Reactor design for the alkylation of ethylene

with benzene to produce ethylbenzene.

D.P. Bothma 25893394

K. Choku 27104419
A. Labuschagne 27032167
D. Stone 25871617
C.J. van der Walt 22823905

CEMI415

BACHELOR OF ENGINEERING
In
CHEMICAL ENGINEERING

North-West University: Potchefstroom Campus

Submitted to:
Prof H. Neomagus

2019-05-18
Executive Summary

Ethylbenzene is a colourless liquid with a global demand of 25 million ton per annum and is mostly
used for the production of styrene through alkylation. Liquid-phased alkylation has high selectivity,
lower temperatures and longer catalyst life. Beta-type zeolite catalysts and packed bed reactors are
preferred for this purpose. The main side reaction is the formation of di-ethylbenzene and the main
form of deactivation is by coking but is reduced by feeding benzene in excess. The whole reaction
process is surface reaction rate controlled.

Reaction rates were found for both main reactions and reaction parameters were gathered from
several literature sources and online chemical property databases. Further development information
for the model was gathered from reactor basics and reaction kinetics as well as some thermodynamics
and heat transfer principles.

The model developed in this paper is that of a packed bed reactor with multiple beds of which the first
is adiabatic and the subsequent four are all near-isothermal with varying cooling. Step-feeding is also
used to improve conversion and decrease energy inefficiency and a benzene to ethylene feed ratio of
7:1 is implemented. The multiple reactions taking place are modelled and flowrate is found constant
due to excess benzene and liquid phase operation.

Catalyst deactivation is neglected due to long life and minimal deactivation while overall effectiveness
factors for industrial scale-up are calculated and implemented, accounting for mass transfer. The
energy balance of reactors with cooling is implemented along with a complex IF-statement to ensure
the reactor operates under step feeding and subsequent cooling conditions.

The final model produces 513.84 kton/annum of ethylbenzene with a catalyst weight of 17.5 tons
spread through the five beds. The ethylene conversion is 95 % and some areas for future improvement
are identified such as more benzene in step-feeds.

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Table of Contents
Executive Summary 2
Nomenclature 4
List of Symbols 4
List of Subscripts 5
List of Abbreviations 5
Introduction 7
Literature survey 9
General Aspects 9
Zeolite catalyst 11
Reaction mechanism 12
Coke formation 13
Model development 14
Reactions to be used: 14
Mole balances: 14
Energy balance: 17
Modeling results 19
Conclusions 24
References 25
Appendix 27
Constants: 27
Energy Balance calculations: 28
Volumetric flow calculations: 30
Overall effectiveness factor excel calculations: 31
Polymath Code: 31
Formulas for reactions: 34

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Nomenclature
List of Symbols

A – Arrhenius equation pre-exponential factor - [-]

Ci – Concentration of component - [mol/L]
Cpi – Specific heat capacity of component - [J/mol.K]
D – Reactor diameter - [m]
dp – Catalyst particle diameter - [m]
E – Activation energy - [J/mol]
Fi – Molar flow of component - [mol/s]
o
Hf (l) – Liquid phase heat of formation - [J/mol]
Hfo(g) – Vapour phase heat of formation - [J/mol]
ΔHrio – Heat of reaction - [J/mol]
K, k – Reaction rate constant - [varied]
L – Reactor length - [m]
P – Pressure - [bar]
R – Ideal gas constant - [J/mol.K]
r – Reaction rate - [mol/L.s]
T – Temperature - [K]
vi – Stoichiometric coefficient - [-]
W – Catalyst weight - [ton]

ηo – Overall effectiveness factor - [-]

ρb – Bed density - [g/L]
υ0 – Volumetric flow - [L/s]

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List of Subscripts

B – Benzene
B1 – Benzene in reaction 1
DEB – Di-ethylbenzene
DEB2 – Di-ethylbenzene in reaction 2
E – Ethylene
E1 – Ethylene in reaction 1
E2 – Ethylene in reaction 2
EB – Ethylbenzene
EB1 – Ethylbenzene in reaction 1
EB2 – Ethylbenzene in reaction 2
r1 – Reaction 1
r2 – Reaction 2
scale – Scaled reaction rate

List of Abbreviations

CSTR – Continuous Stirred Tank Reactor

DEB – Di-ethylbenzene
EB – Ethylbenzene
PFR – Plug Flow Reactor
PBR – Packed Bed Reactor

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List of Figures
Figure 1: Final Design of the reactor ................................................................................... 19
Figure 2: Component flow vs catalyst weight ...................................................................... 20
Figure 3: Ethylene flow vs catalyst weight ........................................................................... 20
Figure 4: Component concentration vs catalyst weight........................................................ 21
Figure 5: Ethylene concentration vs catalyst weight. ........................................................... 21
Figure 6: Ethylene conversion vs catalyst weight ................................................................ 22
Figure 7: Pressure drop vs catalyst weight .......................................................................... 22
Figure 8: Reactor temperature profile vs catalyst weight ..................................................... 23
Figure 9: Reactor cooling vs catalyst weight ....................................................................... 23
Figure 10: DEB Cp fitting curve ........................................................................................... 29

List of Tables
Table 1: Comparison between Y zeolite and beta zeolite (Peregp & Ingallina, 2002) .......... 12
Table 2: Mole balance and concentration equations ........................................................... 15
Table 3: Reactions, rate law and constant, and activation energy data (Ganji et al., 2004) . 16
Table 4: List of equations used to scale reaction rates ........................................................ 16
Table 5: Results summary .................................................................................................. 24
Table 6: Table of constants and manipulatable variables. ................................................... 27
Table 7: Physical properties (NIST, 2019). .......................................................................... 27
Table 8: Heat of formation data (NIST, 2019). ..................................................................... 28
Table 9: Specific heat capacity equations. .......................................................................... 28

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Introduction

Ethylbenzene (EB) is a colourless liquid with an odour similar to gasoline, with concentrations smaller
than 2 ppm at standard conditions in air. EB is present in small quantities in crude oil, and is used for
the production of materials such as styrene, acetone, di-ethylbenzene and cellulose acetate (Ganji, et
al., 2004). A global EB demand of 25 million ton per annum in 2003 was also reported by Ganji, et al.
(2004). It was determined by Tang, et al. (2000) that the average human is exposed to about 130µg of
EB per day from air and food packaging.

The alkylation of ethylene and benzene to produce EB is in important process in the petrochemical
industry, as EB is the main reactant in the styrene production process. More than 95% of all EB
produced is used in styrene production (Hussain et al., 2017). Small scale commercial production of
Styrene initiated in the 1930’s, and it is currently one of the most important monomers in the polymer
industry, with a global market value of $30-$50 billion. A global Styrene production of 14 million ton
per annum by catalytic dehydrogenation of EB was recorded in 1992. Styrene in turn, is an important
intermediate for the production of material such as polystyrene, acrylonitrile-butadiene-styrene (ABS)
resin, acrylonitrile-styrene (AS) resin, styrene-butadiene rubber and others (You, 2006, Tang, et al.,
2000).

An annual global production of 26.4 million metric tons of Styrene from EB in 2010 was reported by
Zarubina (2015), stating that the dehydrogenation of EB is one of the most important industrial
processes.

Historically the alkylation reaction was performed via a continuous stirred tank reactor (CSTR), using
mineral acids such as aluminium chloride as catalyst. High costs associated with corrosion of
equipment forced the development of other catalysts (Yang, 2016). UOP and Mobil-Badger developed
supported zeolite based catalyst, which allowed for vapour phase alkylation at high temperatures and
moderate pressures (Al-Kinany et al., 2012; Yang, 2016). Problems with vapour phase alkylation
include; the formation of by-products such as toluene with concentrations as high as 1,000 to 2,000
ppm, low selectivity towards EB and high rates of catalyst deactivation (Al-Kinany et al., 2012).

The latest trend in commercial production of EB is towards liquid-phase alkylation (Ng et al., 2016).
The advantages of the liquid phase reaction include low reaction temperature, high selectivity and
long catalyst life (Shi et al., 2014). Due to superior activity and selectivity, Beta (β) and MCM-22

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zeolites are the most widely used catalysts in commercial liquid phase alkylation of benzene with
ethylene (Shi et al., 2014).

In this study a model will be constructed from chemical reaction engineering principles for a liquid
phase, zeolite-based, alkylation reactor for the production of 500 kton/year of EB from ethylene and
benzene.

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Literature survey

General Aspects
Ethylbenzene (EB) is an important intermediate product commonly used for the production of styrene
(Al-Kinany et al., 2012). Styrene mainly used for making polystyrene, a common plastic material. EB is
produced through the alkylation reaction of ethylene and benzene shown by reaction 1 below (Shi et
al., 2015). The EB is further alkylated to produce by-products namely; di-ethylbenzene (DEB) (Reaction
2).

These reactions are commonly carried out in packed bed reactors (PBR), either in the gas or liquid
phase (Al-Kinany et al., 2012).

𝐶6 𝐻6 + 𝐶2 𝐻4 → 𝐶6 𝐻5 𝐶𝐻2 𝐶𝐻3 Reaction 1

𝐶6 𝐻5 𝐶𝐻2 𝐶𝐻3 + 𝐶2 𝐻4 → 𝐶10 𝐻14 Reaction 2

Traditionally, in the early 1900’s, the alkylation of benzene in the presence of ethylene was carried
out over a Friedel-Crafts catalyst (𝐴𝐿𝐶𝐿3 − 𝐻𝐶𝐿) at a low temperature (around 160°C). This was
done in the liquid phase due to the corrosive nature of the catalyst. In addition to this, the reactions
took place in glass-lined or brick lined reactors – adding to the capital costs of production (Perego &
Ingallina, 2002). The use of this type of catalyst also meant that the reactor effluent needed to be
washed and neutralized to remove the spent catalyst, yielding an aqueous waste that was difficult to
dispose of (Kirk Other Encyclopedia, 2000). Due to this, the Friedel-Crafts catalyst did not become
very popular. Solid catalysts were introduced in the 1940’s to be utilized in the vapour phase
alkylation of benzene with ethylene. These catalysts were based on amorphous silica-alumina gel
and indicated consistent activity under the conditions used at the time (Kellet & Plucker, 1947).
About 20 years later, zeolite catalysts were introduced and it was found that large pore zeolites
performed better than amorphous silica-alumina gel (Venuti et al.,1966). 1989 marked the year that
Lummus/Unocal/UOP introduced the use of zeolite catalysts in the liquid phase ethylbenzene
process. Y type zeolite was the first to be developed in 1979, but it was later found that larger pore
zeolites were able to overcome the diffusion limitations that were observed during liquid phase
operation (Perego & Ingallina, 2002). Other large pore zeolites included mordenite, ZSM-12 and beta
zeolite catalysts to name a few.

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The gas phase method is carried out at high temperatures (573K – 773K) and moderate pressures (10
– 208 Bar), which leads to higher energy consumption, more cooling systems and strict apparatus
requirements (Al-Kinany et al., 2012). Motivating factors contributing to the liquid phase reaction
include; better catalyst control (Yang et al., 2016), lower operating temperatures (Ng et al., 2016) and
decreased formation of by-products (Khlebnikova et al., 2017).

A liquid phase, zeolite-based alkylation of polymer grade ethylene and benzene in an adiabatic packed
bed reactor (PBR) is exothermic (Dwyer et al., 1984). The liquid based alkylation takes place at
temperatures from 400K to 533K and pressures ranging between 30 – 40 bar (Ng et al., 2017). These
operating conditions allow for lower energy costs, higher catalyst activity and better thermal control
over the reaction according to Shi et al. (2015). Inter-stage cooling may be required due to benzene
acting as a heat carrier during adiabatic operation (Woodle, 2006).

The conversion of ethylene increases with temperature while the selectivity of EB decreases (Shi et
al., 2015). According to Yang et al. (2016) and Han Ng et al. (2017) excess benzene in the feed reduces
coke formation on the catalyst, absorbs the heat of reaction reducing the changes of thermal runaway
and improves the benzene selectivity.

The yield of EB increases with temperature due to the high increase in conversion, while more side
reactions also occur (Al-Kinany et al., 2012). The selectivity of EB is temperature dependent and
decreases with the increase in temperature between 300°C and 400°C and is mostly due to sintering.

PFRs are chosen for the alkylation because they are industrially prevalent (Woodle, 2006). Analyses
performed by Ng et al. (2017), shows that the PFRs tend towards smaller reactor diameters, allowing
greater mixing in the radial direction and validating the PFR assumption. The Reynolds number for
fluid flow through the packed bed should be more than 100 for turbulent flow (Woodle, 2006). The
benzene/ethylene ratio between 3 and 3.5 is recommended by Woodle (2006) for the liquid phase
zeolite based catalytic alkylation.

The void fraction of the zeolite catalyst is 0.48 (Baerlocher et al., 2007). The alkylation reactor contains
two catalytic beds with cooling between each stage (Ng et al., 2017). The liquid-phase zeolite-based
reactions generally result in decreased formation of by-products due to lower operating temperatures
and steric hindrance limits the alkylation reaction rates inhibiting PEB formation (Woodle, 2006).
Luyben (2002) stated that ethylene conversion per bed should be 100% and Ganji et al. (2004) noted
that a typical pressure drop of 200kPa can be expected in alkylation reactors.

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Zeolite catalyst
The zeolite catalyst is readily reproducible, environmentally friendly, less toxic and highly selective in
catalytic reactions (Al-Kinany et al., 2012). The pore size of the catalyst makes it ideal for the alkylation
reaction of ethylene and benzene, increasing the EB diffusion while also preventing the diffusion of
PEB’s (Hansen et al., 2010).The zeolite catalyst does however consist of a high acid strength and acid
amount, catalysing the carbon formation from ethylene (Song et al., 2006). The catalyst has a lifespan
of 6 years under the liquid based conditions have been reported by Yang et al. (2016).

Since its discovery by Wadlinger et al. (1967), the use of the β-zeolite for catalytic reactions has been
investigated because of the easy access to active sites and the silica-rich framework (Yang et al., 2016).
The β-zeolite has a three dimensional pore structure consisting of perpendicular straight channels
(0.66nm x 0.67nm). The interconnections create narrow helical channels with effective pore diameters
of 0.56nm x 0.56nm.

β-zeolite is highly active in the alkylation of benzene with ethylene and ensures higher ethylene
conversion and EB selectivity than for example the Y-zeolite (Cheng et al., 1996). The single-pass
catalyst lifetime for the alkylation reaction using β-zeolite catalyst is 6 to 9 months (Yang et al., 2016).
The ethylbenzene purity is higher than 99.8% and the xylene content is much lower.

The research on liquid phase circulating processes for the production of EB started in 1990 and a highly
active catalyst using β zeolite with high EB stability and selectivity was introduced (Wang et al., 2012).
Later a new generation benzene alkylation catalyst was developed using a smaller β-zeolite as the
active component (Yang et al., 2016). The alkylation can be operated at low benzene/ethylene feed
ratio of 3.5; with EB selectivity of 88% and the total yield of 99.7% (Yang et al., 2016).

The design of a catalyst for a specific process usually involves an in-depth look at how the catalyst
behaves on a nano-scale. Both empirical characterization methods (which include spectroscopy and
the like) and quantum chemical calculations assist in determining the role that the active sites of the
catalyst in reaction mechanisms, as well as provide information about the intrinsic kinetics of the
reactions at play (Rao et al.,2017). It has been empirically found that beta zeolite has a higher
ethylbenzene selectivity that is owed to features in its channel systems (Bellussi et al.,1995). The
table below depicts these findings.

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 Table 1: Comparison between Y zeolite and beta zeolite (Perego & Ingallina, 2002)

Catalyst Conversion Selectivity

(%)
EB DEB TEB Other
Zeolite Y 100 82 8.4 0.7 8.8
Zeolite beta 100 91.1 7.9 0.3 0.7

It is clear that the success of the zeolite catalyst can be owed to its micro-pores that have well
defined structures (Christensen et al., 2003). Despite this great advantage, it is this very property
that makes the mass transport in and out of the pores, a slow process, even slower than the
Knudsen diffusion (which usually limits how well industrial catalysts perform) (Christensen et al.,
2003). Two ways in which to overcome this limitation would be to either increase the pore size or
decrease the crystal size of the zeolite catalyst. One approach would be to construct hierarchical
pores in a single crystal, which would be able to avoid the negative effects of diffusion on
conventional zeolite, as well as maintain the acidity and stability of the zeolite (Shi et al., 2015).
Literature has proven that mesoporous zeolite catalyst is much more active than the conventional
zeolite catalyst. The reason for this would be the improvement in mass transportation in the catalyst
– as the presence of the diffusion limitation is due to lower apparent activation energy (Christensen
et al., 2003). The alkylation of benzene with ethylene is a fast reaction whose rate can be increased
if the size of the catalyst particle were to be reduced, or if the pore structure was to be altered. A
high fluid velocity results in the increase in the external mass transfer coefficient (Ercan et al., 1998).
In order to achieve the lowest effectiveness factor of the catalyst particle in a first order isothermal
reaction, a spherical shape of catalyst should be utilized in the process (Ercan et al., 1998). On an
industrial scale, the alkylator shows that external mass transfer limitations exhibit a contribution of
almost 50% of the total resistance that controls the process (Ercan et al., 1998).

Reaction mechanism
Adsorbed ethylene cannot react with benzene in the form of gas, or with benzene adsorbed on weak
acidic sites (Cheng et al, 1999). The reaction control step of benzene alkylation with ethylene is
expressed as:

𝐶2 𝐻4 + 𝐻𝑂 − 𝑍𝑒𝑜𝑙 ⇄ 𝐶2 𝐻5 − 𝑍𝑒𝑜𝑙 → 𝐶2 𝐻5+ + 𝑂 + − 𝑍𝑒𝑜𝑙

According to Du et al. (2002), there are two modes of adsorption that can occur.

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In mode 1 an ethoxide intermediate is formed as the ethylene molecule adsorbs onto the acidic site
of the zeolite. The ethylene changes into C+-C that has a strong interaction with acidic OH groups
(Du et al., 2002). The benzene molecule interacts with the ethoxide intermediate, subsequently
leading to the ethoxide leaving the zeolite wall. At lower temperatures the adsorbed ethylene has a
low migration capacity, hence the benzene molecules that have low interactions with the acidic OH
cannot easily replace adsorbed ethylene (Kefeng et al., 2011). Benzene can thus not be activated
effectively on the weak acidic sites and alkylation does not occur. For this reason, alkylation of
benzene and ethylene takes place at higher temperatures (573K – 773K) (Al-Kinany et al., 2012).

In mode 2 the benzene molecules contact the β-zeolite first, adsorbs onto the strong acidic sites and
is activated sufficiently. The ethylene then adsorbs onto the same sites with a little weaker acidity or
ethylene replaces some adsorbed benzene and reaction can take place (Du et al., 2002).

An alternative reaction mechanism was proposed by Wang & Chen (2002):

The reaction mechanism follows this trajectory: the benzene molecule adsorbs onto the catalyst, but
only the benzene that was able to adsorb on the strong acidic sites are activated. This is due to the
fact that adsorbed ethylene is unable to react with benzene that is adsorbed to weak acidic sites or
benzene in the gas phase (Wang & Chen, 2002). Therefore two modes exist. Mode 1 involves the
contact of benzene with the beta zeolite first, which is then adsorbed on the strong sites and
activated. The injected ethylene is adsorbed with weaker acidity onto the same sites or ends up
replacing some benzene that is already adsorbed (Wang & Chen, 2002). On the other hand, mode 2
involves the adsorption of ethylene on the beta zeolite. At temperatures around 120°C, the
adsorbed ethylene exhibits a poor migration capacity, thus the benzene that has a weak interaction
with acidic OH cannot replace the adsorbed ethylene with ease. Therefore, alkylation does not take
place. In contrast, at higher temperatures, the ethylene migration capacity is increased, allowing for
benzene to partially adsorb on strong sites. This shows that ethylene and benzene compete to be
adsorbed – following Sabatier’s principle (Wang & Chen, 2002).

Coke formation
The deactivation of the catalyst in the alkylation of ethylene and benzene occurs as the active sites on
the catalyst are blocked by coke formation (Al-Kinany et al., 2012). The coking is mostly due to the
oligomerization of ethylene, because the activated ethylene reacts with other ethylene molecules to
form higher polymer (Shi et al., 2015). For this reason, benzene is always fed in excess to increase the
ethylene and benzene selectivity as well as repress coke formation (Al-Kinany et al., 2012).

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Model development

The methodology in this paper follows the algorithm presented in Fogler (2016).

Reactions to be used:
Ethylbenzene formed by alkylation of ethylene and benzene.

Di-ethylbenzene formed by alkylation of ethylene and ethylbenzene.

It is clear that two parallel reactions take place, thus the relatives rates were determined for each
component and utilized in Polymath.

Mole balances:
This paper involves the production of ethylbenzene in an adiabatic and near-isothermal catalytic
packed bed reactor, with cold shot cooling by step-feeding the ethylene reactant, as well as reactor
cooling (Ng et al., 2016). Five packed beds are employed, with cooling taking place around the last
four beds. The amount of ethylene to be mixed with the feed benzene to the first bed equates to the
amount of ethylene to be step-fed before the second, third and fourth beds - a molar flow of 45
mol/s is the amount of each split. The reactions rates are also divided by the density of the catalyst,
as this paper deals with a heterogeneous system. All constants can be found in the Appendix.

In addition, the volumetric flow rate was determined through the use of Aspen. A benzene stream
was created with the molar flow of that found in our model. This stream was mixed with an ethylene
stream that also had the molar flow of our model. Both streams we diverted to a mixer where they
were subjected to the temperature and pressure of the reactor. The exit volumetric flow rate was
determined. For the simulation the thermodynamic property set of choice was Soave-RK, as this is
suited to petrochemical calculations. It was found that ethylene has a very low volumetric flow, and
the modular addition of ethylene across different reactor stages made very little difference to the
volumetric flow, so much that it was practically insignificant. We could therefore make the
assumption that the volumetric flow remains constant across the various reactor stages. The aspen
calculations can be found in the appendix.

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 Table 2: Mole balance and concentration equations.

Mole Balance Initial Condition Concentration

Rate laws:

Two reactions are considered to take place in the liquid phase, which include the alkylation of
ethylene and benzene to form ethylbenzene, as well as the alkylation of ethylene with ethylbenzene
to form di-ethylbenzene - shown below in table 1. These reactions will take place over Y zeolite
catalyst, although it has been found that beta catalyst exhibits superior ethylbenzene selectivity and
a higher conversion of ethylene (Yang et al., 2016).

Given that the catalyst lasts for about a year and that the beginning of operation with fresh catalyst
is assumed, the deactivation of the catalyst has been deemed negligible in this paper (Yang et al.,
2016). The reactions are exothermic, as can be seen by the negative heats of reaction (see
Appendix), and given this fact, the reactor system is non-isothermal. It is also known that the
reaction on the surface of the catalyst is the rate limiting step, which was taken into account in the
reaction rates aforementioned (You et al., 2006).

It is also known that falsified kinetics play a major part in the reliability of the results in this paper,
thus a plot of particle diameter versus the overall effectiveness factor was constructed, to obtain a
function of overall effectiveness factor in terms of particle diameter. In addition to this, the reaction
rates are multiplied by this function to obtain what the actual reactions rates are on an industrial
scale (Ercan et al., 1998) (see Appendix).

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 Table 3: Reactions, rate law and constant, activation energies (Ganji, et al., 2004)

Reaction Rate Law Unit Rate Constant Unit Activation Energy

Table 4: List of equations used to scale reaction rates.

List of scaled reaction rates

10

11

12

The overall effectiveness factor used to correlate the calculated reaction rates with those
observed on an industrial scale.

𝑛0 = 184898𝑑𝑝2 − 588.23𝑑𝑝 + 0.5386

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Stoichiometry:

Multiple reactions call for the determination of the molar flow of each component in the system
along the five packed beds (which has been modelled as one long bed) (see Appendix). The
concentrations were calculated using the equation below.

𝐹𝑗
𝐶𝑗 =
𝑣𝑜
Energy balance:

For a description of the calculations used to determine the heats of reactions as well as the Cp
values of all the components at reaction temperatures, refer to appendix, heat calculations.

Since only the first reactor bed is operated adiabatically and the rest with cooling, the equation
below was used.

𝑈
𝑑𝑇 𝑟 ′𝐴 Δ𝐻𝑟𝑥 (𝑇) − 𝜌𝑎 (𝑇 − 𝑇𝑎 )
𝑏
=
𝑑𝑊 ∑ 𝐹𝑖 𝐶𝑝𝑖

Modified for our system, the equation becomes:

𝑑𝑇 (𝑟1 𝑑𝐻𝑟1 + 𝑟2 𝑑𝐻𝑟2 )

=
𝑑𝑊 (𝐹𝐸 𝐶𝑝𝐸 + 𝐹𝐵 𝐶𝑝𝐵 + 𝐹𝐸𝐵 𝐶𝑝𝐸𝐵 + 𝐹𝐷𝐸𝐵 𝐶𝑝𝐷𝐸𝐵 )

The maximum value of this ‘cooling’ term was calculated in such a way that the final temperature of
each stage of reactor would not exceed 262°C. The basic idea of the ‘if’ statement is to calculate the
total energy of a system where all ethylene was fed at the start and reacted at the same rate of the
real system. The energy of the ethylene which is not actually in the system is subtracted from the
theoretical system and the energy of cold ethylene is added to the system as well as the
temperature of this new system calculated. This temperature is the real temperature of the system
and is used in all calculations further.

The inlet temperature of the feed benzene was chosen to be 175°C, 25°C for the ethylene in all
splits, while the maximum temperature that the reactor is designed for to prevent catalyst
deactivation is 260°C. The optimal temperature is 244°C (Ebrahimi et al., 2011). Based on literature,
the benzene to ethylene feed ratio is 7:1 (Qi Han Ng et al., 2016).

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The diffusion limitations were accounted for with the use of a function of particle diameter versus
the overall effectiveness factor (Ercan et al., 1998) (see Appendix).

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Modeling results

Figure 1 shows the final design of the

reactor. The reactor bed weights are
2.5 tons for reactor bed 1, 2 and 3.
Bed 4 is 3 tons, bed 5 is 7 tons and all
cooling specifications are shown.

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Figure 2: Component flow rate vs catalyst weight.
Figure 2 above shows the Flow rates of each component as a function of catalyst weight. The step
feeding can clearly be seen.

Figure 3: Ethylene flow rate vs catalyst weight.

For more clarity the flowrate of ethylene alone is shown in Figure 3 above.

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Figure 4: Component concentration rate vs catalyst weight.
Figure 4 above shows the concentration profile of the reactor and again for clarity the profile of
ethylene and ethylbenzene alone is shown below.

Figure 5: Ethylene and benzene concentration vs catalyst weight.

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Figure 6: Ethylene conversion vs catalyst weight.
In Figure 6 above the conversion of ethylene as a function of catalyst weight is shown and in Figure 7
below the pressure drop over the reactor is shown as function of catalyst weight.

Figure 7: Pressure drop vs catalyst weight.

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Figure 8: Reactor temperature profile vs catalyst weight.
Figure 8 above shows the temperature profile over the reactor and the staging in the reactor can
clearly be seen.

Figure 9: Reactor cooling vs catalyst weight.

Finally, Figure 9 above shows the cooling applied to the reactor, with maximum cooling at stage 4
and no cooling at stage 1. It is worth noting that the value of cooling is expressed negatively.

The various inlet parameters are chosen as 500K inlet temperature and 38Bar with ethylene
injections at equal amounts of 45 mol/s feeds. The pressure ranges from 35-0 bars (Woodle, 2006)
and the temperature is chosen to ensure effective reaction rate from the start of the bed. It is worth

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noting that heating any reactant, in the case of cooling by injection, is a form of inefficiency since
heat is being added which will later be preferable to remove. It might thus be worth considering
feeding more benzene and ethylene as side injections to cool the entire mixture and reduce catalyst
weight.

The final results of interest are as follows:

Table 5: Results summary

Pressure drop 21.00 Bar

Conversion 95.00 % ethylene

Ethylbenzene production 168.06 mol/s

Annual ethylbenzene production 513.84 kton/year

Total catalyst weight 17.50 ton

Total Bed Length 7.36 m

Reactor length 7.50 m

Diameter 1.84 m

Particle diameter 0.34 mm

Conclusions

In this paper the literature regarding an alkylation reactor was reviewed and a model reactor
developed in polymath from reactor laws and basics. The reactor shows good performance and
operates adiabatically and isothermally with jacket-type cooling. The final production of 500
kton/annum of ethylbenzene was met and the reactor was optimised for catalyst use.

Some improvements which may be considered are to feed both benzene and ethylene in stages to
increase the amount of temperature reduction and possibly reduce the amount of cooling required.
Another consideration is to account for non-ideal residence time distribution, which would increase
model accuracy.

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References

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 Appendix
Constants:
Table 6: Table of constants and manipulated variables

Value Unit
Constants
𝑅 = 8.314 𝐽
[ . 𝐾]
𝑚𝑜𝑙
𝜌𝑏 = 892.9 𝑔
[ ]
𝐿
Manipulated Variables
𝑑𝑝 = 0.00034 [𝑚]
𝑣0 = 163 𝐿
[ ]
𝑠
𝑊(0) = 0 [𝑔]
𝑊(𝑓) = 78500 [𝑔]
𝑇(0) = 448.15 [𝐾]

Table 7: Physical Properties (NIST, 2019)

MW (g/mol)

Benzene 78,1118

Ethylene 28,0532

Ethylbenzene 106,1650

[heat capacities]
[reaction rate constants]
[density]
[temperature equation]
[pressure equation]

27 | Page
Energy Balance calculations:
Table 8: Heat of formation data (NIST,2019)

vi Hfo (l) Hfo (g)

Benzene 1 49.00 82.90 kJ/mol

Ethylene 1 N/A 52.47 kJ/mol

Ethylbenzene 1 -12.50 29.80 kJ/mol

DEB 1 -72.84 -24.67 kJ/mol

The heat of reaction (ΔHro)is the change in enthalpy for a process for which stoichiometric
quantities of reactants at a specific temperature T and pressure P react completely in a
reaction to form products at the same temperature and pressure (Felder & Rousseau, 2005).
If ΔHro is negative, the reaction is exothermic. The heat of reaction can be calculated by using
standard heat of formation data.

EB: ΔHro = -105.57 kJ/mol

DEB: ΔHro = -64.64 kJ/mol

The Cp values of most of the components were determined by using the temperature
dependant heat capacity formula, with the appropriate parameter, as seen in table 9:

Table 9: Specific heat capacity equations.

Heat Capacity Data (Ideal Gas & Liquid)

1 𝐶𝑝 = 𝐴 + 𝑇 + 𝐶𝑇 2 + 𝑇 3 + 𝑇 4
2 𝐶𝑝 = 𝑅(𝐴 + 𝑇 + 𝐶𝑇 2 + 𝑇 2 + 𝑇 3 )
A B C D E Tmin Tmax Source eq
Benzene (l) 162,94 -344,94 0,85562 0 0 278,68 500 Perry 1
Ethylene (g) 1,424 0,014394 -0,00031 0 0 298 1500 Koretsky 2
Ethylbenzene (l) 154,04 -142,29 0,80539 0 0 178,2 409,35 Perry 1

The heat capacities of mixtures can be calculated with the following formula:

28 | Page
For DEB no parameters relating Cp values to temperature could be found. To solve this problem,
tabulated Cp values were obtained from the NIST chemical database and plotted, in excel, against
their measured temperatures. When these values were cut to mach only our temperature of
operation, a linear trend was observed. Fitting a trendline to the values allowed us to find an equation
relating the Cp of DEB to its temperature. Because of the very good correlation (R2 = 0.9958), this
equation was used in our CRE algorithm.

where x is temperature in K.

29 | Page
Volumetric flow calculations:

v1 v2 v3 v4
l/min 9783,832 9783,86 9783,889 9783,911
kmol/s 0,0162 0,0135 0,0135 0,0108
Cumulative 0,0162 0,0297 0,0432 0,054

l/s 163,0638667 163,0643333 163,0648167 163,0651833

m^3/s 0,163063867 0,163064333 0,163064817 0,163065183

30 | Page
Overall effectiveness factor excel calculations:

Particle diameter Overall effectiveness factor

0,196 0
0,126 0,091
0,034 0,36

Particle diameter vs Overall effectiveness factor

0,4
0,35
0,3
0,25
η 0,2
0,15 Series1
0,1
0,05
0
0 0,05 0,1 0,15 0,2 0,25
dp [m]

Polymath Code:

# Reaction rate equations

r_E1 = -k_r1*C_E/(1+K_EB*C_EB) #mol/L.s

r_E2 = -k_r2 * C_EB*C_E #mol/L.s

r_E1_scale = n_0*r_E1
r_E2_scale = n_0*r_E2
r_B1_scale = r_E1_scale
r_EB1_scale = -r_E1_scale
r_EB2_scale = r_E2_scale
r_DEB2_scale = -r_E2_scale
r_1 = -r_E1_scale
r_2 = -r_E2_scale

r_E = r_E1_scale + r_E2_scale

r_B = r_B1_scale
r_EB = r_EB1_scale + r_EB2_scale

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r_DEB = r_DEB2_scale

#Rate constants

k_r1 = 1.711E5*exp(-E_r1/(R*T)) #1/s

K_EB = -1.5202E-2*exp(-E_EB/(R*T)) #L/mol
k_r2 = 69.45*exp(-E_r2/(R*T)) #L/mol.s

#Activation energies

E_r1 = 6.344E4
E_EB = 3.933E3
E_r2 = 4.703E4

#Constants
R = 8.314 #J/mol.K
rho_b = 892.9 #g/L

#arbitrary constants

d_p = 0.00034 #m (can change, within limits)

v_0 = 163 #pretty much constant L/s
W(0) = 0
W(f) = 78500 #arbitrary g

#Overall effectiveness factor

n_0 = 184898*d_p^2 - 588.23*d_p + 0.5386

#differentials

d(F_E) / d(W) = r_E/(rho_b)

F_E(0) = 54 #mol/s
d(F_B) / d(W) = r_B/(rho_b)
F_B(0) = 1260 #mol/s
d(F_EB) / d(W) = r_EB/(rho_b)

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F_EB(0) = 0 #mol/s
d(F_DEB) / d(W) = r_DEB/(rho_b)
F_DEB(0) = 0 #mol/s

d(T) / d(W) = (r_1*dH_r1 + r_2*dH_r2 )/(F_E*Cp_E + F_B*Cp_B + F_EB*Cp_EB +

F_DEB*Cp_DEB)
T(0) = 448.15

#Concentrations

C_E = F_E/v_0
C_EB = F_EB/v_0
C_B = F_B/v_0
C_DEB = F_DEB/v_0

#std Heat of formations:

H_E = 52470 #J/mol

H_B = 49000 #J/mol
H_EB = -12500 #J/mol
H_DEB = -24670 #J/mol

#std Heat of reactions:

dH_r1_0 = H_EB - H_E - H_B #J/mol

dH_r2_0 = H_DEB - H_EB - H_E #J/mol

#Heat of reactions:

dH_r1 = dH_r1_0 + (Cp_EB - Cp_E - Cp_B)*(T-298.15) #J/mol

dH_r2 = dH_r2_0 + (Cp_DEB - Cp_E - Cp_EB)*(T-298.15) #J/mol

33 | Page
#Heat capacities
Cp_E = R*(1.424+0.014394*T-0.000314*T^2) #J/mol.K
Cp_B = (162.94-344.94*T+0.85562*T^2) #J/mol.K
Cp_EB = (154.04-142.29*T+0.80539*T^2) #J/mol.K
Cp_DEB = (448.68*T + 118863)/1000 #J/mol.K

Formulas for reactions:

Reaction rate equations:
− 𝒓 𝑬 𝒎
𝒓𝑬 = [ . 𝒔]
( + 𝑲𝑬𝑩 𝑬𝑩 ) 𝑳

𝒎
𝒓𝑬 = − 𝒓 𝑬𝑩 𝑬 [ . 𝒔]
𝑳
Rate constants:
𝑬𝒓
𝒓 = ( .𝟕 𝑬 )𝒆( 𝑹𝑻
)
[ ]
𝒔

𝑬𝒓 𝑳
∗ 𝒆( )
𝒓 = 𝟗. 𝑹𝑻 [ ]
𝒎

𝑬𝑬𝑩 𝑳
𝑲𝑬𝑩 = (− . 𝑬− )𝒆( 𝑹𝑻
)
[ . 𝒔]
𝒎

Activation energies:
𝑬𝒓 = . 𝑬
𝑬𝒓 = . 𝟕 𝑬
𝑬𝑬𝑩 = . 𝟗 𝑬
Scaled values for falsified kinetics

𝒓𝑬 ,𝒔𝒄 𝒆 = 𝒓𝑬

𝒓𝑬 ,𝒔𝒄 𝒆 = 𝒓𝑬

𝒓𝑩 ,𝒔𝒄 𝒆 = 𝒓𝑬 ,𝒔𝒄 𝒆

𝒓𝑬𝑩 ,𝒔𝒄 𝒆 = −𝒓𝑬 ,𝒔𝒄 𝒆

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 𝒓𝑬𝑩 ,𝒔𝒄 𝒆 = 𝒓𝑬 ,𝒔𝒄 𝒆

𝒓𝑫𝑬𝑩 ,𝒔𝒄 𝒆 = −𝒓𝑬 ,𝒔𝒄 𝒆

𝒓 = −𝒓𝑬 ,𝒔𝒄 𝒆

𝒓 = −𝒓𝑬 ,𝒔𝒄 𝒆

𝒓𝑬 = 𝒓𝑬 ,𝒔𝒄 𝒆 + 𝒓𝑬 ,𝒔𝒄 𝒆

𝒓𝑩 = 𝒓 𝑩 ,𝒔𝒄 𝒆

𝒓𝑬𝑩 = 𝒓𝑬𝑩 ,𝒔𝒄 𝒆 + 𝒓𝑬𝑩 ,𝒔𝒄 𝒆

𝒓𝑫𝑬𝑩 = 𝒓𝑫𝑬𝑩 ,𝒔𝒄 𝒆

Differentials:

𝑑𝐹𝐸 𝑟𝐸
=
𝑑𝑊 𝜌𝑏
𝑚𝑜𝑙
Where 𝐹𝐸 (0) = 54 [ ]
𝑠

𝑑𝐹𝐵 𝑟𝐵
=
𝑑𝑊 𝜌𝑏
𝑚𝑜𝑙
Where 𝐹𝐵 (0) = 1260 [ 𝑠
]

𝑑𝐹𝐸𝐵 𝑟𝐸𝐵
=
𝑑𝑊 𝜌𝑏
𝑚𝑜𝑙
Where 𝐹𝐸𝐵 (0) = 0 [ 𝑠
]

𝑑𝐹𝐷𝐸𝐵 𝑟𝐷𝐸𝐵
=
𝑑𝑊 𝜌𝑏
𝑚𝑜𝑙
Where 𝐹𝐷𝐸𝐵 (0) = 0 [ 𝑠
]

Concentrations:

35 | Page
 𝐹𝐸
𝐶𝐸 =
𝑣0

𝐹𝐵
𝐶𝐵 =
𝑣0

𝐹𝐸𝐵
𝐶𝐸𝐵 =
𝑣0
𝐹𝐷𝐸𝐵
𝐶𝐷𝐸𝐵 = 𝑣0
+

Constants:

𝐽
𝑅 = 8.314 [ . 𝐾]
𝑚𝑜𝑙
𝑔
𝜌𝑏 = 892.9 [ ]
𝐿

Manipulatible Variables

𝑑𝑝 = 0.00034 [𝑚]

𝐿
𝑣0 = 163 [ ]
𝑠

𝑊(0) = 0

𝑊(𝑓) = 78500 [𝑔]

Where 𝑇(0) = 448.15 [𝐾]

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