CN101213020B - Method for synthesis of carbon nanotubes - Google Patents

Method for synthesis of carbon nanotubes Download PDF

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CN101213020B
CN101213020B CN2006800040835A CN200680004083A CN101213020B CN 101213020 B CN101213020 B CN 101213020B CN 2006800040835 A CN2006800040835 A CN 2006800040835A CN 200680004083 A CN200680004083 A CN 200680004083A CN 101213020 B CN101213020 B CN 101213020B
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catalyst
iron
matrix
amount
dipping
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CN101213020A (en
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S·博德尔
D·科查德
E·杜蒂尔
P·盖拉德
D·普利
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Arkema France SA
Arkema SA
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B01J35/40—
    • B01J35/60—
    • 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
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/605—Products containing multiple oriented crystallites, e.g. columnar crystallites
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B01J35/615—
    • B01J35/66—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/06—Multi-walled nanotubes

Abstract

The invention concerns a method for preparing carbon nanotubes by contacting a carbon source with a multivalent metal and/or metal oxide based catalyst deposited on an inorganic substrate of BET specific surface greater than 50m<2>/g. The resulting carbon nanotubes can be used as agents for improving the mechanical and electrical conductivity properties in polymer compositions.

Description

The synthetic method of CNT
The synthetic method that the objective of the invention is CNT (NTC), this method are in the presence of the metallic catalyst that carries with specific inorganic matrix, in gas phase, to carry out.
Prior art
Today, people know that CNT is because of its mechanical performance, very high shape ratio (length/diameter) and electrical property but the material with lot of advantages.
They are made up of hemisphere end-blocking winding graphite linings, and this hemisphere is made up of pentagon and hexagon near fullerene structure.
People know the nanotube of being made up of individual layer: therefore be referred to as SWNT (english abbreviation of single-walled nanotube), or know the nanotube of being made up of concentric multilayer, therefore be referred to as MWNT (english abbreviation of multiple wall nanotube).Generally speaking, the production of SWNT is than the production difficulty of MWNT.
Can produce CNT according to diverse ways, for example electric discharge, laser ablation method or vapor phase chemical deposition (CVD).
In these technology, this is the seemingly unique technology that can guarantee to produce in large quantities CNT easily of a kind of technology afterwards, guarantees to reach to make them be used for the necessary condition of the cost of polymer and resin application in large quantities.
According to this method, be injected into carbon source in the catalyst with relatively-high temperature degree, described catalyst can be made up of the metal that inoganic solids carries.In these metals, preferably enumerate iron, cobalt, nickel, molybdenum and in these carriers, often aluminium oxide, silica or magnesia.
The carbon source that can consider is methane, ethane, ethene, acetylene, ethanol, methyl alcohol, acetone, even forming gas CO+H 2(HIPCO method).
In relating to the synthetic file of CNT; Can enumerate the WO 86/03455A1 of Hyperion Catalysis International Inc., it is corresponding to EP 225.556B1, and this document can be thought one of basic patent of synthetic NTC; It requires protection almost columniform carbon fibrils (the former title of NTC); Its diameter is 3.5-70nm, and the shape ratio is greater than or equal to 100, and their preparation method.
Make and contain iron (Fe for example 3O 4, Fe that carbon carrier carries, Fe that alumina support carries or contain the Fe that carrier that carbon fibrils processes carries) catalyst contact with the gaseous compound that contains carbon (preferably CO or hydro carbons) and carries out this synthesizing, advantageously can react generation gaseous products (for example CO, H with carbon 2Or H 2O) compound exists down.In these embodiment, these catalyst are to adopt dried dipping, deposition or the preparation of wet impregnation method.
WO 87/07559 corresponding to same applicant's EP 270.666 B1 requires protection to use same reactant and Catalyst Production diameter to be 3.5-70nm, and shape ratio L/D is the fibriilar method of 5-100.
Except being under the situation of benzene, outside operating more than 800 ℃, do not provide any information of relevant productive rate (it should be expressed as every gram catalyst time per unit and generate fibriilar quality) at the gaseous compound that contains carbon.
It improves one's methods some other documentation requirements protection; Continuous fluidized bed for example; It can control the coherent condition (for example referring to the WO02/94713A1 with Tsing-Hua University's name application) of the carbonaceous material of catalyst and generation; Or it improves product to require protection, and for example with WO 02/095097 A1 of Trust é es Of Boston College name application, it prepares the nanotube of the different shape of non-alignment through relying on catalyst property and these reaction conditions.
US 2001/0036549 A1 of Hyperion Catalysis International Inc. described through with the multivalence transition metal or preferably the decomposition of the carbon source that contacts of metal mixture (for example Fe and Mo, Cr, Mn and/or Ce) prepare improving one's methods of NTC, the transition metal that its improvements are to form the catalytic site of a large amount of 3.5-70nm of being of a size of is carried on the inorganic matrix of size less than 400 μ m.
In these instances; This carbon source is hydrogen/mixture of ethylene; Its separately dividing potential drop be 0.66 and 0.33, be 30 minutes 650 ℃ reaction time, this catalyst is in the presence of methyl alcohol, to use ferric nitrate dipping alumina (not provide iron content; Estimate 15%) prepare, the amount of its methyl alcohol is enough to obtain stick with paste; Productive rate is at 30 minutes 6.9g/g, and when adding molybdenum salt, during for about 9-10% of iron content and molybdenum content 1-2%, its productive rate reaches 10.9-11.8.When altogether-when metal was cerium, chromium, manganese, the productive rate of nanotube was respectively 8,3,9.7 and 11.
Confirm that also the efficient of pentanedione iron is not as ferric nitrate.
In embodiment 16, equal basically at 6 o'clock at pH, flood through adding the wet method that ferric nitrate and sodium bicarbonate solution precipitate simultaneously.When iron content is 15% to add fashionablely with semicontinuous in this reactor, the selectivity that this catalyst reaches is 10.5.
Adopt another embodiment of iron and molybdenum wet impregnation to obtain and the same good result of methyl alcohol method.
This file shows that also the molybdenum that is higher than 2.5% content in order to the Mo meter replaces iron disadvantageous more precisely, because the productive rate of equal proportion Fe and Mc (total amount=16.7%) mixture in 30 minutes reaches 8.8.
When using non-porous carrier, the for example employed specific area=100m of Hyperion 2During the Degussa alumina of/g, confirm that a large amount of iron of dipping is difficult, because just skin is that gas is accessibility, these internal layers do not have sufficient catalytic action.
In addition, the technology of using this type carrier is complicated, because the size of these particulates is 20nm, its bulk density is 0.06, has increased the difficulty of industrial use like this.
The objective of the invention is through decomposing the method for the synthetic NTC of carbon source; Carbon source is placed reactor; Preferably in fluidized-bed reactor, under temperature 500-1500 ℃, make this carbon source and one or more oxidation state be zero and/or the multivalence transition metal that is oxide form (positive oxidation state) contact; And reclaim described NTC, it is characterized in that this or these transition metal and/or its one or more oxides are to be higher than 50m with the BET specific area 2/ g, preferably 70m 2/ g to 300m 2The matrix of/g carries; In these carriers, preferably can enumerate these inorganic carriers, advantageously be γ or θ type aluminium oxide.
According to preferred embodiment a kind of; These carriers are easy to flood a certain amount of multivalence transition metal and/or transition metal oxide; For example; The quality of transition metal can be 50 weight % up to this final catalyst, advantageously is the 15-50 weight % of final catalyst, preferably 30-40 weight %.
Advantageously select the size of carrier particles, so that this catalyst has good fluidisation when the NTC synthetic reaction.In reality, in order to guarantee reasonable productive rate, the about in a broad sense 20-500 μ of carrier particles diameter m is preferred.Certainly, if the size of this carrier particles is outside the pointed in front scope, also not exceed scope of the present invention.
Advantageously, under dry gas purges, carry out the dipping of carrier particles, for example in room temperature to the temperature of this solution boiling temperature, when this transition metal is iron with the iron nitrate aqueous solution mode; Select the amount of dipping solution,, thereby guarantee on said carrier particles, to form skin covering of the surface so that these carrier particles contact with the solution of q.s at any time.
It is true " to do " processing; At any time have just in time promptly that to form the necessary amount of liquid of liquid film at the catalytic carrier microparticle surfaces be favourable, because when heating, can avoid these aqueous effluents (nitrate aqueous effluent when this dipping solution contains ferric nitrate for example like this with dry air purging mode; Behind the dipping, the product that obtains is heated to about 300 ℃ with inertia or non-inert gas form, to remove these nitrate).
According to preferred embodiment, in this synthesis reactor, advantageously original position is carried out the reduction reaction of this catalyst in the fluid bed synthesis reactor; And this catalyst ingress of air no longer; Therefore, this or these transition metal, preferred subway keeps metallic forms.
Using the metal oxide form, preferably under the situation of synthetic NTC, this catalyst can directly inject this reaction medium to the catalyst of form of iron oxide, need not pass through reduction step continuously.Therefore advantageously avoid installing the catalyst that reduction reactor and/or storage are the reduction form, and this catalyst should use under inert gas.
This carbon source can be selected from the carbonaceous material of any kind of; For example methane, ethane, propane, butane, other higher aliphatic alkane, benzene, cyclohexane, ethene, propylene, butylene, isobutene, other higher aliphatic alkene, toluene, xylenes, cumene, ethylbenzene, naphthalene, phenanthrene, anthracene, acetylene and senior alkynes, formaldehyde, acetaldehyde, acetone, methyl alcohol, ethanol, carbon monoxide etc., they are independent or mix.
The NTC that obtains according to said method can be used for many technical fields; Especially electronics is (according to temperature and its structure; They can be conductor, semiconductor and insulator), machinery, for example be used for reinforced composite (these NTC than steel firm 100 times and light six times) and motor machine (can or shrink their elongations) technical field through injecting filler.For example can enumerate the purposes of NTC in macromolecule compositions, these macromolecule compositions are used for the purposes of the for example production of packing, oil pipe (fuel line), antistatic coating or the coating of electronic building brick and in the purposes of thermistor, super capacity electrode etc.
Embodiment 1
Use Puralox NWA 155 gamma-aluminas to prepare catalyst, the particulate below the 5 weight % of these Puralox NWA 155 gamma-aluminas is less than 100 μ m, and below 2% greater than 500 μ m, median diameter is about 250 μ m.Below these surface characteristics and voidage characteristic are listed in:
BET surface (m 2/ g) 154
Total pore volume (cm 3/ g) 0.45 (adopt DFT to measure the hole of 0-200nm)
Micro pore volume (cm 3/ g) 0.005 (adopt t-plot to measure the hole of 0-2nm).
In being heated to 100 ℃ 3L jacketed reactor, add the 300g aluminium oxide, use air purge.Utilize pump to inject the ferrous solution that 700ml contains 545g/l anhydrous nitric acid iron continuously then.Target is 15% ferrous metal than (metal quality/catalyst quality), and the interpolation time of this ferrous solution is 10 hours, and this liquid interpolation speed equals evaporation of water speed.
This catalyst placed 100 ℃ of baking ovens 16 hours then.
Embodiment 2
Use the Puralox SCCA 5-150 gamma-alumina of the about 85 μ m of median diameter to prepare catalyst.
Below these surface characteristics and voidage characteristic are listed in:
BET surface (m 2/ g) 148
Total pore volume (cm 3/ g) 0.47 (adopt DFT to measure the hole of 0-200nm)
Micro pore volume (cm 3/ g) 0.0036 (adopt t-plot to measure the hole of 0-2nm)
To prepare catalyst and dipping with embodiment 1 same way as.
Embodiment 3
Use same SCCA 5-150 aluminium oxide, contain the catalyst of 25% iron through dipping preparation under the condition that approaches embodiment 2: the ratio of the iron content of setting in hope is regulated interpolation time and liquor capacity, promptly 16 hours simply.
This catalyst placed 100 ℃ of baking ovens 16 hours then.
Embodiment 4
The catalyst that contains 35% iron through the preparation of dipping SCCA 5-150 aluminium oxide.The ratio of the iron content of setting in hope is regulated interpolation time and liquor capacity, promptly 23 hours simply.
This catalyst placed 100 ℃ of baking ovens 16 hours then.
Embodiment 5
The catalyst that contains 50% iron through the preparation of dipping SCCA 5-150 aluminium oxide.The ratio of the iron content of setting in hope is regulated interpolation time and liquor capacity, promptly 32 hours simply.
This catalyst placed 100 ℃ of baking ovens 16 hours then.
Embodiment 6
The use median diameter is that the C 500-511 gamma-alumina of the Engelhard of 150 μ m prepares catalyst.
Below these surface characteristics and voidage characteristic are listed in:
BET surface (m 2/ g) 206
Total pore volume (cm 3/ g) 0.48 (adopt DFT to measure the hole of 0-200nm)
Micro pore volume (cm 3/ g) 0 (adopt t-plot to measure the hole of 0-2nm)
Adopt the condition of embodiment 3, preparation contains the catalyst of 25% iron.This catalyst place 100 ℃ following 16 hours.
Embodiment 7
The use median diameter is that the C 500-512 θ aluminium oxide of the Engelhard of 70 μ m prepares catalyst.
Below these surface characteristics and voidage characteristic are listed in:
BET surface (m 2/ g) 93
Total pore volume (cm 3/ g) 0.37 (adopt DFT to measure the hole of 0-200nm)
Micro pore volume (cm 3/ g) 0.003 (adopt t-plot to measure the hole of 0-2nm)
With the same terms of embodiment 3 under, adopt immersion process for preparing to contain the catalyst of 25% iron.
Embodiment 8
With the layered catalyst of the about 150g of the quality diameter of packing into is that 25cm, effective depth are to carry out the catalysis test in the reactor of 1m, and this reactor has been equipped with the separator that is used to avoid fine particles is taken to downstream.Under nitrogen, these nitrate are decomposed, under hydrogen and nitrogen (20%/80% volume), be heated to 650 ℃ then 300 ℃ of heating.Under this temperature, setting the ethene flow is 3000NL/ hour, and hydrogen flowing quantity is 1000NL/ hour, and this is 0.75 corresponding to ethylene partial pressure.
Gas flow should be enough to make this solid to substantially exceed the fluidisation limit velocity, still is lower than the speed of flying out simultaneously.
After 60 minutes, stop heating, estimate to generate product amount result.Simultaneously, adopt the microscopic method assessment to generate nanotube amount (generation NTC type: SWNT or MWNT; There is other form of C in
Figure GSB00000015061200061
).
These results come together in the following table:
Figure GSB00000015061200062
As a comparison, the embodiment 10 of US 2001/0036549 has described by hydrogen/mixture of ethylene and has contacted synthetic NTC with the catalyst that contains 12% iron, and this catalyst is to prepare with the alumina that ferric nitrate floods; NTC productive rate at 30 minutes inner catalysts is 5.5.
Embodiment 9
The catalyst of embodiment 4 preparation is added in the reactor of embodiment 8, and 300 ℃ of heating to decompose these nitrate.Cool off this reactor and reclaim this catalyst with air.Therefore that does not stand reduction step also is this catalyst of ferriferous oxide form, and then is added in embodiment 8 reactors that are heated to 650 ℃, and directly in ethene and hydrogen stream, the therein ethylene dividing potential drop is 0.8.React after 60 minutes, stop heating, assessment generates the amount and the quality results of product.Obtain 14.6 productive rate, this result and the result who uses reducing catalyst to obtain are comparable; The NTC that generates is MWNT type/
Figure GSB00000015061200071
10-30nm, and they do not contain other form of carbon.

Claims (8)

1. through decomposing the method for carbon source synthesizing carbon nanotubes, under temperature 500-1500 ℃, to make this carbon source that places fluidized-bed reactor be zero with oxidation state and/or the iron that is oxide form contacts, and reclaim described CNT, it is characterized in that:
-iron and/or its oxide are to use the BET specific area to be 70m 2/ g-300m 2The matrix of/g carries, and this matrix is selected from γ or θ type aluminium oxide,
-use dipping solution this matrix of dipping under dry gas purges that contains at least a molysite to prepare catalyst; And select the amount of dipping solution; So that these carrier particles enough contact with the solution that guarantees the amount of formation skin covering of the surface on said carrier particles at any time with just in time
The amount of-iron is the 15-50 weight % of final catalyst.
2. method according to claim 1 is characterized in that catalyst is iron oxide based.
3. method according to claim 1 and 2, the amount that it is characterized in that iron are the 30-40 weight % of final catalyst.
4. method according to claim 1 and 2 is characterized in that these catalyst particles are the particulate form of diameter 20-500 μ m.
5. method according to claim 1 and 2 is characterized in that said catalyst is through using the iron nitrate aqueous solution impregnation matrix to prepare.
6. method according to claim 5 is characterized in that said catalyst is through using iron nitrate aqueous solution impregnation matrix under the temperature between room temperature to this dipping solution boiling temperature to prepare.
7. method according to claim 1 and 2 it is characterized in that this catalyst original position reduces, and this catalyst contacts no longer with air.
8. method according to claim 1 and 2 is characterized in that this method is continuous.
CN2006800040835A 2005-02-07 2006-02-03 Method for synthesis of carbon nanotubes Active CN101213020B (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
FR0501197 2005-02-07
FR0501197A FR2881734B1 (en) 2005-02-07 2005-02-07 PROCESS FOR THE SYNTHESIS OF CARBON NANOTUBES
FR0510699 2005-10-20
FR0510699A FR2881735B1 (en) 2005-02-07 2005-10-20 PROCESS FOR THE SYNTHESIS OF CARBON NANOTUBES
US72965005P 2005-10-24 2005-10-24
US60/729,650 2005-10-24
PCT/FR2006/000250 WO2006082325A1 (en) 2005-02-07 2006-02-03 Method for synthesis of carbon nanotubes

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FR2901156B1 (en) * 2006-05-16 2009-01-23 Arkema Sa CATALYTIC COMPOSITE BASED ON CATALYTIC ACTIVE CHARCOAL AND CARBON NANOTUBES, PROCESS FOR PRODUCING THE SAME, ELECTRODE AND SUPERCONDENSOR COMPRISING THE CATALYTIC COMPOSITE
EP2213369B1 (en) * 2009-01-15 2015-07-01 Carlo Vittorio Mazzocchia A process for the preparation of a catalyst, a catalyst obtained thereby, and its use in the production of nanotubes
CN106009600B (en) * 2016-07-29 2019-07-23 菏泽学院 Improve polyethylene oxide/polybutylene succinate polyblend mechanical property method
CN113562722B (en) * 2021-08-05 2023-06-20 青岛科技大学 Method for producing carbon nano tube by using semicoke-based catalyst prepared by microfluidization bed

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