WO2009039325A2 - Procédés et dispositifs pour la synthèse de composés utiles - Google Patents

Procédés et dispositifs pour la synthèse de composés utiles Download PDF

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Publication number
WO2009039325A2
WO2009039325A2 PCT/US2008/076924 US2008076924W WO2009039325A2 WO 2009039325 A2 WO2009039325 A2 WO 2009039325A2 US 2008076924 W US2008076924 W US 2008076924W WO 2009039325 A2 WO2009039325 A2 WO 2009039325A2
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Prior art keywords
catalyst
catalytic cell
oxygen
oms
compound
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PCT/US2008/076924
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English (en)
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WO2009039325A3 (fr
Inventor
Victor Stancovski
Steven Lawrence Suib
Boxun Hu
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Catelectric Corp.
University Of Connecticut
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Publication of WO2009039325A2 publication Critical patent/WO2009039325A2/fr
Publication of WO2009039325A3 publication Critical patent/WO2009039325A3/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to methods and apparatus for the activation of a low reactivity, non-polar chemical compound. More specifically, the present invention relates to process for the synthesis of useful compounds from non-polar compounds such as carbon dioxide and the like. The present invention also relates to a method for oxidizing aromatic compounds to oxidized products by electrocatalysis.
  • Some catalysts e.g., transition metal complexes
  • transition metal complexes have been shown to catalyze the reduction of carbon dioxide via hydride complexes, in which the origin of the activated hydrogen is water.
  • Such reactions result usually in a partial reduction of carbon dioxide to carbon monoxide.
  • formaldehyde, methanol and/or methane is potentially very significant.
  • reduction products are particularly important in chemical manufacture (formaldehyde and methanol), as well as fuels (methanol and methane), [see, e.g., "Thermodynamic, Kinetic and Product
  • formaldehyde and its derivatives serve a wide variety of end uses such as for plastics and coatings.
  • Formaldehyde is considered one of the world's most important industrial and research chemicals, owing to the vast number of chemical reactions it can participate in.
  • the commercial forms usually available comprise: the polymer form, which can be reversibly converted to a monomer by the reaction of heat or an acid:
  • the present invention relates to methods and apparatus for activation of a low reactivity, non-polar chemical compound, hi one example embodiment, the method comprises introducing the low reactivity chemical compound to a catalyst. At least one of
  • the catalyst (a) an oxidizing agent or a reducing agent, and (b) a polar compound is provided to the catalyst and the chemical compound.
  • An alternating current is applied to the catalyst to produce an activation reaction in the chemical compound.
  • This activation reaction produces a useful product.
  • the activation reaction may comprise one of a reduction or an oxidation reaction.
  • the polar compound may comprise one of water or steam.
  • One of ammonia, nitric oxide, carbon monoxide, methane, or the like may be added to the water or steam.
  • the polar compound may comprise one of water, ammonia, nitric oxide, and carbon monoxide.
  • polar compounds may be used with the present invention.
  • the chemical compound and the at least one of the oxidizing agent or the reducing agent and the polar compound may be introduced into a chamber containing the catalyst.
  • the low reactivity chemical compound may comprise CO2.
  • the useful product may comprise formaldehyde in at least one of a monomeric and a polymeric form, hi other example embodiments, the useful product may comprise at least one of an aldehyde, trioxane, ethane, ethylene, formaldehyde, and paraformaldehyde.
  • the useful products may contain at least one of carbon, hydrogen, and oxygen.
  • the useful products may comprise at least one of an alcohol compound and an olefin.
  • the chemical compound may comprise an aromatic compound.
  • the aromatic compound may comprise benzene or a benzene derivative.
  • a reducing agent such as hydrogen may be provided to the catalyst and the aromatic compound, and the useful product may comprise cyclohexane or a benzene derivative.
  • an oxidizing agent such as oxygen may be provided to the catalyst and the aromatic compound, and the useful product may comprise at least one of acetophenone, a phenol, or a benzene derivative.
  • the catalyst may comprise one of a precious metal, a semi-conducting oxide, a semi-conducting cermet, and a varistor.
  • catalysts that may be used with the present invention include, but are not limited to catalysts comprising platinum, platinum black, rhodium, rhodium black, palladium, palladium black, silver, manganese oxide, a manganese oxide derivative, molybdenum oxide, a molybdenum oxide derivative, iron oxide, an iron oxide derivative, cerium oxide, a cerium oxide derivative, titanium oxide, doped titanium oxide and related compounds, cobalt oxide, rhodium oxide, zinc oxide, and the like.
  • the catalyst may comprise a catalyst layer applied to a porous ceramic substrate.
  • the catalyst layer may be supported by a layer of a solid electrolyte.
  • the solid electrolyte layer may be one of a continuous layer or a discontinuous layer.
  • the solid electrolyte may comprise one of stabilized zirconia (stabilized with, e.g., gadolinium oxide, samarium oxide, lanthanum oxide, ytterbium oxide, yttrium oxide or other adequate materials known to those skilled in the art), Nafion, other hydrogen ion conducting materials, beta aluminas, or the like
  • the alternating current may be applied across a three-phase boundary at an interface between the catalyst and the solid electrolyte layer.
  • three electrodes may be provided.
  • a reference electrode may be applied to the solid electrolyte layer
  • a counter electrode may be applied between the catalyst and the solid electrolyte layer
  • a working electrode may be applied to the catalyst layer.
  • a polarization impedance of the supported catalyst layer may be monitored.
  • the polarization impedance may be controlled by varying the alternating current, enabling optimization of the activation reaction.
  • a controlled oxygen partial pressure environment may be provided at a level of the supported catalyst layer.
  • the partial pressure of the oxygen at a level of the catalyst layer may be monitored.
  • the monitoring of the partial pressure of the oxygen may comprise monitoring an interfacial impedance of the supported catalyst layer.
  • the partial pressure of oxygen at a level of the catalyst layer may then be determined as a function of the interfacial impedance.
  • the polarization impedance of the supported catalyst layer may be monitored, and the partial pressure of oxygen at the level of the catalyst layer may be determined as a function of the monitored polarization impedance.
  • a momentary value of the alternating current may be determined as a function of the monitored polarization impedance.
  • the amount of the at least one of the oxidizing agent, the reducing agent, and the polar compound provided may be controlled in order to optimize the activation reaction.
  • a ratio of an amount of the chemical compound to an amount of the at least one of the oxidizing agent, the reducing agent, and the polar compound provided may be controlled in order to optimize the activation reaction.
  • heat may be applied to the catalyst in order to optimize the activation reaction.
  • the present invention also generally includes a method for activation of a chemical compound.
  • the chemical compound is introduced to a catalyst.
  • An oxidizing agent or a reducing agent is provided to the catalyst and the chemical compound.
  • An alternating current is applied to the catalyst to produce an activation reaction in the chemical compound.
  • This activation reaction produces a useful product.
  • the chemical compound may comprise a polar compound and the oxidizing or reducing agent may comprise a polar reactant or a nonpolar reactant.
  • the chemical compound may comprise a nonpolar chemical compound and the oxidizing or reducing agent may comprise a polar reactant or a nonpolar reactant.
  • the present invention also encompasses apparatus for activation of a low reactivity, non-polar chemical compound which can be used to carry out the various embodiments of the methods discussed above.
  • the apparatus may comprise a catalyst, a means for introducing the low reactivity chemical compound to the catalyst, a means for providing at least one of (a) an oxidizing agent or a reducing agent, and (b) a polar compound to the catalyst and the chemical compound, and means for applying an alternating current to the catalyst to produce an activation reaction in the chemical compound, such that the activation reaction produces a useful product.
  • the present invention also relates to a method for oxidizing chemical compounds to oxidized products by electrocatalysis comprising: providing a catalytic cell, applying a polarized current or voltage to the catalytic cell and passing a gaseous stream of air or oxygen or a mixture of oxygen and one or more inert gases and the compound to be oxidized over the catalytic cell.
  • the present invention also relates to a method for oxidizing aromatic compounds to oxidized products by electrocatalysis comprising the steps of: providing a catalytic cell comprising a cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2); applying a polarized current or voltage to the catalytic cell; and passing a gaseous stream of air or oxygen or a mixture of oxygen and one or more inert gases and the aromatic compound to be oxidized over the catalytic cell.
  • OMS-2 cryptomelane-type manganese oxide octahedral molecular sieve
  • the catalytic cell comprises a working electrode comprising a substrate having a manganese oxide octahedral molecular sieve catalyst (OMS-2) thereon; a counter electrode and a reference electrode.
  • OMS-2 manganese oxide octahedral molecular sieve catalyst
  • the OMS-2 contains nano-metal particles.
  • the metal contained in the OMS-2 having nano-metal particles is chosen from the group consisting OfNi 2+ , Zn 2+ , Co 2+ , Cu 2+ , Fe 2+ Fe 3+ , V 4+ , V 5+ ,
  • the OMS-2 containing nano-metal particles is Pt-OMS-2.
  • the substrate having manganese oxide octahedral molecular sieve catalyst (OMS-2) is a porous material preferably having a pore size of 5- 20 mesh.
  • the porous substrate is Corning Honeycomb Cordierite®, yttrium stabilized zirconium, Ce ⁇ 2 or Hf ⁇ 2.
  • the catalytic cell comprises a working electrode comprising silver or platinum gauze supported by an insulated pad, the working electrode in contact with the substrate, the substrate having a cryptomelane-type manganese oxide octahedral molecular sieve catalyst thereon (preferably Pt-OMS-2).
  • the counter electrode is a silver or platinum wire and the reference electrode is a silver or platinum wire.
  • the catalytic cell is heated to a temperature of between about 25° and about 900° C, preferably between about 100° and about 450° C.
  • the oxidation is accomplished at a pressure of about 1 atm to about 2 atm.
  • gaseous stream further comprises CO 2 and water vapor alone or in combination.
  • the aromatic compound is a derivative of benzene, preferably the aromatic compound is benzene and the oxidized product is acetophenone.
  • the present invention also relates to a method for oxidizing aromatic compounds to oxidized product by electrocatalysis comprising the steps of: providing a catalytic cell comprising a metal oxide chosen from the group consisting of CuO x , Ni O x , ZnO and VO x (wherein x is an integer from 1-4; applying a polarized current or voltage to the catalytic cell; and passing a gaseous stream of air or oxygen or a mixture of oxygen and one or more inert gases and the aromatic compound to be oxidized over the catalytic cell.
  • the catalytic cell is heated to a temperature of about between about 25°C and about 900 0 C preferably between about 100 0 C and about 450 0 C.
  • the oxidation is accomplished at a pressure of about 1 atm to about 2 atm.
  • the gaseous stream further comprises CO 2 and water vapor alone or in combination.
  • the aromatic compound is a derivative of benzene.
  • the aromatic compound is benzene and the oxidized product is acetophenone.
  • Figure 1 shows an example embodiment of an apparatus in accordance with the present invention
  • FIG. 2 shows a further example embodiment of an apparatus in accordance with the present invention
  • FIG. 3 shows an example embodiment of an electrode arrangement in accordance with the present invention
  • Figure 4 shows NMR analysis results for the output achieved with one example embodiment of the present invention
  • Figure 5 shows NMR analysis results for the output achieved with a further example embodiment of the present invention
  • Figures 6 and 7 show scanning electron microscopy images of the catalyst assembly at different resolutions, respectively, in accordance with an example embodiment of the invention.
  • Figure 8 shows an NMR spectrum for the output achieved with a further example embodiment of the present invention.
  • Figure 9 shows a polarization Bode spectrum from one example embodiment of the present invention.
  • Figure 10 shows a single frequency EIS (Electrochemical Impedance Spectroscopy) spectrum from one example embodiment of the present invention
  • Figure 11 shows a further example embodiment of an apparatus in accordance with the present invention.
  • Figure 12 shows GC-MS results of oxidation of benzene
  • Figure 13 shows MS of peak 3 (Acetophenone) of GCMS of Figure 12;
  • Figure 14 shows MS of peak 3 (p-methylacetophenone) of GCMS of Figure 12.
  • the present invention is the product of a joint research agreement between Catelectric Corp. (Catelectric) and The University of Connecticut and relates to methods and apparatus for activation of a low reactivity, non-polar chemical compound in order to produce useful products.
  • the present invention relates to methods and apparatus for the preparation of useful products, such as, e.g., paraformaldehyde, via the activation (e.g., reduction or oxidation) of carbon dioxide, using water as the source of hydrogen.
  • useful products such as, e.g., paraformaldehyde
  • the reaction is activated via the DECANTM process developed by Catelectric.
  • the DECANTM process is described in Catelectric's U.S. patent no.
  • FIG. 1 shows an example embodiment of an apparatus 10 for activation of a low reactivity, non-polar chemical compound.
  • a low reactivity chemical compound 12 is introduced to a catalyst (e.g., catalyst layer 14).
  • the catalyst layer 14 may be supported on a support 16.
  • At least one of (a) an oxidizing agent or a reducing agent 19, and (b) a polar compound 18 is provided to the catalyst 14 and the chemical compound 12.
  • An alternating current e.g., from current/voltage source 20
  • This activation reaction produces a useful product.
  • the present invention also relates to the oxidation of aromatic compounds preferably benzene and its derivatives by electrocatalysis.
  • aromatic compound refers to an aryl or heteroaryl compound.
  • An aryl compound refers to a mono, bi or tricyclic aromatic C ⁇ -Ci 4 carbocycle, which can be optionally substituted by 1 to 5 substituents. Examples include but are not limited to benzene, toluene, biphenyl phenol, xylene, and napthalene.
  • Heteroaryl refers to a C 2 -C 14 mono, bi or tricyclic ring (optionally substituted with 1-5 substituents, which may be the same or different) containing 1 to 5 heteroatoms in the ring independently chosen from O, S, N and NRl where Rl is Ci-C ⁇ alkyl or H. Examples include but are not limited to pyridine, indole thiophene, furan and isoquinoline. Substituent groups are any substituent with a molecular weight of about 300 or less.
  • Examples include but are not limited to halogen, hydroxy, cyano, -C(O)Ci-6 Ci-Ci 2 alkyl, Ci-Ci 2 alkenyl or alkynyl, halo alkyl, Ci-Ci 2 alkoxy nitro and amino.
  • Compounds which have substituents added to their core structure are termed derivatives. For example tolune and acetophenone are derivatives of benzene.
  • non-polar chemical compound denotes a chemical compound, which, as a whole, has a zero permanent dipole moment.
  • CO 2 is considered to be non-polar, even though it has polar bonds between the individual molecules.
  • polar compound denotes a compound that, as a whole, has a non-zero dipole moment.
  • the activation reaction may comprise one of a reduction or an oxidation reaction.
  • the polar compound 18 may comprise one of water or steam.
  • One of ammonia, nitric oxide, carbon monoxide, methane, or the like may be added to the water or steam.
  • the polar compound 18 may comprise one of water, ammonia, nitric oxide, and carbon monoxide.
  • water or steam
  • the use of water (or steam) will facilitate both an oxidation and a reduction reaction.
  • the chemical compound 12 and the at least one of the oxidizing agent or the reducing agent 19 and the polar compound 18 may be introduced into a chamber 22 containing the catalyst 14.
  • the chamber 22 may comprise a tubular reactor.
  • the alternating current may be controlled by an electronic control device 24.
  • the chemical compound 12 e.g., CO 2
  • the polar compound 18 e.g., water
  • the oxidizing agent (e.g., oxygen) or the reducing agent (e.g. hydrogen) 19 may be introduced from tank 21.
  • the resulting products of the reaction may be passed through an ice-water trap 26 and/or a dry ice/liquid nitrogen trap 28 before being separated in a molecular sieve 30 prior to computer analysis (such as gas chromatography- mass spectrometry (GC-MS), high performance liquid chromatography-mass spectrometry (HPLC-MS), nuclear magnetic resonance (NMR) and other analysis techniques) at analyzer 32.
  • computer analysis such as gas chromatography- mass spectrometry (GC-MS), high performance liquid chromatography-mass spectrometry (HPLC-MS), nuclear magnetic resonance (NMR) and other analysis techniques
  • the low reactivity chemical compound 12 may comprise CO 2 .
  • the useful product may comprise formaldehyde in at least one of a monomeric and a polymeric form.
  • the useful product may comprise at least one of an aldehyde, trioxane, ethane, ethylene, formaldehyde, and paraformaldehyde.
  • the useful products may contain at least one of carbon, hydrogen, and oxygen.
  • the useful products may comprise at least one of an alcohol compound and an olefin.
  • oxygen (O 2 ) may be a result of the reaction.
  • the chemical compound 12 may comprise an aromatic compound.
  • the aromatic compound may comprise benzene or a benzene derivative.
  • the reducing agent 19 such as hydrogen
  • the useful product may comprise cyclohexane or a benzene derivative.
  • an oxidizing agent 19 such as oxygen
  • the useful product may comprise at least one of acetophenone, a phenol, or a benzene derivative.
  • the catalyst 14 may comprise one of a precious metal, a semi-conducting oxide, a semi-conducting cermet, and a varistor.
  • catalysts that may be used with the present invention include, but are not limited to catalysts comprising platinum, platinum black, rhodium, rhodium black, palladium, palladium black, silver, manganese oxide, a manganese oxide derivative, molybdenum oxide, a molybdenum oxide derivative, iron oxide, an iron oxide derivative, cerium oxide, a cerium oxide derivative, titanium oxide, doped titanium oxide and related compounds, cobalt oxide, rhodium oxide, zinc oxide, and the like.
  • catalyst material may generally include oxides of alkali metals, alkaline earths, lanthanides, actinides, transition metals, and nonmetals.
  • the catalyst 14 may comprise a catalyst layer applied to a support 16 such as porous ceramic substrate.
  • the catalyst layer 14 may be supported by a layer 16 of a solid electrolyte.
  • the catalyst 14 may be applied to the solid electrolyte layer 16, which in turn may be applied onto a separate support (not shown).
  • the solid electrolyte layer 16 may be one of a continuous layer or a discontinuous layer.
  • the solid electrolyte 16 may comprise one of stabilized zirconia (stabilized with, e.g., gadolinium oxide, samarium oxide, lanthanum oxide, ytterbium oxide, yttrium oxide or other adequate materials known to those skilled in the art), Nafion, other hydrogen ion conducting materials, beta aluminas, or the like.
  • stabilized zirconia stabilized with, e.g., gadolinium oxide, samarium oxide, lanthanum oxide, ytterbium oxide, yttrium oxide or other adequate materials known to those skilled in the art
  • Nafion sodium fluoride
  • other hydrogen ion conducting materials e.g., sodium ion, other hydrogen ion conducting materials, beta aluminas, or the like.
  • the temperature range of the reactor will be determined by the specific properties of these materials, known to those skilled in the art.
  • the alternating current may be applied across a three-phase boundary at an interface between the catalyst 14 and the solid electrolyte layer 16 via the electronic control device 24.
  • three electrodes may be provided.
  • a reference electrode 40 may be applied to the solid electrolyte layer 16
  • a counter electrode 42 may be applied to the solid electrolyte layer 16
  • a working electrode 44 may be applied to the catalyst layer 14.
  • a polarization impedance of the supported catalyst layer 14 may be monitored.
  • the electronic control device 24 may include means for determining the applied current and voltage. The determination of the polarization impedance from the sensed current is explained in detail in Catelectric's U.S. Patent No. 7,352,392 incorporated by reference in its entirety.
  • the polarization impedance may be controlled by varying the alternating current from electronic control device 24, enabling optimization of the activation reaction.
  • a controlled oxygen partial pressure environment may be provided at a level of the supported catalyst layer.
  • the oxygen may be produced from the solid electrolyte layer 16 under the voltage applied between the working electrode 44 and the reference electrode 40, and is a function of the DECANTM process.
  • the oxygen may be provided from tank 21 ( Figure 2).
  • the partial pressure of the oxygen at a level of the catalyst layer 14 may be monitored.
  • the determining of the partial pressure of oxygen may also be achieved via the electronic control device 24 as a function of a voltage measurement.
  • a monitoring of the partial pressure of the oxygen may comprise monitoring an interfacial impedance of the supported catalyst layer 14.
  • the partial pressure of oxygen at a level of the catalyst layer 14 may then be determined as a function of the interfacial impedance.
  • the polarization impedance of the supported catalyst layer 14 may be monitored as discussed above, and the partial pressure of oxygen at the level of the catalyst layer 14 may be determined as a function of the monitored polarization impedance (e.g., achieved via the electronic control device 24).
  • a momentary value of the alternating current may be determined by the electronic control device 24 as a function of the monitored polarization impedance.
  • the amount of the oxidizing agent or the reducing agent 19 and/or the polar compound 18 provided may be controlled in order to optimize the activation reaction.
  • a ratio of an amount of the chemical compound 12 to an amount of the oxidizing agent or the reducing agent 19 and/or the polar compound 18 provided may be controlled in order to optimize the activation reaction.
  • heat may be applied to the catalyst in order to optimize the activation reaction.
  • Heat may be applied via heating element 34, which is controlled by temperature control unit 36 ( Figure 2).
  • Oxygen 19 may be applied from an oxygen source (e.g., tank 21) or may be generated by controlling the voltage applied to the solid electrolyte layer, as discussed above.
  • the present invention also generally includes a method for the activation of a chemical compound.
  • the chemical compound 12 is introduced to a catalyst 14.
  • An oxidizing agent or a reducing agent 19 is provided to the catalyst 14 and the chemical compound 12.
  • An alternating current is applied to the catalyst 14 to produce an activation reaction in the chemical compound 12.
  • This activation reaction produces a useful product.
  • the chemical compound may comprise a polar compound 12 and the oxidizing or reducing agent 19 may comprise a polar reactant (e.g., water or steam) or a non-polar reactant (oxygen or hydrogen).
  • the chemical compound may comprise a non-polar chemical compound 12 (as discussed above) and the oxidizing or reducing agent 19 may comprise a polar reactant (e.g., water or steam) or a non-polar reactant (oxygen or hydrogen).
  • a polar reactant e.g., water or steam
  • a non-polar reactant oxygen or hydrogen
  • one polar compound like methanol could react with another polar compound like ethanol to form products of value
  • one non- polar compound like benzene could react with another nonpolar compound like methane.
  • the present invention also relates to methods and apparatus for oxidizing chemical compounds (e.g., aromatic compounds 112) by electrocatalysis comprising: providing a catalytic cell 14, applying a polarized current or voltage to the catalytic cell from a current/voltage source 20, and passing an oxidizing agent 19 (such as a gaseous stream of air, oxygen, or a mixture of oxygen and one or more inert gases) and the compound to be oxidized 112 over the catalytic cell 14.
  • an oxidizing agent 19 such as a gaseous stream of air, oxygen, or a mixture of oxygen and one or more inert gases
  • the catalytic cell 14 may comprise a cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2).
  • OMS-2 cryptomelane-type manganese oxide octahedral molecular sieve
  • the catalytic cell 14 comprises a working electrode 44 comprising a substrate having a manganese oxide octahedral molecular sieve catalyst (OMS-2) thereon, a counter electrode 42 and a reference electrode 40.
  • OMS-2 manganese oxide octahedral molecular sieve catalyst
  • the OMS-2 catalyst 14 contains nano-metal particles.
  • the metal contained in the OMS-2 catalyst 14 having nano- metal particles is chosen from the group consisting of Ni 2+ , Zn 2+ , Co 2+ , Cu 2+ , Fe 2+ Fe 3+ , V 4+ , V 5+ , Ti 4+ , Ti 3+ , Cr 3+ , Cr 2+ , Co 3+ , Cu 1+ , Ce 3+ , Ce 4+ , La 3+ , Na + , K + , Ba 2+ , Y 3+ , Zr 4+ , Li + , Sr 2+
  • the OMS-2 catalyst 14 containing nano-metal particles is Pt-OMS-2.
  • the substrate (support 16) having manganese oxide octahedral molecular sieve catalyst (OMS-2) 14 is a porous a porous material preferably having a pore size of 5-20 mesh.
  • the porous substrate 16 is Corning Honeycomb Cordierite® yttrium stabilized zirconium, CeC ⁇ or HfC> 2 .
  • the catalytic cell 14 comprises a working electrode 44 comprising silver or platinum gauze supported by an insulated pad, the working electrode 44 in contact with the substrate 16, said substrate 16 having a cryptomelane-type manganese oxide octahedral molecular sieve catalyst 14 thereon (e.g., Pt-OMS-2).
  • the counter electrode 42 is a silver or platinum wire and the reference electrode 40 is a silver or platinum wire.
  • the catalytic cell is heated to a temperature of between about 25° and about 900° C, preferably between about 100° and about 450° C (e.g., via heating element 34 of Figure 2).
  • the oxidation is accomplished at a pressure of about 1 atm to about 2 atm.
  • gaseous stream further comprises CO2 and water vapor alone or in combination.
  • the aromatic compound 112 is a derivative of benzene, preferably the aromatic compound is benzene and the oxidized product is acetophenone.
  • the catalytic cell 14 may comprise a metal oxide chosen from the group consisting of CuO x , Ni O x , ZnO and VO x (wherein x is an integer from 1- 4).
  • the catalytic cell 14 is heated to a temperature of about between about 25°C and about 900 0 C preferably between about 100 0 C and about 450 0 C. In another embodiment the oxidation is accomplished at a pressure of about 1 atm to about 2 atm.
  • gaseous stream further comprises CO 2 and water vapor alone or in combination.
  • the aromatic compound 112 is benzene and the oxidized product is acetophenone.
  • LP-CVD Liquid-Phase Chemical Vapor Deposition
  • Pt(acac) 2 was used as the platinum precursor.
  • the temperature of the precursor was set at 120-
  • the carrier gas flow rate of the precursor was 500-1000 sccm/min, and the carrier gas was heated to 100-150 C before being introduced into the CVD synthesis tube.
  • Oxygen was used as an oxidant.
  • the oxygen flow rate was set at 80-200 sccm/cm.
  • the total pressure of the CVD reactor was controlled at 5-20 KPa.
  • the platinum deposition time was 1-4 hours.
  • c. Assembling of three electrodes Three electrodes were deposited on the FSZ (calcia) ceramic catalyst as described above in connection with Figure 3. The three electrodes each comprise 0.25mm platinum wires (Alfa Aesar). The three platinum wires were assembled on the FSZ (calcia) using platinum paste (from Engelhard / BASF) and then treated in air at 900 0 C. The reference electrode 40 was directly connected to the support 16 without contact with the platinum layer 14. The counter electrode 42 was assembled before the deposition of the catalyst layer 14 of LP-CVD of platinum, and is in contact with the FSZ support layer 16. The working electrode 44 was deposited on the platinum LP-CVD catalyst layer 14. After assembling the three electrodes, the catalyst assembly with three electrodes was placed in a quartz tube and reduced in 8% hydrogen/helium mixed gas at 600-800 0 C for 4-6 hours.
  • the temperature may be as low as room temperature or higher than 950 0 C; the solid electrolyte can be Nafion, and the catalyst can be platinum black.
  • the solid electrolyte layer 16 can be deposited on a support 16 comprising an inert ceramic substrate (e.g., cordierite catalyst supports provided by Corning Inc. or St. Gobain Co) via any of the appropriate methods known to those skilled in the art.
  • the catalyst 14 can be deposited on the solid electrolyte layer 16 via any of the appropriate methods known to those skilled in the art.
  • the implementation of the process does not require a continuity of the solid electrolyte layer 16 or of the catalyst layer 14. What is necessary is a preponderance of grain boundaries where the catalyst 14 is in contact with the solid electrolyte 16 and sufficient open porosity to allow for the access of the reacting phases to the catalytically active interfaces.
  • Carbon dioxide (CO 2 ) used was zero grade gas from Airgas. Water used was de- ionized water. Water was injected by a peristaltic pump 17, and evaporated by a heated ceramic tube. CO 2 was used as the carrier gas provided from tank 1 1. The molar ratio of CO2 to water was set at 10 to 1 or 5 to 1. The flow of CO2 was monitored by a mass flow meter and was varied between 200 sec/minute and 1600 sec/minute. It should be noted that the water / CO 2 ratio can take any values within the interval 1/1000 to 1000/1, and even outside this range.
  • the system was polarized (via the electronic control device 24 and three electrodes 40, 42, and 44) with a pulsed current at about 1 kHz at average voltages ranging from 0.03 to 0.1 V rms.
  • the current passed averaged between 0.03 and 0.13 mA. This process is described in detail in U.S. patent application no. 11/588,113 mentioned above.
  • the catalyst 14 used in this example was the same as that for example 1.
  • the temperature of the quartz tube reactor was set at 600 0 C.
  • the main product identified by NMR was paraformaldehyde, as shown in Figure 5.
  • a catalyst layer 14 of octahedral manganese oxide OMS-2 was prepared as follows: 5.6g K 2 SO 4 , 8.81 g K 2 S 2 O 8 and 3.77g MnSO 4 and 70ml DI water were added into a 125ml autoclave and put into a 4748 Parr acid digestion bomb for 96 hours; the temperature was maintained at 250 0 C. The solid was washed repeatedly with de-ionized water. The suspension was filtered and stirred overnight at 85 0 C into a beaker with 300 ml de-ionized water. The suspension was coated on the Vesuvius porous ceramic body and was dried at 120 0 C for 12 hours.
  • the as-prepared catalytic assembly was placed in a tube quartz reactor (tubular reactor 22) and connected with the electronic control device 24.
  • the tube quartz reactor 22 was sealed and isolated with an air environment.
  • CO 2 zero grade from Air gas
  • Water was injected with a pre- calibrated peristaltic pump 17. Water was heated by a ceramic tube at above 13O 0 C. Then the reactor 22 was purged with CO 2 .
  • the system was set at slightly higher atmosphere pressure (for example 5 kpa).
  • the electronic control device 24 supplied polarized current or voltage to the catalytic assembly via electrodes 40, 42, and 44.
  • the tube reactor was set at 250-450 0 C.
  • the Pt-OMS-2 catalyst 14 was tested in the CO 2 -H 2 O system starting from 250 0 C and up to 450 0 C. When the reaction started at 250 0 C, it was slow. After 4 hours, the sample was analyzed from the first ice water trap 26 by NMR. The resultant NMR patterns did not show any product. The concentration of products may have been out of the limit or the product yield was very low. The second test was done at 300 0 C. The resultant NMR proton patterns showed a low concentration of paraformaldehyde (about 0.5-1.0% in molar). In particular, the NMR results showed a weak peak of paraformaldehyde at this temperature. The third test was done at 400 0 C.
  • the resultant NMR patterns from the ice water trap 26 and the NMR patterns of the dry ice trap 28 showed stronger peaks of paraformaldehyde at this temperature.
  • the concentration of paraformaldehyde was about 1.0-1.5% in molar.
  • the fourth test was done at 450 0 C.
  • the resultant NMR proton patterns show higher concentrations of paraformaldehyde at this temperature.
  • the concentration of paraformaldehyde was about 3.0-5.0% in molar.
  • the CO 2 flow rate used was 200 seem, and the water injection rate was 9.16 ml/min.
  • a low-pressure chemical vapor deposition (LPCVD) technique was used to deposit a catalyst layer 14 of ZnO on a calcium fully stabilized zirconia (FSZ) support 16.
  • the Zn precursor was Zn(CHCOO) 2 (98+%, Aldrich).
  • the temperature of the FSZ template was set at 300 0 C.
  • the temperature of precursor was set at 160 0 C.
  • the deposition pressure was controlled at 3 kPa.
  • the sample was coated two times. In the second run, the position of the sample was reversed (front to back and top bottom of reactor) to get better uniformity of coating. Each coating time was 4 hours.
  • the total CVD coating time was 8 hours.
  • the sample was heated with a ramp rate at 5 ° C/min and calcined at 600° C for 12 hours in air.
  • Three electrodes were assembled on the ZnO-coated FSZ support as described above in connection with Figure 3. After the ZnO coated FSZ catalyst assembly was calcined, an area of 25 mm2 at the end was pretreated with 5M HCL to remove ZnO. A Platinum reference electrode 40 was assembled at this area. At another end of the cylinder sample, the same method as above was used to remove the ZnO layer, and a platinum wire was connected with the FSZ support layer 16 directly as the counter electrode 42. The working electrode 44 was attached to the ZnO catalyst layer 14. Platinum paste (6082 from BASF) was applied to enable the platinum electrodes to have good contact with the catalyst assembly.
  • Platinum paste 6082 from BASF
  • the CO 2 flow from tank 1 1 was measured with a flowmeter (OMEGA FL-3504G). Water injection was measured by a calibrated peristaltic pump 17 (Watson Marlow Sci400). Water was dropped on heated ceramic frit (>130 0 C) and evaporated in a T tube. Then water was introduced into the reactor with the CO 2 carrier gas.
  • ZnO-FSZ catalyst assembly was placed into a 2-inch quartz tube reactor (e.g., tubular reactor 22). The reactor 22 was heated to 600-700 0 C with a tube furnace (Thermolyne 21100) or via heating element 34. The ZnO-FSZ catalyst assembly was connected with the three electrodes to the electronic control device 24 and polarized by a voltage or a current controlled by the electronic control device 24.
  • the outflow products were cooled by an ice-water trap 26 and a dry ice trap 28.
  • the gas from the reactor was dried by a molecular sieve column 30, then the gas composition was analyzed with an analyzer 32 (e.g., a gas chromatograph (SRI 8610C)).
  • an analyzer 32 e.g., a gas chromatograph (SRI 8610C)
  • a voltage of -2.5 V to 2.5V was applied for the polarization tests for with a potentiostatic EIS mode or single frequency mode.
  • the temperature of CO 2 and H 2 O was set at 600 and 700 0 C.
  • the flow rate of CO 2 was between 200-500 seem.
  • the ZnO coated FSZ assembly was investigated by scanning electron microscopy
  • FIG. 8 is a proton NMR spectrum of the synthesized products.
  • the CO 2 flow rate was set at 320-450 seem; water was injected with a flow rate of 10 mL/hour ( or 207sccm/min).
  • the CO 2 /H 2 O molar ratio was 1.6-2.2. Based on the results shown in Figure 8, one major product was synthesized.
  • the NMR chemical shift is between 4.75 to 5.20 ppm. Small amounts of formaldehyde were present at a chemical shift of 8.25 ppm.
  • the polarization voltage was set at -1.2 V to -1.5 V.
  • the typical polarization bode spectrum is shown in Figure 9.
  • the "A" line is without polarization and the "B” line is with -1.2 V polarizations.
  • the Zmod decreased. For example,
  • Figure 10 is a single frequency EIS spectrum. With the fixed frequency of
  • the Zmod was shown to change with time. This change reflected the dynamic reactions at the surface of the catalytic assembly.
  • the comparison tests showed that if alternating negative and positive polarizations were used, the Zmod would decrease after negative polarization, which increases the reaction rate.
  • K 2 S 2 O8, K 2 SO 4 , and MnSO 4 were mixed with 70 ml Deionized (DI) water in a
  • Porous materials were used as the substrate for (Support 16) loading OMS-2 coating (catalyst 14) at the surface.
  • Corning Honeycomb cordierite was used as the substrate. Its pore sizes are 5-20 mesh.
  • Other porous substrates such as yttrium stabilized zirconium could be used.
  • Counter electrode 42 and reference electrode 40 were assembled first before coating a layer of OMS-2 manganese oxide (catalyst 14). Silver or platinum wires were used as electrode. Silver conductive paste was applied to fix the wires on the substrate 16. After assembled electrodes, the sample was put in an oven for curing at 80 0 C for 6 hours. Then it was calcined at 600 0 C for 8 hours.
  • the other working electrode 44 was assembled by using silver or platinum gauze.
  • the gauze was supported by an insulated pad.
  • the pad was contacted with the substrate.
  • 10-mesh cordierite honeycomb is used as the substrate 16.
  • OMS-2 The pulp-like OMS-2 was stirred and heated to 80-90 0 C for 6 hours in a beaker. OMS-2 pulp-like slurry was dropped to the substrate. By using the evacuation apparatus (Figure T), OMS-2 was uniformly coated on the substrate 16 to provide catalyst layer 14.
  • the working electrode 44 was modified by using droplets of pulp-like OMS.
  • the reference electrode 40 was cleaned by removing OMS-2.
  • the OMS-2 coated substrate was dried at 120 0 C for overnight. e) Chemical vapor deposition of platinum on OMS-2
  • the as-coated OMS-2 sample was put into a quartz tube (tubular reactor 22).
  • the tube was heated in a tube furnace at 300-450 0 C.
  • Pt(acac) 2 (Stream Chemicals Inc.) was used as the precursor and oxygen was used as oxidant (oxidizing agent 19).
  • Argon was used as the carrier gas and preheated to 100-150 0 C.
  • the pressure in the tube was set at 5- 20 kPa.
  • the carrier gas flow was set at 500-1000 seem and oxygen flow was set at 50-200 seem.
  • the LP-CVD time was 1-3 hours.
  • Air was used as carrier gas and oxidant 19.
  • the flow rate was controlled by a Mass flow controller or a rotameter.
  • the concentration of benzene could be diluted by addition of air and other gases. By putting the benzene bubbler in a warm water bath, the concentration of benzene 112 will be increased.
  • the system was set at slightly higher than atmospheric pressure (for example 5kpa).
  • the current/voltage source 20 supplied polarized current or voltage to the catalytic cell 14.
  • the tube reactor temperature was set at 100-450 0 C controlled by heating element 34 of Figure 2.
  • OMS-2 is a mixed valent manganese oxide.
  • Mn has high mixed oxidation states of valence 3 + and A + .
  • Oxygen ion is easy to move between the vacancies of the lattice.
  • a small DC current was applied to the sample at a certain frequency, the impedance of the sample changed more than 10 percent.
  • Oxygen ions could be continuously driven to the surface by positive current (or DC voltage). These oxygen ions could react with benzene.
  • Method 1 Apply a small current on the interface of the catalysts.
  • Galvanostatic EIS graph showed that the reaction was promoted by using a small current.
  • Method 2 Apply a positive or negative voltage on the interface of the catalysts.
  • the present invention encompasses methods, processes, and apparatus for the activation of the reaction between low-reactivity, non-polar molecules (such as CO 2 ) with polar molecules / species
  • a process is provided which leads to the activation of the reaction of carbon dioxide (and of other similar low-reactivity, non-polar molecules) with polar compounds (such as water, steam, or others) in a heterogeneous catalytic reaction.
  • the present invention may be used to activate the following reactions (among others):
  • the present invention provides advantageous methods and apparatus for the activation of carbon dioxide and other low-reactivity molecules.

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Abstract

L'invention concerne des procédés et des dispositifs pour l'activation d'un composé chimique non polaire à basse réactivité. Dans un mode de réalisation donné à titre d'exemple, le procédé comprend la mise en présence du composé chimique à basse réactivité avec un catalyseur. Au moins l'un parmi (a) un agent d'oxydation ou un agent de réduction et (b) un composé polaire est fourni au catalyseur et au composé chimique. Un courant alternatif est appliqué au catalyseur pour produire une réaction d'activation dans le composé chimique. Cette réaction d'activation produit un produit utile. La présente invention concerne également un procédé pour oxyder des composés aromatiques par électrocatalyse pour obtenir des produits oxydés.
PCT/US2008/076924 2007-09-20 2008-09-19 Procédés et dispositifs pour la synthèse de composés utiles WO2009039325A2 (fr)

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