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Synthetic ethanol production in the Middle East: A way to make

environmentally friendly fuels

Article  in  Chemistry and Technology of Fuels and Oils · May 2013

DOI: 10.1007/s10553-013-0421-0

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Chemistry and Technology of Fuels and Oils, Vol. 49, No. 2, May, 2013 (Russian Original No. 2, March-April, 2013)

TECHNOLOGY

SYNTHETIC ETHANOL PRODUCTION IN THE MIDDLE EAST: A WAY

TO MAKE ENVIRONMENTALLY FRIENDLY FUELS

Behrooz Roozbehani, Mojtaba Mirdrikvand, Saeedeh Imani

Moqadam, and Ali Cheshmeh Roshan

Ethanol is synthesized by hydration of ethylene and by fermentation of foodstuffs, sugar-containing

plants, and agricultural wastes. The ethylene hydration process for producing high-purity ethanol for
use as a fuel additive is investigated in the context of Middle East market situations. An ethanol
production plant using zirconium-tungsten catalysts is modeled using HYSYS and Aspen Plus software.
It is shown that the ethanol concentration in the product can be raised from 87% to 99.7% by using an
extractive distillation column. The economic aspects of such an improvement in ethanol purity are
discussed.
Key words: ethanol, ethylene hydration, Middle East, azeotrope, extraction column, fermentation.

According to official statistical data, global ethanol production in 2010 was 102·10 9 liters. Most
ethanol (~97%) is produced by fermentation, and only 7% is produced by hydration of ethylene [1, 2]. The major
producers of synthetic ethanol are plants of multinational companies such as Sasol in Europe and South Africa,
Equistar in the USA, and SADAF in Saudi Arabia [3]. The largest plants, producing 140 kilotons synthetic ethanol
per year, are located in Germany and Scotland [4-6]. The increased production of synthetic ethanol in 2012 compared
with 2012 may be due to the rise in prices for agricultural products and limited agricultural resources.
It is believed that the fermentation method is too uncertain from the standpoint of providing a constant
supply of ethanol in the Middle East region [7]. On the other hand, synthesis of ethanol is economically less
attractive than fermentation in the USA because of the high cost of ethylene and the sufficient supply of agricultural
products. Thus in the USA, production of synthetic ethanol is decreasing while in Saudi Arabia, having features
in common with Iran and other countries in the Middle East, production of synthetic ethanol is growing [7-11].

____________________________________________________________________________________________________
Research Center, Petroleum University of Technology. Abadan School of Chemical Engineering, Abadan,
Iran. E-mail: saeedeh.imani@gmail.com. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2,
pp. 16 – 20, March – April, 2013.

0009-3092/13/4902–0115 2013 Springer Science+Business Media New York 115

116
Fig. 1 Model of ethanol synthesis plant in HYSYS software (explanations in text).
 Some companies produce ethanol by hydration in the Middle East, although such a method is not widely
used [6-9]. In Iran, more than 100 million liters of ethanol is produced by 30 companies using the fermentation
method. Iran represents about 0.05% of global ethanol production [12]. Considering the reduced amount of feedstock
in the Middle East region for fermentation, the presence of the largest ethylene pipelines in the world and the
associated fairly low cost of ethylene, obviously for this region hydration of ethylene is the optimal method for
producing ethanol [13]. This method makes it possible to obtain high-purity ethanol.
Optimization of the ethanol synthesis process includes designing new configurations for the process
flowsheet to reduce production costs. After all, computing and simulation modeling tools for production processes
make it possible to select the optimal technology from the standpoint of the technical and economic
parameters and environmental safety [14]. The goal of our work was to model the process of ethanol synthesis
using HYSYS and ASPEN PLUS software.
The ethylene hydration process was developed about 50 years ago, involving the use of orthophosphoric
acid-impregnated silica gel or diatomaceous earth as the catalysts. Synthesis of ethanol includes three
stages: reaction, recycling of unreacted feedstock, and purification of the ethanol [9, 16, 17]. Fig. 1 shows the
flowsheet for an ethanol synthesis plant, modeled in the HYSYS software. Lines 1 and 3 correspond to the feed
lines at a temperature of 25°C. After mixing with the recycle 26, the feed components reach a temperature
of 85°C (stream 4). The mixture passes through heat exchanger E-201, where it is heated by steam to the reaction
temperature 229°C [9, 17, 18].
Chemical and phase equilibrium. The hydration reaction, occurring in reactor R-201, is an equilibrium
reaction and cannot go to completion. As a result, most of the starting reagents remain in the reactor output
stream. In this work, we modeled hydration on a zirconium—tungsten catalyst [19, 20]. In the reactor, the process
occurs according to the equation:

a
Temperature, °C

b
Enthalpy, kJ/kg·mol

Height of reactor, meters

Fig. 2 Variation in temperature (a) and enthalpy (b) over the height of the reactor.

117
118
Table 1
Component T ci Pc i i Tri Pri B0 B1 i
At reactor inlet temperature
Ethylene 282.4 50.4 0.085 1.777 0.987 -0.0852 0.126 0.959
Water 647.3 220.5 0.344 0.775 0.226 -0.552 -0.3627 0.821
Ethanol 516.2 63.8 0.635 0.973 0.779 -0.358 -0.054 0.731
At reactor outlet temperature
Ethylene 282.4 50.4 0.085 1.777 0.977 -0.0679 0.127 0.971
Water 647.3 220.5 0.344 0.775 0.223 -0.486 -0.239 0.858
Ethanol 516.2 63.8 0.635 0.973 0.772 -0.3133 -0.0068 0.788
0 1
Note. T ci, Pci are the critical temperature and pressure; Tri, Pri are the reduced temperature and pressure; B , B are functions of reduced temperature; i is
the acentric factor of the stream.
 r1
C 2 H 4  H 2 O  C 2 H 5 OH
r2

Fig. 2a shows the temperature profile along the height of the reactor. We see that immediately after the
reagents are mixed, the temperature dramatically rises. Similarly, the enthalpy is maximum at the feed inlet
point (Fig. 2b).
We can write the equations for the rate of the forward reaction r 1 and the rate of the backward
reaction r 2:

k1 PW PE
r1  ;
1  kW PW  k E PE  k A PA 2
k 2 PA
r2 
1  kW PW  k E PE  k A PA 2

where k 1 , k 2 are the rate constants for the forward and backward reactions; P W, P E, P A are the partial pressures of
respectively water, ethanol, and acetaldehyde; k W, k E, k A are the kinetic constants for respectively water, ethanol,
and acetaldehyde (the latter can be neglected).

k  k 0 exp E / RT 

where T is the absolute temperature, K; R is the universal gas constant; E is the activation energy.

k1  1.7723 10 9 exp

 91130 
 RT 
 
3
 kmol/ m cat  h  atm
2

 43915 
k 2  1.3865 10  2 exp
 RT 
 
3
 kmol/ m cat  h  atm
2

 162730 
kW  1.2828 10 17 exp
 RT 
 atm -1  
 35368 
k E  2.085  10 4 exp
 RT

 atm -1



The partial pressures of the components were calculated for total pressure P = 0.1 MPa. The porosity
(void fraction) of the catalyst bed was equal to 0.5; the bulk density was 1800 kg/m 3 . Owing to the use of the
zirconium—tungsten catalyst, the ethanol does not undergo dehydration. However, acetylene in the ethylene
feed stream will react with water to form acetaldehyde:

r3
C 2 H 2  H 2 O  CH 3CHO

The rate of this reaction is expressed by the equation:

119
120
mole fraction
Ethanol content,
Tray number, from top of column

Fig. 3 Ethanol concentration profile on trays of column T-201: 1) vapor phase; 2) “light ethanol”; “heavy” ethanol.

Fig. 4 Flowsheet for additional ethanol purification unit (explanations in text).

 r3  k 3 PAcet

where
  25000 
K 3  10  4 exp
 RT 
 
 kmol/ m 3 cat  h  atm 2 
ΔG 0 8378
ln K     3.3677
RT 8.314  298.15

where G 0 is the Gibbs free energy.

The constant K was calculated assuming the reaction mixture is an ideal gas [21, 22]:

 RT ln K   i Gi  ΔG

where v i , G i 0 are the number of moles and the Gibbs free energy of the reactants.
The constant K is related to the fugacity of the components in the real equilibrium mixture via the equation:


K   fi   i


where f i is the fugacity of the i-th component.
The fugacity of the component reflects the real equilibrium mixture and is a function of temperature,
pressure, and composition [23]. After the thermochemical quantities are determined for the components in the gas
phase, we can formulate the equilibrium condition in the gas phase [24, 25]:

a
Ethanol content,
mole fraction

Tray
Fig. 5 Ethanol concentration profile in liquid phase (a) and gas phase (b) on trays of
extractive distillation column.

121
 
 f i   i yi P

  
 
 i    i fi
i
 P  K
 
 K   f i


where the  i are the fugacity coefficients; the y i are the mole fractions of the reactants in the gas phase.


 i   i    i y i  i  P  K

y etoh etoh
 P 0.01568 
y et et y wat wat

where the subscripts etoh, et, and wat respectively stand for ethanol, ethylene, and water.
The calculated value of K (at 299°C) is 0.01568. The calculated fugacities for the reactants at the reactor
inlet and outlet temperatures are given in Table 1. In the calculation using the data in the table, we obtained the
approximate value for the conversion  e = 0.2598.
The reactor output stream is fed to heat exchanger E-202 (see Fig. 1), where it is cooled down to the
temperature at which ethylene can be separated from ethanol and water. Stream 7 passes through throttle
valve VLV-100 and enters high-pressure separator V-100. The liquid phase from this separator is fed to
low-pressure separator V-101. Streams 9 and 12 (the gas phase from the separators) are fed via combined
stream 14 to absorber column T-201. To control the pressure of streams 9 and 12, a reciprocating flash gas
compressor C-201 is provided. Water (stream 15), absorbing the ethanol, is fed into the top section of
column T-201.
The water from the bottom of column T-201 and the liquid phase from separator E-101 are fed to the
ethanol purification column T-202 through respectively trays 54 and 99. Bottoms 24 of column T-202, having high
water content, pass through cooler E-105, where they are water-cooled. Ethanol purification column T-202 is
equipped with a partial condenser. Separation of steam from the liquid is done in the reflux drum. The liquid phase,
in the form of reflux, is returned to the column while the steam, containing a significant amount of ethanol, is fed
to condenser E-206, where it is water-cooled and condensed. Ethanol is sold to consumers in liquid form, so the
insignificant amount of ethylene vapor from the top section of separation V-102 is fed to the flare to be burned.
The product at the plant outlet contains 87% ethanol (Fig. 3).
Optimization of the ethanol purification stage. A large number of studies have been devoted to the
problem of separating azeotropes of ethanol with water, and most of these papers suggest extractive
purification [24, 25]. Until recently, benzene was mainly used to break azeotropes. However, ethanol obtained by
this purification method is toxic. Today studies are under way on breaking azeotropes using ethylene glycol and
tetraethylene glycol; ethanol produced in this case is not hazardous [25, 26].
The purification process was optimized using the Aspen Plus software (Fig. 4). The ethanol
obtained by the hydration plant is fed to the separation unit. The ethanol is dehydrated by extractive
distillation [27], using ethylene glycol and calcium chloride. Stream 1, containing 87% ethanol, is fed to the
extractive distillation unit. The model simulation established that it possible to bring the ethanol content in the
product (stream 3) up to 99.7%.
The output from the bottom section of the extractive distillation column C-1 (see Fig. 4) is a mixture of
ethylene glycol and water, which enters solvent recovery column C-2 to separate the water from the ethylene

122
glycol and calcium chloride. The maximum temperature in the reboiler of the solvent recovery column
i s 1 5 0 ° C , s i n c e a t h i g h e r t e m p e r a t u r e d e c o m p o s i t i o n o f t h e e t h y l e n e g l y c o l c a n o c c u r. E t h y l e n e
glycol (stream 6) is returned to the process by pump P-1. Fig. 5 shows the ethanol concentration profile in the
liquid and gas phases on the trays of extractive distillation column C-1.
Increasing the ethanol content in the product up to 99.7% means it can be sold at a higher price. Furthermore,
production of 99.7% pure ethanol provides extensive opportunities for selling the product, which can be used in
different industries. Increased costs of agricultural products and their shortage in Iran and consequently the
inability to obtain ethanol by fermentation allow us to conclude that for Iran, ethylene hydration is the most
suitable method for obtaining ethanol, based on available feedstock.

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