CN103180497B - The manufacture method of carbon nano-fiber, carbon complex and manufacture method thereof - Google Patents
The manufacture method of carbon nano-fiber, carbon complex and manufacture method thereof Download PDFInfo
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- CN103180497B CN103180497B CN201180050711.4A CN201180050711A CN103180497B CN 103180497 B CN103180497 B CN 103180497B CN 201180050711 A CN201180050711 A CN 201180050711A CN 103180497 B CN103180497 B CN 103180497B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1278—Carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
Abstract
The invention provides and can reduce quality deviation and the manufacture method manufacturing the carbon nano-fiber of high conductivity expeditiously.Carbon complex and the manufacture method thereof of dispersiveness and conductivity-imparting ability excellence are also provided.The present invention relates to and use calcium carbide furnace gas as raw material and the manufacture method making the carbon nano-fiber of catalyst and contact raw; Also relate to being characterized as and there is carbon black pellet or aggregated particle as core, and carbon black/carbon nano-fiber carbon complex that carbon black and carbon nano-fiber link; And relate to carbon nano-fiber generation catalyst loading is made the manufacture method of its carbon complex contacted with calcium carbide furnace gas on carbon black.
Description
Technical field
The present invention relates to the manufacture method of carbon nano-fiber.In addition, the invention still further relates to the carbon complex using carbon nano-fiber and manufacture method thereof.
Background technology
In the past, resin, rubber etc. is made to give electric conductivity containing carbon black to it.Particularly acetylene black has the chain structure of carbon granule, therefore compares with the carbon black of routine, and conductivity-imparting ability is excellent.In addition, carbon black can play the conductivity-imparting ability of its excellence, as the conductive material of electrode for secondary battery.But in recent years, people's demand does not make the characteristic of the script of resin, battery material etc. reduce the conductive material just can giving higher electric conductivity.
For these problems, propose the scheme using carbon nano-fiber (CNF) as conductive material.The fibrous carbon of CNF to be wire diameter be tens nanometer ~ 100 ran, has the character that high conductivity, high-termal conductivity etc. are excellent, therefore can be used as electroconductive stuffing in base materials such as being filled in resin or high thermal conductivity filler is applied in industrial circle.Make raw material and catalyst exposure and the shape of the CNF obtained is mostly hollow fiber.Sometimes CNT (CNT) can be specially called.
For CNF, although compared with carbon black, its crystallinity is high, the resistance value of powder is low, and owing to existing with the form of the aggregation of its Filament-wound Machine, therefore, bad dispersibility when mixing with resin etc., cannot give full play to conductivity-imparting ability.Therefore, also to being made aggregation disperse to be studied by acid treatment or mechanical agitation process, but CNF is often shortlyer cut-off, and loses speciality originally.So the compound of people to carbon black and CNF is studied.Such as, propose and generate the scheme (patent document 1) of CNF at the reaction scene of acetylene black, but due to acetylene black different from the formation condition of CNF, if therefore generate in same generation place simultaneously, then there is the problem of quality instability.Somebody proposes and generates place importing CNF at carbon black and obtain the scheme (patent document 2) of compound, but because raw material CNF assembles, therefore the containing ratio of CNF in compound cannot be improved, there is the problem that the mobility being difficult to the conductive composition be obtained by mixing at other materials such as maintenance and resins reduces again resistance value simultaneously, do not find satisfactory solution yet at present.
In addition, CNF also by method (patent document 3), the method (patent document 4) making the hydrocarbon of benzene etc. and catalyst metals fluor-complex react of the hydrocarbon and catalyst exposure that make benzene etc., make carbon monoxide (CO) and hydrogen (H
2) the manufacture such as the method (patent document 5) that contacts with the catalyst granules containing metal or metal oxide of mist.When using hydrocarbon as raw material, hydrocarbon is cheap, easily obtains, but the secondary soft coal cigarette (cigarette ash) of another aspect meeting, be easily mixed in product (CNF).Electric conductivity, the thermal conductivity of coal smoke are poorer than CNF, therefore, and the problem that the performance that there is the CNF owing to being mixed into reduces.
On the other hand, at use CO and H
2mist as raw material when, there is the advantage of the pair life easily suppressing coal smoke, but on the other hand, yield or the physical property of CNF easily produce deviation, therefore in productivity, have problem, in addition, the CO as the raw material of industry is not easy to obtain, higher than price with hydrocarbon phase, the price that therefore there is the CNF of generation is the problem such as high also.
[prior art file]
[patent document]
Patent document 1:WO/2007/013678
Patent document 2: Japanese Unexamined Patent Publication 2010-248397 publication
Patent document 3: the clear 62-500943 publication of Japanese Unexamined Patent Application Publication
Patent document 4: Japanese Unexamined Patent Publication 2003-146633 publication
Patent document 5: Japanese Unexamined Patent Publication 2004-300631 publication
Summary of the invention
(inventing problem to be solved)
The present invention proposes in order to CNF manufacture method Problems existing in the past described in solving, and provides and can reduce quality deviation and the method that can manufacture high conductivity CNF expeditiously.In addition, the present invention also provides carbon complex and the manufacture method thereof of dispersiveness and conductivity-imparting ability excellence.
(means of dealing with problems)
That is, the present invention adopts following methods to solve above-mentioned problem.
(1) manufacture method for carbon nano-fiber, is characterized in that: use calcium carbide furnace gas as raw material, make catalyst and contact raw.
(2) manufacture method of the carbon nano-fiber described in above-mentioned (1), is characterized in that: use the calcium carbide furnace gas eliminating moisture as raw material.
(3) manufacture method of above-mentioned (1) or the carbon nano-fiber described in (2), is characterized in that: catalyst is the simple substance of iron family element (iron, cobalt or nickel) or the compound containing iron family element.
(4) manufacture method of the carbon nano-fiber described in above-mentioned (3), is characterized in that: the compound containing iron family element is oxide or the hydroxide of iron family element.
(5) manufacture method of above-mentioned (1) or the carbon nano-fiber described in (2), is characterized in that: catalyst is containing iron group mischmetal or containing the compound containing iron group mischmetal.
(6) manufacture method of the carbon nano-fiber described in above-mentioned (5), is characterized in that: be oxide or the hydroxide containing iron group mischmetal containing the compound containing iron group mischmetal.
(7) manufacture method of the carbon nano-fiber according to any one of above-mentioned (1) ~ (6), it is characterized in that: catalyst comprises powdered substance, and under the temperature/pressure condition of Formed nanofiber, come to use with catalyst fines using the material do not reacted with calcium carbide furnace gas as the carrying body of catalyst simultaneously, and contact with calcium carbide furnace gas.
(8) manufacture method of the carbon nano-fiber described in above-mentioned (7), is characterized in that: the carrying body of catalyst is magnesia and/or aluminium oxide.
(9) manufacture method of the carbon nano-fiber according to any one of above-mentioned (1) ~ (8), it is characterized in that: be configured with catalyst in carbon nano-fiber synthesizer after, first by reducibility gas gatherer, then calcium carbide furnace gas is imported.
(10) manufacture method of the carbon nano-fiber described in above-mentioned (9), is characterized in that: reducibility gas is hydrogen.
(11) carbon black/carbon nano-fiber carbon complex, is characterized in that: having the particle of carbon black or aggregated particle as core, is that carbon black and carbon nano-fiber link.
(12) carbon complex described in above-mentioned (11); it is characterized in that: the surface of the top ends of carbon nano-fiber and the particle of carbon black or aggregated particle optionally links, the fibre length of carbon nano-fiber than the particle of carbon black or the length of aggregated particle long.
(13) carbon complex described in above-mentioned (11), is characterized in that: carbon black is acetylene black.
(14) manufacture method of the carbon complex described in above-mentioned (11), is characterized in that: by carbon nano-fiber generation catalyst loading on carbon black, and make it contact with calcium carbide furnace gas.
(15) manufacture method of the carbon complex described in above-mentioned (14), is characterized in that: use the calcium carbide furnace gas eliminating moisture as raw material.
(16) manufacture method of the carbon complex described in above-mentioned (14), is characterized in that: carbon nano-fiber generation catalyst is the simple substance of iron family element (iron, cobalt or nickel) or the compound containing iron family element.
(17) manufacture method of the carbon complex described in above-mentioned (16), is characterized in that: the compound containing iron family element is oxide or the hydroxide of iron family element.
(18) manufacture method of the carbon complex described in above-mentioned (14), is characterized in that: carbon nano-fiber generation catalyst is containing iron group mischmetal or containing the compound containing iron group mischmetal.
(19) manufacture method of the carbon complex described in above-mentioned (18), is characterized in that: be oxide or the hydroxide containing iron group mischmetal containing the compound containing iron group mischmetal.
(20) manufacture method of the carbon complex described in above-mentioned (14), it is characterized in that: after in carbon nano-fiber generating apparatus, configuration has supported the carbon black of carbon nano-fiber generation catalyst, first by reducibility gas gatherer, then calcium carbide furnace gas is imported.
(21) manufacture method of the carbon complex described in above-mentioned (20), is characterized in that: reducibility gas is hydrogen.
(22) conductive composition, is characterized in that: be filled in resin and/or rubber by the carbon complex described in above-mentioned (11).
(invention effect)
By adopting the manufacture method of carbon nano-fiber of the present invention (CNF), the deviation of quality can be reduced and manufacture the CNF of high conductivity expeditiously, the application as electroconductive stuffing or high thermal conductivity filler of CNF can be promoted, therefore large to the contribution of industrial development.Further, when using calcium carbide furnace gas as fuel, there is burning and with carbon dioxide (CO in the major part of CO contained in calcium carbide furnace gas
2) form discharge into the atmosphere, but method of the present invention to utilize in calcium carbide furnace gas contained CO to manufacture CNF, the CO therefore discharged into the atmosphere
2reduce, the reduction for carrying capacity of environment also has contribution.
In addition, according to the present invention, the carbon complex of dispersed and conductivity-imparting ability excellence, stay in grade can be obtained.
Accompanying drawing explanation
Fig. 1 is an example of the structure of carbon complex of the present invention.
Fig. 2 is an example of the structure of the carbon complex generating on-the-spot importing carbon nano-fiber at carbon black and obtain.
Detailed description of the invention
(embodiment 1)
In the present invention, calcium carbide refers to calcium carbide (CaC
2).Calcium carbide is the acetylene (C used as the raw material of industry or fuel
2h
2) or as the nitrolim (CaCN of nitrogenous fertilizer composition
2) etc. raw material, therefore industrially synthesized widely.Common calcium carbide synthesis is by the carbon (C) of quick lime (CaO) and coke etc. as raw material, in the high temperature furnace being called as furnace of calcium carbide, by utilizing the synthesis procedure of the reaction of formula 1 to carry out.
CaO+3C → CaC
2+ CO (formula 1)
In calcium carbide synthesis procedure, as shown in Equation 1, secondary raw carbon monoxide (CO) gas.CO is harmful to, and directly can not discharge, therefore normally furnace of calcium carbide be made the structure of hermetic type, collect secondary angry body (calcium carbide furnace gas), then by using (formula 2) to carry out harmless treatment as fuel.
CO+ (1/2) O
2→ CO
2(formula 2)
The industrial furnace of the secondary raw gas containing CO is not limited to furnace of calcium carbide, and the angry body (oven gas, blast furnace gas) of pair of the coke oven such as used in Iron industry, blast furnace is also containing CO.But the hydrocarbon contained by oven gas, blast furnace gas, carbon dioxide (CO
2) etc. the composition beyond CO many, the content of CO is only 30% (volume) left and right below, is therefore not suitable for the raw material of CNF.Calcium carbide furnace gas contains CO with the high concentration of 50 ~ 90%, and generates hydrogen (H by the reaction (water gas reaction) of moisture contained in quick lime or coke and carbon
2), therefore, relative to CO, with CO:H
2the ratio of=60:40 ~ 90:10 (volume ratio) contains H
2.In the present invention, life secondary in calcium carbide synthesis procedure, the main angry body of pair containing CO and hydrogen is defined as calcium carbide furnace gas.
Can think that the generation carrying out CNF by CO raw material makes the reaction shown in formula 3 carry out realizing in the presence of a catalyst.From formula 3, just CNF can be generated as raw material, if but in fact do not make H as only there is CO
2coexist, then reactivity significantly reduces.Its reason may be due to raw CO secondary when CNF generates
2make the cause of catalyst oxidation inactivation, and think due to H
2coexist and the reason improving reactivity is due to H
2reduction inhibit the inactivation of catalyst.
2CO → C (CNF)+CO
2(formula 3)
By CO and H
2the mist method of raw material that is used as CNF open and known in patent document 5.Mist is in the past by industrial raw material CO gas and H
2gas is with CO:H
2=40:60 ~ 90:10 isotactic certainty ratio mixes and obtains.Now, mixing is carried out usually at normal temperatures.
On the other hand, the synthesis of calcium carbide is carried out usually under the high temperature of 1600 ~ 2000 DEG C.CO, H contained in calcium carbide furnace gas
2also at high temperature mix, therefore can think, admixture is different from the mist in the past mixed near normal temperature.Inventors etc. newly recognize: at CO and H will mixed under high temperature like this
2mist be used for raw material when, compare with CNF synthetic method in the past, the yield of the CNF of generation significantly improves/stabilisation, therefore can quality bills of materials deviation is little expeditiously CNF, and the characteristic of electrical conductivity also improves/stabilisation, thus completes the present invention.
The principal component of calcium carbide furnace gas is carbon monoxide (CO) and hydrogen (H
2), usually also containing nitrogen (N
2) as safety gas.The concentration of each composition is: CO is 50 ~ 80 volume %, H
2be 10 ~ 30 volume %, N
2for several ~ 30 volume %.In addition, CO, H is removed in calcium carbide furnace gas
2and N
2outside, also containing CO
2, hydrocarbon, hydrogen sulfide, the impurity such as nitrogen oxide and/or oxysulfide, be trace, the generation of CNF almost do not affected.In addition also containing the solid impurity (dust) produced in calcium carbide generation process, they are by filtering (dry method) or washing (wet method) removing.Eliminated the steam containing a few % (volume) in the calcium carbide furnace gas of dust by wet method, this may make catalysqt deactivation, and therefore the removing such as preferred drying machine or dehydration column is to less than 0.1%.
The calcium carbide furnace gas obtained like this is imported in CNF synthetic furnace, by synthesizing CNF with catalyst exposure.Calcium carbide furnace gas can use the inert gas dilution such as nitrogen, argon further.The temperature of preferred synthetic furnace is 300 ~ 700 DEG C, and pressure is 0.01MPa ~ 1MPa.Temperature lower than 300 DEG C or more than 700 DEG C or pressure lower than 0.01MPa time, reaction occur hardly, therefore not preferred.In addition, when pressure is more than 1MPa, the withstand voltage scheme of device is comparatively numerous and diverse, and the improvement effect of not obvious yield or physical property, therefore not preferred.Reaction time is preferably 1 ~ 24 hour.Lower than the growing amount pettiness of 1 hour then CNF, in addition, even if can not significantly increase more than 24 hours growing amounts, therefore all not preferred yet.
Catalyst can use the simple substance of iron family element (iron, cobalt or nickel) or the compound containing iron family element, the oxide of such as iron family element or hydroxide, also can use containing iron group mischmetal or containing the compound containing iron group mischmetal, such as, containing oxide or the hydroxide of iron group mischmetal.These materials can be used alone, and also can use two or more materials simultaneously.
In addition, use the powder of above-mentioned substance as catalyst, further also can with above-mentioned catalyst fines be simultaneously used in that said temperature/pressure condition of generating CNF does not react with calcium carbide furnace gas, such as the material such as magnesia and/or aluminium oxide is as the carrying body of catalyst.
Preferably, configure catalyst in stove after, before importing calcium carbide furnace gas, carry out the activation (activating process) of catalyst in advance.Specifically, first in synthetic furnace, configure catalyst, by be adjusted in stove generate CNF temperature/pressure after, import calcium carbide furnace gas forward direction stove in import several tens minutes ~ mono-hours H
2deng reducibility gas, from catalyst surface except deoxidation or moisture, catalyst can be made thus to activate.
The CNF generated can convection drying or with aqueous acid carry out process remove residual catalyst after dry and make powder, or supply practical application as the slurry be scattered in water or organic solvent.
(embodiment 2)
The carbon complex of present embodiment of the present invention is that carbon black and CNF link.Here, link is not simple contact, and refers to and to be merged reasoningly by Carbonaceous matter, be not easy to be separated, and electronics can not move freely between linked carbon black and CNF with having contact resistance with common mechanically actuated.Therefore, when mixing with other material such as resin, battery material, carbon black and CNF also exist with the state linked, and can obtain good dispersiveness, be endowed high conductivity simultaneously.When separately containing carbon black, addition for resin etc. must be increased to give electric conductivity, the mobility of gained conductive composition is impaired, when separately containing CNF, orientation, winding is there is when mixing with resin etc., therefore be difficult to obtain good dispersiveness, deviation can occur in electric conductivity.In addition, when merely being mixed with CNF by carbon black, both contact conditions easily change, and therefore deviation can increase further.
Carbon complex of the present invention is the carbon complex with following characteristics, and namely having the particle of carbon black or aggregated particle as core, is that carbon black and CNF are formed by connecting.The present inventor improves to make the dispersiveness of carbon complex and conductivity-imparting ability and conducts in-depth research, and found that, the impact of structure on these characteristics of carbon complex is large.That is, centered by carbon black pellet or aggregated particle, at its peripheral part, there is CNF and the structure of both links by obtaining, when mixing with resin etc., the area that the CNF of excellent electric conductivity contacts with resin etc. increases.In addition, in said structure, the gathering of CNF reduces, and is therefore difficult to orientation, winding occur, thus can increases the amount of the CNF mixed to resin etc., conductivity-imparting ability can be made to significantly improve.On the other hand, carbon complex is in the past the structure that carbon black surrounds the peripheral part of the CNF assembled, therefore reduce with the contact area of resin etc., and the major part contacted with resin etc. is carbon black, therefore cannot give full play to the conductivity-imparting ability of CNF in carbon complex.Fig. 1 represents an example of the structure of carbon complex of the present invention, and Fig. 2 represents the example generating the structure of the carbon complex in the past of on-the-spot importing CNF gained at carbon black.
In the present invention, preferably, the surface of the top ends of CNF and the particle of carbon black or aggregated particle optionally links, the fibre length of CNF than the particle of carbon black or the particle diameter of aggregated particle large.Here, the top ends of CNF refers to that CNF generates and the end in the direction of extending.When CNF fibre length than the particle of carbon black or the particle diameter of aggregated particle large, even if the amount of the carbon complex in adding resin etc. to is as in the past, also easily to spread to wide scope in resin etc., therefore can effectively play conductive path function.The fibre length of CNF regulated by reaction of formation temperature, reaction of formation time, was more preferably more than 1 μm.
The kind forming the carbon black of carbon complex of the present invention is not particularly limited, such as, can use thermal black, furnace black, dim, channel black, acetylene black etc., wherein more preferably acetylene black.This is the structure because acetylene black has high-purity, the primary particle of high crystalline connects chaining, therefore excellent electric conductivity.
CNF content in carbon complex of the present invention is preferably 10 ~ 80 quality %.If the content of CNF is lower than 10 quality %, then cannot obtain sufficient electric conductivity, if more than 80 quality %, then make dispersed reduction due to the gathering etc. of CNF.CNF content by joining CNF generation catalyst in CNF generating apparatus, the amount of carbon black, reaction of formation temperature, reaction of formation time regulates.
The manufacture method of carbon complex of the present invention is not particularly limited, such as, can by supporting CNF generation catalyst on carbon black, and make it contact with calcium carbide furnace gas, carbon black pellet Surface Creation CNF and make it link.Owing to being illustrated calcium carbide furnace gas in embodiment 1, therefore description is omitted here.
The calcium carbide furnace gas obtained like this can be imported in CNF generating apparatus and to make itself and catalyst exposure, generating CNF thus.Calcium carbide furnace gas can use the inert gas dilution such as nitrogen, argon further.Preferably, the temperature of synthetic furnace is 300 ~ 700 DEG C, and pressure is 0.01MPa ~ 1MPa.If temperature lower than 300 DEG C or more than 700 DEG C or pressure lower than 0.01MPa, then react and occur hardly, therefore not preferred.In addition, if pressure is more than 1MPa, then the withstand voltage scheme of device is numerous and diverse, and the improvement effect of not obvious yield, physical property, therefore not preferred.Preferably 1 ~ 24 hour reaction time.If lower than 1 hour, then the growing amount pettiness of CNF, even if in addition more than 24 hours, growing amount also can not enlarge markedly, therefore all not preferred.
CNF generation catalyst can use the simple substance of iron family element (iron, cobalt or nickel) or the compound containing iron family element, the oxide of such as iron family element or hydroxide, also can use containing iron group mischmetal or containing the compound containing iron group mischmetal, such as, containing oxide or the hydroxide of iron group mischmetal.These materials can be used alone, and also can use two or more materials simultaneously.
Preferably, CNF generation catalyst loading is on carbon black.Loading method is not particularly limited, the CNF generation catalyst such as the simple substance of iron family element or the compound containing iron family element such as can be made to suspend or be dissolved in the liquid such as ethanol, in this liquid, add carbon black, stirring, mixing, dehydration, drying, support thus.The material powder obtained thus is contacted with calcium carbide furnace gas in CNF generating apparatus, and obtain carbon complex thus, the feature of this carbon complex is: having the particle of carbon black or aggregated particle as core, is that carbon black and CNF link.Moreover because the particle of carbon black or aggregated particle exist with the form of core, therefore the top ends of CNF optionally links, and CNF can be made to grow along multiple directions, can suppress to assemble.In addition, in method in the past, such as, generate the method for carbon black and CNF at same generation scene simultaneously, add in the method for CNF at carbon black generation scene, be difficult to obtain the carbon complex with structure of the present invention.
When generating CNF, before importing calcium carbide furnace gas, preferably carry out the activation (activating process) of catalyst in advance.Specifically, in CNF generating apparatus, configuration has supported the carbon black of CNF generation catalyst, by be adjusted in stove generate CNF temperature/pressure after, in device, import the H of dozens of minutes ~ mono-hours
2deng reducibility gas, from catalyst surface except deoxidation or moisture, thus activating catalyst.Afterwards, the generation of CNF is promoted by importing calcium carbide furnace gas.
The carbon complex generated can convection drying or dry and make powder after removing residual catalyst with aqueous acid process, or supplies practical application as the slurry be scattered in water or organic solvent.By being filled in resin or rubber etc. by carbon complex of the present invention, the conductive composition than excellent electric conductivity in the past can be obtained.
Embodiment
Describe the manufacture method of carbon nano-fiber of the present invention, carbon complex and manufacture method thereof below by way of embodiments and comparative examples in detail.But the present invention is not limited to following embodiment in the scope being no more than its aim.
[embodiment 1]
Use closed type calcium carbide furnace, quick lime (CaO) and petroleum coke (C) are joined in stove, then 25 are applied to the graphite electrode that the central upper from stove is inserted in stove, the electric power of 000kW, make in stove, to be heated to 2000 DEG C, CaO and C is reacted and synthesizes calcium carbide (CaC
2).Collect now secondary raw calcium carbide furnace gas, washing to remove dust, being then stored in hydrolock air accumulator.Extract a part for the calcium carbide furnace gas stored, analyze principal component with gas chromatograph (Shimadzu Seisakusho Ltd. manufactures, GC-14B), analyze micro constitutent with gas detecting tube (GASTEC manufacture), result is as shown in table 1.
[table 1]
Fill containing cobalt oxide (Co in the reaction vessel of quartz glass
3o
4) (Sigma-Aldrich manufactures, " 637025 ", purity 99.8%, average grain diameter 20 ~ 30nm) and magnesia (MgO) (Sigma-Aldrich's manufacture, " 549649 ", average grain diameter 12.8nm, specific area 130m
2/ g) the catalyst of mixed-powder, then container is filled in CNF synthesizer.With inert gas (N in device
2) fill, make pressure be warming up to 600 DEG C after 0.1MPa, with reducibility gas (H
2) replace and keep 30 minutes, then the above-mentioned calcium carbide furnace gas be stored in air accumulator to be imported in stove and to keep 8 hours.Then, N is used
2calcium carbide furnace gas replaced and stops heating, being cooled to open system after room temperature, reclaiming product from reaction vessel.These condition summary sheets are shown in Table 2.
[table 2]
Product is the powder of black.Calculate the output (weight portion) of the product corresponding to every 1 weight portion of the catalyst used as yield.Utilize transmission electron microscope (TEM: NEC manufacture, transmission electron microscope 2000FX, accelerating potential 200kV observe multiplying power 200,000 times) to observe micro-structural, result is the carbon nano-fiber (CNF) of hollow fiber.The external diameter of 10 CNF is measured, using its mean value as CNF diameter by TEM image.For electric conductivity, use p owder resistivity measuring instrument (ANALYTECH Co., Ltd. of Mitsubishi Chemical manufactures, LORESTAGP), measure p owder resistivity value with load 4.9kN, four probe method.Implement 10 synthetic tests under the same conditions, the mean value of calculated yield, CNF diameter and p owder resistivity value and standard deviation.These result summary sheets are shown in Table 3.
[table 3]
[embodiment 2 ~ 4]
Use the calcium carbide furnace gas of embodiment 1, synthesize according to condition shown in table 2 respectively.The result of calculation summary sheet of the morphologic observation of the micro-structural of products therefrom and yield, CNF diameter and p owder resistivity value is shown in Table 3.
[embodiment 5 ~ 7]
Use the calcium carbide furnace gas of the composition shown in table 1, synthesize according to condition shown in table 2 respectively.The result of calculation summary sheet of the morphologic observation of the micro-structural of products therefrom and yield, CNF diameter and p owder resistivity value is shown in Table 3.
[embodiment 8 ~ 14]
Same with embodiment 1 ~ 7, make to be stored in calcium carbide furnace gas in hydrolock air accumulator by dehydration column (daily use chemicals Seiko manufactures, dry post, DC-L4), moisture is reduced to 0.01 volume %.By the principal component of chromatographic gas, analyze micro constitutent with gas detecting tube, result is as shown in table 1.Then synthesize according to the condition same with embodiment 1 ~ 7, the result of calculation summary sheet of the morphologic observation of the micro-structural of products therefrom and yield, CNF diameter and p owder resistivity value is shown in Table 3.
[comparative example 1 ~ 7]
As unstrpped gas, use the gas commercially available CO gas (purity 99.95%) and hydrogen (purity 99.99%) at room temperature mixed according to ratio shown in table 4 to replace calcium carbide furnace gas, in addition synthesize according to the condition same with embodiment 1 ~ 7, the result of calculation summary sheet of the morphologic observation of the micro-structural of products therefrom and yield, CNF diameter and p owder resistivity value is shown in Table 3.
As shown in Table 3, the embodiment (such as comparative example 1 and embodiment 1 and embodiment 8, comparative example 2 and embodiment 2 and embodiment 9, below equally) that comparative example 1 ~ 7 is all identical with the synthesis condition except unstrpped gas compares, and yield is low, fibre diameter is thin, and p owder resistivity value is high.And their standard deviation value is large, and deviation is large.
[comparative example 8 ~ 9]
As unstrpped gas, the oven gas being used in generation when carrying out destructive distillation with coke oven to coal replaces calcium carbide furnace gas, in addition synthesizes according to condition similarly to Example 1, has no the generation of CNF.Be used in the blast furnace gas that produces when utilizing blast furnace coke reducing iron ore as the generation also having no CNF during unstrpped gas.The oven gas used and the composition analysis result of blast furnace gas as shown in table 1.
From embodiment and comparative example, according to manufacture method calcium carbide furnace gas being used as the carbon nano-fiber (CNF) of raw material of the present invention, quality deviation can be reduced and manufacture the CNF with high conductivity expeditiously.And secondary raw calcium carbide furnace gas in calcium carbide synthesis procedure can be used in, as raw material, therefore comparing with using the situation of commercially available CO gas and hydrogen, carbon dioxide (CO can be cut down
2) burst size, and CNF can be manufactured at low cost.
Embodiment 15 uses the calcium carbide furnace gas of synthesis in embodiment 1 to manufacture carbon complex.By 50g furnace black (East Sea Tan Su company manufactures, " SEAST SO ") and 0.5g cobalt oxide (Co
3o
4) powder (Sigma-Aldrich manufacture, " 637025 ", purity 99.8%, average grain diameter 20 ~ 30nm) joins in 500g ethanol, mixes 1 hour with ball mill.Then carry out filtering/dry, obtain material powder.Then, gained material powder is filled in the reaction vessel of quartz glass, container is filled in carbon nano-fiber generating apparatus.Making in device is vacuum atmosphere, then fills inert gas (N
2), make pressure be 0.1Mpa and be warming up to 600 DEG C.Then, the above-mentioned calcium carbide furnace gas be stored in hydrolock air accumulator to be imported in stove and to keep 6 hours.Then, N is used
2calcium carbide furnace gas replaced and stops heating, being cooled to room temperature, then open system, from reaction vessel, reclaiming product.Their formation condition is as shown in table 4.
[table 4]
The assessment item of product and evaluation method thereof are as shown below.
(1) about carbon nano-fiber with or without link, bond sites, by transmission electron microscope, (Jeol Ltd. manufactures, " transmission electron microscope JEM-2000FX ", observes multiplying power 100,000 times) observe fine structure, confirm.
(2) about the fibre length of carbon nano-fiber, measure 10 by transmission electron microscope (observing multiplying power 5000 times), ask its mean value.In addition, the aggregated particle about carbon black is evaluated too, is 500nm.
(3) about the containing ratio of carbon nano-fiber, deduct the weight of material powder from the weight of the product reclaimed, ask the weight of generated carbon nano-fiber to calculate.
(4) about the conductivity-imparting ability of carbon complex, by being evaluated by the specific insulation of following resin complexes of trying to achieve.10 parts by mass carbon complexes are engaged in 90 parts by mass PS resins (Toyo Styrene Co., Ltd. manufactures " H700 "), use mixing roll (manufactured by Toyo Seiki making, " LABO PLASTOMILL "), with mixing 10 minutes of blade rotational speed 30rpm, temperature 220 DEG C.This mixing thing is heated to 200 DEG C, shaping with the exert pressure of 9.8 × 106Pa, make the test film of 2 × 2 × 70mm, use digital multimeter (Yokogawa Motor Co., Ltd, " digital multimeter 7562 "), according to the test method measuring specific insulation of SRI2301.
(5) about the mobility of the dispersiveness in resin and resin combination, evaluated by the following MFI (melt flow index) tried to achieve.The test film used in being measured by specific insulation is cut into the size of 2 × 2 × 5mm, with mobility measuring instrument (manufactured by Toyo Seiki making, melt index apparatus A-111), under the heating of 200 DEG C, under the load of 5kg, measure the quality of the resin combination of every 10 minutes flowed out from the nozzle of internal diameter 2mm.
These results are as shown in table 5.
[table 5]
[embodiment 16]
Raw material carbon black is changed to acetylene black (electrochemically industry manufactures, " HS-100 "), in addition similarly to Example 15, obtain carbon complex.Evaluation result is as shown in table 5.
[embodiment 17]
Fill inert gas (N
2) and make pressure be 0.1MPa, with reducibility gas (NH after being warming up to 600 DEG C
3) replace and keep 30 minutes, the calcium carbide furnace gas be stored in hydrolock air accumulator is imported in stove, in addition similarly to Example 16, obtains carbon complex.Evaluation result is as shown in table 5.
[embodiment 18]
Reducibility gas is changed to H
2, in addition similarly to Example 17, obtain carbon complex.Evaluation result is as shown in table 5.
[embodiment 19,20]
(Sigma-Aldrich manufactures carbon nano-fiber generation catalyst to be changed to cobalt metal, " 266639 ", purity 99.8%, average grain diameter 2 μm), iron-manganese-cobalt alloy (composition 5:2.5:2.5, average grain diameter 30nm), in addition similarly to Example 18, carbon complex is obtained.Evaluation result is as shown in table 5.
[embodiment 21 ~ 26]
Make to be stored in calcium carbide furnace gas in hydrolock air accumulator by dehydration column (daily use chemicals Seiko manufactures, " dry post DC-L4 "), in addition same with embodiment 15 ~ 20, obtain carbon complex.Evaluation result is as shown in table 5.
[embodiment 27 ~ 29]
As shown in table 4 reaction of formation temperature and reaction of formation time to be changed, in addition similarly to Example 24, obtain carbon complex.Evaluation result is as shown in table 5.
[embodiment 30]
By the cobalt oxide (Co mixed with 50g acetylene black
3o
4) the quantitative change more 0.7g of powder, in addition similarly to Example 29, obtain carbon complex.Evaluation result is as shown in table 5.
[comparative example 10]
By 0.5g cobalt oxide (Co
3o
4) powder is filled in the reaction vessel of quartz glass, container is filled in carbon nano-fiber generating apparatus.Making in device is vacuum atmosphere, then fills inert gas (N
2), make pressure be 0.1MPa, and be warming up to 600 DEG C.Then reducibility gas (H is used
2) carry out replacing and keep 30 minutes, then, will to be imported by the calcium carbide furnace gas of dehydration column in stove and keep 6 hours.Then by calcium carbide furnace gas N
2replace and stop heating, being cooled to open system after room temperature, reclaiming the carbon nano-fiber simple substance generated from reaction vessel.Evaluation result is as shown in table 5.
[comparative example 11]
With ball mill, the carbon nano-fiber obtained in comparative example 10 is mixed with acetylene black, obtain mixed powder.Evaluation result is as shown in table 5.
[comparative example 12]
As unstrpped gas, use the gas mixed with the ratio of the commercially available CO gas (purity 99.95%) of 70 volume %, the hydrogen (purity 99.99%) of 15 volume %, the nitrogen (purity 99.99%) of 15 volume %, in addition similarly to Example 24, carbon complex is obtained.Evaluation result is as shown in table 5.
(industrial applicability)
The CNF obtained by manufacture method of the present invention is filled in the matrix such as resin as high conductivity filler, can use as composite in various industrial circle.In addition, carbon complex of the present invention can be used as the conductivity-imparting agent of rubber etc., as battery conductive materials such as one-shot battery, secondary cell, fuel cell, capacitors.
(explanation of Reference numeral)
1: carbon black; 2: carbon nano-fiber.
Claims (11)
1. a manufacture method for carbon nano-fiber, is characterized in that: use calcium carbide furnace gas as raw material, make catalyst and described contact raw.
2. the manufacture method of carbon nano-fiber according to claim 1, is characterized in that: use the calcium carbide furnace gas eliminating moisture as raw material.
3. the manufacture method of carbon nano-fiber according to claim 1, is characterized in that: catalyst is the simple substance of iron family element or the compound containing iron family element.
4. the manufacture method of carbon nano-fiber according to claim 3, is characterized in that: described iron family element is iron, cobalt or nickel.
5. the manufacture method of carbon nano-fiber according to claim 3, is characterized in that: the compound containing iron family element is oxide or the hydroxide of iron family element.
6. the manufacture method of carbon nano-fiber according to claim 1, is characterized in that: catalyst is containing iron group mischmetal or containing the compound containing iron group mischmetal.
7. the manufacture method of carbon nano-fiber according to claim 6, is characterized in that: be oxide or the hydroxide containing iron group mischmetal containing the compound containing iron group mischmetal.
8. the manufacture method of carbon nano-fiber according to claim 1, it is characterized in that: catalyst comprises powdered substance, and under the temperature/pressure condition of Formed nanofiber, come use with catalyst fines simultaneously and contact with calcium carbide furnace gas using the material do not reacted with calcium carbide furnace gas as the carrying body of catalyst.
9. the manufacture method of carbon nano-fiber according to claim 8, is characterized in that: the carrying body of catalyst is magnesia and/or aluminium oxide.
10. the manufacture method of carbon nano-fiber according to claim 1, is characterized in that: configure catalyst in carbon nano-fiber synthesizer after, first by reducibility gas gatherer, then imports calcium carbide furnace gas.
The manufacture method of 11. carbon nano-fibers according to claim 10, is characterized in that: reducibility gas is hydrogen.
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| CN101283055A (en) * | 2005-07-27 | 2008-10-08 | 丹卡新加坡私人有限公司 | Carbon black, method for producing the same, and its use |
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| CN101304945A (en) * | 2005-04-14 | 2008-11-12 | 罗伯特·施勒格尔 | Nanosized carbon material-activated carbon composite |
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