F U E L PR O CE SS I N G TE CH N O LOG Y 89 ( 20 0 8 ) 1 1 48 –1 1 5 2

a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m

w w w. e l s e v i e r. c o m / l o c a t e / f u p r o c

Optimization of the ETBE (ethyl tert-butyl ether)

production process

Eliana Weber de Menezes, Renato Cataluña⁎

Department of Physical Chemistry, Institute of Chemistry, Federal University of Rio Grande do Sul, Avenida Bento Gonçalves, 9500,
CEP-91501-970 Porto Alegre, RS, Brazil

AR TIC LE I N FO ABS TR ACT

Article history: The synthesis of ETBE (ethyl tert-butyl ether) from the reaction of ethanol with isobutene is
Received 14 August 2007 an exothermic reaction of equilibrium. To increase the conversion of isobutene requires
Received in revised form 14 May 2008 operating the reaction system at low temperatures and with excess ethanol in order to
Accepted 14 May 2008 displace the equilibrium towards the products. ETBE and ethanol form an azeotropic mixture
which hinders the recycling of nonreacted ethanol in the process. The purpose of this work is
Keywords: to optimize the synthesis of ETBE eliminating the introduction of water into the system to
ETBE break the ETBE/Ethanol azeotrope. The production process model proposed here eliminates
Azeotropic mixture (ETBE/EtOH) the recycling of ethanol and suggests the use of the azeotropic mixture (ETBE/Ethanol) in the
Gasoline formulation of gasolines. The direct use of the azeotrope in the formulation of automotive
gasolines reduces the implementation and production costs of ETBE.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Oxygenated compounds are known to be important as
components in the formulation of automotive gasolines,
not only as enhancers of gasoline octane ratings [1,2] but also
as reducers of carbon monoxide (CO) and unburned hydro-
carbons (HC), minimizing the emission of volatile organic
compounds [3–6]. The introduction of a minimal percentage
of oxygenated compounds in the formulation of gasolines
has been required by law in most countries which have areas
of low air quality.
Alcohols and ethers are the oxygenated compounds most
commonly used as additives in automotive gasolines, since they
possess the desired characteristics of octane ratings and CO
emission reductions [7]. Some countries prefer ethers rather than
alcohols due to their mixing characteristics, such as low volatility
and compatibility with the hydrocarbons of gasoline [8,9].
Alcohols are substantially more polar than the ethers and
hydrocarbons of gasoline, and may cause phase separation in
the presence of a small amount of water in the gasoline storage
and distribution system [10,11].
Tertiary ethers offer advantages over ethanol due to their low
Reid vapor pressure (RVP), low latent heat of vaporization, and
low solubility in water [7,12]. The most commonly used of these
ethers are MTBE and ETBE. It is worth pointing out that ETBE
is considered semi-renewable, since the raw material for its
production – ethanol – is derived from biomass [7].
ETBE is produced by reacting a C4 stream containing
isobutene with ethanol over an ion-exchange resin catalyst. On
an industrial scale, the conventional process of ETBE synthesis
consists basically of the following stages: pretreatment of the C4
hydrocarbon feed flow, reaction, purification, and recovery of
nonreacted products [13,14]. Nowadays, to minimize implemen-
tation and operating costs, reactive distillation (also called
catalytic distillation) is proposed as an alternative route for
ETBE synthesis, offering high conversion and low implementa-
tion/operating costs in comparison with conventional synthesis
[15–17]. The reactive distillation process combines the reaction
and purification stages in a single unit of the process [18].
In the ETBE production process, nonreacted ethanol forms an
azeotropic mixture with ETBE, which cannot be separated by
distillation. The process of ETBE purification occurs through the

⁎ Corresponding author. Tel.: +55 51 3308 6306; fax: +55 51 3316 7304.
E-mail address: rcv@ufrsgs.br (R. Cataluña).

0378-3820/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2008.05.006
 FUE L PR O CE SS I N G TE CH N O LO G Y 89 ( 20 0 8 ) 1 1 4 8–1 1 5 2 1149

Table 1 – Mean molar composition of the industrial

hydrocarbons load of the C4 cut 2. Experimental
Compounds Concentration (molar%)
2.1. Reaction system and purification
Isobutane 1.7
n-butane 7.6 2.1.1. Reaction
2-transbutene 16.9
The ETBE production process was carried out in a flow, using
1-butene 33.2
Isobutene 36.0
as reagents a mixture of C4 hydrocarbons with 36 mol% of
2-cisbutene 4.6 isobutene (i-C4) and 99.5 mol% of anhydrous ethyl alcohol.
Table 1 presents the mean molar composition of the
industrial load of C4 hydrocarbons. Amberlyst® 15 resin
introduction of water into the system and involves the separa- was used as catalyzer. The schematic diagram in Fig. 1
tion of the ETBE, the C4 hydrocarbon mixture, ethanol and water. depicts the production process.
The introduction of water into the purification process augments The reaction system consists of an adiabatic fixed bed reactor
the costs of implementation and production of ether. For this fed by two cylinders, one containing the reagent ethanol (EtOH)
reason, some technologies use pervaporative separation of the and the other the C4 hydrocarbon mixture under a pressure of
ethanol from the ETBE/alcohol mixture through special mem- 20 bar. The composition of the reagent mixture and the reaction
branes [19–23]. system are controlled by two electronic liquid flow gauges, one
It has been demonstrated that the azeotropic mixture (ETBE/ for ethanol, with a capacity of 405 mL/h, and the other for the C4
ethanol) is less volatile than ethanol and that its octane rating is hydrocarbons mixture, with a capacity of 1380 mL/h. These
higher and its production cost lower than ETBE, thus presenting gauges allow the EtOH/i-C4 ratio and space velocity to be set as
promising potential for application in gasoline formulations [8]. desired. The reagent mixture is heated and fed into the reactor's
The synthesis model proposed here eliminates the recycling lower portion. The temperature of the catalytic stream bed and at
of ethanol and suggests the use of the azeotropic mixture (ETBE/ the exit is monitored with thermocouples inside and outside the
ethanol) as a direct additive in the formulation of automotive reactor to ensure the reaction is in the steady state condition. The
gasolines. reactor's effluent is flashed into a distillation column under

Fig. 1 – Flowchart of the ETBE synthesis. (1) Nitrogen; (2) and (3) Reagents; (4) Adiabatic fixed bed reactor; (5) Distillation column.
PI: Pressure Indicator; TI: Temperature Indicator; TR: Temperature Recorder; TIC: Temperature Indicator Controller; FIC: Flow
Indicator Controller.
1150 F U E L PR O CE SS I N G TE CH N O LOG Y 89 ( 20 0 8 ) 1 1 48 –1 1 5 2
atmospheric pressure, separating the C4 hydrocarbons into
vapor phase and the ethanol, ETBE and byproducts into liquid
phase. The isobutene conversion was evaluated as a function of
the composition of the C4 hydrocarbons in the vapor phase.
The concentration of liquid C4 at the bottom of the column is
negligible.
Normalization of the i
C4 ðloadÞ
Normalization of the i
C4 ðreactors exitÞ
i
C4 conversion ¼
Normalization of the i
C4 ðloadÞ
The composition of the C4 hydrocarbon (reagent) load and the
C4 in the vapor phase (reaction products) was determined by gas
chromatography using a thermal conductivity detector (GC-TCD,
Shimatzu 17A), a “plot” type fused silica capillary column with a
stationary phase of Al2O3/Na2SO4 (50 m×0.53 mm) and Helium
(5.0) as carrier gas. The analytical conditions were: isotherm at
40 °C for 20 min, a heating ramp-up of 20 °C/min up to 190 °C, and
holding at this temperature for 10 min. The injector and detector
temperatures were 180 °C and 220 °C. The split ratio was 1:20 and
the volume of injected sample was 20 µL.
The conversions obtained in the reaction system were
evaluated as a function of the EtOH/i-C4 molar ratio (MR) in the
load and the temperature at the reactor's exit. The molar ratios
evaluated were 1.0, 1.1, 1.2, 1.3, 1.4 and 1.5. The temperature
interval of the reaction was 48 °C to 88 °C, using a single space
velocity of 0.52 h− 1, which was chosen on the basis of previous
experiments, in order to ensure sufficient residence time of the
reactants in the catalytic stream bed to enable the products
leaving the reactor to meet the equilibrium condition. This space
velocity corresponds to the minimum limit of operation of the
flow control of the reactants using a 340 cm3 reactor.
2.1.2. Purification of the reactor's effluent
The effluent from the reaction system was fractionated in a
distillation column to remove the light compounds (C4 excess
hydrocarbons of the reaction). In this first column that
receives the effluent from the reactor, the bottom flow
consists of a mixture (ETBE/EtOH) together with secondary
Fig. 2 – Isobutene conversions as a function of the temperature at the exit from the reactor, considering the distinct EtOH/i-C4
molar ratios (MR) and a space velocity of 0.52 h− 1.
The conversion of isobutene was determined by gas chroma-
tography from the molar balance in the reactor. The calculation
methodology considered normalization of the isobutene in
relation to the saturated hydrocarbons (isobutane and n-butane),
which are considered inert and do not participate in the reaction.
The conversion of isobutene was calculated according to Eq. (1)):
 100 ð1Þ
products of the reaction (tert-butyl alcohol and C8 hydro-
carbons). The product of this bottom flow column is directed
to a second distillation column (under identical conditions as
those of the first). The bottom flow consists of ETBE with a
high degree of purity, together with byproducts of the
reaction, while the top flow consists of the azeotropic ETBE/
EtOH mixture.
The composition of the bottom flow was analyzed by gas
chromatography with flame ionization detector (CG-FID, Varian
39XL), using a fused silica capillary column (CP sil PONA CB) with
a 100% dimethylpolysiloxane active phase (100 m×0.25 mm) and
Helium (5.0) as a carrier gas. The analytical conditions were
isotherm at 40 °C for 20 min, a heating ramp-up of 5 °C/min up to
190 °C, and holding at this temperature for 10 min. The injector
and detector temperatures were 250 °C and 300 °C, respectively.
The initial split ratio was of 1:300, passing on to 1:20 after 2 min of
analysis. The volume of injected sample was 20 µL.
3. Results and discussion
3.1. Evaluation of the parameters of the reactional system
Fig. 2 presents the isobutene conversion profiles adjusted as a
function of the temperature at the exit from the reactor and the
EtOH/i-C4 molar ratios of the feed. The conversions shown here
represent the results of three consecutive assays for each
reaction condition evaluated.
 FUE L PR O CE SS I N G TE CH N O LO G Y 89 ( 20 0 8 ) 1 1 4 8–1 1 5 2 1151

Table 2 – Mass balance of ETBE production with a 100 kg of
C4 hydrocarbons load for the molar ratios (MR) of 1.0 and
1.5 at a temperature of 62 °C
MR i-C4 conversion, (%)⁎ Load (kg) Products (kg)
mEtOH mAzeotrope mETBE
1.0 88 30 20
1.1 89 34 36
1.2 90 36 50
1.3 91 40 66
1.4 91.5 42 80
1.5 92 46 97
⁎ Results extracted from Fig. 2.
As indicated in Fig. 2, at a space velocity of 0.52 h− 1, the
reaction attains the maximum conversion in the temperature
interval of 61 to 67 °C. Because it is a reversible and exothermic
reaction, the increase in temperature exerts a negative effect
on the displacement of the chemical equilibrium; hence, the
higher the temperature the lower the conversion of isobutene
in equilibrium. At temperatures of 50 to 61 °C, the conversion is
directly proportional to the increase in temperature due to the
faster reaction. At temperatures below 61 °C, the conversion is
kinetically controlled while at higher temperatures, the con-
version is controlled by thermodynamic equilibrium.
The increase in ethanol concentration with the increase in
the EtOH/i-C4 molar ratio in the system's feed directly reduces
the velocity of the reaction (according to the Eley-Riedel kinetic
mechanism), but increases isobutene conversion. These results
are compatible with the values reported by Françoisse & Thyrion
[24]. As Fig. 2 indicates, for molar ratios (MR) of 1.0 to 1.2, the
maximum conversions vary from 88 to 90%, while at molar ratios
of 1.3 to 1.5 the conversions vary from 91 to 92%. At a tem-
perature of 65 °C, the molar ratios above 1.2 present practically
the same isobutene conversions.
For MR=1.0, the best operational temperature for maximum
conversion is 59 to 63 °C. As the MR increases, so does the
temperature of maximum conversion. This behavior is caused by
the reaction mechanism. When the ethanol concentration
increases, the reaction rate decreases due to the adsorption of
ethanol in the active sites of the catalyst, making diffusion of the
isobutene inside the particle catalyst difficult, and thus present-
ing a negative reaction order for the ethanol concentration.
According to our chromatographic analysis, the reaction
products of ethanol with isobutene are ETBE, C4 hydrocarbons
(nonreacted), ethanol (nonreacted), TBA (tert-butyl alcohol), SBA
(sec-butyl alcohol), C8 hydrocarbons and, in lesser proportion, C12
hydrocarbons. Higher temperatures favor the formation of
reaction byproducts, leading to the increased production of
compounds with higher molar masses, such as isobutene dimers
(C8) and isobutene trimers (C12). The increase in ethanol
concentration in the load requires a higher temperature to
activate the reaction. This fact, allied with the presence of water
in the ethanol, favors the formation of TBA and, at a lower
concentration, SBA, due to the reaction of the water with the C4
olefins. Based on our experimental results, we found that the
highest formation of secondary products was obtained with a
molar ratio of 1.5 and at a reaction temperature of 87 °C.
3.2. Optimization of the production process
Based on the experimental results summarized in Fig. 2, the
highest production of ETBE (or the greatest conversion of i-C4)
was found to occur with MR 1.5. However, this led to a higher
production of the azeotropic ETBE/EtOH mixture. Table 2
43 presents the mass balance as a function of the molar ratios of
30
1.0 and 1.5 in the feed and a temperature of 62 °C (corresponding
20
to the maximum conversion temperature for MR=1.0), consider-
8
–
ing as base load 100 kg of C4 hydrocarbons (0.66 mol of i-C4).
– According to the results presented in Table 2, as the molar
ratio of EtOH/i-C4 increases, so too does the conversion and
the production of the ETBE/EtOH azeotropic mixture. At a
molar ratio equal to or higher than 1.4, the concentration of
ethanol in the reactor's effluent is higher than in the
composition of the azeotropic mixture. Thus, all the ETBE
produce in the reaction system is concentrated in the top
flow of the fractionation column in the form of azeotrope and
the bottom flow is composed of ethanol plus the secondary
products of the reaction.
As the data in Table 2 indicate, the stoichiometric molar
ratio allows for the highest ETBE production of high grade
purity, minimizing the production of the azeotropic mixture. To
increase the production of ETBE with a high degree of purity,
minimizing or preventing the formation of the azeotropic
mixture, it is necessary to use water in the system. However,
this increases the installation cost of the production plant.
Moreover, the introduction of water leads to the formation of
the azeotropic EtOH/H2O mixture, which makes it difficult to
recycle the ethanol. Some technologies use pervaporative
separation of the ethanol in the azeotropic mixture (ETBE/
EtOH) by means of special membranes. The use of ETBE in
azeotropic form would eliminate the costs related to the
purification stage of the ETBE production process.
In high purity ETBE production units which use water to break
the ETBE/EtOH azeotrope, the recycled ethanol contains water in
its composition, increasing the formation of TBA and SBA
alcohols and reducing the activity of the catalyst.
4. Conclusions
In the synthesis of ETBE using an adiabatic reactor and a space
velocity of 0.52 h− 1, the highest isobutene conversion is obtained
at reaction temperatures ranging from 61 to 67 °C. When the
concentration of EtOH in the load increases, the conversion of i-
C4 in the equilibrium also increases, but the reaction rate toward
ETBE formation decreases.
The azeotropic mixture possesses a potential for application
in gasoline formulations, offering advantages over the use of
ethanol (such as lower volatility and lower solubility in water) and
ETBE (higher octane rating and lower production costs). The
production system without ethanol recycling, considering the
ETBE/EtOH azeotropic mixture as an end product of the system,
minimizes production costs since it does not require the ethanol
purification unit.
The maximum ETBE production with a high degree of
purity and minimal production of the ETBE/EtOH azeotropic
mixture is attained using a stoichiometric molar ratio of
EtOH/i-C4.
1152 F U E L PR O CE SS I N G TE CH N O LOG Y 89 ( 20 0 8 ) 1 1 48 –1 1 5 2
Acknowledgements
The authors acknowledge to the Petrochemical Company of the
Rio Grande do Sul (COPESUL), Brazil, for supplying the raw
material (C4 cut) for the production of the ETBE and thanks the
financial support of the CNPq.
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