WO2024088889A2 - Électrolyseur sous pression, installation d'électrolyse et procédé d'électrolyse - Google Patents

Électrolyseur sous pression, installation d'électrolyse et procédé d'électrolyse Download PDF

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Publication number
WO2024088889A2
WO2024088889A2 PCT/EP2023/079235 EP2023079235W WO2024088889A2 WO 2024088889 A2 WO2024088889 A2 WO 2024088889A2 EP 2023079235 W EP2023079235 W EP 2023079235W WO 2024088889 A2 WO2024088889 A2 WO 2024088889A2
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WO
WIPO (PCT)
Prior art keywords
end plate
pressure
stack
housing body
section
Prior art date
Application number
PCT/EP2023/079235
Other languages
German (de)
English (en)
Other versions
WO2024088889A3 (fr
Inventor
Daniel TADJE
Christian HÄGELE
Original Assignee
Hitachi Zosen Inova Ag
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Application filed by Hitachi Zosen Inova Ag filed Critical Hitachi Zosen Inova Ag
Publication of WO2024088889A2 publication Critical patent/WO2024088889A2/fr
Publication of WO2024088889A3 publication Critical patent/WO2024088889A3/fr

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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/05—Pressure cells
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms

Definitions

  • the above invention relates to a pressure electrolyzer designed according to the preamble of claim 1, in particular a high-pressure electrolyzer, such as an alkaline electrolyzer for water electrolysis.
  • the present invention further relates to an electrolysis system, in particular a water electrolysis system, with a corresponding pressure electrolyzer, and an electrolysis process which is carried out in the electrolyzer.
  • Electrolyzers that operate at a pressure higher than atmospheric pressure are known, for example, from the publications DE 10 2014 010 813 A1 and EP 1 464 730 A1. For reasons of mechanical integrity, these pressure electrolyzers have a pressure-bearing frame construction to protect the electrolysis block, i.e. to protect the cell stack with electrolysis cells. Known pressure electrolyzers carry out electrolysis at a pressure of around 20 to 50 bar.
  • the publication DE 44 18 999 A1 discloses a pressure electrolyzer with a cell block that is installed in a cylindrical pressure tube.
  • the pressure tube is closed at its ends by end flanges, which are also the end flanges of the cell block. In this way, the same pressure conditions prevail inside and outside the cell spaces of the electrolysis cells.
  • both the internal sealing of the electrolysis cells and the external sealing of the tubular pressure vessel are carried out by an axial seal.
  • the electrolyzer must therefore work with very tight tolerances. This axial seal enables proper sealing of the electrolyzer only at a relatively low working pressure of the electrolysis cells.
  • Figure 4 of the document EP 0 212 240 A1 discloses a pressure electrolyzer in which the end flanges of the cell block are cast into a common seal. This seal serves both to seal the electrolysis cells from one another and to seal the interior of the pressure vessel from the environment. Due to the high pressure load, this seal must be very strong in order to withstand the pressure conditions acting on it.
  • High-pressure electrolyzers that carry out electrolysis under high pressure, for example under a pressure of at least 200 bar, such as 350 bar or 700 bar, are called high-pressure electrolyzers.
  • a high-pressure electrolyzer can be used to provide compressed hydrogen, for example, which can be used as a fuel or as an energy source.
  • a pressure electrolyzer designed according to the preamble of claim 1 is known from the publication US 2011/0210012 A1.
  • This pressure electrolyzer is a high-pressure electrolyzer and is used to produce hydrogen.
  • the publication US 2011/0210012 A1 teaches arranging the cell stack, the so-called stack of the electrolyzer, in a cup-shaped pressure vessel that is sealed against the ambient pressure and subjected to the working pressure of the electrolyzer.
  • an end plate of the cell stack forms a stationary head, which is formed in one piece with a lid of the cup-shaped pressure vessel and is equipped with electrical anode and cathode connections.
  • the second end plate of the cell stack forms a moving head, which can move freely in the longitudinal direction relative to the stationary head in response to a thermally induced expansion or contraction of the electrolysis cells.
  • these In order to seal the cell frames of the respective electrolysis cells from each other, these have internal O- Ring seals that surround the cell frames.
  • external seals In order to separate the interior of the pressure vessel from the ambient pressure, external seals are also provided, which are axially clamped between the stationary head and an anode plate of the cell stack ( Figure 2 of US 2011/0210012 A1).
  • the disadvantage of this system is that it is complex in structure and strong mechanical forces act on the anode plate of the cell stack due to the existing pressure difference.
  • US4210511 discloses a pressure electrolyzer with a cell block that is installed in a cylindrical tubular pressure vessel.
  • the tubular pressure vessel comprises a pressure tube and two end flanges, each of which closes one end of the pressure tube in the position of use.
  • the end flanges have axial passages for threaded rods, which threaded rods clamp the end flanges axially between the end flanges by means of nuts attached to them.
  • disks made of electrically insulating material are provided between the nuts and the end flanges.
  • the disks enable the threaded rods to be centered in the respective passages, so that a radial clearance is ensured between the threaded rods and the end flanges.
  • the end wall of the pressure tube has a receiving groove that runs in the circumferential direction and is open radially towards the interior of the pressure tube.
  • the end flanges each have an axially protruding projection carrying a radial seal, which projection is designed to be received in the receiving groove in a sealing manner in the position of use.
  • a holding plate is provided between the end flanges and the cell block, which holds the cells of the cell block in the axial direction in the position of use and at the same time comes into contact with the bottom of the receiving groove.
  • the inner seal of the Electrolysis cells are sealed by an axial seal and the external sealing of the tubular pressure vessel is carried out by a radial seal.
  • the design of the electrolyzer requires machining of the end walls, in particular the manufacture of the receiving groove, which requires tight tolerances.
  • the receiving groove must in fact allow simultaneous axial contact of the holding plate with the bottom of the receiving groove and with the cell block.
  • the electrolyzer must work with very tight tolerances, in particular the thickness tolerance of the cells, in order to enable this contact and to maintain it during operation, so that the mechanical stress on the holding plates and the external seal does not cause a loss of tightness.
  • the electrolyzer experiences an increase in temperature, which causes the cells to expand, resulting in further stress on the holding plates.
  • the discs made of insulating material can suffer mechanically and become damaged over time.
  • CN104911626B discloses a pressure electrolyzer for hydrogen production, which comprises a positive end plate and a negative end plate.
  • Flat cylindrical seals and cell frame assemblies are arranged offset between the positive end plate and the negative end plate. Threaded rods are passed through the positive end plate and the negative end plate to clamp the combined seal and the cell frame assemblies. Sealing against the ambient pressure is achieved via the flat cylindrical seals in the axial direction.
  • the cell block of the pressure electrolyzer is not installed in a cylindrical tubular pressure vessel. For this reason, the cell frame assemblies are exposed to high mechanical stress when a high working pressure is applied.
  • the present The invention is based on the task of developing a pressure electrolyzer of the type mentioned at the beginning in such a way that the pressure electrolyzer can be manufactured as simply and inexpensively as possible.
  • the pressure vessel should seal against the ambient pressure in a simple manner, reliably and for a long time.
  • the pressure electrolyzer should be designed in such a way that the mechanical forces acting on the internal seals and the external seal are as low as possible and the pressure electrolyzer should have as few separate parts as possible.
  • the pressure electrolyzer should have reliable and long-lasting insulation, which prevents short circuits.
  • the present invention is based on the object of providing an electrolysis plant comprising the pressure electrolyzer and a method for providing at least one gas product by means of electrolysis, which method is carried out in the pressure electrolyzer.
  • the invention relates to a pressure electrolyzer for providing at least one gas product, comprising a cell stack with several electrolysis cells designed for electrochemical electrolysis and a pressure vessel sealed against the ambient pressure.
  • the pressure electrolyzer is designed to carry out the electrolysis of water into its elements oxygen and hydrogen, which are formed as gas products.
  • the electrolysis cells are connected in series in an axial direction and clamped between a first stack end plate and another stack end plate.
  • the electrolysis cells each have a cavity in which to which a working pressure is applied, as well as a stabilizing cell frame surrounding the cavity.
  • an internal seal is arranged between two cell frames, whereby the internal seals run around the respective cavities of the electrolysis cells and seal them off from the environment of the electrolysis cells.
  • the internal seals are arranged in the axial direction between the cell frames and clamped between the stack end plates.
  • the preferably cylindrical pressure vessel has a pressure-resistant housing body with an end wall at each of its axial ends, as well as the first stack end plate as the cover surface and the further stack end plate as the base surface.
  • the housing body is clamped between the first stack end plate and the further stack end plate and has at least one external seal designed to seal the interior of the pressure vessel against the ambient pressure.
  • the cell stack is accommodated in the interior of the pressure vessel in a working section of the housing body, in which pressure vessel the working pressure of the electrolysis cells is applied.
  • At least one of the first stack end plate or the further stack end plate has an axial end plate projection.
  • the first stack end plate or the further stack end plate or both stack end plates have an axial end plate projection.
  • the external seal is clamped in the radial direction between the housing body and a sealing section of the end plate projection.
  • the sealing section has a cross section which, in the position of use, is inscribed in the cross section of the working section. Furthermore, the sealing section projects into the working section of the housing body.
  • the end plate projection has a stamping surface on its side facing the cell stack, which in the position of use of the pressure electrolyzer presses the cell stack in the axial direction to clamp the cell stack between the first and the other stack end plate.
  • At least one of the first stack end plate or the further stack end plate comprises a closing plate, which can act as a cover surface or as a base surface, and the end plate projection, which projects axially inward from the closing plate and projects into the working section.
  • the pressure electrolyzer advantageously has fastening elements or fastening rods which clamp the stack end plates together.
  • the fastening elements can have threaded rods as tie rods which clamp the electrolysis cells axially between the stack end plates by means of attached nuts.
  • the fastening elements are preferably electrically insulated from the first stack end plate and the further stack end plate.
  • the sealing section of the end plate projection has a cross section which, in the position of use, is inscribed in the cross section of the working section, the sealing section can be inserted into the pressure vessel.
  • the end plate projection protrudes into the pressure vessel by at least one insertion length of the end plate projection.
  • the cross section defines the cross section running at right angles to the axial direction.
  • the end plate projection protruding into the working section of the housing body allows for greater tolerance in the construction of the pressure electrolyzer, particularly in the thickness tolerance of the electrolysis cells.
  • the end plate projection can protrude more or less into the housing body depending on the deviation from the nominal thickness of the cell stack. This is done without endangering the tightness because the external seal is arranged radially between the sealing section of the end plate projection and the housing body.
  • the tightness of the pressure vessel can be ensured regardless of the design of the end walls of the housing body, because the external seal in the position of use in the working section and not between the end walls and the locking plate.
  • one of the first stack end plate or the further stack end plate is integrally and one-piece formed, i.e. the end plate projection and the closing plate form an inseparable unit, preferably made of a single material.
  • a pressure electrolyzer can comprise a hundred or more electrolysis cells, each of which has a nominal thickness and a thickness tolerance. Consequently, the thickness tolerance is multiplied by a factor of a hundred or more when calculating the total thickness of the cell stack.
  • a thickness tolerance of the electrolysis cells of +/- 0.1 mm, this means a dimension, i.e. a deviation from the nominal dimension, of +/- 10 mm for the cell stack.
  • the end plate projection protrudes into the working section of the housing body, it can protrude more or less depending on the dimension, while its stamping surface presses the cell stack in the axial direction. The end plate projection can thus compensate for the dimension of the cell stack.
  • the working pressure in the pressure vessel is maintained because the external seal is clamped in the radial direction between the housing body and the end plate projection. A larger thickness tolerance is therefore permitted during production. This is advantageous because the production of the electrolysis cells is correspondingly simplified and thus cheaper.
  • the nominal thickness of the cell stack is the sum of the nominal thicknesses of the electrolysis cells.
  • the cell stack dimension is the cumulative deviation of the thicknesses of the electrolysis cells from their nominal thickness.
  • the upper dimension of the cell stack is the highest positive tolerance, i.e. the maximum positive deviation from the nominal thickness. This occurs when each electrolysis cell has the maximum positive deviation from its nominal thickness.
  • the lower dimension of the cell stack is the highest negative tolerance, i.e. the maximum negative deviation from the nominal thickness.
  • the nominal thickness plus the upper dimension gives the maximum dimension, i.e. the maximum thickness of the cell stack.
  • the nominal thickness minus the lower dimension gives the minimum dimension, i.e. the minimum thickness of the cell stack.
  • the end plate projection has a cross section over its entire axial length which, in the position of use, is inscribed in the cross section of the working section.
  • the manufacture of the end plate projection is therefore simplified.
  • the end plate projection can optionally be introduced into the working section over its entire length, whereby larger thickness tolerances can be compensated.
  • the stamping surface is aligned perpendicular to the axial direction in order to have a stamping surface running parallel to the electrolysis cells, which can press the cell stack homogeneously.
  • the stamping surface is in direct contact with the electrolysis cell facing the stamping surface in order to avoid interfaces.
  • the present invention is based on arranging the cell stack in a pressure vessel designed as a closed pressure compartment and between to clamp two stack end plates, wherein at least one external seal designed to seal the interior of the pressure vessel against the ambient pressure is arranged in such a way that the forces which clamp the cell stack and the forces which clamp the external seal act in different directions.
  • the forces acting on the cell stack and the forces acting on the external seal are therefore aligned differently and thus distributed more evenly, whereby the requirements for the stability of the cell stack and the stability of the external seal are lower and these can be made from a larger selection of materials.
  • This also has the advantage that the electrolysis cells are free of the external seal and are therefore easier to manufacture.
  • the end plate projection comprises an inner section and an outer section.
  • the inner section In the use position, the inner section is arranged in the housing body and comes into contact with the cell stack.
  • the sealing section is part of the inner section.
  • the outer section In the use position, the outer section is arranged outside the housing body and is intended to form an axial air gap between the end wall of the housing body and at least one of the first stack end plate or the further stack end plate.
  • the external seal arranged between the end plate projection and the housing body electrically insulates the housing body from at least one of the first stack end plates or from the further stack end plates. Insulation of the fastening elements which clamp the first stack end plate and the further stack end plate together is therefore only necessary for the first stack end plate or the further stack end plate.
  • the end plate projection is electrically insulated from the housing body by an electrically insulating support element. The support element supports a coaxial arrangement of the housing body to the end plate projection.
  • the support element runs radially between the end plate projection and the housing body and preferably lies directly axially against the external seal in order to prevent the external seal from slipping.
  • the axial section of the pressure vessel in which the cell stack is arranged in the position of use defines the working section of the pressure vessel.
  • the working section extends over an axial length which corresponds at least to the sum of the nominal thickness of the cell stack, the upper dimension of the cell stack and an axial reserve length.
  • the reserve length is intended to accommodate the inner section of the end plate projection in the housing body so that the end plate projection, in particular its stamping surface, comes into contact with the cell stack in the use position. At least the sealing section is in the working section. Depending on the actual dimensions of the cell stack, the length corresponding to the upper dimension can also be intended to accommodate the inner section of the end plate projection.
  • An overall axial length of the end plate projection includes the insertion length corresponding to the inner portion and may include a residual length corresponding to an outer portion of the end plate projection extending outside the housing body.
  • the overall axial length of the end plate projection extends from the punch surface to the foot of the end plate projection, which foot is at the level of the closing plate.
  • the total length of the end plate projection is calculated such that an axial air gap between the closing plate and the corresponding end wall of the housing body in position of use. This enables electrical insulation between the housing body and the stack end plate.
  • the total axial length of the end plate projection is at least as large as the sum of the lower dimension of the cell stack to ensure that the end plate projection comes into contact with the cell stack and the thickness of the sealing section to ensure that the sealing section is in the working section for the tightness of the pressure vessel. In the position of use, the insertion length of the end plate projection depends on how large the actual dimension of the cell stack is.
  • the reserve length can also be calculated so that additional electrolysis cells can optionally be included in the cell stack.
  • the total axial length of the end plate projection is calculated so that the end plate projection comes into contact with the cell stack in the position of use.
  • the operating position of the pressure electrolyzer corresponds to an assembled state of the pressure electrolyzer.
  • the working section has a cross-section that allows the cell stack to be accommodated.
  • the cross-section of the cell stack is inscribed in the cross-section of the working section, whereby a radial distance between an inner surface of the housing body and the cell stack can be present over the entire circumference of the cell stack. This allows electrical insulation between the cell stack and the housing body.
  • the working section has the same cross-section over its length.
  • the housing body has the same cross-section as the cross-section of the housing body over the entire length of the housing body. This simplifies the manufacture of the housing body and is therefore more cost-effective.
  • the working section extends over an entire axial length of the housing body. The cell stack can thus be arranged flexibly in the housing body. The cross section of the housing body can remain the same over its entire length.
  • the end plate projection has the same cross-section as the cross-section of the electrolysis cells. In this embodiment, it is ensured that the cell stack is pressed homogeneously in the axial direction by the end plate projection.
  • the housing body is preferably cylindrical, particularly preferably circularly cylindrical, in order to create a radial distribution of the forces exerted by the working pressure.
  • the cross section of the housing body forms a circular cross section which has the same diameter over the axial length of the housing body.
  • the end plate projection has a cross section which, in the position of use, is inscribed in the circular cross section of the working section. Specifically, the longest dimension of the cross section of the end plate projection is smaller than the diameter of the circular cross section.
  • the end plate projection is designed as a circular cylinder, a circular, axially centered disk, which in the position of use extends at least partially into the working section. This embodiment ensures that the cell stack is pressed homogeneously in the axial direction by the end plate projection.
  • the working section extends over the entire length of the housing body so that the housing body can accommodate as many electrolysis cells as possible.
  • the internal seals act in the axial direction and the external seal in the radial direction, ie the internal seals seal in the axial direction and the external seals seal in the radial direction.
  • the forces acting on the internal seals are acting forces are aligned in the direction of the longitudinal axis of the housing body of the pressure vessel, for example horizontally.
  • the forces acting on the external seal are aligned in the direction of the radius of the housing body of the pressure vessel, i.e. in the radial direction. Due to this different alignment of the internal seals and the external seal, the overall mechanical load acting on these seals is reduced. This means that the seals, i.e. the internal seals as well as the external seals, reliably fulfill their sealing function even at very high pressure conditions, can be manufactured from cost-effective material and are designed to be durable.
  • the pressure vessel is formed from the two stack end plates of the cell stack and a tubular or shell-like housing geometry, which forms the housing body and is pressure-tightly connected to the end plates, also called stack end plates, of the electrolysis cell stack.
  • the first stack end plate can be designed as an anodic end plate in its area facing the electrolysis cells, in particular in an area designed as a stamping surface, and the other stack end plate can be designed as a cathodic end plate in its area facing the electrolysis cells, or vice versa.
  • the electrical insulation of the pressure electrolyzer is designed in such a way that an electrical current can flow between the end plates, whereby possible electrical short circuits caused by, for example, fastening elements or the housing body are avoided.
  • the anodic end plate and/or the cathodic end plate may be split into two parts, as described in more detail below.
  • the first stack end plate and the further stack end plate each have an end plate projection.
  • the end plate projection is designed the same for the first stack end plate and the further stack end plate.
  • the first stack end plate and the further stack end plate are designed the same, so that only a single stack end plate needs to be designed, which fits both ends of the housing body.
  • the first stack end plate or the further stack end plate has an end plate projection.
  • This embodiment has the advantage that only one stack end plate, e.g. the first stack end plate, has to be machined in order to form the end plate projection.
  • the further stack end plate can be connected to the housing body in a sealing manner via an external seal arranged between the corresponding end wall of the housing body and the further stack end plate.
  • the stamp surface is directly adjacent to the electrolysis cell facing the stamp surface. This allows a compact embodiment of the pressure electrolyzer to be produced.
  • At least one of the first stack end plate or the further stack end plate is the first stack end plate, which first stack end plate can be detachably connected to the housing body and is designed to close an axial opening of the housing body in a pressure-tight manner.
  • first stack end plate can be detachably connected to the housing body and is designed to close an axial opening of the housing body in a pressure-tight manner.
  • the further stack end plate is designed integrally and pressure-tightly with the housing body. Integral is to be understood as meaning that the housing body and the further stack end plate are connected to one another to form a single complete piece. For example, the housing body and the further stack end plate can be welded together tightly.
  • the pressure vessel can thus be designed as simply as possible because no external seal is required on this side.
  • the external seal runs around the outer circumference of the end plate projection, which end plate projection preferably has a circumferential sealing groove in the sealing section for receiving the external seal.
  • the production of the sealing groove in the end plate projection, in particular in the sealing section of the end plate projection, is less complex than in the inner wall of the housing body.
  • the wall thickness of the housing body can be chosen to be thinner if the sealing groove is formed in the end plate projection. This is advantageous for the manufacturing costs.
  • the external seal acts radially.
  • the external seal is designed as a separate element which is clamped between the housing body and a radial sealing surface, wherein the sealing surface forms a bottom of the sealing groove.
  • the bottom of the sealing groove preferably runs parallel to the axial direction, seen in the longitudinal cross section.
  • the outer circumference of the stack end plates is larger than the outer circumference of the housing body, so that the stack end plates have an outer region extending away from an outer surface of the pressure vessel.
  • the stack end plates are arranged parallel to one another.
  • the stack end plates are clamped together at their outer region by means of at least three fastening elements extending in the direction of the longitudinal axis of the housing body, i.e. in the axial direction, in such a way that the cell stack is clamped axially between the stack end plates, in particular between the stamping surface and the opposite stack end plate.
  • Each electrolysis cell has a surrounding cell frame for stabilization.
  • the internal seal is arranged between two cell frames in the cell stack.
  • the internal seals are each clamped between two cell frames, with the cell frames each having a frame groove for accommodating an internal seal
  • the frame grooves each have a sealing surface which forms a bottom of the frame groove.
  • the bottom of the frame groove runs parallel to the plane of the respective cell frame.
  • the sealing surface of the frame grooves is arranged perpendicular to the sealing surface of the sealing groove.
  • the external seal is designed as a double seal.
  • a further external seal runs around the outer circumference of the end plate projection, which end plate projection preferably has a further sealing groove running around it to accommodate the further external seal. The tightness of the pressure vessel is thus better ensured.
  • the end wall of the housing body which faces the at least one of the first stack end plates or the further stack end plate, runs in a plane extending at right angles to the axial direction.
  • the housing body can thus be manufactured cost-effectively because the end formed by the end wall can be manufactured via a cut without complex machining of the end wall, for example without a groove or without a step.
  • the end wall runs in a plane which can result from a cut transverse to the axial direction.
  • the end wall runs from the outer surface of the housing body to the inner surface of the housing body in one plane, i.e. the transition from the outer surface to the inner surface runs without interruption, for example without interruption by a recess or a groove.
  • both ends of the housing body each run in a plane extending at right angles to the axial direction.
  • the end wall of the housing body runs on both ends in a plane extending at right angles to the axial direction.
  • the fastening elements When clamping the stack end plates, the fastening elements can be electrically insulated from the stack end plates by insulating elements to prevent an electrical short circuit between the poles of the cell block.
  • Stack end plates can have axial passages for the fastening elements, e.g. threaded rods.
  • insulation elements made of electrically insulating material can be provided between the fastening elements and the stack end plates.
  • the insulation elements can be discs, which at the same time enable the fastening elements to be centered in the respective passages, so that a radial clearance is guaranteed between the fastening elements and the stack end plates. It is also possible to provide a housing body made of electrically insulating material.
  • At least one of the first stack end plate or the further stack end plate is designed in the form of an assembly, wherein the closing plate, which acts as a cover surface or as a base surface, and the end plate projection are designed separately, wherein the closing plate and the end plate projection are electrically insulated from one another by a separating layer made of electrically insulating material.
  • the first stack end plate or the further stack end plate or both stack end plates are designed as an assembly.
  • the first stack end plate or the further stack end plate is divided into two parts.
  • the elements of the assembly i.e. the closing plate, the end plate projection and the separating layer, are easier to manufacture because three functions of the stack end plate, namely stability of the pressure electrolyzer, pressure tightness and electrical insulation, can be separated.
  • the selection of materials for the elements of the stack end plate can thus be optimized depending on the function of the elements.
  • the closing plate must act as a pressure element in the axial direction and thereby contribute to the stability of the pressure electrolyzer.
  • the end plate projection which carries the external seal, acts as a sealing element.
  • the separating layer acts as an insulating element between the poles of the cell block.
  • Electrical contact with the cell stack can be established via a passage formed in the closing plate and the separating layer.
  • the manufacture of the stack end plate as an assembly is simplified because there is no need to mill out a base plate to form the end plate projection.
  • the housing body of an electrolyzer can be up to 2.5 meters long and have a diameter of up to 1.5 meters. The milling must adhere to tight tolerances in order to ensure the tightness and mechanical stability of the pressure vessel. Machining the base plate can therefore be difficult, especially with large diameters.
  • This embodiment also has the advantage that no further electrical insulation of the fastening elements is required.
  • the separating layer takes on the function of insulation between the poles of the cell block. Consequently, fewer components are required.
  • the pressure electrolyzer is less susceptible to insulation failure, so that the pressure electrolyzer can be operated more safely.
  • the insulation takes place in one place, namely on the separating layer, which is homogeneously axially pressed between the end plate projection and the closing plate.
  • the separating layer is hardly exposed to any other mechanical loads.
  • the insulation elements are mechanically stressed when the pressure electrolyzer is assembled. If disc-shaped insulation elements are used, they are each pressed between a nut and the stack end plate and subjected to a shear load when the nut is screwed in tightly.
  • the electrical contact to the end plate projection can be made via an electrical connection which is electrically insulated through the separating layer and the closing plate.
  • the first stack end plate and the further stack end plate are each designed in the form of an assembly. This allows a symmetrical construction of the pressure electrolyzer.
  • the first stacking end plate and the further stacking end plate are designed identically, so that only a single stacking end plate needs to be designed, which fits both ends of the housing body.
  • the closing plate is designed as a flat plate of the same thickness everywhere, which is inexpensive to manufacture.
  • the end plate projection extends between the stamping surface and an intermediate surface facing away from the stamping surface, i.e. facing away from the cell stack, which delimits the end plate projection in the axial direction.
  • the stamping surface and the intermediate surface preferably run parallel to one another and perpendicular to the axial direction.
  • the total axial length of the end plate projection extends from the stamping surface to the foot of the end plate projection, which foot is located at the level of the intermediate surface
  • the separating layer has the same shape as the intermediate surface, in particular the same cross-section, in order to cover the intermediate surface in the position of use. This makes it possible to insulate the end plate projection from the closing plate over its entire intermediate surface.
  • the separating layer preferably extends over the entire cross-section of the housing body. The area of the separating layer is therefore larger than the intermediate surface. This prevents electrical bridges between the end plate projection and the closing plate.
  • the overall axial length of the end plate projection is designed such that an axial air gap is present between the locking plate and the front wall of the housing body in the position of use. This enables electrical insulation between the housing body and the locking plate.
  • the overall axial length of the end plate projection and the thickness of the separating layer are designed such that the axial air gap between the closing plate and the end wall is present in the position of use in order to ensure more reliable insulation.
  • the end plate projection is designed as an electrolysis cell, the cell frame of which has a thickened wall on the side facing the closing plate, the thickened wall being intended to accommodate the external seal.
  • the thickened wall consequently comprises the sealing section.
  • the pressure vessel is sealed against the ambient pressure, has the cell stack in its interior and is pressurized when the electrolysis is carried out.
  • the pressure vessel can be pressurized with a pressure of at least 5 bar, preferably at least 30 bar, particularly preferably at least 40 bar when the electrolysis is carried out.
  • the pressure vessel is pressurized with the working pressure of the electrolysis cells when the electrolysis is carried out.
  • the arrangement of the cell stack in the pressure vessel means that when electrolysis is carried out, essentially the same pressure conditions prevail inside the electrolysis cells, i.e. in the cavities of the electrolysis cells, as well as outside the electrolysis cells, and no pressure difference or only a small pressure difference acts on the cell stack, in particular on the end plates of the cell stack.
  • the pressure acting on the individual cell frames of the electrolysis cells is therefore approximately the same on the inside and outside of the electrolysis cells. As a result, significantly lower mechanical forces act on the cell frames and on the internal seals of the electrolysis cells than if the cell stack were exposed to atmospheric pressure. pressure.
  • the cell frames so-called stack frames, and the associated internal seals between the cell frames are not exposed to the pressure difference between the working pressure and the environment, but operate at a very low pressure difference at most. This reduces the risk of failure of the internal seal and thus the risk of lye leaking out of the respective electrolysis cells. Failure of the internal seal would lead to a deterioration in the performance and/or service life of the cell stack.
  • the cell stack Due to the arrangement of the cell stack in the pressure vessel, there is no pressure difference between the environment of the electrolysis cells and the cavities of the electrolysis cells. This means that there are fewer demands on the pressure resistance of the cell stack. This significantly increases the service life of the cell stack, in particular the cell frames and the internal seals. With an electrolysis cell working pressure of 30 bar and a pressure in the pressure vessel of around 30 bar, the service life of the cell frames and internal seals is approximately doubled compared to a conventional cell stack operating at ambient pressure.
  • the cell frames and internal seals can also be made from a wider range of materials because they are exposed to lower mechanical stress.
  • the cell frames can be made from ethylene propylene diene (monomer) rubber, so-called EPDM.
  • the electrolysis in the pressure vessel can be carried out at a working pressure of over 100 bar and up to 700 bar, i.e. at a pressure difference to the environment of the electrolyzer that the electrolysis cells and their seals can hardly or not at all mechanically tolerate.
  • higher working pressures in the cell stack lead to better efficiency and are therefore advantageous.
  • Water is under pressure, which supports the electrolysis reaction.
  • a compressed gas product can be produced at a higher working pressure, e.g. hydrogen under a pressure of 300 bar or higher, so that an additional compressor to compress the gas product for use is no longer necessary.
  • the end plate projection is arranged at a radial distance from the inner surface of the housing body, in particular from the inner surface of the working section, with the external seal extending through the radial distance.
  • the external seal thus also serves as a spacer and supports a coaxial arrangement of the inner surface of the housing body to the stack end plates.
  • the cell stack is also arranged at a radial distance from the inner surface of the housing body, preferably with the same radial distance as the radial distance of the end plate projection.
  • the pressure electrolyzer is preferably designed to provide hydrogen by means of electrochemical electrolysis of water.
  • the present invention also relates to an electrolysis system comprising a pressure electrolyzer according to the type described above and at least one gas storage container which receives the gas product and is designed to separate the gas product from the electrolyte carried along.
  • This electrolysis system benefits from the advantages of the pressure electrolyzer, which is reflected in greater safety and lower maintenance costs.
  • the present invention also relates to a method for providing at least one gas product by means of electrolysis, in particular hydrogen, which method is carried out in a pressure electrolyzer according to one of the embodiments set out above, wherein when carrying out the electrolysis in the interior of the pressure vessel a pressure of at least 5 bar, approximately at least 30 bar, preferably between 40 bar and 50 bar, also preferably over 100 bar, in particular between 150 bar and at least 200 bar, approximately up to 350 bar or up to 700 bar, is present.
  • a pressure of at least 5 bar, approximately at least 30 bar, preferably between 40 bar and 50 bar, also preferably over 100 bar, in particular between 150 bar and at least 200 bar, approximately up to 350 bar or up to 700 bar is present.
  • a working pressure is possible with the embodiments set out because the electrolysis cells are insulated from the ambient pressure of the pressure electrolyzer by the housing body.
  • the housing body can be designed to be optimized for this, as has been set out. Higher working pressures in the pressure vessel lead to better efficiency.
  • a compressed gas product can be produced at a higher working pressure.
  • the gas product e.g. hydrogen
  • the gas product can thus be provided in compressed form and does not need to be compressed further after electrolysis to serve as fuel or for storage. This saves energy and costs for the pressure compressor or avoids the use of another pressure compressor.
  • Fig. 1 shows a side view of a first embodiment of a pressure electrolyzer according to the present invention, which operates according to the method according to the present invention
  • Fig. 2 is a longitudinal section of the pressure electrolyzer of Figure 1 along the line A-A shown in Figure 1;
  • Fig. 3 is a longitudinal section of the pressure electrolyzer of Figure 1 along the line B-B shown in Figure 1;
  • Fig.4 shows a detailed view of the area marked «C» in Figure 2;
  • Fig. 5 is a longitudinal section of another embodiment of the pressure electrolyzer.
  • Fig. 6 shows a detailed view of the area marked «D» in Figure 5.
  • Figure 1 shows a pressure electrolyzer 100 for providing at least one gas product, namely an alkaline electrolyzer for providing hydrogen and oxygen by electrochemical electrolysis of water.
  • the pressure electrolyzer 100 has a cell stack 10 with several electrolysis cells 12 connected in series in the axial direction X.
  • the cell stack has several, in particular at least 10, for example 20, about 60, and even 120, electrolysis cells.
  • the cell stack 10 is arranged between a first stack end plate 22, which is designed as an anodic end plate, and a further stack end plate 24, which is designed as a cathodic end plate.
  • Each electrolysis cell 12 has a cavity arranged between an anodic plate and a cathodic plate and a stabilizing cell frame surrounding the cavity.
  • a working pressure of, for example, 30 bar, 350 bar or 700 bar is present in this cavity.
  • the respective electrolysis cells 12 are therefore designed to a working pressure.
  • a membrane is arranged in the cavity of the electrolysis cells 12. Potassium hydroxide solution serves as the electrolyte.
  • an internal seal 14 is arranged in the cell stack 10 between two cell frames.
  • Figure 4 shows stacked electrolysis cells and internal seals 14, which internal seals are located between the cell frames.
  • the internal seals are each clamped between two cell frames, with the cell frames each having a frame groove for receiving the internal seal.
  • the frame grooves each have a sealing surface which forms a bottom of the frame groove. In this case, the bottom of the frame groove runs parallel to the plane of the respective cell frame.
  • the sealing surfaces of the frame grooves each act on the internal seals in the direction of the longitudinal axis X of the housing body, for example in the horizontal direction.
  • the pressure electrolyzer comprises a pressure vessel 18, which comprises a pressure-resistant, tubular, circular-cylindrical housing body 20, the first stack end plate 22 as the cover surface and the further stack end plate 24 as the base surface.
  • the first stack end plate 22 can be detachably connected to the housing body 20 and is designed to close an axial opening of the housing body 20 in a pressure-tight manner.
  • the cell stack 10 is accommodated in the interior of the pressure vessel 18 in a working section 21 of the housing body.
  • this pressure vessel is subjected to excess pressure, preferably to the working pressure of the cells, for example 30 bar or 350 bar or 700 bar.
  • the cell stack 10 is thus enclosed in a pressure-resistant circular-cylindrical housing body 20, such as a pressure-bearing Pipe, which is axially connected to the stack end plates 22, 24 of the cell stack 10.
  • the stack end plates 22, 24 are connected to the housing body 20 in a pressure-tight manner in the position of use of the pressure vessel.
  • the housing body At its axial end facing the first stack end plate 22, the housing body has an end wall 20a which extends in a plane extending perpendicular to the axial direction X.
  • At least one of the first stack end plate or the further stack end plate has an axial end plate projection.
  • the first stack end plate 22 has the end plate projection 28.
  • an external seal 26 is clamped in the radial direction Y between the housing body 20 and a sealing portion 28a of the end plate projection 28.
  • the end plate projection 28 has a circular cross-section over its entire axial length.
  • the sealing section 28a has the same circular cross-section which, in the position of use, is inscribed in the circular cross-section of the working section 21.
  • the end plate projection 28 has on its side facing the cell stack 10 a stamping surface 23 arranged in the interior of the pressure vessel and oriented perpendicular to the axial direction, which presses the cell stack in the axial direction when the pressure electrolyzer is in the position of use in order to clamp the cell stack between the first and the further stack end plate 24.
  • the further stack end plate 24 also has a stamping surface 25 oriented perpendicular to the axial direction, which is formed by the wall of the further stack end plate 24 facing the cell stack. In this way, the cell stack 10 is clamped between the stack end plates 22, 24. Furthermore, the sealing section 28a protrudes into the working section 21 of the housing body 20.
  • the first stack end plate 22 is designed as an assembly, as can be seen better in Fig. 4.
  • the first stack end plate 22 comprises a closing plate 22a, which acts as a cover surface, the end plate projection 28, and a separating layer 33 formed from electrically insulating material.
  • the closing plate and the end plate projection are thus electrically insulated from one another by the separating layer.
  • a short circuit between the two stack end plates 22, 24 can be prevented by dividing the first stack end plate 22 into two parts which are electrically insulated from each other by the separating layer 33.
  • the external seal 26 runs around the outer circumference of the end plate projection 28.
  • the external seal 26 is a double O-ring as shown in Fig. 4.
  • the end plate projection 28 has two circumferential sealing grooves for receiving the double O-ring.
  • Each O-ring is clamped between the housing body 20 and a radial sealing surface 29, the sealing surface 29 forming a bottom of the sealing groove.
  • the bottoms run parallel to the axial direction X, viewed in longitudinal cross section.
  • the two sealing grooves are spaced apart from each other by a spacer element 27 of the end plate projection 28.
  • the further stack end plate 24 is connected directly, in particular integrally, to the housing body 20 in the embodiment shown.
  • the stack end plates 22, 24 are arranged parallel to one another.
  • the outer circumference of the stack end plates 22, 24 projects beyond the outer circumference of the housing body 20, so that the stack end plates 22, 24 have an outer region or projection extending radially outward from the interior of the pressure vessel.
  • the stack end plates 22, 24 are connected to one another at their protruding region by means of fastening elements 30, 32, in particular tie rods, which extend in the direction of the longitudinal axis X of the housing body 20. clamped so that the cell stack 10 is clamped axially between the stamping surface 23 and the further stack end plate 24.
  • the functions of sealing the cavity of the electrolysis cells and sealing the interior of the pressure vessel are fulfilled by two separate elements, namely the internal seals on the one hand and the external seal on the other.
  • Fig. 4 shows a detailed view of the external seal 26 clamped between the cell stack 10 and the first stack end plate 22.
  • the cell stack is arranged at a radial distance 44 from the pressure vessel, in particular from the housing body 20.
  • the fastening elements 30 and 32 have threaded rods which clamp the electrolysis cells axially between the stack end plates by means of attached nuts.
  • the fastening elements must be electrically insulated from the first stack end plate and the further stack end plate if they are electrically conductive.
  • the separating layer 33 ensures that the further end plate 24 and the end plate projection 28 are electrically insulated.
  • the housing body is electrically insulated from the cell stack over a radial distance 44. The electrical contact to the end plate projection 28 is made via an electrical connection 31 which runs through the separating layer and the closing plate in an electrically insulated manner.
  • a support element 54 is arranged in each of the sealing grooves.
  • the support element 54 extends through the radial distance 44 arranged between the cell stack 10 and the housing body 20 of the pressure vessel.
  • the support element 54 extends in the radial direction between the inner surface of the housing body and the end plate projection 28, and in the axial direction between the external seal 26 and a radial wall of the sealing groove.
  • the support element 54 supports a coaxial arrangement of the inner surface of the housing body to the end plate projection 28.
  • the support element 54 supports the external seal 26, which is particularly advantageous at high pressure in order to prevent the external seal 26 from slipping.
  • the support element 54 is made of electrically insulating material and acts as an insulator element. This has the effect that a short circuit between the inner surface of the housing body and the end plate projection 28 is more reliably prevented.
  • the total axial length of the end plate projection 28 and the thickness of the separating layer 33 are designed such that an axial air gap 56 is present between the closing plate 22a and the end wall 20a in the position of use.
  • the pressure chamber around the cell stack 10 can be flushed with product gas.
  • An inlet 50 is provided for letting in the product gas, for example hydrogen (see Fig. 3).
  • an outlet 52 can be provided for any escaping lye, for example potassium hydroxide solution.
  • the cell stack 10 is arranged in a pressure vessel to which the working pressure of the cell stack 10 is applied.
  • the cell stack 10 and its internal seals 14 are axially clamped between the stack end plates.
  • the internal seals 14 therefore act in an axial direction.
  • the external seal 26 designed to seal the pressure vessel is clamped radially between the stack end plate 22 and the housing body 20.
  • the external seal 26 therefore acts in a radial direction. Since the internal seals 14 are arranged in the pressure chamber and the external seal 26 is an element independent of the internal seals, the internal seal 14 and the external seal 26 are exposed to significantly lower mechanical loads than in conventional electrolyzers operating under ambient pressure.
  • the pressure electrolyzer according to Fig. 5 and Fig. 6 is constructed similarly to the embodiment disclosed in Figs. 1 to 4. Only the differences are discussed below. Identical features are identified by the same reference numerals.
  • the first stack end plate 22 is integral and formed in one piece, ie the closing plate and the end plate projection form a unit.
  • the external seal 26 is also clamped in the radial direction Y between the housing body 20 and the sealing section 28a of the end plate projection 28. Furthermore, the sealing section 28a protrudes into the working section 21 of the housing body 20.
  • the fastening elements 30 and 32 have threaded rods which clamp the electrolysis cells axially between the stack end plates by means of attached nuts.
  • the fastening elements are electrically insulated from the first stack end plate and the further stack end plate.
  • the housing body is electrically insulated from the cell stack.
  • Outlet e.g. outlet for any leaking electrolyte, e.g. for

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Abstract

L'invention concerne un électrolyseur sous pression (100) comprenant un empilement de cellules (10) comportant plusieurs cellules électrolytiques (12) et un récipient sous pression (18) rendu étanche par rapport à la pression ambiante, dans lequel est disposé l'empilement de cellules. Un joint d'étanchéité interne (14) est respectivement disposé entre deux cadres de cellules. Les cellules électrolytiques (12) sont serrées entre une première plaque d'extrémité d'empilement (22) et une autre plaque d'extrémité d'empilement (24). Le récipient sous pression comprend un corps de boîtier (20) résistant à la pression et, en tant que surface de couverture, la première plaque d'extrémité d'empilement (22) et, en tant que surface de base, l'autre plaque d'extrémité d'empilement (24). Au moins une plaque parmi la première plaque d'extrémité d'empilement (22) et l'autre plaque d'extrémité d'empilement (24) comprend une partie saillante de plaque d'extrémité (28) axiale, un joint d'étanchéité (26) externe étant serré dans une direction radiale (Y) entre le corps de boîtier (20) et une partie de joint d'étanchéité de la partie saillante de plaque d'extrémité (28). La partie d'étanchéité présente une section transversale qui est inscrite dans la section transversale de la partie de travail, et fait saillie dans la partie de travail. La partie saillante de plaque d'extrémité (28) comporte une surface de poinçonnage (23) qui pousse l'empilement de cellules (10) dans la direction axiale (X).
PCT/EP2023/079235 2022-10-25 2023-10-20 Électrolyseur sous pression, installation d'électrolyse et procédé d'électrolyse WO2024088889A2 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4210511A (en) 1979-03-08 1980-07-01 Billings Energy Corporation Electrolyzer apparatus and electrode structure therefor
EP0212240A1 (fr) 1985-07-17 1987-03-04 Metkon S.A. Dispositif pour l'électrolyse de solutions
DE4418999A1 (de) 1994-05-31 1995-12-07 Von Hoerner System Gmbh Druckelektrolyseur mit einem gekapselten Zellenblock aus einzelnen Elektrolysezellen
EP1464730A1 (fr) 2003-04-04 2004-10-06 CASALE ChEMICALS S.A. Structure de cadre pour réacteur électrochimique de type filtre-presse
US20110210012A1 (en) 2008-10-27 2011-09-01 Casale Chemicals S.A. High Pressure Electrolyser
DE102014010813A1 (de) 2014-07-23 2016-01-28 Etogas Gmbh Rahmen für eine Elektrolysevorrichtung, Elektrolysezellen-Modul und Elektrolysevorrichtung
CN104911626B (zh) 2015-06-23 2017-09-05 陕西华秦新能源科技有限责任公司 一种高压力水电解制氢电解槽

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4210511A (en) 1979-03-08 1980-07-01 Billings Energy Corporation Electrolyzer apparatus and electrode structure therefor
EP0212240A1 (fr) 1985-07-17 1987-03-04 Metkon S.A. Dispositif pour l'électrolyse de solutions
DE4418999A1 (de) 1994-05-31 1995-12-07 Von Hoerner System Gmbh Druckelektrolyseur mit einem gekapselten Zellenblock aus einzelnen Elektrolysezellen
EP1464730A1 (fr) 2003-04-04 2004-10-06 CASALE ChEMICALS S.A. Structure de cadre pour réacteur électrochimique de type filtre-presse
US20110210012A1 (en) 2008-10-27 2011-09-01 Casale Chemicals S.A. High Pressure Electrolyser
DE102014010813A1 (de) 2014-07-23 2016-01-28 Etogas Gmbh Rahmen für eine Elektrolysevorrichtung, Elektrolysezellen-Modul und Elektrolysevorrichtung
CN104911626B (zh) 2015-06-23 2017-09-05 陕西华秦新能源科技有限责任公司 一种高压力水电解制氢电解槽

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