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Soran University Faculty of Engineering Department of Chemical Engineering
Soran University Faculty of Engineering Department of Chemical Engineering
Faculty of engineering
Department of chemical engineering
20/11/2019
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1 Introduction :
Acetic acid is an important commodity used in chemical industries, with about 9 million tons of
world demands per year. The primary use of this chemical is in the manufacture of assorted
acetate esters, fungicide, organic compounds, organic solvents and the preparation of
pharmaceuticals, cellulose acetate that is important in making film and plastic wares, perfumes
and synthetic fiber.
Sharp odor,
It is found in ocean water, oilfield brines, rain, and at trace concentrations in many plant and
animal liquids. It is central to all biological energy pathways. Fermentation of fruit and vegetable
juices yields 2–12% acetic acid solutions, usually called vinegar (qv). Any sugar-containing sap
or juice can be transformed by bacterial or fungal processes to dilute acetic acid. Theophrastus
(272–287 BC) studied the utilization of acetic acid to make white lead and Andreas Libavius
(AD 1540–1600) distinguished the properties of vinegar from those of ice like (glacial) acetic
acid obtained by dry distillation of copper acetate or similar heavy metal acetates. Lavoisier
believed he could distinguish acetic acid from acetous acid, the hypothetical acid of vinegar,
which he thought was converted into acetic acid by oxidation. Uses include the manufacture of
vinyl acetate and acetic anhydride. Vinyl acetate is used to make latex emulsion resins for paints,
adhesives, paper coatings, and textile finishing agents. Acetic anhydride is used in making
cellulose acetate fibers, cigarette filter tow, and cellulosic plastics.
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PHYSICAL PROPERTIES:
Acetic acid is a clear, colorless, corrosive liquid that has a pungent odor and is a dangerous
vesicant. It has pungent vinegar like odor. The detectable odor is as low as 1 ppm. The liquid is
usually available as glacial acetic acid with less than 1 Wt % water and over 98 % purity.
Besides water, the acid contains traces of impurities such as acetaldehyde, oxidized substances,
iron, and chlorides. Occasionally, the acid may be colored due to the presence of ethyl
acetoacetate. The acetate is easily mistaken for formic acid because it reduces mercuric
chloride. Traces of mercury may cause extensive corrosion by reaction with aluminum.
Aluminum is a common material for containers to ship the acid .Glacial acetic acid is very
hydroscopic. The presence of 0.1 Wt % water lowers the freezing point significantly. Acetic
acid forms azeotropes with many common solvents, such as benzene, pyridine, and dioxane.
Acetic acid is miscible with water, ethanol, acetone, benzene, ether, and carbon tetrachloride.
However, it is not soluble in CS2.The presence of acetaldehyde or formic acid is commonly
revealed by permanganate tests
• Though the molecular weight of acetic acid is 60.05, its apparent molecular weight varies
with both temperature and the other associating substances present.
• A zero dipole moment for unsymmetrical acetic acid structure(is explained by the formation
of symmetric dimmers via hydrogen bonding in which the dipole moments cancel).
• Has a very strong leveling effect on bases and solvolyzes all strong bases to acetate ion,
CH3COO- .
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4. Thermal conductivity : 0.158 W/m2 0C at 200C
5. Heat of melting : 207.1 J/g
6. Heat of vaporization : 394.5J/g at boiling point
7. Specific heat of vapor : 5.029 J/g 0K at 1240C
8. Density : 1.04938 g/ml at 200C
9. Refractive index,ηd : 1.36965
10. Specific heat of solid : 0.837 J/g 0K at 1000K
11. Critical pressure : 57.856 KPa (571.1 atm)
12. Critical temperature : 321.60C
13. Magnetic susceptibility Solid Liquid
Solid : 32.05 10-6 cm3/mol
Liquid : 31.80 10-6 cm3/mol
14. Dielectric constant Solid Liquid
15. Surface tension
16. Flash point, open cup
17. Auto ignition point
18. Lower limit of flammability :
CHEMICAL PROPERTIES:
Many useful materials are made from acetic acid. Acetate esters are formed by reaction of
olefins or alcohols with acetic acid. Acetic acid is also used in the preparation of
pharmaceuticals. Aspirin (acetylsalicylic acid) is formed by the reaction between acetic acid
and salicylic acid.
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This esterification reaction is reversible, however, and the presence of water can lead to
hydrolysis of the aspirin. Thus, an anhydrous (“without water”) reagent could lead to better
yields of product. Acetic anhydride can by prepared by the dehydration of acetic acid at
800OC.
Alternatively, the reaction between the acid chloride and a salt of acetic acid (e.g. sodium
acetate) yields acetic anhydride and a salt.
Reactions with inorganic compounds Acetic acid is mildly corrosive to metals including iron,
magnesium, and zinc, forming hydrogen gas and salts called acetates:
Mg + 2CH3COOH → (CH3COO)2Mg + H2
Decomposition Reactions:
Minute traces of acetic anhydride are formed when very dry acetic acid is distilled. Without a
catalyst, equilibrium is reached after 7 hrs of boiling, but a trace of acid catalyst produces
equilibrium in 20 min. Thermolysis of acetic acid occurs at 442OC and 101.3 KPa (1 atm),
leading by parallel pathways to methane and carbon dioxide, and to ketene and water. Both
reactions have great industrial significance.
Acid–Base Chemistry:
Acetic acid dissociates in water, pKa=4.76 at 25OC. It is a mild acid that can be used for
analysis of bases too weak to detect in water. It readily neutralizes the ordinary hydroxides of
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the alkali metals and the alkaline earths to form the corresponding acetates. Other acids exhibit
very powerful, super acid properties in acetic acid solutions and are thus useful catalysts for
esterification of olefins and alcohols. Nitration conducted in acetic acid solvent are affected
because of the formation of the nitronium ion, (NO2+) Hexamethylenetetramine may be
nitrated in acetic acid solvent to yield the explosive cyclotrimethylenetrinitramine , also known
as cyclonit or RDX.
Acetylation Reactions:
Alcohols may be acetylated without catalysts by using a large excess of acetic acid.
• Over 60% of acetic acid produced goes into polymers derived from either Vinyl acetate (vinyl
esters) or cellulose (cellulose esters).
• Most of poly (vinyl acetate) is used in paints and coatings or used for making poly (vinyl
alcohol) and plastics
• Acetic acid and acetate esters are used extensively as solvents and in organic Synthesis.
• In the production of white lead and chrome yellow pigments, it is used to make lead
available in a soluble form for further reaction to give basic lead carbonate and lead chromate.
• Also used to provide the necessary acidity in the number of processes carried out in an
aqueous media.
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• Dilute acetic acid functions either or both as a preservative and flavoring agent in food stuffs
such as pickled vegetables, condiments, jellies and confectionery.
• Also, lower alkyl esters such as methanol, ethanol, isopropanol and butanol are widely used
as solvents for lacquers and adhesives. Other esters form basis for synthetic flavors for
perfumes and bornyl acetate in the manufacture of synthetic camphor.
1. Acetic anhydride
2. Vinyl acetate
3. Cellulose acetate
4. Monochloro acetic acid
5. Purified Terepthalic acid [PTA]
6. Food Additives [vinegar]
There are mainly three processes that produce acetic acid. They are
Acetaldehyde Oxidation
Methanol Carbonylation
Anaerobic fermentation
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THE SELECTED PROCESS: Methanol Carbonylation
route
Undoubtedly the methanol carbonylation route has a much greater production when compared
to any other processes i.e. it holds 75% of the world’s acetic acid production technologies.
Production of Acetic acid by carbonylation of methanol used to be done by a process named as
Monsanto process where Rhodium catalyst was used as an active catalyst with iodide of metals
such as lithium. The process was carried at 50-60 bar pressure and at a temperature of 150 to
200oC giving a high selectivity of 99% based on the methanol feed. But B.P chemicals came
up with a process named as Cativa that used Iridium catalyst with Hydrogen iodide as the
active catalyst in the system. Henry Drefyus at British Celanese developed a methanol
carbonylation pilot plant as early as 1925. However, a lack of practical materials that could
contain the corrosive reaction mixture at the high pressures needed (200 atm or more)
discouraged commercialization of these routes. The first commercial methanol carbonylation
process, which used a cobalt catalyst, was developed by German chemical company BASF in
1963. In 1968, a rhodium-based catalyst (cis− [Rh(CO)2I2]−) was discovered that could
operate efficiently at lower pressure with almost no byproducts. The first plant using this
catalyst was built by US chemical company Monsanto Company in 1970, and rhodium-
catalyzed methanol carbonylation became the dominant method of acetic acid production. In
the late 1990s, the chemicals company BP Chemicals commercialized the Cativa catalyst
([Ir(CO)2I2]−), which is promoted by ruthenium. This iridium catalyzed process is greener and
more efficient and has largely supplanted the Monsanto process, often in the same production
plants.
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This overcame many limitations of the Monsanto process as
• Lower water concentration was obtained in the product compared to Monsanto process.
• The process now could be carried at a comparatively lesser pressure and temperature.
• Iridium is cheaper than Rhodium, hence reducing the cost of production to a large extent.
The Cativa Process is carried 30-40 bar pressure and at a temperature of 150-180oC giving a
high selectivity of 99%(based on the methanol feed).
Main reaction:
Side Reactions:
The process involves iodomethane as an intermediate, and occurs in three steps. A catalyst,
usually a metal complex, is needed for the carbonylation
By altering the process conditions, acetic anhydride may also be produced on the same plant.
Because both methanol and carbon monoxide are commodity raw materials, methanol
carbonylation long appeared to be an attractive method for acetic acid production. The use of
other less expensive catalyst such as nickel, palladium, and ruthenium in homogeneous systems
has also been investigated. In 1996, BP Amoco commercialized the iridium-based Cativa
technology, which operates with reactor water levels that are comparable to the improved
Monsanto process. The new catalyst is most effective when used in combination with lithium
and ruthenium. The Cativa technology is installed in Sterling’s Texas City acetic acid plant,
which has a capacity of 990 million lb/yr (450,000 t/yr)
This is the catalytic cycle for the carbonylation of methanol using iridium as the catalyst
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ADVANTAGES OF SELECTED PROCESS:
• The selectivity of Cativa process is 99% as compared to the 90% of acetaldehyde oxidation
and even lesser in other processes.
• The methanol used as the feed is comparatively cheaper than the feed in other processes.
• Fermentation process which also seems viable in terms of operation involves a greater
upstream and downstream cost for sterilization of equipment to provide an environment for
microbial growth.
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PROCESS DETAILS
The carbonylation process of methanol is carried out in a continuous stirred tank reactor. The
methanol and carbon monoxide is fed to the reactor from the bottom as feed. The carbon
monoxide is compressed in a compressor to 30 bar before inlet to the reactor to ensure the
reaction is occurs in the liquid phase. The reaction is highly exothermic and hence a cooling
jacket is provided outside the reactor to ensure that the proper temperature of 150oC is
maintained in the reactor. The initial heat required to ignite the reaction is mainly rough age of
steam through the jacket. As the reaction starts, the heat of reaction is used to continue the
reaction and excess heat is removed. The following will be the process flow diagram for
methanol carbonylation route. The unreacted gases are vented out through a scrubber which
also works as a preheater for a part of methanol feed. A part of methanol feed is preheated from
ambient temperature to 60oC as it comes out of the scrubber Another work that is performed
by the side stream is the stripping of entrained liquid in the vent gases and it also ensures that
the loss of product with these gases is minimal. The vent gases generally exit the scrubber at
50oC to the atmosphere.
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The product stream from the CSTR, is rich in acetic acid and containing small
concentrations of methanol, by-product propionic acid and water is made to pass through
the throttling valve to the flash tank where the product is flashed to a reduced pressure of 1
atm. The product from the flash tank is fed to the light end distillation column at a
temperature of 52oC. A recycle stream is pumped from the bottom of the flash tank back to
the CSTR. In the light end distillation column the feed containing acetic acid, water,
propionic acid, methanol and methyl acetate is distilled to separate light ends (methyl
acetate and methanol) from the bottom stream containing acetic acid, propionic acid and
little concentration of water. The acetic acid is generally 87.6 % by wt. which is further
purified in the acid purification unit to obtain the required product. The feed stream enters
at a temperature of about 52oC and the bottom stream leaves the end column at a
temperature of 97oC. In the acid purification unit, the stream enters at a temperature of
97oC. The higher boiling component propionic acid is obtained from the bottom of the
distillation tower where a temperature of 123oC is maintained. Glacial Acetic acid (99.8%
by wt.) is obtained from the top of the distillation tower, maintained at 118oC.
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MATERIAL BALANCE
Material balance is the basis of process design. A material balance taken on complete
process determines the quantities of material required and the products produced. Balance
over individual process unit sets the process stream flows and compositions. Material
balances are also useful tool for study of plant operation and trouble shooting. They can be
used to check the performance against design to check instrument calibration and to locate
the source of material loss.
It is known that 99.8% acetic acid by weight is to be obtained as the overhead product.
Assumed capacity of the plant = 100 TPD = 33400 TPA Because the total working hours
for a plant under operation per a year are 8000 hours so 334 days.
Hence for the 2nd distillation column (acetic acid purification column) the following data
is known We have, XD = 0.998, And D XB = 0.00085, = 100 TPD = 4166.67 kg/hr of
Acetic acid. Taking wt. per hour basis of acetic acid, B= (-)/(-) XF = 0.876 (all in Wt %) =
4166.67 × (0.876-0.998) / (0.00085-0.876)= 580.853 kg Thus, F = D + B = 4747.523 kg.
Hence, the weight and wt. fraction can be arranged for DC-II in the table as:
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Table - Material balance for Distillation column – 2
Now, as assumed remaining methanol is converted to methyl acetate during the throttling
operation. Hence the amount of acetic acid remains constant and can be used to find the
moles (and thus the wt.) of methanol to be used.
Main Reactions:
CH₃OH + CO = CH₃COOH
Side Reactions:
CH₃OH + ½ CO = C2H5COOH
CH₃OH + CO = CH₃COOH
Thus,
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methanol requirement = 69.28 Kmoles = 69.28/0.8192 = 84.57 Kmoles Also, total water is
produced in propionic acid and methyl acetate reaction. ∴ Total water produced = 0.01×
0.9091 × 84.57 + 0.0899 × 84.57
= 8.37 Kmoles
Total water in light end distillation column feed = 9.13 Kmoles Carbon monoxide is taken
7.2%in excess than the methanol feed. ∴ Moles of carbon monoxide = 107.2% × 84.57 =
90.66 Kmoles CO is the excess reagent and Methanol is the limiting reagent. Considering
overall material balance assuming the reactor, scrubber and flash tank as a complete system
we have, Mass of gas in vent = Mass of methanol in + Mass of carbon monoxide in – Mass
of feed in light end distillation column Mass of vent from scrubber = 2709.6228 + 2538.48
– 4945.73 = 296.56 kg Also, 20% in excess promoter, i.e. Hydrogen Iodide and Iridium
Catalyst is assumed to be used in the reactor. Hence, weight of catalyst = 20% excess of
feed methanol = 12981.36 Kg = 12.98 Tons This catalyst is recycled back to the reactor
from the flash tank and hence is not required to be fed again and again
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Table - Material balance for distillation column – I
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EQUIPEMENT DESIGN
AVERAGE MOLECULAR WEIGHT CALCULATION:-
Feed to the DC-II = 4158.828 Kg/hr of acetic acid + 17.83576 Kg/hr of water + 570.857
Kg/hr of Propionic acid = 4747.521 Kg/hr Top product from DC-II Bottom product from
DC-II Feed:- Total flow Molefraction of acetic acid in feed = 4747.521 Kg/hr =
4158.828/4747.521 = 0.876 Average molecular weight calculation: Total no of feed moles
Average molecular weight = 77.961 Kmoles/hr = 4747.521 / 77.961 = 60.895 Kg/Kmole
Distillate:- Total flow rate of distillate Mole fraction of acetic acid in distillate Average
molecular weight calculation Total moles of distillate = 69.2478 + 0.46278 = 69.7105
Kmole/hr Average molecular weight of distillate = 4166.67 /69.7105 = 59.7709 Kg/Kmole
Bottom: Total bottom flow rate Mole fraction of acetic acid Average molecular weight
Total moles Average molecular weight = 580.853 Kg/hr = 0.001 = 580.853 / total moles =
8.269 Kmole/hr = 580.853 / 8.269 = 70.24 Kg/Kmole 55 | P a g e = 99.8% purity of acetic
acid = 98.279% purity of propionic acid = 4166.67 Kg/hr = 0.998
We have following data for DC-2 from material balance XD=0.998, XF=0.876, XB=0.001
Calculation of relative volatility: We need to calculate the vapor pressures of acetic acid
and propionic acid at 370K Vapor pressure for acetic acid: From perry’s handbook we have
values of acetic acid
C1=53.27,C2=-6304.5,C3=-4.2985,C4=8.8865×10-18,C5=6
P = 10.8346
P = e10.8346
P = 50746.62 KPa
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Vapor pressure calculation for propionic acid
ln P = 54.552-19.322-25.29146+0.00303
ln P = 9.941
P = e9.941
P = 20776.33Kpa
α = vapor pressure of acetic acid at 370K /vapor pressure of propionic acid at 370K
α = 50746.62/20776.33 α =2.4425
We know that
y = (α×x)/(1+( α-1)×x)
y = (2.4425×x)/(1+1.4425×x)
As it is saturated liquid q=1 Now Rmin is calculated in the following way Rmin=(1/
α)((XD/XF)-( α×(1-XD)/(1-XF)) Hence by substituting the values of α, XD, XF We have
Rmin=0.45030. Now R = 1.5×Rmin R = 0.67545
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Now by giving equilibrium data and conditions in the excel VBA Macros we obtain the following
curve
Number of stages=15
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SAFETY, HEALTH AND ENVIRONMENT ASPECTS
The goal of chemical plant is not only to produce the chemicals, but to produce them
safely. In the plant’s chain of processes and operations, loss of control anywhere can lead to
accidents and then losses of life and property from hazards. Attempts should be made to
prevent troubles from the inspection while designing, fabricating and operating. Safety
generally involves: 1. Identification and assessments of the hazards 2. Control of hazards 3.
Control of the process by provision of automatic control system, interlocks, alarm trips, etc.
4. Limitation of the loss, by press relief, plant layout, etc...
Inhalation:
Inhalation of concentrated vapors may cause serious damage to the lining of the nose,
throat, and lungs. Breathing difficulties may occur. Neither odor nor degree of irritation are
adequate to indicate vapor concentration.
Ingestion:
Swallowing can cause severe injury leading to death. Symptoms include sore throat,
vomiting, and diarrhea. Ingestion of as little as 1.0 ml has resulted in perforation of the
esophagus.
Skin Contact: Contact with concentrated solution may cause serious damage to the skin.
Effects may include redness, pain, skin burns.High vapor concentrations may cause skin
sensitization.
Eye Contact:
Eye contact with concentrated solutions may cause severe eye damage followed by loss of
sight. Exposure to vapor may cause intense watering and irritation to eyes.
Chronic Exposure:
Repeated or prolonged exposures may cause darkening of the skin, erosion of exposed
front teeth, and chronic inflammation of the nose, throat, and bronchial tubes .
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Persons with pre-existing skin disorders or eye problems, or impaired respiratory function
may be more susceptible to the effects of the substance
Eye Contact:
Check for and remove any contact lenses. In case of contact, immediately flush eyes with
plenty of water for at least 15 minutes. Cold water may be used. Get medical attention
immediately.
Skin Contact:
In case of contact, immediately flush skin with plenty of water for at least 15 minutes
while removing contaminated clothing and shoes. Cover the irritated skin with an
emollient. Cold water may be used.Wash clothing before reuse. Thoroughly clean shoes
before reuse. Get medical attention immediately.
Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial
cream. Seek immediate medical attention.
Inhalation:
If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is
difficult, give oxygen. Get medical attention immediately.
Serious Inhalation:
Evacuate the victim to a safe area as soon as possible. Loosen tight clothing such as a
collar, tie, belt or waistband. If breathing is difficult, administer oxygen. If the victim is not
breathing, perform mouth-to-mouth resuscitation. WARNING: It may be hazardous to the
person providing aid to give mouth-to-mouth resuscitation when the inhaled material is
toxic, infectious or corrosive. Seek immediate medical attention.
Ingestion:
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carbonated bevarages. Loosen tight clothing such as a collar, tie, belt or waistband. Get
medical attention if symptoms appear.
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References
1. Perry’s Chemical Engineering Handbook 8th edition.
5. “The Cativa TM Process for the Manufacture of Acetic Acid” By Jane H. Jones, B.P
Chemicals Ltd.
6. United States Patent, Garland et. al. , Processes for the production of Acetic Acid.
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