Metal ferrite oxygen carriers/catalyst for partial oxidation of methane for production of synthesis gas

Patent metadata

Field	Value
Publication number	US-10106407-B1
Application number	US-201715497708-A
Country	US
Kind code	B1
Filing date	Apr 26, 2017
Priority date	Apr 26, 2017
Publication date	Oct 23, 2018
Grant date	Oct 23, 2018

Abstract

Materials, methods to prepare, and methods of use for partial oxidation of methane. Embodiments include delivering a metal ferrite oxygen carrier to a fuel reactor, wherein the metal ferrite oxygen carrier comprises MFexOy where 1≤x≤3 and 3≤y≤5, and where M comprise a Group II alkali earth metals; and delivering a gaseous stream that contains methane to the metal ferrite oxygen carrier in the fuel reactor and maintaining the fuel reactor at a reducing temperature sufficient to reduce some portion of the metal ferrite oxygen carrier and oxidize some portion of the methane containing gas stream. Embodiments further include generating gaseous products containing H 2 and CO gas in the fuel reactor; withdrawing a product stream from the fuel reactor, where the gaseous products comprise the product stream, and where at least >50 vol. % of the product stream includes CO and H 2 ; oxidizing the reduced carrier in an oxidizing reactor by contacting the reduced carrier and an oxidizing gas at an oxidizing temperature, where the oxidizing gas is comprised of oxygen, and where the oxidizing temperature is sufficient to generate an oxidizing reaction, where the reactants of the oxidizing reaction comprise some portion of the oxygen, some portion of the M component, and some portion of the FecOd component, and further wherein the product of the oxidizing reaction is a re-oxidized carrier that comprises some portion of the MFexOy; and delivering heat generated in the oxidizing reactor to the fuel reactor for the reaction of metal ferrite with methane.

First claim

We claim:

1. A method for partial oxidation of methane comprising:
delivering a metal ferrite oxygen carrier to a fuel reactor, wherein the metal ferrite oxygen carrier comprises MFexOy where 1≤x≤3 and 3≤y≤5, and where M comprise Group II alkali earth metals consisting of at least one of Mg, Ca, Ba, Sr and combinations thereof;
delivering a gaseous stream that contains methane to the metal ferrite oxygen carrier in the fuel reactor and maintaining the fuel reactor at a reducing temperature sufficient to reduce some portion of the metal ferrite oxygen carrier and oxidize some portion of the methane containing gas stream;
generating gaseous products containing H 2 and CO gas in the fuel reactor;
withdrawing a product stream from the fuel reactor, where the gaseous products comprise the product stream, and where at least >50 vol. % of the product stream includes CO and H 2 ;
oxidizing the reduced carrier in an oxidizing reactor by contacting the reduced carrier and an oxidizing gas at an oxidizing temperature, where the oxidizing gas is comprised of oxygen, and where the oxidizing temperature is sufficient to generate an oxidizing reaction, where the reactants of the oxidizing reaction comprise some portion of the oxygen, some portion of the M component, and some portion of the FecOd component, and further wherein the product of the oxidizing reaction is a re-oxidized carrier that comprises some portion of the MFexOy; and
delivering heat generated in the oxidizing reactor to the fuel reactor for the reaction of metal ferrite with methane.

2. The method of claim 1 where the reducing temperature ranges from about 700° C. to about 1100° C.

3. The method of claim 1 wherein 1.5≤x≤2.5 and 3.5≤y≤4.

4. The method of claim 1 wherein MFexOy comprises at least 30 wt. % of the metal ferrite oxygen carrier.

5. The method of claim 4 wherein the metal ferrite oxygen carrier further comprises an inert support that comprises from about 5 wt. % to about 60 wt. % of the metal ferrite oxygen carrier.

6. The method of claim 5 wherein the inert support contains at least one of alumina, silica, zirconia, clay, titania, monolith and combinations thereof.

7. The method of claim 1 wherein methane concentration is greater than 5 vol. %.

8. The method of claim 1 further comprising generating a reduced carrier by mixing the methane containing gas stream and the metal ferrite oxygen carrier in the fuel reactor, where the reduced carrier comprises an M component and an FecOd component, where the M component comprises some portion of the M comprising the MFexOy, and MO and where the FecOd component comprises some portion of the Fe comprising the MFexOy, where c>0 and d≥0.

9. The method of claim 8 where the FecOd component comprises Fe 0 , FeO, Fe 3 O 4 or Fe 2 O 3 and the M component is MO, MCO 3 or MFex-n Oy-m where n<x and m<y.

10. The method of claim 9 wherein oxidization of the reduced carrier occurs in the oxidizing reactor further comprising:
transferring the reduced carrier from the fuel reactor to the oxidizing reactor;
supplying the oxidizing gas to the oxidizing reactor, generating a re-oxidized carrier;
transferring the re-oxidized carrier from the oxidizing reactor to the fuel reactor;
repeating the delivery of the metal ferrite oxygen carrier to the fuel reactor, introducing methane to the metal ferrite oxygen carrier in the fuel reactor; and
withdrawing the product stream from the fuel reactor.

11. The method of claim 10 wherein the oxidizing temperature ranges from about 700° C. to about 1100° C.

12. A method of producing synthesis gas from methane comprising:
delivering a metal ferrite oxygen carrier to a catalytic reactor, where the metal ferrite oxygen carrier comprises MFexOy where 1≤x≤3 and 3≤y≤5, and where M consists of at least one of Mg, Ca, Ba, Sr and combinations thereof, where the MFexOy comprises at least 30 wt. % of the metal ferrite oxygen carrier;
delivering a continuous gas stream containing methane of at least >5 vol. %;
delivering a pure continuous gas stream containing oxygen >1 vol. %;
maintaining the catalytic reactor at a reaction temperature sufficient to reduce some portion of the metal ferrite oxygen carrier and oxidize some portion of the methane containing gas stream;
generating a continuous stream of gaseous products containing H 2 and CO gas in the catalytic reactor; and
withdrawing a product stream from the fuel reactor, where the gaseous products comprise the product stream where at least >50 vol. % of the product stream consists of CO and H 2 .

13. The method of claim 12 wherein the oxygen gas stream is provided by oxygen separated from air.

14. The method of claim 12 further comprising:
decomposing metal oxide or peroxide generating a gaseous oxygen stream by maintaining a temperature sufficient to generate oxygen from the metal oxide/peroxide by decomposition reaction or Chemical looping un-coupling (CLOU) reaction in a CLOU reactor;
transferring the reduced metal oxide/peroxide to the oxidizing reactor;
oxidizing the reduced metal oxide/peroxide by contacting an oxidizing gas comprised of at least oxygen at an oxidizing temperature sufficient to generate an oxidizing reaction, where the reactants of the oxidizing reaction comprise some portion of the oxygen, some portion of the reduced metal oxide/metal peroxide, and where the product of the oxidizing reaction is a re-oxidized metal oxide/peroxide; and
delivering heat generated from the oxidizing reactor to the CLOU reactor.

15. The method of claim 14 wherein the metal oxide and peroxide contain at least one of copper oxide, manganese oxide, peroxides of alkali, Ba or Sr or combination of thereof.

16. The method of claim 14 wherein the decomposition temperature needed to generate oxygen in the CLOU reactor is above 300° C.

17. The method of claim 14 wherein the oxidation temperature in the oxidizing reactor is above 300° C.

Assignees

• Us Energy
• Us Dept Energy

Inventors

• Siriwardane Ranjani V
• Fan Yueying

Classifications

• C01B2203/0261

  containing a catalytic partial oxidation step [CPO] · CPC title

• C01B3/40 Primary

  characterised by the catalyst · CPC title

• B01J23/78

  with alkali- or alkaline earth metals · CPC title

• B01J38/12

  Treating with free oxygen-containing gas · CPC title

• C01B2203/1047

  Group VIII metal catalysts · CPC title