DECOMPOSITION OF MTBE

1. History

Methyltert-butyl ether (MTBE) is known as gasoline additive that raise octane

number to improve fuel performance. Higher octane rated fuels are recognize to
provide higher performance in the gasoline industry. (Anderson, 2012). MTBE is
manufactured from by the reaction of methanol and isobutylene under a liquid phase
synthesis over acid resin catalyst in where isobutene/isobutylene is obtained as a
side product from the said petroleum refinery. (Feely, 2001) However, the supply of
isobutene in this case is limited compared to other methods. While the butane
content in the natural gas is low, this source of C 4 is increasingly attained importance
as various alternatives have been attempt to increase the availability of isobutene,
one of the source of C4.

The manufacturing of MTBE

2. Process Description

This process is for recovering isobutylene by decomposing methyl-tert-butyl

(MTBE) with the presence of acid catalyst in the liquid phase in the reaction
distillation. The product undergo decomposition, is distilled in a distillation column
under reflux which is separating isobutylene from the top column while methanol that
is also produced will preferably be separated from the effluent from the bottom
column.

The acid catalyst used in this process can be different consists of either a mineral
acid such as phosphoric acid or sulfuric acid, organic sulfonic acid or solid acid
catalyst like activated alumina, metal sulphate, silica-alumina or ion exchange resin.
Either way, sulfonated ion exchange resin is the most preferred catalyst because it
did not corrode the equipment used. The catalyst concentration, reaction
temperature and appropriate reaction pressure are preferred to be 0.1 to 20 wt% of
reaction mixture, at 80 - 120 C with 2-5 kg/cm2 respectively. If the temperature used is 60
C, the reaction rate may be too low because the catalyst decomposition formation happens
at the optimum temperature of 150C.

3. Mechanism

The thermal decomposition pathways of MTBE have been investigated using the
G3B3 method. Based on the experimental observation and theoretical calculation,
the pyrolysis channels are provided, especially for primary pyrolysis reactions. The
primary decomposition pathways include formation of methanol and isobutene, CH4
elimination, H2 elimination and C-H, C-C, C-O bond cleavage reactions. Among
them, the formation channel of methanol and isobutene is the lowest energy
pathway, which is in accordance with experimental observation. Furthermore, the
secondary pyrolysis pathways have been calculated as well, including
decomposition of tert-butyl radical, isobutene, methanol and acetone. The radicals
play an important role in the formation of pyrolysis products, for example, tert-butyl
radical and allyl radical are major precursors for the formation of allene and propyne.
Although some isomers (isobutene and 1-butene, allene and propyne, acetone and
propanal) are identified in our experiment, these isomerization reaction pathways
occur merely at the high temperature due to their high activation energies. The
theoretical calculation can explain the experimental results reported in part 1 and
shed further light on the thermal decomposition pathways. (Zhang, 2008)

4. Strength and limitation

It has been hypothesized hitherto that the liquid-phase synthesis of MTBE on ion-
exchange resins proceeds quasi-homogeneously in excess methanol by an ionic
mechanism whose rate-limiting step is the protonation of the alkene, and quasi-
heterogeneously at very low methanol content likely by a concerted proton transfer
involving adsorbed reactants. However, recent knowledge of the reaction involving
the effect of the non-ideality of the liquid phase on the kinetics of the reaction, and
the inhibitor effect of MTBE on the reaction rate, in addition to new data on
byproducts formation, suggest that MTBE synthesis can be looked at as a quasi-
heterogeneous catalysis independently of the methanol content of the liquid phase.
Moreover, a transition between a Eley-Rideal mechanism and an Langmuir-
Hinshelwood one can be assumed as the methanol concentration of the liquid phase
decreases.

The most widely used gasoline additive methyl tert-butyl ether (MTBE) has been
questioned recently, since frequent detection of this compound in groundwater
indicates that it could be a risk to our environment. Consequently, legislative efforts
have been made by some local governments to phase out the use of MTBE. Among
a number of alternative substitutes, ethyl tert-butyl (ETBE) seems to be the more
promised one due to its lower water solubility, suggesting that it could pose less
impact to our water supply. However, a thorough understanding of its environmental
fate is needed before ETBE is widely accepted as a more environmentally friendly
gasoline additive. As a part of this effort, the degradation of MTBE and ETBE as well
as their effects on the fate of aromatic gasoline components, i.e. BTEX (benzene,
toluene, ethyl-benzene and xylenes) were studied on two soils contaminated with
MTBE-blended or ETBE-blended gasoline. During a period of 5 months, the general
aerobic degradation of the gasoline and its different additives were monitored by gas
chromatography thermal conductivity detection (GC-TCD) and concentration
changes of MTBE and ETBE were monitored with the help of gas chromatography -
mass spectrometry (GC-MS). The results of this study showed that the degradation
of MTBE, ETBE and BTEX occurred in all the systems, nevertheless MTBE and
ETBE degraded far more slowly in contrast with the degradation of BTEX, indicating
that MTBE and ETBE are more persistent. When the degradation of MTBE and
ETBE were compared, ETBE decreased a little faster than MTBE, implying that
ETBE advantages slightly in degradation over MTBE. Concerning the effects of
MTBE and ETBE on the fate of BTEX, the results showed that MTBE might enhance
whereas ETBE might inhibit the degradation of BTEX though at a lower level. In
addition, less degradation of MTBE and ETBE was observed in organic-rich soil in
all the cases, probably because that there are more other substrates available for
the microorganisms in organic-rich soil.

5. Current Technology vs New Technology

In petrochemical industry, there have been several processes to develop a highly

efficient of utilization of C 4 fractions. For example, is in the process application of BB
Fraction as Butadiene Source for Preparation of Polymer Derived from Living
Polybutadiene. According to Hiroaka, BB, as the residue after the extraction of
butadiene rarely as an effective raw material has been used mostly for fuel. It is that
recently BB has been made to react with methanol to separate MTBE which can be
used as one of components for gasoline.

Alternatively, other method used is isobutylene as a raw material in producing

other chemical products such as butyl rubber and isoprene. They are Methyl tert-
butyl ether (MTBE) is extensively used as an oxygenate and octane enhancer in
gasoline. Its release to the environment has generated great public and
governmental concern. In this study, we give a brief review of the decomposition of
air toxics by the application of radio frequency (RF) plasma reactors and then
present our study on decomposition of methyl tert-butyl ether by adding hydrogen in
a cold plasma reactor.