aqueous solutions, the ammonium carbonate solution of mass fraction 15%, the ammonium acetate aqueous solution of mass fraction 5%, mass fraction
The 5% APEO aqueous solution, is calculated using medical stone suspension quality as 100%, and the quality of cobalt nitrate solution is hanged for medical stone
The 30% of supernatant liquid, ammonium molybdate solution 5%, sal volatile 40%, ammonium acetate solution 10%, polyoxyethylene ethereal solution are
4%；After being well mixed by coprecipitation, 30 DEG C~50 DEG C, the mixed liquor of precursor is made in reaction 2h, and mixed liquor is added to three streams
In spray body drying machine, it is spray-dried at a temperature of 300 DEG C, the cyclone separator and sack cleaner of three fluid spray dryers
Collection catalyst precursor, catalyst precursor particle diameter 50-150 microns, after it is small in 600 DEG C of temperature lower calcinations 2 by rotary furnace
When, obtain particle diameter 50-100 microns, specific surface area 90m2/g catalyst granules.
Catalyst apply when, above-mentioned catalyst is placed in fixed bed, temperature control at 700-1000 DEG C, be passed through acetone,
Nitrogen, hydrogen volume ratio are 25：65：10 mixed gas, air speed 20h-1, CNT is obtained after separating-purifying.
Embodiment 7
Medical stone powder adds water to be made into 5% suspension, by ferric nitrate, nickel nitrate, citric acid in mass ratio 1：3：5 be made it is total molten
The aqueous solution of matter content mass fraction 50%, the latter's mass are 20% mixing of medical stone suspension quality, after being well mixed, are led to
Sol-gal process 0.48MPa~1.6MPa is crossed, 150 DEG C~200 DEG C, the suspension of iron content, Raney nickel precursor is made in reaction 3h
Liquid, the centrifugal spray drying at a temperature of 240 DEG C, cyclone separator and sack cleaner collection catalyst precursor, before catalyst
Body particle diameter 60-150 microns, after by rotary furnace in 450 DEG C of temperature lower calcinations 3 hours, obtain particle diameter 50-120 microns, compare table
Area 120m2/g catalyst granules.
Catalyst apply when, above-mentioned catalyst is placed in fixed bed, temperature control at 600~800 DEG C, be passed through acetylene,
Argon gas and hydrogen volume ratio 10：85：5 mixed gas, air speed 40h-1, CNT is obtained after separating-purifying.
Embodiment 8
Medical stone powder adds water to be made into the suspension of solid content 25%, by ferric nitrate, ammonium chromate, citric acid in mass ratio 1：3：10
The aqueous solution of total soluble matters content mass fraction 40% is made, the latter's mass is 10% mixing of medical stone suspension quality, is mixed
After uniformly, by sol-gal process 0.48MPa~1.6MPa, 150 DEG C~200 DEG C, body before iron content, chrome catalysts is made in reaction 4h
The suspension of body, the pressure spray dryer at a temperature of 240 DEG C, cyclone separator and sack cleaner collection catalyst precursor,
The particle diameter 90-200 microns of catalyst precursor, after by rotary furnace in 400 DEG C of temperature lower calcinations 2 hours, obtain particle diameter 70-
150 microns, specific surface area 70m2/g catalyst granules.
When catalyst is applied, above-mentioned catalyst is placed in fixed bed, temperature control is passed through ethane, nitrogen at 600-800 DEG C
Air volume is than 2：3 mixed gas, air speed 80h-1, CNT is obtained after separating-purifying.
Embodiment 9
Medical stone powder adds water to be made into the suspension of solid content 35%, by nickel nitrate, citric acid in mass ratio 1：5 are made total soluble matters
The aqueous solution of content mass fraction 30%, the latter's mass are 15% mixing of medical stone suspension quality, after being well mixed, are passed through
Sol-gal process 0.48MPa~1.6MPa, 150 DEG C~200 DEG C, the suspension of nickel-containing catalyst precursor is made in reaction 2h,
Centrifugal spray drying at a temperature of 260 DEG C, cyclone separator and sack cleaner collection catalyst precursor, catalyst precursor grain
Footpath 60-120 microns, after by rotary furnace in 400 DEG C of temperature lower calcinations 2 hours, obtain particle diameter 50-110 microns, specific surface area
200m2/g catalyst granules.
Catalyst apply when, above-mentioned catalyst is placed in fixed bed, temperature control at 700-1000 DEG C, be passed through methane,
Nitrogen, hydrogen volume are than 30：65：5 mixed gas, air speed 65h-1, CNT is obtained after separating-purifying.
Embodiment 10
After medical stone crushes plus water is made into the suspension of solid content 55%, by ferric nitrate, nickel nitrate in mass ratio 1：2 are made
The aqueous solution of total soluble matters content mass fraction 60%, the latter's mass are 5% mixing of medical stone suspension quality, are well mixed
Afterwards, iron content, the suspension of Raney nickel precursor are made by 30 DEG C~50 DEG C of ion-exchange, reaction 3h, suspension adds
Into twin-fluid spray dryer, it is spray-dried at a temperature of 260 DEG C, the cyclone separator and cloth bag of twin-fluid spray dryer
Deduster collection catalyst precursor, catalyst precursor particle diameter 50-150 microns, after be passed into rotary furnace in 600 DEG C of temperature
Lower calcining 2 hours, obtains particle diameter 50-100 microns, specific surface area 90m2/g catalyst granules.
Catalyst apply when, above-mentioned catalyst is placed in fixed bed, temperature control at 700-1000 DEG C, be passed through pentane,
Argon gas, hydrogen volume are than 20：75：5 mixed gas, air speed 75h-1, CNT is obtained after separating-purifying.
Claims (10)
1. a kind of medical stone is the method for preparing catalyst that carrier is used for CNT production, it is characterised in that including following step
Suddenly：(1) carbon nanometer pipe catalytic element is formed nanomorphic distribution on medical stone surface, obtain catalyst precursor；(2) step
(1) catalyst precursor obtained obtains the catalyst for CNT production after high-temperature calcination.
2. preparation method according to claim 1, it is characterised in that step (1) is specially：Medical stone powder adds water to be made into wheat
Meal stone flour suspension, the solution or suspension of the material of carbon nanotubes catalytic elements are added, passes through ion-exchange or dipping
A kind of mixture for preparing carbon nanotubes catalytic elements in method, said mixture is spray-dried, filtering, press filtration, centrifugation
Solvent more than one or both of process is removed, before obtaining the catalyst that catalytic elements nanomorphic is distributed on medical stone surface
Drive body.
3. preparation method according to claim 1, it is characterised in that step (1) is specially：Medical stone powder adds water to be made into wheat
Meal stone flour suspension, precipitating reagent and scattered is added while the solution or suspension of the material for adding carbon nanotubes catalytic elements
Agent, it is above-mentioned by a kind of mixture for preparing carbon nanotubes catalytic elements in coprecipitation, hydro-thermal method, sol-gal process
Mixture is spray-dried, filtering, press filtration, more than one or both of rotary process removes solvent, obtains catalytic elements and receives
Rice state is distributed in the catalyst precursor on medical stone surface.
4. preparation method according to claim 1, it is characterised in that step (1) is specially：Medical stone powder adds water to be made into wheat
Meal stone flour suspension, complexing agent and scattered is added while the solution or suspension of the material for adding carbon nanotubes catalytic elements
Agent, the mixture of carbon nanotubes catalytic elements is prepared by complexometry, said mixture is spray-dried, filtering, press filtration, from
Solvent more than one or both of heart process is removed, obtains the catalyst that catalytic elements nanomorphic is distributed on medical stone surface
Presoma.
5. according to the preparation method described in claim 2,3 or 4, it is characterised in that the medical stone powder suspension solid content is
1%~60%；The carbon nanometer pipe catalytic element be iron, cobalt, nickel, chromium, molybdenum, it is more than one or both of tungsten, it is described carbon containing
The material of nanotube catalytic elements refer to the oxide containing iron, cobalt, nickel, chromium, molybdenum or tungsten, hydroxide, chloride, cyanide,
More than one or both of fluoride, nitrate, sulfate, silicate, acylate, chromate, molybdate, tungstates
Compound or their compound；In the solution or suspension of the material of the carbon nanotubes catalytic elements, above-claimed cpd
Or the Solute mass concentration or solid content of compound are 0.5%-95%；The temperature of the high-temperature calcination is 300 DEG C -1200 DEG C,
Calcination time is 1-24 hours；The spray drying, spray dryer be drying machine with centrifugal spray, Pressuresprayingdrier or
One kind in two/tri- fluid spray dryers, the temperature of spray dryer is 120 DEG C -400 DEG C；The catalyst precursor grain
Footpath scope 50-1000 microns.
6. preparation method according to claim 5, it is characterised in that the medical stone powder suspension solid content be 5%~
40%；In the solution or suspension of the material of the carbon nanotubes catalytic elements, the solute matter of the compound or compound
It is 2%-50% to measure concentration or solid content；The spray drying, the temperature of spray dryer is 200 DEG C -300 DEG C.
7. preparation method according to claim 3, it is characterised in that the precipitating reagent is soluble hydroxide, solvable
It is more than one or both of acid carbonate or bicarbonate, soluble ammonium salt, ammonia, urea；The dispersant be sodium metaphosphate,
Sodium alkyl benzene sulfonate, polyvinyl alcohol, polyethylene glycol oxide, three sections of copolymers of polyoxyethylene-poly-oxypropylene polyoxyethylene type, poly- second
It is one or more kinds of in alkene pyrrolidone；The precipitating reagent dosage is the 50%- of carbon nanometer pipe catalytic element theory mole
150%；Dispersant dosage is the 0.1%-10% of system gross mass.
8. preparation method according to claim 4, it is characterised in that the complexing agent is citric acid, tartaric acid, sweet ammonia
One or two or more kinds in acid, the amine tetraacethyl of second two；The dispersant be sodium metaphosphate, sodium alkyl benzene sulfonate, polyvinyl alcohol,
It is one or two kinds of in polyethylene glycol oxide, polyoxyethylene-poly-oxypropylene polyoxyethylene type three sections of copolymers, polyvinylpyrrolidones
More than；Amount of complex is the 20%-300% of catalytic elements theoretical molar amount；Dispersant dosage is system gross mass
0.1%-10%.
A kind of 9. catalyst for being used for CNT and producing prepared according to any one of claim 1-8 methods described.
A kind of 10. application of the catalyst described in claim 9 in CNT is prepared, it is characterised in that：Catalyst is put
Put in high-temperature service, be passed through the mixed gas containing seven carbon and following organic gas and inert gas and reducibility gas, control
At 500 DEG C -1200 DEG C, mixed gas air speed controls in 0.1h temperature processed-1-100h-1, CNT crude product is prepared, by
Separating-purifying, CNT is made；Wherein high-temperature service is one in roller kilns, rotary furnace, fixed bed, moving bed or fluid bed
Kind.
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| CN114229833A (en) * | 2020-09-09 | 2022-03-25 | 哈尔滨金纳科技有限公司 | Preparation method of carbon nanotube material with easy dispersion and high conductivity |
| CN114340787A (en) * | 2019-09-05 | 2022-04-12 | 赢创运营有限公司 | Material comprising carbon-embedded nickel nanoparticles, method for the production thereof and use as heterogeneous 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 |
| CN115350657A (en) * | 2022-09-19 | 2022-11-18 | 广西信业生物技术有限公司 | Preparation process and application of medical stone novel gel |
| CN115532276A (en) * | 2022-10-12 | 2022-12-30 | 山东碳峰新材料科技有限公司 | Preparation and application of nickel-based carbon nanotube catalyst |
| CN116751567A (en) * | 2023-08-10 | 2023-09-15 | 华南理工大学 | Biological carbon photo-thermal composite shaping phase change material and preparation method and application thereof |
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