WO2012030350A1 - Reformation and hydrogen purification system - Google Patents

Reformation and hydrogen purification system Download PDF

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Publication number
WO2012030350A1
WO2012030350A1 PCT/US2010/047846 US2010047846W WO2012030350A1 WO 2012030350 A1 WO2012030350 A1 WO 2012030350A1 US 2010047846 W US2010047846 W US 2010047846W WO 2012030350 A1 WO2012030350 A1 WO 2012030350A1
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Prior art keywords
hydrogen
reformer
hydrogen purifier
feedstock
purifier
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PCT/US2010/047846
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French (fr)
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WO2012030350A8 (en
Inventor
Daniel R. Herrig
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Azur Anergy Llc
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Priority to PCT/US2010/047846 priority Critical patent/WO2012030350A1/en
Publication of WO2012030350A1 publication Critical patent/WO2012030350A1/en
Publication of WO2012030350A8 publication Critical patent/WO2012030350A8/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/1604—Starting up the process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • Purified hydrogen has become a common fuel source.
  • Fuel cells for example, use purified hydrogen and an oxidant to produce an electrical potential.
  • a reformer and a hydrogen purifier are commonly used.
  • the reformer chemically converts a feedstock over a catalyst to generate impure hydrogen
  • the hydrogen purifier extracts pure hydrogen from the reformate using a hydrogen-selective membrane.
  • Fig. 1 is a block diagram of an example reformation and hydrogen purification system
  • Fig. 2 is a top view of an example reformation and hydrogen purification system
  • Fig. 3 is a front view of the example reformation and hydrogen purification system of Fig. 2;
  • Fig. 4 is a partial cross-sectional view of the example reformation and hydrogen purification system of Fig. 2 taken along line 4-4;
  • Fig. 5 is a partial cross-sectional view of the example reformation and hydrogen purification system of Fig. 2 before ignition of the burner of the reformer;
  • Fig. 6 is a partial cross-sectional view of the example reformation and hydrogen purification system of Fig. 2 after ignition of the burner of the reformer;
  • Fig. 7 is an example input/output diagram of a reformation and hydrogen purification system
  • Fig. 8 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system in standby mode
  • Fig. 9 is a flow diagram illustrating some of the operations associated with an example method of monitoring a reformation and hydrogen purification system.
  • Fig. 10 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system in back-up mode; all arranged in accordance with various embodiments of the present disclosure. Detailed Description of Embodiments
  • Embodiments include, but are not limited to, methods, apparatuses, and systems for hydrogen generation including reformation and hydrogen purification. Other
  • the present disclosure recognizes that providing feedstock to the reformer at a temperature below the operating temperature of the reformer may have detrimental effects. Providing feedstock to the reformer at a temperature below that of the operating temperature may cause the reformer to experience a drop in temperature at least for a period of time. This drop in temperature may result in process variation, and in some cases, stress on the components of the reformer. [0007]
  • the present disclosure also recognizes that using typical hot-surface igniters or spark igniters in conjunction with combustion for heating the reformer may also cause performance issues. The reformation operation is performed at sustained elevated temperatures, temperatures to which the typical hot-surface igniters or spark igniters are directly exposed. As a result, these hot-surface igniters and spark igniters may require frequent replacement due to failure under this continual high-temperature exposure.
  • microprocessor-based controllers for controlling the reformer and/or hydrogen purifier may also be subject to performance issues.
  • the typical reformation and hydrogen purification operation involves elevated temperatures and humidity, either of which may result in early failure of microprocessors.
  • microprocessors sometimes experience glitches, programming errors, and the like, which directly affect the reliability of controllers enlisting microprocessors.
  • microprocessors are susceptible to electromagnetic interference which can cause failure if the microprocessor is not adequately shielded.
  • the present disclosure also recognizes that historical methods of cooling a reformer by blowing a surplus of air over the reformer, or supplying a surplus of air to the combustion region faces practical limits in certain cases as well as performance penalties. Large air blowers, which may be expensive and require a relatively large amount of electrical power to operate, would typically be used to supply large amounts of cooling air. [0010] Furthermore, the present disclosure recognizes that maintaining a hydrogen purifier (utilizing a hydrogen-selective metal membrane) at elevated operating temperatures for periods of hours to days, when air may be present inside the hydrogen purifier, leads to temporary and reversible deterioration in the performance of the purifier.
  • a hydrogen purifier utilizing a hydrogen-selective metal membrane
  • the described reformation and hydrogen purification system may include one or more of a heater block configured to heat the feedstock before the feedstock is routed to the reformer, a hot element igniter proximately disposed to an opening in an outer wall of the annular reactor and configured to ignite the raffinate to provide heat supporting the vaporization of the feedstock, and a non-microprocessor- based controller for controlling, adjusting, and/or monitoring one or more operations of the reformer and/or the hydrogen purifier.
  • a heater block configured to heat the feedstock before the feedstock is routed to the reformer
  • a hot element igniter proximately disposed to an opening in an outer wall of the annular reactor and configured to ignite the raffinate to provide heat supporting the vaporization of the feedstock
  • a non-microprocessor- based controller for controlling, adjusting, and/or monitoring one or more operations of the reformer and/or the hydrogen purifier.
  • FIG. 1 is a block diagram of an example system 100 including a
  • a basic configuration of the apparatus 101 may include a reformer 102, a hydrogen purifier 104, and a controller 106, all coupled together and generally configured as illustrated.
  • the reformer 102 may be configured to receive feedstock, reform the feedstock, and provide the reformate stream to the hydrogen purifier 104.
  • the hydrogen purifier 104 may be configured to purify the reformate to obtain hydrogen, and provide the hydrogen to a fuel cell 1 12, which may be configured to produce an electrical potential for application to an electrical load (not illustrated).
  • the hydrogen purifier 104 may be further configured to route any hydrogen-depleted gas back to the reformer 102 as fuel for heating the reformer 102.
  • the reformer 102 may include a heater block 108 for pre-heating the incoming feedstock, and a hot-element igniter 1 10 for igniting a burner of the reformer 102 for combusting the incoming fuel from the hydrogen purifier 102.
  • the system 100 may further include one or more accumulation tank(s) 162 arranged between the fuel cell 1 12 and the apparatus 101 , as illustrated.
  • the accumulation tank(s) 162 may be configured to hold an amount of purified hydrogen generated by the apparatus 101 , and to route purified hydrogen to the fuel cell 1 12.
  • the accumulation tank(s) 162 may be configured to route hydrogen back to the hydrogen purifier 104 via a reduction return line 164.
  • the reduction return line 164 may allow the system 100 to provide a hydrogen source to the hydrogen purifier 104 to provide a reducing atmosphere to help keep the foils, membranes, or interior surface of the hydrogen purifier 104 reduced. This reduction may limit oxidation, mitigating potential deleterious effect of air and temperature on the surfaces of hydrogen purifier 104.
  • a control valve 172 may be configured to controllably open and close the reduction return line 164 for providing and discontinuing flow of hydrogen from the accumulation tank(s) 162 to the hydrogen purifier 104.
  • the control valve 172 may be any valve suitable for the application including, for example, a solenoid valve or the like, and the control valve 172 may include a flow control orifice.
  • the control valve 172 may be configured to open for a set duration at a set interval, particularly when the system 100 is in standby or off. For example, and without limitation, the controller 106 may control the control valve 172 to open for 5 seconds every hour when the apparatus 101 is in standby or off to keep the hydrogen purifier 104 in a reduced state.
  • the controller 102 may be any device suitable for monitoring, adjusting, and/or controlling a process of reformation, hydrogen purification, and reduction according to the various methods described herein.
  • the controller 102 may be a computing device (e.g., a computer system, a microprocessor, a
  • microcontroller a programmable logic circuit, etc.
  • an embedded controller e.g., an Application Specific Integrated Circuit (ASIC), or some other equivalent
  • ASIC Application Specific Integrated Circuit
  • non- microprocessor-based controller e.g., relay circuit, etc.
  • non-microprocessor-based controllers may be particularly advantageous, especially where reliability and cost may be important design factors.
  • glitches and code issues as well as susceptibility to electromagnetic radiation (e.g., radio and microwave radiation), may be avoided with non-microprocessor-based controllers.
  • Fig. 2 illustrated is a top view of the example reformation and hydrogen purification apparatus 101.
  • Fig. 3 is a front view of the apparatus 101 of Fig. 2
  • Fig. 4 is a partial cross-sectional view of the system 100 of Fig. 2 taken along line 4-4.
  • the apparatus 101 includes the reformer 102 and the hydrogen purifier 104 housed within an insulated chamber 126.
  • the reformer 102 includes an annular reactor 1 14 and a vaporizer coil 1 16 configured to vaporize and reform a liquid feedstock.
  • the annular reactor 1 14 may be filled with a reforming catalyst 152 adapted to react with the vaporized feedstock to produce hydrogen.
  • the liquid feed may comprise any suitable liquid feedstock such as methanol and water. Other alcohols and hydrocarbons, however, plus water may be similarly suitable.
  • Pressurized feedstock may be provided to the reformer 102 at its inlet line 1 18, and the pressurized feedstock is vaporized by the vaporizer coil 1 16.
  • the vaporized feedstock flows into the annular reformer where it chemically reacts over catalyst 152 to produce hydrogen, and usually, various byproducts (sometimes collectively referred to herein as reformate).
  • the reaction is ideally represented as:
  • the reformate is then provided to the hydrogen purifier 104 via its inlet line 120.
  • the inlet line 120 may include a filter 122.
  • the hydrogen purifier 104 may be any suitable hydrogen purifier.
  • the hydrogen purifier 104 may include a cartridge heater, a pressure transducer, and a catalyst (none is illustrated).
  • the cartridge heater may be configured to internally heat the hydrogen purifier 104 to approximately 300-500°C, and the catalyst (e.g., palladium alloy foil or tube, etc.) may allow the hydrogen (H 2 ) to dissolve into very pure atomic hydrogen ( ⁇ ' ).
  • the resulting hydrogen may contain less than 1 ppm CO.
  • the inlet line 120 may include a cooling apparatus 174.
  • the cooling apparatus 174 may be configured to cool the reformate before it enters the hydrogen purifier 104 so that the temperature of the hydrogen purifier 104 may be more easily controlled.
  • the cooling apparatus 174 may comprise a cooling loop and/or a cooling blower.
  • the cooling loop may be configured as suitable for providing cooling of the reformate.
  • the inlet line 120 may be configured to exit the heated insulating chamber 126 to facilitate the cooling of the reformate prior to re-entering the heated insulating chamber 126 for routing to the hydrogen purifier 104, as illustrated.
  • the apparatus 101 then provides the purified hydrogen at the outlet line 124.
  • the outlet line 124 may be coupled to a fuel cell such as the fuel cell 1 12 illustrated at Fig. 1.
  • a heat exchanger 128 may be provided on the outlet line 124 for cooling the purified hydrogen.
  • the heat exchanger 128 may be configured to cool the purified hydrogen using the incoming feedstock, or the water portion of the feedstock in cases in which the methanol (or other alcohol or hydrocarbon) is mixed at point-of-use (immediately prior to reformer 102) with the water.
  • this heat exchange may also advantageously pre-heat the feedstock before reaching the vaporizer coil 1 16 of the reformer 102, which may help reduce temperature fluctuations seen at the reformer 102.
  • the pressure control switch 157 may be configured to turn the system 100 or reformer 102 off/on depending at least in part on the pressure of the accumulator tank(s) 162. For example, if the pressure control switch 157 is set at 60 psi, the reformer 102 will run, putting pure hydrogen into the accumulation tank(s) 162, until the pressure of the accumulation tank(s) 162 reaches 60 psi. The pressure control switch 157 may then shut the system 100 off. Once the accumulation tank(s) 162 has reached a second set point, 40 psi for example, the pressure control switch 157 may then turn the system 100 or reformer 102 back on.
  • the one-way valve 160 may be configured to prevent back flow from the accumulation tank(s) 162 to the hydrogen purifier 104.
  • the one-way valve 160 or similar backflow prevention device, may be configured to allow flow of hydrogen in one direction only, toward the accumulation tank(s) 162 and not back toward the purifier 102.
  • the one-way valve 160 may be any valve suitable for the purpose including, for example, a check valve, a solenoid, or the like.
  • the system 100 may further comprise a vent valve 159, such as a solenoid or the like, configured to allow excess hydrogen (e.g., hydrogen generated by the apparatus 101 ) to be vented from the system 100.
  • the vent valve 159 is essentially a protection device for the hydrogen purifier 104 to prevent or minimize backpressure in the hydrogen 104 purifier. If, for example, the accumulation tank 162 is filled to 60 psi, all the tubing between the hydrogen purifier 104 and the accumulation tank 162 is also at 60 psi. Then, when the system 100 stops, pressure in the hydrogen purifier 104 may be relieved without also emptying the accumulation tank 162 by a combination of the one-way valve 160, which allows flow in one direction, with the vent valve 159.
  • the one-way valve 160 only allows gas to flow toward the accumulation tank 162, and not back toward the hydrogen purifier 102, and as soon as the system 100 shuts down, the vent valve 159 may open and vent the hydrogen that is still in the hydrogen purifier 104, ensuring that no backpressure is seen by the internal components of the hydrogen purifier 104.
  • the vent valve 159 may remain open for 30 seconds to 3 minutes, or more, depending on the situation.
  • the pressure control switch 157 used in conjunction with optional valve 156, may also be used for the purpose of maintaining a reducing atmosphere of hydrogen within hydrogen purifier 104.
  • the system 100 may include a heater block 108 for pre-heating the incoming feedstock.
  • the heater block 108 may be a thermal ballast configured to be heated by an electric heater (such as a cartridge heater), heat generated by the reformer 102, and/or the ambient temperature within the heated insulating chamber 126. To that end, the heater block 108 may abut the outer wall of the reformer 102.
  • the heater block 108 may be sized to provide at least several minutes (e.g., at least 5 minutes, or up to approximately 15 minutes) of heating of the feedstock.
  • the heater block 108 may be formed of any material with a suitable heat capacity for the purpose of pre-heating the feedstock including, for example, stainless steel, aluminum, etc.
  • the reformate stream provided to the hydrogen purifier 104 may include hydrogen and various byproducts. After extracting the purified hydrogen, the hydrogen purifier 104 may be configured to route the hydrogen-depleted gas (sometimes referred to herein as raffinate) back to the reformer 102 via inlet line 130, through optional valve 156 (such as a check valve or pressure relief valve) and to a burner 134 as illustrated. The burner shown in Figs.
  • 2-6 is circular in cross-section and may be a tube formed into a circular shape to more or less approximate the closest vaporizer coil in shape and dimensions.
  • One end of the burner tube may be connected to the raffinate fuel stream and the opposite end may be closed. Multiple openings in the burner tube may allow for raffinate or other fuel gas to exit the tube and combust.
  • Other burner shapes and designs may be accommodated within the scope of the disclosure.
  • valve may be one selected to operate within the elevated temperature environment.
  • Preferred valve seals, or seats may include ceramic, metal, and soft or compressible graphite.
  • the raffinate is mixed with air provided at inlet line 132, and the burner 134 is then ignited by igniter 1 10 for providing the elevated temperature required for vaporization and reformation of the feedstock.
  • igniter 1 10 no additional fuel source may be needed for supporting combustion by the reformer 102.
  • Fig. 5 is a partial cross-sectional view of the system 100 of Fig. 2 before ignition of the burner 134 of the reformer 102
  • Fig. 6 illustrates the system 100 after ignition of the burner 134.
  • the outer wall 140 enclosing the vaporizer coil 1 16 includes an opening 142 above the burner 134, and in proximity to the opening 142 is an igniter element 144 of the igniter 1 10.
  • the igniter 1 10 may be coupled to a power source 146.
  • the raffinate line 130 Before ignition of the burner 134, the raffinate line 130 may be closed off to prevent flow of raffinate into the burner 134. Air passes over the burner 134 and out through the opening 142. To ignite the burner 134, raffinate or other fuel gas is allowed to pass through line 130 into burner 134. When the raffinate reaches the burner 134, the raffinate is ignited by the heated igniter element 144 and fires upward toward the vaporizer coil 1 16. Because the igniter element 144 lays just outside the outer wall 140, burning and/or damage to the igniter element 144 by the flame 148 may be avoided.
  • any suitable igniter may be used for the igniter 1 10.
  • a hot element igniter may be particularly suitable. This type of igniter may have the additional benefit of being capable of remaining in an on state without greatly increasing the risk of damage to the igniter 1 10. Furthermore, this type of igniter does not emit significant
  • the reformer 102 may optionally include one or more thermocouples 138 for monitoring the temperature of the reformer 102.
  • the system 100 may include one or more of a cooling blower for controlling and/or adjusting the temperature of the apparatus 101 , a pump for pumping in the feedstock, and a solenoid valve on the inlet line 1 18 for controlling and/or adjusting the flow of feedstock into the reformer 102.
  • the reformer 102 may include at least one of an electrical cartridge heater or other electrical heater (not illustrated) for controlling and/or adjusting the temperature of the reformer 102.
  • Fig. 7 is an example input/output diagram of a reformation and hydrogen purification system, in accordance with at least some embodiments of the present disclosure. It should be noted that although the
  • input/output diagram illustrates a number of example inputs and outputs, systems within the scope of this disclosure may include more or fewer inputs and/or outputs than that illustrated. As illustrated, the diagram represents various inputs and outputs between the system 100, the feedstock reservoir 150, and the fuel cell 1 12. The inputs and outputs include movement of feedstock and hydrogen as well as the various signals (represented by a ⁇ symbol) between the elements. One or more of the various inputs and/or outputs may be controlled by a controller such as, for example, the controller 106 illustrated in Fig. 1.
  • feedstock is supplied to the system 100 from the feedstock reservoir 150, and any excess feedstock may be returned to the feedstock reservoir 150 from the system 100 as needed.
  • the feedstock reservoir 150 may be configured to communicate, by way of the Feedstock Level signal, an amount of feedstock remaining in the feedstock reservoir 150.
  • the Feedstock Level signal may indicate either a specific amount of feedstock remaining or may instead be a binary signal indicating either sufficient or insufficient quantity of feedstock based at least in part on a predetermined limit.
  • the system 100 may be configured to take some action based at least in part on receipt of the Feedstock Level signal (e.g., shut down, send a signal to an alarm system or master computer, etc.).
  • the system 100 may be configured to indicate either a ready state or a not-ready state, by way of the System Ready/Not Ready signal.
  • the ready state may indicate that the system 100 is ready and in standby, ready to provide hydrogen to the fuel cell 1 12 for back-up power as needed, while the not-ready state may indicate that the system 100 is unavailable, for whatever reason, to provide hydrogen to the fuel cell 1 12 (e.g., insufficient feedstock,
  • the fuel cell 1 12 may be configured to communicate, by way of the System Run signal, to the system 100 to initiate hydrogen generation.
  • the system 100 may be configured to take some action based at least in part on receipt of the System Run signal (e.g., initiate feedstock, start reformation/hydrogen purification operation, etc.).
  • the system 100 may be configured to communicate various states of the system 100 including, for example, a system fault (System Fault signal), low feedstock ⁇ System Feedstock Level Alarm signal), or run (System Operating signal) state.
  • the system 100 may be configured to communicate one or more of these states to an alarm system, master computer, or some other device suitable for monitoring, adjusting, and/or controlling a process of reformation and hydrogen purification according to the various methods described herein.
  • Fig. 8 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system in stand-by mode
  • Fig. 9 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system to produce hydrogen
  • Fig. 10 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system in a back-up mode, all in accordance with at least some embodiments of the present disclosure. It should be noted that although the method is illustrated as a series of sequential steps, the method is not necessarily order dependent. Moreover, methods within the scope of this disclosure may include more or fewer steps than that illustrated.
  • the method 800 may include one or more functions, operations, or actions as is illustrated by any of blocks 802-820. Processing for the method 800 may start with the system 100 in standby mode, as illustrated at block 802, "System in Standby.” From block 802, the method 800 may proceed to decision block 804, "Temp >T1 ?," in which the system 100 determines whether the temperature of the reformer 102 is greater than a predetermined temperature T1. Temperature T1 may be a predetermined minimum operating temperature for the reformer 102. For example, temperature T1 may be, in some embodiments, 350°C. Other temperatures, however, may also be suitable depending on the particular process.
  • the system 100 may be configured to output a signal indicating the not- ready state as illustrated at block 808, "System Not Ready.”
  • the method 800 may then proceed to block 810, "Heat the Reformer,” in which the reformer 102 is heated (by an electric cartridge heater or other suitable heater, or by combustion of a fuel such as natural gas, propane, or LPG), or in which the heat provided to the reformer 102 is increased.
  • the method 800 may then loop back to block 804, "Temp >T1 ?.”
  • the system 100 may be configured to output a signal indicating the ready state as illustrated at block 806, "System Ready.”
  • the system 100 may remain in "System Ready” mode, block 806, for a prolonged period of time ranging from hours to days, or even longer. In this mode, system 100, and particularly the hydrogen purifier 104, are held at an elevated temperature approximately >T1 and approximately ⁇ T2.
  • the accumulation tank(s) 162 may be configured to route hydrogen back to the hydrogen purifier 104 via a reduction return line 164 when the system 100 is in standby or off.
  • the reduction return line 164 may allow the system 100 to provide a hydrogen source to the hydrogen purifier 104 to provide a reducing atmosphere to help keep the foils, membranes, or interior surface of the hydrogen purifier 104 reduced. This reduction may limit oxidation, mitigating potential deleterious effect of air and temperature on the surfaces of hydrogen purifier 104.
  • the hydrogen purifier 104 may not be perfectly sealed with respect to surrounding air, air may eventually infiltrate into the hydrogen purifier 104 and cause a reversible degradation in the performance (hydrogen flux) of the hydrogen purifier 104 comprising one or more hydrogen-permeable metal membranes (such as alloys of palladium with copper).
  • an optional reduction cycle may be employed. This cyclic process is shown as block 807, "Reduction Cycle.”
  • the control valve 172 may be configured to controllably open and close the reduction return line 164 for a set duration at a set interval for providing and discontinuing flow of hydrogen from the accumulation tank(s) 162 to the hydrogen purifier 104 when the system 100 is in standby or off. For example, and without limitation, the control valve 172 valve may be opened for 5 seconds every hour when the system 100 is in standby or off to keep the hydrogen purifier 104 in a reduced state.
  • valve 156 and pressure control switch 157 may be closed to maintain an elevated pressure within the hydrogen purifier 104 and optional pressure sensor (e.g., pressure transducer, etc.) may be used to sense and communicate the pressure to the controller 106.
  • the pressure control switch 157 may be an electrically operated solenoid valve that is controlled in either the open or closed position based on a signal from the controller 106.
  • the valve 156 should be selected to be compatible with the high operating temperatures to which the valve 156 is subjected; ceramic seats, metal seats and/or soft (compressible) graphite seats in the valve 156 may be preferable over polymer materials.
  • the pressure within the hydrogen purifier 104 may slowly decrease over time.
  • the controller 106 may signal the system 100 to turn on, meaning that feedstock is admitted into the reformer 102 wherein the feedstock is converted to reformate that subsequently flows into the hydrogen purifier 104.
  • the duration of time that the system 100 is turned on may also be adjustable within the range of 1 minute to 10 minutes.
  • the system 100 is turned on and allowed to operate until the pressure within the hydrogen purifier 104 increases and reaches a predetermined value, at which time the system 100 is turned off.
  • the method 800 may proceed to decision block 812, "Temp ⁇ T2?,” in which the system 100 determines whether the temperature of the reformer 102 is less than a predetermined temperature T2.
  • Temperature T2 may be a predetermined optimum operating temperature for the reformer 102.
  • temperature T2 may be, in some embodiments, 400°C. Other temperatures, however, may also be suitable depending on the particular process.
  • temperature T2 may be a temperature less than temperature T1.
  • the method 800 may continue to loop back to block 812, "Temp ⁇ T2?,” until such time the temperature of the reformer 102 is less than temperature T2.
  • one or more other such monitoring operations may be additionally or alternatively performed during the time temperature is determined to be at least temperature T2.
  • the method 800 may optionally proceed to block 816, "Go to 900," block 900 being illustrated in Fig. 9.
  • the method 800 may proceed to block 814, "Heat the Reformer,” in which the reformer 102 is heated (by a cartridge heater or other suitable heater including combustion of a fuel gas such as natural gas, propane, or LPG), or in which the heat provided to the reformer 102 is increased.
  • a cartridge heater or other suitable heater including combustion of a fuel gas such as natural gas, propane, or LPG
  • the method 800 may then proceed to decision block 818, "Temp >T2?," in which the system 100 determines whether the temperature of the reformer 102 is greater than the predetermined temperature T2. If the temperature of the reformer 102 remains equal to or below temperature T2, the method 800 may loop back to decision block 818.
  • Fig. 9 is a flow diagram illustrating some of the optional operations associated with an example method 900 of monitoring a reformation and hydrogen purification system, for example, once the system 100 has entered the "System
  • the method 900 may include one or more functions, operations, or actions as is illustrated by any of blocks 902-924. Processing for the method 900 may start at block 902, "Temp >T3?," in which the system 100 determines whether the temperature of the reformer 102 is greater than a
  • Temperature T3 may be a predetermined temperature greater than temperature T2 suitable for operating the reformer 102.
  • temperature T3 may be, in some embodiments, 415°C. Other temperatures, however, may also be suitable depending on the particular process.
  • reforming methanol plus water may be conducted at a lower temperature (such as 300°C to 450°C) whereas reforming other alcohols and/or hydrocarbons plus water may be conducted at a higher temperature (such as 500°C to 800°C).
  • the method 900 may proceed to block 904 or block 905.
  • Two different cooling modes may be used to reduce the temperature T3 to less than the set value.
  • One method uses an optional cooling blower to force an excess volume of air into reformer 102 to reduce the operating temperature.
  • the second method does not use a cooling blower, rather it drives the combustion occurring at burner 134 into a fuel-rich mixture resulting is a reduction in the heat liberated by the combustion process and subsequent cooling.
  • method 900 may proceed to block 904, "Turn Cooling Blower to High Speed,” in which a cooling blower of the system 100 may be set to high speed to cool the reformer 102. If, on the other hand, the temperature is determined to be less than or equal to temperature T3, the method may proceed to block 906, "Turn Cooling Blower to Low Speed,” in which a cooling blower of the system 100 may be set to low speed to allow the reformer 102 to increase in temperature until such point as the temperature exceeds T3. The method 900 may loop back to block 902 from either block 904 or 906.
  • method 900 may proceed to block 905, "Turn Combustion Blower to Low Speed,” in which a combustion blower of system 100 may be set to low speed causing fuel-rich combustion and resulting in cooling the reformer 102. If, on the other hand, the temperature is determined to be less than or equal to temperature T3, the method may proceed to block 907, "Turn Combustion Blower to High Speed,” in which a combustion blower of system 100 may be set to high speed to allow the reformer 102 to increase in temperature until such point as the temperature exceeds temperature T3. The method may loop back to block 902 from either block 905 or 907.
  • the method 900 may proceed to decision block 908, "Temp >T4?," in which the system 100 determines whether the temperature of the reformer 102 is greater than a predetermined temperature T4.
  • Temperature T4 may be a
  • temperature T3 suitable for monitoring a temperature of the reformer 102.
  • temperature T4 may be, in some embodiments, 450°C. Other temperatures, however, may also be suitable depending on the particular process.
  • the method 900 may proceed to block 910, "Shut System Down,” in which the system 100 is shut down, and a signal indicating the fault state is output as illustrated at block 912, "System Fault.”
  • the method 900 may proceed to decision block 914,
  • Feedstock Level Alarm in which the system 100 determines whether the feedstock level is below (or least) a predetermined level. If the feedstock level is determined to be low, the method 900 may proceed to block 916, "Shut System Down,” in which the system 100 is shut down, and a signal indicating the low feedstock level is output as illustrated at block 918, "System Feedstock Level Alarm.”
  • the method 900 may proceed to decision block 920, "Pressure >or ⁇ P Limit?,” in which the system 100 determines whether the pressure of the hydrogen purifier 104 is above or below a predetermined upper or lower limit. If the pressure is determined to be outside the predetermined operating range, the method 900 may proceed to block 922, "Shut System Down,” in which the system 100 is shut down, and a signal indicating the fault state is output as illustrated at block 918, "System Fault.”
  • the method 900 may proceed to some other operation such as, for example, back to decision block 902.
  • the back-up mode may be a mode in which the system 100 provides back-up power to a power grid.
  • Such back-up power may be used, for example, when a main or primary power grid fails or underperforms.
  • the method 1000 may include one or more functions, operations, or actions as is illustrated by any of blocks 802 or 1004-1020. Processing for the method 1000 may start with the system 100 in stand-by mode, as illustrated at block 802, "System in Standby.” From block 802, the method 1000 may proceed to decision block 1004, "Grid Power Lost?,” in which the system 100 determines or is notified by the fuel cell 1 12 or the controller 106 that the grid power has been lost. If the grid power has not been lost, the method 1000 may loop back to stand-by mode at block 802.
  • the method may proceed to block 1006, "Fuel Cell Initiates Start,” in which the fuel cell 1 12 starts providing back-up power to the grid.
  • the fuel cell 1 12 may also send a signal to the system 100 at block 1008, "System Run,” to direct the system 100 to begin hydrogen generation.
  • the method 1000 may then proceed to block 1010, "System Operating,” in which the system 100 outputs a signal indicating that the system 100 is operational.
  • the method 1000 may optionally proceed to decision block 1012, "Pressure >P Minimum,” in which the system 100 determines whether the pressure of the hydrogen purifier 104 is at least a predetermined minimum pressure limit. If the pressure is determined to be below the predetermined pressure limit, the method 1000 may proceed to block 1014, "System Fault,” in which a signal indicating the fault state is output. The system 100 may be prevented from operating in this situation.
  • the method 1000 may proceed to block 1010, "System Operating,” in which a signal indicating that the system 100 is operational is output.
  • the method 1000 may then optionally proceed to block 1016, "Go to 900," block 900 being illustrated in Fig. 9 and as discussed more fully elsewhere.
  • the method 1000 may then proceed to decision block 1018, "Grid Power On?,” in which the system 100 determines or is notified by the fuel cell 1 12 or the controller 106 that the grid power has been restored. If the grid power has not been restored, the method 1000 may loop back to decision block 1018 or optional block 1016.
  • the method 100 may proceed to block 1020, "Fuel Cell Shuts Down," the fuel cell 1 12 may be shut down and the method may loop back to stand-by mode at block 802, in which the system 100 may be placed back into stand-by mode.

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Abstract

Techniques are generally described herein for the design and manufacture of hydrogen generation. Embodiments include, but are not limited to, methods, apparatuses, and systems. Other embodiments may also be disclosed and claimed. Some systems described herein include a reformer, a hydrogen purifier disposed externally to the reformer, an accumulation tank configured to receive purified hydrogen from the hydrogen purifier, and a reduction return line configured to route the purified hydrogen from the accumulation tank to the hydrogen purifier to provide a reducing atmosphere for one or more surfaces of the hydrogen purifier. One or more operations of the reformer and/or the hydrogen purifier may be controlled, adjusted, and/or monitored by a non-microprocessor-based controller.

Description

REFORMATION AND HYDROGEN PURIFICATION SYSTEM
Background
[0001] Unless otherwise indicated herein, the materials described in this section are not prior art to the claims in this application and are not admitted to be prior art by inclusion in this section.
[0002] Purified hydrogen has become a common fuel source. Fuel cells, for example, use purified hydrogen and an oxidant to produce an electrical potential. To produce purified hydrogen, a reformer and a hydrogen purifier are commonly used. In a typical arrangement, the reformer chemically converts a feedstock over a catalyst to generate impure hydrogen, and the hydrogen purifier extracts pure hydrogen from the reformate using a hydrogen-selective membrane.
Brief Description of the Drawings
[0003] Subject matter is particularly pointed out and distinctly claimed in the concluding portion of the specification. The foregoing and other features of the present disclosure will become more fully apparent from the following description and appended claims, taken in conjunction with the accompanying drawings. Understanding that these drawings depict only several embodiments in accordance with the disclosure and are, therefore, not to be considered limiting of its scope, the disclosure will be described with additional specificity and detail through use of the accompanying drawings, in which:
Fig. 1 is a block diagram of an example reformation and hydrogen purification system; Fig. 2 is a top view of an example reformation and hydrogen purification system;
Fig. 3 is a front view of the example reformation and hydrogen purification system of Fig. 2;
Fig. 4 is a partial cross-sectional view of the example reformation and hydrogen purification system of Fig. 2 taken along line 4-4;
Fig. 5 is a partial cross-sectional view of the example reformation and hydrogen purification system of Fig. 2 before ignition of the burner of the reformer;
Fig. 6 is a partial cross-sectional view of the example reformation and hydrogen purification system of Fig. 2 after ignition of the burner of the reformer;
Fig. 7 is an example input/output diagram of a reformation and hydrogen purification system;
Fig. 8 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system in standby mode;
Fig. 9 is a flow diagram illustrating some of the operations associated with an example method of monitoring a reformation and hydrogen purification system; and
Fig. 10 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system in back-up mode; all arranged in accordance with various embodiments of the present disclosure. Detailed Description of Embodiments
[0004] In the following detailed description, reference is made to the
accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the Figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein.
[0005] This disclosure is generally drawn, inter alia, to hydrogen generation. Embodiments include, but are not limited to, methods, apparatuses, and systems for hydrogen generation including reformation and hydrogen purification. Other
embodiments may also be disclosed and claimed.
[0006] The present disclosure recognizes that providing feedstock to the reformer at a temperature below the operating temperature of the reformer may have detrimental effects. Providing feedstock to the reformer at a temperature below that of the operating temperature may cause the reformer to experience a drop in temperature at least for a period of time. This drop in temperature may result in process variation, and in some cases, stress on the components of the reformer. [0007] The present disclosure also recognizes that using typical hot-surface igniters or spark igniters in conjunction with combustion for heating the reformer may also cause performance issues. The reformation operation is performed at sustained elevated temperatures, temperatures to which the typical hot-surface igniters or spark igniters are directly exposed. As a result, these hot-surface igniters and spark igniters may require frequent replacement due to failure under this continual high-temperature exposure.
[0008] The present disclosure further recognizes that the historical use of microprocessor-based controllers for controlling the reformer and/or hydrogen purifier may also be subject to performance issues. The typical reformation and hydrogen purification operation involves elevated temperatures and humidity, either of which may result in early failure of microprocessors. In addition, microprocessors sometimes experience glitches, programming errors, and the like, which directly affect the reliability of controllers enlisting microprocessors. Furthermore, microprocessors are susceptible to electromagnetic interference which can cause failure if the microprocessor is not adequately shielded.
[0009] The present disclosure also recognizes that historical methods of cooling a reformer by blowing a surplus of air over the reformer, or supplying a surplus of air to the combustion region faces practical limits in certain cases as well as performance penalties. Large air blowers, which may be expensive and require a relatively large amount of electrical power to operate, would typically be used to supply large amounts of cooling air. [0010] Furthermore, the present disclosure recognizes that maintaining a hydrogen purifier (utilizing a hydrogen-selective metal membrane) at elevated operating temperatures for periods of hours to days, when air may be present inside the hydrogen purifier, leads to temporary and reversible deterioration in the performance of the purifier.
[0011] In contrast, the described reformation and hydrogen purification system may include one or more of a heater block configured to heat the feedstock before the feedstock is routed to the reformer, a hot element igniter proximately disposed to an opening in an outer wall of the annular reactor and configured to ignite the raffinate to provide heat supporting the vaporization of the feedstock, and a non-microprocessor- based controller for controlling, adjusting, and/or monitoring one or more operations of the reformer and/or the hydrogen purifier.
[0012] Fig. 1 is a block diagram of an example system 100 including a
reformation and hydrogen purification apparatus 101 , arranged in accordance with at least some embodiments of the present disclosure. A basic configuration of the apparatus 101 may include a reformer 102, a hydrogen purifier 104, and a controller 106, all coupled together and generally configured as illustrated.
[0013] In general, the reformer 102 may be configured to receive feedstock, reform the feedstock, and provide the reformate stream to the hydrogen purifier 104. The hydrogen purifier 104 may be configured to purify the reformate to obtain hydrogen, and provide the hydrogen to a fuel cell 1 12, which may be configured to produce an electrical potential for application to an electrical load (not illustrated). The hydrogen purifier 104 may be further configured to route any hydrogen-depleted gas back to the reformer 102 as fuel for heating the reformer 102.
[0014] As discussed more fully below, the reformer 102 may include a heater block 108 for pre-heating the incoming feedstock, and a hot-element igniter 1 10 for igniting a burner of the reformer 102 for combusting the incoming fuel from the hydrogen purifier 102.
[0015] The system 100 may further include one or more accumulation tank(s) 162 arranged between the fuel cell 1 12 and the apparatus 101 , as illustrated. The accumulation tank(s) 162 may be configured to hold an amount of purified hydrogen generated by the apparatus 101 , and to route purified hydrogen to the fuel cell 1 12.
[0016] The accumulation tank(s) 162 may be configured to route hydrogen back to the hydrogen purifier 104 via a reduction return line 164. The reduction return line 164 may allow the system 100 to provide a hydrogen source to the hydrogen purifier 104 to provide a reducing atmosphere to help keep the foils, membranes, or interior surface of the hydrogen purifier 104 reduced. This reduction may limit oxidation, mitigating potential deleterious effect of air and temperature on the surfaces of hydrogen purifier 104.
[0017] In various embodiments, a control valve 172 may be configured to controllably open and close the reduction return line 164 for providing and discontinuing flow of hydrogen from the accumulation tank(s) 162 to the hydrogen purifier 104. The control valve 172 may be any valve suitable for the application including, for example, a solenoid valve or the like, and the control valve 172 may include a flow control orifice. In various embodiments, the control valve 172 may be configured to open for a set duration at a set interval, particularly when the system 100 is in standby or off. For example, and without limitation, the controller 106 may control the control valve 172 to open for 5 seconds every hour when the apparatus 101 is in standby or off to keep the hydrogen purifier 104 in a reduced state.
[0018] The controller 102 may be any device suitable for monitoring, adjusting, and/or controlling a process of reformation, hydrogen purification, and reduction according to the various methods described herein. For example, the controller 102 may be a computing device (e.g., a computer system, a microprocessor, a
microcontroller, a programmable logic circuit, etc.), an embedded controller (e.g., an Application Specific Integrated Circuit (ASIC), or some other equivalent), or a non- microprocessor-based controller (e.g., relay circuit, etc.).
[0019] As the system 100 may experience temperature extremes (both hot and cold) and varying humidity levels, non-microprocessor-based controllers may be particularly advantageous, especially where reliability and cost may be important design factors. In contrast to microprocessor-based controllers, glitches and code issues, as well as susceptibility to electromagnetic radiation (e.g., radio and microwave radiation), may be avoided with non-microprocessor-based controllers.
[0020] Turning now to Fig. 2, illustrated is a top view of the example reformation and hydrogen purification apparatus 101. Fig. 3 is a front view of the apparatus 101 of Fig. 2, and Fig. 4 is a partial cross-sectional view of the system 100 of Fig. 2 taken along line 4-4. As illustrated, the apparatus 101 includes the reformer 102 and the hydrogen purifier 104 housed within an insulated chamber 126.
[0021] The reformer 102 includes an annular reactor 1 14 and a vaporizer coil 1 16 configured to vaporize and reform a liquid feedstock. The annular reactor 1 14 may be filled with a reforming catalyst 152 adapted to react with the vaporized feedstock to produce hydrogen. The liquid feed may comprise any suitable liquid feedstock such as methanol and water. Other alcohols and hydrocarbons, however, plus water may be similarly suitable. Pressurized feedstock may be provided to the reformer 102 at its inlet line 1 18, and the pressurized feedstock is vaporized by the vaporizer coil 1 16. The vaporized feedstock flows into the annular reformer where it chemically reacts over catalyst 152 to produce hydrogen, and usually, various byproducts (sometimes collectively referred to herein as reformate). For embodiments in which the feedstock is methanol and water, for example, the reaction is ideally represented as:
CH3OH + H2O→ [1 -x-y] CO2 + x CO + [3-x-4y] H2 + y CH4 + [x+2y] H2O wherein CO2, CO, H2O and CH4 are the non-hydrogen byproducts.
[0022] The reformate is then provided to the hydrogen purifier 104 via its inlet line 120. In some embodiments, the inlet line 120 may include a filter 122. The hydrogen purifier 104 may be any suitable hydrogen purifier. In an example configuration, the hydrogen purifier 104 may include a cartridge heater, a pressure transducer, and a catalyst (none is illustrated). The cartridge heater may be configured to internally heat the hydrogen purifier 104 to approximately 300-500°C, and the catalyst (e.g., palladium alloy foil or tube, etc.) may allow the hydrogen (H2) to dissolve into very pure atomic hydrogen (Η'). In various embodiments, the resulting hydrogen may contain less than 1 ppm CO.
[0023] The inlet line 120 may include a cooling apparatus 174. The cooling apparatus 174 may be configured to cool the reformate before it enters the hydrogen purifier 104 so that the temperature of the hydrogen purifier 104 may be more easily controlled. In various embodiments, the cooling apparatus 174 may comprise a cooling loop and/or a cooling blower. For some embodiments in which the cooling apparatus 174 comprises a cooling loop, the cooling loop may be configured as suitable for providing cooling of the reformate.
[0024] Moreover, the inlet line 120 may be configured to exit the heated insulating chamber 126 to facilitate the cooling of the reformate prior to re-entering the heated insulating chamber 126 for routing to the hydrogen purifier 104, as illustrated.
[0025] The apparatus 101 then provides the purified hydrogen at the outlet line 124. In various embodiments, the outlet line 124 may be coupled to a fuel cell such as the fuel cell 1 12 illustrated at Fig. 1. As the purified hydrogen leaving the hydrogen purifier 104 may be at an elevated temperature (e.g., 300-500°C), a heat exchanger 128 may be provided on the outlet line 124 for cooling the purified hydrogen. The heat exchanger 128 may be configured to cool the purified hydrogen using the incoming feedstock, or the water portion of the feedstock in cases in which the methanol (or other alcohol or hydrocarbon) is mixed at point-of-use (immediately prior to reformer 102) with the water. In addition to cooling the outgoing purified hydrogen, this heat exchange may also advantageously pre-heat the feedstock before reaching the vaporizer coil 1 16 of the reformer 102, which may help reduce temperature fluctuations seen at the reformer 102.
[0026] The pressure control switch 157 may be configured to turn the system 100 or reformer 102 off/on depending at least in part on the pressure of the accumulator tank(s) 162. For example, if the pressure control switch 157 is set at 60 psi, the reformer 102 will run, putting pure hydrogen into the accumulation tank(s) 162, until the pressure of the accumulation tank(s) 162 reaches 60 psi. The pressure control switch 157 may then shut the system 100 off. Once the accumulation tank(s) 162 has reached a second set point, 40 psi for example, the pressure control switch 157 may then turn the system 100 or reformer 102 back on.
[0027] The one-way valve 160 may be configured to prevent back flow from the accumulation tank(s) 162 to the hydrogen purifier 104. The one-way valve 160, or similar backflow prevention device, may be configured to allow flow of hydrogen in one direction only, toward the accumulation tank(s) 162 and not back toward the purifier 102. The one-way valve 160 may be any valve suitable for the purpose including, for example, a check valve, a solenoid, or the like.
[0028] They system 100 may further comprise a vent valve 159, such as a solenoid or the like, configured to allow excess hydrogen (e.g., hydrogen generated by the apparatus 101 ) to be vented from the system 100. The vent valve 159 is essentially a protection device for the hydrogen purifier 104 to prevent or minimize backpressure in the hydrogen 104 purifier. If, for example, the accumulation tank 162 is filled to 60 psi, all the tubing between the hydrogen purifier 104 and the accumulation tank 162 is also at 60 psi. Then, when the system 100 stops, pressure in the hydrogen purifier 104 may be relieved without also emptying the accumulation tank 162 by a combination of the one-way valve 160, which allows flow in one direction, with the vent valve 159. The one-way valve 160 only allows gas to flow toward the accumulation tank 162, and not back toward the hydrogen purifier 102, and as soon as the system 100 shuts down, the vent valve 159 may open and vent the hydrogen that is still in the hydrogen purifier 104, ensuring that no backpressure is seen by the internal components of the hydrogen purifier 104. The vent valve 159 may remain open for 30 seconds to 3 minutes, or more, depending on the situation.
[0029] The pressure control switch 157, used in conjunction with optional valve 156, may also be used for the purpose of maintaining a reducing atmosphere of hydrogen within hydrogen purifier 104.
[0030] In addition or alternatively to pre-heating the incoming feedstock by heat exchanger 128, the system 100 may include a heater block 108 for pre-heating the incoming feedstock. The heater block 108 may be a thermal ballast configured to be heated by an electric heater (such as a cartridge heater), heat generated by the reformer 102, and/or the ambient temperature within the heated insulating chamber 126. To that end, the heater block 108 may abut the outer wall of the reformer 102. The heater block 108 may be sized to provide at least several minutes (e.g., at least 5 minutes, or up to approximately 15 minutes) of heating of the feedstock. The heater block 108 may be formed of any material with a suitable heat capacity for the purpose of pre-heating the feedstock including, for example, stainless steel, aluminum, etc. [0031] As discussed herein, the reformate stream provided to the hydrogen purifier 104 may include hydrogen and various byproducts. After extracting the purified hydrogen, the hydrogen purifier 104 may be configured to route the hydrogen-depleted gas (sometimes referred to herein as raffinate) back to the reformer 102 via inlet line 130, through optional valve 156 (such as a check valve or pressure relief valve) and to a burner 134 as illustrated. The burner shown in Figs. 2-6 is circular in cross-section and may be a tube formed into a circular shape to more or less approximate the closest vaporizer coil in shape and dimensions. One end of the burner tube may be connected to the raffinate fuel stream and the opposite end may be closed. Multiple openings in the burner tube may allow for raffinate or other fuel gas to exit the tube and combust. Other burner shapes and designs may be accommodated within the scope of the disclosure.
[0032] If the optional valve 156 is employed, the valve may be one selected to operate within the elevated temperature environment. Preferred valve seals, or seats, may include ceramic, metal, and soft or compressible graphite.
[0033] At the reformer 102, the raffinate is mixed with air provided at inlet line 132, and the burner 134 is then ignited by igniter 1 10 for providing the elevated temperature required for vaporization and reformation of the feedstock. In this arrangement, no additional fuel source may be needed for supporting combustion by the reformer 102.
[0034] The igniter 1 10 of the system 100 may be more clearly understood with reference to Figs. 5 and 6. Fig. 5 is a partial cross-sectional view of the system 100 of Fig. 2 before ignition of the burner 134 of the reformer 102, while Fig. 6 illustrates the system 100 after ignition of the burner 134. As illustrated, the outer wall 140 enclosing the vaporizer coil 1 16 includes an opening 142 above the burner 134, and in proximity to the opening 142 is an igniter element 144 of the igniter 1 10. The igniter 1 10 may be coupled to a power source 146.
[0035] Before ignition of the burner 134, the raffinate line 130 may be closed off to prevent flow of raffinate into the burner 134. Air passes over the burner 134 and out through the opening 142. To ignite the burner 134, raffinate or other fuel gas is allowed to pass through line 130 into burner 134. When the raffinate reaches the burner 134, the raffinate is ignited by the heated igniter element 144 and fires upward toward the vaporizer coil 1 16. Because the igniter element 144 lays just outside the outer wall 140, burning and/or damage to the igniter element 144 by the flame 148 may be avoided.
[0036] Any suitable igniter may be used for the igniter 1 10. A hot element igniter may be particularly suitable. This type of igniter may have the additional benefit of being capable of remaining in an on state without greatly increasing the risk of damage to the igniter 1 10. Furthermore, this type of igniter does not emit significant
electromagnetic radiation unlike spark igniters.
[0037] Referring again to the apparatus 101 in general, the reformer 102 may optionally include one or more thermocouples 138 for monitoring the temperature of the reformer 102. In addition, although not illustrated, the system 100 may include one or more of a cooling blower for controlling and/or adjusting the temperature of the apparatus 101 , a pump for pumping in the feedstock, and a solenoid valve on the inlet line 1 18 for controlling and/or adjusting the flow of feedstock into the reformer 102. The reformer 102 may include at least one of an electrical cartridge heater or other electrical heater (not illustrated) for controlling and/or adjusting the temperature of the reformer 102.
[0038] The system 100 and apparatus 101 of Figs. 1 -6 may be more clearly understood with reference to Fig. 7. Fig. 7 is an example input/output diagram of a reformation and hydrogen purification system, in accordance with at least some embodiments of the present disclosure. It should be noted that although the
input/output diagram illustrates a number of example inputs and outputs, systems within the scope of this disclosure may include more or fewer inputs and/or outputs than that illustrated. As illustrated, the diagram represents various inputs and outputs between the system 100, the feedstock reservoir 150, and the fuel cell 1 12. The inputs and outputs include movement of feedstock and hydrogen as well as the various signals (represented by a Δ symbol) between the elements. One or more of the various inputs and/or outputs may be controlled by a controller such as, for example, the controller 106 illustrated in Fig. 1.
[0039] Between the feedstock reservoir 150 and the system 100, feedstock is supplied to the system 100 from the feedstock reservoir 150, and any excess feedstock may be returned to the feedstock reservoir 150 from the system 100 as needed. The feedstock reservoir 150 may be configured to communicate, by way of the Feedstock Level signal, an amount of feedstock remaining in the feedstock reservoir 150. In some embodiments, the Feedstock Level signal may indicate either a specific amount of feedstock remaining or may instead be a binary signal indicating either sufficient or insufficient quantity of feedstock based at least in part on a predetermined limit. The system 100 may be configured to take some action based at least in part on receipt of the Feedstock Level signal (e.g., shut down, send a signal to an alarm system or master computer, etc.).
[0040] Between the fuel cell 1 12 and the system 100, hydrogen is provided to the fuel cell 1 12 from the system 100. In addition, the system 100 may be configured to indicate either a ready state or a not-ready state, by way of the System Ready/Not Ready signal. The ready state may indicate that the system 100 is ready and in standby, ready to provide hydrogen to the fuel cell 1 12 for back-up power as needed, while the not-ready state may indicate that the system 100 is unavailable, for whatever reason, to provide hydrogen to the fuel cell 1 12 (e.g., insufficient feedstock,
overheating, underheating, equipment failure, or some other system fault). Separate signals may be enlisted for the ready state and the not ready state, or instead, a single binary signal may indicate either the ready or the not ready state, the absence of signal indicating the other state.
[0041] The fuel cell 1 12 may be configured to communicate, by way of the System Run signal, to the system 100 to initiate hydrogen generation. The system 100 may be configured to take some action based at least in part on receipt of the System Run signal (e.g., initiate feedstock, start reformation/hydrogen purification operation, etc.).
[0042] The system 100 may be configured to communicate various states of the system 100 including, for example, a system fault (System Fault signal), low feedstock {System Feedstock Level Alarm signal), or run (System Operating signal) state. The system 100 may be configured to communicate one or more of these states to an alarm system, master computer, or some other device suitable for monitoring, adjusting, and/or controlling a process of reformation and hydrogen purification according to the various methods described herein.
[0043] The system 100 of Figs. 1 -6, and the input/output arrangement of Fig. 7, may be more clearly understood with reference to Figs. 8-10. Fig. 8 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system in stand-by mode, Fig. 9 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system to produce hydrogen, and Fig. 10 is a flow diagram illustrating some of the operations associated with an example method of operating a reformation and hydrogen purification system in a back-up mode, all in accordance with at least some embodiments of the present disclosure. It should be noted that although the method is illustrated as a series of sequential steps, the method is not necessarily order dependent. Moreover, methods within the scope of this disclosure may include more or fewer steps than that illustrated.
[0044] Turning first to Fig. 8, with continued reference to the system 100 illustrated in Figs. 1 -6 and input/output arrangement illustrated in Fig. 7, the method 800 may include one or more functions, operations, or actions as is illustrated by any of blocks 802-820. Processing for the method 800 may start with the system 100 in standby mode, as illustrated at block 802, "System in Standby." From block 802, the method 800 may proceed to decision block 804, "Temp >T1 ?," in which the system 100 determines whether the temperature of the reformer 102 is greater than a predetermined temperature T1. Temperature T1 may be a predetermined minimum operating temperature for the reformer 102. For example, temperature T1 may be, in some embodiments, 350°C. Other temperatures, however, may also be suitable depending on the particular process.
[0045] If the temperature is determined to be equal to or less than the
temperature T1 , the system 100 may be configured to output a signal indicating the not- ready state as illustrated at block 808, "System Not Ready." The method 800 may then proceed to block 810, "Heat the Reformer," in which the reformer 102 is heated (by an electric cartridge heater or other suitable heater, or by combustion of a fuel such as natural gas, propane, or LPG), or in which the heat provided to the reformer 102 is increased. The method 800 may then loop back to block 804, "Temp >T1 ?."
[0046] If, on the other hand, the temperature is determined to be greater than temperature T1 , the system 100 may be configured to output a signal indicating the ready state as illustrated at block 806, "System Ready." The system 100 may remain in "System Ready" mode, block 806, for a prolonged period of time ranging from hours to days, or even longer. In this mode, system 100, and particularly the hydrogen purifier 104, are held at an elevated temperature approximately >T1 and approximately <T2.
[0047] As discussed herein, the accumulation tank(s) 162 may be configured to route hydrogen back to the hydrogen purifier 104 via a reduction return line 164 when the system 100 is in standby or off. The reduction return line 164 may allow the system 100 to provide a hydrogen source to the hydrogen purifier 104 to provide a reducing atmosphere to help keep the foils, membranes, or interior surface of the hydrogen purifier 104 reduced. This reduction may limit oxidation, mitigating potential deleterious effect of air and temperature on the surfaces of hydrogen purifier 104. In some instances, since the hydrogen purifier 104 may not be perfectly sealed with respect to surrounding air, air may eventually infiltrate into the hydrogen purifier 104 and cause a reversible degradation in the performance (hydrogen flux) of the hydrogen purifier 104 comprising one or more hydrogen-permeable metal membranes (such as alloys of palladium with copper).
[0048] To mitigate the deleterious effect of air and temperature on said metal membranes, an optional reduction cycle may be employed. This cyclic process is shown as block 807, "Reduction Cycle." The control valve 172 may be configured to controllably open and close the reduction return line 164 for a set duration at a set interval for providing and discontinuing flow of hydrogen from the accumulation tank(s) 162 to the hydrogen purifier 104 when the system 100 is in standby or off. For example, and without limitation, the control valve 172 valve may be opened for 5 seconds every hour when the system 100 is in standby or off to keep the hydrogen purifier 104 in a reduced state.
[0049] Alternatively to using a timed reduction cycle as described above, optional valve 156 and pressure control switch 157 (e.g., a check valve, pressure relief valve, etc.) may be closed to maintain an elevated pressure within the hydrogen purifier 104 and optional pressure sensor (e.g., pressure transducer, etc.) may be used to sense and communicate the pressure to the controller 106. The pressure control switch 157 may be an electrically operated solenoid valve that is controlled in either the open or closed position based on a signal from the controller 106. However, the valve 156 should be selected to be compatible with the high operating temperatures to which the valve 156 is subjected; ceramic seats, metal seats and/or soft (compressible) graphite seats in the valve 156 may be preferable over polymer materials.
[0050] Due to possibly inevitably inherent leaks in the system 100, the pressure within the hydrogen purifier 104 may slowly decrease over time. When the pressure falls to a predetermined value, for example 0.1 psig to 10 psig, the controller 106 may signal the system 100 to turn on, meaning that feedstock is admitted into the reformer 102 wherein the feedstock is converted to reformate that subsequently flows into the hydrogen purifier 104. The duration of time that the system 100 is turned on may also be adjustable within the range of 1 minute to 10 minutes. In another configuration, the system 100 is turned on and allowed to operate until the pressure within the hydrogen purifier 104 increases and reaches a predetermined value, at which time the system 100 is turned off.
[0051] From block 806, the method 800 may proceed to decision block 812, "Temp <T2?," in which the system 100 determines whether the temperature of the reformer 102 is less than a predetermined temperature T2. Temperature T2 may be a predetermined optimum operating temperature for the reformer 102. For example, temperature T2 may be, in some embodiments, 400°C. Other temperatures, however, may also be suitable depending on the particular process. Generally, temperature T2 may be a temperature less than temperature T1. [0052] If the temperature is determined to be at least temperature T2, the method 800 may continue to loop back to block 812, "Temp <T2?," until such time the temperature of the reformer 102 is less than temperature T2. In some embodiments, one or more other such monitoring operations may be additionally or alternatively performed during the time temperature is determined to be at least temperature T2. As illustrated, for example, the method 800 may optionally proceed to block 816, "Go to 900," block 900 being illustrated in Fig. 9.
[0053] Referring back to decision block 812, if the temperature of the reformer 102 is less than temperature T2 at block 812, the method 800 may proceed to block 814, "Heat the Reformer," in which the reformer 102 is heated (by a cartridge heater or other suitable heater including combustion of a fuel gas such as natural gas, propane, or LPG), or in which the heat provided to the reformer 102 is increased.
[0054] The method 800 may then proceed to decision block 818, "Temp >T2?," in which the system 100 determines whether the temperature of the reformer 102 is greater than the predetermined temperature T2. If the temperature of the reformer 102 remains equal to or below temperature T2, the method 800 may loop back to decision block 818.
[0055] When the temperature of the system 100 is greater than temperature T2, the method 800 may proceed to block 820, "Stop Heating the Reformer," in which heating of the reformer 102 is stopped or reduced. The system 100 may be configured to output a signal indicating the ready state as illustrated at block 822, "System Ready." From block 822, the method 800 may loop back to decision block 812, "Temp <T2?." [0056] Fig. 9 is a flow diagram illustrating some of the optional operations associated with an example method 900 of monitoring a reformation and hydrogen purification system, for example, once the system 100 has entered the "System
Operating" method, block 1010 of Fig. 10. The method 900 may include one or more functions, operations, or actions as is illustrated by any of blocks 902-924. Processing for the method 900 may start at block 902, "Temp >T3?," in which the system 100 determines whether the temperature of the reformer 102 is greater than a
predetermined temperature T3. Temperature T3 may be a predetermined temperature greater than temperature T2 suitable for operating the reformer 102. For example, temperature T3 may be, in some embodiments, 415°C. Other temperatures, however, may also be suitable depending on the particular process. Generally, reforming methanol plus water may be conducted at a lower temperature (such as 300°C to 450°C) whereas reforming other alcohols and/or hydrocarbons plus water may be conducted at a higher temperature (such as 500°C to 800°C).
[0057] If the temperature is determined to be greater than temperature T3, the method 900 may proceed to block 904 or block 905. Two different cooling modes may be used to reduce the temperature T3 to less than the set value. One method uses an optional cooling blower to force an excess volume of air into reformer 102 to reduce the operating temperature. The second method does not use a cooling blower, rather it drives the combustion occurring at burner 134 into a fuel-rich mixture resulting is a reduction in the heat liberated by the combustion process and subsequent cooling.
[0058] If T3 exceeds the set value, method 900 may proceed to block 904, "Turn Cooling Blower to High Speed," in which a cooling blower of the system 100 may be set to high speed to cool the reformer 102. If, on the other hand, the temperature is determined to be less than or equal to temperature T3, the method may proceed to block 906, "Turn Cooling Blower to Low Speed," in which a cooling blower of the system 100 may be set to low speed to allow the reformer 102 to increase in temperature until such point as the temperature exceeds T3. The method 900 may loop back to block 902 from either block 904 or 906.
[0059] Alternatively, if T3 exceeds the set value, method 900 may proceed to block 905, "Turn Combustion Blower to Low Speed," in which a combustion blower of system 100 may be set to low speed causing fuel-rich combustion and resulting in cooling the reformer 102. If, on the other hand, the temperature is determined to be less than or equal to temperature T3, the method may proceed to block 907, "Turn Combustion Blower to High Speed," in which a combustion blower of system 100 may be set to high speed to allow the reformer 102 to increase in temperature until such point as the temperature exceeds temperature T3. The method may loop back to block 902 from either block 905 or 907.
[0060] If the temperature is determined to continue to be greater than
temperature T3, the method 900 may proceed to decision block 908, "Temp >T4?," in which the system 100 determines whether the temperature of the reformer 102 is greater than a predetermined temperature T4. Temperature T4 may be a
predetermined temperature greater than temperature T3 suitable for monitoring a temperature of the reformer 102. For example, temperature T4 may be, in some embodiments, 450°C. Other temperatures, however, may also be suitable depending on the particular process. [0061] If the temperature is determined to be greater than temperature T4, the method 900 may proceed to block 910, "Shut System Down," in which the system 100 is shut down, and a signal indicating the fault state is output as illustrated at block 912, "System Fault."
[0062] If, on the other hand, the temperature is determined to be less than or equal to temperature T4, the method 900 may proceed to decision block 914,
"Feedstock Low?," in which the system 100 determines whether the feedstock level is below (or least) a predetermined level. If the feedstock level is determined to be low, the method 900 may proceed to block 916, "Shut System Down," in which the system 100 is shut down, and a signal indicating the low feedstock level is output as illustrated at block 918, "System Feedstock Level Alarm."
[0063] If, on the other hand, the feedstock level is determined to be adequate, the method 900 may proceed to decision block 920, "Pressure >or< P Limit?," in which the system 100 determines whether the pressure of the hydrogen purifier 104 is above or below a predetermined upper or lower limit. If the pressure is determined to be outside the predetermined operating range, the method 900 may proceed to block 922, "Shut System Down," in which the system 100 is shut down, and a signal indicating the fault state is output as illustrated at block 918, "System Fault."
[0064] If, on the other hand, the pressure is determined to be adequate, the method 900 may proceed to some other operation such as, for example, back to decision block 902. [0065] Turning now to Fig. 10, illustrated is a flow diagram illustrating some of the operations associated with an example method 1000 of operating a reformation and hydrogen purification system in back-up mode. The back-up mode may be a mode in which the system 100 provides back-up power to a power grid. Such back-up power may be used, for example, when a main or primary power grid fails or underperforms.
[0066] The method 1000 may include one or more functions, operations, or actions as is illustrated by any of blocks 802 or 1004-1020. Processing for the method 1000 may start with the system 100 in stand-by mode, as illustrated at block 802, "System in Standby." From block 802, the method 1000 may proceed to decision block 1004, "Grid Power Lost?," in which the system 100 determines or is notified by the fuel cell 1 12 or the controller 106 that the grid power has been lost. If the grid power has not been lost, the method 1000 may loop back to stand-by mode at block 802.
[0067] If, on the other hand, the grid power has been lost, the method may proceed to block 1006, "Fuel Cell Initiates Start," in which the fuel cell 1 12 starts providing back-up power to the grid. The fuel cell 1 12 may also send a signal to the system 100 at block 1008, "System Run," to direct the system 100 to begin hydrogen generation. The method 1000 may then proceed to block 1010, "System Operating," in which the system 100 outputs a signal indicating that the system 100 is operational.
[0068] In various embodiments, the method 1000 may optionally proceed to decision block 1012, "Pressure >P Minimum," in which the system 100 determines whether the pressure of the hydrogen purifier 104 is at least a predetermined minimum pressure limit. If the pressure is determined to be below the predetermined pressure limit, the method 1000 may proceed to block 1014, "System Fault," in which a signal indicating the fault state is output. The system 100 may be prevented from operating in this situation.
[0069] If, on the other hand, the system 100 determines that the pressure of the hydrogen purifier 104 is above the predetermined minimum pressure limit, the method 1000 may proceed to block 1010, "System Operating," in which a signal indicating that the system 100 is operational is output.
[0070] The method 1000 may then optionally proceed to block 1016, "Go to 900," block 900 being illustrated in Fig. 9 and as discussed more fully elsewhere.
[0071] The method 1000 may then proceed to decision block 1018, "Grid Power On?," in which the system 100 determines or is notified by the fuel cell 1 12 or the controller 106 that the grid power has been restored. If the grid power has not been restored, the method 1000 may loop back to decision block 1018 or optional block 1016.
[0072] If, on the other hand, the grid power has been restored, the method 100 may proceed to block 1020, "Fuel Cell Shuts Down," the fuel cell 1 12 may be shut down and the method may loop back to stand-by mode at block 802, in which the system 100 may be placed back into stand-by mode.
[0073] With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art may translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity. [0074] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," the term "includes" should be interpreted as "includes but is not limited to," etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to inventions containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (e.g., "a" and/or "an" should typically be interpreted to mean "at least one" or "one or more"); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of "two recitations," without other modifiers, typically means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to "at least one of A, B, and C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances where a convention analogous to "at least one of A, B, or C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B, or C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B."
[0075] Various operations may be described as multiple discrete operations in turn, in a manner that may be helpful in understanding embodiments; however, the order of description should not be construed to imply that these operations are order- dependent. Also, embodiments may have fewer operations than described. A description of multiple discrete operations should not be construed to imply that all operations are necessary. Also, embodiments may have fewer operations than described. A description of multiple discrete operations should not be construed to imply that all operations are necessary.
[0076] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.
[0077] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as "up to," "at least," "greater than," "less than," and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.
[0078] While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

Claims

Claims What is claimed is:
1. A reformation and hydrogen purification system comprising:
a reformer including a vaporizer coil configured to vaporize a feedstock, and an annular reactor at least partially surrounding the vaporizer coil and filled with a reforming catalyst reactive with the vaporized feedstock to generate a reformate;
a hydrogen purifier disposed externally to the reformer and configured to produce purified hydrogen and a raffinate from the reformate;
an accumulation tank configured to receive the purified hydrogen; and
a reduction return line configured to route the purified hydrogen from the accumulation tank to the hydrogen purifier to provide a reducing atmosphere for one or more surfaces of the hydrogen purifier.
2. The system of claim 1 , further comprising a control valve configured to control routing of the purified hydrogen by the reduction return line from the accumulation tank.
3. The system of claim 1 , further comprising an insulated chamber housing the reformer and the hydrogen purifier.
4. The system of claim 3, further comprising a routing line configured to route the reformate from the reformer to the hydrogen purifier, and wherein the routing line is disposed, at least in part, externally to the insulated chamber.
5. The system of claim 4, wherein the routing line includes a cooling loop configured to cool the reformate prior to routing the reformate to the hydrogen purifier.
6. The system of claim 1 , further comprising a non-microprocessor-based controller configured to control, adjust, or monitor one or more operations of at least one of the reformer, the hydrogen purifier, the accumulation tank, and the reduction return line.
7. The system of claim 1 , further comprising a hot element igniter proximately disposed to an opening in an outer wall of the annular reactor and configured to ignite the raffinate to provide heat supporting the vaporization of the feedstock, and a burner disposed within the annular reactor and coupled to the routing line, and wherein the burner is disposed between the opening in the annular reactor and an air inlet configured to provide air to the reformer.
8. The system of claim 7, wherein the opening is disposed between the vaporizer coil and the burner.
9. The system of claim 7, wherein the hot element igniter is disposed outside of the outer wall of the annular reactor.
10. The system of claim 1 , further comprising a first routing line configured to route the raffinate from the hydrogen purifier to the reformer, and a second routing line configured to route the reformate from the reformer to the hydrogen purifier.
1 1. The system of claim 10, wherein the first routing line, second routing line and the reduction return line are disposed externally to the hydrogen purifier and the reformer.
12. The system of claim 10, further comprising a third routing line routing the purified hydrogen from the hydrogen purifier to a heat exchanger disposed between the hydrogen purifier and the accumulation tank.
13. The system of claim 1 , further comprising a fuel cell coupled to the system to receive the purified hydrogen from the accumulation tank.
14. A reformation and hydrogen purification system comprising:
a reformer including a vaporizer coil configured to vaporize a feedstock, and an annular reactor at least partially surrounding the vaporizer coil and filled with a reforming catalyst reactive with the vaporized feedstock to generate a reformate;
a hydrogen purifier disposed externally to the reformer and configured to produce purified hydrogen and a raffinate from the reformate;
an insulated chamber housing the reformer and the hydrogen purifier; and a routing line configured to route the reformate from the reformer to the hydrogen purifier, wherein the routing line is disposed, at least in part, externally to the insulated chamber.
15. The system of claim 14, wherein the routing line includes a cooling loop configured to cool the reformate prior to routing the reformate to the hydrogen purifier.
16. The system of claim 14, further comprising a non-microprocessor-based controller configured to control, adjust, or monitor one or more operations of at least one of the reformer and the hydrogen purifier.
17. The system of claim 14, further comprising a heater block configured to heat the feedstock before the feedstock is routed to the reformer.
18. The system of claim 17, wherein the routing line comprises a first routing line, and wherein the system further comprises a second routing line configured to route the feedstock incoming to the system to the heater block.
19. The system of claim 14, wherein the heater block abuts an outer wall of the reformer.
20. The system of claim 14, further comprising a fuel cell coupled to the system to receive the purified hydrogen.
PCT/US2010/047846 2010-09-03 2010-09-03 Reformation and hydrogen purification system WO2012030350A1 (en)

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