NL1040200C2 - Method for generating energy from a gas flow, and system and plant for energy generation from a flue gas. - Google Patents

Method for generating energy from a gas flow, and system and plant for energy generation from a flue gas. Download PDF

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NL1040200C2
NL1040200C2 NL1040200A NL1040200A NL1040200C2 NL 1040200 C2 NL1040200 C2 NL 1040200C2 NL 1040200 A NL1040200 A NL 1040200A NL 1040200 A NL1040200 A NL 1040200A NL 1040200 C2 NL1040200 C2 NL 1040200C2
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compartment
electrodes
gas
water
energy
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NL1040200A
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Hubertus Victor Marie Hamelers
Olivier Camille Schaetzle
Pieter Maarten Biesheuvel
Cees Jan Nico Buisman
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Stichting Wetsus Ct Excellence Sustainable Water T
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Priority to NL1040200A priority Critical patent/NL1040200C2/en
Priority to PCT/NL2014/050289 priority patent/WO2014182167A1/en
Priority to CA2911342A priority patent/CA2911342A1/en
Priority to EP14725556.6A priority patent/EP2994951B1/en
Priority to US14/889,022 priority patent/US20160156060A1/en
Priority to CN201480031724.0A priority patent/CN105264705B/en
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Publication of NL1040200C2 publication Critical patent/NL1040200C2/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/22Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • H01M8/227Dialytic cells or batteries; Reverse electrodialysis cells or batteries
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44Ion-selective electrodialysis
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668Removal of carbon monoxide or carbon dioxide
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Description

Method for generating energy from a gas flow, and system and plant for energy generation from a flue gas
The present invention relates to a method for generating energy from a gas flow, such as a flue gas, comprising CO2.
Worldwide energy demands are rising. Although the use of renewable energy and/or sustainable energy, like wind energy and solar energy, is growing it is expected that fossil fuels will be the dominant energy source for still some period of time. Plants, such as power plants and process plants, emit still an increasing amount of CO2. To a large extent this C02 emission results from the combustion of fossil fuels. To minimise the effect this CO2 emission may have on the environment and the climate this CO2 emission is captured and stored. One of the practical obstacles against application of this technology is the required energy input.
The object of the present invention is to provide a method for generating energy from a gas flow comprising CO2 that obviates or at least reduces the above stated problems and contributes to an overall efficient energy production and use.
This object is achieved by the method according to the present invention for generating energy from a gas comprising CO2, the method comprising the steps of: - providing a gas flow to a flow channel; - production of cations and anions; - diffusing of the cations towards a cation-selective electrode and of the anions towards an anion-selective electrode; - adsorbing the cations and anions by the electrodes; and - transporting of electrons through an electrical circuit to maintain electro-neutrality of the electrodes and generate electrical energy.
Providing at least two electrodes with one being anion-selective and the other being cation-selective that are capable of sorbing, preferably absorbing (including adsorbing), anions and cations respectively, energy can be generated through this sorption process. Such sorption process starts with the at least two electrodes not yet saturated with ions.
As an example, in a presently preferred embodiment of the invention the gas in the flow channel, including any type of flow compartment, is a flue-gas with a CC>2-level of say 15%. First, the gaseous CO2 absorbs in the water, according to reaction Rl:
Figure NL1040200CD00031
Next, the absorbed CO2 reacts with water to produce carbonic acid {R2), which can dissociate into a proton and a bicarbonate ion (R3). The bicarbonate ion can further dissociate into a carbonate ion and a second proton (R4) according to reactions R2, R3 and R4:
Figure NL1040200CD00032
When the electrodes are not yet saturated with ions, the protons and bicarbonate ions will spontaneously diffuse towards the electrodes. Carbonate may have little effect as this species is expected to have a very low concentration. The presence of the ion exchange membranes (one allowing transport of cations, one allowing that of anions) leads to the protons and bicarbonate ions being absorbed in different electrodes: the proton will be adsorbed in the cation- selective electrode and the bicarbonate ion in the anion-selective electrode. To maintain electro-neutrality, electrons will be transported through the (external) electrical circuit, from the anion-adsorbing side towards the cation-adsorbing electrode. This selective adsorption process thus induces an electric current. This process will continue until the electrodes are saturated.
Anion-selective and cation-selective electrodes can be achieved in different ways. For example, the (carbon) electrodes can be chemically modified by filling the interparticle pores between carbon particles by polyelectrolyte gel and/or by placing an ion-selective layer in front of the electrode such as a membrane. Such ion-exchange membrane is a thin water-filled porous structure containing a high internal concentration of fixed charge groups (e.g. 5 M per volume of water in membrane) of either positive or negative sign. In the case these groups are positive (e.g., from quaternary amine-groups present in the membrane), the membrane has a high selectivity to allow anions (ions of negative sign) passage, while blocking access to cations (such as protons). This is called an anion-exchange membrane. The reverse situation is achieved with sulfonate groups, and this is called a cation-exchange membrane. Other options to provide selective electrodes includes the use of chemically selective inorganic materials .
Each electrode consists of a current collector that connects the system to the outer electrical circuit.
The current collector is in direct contact with a conductive material with a high capacitance, which preferably is a porous carbon electrode. At the high internal surface area within the porous carbons, ions can be stored next to the electrical charge: a so-called electrical double layer (EDL) is formed. The EDL achieves that at the carbon/water interface electronic charge can only be in the carbon, and ions (ionic charge) can only be in the water.
The two charges will be very close, only separated by a few nanometers. In magnitude the two charges cancel one another: thus, overall, the EDL is charge-neutral. When the electrical charge is of negative sign, the electrode will therefore attract and adsorb cations in the water-filled micro-pores in the carbon (next to the carbon surface). This electrode is called the cathode. In the opposite electrode all processes are reversed in sign, this is the anode.
In a presently preferred embodiment the electrode, preferably a porous carbon electrode, is sealed or separated from the flow channel with either a cation exchange membrane or an anion exchange membrane. The space between the membranes, i.e. the flow compartment, is in a presently preferred embodiment filled with water, through which the flue gas is flowing in the form of bubbles. The water provides for an ionic connection between the two different electrodes .
In alternative embodiments the electrodes are separated by C02-selective membranes, or ion-selective membranes without capacitive electrodes. As mentioned earlier, ion-selective electrodes can be applied thereby obviating the need for membranes.
According to the aforementioned operation, at the start there will be a high electrical potential and current, and both will slowly decrease while the electrodes get saturated. After removing the cations and anions from the electrodes in a regeneration step the electrodes can be used again for generation energy from the gas flow.
One of the advantages of generating energy from a gas flow with a relatively high level of C02 is that such gas flows are commonly available, for example as a flue gas.
This renders the energy generation according to the aforementioned method very cost effective. Although the aforementioned method protons and bicarbonate are mentioned as cations and anions it will be understood that it could be possible to use other cations and anions in combination therewith and/or as an alternative thereto. A specific example of flue gas is the waste flue gas produced by a power plant that is known for huge production of CO2.
In an advantageous embodiment according to the present invention the method further comprises the step of desorbing the protons and ions from the electrodes by providing an acceptor gas to the flow channel.
By replacing the donor gas, preferably providing CO2, by an acceptor gas the electrodes are regenerated as the cations, such as the protons, and the anions desorb to the acceptor gas. This provides an effective cycle of absorbing and desorbing that occur alternately in time.
Such a cycle of absorption and desorption with regeneration of the electrodes will be referred to as reversible capacitive absorption of C02. This reversible capacitive absorption is a versatile process making use of the mixing energy that is present in the flue gas.
In an advantageous embodiment according to the present invention the acceptor gas has a relatively low C02 concentration such that C02 is desorbed spontaneously.
When the donor gas is replaced by acceptor gas with a relatively low C02 concentration in the desorption step this will lead to a spontaneous desorption of C02. This desorption will start from the aqueous phase and consequently by diffusing also from the electrodes. To maintain electroneutrality of the electrodes an electric current will start flowing in an opposite direction relative to the current that is produced during the CO2 absorption step. This means that during this desorption step with regeneration of the electrodes also energy can be generated. When the regeneration of the electrodes has been completed, the electrodes can be exposed to the donor gas again and the cycle will start again.
In a presently preferred embodiment the acceptor gas is outside air that has a relatively low CO2 concentration.
To maintain a relatively low CO2 concentration of the acceptor gas this gas should be replenished regularly or even continuously.
In a further advantageous embodiment according to the present invention when desorbing cations and anions from the electrodes, the electrodes are provided with electrical energy to force CO2 desorption to the acceptor gas to produce a gas with a high C02 concentration.
By providing and/or producing an acceptor gas with a relatively high C02 a C02 flow will be generated. In combination with the adsorption step this effectively separates C02 from the original incoming gas, for example a flue gas. For the desorption an electric potential has to be provided because the C02 content of the acceptor gas may have a higher C02 content as compared to the donor gas already at the start of the desorption step and certainly at the end of this desorption step when the electrodes have been regenerated.
Therefore, this separation method provides an alternative to existing gas stripping operations. This may enable a reduction of C02 emissions. As in the first adsorption step energy can be generated the overall energy usage can be kept to a minimum when stripping C02 as compared to conventional techniques involving carbon capture and storage requiring organic solvent, a scrubber and a stripper· using steam thereby requiring an amount of heat such that the overall efficiency of this process is rather limited.
In a further advantageous embodiment according to the present invention energy that is generated when desorbing ions to the acceptor gas is provided to a second set of electrodes and a second flow channel to force C02 desorption to a second acceptor gas for C02 separation.
By operating at least two processes in parallel and/or in series, the energy that is generated in the spontaneous desorption step can be provided to the forced desorption step. This means that part of the C02 desorption is used for energy generation thereby enabling a C02 gas to be produced in the forced desorption process. The forced desorption of the C02 can be performed even without addition of external energy thereby enabling a C02 separation process that can be operated energy-neutral. It can be calculated that 70% of the C02 that is present in a combustion gas or flue gas can be concentrated into a pure C02 flow in such energy efficient combined process. As described above, this is achieved by using a part of the C02 in the flue gas for to generate electrical energy with this electrical energy being used to separate and concentrate another part of the C02.
As a further advantage it can be calculated that although different temperatures have a substantial effect on the amount of electricity that can be generated, the temperature effect on the working point of energy neutral separation is rather limited. This further contributes the practical implementation possibilities for such a combined spontaneous and forced desorption process resulting in an energy effective C02 separation.
Optionally, the method according to the invention may comprise the additional step of transferring the electrodes to another flow, for example from the acceptor gas to the donor gas or vice versa. This means that the electrodes are being switched in stead of the flows. The electrodes can be transferred using a transfer mechanism. The electrodes can be shaped as plates, wires and/or flowable/floating electrodes. Further details of the transfer mechanism and the different embodiments of the transferrable electrodes will be discussed in relation to the system.
In a preferred embodiment of the invention, the method for generating energy from a gas flow comprising CO2 comprises : - providing a first compartment, a second compartment and a third compartment, wherein the first compartment is separated from the second compartment by a cation exchange membrane and the second compartment is separated from the third compartment by an anion exchange membrane; - providing water in the compartments; - providing the gas flow to the second compartment for dissolving the C02 in the water in the second compartment; - production of cations and anions; - diffusing of the cations towards the first compartment and of the anions towards the third compartment, thereby creating a potential difference; and - generate electrical energy.
This method employs a process known as reversed electrodialysis (RED). Conventional methods of reversed electrodialysis make use of the difference in sodium chloride (NaCl) concentration between two water streams. In contrast, the method according to the invention utilizes the concentration difference in dissolved C02 to generate electrical energy. The bicarbonate and carbonate ions will diffuse through the anion exchange membrane to the third compartment, while the protons (H+ ions) diffuse through the cation exchange membrane to the first compartment. This creates a flow of charged particles and hence a current.
Preferably, a stack of alternating anion membranes and cation membranes is used to increase the potential difference created due to the diffusion of the anions and cations .
Preferably, an electrolyte is provided to convert the flow of ions in a flow of electrons, e.g. by means of a redox reaction. The electrolyte may be provided in outer compartments in a reversed electrodialysis stack.
Preferably, the method comprises using a CO2 adsorbing material, such as active carbon. For example, the first, second and/or third compartment are provided with a CO2 adsorbing material.
In a preferred embodiment of the invention, the method for generating energy from a gas flow comprising CO2 comprises the step of: - providing a first compartment and a second compartment, separated by a membrane; - providing water in the compartments; - providing the gas flow to the first compartment for dissolving the CO2 in the water, such that an osmotic pressure between the two compartments forces water from the second compartment to the first compartment, thereby increasing the water level in the first compartment, the method further comprising: - generating electrical energy by connecting the first compartment to a device for generating electrical energy from the pressure of the water in the first compartment.
This method employs a process known as pressure retarded osmosis (PRO). Conventional methods of pressure retarded osmosis make use of the difference in sodium chloride (NaCl) concentration between two water streams. PRO utilizes a membrane which allows passage of water but blocks the ions in the water. Due to the osmotic pressure, fresh water from a first compartment diffuses through the membrane to salt water in a second compartment, thereby increasing the water level in the second compartment. Electrical energy can be generated using this increased water level, by employing conventional water pressure turbines.
In contrast, the invention makes use of the difference in dissolved CO2. The concentration of ions due to dissolved CO2 (protons, bicarbonate and carbonate) is higher in the first compartment than in the second compartment. Therefore, an osmotic pressure establishes over the membrane. Water will diffuse through the membrane from the second compartment, with a low concentration of ions, to the first compartment, with a higher concentration of ions, thereby restoring equilibrium. The water level in the first compartment will thus increase. The increased water level gives rise to an increased water pressure, which can be utilized to drive a turbine, as in conventional hydropower installations .
Preferably, the method comprises using a C02 adsorbing material, such as active carbon. For example, the first and/or second compartment are provided with a C02 adsorbing material.
The invention further relates to a system for energy generation from a flue gas and a plant comprising such system, with the system comprising: - a gas inlet; - at least two capacitive electrodes comprising a current collector and a conductive material with a capacitance; - a flow channel operatively connected to the gas inlet between the at least two electrodes; - wherein the at least one electrode is separated from the flow channel with an anion exchange membrane and at least one electrode is separated from the flow channel with a cation exchange membrane .
Such system and plant provide the same effects and advantages as mentioned in respect of the method. These advantages include an effective energy generation of electrical energy using the afore mentioned method. In addition, C02 can be separated from a flue gas in an energy efficient manner. In fact, the system according to the present invention enables a reversible capacitive adsorption of C02. This enables an efficient energy generation and/or C02 separation.
In an advantageous embodiment according to the present invention the system further comprises a fixed electrolyte structure to minimise gas flow resistance.
In a presently preferred embodiment of the invention the C02 comprising donor gas reacts with water to form carbonic acid that in turn dissociates to produce the ions required for adsorption. This would imply that an electrolyte layer is provided between the at least two electrodes. In a presently preferred embodiment water is used in the flow channel. To minimise the gas flow resistance a fixed electrolyte structure is provided. This minimises the resistance to gas flow thereby contributing to an effective energy generation and/or C02 separation.
In a presently preferred embodiment the fixed electrolyte structure can be solid polymer electrolyte, for example a wire mesh.
In a presently preferred embodiment the electrodes comprise a flat plate. This enables providing a relatively large surface for adsorbing the ions. Alternative for such flat plate configuration, or in addition thereto, the electrodes may comprise wire based electrodes. Such wire shaped electrodes enhance mass transfer as compared to a flat plate as the hydrodynamic resistances may be kept to a minimum. A further advantage of such wire shaped electrodes is the relatively easy fabrication process that may make use of extrusion technology that is capable of producing the absorber structure substantially in one step. This may further improve the efficiency of the system according to the present invention.
In an alternative embodiment of the invention the electrodes comprise floating/flowable electrodes. This may be achieved by providing the electrodes as a suspension.
This renders transfer of the electrodes to the other flow, i.e. donor flow or acceptor flow, more easy.
According to the present invention the system further comprises a transfer mechanism to transfer the electrodes to another flow channel.
As an alternative to replacing the donor gas with the acceptor gas and vice versa, or in combination therewith, a transporting mechanism may transfer the electrodes from a first gas phase to another gas phase. For example, the electrodes are used in a absorption step. After saturation of the electrodes the electrodes are transferred to another flow channel thereby enabling the desorption step and regeneration of the electrodes. This transfer mechanism may switch the positions of the electrodes physically by lifting the electrode from a first system reactor and transfer them to a second system reactor, for example. Other embodiments of this transfer mechanism can be envisaged. For example, the separated electrode particles can be transported as a suspension by a flowing carrier liquid.
Optionally, the system according to the invention comprises one or more buffers. These buffers may comprise ammonia (NH3) and/or an amine, such as monoethanolamine (C2H7NO) , for example. Preferably, the buffer is provided in the flow channel, for example by addition of a buffer solution to water in the flow channel.
The use of a buffer, or a buffer solution, increased the conductivity and the pH difference. This reduces the internal resistance. The increase in pH difference between the air and the C02 saturated solution provides a higher power density. This renders the system according to the invention more effective.
In a further preferred embodiment according to the invention, the system comprises a reversed electrodialysis stack. Such a stack comprises alternating anion and cation exchange membranes, which define chambers which alternating hold water comprising a high concentration of dissolved CO2 and water comprising a low concentration of dissolved CO2.
In a preferred embodiment according to the invention, the system for energy generation from a flue gas comprises: - a first compartment and a second compartment for holding water, separated by a membrane for allowing passage of water but blocking ions; - a gas inlet connected to the first compartment for dissolving the flue gas in water in the first compartment; and - a device for generating electrical energy from water pressure connected to the first compartment for generating electrical energy from pressure of the water in the first compartment.
The features described for the method can also be applied to the system and vice versa.
Further advantages, features and details of the invention are elucidated on the basis of preferred embodiments thereof, wherein reference is made to the accompanying drawings in which: - Figure 1 illustrates a system for performing the method according to the present invention; - Figure 2 illustrates a schematic overview of the method according to the present invention; - Figure 3 illustrates some experimental results with the system of figure 1; - Figure 4 illustrates an alternative embodiment of the system of figure 1; - Figure 5 illustrates a further embodiment of a system according to the present invention; - Figure 6 illustrates experimental results with the embodiment of figure 5; - Figure 7 illustrates a system for performing a second embodiment of the method according to the invention; and - Figure 8 illustrates a system for performing a third embodiment of the method according to the invention;
System 2 (figure 1) comprises flow channel 4, first electrode 6 and a second electrode 8. Electrodes 6, 8 comprise a conductive material 10 with a high capacitance.
In the illustrated embodiment conductive material 10 comprises porous carbon. Current collectors 12 of electrodes 6, 8 are in contact with conductive material 10. At the relatively large internal surface area within the porous carbon 10 ions can be stored or adsorbed. Current collectors 12 are connected by electrical circuit 14. In the illustrated embodiment the ions are stored next to the electrical charge, thereby forming a so-called electrical double layer as mentioned earlier wherein at the carbon/water interface the electronic charge can only be in the carbon and ions (ionic charge) can only be in the water. With an electrical charge of a negative sign the electrode will attract and adsorb cations in the water-filled micropores in the carbon. This electrode behaves as a cathode. In the opposite electrode the processes are reversed and this electrode behaves as an anode. Electrode 6 is separated or sealed from flow channel 4 with cation exchange membrane 16. Electrode 8 is separated and/or sealed from flow channel 4 with anion exchange membrane 18. In the illustrated embodiment flow channel 4 is filled with a liquid 20, in the illustrated embodiment water. Gas, such as flue gas, flows through liquid 20 in the form of bubbles 22. Liquid 20 provides an ionic connection between the at least two electrodes 6, 8.
The method 24 according to the present invention (figure 2) starts with providing gas at inlet 26. In flow channel 4 the reactions R1-R4 described earlier take place in reaction step 28. The cations and anions diffuse towards the electrodes 6, 8 passing the selective membranes 16, 18 in diffusion step 30. The ions are adsorbed and electric energy is generated in electrical circuit 14 in adsorption step 32.
When electrodes 6, 8 are saturated, system 2 is switched from the adsorption state to the desorption state in switching step 34. Next, desorption will take place in desorption step 36. From the adsorption step 32 energy 38 is generated. From desorption step 36 an amount of energy 40 is generated and/or an amount of separated C02 in flow 42 is being generated with optionally an amount of energy 44 being provided to enable C02 separation. The amount of energy 44 can be provided by the generated energy 38, 40 in adsorption step 32 and/or desorption step 36. Alternatively, energy 44 is provided by an external source.
In a first experiment the system 2 is used in an experiment providing C02-saturated water in flow channel 4.
In the experiment an electrical potential will develop using a constant external resistance such that the potential is proportional with the generated current. The experiment results are shown in figure 3 for rise and decrease of electrical voltage (left axis) and power produced (right axis) during adsorption of C02 in a capacitive electrode cell based on system 2 of figure 1.
In a further experiment it is shown that with an increasing replenishment of the acceptor gas relative to the flue gas the amount of available extractable energy increases. This amount of energy strongly depends on the gas temperature. For example, at a temperature of 150°C the flue gas undergoes only limit treatment, while 50°C is a characteristic temperature for system with wet scrubbing and 20°C is a representative ambient temperature. It is estimated that when system 2 is applied to an average power plant the amount of energy that can be harvested is equivalent of up to 10% of the electricity produced in such average power plant.
In a further experiment, in the desorption step 36 a combination is made of spontaneous desorption resulting in a net production of energy 40 and a forced desorption resulting in a production of C02 flow 42. Although the temperature has a certain effect on the electricity that can be generated, the equilibrium between energy consumption for the forced desorption process as compared to the energy generation of the spontaneous energy production in the desorption step surprisingly remains about the same such that at this equilibrium about 70% of the CO2 can be separated in a reversible capacitive adsorption process according to the present invention. Therefore the reversible capacitive absorption of CO2 provides a versatile process that be used for energy generation and CO2 separation that can be applied to power plants and also to refineries, gas and oil exploration, steel production, green houses, etc.
As an alternative to system 2 making use of a bubbling flat plate reactor type, an alternative system 44 (figure 4) can be provided. System 44 comprises a cathode 46 and an anode 48 that are connected through electrical circuits 49. The wire based electrodes 46, 48 further comprise the membranes 50 and a solid polymer electrolyte 52 around which flow 54 comprising CO2 can be provided. In a further alternative configuration (not shown) the electrode can be in the form of a flowing suspension that is pumped slowly around in a closed circuit thereby transporting the electrodes to a second channel 4. In the illustrated embodiment, transfer mechanism 56 that is schematically illustrated transfers electrodes 46, 48 from a first flow chamber 4 to a second flow chamber 4.
In an experiment, cell 58 (figure 5) comprises aluminum end plate 60, hollowed poly-methyl methacrylate plastic plate 62 provided with graphite electrode 64, silicon gasket 66 with graphite foil current collector with an activated carbon coating 68, anion exchange membrane 70 from Fumatech, Teflon gasket 72, polymer spacer 74, cation exchange membrane 76 from Fumatech, graphite foil current collector with an activated carbon coating 78, silicon gasket 80, hollowed poly-methyl methacrylate plastic plate 84 provided with graphite electrode 82, aluminum end plate 86. Cell 58 is connected to circuit 88. Flow 90 enters cell 58 at plate 60, passes through the space provided with spacer 74 and leaves cell 58 at plate 86.
Anion exchange membrane 70 was pre-conditioned in a 0.25M KHC03 solution and refreshed two times (once after 2.5 days and one after one extra days). Cation exchange membrane 76 was pre-conditioned in a 0.25M HC1 solution and refreshed once after 2.5 days. Both electrodes 64, 82 are Norit super 30 based (casted at 500 microns) with 10% pvdf and were soaked in an initially CO2 saturated demi-water solution (sparkling demi-water that progressively degassed), wherein electrodes 64, 82 stayed in this solution for 3.5 days. The CO2 saturated solution was obtained after bubbling CO2 in demi-water. CO2 was bubbling at least lh30 before starting the measurements. The air saturated solution was obtained by bubbling compressed air from the standard building line.
Internal resistance was measured between two electrodes 64, 82 and was 83Ω in the air saturated solution and 13.5 Ω in the CO2 saturated solution. The pH was measured to be 5.53 in the air saturated solution and 3.96 in the CO2 saturated solution. The cell potential (figure 6) is measured in mV.
In CO2 the potential returns to zero due to the saturation effect and flow 90 through cell 58 is switched to air. The potential switches sign and slightly reduces in time. These results illustrate the operation of cell 58 in an embodiment according to the invention.
Further experiments with this experimental setup were performed. Switching the flow of C02~rich and CC>2-poor gas about every 400 seconds shows a measured open cell Voltage of about -15 mV to about +40 mV at a temperature of about 20°C and a partial pressure of 1 bar.
Additional experiments were provided wherein electrodes 6, 8 were provided in a buffer solution. The buffer solution that was used in the experiments was ethanolamine. Results are presented in Table 1 for several pH differences.
Table 1: Power density (mW/m2) versus pH difference pH difference Total energy (mJ) Power density (mW/m2) 0,74 0,0246107 0,0040679 0,79 0,0421384 0,0069881 0,85 0,0672965 0,0111974 0,91 0,1078457 0,0178552 0,98 0,1702072 0,0282736 1,05 0,2461349 0,0409542 1,09 0,3553666 0,0591292 1,15 0,4911211 0,0818535
Results show a higher power density with a larger pH difference thereby showing the effect of providing a buffer.
System 92 (figure 7) comprises a first compartment 94 and a second compartment 96, separated by a membrane 98 of the type that allows passage of water, but is impermeable to ions. Both compartments 94, 96 are provided with water. Second compartment 96 comprises a gas inlet 100 for feeding a CO2 comprising gas in compartment 96. The CO2 dissolves in the water, leading to an increased concentration of protons, carbonate and bicarbonate ions in the water in compartment 96. In contrast, the water in compartment 94 has a relatively low ion concentration. This creates an osmotic pressure between the compartments 94, 96. This forces water through membrane 98 according to arrow 102. The water level of the water in compartment 96 rises as a consequence, as indicated by arrow 104. This increase water level gives rise to an increased water pressure, which is utilized in a hydropower turbine 106.
The compartments 94, 96 can be connected to inlets and/or outlets for continuous and/or batch-wise operation.
System 108 (figure 8) comprises a first inlet 110 for CO2 comprising water. Alternatively, separate inlets are provided for CO2 and water, and a mixing chamber is provided to dissolve the C02 in the water.
System 108 further comprises a water inlet 112, connected to compartments 114, 116, 118. The CO2 comprising water from inlet 110 is fed to adjacent compartments 120, 122, 124.
The outside compartments 126, 128 comprise an electrolyte. These compartments are connected to each other by line 130.
The compartments 114, 116, 118 are separated from compartments 120, 122, 124 by means of cation exchange membranes 132 and anion exchange membranes 134.
Electrolyte compartments 126, 128 are provided with electrodes 136, 138.
Compartments 114, 116, 118, 120, 122, 124 are provided with outlets. System 108 can be operated in continuous or in batchwise operation.
The protons (H+) diffuse through the kation exchange membranes 132 from the C02 rich water to the CO2 poor water, while the carbonate and bicarbonate ions diffuse through the anion exchange membranes. The resulting flow of ions is converted to a flow of electrons by means of the electrolyte in outer compartments 126, 128 and/or the electrodes 136, 138. For example, the electrolyte comprises iron ions (Fe2+ as reductor and/or Fe3+ as oxidator). The reduction and oxidation reaction is as following:
Figure NL1040200CD00211
When the electrodes 136, 138 are connected to an electrical circuit, a current results.
It will be understood that the features of the different embodiments that are illustrated and/or described can be combined. For example, the transfer mechanism 56 illustrated for the wire-based type system 44 can also be applied to the flat plate reactor system 2.
The present invention is by no means limited to the above described preferred embodiments thereof. The rights sought are defined by the following claims, within the scope of which many modifications can be envisaged. It is thus possible according to the invention to make a combination of the described embodiments, features and measures.
Clauses 1. Method for generating energy from a gas flow comprising CO2, the method comprising the step of: - providing a gas flow to a flow channel; - production of cations and anions; - diffusing of the cations towards a cation-selective electrode and of the anions towards an anion-selective electrode; - adsorbing the cations and anions by the electrodes; and - transporting of electrons through an electrical circuit to maintain electro-neutrality of the electrodes and generate electrical energy.
2. Method according to clause 1, further comprising the step of desorbing the cations and anions from the electrodes by providing an acceptor gas through the channel.
3. Method according to clause 2, wherein the acceptor gas has a relatively low CO2 concentration such that CO2 is desorbed.
4. Method according to clause 3, further comprising the step of transporting of electrons through an electrical circuit to maintain electro-neutrality of the electrodes and generate electrical energy during the desorption.
5. Method according to clause 3 of 4, wherein the acceptor gas is outside air.
6. Method according to clause 1 or 2, wherein the electrodes are provided with electrical energy to force CO2 desorption to the acceptor gas to produce a gas with a high CO2 level during the desorption.
7. Method according to clause 4 or 5 and 6, wherein energy that is generated when desorbing ions to the acceptor gas is provided to a second set of electrodes and a second flow channel to force C02 desorption to the second acceptor gas for C02 separation.
8. Method for generating energy from a gas flow comprising C02, the method comprising the step of: - providing a first compartment, a second compartment and a third compartment, wherein the first compartment is separated from the second compartment by a cation exchange membrane and the second compartment is separated from the third compartment by an anion exchange membrane; - providing water in the compartments; - providing the gas flow to the second compartment for dissolving the C02 in the water in the second compartment; - production of cations and anions; - diffusing of the cations towards the first compartment and of the anions towards the third compartment, thereby creating a potential difference; and - generate electrical energy.
9. Method for generating energy from a gas flow comprising CO2, the method comprising the step of: - providing a first compartment and a second compartment, separated by a membrane; - providing water in the compartments; - providing the gas flow to the first compartment for dissolving the CO2 in the water, such that an osmotic pressure between the two compartments forces water from the second compartment to the first compartment, thereby increasing the water level in the first compartment, the method further comprising: - generating electrical energy by connecting the first compartment to a device for generating electrical energy from the pressure of the water in the first compartment.
10. System for energy generation from a flue gas, comprising: - a gas inlet; - at least two capacitive electrodes comprising a current collector and a conductive material with a capacitance; - a flow channel operatively connected to the gas inlet between the at least two electrodes; - wherein the at least one electrode is separated from the flow channel with an anion exchange membrane and at least one electrode is separated from the flow channel with a cation exchange membrane.
11. System according to clause 10 further comprising a fixed electrolyte structure to minimize gas flow resistance .
12. System according to clause 10 or 11, wherein the electrodes comprise a flat plate.
13. System according to clause 10 or 11, wherein the electrodes comprise wire based electrodes.
14. System according to clause 10 or 11, wherein the electrodes comprise flowable or floatable electrodes.
15. System according to one or more of the clauses 10-14, further comprising a transfer mechanism to transfer the electrodes to another flow channel.
16. System according to one or more of the clauses 10-15, further comprising a buffer.
17. System according to one or more of the clauses 10-16, wherein the system comprises a reversed electrodialysis stack.
18. System for energy generation from a flue gas, comprising : - a first compartment and a second compartment for holding water, separated by a membrane for allowing passage of water but blocking ions; - a gas inlet connected to the first compartment for dissolving the flue gas in water in the first compartment; and - a device for generating electrical energy from water pressure connected to the first compartment for generating electrical energy from pressure of the water in the first compartment.
19. Plant comprising a system according to one or more of the clauses 10-18 for generating energy with the flue gas and/or separating of CO2 from the flue gas.

Claims (19)

1. Werkwijze voor het genereren van energie van een gasstroom omvattende CO2, de werkwijze omvattende de stappen: - het voorzien van een gasstroom aan een stroomkanaal; - het produceren van kationen en anionen; - diffusie van de kationen naar een kationselectieve elektrode en van de anionen naar een anionselectieve elektrode; - adsorptie van de kationen en anionen door de elektroden; en - transport van elektronen door een elektrisch circuit voor het behoud van de electroneutraliteit van de elektroden en het genereren van elektrische energie.A method for generating energy from a gas stream comprising CO2, the method comprising the steps of: - providing a gas stream on a flow channel; - producing cations and anions; diffusion of the cations to a cation-selective electrode and of the anions to an anion-selective electrode; adsorption of the cations and anions by the electrodes; and - transport of electrons through an electrical circuit for maintaining the electron neutrality of the electrodes and generating electrical energy. 2. Werkwijze volgens conclusie 1, verder omvattende de stap van desorptie van de kationen en anionen van de elektroden door het voorzien van een acceptorgas aan het stromingskanaal.The method of claim 1, further comprising the step of desorption of the cations and anions of the electrodes by providing a acceptor gas on the flow channel. 3. Werkwijze volgens conclusie 2, waarin het acceptorgas een relatief lage C02 concentratie heeft zodanig dat desorptie van C02 plaats vindt.The method of claim 2, wherein the acceptor gas has a relatively low CO 2 concentration such that desorption of CO 2 takes place. 4. Werkwijze volgens conclusie 3, verder omvattende de stap van het transporteren van elektronen door een elektrisch circuit voor het behouden van de elektroneutraliteit van de elektroden en het genereren van elektrische energie gedurende de desorptie.The method of claim 3, further comprising the step of transporting electrons through an electrical circuit for maintaining the electron neutrality of the electrodes and generating electrical energy during desorption. 5. Werkwijze volgens conclusie 3 of 4, waarin het acceptorgas buitenlucht is.The method according to claim 3 or 4, wherein the acceptor gas is outside air. 6. Werkwijze volgens conclusie 1 of 2, waarin de elektroden zijn voorzien van elektrische energie voor het forceren van CO2 desorptie naar het acceptorgas voor het produceren van een gas met een hoog CO2 niveau gedurende de desorptie.A method according to claim 1 or 2, wherein the electrodes are provided with electrical energy for forcing CO2 desorption to the acceptor gas for producing a gas with a high CO2 level during the desorption. 7. Werkwijze volgens conclusies 4 of 5 en 6, waarin de energie welke is gegenereerd door de desorptie van ionen naar het acceptorgas wordt voorzien naar een tweede set van elektroden en een tweede stromingskanaal voor het forceren van CO2 desorptie naar een tweede acceptorgas voor CO2 scheiding.The method of claims 4 or 5 and 6, wherein the energy generated by the desorption of ions to the acceptor gas is provided to a second set of electrodes and a second flow channel for forcing CO2 desorption to a second acceptor gas for CO2 separation . 8. Werkwijze voor het genereren van energie van een gasstroom omvattende CO2, de werkwijze omvattende de stappen: - het voorzien van een eerste compartiment, een tweede compartiment en een derde compartiment, waarin het eerste compartiment van het tweede compartiment gescheiden wordt door een kationuitwisselmembraan en het tweede compartiment van het derde compartiment gescheiden wordt door een anionuitwisselmembraan; - het voorzien van water in de compartimenten; - het voorzien van een gasstroom aan het tweede compartiment voor het oplossen van het C02 in het water in het tweede compartiment; - het produceren van kationen en anionen; - diffusie van de kationen naar het eerste compartiment en van de anionen naar het derde compartiment, waarmee een potentiaalverschil wordt gecreëerd; en het genereren van elektrische energie.A method for generating energy from a gas stream comprising CO2, the method comprising the steps of: - providing a first compartment, a second compartment and a third compartment, wherein the first compartment is separated from the second compartment by a cation exchange membrane and the second compartment is separated from the third compartment by an anion exchange membrane; - providing water in the compartments; - providing a gas stream to the second compartment for dissolving the CO2 in the water in the second compartment; - producing cations and anions; diffusion of the cations to the first compartment and of the anions to the third compartment, thereby creating a potential difference; and generating electrical energy. 9. Werkwijze voor het genereren van energie van een gasstroom omvattende CO2, de werkwijze omvattende de stappen: - het voorzien van een eerste compartiment en een tweede compartiment, die van elkaar zijn gescheiden door een membraan; - het voorzien van water in de compartimenten; - het voorzien van een gasstroom in het eerste compartiment voor het oplossing van CO2 in het water, zodanig dat een osmotische druk tussen de twee compartimenten het water van het tweede compartiment naar het eerste compartiment drukt, waarmee het waterniveau in het eerste compartiment wordt verhoogd, de werkwijze verder omvattende: - het genereren van elektrische energie door het verbinden van het eerste compartiment met een inrichting voor het genereren van elektrische energie uit de waterdruk in het eerste compartiment.A method for generating energy from a gas stream comprising CO2, the method comprising the steps of: - providing a first compartment and a second compartment, which are separated from each other by a membrane; - providing water in the compartments; - providing a gas stream in the first compartment for the solution of CO2 in the water, such that an osmotic pressure between the two compartments presses the water from the second compartment to the first compartment, whereby the water level in the first compartment is increased, the method further comprising: - generating electrical energy by connecting the first compartment to a device for generating electrical energy from the water pressure in the first compartment. 10. Systeem voor het genereren van energie van een verbrandingsgas, omvattende: - een gasinlaat; - ten minste twee capacitieve elektroden omvattende een stroomcollector en een geleidend materiaal met een capaciteit; en - een stromingskanaal werkzaam verbonden met de gasinlaat voor het voorzien van een ionische verbinding tussen de ten minste twee elektroden, waarin ten minste één elektrode is gescheiden van het stromingskanaal met een kationuitwisselingsmembraan en ten minste één elektrode is gescheiden van het stromingskanaal met een anionuitwisselingsmembraan.A system for generating energy from a combustion gas, comprising: - a gas inlet; - at least two capacitive electrodes comprising a current collector and a conductive material with a capacity; and a flow channel operatively connected to the gas inlet for providing an ionic connection between the at least two electrodes, wherein at least one electrode is separated from the flow channel with a cation exchange membrane and at least one electrode is separated from the flow channel with an anion exchange membrane. 11. Systeem volgens conclusie 10, verder omvattende een vaste elektrolytstructuur voor het minimaliseren van gasstromingsweerstand.The system of claim 10, further comprising a fixed electrolyte structure for minimizing gas flow resistance. 12. Systeem volgens conclusie 10 of 11, waarin de elektroden een vlakke plaat omvatten.The system of claim 10 or 11, wherein the electrodes comprise a flat plate. 13. Systeem volgens conclusie 10 of 11, waarin de elektroden draad-gebaseerde elektroden omvatten.The system of claim 10 or 11, wherein the electrodes comprise wire-based electrodes. 14. Systeem volgens conclusie 8 of 9, waarin de elektroden stromende elektroden omvatten.The system of claim 8 or 9, wherein the electrodes comprise flowing electrodes. 15. Systeem volgens één of meer van de conclusies 10-14, verder omvattende een overzetmechanisme voor het overzetten van de elektroden naar een ander stromingskanaal.The system of one or more of claims 10-14, further comprising a transfer mechanism for transferring the electrodes to another flow channel. 16. Systeem volgens één of meer van de conclusies 10-15, verder omvattende een buffer.The system of any one of claims 10-15, further comprising a buffer. 17. Systeem volgens één of meer van de conclusies 10-16, waarin het systeem een omgekeerde elektrodialyse stapel omvat. \The system of any one of claims 10-16, wherein the system comprises a reverse electrodialysis stack. \ 18. Systeem voor het genereren van energie van een verbrandingsgas, omvattende: een eerste compartiment en een tweede compartiment voor het houden van water, gescheiden door een membraan dat water doorlaat en ionen tegenhoudt; een gasinlaat die is verbonden met het eerste compartiment voor het oplossen van het verbrandingsgas in het water in het eerste compartiment; en een inrichting voor het genereren van elektrische energie uit waterdruk, verbonden met het eerste compartiment voor het genereren van elektrische energie van de druk van het water in het eerste compartiment.A system for generating energy from a combustion gas, comprising: a first compartment and a second compartment for holding water, separated by a membrane that lets water through and retains ions; a gas inlet connected to the first compartment for dissolving the combustion gas in the water in the first compartment; and a device for generating electrical energy from water pressure connected to the first compartment for generating electrical energy from the pressure of the water in the first compartment. 19. Installatie omvattende een systeem volgens één of meer van de conclusies 10-19 voor het genereren van energie met het verbrandingsgas en/of het scheiden van CO2 van het verbrandingsgas.An installation comprising a system according to one or more of claims 10-19 for generating energy with the combustion gas and / or separating CO2 from the combustion gas.
NL1040200A 2013-05-06 2013-05-06 Method for generating energy from a gas flow, and system and plant for energy generation from a flue gas. NL1040200C2 (en)

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NL1040200A NL1040200C2 (en) 2013-05-06 2013-05-06 Method for generating energy from a gas flow, and system and plant for energy generation from a flue gas.
PCT/NL2014/050289 WO2014182167A1 (en) 2013-05-06 2014-05-06 Method for generating energy from a gas flow, and system and plant for energy generation for a flue gas
CA2911342A CA2911342A1 (en) 2013-05-06 2014-05-06 Method for generating energy from a gas flow, and system and plant for energy generation from a flue gas
EP14725556.6A EP2994951B1 (en) 2013-05-06 2014-05-06 Method for generating energy from a gas flow, and system and plant for energy generation from a flue gas
US14/889,022 US20160156060A1 (en) 2013-05-06 2014-05-06 Method for generating energy from a gas flow, and system and plant for energy generation from a flue gas
CN201480031724.0A CN105264705B (en) 2013-05-06 2014-05-06 For the method from the raw energy of gas miscarriage and system and equipment for generating energy from flue gas

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013113A1 (en) * 1978-12-21 1980-07-09 Allied Corporation A process and apparatus for the production of electrical energy from the neutralization of acid and base in a bipolar membrane cell
EP0176446A2 (en) * 1984-09-24 1986-04-02 Aquanautics Corporation System for the extraction and utilization of oxygen and other ligands from fluids
US20120067819A1 (en) * 2009-10-28 2012-03-22 Oasys Water, Inc. Osmotically driven membrane processes and systems and methods for draw solute recovery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013113A1 (en) * 1978-12-21 1980-07-09 Allied Corporation A process and apparatus for the production of electrical energy from the neutralization of acid and base in a bipolar membrane cell
EP0176446A2 (en) * 1984-09-24 1986-04-02 Aquanautics Corporation System for the extraction and utilization of oxygen and other ligands from fluids
US20120067819A1 (en) * 2009-10-28 2012-03-22 Oasys Water, Inc. Osmotically driven membrane processes and systems and methods for draw solute recovery

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