TABLE OF CONTENTS

1.0 INTRODUCTION............................................................................................................. 1

2.0 CONCEPTUAL DESIGN AND FLOWSHEETING ........................................................... 1

2.1 Batch VS Continuous .................................................................................................. 2

2.2 Input-Output Structure ................................................................................................. 3

2.3 Recycle Structure ........................................................................................................ 8

2.2.1 Methanol Absorber Tower ..................................................................................... 8

2.2.2 Methanol Recovery Tower .................................................................................... 9

2.4 Separation Structure .................................................................................................... 9

2.4.1 TBA Tower ............................................................................................................ 9

2.4.2 MTBE Tower ....................................................................................................... 10

2.5 Economic Potential Analysis ...................................................................................... 13

2.6 Environmental Controls ............................................................................................. 14

2.6.1 MTBE Environmental Impacts ............................................................................. 14

2.6.2 Methanol Environmental Impacts ........................................................................ 14

2.6.4 Wastewater Treatment ........................................................................................ 15

2.7 Heat Exchangers and Utilities .................................................................................... 17

2. 8 Process Flow Diagram and Stream Data Condition .................................................. 19

3.0 REFERENCES ............................................................................................................. 23

i
1.0 INTRODUCTION

MTBE is the most widely produced oxygenate. Its raw materials are isobutylene and
methanol. An important reason for the widespread use of MTBE is feedstock flexibility. MTBE
can be made inside the refinery, using petroleum-derived raw materials, or it can be produced
externally, using natural gas feedstocks, thereby ensuring ready availability and reducing
dependence on crude oil for the production of automotive fuels. Isobutylene can be obtained
from either steam cracker operation, fluid catalytic cracker (FCC) operation, butane
dehydrogenation or dehydration of tertiary butyl alcohol [1].

There are two ways to produce MTBE which are conventional process and reactive
distillation process. In conventional process there is mainly a reactor and separate distillation
column with conversion range 87 - 92%. Meanwhile, reactive distillation column is a newly
method for the production of MTBE which is established and date back to the way in 1980 as
the scientist Smith recorded the first patent for the production of MTBE. The method has a lot
of features that makes the process attractive and practical with a conversion reached 99.2%
[2].

In this study, a plant to produce MTBE from dehydration of TBA is chosen due to the
facts that it can produce the highest purity of Isobutylene compared to other methods. The
aim of this study is to design a plant that are capable to produce 250 000 metric tonnes per
year of MTBE from dehydration of tertiary butyl alcohol (TBA).

2.0 CONCEPTUAL DESIGN AND FLOWSHEETING

The conceptual design of a chemical process involves the invention of the process
such as the selection of the process units as well as the interconnection between the units.
The designs are void of detail, dimensions and technical notes and includes the design of
interactions, experiences, processes and strategies. Meanwhile, a flowsheet is the
diagrammatic representation of the process steps [3]. Once the flowsheet structure has been
defined, a simulation of the process can be carried out. A simulation is a mathematical model
of the process which attempts to predict how the process would behave if it was constructed.
Having created a model of the process, we assume the flow rates, compositions, temperature,
and pressure of the feeds. The simulation model then predicts the flow rates, compositions,
temperatures and pressure of the products. It also allows the individual items of equipment in
the process to be sized and predicts how much raw material is being used and how much
energy is being consumed. The performance of the design can then be evaluated [4].

1
2.1 Batch VS Continuous

Batch can be defined as the material that is produced by a single execution of a batch
process, or an entity that represents the production of a single material at any point of time in
the process. The term ‘batch’ refers to both the material produced by and during the process,
and also an entity that represents the production of that material. Batch is considered as a
shortcut term for “the production of a batch”. In some cases, batch processes are more
favourable than continuous processes due to several economic and technical factors such as
having simple processing units like mixers and stirrers versus complex production systems.
Moreover, the multipurpose units which may be used for several processing phases of the
batch could also be used to support multi-product manufacturing within the facility. Batch
manufacturing plants also are comparatively more robust than a continuous plant and the
manufacturing facility is easier to scale up depending on market demand and requirements.
Lastly, batch process has a better control of process of a confined step [5].

Meanwhile, in a continuous process, as suggested by the name, the flow of material

or product is continuous. The materials are being processed in different equipment to yield the
products. Each machine operates in a single steady state and performs a specific processing
function. Continuous transformation of mass, energy and momentum happens, and the
product formed is uniform in time. The process is operated continuously or otherwise stopped
for maintenance, cleaning and irregular working only. The advantages of continuous process
include narrow specification of product, improved asset utilization and also less waste
generated compared to batch process [5].

In this study, which is to design a plant with capacity of 250 000 tonnes per year of
MTBE, the operational condition has been set to be under continuous mode. This is due to
several factors that has been taken into considerations such as the equipment size, product
quality, safety issue, operating and maintenance cost and also the product demand. The
selection of the continuous mode is justified and summarized as Table 1.1 below:

Table 2.1: Advantages of using continuous mode in MTBE production.

Factor Justification
Size The production capacity of MTBE which is 250 000 tonnes per year is
considered as large throughput. Hence, continuous process is more
favourable in terms of economic scale. This is due to the reason that in batch
processes, as the throughput increases, the required size of equipment

2
 would also increase. The technical difficulties would also increase as it is
harder to move large amounts of products from one equipment to another.
Product Continuous process such as in reactive distillation column helps to increase
Quality purity of the product which is MTBE. This is due to the reason that
continuous separation of product is carried out which means that the
products are being separated as soon as it is formed. This operating
condition helps in increasing the yield of product when side reactions are
reduced.
Safety Large chemical plants operating continuously usually have excellent safety
record, and safety procedures are well established. The risks associated
with opening equipment containing chemicals are also being eliminated as
compared to batch.
Operating & Batch process which usually needs bigger size of equipment for large scale
Maintenance production would requires longer periods of time for cleaning and
Cost preparation. Hence, the operability of the plant would be reduced, and the
maintenance cost would be higher.
Product Since MTBE is widely used as gasoline additives which is used by vehicles
Demand to be operated, demand for the product can be considered as non-seasonal
product. Thus, continuous process is needed to ensure continuous
production of MTBE.
Processing Generally, as the throughput increases, continuous processes become more
Efficiency efficient. As an example, fugitive energy losses are reduced, and rotating
equipment such as pumps and compressors operate with higher efficiency.
Recycle of unused reactants and the integration of energy within the process
or plant are standard practices and relatively easy to achieve.

2.2 Input-Output Structure

There are numerous variations on MTBE plant designs. Generally, MTBE production plant
consist of reactor for MTBE production, MTBE recovery section and Methanol recovery
section. In this study, the design for MTBE plant comprises of six main equipment which is:

1. TBA Reactor
2. TBA Tower
3. MTBE Reactor

3
 4. MTBE Tower
5. Methanol Absorber
6. Methanol Recovery Tower

The first step in designing production plant is by constructing a process concept diagram.
It is an important step in determining the inlet and outlet component and the reactions that
takes place inside the reactor. In production of MTBE, the first reaction step is Dehydration of
TBA. TBA is heated and pass through catalyst inside reactor to yield isobutylene and water
as product. The reaction involves 2 mol of TBA in a reversible reaction to produce 2 mol of
isobutylene and 2 mol of water. The equation for Dehydration of TBA can be seen as Equation
1.1 [6]:

2 [(CH3)3COH] 2 [CH2=(CCH3)2 + 2 [H2O] [1.1]

TBA (g) Isobutylene (g) + Water (g)

Further understanding on the process could be done by recognizing the important

parameters of each of the reaction condition. Hence, the reaction condition for dehydration of
TBA can be seen as Table 1.2:

Table 2.2: Parameters and reaction conditions for Dehydration of TBA.

Reaction conditions for Dehydration of TBA
Limiting Reactant TBA [7]
Product Isobutylene, Water [7]
Reaction Temperature and Pressure 110 °C, 6 bar [8]
Reaction Phase Vapor phase [8]
Catalyst Cation exchange resin (Amberlyst-15) [9]
Conversion of Limiting reactant 99.8 % [7]
Product selectivity 99.9 % [7]
Yield 99.7% [7]
Feed preparation for reactor feed Preheating

Meanwhile, the input and output component for dehydration of TBA can be seen as Figure 1.1
below:

4
 Packed Bed Reactor Isobutylene
(TBA Reactor) Unreacted TBA
TBA Water
Temperature: 110°C
Pressure: 6 bar

Figure 2.1: Concept diagram for Dehydration of TBA.

As shown in the figure, the raw material needed for the dehydration is TBA. TBA is
preheated prior to the process as TBA exists as liquid phase at room temperature. TBA would
entering the reactor at vapor phase since the reaction takes place at vapor phase. The
temperature inside TBA reactor is 110 °C at pressure about 6 bar [8]. The reaction inside the
reactor is endothermic. Vapor of TBA would flow through bed of cation exchange resin
catalyst; Amberlyst-15 in which the reaction would takes place [9]. Mass transfer would occur
between TBA and catalyst surface and hence speed up the rate of reaction. Isobutylene would
be formed at 99.8 % conversion of limiting reactant and 99.9 % of product selectivity [7].
However, the remaining of unreacted TBA cannot be disregarded. The main product which is
isobutylene together with water and unreacted TBA would be sent to TBA Tower for separation
of isobutylene from water and unreacted TBA by using flash distillation.

Second step of MTBE production involving etherification of isobutylene and methanol

in to yield MTBE as product and excess methanol. A mol of Isobutylene is reacted with 1 mol
of methanol to produce 1 mol of MTBE. Excess methanol would be sent to the methanol
recovery system. However, the reaction in MTBE reactor would also cause formation of by-
product. Methanol will be degraded to form water and Dimethylether (DME) [10], meanwhile,
Isobutylene would be reacted with water to reversely form TBA. The main reaction for
etherification of isobutylene and methanol to yield MTBE can be seen as Equation 1.2. The
equation to show the degradation of methanol and formation of TBA are being depicted in
Equation 1.3 and Equation 1.4 respectively [11]:

CH2=C(CH3)2 + CH3OH  (CH3)3COCH3 [1.2]

Isobutylene (l) + Methanol (l)  MTBE (l)

5
 2CH3OH  C2H6O + H2O [1.3]

Methanol (l)  DME (l) + Water (l)

CH2=C(CH3)2 + H2O  C4H10O [1.4]

Isobutylene (l) + Water (l)  TBA (l)

The reaction condition for etherification to produce MTBE are listed in Table 1.3.

Table 2.3 : Parameters and reaction conditions for Etherification of MTBE

Reaction conditions for Etherification of MTBE
Limiting Reactant Isobutylene [12]
Excess Reactant Methanol [12]
Main Product MTBE [12]
By-product DME, TBA [12]
Feed Ratio Isobutylene 1: 2 Methanol [8]
Reaction Temperature and Pressure 85 °C, 10 bar [8]
Reaction Phase Liquid phase
Kinetic or Thermodynamic controlled Thermodynamic [11]
Catalyst Cation exchange resin (Amberlyst-15) [9]
Conversion of Limiting reactant 95% [8]
Product selectivity 98% [8]
Feed preparation for reactor feed Preheating

The isobutene conversion (XIB), yield IB to MTBE (YMTBE) and selectivity to MTBE
(SMTBE) using Amberlyst 15 catalyst is 99.8%, 99.7% and 99.9% respectively [8]. However,
there are no reported works on the selectivity of the side reaction during the synthesis of MTBE
from isobutylene and methanol. Several strategies have been used to reduce the production
of these undesirable by-products. First, the ratio of methanol and isobutylene is kept above
one to suppress the dimerization of butane. Reaction temperatures below 100°C can diminish
the formation of dimethyl ether. Finally, the pre-treatment of the feed stream which is removal
of water can prevent the formation of TBA [13]. The input-output component structure of the
main and by-products can be seen as Figure 2.2 below:

6
 Unreacted Methanol
Unreacted Isobutylene
TBA
Packed Bed Reactor DME
Water
Isobutylene (MTBE Reactor)
MTBE
Methanol Temperature: 85 °C
Pressure: 10 bar

Figure 2.2: Concept Diagram for Etherification of MTBE in MTBE Reactor

From the figure above, it can be seen that methanol and isobutylene would be mixed
in stream prior to be fed into reactor. Vapor isobutylene is first to be cooled in condenser to
liquid phase before mixing process with liquid methanol is carried out. Methanol-isobutylene
mixture would be pumped and preheated to the reaction temperature. The reaction would be
carried out at 85 °C and 10 bar [8]. The thermodynamic limitations were proven when the
equilibrium is shifted to the product side when temperature is lowered and the reactants side
when temperature is increased. However, the reaction temperature must be monitored and
controlled as the reaction proceeds exothermically. Installation of temperature indication
controller is crucial to ensure that no safety issue takes place. High reaction temperature also
may cause catalyst destruction [9].

High temperature would destroy the catalyst surface and reducing the area for reaction
to happen. The mixture of methanol and isobutylene would be passed through packed bed
catalyst in which the catalyst used for MTBE reactor is the same as TBA reactor which is
Amberlyst-15. The usage of the same catalyst would reduce the cost in terms of transportation.
As the reaction passed through bed of catalyst at liquid phase, formation of product occurs at
95% conversion of limiting reactant and 98% of product selectivity [8]. The excess methanol
would be sent to the recovery system so that the recycled methanol could be used back in the
process. The path or final destination for each component can be seen as Table 2.4 below:

Table 2.4: Analysis of the component final path for MTBE production.
Component Boiling Point (°C) Role Destination
TBA 82.2 [9] Raw material & By-product Purge
Methanol 64.7 [9] Raw material Recycle
Isobutylene -6.9 [9] Intermediate product Purge
Water 100 [9] By-product Purge
MTBE 55.2 [9] Product Stored
DME -24 [9] By-product Purge

7
2.3 Recycle Structure

The proposed recycle structure is carried out in order to recover the raw materials that
has been used in excess so that efficient usage of raw material can be achieved. For MTBE
plant, the raw materials that has been used in excess is methanol and water. However, after
further consideration, the only raw materials that could be efficiently recycled is methanol. This
is due to the reason that wastewater may contains contaminant even though after purification
system and it will gives an impact to the reaction occurred. Moreover, the cost to purchase the
process water is cheaper compared to the purification system of recycled water.

Other than that, methanol is recycled due to its high volatility and solubility. Methanol
released into the environment would cause air pollution as the volatile organic compound
(VOC) is easily transferred in the air [14]. Methanol released also may get into the water
sources and contaminate the groundwater which has been the source of drinking water [15].
Hence, recycling of methanol is significant to protect the environment other than the main
reason which is to reduce the operational cost. Methanol is recovered through the use of
absorber and distillation column. Recycle stream of methanol would be mixed with fresh
methanol in mixing vessel prior to be fed into reactor.

2.2.1 Methanol Absorber Tower

Figure 2.3: Separation system for methanol water wash by absorption.

Methanol Absorber is used to extract the unreacted methanol. The operating pressure
of the distillation column is maintained at 5 bars and 90 °C [2]. Water is added to the absorber
to extract methanol out of the hydrocarbons mixture. Methanol will dissolve in water to form
methanol-water mixture as the solubility of methanol is very high in water. However, water will
be evolved back from methanol when recycled. This methanol-water mixture is collected as
bottom product and fed to the Methanol Recovery Tower.

8
2.2.2 Methanol Recovery Tower

Figure 2.4: Separation system of methanol recovery tower by using distillation column

Methanol Recovery Tower is used to separate the methanol and water so that
methanol can be recycled back to the reactor. Methanol which comes from hydroxyl group
having a boiling point less than water. At column temperature and pressure of 5 bars and 90
°C [16], methanol would vaporizes leaving water at liquid phase as bottom product. Methanol
is recycled back to the system at 99.9 % while 0.01 % of water would be discharged together
with the waste water to treatment plant [2].

2.4 Separation Structure

Production of MTBE from TBA by indirect method requires four separators namely TBA
Tower, MTBE Tower, Methanol Absorber Tower and Methanol Recovery Tower. Each
separator carries out their own function according to the product needed and the feed entered
[12].

2.4.1 TBA Tower

Figure 2.5: Separation system of TBA Tower by flash distillation.

9
 TBA Tower is used to separate isobutylene from water and unreacted TBA. The
separation was done through flash distillation at 7 bars and 120 °C [2] . Flash distillation can
be considered as the simplest separation process. In this process, a pressurized feed mixture
which is in liquid phase is passed through a heater to pre-heat the feed prior being to the flash
column. In the column, at specified temperature and pressure, there would be substantially
pressure drop causing the feed to partially vaporizes. For dehydration of TBA, isobutylene
vaporizes and would be collected at the top of the tank. Meanwhile, water which is denser
flows downward together with a little portion of isobutylene and unreacted TBA.

2.4.2 MTBE Tower

The alternatives for separation of MTBE can be classified into two which is either by reactive
distillation or by conventional method. In this study, the alternative A which is by reactive
distillation.

Alternatives A: Reactive Distillation Column

Figure 2.6: Separation system of MTBE Tower by reactive distillation column

The separation of MTBE from isobutylene, methanol and water is carried out by using
reactive distillation column. Reactive distillation (RD) is a process in which catalytic chemical
reaction and distillation (fractionation of reactants and products) occur simultaneously in one
single apparatus. The process setup for RD can be classified as a two-phase counter current
fixed-bed catalytic reactor. The introduction of an in-situ separation process in the reaction
zone or vice versa leads to complex interactions between vapor–liquid equilibrium,
mass transfer rates, diffusion and chemical kinetics, which poses a great challenge for design
and synthesis of the systems [17].

10
 The separation process is carried out at 19 bar and 90°C [2]. Reactive distillation
column consists of reaction zone on the upper part and separation zone on the lower part.
These features allow exothermic reaction and separation to be conducted simultaneously.
This is an advantage to the system as it produces high purity of MTBE since separation occurs
as soon as product formed. Reactive distillation occurs at liquid phase reaction with a large
excess of one reactant. It is carried out closer to the stoichiometric feed conditions by using
heterogeneous catalyst. However, the reaction mixture leaving the reactor forms 3 minimum
boiling azeotropes. The following table shows the azeotropic condition of the reaction [18].

Table 2.5: Azeotropic condition of reactive distillation column.

Component Molecular weight Boiling point (K)
Isobutylene 56.12 267
MTBE 88.15 328
MeOH 32.04 338
TBA 74.12 355
Azeotropic mixture (MeOH-MTBE)
Azeotropic temperature 325
Azeotropic composition (mol) (vol)
MTBE 69 % 87 %
MeOH 31 % 13 %

Methanol, water and small amounts of by-products and unreacted reactants would be
vaporized and collected as distillate. A condenser is installed at exit of distillate to enable reflux
to occur. Meanwhile, large amount of MTBE becomes the bottom product. Even though boiling
point of MTBE is less dense than methanol, due to the large amount that present, MTBE would
be heavier and goes downward. The purity of the product which is MTBE is further increased
as a reboiler is installed at the bottom of distillation column. The following are the advantages
of using reactive distillation column [9]:

1. Simplification or elimination of the separation system can lead to significant capital

savings.
2. Improved conversion of reactant approaching 100%. This increase in conversion
gives a benefit in reduced recycle costs.
3. Improved selectivity. Removing one of the products from the reaction mixture or
maintaining a low concentration of one of the reagents can lead to reduction of the
rates of side reactions and hence improved selectivity for the desired products.
4. Significantly reduced catalyst requirement for the same degree of conversion.
5. Avoidance of azeotropes. RD is particularly advantageous when the reactor product
is a mixture of species that can form several azeotropes with each other. RD
conditions can allow the azeotropes to be reacted away in a single vessel.
6. Heat integration benefits. If the reaction is exothermic, the heat of reaction can be
used to provide the heat of vaporisation and reduce the reboiler duty.

11
 7. Avoidance of hot spots and runaways using liquid vaporisation as thermal fly wheel.

Meanwhile, disadvantages of reactive distillation column include higher manufacturing cost,

complex reaction and kinetics, and is a relatively new field.

Alternatives B: Conventional Method

Figure 2.7: Separation system of MTBE Tower by conventional method

In conventional method, the purification of MTBE is carried out in three distillation columns in
series. The complexity of this method is less than the reactive distillation method which the
separation of MTBE follows normal principle of distillation column. Three distillation columns
must be used due to the azeotropic condition of methanol-MTBE that presents. However, the
usage of conventional method is accompanied by high capital costs and maintenance costs.
More equipment means more energy needed and more time spend for cleaning and
preparation unit. Thus, higher cost incurred, and the economic value becomes not feasible
[13].

12
2.5 Economic Potential Analysis

Economic potential and evaluation are an action to make sure the development of the
company especially in terms of company profit. Calculation of economic potential will be based
on the actual output and total use of the production capacities. The pilot design will be tested
before the scale up to the desired plant capacity. Engineer must understand all the process
limitation and can predict what will be happen when the scale up is done whether the process
will deviation much more than a pilot scale. Therefore, safety must be taken as one of the
importance factors to build full capacity plant.

The production cost can be altered by the conversion of MTBE. It is assumed that, the
higher the conversion of MTBE, the higher economic potential for the industry. An economic
potential plot will be based on the conversion is made in order to evaluate the effect of
conversion of product toward the economic potential. For a company, maximum profit is a
must. Therefore, suitable design variable must be chosen properly. Input and output structure,
recycle structure are considered besides economic potential.

The economics potential is done based on the assumptions as stated below:

1. Methanol to isobutylene ratio – 1.1
2. Isobutylene conversion in the reactor – 0.998
3. Selectivity of MTBE in the reactor – 0.98
4. Selectivity of TBA in the reactor – 0.006
5. Total working days per year: 350 days

Annual Cost of Product (MTBE)

= (𝑅𝑀 4663 𝑇𝑜𝑛𝑛𝑒𝑠 𝑀𝑇𝐵𝐸 × 250,000 𝑇𝑜𝑛𝑛𝑒𝑠 𝑀𝑇𝐵𝐸/𝑦𝑒𝑎𝑟)
= 𝑅𝑀 1,165,750,000/𝑦𝑒𝑎𝑟
= RM 1165.750 million/year

Annual Cost of Raw Material (TBA, Methanol)

= (𝑅𝑀 2963 𝑇𝑜𝑛𝑛𝑒𝑠 TBA × 180 000.08 𝑇𝑜𝑛𝑛𝑒𝑠 TBA/𝑦𝑒𝑎𝑟) +
(𝑅𝑀 2323 𝑇𝑜𝑛𝑛𝑒𝑠 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙× 100000.000 𝑇𝑜𝑛𝑛𝑒𝑠 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙/𝑦𝑒𝑎𝑟)
=𝑅𝑀 533,340,237.30/𝑦𝑒𝑎𝑟+𝑅𝑀 232,300,000.00/year
=𝑅𝑀 765,640,237.30/𝑦𝑒𝑎𝑟
=RM 765.640 million/year

13
Economics Potential
= Annual Cost of Products – Annual Cost of Raw Materials
= 𝑅𝑀 1165.750 𝑚𝑖𝑙𝑙𝑖𝑜𝑛/𝑦𝑒𝑎𝑟−𝑅𝑀 765.640 𝑚𝑖𝑙𝑙𝑖𝑜𝑛/𝑦𝑒𝑎𝑟
= RM 400.11 million/year

2.6 Environmental Controls

For each plant, environmental issue must be taken into consideration. Proper waste
disposal is needed to ensure that the by product or effluent from the plant production do not
cause any impact to environment. The waste from MTBE production consists of hydrocarbon
gases from methanol absorber tower and also waste water from methanol recovery tower.
The components in waste water consists of large amounts of MTBE and methanol, also a little
fraction of TBA, isobutylene, and DME.

2.6.1 MTBE Environmental Impacts

Despite its potential benefits on air quality, MTBE has some properties that can cause
problems. MTBE is much more soluble in water than most other components of gasoline. If it
gets in the ground, it can travel faster and farther through groundwater than other gasoline
components. This makes it more likely to contaminate public water systems and private
drinking water wells if gasoline is spilled on the ground or leaks out of underground storage
tanks. Even fairly small amounts of MTBE in water can give it an unpleasant taste and odour,
making the water undrinkable. MTBE also does not break down (biodegrade) easily [19]. As
a result, it is harder to clean up once contamination occurs. In the late 1990s, many community
drinking water 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.

2.6.2 Methanol Environmental Impacts

When burned as fuel, methanol cuts emissions of nitrogen oxides and volatile organic
compounds that form ground-level ozone or “smog.” Methanol is much less reactive than
gasoline in the atmosphere, with the only toxic component of the emissions being
formaldehyde, as compared to dozens of carcinogenic components of gasoline emissions,
which also contains formaldehyde. Methanol is readily biodegradable in both aerobic and
anaerobic environments, with a half-life in surface and groundwater of just one to seven days,

14
compared to a half-life for benzene in groundwater of 10-730 days. A report prepared for the
Methanol Institute by the environmental consulting firm Malcolm Pirnie concluded that relative
to conventional gasoline and diesel fuel, methanol is a safer and more environmentally benign
fuel. In the United States, more than 200 municipal wastewater treatment plants inject
methanol into the treatment system to reduce nitrogen levels in plant effluent that can harm
sensitive aquifers [9].

2.6.4 Wastewater Treatment

Wastewater treatment is a must in any plant. The wastewater from plant cannot be
channelled into the sewage system without being treated. The wastewater from the MTBE
plant may contains a small amount of the feed and product and a small quantity of by-products
such as TBA and DME. According to the site location selected, the wastewater from the plant
is to be treated and should comply with Standard B. The treatment process includes physical,
chemical and biological process to remove the water contaminants. The treated industrial
wastewater (or effluent) may be reused or released to a sanitary sewer or to a surface water
in the environment after treatment. The wastewater in this chemical plant is mixtures of MTBE,
methanol, water, sludge and small amount of TBA and DME. The waste water is treated by
physico-chemical reaction [20]. The flowchart for physical waste water treatment is portrayed
as Figure 2.8 below:

Collection Equalization
Screening
tank tank

Coagulation
and Grit tank
Flocculation
tank

Clarifier Tank

Sludge Air Stripping by using

Dewatering packed tower

Figure 2.8: Flowchart for wastewater treatment process

15
Methanol treatment by Denitrification Process (Chemical Treatment)

To remove methanol in the waste water, denitrification process is used for the plant
waste treatment. The COD value used is based on the COD value of wastewater from other
plants that are in operation. The COD value of 3000 mg/l will be used for design purposes. In
the denitrification process, nitrate is reduced to nitrogen gas by the same facultative,
heterotrophic bacteria involved in the oxidization of carbonaceous material. For reduction to
occur the dissolved oxygen level must be at or near zero and a carbon supply must be
available to the bacteria. Because low carbon content is required for the previous nitrification
step, carbon must be added before denitrification can proceed. A small amount of primary
effluent, bypassed around secondary and nitrification reactors, can be used to supply the
carbon. However, the un-nitrified compounds in this water will be unaffected by the
denitrification process and will appear in the effluent. When essentially complete nitrogen
removal is required, an external source of carbon containing no nitrogen will be required. The
most commonly used external carbon source is methanol, CH3OH. When methanol is added,
the denitrification reaction would become as Equation 2.1 below:

5 1 5 7
𝑁𝑂3− + 𝐶𝐻3 𝑂𝐻 → 𝑁2 + 𝐶𝑂2 + 𝐻2 𝑂 + 𝑂𝐻 − [2.1]
6 2 6 6

Denitrification reaction converted methanol into non-harmful gases such as nitrogen and
carbon dioxide. These gases can be directly released to the environment without causing
much bad effects to the surrounding [21].

Isobutylene Treatment by Air Stripper

Air stripping is a technology that has been proven to productively remove MTBE. In air
stripping, volatile organics are partitioned from water by greatly increasing the surface area of
the contaminated water exposed to air. Air stripping involves continuously contacting the
contaminated water with a large volume of air to transfer a significant fraction of the volatile
organic carbon compounds (VOCs) in the air phase. In addition, the air stripping process is
temperature sensitive, increasing the operating temperature will consequently improve
performance, and reduce tower dimensions, and capital and operations and maintenance
cost. There are a number of air stripping methods commercially available to treat MTBE
contaminated wastewater. These include packed towers, diffused aeration, low-profile (tray)
aeration, and spray aeration. Among the types of aeration devices, packed-tower and low-
profile air strippers are most cost-effective. The packed-tower air strippers can treat up to

16
99.98% efficiency [20]. The process flow diagram for isobutylene treatment by air stripper can
be seen as Figure 2.9 below:

Figure 2.9: Isobutylene gas treatment by Air stripping.

2.7 Heat Exchangers and Utilities

There are eight heat exchangers in total for the production of MTBE. Due to the low
range of temperature used, the utilities used mainly is low pressure steam. Meanwhile, cooling
water is used to cool down the distillate from separator. The summary for operating conditions
for heat exchanger is summarized as Table 2.6 below:

17
 Table 2.6: Heat Exchanger specifications for MTBE plant.
Code Equipment Temperature Operating Conditions No. of
(°C) Pressure Phase Change Types of Utilities Purpose units
(bar)
E-101 TBA Feed Preheater 80 1 From liquid to Low Pressure Steam To heat the TBA feed 1
gas so that phase
changes occur
E-102 TBA Tower Preheater 65 1 No phase Low Pressure Steam To increase 1
changes temperature of
isobutylene-methanol-
unreacted TBA
mixture.
E-103 TBA Tower Condenser 80 6.5 From vapor to Cooling Water To cool the vapor 1
liquid isobutylene to liquid
phase
E-104 MTBE Feed Preheater 28 10 No phase Low Pressure Steam To supply heat to the 1
changes reactant before
entering the reactor
E-105 MTBE Tower Reboiler 130 7.5 From liquid to Low Pressure Steam To supply heat to the 1
vapor process fluid
E-106 MTBE Tower 70 7.5 From vapor to Cooling Water To remove heat from 1
Condenser liquid vapor, for reflux
purpose
E-107 Methanol Recovery 100 1 From liquid to Low Pressure Steam To supply heat to the 1
Tower Reboiler vapor process fluid
E-108 Methanol Recovery 70 1 From vapor to Cooling Water To remove heat from 1
Tower Condenser liquid vapor, for reflux
purpose

18
2. 8 Process Flow Diagram and Stream Data Condition

Figure 2.10: Process Flow Diagram for production of 250 000 metric tonne/year of MTBE by Dehydration of TBA.

19
 Table 2.7: Equipment information for MTBE production

Code Equipment Temperature Operating Conditions No. of

(°C) Pressure Phase Change Purpose units
(bar)
E-101 TBA Feed Preheater 80 1 From liquid to To heat the TBA feed so that 1
gas phase changes occur
P-101 A/B TBA Separator Pump 70 7 Liquid To transport water to waste 1
water treatment plant
R-101 TBA Reactor 110 6 Vapor Dehydration of TBA to 1
isobutylene and water
T-101 TBA Tower 120 7 Liquid-vapor Separation of isobutylene from 1
side products
V-101 Methanol Feed Vessel - - Liquid To mix fresh methanol with 1
recycle methanol
E-102 TBA Tower Preheater 65 1 No phase To increase temperature of 1
changes isobutylene-methanol-unreacted
TBA mixture.
P-102 A/B MTBE Feed Pump 25 8.15 From vapor to To transfer the methanol- 1
liquid isobutylene liquid mixture into
reactor.
R-102 MTBE Reactor 85 10 Liquid Etherification of MTBE 1
T-102 MTBE Tower 90 19 Liquid-vapor Separation of MTBE from 1
undesired product
V-102 MTBE Tower Reflux - - Liquid-vapor To store condensate from 1
Drum condenser
E-103 TBA Tower Condenser 80 6.5 From vapor to To cool the vapor isobutylene to 1
liquid liquid phase
P-103 A/B MTBE Tower Reflux 60 5.5 Liquid-vapor To pump back the liquid 1
Pump condensate into distillation
column

20
T-103 Methanol Absorber 90 5 Liquid-vapor To separate methanol from 1
Tower hydrocarbon by water wash
V-103 Methanol Recovery - - Liquid-vapor To store condensate from 1
Tower Reflux Drum condenser
E-104 MTBE Feed Preheater 28 10 No phase To supply heat to the reactant 1
changes before entering the reactor
P-104 A/B Methanol Recovery 65 4 Liquid To transfer methanol- water 1
Tower Pump mixture into distillation column
T-104 Methanol Recovery 90 5 Liquid-vapor To separate methanol and water 1
Tower in order to recycle methanol to
the feed
P-105 A/B Methanol Recovery 65 1 Liquid-vapor To pump liquid condensate back 1
Tower Reflux Pump to distillation column and recycle
stream.
E-105 MTBE Tower Reboiler 130 7.5 From liquid to To supply heat to the process 1
vapor fluid
E-106 MTBE Tower 70 7.5 From vapor to To remove heat from vapor, for 1
Condenser liquid reflux purpose
E-107 Methanol Recovery 100 1 From liquid to To supply heat to the process 1
Tower Reboiler vapor fluid
E-108 Methanol Recovery 70 1 From vapor to To remove heat from vapor, for 1
Tower Condenser liquid reflux purpose

21
 Table 2.8: Stream information for MTBE Production
Stream
Process Description
No.
1 Transport liquid phase of TBA to heater.
2 Transport vapor phase of TBA to TBA reactor.
3 Transport vapor mixture of methanol, TBA, unreacted TBA and water to heat
exchanger.
4 Transport vapor mixture of methanol, TBA, unreacted TBA and water to TBA
Tower.
5 Transport isobutylene vapor to condenser.
6 Transport isobutylene liquid to mixing point.
7 Transport water to pump.
8 Transport water to waste water treatment.
9 Transport methanol from storage to mixing vessel.
10 Transport mixture of methanol to mixing point.
11 Transport mixture of methanol-isobutylene to pump.
12 Transport mixture of reactant from diaphragm valve to heater.
13 Transport mixture of reactant from heater to reactor.
14 Transport mixture of MTBE, isobutylene, methanol and water from reactor to
reactive distillation column.
15 Transport MTBE product to storage.
16 Transport methanol from diaphragm valve to gate valve.
17 Transport methanol from gate valve to methanol absorber tower.
18 Transport process water from storage to methanol absorber tower.
19 Transport methanol-water mixture to methanol recovery tower.
20 Transport isobutylene gas to gas treatment.
21 Transport methanol-water mixture to pump.
22 Transport water from methanol recovery tower to waste water treatment.
23 Transport recycled methanol from methanol recovery tower to mixing vessel.

22
3.0 REFERENCES

[1] Agency for toxic subtances and disease registry - ATSDR, Methyl tert -Butyl
Ether (MTBE), i (2012) 2.
[2] F. Ancillotti, G. Oriani, E. Pescarollo, S. Arakawa, M. Araki, et al., Production of
methyl tertiary butyl ether from isobutylene, (2011) 5.
[3] T. Spengler, J. Geldermann, S. Hähre, A. Sieverdingbeck, O. Rentz,
Development of a multiple criteria based decision support system for
environmental assessment of recycling measures in the iron and steel making
industry, J. Clean. Prod. 6 (1998) 37–52.
[4] Encyclopedia of Chemical Processing and Design: Volume 65 -- Waste: Nuclear
... - Google Books, (2013).
https://books.google.com.my/books?id=0oZHDwAAQBAJ&pg=PT155&lpg=PT
155&dq=MTBE+plant+design&source= (accessed October 7, 2018).
[5] F. Sarghini, Introductory concepts about batch and continuous precess, (2011).
http://www.federica.unina.it/agraria/equipment-and-industrial-plants-for-food-i
(accessed November 22, 2018).
[6] 10. TBA using Beta Zeolite Catalysts.pdf, (n.d.).
[7] P.E.-W.A. Douglas, United States Patent [ 191, (1977).
[8] M.S. Patel, United States Patent ( 19 ), 09 (1990).
[9] H. Hamid, M.. Ali, Handbook of MTBE and Other Gasoline Oxygenates, 2004.
[10] Handbook of MTBE and Other Gasoline Oxygenates - Google Books, (2004).
https://books.google.com.my/books?id=uGjT9lb75ZkC&pg=PA194&lpg=PA19
4&dq=MTBE+plant+design&source=bl&ots (accessed October 7, 2018).
[11] I.S. Al-mutaz, A.E. Abasaeed, Production of MTBE Using Reactive Distillation
Technology Fahad S . Al-Harthi, (2014).
[12] Production of 400 , 000 Tonnes Per Year of Mtbe Plant Mohd Nazri Ismail
Normariah Abdullah, (n.d.).
[13] Handbook of Petroleum Processing Handbook of Petroleum Processing, n.d.
[14] H. Ogawa, T. Li, Volatile organic compounds in exhaust gas from diesel engines
under various operating conditions, Int. J. Engine Res. 12 (2011) 30–40.
[15] Y.F. Huang, S.Y. Ang, K.M. Lee, T.S. Lee, Quality of Water Resources in
Malaysia, Res. Pract. Water Qual. (2015).
[16] J.F. Knifton, J.C. Edwards, Methyl tert-butyl ether synthesis from tert-butanol via
inorganic solid acid catalysis, Appl. Catal. A Gen. 183 (2016) 1–13.
[17] E. Campus, Modeling of a Reactive Distillation Column : Methyl Tertiary Butyl
Ether ( Mtbe ) Simulation Studies, Engineering. 4 (2003) 13–30.
[18] U. Shafiq, PRODUCTION OF 20 , 000 MTPD OF Methyl Tertiary- Butylene By
Catalytic Conversion Session : 2012-2016 Project Supervisor : Umar Shafiq
National Fertilizer Corporation-Institute of Engineering and, (2017).
[19] World Health Organization, Methyl tertiary-Butyl Ether (MTBE) in Drinking-
water, (2005) 1–18.
www.who.int/water_sanitation_health/dwq/chemicals/MTBE200605.pdf.

23
[20] M. Noradli, B.I.N. Hashim, Treatment of Mtbe in Wastewater By Air Stripping
and, (2010).
[21] Encyclopedia of Chemical Processing and Design: Volume 34 ... - Google
Books, (2013).
https://books.google.com.my/books?id=ABrYesVa3S4C&pg=PA302&lpg=PA3
02&dq=MTBE+plant+design&source=bl&ots=r-6VMpo- (accessed October 7,
2018).

24