The present disclosure relates to electrolysis. Teachings thereof may be embodied in methods and electrolysis systems for electrochemical utilization of carbon dioxide wherein carbon dioxide is introduced into an electrolysis cell and reduced at a cathode.
Currently around 80% of the worldwide energy demand is met by the combustion of fossil fuels, the burning of which gives rise to worldwide annual atmospheric emissions of approximately 34 000 million tonnes of carbon dioxide. This release into the atmosphere is the major contribution of carbon dioxide, which in the case of a lignite power station, for example, can be up to 50 000 tonnes per day. Carbon dioxide is one of the gases known as greenhouse gases, whose negative effects on the atmosphere and the climate are debated. Since carbon dioxide occupies a very low position thermodynamically, it is difficult to reduce it to give reusable products, a fact which has left the actual recycling of carbon dioxide to date within the realm of theory or of academia. Natural breakdown of carbon dioxide is accomplished, for example, by photosynthesis. A replica of the natural photosynthesis process using industrial photocatalysis has to date lacked adequate efficiency.
One alternative is the electrochemical reduction of carbon dioxide. Systematic studies of the electrochemical reduction of carbon dioxide are still a relatively young field of development. Efforts to develop an electrochemical system able to reduce an acceptable volume of carbon dioxide only emerged a few years ago. Laboratory-scale research efforts have shown that, preferentially, metals are to be used as catalysts for the electrolysis of carbon dioxide. While carbon dioxide is reduced almost exclusively to carbon monoxide at silver, gold, zinc, palladium, and gallium cathodes, for example, the reaction products at a copper cathode comprise a multitude of hydrocarbons.
If the electrolyte used in both circuits is the same, prolonged operation of the electrolysis is accompanied by changes both in the pH and also in the ion concentration in the individual solutions. The membrane additionally complicates the construction. If, for example, the anolyte and catholyte used comprise a 0.5 M KHCO3 solution, the cell voltage after a couple of hours increases sharply, since the cations have migrated from the anolyte chamber into the catholyte chamber to the electrode as a result of the electrical voltage applied. Although the osmotic pressure is compensated to start with, or even counteracted after a certain time, the electrical attraction of the cathode is stronger and the migration of cations proceeds primarily in one direction. If the initial concentration is raised or the anolyte is periodically renewed, crystallization of KHCO3 in the catholyte can be found after a few hours. Similar comments also apply in respect of electrolytes whose electrical conductivity is generated by other salts (sulfates, phosphates).
It is therefore necessary for the electrolyte to be regenerated separately. To enable a continual flow of electrolyte, therefore, a sufficient amount of electrolyte must be present in the reservoirs. In a large-scale industrial plant, this necessitates tanks of a considerable size. The teachings of the present disclosure may provide an electrolysis system and also a method for the electrochemical utilization of carbon dioxide, said system and said method alleviating or obviating the problems identified above.
For example, in some embodiments an electrolysis system (100) for carbon dioxide utilization may include: an electrolysis cell (1) having an anode (4) in an anode chamber (2) and having a cathode (5) in a cathode chamber (3), where the cathode chamber (3) is designed to accommodate carbon dioxide and bring it into contact with the cathode (5), where catalysis is enabled of a reduction reaction of carbon dioxide to at least one hydrocarbon compound or to carbon monoxide. In addition, the system may include first and second electrolyte reservoirs (6, 7), a first product gas line (14) from the first electrolyte reservoir (6), and a second product gas line (15) from the second electrolyte reservoir (7). Also, there may be a first connecting line (9) for supplying electrolyte from the first electrolyte reservoir (6) to the anode chamber (2), a second connecting line (10) for taking electrolyte from the anode chamber (2) off to the second electrolyte reservoir (7), a third connecting line (11) for supplying electrolyte from the second electrolyte reservoir (7) to the cathode chamber (3), a fourth connecting line (12) for taking electrolyte from the cathode chamber (3) off to the first electrolyte reservoir (6), and a pressure-equalizing connection (13) which directly connects the first and second electrolyte reservoirs (6, 7).
In some embodiments, there is a pump (42) in the pressure-equalizing connection.
In some embodiments, there are level sensors for both reservoirs.
In some embodiments, the two electrolyte reservoirs (6, 7) are together designed as an individual container having a dividing wall (32) for subdivision into the two electrolyte reservoirs (6, 7), where the dividing wall (32) has an opening (33) as pressure-equalizing connection.
In some embodiments, there are means for the introduction of inert gas, especially nitrogen, into the reservoirs.
In some embodiments, there is a supply line for supplying the carbon dioxide.
In some embodiments, the supply line for supplying the carbon dioxide has an overpressure valve.
In some embodiments, the supply line and the first product gas line are brought together.
In some embodiments, the product gas lines are brought together in an overpressure valve.
As another example, a reduction method for carbon dioxide utilization by means of an electrolysis system (100), may include carbon dioxide is passed through a cathode chamber (3) of an electrolysis cell (1) and is brought into contact with a cathode (5). A reduction reaction of carbon dioxide to at least one hydrocarbon compound or to carbon monoxide is carried out. A first product gas is passed by means of a first product gas line (14) out of the first electrolyte reservoir (6). A second product gas is passed by means of a second product gas line (15) out of the second electrolyte reservoir (7). The electrolyte is passed in a crossflow into and out of the electrolyte cell (1), by electrolyte being passed from a first of two electrolyte reservoirs (6) to the anode chamber (2). Electrolyte is passed from the anode chamber (2) to a second of the two electrolyte reservoirs (7). Electrolyte is passed from the second electrolyte reservoir (7) to the cathode chamber. Electrolyte is passed from the cathode chamber (3) to the first electrolyte reservoir (6). A similar liquid level in the electrolyte reservoirs is brought about by means of a pressure-equalizing connection (13) between the first and second electrolyte reservoirs (6, 7).
Examples and embodiments of teachings of the present disclosure are described again exemplarily with reference to
The electrolysis system of the present disclosure for carbon dioxide utilization, may include:
The system may further comprise:
In some embodiments, a reduction method for carbon dioxide utilization by means of an electrolysis system, may include:
Furthermore, the electrolyte is passed in a crossflow into and out of the electrolysis cell, by
The effect of passing the electrolyte in the crossed flow (crossflow) is that changes occurring in pH are compensated again.
If cations migrate to the cathode, they are transported back again into the anode chamber mechanically by way of the crossflow. A further effect is that the salt concentration in the two electrode chambers remains constant and so salting-out is durably prevented. On the basis of this operating regime, ongoing electrolysis with the same electrolyte in both electrode chambers is possible.
In some embodiments, the electrolysis system comprises a pressure-equalizing connection which directly connects the first and second electrolyte reservoirs. Inequalities in the flow of the electrolyte from the two reservoirs may over prolonged periods, without countermeasures, lead to an unequal electrolyte level in the two reservoirs and even, in the extreme case, to one side of the cell running dry. The pressure-equalizing connection establishes a direct connection of the two reservoirs, which as a result acquire a continually equal liquid level, in analogy to communicating pipes. This prevents one side of the cell running dry.
For the exchange of the liquid electrolyte it is useful for the compensating line at both electrolyte reservoirs to be connected as far downward as possible, as for example in the lower half of the height of the respective reservoir, more particularly in the lower quarter.
In addition to automatic equalization of the liquid level in the reservoirs, it is also possible to carry out a regulated exchange of electrolyte. For that purpose, then, in some embodiments, a pump is present in the pressure-equalizing connection. This pump ensures forced exchange of electrolyte. Control may be carried out using the input signals of fill level sensors for both reservoirs.
In some embodiments, the two reservoirs are separate vessels, in which case the pressure-equalizing connection takes the form, for example, of a pipe between the vessels. In some embodiments, the two reservoirs may be an individual vessel with a dividing wall for subdivision into the two reservoirs, with the dividing wall having an opening as pressure-equalizing connection. The opening as well, of course, may be located in the lower region of the reservoirs, to allow an exchange of the liquid electrolyte even when the liquid level is low.
In some embodiments, the electrolysis system comprises pumps in the first and third connecting lines which convey the electrolyte to anode chamber and cathode chamber. Furthermore, the electrolysis system may comprise a supply line for supplying the carbon dioxide.
In some embodiments, the electrolysis system comprises means for pressure regulation for at least one of the reservoirs. Thus, for example, the feedline for supplying the carbon dioxide may have an overpressure valve. If this valve opens, the carbon dioxide which then flows through can be mixed with the product gas from the first product gas line and the gases can be passed together to an analytical facility and/or to a product gas storage facility. In some embodiments, the product gas lines are brought together in an overpressure valve. As a result, through a suitable choice of the overpressure valve, an equal pressure is ensured in the gas phase in the reservoirs.
In some embodiments, electrolysis system comprises means for the introduction of inert gas, e.g., nitrogen, into the reservoirs. For this purpose, the inlets at the reservoirs may be disposed in the lower region of the respective reservoir, and in the lower region the reservoirs comprise a layer of glass frit which is pervious for the inert gas.
In some embodiments, the cathode of the electrolysis system comprises silver, copper, copper oxide, titanium dioxide, or another metal-oxide semiconductor material. The cathode may also, for example, be a photocathode, in which case it would be possible to operate a photoelectrochemical reduction process for the utilization of carbon dioxide, known as photoassisted CO2 electrolysis. In some embodiments, this system can operate purely photocatalytically. In some embodiments, the electrolysis system comprises a platinum anode. In some embodiments, KHCO3, K2SO4, and K3PO4 are used as electrolyte salts in different concentrations. In some embodiments, potassium iodide KI, potassium bromide KBr, potassium chloride KCl, sodium hydrogencarbonate NaHCO3, sodium sulfate Na2SO4 are used. Other sulfates, phosphates, iodides, or bromides, however, can also be used for increasing the conductivity in the electrolyte. As a result of continual supplying of the carbon-containing gas, there is no need to supply carbonates and/or hydrogencarbonates, which are instead formed in the cathode chamber in operation.
In some embodiments, the cathode (K) has, for example, a surface protection layer. In some embodiments, semiconductor photocathodes, but also, in particular, metallic cathodes, have a surface protection layer. By a surface protection layer is meant that a layer which is relatively thin in comparison to the overall electrode thickness separates the cathode from the cathode chamber. The surface protection layer for this purpose may comprise a metal, a semiconductor, or an organic material. In some embodiments, this is a protective titanium dioxide layer.
The primary aim of the protective effect is to protect the electrode from attack by the electrolyte or by reactants, products or catalysts, and their dissociated ions, in solution in the electrolyte, with consequent dissolving of ions from the electrode, for example. With regards specifically to the electrochemical reduction method in aqueous media, or at least in a medium which contains small quantities of water or of hydrogen, a suitable surface protection layer is very important for the long life and functional stability of the electrode in the process. Even small morphological changes, as a result of corrosive attacks, for example, may influence the overvoltages of hydrogen gas H2 or carbon monoxide gas CO in aqueous electrolytes or water-bearing electrolyte systems. The consequence would be, on the one hand, a drop in the current density and, accordingly, a very low system efficiency for the conversion of carbon dioxide, and, on the other hand, the mechanical destruction of the electrode.
The electrolysis system 100 shown diagrammatically in
Anode 4 and cathode 5 are each connected electrically to a voltage supply. The anode chamber 2 and the cathode chamber 3 of the electrolysis cell 1 shown are each equipped with an electrolyte inlet and electrolyte outlet, via which the electrolyte and also electrolysis byproducts, e.g., oxygen gas O2, from the anode chamber 2 or cathode chamber 3, respectively, are able to flow in and out.
Anode chamber 2 and cathode chamber 3 are tied into an electrolyte circuit via first to fourth connecting lines (9 . . . 12). The flow directions of electrolyte are shown by means of arrows in both circuits. Also tied into the electrolyte circuit, moreover, are first and second reservoirs 6, 7, in which the electrolyte is held. The electrolyte circuit here, unlike known carbon dioxide electrolysis plants, takes the form of a crossflow. To this end, a first of the connecting lines 9 passes electrolyte and, where appropriate, reactants and products mixed therewith or dissolved therein from the first reservoir 6, conveyed by a pump 8a, to the anode chamber 2 and its electrolyte inlet.
From the electrolyte outlet of the anode chamber 2, in turn, a second connecting line 10 passes the electrolyte with admixed substances to the second reservoir 7. The electrolyte is therefore not returned to the original reservoir 6. Electrolyte from the second reservoir 7, in turn, is conveyed through a third connecting line 11 by means of a pump 8b to the cathode chamber 3. Electrolyte from the cathode chamber 3 is passed via a fourth connecting line 12 to the first reservoir 6. In this way, a crossed circuit is produced for the electrolytes, in which a given amount of electrolyte, over time and at least in parts, reaches and travels through not only both reservoirs but also anode and cathode chambers 2 and 3.
The reservoirs 6 and 7 are connected by means of an equalizing pipe 13. The outlets to the equalizing pipe 13 in the reservoirs 6 and 7 are usefully located in the lower part of the reservoirs, to allow the exchange of liquid even when the liquid level is low. The equalizing pipe 13 ensures that neither of the reservoirs 6 and 7 can run empty, and the height of the electrolyte level is the same in both.
Leading out of the first reservoir 6 is a first product gas line 14. This line connected via a first overpressure valve to a supply line 16 for carbon dioxide, which transports the carbon dioxide to the electrolysis cell 1. Via this connection it is possible optionally for carbon dioxide, which if the pressure is exceeded is in part not delivered into the electrolysis cell 1, and also product gas, together with the inert gas from the first reservoir 6, to be passed to an analytical facility and to a product storage facility that is not shown in
A second product gas line 15 from the second reservoir 7 passes together with the joint line, consisting of first product gas line 14 and carbon dioxide supply line 16, to a second overpressure valve 18. This controlled merging of the product gas lines 14, 15 from the reservoirs 6, 7 ensures that the pressure in both reservoirs 6, 7 is the same and therefore that the liquid level is not displaced. In some embodiments, a regulated pressure control system monitors the differential pressure at the GDE, so that the latter does not suffer excessive mechanical loading. The second overpressure valve 18 is set so as to ensure that no product gas of the anode 4 enters the analytical facility.
In some embodiments, at the mixing of H2 and O2, care is taken to ensure that the dilution with N2 is sufficient not to produce an explosive detonating-gas mixture. If this point cannot be ensured, then the two gas streams should be kept separate, and pressure equalization takes place via a separate mechanism.
Another embodiment of the two reservoirs 6, 7 is shown in
A further alternative design is shown in
Equalization in this example is carried out by means of a pump 42. The pump is controlled by control electronics which are not shown in
Number | Date | Country | Kind |
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10 2015 212 503.3 | Jul 2015 | DE | national |
This application is a U.S. National Stage Application of International Application No. PCT/EP2016/062253 filed May 31, 2016, which designates the United States of America, and claims priority to DE Application No. 10 2015 212 503.3 filed Jul. 3, 2015, the contents of which are hereby incorporated by reference in their entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/EP2016/062253 | 5/31/2016 | WO | 00 |