CA2164731A1 - Method for separating off fullerene from fullerene-containing carbon black - Google Patents
Method for separating off fullerene from fullerene-containing carbon blackInfo
- Publication number
- CA2164731A1 CA2164731A1 CA002164731A CA2164731A CA2164731A1 CA 2164731 A1 CA2164731 A1 CA 2164731A1 CA 002164731 A CA002164731 A CA 002164731A CA 2164731 A CA2164731 A CA 2164731A CA 2164731 A1 CA2164731 A1 CA 2164731A1
- Authority
- CA
- Canada
- Prior art keywords
- fullerene
- carbon black
- separating
- carrier gas
- containing carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C01B32/152—Fullerenes
- C01B32/156—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Gasification And Melting Of Waste (AREA)
Abstract
The invention relates to a method for separating off fullerenes from fullerene-containing carbon black. The carbon black is heated by microwaves and blanketed by a carrier gas stream.
Description
? F' ~ I 1 3~ J ~ ~ ~4 7 3 1 Method for separating off fullerene from fullerene-cont~; n; ng carbon black Fullerene-cont~;n;ng carbon black is preferably generated by the method of Rratschmer and Huffman by vaporizing graphite in an electric arc. The C60- and C70-- fullerenes are predominantly isolated by the method known from the literature of toluene extraction with subsequent column chromatography (Kratschmer, W. et al., Nature 347, 1990, p. 354). Only occasionally, to prepare special samples and thin layers, are C60 and C70 purified by sublimation (Lin, J.Z. et al., Appl. Phys. Lett. 62(5), 1993).
Work-up of the fullerene-containing carbon black using solvents has a number of problems:
- large solvent streams owing to low solubility;
- long residence time on the chromatography column, danger of decomposition;
- extensive, energy-intensive solvent work-up.
It has now been found that fullerenes can be separated off from carbon black by means of sublimation, by inputting energy by microwaves which interact with the carbon black, and the sublimed fullerene vapors being separated from the carbon black using an inert gas stream, which can be preheated to 300 to 1000 R, and being deposited in a co~en~ation zone.
The invention thus relates to a method for 6eparating off fullerene from fullerene-contA;n;ng carbon black, in which the carbon black is heated by microwaves and blanketed with a carrier gas stream.
The fullerene-cont~;n;ng carbon black is heated by microwaves to 600 to 1300 ~. The carbon black can be heated by microwaves having a frequency of 433 to 24125 MHz. A blanketing carrier gas stream is used which takes up the vaporizing fullerenes. Entrained carbon black particles are separated off via a heat-resistant filter.
The fullerene-cont~;n;ng carrier gas stream is then 216~7~1 _ - 2 -cooled stepwise for fractional fullerene depo~ition. The sublimation can be carried out at atmoQpheric pressure or at reduced pressure of 5 1000 mbar.
The carrier gas stream can be loaded both in a partial vacuum and also at a slight gage pre~sure.
Operating pre~sures in the range from 1 mbar to 2 bar are possible; the procedure is preferably carried out in the region of the ~hient pressure.
Carrier gases suitable for the process according to the invention are noble gases such as helium, neon and argon and other inert gases. In principle, two or more of said gases can also be u~ed as mixture for the process according to the invention.
The volumetric flow rate of the carrier ga~ can vary in wide range~ and is e~entially dependent on the geometry of the apparatus. Accordingly, the flow velocity can likewise vary in wide ranges. The procedure can be carried out at a flow velocity of 0.1 to 100 m/sec, preferably 5 to 15 m/sec. However, the fullerene can also be di~charged at lower or higher velocities. Preferably, a flow velocity i~ employed which permits the formation of a fluidized bed. However, other flow velocities can be employed which lead to the formation of a fluid bed or a fixed bed through which the flow passes.
The temperature of the gas fed in can also vary in wide ranges and will be guided by which fullerene Qpecies are to be isolated. In order to isolate C60 and/or C70, the carrier gas is preferably preheated to a temperature range of 700 to 1000 R. Depo~ition of the cry6talline fullerenes can, in contrast, occur below approximately 600C.
The combination of heating the fullerene-contain-ing carbon black by microwave~ and blanketing with a carrier gas stream effects a significant velocity-yield increa~e compared with conventional method~ and compared with individual application of the two ~teps. The micro-wave-transport gas-fluidized bed-sublimation method gives high fullerene yields of above 80% within a few minutes duration of irradiation.
~16~731 _ - 3 -The invention i8 described in more detail below with reference to an example:
Example In a commercial laboratory microwave apparatus type MLS 1200 from Buchi GmbH, D-7320 Goppingen, fuller-ene-containing carbon black is heated by microwaves (800 watts) in a vertical quartz glass tube (length: 150 mm, internal diameter: 20 mm). The carbon black sample is held in the vertical tube by a quartz frit. The carrier gas stream, preferably helium, 250 l/h, coming from below flowR through the sample and generates a fluidized bed.
The gas stream further ensures that the sublimed ful-lerenes are carried away into the co~n~ation zone. The condensation zone in this example i~ the space in the quartz tube above the sample, which i8 packed with quartz wool.
The sample was irradiated 5 times for 1 minute at 800 watts. Between the heating phase~ there was in each case a cooling phase of 1 minute. This procedure ensured that the sublimation temperature did not exceed 800C.
HPLC analysis of condensate shows a yield of 80%
and a composition of 75% C60 and 25% C70.
Work-up of the fullerene-containing carbon black using solvents has a number of problems:
- large solvent streams owing to low solubility;
- long residence time on the chromatography column, danger of decomposition;
- extensive, energy-intensive solvent work-up.
It has now been found that fullerenes can be separated off from carbon black by means of sublimation, by inputting energy by microwaves which interact with the carbon black, and the sublimed fullerene vapors being separated from the carbon black using an inert gas stream, which can be preheated to 300 to 1000 R, and being deposited in a co~en~ation zone.
The invention thus relates to a method for 6eparating off fullerene from fullerene-contA;n;ng carbon black, in which the carbon black is heated by microwaves and blanketed with a carrier gas stream.
The fullerene-cont~;n;ng carbon black is heated by microwaves to 600 to 1300 ~. The carbon black can be heated by microwaves having a frequency of 433 to 24125 MHz. A blanketing carrier gas stream is used which takes up the vaporizing fullerenes. Entrained carbon black particles are separated off via a heat-resistant filter.
The fullerene-cont~;n;ng carrier gas stream is then 216~7~1 _ - 2 -cooled stepwise for fractional fullerene depo~ition. The sublimation can be carried out at atmoQpheric pressure or at reduced pressure of 5 1000 mbar.
The carrier gas stream can be loaded both in a partial vacuum and also at a slight gage pre~sure.
Operating pre~sures in the range from 1 mbar to 2 bar are possible; the procedure is preferably carried out in the region of the ~hient pressure.
Carrier gases suitable for the process according to the invention are noble gases such as helium, neon and argon and other inert gases. In principle, two or more of said gases can also be u~ed as mixture for the process according to the invention.
The volumetric flow rate of the carrier ga~ can vary in wide range~ and is e~entially dependent on the geometry of the apparatus. Accordingly, the flow velocity can likewise vary in wide ranges. The procedure can be carried out at a flow velocity of 0.1 to 100 m/sec, preferably 5 to 15 m/sec. However, the fullerene can also be di~charged at lower or higher velocities. Preferably, a flow velocity i~ employed which permits the formation of a fluidized bed. However, other flow velocities can be employed which lead to the formation of a fluid bed or a fixed bed through which the flow passes.
The temperature of the gas fed in can also vary in wide ranges and will be guided by which fullerene Qpecies are to be isolated. In order to isolate C60 and/or C70, the carrier gas is preferably preheated to a temperature range of 700 to 1000 R. Depo~ition of the cry6talline fullerenes can, in contrast, occur below approximately 600C.
The combination of heating the fullerene-contain-ing carbon black by microwave~ and blanketing with a carrier gas stream effects a significant velocity-yield increa~e compared with conventional method~ and compared with individual application of the two ~teps. The micro-wave-transport gas-fluidized bed-sublimation method gives high fullerene yields of above 80% within a few minutes duration of irradiation.
~16~731 _ - 3 -The invention i8 described in more detail below with reference to an example:
Example In a commercial laboratory microwave apparatus type MLS 1200 from Buchi GmbH, D-7320 Goppingen, fuller-ene-containing carbon black is heated by microwaves (800 watts) in a vertical quartz glass tube (length: 150 mm, internal diameter: 20 mm). The carbon black sample is held in the vertical tube by a quartz frit. The carrier gas stream, preferably helium, 250 l/h, coming from below flowR through the sample and generates a fluidized bed.
The gas stream further ensures that the sublimed ful-lerenes are carried away into the co~n~ation zone. The condensation zone in this example i~ the space in the quartz tube above the sample, which i8 packed with quartz wool.
The sample was irradiated 5 times for 1 minute at 800 watts. Between the heating phase~ there was in each case a cooling phase of 1 minute. This procedure ensured that the sublimation temperature did not exceed 800C.
HPLC analysis of condensate shows a yield of 80%
and a composition of 75% C60 and 25% C70.
Claims (4)
1. A method for separating off fullerene from fullerene-containing carbon black, which comprises heating the carbon black by microwaves and blanketing with a carrier gas stream.
2. The method as claimed in claim 1, wherein inert gases are used as carrier gas.
3. The method as claimed in claim 1 or 2, wherein the carbon black is heated by microwaves having a fre-quency of 403 to 24,125 MHz.
4. The method as claimed in one or more of claims 1 to 3, wherein a carrier gas flow velocity of 0.1 to 100 m/sec is employed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4319049A DE4319049A1 (en) | 1993-06-08 | 1993-06-08 | Process for the separation of fullerene from soot containing fullerene |
| DEP4319049.9 | 1993-06-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2164731A1 true CA2164731A1 (en) | 1994-12-22 |
Family
ID=6489923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002164731A Abandoned CA2164731A1 (en) | 1993-06-08 | 1994-05-26 | Method for separating off fullerene from fullerene-containing carbon black |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0705219B1 (en) |
| JP (1) | JPH08510986A (en) |
| CN (1) | CN1124948A (en) |
| AT (1) | ATE151387T1 (en) |
| CA (1) | CA2164731A1 (en) |
| DE (2) | DE4319049A1 (en) |
| DK (1) | DK0705219T3 (en) |
| ES (1) | ES2101542T3 (en) |
| GR (1) | GR3023857T3 (en) |
| WO (1) | WO1994029218A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998033742A1 (en) * | 1997-02-03 | 1998-08-06 | Viktor Ivanovich Petrik | Industrial production of fullerenes |
| FR2764280B1 (en) * | 1997-06-06 | 1999-07-16 | Yvan Alfred Schwob | PROCESS FOR THE MANUFACTURE OF CARBON 60 |
| DE102009045060A1 (en) * | 2009-09-28 | 2011-03-31 | Evonik Degussa Gmbh | Carbon black, a process for its preparation and its use |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE131453T1 (en) * | 1992-05-06 | 1995-12-15 | Hoechst Ag | SEPARATION OF FULLERENES |
-
1993
- 1993-06-08 DE DE4319049A patent/DE4319049A1/en not_active Withdrawn
-
1994
- 1994-05-26 EP EP94918797A patent/EP0705219B1/en not_active Expired - Lifetime
- 1994-05-26 WO PCT/EP1994/001712 patent/WO1994029218A1/en active IP Right Grant
- 1994-05-26 ES ES94918797T patent/ES2101542T3/en not_active Expired - Lifetime
- 1994-05-26 DK DK94918797.5T patent/DK0705219T3/en active
- 1994-05-26 AT AT94918797T patent/ATE151387T1/en active
- 1994-05-26 DE DE59402389T patent/DE59402389D1/en not_active Expired - Fee Related
- 1994-05-26 JP JP7501255A patent/JPH08510986A/en active Pending
- 1994-05-26 CA CA002164731A patent/CA2164731A1/en not_active Abandoned
- 1994-05-26 CN CN94192378A patent/CN1124948A/en active Pending
-
1997
- 1997-06-20 GR GR970401498T patent/GR3023857T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0705219B1 (en) | 1997-04-09 |
| ES2101542T3 (en) | 1997-07-01 |
| DE4319049A1 (en) | 1994-12-15 |
| ATE151387T1 (en) | 1997-04-15 |
| DE59402389D1 (en) | 1997-05-15 |
| JPH08510986A (en) | 1996-11-19 |
| WO1994029218A1 (en) | 1994-12-22 |
| EP0705219A1 (en) | 1996-04-10 |
| CN1124948A (en) | 1996-06-19 |
| DK0705219T3 (en) | 1997-10-20 |
| GR3023857T3 (en) | 1997-09-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |