WO2012150738A1 - 미생물 연료전지를 이용한 중금속 제거 또는 귀금속 회수 방법 - Google Patents
미생물 연료전지를 이용한 중금속 제거 또는 귀금속 회수 방법 Download PDFInfo
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- C02F2201/46—Apparatus for electrochemical processes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Definitions
- the present invention relates to a method for removing heavy metals or recovering precious metals with power generation using microbial fuel cells (MFC) from heavy metals or precious metal containing wastewater.
- MFC microbial fuel cells
- mercury is the cause of environmental pollution and poisoning.
- Mercury exists mainly in three forms: elemental mercury (Hg), inorganic mercury compounds, and organic mercury compounds.
- the compounds of all mercury are called total mercury.
- the inorganic mercury compound is divided into a first mercury salt, a second mercury salt or amalgam, and the organic mercury compound is divided into an alkyl mercury compound.
- All mercury forms are highly toxic and each form has a different effect on human health.
- Methylmercury and Hg 2 Cl 2 are carcinogenic to humans.
- Mercury and its compounds are widely used in paint, pulp and paper manufacturing, oil refining, battery manufacturing, and pharmaceutical processes. Emissions of wastewater containing mercury ions can pollute the surrounding environment and can be seriously damaging to human health, either directly into the water by humans or indirectly through the food chain.
- Wastewater treatment processes containing heavy metals such as mercury include neutralization precipitation method, solvent extraction method, membrane separation method, adsorption and ion exchange resin method, but sedimentation method and solvent extraction method require post-processing because secondary sources are generated. In order to prevent damage to the silver film, pretreatment of the treatment source is essential.
- the ion exchange resin method is widely used for water treatment, but also has the disadvantage of adsorbing minerals contained in the water (Seo Jung-ho, signature bridge, Kwak Young-kyu, Kang Shin-mook, Noh Jong-soo, Lee Kuk-ui, Choi Yun-chan, Journal of Korean Society for Environmental Hygiene , 1998 , 24 (1), 98).
- microorganisms has the property of selectively adsorbing specific heavy metals, and can be used for the treatment of toxic heavy metals contained in industrial wastewater and for the recovery of expensive heavy metals (Seo Jung Ho, Signature Bridge, Shin Muk Kang, Exotic, Choi Yun Chan, Jung Gu Gu , Eui-Yong Kim, Korean Journal of Environmental Hygiene , 1997, 23 (4), 21) ..
- the microbial fuel cell generates a voltage that transfers electrons generated when the microorganism of the anode part decomposes an organic material, which is a substrate, to the reduction electrode part, and is recently used to purify contaminants such as waste water and sediment.
- Korean Patent Publication No. 10-2003-0038240 discloses a fuel cell type biochemical oxygen demand meter using a low nutritional electrochemically active microorganism and a biochemical low concentration oxygen demand measuring method using the same. Doing.
- Korean Patent Publication No. 10-2008-0066460 (2008. 07.
- Korean Patent Publication No. 10-2010-0109234 discloses a dechlorination method using a bioelectrochemical system
- Korean Patent Publication No. 10-2010-0137766 discloses a microbial fuel cell for indirectly oxidizing organic matter in a sediment layer using microorganisms by providing a cathode in a sediment layer deposited on a lower layer such as a lake and an anode on a water surface, and a method of reducing greenhouse effect using the same.
- techniques for removing heavy metals or recovering precious metals using microbial fuel cells are not known.
- microbial fuel cells use organic wastes to remove heavy metals or recover precious metals while simultaneously obtaining power.
- organic matter can also be removed from organic wastewater.
- the electrochemical method is known to have the ability to remove heavy metal ions from contaminated water to very low levels (ppb units) without secondary contamination, thus developing a new sustainable method for treating heavy metal containing wastewater. do.
- Microbial cell technology is hopeful and new, but also conducive to wastewater treatment and power generation (Cheng, SA, Dempsey, BA, Logan, BE, Environ Sci Technol. 2007, 4 , 8149).
- An object of the present invention is to consider the cost and by-products of heavy metals such as mercury in conventional wastewater, and concomitantly utilizes microbial fuel cells (MFC), which are recently used to purify contaminants such as wastewater and sediments. In production, it is intended to provide a method of removing heavy metals or recovering precious metals from wastewater containing heavy metals and precious metals economically without by-products.
- MFC microbial fuel cells
- the heavy metal to be removed is Hg 2+ , Hg + , Cr 6+ , Cr 5+ , Cr 4+ , Cr 3+ , Cr 2+ , As 5+ , As 3+ , Co 2+ , Co 3+ , Cu 2+ , Cu + , U 6+ , Mn 7+ , Mo 6+ , Cd 2+ , Pb 2+ , and the precious metals recovered are Ag + , Au 2+ , Au + , Pd 4 + , Pd 2+ , Pt 4+ , Pt 2+ , Rh 2+ , Ir 3+ , Re 3+ .
- anaerobic microorganisms that can be used in the microbial fuel cell (MFC) of the present invention are as follows; Alpha-proteobacteria, Beta-proteobacteria, Delta-proteobacteria, Clostridia, Shewanella oneidensis MR-1, Shewanella oneidensis DSP-10, Shewanella putrefaciens SR-21, IR-1, MR-1, Geobacter sulfurreducens, Geobacter sulfurreducens KN400, Ochrobactrum anthropi YZ -1, Brevibacillus sp. PTH1, E. coli K12 HB101, Aeromonas hydrophila, Corynebacterium sp.
- MFC03 Leptothrix discophora SP-6, Bacillus licheniformis, Bacillus thermoglucosidasius, Spirulina platensis, Bacillus subtilis, Enterococcus gallinarum, Acetobacter aceti, Gluconobacter roseus.
- the anode electrode and the cathode electrode are made of carbon material such as carbon felt, carbon cloth, carbon rod, carbon paper, carbon brush, and the separator between the electrode chamber is a cation exchange membrane (CEM), composite Membrane, nylon membrane, anion exchange membrane (AEM), and may be provided with two or more microbial fuel cell (MFC).
- CEM cation exchange membrane
- AEM anion exchange membrane
- a single MFC can remove or recover heavy metals directly if the voltage is sufficient.However, if sufficient voltage cannot be obtained in the constitution of a continuous MFC, the voltage from the front MFC is applied to the subsequent MFCs, and the metal ions at both ends can be removed. It is also possible to remove them at the same time. In the case of a multiple MFC configuration composed of two or more MFCs, even if the ion species removed at the front end are not ions of the same metal having a different valence from the rear end, if the voltage generation at the rear end is insufficient, the voltage is sufficient due to the application of the voltage generated at the front end MFC. Therefore, the ionic species can be removed or recovered from the rear end, which is difficult to react with a single MFC.
- the present invention provides a method for generating electricity while simultaneously removing Hg 2+ from solid mercury containing sediments or deposits of metal Hg or Hg 2 Cl 2 from mercury-containing wastewater as a heavy metal.
- the mercury-containing wastewater is preferably adjusted to an initial pH of 2 to 4.8, an initial Hg 2+ concentration of 25 to 100 mg / L, and more preferably to an initial pH using dilute hydrochloric acid.
- Hg 2+ is removed as a solid precipitate or sediment of the metal Hg or Hg 2 Cl 2
- Hg 2+ is removed as a solid precipitate or sediment of the metal Hg or Hg 2 Cl 2
- the electrons generated during the biodegradation of organic matter in the anode chamber are transferred through an external circuit toward the cathode, which reacts with the electron acceptor to generate an electric current. Meanwhile, ions such as protons are transported through the membrane between the electrode chambers to achieve charge neutrality (Kim, JR, Cheng, SA, Oh, SE, Logan, BE, Environ. Sci. Technol . 2007, 41 , 1004 ).
- Hg 2+ is also an electron acceptor which may be used as an MFC due to its high standard potential (when used as an electron acceptor).
- the electrochemical scheme and the potential for the hydrogen standard electrode at 25 ° C. are as follows:
- HCO 3 at pH 7 of the reduction potential is as follows:
- Hg 2+ As the electron acceptor and acetate as the electron donor, an electromotive force of 1.195 V can be theoretically obtained according to Reaction (1) and Reaction (4).
- FIG. 1 is a schematic diagram showing the removal mechanism of the heavy metal and the recovery of the noble metal having the reduction potential of the ear rather than the reduction potential of the organic matter. Removal or recovery of metals of the same kind with different oxidation numbers that do not have a reducing potential at the ear side can be removed or recovered secondary by supplying power to a battery configuration using the same or different metals having a reducing potential at the ear side.
- MFC technology can be used to remove or recover heavy metals or precious metals in wastewater with power generation.
- Hg 2+ can be effectively removed as a solid precipitate or deposit of metal Hg or Hg 2 Cl 2 , in addition to the removal of chromium and arsenic ions, and recovery of silver, gold, palladium, platinum, rhodium, iridium and rhenium ions.
- the use of a double MFC can remove or recover a large number of ions by applying the voltage of the front end MFC to the rear end when the voltage of the rear end MFC is not sufficient.
- 1 is a schematic diagram showing the removal mechanism of the heavy metal and the recovery of the noble metal having the reduction potential of the ear rather than the reduction potential of the organic matter.
- FIG. 2 is a schematic diagram of an MFC for Hg 2+ removal in accordance with the present invention.
- Figure 3 is a graph showing the release Hg concentration for various initial pH in the MFC according to the present invention.
- FIG. 4 and 5 are graphs showing the emission Hg concentration (FIG. 4) and the maximum power density (FIG. 5) against various initial Hg 2+ concentrations in the MFC according to the present invention.
- FIG. 6 is a graph showing the maximum power density and voltage expressed as a function of current density in the MFC according to the present invention.
- FIG. 7 is a schematic showing dual MFC installation for Cr 6+ and Cr 3+ removal.
- 8 to 12 are graphs showing a process of removing Cr 3+ as a solid material in a double MFC according to the present invention as a voltage curve over time.
- 13 and 14 is a graph showing the removal efficiency and the concentration of the remaining Cr 3+ Cr 3+, when the initial concentration be 50 ppm and 100 ppm, respectively.
- 15 is a schematic showing dual MFC installation for As 5+ and As 3+ removal.
- 16 to 20 are graphs showing a process of removing As 3+ from a dual MFC according to the present invention with a voltage curve over time.
- 21 is a graph showing the removal efficiency and the remaining As 3+ concentration of As 3+ 3+ As when the initial concentration of 50 ppm.
- FIG. 23 is a graph showing the change of voltage over time at various Ag + concentrations (25, 50, 100, 200 ppm) using the microbial fuel cell according to the present invention.
- 24 is a graph showing the recovery of Ag over time at various initial Ag + concentrations (25, 50, 100, 200 ppm).
- 25 is a graph showing the recovery of Au over time at various initial Au 3+ concentrations (25, 50, 100 ppm) using the microbial fuel cell according to the present invention.
- 26 is a graph showing the recovery of Pd over time at various initial concentrations of Pd 2+ (25, 50, 100 ppm) using the microbial fuel cell according to the present invention.
- FIG. 27 is a graph showing the recovery of Pt over time at various initial Pt 4+ concentrations (25, 50, 100 ppm) using the microbial fuel cell according to the present invention.
- 29 is a graph showing the recovery of Ir with time at various initial Ir 3+ concentrations (25, 50, 100 ppm) using the microbial fuel cell according to the present invention.
- FIG. 30 is a graph showing the recovery of Re with time at various initial Re 3+ concentrations (25, 50, 100 ppm) using the microbial fuel cell according to the present invention.
- Hg 2+ ions from synthetic mercury wastewater (MWW) using the MFC technique.
- factors affecting the removal efficiency of Hg 2+ such as initial pH and concentration of initial Hg 2+ were considered.
- the cell was fabricated using carbon felt as anode (reduction electrode, positive electrode) and carbon paper as cathode (reduction electrode, negative electrode), and the microbial fuel cell was constructed using the separator between electrode chambers as anion exchange membrane.
- the bisilic MFC used in the present invention was made of plexiglass with each electrode chamber having a capacity of 137 ml (length: 7 cm, diameter: 5 cm). The effective doses were both 120 ml.
- AEM was pretreated by immersion in NaCl solution before use and washed thoroughly with the next distilled water (Kim, JR, Cheng, SA, Oh, SE, Logan, BE, Environ. Sci. Technol . 2007, 41 , 1004).
- AEM membranes is expected to prevent direct migration of Hg 2+ and prevent the influx of harmful agents to the growth of microorganisms.
- concentration of Hg 2+ was not detected from the anode chamber solution. Protons will also be in the same situation as Hg 2+ .
- the pH was well controlled for the batch operation with the use of phosphate buffer.
- FIG. 2 is a schematic diagram of an MFC for Hg 2+ removal in accordance with the present invention.
- Anaerobic inoculation microorganisms were collected at the Okcheon Sewage Treatment Plant. In order to remove dissolved oxygen in 90 ml artificial wastewater (AW) and 30 ml sludge mixture, it was blown with nitrogen gas and pumped into the anode chamber.
- the artificial wastewater contains the following per liter: 1.36 g CH 3 COONaH 2 O, 1.05 g NH 4 Cl, 1.5 g KH 2 PO 4 , 2.2 g K 2 HPO 4 , and 0.2 g yeast extract as an electron donor.
- 0.2 g electron donor was replenished in the anode chamber when the voltage dropped below 25 mV in each cycle.
- the anode chamber was continuously stirred with a magnetic straw.
- the cathode chamber was filled with 120 ml of distilled water and air was injected to use dissolved oxygen as the electron acceptor.
- Anaerobic microorganisms that can be used in the microbial fuel cell (MFC) of the present invention are as follows; Alpha-proteobacteria, Beta-proteobacteria, Delta-proteobacteria, Clostridia, Shewanella oneidensis MR-1, Shewanella oneidensis DSP-10, Shewanella putrefaciens SR-21, IR-1, MR-1, Geobacter sulfurreducens, Geobacter sulfurreducens KN400, Ochrobactrum anthropi YZ -1, Brevibacillus sp. PTH1, E. coli K12 HB101, Aeromonas hydrophila, Corynebacterium sp.
- MFC03 Leptothrix discophora SP-6, Bacillus licheniformis, Bacillus thermoglucosidasius, Spirulina platensis, Bacillus subtilis, Enterococcus gallinarum, Acetobacter aceti, Gluconobacter roseus.
- the artificial wastewater in the anode chamber was replaced with a new artificial wastewater.
- the cathode chamber was refilled with MWW (mercury-containing wastewater).
- MWW dissolves HgCl 2 in distilled water to make this solution of 200 mg / L Hg 2+ and dilute with distilled water as needed to make the required MWW.
- Dilute hydrochloric acid was used to control pH (Yardim, MF, Budinova, T., Ekinci, E., Petrov, N., Razvigorova, M., Minkova, V., Chemosphere 2003, 52 , 835).
- the presence of Cl ⁇ ions was expected to help remove mercury ions with Hg 2 Cl 2 .
- the cathode chamber was continuously blown with N 2 gas (60 ml / min) during the experiment to prevent the dissipation of dissolved oxygen and to mix the solution.
- the initial pH and Hg 2+ concentration effective for removal of Hg 2+ was evaluated in the arrangement.
- the cathode chamber was switched from batch to continuous to maintain a constant Hg 2+ from the MWW reservoir while blowing with N 2 gas.
- the external resistance was changed from 4000 ⁇ to 50 ⁇ . All experiments were performed at 30 ° C. in a thermostatic incubator.
- Coulomb efficiency (CE) was calculated according to the following equation.
- the internal resistance was determined by the slope of the straight portion of the IV curve. At scheduled intervals of 1 or 2 hours, a 1 ml solution was taken from the N 2 outlet of the cathode chamber to analyze the total mercury using ICP emission spectra (ICPE-9000, Shimadzu, Japan). Deposits on the bottom of the cathode chamber were collected by filtration through glass microfiber filters. The chemical form of the deposit was identified by EDS (Quantax 200, Bruke, Germany).
- the release Hg 2+ concentrations for the 5 hour reaction were 3.08 ⁇ 0.07, 4.21 ⁇ 0.34, 4.84 ⁇ 0.00 and 5.25 ⁇ 0.36 mg / L at initial pH 2, 3, 4 and 4.8, respectively.
- the release mercury concentration in the 10 hour reaction ranged from 0.44-0.69 mg / L, indicating 98.22-99.54% removal efficiency.
- This removal efficiency of Hg 2+ was similar to the values reported in the prior art.
- the generation of electricity, the unnecessary exchange of adsorbents such as activated carbon, and the possible treatment of organic matter in the wastewater as electron donors make MFC a hopeful and sustainable technology as opposed to other technologies (Hutchison, A., Atwood, D.). , Santilliann-Jiminez, QE, 2008, J. Hazard Mater., 156 , 458).
- Table 1 below compares the removal efficiency of Hg 2+ according to the method of the present invention with the conventional method.
- FIG. 4 are graphs showing the emission Hg concentration (FIG. 4) and the maximum power density (FIG. 5) against various initial Hg 2+ concentrations according to the present invention (pH 2, external resistance from 4000 ⁇ to 50 ⁇ ). ).
- the release Hg 2+ concentration initially decreased sharply for two hours and slowly slowed down within six hours. Reduction rate of the Hg 2+ is increased with the increase in the initial concentration of Hg 2+. After reacting for 6 hours, the concentration of released Hg 2+ did not change significantly with respect to the concentration of other Hg 2+ .
- the concentration of release Hg 2+ for the 10 hour reaction ranged from 0.44 mg / L to 0.69 mg / L for the concentration of Hg 2+ between 25 mg / L and 100 mg / L.
- the internal resistance decreased from 146.9 ⁇ to 107.9 ⁇ .
- the CE was calculated in the range of 1.55 to 4.04%. The low CE was probably due to dissolved oxygen dissolved in the medium solution that consumed organics during the short discharge period without removing dissolved oxygen with N 2 before pumping into the anode chamber.
- Hg 2+ 1.5 times higher than reduction (433.1 mW / m2 280 mW / m2) (Wang, Z. J., Lim, B. S., Lu, H., Fan, J., Choi, C. S., Bull. Korean Chem. Soc . 2010, 7 , 2025.) If Hg 2+ If it is used only as an electron acceptor, it does not seem to be suitable due to its toxicity. In this embodiment, Hg 2+ Is intended to be removed from the wastewater and power is obtained as a by-product.
- the initial pH in the MFC according to the present invention affected the removal efficiency of Hg 2+ from electrochemical and chemical reactions.
- the concentrations of release Hg 2+ after 5 hours reaction showed 3.08 ⁇ 0.07, 4.21 ⁇ 0.34, 4.84 ⁇ 0.00 and 5.25 ⁇ 0.36 mg / L at pH 2, 3, 4 and 4.8, respectively.
- the concentration of released Hg 2+ at various initial concentrations of Hg 2+ ranged from 0.44 to 0.69 mg / L.
- Initial pH and Hg 2+ concentrations affected both power generation. Lower pH and higher Hg 2+ concentrations resulted in more peak power densities. A maximum power density of 433.1 mW / m 2 was achieved at 100 mg / L Hg 2+ at pH 2.
- Example 2 Removal of them from wastewater contaminated with Cr 6+ / Cr 3+
- FIG. 7 is a schematic showing dual MFC installation for Cr 6+ and Cr 3+ removal. This dual MFC is used to remove and recover by applying the voltage of the front end MFC to the rear end when the voltage of the rear end MFC is not sufficient. In this way, many ions can be removed or recovered.
- FIGS. 8 to 12 are graphs showing a process of removing Cr 3+ as a solid material in a double MFC according to the present invention as a voltage curve over time.
- the initial concentration is 100 ppm. That is, it develops from the microbial fuel cell composed of the acetate organic wastewater and Cr 6+ wastewater at the front end, and theoretically connects the external load resistance to the microbial fuel cell composed of the same organic wastewater and Cr 3+ wastewater with a voltage of about 1.6 V. It is a voltage curve over time that shows the process of removing Cr 3+ as a solid material by supplying it directly instead of.
- the latter battery is applied with a voltage of about 1.05 V.
- the removal of Cr from metal Cr to metal Cr is an energy absorption process that requires power supply from the outside. Therefore, it is analyzed that there is a voltage loss of about 0.55 V from the electromotive force of the front end.
- the voltage applied from the front end drops to about 0.7 V after about 30 hours due to the large concentration overvoltage due to the subsequent removal of Cr 3+ .
- the Cathode electrode chamber of the latter cell which is the Cr 3+ removal step, the precipitation of blue solids was visually observed, and it was possible to separate them with laboratory filter paper.
- the current versus time curve it can be seen that in about 20 hours, the current is lowered to its lowest state and Cr 3+ is almost completely removed.
- 13 and 14 is a graph showing the removal efficiency and the concentration of the remaining Cr 3+ Cr 3+, when the initial concentration be 50 ppm and 100 ppm, respectively. From here, after about 30 hours and the level of the removal processing of the remaining Cr 3+ Cr 3+ showed the concentration of 50 ppm and 100 ppm both 97.26% and 1.37 ppm of the initial Cr 3+. On the other hand, hexavalent chromium is more easily removed than trivalent chromium, resulting in a removal rate of more than 99%.
- Example 3 Removal of them from wastewater contaminated with As 5+ / As 3+
- FIG. 15 is a schematic showing dual MFC installation for As 5+ and As 3+ removal. This dual MFC is used to remove and recover by applying the voltage of the front end MFC to the rear end when the voltage of the rear end MFC is not sufficient. In this way, many ions can be removed or recovered.
- 16 to 20 are graphs showing a process of removing As 3+ from a dual MFC according to the present invention with a voltage curve over time.
- the initial concentration is 50 ppm.
- the energy generated during the reduction of H 3 AsO 4 to HAsO 2 in the front end is supplied to the absorption energy necessary for the precipitation of AsO 2 - in the rear part to remove As 5+ and As 3+.
- the process is shown as an electrochemical signal. These are the reactions that take place in the cathode chamber and the oxidation of acetate, one of the organic wastewaters, occurs at the anode.
- Reduction to HAsO 2 of the shear acid solution H 3 AsO 4 is a second electron reaction and the HAsO 2 generated in the shear AsO 2 of the basic solution - so the reaction was three electron reaction which by the reduction with As, volume if the density of the The shear should be at least 1.5 times.
- a solution of the same concentration and the volume of the front end of the rear end to the quantitative solution AsO 2 should be at least 1.5 times - it is possible to complete the reduction.
- the concentration was doubled to the same volume, and the reaction system was prepared with the front end of 100 ppm and the rear end of 50 ppm.
- the negative electrode of the front end is connected to the positive electrode of the rear end and the positive electrode of the front end is connected to the negative electrode of the rear end to react.
- Table 4 and Figure 21 is a table and graph showing the removal efficiency and the free concentration of As As 3+ 3+ 3+ As when the initial concentration of 50 ppm.
- Table 5 and Fig. 22 is a table and graph showing the removal efficiency and the free concentration of As As 3+ 3+ 3+ As when the initial concentration of 100 ppm.
- the present invention is the first time to recover silver by directly using the electrical energy obtained from organic wastewater containing silver and silver ion wastewater using the microbial fuel cell according to the present invention.
- the module is capable of generating sufficient power even with a forged cell.
- an electrolysis virtual experiment of typically about 3 hours was conducted to recover silver in the cathode chamber.
- various carbon materials which can use not only a carbon brush but also an electrode area such as a carbon felt or a graphite film plate are preferably used.
- the anode is fabricated so as not to affect the reaction of the cathode by using a much larger area than the cathode (about 10 times or more).
- FIG. 23 is a graph showing the change of voltage over time at various Ag + concentrations (25, 50, 100, 200 ppm) using the microbial fuel cell according to the present invention.
- the experiment temperature was 30 ° C. and was loaded at 1000 kPa.
- Table 6 and FIG. 24 show the recovery of Ag over time at various initial Ag + concentrations (25, 50, 100, 200 ppm).
- the solution was analyzed using ICP-AES.
- test module according to the present invention has excellent performance as a silver recovery or removal module and is likely to be a breakthrough in application and utilization in the field.
- the method of the present invention is not only for the recovery of silver from electronic waste or silver plating waste water, but also can be used critically for the recovery of silver by-products and refining of silver minerals in copper mines, and furthermore, it is possible to produce and supply electric power. It is meaningful.
- the silver recovery method described above can be similarly applied to other precious metals such as gold, and the results can also be similar to or better than those for silver.
- the following examples illustrate the recovery of Au, Pd, Pt, Rh, Ir, and Re, all showing recovery rates of 99% or more.
- the recovery of platinum was carried out analogously to the recovery of silver mentioned above using K 2 PtCl 6 solid reagent or H 2 PtCl 6 solid reagent.
- Table 9 and Figure 27 shows the recovery of Pt over time at various initial Pt 4 + concentrations (25, 50, 100 ppm) using a microbial fuel cell according to the present invention.
- KNO 3 of 0.2 M was used and the experiment temperature was 30 ° C. and 1000 kPa was loaded.
- the solution was analyzed using ICP-AES.
- MFC technology can be used to remove or recover heavy metals or precious metals in wastewater with power generation.
- Hg 2+ can be effectively removed as a solid precipitate or deposit of metal Hg or Hg 2 Cl 2 , in addition to the removal of chromium and arsenic ions, and recovery of silver, gold, palladium, platinum, rhodium, iridium and rhenium ions.
- the use of a double MFC can remove or recover a large number of ions by applying the voltage of the front end MFC to the rear end when the voltage of the rear end MFC is not sufficient.
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Abstract
Description
방법 | 초기 농도(mg/L) | 제거효율(%) | 참고 |
이온교환 | 90 | 99.96 | Monteagudo and Ortiz, 2000 |
2-머캡토벤즈이미다졸 점토를 이용한 흡착 | 50 | >99 | Manohar 등, 2002 |
알기닌 개질한 TiO2에 의한 광촉매 제거 | 150 | >99 | Skubal과 Meshkov, 2002 |
복수의 황을 함유한 개방 사슬 리간드 상에 침전 | 30 | 92.83-100 | Hutchison 등, 2008 |
활성탄 흡착 | 40 | 96.29-99.7 | Rao 등, 2009 |
미생물 연료전지 | 25-100 | 98.22-99.54 | 본 발명 |
1번 환원전극실 | 2번 환원전극실 | |
이온 | Cr6+ | Cr3+ |
재료 | 탄소 솔 2.5*2.5 ㎝ | 탄소 천 1.7*1.3 ㎝ |
용적 | 100 mL | 100 mL |
이온 농도 | 200 ppm | 100 ppm |
멤브레인 | CEM | AEM |
pH 값 | 2 | 미조정, 6.4 |
K2SO4 농도 | 200 mM | 200 mM |
교반 방식 | N2 제거 | N2 제거 |
1번 환원전극실 | 2번 환원전극실 | |
이온 | As5+ | As3+ |
재료 | 탄소 솔 2.5*2.5 ㎝ | 탄소 천 1.7*1.3 ㎝ |
용적 | 100 mL | 100 mL |
이온 농도 | 100 ppm | 50 ppm |
멤브레인 | CEM | CEM |
pH 값 | 2 | 미조정, 9.5 |
K2SO4 농도 | 200 mM | 200 mM |
교반 방식 | N2 제거 | N2 제거 |
반응시간/일 | 1 | 2 | 3 | 4 |
남은 As3+ 농도(As3+/ppm) | 0.04 | 0.03 | 0.02 | 0.01 |
제거 효율 % | 99.92 | 99.94 | 99.96 | 99.98 |
반응시간/일 | 1 | 2 | 3 | 4 |
남은 As3+ 농도(As3+/ppm) | 0.20 | 0.10 | 0.06 | 0.04 |
제거 효율 % | 99.80 | 99.90 | 99.94 | 99.96 |
Ag+의 초기 농도 | 25 ppm | 50 ppm | 100 ppm | 200 ppm |
시간/h | Ag 회수효율(%) | Ag 회수효율(%) | Ag 회수효율(%) | Ag 회수효율(%) |
1 | 99.61 | 99.70 | 99.79 | 67.20 |
2 | 99.80 | 99.85 | 99.87 | 99.90 |
3 | 99.80 | 99.85 | 99.90 | 99.94 |
Au3+의 초기 농도 | 25 ppm | 50 ppm | 100 ppm |
시간/h | Au 회수효율(%) | Au 회수효율(%) | Au 회수효율(%) |
1 | 99.7 | 99.60 | 99.50 |
2 | 99.80 | 99.85 | 99.87 |
3 | 99.90 | 99.87 | 99.90 |
Pd2+의 초기 농도 | 25 ppm | 50 ppm | 100 ppm |
시간/h | Pd 회수효율(%) | Pd 회수효율(%) | Pd 회수효율(%) |
1 | 99.50 | 99.40 | 99.30 |
2 | 99.90 | 99.50 | 99.87 |
3 | 99.90 | 99.80 | 99.70 |
Pt4+의 초기 농도 | 25 ppm | 50 ppm | 100 ppm |
시간/h | Pt 회수효율(%) | Pt 회수효율(%) | Pt 회수효율(%) |
1 | 99.7 | 99.60 | 99.40 |
2 | 99.90 | 99.82 | 99.80 |
3 | 99.90 | 99.87 | 99.87 |
Rh3+의 초기 농도 | 25 ppm | 50 ppm | 100 ppm |
시간/h | Rh 회수효율(%) | Rh 회수효율(%) | Rh 회수효율(%) |
1 | 99.40 | 99.50 | 99.20 |
2 | 99.70 | 99.65 | 99.57 |
3 | 99.80 | 99.70 | 99.70 |
Ir3+의 초기 농도 | 25 ppm | 50 ppm | 100 ppm |
시간/h | Ir 회수효율(%) | Ir 회수효율(%) | Ir 회수효율(%) |
1 | 99.37 | 99.26 | 99.12 |
2 | 99.65 | 99.53 | 99.47 |
3 | 99.72 | 99.63 | 99.54 |
Re3+의 초기 농도 | 25 ppm | 50 ppm | 100 ppm |
시간/h | Re 회수효율(%) | Re 회수효율(%) | Re 회수효율(%) |
1 | 99.35 | 99.25 | 99.16 |
2 | 99.56 | 99.47 | 99.29 |
3 | 99.87 | 99.64 | 99.43 |
Claims (18)
- 산화전극과 환원전극, 그리고 양 전극실 사이의 분리막을 구비한 미생물 연료전지(MFC; microbial fuel cells)에서 혐기성 미생물을 이용하여 중금속 함유 폐수로부터 중금속을 제거하는 동시에 전력을 생산하는 방법.
- 제 1 항에 있어서, 제거되는 중금속이 Hg2+, Hg+, Cr6+, Cr5+, Cr4+, Cr3+, Cr2+, As5+, As3+, Co2+, Co3+, Cu2+, Cu+, U6+, Mn7+, Mo6+, Cd2+ 또는 Pb2+인 것을 특징으로 하는 방법.
- 제 1 항에 있어서, 혐기성 미생물이 다음 중에서 선택된 적어도 하나인 것을 특징으로 하는 방법: Alpha-proteobacteria, Beta-proteobacteria, Delta-proteobacteria, Clostridia, Shewanella oneidensis MR-1, Shewanella oneidensis DSP-10, Shewanella putrefaciens SR-21, IR-1, MR-1, Geobacter sulfurreducens, Geobacter sulfurreducens KN400, Ochrobactrum anthropi YZ-1, Brevibacillus sp. PTH1, E. coli K12 HB101, Aeromonas hydrophila, Corynebacterium sp. MFC03, Leptothrix discophora SP-6, Bacillus licheniformis, Bacillus thermoglucosidasius, Spirulina platensis, Bacillus subtilis, Enterococcus gallinarum, Acetobacter aceti, Gluconobacter roseus.
- 제 1 항에 있어서, 산화전극 및 환원전극은 각각 탄소 펠트, 탄소 천, 탄소 봉, 탄소 종이 및 탄소 솔을 포함하는 탄소 재료, 전극실 사이의 분리막은 양이온 교환막(CEM), 복합막, 나일론막 또는 음이온 교환막(AEM)으로 미생물 연료전지를 구성하는 것을 특징으로 하는 방법.
- 제 1 항에 있어서, 미생물 연료전지(MFC)가 2 개 이상 구비되는 것을 특징으로 하는 방법.
- 제 1 항 또는 제 5 항에 있어서, 제거되는 중금속이 Cr6+, Cr3+, As5+ 또는 As3+인 것을 특징으로 하는 방법.
- 산화전극과 환원전극, 그리고 양 전극실 사이의 분리막을 구비한 미생물 연료전지(MFC; microbial fuel cells)에서 혐기성 미생물을 이용하여 귀금속 함유 폐수로부터 귀금속을 회수하는 동시에 전력을 생산하는 방법.
- 제 7 항에 있어서, 회수되는 귀금속이 Ag+, Au2+, Au+, Pd4+, Pd2+, Pt4+, Pt2+, Rh2+, Ir3+ 또는 Re3+인 것을 특징으로 하는 방법.
- 제 7 항에 있어서, 혐기성 미생물이 다음 중에서 선택된 적어도 하나인 것을 특징으로 하는 방법: Alpha-proteobacteria, Beta-proteobacteria, Delta-proteobacteria, Clostridia, Shewanella oneidensis MR-1, Shewanella oneidensis DSP-10, Shewanella putrefaciens SR-21, IR-1, MR-1, Geobacter sulfurreducens, Geobacter sulfurreducens KN400, Ochrobactrum anthropi YZ-1, Brevibacillus sp. PTH1, E. coli K12 HB101, Aeromonas hydrophila, Corynebacterium sp. MFC03, Leptothrix discophora SP-6, Bacillus licheniformis, Bacillus thermoglucosidasius, Spirulina platensis, Bacillus subtilis, Enterococcus gallinarum, Acetobacter aceti, Gluconobacter roseus.
- 제 7 항에 있어서, 산화전극 및 환원전극은 각각 탄소 펠트, 탄소 천, 탄소 봉, 탄소 종이 및 탄소 솔을 포함하는 탄소 재료, 전극실 사이의 분리막은 양이온 교환막(CEM), 복합막, 나일론막 또는 음이온 교환막(AEM)으로 미생물 연료전지를 구성하는 것을 특징으로 하는 방법.
- 제 7 항에 있어서, 미생물 연료전지(MFC)가 2 개 이상 구비되는 것을 특징으로 하는 방법.
- 산화전극과 환원전극, 그리고 양 전극실 사이의 분리막을 구비한 미생물 연료전지(MFC; microbial fuel cells)에서 혐기성 미생물을 이용하여 수은 함유 폐수로부터 Hg2+를 금속 Hg나 Hg2Cl2의 고형 침전물이나 침적물로서 제거하는 동시에 전력을 생산하는 방법.
- 제 12 항에 있어서, 혐기성 미생물이 다음 중에서 선택된 적어도 하나인 것을 특징으로 하는 방법: Alpha-proteobacteria, Beta-proteobacteria, Delta-proteobacteria, Clostridia, Shewanella oneidensis MR-1, Shewanella oneidensis DSP-10, Shewanella putrefaciens SR-21, IR-1, MR-1, Geobacter sulfurreducens, Geobacter sulfurreducens KN400, Ochrobactrum anthropi YZ-1, Brevibacillus sp. PTH1, E. coli K12 HB101, Aeromonas hydrophila, Corynebacterium sp. MFC03, Leptothrix discophora SP-6, Bacillus licheniformis, Bacillus thermoglucosidasius, Spirulina platensis, Bacillus subtilis, Enterococcus gallinarum, Acetobacter aceti, Gluconobacter roseus.
- 제 12 항에 있어서, 산화전극 및 환원전극은 각각 탄소 펠트, 탄소 천, 탄소 봉, 탄소 종이 및 탄소 솔을 포함하는 탄소 재료, 전극실 사이의 분리막은 양이온 교환막(CEM), 복합막, 나일론막 또는 음이온 교환막(AEM)으로 미생물 연료전지를 구성하는 것을 특징으로 하는 방법.
- 제 12 항에 있어서, 미생물 연료전지(MFC)가 2 개 이상 구비되는 것을 특징으로 하는 방법.
- 제 12 항에 있어서, 수은 함유 폐수는 초기 pH를 2 내지 4.8로 조절하는 것을 특징으로 하는 방법.
- 제 12 항에 있어서, 희석한 염산을 사용하여 초기 pH를 조절하는 것을 특징으로 하는 방법.
- 제 12 항에 있어서, 수은 함유 폐수는 초기 Hg2+ 농도를 25 내지 100 ㎎/L로 조절하는 것을 특징으로 하는 방법.
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US20140083933A1 (en) | 2014-03-27 |
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CN103153883A (zh) | 2013-06-12 |
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