HETEROGENEOUS AZEOTROPIC

DEHYDRATION OF ETHANOL TO OBTAIN

A CYCLOHEXANE-ETHANOL MIXTURE
Chemical Engineering Department
University of Alicante (Spain)
e-mail: vgomis@ua.es

Vicente Gomis
Mª Dolores Saquete
Alicia Font
Ricardo Pedraza
Victoria Pastor-Matea
OBJECTIVE

Study the viability of cyclohexane in

the ethanol dehydration to obtain an
ethanol + cyclohexane mixture from
an azeotropic distillation column.

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INTRODUCTION

Key renewable energy policy documents of the EU

1997 White Paper "Energy for the future"
•Doubling the share of renewable energy from 6%
(1997) to 12% (2010)

2003 EU Biofuels Directive (2003/30/EC)
•Target for biofuels in transport: 2% by 2005,
5.75% by 2010

2009 Directive „on the promotion of the use of
energy from renewable sources“ (2009/28/EC)
•Overall EU target : 20% renewable energy in
gross final energy consumption in 2020
•Target of 10% renewable energy in transport in
2020 for all member states

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INTRODUCTION

Ethanol Production
Sectored emissions in Europe

A griculture Waste Benefits of biofuels

8% 2%

Industry • Reduce GHG emissions

8%

Energy • Improve air quality

48%

• Reduce petroleum dependence

Transpo rt
34%
• Improve energy security

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INTRODUCTION

Ethanol Production

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INTRODUCTION

Ethanol dehydration

Pressure Swing Adsorption Azeotropic distillation

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INTRODUCTION

Azeotropic distillation
TERNARY
AZEOTROPE (E) Ethanol

1 00

0
C
D
G
(N)

25
75
(M) A

FEED (G)

Ethanol/Water (D)

50
50
+
Benzene (B)

75
25

ABSOLUTE
(C)
ALCOHOL
M E N

Heterogeneous region

100
0

B
Water 100 75 50 25 0 Benzene

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INTRODUCTION

Possible entrainers

Benzene (Young, 1902)

Gasoline components
Pentane
Acetone
Hexane
Heptane
Toluene
Isooctane
Cyclohexane

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INTRODUCTION

Conventional Process

Raw Ethanol Mixing Fuel

materials Production with
gasoline
Proposed Process

Raw Ethanol + Gasoline Fuel

materials Production
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INTRODUCTION

Cost diminution of:

- Mixing

Advantages

- Transportation

- Storage

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EXPERIMENTAL DESIGN

Study in an experimental Simulation of the industrial process

semi-pilot plant column

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Semi-Pilot Plant Column study

Cyclohexane

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 Semi-Pilot Plant Column study

Operation Variables
• Feed 1: pure cyclohexane. Temperature = 66 ± 1ºC
Flow rate = 41.00 g/min
• Feed 2: water + ethanol mixture (94% wt. of ethanol). Temperature: 63 ±1ºC
Flow rate = 4.38 g/min
• Condenser: Temperature = 35ºC
• Heat exchanger 3: Temperature of the stream leaving HE-3 = 66 ±1ºC

Simulation Variables
 Simulated in Chemcad 6
 Rigorous calculation using the SCDS module (simultaneous correction
method for rigorous fractionation simulation)
 Thermodynamic model: UNIFAC

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Semi-Pilot Plant Column study

Bottoms Product
1.0

0.8
The trends
Weight Fraction

0.6
Ethanol Simulation
observed in the
Cyclohexane Simulation experimental
0.4
Cyclohexane
Ethanol results resemble
0.2
their simulated
Optimal counterparts
0.0
0 50 100 150 200 250

Reboiler Heat Duty (W)

• The ethanol concentration depends on the heat duty

• Only values ranging from 80-100 W permit ethanol concentrations close to 5 % wt.

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Semi-Pilot Plant Column study

Bottoms Product
0.005
Water Simulation
Water
0.004
The trends
Weight Fraction

0.003 observed in the

experimental
0.002 results resemble
their simulated
0.001
counterparts
Too high < 50ppm
0.000
0 50 100 150 200 250

Reboiler Heat Duty (W)

• The concentration of water in the residue stream does vary considerably with respect to
the reboiler heat duty
• As the heat duty increases, the concentration of the water gradually decreases, reaching
values lower than 50 ppm.
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Semi-Pilot Plant Column study

Aqueous phase Water Simulation

1.0 Ethanol Simulation
Water Simulation
0.8 Water
Ethanol
Weight Fraction

Cyclohexane
0.6

0.4
The simulation adequately
reproduces neither the flow
0.2 rate values of the bottom
product and aqueous layer
0.0
0 50 100 150 200 250 obtained experimentally nor
Reboiler Heat Duty (W) the composition of the
streams
• The composition of the aqueous layer is also dependent on the heat duty
• The composition tends to approach that of the plait point of the system.

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Semi-Pilot Plant Column study

Flows
50

The simulation
40
adequately reproduces
Flow (g/min)

30 neither the flow rate

Simulation values of the bottom
Aqueous decant
20
Bottoms Product product and aqueous
layer obtained
10
experimentally nor the
0 composition of the
0 50 100 150 200 250
streams
Reboiler Heat Duty (W)

• The flow rate of the residue is always higher than that of the aqueous layer
• Both flow rates become more similar when the reboiler heat duty increases.

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 Semi-Pilot Plant Column study

Ethanol

0
10

0
UNIFAC non isothermal binodal curve
Experimental non isothermal binodal curve

25
75

UNIFAC phase split prediction

50

50
25

75
Plait Point

10
0

0
Water 100 75 50 25 0 Cyclohexane

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Semi-Pilot Plant Column study
Etanol

100

0
Experimental
UNIFAC
UNIFAC Dortmund
UNIFAC LLE

25
75

50
50

75
25

10
0

0
Agua Ciclohexano
100 75 50 25 0

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Semi-Pilot Plant Column study
Etanol

0
10

0
Experimental
UNIQUAC
NRTL α constante
NRTL α variable

25
75

50
50

75
25

10
0

0
Agua Ciclohexano
100 75 50 25 0

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CONCLUSIONS

 It is possible, through azeotropic distillation, to obtain a mixture of cyclohexane

+ ethanol with concentrations of water lower than 50 ppm without the need
to distill absolute ethanol beforehand. Afterward, the mixture could be directly
employed as a carburant in car engines with no further modifications.
 The most critical parameter of the process is the reboiler heat duty. At lower
values, this produces a mixture of cyclohexane + ethanol with excessive
amounts of water. Whereas, at higher values the azeotropic distillation column
does not work properly, since the top stream condenses giving only one liquid
phase.
 Significant differences in some values are encountered between experimental
and simulated data which can be attributed to the calculation of the liquid-liquid
equilibrium. It is therefore necessary to improve the correlation of the
experimental equilibrium data for determined regions of the ternary system
diagram.

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CONCLUSIONS

The production of dry mixture of

ethanol + cyclohexane seems to be
technically and economically viable

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