Acetica

1.
INTRODUCTION
At the present time, Acetic Acid is used by chemical industries for produce many chemicals.
For example, it’s used for making cellulose acetate, polyvinyl acetate, white lead and acidity
regulators for food industry. That is to say this chemical is very important for produce
chemical compounds that using at many side of life.
The aim of this assigment is giving information about physicochemical properties of Acetic
Acid, market survey that includes production capacities and import & export datas,
availability of raw materials, capacities and prices in the world, flow diagram, mass and heat
balances of the system.
Today, there are five main producing technologies for Acetic Acid in the world. These are
methanol carbonylation, acetaldehyde oxidation, ethylene oxidation, oxidative
fermentation and anaerobic fermentation. Most Acetic Acid is produced by
methanol carbonylation.
This report includes detailed examination of Chiyoda ACETICA, material and energy
balance of all system.
2. PHYSICOCHEMICAL DATA
2.1. METHANOL
Physical Properties of Methanol
Methanol, also called Methyl Alcohol, it is the simplest of a long series of organic compounds
called alcohols; its molecular formula is CH 3 OH. The modern method of preparing methanol
is based on the direct combination of carbon mooxide gas and hydrogen in the presence of a
catalyst at elevated temperatures and pressures. Most methanol is produced from the methane
component of natural gas [1].
Methanol is a colorless liquid, completely miscible with water and organic solvents and is
very hygroscopic. It boils at 64.96 o C and solidifies at – 93.9 o C. It forms explosive mixtures
with air and burns with a nonluminious flame. It is a violent poison; drinking mixtures
containing methanol has caused many cases of blindness or death. Methanol has a settled
odor. Methanol is a potent nerve poison. Key physical properties are;
Melting Point : -97.7 0C
Boiling Point : 65 0C
Relative Density : 0.79
Formula: CH3OH
Molecular weight: 32.042 kg/kmol
Heat of Formation -201.3 MJ/kmol
Gibbs Free Energy -162.62 MJ/kmol
Freezing point: -97.7 °C
Boiling point: 64.6 °C (at atmospheric pressure)
Critical properties:
Critical temperature 512.6 K
Critical pressure 81 bar abs
Critical volume 0.118 m³/kmol
Liquid Properties:
Density 791 kg/m³ at 20 °C
Heat of Vaporization 35278 kJ/kmol
Viscosity:
a = 555.3 b = 260.6
where log(viscosity) = a * ( 1/T - 1/b )
viscosity: mNs/m² T: °K
Vapor Properties:
Heat capacity:
a = 21.152 b = 0.07092 c = 2.59E-05 d = -2.85E-08
where Cp = a + b*T + c*T² + d*T³
Cp: kJ/kmol.K T: °K
Vapour pressure:
a = 18.5875 b = 3626.55 c = -34.29
where ln(P) = a - b/(T+c) P: mmHg; T: °K
within range -16 to 91°C [1]

Chemical properties of Methanol
Combustion of Methanol:
Methanol burns with a pale-blue, non-luminous flame to form carbon dioxide and steam.
2CH3OH + 3O2 ===> 2CO2 + 4H2O
Oxidation of Methanol:
Methanol is oxidized with acidified Potassium Dichromate, K2Cr2O7, or with acidified

Sodium Dichromate, Na2Cr2O7, or with acidified Potassium Permanganate, KMnO4, to form
formaldehyde.
[O]
CH3OH ===> HCHO + H2
Methanol Formaldehyde
2H2 + O2 ===> 2H2O
If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic acid and
then to carbon dioxide and water.
[O] [O]
HCHO ===> HCOOH ===> CO2 + H2O
Formaldehyde Formic Acid
Catalytic Oxidation of Methanol:

The catalytic oxidation of methanol using platinum wire is of interest as it is used in model
aircraft engines to replace the sparking plug arrangement of the conventional petrol engine.
The heat of reaction is sufficient to spark the engine.
Dehydrogenation of Methanol:
Methanol can also be oxidized to formaldehyde by passing its vapor over copper heated to
300 °C. Two atoms of hydrogen are eliminated from each molecule to form hydrogen gas and
hence this process is termed dehydrogenation.
300°C ,Cu
CH3OH ===> HCHO + H2
Methanol Formaldehyde
Dehydration of Methanol:
Methanol does not undergo dehydration reactions. Instead, in reaction with sulphuric acid the
ester, dimethyl sulphate is formed [1].
concentrated
H2SO4
2 CH3OH ===> (CH3)2SO4 + H2O
Methanol Dimethyl Water
Sulphate
Esterification of Methanol
Methanol reacts with organic acids to form esters.
H(+)
CH3OH + HCOOH ===> HCOOCH3 + H2O
Methanol Formic Methyl Water
Acid Formate
Substitution of Methanol with Sodium

Methanol reacts with sodium at room temperature to liberate hydrogen. This reaction is
similar to the reaction of sodium with ethanol.
2 CH3OH + 2 Na ===> 2CH3ONa + H2

Methanol Sodium Sodium Methoxide Hydrogen
Substitution of Methanol with Phosphorus Pentachloride
Methanol reacts with phosphorus pentachloride at room temperature to form hydrogen

chloride, methyl chloride, (i.e. chloroethane) and phosphoryl chloride.
CH3OH + PCl5 ===> HCl + CH3Cl + POCl3

Methanol Phosphorus Hydrogen Methyl Phosphoryl
Pentachloride Chloride Chloride Chloride
Substitution of Methanol with Hydrogen Chloride
Methanol reacts with hydrogen chloride to form methyl chloride (i.e. chloromethane) and
water. A dehydrating agent (e.g. zinc chloride) is used [1].
ZnCl2
CH3OH + HCl ===> CH3Cl + H2O
Methanol Methyl Chloride
2.2. ACETIC ACID
The acid most commonly associated with vinegar, it is the most commercially important
organic acid and is used to manufacture a wide range of chemical products, such as plastics
and acetobacter but, except for making vinegar, is usually made through synthetic processes.
Derivatives of acetic acid which may be formed by substitution reactions. Synonym: ethanoic
acid. A colorless pungent liquid widely used in manufacturing plastics and pharmaceuticals.A
transparent liquid that is part of vinegar, that gives it its characteristic smell [2].
Acetic, or ethanoic, acid is a colorless, corrosive weak acid that freezes into a crystalline solid
at below 16.7 degrees celcius. Its scientific formula is CH3OOO. It is what gives vinegar its
taste and smell. It is also the weakest of carboxylic acids.
Physical Properties of Acetic Acid
Specific heat capacity :

Gaseous acid, cp 1.110 J g−1 K−1 at 25 ◦C
Liquid acid, cp 2.043 J g−1 K−1 at 19.4 ◦C
Crystalline acid, cp 1.470 J g−1 K−1 at 1.5 ◦C
0.783 J g−1 K−1 at −175.8 ◦C
Heat of fusion : 195.5 J/g
Heat of combustion : −874.2 kJ/mol at 20 ◦C
Cryoscopic constant : −269.56 ◦C
Ebullioscopic constant : 270.62 ◦C
Melting point : 6.76 ◦C
Triple-point temperature : 16.93 ◦C
Boiling point : 118.0 ◦C at 101.3 kPa
Density : 1265.85 kg/m3 (solid at mp)
Viscosity : 11.83mPa ・ s at 20◦C
10.97mPa ・ s at 25◦C
8.18mPa ・ s at 40◦C
0.067mPa ・ s at critical point
Dielectric constant : 6.194 at 20 ◦C
Dipole moment : 5.804×10−30 C・m
Electrolyte conductivity : 112.0 pS/m
Refractive index : D 1.372
Enthalpy of formation :
ΔH0 (l, 25 ◦C) −484.50 kJ/mol
ΔH0 (g, 25 ◦C) −432.25 kJ/mol
Normal entropy :
S ◦ (l, 25 ◦C) 159.8 Jmol−1 K−1
S ◦ (g, 25 ◦C) 282.5 Jmol−1 K−1
Flash point :
43 ◦C (closed cup)
57 ◦C (open cup)
Autoignition point : 465 ◦C
Flammability : 4.0 to 16.0 vol % in air
Critical data
pc 5.786MP a
Tc 321.45 ◦C [3].
Chemical properties of Acetic Acid
Acidity
The hydrogen center in the carboxyl group (−COOH) in carboxylic acids such as acetic acid
can separate from the molecule by ionization:
CH3CO2H → CH3CO2- + H+
Because of this release of the proton (H+), acetic acid has acidic character. Acetic acid is a
weak monoprotic acid. In aqueous solution, it has a pKa value of 4.75. Its conjugate base is
acetate (CH3COO−). A 1.0 M solution (about the concentration of domestic vinegar) has
a pH of 2.4, indicating that merely 0.4% of the acetic acid molecules are dissociated.
Cyclic dimer of acetic acid; dashed lines represent hydrogen bonds

Structure
In solid acetic acid, the molecules form pairs (dimers), being connected by hydrogen bonds.
The dimers can also be detected in the vapour at 120 °C(248 °F). Dimers also occur in the
liquid phase in dilute solutions in non-hydrogen-bonding solvents, and a certain extent in pure
acetic acid, but are disrupted by hydrogen-bonding solvents. The dissociation enthalpy of the
dimer is estimated at 65.0–66.0 kJ/mol, and the dissociation entropy at 154–
157 J mol−1 K−1. This dimerisation behaviour is shared by other lower carboxylic acids.
Solvent properties
Liquid acetic acid is a hydrophilic (polar) protic solvent, similar to ethanol and water. With a
moderate relative static permittivity (dielectric constant) of 6.2, it dissolves not only polar
compounds such as inorganic salts and sugars, but also non-polar compounds such as oils
and elements such as sulfur andiodine. It readily mixes with other polar and non-
polar solvents such as water, chloroform, and hexane. With higher alkanes (starting
with octane), acetic acid is not completely miscible anymore, and its miscibility continues to
decline with longer n-alkanes. This dissolving property and miscibility of acetic acid makes it
a widely used industrial chemical. Its solvent properties are mainly of value in the production
of dimethyl terephthalate.
Chemical reactions
Acetic acid undergoes the typical chemical reactions of a carboxylic acid. Upon treatment
with a standard base, it converts to metal acetate and water. With strong bases, it can be
doubly deprotonated to give LiCH2CO2Li. Reduction of acetic acid gives ethanol. The OH
group is the main site of reaction, as illustrated by the conversion of acetic acid to acetyl
chloride. Other substitution derivatives include acetic anhydride; thisanhydride is produced
by loss of water from two molecules of acetic acid. Esters of acetic acid can likewise be
formed via Fischer esterification, andamides can be formed. When heated above 440
°C (824 °F), acetic acid decomposes to produce carbon dioxide and methane, or to
produce ketene and water [4].
Reactions with inorganic compounds
Acetic acid is mildly corrosive to metals including iron, magnesium, and zinc,
forming hydrogen gas and salts called acetates:
Mg + 2 CH3COOH → (CH3COO)2Mg + H2
Because aluminium forms a passivating acid-resistant film of aluminium oxide, aluminium

tanks are used to transport acetic acid. Metal acetates can also be prepared from acetic acid
and an appropriate base, as in the popular "baking soda + vinegar" reaction:
NaHCO3 + CH3COOH → CH3COONa + CO2 + H2O
A colour reaction for salts of acetic acid is iron(III) chloride solution, which results in a
deeply red colour that disappears after acidification. Acetates when heated witharsenic
trioxide form cacodyl oxide, which can be detected by its malodorous vapours.
Biochemistry
At physiological pHs, acetic acid is usually fully ionized to acetate. In biochemistry, acetate
and acetic acid are equivalent.
The acetyl group, derived from acetic acid, is fundamental to all forms of life. When bound
to coenzyme A, it is central to the metabolism of carbohydrates and fats. Unlike longer-chain
carboxylic acids (the fatty acids), acetic acid does not occur in natural triglycerides. However,
the artificial triglyceride triacetin (glycerine triacetate) is a common food additive and is
found in cosmetics and topical medicines.
Acetic acid is produced and excreted by acetic acid bacteria, notable ones being
the Acetobacter genus and Clostridium acetobutylicum. These bacteria are found universally
in foodstuffs, water, and soil, and acetic acid is produced naturally as fruits and other foods
spoil. Acetic acid is also a component of the vaginal lubrication of humans and other primates,
where it appears to serve as a mild antibacterial agent [4].
2.3. PROPIONIC ACID
Propionic acid is a clear, colorless liquid with a slightly sweetish odor. It is soluble in water
and alcohol; melts at -21 C, boils at 141 C. It is used as a preservative in feed and food
industry directly or in the forms of ammonium propionate, calcium and sodium propionates. It
is used to manufacture various propionates which used in the production of pharmaceuticals,
antifungal agents, agrochemicals, plastics, plasticizers, rubber chemicals, dyes, artificial
flavors and perfumery synthetics. It is used also as a solvent and in nickel-electroplating
solutions [5].
Formula CH3CH2COOH
Mol wt. 74.08
Oral rat ld50: 2600 mg/kg
Synonyms hydroacrylic acid; carboxyethane; methylacetic acid; c-3 acid; metacetonic

acid; pseudoacetic acid; ethylformic acid; ethanecarboxylic acid; acide propionique; kyselina
propionova; propanyl acid;
Smiles C(=O)(CC)O
Classification fungicide, bactericide, preservative, acidifying agent
Physical and Chemical Properties
Physical State : clear liquid
Melting Point : - 21 - - 20 C
Boiling Point: 140.7 - 141.7 C
Specific Gravity : 0.990 - 0.998

Solubility in water : miscible
Solvent Solubility :
soluble in almost conventional organic solvents and alcohol
Vapor Density :
pka 4.875 (at 25 c)
log p 0.33 (octanol-water)
Vapor Pressure : 3.53 (mmhg)
Henry Law Constant : 4.45e-07 (atm-m3/mole at 25 c)
Nfpa Ratings Health: 3; Flammability: 2; Reactivity: 0
Flash Point : 50 C
Stability : Stable under ordinary conditions. light sensitive [5].

3.MARKET SURVEY
3.1. Demand & Supply
During the past 5 years, approximately 1.2 million metric tons of new demand for acetic acid
has developed globally. The pie chart below breaks down the regional distribution of acetic
acid supply and demand. It is clear that the Asian region, lead by China, has provided the
most demand growth for acetic acid in recent history. This is particularly the case for TPA, as
China has been adding significant polyester production capacity to meet rapidly growing
demand associated with its WTO participation, and is investing upstream in new TPA capacity
as well. Additionally, acetate esters (oxygenated solvents) are growing in China as reductions
in chlorinated and hydrocarbon solvents are enacted. In other regions of the world, demand
growth has been much more moderate, ranging from flat to slightly positive for non-Asian
regions.
Figure 1 :Acetic Acid Demand by Major Region
Figure 2: Acetic Acid Supply by Major Region [12]
3.2. Production
Global production and consumption of acetic acid in 2010 was approximately 10.7 million
metric tons. China, U.S.A, the rest of Asia and Western Europe account for the majority of the
acetic acid market. Of total global acetic acid capacity, 44% is in China, followed by 21% for
the rest of Asia, 19% in the U.S.A and 6% in Western Europe. These regions make up 90% of
total world capacity.
China accounts for the largest share of acetic acid consumption with 30% of total demand.
The rest of Asia accounted for 27% of global demand, followed by 20% in the United States
and 14% in Western Europe. These regions totaled over 90% of global acetic acid
consumption[13].
About 75% of acetic acid made for use in the chemical industry is made by methanol
carbonylation[14].
Figure 3 : World Consumption of Acetic Acid [14]
3.3. Imports & Exports
TABLE 1 : Import Export Datas of Turkey [15]
Year Flow Weight (kg)
2010 Import 54621982
2010 Export 1900514
2009 Import 49258811
2009 Export 2879706
2008 Import 43805809
2008 Export 1978922
2007 Import 53888764
2007 Export 2938153
2006 Import 49557787
2006 Export 3515640
2005 Import 52368616
2005 Export 2584119
2004 Import 50634504
2004 Export 5614918

2003 Import 51003741
2003 Export 3833920
2002 Import 44137563
2002 Export 2638730
2001 Import 33055588
2001 Export 655524
2000 Import 31208526
2000 Export 537800
3.4. Availability of Raw Materials
Most Acetic Acid is produced by methanol carbonylation processes in the world. In this
process, methanol and carbon monoxide react to produce Acetic Acid. Methanol and carbon
monoxide are raw materials, methanol carbonylation long appeared to be an attractive method
for acetic acid production. For provide the reactions methyliodide and rhodium based catalyst
is used in process. The reason of using the rhodium based catalyst is operate efficiently in low
pressures with very little amount of by products.
3.5. Price in Turkey & in World Market
3.5.1. United States
TABLE 2: United States Exports Acetic Acid [16]
UNITED STATES EXPORTS ACETIC ACID

April 2010
Tons $/Ton
Canada 2313 792
Mexico 28261 619
Argentina 1506 569
Brazil 11401 419
Colombia 600 520
El Salvador 160 663
Honduras 311 672
Belgium 9079 471
Italy 1785 539
Saudi Arabia 14 1513
Taiwan 6142 415
Others 76 1980
3.5.2. Europe
TABLE 3: European Union Exports Acetic Acid [16]
EUROPEAN UNION EXPORTS ACETIC ACID
April 2010
Tons $/Ton
Switzerland 511 785
Algeria 118 1054
Israel 150 535
Others 392 1291

3.5.3. China
TABLE 4: China Export Values [16]
CHINESE IMPORTS ACETIC ACID
May 2010
Tons $/Ton
South Korea 2 1306
Taiwan 65 1972
Others 1 -
3.5.4. Asia
TABLE 5 : Taiwan Export Values [16]
TAIWANESE EXPORTS ACETIC ACID
April 2010
Tons $/Ton
Peru 222 643
Australia 144 640
Bangladesh 222 616
Pakistan 379 568
Vietnam 294 679
China 131 1116
Others 525 641

TABLE 6 : South Korea Export Values [16]
SOUTH KOREAN EXPORTS ACETIC ACID
April 2010
Tons $/Ton
Chile 137 690
Peru 341 612
Jordan 101 632
Bangladesh 161 649
Pakistan 524 588
Philippines 500 391
China 2 1736
Japan 6511 430
Others 477 627

Figure 4 :United States & Asia Acetic Acid Prices
3.5.5. Japan
TABLE 7 : Japan Acetic Acid Export Values [16]
JAPANESE EXPORTS ACETIC ACID
April 2010
Tons $/Ton
Thailand 999 394
South Korea 2002 403
Taiwan 2590 375
Others 5 2279
3.6. Future
Acetic Acid requirement in Turkey, increasing year by year. In 2001, the import value is
31208 tons and at 2010 that is close the present time, it’s 54621 tons.
Figure 5: Future Capacity Values of Turkey [ 15]
3.7. Capacity Determination
Of the total global acetic acid capacity, approximately 65% is in China and the rest of Asia,
followed by 20% in the US and under 10% in northwest Europe.
China accounts for the largest share of acetic acid consumption and, with new capacity
scheduled to come on stream, looks set to continue as the main driver over the next few years.
China and the rest of Asia account for almost 60% of demand, with US consuming 20% and
Europe closer to 15%.
Acetic acid needs of the world in 2035, approximately 1.3 million tons / year, calculated as.
We aimed 75 thousand tons / year producing, in our plant at meeting the need.
3.8. Feasibility
Acetica process is generally more profitable and it has very high efficiency. Our basis is 100
kmol/h and it’s mass flow rate is 3200 kg/h. The import value of methanol is 380 $/ton. For
our basis, first raw material that is methanol costs 1217 $. Other raw material that is carbon
monoxide costs about 635 $.
In this process, 99 kmol acetic acid makes 5,94 tons and it costs 3795 $. Turkey’s import
value for acetic acid is 640 $/ton. For 99 kmol/h flow rate, it’s value 3800 $.
Income – Total Raw Material Cost = 3800 $ - (1217 + 635) $
= 1948 $ profit
So process is profitable and feasible.
4. SELECTION CRITERIA OF PLANT LOCATION
The location of the plant can have a crucial effect on the profitability of a project, and the
scope for future expansion. Many factors must be considered when selecting a suitable site,
and only a brief review of the principal factors will be given ın this section. The principal
factors to be considered are:
 Location, with respect to the marketing area,

 Raw material supply,
 Transport facilities,
 Availability of labour,
 Availability of utilities: water, fuel, power,
 Availability of suitable land,
 Environmental ımpact, and effluent disposal,
 Local community considerations,
 Climate,
 Political strategic considerations.
If we consider these points, Gebze was selected for plant site.
5. PROCESSING ROUTES TO ACETIC ACID
Vinegar is still made by fermentation. However, the most important synthetic routes to acetic
acid are methanol carbonylation and liquid-phase oxidation of butane, naphtha, or
acetaldehyde. Methanol carbonylation has been the method of choice for the past 25 years
and will likely remain the preferred route for large-scale production. Several new technologies
for producing acetic acid are being studied. Showa Denko may produce acetic acid by the gas-
phase reaction of ethylene with oxygen over a supported palladium catalyst that contains a
heteropolyacid or salt. Numerous patents and publications discuss the production of acetic
acid directly from ethane and oxygen. Production of acetic acid and acetate salts by
microorganisms has also received considerable attention [3].
Figure 6: Feedstock Choices and Process Routes for Acetic Acid Production [7]
Originally, acetic acid was produced by aerobic fermentation of ethanol, which is still the
major process for the production of vinegar. The first major commercial process for the
synthetic production of acetic acid was based on the oxidation of acetaldehyde. In an early
process for the conversion of acetylene to acetaldehyde introduced in 1916 in Germany and
used in China until recently, an organo-mercury compound was used as the catalyst.
The toxicity of the mercury catalyst resulted in significant environmental pollution, and as a
result, has essentially been phased out. As the petrochemical industry developed in the 1950s,
the raw material for the production of acetaldehyde shifted to ethylene. Other processes for
the production of acetic acid introduced in the 1950s and 1960s were based on the oxidation
of n butane or naphtha. The major producers of acetic acid via direct oxidation of
hydrocarbons were Celanese (via n-butane) and BP (via naphtha). The homogeneous
methanol carbonylation route to acetic acid that used a homogeneous Ni catalyst was first
commercialized by BASF in 1955. An improved process was later disclosed by BASF in
1960. The process used an iodide-promoted CO catalyst and operated at elevated temperature
(230 ◦C) and pressure (600 atm) [6].
The product yields exhibited by this process were 90, and 70% based on methanol and CO
consumption, respectively. In 1970, Monsanto commercialized an improved homogeneous
methanol carbonylation process using a methyl-iodide-promoted Rh catalyst . Compared to
other acetic acid synthesis routes (ethanol fermentation, and acetaldehyde, n-butane, or
naphtha oxidation), homogeneous Rh catalyzed methanol carbonylation is an efficient route
that exhibits high productivity and yields than the BASF process and exhibited superior
performance: acetic acid yields were 99 and 85% based on methanol and CO consumption,
respectively. Celanese and Daicel further improved the Monsanto process during the 1980s by
adding a lithium or sodium iodide promoter to enable the operation in a reduced water
environment . At lower water concentrations, by-product formation via the water gas shift
reaction is reduced, thus improving raw materials consumption and reducing downstream
separation costs.
Homogeneous metal catalysts less costly than Rh (for example, Ni [16,17,75,76] and Ir [3,18–
24] with other metal additives) have also been investigated. The Ir-based process allows
operation at reactor water levels comparable to those of the improved Celanese process and
was commercialized by BP Chemicals in 1996.
Until recently, virtually all new acetic acid capacity has made use of the homogeneous
methanol carbonylation technology developed by Monsanto and practiced commercially by
all major acetic acid manufacturers, including BP-Amoco, Celanese, and others. As a result,
more than 60% of the world acetic acid production employs the methanol carbonylation[6].
TABLE 8: Acetic Acid Process [6]

5.1. METHANOL CARBONYLATION
Methanol carbonylation (MC) is now the dominant acetic acid production technology,
accounting for over 65% of global capacity. This share is growing as MCis the preferred
technology for most new plants. In general, the good conversion and selectivity achievable by
MC technology, coupled with low cost methanol feedstock and economies of scale enjoyed by
mega-sized plants, result in process economics that are tough to beat [7].
The chemistry of the cobalt- (BASF), rhodium- (Monsanto and Celanese), and iridium
catalyzed (BP) processes is similar in requiring promotion by iodide, but the different kinetics
indicate different rate-determining steps. In all three processes, two important catalytic cycles
are common, one that involves the metal carbonyl catalyst and one that involves the iodide
promoter [3].
5.1.1. BASF
The manufacture of acetic acid from methanol and carbon monoxide at high temperature and
high pressure was described by BASF as early as 1913 [3].
BASF discovered that methanol could be carbonylated to acetic acid. The reaction takes place
according to the following equation:
CH3OH + CO → CH3COOH
BASF started its first methanol carbonylation plant in 1960 using cobalt iodide (CoI2) as a
catalyst. Synthesis took place at around 250 0C and at pressures up to 10 000 psi. The
selectivity to acetic acid from methanol and carbon monoxide was 90% and 70%,
respectively. Two plants utilising this technology were built: one in Germany by BASF, and
the other in the US by Borden Chemical [7].
The cobalt-catalyzed BASF process uses cobalt (II) iodide for in situ generation of
[Co2(CO)8] and hydrogen iodide. Acetyl iodide is formed from the reaction of hydrogen
iodide with the acyl complex to regenerate the cobalt carbonyl anion. Rapid hydrolysis of the
acetyl iodide forms acetic acid and hydrogen iodide. All of the individual steps involved in the
otherwise similar mechanism can be assumed to occur at a lower rate for cobalt than for
rhodium and iridium. This explains the higher temperature needed for the BASF process. In
addition, higher carbon monoxide partial pressures are required to stabilize the [Co(CO)4]−
complex at the higher reactor temperatures. Byproducts in the BASF process are CH4,
CH3CHO, C2H5OH, CO2, C2H5COOH, alkyl acetates, and 2-ethyl-1-butanol [58–60].
About 3.5%of the methanol reactant leaves the system as CH4, 4.5 % as liquid byproducts,
and 2 % is lost as off-gas. Some 10 % of the CO feed is converted to CO2 by the water gas
shift reaction [3].
Figure 7: Reaction cycle proposed for the cobalt-catalyzed methanol carbonylation reaction
(BASF process) [3].
Carbon monoxide, methanol (containing upto 60 % dimethyl ether), catalyst recycle, catalyst
makeup, and methyl iodide recycle (from the wash column) are sent to the hig-pressure
reactor. Part of the relatively low heat of reaction is used to preheat the feed and the rest is
ultimately dissipated through the reaction vent. The reaction product is cooled and sent to the
high-pressure separator. The off-gas goes to the wash column and the liquid is expanded to a
pressure of 0.5 – 1.0 MPa in the intermediate-pressure separator. The gas released is also sent
to the wash column; the liquid from the intermediatepressure separator is sent to the
expansion chamber. The gas from the chamber goes to the scrubber. [3]
The gas from the scrubber and the wash column is discarded as off-gas. Both scrubber
andwash column use the methanol feed to recover methyl iodide and other iodine-containing
volatile compounds; this methanolic solution is returned to the reactor. The acid is purified in
five distillation towers. The first column degasses the crude product; the off-gas is sent to the
scrubber column. The catalyst is then separated as a concentrated acetic acid solution by
stripping the volatile components in the catalyst separation column. The acid is then dried by
azeotropic distillation in the drying column. The overhead of the drying column contains
acetic and formic acids, water, and byproducts that form an azeotrope with water.
Figure 8: Production of acetic acid (BASF process) [3]

a) Preheater; b) Reactor; c) Cooler; d) High-pressure separator; e) Intermediate pressure
separator; f) Expansion chamber; g) Separation chamber; h) Degasser column; i) Catalyst
separation column; k) Drying column; l) Pure acid column; m) Residue column; n) Auxiliary
column; o) Wash column; p) Scrubbing column
5.1.2 MONSANTO
In the 1970s Monsanto developed the rhodium/iodide catalyst system for MC. In 1986,
ownership of the Monsanto technology was acquired by BP Chemicals, which further
developed the process. This technology features acetic acid selectivity greater than 99% based
on methanol.
The rhodium-catalysed methanol carbonylation process is highly selective and operates under
mild reaction pressure (around 500 psi). However, because of the high price of rhodium and
an expensive and elaborate rhodium recovery section, new developments and other catalysts
for MC are continually being investigated [7].
The methanol carbonylation process, “Monsanto Process”, is operated under mild conditions
(180–220 ◦C, 30–40 atm) and exhibits high selectivity to acetic acid based on methanol (99%)
and carbon monoxide (85%) . While the reaction, as shown below, can be carried out in a
variety of rhodium (I) or rhodium (III) complexes, under reaction conditions they are almost
invariably converted to the active catalyst [RhI2(CO)2]−1 [6].
The Monsanto process with rhodium carbonyl catalyst [38255-39-9] and iodide promoter
operatesunder milder conditions than the BASF cobalt-catalyzed process. Methanol and
carbon monoxide selectivities of greater than 99 % and 90 %, respectively, are obtained. The
system is not as sensitive to hydrogen as the BASF process, and therefore reduction products
such as methane and propionic acid are comparatively insignificant.
The chemistry of the rhodium-catalyzed methanol carbonylation reaction has been studied in
detail . Kinetic studies show the reaction to be zero-order in carbon monoxide and methanol,
and first-order in rhodium and iodide promoter. The carbonylation rate is strongly affected by
the reaction media, but the overall kinetics are unaffected by the solvent, which suggeststhat it
does not participate in the transition state of the rate-determining step [3] .
The reaction rate is independent of methanol concentration and carbon monoxide pressure.
The rate-determining step is believed to be the oxidative addition of methyl iodide to the
rhodium center of the rhodium complex, and the reaction rate is essentially of first order in
both catalyst and methyl iodide concentrations under normal reaction conditions:
reaction rate ∝ [catalyst][CH3I] [6].
Figure 9 : Catalytic cycle for rhodium carbonylation [6].
Carbon monoxide and methanol are introduced continuously into a back-mixed liquid phase
reactor at 150 – 200 ◦C and 30 – 60 bar. The noncondensablebyproducts (CO2, H2, and
CH4) are vented from the reactor to control the carbon monoxide 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 iodides such as
methyl iodide, are scrubbed from the vent before the noncondensable 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 and sent to the lightends 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 (c) and
sent to the dehydration column [3].
An aqueous acetic acid overhead stream from (c) is recycled to the reactor and a dry acetic
acid product residue stream is forwarded to a heavy ends column. As a residue stream,
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 sidestream, and the
overheadstream is recycled to the purification section ofthe process.
Figure 10: Production of acetic acid (Monsanto process) [3]
a) Reactor; b) Flasher; c) Light-ends column; d) Dehydration column; e) Heavy-ends

column
5.1.3. CELANESE AO PLUS
In 1978, Hoechst Celanese, now Celanese Chemical, was licensed to operate the Monsanto
acetic acid process commercially in its Clear Lake, Texas, plant. Later, in the 1980s, Celanese
developed its proprietary AO Plus (Acid Optimisation Plus) technology, greatly improving the
Monsanto process.
The AO Plus technology was achieved in part by increasing the rhodium catalyst stability by
adding inorganic iodide (primarily lithium iodide) in high concentrations, above a level not
usually thought to be effective as a catalyst stabiliser and promoter. The addition of lithium
iodide, with methyl iodide, permits a dramatic reduction in water concentration (to roughly 4-
5% water) in the reactor, while maintaining a high carbonylation rate [7].
This subsequently reduces the separation costs involved. In the Celanese AO Plus technology,
this alteration to the catalyst composition allows reactor operation at low water leading to
increased reactor productivity and purification capacity. With this proprietary technology,
methanol carbonylation capacity in Celanese Clear Lake, Texas, has been increased to 1.2m
tonne/year.
The main advantages of the AO Plus technology are increased productivity and lower utility
and capital costs per pound of product. This is achieved, however, in a higher iodide
environment, which could lead to increased corrosion problems and higher residual iodide in
the final product.
High iodide concentration in acetic acid could lead to catalyst poisoning problems in some
downstream applications, such as in vinyl acetate monomer manufacture. To overcome such
problems, Celanese has developed the Silverguard process for the removal of low levels of
iodide impurities from acetic acid [7].
In a patent issued in 1993, Celanese discloses the use of a silver metal ion exchange resin that
removes iodide level to below 2 ppb, as opposed to 10 ppm normally achieved by
conventional methods. Celanese discloses the use of polymeric resins co-ordinated with metal
salts, which react with and precipitate halide impurities from halide contaminated liquids.
One particular advantage of this system is the ability effectively to remove the halide impurity
in a single step, thus avoiding additional distillation and recovery steps. The preferred
polymers are reported to have functional groups capable of forming coordination complexes
with metal salts such as silver or mercury salts [7].
In the 1980s Celanese made innovative improvements to the rhodium catalyst system of the
Monsanto process with the implementation of the proprietary acetic acid optimization (AO)
technology which incorporates catalyst co-promoters. Advantages of AO technology are
enhanced carbonylation rates and increased carbon monoxide and methanol efficiencies at
lower reaction-water concentrations. These modifications represent the most significant
development in rhodium-catalyzed methanol carbonylation since the development of the
Monsanto process. The increased carbonylation rates at low reaction water concentrations are
achieved by catalyst promotion with iodide and acetate anions.
This unique enhancement in catalyst activity is due presumably to the generation of a strongly
nucleophilic fivecoordinate dianionic catalyst species, namely, which is more active than
[Rh(CO)2I2]− toward oxidative addition of methyl iodide [3].
Figure 11: Reaction cycle proposed for the rhodium-catalyzed methanol carbonylation
reaction (Monsanto process) and with inorganic iodide co-promotion (Celanese process) [3]
5.1.4. CATIVA
Due to the limitations and also because of the very attractive price difference between
rhodium and iridium 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 species. Its robustness at extremely low water concentrations (0.5 wt.’%o) is
particularly significant and ideal for optimisation 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 hgher catalyst concentrations can be obtained, making much higher
reaction rates achievable [8].
In 1996, BP announced details of a new advance in MC technology for acetic acid and
claimed significantly lower production costs. The Cativa process uses a catalyst system based
on iridium, in conjunction with several novel promoters, such as rhenium, ruthenium and
osmium. BP claims that the Cativa process offers several advantages over the original
Monsanto/BP technology.The iridium catalyst system has a higher activity compared with the
rhodium process, produces fewer byproducts, and is able to operate at reduced water levels
(less than 5% for Cativa versus 14-15% with the Monsanto process). All of these factors
combine to allow plants to increase their capacity at relatively low capital cost.In addition,
improved carbon monoxide efficiency is achieved and steam consumption is decreased owing
to lower water levels. The Cativa process was first implemented at the Sterling Chemicals'
plant in Texas City, Texas, US, in 1995 and has since been installed in several existing and
new plants [7].
Figure 12 : Catalytic cycle for the carbonylation of methanol using iridium [6]
The reactor in the Cativa TM system does not requite a traditional agitator to stir the reactor
contents. Elimifiating this leads to further operational and maintenance cost savings. The
reactor contents are mixed by the jet mixing effect provided by the reactor cooling loop, in
which material leaves the base of the reactor and passes through a cooler before being
returned to the top of the reactor. A secondary reactor after the main reactor and before the
flash tank further increases CO utilisation by providing extra residence time under plug flow
conditions for residual CO to react and form acetic acid [7].
Figure 13: Simplified process flowsheet for a commercial scale Cativa" methanol
carbonylation plant. The low boiler water removal duties are combined into one, smaller.
distillation column. The size of the high boiler removal column [8]
Model studies have shown that the oxidative addition of methyl iodide to the iridium centre 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 deteimining (as
in the case of rhodium). The slowest step in the cycle is the subsequent migratory insertion of
CO to form the iridium-acyl species, F, which involves the elimination of ionic iodide and the
coordination of an additional CO ligand [8].
5.2. DIRECT OXIDATION OF SATURATED HYDROCARBONS
Liquid-phase oxidation (LPO) of aliphatic hydrocarbons was once practiced worldwide. Due
to competition from carbonylation technology, plants have reduced production by LPO
significantly. The process changes depending on the availability of raw materials. Raw
materials include n-butane and light naphtha. In the United States and Canada, Celanese
employs butane, while BP in the United Kingdom uses light naphtha to produce acetic acid.
Oxidation of hydrocarbons follows similar kinetics, both in the gas and liquid phases,
especially in slightly polar solvents. However, the mechanism of the reaction is very
complicated. The reaction can be considered roughly as a radical chain reaction. For example,
the oxidation of butane proceeds through initiation, oxidation, propagation, and
decomposition steps. The initiation and propagation probably involve radicals abstracting
hydrogen from a secondary carbon atom of butane. Subsequent reaction with oxygen yields
hydroperoxides. These intermediates decomposes to produce acetic acid. Catalysts, agitation,
and high temperature accelerate the decomposition [3].
The oxidation of n-butane and light naphtha (which contains low boiling hydrocarbons,
especially pentanes and hexanes) is carried out at 160-200 C. The oxidation can be carried out
catalytically, usually in the presence of cobalt or manganese, or non-catalytically.
The principal products are acetic acid and methylethylketone. Other organic products,
however, such as ethanol, methanol, formic, propionic and butyric acids are also produced.
The product ratio can be varied somewhat to obtain more of a desired product.
Liquid phase catalytic oxidation of n-butane was introduced by Celanese in 1952 in a large
plant located near Pampa, Texas. This plant is still in operation. A non-catalytic process for
the oxidation of light naphtha was developed by British Distillers in the UK. Oxidation of
naphtha can be effected at lower temperature and pressures than for butanes. The product
composition from naphtha oxidation, however, is far more complex and acetic acid separation
more expensive. Process selection, therefore, depends on feedstock availability and suitable
outlets for the co-products formed [7].
Figure 14 : Oxidation of n-butane in the liquid phase (Chemische Werke H¨uls process) [3]
a) Reactor; b) Air cooler; c) Collector; d) Separation vessel; e) Pressure column; f) Distillation

column
5.3. ACETALDEHYDE PROCESS
Oxidation of acetaldehyde represents a majör process for making acetic acid.
CH3CHO+ 1/2O2 → CH3COOH
Although oxidation reactions are rather complex, a simplified viewis presented here. The
oxidation of acetaldehyde to acetic acid proceeds through a free-radical chain which produces
peracetic acid as an intermediate [3].
Prior to the commercialization of the Monsanto process, most acetic acid was produced by
oxidation of acetaldehyde. This remains the second-most-important manufacturing method,
although it is usually uncompetitive with the carbonylation of methanol.
The acetaldehyde may be produced via oxidation of butane or light naphtha, or by hydration
of ethylene. When butane or light naphtha is heated with air in the presence of various
metal ions, including those of manganese, cobalt, and chromium, peroxides form and then
decompose to produce acetic acid according to the chemical equation
2 C4H10 + 5 O2 → 4 CH3COOH + 2 H2O

The typical reaction is conducted at temperatures and pressures designed to be as hot as
possible while still keeping the butane a liquid. Typical reaction conditions are 150
°C (302 °F) and 55 atm. Side-products may also form, including butanone, ethyl
acetate, formic acid, and propionic acid. These side-products are also commercially valuable,
and the reaction conditions may be altered to produce more of them where needed. However,
the separation of acetic acid from these by-products adds to the cost of the process.
Under similar conditions and using similar catalysts as are used for butane oxidation,
the oxygen in air to produce acetic acid can oxidize acetaldehyde.
2 CH3CHO + O2 → 2 CH3COOH
Using modern catalysts, this reaction can have an acetic acid yield greater than 95%. The
major side-products are ethyl acetate, formic acid, and formaldehyde, all of which have
lower boiling pointsthan acetic acid and are readily separated by distillation[4].
Figure 15: Oxidation of acetaldehyde to acetic acid [3]
a) Reactor; b) Acetaldehyde column; c) Methyl acetate column; d) Finishing column; e)

Column for recovering entrainer; f) Off-gas scrubber column
5.4. OTHER PROCESSES
Acetic Acid from Ethylene
Efforts to convert ethylene directly to acetic acid without going through an acetaldehyde
isolation step have been of interest. Although the price of ethylene generally makes this
process unattractive, some developments are noteworthy. Effective oxidation of ethylene to
acetic acid has been demonstrated with metal oxides such as vanadium pentoxide. Showa
Denko combined palladium with heteropolyacids and patented a catalyst for producing acetic
acid from ethylene and oxygen. The catalyst contains palladium, an heteropolyacid, such as
silicotungstic acid, and potassium tellurite or potassium selenite. The process is operated at
150 ◦C and 0.7MPa. Although water is not consumed in the reaction, the presence of water
enhances the selectivity to acetic acid and is recommended [3].
Acetic Acid from Ethane
Several groups have investigated catalysts for the conversion of ethane to acetic acid .
C2H6 + 3/2O2 −→ CH3CO2H+H2O
Union Carbide developed the Ethoxene process for the production of ethylene from ethane
and oxygen. The earliest catalysts consisted of molybdenum, vanadium, and niobium oxides
and were very selective for ethylene at temperatures below 300 ◦C. Unfortunately, ethane
conversions were low (about 10 %) due to inhibition by the product. Further development
focused on the coproduction of ethylene and acetic acid with a catalyst comprised of
molybdenum, vanadium, niobium, calcium and antimony. The addition of water enhances
acetic acid formation. A later patent discloses that the addition of water and an ethylene
hydration catalyst improves selectivity to acetic acid found that acetic acid production was
favored over ethylene and carbon oxides at temperatures below300 ◦C. Roy et al
demonstrated that the addition of molybdenum enhanced acetic acid selectivity. Desorption of
acetic acid from the catalyst surfacewas speculated to be the ratedetermining step of the
reaction. BP Chemicals claims that the addition of rhenium to mixed metal oxide catalysts [3].
Union Carbide piloted this process in the 1980s, but eventually dropped development. One of
the drawbacks of this route is the limited market opportunity, since acetic acid and ethylene,
in specific ratios, must find outlets.
In 2001, Sabic announced its intention to build a 30 000 tonne/year acetic acid semi-works
plant based on a proprietary catalytic oxidation process. Sabic has not disclosed the detailed
process design of this novel acetic acid production technology [7] .
5.5. SYNTHESIS GAS ROUTE TO ACETIC ACID
A nearby synthesis gas plant to produce CO is normally required to provide feed to an acetic
acid plant. On the contrary, an efficient integrated synthesis and methanol synthesis plant and
acetic acid plant are available by combination of current technology at the natural gas source.
This integrated process could achieve a significant capital cost reduction relative to the
conventional flow scheme. Applying this concept, Haldor Topsoe proposed an integrated
process that includes the synthesis of methanol and dimethyl ether (DME) in a first catalytic
reaction stage and the subsequent carbonylation of methanol and DME into acetic acid.
Although the reaction pressure required for methanol synthesis is higher than the pressure
used in acetic acid synthesis, the combination of methanol synthesis with dimethyl ether
synthesis can reduce the pressure of the first reaction step. The catalyst consists of a mixture
of the catalyst for methanol synthesis (Cu-Zn-Al oxide, etc.) and a dehydration catalyst [6].
The reaction is carried out at approximately 220 ◦C and 40 atm:
CO + 2H2 → CH3OH
2CH3OH → CH3OCH3 + H2O
H2O + CO → CO2 + H2
In the acetic acid synthesis step, carbonylation of DME and methanol to acetic acid is carried
out by the rhodium carbonyl complex catalyst with carbon monoxide being supplied from the
synthesis gas process unit:
CH3OCH3 + 2CO + H2O → 2CH3COOH
Carbonylation reaction conditions of 170–250 ◦C and 25–50 atm, can be used to obtain
acceptable reaction rates in the liquid phase [7]
6. ACETICA
Process development in methanol carbonylation is still continuing. Chiyoda has recently
developed an acetic acid process, Acetica, based on methanol carbonylation technology,
which uses a heterogeneous supported catalyst system and a bubble column reactor. The
technology was unveiled in May 1997 at a technology symposium in China.
The feedstocks are methanol and carbon monoxide, with methyl iodide as a promoter and a
rhodium catalyst complexed to a polyvinylpyridine resin. It is reported that the supported
catalyst system leads to high productivity, improved rhodium management, and produces an
acetic acid yield of more than 99% from methanol.
Like the Celanese AO Plus and BP Cativa processes, the Acetica process can be operated at a
low water content in the range 3-8 wt% of the reactor liquid. Unlike conventional
homogeneous catalytic systems, surplus water is not required to keep the catalyst metal in
solution. The reactor has a low hydrogen iodide concentration and subsequently a less
corrosive environment [9].
Another feature of the process is the use of the bubble column reactor, which eliminates the
need for high pressure seals required with stirred tank reactors. This feature allows the use of
low purity carbon monoxide since operating pressures can be increased (up to 900 psi) to
maintain optimum carbon monoxide partial pressure.
The absence of high pressure seals eliminates leakage concerns at this high pressure. Use of
low purity carbon monoxide can lower feedstock costs and capital investment. Chiyoda has
recently granted a licence for the Acetica process to Guizhou Crystal Organic Chemical
Group in China.
TABLE 9 : Catalyst Systems For Methanol Carbonylation [9].

The primary advantage of these latest advances in methanol carbonylation technology is that
they permit tremendous increases in capacity compared with conventional MC technology
(see chart ), with commensurate decrease in investment dollars per unit volume of acetic acid
product [7].
The rhodium catalyzed methanol carbonylation process is highly selective and operates under
mild reaction pressure (around 500 psia). However, because of the high price of rhodium and
an expensive and elaborate rhodium recovery section, new developments and other catalysts
for methanol carbonylation are continually being investigated. Improvements to the original
Monsanto/BP technology have been introduced by Celanese (AO Plus Process), BP (Cativa
Process), and Chiyoda Corporation (Acetica Process). An overview of Monsanto/BP’s catalyst
system in comparison with that of Celanese AO Plus, BP Cativa, and Chiyoda Acetica
processes is given in the following table [9].
Rh complex catalyst supported on solid resin can be depicted as twointeracting cycles, Methyl
iodide is added ozidatevely to th rodium- dicarbonyl- diiodide complex [RHI 2 (CO)2] to
generate a rhodium methyl complex. This rodium methyl complex rapidly undergoes a methy
migration to a neighboring carbonyl group in the acetyl form and reacts with CO to generate
the rodium acetyl complex. The hydration of acetyl iodide is very rapid in the presence of
water and results in the formation of acetic acid and hyrrogen iodide to complete the cycle
[10].
Catalys Preparation Reactions
Promoter (CH3I). The ACETICA process uses methyl iodide as the promoter for the
carbonylation reaction, as described earlier. ythe method of producing CH 3I in a methyl iodide
generator is
I2 + CO + H2O  2HI + CO
HI + CH3OH  CH3I + H2O
Heterogeneous Catalyst (Rhodium Immobilized on Resin). The ACETICA process is based

on a heterogeneous rhodium catalyst. The nitrogen atoms of the resin pyridine groups become
positivelycharged after quaternization with methyl iodide [10].
Figure 16: Rhodium İmmobilization [11]
By product formations
Gaseous by-product (CO2, H2 ,CH4 ). Gaseous by-product formation reactions, such as water
gas shift and methane formation, also ocur in the carbonylation reactor, but lesses of CO and
methanol by these reactions amount to less than 1 percent of the total feed:
Water gas shift reaction : CO + H2O  CO2 +H2
Methanation : CH3OH + H2  CH4 + H2O
CO + 3H2  CH4 + H2O
Liquid By-Products Very small amounts of liquid by-products are produced at the initial stage
of plant operaton, and their concentrations come to equilibrium, except for some heavy by-
products such as propionic acid. These heavy by-products are eliminated with small purges
from the purification unit [10].
TABLE 10: Acetic acid by the CHIYODA/UOP ACETICA™ process design bases and
assumptions [11]
6.1. PROCESS DEFINITION
The Aspen Plus model is developed to simulate the steady-state production of acetic acid by
low pressure methanol carbonylation in the presence of a heterogeneous rhodium (Rh)
catalyst and the promoter methyl iodide. The process is intended to resemble the
Chiyoda/UOP Acetica™ process, a novel heterogeneous methanol process for the production
of acetic acid. Figure 1 in the Aspen Plus model file shows the process flow diagram, which
consists of both the carbonylation and purification sections. In the Aspen model, Radfrac is
used to represent the distillation columns.
Due to insufficient kinetics information, Aspen Plus RYIELD reactor model is used to
represent R-201. The reactor is considered to have two valid phases; vapor and liquid phases.
Before entering the carbonylation reactor, the fresh methanol (technical grade) feed is split
and fed to two countercurrent absorbers. Methanol is contacted with the reactor offgas
(primarily unconverted CO) in high-pressure absorber C-202 and also with light gases
generated and released downstream in low-pressure absorber C-201. This absorption scheme
maximizes the recovery of valuable methyl acetate and methyl iodide that would otherwise
exit the system with the vent gas, causing unnecessarily high chemical consumption and yield
loss. The methanol feed streams (together with the recovered methyl acetate and methyl
iodide) exiting the absorbers are recombined, heated in E-202, and then mixed with the
effluent from the recycle surge drum to yield the combined liquid feed stream to
carbonylation reactor R-201. Compressed, 98.6% pure CO is introduced at the bottom of R-
201. The carbonylation reaction is carried out continuously at about 180°C (356°F) and 638
psig (42 atm). The heat of reaction is removed by passing the catalystliquid mixture through
the reactor downcomer to generate low-pressure steam that supplies a significant portion of
the plant energy requirements [11].
Catalyst retention in the reactor is essentially 100%. Most of the unreacted CO and other
gaseous by-products are separated from the liquid effluent in V-201. The liquid effluent from
V-201 containing product acetic acid, is introduced to crude fractionating column C-301 to
recover the net acetic acid product, and to reject dissolved CO and light by-product gases into
the combined lowpressure offgas line.
The lighter liquids are phase-separated into aqueous and organic fractions in reflux drum,
with 99% of the aqueous material (mostly water) returned to the reaction system and all of the
organic liquid (mostly methyl iodide promoter and methyl acetate intermediate) recycled to
the reactor. The recovered net acetic product is sent to downstream purification [11].
Figure 17 : Flow Diagram of Acetica Process [10]

7. METHOD OF CALCULATION
Basis: 100 kmol/h CH3OH
 Material Balance Calculations

Overall material balance
Atomic balance
Material balance for streams
 CH3OH + CO → CH3COOH (Selectivity 0.99)
0
 Energy
Balance
Calculations
8.CALCULATIONS
8.1.MATERIAL BALANCE CALCULATIONS
CH3OH CH3COOH
I2 CH3CH2COOH
CO CH3COOCH3, H2O, CO, CO2, CH3I,
HI, CH3OCH3, HCOOH
Basis: 100 kmol/h CH3OH
 Main reaction; CH3OH + CO → CH3COOH (Selectivity 0.99)

 By-products rxns;
CH3OH + CH3COOH CH3CH2COOH + H2O
CH3OH + CH3COOH CH3COOCH3 + H2O
For main rxn;

Expected products yied were >99% and 92% of theoretical values, based on methanol and CO
consumption, respectively, from the ACETICA process.[11]
100 kmol/h CH3OH 99 kmol/h CH3COOH
a kmol/h I2 x kmol/h CH3CH2COOH
108.7 kmol/h CO n kmol/h CH3COOCH3,

y kmol/h H2O,
z kmol/h CO,
k kmol/h CH3I,
t kmol/h CO2,
m kmol/h HI,
b kmol/h CH3OCH3,
g kmol/h HCOOH
Atomic balance;
I : 2a = m + k
C : 100 + 108.7 = 99 * 2 + 3x + z + t + k + 3n + 2b + g
H : 100 * 4 = 99 * 4 + 6x + 2y + 3k + m + 3n + 6b + 2g
O : 100 + 108.7 = 99 * 2 + 2x + y + z + 2t + 2n + b + 2g
Values of a, b, g, k, m, n, t, x, y, z in these equations were solved.
a = 0.115, b = 0.04, g = 0.005, k = 0.06, m = 0.17, n = 0.06, t = 0.639, x = 0.5, y = 0.02,

z = 8.24.
TABLE 11: Overall Data
Component Unit (kmol/h)

CH3OH 100
Input CO 108.7
I2 0.115
CH3COOH
99
CH3CH2COOH 0.5
CH3COOCH3
0.06
H2O 0.02
Output CO 8.24
CO2 0.639
CH3I 0.06
HI 0.17
CH3OCH3 0.04
HCOOH 0.005
0.115 kmol/h I2 0.5 kmol/h CH3CH2COOH
108.7 kmol/h CO 0.06 kmol/h CH3COOCH3,

0.02 kmol/h H2O,
8.24 kmol/h CO,
0.06 kmol/h CH3I,
0.639 kmol/h CO2,
0.17 kmol/h HI,
0.04 kmol/h CH3OCH3,
0.005 kmol/h HCOOH
Material balance for stream 3, 4, 5, 6
Stream 3 was going to low pressure absorption column. This stream was divided into 30% of
the mainstream. (assumption)
(CH3OH)3 = 30 kmol/h
(CH3OH)4 = (CH3OH)2 - (CH3OH)3 = 70 kmol/h
Stream 6 was fed to mixing vessel. 5% of mainstream would be sent there. (assumption)
(CH3OH)6 = 5 kmol/h

Material balance for stream 8
(CH3I)8 = 0.23 kmol/h
(H2O)8 = 0.115 kmol/h
(O2)8 = 0.0575 kmol/h
Stream 19 contained that; (CH3I)19 = 0.05 kmol/h, (CO2)19 = 0.28 kmol/h, (CO)19 = 3 kmol/h,
(HI)19 = 0.06 kmol/h, (CH3COOCH3)19 = 0.1 kmol/h, (CH3OCH3)19 = 0.03 kmol/h,
(CH3COOH)19 = 36 kmol/h, (H2O)19 = 0.2 kmol/h, (CH3CH2COOH)19 = 0.182 kmol/h,
(HCOOH)19 = 0.00212 kmol/h. And stream 20 was three times of stream 19. It contained that;
(CH3I)20 = 0.15 kmol/h, (CO2)20 = 0.84 kmol/h, (HI)20 = 0.18 kmol/h, (CO)20 = 9 kmol/h,
(CH3COOCH3)20 = 0.3 kmol/h, (CH3OCH3)20 = 0.09 kmol/h, (CH3COOH)20 = 108 kmol/h,
(H2O)20 = 0.6 kmol/h, (CH3CH2COOH)20 = 0.545 kmol/h, (HCOOH)20 = 0.00636 kmol/h.
(assumption)
(CH3COOH)13 = 45 kmol/h
(H2O)13 = 0.78 kmol/h
(CH3CH2COOH)13 = 0.2267 kmol/h
(CH3COOCH3)13 = 0.272 kmol/h
(HI)13 = 0.07 kmol/h
(CH3I)13 = 0.2075 kmol/h
(CO)13 = 3.76 kmol/h
(CO2)13 = 0.485 kmol/h
(CH3OCH3)13 = 0.08 kmol/h
(HCOOH)13 = 0.00348 kmol/h
(CH3OH)13 = 95 kmol/h
(H2O)17 = (H2O)39 + (H2O)34 + (H2O)49 = 0.57 kmol/h
(CH3COOCH3)17 = (CH3COOCH3)34 + (CH3COOCH3)39 + (CH3COOCH3)54 = 0.0185 kmol/h
(HI)17 = (HI)34 = 0.009 kmol/h
(CH3I)17 = (CH3I)34 = 0.075 kmol/h
(CO)17 = (CO)34 = 0.45 kmol/h

(CO2)17 = (CO2)34 = 0.042 kmol/h
(CH3OCH3)17 = (CH3OCH3)34 = 0.0045 kmol/h
(CH3COOH)17 = (CH3COOH)34 + (CH3COOH)39 = 9 kmol/h
(CH3CH2COOH)17 = (CH3CH2COOH)34 + (CH3CH2COOH)39 = 0.045 kmol/h
(HCOOH)17 = (HCOOH)34 + (HCOOH)39 + (HCOOH)54 = 0.00136 kmol/h
(H2O)18 = (H2O)23 + (H2O)24 = 0.21 kmol/h
(CH3COOCH3)18 = (CH3COOCH3)23 + (CH3COOCH3)24 = 0.2535 kmol/h
(HI)18 = (HI)23 + (HI)24 = 0.061 kmol/h
(CH3I)18 = (CH3I)23 + (CH3I)24 = 0.1325 kmol/h
(CO)18 = (CO)23 + (CO)24 = 3.31 kmol/h

(CO2)18 = (CO2)23 + (CO2)24 = 0.443 kmol/h
(CH3OCH3)18 = (CH3OCH3)23 + (CH3OCH3)24 = 0.0755 kmol/h
(CH3COOH)18 = (CH3COOH)24 = 36 kmol/h
(CH3CH2COOH)18 = (CH3CH2COOH)24 = 0.1817 kmol/h
(HCOOH)18 = (HCOOH)24 = 0.00212 kmol/h
Stream 34 was occured from 15 % of stream 33. (assumption)
(H2O)34 = 0.03 kmol/h, (CH3COOCH3)34 = 0.015 kmol/h, (CH3OCH3)34 = 0.0045 kmol/h,

(HI)34 = 0.009 kmol/h, (CH3CH2COOH)34 = 0.027 kmol/h, (CH3COOH)34 = 5.4 kmol/h,
(CH3I)34 = 0.075 kmol/h, (HCOOH)34 =0.00032 kmol/h, (CO)34 = 0.45 kmol/h, (CO2)34 =
0.042 kmol/h.
(H2O)20 = (H2O)33 + (H2O)34 = 0.6 kmol/h
(HI)20 = (HI)33 + (HI)34 = 0.18 kmol/h
(CH3I)20 = (CH3I)33 + (CH3I)34 = 0.15 kmol/h
(CO)20 = (CO)33 + (CO)34 = 9 kmol/h
(CO2)20 = (CO2)33 + (CO2)34 = 0.84 kmol/h
(CH3OCH3)20 = (CH3OCH3)33 + (CH3OCH3)34 = 0.09 kmol/h
(CH3COOH)20 = (CH3COOH)33 + (CH3COOH)34 = 108 kmol/h
(CH3CH2COOH)20 = (CH3CH2COOH)33 + (CH3CH2COOH)34 =0.545 kmol/h
(HCOOH)20 = (HCOOH)33 + (HCOOH)34 = 0.00636 kmol/h

Stream 22 contained that; (CH3I)22 = 0.04 kmol/h, (CO2)22 = 0.1 kmol/h, (HI)22 = 0.03 kmol/h,
(CO)22 = 1.5 kmol/h, (CH3COOCH3)22 = 0.01 kmol/h, (CH3OCH3)22 = 0.017 kmol/h.
(assumption)
(H2O)24 = (H2O)19 = 0.2 kmol/h
(CH3COOCH3)24 = (CH3COOCH3)19 - (CH3COOCH3)22 = 0.09 kmol/h

(HI)24 = (HI)19 - (HI)22 = 0.03 kmol/h
(CH3I)24 = (CH3I)19 - (CH3I)22= 0.01 kmol/h
(CO)24 = (CO)19 - (CO)22 = 1.5 kmol/h
(CO2)24 = (CO2)19 - (CO2)22 = 0.18 kmol/h
(CH3OCH3)24 = (CH3OCH3)19 - (CH3OCH3)22 = 0.013 kmol/h
(CH3OH)24 = (CH3OH)21 = 65 kmol/h

(H2O)25 = (H2O)26 = 0.01 kmol/h
(HI)25 = (HI)26 - (HI)29 = 0.031 kmol/h
(CH3I)25 = (CH3I)26 - (CH3I)29 = 0.1225 kmol/h
(CO)25 = (CO)26 - (CO)29 = 1.81 kmol/h
(CO2)25 = (CO2)26 - (CO2)29 = 0.263 kmol/h
(CH3OH)25 = (CH3OH)3 = 30 kmol/h

(H2O)26 = (H2O)28 =0.01 kmol/h
(HI)26 = (HI)27 = 0.171 kmol/h
(CH3I)26 = (CH3I)27 = 0.1425 kmol/h
(CO)26 = (CO)27 = 8.55 kmol/h
(CO2)26 = (CO2)27 = 0.798 kmol/h
Stream 22 contained that; (CH3I)22 = 0.04 kmol/h, (HI)22 = 0.03 kmol/h, (CO)22 = 1.5 kmol/h,
(CO2)22 = 0.1 kmol/h, (CH3OCH3)22 = 0.017 kmol/h, (CH3COOCH3)22 =0.01. (assumption)
Stream 30 was equal to stream 22.
(CH3I)29 = (CH3I)31 - (CH3I)30 = 0.02 kmol/h
(HI)29 = (HI)31 - (HI)30 = 0.14 kmol/h
(CO)29 = (CO)31 - (CO)30 = 6.74 kmol/h

(CO2)29 = (CO2)31 - (CO2)30 = 0.535 kmol/h
Stream 27 contained that; (CH3I)27 = 0.1425 kmol/h, (CH3COOCH3)27 = 0.185 kmol/h, (CO2)27
= 0.798 kmol/h, (HI)27 = 0.171 kmol/h, (CO)27 = 8.55 kmol/h, (CH 3OCH3)27 = 0.085 kmol/h.
(assumption)
(CH3COOH)35 = (CH3COOH)36 = 102.6 kmol/h
(H2O)35 = (H2O)36 = 0.57 kmol/h
(HI)35 = (HI)27 = 0.171 kmol/h

(CH3I)35 = (CH3I)27 = 0.1425 kmol/h
(CO)35 = (CO)27 = 8.55 kmol/h
(CO2)35 = (CO2)27 = 0.798 kmol/h
Material balance for stream 36, 37
Stream 38 was occured from 96.5 % of stream 36. (assumption)
(CH3COOH)37 = 3.6 kmol/h
(H2O)37 = 0.02 kmol/h
(CH3CH2COOH)37 = 0.018 kmol/h
(CH3COOCH3)37 = 0.0035 kmol/h

(CH3COOH)36 = (CH3COOH)37 + (CH3COOH)38 = 102.6 kmol/h
(H2O)36 = (H2O)37 + (H2O)38 = 0.57 kmol/h
(CH3CH2COOH)36 = (CH3CH2COOH)37 + (CH3CH2COOH)38 = 0.518 kmol/h
Stream 28’s light component key was CH3COOCH3 and heavy component key was H2O.
(CH3COOCH3)28 = 0.0265 kmol/h and (H2O)28 = 0.01 kmol/h was accepted. (assumption)
(H2O)38 = (H2O)40 + (H2O)28 = 0.55 kmol/h

(H2O)40 = (H2O)41 - (H2O)45 = 0.54 kmol/h
(CH3COOCH3)40 = (CH3COOCH3)41 = 0.07 kmol/h

(H2O)42 = (H2O)43 = 0.55 kmol/h
(CH3COOCH3)42 = (CH3COOCH3)51 = 0.07 kmol/h

Material balance for streams 45, 46
Stream 48 was fed to recycle surge drum. (H2O)48 = 0.52 kmol/h was accepted. (assumption)
(H2O)46 = (H2O)47 + (H2O)48 = 0.54 kmol/h
(H2O)45 = (H2O)44 - (H2O)46 = 0.01 kmol/h

(CH3COOH)50 = (CH3COOH)58 + (CH3COOH)55 - (CH3COOH)57 = 99 kmol/h

Stream 57 was contained 0.3 kmol/h acetic acid. (assumption)
(CH3COOH)55 = (CH3COOH)57 = 0.3 kmol/h

8.2. ENERGY BALANCE CALCULATIONS
Overall Energy Balance
0.115 kmol/h I2 0.5 kmol/h CH3CH2COOH
108.7 kmol/h CO 0.06 kmol/h CH3COOCH3,

0.02 kmol/h H2O,
8.24 kmol/h CO,
0.06 kmol/h CH3I,
0.639 kmol/h CO2,
0.17 kmol/h HI,
0.04 kmol/h CH3OCH3,
0.005 kmol/h HCOOH
Ĥoverall = Ĥout –Ĥin

= (Ĥ31 + Ĥ47 + Ĥ52 + Ĥ60 + Ĥ56 ) – (Ĥ1+ Ĥ7 + Ĥ10)
= (-3917.52 -13168.8 -5482.97 -6157.93) – (-7458.05 + 56.2422 -3946.2)
Ĥoverall= -17379.21 kj/kg

ĤM-401= Ĥout –Ĥin
=(Ĥ8)-(Ĥ6 + Ĥ7) =( -6209.23) –( 56.24 -96885.8)
ĤM-401= 90620.3 kj/jg

ĤR-401=Ĥout - Ĥin
=(Ĥ20+ Ĥ19) – (Ĥ9 + Ĥ12+ Ĥ13)
ĤR-401=( -7051.62 -7051.5) – (-6209.23 -3927.81 -6979.7)= -30135.5 kj/kg
ĤS-401=Ĥout - Ĥin
=( Ĥ34- Ĥ33) - Ĥ20
ĤS-401=( -7051.89 -7051.26)- (-7051.62)= -7051.53kj/kg
ĤA-401= Ĥout - Ĥin
=( Ĥ24+ Ĥ22) –(Ĥ19 + Ĥ21)
ĤA-401= (-7082.45 -3567.73)-( -7051.8 -7455.57)=3857.19 kj/kg
ĤA-402= Ĥout - Ĥin
= (Ĥ25+ Ĥ29) – (Ĥ3 + Ĥ26)
ĤA-402= (-6303.46 -1106.47) – (-7456.91 -3985.24)= 16639.14 kj/kg

ĤF-401= Ĥout - Ĥin
= (Ĥ36 + Ĥ27) – ( Ĥ35)
ĤF-401= (-7219.73 -6063.73) – (-7017.57) = -6265.89 kj/kg

ĤD-401= Ĥout - Ĥin
=( Ĥ28 + Ĥ40) – ( Ĥ38)
ĤD-401= (-6063.73 -7236.57) – (-7221.87) = -6078.43 kj/kg

ĤD-402 = Ĥout –Ĥin
= ( Ĥ41+ Ĥ50 ) - (Ĥ40 + Ĥ45) = (-109679-6742.72)-( -7236.57-13168.8)
ĤD-402 =-96016.22 kj/kg

ĤX-401 = Ĥout –Ĥin
= (Ĥ51 – Ĥ43) – Ĥ42 = (-5482.68 -13159.7) - (-10438.6)
ĤX-401 = -8203.78 kj/kg
= (Ĥ55 + Ĥ58) – (Ĥ57 + Ĥ50) = (-5996.2-6749.66) - (-7225.14-674.72)
ĤD-403 = -4846 kj/kg

= ( Ĥ56 + Ĥ57 ) – ( Ĥ55) = (-6157.93 -7225.14 ) – (-5996.2 )
ĤD-404 = -7386.87 kj/kg

9. RESULTS
Steam # 1 2 3 4
Component kmol/h kg/h kmol/h kg/h kmol/h kg/h kmol/h kg/h
CO 0 0 0 0
CH3OCH3 0 0 0 0
CH3I 0 0 0 0
CH3COOCH3 0 0 0 0
CH3OH 100 3204,186 100 3204,186 30 961,2558 70 2242,93
H2O 0 0 0 0
HCOOH 0 0 0 0
CH3COOH 0 0 0 0
CH3CH2COOH 0 0 0 0
HI 0 0 0 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0 0 0 0
Total 100 3204,186 100 3204,186 30 961,2558 70 2242,93
State
T °C 298 298 298 298
P (barg) 3 3 3 3
Specific Enthalpy kj/kg -7458,05 -7457,75 -7456,91 -7458,11
enthalpy MJ/h -6638,05 -6637,78 -1991,11 -4646,67

Steam # 5 6 7 8
CO 0 0 0 0
CH3OCH3 0 0 0 0
CH3I 0 0 0 0,23 32,64597
CH3COOCH3 0 0 0 0
CH3OH 65 2082,721 5 160,2093 0 4,77 152,8397
H2O 0 0 0 0,115 2,071757
HCOOH 0 0 0 0
CH3COOH 0 0 0 0
CH3CH2COOH 0 0 0 0
HI 0 0 0 0
I2 0 0 0,115 29,18803 0
O2 0 0 0 0,0575 1,839931
CO2 0 0 0 0
Total 65 2082,721 5 160,2093 0,115 29,18803 5,1725 189,3973
State
T °C 298 298 298 298
P (barg) 3 3 1 1
Specific Enthalpy kj/kg -7457,99 -96885,8 56,2422 -6209,23
enthalpy MJ/h -4314,7 -4311,67 0,456 -326,67

Steam # 9 10 11 12
CO 0 108,7 3044,698 108,7 3044,698 108,7 3044,698
CH3OCH3 0 0 0 0
CH3I 0,23 32,64597 0 0 0
CH3COOCH3 0 0 0 0
CH3OH 4,77 152,8397 0 0 0
H2O 0,115 2,071757 0 0 0
HCOOH 0 0 0 0
CH3COOH 0 0 0 0
CH3CH2COOH 0 0 0 0
HI 0 0 0 0
I2 0 0 0 0
O2 0,0575 1,839931 0 0 0
CO2 0 0 0 0
Total 5,1725 189,3973 108,7 3044,698 108,7 3044,698 108,7 3044,698
State
T °C 298 298 298 453
P (barg) 44 1 44 44
enthalpy MJ/h -326,67 -3337,5 -3458,89 -3321,94

Steam # 13 14 15 16
CO 3,76 105,318 3,31 92,71343 3,31 92,71343 0,45 12,60455
CH3OCH3 0,08 3,685475 0,0755 3,478167 0,0755 3,478167 0,0045 0,207308
CH3I 0,2075 29,45234 0,1325 18,80692 0,1325 18,80692 0,075 10,64542
CH3COOCH3 0,272 20,14936 0,2535 18,77891 0,2535 18,77891 0,0185 1,370453
CH3OH 95 3043,977 95 3043,977 95 3043,977 0
H2O 0,78 14,05192 0,21 3,783209 0,21 3,783209 0,57 10,26871
HCOOH 0,00348 0,160168 0,00212 4,700112 0,00212 4,700112 0,00136 0,062595
CH3COOH 45 2702,338 36 2209,912 36 2209,912 9 540,4676
CH3CH2COOH 0,2267 16,79361 0,1817 7,037461 0,1817 7,037461 0,045 3,333534
HI 0,07 8,953869 0,061 7,802657 0,061 7,802657 0,009 1,151212
I2 0 0 0 0
O2 0 0 0 0
CO2 0,485 21,34461 0,443 16,1955 0,368 16,1955 0,042 1,848399
Total 145,8847 5966,224 136,4076 5427,185 136,4076 5427,185 10,21536 581,9598
State
T °C 453 453 438 453
P (barg) 44 44 44 44
enthalpy MJ/h -11567,5 -10415,3 -10494,2 -1212,5

Steam # 17 18 19 20
CO 0,45 12,60455 3,31 92,71343 3 84,0303 9 252,0909
CH3OCH3 0,0045 0,207308 0,0755 3,478167 0,03 1,382053 0,09 4,14616
CH3I 0,075 10,64542 0,1325 18,80692 0,05 7,09695 0,15 21,29085
CH3COOCH3 0,0185 1,370453 0,2535 18,77891 0,1 7,407854 0,3 22,22356
CH3OH 0 95 3043,977 0 0
H2O 0,57 10,26871 0,21 3,783209 0,2 3,603056 0,6 10,80917
HCOOH 0,00136 0,062595 0,00212 0,097574 0,00212 0,097574 0,00636 0,292721
CH3COOH 9 540,4676 36 2161,871 36 2161,871 108 6485,612
CH3CH2COOH 0,045 3,333534 0,1817 13,46007 0,1817 13,46007 0,545 40,3728
HI 0,009 1,151212 0,061 7,802657 0,06 7,674745 0,18 23,02423
I2 0 0 0 0
O2 0 0 0 0
CO2 0,042 1,848399 0,443 19,49621 0,28 12,32266 0,84 36,96798
Total 10,21536 581,9598 135,6693 5384,264 39,90382 2298,946 119,7114 6896,83
State
T °C 453 398 180 180
P (barg) 43 20 44 44
enthalpy MJ/h -1213,05 -10426,9 -4503,06 -13509,4

Steam # 21 22 23 24
CO 0 1,5 42,01515 1,81 50,69828 1,5 42,01515
CH3OCH3 0 0,017 0,783163 0,0625 2,879278 0,013 0,59889
CH3I 0 0,04 5,67756 0,1225 17,38753 0,01 1,41939
CH3COOCH3 0 0,01 0,740785 0,1635 12,11184 0,09 6,667069
CH3OH 65 2082,721 0 30 961,2558 65 2082,721
H2O 0 0 0,01 0,180153 0,2 3,603056
HCOOH 0 0 0 0,00212 0,097574
CH3COOH 0 0 0 36 2161,871
CH3CH2COOH 0 0 0 0,1817 13,46007
HI 0 0,03 3,837372 0,031 3,965285 0,03 3,837372
I2 0 0 0 0
O2 0 0 0 0
CO2 0 0,1 4,40095 0,263 11,5745 0,18 7,92171
Total 65 2082,721 1,697 57,45498 32,4625 1060,053 103,2068 4324,212
State
T °C 298 438 353 353
P (barg) 32 20 20 20
enthalpy MJ/h -4313,3 -56,94 -1855,28 -8507,22

Steam # 25 26 27 28
CO 1,81 50,69828 8,55 239,4864 8,55 239,4864 0
CH3OCH3 0,0625 2,879278 0,0855 3,938852 0,0855 3,938852 0
CH3I 0,1225 17,38753 0,1425 20,22631 0,1425 20,22631 0
CH3COOCH3 0,1635 12,11184 0,2115 15,66761 0,185 13,70453 0,0265 1,963081
CH3OH 30 961,2558 0 0 0
H2O 0,01 0,180153 0,01 0,180153 0 0,01 0,180153
HCOOH 0 0 0 0
CH3COOH 0 0 0 0
CH3CH2COOH 0 0 0 0
HI 0,031 3,965285 0,171 21,87302 0,171 21,87302 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0,263 11,5745 0,798 35,11958 0,798 35,11958 0
Total 32,4625 1060,053 9,9685 336,4919 9,932 334,3486 0,0365 2,143234
State
T °C 352 450 453 448
P (barg) 2 10 11 9
enthalpy MJ/h -1856,11 -372,5 -361,11 -3,61

Steam # 29 30 31 32
CO 6,74 188,7881 1,5 42,01515 8,24 230,8032 0
CH3OCH3 0,023 1,059574 0,017 0,783163 0,04 1,842738 0
CH3I 0,02 2,83878 0,04 5,67756 0,06 8,516339 0
CH3COOCH3 0,048 3,55577 0,01 0,740785 0,058 4,296555 0
CH3OH 0 0 0 0
H2O 0 0 0 0
HCOOH 0 0 0 0
CH3COOH 0 0 0 0
CH3CH2COOH 0 0 0 0
HI 0,14 17,90774 0,03 3,837372 0,17 21,74511 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0,535 23,54508 0,1 4,40095 0,635 27,94603 0
Total 7,506 237,695 1,697 57,45498 9,203 295,15 0 0
State
T °C 353 438 438 423
P (barg) 3 20 20 2
Specific Enthalpy kj/kg -1106,47 -348,377 -3917,52
enthalpy MJ/h -73,056 -5,56 -321,183

Steam # 33 34 35 36
CO 8,55 239,4864 0,45 12,60455 8,55 239,4864 0
CH3OCH3 0,0855 3,938852 0,0045 0,207308 0,0855 3,938852 0
CH3I 0,1425 20,22631 0,0075 1,064542 0,1425 20,22631 0
CH3COOCH3 0,285 21,11238 0,015 1,111178 0,285 21,11238 0,1 7,407854
CH3OH 0 0 0 0
H2O 0,57 10,26871 0,03 0,540458 0,57 10,26871 0,57 10,26871
HCOOH 0,00604 0,277993 0,00032 0,014728 0,00604 0,277993 0,00604 0,277993
CH3COOH 102,6 6161,331 5,4 324,2806 102,6 6161,331 102,6 6161,331
CH3CH2COOH 0,518 38,37268 0,027 2,000121 0,518 38,37268 0,518 38,37268
HI 0,171 21,87302 0,009 1,151212 0,171 21,87302 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0,798 35,11958 0,042 1,848399 0,798 35,11958 0
Total 113,726 6552,007 5,98532 344,8231 113,726 6552,007 103,794 6217,658
State
T °C 453 453 453 453
P (barg) 44 44 11 11
Specific Enthalpy kj/kg - 7051,26 -7051,89 -7017,57 -7219,73
enthalpy MJ/h -12833,3 -675,46 -12772 -12469,4

Steam # 37 38 39 40
CO 0 0 0 0
CH3OCH3 0 0 0 0
CH3I 0 0 0 0
CH3COOCH3 0,0035 0,259275 0,0965 7,148579 0,0035 0,259275 0,07 5,185498
CH3OH 0 0 0 0
H2O 0,02 0,360306 0,55 9,908404 0,02 0,360306 0,54 9,728251
HCOOH 0,00021 0,009665 0,00583 0,268328 0,00021 0,009665 0,00583 23,01269
CH3COOH 3,6 216,1871 99 5945,144 3,6 216,1871 99 5945,144
CH3CH2COOH 0,018 1,333414 0,5 37,03927 0,018 1,333414 0,5 0,431878
HI 0 0 0 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0 0 0 0
Total 3,64171 218,1497 100,1523 5999,509 3,64171 218,1497 100,1158 5983,502
State
T °C 453 453 453 453
P (barg) 11 11 43 7
enthalpy MJ/h -437,579 -12035,5 -437,78 -12027,8

Steam # 41 42 43 44
CO 0 0 0 0
CH3OCH3 0 0 0 0
CH3I 0 0 0 0
CH3COOCH3 0,07 5,185498 0,07 5,185498 0 0
CH3OH 0 0 0 0
H2O 0,55 9,908404 0,55 9,908404 0,55 9,908404 0,55 9,908404
HCOOH 0,00583 0,268328 0,00583 0,268328 0 0
CH3COOH 0 0 0 0
CH3CH2COOH 0 0 0 0
HI 0 0 0 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0 0 0 0
Total 0,62583 15,36223 0,62583 15,36223 0,55 9,908404 0,55 9,908404
State
T °C 453 453 453 453
P (barg) 7 7 6 7
Specific Enthalpy kj/kg -10438,6 -10438,6 -13159,7 -13167
enthalpy MJ/h -44,5443 -44,5443 -36,22 -36,24

Steam # 45 46 47 48
CO 0 0 0 0
CH3OCH3 0 0 0 0
CH3I 0 0 0 0
CH3COOCH3 0 0 0 0
CH3OH 0 0 0 0
H2O 0,01 0,180153 0,54 9,728251 0,02 0,360306 0,52 9,367946
HCOOH 0 0 0 0
CH3COOH 0 0 0 0
CH3CH2COOH 0 0 0 0
HI 0 0 0 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0 0 0 0
Total 0,01 0,180153 0,54 9,728251 0,02 0,360306 0,52 9,367946
State
T °C 453 453 453 453
P (barg) 7 7 7 7
Specific Enthalpy kj/kg -13168,8 -13166,2 -13168,8 -

13165,747
enthalpy MJ/h -0,659 -35,579 -1,318 -34,26

Steam # 49 50 51 52
CO 0 0 0 0
CH3OCH3 0 0 0 0
CH3I 0 0 0 0
CH3COOCH3 0 0 0,07 5,185498 0,06 4,444712
CH3OH 0 0 0 0
H2O 0,52 9,367946 0 0 0
HCOOH 0 0 0,00583 0,268328 0,005 0,230127
CH3COOH 0 99 5945,144 0 0
CH3CH2COOH 0 0,5 37,03927 0 0
HI 0 0 0 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0 0 0 0
Total 0,52 9,367946 99,5 5982,183 0,07583 5,453826 0,065 4,674839
State
T °C 453 500 453 453
P (barg) 44 5 7 7
Specific Enthalpy kj/kg -4320967 -6742,72 -5482,68 -5482,97
enthalpy MJ/h -11244,1 -11204,5 -8,306 -7,12

Steam # 53 54 55 56
CO 0 0 0 0
CH3OCH3 0 0 0 0
CH3I 0 0 0 0
CH3COOCH3 0,01 0,740785 0,01 0,740785 0 0
CH3OH 0 0 0 0
H2O 0 0 0 0
HCOOH 0,00083 0,038201 0,00083 0,038201 0 0
CH3COOH 0 0 0,3 18,01559 0
CH3CH2COOH 0 0 0,5 37,03927 0,5 37,03927
HI 0 0 0 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0 0 0 0
Total 0,01083 0,778986 0,01083 0,778986 0,8 55,05486 0,5 37,03927
State
T °C 453 453 500 450
P (barg) 7 44 5 4
enthalpy MJ/h -1,186 -1,252 -91,7 -63,357

Steam # 57 58 59 60
CO 0 0 0 0
CH3OCH3 0 0 0 0
CH3I 0 0 0 0
CH3COOCH3 0 0 0 0
CH3OH 0 0 0 0
H2O 0 0 0 0
HCOOH 0 0 0 0
CH3COOH 0,3 18,01559 99 5945,144 99 5945,144 99 5945,144
CH3CH2COOH 0 0 0 0
HI 0 0 0 0
I2 0 0 0 0
O2 0 0 0 0
CO2 0 0 0 0
Total 0,3 18,01559 99 5945,144 99 5945,144 99 5945,144
State
T °C 450 500 450 450
P (barg) 5 5 5 5
enthalpy MJ/h -36,157 -11146,6 -11930,6 -11930,6

10. DISCUSSION
At the production method of acetic acid by using methanol which was carbonylation. There
were many types of methanol carbonylation. These were BASF Process based on Co(CO)4
complex, Monsanto-BP Process based on Rh carbonyl complex, BP-Cativa process based on
Ir carbonyl complex. The Acetica Process based on a heterogeneous Rh catalyst in which the
active Rh complex is chemically immobilized on a polyvinylpyridine resin. We chose to work
with Acetica Process. In comparison with conventional systems, the key features of Chiyoda
Acetica process are;
 Higher productivity: unlike homogeneous catalyst systems, the coıncentration of Rhis

not restricted by solubility limitations of a liquid catalyst. With Acetica, the Rh
concentration can be increased, enabling higher react, on levels.
 Few mechanical problems: The Acetica process employs a unique bubble-column
reactor that has no mechanical aqitator, meaning fewer problems with leakage and
maintenance.
 Moderate corrosive systems: The heterogeneous catalyst system enables the use of
less water in the systems, resulting in a lower concentration of hydrogen iodide which
is the leading contribuctor to corrosion. Zr is used in the reactor system. However, Ti
or hastelloy is acceptable for use in the rest of the system, thereby reducing investment
costs.
 Higher product purity and lower by-product formation: The high degree of catalyst
activity under a low water concentration suppresses the formation of by-products,
resulting in higher product purity.
 Competitive economics: A moderate corrosive system enviroment enables the use of
lower-grade materials. In addition, the higher yield of actic acid and the recovery of
the reaction heat in the reactor system reduce operating costs.
 More flexible for large-scale capacity: Because there are no moving parts or
mechanical equipment in the reactor, Acetica offers more flexible application to larger
plants having an annual capacity such as 200,000 to 500,000 tons.
 Easy catalyst handling: There is no need to recover the rhodium by seperating it from
the reaction liquid.
 Open licensing policy: Chiyoda offers Acetica tecnology based on an open license
policy.
Block diagram was drawn to solve the system more easily. When the equipments were
concerned in this diagram, there was for some comments. For example, the flash vaporization
was required in this system. There were approximately 40 °C difference between the boiling
points of the components. In this case, to put the flash vaporization in the system inevitably.
Acetic acid needs of the world in 2035, approximately 1.3 million tons / year, calculated as.
We aimed 75 thousand tons / year producing, in our plant at meeting the need. We wanted to
meet the needs of Turkey, primarily. As the case import also be considered.
Gebze was selected for plant site. Because;
 Gebze is one of the developed industrial region in Turkey.

 Also there is very close to Istanbul which electricity consumption is the biggest city in
Turkey.
 Gebze has a seaport. So, raw material is supplied from foreign countries. If
unexpected stuation about raw material it can be taken different way.
 Gebze is near to sea and water source. This species to get advantage about all process,
especially cooling water.
 Temperature, pressure, relative humudity, snow and rain potantial and wind velocity
effected to process. So Gebze to prevent good condition about all these parameters.
11. CONCLUSION
- Gebze was selected for plant site.

- Plant capacity was determined by taking of 30 years acetic acid demand of Turkey.
- Iodine was added to mixing vessel.
- Slurry bubble loop reactor was chose the type of reactor.
- Chemcad simulation program is used to find enthalpies of streams for the energy
balance.
12. RECOMMENDATION
Methanol can produce instead buying which is our raw material. Method of coal gasificaton
can be used for production of methanol. By doing some economic analysis, should be agreed
which is more suitable.
13. SYMBOLS
: mass flow rate of CH3OH
: mass flow rate of CO
A,B,C,D : Cp constants
Hi : enthalpy of species I
Hinput : total enthalpy of input stream
Houtput : total enthalpy of output stream
TR : reference temperature
ΔHf : heat of formation
ΔHsystem : enthalpy change for input-output stream
14. REFERENCES
1. http://cetiner.tripod.com/Properties.htm
2. http://chemicalland21.com/petrochemical/acetic%20acid.htm
3. Ullmann, J. (2007), “ Ullmann’s Encyclopedia of Industrial Chemistry”, Willey
4. http://en.wikipedia.org/wiki/Acetic_acid
5. http://www.chemicalland21.com/industrialchem/organic/PROPIONIC%20ACID.htm
6 . Yoneda , N. ,Kusano ,S. , Yasui, M., Pujado, P. ,Wilcher, S. ,(2001), “Recent advances
in processes and catalysts for the production of acetic acid” , Japan
7. Plotkin, J., Song, L.,(2003), “production has more feedstock and production approaches
than any other volume chemical”, Usa
8. Jones. J,H, ( 2000), “The Cativa Process for the Manufacture of Acetic Acid “ , U.K
9. PERP Program – New Report Alert (2003), “ Nexant’s ChemSystems Process

Evaluation/Research Planning program, Acetic Acid “ , NewYork
10. Hosonno, Y., Tasaki, M,(2005), “Handbook of Petrochemicals Production Processes”,
McGraw-Hill, United States
11. Lim, N. (1999), “ Acetic Acid by the Chiyoda/UOP ACETICA™ Process”, Japan
12. http://www.methanolmsa.com/exec/sam/view/id=194/node=117/
13. http://chemical.ihs.com/CEH/Public/Reports/602.5000/
14. http://www.acetic-acid.net/acetic-acid-production
15.TUIK
16. Bann, W., (2010), “ A monthly roundup and alysis of the key factors shaping World
chemical markets”, Tecnon Orbichem

Acetica

Încărcat de

Informații document

Titlu original

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Acetica

Încărcat de

Drepturi de autor:

Formate disponibile

1.

Physical Properties of Methanol

Melting Point : -97.7 0C

Relative Density : 0.79

Molecular weight: 32.042 kg/kmol

Heat of Formation -201.3 MJ/kmol

Gibbs Free Energy -162.62 MJ/kmol

Freezing point: -97.7 °C

Boiling point: 64.6 °C (at atmospheric pressure)

Critical pressure 81 bar abs

Critical volume 0.118 m³/kmol

Density 791 kg/m³ at 20 °C

Heat of Vaporization 35278 kJ/kmol

where log(viscosity) = a * ( 1/T - 1/b )

a = 21.152 b = 0.07092 c = 2.59E-05 d = -2.85E-08

where Cp = a + b*T + c*T² + d*T³

a = 18.5875 b = 3626.55 c = -34.29

where ln(P) = a - b/(T+c) P: mmHg; T: °K

within range -16 to 91°C [1]

2CH3OH + 3O2 ===> 2CO2 + 4H2O

Methanol is oxidized with acidified Potassium Dichromate, K2Cr2O7, or with acidified

2H2 + O2 ===> 2H2O

Formaldehyde Formic Acid

Catalytic Oxidation of Methanol:

Methanol reacts with organic acids to form esters.

Substitution of Methanol with Sodium

2 CH3OH + 2 Na ===> 2CH3ONa + H2

Substitution of Methanol with Phosphorus Pentachloride

Methanol reacts with phosphorus pentachloride at room temperature to form hydrogen

CH3OH + PCl5 ===> HCl + CH3Cl + POCl3

Substitution of Methanol with Hydrogen Chloride

2.2. ACETIC ACID

Specific heat capacity :

Chemical properties of Acetic Acid

can separate from the molecule by ionization:

Cyclic dimer of acetic acid; dashed lines represent hydrogen bonds

Reactions with inorganic compounds

Because aluminium forms a passivating acid-resistant film of aluminium oxide, aluminium

NaHCO3 + CH3COOH → CH3COONa + CO2 + H2O

2.3. PROPIONIC ACID

Mol wt. 74.08

Oral rat ld50: 2600 mg/kg

Synonyms hydroacrylic acid; carboxyethane; methylacetic acid; c-3 acid; metacetonic

Classification fungicide, bactericide, preservative, acidifying agent

Physical and Chemical Properties

Physical State : clear liquid

Boiling Point: 140.7 - 141.7 C

Specific Gravity : 0.990 - 0.998

soluble in almost conventional organic solvents and alcohol

pka 4.875 (at 25 c)

log p 0.33 (octanol-water)

Vapor Pressure : 3.53 (mmhg)

Henry Law Constant : 4.45e-07 (atm-m3/mole at 25 c)

Nfpa Ratings Health: 3; Flammability: 2; Reactivity: 0

Stability : Stable under ordinary conditions. light sensitive [5].

3.1. Demand & Supply

Figure 2: Acetic Acid Supply by Major Region [12]

3.3. Imports & Exports

TABLE 1 : Import Export Datas of Turkey [15]

Year Flow Weight (kg)

2010 Import 54621982

2010 Export 1900514

2009 Import 49258811

where Cp = a + bT + cT² + d*T³