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Rav Agnani 2010
Rav Agnani 2010
a b s t r a c t
Production of anhydrous ethanol in large scale has been made by extractive distillation using conventional solvents
like ethylene-glycol. In the present paper, extractive distillation process is studied to obtain pure ethanol using
ethylene-glycol and tetraethylene-glycol as solvents. Residue curve maps are used to analyse the proposed distilla-
tion processes in interpreting mixture behaviours and feasibility of distillation columns. The industrial process is
simulated at steady state from residue curve map analysis. Simulation results for the ethanol/water mixture using
ethylene-glycol, the conventional solvent, and tetraethylene-glycol, an alternative solvent, are presented. These
results showed that the process using tetraethylene-glycol is reliable, although it requires more energy than the
process with ethylene-glycol. However, ethylene-glycol has a considerable toxicity level while tetraethylene-glycol
is non-toxic.
© 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Extractive distillation; Anhydrous ethanol; Tetraethylene-glycol; Residue curve maps; Clean technology;
Process simulation
∗
Corresponding author. Tel.: +55 44 32614321; fax: +55 44 32614321.
E-mail addresses: ravag@deq.uem.br, mauro.ravagnani@hotmail.com (M.A.S.S. Ravagnani).
Received 18 December 2008; Received in revised form 24 November 2009; Accepted 26 November 2009
0957-5820/$ – see front matter © 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.psep.2009.11.005
68 Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 67–73
where xi and yi are the liquid and the vapour molar fractions
for component i, is the warped time, and c is the number of
components.
Before Eq. (1) integration, it is necessary to find a relation-
ship between the liquid and the vapour phases. For an ideal
vapour ( = 1) in equilibrium with a nonideal liquid ( =/ 1), the
equilibrium equations using the – approached can be used.
In this work, saturation pressures (Psat i
) were calculated
applying the Antoine equation and the coefficients for this
equation are presented in Table 1, for each component (Reid
et al., 1988).
The liquid activity coefficients were calculated using NRTL
model (Renon and Praunitz, 1968) and are presented in
Table 2. Meirelles et al. (1992) obtained the NRTL parameters
for the ethanol/water/ethylene-glycol system by regression
of different experimental isobaric and isothermal data. The Fig. 1 – Flowsheet for the ethanol/water/ethylene-glycol
interaction parameters for the tetraethylene-glycol/water and system.
Table 2 – NRTL parameters for the system ethanol (1)/water (2)/ethylene-glycol (3)/tetraethylene-glycol (4)a .
i j aij (cal/mol) aji (cal/mol) bij (cal/mol K) bji (cal/mol K) ALP ALT (◦ C−1 )
a
These parameters are used along with ˛ = ALP + ALT × t, Gij = exp(−˛ij ij ), and ij = (aij + bij T)/RT, for R = 1.987 cal/mol K.
70 Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 67–73
20 1.59
25 1.43
28 1.39
30 1.39
32 1.39
35 1.43
37 1.49
ratio solvent to feed flow rates (S/F), analysing the reboiler duty
requirement.
The practical number of stages refers to the number of
stages that the column almost did not show variations in the
reboiler duty, i.e., increasing the number of stages the decrease
in the reboiler duty is not considerable. The word “practical”
is used here to mean “feasible number of stages”, instead of
Fig. 2 – Residue curve map for the system
use the name “infinite number of stages”, through Underwood
ethanol/water/ethylene-glycol at 101.3 kPa.
shortcut method. The same is valid for “practical reflux ratio”
to differentiate it from the one calculated from the Underwood
method.
2.1.1. Ethanol/water/ethylene-glycol
The calculated residue curve map (Fig. 2) shows that pure
ethylene-glycol is obtained as bottom product in a distilla-
tion process, from any initial liquid composition. Moreover,
there are no distillation boundaries in this diagram; so, it is
possible to obtain the three pure components in an extrac-
tive distillation process. According to this characterization
result, ethylene-glycol seems to be a reliable solvent to sep-
arate ethanol and water through out extractive distillation
process
At this point, it is quite important to mention that only ther-
modynamically it can be affirmed that the separation of the
ethanol and water mixture using ethylene-glycol as solvent
is possible. Moreover, Rodriguez-Donis et al. (2009b) showed
Fig. 3 – Reboiler duty versus number of stages of the that the product sequence determined from the sole analy-
extractive column for the system sis of thermodynamic properties of residue curve maps and
ethanol/water/ethyelene-glycol. even the occurrence of unidistribution lines and univolatility
Table 4 – Input and optimum conditions for the extractive distillation process with ethylene-glycol as solvent.
Material streams
Vapour fraction 0 0 0 0
Temperature (K) 351.29 298.15 351.31 428.15
Pressure (kPa) 101.3 101.3 101.3 101.3
Molar flow (mol/h) 100.0 300.0 85.00 315.0
Energy streams
Qc1 Qr1
7
Heat flow (10 kJ/h) 94.96 1.393
Unit operations
Number of stages 40
Feed stream position 30
Solvent stream position 3
lines can be unambiguously. In terms of process viability and The best ratio solvent to feed flow (S/F) is 3, since for smaller
optimisation, it is necessary that the operational variables be values the simulation did not converge for the given specifica-
well integrated in the process, such as: number of stages of tions and for greater values the duty requirements increases.
all distillation columns involved, feed and solvent locations, Mainly for nonideal mixture separations, the position of
recycled solvent temperature, ratio solvent to feed flow rates the feed stream influences on the optimised results. Depend-
(S/F), reflux ratios, reboiler duties and productivity. ing on the feed and the solvent stream positions, the energy
Fig. 3 shows the reboiler duty versus the number of stages consumption can be lesser or greater, or even it is not pos-
of the extractive column using ethylene-glycol as solvent. sible to get the simulation convergence. Table 3 shows the
Analysing the presented results, it is observed that the num- values of the reboiler duty as function of the feed stream
ber of practical stages is 40 (the stages are counted from the position for the ethanol/water/ethylene-glycol system. It was
top to the bottom, and the condenser and the reboiler are not considered a column with 40 stages and the solvent stream
computed as stages). in the optimum position (stage number 3). The reboiler
Table 5 – Input and optimum conditions for the extractive distillation process with tetraethylene-glycol as solvent.
Material streams
Vapour fraction 0 0 0 0
Temperature (K) 351.29 298.15 351.31 470.45
Pressure (kPa) 101.3 101.3 101.3 101.3
Molar flow (mol/h) 100.0 200.0 85.00 215.00
Energy streams
Qc1 Qr1
7
Heat flow (10 kJ/h) 34.38 1.798
Unit operations
Number of stages 50
Feed stream position 45
Solvent stream position 3
72 Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 67–73
duty is increased when the solvent stream position is above alternative in substituting the ethylene-glycol in the anhy-
stage 6. Feed stream position that gets the smallest energy drous ethanol production in the ethanol distilleries.
consumption is at stage number 30. For the recovery col- As future works, the optimisation of energy consumption
umn, the best feed stream position is at the middle of the in this process must be considered, as well as the appli-
column. cation of other characterization tools, as the univolatility
The obtained results showed that the best temperature curves.
for the solvent stream is 25 ◦ C. Table 4 presents the input
and optimum results for anhydrous ethanol production with Acknowledgements
ethylene-glycol as solvent.
The authors are grateful to CNPq (571683/1997-
5 + 141893/2002-8), CAPES and Fapesp for the financial
2.1.2. Ethanol/water/tetraethylene-glycol
support.
Although simulation and practical results showed that
ethylene-glycol is a reliable solvent to promote ethanol/water
separation, some studies show that this solvent has a consid- References
erable toxicity level. In the present paper, tetraethylene-glycol
is presented as an alternative solvent to produce anhydrous Boudreau, T.M. and Hill, G.A., 2006, Improved ethanol-water
separation using fatty acids. Process Biochemistry, 41:
ethanol looking for new demands of clean and safe processes.
980–983.
Fig. 4 shows that tetraethylene-glycol is also a reliable sol-
Brüggemann, S. and Marquardt, W., 2004, Shortcut methods for
vent to promote the separation of ethanol/water mixture by nonideal multicomponent distillation. 3. Extractive
extractive distillation process, since the residue curve map distillation column. AIChE Journal, 50: 1129–1149.
does not present any distillation boundary. Doherty, M.F. and Caldarola, G.A., 1985, Design and synthesis of
However, all design and operation conditions must be homogeneous azeotropic distillation. 3. The sequencing of
observed to guarantee the viability of the process and columns for azeotropic and extractive distillations. Industrial
& Engineering Chemistry Research, 24(4): 474–485.
its optimisation. This system was simulated using the
Doherty, M.F. and Malone, M.F., (2001). Conceptual Design of
same input parameters and specifications used for the
Distillation Systems. (McGraw-Hill, New York).
ethanol/water/ethylene-glycol system. Doherty, M.F. and Perkins, J.D., 1978, On the dynamics of
The parametric optimisation was carried out and the distillation processes. I. The simple distillation of
results obtained are summarised in Table 5. multicomponent nonreacting homogeneous liquid mixtures.
Analysing these results, it was concluded that, using Chemical Engineering Science, 33: 281–301.
tetraethylene-glycol as solvent to separate ethanol and Fien, G.J.A.F. and Liu, Y.A., 1994, Heuristic synthesis and shortcut
design of separation process using residue curve maps: A
water, the number of practical stages is 50, correspond-
review. Industrial Engineering and Chemical Research, 33:
ing to a reboiler duty equal to 1.8 × 107 kJ/h. It represents 2505–2522.
a value 1.3 times greater than the energy spent in the Frits, E.R., Lelkes, Z., Fonyo, Z., Rev, E., Markot, M.Cs. and Csendes,
process with ethylene-glycol as solvent. Ethylene-glycol T., 2006, Finding limiting flows of batch extractive distillation
has a enthalpy of vaporization equal to 61.9 ± 6.3 kJ/mol, with interval arithmetics. AIChE Journal, 52: 3100–3108.
while the enthalpy of vaporization of tetraethylene-glycol is Gallaugher, A.F. and Hibbert, H., 1937, Studies on reactions
relating to carbohydrates and polysaccharides. LV. Vapor
99 ± 10 kJ/mol (Gallaugher and Hibbert, 1937). It explains the
pressures of the polyethylene glycols and their derivatives.
higher heat duty required in the process with tetraethylene-
Journal of American Chemical Society, 59: 2521–2525.
glycol. Gerbaud, V., Joulia, X., Rodriguez-Donis, I., Baudouin, O.,
Rosemain, O., Vacher, A. and Castelain, P., 2006, Practical
residue curve map analysis applied to solvent recovery in
3. Concluding remarks
non-ideal binary mixtures by batch distillation processes.
Chemical Engineering and Processing, 45: 672–683.
Residue curve maps are important tools to understand Gmehling, J., Li, J. and Schiller, M., 1993, A Modified UNIFAC
the behaviour of a mixture in its whole range of molar Model. 2. Present Parameter Matrix and Results for Different
composition. In the case of extractive distillation, one Thermodynamic Properties. Ind. Eng. Chem. Res., 32: 178.
Guerreri, G., 1992, Membrane alcohol separation process,
of the main applications of these diagrams is in the
integrated pervaporation and fractional distillation. Chemical
choice of appropriate solvents. The residue curve map of Engineering Research & Design, 70: 501–508.
the ethanol/water/tetraethylene-glycol system shows that Jin, Y., Wang, D. and Wei, F., 2004, The ecological perspective in
tetraethylene-glycol can be used to separate this azeotropic chemical engineering. Chemical Engineering Science, 59(8):
mixture, after suitable choices of design and operating condi- 1885–1896.
tions of the process. Kim, Y.H., 2006, A new fully thermally coupled distillation
The system with tetraethylene-glycol as solvent needs column with postfractionator. Chemical Engineering and
Processing, 45: 254–263.
more energy than the system with ethylene-glycol. Moreover,
Kiva, V.N., Hilmen, E.K. and Skogestad, S., 2003, Azeotropic phase
it is necessary more tetraethylene-glycol than ethylene-glycol. equilibrium diagrams: a survey. Chemical Engineering
Furthermore, when the solvent is the tetraethylene-glycol, the Science, 58: 1903–1953.
extractive column must be larger. Knapp, J.P. and Doherty, M.F., 1994, Minimum entrainer flow for
However, an important consideration must be done in extractive distillation: a bifurcation theoretic approach. AIChE
this paper. Based on the environmental issues, the use of Journal, 40: 243–268.
Langston, P., Hilal, N., Shingfield, S. and Webb, S., 2005,
tetraethylene-glycol as solvent is justified because it is non-
Simulation and optimisation of extractive distillation with
toxic, while the ethylene-glycol has a considerable toxicity
water as solvent. Chemical Engineering and Processing, 44:
level. Taking into account the considerable efforts that have 345–351.
been done to substitute toxic solvents from industrial plants Lee, F.M. and Pahl, R.H., 1985, Solvent screening and conceptual
the use of tetraethylene-glycol must be considered as a viable extractive distillation process to produce anhydrous ethanol
Process Safety and Environmental Protection 8 8 ( 2 0 1 0 ) 67–73 73
from fermentation broth. Industrial Engineering Chemical batch extractive distillation. 1. Azeotropic mixtures with
Process Design & Development, 24: 168–172. heavy entrainer. Industrial & Engineering Chemistry
Letha, P.M. and Gregersen, M., 2005, Ethylene-glycol poisoning. Research, 48: 3544–3559.
Forensic Science International, 155: 179–184. Rodriguez-Donis, I., Gerbaud, V. and Joulia, X., 2009,
Ligero, E.L. and Ravagnani, T.M.K., 2003, Dehydration of ethanol Thermodynamic insights on the feasibility of homogeneous
with salt extractive distillation: a comparative analysis batch extractive distillation. 2. Low-relative-volatility binary
between processes with salt recovery. Chemical Engineering mixtures with a heavy entrainer. Industrial & Engineering
and Processing, 42: 543–552. Chemistry Research, 48: 3560–3572.
Luyben, W.L., 2009, Control of a column/pervaporation process Schladt, L., Ivens, I., Karbe, E., Ruhl-Fehlert, C. and Bomhard, E.,
for separating the ethanol/water azeotrope. Industrial & 1998, Subacute oral toxicity of tetraethylene-glycol and
Engineering Chemistry Research, 48: 3484–3495. ethylene-glycol administered to Wistar rats. Experimental
Meirelles, A., Weiss, S. and Herfurth, H., 1992, Ethanol and Toxicologic Pathology, 50: 257–265.
dehydration by extractive distillation. Journal of Chemical Seader, J.D. and Henley, E.J., (1998). Separation Process Principles.
Technology and Biotechnology, 53: 181–188. (John Wiley & Sons, New York).
Perez, P., Olujic, Z., Graauw, J. and Jansens, P.J., 2006, Modeling Segovia-Hernández, J.G., Hernández, S. and Jiménez, A., 2006, A
and simulation of inorganic shell and tube membranes for short note about energy-efficiency performance of thermally
vapor permeation. Chemical Engineering and Processing, 45: coupled distillation sequences. The Canadian Journal of
973–979. Chemical Engineering, 84: 139–144.
Pinto, R.T.P., Wolf-Maciel, M.R. and Lintomen, L., 2000, Saline Van Dongen, D.B. and Doherty, M.F., 1985, Design and synthesis of
extractive distillation process for ethanol purification. homogeneous azeotropic distillations. 1. Problem formulation
Computers & Chemical Engineering, 24: 1689–1694. for a single column. Industrial Engineering Chemical
Reid, R., Prausnitz, J. and Sherwood, T.K., (1988). The Properties of Fundamental, 24(4): 454–463.
Gases and Liquids. (McGraw Hill, New York). Vorayos, N., Kiatsiriroat, T. and Vorayos, N., 2006, Performance
Renon, H. and Praunitz, J.M., 1968, Local compositions in analysis of solar ethanol distillation. Renewable Energy,
thermodynamic excess functions for liquid mixtures. AIChE 31(15): 2543–2554.
Journal, 14: 135–144. Widagdo, S. and Seider, W.D., 1996, Azeotropic distillation. AIChE
Rodriguez-Donis, I., Gerbaud, V. and Joulia, X., 2009, Journal, 42: 96–130.
Thermodynamic insights on the feasibility of homogeneous