AU2011299918A1 - Magnesium recovery method and magnesium recovery apparatus - Google Patents
Magnesium recovery method and magnesium recovery apparatus Download PDFInfo
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- AU2011299918A1 AU2011299918A1 AU2011299918A AU2011299918A AU2011299918A1 AU 2011299918 A1 AU2011299918 A1 AU 2011299918A1 AU 2011299918 A AU2011299918 A AU 2011299918A AU 2011299918 A AU2011299918 A AU 2011299918A AU 2011299918 A1 AU2011299918 A1 AU 2011299918A1
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- magnesium
- electrolyzed water
- seawater
- anode
- cathode
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- 238000011084 recovery Methods 0.000 title claims abstract description 66
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 49
- 239000011777 magnesium Substances 0.000 title claims abstract description 49
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000013535 sea water Substances 0.000 claims abstract description 67
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 25
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000000446 fuel Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 12
- 229910001447 ferric ion Inorganic materials 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000005192 partition Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 150000002680 magnesium Chemical class 0.000 abstract 2
- 150000005323 carbonate salts Chemical class 0.000 abstract 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 24
- 238000010248 power generation Methods 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- -1 hydroxy ions Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
-
- 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
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B1/18—Alkaline earth metal compounds or magnesium compounds
- C25B1/20—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4618—Supplying or removing reactants or electrolyte
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater 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)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Geology (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 5 APPARATUS Technical Field [0001] The present invention relates to a method and apparatus for recovering 10 magnesium from seawater by electrolysis of seawater. Priority is claimed on Japanese Patent Application No. 2010-203353, filed September 10, 2010, the content of which is incorporated herein by reference. Background Art 15 [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 from the mineral, is unevenly distributed in limited geographical areas, and it would be desirable to establish 20 procurement methods apart from importation of magnesium in order to secure stable supply in the future. [0003] As is well known, magnesium exists as a mineral, and is also contained in seawater. Accordingly, if magnesium could be recovered from seawater, it would 25 greatly contribute to stable supply of magnesium. On the other hand, when recovering 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] 5 Patent Document 1 shows an electrolysis tank for obtaining fresh water, chlorine gas, and magnesium hydroxide from seawater, 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. 10 Citation List Patent Document [0005] Patent Document 1: Japanese Unexamined Patent Application, First Publication No. S51-77586 15 Patent Document 2: Japanese Unexamined Patent Application, First Publication No. 2007-167786 Summary of Invention Technical Problem 20 [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. 25 Solution to Problem [0007] The present invention pertains to a magnesium recovery method including: electrolyzing seawater; separating anodic electrolyzed water and cathodic electrolyzed water produced by electrolysis of the seawater; inputting alkaline material into the anodic 5 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 where a pH of the intermixed water is identical to a pH of the seawater. 10 [0008] In this case, the alkaline material 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] 15 In addition, the present invention pertains to a magnesium recovery 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 20 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 25 treatment tank are intermixed, and discharged in a state where a pH of the intermixed water is identical to a pH of seawater. [0010] In this case, the power-supply unit may have at least one photovoltaic cell, fuel cell, wind power generator, wave power generator, ocean thermal power generator, or 5 solar thermal power generator. The power-supply unit may 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. 10 Advantageous Effects of Invention [0011] According to the magnesium recovery method of the present invention, seawater is electrolyzed, anodic electrolyzed water and cathodic electrolyzed water produced by 15 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 electrolyzed water, and recovered, and the anodic electrolyzed 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, 20 according to the present invention, magnesium can be 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 25 as the alkaline material.
[0013] In the magnesium recovery method of the present invention, 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 ferric ions that are a 5 nutrient of phytoplankton 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 10 which partitions the 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 15 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 intermixing wastewater from the first treatment tank and wastewater from the second treatment tank, wastewater is discharged with a pH identical to that of seawater. Consequently, it is possible to recover magnesium from seawater without 20 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 generator, 25 it is possible to recover magnesium without impact on the environment.
[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 of the power expended in 5 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 material inputted from the alkaline material input device is waste concrete, treatment of 10 waste concrete which is an industrial waste product can be concomitantly performed. [0018] 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 ferric ions, which are a nutrient of phytoplankton, into the ocean. As 15 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] 20 FIG. 1 is 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 CaCO 3 and Mg(OH) 2 in the embodiment. FIG. 3 is a block diagram which shows material balance in the embodiment of the present invention. 25 FIG. 4 is a schematic block diagram which shows the magnesium recovery apparatus of an embodiment of the present invention. Description of Embodiments [0020] 5 Embodiments of the present invention are described below with reference to drawings. [0021] First, the principles of an embodiment of the present invention are described in FIG. 1. 10 [0022] In FIG. 1, 1 indicates 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 15 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 inlet 5, runs uniformly through the interior of the electrolytic treatment container 4, and is discharged from the outlet 6. [0024] 20 Various methods may be adopted as a method of forming the flow of the seawater 7. For example, the electrolytic treatment container 4 may be submerged 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 create water flow by rotating this screw by a motor; or the seawater 7 may be taken in by 25 a pump or the like, and supplied to the inlet 5.
[0025] A barrier 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 5 separated by the barrier membrane 8 is formed inside the electrolytic treatment container 4. [0026] The barrier membrane 8 uses a material and structure through which electric current passes and which prevent or inhibit intermixture of the separated streams. For 10 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 barrier membrane 8, various formats are conceivable such as vertical 15 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 20 electrolytic treatment container 4, a negative electrode (cathode) 11 is provided along the lower wall surface, and the anode 9 and the cathode 11 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 are formed within the electrolytic treatment container 4 by partitioning of the interior of the electrolytic treatment container 4 by the 25 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 photovoltaic power generation, wind power generation, wave power generation, ocean thermal power generation, and solar thermal 5 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 10 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 15 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] 20 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 11 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 electrolyzed 25 water 7b) that flows through the cathode 11 side (cathode-side region 11 a) is directed to the second treatment tank 3. [0032] The 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 5 device 15. The 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 the 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 10 second treatment tank 3, and the deposited Mg(OH) 2 is recovered. The anodic electrolyzed water 7a that flows out from the first treatment tank 2 and the cathodic electrolyzed water 7b that flows out from the second treatment tank 3 are intermixed, and discharged to the ocean after adjustment of pH. [0034] 15 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. 20 [0036] H20 + 1/20 2 + 2e- - 20H- (1) 2H 2 0 + 2e- - 20H- + H 2 (2) [0037] Accordingly, the pH of seawater on the cathode side (cathodic electrolyzed 25 water 7b) increases due to generation of OH- (hydroxy ions), producing CaCO 3 and Mg(OH) 2 , as shown in FIG. 2. In addition, when current-carrying volume per unit area of the cathode 11 is considered as cathode current density Dk (A/m 2), the cathode current density Dk and the precipitation ratio of CaCO 3 and Mg(OH) 2 are as shown in FIG. 2. That is, when the cathode current density Dk increases, the precipitation ratio of 5 Mg(OH) 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/m 2). Precipitation of CaCO 3 gradually decreases and precipitation of Mg(OH) 2 gradually increases up to a cathode current density Dk of 2 (A/m2). Consequently, by controlling the cathode current density Dk, it becomes possible to control the precipitation ratio of CaCO 3 and 10 Mg(OH) 2 , or to selectively precipitate CaCO 3 and Mg(OH) 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/m2 or higher in accordance with FIG. 2 - it is possible to have most of the precipitate be 15 Mg(OH) 2 . [0039] The cathodic electrolyzed water 7b is stored in the second treatment tank 3 in a state where Mg(OH) 2 has precipitated. The precipitated Mg(OH) 2 is deposited in the second treatment tank 3, and the precipitate is recovered by a precipitate recovery means 20 16. [0040] In the aforementioned seawater electrolysis process, oxygen gas is generated on the anode 9 side, and hydrogen gas is generated on the cathode 11 side. The generated hydrogen gas is recovered by the hydrogen recovery device 14, and is supplied to the fuel 25 cell as a reducing agent in the case where a fuel cell is used in the power-supply unit 12.
[0041] Next, in the case 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 ferric ions, thereby 5 lowering the pH of seawater on the anode 9 side (anodic electrolyzed water 7a). [0042] Fe -> Fe 2 + 2e- (3) Fe 2 + 2H 2 0 -> Fe(OH) 2 + 2H+ (4) [0043] 10 The anodic electrolyzed water 7a which flows into the first treatment tank 2 is turned acidic by 2H+. 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(OH) 2 + 2H* Ca + 2H 2 0 (5) 15 [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 Cl 2 is generated, and HCl and HClO are generated in conjunction with the generation of Cl 2 . As HCl is strongly acidic, and as HClO is a harmful substance to living creatures, electrolysis is conducted 20 at a current density that inhibits generation of HCl and HClO to the utmost. However, as stated above, waste concrete (Ca(OH) 2 ) is inputted into the anodic electrolyzed water 7a, whereby the HCl is neutralized by the reaction of: [0045] Ca(OH) 2 + HCl -> CaCl 2 + 2H 2 0 (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 5 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 electrolyzed water 7a and the amount of carbon dioxide gas to be blown into the cathodic electrolyzed water 7b. [0047] Therefore, according to the present invention, as recovery of Mg(OH) 2 can be 10 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 15 also promoted. [0048] 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 side. In the case where a fuel cell is used in the power-supply unit 12, the oxygen gas and the hydrogen 20 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 FIG. 3, components identical to those shown in FIG. 1 are given the same reference symbols. 25 [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(OH) 2 recovery treatment process by controlling the cathode current density Dk. 5 [0051] First, the pH of the cathodic electrolyzed water 7b is set to 10-11, and Ca 2 + and Mg2+ in the seawater are 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(OH) 2 efficiently, the cathode current density Dk is set to 2 [A/m 2] or higher. 10 [0052] Recovery of the Mg(OH) 2 that has precipitated in the second treatment tank 3 is then conducted. The pH of the cathodic electrolyzed water 7b that flows out from the second treatment tank 3 is set to 10-11. Waste concrete is inputted into the first treatment tank 2, and the pH of the anodic electrolyzed water 7a that flows out from the 15 first treatment tank 2 is adjusted to 4-5. The pH of the outflowing 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 electrolyzed water 7b are intermixed. By setting the pH of the discharged wastewater to 8. 0-8. 2, recovery of Mg(OH) 2 can be conducted while discharging wastewater without 20 changing the physical properties of the seawater. Accordingly, there is no impact on the environment. [0053] By refining the recovered Mg(OH) 2 , magnesium metal can be produced. [0054] 25 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 5 circulating seawater inside the electrolysis tank 1, but it is also acceptable to have a batch system in which on-off valves are respectively provided 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] 10 FIG. 4 shows an overview of a Mg(OH) 2 recovery apparatus pertaining 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 15 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 the hydrogen recovery device 14 side of the electrolysis tank 1, and which supplies it to the fuel cell 18, and an oxygen gas recovery 20 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. 25 [0059] The power generated by the fuel cell 18 accumulates in the power-supply unit 12, and the supply of accumulated power is controlled so that a prescribed cathode current density Dk is attained in the cathode 11. Power shortfalls in the amount of power generated by the fuel cell 18 are supplemented by power from photovoltaic power 5 generation, wind power generation, or wave power generation, or by power from electric power plants. [0060] 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 second treatment tank 3) are 10 connected to the electrolysis tank 1. [0061] Acidic water which is the anodic electrolyzed 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. 15 [0062] Alkaline water which is the cathodic electrolyzed 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(OH) 2 has been removed is discharged from the recovery tank 27. 20 [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 25 result that the pH of the wastewater in a state where it is finally released from the recovery apparatus is identical to the pH of seawater, and there is no impact on the environment. [0064] In FIG. 4, 31 indicates a pump which feeds seawater to the electrolysis tank 1, 5 32 indicates a pump which feeds the cathodic electrolyzed water 7b to the recovery tank 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 10 [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. 15 Reference Signs List [0066] 1: electrolysis tank, 2: first treatment tank, 3: second treatment tank, 20 4: electrolytic treatment container, 5: inlet, 7: seawater, 7a: anodic electrolyzed water, 7b: cathodic electrolyzed water, 25 8: barrier film, 9: anode, 9a: anode-side region, 11: cathode, 11 a: cathode-side region, 5 12: power-supply unit, 13: consumable electrode material, 14: hydrogen recovery device, 15: waste concrete input device, 16: carbon dioxide gas blower, 10 18: fuel cell, 21: hydrogen gas recovery line, 22: oxygen gas recovery line, 26: waste concrete tank, 27: recovery tank
Claims (8)
1. A magnesium recovery method comprising: electrolyzing seawater; 5 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 10 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 where a pH of the intermixed water is identical to a pH of the seawater. 15
2. The magnesium recovery method according to claim 1, wherein the alkaline material is waste concrete.
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 20 anodic electrolyzed water in the seawater electrolysis process.
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 25 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 5 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 10 treatment tank, wherein 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. 15
5. The magnesium recovery apparatus according to claim 4, wherein the power-supply unit has at least one of photovoltaic cell, fuel cell, wind power generator, wave power generator, ocean thermal power generator, and solar thermal power generator.
6. The magnesium recovery apparatus according to claim 4, wherein the power-supply 20 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. 25
8. The magnesium recovery apparatus according to claim 4, wherein the anode contains iron as a consumable electrode, and the consumable electrode dissolves ferric ions.
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JP2010-203353 | 2010-09-10 | ||
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 |
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US (1) | US20130161200A1 (en) |
JP (1) | JP5824793B2 (en) |
AU (1) | AU2011299918B2 (en) |
CA (1) | CA2810648C (en) |
GB (1) | GB2497256A (en) |
NO (1) | NO20130459A1 (en) |
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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 |
EP3889110A4 (en) * | 2020-01-22 | 2021-10-06 | Sorimachi, Kenji | Method for fixing carbon dioxide, method for producing fixed carbon dioxide, and device for fixing carbon dioxide |
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JPS61177385A (en) * | 1985-01-30 | 1986-08-09 | Mitsui Eng & Shipbuild Co Ltd | Production of magnesium hydroxide |
JPH07100466B2 (en) * | 1991-04-08 | 1995-11-01 | ウン ゼー チョウ | Solar powered fuel self-contained wide deck multi-legged ship |
JPH0928234A (en) * | 1995-07-19 | 1997-02-04 | Tomoji Tanaka | Cultured fish tank |
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 |
JP2005262158A (en) * | 2004-03-22 | 2005-09-29 | Shimizu Corp | Concrete regenerated fine powder and neutralization method |
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 |
JP5564174B2 (en) * | 2008-03-31 | 2014-07-30 | 株式会社神鋼環境ソリューション | Purification method and apparatus for purification of water containing metal components |
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2010
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- 2011-09-06 GB GB1306089.2A patent/GB2497256A/en not_active Withdrawn
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GB201306089D0 (en) | 2013-05-22 |
CA2810648C (en) | 2016-01-12 |
WO2012033083A1 (en) | 2012-03-15 |
JP2012057230A (en) | 2012-03-22 |
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GB2497256A (en) | 2013-06-05 |
AU2011299918B2 (en) | 2014-09-04 |
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