The present disclosure relates generally to hydrogen-producing fuel processing assemblies and fuel cell systems, and more particularly to feedstock delivery systems therefor.
A hydrogen-producing fuel processing assembly is an assembly of one or more devices or components that includes a fuel processor with a hydrogen-producing region that is adapted to convert one or more feedstocks into a product stream containing hydrogen gas as a majority component. In operation, the hydrogen-producing region is typically operated at an elevated temperature and pressure and contains a suitable catalyst to produce at least hydrogen gas from the feedstock(s) delivered thereto. The composition, flow rate, and properties of the feedstock(s) delivered to the hydrogen-producing region may affect the performance of the hydrogen-generation assembly.
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 a fuel and an oxidant to electricity, a reaction product, and heat. For example, fuel cells may convert hydrogen and oxygen gases into water and electricity. In such fuel cells, the hydrogen gas is the fuel, the oxygen gas is the oxidant, and the water is the reaction product. Fuel cells are typically coupled together to form a fuel cell stack.
A hydrogen-producing fuel cell system is a system that includes a hydrogen-producing processing assembly that is adapted to produce hydrogen gas and a fuel cell stack that is adapted to receive hydrogen gas produced by the fuel processing assembly and to generate an electric current therefrom. When the flow rate of hydrogen gas to the fuel cell stack is affected by the flow rate of feedstock(s) to the hydrogen-producing region of the hydrogen-generation assembly, this may affect the performance of the fuel cell stack and/or its ability to satisfy an applied load thereto.
In many fuel processing assemblies, the feed stream for the hydrogen-producing region is a liquid feed stream. The liquid feed stream is drawn from a suitable source or reservoir by a pump, and thereafter delivered to the hydrogen-producing region, typically after vaporizing the feed stream. In many such fuel processing assemblies, the liquid feed stream includes at least one of water and a carbon-containing feedstock, such as an alcohol or hydrocarbon. The rate at which the feed stream is pumped from the source to the hydrogen-producing region is typically related to the demand for hydrogen gas, with a greater flow rate of the feed stream provided when there is a greater demand for hydrogen gas produced by the fuel processing assembly, and a lesser flow rate when there is a lower demand. Reliable provision of the desired flow rate of the feed stream within a range of flow rates is a design goal for a fuel processing assembly, as the flow rate of feed stream affects the overall performance and/or operating conditions of the fuel processing assembly, and any hydrogen-producing fuel cell system of which the fuel processing assembly forms a portion thereof.
A fuel processing assembly containing a feedstock delivery system 22 according to the present disclosure is shown in
When the carbon-containing feedstock is miscible with water, the carbon-containing feedstock may be, but is not required to be, delivered to the fuel processor in the same feed stream as the water component of feed stream 16, such as shown in
While a single feed stream 16 is shown in
Fuel processor 12 includes any suitable device, or combination of devices, that is adapted to produce via chemical reaction predominately hydrogen gas from feed stream(s) 16. Accordingly, fuel processor 12 includes a hydrogen-producing region 19, in which an output stream 20 containing hydrogen gas is produced by utilizing any suitable hydrogen-producing mechanism(s). Output stream 20 includes hydrogen gas as at least a majority component. Output stream 20 may include one or more additional gaseous components, and thereby may be referred to as a mixed gas stream, which contains hydrogen gas as its majority component, and which also contains other gases.
An illustrative, non-exclusive example of a suitable mechanism for producing hydrogen gas from feed stream(s) 16 delivered by feedstock delivery system 22 is steam reforming, in which a reforming catalyst is used to produce hydrogen gas from at least one 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
Another illustrative example of a suitable hydrogen-producing reaction that may be utilized in hydrogen-producing region 19 is autothermal reforming, in which a suitable autothermal reforming catalyst is used to produce hydrogen gas from water and a carbon-containing feedstock in the presence of air. When autothermal reforming is used, the fuel processor further includes an air delivery assembly 67 that is adapted to deliver an air stream to the hydrogen-producing region, as indicated in dashed lines in
At least the hydrogen-producing region 19 of fuel processing assembly 10 is designed to be operated at an elevated temperature, or within an elevated temperature range, when being utilized to produce hydrogen gas for product hydrogen stream 14. This hydrogen-producing temperature, or temperature range, may be achieved and/or maintained in hydrogen-producing region 19 through the use of a heating assembly 60 or other suitable heat source. Hydrogen-producing steam reformers typically operate at temperatures in the range of 200° C.-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., 375-400° C., and 400-450° 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 19 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 carbon-containing feedstock is, or includes, a hydrocarbon, in some embodiments it may be desirable to include two different hydrogen-producing portions, 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.
At least the hydrogen-producing region 19 of fuel processing assembly 10 also is configured to be operated at an elevated pressure, such as a pressure of at least 40 or at least 50 psi. This pressure may be referred to herein as a hydrogen-producing pressure. Additionally or alternatively, a hydrogen-producing region of a fuel processing assembly may be adapted to operate within a hydrogen-producing pressure range. As illustrative, non-exclusive examples, steam and autothermal reformers are typically operated at such hydrogen-producing pressures as pressures in the range of 40-1000 psi, including pressures in the range of 40-100 psi, 50-150 psi, 50-200 psi, etc. Pressures outside of this range may be used and are within the scope of the present disclosure. For example, in some embodiments, a lower pressure may be sufficient, such as when the hydrogen-producing region is adapted to produce hydrogen gas using a partial oxidation and/or autothermal reforming reaction and/or when the fuel processing assembly does not utilize a pressure-driven separation process to increase the purity of the hydrogen gas produced in the hydrogen-producing region. When the fuel processing assembly includes a purification, or separation, region, such as described herein, this region also may be designed to operate at an elevated pressure and/or within an elevated pressure range and/or at an elevated temperature and/or within an elevated temperature range.
The particular maximum and minimum operating pressures for a particular fuel processing assembly may vary according to a variety of possible factors. Illustrative, non-exclusive examples of such factors may include, but are not 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 if it is also desirable to maintain the purification region at an elevated pressure.
The pressure for at least the hydrogen-producing region of the fuel processing assembly, and in some embodiments also for a pressure-driven purification region thereof, may be provided by the pressure of feed stream 16. Specifically, the pressurized feed stream, or a gas stream produced therefrom, pressurizes these components of the fuel processing assembly. Accordingly, feedstock delivery system 22 may additionally or alternatively be described as pressurizing at least the hydrogen-producing region 19 of the hydrogen-producing fuel processing assembly. It follows then that variations or oscillations in the flow rate and/or pressure of feed stream 16 may affect the operating parameters of other aspects of the fuel processing assembly and/or an associated fuel cell stack.
As an illustrative, non-exclusive example, when fuel processing assembly 10 includes a heating assembly that combusts a portion of the gases produced by the hydrogen-producing region for fuel to heat at least the hydrogen-producing region, it follows that interruptions in the flow of feed stream 16 to the hydrogen-producing region may affect the flow rate of fuel to the heating assembly. This interruption in fuel may affect the temperature of the hydrogen-producing region, which may in turn affect the efficiency and/or amount of hydrogen gas produced in the hydrogen-producing region. This reduction in hydrogen output may affect the ability of the fuel processing assembly to satisfy the demand for hydrogen gas by an associated fuel cell stack, which in turn may affect that fuel cell system's ability to satisfy an applied load. As another illustrative, non-exclusive example, interruptions in the flow rate of feed stream 16 to the hydrogen-producing region of the fuel processing assembly may also affect the pressure within the hydrogen-producing region, and thus in the output stream therefrom, which in turn may affect the performance of any pressure-driven separation process downstream from the hydrogen-producing region. As another illustrative, non-exclusive example, frequent and sudden starting and stopping of the flow of feed stream 16 from the feedstock delivery system may affect components of the feedstock delivery system, such as by causing wear on a pump and/or drive system therefor.
According to the present disclosure, feedstock delivery system 22 is adapted to draw or otherwise receive at least a liquid carbon-containing feedstock from a supply, or source, and to deliver a feed stream 16 containing at least the carbon-containing feedstock for use in at least the hydrogen-producing region of the fuel processing assembly. Feedstock delivery system 22 may utilize any suitable delivery mechanism, such as a positive displacement or other suitable pump or mechanism for propelling and pressurizing liquid fluid streams. When one or more pumps are used, the number, type and capacity of the pumps may vary, such as with respect to the desired flow rate of liquid to be pumped thereby, the desired pressure, or pressure range, to be provided to the liquid, the composition of the liquid, whether or not the flow rate is intended to be selectively varied, etc. Illustrative, non-exclusive examples of pumps that may be used include diaphragm pumps, metering pumps, gear pumps, and the like.
An illustrative, non-exclusive example of a feedstock delivery system 22 according to the present disclosure is shown in
Supply 112 includes any suitable type and/or number of reservoirs and/or other sources from which a liquid inlet stream 110 may be drawn or otherwise received by inlet 106 of pump assembly 100. Illustrative, non-exclusive examples of suitable supplies 112 include tanks, canisters, and other liquid vessels, which may be pressurized or unpressurized. Liquid inlet 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
When feed stream 16 contains both water and a liquid carbon-containing feedstock, the carbon-containing feedstock may be selected to be miscible with water. For example, methanol and many other alcohols are miscible with water. In some embodiments, the feed stream may also include an emulsifier or other suitable additive that promotes mixing of water and a carbon-containing feedstock that otherwise is not, or is not suitably, miscible with water at the operating conditions utilized by the feedstock delivery system. When the feed stream contains two or more feedstocks, the feedstocks may be mixed in a common source, or supply, or may be drawn from separate sources and thereafter mixed.
Pump assembly 100 is adapted to draw or otherwise receive liquid inlet stream 110 from supply 112 and to emit a liquid outlet stream 116 having an increased pressure relative to liquid inlet stream 110 and within a hydrogen-producing pressure range. Accordingly, feedstock delivery system 22 may be described as being adapted to pump a liquid stream containing at least one feedstock for hydrogen-producing region 19 from a liquid feedstock supply. Additionally or alternatively, liquid inlet stream 110 may be referred to as a lower pressure stream, and liquid outlet stream 116 may be referred to as a higher pressure stream. When the pump assembly 100 includes more than one pump, the pumps may cooperate to draw liquid inlet stream 110 and/or emit liquid outlet stream 116. Additionally or alternatively, the pumps may each be adapted to draw a liquid inlet stream 110 from the same or different sources 112 and/or to each emit a liquid outlet stream 116 therefrom. Additionally or alternatively, a pump assembly 100 may be adapted to draw from the liquid supply a liquid inlet stream containing at least a carbon-containing feedstock and to emit a liquid outlet stream at least intermittently within or above the hydrogen-producing pressure range, the pump assembly having an inlet for receiving the liquid inlet stream and an outlet for emitting the liquid outlet stream.
Described in terms of the fluid conduits of, or associated with, feedstock delivery system 22, and as illustrated somewhat schematically in
A pump 102 of a pump assembly 100 may include any suitable drive mechanism and may be powered by any suitable power source, such as are schematically indicated at 151 and 153, respectively, in
Power source 153 may include a component of a hydrogen-producing fuel cell system, such as the subsequently described fuel cell stack and/or energy storage device. Additional illustrative, non-exclusive examples include a power supply that is independent of power output produced by the fuel cell system, such as an external, or dedicated, battery, a line current from an electrical grid, etc. While not required to all embodiments, 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 at least intermittently receiving liquid inlet stream 110 and at least intermittently emitting liquid outlet stream 116, or an off, or unpowered, configuration in which the pump is not emitting liquid outlet stream 116. By at least intermittently receiving and at least intermittently emitting during an on, or active, configuration of a pump, it is meant that a pump may not receive and/or emit a continuous stream at a constant flow rate and/or at a constant pressure, but rather may receive and/or emit a stream in pulses, in a non-constant flow rate, and/or in non-constant pressures, etc., such as may depend on a particular configuration of a pump being used and/or on the power being delivered to the pump. For example, the actual output of the pump may vary with the voltage of the power output delivered to the pump, which in some embodiments may tend to vary, for example, depending on an overall load on a corresponding power supply. In some embodiments, the pump may be a variable speed pump that is designed to selectively operate at two or more speeds and/or within a range of speeds. In some embodiments, the power source for the pump may be configured to regulate the duty cycle, or power, provided to the pump to thereby regulate or control the output of the pump.
In addition to at least one pump 102, feedstock delivery systems 22 according to the present disclosure further include a stall prevention mechanism 160 that is adapted to prevent stalling of a pump 102 during operation of the feedstock delivery system. Specifically, it has been discovered that pumps that are effective for providing a desired flow of feed stream 16 for the fuel processing assembly during moderate-to-high relative flow rates, or utilization, may have difficulty doing so without stalling when utilized at lower flow rates and/or when the desired flow rate is reduced. Stalling may result when pump 102 is a pump in which the pressure immediately downstream of the pump will tend to oscillate during normal use of the pump. An illustrative, non-exclusive example of such a pump is a diaphragm pump, although the present disclosure is not limited to pumps 102 that are diaphragm pumps. However, for the purpose of illustrating how stalling may occur, the following discussion will describe pump 102 as being a diaphragm pump.
Diaphragm pumps are positive displacement pumps, which are sequentially configured between refill cycles (or strokes) and discharge cycles (or strokes), such as responsive to drive assembly 151 propelling movement of the pump's working portion 109. In diaphragm pumps, discharge cycles may also be referred to as compression, or pressurization, cycles. Positive displacement pumps generally, and diaphragm pumps in particular, include inlet and outlet check valves that respectively open and close to permit or preclude flow of fluid, such as liquid feedstocks, into and out of the pump's internal fluid chamber 107. These check valves are schematically illustrated in
Since the pressure upstream of the inlet valve tends to be at or near ambient pressure, opening and closing of the inlet check valve is fairly reliable regardless of the degree of utilization of the pump within its range of rated flow rates and/or changes therein. However, the pressure of liquid outlet stream 116 downstream from the pump may affect the ability of the outlet check valve to reliably open and close. Specifically, the pressure downstream of the pump may prevent the outlet check valve from being able to open, especially when the pump is operating at a lower power or lower output level. As used herein, the terms upstream and downstream refer to the relative locations of the elements being compared in terms of the direction of fluid flow therebetween. For example, and in the context of
When the outlet check valve cannot open, or reliably open, due to the pressure differential across the outlet check valve, the pump may be described as being in a stalled condition. This stalled condition may be described as occurring when the pump is not able to generate a pressure that exceeds the threshold pressure for the pump's outlet check valve to open. This potential for stalling may be especially prevalent when the utilization of the pump is suddenly reduced, such as when it is desirable to reduce, but not stop, the rate at which hydrogen gas is produced by the fuel processing assembly. Illustrative, non-exclusive utilization ranges where stalling may be more likely to occur include when the pump is operating at less than 75%, less than 70%, less than 60%, less than 50%, 40-70%, 50-75%, etc. of capacity, and/or when the pump is transitioned to one of the above operating percentages after being operated at 75-80% or more of its capacity. When the pump stalls, the flow of pressurized liquid therefrom to form liquid outlet stream 116 is interrupted even though drive assembly 151 is attempting to drive the rotation or otherwise actuate the pump's working portion. This has a potential to result in damage to the pump and/or its drive assembly. Once stalled, the pressure in the hydrogen-producing region, and upstream thereof, will tend to reduce over time as the feed stream is reacted in the hydrogen-producing region. When the pressure is sufficiently reduced for the pump to produce a pressure that achieves or exceeds the outlet check valve's threshold pressure, then the outlet check valve is able to open, and flow of liquid outlet stream 116 is resumed.
Feedstock delivery systems 22 according to the present disclosure include stall prevention mechanism 160 and thus are configured to reduce the potential for stalling of the pump, and thereby provide for more reliable delivery of feed stream 16 to the fuel processor. As indicated in
Stall prevention mechanism 160 is also configured to produce a bleed stream 120, at least during the refill cycle of the pump. Bleed stream 120 is emitted from liquid outlet stream 116, or elsewhere downstream from the pump assembly's outlet and upstream from check valve 166. As shown in
In
Also shown in dashed lines in
When implementing stall prevention mechanism 160, it may be desirable to size, relative to the outlet conduit, the bleed conduit 136 and/or the bleed orifice 138 so that the desired degree of pressure reduction is provided. Specifically, if the size of the bleed conduit and/or orifice is too small, stall prevention mechanism 160 may not be able to sufficiently reduce the pressure in outlet conduit 132 during a refill cycle of the pump for the pump to be able to transition to a pressurization cycle without stalling. However, and especially in the case of a conduit and/or orifice that is not selectively opened and closed as the pump alternates between discharge and refill cycles (as optionally discussed herein), it also follows that too large of a bleed conduit and/or orifice may result in a feedstock delivery system that will not be able to effectively provide a feed stream 16 within the required hydrogen-producing pressure range (and/or a sufficient flow rate of such a stream) because too much of liquid outlet stream 116 will flow through the bleed conduit as bleed stream 120. It follows from this latter discussion that the flow rate of pressurized liquid emitted from the pump assembly during a pump's discharge cycle should exceed the flow rate of liquid through bleed conduit 136 during the pressurization cycle.
In some embodiments, at least a portion of the bleed conduit is sized, relative to the outlet conduit, to reduce pressure in the outlet conduit during periods in which the pump assembly is not emitting the liquid outlet stream within or above the hydrogen-producing pressure range, for example, due to the pump assembly including a positive displacement pump that only intermittently emits the liquid outlet stream within or above the hydrogen-producing pressure range. Additionally or alternatively in some embodiments, the bleed conduit may include a bleed orifice that is sized, relative to the outlet conduit, to reduce pressure in the outlet conduit during periods in which the pump assembly is not emitting the liquid outlet stream within or above the hydrogen-producing pressure range, for example, due to the pump assembly including a positive displacement pump that only intermittently emits the liquid outlet stream within or above the hydrogen-producing pressure range.
In some embodiments, it may be helpful to utilize a drive assembly 151 for a pump 102 of a pump assembly 100 that employs a sufficient gear reduction that this parameter is satisfied (i.e., to further ensure an appropriate flow rate of the bleed stream). In experiments in which pump 102 is designed to provide up to 7-8 milliliters per minute of pressurized liquid feedstock(s) at a pressure up to 100 psi, a 90:1 gear reduction has proven effective to result in a pump velocity of 0.5-1 revolution per second. This example is provided for the purpose of illustration and not limitation, as it is within the scope of the present disclosure for the feedstock delivery system to be designed to provide a greater or lesser flow rate, an output stream with a higher or lower pressure, and for the gear reduction (if utilized) to be greater or less than in the above example. It is also within the scope of the present disclosure to utilize more than one pump, more than one reforming region, and/or more than one feedstock delivery system with a fuel processing assembly according to the present disclosure.
Another illustrative, non-exclusive example of a feedstock delivery system 22 with a stall prevention mechanism 160 according to the present disclosure is shown in
As indicated in dashed lines in
When utilized, the restriction valve may be controlled to open and close via any suitable mechanism. In some embodiments, the restriction valve may be controlled to be open when a pump of a pump assembly is in its refill stroke and closed at least slightly after the pump begins its discharge stroke, if not closed before or when the discharge stroke begins. Accordingly, the restriction valve may be operatively linked to the pump assembly. Restriction valve 170 may be controlled by one or more of a variety of mechanisms. Illustrative, non-exclusive examples of such mechanisms include mechanical, electrical, and pressure-driven control mechanisms. Additional examples include controlling the restriction valve responsive to an encoder for the motor or other drive assembly for the motor, responsive to the position of the working portion of the pump, etc. A potential benefit of the stall prevention mechanism of
Another illustrative, non-exclusive example of a feedstock delivery system 22 with a stall prevention mechanism 160 according to the present disclosure is shown in
Another illustrative, non-exclusive example of a feedstock delivery system 22 with a stall prevention mechanism 160 according to the present disclosure is shown in
An illustrative, non-exclusive example of a method according to the present disclosure for delivering feedstock within a hydrogen-producing pressure range to a hydrogen-producing region of a hydrogen-producing fuel processing assembly that is adapted to produce a mixed gas stream containing hydrogen gas as a majority component therefrom may include one or more of the following: (i) drawing a liquid stream from a liquid supply containing at least one carbon-containing feedstock; (ii) pumping the liquid stream at least intermittently within or above the hydrogen-producing pressure range into an outlet conduit; (iii) delivering a delivery stream comprising at least a portion of the liquid stream from the outlet conduit to the hydrogen-producing region; (iv) isolating pressure in the outlet conduit from pressure in the hydrogen-producing region during periods in which the liquid stream is not being pumped within or above the hydrogen-producing pressure range; and (v) reducing pressure in the outlet conduit during periods in which the liquid stream is not being pumped within or above the hydrogen-producing pressure range.
Additionally or alternatively, the reducing pressure in the outlet conduit may include diverting a bleed stream comprising at least a portion of the liquid stream from the outlet conduit through a bleed conduit during periods in which the liquid stream is not being pumped within or above the hydrogen-producing pressure range.
Additionally or alternatively, a method according to the present disclosure may further include delivering the bleed stream to at least one of the liquid supply, the liquid stream upstream of the outlet conduit, and a burner associated with the hydrogen-producing fuel processing assembly.
Additionally or alternatively, a method according to the present disclosure may further include restricting flow of the bleed stream through the bleed conduit during periods in which the liquid stream is being pumped within or above the hydrogen-producing pressure range.
Additionally or alternatively, a method according to the present disclosure may further include restricting flow of the bleed stream through the bleed conduit during periods in which pressure in the outlet conduit is within or above the hydrogen-producing pressure range.
Additionally or alternatively, the pumping the liquid stream may be facilitated by a pump assembly including a positive displacement pump having an internal chamber and that is adapted to receive the liquid stream into the internal chamber during a refill stroke and to discharge the delivery stream from the internal chamber to the outlet conduit within or above the hydrogen-producing pressure range during a discharge stroke.
Additionally or alternatively, a method according to the present disclosure may further include delivering the bleed stream to the internal chamber of the positive displacement pump during the refill stroke of the positive displacement pump.
In many applications, it is desirable for fuel processor 12 and/or fuel processing assembly 10 to produce a product hydrogen stream 14 containing at least substantially pure hydrogen gas. Accordingly, the fuel processor may utilize a process that inherently produces sufficiently pure hydrogen gas. When the output stream contains sufficiently pure hydrogen gas and/or sufficiently low concentrations of one or more non-hydrogen components for a particular application, product hydrogen stream 14 may be formed directly from output stream 20. However, in many hydrogen-producing processes, output stream 20 will be a mixed gas stream that contains hydrogen gas as a majority component along with other gases. Similarly, in many applications, the output stream 20 may be substantially pure hydrogen but still contain concentrations of one or more non-hydrogen components that are harmful or otherwise undesirable in the application for which the product hydrogen stream is intended to be used.
Accordingly, fuel processing assembly 10 may (but is not required to) further include a purification 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. 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. When purification region 24 produces a byproduct stream 28, the purification region may additionally or alternatively be referred to as a separation region, as the region separates the (mixed gas) output stream 20 into hydrogen-rich stream 26 and byproduct stream 28.
Purification region 24 includes any suitable 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 many conventional fuel cell systems (such as proton exchange membrane 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 output 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, non-exclusive 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, hydrogen-producing fuel processing assembly 10 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.
Hydrogen-selective membranes are typically very thin, such as a thin foil that is approximately 0.001 inches thick. It is within the scope of the present disclosure, however, that the membranes may be formed from other hydrogen-permeable and/or hydrogen-selective materials, including metals and metal alloys other than those discussed above as well as non-metallic materials and compositions, and that the membranes may have thicknesses that are greater or less than discussed above. For example, the membrane may be made thinner, with commensurate increase in hydrogen flux. Examples of suitable mechanisms for reducing the thickness of the membranes include rolling, sputtering and etching. 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 output 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 and other devices that convert carbon monoxide to carbon dioxide, and methanation catalyst beds that convert carbon monoxide and hydrogen to methane and water. It is within the scope of the disclosure that fuel processing assembly 10 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. The success of using PSA for hydrogen purification is due to the relatively strong adsorption of common impurity gases (such as CO, CO2, hydrocarbons including CH4, and N2) on the adsorbent material. Hydrogen adsorbs only very weakly and so hydrogen passes through the adsorbent bed while the impurities are retained on the adsorbent material. Impurity gases such as NH3, H2S, and H2O adsorb very strongly on the adsorbent material and are removed from output stream 20 along with other impurities. If the adsorbent material is going to be regenerated and these impurities are present in output stream 20, purification region 24 preferably includes a suitable device that is adapted to remove these impurities prior to delivery of output stream 20 to the adsorbent material because it is more difficult to desorb these impurities.
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. The adsorbent material is commonly in the form of pellets and it is placed in a cylindrical pressure vessel utilizing a conventional packed-bed configuration. Other suitable adsorbent material compositions, forms, and configurations may be used.
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 the context of a fuel processor, or fuel processing assembly, that is adapted to produce a product hydrogen stream that will be used as a feed, or fuel, stream for a fuel cell stack, the fuel processor may be adapted to produce substantially pure hydrogen gas, or even pure hydrogen gas. For the purposes of the present disclosure, substantially pure hydrogen gas refers to hydrogen gas that is greater than 90% pure, and which may be greater than 95% pure, greater than 99% pure, and even greater than 99.5% pure. Suitable fuel processors and fuel processing assemblies, including illustrative (non-exclusive) examples of components and configurations therefor for producing streams of at least substantially pure hydrogen gas are disclosed in U.S. Pat. Nos. 6,319,306, 6,221,117, 5,997,594, 5,861,137, and pending U.S. Patent Publication Nos. 2001/0045061, 2003/0192251, 2003/0223926, 2006/0090397, and 2007/0062116. The complete disclosures of the above-identified patents and patent application publications are hereby incorporated by reference.
In
It is further within the scope of the disclosure that one or more of the components of fuel processing assembly 10 may either extend beyond the shell or be located external at least shell 68. For example, and as previously 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
As also shown in at least FIGS. 1 and 7-9, fuel processing assemblies (and fuel cell systems) according to the present disclosure may include a heating assembly 60 that is adapted to heat at least the hydrogen-producing region, or reforming region, 19 of the fuel processor. 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. Stream 66 may also be referred to as a heated exhaust stream. 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.
In FIGS. 1 and 7-9, heating assembly 60 is shown in an overlapping relationship with fuel processor 12 to graphically represent that it is within the scope of the disclosure that the heating assembly may be located partially or completely within fuel processor 12, such as being at least partially within shell 68, and/or that at least a portion, or all, of the heating assembly may be located external the fuel processor. In this latter embodiment, the hot combustion gases from the burner assembly will be delivered via suitable heat transfer conduits to the fuel processor or other portion of the system(s) to be heated. Illustrative, non-exclusive examples of suitable heating assemblies for use with fuel processing assemblies according to the present disclosure are disclosed in U.S. Patent Application Publication Nos. 2003/0192251, 2003/0223926, and 2006/0272212, the complete disclosures of which are hereby incorporated by reference.
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
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, a fuel cell stack may be adapted to receive at least a portion of product hydrogen stream 14 and a stream of oxygen (which is typically delivered as an air stream), and to produce an electric current therefrom. This is schematically illustrated in
When product hydrogen stream 14 is intended for use in a fuel cell stack, compositions that may damage the fuel cell stack, such as carbon monoxide and carbon dioxide, may be removed from the hydrogen-rich stream, if necessary, such as by purification region 24. For fuel cell stacks, such as proton exchange membrane (PEM) and alkaline fuel cell stacks, it may be desirable for the concentration of carbon monoxide to be less than 10 ppm (parts per million), less than 5 ppm, or even less than 1 ppm. The concentration of carbon dioxide may be greater than that of carbon monoxide. For example, concentrations of less than 25% carbon dioxide may be acceptable in some embodiments, with additional illustrative, non-exclusive examples including concentrations of less than 10%, less than 1%, or even less than 50 ppm. The acceptable minimum concentrations presented herein are illustrative examples, and concentrations other than those presented herein may be used and are within the scope of the present disclosure. For example, particular users or manufacturers may require minimum or maximum concentration levels or ranges that are different than those identified herein.
Fuel cell stack 40 contains at least one, and typically multiple, 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.
The electric current, or electrical output, produced by fuel cell stack 40 may be used to satisfy the energy demands, or applied load, of at least one associated energy-consuming device 46. Illustrative examples of devices 46 include, but should not be limited to, motor vehicles, recreational vehicles, construction or industrial vehicles, boats or other seacraft, tools, lights or lighting assemblies, appliances (such as household or other appliances), households or other dwellings, offices or other commercial establishments, computers, signaling or communication equipment, battery chargers, etc. Similarly, fuel cell stack 40 may be used to satisfy the power requirements of fuel cell system 42, which may be referred to as the balance-of-plant power requirements of the fuel cell system. It should be understood that device 46 is schematically illustrated in
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 at least one battery 52 or other suitable energy-storage, or electricity-storing, device that is adapted to store the electric potential, or power output, produced by fuel cell stack 40. Illustrative, non-exclusive examples of other energy storage devices that may be used include flywheels and capacitors, such as ultracapacitors or supercapacitors. 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
A further illustrative, non-exclusive example of a fuel processing assembly 10 with a feedstock delivery system 22 with a stall prevention mechanism 160 according to the present disclosure is shown in
The feedstock delivery systems, and hydrogen-producing fuel processing and fuel cell systems containing the same that are disclosed herein are applicable to the hydrogen- and energy-production industries, including the fuel cell industries.
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.
This present application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application Ser. No. 61/008,080, which was filed on Dec. 17, 2007, the entire disclosure of which is hereby incorporated by reference.
Number | Name | Date | Kind |
---|---|---|---|
1306221 | Ellis | Jun 1919 | A |
1782824 | Hechenbleikner | Nov 1930 | A |
1848466 | Edmonds | Mar 1932 | A |
2132151 | Fenske et al. | Oct 1938 | A |
2450804 | Loy | Oct 1948 | A |
2609059 | Benedict | Sep 1952 | A |
2824620 | De Rosset | Feb 1958 | A |
3094391 | Mader | Jun 1963 | A |
3144312 | Mertens | Aug 1964 | A |
3208198 | Rubin | Sep 1965 | A |
3336730 | McBride et al. | Aug 1967 | A |
3338681 | Kordesch | Aug 1967 | A |
3344586 | Langley et al. | Oct 1967 | A |
3350176 | Green et al. | Oct 1967 | A |
3356538 | Miekka et al. | Dec 1967 | A |
3368329 | Eguchi et al. | Feb 1968 | A |
3428476 | Langley et al. | Feb 1969 | A |
3439474 | McKinley | Apr 1969 | A |
3447288 | Juda et al. | Jun 1969 | A |
3450500 | Setzer et al. | Jun 1969 | A |
3469372 | Yamauchi et al. | Sep 1969 | A |
3469944 | Bocard et al. | Sep 1969 | A |
3486301 | Bonnet | Dec 1969 | A |
3520803 | Iaconelli | Jul 1970 | A |
3522019 | Buswell et al. | Jul 1970 | A |
3524819 | Guerrieri | Aug 1970 | A |
3534531 | Eguchi et al. | Oct 1970 | A |
3564819 | Neulander et al. | Feb 1971 | A |
3589171 | Haley | Jun 1971 | A |
3655448 | Setzer | Apr 1972 | A |
3665680 | Heuser | May 1972 | A |
3713270 | Farr et al. | Jan 1973 | A |
3761382 | Hammond et al. | Sep 1973 | A |
3782904 | Fletcher | Jan 1974 | A |
3787038 | Tesner et al. | Jan 1974 | A |
3791106 | Haley | Feb 1974 | A |
3837146 | Faure et al. | Sep 1974 | A |
3839110 | Shankoff | Oct 1974 | A |
3849076 | Gryaznov et al. | Nov 1974 | A |
3881891 | Goltsov et al. | May 1975 | A |
3881897 | Faure et al. | May 1975 | A |
3920416 | Houseman | Nov 1975 | A |
3955941 | Houseman et al. | May 1976 | A |
3972695 | Buckley et al. | Aug 1976 | A |
3980452 | Krumm et al. | Sep 1976 | A |
3982910 | Houseman et al. | Sep 1976 | A |
4003343 | Lee | Jan 1977 | A |
4003725 | Bunn, Jr. et al. | Jan 1977 | A |
4056373 | Rubin | Nov 1977 | A |
4078985 | Takeuchi | Mar 1978 | A |
4084934 | Kumazawa | Apr 1978 | A |
4098959 | Fanciullo | Jul 1978 | A |
4098960 | Gagnon | Jul 1978 | A |
4127393 | Timmins et al. | Nov 1978 | A |
4132668 | Gryaznov et al. | Jan 1979 | A |
4134739 | Gulden et al. | Jan 1979 | A |
4175165 | Adlhart | Nov 1979 | A |
4197152 | Palty et al. | Apr 1980 | A |
4214969 | Lawrance | Jul 1980 | A |
4238403 | Pinto | Dec 1980 | A |
4243536 | Prölss | Jan 1981 | A |
4248688 | Gartner et al. | Feb 1981 | A |
4254086 | Sanders | Mar 1981 | A |
4302177 | Fankhanel et al. | Nov 1981 | A |
4313013 | Harris | Jan 1982 | A |
4315893 | McCallister | Feb 1982 | A |
4319923 | Falanga et al. | Mar 1982 | A |
4329157 | Dobo et al. | May 1982 | A |
4331520 | Juda et al. | May 1982 | A |
4349613 | Winsel | Sep 1982 | A |
4381641 | Madgavkar et al. | May 1983 | A |
4387434 | Moncrief, Jr. et al. | Jun 1983 | A |
4400182 | Davies et al. | Aug 1983 | A |
4417905 | Banks et al. | Nov 1983 | A |
4422911 | Juda et al. | Dec 1983 | A |
4430304 | Spurrier et al. | Feb 1984 | A |
4444158 | Yoon | Apr 1984 | A |
4466253 | Jaster | Aug 1984 | A |
4468235 | Hill | Aug 1984 | A |
4472176 | Rubin | Sep 1984 | A |
4473622 | Chludzinski et al. | Sep 1984 | A |
4483690 | Marion et al. | Nov 1984 | A |
4504447 | Spurrier et al. | Mar 1985 | A |
4533607 | Sederquist | Aug 1985 | A |
4553981 | Fuderer | Nov 1985 | A |
4567857 | Houseman et al. | Feb 1986 | A |
4589891 | Iniotakis et al. | May 1986 | A |
4613436 | Wight et al. | Sep 1986 | A |
4642273 | Sasaki | Feb 1987 | A |
4644751 | Hsu | Feb 1987 | A |
4650814 | Keller | Mar 1987 | A |
4654063 | Auvil et al. | Mar 1987 | A |
4655797 | Iniotakis et al. | Apr 1987 | A |
4657828 | Tajima | Apr 1987 | A |
4659634 | Struthers | Apr 1987 | A |
4670359 | Beshty et al. | Jun 1987 | A |
4684581 | Struthers | Aug 1987 | A |
4693945 | Ohyauchi et al. | Sep 1987 | A |
4699637 | Iniotakis et al. | Oct 1987 | A |
4713234 | Weirich et al. | Dec 1987 | A |
4751151 | Healy et al. | Jun 1988 | A |
4781241 | Misage et al. | Nov 1988 | A |
4788004 | Pinto et al. | Nov 1988 | A |
4810485 | Marianowski et al. | Mar 1989 | A |
4820594 | Sugita et al. | Apr 1989 | A |
4838897 | Amano et al. | Jun 1989 | A |
4849187 | Uozu et al. | Jul 1989 | A |
4865624 | Okada | Sep 1989 | A |
4880040 | Pierson et al. | Nov 1989 | A |
4904455 | Karafian et al. | Feb 1990 | A |
4904548 | Tajima | Feb 1990 | A |
4946667 | Beshty | Aug 1990 | A |
4981676 | Minet et al. | Jan 1991 | A |
4999107 | Guerif | Mar 1991 | A |
5030661 | Lywood | Jul 1991 | A |
5032365 | Aono et al. | Jul 1991 | A |
5126045 | Kohlheb et al. | Jun 1992 | A |
5139541 | Edlund | Aug 1992 | A |
5158581 | Coplan | Oct 1992 | A |
5205841 | Vaiman | Apr 1993 | A |
5210059 | Matturo et al. | May 1993 | A |
5215729 | Buxbaum | Jun 1993 | A |
5217506 | Edlund et al. | Jun 1993 | A |
5225080 | Karbachsch et al. | Jul 1993 | A |
5226928 | Makabe et al. | Jul 1993 | A |
5229102 | Minet et al. | Jul 1993 | A |
5259870 | Edlund | Nov 1993 | A |
5306577 | Sprouse | Apr 1994 | A |
5326550 | Adris et al. | Jul 1994 | A |
5335628 | Dunbar | Aug 1994 | A |
5344721 | Sonai et al. | Sep 1994 | A |
5354547 | Rao et al. | Oct 1994 | A |
5376167 | Broutin et al. | Dec 1994 | A |
5382271 | Ng et al. | Jan 1995 | A |
5393325 | Edlund | Feb 1995 | A |
5395425 | Brown | Mar 1995 | A |
5401589 | Palmer et al. | Mar 1995 | A |
5417051 | Ankersmit et al. | May 1995 | A |
RE35002 | Matsubara et al. | Jul 1995 | E |
5432710 | Ishimaru et al. | Jul 1995 | A |
5449848 | Itoh | Sep 1995 | A |
5458857 | Collins et al. | Oct 1995 | A |
5498278 | Edlund | Mar 1996 | A |
5500122 | Schwartz | Mar 1996 | A |
5509942 | Dodge | Apr 1996 | A |
5516344 | Corrigan | May 1996 | A |
5518530 | Sakai et al. | May 1996 | A |
5520807 | Myrna et al. | May 1996 | A |
5525322 | Willms | Jun 1996 | A |
5527632 | Gardner | Jun 1996 | A |
5536405 | Myrna et al. | Jul 1996 | A |
5536488 | Mansour et al. | Jul 1996 | A |
5580523 | Bard | Dec 1996 | A |
5589599 | McMullen et al. | Dec 1996 | A |
5612012 | Soma et al. | Mar 1997 | A |
5614001 | Kosaka et al. | Mar 1997 | A |
5616430 | Aoyama | Apr 1997 | A |
5637259 | Galuszka et al. | Jun 1997 | A |
5637414 | Inoue et al. | Jun 1997 | A |
5639431 | Shirasaki et al. | Jun 1997 | A |
5645626 | Edlund et al. | Jul 1997 | A |
5658681 | Sato et al. | Aug 1997 | A |
5677073 | Kawatsu | Oct 1997 | A |
5679249 | Fendya et al. | Oct 1997 | A |
5688296 | Andrus, Jr. et al. | Nov 1997 | A |
5705082 | Hinson | Jan 1998 | A |
5705916 | Rudbeck et al. | Jan 1998 | A |
5712052 | Kawatsu | Jan 1998 | A |
5714276 | Okamoto | Feb 1998 | A |
5734092 | Wang et al. | Mar 1998 | A |
5738708 | Peachey et al. | Apr 1998 | A |
5741474 | Isomura et al. | Apr 1998 | A |
5741605 | Gillett et al. | Apr 1998 | A |
5759712 | Hockaday | Jun 1998 | A |
5780179 | Okamoto | Jul 1998 | A |
5782960 | Ogawa et al. | Jul 1998 | A |
5795666 | Johnssen | Aug 1998 | A |
5798186 | Fletcher et al. | Aug 1998 | A |
5811065 | Sterenberg | Sep 1998 | A |
5814112 | Elliott et al. | Sep 1998 | A |
5821185 | White et al. | Oct 1998 | A |
5833723 | Kuwabara et al. | Nov 1998 | A |
5858314 | Hsu et al. | Jan 1999 | A |
5861137 | Edlund | Jan 1999 | A |
5874051 | Heil et al. | Feb 1999 | A |
5888273 | Buxbaum | Mar 1999 | A |
5891222 | Hilgendorff et al. | Apr 1999 | A |
5897766 | Kawatsu | Apr 1999 | A |
5897970 | Isomura et al. | Apr 1999 | A |
5904754 | Juda et al. | May 1999 | A |
5931987 | Buxbaum | Aug 1999 | A |
5932181 | Kim et al. | Aug 1999 | A |
5938800 | Verrill et al. | Aug 1999 | A |
5980989 | Takahashi et al. | Nov 1999 | A |
5985474 | Chen et al. | Nov 1999 | A |
5997594 | Edlund et al. | Dec 1999 | A |
5998053 | Diethelm | Dec 1999 | A |
6007931 | Fuller et al. | Dec 1999 | A |
6042956 | Lenel | Mar 2000 | A |
6045772 | Szydlowski et al. | Apr 2000 | A |
6045933 | Okamoto | Apr 2000 | A |
6054229 | Hsu et al. | Apr 2000 | A |
6077620 | Pettit | Jun 2000 | A |
6083637 | Walz et al. | Jul 2000 | A |
6103028 | Juda et al. | Aug 2000 | A |
6103411 | Matsubayashi et al. | Aug 2000 | A |
6152995 | Edlund | Nov 2000 | A |
6165633 | Negishi | Dec 2000 | A |
6168650 | Buxbaum | Jan 2001 | B1 |
6171574 | Juda et al. | Jan 2001 | B1 |
6183543 | Buxbuam | Feb 2001 | B1 |
6183895 | Kudo et al. | Feb 2001 | B1 |
6187066 | Benz et al. | Feb 2001 | B1 |
6190623 | Sanger et al. | Feb 2001 | B1 |
6201029 | Waycuilis | Mar 2001 | B1 |
6221117 | Edlund et al. | Apr 2001 | B1 |
6231831 | Autenrieth et al. | May 2001 | B1 |
6238465 | Juda et al. | May 2001 | B1 |
6242120 | Herron | Jun 2001 | B1 |
6319306 | Edlund et al. | Nov 2001 | B1 |
6332913 | Breitschwerdt et al. | Dec 2001 | B1 |
6350297 | Doyle et al. | Feb 2002 | B1 |
6375906 | Edlund et al. | Apr 2002 | B1 |
6376113 | Edlund et al. | Apr 2002 | B1 |
6379524 | Lee et al. | Apr 2002 | B1 |
6383670 | Edlund et al. | May 2002 | B1 |
6395405 | Buxbaum | May 2002 | B1 |
6458189 | Edlund et al. | Oct 2002 | B1 |
6461408 | Buxbaum | Oct 2002 | B2 |
6494937 | Edlund et al. | Dec 2002 | B1 |
6495277 | Edlund et al. | Dec 2002 | B1 |
6497856 | Lomax, Jr. et al. | Dec 2002 | B1 |
6537352 | Edlund et al. | Mar 2003 | B2 |
6547858 | Edlund et al. | Apr 2003 | B1 |
6562111 | Edlund et al. | May 2003 | B2 |
6569227 | Edlund et al. | May 2003 | B2 |
6596057 | Edlund et al. | Jul 2003 | B2 |
6632270 | Edlund et al. | Oct 2003 | B2 |
6660069 | Sato et al. | Dec 2003 | B2 |
6719831 | Edlund et al. | Apr 2004 | B2 |
6719832 | Edlund et al. | Apr 2004 | B2 |
6723156 | Edlund et al. | Apr 2004 | B2 |
6767389 | Edlund et al. | Jul 2004 | B2 |
6783741 | Edlund et al. | Aug 2004 | B2 |
6824593 | Edlund et al. | Nov 2004 | B2 |
6890672 | Dickman et al. | May 2005 | B2 |
20020182460 | Okamoto | Dec 2002 | A1 |
20030167690 | Edlund et al. | Sep 2003 | A1 |
20030182860 | DeVries | Oct 2003 | A1 |
20030192251 | Edlund et al. | Oct 2003 | A1 |
20040003720 | Beisswenger et al. | Jan 2004 | A1 |
20040065013 | DeVries | Apr 2004 | A1 |
20040083890 | Edlund et al. | May 2004 | A1 |
20040200459 | Bennett et al. | Oct 2004 | A1 |
20050188843 | Edlund et al. | Sep 2005 | A1 |
20050276705 | Pinkerton et al. | Dec 2005 | A1 |
20070062116 | Edlund et al. | Mar 2007 | A1 |
20080222954 | Adams et al. | Sep 2008 | A1 |
Number | Date | Country |
---|---|---|
1238866 | Jul 1988 | CA |
0434562 | Jun 1991 | EP |
1065741 | Jan 2001 | EP |
45-14404 | May 1970 | JP |
45-2642 | Sep 1970 | JP |
57-145276 | Sep 1982 | JP |
1-145302 | Jun 1989 | JP |
1-145303 | Jun 1989 | JP |
1-262903 | Oct 1989 | JP |
4-163860 | Jun 1992 | JP |
4-338101 | Nov 1992 | JP |
6-134244 | May 1994 | JP |
10-263372 | Oct 1998 | JP |
WO 9725649 | Jul 1997 | WO |
WO 9743796 | Nov 1997 | WO |
WO 9930806 | Jun 1999 | WO |
WO 9965097 | Dec 1999 | WO |
WO 0004600 | Jan 2000 | WO |
WO 0027507 | May 2000 | WO |
WO 0112539 | Feb 2001 | WO |
WO 0128662 | Apr 2001 | WO |
WO 0164321 | Sep 2001 | WO |
WO 0183086 | Nov 2001 | WO |
Number | Date | Country | |
---|---|---|---|
20090155642 A1 | Jun 2009 | US |
Number | Date | Country | |
---|---|---|---|
61008080 | Dec 2007 | US |