EP1951933A1 - Reduction electrochimique de dioxyde de carbone a courants paralleles - Google Patents

Reduction electrochimique de dioxyde de carbone a courants paralleles

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Publication number
EP1951933A1
EP1951933A1 EP06804642A EP06804642A EP1951933A1 EP 1951933 A1 EP1951933 A1 EP 1951933A1 EP 06804642 A EP06804642 A EP 06804642A EP 06804642 A EP06804642 A EP 06804642A EP 1951933 A1 EP1951933 A1 EP 1951933A1
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EP
European Patent Office
Prior art keywords
anolyte
cathode
catholyte
gas
carbon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06804642A
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German (de)
English (en)
Other versions
EP1951933A4 (fr
Inventor
Hui Li
Colin Oloman
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Mantra Energy Alternatives Ltd
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Mantra Energy Alternatives Ltd
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Application filed by Mantra Energy Alternatives Ltd filed Critical Mantra Energy Alternatives Ltd
Publication of EP1951933A1 publication Critical patent/EP1951933A1/fr
Publication of EP1951933A4 publication Critical patent/EP1951933A4/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C25B11/044—Impregnation of carbon
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/40—Cells or assemblies of cells comprising electrodes made of particles; Assemblies of constructional parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention is in the field of electrochemistry, encompassing processes for the electro-reduction of carbon dioxide in aqueous systems, and apparatus therefor.
  • the formate salts MHCO 2 (where M is typically Na 1 K or NH 4 ) and formic acid HCO 2 H are commercial chemicals that may be produced by industrial thermochemical processes (Kirk-Othm ⁇ r • Encyclopedia of Chemical Technology, 1991).
  • sodium formate and subsequently formic acid may be obtained by reaction of sodium hydroxide with carbon monoxide, followed by acidolysis with sulphuric acid.
  • Formic acid may also be produced as a co-product in the oxidation of hydrocarbons and by the hydrolysis of methyl formate from the carbonylation of methanol.
  • Processes for the synthesis of formate salts (e.g. KHCO 2 ) by the electro- reduction of carbon dioxide are also known (Chaplin and Wragg, 2003; Sanchez et at., 2001; Akahori et al., 2004; Hui and Oloman, 2005).
  • Carbon dioxide is considered the main anthropogenic cause of climate change. Methods to sequester CO 2 and/or convert it to useful products are therefore needed.
  • that electrochemical cell comprises a pair of spaced apart electrodes, at least one of the electrodes being in the form of a fluid permeable conductive mass separated from the counter electrode by a barrier wall.
  • the electrode mass may be in the form of a bed of particles or a fixed porous matrix. It is composed of an electronically conducting material the surface which is a good electrocatalyst for the reaction to be carried out.
  • Inlets are provided for feeding liquid electrolyte and gas into the electrode mass such that the electrolyte and gas move co-currently through the electrode mass, for example in a direction generally perpendicular to the direction of the current between the electrodes.
  • An outlet is provided for removing solutions containing reaction products from the fluid permeable conductive mass.
  • the invention provides electro-chemical processes for reduction of carbon dioxide, for example converting carbon dioxide to formate salts or formic acid.
  • operation of a continuous reactor with a three dimensional cathode and a two-phase (gas/liquid) catholyt ⁇ flow provides advantageous conditions for electro-reduction of carbon dioxide.
  • the continuous two-phase flow of catholyte solvent and carbon dioxide gas, in selected gas/liquid phase volume ratios provides dynamic conditions that favour the electro-reduction of CO 2 at relatively high effective superficial current densities.
  • relatively high internal gas hold-up in the cathode chamber ⁇ evident in a gas to liquid phase volume ratio > 1 in the feed stream, or > 0.1 within the porous electrode) may provide greater than equilibrium CO 2 concentrations in the liquid phase, facilitating relatively high effective superficial current densities. In some embodiments, these characteristics may for example be achieved at catholyte pH > 7 and relatively low CO 2 partial pressures ( ⁇ 10 bar).
  • the invention involves continuously passing a catholyte mixture through a cathode chamber of an electrochemical reactor.
  • the catholyt ⁇ mixture may include carbon dioxide gas and a liquid catholyt ⁇ solvent containing dissolved carbon dioxide.
  • the catholyte solvent may for example be an aqueous solvent, it may include a dissolved alkali metal or ammonium bicarbonate, and may be maintained at a desired pH, such as in the range of from about 6 to about 9.
  • a catholyte gas to liquid (G/L) volumetric ratio may be maintained, being the ratio of the volume of carbon dioxide gas to the volume of the liquid catholyte solvent.
  • the G/L ratio may be maintained in the cathode chamber, for example in the feed stream or in a porous cathode within the chamber.
  • the process may be operated so that the G/L ratio is greater than a threshold value, such as greater than 1 in the feed, or greater than 0.1 within the porous (3D) cathode.
  • One aspect of the invention involves passing an electric current between a cathode in the cathode chamber and an anode, to reduce dissolved carbon dioxide to form a desired product.
  • the process may be operated so that the effective superficial current density at the cathode is greater than a threshold value, such as 1 kA/m 2 (or 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 kA/m 2) .
  • the electric current in the system may for example be a direct current, driven by an electrochemical cell voltage, and in some embodiments the process may be capable of operating at relatively low electrochemical cell voltages, for example less than 10 Volts.
  • the processes of the invention may be used with relatively dilute input gas streams, for example the carbon dioxide gas concentration in the feed gas may be from 1 to 100%, or any numeric value within this range (in some embodiments yielding a carbon dioxide partial pressure in the cathode chamber less than a threshold value, such as 3, 5 or 10 Bar).
  • a threshold value such as 3, 5 or 10 Bar
  • it may be effective to run processes of the invention at elevated temperatures, which may avoid the necessity for cooling, for example at cathode temperatures above a desired threshold such as 20, 25, 30, 35, 40, 45 or 5O 0 C.
  • cathode chamber pressures and temperatures may vary along the cathode height.
  • the inlet pressure may be greater than outlet pressure (in some embodiments, the pressure drop may for example range from a minimum of about 10, 20, 30, 40, or 50 kPa, up to a maximum of about 500, 600, 700, 800 or 900 kPa).
  • Cathodes for use in the invention may have an effective thickness in the dimension of current flow, such as a porous cathode. These may be referred to as three dimensional (3D) electrodes. Such electrodes may have a selected thickness, such as less than 6, 5, 4, 3, 2, 1 or 0.5mm, and they may have a selected porosity, or range of porosities, such as 5 to 95% or any numeric value within this range, such as 30, 40, 50, 60 or 70%.
  • Cathodes of the invention may be made from a wide variety of selectively electro-active materials, such as tin, lead, pewter, mercury, indium, zinc, cadmium, or other materials such as electronically conductive or non- conductive substrates coated with selectively electro-active materials (e.g. tinned copper, mercury amalgamated copper, tinned graphite or tinned glass).
  • selectively electro-active materials such as tin, lead, pewter, mercury, indium, zinc, cadmium, or other materials such as electronically conductive or non- conductive substrates coated with selectively electro-active materials (e.g. tinned copper, mercury amalgamated copper, tinned graphite or tinned glass).
  • the anode may be in an anode chamber, and the anode chamber may be separated from the cathode chamber by an electrochemical cell membrane.
  • the anolyte in the anode chamber may be an aqueous anolyte, and may for example include a dissolved alkali metal hydroxide, a salt (including an ammonium salt) or an acid, and may have a pH range of from about 0 to about 14, or any pH value or range within this range.
  • the electrochemical cell membrane may be a cation permeable membrane, for example a membrane that permits selected ions to cross the membrane to balance process stoichiometry.
  • the desired products of the process include formate salts, such as ammonium, potassium and sodium formate, or formic acid.
  • the desired product may be separated from the catholyte solvent in a variety of ways. For example, a portion of the catholyte solvent, the recycling catholyte solvent, may be recycled from a cathode chamber outlet to a cathode chamber inlet, and the desired product may be separated from the recycling catholyte solvent. Similarly, at least a portion of the anolyte may be recycled from an anolyte chamber outlet to an anolyte chamber inlet, and an anode co-product may be separated from the recycling anolyte.
  • Joule heating of the anolyte may be used to provide heated anolyte, and the heated anolyte may be used to heat the recycling catholyte solvent to separate the desired product from the recycling catholyte solvent, for example by evaporation with fractional crystallization or vacuum distillation.
  • recycling catholyte, that includes formate may be reacted with the anolyte, to obtain the desired product by an acidolysis reaction.
  • Figure 2 is a schematic illustration of electrochemical cells of the invention, as described in Example 1 , in which the reference numerals denote the following components: 1 and 2: cell bodies; 2, 7 and 9: gaskets; 3: anode feeder, 4: anode spacer; 5: membrane; 6: 3-D cathode (tin-coated copper mesh, tin shot/granules and Pb shot/granules); 8: cathode feeder.
  • Figure 3 shows a sectioned elevation view of the single-cell reactor of the invention, Reactor A, as described in more detail in Example 1.
  • Figure 4 shows a sectioned elevation view of the single-cell reactor of the invention, Reactor B, as described in more detail in Example 1.
  • Figure 5 is a process flow sheet illustrating various aspects of a continuous process for conversion of CO 2 to formate salts or formic acid, involving recycling of catholyte and anolyte.
  • Figure 6 is a process flowsheet (Flowsheet "A"), illustrating an embodiment of the process for converting CO 2 gas to NaHCO 2 (sodium formate) and NaHCO 3 (sodium bicarbonate) with a byproduct of H 2 (hydrogen) and co- product of O 2 (oxygen).
  • Flowsheet "A” illustrating an embodiment of the process for converting CO 2 gas to NaHCO 2 (sodium formate) and NaHCO 3 (sodium bicarbonate) with a byproduct of H 2 (hydrogen) and co- product of O 2 (oxygen).
  • Figure 7 is a formalized version of process Flowsheet A, forming the basis for a steady-state material balance stream table for a process of converting approximately 600 tonnes per day of carbon dioxide gas to sodium formate.
  • Figure 8 illustrates Process Flowsheet B, for which there is a corresponding material and energy balance stream table in the examples.
  • Figure 9 illustrates Process Flowsheet C of the Examples.
  • the invention provides a continuous reactor for electrored ⁇ ction of CO 2 , which may for example be used in a process that converts a feed of carbon dioxide plus water to formate ion (Reaction 1) and consequently produces formate salts or formic acid.
  • the invention may utilize an electrochemical reactor analogous to the trickle bed reactor described by Oloman and Watkinson in U.S. Pat. Nos. 3,969,201 and 4,118,305.
  • the invention may utilize an apparatus for carrying out electrochemical reactions involving gaseous reactants comprising an electrochemical cell having a pair of spaced apart electrodes, at least one of the electrodes, such as the cathode, being in the form of a fluid permeable conductive mass and being separated from the counter electrode by an ionically conductive but electronically insulating layer (such as a membrane or porous diaphragm).
  • the reactor may be operated in a "trickle-bed” mode, with co-current flow of reactant gas and catholyte liquid through a flow-by 3-D cathode.
  • the process parameters of the invention may be adjusted so that this reactor achieves advantageous reactant supply (evident for example as a high gas space velocity, a ratio of the volumetric gas feed flow rate over reactor volume) and mass transfer characteristics.
  • the co-current fluid flow in the cathode may be at any orientation relative to gravity, such as upward or downward.
  • an inlet may be provided for feeding a liquid electrolyte and a gas into the fluid permeable conductive mass
  • an outlet may be provided for removing solutions containing reaction products from the conductive mass.
  • the inlet and outlet may be arranged so that the electrolyte and gas move co-currently through the conductive mass, for example in a direction generally normal to the flow of electric current between the electrodes.
  • the reactor may for example be provided with a cation membrane separator (as described for example in Hui and Oloman, 2005). In alternative embodiments, other types of reactor may be used.
  • the process feed may also include: metal hydroxides and/or metal salts such as MOH, MCI 1 M 2 CO 3 , M 2 SO 4 and M 3 PO 4 where M is typically an alkali metal (Na, K, etc.) or NH 4 ; acids such as H 2 SO 4 , H 3 PO 4 , or HCl; or ammonia (NH 3 ).
  • metal hydroxides and/or metal salts such as MOH, MCI 1 M 2 CO 3 , M 2 SO 4 and M 3 PO 4 where M is typically an alkali metal (Na, K, etc.) or NH 4 ; acids such as H 2 SO 4 , H 3 PO 4 , or HCl; or ammonia (NH 3 ).
  • the feed CO 2 stream to the process may be concentrated, for example to above 80 %vol CO 2 .
  • a relatively dilute gas stream may be used, such as the product gas from combustion of a fossil fuel (typically containing about 10 %vol CO 2 ).
  • feed CO 2 stream Other potentially reactive components of the feed CO 2 stream include oxygen, sulphur oxides, nitrogen oxides and hydrogen sulphide- These may be handled in the process in a variety of ways, for example they may be removed in one or more initial scrubbing steps, so that they are absent or at low concentrations (such as below about 1 %vol) in the feed stream entering the reactor.
  • the total pressure and temperature of the feed CO 2 stream may vary over relatively wide ranges, for example from, respectively, about 100 to 1000 kPa(abs), and about 250 to 550 K.
  • the conversion of CO 2 per pass through the electrochemical reactor may be less than 100%, so that the invention may include provision for recycling the unconverted CO 2 gas as welf as recycling the catholyte liquid.
  • Process steps 1 to 5 in Figure 5 may be included in some embodiments of the invention, briefly characterized as follows with reference to the annotations on the Figure.
  • Step 1 MIX: Continuously mixes the feed water (plus any make-up reagents) with the recycling catholyte, which is then delivered continuously to the reactor cathode chamber.
  • Step 2 [C] Cathode. Continuously drives reaction 1 , along with the side-reaction, Reaction 2, that gives hydrogen by the electro-reduction of water.
  • [0032] Anode. Continuously drives the complimentary anode reaction(s) whose nature depends on the desired products from the process. For example, if the desired main product is a formate salt and the co-product is oxygen then the anode reaction may be Reaction 3.
  • the anode reaction may be respectively Reaction 4 or 5.
  • Other anode reactions may include the generation of peroxy-salts of peroxy-acids, such as peroxy-disulphate (2SO 4 " -> S 2 O 8 2' + 2e " ).
  • the electrode chambers in the reactor may be separated by a membrane that selectively allows the transport of cations from anode to cathode in amounts that balance the desired process stoichiom ⁇ try.
  • these cations may be alkali metal ions (e.g. Na + , K + or NH 4 + ) fed to the anolyte as hydroxides, salts or NH 3 gas, whereas if the desired main product is formic acid the transported cations may include protons (H + ) generated in Reaction 4 and/or fed to the anolyte as an acid.
  • Step 3. SEPARATE: Continuously separates the main product (formate salt or formic acid) and byproduct (hydrogen) from the recycling catholyte.
  • Step 4. MIX: Continuously mixes required anode reagents and water with the recycling anolyte.
  • Step 5 SEPARATE: Continuously separates the anode co-product(s) from the recycling anolyte.
  • carbon dioxide and water may be consumed and/or generated in other reactions, such as Reactions 6, 7 and 8 that occur in the reactor or elsewhere in the process.
  • the process may involve driving the reactor at a relatively high superficial current density (e.g. above 0.5 kA/m 2 ) and current efficiency, for example for formate production (e.g. above 50 %).
  • Processes of the invention may also involve balancing the material and energy requirements of the various process steps to match the required process stoichi ⁇ metry, while maintaining a low specific energy consumption. For example, processes of the invention have demonstrated 75% current efficiency for formate at 1.3 kA/m 2 with a reactor voltage of 3 V at CO 2 pressure of 200 kPa(abs) and temperature of 300 K.
  • the management of water may be important to the material balance and require that water be fed to the cathode and/or anode circuits to match its rate of reaction, electro-osmotic transport and evaporation.
  • the consumption of energy in electrochemical reaction, heating, cooling and pumping may be a contributor to the process cost, and may be kept relatively low by appropriate reactor design and by rationalizing the thermal loads in the process.
  • non-metallic catalysts may be used.
  • U.S. Patent Nos. 5284563 and US 5382332 disclose nickel alkyl cyclam catalysts that may be used for carbon dioxide reduction.
  • G/L flow 1 to 1000 or 10 to 200
  • a high gas space velocity e.g. > 100 h '1 .
  • increasing G/L from about 5to 100 increases the voltage by less than 10 %.
  • G/L hold-up The optimum G/L phase volume (denoted as the "G/L hold-up") ratio depends, in general, on the balance between the effective cathofyte conductivity (usually decreasing with increasing G/L hold-up), the CO 2 mass transfer capacity (usually increasing with increasing G/L hold-up) and the intrinsic temperature and pH dependent kinetics of CO 2 conversion to the un-reactive bicarbonate/carbonate species in the bulk cathofyte liquid phase.
  • G/L gas/liquid
  • the volumetric G/L ratio in the reactor feed stream(s), with the gas volume flow corrected to STP this may for example have a range of about 1 to 1000, 1 to 500, 10 to 200, or 10 to 100 or any numeric value within these ranges.
  • "Hold-up" fraction of pore space (in 3D cathode) occupied by the specified phase at a given moment. Assumed to be constant in steady-state operation of the reactor.
  • G/L[flow] is not equal to G/L[hold-up] because the gas has a shorter residence time in the cathode than the liquid (i.e. gas "slips" past the liquid).
  • the feed stream and internal hold-up values of (i) and (ii) are of course related, since the value of (ii) depends on the value of (i) together with the cathode characteristics, such as porosity (or vokjage), shape factor, and particle size. Similarly, the value of (i) affects the value of (ii), and is also related to the CO 2 mass transfer capacity in the cathode and the gas space velocity of the reactor.
  • Effective CD 1.5 kA/m 2 at CO 2 pressure ⁇ 3 Bar.
  • Effective CD [superficial CD] x [current efficiency for desired product (e.g. formate)]
  • the “superficial current density” is the current passing through the cell divided by the projected surface area of the relevant element, such as the cathode.
  • the "projected surface area” of an element, such as the cathode is surface area of a projection of the element on a plane parallel to the element.
  • the projected surface area is equal to the area of the side of that element facing the other conductive element, for example the projected surface area of the cathode facing the anode.
  • the projected surface area is the area within the outline of the mesh as projected onto a continuous planar surface.
  • the "current efficiency” is the ratio, generally expressed as a percentage, of the actual reaction rate to the rate that would be achieved if all of the current passing through the cell were consumed by relevant reaction, such as the reduction of carbon dioxide.
  • the invention may operate at or near adiabatic conditions (T out, up to about 90 0 C).
  • T out up to about 90 0 C.
  • an increasing temperature actually favours the intrinsic kinetics of the electroreduction of carbon dioxide (ERC) 1 and good CE can be obtained at higher temperatures by manipulating the factors that promote CO 2 mass transfer in a continuous reactor.
  • the ability to operate at high temperature may be important, because the effects of Joule heating at high CD under near adiabatic conditions in the continuous reactor may automatically increase the reaction temperature by up to about 80 0 C.
  • FIG. 1 shows a process flow diagram reflecting this example of the electro-reduction of carbon dioxide (ERC).
  • EEC carbon dioxide
  • Pure COz or the mixture of CO2 (gas) and N 2 (gas) was combined with the catholyte (liquid) at a T junction (mixer), from which the gas and liquid proceeded in slug flow to enter the cathode chamber from the bottom.
  • the electro-chemical reactor was operated with co-current upward multi-phase (G/L) flow on the cathode side.
  • the anolyte which was an aqueous KOH solution, also flowed upward through the anode chamber and was recycled to the anolyte storage tank. All gases and liquids passed through individual rotameters.
  • Liquid flow was controlled at the pumps, while gas flows were controlled by manual valves to assure the appropriate gas and liquid loads in the reactor.
  • the reactor inlet and outlet pressures and temperatures were measured by visual gauges at the points indicated in the flowsheet.
  • pre-cooling or pre-heating of both anolyte and catholyte was employed to keep the temperature at a desired level.
  • Liquid product was withdrawn from the sampling point and analyzed for formate concentration.
  • Gas product from the gas/liquid separator (a packed bed of graphite felt) was controlled by a 3-way valve either to an Orsat gas analyzer for CO 2 and CO analysis, to a wet gas flow meter for flow rate measurement, or to a Tedlar sampling bag for subsequent hydrocarbon analysis with gas chromatograph.
  • Galvanostatic electrolysis of CO 2 was carried out with a DC power supply connecting across the anode and cathode. A voltmeter was also connected to the unit to measure the reactor voltage. All voltages included anode potential, cathode potential and IR drop. The individual electrode potentials were not measured.
  • An automatic pressure control valve was used in the anolyte product line to balance the pressure in the anode chamber against that in the cathode chamber. Such a pressure balance is required to prevent catholyte by-passing the 3-D cathode and/or the bursting of the membrane that can occur when the cathode pressure exceeds the anode pressure.
  • Processes of the invention were performed first in Reactor A (small reactor) and then in a seven-fold big Reactor B (big reactor) to evidence the effects of scale up. Both reactors have the configuration shown in Figure 2.
  • the reactors consist of a cathode feeder plate and a 3-D cathode, a Nafion cation exchange membrane separator, anode spacer/membrane support, an anode feeder plate and gaskets.
  • the cathode mesh, anode mesh and the anode spacer are sealed on their margins by silicone glue, and then the cell assembly is sandwiched between insulated mild steel plates and uniformly compressed with SS bolts to give a balanced fluid distribution.
  • Figure 3 shows a sectioned elevation view of the single-cell Reactor A.
  • the "flow-by" cathode of this reactor had dimensions of 30 mm width and 150 mm height (geometric surface). The thickness of the cathode depended on which 3-D cathode material was used.
  • the thickness of the cathode was the total thickness of these all layers, which ranged from 0.38 to 1.83 mm; for graphite felts and metal granules or shot, the cathode materials were embedded in two layers of Neoprene gasket with the back of the cathode in contact with the cathode feeder, therefore the thickness of the cathode was that of the gasket, i.e. 3.2 mm.
  • the geometric (a.k.a. superficial) cathode area perpendicular to the electric current was 30 mm by 150 mm - 4.5X10 "3 m 2 .
  • Reactor A the applied current ranged from 1 to 14 A with corresponding superficial current density from 0.22 to 3.11 kA rrf 2 .
  • Reactor B tin-coated copper mesh cathodes or tin granule cathodes were used.
  • Figure 4 presents the dimensioned front view and corresponding dimensions of Reactor B with a tin granule fixed-bed cathode.
  • the gasket was purposely made with five triangles on each side to direct the flow toward the centre of the cathode.
  • the superficial cathode area was 3.22x10 '2 m 2 , which was about seven times that of Reactor A (4.5X10 "3 m 2 ).
  • the applied current in Reactor B ranged from 20 to 101 A with corresponding superficial current density 0.62 to 3.20 kA m '2 .
  • Reactor B was assembled with a tin granule fixed-bed cathode, according to the following procedures: (1) A sanded tin plate (99.99 wt% Sn, 3mm thick) cathode feeder was put onto the neoprene gasket; (2) The pretreated tin granules were spread uniformly into a Durabla gasket (3.2 mm thick) on the tin plate, and layers of Netion screen were inserted into the entrance and exit regions of the catholyte flow to distribute the fluid and support the membrane; (3) The wet Nafion 117 membrane was put on top of the tin granule bed, and then, the PVC screen spacer, anode SS mesh, and anode feeder (SS plate) were placed on top of one another in that sequence; (4) Lastly, a cell body was put into place, and 243/8 inch bolts were employed to compress the sandwiched cell uniformly.
  • cathode materials are available for use in alternative aspects of the invention. Carbon dioxide can be electro-chemically reduced on almost all groups of metals in the periodic table to give a variety of products with different levels of selectivity.
  • the following cathode materials may be adapted to particular embodiments: Nano-stuctured Cu deposited on graphite felt; Cu/Sn alloy deposited on graphite felt; nano-structured Sn on Sn mesh, Sn coated plastic mash, Cu mesh; Sn deposited graphite felt; Sn coated copper mesh; Pb plate, shot, granules, grid and Pb-C reticulate; Sn shot and granules.
  • a high (specific) surface area micro or nano- structured deposit on a 3D substrate is desirable.
  • Other potential cathodes are. nano-structured Cu on Cu mesh, nano-structured Sn on Sn mesh, or Sn coated plastic mesh, alternatively with Pb, In or Hg as the electro-active surface.
  • Reactor A using granulated tin cathodes (99.9 wt% Sn) and a feed gas of 100% CO 2 showed slightly better performance than that of the tinned-copper mesh cathodes.
  • the seven fold scaled-up Reactor B used a feed gas of 100% CO 2 with the aqueous catholyte and anolyte respectively [0.5 M KHCO 3 + 2 M KC1] and 2 M KOH 1 at inlet pressure from 350 to 600 kPa(abs) and outlet temperature 295 to 325 K.
  • Reactor B For a superficial current density of 0.6 to 3.1 kA m "2 Reactor B achieved corresponding formate current efficiencies of 91 to 63%, with the same range of reactor voltage as that in Reactor A (2.7 to 4.3 V). Up to 1 M formate was obtained in the catholyte product from a single pass in Reactor B.
  • Cathode ca. 50 mesh tin granules. 150 mm high by 32 mm wide by 3 mm thick
  • Cathode superficial area 45E-4 m2
  • Cathode feeder tin foil supported on a copper plate
  • Example 1 An electrochemical reactor as described in Example 1 was constructed and operated as follows:
  • Anode 304 stainless steel, number 10 mesh (10 mesh/inch)
  • Anode spacer PVC "fly screen”, 10 mesh.
  • Cathode ca. 50 mesh tin granules. 680 mm high by 50 mm wide by 3 mm thick
  • Cathode superficial area 340E-4 m2
  • Cathode feeder 2 mm thick tin plate.
  • Table 2 shows the performance of this reactor.
  • a reactor was constructed as in Example 1 , operation was as in Example 2, except the anolyte was replaced by an acid sodium sulphate solution as follows:
  • the reactor was operated over a current range from 1 to 14 A (0.2 to 3.1 kA/m 2 ) with corresponding formate CE from 80 to 30 % and reactor voltage from 3.5 to 8.0 V.
  • the invention may utilize ammonium cations, to produce ammonium formate.
  • a reactor was constructed as in Example 1 , operation was as in Example 4, except the catholyte potassium cations were replaced by ammonium and the anolyte was replaced by an acid ammonium sulphate solution, as follows:
  • the reactor was operated over 2 hours with formate CE ranging from 35 to 70 % and reactor voltage from 4.6 to 5.2 V.
  • Anode 304 stainless steel number 10 mesh (10 mesh/inch)
  • NaHCO 2 sodium formate
  • NaHCO 3 sodium bicarbonate
  • the feed plus recycle CO 2 is compressed to about 300 kPa(abs) and delivered to the cathode of the electrochemical reactor along with the recycling catholyte, an aqueous solution of NaHCO 2 and NaHCO 3 .
  • the cathode outlet goes to a gas/liquid separator from which the liquid is divided into a direct recycle and a stream from which NaHCO 2 and NaHCO 3 are separated by evaporation and fractional crystallization to give the main cathode products (NaHCO 2 and NaHCO 3 ).
  • the cathode outlet gas goes to a gas separation system (e.g. pressure swing adsorption) that recovers H 2 and delivers th ⁇ unconverted CO 2 to recycle.
  • a gas separation system e.g. pressure swing adsorption
  • the anode side of this process involves a feed of NaOH (sodium hydroxide) whose sodium content (Na + ) is transported across the cation membrane while the hydroxide is converted to oxygen that is recovered as the co-product from a gas/liquid separator.
  • the recycle streams in this process include the necessary compressors and pumps along with heat exchangers (e.g. C1 , C2, C3) to control the reactor temperature in the range of about 300 to 350 K.
  • Figure 8 illustrates the electrosynthesis of formic acid from carbon dioxide and water.
  • the exemplified process converts CO 2 to HCO 2 H (formic acid) with a byproduct of H 2 (hydrogen) and co-product of O 2 (oxygen).
  • the feed plus recycle CO 2 is compressed to about 300 kPa(abs) and delivered to the cathode of the electrochemical reactor (U 1) along with the recycling catholyt ⁇ , an aqueous solution of NH 4 HCO 2 and NH 4 HCO 3 plus (if required) a supporting electrolyte such as NH 4 CI or (NH 4 J 2 SO 4 .
  • the cathode outlet stream goes to a gas/liquid separator (U3) from which the liquid is divided (U5) into a direct recycle and a stream that is passed to a thermochemical acidolysis reactor/separator (U6.U7) where formic acid is obtained by reaction 9 with sulphuric acid (generated in the anolyte) and distilled under partial vacuum to give an overhead product of aqueous formic acid and a bottoms solution of (NH 4 J 2 SO 4 that is recycled to the anode via the mixer U8.
  • the gas stream from U3 passes to a separator (U4) where H 2 is recovered and CO 2 is recycled to the reactor feed via mixer U2, along with CO 2 generated by the side- reaction 7 in the acidolyis reactor.
  • An aqueous solution of (NH 4 J 2 SO 4 and H 2 SO 4 recycles through the anode circuit, supplying NH 4 + and H + cations for transport to the catholyte via the cation membrane.
  • the co-product O 2 gas is generated with protons (H + ) at the anode by reaction 4 and recovered from a gas/lquid separator (U9).
  • the recycling acid anolyte is then divided (U10) to supply H 2 SO 4 for the acidolysis reaction (U6) from which the spent reactant is re-combined with the anolyte (U8).
  • M&E material and energy
  • the conditions of this process may be chosen to promote the main net reaction 10.
  • the characteristics of the process of this example, to promote reaction 10 may be selected as follows: i. Appropriate electrode materials, current density, fluid compositions, fluid loads, pressure and temperature in the electrochemical reactor, ii. Maintaining the anolyte composition with respect to acid and salt to provide cation transport across the membrane in the correct ratio (e.g. HTNH 4 + ) that balances the rates of cathode reactions 1 and 2 and holds the catholyt ⁇ pH in the desired range. iii. A bulk catholyte pH in the range about 4 to 10, preferably 6 to 8. iv.
  • Figure 9 illustrates electro-synthesis of ammonium formate from carbon dioxide, ammonia and water. This process converts CO 2 and NH 3 to NH 4 HCO 2 (ammonium formate) with a byproduct of H 2 (hydrogen) and co-product of O 2 (oxygen).
  • the feed plus recycle CO 2 is compressed and delivered to the cathode of the electrochemical reactor along with the recycling catholyte, an aqueous solution of NH4HCO2 (e.g. > 1 M) with minor amounts of NH 4 HCO 2 (ammonium bicarbonate - e.g. 0.1 M).
  • NH4HCO2 e.g. > 1 M
  • NH 4 HCO 2 ammonium bicarbonate - e.g. 0.1 M
  • Ammonia (NH 3 gas or aqueous solution) is fed to the anolyte circuit where it combines to form (NH 4 )SSO 4 (ammonium sulphate).
  • An aqueous solution of (NH 4 J 2 SO 4 and H 2 SO 4 then recycles through the anode circuit, supplying NH 4 + and H + cations for transport to the catholyte via the cation membrane.
  • the co- product O 2 gas is generated with protons (H + ) at the anode by reaction 4 and recovered from a gas/liquid separator.
  • the ratio [NH 4 + ] / [H + ] is maintained in the anolyte to supply these species to the catholyte at rates that balance the stoichiometry of reactions 1 and 2 and produce a catholyte solution of predominantly ammonium formate at pH in the range about 4 to 8.
  • Variations of this scheme may include for example replacement of
  • anode co-product may be Cl 2 by reaction 5.
  • Anode co-products may also include peroxy-compou ⁇ ds such as ammonium persulphate (NH 4 J 2 S 2 O 8 or persulphuric acid H 2 S 2 Os, etc. by reaction 14.

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Abstract

L'invention concerne, dans diverses formes de réalisation, des procédés électrochimiques de réduction du dioxyde de carbone, par exemple par transformation du dioxyde de carbone en sels de formate ou en acide formique. Dans des formes de réalisation choisies, un réacteur continu utilisant une cathode tridimensionnelle et un flux de catholyte biphasé (gaz/liquide) permet d'obtenir des conditions avantageuses pour l'électroréduction du dioxyde de carbone. Dans ces formes de réalisation, le flux biphasé continu de solvant catholyte et de gaz contenant du dioxyde de carbone présente, dans des rapports choisis de flux en volume des phases gazeuse/liquide, des conditions dynamiques favorisant l'électroréduction d'oxydes de carbone à des densités effectives de courant superficiel et à des vitesses spatiales de gaz relativement élevées, pour des tensions (de bain) relativement faibles (<10 volts) de réacteur. Dans certaines formes de réalisation, une retenue relativement élevée de gaz interne dans la chambre de cathode (notable lorsque le rapport en volume des phases de gaz interne/liquide > 0,1) permet d'obtenir des concentrations de CO2 dans la phase liquide supérieures à la concentration d'équilibre, et facilite aussi l'obtention de densités effectives de courant superficiel relativement élevées. Dans certaines formes de réalisation, ces caractéristiques sont obtenues par exemple à un pH de catholyte > 7 et à des pression partielles de CO2 relativement faibles (< 10 bar). Dans certaines formes de réalisation, lesdites caractéristiques sont obtenues par exemple dans des conditions quasi adiabatiques, avec une température de sortie de catholyte pouvant atteindre environ 80 °C.
EP06804642A 2005-10-13 2006-10-13 Reduction electrochimique de dioxyde de carbone a courants paralleles Withdrawn EP1951933A4 (fr)

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US20080223727A1 (en) 2008-09-18
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CN101657568A (zh) 2010-02-24
CN101657568B (zh) 2013-05-08
WO2007041872A1 (fr) 2007-04-19
JP2009511740A (ja) 2009-03-19
AU2006301857A1 (en) 2007-04-19
US20160068974A1 (en) 2016-03-10
WO2007041872B1 (fr) 2007-07-19
US20140299482A1 (en) 2014-10-09

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