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In order to obtain the required amount of acetylene for the polymerization step,
it is selectively hydrogenated to ethylene in an adiabatic fixed bed catalytic reactor.
The reaction should be selective because multiple chain reactions can occur during a
hydrogenation reaction if it is not thoroughly controlled. Almost all of these chain
reactions are undesired and must be avoided. A fixed-bed reactor includes one or more
tubes filled with catalyst particles and work vertically. Commercially, acetylene
selective hydrogenation can be performed based on two scenarios; namely front-end
and tail-end; which depends on feed condition. Figure 2.31 and Figure 2.32 show how
front-end and tail-end hydrogenation is set up respectively.
Figure 2.35 shows the graph of acetylene conversion for different types of
catalyst used. It can be observed that the 25% Pd 75% Ag alloy catalyst combination
produce very high conversion of acetylene and low ethane production. A highly
selective catalyst will have very low ethane production, even at high conversion, where
the amount of acetylene in the reactants is small. Different Ni-Zn catalysts were
compared with a model Pd-Ag catalyst. Pure Pd has considerably good selectivity,
whereas the Pd-Ag alloy shows a very high selectivity even at steep conversions.
Nickel is considerably worse than palladium, but as seen in the figure, adding
increasing amounts of zinc increases the selectivity substantially. The Ni-Zn catalyst
containing the highest percentage of zinc had a selectivity level comparable to the Pd-
Ag catalyst that was tested. Nevertheless, the Pd-Ag catalyst was still chosen because
it is established, effective and widely used in acetylene hydrogenation.
Figure 2.35: Ethylene Conversion (%) for Various Types of Catalyst (Nørskov et.
al.,2009)
There are a few important assumptions that should be made and followed in
the chemical engineering design of the fixed bed adiabatic reactor (R-102), which is
used in the conversion of acetylene. Those assumptions are as follows:
There are three main model equations considered for the reactions taking place
in an acetylene hydrogenation reactor (Bos et al., 1993; Westerterp et al., 2002). The
primary overall reactions taking place in the reactor are shown in equation 2.35, 2.36
and 2.37.
Reactions 2.35 and 2.36 are the main reactions occurring in such systems.
However, there are also some side reactions which uncontrollably occur during
acetylene hydrogenation. The most important side reaction is shown in equation 2.37,
which is the direct hydrogenation of acetylene to ethane. There is also a tendency for
hydrogenated to heavier products called green oils via oligomerization process.
Nonetheless, according to Leviness et al. (1984) and Sarkani et al. (1984) even direct
hydrogenation of acetylene to ethane and oligomerisation can be neglected.
Table 2.1: Kinetic Model of Reactions in Fixed Bed Reactor (Khold et al.,2016)
Equation Rate Equation
2.37 Negligible
−𝐸𝑎,𝑖
𝑘𝑖 = 𝑘𝑖,0 exp( ) (2.38)
𝑅𝑇
Based on equation 2.38, 𝐸𝑎 is the activation energy (J/mol), 𝑘𝑖 is the reaction
rate constant (𝑘𝑚𝑜𝑙/𝑘𝑔. 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡. 𝑠𝑒𝑐 𝑏𝑎𝑟 2 𝑜𝑟 𝑏𝑎𝑟 −1 ), R is the gas constant
(8.314 𝑘𝐽/𝑘𝑚𝑜𝑙. 𝐾) and T is the temperature (Kelvin). Applying equation 2.38, the
rate constants k1 to k6 can be calculated. Table 2.2 shows the values of calculated rate
constants and their respective activation energies.
The values obtained in Table 2.2 can be substituted into equations 2.35, 2.36
and to obtain the following values. The complete values could not be obtained because
there is no specific partial pressure value given.
𝑟 48.01𝑃𝐶 𝐻 𝑃𝐻
2 2 2
(2.39)
𝐶2 𝐻2 =
(1+584.59𝑃𝐶 𝐻 )(1+2.86𝑃𝐻 )
2 2. 2
Based on equations 2.39 and 2.40, the reaction rate of the two main reactions
in this process can be obtained. The values of the partial pressure are not measured and
varies depending on many factors. Therefore, the value of partial pressure is not
included.
2.3.7 Reactor Volume
A plug flow pattern is considered for the reactor. Therefore, the sizing of the
reactor should be according to a Plug Flow Reactor (PFR) design. The volume of a
PFR is shown in equation 2.41. The volume is calculated considering the main reaction
which takes place which is the selective hydrogenation of acetylene in equation