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Title:
CONVERSION OF METHANE TO DIMETHYL ETHER
Document Type and Number:
WIPO Patent Application WO/2018/004992
Kind Code:
A1
Abstract:
Herein disclosed is a method of producing dimethyl ether (DME) comprising introducing one or more feed streams comprising methane and carbon dioxide into a reformer to generate synthesis gas; and converting synthesis gas to DME in one step. In some cases, the reformer comprises a Ni catalyst. In some cases, the reformer is a pressurized fluidized bed dry reforming reactor. In some cases, the reformer comprises a hydrogen membrane. The hydrogen membrane removes hydrogen contained in the synthesis gas and shifts reforming reactions toward completion.

Inventors:
WRIGHT, Harold A. (1305 Indian Paintbrush Lane, Longmont, Colorado 3, 805503, US)
ROBERTSON, Mark K. (275 South Dahlia Street, Denver, Colorado, 80246, US)
JIANG, Weibin (10935 E. Berry Avenue, Englewood, Colorado, 80111, US)
Application Number:
US2017/035657
Publication Date:
January 04, 2018
Filing Date:
June 02, 2017
Export Citation:
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Assignee:
RES USA, LLC (10170 Church Ranch Way, Suite 200Westminster, Colorado, 80021, US)
International Classes:
C07C41/01; B01D71/02; B01J8/18; B01J23/755; B01J29/072; B01J29/46; C07C43/04
Attorney, Agent or Firm:
WESTBY, Timothy S. (Porter Hedges LLP, 1000 Main St 36th Floo, Houston Texas, 77002, US)
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Claims:
CLAIMS

What is claimed is:

1. A method of producing dimethyl ether (DME) comprising

introducing one or more feed streams comprising methane and carbon dioxide into a reformer to generate synthesis gas; and

converting synthesis gas to DME in one step.

2. The method of claim 1 wherein said reformer comprises a Ni catalyst.

3. The method of claim 1 wherein said reformer is a pressurized fluidized bed dry reforming reactor.

4. The method of claim 1 wherein the reformer comprises a hydrogen membrane.

5. The method of claim 4 wherein said hydrogen membrane removes hydrogen contained in the synthesis gas and shifts reforming reactions toward completion.

6. The method of claim 4 wherein said hydrogen membrane comprises Pd alloy membranes, or Pd alloys supported on ceramic or metal substrates.

7. The method of claim 4 wherein said hydrogen membrane is placed vertically in said reformer as hydrogen membrane tubes hanging from the top of the reformer.

8. The method of claim 4 wherein said hydrogen membrane is coated with an erosion resistant layer.

9. The method of claim 1 wherein said one or more feed streams enter the bottom of the reformer via a manifold or distributor.

10. The method of claim 9 wherein said one or more feed streams fluidize the catalyst in the reformer.

11. The method of claim 1 wherein reformed gas exits the top of the reformer and is separated from spent catalyst.

12. The method of claim 11 wherein spent catalyst is routed to a regenerator in which the catalyst is regenerated.

13. The method of claim 12 wherein regenerated catalyst is returned to the reformer.

14. The method of claim 11 wherein the reformer comprises a cyclone for solid gas separation.

15. The method of claim 1 wherein said reformer uses no process water and requires no oxygen.

16. The method of claim 1 wherein a bi -functional catalyst is used to convert synthesis gas to DME in one step.

17. The method of claim 16 wherein said bi-functional catalyst is capable of methanol synthesis and dehydration.

18. The method of claim 16 wherein said bi-functional catalyst comprise Ni/Ce-Zr02/A1203, , CuO-ZnO-A1203 (CZA) over Clinoptilolite, CZA over gamma-alumina, CZA over zeolites, wherein said zeolites include ferrierite, Zr02, ZSM-5, NaY, HY.

19. The method of claim 1 wherein a multi -tubular fixed bed reactor is used for converting synthesis gas to DME.

20. The method of claim 18 wherein said multi -tubular fixed bed reactor is placed inside a shell, wherein water is circulated.

21. The method of claim 1 comprising recovering and separating DME as product.

22. The method of claim 1 comprising collecting and separating carbon dioxide for recycle to the reformer.

Description:
CONVERSION OF METHANE TO DIMETHYL ETHER

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0001] Not applicable.

BACKGROUND

Field of the Invention

[0002] This disclosure relates generally to the conversion of methane to dimethyl ether. More particularly, this disclosure relates to the conversion of methane to dimethyl ether via dry reforming.

Background of Invention

[0003] Dimethyl ether (DME), also known as methoxymethane, is the organic compound with the formula CH 3 OCH 3 , simplified to C 2 H 5 O. The simplest ether, it is a colorless gas that is a useful precursor to other organic compounds and an aerosol propellant and is being studied as a future energy option. It is an isomer of ethanol.

[0004] The largest use of dimethyl ether is as a blendstock in liquefied petroleum gas (LPG). Dimethyl ether can also be used as a diesel fuel substitute in compression ignition engines.

[0005] DME is typically produced by dehydration of methanol:

2 CH 3 OH→ (CH 3 ) 2 0 + H 2 0

[0006] The required methanol is obtained from synthesis gas (syngas). It is possible for the methanol to be obtained from organic waste or biomass.

[0007] However, it is desirable to have lower natural gas consumption per liter of DME produced, less process water consumption, less oxygen consumption, and lower greenhouse gas (GHG) emissions. As such, there is continuing interest and need to develop new methods and systems to produce dimethyl ether (DME).

SUMMARY

[0008] Herein disclosed is a method of producing dimethyl ether (DME) comprising introducing one or more feed streams comprising methane and carbon dioxide into a reformer to generate synthesis gas; and converting synthesis gas to DME in one step.

[0009] In an embodiment, the reformer comprises a Ni catalyst. In an embodiment, the reformer is a pressurized fluidized bed dry reforming reactor. In an embodiment, the reformer comprises a hydrogen membrane. In an embodiment, the hydrogen membrane removes hydrogen contained in the synthesis gas and shifts reforming reactions toward completion. In an embodiment, the hydrogen membrane comprises Pd alloy membranes, or Pd alloys supported on ceramic or metal substrates. In an embodiment, the hydrogen membrane is placed vertically in the reformer as hydrogen membrane tubes hanging from the top of the reformer. In an embodiment, hydrogen is collected from the hydrogen membrane tubes via one or more internal manifolds and sent to an external hydrogen collection system.

[0010] In an embodiment, the one or more feed streams enter the bottom of the reformer via a manifold or distributor. In an embodiment, the one or more feed streams fluidize the catalyst in the reformer.

[0011] In an embodiment, reformed gas exits the top of the reformer and is separated from spent catalyst. In an embodiment, spent catalyst is routed to a regenerator in which the catalyst is regenerated. In an embodiment, regenerated catalyst is returned to the reformer. In an embodiment, the reformer comprises a cyclone for solid gas separation. In an embodiment, the reformer uses no process water and requires no oxygen.

[0012] In an embodiment, a bi-functional catalyst is used to convert synthesis gas to DME in one step. In an embodiment, the bi-functional catalyst is capable of methanol synthesis and dehydration. In an embodiment, the bi-functional catalyst comprise Ni/Ce-Zr02/A1203 with methanol dehydration catalyst (gamma-alumina), bifunctional nanocatalysts, CuO-ZnO- A1203 (CZA) over Clinoptilolite, CZA over various zeolites including ferrierite, Zr02, ZSM-5, NaY or HY.

[0013] In an embodiment, a multi-tubular fixed bed reactor is used for converting synthesis gas to DME. In an embodiment, the multi-tubular fixed bed reactor is placed inside a shell, wherein water is circulated.

[0014] In an embodiment, the method further comprises recovering and separating DME as product. In an embodiment, the method further comprises collecting and separating carbon dioxide for recycle to the reformer.

[0015] The foregoing has outlined rather broadly the features and technical advantages of the invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter that form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] For a detailed description of the preferred embodiments of the invention, reference will now be made to the accompanying drawings in which:

[0017] Figure 1 is a simplified block flow diagram illustrating the process for the production of DME from natural gas, according to an embodiment of this disclosure.

[0018] Figure 2 is a sketch illustrating the configuration of a reformer reactor, according to an embodiment of this disclosure.

[0019] Figure 3 is a diagram graph illustrating the ability to produce a 1 : 1 H 2 :CO syngas at elevated pressure and reduced temperature in the reforming reactor, according to an embodiment of this disclosure.

[0020] Figure 4 shows an experimental set up of dry reforming, according to an embodiment of this disclosure.

[0021] Figure 5 illustrates an overall process flow sheet for process integration, according to an embodiment of this disclosure.

DETAILED DESCRIPTION

[0022] Herein disclosed is a method of producing dimethyl ether (DME) comprising introducing one or more feed streams comprising methane and carbon dioxide into a reformer to generate synthesis gas; and converting synthesis gas to DME in one step.

[0023] In an embodiment, the reformer comprises a Ni catalyst. In an embodiment, the reformer is a pressurized fluidized bed dry reforming reactor. In an embodiment, the reformer comprises a hydrogen membrane. In an embodiment, the hydrogen membrane removes hydrogen contained in the synthesis gas and shifts reforming reactions toward completion. In an embodiment, the hydrogen membrane comprises Pd alloy membranes, or Pd alloys supported on ceramic or metal substrates. In an embodiment, the membrane is coated with an erosion resistant layer. In an embodiment, the hydrogen membrane is placed vertically in the reformer as hydrogen membrane tubes hanging from the top of the reformer. In an embodiment, hydrogen is collected from the hydrogen membrane tubes via one or more internal manifolds and sent to an external hydrogen collection system. [0024] In an embodiment, the one or more feed streams enter the bottom of the reformer via a manifold or distributor. In an embodiment, the one or more feed streams fluidize the catalyst in the reformer.

[0025] In an embodiment, reformed gas exits the top of the reformer and is separated from spent catalyst. In an embodiment, spent catalyst is routed to a regenerator in which the catalyst is regenerated. In an embodiment, regenerated catalyst is returned to the reformer. In an embodiment, the reformer comprises a cyclone for solid gas separation. In an embodiment, the reformer uses no process water and requires no oxygen.

[0026] In an embodiment, a bi-functional catalyst is used to convert synthesis gas to DME in one step. In an embodiment, the bi-functional catalyst is capable of methanol synthesis and dehydration. In an embodiment, the bi-functional catalyst comprise Ni/Ce-Zr02/A1203, CuO- ZnO-A1203 (CZA) over Clinoptilolite, CZA over gamma-alumina, CZA over various zeolites including ferrierite, Zr02, ZSM-5, NaY or HY.

[0027] In an embodiment, a multi-tubular fixed bed reactor is used for converting synthesis gas to DME. In an embodiment, the multi-tubular fixed bed reactor is placed inside a shell, wherein water is circulated.

[0028] In an embodiment, the method further comprises recovering and separating DME as product. In an embodiment, the method further comprises collecting and separating carbon dioxide for recycle to the reformer.

[0029] The overall chemical reaction for the process envisaged for the production of Dimethyl

Ether (DME) (C 2 H 6 0) from methane and carbon dioxide is: 3 CH 4 + C0 2 = 2 C 2 H 6 0.

[0030] In this process, carbon dioxide is consumed and converted into a useful product DME that can be used as a transportation fuel including as a replacement for diesel.

[0031] The dry reforming step uses a fluidized bed reactor with a Ni catalyst to convert methane to syngas. CH 4 + C0 2 = 2H 2 + 2CO

[0032] It is generally not easy to get to a H 2 to CO ratio of 1 in the product in practice. Catalysts often coke, deactivate, or are limited in the conversion of methane and result in a lower H 2 to CO ratio than desired.

[0033] The syngas to DME reaction can be written as: 6 H 2 + 6 CO = 2 C 2 H 6 0 (DME) + 2 C0 2

[0034] In some cases, the fluidized bed dry reforming reactor also contains a hydrogen membrane to preferentially remove hydrogen produced and force the reaction toward full conversion of the C0 2 and methane. [0035] This dry reforming process is superior to other routes for the production of DME. It uses less natural gas than competing processes, uses no process water, and requires no oxygen plant, and has significantly lower greenhouse gas (GHG) emissions than the competing processes for DME production.

[0036] Figure 1 shows a simplified block flow diagram for this process. Figure 1 also illustrates flows and balances for a commercial process for the production of DME from natural gas.

[0037] Dry reforming. A pressurized fluidized bed (dry) reforming reactor utilizing Pd alloy membranes, or Pd alloy membranes supported on ceramic or other metal substrates inserted into the fluidized bed for the purpose of permeating H 2 generated in the dry reforming reaction. A hydrocarbon feed stream, containing carbon dioxide or co-fed with carbon dioxide, is fed and distributed into the base of the fluidized bed reformer, via a manifold or distributor. The reformer vessel is partially filled with a nickel based catalyst, suitable for dry reforming operating conditions.

[0038] Reformed gas exits the top of the fluidized bed reformer, where it is separated from the catalyst. Spent catalyst is routed to a regenerator, where the catalyst is regenerated in an oxidizing environment. The regenerated catalyst is returned to the Reformer. In an embodiment, hydrogen produced in the reformer is extracted from the reformer fluidized bed, via multiple vertically oriented palladium alloy supported on porous steel tubes or ceramic substrates or other metallic substrates, essentially 100% selective to H 2 , located within the fluidized bed. The permeated H 2 is collected from the multiple membrane tubes via internal manifold(s), which route the H 2 to an external collection system. In an embodiment, the membrane is coated with an erosion resistant layer.

[0039] As H 2 is permeated from the fluidized bed reformer, the dry reforming equilibria is shifted such that dry reforming reactions can proceed to completion. The H 2 permeation facilitates the high degree of dry reforming, without the use of any steam or oxygen injection into the reformer, at lower reforming temperatures and higher pressures than without the H 2 membranes.

[0040] Reformer / reforming reactor / reformer reactor. In an embodiment, Figure 2 shows the configuration of the reformer reactor. The reformer operates at approximately 600-700°C at a pressure of 700 - 800 kPa. Catalyst is fluidized by the incoming methane (or other hydrocarbon) and carbon dioxide feed. The feed gas passes through a gas distributor. The catalyst-gas mixture is in a fluidized bed. Inside the fluidized bed the hydrogen membranes tubes are placed hanging from the top of the reformer. The methane and carbon dioxide are reacted over the fluidized catalyst. The reaction will cause the formation of hydrogen and carbon monoxide via the dry reforming reaction.

[0041] In an embodiment, hydrogen will permeate through the membranes and be collected as hydrogen product leaving the reactor. The methane and carbon dioxide will continue to react as some of the hydrogen permeates away producing more hydrogen and carbon monoxide.

[0042] In some embodiments, the reformer has a top section that contains a cyclone for solid gas separation. Some amount of catalyst will continue to be transported toward the top of the reactor. The gas/catalyst mixture will enter the cyclone and the solid catalyst particles will separate from the gas and fall back toward the bottom of the reactor. The gas produced leaves the top of the reformer. Catalyst also leaves the reformer through an exit and the catalyst will then proceed to the regenerator. Regenerated catalyst enters the reformer catalyst bed as hot catalyst that supplies heat to the reformer. The catalyst will enter at approximately 900- 1000 °C. The catalyst residence time in the reformer is in the range of 0.5 - 4 minutes. The fluidized bed is preferentially operated in turbulent regime. The gas superficial velocity is in the range of 1 - 3 m/s.

[0043] The Nickel catalyst in the reformer with a mean particle size of approximately 200 microns and a nickel content of 2- 6 wt% on an alpha alumina support. For use in the system, the catalyst must be fluidizable, generically spherical, and must be attrition resistant during operation. Suitable nickel alumina catalyst is disclosed, for example, in international patent application number PCT/US2005/036588, which is hereby incorporated herein in its entirety for all purposes not contrary to this disclosure and suitable nickel catalyst is disclosed, for example, in U.S. Patent 7,915, 196 hereby incorporated herein in its entirety for all purposes not contrary to this disclosure.

[0044] Hydrogen Membranes. The addition of the hydrogen membranes to the reformer is optional but preferred. H 2 produced in the reformer is extracted from the reformer fluidized bed, via multiple vertically oriented palladium alloy supported on a porous ceramic substrate, essentially 100% selective to H 2 , located within the fluidized bed. The permeated H 2 is collected from the multiple membrane tubes via internal manifold(s), which route the H 2 to an external collection system. In an embodiment, the membrane is coated with an erosion resistant layer. [0045] As H 2 is permeated from the fiuidized bed reformer (the fuel reactor), the dry reforming equilibria is shifted such that dry reforming reactions can proceed more or less to completion. The H 2 permeation facilitates a higher degree of dry reforming, without the use of any steam or oxygen injection into the reformer, at lower reforming temperatures and higher pressures than without the H 2 membranes. Figure 3 is a diagram illustrating the ability to produce a 1 : 1 H 2 :CO syngas at elevated pressure and reduced temperature in the reforming reactor. Figure 4 shows an experimental set up of dry reforming.

[0046] Metallic membranes or metal coated ceramic supported membranes are hung inside the dual fluidized bed reactor, such as Pd or Pd alloy coated cylindrical structures hung inside the fiuidized bed reactor or any other suitable structures. In an embodiment, the membrane is coated with an erosion resistant layer. Palladium (Pd) based membranes have high hydrogen permeability and an almost infinite selectivity to hydrogen. A thin coating of Pd or Pd alloy 2 - 50 microns thick (with the minimal thickness being preferred for permeation but slightly thicker membranes desired for long term stability of the membrane) is deposited on the cylindrical support material. Ag, Pt, Au, Rh, Ru, and Pb additives have been added to the Pd to form alloys and improve hydrogen permeability. Self-supporting tubular hydrogen membranes have been successfully scaled up and are also contemplated for use in this catalytic membrane reactor/reformer.

[0047] The permeation rate through the hydrogen membranes varies significantly. The hydrogen permeation flux rates can vary from 10 -300 NM3 H2/hr/m2 of membrane area with the preferred range of 20-80 NM3 H2/hr/m2. The permeate pressure is relatively low at sub- atmospheric pressure (as low as 1 psia or approximately 7 kPa). The proper choice of the balance between membrane surface area, hydrogen permeation, and overall reactor performance dictate the exact configuration of the reactor/reformer system.

[0048] The hydrogen product that goes to the manifold is then compressed and blended back with the reformer product gas to produce a combined syngas with a 1 : 1 hydrogen to carbon monoxide ratio. In some cases, sweep gas on the permeate side of the membrane is used to increase the flux at a higher pressure and reduce compression costs. If sweep gas is needed or desired, syngas or reformer product gas or steam is used as the sweep gas.

[0049] Regenerator. Catalyst from the reformer is sent to the regenerator. The catalyst in the reformer can become deactivated by contaminants or by carbon deposited on the catalyst during the dry reforming reaction. Carbon formation during dry reforming reaction is one of the common problems with dry reforming process that uses a fixed bed. One of the advantages of using a fluidized bed reactor is that the catalyst can be regenerated frequently in air.

[0050] In an embodiment, the regenerator operates at approximately 900 - 1000 °C and catalyst is fluidized by air supplied by an air blower or other means at the bottom of the regenerator. Any carbon on the catalyst is burned off in the regenerator. In one embodiment, the regenerator is a fast fluidized bed or a turbulent dense bed where the air and catalyst are mixed at the bottom of the regenerator and the catalyst is conveyed to the top of the regenerator where the catalyst and flue gas are separated out. The superficial gas velocity in the regenerator dense bed is maintained at 1-3 m/s. The hot catalyst then recirculates to the entry nozzle on the reformer. In some embodiments, there is very little or no excess oxygen at the top of the regenerator or in the dense bed. In some cases, secondary air is added at top of regenerator after catalyst separation.

[0051] In cases wherein carbon on the catalyst is not sufficient to keep the regenerator at the high temperature needed, supplemental fuel can be burned in the regenerator to heat the regenerator to operating temperature. In one embodiment, a mixer/burner is placed in the regenerator or adjacent to the regenerator vessel. Fuel and air are mixed and burned in the burner with the combustion product gases flowing into the regenerator and supplying any needed heat to the system. In an embodiment, methane is used as the supplemental fuel to the regenerator. In other embodiments, other fuels to the regenerator are used, such as renewable fuels including landfill gas, bio-ethanol, bio-digester gas, pyrolysis oils and liquid fuels, spent glycerol, biomass derived syngas. Alternatively, biomass is used in a biomass boiler where the hot flue gas from the boiler is used to heat the regenerator to operating temperature.

[0052] DME Production from Syngas. The hydrogen from the manifold is compressed and blended with the reformer product gas to produce a 1 : 1 H2/CO ratio syngas. The blended syngas is compressed to approximately 5500 kPa. The blended syngas is reacted to produce primarily a Dimethyl Ether product by this reaction: 6 H 2 + 6 CO = 2 C 2 H 6 0 (DME) + 2 C0 2

[0053] In various embodiments, a single step is used to convert syngas to DME. There are multiple-step reactions that can also obtain DME as a product including a first step where syngas is converted to methanol and then methanol is dehydrated to DME. For one step synthesis, a bi-functional catalyst is used that does methanol synthesis and dehydration. There are a number of catalysts that can produce DME, such as mixtures of methanol catalyst (CuO/ZnO/A1203) with methanol dehydration catalysts (gamma-alumina). Other bifunctional catalysts such as Ni/Ce-Zr02/A1203, CuO-ZnO-A1203 (CZA) over Clinoptilolite, CZA over various zeolites including ferrierite, Zr02, ZSM-5, NaY or HY, are also used.

[0054] In an embodiment, slurry reactors and fixed bed reactors are used to produce DME from syngas. In an embodiment, a multi-tubular fixed bed reactor is used to produce DME from syngas to take advantage of the exothermic DME reaction and to better control reactor temperature and avoid hot spots.

[0055] In an embodiment, the conversion reactor has individual tubes of 20 - 30 mm in diameter filled with catalyst pellets. Syngas passes through the tubes and react to produce DME. In some embodiments, the reactor tubes are placed inside a shell. In some cases, inside the shell and around the tubes, water is circulated to regulate reactor temperature. Through the heat release in the reactor tubes, steam is generated in the shell.

[0056] In further embodiments, DME product is recovered from the outlet of the multi-tubular reactor and separated as product. C0 2 byproduct, produced in the DME synthesis loop, is separated for recycle to the dry reformer, via conventional distillation. The additional CO2 required to satisfy the dry reforming stoichiometry is recovered from the pressurized regenerator flue gas, using an amine unit with a solvent such as methyldiethanolamine (MDEA). The CO2 is then recycled as feed to the dry reforming reactor.

[0057] Process integration. In an embodiment as shown in Figure 5, the process as described herein is integrated for commercial application. The components in Figure 5 are explained in Table 1. Other altemative and equivalent arrangements are also possible, which are considered to be within the scope of this disclosure.

Table 1

10 Fluidizing nitrogen

12 Hydrogen

14 Natural gas feedstock

16 External fluegas

18 Natural gas knockout drum

20 Hydrodesulfurizer feed/effluent exchanger

22 Hydrodesulfurizer feed preheater

28 Hydrodesulfurizer vessel

30 C02 plus loop purge Natural gas fuel

Natural gas plus C02 feed

Reformer

Recycle gas

Hydrogen

Hydrogen compressor

Reactor effluent

Recycle compressor

Synthesis gas knockout drum

Process condensate

Air compressor

Synthesis gas compressor

Synthesis gas

Converter (DME Reactor)

Converter Steam Drum

Circulator

Hydrogen permeate

Fuelgas

Loop Purge Recycle Dimethyl ether (DME) DME Column

C02 Column

C02 Compressor

Expander

Methanol Column

Methanol

Fusel oil

Wastewater

Amine Regenerator Amine Pump

C02 Absorber

Fluegas Compressor Table 2

[0058] Advantages. The process as described herein has many advantages over existing processes for the production of DME. This process has (1) lower natural gas consumption per liter of DME produced, (2) no process water consumption, (3) no oxygen consumption, and (4) lower greenhouse gas (GHG) emissions per liter of DME produced. The details of these advantages are shown in Table 2 as this process is compared with tri-reforming schemes.

[0059] While preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g. , from about 1 to about 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13, and so forth). Use of the term "optionally" with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both altematives are intended to be within the scope of the claim. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, and the like. [0060] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent they provide exemplary, procedural or other details supplementary to those set forth herein.