2.

3 Choice of process

In subtopic 2.2, we have discussed the comparison between three alternatives process to produce
MTBE. From our research, we had found MTBE can be produced from three ways which are
from n-butane (method 1), isobutylene (method 2) and tert-butyl alcohol (TBA) (method 3).
They are compared in terms of green chemistry and sustainability, environmental impact, energy
consumption, flexibility of operation and safety factors and waste management. Thus, in order to
select the most suitable process among these three, we need to consider their advantages and
drawbacks of every process. Finally we have decided to choose the second process; production
of MTBE from isobutylene as the best process to produce MTBE. Among the three alternatives
of the process suggested, the direct synthesis of MTBE from isobutylene and methanol is the
most applicable route path since it has few advantages among other routes. So, it will further
discussed on several aspects below.

2.3.1 Safety and Health Issues:

First and foremost, the selection is done by considering the safety and health issues. Safety and
health issues always be the most crucial issue when selecting the material to be used in the plant
because it involves thousands lives of people; including workers and people nearby.
Firstly, we will analyze this issue from the aspect of temperature and pressure. Desired
temperature should be maintained throughout the process to prevent possible run away from being
occurred. For method 1, there are three steps involved, which are isomerization, dehydrogenation and
etherification. From these three steps, isomerization and etherification (Ethermax) process are
exothermic process while dehydrogenation is endothermic process. For exothermic process, low
temperature is favored where the desired temperature for isomerization is 110-170C and
etherification is 50-85C. However, for dehydrogenation, high temperature is required which is 600
to 610C.
For method 2, production of MTBE from isobutylene involves only one step reaction which is
etherification and its desired temperature is from 50 to 85C.

For method 3, it involved one extra step reaction than method 2, dehydration and etherification.
Both reactions, endothermic and exothermic are involved.
The major disadvantages of chemical energy such as endothermic and exothermic reaction are
pollution and its potential to give humans various kinds of health conditions. This is kind of the
main reason why scientists and researchers are looking for other alternative sources of energy
that is less harmful to the environment. Furthermore, global warming has intensified in the recent
years because of extreme pollution in the different parts of the world, and through alternative
energy sources, its effects can be lessened or even controlled.[1]

Next, we will discuss about the pressure. Likewise as temperature, pressure also needs to be
maintained within the desired range. Dealing with high pressure may cause some accidents like
rupture of reactor or even explosion will occur.

In method 1, the desired pressure for isomerization process is 2.5-3.2MPa. It can be categorized
as high pressure and needs extra precaution while handling it. For dehydrogenation and
etherification process, moderate pressure is applied. Lastly, atmospheric pressure is required in
method 3 which is the lowest pressure required compared to the others two methods.

Raw materials used during the process also need to be considered as they can lead to safety and
health problem. For example, if the raw material used is hazardous, health problem will arise.
However, most of chemical substance has negative impacts towards health so it depends on us to
determine the using of material that is less harmful to people and surrounding.

In method 1, 2 and 3, all these processes use different raw materials to produce MTBE. They are n-
butane, isobutylene and tert-butyl alcohol. These raw materials were studied on how severe they
are towards environment and ways handling them. Basically, all of them are flammable so they
must be kept away from heat, sparks, open flames or hot surfaces.

For method 1, n-butane is a colorless, flammable gas at room temperature. The toxicity of
butane is low. Huge exposure concentrations can be assumed in butane abuse. The predominant
effects observed in abuse cases are central nervous system (CNS) and cardiac effects. Case
studies also reveal that serious brain damage and underdeveloped organs can occur in fetuses in
case of high single exposures during the week 27 or 30 of pregnancy.[1] However, Exposure to

low concentrations of n-butane has not been reported to cause adverse effects in humans.[2]
For method 2, isobutylene is used. Isobutylene is a colorless gas, or a liquid under pressure, with
a sweet, gasoline odor. Isobutylene can affect you when breathed in. Exposure to isobutylene can
irritate eyes, nose throat. Inhalation of moderate concentration of isobutylene will cause
dizziness, drowsiness and unconsciousness.[3]

For method 3, TBA is a volatile and colorless liquid. Tert-Butyl alcohol primarily impairs the
central nervous system and may cause headache, muscle weakness, giddiness, incoordination,
confusion, nausea and/or vomiting. Irritation of skin, eyes, and throat, coughing, and shortness of
breath may also be noted. It may also be irritating to skin upon direct contact (HSDB, 1995).[4]

Among the three raw materials, TBA has been classified as the most hazardous under Global
Harmonized System of Classification and Labeling of Chemicals (GHS) for its health effects.[5]
Therefore, extra careful is needed when handle with TBA compared to isobutylene and butane.

As a conclusion, from the aspect of safety and health issues method 2 is more applicable route
path rather than other methods because its reaction path needs low temperature and moderate
pressure. In addition, the raw material used in method 2, isobutylene is not as hazard as TBA.

2.3.2 Environmental Issues:

Our environment is constantly changing, no denying regarding this fact. As our

environment changes, so does the need to become increasingly aware of the problems
that surround it. People need to be aware of what types of environmental problems our
planet is facing.[6] Environmental issue is defined as problems with the planet's systems (air,
water, soil, etc.) that have developed as a result of human interference or mistreatment of the
planet.
In this part, we will focus on the side products produced during the reaction. However, the
product itself which is MTBE will bring some environmental issues. MTBE is irritating to the
skin. If this liquid is swallowed, aspiration into the lungs may result in chemical pneumonitis.
Exposure far above the OEL could cause lowering of consciousness. But, it has no long term
effect. [7]
For method 1, there are several by-products produced during dehydrogenation process. Methane
is one of the by-products. On a local scale, build up of methane poses an explosion hazard which
can result in evacuation of areas over old landfills or mines. Methane does not contribute
significantly to the formation of ground level ozone or photochemical smogs compared to other
volatile organic compounds (VOCs). The main impact of methane is on a global scale, as a
greenhouse gas. Even the level of methane in the environment is relatively low, its high "global
warming potential" ranks it amongst the worst of the greenhouse gases. Methane able to absorb
infrared radiation at a rate of 21 times greater than greenhouse gas, CO 2.[8] So, if the by-product is
not handle properly and its exposure to the atmosphere will lead to greenhouse phenomena.
In method 2, one of the by-products released is di-isobutylene which is very toxic to aquatic life
with long lasting effects. The table below gives an overview of the environmental assessment
results for di-isobutylene.[9]

Lastly, for method 3, by-products produced are water and dimethyl ether. As we know, water is
totally non-hazardous and not harmful to the environment. Though, dimethyl ether is extremely
flammable and may form potentially explosive mixtures with air. Thus, we should not release it
to surrounding environment to prevent soil and water pollution.

Based on the explanation above, we can conclude that method 3 is more applicable route path in
the aspect of environmental issues compare to method 2 since it has only two by-products. Thus,
it can be easily handle.
2.3.3 Public Issues:

Despite its potential benefits on air quality, MTBE has some properties that lead to the arising of
some problems. MTBE is much more soluble in water than most other components of gasoline.
Mishandling of MTBE will cause it to travel faster and farther through groundwater than other
gasoline components. This problem will increase the tendency of MTBE to contaminate public
water systems and private drinking water if there is any spillage of gasoline on the ground or
leaks out of underground storage tanks.

During late of 1990s, many communities drinking water in US supplies in areas that used a lot of
MTBE were found to have detectable levels of MTBE. Since then, MTBE use in gasoline has
been phased out because of concerns about groundwater contamination. Although it is not clear
what effects MTBE in drinking water might have on health, many states have passed laws
limiting or banning the use of MTBE in gasoline. As part of the Energy Policy Act of 2005,
Congress voted to remove the oxygen content requirement for reformulated gasoline. This
problem went into effect in 2006. Since then, companies have switched from using MTBE to
using ethanol instead in their gasoline for a number of reasons, including state laws banning
MTBE use, concerns over possible legal liability, and government tax subsidies for using
ethanol. According to the US Environmental Protection Agency (EPA), MTBE has not been
used in significant quantities in gasoline since 2005.[9]

In Glennville, California, MTBE was detected in drinking water at some of the highest levels of
MTBE ever recorded. One well tested at 20,000 parts per billion. As of November 2009, MTBE had
been detected in 27 of approximately 4800 active and standby public groundwater sources at
concentrations greater than the SMCL (secondary maximum contaminant level) of 5.0g/L. MTBE
was detected above the MCL (maximum contaminant level) of 13g/L in 9 of those active and
standby public groundwater sources, and has also been detected in significant concentrations in
domestic and in small water system wells in many parts of the state. However, groundwater in
some areas of the country might still contain MTBE. And MTBE is still being used as a gasoline
additive in other parts of the world.[10]
.

From the problems mentioned above, it shows that contamination of water sources by MTBE is
one of the serious public issues caused by MTBE plant. Fairly small amounts of MTBE in water
can give it an unpleasant taste and odor, making the water undrinkable. MTBE also does not
break down (biodegrade) easily. As a result, it is harder to clean up once contamination
occurs.[9]

Next we will talk about the process involved in each method. As mentioned previously,
production of MTBE by method 1 requires 3 basic steps. It is obviously needs extra cost since
the plant should be large enough to ensure all these three steps are done. Next, we proceed to
method 2 which requires only one step. The greater the number of steps involve, the complex the
process is. So, we can simply say that method 1 is a bit difficult to handle and more complex
than method 2. It might require more piping, reactor and other equipment in the plant. Thus, the
cost will be much higher. In method 3, the dehydration of TBA and water is produced together
with MTBE. So, separation process will involve to separate the water from MTBE. Besides,
necessary treatment is required for water before it discharge to the environment in order to
ensure water is free of MTBE. Thus, method 3 has the highest probability to cause contamination
of water sources if treatment of by-product which is water is not carry out well. Another
hypothesis can be made is, the complex the process is, the greater the possibilities of leaking to
be occurred.
In conclusion, method 2 is chosen over other methods because the process is less complex and
surely the cost needed is lesser than others.
2.3.4 Flexibility and Controllability:
From the aspect of the availability of the feedstock, we will concentrate on the availability of raw
material. The easiest way to get the raw materials should be taken into account to reduce the cost
needed for transportation of the raw materials to the plant.
For method 1, butane is used as raw material. Butane is not made or manufactured, it is
found naturally in combination with other hydrocarbons. Butane is a naturally occurring gas
but butane does not occur purely by itself.[11] Butanes are recovered from raw natural gas and
from petroleum refinery streams that result from catalytic cracking, catalytic reforming, and
other refinery operations. The most common separation techniques are based on a vapor-liquid,
two-phase system by which liquid butane is recovered from the feed gas.[12] The similarities
between butane and raw material in method 2, iso-butylene is, both are highly abundant in the
world. Furthermore, there are a lot of Refinery/Petrochemical Plants in the world for example
Saudi Arabia, Venezuela and China that can supply the demand of the feedstock to our plant.
Malaysia might has less supply of this feedstock, so we need to obtain them from other countries.
Conversely, tert-butyl alcohol (TBA) is obtained as a side product from the propylene oxide
(PO) manufacturing plant. So, it is highly depending on the production of PO. If there is shortage
on production of PO, amount of TBA produced also will be affected. In addition, the price of
TBA is also slightly higher than isobutylene.

Hence, we can conclude that method 2 is more flexible compared to other alternatives for the
production of MTBE.

In section 2.1, we have been discussed about the temperature and pressure involve. In term of
flexibility, method 3 might be the best choice since it can be handle under atmospheric pressure
while others has their own range for both temperature and pressure. For method 1, since it
involves 3 basic steps, it needs different range of temperature for each step. Besides, the pressure
that required to promote the isomerization in method 1 is as high as 2180kPa. This actually increase
the difficulty and complexity in controlling the reaction.

In Method 2, it has the lowest desired temperature wider range for production of MTBE. The
required pressure is moderate which is below than 4.8MPa.
From the aspect of controllability, method 2 is the best alternative and technology. After long
explanation been discussed, method 2 is labeled as the least complex process compared to others
MTBE production plants. Hence, the process can be easily controlled. In this method, less unit
operation is used. So when the number of unit operations is less, the amount of energy needed to
operate the plant also will remain low. Thus, Method 2 is chosen as the route to produce MTBE.

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