WO2017014635A1 - Procédé et réacteur permettant une réduction électrochimique du dioxyde de carbone - Google Patents

Procédé et réacteur permettant une réduction électrochimique du dioxyde de carbone Download PDF

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Publication number
WO2017014635A1
WO2017014635A1 PCT/NL2016/050545 NL2016050545W WO2017014635A1 WO 2017014635 A1 WO2017014635 A1 WO 2017014635A1 NL 2016050545 W NL2016050545 W NL 2016050545W WO 2017014635 A1 WO2017014635 A1 WO 2017014635A1
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carbon dioxide
cathode
anode
compartment
pressure
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Robert Christiaan Franciscus DE KLER
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Coval Energy Ventures BV
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Coval Energy Ventures BV
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Priority to ES16757367T priority Critical patent/ES2824158T3/es
Priority to EP16757367.4A priority patent/EP3325692B1/fr
Priority to DK16757367.4T priority patent/DK3325692T3/da
Publication of WO2017014635A1 publication Critical patent/WO2017014635A1/fr
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    • 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
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • 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
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • the invention is directed to a method for electrochemically reducing carbon dioxide, and to an electrochemical reactor.
  • One possible way of mitigating carbon dioxide emissions is to convert carbon dioxide into economically valuable materials, such as fuels and industrial chemicals. If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that can be stored for later use will be possible.
  • thermodynamic stability of carbon dioxide is by-passed by a simple one-electron reduction at an electrode, leading to in situ generation of reactive intermediates. Often, room temperature conditions are sufficient, considering that the energy of the electrons is determined by the applied voltage. Since the electrochemical reduction takes place on a cathode surface, the need for complex homogeneous organometallic catalysts is minimised. Furthermore, electricity will be increasingly of renewable origin in the future, making organic electro-synthesis a promising technology for environmentally friendly chemical processes.
  • the electrochemical reduction of carbon dioxide can be applied for the synthesis of fuels like formic acid, methanol or methane. This allows storage of electric energy from periodic sustainable origin, like solar or wind energy.
  • Electro-synthesis is typically carried out in an electrochemical reactor connected to an external voltage or current source.
  • electrochemical reactors can be categorised into undivided and divided cells.
  • a divided cell has a cathode compartment with a cathode, an anode compartment with an anode, and an interface (or divider or separator) between cathode compartment and anode compartment.
  • the interface in a divided cell functions as a separator. It is a barrier for specific species while allowing the transport of other species.
  • the separator controls the flow of ions between the two compartments. In particular, the separator may selectively allow the transport of cations from the anode compartment into the cathode compartment while simultaneously preventing the transport of anions in the opposite direction.
  • the separator may selectively allow the transport of anions from the cathode compartment into the anode compartment while preventing the transport of cations in the opposite direction.
  • control over ion flow provides a means to enhance or enforce the desired reaction chemistry to occur in the fluids contained in the individual compartments with respective electrodes, and increase the current efficiency by preventing the cycling of species by sequential oxidation and reduction.
  • the electrochemical reduction of carbon dioxide is a promising application in the field of electrochemistry.
  • materials can be produced including formic acid, formates, carbon monoxide, hydrogen, syngas, methanol, methane, and propane.
  • Products and process efficiencies depend amongst others on cell configuration, cathode material, surface area of the electrode, porosity of the electrode, catalyst, electrolyte (anolyte as well as catholyte) participating in reaction chemistry or acting as pH buffer, and process conditions like temperature, pressure, applied fluid flow, (over)potential, etc.
  • a conventional configuration in the electrochemical reduction of carbon dioxide comprises a divided cell with a cation exchange membrane (proton exchange membrane or cation membrane) separating an aqueous anolyte and catholyte.
  • Protons from water splitting
  • /or cations from the specific anolyte transfer to the cathode compartment where they react with the reduced carbon dioxide.
  • Products formed are retained in the cathode compartment, while typically oxygen evolves at the anode.
  • US-A-2008/0 223 727 describes a continuous co-current electrochemical reduction of carbon dioxide using a catholyte mixture with a specific volume ratio of carbon dioxide gas and liquid catholyte solvent.
  • a fuel like hydrogen is fed as a gas to the anode compartment.
  • the protons produced by direct splitting of the hydrogen fuel at the anode, transfer through the cation exchange membrane to react with the reduced carbon dioxide as in the previously mentioned configuration.
  • an anion exchange membrane is employed as separator.
  • the reduction of carbon dioxide at the cathode under wet conditions leads to the production of hydroxide ions that transfer through the anion exchange membrane and react with a hydrogen fuel at the anode to produce water.
  • the product of the carbon dioxide reduction is retained in the cathode compartment.
  • the above reactor configurations have in common that they use an ion selective membrane of either the cation or the anion exchange type, and the use of an aqueous phase where at the cathode compartment carbon dioxide is solubilised in the aqueous phase. Reduction and oxidation take place in the cathode compartment and the anode compartment of the electrochemical reactor, respectively.
  • Bipolar membrane technology is relatively unexplored and finds an increasing number of applications in electro-catalytic membrane reactors (Balster et al., Chemical Engineering and Processing 2004, 43, 1115-1127).
  • a bipolar membrane is catalytically active and may contribute to
  • Bipolar membranes are known to be part of electro-dialysis stack design, and are configured together with anion and cation exchange membranes.
  • a bipolar membrane is a synthetic membrane comprising two oppositely charged ion-exchanging layers in contact with each other.
  • the bipolar membrane may be considered the combination of a cation exchange membrane and an anion exchange membrane. By this arrangement of charged layers, the bipolar membrane is not effective in transporting either cations or anions across the full width of the membrane, and is to be distinguished from the ion selective membranes employed in the conventional electrochemical reduction of carbon dioxide.
  • problems associated with the conventional electrochemical processes include low availability of gaseous reactant at atmospheric pressure, substantial over potentials at the electrodes (stack), a high internal resistance to overcome (low power density), co-transport of anolyte with protons through cation exchange membrane and competitive reaction of these with the anion in the cathode compartment and a requirement for a secondary chemical conversion outside the main electrochemical reactor, low water dissociation rate, difficulties in achieving full conversion of a liquid and a gaseous reactant in a single pass through an electrochemical reactor operated in continuous mode, integrity of a thin membrane during pressurisation or depressurisation in particular with a gaseous phase on one side and a liquid phase on the other side.
  • Objective of the invention is to overcome one or more of these problems faced in the prior art.
  • the invention is directed to a method for electrochemically reducing carbon dioxide, comprising
  • a separator comprising a bipolar membrane, a
  • charge-mosaic membrane or a layered mixture of anion and cation exchange resins, and wherein the pressure in the electrochemical reactor is 20 bara or more.
  • the separator participates in the intended reaction chemistry instead of only transferring either cations or anions as being state of the art in carbon dioxide
  • the method of the invention advantageously allows for high electric power density, low voltage
  • the separator can comprise (or consist of) a bipolar membrane, a charge-mosaic membrane, or a layered mixture of anion and cation
  • a bipolar membrane is defined as a synthetic membrane comprising two oppositely charged ion-exchanging layers in contact with each other.
  • a charge-mosaic membrane is defined as a membrane having a charge structure comprised of cation-exchange domains and anion-exchange domains which are alternately aligned and each of which penetrates the membrane from one side to the other side.
  • the separator may also be a permeable layer confining a mixture of a cation exchange resin and an anion exchange resin.
  • the separator comprises or consists of a bipolar membrane.
  • the separator may be in direct electrical contact with the cathode and/or anode of the electrochemical reactor.
  • the separator may be in indirect electrical contact with the cathode and/or anode of the electrochemical reactor via an electrically conductive liquid, such as an electrolyte, or more specifically a catholyte or anolyte.
  • the method of the invention may be performed in various embodiments that allow reduction of carbon dioxide using different configurations of the electrochemical reactor.
  • water can be split at the separator, thereby producing OH- ions and H + ions.
  • the feed with carbon dioxide (which can be present in different forms such as carbon dioxide, carbonic acid, bicarbonate, carbonate, etc.) can be reduced in the cathode compartment while
  • the separator preferably comprises a cation exchange layer and an anion exchange layer in contact with each other at a junction, wherein the cation exchange layer faces the cathode and the anion exchange layer faces the anode.
  • This configuration may be represented by the following overall reactions.
  • electrochemical reactor 100 comprises a cathode compartment 110, a separator 120, and an anode compartment 130.
  • carbon dioxide can be reduced in the cathode compartment (where the carbon dioxide can be present in different forms such as carbon dioxide, carbonic acid, bicarbonate, carbonate, etc.), thereby producing OH- ions.
  • water can be oxidised to produce H + ions.
  • the OH- ions and H + ions can be recombined at the separator, thereby producing water.
  • the separator preferably comprises a cation exchange layer and an anion exchange layer in contact with each other at a junction, wherein the anode exchange layer faces the cathode and the cation exchange layer faces the anode.
  • This configuration may be represented by the following overall reactions.
  • the electrochemical reactor 100 comprises a cathode compartment 210, a separator 220, and an anode compartment 230.
  • the separator comprises a cation exchange layer and an anion exchange layer in contact with each other at a junction, wherein the cation exchange layer faces the cathode and the anion exchange layer faces the anode.
  • the separator comprises a cation exchange layer and an anion exchange layer in contact with each other at a junction, wherein the anion exchange layer faces the cathode and the cation exchange layer faces the anode.
  • the electrochemical reactor can advantageously be free of liquid electrolyte, such as catholyte and/or anolyte.
  • the electrochemical reactor is free of catholyte.
  • the cathode and bipolar membrane can be in direct contact in order to minimise electrical resistance.
  • Carbon dioxide can, for example be supplied as dense gas to the cathode compartment, and water may be supplied either to the cathode compartment or to the anode compartment in the appropriate amount to wet the cathode and anode structure thereby forming a reactive layer.
  • the absence of liquid electrolyte is highly preferred, as the presence of liquid electrolyte can lead to the production of undesirable by-products.
  • the method may be operated continuously, semi-continuously, or in batch. It is preferred to perform the method of the invention in a continuous mode.
  • the method of the invention further comprises releasing oxygen from the anode compartment, and collecting reduced carbon dioxide product or product mixture from the cathode compartment.
  • the reduced carbon dioxide product or product mixture can comprise one or more components from a group of molecules referred to as platform chemicals, such as alkanes, alkenes, syngas, carboxylic acids, alcohols, including diols, aldehydes, and ketones. More specifically, the carbon dioxide product or product mixture can comprise one or more components selected from the group consisting of carbon monoxide, hydrogen, syngas, formic acid, a formate, methanol, acetaldehyde, methane, and ethane. Preferably, the reduced carbon dioxide or product mixture comprises one or more selected from the group consisting of methanol, formic acid, a formate, and acetaldehyde. Accordingly, the method can involve the conversion of carbon dioxide into one or more of these platforms.
  • the method comprises the
  • the product that is obtained may be controlled by varying the applied voltage.
  • a water feed is introduced into the anode compartment.
  • This water feed may be supplied in liquid form, in vapour form or in gaseous form.
  • the water feed comprises at least water, but may further comprise other components such as one or more selected from the group consisting of pH control agents, conductivity control agents, and reactivity inhibitors. It is also possible that the water feed is water.
  • the water feed is a feed that has water as main component.
  • a carbon dioxide feed is introduced into the cathode compartment.
  • This carbon dioxide feed may be supplied in one of the following phase, as a supercritical phase, in a liquid phase, in a dense phase, in a vapour phase or in a gaseous phase.
  • the carbon dioxide feed is in a dense phase.
  • dense phase carbon dioxide refers to carbon dioxide in either liquid form or supercritical form.
  • the carbon dioxide itself may be liquid, or it may be a solute in a liquid solvent, such as water.
  • the carbon dioxide feed comprises at least carbon dioxide, but may further comprise other components, such as one or more selected from the group consisting of water droplets, aerosols, pH control agents, conductivity control agents, and compounds for mediated electrochemical conversion.
  • the carbon dioxide feed is a feed that has carbon dioxide as main component.
  • the carbon dioxide feed comprises a majority of carbon dioxide and a minority of water.
  • the carbon dioxide feed is pre-conditioned in a dedicated vessel to obtain high concentrations of reactive species (CO2, carbonic acid, bicarbonate, and carbonate) for carbon dioxide reduction.
  • the carbon dioxide feed is suitably pre-conditioned in terms of pressure, temperature, and pH, and preferably consists of a mixture of carbon dioxide and water with an excess of carbon dioxide.
  • the carbon dioxide is preferably fed to the reactor in a dense phase and water is preferably partly solubilised in the dense carbon dioxide phase, whereby the dense phase carbon dioxide will be highly concentrated with ionic reactive species.
  • reactive species are formed by a reaction between water and the carbon dioxide during the pre-conditioning step, and (additional) ionic reactive species can be formed during the contacting in the electrochemical reactor of the dense phase carbon dioxide with the membrane where the membrane is saturated with water.
  • the pressure of the carbon dioxide feed is preferably 20 bara or more, such as 30 bara or more, even more preferably 50 bara or more, and most preferably 60 bara or more. Usually, the pressure of the carbon dioxide feed will not exceed 200 bara. More preferably, the pressure of the carbon dioxide feed will be 150 bara or less, even more preferably 100 bara or less, and most preferably 80 bara or less.
  • the carbon dioxide feed may have a density of 10-1000 kg/m 3 , preferably a density of 100-980 kg/m 3 , and more preferably a density of
  • Both water feed and carbon dioxide feed may be introduced into the electrochemical reactor continuously or intermittently. It is also possible to introduce the water feed and carbon dioxide feed into the electrochemical reactor in a batch wise fashion.
  • This oxygen can be released from the anode compartment via an anode compartment outlet. It is preferred that the rate of introducing the carbon dioxide feed and the rate of releasing the oxygen is monitored and controlled. This may be realised, for instance, by releasing oxygen when the absolute pressure thereof is 0.2 bar or more higher than the pressure of the carbon dioxide feed, preferably 0.3-1.0 bar higher than the pressure of the carbon dioxide feed, and more preferably 0.4-0.8 bar higher than the pressure of the carbon dioxide feed. This control can advantageously prevent mechanical damages by avoiding large pressure differences in the system.
  • the pressure difference between the anode and the cathode compartment i.e. the pressure difference over the membrane, will be used to control the rate of introducing the carbon dioxide feed and releasing the oxygen.
  • the oxygen maybe released, for instance, when the pressure difference between the anode and the cathode
  • compartment is 0.2 bar or more, preferably in the range of 0.2-1.0 bar pressure difference, and more preferably in the range of 0.3-0.8 bar pressure difference.
  • This control of the feeding and the release of the various streams can be achieved, by an advanced pressure control system, employing pressure transducers, pressure transmitters, pressure controllers, and pressure differential transducers.
  • the carbon dioxide feed can be fed to the carbon dioxide feed
  • electrochemical reactor at a fixed pressure (e.g. in the range of 20-100 bara), thereby guaranteeing an automatic supplementation of this reactant.
  • Fluctuations in the water feed can be damped by using, for example, an expansion chamber, pusher bellows, etc.
  • an expansion chamber for both the water feed stream and the carbon dioxide feed stream a
  • thermoconditioning step is included.
  • a pressurised, thermostatic vessel or hydraulic accumulator is employed to assure stable pressure and temperature levels for the feed streams.
  • the water feed supplied at the anode can be in direct contact with the produced gaseous oxygen.
  • the pressure thereof can be at an absolute pressure with a set-point for a control valve to release oxygen slightly higher than the carbon dioxide feed pressure, for example 0.5 bar higher than the carbon dioxide feed pressure.
  • the pressure difference over the membrane and the pressure difference between the various streams will not exceed the pressure of the operational window.
  • the pressure difference over the membrane should be in the range of 0.3-0.8 bar.
  • the command signal for the valve can be derived from a sensor that monitors an absolute pressure.
  • the liquid reactants contact the pressure hull of the vessel.
  • a sensor may be employed that monitors a pressure differential between the carbon dioxide feed and released oxygen and controls and overrules the absolute pressure signal command.
  • the pressure differential signal can affect the operation of a valve connected to the cathode compartment inlet to adjust the rate of carbon dioxide feed introduction and a valve at the anode compartment outlet to adjust the rate of oxygen release.
  • the discharge rate of the reduced carbon dioxide product or product mixture may be controlled using a control valve connected to the cathode compartment outlet.
  • the pressure in the electrochemical reactor is 20 bara or more, preferably 30 bara or more, even more preferably 50 bara or more, and most preferably 60 bara or more. Usually, the pressure in the electrochemical reactor will not exceed 200 bara. More preferably, the pressure in the electrochemical reactor will be 150 bara or less, even more preferably 100 bara or less, and most preferably 80 bara or less.
  • an overpressure is maintained in the anode compartment with respect to the cathode compartment.
  • the separator divides the reactor in two compartments, wherein the anode compartment suitably contains a liquid phase (such as an aqueous liquid), while the cathode compartment suitably contains a gaseous phase (such as a carbon dioxide gas).
  • the liquid phase is difficult to compress, while the gaseous phase can be more easily compressed. Possible pressure fluctuations that may occur in the system could lead to transport of the liquid through the membrane in the direction of the gaseous phase. In order to prevent this from happening, it is preferred to employ a small
  • this overpressure can facilitate the diffusion of H + ions in the bipolar membrane.
  • the over-pressure can, for example, be in the range of 0.2-0.5 bar, such as 0.3-0.4 bar.
  • the reduced carbon dioxide product or product mixture can be further purified after being collected using one or more of the state of the art separation methods, such as distillation, absorption or membrane
  • Such purification may comprise one or more from the group of membrane separations consisting of ultrafiltration, nanofiltration, pervaporation, vapour permeation, and membrane distillation.
  • Such purification methods can be based on the difference in molecular size and/or affinity for a membrane material.
  • the method comprises a step wherein the reduced carbon dioxide product or product mixture is subjected to dehydration.
  • dehydration may, for instance, involve dehydration of methanol and/or acetaldehyde.
  • the residual or permeate of a purification step of the reduced carbon dioxide product or product mixture can optionally be recycled to the carbon dioxide feed, optionally after recompression.
  • the temperature in the electrochemical reactor during the method of the invention is preferably 20 °C or less, and may be even cooler, such as 10 °C or less, or even 5 °C or less.
  • the temperature will normally not be below 0 °C.
  • Such relatively low temperatures can be achieved by active cooling of the electrochemical reactor and/or by introducing low temperature water feed and/or low temperature carbon dioxide feed (e.g. by active cooling of the feed).
  • the reduced carbon dioxide product or product mixture can be collected. This may be accomplished by removing reduced carbon dioxide product or product mixture from the cathode compartment via a cathode compartment outlet. Such outlet is typically located at the bottom of the cathode compartment. The product or product mixture can then suitably be collected in a separate volume, before optionally being processed further.
  • the electrical potential between the anode and the cathode can be applied using an external power supply that is connected to the electrodes (anode and cathode).
  • the electrical potential should be sufficient to drive the reaction, and more in particular for the cathode to reduce carbon dioxide into a reduced carbon dioxide product or product mixture.
  • the invention is directed to an electrochemical reactor, preferably for performing a method as described herein, said reactor comprising an anode compartment separated from a cathode compartment by a separator, wherein said cathode compartment is in contact with a cathode and said anode compartment is in contact with an anode,
  • said anode compartment comprising an anode compartment inlet for feeding water and an anode compartment outlet for releasing oxygen
  • said cathode compartment comprising a cathode compartment inlet for feeding carbon dioxide and a cathode compartment outlet for collecting reduced carbon dioxide product or product mixture
  • said separator is selected from the group consisting of a bipolar membrane, a charge-mosaic membrane, and a layered mixture of anion and cation exchange resins, said electrochemical reactor being configured to operate at a pressure of 20 bara or more.
  • the cathode and/or the anode may be embedded in the separator.
  • the cathode and/or anode may be embedded in one of the ion exchange layers of the bipolar membrane.
  • the cathode is preferably embedded in one of the ion exchange layers, and the anode is embedded in the other ion exchange layer.
  • the separator preferably comprises a cation exchange layer and an anion exchange layer.
  • the separator can then be oriented in the electrochemical reactor such that the cation exchange layer faces the cathode and the anion exchange layer faces the anode.
  • the separator can be oriented in the electrochemical reactor such that the anion exchange layer faces the cathode and the cation exchange layer faces the anode.
  • the electrochemical reactor is configured to operate at a pressure of 20 bara or more, more preferably 30 bara or more, even more preferably 50 bara or more, such as 60 bara or more.
  • the pressure in the electrochemical reactor will not exceed 200 bara.
  • the pressure in the electrochemical reactor is preferably 150 bara or less, more preferably 100 bara or less, such as 80 bara or less.
  • the separator may be mechanically supported on at least one side. It is also possible to mechanically confine the separator between two mechanical supports.
  • the reactor can further be mechanically supported by a holder, which may hold the mechanical support.
  • the reactor can suitably further comprise a water feed line, a carbon dioxide feed line, an oxygen release line, and a reduced carbon dioxide product collection line. The water feed line is then connected to the anode compartment inlet, the carbon dioxide feed line is then connected to the cathode compartment inlet, the oxygen release line is then connected to the anode compartment outlet, and the reduced carbon dioxide product collection line is then connected to the cathode compartment outlet.
  • the oxygen release line and/or the anode compartment inlet comprises a pressure valve which is operably linked to a pressure sensor for measuring the pressure difference between the carbon dioxide feed line and the oxygen release line.
  • the carbon dioxide feed line and/or the cathode compartment inlet may comprise a pressure valve which is operably linked to a pressure sensor for measuring the pressure difference between the carbon dioxide feed line and the oxygen release line.
  • the pressure valve at the oxygen release side may further be operably linked to a pressure sensor for measuring the absolute pressure in the oxygen release line.
  • the invention is directed to a electrochemical reaction module, comprising two or more electrochemical reactors as described herein in parallel.
  • a stack of repeat units (300) as shown in figure 4a may be placed in a high pressure reaction vessel as shown in figure 4b.
  • the repeat unit (300) shown in figure 4a contains a bipolar membrane (100) confined between two constructive parts of similar design that form the cathode compartment and the anode compartment, respectively.
  • Each part consists of a holder (320) for conductive mechanical support (310).
  • the cathode compartment has a port (330) opening to a common cathode feed volume.
  • the anode compartment has a port (340) opening to a common anode feed volume.
  • Figure 4b shows a stack of the repeat units (300) in a high pressure reaction vessel.
  • the high pressure vessel consists of two parts.
  • the upper part (420) is only a cover and can be removed for access to the electrodes and membranes.
  • the lower part (410) supports the stack of cathode-bipolar membrane-anode repeat units, which physically separates the cathode compartment of the reactor vessel at the bottom of the reactor vessel from the anode compartment of the reactor vessel at the top of the reactor vessel.
  • the lower part has two entry ports; one for the cathode feed (430), for example carbon dioxide at high pressure, and for the anode feed (440), for example water.
  • the lower part has two exit ports; one for the reaction product(s) at the cathode side (450), and one for the anode side (460).
  • the tubing connected to entry and exit ports can be brought to the desired level inside the high-pressure electrochemical reactor vessel.
  • the lower part of the reactor vessel also contains the connection ports to a differential pressure sensing device (470). Albeit not show, it is clear that pressure sensing devices for sensing cathode compartment pressure and/or anode compartment pressure can be mounted on the lower part of the reactor vessel.
  • a number of such high pressure reaction vessels may, for instance, be operated in parallel.
  • An example thereof is shown in figure 3.
  • water (1) and carbon dioxide (2) feeds are fed to respectively the anode and the cathode chambers of the high pressure reaction vessel.
  • the product mixture (3) is collected at the bottom of the reaction and is purified in a separation unit.
  • the product (4) (here formic acid), leaves the system.
  • Oxygen (5) evolves at the anode and leaves the system as a gas from the anode chamber.
  • the permeate of the separation unit (10) is recompressed and recycled into the dense carbon dioxide feed stream (2).
  • a further example of an electrochemical reactor is shown in figure 5.
  • the reactor (500) contains a bipolar membrane (100) in a cylindrical configuration.
  • the bipolar membrane has a mechanical support (510). This mechanical support allows a dense gas phase reactant (e.g.
  • the anode chamber is in open contact with the common anode chamber volume (540).
  • a stack of these electrochemical reactors (500) may be placed in a high pressure reaction vessel, for example in a similar fashion as shown in figure 4b, or as a single unit in a high pressure tube, the aggregate being a tube-in-tube electrochemical reactor.
  • a high pressure electrochemical cell was designed in order to have optimal dimensions for the reactor. This is, in particular, relevant for the volume of the electrolyte compartments, the surface area of the membrane, and the surface area of the electrodes.
  • the operating conditions are, typically, in the range of 1- 100 bar and temperatures are in the range of 5-50 °C.
  • the use of a high pressure, dense phase mixture of carbon dioxide and water has as main advantage that high concentrations of ionic, reactive species especially, bicarbonate (HCO3 " ) and carbonate (CO3 2" ) will be formed.
  • the presence of the ionic carbonate species (HCO3 " and CO3 2" ) avoids the need of using an additional electrolyte solution. More specifically, in the proposed reactor configuration there is no need to use a catholyte and/or anolyte solution.
  • Table 1 shows the amount of CO2 (concentration of CO2 per litre) when CO2 is solubihsed in water up to a pressure of 10 bar. In this case the CO2 concentration is also referred to as the CO2 solubility.
  • Table 2 shows the maximum amount (concentration of CO2 per litre) that can be achieved at the given conditions in the case where a small amount of water is added to a CO2 dense phase. For the two situations a temperature of 20 °C is taken, which might require some cooling of the reactor.
  • a relatively small reaction volume can be used, as compared to the conventional electrochemical cells that employ an electrolyte solution.
  • the typical conditions that are applied are atmospheric pressures, and as a result the mass-based ratio of the reactant CO2, to be consumed in the reduction reaction, to the water (in the electrolyte solution) is well below unity.
  • the mass-based CO2 to water ratio is in the order of 0.001-0.005 (1 to 5 g CO2 per litre water). While in the case of starting with a dense phase CO2, the envisaged CO2 to water (mass-based) ratio will be close to unity, based on densities and operation above 50 bar and temperatures below 20 °C.
  • a small reaction volume assures a small(er) distance between the electrodes and the bipolar membrane, with as main result a minimal resistance for the electrical current, and the optimal (minimum) ratio of reaction volume to electrode surface area also assures a high current density. Furthermore, because of the difference in density between the dense CO2 phase and the liquid formic acid phase, with a density of formic acid of 1.22 kg/1 there will be a separation of the product from the reactants.
  • the use of the bipolar membrane will assure a high flux of (only) protons (hydrogen ions, H + ions) across the membrane into the dense CO2 phase.
  • the use of the bipolar membrane for the water splitting, into OH " and H + is an essential step for high selective reduction of carbon dioxide, with a bipolar membrane only hydrogen ions will flow into the dense CO2 phase with the bicarbonate and carbonate ions. Again, the absence of additional ions that are normally exchanged across ion exchange membranes used in electro-catalytic reduction of CO2 will assure no unwanted side reactions.
  • the reactor configuration is ideally suited for the production of formic acid, by providing flexible operation to achieve the required and selected over-potential for carbon dioxide reduction, according to the following reactions/steps:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention se rapporte à un procédé de réduction électrochimique du dioxyde de carbone et à un réacteur électrochimique. Le procédé de l'invention permettant une réduction électrochimique du dioxyde de carbone, consiste à : a) introduire une alimentation en eau dans un compartiment anodique d'un réacteur électrochimique, ledit compartiment anodique comprenant une anode ; b) introduire une alimentation en dioxyde de carbone dans un compartiment cathodique d'un réacteur électrochimique, ledit compartiment cathodique comportant une cathode ; c) appliquer un potentiel électrique entre l'anode et la cathode dans le réacteur électrochimique suffisant pour permettre à la cathode de réduire le dioxyde de carbone en un produit de dioxyde de carbone réduit ou en un mélange de produits, ledit compartiment anodique étant séparé dudit compartiment cathodique par un séparateur comprenant une membrane bipolaire, une membrane mosaïque de charge, ou un mélange stratifié de résines d'échange d'anions et de cations, de préférence le séparateur comprenant une membrane bipolaire et la pression dans le réacteur électrochimique étant égale ou supérieure à 20 bars.
PCT/NL2016/050545 2015-07-22 2016-07-21 Procédé et réacteur permettant une réduction électrochimique du dioxyde de carbone Ceased WO2017014635A1 (fr)

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ES16757367T ES2824158T3 (es) 2015-07-22 2016-07-21 Método y reactor para reducir electroquímicamente dióxido de carbono
EP16757367.4A EP3325692B1 (fr) 2015-07-22 2016-07-21 Procédé et réacteur de réduction électrochimique de dioxyde de carbone
DK16757367.4T DK3325692T3 (da) 2015-07-22 2016-07-21 Fremgangsmåde og reaktor til elektrokemisk reduktion af carbondioxid

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Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019051609A1 (fr) * 2017-09-14 2019-03-21 The University Of British Columbia Systèmes et procédés de réduction électrochimique de dioxyde de carbone
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CN110651068A (zh) * 2017-05-22 2020-01-03 西门子股份公司 用于co2的电化学还原的双膜结构
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US20200318247A1 (en) * 2016-05-31 2020-10-08 Siemens Aktiengesellschaft Method and Device for the Electrochemical Utilization of Carbon Dioxide
US10822709B2 (en) 2016-05-03 2020-11-03 Opus 12 Incorporated Reactor with advanced architecture for the electrochemical reaction of CO2, CO and other chemical compounds
US20210031137A1 (en) * 2018-02-14 2021-02-04 Nedertandse Organisatie voor toegepast natuurwetenschappelijk onderzoek TNO Integrated electrochemical capture and conversion of carbon dioxide
JP2021046576A (ja) * 2019-09-17 2021-03-25 株式会社東芝 電気化学反応装置
WO2021207857A1 (fr) * 2020-04-17 2021-10-21 The University Of British Columbia Conversion électrolytique d'ions contenant du carbone à l'aide d'électrodes métalliques poreuses
EP3818193A4 (fr) * 2018-07-10 2022-04-06 Saipem S.p.A. Procédé et système de production de monoxyde de carbone et de dihydrogène à partir d'un gaz contenant du co2
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US11512403B2 (en) 2018-01-22 2022-11-29 Twelve Benefit Corporation System and method for carbon dioxide reactor control
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WO2026063783A1 (fr) 2024-09-20 2026-03-26 Gaft Innovations B.V. Concentration en acide formique
US12617679B2 (en) 2019-04-08 2026-05-05 Haldor Topsøe A/S Chemical synthesis plant

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111910211B (zh) * 2020-06-22 2021-11-19 西安交通大学 一种连续流动光电催化co2还原反应系统
NL2031327B1 (en) * 2022-03-18 2023-09-29 Univ Delft Tech Carbon capture and conversion

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080223727A1 (en) 2005-10-13 2008-09-18 Colin Oloman Continuous Co-Current Electrochemical Reduction of Carbon Dioxide
CN102912374A (zh) 2012-10-24 2013-02-06 中国科学院大连化学物理研究所 一种以双极膜为隔膜的电化学还原co2电解池及其应用
US20130105304A1 (en) 2012-07-26 2013-05-02 Liquid Light, Inc. System and High Surface Area Electrodes for the Electrochemical Reduction of Carbon Dioxide
US20130186771A1 (en) * 2010-09-24 2013-07-25 Det Norske Veritas As Method and Apparatus for the Electrochemical Reduction of Carbon Dioxide
US20140038019A1 (en) * 2012-07-31 2014-02-06 Gas Technology Institute Bipolar ion exchange membranes for batteries and other electrochemical devices
WO2014043651A2 (fr) 2012-09-14 2014-03-20 Liquid Light, Inc. Cellule électrochimique à haute pression et processus pour la réduction électrochimique de dioxyde de carbone

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080223727A1 (en) 2005-10-13 2008-09-18 Colin Oloman Continuous Co-Current Electrochemical Reduction of Carbon Dioxide
US20130186771A1 (en) * 2010-09-24 2013-07-25 Det Norske Veritas As Method and Apparatus for the Electrochemical Reduction of Carbon Dioxide
US20130105304A1 (en) 2012-07-26 2013-05-02 Liquid Light, Inc. System and High Surface Area Electrodes for the Electrochemical Reduction of Carbon Dioxide
US20140038019A1 (en) * 2012-07-31 2014-02-06 Gas Technology Institute Bipolar ion exchange membranes for batteries and other electrochemical devices
WO2014043651A2 (fr) 2012-09-14 2014-03-20 Liquid Light, Inc. Cellule électrochimique à haute pression et processus pour la réduction électrochimique de dioxyde de carbone
CN102912374A (zh) 2012-10-24 2013-02-06 中国科学院大连化学物理研究所 一种以双极膜为隔膜的电化学还原co2电解池及其应用
CN102912374B (zh) * 2012-10-24 2015-04-22 中国科学院大连化学物理研究所 一种以双极膜为隔膜的电化学还原co2电解池及其应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BALSTER ET AL., CHEMICAL ENGINEERING AND PROCESSING, vol. 43, 2004, pages 1115 - 1127

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