WO1993009060A1 - Method for the production of h2o2 using fullerenes - Google Patents
Method for the production of h2o2 using fullerenes Download PDFInfo
- Publication number
- WO1993009060A1 WO1993009060A1 PCT/US1992/009052 US9209052W WO9309060A1 WO 1993009060 A1 WO1993009060 A1 WO 1993009060A1 US 9209052 W US9209052 W US 9209052W WO 9309060 A1 WO9309060 A1 WO 9309060A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fullerene
- fullerenes
- solution
- molecule
- solvent
- Prior art date
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Classifications
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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
-
- 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
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/024—Preparation from organic compounds from hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/029—Preparation from hydrogen and oxygen
-
- 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
Definitions
- This invention is a process for the production of H 2 0 2 using fullerenes, including buckminster-fullerene.
- the process involves the hydrogenation of the fullerenes and the reaction of the hydrogenated fullerenes with 0 2 to produce H 2 0 2 .
- the process utilizes a hydrogenation catalyst and may involve a single phase reaction medium either aqueous or solvent-laden or a two-phase reaction mixture of a solvent and water.
- the solvent solvates the fullerenes and may solvate the hydrogenation catalyst.
- the H 2 0 2 enters the water phase for removal from the process.
- H 2 0 2 is a weakly acidic, clear, colorless liquid miscible in all proportions with water. It is widely used in bleaching operations, in the preparation of other peroxygen compounds, and as an oxidizing agent.
- H 2 0 2 is currently made using a process involving an anthraquinone compound as the hydrogen carrier.
- This process was first operated in Germany during World War II.
- an alkyl-anthraquinone such as a 2-alkyl-anthraquinone is dissolved in a in a solvent system such as a mixture of benzene and C 7 -C 9 alcohols, trialkylphosphates, tetraalkyl-substituted ureas, dialkylcarboxylic acid amides, 1 ,3,5-tritetraalkylazene, 2,6- dialkylcyclohexane, pivalic esters, mono- and diacetylbenzoquinone, and diacetylbenzene.
- a solvent system such as a mixture of benzene and C 7 -C 9 alcohols, trialkylphosphates, tetraalkyl-substituted ureas, dialkylcarbox
- the dissolved anthraquinone or "working solution” is mixed with with hydrogen and a hydrogenation catalyst such as palladium-black, Raney nickel, or nickel boride.
- a hydrogenation catalyst such as palladium-black, Raney nickel, or nickel boride.
- the anthraquinone is reduced to the corresponding anthraquinol (or anthrahydroquinone).
- the working solution is separated from the catalyst and contacted with air to again produce the anthraquinone.
- Simultaneously H 2 0 2 is formed and is then extracted with H 2 0 to form an H 2 0 2 solution.
- the H 2 0 2 solution is purified and concentrated if needed.
- the working solution is recycled.
- the inventive process does not involve the use of anthraquinone but instead uses fullerenes as the hydrogen carrier.
- This invention is a process for the production of H 2 0 2 using fullerenes.
- the process involves the catalytic hydrogenation of the fullerenes and the reaction of the hydrogenated fullerenes with 0 2 to produce H 2 0 2 .
- the process may utilize a two-phase reaction mixture of a solvent and water, a single aqueous or solvent phase is also applicable.
- the H 2 0 2 is extracted into the water phase for removal from the process.
- This invention is a process for the production of H 2 0 2 using fullerenes.
- the process involves the catalytic hydrogenation of the fullerenes and the reaction of the hydrogenated fullerenes with 0 2 to produce H 2 0 2 .
- the process may utilize a two-phase reaction mixture of a solvent and water or an aqueous or solvent single phase. In the two-phase or solvent reaction mixture, the solvent solvates the fullerenes and any applicable hydrogenation catalyst.
- the H 2 0 2 is extracted into the water phase for removal from the process.
- Fullerenes are representative of a set of carbon molecules which have been shown to have both aromatic and olefinic character.
- the simplest of the fullerene molecules is a sperical C 60 molecule, called buckminster-fullerene, with the geometry of a truncated icosahedron - a polygon with 60 vertices and 32 faces, 12 of which are pentagons and 20 are hexagons.
- Other fullerene molecules have been identified and include C 70 , C 76 , C 78 , C 8 , C 90 , C 94 , and others up to C 266 . See, Parker et al. J.Am. Chem. Soc. 1991 , 1 13. 7499-7503.
- C 60 buckminster-fullerene may be hydrogenated to form a C 60 H 3 ⁇ molecule and subsequently dehydrogenated to C ⁇ 0 without substantial alteration of the molecule.
- Hawkins et al have shown [J. Org. Chem. 1990, 55, 6250-6252 and Science 1991 , 25_2, 312-313] that C ⁇ 0 buckminster-fullerene may be functionalized. Hawkins et al utilizes osmium tetraoxide and pyridine to produce an ester.
- Cioslowsk ⁇ has reported [J. Am. Chem. Soc. 1991, 113, 4139-4141] that C ⁇ 0 buckminster-fullerene could form cages about several ions including F " , Ne, Na + , Mg 2+ , and Al 3+ .
- the fullerene molecule used in the inventive process may be any of the molecules listed above or others of the genre and, as required by the choice of solvent and hydrogenation catalyst, may be alkylated, fluorinated, modified to contain a metal or molecule within the fullerene molecule or to contain a metal on the fullerene surface or in the fullerene cage.
- the fullerene molecule may be complexed with a metal-containing ligand which may act as a hydrogenation component integrated with the fullerene.
- the fullerene molecule may be converted into a heterogeneous form by the proceses noted above.
- the molecule used in the process and containing the fullerene core may desirably be converted to one having a metal- containing hydrogenation catalyst, e.g., platinum group metals such as Pd, Pt, Ru, etc., complexed to the fullerene molecule (e.g., C 60 [(ML n ) where "M” is one or more of the noted hydrogenation metals and "L” represents one or more ligands as needed to stabilize the metals) or adsorbed on the surface or substituted for one or more carbon atoms in the fullerene core.
- a metal- containing hydrogenation catalyst e.g., platinum group metals such as Pd, Pt, Ru, etc.
- This invention is a process for the production of H 2 0 2 using a molecule containing the fullerene core.
- the process involves the hydrogenation of the fullerene and the reaction of the hydrogenated fullerene with 0 2 to produce H 2 0 2 .
- the process may utilize a two-phase reaction mixture of a solvent and water.
- the solvent may solvate the fullerenes and any applicable hydrogenation catalyst. If the fullerenes have been modified to a heterogeneous form, the solvent need not solvate the catalyst and fullerene.
- the H 2 0 2 is extracted into the water phase for removal from the process.
- the process may also be operated in a single liquid phase and either in continuous or in batch mode.
- one or more of the fullerene core carbons is replaced with a hydrogenation metal, e.g., Pd, so that the hydrogenation catalyst is a part of the fullerene structure.
- a hydrogenation metal e.g., Pd
- These structures are soluble in hydrocarbon solvents which are not miscible with water and which would not oxidize under the peroxide synthesis conditions.
- the solvents should be substantially insoluble in water or in aqueous solutions containing H 2 0 2 , e.g., aromatics or chlorinated aliphatics.
- an organic solution of C- ⁇ Pd, (where "z” represents the number of carbons necessary to form a determinate fullerene structure) is contacted with a water phase and then reacted with a mixture of H 2 /0 2 (outside of explosive limits) to produce hydrogen peroxide.
- the relative rates of hydrogenation/oxidation determine the various structures C ⁇ . y Pd x H y which are present in solution.
- the peroxide which is formed is not soluble in the hydrocarbon and therefore is continuously extracted into the aqueous phase. As a result, it does not displace oxygen as the oxidant in the hydrocarbon phase thus avoiding reduction to water and giving high selectivity to hydrogen peroxide.
- the fullerene cores are stable under the reaction conditions which make it possible to attain high (e.g., > 20%) concentrations of H 2 0 2 without peroxide contamination or catalyst/reaction carrier degradation.
- the fullerene containing molecule is desirably used in as high a concentration as is possible to provide the highest production rates but obviously lower concentrations would be acceptable.
- the reaction should be operated at as low a temperature and pressure as is convenient so to simplify the cooling of the reaction mixture and obviate the need for expensive pressure vessels.
- the reaction is operated at room temperature and at atmospheric pressure although temperatures from below room temperature to about 100°C and pressures from about atmospheric to about 500 psig are appropriate.
- the process may also be operated in a continuous fashion, e.g., contact of the hydrocarbon/fullerene/hydrogenation catalyst mixture with hydrogen, followed by contact of the hydrogenated fullerenes with oxygen and water to form an H 2 0 2 solution, and recycle of the fullerenes.
- the process may also be be operated semi-continuously with the cycling of H 2 /0 2 mixtures and water.
- the fullerene-containing hydrogen carrier may be alkylated, fluorinated, or made to contain a metal or molecule within the fullerene molecule. These modifications to the fullerene containing core molecule are a matter of technical choice to tailor the solubility of the fullerene molecule to the chosen solvent or to modify the reaction rate of the fullerene molecule or to enhance the stability of the fullerene molecule.
- the manner by which the fullerene-containing molecule is reduced may be changed in a number of ways.
- the molecule containing the fullerene core may desirably be converted to one having a hydrogenation metal, e.g., Pd, Pt, Ru, etc., complexed to the fullerene molecule (e.g., C 60 [(ML n ) where "M” is one or more of the noted hydrogenation metals and "L” represents one or more ligands as needed to stabilize the metals) or adsorbed on the surface or substituted for one or more carbon atoms in the fullerene core. Attachment of the catalytic metal to the surface of the fullerene core likely provides added stabilization of the metal complex.
- the hydrogenation catalyst may be homogeneous and dissolved in the hydrocarbon layer. Salts or complexes of the hydrogenation catalysts, e.g., Pd, Pt, Ni (using ligands such as phosphines or aryl groups which stabilize the metal and allow it to be solubilized in the hydrocarbon phase) are appropriate.
- the dissolved catalyst should be selected also using the criteria that it not degrade by oxidation.
- a heterogeneous hydrogenation catalyst comprising, e.g., platinum group metals such as Pd, Pt, Ru, etc., is useful so long as the catalyst is preferentially wet by the hydrocarbon phase.
- platinum group metals such as Pd, Pt, Ru, etc.
- An example of such a catalyst is palladium on partially fluorinated carbon.
- the catalyst in this example also produces H 2 0 2 independently of the fullerene.
- Another variation involves a one-liquid-phase (hydrocarbon or aqueous) system having a catalyst system which repels H 2 0 2 so that it does not return to the active catalyst site.
- Partially alkylated or fluorinated fullerenes hydrogen carrier systems (such as C ⁇ 0 PdF ⁇ in a heterogeneous catalyst or C ⁇ oFe with adsorbed Pd°) have the desired properties.
- Another variation includes the concept of forming the fullerene into a heterogeneous form.
- Still another variation is the use of an electrode of fullerene which would then be reduced with electrons.
- the surface would be protonated by protons in solution. Reaction with oxygen would then produce H 2 0 2 .
- the protons would be replenished by oxidation of hydrogen at the other electrode made of a conductive material.
- a proton conducting between the electrodes would have the advantage of not allowing 0 2 and 0 2 in the same compartment.
- the process may be operated in a batch mode; the oxygen and the hydrogen are alternated over the fullerene containing solution.
- This Example demonstrates the use of fullerene as a hydrogen carrier in a process of producing H 2 0 2 .
- a C 60 -fullerene solution containing a Pd catalyst was contacted with H 2 at temperatures between 45-65 °C. The solution was then contacted with 0 2 . A white silky precipitate formed. Testing of the solution with KMn0 4 indicated the presence of H 2 0 2 .
- the hydrogenated solution was contacted with a solution of eAQ and extracted.
- the amount of H 2 0 2 formed was equal to about 30% of hydrogen under the assumption that the hydrogenated fullerene had the formula C 60 H 36 .
- the white precipitate was also formed.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/081,252 US5376353A (en) | 1991-10-28 | 1992-10-26 | Method for the production of H2 O2 using Fullerenes |
JP5508482A JPH06504029A (ja) | 1991-10-28 | 1992-10-26 | フラーレンを用いたh↓2o↓2の製造方法 |
NO93932330A NO932330L (no) | 1991-10-28 | 1993-06-24 | Fremgangsmaate for fremstilling av h2o2 ved aa anvende fullerener |
FI932982A FI932982A (fi) | 1991-10-28 | 1993-06-28 | Foerfarande foer framstaellning av h2o2 genom att anvaenda fullerener |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US78225491A | 1991-10-28 | 1991-10-28 | |
US782,254 | 1991-10-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993009060A1 true WO1993009060A1 (en) | 1993-05-13 |
Family
ID=25125497
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/009052 WO1993009060A1 (en) | 1991-10-28 | 1992-10-26 | Method for the production of h2o2 using fullerenes |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0564644A1 (fi) |
JP (1) | JPH06504029A (fi) |
AU (1) | AU3055492A (fi) |
CA (1) | CA2099360A1 (fi) |
FI (1) | FI932982A (fi) |
NO (1) | NO932330L (fi) |
WO (1) | WO1993009060A1 (fi) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994006736A1 (de) * | 1992-09-16 | 1994-03-31 | Hoechst Aktiengesellschaft | Verfahren zur sensibilisierten photooxygenierung von ungesättigten verbindungen |
CN111554944A (zh) * | 2020-05-21 | 2020-08-18 | 中国科学院福建物质结构研究所 | 一种中空介孔碳球的应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4131646A (en) * | 1977-09-16 | 1978-12-26 | E. I. Du Pont De Nemours And Company | Preparation of hydrogen peroxide from dihydroanthracene hydroperoxides |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE25839T1 (de) * | 1983-06-22 | 1987-03-15 | Du Pont | Verfahren zur katalytischen herstellung von wasserstoffperoxid aus sauerstoff und wasserstoff. |
-
1992
- 1992-10-26 JP JP5508482A patent/JPH06504029A/ja active Pending
- 1992-10-26 CA CA002099360A patent/CA2099360A1/en not_active Abandoned
- 1992-10-26 EP EP92924120A patent/EP0564644A1/en not_active Ceased
- 1992-10-26 AU AU30554/92A patent/AU3055492A/en not_active Abandoned
- 1992-10-26 WO PCT/US1992/009052 patent/WO1993009060A1/en not_active Application Discontinuation
-
1993
- 1993-06-24 NO NO93932330A patent/NO932330L/no unknown
- 1993-06-28 FI FI932982A patent/FI932982A/fi not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4131646A (en) * | 1977-09-16 | 1978-12-26 | E. I. Du Pont De Nemours And Company | Preparation of hydrogen peroxide from dihydroanthracene hydroperoxides |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994006736A1 (de) * | 1992-09-16 | 1994-03-31 | Hoechst Aktiengesellschaft | Verfahren zur sensibilisierten photooxygenierung von ungesättigten verbindungen |
CN111554944A (zh) * | 2020-05-21 | 2020-08-18 | 中国科学院福建物质结构研究所 | 一种中空介孔碳球的应用 |
Also Published As
Publication number | Publication date |
---|---|
NO932330D0 (no) | 1993-06-24 |
CA2099360A1 (en) | 1993-04-29 |
NO932330L (no) | 1993-08-12 |
EP0564644A4 (fi) | 1994-03-30 |
AU3055492A (en) | 1993-06-07 |
EP0564644A1 (en) | 1993-10-13 |
FI932982A0 (fi) | 1993-06-28 |
FI932982A (fi) | 1993-08-16 |
JPH06504029A (ja) | 1994-05-12 |
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