WO2023144802A1 - Cellule électrolytique pour la production de h2 - Google Patents

Cellule électrolytique pour la production de h2 Download PDF

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Publication number
WO2023144802A1
WO2023144802A1 PCT/IB2023/050827 IB2023050827W WO2023144802A1 WO 2023144802 A1 WO2023144802 A1 WO 2023144802A1 IB 2023050827 W IB2023050827 W IB 2023050827W WO 2023144802 A1 WO2023144802 A1 WO 2023144802A1
Authority
WO
WIPO (PCT)
Prior art keywords
water solution
electrolytic cell
electrolysis
metal sheet
cell according
Prior art date
Application number
PCT/IB2023/050827
Other languages
English (en)
Inventor
Andrea Capriccioli
Original Assignee
Eos Energetics S.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eos Energetics S.R.L. filed Critical Eos Energetics S.R.L.
Publication of WO2023144802A1 publication Critical patent/WO2023144802A1/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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B9/13—Single electrolytic cells with circulation of an electrolyte
    • C25B9/15—Flow-through 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

Definitions

  • the present invention relates to an electrolytic cell for the production of hydrogen (H 2 ) .
  • renewable energy sources have led to the need to develop energy storage systems .
  • Renewable Energy Sources are , by their nature , non-programmable and their availability does not always coincide with our needs . It is , therefore , necessary to try to store that energy that is sold of f cheaply and which could not be put into the electricity distribution network .
  • One of the most promising solutions is to use this energy to produce the first of the energy carriers : hydrogen .
  • the storage and the use of hydrogen will allow us to obtain energy when we need it .
  • This gas is an energy carrier that can meet energy demands and, above all , has a very low environmental impact since it does not produce pollutants such as carbon dioxide or greenhouse gases .
  • Hydrogen can be used to obtain both thermal energy, thanks to its combustion, and electrical energy, thanks to special electrochemical devices called fuel cells . In both cases , hydrogen binds to oxygen forming water as the only reaction product , which makes it extremely environmental ly friendly .
  • Hydrogen has the additional advantage of being able to be produced in a non-polluting manner, using a photovoltaic cell system to produce the current necessary for the dissociation by electrolysis of the water solution .
  • hydrogen has the great advantage of being extremely light and of therefore possessing a high energy density per unit mass .
  • electrolysis can be used to break down water into oxygen and hydrogen gases .
  • electrolytic cell The device in which the electrolysis of the water solution takes place is called electrolytic cell .
  • the electrolytic cell is composed of two hal f-elements , also called hal f-cells , kept separate by a semi -permeable membrane , or they are contained in separate containers and connected by a salt bridge .
  • the function of the semi- permeable membrane and of the salt bridge is to allow the passage of an internal ionic current that is necessary so that in each of the hal f-elements the necessary conditions are maintained to favour the respective redox reaction .
  • the purpose of the semi-permeable membrane is to keep the two gases produced separate from each other, while still allowing the passage of ions .
  • an electrolytic cell in the electrolysis of the water solution, an electrolytic cell must be used, whose components are able to guarantee the separation of the hydrogen and oxygen produced .
  • the presence of the structural salt bridge or of the semi-permeable membrane constitutes a signi f icant cost in the global economy of the electrolysers . This cost derives both from the energy consumptions linked to the activity of the salt bridge and from the intrinsic value of the semi-permeable membranes .
  • Patent EP3571332B1 in the name of the Applicant describes an electrolytic cell which does not require either a structural salt bridge or a semi-permeable membrane .
  • the electrolytic cell described in EP3571332B1 substantially provides for a double passage of the water solution through an electrode consisting of a metal sheet , wherein a plurality of holes are obtained and wherein the electrolysis takes place exclusively during the second crossing of the respective electrode .
  • This characteristic and the continuous recirculation of the water solution guarantee an automatic separation of the two gases produced during the electrolysis and, at the same time , a passage of the ions between the two hal f-elements .
  • the two gases produced during the electrolysis will not be able to mix with each other, since , after being produced exclusively inside the holes of the respective metal sheet , they are each pushed into a respective discharge tank to be then treated by a respective degasser .
  • Object of the present invention is an electrolytic cell for the electrolysis of a water solution, whose essential characteristics are reported in Claim 1 and whose auxiliary or preferred characteristics are reported in the dependent Claims.
  • any position indications such as “vertical”, “horizontal”, “above”, “below”, “upper” and “lower”, is relative to the operating position of the electrolytic cell as shown in the attached Figures.
  • the operating position of the electrolytic cell according to the present invention cannot be different from that shown.
  • FIG. 1 is a perspective view, as a whole and with parts represented in schematic form, of an electrolyser according to the present invention
  • FIG. 3 is a rear perspective view of a portion of one of the half-elements of the electrolytic cell of Figure 1 with parts removed for clarity's sake;
  • Figure 4 is a section along line IV-IV of Figure 3;
  • FIG. 5 is an exploded view with parts removed for clarity's sake of a half-element of the cell of Figure 4.
  • FIG 1 denotes as a whole an electrolytic cell according to the present invention.
  • the electrolytic cell 1 is composed of two separate units 2 and 3 coupled together to define internally an electrolysis chamber C ( Figure 2) , in which the water solution to be electrolyzed is housed as will be described below, and two water solution external recirculation circuits 4 each of which is connected to a respective degasser 5 . Both the external recirculation circuits 4 and the degassers 5 are shown in Figure 1 in an extremely schematic form .
  • the electrolysis chamber C is internally subdivided into a plurality of compartments which are crossed by the water solution during the di f ferent steps of the electrolysis process to which it i s sub j ected .
  • Each of the hal f-elements 2 and 3 comprises an inlet sleeve 7 for feeding the respective hal f-element with the water solution and an outlet sleeve 8 to allow the water solution and the gases produced by the respective hal felement to outflow .
  • the external recirculation circuits 4 hydraulically connect the outlet sleeve 8 of the hal f-element 2 with the inlet sleeve 7 of the hal f-element 3 , and the outlet sleeve 8 of the hal f-element 3 with the inlet sleeve 7 of the hal f-element 2 .
  • the water solution that together with the gas produced by the electrolysis comes out of one half-element is introduced into the other hal f-element , after the passage through the degasser 5 .
  • the two external recirculation circuits 4 are operated by two respective known pumps not shown nor described for simplicity' s sake .
  • each of the hal f-elements 2 or 3 comprises an electrode composed of a metal sheet 10 , one front surface 10a of which is covered by an insulating coating .
  • the metal sheet 10 as well as in the insulating coating that covers the front surface 10a thereof , there are obtained a plurality of holes 11 and a plurality of vertical slits 12 parallel to each other .
  • each of the hal f-elements 2 and 3 comprises a feeding tank 13 and a discharge tank 14 , which is faced by the rear surface 10b of the metal sheet 10 .
  • the feeding tank 13 is hydraulically connected to the inlet sleeve 7 through a water solution inlet opening 15 and to the vertical slits 12 through hollow partitions 16 and made of insulating material .
  • each of the hollow partitions 16 defines a hydraulic connection 16a between the feeding tank and the vertical slits 12 .
  • the discharge tank 14 is hydraulically connected to the outlet sleeve 8 through a water solution outlet opening 17 and receives directly from the holes 11 the water solution/gas mixture deriving from the electrolysis process .
  • both the feeding tank 13 and the discharge tank 14 are delimited by a same oblique wall 18 which determines a vertical narrowing thereof .
  • the presence of the oblique wall 18 gives the tanks 13 and 14 a triangular vertical section .
  • the inlet 15 and outlet 17 openings are obtained in the larger portion of the respective tanks 13 and 14 .
  • the feeding tank 13 has a large section in the lower part of the cell for the passage of the incoming fluid and then narrows down towards the upper part of the cell with gradually smaller sections .
  • the discharge tank has a narrow section in the lower part of the cell and then widens towards the upper part of the cell with gradually larger sections where , therefore , the flow rate of the outgoing electrolysis fluid and gas is maximum .
  • the narrowing/widening conformation of the tanks 13 and 14 ensures an improvement of the water solution speed distribution and the usage of all the surfaces of the metal sheet 10 , in which the electrolysis takes place and, therefore , the generation of the gases .
  • the discharge tank 14 is broken down into a plurality of vertical compartments defined by the hollow partitions 16 and by the oblique wall 18 and by an upper hori zontal duct which is faced by the outlet opening 17 .
  • the electrolytic cell 1 comprises a plurality of conveying and sti ffening cross members 19 housed inside the hollow partitions 16 , i . e . in the hydraulic connections 16a .
  • the presence of the cross members 19 guarantees a better distribution of the fluid and at the same time guarantees a sti f fening of the walls of the hollow partitions 16 .
  • the electrolytic cell 1 compri ses a plurality of dividing partitions 20 housed vertically in the feeding tank 13 .
  • the presence of the dividing walls 20 leads to a further optimi zation of the flow of the water solution .
  • the dividing partitions 20 by reali zing a sort of channels , allow to have , also along the entire vertical development of the metal sheet 10 , the maximum uni formity and correct distribution of the fluid flow rates .
  • Each of the dividing partition 20 comprises at a lower end thereof a curved conveying portion 21 facing said water solution inlet opening 15 .
  • the conveying portions 21 have a staggered position relative to one another from the top to the bottom moving away from said inlet opening 15 .
  • the conveying portions 21 deflect the incoming water solution (having a hori zontal speed) upwards and have the further task of " sectioning" the incoming flow in equal parts , subdividing it and sending very similar flow rates to the various vertical channels reali zed by the dividing partitions 20 .
  • FIG. 3 there is shown a plurality of conveying deflectors 22 housed in the upper hori zontal duct of the discharge tank 14 and each of which extends in the area of a dividing partition 20 .
  • the conveying deflectors 22 have the function of ef fectively deflecting the flow of water solution and of gas from the vertical compartments towards the outlet opening 17 .
  • the conveying deflectors 22 have a staggered position relative to one another from the top to the bottom moving close to the outlet opening 17 .
  • Each of the electrodes comprises a hydraulic resistance layer 23 , whose task is to achieve a pressure drop of at least 1 . 5 Pa in the passage of the electrolyte from the electrolysis chamber C to the discharge tank 14 ( second crossing of the metal sheet 10 by the water solution) .
  • the hydraulic resistance layer 23 is an electrically insulating layer arranged to cover the holes 11 of the respective metal sheet 10 and having a mesh structure with a US mesh number ranging from 70 to 30 ( 0 . 2 and 0 . 6 mm) .
  • the US mesh number is an Anglo-Saxon unit of measurement corresponding to the number of meshes per linear inch (US mesh) .
  • the mesh structure of the layer 23 is not shown in Figures 2 and 5 for convenience .
  • Each of the layers 23 has a thickness of the order of one-tenth of a mm ( approximately 0 . 05- 0 . 25 mm) and adheres to the non-perf orated portions of the metal sheet 10 to which it is coupled . After passing this layer 23 , in the perforated areas , the water solution comes into contact with the internal surface of the holes of the metal sheet 10 causing electrolysis . The internal surface of the holes is the only electrically active surface with which the water solution comes into contact .
  • the primary task of the layer 23 is to reali ze a hydraulic resistance to the flow o f the water solution .
  • the consequent pressure drop must have a suf ficient value
  • the front dimensions of the electrodes 10 are of the order of decimetres ( 10 -1 m) with a thickness of the order of millimetres ( 10 ⁇ 3 m) .
  • the dimensions are about 3x4 dm with a thickness of 2 mm .
  • the distance between the two electrodes must be as short as possible and in the current example it has been set at about 2 mm .
  • the thickness of the electrical insulating coating deposited on the non-perf orated parts of the electrode surfaces 10a is of the order of microns ( 10 ⁇ 6 m) .
  • the layer shows a thickness of about 40 pm .
  • the pressure drop of the water solution leads to a more uni form distribution of the speeds of the water solution itsel f through all the holes in the hori zontal sections .
  • the uni formity of the speeds of the water solution ( thanks to the presence o f the layer 23 ) that crosses the electrode is the first condition for ( i ) ensuring that there are no points where the water solution is stopped and that it can therefore not drag the produced gas towards the outlet ; ( ii ) distributing the electrolysis current on the maximum surface of the holes , allowing the maximum yield of the electrode and a uni formly distributed generation of the gases ; ( iii ) allowing a larger scale up of the electrolytic cell from the fluid-dynamic point of view .
  • each of the half-elements 2 and 3 comprises a plurality of flow deflectors 24 each of which is arranged in front of a respective slit 12 of the metal sheet 10 , and has the function of deflecting the flow of water solution coming from the feeding tank 13 onto the holes 11 of the same metal sheet 10 .
  • the water solution enters from the inlet sleeve 7 and, through the opening 15 , is distributed in the feeding tank 13 in order to meet the conveying portions 21 , deflect upwards by flowing through the channels delimited by the dividing partition 20 , run along the hydraulic connections 16a and, then, outflow from the vertical slits 12 thus crossing the metal sheet 10 for the first time .
  • the water solution outflows from the vertical slits 12 it meets the flow deflectors 24 which deflect it against the front surface 10a .
  • the water solution is forced to cross the metal sheet 10 a second time after undergoing the pressure drop by the layer 23 .
  • the second crossing in the opposite direction to the first one ) takes place through the holes 11 .
  • the water solution once the flow deflectors 24 have been met , pas ses through the hydraulic resistance layer 23 which achieves a pressure drop ranging from 1 . 5 Pa to 10 Pa .
  • the water solution undergoes the electrolysis process as the metal sheet 10 is connected to a voltage generator .
  • the electrolysis of the water solution takes place exclusively during the second crossing of the metal sheet 10 through the holes 11 .
  • the first crossing of the metal sheet 10 takes place through the vertical slits 12 which are protected by the electrically insulated hollow partitions 16 and the front surface 10a is covered by the insulating coating, while the internal walls of the holes are the only electrically conductive portions with which the water solution comes into contact .
  • the hollow partitions 16 and the insulating coating arranged on the surface 10a ensure that the water solution coming from the feeding tank 13 , before crossing the metal sheet 10 for the second time , cannot come into contact with any electrically conductive surface .
  • the water solution and the gas produced by the electrolysis pass into the discharge tank 14 ( firstly vertical compartments and then upper hori zontal duct ) and from here , helped by the action of the conveying de flectors 22 , exit from the opening 17 .
  • the water solution and the produced gas cross the outlet sleeve 8 and pass into the external recirculation circuit 4 where they are separated by the respective degasser 5 . While the produced gas is collected, the water solution continues in the external recirculation circuit 4 to be introduced into the feeding tank 13 of the other hal f-element , or of the same hal felement , through the inlet sleeve 7 .
  • the metal sheet 10 may comprise equivalent lamellate portions consisting of a plurality of mutually parallel lamellae , the extended surfaces of which constitute the active electrolysis surfaces .
  • each of the lamellate portions will be arranged side-by- side to a vertical slit 12 , such that the water solution outflowing from the vertical slit 12 will be deflected by the relative flow deflector 24 towards the lamellate portion itsel f .
  • the water solution will then be forced to cross backwards firstly the layer 23 and then the metal sheet in the area of the lamellate portion undergoing, during its crossing, the electrolysis process by means of the active surfaces of the lamellae .

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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)
  • Fuel Cell (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Cellule électrolytique (1) pour l'électrolyse d'une solution aqueuse comprenant deux demi-éléments (2, 3) qui comprennent chacun une électrode respective comprenant une feuille métallique (10) reliée à un générateur de tension et logée dans une chambre d'électrolyse (C) définie entre les deux demi-éléments (2, 3), et des moyens (4) pour la recirculation continue de la solution aqueuse à l'intérieur de la chambre d'électrolyse (C). Dans chacune des feuilles métalliques (10), (i) une pluralité d'ouvertures d'électrolyse (11) présentant des parois latérales définissant des surfaces d'électrolyse actives de semelle et conçues pour permettre à une solution aqueuse de s'écouler d'une surface avant (10a) à une surface arrière (10b) de la feuille métallique (10) et (ii) une pluralité de fentes verticales (12) permettant à une solution aqueuse de s'écouler de la surface arrière (10b) à la surface avant (10a) de la feuille métallique (10) sont obtenues. Chacune des électrodes comprend une structure de résistance hydraulique conçue pour réaliser une perte de pression de 1,5 Pa à 10 Pa dans le passage d'une solution aqueuse de la surface avant (10a) à la surface arrière (10b) de la feuille métallique (10).
PCT/IB2023/050827 2022-01-31 2023-01-31 Cellule électrolytique pour la production de h2 WO2023144802A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102022000001544A IT202200001544A1 (it) 2022-01-31 2022-01-31 Cella elettrolitica per la produzione di h2
IT102022000001544 2022-01-31

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WO2023144802A1 true WO2023144802A1 (fr) 2023-08-03

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1143334A (fr) * 1980-06-10 1983-03-22 Chemetics International Ltd. Electrodes composites pour piles electrolytiques sans diaphragme employees en production de chlorates et d'hypochlorites (i)
WO1988003966A1 (fr) * 1986-11-20 1988-06-02 Fmc Corporation Element de production de peroxyde d'hydrogene
US6596136B1 (en) * 1998-10-30 2003-07-22 Uhdenora Technologies S.R.L. Membrane electrolytic cell with active gas/liquid separation
JP2013112864A (ja) * 2011-11-29 2013-06-10 Tokyo Metropolitan Industrial Technology Research Institute 電解セル
EP3571332B1 (fr) * 2017-01-18 2021-02-17 Andrea Capriccioli Cellule électrolytique pour la production de h2
WO2021214318A1 (fr) * 2020-04-23 2021-10-28 Spi Consulting Srl Appareil pour générer de l'hydrogène et de l'oxygène par électrolyse alcaline et procédé correspondant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1143334A (fr) * 1980-06-10 1983-03-22 Chemetics International Ltd. Electrodes composites pour piles electrolytiques sans diaphragme employees en production de chlorates et d'hypochlorites (i)
WO1988003966A1 (fr) * 1986-11-20 1988-06-02 Fmc Corporation Element de production de peroxyde d'hydrogene
US6596136B1 (en) * 1998-10-30 2003-07-22 Uhdenora Technologies S.R.L. Membrane electrolytic cell with active gas/liquid separation
JP2013112864A (ja) * 2011-11-29 2013-06-10 Tokyo Metropolitan Industrial Technology Research Institute 電解セル
EP3571332B1 (fr) * 2017-01-18 2021-02-17 Andrea Capriccioli Cellule électrolytique pour la production de h2
WO2021214318A1 (fr) * 2020-04-23 2021-10-28 Spi Consulting Srl Appareil pour générer de l'hydrogène et de l'oxygène par électrolyse alcaline et procédé correspondant

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IT202200001544A1 (it) 2023-07-31

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