WO2024137896A1 - Liquid electrolyzer for single-conversion-step electrocatalytic reduction of co2 to ethylene glycol - Google Patents

Liquid electrolyzer for single-conversion-step electrocatalytic reduction of co2 to ethylene glycol Download PDF

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Publication number
WO2024137896A1
WO2024137896A1 PCT/US2023/085274 US2023085274W WO2024137896A1 WO 2024137896 A1 WO2024137896 A1 WO 2024137896A1 US 2023085274 W US2023085274 W US 2023085274W WO 2024137896 A1 WO2024137896 A1 WO 2024137896A1
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Prior art keywords
ethylene glycol
catalyst
alkali
cathode
electrolyzer
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PCT/US2023/085274
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French (fr)
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Anders B. LAURSEN
Karin U. D. CALVINHO
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Renewco2 Inc.
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Publication of WO2024137896A1 publication Critical patent/WO2024137896A1/en

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/033Liquid electrodes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091Electrodes 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
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00Diaphragms; Spacing elements
    • C25B13/02Diaphragms; Spacing elements characterised by shape or form
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00Electrolytic production of organic compounds
    • C25B3/01Products
    • C25B3/07Oxygen containing compounds
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00Electrolytic production of organic compounds
    • C25B3/20Processes
    • C25B3/25Reduction
    • C25B3/26Reduction of carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417Polyolefins

Definitions

  • the presently disclosed technology relates generally to the electrolytic production of glycol, ethylene glycol, and/or monoethlyene glycol (MEG) from carbon sources, originating from but not limited to oil, gas, coal, or biomass or from captured carbon sources.
  • glycol ethylene glycol
  • MEG monoethlyene glycol
  • thermochemical and electrocatalytic Known systems for the reduction of carbon dioxide fall into two groups: thermochemical and electrocatalytic.
  • the former has been demonstrated in a multi-step reaction for the production of syn-gas a mixture of carbon monoxide and hydrogen, which is further processed to make compounds such as methanol or long-chain hydrocarbons or waxes (e.g., by the Fisher- Tropsch reaction).
  • the former precursor then has to be converted to either formaldehyde by reoxidation followed by reaction to ethylene glycol by a process commercialized by Eastman Company, or for the latter thermally cracked to ethylene followed by the legacy process conversion to ethylene glycol.
  • Liquid phase membrane electrolyzers are well-known for reduction of water to hydrogen or for reducing carbon dioxide (CO2) to gaseous products such as carbon monoxide, methane, or ethylene, or liquid products such as formate an ethanol (see, e.g., U.S. Patent Nos. 10,648,091 and 11,417,901, as well as European Patent No. 2382174 A2).
  • U.S. Patent No. 10,676,833 which is herein incorporated by reference, discloses a catalyst and co-catalyst in an electrode of given particle sizes, with binders aggregating the catalyst to the electrode support.
  • the electrode in the prior art is described as being utilized with an anode in an undefined electrolyzer.
  • the prior art describes how to obtain a crude solution of hydrocarbons in an aqueous solution mixed with supporting electrolyte, reaction intermediates and homogeneous co-catalyst.
  • One purpose of the presently disclosed technology is to integrate a two component electrocatalytic electrode into an electrolyzer unit, which allows the conversion of a carbon source, such as carbon dioxide, to an ethylene glycol reaction in one reactor, thereby increasing the process efficiency and utilizing electricity as the energy input for the reaction.
  • Electricity can be provided from renewable sources or from a mixture of power production (e.g., fossil fuel).
  • the presently disclosed technology combines a carbon dioxide reducing catalyst and co-catalyst into an electrolyzer to obtain a crude reaction product.
  • the combination of an electrocatalytic electrode with two components both an electrocatalyst and a co-catalyst into one system has not been demonstrated in an electrolyzer, such as that described below.
  • the presently disclosed technology describes for the first time how to incorporate two component electrocatalytic electrodes into a liquid phase membrane electrolyzer cell for the production of mono-ethylene glycol.
  • the presently disclosed technology produces di-ethylene glycol, and in another embodiment the presently disclosed technology produces tri-ethylene glycol, and in another embodiment the presently disclosed technology produces mixtures of ethylene glycol (monomer, dimer, and/or trimer).
  • FIG. 1 is a schematic diagram of one embodiment of the presently disclosed technology
  • FIG. 2 is a schematic diagram of another embodiment of the presently disclosed technology
  • FIG. 3 is a schematic diagram of yet another embodiment of the presently disclosed technology.
  • Fig. 4 is another schematic diagram of one embodiment of the presently disclosed technology.
  • the term “catalyst” or “electrocatalyst” refers to a material capable of promoting the electrochemical reduction of a carbon-based reactant.
  • the carbon-based reactant is chosen from CO2, CO, and/or an inorganic carbon, or a combination thereof.
  • this material binds the hydrogen (e.g., hydride, hydrogen atom or proton) and delivers it to the CO2 reduction intermediate or surface bound C0 2 .
  • co-catalyst refers to a material which does not independently reduce a carbon-based reactant to the products of interest, but either (a) promotes the formation of one or more reaction products that are not achieved by the electrocatalyst alone, or (b) alters the product distribution of products achieved on the electrocatalyst to yield significantly more of a desired product.
  • the co-catalyst affects the nature or distribution of products by interacting with the electrocatalyst or reaction intermediates. For industrial applications a reaction, selectivity in the range of 60-99.99% towards the product of interest are considered preferential.
  • CO 2 could refer to any form of CO2, gaseous, dissolved that is in the form of carbonic acid, bicarbonate, or carbonate or alternatively partly reduced as CO.
  • gaseous dissolved that is in the form of carbonic acid, bicarbonate, or carbonate or alternatively partly reduced as CO.
  • electrocatalysts systems are as defined in prior art U.S. Patent No. 10,676,833.
  • Liquid phase electrolyzers with percolator liquid compartment are described in the patent literature for chlorine and alkali hydroxide (e.g., U.S. 2005/0183951, U.S. 9,562,294, and U.S. 8,247,098).
  • the liquid percolator design could never have been predicted for the production of ethylene glycol prior to the discovery of the Rutgers University catalysts systems, such as that disclosed in U.S. Patent No. 10,676,833. Even still the implementation of a multi-catalyst system into a conventional percolator electrolyzer could not have been predicted to require extremely high catalyst loadings.
  • the percolator medium could be chosen from materials stable in carbonate and alkali media present during reaction, such as glass, poly-tetrafluoroethylene, poly- diflouroethylene, poly-ethersulfone, poly-urethane, poly-ethylene (ultrahigh density, high and low density), polypropylene, or similar materials fabricated into a porous structure with a void volume in the range of exactly or approximately 20-75%, such as foam, mesh, cloth, or paper.
  • materials stable in carbonate and alkali media present during reaction such as glass, poly-tetrafluoroethylene, poly- diflouroethylene, poly-ethersulfone, poly-urethane, poly-ethylene (ultrahigh density, high and low density), polypropylene, or similar materials fabricated into a porous structure with a void volume in the range of exactly or approximately 20-75%, such as foam, mesh, cloth, or paper.
  • materials stable in carbonate and alkali media present during reaction such as glass, poly-tetra
  • the electrode is fabricated by dispersion of catalyst powder in a suspension consisting of water, commercial poly-tetrafluoroethylene suspensions (primary particles size from 50-500nm) with anionic surfactants, water, and 0-50% by dry weight of carbon black (carbon particle size between 30-1500 nm).
  • catalyst is then coagulated into a paste by addition of 1 -propanol under continuous agitation.
  • the paste can then optionally be applied to a metal mesh support.
  • this support is an aluminum 200x200 mesh.
  • this support is a deactivated stainless steel mesh.
  • the resulting electrode can optionally be cold or hot pressed to form the final electrode.
  • the final electrode composition can contain from 15-50% dry weight basis polytetrafluroethylene.
  • the electrolyzer is constructed as described in Fig. 3.
  • a cathode flow field can be constructed in titanium or stainless steel.
  • the cathode described in the paragraph immediately above can be placed on top of the flow field with a gasket frame with a thickness that is less than that of the electrode to allow for compression and electrical contact to be made. In one optional embodiment, the thickness is reduced by 1-10% of the electrode.
  • a gasket can be placed on top of the cathode with an opening the size of the active area. Considering the active area as a square or rectangle (with or without rounded corners), the typical gasket has a reduced side length of the opening of approximately 10% from that of the cathode catalyst coated area.
  • a liquid flow compartment can be placed atop the cathode membrane assembly.
  • the compartment can be connected to a reservoir with the catholyte and connected with a pump to circulate electrolyte in either a single pass or recirculating mode of operation.
  • the thickness of this compartment is in this example 1.5 mm and the flow compartment is outfitted with a percolator made from polypropylene.
  • a cathode membrane can be placed atop another gasket.
  • this membrane is Nafion 212 cation exchange membrane; another gasket as the one above is placed to seal the membrane.
  • the two gaskets and cathode membrane are combined into a frame and gasket assembly.
  • An anode can be placed atop the membrane and gasket assembly.
  • the anode is in this example a titanium mesh coated with metallic Ru/Ir alloy as the active anode catalyst.
  • the anode electrode can be positioned with an anode frame using the same thickness constraints described for the cathode.
  • the anode is spot welded to the anode flow field to reduce contact resistance under anodic operating conditions. In the absence of spot welding, the anode and anode flow fields will both grow a native oxide that will decrease conductivity and thereby the performance of the cell.
  • the single cell described herein is in one embodiment compressed by bolding anode and cathode flow fields together to achieved cell compression. Multiple cells can then be stacked together to achieve the final operating stack. In another embodiment the cells are assembled together in stacks before compressing multiple cells into one stack assembly.
  • the carbon source CO2, CO, or inorganic CO2 solutions, or combinations thereof, is circulated through the cathode flow field with a flow rate of 1-900 milliliter/min/cm 2 active area.
  • the catholyte can be circulated through the liquid compartment with a flow rate of 1-900 milliliter/min/cm 2 active area; the accumulated product crude is obtained from this.
  • the catholyte is circulated in a single pass mode building the final product concentration; alternatively the catholyte is circulated continuously with a smaller product crude stream being removed and replaced with fresh catholyte.
  • the anode product can be obtained from the anode flow field by flowing an anolyte that can be a gas or liquid with supporting electrolyte. In one example, this anolyte is an aqueous 0.5M potassium bicarbonate solution.
  • the liquid cathode electrolyte contains between 0 and 2M alkali or alkali earth cation and carbonate anions.
  • the anion is phosphate, pyrophosphate, sulphate, or borate.
  • one embodiment of the presently disclosed technology produces a liquid crude with a low concentration (e.g., 0.001%-7% product concentration).
  • the presently disclosed technology produces a high product concentration (e.g., 7%-50%) from the cathode side of the LPM-EC system.
  • the cell is operated at 0.1mA/cm 2 -lA/cm 2 and the product recovered will be a crude containing reaction intermediates (formate, formaldehyde, glyceraldehyde, glycolaldehyde, methylglyoxal, and/or furandiol or mixtures thereof), mono/di/tri ethylene glycol or mixtures thereof, supporting electrolyte with pKa’s in the range of 3-9 for instance, such as alkali or alkali earth carbonates, sulphates, phosphates, hypophosphates, citrates, or borates and the in one iteration homogenous co-catalyst and in other iterations residue from the immobilized co-catalyst.
  • reaction intermediates formate, formaldehyde, glyceraldehyde, glycolaldehyde, methylglyoxal, and/or furandiol or mixtures thereof
  • liquid crude refers to mono-ethylene glycol, di-ethylene glycol, and/or tri-ethylene glycol.
  • the phrase “liquid crude” optionally refers to the product stream with the ethylene glycols and any formate and methyl glyoxal, furan diol impurities that will need to be removed later.
  • a difference between the embodiment shown in Fig. 2 and that shown in Fig. 3 is the presence of a gap or spacing in the latter.
  • the inclusion or omittance of the gap is the result of how the anolyte is fed.
  • the feed is from the back penetrating the porous electrode. Therefore, in the embodiment shown in Fig. 2, the anode electrode is in physical contact with the membrane.
  • the liquid is allowed to run in front of the anode, so the anode is physically separated or spaced-apart from the membrane by a gap or spacing.
  • the gap can be between 0.1- 10 mm wide.
  • Figs. 1-3 each show a form of CO2 recycling in accordance with the presently disclosed technology.
  • the liquid crude and CO2 depleted streams exits the cell together and are separated by a gas-disengagement unit.
  • the CO2 is then fed into the incoming reactant stream of CO2 to the cathode.
  • unique features of the presently disclosed technology include:
  • the single step conversion process of the presently disclosed technology will reduce capital costs and thereby improve profitability.
  • the presently disclosed technology thus provides for the production of mono-ethylene glycol, di-ethylene glycol, and/or tri-ethylene glycol from CO2 in a single reaction conversion step.
  • One commercial advantage of the presently disclosed technology is a product that has a negative carbon footprint, which is a market differentiator (e.g., commands a sur-charge in current market), which is not available from prior art processes.
  • Another commercial advantage of the presently disclosed technology is the process can be installed as an add-on process (e.g., retrofit) on existing facilities or as a stand-alone facility.
  • a method for the employing an electrocatalytic cathode containing both a electrocatalyst and co-catalyst in a liquid phase membrane electrolyzer employing a liquid layer cathode with a percolation layer to reduce hydrostatic pressure effects on the cathode for the electro-reduction of CO2, CO, and/or inorganic carbon (carbonate/bicarbonate anions/carbonic acid) to ethylene glycol in a single reactor.
  • Embodiment 2A The combination of Embodiment 1 A, wherein the cathode comprises an electrocatalyst, co-catalyst to direct the carbon product selectivity.
  • Embodiment 1 A is a transition metal phosphide and the co-catalyst is a Lewis/Bronsted acid and base pair.
  • the percolator medium is chosen from materials stable in carbonate and alkali media present during reaction, such as glass, polytetrafluoroethylene, poly-diflouroethylene, poly-ethersulfone, poly-urethane, poly-ethylene (ultrahigh density, high and low density), polypropylene, or similar materials fabricated into a porous structure with a void volume in the range of exactly or approximately 20-75%, such as foam, mesh, cloth, or paper.
  • materials stable in carbonate and alkali media present during reaction such as glass, polytetrafluoroethylene, poly-diflouroethylene, poly-ethersulfone, poly-urethane, poly-ethylene (ultrahigh density, high and low density), polypropylene, or similar materials fabricated into a porous structure with a void volume in the range of exactly or approximately 20-75%, such as foam, mesh, cloth, or paper.
  • Embodiment 1 A The combination of Embodiment 1 A, the liquid crude produced at the cathode contains ethylene glycol, methyl glyoxal, furandiol, and formic acid.
  • Embodiment 1 A The combination of Embodiment 1 A, the produced ethylene glycol undergoes polymerization to di-ethylene glycol, and or tri-ethylene glycol in addition to mono-ethylene glycol.
  • Embodiment 1 A the cathode distance to the solid electrolyte is optimized to facilitate ionic conductivity with the electrolyte and liquid product diffusion into the percolation layer.
  • Embodiment 1 A The combination of Embodiment 1 A, the catholyte is 0 and 2M alkali or alkali earth cation and whereas the anion is carbonate, phosphate, pyrophosphate, sulphate, or borate or mixtures thereof.
  • Embodiment 1 A the anode distance to the solid electrolyte is optimized to facilitate ionic conductivity with the electrolyte and oxygen bubble release.
  • Embodiment 6 A a liquid analyte is flowed which contains ionic conductive supporting electrolyte salts, such as alkali or alkali-earth metal salts contains cations such as Na, K, Rb, Cs, Mg, Ca, Sr, Ba or combinations thereof.
  • ionic conductive supporting electrolyte salts such as alkali or alkali-earth metal salts contains cations such as Na, K, Rb, Cs, Mg, Ca, Sr, Ba or combinations thereof.
  • Embodiment 10A the alkali metal salt anion is carbonates, sulphates, phosphates, hypophosphates, citrates, or borates., or combinations thereof.

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Abstract

A method and system can be configured to integrate a two component electrocatalytic electrode into a working electrolyzer unit, which allows for the conversion of carbon dioxide to an ethylene glycol reaction crude in one reactor. This system increases the process efficiency and utilizes electricity as the energy input for the reaction.

Description

LIQUID ELECTROLYZER FOR SINGLE-CONVERSION-STEP ELECTROCATALYTIC REDUCTION OF CO2 TO ETHYLENE GLYCOL
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims priority to U.S. Provisional Patent Application No. 63/476,384 filed December 21, 2022, the entire disclosure of which is hereby incorporated by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] This invention was made with government support under DE-SC0020615, and DE- SC0014664 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
FIELD
[0003] The presently disclosed technology relates generally to the electrolytic production of glycol, ethylene glycol, and/or monoethlyene glycol (MEG) from carbon sources, originating from but not limited to oil, gas, coal, or biomass or from captured carbon sources.
BACKGROUND
[0004] Conventional production of ethylene glycol from carbon sources, such as oil, gas, coal, or biomass, includes multiple reaction steps each done at different reaction conditions, such as temperature and pressure. This prior art process can be undesirable because it decreases efficiencies both in terms of energy and conversion efficiencies. These inefficiencies or losses are primarily due to lack of an efficient catalyst that can convert the feedstock (e.g., oil, natural gas, coal, bio-ethanol, and/or bio-mass) in fewer steps, or ideally one step, to achieve the final product. As a result, this prior art production of ethylene glycol from fossil resources, such as oil, gas, or coal, contributes significantly to global carbon dioxide emissions.
[0005] By far the majority, perhaps 90+%, of ethylene glycol is commercially produced in a multi-step process from hydrocarbon feedstocks, via ethylene, then catalytic oxidation of ethylene to ethylene oxide, and finally ethylene oxide hydration to produce ethylene glycol, plus dimers and trimers of the glycol. This is a costly and environmentally challenged process. First, the dominant commercial process for ethylene production, high temperature steam cracking of hydrocarbon feedstocks, is highly energy intensive. In the US, natural gas liquids are a common feedstock, although heavier feeds are also used. For European and Japanese ethylene production, the situation is worse, as heavier feedstocks are still predominant and from these feedstocks, ethylene production is non-selective, requiring energy and capital intensive for separation from many coproducts. Secondly, ethylene oxide production is a costly process that generates a substantial carbon dioxide byproduct. And finally, the hydration of ethylene oxide in an excess of water requires a capital and energy intensive process to recover the desired polymer grade ethylene glycol.
[0006] Current carbon dioxide reduction (CO2RR) suffers from three major constraints: 1) high electricity costs, 2) low relative price of bulk chemicals, and 3) low energy efficiency. Prior art processes are described in U.S. Patent Nos. 10,329,676, 7,972,484, 8,247,098, International Publication No. WO 2012139741 and U.S. Publication No. 2005/0183951.
[0007] Conversion of bio-mass by pyrolysis or fermentation/dehydration to ethylene glycol or ethylene, respectively (the latter is converted to ethylene glycol through the aforementioned process), reduces the process carbon foot-print but still emits large quantities of carbon dioxide. All of the above processes require the combustion of fuels (e.g., bio-fuels or conventional) to provide the energy input of the chemical reactions.
[0008] Known systems for the reduction of carbon dioxide fall into two groups: thermochemical and electrocatalytic. The former has been demonstrated in a multi-step reaction for the production of syn-gas a mixture of carbon monoxide and hydrogen, which is further processed to make compounds such as methanol or long-chain hydrocarbons or waxes (e.g., by the Fisher- Tropsch reaction). The former precursor then has to be converted to either formaldehyde by reoxidation followed by reaction to ethylene glycol by a process commercialized by Eastman Company, or for the latter thermally cracked to ethylene followed by the legacy process conversion to ethylene glycol.
[0009] Liquid phase membrane electrolyzers (LP-ECs) are well-known for reduction of water to hydrogen or for reducing carbon dioxide (CO2) to gaseous products such as carbon monoxide, methane, or ethylene, or liquid products such as formate an ethanol (see, e.g., U.S. Patent Nos. 10,648,091 and 11,417,901, as well as European Patent No. 2382174 A2).
[0010] U.S. Patent No. 10,676,833, which is herein incorporated by reference, discloses a catalyst and co-catalyst in an electrode of given particle sizes, with binders aggregating the catalyst to the electrode support. The electrode in the prior art is described as being utilized with an anode in an undefined electrolyzer. The prior art describes how to obtain a crude solution of hydrocarbons in an aqueous solution mixed with supporting electrolyte, reaction intermediates and homogeneous co-catalyst.
[0011] Further background is provided in the white paper titled, “RenewCO2 Catalyst Technology”.
SUMMARY
[0012] In an environmentally aware world, the burdensome, prior art process described above begs replacement with a more selective, direct route.
[0013] One purpose of the presently disclosed technology is to integrate a two component electrocatalytic electrode into an electrolyzer unit, which allows the conversion of a carbon source, such as carbon dioxide, to an ethylene glycol reaction in one reactor, thereby increasing the process efficiency and utilizing electricity as the energy input for the reaction. Electricity can be provided from renewable sources or from a mixture of power production (e.g., fossil fuel).
[0014] In one embodiment, the presently disclosed technology combines a carbon dioxide reducing catalyst and co-catalyst into an electrolyzer to obtain a crude reaction product. The combination of an electrocatalytic electrode with two components both an electrocatalyst and a co-catalyst into one system has not been demonstrated in an electrolyzer, such as that described below.
[0015] In one embodiment, in contrast to the prior art, the presently disclosed technology describes for the first time how to incorporate two component electrocatalytic electrodes into a liquid phase membrane electrolyzer cell for the production of mono-ethylene glycol. In another embodiment, the presently disclosed technology produces di-ethylene glycol, and in another embodiment the presently disclosed technology produces tri-ethylene glycol, and in another embodiment the presently disclosed technology produces mixtures of ethylene glycol (monomer, dimer, and/or trimer).
BRIEF DESCRIPTION OF THE DRAWINGS:
[0016] The foregoing summary, as well as the following detailed description of the presently disclosed technology, will be better understood when read in conjunction with the appended drawings, wherein like numerals designate like elements throughout. For the purpose of illustrating the presently disclosed technology, there are shown in the drawing’s various illustrative embodiments. It should be understood, however, that the presently disclosed technology is not limited to the precise arrangements and instrumentalities shown. In the drawings:
[0017] Fig. 1 is a schematic diagram of one embodiment of the presently disclosed technology;
[0018] Fig. 2 is a schematic diagram of another embodiment of the presently disclosed technology;
[0019] Fig. 3 is a schematic diagram of yet another embodiment of the presently disclosed technology; and
[0020] Fig. 4 is another schematic diagram of one embodiment of the presently disclosed technology.
DETAILED DESCRIPTION
[0021] While systems, devices and methods are described herein by way of examples and embodiments, those skilled in the art recognize that the presently disclosed technology is not limited to the embodiments or drawings described. Rather, the presently disclosed technology covers all modifications, equivalents and alternatives falling within the spirit and scope of the appended claims. Features of any one embodiment disclosed herein can be omitted or incorporated into another embodiment.
[0022] Any headings used herein are for organizational purposes only and are not meant to limit the scope of the description or the claims. As used herein, the word “may” is used in a permissive sense (i.e., meaning having the potential to) rather than the mandatory sense (i.e., meaning must). Unless specifically set forth herein, the terms “a,” “an” and “the” are not limited to one element but instead should be read as meaning “at least one.” The terminology includes the words noted above, derivatives thereof and words of similar import.
[0023] The prior art, including U.S. Patent No. 10,676,833, does not describe specific strategies for limiting co-catalyst concentration in the reaction solution by heterogenization/immobilization. It would be beneficial to provide industry and consumers with green alternatives to prior art processes. The presently disclosed technology makes-up for the above and other deficiencies of the prior art.
[0024] For the avoidance of confusion, the term “catalyst” or “electrocatalyst” refers to a material capable of promoting the electrochemical reduction of a carbon-based reactant. In some embodiments, the carbon-based reactant is chosen from CO2, CO, and/or an inorganic carbon, or a combination thereof. In some embodiments, this material binds the hydrogen (e.g., hydride, hydrogen atom or proton) and delivers it to the CO2 reduction intermediate or surface bound C02.
[0025] The term “co-catalyst” refers to a material which does not independently reduce a carbon-based reactant to the products of interest, but either (a) promotes the formation of one or more reaction products that are not achieved by the electrocatalyst alone, or (b) alters the product distribution of products achieved on the electrocatalyst to yield significantly more of a desired product. In some embodiments, the co-catalyst affects the nature or distribution of products by interacting with the electrocatalyst or reaction intermediates. For industrial applications a reaction, selectivity in the range of 60-99.99% towards the product of interest are considered preferential. Here, CO2 could refer to any form of CO2, gaseous, dissolved that is in the form of carbonic acid, bicarbonate, or carbonate or alternatively partly reduced as CO. As an example of possible co-catalyst and electrocatalysts systems are as defined in prior art U.S. Patent No. 10,676,833.
[0026] Liquid phase electrolyzers with percolator liquid compartment are described in the patent literature for chlorine and alkali hydroxide (e.g., U.S. 2005/0183951, U.S. 9,562,294, and U.S. 8,247,098). The liquid percolator design could never have been predicted for the production of ethylene glycol prior to the discovery of the Rutgers University catalysts systems, such as that disclosed in U.S. Patent No. 10,676,833. Even still the implementation of a multi-catalyst system into a conventional percolator electrolyzer could not have been predicted to require extremely high catalyst loadings.
[0027] Optionally, the percolator medium could be chosen from materials stable in carbonate and alkali media present during reaction, such as glass, poly-tetrafluoroethylene, poly- diflouroethylene, poly-ethersulfone, poly-urethane, poly-ethylene (ultrahigh density, high and low density), polypropylene, or similar materials fabricated into a porous structure with a void volume in the range of exactly or approximately 20-75%, such as foam, mesh, cloth, or paper. A person skilled in the art will be able to identify other materials, combinations thereof, and specific porous structures that could also be used and beneficial.
[0028] In one embodiment, the electrode is fabricated by dispersion of catalyst powder in a suspension consisting of water, commercial poly-tetrafluoroethylene suspensions (primary particles size from 50-500nm) with anionic surfactants, water, and 0-50% by dry weight of carbon black (carbon particle size between 30-1500 nm). Optionally, catalyst is then coagulated into a paste by addition of 1 -propanol under continuous agitation. The paste can then optionally be applied to a metal mesh support. In one optional embodiment, this support is an aluminum 200x200 mesh. In another optional embodiment, this support is a deactivated stainless steel mesh. The resulting electrode can optionally be cold or hot pressed to form the final electrode. The final electrode composition can contain from 15-50% dry weight basis polytetrafluroethylene.
[0029] In one embodiment of the presently disclosed technology, the electrolyzer is constructed as described in Fig. 3. A cathode flow field can be constructed in titanium or stainless steel. The cathode described in the paragraph immediately above can be placed on top of the flow field with a gasket frame with a thickness that is less than that of the electrode to allow for compression and electrical contact to be made. In one optional embodiment, the thickness is reduced by 1-10% of the electrode. A gasket can be placed on top of the cathode with an opening the size of the active area. Considering the active area as a square or rectangle (with or without rounded corners), the typical gasket has a reduced side length of the opening of approximately 10% from that of the cathode catalyst coated area. A liquid flow compartment can be placed atop the cathode membrane assembly. The compartment can be connected to a reservoir with the catholyte and connected with a pump to circulate electrolyte in either a single pass or recirculating mode of operation. The thickness of this compartment is in this example 1.5 mm and the flow compartment is outfitted with a percolator made from polypropylene. A cathode membrane can be placed atop another gasket. In one example this membrane is Nafion 212 cation exchange membrane; another gasket as the one above is placed to seal the membrane. In one embodiment the two gaskets and cathode membrane are combined into a frame and gasket assembly. An anode can be placed atop the membrane and gasket assembly. The anode is in this example a titanium mesh coated with metallic Ru/Ir alloy as the active anode catalyst. The anode electrode can be positioned with an anode frame using the same thickness constraints described for the cathode. In one optional embodiment, the anode is spot welded to the anode flow field to reduce contact resistance under anodic operating conditions. In the absence of spot welding, the anode and anode flow fields will both grow a native oxide that will decrease conductivity and thereby the performance of the cell. The single cell described herein is in one embodiment compressed by bolding anode and cathode flow fields together to achieved cell compression. Multiple cells can then be stacked together to achieve the final operating stack. In another embodiment the cells are assembled together in stacks before compressing multiple cells into one stack assembly. These stack are operated in a serial mode by applying a bias across the end cathode and anode flow fields. The carbon source: CO2, CO, or inorganic CO2 solutions, or combinations thereof, is circulated through the cathode flow field with a flow rate of 1-900 milliliter/min/cm2 active area. The catholyte can be circulated through the liquid compartment with a flow rate of 1-900 milliliter/min/cm2 active area; the accumulated product crude is obtained from this. In one embodiment the catholyte is circulated in a single pass mode building the final product concentration; alternatively the catholyte is circulated continuously with a smaller product crude stream being removed and replaced with fresh catholyte. The anode product can be obtained from the anode flow field by flowing an anolyte that can be a gas or liquid with supporting electrolyte. In one example, this anolyte is an aqueous 0.5M potassium bicarbonate solution.
[0030] Optionally, the liquid cathode electrolyte contains between 0 and 2M alkali or alkali earth cation and carbonate anions. In another embodiment, the anion is phosphate, pyrophosphate, sulphate, or borate. A person skilled in the art would understand that other supporting electrolytes can be used and can be beneficial.
[0031] Optionally, one embodiment of the presently disclosed technology produces a liquid crude with a low concentration (e.g., 0.001%-7% product concentration). In another embodiment, the presently disclosed technology produces a high product concentration (e.g., 7%-50%) from the cathode side of the LPM-EC system.
[0032] Optionally, the cell is operated at 0.1mA/cm2-lA/cm2 and the product recovered will be a crude containing reaction intermediates (formate, formaldehyde, glyceraldehyde, glycolaldehyde, methylglyoxal, and/or furandiol or mixtures thereof), mono/di/tri ethylene glycol or mixtures thereof, supporting electrolyte with pKa’s in the range of 3-9 for instance, such as alkali or alkali earth carbonates, sulphates, phosphates, hypophosphates, citrates, or borates and the in one iteration homogenous co-catalyst and in other iterations residue from the immobilized co-catalyst.
[0033] In one embodiment, in Fig. 1, the phrase “liquid crude” refers to mono-ethylene glycol, di-ethylene glycol, and/or tri-ethylene glycol. Alternatively or additionally, in Fig. 1, the phrase “liquid crude” optionally refers to the product stream with the ethylene glycols and any formate and methyl glyoxal, furan diol impurities that will need to be removed later.
[0034] A difference between the embodiment shown in Fig. 2 and that shown in Fig. 3 is the presence of a gap or spacing in the latter. The inclusion or omittance of the gap is the result of how the anolyte is fed. In the embodiment shown in Fig. 2, the feed is from the back penetrating the porous electrode. Therefore, in the embodiment shown in Fig. 2, the anode electrode is in physical contact with the membrane. In contrast, in the embodiment shown in Fig. 3, the liquid is allowed to run in front of the anode, so the anode is physically separated or spaced-apart from the membrane by a gap or spacing. Optionally, in one embodiment, the gap can be between 0.1- 10 mm wide.
[0035] Figs. 1-3 each show a form of CO2 recycling in accordance with the presently disclosed technology. In one embodiment, the liquid crude and CO2 depleted streams exits the cell together and are separated by a gas-disengagement unit. The CO2 is then fed into the incoming reactant stream of CO2 to the cathode.
[0036] In one embodiment, unique features of the presently disclosed technology include:
1) Single-step conversion of carbon dioxide to ethylene glycols (monomer, dimer, or trimer); and/or
2) Reaction intermediates and salts can be recycled into the electrolyzer realizing a higher conversion efficiency.
[0037] None of the prior art techniques are carbon negative, as is the presently disclosed technology.
[0038] The single step conversion process of the presently disclosed technology will reduce capital costs and thereby improve profitability. The presently disclosed technology thus provides for the production of mono-ethylene glycol, di-ethylene glycol, and/or tri-ethylene glycol from CO2 in a single reaction conversion step. One commercial advantage of the presently disclosed technology is a product that has a negative carbon footprint, which is a market differentiator (e.g., commands a sur-charge in current market), which is not available from prior art processes. Another commercial advantage of the presently disclosed technology is the process can be installed as an add-on process (e.g., retrofit) on existing facilities or as a stand-alone facility.
[0039] A skilled artisan would not have thought of developing, or even been able to develop, the presently disclosed technology unless and until the catalyst disclosed in U.S. Patent No. 10,676,833 was invented.
[0040] The following exemplary embodiments further describe optional aspects of the presently disclosed technology and are part of this Detailed Description. These exemplary embodiments are set forth in a format substantially akin to claims (each with numerical designations followed by a capital letter), although they are not technically claims of the present application. The following exemplary embodiments refer to each other in dependent relationships as “embodiments” instead of “claims.”
[0041] 1A. A method for the employing an electrocatalytic cathode containing both a electrocatalyst and co-catalyst in a liquid phase membrane electrolyzer employing a liquid layer cathode with a percolation layer to reduce hydrostatic pressure effects on the cathode for the electro-reduction of CO2, CO, and/or inorganic carbon (carbonate/bicarbonate anions/carbonic acid) to ethylene glycol in a single reactor.
[0042] 2A. The combination of Embodiment 1 A, wherein the cathode comprises an electrocatalyst, co-catalyst to direct the carbon product selectivity.
[0043] 3 A. The combination of Embodiment 1 A, the electrocatalyst is a transition metal phosphide and the co-catalyst is a Lewis/Bronsted acid and base pair.
[0044] 4A. The combination of Embodiment 1 A, the percolator medium is chosen from materials stable in carbonate and alkali media present during reaction, such as glass, polytetrafluoroethylene, poly-diflouroethylene, poly-ethersulfone, poly-urethane, poly-ethylene (ultrahigh density, high and low density), polypropylene, or similar materials fabricated into a porous structure with a void volume in the range of exactly or approximately 20-75%, such as foam, mesh, cloth, or paper.
[0045] 5 A. The combination of Embodiment 1 A, the liquid crude produced at the cathode contains ethylene glycol, methyl glyoxal, furandiol, and formic acid.
[0046] 6 A. The combination of Embodiment 1 A, the produced ethylene glycol undergoes polymerization to di-ethylene glycol, and or tri-ethylene glycol in addition to mono-ethylene glycol.
[0047] 7A. The combination of Embodiment 1 A, the cathode distance to the solid electrolyte is optimized to facilitate ionic conductivity with the electrolyte and liquid product diffusion into the percolation layer.
[0048] 8 A. The combination of Embodiment 1 A, the catholyte is 0 and 2M alkali or alkali earth cation and whereas the anion is carbonate, phosphate, pyrophosphate, sulphate, or borate or mixtures thereof.
[0049] 9A. The combination of Embodiment 1 A, the anode distance to the solid electrolyte is optimized to facilitate ionic conductivity with the electrolyte and oxygen bubble release.
[0050] 10A. The combination of Embodiment 6 A, a liquid analyte is flowed which contains ionic conductive supporting electrolyte salts, such as alkali or alkali-earth metal salts contains cations such as Na, K, Rb, Cs, Mg, Ca, Sr, Ba or combinations thereof.
[0051] 11 A. The combination of Embodiment 10A, the alkali metal salt anion is carbonates, sulphates, phosphates, hypophosphates, citrates, or borates., or combinations thereof.
[0052] While the presently disclosed technology has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. It is understood, therefore, that the presently disclosed technology is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present presently disclosed technology as defined by the appended claims.

Claims

CLAIMS What is claimed is:
1. A method comprising: employing an electrocatalytic cathode containing both an electrocatalyst and a co-catalyst in a liquid phase membrane electrolyser employing a liquid layer cathode with a percolation layer for electro-reduction of carbon dioxide (CO2), carbon monoxide (CO), or inorganic carbon to afford a reduction product comprising ethylene glycol.
2. The method of claim 1, wherein the electrocatalytic cathode comprises an electrocatalyst, a co-catalyst.
3. The method of claim 2, wherein the liquid phase membrane electrolyzer comprises a solid electrolyte.
4. The method of claim 1, wherein the electrocatalyst is a transition metal phosphide and the co-catalyst is a Lewis/Bronsted acid and base pair.
5. The method of claim 1, wherein the electrolyzer further comprises a percolator medium composed of a material stable in carbonate and alkali media present during the reaction.
6. The method of claim 5, wherein the percolator medium is selected from the group consisting of glass, poly-tetrafluoroethylene, poly-difluoroethylene, poly-ethersulfone, polyurethane, poly-ethylene, polypropylene.
7. The method of claim 6, wherein the poly-ethylene is ultrahigh density, high density, or low density.
8. The method of claim 5, wherein the percolator medium is fabricated into a porous structure with a void volume in the range of exactly or approximately 20-75%.
9. The method of claim 8, wherein the porous structure is selected from the group consisting of foam, mesh, cloth, and paper.
10. The method of claim 1, wherein liquid crude produced at the cathode comprises a compound selected from the group consisting of ethylene glycol, methyl glyoxal, furandiol, and formic acid.
11. The method of claim 1 , wherein the reduction product further comprises a compound chosen from to di-ethylene glycol and tri-ethylene glycol.
12. The method of claim 1, further comprising: optimizing a distance between the cathode and the solid electrolyte to facilitate ionic conductivity with the electrolyte and liquid product diffusion into the percolation layer.
13. The method of claim 1, wherein the electrolyzer contains a catholyte consisting of 2M or less of a salt containing an alkali or alkali earth cation.
14. The method of claim 13, wherein the catholyte comprises an anion selected from the group consisting of carbonate, phosphate, pyrophosphate, sulphate, borate, and mixtures thereof.
15. The method of claim 1, wherein the electrolyzer consists of one or more salts, each of said salts contains an alkali or alkali earth cation, and the total concentration of said salts is 2 M or less.
16. The method of claim 1, further comprising: optimizing a distance between the anode and the solid electrolyte to facilitate ionic conductivity with the electrolyte and oxygen bubble release.
17. The method of claim 16, further comprising: flowing a liquid analyte comprising an ionic conductive supporting electrolyte salts consisting of one or more supporting electrolyte cations, which may be the same or different, and one or more supporting electrolyte anions, which may be the same or different.
18. The method of claim 17, wherein at least one of the one or more supporting electrolyte cations is selected from the group consisting of alkali and alkali-earth metal cations.
19. The method of claim 18, wherein at least one of the one or more supporting electrolyte cations is selected from the group consisting of Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof.
20. The method of claim 19, wherein each of the supporting electrolyte anions is selected from the group consisting of carbonates, sulphates, phosphates, hypophosphates, citrates, or borates, or combinations thereof.
21. A system comprising: an electrocatalytic cathode containing both an electrocatalyst and a co-catalyst in a liquid phase membrane electrolyser employing a liquid layer cathode with a percolation layer for electro-reduction of carbon dioxide (CO2), carbon monoxide (CO), or inorganic carbon to afford a reduction product comprising ethylene glycol.
22. The system of claim 21, wherein the electrocatalytic cathode comprises an electrocatalyst, a co-catalyst.
23. The system of claim 22, wherein the liquid phase membrane electrolyzer comprises a solid electrolyte.
24. The system of claim of claim 21, wherein the electrocatalyst is a transition metal phosphide and the co-catalyst is a Lewis/Bronsted acid and base pair.
25. The system of claim of claim 21, wherein the electrolyzer further comprises a percolator medium composed of a material stable in carbonate and alkali media present during the reaction.
26. The system of claim 25, wherein the percolator medium is fabricated into a porous structure with a void volume in the range of exactly or approximately 20-75%.
27. The system of claim 21, wherein the reduction product further comprises a compound chosen from to di-ethylene glycol and tri-ethylene glycol.
PCT/US2023/085274 2022-12-21 2023-12-21 Liquid electrolyzer for single-conversion-step electrocatalytic reduction of co2 to ethylene glycol WO2024137896A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400559A (en) * 1982-06-14 1983-08-23 The Halcon Sd Group, Inc. Process for preparing ethylene glycol
US20010045364A1 (en) * 2000-03-30 2001-11-29 Hockaday Robert G. Portable chemical hydrogen hydride system
US20050183951A1 (en) * 2002-06-04 2005-08-25 Dario Oldani Distributing element for electrolyte percolation electrochemical cell
CN102912374A (en) * 2012-10-24 2013-02-06 中国科学院大连化学物理研究所 Electrochemical reduction CO2 electrolytic tank using bipolar membrane as diaphragm and application of electrochemical reduction CO2 electrolytic tank
US20200347502A1 (en) * 2015-10-09 2020-11-05 Rutgers, The State University Of New Jersey Nickel Phosphide Catalysts for Direct Electrochemical CO2 Reduction to Hydrocarbons

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400559A (en) * 1982-06-14 1983-08-23 The Halcon Sd Group, Inc. Process for preparing ethylene glycol
US20010045364A1 (en) * 2000-03-30 2001-11-29 Hockaday Robert G. Portable chemical hydrogen hydride system
US20050183951A1 (en) * 2002-06-04 2005-08-25 Dario Oldani Distributing element for electrolyte percolation electrochemical cell
CN102912374A (en) * 2012-10-24 2013-02-06 中国科学院大连化学物理研究所 Electrochemical reduction CO2 electrolytic tank using bipolar membrane as diaphragm and application of electrochemical reduction CO2 electrolytic tank
US20200347502A1 (en) * 2015-10-09 2020-11-05 Rutgers, The State University Of New Jersey Nickel Phosphide Catalysts for Direct Electrochemical CO2 Reduction to Hydrocarbons

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