본 연구는 전기투석과 용매추출을 융합한 희유금속 회수 공정에서 분리막과 음이온교환막의 개질을 통해 유기상 과 수상에 대한 분리막의 낮은 젖음성 및 AEM을 통한 수소이온 투과로 인한 금속이온의 회수 효율 감소를 개선하였다. 구체 적으로, 분리막 표면 중 한면은 polydopamine (PDA) 통한 친수성 개질, 다른 면은 SiO2 또는 graphene oxide를 통한 친유성 개질을 함으로써 분리막의 젖음성을 개선하였다. 또한, 음이온교환막의 표면을 polyethyleneimine, PDA, poly(vinylidene fluoride) 등을 이용, 개질해 수분 흡수(Water uptake) 감소 및 기공구조 변화를 통해 수소이온 수송을 억제해 수소이온 투과를 억 제할 수 있다. 개질된 막 표면 형상과 화학적 특성 및 조성은 주사전자현미경과 푸리에변환 적외선 분광법을 통해 확인되었 고, 이를 구리 이온 회수 시스템에 적용해 향상된 추출 및 탈거 효율과 수소이온 수송 억제능을 확인하였다.

This study used a packed column reactor and a horizontal flow mesh reactor to examine the removal of copper ions from aqueous solutions using pine bark, a natural adsorbent prepared from Korean red pine (Pinus densiflora). Both equilibrium and nonequilibrium adsorption experiments were conducted on copper ion concentrations of 10mg/L, and the removals of copper ions at equilibrium were close to 95%. Adsorption of copper ions could be well described by both the Langmuir and Freundlich adsorption isotherms. The bark was treated with nitric acid to enhance efficiency of copper removal, and sorption capacity was improved by about 48% at equilibrium; mechanisms such as ion exchange and chelation may have been involved in the sorption process. A pseudo second-order kinetic model described the kinetic behavior of the copper ion adsorption onto the bark. Regeneration with nitric acid resulted in extended use of spent bark in the packed column. The horizontal flow mesh reactor allowed approximately 80% removal efficiency, demonstrating its operational flexibility and the potential for its practical use as a bark filter reactor.

본 연구에서는 하이드라진 기조의 환원성 제염제를 이용한 마그네타이트 산화물의 용해를 다루고 있다. 마그네타이트로부터의 Fe(Ⅱ) 및 Fe(Ⅲ)의 용해는 protonation, surface complexation 및 reduction에 의해 지배를 받는다. 하이드라진과 황산은 산소결합을 파괴하거나 Fe(Ⅲ)이온을 Fe(Ⅱ)이온으로 환원시키기 위한 수소 및 전자를 각각 제공하게 된다. 속도론적 관점에서 보다 효율적인 용해를 위하여 다수의 전이금속의 영향을 분석하여 Cu(Ⅱ) 이온이 효과적임을 확인한 바 있다. Cu(Ⅰ) 이온은 Cu(Ⅱ) 이온으로 산화되는 동안 전자를 방출하여 Fe(Ⅲ) 이온을 환원시키고 다시 하이드라진에 의해 Cu(Ⅰ) 이온으로 환원되게 된다. 본 연구를 통해 제염용액에 매우 적은 양의 구리 이온 (약 0.5 mM)을 첨가함에 따라 평균 40% 용해속도가 향상됨을 확인하였고, 특히 특정 조건에서는 70% 이상 용해속도가 향상 됨을 확인하였다. 구리 이온이 하이드라 진과 배위결합을 이루는 지에 대해서는 아직 명확하지 않으나, 분명한 것은 Cu(Ⅱ)/H+/ N2H4으로 이루어진 제염제는 효과적인 용해성능을 가지고 있다는 것이다.

탄소전극과 이온교환막을 결합한 축전식 탈염(CDI)을 이용하여 셀 구조와 셀 전위에 따른 구리 이온의 제거 특성을 연구하였다. 탄소전극과 이온교환막의 결 합 방식에 따라 4종류의 셀에 대해 실험한 결과 양이온, 음이온교환막을 결합한 셀(MCDI)에서 구리 이온의 제거율과 전하효율이 가장 높은 것으로 나타났다. 셀 전위에 따른 영향을 분석한 결과 0.6 V 이하에서는 전기이중층에 의한 전기 흡착(electrosoprtion)에 의해, 그리고 0.6 V 이상에서는 구리 이온의 전착 (electrodepostion)반응에 의해 구리 이온이 제거됨을 확인하였다. 또한 1.2 V 이상에서는 물이 전기분해되어 전하효율이 감소하였다. MCDI 셀의 운전결과 전하효율은 80% 정도로 구리 이온을 포함한 중금속 이온을 제거하는데 효과적인 것으로 판단되었다.

탄소전극과 이온교환막을 결합한 막결합 축전식 탈염(MCDI) 셀을 이용하여 환원전위가 다른 Na+과 Cu2+ 이온 혼합용액에서 Cu2+ 이온의 제거 특성을 연구 하였다. MCDI 셀에 일정한 전류밀도(1.5 mA/cm2)를 공급하면서 탈염을 실시한 결과 Cu2+ 이온은 일정한 제거속도를 유지하였지만 Na+ 이온의 제거량은 시간에 따라 감소하였다. 이는 Cu2+ 이온은 전착반응에 의해, Na+ 이온은 전기흡착 반응에 의해 제거되기 때문인 것으로 판단된다. Cu2+ 이온의 당량비가 0.14, 0.38, 0.50인 혼합용액을 탈염한 결과 제거된 이온 중 Cu2+ 이온의 당량비는 각 각 0.27, 0.60, 0.79로 나타났다. 이를 통해 Cu2+ 이온의 전착반응에 의해 혼합용 액에서 Cu2+ 이온의 제거율을 증가시킬 수 있음을 알 수 있었다.

본 연구는 인쇄회로기판(PCB) 제조 시 에칭공정에서 발생되는 구리이온(Cu+2)을 고농도로 함유한 황산 폐에칭액을 NF 막분리법을 사용하여 에칭액 회수와 구리이온 처리를 효율적으로 수행하기 위한 NF 막여과 공정의 운전 조건을 설정하기 위한 기본 자료를 확보하는데 있다. 이를 위해 미국 Koch사의 SelRO MPS-34 4040 NF 막을 대상으로 구리이온을 고농도(5~25 g/L)로 함유한 모의 황산 폐에칭액의 회분식(dead-end) 나노여과 실험을 수행하여 투과 플럭스와 구리이온의 총괄 배제도를 측정하였다. 이 결과 황산용액에의 막 보관기간이 길수록, 황산용액의 pH가 낮을수록 황산에 의한 NF 막의 손상이 더 크게 발생하여 순수 투과 플러스가 증가하였다. 황산 폐에칭액의 투과 플럭스는 황산용액 내 구리이온의 농도가 증가할수록 막 표면에의 구리이온 농축(농도분극)의 증가에 따라 감소하였으며, 구리이온의 배제도는 구리이온의 농도가 높을수록, pH가 낮을수록, 황산용액 내의 막 보관기간이 길수록 낮아져 초기 37%에서 최소 15% 수준으로까지 감소하였다.

In this study, PAN-SZ (polyacrylonitrile scoria zeolite) beads were prepared by immobilizing Na-A zeolite (SZ-A) synthesized from Jeju volcanic rocks (scoria) on the polymer PAN. FT-IR and TGA analysis results confirmed that the SZ-A was immobilized in the PAN-SZ beads. SEM images showed that the PAN-SZ beads are a spherical shape with 2 mm diameter and exhibit a porous inner structure inside the bead. The most suitable mixing ratio of PAN to SZ-A as the adsorbent for removing Sr ions was PAN/SZ-A = 0.2 g/0.3 g. The adsorption kinetic data for Cu and Sr ions were fitted well with the pseudo-second-order model. The Cu and Sr ion uptakes followed a Langmuir isotherm model and the maximum adsorption capacities at 20℃ were 84.03 mg/g and 75.19 mg/g, respectively. The amount of Sr ion adsorbed by SZ-A on the PAN-SZ beads was about 160 mg/g, which was similar to that adsorbed by SZ-A powder. Thus, the PAN-SZ beads prepared in this study are considered to be effective adsorbents for removing metal ions in aqueous solutions.

PVA-D2EHPA/TOPO beads containing two extractants, di-(2-ethylhexyl) phosphoric acid (D2EHPA) and trioctylphoshine oxide (TOPO) were prepared for the removal of copper ions from aqueous solution. The prepared PVA-D2EHPA/TOPO beads were characterized by SEM and FT-IR. The removal characteristics of copper ions by PVA-D2EHPA/TOPO beads was investigated using batch and continuous systems. In batch experiments, the maximum removal capacity calculated from Langmuir isotherm model was 18.6 mg/g and the optimal pH was in the range of 4.5 ∼6. The continuous experiments showed that the removal capacity of copper ions increased with increasing inlet copper ion concentrations and bed heights, but decreased with increasing inlet flow rates.

The adsorption performance of cupper and zinc ions(Cu2+ and Zn2+) in aqueous solution was investigated by an adsorption process on reagent grade Na-A zeolite(Z-WK) and Na-A zeolite (Z-C1) prepared from coal fly ash. Z-C1 was synthesized by a fusion method with coal fly ash from a thermal power plant. Batch adsorption experiment with Z-C1 was employed to study the kinetics and equilibrium parameters such as initial metal ions concentration and adsorption time of the solution on the adsorption process. Adsorption rate of metal ions occurred rapidly and adsorption equilibrium reached at less than 120 minutes. The kinetics data of Cu2+ and Zn2+ ions were well fitted by a pseudo-second-order kinetics model more than a pseudo-first-order kinetics model. The equilibrium data were well fitted by a Langmuir model and this result showed Cu2+ and Zn2+ adsorption on Z-C1 would be occupied by a monolayer adsorption. The maximum adsorption capacity(qmax) by the Langmuir model was determined as Cu2+ 99.8 mg/g and Zn2+ 108.3 mg/g, respectively. It appeared that the synthetic zeolite, Z-C1, has potential application as absorbents in metal ion recovery and mining wastewater.

Adsorption on goethite of individual component from a solution containing phosphate, sulfate, or copper ion was investigated. Competitive adsorption in the binary and ternary solution systems composed of phosphate, sulfate, and copper ions was also investigated. In competitive adsorption systems with phosphate and sulfate ions, the presence of phosphate ion reduced the adsorption of sulfate ion largely. On the other hand, the presence of sulfate ion caused only a small decrease in phosphate adsorption. This result suggests that phosphate ion is a stronger competitor for adsorption on goethite than sulfate ion, which is consistent with the higher affinity of phosphate for the surface compared to sulfate ion. Compared to the results from single-sorbate systems, adsorption of copper ion in the binary system of sulfate ion and copper ion was found to be enhanced in the presence of sulfate ion. Addition of sulfate ion to the binary system of copper ion and phosphate ion resulted in a small enhancement in copper sorption. This result implies that the presence of sulfate ion promotes adsorption of the ternary complex FeOHCuSO4. The adsorption isotherms could be well described by the Langmuir adsorption equation.

Adsorption of phosphate, sulfate, and copper ion to goethite was investigated. Goethite was prepared in the alkaline solution. In the single adsorbate systems, the final equilibrium plateau reached within 20 min. The adsorption isotherms of the individual ions could be well described by the Langmuir equation. The maximum adsorption capacities (qmax) were calculated as 0.483 mmol/g and 0.239 mmol/g at pH 3 for phosphate and sulfate ion, and 0.117 mmol/g at pH 6 for copper ion, respectively. In competitive adsorption system with phosphate and sulfate, phosphate ion was a stronger competitor for adsorption on goethite than sulfate ion, which was consistent with higher affinity of phosphate ion for the surface compared to sulfate ion. The existence of sulfate ion enhanced the adsorption of copper ion but the adsorption of sulfate was inhibited when copper ion was present.

To find heavy metal-specific effects on the photosynthetic apparatus of higher plants, we investigated effects of CuCl_2, HgCl_2 and ZnCl_2 on electron transport activity and chlorophyll fluorescence induction kinetics of chloroplasts isolated from barley seedlings. Effects on some related processes such as germination, growth and photosynthetic pigments of the test plants were also studied. Germination and growth rate were inhibited in a concentration-dependent manner by these metals. Mercury was shown to be the most potent inhibitor of germination, growth and biosynthesis of photosynthetic pigments of barley plants. In the inhibition of electron transport activity, quantum yield of PSⅡ, and chlorophyll fluorescence induction kinetics of chloroplasts isolated from barley seedlings, mercury chloride showed more pronounced effects than other two metals. Contrary to the effects of other two metals, mercury chloride increased variable fluorescence significantly and abolished qE in the fluorescence induction kinetics from broken chloroplasts of barley seedlings. This increase in variable fluorescence is due to the inhibition of the electron transport chain after PSⅡ and the following dark reactions. The inhibition of qE could be attributed to the interruption of pH formation and de-epoxidation o1 violaxathin to zeaxanthin to thylakoids by mercury. This unique effect of mercury on chlorophyll fluorescence induction pattern could be used as a good indicator for testing the presence and/or the concentration of mercury in the samples contaminated with heavy metals