• Journal of Soil and Groundwater Environment
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• v.12 no.2
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• pp.27-36
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• 2007

A recent study showed that MTBE can be degraded by Fenton's Reagent (FR). The treatment of MTBE with FR, however, has a definite limitation of extremely low pH requirement (optimum pH $3{\sim}4$) that makes the process impracticable under neutral pH condition on which the ferrous ion precipitate forming salt with hydroxyl anion, which result in the diminishment of the Fenton reaction and incompatible with biological treatment. Consequently, this process using only FR is not suitable for in-situ remediation of MTBE. In order to overcome this limitation, modified Fenton process using NTA, oxalate, and acetate as chelating reagents was introduced into this study. Modified Fenton reaction, available at near neutral pH, has been researched for the purpose of obtaining high performance of oxidation efficiency with stabilized ferrous or ferric ion by chelating agent. In the MTBE degradation experiment with modified Fenton reaction, it was observed that this reaction was influenced by some factors such as concentrations of ferric ion, hydrogen peroxide, and each chelating agent and pH. Six potential chelators including oxalate, succinate, acetate, citrate, NTA, and EDTA were tested to identify an appropriate chelator. Among them, oxalate, acetate, and NTA were selected based on their remediation efficiency and biodegradability of each chelator. Using NTA, the best result was obtained, showing more than 99.9% of MTBE degradation after 30 min at pH 7; the initial concentration of hydrogen peroxide, NTA, and ferric ion were 1470 mM, 6 mM, and 2 mM, respectively. Under the same experimental condition, the removal of MTBE using oxalate and acetate were 91.3% and 75.8%, respectively. Optimum concentration of iron ion were 3 mM using oxalate which showed the greatest removal efficiency. In case of acetate, $[MTBE]_0$ decreased gradually when concentration of iron ion increased above 5 mM. In this research, it was showed that modified Fenton reaction is proper for in-situ remediation of MTBE with great efficiency and the application of chelatimg agents, such as NTA, was able to make the ferric ion stable even at near neutral pH. In consequence, the outcomes of this study clearly showed that the modified Fenton process successfully coped with the limitation of the low pH requirement. Furthermore, the introduction of low molecular weight organic acids makes the process more available since these compounds have distinguishable biodegradability and it may be able to use natural iron mineral as catalyst for in situ remediation, so as to produce hydroxyl radical without the additional injection of ferric ion.

• Applied Chemistry for Engineering
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• v.8 no.4
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• pp.582-588
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• 1997

Synthetic reaction of TAME, ETBE, and MTBE compounds used largely for gasoline octane number enhancer to prevent air pollution was investigated using heteropolyacid catalyst in a fixed bed flow reactor. In the synthetic reaction of TAME, ETBE and MTBE, after hetero atom being replaced with poly atom, the activity of the catalyst, $H_4SiW_{12}O_{40}$ with coordinated bond with W and an hetero atom of Si was the highest among the catalysts tested. Also the activity depended upon the metals replaced which are related to the catalyst acidity. $FeHPW_{12}O_{40}$ and $K_3PM_{o12}O_{40}$ catalysts showed high activity in TAME synthesis, while they were not effective in ETBE and MTBE synthesis. In this study catalysts showing high activity were selected and mixed with equal weight combination of $H_4SiW_{12}O_{40}$ and $Sr_2SiW_{12}O_{40}$ ;$H_4SiW_{12}O_{40}$ and $NaH_2PW_{12}O_{40}$ ; $Fe_{1.5}PW_{12}O_{40}$ and $Mg_2SiW_{12}O_{40}$ ; $Mg_2SiW_{12}O_{40}$ and $Ba_2SiW_{12}O_{40}$. The mixed heteropolyacid catalysts showed higher TBA conversion rate and better selectivity of ETBE and MTBE than the single catalysts.

• Journal of the Korean GEO-environmental Society
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• v.15 no.5
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• pp.39-46
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• 2014

The objectives of this study were to determine biodegradation and characteristics of BTEX and MTBE under aerovic-anaerobic conditions and evaluate the potential of natural attenuation method in denitrifying condition.. In the single-substrate experiments, all of the BTEX compounds were degraded under all the conditions. but, lower degradation of benzene and p-xylene were observed under aerobic condition due to the lack of oxygen initially supplied. In the mixed-substrate experiments, BTEX degradation was delayed compared to that in the single-substrate experiments due to a competition of the substrates. Biodegradation of MTBE was observed only under denitrifying conditions and we expected that MTBE mineralized to $CO_2$ without the accumulation of TBA. We also conducted to determine the effect of initial nitrate concentration on BTEX and MTBE degradation. At low nitrate concentration (<50 mg/L), BTEX degradations were limited by the lack of electron acceptor and BTEX degradation was inhibited at high nitrate concentration (>200 mg/L). The results in this study indicated that biotransformation could be applied to the gasoline-contaminated region under aerovic-anaerobic.

• Korean Membrane Journal
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• v.2 no.1
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• pp.36-47
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• 2000

This paper deals with the separation of MTBE-methanol mixtures using crosslinked Poly(vinyl alcohol)(PVA) membranes with sulfur-succinic acid(SSA) as a crosslinking agent by pervaporation and vapor permeation technique. The operating temperatures, methanol concentration in feed mixtures, and SSA concentrations in PVA membranes were varied to investigate the separation performance of PVA/SSA membranes and the optimum separation characteristics by pervaporation and vapor permeation. And also, for PVA/SSA membranes, the swelling measurements were carried out to study the transport phenomena. The swelling measurements were carried out for pure MTBE and methanol, and MTBE/methanol=90/10, 80/20 mixtures using PVA/SSA membranes with varying SSA compositions. There are two factors of the membrane network and the hydrogen bonding. In pervaporation separation was also carried out for MTBE/methanol=90/10, 80/20 mixtures at various temperatures. The sulfuric acid group in SSA took an important role in the membrane performance. The crosslinking effect might be over the hydrogen bonding effect due to the sulfuric acid group at 3 and 5% SSA membranes, and this two factors act vice versa on 7% SSA membrane. In this case, the 5% SSA membrane shows the highest separation factor of 2,095 with the flux of 12.79g/㎡$.$hr for MTBE/methanol=80/20 mixtures at 30$^{\circ}C$ which this mixtures show near the azeotopic composition. Compared to pervaporation, vapor permeation showed less flux and similar separation factor. In this case, the flux decreased significantly because of compact structure and the effect of hydrogen bonding. In vapor permeation, density or concentration of methanol in vaporous feed is lower than that of methanol in liquid feed, as a result, the hydrogen bonding portion between the solvent and the hydroxyl group in PVA is reduced in vapor permeation. In this case, the 7% SSA membranes shows the highest separation factor of 2,187 with the flux of 4.84g/㎡$.$hr for MTBE/methanol=80/20 mixtures at 30$^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.3049-3052
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• 2009

Methyl tert-butyl ether (MTBE) is added to gasoline to enhance the octane number of gasoline, tert-butyl alcohol (TBA) is major degradation intermediate of MTBE in environment, and benzene, toluene, ethyl benzene and xylene (BTEX) are also major constituents of gasoline. In this study, a simplified headspace analysis method was adapted for simultaneous determination of MTBE, TBA and BTEX in ground water samples. The sample 5.0 mL and 2 g NaCl were placed in a 10 mL vial and the solution was spiked with fluorobenzene as an internal standard and sealed with a cap. The vial was placed in a heating block at 85 $^{\circ}C$ for 30 min. The detection limits of the assay were 0.01 ${\mu}$g/L for MTBE and BTEX, and 0.02 ${\mu}$g/L for TBA. The method was used to analyze 110 ground water samples from various regions in Korea, and to survey the their background concentration in ground water in Korea. The samples revealed MTBE concentrations in the range of 0.01 - 0.45 ${\mu}$g/L (detection frequency of 57.3%), TBA concentrations in the range of 0.02 - 0.08 ${\mu}$g/L (detection frequency of 5.5%), and total BTEX concentrations in the range of 0.01 - 2.09 ${\mu}$g/L (detection frequency of 87.3%). The developed method may be used when simultaneously determining the amount of MTBE, TBA and BTEX in water.

• Membrane Journal
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• v.2 no.1
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• pp.36-36
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• 1992

This paper deals with the separation of MTBE-methanol mixtures using crosslinked Poly(vinyl alcohol)(PVA) membranes with sulfur-succinic acid(SSA) as a crosslinking agent by pervaporation and vapor permeation technique. The operating temperatures, methanol concentration in feed mixtures, and SSA concentrations in PVA membranes were varied to investigate the separation performance of PVA/SSA membranes and the optimum separation characteristics by pervaporation and vapor permeation. And also, for PVA/SSA membranes, the swelling measurements were carried out to study the transport phenomena. The swelling measurements were carried out for pure MTBE and methanol, and MTBE/methanol=90/10, 80/20 mixtures using PVA/SSA membranes with varying SSA compositions. There are two factors of the membrane network and the hydrogen bonding. In pervaporation separation was also carried out for MTBE/methanol=90/10, 80/20 mixtures at various temperatures. The sulfuric acid group in SSA took an important role in the membrane performance. The crosslinking effect might be over the hydrogen bonding effect due to the sulfuric acid group at 3 and 5% SSA membranes, and this two factors act vice versa on 7% SSA membrane. In this case, the 5% SSA membrane shows the highest separation factor of 2,095 with the flux of 12.79g/㎡·hr for MTBE/methanol=80/20 mixtures at 30℃ which this mixtures show near the azeotopic composition. Compared to pervaporation, vapor permeation showed less flux and similar separation factor. In this case, the flux decreased significantly because of compact structure and the effect of hydrogen bonding. In vapor permeation, density or concentration of methanol in vaporous feed is lower than that of methanol in liquid feed, as a result, the hydrogen bonding portion between the solvent and the hydroxyl group in PVA is reduced in vapor permeation. In this case, the 7% SSA membranes shows the highest separation factor of 2,187 with the flux of 4.84g/㎡·hr for MTBE/methanol=80/20 mixtures at 30℃.

• Journal of the Korean Applied Science and Technology
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• v.33 no.1
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• pp.118-128
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• 2016

As the interest on the air-pollution is gradually rising up at home and abroad, automotive and fuel researchers have been working on the exhaust emission reduction from vehicles through a lot of approaches, which consist of new engine design, innovative after-treatment systems, using clean (eco-friendly alternative) fuels and fuel quality improvement. This research has brought forward two main issues : exhaust emission and PM (particulate matter) particle emissions of gasoline vehicle. Exhaust emission and PM particle of automotive had many problem that cause of ambient pollution, health effects. In addition, researcher studied the environment problems of the MTBE contained in the fuel as oxygenate additives. The researchers have many data about the health effects of ingestion of MTBE. However, the data support the conclusion that MTBE is a potential human carcinogen at high doses. Based on the oxygenated fuel additive types (MTBE, Bio-ETBE, Bio-ethanol, Bio-butanol), this paper discussed the influence of oxygen contents on gasoline fuel properties and evaporative emission characteristics. Also, this paper assessed the acceleration and power performance of gasoline vehicle for the fuel property.

• Journal of the Korean GEO-environmental Society
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• v.12 no.10
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• pp.57-62
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• 2011

This study investigated the effects of various inorganic anions($Cl^-$, $NO_3{^-}$, $HCO_3{^-}$) on the Methyl tert Butyl Ether(MTBE) degradation by photocatalysis using statistical method. Generally, this process in general demands the generation of hydroxyl radicals(OH radical) in solution in the presence of UV light. The generation of radicals were affected by inorganic anions in solution that inhibited the photodegradation by their trapping hydroxyl radicals. The effects of inorganic anions were mathematically described as the independent variables such as $Cl^-$, $NO_3{^-}$, and $HCO_3{^-}$, and these were designed by mixture analysis that was one of the response surface methodology(RSM). Regression analysis on ANOVA showed significant p-value(p<0.0001) and high coefficients for determination value($R^2$=99.28%, ${R^2}_{adj}$=98.91%). Contour and response surface plots showed that the effects of inorganic anions for MTBE photodegradation based on $UV/H_2O_2$ process. In the result, $Cl^-$ and $HCO_3{^-}$ inhibited the photodegradation of the MTBE by their trapping hydroxyl radicals, and the interaction by these two factors was observed.

• Journal of the Korean Applied Science and Technology
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• v.25 no.2
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• pp.252-256
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• 2008

We investigated phase separation by adding different concentrations of MTBE, to the mixtures of naphtha, ethanol and water. The phase separation temperatures of the Naphtha-Ethanol-Water solutions have dropped when the concentration of MTBE increases more. When adding IPA and IBA to the solutions of Gasoline-Ethanol and Gasoline base-Ethanol individually, IBA shows lower temperatures of phase separation than IPA, and it shows synergistic effect when mixtures of IPA and IBA is applied.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 2002.11a
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• pp.31-37
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• 2002

미국의 캘리포니아에서는 1995년도부터 휘발유의 옥탄가 향상제로 첨가되는 메틸 터셔리 부틸 이스(Methyl tert-Butyl Ether, MTBE)의 사용을 금지시켰다. MTBE의 사용이 금지된 가장 큰 이유는 MTBE의 물에 패한 용해도가 높아서 주유소 지하저장 탱크를 통하여 지하수를 오염시키고 저장탱크 바닥의 물을 배출시킴으로 인하여 지표수도 오염시키는 문제가 있었기 때문이다.(중략)