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WO2024211335A1 - Procédés de production de réactifs caustiques à partir de saumures - Google Patents

Procédés de production de réactifs caustiques à partir de saumures Download PDF

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Publication number
WO2024211335A1
WO2024211335A1 PCT/US2024/022727 US2024022727W WO2024211335A1 WO 2024211335 A1 WO2024211335 A1 WO 2024211335A1 US 2024022727 W US2024022727 W US 2024022727W WO 2024211335 A1 WO2024211335 A1 WO 2024211335A1
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WO
WIPO (PCT)
Prior art keywords
alkali hydroxide
kwh
aqueous solution
cathode
anode
Prior art date
Application number
PCT/US2024/022727
Other languages
English (en)
Inventor
David Jassby
Eric Hoek
Fan Yang
Dante SIMONETTI
Gaurav SANT
Original Assignee
The Regents Of The University Of California
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Regents Of The University Of California filed Critical The Regents Of The University Of California
Publication of WO2024211335A1 publication Critical patent/WO2024211335A1/fr

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Classifications

    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • 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

Definitions

  • caustic e.g., NaOH
  • caustic solutions are emerging as a key component in enabling the transition towards carbon-free industrial processes, such as CO2-free cement manufacturing, and CO2 capture and sequestration.
  • Traditional caustic manufacturing revolves around the chlor-alkali process, of which there are several versions, such as the membrane, diaphragm, and oxygen depolarized cathode electrolysis. In all these process configurations, an anode and cathode are separated by a hydraulic separator (diaphragm or ion exchange membrane), and immersed into a high- salinity environment (typically a 25% NaCl aqueous solution).
  • a hydraulic separator diaphragm or ion exchange membrane
  • chloride ions are oxidized on the anode to generate chlorine, while water is reduced on the cathode to generate hydroxide ions and hydrogen gas.
  • water is heated to 90° C to increase process efficiency.
  • Typical NaOH concentrations resulting from traditional chlor-alkali reactors range between 10%-30%, and further concentration (if desired) is achieved through water evaporation and NaOH precipitation. 1
  • the main cost components are: i) the energy (electricity) needed to drive the electrolysis reactions (-70% of total OpEx); and ii) the membrane/electrode cost, which varies with system size, with an average of $4,500/m 2 of electrode area.
  • typical energy requirements of traditional chlor-alkali processes range between 2-3 kWh/kg NaOH. Therefore, there is a large incentive to minimize both the energy consumption associated with caustic production, as well as the size of the electrodes in the electrochemical reactor.
  • Unfortunately there is a tension between these two goals, as smaller electrode areas result in higher current densities, which can lead to reduced energy efficiencies and overall higher energy consumption.
  • the present disclosure provides methods of producing an alkali hydroxide comprising passing an aqueous solution between an anode and a cathode, wherein the cathode is permeable; the aqueous solution comprises dissolved ions; and the aqueous solution permeates the cathode, thereby producing the alkali hydroxide.
  • the present disclosure provides electrodes comprising the anodes and cathodes disclosed herein.
  • the present disclosure provides systems for performing the methods disclosed herein.
  • FIG. 1 is an illustration of caustic production process. Pressurized feed (brine) flowing between the anode and cathode is forced through the porous cathode, generating a high-pH permeate that contains H2 that can be further collected and utilized. The remaining feed, known as the retentate, becomes acidified and contains Ch that also can be collected.
  • the physical flexibility of the materials enable the efficient packaging of the assembly into a spiral-wound configuration - the image depicts an assembly with >1 m 2 of cathode area.
  • FIG 2A shows the Specific Energy Consumption (SEC) of caustic production as a function of membrane flux, with a minimum SEC measured at 1,300 LMH, with a 3% NaCl solution and 2 V potential applied.
  • SEC Specific Energy Consumption
  • FIG. 2B shows the SEC of caustic solution production as a function of applied potential with a 3% NaCl solution and a flux of 1,300 LMH.
  • FIG. 3 shows a process flow diagram of a proposed caustic production and Ca(OH)2 and Mg(OH)2 production system.
  • Brine e.g., seawater, groundwater, produced water, or leachate
  • NF a Ca- and Mg-rich solution and aNaCl solution that is fed to the chlor-alkali reactor.
  • the stream is split again to yield an acidic stream that contains CI2, and a caustic stream that contains H2.
  • the H2 is recovered, while the caustic stream is returned to the Ca- and Mg-rich stream from the NF to induce precipitation and recovery of Mg(0H)2 and Ca(0H)2 solids.
  • an electrolysis system capable of generating caustic brines at a specific energy consumption (SEC) of 1.7 kWh/kg NaOH.
  • pressurized water 100 psi
  • anode Pt-coated Ti
  • porous cathode Composed of Ni- coated carbon nanotubes deposited on a porous polymeric support
  • Feed water (containing dissolved ions) flows between the anode and cathode, with a portion of the feed being pushed through the cathode (the permeate) at a rate that is dependent on the membrane (cathode) permeability and the applied pressure (FIG. 1).
  • the system configuration generates a permeate stream with a pH of 12.5 (with a feed pH of 6)
  • a feed pH of 6 it is likely that looping the permeate into the feed could yield dramatically higher pH values in the permeate, albeit with the tradeoff of reducing SEC. Therefore, it is predicted that the value of the proposed system is in the generation of dilute caustic solutions from low-quality feed stock (e.g., seawater).
  • a softening step may be needed to remove divalent cations from the feed.
  • Nanofiltration (NF) can readily achieve >99% removal of such cations from seawater, at an energy intensity of between 0.4 - 0.6 kWh/m 3 of treated water.
  • seawater as a feed stock, and a final product pH of 12.5
  • the additional energy needed to desalinate seawater is 0.4 kWh/kgNaOH, bringing the overall SEC of certain embodiments of the present disclosure to 2.1 kWh/kgNaOH.
  • the SEC reported by traditional chloralkali processes assume the use of deionized water and pure salts, the provision of which is not included in the SEC values (2-3 kWh/kg NaOH) that are reported; in other words, the actual energy demand of the process is higher.
  • Dilute caustic streams have many potentially useful applications, as they can facilitate the precipitation of solids such as Mg(OH)2 (useful for subsequent CO2 capture and sequestration) and Ca(OH)2 (a promising carbon-free cement precursor).
  • An example of a process train that utilizes the proposed electrolysis system and a generic brine to generate these solids is presented in FIG. 3.
  • NF is used to separate Ca and Mg from a brine to form 2 streams: i) a stream enriched in Ca and Mg, and ii) a high-salinity stream containing primarily NaCl.
  • the second stream is fed to the electrolyzer producing a high pH caustic stream (the permeate) and a chlorine-containing stream (the retentate).
  • the permeate is then mixed (titrated) into the Ca and Mg rich stream from the NF process to sequentially precipitate first CaCCh and Mg(OH)2 (at pH 10.5), and then Ca(OH)2 (at pH 12).
  • the amounts of recoverable Ca and Mg solids are dependent on their initial concentrations in the brine, as well as the availability of caustic from the electrolysis reactor.
  • the present disclosure provides methods of producing an alkali hydroxide comprising passing an aqueous solution between an anode and a cathode, wherein: the cathode is permeable; the aqueous solution comprises dissolved ions; and the aqueous solution permeates the cathode, thereby producing the alkali hydroxide.
  • the alkali hydroxide is sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, or magnesium hydroxide. In certain preferred embodiments, the alkali hydroxide is sodium hydroxide.
  • the aqueous solution is brine, seawater, produced water, grey water (e.g., water that already has been used domestically, commercially, or industrially), a hot stream (e.g., frack water), a saline stream, water from mine drainage, or industrial cleaning.
  • the aqueous solution is brine (e.g., an aqueous solution of Na2SO4, K2SO4, NaF, KF, Nal, KI, NaNCh, KNO3, Ca(NO 3 ) 2 , Mg(NO 3 ) 2 , or MgSC ).
  • the aqueous solution is an aqueous solution of 3% sodium chloride. In some embodiments, the aqueous solution is seawater. In other embodiments, the aqueous solution is produced water.
  • the aqueous solution has a flow that is perpendicular to the cathode and the anode.
  • the aqueous solution is pressurized. In further embodiments, the aqueous solution has a pressure of about 50 psi, about 75 psi, about 100 psi, about 125 psi, about 150 psi, about 175 psi, or about 200 psi. In certain embodiments, the aqueous solution has a pressure of about 100 psi. In some embodiments, the aqueous solution has a pressure greater than 90 psi.
  • the anode comprises a transition group metal (e.g., Ni, such as Ni(OH) 2 ), Co, NiCo alloy, or Pt).
  • the transition group metal is a noble metal, preferably platinum.
  • the anode comprises titanium. In some such embodiments, the anode comprises platinum and titanium.
  • the cathode comprises a first layer (e.g., a conductive layer) and a porous support.
  • the first layer is disposed (e.g., deposited) on the porous support.
  • the first layer comprises a transition group metal, e.g., a group 10 metal. In certain such embodiments, the first layer comprises nickel. In certain embodiments, the first layer further comprises a carbonaceous material, e.g., carbon nanotubes, carbon fiber, or carbon felt. In certain preferred embodiments, the first layer further comprises carbon nanotubes. In some embodiments, the first layer comprises nickel coated carbon nanotubes.
  • the porous support is a porous polymeric support.
  • the polymeric support comprises polysulfone, polyethersulfone, PVFD, PTFE, PAN, PEEK, polyimide, polyamide, or cellulose acetate.
  • the porous support has pores which have an average diameter of 0.5 nm to 10,000 nm.
  • the cathode is permeable to H2. In some embodiments, the cathode is permeable to water.
  • the method produces Ch and the Ch does not permeate the cathode. In certain embodiments, the method produces O2 and the O2 does not permeate the cathode.
  • the alkali hydroxide is produced at a specific energy consumption (SEC) of about 0.5 kWh/kg of alkali hydroxide, about 0.6 kWh/kg of alkali hydroxide, about 0.7 kWh/kg of alkali hydroxide, about 0.8 kWh/kg of alkali hydroxide, about 0.9 kWh/kg of alkali hydroxide, about 1.0 kWh/kg of alkali hydroxide, about 1.1 kWh/kg of alkali hydroxide, about 1.2 kWh/kg of alkali hydroxide, about 1.3 kWh/kg of alkali hydroxide, about 1.4 kWh/kg of alkali hydroxide, about 1.5 kWh/kg of alkali hydroxide, about 1.6 kWh/kg of alkali hydroxide, about 1.7 kWh/kg of alkali hydroxide, about 1.8 kWh/kg of alkali hydroxide, or about 1.9 kWh/kg of alkali hydroxide.
  • SEC specific energy consumption
  • the alkali hydroxide is produced at a specific energy consumption (SEC) of about 1.1 kWh/kg of alkali hydroxide, about 1.2 kWh/kg of alkali hydroxide, about 1.3 kWh/kg of alkali hydroxide, about 1.4 kWh/kg of alkali hydroxide, about 1.5 kWh/kg of alkali hydroxide, about 1.6 kWh/kg of alkali hydroxide, or about 1.7 kWh/kg of alkali hydroxide.
  • the alkali hydroxide is produced at a specific energy consumption (SEC) of about 1.2 kWh/kg of alkali hydroxide.
  • the alkali hydroxide is produced at a specific energy consumption (SEC) of about 1.7 kWh/kg of alkali hydroxide. In certain embodiments, the alkali hydroxide is produced at a specific energy consumption (SEC) of below 2.0 kWh/kg of alkali hydroxide. In some embodiments, the alkali hydroxide is produced at a specific energy consumption (SEC) of below 2.5 kWh/kg of alkali hydroxide. In certain embodiments, the alkali hydroxide is produced at a specific energy consumption (SEC) of below 3.0 kWh/kg of alkali hydroxide. In some embodiments, the method is performed at a voltage of about 1 V to about 10 V.
  • the method is performed at a voltage of about 2.0 V, about 2.1 V, about 2.2 V, about 2.3 V, about 2.4 V, about 2.5 V, about 2.6 V, about 2.7V, about 2.8 V, about 2.9 V, or about 3.0V. In some embodiments, the method is performed at a voltage of about 2.5 V.
  • the method further comprises treating the aqueous solution to remove divalent cations (e.g., divalent alkali metal cations, such as CaCOs and Mg(OH)2) prior to passing the aqueous solution between the anode and the cathode.
  • treating the aqueous solution to remove divalent cations comprises filtering the aqueous solution using a membrane (e.g, a nanofiltration membrane).
  • the membrane is a nanofiltration membrane.
  • the membrane is a reverse osmosis membrane.
  • the anode is an oxygen selective anode.
  • the present disclosure provides an electrode system comprising the anode and cathodes disclosed herein.
  • the electrode is configured as a spiral-wound electrode.
  • the present disclosure provides an electrolysis system comprising: an inlet in fluid communication with a first outlet and a second outlet; a junction that connects each of the first and second outlets with the inlet; a power source; an anode as defined herein, the anode coupled to the power source and disposed in the junction; and a cathode as defined herein, the cathode coupled to the power source and disposed in the junction so as to separate the second outlet from a fluid path connecting the inlet and the first outlet.
  • the anode and the cathode are disposed facing one another.
  • the present disclosure provides a system as set forth in FIG. 3.
  • systems and methods of the present disclosure comprise an oxygen-selective anode that is selective for the Oxygen Evolution Reaction (OER) over the Chlorine Evolution Reaction (C1ER) pathway, for example, in embodiments wherein the aqueous solution comprises chloride (C1‘) ions.
  • the oxygen- selective anode comprises double-layered coatings, e.g., by overlaying a Cl'-blocking on an OER-catalyzing layer.
  • the Cl'-blocking outer layer usually comprises negatively charged materials that repel the negatively charged Cl" ion, while letting water, oxygen, and cationic species (Na + , H + , etc.) pass through the outer layer to the active layers beneath.
  • the anode durability and overpotential are based on the underlying OER catalyst.
  • the most durable anodes generally rely on a heavy loading of IrOx, which can lastingly endure acidic and chlorinated environments. For instance, either pure IrCh or a IrCh contents > 80 at.% (> 90 wt.%) is needed to ensure the longevity of the anodes.
  • the tightening of global Ir production and price presents a barrier to large-scale production and use of these anodes.
  • Exemplary PGM-free anodes are provided below, suitable for use in certain embodiments of the systems and methods described herein. Table 2. PGM-free, ER-selective catalysts from literature reports
  • the terms “optional” or “optionally” mean that the subsequently described event or circumstance may occur or may not occur, and that the description includes instances where the event or circumstance occurs as well as instances in which it does not.
  • “optionally substituted alkyl” refers to the alkyl may be substituted as well as where the alkyl is not substituted.
  • alkalinizing refers to a process of increasing the pH of a given solution, e.g, alkalinizing the first solution to prepare an alkaline solution with a higher pH.
  • the term “acidifying” or “acidification” as used herein refers to a process of decreasing the pH of a given solution.
  • the given solution may be of any starting pH before undergoing the acidifying, e.g. the solution may already have a pH below 7 before a step of acidifying the solution is performed.
  • ionic communication refers to the ability for ions to freely flow between two objects or regions of an object, e.g, between the cathodic chamber and anodic chamber of an electrochemical cell, in accordance with local chemical gradients.
  • Nonlimiting examples of such gradients include flow of ions from an area of high electrical potential to low electrical potential, from high ion concentration to low ion concentration, and from high chemical potential to low chemical potential.
  • two objects or regions may be physically separated by a semi-permeable barrier (e.g., not in fluid communication) but still be in ionic communication, e.g., by virtue of ion diffusion or transport through the barrier.
  • austic refers to compositions comprising basic components, preferably sodium hydroxide.
  • austic brine or “caustic solution” refers to an aqueous solution comprising basic components, preferably sodium hydroxide.

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

Abstract

L'invention concerne des procédés et des systèmes de production de saumures caustiques (par exemple, de l'hydroxyde de sodium aqueux).
PCT/US2024/022727 2023-04-04 2024-04-03 Procédés de production de réactifs caustiques à partir de saumures WO2024211335A1 (fr)

Applications Claiming Priority (2)

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US202363456971P 2023-04-04 2023-04-04
US63/456,971 2023-04-04

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160168732A1 (en) * 2013-07-31 2016-06-16 Aquahydrex Pty Ltd. Electro-synthetic or electro-energy cell with gas diffusion electrode(s)
US20220040639A1 (en) * 2019-06-14 2022-02-10 The Regents Of The University Of California Alkaline cation enrichment and water electrolysis to provide co2 mineralization and global-scale carbon management

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160168732A1 (en) * 2013-07-31 2016-06-16 Aquahydrex Pty Ltd. Electro-synthetic or electro-energy cell with gas diffusion electrode(s)
US20220040639A1 (en) * 2019-06-14 2022-02-10 The Regents Of The University Of California Alkaline cation enrichment and water electrolysis to provide co2 mineralization and global-scale carbon management

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KUMAR AMIT, PHILLIPS KATHERINE R., THIEL GREGORY P., SCHRÖDER UWE, LIENHARD JOHN H.: "Direct electrosynthesis of sodium hydroxide and hydrochloric acid from brine streams", NATURE CATALYSIS, NATURE PUBLISHING GROUP UK, vol. 2, no. 2, pages 106 - 113, XP093220983, ISSN: 2520-1158, DOI: 10.1038/s41929-018-0218-y *

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