The present invention relates to an electrolyzer for producing hydrogen and oxygen from water under high pressure, the water being present as an electrolyte of potassium or sodium hydroxide. The invention also relates to a corresponding method for producing hydrogen and oxygen from water under high pressure. More specifically, the present invention relates to a design minimizing the parasitic current affiliated with imbedded lye and/or hydrogen/oxygen flow channels inside the electrolyzer body.
Electrolyzers are used in the industry for producing hydrogen and oxygen. There exist many types of electrolyzers functioning in different ways depending on the electrolyte material involved. For producing hydrogen and oxygen, the electrolyzers in use are mainly of the PEM type or the alkaline type. PEM electrolyzers use pure water as the electrolyte, electrodes made from noble metals (e.g. Pt/Pd on the cathode side and Ir/Ru on the anode side), and a proton-conducting Polymer Electrolyte Membrane (PEM) which is often a perfluorinated sulfonic acid polymer separating the electrodes and oxygen and hydrogen. An over-voltage must be applied to the electrodes to enable the electrolysis to take place and the pressure must be at a relatively low level, due to the fragile PEM membrane. Alkaline electrolyzers, on the other hand, use an electrolyte of KOH or NaOH dissolved in water. This allows the use of cheap electrodes often based on nickel. The membrane is porous allowing electrolytes and ions to pass from one side to the other and at the same time prohibiting a cross-over flow of oxygen and hydrogen between the anode side and the cathode side. The optimum voltage for driving the process is typically between 2.0 and 2.5 volts.
A problem with all electrolyzers is that the gases are produced as bubbles that will cling to the electrodes and at least partially fill the chamber of the electrolysis cell. This will restrict the available contact area between electrolyte and electrodes, and thus, reduce the efficiency of the cells. Trying to solve this problem, alkaline electrolyzers have been operated at high pressure, as the design of these electrolyzers will stand the pressure. The high pressure will compact the bubbles and increase the contact area. A benefit of this being the possibility to store the produced oxygen and hydrogen directly at elevated pressure without using a subsequent compressor step. A drawback of this method is that the alkaline electrolyte becomes very aggressive (corrosive) at high pressure and the operating temperature is typically above 80° C.
Another drawback of alkaline electrolyzers is that some of the current supplied to the cell stack will not go the proper way from one electrode to the other, but may pass outside the stacked cells in the conducting electrolyte supplied through lye inflow channels and lye/gas outlet/outflow channels. These shunt currents are directly linked to a loss in the overall efficiency, and are known in the field as parasitic currents due to their undesirable character within electrolyzers. Contributing to the loss is both the lye inflow channels and the lye/gas outflow channels where the electrolyte will be carried away together with the gas stream (about 50% by volume). Both inflow and outflow channels on the hydrogen side and oxygen side, respectively, will conduct shunt/parasitic current. The electrolyte is separated from the gas in outside separators, and returned to the electrolyte through inflow channels.
Furthermore, the shunt currents will generate some gas in the respective gas channel, both hydrogen and oxygen gas, which means that some oxygen is generated in the hydrogen outlet channel and some hydrogen is generated in the oxygen outlet channel. Thus, the produced gases are not entirely pure and may have to be further cleaned before use. Thus, shunt currents will not only lower the efficiency but also lower the quality of the generated hydrogen and oxygen gas.
Hence, an improved alkaline electrolyzer eliminating the above-mentioned drawbacks would be advantageous, and in particular, a more efficient and/or reliable alkaline electrolyzer that can produce hydrogen/oxygen with a higher purity would be an additional advantageous.
It is an object of the present invention to provide an alkaline high-pressure electrolyzer with higher efficiency than prior art designs. It is a further an object of the present invention to provide an alkaline high-pressure electrolyzer with low or reduced shunt currents relative to prior art designs.
Thus, one aspect of the invention relates to an alkali highpressure electrolyzer for splitting water into hydrogen and oxygen, said electrolyzer comprising a stack of electrolysis cells, the cells comprising:
The invention is particularly, but not exclusively, advantageous for obtaining significantly reduced shunt currents when performing H2 production by electrolysis due to the first and second intermediate lye channels, and common hydrogen and oxygen outlet channels having extended lengths with correspondingly increased current path length and thereby increased resistance as seen by the shunt currents. Initial tests performed by the inventor indicate that the hydrogen production can be increased up to 23%, which is a remarkable result, cf. detailed description below, especially
Furthermore, the present invention will facilitate the production of hydrogen/oxygen with a higher purity due to the elimination of hydrogen/oxygen production in the inflow/outflow channels in the oxygen and hydrogen circuits.
Prior to discussing the present invention in further details, the following terms and conventions will first be defined:
In some embodiments, the first and second lye inlet channels may be located external to the electrolyzer stack, which may facilitate further increasing the path length of flow, and the hence reduce the shunt current.
Alternatively or additionally, the intermediate lye channels may beneficially be electrically isolated tubes or hoses connecting the first and second lye inlet channels to the respective cathodes and anodes in the stack.
In other embodiments, the spatial paths of the intermediate lye channels connecting the first and second lye inlet channels to the respective cathodes and anodes in the stack forming electrical insulated flow channels may have lengths being larger than a corresponding minimum length in order to reduce the shunt currents. As defined above, said minimum length may be taken as the shortest possible length and hence the intermediate lye channels will have an additional increased flow length according to the present invention. More specifically, the spatial paths of the intermediate lye channels connecting the first and the second lye inlet channels to the respective cathodes and anodes in the stack forming electrical insulated flow channels having lengths being at least 5 cm long, preferably at least 10 cm long, most preferably at least 20 cm long. In a certain layout, the non-conducting flow channels could be up to 20 cm long. Alternatively, they could be up to 30 cm long. More alternatively, they could be up to 40 cm long or even longer.
In still other embodiments, the electrolyzer may have at least part of the spatial paths of the intermediate lye channels being non-linear, preferably being at least partially curved, twisted, and/or spiralling, so as to increase the flow path, especially longer than the defined minimum length.
In advantageous embodiments, the hydrogen and oxygen outlet channels may be located external to the electrolyzer stack, which may facilitate further increasing the flow path length, and hence, reduce the shunt currents.
Alternatively or additionally, the intermediate hydrogen and oxygen channels may be tubes or hoses connecting the cathodes to the hydrogen outlet channel and the anodes to the oxygen outlet channel.
In some embodiments, the spatial paths of the intermediate hydrogen and oxygen channels connecting the cathodes to the hydrogen outlet channel and the anodes to the oxygen outlet channel forming electrical insulated flow channels may have lengths being larger than a corresponding minimum length in order to reduce the shunt current. More specifically, the spatial paths of the intermediate hydrogen and oxygen channels connecting the cathodes to the hydrogen outlet channel and the anodes to the oxygen outlet channel forming electrical insulated flow channels having lengths, which may be at least 5 cm long, preferably at least 15 cm long, most preferably at least 35 cm long. In certain embodiments, the length could be up to 40 cm long, preferably at least 50 cm long, most preferably at least 70 cm long.
In some embodiments, the spatial paths of the intermediate hydrogen and oxygen channels may be non-linear, preferably being at least partially curved, twisted, and/or spiralling etc. for increasing the flow path length, and hence reduce the shunt current.
In some embodiments, the intermediate hydrogen and oxygen channels may be connected to the cathode and the anode, respectively, through the rim of the bi-polar plate, the intermediate channels being connected by connection points to the rim in points offset from each other along the periphery of the rim. More specifically, these connection points may be alternately offset along the rim compared to neighbouring bi-polar plates for an improved design.
In still other advantageous embodiments, the intermediate hydrogen and oxygen channels may be passing an elevated position before entering the respective hydrogen and oxygen outlet channels, i.e. the elevated position may form a local maximum in the flow channel. This may further increase the flow path length, and hence reduce the shunt current.
In some beneficial embodiments, the tubes or hoses are made from electrically insulating materials, preferably polymer or ceramic material.
In some particularly beneficial embodiments, the electrolyzer may be arranged with circumferential positions, as seen from an end point of the stack of electrolysis cells, of:
In a particular embodiment, the electrolyzer may have a sub-set of the electrolysis cells from the stack, which may be operated without the remaining electrolysis cells outside the sub-set being operated. This can, for example, be obtained in a generalized N cell electrolyzer system grouped into N/x sub-groups, where the flow from the x groups of x cells is merged into individual manifolds before being combined in the shared manifold. In this segmented approach, there is an increased shunt resistance only for a part of the stack of electrolysis cells, which may—in some embodiments—be a particular advantage of the invention.
In a second aspect, the invention relates to an alkali high-pressure electrolyzer for splitting water into hydrogen and oxygen, said electrolyzer comprising a stack of electrolysis cells, the cells comprising:
Advantageously, in the second aspect of the present invention, the various combinations of first and second intermediate lye channels conducting lye with various combinations of intermediate hydrogen and oxygen channels can also be implemented in the context of the present invention as the skilled person will readily understand from the general teaching and principle of the first aspect of the invention. This is explained in more detail in connection with
Advantageously, in the third aspect of the present invention, the invention relates to a method for performing alkali high-pressure electrolysis by splitting water into hydrogen and oxygen in an electrolyzer comprising a stack of electrolysis cells, the cells comprising:
Advantageously, in the third aspect of the present invention, the various steps of conducting lye via the first and second intermediate lye channels with the various steps of conducting hydrogen and oxygen via the intermediate channels can also be implemented for reduced shunt currents in the context of the present invention as the skilled person will readily understand from the general teaching and principle of the first and/or second aspect of the invention.
In the fourth aspect, the present invention relates to an advantageous application of a Polymer Electrolyte Membrane (PEM) electrolyzer for splitting water into hydrogen and oxygen, said electrolyzer comprising a stack of electrolysis cells, the cells comprising:
Advantageously, in the fourth aspect of the present invention, the general teaching and principle of the invention according to the first, second, and/or third aspect can readily be applied generally for an electrolyzer system of the PEM-type like the skilled person in electrolysis will immediately understand, because also for PEM electrolysis shunt currents are not desirable for efficient and/or reliable hydrogen production. Thus, relative to the alkaline electrolysis, the lye is replaced with substantially deionized water supplied to cathodes and/or anodes of cells in the PEM electrolysis system. It may be an advantage that there is an improved cleanliness of the generated oxygen and hydrogen due to reduced/elimination of hydrogen formed in the oxygen-related flow channels and oxygen formed in the hydrogen-related flow channels.
The first, second, third, and fourth aspects of the present invention may each be combined with any of the other aspects. These and other aspects of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter.
The invention will now be described in detail with reference to the appended drawings, in which
The lye channels 4a, 4b are supplying lye to each cell through small openings 5a, 5b, i.e. the common inlet channel 4a supplying lye to the cathode sides 3a of the cells through the openings 5a, while the common channel 4b is supplying lye to the anode sides 3b of the cells through the openings 5b.
A schematic view of a conventional bi-polar plate is shown in
A shortcoming of this arrangement is that some of the electric current supplied to the end plates 11 (in
Briefly stated,
Thus, an alkali high-pressure electrolyzer for splitting water into hydrogen and oxygen is shown, preferably operating at a pressure from around atmospheric pressure up to 10, 20, 30, 40 bar or even higher. The electrolyzer comprises a stack of electrolysis cells with cathodes 3a and anodes 3b, and corresponding membranes 2 separating the cathodes from the anodes. Additionally, bi-polar plates 6 are supporting the cathodes and anodes. Insulating gaskets 10 are separating the cells as shown in
The invention is particular in that the lye supplying channels include first and second lye inlet channels 4a, 4b conveying lye into the stack of electrolysis cells with a multitude of first intermediate lye channels 5a conducting lye from the first lye inlet channel 4a to each cathode 3a in the stack, and a multitude of second intermediate lye channels 5b conducting lye from the second lye inlet channel 4b to each anode 3b in the stack, cf. also end view in the lower part of
Additionally, the hydrogen conducting channels include a common hydrogen outlet channel 7a and a multitude of intermediate hydrogen channels 8a conducting hydrogen from each cathode 3a to the common hydrogen outlet channel 7a, and the oxygen conducting channels include a common oxygen outlet channel 7b and a multitude of intermediate oxygen channels 8b conducting oxygen from each anode 3b to the common oxygen outlet channel 7b. cf. also end view in the upper part in
In the upper part of
Referring to
Moreover, it is further apparent that only one side of the upper intermediate hydrogen and oxygen channels 8a, 8b, e.g., the left intermediate channel 8b could be applied within the context of the present invention. Likewise, is further apparent that only one side of the lower intermediate lye channel, e.g., the right intermediate lye channel 5b could be applied within the context of the present invention, and still some advantage i.e. a reduced shunt current could be obtained.
Two test units were constructed and tested according to the present invention: Unit (i) based on conventional technology with two long internal lye/H2O feed channels for the H2/cathode and the O2/anode systems, respectively. Hereto, two internal exit channels for the lye/H2O/O2 and lye/H2O/H2 exit lines.
Unit (ii) based on the present invention with individual external input and external output channels for lye/H2O feeds and external lye/H2O/O2 and lye/H2O/H2 exit lines from the anode and cathode parts of the cells, respectively.
Tabel 1 below provides the measured H2 flow as a function of the supplied current to the conventional electrolyzer configuration as well as for the present invention.
The amount of hydrogen produced by an electrolyzer unit can in principle be expressed as:
In other words, doubling the number of cells or doubling the current, I, through the cell stack will cause a doubling of the amount of produced hydrogen. The efficiency constant μ is related to a lowering in the overall electrolyzer efficiency cause by the shunt current running in the flow channels. Depending on the electrolyzer size and/or current load, the efficiency μ is typically between 0.9 and 1 where a value close to 1 is obtainable with the present invention. For the current measurement in the case of the smaller electrolyzer illustrated in the present case it corresponds to an increase from around μ=0.8 to around μ=1.
The shunt resistance (SR) can be modelled by a simple Ohmic model:
Hence, increasing the length of the non-conducting tubings will increase the shunt resistance increasing the overall electrolyzer efficiency. In principle, the longer tubings the better although in practice this is not feasible because of the required flow of ingoing lye and/or outgoing flow of hydrogen and oxygen. Tubing with a length between 10-30 cm is recommended within the teaching and principle of the present invention, though of course longer tube lengths, e.g. 30-50 cm or 50-80 cm, can also be contemplated in the context of the present invention.
Hence, decreasing the cross-sectional area of the non-conducting tubings would additionally or alternatively, increase the shunt resistance. Typically, tube diameters may be values like 0.635 cm/0.25 inch, 0.32 cm/0.125 inch, 0.165 cm/0.063 inch or other standard diameters, etc.
As the skilled person will understand, these steps may be performed substantially simultaneously or in a sequence of steps depending on the specific embodiment of the present invention.
Although the present invention has been described in connection with the specified embodiments, it should not be construed as being in any way limited to the presented examples. The scope of the present invention is set out by the accompanying claim set. In the context of the claims, the terms “comprising” or “comprises” do not exclude other possible elements, steps, or designs. Also, the mentioning of references such as “a” or “an”, etc. should not be construed as excluding a plurality. The use of reference signs in the claims with respect to elements indicated in the figures shall also not be construed as limiting the scope of the invention. Furthermore, individual features mentioned in different claims, may possibly be advantageously combined, and the mentioning of these features in different claims does not exclude that a combination of features is not possible and advantageous.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20211575 | Dec 2021 | NO | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/087587 | 12/22/2022 | WO |