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Ethanol Production via Direct Hydration of

Ethylene: A review

Conference Paper August 2014


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3 authors:

Nur Syaera Hidzir Zalizawati Abdullah

Universiti Teknologi MARA Universiti Teknologi MARA


Ayub Md. Som

Universiti Teknologi MARA


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Ethanol Production via Direct Hydration of Ethylene: A review

Nur Syaera Hidzir1,a, Ayub Md Som2,b and Zalizawati Abdullah3,c
Faculty of Chemical Engineering, Universiti Teknologi Mara, 40450 Shah Alam,
Selangor, Malaysia
syaera88@gmail.com, bayub522@salam.uitm.edu.my, czalizawati8653@salam.uitm.edu.my

Keywords: Ethanol Production, Direct Hydration of Ethylene, Fixed Bed Reactor

Abstract. The world ethanol production has recently seen an incremental growth mainly due
to economic and environmental security concerns, worldwide. Ethanol has good burning
characteristics and may be considered as attractive transportation fuel alternates. An analysis
of the synthetic ethanol production via direct hydration process is presented in this study.
Since 1947, synthetic ethanol has been produced via direct hydration of ethylene replacing the
indirect hydration of ethylene. The development of the process model is crucial as it involves
with rigorous non-linear or complex equations for its sustainable future growth. In order to
gain better yield, product quality as well as flexibility and lower energy consumption of the
reactor used for the ethanol production, there is a great interest to develop an effective model-
based control system for the process. Developing the effective control strategy is the major
challenge so as to construct a suitable model which employs the dynamics of the process. In
this study, an overview of the ethanol production via direct hydration of ethylene is carried
out in order to give in-depth understandings on the complexity of its process dynamics and
possible strategies ahead to overcome the problems.

Ethanol is a liquid substance that is volatile, colorless and has a slight odor. It
apparently burns with smokeless blue flames that are not always visible in normal light. It
presents widely in nature and has many applications in the industrial and pharmaceutical
sectors as a solvent of substances intended for human contact consumption, including scents,
flavorings, colorings, and medicines [1]. Ethanol is also used with mixed gasoline and in
100% ethanol fueled vehicles [2]. Ethanol production had an extreme requirement globally as
a fuel additive as 1.02 1011 liters were produced in 2010 [3][4]. Most of the ethanol
produced is used as motor fuel or an additive in gasoline to improve its octane level. As a
liquid fuel, ethanol has long-term advantages. Ethanol has good properties for spark ignition
with the motor octane number (MON) and research octane number (RON) of 90 and 109,
respectively that is much greater than regular gasoline which is 88 [2]. The increase in the
world ethanol production is mainly due to the economic and environmental security concern,
worldwide. At certain countries like Europe, India, China, and Brazil, the ethanol production
is aimed for reducing petroleum import and increasing the consumption and production of
renewable fuel [5]. There are several ways to produce ethanol production such as
fermentation of ethanol, indirect hydration (esterification-hydrolysis) process and direct
hydration of ethylene [6]. Ethanol is produced by petrochemical through direct and indirect
hydration as well as via biological processes by fermenting sugars with yeast [7][3]. Most of
the industrial processes were done by fermentation process but the output was not reliable.

Direct hydration of ethylene

In 1947, the catalytic direct hydration of ethylene was first introduced by Shell [8].
The ethanol is manufactured through a chemical reaction of the ethylene with water vapors.

The ethylene and water reagent used in the process were preferred to be pure [9]. The reaction
involved is reversible and exothermic. The reaction of the direct hydration of ethylene
consists of three processes namely; reaction, recovery and purification, as well as production
of anhydrous ethanol as shown in the following equations[10][11][12][13]:

( ) ( ) ( ) (1)


( ) (3)

The rate of reaction:

( )

( )

( )

( )

r1, r2, r3, r4, r5 Rate of reaction
k1, k2, k3, k4, k5 Reaction constant
p Partial pressure
pw Water partial pressure
pA Acetaldehyde partial pressure
pE Ethanol partial pressure
pDEE Diethyl ether partial pressure
K Equilibrium constant
Kw Water equilibrium constant
KE Ethanol equilibrium constant
KA Acetaldehyde equilibrium constant
KDEE Diethyl ether equilibrium constant

By using the excess of the water vapour, the reaction will move to the right according
to Le Charteliers Principle. The catalyst used in this process is phosphoric (V) acid coated
onto a solid silicon dioxide [14]. The reaction zone should be free of any liquid water as it
will hydrolyse the acid catalyst to undesired catalyst species (Si(HPO4)2H2O) and may also
serve to degrade the catalyst [15]. To avoid catalyst losses, water/ethylene mole ratio of less
than one is used. The operation is conducted with a molar ratio H2O/C2H2 of 0.6. The direct
hydration of ethylene is accomplished at 250 300oC and 70 80 atm [16][17]. Ethylene and
high temperature water vapour are mixed and then passed over an acidic catalyst. The
conversion of ethylene is limited to 4-5% under this condition and the ethylene is recycled.
The ethanol selectivity to ethylene used is 98.5 molar percent [17][18].

Catalyst used in the process

The direct hydration of the ethylene has been carried out since about 60 years ago in
the chemical industry over catalyst consisting of the silica gel with a high loading of
phosphoric acid [19]. Catalyst is characterised as the supported liquid phase and the catalytic
active bound on a carrier as the concentrated liquid acid [15][19]. Phosphoric acid on silica

gel is more resistant to leaching than the acid on metal phosphate. The Silica gel-supported
phosphoric acid catalyst (H3PO4/SiO2) is used in the industry as it has high selectivity in
excess ethylene [20]. The ethanol production rate increases remarkably with increasing
phosphoric acid loadings. Phosphoric acid present in liquid like form on silica gel has a pure
acidic nature. The higher condensed phosphates take longer time to be hydrolysed. The
amount of the catalyst phosphoric acid was described by Cavani et. al. [14].
There have been several researches on the hydration of ethylene over different metal
phosphates (metal: Ge, Zr, Ti and Sn) and phosphoric acid impregnated metal phosphates at
high pressure [14][19][21]. These catalyst effects were compared with phosphoric acid on
silica and the result showed that the conversions were slightly higher by using the
impregnated metal phosphates [19]. The research conducted using the metal phosphates
shows that more rates of ethanol were produced as shown in table 1 [21].
Table 1. Rate of ethanol based on the catalyst used for the process

Catalyst Rate of ethanol (mol / g.min)

Ge 0.47
Zr 0.064
Ti 0.26
Sn 0.94
Si 0.92
H3PO4/SiO2 0.13
Source: Isobe et al., 2000, for illustration purposes only

Reactor used for the process

Fixed bed reactor is a reactor in which a stationary solid catalyst is used to carry out
reactions whereby the reactant is in mobile fluid phase that takes place on the surface of the
catalyst [22][23][24]. The reactant diffuses, adsorbs and reacts on the active surface of the
catalyst. Catalytic fixed bed reactors are the most widely used reactor for gas phase reactants
as well as in the production and synthesis of large scale basics chemicals and intermediates.
Fixed bed reactor is usually modelled and optimised using the continuum models that
are grouped in two categories namely; pseudo-homogeneous and heterogeneous model
[25][26][27]. If the differences between the fluid and solid phase conditions are significant,
heterogeneous model has to be considered in spite of the pseudo-homogeneous model with
average properties. The pseudo-homogeneous model does not take into account explicitly for
the presence of the catalyst in contrast to heterogeneous model which, in turns leads to the
separate conservation equations for fluid phase in the catalyst pores [28][24][29].
In the pseudo-homogeneous model, it is assumed that the catalyst surface is totally
exposed to the fluid conditions and there is no resistance to particle heat and mass transfer
taken place. On the other side, the heterogeneous model takes conservation equations for both
phases into account. The simplest pseudo-homogeneous model describes only axial profiles of
the radially average temperatures and concentrations. Since the only transport mechanism
taken into account is convection, it is referred to a plug-flow model [30].
( ) (9)
( ) ( ) (10)
us Space velocity
Ri Reaction rate
cp Specific heat capacity
Ci Concentration of component i
T Temperature
f Fluid density

Tw Water temperature
RT Heat generation per unit reactor volume
Uw overall heat transfer coefficient based on the bed side heat transfer area
z Axial variable

The simplest one-dimensional heterogeneous model takes into account on the

temperature and concentration differences between bulk fluids and catalyst surface [30].

Fluid phase:
( ) (11)
( ) ( ) (12)

Solid phase:
( ) ( ) (13)
( ) ( ) (14)

Cis Concentration of component i on catalyst surface
Cs Concentration of solid particles
kf Mass transfer coefficient
av Catalyst surface area per volumetric unit of reactor
hf Heat transfer coefficient

Several authors have studied the steady-state modelling of catalytic fixed bed reactor
but they have yet to discover the best model to be used due to lack of reliable data which
cause ineffectiveness and inaccuracy of the model. The model for the catalytic reactor is
divided into three phases namely: the fluid, the solid and the absorbed-phase. Sheintuch &
Nekhamkina (2001) modelled the reactor based on the conventional model on the heat and
mass transfer resistances and the balances. Shahrokhi & Baghmisheh (2005) modelled the
reactor based on the following assumption: (1) one-dimensional heterogeneous model, (2)
dispersion of mass and energy in axial and radial direction are negligible, (3) transient for the
mass and energy balances are considered, and (4) catalyst deactivation is neglected because
the large time constant.

The increase in the world ethanol production is mainly due to the economic and
environmental security concern. Ethanol is increasingly being used as a transport fuel in
different ways. Even though ethanol production is an established industrial process, there is
lack of development in the process model. It is recommended that further studies need to be
conducted to develop an effective model-based system comprises non-linear, complex
equations which govern the process dynamics, i.e. catalytic fixed bed reactor for ethanol
production, preferably using process modeling software (eg. gPROMS). Several simulation
and optimization works need to be carried out using the proposed model-based equations or
process control systems in order to gain better yield, product quality as well as flexibility and
lower energy consumption for the reactor in the ethanol production.

This research was funded by Ministry of Higher Education (MOHE) Malaysia through ERGS
Fund and Research Management Institute (RMI) (600-RMI/ERGS 5/3(46/2012)) Universiti
Teknologi Mara. We thank them all for the financial support given.

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