JP2008037696A - Nanocarbon material production apparatus and nanocarbon material purification method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nanocarbon material production apparatus capable of producing a nanocarbon material aggregating little and having improved dispersibility and a nanocarbon material purification method. <P>SOLUTION: The nanocarbon material production apparatus comprises a nanocarbon material production part 15 for producing a catalyst-attached nanocarbon material by a fluidized bed reactor, an acid treatment device 17 which disperses the resultant catalyst-attached nanocarbon material in an acid solution 16 and dissolves and separates a catalyst with the acid solution 16, a water washing device 19 for washing the acid-treated nanocarbon material 18 with water, a drying device 24 which dries the water-washed nanocarbon material 18 after its filtration with a filtration device 23, and a finely pulverizing device 25 for finely pulverizing the dried nanocarbon material to give a purified nanocarbon material 26. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a nanocarbon material manufacturing apparatus and a nanocarbon material refining method with improved dispersibility of a nanocarbon material.

  The carbon nanotube is a tubular carbon polyhedron having a structure in which a graphite (graphite) sheet is closed in a cylindrical shape. The carbon nanotube includes a multi-layer nanotube having a multilayer structure in which a graphite sheet is closed in a cylindrical shape, and a single-wall nanotube having a single-layer structure in which a graphite sheet is closed in a cylindrical shape.

  One multi-walled nanotube was discovered by Iijima in 1991. That is, it was discovered that multi-walled nanotubes exist in the carbon mass deposited on the cathode of the arc discharge method (Non-Patent Document 1). Since then, research on multi-walled nanotubes has been actively conducted, and in recent years, it has become possible to synthesize a large number of multi-walled nanotubes.

  In contrast, single-walled nanotubes have an inner diameter of approximately 0.4 to 10 nanometers (nm), and their synthesis was simultaneously reported in 1993 by a group of Iijima and IBM. The electronic state of single-walled nanotubes has been predicted theoretically, and it is thought that the electronic properties change from metallic properties to semiconducting properties depending on how the spiral is wound. Therefore, such single-walled nanotubes are considered promising as future electronic materials.

  Other applications of single-walled nanotubes include conductive composite materials, nanoelectronic materials, field electron emitters, highly directional radiation sources, soft X-ray sources, one-dimensional conducting materials, high thermal conducting materials, hydrogen storage materials, etc. It has been. Further, it is considered that the use of single-walled nanotubes is further expanded by functionalization of the surface, metal coating, and inclusion of foreign substances.

Conventionally, the single-walled nanotubes described above are manufactured by mixing a metal such as iron, cobalt, nickel, or lanthanum into a carbon rod of an anode and performing arc discharge (Patent Document 1).
However, in this manufacturing method, in addition to single-walled nanotubes, multi-walled nanotubes, graphite, and amorphous carbon are mixed in the product, and not only the yield is low, but also the diameter and length of single-walled nanotubes vary. It was difficult to produce single-walled nanotubes with relatively uniform diameter and length in high yield.

  In addition to the arc method described above, a vapor phase pyrolysis method, a laser sublimation method, a condensed phase electrolysis method, and the like have been proposed as methods for producing carbon nanotubes (Patent Documents 2 to 4).

  However, any of the production methods disclosed in these documents is a laboratory or small-scale production method, and there is a problem that the yield of the carbon material is low and the purity is particularly low.

  Therefore, the present applicant has previously proposed an apparatus and method for producing carbon nanofibers, which are nano-unit carbon materials that can be continuously mass-produced using a fluidized bed reaction method (Patent Document 5).

S, Iijima, Nature, 354, 56 (1991) Japanese Patent Laid-Open No. 06-280116 Japanese Patent No. 3100962 Japanese Patent Publication No. 2001-520615 JP 2001-139317 A JP 2004-76197 A

  In the production of nano-unit carbon materials by the previously proposed fluidized bed reaction method, the fluidized catalyst that combines the fluidized material and the catalyst uses secondary particles that are granulated from primary particles and coarsened. A bubble-bed fluidized bed reactor is formed to allow sufficient reaction time of the catalyst particles, but the carbon material is generated while being complicatedly entangled inside the secondary particles, which are the primary particles. Therefore, there is a problem that the carbon material is agglomerated with the progress of generation and the dispersibility is lowered.

That is, as shown in FIG. 5, the catalyzed nanocarbon material 106 in which the nanocarbon material is grown from the catalyst dissolves the catalyst by acid treatment using the acid 110 to obtain the purified nanocarbon material 111. Then, when performing filtration operation and drying, there is a problem that the nanocarbon materials are entangled and become a nanocarbon material aggregate 112.
When this aggregate is mixed with, for example, a resin or the like, it becomes a cause of ubiquity, and it is desired to prevent the aggregation of the nanocarbon material in the purification process.

  The cause of the aggregation of the nanocarbon material is that, in the production of the nanocarbon material using a fluidized bed reactor, as shown in FIG. 6, a plurality of catalysts 103 composed of the active component 102 supported on the carrier 101 are granulated. By using the catalyst granulated body 104 made as a fluidizing material.

  That is, in the fluidized bed reactor, the catalyst granule 104 grows the nanocarbon material 105 from the active component 102 as shown in FIG. 7 by supplying the carbon raw material. Since the nanocarbon material grows in a gap between the catalysts 103 in a complicated manner, even after the catalyst 103 is dissolved and removed by acid treatment, the nanocarbon material is dried without being untangled. It is assumed that the material aggregate 112 is obtained.

  Also, in recent years, various uses of carbon materials have been expanded, but since the range of applications of carbon materials with improved dispersibility is widened, it is possible to efficiently produce a large amount of nanocarbon materials with little aggregation The advent of methods and devices is desired.

  In view of the above circumstances, an object of the present invention is to provide a nanocarbon material production apparatus and a nanocarbon material purification method capable of efficiently producing a carbon material with improved dispersibility and a large amount and less aggregation. To do.

  The first invention of the present invention for solving the above-mentioned problems is an acid treatment device in which a nanocarbon material with a catalyst is dispersed in an acid solution, and the catalyst is dissolved and separated by the acid solution, and the acid-treated nanocarbon. A nanocarbon material manufacturing apparatus comprising a water washing apparatus for washing a material, a drying apparatus for drying the washed nanocarbon material, and a fine grinding apparatus for finely grinding the dried nanocarbon material.

  A second invention is the nanocarbon material manufacturing apparatus according to the first invention, wherein the acid treatment apparatus is an ultrasonic acid treatment apparatus.

  A third invention is the nanocarbon material production apparatus according to the first or second invention, wherein a surfactant is added to one or both of the acid treatment apparatus and the water washing apparatus.

  A fourth invention is the nanocarbon material manufacturing apparatus according to any one of the first to third inventions, wherein the drying apparatus is a heat drying apparatus, a freeze drying apparatus, or a spray drying apparatus.

  According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the apparatus includes a fine pulverization / classification device that is provided on the upstream side of the dispersion treatment device and finely pulverizes / classifies the nanocarbon material with catalyst. It is in the nano-carbon material manufacturing equipment that is characterized.

  A sixth aspect of the present invention is the nanocarbon according to any one of the first to fifth aspects, further comprising a heat treatment device that is provided on the upstream side of the dispersion treatment device and heat-treats the nanocarbon material with catalyst. In material production equipment.

  A seventh invention is the nanocarbon material production apparatus according to any one of the first to sixth inventions, wherein the production apparatus for producing the catalyst-coated nanocarbon material is a fluidized bed reactor.

  According to an eighth aspect of the present invention, in the seventh aspect of the invention, there is provided a nanocarbon material production apparatus using a fluidized bed reactor, comprising a fluidized catalyst supply device for supplying a fluidized catalyst to be supplied to the fluidized bed reactor.

  A ninth invention is the nanocarbon material production apparatus using a fluidized bed reactor according to the eighth invention, wherein the fluidized catalyst has a particle size of 200 μm to 5 mm.

  A tenth aspect of the invention includes a nanocarbon material comprising the nanocarbon material manufacturing apparatus according to any one of the first to ninth aspects and a resin mixing apparatus that mixes the obtained nanocarbon material with a resin. It exists in the manufacturing system of a resin composition.

  In an eleventh aspect, the nanocarbon material with catalyst is dispersed in an acid solution and the catalyst is separated, and after the acid treatment, the water washing step of washing the nanocarbon material with water, and the water-washed nanocarbon material are dried. The present invention resides in a method for purifying a nanocarbon material comprising a drying step.

  A twelfth invention is the nanocarbon material purification method according to the eleventh invention, wherein the acid treatment step is performed by ultrasonic treatment.

  A thirteenth aspect of the invention is the nanocarbon material refining method according to the eleventh or twelfth aspect of the invention, further comprising a pulverization / classification step of pulverizing / classifying the nanocarbon material with catalyst before the acid treatment step. It is in.

  A fourteenth aspect of the invention is a nanocarbon material refining method according to any one of the eleventh to thirteenth aspects, further comprising a heat treatment step of heat-treating the nanocarbon material with catalyst before the acid treatment step. is there.

  The fifteenth aspect of the invention includes a resin mixing step of purifying the nanocarbon material using any one of the eleventh to fourteenth nanocarbon material purification methods and then mixing the separated nanocarbon material with the resin. It is in the manufacturing method of the nanocarbon material resin composition characterized.

  According to the present invention, it is possible to provide a nanocarbon material with good dispersibility by dissolving and removing the catalyst from the aggregated carbon material with an acid, followed by drying and high-dispersion with a fine pulverizer.

  Hereinafter, the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited by this embodiment. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

[Embodiment 1]
A schematic diagram of a nanocarbon material production apparatus according to the present embodiment is shown in FIG.
As shown in FIG. 1, the nanocarbon material manufacturing apparatus 10A according to Embodiment 1 includes a nanocarbon material manufacturing unit 15 that manufactures a catalyst-coated nanocarbon material using a fluidized bed reactor, and the obtained catalyst-coated nanocarbon material. Is dispersed in the acid solution 16, and an acid treatment device 17 for dissolving and separating the catalyst by the acid solution 16, a water washing device 19 for washing the acid-treated nanocarbon material 18, and a filtration device for washing the washed nanocarbon material 18. 23, a drying device 24 for drying after filtration, and a fine grinding device 25 for finely grinding the dried nanocarbon material to obtain a purified nanocarbon material 26.
In FIG. 1, reference numeral 20 denotes a recovery device that separates the nanocarbon material with catalyst and the fluidized catalyst, 21 denotes a reuse line that reuses the separated fluidized catalyst again in the fluidized bed reactor 13, and 22 denotes exhaust gas. Each is illustrated.

  As a drying device for drying the nanocarbon material after being filtered by the filtering device 23, any one of a heat drying device, a freeze drying device, or a spray drying device is used.

  Here, the heating and drying apparatus includes a first drying method for performing a drying operation at 400 ° C. or lower in the presence of air and a second drying method for performing a drying operation at 1000 ° C. or lower in an inert gas atmosphere. Can be used.

  Freeze-drying is a method of removing moisture by a freeze-drying method in which a liquid is sublimated after freezing and dried at once. As a result, entanglement of the nanocarbon material due to heating can be prevented, and a fluffy nanocarbon material can be obtained.

In addition, the effect of preventing entanglement can be increased by pulverizing with the fine pulverizer 25 and drying after freezing. Further, as a pulverization method, for example, a jet mill, a hammer mill, a roll mill, a ball mill, a bead mill, a mortar or the like that can be pulverized in a normal state while maintaining a frozen state can be used, but there is no need to specifically limit them.
The pulverized particle size is preferably smaller, and the particle size is preferably 1 μm or less, more preferably submicron or less.

  In order to maintain the frozen state, the environment to which the powder is exposed may be lowered. Further, the pulverizer itself may be installed in a low temperature environment.

  Further, ball milling or the like may be performed in a cryogenic solvent using liquid nitrogen or the like.

  In addition to freeze-drying, spray drying using a spray dryer may be performed.

  When the catalyst is removed by the acid treatment device 17, the dispersion may be performed by, for example, a stirring device or an ultrasonic homogenizer. Here, as an acid used in the acid treatment apparatus 17, it is preferable to use strong acids, such as a sulfuric acid, hydrochloric acid, nitric acid, aqua regia, for example. In addition to a strong acid, an auxiliary agent such as hydrogen peroxide may be added.

  Further, in the acid treatment device 17, the dispersing action may be promoted by using a surfactant 27. Here, as the surfactant to be used, any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant may be used. For example, inorganic acid esters, cyclic ethers, Carboxylic anhydride, dicarboxylic acid, aliphatic carboxylic acid, unsaturated carboxylic acid, alicyclic ketone, alicyclic alcohol, aliphatic alcohol, aliphatic chlorine compound, aliphatic amine, aliphatic nitrile, unsaturated fatty acid, carboxamide Directional group polyamide, azo compound, pyrene functionalized block copolymer, cellulose derivative, long-chain benzenediazonium, glucose oxidase, nitrile alicyclic compound, quinoid compound, polyol, diol, diamine, diene and the like.

  Specifically, pyridinium, polyphenylene sulfide, polyvinylidene fluoride, polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyethyleneimine, polypropylene oxide, polymethyl methacrylate, polyvinylpyrrolidone, polyacrylic acid, polyaspartic acid, phospholipid, lecithin , Carboxymethyl cellulose, steroid, saccharide, oligomer, alkyl benzene, chitosan, olefin compound, sugar alcohol, gelatin, linear alkylbenzene sulfonate (LAS), alkylbenzene sulfonate (ABS), sodium dodecyl sulfate (SDS), sodium Examples include sulfonic acid formamide (NSF) and sodium cholate.

  Here, the agglomerated carbon material is grown from the active component of the catalyst granule 104 as shown in FIG. Further, the catalyst granule 104 is obtained by aggregating or agglomerating primary particles made of a carrier carrying an active ingredient, and the particle size of the catalyst granule 104 as a secondary particle is 200 μm to 5 mm, preferably 500 μm to 2000 μm, more preferably 500 μm to 1000 μm.

  Here, in order to obtain a catalyst granulated body in which primary particles are aggregated or aggregated, the primary particles are granulated with a binder, or after pressing the primary particles with a pressure device to obtain a molded body, a predetermined particle size is obtained. Is obtained by sizing so that

Further, the specific surface area of the catalyst composed of the secondary particles is preferably 100 m ² or more from the viewpoint of improving the yield of the carbon material from the viewpoint of improving the yield.

In addition, since the carrier has innumerable pores, the growth space of the carbon material is limited by the (small pore diameter) / (large pore diameter) ratio of the carrier, particularly in the size of the pores. The entanglement dispersibility is affected. When the small pore diameter is 5 nm and the large pore diameter is 100 nm as the representative diameter, the pore volume ratio of the pore system is 20 or less, preferably 10 or less. This is because when the ratio exceeds 20, the carbon material grown on the carrier is more strongly entangled and the dispersibility is lowered.
As a result, when the ratio exceeds 20, the active component is dispersed in the pores having a narrow diameter (φ) of the carrier, and the nanocarbon material grows from the active component. It will be entangled. Such an entangled nanocarbon material does not have good dispersibility in, for example, a solution or a resin.

  On the other hand, when the ratio is 20 or less, preferably 10 or less, the active ingredient is dispersed on a flat surface of the carrier and the nanocarbon material grows from the active ingredient. As a result, the nanocarbon material is all straight. The percentage of the growth is increased. As a result, for example, dispersibility in a solution, a resin, or the like is improved.

  As an example, when the representative diameter of the small pore diameter is 5 nm and the representative diameter of the large pore diameter is 50 nm, the ratio is 5 or less, preferably 3 or less, more preferably 1 or less.

As another example, when the representative diameter of the small pore diameter is 5 nm and the representative diameter of the large pore diameter is 100 nm, the ratio is 10 or less, preferably 8 or less, more preferably 3 or less. Good.
This is preferable because the dispersibility becomes higher as the pores are relatively large, such as 50 nm and 100 nm, with respect to the pores of 5 nm.

Here, when the small pore diameter is 30 nm or less, preferably 0.1 to 30 nm, and the large pore diameter is 30 nm or more, preferably 30 to 200 nm, the ratio is 20 or less. , Preferably 10 or less.
When the pore size distribution is small, the size is not determined with 30 nm as a boundary. For example, the size may be determined with 20 nm, 15 nm, or 10 nm as a boundary.

  In the nanocarbon material according to the present invention, the proportion of the bundle carbon material existing in a bundled state without the nanocarbon material being isolated is 1 to 95%, more preferably 1 to 80%. desirable. In the present invention, the bundle carbon material is an aggregate of two or more carbon materials, and includes those having a small number of aggregates and a large number of aggregates.

The structure of the carbon material of the present invention is preferably any of a fibrous structure, a granular structure, and a tubular structure.
Here, the granular form is formed by a collection of crystallites composed of a graphite layer made of one carbon hexagonal mesh surface.
The fibrous structure is formed by laminating carbon hexagonal mesh surfaces, and the laminating method is a fiber axis, the so-called platelet laminating oblique direction (1 to 89 °) is the fiber axis, so-called herring Bone (Herringbone) or fishbone (Fishbone) structure, one having a fiber axis perpendicular to the stacking direction, so-called tubular, ribbon (Ribbon) or pararail structure. In addition, the herringbone structure has a pair of diagonals, and the slopes of both do not have to be equal.

The carbon material of the present invention has a tube shape, and the tube wall is preferably a single layer or a double layer structure.
Here, in the case of a single layer, the concentration is 20 to 99%, more preferably 85 to 99%. Further, the combined concentration of the single layer and the two layers is 20 to 99%, more preferably 75 to 99%.

  Furthermore, it is preferable that the ratio of the carbon hexagonal network surface having a multilayer structure of three or more layers is 1.3 to 30%, more preferably 1.3 to 15%.

  The diameter of the nanocarbon material is preferably 0.4 nm or more, but preferably has a diameter of 0.4 to 3.5 nm, more preferably 1.5 to 3.5 nm. The ratio of those having a diameter of 1.5 to 3.5 nm is preferably 85%.

  Examples of the active component include V, Cr, Mn, Fe, Co, Ni, Cu, Zn, W, and any one of these, or a combination thereof. It is not limited to these.

Examples of the carrier include aluminum compounds such as alumina, silica, sodium aluminate, alum, and aluminum phosphate, calcium compounds such as calcium oxide, calcium carbonate, and calcium sulfate, and magnesium compounds such as magnesium oxide, magnesium hydroxide, and magnesium sulfate. Examples thereof include apatite systems such as calcium phosphate and magnesium phosphate, but the present invention is not limited thereto. Moreover, these may contain 2 or more types.
Here, the _{^{apatite, M 10 2+ (Z 5- O}} 4) 6 X 2 - composition mineral with M, ZO _4, each element as follows with respect to X, alone or in two or more The one that enters in a solid solution state.
M: Ca, Pb, Ba, Sr, Cd, Zn, Ni, Mg, Na, K, Fe, Al and other _{ZO 4: PO 4, AsO 4} , VO 4, SO 4, SiO 4, CO 3
X: F, OH, Cl, Br, O, I

Further, as the carrier, mesoporous materials such as talc (MgAl ₂ O ₃ ), other minerals, zeolite, and mesoporous silicate may be used.

In addition, due to the interaction between the active component and the carrier, a diffusion layer of both is formed on the surface of the carrier, the diffusion layer covers a part of the active component catalyst, and the exposed portion of the active component catalyst is refined It is good also as what you did.
In this case, since the nanocarbon material grows only from the refined active component portion, only a single-layer nanocarbon material can be produced satisfactorily.

Next, an example of using a fluidized bed reactor as a reactor will be described with reference to FIG. In the present embodiment, a catalyst for producing a nanocarbon material of secondary particles having a predetermined particle size, which is formed by compacting primary particles made of a carrier (magnesium oxide) carrying an active ingredient (iron), has a catalytic action and a fluid action. A fluid catalyst is also used.
As shown in FIG. 2, the nanocarbon material manufacturing unit 15 according to the present embodiment is a fluidized bed reaction unit 62-1 filled with a fluidized catalyst 61 that serves as both a catalyst and a fluidizing material, and a carbon source. A raw material supply device 63 for supplying the carbon raw material 11 into the fluidized bed reaction unit 62-1, a fluidized catalyst supply device 64 for supplying a fluidized catalyst 61 into the fluidized bed reaction unit 62-1, and the fluidized bed reaction unit. The free board part 62-2 which has the space where the fluid catalyst 61 which is the fluid material in 62-1 scatters and flows down, and the fluid gas which introduces into the fluidized bed reaction part 62-1 and causes the fluid catalyst 61 inside to flow. A fluid gas supply device 66 for supplying 65, a heating unit 62-3 for heating the fluidized bed reaction unit 62-1, an exhaust gas processing device 67 for processing the exhaust gas 22 discharged from the free board unit 62-2, The fluidized bed reaction section 62 The catalyst-containing nano-carbon material 14 from 1 extracted by the recovery line 68 is for and a recovery device 20 for recovering.

The fluidized bed reaction mode of the fluidized bed reaction section 62-1 includes a bubble type fluidized bed type and a jet type fluidized bed type, and any one may be used in the present invention.
In this embodiment, the fluidized bed reactor 62 is comprised from the fluidized bed reaction part 62-1, the free board part 62-2, and the heating part 62-3. The free board section 62-2 preferably has a larger flow path cross-sectional area than the fluidized bed reaction section 62-1.

The carbon raw material 11 that is a raw material gas supplied from the raw material supply device 63 may be any compound as long as it is a compound containing carbon, such as CO, CO ₂ , methane, ethane, propane, hexane, and the like. Alkanes, unsaturated organic compounds such as ethylene, propylene and acetylene, aromatic compounds such as benzene and toluene, organic compounds having oxygen-containing functional groups such as alcohols, ethers and carboxylic acids, polymers such as polyethylene and polypropylene Examples of the material include petroleum, coal (including coal conversion gas), and the like, but the present invention is not limited thereto. Further, in order to control the oxygen concentration, two or more oxygen-containing carbon sources CO, CO ₂ , alcohols, ethers, carboxylic acids and the like and a carbon source not containing oxygen can be supplied in combination.

  This carbon raw material 11 is supplied in a gas state into the fluidized bed reaction section 62-1, and a uniform reaction is performed by stirring with the fluidized catalyst 61 that is a fluidized material, thereby growing the nanocarbon material. At this time, an inert gas is separately introduced into the fluidized bed reaction section 62-1 as the fluidized gas 65 by the fluidized gas supply device 66 so as to satisfy the predetermined fluidization conditions.

  And the inside of the fluidized bed reaction part 62-1 is made into the temperature range of 300 degreeC-1300 degreeC by the heating part 62-3, More preferably, it is the temperature range of 400 degreeC-1200 degreeC, and carbon raw materials 11, such as methane, are impurity carbon decomposition products Nanocarbon materials are synthesized by contacting the catalyst for a certain period of time in a coexisting environment.

  In addition to the cyclone, the recovery device 20 may be a known separation means such as a bag filter, a ceramic filter, or a sieve.

  Further, as described above, the catalyst-attached nanocarbon material 14 separated by the recovery device 20 separates the attached catalyst by the acid treatment device 17, the water washing device 19, the filtration device 23, the drying device 24, and the fine grinding device 25. Then, it is refined and collected as a purified nanocarbon material (for example, carbon nanotube, carbon nanofiber, etc.) 26 in nano units.

  As described above, according to the present embodiment, a nanocarbon material with a catalyst can be obtained when producing a nanocarbon material by a fluidized bed reaction. However, using the acid solution 16, the nanocarbon material 14 with a catalyst is obtained. After removing the catalyst from the substrate, it is washed with water and then dried to remove the moisture, and only the purified nanocarbon material 26 can be obtained.

  When the obtained purified nanocarbon material 26 is mixed with the resin, the kneading operation using a biaxial kneading apparatus, the non-aqueous solvent is used to disperse the resin, and the solvent is then removed to obtain the resin kneaded product. A resin sheet or the like is obtained.

At this time, an ionic liquid can be used as a solvent in addition to the non-aqueous solvent as a solvent for dispersing the purified nanocarbon material 26.
Here, as the ionic liquid, a pyridine-based ionic liquid, an alicyclic amine-based ionic liquid, an aliphatic amine-based ionic liquid, or the like can be used depending on the difference in the basic structure of the cation.
Moreover, as an ionic liquid which consists of imidazolium ion, a cation can mention the alkyl imidazolium ion, the alkyl pyridinium ion, the alkyl ammonium ion, or the alkyl phosphonium ion etc., for example.

Moreover, you may make it melt | dissolve in a separated liquid what becomes molten salt at high temperature.
Examples of the salt that becomes a molten salt at high temperatures include alkali halides such as halogen compounds (for example, KCL (melting point: 776 ° C.), Li—Na—K—Cl complex salt (for example, 346 ° C.), AlCl ₃ (170.9 ° C.), etc. Etc.
Further, there may be mentioned ammonium salts such as NH ₄ HSO ₄ (melting point 146 ° C.).
Furthermore, when resin kneading is performed, an optimum kneading state may be created by mutually adjusting the melting temperature of the resin and the temperature of the molten salt melting temperature.
The kneading state can be controlled by adjusting the viscosity of the resin and the ionic liquid, or by adjusting the viscosity of the resin> the ionic liquid, or the viscosity of the resin <the viscosity of the ionic liquid.

For example, when polycarbonate (PC) is used as a resin, it is melted at 250 ° C., and a melt in which the purified nanocarbon material 26 is dispersed in AlCl ₃ and NaCl composite salt (adjusted to a melting point of 240 ° C.) is kneaded. You may do it.

[Embodiment 2]
FIG. 3 shows a schematic diagram of the nanocarbon material manufacturing apparatus according to the present embodiment. In addition, about the member same as Embodiment 1, the same code | symbol is attached | subjected and the description is abbreviate | omitted.
As shown in FIG. 3, the nanocarbon material manufacturing apparatus 10B according to the second embodiment is provided on the upstream side of the acid treatment apparatus 17 in the nanocarbon material manufacturing apparatus 10A of the first embodiment. A fine pulverizing / classifying device 31 for finely pulverizing / classifying the carbon material 14 to, for example, 1 μm or less is provided.

By classifying after fine pulverization, the granulated catalyst on which a nanocarbon material of about 500 to 1000 μm is grown is pulverized to a catalyst of 1 μm or less, preferably a submicron or less.
As a result, the finely pulverized nanocarbon material 32 can be obtained, and then the separation efficiency can be improved by dissolving the catalyst with the acid solution 16.

As a pretreatment of the carbon material dispersion method according to the present invention, the aggregated carbon material is highly dispersed by a physical crushing method.
Here, as the physical crushing method in the present invention, it is particularly preferable to use a collision generated by the turbulent energy of the fluid. This is because, for example, according to a general ultrasonic dispersion method for improving dispersibility, the graphene sheet constituting the carbon material is broken and damaged as the carbon material. Therefore, by using the turbulent energy of the fluid, the aggregated nanocarbon material is unraveled from time to time without destroying the graphene sheet structure constituting the carbon material.

  Moreover, as a physical crushing means, you may make it use either the wet crushing method or the dry crushing method which crushes in the state which disperse | distributed the carbon material in the solvent.

Here, examples of the wet crushing method include a ball mill method and a nanomizer method.
Examples of the dry crushing method include a jet mill method and a ball mill method.

  In this way, when the consolidated secondary particles are used as a flow catalyst, nanocarbon materials that grow from the active components of the primary particles that form the secondary particles are grown and intertwined. The device 31 will be entangled.

  According to the present invention, it is possible to provide a nanocarbon material 18 that has good lysis efficiency and no entanglement of the catalyst using the acid solution 16 by highly dispersing the agglomerated carbon material by physical crushing. It will be possible. In particular, the aggregates can be efficiently crushed by using the collision generated by the turbulent energy of the fluid using a jet mill.

  As a result, mass production of nanocarbon materials having improved dispersibility and extremely high purity can be realized as a product.

[Embodiment 3]
FIG. 4 shows a schematic diagram of the nanocarbon material manufacturing apparatus according to the present embodiment. In addition, about the member same as Embodiment 1, the same code | symbol is attached | subjected and the description is abbreviate | omitted.
As shown in FIG. 4, the nanocarbon material manufacturing apparatus 10C according to the third embodiment is provided on the upstream side of the acid treatment apparatus 17 in the nanocarbon material manufacturing apparatus 10A of the first embodiment. It has a heat treatment device 33 that heat-treats the carbon material 14 to form a nano-carbon material overheated product 34 with catalyst.

  Here, the heat treatment operation of the heat treatment apparatus 33 in the present invention includes a first heat treatment method for performing an operation of separating the catalyst from the nanocarbon material in an oxidizing atmosphere, and the surface of the nanocarbon material in an inert gas atmosphere. One or both of the second heat treatment method for performing the operation of reforming is performed.

Here, in the air atmosphere that is the first heat treatment, the heating temperature at the time of separating the nanocarbon material from the catalyst separation is preferably 400 ° C. or less, and preferably 200 to 300 ° C.
For example, when the active ingredient supported on the carrier is Fe, the bonded portion between the Fe and the nanocarbon material disappears by combustion, and the nanocarbon material can be separated.

  In the inert gas atmosphere as the second heat treatment, the heating temperature for modifying the surface of the nanocarbon material is 1100 ° C. or lower, more preferably 950 ° C. or lower.

In addition, when heat treatment is performed in an inert gas (for example, nitrogen) atmosphere, functional groups (for example, CO, O, etc.) on the surface of the nanocarbon material are removed, making it easy to become familiar with the resin (for example, PC).
Note that either the first heat treatment or the second heat treatment may be performed first.

  Moreover, in this invention, you may make it perform any one or both of the fine grinding process which concerns on 2nd Embodiment, and the heat processing of 3rd Embodiment. In both processes, the order may be performed first.

  The obtained purified nanocarbon material with little entanglement can obtain a conductive resin composition through a step of mixing and dispersing in a resin using a known resin mixing device (kneading device, solvent mixing device, etc.).

  Here, the resin for dispersing the nanocarbon material is not particularly limited, and for example, any of a thermoplastic resin and a thermosetting resin can be used.

  Here, examples of the thermoplastic resin include polyamide resin, polyacrylonitrile resin, polyamide resin, polyimide resin, polyester resin, polyethylene resin, polycarbonate resin, polyketone resin, polysulfone resin, polystyrene resin, polypropylene resin, polyphenylene oxide resin, and polyphenylene. Sulfide resin, polymethyl methacrylate resin, polyvinyl chloride resin, polybenzimidazole resin, ethylene vinyl acetate copolymer resin, cellulose acetate resin, fluorine resin, silicon resin, acrylonitrile-ethylene / propylene-styrene resin (AES resin), Acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-butadiene-methyl methacrylate-styrene resin (ABMS resin), Acrylonitrile -n- butyl acrylate - styrene resin (AAS resin), methyl methacrylate - butadiene - styrene resin (MBS resin), can be mentioned rubber-modified polystyrene (high impact polystyrene) or the like.

  Examples of the thermosetting resin include aniline resin, epoxy resin, xylene resin, diallyl phthalate resin, phenol resin, furan resin, polyurethane resin, melamine resin, urea resin and the like.

  Moreover, you may make it obtain the foamed foam by using a foaming agent, for example.

  Moreover, you may make it add well-known additives, such as a filler, a softening agent, a plasticizer, a processing aid, a lubricant, an anti-aging agent, an ultraviolet absorber, a crosslinking agent, to a resin as needed.

  As described above, the method for dispersing a carbon material according to the present invention has a good dispersibility by highly dispersing a carbon material obtained by agglomeration using a non-aqueous solvent, and a nanocarbon material having improved dispersibility. Can be provided.

It is the schematic of the nanocarbon material manufacturing apparatus which concerns on 1st Embodiment. It is the schematic of a nanocarbon material manufacturing apparatus. It is the schematic of the nanocarbon material manufacturing apparatus which concerns on 2nd Embodiment. It is the schematic of the nanocarbon material manufacturing apparatus which concerns on 3rd Embodiment. It is the schematic of the purification method by the conventional acid treatment. It is a schematic diagram of a catalyst granulation body. It is a schematic diagram of the nanocarbon material with a catalyst.

Explanation of symbols

10A to 10C Nanocarbon material production equipment 14 Nanocarbon material with catalyst 15 Nanocarbon material production equipment 16 Acid solution 17 Acid treatment equipment 19 Water washing equipment 23 Filtration equipment 24 Drying equipment 25 Fine grinding equipment 26 Purified nanocarbon materials

Claims (15)

An acid treatment apparatus in which a nanocarbon material with a catalyst is dispersed in an acid solution, and the catalyst is dissolved and separated by the acid solution;
A water rinsing apparatus for rinsing the acid-treated nanocarbon material;
A drying device for drying the washed nanocarbon material;
An apparatus for producing a nanocarbon material, comprising a pulverizing apparatus for pulverizing a dried nanocarbon material. In claim 1,
The nanocarbon material manufacturing apparatus, wherein the acid treatment apparatus is an ultrasonic acid treatment apparatus. In claim 1 or 2,
A nanocarbon material manufacturing apparatus comprising a surfactant added to one or both of the acid treatment apparatus and the water washing apparatus. In any one of Claims 1 thru | or 3,
The nanocarbon material manufacturing apparatus, wherein the drying apparatus is a heat drying apparatus, a freeze drying apparatus, or a spray drying apparatus. In any one of Claims 1 thru | or 4,
An apparatus for producing a nanocarbon material, comprising a fine pulverization / classification device provided on the upstream side of the dispersion treatment device, for finely pulverizing / classifying the nanocarbon material with catalyst. In any one of Claims 1 thru | or 5,
An apparatus for producing a nanocarbon material, comprising a heat treatment apparatus provided on the upstream side of the dispersion treatment apparatus for heat-treating the nanocarbon material with a catalyst. In any one of Claims 1 thru | or 6,
An apparatus for producing a nanocarbon material, wherein the production apparatus for producing the nanocarbon material with catalyst is a fluidized bed reactor. In claim 7,
An apparatus for producing a nanocarbon material using a fluidized bed reactor, comprising a fluidized catalyst supply device for supplying a fluidized catalyst to be supplied to the fluidized bed reactor. In claim 8,
An apparatus for producing a nanocarbon material using a fluidized bed reactor, wherein the fluidized catalyst has a particle size of 200 μm to 5 mm. The nanocarbon material manufacturing apparatus according to any one of claims 1 to 9,
A resin composition production system comprising a nanocarbon material, comprising: a resin mixing device that mixes the obtained nanocarbon material with a resin. An acid treatment step of dispersing the catalyst-coated nanocarbon material in an acid solution and separating the catalyst;
After the acid treatment, a water washing step of washing the nanocarbon material with water,
A method for refining a nanocarbon material, comprising a drying step of drying the nanocarbon material washed with water. In claim 11,
The method for purifying a nanocarbon material, wherein the acid treatment step is performed by ultrasonic treatment. In claim 11 or 12,
A nanocarbon material refining method comprising a pulverizing / classifying step of pulverizing / classifying a nanocarbon material with catalyst before the acid treatment step. In any one of Claims 11 thru | or 13,
Before the said acid treatment process, it has the heat processing process which heat-processes the nanocarbon material with a catalyst, The nanocarbon material refinement | purification method characterized by the above-mentioned. After purifying the nanocarbon material using the nanocarbon material purification method according to any one of claims 11 to 14,
A method for producing a nanocarbon material resin composition comprising a resin mixing step of mixing the separated nanocarbon material with a resin.

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