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Table of Contents

Identification of Product Chemistry, Properties, Uses, World Market and Projected


Market Growth....................................................................................................... 2
Acetic acid properties......................................................................................... 2
Methanol Carbonylation (Monsanto process)......................................................3
References............................................................................................................. 8

Identification of Product Chemistry, Properties, Uses,


World Market and Projected Market Growth
Acetic acid properties
Acetic acid is a clear colourless liquid that is very corrosive and has a
noticeable odour. The odour can be detected when concertation is as low
as 1ppm. A table summarising the physical properties is below;
Acetic Acid
Appearance

Molecular weight
Boiling point
Melting point
Critical temperature
Critical pressure
Flash point
Auto ignition
temperature
Density
25C
Vapour density
Viscosity 25C
Solubility in water
Std. enthalpy of
formation fH298
Std. enthalpy of
combustion cH298
Std. molar entropy
S298

Colourless
liquid with
strong odour
60.05 g/mol
118C
16.5C
374C
57.856kpa
(571.1atm)
57C
463C
1049 kg/m3
1044.6 kg/m3
2.07
1.056 mPa-s
soluble
-483.16 kj mol-1
-875.5 kj mol-1
158.0 kj-1 mol-1

Perrys chemical Engineering handbook Antoine Constants for Cp


(J/Kmol)
Specific
Heat
Capacities
Componen
t

c1

c2

c3

Acetic Acid
139640
-32.8
0.9
2
3
Using equation Cp= C1 +C2T+C3T + C4T +C4T4

c4

c5

Methanol Carbonylation (Monsanto process)


Acetic Acid manufactured via carbonylation of Methanol Monsanto process
uses a homogeneous catalyst which is usually a Rhodium-based catalyst.
The main reactions that take place inside the reactor and in the presence
of the catalyst are as follows:

CH3OH + HI CH3I + H2O


CH3I + CO CH3COI
CH3COI + H2O CH3COOH + HI

(1)
(2)
(3)

The process characteristically takes place at a high pressure and


temperature which are in the region of between 10-30 bar and 175-200C.
Using a Methyl Iodine (CH3I) Rhodium complex as a catalyst is the most
common type catalyst used for this process as it achieves a very high
conversion rate of around 99% from the methanol at the temperatures
and pressures discussed above. A study of the reaction kinetics shows
that the methanol reaction is a zero order reaction while the rhodium and
iodide promoter are both first order reactions. The most dominant side
reaction that occurs in this process, is the production of methyl acetate
which can be a valuable side product if extracted and separated from the
main product or can be easily recycled to drive down running costs. The
production of methyl acetate is equilibrium limited and varies and
changes with any temperature or pressure change.. The reaction that
occurs to produce methyl acetate is as follows:
CH3OH + CH3COOH CH3COOCH3 + H2O (4) (esterification reaction)

An assumption can be made that all methyl acetate that does make it
back into the reactor via the recycle streams will react with any of the
water that is and that around 50% of the unreacted methanol leaving the
reactor then reacts to form methyl acetate.
Other by products produced during the process are; dimethyl ether,
methyl acetate, acetoaldehyde, butyraldehyde, ethyl acetate and
propinoic acid.

(Ullmanns, 2003, p. 159)

a)
b)
c)
d)
e)

Reactor
Flasher
Light ends column
Dehydration column
Heavy ends column

To begin the process Methanol and compressed Carbon monoxide (30 bar
to ensure the reaction occurs in the liquid phase) enter a sparged tubular
reactor under the reaction conditions mentioned above (10-30 bar and
between 175-200C) in order for the reaction to occur. The reaction is
highly exothermic and therefore a cooling mechanism for the rector such
as a cooling jacket is needed to ensure a stable temperature is kept and
the excess heat is removed. The hydrocarbon vapour stream exiting the
top of the reactor is mainly composed of unreacted gasses and can be
easily recovered using a scrubber for recycling. The resultant reacted
mixture (vapour phase) is then expanded by the use of a flasher or turbine
to recover duty to compress air for use in the reactor and to also recover
any of the catalyst which is then sent back to the reactor. The flasher
condenses the hydrocarbons and the light hydrocarbons are then
separated by the subsequent column to a cut point of 80C and either
recycled or sent to storage for further treatment and separation. The low
boilers that are separated are dimethyl ether, methyl acetate,
acetaldehyde, butyraldehyde and ethyl acetate. The Remaining mixture
from the column along with the main product is then sent through to the
dehydration column (d), in which the top organic layer taken from the
column is very rich in hydrocarbons and is sent back to the reactor for
recycling. The bottoms aqueous layer from the dehydration column is
distilled to recover the hydrocarbons and then also recycled back to the
reactor. The remaining hydrocarbon free product consists of volatile
oxygenated derivatives (aldehydes, ketones, esters and alcohols), water,
volatile monocarboxylic acids (formic, acetic, propinoic and butyric from
butane), and a mixture of non-volatile materials (difunctional acids,
butyrolactone, condensation products, catalyst residues etc.). The volatile
substances mentioned above can then be further recovered as mixtures or
individual and sold as by-products or recycled back to the reactor to drive
the running costs down. Most of these volatile products that were
separated can generate acetic acid on further oxidation and treatment.
The separation of water and formic acid from the acetic acid product
mixture involves the use of several distillation columns. Water removal is
difficult and very costly when compared to the rest of the purification
process it is carried out by azeotropic distillation with entrainment agents
such as ethers. Formic acid is then separated from the resulting
anhydrous acetic acid by again further distillation with an azeotroping
agent which will result in a mixture of higher boiling acids and acetic acid.
These remaining higher boiling acids are then separated from the acetic
acid product as a residue stream from the bottom of the tower by
distillation. An option to add hydrocarbons such as heptane and isooctane
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to the reactor to improve separation by forming a high boiling azeotrope


with formic acid exists that might help drive the plant running and
equipment costs down. The non-volatile residue can usually be burned off
to recover energy to heat other parts of the process. Traces of iodine that
may remain in the product acetic acid produced may be removed to
increase the purity of the acid by fractional crystallisation or by addition of
small amounts of methanol followed by distillation of the methyl iodide
that subsequently forms. A small amount of propionic acid is also made
and is typically found in the residue of the acetic acid finishing system and
can be removed from the residue by purging the column bottoms and can
be a viable product on its own.

A More detailed flow sheet can be seen in the page below.

(othmer, 2013, p. 78)

Physical properties of all substances involved


Standards

dimet
ylethe
r

methy
l
acetat
e

acetaldeh
yde

butyraldeh
yde

ethyl
propinoi
acetate c acid

Molecular

46.08

74.08

44.05

72.11

88.11

74.08

weight [g/mol]
Boling point

-24.8

56.9

20.2

74.8

77.1

141.15

[C]
Auto-ignition

350

454

175

230

260

512

126.9

237

188

263.95

257

334

[C]
Melting point

-141.5

-98

-123.37

-96.86

-83.6

-20.5

[C]
Hvap (298K)

19.3

32.29

25.76

33.6

35.7

51

[kJ/mol]
Hform (298K)

-184.1

-410

-166

-238.1

-444

-510.8

[kJ/mol]
Density

668.3

934.2

784

801.6

897

987.97

65.57

86.03

55.32

164.7

113.64

152.8

temperature
[C]
Critical
temperature

(20C)
[kg/m3]
Heat
capacity
[J/molK]

References
haynes, 2014. CRC handbook of chemistry and physics
othmer, K., 2000. Encyclopedia of chemical technology volume 1 (4th edition)
Quincy, 2010. National fire protection association; fire protection guide to
hazardous material.
Ullmanns, 2003. Ullmanns Encyclopedia of Indutrial Chemistry volume 1

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