[go: up one dir, main page]

WO1995006001A1 - Procede de preparation de fullerenes - Google Patents

Procede de preparation de fullerenes Download PDF

Info

Publication number
WO1995006001A1
WO1995006001A1 PCT/EP1994/002770 EP9402770W WO9506001A1 WO 1995006001 A1 WO1995006001 A1 WO 1995006001A1 EP 9402770 W EP9402770 W EP 9402770W WO 9506001 A1 WO9506001 A1 WO 9506001A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
fullerenes
pyrolysis
solvent
aromatic
Prior art date
Application number
PCT/EP1994/002770
Other languages
English (en)
Inventor
Roger Taylor
Original Assignee
Hoechst Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst Aktiengesellschaft filed Critical Hoechst Aktiengesellschaft
Priority to EP94925463A priority Critical patent/EP0717721A1/fr
Priority to JP7507339A priority patent/JPH09501648A/ja
Publication of WO1995006001A1 publication Critical patent/WO1995006001A1/fr

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
    • C01B32/154—Preparation
    • 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

Definitions

  • the present invention relates to a novel process for the preparation of fullerenes.
  • the known process enables the production of fullerenes in relatively large quantities, the method does have a number of disadvantages.
  • the process is essentially a batch process since the graphite rods (which are expensive) are consumed in the process.
  • various techniques have been employed to try to increase the production per batch such techniques tend to be complex and costly.
  • the reaction produces a large quantity of an extremely light and static soot. Removal of the soot from the reaction system is a difficult task and is potentially hazardous since the by-products formed and perhaps even the fullerenes themselves may be carcinogenic.
  • Other methods for the preparation of fullerenes have been devised but they all suffer from disadvantages; they are essentially batch processes and/or they are very costly or result in large amounts of by-products.
  • a process for the preparation of fullerenes which comprises subjecting one or more optionally substituted aromatic hydrocarbons to pyrolysis. Whilst the presence of relatively small concentrations of oxygen may not be detrimental it is desirable to takes steps to minimize the oxygen content of the pyrolysis reaction environment. This may, for example, be achieved by using an inert gas atmosphere, for example helium, argon or nitrogen or, alternatively, the pyrolysis may be performed in vacuo.
  • the process according to the present invention has the advantages that it enables inexpensive materials to be used as the feedstock, can be performed using simple apparatus and may be adapted to provide a continous production process.
  • the reaction products may also be recovered in a less hazardous manner.
  • aromatic hydrocarbons polycyciic aromatic hydrocarbons are preferred, in particular those having 10 - 32 carbon atoms for example anthracene, phenanthrene, fluoranthene, ovalene, corannulene and naphthalene, naphthalene being especially preferred.
  • the pyrolysis is conveniently performed in the gas phase at a temperature between 500 ° and 3000 °C, preferably between 800 ° and 1500 °C, most preferably around 1000 °C.
  • a preferred method for performing the process according to the present invention is to pass the vaporised aromatic feedstock material through a tube heated to the appropriate temperature.
  • the tube may be made of any suitable material such as, for example, silica (for temperatures up to approximately 1300 °C), a metal, for example iron, steel, nickel and copper (up to temperatures just below their melting points) or ceramic materials.
  • the rate of evaporation of aromatic feedstock is desirably kept below 600 mg min "1 ; when using naphthalene a rate of evaporation of around 200 mg min '1 is particularly preferred.
  • the flow rate for a 1 cm diameter tube is typically up to 50 ml min '1 for a heated region up to 5 cm in length. With larger tubes and/or longer or multiple heated regions appropriate adjustments to the flow rate may be made.
  • the process according to present invention may be assisted by the use of a suitable catalyst, preferably a metal or metal containing catalyst, for example, nickel powder, palladium on carbon or metallic or non-metallic oxides.
  • a suitable catalyst preferably a metal or metal containing catalyst, for example, nickel powder, palladium on carbon or metallic or non-metallic oxides.
  • the fullerenes produced are subsequently isolated from the effluent gases from the pyrolysis reaction.
  • the preferred method for achieving this is firstly to pass the effluent gas into a cooling system, for example a cooling core where the majority of the pyrolysis product will collect. Cooling may be achieved by any suitable coolant, for example water, ice or dry-ice.
  • the gas stream is then passed through one or more solvent scrubbers, the pyrolysis reaction tube and cooling core are washed out, the resulting solvent slurry of the products is filtered and the filter cake is thoroughly washed.
  • the solvent used in the scrubbers and for the subsequent washing steps is conveniently one in which the unwanted by-products dissolve, for example a ketone, especially acetone, or an ether, especially diethyl ether.
  • the filter cake is then washed with a suitable solvent in which fullerenes are soluble, for example carbon disulfide, toluene, benzene, xylenes or 1,2-dichlorobenzene.
  • the resulting solution may then be concentrated and purified by the standard methods for the purification of fullerenes. Separation of the various fullerenes produced may then be achieved by standard chromatographic methods. Examples of suitable methods include those devised by R. Taylor et al (J. Chem. Soc, Chem. Comm., pp 1423 - 1425, 1990).
  • the by-products obtained in the process which are soluble in the polar solvent used include fullerene precursors and these may be recycled to increase the yield of the process. Such recycling of precursors allows for a continous preparation process.
  • naphthalene as the aromatic hydrocarbon the principal fullerenes produced in the process are Cgg and C 70 .
  • aromatic hydrocarbons as feedstock, either individually or in combination, may result in production of other fullerenes.
  • the process according to the present invention may also be useful in the production of endohedral fullerene metal complexes.
  • the standard synthesis of endohedral fullerene complexes entails a slight modification of the basic Kratschmer method i. e. resistive vaporisation of graphite impregnated with metal oxides or graphite rods into which metal rods have been drilled.
  • the yield of endohedral complexes from such a process is, however, very low.
  • the process of the present invention may be modified by passing the vaporised aromatic feedstock over a metal source heated to an appropriate temperature resulting in the production of endohedral fullerene complexes containing the metal of the source.
  • Metal sources used for the endohedral fullerene metal complex are for example sole metals, metal halides, metal oxides and/or metal carbonates.
  • Example 1 A deposit of naphthalene was placed at the inlet end of a 1 cm diameter Pyrex ® glass tube of 40 cm length. Argon was passed through the apparatus at the rate of 15 ml min '1 for a few minutes, the naphthalene was gently heated with a butane torch and a 2 cm length near the outlet end of the tube was heated with a propane/oxygen torch to approximately 1000 °C. As the naphthalene vapour passed over the heated region pyrolysis occurred.
  • the effluent gases were passed through an outlet of the tube into a glass coil immersed in dry ice and then into a triple batch of acetone scrubbers.
  • the contents of the tube and cooling coil were washed out with acetone and combined with the acetone from the scrubbers.
  • the acetone slurry of the products were filtered and washed thoroughly with acetone to leave a black sooty deposit. This was then washed with carbon disulfide to give a deep red solution.
  • the solution was concentrated and purified by standard techniques to produce Cg Q and C 70 , the combined yield of Cg Q and C 70 being approximately 0,5 %.
  • iii) m/z 624/622/620.
  • iv) m/z 752/750/748/746. Evidenve of e. g. tetranaphthylbenzofluoranthene with further ring closures and elimination of up to twenty-two hydrogens.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Un procédé de préparation de fullerènes consiste à soumettre un ou plusieurs hydrocarbures aromatiques, avec une substitution éventuelle, à une pyrolyse.
PCT/EP1994/002770 1993-08-20 1994-08-19 Procede de preparation de fullerenes WO1995006001A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP94925463A EP0717721A1 (fr) 1993-08-20 1994-08-19 Procede de preparation de fullerenes
JP7507339A JPH09501648A (ja) 1993-08-20 1994-08-19 フラーレン類の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB939317342A GB9317342D0 (en) 1993-08-20 1993-08-20 Process for the preparation of fullerenes
GB9317342.5 1993-08-20

Publications (1)

Publication Number Publication Date
WO1995006001A1 true WO1995006001A1 (fr) 1995-03-02

Family

ID=10740789

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/002770 WO1995006001A1 (fr) 1993-08-20 1994-08-19 Procede de preparation de fullerenes

Country Status (6)

Country Link
EP (1) EP0717721A1 (fr)
JP (1) JPH09501648A (fr)
CN (1) CN1131408A (fr)
CA (1) CA2169846A1 (fr)
GB (1) GB9317342D0 (fr)
WO (1) WO1995006001A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6083469A (en) * 1998-04-10 2000-07-04 Leftin; Harry Paul Pyrolysis process for making fullerenes
WO2003076335A1 (fr) * 2002-03-13 2003-09-18 Mitsubishi Chemical Corporation Procede de production de fullerenes et procede de separation de ceux-ci
EP1300363A3 (fr) * 2001-10-04 2005-01-12 Canon Kabushiki Kaisha Procede de preparation de fullerene
US7001581B2 (en) 2001-10-04 2006-02-21 Canon Kabushiki Kaisha Method for producing nanocarbon materials
EP2059474A4 (fr) * 2006-08-31 2011-08-24 Nano C Inc Recueil direct dans une phase liquide, et traitement de matériaux fulleréniques

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1059875C (zh) * 1998-09-30 2000-12-27 太原理工大学 金属纳米微粒修饰洋葱状富勒烯及制造方法
US7150863B2 (en) * 2001-08-30 2006-12-19 Tda Research, Inc. Polynuclear aromatic hydrocarbons for fullerene synthesis in flames
CN102060290B (zh) * 2010-12-02 2012-09-26 中国科学院理化技术研究所 一种利用生物质燃烧法生产富勒烯的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
K.F. LANG ET AL., CHEMISCHE BERICHTE, vol. 90, no. 12, 1957, WEINHEIM DE, pages 2888 - 2893 *
R. TAYLOR ET AL., NATURE, vol. 366, no. 6457, LONDON GB, pages 728 - 731 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6083469A (en) * 1998-04-10 2000-07-04 Leftin; Harry Paul Pyrolysis process for making fullerenes
EP1300363A3 (fr) * 2001-10-04 2005-01-12 Canon Kabushiki Kaisha Procede de preparation de fullerene
US6953564B2 (en) 2001-10-04 2005-10-11 Canon Kabushiki Kaisha Method for producing fullerenes
US7001581B2 (en) 2001-10-04 2006-02-21 Canon Kabushiki Kaisha Method for producing nanocarbon materials
WO2003076335A1 (fr) * 2002-03-13 2003-09-18 Mitsubishi Chemical Corporation Procede de production de fullerenes et procede de separation de ceux-ci
EP2059474A4 (fr) * 2006-08-31 2011-08-24 Nano C Inc Recueil direct dans une phase liquide, et traitement de matériaux fulleréniques
US8883113B2 (en) 2006-08-31 2014-11-11 Nano-C, Inc. Direct liquid-phase collection and processing of fullerenic materials

Also Published As

Publication number Publication date
CA2169846A1 (fr) 1995-03-02
JPH09501648A (ja) 1997-02-18
EP0717721A1 (fr) 1996-06-26
GB9317342D0 (en) 1993-10-06
CN1131408A (zh) 1996-09-18

Similar Documents

Publication Publication Date Title
US8137653B1 (en) System and method for producing carbon nanotubes
Tendeloo et al. Purification of catalytically produced multi-wall nanotubes
US2002003A (en) Production of acetylene and carbon black
US8551413B2 (en) System and method for producing carbon nanotubes
EP0500914B1 (fr) Nouvelle forme de carbone
EP1692077B1 (fr) Procede destines a la production de nanostructures de carbone
EP0656870A4 (fr) Procedes et appareils permettant de produire des fullerenes.
US5393955A (en) Preparation of fullerenes and apparatus therefor
EP0717721A1 (fr) Procede de preparation de fullerenes
US3138435A (en) Deposition apparatus and method for forming a pyrolytic graphite article
US7192567B1 (en) Precursor soot synthesis of fullerenes and nanotubes without formation of carbonaceous soot
JPH06183712A (ja) フラーレン類の製造方法
JPH0656414A (ja) フラーレン類の製造方法
US20100249447A1 (en) Purification of fullerene derivatives from various impurities
Pradeep et al. Preparation of buckminsterfullerene, C60
WO2003076335A1 (fr) Procede de production de fullerenes et procede de separation de ceux-ci
US6083469A (en) Pyrolysis process for making fullerenes
Homer XCVI.—The Friedel-Crafts' reaction applied to naphthalene. The action of di-, tri-, and tetra-alkyl halides. Preparation of αβα′ β′-dinaphthanthracene
CA2164731A1 (fr) Methode pour separere le fullerene du noir de carbone renfermant ce compose
JPH09227111A (ja) フラーレンの分離精製装置及び分離精製法
JP4426244B2 (ja) カーボンナノチューブの製造方法および精製方法
JPH0632606A (ja) フラーレン類の製造方法
JPS5976922A (ja) 炭素繊維の製造法
JP2002088591A (ja) 微細炭素繊維の製造方法
RU96105994A (ru) Способ получения фуллеренов

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 94193118.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN JP RU US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994925463

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 1996 586788

Country of ref document: US

Date of ref document: 19960201

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2169846

Country of ref document: CA

WWP Wipo information: published in national office

Ref document number: 1994925463

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1994925463

Country of ref document: EP