• Title/Summary/Keyword: gas selectivity

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Gas Permeation Properties of Sulfonated 6FDA-Based Polyimide Membranes Exchanged with Metal Ions (금속이온이 치환된 설폰화된 6FDA계 폴리이미드 막의 기체 투과 특성)

  • Im, Hyeon-Soo;Lee, Byung-Seong;Lee, Bo-Sung;Yoon, Seok-Won;Koh, Hyung-Chul;Lee, Choong-Sub;Ha, Seong-Yong;Cheong, Seong-Ihl;Rhim, Ji-Won
    • Polymer(Korea)
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    • v.33 no.6
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    • pp.555-560
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    • 2009
  • Sulfonic acid of the sulfonated 6FDA-based polyimides were exchanged with the monovalent ($Li^+$, $Na^+$, $K^+$) and divalent ($Mg^{2+}$, $Ca^{2+}$, $Ba^{2+}$) ions. The effect of metal cations exchanged sulfonated polyimides was investigated in terms of gas permeability and selectivity for $CO_2$, $O_2$ and $N_2$ gases. Thermogravimetric analysis showed that thermal stability of sulfonated polyimide was improved by exchanged metal cations. The permeabilities of monovalent cation-exchanged, sulfonated polyimide were reduced as the ion radius reduced [$Li^+$(0.059 nm)>$Na^+$(0.102 nm)>$K^+$(0.138 nm)], and those of divalent cations exchanged were determined by the ionic radii and electrostatic crosslinking between the polymer and metal cations, whereas the selectivities of all the metal cation-exchanged, sulfonated polyimides for $CO_2/N_2$ and $O_2/N_2$, were higher than those of sulfonated polyimide membranes. The sulfonated polyimide exchanged with the potassium cation showed the $O_2$ permeability of 89.98 Barrer [$1\times10^{-10}\;cm^3$(STP) $cm/cm^2{\cdot}s{\cdot}cmHg$] and the sulfonated polyimide exchanged with the lithium cation showed the $O_2/N_2$ selectivity of 12.9.

CO2 Methanation Characteristics over Ni Catalyst in a Pressurized Bubbling Fluidized Bed Reactor (가압 기포 유동층 반응기에서의 Ni계 촉매 CO2 메탄화 특성 연구)

  • Son, Seong Hye;Seo, Myung Won;Hwang, Byung Wook;Park, Sung Jin;Kim, Jung Hwan;Lee, Do Yeon;Go, Kang Seok;Jeon, Sang Goo;Yoon, Sung Min;Kim, Yong Ku;Kim, Jae Ho;Ryu, Ho Jeong;Rhee, Young Woo
    • Korean Chemical Engineering Research
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    • v.56 no.6
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    • pp.871-877
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    • 2018
  • Storing the surplus energy from renewable energy resource is one of the challenges related to intermittent and fluctuating nature of renewable energy electricity production. $CO_2$ methanation is well known reaction that as a renewable energy storage system. $CO_2$ methanation requires a catalyst to be active at relatively low temperatures ($250-500^{\circ}C$) and selectivity towards methane. In this study, the catalytic performance test was conducted using a pressurized bubbling fluidized bed reactor (Diameter: 0.025 m and Height: 0.35 m) with $Ni/{\gamma}-Al_2O_3$ (Ni70%, and ${\gamma}-Al_2O_3$30%) catalyst. The range of the reaction conditions were $H_2/CO_2$ mole ratio range of 4.0-6.0, temperature of $300-420^{\circ}C$, pressure of 1-9 bar, and gas velocity ($U_0/U_{mf}$) of 1-5. As the $H_2/CO_2$ mole ratio, temperature and pressure increased, $CO_2$ conversion increases at the experimental temperature range. However, $CO_2$ conversion decreases with increasing gas velocity due to poor mixing characteristics in the fluidized bed. The maximum $CO_2$ conversion of 99.6% was obtained with the operating condition as follows; $H_2/CO_2$ ratio of 5, temperature of $400^{\circ}C$, pressure of 9 bar, and $U_0/U_{mf}$ of 1.4-3.

Steam Reforming of Hydrothermal Liquefaction Liquid from Macro Algae over Ni-K2TixOy Catalysts (Ni-K2TixOy 촉매를 이용한 해조류 유래 수열 액화 원료의 수증기 개질 반응 연구)

  • Park, Yong Beom;Lim, Hankwon;Woo, Hee-Chul
    • Clean Technology
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    • v.23 no.1
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    • pp.104-112
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    • 2017
  • Hydrogen production via steam reforming of liquefaction liquid from marine algae over hydrothermal liquefaction was carried out at 873 ~ 1073 K with a commercial catalyst and Ni based $K_2Ti_xO_y$ added catalysts. Liquefaction liquid obtained by hydrothermal liquefaction (503 K, 2 h) was used as a reactant and comparison studies for catalytic activity over different catalysts (FCR-4-02, $Ni/K_2Ti_xO_y-Al_2O_3$, $Ni/K_2Ti_xO_y-SiO_2$, $Ni/K_2Ti_xO_y-ZrO_2/CeO_2$ and Ni/$K_2Ti_xO_y$-MgO), reaction temperature were performed. Experimental results showed Ni/$K_2Ti_xO_y$ based catalysts ($Ni/K_2Ti_xO_y-Al_2O_3$, $Ni/K_2Ti_xO_y-SiO_2$, Ni/$K_2Ti_xO_y-ZrO_2$/ $CeO_2$ and Ni/$K_2Ti_xO_y$-MgO) have a higher activity than commercial catalyst (FCR-4-02) and In particular, a product composition was different depending on support materials. An acidic support ($Al_2O_3$) and a basic support (MgO) led to a higher selectivity for CO while a neutral support ($SiO_2$) and a reducing support ($ZrO_2/CeO_2$) resulted in a higher $CO_2$ selectivity due to water gas shift reaction.

전이금속 (Ru$^{3+}$, Ni$^{2+}$, Cu$^{2+}$, Pd$^{2+}$)-Polyaza(N$_4$) 착물의 합성과 올레핀 산화반응에 대한 촉매적 활성

  • Park, Yu Cheol;Kim, Seong Su;Na, Hun Gil;Lee, Dong Cheol;Sin, Sang Hui;Byeon, Jong Cheol
    • Journal of the Korean Chemical Society
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    • v.38 no.4
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    • pp.295-301
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    • 1994
  • The Ru(Ⅲ), Ni(Ⅱ), Cu(Ⅱ), and Pd(Ⅱ) complexes of N$_4$-polydentate ligands(meso-Me$_6$-[14]-ane, rac-Me$_6$-[14]-ane, and cyclam) have been prepared and their catalytic activity and selectivity in the oxidation of olefins in the presence of oxidant such as NaOCl, H$_2$O$_2$, t-BuOOH, and PhIO studied. The oxidations of cyclohexene, 1-hexene, cyclooctene, 1-octene, and styrene as substrates have been investigated gas chromatographically. The Ru(Ⅲ)-N$_4$ complexes showed high selectivity for epoxide in the catalyzed oxidation of olefins with NaOCl. The catalytic activities of Ru(Ⅲ)-N$_4$ complexes were discussed in terms of the flexibility of N$_4$-polydentate ligands, the Ru(Ⅲ)-Cl bond interaction and the steric effect of oxidants. The oxidation of 1-octene using PhIO as oxidant was carried out to verify. The Pd(Ⅱ) complex turned out to be more active catalyst than the Ni(Ⅱ) complexes.

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Magnetized inductively coupled plasma etching of GaN in $Cl_2/BCl_3$ plasmas

  • Lee, Y.H.;Sung, Y.J.;Yeom, G.Y.
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 1999.10a
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    • pp.49-49
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    • 1999
  • In this study, $Cl_2/BCI_3$ magnetized inductively coupled plasmas (MICP) were used to etch GaN and the effects of magnetic confinements of inductively coupled plasmas on the GaN etch characteristics were investigated as a function of $Cl_2/BCI_3$. Also, the effects of Kr addition to the magnetized $Cl_2/BCI_3$ plasmas on the GaN etch rates were investigated. The characteristics of the plasmas were estimated using a Langmuir probe and quadrupole ma~s spectrometry (QMS). Etched GaN profiles were observed using scanning electron microscopy (SEM). The small addition of $Cl_2/BCI_3$ (10-20%) in $Cl_2$ increased GaN etch rates for both with and without the magnetic confinements. The application of magnetic confinements to the $Cl_2/BCI_3$ inductively coupled plasmas (ICP) increased GaN etch rates and changed the $Cl_2/BCI_3$ gas composition of the peak GaN etch rate from 10% $BCI_3$ to 20% $BCI_3$. It also increased the etch selectivity over photoresist, while slightly reducing the selectivity over $Si0_2$. The application of the magnetic field significantly increased positive $BCI_2{\;}^+$ measured by QMS and total ion saturation current measured by the Langmuir probe. Other species such as CI, BCI, and CI+ were increased while species such as $BCl_2$ and $BCI_3$ were decreased with the application of the magnetic field. Therefore, it appears that the increase of GaN etch rate in our experiment is related to the increased dissociative ionization of $BCI_3$ by the application of the magnetic field. The addition of 10% Kr in an optimized $Cl_2/BCI_3$ condition (80% $Cl_2/$ 20% $BCI_3$) with the magnets increased the GaN etch rate about 60%. More anisotropic GaN etch profile was obtained with the application of the magnetic field and a vertical GaN etch profile could be obtained with the addition of 10% Kr in an optimized $Cl_2/BCI_3$ condition with the magnets.

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Separation of $H_2$ and $N_2$ Gases by PTMSP-NaY Zeolite Composite Membranes (PTMSP-NaY Zeolite 복합막에 의한 수소-질소 기체 분리에 관한 연구)

  • Kim, Ok-Su;Hong, Se Ryeong
    • Membrane Journal
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    • v.24 no.4
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    • pp.285-291
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    • 2014
  • The PTMSP[Poly(1-trimethylsilyl-1-propyne)]-NaY zeolite composite membranes were prepared by adding 0~50 wt% NaY zeolite to PTMSP. In order to investigate the characteristics of these membranes, we used the analytical methods such as FT-IR, $^1H$-NMR, GPC, DSC, TGA, and SEM. Gas permeation experiments were carried out at $23{\sim}26^{\circ}C$, $2kgf/cm^2$, and the permselectivity of $H_2$ and $N_2$ gases through the composite membranes was studied as a function of the NaY zeolite contents. According to TGA measurements, when NaY zeolite was inserted within the PTMSP, thermal stability of PTMSP was enhanced. Based on SEM observation, NaY zeolite was dispersed in the PTMSP-NaY zeolite composite membrane with a size of $1.5{\mu}m$. The permeability of $H_2$ and $N_2$ through the PTMSP-NaY zeolite composite membranes increased as NaY zeolite content increased. On the contrary, the selectivity($H_2/N_2$) of the PTMSP-NaY zeolite composite membranes decreased as zeolite content increased.

Effect of Cu Addition in Cu/Fe/Zr-Mixed Metal Oxide Mediums for Two-step Thermochemical Methane Reforming (2단계 열화학 메탄 개질을 위한 Cu/Fe/Zr-혼합 산화물 매체 내 Cu 첨가 효과)

  • Cha, Kwang-Seo;Kim, Hong-Soon;Lee, Dong-Hee;Jo, Won-Jun;Lee, Young-Seak;Kim, Young-Ho
    • Applied Chemistry for Engineering
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    • v.18 no.6
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    • pp.618-624
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    • 2007
  • thermochemical methane reforming consisting of two steps on Cu/Fe/Zr mixed oxide media was carried out using a fixed bed infrared reactor. In the first step, the metal oxide was reduced with methane to produce CO, $H_2$ and the reduced metal oxide in the temperature of 1173 K. In the second step, the reduced metal oxide was re-oxidized with steam to produce $H_2$ and the metal oxide in the temperature of 973 K. The reaction characteristics on the added amounts of Cu in Cu/Fe/Zr mixed oxide media and the cyclic tests were evaluated. With the increase of the added amount of Cu in Cu/Fe/Zr mixed oxide media, the conversion of $CH_4$, the selectivity of $CO_2$ and the $H_2/CO$ molar ratio were increased, while the selectivity of CO was decreased in the first step. On the other hand, the evolved amount of $H_2$ was decreased with increasing the added amount of Cu in the second step. The $Cu_xFe_{3-x}O_4/ZrO_2$ medium added with Cu of x = 0.7 showed good regeneration properties in the 10th cyclic tests indicating that the medium had high durability. In addition, the gasification of the deposited carbon in the water splitting step was promoted with the addition of Cu in the media.

Dry Etching of PMMA and Polycarbonate in a Diffusion Pump-based Capacitively Coupled O2 Plasma (확산펌프 기반의 O2 축전결합 플라즈마를 이용한 PMMA와 폴리카보네이트의 건식 식각)

  • Park, Ju-Hong;Lee, Seong-Hyun;Choi, Jyoung-Hoon;Noh, Ho-Sub;Lee, Je-Won
    • Korean Journal of Materials Research
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    • v.19 no.8
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    • pp.421-426
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    • 2009
  • We report on the capacitively coupled O2 plasma etching of PMMA and polycarbonate (PC) with a diffusion pump. Plasma process variables were process pressure and CCP power at 5 sccm $O_2$ gas flow rate. Characterization was done in order to analyze etch rate, etch selectivity, surface roughness, and morphology using stylus surface profilometry and scanning electron microscopy. Self bias decreased with increase of process pressure in the range of 25$\sim$180 mTorr. We found an important result for optimum pressure for the highest etch rate of PMMA and PC, which was 60 mTorr. PMMA and PC had etch rates of 0.46 and 0.28 ${\mu}m$/min under pressure conditions, respectively. More specifically, etch rates of the materials increased when the pressure changed from 25 mTorr to 60 mTorr. However, they reduced when the pressure increased further after 60 mTorr. RMS roughnesses of the etched surfaces were in the range of 2.2$\sim$2.9 nm. Etch selectivity of PMMA to a photoresist was $\sim$1.5:1 and that of PC was $\sim$0.9:1. Etch rate constant was about 0.04 ${\mu}m$/minW and 0.02 ${\mu}m$/minW for PMMA and PC, respectively, with the CCP power change at 5 sccm $O_2$ and 40 mTorr process pressure. PC had more erosion on the etched sidewall than PMMA did. The OES data showed that the intensity of the oxygen atomic peak (777.196 nm) proportionally increased with the CCP power.

Cross-Linked PGMA-co-PMMA/DAAB Membranes for Propylene/Nitrogen Separation (프로필렌/질소 분리를 위한 가교 구조의 PGMA-co-PMMA/DAAB 분리막)

  • Kim, Na Un;Park, Byeong Ju;Kim, Jong Hak
    • Membrane Journal
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    • v.30 no.4
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    • pp.252-259
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    • 2020
  • Olefins are industrially important materials used for the synthesis of various petrochemicals. During the polymerization process, unreacted olefin monomers are discharged together with a large amount of nitrogen. For economic benefits, these olefin gases should be efficiently separated from nitrogen. In this study, a poly(glycidyl methacrylate-co-methyl methacrylate) (PGM) comb-like copolymer was synthesized and 4,4'-diaminoazobenzene (DAAB) was introduced to the copolymer to prepare a cross-linked membrane for C3H6/N2 separation. PGM and DAAB were readily reacted at room temperature through an epoxide-amine reaction without additional thermal treatment. PGM-based membrane, which is a glassy polymer, showed a faster permeation of N2 compared to C3H6. The pristine PGM membrane exhibited the N2 permeability of 0.12 barrer and the high N2/C3H6 selectivity of 32.4. As DAAB was introduced as a cross-linker, the thermal stability of the membrane was significantly improved, which was confirmed by TGA result. The N2/C3H6 selectivity was decreased at 1 wt% of DAAB content, but the N2 permeability increased by approximately 4.7 times. We analyzed N2/C3H6 gas separation properties through a glassy polymer-based membrane, which has not been widely studied. Also, we proposed that thermal stability of the membrane can be greatly improved by the cross-linking method.

Olefin Separation Membranes Based on PEO/PDMS-g-POEM Blends Containing AgBF4/Al(NO3)3 Mixed Salts (AgBF4/Al(NO3)3 혼합염이 포함된 PEO/PDMS-g-POEM 블렌드 기반의 올레핀 분리막)

  • Kim, Sang Jin;Jung, Jung Pyu;Park, Cheol Hun;Kim, Jong Hak
    • Membrane Journal
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    • v.25 no.6
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    • pp.496-502
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    • 2015
  • Facilitated transport is one of the possible solutions to simultaneously improve permeability and selectivity, which is challenging in conventional polymer-based membranes. Olefin/paraffin separation using facilitated transport membrane has received much attention as an alternative solution to the conventional distillation process. Herein, we report olefin separation composite membranes based on the polymer blends containing $AgBF_4/Al(NO_3)_3$ mixed salts. Free radical polymerization process was used to synthesize an amphiphilic graft copolymer of poly(dimethyl siloxane)-graft- poly(ethylene glycol) methyl ether methacrylate (PDMS-g-POEM). In addition, poly(ethylene oxide) (PEO) was introduced to the PDMS-g-POEM graft copolymer to form polymer blends with various ratios. The propylene/propane mixed-gas selectivity and permeance reached up to 5.6 and 10.05 GPU, respectively, when the PEO loading was 70 wt% in polymer blend. The improvement of olefin separation performance was attributed to the olefin facilitating silver ions as well as the highly permeable blend matrix. The stabilization of silver ions in the composite membrane was achieved through the introduction of $Al(NO_3)_3$ which suppressed the reduction of silver ions to silver particles.