US3755128A - Electrolysis system and method - Google Patents
Electrolysis system and method Download PDFInfo
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- US3755128A US3755128A US00072250A US3755128DA US3755128A US 3755128 A US3755128 A US 3755128A US 00072250 A US00072250 A US 00072250A US 3755128D A US3755128D A US 3755128DA US 3755128 A US3755128 A US 3755128A
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 43
- 239000007787 solid Substances 0.000 claims description 45
- 239000007789 gas Substances 0.000 abstract description 105
- 230000008569 process Effects 0.000 abstract description 3
- 238000004804 winding Methods 0.000 description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
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Images
Classifications
-
- 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
Definitions
- An electrolysis apparatus and method including means for decomposing an electrolyte intoone or more gas products, and also including means responsive to the pressure or flow condition of one of the product gases for controlling the electrical input to the electrolysis cell whereby to match the gas generation rate and the gas demand rate in the electrolysis system. Electrical power cost of the electrolysis process, a major operating expense, will be reduced if .the gas generation rate responds to the demand rate. x
- the product gas demand function such as product gas pressure or flow rate is converted into'an electrical control signal which is fed to a feedback network which controls the direct current output of the'p'ower supply tothecell',.tothereby cause a gas generation rate equaling the demand rate.
- the gas demand function which is measured compensates automatically for varying operating, conditions which affect gas generation rate such as ambient temperature, cell electrolytephenom ena, andlong term aging characteristics of the electrolysis-cell.
- Control signals representing'variou's other parameters of the electrolysis system'such ashighand low limits for electrolysis current may also b'e'fed -into the feedback network to control the current flowfrom' the BACKGROUND OF THE INVENTION 1'.
- Field of the Invention This'invention relates toan electrolysis'system, and
- Electrolysis systems are known in the prior art in which a' direct current isapplied across a pair of electrodes in'contactwith an'electrol'yte toca'u'se decomposition of the electrolyte into one or more productgases.
- Onesuch'system involving an aqueous electrolyte and hydrogen" and oxygen product gases, is'shown inU.S2 Pat. No: 3-,4l0,770,.granted t o Lester B'uechler'on' Nov. I2, 1968.
- the system of-the Buechlerpatentjust mentioned consists essentiallyof six parts: (l-)"an'electrolysis-module (a stack of cells); (2) a recirculating electrolyte loop; (13") water addition "equipmenti (4 "ox ygen manifolding; (5')' hydrogen manifolding; and (6) a-direct currentpower supply.
- anelectrolysis appa rat'us'and method including means for decomposing an' electrolyte'into one" or more gas products,-andalsoineluding means responsive'to the pressure or flow condition of one of the product gases for controlling theelectricalinputto the electrolysis cellwhefeb'y'tomatch the gas generation rate and the gas demand ratein' the electrolysis'system. Electrical power cost ofthe electrolysis process, a major operating expense, will be redircedif the gas generation'rate resp'ondsto the demandrate.
- the product gas demand function such as product gas'pressure or flow rate is converted into an electrical control signal whichis fed'to a feedback network which controls-the directcurrent output of thepower supply to the cell, to thereby cause gas generation rate equaling the'demand rate.
- the gas demand'function which is measured compensates'automatically for varying opcrating conditions which afiect gas generation rate such asambient temperature, cell electrolyte phenomena, andlong term aging characteristics of the electrolysis'cell.
- Control signals representing various other parameters of the electrolysis system such as high andlow limits for electrolysis current may also'be fed'in'to the feedback network to control the current flow from the powersupply to the cell.
- FIG. 1 is a schematic view of an electrolysisapparatusand system embodying the automatic control featuresof the invention
- FIG. 2 is a schematic diagram of control circuitry whichmay be incorporated in'the system and'apparatus of the present invention to control the gas generation rate'as a function of the gas demand rate and alsoas a function of other factors;
- FIG. 3 is a schematic diagram of another control circuit which may be used to control'the gas generation rate as afunction of thegas demand rate also as'afunction of other factors; and I FIG. 4 is a vector diagram showing the various'electrical relationships in the circuit of FIG. 3.
- FIG. 1 there'is shown an'ele'ctrolysis system and apparatus which except for the'auto-.
- the aqueous electrolysis system and apparatus of FIG.1 comprises a cell having a pair of gas perme able electrodes, namely, cathode l1 and anode 12, in direct contact with the opposite surfaces of the electrolyte matrix 13 which is saturated with an aqueous electrolyte. Electrodes 1 l and 12 are connected by leads 15 and 16 to a source of direct current generally indicated at 14 to be described more fully hereinafter. The quantity of gas produced is directly proportional to the number of electrolysis cells and to the current flow through each cell. Electrolyte matrix 13 is a porous diaphragm of asbestos fibers or other material which is resistant to attack by caustic alkali solution or other electrolyte.
- the thickness of the electrodes 11, 12 and the matrix 13, as shown in FIG. 1, have been exaggerated for purposes of clarity in description.
- the electrodes 11 and 12 and the electrolyte matrix 13 are supported in housing 17 which forms a gas chamber 18 with the cathode 11 and an electrolyte chamber 19 with the anode 12.
- the aqueous electrolyte 20 is contained in the electrolyte chamber 19.
- the electrolyte matrix 13, saturated with the aqueous electrolyte, serves a dual function.
- the matrix 13 maintains intimate contact between the interface of the electrolyte and the gas permeable electrodes 1 1 and 12 and also serves as a gas impervious barrier to prevent mixing of the gas product's.
- Electrolyte is supplied to the cell by the circulation of electrolyte solution from separator 22 to electrolyte chamber 19 by means of pump 23 through conduits 24, 25 and 26.
- the gas generated at the electrode 12 adjacent the electrolyte chamber 19 is removed from the electrolyte chamber entrained in the circulating electrolyte solution.
- the aqueous electrolyte 20 impelled by the driving force of. the gas bubbles present in it, is forced from the electrolyte chamber 19 through conduit means 24 and passes to electrolyte separator 22 where the gas produced at the electrode 12 and entrained in the aqueous electrolyte 20 is extracted and separated from the circulating electrolyte solution.
- Design details for the separator 22 are not shown as separators of this type are well known in the art.
- Water consumed in electrolysis is replaced by means of water storage means from which water is fed in controlled amounts to separator 22 via conduit 31 to maintain the electrolyte at optimum concentration.
- Valve 32 regulates the addition of water to the electrolyte solution in separator 22 at a rate determined to replace the water consumed by electrolysis.
- the oxygen gas produced at anode electrode 12 is withdrawn overhead from the separator 22 via conduit 33, through differential pressure regulator or control valve 58, and through connected conduit 59. Oxygen not required for maintaining system pressure is discharged through conduit or plumbing" 59.
- the degassed electrolyte passes out of the separator 22 via conduit means 25 to pump 23 wherein it is directed via conduit means 26 back to the electrolyte chamber l9.v
- the hydrogen gas produced at cathode electrode 11 is evolved into gas chamber 18 and the chamber 18 is maintained under pressure by regulating the passage of gas out of the chamber.
- the gas that is removed from gas chamber 18 is passed by conduit 50 through valve 60 and thence externally of the system through conduit 61.
- Demand for hydrogen gas is generated by valve 60 or by a system of valves and control devices in response to the variable demand requirements of a gas demanding load external of the system.
- Hydrogen demand is discharged by conduit or plumbing 61.
- Valve 60 and conduit 61 are both located external to the electrolysis and control'syste'm but interface with the electrolysis and control system at 62.
- the valve 58 opens or closes in response to this pressure to provide a decrease or increase in the oxygen gas pressure in oxygen conduit 33 so as to maintain an appropriate differential pressure across the cell 10 and avoid leakage ofelectrolyte solution through the matrix 13 to chamber 18.
- the electrolyte in the capillary matrix 13 adjacent electrode 11 is constantly replenished with electrolyte solution. Since the gas produced at electrode 11 is not entrained in the electrolyte, the need for a separator unit to disentrain gas produced at electrode 11 from the electrolyte is eliminated.
- the hydrogen manifold pressure in conduit 50 is the independent or reference pressure for the differential pressure valve 58 and the oxygen manifold 33 pressure is the dependent or following pressure. Oxygen not required for maintaining manifold 33 pressure is discharged through conduit or plumbing 59.
- valve 58 could be placed in conduit 50 instead of in conduit 33 as shown, in which case the oxygen pressure in conduit or manifold 33 would be used as the reference pressure.
- the demand function transducer device 51 senses a gas flow or pressure condition in hydrogen manifold 50
- the transducer device 51 could instead sense a gas flow or pressure condition in oxygen manifold 33.
- the differential pressure valve 58 is located in hydrogen manifold 50 and the pressure in oxygen rnanifold 33 is used as the reference pressure for the difl'erential pressure system, then the demand function transducer device 51 should also be located in oxygen manifold 33.
- a multicellular apparatus comprising a plurality of the unit cells may be connected in series and clamped into a compressed face-to-face relationship along a common axis to form a module or stack of cells.
- such assemblies are preferred for efficient, quantitative production of hydrogen and oxygen.
- the polarity connections of the direct current input power to the cell electrodes 11 and 12 are such that electrode 12 is derstood that instead of the preferred: arrangement just referredto, the polarity connections of the power supply tothe electrolysis CCllZCOllld be the reverse of those just described, so that.
- electrode L1 is the anode at which oxygenis evolved andelectrode 12 is the cathode atwhichhydrogenis evolved.
- FIG. 1 the power supply. generally indicated-at l4- hasits electricaloutputconnected by conductors or cables 15 and 1 6 to the electrodes 11 and 12 of the cell 10.
- An electrical transducer device 512 which;.may sense either gas pressure or, gasflowconditions in: the hydrogen manifold 50, depending upon the a particular. type of transducer device 51 which is used, is electrically connected by. conductor means schematically indicated at:
- the feedbacknetwork. 531in-response toa control signal or signals applied-thereto controlsthe power supply 14 via conductor means .73, to provide a .variable electrolysis current tothe electrolysis cell via.cables.ilSfand 16.
- transducer 51 pressure or ofth'e gasvflow condition sensed by transducer 51, depending. upon whether transducer device -51 isfof atype which sensesi gas pressure or gas flow. in this .mannera given pressure or flow.rate.of.the
- transducer -5 1 detects av pressure. drop. in hydrogen.
- iftransducer 51 detects-a'pressure increase in hydrogen.manifoldSOEwhichis indicative of decreased demand for.hydrogen,.itwilltransmit aproportional signal to, feedback network 53 which: willcausefeedback network:53-to causeareduction in the direct-current output-ofpower'. supply 14 .to the electrodes l l .and 12 jofcellsllhothereby decrease. the gas generation rate of cell @l0until the pressure in hydrogen I manifold -50'is returnedLto the set point;
- thermaland mass flowq considerations require that the maximumand minimum electrolysis currents be limited .-to ,preselectedvalues.
- AsensorSS connected in current,sensingrelation.tocable.l6 (or 15) leading, from power. supply l4. to.one of.:.theelectrodes of cell 10 is: used toquantitativelysense the electrolysiscurrent and to feed a signal via conductor means 77 into the feedback network 53 to limit the maximum and minimum-current supplied by'power supply to electrolysis cell 10 to maximum and minimum values.
- the feedback network and associated powersupply may be of the type shown and described, for example, in U.S. Pat. No. 3,333,178 granted to Roland L. Van Allen and Charles E. l-lardies on July 25, 1967, and'th'e teachings of U.S. Pat. No. 3,333,178 to Van Allen and Hardies are hereby incorporated by reference into the present application;
- the feedback network 53 and power supply 14 may assume the form shown in FIG. 4 of the aforementionedVan Allen et al. patentwhich is substantially embodied in FIG 2 of the present application.
- FIG. 20f a feedback network and thyristor power supply utilizing solid state devicesgenerally indicated at 100 and 100 of the type having thyratron characteristics.
- the device exhibits the characteristics of a rectifier, while the device presents a high impedance to the flow of current between the main terminals in the opposite'direction that is, a high forward impedance, until the device is energizedor fired upon'zapplication of a control signal to the gateorcontrol terminal.
- the forward impedancewith respect to the main current carrying terminals abruptly drops to an extremely low value, and the flow ofcurrent through the device between the main. cu'rrent carlrying terminals is independent of and does not require application of a control orenergizing signal tothe gate terminal and will continue so long as a potential-is maintained across the main current carrying electrodes.
- the device returns to its normal or unenergized condition, presenting'a'high forward-impedance, and will not pass current although a potential is applied across the main'current carrying electrodes, providing a breakdown potential is not reached, until a control signal is applied to-the gate ter minal to again energize the device.
- the combined feedback network and'power supply shown in FIG. 2 comprises a pair of solid state devices having thyratron characteristics 100 and 100, each including an anode terminal 102, 102' which are respectively connected to opposite terminals 104, 104' of a center tapped transformer secondary generally indicated at 106.
- the circuit of FIG. 2 is analogous to a full-wave center tap rectifier and provides a controlled flow of load output current to the input electrical terminals of the electrolysis cell during each half cycle of the applied voltage across transformer secondary 106, the current conduction period during each half cycle depending upon the cumulative effect of the control signals applied to the feedback network 53, as will be explained more fully hereinafter.
- the solid state devices 100, 100 also each respectively include a cathode terminal 108, 108', respectively, which are connected to each other and also to the output or load terminal 116 which is connected to cable 16 leading to electrode 12 of the electrolysis cell.
- the other cable 15 leading to the electrolysis cell is connected to the center tap 118 of the transformer secondary 106.
- the solid state devices 100 and 100 each include a gate or control terminal 120, 120, respectively.
- the apparatus further includes a pair of saturable magnetic cores 122 and 122', respectively, preferably constructed of a material presenting a substantially rectangular hysteresis characteristic.
- Two control windings 124, 126 are provided for the saturable magnetic cores 122 and 122', each of the two windings 124, 126 being common to both of the saturable magnetic cores 122 and 122'.
- windings 124, 126 are adapted to be energized with direct current control voltages to control the degree of saturation of saturable magnetic cores 122, 122.
- the control voltage across control winding 124 may be derived, for example, from the output voltage signal of transducer device 51 which monitors either the gas pressure or the gas flow in the hydrogen manifold 50, depending on the type of transducer device 51 which is used.
- the control voltage across control winding 126 for example, may be a signal derived from the current sensing device 55, FIG. 1, and diagrammatically shown as being connected by conductor means 77 to the feedback network to limit the direct current supplied by the power supply 14 to electrolysis cell 10 to maximum and minimum values.
- the minimum input current to cell 10 is set at a value which provides a minimum gas product rate sufficient to provide dilution of gas from leaks or gas migration from cavity across the capillary matrix 13 to cavity 18. In this way, a maximum gas purity in cavity 18 is maintained.
- the gas generation rate may exceed the demand rate. This condition results in an increased hydrogen pressure which is relieved by regulator valve 79 connected to hydrogen manifold line 50, regulator valve 79 permitting the escape of hydrogen gas through relief conduit 81.
- each gate winding 130, 130' Connected in circuit with each of the solid state thyratron devices 100 and 100' is a gate winding 130, 130'.
- One end of each gate winding 130, 130' is connected to the terminal 104 or 104 of the secondary winding 106 and to anode terminal 102', 102 in series with a solid state rectifier 132, 132'.
- the opposite end of each gate winding 130, 130' is connected through a resistor 134, 134', to the gate or control element terminal 120, 120 of the solid state thyratron device 100,
- Each of the respective gate windings 130, 130' is mounted on or in magnetic association with one of the respective saturable cores 122, 122', respectively.
- control windings 124, 126 and the gate windings 130, 130 each are shown with a dot which indicates winding sense or polarity relationship.
- Gate winding 130 in the circuit of solid state device 100 presents a high impedance, since core 122 is not saturated at this instant and no power is applied across the load output terminals and 116. Current, however, will flow through the gate circuit of coil 130, i.e., through coil 130, resistor 134, gate terminal 120, through a portion of solid state device 100, cathode terminal 108, and across load terminals115, 116, back to center tap 118 of transformer secondary 106, to thereby carry the magnetic material of core 130 toward one level of saturation, the parameters of the gate circuit being selected to insure adequate current flow to effect this'performance.
- Core 122 will be driven to saturation at some point during the half cycle of the alternating current supply source which is positive relative to the anode terminal 102 of solid state device 100, as determined by the combined effect of the vectorial sum of the control signals applied to the windings 124 and 126.
- the impedance of gate winding 130 abruptly drops with aconcomitant increase in current through gate winding 130.
- the abrupt current variation through gate winding 130 is applied as a control signal through resistor 134 to gate terminal of solid state device 100 to energize or fire the device 100 within a microsecond or less following saturation of core 122.
- the forward impedance of solid state device 100 abruptly drops very close to zero and the power supply is connected across load terminals 115, 116 through the remaining portion of the half cycle.
- the solid state device 100 when fired presents a substantially complete short circuit across gate winding and thereby terminates the control signal from gate winding 130 to gate terminal 120 of the solid state device l00.
- the arrangement for producing and applying a control signal to the gate terminal of the solid state device provides an automatic clipping or limiting operation which prevents application of a control signal of a magnitude which exceeds the design limitations of the solid state device.
- the respective solid state devices 100 and 100' and the circuits associated therewith reverse their respective relationships from those described for the first half cycle of applied voltage. That is, the solid state device 100' now presents a high forward impedance and the solid state device-100 presents a high re-. verse impedance.
- the solid state device'100' becomes conductive or fires at a predetermined angular condition in the second half cycle of applied voltage in the same manner as described in connection with the solid state device lduringthefirst half cycle of applied voltage. When fired, the forward impedance of the solid state device 100' abruptly drops very close to zero and:the powersupply is'connectedacross the load ter-:
- phase angle shifting'system' of the U.S. Pat. No. 3,333,178 to Van Allen-etal, hereinbefore described,- are set-forth insprague Technical Paper'No. 63-9, published by Sprague Electric Company, North Adams, .Massachusetts, entitled The Silicon Con-- patented form of wide angle phase-shifting circuit con trolled by a saturable reactor.
- This special form offers a. full 180 rangeof linear phaseshift using a small (4 millwatt) direct current control'signaland provides a steeply rising gate pulsewhich tri'ggers the firing 'of'the thyratron type solid state device.
- This Silicontrol gate drive is manufactured and sold by-Sprague-Electric Company of North Adams, Massachusetts.
- an input transformer generally indicated at 150 including a primary winding 152 to which is applied, forexample; 1 15 volt, 60'cycles per second alternating current-electric power;
- Transformer 150 includes a-secondary winding-154.
- Acrossthe terminals Band X of thetransformer secondary winding 154 is connected a fixed phaseshiftnetwork RC, which establishes a base linevoltage E across resistor R as shown in the vector; diagram of FIG. 4.
- a pulse forming network generally indicated in block diagram form at 156 in FIG. 3 is connectedacros's'the centertap terminal 0 of the transformer secondary 154 and also across the terminal Pwhich is the junction point between the inductance L and the capacitance C in the series'resonantnetwork across the resistance R.
- the circular locus isrnade to pass through the input potential point X on the vector diagram, and since angle X A B is a right angle, the vector'X'B' is a diameter of the circle'an'dthe input center tap'O' is at the-center'of the'circle.
- the vector 0'? then represents an output that can be taken from the network, varyingin phase angle by approximately 300 while remaining constantin amplitude'e- Two silicon controlled rectifiersSCR No. 1 and SCR 7 No. 2 (not shown') may be connected to provide recti- 25 fied direct' current to'theelectrodes'llyl2 of cell 10, the magnitude of the current flow to cell 10 being con trolled during both half cycles of alternating current across transformer 150 by the circuit of FIG. 3.
- the inductor L takes the form of a specially designed saturable reactor 155 whose indu'ctanceis varied by saturating its core to a greater or less degree by passing: varying amounts of direct current through the control windings 1-2, 3-4.
- the output voltage across the terminals O, P, are formed into pulse" spikes the pulse forming network 156 which drives the coupling transformer generally indicated at 158.
- the pulse" spikes are delivered on alternate half cycles from'terrninals G and 6,, which are each respectively connected to the'gate or control terminal of one of a'pair solid state thyratron devices,(not shown) which 'in this case across resistor R-is a series resonant circuit consisting of FIG. 4, the primed letters such as A'P, etc., correare the pair of silicon controlled rectifiers SCR No. l and SCR No. 2, the terrninalsK K, of the circuit of FIG. 3 being connected to the cathode terminals of the respective solid state. devices.
- the control windings l-2, 3-4 whichcontrol the degree of saturation of the saturable core reactor and hence control the value of the inductance L in the phase shift circuit, derive their signal voltages fromthe sources as set forth in the example of- FIGS. 1' and 2.
- the voltage signal across control winding l-2 of FIG. 3 may be'the signal from the transducer device 51 indicating the gas pressure or flow'condition in the hydrogen manifold 50.
- the voltage signal across control winding 3-4. may be derived from the curr'ent transducer device 55 in current sensing relation to con ductoror cable 16 between the thyristor powersupply l4 and the electrode 12, to indicate the direct current flow to cell 10.
- the feedback and power ⁇ supply systems shown in FIGS. 2 and 3 are by way of example only and that other suitable types of feedback and power supply systems may be substitutedthe'refon;
- trimmers in accordance with the invention an apparatus for and method of rnatchingthe gas generationrate V with the gas demand rate in an electrolysis systemby' measuring a demand function such as gas pressure or gas flow, and adjusting the input direct current to the electrodes of the electrolysis cell in accordance with the sensed demand function whereby to match the gas generation and demand rates.
- a demand function such as gas pressure or gas flow
- This matching of gas generation rate with gas demand rate results in important savings in the cost of electrical current input to the electrolysis cell.
- a very important advantage of the apparatus and method is that in sensing the gas pressure or gas flow and controlling the input current to the electrolysis cell as a function of the sensed gas pressure or gas flow as taught by the present invention, not only is the gas output of the cell varied in accordance with the varying gas demand rate of the external gas demanding load, but also automatic and inherent compensation is simultaneously made without further adjustment for such varying operating conditions as ambient temperature, module electrolyte phenomena, and long term aging characteristics of the electrolysis cell.
- An electrolysis system for decomposing an electrolyte into at least one product gas, comprising an electrolysis cell having terminals and adapted to have an electrolyte therein, said cell being adapted to generate at least one product gas upon the connection of direct current across the terminals of said cell, the generation of said one product gas by said cell being a function of the direct current input to said cell, means in circuit relationship for supplying a variable direct current to said cell terminals whereby said one product gas is generated by said cell, means for sensing the flow rate of a product gas generated by said cell, and feedback network means coupled directly between said sensing means and said direct current supplying means for controlling the variable direct current input to said cell as a function of the condition sensed.
- An electrolysis system as defined in claim 1 in which said means for supplying direct current to said cell comprises at least one thyratron type solid state device, and wherein said feedback network produces an output electrical signal that controls the load current conduction through said solid state device whereby to control the electrical current input to said cell.
- An electrolysis system for decomposing an electrolyte into at least one product gas, comprising an electrolysis cell having terminals and adapted to have an electrolyte therein, said cell being adapted to generate at least one product gas upon the connection of direct current across the terminals of said cell, the generation of said one product gas by said cell being a function of the direct current input to said cell, means in circuit relationship for supplying a variable direct current to said cell terminals whereby said one product gas is generated by said cell, means for sensing a condition of a product gas generated by said cell, feedback network 'means coupled'directly between said sensing means and said direct current supplying means for controlling the variable direct current input to said cell as a function of the condition sensed, and sensor means'connected in current sensing relation between said direct current supply means and said cell and connected to said feedback network means for limiting the maximum and minimum current supplied by said direct current supply means to said cell to predetermined maximum and minimum values.
- the method of controlling the rate of gas generation in an electrolysis system of the type including an electrolysis cell in which at least one product gas is generated by said cell upon the connection of direct current to the terminals of said cell and in which the generation of said one product gas by said cell is a function of the direct current input to said cell, which comprises the steps of sensing the flow rate from said cell of said one product gas generated by said cell, and of controlling the direct current input applied to said cell as a function of the flow rate sensed whereby to control the rate of gas generation by said cell.
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Abstract
An electrolysis apparatus and method including means for decomposing an electrolyte into one or more gas products, and also including means responsive to the pressure or flow condition of one of the product gases for controlling the electrical input to the electrolysis cell whereby to match the gas generation rate and the gas demand rate in the electrolysis system. Electrical power cost of the electrolysis process, a major operating expense, will be reduced if the gas generation rate responds to the demand rate.
Description
United States Patent 91 H'erwig ELECTROLYSIS SYSTEM AND METHOD Warren E. Herwig, Greenfield, Wis. Assignee: Isotopes, Inc., westwood, Filed: Sept. 15, 1970 Appl. No.: 72,250
Inventor:
u.s. c1. 204/230, 2047129 1111. c1 801k 3/00, c01 13/0 Field of Search ..204/228-230, 129
[56] References Cited UNITED STATES PATENTS 8/1969 1 Wallinder 204/228 12/1969 Emich et al..' 204/228 X 8/1967 Hagen 204/230 '2/1970 Zeff et'al. 204/129 X 7' 6/5 DE/WI/Vi/A/G 240/40 1111 3,755,128 1451 Aug. 28,- 1973 1,581,944 4/1926 Hausmeister 204/230 X Primary Examiner-John H.- Mack Assistant Examiner-D. R. Valentine Anomey-Fleit, Gipple 82 Jacobson [57] ABSTRACT An electrolysis apparatus and method including means for decomposing an electrolyte intoone or more gas products, and also including means responsive to the pressure or flow condition of one of the product gases for controlling the electrical input to the electrolysis cell whereby to match the gas generation rate and the gas demand rate in the electrolysis system. Electrical power cost of the electrolysis process, a major operating expense, will be reduced if .the gas generation rate responds to the demand rate. x
5 Claims, 4 Drawing Figures v PATENTEBmsze ms 7 v SHED 2 0F 2 54 Z mm ZN aw m 7 mm 7 ii I 7 ma 5 f, mam
more particularly toan' apparatusfor anda method of matching the gas generationrate in'andthe gas-demand rate on an electrolysis system.
2. Description of the Prior Art Electrolysis systemsare known in the prior art in which a' direct current isapplied across a pair of electrodes in'contactwith an'electrol'yte toca'u'se decomposition of the electrolyte into one or more productgases. Onesuch'system, involving an aqueous electrolyte and hydrogen" and oxygen product gases, is'shown inU.S2 Pat. No: 3-,4l0,770,.granted t o Lester B'uechler'on' Nov. I2, 1968. The system of-the Buechlerpatentjust mentioned consists essentiallyof six parts: (l-)"an'electrolysis-module (a stack of cells); (2) a recirculating electrolyte loop; (13") water addition "equipmenti (4 "ox ygen manifolding; (5')' hydrogen manifolding; and (6) a-direct currentpower supply. Thesy'stem of-the aforementioned Buechler' patent as well as other known electrolysis systems encounter operating problems when the operating requirements are increased from those of ='a continuous'steady state operation we variable demandwith minim'u'm operator attendance. In
prior art electrolysis'systems, operator attendance is requiredfor'adjustmentof the electrolysis'current due to: ('1) changes in gas demand; ('2) changesin ambient conditions affectingthe rate of gasproduction; (3
changes inthe system parametersaffecting the rate of gas production; and (4') cell aging -'characteristicsaffecting. rate of gas production.
SUMMARY OF THE INVENTION Accordingly, it is'a'n object of the'present-invention to provide 'anelectrolysis system and apparatus which It: isa further object of the invention to provide an electrolysis system and apparatus whichis substantially automatic in its operation *and which does not require operator attendance for adjusting the gas generation rate.
It is a further object of the invention to provide an aqueous electrolysis system, apparatus and method in accordance with which the electrolysis current is automatically adjusted to compensate for changes in gas demand, for changes in ambient conditions affecting the rate of gas production, for changes in system parameters such'as electrolyte temperature affecting the rate of gas production, and to compensate for cell aging characteristics affecting the rate'of gas production.
In achievement of these objectives there is provided in accordance with this invention" anelectrolysis appa rat'us'and method including means for decomposing an' electrolyte'into one" or more gas products,-andalsoineluding means responsive'to the pressure or flow condition of one of the product gases for controlling theelectricalinputto the electrolysis cellwhefeb'y'tomatch the gas generation rate and the gas demand ratein' the electrolysis'system. Electrical power cost ofthe electrolysis process, a major operating expense, will be redircedif the gas generation'rate resp'ondsto the demandrate.
The product gas demand function such as product gas'pressure or flow rate is converted into an electrical control signal whichis fed'to a feedback network which controls-the directcurrent output of thepower supply to the cell, to thereby cause gas generation rate equaling the'demand rate. The gas demand'function" which is measured compensates'automatically for varying opcrating conditions which afiect gas generation rate such asambient temperature, cell electrolyte phenomena, andlong term aging characteristics of the electrolysis'cell. Control signals representing various other parameters of the electrolysis system such as high andlow limits for electrolysis current may also'be fed'in'to the feedback network to control the current flow from the powersupply to the cell.
Further objects and advantages of the invention will become apparent from "thefollowing'description taken in'conjunction withaccompanying drawings in which: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of an electrolysisapparatusand system embodying the automatic control featuresof the invention;
FIG. 2 'is a schematic diagram of control circuitry whichmay be incorporated in'the system and'apparatus of the present invention to control the gas generation rate'as a function of the gas demand rate and alsoas a function of other factors;
FIG. 3 is a schematic diagram of another control circuit which may be used to control'the gas generation rate as afunction of thegas demand rate also as'afunction of other factors; and I FIG. 4 is a vector diagram showing the various'electrical relationships in the circuit of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to FIG. 1, there'is shown an'ele'ctrolysis system and apparatus which except for the'auto-.
to Lester W. Buechler, on Nov. 12, 1968, theteachings" of which patent are hereby incorporatedbyreference into this application.
The aqueous electrolysis system and apparatus of FIG.1 comprises a cell having a pair of gas perme able electrodes, namely, cathode l1 and anode 12, in direct contact with the opposite surfaces of the electrolyte matrix 13 which is saturated with an aqueous electrolyte. Electrodes 1 l and 12 are connected by leads 15 and 16 to a source of direct current generally indicated at 14 to be described more fully hereinafter. The quantity of gas produced is directly proportional to the number of electrolysis cells and to the current flow through each cell. Electrolyte matrix 13 is a porous diaphragm of asbestos fibers or other material which is resistant to attack by caustic alkali solution or other electrolyte. The thickness of the electrodes 11, 12 and the matrix 13, as shown in FIG. 1, have been exaggerated for purposes of clarity in description. The electrodes 11 and 12 and the electrolyte matrix 13 are supported in housing 17 which forms a gas chamber 18 with the cathode 11 and an electrolyte chamber 19 with the anode 12. The aqueous electrolyte 20 is contained in the electrolyte chamber 19.
The electrolyte matrix 13, saturated with the aqueous electrolyte, serves a dual function. The matrix 13 maintains intimate contact between the interface of the electrolyte and the gas permeable electrodes 1 1 and 12 and also serves as a gas impervious barrier to prevent mixing of the gas product's.
Electrolyte is supplied to the cell by the circulation of electrolyte solution from separator 22 to electrolyte chamber 19 by means of pump 23 through conduits 24, 25 and 26. The gas generated at the electrode 12 adjacent the electrolyte chamber 19 is removed from the electrolyte chamber entrained in the circulating electrolyte solution.
During the operation of the cell, the aqueous electrolyte 20, impelled by the driving force of. the gas bubbles present in it, is forced from the electrolyte chamber 19 through conduit means 24 and passes to electrolyte separator 22 where the gas produced at the electrode 12 and entrained in the aqueous electrolyte 20 is extracted and separated from the circulating electrolyte solution. Design details for the separator 22 are not shown as separators of this type are well known in the art. Water consumed in electrolysis is replaced by means of water storage means from which water is fed in controlled amounts to separator 22 via conduit 31 to maintain the electrolyte at optimum concentration. Valve 32 regulates the addition of water to the electrolyte solution in separator 22 at a rate determined to replace the water consumed by electrolysis.
The oxygen gas produced at anode electrode 12 is withdrawn overhead from the separator 22 via conduit 33, through differential pressure regulator or control valve 58, and through connected conduit 59. Oxygen not required for maintaining system pressure is discharged through conduit or plumbing" 59. The degassed electrolyte passes out of the separator 22 via conduit means 25 to pump 23 wherein it is directed via conduit means 26 back to the electrolyte chamber l9.v
The hydrogen gas produced at cathode electrode 11 is evolved into gas chamber 18 and the chamber 18 is maintained under pressure by regulating the passage of gas out of the chamber. The gas that is removed from gas chamber 18 is passed by conduit 50 through valve 60 and thence externally of the system through conduit 61. Demand for hydrogen gas is generated by valve 60 or by a system of valves and control devices in response to the variable demand requirements of a gas demanding load external of the system. Hydrogen demand is discharged by conduit or plumbing 61. Valve 60 and conduit 61 are both located external to the electrolysis and control'syste'm but interface with the electrolysis and control system at 62.
When a direct current is initially applied to the apparatus at cathode 11 and anode 12, as will be described hereinafter, gas generated at electrode 11 is collected in the chamber 18 until the pressure of the gas in the chamber 18 exceeds the pressure of the gas generated at electrode 12. This occurs in a relatively short time interval and if any electrolyte is present in chamber 18 it will be forced through the capillary matrix to chamber 19. The differential pressure control valve 58 in oxygen conduit 33 maintains a preset pressure differential between the hydrogen gas pressure in gas chamber 18 and the pressure of the oxygen gas in conduit 33 leading from separator 22. The hydrogen gas pressure in conduit 50 is monitored to valve 58 by conduit 72 connected between conduit 50 and differential pressure control valve 58.
As the pressure of the gas produced at the electrode 12 is raised or lowered, the valve 58 opens or closes in response to this pressure to provide a decrease or increase in the oxygen gas pressure in oxygen conduit 33 so as to maintain an appropriate differential pressure across the cell 10 and avoid leakage ofelectrolyte solution through the matrix 13 to chamber 18. In this manner, the electrolyte in the capillary matrix 13 adjacent electrode 11 is constantly replenished with electrolyte solution. Since the gas produced at electrode 11 is not entrained in the electrolyte, the need for a separator unit to disentrain gas produced at electrode 11 from the electrolyte is eliminated.
The hydrogen manifold pressure in conduit 50 is the independent or reference pressure for the differential pressure valve 58 and the oxygen manifold 33 pressure is the dependent or following pressure. Oxygen not required for maintaining manifold 33 pressure is discharged through conduit or plumbing 59.
It will also be understood that in the pressure differential control system, the valve 58 could be placed in conduit 50 instead of in conduit 33 as shown, in which case the oxygen pressure in conduit or manifold 33 would be used as the reference pressure.
Also, while in the system illustrated in FIGJ, the demand function transducer device 51 senses a gas flow or pressure condition in hydrogen manifold 50, the transducer device 51 could instead sense a gas flow or pressure condition in oxygen manifold 33. I
If the differential pressure valve 58 is located in hydrogen manifold 50 and the pressure in oxygen rnanifold 33 is used as the reference pressure for the difl'erential pressure system, then the demand function transducer device 51 should also be located in oxygen manifold 33.
As is obvious'to one skilled in the art, a multicellular apparatus comprising a plurality of the unit cells may be connected in series and clamped into a compressed face-to-face relationship along a common axis to form a module or stack of cells. In commercial applications such assemblies are preferred for efficient, quantitative production of hydrogen and oxygen.
In -the illustrated embodiment of FIG. 1, the polarity connections of the direct current input power to the cell electrodes 11 and 12 are such that electrode 12 is derstood that instead of the preferred: arrangement just referredto, the polarity connections of the power supply tothe electrolysis CCllZCOllld be the reverse of those just described, so that. electrode L1 is the anode at which oxygenis evolved andelectrode 12 is the cathode atwhichhydrogenis evolved.
ltwill be notedin the schematic diagram of. FIG. 1 that: the power supply. generally indicated-at l4- hasits electricaloutputconnected by conductors or cables 15 and 1 6 to the electrodes 11 and 12 of the cell 10. An electrical transducer device 512 which;.may sense either gas pressure or, gasflowconditions in: the hydrogen manifold 50, depending upon the a particular. type of transducer device 51 which is used, is electrically connected by. conductor means schematically indicated at:
75, to-thefinputof the, feedbackinetwork'53i As willsbe explaineddnmore: detail hereinafter, the feedbacknetwork. 531in-response toa control signal or signals applied-thereto controlsthe power supply 14 via conductor means .73, to provide a .variable electrolysis current tothe electrolysis cell via.cables.ilSfand 16.
The ,electrolysis. current;is therefore a function of the.
gas. pressure or ofth'e gasvflow condition sensed by transducer 51, depending. upon whether transducer device -51 isfof atype which sensesi gas pressure or gas flow. in this .mannera given pressure or flow.rate.of.the
transducer -5 1 detects av pressure. drop. in hydrogen.
manifold-50. which istindicative of increased demand for hydrogen, it will.transmit aproportional signalto feedback network 53;.whichywill cause feedback network53=to causean-increase inthedirect current flow to cell-"lozfromjpower supply sufficient to. increase the gas generation 1 rate of. cell 10 untilthe pressure in hydrogenmanifold sfli is returned to the set point.
Conversely, iftransducer 51 detects-a'pressure increase in hydrogen.manifoldSOEwhichis indicative of decreased demand for.hydrogen,.itwilltransmit aproportional signal to, feedback network 53 which: willcausefeedback network:53-to causeareduction in the direct-current output-ofpower'. supply 14 .to the electrodes l l .and 12 jofcellsllhothereby decrease. the gas generation rate of cell @l0until the pressure in hydrogen I manifold -50'is returnedLto the set point;
The thermaland mass flowq considerations require that the maximumand minimum electrolysis currents be limited .-to ,preselectedvalues. AsensorSS connected in current,sensingrelation.tocable.l6 (or 15) leading, from power. supply l4. to.one of.:.theelectrodes of cell 10 is: used toquantitativelysense the electrolysiscurrent and to feed a signal via conductor means 77 into the feedback network 53 to limit the maximum and minimum-current supplied by'power supply to electrolysis cell 10 to maximum and minimum values.
The feedback network and associated powersupply may be of the type shown and described, for example, in U.S. Pat. No. 3,333,178 granted to Roland L. Van Allen and Charles E. l-lardies on July 25, 1967, and'th'e teachings of U.S. Pat. No. 3,333,178 to Van Allen and Hardies are hereby incorporated by reference into the present application; Thus, for example, the feedback network 53 and power supply 14 may assume the form shown in FIG. 4 of the aforementionedVan Allen et al. patentwhich is substantially embodied in FIG 2 of the present application. There is shown in FIG. 20f the present application a feedback network and thyristor power supply utilizing solid state devicesgenerally indicated at 100 and 100 of the type having thyratron characteristics. A number of solid state devices-of this character are now available'to the industry. General Electric Company offers devices identifiedas-Silicon Controlled Rectifiers (SCRs) and'Westin'ghouse Electric. Corporation produces devices of this type identified bythe name Trinistors.
The solid state-devices of the type indicated'at 100 and 100' in FIG. 2'include three terminals, two which (102, 108) maybe consideredas maincurrent carrying terminals and the third (120) as a gate or control terminal. These devices are so characterized that with respect to the main current carrying terminals the device at all times presents ahigh impedance to current flow in one direction, that is a high reverse impedance, and
in this respect, the device exhibits the characteristics of a rectifier, while the device presents a high impedance to the flow of current between the main terminals in the opposite'direction that is, a high forward impedance, until the device is energizedor fired upon'zapplication of a control signal to the gateorcontrol terminal.
When the device isfired, the forward impedancewith respect to the main current carrying terminals abruptly drops to an extremely low value, and the flow ofcurrent through the device between the main. cu'rrent carlrying terminals is independent of and does not require application of a control orenergizing signal tothe gate terminal and will continue so long as a potential-is maintained across the main current carrying electrodes. When the potential across the main'currentcarrying electrodes is extinguished, the device returns to its normal or unenergized condition, presenting'a'high forward-impedance, and will not pass current although a potential is applied across the main'current carrying electrodes, providing a breakdown potential is not reached, until a control signal is applied to-the gate ter minal to again energize the device. v
, It is apparent from theforegoing that-this class of solid state devices possess certain operational charac teristics of a thyratron and may therefore be described as solid state thyratrons or solid state devices pos-- sessing thyratron characteristics. The latter termsfare used throughout this description and inthe appended claims to define solid state devices of the class de-. scribed hereinbefore. Furthermore, as a descriptive aid, the main current-carrying terminals of the solid state devices of the class described hereinbefore are re-' ferred to herein and in the appended claims as anode terminal" and herein and in the appended "claims as anode terminal and -cathode termina although'the" terms anode and cathodeT are not generally employed in connection with solid state devices, and probably would not be used to designate the components of these solid state devices to which the main current carrying terminals are connected.
Referring now more specifically to FIG. 2, the combined feedback network and'power supply shown in FIG. 2 comprises a pair of solid state devices having thyratron characteristics 100 and 100,, each including an anode terminal 102, 102' which are respectively connected to opposite terminals 104, 104' of a center tapped transformer secondary generally indicated at 106. The circuit of FIG. 2 is analogous to a full-wave center tap rectifier and provides a controlled flow of load output current to the input electrical terminals of the electrolysis cell during each half cycle of the applied voltage across transformer secondary 106, the current conduction period during each half cycle depending upon the cumulative effect of the control signals applied to the feedback network 53, as will be explained more fully hereinafter. The solid state devices 100, 100 also each respectively include a cathode terminal 108, 108', respectively, which are connected to each other and also to the output or load terminal 116 which is connected to cable 16 leading to electrode 12 of the electrolysis cell. The other cable 15 leading to the electrolysis cell is connected to the center tap 118 of the transformer secondary 106.
The solid state devices 100 and 100 each include a gate or control terminal 120, 120, respectively. The apparatus further includes a pair of saturable magnetic cores 122 and 122', respectively, preferably constructed of a material presenting a substantially rectangular hysteresis characteristic. Two control windings 124, 126 are provided for the saturable magnetic cores 122 and 122', each of the two windings 124, 126 being common to both of the saturable magnetic cores 122 and 122'. windings 124, 126 are adapted to be energized with direct current control voltages to control the degree of saturation of saturable magnetic cores 122, 122. The control voltage across control winding 124 may be derived, for example, from the output voltage signal of transducer device 51 which monitors either the gas pressure or the gas flow in the hydrogen manifold 50, depending on the type of transducer device 51 which is used. The control voltage across control winding 126 for example, may be a signal derived from the current sensing device 55, FIG. 1, and diagrammatically shown as being connected by conductor means 77 to the feedback network to limit the direct current supplied by the power supply 14 to electrolysis cell 10 to maximum and minimum values. The minimum input current to cell 10 is set at a value which provides a minimum gas product rate sufficient to provide dilution of gas from leaks or gas migration from cavity across the capillary matrix 13 to cavity 18. In this way, a maximum gas purity in cavity 18 is maintained.
Upon conditions of low hydrogen gas demand, the gas generation rate may exceed the demand rate. This condition results in an increased hydrogen pressure which is relieved by regulator valve 79 connected to hydrogen manifold line 50, regulator valve 79 permitting the escape of hydrogen gas through relief conduit 81.
Connected in circuit with each of the solid state thyratron devices 100 and 100' is a gate winding 130, 130'. One end of each gate winding 130, 130' is connected to the terminal 104 or 104 of the secondary winding 106 and to anode terminal 102', 102 in series with a solid state rectifier 132, 132'. The opposite end of each gate winding 130, 130' is connected through a resistor 134, 134', to the gate or control element terminal 120, 120 of the solid state thyratron device 100, Each of the respective gate windings 130, 130' is mounted on or in magnetic association with one of the respective saturable cores 122, 122', respectively.
The control windings 124, 126 and the gate windings 130, 130 each are shown with a dot which indicates winding sense or polarity relationship.
In the operation of the apparatus of FIG. 2, assume that the alternating current power supply at transformer secondary winding terminals 104 and 104 has passed through zero potential and is beginning a half cycle which is positive relative to the anode terminal 102 of solid state device 100 and negative with respect to the anode terminal 102' of solid state device 100'. Under this condition, the solid state device 100 presents a high forward impedance since the control element 120 of solid state device 100 is nonenergized, and the solid state device 100' presents a high reverse impedance. Rectifier 132' blocks current flow through gate winding 130' of saturable core 122'. Gate winding 130 in the circuit of solid state device 100 presents a high impedance, since core 122 is not saturated at this instant and no power is applied across the load output terminals and 116. Current, however, will flow through the gate circuit of coil 130, i.e., through coil 130, resistor 134, gate terminal 120, through a portion of solid state device 100, cathode terminal 108, and across load terminals115, 116, back to center tap 118 of transformer secondary 106, to thereby carry the magnetic material of core 130 toward one level of saturation, the parameters of the gate circuit being selected to insure adequate current flow to effect this'performance.
At the instant core 122 saturates, the impedance of gate winding 130 abruptly drops with aconcomitant increase in current through gate winding 130. The abrupt current variation through gate winding 130 is applied as a control signal through resistor 134 to gate terminal of solid state device 100 to energize or fire the device 100 within a microsecond or less following saturation of core 122. When fired, the forward impedance of solid state device 100 abruptly drops very close to zero and the power supply is connected across load terminals 115, 116 through the remaining portion of the half cycle. The solid state device 100 when fired presents a substantially complete short circuit across gate winding and thereby terminates the control signal from gate winding 130 to gate terminal 120 of the solid state device l00. Thus, the arrangement for producing and applying a control signal to the gate terminal of the solid state device provides an automatic clipping or limiting operation which prevents application of a control signal of a magnitude which exceeds the design limitations of the solid state device.
Upon the next half cycle of applied alternating current voltage, when the input power of transformer sec- 9 ondary winding 106 is positive with respect to the anode terminal 102 of solid state device 100 and negative with respect to the anode terminal 102 of solid state device 100, the respective solid state devices 100 and 100' and the circuits associated therewith reverse their respective relationships from those described for the first half cycle of applied voltage. That is, the solid state device 100' now presents a high forward impedance and the solid state device-100 presents a high re-. verse impedance. The solid state device'100' becomes conductive or fires at a predetermined angular condition in the second half cycle of applied voltage in the same manner as described in connection with the solid state device lduringthefirst half cycle of applied voltage. When fired, the forward impedance of the solid state device 100' abruptly drops very close to zero and:the powersupply is'connectedacross the load ter-:
Other control systems which may be used instead of the phase angle shifting'system' of the U.S. Pat. No. 3,333,178 to Van Allen-etal, hereinbefore described,- are set-forth insprague Technical Paper'No. 63-9, published by Sprague Electric Company, North Adams, .Massachusetts, entitled The Silicon Con-- patented form of wide angle phase-shifting circuit con trolled by a saturable reactor. This special form offers a. full 180 rangeof linear phaseshift using a small (4 millwatt) direct current control'signaland provides a steeply rising gate pulsewhich tri'ggers the firing 'of'the thyratron type solid state device. This Silicontrol gate drive is manufactured and sold by-Sprague-Electric Company of North Adams, Massachusetts. Referring now to FIG. 3, there 'is shown an input transformer generally indicated at 150including a primary winding 152 to which is applied, forexample; 1 15 volt, 60'cycles per second alternating current-electric power; Transformer 150 includes a-secondary winding-154. Acrossthe terminals Band X of thetransformer secondary winding 154 is connected a fixed phaseshiftnetwork RC, which establishes a base linevoltage E across resistor R as shown in the vector; diagram of FIG. 4. Connected spond to the same unprirned letters of the circuit diagram of FIG. 3.
When the inductance of L is alter d slightly, the relative lengths of vectors A'P.', P'B" are effectively varied and if the angle 4) is made to stay constant, by careful design, the point P, will in effect, move around the dotted circle of the vector diagram of FIG; 4. A pulse forming network generally indicated in block diagram form at 156 in FIG. 3 is connectedacros's'the centertap terminal 0 of the transformer secondary 154 and also across the terminal Pwhich is the junction point between the inductance L and the capacitance C in the series'resonantnetwork across the resistance R.
By careful design, the circular locus isrnade to pass through the input potential point X on the vector diagram, and since angle X A B is a right angle, the vector'X'B' is a diameter of the circle'an'dthe input center tap'O' is at the-center'of the'circle.
The vector 0'? then represents an output that can be taken from the network, varyingin phase angle by approximately 300 while remaining constantin amplitude'e- Two silicon controlled rectifiersSCR No. 1 and SCR 7 No. 2 (not shown') may be connected to provide recti- 25 fied direct' current to'theelectrodes'llyl2 of cell 10, the magnitude of the current flow to cell 10 being con trolled during both half cycles of alternating current across transformer 150 by the circuit of FIG. 3. I
The inductor L takes the form of a specially designed saturable reactor 155 whose indu'ctanceis varied by saturating its core to a greater or less degree by passing: varying amounts of direct current through the control windings 1-2, 3-4. The output voltage across the terminals O, P, are formed into pulse" spikes the pulse forming network 156 which drives the coupling transformer generally indicated at 158. Due to theblocking action of the two output diodes 162A, 1628, the pulse" spikes are delivered on alternate half cycles from'terrninals G and 6,, which are each respectively connected to the'gate or control terminal of one of a'pair solid state thyratron devices,(not shown) which 'in this case across resistor R-is a series resonant circuit consisting of FIG. 4, the primed letters such as A'P, etc., correare the pair of silicon controlled rectifiers SCR No. l and SCR No. 2, the terrninalsK K, of the circuit of FIG. 3 being connected to the cathode terminals of the respective solid state. devices. The control windings l-2, 3-4, whichcontrol the degree of saturation of the saturable core reactor and hence control the value of the inductance L in the phase shift circuit, derive their signal voltages fromthe sources as set forth in the example of- FIGS. 1' and 2. For example; the voltage signal across control winding l-2 of FIG. 3 may be'the signal from the transducer device 51 indicating the gas pressure or flow'condition in the hydrogen manifold 50. The voltage signal across control winding 3-4.may be derived from the curr'ent transducer device 55 in current sensing relation to con ductoror cable 16 between the thyristor powersupply l4 and the electrode 12, to indicate the direct current flow to cell 10. It will be understood that the feedback and power} supply systems shown in FIGS. 2 and 3 are by way of example only and that other suitable types of feedback and power supply systems may be substitutedthe'refon;
It can be seen from the foregoing trimmers is provided in accordance with the invention an apparatus for and method of rnatchingthe gas generationrate V with the gas demand rate in an electrolysis systemby' measuring a demand function such as gas pressure or gas flow, and adjusting the input direct current to the electrodes of the electrolysis cell in accordance with the sensed demand function whereby to match the gas generation and demand rates. This matching of gas generation rate with gas demand rate results in important savings in the cost of electrical current input to the electrolysis cell.
It will also be noted that a very important advantage of the apparatus and method is that in sensing the gas pressure or gas flow and controlling the input current to the electrolysis cell as a function of the sensed gas pressure or gas flow as taught by the present invention, not only is the gas output of the cell varied in accordance with the varying gas demand rate of the external gas demanding load, but also automatic and inherent compensation is simultaneously made without further adjustment for such varying operating conditions as ambient temperature, module electrolyte phenomena, and long term aging characteristics of the electrolysis cell.
While there have been shown and described particular embodiments of the invention, it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the invention and, therefore, it is aimed to cover all such changes and modifications as fall within the true spirit and scope of the invention.
The embodiments of the invention in whichan exclusive property or privilege is claimed are defined as follows:
1. An electrolysis system for decomposing an electrolyte into at least one product gas, comprising an electrolysis cell having terminals and adapted to have an electrolyte therein, said cell being adapted to generate at least one product gas upon the connection of direct current across the terminals of said cell, the generation of said one product gas by said cell being a function of the direct current input to said cell, means in circuit relationship for supplying a variable direct current to said cell terminals whereby said one product gas is generated by said cell, means for sensing the flow rate of a product gas generated by said cell, and feedback network means coupled directly between said sensing means and said direct current supplying means for controlling the variable direct current input to said cell as a function of the condition sensed.
2. An electrolysis system as defined in claim 1 in which said condition sensed is the flow rate from said cell of said one product gas.
3. An electrolysis system as defined in claim 1 in which said means for supplying direct current to said cell comprises at least one thyratron type solid state device, and wherein said feedback network produces an output electrical signal that controls the load current conduction through said solid state device whereby to control the electrical current input to said cell.-
4. An electrolysis system for decomposing an electrolyte into at least one product gas, comprising an electrolysis cell having terminals and adapted to have an electrolyte therein, said cell being adapted to generate at least one product gas upon the connection of direct current across the terminals of said cell, the generation of said one product gas by said cell being a function of the direct current input to said cell, means in circuit relationship for supplying a variable direct current to said cell terminals whereby said one product gas is generated by said cell, means for sensing a condition of a product gas generated by said cell, feedback network 'means coupled'directly between said sensing means and said direct current supplying means for controlling the variable direct current input to said cell as a function of the condition sensed, and sensor means'connected in current sensing relation between said direct current supply means and said cell and connected to said feedback network means for limiting the maximum and minimum current supplied by said direct current supply means to said cell to predetermined maximum and minimum values.
5. The method of controlling the rate of gas generation in an electrolysis system of the type including an electrolysis cell in which at least one product gas is generated by said cell upon the connection of direct current to the terminals of said cell and in which the generation of said one product gas by said cell is a function of the direct current input to said cell, which comprises the steps of sensing the flow rate from said cell of said one product gas generated by said cell, and of controlling the direct current input applied to said cell as a function of the flow rate sensed whereby to control the rate of gas generation by said cell. t I t t
Claims (5)
1. An electrolysis system for decomposing an electrolyte into at least one product gas, comprising an electrolysis cell having terminals and adapted to have an electrolyte therein, said cell being adapted to generate at least one product gas upon the connection of direct current across the terminals of said cell, the generation of said one product gas by said cell being a function of the direct current input to said cell, means in circuit relationship for supplying a variable direct current to said cell terminals whereby said one product gas is generated by said cell, means for sensing the flow rate of a product gas generated by said cell, and feedback network means coupled directly between said sensing means and said direct current supplying means for controlling the variable direct current input to said cell as a function of the condition sensed.
2. An electrolysis system as defined in claim 1 in which said condition sensed is the flow rate from said cell of said one product gas.
3. An electrolysis system as defined in claim 1 in which said means for supplying direct current to said cell comprises at least one thyratron type solid state device, and wherein said feedback network produces an output electrical signal that controls the load current conduction through said solid state device whereby to control the electrical current input to said cell.
4. An electrolysis system for decomposing an electrolyte into at least one product gas, comprising an electrolysis cell having terminals and adapted to have an electrolyte therein, said cell being adapted to generate at least one product gas upon the connection of direct current across the terminals of said cell, the generation of said one product gas by said cell being a function of the direct current input to said cell, means in circuit relationship for supplying a variable direct current to said cell terminals whereby said one product gas is generated by said cell, means for sensing a conditiOn of a product gas generated by said cell, feedback network means coupled directly between said sensing means and said direct current supplying means for controlling the variable direct current input to said cell as a function of the condition sensed, and sensor means connected in current sensing relation between said direct current supply means and said cell and connected to said feedback network means for limiting the maximum and minimum current supplied by said direct current supply means to said cell to predetermined maximum and minimum values.
5. The method of controlling the rate of gas generation in an electrolysis system of the type including an electrolysis cell in which at least one product gas is generated by said cell upon the connection of direct current to the terminals of said cell and in which the generation of said one product gas by said cell is a function of the direct current input to said cell, which comprises the steps of sensing the flow rate from said cell of said one product gas generated by said cell, and of controlling the direct current input applied to said cell as a function of the flow rate sensed whereby to control the rate of gas generation by said cell.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US7225070A | 1970-09-15 | 1970-09-15 |
Publications (1)
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US00072250A Expired - Lifetime US3755128A (en) | 1970-09-15 | 1970-09-15 | Electrolysis system and method |
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Cited By (41)
Publication number | Priority date | Publication date | Assignee | Title |
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US3870616A (en) * | 1973-01-02 | 1975-03-11 | Gen Electric | Current controlled regulation of gas evolution in a solid polymer electrolyte electrolysis unit |
US3980053A (en) * | 1974-07-03 | 1976-09-14 | Beeston Company Limited | Fuel supply apparatus for internal combustion engines |
US4078985A (en) * | 1975-11-21 | 1978-03-14 | Nippon Soken, Inc. | Hydrogen generator |
US4539086A (en) * | 1983-08-31 | 1985-09-03 | Japan Storage Battery Company Limited | Oxygen concentration controlling method and system |
US4689133A (en) * | 1985-03-29 | 1987-08-25 | The Dow Chemical Company | Directly electrically coupled fuel cell-electrolysis cell system |
US4822469A (en) * | 1987-03-08 | 1989-04-18 | Stec Inc. | Electrical power supply for an electrolytic gas generator |
US5158656A (en) * | 1991-03-22 | 1992-10-27 | Electron Transfer Technologies, Inc. | Method and apparatus for the electrolytic preparation of group IV and V hydrides |
EP0766752A1 (en) * | 1994-04-12 | 1997-04-09 | OxyCell | Oxygen supply and removal apparatus |
US6024935A (en) * | 1996-01-26 | 2000-02-15 | Blacklight Power, Inc. | Lower-energy hydrogen methods and structures |
US6248221B1 (en) * | 1995-12-26 | 2001-06-19 | Randolph R. Davis | Electrolysis apparatus and electrodes and electrode material therefor |
WO2002008494A1 (en) * | 2000-07-20 | 2002-01-31 | Proton Energy Systems | Fan flow sensor for proton exchange membrane electrolysis cell |
US20030129117A1 (en) * | 2002-01-02 | 2003-07-10 | Mills Randell L. | Synthesis and characterization of a highly stable amorphous silicon hydride as the product of a catalytic hydrogen plasma reaction |
US6652732B2 (en) | 2000-07-20 | 2003-11-25 | Proton Energy Systems, Inc. | Fan flow sensor for proton exchange membrane electrolysis cell |
US20040095705A1 (en) * | 2001-11-28 | 2004-05-20 | Mills Randell L. | Plasma-to-electric power conversion |
US20040118348A1 (en) * | 2002-03-07 | 2004-06-24 | Mills Randell L.. | Microwave power cell, chemical reactor, and power converter |
US20040206024A1 (en) * | 2001-08-28 | 2004-10-21 | Wolfgang Graf | System comprising a glazing element and a gas supply device |
US20040247522A1 (en) * | 2001-11-14 | 2004-12-09 | Mills Randell L | Hydrogen power, plasma, and reactor for lasing, and power conversion |
US20050202173A1 (en) * | 2002-05-01 | 2005-09-15 | Mills Randell L. | Diamond synthesis |
US20050209788A1 (en) * | 2003-07-21 | 2005-09-22 | Mills Randell L | Method and system of computing and rendering the nature of the chemical bond of hydrogen-type molecules and molecular ions |
US20060088138A1 (en) * | 2004-04-07 | 2006-04-27 | Andre Jouanneau | Method and apparatus for the generation and the utilization of plasma solid |
US20060185987A1 (en) * | 2005-02-22 | 2006-08-24 | Sigma-Aldrich Co. | Integrated electrochemical reactor and process therefor |
US20060233699A1 (en) * | 2003-04-15 | 2006-10-19 | Mills Randell L | Plasma reactor and process for producing lower-energy hydrogen species |
US20070007127A1 (en) * | 2002-01-22 | 2007-01-11 | Proton Energy Systems, Inc. | Electrolysis Cell System with Cascade Section |
US20070198199A1 (en) * | 2004-07-19 | 2007-08-23 | Mills Randell L | Method and system of computing and rendering the nature of the chemical bond of hydrogen-type molecules and molecular ions |
US20070246373A1 (en) * | 2006-04-20 | 2007-10-25 | H2 Pump Llc | Integrated electrochemical hydrogen separation systems |
US20080034287A1 (en) * | 2004-05-17 | 2008-02-07 | Mills Randell L | Method and System of Computing and Rendering the Nature of the Excited Electronic States of Atoms and Atomic Ions |
US20080199744A1 (en) * | 2007-02-21 | 2008-08-21 | Samsung Electro-Mechanics Co., Ltd. | Hydrogen generating apparatus, fuel cell power generation system, method of controlling hydrogen generating quantity and recorded medium recorded program performing the same |
US20080213642A1 (en) * | 2007-02-21 | 2008-09-04 | Samsung Electro-Mechanics Co., Ltd. | Hydrogen generating apparatus and fuel cell power generation system controlling amount of hydrogen generation |
EP1970472A1 (en) * | 2007-03-16 | 2008-09-17 | Samsung Electro-mechanics Co., Ltd | Hydrogen generating apparatus and fuel cell power generation system controlling amount of hydrogen generation |
US20080304522A1 (en) * | 2006-04-04 | 2008-12-11 | Mills Randell L | Catalyst laser |
US20090107893A1 (en) * | 2007-10-26 | 2009-04-30 | Becton, Dickinson And Company | Deflection plate |
US20090123360A1 (en) * | 1997-07-22 | 2009-05-14 | Blacklight Power, Inc. | Inorganic hydrogen compounds |
US20090129992A1 (en) * | 1997-07-22 | 2009-05-21 | Blacklight Power, Inc. | Reactor for Preparing Hydrogen Compounds |
US20090142257A1 (en) * | 1997-07-22 | 2009-06-04 | Blacklight Power, Inc. | Inorganic hydrogen compounds and applications thereof |
US20090159454A1 (en) * | 2007-12-20 | 2009-06-25 | Air Products And Chemicals, Inc. | Divided electrochemical cell and low cost high purity hydride gas production process |
US20090177409A1 (en) * | 2004-01-05 | 2009-07-09 | Mills Randell L | Method and system of computing and rendering the nature of atoms and atomic ions |
US7773656B1 (en) | 2003-10-24 | 2010-08-10 | Blacklight Power, Inc. | Molecular hydrogen laser |
US20110104034A1 (en) * | 1997-07-22 | 2011-05-05 | Blacklight Power Inc. | Hydride compounds |
US8636881B2 (en) | 2010-07-12 | 2014-01-28 | Michael A. May | Integrated electrochemical reactor and process therefor |
US10214821B2 (en) | 2012-05-28 | 2019-02-26 | Hydrogenics Corporation | Electrolyser and energy system |
US10465302B2 (en) | 2014-08-07 | 2019-11-05 | Marathon Systems, Inc. | Modular gaseous electrolysis apparatus with actively-cooled header module, co-disposed heat exchanger module and gas manifold modules therefor |
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US1581944A (en) * | 1923-11-17 | 1926-04-20 | Hausmeister Paul | Production of compressed gases by electrolysis |
US3336215A (en) * | 1963-12-30 | 1967-08-15 | Continental Oil Co | Apparatus for the production of a gas by electrolysis including pressure responsive means for monitoring and controlling said electrolysis |
US3462356A (en) * | 1964-10-14 | 1969-08-19 | Catylators Ltd | Control of current in electrolytic apparatus |
US3485742A (en) * | 1967-05-10 | 1969-12-23 | Nat Distillers Chem Corp | Pressure responsive control circuit for an electrolysis-type hydrogen generator |
US3497312A (en) * | 1964-01-23 | 1970-02-24 | Us Navy | Atmosphere regeneration method for closed environmental vehicles |
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US1581944A (en) * | 1923-11-17 | 1926-04-20 | Hausmeister Paul | Production of compressed gases by electrolysis |
US3336215A (en) * | 1963-12-30 | 1967-08-15 | Continental Oil Co | Apparatus for the production of a gas by electrolysis including pressure responsive means for monitoring and controlling said electrolysis |
US3497312A (en) * | 1964-01-23 | 1970-02-24 | Us Navy | Atmosphere regeneration method for closed environmental vehicles |
US3462356A (en) * | 1964-10-14 | 1969-08-19 | Catylators Ltd | Control of current in electrolytic apparatus |
US3485742A (en) * | 1967-05-10 | 1969-12-23 | Nat Distillers Chem Corp | Pressure responsive control circuit for an electrolysis-type hydrogen generator |
Cited By (56)
Publication number | Priority date | Publication date | Assignee | Title |
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US3870616A (en) * | 1973-01-02 | 1975-03-11 | Gen Electric | Current controlled regulation of gas evolution in a solid polymer electrolyte electrolysis unit |
US3980053A (en) * | 1974-07-03 | 1976-09-14 | Beeston Company Limited | Fuel supply apparatus for internal combustion engines |
US4078985A (en) * | 1975-11-21 | 1978-03-14 | Nippon Soken, Inc. | Hydrogen generator |
US4539086A (en) * | 1983-08-31 | 1985-09-03 | Japan Storage Battery Company Limited | Oxygen concentration controlling method and system |
US4689133A (en) * | 1985-03-29 | 1987-08-25 | The Dow Chemical Company | Directly electrically coupled fuel cell-electrolysis cell system |
US4822469A (en) * | 1987-03-08 | 1989-04-18 | Stec Inc. | Electrical power supply for an electrolytic gas generator |
US5158656A (en) * | 1991-03-22 | 1992-10-27 | Electron Transfer Technologies, Inc. | Method and apparatus for the electrolytic preparation of group IV and V hydrides |
EP0766752A4 (en) * | 1994-04-12 | 1997-09-17 | Oxycell | Oxygen supply and removal apparatus |
EP0766752A1 (en) * | 1994-04-12 | 1997-04-09 | OxyCell | Oxygen supply and removal apparatus |
US6248221B1 (en) * | 1995-12-26 | 2001-06-19 | Randolph R. Davis | Electrolysis apparatus and electrodes and electrode material therefor |
US6024935A (en) * | 1996-01-26 | 2000-02-15 | Blacklight Power, Inc. | Lower-energy hydrogen methods and structures |
US20110104034A1 (en) * | 1997-07-22 | 2011-05-05 | Blacklight Power Inc. | Hydride compounds |
US20090123360A1 (en) * | 1997-07-22 | 2009-05-14 | Blacklight Power, Inc. | Inorganic hydrogen compounds |
US20090129992A1 (en) * | 1997-07-22 | 2009-05-21 | Blacklight Power, Inc. | Reactor for Preparing Hydrogen Compounds |
US20090142257A1 (en) * | 1997-07-22 | 2009-06-04 | Blacklight Power, Inc. | Inorganic hydrogen compounds and applications thereof |
WO2002008494A1 (en) * | 2000-07-20 | 2002-01-31 | Proton Energy Systems | Fan flow sensor for proton exchange membrane electrolysis cell |
US6652732B2 (en) | 2000-07-20 | 2003-11-25 | Proton Energy Systems, Inc. | Fan flow sensor for proton exchange membrane electrolysis cell |
US7774997B2 (en) * | 2001-08-28 | 2010-08-17 | Interpane Entwicklungs-Und Beratungsgesellschaft Mbh & Co. Kg | System comprising a glazing element and a gas supply device |
US20040206024A1 (en) * | 2001-08-28 | 2004-10-21 | Wolfgang Graf | System comprising a glazing element and a gas supply device |
US20040247522A1 (en) * | 2001-11-14 | 2004-12-09 | Mills Randell L | Hydrogen power, plasma, and reactor for lasing, and power conversion |
US20090196801A1 (en) * | 2001-11-14 | 2009-08-06 | Blacklight Power, Inc. | Hydrogen power, plasma and reactor for lasing, and power conversion |
US20040095705A1 (en) * | 2001-11-28 | 2004-05-20 | Mills Randell L. | Plasma-to-electric power conversion |
US20090068082A1 (en) * | 2002-01-02 | 2009-03-12 | Blacklight Power, Inc. | Synthesis and characterization of a highly stable amorphous silicon hydride as the product of a catalytic hydrogen plasma reaction |
US20030129117A1 (en) * | 2002-01-02 | 2003-07-10 | Mills Randell L. | Synthesis and characterization of a highly stable amorphous silicon hydride as the product of a catalytic hydrogen plasma reaction |
US20070007127A1 (en) * | 2002-01-22 | 2007-01-11 | Proton Energy Systems, Inc. | Electrolysis Cell System with Cascade Section |
US20040118348A1 (en) * | 2002-03-07 | 2004-06-24 | Mills Randell L.. | Microwave power cell, chemical reactor, and power converter |
US20050202173A1 (en) * | 2002-05-01 | 2005-09-15 | Mills Randell L. | Diamond synthesis |
US20060233699A1 (en) * | 2003-04-15 | 2006-10-19 | Mills Randell L | Plasma reactor and process for producing lower-energy hydrogen species |
US20050209788A1 (en) * | 2003-07-21 | 2005-09-22 | Mills Randell L | Method and system of computing and rendering the nature of the chemical bond of hydrogen-type molecules and molecular ions |
US7188033B2 (en) | 2003-07-21 | 2007-03-06 | Blacklight Power Incorporated | Method and system of computing and rendering the nature of the chemical bond of hydrogen-type molecules and molecular ions |
US7773656B1 (en) | 2003-10-24 | 2010-08-10 | Blacklight Power, Inc. | Molecular hydrogen laser |
US20090177409A1 (en) * | 2004-01-05 | 2009-07-09 | Mills Randell L | Method and system of computing and rendering the nature of atoms and atomic ions |
US20060088138A1 (en) * | 2004-04-07 | 2006-04-27 | Andre Jouanneau | Method and apparatus for the generation and the utilization of plasma solid |
US7689367B2 (en) | 2004-05-17 | 2010-03-30 | Blacklight Power, Inc. | Method and system of computing and rendering the nature of the excited electronic states of atoms and atomic ions |
US20080034287A1 (en) * | 2004-05-17 | 2008-02-07 | Mills Randell L | Method and System of Computing and Rendering the Nature of the Excited Electronic States of Atoms and Atomic Ions |
US20070198199A1 (en) * | 2004-07-19 | 2007-08-23 | Mills Randell L | Method and system of computing and rendering the nature of the chemical bond of hydrogen-type molecules and molecular ions |
US20060185987A1 (en) * | 2005-02-22 | 2006-08-24 | Sigma-Aldrich Co. | Integrated electrochemical reactor and process therefor |
US7767066B2 (en) | 2005-02-22 | 2010-08-03 | Michael A. May | Integrated electrochemical reactor and process therefor |
US20080304522A1 (en) * | 2006-04-04 | 2008-12-11 | Mills Randell L | Catalyst laser |
US20070246373A1 (en) * | 2006-04-20 | 2007-10-25 | H2 Pump Llc | Integrated electrochemical hydrogen separation systems |
US8551302B2 (en) | 2007-02-21 | 2013-10-08 | Samsung Electro-Mechanics Co., Ltd. | Hydrogen generating apparatus and fuel cell power generation system controlling amount of hydrogen generation |
US20080199744A1 (en) * | 2007-02-21 | 2008-08-21 | Samsung Electro-Mechanics Co., Ltd. | Hydrogen generating apparatus, fuel cell power generation system, method of controlling hydrogen generating quantity and recorded medium recorded program performing the same |
US20080213642A1 (en) * | 2007-02-21 | 2008-09-04 | Samsung Electro-Mechanics Co., Ltd. | Hydrogen generating apparatus and fuel cell power generation system controlling amount of hydrogen generation |
US7879205B2 (en) * | 2007-02-21 | 2011-02-01 | Samsung Electro-Mechanics Co., Ltd. | Hydrogen generating apparatus, fuel cell power generation system, method of controlling hydrogen generating quantity and recorded medium recorded program performing the same |
EP1970472A1 (en) * | 2007-03-16 | 2008-09-17 | Samsung Electro-mechanics Co., Ltd | Hydrogen generating apparatus and fuel cell power generation system controlling amount of hydrogen generation |
US20090107893A1 (en) * | 2007-10-26 | 2009-04-30 | Becton, Dickinson And Company | Deflection plate |
US7880108B2 (en) * | 2007-10-26 | 2011-02-01 | Becton, Dickinson And Company | Deflection plate |
US20090159454A1 (en) * | 2007-12-20 | 2009-06-25 | Air Products And Chemicals, Inc. | Divided electrochemical cell and low cost high purity hydride gas production process |
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US9738982B2 (en) | 2007-12-20 | 2017-08-22 | Versum Materials Us, Llc | Divided electrochemical cell and low cost high purity hydride gas production process |
US8636881B2 (en) | 2010-07-12 | 2014-01-28 | Michael A. May | Integrated electrochemical reactor and process therefor |
US10214821B2 (en) | 2012-05-28 | 2019-02-26 | Hydrogenics Corporation | Electrolyser and energy system |
US10435800B2 (en) | 2012-05-28 | 2019-10-08 | Hydrogenics Corporation | Electrolyser and energy system |
US11268201B2 (en) | 2012-05-28 | 2022-03-08 | Hydrogenics Corporation | Electrolyser and energy system |
US11761103B2 (en) | 2012-05-28 | 2023-09-19 | Hydrogenics Corporation | Electrolyser and energy system |
US10465302B2 (en) | 2014-08-07 | 2019-11-05 | Marathon Systems, Inc. | Modular gaseous electrolysis apparatus with actively-cooled header module, co-disposed heat exchanger module and gas manifold modules therefor |
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