1.

Process Details

The major factor that could affect the reactor design and overall process design can be
identified by analysing the mechanism and the reaction process.
1.4.1

Chemistry

The reactor is designed at low per-pass conversion, which is 15 35 % for the acetic acid
and 8 10 % for ethylene (Weissermel & Arpe 2003). While, the oxygen concentration in
the reaction mixture should be kept below than 8 % based on an acetic acid free mixture to
avoid an explosion danger on ethylene (Coward & Jones, 1952). Continuous and reliable O 2
analyzers need to be installed in the process inlet of the reactor to monitor the oxygen
composition. Because of the mechanical construction limit of the process vessels, the
pressure in the gas recycle loop and distillation column cannot exceed 140 psia (Luyben &
Tyrus, 1998).
The synthesis of vinyl acetate from ethylene, acetic acid and oxygen over Pd/Au
catalyst is an important industrial process. In the VAM process, the catalyst normally in the
form of spherical silica particle of 5 mm diameter that consist of 0.151.5 wt% Pd, 0.21.5 wt
% Au, 410 wt% KOAc (Xin et al., 2015). Gold plays an important role in the catalyst to
isolating the palladium sides in order to facilitate the coupling of surface species forming
VAM. Other than that, addition of gold could improve catalytic selectivity by inhibiting
undesirable by-products such as CO and CO 2, as well as surface carbon (Li et al., 2012). In
the catalytic chemical reaction mechanisms, KOAc contributes to the formation of the acetic
acid layer, which further prevents the combustion of ethylene. KOAc also will enhance the
formation of actives sides through the solvatation of palladium complexes(Motahari et al.,
2012). Consequently, the reaction kinetics is not sensitive to the concentration of the acetic
acid, but the presence of some water is necessary to activate the catalyst.

1.4.2

Kinetics

On the other hand, ethylene and oxygen are involved in kinetics through a complex
adsorption or surface reaction mechanism. The formation of VAM can be represented by a
power-law kinetics including only ethylene and oxygen (Motahari et al., 2012):

r va =K 1 PC

1
2

PO

H4

(3)

Where P is the partial pressure of the component and exponent 1 is 0.35 - 0.38 and 1 is
0.18 - 0.21 indicating strong adsorption limitations. The reaction constant is given by
equation (4), in which the energy of activation depends on the Pd content.

K 1= A1 exp(

E
)
RT

(4)

Similar kinetics has been determined to describe the secondary combustion reaction, but
with reaction order very different from the main reaction:
2

r C O =K 2 PC H PO
2

(5)

Table 3 present the kinetic information for the main reactions, in which the frequency factors
have been calculated from the turnover-frequency (TOF) data (Han et al., 2005). TOF give
the number of molecular reactions or catalytic cycles occurring at center per unit of time.

TOF=

volumetric rate of reaction mole A l cat

=
=s1
number of center /volume l cat s mole Me

(6)

Table 1: Kinetics parameters for VAM synthesis over Pd/Au/SiO2 catalysts (Han et al.,
2005; Luyben & Tyrus, 1998).
Reactions
C2H4 + CH3COOH + 0.5O2
C2H3OOCCH3 + H2O
C2H4 + 3O2 2CO2 + 2

Power-law kinetics
C2H4
O2
0.36
0.20
-0.31

0.82

Kinetic constants
E (J/mol)
A1
A2
15000
2.65 x 10-4
7.95 x 10-5
21000

7.50 x 10-4

2.25 x 10-4

H2O

1.4.3

Thermodynamics

Thermodynamic of a reaction is important to determine it reaction properties (exothermic or

endothermic) and it reversibility (reversible or irreversible). Reaction exothermic or

HRo
endothermic) can be determine based on the value of the heat of reaction (

).

Heat of reaction for both reaction is calculated based on the change in the enthalpy.

Hof
Table 4: Amount of heat of formation,

for each component at 1 atm and 25C

(NIST, 2016)

Component

Hof
(kJ/mol)
52.4
-434.84
0
-313.6
-241.83
-393.52

Ethylene
Acetic Acid
Oxygen
Vinyl Acetate Monomer
Water
Carbon dioxide

o
HPr
oduct

HRo
Rection 1.6

o
HRe
ac tan t

Hof H2O

HofVAM
=(

HoC2H4
)-(

HoC2H4O2
-

HoO2
-

= (-313.6 241.83) - (52.4 434.84)

= -172.99 kL/mol

HRo
*Negative value

for reaction 1.6 show the reaction exothermic.

o
HPr
oduct

HRo
Rection 1.7

o
HRe
ac tan t

=(

HoC2H4

2Hof H2O

Hof CO2
+

)-(

HoO2
-

= (2(-393.52) 2(241.83)) - (52.4 0)

= -1323.1 kL/mol

HRo
*Negative value

for reaction 1.7 show the reaction exothermic.

As both reaction has high exothermic effect, thus it is necessary to take some measures in
order to moderate the temperature increase. This process constraint can be control by
diluting the reaction mixture with some inert gas such as ethane.
To achieve optimum condition, the reaction will operate in temperature around 150 160C,
the reaction temperature should be above 150C in order to bring the salt activator into the
molten state. However, temperatures higher than 150C have only a moderate effect on the
reaction rate because of low activation energy, but it may decrease considerably the

selectivity. A hot spots above 200 C will cause a permanent catalyst deactivation (Kumar et
al., 2007), this problem may be prevent by diluting the catalyst in the entry zone and/or by
manipulating the pressure of the raising steam.
While the reaction pressure around 8 10 bar. Even through higher pressure has a positive
effect on productivity, but affects the selectivity negatively since increased adsorption of
ethylene on the catalytic sites favours the combustion reaction.