Method and apparatus for electrochemical production of ozone

• US 5,460,705 A
• Filed: 07/13/1993
• Issued: 10/24/1995
• Est. Priority Date: 07/13/1993
• Status: Expired due to Term

• Current Assignee: Lynntech International, Ltd.
• Original Assignee: Lynntech Incorporated
• Inventors: Murphy, Oliver J., Hitchens, G. Duncan
• Primary Examiner(s): Gorgos, Kathryn
• Application Number:
  US08/091,752
• Time in Patent Office: 833 Days
• Field of Search: 204/254, 204/255, 204/256, 204/282, 204/283, 204/290 R, 204/290 F, 204/252, 204/257, 204/258, 429/42
• US Class Current: 204/252
• CPC Class Codes: B01D 53/22 by diffusion manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00
• CPC Class Codes: B01D 53/326 in electrochemical cells
• CPC Class Codes: B01F 23/12 with vaporisation of a liquid disinfection, sterilisation or deodorisation of air A61L9/00
• CPC Class Codes: B01J 19/2475 Membrane reactors
• CPC Class Codes: B01J 2208/00061 of the reactants
• CPC Class Codes: B01J 2208/00132 Tubes
• CPC Class Codes: B01J 2208/00256 in a heat exchanger for the heat exchange medium separate from the reactor
• CPC Class Codes: B01J 2208/00539 Pressure
• CPC Class Codes: B01J 2208/00584 Controlling the density
• CPC Class Codes: B01J 2219/00063 of the reactants
• CPC Class Codes: B01J 2219/00081 Tubes
• CPC Class Codes: B01J 2219/00099 the reactor being immersed in the heat exchange medium
• CPC Class Codes: B01J 2219/00103 in a heat exchanger separate from the reactor
• CPC Class Codes: B01J 2219/00162 controlling the pressure
• CPC Class Codes: B01J 2219/00171 controlling the density
• CPC Class Codes: B01J 8/009 Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
• CPC Class Codes: C02F 1/32 with ultraviolet light
• CPC Class Codes: C02F 1/4618 for producing "ionised" acidic or basic water
• CPC Class Codes: C02F 1/4672 by electrooxydation
• CPC Class Codes: C02F 1/78 with ozone C02F1/4672 takes precedence
• CPC Class Codes: C02F 2001/46128 : Bipolar electrodes
• CPC Class Codes: C02F 2001/46142 : Catalytic coating
• CPC Class Codes: C02F 2001/46166 : Gas diffusion electrodes
• CPC Class Codes: C02F 2101/30 : Organic compounds
• CPC Class Codes: C02F 2201/46115 : Electrolytic cell with membranes or diaphragms
• CPC Class Codes: C02F 2201/46195 : Cells containing solid electrolyte
• CPC Class Codes: C02F 2201/782 : Ozone generators
• CPC Class Codes: C02F 2303/04 : Disinfection
• CPC Class Codes: C02F 2305/023 : Reactive oxygen species, singlet oxygen, OH radical
• CPC Class Codes: C25B 1/13 : Ozone
• CPC Class Codes: C25B 1/30 : Peroxides
• CPC Class Codes: C25B 13/02 : characterised by shape or form
• CPC Class Codes: C25B 9/19 : with diaphragms
• CPC Class Codes: H01M 2300/0082 : Organic polymers
• CPC Class Codes: H01M 8/0202 : Collectors; Separators, e.g. bipolar separators; Interconnectors
• CPC Class Codes: H01M 8/0289 : Means for holding the electrolyte solid polymer electrolytes H01M8/1018
• CPC Class Codes: H01M 8/04291 : Arrangements for managing water in solid electrolyte fuel cell systems H01M8/04119 takes precedence
• CPC Class Codes: H01M 8/1007 : with both reactants being gaseous or vaporised H01M8/12 takes precedence
• CPC Class Codes: H01M 8/1023 : having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• CPC Class Codes: H01M 8/1039 : halogenated, e.g. sulfonated polyvinylidene fluorides
• CPC Class Codes: H01M 8/186 : by electrolytic decomposition of the electrolytic solution or the formed water product
• CPC Class Codes: Y02C 20/30 : of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

An electrolytic cell for the production of ozone utilizing an anodic electrocatalyst and a membrane and electrode assembly formed by bonding a polytetrafluoroethylene-containing, proton exchange polymer-impregnated, gas diffusion cathode to a proton exchange membrane.

Claims

1. An electrolytic cell for the production of ozone comprising:

an anode comprising a porous sintered substrate and an electronically conducting, hydrophilic, ozone-forming catalyst coating thereon, wherein the substrate is formed by sintering particulate materials selected from the group consisting of titanium, titanium suboxides, platinum, tungsten, tantalum, hafnium and niobium, and wherein the catalyst coating comprises a catalyst selected from the group consisting of lead dioxide, platinum-tungsten alloys and mixtures, glassy carbon and platinum;

a gas diffusion cathode comprising a polytetrafluoroethylene-bonded, semi-hydrophobic catalyst layer comprised of a proton exchange polymer and a metal selected from the group consisting of platinum, palladium, gold, iridium, nickel and mixtures thereof, supported on a hydrophobic gas diffusion layer comprising carbon cloth or carbon paper fiber impregnated with a sintered mass derived from fine carbon powder and a polytetrafluoroethylene emulsion; and

a proton exchange membrane having a first side bonded to the catalyst layer of the gas diffusion cathode and a second side in contact with the anodic catalyst coating.

2. The electrolytic cell of claim 1 wherein the catalyst coating on the substrate of the gas diffusion cathode is comprised of platinum.

3. The electrolytic cell of claim 1 wherein the catalyst coating on the metal substrate of the anode is comprised of porous titanium.

4. The electrolytic cell of claim 1 wherein the proton exchange membrane is comprised of a perfluorinated sulfonic acid polymer.

5. The electrolytic cell of claim 1 wherein the catalyst coating on the metal substrate of the anode and the catalyst layer of the gas diffusion cathode further comprise a perfluorinated sulphonic acid polymer.

6. The electrolytic cell of claim 1 wherein the metal substrate of the anode is coated with a thin layer of a noble metal selected from the group consisting of platinum, gold, iridium and palladium, and wherein the layer of noble metal is coated with the anodic catalyst coating.

7. The electrolytic cell of claim 1 wherein the metal substrate of the anode is coated with lead dioxide.

8. An apparatus for the electrolytic generation of ozone comprising:

(a) a plurality of individual electrolytic cells having;

(i) an anode comprising a smooth, flat, rigid porous sintered substrate and a catalyst coating, wherein the substrate is formed by sintering particulate materials selected from the group consisting of porous titanium, titanium suboxides, platinum, tungsten, tantalum, hafnium and niobium, and wherein the catalyst coating is selected from the group consisting of lead dioxide, platinum-tungsten alloys and mixtures, glassy carbon and platinum;

(ii) a gas diffusion cathode comprising a polytetrafluoroethylene-bonded, semi-hydrophobic catalyst layer supported on a hydrophobic gas diffusion layer, wherein the catalyst layer is comprised of a proton exchange polymer, polytetrafluorethylene polymer and a metal selected from the group consisting of platinum, palladium, gold, iridium, nickel and mixtures thereof, and wherein the gas diffusion layer has a carbon cloth or carbon paper fiber impregnated with a sintered mass derived from fine carbon powder and a polytetrafluoroethylene emulsion;

(iii) a proton exchange membrane having a first side bonded to the catalyst layer of the gas diffusion cathode and a second side in contact with the anodic catalyst coating;

(iv) a first electrically insulating, chemically resistant gasket disposed around the edge of the anode having sections removed for internal manifolding to allow fluid flow to and from the anode;

(v) a second electrically insulating, chemically resistant gasket disposed around the gas diffusion cathode having sections removed for internal manifolding to allow fluid flow to and from the cathode;

(vi) a first expanded metal sheet communicating electrically with the anode and facilitating fluid flow over the complete surface of the anode; and

(vii) a second expanded metal sheet communicating electrically with the cathode and facilitating fluid flow over the complete surface of the cathode;

(b) wherein each of the individual electrolytic cells are positioned in a filter-press arrangement and connected in a series electrical circuit;

(c) a fluid impervious bipolar plate selected from the group consisting of dense titanium, tantalum, hafnium, zirconium, stainless steels, and other high chromium/nickel-containing alloys disposed between each of the individual electrolytic cells, wherein said bipolar plate has a first side in electrical contact with the first expanded metal sheet of a first adjacent cell and a second side in electrical contact with the second expanded metal sheet of a second adjacent cell;

(d) first and second end plates having electrical connection means, an oxygen gas or air inlet port, a water inlet port, a cathode product outlet port and an anode product outlet port; and

(e) clamping means for securing the end plates and electrolytic cells tightly together.

9. The apparatus of claim 8 further comprising means for electrically isolating the first end plate from the second end plate.

10. The electrolytic cell of claim 8 wherein the metal substrate of the anode is coated with a thin layer of a noble metal selected from the group consisting of platinum, gold, iridium and palladium, and wherein the layer of noble metal is coated with the anodic catalyst material.