• Title/Summary/Keyword: Hydrogen enrichment

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Structure and Reactivity of Bimetallic Catalyst (이원금속 촉매의 구조와 반응성)

  • Yie, Jae-Eue
    • Applied Chemistry for Engineering
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    • v.3 no.1
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    • pp.24-34
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    • 1992
  • Recent studies dealing with the fundamental understanding and applications of bimetallic catalysts are discussed. Bimetallic catalysts have had a major industrial impact, specifically for the reforming of petroleum naphtha, for the hydrogen reduction of carbon monoxide, and for the three way catalytic converter system. The action of the bimetallic catalysts in these reactions may be interpreted in terms of ensembles, electronic influences and surface structure. Various combinations of metal pairs have been considered in order to evaluate the role played by the added metals. For catalyst selectivity control, the possibility of surface enrichment of one element has been recognised. More generally, the influence of preparative variables on the formation of supported catalysts has been clarified, In particular by temperature programmed reduction (TPR). Information on the structure of bimetallic catalysts has been obtained with chemical probes, such as chemisorption and reaction rate measurement and physical probes, such as extended X-ray absorption fine structure (EXAFS), scanning transmission electron microscopy (STEM) and Xe-NMR.

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Hydrogenotrophic Sulfate Reduction in a Gas-Lift Bioreactor Operated at $9^{\circ}C$

  • Nevatalo, Laura M.;Bijmans, Martijn F. M.;Lens, Piet N. L.;Kaksonen, Anna H.;Puhakka, Jaakko A.
    • Journal of Microbiology and Biotechnology
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    • v.20 no.3
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    • pp.615-621
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    • 2010
  • The viability of low-temperature sulfate reduction with hydrogen as electron donor was studied with a bench-scale gas-lift bioreactor (GLB) operated at $9^{\circ}C$. Prior to the GLB experiment, the temperature range of sulfate reduction of the inoculum was assayed. The results of the temperature gradient assay indicated that the inoculum was a psychrotolerant mesophilic enrichment culture that had an optimal temperature for sulfate reduction of $31^{\circ}C$, and minimum and maximum temperatures of $7^{\circ}C$ and $41^{\circ}C$, respectively. In the GLB experiment at $9^{\circ}C$, a sulfate reduction rate of 500-600 mg $l^{-1}d^{-1}$, corresponding to a specific activity of 173 mg ${SO_4}^{2-}g\;VSS^{-1}d^{-1}$, was obtained. The electron flow from the consumed $H_2$-gas to sulfate reduction varied between 27% and 52%, whereas the electron flow to acetate production decreased steadily from 15% to 5%. No methane was produced. Acetate was produced from $CO_2$ and $H_2$ by homoacetogenic bacteria. Acetate supported the growth of some heterotrophic sulfate-reducing bacteria. The sulfate reduction rate in the GLB was limited by the slow biomass growth rate at $9^{\circ}C$ and low biomass retention in the reactor. Nevertheless, this study demonstrated the potential sulfate reduction rate of psychrotolerant sulfate-reducing mesophiles at suboptimal temperature.

Petrochemistry of the Soyeonpyeong titaniferous iron ore deposits, South Korea (소연평도 함티타늄 자철광상의 암석지구화학적 연구)

  • Kim, Kyu Han;Lee, Jung Eun
    • Economic and Environmental Geology
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    • v.27 no.4
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    • pp.345-361
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    • 1994
  • Lens shaped titanomagnetite ore bodies in the Soyeonpyeong iron mine are embedded in amphibolites, which were intruded into Precambrian metasediments such as garnet-mica schist, marble, mica schist, and quartz schist. Mineral chemistry, K-Ar dating and hydrogen and oxygen stable isotopic analysis for the amphibolites and titanomagnetite ores were conducted to interpret petrogenesis of amphibolite and ore genesis of titanomagnetite iron ore deposits. Amphibolites of igneous origin have unusually high content of $TiO_2$, ranging from 0.94 to 6.39 wt.% with an average value of 4.05 wt.%. REE patterns of the different lithology of the amphibolite show the similar trend with an enrichment of LREE. Amphiboles of amphibolites are consist mainly of calcic amphiboles such as ferro-hornblende, tschermakite, ferroan pargasite, and ferroan pargasitic hornblende. K-Ar ages of hornblende from amphibolite and gneissic amphibolite were determined as $440.04{\pm}6.39Ma$ and $351.03{\pm}5.21Ma$, respectively. This indicates two metamorphic events of Paleozoic age in the Korean peninsula which are correlated with Altin orogeny in China. The titanomagnetite mineralization seems to have occurred before Cambrian age based on occurrence of orebodies and ages of host amphibolites. The Soyeonpyeong iron ores are composed mainly of titanomagnetite, ilmenite, and secondary minerals such as ilmenite and hercynite exsolved in titanomagnetite. The temperature and the oxygen fugacity estimated by the titanomagnetite-ilmenite geothermometer are $500{\sim}600^{\circ}C$ (ave. $550^{\circ}C$) and about $2{\pm}10^{-23}bar$, respectively. Hornblendes from ores and amphibolites which responsible for magnetite ore mineralization, have a relatively homogeneous isotopic composition ranging from +0.8 to +3.9 ‰ in ${\delta}^{18}O$ and from -87.8 to -113.3 ‰ in ${\delta}D$. The calculated oxygen and hydrogen isotopic compositions of the fluids which were in equilibrium with hornblende at $550^{\circ}C$, range from 2.8 to 5.9‰ in ${\delta}^{18}O_{H2O}$ and from -60.41 to -81.31 ‰ in ${\delta}D_{H2O}$. The ${\delta}^{18}O_{H2O}$ value of magnetite ore fluids are in between +6.4 to + 7.9 ‰. All of these values fall in the range of primary magmatic water. A slight oxygen shift means that $^{18}O$-depleted meteoric water be acted with basic fluids during immiscible processes between silicate and titaniferous oxide melt. Mineral chemistry, isotopic compositions, and occurences of amphibolites and orebodies, suggest that the titanomagnetite melt be separated immisciblely from the titaniferous basic magma.

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$H_{2}S$ Removal and $CO_{2}/CH_{4}$ Separation of Ternary Mixtures Using Polyimide Hollow Fiber Membrane (폴리이미드 중공사막을 이용한 혼합기체로부터 $H_{2}S$ 제거 및 $CO_{2}/CH_{4}$ 분리에 관한 연구)

  • Park, Bo-Ryoung;Kim, Dae-Hoon;Jo, Hang-Dae;Seo, Yong-Seog;Hwang, Taek-Sung;Lee, Hyung-Keun
    • Korean Chemical Engineering Research
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    • v.49 no.2
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    • pp.250-255
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    • 2011
  • In this study, by using the polymeric membrane separation process, the $CO_{2}/CH_{4}$ separation and $H_{2}S$ removal from biogas were performed in order to $CH_{4}$ purification and enrichment for the fuel cell energy source application. Fibers were spun by dry/wet phase inversion method. The module was manufactured by fabricating fibers after surface coating with silicone elastomer. The scanning electron microscopy(SEM) studies showed that the produced fibers typically had an asymmetric structure; a dense top layer supported by a porous, sponge substructure. The permeance of $CO_{2}$ and $CO_{2}/CH_{4}$ selectivity increased with pressure and temperature. Mixture gas with increasing pressure and temperature, removal efficiency of the $CO_{2}$ and $H_{2}S$ were decreased while concentration of $CH_{4}$ was increased up to 100%. When retentate flow rate was increased with the decreasing of pressure and temperature the $CH_{4}$ recovery ratio in retentate side was increased while the $CH_{4}$ purity in retentate side was decreased.

A Geochemical Study on Pyrophyllite Deposits and Andesitic Wall-Rocks in the Milyang Area, Kyeongnam Province (경남 밀양지역 납석광상과 안산암질 모암의 지구화학적 연구)

  • Oh, Dae-Gyun;Chon, Hyo-Taek;Min, Kyoung-Won
    • Economic and Environmental Geology
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    • v.25 no.1
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    • pp.27-39
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    • 1992
  • Several pyrophyllite deposits occur around the Milyang area where Cretaceous andesitic rocks and spatially related granitic rocks are widely distributed. Pyrophyllite ores consist mainly of pyrophyllite, and quartz with small amount of sericite, pyrite, dumortierite, and diaspore. The andesitic rocks and spatially related granitic rocks in this area suggest that they could be formed from the same series of a calc-alkaline magma series. The contents of $SiO_2$, $Al_2O_3$, LOI(loss on ignition) are enriched, and $K_2O$, $Na_2O$, CaO, MgO, $Fe_2O_3$ are depleted in altered andesitic rocks and ores. Enrichment of As, Cr, Sr, V, Sb and depletion of Ba, Cs, Ni, Rb, U, Y, Co, Sc, Zn are characteristic during mineralization. The pyrophyllite ores can be discriminated from the altered-and unaltered wall-rocks by an increasing of $(La/Lu)_{cn}$ from 4.18~22.13 to 8.98~55.05. In R-mode cluster analysis, Yb-Lu-Y, La-Ce-Hf-Th-U-Zr, $TiO_2-V-Al_2O_3$, Sm-Eu, $CaO-Na_2O-MnO$, Cu-Zn-Ag, $K_2O-Rb$ are closely correlated. In the discriminant analysis of multi-element data, $P_2O_5$, As, Cr and $Fe_2O_3$, Sr are helpful to identify the ores from the unaltered-and altered wall-rocks. In the factor analysis, the factors of alteration of andesitic rocks and ore mineralization were extracted. In the change of ions per unit volume, $SiO_2$, $Al^{3+}$ and LOI are enriched and $Na^+$, $K^+$, $Ca^{2+}$, $Mg^{2+}$, $Mn^{2+}$ and $Fe^{3+}$ are depleted during the alteration processes. The Milyang and the Sungjin pyrophyllite deposits could be mineralized by hydrothermal alteration in a geochemical condition of low activity ratio of alkaline ions to hydrogen ion with reference to spatially related granitic rocks.

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Autotrophic Perchlorate-Removal Using Zero-Valent Iron and Activated Sludge: Batch Test (영가철과 활성슬러지를 이용한 독립영양방식의 퍼클로레이트 제거: 회분배양연구)

  • Ahn, Yeong-Hee;Ha, Myoung-Gyu
    • Journal of Life Science
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    • v.21 no.3
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    • pp.444-450
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    • 2011
  • Perchlorate ($ClO_4^-$) is a contaminant found in surface water and soil/ground water. Autotrophic perchlorate-reducing bacteria (PRB) use hydrogen gas ($H_2$) as an electron donor to remove perchlorate. Since iron corrosion can produce $H_2$, feasibility of autotrophic perchlorate-removal using zero-valent iron (ZVI) was examined in this study using activated sludge that is easily available from a wastewater treatment plant. Batch test showed that activated sludge microorganisms could successfully degrade perchlorate in the presence of ZVI. The perchlorate biodegradation was confirmed by molar yield of $Cl^-$ as perchlorate was degraded. Scanning electron microscope revealed that rod-shaped microorganisms on the surface of iron particles used for the autotrophic perchlorate-removal, suggesting that iron particles could serve as supporting media for the formation of biofilm as well. DGGE analyses revealed that microbial profile of the inoculum (activated sludge) was different from that of biofilm sample obtained from the ZVI-added enrichment culture used for $ClO_4^-$-degradation. A major band of the biofilm sample was most closely related to the class Clostridia.

Adhesion of Model Molecules to Metallic Surfaces, the Implications for Corrosion Protection

  • de Wit, J.H.W.;van den Brand, J.;de Wit, F.M.;Mol, J.M.C.
    • Corrosion Science and Technology
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    • v.7 no.1
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    • pp.50-60
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    • 2008
  • The majority of the described experimental results deal with relatively pure aluminium. Variations were made in the pretreatment of the aluminum substrates and an investigation was performed on the resulting changes in oxide layer composition and chemistry. Subsequently, the bonding behavior of the surfaces was investigated by using model adhesion molecules. These molecules were chosen to represent the bonding functionality of an organic polymer. They were applied onto the pretreated surfaces as a monolayer and the bonding behavior was studied using infrared reflection absorption spectroscopy. A direct and clear relation was found between the hydroxyl fraction on the oxide surfaces and the amount of molecules that subsequently bonded to the surface. Moreover, it was found that most bonds between the oxide surface and organic functional groups are not stable in the presence of water. The best performance was obtained using molecules, which are capable of chemisorption with the oxide surface. Finally, it was found that freshly prepared relatively pure aluminum substrates, which are left in air, rapidly lose their bonding capacity towards organic functional groups. This can be attributed to the adsorption of contamination and water to the oxide surface. In addition the adhesion of a typical epoxy-coated aluminum system was investigated during exposure to water at different temperatures. The coating was found to quite rapidly lose its adhesion upon exposure to water. This rapid loss of adhesion corresponds well with the data where it was demonstrated that the studied epoxy coating only bonds through physisorptive hydrogen bonding, these bonds not being stable in the presence of water. After the initial loss the adhesion of the coating was however found to recover again and even exceeded the adhesion prior to exposure. The improvement could be ascribed to the growth of a thin oxyhydroxide layer on the aluminum substrate, which forms a new, water-stable and stronger bond with the epoxy coating. Two routes for improvement of adhesion are finally decribed including an interphasial polymeric thin layer and a treatment in boiling water of the substrate before coating takes place. The adhesion properties were finely also studied as a function of the Mg content of the alloys. It was shown that an enrichment of Mg in the oxide could take place when Mg containing alloys are heat-treated. It is expected that for these alloys the (hydr)oxide fraction also depends on the pre-treatment and on the distribution of magnesium as compared to the aluminium hydroxides, with a direct impact on adhesive properties.

COATED PARTICLE FUEL FOR HIGH TEMPERATURE GAS COOLED REACTORS

  • Verfondern, Karl;Nabielek, Heinz;Kendall, James M.
    • Nuclear Engineering and Technology
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    • v.39 no.5
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    • pp.603-616
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    • 2007
  • Roy Huddle, having invented the coated particle in Harwell 1957, stated in the early 1970s that we know now everything about particles and coatings and should be going over to deal with other problems. This was on the occasion of the Dragon fuel performance information meeting London 1973: How wrong a genius be! It took until 1978 that really good particles were made in Germany, then during the Japanese HTTR production in the 1990s and finally the Chinese 2000-2001 campaign for HTR-10. Here, we present a review of history and present status. Today, good fuel is measured by different standards from the seventies: where $9*10^{-4}$ initial free heavy metal fraction was typical for early AVR carbide fuel and $3*10^{-4}$ initial free heavy metal fraction was acceptable for oxide fuel in THTR, we insist on values more than an order of magnitude below this value today. Half a percent of particle failure at the end-of-irradiation, another ancient standard, is not even acceptable today, even for the most severe accidents. While legislation and licensing has not changed, one of the reasons we insist on these improvements is the preference for passive systems rather than active controls of earlier times. After renewed HTGR interest, we are reporting about the start of new or reactivated coated particle work in several parts of the world, considering the aspects of designs/ traditional and new materials, manufacturing technologies/ quality control quality assurance, irradiation and accident performance, modeling and performance predictions, and fuel cycle aspects and spent fuel treatment. In very general terms, the coated particle should be strong, reliable, retentive, and affordable. These properties have to be quantified and will be eventually optimized for a specific application system. Results obtained so far indicate that the same particle can be used for steam cycle applications with $700-750^{\circ}C$ helium coolant gas exit, for gas turbine applications at $850-900^{\circ}C$ and for process heat/hydrogen generation applications with $950^{\circ}C$ outlet temperatures. There is a clear set of standards for modem high quality fuel in terms of low levels of heavy metal contamination, manufacture-induced particle defects during fuel body and fuel element making, irradiation/accident induced particle failures and limits on fission product release from intact particles. While gas-cooled reactor design is still open-ended with blocks for the prismatic and spherical fuel elements for the pebble-bed design, there is near worldwide agreement on high quality fuel: a $500{\mu}m$ diameter $UO_2$ kernel of 10% enrichment is surrounded by a $100{\mu}m$ thick sacrificial buffer layer to be followed by a dense inner pyrocarbon layer, a high quality silicon carbide layer of $35{\mu}m$ thickness and theoretical density and another outer pyrocarbon layer. Good performance has been demonstrated both under operational and under accident conditions, i.e. to 10% FIMA and maximum $1600^{\circ}C$ afterwards. And it is the wide-ranging demonstration experience that makes this particle superior. Recommendations are made for further work: 1. Generation of data for presently manufactured materials, e.g. SiC strength and strength distribution, PyC creep and shrinkage and many more material data sets. 2. Renewed start of irradiation and accident testing of modem coated particle fuel. 3. Analysis of existing and newly created data with a view to demonstrate satisfactory performance at burnups beyond 10% FIMA and complete fission product retention even in accidents that go beyond $1600^{\circ}C$ for a short period of time. This work should proceed at both national and international level.