본 총설은 분리막기술이 적용된 수소생산에 대한 개론으로, 특히, 암모니아를 수소운반체로 이용하는 수소생산에 대한 연구결과를 중점적으로 서술하였다. 암모니아를 수소운반체로 적용한 수소생산은 추가적인 탄소생성이 없다는 점 외에 여러 측면에 있어 이점이 있다. 많은 연구들이 고순도 수소 분리 및 생산을 위한 분리막 개발을 위해 진행되고 있으며, 이들 중 팔라듐을 기본으로 한 분리막(예를 들어, 다공성 세라믹 또는 다공성 금속 지지체와 팔라듐 합금의 얇은 선택층으로 이루어진 분리막)에 대한 연구가 활발하다. 반면에, 효율적인 암모니아 분해를 위해서는 주로 루테늄 촉매가 적용되고 있으며, 루테늄과 지지체 및 촉진제로 이루어진 루테늄에 기반을 둔 촉매에 대한 연구발표가 다수 존재한다. 수소생산을 위한 분리막 반응기 형태로는 충전층, 유동층, 그리고 마이크로반응기 등이 있으며, 이들의 최적화 및 원활한 물질전달 연구는 현재진행형 이다. 또한, 높은 암모니아 분해율, 고순도 수소생산 및 높은 수소생산율을 얻기 위해 분리막과 촉매의 다양한 조합에 대한 연구 및 분리막과 촉매의 역할을 동시에 구현할 수 있는 분리막에 대한 연구가 발표되고 있다.
This study is focused on manganese (Mn(II)) removal by potassium permanganate (KMnO4) in surface water. The effects of bicarbonate on Mn(II) indicated that bicarbonate could remove Mn(II), but it was not effectively. When 0.5 mg/L of Mn(II) was dissolved in tap water, the addition of KMnO4 as much as KMnO4 to Mn(II) ratio is 0.67 satisfied the drinking water regulation for Mn (i.e. 0.05 mg/L), and the main mechanism was oxidation. On the other hand, when the same Mn(II) concentration was dissolved in surface water, the addition of KMnO4, which was the molar ratio of KMnO4/Mn(II) ranged 0.67 to 0.84 was needed for the regulation satisfaction, and the dominant mechanisms were both oxidation and adsorption. Unlike Mn(II) in tap water, the increasing the reaction time increased Mn(II) removal when KMnO4 was overdosed. Finally, the optimum conditions for the removals of 0.5 - 2.0 mg/L Mn(II) in surface water were both KMnO4 to Mn(II) ratio is 0.67 - 0.84 and the reaction time of 15 min. This indicated that the addition of KMnO4 was the one of convenient and effective methods to remove Mn(II).
First of all, Fe or/and Mn immobilized granular activated carbons (Fe-GAC, Mn-GAC, (Fe, Mn)-GAC) were synthesized and tested to remove arsenate (As(V)). The results in batch test indicated that Fe-GAC removed As(V) effectively, even though the surface area of Fe-GAC was reduced largely. Moreover, adsorption isotherm test indicated that the experimental data fit well with Langmuir model and the maximum adsorption capacity (qmax) of Fe-GAC for As(V) was 3.49 mg g-1, which was higher than GAC (2.24 mg g-1). In column test, the simulated water, which consisted of As(V), Fe(III), Mn(II) and Ca(II) in tap water, was used. Fe-GAC column with 1 hr of pre-washing time treated As(V) effectively while GAC column removed Fe(III) better than Fe-GAC column. Moreover, the increasing pre-washing time from 1 to 9 hour in Fe-GAC column enhanced Fe(III) removal with little negative impact of As(V) removal. Mostly, the column filled with Fe-GAC and GAC (i.e. the mass ratio of Fe-GAC:GAC = 2:8) showed the higher treatability of both As(V) and Fe(III), even it operated with 1 hr pre-washing time.
The characteristics of filter/adsorber granular activated carbon (F/A GAC) were investigated by measuring various parameters, which include surface area, pore volume, abrasion number, floater, and water-soluble ash. The correlation between parameters was also evaluated. Moreover, rapid small-scale column test (RSSCT) was conducted for adsorption characteristics. Thirteen F/A GAC were tested, and the average values of abrasion number and water-soluble ash were 88.9 and 0.15%, respectively. F/A GAC with the larger external surface area and greater mesopore volume had the lower abrasion number, which indicated that it was worn out relatively easily. Water-soluble ash of coconut-based GAC (about 2.6%) was greater than that of coal-based GAC (less than 1%), and the pH of solution was increased with GAC, which had the higher water-soluble ash. On the other hand, floater of thirteen F/A GAC was divided as two groups, which one group had relatively higher floater (2.7~3.5%) and the other group had lower floater (approximately 0.5%). The results of RSSCT indicated that coconut-based GAC (i.e. relatively higher water-soluble ash) had less adsorption capacity. Moreover, adsorption capacity of coal-based GAC with larger surface area and greater mesopore volume was superior to others.
The effect of activated carbon particle diameter (i.e. US sieve No. 8×10 (dp ≈ 2.19 mm), 18×20 (dp ≈ 0.92 mm), 50×60 (dp ≈ 0.27 mm) and 170×200 (dp ≈ 0.081 mm)) on caffeine adsorption is investigated. BET surface area was increased with decreasing particle diameter (dp), and caffeine adsorption rates increased with decreasing dp. Moreover, pseudo-second order model is predicted the experimental data more accurately than pseudo-first order model, and the fastest rate constant (k2) was 1.7 g mg-1 min-1 when dp was 0.081 mm. Surface diffusion coefficient (Ds) was decreased with decreasing dp based on the minimum sum of square error (SSE). Practically, certain ranges of Ds are acceptable with high reliability (R2) and it is determined that the effect of dp on Ds is unclear. The effect of pH on caffeine adsorption indicated the dependency of m/L ratio (mass liquid ratio) and pHPZC. The pHPZC (i.e. 7.9 ± 0.2) was not affected by dp. The higher caffeine adsorption at pH 4 and pH 7 than at pH 10 is due to pHPZC, not pka of caffeine.
Two step rapid filter system as a pre-treatment for the injected water into aquifer storage and recovery (ASR) in Korea was developed to reduce physical blockage and secure the volume of the injected water. First, single rapid sand filters with three different media sizes (0.4~0.7, 0.7~1.0 and 1.0~1.4 mm) were tested. Only two sizes (0.4~0.7 and 0.7~1.0 mm) satisfied target turbidity, below 1.0 NTU. However, they showed the fast head loss. To prevent the fast head loss and secure the volume of the injected water, a rapid anthracite filter with roughing media size (2.0~3.4 mm) were installed before a single rapid sand filter. As results, both the target turbidity and reduction of head loss were achieved. It was determined that the media size for a rapid sand filter in two step rapid filter system (i.e. a rapid anthracite filter before a rapid sand filter) was 0.7~1.0 mm. In addition, the effects of coagulant doses on the removal of natural organic matter (NOM), which might cause a biological clogging, were preliminarily evaluated, and the values of UV254, dissolved organic carbon (DOC) and SUVA were interpreted.