1

INTRODUCTION

Methyl tert-butyl ether, also known as methyl tertiary butyl ether and MTBE, is an
organic compound with molecular formula (CH
3
)
3
COCH
3
. MTBE is a volatile, flammable, and
colorless liquid that is immiscible with water. It has a minty odor vaguely reminiscent of diethyl
ether, leading to unpleasant taste and odor in water. MTBE is a gasoline additive, used as an
oxygenate to raise the octane number. Its use is controversial in the US and declining in that
country in part because of its occurrence in groundwater and legislation favoring ethanol.
Worldwide production of MTBE has been constant at about 18 million tons/y (2005) owing to
growth in Asian markets which are less subject to ethanol subsidies.
MTBE is manufactured via the chemical reaction of methanol and isobutylene. Methanol
is derived from natural gas, and isobutylene is derived from butane obtained from crude oil or
natural gas, thus MTBE is derived from fossil fuels. In the United States, it was produced in very
large quantities (more than 200,000 barrels per day in 1999) during its use as a fuel additive.
MTBE is almost exclusively used as a fuel component in fuel for gasoline engines. It is
one of a group of chemicals commonly known as oxygenates because they raise the oxygen
content of gasoline. The uses of MTBE are as anti-knocking agent, alternatives to MTBE as an
anti-knock agent and as a solvent.
Firstly, in the US it has been used in gasoline at low levels since 1979 to replace
tetraethyl lead and to increase its octane rating helping prevent engine knocking. Oxygenates
help gasoline burn more completely, reducing tailpipe emissions from pre-1984 motor vehicles;
dilutes or displaces gasoline components such as aromatics (e.g., benzene) and sulfur; and
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optimizes the oxidation during combustion. Most refiners chose MTBE over other oxygenates
primarily for its blending characteristics and low cost.
Secondly, other compounds are available as additives for gasoline including ethanol and
some ethers such as tert-amyl methyl ether (TAME).Ethanol has been advertised as a safe
alternative by the agricultural interest groups in the USA and Europe. Its lack of toxicity is not
different from MTBE, but as a polar solvent, it drives off nonpolar hydrocarbons from the
gasoline, a problem that MTBE does not cause. Some volatile hydrocarbons in gasoline vapors
are carcinogens, and gasoline vapors produce photochemical smog. Ethanol's higher cost
requires government intervention in the form of subsidies or mandated usage to be competitive.
In 2003, California was the first U.S. state to start replacing MTBE with ethanol. Several
other states started switching soon thereafter.Advocates of both sides of the debate in the
United States sometimes claim that gasoline manufacturers have been forced to add MTBE to
gasoline by law. It might be more correct to say they have been induced to do so, although any
oxygenate would fulfill the law.An alternative to straight ethanol is the related ether ETBE, which
is manufactured from ethanol and isobutene. Its performance as an additive is similar to MTBE,
but due to the higher price of ethanol compared to methanol, it is more expensive.Higher quality
gasoline is also an alternative, i.e., so that additives such as MTBE are unnecessary. Iso-octane
itself is used. MTBE plants can be retrofitted to produce iso-octane from isobutylene.
Then,as a solvent, MTBE possesses one distinct advantage over most ethers - it has a
reduced tendency to form explosive organic peroxides. Opened bottles of diethyl ether or THF
can build up dangerous levels of these peroxides in months, whereas samples of MTBE are
usually safe for years (but they should still be tested periodically). For this reason (as well as its
higher boiling point), MTBE is used as a solvent extensively in industry, where safety concerns
and regulations make working with diethyl ether, THF, or other ethers much more difficult and
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expensive. However, despite the popularity of MTBE in industrial settings, it is rarely used as a
solvent in academia with some exceptions.MTBE forms azeotropes with water (52.6 C; 96.5%
MTBE) and methanol (51.3 C; 68.6% MTBE). Although an ether, MTBE is a poor Lewis base
and does not support formation of Grignard reagents. It is also unstable toward strong acids. It
reacts dangerously with bromine.















4


PROCESS OVERVIEW
MTBE (Methyl-tert-Butyl Ether) is a volatile, low viscosity clear liquid at room
temperature with an ether odour; boiling point 55.2 C; melting point -109 C. MTBE is flammable
and can form explosive mixtures with air. It is slightly soluble in water and very soluble ethers
and alcohol and in most organic solvents including hydro carbons. MTBE is an ether which
contains an oxygen atom bonded to two carbon atoms. In Methyl-tert-Butyl Ether, one carbon
atom is that of a methyl group and the other is the central atom in a tertiary butyl group.
MTBE is prepared by reacting isobutylene contained in a mixed C4 stream with
methanol in the presence of an acidic ion-exchange resin catalyst such as sulfonated styrene
linked with divinyl benzene at 100 C. Isobutylene can also be prepared from TBA by
dehydration and from n-butane by isomerization without dehydration. The most quantity
produced worldwide is used as an oxygenate to gasoline. It is added both to increase octane
enhancement to replace banned tetraethyl lead and to raise the oxygen content in gasoline. It is
known that MTBE in fuel reduces exhaust emissions of VOC (volatile organic compounds:
acetaldehyde, benzene, 1,3-butadiene, ethylbenzene, formaldehyde, toluene, xylenes, and
particulate organic matter) except formaldehyde. Ozone is formed by the reaction of sunlight
with NOx and VOCs.
Some quantity of MTBE is used in the preparation of isobutene. With strong solvating
capabilities for a wide variety of compounds including unsaturated hydrocarbons and steroids,
MTBE is used as a reaction medium and extraction solvent to replace methylene chloride,
aromatics, and other ethers. MTBE is a non-chlorinated process solvent. It is used as a solvent
for chromotographic techniques. The sterically hindered tertiary butyl group imparts stability. It
possesses a much lower tendency to form explosive organic peroxides than most ethers. It has
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also an acid stability compare to other diether acetals. It forms azeotrope with water (52 - 53 C)
and methanol (51 - 52 C). It is used as a solvent in Grignard synthesis and other organometallic
reactions. It is used as an anionic and cationic polymerization solvent.
















6

EXAMPLE PROCESS FLOW DIAGRAM 1



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EXAMPLE PROCESS FLOW DIAGRAM 2








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ESTIMATION COST FOR DESIGN BASIS FOR MTBE
Based on a review of data on the typical MTBE concentrations and flow rates required to
treat, available from USGS studies (Squillace et al., 1996; Delzer, 1996), and CAL-DHS (1998)
information, two general cases have been identified: (1) low concentration (30-100 ug/L) levels
and high flow rates, in the range of 500-1000 gpm (gallons per minute), which are typical of
contaminated drinking water supplies, whether from surface waters or from groundwater
pumping wells; and (2) high concentration (100-5000 ug/L) and low flow rates, in the range of
10-500 gpm, typical of groundwater wells near the source of contamination, usually a leaking
underground storage tank. Ten combinations of flow rate and concentration were selected as
the influent characteristics, as indicated in Table 1 :
Table 1. Combinations of MTBE Concentration and Flow rate Used for Design
CASE 1 2 3 4 5 6 7 8 9 10
Concentration (ug/L) 100 100 100 500 1000 5000 100 500 1000 5000
Flow rate (gpm) 1000 500 100 100 100 100 10 10 10 10
Although USEPA has in effect a 35 ug/L advisory level, we consider the CAL-DHS
secondary MCL level (5 ug/L) as the treatment goal in our design calculations. For some
selected cases we evaluate the cost differential between treatment to a 5 ug/L level and a 35
ug/L level.
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Capital costs are amortized over a 20 year horizon, at a 4% discount rate. Operation and
Maintenance (O&M) costs include operator(s) for the units, materials and electrical power, as
well as fuel for the thermal treatment when considered. The costs estimated here are at the
feasibility level (accuracy of at best -30% to +50%). For all the technologies considered,
additional costs may be required for pretreatment, depending on influent conditions, and post
treatment polishing or storage.
Equipment costs are calculated using the CapCost software (Turton et al., 1998). To
estimate the total capital costs, the following factors are applied:
(1) piping, electrical and valves (30% of equipment)
(2) site work (10% of equipment)
(3) contractor fees (15% of equipment plus items 1 and 2)
(4) engineering costs (15% on top of equipment plus items 1, 2, and 3)
(5) contingency (20% on top of all previous costs)
O&M costs are calculated based on electrical power requirements (at $0.08/kW-h), fuel
(at $1.6/million BTU and 3 BTU/scfm), labor (at $30/hr), materials considering 3% of equipment
per year, and contingency plus administrative of 15% on top of all other O&M costs.
The following sections present design considerations and cost estimates for air stripping,
granular activated carbon, ozone/hydrogen peroxide oxidation, and hollow fiber membranes.
The advantages and disadvantages of each technology are also discussed. Section 6
summarizes the cost estimates for the various technologies and provides recommendations for
the various cases studied. Experimental studies were conducted to verify parameter values
required for the calculations. The results are presented in the relevant sections.
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PROCESS AND MEASUREMENT
1) DISCLAIMER

Methyl tert-butyl ether (MTBE) is a flammable liquid with a distinctive, disagreeable odor.
It is made from blending chemicals such as isobutylene and methanol, and has been used since
the 1980s as an additive for unleaded gasolines to achieve more efficient burning.MTBE is also
used to dissolve gallstones. Patients treated in this way have MTBE delivered directly to their
gallbladders through special tubes that are surgically inserted.
MTBE quickly evaporates from open containers and surface water, so it is commonly
found as a vapor in the air. Small amounts of MTBE may dissolve in water and get into
underground water. It remains in underground water for a long time. MTBE may stick to
particles in water, which will cause it to eventually settle to the bottom sediment. MTBE may be
broken down quickly in the air by sunlight. MTBE does not build up significantly in plants and
animals.
Breathing small amounts of MTBE for short periods may cause nose and throat irritation.
Some people exposed to MTBE while pumping gasoline, driving their cars, or working in gas
stations have reported having headaches, nausea, dizziness, and mental confusion. However,
the actual levels of exposure in these cases are unknown. In addition, these symptoms may
have been caused by exposure to other chemicals. There is no data on the effects in people of
drinking MTBE. Studies with rats and mice suggest that drinking MTBE may cause
gastrointestinal irritation, liver and kidney damage, and nervous system effects.


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There is no evidence that MTBE causes cancer in humans. One study with rats found that
breathing high levels of MTBE for long periods may cause kidney cancer. Another study with
mice found that breathing high levels of MTBE for long periods may cause liver cancer. The
Department of Health and Human Services (DHHS), the International Agency for Research on
Cancer (IARC), and the EPA have not classified MTBE as to its carcinogenicity.
MTBE and its breakdown product, butyl alcohol, can be detected in your breath, blood,
or urine for up to 1 or 2 days after exposure. These tests aren't available at most doctors'
offices, but can be done at special laboratories that have the right equipment. There is no other
test specific to determining MTBE exposure.
The EPA has issued guidelines recommending that, to protect children, drinking water
levels of MTBE not exceed 4 milligrams per liter of water (4 mg/L) for an exposure of 1-10 days,
and 3 mg/L for longer-term exposures.
EXPOSURE PATHWAYS
Touching the skin or breathing contaminated air while pumping gasoline
Breathing exhaust fumes while driving a car
Breathing air near highways or in cities
Drinking, swimming, or showering in water that has been contaminated with MTBE
Receiving MTBE treatment for gallstones



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2) ABSTRACT
We developed an isotope-dilution method for measuring methyl tert-butyl ether (MTBE)
and tert-butyl alcohol (TBA) in whole human blood using a purge-and-trap gas chromatographic-
mass spectrometric method. The labeled analogues for MTBE and TBA were [2H12]methyl tert-
butyl ether and [2H9]-tert-butyl alcohol, respectively. Volatiles were removed from the blood by
direct helium purging of the liquid; were trapped on a Tenax trap; and were desorbed,
cryofocused, and chromatographed on a DB-624 capillary column that was connected directly to
the ion source of a mass spectrometer. Detection was by mass analysis using a double-
focusing magnetic-sector mass spectrometer operating in the full-scan mode at the medium
mass resolution of 3000.
For the isotope-dilution method, the minimum detection limits in blood (5-10 mL) are
0.01 microgram/L for MTBE and 0.06 microgram/L for TBA. The isotope-dilution method proved
to be a big improvement in recovery, reproducibility, and sensitivity over our previous analytical
method, which used the labeled ketone, [4-2H3]-2-butanone, as the internal standard for both
MTBE and TBA. The isotope-dilution method has sufficient sensitivity for monitoring blood levels
of MTBE and TBA in populations exposed to oxygenated fuels containing MTBE.







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REFERENCE
1. http://en.wikipedia.org/wiki/methyl_tert-butyl_ether...
excess on 01/05/2014 at 2.45pm
2. http://www.epn.gov/mtbe/faq.htm#concerns...
excess on 01/05/2014 at 3.45pm
3. http://monographs.iarc.fr
excess on 01/05/2014 at 4.45pm
4. INSTEP Notebook
5. MMSB/PPMSB SDN BHD manual/procedure of a MTBE plant ISO 9001 : 2000
6. http://pww.datakimia.petronas.com.my/datakimia/msds.exe?....
excess on 01/05/2014 at 5.45pm
7. Chemwatch Material Safety Data Sheet (REVIEW)