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2.

0 Design of Hydrogenation Reactor

2.1 Process Description

Large-scale productions of ethylene are primarily carried out by steam-


cracking of saturated hydrocarbons, which leads to impurities in the form of acetylene
in the ethylene product slate. Much of the ethylene is used in processes where
acetylene is undesirable. One process where the acetylene is particularly undesired is
the important polymerization of ethylene into polyethylene. The acetylene
concentration in the ethylene feed can be reduced by selective hydrogenation to
ethylene. A high selectivity is necessary to get the acetylene reduced to the desired low
levels of a few ppm without hydrogenating ethylene to ethane.

Acetylene hydrogenation process is a purification step for ethylene and


propylene. Trace amounts of methyl acetylene(MA) and acetylene are formed as a
result of steam cracking in furnaces. The amount of acetylene and MA formed is
depends on the furnace feed, together with the furnace design and operating conditions.
Acetylene will fractionate with ethylene; MA will fractionate with propylene. These
components can only be present in concentrations of < 1 ppm in polymer grade
ethylene and propylene. The common method for removal of acetylene and MA is via
selective hydrogenation using an adiabatic fixed bed reactor in vapor phase.

2.3 Chemical Engineering Design of Acetylene Hydrogenation Reactor(R-102)

As mentioned in Section 2.1, Acetylene removal is an essential step for the


purification of ethylene and in polymerization units in order to prevent formation of
highly explosive metal acetylides compounds. Many considerations and assumptions
need to be made in the design of a fixed bed reactor. This is mainly due to the unstable
behaviour of catalysts and the complex reaction mechanisms of acetylene
hydrogenation.
2.3.1 Reactor Selection

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 2.31: Front-end Acetylene Hydrogenation Setup (Rahimpour et al., 2012)

Figure 2.32: Tail-end Acetylene Hydrogenation Setup (Rahimpour et al., 2012)


According to Figure 2.31, it can be seen that in a front-end setup,
hydrogenation takes place before the removal of lighter components such as H2,
CH4 and CO and the feed with high excess of hydrogen directly enters the reactors.
On the other hand, Figure 2.32 illustrates that in tail-end hydrogenation process,
hydrogenation takes place after the removal of lighter hydrocarbons (H2, CH4 and CO)
(Rahimpour et al., 2012). The main advantage of tail-end hydrogenation is that it
minimises ethylene loss compared to front-end hydrogenation units that have higher
ethylene loss (Spaether,2011). Rahimpour et al. also mention that most plants use tail-
end hydrogenation to purify ethylene and propylene. Therefore, the tail-end
hydrogenation unit is used. The only problem with this method is that one reactor can
only eliminate 60 % - 70% of the acetylene content. A steep rise in temperature of the
lead bed is seen caused by the highly exothermic nature of acetylene hydrogenation
reaction, which may lead to catalyst sintering and physical damages to the process
equipment. The solution which can be proposed to this problem is to use a second
reactor to remove the remaining acetylene. Two fixed beds with a primary lead bed
(LB) and a second bed called guard bed (GB) can be used. The remaining acetylene is
eliminated in the second bed called guard bed (GB). Utilising a guard bed will help
maintain the acetylene concentration below 1 ppm (Khold et al., 2016). Figure 2.33
shows the setup of a tail-end unit with a second reactor.

Figure 2.33: Improved Tail-end Hydrogenation Unit (Khold et al., 2016)


Based on Figure 2.3, it is illustrated that pure hydrogen is added to the ethylene
rich stream of deethanizer. Then, the outlet stream is cooled and sent to LB where it is
mixed with the pure hydrogen. The outlet stream of GB is subsequently cooled down
and injected into a scrubber called green oil knock-out pot. High concentrations of
acetylene present in the unit inlet could produce a large amount of C4 + and green oil.
These chemicals may interrupt operation of the C2 fractionators and could be
eliminated by installing a green oil knock-out pot. Figure 2.33 also shows two extra
reactors present in the hydrogenation unit. When beds 1 and 2 are utilized, bed 3 and
4 are out of service. The catalysts need to be regenerated after a 360-day run period. It
is a vital process that needs to be carried out, in order to avoid catalyst sintering and
physical damage other than using a second reactor.

2.3.2 Selection of Catalysts

A wide selection of catalyst has been studied for hydrogenation of acetylene


since catalysts in the form of nickel sulphide were first tested (Anderson et al., 1948).
Nickel or zinc-based catalysts on alumina or silica (Muller et al., 1987), cadmium,
calcium, barium, strontium or magnesium on Cr2O3 (Weisang and Engelhard, 1970)
as well as copper on alumina, magnesia or silica (Taghavi et al., 1978) have been
utilised in certain cases. The most suitable metal to use as a catalyst for this process
was palladium on the base of alumina and after that the researchers worked to improve
its selectivity and resistance (Godinez et al., 1995). Most past research in acetylene
hydrogenation suggest that most common commercially used catalyst is Pd/alumina
(Brodzinski and Cybulski, 2000; Vincent and Gonzalez, 2001 & Vincent and
Gonzalez, 2002). Recent studies however, show bimetallic, palladium promoted with
a second metal, like silver. Figure 2.34 shows the different types of catalysts used
commercially. The Pd-Ag catalyst is known to be widely used in industries to remove
Acetylene (Nørskov et al.,2009).
Figure 2.34: PRICAT Pd and HTC Catalysts (Holland et al.,2018)

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)

2.3.3 Assumptions in R-102 Design

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:

 A homogenous reactor model is considered in the design


 The reactor operates in an unsteady state condition
 Radial difference in temperature and concentration is ignored.
 Axial heat and mass diffusion are neglected due to high gas velocity.
 Catalyst deactivation is considered in the reactor.
 Bed porosity is constant, making the reactor symmetrical.
 The gas mixture is regarded as an ideal gas.
 Lateral heat loss is neglected (adiabatic reactor).
 Pressure drop along the reactor is ignored.
2.3.4 Properties of Reactant(Acetylene)

As mentioned in Section 2.1, acetylene is a dangerous and undesired by-


product during ethylene synthesis. Depending on the feed and cracking conditions,
about 0.5–2.5 ton of acetylene is produced for 100 ton of ethylene synthesised.
Acetylene is a form of contaminant for catalysts included in a polymerization unit.
Maximum acetylene content for catalyst of the polymerization cannot exceed 1 ppm;
otherwise, it leads to formation of metal acetylides, which are highly explosive.
Furthermore, acetylene presence above the tolerance level can cause irreversible
damage of the catalysts used in downstream processes of the steam cracker (for
example Ziegler–Natta catalysts in the polymerization of ethylene) Hence, acetylene
has to be eliminated from ethylene to assure an acetylene free stream (Bos et al.,1993
& Rahimpour et al.,2012).

2.3.5 Main Reaction Models

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.

𝐶2 𝐻2 + 𝐻2 → 𝐶2 𝐻4 ∆𝐻𝑟 = −42.2 kcal/mol (𝟐. 𝟑𝟓)

𝐶2 𝐻4 + 𝐻2 → 𝐶2 𝐻6 ∆𝐻𝑟 = −33.1 kcal/mol (𝟐. 𝟑𝟔)

𝐶2 𝐻2 + 2𝐻2 → 𝐶2 𝐻6 ∆𝐻𝑟 = − − 75.3 kcal/mol (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.

2.3.6 Kinetic Rate Model

Three dominant reactions occurring in acetylene hydrogenation process are


acetylene hydrogenation to ethylene, ethylene hydrogenation to ethane and direct
hydrogenation of acetylene to ethane. The kinetic rate models of equations 2.35,2.36
and 2.37 are shown in table 2.1.

Table 2.1: Kinetic Model of Reactions in Fixed Bed Reactor (Khold et al.,2016)
Equation Rate Equation

2.35 𝑟 𝑘1 𝑃𝐶2𝐻2 𝑃𝐻2


𝐶2𝐻2 =
(1+𝑘2 𝑃𝐶2𝐻2 )(1+𝑘3 𝑃𝐻2 )
.

2.36 𝑟 𝑘4 𝑃𝐶2𝐻4 𝑃𝐻2


𝐶2 𝐻6 = 1.25
(1+𝑘5 𝑃𝐶2𝐻2 ) (1+𝑘6 𝑃𝐻2 )
.

2.37 Negligible

According to the rate models in Table 2.1, 𝑟𝑖 is the rate of reaction


(𝑚𝑜𝑙/𝑘𝑔. 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡. sec) of species i. 𝑘𝑖 is the reaction rate constant (𝑘𝑚𝑜𝑙/
𝑘𝑔. 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡. 𝑠𝑒𝑐 𝑏𝑎𝑟 2 𝑜𝑟 𝑏𝑎𝑟 −1 ). 𝑃𝑖 is the partial pressure (Pa) of component i. The
rate constants, ki have to be calculated before the reaction rates can be obtained. The
Arrhenius equation is applied to compute the constant parameters of the rate equations.
It is shown in equation 2.38

−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.

Table 2.2: Constant Parameters of the Rate Equations (Khold et al.,2016)


Rate ki,0 Ea,i
2 −1
Constant (kmol/kg. catalyst. sec bar or bar ) (kJ/kmol)
k1 48.01 1220.5
k2 584.59 −5558.7
k3 2.86 −3361.3
k4 202.67 39774.2
k5 0.07 −12493.4
k6 2.89 −3325.6

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

𝑟 202.67𝑃𝐶2 𝐻4 𝑃𝐻2 (𝟐. 𝟒𝟎)


𝐶2 𝐻6 = 1.25
(1+0.07𝑃𝐶2 𝐻2 ) (1+2.89𝑃𝐻2 )
.

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