The present disclosure is directed generally to hydrogen-generation assemblies that include pressure swing adsorption assemblies, and more particularly to systems and methods for recovering energy from pressure swing adsorption assemblies.
A hydrogen-generation assembly is an assembly that includes a fuel processing system that is adapted to convert one or more feedstocks into a product stream containing hydrogen gas as a majority component. 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 into water and electricity. In such fuel cells, the hydrogen is the fuel, the oxygen is the oxidant, and the water is the reaction product. Fuel cells typically require high purity hydrogen gas to prevent the fuel cells from being damaged during use. The product stream from the fuel processing system of a hydrogen-generation assembly may contain impurities, illustrative examples of which include one or more of carbon monoxide, carbon dioxide, methane, unreacted feedstock, and water. Therefore, there is a need in many conventional fuel cell systems to include suitable structure for removing impurities from the impure hydrogen stream produced in the fuel processing system.
A pressure swing adsorption (PSA) process is an example of a mechanism that may be used to remove impurities from an impure hydrogen gas stream by selective adsorption of one or more of the impurities present in the impure hydrogen stream. The adsorbed impurities can be subsequently desorbed and removed from the PSA assembly. PSA is a pressure-driven separation process that utilizes a plurality of adsorbent beds. The beds are cycled through a series of steps, such as pressurization, separation (adsorption), depressurization (desorption), and purge steps to selectively remove impurities from the hydrogen gas and then desorb the impurities. The PSA assembly produces a product hydrogen stream with substantially reduced impurities.
The PSA process may include streams and/or steps in which energy may be recovered and/or reused. For example, the pressure of the product hydrogen stream from the PSA assembly may need to be regulated before that product stream is used in various applications, such as fuel for electrochemical fuel cells. Regulation of pressure typically involves the loss of mechanical energy associated with the product hydrogen stream, which may otherwise be recovered and/or reused.
The present disclosure is directed to PSA assemblies with at least one energy recovery assembly, as well as to hydrogen-generation assemblies and/or fuel cell systems containing the same, and to methods of operating the same. The PSA assemblies include at least one adsorbent bed, and typically a plurality of adsorbent beds, that include an adsorbent region including adsorbent adapted to remove impurities from a mixed gas stream containing hydrogen gas as a majority component and other gases. The mixed gas stream may be produced by a hydrogen-producing region of a fuel processing system, and the PSA assembly may produce a product hydrogen stream that is consumed by a fuel cell stack to provide a fuel cell system that produces electrical power. The energy recovery assemblies are configured to recover mechanical energy from the product hydrogen stream and to apply the recovered mechanical energy to one or more components of the PSA assembly, the hydrogen-generation assembly, and/or the energy producing system. In some embodiments, the energy recovery assembly includes a gas motor configured to recover mechanical energy from the product hydrogen stream produced by the PSA assembly. In some embodiments, the gas motor is adapted to transition between a plurality of operating states based, at least in part, on the pressure of the product hydrogen stream. In some embodiments, the hydrogen-generation assembly is configured to produce the product hydrogen stream regardless of the operating state of the gas motor. In some embodiments, the energy recovery assembly includes a pressure regulator configured to regulate the pressure of the product hydrogen stream regardless of the operating state of the gas motor. In some embodiments, the energy recovery assembly is configured to apply the recovered mechanical energy to at least a vacuum pump that is configured to generate a purging vacuum and/or a purging vacuum supply for a purge system of the pressure swing adsorption assembly. In some embodiments, the purge system is configured to selectively purge the one or more adsorbent beds of the PSA assembly regardless of the purging vacuum and/or purging vacuum supply generated by the vacuum pump.
As discussed in more detail herein, hydrogen-generation assemblies and/or fuel cell systems according to the present disclosure include a separation assembly that includes at least one pressure swing adsorption (PSA) assembly that is adapted to increase the purity of the hydrogen gas that is produced in the hydrogen-generation assembly and/or consumed in the fuel cell stack. In a PSA process, gaseous impurities are removed from a stream containing hydrogen gas. PSA is 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. These impurities may thereafter be desorbed and removed, such as in the form of a byproduct stream. The success of using PSA for hydrogen purification is due to the relatively strong adsorption of common impurity gases (such as, but not limited to, 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.
As discussed in more detail herein, a PSA process typically involves repeated, or cyclical, application of at least pressurization, separation (adsorption), depressurization (desorption), and purge steps, or processes, to selectively remove impurities from the hydrogen gas and then desorb the impurities. Accordingly, the PSA process may be described as being adapted to repeatedly enable a PSA cycle of steps, or stages, such as the above-described steps. The degree of separation is affected by the pressure difference between the pressure of the mixed gas stream delivered to the PSA assembly and the pressure of the byproduct (impurity) stream purged or otherwise exhausted from the PSA assembly. Accordingly, the desorption and/or purge steps typically will include reducing the pressure within the portion of the PSA assembly containing the adsorbed gases, and optionally may even include drawing a vacuum (i.e., reducing the pressure to less than atmospheric or ambient pressure) on that portion of the assembly. Similarly, increasing the feed pressure of the mixed gas stream to the adsorbent regions of the PSA assembly may beneficially affect the degree of separation during the adsorption step.
As illustrated schematically in
Regardless of its construction or components, the feedstock delivery system 58 is adapted to deliver to fuel processing system 64 one or more feedstocks via one or more streams, which may be referred to generally as feedstock supply stream(s) 68. In the following discussion, reference may be made only to a single feedstock supply stream, but is within the scope of the present disclosure that two or more such streams, of the same or different composition, may be used. In some embodiments, air may be supplied to the fuel processing system 64 via a blower, fan, compressor or other suitable air delivery system, and/or a water stream may be delivered from a separate water source.
Fuel processing system 64 includes any suitable device(s) and/or structure(s) that are configured to produce hydrogen gas from the feedstock supply stream(s) 68. As schematically illustrated in
Illustrative examples of suitable mechanisms for producing hydrogen gas from feedstock supply stream 68 include steam reforming and autothermal reforming, in which reforming catalysts are used to produce hydrogen gas from a feedstock supply stream 68 containing water and at least one carbon-containing feedstock. Other examples of suitable mechanisms for producing hydrogen gas include pyrolysis and catalytic partial oxidation of a carbon-containing feedstock, in which case the feedstock supply stream 68 does not contain water. Still another suitable mechanism for producing hydrogen gas is electrolysis, in which case the feedstock is water. Illustrative examples of suitable carbon-containing feedstocks include at least one hydrocarbon or alcohol. Illustrative examples of suitable hydrocarbons include methane, propane, natural gas, diesel, kerosene, gasoline and the like. Illustrative examples of suitable alcohols include methanol, ethanol, and polyols, such as ethylene glycol and propylene glycol.
The hydrogen-generation assembly 46 may utilize more than a single hydrogen-producing mechanism in the hydrogen-producing region 70 and may include more than one hydrogen-producing region. Each of these mechanisms is driven by, and results in, different thermodynamic balances in the hydrogen-generation assembly 46. Accordingly, the hydrogen-generation assembly 46 may further include a temperature modulating assembly 71, such as a heating assembly and/or a cooling assembly. The temperature modulating assembly 71 may be configured as part of the fuel processing system 64 or may be an external component that is in thermal and/or fluid communication with the hydrogen-producing region 70. The temperature modulating assembly 71 may consume a fuel stream, such as to generate heat. While not required in all embodiments of the present disclosure, the fuel stream may be delivered from the feedstock delivery system. For example, and as indicated in dashed lines in
The temperature modulating assembly 71 may include one or more heat exchangers, burners, combustion systems, and other such devices for supplying heat to regions of the fuel processing system and/or other portions of assembly 56. Depending on the configuration of the hydrogen-generation assembly 46, the temperature modulating assembly 71 may also, or alternatively, include heat exchangers, fans, blowers, cooling systems, and other such devices for cooling regions of the fuel processing system 64 or other portions of assembly 56. For example, when the fuel processing system 64 is configured with a hydrogen-producing region 70 based on steam reforming or another endothermic reaction, the temperature modulating assembly 71 may include systems for supplying heat to maintain the temperature of the hydrogen-producing region 70 and the other components within a selected hydrogen-producing temperature range, such as above a threshold hydrogen-producing temperature.
When the fuel processing system is configured with a hydrogen-producing region 70 based on catalytic partial oxidation or another exothermic reaction, the temperature modulating assembly 71 may include systems for removing heat, i.e., supplying cooling, to maintain the temperature of the fuel processing system within a selected hydrogen-producing temperature range, such as below a threshold hydrogen-producing temperature. As used herein, the term “heating assembly” is used to refer generally to temperature modulating assemblies that are configured to supply heat or otherwise increase the temperature of all or selected regions of the fuel processing system. As used herein, the term “cooling assembly” is used to refer generally to temperature moderating assemblies that are configured to cool, or reduce the temperature of, all or selected regions of the fuel processing system.
In
As also shown in
As illustrated in
As indicated in dashed lines in
Illustrative examples of suitable fuels include one or more of the above-described carbon-containing feedstocks, although others may be used. As an illustrative example of temperatures that may be achieved and/or maintained in hydrogen-producing region 70 through the use of heating assembly 71, 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 a similar 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 that the separation region may be implemented within system 22 anywhere downstream from the hydrogen-producing region and upstream from the fuel cell stack. In the illustrative example shown schematically in
The hydrogen-generation assembly 46 preferably is adapted to produce at least substantially pure hydrogen gas, and even more preferably (although not required), the hydrogen-generation assembly is adapted to produce pure hydrogen gas. For the purposes of the present disclosure, substantially pure hydrogen gas is greater than 90% pure, preferably greater than 95% pure, more preferably greater than 99% pure, and even more preferably greater than 99.5% or even 99.9% pure. Illustrative, nonexclusive examples of suitable fuel processing systems 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.
Hydrogen gas from the fuel processing system 64 may be delivered to one or more of the storage device 62 and the fuel cell stack 24 via product hydrogen stream 42. Some or all of hydrogen stream 42 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. With reference to
Proton exchange membrane fuel cells typically utilize a membrane-electrode assembly 26 consisting of an ion exchange, or electrolytic, membrane 28 located between an anode region 30 and a cathode region 32. Each region 30 and 32 includes an electrode 34, namely an anode 36 and a cathode 38, respectively. Each region 30 and 32 also includes a support 39, such as a supporting plate 40. Support 39 may form a portion of the bipolar plate assemblies that are discussed in more detail herein. The supporting plates 40 of fuel cells 20 carry the relative voltage potentials produced by the fuel cells.
In operation, hydrogen gas from product hydrogen stream 42 is delivered to the anode region, and oxidant 44 is delivered to the cathode region. A typical, but not exclusive, oxidant is oxygen. As used herein, hydrogen refers to hydrogen gas and oxygen refers to oxygen gas. The following discussion will refer to hydrogen as the proton source, or fuel, for the fuel cell (stack), and oxygen as the oxidant, although it is within the scope of the present disclosure that other fuels and/or oxidants may be used. Hydrogen and oxygen 44 may be delivered to the respective regions of the fuel cell via any suitable mechanism from respective sources 47 and 48. Illustrative examples of suitable sources 47 of hydrogen include a hydrogen storage device, fuel processing system, or other pressurized source of hydrogen gas. Illustrative examples of suitable sources 48 of oxygen 44 include a pressurized tank of oxygen or air, or a fan, compressor, blower or other device for directing air to the cathode region.
Hydrogen and oxygen typically combine with one another via an oxidation-reduction reaction. Although membrane 28 restricts the passage of a hydrogen molecule, it will permit a hydrogen ion (proton) to pass through it, largely due to the ionic conductivity of the membrane. The free energy of the oxidation-reduction reaction drives the proton from the hydrogen gas through the ion exchange membrane. As membrane 28 also tends not to be electrically conductive, an external circuit 50 is the lowest energy path for the remaining electron, and is schematically illustrated in
Also shown in
In practice, a fuel cell stack 24 will typically contain a plurality of fuel cells with bipolar plate assemblies separating adjacent membrane-electrode assemblies. The bipolar plate assemblies essentially permit the free electron to pass from the anode region of a first cell to the cathode region of the adjacent cell via the bipolar plate assembly, thereby establishing an electrical potential through the stack that may be used to satisfy an applied load. This net flow of electrons produces an electric current that may be used to satisfy an applied load, such as from at least one of an energy-consuming device 52 and the energy-producing system 22.
For a constant output voltage, such as 12 volts or 24 volts, the output power may be determined by measuring the output current. The electrical output may be used to satisfy an applied load, such as from energy-consuming device 52.
The at least one energy-consuming device 52 may be electrically coupled to the energy-producing system 22, such as to the fuel cell stack 24 and/or one or more energy-storage devices 78 associated with the stack. Device 52 applies a load to the energy-producing system 22 and draws an electric current from the system to satisfy the load. This load may be referred to as an applied load, and may include thermal and/or electrical load(s). It is within the scope of the present disclosure that the applied load may be satisfied by the fuel cell stack, the energy-storage device, or both the fuel cell stack and the energy-storage device. Illustrative examples of devices 52 include motor vehicles, recreational vehicles, boats and other sea craft, and any combination of one or more residences, commercial offices or buildings, neighborhoods, tools, lights and lighting assemblies, appliances, computers, industrial equipment, signaling and communications equipment, radios, electrically powered components on boats, recreational vehicles or other vehicles, battery chargers and even the balance-of-plant electrical requirements for the energy-producing system 22 of which fuel cell stack 24 forms a part. As indicated in dashed lines at 77 in
In
Additionally, the energy recovery assembly may be configured to apply recovered energy 202 to one or more components of energy-producing system 22. For example, recovered energy 202 may be applied to one or more components of hydrogen-producing region 70, temperature modulating assembly 71, separation region 72 (including the subsequently described pressure swing adsorption assemblies), and/or fuel cell stack 24. As a further non-exclusive example, this recovered energy may be applied by using it to drive, or to assist in the driving, of pumps, compressors, blowers, and the like, which in turn may be adapted to assist in the operation of a component of system 22, such as one of the components discussed herein. It is within the scope of the disclosure that at least a portion of recovered energy 202 may be applied to component(s), device(s), and/or system(s) outside of energy-producing system 22. It is within the scope of the disclosure that energy recovery assembly 200 may alternatively, or additionally, recover other suitable type(s) of energy from an energy producing system, such as heat or thermal energy. It also is within the scope of the disclosure that the energy recovery assembly alternatively, or additionally, is adapted to recover energy from other suitable stream(s) and/or component(s) of the energy producing system. Illustrative examples of suitable streams include reflux streams, blowdown streams, purge streams, feed streams, etc.
In
In the illustrative example, distribution assembly 102 is adapted to selectively deliver mixed gas stream 74 to the plurality of beds and to collect and exhaust byproduct stream 76, and distribution assembly 104 is adapted to collect the purified hydrogen gas that passes through the beds and which forms product hydrogen stream 42. The distribution assemblies may be configured for fixed or rotary positioning relative to the beds. Furthermore, the distribution assemblies may include any suitable type and number of structures and devices to selectively distribute, regulate, meter, prevent and/or collect flows of the corresponding gas streams. As illustrative, non-exclusive examples, distribution assembly 102 may include mixed gas and exhaust manifolds, or manifold assemblies, and distribution assembly 104 may include product and purge manifolds, or manifold assemblies. In practice, PSA assemblies that utilize distribution assemblies that rotate relative to the beds may be referred to as rotary pressure swing adsorption assemblies, and PSA assemblies in which the manifolds and beds are not adapted to rotate relative to each other to selectively establish and restrict fluid connections may be referred to as fixed bed, or discrete bed, pressure swing adsorption assemblies. Both constructions are within the scope of the present disclosure.
Gas purification by pressure swing adsorption involves sequential pressure cycling and flow reversal of gas streams relative to the adsorbent beds. In the context of purifying a mixed gas stream comprised of hydrogen gas as the majority component, the mixed gas stream is delivered under relatively high pressure to one end of the adsorbent beds and thereby exposed to the adsorbent(s) contained in the adsorbent region thereof. Illustrative examples of delivery pressures for mixed gas stream 74 include pressures in the range of 40-200 psi, such as pressures in the range of 50-150 psi, 50-100 psi, 100-150 psi, 70-100 psi, etc., although pressures outside of this range are within the scope of the present disclosure. As the mixed gas stream flows through the adsorbent region, carbon monoxide, carbon dioxide, water and/or other ones of the impurities, or other gases, are adsorbed, and thereby at least temporarily retained, on the adsorbent. This is because these gases are more readily adsorbed on the selected adsorbents used in the PSA assembly. The remaining portion of the mixed gas stream, which now may perhaps more accurately be referred to as a purified hydrogen stream, passes through the bed and is exhausted from the other end of the bed. In this context, hydrogen gas may be described as being the less readily adsorbed component, while carbon monoxide, carbon dioxide, etc., may be described as the more readily adsorbed components of the mixed gas stream. The pressure of the product hydrogen stream is typically reduced prior to utilization of the gas by the fuel cell stack.
To remove the adsorbed gases, the flow of the mixed gas stream is stopped, the pressure in the bed is reduced, and the now desorbed gases are exhausted from the bed. The desorption step often includes selectively decreasing the pressure within the adsorbent region through the withdrawal of gas, typically in a countercurrent direction relative to the feed direction. This desorption step may also be referred to as a depressurization, or blowdown, step. This step often includes or is performed in conjunction with the use of a purge gas stream, which is typically delivered in a countercurrent flow direction to the direction at which the mixed gas stream flows through the adsorbent region. An illustrative example of a suitable purge gas stream is a portion of the product hydrogen stream, as this stream is comprised of hydrogen gas, which is less readily adsorbed than the adsorbed gases. Other gases may be used in the purge gas stream, although these gases preferably are less readily adsorbed than the adsorbed gases, and even more preferably are not adsorbed, or are only weakly adsorbed, on the adsorbent(s) being used.
As discussed herein, the desorption and/or purge steps may include drawing an at least partial vacuum on the bed, but this is not required. Drawing the at least partial vacuum on the bed may occur during the entire desorption and/or purge steps. Alternatively, drawing the at least partial vacuum on the bed may occur during one or more portions of the desorption and/or purge steps, such as one or more of the beginning of the desorption step, the middle of the desorption step, the end of the desorption step, the beginning of the purge step, the middle of the purge step, the end of the purge step, and/or any suitable combination of those portions. In some embodiments, the at least partial vacuum may be applied during at least the middle and/or end of the purge step to remove the impurities that would not otherwise be removed without the at least partial vacuum.
While not required, it is often desirable to utilize one or more equalization steps, in which two or more beds are fluidly interconnected to permit the beds to equalize the relative pressures therebetween. For example, one or more equalization steps may precede the desorption and pressurization steps. Prior to the desorption step, equalization is used to reduce the pressure in the bed and to recover some of the purified hydrogen gas contained in the bed, while prior to the (re)pressurization step, equalization is used to increase the pressure within the bed. Equalization may be accomplished using cocurrent and/or countercurrent flow of gas. After the desorption and/or purge step(s) of the desorbed gases is completed, the bed is again pressurized and ready to again receive and remove impurities from the portion of the mixed gas stream delivered thereto.
For example, when a bed is ready to be regenerated, it is typically at a relatively high pressure and contains a quantity of hydrogen gas. While this gas (and pressure) may be removed simply by venting the bed, other beds in the assembly will need to be pressurized prior to being used to purify the portion of the mixed gas stream delivered thereto. Furthermore, the hydrogen gas in the bed to be regenerated preferably is recovered so as to not negatively impact the efficiency of the PSA assembly. Therefore, interconnecting these beds in fluid communication with each other permits the pressure and hydrogen gas in the bed to be regenerated to be reduced while also increasing the pressure and hydrogen gas in a bed that will be used to purify impure hydrogen gas (i.e., mixed gas stream 74) that is delivered thereto. In addition to, or in place of, one or more equalization steps, a bed that will be used to purify the mixed gas stream may be pressurized prior to the delivery of the mixed gas stream to the bed. For example, some of the purified hydrogen gas may be delivered to the bed to pressurize the bed. While it is within the scope of the present disclosure to deliver this pressurization gas to either end of the bed, in some embodiments it may be desirable to deliver the pressurization gas to the opposite end of the bed than the end to which the mixed gas stream is delivered.
The above discussion of the general operation of a PSA assembly has been somewhat simplified. Illustrative examples of pressure swing adsorption assemblies, including components thereof and methods of operating the same, are disclosed in U.S. Pat. Nos. 3,564,816, 3,986,849, 5,441,559, 6,692,545, and 6,497,856, and U.S. patent application Ser. Nos. 11/055,843 and 11/058,307; the complete disclosures of these patents and patent applications are hereby incorporated by reference for all purposes.
In
When the PSA assembly includes a desiccant or other water-removal composition or device, it may be positioned to remove water from the mixed gas stream prior to adsorption of other impurities from the mixed gas stream. One reason for this is that water may negatively affect the ability of some adsorbents to adsorb other components of the mixed gas stream, such as carbon monoxide. An illustrative example of a water-removal device is a condenser, but others may be used between the hydrogen-producing region and adsorbent region, as schematically illustrated in dashed lines at 122 in
The adsorbent(s) may be present in the bed in any suitable form, illustrative examples of which include particulate form, bead form, porous discs or blocks, coated structures, laminated sheets, fabrics, and the like. When positioned for use in the beds, the adsorbents should provide sufficient porosity and/or gas flow paths for the non-adsorbed portion of the mixed gas stream to flow through the bed without significant pressure drop through the bed. As used herein, the portion of a bed that contains adsorbent will be referred to as the adsorbent region of the bed. In
In the illustrated example shown in
During use of an adsorbent bed, such as bed 100, to adsorb impurity gases (namely the gases with greater affinity for being adsorbed by the adsorbent), a mass-transfer zone will be defined in the adsorbent region. More particularly, adsorbents have a certain adsorption capacity, which is defined, at least in part, by the composition of the mixed gas stream, the flow rate of the mixed gas stream, the operating temperature and/or pressure at which the adsorbent is exposed to the mixed gas stream, any adsorbed gases that have not been previously desorbed from the adsorbent, etc. As the mixed gas stream is delivered to the adsorbent region of a bed, the adsorbent at the end portion of the adsorbent region proximate the mixed gas delivery port will remove impurities from the mixed gas stream. Generally, these impurities will be adsorbed within a subset of the adsorbent region, and the remaining portion of the adsorbent region will have only minimal, if any, adsorbed impurity gases. This is somewhat schematically illustrated in
As the adsorbent in the initial mass transfer zone continues to adsorb impurities, it will near or even reach its capacity for adsorbing these impurities. As this occurs, the mass transfer zone will move toward the opposite end of the adsorbent region. More particularly, as the flow of impurity gases exceeds the capacity of a particular portion of the adsorbent region (i.e., a particular mass transfer zone) to adsorb these gases, the gases will flow beyond that region and into the adjoining portion of the adsorbent region, where they will be adsorbed by the adsorbent in that portion, effectively expanding and/or moving the mass transfer zone generally toward the opposite end of the bed.
This description is somewhat simplified in that the mass transfer zone often does not define uniform beginning and ending boundaries along the adsorbent region, especially when the mixed gas stream contains more than one gas that is adsorbed by the adsorbent. Similarly, these gases may have different affinities for being adsorbed and therefore may even compete with each other for adsorbent sites. However, a substantial portion (such as at least 70% or more) of the adsorption will tend to occur in a relatively localized portion of the adsorbent region, with this portion, or zone, tending to migrate from the feed end to the product end of the adsorbent region during use of the bed. This is schematically illustrated in
During use of the PSA assembly, the mass transfer zone will tend to migrate toward and away from ends 124 and 126 of the adsorbent region. More specifically, and as discussed, PSA is a cyclic process that involves repeated changes in pressure and flow direction. The following discussion will describe the PSA cycle with reference to how steps in the cycle tend to affect the mass transfer zone (and/or the distribution of adsorbed gases through the adsorbent region). It should be understood that the size, or length, of the mass transfer zone will tend to vary during use of the PSA assembly, and therefore tends not to be of a fixed dimension.
At the beginning of a PSA cycle, the bed is pressurized and the mixed gas stream flows under pressure through the adsorbent region. During this adsorption step, impurities (i.e., the other gases) are adsorbed by the adsorbent(s) in the adsorbent region. As these impurities are adsorbed, the mass transfer zone tends to move toward the distal, or product, end of the adsorbent region as initial portions of the adsorbent region become more and more saturated with adsorbed gas. When the adsorption step is completed, the flow of mixed gas stream 74 to the adsorbent bed and the flow of purified hydrogen gas (at least a portion of which will form product hydrogen stream 42) are stopped. While not required, the bed may then undergo one or more equalization steps in which the bed is fluidly interconnected with one or more other beds in the PSA assembly to decrease the pressure and hydrogen gas present in the bed and to charge the receiving bed(s) with pressure and hydrogen gas. Gas may be withdrawn from the pressurized bed from either, or both of, the feed or the product ports. Drawing the gas from the product port will tend to provide hydrogen gas of greater purity than gas drawn from the feed port. However, the decrease in pressure resulting from this step will tend to draw impurities in the direction at which the gas is removed from the adsorbent bed. Accordingly, the mass transfer zone may be described as being moved toward the end of the adsorbent bed closest to the port from which the gas is removed from the bed. Expressed in different terms, when the bed is again used to adsorb impurities from the mixed gas stream, the portion of the adsorbent region in which the majority of the impurities are adsorbed at a given time, i.e., the mass transfer zone, will tend to be moved toward the feed or product end of the adsorbent region depending upon the direction at which the equalization gas is withdrawn from the bed.
The bed is then depressurized, with this step typically drawing gas from the feed port because the gas stream will tend to have a higher concentration of the other gases, which are desorbed from the adsorbent as the pressure in the bed is decreased. This exhaust stream may be referred to as a byproduct, or impurity stream, 76 and may be used for a variety of applications, including as a fuel stream for a burner or other heating assembly that combusts a fuel stream to produce a heated exhaust stream. As discussed, hydrogen-generation assembly 46 may include a heating assembly 71 that is adapted to produce a heated exhaust stream to heat at least the hydrogen-producing region 70 of the fuel processing system. According to Henry's Law, the amount of adsorbed gases that are desorbed from the adsorbent is related to the partial pressure of the adsorbed gas present in the adsorbent bed. Therefore, the depressurization step may include, be followed by, or at least partially overlap in time, with a purge step, in which gas, typically at low pressure, is introduced into the adsorbent bed. This gas flows through the adsorbent region and draws the desorbed gases away from the adsorbent region, with this removal of the desorbed gases resulting in further desorption of gas from the adsorbent. As discussed, a suitable purge gas is purified hydrogen gas, such as previously produced by the PSA assembly. Typically, the purge stream flows from the product end to the feed end of the adsorbent region to urge the impurities (and thus reposition the mass transfer zone) toward the feed end of the adsorbent region. It is within the scope of the disclosure that the purge gas stream may form a portion of the byproduct stream, may be used as a combustible fuel stream (such as for heating assembly 71), and/or may be otherwise utilized in the PSA or other processes.
The illustrative example of a PSA cycle is now completed, and a new cycle is typically begun. For example, the purged adsorbent bed is then repressurized, such as by being a receiving bed for another adsorbent bed undergoing equalization, and optionally may be further pressurized by purified hydrogen gas delivered thereto. By utilizing a plurality of adsorbent beds, typically three or more, the PSA assembly may be adapted to receive a continuous flow of mixed gas stream 74 and to produce a continuous flow of purified hydrogen gas (i.e., a continuous flow of product hydrogen stream 42). While not required, the time for the adsorption step, or stage, often represents one-third to two-thirds of the PSA cycle, such as representing approximately half of the time for a PSA cycle.
The adsorption step preferably should be stopped before the mass transfer zone reaches the distal end (relative to the direction at which the mixed gas stream is delivered to the adsorbent region) of the adsorbent region. In other words, the flow of mixed gas stream 74 and the removal of product hydrogen stream 42 preferably should be stopped before the other gases that are desired to be removed from the hydrogen gas are exhausted from the bed with the hydrogen gas because the adsorbent is saturated with adsorbed gases and therefore can no longer effectively prevent these impurity gases from being exhausted in what desirably is a purified hydrogen stream. This contamination of the product hydrogen stream with impurity gases that desirably are removed by the PSA assembly may be referred to as breakthrough, in that the impurities gases “break through” the adsorbent region of the bed. Conventionally, carbon monoxide detectors have been used to determine when the mass transfer zone is nearing or has reached the distal end of the adsorbent region and thereby is, or will, be present in the product hydrogen stream. Carbon monoxide detectors are used more commonly than detectors for other ones of the other gases present in the mixed gas stream because carbon monoxide can damage many fuel cells, such as proton exchange membrane (PEM) fuel cells, when present in even a few parts per million (ppm). While effective, and within the scope of the present disclosure, this detection mechanism requires the use of carbon monoxide detectors and related detection equipment, which tends to be expensive and increase the complexity of the PSA assembly.
As introduced in connection with
As discussed in connection with
In the illustrative embodiments shown in
Although not required,
In an implemented embodiment of PSA assembly 73, any suitable number, structure and construction of manifolds and fluid conduits for the fluid streams discussed herein may be utilized. Similarly, any suitable number and type of valves or other flow-regulating devices 170 and/or sensors or other property detectors 172 may be utilized, illustrative, non-exclusive examples of which are shown in
While not required, it is within the scope of the present disclosure that the PSA assembly may include, be associated with, and/or be in communication with a controller that is adapted to control the operation of at least portions of the PSA assembly and/or an associated hydrogen-generation assembly and/or fuel cell system. A controller is schematically illustrated in
As discussed above, the degree of separation between hydrogen and the other gases from the mixed gas stream is affected by the pressure difference between the pressure of the mixed gas stream 74 delivered to the PSA assembly's beds and the pressure of the byproduct stream 76 exhausted from the PSA assembly beds. Thus, a greater pressure difference between the pressure of the mixed gas stream and the pressure of the byproduct stream may lead to greater separation or recovery of hydrogen from the other gases of the mixed gas stream. Therefore, for a determined, or selected mixed gas stream pressure, the degree of separation may be increased by reducing the pressure of the byproduct stream, such as by drawing an at least partial vacuum on the bed(s) via a vacuum system during at least part of the desorption and/or purge steps.
Although not required to all embodiments, PSA assemblies 73 according to the present disclosure may include, or be in communication with, a vacuum system that is configured to draw at least a partial vacuum on one or more beds of the PSA assembly to assist in the desorption and/or purging steps of the PSA process. For example, illustrative examples of PSA assemblies 73 that include a vacuum system are shown in
In the illustrative examples shown in
Expressed in slightly different terms, the purge system is adapted to generate an at least partial vacuum, which may be referred to as a purging vacuum, that is selectively applied to at least one of the beds of the PSA assembly during the purging and/or desorption steps of the PSA process. In the illustrative example shown in
The vacuum system may be powered, or driven, by any suitable method(s) and/or system(s). Although not required,
Vacuum system 160 and/or energy-recovery assembly 200 may be configured to be optional, or supplementary, component(s) of purge system 146 and hydrogen-generating and/or fuel cell systems containing the same. The purge system is thus configured to suitably purge one or more of adsorbent beds 100 of PSA assembly 73 regardless of the amount of purging vacuum, if any, generated by vacuum pump 162 and/or stored in purging vacuum supply 164. By “regardless of,” it is meant that the purge system is configured to suitably purge the adsorbent beds whether or not the vacuum system is assisting in the desorption and/or purge steps of the PSA process. When the vacuum system is generating a sufficient vacuum supply to assist in one or both of these steps, then the PSA assembly may be able to increase the amount of hydrogen gas present in the product hydrogen stream, as compared to the amount that would be present without vacuum-assisted desorption/purging. However, the product hydrogen stream produced without this vacuum-assistance should still be of sufficient quantity and purity for use as a reasonable fuel stream for the fuel cell stack.
Accordingly, the PSA assemblies, hydrogen-generation assemblies, and/or fuel cell systems that include energy-recovery assemblies and/or vacuum systems according to the present disclosure may be configured to operate and suitably purify and/or generate an electric current from the produced hydrogen gas regardless of whether the vacuum system and/or energy-recovery assembly are operating. Therefore, these components may be considered to be optional performance-enhancing or performance-boosting components because they may increase the product hydrogen recovered when they are operating, but they will not interfere with the operation of the fuel cell (or other) system when they are not operating. In other words, it is within the scope of the present disclosure that the vacuum system and energy-recovery assembly are not required to be operational for PSA assembly 73 to operate to suitably separate the mixed gas stream into the product hydrogen and byproduct streams. Accordingly, purge system 146 may be adapted to suitably purge the adsorbent beds of the PSA assembly regardless of whether the vacuum system is generating a vacuum and/or regardless of whether the vacuum supply chamber includes a vacuum supply and/or whether energy-recovery assembly 200 is generating mechanical energy from the product hydrogen stream to drive the operation of the vacuum system.
Gas motor 204 may be selectively configured among, or between, a plurality of operating states. Those operating states include at least an energy recovering operating state, in which the gas motor is recovering mechanical energy from the product hydrogen stream, and an idle operating state, in which the gas motor is not recovering mechanical energy from the product hydrogen stream. It is within the scope of the disclosure that gas motor 204 may be selectively configured among additional defined operating states, including a transition operating state in which the gas motor is transitioning between the energy recovering operating state and the idle operating state.
The gas motor may be configured to operate among the plurality of operating states based, or responsive, at least in part, on one or more PSA process parameters, such as the pressure of the product hydrogen stream. For example, the gas motor may be configured to transition (or self-start) from the idle operating state to the energy recovering operating state responsive, at least in part, to when the pressure of the product hydrogen stream exceeds a threshold pressure. The threshold pressure may be any suitable predetermined pressure. The threshold pressure may be inherent in the energy-recovery system, such as the pressure required to drive the gas motor or other energy recovery device. It is also within the scope of the present disclosure that the threshold pressure may relate to one or more process goals, such as optimizing when the gas motor is in the energy recovering operating state, ensuring that the product hydrogen stream exhausted from the gas motor or other energy recovery device retains sufficient pressure for use as a fuel for fuel cell stack 24, etc. In some embodiments it may be desirable to utilize a threshold pressure that is at least 60 psi, at least 65 psi, in the range of 60-75 psi, etc. It is within the scope of the disclosure, however, that threshold pressures greater than or less than these illustrative threshold pressures may be used.
The gas motor may in addition, or alternatively, be configured to transition from the idle operating state to the energy recovering operating state responsive, at least in part, to when the pressure of the product hydrogen stream is within a specified pressure range. The specified pressure range may be any suitable predetermined pressure and may relate to one or more process goals, illustrative, non-exclusive examples of which are discussed above. For example, the specified pressure range may be 65 to 120 psi because any pressure less than that range may be too low for efficient use and any pressure greater than that range may be beyond the design of industrial pneumatics. It is within the scope of the disclosure, however, that other specified pressure ranges may be used.
Additionally, or alternatively, the gas motor may be configured to transition from the energy recovering operating state to the idle operating state responsive, at least in part, to when the pressure of the product hydrogen stream falls below a lower threshold pressure, exceeds an upper threshold pressure, and/or falls outside a specified pressure range. The lower and upper threshold pressures may be any suitable predetermined pressures and may relate to one or more process goals. For example, the lower threshold pressure may be set at 65 psi and the upper threshold pressure may be set at 120 psi for at least the reasons discussed in the illustrative examples above. It is within the scope of the disclosure, however, that lower threshold pressures greater than or less than 65 psi may be used. Additionally, it is within the scope of the disclosure that upper threshold pressures less than or greater than 120 psi may be used.
It is within the scope of the disclosure that the gas motor be configured to transition between the plurality of operating states based, at least in part, on other PSA process parameters, such as temperature of the product hydrogen stream, pressure of the mixed gas stream, the vacuum supply, the current stage of the PSA process, etc. Additionally, it is within the scope of the disclosure that the gas motor be configured to transition between the plurality of operating states based, at least in part, on process parameters other than those associated with the PSA process, such as process parameters associated with the fuel processing system and/or the fuel cell stack.
Illustrative (non-exclusive) examples of gas motors are shown in
Gas motor 204 includes a working portion 214 disposed between the inlet and outlet ports, where the inlet and outlet ports and the working portion are in fluid communication with the product hydrogen stream, as shown in
An illustrative, non-exclusive example of a suitable gas motor is a piston-driven air motor that has been sealed to prevent hydrogen gas from leaking. Illustrative examples include the high purity series of air motors from Dynatork Air Motors. It is within the scope of the disclosure, however, that gas motor 204 may include other devices, such as expander(s) and the like that are configured to recover or otherwise extract or produce mechanical energy from product hydrogen stream 42.
Illustrative examples of mechanical couplings are shown in
Although gas motor 204 is shown to be mechanically connected to vacuum pump 162 via mechanical coupling 206, it is within the scope of the disclosure that gas motor 204 may be connected to other components of energy producing system 22 in addition to, or as an alternative to, the vacuum pump. For example, it is within the scope of the disclosure that gas motor 204 may be mechanically connected to natural gas or other compressor(s), carbon-containing feed compressor(s), cathode blower(s), anode recirculator(s), and/or fuel cell coolant pump(s) of the energy producing system. It may be preferable to mechanically connect the gas motor to the largest balance-of-plant (BOP) loads of energy producing system 22 and thus configure the gas motor to apply recovered energy to those loads. Additionally, or alternatively, gas motor 204 may be mechanically connected to one or more components outside of energy-producing system 22, such as energy-consuming device 52.
As an illustrative example of another illustrative embodiment of energy recovery and reuse assembly 226, gas motor 204 may be mechanically connected to a mixed gas stream feed compressor, which is configured to increase the pressure of the hydrogen-containing mixed gas stream that is delivered to the PSA assembly for purification. That increase of pressure provides a greater pressure difference between the pressure of the mixed gas stream and the pressure of the byproduct stream, which may lead to a greater degree separation or recovery of hydrogen from the other gases of the mixed gas stream. Alternatively, the gas motor may be mechanically connected to both the vacuum pump and the mixed gas stream feed compressor to potentially provide an even greater pressure difference between the pressure of the mixed gas stream and the pressure of the byproduct stream, which may lead to an even greater degree of separation or recovery of hydrogen from the other gases of the mixed gas stream.
As illustrated in
It should be understood that the energy-recovery assembly and vacuum systems described herein are optional, or supplementary, components of the hydrogen-generation assembly. The operation (or non-operation) of these components, including gas motor 204, is thus independent, or regardless, of the ability of the PSA (or other separation) assembly to produce the product hydrogen stream. Additionally, pressure regulator 224 is configured to regulate the pressure of the product hydrogen stream independent, or regardless, of the operating state of the gas motor. Gas motor 204 is thus not required for the hydrogen-generation assembly to produce hydrogen or to regulate the pressure of the hydrogen. The energy recovery and reuse assembly and/or gas motor may therefore be considered an optional operational enhancement, performance enhancing, or performance-boosting component because it recovers energy when operating but is not required by the hydrogen-generation assembly to produce the product hydrogen stream and/or to regulate the pressure of the product hydrogen stream.
In
Although discussed herein in the context of a PSA assembly for purifying hydrogen gas, it is within the scope of the present disclosure that the energy recovery assemblies disclosed herein, as well as the methods of operating the same, may be used in other applications.
The pressure swing adsorption assemblies and hydrogen-generation and/or fuel cell systems including the same are applicable in the gas generation and fuel cell fields, including such fields in which hydrogen gas is generated, purified, and/or consumed to produce an electric current.
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.