GB2497256A - Magnesium recovery method and magnesium recovery apparatus - Google Patents

Magnesium recovery method and magnesium recovery apparatus Download PDF

Info

Publication number
GB2497256A
GB2497256A GB1306089.2A GB201306089A GB2497256A GB 2497256 A GB2497256 A GB 2497256A GB 201306089 A GB201306089 A GB 201306089A GB 2497256 A GB2497256 A GB 2497256A
Authority
GB
United Kingdom
Prior art keywords
magnesium
seawater
anode
electrolyzed water
cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB1306089.2A
Other versions
GB201306089D0 (en
Inventor
Tatsushi Iwamoto
Kenichi Akamine
Junichi Okuyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IHI Corp
Original Assignee
IHI Corp
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 IHI Corp filed Critical IHI Corp
Publication of GB201306089D0 publication Critical patent/GB201306089D0/en
Publication of GB2497256A publication Critical patent/GB2497256A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00Compounds of magnesium
    • C01F5/14Magnesium hydroxide
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/18Alkaline earth metal compounds or magnesium compounds
    • C25B1/20Hydroxides
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/46115Electrolytic cell with membranes or diaphragms
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/4618Supplying or removing reactants or electrolyte
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/133Renewable energy sources, e.g. sunlight
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

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

Abstract

In this magnesium recovery method and this magnesium recovery apparatus, anodically electrolyzed water (7a) and cathodically electrolyzed water (7b) both generated by the electrolysis of seawater are separated from each other, an alkaline material is introduced into the anodically electrolyzed water to adjust the pH value of the anodically electrolyzed water, magnesium is allowed to precipitate in the cathodically electrolyzed water in the form of magnesium hydroxide and is then recovered, the pH-adjusted anodically electrolyzed water and the cathodically electrolyzed water after the fixing of a carbonate salt are joined together, and the joined solution is adjusted to the same pH value as that of seawater and is then discharged. In this manner, magnesium can be recovered from seawater while minimizing an environmental load.

Description

DESCRIPTION
Title of invention
MAGNESIUM RECOVERY METHOD AND MAGNESIUM RECOVERY
APPARATUS
Technical Field
[0001] The present invention relates to a method and apparatus for recovering magnesium from seawater by electrolysis of seawatet Priority is claimed on Japanese Patent Application No. 2010-203353, tiled September 10,2010, the content of which is incorporated herein by reference.
Background Art
[0002] In recent years, high specific strength magnesium has garnered attention as a next-generation structural material, and its demand is expected to increase hereafter.
However, magnesium, which is primarily refined 11cm the mineral, is unevenly distributed in limited geographical areas, and it would be desirable to establish procurement methods apart from importation of magnesium in order to secure stable supply in die future.
[0003] As is well known, magnesium exists as a mineral, and is also contained iii seawater. Accordingly, if magnesium could be recovered from seawater, it would greatly contribute to stable supply of magnesium. On the other hand, when recovering
I
large quantities of magnesium from seawater, there is the possibility of impacting the environment, such as by changing seawater composition. Accordingly, magnesium recovery from seawater must be conducted without impact on the environment.
[0004] Patent Document I shows an electrolysis tank for obtaining iIesh water, chiorne gas, and magnesium hydroxide from seawatci; and Patent Document 2 shows a method in which pH of deep seawater is electrolyzed, or pH is raised by addition of alkali, and hydroxides such as Mg and Ca are precipitated, and recovered as precipitate.
Citation List Patent Document [0005] Patent Document!: Japanese Unexamined Patent Application, First Publication No. 551-77586 Patent Document 2: Japanese Unexamined Patent Application, First Publication No. 2007-167786
Summary of Invention
Technical Problem [0006] In light of the pertinent circumstances, the present invention offers a magnesium recovery method and magnesium recovery apparatus which are capable of recovering magnesium from seawater without imposing burdens on the environment.
Solution to Problem [0007] The present invention pertains to a magnesium recovery method including: electrolyzing seawater; separating anodic electrolyzed waler and cathodic eleetrolyzed water produced by electrolysis of the seawater; inputting alkaline material into the anodic electrolyzed water to adjust pFI; precipitating magnesium as magnesium hydroxide in the cathodic electrolyzed water, and recovering the magnesium hydroxide; and intermixing the anodie electrolyzed water after pH adjustment and the cathodic electrolyed water after recovery of the magnesium hydroxide and discharging the inter nixed water in a state where a pH of the intermixed water is identical to a pH of the seawater.
[0008] In this case, the alkaline mater al may be waste concrete. Iron, which is a soluble metal, may be used in the anode-side electrode to cause dissolution of ferric ions in the anodic electrolyzed water in the seawater electrolysis process.
[0009] In addition, the present invention pertains to a magnesium rceovcry apparatus, including: an electrolysis tank having an anode and a cathode; a barrier film which partitions an interior of the electrolysis tank into an anode-side region containing the anode, and a cathode-side region containing the cathode; a first treatment tank which stores anodic electrolyzed water produced in the anode-side region; a second treatment tank which stores cathodic electrolyzed water produced in the cathode-side region; a power-supply unit which supplies power to the anode and the cathode; an alkaline material input device which inputs alkaline material to the first treatment tank; and a recovery unit which recovers magnesium hydroxide precipitated in the second treatment tank, in which wastewater from the first treatment tank and wastewater from the second treatment tank are intermixed, and discharged in a state where a pH of the intermixed water is identical to a pH of seawater.
[00101 In this case, the power-supply unit may have at least one photovoltaic cell, fuel cell, wind power generator, wave power generatol; ocean thermal power generatoi; or solar 6 thermal power generator. The power-supply unit nay contain a fuel cell which uses hydrogen gas generated on the cathode-side region, and oxygen gas generated on the anode-side region. The alkaline material inputted from the alkaline material input device may be waste concrete. Furthermore, the anode may contain iron as a consumable electrode, and the consumable electrode may dissolve ferric ions.
Advantageous Birects of Invention [0011] According to (he magnesium recovery method of the present invention, seawater is electrolyzed, anodic electrolyzed water and cathodic electrolyzed water produced by to the electrolysis of seawater are separated, alkaline material is inputted into the anodic electrolyzed water to adjust pH, magnesium is precipitated as magnesium hydroxide in the cathodic clcctrolyzed water, and recovered, and the anodic eleotrolyzed water after pH adjustment and the cathodic electrolyzed water after magnesium hydroxide recovery are intermixed, and discharged with a pH identical to that of seawater. Consequently, according to the present invention, magnesium can he recovered from seawater without impact on the environment.
[0012] In the magnesium recovery method of the present invention, it is possible to concomitantly perform treatment of industrial waste products when using waste concrete 26 as the alkaline material.
[0013] In the magnesium recovery method of the present invefflion, when using iron, which is a soluble metal, in the anode-side electrode, ferric ions are dissolved in the anodic electrolyzed water in the seawater electrolysis process, and lerrie ions that are a nutrient ofphytoplankton are supplied into the ocean. As a result, propagation of phytoplankton is promoted, achieving fixation of carbon dioxide gas by phytoplankton.
[0014] According to the magnesium recovery apparatus of the present invention, there is provided: an electrolysis tank which has an anode and a cathode; a barrier membrane which partitions the interior of the electrolysis tank into an anode-side region containing the anode, and a cathode-side rcgion containing the cathode; a first treatment tank which stores anodic electrolyzed water produced in the anode-side region; a second treatment tank which stores cathodic electrolyzed waler produced in the cathode-side region; a power-supply unit which supplies power to the anode and the cathode; an alkaline material input device which inputs alkaline material into the first treatment tank; and a recovery unit which recovers magnesium hydroxide precipitated in the second treatment tank, in which by intcrmixing wastewater from the first treatment tank and wastewater from the second treatment tank, wastewater is discharged with a pH identical to that of scawatet Consequently, it is possible to recover magnesium from seawater without impact on the environment.
[0015] In the magnesium recovery apparatus of the present invention, when the power-supply unit has at least one photovoltaic cell, fuel cell, wind power generator, wave power generator, ocean thermal power generator, or solar thermal power generatom; it is possible to recover magnesium without impact on the environment.
S
[0016] In the magnesium recovery apparatus of the present invention, when the power-supply unit contains a fuel cell which uses hydrogen gas generated on the cathode side, and oxygen gas generated on the anode side, a portion olthe power expended in seawater electrolysis is again used in seawater electrolysis. Consequently, energy conservation is achieved, [0017] In the magnesium recovery apparatus of the present invention, when the alkaline matcria[ inputted from the alkaline material input device is waste concrete, treatment of waste concrete which is an industrial waste product can be concomitantly performed, [00181 In the magnesium recovery apparatus of the present invention, when the anode includes iron as a consumable electrode, the consumable electrode dissolves ferric ions, thereby supplying ferrie ions, which are a nutrient of phytoplankton, into the occan. As a result, the excellent effects are obtained that propagation of phytoplankton is promoted, and fixation of carbon dioxide gas by phytoplankton is achieved.
Brief Description of Drawings
[0019] FIG. us a schematic view of an embodiment of the present invention.
FIG, 2 is a graph which shows cathode current density and the precipitation ratio of CaCO3 and Mg(OH)2 in the embodiment.
FIG 3 is a block diagram which shows material balance in the embodiment of the present invention.
FIG. 4 is a schematic block diagram which shows the magnesium recovery apparatus of an embodiment of the present invention.
Description of Embodiments
[0020J Embodiments of the present invention are described below with reference to drawings.
[0021J First, the principles of an embodiment of the present invention are described in FIG 1.
[00221 In FIG. 1, 1 incUcates an electrolysis tank, 2 indicates a first treatment tank, and 3 indicates a second treatment tank.
[0023] The electrolysis tank 1 has an electrolytic treatment container 4 made of corrosion-resistant material such as stainless steel, and the electrolytic treatment container 4 has an inlet 5 at the upstream end, and an outlet 6 at the downstream end, Seawater 7, which flows in from the inlets, runs uniformly through the interior of the electrolytic treatment container 4, and is discharged from the outlet 6.
[0024] Various methods may he adopted as a method of forming the flow of the seawater 7.
For example, the electrolytic treatment container 4 may be submcrgcd in water to utilize ocean current, and have the seawater 7 flow through the interior of the electrolytic treatment container 4; or a screw or the like may be provided in the inlet 5 to crcatc water flow by rotating this screw by a motor; or the seawater 7 may be taken in by a pump or the like, and supplied to the inlet 5.
[0025] A harrier membrane 8 is provided inside the electrolytic treatment container 4 in the flow direction of the seawater. The barrier membrane 8 partitions the interior of the electrolytic treatment container 4 in two, with the result that a flow of the seawater 7 separated by the barrier membrane 8 is formed inside the electrolytic treatment container 4.
[0026] The barrier membrane 8 uses a material and structurc through which electric current passes and which prevent or inhibit intermixture of the separated streams, For example, one may use unglazed plates in tile form laid out in rows, or porous sheets or the like made of synthetic resin.
[0027] in the case where the interior of the electrolytic treatment container 4 is partitioned by the battier membrane 8, various formats are conceivable such as vertical partitioning, lateral partitioning, and concentric partitioning, but the following is a description of the case where the interior of the electrolytic treatment container 4 is vertically partitioned by the barrier membrane 8.
[0028] A positive electrode (anode) 9 is provided along the upper wall surface of the electrolytic treatment container 4, a negative electrode (cathode) II is provided along thc lower wall surface, and the anode 9 and the cathode II are respectively connected to a positive pole and negative pole of a power-supply unit 12. Accordingly, an anode-side region 9a and cathode-side region 11 a arc formed within the electrolytic treatment container 4 by partitioning of the interior of the electrolytic treatment container 4 by the barrier membrane 8.
[0029] The power source of the power-supply unit 12 is optional, but a power supply source utilizing natural energy such as photovollaic power generation, wind power generation, wave power generation, ocean thermal power generation, and solar thermal power generation, or a fuel cell which has harmless emissions are preferable. A composite device composed of two or more power sources such as photovoltaic power generation, wind power generation, wave power generation, ocean thermal power generation, solar thermal power generation, and a fuel cell may also be used, Furthermore, in the case where power is supplied from an electric power plant, it is also acceptable to utilize nighttime surplus power, [0030] As the anode 9, an anode is used in which a soluble metal is inputted as a consumable electrode material 13 into a bucket (consumable electrode storage container) of reticular or porous plates of an insoluble metal such as titanium. Iron is preferable as the inputted consumable electrode material 13. Not only is iron easy to obtain as waste material, but the ferric ions that dissolve serve as nutrients for propagation of phytoplankton. As a result, phytoplankton is propagated by supplying ferric ions to the seawater, and carbon dioxide gas fixation by phytoplankton can also be anticipated.
[0031] The cathode 11 uses platinized titanium or the like. A hydrogen recovery device 14 is provided in the vicinity of the cathode 11 or opposite the cathode 11, and the hydrogen recovery device 14 recovers hydrogen gas generated on the cathode ii side Seawater (anodic electrolyzed water 7a) that flows through the anode 9 side (anode-side region 9a) is directed to the first treatment tank 2, and seawater (cathodic clectrolyzed water 7b) that flows through the cathode 11 side (cathode-side region 11 a) is directed to the second treatment tank 3.
[0032] l'he first treatment tank 2 has a waste concrete input device 15, and concrete that is waste material is inputted into the first treatment tank 2 by the waste concrete input device 15. l'he inputted waste concrete is preferably pulverized with a large surface area, and removal of aggregate such as sand, rocks and the like is more preferable.
[0033] Hydrogen gas recovered in (lie seawater 7 is supplied as a reducing agent of the fuel cell to the second treatment tank 3. Precipitated Mg(OH)2 is deposited in the second treatment lank 3, and the deposited Mg(OU)2 is recovered. The anodie electrolyzed water 7a that flows out from the first treatment tank 2 and the cathodic electrolyzed water lb that flows out from the second treatment tank 3 are intermixed, and discharged to (he ocean after adjustment of pH.
[0034] The operations of the present embodiment are described below.
[0035] Electrolysis of seawater occurs by applying voltage between the anode 9 and the cathode 11 to cause energization between the anode 9 and cathode 11, and it is primarily the reactions of the following formulas (1) and (2) that occur on the cathode 11 side.
[0036] 20+ l/20z+26-20W (1) 2H20 + 2e -* 20W + H2 (2) [0037] Accordingty, the pH of seawater on the cathode side (cathodic electrolyzed water 7b) increases due to generation of OfF (hydroxy ions), producing CaCO3 and Mg(OH)2, as shown in FIG 2, In addition, when current-carrying volume per unit area of the cathode ills considered as cathode current density Ok (A/rn2), the cathode current density Dk and the precipitation ratio of CaCO3 and Mg(OH)2 are as shown in FIG 2.
That is, when the cathode current density Dk increases, thc precipitation ratio of Mg(OII)2 increases, and a saturated condition ensues with respect to precipitation of Mg(OH)2 at the point where cathode current density Dk exceeds 2 (A/rn2). Precipitation of CaCO3 gradually decreases and precipitation of Mg(OT-J)2 gradually increases up to a cathode currcnt density Ok of 2 (A/rn2). Consequently, by controlling the cathode current density Dk, it becomes possible to control the precipitation ratio of CaCO3 and Mg(OH)2, or to selectively precipitate CaCO3 and Mg(OTI)2.
[0038] Therefore, by conducting electrolysis with cathode current density Dk set high -that is, by conducting electrolysis of seawater at a cathode current density Dk of 2 [A/rn2] or higher in accordance with FIG. 2 it is possible to have most of the precipitate be Mg(OII)2.
[0039] The cathodic electrolyzed water lb is stored in the second treatment tank 3 in a state where Mg(OH)2 has precipitated. The precipitated Mg(Ol-l)2 is deposited in the second treatment tank 3, and the precipitate is recovered by a precipitate recovery means 16.
[00401 In the aforementioned seawater electrolysis process, oxygen gas is generated on the anode 9 side, and hydrogen gas is generated on the eathodc 11 side. The generated hydrogen gas is recovered by the hydrogen recovery device 14, and is supplied to the fuel 26 ccli as a reducing agent in the case where a fuel cell is used in the power-supply unit 12.
[0041] Next, in the ease where iron is used as the consumable electrode material 13 on the anode 9 side, the following reactions occur, dissolving the iron, Furthermore, ferrous hydroxide occurs and H is produced by hydrolysis of ferrie ions, thereby lowering the pH of seawater on the anode 9 side (anodic electrolyzed water 7a).
[0042] Fe Fc2+26 (3) Pe2 ± 2H20 -* Fe(OH)2 -H 2t (4) [0043] The anoclie olectrolyzed water 7a which flows into the first treatment tank 2 is turned acidic by 2Ht. When waste concrete (Ca(OH)2) is inputted into the first treatment tank 2, the acidic seawater is neutralized by the waste concrete according to the following formula, Ca(0H)2 + 21-l -Ca2 + 21-120 (5) [0044] In the case where an insoluble metal is used in the anode 9, or when seawater electrolysis is conducted at a high current density, chlorine Cl2 is generated, and HC1 and FICIO are generated in conjunction with the generation of Cl2. As HCI is strongly acidic, and as HCIO is a harnthul substance to living creatures, electroTysis is conducted at a current density that inhibits generation of UC! and HCIO to the utmost. Howevei; as stated above, waste concrete (Ca(OH)2) is inputted into the anodic eleetrolyzed water 7a, whereby the IIC1 is neutralized by the reaction of: [0045] Ca(OH)z + HCI -* CaCI2 + 2H20 (6) [0046] The seawater that has been neutralized and treated in the first treatment tank 2 is then intermixed with the seawater discharged from the second treatment tank 3, and released into the ocean. In this case, the pH of the seawater after intermixture is adjusted to 8. 0-that is, to a pH identical to that of seawater -by controlling the amount of concrete to be dissolved in the anodic eleotrolyzed water 7a and the amount of carbon dioxide gas to be blown into the cathodic elcctrolyzcd water 7b.
[0047] Therefore, according to the present invention, as recovery of Mg(OH)2 can bc continuously conducted, and as waste concrete is used in the fixation treatment process, treatment of industrial waste material can be conducted in parallel. Furthermore, as the seawater that is discharged after recovery of Mg(OH)2 has a pH identical to that of natural seawater, there is no environmental impact. As the ferric ions dissolved in the electrolytic process cause propagation of phytoplankton, fixation of carbon dioxide gas is also promoted.
[00481 As stated above, in the seawater electrolysis process, oxygen gas is generated on the anode 9 side, and hydrogen gas is generated on the cathode 11 sidc. In the case where a fuel cell is used in the power-supply unit 12, the oxygen gas and the hydrogen gas are supplied to the fuel cell, serving as fuel for power generation.
[0049] Next, an example of material balance in the foregoing embodiment is described with reference to FIG. 3. In FlU. 3, components identical to those shown in FIG. 1 are given the same reference symbols.
[0050] Electrolytic reaction is varied by varying the cathode current density Dk, and electrolytic reaction is promoted by increasing the cathode current density Dk.
therefore, it is possible to control pH on the anode 9 side and the cathode 11 side in the Mg(OR)2 recovery treatment process by controlling the cathode current density Dk.
[0051] First, the pH of the cathodic eleetro1yed water 7b is set to 10-11, and Ca2' and Mg2 in the seawater arc entirely precipitated by electrolysis. At this time, the pH of the anodic electrolyzed water 7a is on the order of 3-4. In order to conduct recovery of Mg(OH2 efficiently, the cathode current density Dk is set to 2 EAJm2] or higher.
[00521 Recovery of the Mg(OH)2 that has precipitated in the second treatment tank 3 is then conducted. The pH of the cathodic electrolyzcd water 7b that flows out from the second treatment tank 3 is set to 10-1 t. Waste concrete is inputted into the first treatment tank 2, and the pH of the anodic eleetrolyzed water 7a that flows out from the first treatment tank 2 is adjusted to 4-5. The pH of the otitflowing anodic electrolyzed water 7a is but one example, and the input amount of the aforementioned waste concrete is adjusted so that pH is 8. 0-8. 2 when the anodic electrolyzed water 7a and the cathodic eleetrolyzed water 7b are intermixed, By setting the pFl of the discharged wastewatcr to 8. 0-8. 2, recovery of Mg(OH)2 can be conducted while discharging wastewater without changing the physical properties of the scawateL Accordingly, there is no impact on the environment, [0053] By refining the recovered Mg(OH)2, magnesium metal can be produced.
[0054] In the foregoing embodiment, waste concrete is used as the neutralizer of the anodic electrolyzed water 7a, but any neutralizer is acceptable provided that it is waste material having alkalinity, such as the coal ash produced in thermoelectric power plants.
[0055] In the foregoing embodiment, seawater electrolysis is conducted while circulating seawater inside the electrolysis tank 1, but it is also acceptable to have a batch system in which on-off valves are respectively providcd in the inlet 5 and the outlet 6, seawater electrolysis is conducted in a state where the inlet 5 and the outlet 6 are closed, and the seawater inside the electrolysis tank 1 is replaced after electrolytic treatment.
[0056] FIG. 4 shows an overview of a Mg(O1-I)2 recovery apparatus pcrtaming to an embodiment of the present invention.
[0057] In FIG 4, components identical to those shown in FIG. 1 are given the same reference symbols. Moreover, in the embodiment shown in FIG. 4, a fuel cell 18 is shown as the power source.
[0058] In this apparatus, a hydrogen gas recovery line 21 is provided which recovers hydrogen gas that is generated on thc hydrogen recovery device 14 side of the electrolysis tank 1, and which supplies it to the fuel cell 18, and an oxygen gas recovery line 22 is provided which recovers oxygen gas that is generated on the anode 9 side of the electrolysis tank 1, and which supplies it to the fuel cell 18. The hydrogen gas recovery line 21 and the oxygen gas recovery line 22 respectively have gas flow-rate regulation blowers 23 and 24 to regulate the flow rate of the oxygen gas and the hydrogen gas that are supplied to the fuel cell 18.
[0059] The power generated by the fuel cell 18 accumulates in the power-supply unit 12, J5 and the supply of accumulated power is controlled so that a prescribed cathode current density Dk is attained iii the cathode 11. Power shortfafls in the amount of power generated by the the! cell 18 are supplemented by power from photovoltaic power generation, wind power generation, or wave power generation, or by power from electric power plants.
[00601 A seawater supply line 25, a waste concrete tank 26 (equivalent to the first treatment tank 2), and a recovery tank 27 (equivalent to the sccond treatment tank 3) are connected to the electrolysis tank 1.
[006!] Acidic water which is the anodic electiolyzed water 7a is supplied to the waste concrete tank 26, waste concrete is inputted into the waste concrete tank 26, pH is adjusted so that the water is weakly acidic, and the adjusted water is discharged.
[0062] Alkaline water which is the cathodic clectrolyzed water 7b containing Mg(OH)2 is supplied to the recovery tank 27. The Mg(OH)2 that has precipitated in the recovery tank 27 is recovered, and the cathodic electrolyzed water 7b (alkaline water) from which Mg(OI-I)2 has been removed is discharged from the recovery tank 27.
[0063] After the acidic water that has been discharged from the waste concrete tank 26 and the alkaline water that has been discharged from the recovery tank 27 are intermixed, discharge is conducted from the recovery apparatus into the ocean. The pH of the wastewater is adjusted by the intermixing of acidic water and alkaline water, with the result that the pH of the wastewater in a state where it is finally released fiom the recovery apparatus is identical to the pH of seawatei; and there is no impact on the environment.
fOOó4j In FIG. 4, 31 indicates a pump which feeds seawater to the electrolysis tank 1, 32 indicates a pump which feeds the cathodic electrolyzed water 7b to the recovery Lank 27, 33 indicates a pump that serves to discharge water from the waste concrete tank 26, and 34 indicates a pump that serves to discharge water from the recovery tank 27.
Industrial Applicability
[0065] According to the present invention, it is possible to provide a magnesium recovery method and a magnesium recovery apparatus which enable recovery of magnesium from seawater while minimizing impact on the environment.
Reference Signs List [0066] 1: electrolysis tank, 2: first treatment tank, 3: second treatment tank, 4: electrolytic treatment container, 5: inlet, 7: seawater, 7a: anodie electrolyzed watei; 7b: cathodic clcctrolyzed water, 8: barrier film, 9: anode, 9a: anode-side region, 11: cathode, 11 a: cathode-side region, 12: power-supply unit, 13: consumable electrode material, 14: hydrogen recovery device, 15: waste concrete input device, 16: carbon dioxide gas blower, 18: fuel cell, 21: hydrogen gas recovery line, 22: oxygen gas recovery line, 26: waste concrete tank, 27: ICCO Ve17 tank

Claims (1)

  1. <claim-text>CLAIMS1 A magnesium recovery method comprising: electrolyzing seawater; separating anodic electrolyzed water and cathodic electrolyzed water produced by electrolysis of the seawater; inputting alkaline material into the anodic electrolyzed water to adjust pH; precipitating magnesium as magnesium hydroxide in the cathodic electrolyzed water, and recovering the magnesium hydroxide; and intermixing the anodic electrolyzed water after pH adjustment and the cathodic electrolyzed water after recovery of the magnesium hydroxide, and discharging the intermixed water in a state rhere a pH of the intermixed water is identical to a pH of the seawater.</claim-text> <claim-text>2. The magnesium recovery method according to claim 1, wherein the alkaline material is waste concrete.</claim-text> <claim-text>3. The magnesium recovery method according to claim 1, wherein iron, which is a soluble metal, is used in the anode-side electrode to cause dissolution of ferric ions in the anodie electrolyzed water in the seawater electrolysis process.</claim-text> <claim-text>4. A magnesium recovery apparatus, comprising: an electrolysis tank having an anode and a cathode; a barrier film which partitions an interior of the electrolysis tank into an anode-side region containing the anode, and a cathode-side region containing the cathode; a first treatment tank which stores anodic electroTyzed water produced in the anode-side region; a second treatment tank which stores cathodic electrolyzed water produced in tile cathode-side region; a power-supply unit which supplies power to the anode and the cathode; an alkaline material input device which inputs alkaline material to the first treatment tank; and a recovery unit which recovers magnesium hydroxide precipitated in the second treatment tank, wherein wastewater from the first treatment tank nd wastewater from the second treatment tank are intermixed, and discharged in a state where a piT of the intermixed water is identical to a pH of seawater.</claim-text> <claim-text>5. The magnesium recovery apparatus according to claim 4, wherein the powersuppIy unit has at least one of photovoitaic cell, fuel cell, wind power generator, wave power generatol; ocean thermal power generatol; and solar thermal power generatot 6. The magnesium recovery apparatus according to claim 4, wherein the power-supply unit contains a fuel cell which uses hydrogen gas generated on the cathode-side region, and oxygen gas generated on the anode-side region.7. The magnesium recovery apparatus according to claim 4, wherein the alkaline material inputted from the alkaline material input device is waste concrete.8. The magnesium recovery apparatus according to claim 4, wherein the anode contains iron as a consumable electrode, and the consumable electrode dissolves feiric ions.</claim-text>
GB1306089.2A 2010-09-10 2011-09-06 Magnesium recovery method and magnesium recovery apparatus Withdrawn GB2497256A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010203353A JP5824793B2 (en) 2010-09-10 2010-09-10 Magnesium recovery method and magnesium recovery device
PCT/JP2011/070236 WO2012033083A1 (en) 2010-09-10 2011-09-06 Magnesium recovery method and magnesium recovery apparatus

Publications (2)

Publication Number Publication Date
GB201306089D0 GB201306089D0 (en) 2013-05-22
GB2497256A true GB2497256A (en) 2013-06-05

Family

ID=45810681

Family Applications (1)

Application Number Title Priority Date Filing Date
GB1306089.2A Withdrawn GB2497256A (en) 2010-09-10 2011-09-06 Magnesium recovery method and magnesium recovery apparatus

Country Status (8)

Country Link
US (1) US20130161200A1 (en)
JP (1) JP5824793B2 (en)
AU (1) AU2011299918B2 (en)
CA (1) CA2810648C (en)
GB (1) GB2497256A (en)
NO (1) NO20130459A1 (en)
SG (1) SG188458A1 (en)
WO (1) WO2012033083A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9499880B2 (en) 2015-03-06 2016-11-22 Battelle Memorial Institute System and process for production of magnesium metal and magnesium hydride from magnesium-containing salts and brines
KR101710283B1 (en) * 2015-11-11 2017-03-08 고려대학교 산학협력단 Highly selective magnesium recovery apparatus and Highly selective magnesium recovery method using thereof
CN107164777B (en) * 2017-05-12 2019-01-25 中国科学院过程工程研究所 A kind of method of film electrolysis separating magnesium and enriching lithium from salt lake brine with high magnesium-lithium ratio
US10968126B2 (en) 2017-07-07 2021-04-06 Katz Water Tech, Llc Pretreatment of produced water to facilitate improved metal extraction
JP6783436B1 (en) 2019-08-29 2020-11-11 健司 反町 Carbon dioxide fixation method, immobilization carbon dioxide production method, and immobilization carbon dioxide production equipment
JP7008305B2 (en) * 2020-01-22 2022-01-25 健司 反町 How to fix carbon dioxide and how to make fixed carbon dioxide
US20210308623A1 (en) * 2020-01-22 2021-10-07 Kenji SORIMACHI Method for fixing carbon dioxide, method for producing fixed carbon dioxide, and carbon dioxide fixation apparatus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61177385A (en) * 1985-01-30 1986-08-09 Mitsui Eng & Shipbuild Co Ltd Production of magnesium hydroxide
JPH04325391A (en) * 1991-04-08 1992-11-13 Un Zee Cho Solar heated fuel self-feed type wide deck multi-leg ship
JPH0928234A (en) * 1995-07-19 1997-02-04 Tomoji Tanaka Cultured fish tank
JP2005262158A (en) * 2004-03-22 2005-09-29 Shimizu Corp Concrete regenerated fine powder and neutralization method
JP2009262124A (en) * 2008-03-31 2009-11-12 Kobelco Eco-Solutions Co Ltd Method and apparatus for purification treatment of metal component-containing water

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5891320A (en) * 1996-03-11 1999-04-06 Wurzburger; Stephen R. Soluble magnesium hydroxide
US6190530B1 (en) * 1999-04-12 2001-02-20 International Business Machines Corporation Anode container, electroplating system, method and plated object
US6375825B1 (en) * 1999-10-28 2002-04-23 Chemical Products Corporation Process for the production of alkaline earth hydroxide
JP2007098352A (en) * 2005-10-07 2007-04-19 Kido Toshihiro Functional water making apparatus and functional water making method
US8177946B2 (en) * 2007-08-09 2012-05-15 Lawrence Livermore National Security, Llc Electrochemical formation of hydroxide for enhancing carbon dioxide and acid gas uptake by a solution

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61177385A (en) * 1985-01-30 1986-08-09 Mitsui Eng & Shipbuild Co Ltd Production of magnesium hydroxide
JPH04325391A (en) * 1991-04-08 1992-11-13 Un Zee Cho Solar heated fuel self-feed type wide deck multi-leg ship
JPH0928234A (en) * 1995-07-19 1997-02-04 Tomoji Tanaka Cultured fish tank
JP2005262158A (en) * 2004-03-22 2005-09-29 Shimizu Corp Concrete regenerated fine powder and neutralization method
JP2009262124A (en) * 2008-03-31 2009-11-12 Kobelco Eco-Solutions Co Ltd Method and apparatus for purification treatment of metal component-containing water

Also Published As

Publication number Publication date
AU2011299918A1 (en) 2013-05-02
CA2810648C (en) 2016-01-12
SG188458A1 (en) 2013-04-30
GB201306089D0 (en) 2013-05-22
US20130161200A1 (en) 2013-06-27
CA2810648A1 (en) 2012-03-15
NO20130459A1 (en) 2013-04-16
JP5824793B2 (en) 2015-12-02
WO2012033083A1 (en) 2012-03-15
AU2011299918B2 (en) 2014-09-04
JP2012057230A (en) 2012-03-22

Similar Documents

Publication Publication Date Title
US9302216B2 (en) Carbon dioxide gas fixation method and carbon dioxide gas fixation apparatus
AU2011299918B2 (en) Magnesium recovery method and magnesium recovery apparatus
CN105585182A (en) Ballast water treatment equipment
CN108675403A (en) A kind of method of electrochemistry struvite crystallization recycling sewerage nitrogen and phosphor
CN102491456A (en) Method and device of electrochemical descaling, corrosion inhibition, sterilization and algae removal for cooling circulating water
CN206940502U (en) A kind of electrochemical desalting water softening device of efficiently spontaneous crystallization
KR102207458B1 (en) A fresh water system capable of producing hydrogen gas
CN104261573A (en) Electrochemical water scale removal device
KR20120114182A (en) A seawater electrolysi and fuel cell complex system
KR20210010937A (en) A fresh water system capable of producing hydrogen gas
KR101427563B1 (en) Seawater electrolytic apparatus
CN107253782A (en) A kind of ferrikinetics electrochemistry Fenton method for treating water and device
CN105399187A (en) Method for resource utilization of steel wire rope pickling waste liquor
CN105036423A (en) Electrolytic treatment system of ship domestic sewage
CN203613055U (en) Treatment device for wastewater with high salinity and chlorine
CN207062049U (en) A kind of ferrikinetics electrochemistry Fenton water treatment facilities
Arakcheev et al. Automated production system for reagents used in water and wastewater processing
RU2540616C2 (en) Method of decontamination of water systems with mineralised industrial waters in form of hypochlorite solutions
CN212198853U (en) Desulfurization wastewater full electric drive processing system of coal-fired power plant
Hussain et al. Nitrogen and phosphorus recovery as struvite from nutrient rich wastewater using electrochemical method: A review
CN102259961B (en) Method for comprehensively utilizing supernatant of calcium carbide slurry and dilute brine generated by electrolysis
TWI755644B (en) A method for removing ammonia nitrogen from waste water
CN107792969A (en) A kind of high salinity waste water recycling electrochemical treatments technique
CN102807269A (en) Microelectrolysis catalytic device for sewage treatment equipment
Arakcheev et al. Complex Automated Electrolysis Unit for Wastewaters Treatment and Drinking Water Purification

Legal Events

Date Code Title Description
WAP Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1)