DK181123B1 - An electrolysis system - Google Patents

An electrolysis system Download PDF

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Publication number
DK181123B1
DK181123B1 DKPA202100068A DKPA202100068A DK181123B1 DK 181123 B1 DK181123 B1 DK 181123B1 DK PA202100068 A DKPA202100068 A DK PA202100068A DK PA202100068 A DKPA202100068 A DK PA202100068A DK 181123 B1 DK181123 B1 DK 181123B1
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Prior art keywords
chamber
electrolyte solution
electrolysis
cathode
outlet
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DKPA202100068A
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Danish (da)
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Stiesdal Henrik
Schibsbye Karsten
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Stiesdal Hydrogen As
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Priority to DKPA202100068A priority Critical patent/DK181123B1/en
Priority to PCT/DK2022/050010 priority patent/WO2022156869A1/en
Publication of DK202100068A1 publication Critical patent/DK202100068A1/en
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Publication of DK181123B1 publication Critical patent/DK181123B1/en

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/083Separating products
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/02Process control or regulation
    • C25B15/021Process control or regulation of heating or cooling
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/085Removing impurities
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087Recycling of electrolyte to electrochemical cell
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60Constructional parts of cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60Constructional parts of cells
    • C25B9/67Heating or cooling means
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70Assemblies comprising two or more cells
    • C25B9/73Assemblies comprising two or more cells of the filter-press type
    • C25B9/75Assemblies comprising two or more cells of the filter-press type having bipolar electrodes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70Assemblies comprising two or more cells
    • C25B9/73Assemblies comprising two or more cells of the filter-press type
    • C25B9/77Assemblies comprising two or more cells of the filter-press type having diaphragms
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

An electrolysis system for production of hydrogen and/or oxygen comprising a stack of electrolysis cells inside a pressure vessel. Each electrolysis cell in the stack comprises a membrane and a cassette made of a bipolar plate sandwiched by a cathode and an anode forming a cathode compartment and an anode compartment on each side of the bipolar plate. The cassette has an inlet for water and an outlet for hydrogen. The inlet and/or outlet may be arranged with fluid separation means and cooling means may cool the electrolyte solution in order to reduce generation of electrolyte vapor so that together with the separation means the escape of electrolyte solution from a cassette is reduced such that the cells have a higher degree of electrical insulation for reducing cross currents.

Description

DK 181123 B1 1 An electrolysis system
DESCRIPTION The present disclosure relates to an electrolysis system for production of hydrogen by electrolysis of water preferably using an alkali electrolyte such as potassium hydroxide. In particular, it relates to an electrolysis system as per the preamble of the independent claim.
During operation of prior art systems, hydrogen released at the cathode rises upwards and the released gas together with increasing temperature causes electrolyte solution in liquid and vapor form to rise upwards as well. Electrolyte solution may therefore exit together with hydrogen gas.
An example is disclosed in US2014/069808. The electrolyser therein is provided modu- lar, each module comprising a structural plate that defines a degassing chamber and a half cell chamber opening. External reinforcing means contact the structural plate for mitigating outward displacement of the structural plate in response to fluid pressure within the structural plate. The structural plate and the external reinforcing means define interlocking features for achieving contact and corresponding mechanical reinforce- ment. Electrolyte flows through a passage of the structural plate into a canal, which then with added water flows back through a second passage. Accordingly, gas and electro- lyte are not separated.
When using a strong bases as electrolyte the circulation and cooling of electrolyte solu- tion sets higher demands to the hardware used for the cooling and circulation, and it reduces how much voltage that can be applied across the stack of electrolysis cells.
It is an object of the present invention to dispense with pumps and extensive pipeline routing outside of the stack, and achieve a higher degree of electrical insulation between electrolysis cells of the stack such that the voltage can be increased thereby increasing the energy conversion efficiency.
The above object and advantages together with numerous other objects and ad- vantages, which will be evident from the description of the present invention, are
DK 181123 B1 2 achieved by an electrolysis system for production of hydrogen as defined in the inde- pendent claim. Cooling means are arranged for transferring heat away from said electrolyte solution in said cathode compartment. The invention will now be explained in more detail below by means of examples with reference to the accompanying drawings.
The invention may, however, be embodied in different forms than depicted below, and should not be construed as limited to any examples set forth herein. Rather, any exam- ples are provided so that the disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like reference numerals refer to like elements throughout. Like elements will, thus, not be described in detail with respect to the description of each figure.
Fig. 1 shows a cutaway view of an electrolysis system 10 producing hydrogen during intended use of the system.
The electrolysis system comprises a plurality of electrolysis cassettes including a first electrolysis cassette 12.
The plurality of electrolysis cassettes are stacked next to each other along the length of the electrolysis system (along the longitudinal axis X) and constitute a stack of elec- trolysis cassettes.
The hydrogen is produced by decomposing water, and oxygen is therefore released as well. The electrolysis system may be used for other types of electrolysis.
Each cassette comprises a cathode compartment having a cathode and an anode compartment having an anode.
A cassette may be made as a bipolar plated sandwiched by a first electrode plate con- stituting the cathode, and a second electrode plate constituting the anode.
DK 181123 B1 3 The stack is stacked so that an anode compartment of a respective cassette is fol- lowed by the cathode compartment of the next cassette in the stack — membranes (not shown) are between each cassette.
Alternatively, the stack may be arranged such that cathode and anode are across from each other and the cathodes are along a line parallel with the anodes. Such a stacking requires more use of material for the cells.
The stack may be sandwiched by a pair of terminals, one terminal at each end of the stack. Each terminal may be an aluminum plate.
A DC voltage may be applied across the terminals thereby establishing an electric field through the stack. The voltage may be in the low voltage (75 to 1500 volt DC) or me- dium voltage (more than 1500 volt DC), and a preferred voltage may be 850 volt DC.
When the potential is applied, current is directed from the plus potential (anode) to mi- nus potential (cathode), and electrons vice versa. Electrons enter the electrolysis solu- tion at the cathode where hydrogen is released, and hydroxide ions flow from the cath- ode compartment in one cassette to the anode compartment in the neighboring cas- sette.
Electrolysis takes place in each cassette of the stack except for the compartment adja- cent the terminal at the first end of the stack and the compartment adjacent the termi- nal at the other end of the stack.
The hydrogen exits from the system/stack in two pipelines 14a, 14b, i.e. a first hydro- gen pipeline 14a exiting from the front of the system, and a second hydrogen pipeline 14b exiting from the back of the system, and being led to the front.
A single pipeline may be used to transport hydrogen from the system. However, with two pipelines the diameter of the pipelines can be smaller compared to just having one pipeline.
Similarly, the oxygen exits from the system in two pipelines 16a, 16b, i.e. a first oxygen pipeline 16a exiting from the front of the system, and a second oxygen pipeline 16b exiting from the back of the system, and being led to the front.
DK 181123 B1 4 The plus and minus terminal may be interchanged such that the direction of the elec- tric field between the pair of terminals may be switched. In this way the anodes and cathodes may be interchanged such that the wear on the cathodes may be reduced.
The switching may be arranged in time intervals such that in a first time interval, the electric field is directed opposite the direction of the electric field in a second time inter- val.
A three way valve may be arranged at the outlets from the stack to control the flow of hydrogen and oxygen out of the stack so that the hydrogen and oxygen and directed to the intended pipelines in order to transport the hydrogen and oxygen away from the stack. Water may be led to each cassette by a supply line 17. From the supply line 17, branch lines may extend up to each cassette. The stack is inside a pressure vessel 18. The pressure vessel constitutes a container arranged to hold a fluid (gas or liquid) at a pressure substantially different from the am- bient pressure. This allows for the stack to be pressurized such that the hydrogen may exit as pressurized gas, and the oxygen may as well exit as pressurized gas. A regulator 19 such as a pump or valve may be used to regulate the pressure inside the pressure vessel.
A preferred pressure may be 35 bar or 100 bar (such as 10 to 200 bar or 20 to 150 bar), and the pressure may be regulated with +/- 0.1 bar. A pressure sensor (not shown) such as a pressure gauge may be placed on any of the pipelines leading hydrogen or oxygen from the electrolysis system. In this way the pressure of for example the hydrogen may be measured, and a feedback to the regu- lator 19 may be provided for regulating the pressure inside the pressure vessel, i.e. if the pressure sensor shows an increased pressure of the hydrogen, the regulator may increase the pressure inside the pressure vessel such that the pressure in the pres- sure vessel corresponds to the pressure in the pipeline or vice versa.
DK 181123 B1 Instead of a pressure vessel, the stack could be placed at normal air pressure (stand- ard atmosphere pressure), and a pump could be used to pressurize the hydrogen gas exiting from the electrolysis system for providing pressurized hydrogen.
5 Inthe figure, four additional pipelines are shown. These may be used as cooling pipe- lines extending trough the inside of each cassette such that the electrolyte solution may come in direct contact with a cooling pipeline.
A first cooling pipeline 20a may transports cooling fluid into the stack at the bottom at the first end of the stack.
A second cooling pipeline 20b may transports cooling fluid into the stack at the bottom at the second end of the stack.
As an alternative, one pipeline may be used to transport cooling fluid into the stack. Using two cooling pipelines into the stack provides a more efficient cooling compared to one pipeline with the same diameter.
The cooling fluid exits from the stack via a third cooling pipeline 20c exiting at the top atthe first end of the stack.
The cooling fluid also exits from the stack via a fourth cooling pipeline 20d exiting at the top at the second end of the stack.
The pipelines may be interchanged, i.e. cooling fluid may enter into a cassette at the top of the cassette instead of at the bottom.
Alternatively, the stack may be cooled by cooling fluid being put in motion inside the pressure vessel, for example by having a pump (not shown) for pumping cooling fluid around inside the pressure vessel.
Such a cooling fluid may be air or a liquid not prone to electrolysis such that electroly- sis out in the pressure vessel can be avoided. It may also be hydrogen gas released from the cells in the stack during operation of the electrolysis system.
DK 181123 B1 6 The stack may be assembled and placed in a first frame for supporting the stack. The stack may be held together in the longitudinal direction by a number of nuts and bolts. This may ensure a seal such that electrolysis solution does not exit into the pressure vessel.
The pressure vessel may comprise a second frame for supporting the assembly of the stack and first frame. The pressure vessel may be constructed as a steel pipe or glass fiber, and may have a hemispherical shaped steel plate at each end.
Fig. 2 shows an example of a cathode or anode, i.e. electrode in the form of an elec- trode plate 30.
The details explained below regarding the electrode may be the same whether the electrode is a cathode or an anode, i.e. whether the electrode is an anode or cathode depends on the direction of an applied electric field through the stack.
The electrode plate may be of stainless steel with a thickness of about 0.5 mm (such as between 0.1 mm to 1 cm, or 0.1 to 2 mm), and may be embossed into a shape such that it defines a volume 32 for an electrolyte solution.
The embossing operation may be accomplished with a combination of pressure and heat or pressure alone. Hereby may be formed a depression in the plate.
The area 34 extending along the edge of the plate and about 5 mm inwards (such as 1 to 15 mm) from the edge may be planar and may be used as a contact area for estab- lishing an electric connection to a bipolar plate (not shown), which may be welded to the electrode plate (for providing transport of electrons between the cathode and an- ode), i.e. such that the anode and cathode are galvanic connected, preferably via the bipolar plate.
Additional electrical connections may be provided inside the volume such as a first ridge 36a and optionally a second ridge 36b. Additional electrical connections, or a greater area 34 may provide for higher current.
DK 181123 B1 7 A ridge may be provided by pressing the electrode plate with a die having a depres- sion corresponding to the inverse of the ridge. An additional electrical connection may also be formed by welding a spacer at a posi- tion inside the volume. The electrical connection (ridge or spacer) may have a height such that it will contact the bipolar plate connected to the electrode plate.
The electrode plate has perforations including a first perforation 37 for the flow of ions through the perforations. The electrolysis reaction takes place at the perforations. Each perforation may be made by laser cutting (such as flying cut), and may extend horizontally as shown in the figure, or it may extend vertically. Alternatively, the perfo- rations may be punched out, and they may have shapes other than as rectangular ap- ertures, such as round, star shaped or elliptical.
The figure illustrates four areas having perforations. There may be more or less than four areas with perforations.
A third ridge 38 may form a loop inside the volume and define a second volume or channel 40 constituting a cooling channel. The cooling channel may extend from the bottom of the electrode plate to the top.
As an alternative or supplement to extending through the compartment/volume defined by the electrode, the cooling channel may extend between a pair of bipolar plates, which may be arranged between the cathode and anode, or it may extend between two cells.
The electrode may comprise an opening 42 constituting a cooling inlet for transporting cooling fluid into the cooling channel from a cooling pipeline leading cooling fluid to the system.
The electrode may comprise an opening 44 constituting a cooling outlet for transport- ing cooling fluid out from the cooling channel 40.
DK 181123 B1 8 Alternatively, the cooling fluid may enter at the opening at the top and exit at the open- ing at the bottom of the electrode plate. The third ridge may also function as an electrical connection to a bipolar plate con- nected to the electrode plate. A fourth ridge 47 may be placed adjacent the third ridge such that a passage 48 con- stituting a cooling passage may be defined between the third ridge and the fourth ridge.
The cooling passage 48 extends in an area of the electrode plate without perforations such that no electrolysis takes place in the cooling passage. The arrows illustrated in fig. 2 shows the flow of electrolyte solution during operation.
As electrolysis takes place at a respective perforation, the released gas will rise up- wards towards the top of the electrode plate. The cooling passage 48 allows for the electrolyte solution to be cooled when it passes through the cooling passage back down towards the bottom of the plate. The cooling channel 40 may be at an offset with respect to the centerline of the elec- trode plate. The cooling passage may be cooled from the bipolar plate, due to a sec- ond cooling channel of the second electrode plate on the other side of the bipolar plate —the second electrode plate being turned 180 degrees around a vertical centerline. In the stack, the backside of the electrode plate 30 will face a backside of a third elec- trode plate (turned 180 degrees around a vertical centerline), and the cooling passage may also be cooled by the cooling channel of the third electrode, i.e. cooled from the backside. In total, the cooling passage 48 may be cooled from one, two or up to three sides. The fourth ridge may also function as an electrical connection to a bipolar plate con- nected to the electrode plate.
DK 181123 B1 9 The backside of the electrode plate, i.e. the side opposite the inner side of the elec- trode plate where the ridges are, may have an recess 51 extending 360 degrees around the perforations — the recess will in effect appear as a ridge when seen from the inside of the volume, but the ridge being lower than the other ridges described above. A gasket such as an O-ring may be placed in the recess. As an alternative to using an O-ring in a recess, glue or a liquid gasket may be used to ensure a seal.
The plate may have an opening 46 constituting a gas outlet for transporting released gas out of the volume 32. The gas outlet may be placed at the top of the electrode plate, optionally at a corner of electrode plate.
The plate may comprise a separator for separating any electrolyte solution mixed with the released gas for reducing the amount of electrolyte solution exiting with the re- leased gas.
The separator may comprise a fifth ridge 49 may define a passage 50 for leading re- leased gas towards the gas outlet. The passage 50 may be between the fifth ridge and the top of the electrode plate.
The highest point on the fifth ridge 52 may be positioned higher than the gas outlet.
The fifth ridge may extend from the gas outlet with an angle such as an angle between 0 to 30 degrees for forcing electrolyte solution downwards.
The fifth ridge may also function as an electrical connection to a bipolar plate con- nected to the electrode plate.
The figure shows an opening 54 constituting a gas outlet for transporting gas released from the other electrode of the cassette. The volume 32 is not in fluid communication with the opening 54. The opening 54 is placed at a corner opposite the opening 46.
DK 181123 B1 10 The electrode plate may have an opening 56a constituting a water inlet for transporting water into the volume 32. The water inlet may be placed at the bottom of the electrode plate.
Alternatively, the water inlet may be arranged at the top of the electrode plate such as above the surface of the electrolyte solution such that water may be added by dripping down into the electrolyte solution.
It may be measured by means of a sensor such as a flow sensor, how much gas is produced by the electrolysis system or in an electrode compartment in order to add a corresponding amount of water.
Alternatively, a sensor such as a level sensor or pressure sensor (at the bottom of the compartment for example) may measure the level of the electrolyte solution for deter- mining the amount of electrolyte solution in the compartment.
The surface of the electrolyte solution may refer to when the electrolysis plant is at standstill and not operating.
An additional water inlet 56b may be provided.
Fig. 3 shows another example of an electrode plate. The plate has four areas with perforations where electrolysis takes place. There may be more or less than four areas with perforations.
Ridges 58a,b,c extend between the areas. The ridges constitute electric connections to a bipolar plate as explained in more detail in connection with fig. 2.
Contrary to the plate shown in fig. 2, the plate of fig. 3 does not have an internal chan- nel for a flow of cooling fluid. Instead the plate has a ridge 60a adjacent an edge 61a of the plate for defining a passage 62a. The passage may be between the ridge and the edge.
The edge 61a is a vertical arranged edge, extending from top to bottom of the plate.
DK 181123 B1 11 The ridge 60a may also function as an electrical connection to a bipolar plate con- nected to the electrode plate. The passage is without perforations. The electrolyte solution may flow upwards at the four areas with electrolysis and circulate back down in the passage. Since the passage is at the edge, the electrolyte solution may release heat at the edge and be cooled. The effect may be increased by having a flow of cooling fluid outside the plate at the edge.
The plate may have a ridge 60b adjacent an edge 61b opposite the edge 61a for defin- ing a passage 62b. The passage may be between the ridge and the edge.
The ridge 60b may also function as an electrical connection to a bipolar plate con- nected to the electrode plate.
The passage is without perforations. The electrolyte solution may flow upwards at the four areas with electrolysis and circulate back down in the passage.
The ridge 60b may also function as an electrical connection to a bipolar plate con- nected to the electrode plate.
The “internal” cooling shown in fig. 2, i.e. defined by the ridge 32 and openings 42, 44 may be included in the plate of fig. 3.
The plate shown in fig. 3 comprises an opening 56 constituting a water inlet for trans- porting water into the volume 32. The water inlet may be placed at the bottom of the plate.
The plate may comprise a separator for stopping flow of electrolyte solution out through the water inlet, for example in the case where the electrolyte solution is heav- ier than water.
The separator may comprise a first ridge 64, which may define a first passage 66 for leading water from the water inlet and through the passage into the volume 32.
DK 181123 B1 12 The first passage 66 may be between the first ridge and the bottom of the electrode plate, i.e. part of the first passage is below the water inlet. The first ridge may have an end 68 defining an outlet from the first passage leading the water out into the volume.
A second ridge 70 may be placed above the first ridge 64 and defining a second pas- sage 72 between the ridges 64, 70.
Inthe second passage 72, the water flow may be in the opposite direction than the wa- ter flow in the first passage 66. The first ridge and/or the second ridge may also function as an electrical connection to a bipolar plate connected to the electrode plate.
Fig. 4 shows an exploded view of parts of a stack of an electrolysis system. The parts in fig. 4 are shown along a bend line for illustrative purpose. An electrode plate 30 as described in connection with fig. 2 is shown to the left of a bi- polar plate 74. The electrode plate constitutes a cathode. The depression in the cathode forms a volume, which is enclosed when the bipolar plate is connected to the cathode for example by welding along the edge of the cath- ode.
The volume enclosed by the cathode and the bipolar plate may constitute a cathode compartment. The electrolysis takes place at the perforations of the electrode plate. The openings (inlets and outlets into the volume) may be sealed by gaskets.
An electrolyte solution is illustrated in the volume with the surface 76. The electrolyte solution may cover the highest placed perforation in the cathode, and the surface of the electrolyte solution may be below the gas outlet 46, i.e. the volume is partly filled with electrolyte solution for preventing that the electrolyte solution flows out of the gas outlet — the electrolyte solution may occupy a volume of the cathode
DK 181123 B1 13 compartment such that the hydrogen gas exiting from the hydrogen outlet is mixed with less than 10 % electrolyte solution in vapor state, such as 5 % or 1 %. The passage 50 may be provided to increase the separation so that a larger part of the cathode compartment can be filled with electrolyte solution. The electrolyte solution may be water or water mixed with a base such as potassium hydroxide (KOH). Instead of embossing the electrode plate, the bipolar plate may be embossed such that a depression in the bipolar plate forms the volume for the electrolyte solution. The ridges of the electrode plate may in that case be on the bipolar plate, and the electrode plate may be planar/flat — except for any recess for a gasket.
The area for perforations on the electrode plate may be increased when it is the bipo- lar plate that is embossed. To the right of the bipolar plate is shown a second electrode plate constituting an an- ode 78. The anode may be a copy of the cathode, and turned 180 degrees around a vertical axis. Like the cathode, the depression in the anode forms a volume, which may be enclosed when put together with the bipolar plate, thus forming an anode compartment.
As for the cathode, the electrolyte solution has a surface 79 below the gas outlet 80. Instead of embossing the anode, two bipolar plates may be provided and embossed such that a depression in the first bipolar plate may form the volume for the electrolyte solution of the cathode as explained above, and a depression in the second bipolar plate may form the volume for the electrolyte solution of the anode. The ridges of the anode plate may in that case be on the second bipolar plate. When using two bipolar plates, cooling fluid may be introduced between the two bipo- lar plates for cooling the anode and cathode compartments respectively. In this way, the entire area of electrode plates may be used for perforations.
DK 181123 B1 14 It is contemplated that the cassette comprises the cathode 30, bipolar plate 74, and anode 78.
A compartment/electrode plate may be arranged such that the electrolyte solution will circulate substantially around an axis parallel to the longitudinal axis X of the stack. “Substantially” meaning that more electrolyte solution circulate around the axis parallel to the longitudinal axis than around axis with other directions. For example, the depth of the compartment may be so that the electrolysis solution will have such a circula- tion, i.e. a narrow compartment may be formed for forcing the electrolyte solution to circulate in such a way. An electrode plate may have a width of about 1 m (such as between 0.3 to 2 m), and it may have a height of 1 m (such as between 0.5 to 2 m).
The electrode plates may be embossed to a depth such that the length/total depth of the cassette (from the backside of the cathode to the backside of the anode) is about 4 mm (such as between 1 mm to 20 mm, or 1 mm to 10 mm) — given a plate thickness of about 0.5 mm.
Such dimensions of an electrode plate also provides that a high number of cassettes may be stacked together while applying a high voltage as possible across the stack. Between the cassettes in the stack are membranes, i.e. in fig. 4 is shown a membrane 82atothe left of the cassette, and a membrane 82b to the right of the cassette. Each membrane between neighboring cassettes may be an electrical insulator for electrically insulating neighboring cassettes.
An electrolysis cell includes a cassette and a membrane. The membrane is permeable to flow of ions such that the ions may flow through the membrane from the compartment on the first side of the membrane to the compart- ment on the other side of the membrane.
DK 181123 B1 15 The membrane may be hydrophile, and it may be made of cotton, Aramid, Teflon or PES. Fig. 5 shows a second exploded view of part of a stack. In total, five cassettes are il- lustrated in the view.
During electrolysis, ions will flow between an anode compartment 78b and a cathode compartment 30, through membrane 82a.
Likewise ions will flow between a anode compartment 30b, and a cathode compart- ment 78, through membrane 82b. The combined volume of anode compartment 78b and cathode compartment 30 con- stitutes a sealed volume having an electrolyte solution. A gasket on the backside of the electrode plate constituting the cathode compartment 30 may press against the electrode plate constituting the anode compartment 78b for sealing the combined vol- ume. The electrode plate constituting the anode compartment may also have a gasket on its backside.
Arrow 84 illustrates the transport of hydrogen gas out from the cathode compartments, while arrow 86 illustrates the transport of oxygen out from the anode compartments. The cassette constituted by anode 30, bipolar plate 74, and cathode 78 is illustrated as being in the center of the stack. For the cassettes to the left of this center cassette, the gas is transported to the left, and for the cassettes to the right of this center cassette, the gas is transported to the left. Fig. 6 shows a perspective of a stack in a frame.
A pressure vessel is not shown in the figure. Each electrode plate used in the stack may correspond to the electrode plate de- scribed in connection with fig. 3, i.e. each electrode plate has a water inlet at the bot- tom of the electrode plate, and a separator element for preventing electrolyte solution to flow out through the water inlet.
DK 181123 B1 16 The outlet of oxygen from the stack is in fluid communication with a container 86 con- stituting an oxygen container. The oxygen container may be flexible such that it can expand and increase its volume or contract such that it can decrease its volume, i.e. act as a buffer for storing a volume of oxygen for facilitating a regulation of the pres- sure in the stack, because it is desirable that the hydrogen and oxygen is at substan- tially the same pressure. The oxygen container may be made as a tube in an elastic material such as rubber. The oxygen container is outside the stack, but inside any pressure vessel enclosing the stack for pressurizing the stack. The oxygen container extends over the top of the stack, but may also extend or either side of the stack or below the stack. The oxygen may be transported to an outlet in the pressure vessel for letting oxygen out of the pressure vessel, i.e. the oxygen container may be in fluid communication with the outlet. The outlet may comprise a valve. The oxygen container may also function as a valve, i.e. if the pressure of the hydrogen inside the pressure vessel is greater than the pressure of the oxygen, the oxygen con- tainer is pressed together and the flow of oxygen through the oxygen container may be reduced — the volume of the oxygen container is reduced. If the pressure of the hydrogen inside the pressure vessel is lower than the pressure of the oxygen, the oxygen container expands and the flow through the oxygen container is increased — the volume of the oxygen container is increased.
There may be a second outlet of oxygen from the stack, for example at the opposite end of the stack than the first outlet described above, and the second outlet of oxygen from the stack may be in fluid communication with a second oxygen container that may correspond to the first oxygen container.
The hydrogen may exit from the stack at openings at each end of the stack. Alterna- tively, the hydrogen may exit from the stack at an opening at one end of the stack. The hydrogen may exit into the pressure vessel.
DK 181123 B1 17 During operation of the electrolysis system hydrogen will build up in the volume of the pressure vessel, when a desired pressure is reached, surplus hydrogen may be trans- ported out of the pressure vessel via a regulator such as a valve. This may be used to regulate the pressure inside the pressure vessel, i.e. if the pressure becomes too low, the regulator can be closed for a while for increasing the pressure, or if the pressure is too high, the regulator may open and let additional hydrogen out of the pressure ves- sel. An outlet for letting hydrogen out from the stack may be at one end of the stack or at both ends of the stack. The outlet may be in fluid communication with a pipeline 88 extending inside the pres- sure vessel (and outside the stack) for transporting electrolyte solution, that have ex- ited as vapor together with the released gas, back into the stack.
The pipeline may extend with an inclination such that it has a fall towards the opposite end of the stack than the hydrogen outlet. At the opposite end, the pipeline may be in fluid communication with a riser pipe for leading down to the water inlet at the bottom of the stack, i.e. the electrode plates has the water inlets at the bottom.
At the top of the riser pipe may be a T-section 90 having an opening for letting out hy- drogen gas while condensed electrolysis solution flows down through the riser pipe. The opening may face upwards.
Atthe water inlet, there may be a T-section 92 for connection to the riser pipe and a water pipeline for supply of water. The pipeline 88 may be cooled by means of a cooling element for condensing electrol- ysis vapor into liquid form. The cooling element may be copper wire wound around the pipeline. A second outlet may be in fluid communication with a pipeline 94 for the same function as the first pipeline 88.
The pipeline 90 may extend with an inclination such that it has a fall towards the oppo- site end of the stack than the second hydrogen outlet. At the opposite end, the pipeline
DK 181123 B1 18 may be in fluid communication with a second riser pipe for leading down to a second water inlet at the bottom of the stack. At the second water inlet, there may be a second T-section for connection to the sec- ond riser pipe and a second water pipeline for supply of water. The pipeline 90 may be cooled by means of a second cooling element for condensing electrolysis vapor into liquid form. The cooling element may be copper wire wound around the pipeline.
Summary An electrolysis system for production of hydrogen and/or oxygen comprising a stack of electrolysis cells inside a pressure vessel.
Each electrolysis cell in the stack comprises a membrane and a cassette made of a bi- polar plate sandwiched by a cathode and an anode forming a cathode compartment and an anode compartment on each side of the bipolar plate.
The cassette has an inlet for water and an outlet for hydrogen. The inlet and/or outlet may be arranged with fluid separation means and cooling means may cool the electro- lyte solution in order to reduce generation of electrolyte vapor so that together with the separation means the escape of electrolyte solution from a cassette is reduced such that the cells has a higher degree of electrical insulation for reducing cross currents.

Claims (9)

DK 181123 B1 19 PATENTKRAVDK 181123 B1 19 PATENT CLAIM 1. Elektrolysesystem til fremstilling af brint, hvilket elektrolysesystem omfatter - en elektrolytopløsning, -en stak af elektrolyseceller indbefattende en første elektrolysecelle og en anden elek- trolysecelle, hvilken første elektrolysecelle omfatter en katodeplade (30) og en mem- bran (82A), hvor katodepladen (30) har en første side, hvorpå membranen (82A) er til- vejebragt og en anden, modsat side; - et første kammer på den anden side, som er et brintproducerende katodekammer in- deholdende elektrolytopløsningen til frigivelse af brintgas, hvor katodepladen (30) defi- nerer i det mindste en del af en væg i det første kammer og omfatter perforeringer (37) til fluid-kommunikation af elektrolytopløsningen med membranen (82A), og i hvilken en elektrolysereaktion finder sted under drift og for strømning af ioner gennem perforerin- gerne (37); -etførste indløb (42), der udgør et vandindløb til at tilføre vand til den første elektroly- secelle, - et første udløb, inklusive en udløbsrørledning (14a, 14b), og som udgør et brintudløb til transport af brintgas fra den første elektrolysecelle, hvor brintudløbet er anbragt over en overflade af elektrolytopløsningen i det første kammer, -kølemidler til transfer af varme væk fra elektrolytopløsningen, hvor brintudløbet er indrettet til at adskille elektrolytopløsningen fra brintgassen for at beholde elektrolytopløsningen i det første kammer til elektrisk isolering af den første elektrolysecelle og den anden elektrolysecelle fra krydsstrømme; hvor katode- pladen (30) har en åbning (46) i strømningskommunikation med udløbsrørledningen (14a, 14b) til frigivelse af brintgas ud af katodekammeret (78) gennem åbningen (46) og ind i udløbsrørledningen (14a, 14b), kendetegnet ved, at åbningen (46) er anbragt over overfladen (76) af elektrolytopløs- ningen i katodekammeret (78) for at forhindre flydende elektrolyt i at strømme gennem åbningen (46) og ind i udløbsrørledningen (14a, 14b).1. Electrolysis system for the production of hydrogen, which electrolysis system comprises - an electrolyte solution, - a stack of electrolysis cells including a first electrolysis cell and a second electrolysis cell, which first electrolysis cell comprises a cathode plate (30) and a membrane (82A), where the cathode plate (30) has a first side on which the membrane (82A) is provided and a second, opposite side; - a first chamber on the other side, which is a hydrogen-producing cathode chamber containing the electrolyte solution for releasing hydrogen gas, the cathode plate (30) defining at least part of a wall in the first chamber and comprising perforations (37) for fluid communication of the electrolyte solution with the membrane (82A) and in which an electrolysis reaction takes place during operation and for the flow of ions through the perforations (37); - a first inlet (42) which constitutes a water inlet for supplying water to the first electrolysis cell, - a first outlet, including an outlet pipeline (14a, 14b), and which constitutes a hydrogen outlet for transporting hydrogen gas from the first electrolysis cell, wherein the hydrogen outlet is disposed above a surface of the electrolyte solution in the first chamber, -cooling means for transferring heat away from the electrolyte solution, wherein the hydrogen outlet is arranged to separate the electrolyte solution from the hydrogen gas to retain the electrolyte solution in the first chamber for electrically insulating the first electrolytic cell and the second electrolysis cell from cross currents; wherein the cathode plate (30) has an opening (46) in flow communication with the outlet conduit (14a, 14b) for releasing hydrogen gas out of the cathode chamber (78) through the opening (46) and into the outlet conduit (14a, 14b), characterized by that the opening (46) is located above the surface (76) of the electrolyte solution in the cathode chamber (78) to prevent liquid electrolyte from flowing through the opening (46) and into the outlet conduit (14a, 14b). 2. Elektrolysesystem ifølge et hvilket som helst af de foregående krav, hvor kølemid- lerne omfatter et overfladeområde af en væg af det første kammer, som er katode- kammeret, hvilket overfladeområde vender mod det indre af det første kammer, og ud- gør et køleområde.2. An electrolysis system according to any one of the preceding claims, wherein the cooling means comprise a surface area of a wall of the first chamber, which is the cathode chamber, which surface area faces the interior of the first chamber, and forms a cooling area. DK 181123 B1 20DK 181123 B1 20 3. Elektrolysesystem ifølge et hvilket som helst af de foregående krav, hvor den første elektrolysecelle omfatter et andet kammer, som er et anodekammer (78B), indbefat- tende en anden elektrode, som er en anode (78), og elektrolytopløsningen, hvor den første elektrolysecelle omfatter en bipolær plade (74) eller et par bipolære plader mel- Jem det første kammer og det andet kammer.3. An electrolysis system according to any one of the preceding claims, wherein the first electrolysis cell comprises a second chamber, which is an anode chamber (78B), containing a second electrode, which is an anode (78), and the electrolyte solution, in which the first electrolytic cell comprises a bipolar plate (74) or a pair of bipolar plates between the first chamber and the second chamber. 4. Elektrolysesystem ifølge krav 3, hvor den bipolære plade (74) er kølet ved hjælp af en kølevæske.4. Electrolysis system according to claim 3, where the bipolar plate (74) is cooled by means of a cooling liquid. 5. Elektrolysesystem ifølge krav 3 eller 4, hvor katodepladen (30) omfatter en kant (49), der definerer en udgangspassage (50) i katodekammeret (30B) for at lede brint- gassen mod gasudløbet (46), hvor kanten (49) også fungerer som en elektrisk forbin- delse mellem katodepladen (30) og den bipolære plade (74) på den anden side af ka- todepladen.5. Electrolysis system according to claim 3 or 4, wherein the cathode plate (30) comprises an edge (49) defining an exit passage (50) in the cathode chamber (30B) to direct the hydrogen gas towards the gas outlet (46), where the edge (49) also acts as an electrical connection between the cathode plate (30) and the bipolar plate (74) on the other side of the cathode plate. 6. Elektrolysesystem ifølge krav 5, hvor udgangspassagen (50) leder brintgassen i det væsentlige horisontalt mod brintgasudløbet (46).6. Electrolysis system according to claim 5, wherein the outlet passage (50) guides the hydrogen gas essentially horizontally towards the hydrogen gas outlet (46). 7. Elektrolysesystem ifølge et hvilket som helst af de foregående krav, hvor kølemid- Jerne omfatter en kølepassage (40) gennem katodekammeret (30B) til strømning af elektrolytopløsningen gennem kølepassagen (40).An electrolysis system according to any one of the preceding claims, wherein the cooling means comprises a cooling passage (40) through the cathode chamber (30B) for flow of the electrolyte solution through the cooling passage (40). 8. Elektrolysesystem ifølge krav 7, hvor kølepassagen er uden perforeringerne (74).8. Electrolysis system according to claim 7, where the cooling passage is without the perforations (74). 9. Elektrolysesystem ifølge et hvilket som helst af de foregående krav, hvor det første kammer definerer et volumen, og elektrolytopløsningen i det første kammer optager mindre end 100 % af volumenet, såsom mindre end 95 % af volumenet eller mellem 80 til 95 % af nævnte volumen.An electrolysis system according to any one of the preceding claims, wherein the first chamber defines a volume and the electrolyte solution in the first chamber occupies less than 100% of the volume, such as less than 95% of the volume or between 80 to 95% of said volume.
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