PROCESS SIMULATION AND COMPUTER AIDED DESIGN

(BKF3553)
SEMESTER II 2022/2023
GROUP PROJECT

Title of Assignment : PRODUCTION OF MTBE

Section : 01
Lecturer’s Name : DR. AAINAA IZYAN BINTI NAFSUN

Name MATRIC ID
SUBASH RAO A/L POTHORAJOO KA21093

NIK MUHAMMAD HARIZ BIN NIK MOHD ZAIDI KA20019

AMIRUL IKMAL BIN SEJAL KA20052

FACULTY OF CHEMICAL AND PROCESS ENGINEERING TECHNOLOGY

UNIVERSITI MALAYSIA PAHANG
 TABLE OF CONTENTS

1.0 INTRODUCTION TO MTBE ....................................................................................................... 1

1.1 APPLICATION ........................................................................................................................... 3
1.2 MARKET SURVEY ................................................................................................................... 4
1.2.1 World Market ......................................................................................................................... 4
1.2.2 Asia Market ............................................................................................................................ 4
1.2.3 Demand .................................................................................................................................. 5
1.2.4 Future Forecast....................................................................................................................... 6
1.3 SYNTHESIS ROUTE ................................................................................................................. 8
1.3.1 Direct Etherification............................................................................................................... 8
1.3.2 Trans Etherification ................................................................................................................ 9
1.3.3 Indirect Etherification .......................................................................................................... 10
1.3.4 Chosen Process Synthesis Route.......................................................................................... 11
2.0 THERMODYNAMICS MODEL ................................................................................................ 13
3.0 THERMODYNAMIC BINARY ANALYSIS .............................................................................. 14
4.0 PROCESS FLOW DIAGRAM .................................................................................................... 17
5.0 PLANT CAPACITY ..................................................................................................................... 19
6.0 REACTOR SIMULATION .......................................................................................................... 20
7.0 SEPARATOR SIMULATION...................................................................................................... 29
7.1 Shortcut Distillation Column (DSTWU) ................................................................................. 29
7.2 Optimization to Determine Optimum Number of Stages Reflux ......................................... 32
7.3 RADFRAC Model ..................................................................................................................... 34
7.3.1 Distillation Column (T-101) ................................................................................................. 34
8.0 PROCESS SIMULATION WITHOUT RECYCLE SYSTEM................................................. 41
9.0 PROCESS SIMULATION WITH RECYCLE SYSTEM ......................................................... 43
9.1 Comparison of Properties Before and After Recycle ............................................................. 45
10.0 REFERENCES ............................................................................................................................ 46
1.0 INTRODUCTION TO MTBE

Methyl tert-butyl ether (MTBE) is a chemical compound as shown in figure 1.0 that has been
used extensively as a fuel additive in gasoline.

Figure 1.0 MTBE in 2D & 3D structures

It is a volatile, colourless liquid with a distinctive odour. MTBE is produced by combining

methanol and isobutylene, which are derived from petroleum. Physical and chemical properties
of MTBE is shown in table 1.0.

Table 1.0: Physical and chemical properties of MTBE

PROPERTY VALUE, DESCRIPTION

Appearance (physical state, colour etc) Clear, colourless liquid
Odour Characteristic ethereal odour
Melting point/freezing point -109oC
Initial boiling point and boiling range 55oC
Flash point –33o C (ASTM D56)
Evaporation rate 8.04 (Normal Butyl Acetate = 1)
Upper/lower flammability or explosive 2% to 15% [vol% in air]
limits
Vapour pressure 27.9 kPa at 20oC
Vapour density 3.1 g/l

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 Relative density 0.74
Solubility 4.8 g/100g OF WATER
Auto-ignition temperature 374oC
Molecular mass 88.2

It is known for its reactivity and chemical stability, remaining stable under normal usage
conditions without undergoing hazardous polymerization. It exhibits a lower likelihood of
forming peroxides compared to other ethers. However, certain precautions should be taken to
ensure safety. High temperatures, open flames, sparks, and the use of un-grounded electrical
equipment should be avoided. MTBE should not encounter strong oxidizers, acids, or bases,
and the use of Viton and Flourel elastomers in seals is not recommended. In the event of
combustion, MTBE can produce hazardous decomposition products such as carbon monoxide
(CO), carbon dioxide (CO2), and reactive hydrocarbons. It's important to note that the vapor
of MTBE is heavier than air, which means it can travel along the ground and pose a risk of
distant ignition. Adhering to proper handling and storage practices is essential to minimize
potential hazards associated with MTBE.

MTBE has been evaluated by organizations such as the U.S. Environmental Protection Agency
(EPA), World Health Organization (WHO), Agency for Toxic Substances and Disease Registry
(ATSDR), and European Chemicals Agency (ECHA) regarding its safety. The EPA has
classified MTBE as a potential human carcinogen and established maximum contaminant
levels in drinking water. Meanwhile, the WHO considers MTBE a compound of possible health
concern and recommends monitoring its levels in drinking water. The ATSDR provides
information on the potential health effects of MTBE exposure and offers exposure limit
recommendations as well. The ECHA assesses the hazards and risks of MTBE under the
REACH regulation. These evaluations aim to ensure the safe handling of MTBE and minimize
potential risks to human health and the environment.

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1.1 APPLICATION

MTBE became commercially available in the late 1970s and early 1980s as a fuel
additive. Its production and commercial importance grew significantly after 1945, as large-
scale manufacturing of the precursor ethylene oxide became widespread. By the mid-1970s,
industrial quantities of pure, colourless MTBE were being produced. It was initially introduced
as a replacement for lead additives, which were phased out due to their harmful effects on
human health and the environment. Methyl tert-Butyl Ether (MTBE) was first added to
gasoline in Europe in 1973 to replace lead as an anti-knocking agent and as an octane enhancer
(CAL-EPA, 1998). U.S. EPA approved it as a blending component in the U.S. in 1979, to
eliminate the use of leaded gasoline. Typical MTBE levels used by refiners were around 2-3%
by volume, blended in different proportions to achieve performance standards. MTBE's ability
to increase the octane rating of gasoline and its oxygenate properties made it an attractive
alternative.

During the 1990s, the use of MTBE increased significantly in many countries,
particularly in the United States, Europe, and parts of Asia. This growth was driven by the need
to meet stricter air quality regulations and reduce the emissions of pollutants from automobiles.
MTBE was widely used as an octane booster and oxygenate additive in gasoline formulations
to improve engine performance and reduce air pollution. By enhancing combustion, MTBE
helps reduce engine knocking and allows for higher compression ratios, resulting in improved
fuel efficiency. However, the use of MTBE has declined in many regions due to concerns about
its environmental impact, particularly its potential to contaminate water sources. Many
countries have implemented restrictions or phased out its use as a fuel additive. Alternative fuel
additives like ethanol have gained prominence as substitutes for MTBE.

Currently, the use of MTBE is limited in various regions, and its primary applications
have shifted to other industries. MTBE is used as a solvent in the manufacturing of chemicals,
such as pharmaceuticals, pesticides, and coatings. It is also employed as an extraction agent in
various processes. For example, MTBE is used as a solvent in the production of pharmaceutical
products such as injections, oral solutions, and topical medications. It aids in dissolving active
pharmaceutical ingredients (APIs) and other components to create homogeneous formulations.
However, the overall usage of MTBE has significantly decreased compared to its previous
application as a gasoline additive.

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1.2 MARKET SURVEY

1.2.1 World Market

Since 1992, the MTBE market has shown robust, ongoing expansion. For instance, the global
consumption in 1998 was nearly 19.5 million tonnes, over twice what it was in 1992, or a 12%
annual growth rate. With US consumption slightly dropping and increasing in other regions of
the world, current trends point to a minor growth in 2000 of up to 20 million tonnes (EEA
2000). The role of MTBE in American petrol increased quickly through 1995, as shown in
figure 1.1.

Figure 1.2.1: MTBE’s role in U.S. gasoline grew rapidly through 1995.

1.2.2 Asia Market

Most Asian nations, including Malaysia, Singapore, Philippines, Thailand, Hong Kong,
Taiwan, South Korea, and Japan, have already phased out lead in their petrol pool in favour of
oxygenates such MTBE. MTBE is the most frequently used oxygenate in Asia due to its
relative simplicity in blending with petrol, ease of transportation and storage, and
comparatively low cost and ample availability.

For nations like Thailand and South Korea, MTBE is not required to be blended with the petrol.
For instance, South Korea requires a minimum oxygenate level of 0.5% in the summer and
1.3% to 2.3% in the winter for petrol. MTBE is mostly used as an octane booster to substitute
lead in other Asian countries.

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1.2.3 Demand
The US West Coast's consumption of 4.1 million tonnes of MTBE annually is at risk
because of legislation in place from 1998 to 2010. It affects 80% of PETRONAS' exports of
MTBE to the US. This simulation mod is represented in figure 1.2.

Figure 1.2.2: World MTBE demand (1998-2010)

About 250,000 b/d of the world's MTBE is consumed in the United States. The majority of
MTBE is used to ensure that petrol delivered to RFG or winter carbon monoxide zones
complies with statutory oxygen content regulations. Octane enhancement may be done with a
tiny amount.

The demand for MTBE in Europe is thought to be over 60,000 b/d. About 6,000 b/d of MTBE
is exported to the United States and is primarily used in Europe for octane enhancement. MTBE
consumption in Eastern Europe is presently around 10,000 b/d. The demand for MTBE in Asia
is anticipated to increase significantly more quickly than in other parts of the world. Since the
early rapid growth was fueled by the lead phase down, which should be virtually complete by
2000, the pace will drop off in the latter part of the decade from approximately 12% per year
to roughly 8% by the turn of the century. The area will be a net importer of MTBE during the
period, primarily from the Middle East.

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1.2.4 Future Forecast
MTBE has its own unique market dynamics and demand drivers. In 2022, MTBE global
market size was valued at USD 16.8 billion. In the projected period from 2022 to 2030, the
MTBE market size is expected to grow at a moderate CAGR of 3.6% as shown in figure 1.3.

Figure 1.2.3 Global Market Forecast for MTBE (2022-2030)

The forecasted market value of MTBE is expected to surpass USD 22.4 billion. MTBE's
primary use as a fuel additive in gasoline has experienced a decline in several regions due to
environmental concerns. As a result, the market dynamics for MTBE have shifted, and its
applications have diversified. While gasoline blending remains a significant application, the
use of MTBE as a solvent in various industries, such as chemicals, pharmaceuticals, and
coatings, has gained prominence.

Factors driving the growth of the MTBE market include:

Solvent Applications

• Industrial Applications
• Regional Market Dynamics
• Substitutes and Competitive Landscape

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MTBE's solvency properties make it suitable for use in various industries. It is utilized as a
solvent in chemical reactions, pharmaceutical formulations, ink production, and adhesives. The
demand for MTBE in these applications is driven by factors such as manufacturing processes,
formulation requirements, and market trends. In terms of industrial applications, MTBE finds
applications in diverse industries beyond fuel blending. It is used as an extraction agent,
cleaning solvent, and in the production of various chemicals. The demand for MTBE in these
industrial applications is influenced by factors such as industrial growth, technological
advancements, and product requirements. At the same time, the demand for MTBE varies
across different regions based on factors such as fuel consumption patterns, industrial
development, and regulatory frameworks. Emerging economies with growing industrial sectors
and increasing fuel demand may present opportunities for MTBE market growth. Not
forgetting the fact that MTBE faces competition from alternative fuel additives, such as
ethanol, which have gained prominence due to environmental concerns. The availability and
pricing of alternative additives can impact the demand for MTBE. Additionally, the
competitive landscape of MTBE producers and their market shares can influence the market
dynamics.

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1.3 SYNTHESIS ROUTE

1.3.1 Direct Etherification

Methyl tertiary butyl ether (MTBE) is produced directly by the reaction of methanol with
isobutylene. This process is known as direct etherification synthesis. As a result of its simplicity
and effectiveness, this technology is frequently utilised in industrial manufacturing. Strong
acids, such as sulfuric acid (H2SO4), or acidic ion-exchange resins are frequently used to
catalyse the process. By creating the requisite acidic conditions for protonation of the reactants
and subsequent ether bond formation, the acid catalyst aids in accelerating the reaction.

The reaction can be represented by the following equation:

CH3OH + (CH3)3CCH=CH2 → (CH3)3COCH3

In this equation, methanol (CH3OH) and isobutylene ((CH3)3CCH=CH2) react to produce

MTBE ((CH3)3COCH3) and water (H2O) as a byproduct.

To maximise the conversion and yield of MTBE, the reaction is normally conducted under a
controlled temperature and pressure. Following the reaction, the mixture is often put through a
separation process to separate the MTBE from unreacted methanol, isobutylene, and other
contaminants using distillation or extraction.

The strong reactivity of isobutylene and methanol favours direct etherification, which makes it
an easy and effective technique for producing MTBE. The possibility of unfavourable side
reactions, such as the oligomerization or polymerization of isobutylene, which might result in
the development of undesired byproducts, is one drawback of this approach. The desired
amount of MTBE is produced while minimising these side reactions through careful process
control and the use of the right catalysts.

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1.3.2 Trans Etherification
Lower ethers, such as dimethyl ether (DME), are transformed into methyl tertiary butyl ether
(MTBE) by interacting with isobutylene in the MTBE trans etherification synthesis method.
This approach, which can be used instead of direct etherification, has some benefits in terms
of process adaptability and feedstock accessibility. Solid acid catalysts, such as zeolites or
acidic ion-exchange resins, are generally used to catalyse the process. These catalysts offer
acid sites that help the reaction between DME and isobutylene to etherify.

The overall reaction can be represented by the following equation:

(CH3)2O + (CH3)3CCH=CH2 → (CH3)3COCH3

In this equation, DME ((CH3)2O) and isobutylene ((CH3)3CCH=CH2) react to produce

MTBE ((CH3)3COCH3).

The trans etherification process has several benefits. By employing lower ethers, which
can be produced from a variety of sources, such as biomass or natural gas, it first offers an
alternate source of isobutylene. As a result, there are more possibilities for feedstock and less
reliance on certain starting materials. Second, using solid catalysts makes it possible to operate
continuously and can make the separation and purification processes simpler.

Depending on the concentrations of the catalyst and reactants, the reaction is normally
conducted at certain temperature and pressure settings. Depending on the needs of the industrial
plant, the choice of catalyst, the nature of the reactions, and the design of the process may
change. Following the reaction, the mixture is usually put through separation procedures such
distillation or extraction to separate the MTBE from unreacted DME, isobutylene, and other
substances.

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1.3.3 Indirect Etherification
In a two-step procedure, the indirect etherification synthesis of methyl tertiary butyl ether
(MTBE) transforms isobutylene into MTBE via the intermediary chemical tert-butyl alcohol
(TBA). This approach offers an alternate mechanism for MTBE synthesis and is frequently
used in industrial manufacturing. Isobutylene is hydrated in the first step of the procedure,
turning it into tert-butyl alcohol. Strong acid catalysts, like sulfuric acid (H2SO4) or acidic ion-
exchange resins, are commonly used to catalyse the reaction.

The reaction can be represented by the following equation:

(CH3)3CCH=CH2 + H2O → (CH3)3CCH2OH

In this equation, isobutylene ((CH3)3CCH=CH2) reacts with water (H2O) to form tert-butyl
alcohol ((CH3)3CCH2OH).

Tert-butyl alcohol is esterified with methanol in the second stage to create MTBE. Like the
direct etherification method, the reaction is normally carried out in the presence of an acid
catalyst.

The reaction can be represented by the following equation:

(CH3)3CCH2OH + CH3OH → (CH3)3COCH3 + H2O

In this equation, tert-butyl alcohol ((CH3)3CCH2OH) reacts with methanol (CH3OH) to yield
MTBE ((CH3)3COCH3) and water (H2O).

Following each stage, the reaction mixture is usually put through separation procedures like
distillation or extraction to purify MTBE and get rid of any unreacted byproducts or starting
ingredients. Regarding flexibility and control over the reaction steps, the indirect etherification
approach has some benefits. It is possible to use isobutylene in a more regulated manner and
to individually optimise the reaction conditions for each step by employing tert-butyl alcohol
as an intermediary. Tert-butyl alcohol's use as an intermediary also makes it possible to create
other beneficial compounds than MTBE.

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Overall, the hydration of isobutylene to tert-butyl alcohol, followed by the esterification of tert-
butyl alcohol with methanol to form MTBE, is the indirect etherification synthesis pathway for
MTBE. This approach allows for efficient MTBE production with the potential for the
development of other useful chemical intermediates by providing flexibility and control over
the reaction stages.

1.3.4 Chosen Process Synthesis Route

Methyl tertiary butyl ether (MTBE) is synthesised via the direct etherification method for
several reasons:

1. Simplicity and Efficiency: The direct etherification process creates MTBE in a single step
by reacting methanol with isobutylene. The reaction scheme's simplicity makes the
procedure easier to understand and more effective. Because there are fewer steps involved,
the production process is less complicated and expensive.

2. High Reactivity: The direct etherification reaction is quick and effective because
isobutylene and methanol have high reactivity. Due to the high reactivity, MTBE can be
produced in large quantities and with a high yield in a very short amount of time.

3. Well-established Technology: The direct etherification process has been thoroughly

investigated and used to produce MTBE on an industrial scale. Long-standing technologies
and dependable production techniques have resulted from the optimisation of process
variables, catalysts, and reaction conditions over time.

4. Cost-effectiveness: In comparison to other methods, direct etherification has lower costs.

The economic viability of this approach is aided by the readily available and reasonably
priced starting ingredients, methanol and isobutylene. Cost-effectiveness is further
increased by the streamlined process steps and lower energy requirements.

5. Fewer Byproducts: When compared to other synthesis methods, the direct etherification
process often produces fewer undesirable byproducts. As a result, fewer separation and

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 purification stages are required, which lowers manufacturing costs and enhances the purity
of the finished MTBE product.

6. Scalability: It is simple to scale up the direct etherification process to satisfy the needs of
industrial production. Larger reaction volumes can be accommodated by adjusting the
reaction conditions and catalyst systems, making it appropriate for manufacture on an
industrial scale.

The direct etherification pathway is frequently chosen because of its simplicity, effectiveness,
cost-effectiveness, and well-established technology, even though trans etherification, and
indirect etherification each have their own benefits. However, the final decision on the
synthesis method is dependent on the production requirements, the accessibility of feedstocks,
and other elements; many routes may be used depending on the specifics of each situation. In
this case, we chosen direct etherification method.

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2.0 THERMODYNAMICS MODEL

MTBE: C5H12O (Non-Polar); Methanol: CH3OH (Polar); Isobutylene: C4H8 (Non-Polar).

In the given effluent, we have three compounds: MTBE (C5H12O), methanol (CH3OH), and
isobutylene (C4H8). Among these compounds, MTBE and isobutylene are considered non-
electrolytes, meaning they do not readily dissociate into ions when dissolved in a solvent. On
the other hand, methanol is classified as a weak electrolyte, which means it partially dissociates
into ions when dissolved in a solvent. Since methanol is a weak electrolyte, it exhibits some
level of ionic behavior in solution, although not as pronounced as strong electrolytes. However,
it's important to note that the extent of ionization for weak electrolytes like methanol is
relatively low. Therefore, when considering the overall behavior of the effluent, we can
approximate it as a polar, non-electrolyte mixture.

In this context, the term "polar" refers to the presence of a polar compound (methanol) in the
mixture. Polar compounds have an uneven distribution of charge within their molecules,
resulting in a positive and negative end. Methanol, with its polar hydroxyl group (OH), exhibits
this uneven charge distribution. Regarding the electrolyte nature, since only methanol is a weak
electrolyte and the other compounds are non-electrolytes, the overall effluent can be considered
a non-electrolyte mixture. This implies that the compounds in the effluent do not readily
dissociate into ions when mixed and dissolved in a solvent. Considering these factors, we can
characterize the effluent as a polar, non-electrolyte mixture due to the presence of methanol
as a weak electrolyte and the non-electrolyte nature of the other two compounds (MTBE and
isobutylene). At the same time, this process took place in pressure lower than 10 bar and all
three compounds are commonly used thus all the interaction parameters are available in Aspen
Plus. About the miscibility, it consists of organic and inorganic compounds which are not
miscible to each other. Hence, two liquid phases will occur in this condition with one layer of
MTBE and isobutylene and another layer of methanol. Refer to the Eric Carlson’s
recommendation, the non-polar non-electrolyte mixture at the condition of atmospheric
pressure, lesser than 10 bar, with available of interaction parameters and the existence of two
liquid phase, hence the two suitable thermodynamics properties method that suitable for this
process is NRTL.

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3.0 THERMODYNAMIC BINARY ANALYSIS

Binary analysis functions are set in Aspen Plus to obtain a graph of T-xy that shows the
miscibility of a binary mixture with two unique components that are meant to be separated to
detect the existence of azeotropes in the reactor products. When looking at heavy components
such as diisobutylene and methanol, diisobutylene can be separated from MTBE without any
problem as shown in figure 3.1.

Figure 3.1: T-xy Diagram for Binary Mixture of Diisobutylene and MTBE

The same can’t be said for methanol as shown in figure 3.2.

Figure 3.2: T-xy Diagram for Binary Mixture of Methanol and MTBE

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Based on the figure, it shows occurrence of azeotrope between methanol and MTBE. Hence a
common distillation column can’t be used to separate these mixtures as enhanced distillation
or other separation techniques like extraction must be used to successfully separate the
methanol azeotropes from MTBE in T-101. Same binary analysis can be done for T-102 but a
common distillation column can be used to separate these mixtures as it shows no occurrence
of azeotrope. This is influenced by the fact that only methanol has azeotropes with MTBE and
most methanol (99.99%) is separated from MTBE during first separation in T-101.

The light components are separated from the MTBE in the second separation in T-102. Since
they are in distinct states and have low boiling temperatures, light components can be separated
without any problems, negating the need to use the binary analysis function to check their
miscibility with MTBE in T-102, however the analysis is done to prove the theory as shown in
figure 3.3,3.4,3.5.

Figure 3.3: T-xy Diagram for Binary Mixture of Isobutylene and MTBE

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 Figure 3.4: T-xy Diagram for Binary Mixture of 1-butene and MTBE

Figure 3.5: T-xy Diagram for Binary Mixture of 2-butene and MTBE

Based on those figures, these light components can be separated from MTBE without any
problems. Hence, enhanced distillation or other separation techniques like extraction are not
needed for T-102.

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 T= 271 K
4.0 PROCESS FLOW DIAGRAM P = 1 bar

T= 276 K T-102
P = 1 bar

T= 328 K T= 324 K
T= 292 K P = 8 bar
T= 298 K P = 1 bar P = 1 bar
P = 1 bar MIX-101
Butenes 4
T-101
9
2 3
E-101

R-101 MTBE
T= 372 K
P = 1 bar
T= 298 K
7
P = 1 bar 1
5

T= 328 K
P = 8 bar

Methanol

PROCESS FLOW DIAGRAM OF METHYL TERT- BUTYL ETHER

(MTBE) PRODUCTION WITHOUT RECYCLE STREAM 17 | P a g e
 T= 372 K
P = 1 bar
11

S-101

T= 271 K
T= 372 K P = 1 bar 8
P = 1 bar

10

T= 276 K T-102
P = 1 bar

T= 328 K T= 324 K
T= 292 K
T= 298 K P = 8 bar P = 1 bar
P = 1 bar
P = 1 bar MIX-101
Butenes 4
T-101
9
2 3
E-101

R-101 MTBE

T= 298 K
P = 1 bar
1
5 T= 372 K
P = 1 bar
T= 328 K
P = 8 bar 7

Methanol

PROCESS FLOW DIAGRAM OF METHYL TERT- BUTYL ETHER

(MTBE) PRODUCTION WITH RECYCLE STREAM 18 | P a g e
5.0 PLANT CAPACITY

The plant is assumed to be operated in continuous mode for a period of 333 days in a year. In
other words, the number of operating hours was set at 8000 hours.

Isobutylene molecular weight = 56.106 g/mol

MTBE molecular weight = 88.15 g/mol
100000𝑀𝑀𝑀𝑀 1000𝑘𝑘𝑘𝑘 1𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 1𝑦𝑦𝑦𝑦
× × × = 141.804 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘/ℎ𝑟𝑟
𝑦𝑦𝑦𝑦 𝑀𝑀𝑀𝑀 88.15 𝑘𝑘𝑘𝑘 8000ℎ𝑟𝑟
Assumption: Yield = 97%
Conversion = 90.2% (Rule of Thumb)
Recovery = 99.3 %
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
𝑌𝑌𝑌𝑌𝑌𝑌𝑌𝑌𝑌𝑌 × 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 × 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 =
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑜𝑜𝑜𝑜 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 = 163.215 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 ⁄ℎ𝑟𝑟

163.215 𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 56.106 𝑘𝑘𝑘𝑘

𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤ℎ𝑡𝑡 = × = 9157.360 𝑘𝑘𝑘𝑘⁄ℎ𝑟𝑟
ℎ𝑟𝑟 1𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘

According to the calculations from above, the feed given below allows us to produce 100,000
MTA of MTBE, which is the necessary capacity. The obtained values were substituted into the
feed stream and simulation was run. However, the actual production was not at desired capacity
as the results of the production amount ends lower than 100,000 MTA.The isobutylene and
methanol feed are adjusted to obtain desired plant capacity and the process is explained in the
reactor simulation as the conditions of reactor are adjusted as well to obtain the desired plant
capacity.

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6.0 REACTOR SIMULATION

Using the reaction information given in the project handout, the reactions including the main,
and side of the reaction are filled out with the correct information as shown in figure 6.1.

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Figure 6.1: Reaction and reaction kinetics

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The reactor and feed condition must first be set up to calculate the appropriate flow rate of
reactants to the reactor. Referring to (Methyl-Tert-Butyl-Ether Synthesis Reactor Modelling
and Optimization Using an Aspen Custom Modeler | Request PDF, 2017), the reactor and feed
condition configuration are inserted. The ratio of isobutylene to methanol for the initial rate of
feed entering the reactor is fixed at 1.1. The main feed must flow at a total of 478.26 kmol/hr
to maintain an isobutylene fraction of 0.23 when methanol is utilized at a rate of 100 kmol/hr
and 110 kmol/hr of isobutene is required. The initial setting for the feed's temperature and
pressure is 55°C and 8 bar. A multi-tube packed bed reactor with 100kg of catalyst made of
ion-exchange resin is the reactor in use. At an inlet temperature of 55 oC and pressure of 8 bar,
the reactor is operational.

The configuration of the reactor is as shown in figure 6.2.

Figure 6.2: Packed Bed Reactor’s Configuration.

The simulation is run however, the desired production rate of MTBE wasn’t achieved.
Therefore, to find the amount of feed required to produce 100000 MTA of MTBE, the design
spec function will be used as shown in figure 6.3.

Figure 6.3: Design spec input

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Setting a targeted value of 100000 MTA of MTBE to be produced in the reactor’s outlet, both
the isobutyl feed and the methanol feed will be varied at the same time to find the optimal
amount of each respectively. After the simulation is run again, the designated feed results will
be obtained as shown in figure 6.4 and 6.5.

Figure 6.4: Design spec results for isobutyl mixture feed

Figure 6.5: Design spec results for pure methanol feed

From the design specs, the calculated results for isobutylene mixture feed required is 816.616
kmol/hr and the amount of methanol feed required is 134.18 kmol/hr. The reactor's conversion
can still be enhanced even though it has already produced 100000 MTA of MTBE under the
previous reactor parameters. One of the reactor's parameters can be used in a sensitivity
analysis to accomplish this. The range of reactor length is chosen in the range of 1m to 10m at
an increment of 0.1m per iteration, with other feed and reactor parameters (pressure,
temperature, catalyst weight, etc.) set as constants. The values from the sensitivity analysis tab
are entered as shown in figure 6.6 and 6.7.

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 Figure 6.6: Sensitivity analysis of reactor length (part 1)

Figure 6.7: Sensitivity analysis of reactor length (part 2)

Once the targeted parameters and values are inserted, the simulation is run, and the data results
are tabulated in figure 6.8. From the results, a graph of MTBE production per annum vs the
length of reactor in meters is developed as shown below in figure 6.9.

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 Figure 6.8: Sensitivity analysis results of reactor length

Figure 6.9: Graph of MTBE production per annum vs the length of reactor.
From the curve, it can be observed that as the length of the reactor increases, the amount of
MTBE produced per annum increases until it reaches around 1.8m to around 2.1m, which is
significantly lower than the length currently used, which is 6m. This can reduce construction
material costs while marginally increasing the yield as shown in figure 6.10.

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 Figure 6.10: Adjustment for reactor length
The number of tubes utilised for the reactor, abbreviated NTUBES, can also be optimised after
reactor length has been corrected. The parameters are left unchanged from the previous
analysis, while the range of reactor tube numbers is chosen between 1000 and 10000 with an
increase of 101 tubes per iteration as shown in figure 6.11.

Figure 6.11: Sensitivity analysis of number of tubes

Once the targeted parameters and values are inserted, the simulation is run, and the data results
are tabulated in figure 6.12. From the results, a graph of MTBE production per annum vs the
number of tubes is developed as shown below in figure 6.13.

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 Figure 6.12: Sensitivity analysis results of number of tubes

Figure 6.13: Graph of MTBE production per annum vs the number of tubes
The graph of annual MTBE output versus reactor tube count is produced using the findings.
The more tubes used; the more MTBE is produced. However, the pace of growth slows down
once the number reaches about 8000. The maximum number of tubes that can be used while
still producing the required 100000 MTA of MTBE is approximately 8182 tubes. The final
reactor specification is as shown in figure 6.14.

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 Figure 6.14: Revised reactor configuration

The simulation is run, and mass flowrate results are shown in figure 6.15.

Figure 6.15: Reactor’s stream result

Using the revised reactor configuration, we were able to produce the required 100000 MTA of
MTBE while reducing the length and number of tubes from the original reactor configuration
based on reviewed literature.

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7.0 SEPARATOR SIMULATION

7.1 Shortcut Distillation Column (DSTWU)

Figure 7.1.1: DSTWU column

Based on Figure 7.1, we design the first column known as T-101. The light key is set as MTBE
with recovery of 99.9 % and the heavy key was set as methanol with 0.1% recovery, both at
the distillate stream as shown in figure 7.1.2. Methanol was chosen as heavy key instead of
MTBE as methanol’s boiling point is higher than MTBE as Aspen Plus simulation for
distillation column is dependent on the boiling point in terms of heavy and light key.

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 Figure 7.1.2: DSTWU (T-101) Setup
After initial setup, the simulation was run and the results of the DSTWU parameters were
shown as in figure 7.1.3.

Figure 7.1.3: DWSTU (T-101) Results

The same steps were followed when designing the second column known as T-102. The light
key is set as 2-butene with recovery of 99.9 % and the heavy key was set as MTBE with 0.1%
recovery, both at the distillate stream as shown in figure 7.1.4. The feed this time is from the
top outlet stream from T-101 as we want to obtain the MTBE as pure as possible as we separated
it from methanol initially.

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 Figure 7.1.4: DSTWU (T-102) Setup
After initial setup, the simulation was run and the results of the DSTWU parameters were
shown as in figure 7.1.5.

Figure 7.1.5: DWSTU (T-102) Results

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7.2 Optimization to Determine Optimum Number of Stages Reflux

Figure 7.2.1 Table of RR vs NS for (T-101)

Based on Figure 7.2.1, the results obtained from figure 7.1.3 where the minimum number of
stages is 24. Therefore, the initial number of stages= 24. The final number of stages can be first
set as the actual number of stages and further adjusted to get the minimum point in the plot of
NS*RR vs NS. The simulation was run, and the results were tabulated as shown in figure 7.2.2.

Figure 7.2.2: NS vs RR (T-101)

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The data where NS*RR and NS was then plotted into excel and the minimum point of the graph
was observed as the minimum point indicates the optimum number of stages as shown in figure
7.2.3.

NS*RR vs NS
60

50

40
NS*RR

30

20

10
20 25 30 35 40 45 50 55 60 65
NS

Figure 7.2.3: NS*RR vs NS (T-101)

Based on the graph, the optimum number of stages for T-101 was 51 stages. The same steps
were repeated for T-102. And the graph is as shown in figure in figure 7.2.4.

NS*RR vs NS

21
NS*RR

11

1
5 7 9 11 13 15 17 19 21 23 25
NS

Figure 7.2.4: NS*RR vs NS (T-102)

Based on the graph, the optimum number of stages for T-102 was 16 stages.

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7.3 RADFRAC Model

For the input for the RADFRAC column, the values obtained from the results of the shortcut
distillation column was set as input. The number of stages was set after the optimization was
done where we obtained 51 stages for T-101 and 16 stages for T-102.

7.3.1 Distillation Column (T-101)

The condenser is set as total condenser with reflux ratio of 0.434, distillate to feed fraction of
0.95 and number of stages of 51 under the configuration tab as shown in figure 7.3.1.

Figure 7.3.1: T-101 (RADFRAC) setup

Under the stream tab, the number of stages for the feed stage is set as 25 above the stage as
shown in figure 7.3.2.

Figure 7.3.2: Above Stage Number for T-101

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Under the pressure tab, the condenser pressure is set as 1 bar as shown in figure 7.3.3.

Figure 7.3.3: Pressure Setup for T-101

7.3.2 Distillation Column (T-102)

Same step was repeated for T-102 as shown in figure 7.3.4.

Figure 7.3.4: T-102 (RADFRAC) setup

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Under the stream tab, the number of stages for the feed stage is set as 8 above the stage as
shown in figure 7.3.5.

Figure 7.3.5: Above Stage Number for T-102

Under the pressure tab, the condenser pressure is set as 1 bar as shown in figure 7.3.6.

Figure 7.3.6: Pressure Setup for T-102

After simulation was run, it was observed that the mass purity of MTBE recovered from the
final distillation column didn’t reach the product specification which was 95wt%. To resolve
this issue, design spec was used to obtain the desired product specification.

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Under Flow sheeting Options, a new Design Spec named 1 is created as shown in figure 7.3.7.

Figure 7.3.7: Design Spec 1

Under Specification section, the variable Mass purity, 0.95, PRODUCT is created with the
specification of the mass purity and a target of 0.95 as shown in figure 7.3.8.

Figure 7.3.8: Mass purity specification

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Under component section the MTBE is selected as the component of interest and the base
component is selected all the available components as shown in figure 7.3.9.

Figure 7.3.9: Base components in DS-1

Figure 7.3.10: Feed/Product streams

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Under Flow sheeting Options, a new vary named 1 is created as shown in figure 7.3.11.

Figure 7.3.11: Vary 1

Under the specification tab, the Distillate to feed ratio, 0.01, 0.9999 is created and the distillate
to feed ratio is the adjusted variable and the upper lower boundary of 0.01 and upper boundary
of 0.9999 is adjusted as shown in figure 7.3.12.

Figure 7.3.12: Distillate to Feed Ratio

The simulation is ready to run. By checking the stream results shown in figure 7.3.13, it is
shown that the target purity and production capacity is achieved through Design Spec.

T-101 (Top) T-102 (Botom) T-102 (Top)

Figure 7.3.13: Mass Fractions in T-102

The production of MTBE of 95 wt% was achieved after target is reached.

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 106.752
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝑜𝑜𝑜𝑜 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝑖𝑖𝑖𝑖 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 =
106.776
= 0.9998 × 100%
= 99.978 %

The production of MTBE achieved 99.978 % of recovery.

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8.0 PROCESS SIMULATION WITHOUT RECYCLE SYSTEM

The PFD of process without recycle stream is shown in Figure 8.1 as below:

Figure 8.1: PFD of Process Without Recycle Stream

The simulation will be run without the inclusion of a recycle stream and the data results will
be shown in figure 8.2.

Figure 8.2: Mass Flowrate of T-102 Without Recycle Stream in kg/hr.

9410.18
𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝑜𝑜𝑜𝑜 𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 =
9905.46
= 0.95 × 100%
= 95 %

For the simulation of the process without recycle stream, we can achieve the targeted purity of
0.95 using design spec function. However, due to around 11754.6 tons/year of MTBE lost in
the T1-BOTT stream during the first stage of distillation, we were unable to meet the required
100 000 MTA of 95% purity MTBE produced through the plant as shown in figure 8.3.

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 Figure 8.3: Mass Flowrate of T-102 Without Recycle Stream in tons/year.

To rectify this issue, we included a recycle stream which will help to achieve the desired target
of 100 000 MTA MTBE with 95% purity. Before proceeding to the next part, in terms of heat
energy that used in the whole process without recycle, the heat duty of each equipment is
calculated and summed up.

Total Heat Duty = [ E-101 + R-101 + T-101 + T-102 ] kW

= [ -3573.11 + -1844.18 + -7750.61 + -5455.87 ] kW

= -18623.770 kW

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9.0 PROCESS SIMULATION WITH RECYCLE SYSTEM

The PFD of process with recycle stream is shown in Figure 9.1 as below:

Figure 9.1: PFD of Process with Recycle Stream

The simulation will be run with the inclusion of a recycle stream to fulfil the demand of 100000
MTA of MTBE with 95% purity. With the use of a stream splitter, the T1-BOTT stream which
contains a decent amount of MTBE lost, can be retrieved back into the mainstream. The split
fraction setup is as shown in figure 9.2.

Figure 9.2: Split fraction setup for MTBE recycle.

Through trial and error, the highest recyclable fraction that can be used without encountering
convergence error or mass balance error in the simulation is around 35%. The rest will be
exiting through a purge stream, where it will then be disposed of accordingly. This helps
prevent the build-up of impurities within the stream. The simulation is then run, and the data
results are shown in figure 9.3.

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 Figure 9.3: Data Results of T-102 with Recycle Stream

As seen in the above figure, the quantity of MTBE lost in the T1-BOTT stream can be
decreased with the addition of a recycle stream to just about 736.7 tons/year as opposed to
11754.6 tons/year lost without the recycle. The T2-BOTT stream, which contains 102360 MTA
of MTBE with a purity of 95%, is the most significant of all. With this, we can meet the demand
for 100 000 MTA of MTBE with 95 wt% purity.

In terms of heat energy that used in the whole process with recycle, the heat duty of each
equipment is calculated and summed up.

Total Heat Duty = [ E-101 + R-101 + T-101 + T-102 ] kW

= [ -3620.7 + -1838.84 + -7945.49 + -5449.97 ] kW

= -18855 kW

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9.1 Comparison of Properties Before and After Recycle

Table 9.1: Comparison of Properties Before and After Recycle

PROPERTIES BEFORE RECYCLE AFTER RECYCLE

Production Capacity of
MTBE 90929.3 102360
(Metric tons /annum)

Weight Percentage of
MTBE Produced (wt%) 95 95

Target Production Rate

and Purity
Partially Achieved Achieved

Heat Duty (kW) -18623.770 -18855

Number of Equipment 5 6

According to Table 9.1, the main difference before and after recycle stream introduced into the
system is the production capacity of MTBE where the desired production capacity of 100 000
MTA of MTBE is only achieved when recycle stream is introduced. Due to that, the target of
production rate and purity is partially achieved when recycle stream is not introduced as the
target of production rate of 100 000 MTA of MTBE isn’t achieved. This recycle stream strategy
is beneficial as when comparing in terms of heat duty, it shows insignificant change therefore
this strategy is very helpful in terms of cost and production target.

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10.0 REFERENCES

1. Aspen Technology. (2013). Aspen Physical Property System: Physical Property

Methods. Aspen Technology, Inc, 1–234.
http://profsite.um.ac.ir/~fanaei/_private/Property Methods 8_4.pdf

2. Badra, J., Alowaid, F., Alhussaini, A., Alnakhli, A., & AlRamadan, A. S. (2022).
Understanding of the octane response of gasoline/MTBE blends. Fuel, 318.
https://doi.org/10.1016/j.fuel.2022.123647

3. Elkanzi, E. M. (1996). Optimization of MTBE synthesis in a fixed-bed reactor system.

Chemical Engineering and Processing: Process Intensification, 35(2).
https://doi.org/10.1016/0255-2701(95)04122-2

4. Hauan, S., Hertzberg, T., & Lien, K. M. (1997). Multiplicity in reactive distillation of
MTBE. Computers and Chemical Engineering, 21(10). https://doi.org/10.1016/S0098-
1354(96)00322-5

5. Methyl-Tert-Butyl-Ether Synthesis Reactor Modelling and Optimization Using an

Aspen Custom Modeler | Request PDF. (2017). ResearchGate; ResearchGate.
https://www.researchgate.net/publication/325035676_Methyl-Tert-Butyl-
Ether_Synthesis_Reactor_Modelling_and_Optimization_Using_an_Aspen_Custom_M
odeler

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