CH4016 – Comprehensive Design Project I
Process Analysis
Group 10 - Acetic Acid Production Process
Supervised by: Dr. Mahinsasa Rathnayake
Group Members: 200217B – HETTIGE S.H.
180145X – DILSHAN B.G.T.
200632R – SUVETHIGA J.
200562C – SAMARASIRI Y.M.A.C.
200761K – MADHUSANKA M.K.A.
Department of Chemical & Process Engineering
University of Moratuwa
Table of Contents
Introduction .....................................................................................................................3
Process Pathways .............................................................................................................4
Methanol Carbonylation ......................................................................................................... 4
Aldehyde Oxidation ................................................................................................................ 5
Hydrocarbon Oxidation .......................................................................................................... 5
Submerged Fermentation Route ............................................................................................. 5
Methanol Carbonylation ...................................................................................................6
Monsanto Process ................................................................................................................... 7
Cativa process......................................................................................................................... 9
Process Flow Diagrams ..................................................................................................12
Introduction
Acetic acid, also known as ethanoic acid, is a colorless liquid with a pungent, vinegar-like odor.
It's a fundamental organic acid, containing a carboxylic acid group (COOH) that gives it its
acidic properties. Acetic acid as the key component of vinegar, which is typically a 4% solution
of acetic acid in water. [1]
Chemical Properties:
• Formula: CH₃COOH (or C₂H₄O₂)
• Melting Point: 16-17 °C
• Boiling Point: 118 °C
• Pungent odour
• Corrosive in concentrated forms
Uses of Acetic Acid[2]
Food Industry: Acetic acid is a crucial ingredient in the production of vinegar, which is used
extensively in cooking, food preservation, and flavor enhancement.
Chemical Industry: It serves as a versatile chemical intermediate in the synthesis of numerous
chemicals, including acetate esters, acetic anhydride, and vinyl acetate monomer.
Cleaning and Disinfecting: Due to its antibacterial properties, acetic acid is used in household
cleaning products, particularly for surfaces and windows, where it effectively removes stains
and disinfects.
Medical Applications: In medicine, acetic acid finds use in otic solutions for treating ear
infections caused by bacteria and fungi.
Laboratory Applications: Acetic acid is a common solvent and reagent in laboratories for
various chemical reactions and extractions. It is also used in analytical chemistry as a standard
for titrations.
Process Pathways
Acetic acid is a key component in the global chemical industry due to its use in wide range of
applications. Hence, the demand for acetic acid remains at considerably large quantities [3]. In
order to achieve this demand and thereby forego any mismatch in supply and demand, acetic
acid is synthesised through numerous process pathways by various manufacturers. Notably,
process pathway is also dependent on the end application of the synthesised acetic as well. It
was identified that acetic acid is primarily manufactured through following for pathways [3],
[4].
1. Methanol Carbonylation
2. Aldehyde Oxidation Chemical Synthesis
3. Hydrocarbon Oxidation
4. Submerged Fermentation - Fermentation Process
Methanol Carbonylation
This chemical process path of manufacturing acetic acid is the most widely followed pathway
industrially across the globe for manufacturing acetic acid [4]. Key reaction of the process is
as follows.
150−200 ℃
30−50 𝑏𝑎𝑟
𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 + 𝐶𝑎𝑟𝑏𝑜𝑛 𝑚𝑜𝑛𝑜𝑥𝑖𝑑𝑒 → 𝐴𝑐𝑒𝑡𝑖𝑐 𝐴𝑐𝑖𝑑 + 𝐹𝑜𝑟𝑚𝑖𝑐 𝐴𝑐𝑖𝑑 + 𝐹𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
Various types of catalysts are utilized to enhance the rate of production of acetic acid. Summary
of the advantages and disadvantages of this process pathway is as follows.
Advantages: High conversion rates are observed compared to other pathways.[5][6][7]
Process is comparatively cost effective and enables for process flexibility to
optimize the production.[8]
Significantly high temperatures and pressures are not required which drives
down the utility cost.
Disadvantages: Significant costs must be incurred for acquiring the catalysts required.[9]
Catalyst recovery is complex.
Poses significant threat to the environment.[10][11]
Aldehyde Oxidation
Typically, acetaldehyde is utilized as the raw material in this process which is then oxidized to
yield acetic acid. This is carried out in the presence of metallic catalyst and at the operating
temperature of 150 ºC and a pressure of 55 bar. [3][4]
150 ℃
55−60 𝑏𝑎𝑟 𝐴𝑐𝑒𝑡𝑖𝑐 𝐹𝑜𝑟𝑚𝑖𝑐 𝐸𝑡ℎ𝑦𝑙
𝐴𝑐𝑒𝑡𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 + 𝑂𝑥𝑦𝑔𝑒𝑛 → + + 𝐹𝑜𝑟𝑚𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 +
𝐴𝑐𝑖𝑑 𝐴𝑐𝑖𝑑 𝐴𝑐𝑒𝑡𝑎𝑡𝑒
Strengths and shortcomings of this process are discussed below.
Advantages: High conversion rates similar to that of Methanol Carbonylation method.
Potential for by-product utilization exists.
Disadvantages: Safety concerns take precedence as significantly high pressures are involved.
Poses a threat to environment with the generated waste.
Significant purification costs are involved to ensure the purity of the product.
Hydrocarbon Oxidation
Primarily, petroleum stocks such as butane and naphtha are used as raw materials in this process
to produce acetic acid. Due to the formation of other by-products such as acetone, formic acid,
propionic acid, pure acetic acid cannot be obtained in an economically feasible manner (). Key
reaction involved is given below.[9][3][12]
150−230 ℃
55−60 𝑏𝑎𝑟
𝐵𝑢𝑡𝑎𝑛𝑒 + 𝑂𝑥𝑦𝑔𝑒𝑛 → 𝐴𝑐𝑒𝑡𝑖𝑐 𝐴𝑐𝑖𝑑 + 𝐹𝑜𝑟𝑚𝑖𝑐 𝐴𝑐𝑖𝑑 + 𝑃𝑟𝑜𝑝𝑖𝑜𝑛𝑖𝑐 𝐴𝑐𝑖𝑑
Advantages: Availability of feedstock.[13]
Relatively less complex compared to other chemical synthesis routes.
Disadvantages: Comparatively less yield is obtained.[14]
High pressures are involved which is a safety concern.
Submerged Fermentation Route
One of the key applications of acetic acid is in the food industry as Vinegar. Acetic acid utilized
in the food industry is primarily produced through fermentation of ethanol using Acetobacter
bacteria in a Frings Acetator[4][15][16]. Key reaction pathway is given below.
𝐸𝑡ℎ𝑎𝑛𝑜𝑙 → 𝐴𝑐𝑒𝑡𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 → 𝐴𝑐𝑒𝑡𝑖𝑐 𝐴𝑐𝑖𝑑
Advantages: High levels of yield. [4]
Does not produce toxic waste. [16]
Expensive catalysts are not required.
Disadvantages: Requires cooling as the process generates considerable amount of heat. [4][17]
Scalability issues stemming from the unavailability of suitable
bacteria.[18][19]
Quality constraints of substrates.[19]
By considering forementioned advantages and disadvantages of each process pathway,
Methanol Carbonylation is selected as the process path for the plant in the design phase.
Comprehensive evaluation will be included in the interim report 1.
Methanol Carbonylation
Methanol carbonylation process is an industrial method that is considered as a more efficient
way to produce acetic acid (CH₃COOH) by reacting methanol (CH₃OH) with carbon monoxide
(CO) in the presence of a catalyst. Methanol and carbon monoxide are reacted in the liquid
phase in the presence of a catalyst at 150-200°C temperature and 30-50 bar pressure to produce
acetic acid with 95% selectivity and 5% side products such as formic acid and formaldehyde
[3]. This process gained prominence with the development of the Monsanto process in the
1960s and was later refined by the Cativa process introduced by BP Chemicals in the 1990s.
Summary of the key reactions taking place is given below.
150−200 ℃
30−50 𝑏𝑎𝑟
𝐶𝐻3 𝑂𝐻 + 𝐶𝑂 → 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶𝑂𝑂𝐻 + 𝐶𝐻2 𝑂
The primary key reactions involved in the methanol carbonylation process are as follows:
1. Formation of Methyl Iodide:
CH3OH + HI → CH3I + H2O
2. Carbonylation:
CH3I + CO → CH3COI
3. Hydrolysis:
CH3COI + H2O → CH3COOH + HI
Figure 1: Methanol Carbonylation Reaction Scheme[8]
However, Methanol Carbonylation pathway is also practiced under two different process as
Monsanto Process and Cativa Process based on the catalyst used,
Monsanto Process
The Monsanto process, a landmark achievement in the chemical industry, revolutionized acetic
acid production by introducing a highly efficient and selective catalytic method. Developed in
the 1960s by the Monsanto company, it replaced the traditional fermentation process, which
was slow, inefficient, and prone to contamination.
The Monsanto process, a revolutionary advancement in acetic acid production, stands out for
its highly efficient and selective catalytic approach. It utilizes a homogeneous catalyst,
meaning the catalyst is dissolved within the reaction mixture, allowing for intimate contact
between the catalyst and reactants, leading to rapid reaction rates. The heart of the process lies
in a rhodium-based catalyst, specifically [Rh(CO)2I2]-, which exhibits exceptional activity and
selectivity for the carbonylation of methanol.
To achieve high conversion rates, the process operates under high pressure (30-60 atm) and
temperature (150-200°C). Methyl iodide (CH3I) plays a crucial role as a promoter, facilitating
the formation of the active rhodium species and maintaining the catalytic cycle[20].
Key reactions
Acetic acid formation reaction
1. Methanol Carbonylation: Methanol reacts with carbon monoxide in the presence of
the rhodium catalyst to form methyl iodide (CH3I).
2. Oxidative Addition: The methyl iodide undergoes oxidative addition to the rhodium
catalyst, forming a rhodium-methyl complex.
3. Carbonylation: Carbon monoxide inserts into the rhodium-methyl bond, forming a
rhodium-acetyl complex.
4. Reductive Elimination: The rhodium-acetyl complex undergoes reductive
elimination, releasing acetic acid and regenerating the rhodium catalyst.
When the water content is high (8%), the rate-determining step in the process is to add the
oxidant methyl iodide to the rhodium center. Then the reaction is first order in both
[Rh(CO)2I2]- and CH3I concentrations, and independent of other concentration and
parameters. But when water content is lower than 8%, rate determination reaction is reductive
elimination reaction.
Water gas shift reaction
In the Monsanto process, the water shifted reaction is a side reaction which reduces the reaction
rate and yield. In the presence of rhodium, the reaction between H 2O and CO takes place.
[Rh(CO)2I2]- + 2HI → [Rh(CO)2I4]- + H2
[Rh(CO)2I4]- + H2O + CO → [Rh(CO)2I2]- + CO2 + 2HI
Overall reaction:
H2O + CO → CO2 + H2
So, water gas shifted reaction minimizes the CO and gases byproduct dilute the present CO in
the reactor, that reduces the main reaction as well as yield of the production.
Formation of propanoic acid
The presence of ethanol in methanol mixture as an impurity, ethanol form propanoic acid with
the support of Rhodium catalyst. But the accounted propanoic acid amount is higher than the
expected amount. Which shows that the raw material (methanol) is consumed to produce
propanoic acid.
Formation of acetaldehyde
Rhodium-acyl reacts with HI acetaldehyde and [RhI 4CO]-. That causes the loss of catalyst in
the process. That also reduces the yield of acetic acid production.
[RhI3(CO)(COCH3)]- + HI → [RhI4(CO)2I4]- + CH3CHO
[RhI4(CO)2I4]- → RhI3 + I- + CO
Advantages
• High conversion rates: The process achieves high conversion rates of methanol to acetic
acid, maximizing efficiency and minimizing wastage.
• Mild reaction conditions: Compared to conventional methods, the Monsanto process
operates under relatively mild conditions, reducing energy consumption and
minimizing environmental impact.
Disadvantages
• Catalyst Cost: Since rhodium is a precious metal, the catalyst is expensive.
• Catalyst Deactivation: Rhodium catalysts can become inactive over time, requiring
periodic replacement or regeneration.
• Water Gas Shift Reaction: Rhodium catalyst can catalyze the water gas shift reaction
which consumes carbon monoxide and generates carbon dioxide. This reduces the
overall efficiency of the process.
Cativa process
The Cativa process, developed by BP Chemicals in the late 1990s, offers significant
improvements in efficiency, cost-effectiveness and environmental friendliness.
The Cativa process uses a unique catalyst system based on iridium, a more stable metal than
the rhodium used in the Monsanto process. This allows for operation at lower water
concentrations, leading to reduced energy consumption and improved catalyst stability. The
Cativa process typically operates at temperatures similar to the Monsanto process (around 180-
200°C). Furthermore, the Cativa process utilizes promoters that enhance the iridium catalyst’s
performance, resulting in higher reaction rates and a higher yield on carbon monoxide[21].
Key reactions
Figure 2: Cativa Process Reaction Scheme
Catalytic Cycle
• Active Catalyst: The primary active catalyst species is [Ir(CO)2I3Me]-, an anionic
iridium complex.
• Oxidative Addition: The cycle begins with the oxidative addition of methyl iodide
(Mel) to the iridium center, forming an iridium-methyl complex.
• Carbon Monoxide Insertion: Carbon monoxide (CO) then inserts into the Ir-Me bond,
forming an acyl complex.
• Reductive Elimination: The acyl complex undergoes reductive elimination, releasing
acetic acid (CH3COOH) and regenerating the active catalyst [Ir(CO)2I3Me]-.
Research shows that oxidation addition reaction rate is 150 times faster than the Monsanto
method which implies the high reaction rate should be achieved at low iodide concentrations
[21]. Using Iodide capturing promoters, the bottleneck of Iodide concentration can be
prevented through the process.
Eg: Simple iodide complexes of zinc, cadmium, mercury, gallium and indium
: Carbonyl-iodide complexes of tungsten, rhenium, ruthenium and osmium
Promoters,
• Increase activity of catalyst
• Stabilizing active species
• Facilitating CO Insertion
• Preventing Catalyst Deactivation
• Reducing Catalyst Poisoning
• Enhanced Selectivity
Advantages
• Higher reaction rate compared to Monsanto process.
• Lower water content compared to Monsanto process
o Reduce by-product formation: methyl acetate
o Increase catalyst stability and expand lifetime of catalyst.
o Reduce energy consumption.
• More Environmentally Friendly
o Lower by-product formation reduces environmental impact.
o Lower energy consumption reduces carbon footprint.
• Lower operating cost
o Compared with Monsanto process, lower operating cost due to the lower by-product
formation and lower process steps.
• Improved safety
o Operating at low pressure compared to the Monsanto process.
Disadvantages
• Potential for corrosion
• Sensitive to impurities; sulfur and nitrogen compounds, which can deactivate the
catalyst.
Importantly in Cativa process, due to the low water content that reduces the downstream
process which in turn reduces the number of distillation column or capacity of distillation
columns.
Compared with the above advantages and disadvantages most preferable method for acetic acid
production is Cativa process.
Process Flow Diagrams
References
[1] Kirk‐Othmer Encyclopedia of Chemical Technology. Wiley, 2000. doi:
10.1002/0471238961.
[2] H. Ebner, “l 2 Acetic Acid.”
[3] P. Pal and J. Nayak, “Acetic Acid Production and Purification: Critical Review
Towards Process Intensification,” Separation and Purification Reviews, vol. 46, no. 1.
Taylor and Francis Inc., pp. 44–61, Jan. 02, 2017. doi:
10.1080/15422119.2016.1185017.
[4] G. Deshmukh and H. Manyar, “Production Pathways of Acetic Acid and Its Versatile
Applications in the Food Industry,” in Biotechnological Applications of Biomass,
IntechOpen, 2021. doi: 10.5772/intechopen.92289.
[5] A. Haynes, “Catalytic Methanol Carbonylation,” in Advances in Catalysis, vol. 53, no.
C, 2010, pp. 1–45. doi: 10.1016/S0360-0564(10)53001-3.
[6] J. H. Jones, “The Cativa’"’ Process for the Manufacture Plant of Acetic Acid Location
Year Debottlenecking or increased throughput achieved, % IRIDIUM CATALYST
IMPROVES PRODUCTIVITY IN AN ESTABLISHED INDUSTRIAL PROCESS.”
[7] G. J. Sunley and D. J. Watson, “High productivity methanol carbonylation catalysis
using iridium The Cativa TM process for the manufacture of acetic acid,” 2000.
[8] P. M. Maitlis, A. Haynes, G. J. Sunleyb, and M. J. Howardb, “Methanol carbonylation
revisited: thirty years on*,” 1996.
[9] N. Yoneda, S. Kusano, M. Yasui, P. Pujado, and S. Wilcher, “Recent advances in
processes and catalysts for the production of acetic acid,” 2001.
[10] F. Li, B. Chen, Z. Huang, T. Lu, Y. Yuan, and G. Yuan, “Sustainable catalysts for
methanol carbonylation,” Green Chemistry, vol. 15, no. 6, pp. 1600–1607, 2013, doi:
10.1039/c3gc00024a.
[11] J. L. Martín-Espejo, J. Gandara-Loe, J. A. Odriozola, T. R. Reina, and L. Pastor-Pérez,
“Sustainable routes for acetic acid production: Traditional processes vs a low-carbon,
biogas-based strategy,” Science of the Total Environment, vol. 840. Elsevier B.V., Sep.
20, 2022. doi: 10.1016/[Link].2022.156663.
[12] M. Soliman, Y. Al-Zeghayer, A. S. Al-Awadi, and S. Al-Mayman, “Economics of
Acetic Acid Production by Partial Oxidation of Ethane,” APCBEE Procedia, vol. 3,
pp. 200–208, 2012, doi: 10.1016/[Link].2012.06.070.
[13] J. L. Martín-Espejo, J. Gandara-Loe, J. A. Odriozola, T. R. Reina, and L. Pastor-Pérez,
“Sustainable routes for acetic acid production: Traditional processes vs a low-carbon,
biogas-based strategy,” Science of the Total Environment, vol. 840. Elsevier B.V., Sep.
20, 2022. doi: 10.1016/[Link].2022.156663.
[14] P. Pal and J. Nayak, “Acetic Acid Production and Purification: Critical Review
Towards Process Intensification,” Separation and Purification Reviews, vol. 46, no. 1.
Taylor and Francis Inc., pp. 44–61, Jan. 02, 2017. doi:
10.1080/15422119.2016.1185017.
[15] C. Hidalgo et al., “Effect of barrel design and the inoculation of Acetobacter
pasteurianus in wine vinegar production,” Int J Food Microbiol, vol. 141, no. 1–2, pp.
56–62, Jun. 2010, doi: 10.1016/[Link].2010.04.018.
[16] B. Ndoye, S. Lebecque, J. Destain, A. T. Guiro, and P. Thonart, “A new pilot plant
scale acetifier designed for vinegar production in Sub-Saharan Africa,” Process
Biochemistry, vol. 42, no. 11, pp. 1561–1565, Nov. 2007, doi:
10.1016/[Link].2007.08.002.
[17] K. K. Rosada, “Enhanced acetic acid production from manalagi apple (Malus
sylvestris mill) by mixed cultures of Saccharomyces cerevisiae and Acetobacter aceti
in submerged fermentation,” in Journal of Physics: Conference Series, Institute of
Physics Publishing, May 2018. doi: 10.1088/1742-6596/1013/1/012171.
[18] Z. Wang et al., “Mixed culture of Saccharomyces cerevisiae and Acetobacter
pasteurianus for acetic acid production,” Biochem Eng J, vol. 79, pp. 41–45, Oct.
2013, doi: 10.1016/[Link].2013.06.019.
[19] K. Witjitra, M. M. Shah, and M. Cheryan, “Effect of nutrient sources on growth and
acetate production by Clostridium thermoaceticum.”
[20] G. J. Sunley and D. J. Watson, “High productivity methanol carbonylation catalysis
using iridium,” Catal Today, vol. 58, no. 4, pp. 293–307, May 2000, doi:
10.1016/S0920-5861(00)00263-7.
[21] J. H. Jones, “The CativaTM Process for the Manufacture of Acetic Acid,” Platin Met
Rev, vol. 44, no. 3, pp. 94–105, Jul. 2000, doi: 10.1595/003214000X44394105.