Electrochemical Metal Removal
20240325976 ยท 2024-10-03
Inventors
- Roberta Veronezi Figueiredo ('s-Gravenhage, NL)
- Amanda Cristina Garcia (Leiden, NL)
- Dhruva Ajit Marathe ('s-Gravenhage, NL)
- Elena P?rez Gallent (Leiden, NL)
- Juliana Garcia Moretz-Sohn Monteiro (Schiedam, NL)
- Earl Lawrence Vincent Goetheer (Mol, BE)
Cpc classification
B01D61/445
PERFORMING OPERATIONS; TRANSPORTING
B01D2252/2023
PERFORMING OPERATIONS; TRANSPORTING
B01D61/463
PERFORMING OPERATIONS; TRANSPORTING
C25D5/003
CHEMISTRY; METALLURGY
B01D53/1425
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D53/96
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention is in the field of CO.sub.2 capture. In particular the invention relates to a method for capturing CO.sub.2 from a CO.sub.2-containing feed gas stream, wherein the method comprises at least partially removing dissolved transition metal ions by electrodeposition. The invention further relates to a system for the method.
Claims
1. A method for capturing CO.sub.2 from a CO.sub.2-containing feed gas stream, wherein the method comprises: providing the feed gas stream in an absorber comprising a solvent to absorb CO.sub.2 in the solvent to obtain a CO.sub.2-rich solvent stream and a CO.sub.2-lean gas stream; leading the CO.sub.2-rich solvent stream to a regenerator to obtain a CO.sub.2-lean solvent stream and a CO.sub.2-rich gas stream; wherein the CO.sub.2-rich solvent stream and/or the CO.sub.2-lean solvent stream comprise dissolved transition metal ions; wherein the method further comprises at least partially removing the dissolved transition metal ions from the CO.sub.2-rich solvent stream and/or the CO.sub.2-lean solvent stream comprising electrodeposition of the dissolved transition metal ions in an electrochemical cell to obtain a metal deposit.
2. The method according to claim 1, wherein the CO.sub.2-rich solvent stream and the CO.sub.2-lean solvent stream comprises a CO.sub.2 capture solvent.
3. The method according to claim 1, wherein the transition metal ions are selected from the group consisting of iron cations, nickel cations, chromium cations, cobalt cations, manganese cations and a combination thereof.
4. The method according to claim 1, wherein the electrochemical cell is a one-compartment electrochemical cell comprising a cathode and an anode.
5. The method according to claim 1, wherein the electrochemical cell is a two-compartment electrochemical cell comprising a cathodic compartment comprising a cathode and an anodic compartment comprising an anode.
6. The method according to claim 5, wherein the two-compartment electrochemical cell further comprises a bipolar membrane comprising an anion exchange layer, a cation exchange layer and an interface layer, wherein the bipolar membrane separates the anodic compartment and the cathodic compartment.
7. The method according to claim 6, wherein the anion exchange layer of the bipolar membrane faces the cathodic compartment.
8. The method according to claim 1, wherein the transition metal concentration in the CO.sub.2-rich solvent stream and/or the CO.sub.2-lean solvent stream is at least 5 ppm.
9. The method according to claim 1, wherein the method further comprises feeding at least part of the CO.sub.2-rich solvent stream and/or at least part of the CO.sub.2-lean solvent stream to the electrochemical cell; applying a reductive potential to reduce and/or an oxidative potential to oxidize the transition metal ions to obtain a metal deposit and a metal-lean fraction.
10. The method according to claim 9, wherein the metal-lean fraction is fed to the absorber.
11. The method according to claim 1, wherein the method further comprises removing the metal deposit.
12. The method according to claim 1, wherein the method is a continuous method.
13. A method for at least partially removing transition metal ions from a solution, wherein the method comprises electrodeposition of the metal ions in a two-compartment electrochemical cell comprising a bipolar membrane comprising an anion exchange layer, a cation exchange layer and an interface layer, wherein the bipolar membrane separates a cathodic compartment from an anodic compartment.
14. A system for capturing CO.sub.2 from a CO.sub.2-containing feed gas stream according to the method of claim 1, wherein the system comprises; an absorber comprising a feed fluid inlet and CO.sub.2-rich solvent outlet; a regenerator comprising a CO.sub.2-rich solvent inlet and a CO.sub.2-lean solvent outlet; an electrochemical cell comprising a metal-rich fraction inlet and a metal-lean fraction outlet, wherein the CO.sub.2-rich solvent outlet is in fluid connection with the CO.sub.2-rich solvent inlet and/or in fluid connection with the metal-rich fraction inlet; wherein the CO.sub.2-lean solvent outlet is in fluid connection with the metal-rich fraction inlet and/or in fluid connection with the feed fluid inlet; wherein the metal-lean fraction outlet is in fluid connection with the feed fluid inlet and/or in fluid connection with the CO.sub.2-rich solvent inlet.
15. The system according to claim 14 wherein the CO.sub.2-lean solvent outlet is in fluid connection with the metal-rich fraction inlet, the metal-lean fraction outlet is in fluid connection with the fluid inlet and the CO.sub.2-rich solvent outlet is in fluid connection with the CO.sub.2-rich solvent inlet.
16. The method of claim 1 wherein the electrodeposition comprises electroreduction.
17. The method of claim 2 wherein the CO.sub.2 capture solvent comprises an amine based liquid.
18. The method of claim 2 wherein the CO.sub.2 capture solvent comprises a glycol-based liquid and/or a liquid comprising an amino acid.
19. The method of claim 2 wherein the CO.sub.2 capture solvent comprises aminomethyl propanol (AMP), methyl diethanolamine (MDEA), or monoethanolamine (MEA) or combinations thereof.
20. The method of claim 9, comprising feeding at least part of the CO.sub.2-rich solvent stream and/or at least part of the CO.sub.2-lean solvent stream to the cathodic compartment of the electrochemical cell.
Description
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[0020]
[0021] Thus, in a first aspect the present invention is directed to a method for CO.sub.2 capture from a CO.sub.2-containing feed gas stream (10). The method is schematically illustrated as flow-chart in
[0022] The method may be performed at ambient temperature and pressure, but as well at temperature and pressure conditions present in the capture plant. The method according to the present invention may allow for a reduced waste management, avoid fast degradation of the solvents and increase the lifetime of both solvent and industrial equipment.
[0023] The CO.sub.2-containing feed gas stream may be any feed gas that comprises carbon dioxide. Examples include, but are not limited to flue gasses from industrial processes, air, exhaust gasses and natural gas. The feed gasses may further comprise other gasses such as molecular oxygen and/or molecular nitrogen.
[0024] The feed gas enters an absorber in which during use a solvent is provided and reacts with the carbon dioxide to absorb the CO.sub.2. Such solvents typically comprise amine-based solvents. Preferably the solvent comprises a CO.sub.2 capture solvent (i.e. a liquid that reacts with the CO.sub.2), herein also referred to as capture solvent. Examples of suitable CO.sub.2 capture solvent include amine-based liquids such as piperazine, glycol-based liquids and/or liquids comprising an amino-acid. More specific examples are for instance alkanolamines, such as monoethanolamine (MEA), aminomethyl propanol (AMP), methyl diethanolamine (MDEA) and combinations thereof such as a blend of 27 wt % AMP and 13 wt % piperazine (CESAR1). The CO.sub.2 reacts with such solvents to produce i.a. charged species, in particular carbamate, bicarbonate and carbonate ions and protonated amines. Accordingly, the solvent streams typically comprises these solvents. The solvent may further comprise water but it may also be anhydrous. The solvent may for instance be an aqueous solution of MEA.
[0025] It may be preferred to subject the CO.sub.2-lean solvent stream to electroreduction. Considering MEA as capture solvent, for example, the CO.sub.2-lean loading is preferably around 0.2 mol CO.sub.2/mol amine.
[0026] The CO.sub.2 plant, in particular the absorber, regenerator and/or the pipes, typically comprise stainless steel housing. Accordingly, the corrosion due to the degradation products typically result in the release of transition metal ions in the liquid. These transition metal are typically iron cations, nickel cations, chromium cations, cobalt cations and/or manganese cations. Cations are herein used to refer to any individual or combination of oxidation states of the metal. For instance iron cations refer to Fe(II), Fe(III), Fe(IV) and/or Fe(VI). Similarly, nickel cations may refer to Ni(I), Ni(II), Ni(III) and/or Ni(IV). Chromium cations is used for Cr(I), Cr(II), Cr(III), Cr(IV), Cr(V) and/or Cr(VI). Cobalt cations may refer to Co(I), Co(I), Co(III), Co(IV) and/or Co(V). Manganese cations may be Mn(I), Mn(II), Mn(III), Mn(IV), Mn(V), Mn(VI) and/or Mn(VII). Generally, in the solvent the metal ions include Fe(II), Fe(III), Ni(II), Ni(III), Cr(III), Cr(VI), Co (II), Co(III) and/or Mn(II). Typically, the metal ions are iron cations, nickel cations and/or chromium cations, mainly iron cations. Iron cations are typically present in higher concentrations and accordingly, the transition metal cations are typically Fe(II) and/or Fe(III). The Roman numerals in the brackets indicate the oxidative state, e.g. Fe(II) is Fe.sup.2+.
[0027] Typically, the transition metal concentration in the CO.sub.2-rich solvent stream and/or the CO.sub.2-lean solvent stream depends on the nature of the feed gas and solvent used. For a stable operation with minimal corrosion and degradation, a metal concentration of less than 5 mg/kg is typically preferred. If no reclaiming process is used, the iron concentration increases over time, typically reaching values much higher than 5 mg/kg, up to 50-100 mg/kg, a point at which operation of the plant needs to be stopped. Accordingly, the method of the present application can be applied to a transition metal concentration in the CO.sub.2-rich solvent stream and/or the CO.sub.2-lean solvent stream of at least 5 mg/kg, preferably at least 15 mg/kg, such as at least 20 mg/kg.
[0028] The dissolved metal ions are at least partially removed through electrodeposition, such as electroreduction or electro-oxidation of the dissolved transition metal ions in an electrochemical cell (1) to obtain a metal deposit. The electrodeposition is carried out in an electrochemical cell. Electroreduction is generally based on the application of an electric current or a reductive potential to discharge cationic species in an electrolyte via an electron-accepting step at the cathode. Electro-oxidation is generally based on the application of an electric current or an oxidative potential to increase the positive charge of a species in an electrolyte via an electron-donating step at the anode. The cells typically comprise a cathode and an anode that are separated by an electrolyte and/or membrane. Additionally, as conventional in the art, the cell may comprise one or more reference electrodes that may be used to control the cathode and/or anode potential. The process can be run galvanostatically (i.e. by applying a current) or potentiostatically (i.e. by applying a potential on either the cathode, anode or cell).
[0029] During electroreduction, a reductive potential or a reductive current is typically applied to the cathode. The reductive potential or current may be specifically chosen such that it allows for the selective reduction of the targeted species (i.e. the metal ion(s)). Accordingly, the reductive potential typically varies depending on the conditions such as the cathode material, the cation(s) to be reduced and the electrolyte composition. During electro-oxidation, an oxidative potential or a oxidative current is typically applied to the anode. The oxidative potential or current may be specifically chosen such that it allows for the selective oxidation of the targeted species. Accordingly, the oxidative potential typically varies depending on the conditions such as the anode material, the species to be oxidized and the electrolyte composition.
[0030] Generally, the potential applied at the cathode is preferably between ?3 and +3V vs Ag/AgCl, preferably between 0 and ?3V vs Ag/AgCl. As an example, for the reduction of Fe(II) to Fe(0) on a graphite electrode in a 30% MEA aqueous solution with Ag/AgCl as reference electrode, the reductive potential applied may be between ?0.8 and ?1.5V, such as between ?1.0 and ?1.4V. This potential is particularly favorable for reduction of iron cations. Further, the potential may be amended over time, to for instance first reduce or oxidize a first metal followed by the reduction or oxidation of a second metal. Alternatively or additionally, multiple electrochemical cells may be employed to selectively reduce or oxidize the individual metal ions. As the metals may be similar (i.e. close in the period table) the metals may have an overlapping reduction and/or oxidation potential that may result in the reduction or oxidation of more than one metal ion at a particular applied reduction potential.
[0031] A combination of electro-oxidation and electroreduction may also be applied. For instance, when multiple electrochemical cells are employed. A first electrochemical cell may be used to oxidize a first metal and a second electrochemical cell may be employed to reduce a second metal or vice versa.
[0032] In order to minimize or prevent any losses of oxidizable species in the solvent, such as carbamate ions, amines or protonated amines, the electrochemical cell is preferably a two-compartment electrochemical cell. However, a one-compartment cell comprising a cathode and an anode may suffice for a capture solvent that is stable. A suitable two-compartment electrochemical cell is illustrated in
[0033] A bipolar membrane is schematically illustrated in
[0034] It is even more preferred that the electrochemical cell is a two-compartment electrochemical flow cell. In such a flow cell, the to be treated liquid (i.e. the CO.sub.2-lean solvent and/or the CO.sub.2-rich solvent) is typically fed to and flows through the cathodic compartment. The anodic compartment may comprise any conventional electrolyte.
[0035] Another two-compartment electrochemical cell is illustrated in
[0036] In the two-compartment flow cell as illustrated in
[0037] The preferred bipolar membrane configuration may beneficially assist in resisting a pH change in the compartments as protons generated in the anodic compartment will consume the hydroxyl anions present in the cathodic compartment in the membrane interfacial layer. Preferably, the electrodeposition comprises electroreduction and an electrochemical cell according to
[0038] In a preferred embodiment a reduction potential or current is applied. In such cases, the metal cations are typically reduced. The metal cations may be reduced to e.g. its elemental state, hydroxide, oxide and/or oxide hydroxide. For instance, Fe(II) may accept two electrons from the cathode and form a metal deposit of elemental iron. Alternatively or additionally, the Fe(II) may form a metal deposit of iron hydroxide, iron oxide or iron oxide hydroxide. Without wishing to be bound by theory the present inventors believe that the reduced metal at the cathode may re-oxidize after the reductive potential is removed. Accordingly, the metal deposit may comprise metallic metal, metal oxide, metal oxide hydroxide and/or metal hydroxides.
[0039] Dependent on the metal deposit, the metal deposit may be removed from the electrochemical cell for instance by filtration and/or electrochemical regeneration of the electrodes. Filtration may for instance be used in case the metal deposit is not too strongly adhered to the cathode and/or anode but present as e.g. a precipitate, while for a more strongly adhered metal deposit to the cathode and/or anode the metal deposit is typically removed by electrochemical regeneration of the electrodes. The metal is typically removed from the CO.sub.2-capture plant and thus tends to break the autocatalytic solvent degradation cycle. As the metal deposit typically forms on the cathode and/or the anode, the cathode and/or anode may also be replaced and/or removed, cleaned or regenerated (e.g. scraping and/or electrochemical treatment) and placed back. The cathode and/or anode may comprise any suitable material including for example carbon and/or metals such as titanium, nickel, and/or iron. A further suitable material for the anode comprises gold-coated quartz crystals. Preferably, the cathode and/or anode comprises graphite. See e.g. Van Khanh Nguyen and Yeonghee Ahn, Journal of Environmental Management 211 (2018) 36-41 and Carlos G. Morales-Guio et al., J. Am. Chem. Soc. 2016, 138, 28, 8946-8957. Graphite electrodes are preferred as they are typically cheap. The electrode surface area may be amended to allow for a more optimal metal ion removal.
[0040] Further, as the transition metal ions are deposited a metal-lean fraction (16) remains. The metal-lean fraction typically comprises the solvent that can be reused in the absorber of the CO.sub.2 capture system. The metal-lean fraction may accordingly be less corrosive and an increased lifetime of the industrial equipment as well as the solvent may be achieved. Accordingly, it is preferred that the metal-lean fraction is fed to the absorber. A schematic overview is illustrated in
[0041] In a preferred embodiment, the method is a continuous method as this typically allows for the CO.sub.2 capture process to remain active. If the method is employed continuously, the anolyte may require occasional or continuous refreshing.
[0042] The invention is further related to a method for at least partially removing transition metal ions from a solution. The method comprises electrodeposition, preferably electroreduction, of the metal ions in a two-compartment electrochemical cell comprising a bipolar membrane (6). The bipolar membrane separates a cathodic compartment (2) from an anodic compartment (4). Preferably wherein the anion exchange layer faces the cathodic compartment.
[0043] In a further aspect, the invention is related to a system (100) for the method according to the present invention. Several embodiments are illustrated in
[0044] An alternative embodiment is illustrated in
[0045]
[0046]
[0047] In another alternative embodiment, the electrochemical cell may be placed between the regenerator and the absorber as for instance illustrated in
[0048] A schematic overview of a suitable system is illustrated in
[0049] Accordingly, the electrochemical cell for the method according to the present invention may be located at any place in the solvent loop of a CO.sub.2 capture system, to allow for in-situ metal removal. Part of the liquids may for instance be tapped or bypassed to be subjected to electrodeposition. As at least part of the liquids is subjected to electrodeposition, the metal ions may be removed from these liquids allowing for a sufficient purification to continue the process with minimal corrosion and degradation.
[0050] A schematic overview of a preferred system is illustrated in
[0051] For the purpose of clarity and a concise description features are described herein as part of the same or separate embodiments, however, it will be appreciated that the scope of the invention may include embodiments having combinations of all or some of the features described.
[0052] The invention may further be illustrated by the following non-limiting examples.
EXAMPLE 1CELL POTENTIAL
[0053] Two batch experiments were performed using an aqueous MEA solution with approximately 30 ppm Fe.sup.2+ concentration and a CO.sub.2 loading of approximately 0.48 mol CO.sub.2/mol MEA (typical rich loading). In a first two-compartment cell a potential of ?1.3V was applied. In the second two-compartment cell a potential of ?0.6V was applied. Graphite cathodes of 1 cm.sup.2 surface area were used in both cells.
[0054]
EXAMPLE 2ELECTRODE SURFACE AREA
[0055] Two experiments were carried out in a two-compartment electrochemical flow cell with 10 cm.sup.2 cathode surface area to determine if the increase in cathode surface area from 1 cm.sup.2 (Example 1) to 10 cm.sup.2 has an effect. Both experiments used aqueous MEA solutions. A first solution comprised approximately 75 ppm Fe.sup.2+, the second solution comprised approximately 35 ppm Fe.sup.2+. Both solutions had a CO.sub.2 loading of roughly 0.23 mol CO.sub.2/mol MEA (typical lean loading). The applied potential in both two-compartment cells was ?1.3 V.
[0056] The results are illustrated in
EXAMPLE 3DURATION
[0057] Two batch experiments were carried out using aqueous MEA solutions in a two-compartment electrochemical flow cell. The first solution had an Fe.sup.2+ concentration of approximately 35 ppm and the second solution approximately 15 ppm. Both solutions had a CO.sub.2 loading of roughly 0.25 mol CO.sub.2/mol MEA. The applied potential in both cells was ?1.3V. The cathode was a polished graphite cathode plate with a surface area of 10 cm.sup.2 and the anode was a Pt anode plate.
[0058] The iron concentration over time is illustrated in