CN102120570A - Device and process method for continuously producing carbon nanotubes - Google Patents
Device and process method for continuously producing carbon nanotubes Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 40
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
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- 238000003672 processing method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
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- 239000000463 material Substances 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
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- 238000001354 calcination Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention discloses a device for continuously producing carbon nanotubes, which consists of a feeder, a reduction reactor, a synthesis reactor and a product collector which are connected in series in turn, wherein the reduction reactor is a fluidized bed reactor; and the synthesis reactor is a spouted bed reactor. The invention also discloses a process method for continuously producing carbon nanotubes based on the device. The catalyst reduction and deposition preparation of the carbon nanotubes are respectively realized by the fluidized bed and the spouted bed, so that the process conditions can be regulated in a wider range, the fluidized state of agglomerated nanoparticles in the beds is ensured, and the high-quality carbon nanotubes are continuously produced.
Description
Technical field
The present invention relates to technical field of nano material, relate in particular to a kind of production equipment and processing method of carbon nanotube.
Background technology
Carbon nanotube has typical stratiform hollow structure feature, has certain included angle between the synusia of formation carbon nanotube, and the pipe shaft of carbon nanotube is the director circle tubular construction, and great majority are made up of the pentagonal section.The pipe shaft of carbon nanotube is several layers to tens of layers the coaxial pipe of being made up of hexagon carbocyclic ring microstructure unit, and the distance that is maintained fixed between layer and the layer is about 0.34nm, and diameter is generally 2～20nm; Terminal cap moiety is served as reasons and is contained the polygonized structure that pentagonal carbocyclic ring is formed, and perhaps is called the many wall constructions of polygon taper, is a kind of One-dimensional Quantum material with special construction.Because its particular structure, the research of carbon nanotube has important in theory meaning and potential using value, and these application comprise fields such as structure enhancing, molecular wire, nano semiconductor material, support of the catalyst, molecular absorption agent and near field emissive material.
At present, the preparation method of prior art carbon nanotube mainly contains arc process, CVD pyrolysis method and laser ablation method.Wherein arc process is in inert gas atmosphere, and two root graphite electrode direct-current discharges produce carbon nanotube on negative electrode.The CVD pyrolysis method adopts transition metal to make catalyzer exactly, and under the condition of 700～1600K, the decomposition by hydrocarbon polymer obtains carbon nanotube.The laser ablation method adopts the graphite target in the laser ablation High Temperature Furnaces Heating Apparatus, carbon nanotube just is present in the graphite evaporate that rare gas element carries secretly, the carbon atom of free state or carbon atom group takes place to arrange again and forms carbon nanotube, and the diameter of prepared carbon nanotube and diameter Distribution depend primarily on reaction conditionss such as the kind, growth temperature of preparation method, catalyzer.At present, the technology of producing multi-walled carbon nano-tubes by the catalysis hydrocarbon cracking has had commercial size, but the smooth fluidisation, the reaction bed body that how to ensure monodimension nanometer material do not occur luming, do not produce localized hyperthermia and density unevenness and realize that serialization production etc. is the difficult problem that the carbon nanotube production industry is difficult to overcome always.At present, prior art all is only to use independent fluidized-bed to carry out the prepared in reaction carbon nanotube, the inreal production that realizes serialization, and can't be in relative broad range the adjusting process condition, be difficult to control the stability of fluidized state and mass-and heat-transfer, thereby can't guarantee to continuously produce high-quality carbon nanotube.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the device of a kind of fluidized-bed and the placed in-line producing Nano carbon tubes continuously of spouted bed is provided, the fluidized state under the air-flow effect with control catalyst and product, improve the stability of whole process mass-and heat-transfer, guarantee the fluidized state of bed agglomeration of nano-size particle and continuously produce high-quality carbon nanotube.Another object of the present invention is to provide a kind of processing method of producing Nano carbon tubes continuously.
Purpose of the present invention is achieved by the following technical programs:
The device of a kind of producing Nano carbon tubes continuously provided by the invention is by placed in-line feeder, reduction reactor, synthesis reactor and product collector are formed successively; Described reduction reactor is a fluidized-bed reactor, and described synthesis reactor is spouted bed bioreactor.Apparatus of the present invention are with fluidized-bed reactor and the series connection of spouted bed bioreactor, fluidized-bed reactor wherein is that reduction reactor is used for reduction preparation metallic catalyst, spouted bed bioreactor is that synthesis reactor is used to produce carbon nanotube, by being divided into relatively independent stage and step, improved the stability of product and the handiness of operation, and realized from being fed to the serialization production of discharging.
Another object of the present invention is achieved by the following technical programs:
The processing method of a kind of producing Nano carbon tubes continuously provided by the invention is by Preparation of catalysts and based on placed in-line feeder, reduction reactor, synthesis reactor and product collector make successively; Described reduction reactor is a fluidized-bed reactor, and described synthesis reactor is spouted bed bioreactor; May further comprise the steps:
A. the adding of catalyzer
Catalyzer is added in the feeder, vacuumize and feed nitrogen, detect oxygen concentration to determine the security of system;
B. reducing catalyst
By feeder described catalyzer is added in the fluidized-bed of reduction reactor, under nitrogen and hydrogen gas mixture, carry out reduction reaction, N in 450～900 ℃
2: H
2Volume ratio=0.4～1: 1, the recovery time is 30～180min, makes the transition metal oxide particle be reduced to the elemental metals nano particle;
C. synthesizing carbon nanotubes
Catalyzer after the reduction enters in the spouted bed of synthesis reactor, feeds nitrogen, hydrogen and carbon source gas in 500～900 ℃ and reacts N
2: H
2: the volume ratio of carbon source gas=0.3～1: 0.5～1: 1, the air speed of reaction process is 10～10000 hours
～1, the void tower flow velocity of gas is 0.08～2m/s, reaction time is 50～150min; Reaction product enters product collector;
D. collect product
The carbon nano tube products that obtains enters the material stock tube of band nitrogen protection in the product collector, promptly gets the carbon nanotube finished product after cooling.
Processing method of the present invention, catalyzer are reduced under the acting in conjunction of hydrogen and nitrogen in fluidized-bed and are made metallic catalyst; Utilize the catalytic effect of transition metal nanoparticles and the template effect of carrier, in spouted bed,, on support of the catalyst, grow carbon nanotube through chemical gaseous phase deposition.The easy stdn of operating process of the present invention is fit to serialization large-scale commercial production carbon nanotube.
Further, among the described step b of processing method of the present invention, at first feed nitrogen, and increase tolerance gradually and make that gas-solid is fully contacted mutually in the fluidized-bed; Feeding hydrogen then fully contacts with the fluidizing solid phase and carries out reduction reaction; Reaction finishes, and strengthens nitrogen flow gradually, and the catalyst feed after the reduction is discharged in the spouted bed of synthesis reactor from overflow port.Among the described step c, at first feed nitrogen, and increase tolerance gradually and make bed be spouted state; By jet hole carbon source gas and hydrogen are sprayed in the bed centre pipe then and carry out abundant contact reacts with solid phase; Reaction finishes, and strengthens nitrogen flow gradually, makes resultant be discharged to product collector from overflow port.
The described carbon source gas of processing method of the present invention is acetylene, methane, propane.
In addition, aspect Preparation of Catalyst, the described catalyzer of processing method of the present invention is by carrier and one or more VIII main group metal element water-soluble salts, through stirring, dry, make after calcining, grind, sieving; The carrier addition is 1～5 times of metallic element water-soluble salt quality.Preferably, described VIII main group metal element water-soluble salt is the one or more combination of Xiao Suangu, nickelous nitrate, iron nitrate; With Xiao Suangu: nickelous nitrate: the mol ratio of iron nitrate=0～4: 1: 0～4 are advisable, preferred, Xiao Suangu: nickelous nitrate: the mol ratio of iron nitrate=1～4: 1: 1～4.Described carrier is alumina gel, silicon-dioxide, magnesium oxide or diatomite.
The present invention has following beneficial effect:
(1) apparatus of the present invention combine the characteristics of fluidized-bed and spouted bed bioreactor, and compact construction is practical.
(2) can height CONTROL PROCESS condition and parameter, and realize helping guaranteeing the large-scale production of product from being fed to the serialization production of discharging, realize the widespread use of product.
(3) can realize conducting heat and moving heat on large-scale device, realize that temperature, concentration are carried out the growth of carbon nanotube equably in the bed, no local superheating and bonding phenomenon take place.
(4) be applicable to that the wide range regulation processing condition are to satisfy the needs of different activities Catalyst Production carbon nanotube, and can be divided into relatively independent stage and step, improve the utilization ratio of catalyzer and gas, reduced environmental pollution, and improved the stability of product and the handiness of operation.The easy stdn of operating process is fit to serialization large-scale commercial production carbon nanotube.
Description of drawings
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing:
Fig. 1 is the structural representation of producing Nano carbon tubes continuously device in the embodiment of the invention.
Among the figure: feeder 1, reduction reactor 2, synthesis reactor 3, product collector 4
Embodiment
Figure 1 shows that producing Nano carbon tubes continuously device embodiment of the present invention, by placed in-line feeder 1, reduction reactor 2, synthesis reactor 3 and product collector 4 are formed successively, wherein reduction reactor 2 is a fluidized-bed reactor, and synthesis reactor 3 is spouted bed bioreactor.
Embodiment one:
The processing method of present embodiment producing Nano carbon tubes continuously, wherein the Preparation of catalysts process is as follows: Xiao Suangu and nickelous nitrate is soluble in water according to 0.6: 1 molar ratio, after stirring, adding 5 times of alumina gels to the metal-salt quality mixes, 120 ℃ of dryings 2 hours, put into retort furnace in 600 ℃ of calcinings 3 hours, grind, stand-by after 200 orders sieve.
Based on production equipment shown in Figure 1, the processing method step of present embodiment producing Nano carbon tubes continuously is as follows:
A. the adding of catalyzer
The catalyzer of above-mentioned preparation is added in the feeder 1, vacuumize and reach 600mmHg and feed nitrogen, detect oxygen concentration, if oxygen concentration is less than 100PPM, then system has security.
B. reducing catalyst
Catalyzer is added in the fluidized-bed of reduction reactor 2 by feeder 1, at first feed nitrogen, heating rising nitrogen and bed temperature, and increase tolerance gradually and make that gas-solid is fully contacted mutually in the fluidized-bed; Feeding hydrogen then fully contacts with the fluidizing solid phase and carries out reduction reaction; Temperature of reaction is 500 ℃, N
2: H
2Volume ratio=1: 1, the recovery time is 50min, makes the transition metal oxide particle be reduced to the elemental metals nano particle; Reaction finishes, and strengthens nitrogen flow gradually, and the catalyst feed after the reduction is discharged in the spouted bed of synthesis reactor 3 from overflow port.
C. synthesizing carbon nanotubes
Catalyzer after the reduction enters in the spouted bed of synthesis reactor 3, at first feeds nitrogen, heating rising nitrogen and bed temperature, and increases tolerance gradually and make bed be spouted state; By jet hole acetylene and hydrogen are sprayed in the bed centre pipe then and carry out abundant contact reacts with solid phase; Temperature of reaction is 600 ℃, N
2: H
2: C
2H
2Volume ratio=1: 1: 1, the air speed of reaction process is 5000 hours
～1, the void tower flow velocity of gas is 0.8m/s, reaction time is 50min; Reaction finishes, and strengthens nitrogen flow gradually, makes resultant be discharged to product collector 4 from overflow port.
D. collect product
The carbon nano tube products that obtains enters the material stock tube of band nitrogen protection in the product collector 4, promptly gets the carbon nanotube finished product after refrigerant is expected 120 ℃.
The parameter and the performance of gained carbon nanotube product are as follows: purity＞90%, external diameter 10～30nm, length 10～30 μ m, specific surface area＞150m
2/ g, black, bulk density 0.14g/cm
3
Embodiment two:
The processing method of present embodiment producing Nano carbon tubes continuously is with embodiment one difference:
(1) in the Preparation of catalysts process, metal-salt uses nickelous nitrate; Carrier is a magnesium oxide, and its consumption is 2 times of metal-salt quality; Calcining temperature is 500 ℃.
(2) among the step b, N
2: H
2Volume ratio=0.4: 1, the recovery time is 30min.
(3) among the step c, temperature of reaction is 900 ℃, and carbon source gas is methane, N
2: H
2: CH
4Volume ratio=0.3: 0.5: 1, the air speed of reaction process is 10000 hours
～1, the void tower flow velocity of gas is 0.5m/s, reaction time is 60min.
The parameter and the performance of gained carbon nanotube product are as follows: purity＞88%, external diameter 15～30nm, length 10～30 μ m, specific surface area＞120m
2/ g, black, bulk density 0.14g/cm
3
Embodiment three:
The processing method of present embodiment producing Nano carbon tubes continuously is with embodiment one difference:
(1) in the Preparation of catalysts process, adopts Xiao Suangu and iron nitrate, Xiao Suangu: iron nitrate mol ratio=1: 4; The consumption of alumina catalyst support gel is 3 times of metal-salt quality; Calcining temperature is 500 ℃.
(2) among the step b, temperature of reaction is 450 ℃, and the recovery time is 180min.
(3) among the step c, temperature of reaction is 700 ℃, and carbon source gas is propane, N
2: H
2: C
3H
6Volume ratio=0.5: 1: 1, the air speed of reaction process is 5000 hours
～1, reaction time is 70min.
The parameter and the performance of gained carbon nanotube product are as follows: purity＞92%, external diameter 10～35nm, length 15～30 μ m, specific surface area＞130m
2/ g, black, bulk density 0.14g/cm
3
Embodiment four:
The processing method of present embodiment producing Nano carbon tubes continuously is with embodiment one difference:
(1) in the Preparation of catalysts process, adopts Xiao Suangu, nickelous nitrate and iron nitrate, Xiao Suangu: nickelous nitrate: iron nitrate mol ratio=1: 1: 2; Carrier is a silicon-dioxide, and its consumption is 1 times of metal-salt quality; Calcining temperature is 500 ℃.
(2) among the step b, temperature of reaction is 900 ℃, and the recovery time is 60min.
(3) among the step c, temperature of reaction is 500 ℃, N
2: H
2: C
2H
2Volume ratio=1: 0.5: 1, the air speed of reaction process is 9000 hours
～1, the void tower flow velocity of gas is 1.5m/s, reaction time is 100min.
The parameter and the performance of gained carbon nanotube product are as follows: purity＞90%, external diameter 20～30nm, length 10～30 μ m, specific surface area＞100m
2/ g, black, bulk density 0.14g/cm
3
The processing method of producing Nano carbon tubes continuously of the present invention, its proportioning raw materials consumption and processing parameter are not limited to above-mentioned listed examples.
Claims (10)
1. the device of a producing Nano carbon tubes continuously is characterized in that: by placed in-line feeder (1), reduction reactor (2), synthesis reactor (3) and product collector (4) are formed successively; Described reduction reactor (2) is a fluidized-bed reactor, and described synthesis reactor (3) is spouted bed bioreactor.
2. the processing method of a producing Nano carbon tubes continuously is characterized in that: by Preparation of catalysts and based on placed in-line feeder (1), reduction reactor (2), synthesis reactor (3) and product collector (4) make successively; Described reduction reactor (2) is a fluidized-bed reactor, and described synthesis reactor (3) is spouted bed bioreactor; May further comprise the steps:
A. the adding of catalyzer
Catalyzer is added in the feeder (1), vacuumize and feed nitrogen, detect oxygen concentration to determine the security of system;
B. reducing catalyst
By feeder (1) described catalyzer is added in the fluidized-bed of reduction reactor (2), under nitrogen and hydrogen gas mixture, carry out reduction reaction, N in 450～900 ℃
2: H
2Volume ratio=0.4～1: 1, the recovery time is 30～180min, makes the transition metal oxide particle be reduced to the elemental metals nano particle;
C. synthesizing carbon nanotubes
Catalyzer after the reduction enters in the spouted bed of synthesis reactor (3), feeds nitrogen, hydrogen and carbon source gas in 500～900 ℃ and reacts N
2: H
2: the volume ratio of carbon source gas=0.3～1: 0.5～1: 1, the air speed of reaction process is 10～10000 hours
～1, the void tower flow velocity of gas is 0.08～2m/s, reaction time is 50～150min; Reaction product enters product collector (4);
D. collect product
The carbon nano tube products that obtains enters the material stock tube of band nitrogen protection in the product collector (4), promptly gets the carbon nanotube finished product after cooling.
3. the processing method of producing Nano carbon tubes continuously according to claim 2 is characterized in that: among the described step b, at first feed nitrogen, and increase tolerance gradually and make that gas-solid is fully contacted mutually in the fluidized-bed; Feeding hydrogen then fully contacts with the fluidizing solid phase and carries out reduction reaction; Reaction finishes, and strengthens nitrogen flow gradually, and the catalyst feed after the reduction is discharged in the spouted bed of synthesis reactor (3) from overflow port.
4. the processing method of producing Nano carbon tubes continuously according to claim 2 is characterized in that: among the described step c, at first feed nitrogen, and increase tolerance gradually and make bed be spouted state; By jet hole carbon source gas and hydrogen are sprayed in the bed centre pipe then and carry out abundant contact reacts with solid phase; Reaction finishes, and strengthens nitrogen flow gradually, makes resultant be discharged to product collector (4) from overflow port.
5. according to the processing method of claim 2 or 4 described producing Nano carbon tubes continuouslies, it is characterized in that: described carbon source gas is acetylene, methane, propane.
6. the processing method of producing Nano carbon tubes continuously according to claim 2 is characterized in that: described catalyzer is by carrier and one or more VIII main group metal element water-soluble salts, through stirring, dry, make after calcining, grind, sieving; The carrier addition is 1～5 times of metallic element water-soluble salt quality.
7. the processing method of producing Nano carbon tubes continuously according to claim 6, it is characterized in that: described VIII main group metal element water-soluble salt is the one or more combination of Xiao Suangu, nickelous nitrate, iron nitrate.
8. the processing method of producing Nano carbon tubes continuously according to claim 7 is characterized in that: described Xiao Suangu: nickelous nitrate: the mol ratio of iron nitrate=0～4: 1: 0～4.
9. the processing method of producing Nano carbon tubes continuously according to claim 8 is characterized in that: described Xiao Suangu: nickelous nitrate: the mol ratio of iron nitrate=1～4: 1: 1～4.
10. the processing method of producing Nano carbon tubes continuously according to claim 6, it is characterized in that: described carrier is alumina gel, silicon-dioxide, magnesium oxide or diatomite.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628183A (en) * | 2013-12-06 | 2014-03-12 | 天津大学 | Method for large-scale production of continuous carbon nano tube fiber |
| CN104401966A (en) * | 2014-11-28 | 2015-03-11 | 湖南顶立科技有限公司 | Continuous type production equipment and method of carbon nano tube |
| CN105776176A (en) * | 2016-02-25 | 2016-07-20 | 佛山市南海万兴材料科技有限公司 | Nano-carbon powder preparation device |
| CN106379885A (en) * | 2016-08-31 | 2017-02-08 | 潍坊昊晟碳材料有限公司 | Efficient preparation method of carbon nanotubes or graphene |
| CN106395793A (en) * | 2016-08-31 | 2017-02-15 | 潍坊昊晟碳材料有限公司 | Reduction activation-reaction coupled high-efficiency preparation method for carbon nanotube |
| CN106395794A (en) * | 2016-08-31 | 2017-02-15 | 潍坊昊晟碳材料有限公司 | Efficient continuous preparation method of coupled fluidized bed carbon nanotubes |
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| CN106379885B (en) * | 2016-08-31 | 2019-11-19 | 潍坊昊晟碳材料有限公司 | A kind of high efficiency preparation method of carbon nanotube or graphene |
| CN114247387A (en) * | 2021-12-20 | 2022-03-29 | 广州盛泰诺新材料科技有限公司 | High-efficiency continuous production process and device for high-quality silicone oil |
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| CN114471384A (en) * | 2021-12-31 | 2022-05-13 | 佛山市格瑞芬新能源有限公司 | Fluidized bed reaction system for improving production efficiency of carbon nano tube and carbon nano tube production method |
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| CN115477300A (en) * | 2022-08-03 | 2022-12-16 | 烯湾科城(广州)新材料有限公司 | Carbon nano tube, fluidized bed preparation process thereof and conductive agent |
| CN115477300B (en) * | 2022-08-03 | 2024-05-07 | 烯湾科城(广州)新材料有限公司 | Carbon nanotube, fluidized bed preparation process thereof and conductive agent |
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