2022

A study of feasibility for the produc

Name
Abstract
This study presents the findings of a feasibility study for the manufacture of acetic acid at a rate
of 100,000 tonnes per year. It is being investigated if the methanol carbonylation method, the
acetaldehyde oxidation route, and the direct oxidation of the n-butane process route are all
technically, environmentally, and financially feasible. An in-depth analysis of the main literature
that is currently accessible is used to conduct the assessment of the project's technical feasibility.
The atom economy, energy use, raw materials and process dangers are the indicators that are
used in the investigation of environmental feasibility. The discounted cash flow rate of return is
utilized in order to evaluate the economically viable alternatives. It has been demonstrated that,
out of the three different ways that have been researched, the Methanol carbonylation pathway is
the most promising technique for obtaining acetic acid.

1
Table of Contents
1. Introduction:................................................................................................................................7

1.1 General Information...............................................................................................................7

1.2 Acetic acid history.................................................................................................................7

1.3 Material Properties.................................................................................................................8

1.3.1 Physical Properties..........................................................................................................8

1.3.2 Chemical properties.........................................................................................................9

1.4 Applications of acetic acid:..................................................................................................10

1.4.1 Food Industry................................................................................................................10

1.4.2 Household Uses.............................................................................................................10

1.4.3 Medical Use...................................................................................................................10

1.4.4 Industrial Use................................................................................................................11

1.5 Global Scenario:...................................................................................................................11

2. Different manufacturing processes............................................................................................13

2.1 Fermentation routes..............................................................................................................14

2.1.1 Orleans Process.............................................................................................................15

2.1.2 Generator or Trickle Fermentation................................................................................16

2.1.3 Submerged Fermentation..............................................................................................17

2.2 Selected Process...................................................................................................................18

3. Technical feasibility...................................................................................................................18

3.1 Technical brief.....................................................................................................................18

3.2 Mass flow rate......................................................................................................................19

3.2 Working week definition.....................................................................................................19

3.3 Methanol carbonylation route..............................................................................................20

3.3.2 Enthalpy of Formation of Methanol carbonylation route..............................................22

2
 3.3.3 Physical Properties of Raw Materials...........................................................................22

3.3.4 Advantages of Methanol carbonylation route...............................................................22

3.4 Acetaldehyde oxidation....................................................................................................23

3.4.1 Enthalpy of Formation of Acetaldehyde oxidation route..............................................24

3.5 The direct oxidation of n-butane:.....................................................................................25

3.5.1 Enthalpy of Formation of Acetaldehyde oxidation route..............................................26

3.6 Location of the plant............................................................................................................27

3.7 Summary of technical feasibility.........................................................................................28

4. Environmental feasibility...........................................................................................................29

4.1 Introduction..........................................................................................................................29

4.2 Acetic Acid..........................................................................................................................29

4.3 Methanol carbonylation route..............................................................................................31

4.3.1 Material Identification...................................................................................................31

4.3.2 Hazard identification.....................................................................................................31

4.3.4 Catalyst ecology............................................................................................................32

4.4 Acetaldehyde oxidation........................................................................................................32

4.4.1 Material Identification...................................................................................................32

4.4.2 Atom economy..............................................................................................................32

4.4.3 Catalyst ecology............................................................................................................33

4.5 The direct oxidation of n-butane..........................................................................................33

4.5.1 Material Identification...................................................................................................33

4.5.2 Atom economy..............................................................................................................33

4.5.3 Catalyst ecology............................................................................................................34

5. Economic Feasibility.................................................................................................................35

5.1 Fixed Capital Cost................................................................................................................35

3
 5.2 ISBL Cost.............................................................................................................................35

5.3 Functional Units...................................................................................................................35

5.4 Cost on UK Basis.................................................................................................................36

5.5 OSBL Cost...........................................................................................................................37

5.6 Engineering Costs................................................................................................................37

5.7 Contingency Cost.................................................................................................................37

5.8 Operational Costs.................................................................................................................38

5.9 Fixed Cost............................................................................................................................38

5.10 Variable Costs....................................................................................................................38

5.11 Working Capital.................................................................................................................39

5.12 Plant Start-Up Schedule.....................................................................................................39

5.13 Project Evaluation..............................................................................................................40

5.14 Depreciation.......................................................................................................................40

5.15 Taxable Income..................................................................................................................41

5.16 Methanol Carbonylation......................................................................................................0

5.17 Acetylene Oxidation............................................................................................................2

5.18 Butane Oxidation.................................................................................................................4

5.19 Summary of economic feasibility........................................................................................6

6. Overall summary.........................................................................................................................8

7. References....................................................................................................................................9

4
List of Figures

Figure 1 Acetic acid global demand 2020 ................................................................................................10

Figure 2 Acetic acid global supply 2020 ......................................................................................10
Figure 3 Global acetic acid consumption .....................................................................................11
Figure 4 Applications and commercial approaches for the production of acetic acid ..................12
Figure 5 Orleans Process Barre ....................................................................................................14
Figure 6 Generator fermentation or Trickle method .....................................................................15
Figure 7 Submerg Process……………………………………………………………………...16
Figure 8 Semi-Continuous Process................................................................................................16
Figure 9 Carbonylation technique for acetic acid production ......................................................18
Figure 10 the catalytic cycle for the carbonylation of methanol using iridium as the catalyst.....20
Figure 11 Process flow diagram of Methanol carbonylation route ..............................................22
Figure 12 Process flow diagram Acetaldehyde oxidation route ...................................................24
Figure 13 Oxidation of hydrocarbons to produce acetic acid .......................................................25
Figure 14 Process flow diagram via the direct oxidation of n-butane rout ..................................26
Figure 15 Detailed Plant Location Map.........................................................................................26
Figure 16 Cash flow analysis diagram.............................................................................................6
Figure 17 Internal rate of return diagram........................................................................................7

5
List of Tables

Table 1 Physical Properties of acetic acid ......................................................................................7

Table 2 Components Enthalpy of formation at 298.1K ................................................................21
Table 3 Components Enthalpy of formation at 298.1K ................................................................23
Table 4 Components Enthalpy of formation at 298.1K ................................................................25
Table 5 Summary table for technical feasibility............................................................................27
Table 6 Hazard statement of acetic acid .......................................................................................28
Table 7 Precautionary statements of acetic acid............................................................................29
Table 8 Summary table for environmental feasibility...................................................................33
Table 9 Three processes and their costs........................................................................................35
Table 10 Fixed Capital Cost on UK Basis, 2022...........................................................................36
Table 11 Variable Cost of Production at Maximum Capacity......................................................38
Table 12 Cash flow analysis for methanol carbonylation process..................................................0
Table 13 Cash flow analysis for acetylene oxidation process.........................................................2
Table 14 Cash flow analysis for butane oxidation process..............................................................4
Table 15 Final route summary.........................................................................................................8

6
1. Introduction:
1.1 General Information
The annual demand for acetic acid around the globe is approximately 9 million tonnes, making it
a significant commodity that is utilised in the chemical industry. This substance is primarily
employed in the production of a wide variety of organic compounds, acetate esters, organic
solvents, fungicide, medicines, cellulose acetate, which is crucial in the creation of film and
plastic commodities, fragrances, and synthetic fibres (Jones,
2009).

Acetic acid (CH3COOH) is an organic acid that has a

 Pungent odor,
 Burning taste, and
 Blistering qualities that are particularly harmful.

It may be found in trace amounts in the liquids of many different plants and animals, as well as
in rainwater, oilfield brines, and ocean water. It plays an essential role in each and every one of
the cellular energy processes. Vinegar is a solution of acetic acid that is produced by the
fermentation of vegetable and fruit juices. Bacteria and fungi may break down the sugar in any
kind of sap or juice to produce acetic acid (Jones, 2009).

1.2 Acetic acid history

In the third century BC, the Greek philosopher Theophrastus explained how acetic acid operated
on metals to make colors valuable in painting. These included white lead and combination of
copper salts that included copper (II) acetate. Sapa was a very sweet syrup that was produced by
the ancient Romans by boiling sour wine. Lead poisoning was a problem among the Roman elite
because the sapa that was made in lead pots included a high concentration of lead acetate. Lead
acetate is a pleasant chemical that is also known as sugar of lead (Goldberg, 2002).

Andreas Libavius, a German alchemist who worked in the 16th century, provided a description
of the ketonic decarboxylation process that led to the creation of acetone from the dry distillation
of lead acetate. Because the presence of water in vinegar has such a significant impact on the
characteristics of acetic acid, scientists have traditionally held the misconception that glacial

7
acetic acid and the acid that may be found in vinegar are two entirely distinct entities (Goldberg,
2002).

1.3 Material Properties

1.3.1 Physical Properties
Acetic acid is a reactive liquid that is transparent, colorless, and odorless. It also has a strong
smell, and it is a hazardous vesicant. It has a harsh vinegar-like odor. The odor may be detected
at concentrations as low as 1 ppm. The liquid is often offered as glacial acetic acid, which has a
water content of less than 1% by weight and a purity level of more than 98%. The acid has trace
amounts of contaminants such as acetaldehyde, oxidized compounds, iron, and chlorides in
addition to the water that it starts with. Due to the possible inclusion of ethyl acetoacetate, the
acid may occasionally take on a colored appearance. Because it lowers the concentration of
mercuric chloride, the acetate is frequently confused with formic acid. Through their interaction
with aluminum, even small amounts of mercury can cause severe corrosion. Aluminum is a
typical choice for the containers that are used to transport acid. The acetic acid found in glaciers
has a high hydroscopicity. When 0.1 weight percent of water is present, the freezing point drops
dramatically. A wide variety of popular solvents, such as dioxane, pyridine, and benzene, can
cause acetic acid to form azeotropes with them. There are a number of solvents, including
acetone, water, ethanol, benzene, carbon tetrachloride, ether, and acetone, that are compatible
with acetic acid (Cheung, 2011).

Table 1 Physical Properties of acetic acid [3]

Parameter Value Parameter Value Unit

Chemical formula CH₃COOH -

CAS no 64-19-7 -

Concentration 99.7 (% by mass, wt/wt)

Lower Explosive Limit 4.0 % Vol

Melting point 289.75 K

Upper Explosive Limit 19.9 % Vol

Boiling point 390.9 K

Molecular weight 60.1 g.mol-1

8
 Flash point 312.59 K

Density 1040 kg/m³

FREEZING POINT 62 °F

SOLUBILITY Miscible -
VAPOR PRESSURE mmHg mmHg

Ionization Potential 10.66 eV

1.3.2 Chemical properties

Many valuable products are created from acetic acid. When olefins or alcohols are reacted with
acetic acid, acetate esters are produced as a byproduct. In addition, acetic acid is utilized in the
manufacturing process of certain medications. The chemical process that produces aspirin, also
known as acetylsalicylic acid, involves salicylic acid and acetic acid.

However, this esterification reaction may be reversed, and the water present can cause the aspirin
to be hydrolyzed. Therefore, an anhydrous (which literally means "without water") reagent can
result in higher product yields. At a temperature of 800 degrees Celsius, acetic acid may be
dehydrated to produce acetic anhydride (Cheung, 2011).

Alternately, acetic anhydride and a salt can be obtained through the reaction between a salt of
acetic acid and acid chloride such as sodium acetate. This reaction produces acetic anhydride.

9
1.4 Applications of acetic acid:
Acetic acid has a wide variety of applications. Therefore, in addition to just functioning as a food
preservative (vinegar), the acid is utilized in a wide variety of contexts and applications. Among
the most common and significant applications are:

 Food Industry
 Household
 Medicinal Uses
 Industrial Use

1.4.1 Food Industry

1. The most typical applications for acetic acid in the food business are commercial pickling
processes and condiments such as ketchup mayonnaise and mustard.

2. It may also be used as a spice for a variety of foods, such as salads and other dishes.

3. when vinegar is combined with alkaline chemicals like baking soda, a gas is produced that
aids in the rise of baked products.

1.4.2 Household Uses

Vinegar is primarily made from acetic acid, which is often found in a diluted solution. Vinegar is
a common home product that has a variety of applications, including cleaning, washing, cooking,
and many more. As we well know. In order to prevent the growth of germs and fungi, farmers
typically apply acetic acid to the silage that their cattle consume.

1.4.3 Medical Use

The area of medicine makes extensive use of acetic acid for a variety of applications. The most
significant application of this phrase is that;

1. It is employed as an agent to lyse (destroy cells by the action of lysin) red blood cells prior to
the examination of white blood cells.

2. It has been observed that drinking vinegar might bring down high levels of sugar in the blood.

3. It is effective as an antiseptic against a wide variety of bacteria, including streptococci,

staphylococci, pseudomonas and enterococci.

10
4. It is also utilized in the screening process for cervical cancer, as well as in the treatment of
infections.

1.4.4 Industrial Use

As a chemical reagent, acetic acid is frequently used in the production of a variety of chemical
compounds, including acetic anhydride, ester, vinyl acetate monomer, vinegar, and a great deal
of other polymeric materials. It is also used in a number of industrial processes for the
production of substrates. Because it may be employed as a solvent for recrystallization, it is also
put to use in the process of purifying organic molecules.

In addition to these applications, acetic acid is utilized in the production of a variety of other
products, including inks, dyes, and fragrances. Additionally, it is involved in the production of
rubber and plastic goods in several sectors (Briggs, 2009).

1.5 Global Scenario:

An analysis of the market for glacial acetic acid reveals that there is a significant gap between
the demand for it and the supply of it. Recent data demonstrates that Asia's overall generating
capability is diminishing, despite the fact that overall acetic acid production remains healthy
across the world. The vast majority of acetic acid that is generated in Asia is used domestically,
while the remainder is exported due to the ease and low cost with which it may be processed
(Chen, 2015).

Figure 1 Acetic acid global demand 2020 [2]

11
 Figure 2 Acetic acid global supply 2020 [2]

The 2013 demand and supply chart show that Europe can only supply 7% of the 10% demand.
Other continents provide the rest of the need (Chen, 2015).

Figure 3 Global acetic acid consumption [3]

According to research that was conducted recently, the total amount of virgin acetic acid that is
generated throughout the world is believed to be 5MMTPA (million metric tonnes per year).
Approximately half of this amount is manufactured in the United States. The output in Japan is
now around 0.8 MT, whereas European production is roughly 1 MTA but is on the decline. Each
year, another 1.6 MT are recycled, increasing the total amount available on the global market to
6.55 MTA. BP Chemicals and Celanese are the two companies that manufacture the most virgin
acetic acid globally. Other notable producers are Svensk Etanolkemi, Samsung, Eastman, and
Millennium Chemicals, as well as Sterling Chemicals and Eastman. China has 45% of the
world's total capacity to produce acetic acid (virgin acid), followed by the rest of Asia (22%), the

12
United States (19%), and western Europe (7%). These areas account for 90 percent of the total
capacity in the planet (Chen, 2015).

2. Different manufacturing processes

Figure 4 illustrates the general processes involved in the manufacturing of acetic acid as well as
its many uses. Chemical and fermentative production are the two primary methods that are used
to meet the demand that is now being met in the manufacturing industry. The Cavita process,
also known as the carbonylation of methanol, oxidation of ethylene and oxidation of
aldehyde are three of the most important processes utilized in the production of chemicals. The
primary companies involved are BASF and BP Chemicals both of which take the carbonylation
approach. The creation of acetic anhydride, C1-C4, vinyl acetate monomer (VAM), acetates, and
the use of acetic acid as a solvent in the manufacturing of terephthalic acid are the primary
contributors to the vast majority of the world's demand for acetic acid (PET) (Cheung, 2011).
VAM is one of the primary chemicals that are utilized in the polymer industry. It finds
applications as an emulsifier, in resins, as an intermediary in surface coating agents, in acrylic
fiber, and in polymer wires. As a byproduct of condensation rection, it is also put to use in the
textile sector to facilitate the production of synthetic fibers. Cellulose acetate, which is used in
synthetic fabrics and silver-based photographic films, is a byproduct of the other condensation
process of acetic acid, which yields acetic anhydride as a typical acetylation agent. Among the
most common esters that may be generated from acetic acid are n-butyl acetate, ethyl acetate,
propyl acetate and isobutyl acetate. These esters are often put to use as solvents for inks, paints,
and coatings. The process of recrystallization, which is used to purify organic molecules, benefits
greatly from the use of glacial acetic acid, which is an excellent polar protic solvent. A number
of academics are now focusing their efforts on the development of a sustainable method that has
a straightforward design with the goal of meeting the present demand for acetic acid. Multiple
catalytic systems, both homogeneous and heterogeneous, have been described for the
carbonylation of acetic acid (De Vero, 2013).

13
Figure 4 Applications and commercial approaches for the production of acetic acid [4]

2.1 Fermentation routes

The fermentation process is most commonly used for the production of vinegar, which is an
acetic acid of food-grade quality. This method relies mostly on the utilization of sustainable
carbon resources including syrup, date, apple, pear, cane, vine, grape and beer. The fermentation
process can essentially be broken down into two stages: the first stage involves yeast, and the
second stage involves bacteria that produce acetic acid (AAB). Oxidative fermentation with the
use of AAB is the method that is used in the industrial manufacturing of vinegar. There are 10
different categorized genera, however the two most common species are Gluconacetobacter
and Acetobacter. Conventionally, Acetobacter pasteurianus is utilized in the industrial
manufacture of vinegar with a concentration that is lower than or equal to 6% by volume. On the
other hand, Gluconacetobacter europaeus is used in the production of vinegar with a high
concentration (10% vol/vol). The cost of the acetic acid might change depending on the sort of
source that was used to make it as well as the area in where it was produced. Vinegar and acetic
acid can be produced using a variety of processes, including conventional techniques that include
the use of oak barrels (the Orleans Process) and surface culture (the The trickle or Generator

14
Process), as well as submerged fermentation. Acetic acid is an essential component of a great
deal of different dietary items. The requirement for huge quantities of the vinegar makes
industrial fermentation systems necessary. These systems must be able to produce quantities that
can be accurately controlled. The commercial manufacturing of acetic acid has seen a significant
improvement thanks to the development of a great number of technical instruments. In most
cases, these enhancements increase the rate at which ethanol is converted into acetic acid in the
influence of acetic acid bacteria (Cheung, 2011).

2.1.1 Orleans Process

The French process, also known as the Orleans process, is a method for acetifying wine that has
been in use in France continuously from the year 1675. In this method, acetification is difficult to
achieve with alcohol solutions that contain less than 5% of wine. When the alcohol content of the
finished product is lower than this threshold, the mash must be fortified with phosphates and
nitrogenous compounds, and the end product must be labelled as "spirit vinegar." It was stated
that the Orleans method was the best way for producing good grade table vinegar, and that it was
the sole process that could generate pure wine vinegar. In this step, alcohol-fermenting liquid is
poured into wood barrels (shown in Figure 8) from which they are taken and filled to about three
quarters of their capacity. In the beginning, holes are bored only at edges of the barrel just few
inches above the surface of the liquid. The holes are not filled up and instead have a fine screen
placed over them (Fiume, 2003).

Figure 5 Orleans Process Barre [16]

Second, the barrel receives an addition of new vinegar comprising around 22–27% of the total
volume. The fresh vinegar is added for the purpose of acidifying the liquid to a level that is
optimal for the development of the bacteria that produce vinegar. Vinegar germs fall into the
liquid from the surrounding air and begin to build a coating of gelatinous slime on the surface of
the vinegar. At temperatures ranging from 75°F to 80°F, the liquid is allowed to ferment for
15
approximately two to three months. After this period of time has passed, a quarter to a third of
the vinegar can be removed for the sake of bottling, and an equal amount of an alcoholic
beverage can be added. This process yields 75-85% of the theoretical amount of product.
Vinegar must have fresh supplies of alcohol given to it on a regular basis; otherwise, the acetic
acid may start to deteriorate (Garcia, 2013).

2.1.2 Generator or Trickle Fermentation

In the early years of the nineteenth century, a German scientist named Krimen created a
procedure for producing vinegar that was first known as the trickling method and is now more
often known as the generator fermentation or fast process. This method calls for the cultivation
of bacteria, which then results in the formation of a thick layer of slime surrounding a substance
that does not compress, such as shavings of beech wood, coke or charcoal. The material that did
not compress was loaded into enormous wood tanks (Figure 9) with a capacity of 1800 cubic
feet, which were placed on top of a floor made of a perforated wood grating (Krimen, 2003).

Figure 6 Generator fermentation or Trickle method [18]

While this occurs, the re-circulated fermentation liquid slowly drips down over the packaging
toward the bottom of the vessel. At the same time, air is drawn in from the bottom of the vessel
and moved upward via the inlets. The amount of oxygen present in the environment is directly
related to the rate of acetification. If there is a restricted supply of air, then there will be a
16
reduced amount of acetic acid produced, and the temperature of the generator will be lower.
However, if there is an excessive supply of air, then there will be an excess amount of
production, and the temperature will be greater It is necessary to keep a constant eye on the
generators in order to detect any signs of excessive oxidation or temperatures that are not
appropriate. It takes roughly three to seven days to complete the operation. After removing two
thirds of the finished vinegar product from the tank, new mash is added to the mixture. The
replacement mash is added to the tank in a gradual and steady stream until the working level for
acetifying the solution as well as the starting temperature of 22 degrees Celsius are both attained.
The yield of acetic acid is 95%.

The range of temperatures between 30 and 35 degrees Celsius is ideal for the operation of a
generator. When oxidized to acetic acid, one gallon of 190 proof alcohol produces around 25,000
to 30,000 Btu of heat. Acetobacter thrives best at a temperature of around 35 degrees Celsius. It
is vital to have a mechanism that controls the temperature in order to avoid overheating the
bacteria, which would lead to their death (Michel, 1992).

2.1.3 Submerged Fermentation

Submerged culture (Figure 10) is currently the most widely used production technique since it
enhances the standard fermentation conditions of heating, aeration and stirring etc. Because
generator culture methods are both time-consuming and costly, submerged fermentors have now
become increasingly popular for usage on an industrial scale. During this stage of the process,
the mash is agitated and aerated on a regular basis. During the fermentation process, the
fermenters are often equipped with heat exchangers so that the temperature may be kept at the
ideal level. The semi-continuous mode of operation is the standard method of operation in
industries (Figure 11). This process involves the creation of many consecutive cycles of
acetification that are not connected to one another.

Figure 7 Submerged Process [19] Figure 8 Semi-Continuous Process [20]

17
At the conclusion of each cycle, a predetermined quantity of acetic acid is discarded and the
space it occupied is replenished with mash. 86 degrees Fahrenheit or 30 degrees Celsius was the
optimal temperature for the commercial manufacturing of 11 to 12% vinegar. Above 86 degrees
Fahrenheit, the bacteria are in risk of being damaged. In addition to this, the condition of the
bacteria influences the amount of acetic acid that is generated (Nakano, 2016). The yield of
acetic acid is 98%

2.2 Selected Process

Only conventional routes are considered for technical, economic and environmental feasibility
because of their wide uses in commercial industries, easy availability of raw materials and their
environmental applications. The selected processes are;

 Methanol carbonylation route

 Acetaldehyde oxidation
 The direct oxidation of n-butane

3. Technical feasibility
3.1 Technical brief
The following are some of the fixed needs and parameters for the project:

The goal of this project is to build a new plant capable of producing 100,000 tonnes per year of
technical grade acetic acid with a purity level of 77% when mixed with water, with the plant
designed to be operational for 8000 hours per year.

• Any big pieces of equipment you buy should have their capacity increased by 120% to make
room for future growth.

• These prices are based on January 2022, and they will rise every year on January 1st, according
to the UK Consumer Price Index.

Starting in June 2022, all economic information must be given in terms of pounds sterling
(UK£), and this must be done every month.

The internal rate of return on investment (IRR) should be more than 20%, taking into account the
product's anticipated lifespan of 20 years.

18
•The design adheres to all HSE and environmental criteria as well as design rules, and even
exceeds them.

• Efficient use of resources, such as byproducts, energy, and materials.

• The plant's ability to function autonomously using its own automation and to provide adequate
performance data for process optimization.

3.2 Mass flow rate

In order for the facility to have a 20% over capacity permit, it must be capable of generating
120,000 kg of acetic acid every year. The highest mass flowrate of the acetic acid product stream
will be when considering this time period's anticipated total operating duration of 8000 hours.
(120,000/8000) = 15 kg/hr or 0.004 kg/s.

3.2 Working week definition

It will be essential to run both a day shift and a night shift, as well as a seven-day working week
(including bank holidays), and the expense of doing so will need to be accounted for. This will
be necessary in order to attain an annual operating time of 8000 hours. Three days of downtime
are planned for the Christmas (or comparable national annual holiday) period, and another half-
day each week is set aside for shutdown, inspection, maintenance, and start-up during the course
of the year.

'Permitting a yearly public holiday:

365 days−3 days=362 days

Taking into account the closure of one-half day every week:

6.5
362 days × =336.14 days
7

The last accessible working hours are as follows:

336.14 days ×24 h per days=8067 h ours

At this point, it doesn't matter much what the exact plan is, but it's possible that the half day
every week will be used on a different schedule, like once every two weeks.

19
3.3 Methanol carbonylation route
The methanol carbonylation pathway produces 75% of the world's acetic acid. When Rhodium
catalyst was utilized as an active catalyst with iodide of metals like lithium, a method known as
the Monsanto process was developed for producing acetic acid by carbonylation of methanol.
The procedure was carried out at a pressure of 50–60 bar and a temperature ranging from 150–
200 degrees Celsius, which led to a high purity of 98.9% based on the supply of methanol.
However, B.P. Chemicals developed a method known as Cativa, which involved the utilization
of an iridium catalyst in conjunction with hydrogen iodide as the system's active catalyst.

Figure 9 Carbonylation technique for acetic acid production [4]

As early as 1925, Henry Drefyus, working for British Celanese, built a pilot unit for the
methanol carbonylation process. However, commercialization of these approaches was hampered
since there were not enough materials that were both practicable and capable of containing the
corrosive reaction mixture at the high pressures required (at least 200 atm). In 1963, the German
chemical firm BASF was responsible for the development of the first commercial methanol
carbonylation method. This process made use of a cobalt catalyst. The year 1968 saw the
discovery of a rhodium-based catalyst, which had the ability to function well at lower pressures
while producing nearly no byproducts (Navarro, 2013).

3.3.1 This overcame many limitations of the Monsanto process as

• When compared to the Monsanto procedure, the water content in the final product was much
lower.

• The procedure may now be carried out at a temperature and pressure that are far lower than
before.

• There was a decrease in the total number of distillation units.

20
• Iridium is more affordable than rhodium, which helps to bring down overall production costs to
a significant degree. Using a pressure of 30–40 bar and a temperature of 150–200 degrees
Celsius, the Cativa Process achieves a high selectivity of 99% (Cheung, 2011). The reactions are:

Major reaction:

CH3OH + CO → CH3COOH

Other Reactions:

CH3OH + CO → C2H5COOH

CH3COOH + CH3OH → CH3COOCH3

Iodomethane acts as an intermediary in the process, which takes place over the course of three
stages. For the carbonylation process to take place, you will need a catalyst, which is often a
metal complex (step 2).

CH3OH + HI → CH3I + H2O

CH3I + CO → CH3COI

CH3COI + H2O → CH3COOH + HI

21
 Figure 10 the catalytic cycle for the carbonylation of methanol using iridium as the catalyst [10]

3.3.2 Enthalpy of Formation of Methanol carbonylation route

Table 2 Components Enthalpy of formation at 298.1K [12]

Compound ∆ f H ° ( kJ mol−1 )
Methanol -238.42
Carbon monoxide -110.5
Acetic acid -484.9
Formic Acid -431.65
Formaldehyde -109.15

Using Hess’s Law (Equation 8) and the values from Table 6, it is useful to calculate the heat of reaction
∆ rx H ° .

∆ rx H °= ∑ ∆f H °− ∑ ∆f H °
products reactants

[ (−484.9 ) + (−431.65 )+ (−109.15 ) ]−[ (−238.42 ) + (−110.5 ) ]=−676.78 kJ mol−1

22
3.3.3 Physio-chemical Properties of Raw Materials

3.3.4 Advantages of Methanol carbonylation route

The following are some advantages that the selected procedure offers over other processes:

• Cativa's selectivity is 99%, compared to 90% for acetaldehyde oxidation and other methods.

• When compared to other procedures, this one is less expensive.

• The cost of the feedstock, which is methanol, is significantly lower than the cost of feedstock
used in other processes.

• The reaction in the liquid phase is straightforward to regulate (Rutherford, 1992).

23
Figure 11 Process flow diagram of Methanol carbonylation route (Cheung, 2011)

3.4 Acetaldehyde oxidation

In most cases, air or oxygen is used in conjunction with manganese acetate as a catalyst in order
to carry out the process of continuous oxidation of acetaldehyde while it is in the liquid phase.
The reaction mixture, which includes acetaldehyde that has been diluted with crude acid and a
solution of manganese acetate, is pumped upward through the oxidation tower.

The reaction conditions are 150 degrees Celsius at 50-60 bar but when oxygen is employed, they
adequate to retain the acetaldehyde in liquid form. The reaction mixture is removed from the
very top of the distillation tower and then continually diluted in as many as three different
distillation columns. At this point, crude acid is poured into the uppermost part of the distillation
column. Other volatile components are removed through the column's uppermost opening, and a
residue comprising manganese acetate is extracted from the column's lowermost opening. In the
second column, the fore-run is removed while it is still boiling at a low temperature, and between

24
99.6 and 99.8 percent pure acetic acid is removed immediately above the reboiler. The method
may be explained in more detail using the following format:

Oxidation is often carried out using oxygen in the Hoechst Process. This process runs
continuously at temperatures between 50 and 70 degrees Celsius in stainless steel oxidation
towers known as bubble columns. Acetic acid is used as the solvent. Temperatures of at least 50
degrees Celsius are required in order to produce a satisfactory level of peroxide breakdown and,
consequently, a satisfactory level of oxidation rate. The heat generated by the reaction is
dissipated by passing the mixture that is being oxidized across a cooling system. Formic acid,
carbon dioxide, and trace quantities of carbon monoxide and water are the products of the
oxidative breakdown of acetic acid when the temperature is carefully controlled. The selectivity
of acetic acid is between 95 and 97%. Distillation is used to separate the byproducts, which
include carbon dioxide (CO2), formic acid, methyl acetate, methanol, and methyl formate.
Formaldehyde is also produced, but it is separated from the other byproducts (Saichana, 2017).

25
3.4.1 Enthalpy of Formation of Acetaldehyde oxidation route
Table 3 Components Enthalpy of formation at 298.1K [12]

Compound ∆ f H ° ( kJ mol−1 )
Acetaldehyde -191.70
Oxygen 0
Acetic acid -484.9
Formic Acid -431.65
Formaldehyde -109.15
Ethyl Acetate -480
Hess's Law and the information from Table 6 can help you figure out the heat of reaction, which is
written as ∆ rx H ° .

∆ rx H °= ∑ ∆f H °− ∑ ∆f H °
products reactants

[ (−484.9 ) + (−431.65 )+ (−109.15 ) + (−480 ) ]−[ (−190.70 ) + ( 0 ) ]=−1315 kJ mol−1

Figure 12 Process flow diagram Acetaldehyde oxidation route (Saichana, 2017).

26
3.4.2 Physio-chemical Properties of Raw Materials

3.5 The direct oxidation of n-butane:

Butane and naphtha, both which are obtained from petroleum stock, are two examples of the
types of hydrocarbons that are employed in the production of acetic acid employing chromium
acetate and cobalt acetate as catalysts. A much greater temperature range (150–230 degrees
Celsius) and pressure are required for the reaction to continue (50–60 bar). A number of
additional byproducts, in addition to acetic acid, are produced as a result of the process,
including acetone, formic acid, and propionic acid. The process begins with petroleum feedstock,
which includes a combination of hydrocarbons. Because of this, the method does not result in the
production of pure acetic acid. For the production of a combination of volatile fatty acids, this
technique works much more effectively.

27
Figure 13 Oxidation of hydrocarbons to produce acetic acid [5]

The oxidation of acetaldehyde, which results in the generation of acetic acid, has been the
subject of a significant amount of patent research. Since 1912, it has been used for commercial
purposes in Germany, and since 1921, it has been used in the United Kingdom. Even in many
different processes, acetaldehyde serves primarily as an intermediary step in the manufacture of
acetic acid. The following are the four most prevalent and important methods that lead to
acetaldehyde (Togeas, 2005):

i) The hydration of acetylene that occurs in the liquid phase.

ii) The partial oxidation of ethyl alcohol or the dehydrogenation of ethyl alcohol in the vapor
phase.

iii) The oxidation of ethylene that occurs in the liquid phase.

iv) The process in which saturated hydrocarbons are oxidized at high temperatures.

3.5.1 Enthalpy of Formation of Acetaldehyde oxidation route

Table 4 Components Enthalpy of formation at 298.1K [12]

Compound ∆ f H ° ( kJ mol−1 )
Butane -125.82
Oxygen 0
Acetic acid -484.9
Formic Acid -431.65
Propionic Acid -454.32

Hess's Law and the information from Table 6 can help you figure out the heat of reaction, which is
written as ∆ rx H ° .

∆ rx H °= ∑ ∆f H °− ∑ ∆f H °
products reactants

28
 [ (−484.9 ) + (−431.65 )+ (−454.32 ) ]− [(−125.82 )+ ( 0 ) ]=−1245 kJ mol−1

Figure 14 Process flow diagram via the direct oxidation of n-butane rout (Cheung, 2011)

3.5.2 Physio-chemical Properties of Raw Materials

29
3.6 Location of the plant
Locations for the plants have been proposed based on the requirements of the various operations.
In Sheffield, where demand for acetic acid is expected to rise and supplies of methanol and CO
are abundant. Sheffield is well-known all throughout the world for being an important center of
manufacturing. The city's prominence as an industrial hub in England throughout the 1800s,
1900s, and the early part of the 20th century may be attributed to the success of its
manufacturing sector.

Figure 15 Detailed Plant Location Map

3.7 Summary of technical feasibility

The technical feasibility brief will only take into account the challenges of building and
operating the facility in order to produce a product that meets specifications. Because the author
views issues regarding the availability of raw materials and the placement of plants as primarily
being of relevance to the economy, these topics will be discussed in the section under
"Economic." Efficiency in the use of energy, emissions from the site, risks posed by raw
materials and finished products, and related topics will not be discussed in the Environmental
Section. On a scale from one to ten, with ten being the best possible route and one representing
the worst possible route, each of the routes will be rated. At the conclusion of the report, we will
be employing the same grading system. Doing so will make it possible to arrive at an overall
grade and recommend a course of action at the end of the document.

Table 5 Summary table for technical feasibility

Route Feeds Products Rxn Rxn Score

TK P Bar

30
 Methanol Methanol Acetic Acid 423-473 30-50 7
carbonylation CO Formic Acid
route Formaldehyde
Acetaldehyde Acetaldehyde Acetic Acid 423 55-60 6
oxidation O2 Formic Acid
Formaldehyde
Ethyl Acetate
The direct Butane Acetic Acid 423-503 55-60 6
oxidation of n- O2 Formic Acid
butane Propionic Acid

Methanol carbonylation approach advantages from 100% acetic acid selectivity, near ambient
working pressure, easy liquid phase reaction, lowest operating temperature, and extensive
industry knowledge; much of the R&D has already been done.

The oxidation of acetaldehyde is beneficial because of its straightforward 2:1 chemistry and
separation strategy. It is the sole technique that offers near-complete conversion without
producing any significant by-products, making it unique. However, in order to make the reaction
possible, you will need extremely high pressures, temperatures, along with a certain type of
catalyst. Additionally, you will need an ethylene pipeline to feed the raw ingredients.

The direct oxidation of n-butane has the benefit of creating a valuable by-product while only
requiring butane as a feed stock. This is a significant advantage. It is also the only one of the
three processes that does not make use of nutrients that are acidic. The high working pressure
and temperature, in addition to the more complicated separation scheme, are the sources of the
problems. If the reaction isn't carefully controlled, the procedure could make a lot of different
things in addition to what was intended.

31
4. Environmental feasibility
4.1 Introduction
In order to provide a fair comparison between the processes with regard to the local and wider
environmental impact, the environmental considerations will be made using the rules and codes
that are now in effect in the United Kingdom and the overriding EU legislation. This will be
done without enabling the place of operation to exaggerate or hide a problem with one process
versus another. The Health and Safety Executive is the regulatory organisation responsible for
safety in the United Kingdom (HSE). To demonstrate conformity with the EU Seveso III
directive, the Health and Safety Executive (HSE) has made the control of major accident hazards
rules 2015 (COMAH) mandatory (Health and Safety Executive, 2015). These laws give specific
instructions and tips to places that work with a certain number of dangerous substances (Unger,
1996).

4.2 Acetic Acid

Acetic acid will be discussed first since it is the only reagent that is utilized in all three processes,
despite the fact that countless other reagents have been described. The comparisons will be made
without taking acetic acid into account. The following table provides information that was
collected from the material safety data sheet for acetic acid. This information will be used to
comment more on the many elements of acetic acid handling that will need to be examined
(Yamada, 2016).

Table 6 Hazard statement of acetic acid [15]

Hazard statements (GHS US) Description

H226 Flammable liquid and vapor

H332 Harmful if inhaled

H314 Causes severe skin burns and eye damage

H318 Causes serious eye damage

32
 H402 Harmful to aquatic life

Table 7 Precautionary statements of acetic acid

Precautionary statements (GHS US) Description

P210 Keep away from heat, sparks, open flames, hot

surfaces. - No smoking.
P233 Keep container tightly closed.

P240 Ground/bond container and receiving

equipment.
P241 Use explosion-proof electrical, ventilating,
lighting equipment.
P242 Use only non-sparking tools.

P243 Take precautionary measures against static

discharge.

In the United Kingdom, flammable atmospheres are governed by Atmospheres Regulations

(DSEAR). There are zoning grades that range from 0 to zone 2. Zone 0 denotes the presence of a
persistently flammable atmosphere, Zone 1 denotes an area in which the occurrence of a
flammable atmosphere is likely, and Zone 2 denotes an area in which the occurrence of a
flammable atmosphere is possible. A region that does not have the potential to have a
combustible environment is referred to as a none designated area.

Even when the temperature is at room standard, any vessel or piece of equipment that contains
acetic acid is required to be constructed with the appropriate considerations for a DSEAR zone 0
region in the headspace. The region immediately around any connections, port holes, or pressure
relief valves leading to these locations will be considered to be in Zone 1 of the categorization
system. The price of plant life is increased by low value DSEAR zoning.

33
Due to the fact that acetic acid is volatile at room temperature, it is reasonable to anticipate that
vapor discharges will occur from storage containers both during the filling process and as a result
of the fluctuating temperatures that occur during the day.

When combined with air, the vapor of acetic acid can produce explosive combinations. Acetic
acid with oxidizers including chromic acid, ammonium nitrate, sodium peroxide, nitric acid, and
phosphorus trichloride can react violently, causing fires or explosions (Jones, 2009).

4.3 Methanol carbonylation route

4.3.1 Material Identification
 Methanol
 Carbon Monoxide
 Acetic Acid
 Formic Acid
 Formaldehyde

4.3.2 Hazard identification

Poison Danger! When ingested, corrosive liquid and mist can cause serious burns throughout the
entirety of the body and even be deadly. When breathed in, it causes harm. Damage to the teeth
and lungs may result from inhalation. flammable liquid and vapor.
4.3.3 Atom economy

The atom economy of the process is defined in below Equation:

molar mass of desired products

Atom Economy ( % )= ×100
molar mass of total products

100 ( 60.052+60.052
46.03+30.031 )
=44.12 %

34
The estimate is based on the supposition that acetic acid has a selectivity of one hundred percent,
which has been demonstrated to be a valid assumption for the esterification process. It does not
take into account any issues that may arise with separation or equilibrium.

4.3.4 Catalyst ecology

According to the assessment of the relevant literature, homogeneous sulfuric acid is a widely
used industrial catalyst. This is taken away from the finished product and added to the stream of
aqueous effluent, which is detrimental to the environment and expensive to replenish. The use of
heterogeneous ion exchange resins and supported high performance anion exchangers has been
shown to have a great deal of success in the research literature, which will eliminate the problem
of catalysts being lost down drains. Homogeneous catalysts are preferred for reasons related to
the economy, while heterogeneous catalysts are preferred for reasons related to the environment
(Goldberg, 2002).

4.4 Acetaldehyde oxidation

4.4.1 Material Identification
 Acetaldehyde
 O2
 Acetic Acid
 Formic Acid
 Formaldehyde
 Ethyl Acetate

4.4.2 Atom economy

Using Atom Economy Equation:

molar mass of desired products

Atom Economy ( % )= ×100
molar mass of total products

100 ( 60.052+ 46.03+30.031+88.11

60.052
)=26.78 %

35
One of the primary motivating factors is the potential maximum atom economy that may be
achieved with the Acetaldehyde oxidation route. Due to the creation of undesired chemicals,
namely diethyl ether and ethanol, which need to be removed from the product, the real atom
economy is somewhere in the range of 96 to 98%.

4.4.3 Catalyst ecology

It has been demonstrated that the acetaldehyde oxidation process may be successfully catalyzed
by tungstosilicic acid (HPA) that is supported on silica. The presence of a modest water stream,
in conjunction with the support provided by silica, contributed to a catalyst life of two years.
According to the material safety data sheet, this substance does not pose any threats to the
aquatic life or the environment.

4.5 The direct oxidation of n-butane

4.5.1 Material Identification
• Butane • O2

• Acetic Acid • Formic Acid

• Propionic Acid

4.5.2 Atom economy

Using Atom Economy Equation:

molar mass of desired products

Atom Economy ( % )= ×100
molar mass of total products

100 ( 60.052+60.052
46.03+74.08 )
=33.33 %

Because acetaldehyde reacts with itself, side products will be produced, which will result in the
overall atom economy of the process being somewhat lower than it would have been otherwise.
The process parameters can be controlled to a large extent in order to reduce this (Cheung,
2011).

36
4.5.3 Catalyst ecology
The copper chromate type was used for the catalysts that were mentioned in the research. The
described industrial method included the employment of a second reactor equipped with a
ruthenium-on-carbon catalyst in order to selectively hydrogenate molecules that, under normal
circumstances, would render the catalysts inactive upon recirculation. On the material safety data
sheet for copper chromate, there are various statements that could be cause for worry. Because it
is an oxidizing agent, it will make flames worse. It also causes damage to the respiratory system
and has hazard statements for both acute and chronic toxicity in aquatic environments. Even
when this catalyst is put to use in a non-homogeneous manner, there is still the possibility that it
may be harmful to the natural environment in the area if it were to be discharged into the water
effluent (Cheung, 2011).

Table 8 Summary table for environmental feasibility

Route Feeds Products Rxn Rxn Score

TK P Bar
Methanol Methanol Acetic Acid 423-473 30-50 6
carbonylation CO Formic Acid
route Formaldehyde
Acetaldehyde Acetaldehyde Acetic Acid 423 55-60 5
oxidation O2 Formic Acid
Formaldehyde
Ethyl Acetate
The direct Butane Acetic Acid 423-503 55-60 5
oxidation of n- O2 Formic Acid
butane Propionic Acid

37
5. Economic Feasibility
5.1 Fixed Capital Cost
The first step in the cost analysis is the determination of fixed capital costs of the plant based on
the three selected processes. The detailed breakdown of fixed capital investment required for
each project is:

5.2 ISBL Cost

The ISBL costs include the costs for procurement and installation of all process equipment and
machinery. In the absence of design data, the ISBL cost can be estimated through either
historical data or through correlations.

Historical plant data are available for acetic acid production through carbonylation route.
However, the range for correlation is not applicable to our plant throughput.

In the absence of historical data correlation provided by Bridgewater & Mumford, and by Timms
can be used for ISBL investment. Since the plant primarily involves liquid phase so the relation
provided by Bridgewater & Mumford is used for ISBL investment of all three routes:

( )
0.665
Q −0.17
× exp ( 2.58 ×10 )
−3 −7 −0.22 −0.064
C=1.44 × 10 N ×T max × Pmax
s

Where

C = Plant Cost in dollars on U.S Gulf Cost Basis for the year 2010

N = Number of functional units

Q = Plant throughput, MT/yr

s = Reactor Conversion

5.3 Functional Units

Functional units include all those unit operations or processes which are needed for a significant
process step or function, such as a reaction, separation, or other major unit operation. Normally,
pumps and heat exchangers are not considered functional units unless they have substantial cost,
for example, compressors, refrigeration systems, or process furnaces.

38
Table 9 Three processes and their costs

Methanol Acetaldehyde Direct Oxidation of n-

Process
Carbonylation Oxidation Butane
Capacity (Q)
120,000 120,000 120,000
MT/yr
Functional Units (N) 5 6 6
Conversion (s)
95% 95% 50%
%
Maximum Temperature
200 150 220
°C
Maximum Pressure
50 60 60
atm
Cost, 2010 USGC (£) £ 26,236,088 £ 33,151,199 £ 46,695,763
Cost, 2010 USGC (£) £ 22,813,989 £ 28,827,130 £ 40,605,011

5.4 Cost on UK Basis

In order to calculate the cost of plant on UK basis, the ISBL investment calculated using the
correlation is multiplied with a location factor.

Cost of Plant ∈UK =Cost of Plant on USGC × LF2022

The location factor for the UK for the year 2022 is calculated using the equation:

US Dollar∈2022 Pound Sterling∈2003

L F 2022 =L F 2003 × ×
Pound Sterling 2022 US Dollar∈2003

US Dollar∈2003
=0.61
Pound Sterling 2003
US Dollar∈2022
=0.87
Pound Sterling 2022
L F 2022 = 1.02 × 0.87/0.61
= 1.45

The ISBL cost in 2022, is calculated using the plant cost indexes. The plant cost index for year
2010 was 532.9 while for 2022 it is 708.

39
5.5 OSBL Cost
The outside battery limit costs are estimated to be 30% of ISBL cost in each case. These costs
will cover up for the building of electrical substations, cooling towers, labs, offices etc. If not a
lot of information is available, a rule of thumb is to use 20 to 40% of the ISBL costs as an
estimate for OSBL. However, once detailed information such as the exact site and plant layout
are known, OSBL costs can be calculated in a manner similar to the ISBL costs. This is why
30% is used as an average of the percentage range.

5.6 Engineering Costs

The engineering costs cover costs for detailed engineering design of equipment, platforms,
piping and control systems etc. As an initial estimate they are taken to be 10% of ISBL and
OSBL investment.

5.7 Contingency Cost

Contingency charges are extra costs added into the project budget to allow for variation from the
cost estimate. At this stage of cost estimation, they are taken to be 10% of ISBL and OSBL
investment.

Table 10 Fixed Capital Cost on UK Basis, 2022

Fixed Capital Cost on UK Basis, 2022

Direct Oxidation of n-
Process Methanol Carbonylation Acetaldehyde Oxidation
Butane

ISBL £ 22,813,989 £ 55,370,555 £ 77,993,266

OSBL £ 13,146,192 £ 16,611,166 £ 23,397,980

Engineering £ 5,696,683 £ 7,198,172 £ 10,139,125

Contingency £ 5,696,683 £ 7,198,172 £ 10,139,125

Total Fixed Capital £ 68,360,197 £ 86,378,066 £ 121,669,495

40
5.8 Operational Costs
The operational costs of the plant are divided into fixed and variable costs. The fixed costs
include expenses such as labor pays, maintenance, land rents etc. and remain constant regardless
of production rate. The variable costs include the expenses due to raw material cost and utilities
consumption. The detailed calculations are:

5.9 Fixed Cost

 The maintenance costs are estimated to be 5% of ISBL costs.
 Property taxes are estimated to be 2% of ISBL costs.
 It is assumed that 5 operators work per shift, with a total of 4 rotating shifts. Each
operator on average is paid £40,000 per year.
 The supervision costs are budgeted to be 25% of operating labor costs.
 The direct salary overhead is estimated to be 60% of operating labor and supervision
costs

5.10 Variable Costs.

To calculate variable costs associated with the production, a material balance is required. Since
Class 5 estimate is being done, so for material balance only reactor conversion is used to find out
the raw material requirements.

The utilities for each process are estimated to be 10% of raw materials cost. The detailed
variable cost calculation is tabulated below:

41
Table 11 Variable Cost of Production at Maximum Capacity

Variable Cost of Production at Maximum Capacity

Methanol Direct Oxidation of n-
Process Acetaldehyde Oxidation
Carbonylation Butane
Methanol Acetaldehyde Butane
Raw Materials
CO Oxygen Oxygen
Annual Consumption Methanol - 67,369 Acetaldehyde - 92,632 Butane - 116,000
(tons) CO - 58,948 Oxygen - 67,368 Oxygen - 160,000
1
Methanol - £ 443 Acetaldehyde3 - £ 1,304 Butane4 - £ 721
Unit Cost (£/ton) 2
CO - £ 174 Oxygen - £ 0 Oxygen5 - £0
Methanol Acetaldehyde Butane
£ 29,876,687 £ 120,823,799 £ 83,721,739
Raw Material Cost Carbon Monoxide Oxygen Oxygen
(£/year) £ 10,251,826 £0 £0
Total Total Total
£ 40,128,513 £ 120,823,799 £ 83,721,739
Utilities Cost @10%
£ 4,012,851 £ 12,082,380 £ 8,372,174
(£/year)
Total Variable Cost
£ 44,141,364 £ 132,906,178 £ 92,093,913
(£/year)

5.11 Working Capital

The working capital is amount of money needed for initial startup and to maintain inventories.
The working capital is estimated to be 5 weeks of raw material cost. The working capital will be
released at the end of project adding to the cash flow.

5.12 Plant Start-Up Schedule

The startup schedule for all the process is taken to be same for comparison purposes. The
detailed startup schedule is:

1
https://www.macrotrends.net/2549/pound-dollar-exchange-rate-historical-chart
2
https://www.forbes.com/advisor/money-transfer/currency-converter/gbp-usd/
3
Methanex
4
NREL
5
Chem Analyst

42
 Years Costs Revenues

1st Year 30% of Fixed Capital 0

2nd Year 60% of Fixed Capital 0

10% of Fixed Capital + Working Capital + Fixed Costs +
3rd Year 30% of design basis
30% Variable Costs
4th Year + Fixed Cost + 100% of Variable Costs 100% of Design Revenue

5.13 Project Evaluation

Each of the three processes are evaluated using Net Present Value criterion. The NPV uses the
rate of return of investment imposed on the capital acquired for the project to give the money a
time value. The NPV is given according to the formula:

C Fn
NPV =∑
( 1+ i )n

Where CF is the cash flow, and n represents the project year. The interest rate for all three
projects is set at 12% whereas the tax rate is 25%.

The internal rate of return (IRR) is the interest rate for which the NPV at the end of project will
be zero. If the IRR of the project is greater than the interest rates the project will be profitable
and vice versa.

5.14 Depreciation
Depreciation charges are the most common type of tax allowance used by governments as an
incentive for investment. Depreciation is a noncash charge reported as an expense, which
reduces income for taxation purposes. Depreciation charges can be thought of as an allowance
for the “wear and tear, deterioration or obsolescence of the property” as a result of its use. For all
three projects straight line depreciation method will be used. The annual depreciation charge is
calculated as:

Cd
D i=
n

43
5.15 Taxable Income
The amount of tax that must be paid in a given year is calculated by multiplying the taxable
income by the tax rate. The taxable income is given by:

Taxable Income=Gross Profit−Tax Allowances

The most common type of tax allowance is depreciation which is used in the cash flow analysis
for this project. The taxes are paid based on previous year income.

44
5.16 Methanol Carbonylation
The cash flow analysis for methanol carbonylation process is tabulated below. The fixed capital is depreciated for a period of 20 years giving a
depreciation allowance of 3.42M. The construction of the plant is carried out in two years. In the 3rd year of the project, the plant becomes
operational and is operated at 30% of design capacity. The taxes are paid from the 4th year of the project. From the table it can be seen that the
NPV for the project becomes positive in the 4th year indicating that the project will provide a good return. The NPV of project at the end of plant
life is £ 386.34M. The Internal Rate of Return for the project is calculated to be 65.64%. Both the indicators (NPV and IRR) indicate that the
project will be a profitable one.

Table 12 Cash flow analysis for methanol carbonylation process

Methanol Carbonylation Route - Cash Flow Analysis (In Million £)

Project Capital Operating Taxable Cash Present Value
Revenue Gross Profit Depreciation Tax Paid NPV
Year Cost Cost Income Flow of CF
2023 £ 20.51 £- £- £- £- £- £- -£ 20.51 -£ 20.51 -£ 20.51

2024 £ 41.02 £- £- £- £- £- £- -£ 41.02 -£ 36.62 -£ 57.13

2025 £ 14.16 £ 43.83 £ 17.91 £ 25.92 £ 3.42 £ 22.50 £- £ 11.75 £ 9.37 -£ 47.76

2026 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 52.54 £ 4.78

2027 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 46.91 £ 51.69

2028 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 41.88 £ 93.57

2029 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 37.40 £ 130.97
2030 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 33.39 £ 164.36

2031 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 29.81 £ 194.17

2032 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 26.62 £ 220.79

2033 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 23.77 £ 244.55

2034 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 21.22 £ 265.77

2035 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 18.95 £ 284.72

2036 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 16.92 £ 301.63

2037 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 15.10 £ 316.74

2038 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 13.49 £ 330.22

2039 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 12.04 £ 342.26

2040 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 10.75 £ 353.01

2041 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 9.60 £ 362.61

2042 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 8.57 £ 371.18

2043 £- £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 73.81 £ 7.65 £ 378.83

2044 -£ 7.33 £ 146.09 £ 48.81 £ 97.28 £ 3.42 £ 93.86 £ 23.47 £ 81.14 £ 7.51 £ 386.34

1
5.17 Acetylene Oxidation
The cash flow analysis for acetylene oxidation process is tabulated below. Straight line depreciation method is used for the calculation of fixed
capital depreciation. For the 3rd year of the project in which the plant is run at reduced capacity, the operating costs exceed the revenues,
yielding negative taxable income. From year 4 (2026) onwards the project starts to generate profit and taxes are paid from 5th year (2027)
onwards. The NPV for the project at the end of plant life is -£ 48.17 M. The internal rate of return for this method is calculated to be 3.54%.
Both the NPV and IRR indicate that the project is not good for investment.

Table 13 Cash flow analysis for acetylene oxidation process

Acetylene Oxidation Route - Cash Flow Analysis (In Million £)

Project Capital Operating Taxable Cash Present Value
Revenue Gross Profit Depreciation Tax Paid NPV
Year Cost Cost Income Flow of CF
2023 £ 25.91 £- £- £- £- £- £- -£ 25.91 -£ 25.91 -£ 25.91

2024 £ 51.83 £- £- £- £- £- £- -£ 51.83 -£ 46.27 -£ 72.19

2025 £ 24.12 £ 43.83 £ 44.95 -£ 1.12 £ 4.32 -£ 5.44 £- -£ 25.24 -£ 20.12 -£ 92.31

2026 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £- £ 8.10 £ 5.77 -£ 86.54

2027 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 4.55 -£ 81.99

2028 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 4.06 -£ 77.93

2029 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 3.63 -£ 74.30

2030 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 3.24 -£ 71.07

2
2031 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 2.89 -£ 68.18

2032 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 2.58 -£ 65.59

2033 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 2.30 -£ 63.29

2034 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 2.06 -£ 61.23

2035 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 1.84 -£ 59.39

2036 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 1.64 -£ 57.75

2037 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 1.46 -£ 56.29

2038 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 1.31 -£ 54.98

2039 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 1.17 -£ 53.81

2040 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 1.04 -£ 52.77

2041 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 0.93 -£ 51.84

2042 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 0.83 -£ 51.01

2043 £- £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 7.16 £ 0.74 -£ 50.27

2044 -£ 15.48 £ 146.09 £ 137.98 £ 8.10 £ 4.32 £ 3.79 £ 0.95 £ 22.64 £ 2.10 -£ 48.17

3
5.18 Butane Oxidation
The cash flow analysis for butane oxidation process is tabulated below. The fixed capital is depreciated for a period of 20 years giving a
depreciation allowance of £ 6.08 M. The construction of the plant is carried out in two years. In the 3rd year of the project, the plant becomes
operational and is operated at 30% of design capacity. The taxes are paid from the 4th year of the project. From the table it can be seen that the
NPV for the project becomes positive in the 9th year (2031) indicating that the project will provide a good return. The NPV of the project at the
end of plant life is £ 110.43M. The Internal Rate of Return for the project is calculated to be 23.73%. Both the indicators (NPV and IRR)
indicate that the project will be a profitable one. It is also worth mentioning that the mass of byproducts formed in the butane oxidation process
is much greater than the other two processes. Since no data about their quantities was available at the time of this analysis, they were ignored. By
including the revenue generated by those byproducts, both the NPV and IRR will increase even further.

Table 14 Cash flow analysis for butane oxidation process

n-Butane Oxidation Route - Cash Flow Analysis (In Million £)

Project Capital Operating Taxable Cash Present Value
Revenue Gross Profit Depreciation Tax Paid NPV
Year Cost Cost Income Flow of CF
2023 £ 36.50 £- £- £- £- £- £- -£ 36.50 -£ 36.50 -£ 36.50

2024 £ 73.00 £- £- £- £- £- £- -£ 73.00 -£ 65.18 -£ 101.68

2025 £ 16.68 £ 43.83 £ 34.29 £ 9.54 £ 6.08 £ 3.45 £- -£ 7.14 -£ 5.69 -£ 107.37

2026 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 26.35 -£ 81.02

2027 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 23.53 -£ 57.49

2028 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 21.01 -£ 36.49

4
2029 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 18.76 -£ 17.73

2030 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 16.75 -£ 0.98

2031 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 14.95 £ 13.97

2032 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 13.35 £ 27.32

2033 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 11.92 £ 39.24

2034 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 10.64 £ 49.88

2035 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 9.50 £ 59.38

2036 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 8.48 £ 67.87

2037 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 7.58 £ 75.44

2038 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 6.76 £ 82.21

2039 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 6.04 £ 88.25

2040 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 5.39 £ 93.64

2041 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 4.81 £ 98.45

2042 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 4.30 £ 102.75

2043 £- £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 37.02 £ 3.84 £ 106.59

5
 2044 -£ 4.51 £ 146.09 £ 98.75 £ 47.33 £ 6.08 £ 41.25 £ 10.31 £ 41.53 £ 3.84 £ 110.43

5.19 Summary of economic feasibility

The NPV of all three processes is represented graphically below. The graph indicates that for both Methanol carbonylation route and the butane
oxidation route, the project yields positive NPV at the end of plant life, whereas for acetylene oxidation route, the NPV will be negative.

£500
Cas h Flo w Analys is
Methanol Carbonylation
£400
Acetylene Oxidation
Net Present Value (million £)

Butane Oxidation
£300

£200

£100

£-

-£100

-£200
2023 2025 2027 2029 2031 2033 2035 2037 2039 2041 2043 2045

Project Year

Figure 16 Cash flow analysis diagram

6
The Internal Rate of Return for the three processes is graphically shown below along with the Interest Rate chosen for cash flow analysis. Here,
again the IRR shows that methanol carbonylation and butane oxidation routes are good for investment, whereas the acetylene process won’t be
feasible economically

Internal Rate of Return

70%

60%

50%

40%

30%

20%

10%

0%
Methanol Carbonylation Acetylene Oxidation Butane Oxidation Interest Rate

Figure 17 Internal rate of return diagram

7
6. Overall summary
Table 9 has been produced using the scores from each section and multiplying them together
with a total 300.

Table 15 Final route summary

Technical Environmental Economic Total

Methanol 7 6 7 200
carbonylation
route

Acetaldehyde 6 5 2 130
oxidation

The direct 6 5 4 150

oxidation of n-
butane

The methanol carbonylation approach emerges as the clear winner when compared to the others.
The simplicity of the methanol carbonylation approach in both its architecture and its reactions
has been shown to be advantageous throughout the study. Because there is a lot of information
accessible regarding the acetic acid by methanol carbonylation method, which is knowledge that
is not as easily accessed as the acetaldehyde oxidation and n butane route, the methanol
carbonylation route is the one that is suggested for use in this feasibility study.

8
7. References

Alen, M. “Acetic acid for industrial use.” Available at: https://doi.org/10.3403/00177527u.

Andrés-Barrao, C. and Barja, F. (2017) “Acetic acid bacteria strategies contributing to acetic
acid resistance during oxidative fermentation,” Acetic Acid Bacteria, pp. 92–119.
Available at: https://doi.org/10.1201/9781315153490-5.

Briggs, J.M., Nguyen, T.B. and Jorgensen, W.L. (2009) “Monte Carlo simulations of liquid
acetic acid and methyl acetate with the OPLS potential functions,” The Journal of Physical
Chemistry, 95(8), pp. 3315–3322. Available at: https://doi.org/10.1021/j100161a065.

Chen, F. and Gullo, M. (2015) “4th international conference on acetic acid bacteria - vinegar and
other products (aab 2015),” Acetic Acid Bacteria, 4(1s). Available at:
https://doi.org/10.4081/aab.2015.5518.

Cheung, H., Tanke, R.S. and Torrence, G.P. (2011) “Acetic acid,” Ullmann's Encyclopedia of
Industrial Chemistry [Preprint]. Available at:
https://doi.org/10.1002/14356007.a01_045.pub2.

De Vero, L. and Giudici, P. (2013) “Significance and management of acetic acid bacteria culture
collections,” Acetic Acid Bacteria, 2(1s), p. 9. Available at:
https://doi.org/10.4081/aab.2013.s1.e9.

Driver, T.G. (2010) “Acetic acid, 2-azido-, methyl ester; acetic acid, 2-azido-, ethyl ester; acetic
acid, 2-azido-, 1,1-dimethylethyl ester,” Encyclopedia of Reagents for Organic Synthesis
[Preprint]. Available at: https://doi.org/10.1002/047084289x.rn01146.

Fiume, M.Z. (2003) “Final report on the safety assessment of triacetin,” International Journal of
Toxicology, 22(3), pp. 1–10. Available at: https://doi.org/10.1080/747398359.

Garcia Garcia, I. and Gullo, M. (2013) “Acetic acid bacteria: Features and impact in bio-
applications,” Acetic Acid Bacteria, 2(1s), p. 1. Available at:
https://doi.org/10.4081/aab.2013.s1.e1.

Goldberg, R.N., Kishore, N. and Lennen, R.M. (2002) “Thermodynamic quantities for the
ionization reactions of buffers,” Journal of Physical and Chemical Reference Data, 31(2),
pp. 231–370. Available at: https://doi.org/10.1063/1.1416902.

Jones, R.E. and Templeton, D.H. (2002) “The crystal structure of acetic acid,” Acta
Crystallographica, 11(7), pp. 484–487. Available at:
https://doi.org/10.1107/s0365110x58001341.

9
Krimen, L.I. (2003) “Acetic formic anhydride,” Organic Syntheses, pp. 1–1. Available at:
https://doi.org/10.1002/0471264180.os050.01.

Michel, S. (1992) “Acetic anhydride,” Acetic Acid and its Derivatives, pp. 161–176. Available
at: https://doi.org/10.1201/9781482277272-20.

Nakano, S. and Ebisuya, H. (2016) “Physiology of acetobacter and Komagataeibacter spp.:

Acetic acid resistance mechanism in acetic acid fermentation,” Acetic Acid Bacteria, pp.
223–234. Available at: https://doi.org/10.1007/978-4-431-55933-7_10.

Navarro, D. et al. (2013) “Acetic acid bacteria in grape must,” Acetic Acid Bacteria, 2(1s), p. 4.
Available at: https://doi.org/10.4081/aab.2013.s1.e4.

Rutherford, F. (1992) “Acetic acid,” Acetic Acid and its Derivatives, pp. 89–116. Available at:
https://doi.org/10.1201/9781482277272-17.

Saichana, N. (2017) “Improvements of acetic acid bacterial strains: Thermotolerant properties of

acetic acid bacteria and genetic modification for strain development,” Acetic Acid Bacteria,
pp. 142–161. Available at: https://doi.org/10.1201/9781315153490-7.

Togeas, J.B. (2005) “Acetic acid vapor: 2. A statistical mechanical critique of vapor density
experiments,” The Journal of Physical Chemistry A, 109(24), pp. 5438–5444. Available at:
https://doi.org/10.1021/jp058004j.

Unger, T.A. (1996) “2 naphthyloxy acetic acid (Naphthoxy acetic acid),” Pesticide Synthesis
Handbook, p. 775. Available at: https://doi.org/10.1016/b978-081551401-5.50593-1.

Yamada, Y. (2016) “Systematics of acetic acid bacteria,” Acetic Acid Bacteria, pp. 1–50.
Available at: https://doi.org/10.1007/978-4-431-55933-7_1.

10