CHAPTER 1.0 INTRODUCTION

1.1 BACKGROUND

Zimbabwe imports all of its petroleum which is then refined to produce various petroleum

products like petrol and diesel oil. Despite government’s support for the use of unleaded and

leaded petrol which is a health hazard. The use of petrol without fuel oxygenate poses an

environmental threat, Oxygenates help petrol burn more completely, reducing emissions from

motor vehicles; dilutes or displaces gasoline components such as aromatics (e.g., benzene) and

sulphur; and optimizes the oxidation during combustion and they help raise the oxygen content

of petrol. Our group proposes the use of methyl tertiary-butyl ether (MTBE) as an alternative

petrol additive/oxygenates to lead and other additives hence the need for a feasibility study on

the production of MTBE production in Zimbabwe. MTBE fuel blends are likely to have

substantial air quality benefits. Use of MTBE decreases gasoline overall cancer potential by

displacing more potent carcinogenic materials in gasoline. MTBE is approximately seven times

less potent than benzene and twenty five times less potent than 1, 3-butadiene, toxic components

found in gasoline and motor vehicle emissions. Releases of petrol containing either MTBE or

lead could have an impact on some drinking water sources, although the impacts associated with

MTBE tend to relate to aesthetics (i.e. Taste and odor), whereas the impacts associated with lead

generally relate to health risk.

1.2 USES AND IMPORTANCE OF MTBE

MTBE is an octane enhancer that prevents engines from knocking

MTBE is used extensively as a fuel additive in petrol blending

MTBE-petrol blend is eco-friendly so it is better to use it and reduce pollution.

MTBE-Petrol blends are compatible with most cars

MTBE is also used as a chemical intermediate to produce high purity isobutylene

High purity MTBE is being used as a process reaction solvent in the pharmaceuticals

industry

Minor use patterns are use as chromatographic eluent and use as a therapeutic agent for in

vivo dissolution of cholesterol gallstones in humans

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ALTERNATIVES FOR MTBE

ETBE (Ethyl tertiary butyl ether), TAME (Tert amyl methyl ether), DIPE(Di isopropyl

ether. These are all ethers like MTBE. There is no field data available due to limited use

of them.

Alkalytes: these are a mixture of high octane, low vapor pressure compounds that are

produced from crude oil through a catalytic cracking process. They have low solubility in

water and are likely not to pose the same risks to water resources. They also increase

price of reformulated gasoline.

Aromatics; these are high in octane and may cause health risks i.e carcinogens, lower

potency central nervous system and liver toxicants.

Lead ;tetrahedral lead is used to reduce engine knocking, boost octane rating and help

with wear and tear on valve seats within the motor. Lead tends to clog up catalytic

converters making them inoperable. It is poisonous to humans.

1.3 PROBLEM STATEMENT

Currently there is no local production of MTBE in Zimbabwe; the country is using lead ,ETBE,

as a fuel additive. Nevertheless, there has been a public outcry rejecting the use of lead with

problems emanating from it being poisonous to human health. We seek to investigate the

technical and economic feasibility of producing MTBE in Zimbabwe.

1.4 JUSTIFICATION

MTBE production is cheaper since the raw materials are locally available

In Africa there is no production of MTBE, the proposal of a cost effective MTBE

production process will go a long way in alleviating Africa’s energy challenges.

The country can export excess MTBE to other African countries.

Availability of MTBE can go a long way in solving environmental problems associated

with the widespread use of leaded and unleaded petrol.

1.5 RESEARCH FOCUS

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This study was conducted to find a technical and economic feasible process for the production of

MTBE in Zimbabwe from locally available raw materials that will account for maximum

production and better quality. The project aims to find a process that is energy-efficient and

affordable technology in the production of MTBE and increase its market potential.

1.6 RESEARCH QUESTIONS

Is the process cost effective?

Is the process environmentally friendly?

Are the products environmentally friendly?

How can Zimbabweans benefit from MTBE?

How does MTBE production in Zimbabwe affect its economy?

1.7 SCOPE

The project will focus on effect of pressure, temperature and catalyst on the production of MTBE

and conversion of isobutylene. The results from the experiments will be used to design the

process and the equipment used for the production process.

1.8 STUDY HYPOTHESIS

H0-It is feasible to produce MTBE in Zimbabwe

H0-It is technically and economically feasible to produce MTBE

H1-It is not feasible to produce MTBE in Zimbabwe

H1-It is not technically and economically feasible to produce MTBE

1.9 PROJECT OBJECTIVES

To design a process that is economically and technically feasible.

To make an affordable and cheap fuel additive of which MTBE is cheap.

To make a petrol blend with a long shelf life. MTBE- petrol blend has a shelf life of

several years

To make a petrol blend that is environmentally friendly

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CHAPTER 2.0: LITERATURE REVIEW

Currently there is no local production of MTBE (Methyl tertiary-Butyl ether) in

Zimbabwe.MTBE is being produced in countries such as China, Saudi Arabia, Malaysia and

Singapore. Methyl tertiary butyl ether (MTBE) is produced by reacting isobutene with methanol

over a catalyst bed in the liquid phase under mild temperature and pressure (Collignon, 1996).

Isobutene can be obtained from stream cracker raffinate or by the dehydrogenation of isobutene

from refineries. Ether in general is a compound containing an oxygen atom bonded to two carbon

atoms. In MTBE one carbon atom is that of a methyl group – CH3 and the other is the central

atom of a tertiary butyl group, -C (CH3)). At room temperature, MTBE is a volatile, flammable,

colorless liquid with a distinctive odor. It is miscible with water but at high concentrations it will

form an air-vapor explosive mixture above the water, which can ignite by sparks or contact with

hot surfaces.MTBE has good blending properties and about 95% of its output is used in gasoline

as an octane booster and an oxygenate (providing oxygen for cleaner combustion and reduced

carbon monoxide emissions). It is also used to produce pure isobutene from C4 streams by

reversing its formation reaction. It is a good solvent and extractant. (Casebook#4, Rev 1.Methyl

Tertiary Butyl Ether (MTBE) Plant. March 1995)

Table 1 Physical properties of MTBE

Chemical formula C5H12O

Oxygen content 18.2 wt.%

Molecular structure (CH3)4CO

Physical state (at normal temperature and

pressure)

Colorless liquid

Boiling point 55.2Oc

Melting point -108.6oC

Flash point 30oC

Auto ignition temperature 425oC

Flammable limits in air 1.5 – 8.5%

Relative density 0.7405g/ml at 20oC

Vapor pressure 245 mm Hg at 25oC

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Reactive index 1.3690

Color Colorless

Figure 1: MTBE structure

2.1 METHODS USED FOR THE PRODUCTION OF MTBE

There are nine methods of producing MTBE implemented under license as the following:

1. UOP-Oleflex Process

2. Phillips Etherification Process

3. ABB Lummus Catofin Process

4. Snamprogetti Process.

5. Standard (Huls) process

6. ETHERMAX process (by Huls AG and UOP)

7. Refinery or Petrochemical plants

8. Merchant plants

9. Tertiary Butyl Alcohol

2.1.1 UOP-Oleflex Process

The UOP-Oleflex process uses multiple side-by-side, radial flow, and moving-bed reactors

connected in series. Preheated feed and interstage heaters supply the heat of reaction. The

reaction is carried out over platinum supported on alumina, under near isothermal Conditions.

The catalyst system employs UOP's Continuous Catalyst Regeneration (CCR) technology. The

bed of catalyst slowly flows concurrently with the reactants and is removed from the last reactor

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and regenerated in a separate section. The reconditioned catalyst is then returned to the top of the

first reactor. The typical processes involved are the deisobutenization, the isomerization and the

dehydrogenation process that has been commercial in Malaysia. (Quintain,2013)

2.1.2 Phillips Etherification process (by Philips Petroleum Co.)

This process uses olefins (i.e. isoamylene and isobutylene) to react with methanol over

acidicIon-exchange resin. Mixed olefins from a fluid catalytic cracking unit (FCCU) or steam

Cracker, along with fresh alcohol are fed to the reactor section. The reactor operation is liquid

phase at mild temperature and pressure. In case of MTBE, high purity MTBE is removed as a

bottom product from the fractionator and all the unreacted methanol is taken overhead. The

overhead product is then stripped of methanol in an extractor using water. The extract is sent to

the fractionator, while the denuded water is returned to the methanol extractor. (Quintain,2013)

2.1.3 ABB Lammus Catofin Process

The ABB Lummus Catofin Process uses a relatively inexpensive and durable Chromium oxide–

alumina as catalyst for the dehydrogenation process. This catalyst can be easily and rapidly

regenerated under severe conditions without loss in activity. Dehydrogenation is carried out in

the gas phase over fixed beds. Because the catalyst cokes up rapidly, five reactors are typically

used. Two are on stream, while two are being regenerated and one is being purged. The reactors

are cycled between the reaction and the reheat/regeneration modes, and the thermal inertia of the

catalyst controls the cycle time, which is typically less than 10 minutes. The chromium catalyst

is reduced from Cr6+ to Cr3+ during the dehydrogenation cycle. The raw materials used to

produce MTBE by using this method are butanes, hydrogen and as well as recycled isobutene

from the system itself. In this process, there is an isostripper column, which separates the

heavies, and the light ends from which then could produce MTBE.(Hutchings,1992)

2.1.4 Snamprogetti Process

Similar to Philips Etherification Process, ethers are produced by the addition of alcohol to

reactive olefins in the presence of an ion exchange resin at mild temperature and pressure.

The feed passes through two reactors in series – an isothermal tubular reactor and an adiabatic

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drum reactor. The second reactor effluent goes to the product fractionation tower where the ether

product leaves the bottom stream and hydrocarbon is recovered overhead. In the MTBE process,

methanol in the overhead stream is extracted with water in the water removal tower. The extract

from the bottom enters the methanol-water fractionator, while the water overhead is recycled to

reactor feed. (Quintain,2013)

2.1.5 Standard (Huls) Process

The key feature of this process is the fixed bed MTBE reactor used prior to the azeotropic

distillation column .Conversions of isobutylene to MTBE are in the range 85-95%.In many

plants two reactors are used in tandem, along with recycle in order to increase the overall

conversion closer to 99%.(Quintain,2013)

2.1.6 ETHERMAX Process

This process which uses reactive distillation technology is developed by combined expertise

of Huls AG and UOP. The feed consists of methanol and hydrocarbon streams containing

reactive tertiary olefins such as isoamylene and isobutylene. Reaction takes place over an acidic

ion exchange resin at mild temperature and moderate pressure. In the MTBE case, feed first

passes through an optional water wash system to remove the resin contaminants. The majority of

the reaction is carried out in a simple fixed-bed reactor. The reactor effluent feeds the reactive

distillation column containing a proprietary packing where simultaneous reaction of the

remaining isobutylene and distillation occur. Overhead from the reactive distillation column is

routed to methanol recovery, a simple counter current extraction column using water, and a

methanol-water distillation column. The recovered methanol is recycled to the reactor section.

Hydrocarbon raffinate is typically sent to a downstream alkylation or oligomerization unit.

(Quintain,2013)

Refinery or Petrochemical

Isobutylene produced is a by product in refinery catalytic crackers and in petrochemical ethylene

plants, is reacted with methanol to produce MTBE.

Merchant plants

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Normal butane is isomerized to isobutene, the isobutene is dehydrogenated to isobutylene and

then combined with methanol to produce MTBE.

TBA Plants

Tertiary butyl alcohol is a byproduct of propylene oxide production process. The TBA is reacted

with methanol to produce MTBE.

2.2 PROCESS SELECTION

Suitable process, which is gives a lot of profit and less problem is an important in order to

determine the feasibility of the project. This section will briefly discuss the best process selected

based on a few criteria. It covers general consideration, detailed consideration for process

selection and conclusion on the process selection.

Phillips Etherification process (by Philips Petroleum Co.) process will be chosen as the method

to produce MTBE.

2.2.1 PROCESS DESCRIPTION

MTBE is manufactured by catalytically reacting methanol and isobutylene in a fixed bed reactor

at a moderator pressure and temperature. The reaction is reversible and exothermic, and is

carried out in the liquid phase over a fixed bed of sulphonated ion-exchange resin-type catalyst.

It is highly selective since methanol reacts prefentially with the isobutylene in the mixed butenes

(Quintain, 2013).In this MTBE process, an isobutylene-rich mixed C4 stream is mixed with fresh

methanol and a small amount of recycle methanol and fed to the reactor section. The reactor is

cooled to prolong catalyst life and to minimize the undesirable side reactions such as the

dimerization of isobutylene (Hutchings,1992). Temperatures below 94oC are recommended. The

reactor is adiabatic, and the reaction is exothermic. Therefore, the heat generated by the reaction

raises the temperature of the exit stream. The exit temperature is a function of the conversion.

The reaction must be run at a pressure and temperature to ensure that all components remain in

the liquid phase in the reactor. Methanol must be present in the reactor feed at a minimum 200%

excess to suppress undesired side reactions that produce undesired products.

(Collignon,1996).The Philips Etherification process uses three distillator but for our process

design we will employ two fractional distillators due to the replacement of mixed butenes with

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just isobutylene in the process, thus saving money. In the original etherification process,

methanol is recycled to the reactor feed whilst butenes and the unreacted methanol are treated as

waste.In our process design we recycle both the unreacted methanol and isobutylene, thus

maximizing on raw materials and profits.

Chemical Reaction

The reaction is facilitated by a sulphonated ion-exchange resin catalyst. The reaction is:

CH 3OH +(CH 3 )2 C=CH 2 ←⃗(CH 3 )3C−O−CH 3

2.2.2 ADVANTAGES OF THE PROCESS

More detailed reasons for the selection of this process are:

High conversion (greater than 98 %) with few by-products compared to other process

The process operates under low pressure and has a low pressure drop and this means that

the fluidized bed is physically not harmful to anyone.

As the Temperature is not high; this means that the process is not as dangerous as other

high temperature-operated process.

Higher per pass conversion and at least 1-2% higher catalyst selectivity as a result of

lowest operating pressure and temperature.

No catalyst losses.

2.2.3 PROCESS EQUIPMENT

1. Reactor

Several reactor types may be considered for use in this process such as:

An adiabatic, packed bed reactor

An “isothermal,” packed bed reactor

A packed bed reactor with heat exchange

For our process we are going to use an adiabatic packed bed reactor:

A packed bed reactor consists of a vessel containing one or several tubes of packed catalyst

particles in a fixed, non-mobile bed (Rase, 1990). Packed bed reactors are an economical choice

in large scale production. This is due to the fact that they can operate nearly continuously due to

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the long catalyst life; which leads to savings in annual costs and shutdown costs. Reactors with a

single adiabatic bed are traditionally used in either exothermic or endothermic reactions.

However, they are primarily used for exothermic reactions in industrial practice (Satterfield,

1996). This type of adiabatic reactor is the least expensive to produce and is used as often as is

practical. Maintaining an adiabatic state conserves energy and can result in large savings for a

company. A packed bed reactor with adiabatic beds in series is used for high conversion

reactions with no heat transfer to the environment. Other advantages for using an adiabatic

packed bed reactor are Higher conversion per unit mass of catalyst than other catalytic reactors,

Low operating cost, Continuous operation, No moving parts to wear out, Catalyst stays in the

reactor, Reaction mixture/catalyst separation is easy.

2. Distillation Columns

Batch Columns

In batch operation, the feed to the column is introduced batch-wise. That is, the column is

charged with a 'batch' and then the distillation process is carried out. When the desired task is

achieved, a next batch of feed is introduced.

Continuous Columns

In contrast, continuous columns process a continuous feed stream. No interruptions occur

unless there is a problem with the column or surrounding process units. They are capable of

handling high throughputs.

Our process will use a continuous tray type column where trays of various designs are used to

hold up the liquid to provide better contact between vapor and liquid, hence better separation.

The process will therefore use a fractional distillater which is the most common form of

separation technology used in petroleum refineries, petrochemical and chemical plants, natural

gas processing and cryogenic air separation plants. In most cases, the distillation is operated at

a continuous steady state. New feed is always being added to the distillation column and

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products are always being removed. Unless the process is disturbed due to changes in feed,

heat, ambient temperature, or condensing, the amount of feed being added and the amount of

product being removed are normally equal. This is known as continuous, steady-state fractional

distillation. The advantages of using a plate column are: Most cost efficient distillation column

for diameters greater than 0.6 m,the liquid/vapor contact in the cross-flow of plate columns is

more effective than the countercurrent-flow in packed columns, Cooling coils can easily be

added to the plate column(cryogenic applications),Can handle high liquid flow rates cost-

effectively.(encyclopedia.che.engin.umich.edu/Pages/SeparationsChemical/

DistillationColumns/DistillationColumns.html)

3. Heat Exchangers

There are 3 types of heat exchangers namely:

Shell and tube heat exchanger

Plate heat exchanger

Adiabatic wheel heat exchanger

The process will use a shell and tube heat exchanger, Shell and tube heat exchangers are

comprised of multiple tubes through which liquid flows. The tubes are divided into two sets:

the first set contains the liquid to be heated or cooled. The second set contains the liquid

responsible for triggering the heat exchange, and either removes heat from the first set of tubes

by absorbing and transmitting heat away—in essence, cooling the liquid—or warms the set by

transmitting its own heat to the liquid inside. When designing this type of exchanger, care must

be taken in determining the correct tube wall thickness as well as tube diameter, to allow

optimum heat exchange. (R. Shankar Subramanian. Shell-and-Tube Heat Exchangers)

Advantages

Here are the main advantages of shell-and-tube heat exchanger:

The pressures and pressure drops can be varied over a wide range.

Thermal stresses can be accommodated inexpensively.

There is substantial flexibility regarding materials of construction to accommodate

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corrosion and other concerns. The shell and the tubes can be made of different

materials.

Extended heat transfer surfaces (fins) can be used to enhance heat transfer.

Cleaning and repair are relatively straightforward, because the equipment can be dismantled for this purpose.( http://www.thomasnet.com/articles/process-equipment/heat-exchanger-types)

4. Pumps

Classification of Pumps

Pumps used in process industries may be broadly classified in two main types:

• Dynamic (Kinetic), and

• Positive-displacement.

Dynamic Pumps

Dynamic (kinetic) pumps such as centrifugal pumps are pumps in which energy is imparted

to the pumped liquid by means of a moving Impeller or Propeller rotating on a shaft. The

kinetic energy imparted to the fluid in terms of velocity by the moving impeller is converted

to pressure as the liquid leaves the Impeller and moves through a stationary volute or diffuser

casing. (http://www.pumpscout.com/all-pump-types)

Positive-displacement Pumps

Positive-displacement pumps are those pumps in which energy is imparted to liquid in a

fixed displacement volume such as a casing or cylinder by the rotating motion of gears,

screws or vanes, by reciprocating pistons or by plunger.( http://www.pumpscout.com/all-

pump-types)

The process will use centrifugal pumps, which are often the best choice for low viscosity

(thin) liquids (MTBE and isobutylene) and high flow rates. The pump uses one or more

impellers that attach to and rotates with the shaft. The rotation of the impeller creates energy

that moves liquid through the pump and pressurizes the liquid to move it through the piping

system.(http://www.energymanagertraining.com/Journal/24092005/SelectionofPumpsforProc

essIndustries.pdf)

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For experimental design in research methodology the mixed butanes stream is replaced by a

stream of pure isobutylene to react with the methanol. The feed components have been altered

therefore the Philips etherification process has to be modified in the process design chapter in

order for it to align with our experimental design and results in the following two chapters.

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CHAPTER 3.0: RESEARCH METHODOLOGY

3.1 DATA COLLECTING METHODS AND SOURCES

Internet

Experimental results

Consultation of expert engineers

Chemical engineering journals

Relevant chemical engineering textbooks

Interviews

3.2 RESEARCH OBJECTIVES

To find a way to minimize MTBE production costs in Zimbabwe

Information on problems encountered during MTBE production

How to increase the conversion of the process

To find out the amounts of the reactants needed

To find out limitations of the process using a single reactor

To find out limitations of the process using a non-reactive fractional distillator

To find out the standards required for the methanol quality and compare to our local

methanol quality

3.3 INTERVIEWS

We visited some industries in the petrochemicals sector and carried out interviews to find out

information about;

Amount of methanol produced per day

Amount of isobutylene and mixed butenes available and how much can be imported

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3.4 EXPERIMENTAL PLAN

Several experiments were carried out in order to determine the quality or purity of methanol

obtained from NCP Distillers, the amount of MTBE obtained per kilogram of methanol and

isobutylene, the composition of the product obtained from the reaction of methanol and

isobutylene and also the conditions under which a high yield of MTBE is produced. Furthermore,

finding a rough estimate of the cost for producing MTBE at a low scale then scaling it up to

industrial level. The experiments carried out were:

Experiment to determine the amount of MTBE produced from one kilogram of methanol

and one kilogram of isobutylene.

How the yield of MTBE changes with change in temperature, amount of catalyst and

change in pressure.

Experiment to determine the purity of methanol

After obtaining the product from the reaction of methanol and isobutylene the following tests

were to be done

Jones oxidation test for alcohols

Iodine test for ethers

3.4.1 EXPERIMENTAL PROCEDURE

I. Catalytic reaction: Methanol was obtained from NCP distillers and isobutylene from

Masasa chemical suppliers. 0. 5 grams of sulphonated ion exchange resin catalyst was

incorporated into the fixed bed. 50 grams of methanol feed and 25 grams (42.5 cm 3) of

isobutylene feed were put into the reaction vessel using a syringe pump and sealed. The

experiment was carried out in a stainless steel fixed bed reactor containing a magnetic

stirrer at 30 bars and 90oC over a period of 2 hrs. Note density of isobutylene =

0.5879g/cm3

II. Fractional distillation: The product stream from the catalytic reaction was put into a

fractional distillatory to separate MTBE and the unreacted methanol. The boiling point

for MTBE is 55.2oC.The boiling point for methanol is 64.7oC and the boiling point of

isobutylene is -6.9oC.So as the MTBE reached its boiling point it turned into vapor and

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condensed in the condenser and then collected as product. Hence what remained in the

distillation column was collected.

3.4.2 TESTING FOR THE PURITY OF METHANOL

Aim

Determining the purity of methanol

Apparatus

Beaker, methanol and hydrometer

Procedure

250ml of methanol were placed in a beaker

A hydrometer was placed inside the beaker such that it floated on the methanol

3.4.3 JONES OXIDATION TEST FOR ALCOHOLS

Aim

To test for the presence of methanol in the product

Reagents

Chromium trioxide, condensate

Conditions

Temperature of 25oC

Apparatus

Test tube, dropper

Procedure

A small sample of the condensate was put into the test tube

two drops of chromium trioxide were added

The tube was observed for an immediate (2-5 sec) color change

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3.4.4 EXPERIMENT: IODINE TEST FOR ETHERS

Aim

To test for the presence of MTBE in the product

Reagents

Potassium iodide, condensate

Conditions

Temperature of 25oC

Apparatus

Test tube, dropper

Procedure

Aqueous Potassium iodide solution was added into the test tube containing a sample of

the product and observed

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CHAPTER 4.0: RESULTS AND ANALYSIS

4.1 RESULTS FOR THE CATALYTIC AND FRACTIONAL DISTILLATION

EXPERIMENT

Table 2 Results for the catalytic and fractional distillation experiment

Experiment Pressure(bars) Temperature(oC) Mass

collected(g)

Mass left in

distillation flask

1 20 50 47.78 22.56

2 20 70 49.17 21.75

3 20 90 51.73 20.94

4 20 100 50.45 22.10

5 20 110 46.89 21.36

6 20 150 40.75 20.67

7 20 200 35.98 19.55

Table 3 % conversion of isobutylene

Temperature(oC) % conversion

50 81.36

70 83.68

90 90.68

100 90.20

110 73.00

150 45.68

200 22.12

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40 60 80 100 120 140 160 180 200 2200

10

20

30

40

50

60

70

80

90

100

Temperature(oC)

% co

nver

sion

Figure 2 graph of % isobutylene conversion against temperature

4.2 DISCUSSION OF RESULTS

Using experiment number 3 with the highest % conversion for isobutylene 51.73g of product

was condensed and collected, 20.94g was left in the fractional distillatory. Hence composition of

collected product and the remainder must be determined and the percentage conversion of

isobutylene the limiting reactant.

MTBE was condensed and collected.

Expected amount of product in fractional distillatory = mass of feed - mass of collected product

= 75g-51.73g=23.27g

It was expected that 23.27g would remain in the fractional distillatory but only 20.94 g was

obta3ined.19 | P a g e

Amount of product that evaporated = mass of expected product in fractional distillatory -

actual mass of product that remained in fractional distillatory

=23.27g-20.94g=2.33g

Since isobutylene has a boiling point of -6.9oC it was concluded that 2.33g of isobutylene

evaporated.

Mass of isobutylene that reacted = mass of isobutylene feed - mass of evaporated product

= 25g – 2.33g = 22.67g

% conversion of isobutylene = (mass of reacted isobutylene/mass of isobutylene feed)*100

= (22.67/25.00)*100 = 90.68%

CONDENSATE ANALYSIS

If 22.67g of isobutylene reacted then 22.67g of methanol reacted to produce 45.34g of MTBE.

% composition of MTBE in condensate = (mass of mtbe produced/mass of condensate)*100

= (45.34g/51.73g)*100 = 88%

Therefore % composition of methanol in condensate = 12%

DISTILLATORY PRODUCT ANALYSIS

If methanol fed is 94% pure then the remaining 6% is water

Amount of water in methanol feed = 0.06*50g = 3g

Amount of methanol in feed = 47g

Therefore amount of methanol that remained in the fractional distillatory = mass of distillatory

product – mass of water in feed = 20.94 – 3 = 17.94g

% composition of methanol = (mass of methanol/mass of product)*100

= (17.94/20.94)*100 = 86%

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% composition of water = 14%

4.3 RESULTS FOR LABORATORY TESTS CARRIED OUT

4.3.1 Test for methanol purity

R esults

The specific gravity of methanol was found to be 0.8038

Therefore methanol purity=1-specific gravity of sample/1-specific gravity of pure methanol

Methanol purity=1-0.8038/1-0.7913

=0.1962/0.2087=0.94

=0.94*100%

Methanol purity=94%

The sample of therefore contains 94% methanol and 6% water, this water should be accounted

for in mass and energy balance in the following chapter

4.3.2 Test for alcohol

Results

Formation of an opaque suspension with a green to blue after two drops of chromium trioxide

was observed color was observed. This implies that a primary alcohol is present in our product.

Hence we can conclude that methanol is present in our product since it was fed in excess.

4.3.3 Test for ether

Results

Formation of a tan solution after 3 drops of potassium iodide was observed. This implies that

ether is present in our product. Hence we can conclude that MTBE which is a major constituent

of our product is present in the product obtained

CHAPTER 5.0 PROCESS DESIGN

5.1 PROCESS FLOW DIAGRAM

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Figure 3: Process Flow Diagram

PROCESS INFORMATION

E-1 Methanol storage tank

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E-3 MTBE reactor

E-4 distillation column for separation of methanol, isobutylene and methanol

E-5 distillation column for separation of methanol, isobutylene and water

E-2 Isobutylene storage tank

E-10 MTBE storage tank

Stream 1 Methanol-isobutylene feed stream

Stream 3 Stream contains MTBE, excess methanol and unreacted isobutylene

Stream 7 Stream contains 88%wt MTBE and 12%wt methanol

Stream 4 Stream contains 77%wt methanol, 13%wt water and 10%wt isobutylene

Stream 6 Methanol and isobutylene recycle stream

Stream 5 Waste water stream

5.2 PROCESS DESCRIPTION

Methanol and isobutylene are fed into the MTBE reactor, MTBE is produced and excess

methanol and isobutylene remains. The excess reactants and the product are separated in the

distillation column E-4 and a stream which contains 88%wt MTBE and 12%wt methanol is

collected as product. The overhead stream from column E-4 which contains 77%wt methanol,

13%wt water and 10%wt isobutylene is fed into distillation column E-5 were methanol and

isobutylene are recycled while the water is collected as waste.

5.3 MASS BALANCE

5.3.1 MTBE REACTOR

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Basis: 100Kmol/hr. Combined feed to the reactor

5.3.2 DISTILLATOR E-3

Figure 6: E-4 material balance

5.3.3 DISTILLATOR E-5

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26.69kmo/hr.CH3OH

3.08kmol/hr.C4H8

59.84kmol/hr. C5H12O

34.86kmol/hr. CH3OH

3.08kmol/hr. C4H8

2.22kmol/hr. H2O

59.84kmol/hr. C5H12O

8.16kmol/hr. CH3OH

2.22kmol/hr. H2O

3.08kmol/hr. C4H8

26.69kmo/hr. CH3OH

0.598 C5H12O

0.349 CH3OH

0.031 C4H8

0.022 H2O

Figure 7: E-5 material balance

CALCULATIONS

MTBE Reactor

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H2O

2.22kmo/hr.

2.22kmol/hr. H2O

3.08kmol/hr.C4H8

26.69kmol/

From experimental results isobutylene overall conversion is 90.68% therefore number of moles

of isobutylene that reacted are: 0.9068*0.33*100 = 29.92kmol/hr.

Table 4: MTBE reactor stoichiometric balances

CH3OH (kmol/hr.) C4H8(kmol/hr.)

Moles 67 33

Stoichiometric moles 1 1

Actual moles 2 1

Reacted moles 29.92 29.92

Unreacted moles 37.08 3.08

Moles of MTBE produced = 100kmol/hr. – (37.08+ 3.08) kmol/hr.

= 59.84kmol/hr.

INPUT = OUTPUT

%MTBE = 59.84/100*100 = 59.8%

%CH3OH + H2O = 37.08/100*100 = 37.1%

%C4H8 = 3.08/100*100 = 3.1%

%Water in product stream = 0.06*37.08 = 2.22/100*100 = 2.2%

Therefore mass of methanol in product = 37.08– 2.22 = 34.86kmol/hr.

Distillatory E-4

Methanol balance

From experimental results If Stream 7 composition is 88%wt MTBE and 12%wt CH3OH then

If 88%wt = 59.84kmol/hr. C5H12O then 12% CH3OH = x

By simple proportion, moles of CH3OH in Stream 7 = 12/88*59.84 = 8.16kmol/hr.

Moles of methanol in Stream 4 = 34.85 – 8.16 = 26.69kmol/hr.

5.4 ENERGY BALANCE

The equation that we used to calculate the power Q or W at each equipment is:

26 | P a g e

Q – W = ∆HR+ (-∆Hin) + (∆Hout) + (∆KE) + (∆PE)

To calculate ∆H, first we need to find the Cp values for every component in each of the Stream.

To find the Cp values, we need to use this equation to find the values of Cp

Cp = a + bT + cT2 + dT3

The values of a, b, c and d are taken from Appendix D, Coulson and Richardson Chemical

Engineering, Volume 6. If the temperature and pressure is more than the critical temperature and

pressure of the component, we need to find the (Cp– Cpo) for that specific component. But as for

all of our temperatures and pressures none of them exceed the critical temperature and pressure;

we need not to find the (Cp– Cpo)

To find the value of ∆H, we use this equation:

∆H = ∫T1T2CpdT x (n)

Should there is any reaction in the process; we need also to find the values of ∆HR which takes

place in the equipment. The equation, which we used to find ∆HR is:

∆HR= (∆ĤF product- ∆ĤF reactant) x n

5.4.1 MTBE REACTOR

Figure 10: MTBE reactor energy balance

Table 5: Stream 2

Substance Flow rates Hf To T H

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T = 101oC,

P = 2000kPa

T = 94oC,

P = 2000kPa

(kmol/hr.) kJ/kmol K K kJ/hr.

CH3OH 67 -238600 298 367 609400

C4H8 33 -16830 298 367 343480

∑H =95288 0

Table 6: Stream 3

Substance N

kmol/hr.

Hf

kJ/kmol.

To

K

T

K

H

kJ/hr.

CH3OH 34.90 -238600 298 374 351200

C4H8 3.10 -16830 298 374 35670

C5H12 59.84 -277250 298 374 670390

H2O 2.20 -242000 298 374 6.10

∑H =1063360

Stream 2

∑Hr = 67*(-238600) + 33*(-16830) =-4286.34kW

Stream 3

∑Hr = 34.9*(-238600) + 3.10*(-16830) + 59.84*(-277250) +2.20*(-242000) = -7083.99kW

Energy balance

Q - W = ∑Hr + ∑Hout - ∑Hin + KE +PE

KE = 0

PE = 0

H = ∑Hr + ∑Hout - ∑Hin

∑Hr. = ∑Hr. (products) - ∑Hr. (reactants)

∑Hr. = -7083.99-(-4286.34) = - 2797.65kW

H = (-2797.65) + 295.38-(264.69)

H = -2766.96kW

H = Q = -2766.96kW

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5.4.2 DISTILLATOR E-4

Figure 11: E-4 energy balance

Table 7: Stream 3

Substance N Hf To Tf H

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P = 400KPa

T = 103.3oC

T = 64.5oC

P = 450kPa

T = 53.3oC

P = 305kPa

kmol/hr. kJ/kmol K K kJ/hr.

C5H12O 59.84 -277250 298 337.5 333170

CH3OH 34.90 -238600 298 337.5 178300

C4H8 3.10 -16830 298 337.5 28160

H2O 2.20 -285840 298 337.5 3150

∑H = 542780

Table 8: Stream 7

Substance N

kmol/hr.

Hf

kJ/kmol.

To

K

T

K

H

kJ/hr.

C5H12O 59.84 -277250 298 376.3 692550

CH3OH 8.16 -238600 298 376.3 84720

∑H =777270

Table 9: Stream 4

Substance N

kmol/hr.

Hf

kJ/kmol

To

K

T

K

H

kJ/hr.

CH3OH 26.69 -238600 298 326.3 96980

C4H8 3.08 -16830 298 326.3 12807

H2O 2.22 -285840 298 326.3 2280

∑H = 112130

Energy balance

Q - W = ∑Hr + ∑Hout - ∑Hin + KE +PE

W=0

∑Hr=0

PE=0

KE=0

Q = ∑Hout - ∑Hin

Q = (215.91 + 31.15)-(150.77)

Q = 96.29kW

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5.4.3 DISTILLATOR E-5

Figure 12: E-5 energy balance

Table 10: Stream 4

Substance N Hf To T H

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T = 53.3oC

P = 100kPa

T = 30oC

P = 100kPa

T = 40oC

P = 100kPa

kmol/Hr. kJ/kmol K K kJ/hr.

CH3OH 26.69 -238600 298 313 50950

C4H8 3.08 -16830 298 313 6770

H2O 2.22 -283840 298 313 2850

∑H = 60170

Table 11: Stream 6

Substance N

kmol/hr.

Hf

kJ/kmol

To

K

T

K

H

kJ/hr.

C4H8 3.08 -16830 298 326 6770

CH3OH 26.69 -238600 298 326 95930

∑H = 102700

Table 13: Stream 5

Substance N

kmol/hr.

Hf

kJ/kmol

To

K

Tf

K

H

kJ/hr.

H2O 2.22 -238840 298 303 400

Energy balance

Q - W = ∑Hr + ∑Hout - ∑Hin + KE +PE

W=0

∑Hr=0

PE=0

KE=0

Q = ∑Hout - ∑Hin

Q = (1.88 + 26.65+0.11)-16.71

Q = 11.93kW

5.5.4 Energy balance around preheater E-6

32 | P a g eStream 1

Table 14: Stream 1

Substance Flow rates

(kmol/hr.)

Hf

kJ/kmol

To

K

T

K

H

kJ/hr.

CH3OH 67 -238600 298 298 0

C4H8 33 -16830 298 398 0

∑H = 0

Table 15: Stream 2

Substance Flow rates

(kmol/hr.)

Hf

kJ/kmol

To

K

T

K

H

kJ/hr.

CH3OH 67 -238600 298 367 609400

C4H8 33 -16830 298 367 343480

∑H =95288 0

Q = ∑Hout - ∑Hin

Q = 246.69 – 0

Q = 246.69 kW

5.5 SAFETY HEALTH AND ENVIRONMENTAL ANALYSIS

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Stream 2

For years, those employed in the chemical industry have known that the safe operation of

Chemical plant is essential to the industry’s continued ability to survive. The human, Political

and financial costs of having accidents are just too high for the chemical industry to not exhibit

excellence in their efforts to operate plants in safe and environmentally responsible ways.

The chemical industry has an outstanding record in both transportation safety and the safe

operations of its processes. That effort has resulted in a dramatic and steady decline in releases

and waste produced at chemical sites.

Actions that should be taken to avoid serious chemical plant accidents are as follows:

1. In most cases involving large volumes of highly hazardous chemicals, excess flow valves

are in place that would stop a rapid flow of the chemicals.

2. When highly hazardous chemicals are involved, processes have fixed protection, as well

as trained emergency response teams that could handle the incident.

3. Appropriate reaction control or inhibiting systems are in place to interrupt runaway

reactions if cooling, heating and pressure relief are not considered adequate.

4. Control systems are designed to detect heat or pressure of a chemical reaction and to

control that reaction.

5. Work more closely with local and state law enforcement groups.

5.5.1 ISOBUTYLENE

- Colorless liquefied gas, odorless.

- Flammable gas. May cause flash fire

- Contents under pressure

- Detection of leak via sense of smell may not be possible if odorant has degraded

- Contact with liquefied gas can cause frostbite

- Liquid can cause eye and skin injury

- Reduces oxygen available for breathing

Physical and Chemical Properties

Appearance and odor: colorless liquefied gas, odorless.

Ph.: Na

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Vapor pressure: 72 psia @ 37.8 ºc

Vapor density (air=1): 2.1

Boiling point: -12°c (10.4°f)

Solubility: negligible

Percent volatile: 100 % volume

Specific gravity: 0.564 @ 15.6 ºc

Evaporation rate: >1

Immediate Health Effects:

Eye: Because the liquid product evaporates quickly, it can have a severe chilling effect on eyes

and can cause local freezing of tissues (frostbite). Symptoms may include pain, tearing,

reddening, swelling and impaired vision.

Skin: Because the liquid product evaporates quickly, it can have a severe chilling effect on

skin and can cause local freezing of tissues (frostbite). Symptoms may include pain,

itching, discoloration, swelling, and blistering. Not expected to be harmful to internal organs if

absorbed through the skin.

Ingestion: Material is a gas and cannot usually be swallowed.

Inhalation: This material can act as a simple asphyxiate by displacement of air.

Symptoms of asphyxiation may include rapid breathing, in coordination, rapid fatigue, excessive

salivation, disorientation, headache, nausea, and vomiting. Convulsions, loss of consciousness,

coma, and/or death may occur if exposure to high concentrations continues.

First Aid Measures

Eye: Flush eyes with water immediately while holding the eyelids open. Remove contact

lenses, if worn, after initial flushing, and continue flushing for at least 15 minutes. Get

immediate medical attention.

Skin: Skin contact with the liquid may result in frostbite and burns. Soak contact area in tepid

water to alleviate the immediate effects and get medical attention.

Ingestion: No specific first aid measures are required because this material is a gas and cannot

usually be swallowed.

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Inhalation: For emergencies, wear a nose approved air-supplying respirator. Move the exposed

person to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give

oxygen. Get immediate medical attention.

5.5.2 METHANOL

Methanol synonyms with Methyl alcohol and in chemical family alcohol with the formula

CH3OH. Methanol is a clear, colorless, mobile, volatile, flammable liquid and it’s soluble in

water, alcohol and ether.

Physical and Chemical properties

Physical state: liquid

Boiling Point: 64.7oC

Vapor Pressure (20oC): 128 mb

Vapor Density (air=1): 1.11

Solubility in water, %wt: full

Specific Gravity: 0.792 g/cm3

Appearance and odor: liquid-colorless-odor specific

Fire and Explosion Hazard data:

Flash point: closed cup: 12oC

Flammable limits, % vol: Lel: 6, Uel: 36.5

Extinguishing media: Foam – CO2 –halogenated agents

Special firefighting: Avoid contact with oxidizing materials

Unusual fire and explosion: Moderate

Reactivity Data

Stability: Medium

Conditions to avoid: Oxidizing materials

Incompatibility: Sulfo-chromic mixtures

36 | P a g e

Special Precautions

Precaution to be taken in handling and storing Methanol: store in iron or steel Containers

or tanks. Small quantities can be stored in reinforced glass containers.

5.5.3 MTBE

MTBE is chemically stable; it does not polymerize, nor will decompose under normal conditions

of temperature and pressure. Unlike most ether, MTBE does not tend to form peroxides (auto-

oxidize). The physical state of MTBE is that MTBE is in the form of liquid at room temperature

(25oC). It is a colorless liquid with the billing point at 55.2oC. The freezing point of MTBE is –

108.6oC –163.5oC. The density of MTBE at 25oC is 735g/cm3.

Physical dangers

MTBE is non-reactive. It does not react with air, water, or common materials of

construction. The reactivity of MTBE with oxidizing materials is probably low. However,

without definitive information, it should be assumed that MTBE reacts with strong oxidizers,

including peroxides.

Chemical dangers

MTBE is highly flammable and combustible when exposed to heat or flame or spark, and it is a

moderate fire risk. Vapors may form explosive mixtures with air. It is unstable in acid solutions.

Fire may produce irritating, corrosive or toxic gases. Runoff from fire control may contain

MTBE and its combustion products.

Inhalation risk

Like other ethers, inhalation of high levels of MTBE by animals or humans results in the

depression of the central nervous system. Symptoms observe red in rats exposed to 4000 or 8000

ppm in air included labored respiration, ataxia, decreased muscle tone, abnormal gait, impaired

treadmill performance, and decreased grip strength. These symptoms were no longer evident 6

hours after exposure ceased. A lower level of MTBE, 800ppm did not produce apparent effects

(Daughtrey et al., 1997). A number of investigations have been conducted to examine the self-

reported acute MTBE in gasoline vapors during use by consumers. This research includes both

epidemiological studies and studies involving controlled exposure of volunteers to MTBE

at concentrations similar to those encountered in refueling an automobile (Reviewed in

37 | P a g e

USEPA, 1997, and California EPA, 1998). In general, the studies involving controlled

human exposures in chambers to levels of MTBE similar to those experienced during refueling

and driving an automobile have not shown effects of MTBE on physical symptoms (e.g.

irritation), mood, or performance based tests of neurobehavioral function.

.

5.5.4 ENVIRONMENTAL CONSDIDERATIONS

Nowadays, environmental issues become very important. Besides this, a good waste treatment

system is also important in order to reduce and minimize environmental pollutants. The

chemical waste in the form of solid, liquid and gases must be treated before being discharged

into sewage, drain and atmospheres.

Any chemical plant to be set up in Zimbabwe must follow the rules and regulations

under the Environmental Management Act (Chap 20:27) Section 140 as read with Statutory

Instrument 10 of 2007 (Hazardous Waste Management), is the legislation that regulates handling

of hazardous waste, and are the legal instrument used to manage hazardous waste in the country.

Under these regulations, no person shall generate, store, sell, transport, use, recycle, discharge or

dispose of hazardous waste to the environment except under a licence from the Environmental

Management Agency (EMA).

The plant owner or waste generator must ensure that waste generated is disposed

appropriately to prevent environmental pollution. The proper and suitable methods should be

implemented in dealing with the waste disposal. MTBE plant is not excluded from these

regulations. As our plant produces MTBE which is not hazardous to the environment and

humans if safety measures are taken into consideration. These environmental considerations

depend on the location of our plant.

38 | P a g e

CHAPTER 6.0 ECONOMIC ANALYSIS

6.1 Pricing and distribution

Over the period 2000-2010 the price of MTBE fluctuated between $0.39 - $0.50/kg.The price

has remained essentially stable over the last few years, the price of MTBE in the USA market is

USD0.34/kg whilst in the European market the price is USD0.31/kg. The price fluctuations are

mainly caused by crude oil prices. We are projecting a selling price of USD0.50/kg.

6.2 Plant capacity

Commercial production of MTBE started in Europe in 1973 and in the US in 1979. Total

Worldwide production capacity in 1998 was 23.5 million tones and the actual production was 18

million tones. The expected production capacity for the project is 60 000 tons per annum based

on 330 working days. 670 kg and 330 kg of feed will produce 598 kg of MTBE.

6.3 Outline of the production schedule

During the first two years of production, full capacity utilization may not be utilized. This is due

to lack of manufacturing and marketing experiences. Thus in the first and second year of

production only 60%-80% of the plant capacity will be utilized. Then afterwards full capacity

can be utilized.

6.4 Raw materials

Zimbabwe has the largest known reserves of methane in Southern Africa; our project intends to

utilize this abundant natural resource which is lying dormant for the benefit of the nation. This

means both methanol and isobutylene can be produced locally from the methane. At full capacity

the actual raw material requirement is 67 000 tons methanol and 33 000 tons isobutylene at an

estimated cost of USD 24 990 000.

6.5 Land and buildings

The cost of land and buildings is estimated to be USD 300 000.

6.6 Location and site

The best location is the source of the raw materials to minimize transport costs, therefor the plant

can be set up in proximity to the methane reserves.

Table 13: Fixed assets and fixed costs

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FIXED ASSETS COST

(X$1000)

FIXED COSTS AMOUNT

(X$1000)

Land and Buildings 300 Depreciation 480

Vehicles 50 Interest 240

Installation labor 100 Taxes 180

MTBE reactor 200 Insurance 120

Distillation column x2 120

Storage tanks x3 45

Piping 5

Plant maintenance 5

Total 825 Total 1020

Table 14: Raw material cost and factory overheads

RAW MATERIALS COST

(X$1000)

FACTORY OVERHEADS COST

(X$1000)

Methanol 16080 Security 120

Isobutylene 8910 Employee benefits 60

Catalyst 800 Medical allowance 60

Total 25790 Total 240

Table 15: General expenses

GENERAL EXPENSES COST (X$1000)

Administrative 240

Research and Development 60

Employees 120

Marketing 60

Total 480

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6.6 Financial analysis

The financial analysis of this project is based on the data presented in the previous chapters and

the following assumptions:-

Construction 1 year

Source of finance 50% equity and 50% bank loan

Bank interest 10% per annum

Accounts receivables 30 days

Raw materials 30 days

Work in progress 1 day

Cash in hand 5 days

Accounts payable 30 days

6.7 Financial evaluation

6.7.1 Profitability

According to projected income statement, the project will start generating profit in the first year

of operation. Important ratios such as profit to total sales, net profit to equity and net profit plus

interest on total investment (return on investment) show an increasing trend during the lifetime

of the project.

6.7.2 Break Even Analysis

The break-even point of the project including cost of finance when it starts to operate at full

capacity (year 3) is estimated by using income statement projection.

Sales = 60 000 000 kg X $0.50/kg

= $30 000 000

Total Variable Cost = $25 790 000

Total Fixed Cost = $1 740 000

Total Cost = Total Variable Cost + Total Fixed Cost

= $25 790 000 + $1 740 000

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= $25 964 000

Break-even point = Fixed cost X 100%

Sales-Variable Cost

= $1 740 000 X 100%

$30 000 000-$25 790 000

= 41.3%

BREAK EVEN PLOT

Assuming a linear relationship between variable costs and production rate the following is

realized.

30

$(mill) Sales income

Total costs

Variable costs

Fixed costs

1,74

0 41.3 50 100

% CAPACITY

Figure 13: Break even plot

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6.7.3 Return on Investment

Return on Investment of the project =( Profit/total investment capital) X 100%

Profit = Sales – cost of production

= $30 000 - $25 790 000

= $4 210 000

ROI = ($4 210 000/$28 000 000) X 100%

= 15%

6.7.4 Payback period

The investment cost and income statement projections are used to project the payback period.

Payback = Fixed Capital Investment/ (Annual Profit + Depreciation)

Payback period = $28 000 000/ ($4 210 000 + $480 000) = 6 years

6.7.5 Economic benefits

The project can create employment, improve infrastructure in Zimbabwe, supply the national

needs and generate huge amounts of tax revenue for the government. The project creates an

opportunity to put Zimbabwe on the world market.

43 | P a g e

CHAPTER 7.0 CONCLUSION AND RECOMMENDATIONS

7.1 CONCLUSION

MTBE production could the county’s answer to the high dependence of using leaded and

unleaded petrol. The production of MTBE using our proposed process is an efficient technology

with 90.68% conversion of isobutylene, the process produces water, an environmentally friendly

waste product.

7.2 RECOMMENDATIONS

From our analysis it is clear that use of petrol without fuel oxygenate results in emission of flue

gasses that pose a danger to the environment. However, the implementation of MTBE as a fuel

additive will involve the following benefits:

Significant reduction in air pollution due to the reduction in flue gas emission. Improvement of competiveness as MTBE has a lower cost as compared to other

additives. Job creation

Likewise implementation of this project will provide for the ever sought for clean solutions. The production of this product also promises huge exports that will turn over the current economic situation in Zimbabwe.

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APPENDIX

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