US20060118428A1 - System for generating hydrogen and method thereof - Google Patents
System for generating hydrogen and method thereof Download PDFInfo
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- US20060118428A1 US20060118428A1 US11/050,931 US5093105A US2006118428A1 US 20060118428 A1 US20060118428 A1 US 20060118428A1 US 5093105 A US5093105 A US 5093105A US 2006118428 A1 US2006118428 A1 US 2006118428A1
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- hydrogen gas
- pressure
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the present disclosure relates to an electrochemical cell system and especially relates to a system for stopping the generation of hydrogen in the event of a fault condition.
- Electrochemical cells are energy conversion devices, usually classified as either electrolysis cells or fuel cells.
- An electrolysis cell functions as a hydrogen generator by electrolytically decomposing water to produce hydrogen and oxygen gases, and functions as a fuel cell by electrochemically reacting hydrogen with oxygen to generate electricity.
- FIG. 1 a partial section of a typical proton exchange membrane electrolysis cells is detailed.
- process water is fed into a cell on the side of the oxygen electrode (in an electrolytic cell, the anode) to form oxygen gas, electrons, and protons.
- the electrolytic reaction is facilitated by the positive terminal of a power source electrically connected to the anode and the negative terminal of the power source connected to a hydrogen electrode (in an electrolytic cell, the cathode).
- a cathode feed electrolysis cell (not shown), process water is fed on the hydrogen electrode, and a portion of the water migrates from the cathode across the membrane to the anode where protons and oxygen gas are formed. A portion of the process water exits the cell at the cathode side without passing through the membrane. The protons migrate across the membrane to the cathode where hydrogen gas is formed.
- the typical electrochemical cell system includes a number of individual cells arranged in a stack, with the working fluid directed through the cells via input and output conduits formed within the stack structure. The cells within the stack are sequentially arranged, each including a cathode, a proton exchange membrane, and an anode.
- the anode, cathode, or both are gas diffusion electrodes that facilitate gas diffusion to the membrane.
- Each cathode/membrane/anode assembly (hereinafter “membrane electrode assembly”, or “MEA”) is typically supported on both sides by flow fields comprising screen packs or bipolar plates. Such flow fields facilitate fluid movement and membrane hydration and provide mechanical support for the MEA. Since a differential pressure often exists in the cells, compression pads or other compression means are often employed to maintain uniform compression in the cell active area, i.e., the electrodes, thereby maintaining intimate contact between flow fields and cell electrodes over long time periods.
- a method of generating hydrogen gas including the steps of disassociating hydrogen from a reactant to form hydrogen gas. Monitoring a pressure of the hydrogen gas and comparing the pressure of the hydrogen gas to a threshold parameter. Finally generating a signal in response to the pressure being less than the threshold parameter.
- a method of generating hydrogen gas including the steps of electrochemically separating hydrogen from water. Forming hydrogen gas and monitoring the pressure of the hydrogen gas. Comparing the hydrogen gas pressure to a minimum threshold parameter. Measuring the length of time the hydrogen gas pressure is less than the minimum threshold parameter and finally, generating a signal if said length of time exceeds a second parameter.
- a system for generating hydrogen gas having at least one electrochemical cell.
- a hydrogen management system coupled fluidly coupled to the electrochemical cell.
- a pressure sensor coupled to said hydrogen management system and a control panel electrically coupled to said pressure sensor.
- FIG. 1 is a schematic diagram of a partial prior art electrochemical cell showing an electrochemical reaction
- FIG. 2 is an illustration in a perspective view of an exemplary embodiment of a hydrogen generation system
- FIG. 3 is an illustration of a piping and instrumentation diagram of the hydrogen generation system of FIG. 2 ;
- FIG. 4 is a perspective view illustration of the water management system of FIG. 2 ;
- FIG. 5 is a perspective view illustration of a oxygen-water phase separator and water management manifold of FIG. 2 ;
- FIG. 6 is a plan view illustration of a water deionizing filter and water restrictor of FIG. 2 ;
- FIG. 7 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to excessive LEL levels
- FIG. 8 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to high water temperature
- FIG. 9 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to high or low electrochemical cell voltage
- FIG. 10 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to a power supply failure
- FIG. 11 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to low inlet ionized water flow.
- FIG. 12 is a state transition diagram illustrating an exemplary embodiment for control methodology in low system output pressure conditions.
- Hydrogen gas is a versatile material having many uses in industrial and energy application ranging from the production of ammonia, and cooling of electrical generators to the powering of vehicles being propelled into space. While being the most abundant element in the universe, hydrogen gas is not readily available, and must be extracted from other material. Typically, large production facilities which reform methane through a steam reduction process are used to create large quantities of hydrogen gas which is then stored in containers or tanks and shipped to a customer for use in their application.
- Electrochemical cells 14 typically include one or more individual cells arranged in a stack, with the working fluids directed through the cells within the stack structure.
- the cells within the stack are sequentially arranged, each including a cathode, proton exchange membrane, and an anode (hereinafter “membrane electrode assembly”, or “MEA” 119 ) as shown in FIG. 1 .
- Each cell typically further comprises a first flow field in fluid communication with the cathode and a second flow field in fluid communication with the anode.
- the MEA 119 may be supported on either or both sides by screen packs or bipolar plates disposed within the flow fields, and which may be configured to facilitate membrane hydration and/or fluid movement to and from the MEA 119 .
- Membrane 118 comprises electrolytes that are preferably solids or gels under the operating conditions of the electrochemical cell.
- Useful materials include, for example, proton conducting ionomers and ion exchange resins.
- Useful proton conducting ionomers include complexes comprising an alkali metal salt, alkali earth metal salt, a protonic acid, a protonic acid salt or mixtures comprising one or more of the foregoing complexes.
- Counter-ions useful in the above salts include halogen ion, perchloric ion, thiocyanate ion, trifluoromethane sulfonic opn, borofuoric ion, and the like.
- Such salts include, but are not limited to, lithium fluoride, sodium iodide, lithium iodide, lithium perchlorate, sodium thiocyanate, lithium trifluoromethane sulfonate, lithium borofluoride, lithium hexafluorophosphate, phosphoric acid, sulfuric acid, trifluoromethane sulfonic acid, and the like.
- the alkali metal salt,. alkali earth metal salt, protonic acid, or protonic acid salt can be complexed with one or more polar polymers such as a polyether, polyester, or polyimide, or with a network or cross-linked polymer containing the above polar polymer as a segment.
- Useful polyethers include polyoxyalkylenes, such as polyethylene glycol, polyethylene glycol monoether, and polyethylene glycol diether; copolymers of at least one of these polyethers, such as poly(oxyethylene-co-oxypropylene)glycol, poly(oxyethylene-co-oxypropylene)glycol monoether, and poly(oxyethylene-co-oxypropylene)glycol diether; condensation products of ethylenediamine with the above polyoxyalkylenesl; and esters, such as phosphoric acid esters, aliphatic carboxylic acid esters or aromatic carboxylic acid esters of the above polyoxyalkylenes.
- Copolymers of, e.g., polyethylene glycol monoethyl ether with methacrylic acid exhibit sufficient ionic conductivity to be useful.
- Ion-exchange resins useful as proton conducting materials include hydrocarbon and fluorocarbon-type resins.
- Hydrocarbon-type ion-exchange resins include phenolic resins, condensation resins such as phenol-formaldehyde, polystyrene, styrene-divinyl benzene copolymers, styrene-butadiene copolymers, styrene, styrene-divinylbenzene-vinylchloride terpolymers, and the like, that can be imbued with cation-exchange ability by sulfonation, or can be imbued with anion-exchange ability by chloromethylation followed by conversion to the corresponding quatemary-amine.
- Fluorocarbon-type ion-exchange resins can include, for example, hydrates of tetrafluoroethylene-perfluorosulfonyl ethoxyvinyl ether or tetrafluoroethylene-hydroxylated (perfluorovinylether) copolymers and the like.
- fluorocarbon-type resins having sulfonic, carboxylic and/or phosophoric acid functionality are preferred.
- Fluorocarbon-type resins typically exhibit excellent resistance to oxidation by halogen, strong acids, and bases.
- One family of fluorocarbon-type resins having sulfonic acid group functionality is NAFIONTMresins (commercially available from E.I. du Pont de Nemours and Company, Wilmington, Del.).
- Electrodes 114 and 116 comprise catalyst suitable for performing the needed electrochemical reaction (i.e. electrolyzing water to produce hydrogen and oxygen). Suitable electrodes comprise, but are not limited to, platinum, palladium, rhodium, carbon, gold, tantalum, tungsten, ruthenium, iridium, osmium, and the like, as well as alloys and combinations comprising one or more of the foregoing materials. Electrodes 114 and 116 can be formed on membrane 118 , or may be layered adjacent to, but in contact with or in ionic communication with, membrane 118 .
- Flow field members (not shown) and support membrane 118 allow the passage of system fluids, and preferably are electrically conductive, and may be, for example, screen packs or bipolar plates.
- the screen packs include one or more layers of perforated sheets or a woven mesh formed from metal or strands. These screens typically comprise metals, for example, niobium, zirconium, tantalum, titanium, carbon steel, stainless steel, nickel, cobalt and the like, as well as alloys and combinations comprising one or more of the foregoing metals.
- Bipolar plates are commonly porous structures comprising fibrous carbon, or fibrous carbon impregnated with polytetrafluoroethylene or PTFE (commercially available under the trade name TEFLON® from E.I. du Pont de Nemours and Company).
- WOMS water oxygen management system 16
- the WOMS 16 maintains all of the water fluid functions within the electrochemical system 12 , including separating the oxygen gas from the water, manifolding of water lines, monitoring of water quality, deionizing of the water, all of which will be described in more detail herein.
- the hydrogen gas exits the electrochemical cells 14 along with a small amount of water which is carried over with the hydrogen protons during the process of electrolyzing the water.
- This hydrogen-water mixture is directed into a hydrogen gas management system 18 (hereinafter referred to as “HGMS”) for further processing.
- HGMS 18 separates the water from the hydrogen gas and processes the gas using optional drying apparatus to further minimize water contamination.
- the hydrogen gas exits the system 12 through a port 20 for use in the end application.
- the electrochemical system 12 includes further subsystems, such as a ventilation system 22 , power supply modules 24 , control panels 26 , a user input panel 28 and combustible gas sensor calibration system 30 . If should be noted that the cabinet 32 of electrochemical system 12 is divided by a partition 34 which separates the electrical compartment 36 from the gas generation compartment 38 to prevent any inadvertent exposure of hydrogen gas to electrical sources.
- the WOMS 16 is best seen in FIG. 4 6 .
- Deionized water is fed from an external source to the phase separator and water manifold 40 via a water inlet conduit 42 .
- An optional filter 44 may be coupled to the water inlet conduit 42 to provide additional protection against contaminants from entering the system 12 .
- water enters via conduit 42 filling the phase separator body 46 until the desired water level is detected by sensor 48 causing the solenoid valve 50 to close.
- the solenoid valve 50 opens to provide additional water to the system.
- the phase separator and water manifold 40 is mounted to the cabinet by bracket 43 .
- water is discharged from the phase separator body 46 through conduit 52 to pump 54 .
- An optional heat exchanger 56 may be used to reduce the temperature of the water.
- the water enters the manifold 58 via conduit 60 .
- a plurality of outlets 62 and 64 provide water to the electrochemical cells 14 and the guard bed 66 .
- Outlets 62 feed water via conduits 68 past flow switches 133 to the electrochemical cells 14 .
- Flow switches 133 are electrically connected to the control circuits of power supply 24 . In the event that flow is interrupted in conduit 68 , the flow switch will send a signal to the power supply 24 which causes the electrical power to be disconnected to the electrochemical cell 14 which the interrupted conduit was providing water.
- Manifold 58 also includes a conductivity sensor 70 which measures the quality of the water in the system 12 .
- the sensor 70 is typically a water conductivity and temperature sensor (commercially available as Model RC-20/PS102J2 manufactured by Pathfinder Instruments). Since these types of sensor require the water to be flowing in order to maintain accurate measurements, the placement of the sensor 70 is important.
- the sensor 70 By placing the sensor 70 at the end of the manifold 58 adjacent to the outlet to guard bed 66 , two functions may be accomplished by sensor 70 . First, the sensor 70 will measure the quality of the water. Once the water quality falls below a predetermined threshold, typically 1 to 5 microSiemens/cm, the system 12 will be shut down to prevent contaminants from damaging the electrochemical cells 14 . Additionally, since the sensor 70 requires flowing water for accurate measurements, if the guard bed, or any of the conduits or valves attached thereto become plugged, the water will stop flowing and the conductivity sensor 70 will also read an erroneously high conductivity, which will indicate to the system 12 that there is a problem and the process should be shut down.
- a predetermined threshold typically 1 to 5 microSiemens/cm
- the guard bed 66 includes a manifold 73 which receives the water from conduit 72 and forces the water through a screen 74 which filter any particulate matter from entering the main body 75 of the guard bed 66 .
- the water exits the guard bed 66 through the manifold 73 via a volume restrictor 76 .
- the restrictor 76 (commercially available under Model 58.6271.1 manufactured by Neoperl, Inc.) limits the amount volume that can pass through the guard bed 66 over a wide range of pressures.
- the restrictor 76 can be appropriately sized to maintain a water volume flowing through the guard bed 66 at a level that maintains adequate water flow to the electrochemical cells 14 . Water returns from the guard bed 66 to the inlet 79 in return manifold 78 via conduit 77 .
- the oxygen-water mixture returns to the phase separator 40 via conduits 80 .
- Return manifold 78 receives the conduct 80 through inlets 82 .
- the oxygen-water mixture travels along the return manifold 78 which empties into the phase separator body 46 .
- the liberated gas exits the separator body 46 via conduit 84 and exhausts into the cabinet 32 through outlet 86 .
- a combustible gas sensor 88 monitors the gas exiting the outlet 86 to warn if any combustible gases exceed predetermined levels.
- the separated water in the body 46 is then reused within the system 12 as described herein above.
- the hydrogen gas, mixed with water is processed by the HGMS 18 .
- the HGMS 18 receives the water via manifold 90 .
- a hydrogen water phase separator 92 causes nearly all the hydrogen gas to be separated from the liquid water.
- the hydrogen gas exits the separator 92 via conduit 94 while the water collects in the bottom of the separator 92 .
- a back pressure regulator 154 described herein assures a minimum hydrogen gas pressure for delivery of product hydrogen gas and for return of water from the phase separator 92 . By virtue of the pressurization a small amount of hydrogen gas is dissolved in the water.
- the water with dissolved hydrogen exits and is depressurized via valves 152 and the resultant mixture then flows via conduit 96 which returns to the oxygen-water phase separator 46 .
- the water with dissolved hydrogen exits and is depressurized via valves 152 and conduit 96 and enters a hydrogen-water phase separator 150 .
- the resultant hydrogen gas is vented into the cabinet 38 and the water returns to the oxygen-water phase separator 46 via conduit 151 .
- the hydrogen gas travels via conduit 94 to a dryer 98 , 99 which further dries the gas to a desired level, typically to less than 10 parts per million by volume at standard temperature and pressure.
- the dryers 98 , 99 are connected by a manifold 120 which alternates the hydrogen gas between the two dryers 98 , 99 on a predetermined time interval.
- These dryers which are typically referred to as pressure swing or swing-bed type dryers contain a dessicant which dries the hydrogen gas to a desired level.
- the system 12 will switch the gas flow from one dryer 98 to the other dryer 99 .
- the amount of time the gas will flow through an individual dryer 98 , 99 will depend on how quickly the desiccant in the dryer 98 , 99 becomes saturated with water. Prior to this saturation point, the gas flow and switched and the system 12 will regenerate the saturated dryer 98 , 99 with a small slip stream of depressurized dry gas processed by the alternate dryer.
- the pressure of the hydrogen gas is measured by pressure sensor 155 .
- the pressure sensor 155 provides a feedback to the control panel 28 for determining the appropriate amount of electrical power to provide to the electrochemical cells 14 .
- the amount of electrical power provided by the control panel 28 determines the production rate of the electrochemical cells which in turn affects the output pressure of the hydrogen gas.
- the system 12 By controlling the pressure measured at pressure sensor 155 slightly above the set pressure of pressure regulator 154 , the system 12 is able to maintain an output hydrogen gas pressure to the end user within ⁇ 0.5 bar without the use of a hydrogen buffer tank which was required hereto before.
- the control panel 28 operates to control the pressure at pressure sensor 155 at a point 0.1 to 3 barg greater than the pressure regulator 154 set point.
- the hydrogen gas exits the system 12 via outlet 20 for use by the end-user.
- the system 12 also includes a ventilation system 22 which provides fresh air to the interior of the gas generation compartment 38 .
- a fan 124 adjacent to a louvered grill 122 draws in external air. The air travels down the duct 126 and enters the interior portion of the gas generation compartment 38 adjacent the electrochemical cells 14 . To exit the compartment 38 , the air must traverse the length of the compartment 38 and exit through louvered grill 128 . Due to the flow of air, the oxygen exhausted by the oxygen-water phase separator vent 86 is quickly removed from the system 12 . Any hydrogen which escapes, such as hydrogen vented from the phase separator 150 , is exhausted into the flow of air, diluted and quickly removed from system 12 .
- Sensor 160 detects a loss of air ventilation and automatically causes the system 12 to shut down, stopping the production of oxygen and hydrogen. Additionally, a combustible gas sensor 130 is positioned adjacent to the exit grill 128 . In the event that combustible gas levels in the vent air stream reach unacceptable levels, the system 12 is automatically shut down for maintenance or repair.
- Combustible gas sensors such as sensors 130 and 88 , typically use a technology referred to as a “catalytic bead” type sensor (commercially available under the trade name Model FP-524C by Detcon, Inc.). These sensors monitor the percentage of lower flammable limit (“LFL”) of combustible gas in a product gas stream.
- LFL lower flammable limit
- This LFL measurement represents the percentage of a combustible gas, such as hydrogen, propane, natural gas, in a given volume of air (e.g. the LFL for hydrogen in air is 4% by volume).
- These sensors 88 , 130 require periodic calibration to ensure adequate performance. Calibration procedures typically require a user to use a bottle of premixed calibration gas which is manufactured with a predetermined mixture of hydrogen and air.
- the mixture is usually 25-50% of the lower flammable limit of the combustible gas.
- the system 12 is configured to either automatically calibrate the sensors on a periodic basis, or to facilitate manual calibration by eliminating the need for the user to access the gas generation compartment.
- the auto-calibration system 30 of the preferred embodiment includes a bottle of premixed calibration gas 132 , a solenoid valve block 134 , an external port 136 and conduits 138 , 140 , 142 , 143 .
- the combustible gas calibration system 30 is triggered either when activated by the user via the interface panel 28 or at a predetermined interval by the control panel 26 . If the activation is triggered by the interface panel, the user is given the choice of either manually connecting an external calibration bottle to port 136 or use the internal calibration gas 132 . If the user selects to use the external bottle, they are instructed by the interface panel 28 to connect the bottle. If the user selects to use the internal calibration gas, the control panel 26 opens a solenoid valve 144 in the valve block 134 to allow the combustible gas mixture into conduits 138 , 140 . Orifices 145 , 146 in conduits 138 and 140 respectively are sized to allow the appropriate amount of gas into the conduit.
- the gas travels along the conduits 138 , 140 to the combustible gas sensors 88 , 130 .
- the control panel 26 monitors the levels of combustible gas measured by the sensors 88 , 130 . If the level measured is not equal to the level present in the premixed calibration gas, the control panel adjusts the combustible gas sensors 88 , 130 until the appropriate levels are reached.
- the sequence operates essentially the same as described above. If the calibration settings of out of adjustment by a predetermined amount, the control panel may optionally signal a warning to advise the user and/or shorten the time period between calibrations.
- the system 12 contains a number of health monitoring processes which allow for corrective actions to automatically adjust the operation of the system 12 .
- a number of the components, such as the electrochemical cell 14 or the power supplies are modular. This modularity provides additional benefits in the event that a fatal error occurs in one module.
- the system 12 is enabled to adjust the operation of the system to accommodate the error and perform in a degraded mode until repairs or maintenance can be performed. This allows the end-user to continue operation without a major impact on their processes.
- control panel 26 and the power supplies 24 may include, but not be limited to, a processor(s), computer(s), memory, storage, register(s), timing, interrupt(s), communication interface(s), and input/output signal interfaces, and the like, as well as combinations comprising at least one of the foregoing.
- control panel 26 may include input signal processing and filtering to enable accurate sampling and conversion or acquisitions of such signals from communications interfaces. Additional features of control panel 26 and certain processes, functions, and operations therein are thoroughly discussed at a later point herein.
- control panel 26 may also include power distribution components, such as but not limited to, circuit breakers, relays, contactors, fuses, dc-dc power conditioners, and the like, as well as combinations comprising at least one of the foregoing. These power distribution components allow power to be provided to components, such as pumps, fans and solenoid valves, within the system 12 . During normal mode, current is varied to the electrochemical cells 14 to provide the appropriate product level of hydrogen gas required by the user.
- a state transition diagram depicting an exemplary method of control process 200 for the system 12 is provided.
- the process 200 includes numerous modes and the criterion, requirements, events and the like to control changes of state among the various modes.
- the process 200 typically operates in normal mode 210 monitoring and evaluating various sensors and states to ascertain the status of the system 12 . Such monitoring may include the evaluation of combustible gas levels in the vent stream from sensors 88 , 130 . If the percentage of the lower flammability limit (hereinafter referred to as “LFL”) trends upwards over time and the level of LFL remains below a threshold, the process 200 transfers to a log mode 212 which records the LFL data and sends a warning to the user interface 28 .
- LFL percentage of the lower flammability limit
- the process 200 transfers to diagnostic mode 214 to evaluate the electrochemical cells 14 .
- the diagnostic mode 214 operates each electrochemical cell 14 individually while monitoring the LFL measurements from sensor 88 , 130 . If the LFL measurements is greater than a shutdown level, or if the LFL measurements do not drop, or if there is only one electrochemical cell 14 is operating then the process 200 transfers to shutdown mode 216 to stop the processes of system 12 in an orderly manner.
- Process 200 uses alert mode 218 to notify the user.
- the process 200 transfers to degraded mode 220 .
- the degraded mode 220 turns off the appropriate modules in the power supply 24 to remove electrical power from the faulty electrochemical cell 14 from operation.
- Log mode 212 records the appropriate data and alerts the user. Once the system 12 has been shut down and properly services, process 200 is reset to a normal mode 210 .
- Another error state which may be encountered by the system 12 is excessive water temperature in the manifold 58 . Temperature measurements from the sensor 70 are acquired, monitored and analyzed by process 200 while in the normal operating mode 210 . If normal mode 210 detects that the temperature is trending upwards and the actual water temperature is less than a predetermined threshold, the process 200 transfers to log mode 212 where the information is recorded and sends warning to the user.
- the process 200 transfers to degraded mode 222 .
- degraded mode 222 the electrical current output of power supplies 24 is reduced to lower the hydrogen gas output of the electrochemical cells 14 .
- the process 200 transfers to log mode 212 to log the temperature information and warn the user of the degraded performance of the system 12 .
- process 200 is reset to a normal mode 210 . If the temperature measured by sensor 70 remains above a second predetermined threshold, typically equal to the maximum operating temperature of the guard bed 66 , the process 200 transfers to shut down mode 216 to stop the processes of system 12 in an orderly manner.
- Process 200 uses alert mode 218 to notify the user.
- Another error condition which may be experienced by the system 12 is a low voltage or high voltage condition in the electrochemical cells 14 .
- normal mode 210 detects an upward or downward trend in the voltage
- the process 200 transfers to log mode 212 which records the information and sends a warning to the user.
- the process 200 transfers to diagnostic mode 228 to determine which electrochemical cell is operating outside of normal parameters. If there is only one electrochemical cell 14 operating, process 200 transfers to shutdown mode 216 to stop the processes of system 12 in an orderly manner.
- Process 200 uses alert mode 218 to notify the user.
- process 200 transfers to degraded mode 226 which disables the power supplies which provide electrical power to the faulty electrochemical cell and continues to operate the system 12 with the remaining electrochemical cells.
- Degraded mode 226 FIG. 9
- log mode 212 records the information and sends a warning to the user.
- process 200 is reset to a normal mode 210 . If the voltages once again rise above the predetermined thresholds, or fall below a predetermined threshold, the process 200 once again transfers to diagnostic mode 228 and repeats the sequence describe above once again. This process continues until the system 12 is repaired or reset, or until the last electrochemical cell is determined to be faulty.
- another error which the system 12 may encounter is a faulty power supply module in the power supply 24 .
- the process 200 transfers to diagnostic mode 230 .
- the diagnostic mode 230 interrogates each of the modules in the power supply 24 to determine which of the individual modules are faulty. Once the diagnostic mode 230 determines which module is faulty, the process 200 transfers to degraded mode 232 which disables the faulty power supply modules and continues operation. It should be appreciated that if multiple power supply modules are required to operate a single electrochemical cell 14 , then degraded mode 232 will disable all the power supply modules associated with the faulty module.
- the process 200 also transfers to log mode 212 to record the appropriate power supply information and send a warning to the user.
- the process 200 then continues the operation of the system 12 in degraded mode. Once the system 12 has been shut down and properly services, process 200 is reset to a normal mode 210 . If another power supply should fail, the sequence of modes repeats when the process 200 transfers back to diagnostic mode 230 . In the event that there are not enough power supply modules remaining to operate a single electrochemical cell 14 , then the process 200 transfers to shutdown mode 216 to stop the processes of system 12 in an orderly manner. Process 200 uses alert mode 218 to notify the user.
- Another type of error that may be encountered by the system 12 is a low inlet ionized water flow.
- a steady supply of fresh deionized water is typically required. If the flow of deionized water should be reduced or stop due to a problem with the external supply of water 17 then the system may be damaged if there is not enough deionized water to supply the electrochemical cells 14 .
- Water flow from deionizer 17 is determined by measure the amount of time is required to change the level of water measured by sensor 48 in the oxygen-water phase separator 46 . As shown in FIG.
- the process 200 transfers to diagnostic mode 234 which determines what hydrogen gas production rate can be achieved with the available deionized water inlet flow.
- the process 200 then transfers to degraded mode 236 which reduces the current produced by the power supplies 24 to reduce the hydrogen production rate of the electrochemical cells 14 .
- Degraded mode 236 continues to monitor and analyze the deionized water inlet flow in the manner described above. Once the system 12 has been shut down and properly services, or if the flow of deionized water flow returns to a normal operating state, the process 200 is reset to a normal mode 210 . If the water flow continues to trend downward, the process 200 transfers to log mode 212 records the information and sends a warning to the user.
- the process 200 transfers back to the diagnostic mode 234 and the sequence repeats as described above until the inlet flow falls beneath a minimum operating level. Once the minimum operating level is achieved, the process 200 transfers to shutdown mode 216 to stop the processes of system 12 in an orderly manner. Process 200 uses alert mode 218 to notify the user.
- the last example of an error that may be encountered by the system 12 is low gas output pressure.
- a drop in output pressure may indicate a fault condition requiring maintenance or operator intervention to prevent damage.
- Output pressure of the system 12 is measured by pressure sensor 155 which transmits a signal indicative of the gas pressure to the control panel 28 .
- the control panel 28 monitors the actual gas pressure signal and compares the signal to a parameter indicative of a minimum threshold pressure. If the actual gas pressure drops below a minimum threshold pressure, the process 200 transfers to diagnostic mode 238 which monitors 240 the actual output pressure for a predetermined amount of time. If the actual pressure stays below the minimum threshold pressure, process 200 optionally enters log mode 212 and records the information and sends a warning to the user.
- process 200 is reset and transfers back to normal operating mode 210 . However, if actual gas pressure measured by pressure sensor 155 remains below the minimum threshold pressure for the predetermined amount of time, process 200 transfers back to shut down mode 16 via diagnostic mode 238 to stop the processes of system 12 in an orderly manner. Process 200 uses alert mode 218 to notify the user.
- the minimum threshold pressure is lower than the operating pressure required by the operator, and more preferably at least 10% lower than the operating pressure. In the exemplary embodiment, the operating pressure is 200 psi, and the minimum threshold pressure is 180 psi. It should be appreciated that the actual values may be set to any that are necessary or desired by the operator for a given application.
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Abstract
Description
- The present application is a Continuation-In-Part application and claims priority to patent application Ser. No. 11/004,185 filed on Dec. 3, 2004 which is incorporated herein by Reference.
- The present disclosure relates to an electrochemical cell system and especially relates to a system for stopping the generation of hydrogen in the event of a fault condition.
- Electrochemical cells are energy conversion devices, usually classified as either electrolysis cells or fuel cells. An electrolysis cell functions as a hydrogen generator by electrolytically decomposing water to produce hydrogen and oxygen gases, and functions as a fuel cell by electrochemically reacting hydrogen with oxygen to generate electricity. Referring to
FIG. 1 , a partial section of a typical proton exchange membrane electrolysis cells is detailed. In a typical anode feed water electrolysis cell (not shown), process water is fed into a cell on the side of the oxygen electrode (in an electrolytic cell, the anode) to form oxygen gas, electrons, and protons. The electrolytic reaction is facilitated by the positive terminal of a power source electrically connected to the anode and the negative terminal of the power source connected to a hydrogen electrode (in an electrolytic cell, the cathode). - The oxygen gas and a portion of the process water exit the cell, while protons and water migrate across the proton exchange membrane to the cathode where hydrogen gas is formed. In a cathode feed electrolysis cell (not shown), process water is fed on the hydrogen electrode, and a portion of the water migrates from the cathode across the membrane to the anode where protons and oxygen gas are formed. A portion of the process water exits the cell at the cathode side without passing through the membrane. The protons migrate across the membrane to the cathode where hydrogen gas is formed. The typical electrochemical cell system includes a number of individual cells arranged in a stack, with the working fluid directed through the cells via input and output conduits formed within the stack structure. The cells within the stack are sequentially arranged, each including a cathode, a proton exchange membrane, and an anode.
- In certain conventional arrangements, the anode, cathode, or both are gas diffusion electrodes that facilitate gas diffusion to the membrane. Each cathode/membrane/anode assembly (hereinafter “membrane electrode assembly”, or “MEA”) is typically supported on both sides by flow fields comprising screen packs or bipolar plates. Such flow fields facilitate fluid movement and membrane hydration and provide mechanical support for the MEA. Since a differential pressure often exists in the cells, compression pads or other compression means are often employed to maintain uniform compression in the cell active area, i.e., the electrodes, thereby maintaining intimate contact between flow fields and cell electrodes over long time periods. Pumps are used to move the reactants and products to and from the electrochemical cell, which is connected to the liquid and gas storage devices by a system of pipes. This use of external pumps and storage areas both limits the ease with which electrochemical cells may be transported, and complicates the use of electrochemical cells in locations where pumps and storage tanks are difficult to introduce or operate. While existing electrochemical cell systems are suitable for their intended purposes, there still remains a need for improvements, particularly regarding operation of electrochemical cell systems with multiple electrochemical cell stacks and their operation.
- A method of generating hydrogen gas including the steps of disassociating hydrogen from a reactant to form hydrogen gas. Monitoring a pressure of the hydrogen gas and comparing the pressure of the hydrogen gas to a threshold parameter. Finally generating a signal in response to the pressure being less than the threshold parameter.
- A method of generating hydrogen gas including the steps of electrochemically separating hydrogen from water. Forming hydrogen gas and monitoring the pressure of the hydrogen gas. Comparing the hydrogen gas pressure to a minimum threshold parameter. Measuring the length of time the hydrogen gas pressure is less than the minimum threshold parameter and finally, generating a signal if said length of time exceeds a second parameter.
- A system for generating hydrogen gas having at least one electrochemical cell. A hydrogen management system coupled fluidly coupled to the electrochemical cell. A pressure sensor coupled to said hydrogen management system and a control panel electrically coupled to said pressure sensor.
- Referring now to the drawings, which are meant to be exemplary and not limiting, and wherein like elements are numbered alike:
-
FIG. 1 is a schematic diagram of a partial prior art electrochemical cell showing an electrochemical reaction; -
FIG. 2 is an illustration in a perspective view of an exemplary embodiment of a hydrogen generation system; -
FIG. 3 is an illustration of a piping and instrumentation diagram of the hydrogen generation system ofFIG. 2 ; -
FIG. 4 is a perspective view illustration of the water management system ofFIG. 2 ; -
FIG. 5 is a perspective view illustration of a oxygen-water phase separator and water management manifold ofFIG. 2 ; -
FIG. 6 is a plan view illustration of a water deionizing filter and water restrictor ofFIG. 2 ; -
FIG. 7 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to excessive LEL levels; -
FIG. 8 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to high water temperature; -
FIG. 9 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to high or low electrochemical cell voltage; -
FIG. 10 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to a power supply failure; -
FIG. 11 is a state transition diagram illustrating an exemplary embodiment for control methodology in degraded modes of operation due to low inlet ionized water flow. -
FIG. 12 is a state transition diagram illustrating an exemplary embodiment for control methodology in low system output pressure conditions. - Hydrogen gas is a versatile material having many uses in industrial and energy application ranging from the production of ammonia, and cooling of electrical generators to the powering of vehicles being propelled into space. While being the most abundant element in the universe, hydrogen gas is not readily available, and must be extracted from other material. Typically, large production facilities which reform methane through a steam reduction process are used to create large quantities of hydrogen gas which is then stored in containers or tanks and shipped to a customer for use in their application.
- Increasing, due to logistics and security concerns, it has become more desirable to produce the hydrogen closer to the end point of use. The most desirable method of production allows the user to produce the hydrogen as it is needed at the point of use. To achieve this, hydrogen generators typical disassociate hydrogen from a reactant fuel source such as water, natural gas, propane, or methane. In the exemplary embodiment, water electrolysis is used to produce the hydrogen gas as it is needed. Referring to
FIG. 1 andFIG. 2 , andelectrochemical system 12 of the present invention is shown.Electrochemical cells 14 typically include one or more individual cells arranged in a stack, with the working fluids directed through the cells within the stack structure. The cells within the stack are sequentially arranged, each including a cathode, proton exchange membrane, and an anode (hereinafter “membrane electrode assembly”, or “MEA” 119) as shown inFIG. 1 . Each cell typically further comprises a first flow field in fluid communication with the cathode and a second flow field in fluid communication with the anode. The MEA 119 may be supported on either or both sides by screen packs or bipolar plates disposed within the flow fields, and which may be configured to facilitate membrane hydration and/or fluid movement to and from theMEA 119. -
Membrane 118 comprises electrolytes that are preferably solids or gels under the operating conditions of the electrochemical cell. Useful materials include, for example, proton conducting ionomers and ion exchange resins. Useful proton conducting ionomers include complexes comprising an alkali metal salt, alkali earth metal salt, a protonic acid, a protonic acid salt or mixtures comprising one or more of the foregoing complexes. Counter-ions useful in the above salts include halogen ion, perchloric ion, thiocyanate ion, trifluoromethane sulfonic opn, borofuoric ion, and the like. Representative examples of such salts include, but are not limited to, lithium fluoride, sodium iodide, lithium iodide, lithium perchlorate, sodium thiocyanate, lithium trifluoromethane sulfonate, lithium borofluoride, lithium hexafluorophosphate, phosphoric acid, sulfuric acid, trifluoromethane sulfonic acid, and the like. The alkali metal salt,. alkali earth metal salt, protonic acid, or protonic acid salt can be complexed with one or more polar polymers such as a polyether, polyester, or polyimide, or with a network or cross-linked polymer containing the above polar polymer as a segment. Useful polyethers include polyoxyalkylenes, such as polyethylene glycol, polyethylene glycol monoether, and polyethylene glycol diether; copolymers of at least one of these polyethers, such as poly(oxyethylene-co-oxypropylene)glycol, poly(oxyethylene-co-oxypropylene)glycol monoether, and poly(oxyethylene-co-oxypropylene)glycol diether; condensation products of ethylenediamine with the above polyoxyalkylenesl; and esters, such as phosphoric acid esters, aliphatic carboxylic acid esters or aromatic carboxylic acid esters of the above polyoxyalkylenes. Copolymers of, e.g., polyethylene glycol monoethyl ether with methacrylic acid exhibit sufficient ionic conductivity to be useful. - Ion-exchange resins useful as proton conducting materials include hydrocarbon and fluorocarbon-type resins. Hydrocarbon-type ion-exchange resins include phenolic resins, condensation resins such as phenol-formaldehyde, polystyrene, styrene-divinyl benzene copolymers, styrene-butadiene copolymers, styrene, styrene-divinylbenzene-vinylchloride terpolymers, and the like, that can be imbued with cation-exchange ability by sulfonation, or can be imbued with anion-exchange ability by chloromethylation followed by conversion to the corresponding quatemary-amine.
- Fluorocarbon-type ion-exchange resins can include, for example, hydrates of tetrafluoroethylene-perfluorosulfonyl ethoxyvinyl ether or tetrafluoroethylene-hydroxylated (perfluorovinylether) copolymers and the like. When oxidation and or acid resist is desirable, for instance, at the cathode of a fuel cell, fluorocarbon-type resins having sulfonic, carboxylic and/or phosophoric acid functionality are preferred. Fluorocarbon-type resins typically exhibit excellent resistance to oxidation by halogen, strong acids, and bases. One family of fluorocarbon-type resins having sulfonic acid group functionality is NAFION™resins (commercially available from E.I. du Pont de Nemours and Company, Wilmington, Del.).
-
Electrodes 114 and 116 comprise catalyst suitable for performing the needed electrochemical reaction (i.e. electrolyzing water to produce hydrogen and oxygen). Suitable electrodes comprise, but are not limited to, platinum, palladium, rhodium, carbon, gold, tantalum, tungsten, ruthenium, iridium, osmium, and the like, as well as alloys and combinations comprising one or more of the foregoing materials.Electrodes 114 and 116 can be formed onmembrane 118, or may be layered adjacent to, but in contact with or in ionic communication with,membrane 118. - Flow field members (not shown) and
support membrane 118, allow the passage of system fluids, and preferably are electrically conductive, and may be, for example, screen packs or bipolar plates. The screen packs include one or more layers of perforated sheets or a woven mesh formed from metal or strands. These screens typically comprise metals, for example, niobium, zirconium, tantalum, titanium, carbon steel, stainless steel, nickel, cobalt and the like, as well as alloys and combinations comprising one or more of the foregoing metals. Bipolar plates are commonly porous structures comprising fibrous carbon, or fibrous carbon impregnated with polytetrafluoroethylene or PTFE (commercially available under the trade name TEFLON® from E.I. du Pont de Nemours and Company). - Referring now to
FIG. 2 andFIG. 3 , after the water is disassociated in theelectrochemical cells 14 into hydrogen and oxygen gas, the respective gases leave theelectrochemical cells 14 for further downstream processing. The oxygen, mixed with process water which was not decomposed, is directed into a water oxygen management system 16 (herein after referred to as “WOMS”). TheWOMS 16 maintains all of the water fluid functions within theelectrochemical system 12, including separating the oxygen gas from the water, manifolding of water lines, monitoring of water quality, deionizing of the water, all of which will be described in more detail herein. - The hydrogen gas exits the
electrochemical cells 14 along with a small amount of water which is carried over with the hydrogen protons during the process of electrolyzing the water. This hydrogen-water mixture is directed into a hydrogen gas management system 18 (hereinafter referred to as “HGMS”) for further processing. TheHGMS 18 separates the water from the hydrogen gas and processes the gas using optional drying apparatus to further minimize water contamination. Finally, the hydrogen gas exits thesystem 12 through aport 20 for use in the end application. - The
electrochemical system 12 includes further subsystems, such as aventilation system 22,power supply modules 24,control panels 26, auser input panel 28 and combustible gassensor calibration system 30. If should be noted that thecabinet 32 ofelectrochemical system 12 is divided by apartition 34 which separates theelectrical compartment 36 from thegas generation compartment 38 to prevent any inadvertent exposure of hydrogen gas to electrical sources. - The
WOMS 16 is best seen inFIG. 4 6. Deionized water is fed from an external source to the phase separator andwater manifold 40 via awater inlet conduit 42. An optional filter 44 may be coupled to thewater inlet conduit 42 to provide additional protection against contaminants from entering thesystem 12. Upon startup of thesystem 12, water enters viaconduit 42 filling thephase separator body 46 until the desired water level is detected bysensor 48 causing thesolenoid valve 50 to close. During operation, when thewater level sensor 48 detects the water level in the phase separator drop below a predetermined threshold, thesolenoid valve 50 opens to provide additional water to the system. The phase separator andwater manifold 40 is mounted to the cabinet bybracket 43. - Once the appropriate water level is achieved and the
system 12 is operating, water is discharged from thephase separator body 46 throughconduit 52 to pump 54. Anoptional heat exchanger 56 may be used to reduce the temperature of the water. After leaving thepump 54, the water enters the manifold 58 viaconduit 60. A plurality ofoutlets electrochemical cells 14 and theguard bed 66.Outlets 62 feed water viaconduits 68 past flow switches 133 to theelectrochemical cells 14. Flow switches 133 are electrically connected to the control circuits ofpower supply 24. In the event that flow is interrupted inconduit 68, the flow switch will send a signal to thepower supply 24 which causes the electrical power to be disconnected to theelectrochemical cell 14 which the interrupted conduit was providing water. Any additional water not directed to theelectrochemical cells 14 exits the manifold 58 viaoutlet 64 to be filtered byguard bed 66. As will be explained in more detail herein, theguard bed 66 includes a restrictor for preventing excess flow throughoutlet 64 which prevents theelectrochemical cells 14 from being starved of water which could adversely affect their performance and reduce their operating life.Manifold 58 also includes aconductivity sensor 70 which measures the quality of the water in thesystem 12. Thesensor 70 is typically a water conductivity and temperature sensor (commercially available as Model RC-20/PS102J2 manufactured by Pathfinder Instruments). Since these types of sensor require the water to be flowing in order to maintain accurate measurements, the placement of thesensor 70 is important. By placing thesensor 70 at the end of the manifold 58 adjacent to the outlet to guardbed 66, two functions may be accomplished bysensor 70. First, thesensor 70 will measure the quality of the water. Once the water quality falls below a predetermined threshold, typically 1 to 5 microSiemens/cm, thesystem 12 will be shut down to prevent contaminants from damaging theelectrochemical cells 14. Additionally, since thesensor 70 requires flowing water for accurate measurements, if the guard bed, or any of the conduits or valves attached thereto become plugged, the water will stop flowing and theconductivity sensor 70 will also read an erroneously high conductivity, which will indicate to thesystem 12 that there is a problem and the process should be shut down. - Once the water enters
outlet 64, it moves to theguard bed 66 viaconduit 72. Theguard bed 66 includes a manifold 73 which receives the water fromconduit 72 and forces the water through ascreen 74 which filter any particulate matter from entering themain body 75 of theguard bed 66. After being treated in thebody 75, the water exits theguard bed 66 through the manifold 73 via avolume restrictor 76. The restrictor 76 (commercially available under Model 58.6271.1 manufactured by Neoperl, Inc.) limits the amount volume that can pass through theguard bed 66 over a wide range of pressures. By knowing the output ofpump 54 and operating requirements ofelectrochemical cells 14, the restrictor 76 can be appropriately sized to maintain a water volume flowing through theguard bed 66 at a level that maintains adequate water flow to theelectrochemical cells 14. Water returns from theguard bed 66 to theinlet 79 inreturn manifold 78 viaconduit 77. - As described herein above, after the water is decomposed into hydrogen and oxygen gas by
electrochemical cells 14, the oxygen-water mixture returns to thephase separator 40 viaconduits 80.Return manifold 78 receives theconduct 80 throughinlets 82. The oxygen-water mixture travels along thereturn manifold 78 which empties into thephase separator body 46. As the mixture enters thebody 46, it impinges on the inner walls and surfaces, causing the water to separate under the influence of gravity and surface tension out of the gas and collect in the bottom of theseparator body 46. The liberated gas exits theseparator body 46 viaconduit 84 and exhausts into thecabinet 32 throughoutlet 86. Acombustible gas sensor 88 monitors the gas exiting theoutlet 86 to warn if any combustible gases exceed predetermined levels. The separated water in thebody 46 is then reused within thesystem 12 as described herein above. - Once the
electrochemical cells 14 decompose the water, the hydrogen gas, mixed with water is processed by theHGMS 18. As best seen inFIG. 3 , theHGMS 18 receives the water viamanifold 90. A hydrogenwater phase separator 92 causes nearly all the hydrogen gas to be separated from the liquid water. The hydrogen gas exits theseparator 92 via conduit 94 while the water collects in the bottom of theseparator 92. Aback pressure regulator 154 described herein assures a minimum hydrogen gas pressure for delivery of product hydrogen gas and for return of water from thephase separator 92. By virtue of the pressurization a small amount of hydrogen gas is dissolved in the water. In the preferred embodiment, the water with dissolved hydrogen exits and is depressurized via valves 152 and the resultant mixture then flows viaconduit 96 which returns to the oxygen-water phase separator 46. In an alternate embodiment, the water with dissolved hydrogen exits and is depressurized via valves 152 andconduit 96 and enters a hydrogen-water phase separator 150. In this alternate embodiment the resultant hydrogen gas is vented into thecabinet 38 and the water returns to the oxygen-water phase separator 46 viaconduit 151. The hydrogen gas travels via conduit 94 to a dryer 98,99 which further dries the gas to a desired level, typically to less than 10 parts per million by volume at standard temperature and pressure. The dryers 98,99 are connected by a manifold 120 which alternates the hydrogen gas between the two dryers 98,99 on a predetermined time interval. These dryers, which are typically referred to as pressure swing or swing-bed type dryers contain a dessicant which dries the hydrogen gas to a desired level. Periodically, thesystem 12 will switch the gas flow from one dryer 98 to the other dryer 99. The amount of time the gas will flow through an individual dryer 98, 99 will depend on how quickly the desiccant in the dryer 98, 99 becomes saturated with water. Prior to this saturation point, the gas flow and switched and thesystem 12 will regenerate the saturated dryer 98, 99 with a small slip stream of depressurized dry gas processed by the alternate dryer. After leaving the hydrogen gas driers 98, 99, the pressure of the hydrogen gas is measured bypressure sensor 155. Thepressure sensor 155 provides a feedback to thecontrol panel 28 for determining the appropriate amount of electrical power to provide to theelectrochemical cells 14. The amount of electrical power provided by thecontrol panel 28 determines the production rate of the electrochemical cells which in turn affects the output pressure of the hydrogen gas. By locating thepressure sensor 155 upstream from thepressure regulator 154, thecontrol panel 28 is able to compensate for pressure fluctuations that result due to the cycling of the gas driers 98,99,phase separator 92 drain cycles and changes in customer demand. By controlling the pressure measured atpressure sensor 155 slightly above the set pressure ofpressure regulator 154, thesystem 12 is able to maintain an output hydrogen gas pressure to the end user within ±0.5 bar without the use of a hydrogen buffer tank which was required hereto before. Typically, thecontrol panel 28 operates to control the pressure atpressure sensor 155 at a point 0.1 to 3 barg greater than thepressure regulator 154 set point. The hydrogen gas exits thesystem 12 viaoutlet 20 for use by the end-user. - As mentioned herein above, the
system 12 also includes aventilation system 22 which provides fresh air to the interior of thegas generation compartment 38. Afan 124 adjacent to alouvered grill 122 draws in external air. The air travels down the duct 126 and enters the interior portion of thegas generation compartment 38 adjacent theelectrochemical cells 14. To exit thecompartment 38, the air must traverse the length of thecompartment 38 and exit throughlouvered grill 128. Due to the flow of air, the oxygen exhausted by the oxygen-waterphase separator vent 86 is quickly removed from thesystem 12. Any hydrogen which escapes, such as hydrogen vented from thephase separator 150, is exhausted into the flow of air, diluted and quickly removed fromsystem 12.Sensor 160 detects a loss of air ventilation and automatically causes thesystem 12 to shut down, stopping the production of oxygen and hydrogen. Additionally, acombustible gas sensor 130 is positioned adjacent to theexit grill 128. In the event that combustible gas levels in the vent air stream reach unacceptable levels, thesystem 12 is automatically shut down for maintenance or repair. - Combustible gas sensors such as
sensors sensors system 12 is configured to either automatically calibrate the sensors on a periodic basis, or to facilitate manual calibration by eliminating the need for the user to access the gas generation compartment. The auto-calibration system 30 of the preferred embodiment includes a bottle of premixedcalibration gas 132, asolenoid valve block 134, anexternal port 136 andconduits - In operation, the combustible
gas calibration system 30 is triggered either when activated by the user via theinterface panel 28 or at a predetermined interval by thecontrol panel 26. If the activation is triggered by the interface panel, the user is given the choice of either manually connecting an external calibration bottle toport 136 or use theinternal calibration gas 132. If the user selects to use the external bottle, they are instructed by theinterface panel 28 to connect the bottle. If the user selects to use the internal calibration gas, thecontrol panel 26 opens asolenoid valve 144 in thevalve block 134 to allow the combustible gas mixture intoconduits Orifices conduits conduits combustible gas sensors control panel 26 monitors the levels of combustible gas measured by thesensors combustible gas sensors - If the calibration is triggered by the expiration of the predetermined time limit, the sequence operates essentially the same as described above. If the calibration settings of out of adjustment by a predetermined amount, the control panel may optionally signal a warning to advise the user and/or shorten the time period between calibrations.
- In the event that abnormal operating conditions or parameters such as the combustible gas sensor calibration are detected, the
system 12 contains a number of health monitoring processes which allow for corrective actions to automatically adjust the operation of thesystem 12. In the preferred embodiment of thesystem 12, a number of the components, such as theelectrochemical cell 14 or the power supplies are modular. This modularity provides additional benefits in the event that a fatal error occurs in one module. As will be described in more detail herein, when a fatal error occurs, thesystem 12 is enabled to adjust the operation of the system to accommodate the error and perform in a degraded mode until repairs or maintenance can be performed. This allows the end-user to continue operation without a major impact on their processes. - In order to perform the prescribed functions and desired processing, as well as the computations therefore (e.g. the control algorithms for hydrogen generation, and the like),
control panel 26 and the power supplies 24 may include, but not be limited to, a processor(s), computer(s), memory, storage, register(s), timing, interrupt(s), communication interface(s), and input/output signal interfaces, and the like, as well as combinations comprising at least one of the foregoing. For example,control panel 26 may include input signal processing and filtering to enable accurate sampling and conversion or acquisitions of such signals from communications interfaces. Additional features ofcontrol panel 26 and certain processes, functions, and operations therein are thoroughly discussed at a later point herein. - During a normal mode of operation, the power supplied from the power supplies 24 to the
control panel 26 and theelectrochemical cells 14 to produce hydrogen gas as described herein above. In addition to the processing functions previously discussed,control panel 26 may also include power distribution components, such as but not limited to, circuit breakers, relays, contactors, fuses, dc-dc power conditioners, and the like, as well as combinations comprising at least one of the foregoing. These power distribution components allow power to be provided to components, such as pumps, fans and solenoid valves, within thesystem 12. During normal mode, current is varied to theelectrochemical cells 14 to provide the appropriate product level of hydrogen gas required by the user. - Referring to
FIG. 7 , a state transition diagram depicting an exemplary method ofcontrol process 200 for thesystem 12 is provided. Theprocess 200 includes numerous modes and the criterion, requirements, events and the like to control changes of state among the various modes. Theprocess 200 typically operates innormal mode 210 monitoring and evaluating various sensors and states to ascertain the status of thesystem 12. Such monitoring may include the evaluation of combustible gas levels in the vent stream fromsensors process 200 transfers to alog mode 212 which records the LFL data and sends a warning to theuser interface 28. - Should the
process 200 detect that the LFL exceeds a predetermined threshold, which may indicate that repair or preventative action is needed, the process transfers todiagnostic mode 214 to evaluate theelectrochemical cells 14. To determine if the high LFL measurement is due to a faulty or wornelectrochemical cell 14, thediagnostic mode 214 operates eachelectrochemical cell 14 individually while monitoring the LFL measurements fromsensor electrochemical cell 14 is operating then theprocess 200 transfers toshutdown mode 216 to stop the processes ofsystem 12 in an orderly manner.Process 200 usesalert mode 218 to notify the user. - If the
diagnostic mode 214 determines whichelectrochemical cell 14 is responsible for the high LFL levels, then theprocess 200 transfers todegraded mode 220. Thedegraded mode 220 turns off the appropriate modules in thepower supply 24 to remove electrical power from the faultyelectrochemical cell 14 from operation.Log mode 212 records the appropriate data and alerts the user. Once thesystem 12 has been shut down and properly services,process 200 is reset to anormal mode 210. - Another error state which may be encountered by the
system 12 is excessive water temperature in themanifold 58. Temperature measurements from thesensor 70 are acquired, monitored and analyzed byprocess 200 while in thenormal operating mode 210. Ifnormal mode 210 detects that the temperature is trending upwards and the actual water temperature is less than a predetermined threshold, theprocess 200 transfers to logmode 212 where the information is recorded and sends warning to the user. - If the water temperature measured by
sensor 70 exceeds a predetermined threshold, theprocess 200 transfers todegraded mode 222. Indegraded mode 222, the electrical current output ofpower supplies 24 is reduced to lower the hydrogen gas output of theelectrochemical cells 14. Theprocess 200 transfers to logmode 212 to log the temperature information and warn the user of the degraded performance of thesystem 12. Once thesystem 12 has been shut down and properly services,process 200 is reset to anormal mode 210. If the temperature measured bysensor 70 remains above a second predetermined threshold, typically equal to the maximum operating temperature of theguard bed 66, theprocess 200 transfers to shut downmode 216 to stop the processes ofsystem 12 in an orderly manner.Process 200 usesalert mode 218 to notify the user. - Another error condition which may be experienced by the
system 12 is a low voltage or high voltage condition in theelectrochemical cells 14. Ifnormal mode 210 detects an upward or downward trend in the voltage, theprocess 200 transfers to logmode 212 which records the information and sends a warning to the user. If the voltage required to operate theelectrochemical cells 14 drops below a threshold, rises above a threshold and there is current being drawn by theelectrochemical cells 14, theprocess 200 transfers todiagnostic mode 228 to determine which electrochemical cell is operating outside of normal parameters. If there is only oneelectrochemical cell 14 operating,process 200 transfers toshutdown mode 216 to stop the processes ofsystem 12 in an orderly manner.Process 200 usesalert mode 218 to notify the user. - If there are more than two
electrochemical cells 14 available,process 200 transfers todegraded mode 226 which disables the power supplies which provide electrical power to the faulty electrochemical cell and continues to operate thesystem 12 with the remaining electrochemical cells. Degraded mode 226 (FIG. 9 ) continues to monitor and analyze the electrochemical cell voltages and similar to the operation described above if an upward or downward trend is detected, theprocess 200 transfers to logmode 212 records the information and sends a warning to the user. Once thesystem 12 has been shut down and properly services,process 200 is reset to anormal mode 210. If the voltages once again rise above the predetermined thresholds, or fall below a predetermined threshold, theprocess 200 once again transfers todiagnostic mode 228 and repeats the sequence describe above once again. This process continues until thesystem 12 is repaired or reset, or until the last electrochemical cell is determined to be faulty. - Referring to
FIG. 10 , another error which thesystem 12 may encounter is a faulty power supply module in thepower supply 24. If theprocess 200 while innormal mode 210 detects a power supply failure, theprocess 200 transfers todiagnostic mode 230. Thediagnostic mode 230 interrogates each of the modules in thepower supply 24 to determine which of the individual modules are faulty. Once thediagnostic mode 230 determines which module is faulty, theprocess 200 transfers todegraded mode 232 which disables the faulty power supply modules and continues operation. It should be appreciated that if multiple power supply modules are required to operate a singleelectrochemical cell 14, then degradedmode 232 will disable all the power supply modules associated with the faulty module. Theprocess 200 also transfers to logmode 212 to record the appropriate power supply information and send a warning to the user. Theprocess 200 then continues the operation of thesystem 12 in degraded mode. Once thesystem 12 has been shut down and properly services,process 200 is reset to anormal mode 210. If another power supply should fail, the sequence of modes repeats when theprocess 200 transfers back todiagnostic mode 230. In the event that there are not enough power supply modules remaining to operate a singleelectrochemical cell 14, then theprocess 200 transfers toshutdown mode 216 to stop the processes ofsystem 12 in an orderly manner.Process 200 usesalert mode 218 to notify the user. - Another type of error that may be encountered by the
system 12 is a low inlet ionized water flow. In order to maintain operation of thesystem 12, a steady supply of fresh deionized water is typically required. If the flow of deionized water should be reduced or stop due to a problem with the external supply of water 17 then the system may be damaged if there is not enough deionized water to supply theelectrochemical cells 14. Water flow from deionizer 17 is determined by measure the amount of time is required to change the level of water measured bysensor 48 in the oxygen-water phase separator 46. As shown inFIG. 11 , ifnormal mode 210 determines that the flow rate of the inlet deionized water is too low, theprocess 200 transfers todiagnostic mode 234 which determines what hydrogen gas production rate can be achieved with the available deionized water inlet flow. Theprocess 200 then transfers todegraded mode 236 which reduces the current produced by the power supplies 24 to reduce the hydrogen production rate of theelectrochemical cells 14.Degraded mode 236 continues to monitor and analyze the deionized water inlet flow in the manner described above. Once thesystem 12 has been shut down and properly services, or if the flow of deionized water flow returns to a normal operating state, theprocess 200 is reset to anormal mode 210. If the water flow continues to trend downward, theprocess 200 transfers to logmode 212 records the information and sends a warning to the user. - If the inlet water flow declines below a second threshold, the
process 200 transfers back to thediagnostic mode 234 and the sequence repeats as described above until the inlet flow falls beneath a minimum operating level. Once the minimum operating level is achieved, theprocess 200 transfers toshutdown mode 216 to stop the processes ofsystem 12 in an orderly manner.Process 200 usesalert mode 218 to notify the user. - The last example of an error that may be encountered by the
system 12 is low gas output pressure. Referring toFIG. 12 , once thesystem 12 is at a normal operating state, a drop in output pressure may indicate a fault condition requiring maintenance or operator intervention to prevent damage. Output pressure of thesystem 12 is measured bypressure sensor 155 which transmits a signal indicative of the gas pressure to thecontrol panel 28. During thenormal operating mode 210, thecontrol panel 28 monitors the actual gas pressure signal and compares the signal to a parameter indicative of a minimum threshold pressure. If the actual gas pressure drops below a minimum threshold pressure, theprocess 200 transfers todiagnostic mode 238 which monitors 240 the actual output pressure for a predetermined amount of time. If the actual pressure stays below the minimum threshold pressure,process 200 optionally enterslog mode 212 and records the information and sends a warning to the user. - If the actual gas pressure returns to the desired pressure,
process 200 is reset and transfers back tonormal operating mode 210. However, if actual gas pressure measured bypressure sensor 155 remains below the minimum threshold pressure for the predetermined amount of time,process 200 transfers back to shut downmode 16 viadiagnostic mode 238 to stop the processes ofsystem 12 in an orderly manner.Process 200 usesalert mode 218 to notify the user. Preferably, the minimum threshold pressure is lower than the operating pressure required by the operator, and more preferably at least 10% lower than the operating pressure. In the exemplary embodiment, the operating pressure is 200 psi, and the minimum threshold pressure is 180 psi. It should be appreciated that the actual values may be set to any that are necessary or desired by the operator for a given application. - While preferred embodiments have been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. For example, while the embodiments shown referred specifically to an electrochemical system have three electrochemical cells, it would also equally apply to a system having two, four or more electrochemical cells. Accordingly, it is to be understood that the present invention has been described by way of illustrations and not limitation.
Claims (20)
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Cited By (11)
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US9206043B2 (en) | 2009-02-20 | 2015-12-08 | Marine Power Products Incorporated | Method of and device for optimizing a hydrogen generating system |
US10118821B2 (en) | 2009-02-20 | 2018-11-06 | Marine Power Products Incorporated | Method and apparatus for efficient on-demand production of H2 and O2 from water using waste heat and environmentally safe metals |
US11214486B2 (en) | 2009-02-20 | 2022-01-04 | Marine Power Products Incorporated | Desalination methods and devices using geothermal energy |
US9067186B2 (en) | 2009-02-20 | 2015-06-30 | Marine Power Products Incorporated | Stability control of a hydrogen generating system and method |
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US20130062215A1 (en) * | 2011-09-13 | 2013-03-14 | Honda Motor Co., Ltd. | Water electrolysis system and method of stopping operation of water electrolysis system |
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US10370595B2 (en) | 2012-03-13 | 2019-08-06 | Marine Power Products Incorporated | System for and method of using on-site excess heat to convert CO2 emissions into hydrocarbons income at coal-fired power plants |
US10145015B2 (en) | 2012-12-05 | 2018-12-04 | Marine Power Products Incorporated | Hydrogen generating system and method using geothermal energy |
FR3078829A1 (en) * | 2018-03-12 | 2019-09-13 | Pierre Rene Ferdinand Millet | METHOD FOR MULTIPHYSICAL CHARACTERIZATION OF STACKS OF ELECTROCHEMICAL OR PHOTOELECTROCHEMICAL CELLS |
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