TECHNICAL PAPERS
Aug 15, 2002

Novel Bifunctional Aluminum for Oxidation of MTBE and TAME

Publication: Journal of Environmental Engineering
Volume 128, Issue 9

Abstract

The transformation of methyl tert-butyl ether (MTBE) and tert-amyl methyl ether (TAME) using bifunctional aluminum in the presence of dioxygen (O2) has been examined. Bifunctional aluminum, prepared by sulfating zero-valent aluminum with sulfuric acid, is an innovative extension of zero-valent metal technology. It has a dual functionality of simultaneously decomposing both reductively and oxidatively degradable contaminants. Bifunctional aluminum is capable of utilizing dioxygen through a reductive activation process to degrade oxygenates at ambient temperature and pressure where oxygenates are stable. The reductive activation of dioxygen is a new concept for oxygenate treatments for which most of oxidative technologies require strong oxidants. Results indicate that aluminum serves as a reductant to create favorable reducing conditions while sulfur-containing species, generated by the sulfation of aluminum at the metal surface, are considered to act as active sites. MTBE and TAME underwent similar parallel reaction pathways where the oxidation occurred on both sides of ether linkage. The oxidation of MTBE produced primarily tert-butyl alcohol, tert-butyl formate, methyl acetate, and acetone while tert-amyl alcohol, tert-amyl formate, methyl acetate, methyl ethyl ketone, and acetone accounted for 71.7% of the TAME lost. A postulated mechanism rationalizing the oxidation of oxygenates by bifunctional aluminum is proposed.

Get full access to this article

View all available purchase options and get full access to this article.

References

Akita, M., and Moro-oka, Y.(1998). “Reductive activation of dioxygen: A new concept for the catalytic oxidation.” Catal. Today, 44, 183–188.
Barreto, R. D., Gray, K. A., and Anders, K.(1995). “Photocatalytic degradation of methyl tert-butyl ether in TiO2 slurries: A proposed reaction scheme.” Water Res., 29, 1242–1248.
Bielaski, A., and Haber, J. (1991). Oxygen in catalysis, Marcel Dekker, New York.
Burris, D. R., Campbell, T. J., and Manoranjan, V. S.(1995). “Sorption of trichloroethylene and tetrachloroethylene in batch reactive metallic iron-water system.” Environ. Sci. Technol., 29, 2850–2855.
Butler, P. E.(1964). “The mass spectra of organic molecules. The rearrangement of acetylenic ethers under electron impact.” J. Org. Chem., 29, 3024–3028.
California Environmental Protection Agency (Cal–EPA). (1998). “Fact sheet: Arcadia wellfield/Charnock sub-basin MTBE projects.” Santa Monica, Calif.
Chen, C. T., Tafuri, A. N., Rahman, M., Foerst, M. B., Pfetzing, E., and Taylor, M. (1995). “Oxidation of methyl t-butyl ether (MTBE) using Fenton’s reagent.” Proc. 88th Annual Meeting of the Air & Waste Management Association, San Antonio, Tex., Paper No. 95-WA91.03.
Church, C. D., Pankow, J. F., and Tratnyek, P. G.(1999). “Hydrolysis of tert-butyl formate: Kinetics, products, and implications for the environmental impact of methyl tert-butyl ether.” Environ. Toxical. Chem., 18, 2789–2796.
Gillham, R. W., and O’Hannesin, S. F.(1994). “Enhanced degradation of halogenated aliphatics by zero-valent iron.” Ground Water, 32, 958–967.
Idriss, H., and Seebauer, E. G.(1996). “Fast photoreactions of oxygenates on tropospheric fly ash particles.” J. Vac. Sci. Technol. A, 14, 1627–1632.
Japar, S. M., Wallington, T. J., Richert, J. F. O., and Ball, J. C.(1990). “The atmospheric chemistry of oxygenated fuel additives: t-butyl alcohol, dimethyl ether, and methyl t-butyl ether.” Int. J. Chem. Kinet., 22, 1257–1269.
Johnson, R., Pankow, J., Bender, D., Price, C., and Zogorski, J.(2000). “MTBE: To what extent will past releases contaminate community water supply wells?” Environ. Sci. Technol., 34, 210A–217A.
Kadi, B. E., and Baronnet, F. J.(1995). “Study of the oxidation of unsymmetrical ethers (ETBE, TAME) and tentative interpretation of their high octane numbers.” J. Chim. Phys., 92, 706–725.
Kang, J. W., and Hoffmann, M. R.(1998). “Kinetics and mechanism of the sonolytic destruction of methyl tert-butyl ether by ultrasonic irradiation in the presence of ozone.” Environ. Sci. Technol., 32, 3194–3199.
Langer, S., Ljungstrom, E., Wangberg, I., Wallington, T. J., Hurley, M. D., and Nielsen, O. J.(1996). “Atmospheric chemistry of di-tert-butyl ether: rates and products of the reactions with chlorine atoms, hydroxyl radicals, and nitrate radicals.” Int. J. Chem. Kinet., 28, 299–306.
Liang, S., Palencia, L. S., Yates, R. S., Davis, M. K., Bruno, J., and Wolfe, R. L.(1999). “Oxidation of MTBE by ozone and peroxone processes.” J. Am. Water Works Assoc., 91, 104–114.
Lien, H. L., and Wilkin, R. (2002). “MTBE oxidation by bifunctional aluminum.” Proc. Third International Conf. on Remediation of Chlorinated and Recalcitrant Compounds, Monterey, Calif.
Lien, H. L., and Zhang, W. (2000). “Simultaneous oxidation of MTBEand reduction of carbon tetrachloride using acidified aluminum.” Proc., 219th National Meeting of American Chemical Society, Div. Environ. Chem., Vol. 40, San Francisco, Calif., 234–236.
Matouq, M., and Goto, S.(1993). “Kinetics of liquid phase synthesis of methyl tert-butyl ether from tert-butyl alcohol and methanol catalyzed by ion exchange resin.” Int. J. Chem. Kinet., 25, 825–831.
Misono, M., and Okuhara, T.(1993). “Solid superacid catalysts.” CHEMTECH, 23(11), 23–29.
Mitani, M. M., Keller, A. A., Bunton, C. A., Rinker, R. G., and Sandall, O. C.(2002). “Kinetics and products of reactions of MTBE with ozone and ozone/hydrogen peroxide in water.” J. Haz. Mat., B89, 197–212.
Morrison, R. T., and Boyd, R. N. (1987). Organic chemistry. 5th Ed., Allyn and Bacon, Inc., Boston.
Otsuka, K., Yamanaka, I., and Hosokawa, E.(1990). “A fuel cell for the partial oxidation of cyclohexane and aromatics at ambient temperatures.” Nature (London), 345, 697–698.
Puls, R. W., Powell, R. M., Blowes, D. W., Gillham, R. W., Schultz, D., Sivavec, T., Vogan, J. L., Powell, P. D., and Landis, R. (1998). “Permeable reactive barrier technologies for contaminant remediation.” Rep. No. EPA/600/R-98-125, Office of Research and Development, Washington D.C.
Raese, J. W., Sandstrom, M. W., and Rose, D. L. (1995). “U.S. geological survey method for methyl tert-butyl ether and other fuel oxygenates.” U.S. Geological Survey Fact Sheet FS-219-95, U.S. Geological Survey; Washington, DC.
Schuberth, J.(1991). “Volatile compounds detected in blood of drunk drivers by headspace/capillary gas chromatography/ion trap mass spectrometry.” Biol. Mass Spectrom, 20, 699–702.
Sheldon, R. A., ed. (1994). Metalloporphyrins in catalytic oxidations, Marcel Dekker, New York.
Sheldon, R. A., and Kochi, J. K. (1981). Metal-catalyzed oxidations of organic compounds, Academic, New York.
Smith, D. F., Kleindienst, T. E., Hudgens, E. E., Mclever, C. D., and Buffalini, J. J.(1991). “The photooxidation of methyl tertiary butyl ether.” Int. J. Chem. Kinet., 23, 907–924.
Song, X., and Sayari, A.(1996). “Sulfated zirconia-based strong solid-acid catalysts: Recent progress.” Catal. Rev. - Sci. Eng., 38, 329–412.
Speth, T. F., and Miltner, R. J.(1990). “Technical note: adsorption capacity of GAC for synthetic organics.” J. Am. Water Works Assoc., 82, 72–75.
Squillace, P. J., Pankow, J. F., Korte, N. E., and Zogorski, J. S.(1997). “Review of the environmental behavior and fate of methyl tert-butyl ether.” Envir. Toxicol. Chem., 16, 1836–1844.
Squillace, P. J., Zogorski, J. S., Wilber, W. G., and Price, C. V.(1996). “Preliminary assessment of the occurrence and possible sources of MTBE in groundwater in the United States, 1993-1994.” Environ. Sci. Technol., 30, 1721–1730.
Stefan, M. I., Mack, J., and Bolton, J. R.(2000). “Degradation pathways during the treatment of methyl tert-butyl ether by the UV/H2O2 process.” Environ. Sci. Technol., 34, 650–658.
Stevens, W., and Van Es, A.(1964). “Mixed carboxylic acid anhydrides.” Recueil, 83, 1287–1293.
vel Leitner, N. K., Papailhou, A.-L., Croue, J. P., Peyrot, J., and Dore, M.(1994). “Oxidation of methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (EBTE) by ozone and combined ozone/hydrogen peroxide.” Ozone. Sci. Eng., 16, 41–54.

Information & Authors

Information

Published In

Go to Journal of Environmental Engineering
Journal of Environmental Engineering
Volume 128Issue 9September 2002
Pages: 791 - 798

History

Received: Feb 13, 2002
Accepted: Feb 14, 2002
Published online: Aug 15, 2002
Published in print: Sep 2002

Permissions

Request permissions for this article.

Authors

Affiliations

Hsing-Lung Lien, A.M.ASCE
Assistant Professor, Dept. of Civil and Environmental Engineering, National Univ. of Kaohsiung, Kaohsiung, Taiwan (corresponding author).
Weixian Zhang, M.ASCE
Associate Professor, Dept. of Civil and Environmental Engineering, Lehigh Univ., Bethlehem, PA 18015.

Metrics & Citations

Metrics

Citations

Download citation

If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.

Cited by

View Options

Get Access

Access content

Please select your options to get access

Log in/Register Log in via your institution (Shibboleth)
ASCE Members: Please log in to see member pricing

Purchase

Save for later Information on ASCE Library Cards
ASCE Library Cards let you download journal articles, proceedings papers, and available book chapters across the entire ASCE Library platform. ASCE Library Cards remain active for 24 months or until all downloads are used. Note: This content will be debited as one download at time of checkout.

Terms of Use: ASCE Library Cards are for individual, personal use only. Reselling, republishing, or forwarding the materials to libraries or reading rooms is prohibited.
ASCE Library Card (5 downloads)
$105.00
Add to cart
ASCE Library Card (20 downloads)
$280.00
Add to cart
Buy Single Article
$35.00
Add to cart

Get Access

Access content

Please select your options to get access

Log in/Register Log in via your institution (Shibboleth)
ASCE Members: Please log in to see member pricing

Purchase

Save for later Information on ASCE Library Cards
ASCE Library Cards let you download journal articles, proceedings papers, and available book chapters across the entire ASCE Library platform. ASCE Library Cards remain active for 24 months or until all downloads are used. Note: This content will be debited as one download at time of checkout.

Terms of Use: ASCE Library Cards are for individual, personal use only. Reselling, republishing, or forwarding the materials to libraries or reading rooms is prohibited.
ASCE Library Card (5 downloads)
$105.00
Add to cart
ASCE Library Card (20 downloads)
$280.00
Add to cart
Buy Single Article
$35.00
Add to cart

Media

Figures

Other

Tables

Share

Share

Copy the content Link

Share with email

Email a colleague

Share