본 연구에서는 산화된 피복관으로부터 염소화 공정을 통해 Zr을 선택적으로 회수하기 위한 연구의 일환으로, 단면이 개방 된 ZIRLO 피복관의 염소화 반응 속도식을 열중량분석기를 이용하여 분석하였다. 실험을 통해 산화된 ZIRLO 피복관은 400 도 염소화 조건에서 염소 기체와 반응하지 않는 것으로 확인되었다. 하지만 피복관 한쪽 혹은 양쪽 끝의 새로운 단면이 개방 될 경우 ZIRLO의 염소화 반응이 가능함을 확인하였고 반응을 완료하기까지 8 시간이 소요되었다. 이는 반응 완료까지 7 시 간이 소요된 산화되지 않은 피복관에 비하여 반응시간이 14% 증가한 것이다. Sharp-Hancock 식을 이용하여 단면이 개방된 ZIRLO 피복관과 염소 기체의 반응을 모사하기 위한 구조함수를 도출하였으며, 부피축소 모델이 본 연구 조건에서 가장 적 합한 구조 함수로 확인되었다. 또한, 본 연구를 통해 ZIRLO 피복관의 표면이 산화되어 있는 조건에서도 단면노출을 통해 염 소화 공정에 적용이 가능함을 확인하였다.

본 연구에서는 산화 공정이 Zircaloy-4 (Zry-4) 피복관의 염소화 반응 속도에 미치는 영향을 연구하기 위하여 Zry-4 피복관의 염소화 반응 실험을 수행하였다. 2시간 마다 반응 생성물을 회수하며 총 6 시간 동안 염소화 반응 실험을 수행하였고, 이를 통해 500도에서 10 시간 동안 산화된 Zry-4의 경우 초기 0-2 시간 구간에서 반응 속도가 현저히 저하되는 것을 확인하였다. 반응 잔류물은 fresh Zry-4와 산화된 Zry-4에서 각각 초기무게의 0.95, 1.65wt%로 확인되었다. 회수된 Zr의 순도는 두 경우 모두 99.61wt%로 동일하였다. 반응 속도의 정량적 분석을 위해 피복관의 반응 시간을 0.5, 1, 2, 4 시간인 경우에 대해 실험을 수행하였다. 실험 결과 분석을 통해 fresh Zry-4의 경우 전 영역에 걸쳐 23.35wt%/h의 단위 시간당 무게감소를 확인할 수 있었고, 산화된 Zry-4의 경우 반응 속도가 두 영역으로 나뉘는 것을 확인하였다. 산화된 Zry-4의 무게 감소 속도는 0-20wt% 영역에서는 17.12wt%/h, 20-100wt% 영역에서는 27.16wt%/h으로 나타났다.

본 논문에서는 염소화 반응을 통해 Zircaloy-4 (Zry-4) 피복관으로부터 Zr의 회수 연구를 수행하였다. 피복관의 Zr을 전부 ZrCl4로 전환시키기 위해, Zry-4 피복관을 380도에서 70 cc/min Cl2 + 70 cc/min Ar 기체를 이용하여 8시간 동안 반응시켰다. 피복관의 초기 무게는 51.7 g이었으나, 8 시간 반응 후에는 0.49 g만이 잔류물로 남아있는 것을 확인하였는데 이는 초기 무게의 0.95wt%에 해당하는 값이다. 반응 생성물의 무게는 121.7 g 이었으며, Zr의 순도는 99.80wt%였다. 주요 불순물로는 Fe (0.18wt%)와 Sn (0.02wt%)를 확인할 수 있었다. 실험 결과를 통해 확인한 Zr의 회수율은 96.95wt%였으며, 실험상손실은 2.34wt%로 확인되었다. 반응 잔류물의 관찰을 통해 염소화 반응이 길이 방향으로 주로 일어나며, 표면의 산화층이 반응 잔류물로 남는다는 것을 확인할 수 있었다. 본 연구를 통해 확인된 Zr의 높은 순도와 회수율은 염소화 공정이 폐 피복관 처리 방법으로 매우 유망한 기술임을 의미한다고 볼 수 있다.

It has been confirmed that some Trihalomethanes (THMs) suspected as carcinogens, can be formed during chlorination for water supply through the reaction of chlorine and humic substances in water. The electrochemical characteristics on activated carbon fiber filter (ACF) electrode were investigated to remove the THMs in the chlorination process of drinking water. The electrochemical removal efficiency depended on the applied voltage and flow rate. In this study, the best result showed that the removal efficiency of THMs was higher than 99%.

This study was conducted to recover the aluminum from water treatment plant sludge containing alumina. The optimum reaction conditions about chlorination of sludge with NH4Cl are as follows: the weight ratio of sludge to NH4Cl is 4, the reaction time is 60min, and the temperature is 300℃. And the result of leaching time test showed that the highest yield of alumina at 160℃ was 96% but the result of leaching test at 160℃ was little better than that of leaching test at 100℃ while the leaching concentration of HCl was 4N. The optimum reaction conditions of chlorinated sludge with NH4Cl, gave the highest yield of 95.41% based on aluminum.

사염화우라늄 제조를 위해 염소가스와 탄소를 이용한 이산화우라늄의 염소화반응에 대하여 연구하였다. 이론적측면에서 열화학적 자료를 이용한 계산을 통하여 일어날 수 있는 반응들을 확인하였으며, 염소화반응이 진행되는 동안 초래될 현상에 대하여 검토하였다. 실험결과로 부터 반응온도, 반응시간 및 질소가스 주입비율이 사염화우라늄 제조에 미치는 영향을 정량적으로 평가하였다. 순수한 이산화우라늄을 사용한 사염화우라늄 제조공정에서의 적절한 반응시간과 반응온도는 각각 약 2시간과 500˚C-700˚C범위였으며, 질소가스의 적정 주입량은 염소가스의 약 50%로 나타났다.

사염화우라늄을 제조하기 위한 가장 효율적인 반응계는 이산화우라늄, 염소가스와 탄소분말이다. 여러 가지 실험변수 가운데 이산화우라늄의 염소화반응에 사용된 염소가스 주입량과 탄소의 양이 사염화우라늄 제조에 미치는 영향에 관하여 연구하였다. 각각의 실험변수들에 대한 전화율과 휘발률 계산을 통해 효율적인 반응을 위한 적정 염소가스 주입량과 탄소의 양을 구하였고, 이산화우라늄의 증가함에 따라 직접접촉에 의한 기체-고체반응에서는 전화율과 휘발률은 증가했으나 이후 과량을 첨가함에 따라 감소하였고, 용융염내의 기체-액체반응에서는 전화율의 미미한 증가와 휘발률의 감소를 확인하였가. 염소주입량이 증가함에 따라 전화율과 휘발률이 증가했으며, 과량의 염소가수 주입시 고이온가 염화물의 생성량이 증가하였다.

In this research, heavy metals and T-P removal characteristics of plated wastewater are derived using BPC(Break Point Chlorination) process. AA sedimentation pond outflow(Influence) was evaluated for the removal efficiency of heavy metal(Ni) and T-P at a reaction time of 25 minutes by NaOCl input volume(9, 11, 13 and 15 mL). In the case, the higher the NaOCl input volumes, the higher the ORP values were maintained and the higher the removal efficiency tended to be. On the other hand, T-P was judged to have a low relationship between the ORP value and the removal efficiency. In addition, the efficiency of removal heavy metals and T-P in the plated wastewater by injecting 10 mL, 15 mL, 20 mL and 25 mL NaOCl, increased as the amount of NaOCl injected increased, the amount of NaOH input for pH increased. It was found that suspended solid in effluence also increased. It was also observed that the color of the plating wastewater changed from yellowish green to green to charcoal gray to black as the amount of NaOCl injected increased. Treatment characteristics of the reaction time, the longer the reaction time with the substance to be treated after the input of NaOCl, the more the heavy metal removal efficiency tended to increase. Through XRF analysis of the sludge, the constituents in the sludge such as NaCNO, CNCl, Na3PO4, CrO4, 2Na2CrO4 and 2NaNO3 will be analyzed in detail, and the mechanisms of the reaction between the plated wastewater and the complex compound will be elucidated.

Formation of disinfection by-products (DBPs) including trihalomethans (THMs) and haloacetic acids (HAAs) from chlorination of six different species (Chlorella vulgaris, Scenedesmus sp., Anabaena cylindrical, Microcystis aeruginosa, Asterionella formosa and Aulacoseira sp.) of algal extracellular organic matter (EOM). The EOM characteristics evaluation of six algal species reaching at the stationary phase in the growth curve showed most of its SUVA254 showed below 1 and this means hydrophilic organic matter is much higher than hydrophobic organic matter. Chloroform formation potential (CFFP), dichloroacetic acid formation potential (DCAAFP) and trichloroacetic acid formation potential (TCAAFP) were mainly composed of THMFP and HAAFP in the EOM of various algal species. In the case of THMFP/DOC and HAAFP/DOC values, EOM of blue-green algae has appeared highest and EOM of green algae and diatom in order. THMFP/DOC was higher than HAAFP/DOC in EOM of blue-green algae. In comparison of formation potential by unit DOC composed of HAAFP in algal species EOM, DCAAFP/DOC was 1.5 times to 7.5 time higher than TCAAFP/DOC in the EOM of blue-green algae, while DCAAFP/DOC was found to be relatively high compared to TCAAFP/DOC in the EOM of green algae and diatom.

This study was carried out to investigate the characteristics of disinfection by-products (DBPs-trihalomethanes (THMs), haloacetic acids (HAAs) and haloacetonitriles (HANs) formation in chlorination of principal raw waters used for drinking water on Jeju Island, Korea. The domestic water supply of other area and humic acid solution (HA) were used as a reference point. The effects of chlorine contact time, solution temperature and pH on DBPs formation potential (DBPFP) were investigated for raw waters. In addition, the effect of Br- was studied for HA. The DBPFP (THMFP, HAAFP and HANFP) were increased with increasing chlorine contact time. Comparing the individual DBPFPs for raw waters, they decreased in the order of HAAFP > THMFP ≥ HANFP. As the solution temperature was increased, the THMFP, HAAFP and HANFP increased. With increasing the solution pH, the THMFP was increased, but HAAFP and HANFP were decreased. With the addition of 0.3 mg/L Br- for HA, the DBPFP was increased and the major chemical species changed: from trichloromethane to dibromochloromethane and tribromomethane for THMs; from dichloroacetic acid and trichloroacetic acid to tribromoacetic acid for HAAs; and from dichloroacetonitrile to dibromoacetonitrile for HANs.

The chlorination pattern of naphthalene vapor when passed through a 1 cm particle bed of 0.5% (mass) copper (II) chloride (CuCl2) mixed with silicon dioxide (SiO2) was studied. Gas streams consisting of 92% (molar) N2, 8% O2 and 0.1% naphthalene vapor were introduced to an isothermal flow reactor containing the CuCl2/SiO2 particle bed. Chlorination of naphthalene was studied from 100 to 400 °C at a gas velocity of 2.7 cm/s. Mono through hexachlorinated naphthalene congeners were observed at 250 °C whereas a broader distribution of polychlorinated naphthalenes (PCNs) including hepta and octachlorinated naphthalenes was observed at 300 °C. PCN production was peak at 250 °C with 3.07% (molar) yield, and monochloronaphthalene (MCN) congeners were the major products at two different temperatures. In order to assess the effect of a residence time on naphthalene chlorination, an experiment was also conducted at 300 °C with a gas velocity of 0.32 cm/s. The degree of naphthalene chlorination increased as a gas velocity decreased.

Formation of disinfection by-products (DBPs) including trihalomethans (THMs), haloacetic acid (HAAs), haloacetonitriles (HANs) and others from chlorination of algogenic organic matter (AOM) of Microcystis sp., a blue-green algae. AOM of Microcystis sp. exhibited a high potential for DBPs formation. HAAs formation potential was higher than THMs and HANs formation potential. The percentages of dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) formation potential were 43.4% and 51.4% in the total HAAs formation potential. In the case of HANs formation potential, percentage of dichloroacetonitrile (DCAN) formation potential was 97.7%. Other DBPs were aldehydes and nitriles such as acetaldehyde, methylene chloride, isobutyronitrile, cyclobutanecarbonitrile, pentanenitrile, benzaldehyde, propanal, 2-methyl, benzyl chloride, (2-chloroethyl)-benzene, benzyl nitrile, 2-probenenitrile and hexanal.

최근 수자원 내에서 미량오염물질이 번번히 발견되고 있고(Lee, 2012) 이중 항생제 내성도 하나의 미량 오염물질로 간주 될 수 있다. 수자원내 항생제 내성 유전자는 환경 내 항생제 내성균의 증가를 일으켜 궁극적으로 병원균 내의 항생제 내성균의 증가를 초래할 수 있다(Kim et al., 2010). 소독은 병원성 미생물 및 잠재적 위해성을 가진 미생물을 불활성화 시키기 위한 공정이며, 수처리 공정에서 소독방법은 염소소독, 오존, UV 또는 전자빔이 선택되어 왔다(Gehr et al., 2003). 본 연구에서는 강력한 산화 기법중의 하나인 오존 소독과 전통적 기법인 염소소독을 비교하는데 목적이 있다.

The formation characteristics of trihalomethanes (THMs) and haloacetic acids (HAAs) were investigated in chlorination of raw water of different organic mallet characteristics. The samples used in this study were hydrophobic (N-HPO) and hydrophilic fraction (N-HPI) (which were concentrated and separated from Nakdong river water), and humic acid (HA) (which is known as a strong hydrophobic acid) as a reference organic matter, the specific UV absorbance (SUVA) of which was 2.19, 1.15 and 7.92, respectively. With increasing chlorine contact time, THMFP and HAAFP (the formation potential of THMs and HAAs) increased, but their increase was different depending on the organic mallet characteristics (i.e., for N-HPI, THMFP was higher than HAAFP, but the inverse result was obtained for N-HPO and HA and the ratio between them was greater for HA), and the mainly formed chemical species were CHCI3 in case of THMs and dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) in case of HAAs for N-HPO and HA (and the ratios of CHCI3 to total THMs and DCAA and TCAA to total HAAs for HA were higher than those for N-HPO), but for N-HPI, the ratio of brominated THMs was a little higher than that of CHCI3 and the ratio of DCAA and TCAA to total HAAs was lower than that of N-HPO, although they are main chemical species in case of HAAs. Comparing THMFP and HAAFP with the increase in bromide concentration added with those in not adding it, the former increased greatly and its increase was higher for the organic mallet with stronger hydrophobicity, but the latter was lower for N-HPO and N-HPI and was similar for HA. The main chemical species with increasing bromide concentration were CHBt3 in case of THMs regardless of organic matter characteristics, and dibromoacetic acid (DBAA) for N-HPO and N-HPI, DBAA and tribromoacetic acid (TBAA) for HA in case of HAAs. With increasing reaction temperature and pH, THMFP and HAAFP increased for the former, but for the latter, THMFP increased and HAAFP decreased, although the rate of increase or decrease was different with organic mallet characteristics.

The effective removal of microcystins by chlorination was investigated on a laboratory scale. With an initial chl.a concentration of more than 1,000 μg /ℓ, the required chlorine dose for the effective removal of microcystins from the raw water was more than 8.0 mg/ℓ. Whereas, a chlorine dose of 3.0 mg/ℓcould effectively remove microcystins from raw water containing a chl.a concentration of less than 1,000 μg /ℓ. The microcystin removal was more effective below pH 8.0, plus the optimum pH range was unrelated to the concentration of toxic algal material. Although chlorination is one of the most effective methods for reducing the toxin from blue-green algae, it causes cell lysis and toxin release. However, it was demonstrated that the released cell lysates and toxins could be effectively removed by a higher dose of the oxidant. The highest removal efficiency of dissolved microcystins(initial concentration: 280 μg L \^ -1/) was with a chlorine dose of 5.0 mg/ℓ.