The present disclosure is directed generally to hydrogen generation assemblies, components thereof, and energy production assemblies.
A hydrogen generation assembly is an assembly that converts one or more feedstocks into a product stream containing hydrogen gas as a majority component. The feedstocks may include a carbon-containing feedstock, and in some embodiments, may additionally include water. The feedstocks are delivered to a hydrogen-producing region of the hydrogen generation assembly from a feedstock delivery system, typically with the feedstocks being delivered under pressure and at elevated temperatures. The hydrogen-producing region is often associated with a temperature modulating assembly, such as a heating assembly or cooling assembly, which consumes one or more fuel streams to maintain the hydrogen-producing region within a suitable temperature range for effectively producing hydrogen gas.
The produced hydrogen gas may be used in a variety of applications. One such application is energy production, such as in electrochemical fuel cells. An electrochemical fuel cell is a device that converts fuel and an oxidant to electricity, a reaction product, and heat. For example, fuel cells may convert hydrogen and oxygen into water and electricity. In such fuel cells, the hydrogen is the fuel, the oxygen is the oxidant, and the water is a reaction product. Fuel cell stacks include a plurality of fuel cells and may be utilized with a hydrogen generation assembly to provide an energy production assembly. The fuel cell stack may be associated with an air delivery system to deliver an air stream thereto and/or a temperature modulating assembly to maintain the fuel cell stack within a suitable temperature range for generating electricity.
The present disclosure relates to assemblies, systems, devices, and methods that are adapted to produce hydrogen gas from one or more feedstocks for use in electrochemical fuel cells or in other applications, as well as energy production assemblies incorporating the same. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, are adapted for portable applications. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, are free of pumps and other electrically powered fluid delivery systems. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, include pumps or other feedstock delivery systems that are adapted to draw one or more feed streams from a supply, which in some embodiments is an unpressurized or low pressure supply. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, are free of electrically powered controllers. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, include a controller, which in some embodiments is an electrically powered controller, and in some embodiments is a computerized, or computer-implemented, controller. In some embodiments, the hydrogen generation assemblies, and energy production assemblies incorporating the same, are adapted to produce purified hydrogen gas without requiring a powered feedstock delivery system or heating or other temperature modulation assembly. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, include an electrically powered feedstock delivery system and/or heating or other temperature modulation assembly. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, are adapted to startup from an off operating configuration, to transition from the startup operating configuration to a hydrogen-producing and/or energy-producing operating configuration, and to maintain the selected operating configuration with minimal user inputs and/or balance-of-plant requirements. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, are adapted to start up using a liquid-fueled burner assembly. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, are adapted to start up using a gas-fueled burner assembly. In some embodiments, the hydrogen generation assemblies, and energy production assemblies incorporating the same, include a feedstock delivery system that is adapted to utilize a recycle stream and at least one of a flow restrictor and a pressure-actuated valve to regulate the flow rate and/or pressure at which the feed stream is delivered to the hydrogen-producing region of the fuel processor. In some embodiments, the hydrogen generation assemblies, and/or energy production assemblies incorporating the same, are adapted to be portable assemblies. In some embodiments, the hydrogen generation assemblies are adapted to produce less than 15 slm of hydrogen gas, and in some embodiments, less than 10 slm, or optionally even less than 5 μm, of hydrogen gas when operating at full capacity. In some embodiments, the energy production assemblies incorporating hydrogen generation assemblies according to the present disclosure are adapted to have a rated power output of at least 100 watts and/or not more than 1000 watts, and optionally 100400 watts, 200-600 watts, and/or 400-800 watts.
A hydrogen generation assembly according to the present disclosure is schematically illustrated in
Examples of suitable mechanisms for producing hydrogen gas from feed stream(s) 16 delivered by feedstock delivery system 22 include steam reforming and autothermal reforming, in which reforming catalysts are used to produce hydrogen gas from a feed stream 16 containing a carbon-containing feedstock 18 and water 17. In a steam reforming process, hydrogen-producing region 19 contains a suitable steam reforming catalyst 23, as indicated in dashed lines in
Other suitable mechanisms for producing hydrogen gas include pyrolysis and catalytic partial oxidation of a carbon-containing feedstock, in which case the feed stream does not contain water. Examples of suitable carbon-containing feedstocks 18 include at least one hydrocarbon or alcohol. Examples of suitable hydrocarbons include methane, propane, natural gas, diesel, kerosene, gasoline and the like. Examples of suitable alcohols include methanol, ethanol, and polyols, such as ethylene glycol and propylene glycol. It is within the scope of the present disclosure that hydrogen generation assembly 10 may utilize more than a single hydrogen-producing mechanism in the hydrogen-producing region 19.
Fuel processing assemblies 31 according to the present disclosure may (but are not required to) further include a purification, or separation, region 24, in which a hydrogen-rich stream 26 is produced from the output, or mixed gas, stream. Hydrogen-rich stream 26 contains at least one of a greater hydrogen concentration than output stream 20 and a reduced concentration of one or more of the other gases or impurities that were present in the output stream. Purification region 24 is schematically illustrated in
Purification region 24 may, but is not required to, produce at least one byproduct stream 28. Byproduct stream 28 may contain no hydrogen gas, or it may contain some hydrogen gas. When present, byproduct stream 28 may be exhausted, sent to a burner assembly or other combustion source, used as a heated fluid stream, stored for later use, or otherwise utilized, stored or disposed of. It is within the scope of the disclosure that byproduct stream 28 may be emitted from the purification region as a continuous stream responsive to the delivery of output stream 20 to the purification region, or intermittently, such as in a batch process or when the byproduct portion of the output stream is retained at least temporarily in the purification region.
While not required, it is within the scope of the present disclosure that fuel processing system 31 may include one or more purification regions that are adapted to produce one or more byproduct streams containing sufficient amounts of hydrogen gas to be suitable for use as a fuel, or feedstock, stream for a heating assembly for the fuel processing system. In some embodiments, the byproduct stream may have sufficient fuel value (i.e., hydrogen content) to enable the heating assembly, when present, to maintain the hydrogen-producing region at a desired operating temperature or within a selected range of temperatures. Therefore, while not required, it is within the scope of the present disclosure that the byproduct stream may include hydrogen gas, such as 10-30 wt % hydrogen gas, 15-25 wt % hydrogen gas, 20-30 wt % hydrogen gas, at least 10 or 15 wt % hydrogen gas, at least 20 wt % hydrogen gas, etc.
It is within the scope of the present disclosure that the purification, or separation, region and the hydrogen producing region may be housed together in a common shell, or housing, 68. It is within the scope of the present disclosure that the separation region is separately positioned relative to the hydrogen-producing region but in fluid communication therewith to receive the mixed gas stream therefrom. It is also within the scope of the present disclosure that the hydrogen generation assembly does not include a separation region.
Purification region 24 includes any suitable mechanism, device, or combination of devices, that are adapted to reduce the concentration of at least one component of output stream 20. In most applications, hydrogen-rich stream 26 will have a greater hydrogen concentration than output, or mixed gas, stream 20. However, it is also within the scope of the disclosure that the hydrogen-rich stream will have a reduced concentration of one or more non-hydrogen components that were present in output stream 20, yet have the same, or even a reduced overall hydrogen concentration as the output stream. For example, in some applications where product hydrogen stream 14 may be used, certain impurities, or non-hydrogen components, are more harmful than others. As a specific example, in conventional fuel cell systems, carbon monoxide may damage a fuel cell stack if it is present in even a few parts per million, while other non-hydrogen components that may be present in stream 20, such as water, will not damage the stack even if present in much greater concentrations. Therefore, in such an application, a suitable purification region may not increase the overall hydrogen concentration, but it will reduce the concentration of a non-hydrogen component that is harmful, or potentially harmful, to the desired application for the product hydrogen stream.
Illustrative examples of suitable devices for purification region 24 include one or more hydrogen-selective membranes 30, chemical carbon monoxide removal assemblies 32, and pressure swing adsorption systems 38. It is within the scope of the disclosure that purification region 24 may include more than one type of purification device, and that these devices may have the same or different structures and/or operate by the same or different mechanisms. As discussed herein, hydrogen-producing fuel processing assembly 31 may include at least one restrictive orifice or other flow restrictor downstream of at least one purification region, such as associated with one or more of the product hydrogen stream, hydrogen-rich stream, and/or byproduct stream.
Hydrogen-selective membranes 30 are permeable to hydrogen gas, but are at least substantially, if not completely, impermeable to other components of output stream 20. Membranes 30 may be formed of any hydrogen-permeable material suitable for use in the operating environment and parameters in which purification region 24 is operated. Examples of suitable materials for membranes 30 include palladium and palladium alloys, and especially thin films of such metals and metal alloys. Palladium alloys have proven particularly effective, especially palladium with 35 wt % to 45 wt % copper. A palladium-copper alloy that contains approximately 40 wt % copper has proven particularly effective, although other relative concentrations and components may be used within the scope of the disclosure. Examples of various membranes, membrane configurations, and methods for preparing the same are disclosed in U.S. Pat. Nos. 6,221,117, 6,319,306, and 6,537,352, the complete disclosures of which are hereby incorporated by reference for all purposes.
Chemical carbon monoxide removal assemblies 32 are devices that chemically react carbon monoxide and/or other undesirable components of stream 20, if present in output stream 20, to form other compositions that are not as potentially harmful. Examples of chemical carbon monoxide removal assemblies include water-gas shift reactors to produce hydrogen gas and carbon dioxide from water and carbon monoxide, partial oxidation reactors that are adapted to convert carbon monoxide into carbon dioxide, and methanation catalyst regions, or beds, that convert carbon monoxide and hydrogen to methane and water. It is within the scope of the disclosure that fuel processing assembly 31 may include more than one type and/or number of chemical removal assemblies 32.
Pressure swing adsorption (PSA) is a chemical process in which gaseous impurities are removed from output stream 20 based on the principle that certain gases, under the proper conditions of temperature and pressure, will be adsorbed onto an adsorbent material more strongly than other gases. Typically, it is the impurities that are adsorbed and removed from output stream 20. Adsorption of impurity gases occurs at elevated pressure. When the pressure is reduced, the impurities are desorbed from the adsorbent material, thus regenerating the adsorbent material. Typically, PSA is a cyclic process and requires at least two beds for continuous (as opposed to batch) operation. Examples of suitable adsorbent materials that may be used in adsorbent beds are activated carbon and zeolites, especially 5 Å (5 angstrom) zeolites. PSA system 38 also provides an example of a device for use in purification region 24 in which the byproducts, or removed components, are not directly exhausted from the region as a gas stream concurrently with the purification of the output stream. Instead, these byproduct components are removed when the adsorbent material is regenerated or otherwise removed from the purification region.
In
In
It is further within the scope of the disclosure that one or more of the components of fuel processing assembly 31 may either extend beyond the shell or be located external at least shell 68. For example, and as discussed, purification region 24 may be located external shell 68, such as with the purification region being coupled directly to the shell (as schematically illustrated in
In the illustrative, non-exclusive embodiment shown in
In some fuel processing assemblies according to the present disclosure, heating assembly 60 includes a burner assembly 62 and may be referred to as a combustion-based, or combustion-driven, heating assembly. In a combustion-based heating assembly, the heating assembly 60 is adapted to receive at least one fuel stream 64 and to combust the fuel stream in the presence of air to provide a hot combustion stream 66 that may be used to heat at least the hydrogen-producing region 19 of the fuel processor. As discussed in more detail herein, air may be delivered to the heating assembly via a variety of mechanisms. In
It is within the scope of the disclosure that combustion stream 66 may additionally or alternatively be used to heat other portions of the fuel processing assembly and/or fuel cell systems with which heating assembly 60 is used. It is also within the scope of the present disclosure that other configurations and types of heating assemblies 60 may be utilized. As an illustrative example, a heating assembly 60 may be an electrically powered heating assembly that is adapted to heat at least the hydrogen-producing region of the fuel processing assembly by generating heat using at least one heating element, such as a resistive heating element. Therefore, it is not required that heating assembly 60 receive and combust a combustible fuel stream to heat hydrogen-producing region 19 to a suitable hydrogen-producing temperature. Additional non-exclusive examples of heating assemblies that may be utilized in hydrogen generating assemblies, hydrogen-producing fuel processing assemblies, fuel cell systems, and the like according to the present disclosure are disclosed in U.S. patent application Ser. No. 11/226,810, which is entitled “Hydrogen-Producing Fuel Processing Assemblies, Heating Assemblies, and Methods of Operating the Same,” was filed on Sep. 13, 2005, and the complete disclosure of which is hereby incorporated by reference for all purposes.
As also schematically illustrated in
Depending on the configuration of the hydrogen generation assembly 10 and the fuel processing system 31, the heating assembly 60 may be configured to heat the feedstock delivery system, the feedstock supply streams, the hydrogen-producing region, the purification (or separation) region, or any combination of these elements or selected components thereof. The heating of the feedstock supply streams may include vaporizing liquid reactant streams or components of the hydrogen-production fluid used to produce hydrogen gas in the hydrogen-producing region. In such an embodiment, the fuel processing system may be described as including a vaporization region 69. The heating assembly 60 may also be configured to heat other components of the hydrogen generation assembly 10. For example, the heated exhaust stream may be adapted to heat a pressure vessel or other canister containing the heating fuel and/or the hydrogen-production fluid that form at least portions of streams 16 and 64. While not required, increasing the temperature of a vessel may increase the pressure of the fluids stored within the vessel, which may be desirable in some applications.
As an illustrative example of temperatures that may be achieved and/or maintained in hydrogen-producing region 19 through the use of heating assembly 60, steam reformers typically operate at temperatures in the range of 200° C. and 900° C. Temperatures outside of this range are within the scope of the disclosure. When the carbon-containing feedstock is methanol, the steam reforming reaction will typically operate in a temperature range of approximately 200-500° C. Illustrative subsets of this range include 350-450° C., 375-425° C., and 375-400° C. When the carbon-containing feedstock is a hydrocarbon, ethanol or another alcohol, a temperature range of approximately 400-900° C. will typically be used for the steam reforming reaction. Illustrative subsets of this range include 750-850° C., 725-825° C., 650-750° C., 700-800° C., 700-900° C., 500-800° C., 400-600° C., and 600-800° C. It is within the scope of the present disclosure for the hydrogen-producing region to include two or more zones, or portions, each of which may be operated at the same or at different temperatures. For example, when the hydrogen-production fluid includes a hydrocarbon, in some embodiments it may be desirable to include two different hydrogen-producing portions, or regions, with one operating at a lower temperature than the other to provide a pre-reforming region. In such an embodiment, the fuel processing system may alternatively be described as including two or more hydrogen producing regions.
Hydrogen-producing fuel processing assemblies, or hydrogen generation assemblies 10, according to the present disclosure may include a feedstock delivery system 22 that is adapted to selectively deliver at least one feed stream 16 to at least the hydrogen-producing region of the fuel processing/generating assembly. In some embodiments, the feedstock delivery system is further adapted to at least selectively deliver fuel stream 64 to a burner 62 or other heating assembly 60 that is adapted to heat at least the hydrogen-producing region 19, such as to heat (and optionally maintain) the region at a suitable hydrogen-producing temperature. Feedstock delivery system 22 may utilize any suitable delivery mechanism, such as a positive displacement or other suitable pump or mechanism for propelling liquid fluid streams. In some embodiments of feedstock delivery systems 22 according to the present disclosure, the delivery system is adapted to deliver the at least one feed stream and/or the fuel stream without requiring the use of pumps or other electrically powered fluid-delivery mechanisms.
In the embodiment shown schematically in
While a single feed stream 16 is shown in
When the heating assembly forms a portion of the fuel processing assembly, such as schematically illustrated in the illustrative embodiment shown in
The hydrogen-production fluid 15 may include one or more fluids that may be utilized as reactants to produce product hydrogen stream 14, such as described above. The composition of the hydrogen-production fluid 15 may be selected based on the configuration of the hydrogen-generation assembly 10 and/or the mechanism by which hydrogen is produced in the hydrogen-producing region. For example, the hydrogen-production fluid 15 may include at least one carbon-containing feedstock, water, or a combination of water and a carbon-containing feedstock. Illustrative examples of carbon-containing feedstocks are previously presented herein. When the hydrogen-producing region is adapted to receive water and a carbon-containing feedstock as reactants to produce hydrogen gas, either or both of these reactants may be supplied as the hydrogen-production fluid by the feedstock delivery system.
For example, when a carbon-containing feedstock is used that is miscible with water, such as methanol or another water-soluble alcohol, the feedstock delivery system may be (but is not required to be) adapted to deliver a hydrogen-production fluid 15 that contains a mixture of water and the carbon-containing feedstock. The ratio of water to carbon-containing feedstock in such a fluid stream may vary according to such factors as the particular carbon-containing feedstock being used, user preferences, the design of the hydrogen-production region, etc. Typically the molar ratio of water to carbon will be approximately 1:1 to 3:1. Mixtures of water and methanol will typically be delivered at or near a 1:1 molar ratio (31 vol % water, 69 vol % methanol), while mixtures of hydrocarbons or other alcohols will typically be delivered at a molar ratio greater than 1:1 water-to-carbon.
As a further illustrative example, a reforming feed stream 16 may contain approximately 25-75 vol % methanol or ethanol or another suitable water-miscible carbon-containing feedstock, and approximately 25-75 vol % water. For feed streams formed (at least substantially) of methanol and water, the streams will typically contain approximately 50-75 vol % methanol and approximately 25-50 vol % water. Streams containing ethanol or other water-miscible alcohols will typically contain approximately 25-60 vol % alcohol and approximately 40-75 vol % water. An example of a particularly well-suited feed stream for hydrogen-generating assemblies that utilize steam reforming or autothermal reforming reactions contains 69 vol % methanol and 31 vol % water, although other compositions and liquid carbon-containing feedstocks may be used without departing from the scope of the present disclosure.
While not required, it is within the scope of the present disclosure that such a feed stream that contains both water and at least one carbon-containing feedstock may be used as the feed stream for hydrogen-producing region 19 and as a combustible fuel stream for a heating assembly that is adapted to heat at least the hydrogen-producing region of the fuel processing assembly. A potential benefit of such a construction is that the hydrogen generation assembly that produces hydrogen gas from water and a carbon-containing feedstock does not need to include more than a single supply 112, if the water and water-soluble liquid carbon-containing feedstock are premixed. If not, then the hydrogen generation assembly still only requires a water supply and a carbon-containing feedstock supply.
It is also within the scope of the present disclosure that a feedstock delivery system 22 may deliver the components of the hydrogen production fluid, or feed stream, to the fuel processing assembly in two or more streams, with these streams having the same or different compositions. For example, when the fuel processor is adapted to produce hydrogen gas from a carbon-containing feedstock and water, these components are typically delivered in separate streams, and optionally (at least until both streams are vaporized or otherwise gaseous), when they are not miscible with each other, such as shown in
It is within the scope of the present disclosure that heating fuel 13 may include any combustible liquid and/or gas that is suitable for being consumed by heating assembly 60 to provide the desired heat output. Some heating fuels 13 according to the present disclosure will be gases when delivered and combusted by heating assembly 60, while others will be delivered to the heating assembly as a liquid stream. Illustrative examples of suitable heating fuels include the previously discussed carbon-containing feedstocks, such as methanol, methane, ethane, ethanol, ethylene, propane, propylene, butane, and butanes, amongst others. Additional examples include low molecular weight condensable fuels such as liquefied petroleum gas, ammonia, lightweight amines, dimethyl ether, and low molecular weight hydrocarbons. Although not required to all embodiments, the heating fuel stream and the hydrogen-production fluid stream may have different individual or overall compositions and may be discharged from the feedstock delivery system in different phases. For example, one of the streams may be a liquid stream while the other is a gas stream. In some embodiments, both of the streams may be liquid streams. In some embodiments, both of the streams may be gas streams. In embodiments of a hydrogen generation assembly that include a temperature modulating assembly in the form of a cooling assembly instead of a heating assembly (such as may be used when an exothermic hydrogen-generating process is utilized instead of an endothermic process like steam reforming), it is within the scope of the present disclosure that the feedstock delivery system may be adapted to supply a fuel or coolant stream to the assembly. Any suitable fuel or coolant fluid may be used.
Illustrative, non-exclusive examples of suitable feedstock delivery systems that may be used with hydrogen-producing fuel processing assemblies (or hydrogen-generation assemblies) according to the present disclosure are disclosed in U.S. patent application Ser. Nos. 11/228,637, 11/096,827, and 60/623,894, the complete disclosures of which are hereby incorporated by reference for all purposes. The above-incorporated applications also disclose additional examples of fuel processing assemblies, fuel cell systems, the components therefor, and methods for operating the same that may selectively be used and/or integrated with other components disclosed, illustrated and/or incorporated herein. Illustrative, nonexclusive examples of suitable hydrogen generation assemblies, and components thereof, are disclosed in U.S. Pat. Nos. 6,221,117, 5,997,594, 5,861,137, and pending U.S. Patent Application Publication Nos. 2001/0045061, 2003/0192251, and 2003/0223926. The complete disclosures of the above-identified patents and patent applications are hereby incorporated by reference for all purposes. Additional examples are disclosed in U.S. patent application Ser. Nos. 10/945,783, 11.226,810, and 11/228,637, the complete disclosures of each of which are hereby incorporated by reference for all purposes.
As discussed, product hydrogen stream 14 may be used in a variety of applications, including applications where high purity hydrogen gas is utilized. An example of such an application is as a fuel, or feed, stream for a fuel cell stack. A fuel cell stack is a device that produces an electrical potential from a source of protons, such as hydrogen gas, and an oxidant, such as oxygen gas. Accordingly, hydrogen generation assembly 10 may include or be coupled to at least one fuel cell stack 40, which is adapted to receive at least a portion of product hydrogen stream 14 and an air or other oxidant stream 81 to produce an electrical power output therefrom. This is schematically illustrated in
As used herein, hydrogen generation assembly 10 may also be described as being a fuel processing system, a fuel processing assembly, and/or a hydrogen-producing fuel processing system (or assembly). As used herein, energy-producing system 42 may be referred to as a fuel cell system or a hydrogen-producing fuel cell system. The present application incorporates by reference many different applications that disclose fuel processing assemblies, fuel cell systems, or components thereof. It is within the scope of the present disclosure that these systems and components, including the variations disclosed, illustrated, and incorporated therein and herein may be selectively combined and used or integrated together without departing from the scope of the present disclosure.
Stack 40 includes at least one fuel cell 44, and typically includes a plurality of fuel cells 44 that are adapted to produce an electric current from an oxidant, such as air, oxygen-enriched air, or oxygen gas, and the portion of the product hydrogen stream 14 delivered thereto. A fuel cell stack typically includes multiple fuel cells joined together between common end plates 48, which contain fluid delivery/removal conduits, although this construction is not required to all embodiments. Examples of suitable fuel cells include proton exchange membrane (PEM) fuel cells and alkaline fuel cells. Others include solid oxide fuel cells, phosphoric acid fuel cells, and molten carbonate fuel cells.
Fuel cell stack 40 may have any suitable construction. Illustrative examples of fuel cell stacks, and components thereof, are disclosed in U.S. Pat. Nos. 4,214,969, 4,583,583, 5,300,370, 5,484,666, 5,879,826, 6,057,053, and 6,403,249, the complete disclosures of which are hereby incorporated by reference. Additional examples are disclosed in U.S. Provisional Patent Application Ser. Nos. 60/623,156 and 60/630,710, the complete disclosures of which are hereby incorporated by reference for all purposes. Additional illustrative, non-exclusive examples of suitable fuel cell systems, stacks, and components thereof, that may be utilized in fuel cell systems, including hydrogen-producing fuel cell systems that include a hydrogen-producing fuel processing assembly, according to the present disclosure are disclosed in U.S. patent application Ser. No. ______, which was filed on Oct. 28, 2005, is entitled “Fuel Cell Stack Compression Systems, and Fuel Cell Stacks and Fuel Cell Systems Incorporating the Same,” the complete disclosure of which is hereby incorporated by reference for all purposes. Further examples of fuel cell systems, stacks, and components thereof, that may be utilized in fuel cell systems, including hydrogen-producing fuel cell systems that include a hydrogen-producing fuel processing assembly, according to the present disclosure are disclosed in U.S. patent application Ser. No. 11/150,615, which is entitled “Partitioned Fuel Cell Stacks and Fuel Cell Systems Including the Same,” was filed on Jun. 10, 2005, and the complete disclosure of which is hereby incorporated by reference for all purposes.
It is within the scope of the present disclosure that hydrogen generation assemblies 10 according to the present disclosure may be used in other applications in which it is desirable to have a source of hydrogen gas and/or may be used to produce hydrogen gas for storage and later consumption. In other words, while hydrogen generation assemblies 10 according to the present disclosure may be utilized with fuel cell stacks to provide a fuel cell system for satisfying an applied electrical load, it is also within the scope of the present disclosure that the hydrogen generation assemblies may be utilized independent of fuel cell stacks.
Energy producing, or fuel cell, system 42 may be adapted to supply power to meet the applied load from at least one energy-consuming device 46. Illustrative examples of energy-consuming devices include, but should not be limited to, motor vehicles, recreational vehicles, construction or industrial vehicles, boats and other sea craft, and any combination of one or more residences, commercial offices or buildings, neighborhoods, tools, lights and lighting assemblies, radios, appliances (including household appliances), computers, industrial equipment, signaling and communications equipment, radios, electrically powered components on boats, recreational vehicles or other vehicles, battery chargers, autonomous battery chargers, mobile devices, mobile tools, emergency response units, life support equipment, monitoring equipment for patients, and even the balance-of-plant electrical requirements for the energy-producing system 42 of which fuel cell stack 40 forms a part. As used herein, energy-consuming device 46 is used to schematically and generally refer to one or more energy-consuming devices that are adapted to draw power from an energy producing system, or fuel cell system, according to the present disclosure. It is also within the scope of the present disclosure that an energy-producing system according to the present disclosure, including such a system that includes a hydrogen generation assembly (or hydrogen-producing fuel processing assembly) according to the present disclosure, may be integrated or otherwise coupled to, or commonly housed within, at least one energy-consuming device to provide an energy-producing and consuming assembly, or system, as indicated generally at 56 in
In the context of a portable energy producing system according to the present disclosure, the rate at which the hydrogen generation assembly is adapted to produce hydrogen gas, and the rated power output of fuel cell stack 40 contribute or otherwise define the number and/or type of energy-consuming devices that system 22 may be adapted to power. Therefore, although not required by all fuel energy producing systems (or hydrogen-producing fuel cell systems), including (but not limited to) smaller, portable energy producing systems according to the present disclosure, the system may be designed or otherwise configured to have a rated/intended maximum power output, and corresponding hydrogen gas production rate, of 1000 watts or less. In some embodiments, the system may be designed or otherwise configured to have a rated/intended maximum power output, and corresponding hydrogen gas production rate, and in some embodiments to have a rated/intended maximum power output of 500 watts or less. In some embodiments, the system may be designed or otherwise configured to have a rated/intended maximum power output, and corresponding hydrogen gas production rate, of 300 watts or less, or even 250 watts. The systems will typically have a rated, or maximum, power output of at least 100 watts, although this is not required to all embodiments. Illustrative, non-exclusive examples of power outputs of 1000 watts or less that may be utilized by systems according to the present disclosure include, but should not be limited to 800-500 watts, 500-750 watts, 750-1000 watts, 200-500 watts, 250-500 watts, 300-600 watts, and 400-800 watts. Illustrative, non-exclusive examples of power outputs of 500 watts or less that may be utilized by systems according to the present disclosure include, but should not be limited to, 25-500 W, 50-200 W, 50-250 W, 150-250 W, 350-450 W, 100-400 W, 100-300 W, and 250-450 W. Illustrative, non-exclusive examples of power outputs of 300 watts or less that may be utilized by systems according to the present disclosure include, but should not be limited to 100-300 watts, 75-300 watts, 100-200 watts, 200-300 watts, 150-300 watts, and 250-300 watts. Typically these systems will be relatively lightweight and compact, such as sized for manual transport by an individual.
When fuel cell systems 42 are adapted to have a rated power output of 1 kW or less, such as discussed above, the corresponding hydrogen generation assembly 10 may be configured to provide an appropriate flow rate of hydrogen gas in product hydrogen stream 14 to enable the fuel cell stack, or stacks, to produce this power output. For example, the hydrogen generation assemblies illustrated herein may be adapted to produce less than 20 slm of hydrogen gas when operating at full capacity, with illustrative subsets of this range including less than 15 slm, less than 10 slm, less than 5 slm, 13-15 μm, 3-5 slm, and 2-4 slm of hydrogen gas. For a system 44 rated to produces 250 watts/hr, an illustrative, non-exclusive example of a suitable capacity for hydrogen generation assembly 10 is 3-4 slm of hydrogen gas.
However, it is within the scope of the present disclosure that hydrogen generation assemblies (and energy-producing systems incorporating the same) according to the present disclosure may be constructed to any suitable scale, such as depending upon the desired flow rate of hydrogen gas in product hydrogen stream 14, the desired rated output of the energy producing system, the type and/or number of energy-consuming devices to be powered by the energy producing assembly, limitations on available size for the hydrogen generation assembly and/or the energy production assembly, etc. In some embodiments, it may be desirable to produce energy-production assemblies according to the present disclosure that have a rated (designed) power output in the range of 1-2 kW, with the assembly including a hydrogen generation assembly adapted to provide the requisite hydrogen gas to produce the required electricity to satisfy such an applied load. In other applications, it may be desirable for the assembly to have a power output in the range of 4-6 kW, such as to provide power to a household or other residence, small office, or other energy-consuming device with similar energy requirements.
It is within the scope of the present disclosure that embodiments of hydrogen generation assemblies, fuel processing assemblies, feedstock delivery systems, fuel cell stacks, and/or fuel cell systems that are disclosed, illustrated and/or incorporated herein may be utilized in combinations of two or more of the corresponding components to increase the capacity thereof. For example, if a particular embodiment of a hydrogen generation assembly is adapted to produce 34 slm of hydrogen gas, then two such assemblies may be used to produce 6-8 slm of hydrogen gas. Accordingly, the assemblies and systems disclosed herein may be referred to as scalable systems. It is within the scope of the present disclosure that the hydrogen generation assemblies, fuel processing assemblies, fuel cell stacks, fuel processors, and/or heating assemblies described, illustrated and/or incorporated herein may be configured as modular units that may be selectively interconnected together.
Fuel cell stack 40 may receive all of product hydrogen stream 14. Some or all of stream 14 may additionally, or alternatively, be delivered, via a suitable conduit, for use in another hydrogen-consuming process, burned for fuel or heat, or stored for later use. As an illustrative example, a hydrogen storage device 50 is shown in dashed lines in
Fuel cell system 42 may also include a battery 52 or other suitable electricity-storing device that is adapted to store the electric potential, or power output, produced by stack 40. Similar to the above discussion regarding excess hydrogen, fuel cell stack 40 may produce a power output in excess of that necessary to satisfy the load exerted, or applied, by device 46, including the load required to power fuel cell system 42. In further similarity to the above discussion of excess hydrogen gas, this excess power output may be used in other applications outside of the fuel cell system and/or stored for later use by the fuel cell system. For example, the battery or other storage device may provide power for use by system 42 during startup or other applications in which the system is not producing electricity and/or hydrogen gas. In
It is within the scope of the present disclosure that hydrogen generation assemblies and/or fuel cell systems may be free from computerized controllers and control systems. In such an embodiment, the system may be less complex in that it may not include as many sensors, communication linkages, actuators, and the like, and it may have lower balance of plant requirements than a comparable assembly or system that includes a controller. However, in some embodiments, it may be desirable to include a controller, such as to automate one or more operations of the assembly or system, to regulate the operation of the assembly or system, etc. In
As indicated in dashed lines in
Fuel processors 12, heating assemblies 60, and feedstock delivery systems 22 according to the present disclosure may be configured in any of the arrangements described, illustrated and/or incorporated herein. In some embodiments, features or aspects from one or more of the above described configurations may be combined with each other and/or with additional features described herein. For example, it is within the scope of the present disclosure that fuel processing assemblies 10 that include at least one purification region 24 may (but are not required to) house the hydrogen-producing region 19 and at least a portion of the purification region together in a common housing, with this housing optionally being located within the shell 68 of the fuel processor. This is schematically illustrated in
As indicated in dashed lines in
An illustrative, less schematic example of a fuel processor that includes a hydrogen producing region and at least on purification region 24 housed within a common, sealed, shell 27 is shown in
As shown, shell 27 includes end plates 262 and 264, which are adapted to be secured together to define a sealed pressure vessel having an interior compartment 265 in which the hydrogen-producing and separation regions are supported. Any suitable process may be utilized to seal the portions of shell 27 together. Also shown is a support 266 for membrane 30. Support 266 should be formed from a porous material through which the portion of the mixed gas stream that permeates through membrane 30 may flow. Also shown are various support plates and sealing gaskets 268 and 270.
It is within the scope of the present disclosure that more than a single membrane 30 or other purification device may be used in a single shell 27 and/or fuel processing assembly 31. This is schematically illustrated in dashed lines in
Another illustrative example of a suitable configuration for a fuel processor that includes a sealed shell 27 that contains a hydrogen-producing region 19 and at least one purification (or separation) region 24 is shown in
Similar to the illustrative example of
In
As indicated in
As illustrated, the plates and gaskets are sized with asymmetrical shapes so that these components may only be located in the housing in a predetermined configuration. This is not required, but it may assist in assembly of the components because they cannot be inadvertently positioned in the housing in a backwards or upside-down configuration. In the illustrative example of a suitable asymmetrical shape, a corner region 278 of the various components within the shell has a different shape than the other corner regions, with this difference being sufficient to permit that corner to be only inserted into one of the corresponding corner regions of the shell's internal compartment. Accordingly, the shell may be described as being keyed, or indexed, to define the orientation of the gaskets, frames, supports and similar components that are stacked therein.
In
Shell 27 may further include a chemical purification region, such a region containing a suitable methanation catalyst 32. Additionally or alternatively, the methanation catalyst, when present, may be contained downstream of shell 27, such as in the conduit through which the hydrogen-rich stream leaves the housing, as indicated in dashed lines in
An illustrative, non-exclusive example of a hydrogen generation assembly 10 according to the present disclosure is shown schematically in
For the purpose of providing a specific, although not exclusive or required, example, the following discussion will refer to the carbon-containing feedstock as including or being methanol and the heating fuel as including or being propane. It is within the scope of the present disclosure that other mechanisms for producing hydrogen gas from hydrogen-production fluid 15 may additionally or alternatively be used. Similarly, other heating fuels and hydrogen production fluids may be used. For example, fluid 15 may be include water, such as up to, or even more than 25 wt % water, in addition to methanol or another water-soluble carbon-containing feedstock. As another example, the combustible fuel may be a liquid when delivered to the heating assembly and/or when withdrawn from the feedstock delivery system. In
In the illustrated example shown in
The heating assembly typically also receives an air stream to support the combustion occurring therein. The air stream may be delivered via any suitable air delivery assembly, such as a blower, fan, compressor, or the like. It is also within the scope of the present disclosure that the air is drawn from the environment within which the heating assembly is used, with no air delivery assembly, much less an electrically powered air delivery assembly, being required. As a further variation, when the hydrogen generation assembly is coupled to a fuel cell stack and/or an energy-storage device, the stack and/or energy-storage device may power an air delivery assembly. In the illustrative example, air stream 74 is combined with the heating fuel supply stream 64 prior to entering the heating assembly. As shown, the air stream is mixed with heating fuel 13 at an air entrainment area 214 prior to entering the heating assembly. Additionally or alternatively, the air supply may enter the heating assembly 60 separately from the heating fuel.
The heated exhaust stream 66 from the heating assembly is shown heating the hydrogen-production fluid 15 prior to the fluid being delivered to the hydrogen-producing region, with the heated exhaust stream also heating the hydrogen-producing region. When the heating fluid is a liquid stream when it is delivered to the fuel processor, the stream may be vaporized by the heated exhaust stream from the heating assembly in a vaporization region 69. In
As illustrated in
As also shown in
When the byproduct stream has sufficient fuel value to be used as a fuel stream for heating assembly 60, at least a portion of the byproduct stream may be delivered to the heating assembly for consumption as a fuel stream. This is illustrated in the example shown in
In the illustrative example shown in
For example, the hydrogen-production fluid 15 may be delivered to hydrogen-producing region 19 at a pressure in the range of 50-250 psi, with this pressure being established at least in part by the pressure at which the hydrogen-production fluid is discharged from the feedstock delivery system (including, but not limited to, from the subsequently discussed pressure vessel 59 or any other pressurized source 499 used in a particular embodiment). The pressure in byproduct stream 28 and product hydrogen stream 14 will be less than the delivery pressure, at least partially due to the pressure-driven separation process described in the illustrative example. In times at which there is demand for the hydrogen gas produced by the hydrogen generation assembly, the hydrogen gas is drawn from the fuel processing system as it is rated from the mixed gas stream. Similarly, the byproduct stream is also withdrawn from the fuel processing system. Some backpressure on the byproduct stream may increase the separation produced in the separation region by urging more hydrogen gas to pass through the hydrogen-selective membrane than would occur if orifice 232 was not exerting backpressure on the byproduct stream, and thereby the rest of the fuel processing system.
When there is less demand for product hydrogen stream 14, the flow rate of hydrogen gas in this stream may be limited or even stopped, via a suitable valve assembly or other flow-regulating device, such as may be included downstream from separation region 24. When this occurs, there will be a greater partial pressure of hydrogen gas on the permeate side of the hydrogen-selective membrane, thereby resulting in less hydrogen gas permeating through the membrane. This, in turn, results in more hydrogen gas and a greater overall flow rate in byproduct stream 28. Without restricting or otherwise limiting the flow of this stream, the stream would simply flow to the heating assembly or other destination. This may not negatively affect the operation of the system; however, it may be wasteful from a hydrogen-production fluid standpoint. In some embodiments, the increased flow of byproduct stream 28 and/or the additional hydrogen content of this stream may cause the overall temperature of the hydrogen-producing region to be increased because the burner assembly is consuming more fuel and/or fuel having a greater heating value. It is also possible that the flow rate of byproduct stream 28, if sufficiently high, may flood or otherwise impair the operation of the burner. It is within the scope of the present disclosure to include bypass valves, vents, and other structure to selectively divert a portion of the byproduct stream so that it is not delivered as heating fuel to the burner assembly. As discussed, this also may not be a concern in some embodiments, such as when the byproduct stream is not consumed as a heating fuel for a heating assembly for the fuel processing system.
By exerting backpressure on the system via orifice 232 or other suitable structure, the backpressure may result in less comparative flow of hydrogen-production fluid from the feedstock delivery system during times when the flow rate of product hydrogen stream is limited or stopped, such as from a position downstream from the separation assembly. A potential benefit of using orifice 232 is that the operation of the hydrogen generation assembly is automatically regulated, or stabilized, through the presence of the orifice without requiring complex, typically electrically powered, controllers, sensors and/or related structure. Filter 230 and/or orifice 232 may be, but are not required to be, utilized with any of the hydrogen generation assemblies described, illustrated, and/or incorporated herein.
During startup of the hydrogen generation assembly, heating fuel 13 is initially delivered to the heating assembly, where it is ignited through any suitable mechanism to produce exhaust stream 66. This stream, in turn, is used to heat at least the hydrogen-producing region to a suitable temperature for producing hydrogen gas from the particular fluid 15 being utilized (i.e., to at least a minimum hydrogen-producing temperature). In embodiments of hydrogen generation assemblies 10 that utilize a controller, the controller may be adapted to detect whether ignition of the fuel has commenced. This detection may utilize any suitable sensor. Illustrative, non-exclusive examples of which include optical sensors and thermal sensors, such as thermocouples. If ignition did not occur, the controller may be configured to stop the flow of fuel and/or fluid by the feedstock delivery system (such as by closing valves 41 and 43, stopping pumps that are utilized to propel the fuel/fluid, etc.).
Once the hydrogen-producing region is sufficiently preheated, the flow of heating fuel may be stopped and the flow of hydrogen-production fluid may commence. This transition may (but is not required to) include a brief period in which neither fuel 13 nor fluid 15 are delivered to the hydrogen-producing region or the heating assembly, or no such period may occur. For example, the flow of fuel 13 may be stopped as the flow of fluid 15 is started, or there may be a period in which fuel 13 is being delivered to heating assembly 60 and hydrogen-production fluid is being delivered to hydrogen-producing region 19. In the illustrative example, the reactants utilized in hydrogen-producing region 19 are delivered in stream 64. However, it is within the scope of the present disclosure that the hydrogen-producing region receives at least one additional reactant or other fluid stream. A benefit of all of the reactants being delivered in stream 64 is that the reactants may be heated as a unit, are at the same pressure, and do not require separate delivery systems or mechanisms.
As discussed, and while not required to all embodiments, it is within the scope of the present disclosure that hydrogen generation assembly 10, and/or energy-producing systems 42 incorporating the same, may be constructed to have minimal, if any, balance-of-plant power requirements. By this it is meant that the system may be implemented without requiring much of the fluid-delivery equipment, controllers, and other electronic equipment conventionally utilized for these assemblies and/or systems. As discussed, the heating fuel and hydrogen-production fluid may be stored under pressure, even in embodiments in which one of these fluids is a liquid as dispensed from the feedstock delivery system. For example, the hydrogen-production fluid may be an alcohol, a liquid hydrocarbon, and/or a mixture of water with a liquid alcohol or hydrocarbon. Where conventionally a pump and/or compressor would be utilized to drawn this stream from a supply and to deliver it under a suitable pressure to the hydrogen-producing region, the feedstock delivery systems discussed, illustrated and/or incorporated herein may be (but are not required to be) adapted to draw and deliver the heating fuel to the hydrogen generation assembly's heating assembly and the hydrogen-production fluid to the assembly's hydrogen-producing region without requiring the use of pumps or compressors. Furthermore, the fuel and fluid may be commonly housed in a fuel canister and yet still be available for separate delivery. The consolidation of both the fuel and fluid into the same pressure vessel may increase the compactness and/or portability of the system. Illustrative, non-exclusive examples of feedstock delivery systems that utilize such a canister, or pressurized vessel, are discussed in connection with
As discussed, it is within the scope of the present disclosure that the flow of the heating fuel and hydrogen-production fluid may be controlled by a valve assembly, such as when the heating fuel and hydrogen-production fluid are stored or available in a pressurized condition. As an illustrative example, the flows may be regulated by valve assembly 60, such as which may include two valves or a three-way or other valve that provides for at least three flow configurations. Therefore, responsive to a first user input that initiates the flow of heating fuel to the burner assembly, the hydrogen producing region will start being preheated, either upon initiating the flow of the heating fluid or upon also actuating an ignition source.
This actuation of the ignition source, when necessary, may be coupled to the actuation of the valve assembly so as to occur automatically responsive to actuation of the valve assembly, or may be independently initiated, such as by an operator. Ignition may be manually actuated, such as by a user when the flow of heating fuel is initiated. It is also within the scope of the present disclosure that the ignition source is adapted to ignite automatically upon receipt of the heating fuel stream, such as when the ignition source includes a combustion catalyst. As a further example, the ignition source may be operatively coupled to the switch used to initiate the flow of heating fuel to the heating assembly so that the ignition source is actuated as, or within a selected time period after, the flow of heating fuel is commenced. As yet a further illustrative, non-exclusive example, when the system includes a battery 52 or other energy-storage device, such as a capacitor, ultracapacitor, or flywheel, this device may be utilized to power the ignition source for a sufficient period to initiate combustion of the heating fuel.
For a steam reforming reaction utilizing a hydrogen-production fluid containing methanol and water, the hydrogen-production region is preferably heated to at least 300° C. Illustrative examples of threshold preheating temperatures include 300° C., 325° C., 350° C., 375° C., 400° C., a temperature of at least 350° C., a temperature in the range of 350-450° C., a temperature in the range of 350-400° C., a temperature in the range of 375-425° C., etc. The desired threshold temperature upon detection of which the flow of hydrogen-production fluid will be commenced may vary depending upon such factors as the mechanism by which hydrogen gas is produced, whether the heating assembly will continue to be supplied with heating fuel after the flow of hydrogen-production fluid is commenced, the rate and/or time period for which this supply of heating fuel will continue to be supplied to the heating assembly, the composition of the hydrogen-production fluid, the environment in which the hydrogen-generation assembly is being used, user preferences, etc.
The determination that the hydrogen-producing region has been heated to a selected threshold temperature may be accomplished via any suitable mechanism and/or method. For example, a temperature sensor may be used to indicate the temperature of the hydrogen-producing region. An operator may manually detect the temperature, and if it is within an acceptable temperature range, commence the flow of hydrogen-production fluid to the hydrogen-producing region and/or stop or reduce the flow of heating fuel to the heating assembly, such as by simply actuating valve assembly 60. It is also within the scope of the present disclosure that the temperature sensor is coupled to the valve assembly, such as via a suitable temperature-driven solenoid or actuator, to automatically commence the flow of hydrogen-production fluid and/or reduce or stop the flow of heating fuel when the preselected threshold temperature has been detected. For example, a bimetallic temperature sensor, solenoid or other detector or actuator may be utilized.
The time required to preheat the hydrogen-producing region should be reproducible as long as the heating fuel, operating environment or other parameters are not changed. Therefore, a timer may be used to indicate when an acceptable amount of time has elapsed, with this threshold time corresponding to a previously determined time period within which the hydrogen-producing region was preheated to an acceptable temperature. The timer may be adapted to provide a visual, audible or other signal to an operator. It is also within the scope of the disclosure that the timer is coupled to the valve assembly to automatically commence the flow of hydrogen-production fluid and/or to stop or reduce the flow of heating fuel upon expiration of the preselected time period.
When the hydrogen-producing region has been heated to a suitable temperature for producing hydrogen gas via the steam reforming or other mechanism by which the region is adapted to operate, and the flow of hydrogen-production fluid to the hydrogen-production region has commenced, hydrogen gas will start being produced in the hydrogen-production region upon delivery of fluid 15 thereto. As discussed, it is within the scope of the present disclosure that this may have occurred by two actuations of the valve assembly, or less, and optionally with actuation of an ignition source. The byproduct stream produced in separation region 24 may be adapted to have sufficient fuel value to provide the heating fuel for the heating assembly when the hydrogen generation assembly is producing a product hydrogen stream. Therefore, the assembly may be self-sustaining within a range of suitable operating temperatures as long as the supply of hydrogen-production fluid is not exhausted. Should this occur the system may be adapted to automatically shutdown because the lack of flow of hydrogen-production fluid also means that there will not be a flow of product hydrogen steam 66 or byproduct stream 28.
When hydrogen generation assembly 10 is coupled to a fuel cell stack 40 to provide an energy-producing system 42, the stack may be adapted to automatically produce an electric current upon delivery of product hydrogen stream 14 and an air stream 74 or other oxidant stream to the fuel cell stack. The flow of hydrogen gas to the stack will typically occur within seconds after the flow of fluid 15 to the preheated fuel processing system is commenced. The air stream may be adapted to be automatically delivered to the fuel cell stack, such as when the stack includes an open cathode construction in which air is drawn automatically from the environment in which the stack is used without requiring fans, blowers, or compressors. In such an embodiment, the energy-producing system automatically produces this current and/or powers the operation of an energy-consuming device (which may be electronically connected to the energy-producing system 42 and/or integrated therewith), while only requiring the minimal operator inputs and/or described above. In some embodiments, the fuel cell stack may include an electrically powered fan or blower that is powered by the fuel cell stack, with an initial supply of air being provided by the operator. As a further variation, this initial supply may be provided by a fan or other blower that is powered by a battery or other energy-storage device. Upon generation of an electric current in the fuel cell stack, this battery or other energy-storage device would no longer be needed, as the stack could meet the power requirements of such an air delivery system. When an electric ignition source and/or time is utilized in the heating assembly and/or hydrogen generation assembly, the battery or other energy-storage device may also provide the power thereto. In experiments, the energy requirements of these devices tend to be very small and of short duration, although this is not required to all embodiments.
Illustrative, non-exclusive examples of fuel processing assemblies 31, and hydrogen generation assemblies 10 containing the same, that are adapted to produce product hydrogen stream 14, are discussed with respect to
By returning briefly to
When gaseous fuels 13 are utilized during startup of the hydrogen generation assembly and byproduct stream 28 is utilized as the fuel for heating assembly 60 when the hydrogen generation assembly is in a hydrogen-producing operating state, the gaseous streams may be exposed to an ignition source (or existing flame) and positioned relative to the hydrogen-producing region via any suitable mechanism and/or structure. An illustrative, non-exclusive example of a suitable configuration is for the gas streams to flow through a nested burner assembly that defines generally parallel flow paths for each of the gas streams and/or which establishes flow paths that that position each of the gas streams at a suitable position relative to the hydrogen-producing region.
In
As shown in
As discussed, some feedstock delivery systems 22 for hydrogen generation assemblies according to the present disclosure are adapted to deliver streams of liquid combustible fuel 13 to the heating assembly. Some liquid combustible fuel streams may not be readily ignited and/or combusted at certain operating temperatures within which the hydrogen generation assembly may be utilized. As a non-exclusive example, the fuel stream may be delivered to the heating assembly as a liquid fuel stream at a temperature in the range of approximately 25° C. to approximately 100° C., although temperatures above and below this illustrative range may be used without departing from the scope of the present disclosure. As used herein, “liquid” or “liquid-phase” is meant to refer to fuel streams that include at least a majority, if not most or even all, or nearly all, of the fuel in the liquid phase at the operating parameters at which the fuel stream is delivered to the heating assembly. Additionally, when fuel stream 64 includes a carbon-containing feedstock 18 or is a composite stream (such as the subsequently discussed composite stream 90) that includes carbon-containing feedstock and water, the fuel stream that is delivered to heating assembly 60 may be in the liquid phase at operating parameters at which it is delivered to the heating assembly. The operating parameters discussed above are not intended to be exclusive examples. Instead, they are meant to illustrate typical parameters, with parameters outside of these ranges still being within the scope of the disclosure. In many applications, such as heating assemblies incorporated in fuel processing assemblies for use in portable or mobile uses, the operating parameters for delivery of fuel stream 64 may vary widely depending on the environmental conditions in which the fuel processing assembly is used. For example, fuel processing assemblies may deliver fuel stream 64 to heating assembly 60 at temperatures ranging from lower than 0° C. to higher than 100° C.
Illustrative, non-exclusive examples of other temperature ranges within which the fuel processing assemblies may be used include temperatures of less than 30° C., less than 20° C., less than 10° C., less than −10° C., less than −20° C., less than −30° C., less than 40° C., temperatures in the range of −50° C. and 100° C., temperatures in the range of −50° C. and 50° C., temperatures in the range of −50° C. and 30° C., temperatures in the range of −30° C. and 50° C., and temperatures in the range of −30° C. and 30° C. As discussed, during startup of the fuel processing assembly, the heating assembly is adapted to receive and initiate combustion of a liquid fuel stream. Some liquid fuels may not be liquids in regions of the illustrative temperature ranges described above, and accordingly, the composition of the liquid fuel to be used may be selected with factors that include the expected ambient temperature around the fuel processing assembly. For example, methanol will not be a liquid at 100° C.
In
Heating assembly 60 is illustrated in
As illustrated schematically in
As illustrated in
In some embodiments, fuel chamber 376 may include a full or partial top member 404 for enclosing, either completely or partially, the fuel chamber. When fuel chamber 376 includes a full, or closed, top member to form a substantially closed combustion chamber, fuel chamber 376 also may include one or more air inlets 399 to allow air to enter the fuel chamber for combustion, such as air stream 74 described above, and also may include one or more exhaust ports. The air inlets and exhaust ports may be configured for natural air flow or may be coupled to pumps, blowers, compressors, valves, or other equipment for controlled or pressurized fluid flow. An inlet port 399 for air stream 74 is also shown in dashed lines in
The at least one fuel chamber is configured to receive at least a portion of fuel stream 64, which contains a combustible fuel (13) according to the present disclosure. Fuel stream 64 includes a carbon-containing feedstock 18 may include additional components such as water, air, oxygen, hydrogen, or other components that are combustible, non-combustible, and/or necessary for combustion, such as air or oxygen. While a single fuel stream 64 is shown in
The heating assembly 60 shown in
Examples of suitable heating and ignition sources 378 include at least one of a spark plug, a glow plug, a pilot light, a combustion catalyst, glow plugs in combination with combustion catalysts, electrically heated ceramic igniters, and the like. In some embodiments, heating and ignition source 378 includes an electrical resistance heating element either alone or in combination with an igniter, such as a spark plug. A glow plug is one example of an electrical resistance heating element that may be used alone to both heat and ignite the carbon-containing fuel received by the fuel chamber. Heating and ignition source 378 may include an electrical resistance heating element configured to be heated to a temperature sufficiently hot, also referred to as a red hot or glowing hot temperature, to ignite the carbon-containing fuel in fuel chamber 376.
As illustrated in solid lines in
In operation, and as described above, fuel stream 64 may be delivered to heating assembly 60 as a liquid, or at least partially in a liquid phase. Fuel stream 64 may be delivered to fuel chamber 376 under operating conditions, or delivery conditions, that include a first temperature and a first pressure. The carbon-containing feedstock(s) delivered to the fuel chamber may have a flash point, or minimum ignition temperature, that is higher than the first temperature at which the carbon-containing feedstock(s) is delivered to the fuel chamber. As used herein, “flash point” refers to the minimum temperature at which the vapor pressure of the liquid is sufficient to form an ignitable mixture with air near the surface of the liquid. The flash point for the fuel stream received by fuel chamber 376 may depend upon such factors as the carbon-containing feedstock in the fuel stream, the relative concentrations of carbon-containing feedstock and other components in the fuel stream, the conditions in the fuel chamber, etc.
While the flash point refers to the minimum temperature at which a liquid fuel will have a vapor pressure above its surface sufficient to form an ignitable mixture with air, whether the mixture will ignite is dependent upon the concentration of the combustible fuel vapor in the air at the location of the ignition source. For example, if the ignition source is spaced-apart from the surface of the liquid carbon-containing feedstock, a number of factors may have diluted the concentration of the combustible fuel vapor. The lower flammability limit is often used to refer to the minimum concentration of the combustible fuel vapor in air for which a flame can propagate. As used herein, “ignition vapor pressure” may be used to refer to the minimum vapor pressure at which ignition of the fuel in air will occur.
The temperature of the liquid carbon-containing feedstock in fuel chamber 376 necessary to produce an ignitable vapor concentration (i.e., a concentration at least equal to the lower flammability limit) may be higher than the flash point temperature and will be referred to herein as the ignition temperature. While the ignition temperature accounts for environmental factors such as availability of fresh air in the vapor space above the liquid fuel in the area adjacent the ignition source and the ability of the fuel vapor to exit the fuel chamber, the ignition temperature will be referred to herein as a property of the carbon-containing fuel.
The fuel stream may enter the fuel chamber at a first temperature and may have an ignition temperature greater than the first temperature. In some embodiments, the carbon-containing fuel delivered to the fuel chamber may have an ignition partial pressure, and the carbon-containing fuel in the fuel chamber may have an initial partial pressure less than its ignition partial pressure. In some applications of heating assembly 60, the first temperature (delivery temperature) of fuel stream 64 may be such that there is substantially no carbon-containing feedstock in the vapor phase. In other applications, the fuel stream may be delivered at a first temperature at which there is some carbon-containing feedstock in the vapor phase. However, in many applications the concentration of carbon-containing feedstock in the vapor phase at the first temperature will not be sufficient to form a flammable mixture at the location of heating and ignition source 378. That is, the first temperature will be less than the ignition temperature of the carbon-containing fuel. Cold weather applications and configurations where fuel stream 64 includes a composite stream having water and carbon-containing feedstock are exemplary, though not exclusive, applications where the first temperature will not yield sufficiently high concentrations of carbon-containing feedstock vapor, or fuel vapor, to form an ignitable mixture at the heating and ignition source.
With continued reference to
Heating assembly 60 also includes a heating and ignition source 378, as described briefly above. As illustrated in
With continuing reference to
As discussed, heating and ignition source 378 may include one or more devices. Regardless of the configuration, heating and ignition source 378 may be understood to provide a heating area and an ignition area. The heating area and the ignition area may be separate portions of the source 378, they may be the same portions of the source, or they may include overlapping portions of the source. In a unitary heating and ignition source disposed entirely in the fuel vapor region, for example, the heating area and the ignition area may be coextensive. In multi-component heating and ignition sources, one component may be (at least primarily) configured to heat the liquid while the other component is (at least primarily) configured to ignite the vapor. Additionally or alternatively, a unitary device may be configured with two or more portions of different constructions, such as of different materials, to impart different characteristics or features as discussed herein. One such portion may be better suited (i.e., primarily configured) to heat the liquid while the other portion is better suited to ignite the fuel. Moreover, a unitary heating and ignition source of consistent construction, or any other heating and ignition source, may be disposed with a first portion in the liquid fuel and a second portion in the fuel vapor. In such a configuration, the portion in the liquid fuel may be considered a heating area while the portion in the fuel vapor may be considered an ignition area and, in some applications, a heating source.
As discussed above, heating and ignition source 378 may comprise any number of devices, structures, circuits, members, and/or materials. In some embodiments, heating and ignition source 378 may include an electrical resistance heating element 400. Electrical resistance heating element 400 may include a conventional wire made of suitable electrically resistant materials that generate heat upon receipt of an electric current. Illustrative, non-exclusive examples of such materials include tungsten and Nichrome alloys (such as 80Ni20Cr and 60Ni16Cr24Fe). Additionally, the materials used in electrical resistance heating element 400 may be selected based on their performance in the conditions of the fuel chamber, such as having a high thermal breakdown temperature, being non-reactive with the carbon-containing fuels in the fuel chamber, and being otherwise suitable under other conditions that may affect the ability of the heating and ignition source to heat and ignite the fuel in the fuel chamber. Exemplary materials include silicon-carbide and other refractory materials. It is within the scope of the present disclosure that any suitable material or combination of materials may be used in heating and ignition source 378. The particular materials used in a given embodiment may depend on such factors as the carbon-containing feedstock in the fuel stream, the hydrogen-producing mechanism(s) utilized by the fuel processor, the configuration of the heating assembly and fuel chamber, the configuration and disposition of the heating and ignition source, etc.
With continued reference to
As discussed, heating assembly 60 (and/or burner assembly 62) may include a primary burner assembly 358 in addition to start-up burner assembly 356. In
Additionally, fuel chamber 376 may optionally include at least one baffle 406, illustrated in dotted lines in
Ignition chamber 408 may be configured to at least partially confine the fuel vapor evaporating from the liquid fuel as the heating and ignition source heats the fuel chamber. By at least partially confining the fuel vapor, ignition chamber 408 may facilitate or assist in initiating ignition of the (heated) fuel by reducing the dissipation of the fuel vapor and minimizing the possibility that fuel vapor can be blown away from the heating and ignition source by environmental conditions. These factors otherwise could result in an actual ignition temperature or flash point that is above the theoretical ignition temperature or flash point of the particular fuel composition. When fuel chamber 376 includes an ignition region 380, such as ignition chamber 408, it is within the scope of the present disclosure that the ignition region may be in communication with the combustion region such that the flame and combustion initiated in the ignition region can propagate to the combustion region. This is illustrated in
With reference to
Heating assemblies 60 according to the present disclosure may be used with fuel processing assemblies that do not include a vaporization region for the feed stream for the hydrogen-producing (reforming) region of the fuel processor and/or may include a vaporization region that is not directly heated by stream 66 and/or which is not positioned between the heating assembly and region 19. When configured with a vaporization region that includes at least one length of tubing or other enclosed region in which the feed stream is vaporized by heat exchange with the heated exhaust stream 66 from the heating assembly flowing external the tubing or other region through which the feed stream flows to be vaporized, tubing/region 415 may be formed or shaped in any configuration designed to provide a desired amount of exposure time, and coincident heat transfer, in the vaporization region for the feed stream prior to entering the fuel processor.
In some embodiments, transport medium 410 may be porous or otherwise adapted to absorb the liquid fuel in fuel chamber 376. Absorbent materials 422 in transport medium 410 may enable the transport medium to prevent spillage of the liquid fuel during transport of a fuel processing assembly having a fuel chamber that is not substantially closed, such as a fuel chamber configured as an at least substantially open-topped reservoir. The absorbent materials may draw in the liquid fuel and be adapted to move the liquid fuel to the top 412 as liquid fuel is consumed. When transport medium 410 is adapted to at least temporarily absorb the liquid fuel that is delivered to the fuel chamber, the transport medium may also be described as a containment medium, in that the liquid fuel that is absorbed by the medium (prior to being combusted) is prevented from spilling from the fuel region, such as if the fuel chamber were suddenly tilted or overturned.
Additionally or alternatively, transport medium 410 may include fibers, tubes or other structures 424 that are adapted to wick, such as by capillary action, the liquid fuel from the bottom of the fuel chamber to the top 412 of transport medium 410, as shown more clearly in
Transport medium 410 may, but is not required to in all embodiments, provide a flame-holding surface in the fuel chamber. For example, transport medium 410 may be configured to provide a flame-holding, or flame-positioning, top surface that is spaced from the fuel processor 12, hydrogen-producing region 19, vaporization region 69, or other portion of hydrogen generation assembly 10 and/or fuel processing assembly 31 by a predetermined distance to obtain desired heating properties and thermal communication between the flame of the heating assembly 60 and the remaining components of fuel processing assembly 10. One advantage of utilizing transport medium 410 is that the flame of the combustion can be maintained at a consistent distance from the other components throughout the combustion process even as the liquid fuel is consumed.
The top 412 of transport medium 410 may be spaced from heating and ignition source 378 by a first distance, from top member 404 by a second distance, from vaporization region 69 by a third distance, and from hydrogen-producing region 19 by a fourth distance. It is within the scope of the present disclosure that any or all of the distances and any other spacing between transport medium 410 and other components of hydrogen generation assembly 10 may be varied to obtain selected, or desired, thermal communication between the components. It is within the scope of the present disclosure that the first distance may be zero, or nearly zero, or even that the heating and ignition source may extend at least partially into, or otherwise below the upper surface of, the transport medium, which may be described as corresponding to a negative first distance.
Also shown in
It is within the scope of the present disclosure for the primary burner assembly to extend within the liquid fuel region of the start-up burner assembly. While this construction is not required, it enables the flames produced by the burner assemblies to extend at the same or similar heights. As discussed, the relative distances between the portions of the fuel processing assembly to be heated and the components of the heating assembly may vary within the scope of the present disclosure. In some embodiments, it may be desirable to have these components relatively closely together so as to not diminish or otherwise less efficiently utilize the heat value of the heated combustion stream. However, the geometry and construction of the fuel processing assembly may provide structural (i.e., space and size) constraints that impair this optional design objective. By recessing the primary burner assembly within the fuel region of the start-up burner assembly (for example, instead of locating it above the liquid fuel region of the start-up burner assembly), the thickness of the burner assembly, or perhaps more specifically the distances between the flames produced by the start-up and primary burner assemblies and the hydrogen-producing region, may be comparatively reduced.
When the fuel chamber includes a transport medium and a primary burner assembly that extend within the liquid fuel region of the fuel chamber, the medium and burner assembly may be oriented in any suitable configuration within this region of the fuel chamber. As illustrative, non-exclusive examples, the transport medium may extend on opposed sides, and optionally beneath, the primary burner assembly, the primary burner assembly may be received within a recess or other passage in the transport medium, etc.
Another illustrative example of a hydrogen generation assembly 10 with a fuel processing assembly 31 having a heating assembly 60 according to the present disclosure is shown in
In the illustrated example, the primary burner assembly 358 includes an elongate conduit that extends at least generally parallel to the hydrogen-producing region and vaporization region of the fuel processor, with the primary burner assembly including apertures 428 through which a gaseous fuel stream is emitted and combusted from the primary burner assembly. In the illustrated example, primary burner assembly 358 is adapted to receive the byproduct stream 28 from region 25, which contains hydrogen-producing region 19 and at least one purification region 24. Although not required, region 25 is shown including a housing 27 that includes hydrogen-producing region 19, such as may include a stream or other reforming catalyst. Housing 27 may further contain at least one hydrogen-selective membrane and/or methanation catalyst that is adapted to separate the mixed gas stream produced in the hydrogen-producing region into product hydrogen stream 14 and byproduct stream 28.
During startup of a hydrogen generation assembly with a feedstock delivery system or other mechanism for utilizing a liquid combustible fuel stream for the heating assembly during start up of the hydrogen generation assembly, at least a portion (if not all) of the fuel stream is delivered to the heating assembly as a liquid fuel stream. The liquid fuel stream is thereafter ignited and combusted with an air stream, or ambient air, to produce a heated combustion stream that is used to heat the steam reformer. As discussed, in some embodiments, the fuel stream may have at least one of the same components as the hydrogen production fluid, and in some embodiments may have the same composition as this stream, including (but not limited to) compositions that include at least 25 vol % water.
In some embodiments, a pump, such as a positive displacement pump, may be used and adapted to provide a predetermined volume of the liquid fuel stream, which may also be described as a predetermined quantity of liquid, carbon-containing feedstock, to the fuel chamber of the heating assembly. In some embodiments, a controller may be used to control the operation of the pump. On other embodiments, the pump may be manually actuated and/or the predetermined volume may be manually poured or otherwise introduced into the fuel chamber. As discussed, the liquid fuel stream is delivered to the fuel chamber and retained therein as a liquid supply of fuel that is consumed during at least startup of the fuel processing assembly. Therefore, unlike a heating assembly that consumes the fuel stream as it is delivered thereto, the start-up burner assembly of the present disclosure at least temporarily stores a volume of liquid fuel. In some embodiments, the fuel stream may be configured to provide a stream of carbon-containing feedstock during at least the start up phase and, optionally, during the (hydrogen-producing) operating state of the fuel processor.
The fuel stream is delivered to the fuel chamber and is heated by the heating and ignition source to increase the vapor pressure of the carbon-containing fuel in the fuel vapor region of the start up burner assembly. The fuel vapor is ignited by the heating and ignition source and the combustion of the fuel begins. The heat of combustion adjacent the ignition source will radiate and heat the adjacent liquid fuel to further increase the vapor pressure of the carbon-containing fuel in the fuel chamber, allowing the flame and combustion to propagate throughout the fuel chamber. The temperature at which the fuel vapor ignites is determined by a number of factors, as discussed above. When the temperature in the fuel chamber adjacent the heating and ignition source reaches the ignition temperature, the fuel vapor is ignitable. In some embodiments, the fuel vapor ignites, or is ignited, upon being heated to the ignition temperature. In other embodiments, the fuel vapor only ignites when the surface temperature of the heating and ignition source reaches the heating element ignition temperature, or the temperature at which the surface of the heating element is sufficiently hot to ignite the fuel vapor (such as glowing hot or red hot).
Because the combustion may propagate through the fuel chamber, the heating and ignition source may be significantly smaller than the size of the fuel chamber. For example, the heating and ignition source may be a localized heat source. A localized heat source is a heating element that is substantially smaller than the fuel chamber. The liquid fuel disposed in the fuel chamber has a top surface having a surface area. The localized heat source may be coiled, linear, or otherwise configured as described above and may be disposed above, or partially above, the top surface of the liquid fuel. The localized heat source may have a footprint (i.e., occupy a space) corresponding to the surface area of liquid fuel corresponding or aligned with the localized heat source. The footprint of the localized heat source may be substantially smaller than the surface area of the liquid fuel in the fuel chamber. For example, the footprint may correspond to only 20% of the surface area of the liquid fuel region. In other embodiments, the heating and ignition source may be sized to have a footprint corresponding to only 10%, 5%, or smaller amounts of the surface area. It is within the scope of the present disclosure that the heating and ignition source be larger, or correspond with a larger percentage of the liquid fuel surface area, and that the heating and ignition source may be still smaller. The size of the heating and ignition source and the configuration of the fuel chamber (i.e., whether there are baffles, top members, disposition of the heating and ignition source, etc.) may affect the ignition temperature of the carbon-containing fuel and may also affect the heating element ignition temperature. Moreover, the size and location of the ignition region and combustion region will be determined by the configuration of the heating and ignition source, as described above.
Once combustion is initiated in the start-up burner assembly, the combustion continues, in some cases aided by the transport medium, at least until the reformer or other hydrogen-producing region is heated to a selected, or predetermined, temperature. In embodiments utilizing a metered pump to dispense a predetermined amount of carbon-containing feedstock into the fuel chamber, the amount of fuel dispensed may be calculated to contain at least enough carbon-containing feedstock to raise the temperature of the hydrogen-producing region to the predetermined temperature. In some embodiments, the predetermined temperature to which the start-up burner assembly is adapted to heat the reformer is greater or less than the operating temperature of the hydrogen-producing region. For example, the selected, or predetermined, temperature to which the start-up burner assembly raises the reformer may be a certain amount above or below the desired operating, or reforming, temperature, such as 25-125° C., 25-75° C., 50-100° C., etc., less than or greater than the reforming temperature.
In embodiments utilizing a metered pump that delivers a predetermined quantity of fuel to the start-up burner assembly, the start-up burner assembly may be configured to combust the fuel until all the fuel is combusted, at which point the primary burner assembly may be operated to maintain the operating temperature of the fuel processing assembly. In exothermic fuel processing assemblies, the start-up burner assembly may be operated to raise the fuel processing assembly to the predetermined temperature, sufficient to begin operating the hydrogen-producing mechanism, and/or to vaporize or otherwise preheat the feed stream(s) for the fuel processor. At this point, the exothermic reaction of the hydrogen-producing region may be used to maintain the operating temperature of the hydrogen-producing region.
In embodiments not utilizing a metered pump (or other delivery mechanism that is adapted to dispense a predetermined quantity of the carbon-containing fuel stream to the fuel chamber), the liquid combustible fuel stream may be delivered to the start-up burner assembly until the hydrogen-producing region is heated to a predetermined temperature. In this embodiment, the predetermined temperature may be still lower than the temperature discussed above (i.e., there may be a greater difference between the predetermined temperature and the reforming temperature). One reason for this is that the fuel chamber may contain a certain amount of liquid fuel that is yet uncombusted when the fuel stream stops flowing to the start-up burner assembly, which liquid fuel will be combusted to further raise the temperature of the hydrogen generation assembly even after the liquid combustible fuel stream stops flowing to the start-up burner assembly.
As compared to the embodiment with the metered pump, an embodiment with a continual flow of fuel to the start-up burner assembly may have at least one additional feature, such as a temperature- or time-based flow controller and/or a liquid fuel, ignition chamber separator. The temperature- or time-based flow controller may be adapted to automatically stop, either abruptly or gradually, the flow of the liquid combustible fuel stream to the start-up burner assembly when the predetermined temperature is reached, such as by measuring the temperature directly or by measuring the time and comparing it to empirical temperature/time tables. It is within the scope of the present disclosure that the flow of the fuel stream may also be controlled manually in some embodiments. Additionally, the start-up burner assembly may include a liquid fuel ignition chamber separator to prevent newly added fuel and carbon-containing feedstock from cooling the liquid fuel already being heated by the heating and ignition source.
Also within the scope of the present disclosure are start-up heating assemblies that utilize a metered pump to provide an initial quantity of liquid fuel to be heated and ignited and then a continuous feed of the liquid combustible fuel stream after ignition and combustion has begun, to ensure continued combustion until the predetermined temperature is obtained.
Whether a metered pump and predetermined volume is utilized, a continuous feed of the fuel stream may be utilized, or some combination of the two, upon heating the hydrogen-producing region to the predetermined temperature at which the feed stream can be delivered to the hydrogen-producing region, the feed stream may be directed to the reforming region and hydrogen production may begin. In embodiments where a common stream, such as a composite stream containing water and carbon-containing feedstock, is used as both the feed stream and the fuel stream, the transition between supplying the fuel stream and supplying the feed stream may be instantaneous, gradual, or there may be a break between supplying the fuel stream and supplying the feed stream, such as when a metered pump is used to deliver a predetermined quantity of fuel to the heating assembly.
As hydrogen gas is produced in the reforming region of the steam reformer, and then purified in one or more purification regions, a gaseous byproduct stream may be produced and may be delivered to the heating assembly to be used as a fuel stream by the primary burner assembly. In some applications, such as most steam reformers in which the carbon-containing feedstock is methanol, the byproduct stream should have sufficient heating value that the heating assembly will not require any additional liquid fuel, such as additional carbon-containing feedstock from the feed stream for the hydrogen-producing region. However, when other carbon-containing feedstocks, and especially hydrocarbons, are used, it may be necessary either to continue to supply the primary burner assembly with carbon-containing feedstock, such as from the feed stream or another source, and/or to use some of the product hydrogen stream as a fuel stream in order to provide sufficient fuel to maintain the temperature of the reformer.
As discussed previously, hydrogen generation assemblies 10 according to the present disclosure may utilize any suitable type and/or number of feedstock delivery systems 22 appropriate for the feed and/or fuel streams to be delivered thereby. As also discussed, some feedstock delivery systems include pumps or other electrically powered propulsion mechanisms, while others do not required or otherwise utilize pumps. Some feedstock delivery systems are in fluid communication with a pressurized supply (112) of fuel or feed, while others are in fluid communication with an unpressurized, or low pressure, supply that requires external forces to propel the fluid to the fuel processing assembly, such as to the hydrogen producing region or the heating assembly thereof. While the fuel and feed streams may be separately stored and delivered, it is also within the scope of the present disclosure that this complete separation is not required, as illustrated with respect to
According to an aspect of the present disclosure, which is not required to all embodiments, a liquid-phase carbon-containing feedstock 84 may be used for both carbon-containing feedstock portion 18 of feed stream 16 for reforming region 19 and carbon-containing feedstock portion 65 of fuel stream 64 for heating assembly 60, such as schematically illustrated in
In the illustrative example shown in
The distribution of liquid carbon-containing feedstock 84 between the hydrogen-producing region and the heating assembly may be manually controlled. However, in many embodiments, it may be desirable for the distribution to be predetermined and/or at least partially automated, such as by including a controller 88 that selectively regulates the delivery of feedstock 84 between the hydrogen-producing region and the heating assembly. An example of a suitable controller for a steam reforming fuel processor is disclosed in U.S. Pat. No. 6,383,670, the complete disclosure of which is hereby incorporated by reference. In some embodiments, controller 88 and/or valve assembly 86 may be configured to allow a predetermined initial volume of carbon-containing feedstock into heating assembly 60, as will be discussed in greater detail herein.
As discussed previously, in the context of a steam reformer or other fuel processor that produces hydrogen gas from water and a carbon-containing feedstock, feed stream 16 may be at least substantially, and typically entirely, comprised of a mixture of water and a liquid-phase carbon-containing feedstock 84 that is preferably miscible in, or with, water. As such, a single (composite) feed stream 90 containing water 17 and carbon-containing feedstock 84 can be consumed as both the hydrogen-producing feed stream 16 for the reforming reaction, as well as the heating assembly fuel stream 64. Further reduction in the supplies, delivery systems, flow regulators, delivery conduits and the like may be achieved according to another aspect of the present disclosure by feed stream 16 and fuel stream 64 both containing the same liquid carbon-containing feedstock 84 and water 17, with the carbon-containing feedstock preferably being miscible in water. This is schematically illustrated in
Similar to the previously discussed alternatives of
The relative amounts of water 17 and liquid carbon-containing feedstock 84 in composite feed stream 90 may vary within the scope of the present disclosure. For example, the ratio may depend upon such factors as the particular carbon-containing feedstock being used, the hydrogen-producing mechanism being used in the fuel processor, user preferences, the catalyst being utilized, the demand for hydrogen gas, the efficiency of the reforming catalyst, etc. The relative concentrations of these components may be expressed in terms of a ratio of water to carbon. When feedstock 84 is methanol, a 1:1 molar ratio of steam to carbon has proven effective. When feedstock 84 is ethanol, a steam-to-carbon molar ratio of 2-3:1 has proven effective. When feedstock 84 is a hydrocarbon, a steam-to-carbon molar ratio of approximately 3:1 is typically used. However, the illustrative ratios described above are not meant to be exclusive ratios within the scope of the disclosure, and others, including greater and lesser ratios, may be used.
In
Another illustrative, non-exclusive example of a suitable feedstock delivery system 22 that may be used with hydrogen generation assemblies 10 according to the present disclosure is shown in
Pump 102 may be powered by any suitable power source; illustrative, non-exclusive examples of which include a component of hydrogen-producing fuel cell system 42, such as fuel cell stack 40 and/or energy storage device 52. Additional illustrative examples include a power supply that is independent of power output produced by the fuel cell system, such as an external, or dedicated, battery, an electrical grid, etc. While not required, pump 102 may be a single-speed, or single-output, pump that is adapted to either be in an on, or active, configuration in which the pump is receiving liquid stream 110 and emitting liquid stream 116, or an off, or unpowered, configuration in which the pump is not emitting stream 116. The actual output of the pump will vary with the voltage of the power output delivered to the pump, which may tend to vary.
As discussed, pump assembly 100 includes at least one pump. Accordingly, it is within the scope of the present disclosure that pump assembly 100 may include a single pump 102 or more than one pump 102. When the pump assembly includes more than one pump, the pumps may cooperate to draw liquid stream 110 and/or emit outlet stream 116. Additionally or alternatively, the pumps may each be adapted to draw a liquid stream 110 from the same or different sources 112 and/or to each emit an outlet stream 116 therefrom.
Supply 112 includes any suitable type and/or number of reservoirs and/or other sources from which the liquid stream may be drawn or otherwise received by an inlet 106 of a pump 102 of pump assembly 100. Illustrative, non-exclusive examples of suitable supplies 112 include tanks, canisters, and other liquid vessels, which may or may not be pressurized. Liquid stream 110 contains at least one component of feed stream 16, such as water 17 and/or a carbon-containing feedstock 18. As indicated in
As shown in
Described in terms of the fluid conduits of, or associated with, feedstock delivery system 22, and as illustrated somewhat schematically in
In the illustrative example shown in
Although not required to all embodiments, it is within the scope of the present disclosure that pump 102 is adapted to continuously draw stream 110 thereto and to emit liquid stream 116 therefrom, with it being within the scope of the present disclosure that the pump may be adapted to deliver a greater flow rate of stream 116 than is desired, or in some embodiments even able to be present in feed stream 16. Accordingly, the pump may be described as providing an output stream having a greater flow rate of liquid than the flow rate of feed stream 16 that is produced therefrom and delivered to the hydrogen-producing region (or other portion) of fuel processor 12. In such a configuration, the pump may be described as being configured to provide excess liquid, or excess flow rate, in output stream 116, thereby providing a flow of liquid that forms recycle stream 136.
By maintaining the pump in an operating state that provides an output stream 116 that contains a greater amount of feedstock than required by the hydrogen-producing region, the pump may be configured to maintain a constant output regardless of the hydrogen demand, or requirements, of the hydrogen-producing region, at least when the hydrogen-producing region is in a hydrogen-producing operating state. In some embodiments, the pump may be configured to maintain a flow rate of liquid feedstock that exceeds the hydrogen-producing region's maximum demand for the feedstock (i.e., the demand for the feedstock when the hydrogen-producing region is at its maximum rated production rate and/or when the hydrogen-producing region is producing sufficient hydrogen gas to produce a power output at the maximum rated power output of the fuel cell stack). In some embodiments, the feedstock delivery system may be adapted to provide an output stream that has a flow rate that is at least 10%, at least 25%, or even at least 50% greater than the amount of feedstock required by the hydrogen-producing region. However, because of the self-regulating nature of the feedstock delivery system, the excess feedstock is not wasted, and instead is recycled through the feedstock delivery system, where it may be reused or returned to the feedstock supply.
In
Flow restrictor 140 may include any suitable structure that is configured to restrict the flow path of the recycle stream through recycle conduit 136. As an illustrative, non-exclusive example, the flow restrictor may include an orifice 142 having an opening 144 of smaller cross-sectional area than a portion of recycle conduit 136 upstream of the orifice and/or of smaller cross-sectional area than delivery conduit 134. An example of such an orifice is schematically illustrated in
Pressure-actuated valve 150 is adapted to selectively permit the recycle stream to bypass the flow restrictor and thereby not be subjected to the backpressure created by the restrictive orifice 142 or other flow restrictor 140 and yet still be able to be returned to the supply or other portion of the feedstock delivery system that is upstream of the pump's working portion. Illustrative, non-exclusive examples of suitable pressure-actuated valves include pressure relief valves and check valves that are fluidly connected to as described herein, namely, to selectively restrict and permit liquid flow to a bypass conduit that enables the liquid to bypass the flow restrictor. As graphically indicated in
Pressure-actuated valve 150 is normally adapted, or biased, to restrict flow through bypass conduit 152 when the pressure in recycle stream 136 upstream of the flow restrictor (i.e., between output conduit 132 and flow restrictor 140) is less than a threshold recycle pressure. This configuration may be referred to as the closed, or flow-restricting, configuration of the pressure-actuated valve. However, when the pressure reaches (or exceeds) this threshold recycle pressure, the pressure-actuated valve is adapted to automatically permit liquid from upstream of orifice 140 to flow through bypass conduit 152.
When the pressure reaches (or exceeds) this threshold recycle pressure and the pressure-actuated valve is (automatically) configured to its actuated configuration responsive thereto, at least a portion of recycle stream 120 may flow through the bypass conduit, thereby reducing the pressure of the liquid upstream of the flow restrictor. This may also reduce the pressure of the feed stream delivered by the feedstock delivery system. The threshold recycle pressure may be the same as the maximum, or threshold, delivery pressure that is acceptable for feed stream 16. However, it is also within the scope of the present disclosure that these pressures are not the same. For example, the threshold recycle pressure may be selected to be less than the threshold delivery pressure, such as by a determined increment, to provide a buffer or pressure differential between the pressure at which the pressure-actuated valve is designed to permit flow through the bypass conduit (and thereby reduce the pressure in the delivery and other associated streams) and the maximum pressure at which the delivery conduit and/or fuel processing assembly is designed, or desired, to receive the feed stream.
As indicated herein, at least the hydrogen-producing region of fuel processing assembly 31 may be designed to operate at an elevated pressure, such as a pressure of at least 50 psi. When the fuel processing assembly includes a purification, or separation, region, such as described herein, this region may also be designed to operate at an elevated pressure. The particular maximum and minimum operating pressures for a particular fuel processing assembly will tend to vary according to a variety of possible factors. Illustrative examples of such factors may include, but may not be limited to, the hydrogen-producing reaction utilized in hydrogen-producing region 19, the composition of feed stream 16, the viscosity of the liquid in feed stream 16, the delivery conduit construction, size, and/or configuration, the construction of the fuel processing assembly, the pressure requirements of the fuel processing assembly and/or fuel cell system downstream from the hydrogen-producing region, design choices and tolerances, etc. For example, some fuel processing assemblies may be designed to maintain an elevated pressure in at least the hydrogen-producing region, and optionally at least one purification region thereof by utilizing a restrictive orifice or other suitable flow restrictor downstream of the hydrogen-producing region, and optionally downstream of a purification region that is also preferably maintained at an elevated pressure.
The amount of liquid (i.e., the percentage of recycle stream 120) that flows through conduit 152 may vary within the scope of the present disclosure. In some embodiments, the entirety of the stream that forms recycle stream 120 may flow through the bypass conduit when the pressure-actuated valve is in its actuated, or flow-permitted, configuration. In other embodiments, some of stream 120 may also flow through orifice 142 or other flow restrictor 140 even in periods in which the pressure-actuated valve is in this actuated configuration.
When present, pressure-actuated valve 150 may include a valve, or valve member, 156 and a biasing mechanism 158 that is adapted to bias the valve from its actuated configuration to its closed configuration. Biasing mechanism 150 may include any suitable structure or device adapted to provide the above-described biasing and yet permit the pressure-actuated valve to be configured to its actuated configuration when the threshold recycle pressure is reached, or exceeded. An illustrative, non-exclusive example of a suitable biasing mechanism is a spring or other resilient member that exerts a biasing force against the valve member in a direction that opposes the force exerted upon the pressure-actuated valve by the liquid in the recycle stream upstream of the flow restrictor. In other words, the liquid stream upstream from the flow restrictor may exert a force that urges the pressure-actuated valve from its closed configuration to its actuated configuration. This force is applied against the bias of, or the force exerted by, biasing mechanism 158. When the force exerted by the stream exceeds the force exerted by the biasing mechanism, the pressure-actuated valve is configured to its actuated configuration. Otherwise, when the stream pressure exerts a force to the pressure-actuated valve that is less than the force applied by the biasing mechanism, the pressure-actuated valve is adapted to remain in its closed configuration. Biasing mechanism 158 may also function as a pressure detector, or pressure sensor, that is adapted to detect when the pressure of the liquid stream emitted by the pump assembly exceeds a threshold pressure, such as a threshold recycle or delivery pressure. Specifically, when the pressure of the liquid, as applied against the biasing mechanism, is sufficient to overcome the force exerted by the biasing mechanism, then the threshold pressure is exceeded. Accordingly, the biasing mechanism may be adapted to exert a biasing force that sets or corresponds to the threshold pressure, such as the threshold recycle or delivery pressure.
Biasing mechanism 158 is preferably further adapted to automatically return the pressure-actuated valve to its closed configuration, such as when the pressure detected thereby (or applied thereto) decreases to below the threshold recycle pressure, when the pressure decreases to a level that is not sufficient to overcome the biasing force exerted by the biasing mechanism, and/or after a predetermined time period has elapsed since the pressure-actuated valve was configured to its actuated configuration. In other words, it is within the scope of the present disclosure that the pressure-actuated valve is configured to remain in its actuated configuration, once configured thereto, for at least a predetermined minimum time period. It is also within the scope of the present disclosure that the pressure-actuated valve may be configured to automatically transition between its actuated and closed configurations responsive entirely to the forces exerted thereto by the liquid steam and the biasing mechanism.
It is within the scope of the present disclosure that a feedstock delivery system 22 according to the present disclosure may not include both flow restrictor 140 and pressure-actuated valve 150. For example, the feedstock delivery system may include a flow restrictor 140, such as described herein, without a pressure-actuated valve (and accordingly without bypass conduit 152). As another example, the feedstock delivery system may include a pressure-actuated valve 150, such as descried herein, without a flow restrictor that creates backpressure on the outlet stream and which is selectively bypassed using the pressure-actuated valve. In such an embodiment, the bypass conduit would not be present, and the pressure-actuated valve would selectively create backpressure to the outlet (and delivery) streams in its closed configuration, in which flow of the recycle stream is restricted by the pressure-actuated valve. When the pressure exceeds a threshold pressure, as described herein, the pressure-actuated valve is transitioned or otherwise urged to its actuated configuration, in which at least a portion of the outlet stream is recycled to supply 112 or another portion of the delivery system upstream of the pump's working portion.
As discussed, if system 22 does not include a pressure-actuated valve, there is a potential for the pressure to increase beyond selected threshold pressures if the flow restrictor fails, is clogged or otherwise is not able to properly function. However, system 22 and/or fuel processing assemblies and/or fuel cell systems containing feedstock delivery system 22 may include other suitable mechanisms for detecting and reacting to pressures that near or exceed a selected threshold pressure. For example, systems that include a controller may include a pressure sensor that is adapted to measure the pressure in output stream 116, upstream of flow restrictor 140, or in another suitable location, with the controller being adapted to control the operation of at least feedstock delivery system 22 responsive to a pressure that exceeds or nears a selected threshold.
As another example, if feedstock delivery system 22 is implemented without a flow restrictor, then pressure-actuated valve 150 will still be able to selectively reduce the pressure in output stream 116, feed stream 16, etc., responsive to when the pressure in these streams exceeds a selected threshold pressure, such as the above-discussed threshold recycle pressure or threshold delivery pressure. Because such a feedstock delivery system 22 does not include a flow restrictor that establishes some backpressure within system 22 while also permitting a recycle stream to flow therethrough, the pressure in the system will tend to oscillate. More specifically, the liquid pressure will tend to increase as the pump emits a greater flow rate of liquid than is consumed in hydrogen-producing region 19. This increase will tend to continue until the pressure-actuated valve is transitioned from its closed configuration to its actuated configuration. Thereafter, the pressure will tend to decrease until the pressure-actuated valve returns to its closed configuration, at which time the liquid pressure will tend to begin increasing again. This oscillation in the liquid pressure, such as the pressure of feed stream 16 may affect the flow rate of hydrogen gas produced by the fuel processor, which in turn may affect the power output produced by the fuel cell stack. The systems should still be operational, but may not be maintained in as steady, or constant, of operating state due to the pressure fluctuation, or oscillation, in the feedstock delivery system.
As discussed, some feedstock delivery systems 22 accordingly to the present disclosure are adapted to deliver a liquid stream and a gas stream. An illustrative, non-exclusive example of such a feedstock delivery system may be utilized to deliver a liquid hydrogen-production fluid (15) to a hydrogen-producing region of a fuel processing assembly and a gaseous combustible fuel stream (13) to a heating assembly, or vice versa.
In the illustrative examples, the feedstock delivery systems 22 includes pressurized sources 499 of heating fuel 13 and hydrogen-production fluid 15. Illustrative examples of sources 499 include pressurized tanks or other pressure vessels that contain one or both of fuel 13 and fluid 15 under pressure; however, any suitable pressurized source may be used without departing from the scope of the present disclosure. Because these components of feedstock supply streams 11 are available under pressure from the feedstock delivery system, hydrogen generation assembly 10 does not require the use of mechanical pumps, compressors, or other electrically powered components to draw the heating fuel and/or hydrogen-production fluid from sources 499 and to deliver streams under pressure to the hydrogen-producing region and heating assembly of fuel processing system 31. Instead, the streams are automatically propelled from the pressurized source upon opening of a valve or other suitable flow-regulating device that selectively permits or restricts flow of the streams from the feedstock delivery system to the fuel processing system. These flow-regulating devices are schematically illustrated in
It is within the scope of the present disclosure that feedstock delivery system 22 may include a pressure vessel 459 that contains both heating fuel 13 and hydrogen production fluid 15 and which is adapted to separately deliver streams containing the fuel or fluid, such as responsive to the configuration of the valve assembly. An illustrative example of such a feedstock delivery system is shown in
In vessel 459, one of fuel 13 and fluid 15 may be adapted to be discharged from the pressure vessel under its own pressure while the other of fuel 13 and fluid 15 may be adapted to be discharged from the pressure vessel under pressure applied thereto, such as from the first of fuel 13 and fluid 15. For example, the heating fuel may be disposed in the pressure vessel for delivery, under its own pressure, to the heating assembly 460. The hydrogen-production fluid may be disposed in the pressure vessel 459 for delivery, under pressure applied by the heating fuel, to the hydrogen-producing region 19. The hydrogen-production fluid and the heating fuel are maintained at least substantially separate in the pressure vessel, such as in an interior cavity of the pressure vessel. By this it is meant that fuel 13 and fluid 15 are not intermixed throughout the pressure vessel. Instead, the heating fuel and the hydrogen-production fluid are maintained in discrete, identifiable regions of the pressure vessel, with little or no mixing of fuel 13 and fluid 15. For example, the heating fuel may be a gas and the hydrogen-production fluid may be a liquid, with the fuel and fluid being separated by an interface 500 in the pressure vessel. As another example, the heating fuel and the hydrogen-production fluid may be immiscible and separated by an interface 500 in the pressure vessel. While not required, this interface 500 may be formed from the fluid interface between the heating fuel and the hydrogen-production fluid interface layer in the pressure vessel 459. As a further example, the heating fuel and the hydrogen-production fluid may be separated by a physical, or structural, separating member, such as the subsequently described pressure transmitters, that forms the interface 500.
The pressure vessel may also be described as a fuel canister, fuel cartridge, or a feedstock canister or cartridge. As discussed in more detail herein, in some embodiments, it may also be described as a dual fuel or a combined fuel-feedstock canister or cartridge. While illustrated with a single pressure vessel and a single valve assembly, the feedstock delivery system 22 may include more than one pressure vessel and/or more than one valve assembly without departing from the scope of the present disclosure. Additionally, more than one pressure vessel 459 may be in fluid communication with a single valve assembly. In the illustrative example shown in
In
When used to pressurize and propel the hydrogen-production fluid, as discussed above, the heating fuel 13 may also be referred to as a pressurizing fuel. Correspondingly, the hydrogen-production fluid 15 may also be referred to as a pressurized fuel or fluid. When the heating fuel is disposed in the pressure vessel, it is stored under its own pressure, which is sufficient to apply pressure on the hydrogen production fluid 15. The pressurizing heating fuel 13 may be selected to exist in vessel 459 as a two-phase system, including a liquid phase and a vapor phase. This may enable the pressure vessel to maintain a constant, or substantially constant, pressure on the hydrogen-production fluid 15, especially when the temperature of the pressure vessel remains constant. For example, the heating fuel may be selected to be at vapor-liquid equilibrium when the feedstock delivery system 22 is in hydrogen-generation configuration. An illustrative example of a two-phase pressurizing fuel 13 is shown in
In
As discussed, valve assembly 460 is adapted to regulate the flow, or discharge, of the heating fuel and the hydrogen-production fluid from the pressure vessel. Valve assembly 460 includes at least one valve and may include any suitable structure for selectively regulating the flow of streams from the pressure vessel. The schematic representations of valve assembly 460 in
Valve assembly 460 is adapted to selectively and separately discharge the hydrogen-production fluid and the heating fuel from pressure vessel 459. For example, valve assembly 460 may be adapted to allow selective discharge of the heating fuel and the hydrogen-production fluid, but to not allow the discharge of the heating fuel and the hydrogen-production fluid together as a single stream. In some embodiments, this discharge of the hydrogen-production fluid may be under pressure applied by the heating fuel. It is within the scope of the present disclosure that the relationship may be reversed, with the heating fuel being discharged under pressure applied by the hydrogen-production fluid.
The valves and/or valve assembly may be adapted to simply either permit or restrict flow of the corresponding stream through a fixed orifice size. It is also within the scope of the present disclosure that the valves and/or valve assembly may be adapted to provide an adjustable, or variable, flow of either or both of the streams, such as to adjust the relative size of an orifice through which the streams flow through the valve assembly. It is within the scope of the present disclosure that the valve assembly may be actuated, such as between flow and no-flow configurations and/or to adjust the relative rate of flow therethrough, via any suitable mechanism. Illustrative examples include valve assemblies that are adapted to be manually actuated, such as by an individual proximate the valve assembly, actuated by a controller or other electronic device or signal, or automatically actuated responsive to detection or occurrence of a predetermined triggering event, such as a detected temperature, pressure, flow condition, etc.
As graphically illustrated in
The three-way valve or other implemented valve assembly 460 may be configured to permit, or enable, the discharge of the heating fuel until a predetermined condition is met before permitting, or enabling, the discharge of the hydrogen-producing fluid. The predetermined condition may include the passage of a predetermined amount of elapsed time from the initiation of the heating configuration. In embodiments where the feedstock delivery system is supplying a heating fuel to a heating assembly in a hydrogen generation assembly, the predetermined condition may include the hydrogen generation assembly reaching a predetermined operating temperature. The valve assembly 60 may be configured to allow selection of the hydrogen-generation configuration upon the occurrence of other such predetermined conditions.
Such a three-way valve (or other implementation of valve assembly 60) may include a control mechanism that allows selection of the heating configuration from the off configuration, but prevents selection of the hydrogen-generation configuration until the predetermined condition occurs or is otherwise detected, which releases the control mechanism and permits the selection of the hydrogen-generation configuration. The valve assembly may permit selection of the heating configuration and be adapted to automatically switch to the hydrogen-generation configuration when the predetermined condition occurs or is otherwise detected. It is also within the scope of the present disclosure that a valve assembly is used that does not restrict the simultaneous flow of both fuel 13 and fluid 15.
Additional examples of suitable feedstock delivery systems 22 that include pressure vessels 459 containing heating fuel 13 and hydrogen-production fluid 15 in pressurizing-pressurized relationships and which may be used in hydrogen generation assemblies according to the present disclosure are disclosed in U.S. Provisional Patent Application Ser. No. 60/623,259, which is entitled “Feedstock Delivery Systems, Fuel Processing Systems, and Hydrogen Generation Assemblies Including the Same,” was filed on Oct. 29, 2004, and the complete disclosure of which is hereby incorporated by reference. Additional non-examples are disclosed in U.S. patent application Ser. No. 11/096,827, the complete disclosure of which is hereby incorporated by reference for all purposes.
Similar to the hydrogen generation assembly 10 schematically illustrated in
The pressure vessel 459 is shown in
Illustrative examples of hydrogen-producing fuel cell systems 42, hydrogen-producing fuel processing assemblies 10, and feedstock delivery systems 22 have been schematically illustrated herein. These systems may, but are not required to, include additional components, such as air/oxidant supplies and delivery systems, heat exchange assemblies and/or sources, controllers, sensors, valves and other flow controllers, power management modules, etc. It is within the scope of the present disclosure to selectively include one or more of these components. Similarly, although a single fuel processor 12 and/or a single fuel cell stack 40 are shown the figures, it is within the scope of the disclosure that more than one of either or both of these components may be used.
The present disclosure is applicable to the hydrogen-production, feedstock delivery, and power generation fields.
It is believed that the disclosure set forth above encompasses multiple distinct inventions with independent utility. While each of these inventions has been disclosed in its preferred form, the specific embodiments thereof as disclosed and illustrated herein are not to be considered in a limiting sense as numerous variations are possible. The subject matter of the inventions includes all novel and non-obvious combinations and subcombinations of the various elements, features, functions and/or properties disclosed herein. Similarly, where the claims recite “a” or “a first” element or the equivalent thereof, such claims should be understood to include incorporation of one or more such elements, neither requiring nor excluding two or more such elements.
It is believed that the following claims particularly point out certain combinations and subcombinations that are directed to one of the disclosed inventions and are novel and non-obvious. Inventions embodied in other combinations and subcombinations of features, functions, elements and/or properties may be claimed through amendment of the present claims or presentation of new claims in this or a related application. Such amended or new claims, whether they are directed to a different invention or directed to the same invention, whether different, broader, narrower, or equal in scope to the original claims, are also regarded as included within the subject matter of the inventions of the present disclosure.
The present application claims priority to U.S. Provisional Patent Application Ser. Nos. 60/623,894 and 60/717,641, the complete disclosures of which are hereby incorporated by reference for all purposes.
Number | Date | Country | |
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60623894 | Oct 2004 | US | |
60717641 | Sep 2005 | US |