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A Study on Acetic Acid Manufacturing Plant

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DOI: 10.13140/RG.2.2.22187.04642

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 Che 308
Chemical Process Industries

Term Paper on

ACETIC ACID
MANUFACTURING PLANT
Authors:
Group 6 (A1)
Md. Ajmain Shakib- 1802026
Syeda Kaniz Fahima Rova- 1802027
Samiha Raisa Alam- 1802028
Md. Intesar Farhan Labib- 1802029
Md. Tuhin Mahmud- 1802030

Submitted to:
Dr. Iqbal Mahmud, Professor Emeritus, ChE, BUET
Dr. Md. Shahinoor Islam, Associate Professor, ChE, BUET
Dr. Iftheker Ahmed Khan, Assistant Professor, ChE, BUET
Md. Burhan Kabir Suhan, Lecturer, ChE, BUET
Zarin Tasnim Juthi, Lecturer, ChE, BUET
Tanzim Ur Rahman, Lecturer, ChE, BUET

ii
Authors and Contribution:
Name Student ID Contribution

Md. Ajmain Shakib 1802026 1. Local and market analysis of acetic acid

2. Global market analysis of propionic acid

3. Energy balance around heavy end column

4. Compilation

Kaniz Fahima Rova 1802027 1. Process chemistry

2. Process description,

3. Energy intensity,

4. Advantages of Cativa process,

5. Energy balance around light end column

Samiha Raisa Alam 1802028 1. Summary,

2. Background of the study,

3. Raw materials,

4. Energy balance around flasher,

5. Conclusion

Md. Intesar Farhan 1802029 1. Process flow diagram,

Labib
2. Process block diagram,

3. Material balance of the process,

4. Energy balance around the reactor.

Md. Tuhin Mahmud 1802030 1. Waste management,

2. Environmental impact,

3. Energy balance around mixing unit.

iii
Statement of Academic Integrity:
The authors of this term paper hereby certify that none of the works included in the paper,
titled "Acetic Acid Manufacturing Plant," which is based on the sessional course Chemical
Process Industries (ChE-308), were directly plagiarized or otherwise violated academic
integrity except for complete theoretical parts. During the writing of this report, all instances
of plagiarism were avoided, and only credible sources were used and cited appropriately.

Authors:

Md. Ajmain Shakib (1802026)

Kaniz Fahima Rova (1802027)

Samiha Raisa Alam (1802028)

Md. Intesar Farhan Labib (1802029)

Md. Tuhin Mahmud (18020230)

Department of Chemical Engineering

Bangladesh University of Engineering and Technology

iv
Summary:
Acetic acid has been a crucial commodity in human civilization for a very long time. Initially
being used as a necessary food additive, preservative, and disinfectant, its applications has
now spread to several sectors such as, chemical industry, pharmaceutical industry, cosmetic
industries etc. The production of acetic acid has been under constant development since the
1950s, maintaining pace with its ever-rising demand. The production method used for the
manufacture of the majority of acetic acid is methanol carbonylation pathway and the most
effective pathway is the Cativa process. A comparative discussion of the pathways for acetic
acid manufacturing has been made in this paper with a focus on the prevalent Cativa process.
Material and energy balances were carried out for the different unit operations involved
within Cativa process. The process parameters were calculated for a 90% yield of CH 3COOH
and 5% (of fresh feed) recycle of CH3OH. For a feed of 1000 kmol/day CH3OH, a final
product of 905.896 kmol/day of 99.3mol% of CH3COOH was obtained. The Iridium based
catalysts are recycled and reused within the process. The range of applications of acetic acid
is widening day by day with establishment of chemical industries globally as well as in
Bangladesh. Thus, the manufacture of acetic acid demands to be more sophisticated,
sustainable, and energy effective. The Cativa process principle, with some modifications, is
the ideal pathway for production as reviewed in this paper.

v
Acknowledgement:
The respected teachers of the course "CHE 308: Chemical Process Industries," who have
worked tirelessly to deliver insights regarding the industry-specific applications of chemical
processes during the entirety of the course, have the authors' deepest gratitude.

Throughout the writing and compilation of this dissertation, their encouragement, direction,
and insightful criticism have repeatedly enabled us to stay motivated and comprehend the
complexities and technicalities of the acetic acid industry.

Authors:

Md. Ajmain Shakib (1802026)

Kaniz Fahima Rova (1802027)

Samiha Raisa Alam (1802028)

Md. Intesar Farhan Labib (1802029)

Md. Tuhin Mahmud (18020230)

Department of Chemical Engineering

Bangladesh University of Engineering and Technology

vi
Table of Contents
Authors and Contribution: ....................................................................................................... iii

Statement of Academic Integrity: ............................................................................................. iv

Summary: ................................................................................................................................... v

Acknowledgement: ................................................................................................................... vi

Table of Contents .....................................................................................................................vii

List of Figures ........................................................................................................................... ix

List of Tables ............................................................................................................................. x

1.Background of the Study: ....................................................................................................... 1

1.1 Introduction: ..................................................................................................................... 1

1.2 Application of Acetic Acid: ............................................................................................. 1

1.3 Production Process of Acetic Acid: ................................................................................. 3

1.4 Raw Materials and Availability of Raw Materials: ......................................................... 4

2. Market Analysis ..................................................................................................................... 9

2.1 Global Market of Acetic Acid.......................................................................................... 9

2.2 Acetic Acid Market in Bangladesh ................................................................................ 14

2.3 Global Market of Propionic Acid: ................................................................................. 16

3. Process Selection ................................................................................................................. 19

3.1 Chemistry and Reaction Conditions: [23],[24]................................................................... 19

3.2 Energy intensity: [24]....................................................................................................... 22

3.3 Process description: ....................................................................................................... 23

4. Process Flow Diagram: ........................................................................................................ 25

5. Process Block Diagram: ....................................................................................................... 26

6.Material Balance: .................................................................................................................. 27

7.Energy Balance ..................................................................................................................... 31

7.1 Energy Balance around the Reactor:[26],[28],[29] ............................................................... 31

vii
 7.2 Energy Balance Around Flasher:[26],[28],[29] .................................................................... 35

7.3 Energy Balance around the Light End Column ............................................................. 37

7.4 Energy Balance around Mixing Unit: [26],[28],[29] ............................................................ 41

7.5 Energy Balance Around Heavy End Column: [26],[28],[29] ................................................ 44

8. Waste Management and Environment Impact ..................................................................... 49

8.1 What is waste ................................................................................................................. 49

8.2 Source of waste .............................................................................................................. 49

8.3 Classification of waste ................................................................................................... 49

8.4 Waste released from acetic acid plant ............................................................................ 50

8.5 Environmental impact of the waste................................................................................ 50

8.6 Waste Management ........................................................................................................ 53

8.7 The Benefits of Waste Management .............................................................................. 54

9. Conclusion: .......................................................................................................................... 55

10. References: ......................................................................................................................... 56

viii
List of Figures
Figure 1: Applications of Acetic Acid in Chemical and Food Sectors Globally. ...................... 2
Figure 2: The Demand of Acetic Acid by Applications. [10].................................................... 3
Figure 3: Global Methanol Market Share by Feedstock. (Source: ResearchDive, Global
Methanol Market Analysis [14]) ................................................................................................ 5
Figure 4: Global Methanol Market by Region. (Source: Methanol Market Research Report,
Polaris Market Research [15]) ................................................................................................... 6
Figure 5: Methanol Import Data of Bangladesh. (Source: Methanol Alcohol Import Data of
Bangladesh,www.exportgenius.in) [16] .................................................................................... 7
Figure 6: Global High Pressure Carbon Monoxide Market, by region. (Source: Data Bridge
Market Research Market Analysis Study, 2022) [17] ............................................................... 8
Figure 7: Top acetic acid exporting countries from different continents (18) ........................... 9
Figure 8: Top acetic acid importing countries from different continents (18) ........................ 10
Figure 9: Worldwide growth of exporters of acetic acid from 2015 to 2020 (18)................... 11
Figure 10: Worldwide growth of importers of acetic acid from 2015 to 2020 (18) ................ 12
Figure 11: Color grading of acetic acid exporting and importing countries in 2020 (18) ....... 13
Figure 12: Global acetic acid market share by region in 2019 (19)......................................... 14
Figure 13: Acetic acid import origin and corresponding values in 2020 for Bangladesh (20) 14
Figure 14: Acetic acid import origin growth from 2015 to 2020 for Bangladesh (20) ........... 15
Figure 15: Change in acetic acid import market from 2015 to 2020 for Bangladesh (20) ...... 16
Figure 16: Global consumption of propionic acid in 2019 (21) .............................................. 17
Figure 17: Worldwide market volume of propionic acid from 2015 to 2021 (22) .................. 18
Figure 18: Reaction cycle proposed for iridium catalyzed methanol carbonylation reaction
(Cativa process) ....................................................................................................................... 21
Figure 19: Process flow diagram of acetic acid plant .............................................................. 25
Figure 20: Process flow diagram of acetic acid plant. ............................................................. 25
Figure 21: Balanced Reactor .................................................................................................... 31
Figure 22: Balanced light end column .................................................................................... 37
Figure 23: Balanced mixing unit.............................................................................................. 41
Figure 24: Balanced heavy end column ................................................................................... 44

ix
Figure 25: Waste classification by origin. Different activities generate different types of
waste[31] .................................................................................................................................. 49
Figure 26: Visual Impacts of Climate Change Evidence [37] ................................................. 52
Figure 27: Waste Management procedure ............................................................................... 53

List of Tables
Table 1: Enthalpy Input-Output Table for Reactor…………………………………………..32

Table 2: Enthalpy Input-Output Table for Flasher…………………………………………...35

Table 3: Enthalpy Input-Output Table for Light End Column……………………………….38

Table 4: Enthalpy Input-Output Table for Mixing Unit……………………………………...42

Table 5: Enthalpy Input-Output Table for Heavy End Column……………………………...44

x
1.Background of the Study:
1.1 Introduction:

Acetic acid is commodity chemical that holds an important place in the food industry and the
chemical industry. Acetic acid is an organic compound with the chemical formula
CH3COOH. It is a clear liquid with a sour taste and distinct odor, which melts at 16.6 ℃ and
boils at 117.9 ℃ [1]. With a global demand of approximately 15 million tons per year, the
production process of acetic acid is continuously being developed into more efficient and
sustainable pathways [2]. Several years ago, acetic acid was used to heal wounds and as a
remedy against diseases. The organic acid has been used as food preservative since as long as
5000 BC [3]. The 4% solution of the acid, vinegar is a familiar ingredient in food industry
and households. Since the 1950’s, acetic acid has been widely used as a raw material for
several commercial industrial processes in food, pharmaceuticals, cosmetics, textile etc.
industries, making it a commercially important commodity [4]. Due to its ever-increasing
demand, the production process for acetic acid manufacture has gone through several changes
since its development many years ago. Vinegar was first obtained by fermenting fruit syrups,
and the principle of fermentative production is still widely used for the manufacture of
vinegar. The commercial requirement of acetic acid has demanded for a more efficient
method of synthetic production which has been met by the development of processes likes
methanol carbonylation, aldehyde oxidation, hydrocarbon oxidation etc. [5]. With an average
growth rate of production of 5% per year [6], and the increasing demand for the chemical in
south- Asian regions, it has become imperative to establish a more sustainable and efficient
manufacturing process for acetic acid production.

1.2 Application of Acetic Acid:

Acetic acid is widely used in chemical industries as an important chemical building block in
the commercial production of important commodities. The uses of acetic acid in food
industry are also widespread and newer applications are being innovated continuously. In the
chemical sector, acetic acid is used to produce vinyl acetate (Vinyl Acetate Monomer, VAM),
which is an important component in the textile and polymer industries. Acetic anhydride, a
vital chemical building block in pharmaceutical, plasticizer, textile fiber, and photo film
industries [2]. It is also used as a solvent in important chemical synthesis, such as, in the
production of Purified Terephthalic Acid (PTA) production. PTA is a raw material for the
1
production of polyester (PET) fiber, film, and resin [7]. Besides, acetic esters produced from
acetic acid are widely used as solvents in many chemical processes. In the food sector, acetic
acid is widely used as vinegar, its 4% aqueous solution. Besides its uses as a food additive
and food preservative, it is also being used as an anti-microbial agent in food industries.
Acetic acid is also used in the manufacture of edible packaging, contributing towards
sustainability in the food industry [8,9].

Dyes, herbicides,
Chloroacetic acid
disinfectant
Medicine, photo
Acetic anhydride
films, textile fibre

Chemical Sector Acetic ester Solvent

Acetic Acid

Acetate salts Medicine, dyes

Vinyl acetate
Textile industry
(VAM)

Food additive

Preservative
Food Sector
Antimicrobial
agent

Edible packaging

Figure 1: Applications of Acetic Acid in Chemical and Food Sectors Globally.

2
 Demand of Acetic Acid by Applications

Others
19%

Vinyl Acetate Vinyl Acetate Monomer (VAM)

Monomer (VAM)
Acetic anhydride
37%
Acetates Purified Terephthalic Acid (PTA)
12%
Acetates
Others
Purified Terephthalic
Acid (PTA)
18% Acetic anhydride
14%

Figure 2: The Demand of Acetic Acid by Applications. [10]

1.3 Production Process of Acetic Acid:

Acetic acid was first produced by the aerobic fermentation of ethanol, which is still the
manufacturing procedure used for vinegar production [7]. The first synthetic process for the
manufacture of acetic acid, which was acetaldehyde oxidation, was industrialized in Germany
in 1914 [10]. The acetaldehyde oxidation process used an organometallic compound as
catalyst, which had adverse effects on the environment and health [7]. Because of its
environmental impacts, the acetaldehyde oxidation process was quickly phased out with the
revolutionary innovation of the Hoechst- Wacker process in 1959, which employed ethylene
as its raw material. At the same time, the hydrocarbon oxidation process was industrialized
with the industrialization of liquid phase oxidation of n-butane in 1952, and
commercialization of liquid phase oxidation of naptha in 1956 [10]. The drawbacks of these
processes were the large amounts of oxidation by-products, and very complex and expensive
separation and recovery processes. By 1955, a homogenous methanol carbonylation pathway
for the manufacture of acetic acid was developed which used carbon monoxide and methanol
as raw materials. The methanol carbonylation process was commercialized by BASF
(Germany) in 1960 which used an iodide-promoted CO catalyst. Later in 1970, Monsanto
(USA) commercialized an improved process that employed a methyl-iodide promoted Rh
3
catalyst [4, 11]. The Monsanto process was superior to the previously used methods (ethanol
fermentation, and acetaldehyde, n-butane, or naphtha oxidation) in terms of efficiency, yield
and environmental impacts. The acetic acid yields by the Monsanto process were 99% and
85% based on methanol and CO consumptions respectively [12]. Homogenous metal
catalysts that employ less costly metals than Rh were later developed among which the
Cativa process using Iridium (Ir) catalyst industrialized by BP chemicals is significant [7].

1.4 Raw Materials and Availability of Raw Materials:

The primary raw materials for acetic acid manufacture include methanol and carbon
monoxide. Rhodium and Iridium based catalysts are also vital raw materials for the process.
The carbon monoxide is usually synthesized from syngas production and then consequent
separation. The production of syngas requires methane (natural gas) and a reforming agent
(steam, oxygen, carbon dioxide, or a combination) [6]. One of the challenges in acetic acid
manufacture is the wavering prices of methanol [13]. The increasing number of chemical
industries in South-East Asian countries is driving the methanol market to expand in size, but
the demands are still somewhat higher than the supply. the instability of the fossil fuel market
also reflects in the prices of methanol. Globally, the methanol is produced from feedstock
containing coal, natural gas, or other fuels.

4
Figure 3: Global Methanol Market Share by Feedstock. (Source: ResearchDive, Global Methanol
Market Analysis [14])

5
The methanol supply is increasing at a steady pace worldwide along with the flourish of
chemical industries and process innovations. Considering the significant growth potential for
acetic acid plant in Bangladesh, the methanol market possesses potential for significant
growth.

Figure 4: Global Methanol Market by Region. (Source: Methanol Market Research Report, Polaris
Market Research [15])

Currently, Bangladesh imports methanol mostly from Malaysia, Singapore, Germany, India,
and United States.

6
 Net Weight Methanol Imported (kg)

Malaysia Singapore USA Germany India

Figure 5: Methanol Import Data of Bangladesh. (Source: Methanol Alcohol Import Data of
Bangladesh,www.exportgenius.in) [16]

Carbon monoxide is another primary raw material used in acetic acid manufacture. The
global high pressure carbon monoxide market is expected to expand vastly due to its
increased demand in the near future. The local high pressure carbon monoxide in the Asia
Pacific is also expected to grow in the coming years [17].

7
Figure 6: Global High Pressure Carbon Monoxide Market, by region. (Source: Data Bridge Market
Research Market Analysis Study, 2022) [17]

8
2. Market Analysis
Recent trade data of acetic acid and the heavy end byproduct propionic acid are discussed in
this section based on global and local markets.

2.1 Global Market of Acetic Acid

With a total transaction of $1.48 billion in 2020, acetic acid ranked as the 1507th most traded
product globally. Acetic acid trade accounts for 0.0088% of total global trade. Acetic acid
exports fell by -15.1% between 2019 and 2020, from $1.74 billion to $1.48 billion. This trend
is obvious due to the impact of Covid-19 on transportation systems. (18)

Figure 7: Top acetic acid exporting countries from different continents (18)

In 2020, a total of $1.48 billion in acetic acid was exported worldwide. The top exporter was
the United States ($364M) with a percentage of 24.6 of total export. Then arrived China
9
($149M) with a percentage of 10.1 of total export. Next Malaysia ($134M) with 9.08 percent.
Finally United Kingdom ($131M), and Singapore ($128M) with a percentage of 8.83 and
8.66 respectively. Besides the countries discussed above, Chinese Taipei ($123M), Belgium
($110M), South Korea ($81.1M), and Saudi Arabia ($53.3M) contributed much to the global
market. (18)

Figure 8: Top acetic acid importing countries from different continents (18)

In 2020, the top importer of Acetic acid was India ($324M) with 21.9 percent of total
imports. Then came Germany ($166M), Belgium ($164M), Mexico ($132M), and the
Netherlands ($71.1M) with a percentage of 11.2, 11.1, 8.95, 4.81 for total imports
respectively.

In the following figures 9,10, the growth of exporters and importers is demonstrated between
2015 and 2020.

10
In figure 9, it is clear that between 2015 and 2020, the exports of acetic acid grew faster in
Belgium ($53.6M), Serbia ($34.5M), Saudi Arabia ($27.5M), United Kingdom ($18.3M),
and Singapore ($7.68M).

Figure 9: Worldwide growth of exporters of acetic acid from 2015 to 2020 (18)

From figure 10, it is reported that between 2015 and 2020, the imports of acetic acid grew
faster in the Netherlands ($43M), Germany ($36.5M), India ($17.3M), Poland ($7.94M), and
United Kingdom ($6.99M).

11
 Figure 10: Worldwide growth of importers of acetic acid from 2015 to 2020 (18)

Moreover, the recent (2020) and the previous 5 years (2020-2015) export and import data
analysis combinedly state that a huge worldwide expansion of the acetic acid market occurred
in the past 5 years. This also implies the increasing number of consumers for acetic acid and
different derivatives of acetic acid; which tend to increase in the future as well. (18)

12
Figure 11: Color grading of acetic acid exporting and importing countries in 2020 (18)

Which nations export or import the most acetic acid is depicted on this map. Based on the
variation in acetic acid exports and imports in 2020, each nation is given a different color.
The nations with the highest trade surplus between acetic acid exports and imports in 2020
were the United States ($350M), Malaysia ($131M), China ($129M), the United Kingdom
($118M), and Chinese Taipei ($115M). On the other hand, India ($316M), Germany
($141M), Mexico ($131M), Brazil ($60.2M), and the Netherlands ($58.1M) were the nations
with the highest trade deficits in imports and exports of acetic acid in 2020. (18)

13
2.2 Acetic Acid Market in Bangladesh

Figure 12: Global acetic acid market share by region in 2019 (19)

Though the Asia Pacific region occupied most of the area of the pie chart (19), the market in
Bangladesh is not that large. Still, Bangladesh relies on imported acetic acid to fill the market
demand. In 2020, Bangladesh imported $8.38M in acetic acid and became the 26th largest
importer of acetic acid in the world. In the same year, Acetic acid was the 759th most
imported product in Bangladesh.(20)

14

Figure 13: Acetic acid import origin and corresponding values in 2020 for Bangladesh (20)
In 2020, Bangladesh imported $8.38M in Acetic acid, mainly from South Korea ($4.17M)
with a percentage of 49.8 of total import. After that, India ($2.76M), China ($563k), Malaysia
($357k), and Chinese Taipei ($343k) followed with a percentage of 32.9, 6.71, 4.25, 4.09 of
total imports respectively. (20)

Figure 14: Acetic acid import origin growth from 2015 to 2020 for Bangladesh (20)

Though South Korea is the prime supplier of acetic acid in Bangladesh, in the past 5 years
(2015-2020) import growth rate decreased by $3.79M for South Korea. Whereas, India held
the highest growth rate of $1.24M. The data signifies the geopolitical interest of Bangladesh
in acetic acid importing also the rise of the acetic acid market in India. (20)

15
Figure 15: Change in acetic acid import market from 2015 to 2020 for Bangladesh (20)

2.3 Global Market of Propionic Acid:

The propionic acid industry can be regarded as worldwide given that there are only six large
manufacturers globally, with trade having a substantial impact on the global supply/demand
pattern. The majority of production capacity is operated by western companies, and it is
geographically concentrated in Western Europe, the United States, and to a lesser extent in
China. (21)

Some of the main uses of propionic acid are,

• Prevention of mold growth in animal feed storage

• Serves as an additive to food preservation
• In the manufacture of herbicides and diethyl ketone
• Smaller-volume applications include cellulose acetate propionate, solvent esters,
flavors and fragrances, and plasticizers

16
In the figure 16, it is clear that major users of propionic acid are Western Europe and

Figure 16: Global consumption of propionic acid in 2019 (21)

the United States. On the other hand, Asia pacific region excluding China is the
second least user of propionic acid. This is mainly because propionic acid is used to
prevent mold growth in animal feed storage but the Asia region is not dependent on
storage feed. Moreover, ruminants (e.g., cattle, sheep) show a higher tolerance to
mold compared with poultry and pigs. Actually, in Asia ruminants are the major live
stocks, and poultry feed is treated differently.(21)

17
Figure 17: Worldwide market volume of propionic acid from 2015 to 2021 (22)

In the figure 17 a rising market for propionic acid is demonstrated. A decrease in the market
volume of propionic acid is observed from 457.64 metric tons to 430.78 metric tons in the
period from 2019 to 2020. This decrease in the trend is observed due to the Covid-19 impact.
(22)

18
3. Process Selection
Monsanto in the early 1960s also discovered that iridium, like rhodium, is an effective
methanol carbonylation catalyst. This catalyst system has since been developed commercially
by BP in the early 1990s and is known as the Cativa process. This process was utilized to
convert the original rhodium-catalyzed methanol carbonylation plant in Texas City to an
iridium-based process. Several advantages claimed by BP for the Cativa process over the
conventional rhodium-catalyzed high reaction water carbonylation process include superior
catalyst stability, operation at lower reaction water, and less liquid byproducts.

3.1 Chemistry and Reaction Conditions: [23],[24]

Similar to the rhodium-based carbonylation processes, the reaction chemistry of the BP

iridium-catalyzed methanol carbonylation is well characterized. The iridium-catalyzed
reaction proceeds through a series of similar reaction pathways to the rhodium-catalyzed
system but involves a different rate-determining step. The proposed rate-determining step is
methyl migration to form the iridium acyl complex. This pathway involves the elimination of
iodide and the subsequent addition of carbon-mono-oxide. The direct dependence of the
reaction rate on carbon monoxide concentration and the inhibiting effect of low
concentrations of iodide are consistent with the rate-determining step. The proposed catalytic
scheme for the reaction is given in the following figure.
Model studies at 25°C demonstrate that the oxidative addition of methyl iodide to iridium is
about 120 – 150 times faster than for rhodium. However, methyl migration on iridium is 105
to 106 times slower than for rhodium.
The main byproducts of the iridium-catalyzed process are carbon dioxide and hydrogen via
the following water gas shift reaction.
CO + H2O CO2 + H2
The mechanism of this reaction is similar to the rhodium-catalyzed process. The production
of CH4 derived from methanol is higher for iridium than for rhodium. This observation is
consistent with the greater stability of the methyl-iridium (III) complex associated with the
hydrogenation of the iridium – carbon bond. Other transition-metal complexes have been
investigated as promising catalysts for methanol carbonylation, in particular, nickel
complexes by Halcon and Rhône-Poulenc.
To understand the iridium system, Forster and co-workers recognized and defined three
distinct reaction regions (Obviously, overlapping regions existed that demonstrated mixed
behavior) Each reaction region exhibited distinctly different kinetics and contained a different
predominant iridium species. These regions were defined as follows:
Region 1: A region in which the solution contained low concentrations of methyl iodide,
water, and anionic iodide
Region 2: A region that contained increased levels of anionic iodide
19
Region 3: A region characterized by the presence of high concentrations of either methanol or
water
In region 1, the form of the iridium was Ir(CO)3I. In this region, the reaction was inhibited by
increasing carbon monoxide pressures. This observation implied that, in the rate-controlling
step, a carbon monoxide ligand dissociates prior to the initiation of catalysis. The unstable
Ir(CO)2I complex was inferred as the species that actually reacted with methyl iodide.
Presumably this generated another unstable iridium species, MeIr(CO)2I2. Evidence obtained
from region 2 (vide infra) suggested that this complex adds an additional carbon monoxide
ligand yielding MeIr(CO)3I2. This species could undergo the successive insertions and
eliminations necessary to ultimately generate products.
The predominant form of iridium observed in region 2 was MeIr(CO)2I3. The formation of a
stable methyl iridium species contrasted sharply with the rhodium system in which carbon
monoxide insertion was spontaneous. Forster has suggested that the generally higher carbon-
metal bond strengths observed in methyl iridium species (compared to methyl-rhodium
species) might account for the difference between the two systems. Kinetically, in region 2
the reaction was accelerated by increasing carbon monoxide pressures, but was inhibited by
anionic iodide. The interpretation of these observations was that the observed complex,
MeIr(CO)2I3, must first dissociate an iodide ligand, generating an unstable MeIr(CO)2I2, and
then add an additional carbon monoxide to generate MeIr(CO)3I2. The connection between
regions 1 and 2 is readily apparent at this point as the MeIr(CO)3I2 is common to both
reaction regions.

HI + Ir(CO)2I2 HIr(CO)2I3
Ir(CO)2I2 + MeI MeIr(CO)2I3

In the third region, HIr(CO)2I3 was the predominant Ir species. The rate was independent of
CO but displayed an apparent dependence on methanol concentration. Of the carbonylations
mentioned to date, this represented the first process to exhibit a positive dependence on
methanol. Forster and co-workers have presented a rationalization for the HIr(CO)2I3 and its
entry into the catalytic cycle. These authors demonstrated that the addition of HI to Ir(CO)2I2
(the Ir analog of the active species in the rhodium-catalyzed process) was demonstrated to
rapidly establish an equilibrium with HIr(CO)2I3, as shown in the first reaction below. Forster
and co-workers postulated that the reaction of methyl iodide with Ir(CO)2I2 shown in the
second reaction below is irreversible, removing the Ir(CO)2I2 species and generating
MeIr(CO)2I3 in the process, and proceeded to demonstrate the stoichiometric reaction. The
chemistry of MeIr(CO)2I3 has been discussed previously, and this species forms the
connection between region 2 and region 3. The dependence on methanol has never been
completely rationalized.
Although the presence of the three reaction regions made the mechanistic interpretation very
difficult, the ingenious work represented above allowed Forster and co-workers to present a
coherent mechanism that integrated all three regions into a single comprehensive mechanism.
20
 This mechanism, shown in the following figure, is consistent with all the spectroscopic data,
the kinetic data, and the extensive list of known stoichiometric reactions assembled for this.

Figure 18: Reaction cycle proposed for iridium catalyzed methanol carbonylation reaction (Cativa
process)

21
3.2 Energy intensity: [24]

It represents the primary energy consumed per unit of output. A difference should be
observed between the energy developed by utility and the primary energy spent for produce
it. An efficiency of 80 % can be assumed for steam generation by fuel combustion and 40%
for electricity production by modern power plants. Here is assumed that an electrical kWh
needs three times primary (thermal) energy. In the base case, the separation section requires
13.5 MW steam from which 6.2 MW available as LP generated steam, hence only 7.3 MW
must be supplied as LP and MP steam. The electricity consumption regards 1450 kW power
for the CO compression, plus 150 MW for pumping, mixing and process control, hence a
total of 1600 kW or 4.8 MW thermal energy. To this one may add 0.26 MW required by
cooling-water conditioning via cooling towers (≈2% from 13 MW of C-1 and C-2
condensers) and 0.2 MW for refrigeration. The total used energy is then MW. Taking an
uncertainty factor of 20%, the total load is 15 MW. The energy intensity is then 2.16 MJ/kg.
For the eco-efficient process, the reaction section generates 5.4 MW as LP steam, which
covers the reboiler of D-1, while 9 MW of waste heat is converted into 1746 KW electricity.
Column D-2 is fully driven by a heat pump that needs 1160 kW electricity. In addition, 1450
kW is used for CO compression and 150 kW for pumping and process control. Hence the
electricity consumption is 2760 kW, but only 2760-1746= 1014 kW should be imported,
which is equivalent to 3.1 MW of primary energy. The process needs also 1 MW for feed
preheating (units H-1 and H-2). The cooling water conditioning referring to D-1 condenser is
0.02x10 = 0.2 MW, while for refrigeration 0.2 MW is assumed. The total load for the
reaction and separation sections is 4.5 MW, which rises to 5.4 MW after applying 20%
uncertainty. It results that energy intensity is 0.78 MJ/kg, or 64% reduction compared with
the base-case.

22
3.3 Process description:

Since the Cativa process as demonstrated in the Sterling Plant at Texas City, Texas is a
retrofit of the original Monsanto process, the overall general process is presumably the same,
possibly with some modifications (such as here the process is based on iridium not on
rhodium). Due to the limitations of the prior processes and also because of the very attractive
price difference between rhodium ($5200 per troy oz) and iridium ($300 per troy oz) which
existed in 1990, research into the use of iridium as a catalyst was resumed by BP in 1990,
after earlier work by Monsanto. The initial batch autoclave experiments showed significant
promise, and the development rapidly required the coordinated effort of several diverse
teams.

One early finding from the investigations was of the extreme robustness of the iridium
catalyst. Its robustness at extremely low water concentrations (0.5 wt.%) is particularly
significant and ideal for optimization of the methanol carbonylation process. The iridium
catalyst was also found to remain stable under a wide range of conditions that would cause
the rhodium analogues to decompose completely to inactive and largely irrecoverable
rhodium salts. Besides this stability, iridium is also much more soluble than rhodium in the
reaction medium and thus higher catalyst concentrations can be obtained, making much
higher reaction rates achievable.

Model studies have shown that the oxidative addition of methyl iodide to the iridium center is
about 150 times faster than the equivalent reaction with rhodium. This represents a dramatic
improvement in the available reaction rates, as this step is now no longer rate determining (as
in the case of rhodium.

For the above reasons, Cativa process is chosen over the other processes for the production of
acetic acid.

Carbon monoxide and methanol are introduced continuously into a back-mixed liquid-phase
reactor at ca. 150°– 200°C and 30 – 60 bar. The non-condensable byproducts (CO2, H2, and
CH4) are vented from the reactor to control the carbon-mono-oxide partial pressure in the
reactor. The off-gas from the reactor and the purification sections of the process are
combined and sent to a vent recovery system in which the light ends, including organic

23
iodides such as methyl iodide, are scrubbed from the vent before the non-condensable gases
are flared. The light ends from the vent recovery system are recycled to the reactor. The
reactor solution is forwarded to the flasher where the catalyst is separated as a residue stream
from the crude acetic acid product and recycled to the reactor. The crude acetic acid, which
contains methyl iodide, methyl acetate, and water, is taken overhead in and sent to the light-
ends column. The light components (methyl iodide, methyl acetate, and water) are recycled to
the reactor as a two-phase overhead stream, while wet acetic acid is removed as a side stream
from and sent to the dehydration column. Water is chemically absorbed, and a more-dry
acetic acid product residue stream is forwarded to a heavy ends column. As a residue stream
in, propionic acid, which is the major liquid byproduct of the process is removed with other
higher boiling carboxylic acids. Product acetic acid is removed in as a side stream, and the
overhead stream is recycled to the purification section of the process.[4]

24
4. Process Flow Diagram:

20: Process flow diagram of acetic acid plant

Figure 19: plant.

25
5. Process Block Diagram:

sbjgbkjsbd

26
6.Material Balance:
Basis:
1000 kmol/day fresh CH3OH fed.
Reactions:
1. CH3OH + CO CH3COOH
2. 2CH3OH + CO C2H5COOH + H2O
3. CH3OH + CH3COOH CH3COOCH3 + H2O
Additional information for reactor:
1. Assume that,
Recycled CH3OH from light end column is 5% of the fresh CH3OH feed

𝑛1
0.05= 1000

So, n1 = 50 kmol/day
2. From literature,[25]
(i) Yield of CH3COOH is 90% in the reactor

Yield=0.9
𝑛2
or, 0.9= 1050

So, n2=945 kmol/day

(ii) 90.91% conversion of CH3OH in the reactor

(1000+𝑛1 )− 𝑛5
= 0.9091
1000+𝑛1
or, 𝑛5 =1050 × (1-0.9091)

So, 𝑛5 = 95.445 kmol/day

(iii)Assume that, 100% conversion of CO is obtained.

Now,
CH3OH reacted= (1050-95.455) kmol/day
= 954.555 kmol/day
From reaction-1,
CH3OH + CO === CH3COOH
Stoichiometric ratio, 1 1 1
Reacted, 945 945 945
27
Remaining CH3OH reacted to form C2H5COOH which is (954.555-945) kmol/day
= 9.555 kmol/day
From reaction-2,
2CH3OH + CO C2H5COOH + H2O
Stoichiometric ratio, 2 1 1 1
Reacted, 9.555 4.78 4.78 4.78
So, n6= Stoichiometric amount of CO required for CH3COOH C2H5COOH
= (945+ 4.78) kmol/day
= 949.78 kmol/day
And n4= 4.78 kmol/day
Additional information for light end column:
3. 100% recovery of unreacted CH3OH.
n9= n1 = 50 kmol/day
4. From literature,[25]
Mole fraction of H2O in the side stream of light end column is 0.013 kmol/kmol
mixture.
In flasher,
CH3OH reacted= (95.445-50) kmol/day
= 45.445 kmol/day
From reaction-3,
CH3OH + CH3COOH CH3COOCH3 + H2O
Stoichiometric ratio, 1 1 1 1
Reacted, 45.445 45.445 45.445 45.445

So, n8= 45.445 kmol/day ,

n7= n4+ H2O produced from reaction-3
= (4.78+ 45.445) kmol/day
= 50.225 kmol/day
And n6= n2- CH3COOH consumed in reaction-3
= (945-45.445) kmol/day
= 899.555 kmol/day
28
From additional information-4,
𝑛10
0.013= 𝑛10 +899.555+4.78

or, 0.013 × (899.555+ 4.78) = n10 × (1-0.013)

So, n10= 11.91 kmol/day
H2O balance around light end column,
50.225= n11+ 11.91
So, n11= 38.315 kmol/day
From literature,[25]
Final product composition of acetic acid is, 99.8(wt)% CH3COOH and 0.2(wt)% H2O
99.8

Mole fraction of, CH3COOH = 99.8600.2 kmol/kmol mixture

+
60 18

= 0.993 kmol/kmol mixture

Mole fraction of, H2O = (1-0.993) kmol/kmol mixture
= 0.007 kmol/kmol mixture
Composition of propionic acid byproduct is: 98.3(wt)% C2H5COOH and 1.7(wt)% H2O
98.3
74
Mole fraction of, CH3COOH = 98.3 1.7 kmol/kmol mixture
+
74 18

= 0.934 kmol/kmol mixture

Mole fraction of, H2O = (1-0.934) kmol/kmol mixture
= 0.066 kmol/kmol mixture
CH3COOH balance around the marked area,
899.555 = 0.993 × n13
So, n13= 905.896 kmol/day
C2H5COOH balance around the marked area,
4.78 = 0.934 × n14
So, n14= 5.12 kmol/day

H2O balance around the marked area,

11.91 = n12 + 0.007 × 905.896 + 0.066 × 5.12
29
 So, n14= 5.23 kmol/day
Additional information for heavy end column:
5. (i) Assume that,
Recycle ratio of CH3COOH stream to the final product= 1/100
or, n15/905.896 = 1/100
So, n15= 9.05896 kmol/day
(ii) Again assume that,
Mole fraction of CH3COOH in recycle stream is= 0.7 kmol/kmol mixture
Mole fraction of CH3COOH in recycle stream is= 0.3 kmol/kmol mixture

CH3COOH balance around the mixing point,

n16 = 0.7 × 9.05896+ 899.555
So, n16= 905.896 kmol/day
H2O balance around the mixing point,
n17 = 0.3 × 9.05896+ 11.91
So, n17 = 14.63 kmol/day
H2O balance around dehydrator,
14.63 = 5.23+ n18
So, n17 = 9.4 kmol/day

30
7.Energy Balance
7.1 Energy Balance around the Reactor:[26],[28],[29]

Figure 21: Balanced Reactor

We know,

𝛥𝐻 + 𝛥𝐸𝑘 + 𝛥𝐸𝑝 = 𝑄 − 𝑊𝑠

As here, there is no velocity and height change involved,

𝛥𝐸𝑘 = 0 𝑘𝐽/𝑚𝑜𝑙

𝑎𝑛𝑑 𝛥𝐸𝑝 = 0 𝑘𝐽/𝑚𝑜𝑙

Again, no shaft work is obtained here.

̂𝑖𝑛 -∑ 𝑛𝑖 𝐻
So, Q= 𝛥𝐻 = ∑𝑜𝑢𝑡 𝑛𝑖 𝐻 ̂𝑖𝑛
𝑖𝑛

31
Reference: C(s), H2(g) and O2(g) at 250C and 1 atm

Table 1: Enthalpy Input-Output Table for Reactor.

Component nin (kmol/day) ̂ 𝒊𝒏 (𝒌𝑱/𝒌𝒎𝒐𝒍)

𝑯 nout (kmol/day) ̂ 𝒐𝒖𝒕 (𝒌𝑱/𝒌𝒎𝒐𝒍)
𝑯

CH3OH(fresh) 100 ̂1 = -235.69 x 103

𝐻 - −

CH3OH(outlet) - - 95.445 ̂3 = -77.84 x 103

𝐻

CO 949.78 ̂2 = -110.42x103
𝐻 - −

CH3COOH - - 945 ̂4 = -468x 103

𝐻

C2H5COOH - - 4.78 ̂5 = -487.495 x 103

𝐻

H2O - - 4.78 ̂6 = -2.7632 x 103

𝐻

CH3OH(recycle) 50 ̂7 = -235.52 x 103

𝐻 -

60
̂1 = 𝛥Hf0(250C) + ∫ 𝐶𝑝(𝐶𝐻 𝑂𝐻) 𝑑𝑇
𝐻
25 3

60
= -238.6+ ∫25 (75.86 × 10−3 + 16.83 × 10−5 𝑇) 𝑑𝑇

= -235.69 × 103 kJ/kmol

̂2 = 𝛥Hf0(250C) + 𝑉̂ 𝛥𝑃
𝐻

1
= -110.52×103 + × (29.6 − 1) × 101325 × 28 × 10-3
789

= -110.42×103 kJ/kmol

150
̂3 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝑂𝐻) 𝑑𝑇+ 𝑉̂ 𝛥𝑃
25

60 1
= -201.2+ ∫25 (42.93 × 10−3 + 8.301 × 10−5 𝑇) 𝑑𝑇 + × (29.6 − 1) × 101325 ×
792

32 × 10-3

= -77.84 × 103 kJ/kmol

32
 423
̂4 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻) 𝑑𝑇 + 𝑉̂ 𝛥𝑃
298

423
= -486.18 × 103 + ∫298 (1.3964 × 105 + 3.208 × 102 𝑇 + 8.985 × 10−1 𝑇 2 ) ×
1
10−3 𝑑𝑇 + 1049 × (29.6 − 1) × 101325 × 60 × 10−3

= -4.68 × 105 kJ/kmol

423
̂5 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶2𝐻5 𝐶𝑂𝑂𝐻) 𝑑𝑇 + 𝑉̂ 𝛥𝑃
298

423
= -510 × 103 + ∫298 (2.1366 − 7.027 × 102 𝑇 + 1.6605 𝑇 2 ) × 10−3 𝑑𝑇 +

1
+ 993 × (29.6 − 1) × 101325 × 74 × 10−3

= -4.87495 × 105 kJ/kmol

150
̂6 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐻2 𝑂) 𝑑𝑇 +𝑉̂ 𝛥𝑃
25

150 1
= -285.84 × 103+ ∫25 (75.4) 𝑑𝑇 + 1000 × (29.6 − 1) × 101325 × 18 × 10-3

= -2.7632 × 103 kJ/kmol

We know,

𝛥𝐻 + 𝛥𝐸𝑘 + 𝛥𝐸𝑝 = 𝑄 − 𝑊𝑠

As here, there is no velocity and height change involved,

𝛥𝐸𝑘 = 0 𝑘𝐽/𝑚𝑜𝑙

𝑎𝑛𝑑 𝛥𝐸𝑝 = 0 𝑘𝐽/𝑚𝑜𝑙

Again, no shaft work is obtained here.

So,

̂𝑖𝑛 -∑ 𝑛𝑖 𝐻
Q= 𝛥𝐻 = ∑𝑜𝑢𝑡 𝑛𝑖 𝐻 ̂𝑖𝑛
𝑖𝑛

33
= -7.73 x 109 kJ/day

=89.468×103KW

34
 7.2 Energy Balance Around Flasher:[26],[28],[29]

150℃, 29.6 atm 52℃, 1 atm

Flasher
n2 = 945 kmol/d CH3COOH n6= 899.555 kmol/d CH3COOH

n3= 4.78 kmol/d C2H5COOH n3= 4.78 kmol/d C2H5COOH

n4= 4.78 kmol/d H2O n7= 50.225 kmol/d H2O

n5= 95.445 kmol/d CH3OH n8= 45.445 kmol/d CH3COOCH3

n9= 50 kmol/d CH3OH

Ref: C (s), H2 (g), O2 (g), N2 (g) at 25℃, 1 atm.

Table 2: Enthalpy Input-Output Table for Flasher.

Species ̇ (kmol/day)
𝒏𝒊𝒏 𝑯̂𝒊𝒏 (kJ/mol) ̇ (kmol/day)
𝒏𝒐𝒖𝒕 ̂
𝑯 𝒐𝒖𝒕 (kJ/mol)

CH3COOH 945 ̂1 =-451.92

𝐻 899.555 ̂5 =-482.86
𝐻

C2H5COOH 4.78 ̂2 =-448.97

𝐻 4.78 ̂6 =-506.18
𝐻

H2O 4.78 ̂3 =-237.86

𝐻 50.225 ̂7 =-283.8
𝐻

CH3COOCH3 - - 45.445 ̂8 =-402.11

𝐻

CH3OH 95.445 ̂4 = -196.66

𝐻 50 ̂9 = -236.55
𝐻

330 423
̂1 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻,𝑙) 𝑑𝑇 + 𝛥Hv0+ ∫ 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻,𝑣) 𝑑𝑇
298 330

330 423
= −486.18 + ∫298 0.1231𝑑𝑇 + 24.39+ ∫330 0.0634𝑑𝑇

̂1 = -451.92 KJ/mol
𝐻

35
 414 423
̂2 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶2𝐻5 𝐶𝑂𝑂𝐻,𝑙) 𝑑𝑇+ 𝛥Hv0 + ∫ 𝐶𝑝(𝐶2 𝐻5 𝐶𝑂𝑂𝐻,𝑣) 𝑑𝑇
298 414

414 423
= −510.8 + ∫298 (129.7 − 0.1263𝑇) × 10−3 𝑑𝑇+ 51 + ∫414 0.1108𝑑𝑇

̂2 = -448.97 KJ/mol
𝐻

100 150
̂3 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐻2 𝑂,𝑙) 𝑑𝑇+ 𝛥Hv0 +∫ 𝐶𝑝(𝐻2 𝑂,𝑣) 𝑑𝑇
25 100

100 150
= −285.84 + ∫25 75.4 × 10−3 𝑑𝑇+ 40.66 +∫100 33.46 × 10−3 𝑑𝑇

̂3 = -237.86 KJ/mol
𝐻

64.7 150
̂4 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝑂𝐻,𝑙) 𝑑𝑇 +𝛥Hv0+ ∫ 𝐶𝑝(𝐶𝐻3 𝑂𝐻,𝑣) 𝑑𝑇
25 64.7

64.7 150
= −238.6 + ∫25 75.86 × 10−3 𝑑𝑇 +35.27+ ∫64.7 42.93 × 10−3 𝑑𝑇

̂4 = -196.66 KJ/mol
𝐻

325
̂5 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻,𝑙) 𝑑𝑇
298

325
= −486.18) + ∫298 123.1 × 10−3 𝑑𝑇

̂5 = -482.86 KJ/mol
𝐻

350
̂6 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶2𝐻5 𝐶𝑂𝑂𝐻,𝑙) 𝑑𝑇
298

350
= −510.8 + ∫298 (129.7 − 0.1263𝑇) × 10−3 𝑑𝑇

̂6 = -506.18 KJ/mol
𝐻

52
̂7 = 𝛥Hf0(250C) + ∫ 𝐶𝑝(𝐻 𝑂,𝑙) 𝑑𝑇
𝐻
25 2

52
=−285.84+ ∫25 75.4 × 10−3 𝑑𝑇

̂7 = -283.8 KJ/mol
𝐻

350
̂8 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ,𝑙) 𝑑𝑇
298

36
 350
= −409.4 + ∫298 140.2 × 10−3 𝑑𝑇

̂8 = -402.11 KJ/mol
𝐻

52
̂9 = 𝛥Hf0(250C) + ∫ 𝐶𝑝(𝐶𝐻 𝑂𝐻,𝑙) 𝑑𝑇
𝐻
25 3

52
= −238.6 + ∫25 75.86 × 10−3 𝑑𝑇

̂9 = -236.55 KJ/mol
𝐻

̂𝑖 -∑ 𝑛𝑖 𝐻
Q= 𝛥𝐻 = ∑𝑜𝑢𝑡 𝑛𝑖 𝐻 ̂𝑖
𝑖𝑛

= 32.01 × 106 kJ/day

=370.49 kW

7.3 Energy Balance around the Light End Column:[26],[28],[29]

Figure 22: Balanced light end column

37
We know,
𝛥𝐻 + 𝛥𝐸𝑘 + 𝛥𝐸𝑝 = 𝑄 − 𝑊𝑠

As here, there is no velocity and height change involved,

𝛥𝐸𝑘 = 0 𝑘𝐽/𝑚𝑜𝑙

𝑎𝑛𝑑 𝛥𝐸𝑝 = 0 𝑘𝐽/𝑚𝑜𝑙

Again, no shaft work is obtained here.

̂𝑖𝑛 -∑ 𝑛𝑖 𝐻
So, Q= 𝛥𝐻 = ∑𝑜𝑢𝑡 𝑛𝑖 𝐻 ̂𝑖𝑛
𝑖𝑛

Reference:

C(s), H2(g), O2(g) at 250C and 1 atm.

Table 3: Enthalpy Input-Output Table for Light End Column.

Component nin (kmol/day) ̂ 𝒊𝒏 (𝒌𝑱/𝒌𝒎𝒐𝒍)

𝑯 nout ̂ 𝒐𝒖𝒕 (𝒌𝑱/𝒌𝒎𝒐𝒍)
𝑯
(kmol/day)

CH3COOH 899.555 ̂1 =-482.752 x 103

𝐻 899.555 ̂6 =-476.595 x 103
𝐻

C2H5COOH 4.78 ̂2 = -505.788 x 103

𝐻 4.78 ̂7 = -498.126 x 103
𝐻

H2O(inlet) 50.225 ̂3 = -283.8042 x 103

𝐻 - -

H2O(downstream) - - 11.91 ̂8 = -280.41 x 103

𝐻

CH3OH 50 ̂4 =-236.37 x 103

𝐻 50 ̂9 = -235.52 x 103
𝐻

CH3COOCH3 45.445 ̂5 = -407.464 x 103

𝐻 45.445 ̂10= -406.697 x 103
𝐻

H2O(upstream) - - 38.315 ̂11= -283.05 x 103

𝐻

325
̂1 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻) 𝑑𝑇
298

325
= -486.18 × 103 + ∫298 (1.3964 × 102 + 3.208 × 10−1 𝑇 + 8.985 × 10−4 𝑇 2 ) 𝑑𝑇

= -482.752 × 103 kJ/kmol

38
 325
̂2 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶2𝐻5 𝐶𝑂𝑂𝐻) 𝑑𝑇
298

325
= -510 × 103 + ∫298 (2.1366 − 7.027 × 102 𝑇 + 1.6605 𝑇 2 ) × 10−3 𝑑𝑇

= -505.788 × 103 kJ/kmol

52
̂3 = 𝛥Hf0(250C) + ∫ 𝐶𝑝(𝐻 𝑂) 𝑑𝑇
𝐻
25 2

52
= -285.84 × 103+ ∫25 (75.4) 𝑑𝑇

= -283.8042 × 103 kJ/kmol

52
̂4 = 𝛥Hf0(250C) + ∫ 𝐶𝑝(𝐶𝐻 𝑂𝐻) 𝑑𝑇
𝐻
25 3

52
= -238.6 + ∫25 (75.86 × 10−3 + 16.83 × 10−5 𝑇) 𝑑𝑇

= -236.37 × 103 kJ/kmol

325
̂5 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ) 𝑑𝑇
298

325
= -409.4 × 103 + ∫298 (6.126 × 104 + 2.709 × 102 𝑇 ) × 10−3 𝑑𝑇

= -407.464 × 103 kJ/kmol

370
̂6 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻) 𝑑𝑇
298

370
= -486.18 × 103 + ∫298 (1.3964 × 102 + 3.208 × 10−1 𝑇 + 8.985 × 10−4 𝑇 2 )𝑑𝑇

= -476.595 × 103 kJ/kmol

325
̂7 = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶2𝐻5 𝐶𝑂𝑂𝐻) 𝑑𝑇
298

325
= -510 × 103 + ∫298 (2.1366 − 7.027 × 102 𝑇 + 1.6605 𝑇 2 ) × 10−3 𝑑𝑇

= -498.126 × 103 kJ/kmol

97
̂8 = 𝛥Hf0(250C) + ∫ 𝐶𝑝(𝐻 𝑂) 𝑑𝑇
𝐻
25 2

39
 52
= -285.84 × 103+ ∫25 (75.4) 𝑑𝑇

= -280.41 × 103 kJ/kmol

52
̂9 = 𝛥Hf0(250C) + ∫ 𝐶𝑝(𝐶𝐻 𝑂𝐻) 𝑑𝑇
𝐻
25 3

97
= -238.6 + ∫25 (75.86 × 10−3 + 16.83 × 10−5 𝑇) 𝑑𝑇

= -235.52 × 103 kJ/kmol

335
̂10 = = 𝛥Hf0(250C) + ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻3 ) 𝑑𝑇
298

335
= -409.4 × 103 + ∫298 (6.126 × 104 + 2.709 × 102 𝑇 ) × 10−3 𝑑𝑇

= -406.697 x 103 kJ/kmol

62
̂11 = 𝛥Hf0(250C) + ∫ 𝐶𝑝(𝐻 𝑂) 𝑑𝑇
𝐻
25 2

62
= -285.84 × 103+ ∫25 (75.4) 𝑑𝑇

= -283.05 × 103 kJ/kmol

So,

̂𝑖𝑛 -∑ 𝑛𝑖 𝐻
Q= 𝛥𝐻 = ∑𝑜𝑢𝑡 𝑛𝑖 𝐻 ̂𝑖𝑛
𝑖𝑛

= 5.114 × 106 kJ/day

=59.19KW

40
7.4 Energy Balance around Mixing Unit: [26],[28],[29]

Figure 23: Balanced mixing unit

For this unit,

𝑄 = 𝛥𝐻

̂𝑖𝑛 -∑ 𝑛𝑖 𝐻
Q= 𝛥𝐻 = ∑𝑜𝑢𝑡 𝑛𝑖 𝐻 ̂𝑖𝑛
𝑖𝑛

41
Reference:

H2O (l), CH3COOH(l) , C2H5COOH(l) at 250C and 1 atm.

Table 4: Enthalpy Input-Output Table for Mixing Unit.

nin nout
Component ̂ 𝒊𝒏 (𝒌𝑱/𝒎𝒐𝒍)
𝑯 ̂ 𝒐𝒖𝒕 (𝒌𝑱/𝒎𝒐𝒍)
𝑯
(kmol/day) (kmol/day)

CH3COOH(l) (Inlet) 899.555 0 − −

CH3COOH(l) (recycle) 6.3413 ̂15.1= 1.6

𝐻 − −

CH3COOH(l) (Outlet) − − 905.896 ̂7 = 0.984

𝐻

C2H5COOH(l) (Inlet) 4.78 0 − −

C2H5COOH(l) (Outlet) − − 4.78 ̂3 = 0.6677

𝐻

H2O (l) (Inlet) 11.91 0 − −

H2O(v) (recycle) 2.7177 ̂15.2= 41.2282

𝐻 − −

H2O(v) (Outlet) − − 14.63 ̂17 = 40.8822

𝐻

383
̂15.1= ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻)(𝑙) 𝑑𝑇
378

383
= ∫370 0.1231𝑑𝑇

=1.6 kJ/mol

100 110
̂15.2= ∫
𝐻 𝐶𝑝(𝐻2 𝑂)(𝑙) 𝑑𝑇 +𝛥Hv(1000C) + ∫ 𝐶𝑝(𝐻2 𝑂)(𝑣) 𝑑𝑇
97 100

100
110

= ∫ 0.0754𝑑𝑇 + 40.656 + ∫ (33.46 × 10−3 + 0.688 × 10−5 𝑇)𝑑𝑇

100
97

= 0.2262+ 40.656+0.342

= 41.2282 kJ/mol
42
 378
̂7 = ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻)(𝐼) 𝑑𝑇
370

378
= ∫370 0.1231𝑑𝑇

=0.984 kJ/mol

378
̂3 = ∫
𝐻 𝐶𝑝(𝐶2𝐻5 𝐶𝑂𝑂𝐻)(𝑙) 𝑑𝑇
370

378
= ∫370 (0.1297 − 0.1263 × 10−3 𝑇) 𝑑𝑇

=0.6677

100 105
̂17 = ∫
𝐻 𝐶𝑝(𝐻2 𝑂)(𝑙) 𝑑𝑇 +𝛥Hv(1000C) + ∫ 𝐶𝑝(𝐻2 𝑂)(𝑣) 𝑑𝑇
97 100

100
110

= ∫ 0.0754𝑑𝑇 + 40.656 + ∫ (33.46 × 10−3 + 0.688 × 10−5 𝑇)𝑑𝑇

100
97

= 0.2262+ 40.656+0.1712

= 41.8822 kJ/mol

̂𝑖𝑛 -∑ 𝑛𝑖 𝐻
Q= 𝛥𝐻 = ∑𝑜𝑢𝑡 𝑛𝑖 𝐻 ̂𝑖𝑛
𝑖𝑛

=(905.896×0.984+4.78×0.6677+14.63×40.8822−6.3413×1.6−2.7177×41.2282) ×103
=1370.508×103 kJ/day
1370.508×103
= kJ/s
24×60×60

=15.86 kW

43
7.5 Energy Balance Around Heavy End Column: [26],[28],[29]

Figure 24: Balanced heavy end column

Reference: H2O (l), CH3COOH(l), C2H5COOH(l) at 250C and 1 atm

44
Table 5: Enthalpy Input-Output Table for Heavy End Column.

Component nin (kmol/day) ̂ 𝐢𝐧 (𝐤𝐉/𝐤𝐦𝐨𝐥)

𝐇 nout (kmol/day) ̂ 𝐨𝐮𝐭 (𝐤𝐉/𝐤𝐦𝐨𝐥)
𝐇

CH3COOHIn 905.896 28.096 ×103 - -

C2H5COOHIn 4.78 -3.754 ×103 - -

H2OIn 9.4 6.032 ×106 - -

CH3COOHRecycle - - 6.341 30.055 ×103

H2ORecycle - - 2.718 6.03 ×106

CH3COOHTop - - 899.554 33.242 ×103

H2OTop - - 6.341 6.298 ×106

C2H5COOHBottom - - 4.782 -4.172 ×103

H2OBottom - - 0.338 7.39 ×106

̂ in = 82.135 ×106 KJ/day

Σ ninH ̂ out = 88.896 ×106 KJ/day
Σ noutH

Assumptions:

Feed and bottom stream are assumed to be in liquid phase whereas top and recycle stream are
assumed to be in vapor phase. Negligible kinetic and potential energy change with no shaft
work present in the system. So the energy balance equation becomes Q = 𝛥𝐻

378
̂𝑖𝑛(𝐸𝐴) = ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻) 𝑑𝑇
298

378
= ∫298 (1.3964 × 102 + 3.208 × 10−1 𝑇 + 8.985 × 10−4 𝑇 2 ) 𝑑𝑇

= 28.096 ×103 kJ/kmol

383
̂𝑅(𝐸𝐴) = ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻) 𝑑𝑇
298

383
= ∫298 (1.3964 × 102 + 3.208 × 10−1 𝑇 + 8.985 × 10−4 𝑇 2 ) 𝑑𝑇

= 30.055 ×103 kJ/kmol

45
 391
̂𝑇(𝐸𝐴) = ∫
𝐻 𝐶𝑝(𝐶𝐻3 𝐶𝑂𝑂𝐻) 𝑑𝑇
298

391
= ∫298 (1.3964 × 102 + 3.208 × 10−1 𝑇 + 8.985 × 10−4 𝑇 2 ) 𝑑𝑇

= 33.242 ×103 kJ/kmol

378
̂𝑖𝑛(𝑃𝐴) = ∫
𝐻 𝐶𝑝(𝐶2 𝐻5 𝐶𝑂𝑂𝐻) 𝑑𝑇
298

378
= ∫298 (2.1366 × 10−3 𝑇 − 7.027 × 10−1 𝑇 + 1.6605 × 10−3 𝑇 2 ) 𝑑𝑇

= -3.754 ×103 kJ/kmol

396
̂𝐵(𝑃𝐴) = ∫
𝐻 𝐶𝑝(𝐶2𝐻5 𝐶𝑂𝑂𝐻) 𝑑𝑇
298

396
= ∫298 (2.1366 × 10−3 𝑇 − 7.027 × 10−1 𝑇 + 1.6605 × 10−3 𝑇 2 ) 𝑑𝑇

= -4.172 ×103 kJ/kmol

105
̂𝑖𝑛(𝑊) = ∫
𝐻 𝐶𝑝(𝐻2 𝑂) 𝑑𝑇
25

105
= ∫25 (75.4) 𝑑𝑇

= 6.032 ×106 kJ/kmol

123
̂𝐵(𝑊) = ∫
𝐻 𝐶𝑝(𝐻2 𝑂) 𝑑𝑇
25

123
= ∫25 (75.4) 𝑑𝑇

= 7.39 ×106 kJ/kmol

100 118
̂𝑇(𝑊) = ∫
𝐻 𝐶𝑃(𝐻 ̂𝑣
𝑑𝑇 + 𝛥𝐻 +∫ 𝐶𝑃(𝐻 𝑑𝑇
2 𝑂)𝑙 (𝐻
2 𝑂) 2 𝑂)𝑣
25 100

100 118
=∫25 75 ⋅ 4 𝑑𝑇 + 40.656 + ∫100 (33.46 + 0.688 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 −
3.593 × 10−12 𝑇 3 ) 𝑑𝑇

= 6.298 ×106 KJ/Kmol

46
 100 110
̂𝑅(𝑊) = ∫
𝐻 𝐶𝑃(𝐻 ̂𝑣
𝑑𝑇 + 𝛥𝐻 +∫ 𝐶𝑃(𝐻 𝑑𝑇
2 𝑂)𝑙 (𝐻
2 𝑂) 2 𝑂)𝑣
25 100

100 110
=∫25 75 ⋅ 4 𝑑𝑇 + 40.656 + ∫100 (33.46 + 0.688 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 −
3.593 × 10−12 𝑇 3 ) 𝑑𝑇

= 6.03 ×106 KJ/Kmol

Enthalpy of ethanoic acid input,

̂𝑖𝑛(𝐸𝐴)
𝐻𝑖𝑛(𝐸𝐴) = 𝑛16 𝐻

= 905 ⋅ 896 × 28.096 × 103 KJ/day

= 25.452 ×106 KJ/day

Enthalpy of propionic acid input,

̂𝑖𝑛(𝑃𝐴)
𝐻𝑖𝑛(𝑃𝐴) = 𝑛3 𝐻

= 4.78 × (−3.754 × 103 ) KJ/day

= -17.944 ×103 KJ/day

Enthalpy of water input,

̂𝑖𝑛(𝑊)
𝐻𝑖𝑛(𝑊) = 𝑛18 𝐻

= 9.4 × 6.032 × 106 KJ/day

= 56.7 ×106 KJ/day

Enthalpy of propionic acid in bottom product,

̂𝐵(𝑃𝐴)
𝐻𝐵(𝑃𝐴) = 𝑛𝐵(𝑃𝐴) 𝐻

= 0.934 × 5.12 × (−4.172 × 103 ) KJ/day

= -19.95 ×103 KJ/day

Enthalpy of water in bottom product,

̂𝐵(𝑊)
𝐻𝐵(𝑊) = 𝑛𝐵(𝑊) 𝐻
47
 = 0.066 × 5.12 × 7.39 × 106 KJ/day

= 2.497 ×106 KJ/day

Enthalpy of ethanoic acid in top product,

̂𝑇(𝐸𝐴)
𝐻𝑇(𝐸𝐴) = 𝑛𝑇(𝐸𝐴) 𝐻

= 905 ⋅ 896 × 0.993 × 33.242 × 103 KJ/day

= 29.903 ×106 KJ/day

Enthalpy of water in top product,

̂𝑇(𝑊)
𝐻𝑇(𝑊) = 𝑛𝑇(𝑊) 𝐻

= 905.896 × 0.007 × 6.298 × 106 KJ/day

= 16.387 ×106 KJ/day

Enthalpy of ethanoic acid in recycle stream,

̂𝑅(𝐸𝐴)
𝐻𝑅(𝐸𝐴) = 𝑛𝑅(𝐸𝐴) 𝐻

= 9.059 × 0.7 × 30.055 × 103 KJ/day

= 190.586 ×103 KJ/day

Enthalpy of water in recycle stream,

̂𝑅(𝑊)
𝐻𝑅(𝑊) = 𝑛𝑅(𝑊) 𝐻

= 9.059 × 0.3 × 6.03 × 106 KJ/day

= 190.586 ×103 KJ/day

Now,

̂𝑖𝑛 -∑ 𝑛𝑖 𝐻
Q= 𝛥𝐻 = ∑𝑜𝑢𝑡 𝑛𝑖 𝐻 ̂𝑖𝑛
𝑖𝑛

= 6.762 ×106 kJ/day

= 78.264 KW

48
8. Waste Management and Environment Impact
8.1 What is waste

Waste is defined as unwanted and unusable materials and substances that are not used by
their producer. Unwanted materials may be by-products of the manufacturing process, such
as fly ash from a furnace. However, the material may have value from someone else's point
of view. The waste we see around us is also known as garbage.[30]

8.2 Source of waste

Figure 25: Waste classification by origin. Different activities generate different types of waste[31]

8.3 Classification of waste

Waste can be classified Based on source, health, and environmental impact

Non-hazardous/solid waste
Non-hazardous is all waste that has not been classified as hazardous: paper, plastic, glass,
metal and beverage cans, organic waste, etc. Although not hazardous, solid waste can have a
serious impact on the environment and health if left uncollected and processed. [31&32]

49
Hazardous waste
Hazardous waste is waste that can cause damage to the environment and human health and
therefore requires special and separate treatment and handling. Chemical and physical
characteristics determine the exact collection and recycling process. Flammability,
corrosiveness, toxicity, ecotoxicity and explosiveness are the main characteristics of
hazardous waste. Liquid, gaseous and dust wastes require special treatment as a matter of
priority in order to prevent waste dispersion. Chemical treatment, incineration or high-
temperature treatment, safe storage, recovery and recycling are possible ways of treating
hazardous waste. The most hazardous wastes are generated from industrial production. They
are among the special types of hazardous waste. [31&32]

8.4 Waste released from acetic acid plant

Heavy metal is the main waste in the acetic acid production plants. Iridium metal is used as a
catalyst and iodine is used as a promotor. This two-element react with carbon monoxide and
form complex in different oxidation states of Iridium. Number of parallel reactions occur
during methanol carbonylation process and create a lot of by product. Such as methyl acetate
(CH3OOCCH3), Water (H2O), Hydrogen Iodide (HI), Dimethyl ether (CH3-O-CH3), Carbon
dioxide (CO2), Hydrogen (H2), Methane (CH4), propanoic acid (CH3CH2COOH),
acetaldehyde (CH3CHO). For a reactor 100% conversion is not possible so methanol and
carbon monoxide are also released from the plant.[22]
For maintain the specific temperature of the reactor fuel is burned. For this reason, a lot of
gas like SOX, NOX, CO and CO2 produced.
During separation process the by product is released from different type of column.
For cooling purposes, a lot of water is needed which is released as wastewater.

8.5 Environmental impact of the waste

Carbon dioxide, water vapor, methane, and nitrous oxide are greenhouse gases. These gases
cause global warming. Global warming is the gradual increase in the average temperature of
the earth's atmosphere because more energy is hitting the earth from the sun that is being
trapped in the atmosphere and not being released into space. Greenhouse gases are changing
the climate, which is slowly making our planet uninhabitable.
Sulfur dioxide is another waste that has a dangerous effect on the environment. When sulfur
dioxide combines with water and air, it forms sulfuric acid, which is the main component of
acid rain. Acid rain can:
✓ cause deforestation
✓ acidify waterways to the detriment of aquatic life
✓ corrode building materials and paints.
50
Sulfur dioxide also has health effects, affecting the respiratory system, especially lung
function, and can irritate the eyes. Sulfur dioxide irritates the respiratory tract and increases
the risk of infections. It causes coughing, and mucus production and aggravates conditions
such as asthma and chronic bronchitis.[33]
Carbon monoxide (CO), known as the Invisible Killer, is a colorless, odorless, poisonous gas
that released from acetic acid plants. Breathing air with high concentrations of carbon
monoxide reduces the amount of oxygen that can be carried in the bloodstream to vital organs
such as the heart and brain. At very high levels, such as indoors or in other enclosed
environments, CO can cause dizziness, confusion, unconsciousness, and death.[34]
Very high levels of CO are not likely to occur outdoors. However, when CO levels are
elevated outdoors, they can be of particular concern for people with some types of heart
disease. These people already have a reduced ability for getting oxygenated blood to their
hearts in situations where the heart needs more oxygen than usual. They are especially
vulnerable to the effects of CO when exercising or under increased stress. In these situations,
short-term exposure to elevated CO may result in reduced oxygen to the heart accompanied
by chest pain also known as angina.[34]
Methanol is less toxic to aquatic and terrestrial organisms, and the effects of environmental
exposure to methanol are not seen in spills. Methanol can affect animals, birds, and fish,
causing their death. Exposure may also result in reduced plant growth. Long-term exposure to
methanol can affect the fertility of biota and affect their appearance or behavior.[35]
Heavy metals enter the food chain and destroy ecosystems. Heavy metals also affect the
biodegradability of organic pollutants, making them less biodegradable and leading to the
double effect of environmental pollution. Iridium is a heavy metal used as a catalyst in the
production of acetic acid. These metal complexes are released into the environment with by-
products. As it is non-biodegradable, it easily enters the food chain. It poses a threat to
various types of aquatic animals, amphibians, fish, and terrestrial animals.[36]

51
Figure 26: Visual Impacts of Climate Change Evidence [37]

52
8.6 Waste Management

In simple terms, it can be defined as the collection, transport, and disposal of garbage,
sewage, and other waste materials. The process of waste management includes the
management of solid and liquid waste. During handling, it also offers different solutions to
recycle items that are not classified as waste. Thus, the whole concept boils down to
recycling waste as a valuable resource, and considering our current environmental climate,
this process is crucial for all households and businesses.
Carbon monoxide is more dangerous than carbon dioxide. Therefore, if carbon monoxide is
oxidized to carbon dioxide, the bad effects on the environment will be reduced. Iridium
complex compounds cannot be discharged directly into rivers. This metal complex should be
buried in the ground outside the locality. Methanol is very toxic. So, it must be recycled.
Methanol vapor can be absorbed by water and used later.
ETP plant must be established in the production and which can reduce the toxicity of the
gases and by using catalyst metal can be converted with less hazardous compound.
Utility plant is also an important part of every chemical industry. This plant treated the
wastewater and convert it to drinkable water. This water uses for different purposes.
Wastewater can also be use process heating.

Figure 27: Waste Management procedure

53
8.7 The Benefits of Waste Management

Better Environment
Perhaps the biggest advantage of waste management is that it ultimately leads to a better and
newer environment. Landfills also contribute to people's livelihood by helping them to avoid
diseases. The best part: all this happens when the unnecessary is disposed of properly and
hygienically.[38]
Reduces Pollution
When waste is treated properly, it not only eliminates the next waste but also reduces the
impact and concentration of harmful greenhouse gases such as carbon dioxide, carbon
monoxide and methane that are often released from waste. collected in the trash. Waste
management reduces our dependence on garbage and also greatly reduces the number of
items that have a negative impact on our environment.[38]
Creates Employment
Recycling is one of the biggest aspects of waste management and helps save energy over
time. One of the greatest examples of this benefit can be traced back to paper recycling
practices.[38]

54
9. Conclusion:
Acetic acid has been closely associated with human civilization since a long time. It is an
important chemical building block used for the production of several chemical entities. The
innovation and establishment of different new chemical industries demand for a larger
production of acetic acid. An expansion of acetic acid manufacturing plant would require
more sustainable and eco-friendly solutions to the prevalent drawbacks within the process.
The demand for acetic acid can be met by developing more efficient and sophisticated
separation and recovery process. Since the raw materials for the process can be sourced from
syngas, there is an opportunity for the process to become more eco-friendly by utilising the
syngas by-products. The energy balance also revealed that a huge amount of heat is produced
in the reactor. This waste heat has potential to be recovered and reused in process heating or
other applications making the process more cost-effective. The modern food industry could
also be benefitted with a more sophisticated and high-capacity fermentative production
process for vinegar production. Overall, the acetic acid manufacture plant possesses potential
to become a high-impact chemical plant with sustainable production pathways.

55
10. References:
1. Brown, William H.. "acetic acid". Encyclopedia Britannica, 5 Feb. 2020,
https://www.britannica.com/science/acetic-acid. Accessed 14 August 2022.
2. Deshmukh, Gunjan P. and Haresh G. Manyar. “Production Pathways of Acetic Acid and Its
Versatile Applications in the Food Industry.” Biotechnological Applications of Biomass (2021):
n. pag.
3. Solieri, Lisa; Giudici, Paolo (2009). Vinegars of the World || . , 10.1007/978-88-470-0866-3(), –.
doi:10.1007/978-88-470-0866-3
4. Cheung, H., Tanke, R.S. and Torrence, G.P. (2011). Acetic Acid. In Ullmann's Encyclopedia of
Industrial Chemistry, (Ed.). https://doi.org/10.1002/14356007.a01_045.pub2
5. Maitlis, Peter M.; Haynes, Anthony; Sunley, Glenn J.; Howard, Mark J. (1996). Methanol
carbonylation revisited: thirty years on. Journal of the Chemical Society, Dalton Transactions,
(11), 2187–. doi:10.1039/DT9960002187
6. Medrano-García, J. D., Ruiz-Femenia, R., & Caballero, J. A. (2019). Revisiting Classic Acetic
Acid Synthesis: Optimal Hydrogen Consumption and Carbon Dioxide Utilization. 29th European
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