Conversion of carbonaceous fuels into carbon free energy carriers

• US 9,376,318 B2
• Filed: 10/01/2014
• Issued: 06/28/2016
• Est. Priority Date: 09/26/2008
• Status: Active Grant

• Current Assignee: Ohio State University
• Original Assignee: Ohio State University
• Inventors: Fan, Liang-Shih, Li, Fanxing
• Primary Examiner(s): YOUNG, NATASHA E
• Application Number:
  US14/504,295
• Publication Number:
  US 20150093577A1
• Time in Patent Office: 636 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 19/245 placed in series
• CPC Class Codes: B01J 2219/19 Details relating to the geometry of the reactor
• CPC Class Codes: B01J 2219/24 Stationary reactors without moving elements inside
• CPC Class Codes: B01J 23/745 Iron
• CPC Class Codes: B01J 23/94 of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/50 characterised by their shape or configuration
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/0063 Granulating
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/18 with gases containing free hydrogen
• CPC Class Codes: C01B 3/02 Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
• CPC Class Codes: C01B 3/344 using non-catalytic solid particles
• CPC Class Codes: C04B 2235/3201 Alkali metal oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3217 Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• CPC Class Codes: C04B 2235/3232 Titanium oxides or titanates, e.g. rutile or anatase
• CPC Class Codes: C04B 2235/3427 Silicates other than clay, e.g. water glass
• CPC Class Codes: C04B 2235/349 Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
• CPC Class Codes: C04B 2235/5427 millimeter or submillimeter sized, i.e. larger than 0,1 mm
• CPC Class Codes: C04B 35/6265 involving reduction or oxidation
• CPC Class Codes: C04B 35/62655 : Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
• CPC Class Codes: C04B 35/62675 : characterised by the treatment temperature
• CPC Class Codes: C04B 35/62695 : Granulation or pelletising devices for shaping artificial aggregates from ceramic mixtures B28B1/004
• CPC Class Codes: C04B 35/62826 : Iron group metal oxides
• CPC Class Codes: C04B 35/6316 : Binders based on silicon compounds
• CPC Class Codes: C04B 35/6365 : Cellulose or derivatives thereof
• CPC Class Codes: C10J 2300/0916 : Biomass
• CPC Class Codes: C10J 2300/093 : Coal
• CPC Class Codes: C10J 2300/0943 : Coke
• CPC Class Codes: C10J 2300/0959 : Oxygen
• CPC Class Codes: C10J 2300/0969 : Carbon dioxide
• CPC Class Codes: C10J 2300/0976 : as steam
• CPC Class Codes: C10J 2300/1671 : with the production of electricity
• CPC Class Codes: C10J 2300/1807 : Recycle loops, e.g. gas, solids, heating medium, water
• CPC Class Codes: C10J 2300/1869 : with one stream being air, oxygen or ozone
• CPC Class Codes: C10J 2300/1884 : with one stream being synthesis gas
• CPC Class Codes: C10J 3/12 : using solid heat-carriers
• CPC Class Codes: C10J 3/463 : in stationary fluidised beds
• CPC Class Codes: C10J 3/485 : Entrained flow gasifiers
• CPC Class Codes: C10J 3/725 : Redox processes
• CPC Class Codes: F23C 2900/99008 : Unmixed combustion, i.e. without direct mixing of oxygen gas and fuel, but using the oxygen from a metal oxide, e.g. FeO
• CPC Class Codes: F23C 99/00 : Subject-matter not provided for in other groups of this subclass
• CPC Class Codes: Y02E 20/16 : Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
• CPC Class Codes: Y02E 20/34 : Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 20/584 : Recycling of catalysts
• CPC Class Codes: Y10T 428/2982 : Particulate matter [e.g., sphere, flake, etc.]

Abstract

A system for converting fuel is provided and includes a first reactor comprising a plurality of ceramic composite particles, the ceramic composite particles comprising at least one metal oxide disposed on a support, wherein the first reactor is configured to reduce the at least one metal oxide with a fuel to produce a reduced metal or a reduced metal oxide; a second reactor configured to oxidize at least a portion of the reduced metal or reduced metal oxide from the said first reactor to produce a metal oxide intermediate; a source of air; and a third reactor communicating with said source of air and configured to regenerate the at least one metal oxide from the remaining portion of the solids discharged from the said first reactor and the solids discharged from the said second reactor by oxidizing the metal oxide intermediate.

Claims

1. A method of preparing ceramic composite particles comprising:

mixing a metal oxide with at least one ceramic material to form a mixture;

granulating said mixture by adding a binding material;

drying said granulated mixture;

processing said dried, granulated mixture into particle form such that the length of said particles is greater than about 200 μ

m;

heat treating said particles at a temperature of from about 500 to about 1500°

C.; and

reducing and oxidizing said particles.

2. The method of claim 1, wherein the ceramic material is in powder form.

3. The method of claim 1, wherein the binder material is starch, sodium silicate, potassium silicate, or a combination thereof.

4. The method of claim 1, wherein a promoter material is adding in the mixing step before granulation.

5. The method of claim 4, wherein the promoter material comprises a pure metal, a metal oxide, a metal sulfide, or a combination thereof.

6. The method of claim 4, wherein the promoter material comprises Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, B, P, V, Cr, Mn, Co, Cu, Zn, Ga, Mo, Rh, Pt, Pd, Ag, Ru, or a combination thereof.

7. The method of claim 4, wherein the ceramic composite comprises up to about 20% by weight of the promoter material.

8. The method of claim 1, wherein the metal oxide comprises Fe, Cu, Ni, Co, Mn, In, or a combination thereof.

9. The method of claim 1, wherein ceramic material comprises SiC, an oxide of Al, Zr, Ti, Y, Si, La, Sr, or Ba, or a combination thereof.

10. The method of claim 1, wherein the ceramic material comprises a natural ore.

11. The method of claim 1, wherein the ceramic material comprises bentonite or sepiolite.

12. The method of claim 1, wherein the ceramic composite comprises Fe₂O₃ supported on a support that is a mixture of alumina (Al₂O₃) and Anatase (TiO₂).

13. The method of claim 1, wherein the step of drying said granulated mixture comprises drying at temperature of about 50°

C. to about 500°

C. in an air or nitrogen atmosphere.

14. The method of claim 1, wherein the step of drying said granulated mixture reduces the moisture content of the mixture to below 10%.

15. The method of claim 1, wherein the step of granulating said mixture by adding a binding material further comprises adding water to said mixture.

16. The method of claim 1, wherein the step of processing said dried, granulated mixture into particle form such that the length of said particles is greater than about 200 μ

m, comprises processing said dried, granulated mixture into pellets.

17. The method of claim 16, wherein the pellets are produced by extrusion, granulation, or pressurization.

18. The method of claim 16, where the pellets are produced by pressurization at pressures of 0.1 to 25 MPa.

19. A ceramic composite as claimed in claim 1 that can perform reduction-oxidation reactions for more than 100 cycles without significantly losing its reactivity.

20. A ceramic composite as claimed in claim 1 that can react with different ranks of coal, syngas, and methane for more than 7 cycles without significantly losing its reactivity.