A simple preparation method for rare-earth phosphate nano materials using an ionic liquid-driven supported liquid membrane system

Panpan Zhao,Fan Yang,Zhigang Zhao,Qiuxiao Liao,Yang Zhang,Peng Chen,Wanghuan Guo,Ruixi Bai 한국공업화학회 2017 Journal of Industrial and Engineering Chemistry Vol.54 No.-

For the first time, our group has developed a novel, high-flux strategy for shape-controlled synthesis of rare earth nano-materials (CePO4) using ionic liquid(IL)-driven supported liquid membrane (HVHP, DUPAPORE1) system. The system contains three phases including a supply phase of rare earth ions, a feed phase of phosphates, and ionic liquid-driven supporting liquid membrane phase. The imidazolium IL-driven supported liquid membrane is promising for nano-synthetic reaction of CePO4. The anion types of immersed imidazolium IL have a critical role in the formation rate of CePO4 nano-materials. Moreover, the adding SO4 2 anion or adjustment of pH in supply phase containing Ce(III) ions could control effectively the morphology of the CePO4 nano-materials. The result can be regarded as a good example, the IL:[C4mim][Tf2N] driven support liquid membrane systems can be used to prepare nano-wire and nano-sphere structures of CePO4 with high efficiency and flux. Besides, the IL-driven supported liquid membrane can be cycled many times by using the back flush activation method.

상분리법을 통하여 제조된 새로운 개념의 지지형 액막의 기체투과특성

최평호,김범식,이정민,김철웅,구기갑,이상학 한국공업화학회 2004 공업화학 Vol.15 No.1

새로운 지지형 액막(SLM)을 용매 증발에 따른 1차, 2차 상분리법으로 3성분 고분자 용액으로부터 제조하였다. 액막재로 이온액인 BMIBF_(4) (BMI+ =1-(1-butyl)-3-methylimidazolium, BF_(4)=tetra-fluoro boratr)와 매트릭스 고분자로 polyvinylidenefluoride(PVDF)가 사용되었다. 이 고정화 액막의 O_(2), N_(2) 그리고 CO_(2) 기체 투과특성을 여러 조작 조건에서 조사하였다. SLM은 가혹한 조건에서 조작하였음에도 불구하고 오랜 시간동안 높은 CO_(2) 투과도 및 선택성을 유지하였다. 투과거동을 나타내는 인자인 투과도, 확산도, 그리고 용해도를 연속 측정 장치를 통하여 구함으로써 특성을 관찰하였다. SLM은 다른 기체에 비하여 CO_(2)에 대해서 높은 투과도와 선택도를 갖고 있었다. 특히, 막내 CO_(2)의 용해도는 다른 기체들에 비하여 매우 높은 반면 확산도는 큰 차이를 보이지 않았다. 또한 막내 이온액의 조성은 CO_(2) 용해도에 영향을 관찰할 수 있었다. 막내 이온액의 조성이 증가함에 따라서 CO_(2) 의 투과도 및 선택도가 극격히 증가하였다. 이는 SLM를 통한 기체 투과에 있어서 용해도가 주인자로 큰 영향을 끼침으로써 막내 이온액 조성 증가 SLM의 투과에 큰 영향을 미침을 확인하였다. The new supported liquid membranes (SLMs) were fabricated from ternary polymer solution contained ionic liquid in which primary and secondary phase separations were induced by the solvent by the solvent evaporaton. The used ionic liquid and polymer matrix were BMBF_(4) (BMI+=-(1-butyl)-3-methylimidazolium, BF_(4)-tetra-fluoro boratel and polyvinylidene fluoride (PVDF). Gas permeation properties of the SLM to O_(2), N_(2) and CO_(2) were studied at various operating conditions. Although the SLM were operated under severe operating condition, it maintained high CO_(2) permeability and selectivity for quite long time. The solubility coefficient of CO_(2) in the membrace was very high in comparison with those of other gases; whereas there was no big difference in the diffusivity between CO and other gases. Moreover, in the permeation of pure gases, it is observed that the ionic liquid content in the membrane affected the solubility of CO_(2) in the memhranc. With increasing ionic liquid content in the membrane, the permeability and selectivity of CO_(2) increase significantly. There fore, in the permeation of gases through SLM, the overall permeation performances weir affected mainly by solubility coefficient. This observation can be discussed in terms of the influence of solubility coefficient with ionic liquid content in the membrane.

Extraction separation of toluene/cyclohexane with hollow fiber supported ionic liquid membrane

Fan Zhang,Zhongqi Ren,Wei Sun,Junteng Liu,Weidong Zhang 한국화학공학회 2014 Korean Journal of Chemical Engineering Vol.31 No.6

A supported liquid membrane with ionic liquid was used for the separation of toluene/cyclohexane. Theinteractions of ionic liquid with toluene and cyclohexane were calculated and experimentally studied by quantum chemicalcalculation and liquid-liquid extraction process. The results showed [BPy][BF4] have stronger interaction with toluenethan that with cyclohexane. The selectivity of SILM processes was larger than 10 at the temperature of 323 K and theflow rate of 13.5 mL·min-1 on both shell side and lumen side. Due to the higher viscosity of IL, SILM process hadgood long-term stability. As the effects of mass transfer driving force of SILM process, the flux and removal efficiencyincreased with increase of initial toluene concentration, while the selectivity decreased because of the competitive transport. Base on the resistance in-series model and experimental results, the mass transfer resistance was mainly lay liquidmembrane phase. The influence of flow rates on both sides was slight. The higher temperature could enhance the masstransfer performance significantly. The removal efficiency increased from 28.2% to 45.1% with the increasing of operationtemperature from 298 K to 323 K.

Stabilization of [BMIM][PF6] ionic liquid membrane in structurally optimized multilayer ceramic support through aqueous DEA solution for CO2/CH4 separation

Hamid Reza Mahdavi,Mehran Arzani,Hamed Faramarzi,Omid Bakhtiari,Toraj Mohammadi 한국공업화학회 2023 Journal of Industrial and Engineering Chemistry Vol.127 No.-

The stability of the ceramic supported liquid membranes (SLMs) is one of the most interesting researchsubjects. In this work, the SLMs’ stability for CO2/CH4 separation was investigated. Following pressing a-Al2O3 substrates at 400, 600, and 800 bar, colloidal and polymeric TiO2 intermediate and top layers werecoated. Aqueous diethanolamine (DEA) solution was used as solvent in the SLM to optimize supportstructure based on CO2/CH4 separation performance. The pressed support at 800 bar and coated withTiO2 demonstrated best performance and selected for further study. Subsequently, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) ionic liquid (IL) was immobilized inside theselected support and used as the supported ionic liquid membrane (SILM) for CO2/CH4 separation. TheSILM separation performance was evaluated under different pressures and temperatures. Temperaturewas found to has greater effect than pressure due to a decrease in IL’s viscosity and an increase in penetrantdiffusivity. At 25 C and 1 bar, SILM exhibited consistent and reliable performance as CO2 and CH4permeabilities of 244.0 and 7.4 Barrer, respectively, and CO2/CH4 selectivity of 33.0 over 6 h. The findingscontribute to understanding the implementation of multilayer ceramic SILMs for CO2/CH4 separation andhighlight its potential along with opening up new avenues.

이산화탄소 분리를 위한 이온성액체 지지분리막의 제조

최미영,정건용 한국막학회 2012 멤브레인 Vol.22 No.4

본 연구는 이산화탄소를 효율적으로 분리하기 위한 이온성액체 지지분리막 제조를 목적으로 한다. 공칭크기 0.1 mum PVDF 정밀여과막에 이온성액체인 [bmim][PF6] (1-butyl-3-methylimidazolium hexafluorophosphate)를 분리막 세공내로 흡입시켜 고정화하였다. 제조된 이온성액체 지지막에 대한 N2, H2, CO2 기체의 투과도는 0.075, 0.203, 1.380 GPU로 측정되었으며 CO2/N2, H2/N2의 선택도는 각각 14.2와 2.69이었다. 또한 이온성액체 지지분리막은 이온성 액체가 운전압력 2.0 bar까지 세공 내에 고정되어 안정적으로 운전 가능하였다. The study is aiming to prepare supported ionic liquid membranes for carbon dioxide separation efficiently. The ionic liquid, [bmim][PF6] (1-butyl-3-methyl-imidazolium hexafluorophosphate) was fixed in the pores of PVDF micro-filtration membrane with a nominal pore size 0.1 mum. The permeabilities of N_2, H2 and CO2 gases through the prepared ionic liquid membrane were 0.075, 0.203 and 1.380 GPU, respectively. The selectivities of CO2/N2, H2/N2 were 14.2 and 2.69, respectively. Also, the supported ionic liquid membrane could be operated stably up to 2.0 bar with the immobilization of ionic liquid in the pores.

상온 이온액을 이용한 고온 무수 PEMFC용 고정화 액막의 온도에 따른 이온전도도 거동

김범식,변용훈,박유인,이상학,이정민,구기갑 한국막학회 2006 멤브레인 Vol.16 No.4

이온전도도가 높은 상온 이온액을 이용하여 저온, 고온 상분리에 의한 multi-stage phase separation process로 새로운 고정화 이온액 전해질 막(supported ionic liquid electrolyte membranes, SILEMs)을 제조하였다. PVDF와 imidazolium계 이온액을 각각 분리막 소재와 전해액으로 사용하였다. 이온전도도 특성을 알아보기 위해 SILEMs을 LCR meter를 이용 해 30℃부터 130℃까지 실험하였다. 가습조건에서 cast Nafion 막의 이온전도도는 30℃부터 100℃까지는 직선적으로 증가하였으나 그 이후에는 감소하였다. 그러나 SILEMs의 경우 운전온도의 증가에 따라 이온전도도가 증가하였다. 또한 SILEMs의 이온전도도 거동은 가습과 관계없이 거의 같았다. SILEMs의 이온전도도는 30℃에서 2.7x10 -3 S/cm이었고 온도가 130℃까지 증가함에 따라 2.2x10 -2 S/cm까지 거의 직선적으로 증가하였다. SiO2를 이용하여 SILEMs의 물리적 성질에 대한 무기첨가제의 영향에 관하여 연구하였다. SILEMs에 SiO2의 첨가는 비록 약간의 이온전도도 감소는 있으나 SILEMs의 기계적 강도를 향상시킬 수 있었다. Novel SILEMs were prepared by multi-stage phase separation process combined by the low temperature phase separation (LTPS) and the high temperature phase separation (HTPS) using room temperature ionic liquids (RTILs) which have a high ionic conductivity. PVDF and imidazolium series ionic liquids were used as membrane material and electrolyte, respectively. To study the ion conducting properties, the SILEMs were tested using LCR meter at temperature controlled from 30 to 130℃. Under humid conditions, with increasing temperature from 30 to 100℃, the ion conductivity of the cast Nafion ® membrane increased linearly, but then started to decrease after 100℃. However, in the case of the SILEMs, with increasing operating temperature, the ion conductivity increased. Also, the ion conductivity behaviors of the SILEMs were almost same, regardless of humidity. The ion conductivity of the SILEMs was 2.7x10 -3 S/cm and increased almost linearly up to 2.2x10 -2 S/cm with increasing temperature to 130℃. The effects of an inorganic filler on the physical properties of the SILEMs were studied using the SiO2. The addition of SiO2 could improve the mechanical strength of the SILEMs, though the ionic conductivity was decreased slightly.