• Title/Summary/Keyword: Zeolites

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Dehydration of Lactic Acid to Bio-acrylic Acid over NaY Zeolites: Effect of Calcium Promotion and KOH Treatment (NaY 제올라이트 촉매 상에서 젖산 탈수반응을 통한 바이오아크릴산 생산: Ca 함침 및 KOH 처리 영향)

  • Jichan, Kim;Sumin, Seo;Jungho, Jae
    • Clean Technology
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    • v.28 no.4
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    • pp.269-277
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    • 2022
  • With the recent development of the biological enzymatic reaction industry, lactic acid (LA) can be mass-produced from biomass sources. In particular, a catalytic process that converts LA into acrylic acid (AA) is receiving much attention because AA is used widely in the petrochemical industry as a monomer for superabsorbent polymers (SAP) and as an adhesive for displays. In the LA conversion process, NaY zeolites have been previously shown to be a high-activity catalyst, which improves AA selectivity and long-term stability. However, NaY zeolites suffer from fast deactivation due to severe coking. Therefore, the aim of this study is to modify the acid-base properties of the NaY zeolite to address this shortcoming. First, base promoters, Ca ions, were introduced to the NaY zeolites to tune their acidity and basicity via ion exchange (IE) and incipient wetness impregnation (IWI). The IWI method showed superior catalyst selectivity and stability compared to the IE method, maintaining a high AA yield of approximately 40% during the 16 h reaction. Based on the NH3- and CO2-TPD results, the calcium salts that impregnated into the NaY zeolites were proposed to exit as an oxide form mainly at the exterior surface of NaY and act as additional base sites to promote the dehydration of LA to AA. The NaY zeolites were further treated with KOH before calcium impregnation to reduce the total acidity and improve the dispersion of calcium through the mesopores formed by KOH-induced desilication. However, this KOH treatment did not lead to enhanced AA selectivity. Finally, calcium loading was increased from 1wt% to 5wt% to maximize the amount of base sites. The increased basicity improved the AA selectivity substantially to 65% at 100% conversion while maintaining high activity during a 24 h reaction. Our results suggest that controlling the basicity of the catalyst is key to obtaining high AA selectivity and high catalyst stability.

Synthetic Study of Zeolites from Some Glassy Rocks (II) : Dissolution Behavior of Perlite and Zeolite Synthesis in Alkaline Aqueous Solution (유리질 암석으로부터 제올라이트 합성에 관한 연구(Ⅱ) : 알칼리 용액에서 진주암의 용해 거동과 제올라이트의 합성)

  • Noh, Jin-Hwan
    • Journal of the Mineralogical Society of Korea
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    • v.5 no.2
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    • pp.61-71
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    • 1992
  • Through the low-temperature(60-150${\circ}C$) hydrothermal treatment of perlite with the alkaline solution at various NaOH concentrations, the mode of volcanic glass alteration and resultant zeolite formation were investigated in a closed system. At a temperature of 80${\circ}C$ and alkalinities of pH range 8 to 12, corresponding to the natural environments of diagenetic zeolite formation, only weak dissolution of perlitic glass occurs without zeolite formation despite the residence time of 100 days. Activities of Si and Al increase progressively, as a consequence of increasing pH, whereas activity ratios of Si/Al decrease. Zeolites were synthesized from perlite in the alkaline solution at above 0.1M NaOH concentrations. Below the temperature of 100${\circ}C$ Na-P was mainly formed, whereas analcime was the dominant zeolite at the temperature range of 100-150${\circ}C$. During Na-P synthesis chabazite and Na-X were also formed as by-products in case of lower proportion of solution/sample(<10ml/g) and higher NaOH concentraion (>3M), respectively. The alteration modes of perlite in the zeolite synthesis reflect that the formation of synthetic zeolites occurs as an incongruent dissolution likely with the diagenetic formation of natural zeolites from volcanic glass. Considering much difference in reaction kinetics between natural and synthetic systems, however, the evaluated synthetic conditions in these experiments were not directly applicable to the natural diagenetic system.

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Characterization of Natural Zeolite and Study of Adsorption Properties of Heavy Metal Ions for Development of Zeolite Mine (제올라이트 광산개발을 위한 천연 제올라이트의 특성 분석 및 중금속 이온 흡착 특성 연구)

  • Kim, Hu Sik;Kim, Young Hun;Baek, Ki Tae;Lim, Woo Taik
    • Journal of the Mineralogical Society of Korea
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    • v.28 no.4
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    • pp.299-308
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    • 2015
  • The six natural zeolites collected in Pohang area, Kyungsangbuk-do, Korea, were characterized by XRD, XRF, DTA, TGA, and CEC analysis. The primary species of these zeolite are modenite, albite, and quarts in Kuryongpo-A (Ku-A), Kuryongpo-B (Ku-B), Kuryongpo-C (Ku-C), Donghae-A (Dh-A), Donghae-B (Dh-B), and Donghae-C (Dh-C) samples. The XRF analysis showed that the six zeolites contain Si, Al, Na, K, Mg, Ca, and Fe. Cation exchange capacity of Kuryongpo-C (Ku-C) zeolite was the highest compared to other zeolites. The capabilities of removing heavy metal ions such as $Pb^{2+}$, $Cd^{2+}$ and $Cu^{2+}$ were compared. The effect of reaction time in removing heavy metal ions was studied. The experimental results showed that the efficiency of removal was low for $Pb^{2+}$, $Cd^{2+}$ and $Cu^{2+}$ ions. These may be caused by the low content of zeolite in the six natural zeolites. This indicates that the adsorption capacity roughly tends to depend on the zeoite contents, ie., the grade of zeolite ore.

Removal of Heavy Metal Ions in Wastewater Using Zeolite Minerals (제올라이트광물을 이용한 폐수중의 중금속제거)

  • Yim Chai Suk;Yim Going
    • Korean Journal of Materials Research
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    • v.14 no.3
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    • pp.229-234
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    • 2004
  • All the applications of natural zeolites make use of one or more of their physical and chemical properties: adsorption, ion-exchange and related molecular sieve properties, dehydration and rehydration, and siliceous composition. Accordingly, the applications of zeolite have been carried out in the various aspects because of its large cation exchange capacity and adsorption properties. In this paper, the adsorption effect of heavy metal ions in wastewater on zeolite mineral by batch adsorption process is studied. The amounts of adsorbed ions were variable by original pH and ionic concentration, especially original pH of solution had an important effect on the adsorption. In case of low pH solution, e.g. below 3.0, clinoptilolite adsorbed $Pb^{2+}$ ,$ Cd ^{2+ }$ , $Cu^{2+}$ and $Zn^{ 2+}$ , but mordenite almost did not adsorb except $Pb^{2+}$ . Under the same conditions, these ions were more adsorbed on clinoptilolite than on mordenite mineral. The velocity of adsorption was relatively fast and it was confirmed by shaking test that the equilibrium of adsorption could be attained in about one hour. The species of exchangeable cation of zeolite had an effect on its removing ability and zeolite of the sodium-exchanged type was the best.

Dehydration of Methanol to Dimethyl Ether over ZSM-5 Zeolite

  • Jiang, Shan;Hwang, Jin-Soo;Jin, Tai-Huan;Cai, Tianxi;Cho, Wonihl;Baek, Young-Soon;Park, Sang-Eon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.2
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    • pp.185-189
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    • 2004
  • Methanol dehydration to dimethyl ether (DME) has been investigated over ZSM-5 zeolites and compared with that of ${\gamma}-Al_2O_3$. Although the catalytic activity was decreased with an increase in silica/alumina ratio, the DME selectivity increased. H-ZSM-5 and NaH-ZSM-5 zeolites were more active for conversion of methanol to DME than ${\gamma}-Al_2O_3$. $Na^+$ ion-exchanged H-ZSM-5 (NaH-ZSM-5) shows higher DME selectivity than H-ZSM-5 due to the selective removal of strong acid sites.

ZanF를 이용한 카드뮴(Cd)과 6가 크롬(Cr(VI))의 동시제거

  • 이승학;이광헌;명동일;박준범
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.04a
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    • pp.143-146
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    • 2004
  • Natural zeolites have exhibited high sorption capacity for inorganic cations including heavy metals and ammonium. Moreover, they were proven to be effective for environmental applications such as permeable barriers for controlling the spread of cation-contaminated groundwater. However zeolites have little or no affinity for anionic species like chromium, as they possess a net negative structural charge. To achieve the simultaneous sorption for anionic contaminants, surfactant-modified zeolite (SMZ) has been employed as the possible sorbents. Current study focuses on simultaneous removal of heavy metals having different ionic form in aqueous solution, cadmium (C $d^{2+}$) and chromium (Cr $O_{4}$$^{2-}$), using newly developed materials, ZanF. ZanF, a potential alternative to SMZ, was derived from zeolite modified by Fe(II) chloride followed by reduction with sodium borohydride. Batch experiments were performed to estimate the removal efficiency of ZanF at different conditions. Under different pH ranging from 2 to 6, removal efficiency was investigated. And C $d^{2+}$ removal efficiency was estimated by varying background concentration of Cr $O_{4}$$^{2-}$, and vice versa. With the test results, ZanF was expected to be a possible reactive materials alternative to SMZ in permeable reactive barriers (PRBs) for treating the contaminated groundwater with cationic and anionic heavy metals.als.

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The Effects of Zeolite Structure and Ion-exchange Material on NH3-SCR Reaction (제올라이트 종류 및 이온교환 물질에 따른 NH3-SCR 촉매 반응 특성)

  • Hwang, Inhye;Lee, Junho;Kim, Hongsuk;Jeong, Youngil
    • Transactions of the Korean Society of Automotive Engineers
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    • v.22 no.1
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    • pp.135-141
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    • 2014
  • $NH_3$-SCR has high NOx removal efficiency approximately 80~90%. Recently, the copper or iron ion-exchanged zeolite catalysts are widely used as automobile SCR catalysts. In this paper, the effect of the space velocity, temperature of reaction and $NO_2$ addition on the $NH_3$-SCR reaction were studied using various zeolite SCR catalysts. The test was conducted with small sized fresh catalysts in a laboratory fixed-bed flow reactor system using simulated gases. It is found that the activity of the BEA is better than MFI. It seems that three-dimensional framework and a wide pore entrance of BEA enhances the SCR activity. It is also found that low temperature activity of Cu-zeolites was better than Fe-zeolites. Once $NO_2$ was added, the NOx conversion activity of the Cu-zeolite was slightly enhanced, whereas remarkable improvement was achieved by Fe-zeolite.