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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
c1
c2
c3
Acetic Acid
139640
-32.8
0.9
2
3
Using equation Cp= C1 +C2T+C3T + C4T +C4T4
c4
c5
(1)
(2)
(3)
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.
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
6
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
10