Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions

• US 6,332,968 B1
• Filed: 01/26/2000
• Issued: 12/25/2001
• Est. Priority Date: 03/13/1987
• Status: Expired due to Fees

• Current Assignee: Standard Oil Company (BP PLC)
• Original Assignee: Standard Oil Company (BP PLC)
• Inventors: Cable, Thomas L., Frye, John G. Jr., Mazanec, Terry J., Kliewer, Wayne R.
• Primary Examiner(s): Valentine, Donald R.
• Application Number:
  US09/491,609
• Time in Patent Office: 699 Days
• Field of Search: 205/763, 205/764, 205/765, 205/334, 205/343, 205/687, 205/770, 95/54
• US Class Current: 205/334
• CPC Class Codes: B01D 2323/08 Specific temperatures applied
• CPC Class Codes: B01D 2323/081 Heating
• CPC Class Codes: B01D 2323/10 Specific pressure applied
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 2325/26 Electrical properties
• CPC Class Codes: B01D 53/326 in electrochemical cells
• CPC Class Codes: B01D 67/0041 by agglomeration of particles in the dry state
• CPC Class Codes: B01D 67/00411 by sintering
• CPC Class Codes: B01D 67/0044 by chemical reaction
• CPC Class Codes: B01D 67/0046 by slurry techniques, e.g. die or slip-casting
• CPC Class Codes: B01D 67/0083 Thermal after-treatment
• CPC Class Codes: B01D 67/0093 Chemical modification
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 69/145 containing embedded catalysts
• CPC Class Codes: B01D 71/02 Inorganic material
• CPC Class Codes: B01D 71/0215 Silicon carbide; Silicon nitride; Silicon oxycarbide
• CPC Class Codes: B01D 71/022 Metals
• CPC Class Codes: B01D 71/02231 Palladium
• CPC Class Codes: B01D 71/024 Oxides
• CPC Class Codes: B01D 71/0271 : Perovskites
• CPC Class Codes: B01J 12/007 : in the presence of catalytically active bodies, e.g. porous plates
• CPC Class Codes: B01J 19/2475 : Membrane reactors
• CPC Class Codes: B01J 2208/00044 : Temperature measurement
• CPC Class Codes: B01J 2208/00106 : by indirect heat exchange
• CPC Class Codes: B01J 2208/00309 : with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
• CPC Class Codes: B01J 2208/00336 : adding a temperature modifying medium to the reactants
• CPC Class Codes: B01J 2208/00345 : Cryogenic coolants
• CPC Class Codes: B01J 2208/00548 : Flow
• CPC Class Codes: B01J 2208/00628 : Controlling the composition of the reactive mixture
• CPC Class Codes: B01J 2219/00058 : Temperature measurement
• CPC Class Codes: B01J 2219/00117 : with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
• CPC Class Codes: B01J 2219/00123 : adding a temperature modifying medium to the reactants
• CPC Class Codes: B01J 2219/00126 : Cryogenic coolants
• CPC Class Codes: B01J 2219/00164 : controlling the flow
• CPC Class Codes: B01J 2219/00186 : controlling the composition of the reactive mixture
• 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: C01B 13/0255 : characterised by the type of membrane
• CPC Class Codes: C01B 13/0288 : Combined chemical and physical processing
• CPC Class Codes: C01B 2203/0261 : containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/1035 : Catalyst coated on equipment surfaces, e.g. reactor walls
• CPC Class Codes: C01B 2203/1241 : Natural gas or methane
• CPC Class Codes: C01B 2203/1258 : Pre-treatment of the feed
• CPC Class Codes: C01B 2210/0003 : Chemical processing
• CPC Class Codes: C01B 2210/0012 : characterised by the membrane
• CPC Class Codes: C01B 2210/0071 : Sulfur oxides
• CPC Class Codes: C01B 2210/0075 : Nitrogen oxides
• CPC Class Codes: C01B 3/36 : using oxygen or mixtures containing oxygen as gasifying agents
• CPC Class Codes: C01B 3/386 : Catalytic partial combustion
• CPC Class Codes: C01C 3/0216 : characterised by the catalyst used
• CPC Class Codes: C01C 3/0225 : characterised by the synthesis reactor
• CPC Class Codes: C01C 3/0233 : making use of fluidised beds, e.g. the Shawinigan-process
• CPC Class Codes: C01G 45/006 : Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen manganates, manganites or permanganates C01G45/12
• CPC Class Codes: C01G 45/1271 : of the type [Mn2O8]n-, e.g. (LaSr3)Mn2O8
• CPC Class Codes: C01G 49/0036 : containing one alkaline earth metal, magnesium or lead
• CPC Class Codes: C01G 49/0054 : containing one rare earth metal, yttrium or scandium
• CPC Class Codes: C01G 49/0072 : containing manganese
• CPC Class Codes: C01G 49/009 : Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01G 51/68 : containing rare earth, e.g. La0.3Sr0.7CoO3
• CPC Class Codes: C01P 2002/34 : perovskite-type (ABO3)
• CPC Class Codes: C01P 2002/52 : containing elements as dopants
• CPC Class Codes: C01P 2002/54 : one element only
• CPC Class Codes: C01P 2004/03 : obtained by SEM
• CPC Class Codes: C01P 2004/80 : Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: C01P 2004/84 : one phase coated with the other
• CPC Class Codes: C01P 2006/12 : Surface area
• CPC Class Codes: C01P 2006/40 : Electric properties
• CPC Class Codes: C25B 1/00 : Electrolytic production of inorganic compounds or non-metals
• CPC Class Codes: C25B 13/00 : Diaphragms; Spacing elements
• CPC Class Codes: C25B 3/23 : Oxidation halogenation C25B3/27
• CPC Class Codes: C25B 5/00 : Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
• CPC Class Codes: H01M 8/12 : operating at high temperature, e.g. with stabilised ZrO2 electrolyte
• CPC Class Codes: H01M 8/1231 : with both reactants being gaseous or vaporised
• CPC Class Codes: H01M 8/1246 : the electrolyte consisting of oxides
• 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

Electrochemical processes using solid gas-impervious membranes are disclosed for gas cleanup by (A) providing an electrochemical cell comprising first and second zones separated by a solid gas-impervious membrane comprising a mixed metal oxide material of a perovskite structure having electron conductivity and oxygen ion conductivity, (B) passing a gas containing N₂O, NO, NO₂, SO₂, SO₃, or a mixture thereof, in contact with the membrane in the first zone, and (C) passing a gas capable of reacting with oxygen in contact with the membrane in the second zone. More particularly, the mixed metal oxide material of a perovskite structure comprises a combination of elements selected from the group consisting of lanthanides, alkaline earth metals, Y, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, and Nb, oxides thereof, and mixtures of these metals and metal oxides. Advantageously a catalyst is present in the first zone.

Claims

1. An electrochemical process for gas cleanup which comprises

(A) providing an electrochemical cell which comprises first and second zones separated by a solid gas-impervious membrane comprising a mixed metal oxide material of a perovskite structure having electron conductivity and oxygen ion conductivity,

(B) passing a gas containing N₂O, NO, NO₂, SO₂, SO₃, or a mixture thereof, in contact with the membrane in the first zone, and

(C) passing a gas capable of reacting with oxygen in contact with the membrane in the second zone.

2. The electrochemical process of claim 1 wherein the mixed metal oxide material of a perovskite structure comprises a combination of elements selected from the group consisting of lanthanides, alkaline earth metals, Y, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, and Nb, oxides thereof, and mixtures of these metals and metal oxides.

3. The electrochemical process of claim 1 wherein the mixed metal oxide material of a perovskite structure comprises a combination of elements selected from the group consisting of La, Co, Y, Sr, Ca, Fe, Cr, oxides thereof, and mixtures of these metals and metal oxides.

4. The electrochemical process of claim 1 wherein the gas containing N₂O, NO, NO₂, SO₂, SO₃, or a mixture thereof, is derived from burning of a sulfur-containing fuel.

5. The electrochemical process of claim 1 wherein the gas passed in contact with the membrane in the first zone comprises SO₂ or SO₃, or a mixture thereof.

6. The electrochemical process of claim 1 wherein a catalyst is present in the first zone.

7. An electrochemical process for gas cleanup which comprises

(A) providing an electrochemical cell which comprises first and second zones separated by a solid gas-impervious membrane comprising a mixed metal oxide material of a perovskite structure containing a combination of elements selected from the group consisting of La, Co, Y, Sr, Ca, Fe, Cr, oxides thereof, and mixtures of these metals and metal oxides and a catalyst in the first zone,

(B) heating the electrochemical cell to a temperature of from about 300°

C. to about 1000°

C.,

(C) passing a gas containing N₂O, NO, NO₂, SO₂, SO₃, or a mixture thereof in contact with the membrane in the first zone, and

(D) passing hydrogen, methane or natural gas, or a mixture thereof, in contact with the membrane in the second zone.

8. An electrochemical process for gas cleanup which comprises

(A) providing an electrochemical cell which comprises first and second zones separated by a solid gas-impervious membrane comprising a mixed metal oxide material of a perovskite structure having electron conductivity and oxygen ion conductivity,

(B) passing a gas containing N₂O, NO, NO₂, SO₂, SO₃, or a mixture thereof, in contact with the membrane in the first zone, and

(C) passing a gas capable of reacting with oxygen in contact with the membrane in the second zone,

wherein the mixed oxide material of a perovskite structure comprises a lanthanide in combination with Co, Sr or an oxide thereof.

9. An electrochemical process for gas cleanup which comprises

(A) providing an electrochemical cell which comprises a first zone with a catalyst and a second zone separated from the first zone by a solid gas-impervious membrane having first and second surfaces contiguous respectively with the first and second zones and comprising a mixed metal oxide material of a perovskite structure having electron conductivity and oxygen ion conductivity,

(B) passing a gas containing N₂O, NO, NO₂, SO₂, SO₃, or a mixture thereof, in contact with the membrane in the first zone, and

(C) passing a gas capable of reacting with oxygen in contact with the membrane in the second zone,

wherein the catalyst is present as a coating on the first surface of the membrane.

10. An electrochemical process for gas cleanup which comprises

(A) providing an electrochemical cell which comprises a first zone with a catalyst and a second zone separated from the first zone by a solid gas-impervious membrane having first and second surfaces contiguous respectively with the first and second zones and comprising a mixed metal oxide material of a perovskite structure having electron conductivity and oxygen ion conductivity,

(B) passing a gas containing N₂O, NO, NO₂, SO₂, SO₃, or a mixture thereof, in contact with the membrane in the first zone, and

(C) passing a gas capable of reacting with oxygen in contact with the membrane in the second zone,

wherein the catalyst is present on a support adjacent to the first surface of the membrane.