Conversion of carbonaceous fuels into carbon free energy carriers

• US 10,081,772 B2
• Filed: 06/23/2016
• Issued: 09/25/2018
• 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:
  US15/191,249
• Publication Number:
  US 20160376512A1
• Time in Patent Office: 824 Days
• 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 and 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 for by oxidizing the metal oxide intermediate.

Claims

1. A system for converting fuel comprising:

a first reactor comprising a shell side, a tube side, and a plurality of ceramic composite particles, with the ceramic composite particles comprising at least one metal oxide disposed on a support;

a first inlet for providing a fuel to said shell side of said first reactor; and

a second inlet for providing an oxygen-containing gas to said tube side of said first reactor;

wherein the first reactor is configured to reduce the at least one metal oxide with said fuel to produce a reduced metal or a reduced metal oxide, and wherein at least a portion of the composite particles and fuel are directly sent to said tube side of said first reactor where the heat of combustion provides heat to the reaction in said shell side of said first reactor;

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 and a hydrogen rich gas stream wherein sub-stoichiometric amounts of steam and/or CO₂ are introduced to the second reactor so that more heat is produced in the combustor;

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, optionally the solids discharged from the said second reactor, by oxidizing the metal oxide intermediate.

2. The system of claim 1, wherein the fuel is a solid fuel selected from the group consisting of coal, biomass, tar, pet coke, tar sands, oil sands, oil shades and combinations thereof.

3. The system of claim 1, wherein at least one of the first reactor and second reactor has a funnel shaped outlet to allow more controlled and homogenous movements of solids.

4. The system of claim 1, wherein at least one of the first reactor, second reactor, and third reactor are connected via a non-mechanical gas sealing and solids control flow devices selected from the group consisting of a loop seal, an L-valve, a J-valve, an N-valve, and a zone seal.

5. The system of claim 1, wherein the first reactor has an annular opening between the first stage and the second stage which allows gas to move from both the solid discharge port of the first stage and the ceiling of the annular opening.

6. The system of claim 1, wherein said second reactor is a moving bed reactor with one or more stages, a multistage moving bed, a rotary kiln, or a step reactor countercurrent flow between the solids and the gas.

7. The system of claim 1, wherein the second reactor includes a funnel-shaped outlet.

8. The system of claim 1, wherein the third reactor is a fast fluidized bed reactor, an entrained bed reactor, a transport bed reactor, or a mechanical conveying system.

9. The system of claim 1, wherein the third reactor comprises two stages, with the first stage located at the bottom being bubbling or turbulent fluidized bed reactor and the second stage being an entrained bed, fast fluidized bed or transport bed reactor.

10. The system of claim 1, wherein the third reactor is exothermic and at least part of the heat generated in the third reactor is integrated back to the first reactor to assist the reaction in the first reactor.

11. The system of claim 1, wherein oxygen is introduced to the first reactor to partially compensate for the heat required in the first reactor.

12. The system of claim 1, wherein the first reactor reduces the ceramic composite particles by 20% to 85%.

13. The system of claim 1, wherein the first reactor converts the fuel into an exhaust gas stream that contains at least CO₂ and steam.

14. The system of claim 1, wherein the second reactor converts at least 40% of the gaseous input into product.

15. The system of claim 1, wherein the ceramic composite particles are mixed with a catalyst.

16. The system of claim 15, wherein the catalyst is a water gas shift catalyst, a steam methane reforming catalyst, or a combination thereof.

17. The system of claim 15, wherein the catalyst comprises 0.01% to 30% by weight of the composite particles.

18. A system for converting fuel comprising:

a first reactor comprising a shell side, a tube side, and a plurality of ceramic composite particles, with the ceramic composite particles comprising at least one metal oxide disposed on a support;

a first inlet for providing a fuel to said shell side of said first reactor; and

a second inlet for providing an oxygen-containing gas to said tube side of said first reactor;

wherein the first reactor is configured to reduce the at least one metal oxide with said fuel to produce a reduced metal or a reduced metal oxide, and wherein at least a portion of the composite particles and fuel are directly sent to said tube side of said first reactor where the heat of combustion provides heat to the reaction in said shell side of said first reactor;

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 and a hydrogen rich gas stream;

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, optionally the solids discharged from the said second reactor, by oxidizing the metal oxide intermediate;

wherein the ceramic composite particles are mixed with a catalyst, and wherein the catalyst is a water gas shift catalyst, a steam methane reforming catalyst, or a combination thereof.

19. A system for converting fuel comprising:

a first reactor comprising a shell side, a tube side, and a plurality of ceramic composite particles, with the ceramic composite particles comprising at least one metal oxide disposed on a support;

a first inlet for providing a fuel to said shell side of said first reactor; and

a second inlet for providing an oxygen-containing gas to said tube side of said first reactor;

wherein the first reactor is configured to reduce the at least one metal oxide with said fuel to produce a reduced metal or a reduced metal oxide, and wherein at least a portion of the composite particles and fuel are directly sent to said tube side of said first reactor where the heat of combustion provides heat to the reaction in said shell side of said first reactor;

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 and a hydrogen rich gas stream;

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, optionally the solids discharged from the said second reactor, by oxidizing the metal oxide intermediate;

wherein the ceramic composite particles are mixed with a catalyst, and wherein the catalyst comprises 0.01% to 30% by weight of the composite particles.