Accepted Manuscript

Title: Benzene alkylation with ethylene: the way to increase

the process efficiency

Authors: Elena Khlebnikova, Elena Ivashkina, Irena

Dolganova

PII: S0255-2701(17)30142-3
DOI: http://dx.doi.org/doi:10.1016/j.cep.2017.07.002
Reference: CEP 7020

To appear in: Chemical Engineering and Processing

Received date: 21-2-2017

Revised date: 29-6-2017
Accepted date: 2-7-2017

Please cite this article as: Elena Khlebnikova, Elena Ivashkina, Irena Dolganova,
Benzene alkylation with ethylene: the way to increase the process efficiency, Chemical
Engineering and Processinghttp://dx.doi.org/10.1016/j.cep.2017.07.002

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 Benzene alkylation with ethylene: the way to increase the process efficiency

Elena Khlebnikova, Elena Ivashkina, Irena Dolganova*

National Research Tomsk Polytechnic University, Tomsk 634050, Russia

Graphical abstract

Highlights
 The possibility to improve alkylation performance by means of mixing
intensifying was studied.
 Intensifying the mixing process will bring the alkylation from diffusion into
kinetic region.
 Changing the way of reagents injection into the mixing chamber is reasonable.

Ethylbenzene is the main ingredient to obtain textile fabric, plastics, detergents, etc. The current
industrial ethylbenzene production method includes mainly zeolite catalyst. However, liquid acidic
catalysts such are also still used. In contrast to zeolite alkylation technology, there is much less
information on how to improve the alkylation unit performance. The present research investigates the
possibility of obtaining this goal by intensifying the reagents mixing before the alkylation reactor. We
present the results of the mixing chamber hydrodynamic modeling clearly showing that it is reasonable
to change the way of reagents injection: benzene-into the first, circulating catalyst into the second and
fresh catalyst into the third pipe branch along the ethylene flow. This will intensify the mixing process
and reduce the size of the catalyst droplets bringing the alkylation from diffusion into kinetic region.
This variant of reagents injection will also ensure the uniformity of reagents distribution. The
possibility to decrease the circulating catalyst flow rate from 8000 to 5000 (kg h-1) without changing
the mixing efficiency also demonstrates the feasibility of the proposed solution.

Keywords: Hydrodynamics; mixing; optimization; droplets; mixers; simulation.

Introduction
The alkylation of aromatic hydrocarbons with alkenes is of industrial interest as a method to
obtain intermediate products in the chemical industry [1–3]. These products are necessary to obtain
textile fabric, plastics, detergents, etc. Among the aromatic products obtained by synthesis is
ethylbenzene, which is principally used to obtain phenol and acetone [4,5].
The benzene alkylation is referred to as key point of the ethylbenzene manufacturing and is
essential for a wide range of industrial technologies [6]. The fundamental differences in technological
schemes are related to the reaction phase and vessel system. Most production methods have
approximately 95 % conversion. These encompass the gas-phase reaction, liquid-phase process using
an AlCl3 acid catalyst, and a liquid phase reaction in fixed bed reactors using a zeolite catalyst.
Experimantally, it was found that the main products of the benzene alkylation with ethylene are
ethylbenzene, polyethylbenzene and diphenylethane.
Despite the fact that zeolite-using alkylation technologies are more promising, many of refineries
(especially in Russia and in China) still use liquid acidic catalysts [7,8]. The possibility of transition to
heterogeneous zeolite catalysts is not always economically practical, therefore the perspective solution
of the existing technological problems is installation of new mixing equipment in front of the reactor
unit [9].
A considerable amount of literature has been published on ethylbenzene manufacturing. A
number of studies have reported using of selective zeolite catalysts [9–19]. These findings refer to the
special pore structure of zeolites, catalysts activity and stability, kinetics of hydrocarbons
transformations. Surveys such as that conducted by Hansen (2009) and Ercan (1988) analyze mass-
transfer effects and diffusion limitations [14,15]. Several studies focus on finding the ways to improve
the alkylation process. These propose novel industrial process designed for the highly selective
production of ethylbenzene [17,20], new ways to perform alkylation in a packed reactive distillation
column in order to avoid catalyst deactivation [21], an approach to reduce the unit's energy
consumption by using the newly designed scheme (two double-bed alkylation reactors converted into
four single-bed reactors) [22]. There are also reports on transalkylation or disproportion reactions
occurring simultaneously with alkylation [23,24]. Several mathematical models were developed to
describe the alkylation reactors behavior [24–26].
In contrast to alkylation modeling and surveys on zeolite catalysts , there is much less
information about approaches to improve the existing liquid acid-catalyzed units. The purpose of the
present work was to estimate the feasibility of mixing device reconstruction in order to intensify the
reactants mixing. This will likely increase efficiency of alkylation and reduce the required catalyst
supply. The intensification of the reactants mixing in front of before the catalytic reactor allows
acceleration of chemical reactions by increasing the phase interface of the mixed components so that it
is possible to reduce a supply of liquid corrosion-active catalyst. In this case, the considered classical
process of alkylation of benzene with ethylene achieves the efficiency of the “Monsanto-Lummus
Crest” technology.

Object and methodology of research

Object of research
The alkylator is a hollow columned-type device with a bubbler (Fig. 1). Gaseous ethylene is
mixed with benzene and catalyst complex in the in the external mixing chamber. Alkylation occurs
under the following conditions: 383-408 K and 0.05-0.3 MPa. Optimal weight ratio – benzene: ethylene
is (8-14): 1.

The mixing elements in the mixing chamber are metal rods in the form of curved plates arranged
directly along the flow direction. The mixing chamber model in longitudinal section is presented in Fig.
2.
We have chosen this type of mixing as the enterprise that is the object of our research
collaborates. From the proposed nozzles we chose mixing nozzle that is made of corrugated plates and
form open, intersecting channels in which the flow is divided into many substreams. This chamber is
used in the turbulent and transitional flow regime, in particular, to intensify mass transfer between
fluids.
Constructional parameters of the mixing chamber are presented in Table 1.

Hydrodynamic modeling

To develop the hydrodynamic model of the mixing chamber we used the Comsol Multiphysics
4.2 software that has a graphical and interactive simulation [27,28]. Physical properties of the mixed
substances (ethylene, benzene, fresh and circulating catalyst complexes) are presented in Table 2.

Hydrodynamic modeling was performed at a temperature of 333 K and under a pressure of 0.5
MPa. These are the the mixing chamber operating parameters.

Numerical formulation and governing equations

The Turbulent Two-Phase Flow system was used in this study. Such system is used to track the
interface between two immiscible fluids. The flow is assumed to be turbulent; that is, its Reynolds
number for ethylene in mixing element is equal to 91944.
The stationary three-dimensional flow of an incompressible Newtonian fluid in a static mixer was
simulated using a system of differential equations of momentum transfer and the equation of non-
inversion Eqs. (1) and (2).

  (  w)  0 (1)
  
`   (  w w)  P    ( )   g (2)
 
P – pressure; w – flow velocity vector;  – density of the liquid; g – vector of the acceleration of
gravity; – stress tenser determined as in Eq. 3 below:
  
   ( w  w )
T
(3)
After that, we used the semi-empirical differential models of turbulence (standard k-ɛ model),
Eqs. (4) and (5):
   i k 
(  kw i )  (   )   Gk  Gb   (4)
xi x j   k x j 
   i    2
(  kw i )   (   )   G (G  C G )  C  (5)
xi x j    x j  1 k k 3 b 2
k
Here C1 , C2 , k ,   – standard parameters of the series of k-ɛ models; Gk – rate of the turbulence
energy generation; k – kinetic energy of the turbulence; ɛ - rate of the dissipation of the kinetic energy
of the turbulence; μ1 – effective coefficient of viscosity which is calculated as presented in Eq. 6:
k2
1   C (6)

Where Cμ is a model constant.
This turbulence model was used as the most appropriate to model the wide range of turbulent flows in
the shaped-form channels.
The velocity component normal to the wall to zero (Eq. 7):
un  o (7)
 This boundary condition prescribes a no-slip condition for solid walls in a turbulent flow.
Wall Functions below are used to model the thin region near the wall with high gradients in the
flow variables (Eqs. 8-11):
u
(   T )(u  (u )T )  n   T utan g (8)

w

utang  u  (u  n)n (9)

k  n  o (10)
C k2
   (11)
kv w 
Velocity was used as a boundary condition for the inlets, the pressure equaled to 0.1 MPa was
used as a boundary for the outlet.
To estimate the standard deviation of the catalyst concentration we used the Particle Tracing for
Fluid Flow model.

The solution method

Differential equations were approximated on the computational grid on the assumption that each
cell represents a finite volume in which the rates of change of physical quantities are balanced by the
fluxes of these quantities through the faces of the cell.
“Comsol Multiphysics” uses four types of different three-dimensional elements - tetrahedrons
(tetrahedrons), hexahedrons (hexahedra), prisms and pyramids. These four elements can be used in
various combinations to construct a grid of any two-dimensional and three-dimensional model.
Elements of three types of hexahedrons, prisms and pyramids should be used when necessary, since
these elements can not always be used to construct a grid for detailed geometry. The tetrahedral
element is the basic element type for most physical tasks in the “Comsol Multiphysics” software.
Tetrahedra are also known as simplexes, which means the following: for any three-dimensional body
with the exception of the profile or topology, it is possible to construct a grid of tetrahedra, and they are
also the only elements that can be used to thicken the adaptive grid. For these reasons, tetrahedra were
chosen as the grid elements.
Convergence on the grid is estimation of the accuracy of the solution obtained. If a small grid size
is used, the solution results will be more accurate, but the calculation time will be significantly
increased. When constructing the mixer grid, several grid sizes were used. A smaller mesh was used for
the regions of the mixing elements. As a result, the generated grid included 85477 cells (Fig. 3).

The evaluation of the mixing quality

The efficiency of the mixing process characterizes the quality of the technological system and
depends generally on the physical process occurring in the mixer. There are three groups of parameters
to estimate the mixing efficiency:
- Parameters that depend on macro characteristics of the flow, e.g. the process of
homogenization. The measure of the mixing efficiency in this case is the flow uniformity.
- Parameters that depend on the micro characteristics of the flow (emulsification, dispersion):
the interfacial surface, dispersed composition, etc.
- Parameters that depend on the boundary flow, namely, on the phenomena of heat and mass
transfer at the interfaces of the phases: the mass transfer coefficient, the thickness of the boundary layer.
One of the suitable parameters for estimating the degree of mixing nonuniformity is the average
striation of the bands.
Considering the performed hydrodynamic study for the mixing chamber cross-section (Fig. 4),
we obtained the profiles of the liquid phase distribution.
 To determine the standard deviation of the concentration, we considered the system of
components as two-components mixture. If the gas phase-ethylene concentration is equal to c1, where
0≤c1≤1, then the concentration of the liquid phase (mixture of benzene and catalyst complexes) is
C2=(1-C1). We divided the cross-section at the output from the mixer by N concentration measuring
points. The partitioning must take place in such a way that the product of the area of each divided
area by the local speed normal to this area was equal for each measuring point, which will correspond
to the volume flow. Then the average concentration can be found from the Eq. 12:
1 N V1
C1   C1,n  (12)
N n 1 V1  V2
Where C1 - the concentration of the first component in the n region, and V1, V2 - volumetric flow rates
of the components. Then the standard deviation of concentration is presented in Eq. 13:
1 N
S1   (C1,n  C1 )
N  1 n 1
(13)

Relative standard deviation of concentration is presented in Eq. 14:

S1
RSD  (14)
C1 (1  C1 )
If RSD = 1 it is assumed that the components at the outlet from the mixer are absolutely unmixed.
For RSD→1, a complete homogenization of the mixture is observed.
Results and discussion
Defining the macrokinetic region of benzene alkylation with ethylene

The necessity of new mixing chamber before the reactor block stems from calculations
confirming that more effective components mixing will bring alkylation to kinetic region in the
alkylation reactor so that the reaction rate will depend completely on the rate of chemical
transformations. To estimate the coefficients of molecular diffusion of ethylene and catalyst we used
Eqs. (15) and (16):

7.4 108 T ( M B )0.5

DAB  (15)
 BVA0.6

7.4 108 T ( M C )0.5

DAC  (16)
CVA0.6
where DAB (DAC) – coefficient characterizing molecular diffusion of ethylene in benzene (catalyst) (m2
s-1); MB (MC) – molecular mass of benzene (catalyst) (g mol-1); μB (μC) – viscosity of benzene (catalyst),
cP; VA – molar volume of ethylene, cm3 mol-1; Т – temperature, К.
In the current research, we did not consider the pressure drop. Hydrodynamic modeling was
performed at 333 K and 0.5 MPa.
Physical properties of substances depending on temperature were determined at a temperature of
393 K.
Under these conditions, DAB and DAC equaled to 1.13∙10-8 and 2.33∙10-8(m2 s-1) respectively. If
velocity of the catalyst droplet is similar to that of the reagents flow, the Eq. (17) is applicable:
D  Nu
Nu  3.6   AC (17)
dk
where Nu – the Nusselt number; dк – diameter of the catalyst droplet (m).
The calculations above show that diffusion of the reagents into catalyst phase does not influence
the process rate significantly, Eq. (18).
 k '  V
k *   k*  k '  ki  Cbenz (18)
F
where k*– reaction rate constant per unit area (m s-1); β – mass-transfer factor (m s-1); F – area of the
droplet surface, m2; ki'– reaction rate constant of the first order (s-1); ki – reaction rate constant of the i-
th reaction (m3 mol-1 s-1); Cbenz – the benzene averaged concentration (mol m-3); ΔV– volume of the
catalyst drop, m3.
For results of calculations performed for desired alkylation reaction, see Table 3.

The obtained results clearly indicate that installing the new mixing equipment allows reducing
the diameter of catalyst droplets from 25 mm to 0.5 mm, and this intensifies the internal diffusion of
reagents in comparison with the rate of chemical reaction, as presented in Eq. (19):
DAB
 F  ki'  V (19)
r
where Δr – radius of the catalyst droplet, m.
Table 4 presents results of comparing the contribution of the internal diffusion and the rate of
chemical reaction to change of the reagents concentration.

The results presented in Table 4 unequivocally indicate that alkylation process is limited by the
D
internal diffusion of the reagents if diameter of the catalyst droplet 3equals 25 mm ( AB  F  ki'  V ).
r
If it equals 0.5 mm, there is a reverse situation and the diffusion rate is much more significant
D
( AB  F  ki'  V ). Thus, it was proven that reducing the catalyst droplet and intensifying mixing
r
brings the alkylation from diffusion into kinetic region. With that, the influence of the external
diffusion recedes ( k *   if the droplet diameter is 25 mm; k *   if the droplet diameter is 0.5
mm).
With due consideration of the results obtained via the performed calculations it may safely be
said that using the new mixing chamber will improve the alkylation process by intensifying the
reagents mixing.

Ensuring the effective use of the mixing chamber

The next important problem solved in current research was defining the optimal way of reagents
injecting into the mixing chamber. A commercial solver COMSOL Multiphysics 4.2 has been used to
develop the hydrodynamic model of the mixing chamber carry out the numerical simulations.
Three variants of reagents injecting were examined.
The first variant
 Benzene is injected into the second pipe branch along the ethylene flow and circulating catalyst
into the third. The figure below shows the ethylene distribution and its concentration in the flow (Fig.
5).

At such mode of flows injecting into the mixing chamber it is used incompletely. Moreover, at
the outlet from the mixing chamber the flow stratifies. As presented in the isosurface above, the
ethylene distribution is nonuniform and varies from 0.86 to 0.91 (mol m-3). The velocity at the lower
part is 8-14 (m s-1), and the liquid phase is distributed mainly in the outer part of the mixing chamber.
The second variant
Further evidence comes from studies on the second variant of the reagents injection: the
circulating catalyst is injected into the second pipe branch along the ethylene flow and benzene into the
third.
The concentration profiles are quite similar to the first variant of the flows injection. We observe
the same flow stratification at the outlet and can conclude that the mixing chamber is also used
incompletely. The ethylene distribution in such a variant varies from 0.86 to 0.99 (mol m -3), the
velocities at the lower part are 7-14 (m s-1).
The third variant
To improve the mixing chamber and finally the alkylation reactor performance we proposed to
modify the way of the reagents injection (Fig. 6).
The specificity of the presented variant is in the way of flows distribution: benzene is injected
into the first pipe branch along the ethylene flow, the circulating catalyst into the second and the fresh
catalyst into the third. For this variant we observed markedly intensive reagents and catalyst mixing
(Fig.7, 8).

The provided figures indicate that at such a variant of flows distribution the use of the upper part
of the mixing chamber is maximized, as expected. Just after the second pipe branch there is a uniform
reagents distribution in the lower part of the chamber body, and the ethylene concentration stabilizes at
the level of 0.89 (mol m-3). The velocities vary from 2 to 14 (m s-1). Regarding the catalyst
concentration, it is about 110 (mol m-3). The catalyst is distributed uniformly after the upper part of the
mixing chamber.
The circulating catalyst flow rate depends on that of the reagents and varies from 5000 to 10000
(kg h-1) (the regulated data). For studied reagents flow rate, the current circulating catalyst flow rate
was 8000 (kg h-1). During the research, we tried to examine the possibility of decreasing the flow rate
of the circulating catalyst to 5000 (kg h-1). As is presented in Fig. 8, it is possible to decrease it from
8000 to 5000 (kg h-1) without changing the mixing efficiency.
The catalyst concentration is lower: 80 instead of 110 (mol m-3). However, its distribution is not
less uniform. From now we assume that changing the way of catalyst injection allows improving the
reagents mixing process due to decreasing the circulating catalyst flow rate and increasing the catalyst
distribution uniformity.

Results of the mixing quality evaluation

The cross-sectional position characterizes the distribution plane of the mixing components at the
outlet from the mixing chamber. The standard deviation of the concentration was determined using the
methodology described in the section “The evaluation of the mixing quality”. As presented in Fig. 9, at
the output of the apparatus the pattern consists of alternating bands of different colors, the thickness of
which determines the mixing efficiency.
 Analyzing the obtained concentration profiles allowed us to find that the liquid phase
concentration varies from 0.1 to 0.15 volume ratio (Fig. 9a) for the first variant of injection and from
0.14 to 0.15 for the third variant (Fig. 9b). The best profile of concentration distribution at the outlet of
the mixer is observed for the third variant of injection.
For the investigated ways of the reagent injection, the relative deviations of concentrations were
0.0663 and 0.0048, for the first and third variants, respectively. Thus, the third variant of the reagents
injection (benzene is injected into the first pipe branch along the ethylene flow, the circulating catalyst
into the second and the fresh catalyst into the third) is the best and can be recommended as optimal.

Conclusions
In this paper we propose the approach to improving the ethylbenzene manufacturing process by
intensifying the reagents mixing. The salient points of our research are as follows.
The liquid phase concentration varies from 0.1 to 0.15 volume ratio for the first variant of
injection and from 0.14 to 0.15 for the third variant. The best profile of concentration distribution at the
outlet of the mixer is observed for the third variant of injection. The results of hydrodynamic modeling
indicate that it is reasonable to change the way of reagents injection: benzene-into the first, circulating
catalyst into the second and fresh catalyst into the third pipe branch along the ethylene flow. This will
intensify the mixing process and reduce the size of the catalyst droplets bringing the alkylation from
diffusion into kinetic region. This variant of reagents injection will also ensure the uniformity of
reagents distribution. This also allows decreasing the circulating catalyst flow rate from 8000 to 5000
(kg h-1) without changing the mixing efficiency.
As the problem optimal reagents mixing will remain even if the sulfonation apparatus
construction is changed, the results of our research represent an excellent initial step toward designing
and modeling the construction of new reactors and mixing equipment. Our findings add to a growing
body of literature on ethylbenzene and provide a blueprint for a new way to improve alkylation process
by intensifying the reagents mixing. We believe that our results might be useful both for technological
unit staff and for the educational process.
In our future research we intend to concentrate on improving the alkylation reactor performance
with use of the developed computer modeling system considering the process unsteadiness [29], as
discussed in [30–32].

Acknowledgements:
This research was supported by the Grant of the President of Russia № MD-5019.2016, financed by
Russian Government, “Developing the scientific base for resource efficient technology of alkanes
treating in the technology of synthetic detergents manufacturing”. The experimental calculations are
carried out at Tomsk Polytechnic University within the framework of Tomsk Polytechnic University
Competitiveness Enhancement Program grant.

REFERENCES

[1] G. Caeiro, R.H. Carvalho, X. Wang, M.A.N.D.A. Lemos, F. Lemos, M. Guisnet, F. Ram??a
Ribeiro, Activation of C2-C4 alkanes over acid and bifunctional zeolite catalysts, J. Mol. Catal.
A Chem. 255 (2006) 131–158. doi:10.1016/j.molcata.2006.03.068.

[2] A. Alotaibi, H. Bayahia, E.F. Kozhevnikova, I. V. Kozhevnikov, Selective Alkylation of

Benzene with Propane over Bifunctional Pt-Heteropoly Acid Catalyst, ACS Catal. 5 (2015)
5512–5518. doi:10.1021/acscatal.5b01102.
[3] A. Corma, V. Martı́nez-Soria, E. Schnoeveld, Alkylation of Benzene with Short-Chain Olefins
over MCM-22 Zeolite: Catalytic Behaviour and Kinetic Mechanism, J. Catal. 192 (2000) 163–
173. doi:10.1006/jcat.2000.2849.

[4] J.J. Clayden, N. Greeves, S. Warren, P. Wothers, Organic Chemistry, 2001. doi:10.1086/278635.

[5] J. Clayden, N. Greeves, S. Warren, P. Wothers, Organic Chemistry, Am. Nat. 40 (2001) 1990–
1992. doi:10.1086/278635.

[6] W. Yang, Z. Wang, H. Sun, B. Zhang, Advances in development and industrial applications of
ethylbenzene processes, Chinese. 37 (2016) 16–26. doi:10.1016/S1872.

[7] K. Srirattnai, S. Damronglerd, S. Omi, S. Roengsumran, A. Petsom, G.H. Ma, Encapsulated

AlCl3: A convenient catalyst for the alkylation of benzene with dodecene, Tetrahedron Lett. 43
(2002) 4555–4557. doi:10.1016/S0040-4039(02)00702-5.

[8] K.E. Kharlampidi, I.R. Izmailov, N.N. Batyrshin, Alkylation of benzene with 1-butene in the
presence of AlCl3., Russ. J. Gen. Chem. (Translation Zhurnal Obs. Khimii). 70 (2000) 278–280.

[9] S. Namuangruk, P. Pantu, J. Limtrakul, Alkylation of benzene with ethylene over faujasite
zeolite investigated by the ONIOM method, J. Catal. 225 (2004) 523–530.
doi:10.1016/j.jcat.2004.04.016.

[10] M.C. Al-Kinany, H. a. Al-Megren, E. a. Al-Ghilan, P.P. Edwards, T. Xiao, A.S. Al-Shammari, S.
a. Al-Drees, Selective zeolite catalyst for alkylation of benzene with ethylene to produce
ethylbenzene, Appl. Petrochemical Res. 2 (2012) 73–83. doi:10.1007/s13203-012-0022-6.

[11] K.A. Becker, H.G. Karge, W.D. Streubel, Benzene alkylation with ethylene and propylene over
H-mordenite as catalyst, J. Catal. 28 (1973) 403–413. doi:10.1016/0021-9517(73)90133-4.

[12] A. Corma, V. Martínez-Soria, E. Schnoeveld, Alkylation of Benzene with Short-Chain Olefins

over MCM-22 Zeolite: Catalytic Behaviour and Kinetic Mechanism, J. Catal. 192 (2000) 163–
173. doi:10.1006/jcat.2000.2849.

[13] Y. Du, H. Wang, S. Chen, Study on alkylation of benzene with ethylene over β-zeolite catalyst
to ethylbenzene by in situ IR, J. Mol. Catal. A Chem. 179 (2002) 253–261. doi:10.1016/S1381-
1169(01)00384-3.

[14] C. Ercan, F.M. Dautzenberg, C.Y. Yeh, H.E. Barner, Mass-Transfer Effects in Liquid-Phase
Alkylation of Benzene with Zeolite Catalysts, Ind. Eng. Chem. Res. 37 (1998) 1724–1728.
doi:10.1021/ie970797b.

[15] N. Hansen, R. Krishna, J.M. VanBaten, A.T. Bell, F.J. Keil, Analysis of diffusion limitation in
the alkylation of benzene over H-ZSM-5 by combining quantum chemical calculations,
molecular simulations, and a continuum approach, J. Phys. Chem. C. 113 (2009) 235–246.
doi:10.1021/jp8073046.

[16] N. Hansen, T. Brüggemann, A.T. Bell, F.J. Keil, Theoretical investigation of benzene alkylation
with ethene over H-ZSM-5, J. Phys. Chem. C. 112 (2008) 15402–15411. doi:10.1021/jp8036022.

[17] K. Liu, S. Xie, S. Liu, G. Xu, N. Gao, L. Xu, Catalytic role of different pore systems in MCM-
 49 zeolite for liquid alkylation of benzene with ethylene, J. Catal. 283 (2011) 68–74.
doi:10.1016/j.jcat.2011.07.004.

[18] L.M. Tiako Ngandjui, D. Louhibi, F.C. Thyrion, Kinetic analysis of diethylbenzene-benzene
transalkylation over faujasite Y, Chem. Eng. Process. Process Intensif. 36 (1997) 133–141.
doi:10.1016/S0255-2701(96)04179-7.

[19] B. Zhang, Y. Ji, Z. Wang, Y. Liu, H. Sun, W. Yang, P. Wu, Liquid-phase alkylation of benzene
with ethylene over postsynthesized MCM-56 analogues, Appl. Catal. A Gen. 443–444 (2012)
103–110. doi:10.1016/j.apcata.2012.07.028.

[20] S. Liu, F. Chen, S. Xie, P. Zeng, X. Du, L. Xu, Highly selective ethylbenzene production
through alkylation of dilute ethylene with gas phase-liquid phase benzene and transalkylation
feed, J. Nat. Gas Chem. 18 (2009) 21–24. doi:10.1016/S1003-9953(08)60071-7.

[21] Z. Qi, R. Zhang, Alkylation of benzene with ethylene in a packed reactive distillation column,
Ind. Eng. Chem. Res. 43 (2004).

[22] A.N. Ebrahimi, A.Z. Sharak, S.A. Mousavi, F. Aghazadeh, A. Soltani, Modification and
optimization of benzene alkylation process for production of ethylbenzene, Chem. Eng. Process.
Process Intensif. 50 (2011) 31–36. doi:10.1016/j.cep.2010.10.011.

[23] M.C. Al-Kinany, B.Y. Jibril, S.H. Al-Khowaiter, M.A. Al-Dosari, H.A. Al-Megren, S.M. Al-
Zahrani, K.I. Al-Humaizi, Low temperature transalkylation of o-diethylbenzene with benzene to
ethylbenzene using triflic acid as a catalyst, Chem. Eng. Process. Process Intensif. 44 (2005)
841–846. doi:10.1016/j.cep.2004.08.011.

[24] S.M. Al-Zahrani, M.C. Al-Kinany, K.I. Al-humaizi, S.H. Al-Khowaiter, Transalkylation and
isomerization of ortho-diethylbenzene with benzene using trifluoromethanesulphonic acid
catalyst: kinetic analysis, Chem. Eng. Process. Process Intensif. 41 (2002) 321–327.
doi:10.1016/S0255-2701(01)00148-9.

[25] H. Ganji
Alkylation Process Reactors For Production Of Ethylbenzene, Pet. Coal. 46 (2004) 55–63.

[26] A. Chianese, M.C. Annesini, R. De Santis, L. Marrelli, A model of a pilot bubble column reactor
for benzene alkylation by ethylene, Chem. Eng. J. 22 (1981) 151–158. doi:10.1016/0300-
9467(81)80033-0.

[27] Comsol, Multiphysics COMSOL, 2010. doi:10.1007/s10237-010-0257-z.

[28] COMSOL Inc., COMSOL Multiphysics, 2013.

[29] E. Ivanchina, E. Ivashkina, I. Dolganova, E. Frantsina, I. Dolganov, Influence of alkylaromatic

hydrocarbons on the efficiency of linear alkylbenzene sulfonic acid synthesis, Chem. Eng. J.
(2017). doi:10.1016/j.cej.2017.06.032.

[30] S.A. Koshkin, L.A. Ignatova, E.N. Ivashkina, I.O. Dolganova, Modeling of Transalkylation
Stage of Ethylbenzene Manufacturing with Zeolite-catalysts, in: Procedia Eng., 2016.
doi:10.1016/j.proeng.2016.07.622.
[31] E. Ivanchina, E. Ivashkina, E. Frantsina, I. Dolganova, S. Ivanov, Increasing the Selectivity of
Synthesis Stages for Linear Alkyl Benzenes, Curr. Org. Synth. 14 (2017) 342–352.

[32] E. Khlebnikova, A. Bekker, E. Ivashkina, I. Dolganova, E. Yurev, Thermodynamic Analysis of

Benzene Alkylation with Ethylene., Procedia Chem. 15 (2015) 42–48.
doi:10.1016/j.proche.2015.10.007.
Fig.1.
Alkylation reactor scheme

Fig.2.
Scheme of the mixing chamber
Fig. 3.
Generated calculation grid

Fig. 4.
The mixing chamber cross-section
Fig. 5.
Profile of ethylene distribution (2 sec after injection)

Fig. 6.
The modified variant of flows injection

Fig. 7. Fig. 8.
Profile of ethylene distribution (2 sec after Catalyst concentration (2 sec after injection)
injection)
 (a) (b)
Fig. 9.
The distribution of the liquid phase in the mixing chamber cross section for the first (a) and the third (b)
variants of injection

Table 1.
The design parameters of the chamber.
Parameter Value
The length of the pipe section (m) 2
Diameter of the pipe (m) 0.15
Diameter of dry benzene pipe (m) 0.08
Diameter of circulating catalytic complex pipe (m) 0.08
Diameter of fresh catalytic complex pipe (m) 0.05
Diameter of the mixing element (m) 0.15

Table 2.
Physical properties of the mixed flows.

Circulating
Benzene Fresh catalyst Ethylene
catalyst
Molar mass (kg mol-1) 0.0781 0.0852 0.0927 0.024
Density (kg m-3) 845 997 1055 5
Viscosity (cP) 0.4378 0.4069 0.4288 1.11·10-2
Flow rate (kg h-1) 13968 1998 7992 1199
Linear rate (m s-1) 0.913 0.283 0.566 3.77
Table 3.
Values of mass-transfer factors and reaction rate constants for different diameters of the catalyst droplet
at a temperature of 393 K.
Diameter of the catalyst droplet: Diameter of the catalyst droplet:
25 mm 0.5 mm
Reaction Mass-transfer Reaction rate Mass-transfer Mass-transfer
-1 -1
factor (m s ) constant per unit factor (m s ) factor (m s-1)
area (m s-1)
Benzene + Ethylene
9,04∙10-7 1,21∙10-5 4,52∙10-5 2,41∙10-7
→ Ethylbenzene

Table 3.
Contribution of the internal diffusion and the rate of chemical reaction to change of the reagents
concentration (at a temperature of 393 K).

Diameter of the catalyst droplet: Diameter of the catalyst droplet:

25 mm 0.5 mm
DАВ DАВ
Reaction  F (m3 s-1) k   V (m3 s-1)  F (m3 s-1) k   V (m3 s-1)
r r
Benzene + Ethylene →
3,65∙10-9 2,37∙10-8 7,31∙10-11 1,89∙10-13
Ethylbenzene