• Title/Summary/Keyword: hydrothermal reduction

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Characterisitics of Redox Reaction of the Magnetite Powder Prepared by Hydrothermal Synthesis (수열합성법으로 합성된 마그네타이트 분말에 대한 산화.환원 특성)

  • Park, Sung Youl;Kang, Min Pil;Rhee, Young Woo;Nam, Sung Chan
    • Korean Chemical Engineering Research
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    • v.43 no.6
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    • pp.751-755
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    • 2005
  • Carbon dioxide, included in the flue gas from the combustion of fossil fuel, was known as a representative green house gas and various removal and utilization technologies of it has been studied for the prevention of global warming. This study was performed as an effort to find out a method to reuse carbon dioxide separated from flue gas by magnetite powder. Magnetite powder was synthesized using various oxidizers and alkalinity controlled aqueous solutions of $FeSO_4{\cdot}7H_2O$ and NaOH at 50, 80, 90, $100^{\circ}C$ and analyzed by XRD and SEM. The analysis results showed that magnetite powder synthesized at higher alkalinity and temperature had crystalline spinel and cubic structure. The reduction by hydrogen and the oxidation by carbon dioxide of synthesized powder were studied by TGA. The results showed that magnetite powder synthesized at low alkalinity and temperature was non-cubical amorphous but crystalline and cubical at high alkalinity and temperature. Comparing magnetite powders synthesized using oxidants(air and oxygen) and nitrogen, magnetite powder using more oxygen containing oxidant synthesized more crystalline magnetite powder. The experimental results of redox reaction of the synthesized magnetite powder showed that the reduction by hydrogen and the oxidation by carbon dioxide were seldom observed below $400^{\circ}C$ and observed well at $500^{\circ}C$. Magnetite powder synthesized at $100^{\circ}C$ and alkalinity(molal concentration ratio of $FeSO_4{\cdot}7H_2O$ to NaOH) of 2.0 using $O_2$ showed the highest reduction of 27.15 wt% and oxidation of 26.73 wt%, especially at reaction temperature of $500^{\circ}C$.

Potential Study for the Sedimentary Exhalative Pb-Zn Mineralization in Dyusembay Area, Kazakhstan (카자흐스탄 듀셈바이지역의 퇴적분기형 연-아연 광화작용에 대한 잠재력 연구)

  • No, Sang-gun;Lee, Seung-han;Park, Ki-woong;Jeong, Hyeon-guk;Yun, Ji-seong;Kim, Sun-ok;Park, Maeng-eon
    • Economic and Environmental Geology
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    • v.51 no.3
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    • pp.213-222
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    • 2018
  • Metasediment-hosted Pb-Zn mineralized zone has been found in Dyusembay of Kazakhstan. Its petrological properties, metal index, alteration index and redox-sensitivity are compared with those of SEDEX type deposit. Mineralization is developed along foliation of host rock (graphitic phyllite) and controlled by folds and faults; major ore minerals including pyrite, pyrrhotite, sphalerite, and galena are disseminated or interlayered with fine-grained quartz. The margin of the mineralized zone is metamorphosed accompanying sericite and chlorite. Hydrothermal brecciation and Pb-Zn mineralization formed in quartz-calcite stockworks are confirmed at the around of Maytyubin granitoid intrusions. The mineralization is classified into three types according to those of occurrence, paragenesis, chemical composition and isotopic characteristics. Type 1 whose fine-grained pyrite, pyrrhotite and sphalerite are formed in parallel yet discontinuous to well-developed foliations of the host rock; its geochemistry is similar to those of the earlier stage in SEDEX-type mineralization. In case of type 2, the ore minerals of which are concentrated being parallel to a foliation by regional metamorphism, and most of them associated with quartz and muscovite (${\pm}$ biotite) paragenetically. Type 3 is formed in the hydrothermal breccia zone whose ore minerals are controlled by foliation and breccia and developed in quartz ${\pm}$ calcite veins having a form such as stratification, stockwork or veinlets. Host rocks in the mineralized zone indicate homogeneous metamorphic grade and there is no specific alteration zonation. Also, all types (type 1, type 2, and type 3) represent similar REEs patterns, it can be interpreted that these are originated from a same source. Sulphides occurred in mineralized zone indicate a limited range of sulphur isotope values (type 2, ${\delta}^{34}S=-13.3{\sim}-11.7$‰; type 3, ${\delta}^{34}S=-13.9{\sim}-8.2$‰), and a result of geothermometry presents different temperature ranges: type 2($251{\pm}38^{\circ}C{\sim}277{\pm}40^{\circ}C$); type 3($360{\pm}2^{\circ}C$ to $537{\pm}29^{\circ}C$). It is estimated to be due to the effect of metamorphism and Maytyubin granitoid intrusions, respectively. In addition, ternary chart of thorium, scandium, and zircon for discrimination of tectonic setting and redox sensitivity using V/Mo values indicate that hydrothermal sediments put on reduction environment after precipitation, before being affected by metamorphism and intrusion activity. Geochemical data are plotted on a distal trend of SEDEX-type with discrimination plot using SEDEX index. As a result, petrological-geochemical properties demonstrate that Dyusembay Pb-Zn mineralized zone is comparable to distal-type of SEDEX deposit.

Mineral Products and Characteristics of Phase Transformation after Hydrothermal Treatment according to the Synthetic Method and Cation Combination during Birnessite Synthesis (버네사이트 합성 시 합성 방법 및 양이온 조건에 따른 생성 광물 및 열수처리 후 상전이 특성)

  • Min, Soyoung;Kim, Yeongkyoo
    • Economic and Environmental Geology
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    • v.52 no.6
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    • pp.509-517
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    • 2019
  • The birnessite (7Å manganate, δ-MnO2) which is a manganese oxide and comprises manganese nodules, is a major manganese mineral on the earth surface and a precursor in the synthesis of todorokite. In this study birnessite was synthesized by three different methods: Feng et al. (2004) and Luo et al. (1998) based on redox reaction and Ma et al. (1999) based on reduction reaction. 12 birnessite samples were synthesized by different combinations of Na+ and K+ cations based on the base (OH-) and permanganate (MnO4-) reagents in the synthesis. The mineral compositions of synthesized birnessite were identified by XRD, and the two cation ratio in the mineral was measured by ICP. The products obtained after hydrothermal treatment of Mg-buserite, by the precursor of birnessite, was examined by XRD, and then phase transition to todorokite and their characteristics were compared. Our results show that the byproducts and the characteristics of phase transition by each synthetic method have different trends. Hausmannite (γ-Mn3O4) and feitknechtite (β-MnOOH) were formed by both methods in the redox reaction mechanism. By Feng et al. (2004)'s method, manganite (γ-MnOOH) phase only appeared when cation was predominantly Na+. Two birnessite samples synthesized by redox reaction mechanism showed phase transition to todorokite (10Å manganate, OMS-1) when both NaOH and KMnO4 were used together. However, single-phase birnessite was formed by Ma et al. (1999)'s method, and phase transition was confirmed only for the sample when the cation was only composed of Na+.

Glycerol Steam Reforming for Hydrogen Production on Metal-ceramic Core-shell CoAl2O4@Al Composite Structures (금속-세라믹 Core-Shell CoAl2O4@Al 구조체를 적용한 불균일계 촉매의 글리세롤 수소전환 반응특성)

  • Kim, Jieun;Lee, Doohwan
    • Clean Technology
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    • v.21 no.1
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    • pp.68-75
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    • 2015
  • In this study, we investigated the structure and properties of a highly heat conductive metal-ceramic core-shell CoAl2O4@Al micro-composite for heterogeneous catalysts support. The CoAl2O4@Al was prepared by hydrothermal surface oxidation of Al metal powder, which resulted in the structure with a high heat conductive Al metal core encapsulated by a high surface area CoAl2O4 shell. For comparison, CoAl2O4 was also prepared by co-precipitation method and also utilized for a catalyst support. Rh catalysts supported on CoAl2O4@Al and CoAl2O4 were prepared by incipient wetness impregnation and characterized by N2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), CO chemisorption, and temperature-programmed reduction (TPR). The properties of catalysts were investigated for glycerol steam reforming reaction for hydrogen production at 550 ℃. Rh/CoAl2O4@Al exhibited about 2.8 times higher glycerol conversion turnover frequency (TOF) than Rh/CoAl2O4 due to facilitated heat transport through the core-shell structure. The CoAl2O4@Al and CoAl2O4 also showed some catalytic activities due to a partial reduction of Co on the support, and a higher catalytic activity was also found on the CoAl2O4@Al core-shell than CoAl2O4. These catalysts, however, displayed deactivation on the reaction stream due to carbon deposition on the catalysts surface.

Geochemical Evolution of CO2-rich Groundwater in the Jungwon Area (중원 지역 탄산수의 지구화학적 진화)

  • 고용권
    • Economic and Environmental Geology
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    • v.32 no.5
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    • pp.469-483
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    • 1999
  • Two different types of deep groundwaters occur together in the Jungwon area: $CO_2$-rich water and alkali water. Each water shows distrinct hydrogeochemical and environmental isotopic characteristics. The $CO_2$-rich waters are characterized by lower pH(6.0~6.4), higher Eh (25~85mV) and higher TDS content (up to 3,300 mg/l), whereas the alkali type waters have higher pH (9.1~9.5), lower Eh (-136~-128mV) and lower TDS content (168~254 mg/l). The CO2-rich waters ($Pco_2$=up to 1atm) were probably evolved by the local supply of deep $CO_2$ during the deep circulation, resulting in enhanced dissolution of surrounding rocks to yield high concentrations of $Ca^{2+}, Na^+, Mg^{2+}, K^+\; and \;HCO_3\;^-$ under low pH conditions. On the other hand, the alkali type waters ($Pco_2$=about 10-4.6 atm) were evolved through lesser degrees of simple wate/rock (granite) interaction under the limited suppy of $CO_2$. The alkali waters are relatively enriched in F- (up to 14mg/l), whereas the F- concentration of$CO_2$-rich water is lower (2.2~4.8 mg/l) due to the buffering by precipitation of fluorite. The oxygen-hydrogen isotopes and tritium data indicate that compared to shaltion ($\delta$18O=-9.5~-7.8$\textperthousand$),two different types fo deep groudwaters (<1.0TU)were both derived from pre-thermonuclear (more than 40 years old) meteoric waters with lighter O-H isotopic composition ($\delta$18O=-9.5~-7.8$\textperthousand$) and have evolved through prolonged water/rock interaction. The $CO_2$-rich waters also show some degrees of isotopic re-equilibration with $CO_2$ gas. The $\delta^{34}S$ values of dissolved sulfates (+24.2~+27.6$\textperthousand$) in the $CO_2$-rich waters suggest the reduction of sulfate by organic activity at depths. The carbon isotope data show that dissolved carbon in the $CO_2$-rich waters were possibly derived either from dissolution of calcite or from deep $CO_2$ gas. However, strontium isotope data indicate Ca in the $CO_2$-rich waters were derived mainly from plagioclase in granite, not from hydrothermal calcites.

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Electrochemical Properties of Using MnO2-HCS Composite for Supercapacitor (MnO2-HCS 복합체를 이용한 슈퍼커패시터의 전기화학적 특성)

  • Jin, En Mei;Jeong, Sang Mun
    • Clean Technology
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    • v.24 no.3
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    • pp.183-189
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    • 2018
  • Hollow carbon spheres (HCS) and carbon spheres (CS) were prepared by a hydrothermal reaction and they were introduced as a substrate for the deposition of $MnO_2$ nanoparticles. The $MnO_2$ nanoparticles were deposited on the carbon surface by a chemical redox deposition method. After deposition, the $MnO_2$ nanoparticles were uniformally distributed on the carbon surface in a slit-shape, and sparse $MnO_2$ slits appeared on the HCS surface. The $MnO_2-HCS$ showed an initial specific capacitance of $164.1F\;g^{-1}$ at scan rate of $20mv\;s^{-1}$, and after 1,000 cycles, the specific capacitance was maintained to $141.3F\;g^{-1}$. The capacity retention of $MnO_2-HCS$ and $MnO_2-CS$ were calculated to 86% and 78% in the cycle performance test up to 1,000 cycles, respectively. $MnO_2-HCS$ showed a good cycle stability due to the mesoporous hollow structure which can cause a faster diffusion of the electrolyte and can easily adsorb and desorb $Na^+$ ions on the surface of the electrode.

Skarn Formation in Metamorphic Rocks of the Chungju Mine Area (충주광산 지역 계명산층의 텅스텐 스카른화작용)

  • Kim, Gun-Soo;Park, Maeng-Eon
    • Economic and Environmental Geology
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    • v.28 no.3
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    • pp.185-197
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    • 1995
  • Tungsten skarns in the Chungju mine which consists mainly of strata-bound type iron ore deposits are found in the vicinity of the contact between the age-unknown Kyemeongsan Formation and granitic rock intrusions of Mesozoic age($134{\pm}2Ma$). Tungsten skarns were formed extensively from alumina and silica-rich schistose rocks by the introduction of calcium and iron from hydrothermal solution. The skarns comprise a metasomatic column and are subdivided into four facies; garnet facies, wollastonite facies, epidote facies and chlorite facies. The skarn process in time-evolutional trend can be divided broadly into the four facies in terms of the paragenetic sequence of calc-silicates and their chemical composition. Skarn and ore minerals were formed in the following sequence; (1) garnet facies, adjacent to biotite granite, containing mainly garnet(>Ad96) and magnetite, (2) wollastonite facies containing mainly wollastonite and garnet(Ad95~60), (3) epidote facies, containing mainly epidote(Ps35~31), quartz, andradite-grossular(Ad63~50), and scheelite, (4) chlorite facies, adjacent to and replacing schist, containing mainly chrolite, muscovite, quartz, calcite, epidote(Ps31~25), hematite and sulfides. The mineral assemblage and mineral compositions. suggest that the chemical potentials of Ca and Fe increased toward the granitic rock, and the component Al, Mg, K, and Si decreased from the host rock to granitic rock. The homogenization temperature and salinity of fluid inclusion in scheelite, quartz and epidote of epidote facies skarn is $300-400^{\circ}C$ and 3-8wt.% eqiv. NaCl, respectively. ${\delta}^{34}S$ values of pyrite and galena associated with chlorite facies skarn is $9.13{\sim}9.51%_{\circ}$ and $5.85{\sim}5.96%_{\circ}$, respectively. The temperature obtained from isotopic com· position of coexisting pyrite-galena is $283{\pm}20^{\circ}C$. Mineral assemblages and fluid inclusion data indicate that skarn formed at low $X_{CO_2}$, approximately 0.01. Temperature of the skarn mineralization are estimated to be in the range of $400^{\circ}C$ to $260^{\circ}C$ and pressure to be 0.5 kbar. The oxygen fugacity($fo_2$) of the skarn mineralization decreased with time. The early skarn facies would have formed at log $fo_2$ values of about -25 to -27, and late skarn facies would have formed at log $fo_2$ values of -28 to -30. The estimated physicochemical condition during skarn formation suggests that the principal causes of scheelite mineralization are reduction of the ore·forming fluid and a decrease in temperature.

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Utilization of Plant Phytase to Improve Phosphorous Availability for Broiler (육계의 인 이용율 향상을 위한 식물성 Phytase의 이용)

  • Kim, B.H.;Namkung, H.;Paik, I.K.
    • Journal of Animal Science and Technology
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    • v.44 no.4
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    • pp.407-418
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    • 2002
  • This study was conducted to evaluate the efficacy of wheat and wheat bran  as the source of phytase in a 5 week broiler feeding trial. One thousand day-old broiler chickens(Ross$^{(R)}$) were divided into 20 pens of 50 broilers(25 male and 25 female) each. Four pens were randomly arranged to one of the five dietary treatments: T1, control diet containing normal nonphytate P(NPP) ;  T2, T1 - 0.1% NPP; T3, T2 + 600IU microbial phytase(NOVO$^{(R)}$) per kg diet; T4, T2 + 600IU plant phytase from wheat and wheat bran; T5, T2 + 600IU plant phytase from wheat and hydrothermally treated wheat bran. Reduction of NPP level by 0.1%(T2) reduced weight gain and feed intake but plant phytase treatments(T4 and T5) recovered the lost performance. Plant phytase treatments showed better (p<0.05) weight gain and intake than the microbial phytase treatment(T3). There was no difference between regular wheat bran treatment(T4) and hydrothermally treated wheat bran treatment(T5). Mortality was the highest by low NPP diet(T2). Availability of ether extract and crude ash of grower diet was the highest(p<0.05) in normal wheat bran diet(T4). Availability of Ca and P of grower diet was the highest(p<0.05) in T4 followed by T3 and T5. Availability of Mg, Fe and Zn was drastically improved by phytase treatments(T3, T4 and T5). Excretion of Ca, P, Mg, Fe and Zn was the lowest(p<0.05) with microbial phytase treatment(T3). Serum level of Ca and Mg was the highest(p<0.05) with the low NPP treatment(T2). Tibial ash content of T2 and T3 was lower(p<0.05) than that of T1, T4 and T5. However, tibial Ca content was higher(p<0.05) in T1 and T2 than other treatments. Tibial P and Mg contents were the highest(p<0.05) in T1. It was concluded that plant phytase from wheat bran can be effectively used to improve P utilization. Hydrothermal treatment of wheat bran prior to inclusion in the diet had no beneficial effects.

Preparation and Characterization of $Cu/Ce_xZr_{1-x}O_2$ Catalysts for Preferential Oxidation of Carbon Monoxide (일산화탄소의 선택적 산화반응을 위한 $Cu/Ce_xZr_{1-x}O_2$ 촉매의 합성과 특성분석)

  • Lee, So-Yeon;Lee, Suk-Hee;Cheon, Jae-Kee;Woo, Hee-Chul
    • Clean Technology
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    • v.13 no.1 s.36
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    • pp.54-63
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    • 2007
  • Even traces of CO in the hydrogen-rich feed gas to proton exchange membrane fuel cells (PEMFC) poison the platinum anode electrode and dramatically decrease the power output. In this work, a variety of catalytic materials consisting of $Cu/Ce_xZr_{1-x}O_2$, (x = 0.0-1.0) were synthesised, characterized and tested for CO oxidation and preferential oxidation of CO (PROX). These catalysts prepared by hydrothermal and deposition-precipitation methods. The catalysts were characterized by XRD, XRF, SEM, BET, $N_2O$ titration and oxygen storage capacity (OSC) measurement. The effects of composition of the support and degree of excess oxygen were investigated fur activity and $CO_2$ selectivity with different temperatures. The composition of the support markedly influenced the PROX activity. Among the various $Cu/Ce_xZr_{1-x}O_2$ catalysts having different composition, $Cu/Ce_{0.9}Zr_{0.1}O_2$ and $Cu/Ce_{0.7}Zr_{0.3}O_2$ showed the highest activities (>99%) and selectivities (ca.50%) in the temperature range of $150{\sim}160^{\circ}C$. It was found that by using of $Ce_xZr_{1-x}O_2$ mixed oxide support which possesses a high oxygen storage capacity, oxidation-reduction activity of Cu-based catalyst was improved, which resulted in the increase of catalytic activity and selectivity of CO oxidation in excess $H_2$ environments.

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Distribution of Agalmatolite Mines in South Korea and Their Utilization (한국의 납석 광산 분포 현황 및 활용 방안)

  • Seong-Seung Kang;Taeyoo Na;Jeongdu Noh
    • The Journal of Engineering Geology
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    • v.33 no.4
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    • pp.543-553
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    • 2023
  • The current status of domestic a agalmatolite mines in South Korea was investigated with a view to establishing a stable supply of agalmatolite and managing its demand. Most mined agalmatolite deposits were formed through hydrothermal alteration of Mesozoic volcanic rocks. The physical characteristics of pyrophyllite, the main constituent mineral of agalmatolite, are as follows: specific gravity 2.65~2.90, hardness 1~2, density 1.60~1.80 g/cm3, refractoriness ≥29, and color white, gray, grayish white, grayish green, yellow, or yellowish green. Among the chemical components of domestic agalmatolite, SiO2 and Al2O3 contents are respectively 58.2~67.2 and 23.1~28.8 wt.% for pyrophyllite, 49.2~72.6 and 16.5~31.0 wt.% for pyrophyllite + dickite, 45.1 and 23.3 wt.% for pyrophyllite + illite, 43.1~82.3 and 11.4~35.8 wt.% for illite, and 37.6~69.0 and 19.6~35.3 wt.% for dickite. Domestic agalmatolite mines are concentrated mainly in the southwest and southeast of the Korean Peninsula, with some occurring in the northeast. Twenty-one mines currently produce agalmatolite in South Korea, with reserves in the order of Jeonnam (45.6%) > Chungbuk (30.8%) > Gyeongnam (13.0%) > Gangwon (4.8%), and Gyeongbuk (4.8%). The top 10 agalmatolite-producing mines are in the order of the Central Resources Mine (37.9%) > Wando Mine (25.6%) > Naju Ceramic Mine (13.4%) > Cheongseok-Sajiwon Mine (5.4%) > Gyeongju Mine (5.0%) > Baekam Mine (5.0%) > Minkyung-Nohwado Mine (3.3%) > Bugok Mine (2.3%) > Jinhae Pylphin Mine (2.2%) > Bohae Mine. Agalmatolite has low thermal conductivity, thermal expansion, thermal deformation, and expansion coefficients, low bulk density, high heat and corrosion resistance, and high sterilization and insecticidal efficiency. Accordingly, it is used in fields such as refractory, ceramic, cement additive, sterilization, and insecticide manufacturing and in filling materials. Its scope of use is expanding to high-tech industries, such as water treatment ceramic membranes, diesel exhaust gas-reduction ceramic filters, glass fibers, and LCD panels.