WO2013082811A1 - Appareil et procédé permettant une production électrochimique de composés apparentés à un oxydant - Google Patents

Appareil et procédé permettant une production électrochimique de composés apparentés à un oxydant Download PDF

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Publication number
WO2013082811A1
WO2013082811A1 PCT/CN2011/083772 CN2011083772W WO2013082811A1 WO 2013082811 A1 WO2013082811 A1 WO 2013082811A1 CN 2011083772 W CN2011083772 W CN 2011083772W WO 2013082811 A1 WO2013082811 A1 WO 2013082811A1
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WIPO (PCT)
Prior art keywords
gas diffusion
electrochemical cell
diffusion cathode
gas
ion exchange
Prior art date
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PCT/CN2011/083772
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English (en)
Inventor
Zijun Xia
Hai Yang
Chihyu Caroline SUI
Qunjian Huang
Shizhong Wang
John H Barber
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General Electric Company
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Application filed by General Electric Company filed Critical General Electric Company
Priority to PCT/CN2011/083772 priority Critical patent/WO2013082811A1/fr
Priority to TW101145330A priority patent/TWI564434B/zh
Priority to ARP120104573A priority patent/AR089098A1/es
Publication of WO2013082811A1 publication Critical patent/WO2013082811A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—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
    • C25B11/02—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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes
    • C02F2001/46166—Gas diffusion electrodes

Definitions

  • the present disclosure relates generally to the production of oxidant-based chemicals and in particular to the electrochemical production of oxidant-based biocides.
  • Oxidant-based biocides are an established treatment used to control the levels of the microorganisms within industrial water circulation systems. Depending upon the specifications of the industrial water circulation system, oxidant-based biocidal treatment programs can include a continuous maintenance dose, an intermittent maintenance dose or periodic high doses. Therefore, operators typically require large supplies of oxidant-based biocides at all times for biocidal maintenance regimes and to address any microbial outbreaks.
  • Sodium hypochlorite is one example of an oxidant-based biocide.
  • Sodium hypochlorite is produced by chloralkali processes, such as membrane based processes that take place in electrochemical cells.
  • the electrochemical cells include at least one anode and one cathode with a membrane that is selectively permeable to positively charged cations.
  • the cation permeable membrane separates the electrochemical cell into an anolyte chamber and catholyte chamber.
  • a solution of sodium chloride is introduced into the anolyte chamber where negatively charged chlorine ions undergo an oxidation reaction to form chlorine gas:
  • the chlorine gas and the sodium hydroxide can be mixed under controlled conditions to produce sodium hypochlorite.
  • Membrane-based chloralkali manufacturing exhibits a direct relationship between the voltage, also referred to as the working potential, applied to the electrochemical cell and the production of chloralkali products. Due to this relationship and the high demand for chloralkali products, the chloralkali manufacturing industry is a very large consumer of electricity. Therefore, there is a need for improved energy consumption in chloralkali manufacturing processes.
  • the gas diffusion membrane electrolysis cell 10 includes an electric power source 100, an anode 12, a gas diffusion cathode 14 and a cation permeable membrane 18.
  • the cation permeable membrane 18 separates the feed space into an anolyte chamber 16A and a catholyte chamber 16B.
  • the gas diffusion cathode 14 is permeable to gas, such as oxygen, which reacts with the reduced water to produce hydroxide radicals in the catholyte chamber 16B.
  • a sodium chloride solution is introduced into the anolyte chamber 16A and the negatively charged chlorine ions are oxidized to form chlorine gas, while the positively charged sodium ions cross the cation permeable membrane 18 to form sodium hydroxide.
  • a gas diffusion membrane electrochemical cell demonstrates improved energy consumption in comparison to a non-gas diffusion membrane-based electrolysis cell operating at the same current density.
  • the gas diffusion membrane electrolysis cell still requires the use of costly cation permeable membranes that can be subject to fouling, which impedes efficiency and increases maintenance and capital replacement costs.
  • An electrochemical cell for the production of oxidant-based biocides is described in the detailed description below.
  • the electrochemical cell comprises an electric power supply, an anode spaced from a gas diffusion cathode and a plenum adapted to receive gas.
  • the gas diffusion cathode includes an ion exchange coating on the surface that faces the anode.
  • the plenum communicates with the gas diffusion cathode.
  • a concentrated feed solution is introduced into the feed space that is between the gas diffusion cathode and the anode of the electrochemical cell.
  • oxygen from the plenum enters the gas diffusion cathode.
  • the oxygen is reduced to produce hydroxide radicals.
  • the hydroxide radicals are transported by the ion exchange coating to react within the feed space to produce an oxidant-based biocide.
  • the ion exchange coating has properties that provide protection of the gas diffusion electrode.
  • the protection includes physical protection of a high surface area region within the gas diffusion cathode. This physical protection permits flow rates that are higher than those used in a typical membrane based, gas diffusion electrochemical cell. Higher flow rates of the feed solution may increase the current efficiency and productivity of the electrochemical cell.
  • the ion exchange coating also provides chemical protection by preventing chemical reactions that can degrade the high surface area region within the gas diffusion cathode. Additionally, the ion exchange coating transports the hydroxide ions from within the gas diffusion cathode to react within the feed space.
  • this transport decreases the resistance of the gas diffusion cathode in comparison to a gas diffusion cathode that merely relies upon diffusion as the mechanism to transport the hydroxide ions out of the gas diffusion cathode. In this manner, the resistance at the gas diffusion cathode is decreased and the working potential requirements of the electrochemical cell are also decreased.
  • Figure 1 is a cross-sectional schematic drawing of a prior art gas diffusion membrane process.
  • Figure 2 is a cross-sectional schematic drawing of an electrochemical cell for the production of oxidant-based biocides.
  • Figure 3 is a schematic drawing of a water treatment system.
  • Figures 4A, 4B, 4C and 4D are line graphs depicting the experimental productivity (g/day) results from four concentrations of feed solution processed by the electrochemical cell of Figure 2.
  • Figure 5A, 5B, 5C and 5D are line graphs depicting the experimental current efficiency (%) results from four concentrations of feed solution processed by the electrochemical cell of Figure 2.
  • Figure 6A, 6B, 6C and 6D are line graphs depicting the experimental energy consumption (kWh/kg) results from four concentrations of feed solution processed by the electrochemical cell of Figure 2.
  • Figure 7 is a line graph depicting the experimental productivity (g/day) results from two electrochemical cells running in series.
  • Figure 8 is two line graphs representing the relationship between current and the open circuit voltage, over time, when current is applied to a control electrode and an ion exchange coated electrode.
  • An electrochemical cell for the production of oxidant-based biocides comprises an electric power source, an anode, a gas diffusion cathode and a plenum of gas.
  • the gas diffusion cathode includes an ion exchange coating on the surface that faces the anode.
  • the plenum of gas is in communication with the gas diffusion cathode.
  • FIG. 2 depicts an electrochemical cell 20 for the production of oxidant-based biocides.
  • the electrochemical cell 20 comprises an electric power source 100, a feed space 26, a gas space 28, an anode 22 and a gas diffusion cathode 24.
  • the electric power source 100 is a DC source of electric current that flows through an electrolytic circuit.
  • the electrolytic circuit is complete when an electrolyte containing fluid is present in the feed space 26.
  • the ions within the electrolytic fluid transfer the electric current between the anode 22 and the gas diffusion cathode 24.
  • the source of electric power supply can be an AC power source.
  • the feed space 26 is positioned between the anode 22 and the gas diffusion cathode 24.
  • the feed space 26 is adapted to receive a feed solution that contains dissociated anions and cations.
  • the feed solution can be a sodium chloride solution that contains dissociated chloride anions and sodium cations.
  • the feed space 26 does not require a selectively permeable membrane.
  • the gas space 28 is a plenum in fluid communication with the gas diffusion electrode 24.
  • the gas space 28 is adapted to receive and transfer a gas that has at least some oxygen, for example pure oxygen gas or a gas mixture that contains at least some oxygen, such as air.
  • the anode 22 comprises an electrode substrate composed, for example, of titanium or a titanium alloy.
  • the anode 22 may be generally planar in shape with a first anode side 21 and a second anode side 23.
  • the second anode side 23 is in fluid communication with the feed space 26.
  • the gas diffusion cathode 24 may be generally planar in shape, with a first cathode side 25 and a second cathode side 27.
  • the first cathode side 25 is in fluid communication with the feed space 26 and the second cathode side 27 is in fluid communication with the gas space 28.
  • the gas diffusion cathode 24 has a current collector (not shown) comprising, for example, a titanium mesh.
  • the current collector conducts the electric current from the electric power source 100 through to the reacting part of the gas diffusion cathode 24.
  • the reacting part of the gas diffusion cathode 24 may be a high surface area, activated carbon substrate located between the first cathode side 25 and the second cathode side 27.
  • the first cathode side 25 is water permeable to allow water to enter into the activated carbon substrate from the feed space 26.
  • the second cathode side 27 is permeable to gas which allows gas to enter the activated carbon substrate from the gas space 28.
  • the oxygen gas reacts with the liquid water in a four electron reduction reaction:
  • the hydroxide ions produced by the four electron reduction reaction move from the solid phase of the gas diffusion cathode 24 to the feed space 26 through an ion exchange coating 30.
  • the ion exchange coating 30 is positioned on the first cathode side 25.
  • the ion exchange coating 30 is composed of an insoluble, and optionally gas impermeable, cross-linked polymer that has ion exchange properties.
  • the polymer can be stable in the presence of strong oxidants (such as chlorine, hydrogen peroxide, ozone, hypochlorite species, and the like), or other chemicals such as caustics (such as sodium hydroxide, potassium hydroxide, and the like).
  • the polymer is stable in both oxidants and caustics.
  • the term “stable” refers to the polymer not reacting, such as degrading, decomposing, corroding or otherwise, in the presence of strong oxidants and/or caustics under normal operational conditions throughout a useful lifespan. By not reacting in this manner, the polymer maintains the ion exchange properties, and other useful properties, through the practical life span of the gas diffusion cathode 24.
  • the polymer can be acrylamide based or acrylic based.
  • the polymer described in U.S. 7,968,663 to MacDonald et al., the disclosure of which is hereby incorporated into this application by reference, is an anion exchange polymer of the formula:
  • R is -[CH 2 - CH(OH)] 2 -W;
  • Ri is hydrogen or a C 1 -C 12 alkyl group; a is from about 0 to about 0.75, b and c are each independently, from about 0.25 to about 1.0;
  • Z is oxygen or N-R 3 ;
  • R 2 is -[CH 2 ] literal-;
  • R 3 is hydrogen or -[CH 2 ] m -CH 3 ;
  • R 4 and R 5 are each, independently, -[CH 2 ] m -CH 3 ;
  • X is selected from the group consisting of CI, Br, I and acetate;
  • W is a bridging group or atom;
  • m is an integer from 0 to 20;
  • n is an integer from 1 to 20; and
  • Y is selected from the group consisting of
  • This polymer as disclosed by MacDonald et al., is an example of an acrylamide based polymer that is suitable for the ion exchange coating 30 and that is stable in the presence of chlorine and sodium hydroxide.
  • the ion exchange coating 30 can be a cross-linked polymer of the monomer compound below:
  • This second polymer is an example of an acrylamide based polymer that is suitable for the ion exchange coating 30 and that is stable in the presence of chlorine.
  • the ion exchange coating 30 transports hydroxide ions out of the activated carbon substrate of the gas diffusion cathode 24 and into the feed space 26.
  • the molar ratio of the chemical species relative to each other can drive the overall reaction of:
  • the second anode side 23 is very close to the surface of the ion exchange coating 30 making the dimensions of the feed space 26 very tight.
  • This tight feed space 26 is large enough to permit the flow of feed solutions into, and the reaction products out of, the electrochemical cell 20.
  • This optional feature may improve the efficiency of the overall reaction (5) from above.
  • the gas within the gas space 28 may be air and contain trace gases such as carbon dioxide, helium, hydrogen and the like.
  • the presence of carbon dioxide within the gas space 28 may require a water softening treatment (not shown) of the feed solution prior to introduction into the feed space 26.
  • the water softening reduces or removes water hardness ions such as calcium, magnesium, potassium, strontium, barium, and the like.
  • the water softening treatment prevents the reaction of the carbon dioxide with the water hardness ions which can lead to the formation of undesirable carbonate ions and salts within the gas diffusion cathode 24.
  • Carbonate ions and salts can decrease the rate of gas diffusion, which impairs the efficiency of the gas diffusion cathode 24. Further, carbonate ions can impair or compete with the transport of hydroxide ions by the ion exchange coating 30.
  • a metal oxide catalyst coating (not shown) is coated on at least the second anode side 23 that communicates with the feed space 26.
  • the metal oxide catalyst coating can be ruthenium oxide, iridium oxide and the like. The metal oxide catalyst coating increases the efficiency of the oxidation of the chlorine ions to produce chlorine gas and electrons, see equation (1 ) above.
  • the activated carbon substrate contains catalytic particles.
  • Suitable catalytic particles are selected from platinum, ruthenium, iridium, rhodium and manganese dioxide and the like. The catalytic particles increase the efficiency of the hydroxide ion producing reaction (4) from above.
  • the current collector is made of nickel mesh or a mesh composed of a conductive titanium and nickel alloy.
  • a coating of polytetrafluroethylene (PTFE) can be positioned on the second cathode side 27 of the gas diffusion cathode 24 to provide a hydrophobic barrier to the gas space 28.
  • At least two electrochemical cells 20 can be placed in series so that the feed solution flows from one electrochemical cell 20 to the next. This series arrangement can increase the production of oxidant- based biocides.
  • an electrolyte feed solution for example sodium chloride
  • an electrolyte feed solution for example sodium chloride
  • the presence of dissociated sodium ions and chloride ions allows the electric circuit to be completed between the anode 22 and the gas diffusion cathode 24.
  • the complete electric circuit provides a flow of electrons to drive the oxidation reaction to produce oxidation products at the anode 22. For example, see equation (1 ).
  • the flow of electrons also drives the reduction reaction to produce reduction products at the gas diffusion cathode 24, for example, see equation (4).
  • the feed solution is sodium chloride
  • chlorine ions are oxidized into chlorine gas at the anode 22.
  • oxygen from the gas space 28 is reduced to form hydroxide ions.
  • the ion exchange coating 30 of the gas diffusion cathode 24 transports the hydroxide ions out of the gas diffusion cathode 24 to react with the chlorine gas to produce sodium hypochlorite within the feed space 26.
  • FIG. 3 depicts the use of the electrochemical cell 20 in a water treatment system 150 for the treatment of a target water circulation system.
  • the water treatment system 150 comprises an input line 152, an output line 154 and a downstream process 156.
  • the input line 152 conducts a feed solution towards the electrochemical cell 20, which is adapted to receive the feed solution within the feed space 26.
  • the output line 154 conducts the electrochemical products (for example sodium hypochlorite and sodium chloride) away from the feed space 26 to the downstream process 156.
  • the water treatment system 150 can be physically located close enough to the target water circulation system that the output line 154 can conduct the oxidant-based biocide products directly into the target water circulation system, shown as the downstream process 156 in Figure 3.
  • the downstream process 156 can include a storage vessel (not shown) where the electrochemical products are stored for introduction into the target industrial water circulation system as needed, for example, if the electrochemical cell 20 production exceeds the demands of the target water circulation system.
  • the water treatment system 150 is located at a different physical location than the target water circulation system.
  • the downstream process 156 is a storage vessel to store the oxidant-based biocide products for transport to the target water circulation system.
  • a recirculation line 158 (shown as the dotted lines in Figure 3) is included to recirculate at least a portion of the electrochemical products back into the input line 152 or directly into the electrochemical cell 20.
  • the recirculation line 158 can include a pumping system (not shown) and possibly a secondary storage vessel (not shown).
  • Table 3 below, provides a comparison of some of the calculated characteristics of a typical membrane based, electrolysis cell and the electrochemical cell 20.
  • Table 3 A comparison of the calculated characteristics of typical membrane based, electrolysis cell and the electrochemical cell 20.
  • the advantages of the electrochemical cell 20 at least include: a decreased working potential; decreased energy consumption per mass of product; minimal to no hydrogen gas production, which can pose safety hazards; a wide range of feed solution concentration, up to and including a saturated feed solution; increased product concentration; and decreased water consumption per mass of product.
  • both the anode 22 and the gas diffusion cathode 24 are 16cm x 8cm in size and the anode 22 is a commercially available titanium coated electrode.
  • the catalytic particles within the activated carbon substrate are manganese dioxide.
  • the ion exchange coating 30 is a product of copolymerizing and cross-linking reaction of the monomer structure provided below:
  • Figures 4, 5, 6 and 7 depict the outcomes measured during this experiment. During the experiment, four different concentrations of sodium chloride feed solution were used: 50g/l, 100g/l, 200g/l and 300g/l.
  • the feed solution was introduced into the feed space 26 at various flow rates, as shown by the X-axis values of Figures 3, 4, 5 and 6. Additionally, the flow rate of air through the gas space 28 was approximately 2 to 6 times higher than the stoichiometric requirements of the four-electron reduction of oxygen, see reaction (4) from above.
  • Figure 4 demonstrates that the electrochemical cell 20 produces sodium hypochlorite product at various feed solution concentrations and various current densities.
  • the highest feed solution concentration of 300g/l, as shown in Figure 4D, has the highest production of all the feed solution concentrations tested.
  • the highest current density of 258 mA/cm 2 causes the highest production of all parameters tested.
  • Figure 5 demonstrates that a current efficiency of substantially greater than 80% can be achieved with the electrochemical cell 20.
  • the current efficiency is calculated by comparing the stoichiometry of the overall reaction; see reaction (5) from above, wherein the transfer of 2 mols of electrons generates 1 mol chlorine gas and 2 mol hydroxide ions, which ultimately generated 1 mol of NaCIO. This one mol of sodium hypochlorite is compared to the amount of sodium hypochlorite actually produced to determine current efficiency.
  • Figure 6 demonstrates that the electrochemical cell 20 can operate with an energy consumption of approximately 3 kWhr/kg of sodium hypochlorite produced.
  • Figure 7 demonstrates that placing two electrochemical cells 20 in series increases the overall production of sodium hypochlorite.
  • Table 4 presents the comparative data of current efficiency and resistance between a blank calendered electrode; a calendered electrode with a selectively permeable ion exchange membrane; a screen printed electrode with a selectively permeable ion exchange membrane; and a calendered coated electrode, coated with the ion exchange coating 30, as described above.
  • a sodium chloride feed solution at a concentration of 800ppm and at a flow rate of 10cm/s was utilized.
  • Table 4 - A comparison of current efficiency and resistance of various electrode arrangements.
  • the calendered and coated electrode demonstrated an approximate 56% reduction in resistance, at the same current efficiency, in comparison to the calendered electrode with the selectively permeable ion exchange membrane.
  • the calendered and coated electrode demonstrated an approximate 40% reduction in resistance, at the same current efficiency, in comparison to the screen printed electrodes with a selectively permeable ion exchange membrane.
  • Figure 8 demonstrates the comparison in energy consumption between a titanium coated carbon electrode that is used with a selectively permeable ion exchange membrane and a coated electrode that is coated with the ion exchange coating 30, as described above. At the onset of the current, the voltage is 53% lower in the anion exchange coated electrode.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

La présente invention se rapporte à une cellule électrochimique qui comprend une source d'alimentation électrique, une anode, une cathode à diffusion de gaz et un espace gazeux en communication avec la cathode à diffusion de gaz. La cathode à diffusion de gaz comprend un revêtement échangeur d'ions qui fait face à l'anode. Le revêtement échangeur d'ions est un polymère qui protège également la cathode à diffusion de gaz. Une solution d'alimentation circule entre le revêtement échangeur d'ions et l'anode. L'espace gazeux contient au moins l'oxygène gazeux qui se diffuse dans la cathode à diffusion de gaz. Dans la cathode à diffusion de gaz, l'oxygène réagit pour produire des radicaux d'hydroxyde. Le revêtement échangeur d'anions transporte les radicaux d'hydroxyde provenant de la cathode à diffusion de gaz afin de produire électrochimiquement des biocides à base d'oxydant.
PCT/CN2011/083772 2011-12-09 2011-12-09 Appareil et procédé permettant une production électrochimique de composés apparentés à un oxydant WO2013082811A1 (fr)

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PCT/CN2011/083772 WO2013082811A1 (fr) 2011-12-09 2011-12-09 Appareil et procédé permettant une production électrochimique de composés apparentés à un oxydant
TW101145330A TWI564434B (zh) 2011-12-09 2012-12-03 用於電化學製造與氧化劑有關之化合物的裝置及方法
ARP120104573A AR089098A1 (es) 2011-12-09 2012-12-05 Un aparato y metodo para la produccion electroquimica de compuestos oxidantes relacionados

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US9828313B2 (en) 2013-07-31 2017-11-28 Calera Corporation Systems and methods for separation and purification of products
US9957621B2 (en) 2014-09-15 2018-05-01 Calera Corporation Electrochemical systems and methods using metal halide to form products
US9957623B2 (en) 2011-05-19 2018-05-01 Calera Corporation Systems and methods for preparation and separation of products
US10266954B2 (en) 2015-10-28 2019-04-23 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
CN110366608A (zh) * 2017-03-06 2019-10-22 懿华水处理技术有限责任公司 用于在电化学次氯酸盐生成期间氢减少的可持续氧化还原剂供应的脉冲电源
US10556848B2 (en) 2017-09-19 2020-02-11 Calera Corporation Systems and methods using lanthanide halide
US10590054B2 (en) 2018-05-30 2020-03-17 Calera Corporation Methods and systems to form propylene chlorohydrin from dichloropropane using Lewis acid
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US9828313B2 (en) 2013-07-31 2017-11-28 Calera Corporation Systems and methods for separation and purification of products
US10287223B2 (en) 2013-07-31 2019-05-14 Calera Corporation Systems and methods for separation and purification of products
US9957621B2 (en) 2014-09-15 2018-05-01 Calera Corporation Electrochemical systems and methods using metal halide to form products
US10266954B2 (en) 2015-10-28 2019-04-23 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10844496B2 (en) 2015-10-28 2020-11-24 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
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