Professional Documents
Culture Documents
Extractive Distillation and Pressure Swing Distillation For THFethanol Separation
Extractive Distillation and Pressure Swing Distillation For THFethanol Separation
Received: 29 March 2014 Revised: 29 May 2014 Accepted article published: 5 June 2014 Published online in Wiley Online Library:
Abstract
BACKGROUND: During the synthesis of a liquid crystal monomer, an effluent including tetrahydrofuran(THF) and ethanol is
produced. Since THF and ethanol are both important solvents used in the chemical industry, it is necessary to separate the
mixture of THF and ethanol for reuse. However, it is hard to effectively separate the mixture via simple distillation because a
minimum azeotrope is formed in the binary system.
RESULT: Extractive distillation and pressure-swing distillation are adopted to separate the mixture and carefully optimized to
achieve minimization of the total annual cost (TAC). A comparison between the two processes is carried out. Pressure-swing
distillation is used to separate mixtures of THF and ethanol with various compositions.
CONCLUSION: The results indicate that pressure-swing distillation performs better than extractive distillation from the
standpoint of both economic considerations and product purity. The feasible sequence of high and low pressure of two columns
in a pressure-swing distillation is related to the feed composition.
© 2014 Society of Chemical Industry
UNIQUAC parameter
the number of trays (in Aspen Plus, the first and the last stages
Table 3. Impact of pressure on the boiling point of the pure
are the reflux drum and reboiler, respectively). The diameter of a component
column is determined by the ‘Tray Sizing’ function in Aspen Plus,
and ‘sieve tray’ was used. The cost of the pump is not included Boiling point (K)
in the capital cost because it is much smaller than the main Pressure (atm) THF Ethanol
distillation equipment cost. The basis of the economics, the sizing
relationships and parameters are listed in Table 2. The operating 1 339.12 351.46
time of the distillation system is set at 8000 h per year. 8 421.46 415.87
9 427.55 420.35
10 433.12 424.53
EXTRACTIVE DISTILLATION 12 443.16 435.28
For the extractive distillation system, there are two significant 13 447.72 428.37
design optimization variables, i.e. the solvent-to-feed ratio and
the reflux ratio (RR) after the solvent is selected. The extractive
distillation was investigated in the following order. In the extraction column, the distillate product is THF with a purity
of 99.9 mol %, and the bottom stream mainly contains ethanol
and ethylene glycol with a THF concentration ≤ 0.1 mol %. In the
Selection of solvent recovery column, the efficient separation of ethanol and ethylene
The separation of THF and ethanol was studied via extractive glycol is achieved and ethanol as the distillate product with a
distillation by Huang.42 In his study, the effect of different organic content of 99.9 mol % leaves the column from the top and the
solvents, such as ethylene glycol, dimethylformamide (DMF), bottom stream consists of almost pure ethylene glycol with a trace
dimethyl sulfoxide (DMSO) and N-methyl pyrrolidone, on the rel- amount of ethanol and THF.
ative volatility of THF and ethanol was investigated in detail. The
results showed that ethylene glycol is a suitable solvent for sepa-
Optimization of solvent flow rate
rating THF and ethanol. However, the flowsheet he provided was
Separation depends on the solvent flow rate in the extraction
not optimized to minimize the TAC of the process. In this work, the
column. It can be seen from Fig. 4 that with the same RR, the purity
extractive distillation process is optimized when ethylene glycol is
of the distillate product (THF) increases with an increasing amount
used as the solvent.
of solvent. For different solvent flow rates, the impurity content
displayed a trend of first declining and then rising with increasing
Design requirements RR, indicating that a lowest impurity content of the product can be
The flow rate of the mixture is 100 kmol h−1 , with content of 50 mol obtained. To achieve the desired distillate purity of 99.9 mol % THF,
% THF and 50 mol % ethanol. The initial stage numbers in the the minimum solvent-to-feed ratio is 2.09, and the corresponding
extraction and recovery columns are set at 55 and 10, respectively. solvent flow rate is 209 kmol h−1 .
Selection of pressure design distillate composition x D1 is set as 83.82 mol % THF, while
The composition of the azeotrope changes significantly with the azeotrope contains 25.67 mol % THF at 10 atm and the design
pressure. The larger the composition changes, the smaller the distillate composition x D2 is set as 27.67 mol % THF. The desired
recycle flow rate and the energy consumption in the two reboilers compositions of the two product streams are x B1 = 99.9 mol %
become, suggesting that it is appropriate to select a higher pres- ethanol and x B2 = 99.9 mol % THF, respectively. The flow rates of
sure in the high-pressure column.32 However, the pressure should the two distillate streams, D1 = 64.3 kmol h−1 and D2 = 14.3 kmol
not be higher than that is compatible with heating steam. The h−1 , are calculated by the mass balance in the two columns. The
impact of pressure on the boiling point of the two components is obtained results are used as the initial values for the operating
shown in Table 3. Therefore, a medium-pressure stream of 10 atm is specifications in Aspen Plus. However, the corresponding TAC
selected in the high-pressure column for which the minimum tem- values are large, which requires us to find the optimal distillate flow
perature difference required in the reboiler is 20 K, which can sig- rates and the corresponding RRs to minimize the TAC.
nificantly reduce the energy costs. In addition, low-pressure steam
was used in the low-pressure column which is operated at 1 atm. Optimum distillate flow rates and RRs
When the distillate flow rate in the high-pressure column is 14.3
Calculation of distillate flow rates kmol h−1 , the RR value in the high-pressure column is so large
Empirically, the overhead distillate composition from the low- that it leads to an excessive energy cost when the desired purity
pressure column is slightly lower than that of the low-pressure is achieved. Therefore, the distillate flow rate D2 and the RRs in the
azeotrope, whereas the composition in the high-pressure column two columns are varied to find values that minimize the TAC on
is slightly higher than that of the high-pressure azeotrop.30 In the the premise that the desired purities are achieved. Figure 8 shows
literature, most design values for the composition of the distillate the effect of the RR pairs in the two columns on the TAC for each
streams are ∼2 mol % different from the corresponding minimum D2 flow rate. The minimum TAC is achieved at the 35-35-stage
azeotropic composition.33 For the mixture of THF and ethanol when the D2 flow rate is 32.5 kmol h−1 , RR1 is 1.80 and RR2
system, the azeotrope contains 85.82 mol % THF at 1 atm and the is 3.16. The corresponding content of THF in D2 is 51.4 mol %,
Figure 10. Flowsheet of pressure-swing distillation for feed composition of 50 mol % THF.
Figure 11. Flowsheet of pressure-swing distillation for feed composition of 90 mol % THF.
Figure 12. Flowsheet of pressure-swing distillation for feed composition of 10 mol % THF.
25 Zhang ZG, Huang DH, Lv M, Jia P, Sun DZ and Li WX, Entrainer 35 Muñoz R, Montón J, Burguet M and de la Torre J, Separation of
selection for separating tetrahydrofuran/water azeotropic mixture isobutyl alcohol and isobutyl acetate by extractive distillation and
by extractive distillation. Sep Purif Technol 122:73–77 (2014). pressure-swing distillation: simulation and optimization. Sep Purif
26 Chen Q and Gu ZG, Process design and optimization of extractive Technol 50:175–183 (2006).
distillation for butanol-isobutanol separation by Aspen Plus. Mod 36 Luyben WL, Comparison of extractive distillation and pressure-swing
Chem Ind 34:145–148 (2014). distillation for acetone-methanol separation. Ind Eng Chem Res
27 Phimister JR and Seider WD, Semicontinuous, pressure-swing distilla- 47:2696–2707 (2008).
tion. Ind Eng Chem Res 39:122–130 (2000). 37 Lladosa E, Montón JB and Burguet M, Separation of di-n-propyl ether
28 Repke JU, Klein A and Forner F, Homogeneous azeotropic distillation and n-propyl alcohol by extractive distillation and pressure-swing
in an energy-and mass-integrated pressure swing column system. distillation: computer simulation and economic optimization. Chem
Comput Chem Eng 18:757–762 (2004). Eng Process 50:1266–1274 (2011).
29 Repke JU, Forner F and Klein A, Separation of homogeneous 38 Modla G and Lang P, Removal and recovery of organic solvents
azeotropic mixtures by pressure swing distillation–analysis of from aqueous waste mixtures by extractive and pressure swing
the operation performance. Chem Eng Technol 28:1151–1157 distillation. Ind Eng Chem Res 51:11473–11481 (2012).
(2005). 39 Wang Q, Yu B and Xu C, Design and control of distillation system for
30 Repke JU, Klein A, Bogle D and Wozny G, Pressure swing batch methylal/methanol separation. Part 1: extractive distillation using
distillation for homogeneous azeotropic separation. Chem Eng Res dmf as an entrainer. Ind Eng Chem Res 51:1281–1292 (2012).
Des 85:492–501 (2007). 40 Yu B, Wang Q and Xu C, Design and control of distillation system for
31 Modla G, Pressure swing batch distillation by double column systems methylal/methanol separation. Part 2: pressure swing distillation
in closed mode. Comput Chem Eng 34:1640–1654 (2010). with full heat integration. Ind Eng Chem Res 51:1293–1310 (2012).
32 Wang Y, Cui P and Zhang Z, Heat-integrated pressure-swing distillation 41 Luyben WL, Comparison of extractive distillation and pressure-swing
process for separation of tetrahydrofuran/methanol with different distillation for acetone/chloroform separation. Comput Chem Eng
feed composition. Ind Eng Chem Res 53:7186–7194 (2014). 50:1–7 (2013).
33 Luyben WL, Pressure-swing distillation for minimum-and maximum- 42 Huang C, Separation of binary azeotrope tetrahydrofuran-ethanol by
boiling homogeneous azeotropes. Ind Eng Chem Res extractive distillation. ME Dissertation, Tianjin University, Tianjin,
51:10881–10886 (2012). Tianjin, (2008).
34 Luyben WL, Comparison of pressure-swing and extractive-distillation
methods for methanol-recovery systems in the tame reactive-
distillation process. Ind Eng Chem Res 44:5715–5725 (2005).