Compact efficient hydrogen reactor
11749822 · 2023-09-05
Assignee
Inventors
- Jason L. Stimits (Loughborough, GB)
- RUSSELL BARTON (LOUGHBOROUGH, GB)
- Douglas A. Knight (Loughborough, GB)
- Iain M. Fraser (Loughborough, GB)
- Hao Huang (Loughborough, GB)
- Sandra H. Withers-Kirby (Loughborough, GB)
- Philbert C. Spencer (Loughborough, GB)
- Piotr Marcin Kleszyk (Loughborough, GB)
- Hossein Ostadi (Loughborough, GB)
Cpc classification
H01M8/0631
ELECTRICITY
C01B3/065
CHEMISTRY; METALLURGY
C01B3/08
CHEMISTRY; METALLURGY
Y02E60/36
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J19/28
PERFORMING OPERATIONS; TRANSPORTING
C01B2203/041
CHEMISTRY; METALLURGY
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
Y02E60/32
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
B01J19/28
PERFORMING OPERATIONS; TRANSPORTING
C01B3/06
CHEMISTRY; METALLURGY
C01B3/08
CHEMISTRY; METALLURGY
Abstract
Methods and devices and aspects thereof for generating power using PEM fuel cell power systems comprising a rotary bed (or rotatable) reactor for hydrogen generation are disclosed. Hydrogen is generated by the hydrolysis of fuels such as lithium aluminum hydride and mixtures thereof. Water required for hydrolysis may be captured from the fuel cell exhaust. Water is preferably fed to the reactor in the form of a mist generated by an atomizer. An exemplary 750 We-h, 400 We PEM fuel cell power system may be characterized by a specific energy of about 550 We-h/kg and a specific power of about 290 We/kg. Turbidity fixtures within the reactor increase turbidity of fuel pellets within the reactor and improve the energy density of the system.
Claims
1. A rotatable reactor comprising: an outer housing; a fuel containment insert (1000) configured to rotate within the outer housing; a solid fuel (600) inside the reactor (509) of the fuel containment insert; at least one liquid inlet in fluid communication with the containment insert; at least one atomizer in fluid communication with the liquid inlet; at least one hydrogen outlet in fluid communication with the containment insert; wherein at least one of the containment insert and the containment insert and liquid inlet are removable from the outer housing; wherein the reactor comprises an outer shell (1201) and an inner shell (1202) which further contains a perforated core (1203) comprising perforations (1204), said core is configured to contain the solid fuel and allow byproducts produced during hydrolysis of the solid fuel to pass through the perforations of the perforated core.
2. The reactor of claim 1 wherein the solid fuel comprises fuel pellets, and the fuel pellets are between about 4 mm and about 15 mm in diameter.
3. The reactor of claim 1 further comprising a liquid reservoir (506) in fluid communication with the liquid inlet.
4. The reactor of claim 3 wherein the liquid reservoir further comprises: an electrical solenoid to open and close liquid flow to the liquid inlet; and, an end cap (513) with an external portion (513′) and a plunger portion (513″) the plunger portion being driven by a spring (512) configured to pressurize the fluid reservoir.
5. The reactor of 1 further comprising a fluid pump in fluid communication with a fluid supply and the liquid inlet.
6. The reactor of claim 1 further comprising at least one turbidity fixtures (602) and stirring element (604) formed as part of or affixed to an interior surface (510) of the reactor.
7. The reactor of claim 1 wherein solid the fuel comprises lithium aluminum hydride.
8. The reactor of claim 1 wherein solid the fuel comprises an admixture of lithium aluminum hydride and an additive comprising at least one of AlCl.sub.3, MgCl.sub.2, BeCl.sub.2, CuCl.sub.2, LiCl, NaCl, and KCl.
9. The reactor of claim 8 wherein the amount of additive in the admixture is between 5 wt.-% and 30 wt.-%.
Description
DRAWINGS
(1) The foregoing aspects and many of the attendant advantages of this disclosure will become more readily appreciated as the same becomes better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17) The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the disclosure. All reference numerals, designators and callouts in the figures and Appendices are hereby incorporated by this reference as if folly set forth herein. The failure to number an element in a figure is not intended to waive any rights. Unnumbered references may also be identified by alpha characters in the figures. All callouts in figures are hereby incorporated by this reference as if fully set forth herein.
(18) The following detailed description includes references to the accompanying drawings, which form a part of the detailed description. The drawings show, by way of illustration, specific embodiments in which the fuel cell systems and methods may be practiced. These embodiments, which are also referred to herein as “examples” or “options,” are described in enough detail to enable those skilled in the art to practice the present invention. The embodiments may be combined, other embodiments may be utilized or structural or logical changes may be made without departing from the scope of the invention. The following detailed description is, therefore, not to be taken in a limiting sense and the scope of the invention is defined by the appended claims and their legal equivalents.
(19) In this document, the terms “a” or “an” are used to include one or more than one, and the term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation.
DETAILED DISCLOSURE
(20) Particular aspects of the disclosure are described below in considerable detail for the purpose for illustrating its principles and operation. However, various modifications may be made, and the scope of the invention is not limited to the exemplary aspects described.
(21) The fuel cell power system schemes described below target methods and devices that lead to efficient and lightweight power systems for applications such as unmanned aerial vehicles. In one aspect 100 (
(22) The fuel cell power system may optionally include a hydrogen storage component (e.g. metal hydride) that may provide hydrogen required for start-up. In this case, water for start-up may not be required. The hydrogen storage component may be recharged with the hydrogen that is produced. The fuel cell power system may also contain a small Li-ion battery for providing power during start-up and for handling peak loads.
(23) In the fuel cell system described in
(24)
(25) In a second aspect of the fuel cell power system, water recovery from the fuel cell may be accomplished without the use of a condenser or a humidifier. In the scheme 200 (
(26) A single air blower may be used to provide both reactant air and coolant air to fuel cell 211. In this case, active cooling of the water collection components 204 may be required using water from the water storage 206. Uncondensed gases (unreacted oxygen, nitrogen) in the cathode exhaust would have to be vented at a suitable point: for example, from the water storage 206 or a gas/liquid separator such as a flash tank. Use of a closed cathode stack in fuel cell 211 may require a stack purge after change out of reactor 209 using an inert gas.
(27) In a third aspect of the fuel cell power system (
(28) The requirements of the target fuel cell power application generally dictates the choice between open cathode fuel cell stack schemes (
(29) When applications permit the use of external water, but require a simple and lightweight fuel cell power system, schemes that do not involve hydrogen recirculation may be considered.
(30) In the above aspects and their embodiments, components that include, but are not limited to, liquid feed pump or spring or other mechanism for producing pressurized water, atomizer or atomizing nozzle, micro water control valve, reactor, hydrogen pumps, water storage, and the hydrogen recirculation stream flow restrictor may be interchangeably used. The liquid feed pump could comprise of a miniature piezoelectric pump or other micro pump designs that can output 300 ml/h of water to generate hydrogen from LAH to support a 400 We, 750 We-h fuel cell power system. The parasitic power requirement of the pump is expected to be below 0.5 W. Alternatively, the parasitic loss due to the water pump can be substantially reduced by replacing the water pump with a spring mechanism that pressurizes the water reservoir and, when coupled with a micro water valve, allows water to be controllably dispensed through the atomizing nozzle. The atomizer may be closely coupled to reactor to prevent condensation of water into large droplets. The parasitic power requirement for an ultrasonic atomizer is expected to be less than 5 W. Water storage may be in the form of a flexible bladder that can store 50 g to 300 g of water depending on the requirements of a particular application. The hydrogen recirculation blower is also lightweight (<150 g) with a preferable capacity of at least 50 SLPM at 50 mbar.
(31) Any feasible combination of the concepts described above may be employed to yield a suitable fuel cell power system. For example, in process schemes that use either open cathode or closed cathode stacks without the use of hydrogen recirculation, dry hydrogen exiting the reactor may be humidified by cathode air exhaust (using a suitable humidifier) prior to feeding to the anode side of the stack. Using humidified hydrogen is known to increase the lifetime of air cooled PEM fuel cell stacks.
(32) The process schemes and fuel cell power systems described above system require hydrogen generation at a sufficient rate in the reactor to support the power output from the fuel cell as well as maintain the recirculation rate required. The inventors observed unsatisfactory hydrogen generation rates and yields during vapor phase hydrolysis in a conventional fixed bed reactor. As shown in
(33) A reactor that is suitable for use in the above described process schemes is a rotary bed reactor or rotatable reactor. An exemplary rotary bed reactor 800, as shown in
(34) Table 1 shows the forecasted specific energy and specific power using an open cathode fuel cell power system nm without hydrogen recirculation or water recovery. A rotary bed reactor is used. The specific energy of about 550 We-h/kg is >2× better than Li-ion batteries. The specific power of about 290 W-e/kg is >5× better than that disclosed in U.S. Pat. No. 9,005,572 for a 33 We fuel cell power system.
(35) TABLE-US-00001 TABLE 1 Metric Value Energy (W-h) 750 Power (W) 400 Fuel Cell stack (g) 250 Power/control electronics (g) 60 Li-ion battery (g) 120 Fluidic circuitry (g) 10 LAH Fuel Cartridge (g) 450 Case (g) 80 Total (g) 1370 Specific Energy (Wh/kg) 547 Specific Power (W/kg) 292
(36)
(37)
(38) Perforated core is configured to engage with d liven gear 1205 and may preferably rotate (along with shell 1202) at 2 rpm to 25 rpm. Perforated core 1203 may be made of injected molded plastic that includes PEEK and ULTEM and has first end 1207 and a second end 1208 opposite to the first end. End 1208 may be closed using a plastic end cap 1209. Fuel (e.g. LAH) particles are disposed in the region 1206 between shell 1202 and perforated core 1203. Assembly 1210 shown in
(39) As described above, water mists may be generated using an atomizer. It has been found that using water in the form of a mist (dispersed water droplets) increases the hydrogen generation rate compared to water vapor. When water is in the form of a mist, the water droplets increases the actual mass of water per unit volume entering the reactor. Compared to humidified recirculating hydrogen that contains water vapor, the use of water mist increases the rate of hydrogen generation and fuel utilization. Devices such as fuel injector for combustion engines may also be modified and used to atomize water and generate the water spray or mist. Strictly controlling the mist output rates would avoid issues such as start/stop outgassing or pressure spikes commonly seen when feeding liquid water.
(40)
(41) The fluid container 506 with an interior surface 506′ is also provided. The rotatable fuel reactor 509 and fluid container 506 connect via the mating guide 612 and the cooperating mating guide 614 at a fluid interface 610. The connection provides for controlled fluid delivery to the containment insert 1000 and disassociation of at least one of the fluid container and the containment insert 1000 from the system. The disassociation includes removal and replacement. The fluid container 506 may be reversibly sealed via a cap 513. The fluid container maybe refillable. Fluid is kept at pressure above ambient pressure preferably between 5-50 psi to maintain adequate fluid pressure for atomization of the fluid through the atomizing nozzle 508. Fluid can be kept at pressure by various mechanisms including external pump or via integration of a spring 512 and cap 513. The spring 512 provides a force by which the interior portion of the end cap acts as a plunger to exert pressure on the fluid in the fluid container. Fuel reactor 509 is rotated by motor 514. Fluid injection rate through the atomizer 508 may be controlled via a solenoid valve 515 that is actuated and may be controlled via a microprocessor or controller. A fluid input 625 provides a fluid connection via the solenoid valve to the atomizer 508. Fluid in the form of mist exit at the reactor fluid input 508′ when the fluid entering the atomizer is pressurized. Those of ordinary skill in the art will recognize that a plentitude of controllers exist in the art and the invention scope is not limited to one particular control scheme. The control may be deployed based on at least one of fluid pressure, hydrogen pressure, hydrogen flow, temperature. time, hydrogen output, voltage or other measured system paran1eter(s). Optionally, a removable lightweight protective outer shell 516 may be added. To reduce cost, all components can be reusable and/or refillable. The rotating mechanism such as a motor or motor and gear system 514 is configured to rotate the reactor while leaving the hydrogen output connection 650 free to connect a fuel cell 700 or other hydrogen using or storing device. Between the output connection 650 and the inside of the reactor 509′ is a filter 690 to prevent fine particles from being passed into the H2 output stream. A control valve 675 may be added to at least one of relive pressure in an over pressurized system or to prevent backflow when hydrogen production is halted. Fluid may be between 100% and about 80% water by volume. In some instances heat exchange fixtures such as fins 900 are added to, or formed as part of, the fuel reactor 509. In some instance the heat exchange fixtures 900 may form a part of the turbidity fixtures. In some instances extended fins 900 from the exterior of the reactor coincide with raised or lowered regions on the interior of the reactor.
(42) Turbidity fixtures may be sized and/or positioned to enhance dispersion of fuel pellets during hydrolysis. By sizing and spacing the turbidity fixtures to correspond to the fuel pellet size and shape greater exposure of fluid to fuel is achieved and spent fuel which may crust onto the pellet is dislodged thereby exposing fuel. A system which matches fuel pellet morphology and turbidity fixtures may improve energy density.
(43)
(44) Suitable fuels for use in the rotary bed reactor as described in this disclosure include lithium aluminum hydride (LAH), with purity of at least 95%. The fuel is preferably formulated in the form of particles or tablets. If needed, certain additive materials such as activation agents or catalysts may be added to LAH to maximize hydrogen production from the fuel. Exemplary fuels and materials include, but are not limited to, those disclosed in commonly owned U.S. Pat. No. 8,636,961, and entitled “FUELS FOR HYDROGEN GENERATING CARTRIDGES.” which is incorporated by reference herein in its entirety. Exemplary fuels and materials may also include, but are not limited to those disclosed in, U.S. Pat. No. 7,393,369, entitled “APPARATUS, SYSTEM, AND METHOD FOR GENERATING HYDROGEN,” U.S. Pat. No. 7,438,732, entitled “HYDROGEN GENERATOR CARTRIDGE,” and U.S. Pat. No. 8,357,213, entitled “APPARATUS, SYSTEM, AND METHOD FOR PROMOTING A SUBSTANTIALLY COMPLETE REACTION OF AN ANHYDROUS HYDRIDE REACTANT,” which are all incorporated by reference herein in their entirety. Preferable additives include chloride salts that include, but are not limited to, AlCl.sub.3, MgCl.sub.2, BeCl.sub.2, CuCl.sub.2, LiCl, NaCl, and KCl. The amount of these additives in the fuel could be up to 65 wt.-%. Preferably, the amount of these additives in the fuel is between about 5 wt.-% and about 30 wt-%. A preferred alternative is to use LAH without any additives and to use preferred reactor designs such as the rotary bed reactor as described above. Other fuel candidates include sodium aluminum hydride, sodium borohydride, and sodium silicide.
(45) Air cooled stacks and methods of operation of the stacks are described in commonly owned U.S. Pat. No. 8,263,277 entitled “REHYDRATION OF FUEL CELLS,” and U.S. Pat. No. 8,323,846 entitled “FUEL CELL GAS DISTRIBUTION,” which are incorporated by reference herein in their entirety.
(46) The Abstract is provided to comply with 37 C.F.R. § 1.72(b), to allow the reader to determine quickly from a cursory inspection the nature and gist of the technical disclosure. It should not be used to interpret or limit the scope or meaning of the claims.
(47) Although the present disclosure has been described in connection with the preferred form of practicing it, those of ordinary skill in the art will understand that many modifications can be made thereto without departing from the spirit of the present disclosure. Accordingly, it is not intended that the scope of the disclosure in any way be limited by the above description.
(48) While the methods and fuel cell power systems have been described in terms of what are presently considered to be the most practical and preferred implementations, it is to be understood that the disclosure need not be limited to the disclosed implementations. It is intended to cover various modifications and similar arrangements included within the spirit and scope of the claims, the scope of which should be accorded the broadest interpretation so as to encompass all such modifications and similar structures. The present disclosure includes any and all implementations of the following claims.
(49) It should also be understood that a variety of changes may be made without departing from the essence of the disclosure. Such changes are also implicitly included in the description. They still fall within the scope of this disclosure. It should be understood that this disclosure is intended to yield a patent covering numerous aspects of the disclosure both independently and as an overall system and in both method and apparatus modes.
(50) Further, each of the various elements of the disclosure and claims may also be achieved in a variety of manners. This disclosure should be understood to encompass each such variation, be it a variation of an implementation of any apparatus implementation. a method or process implementation, or even merely a variation of any element of these.
(51) Particularly, it should be understood that as the disclosure relates to elements of the disclosure, the words for each element may be expressed by equivalent apparatus terms or method terms—even if only the function or result is the same.
(52) Such equivalent, broader, or even more generic terms should be considered to be encompassed in the description of each element or action. Such terms can be substituted where desired to make explicit the implicitly broad coverage to which this disclosure is entitled.
(53) It should be understood that all actions may be expressed as a means for taking that action or as an element which causes that action.
(54) Similarly, each physical element disclosed should be understood to encompass a disclosure of the action which that physical element facilitates.
(55) Any patents, publications, or other references mentioned in this application for patent are hereby incorporated by reference. In addition, as to each term used it should be understood that unless its utilization in this application is inconsistent with such interpretation common dictionary definitions should be understood as incorporated for each term and all definitions, alternative terms, and synonyms such as contained in at least one of a standard technical dictionary recognized by artisans and the Random House Webster's Unabridged Dictionary, latest editions are hereby incorporated by reference.
(56) To the extent that insubstantial substitutes are made, to the extent that the applicant did not in fact draft any claim so as to literally encompass any particular implementation, and to the extent otherwise applicable, the applicant should not be understood to have in any way intended to or actually relinquished such coverage as the applicant simply may not have been able to anticipate all eventualities: one skilled in the art, should not be reasonably expected to have drafted a claim that would have literally encompassed such alternative implementations.
(57) Further, the use of the transitional phrase “comprising” is used to maintain the “‘open-end” claims herein, according to traditional claim interpretation. Thus, unless the context requires otherwise, it should be understood that the term “compromise” or variations such as “comprises” or “comprising,”’ are intended to imply the inclusion of a stated element or step or group of elements or steps but not the exclusion of any other element or step or group of elements or steps. Such terms should be interpreted in their most expansive forms so as to afford the applicant the broadest coverage legally permissible.