Rigorous Design and Simultaneous Optimization of Extractive Distillation

Systems Considering the Effect of Column Pressures

Chengtian Cui and Jinsheng Sun*
School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, P. R. China

1. The basic thermodynamic data

The basic thermodynamic data for the three case studies are listed below.
Table A1. UNIQUAC binary interaction parameters for n-heptane/isobutanol/NMP system

Component i n-heptane n-heptane

Component j isobutanol NMP

Aij 6.7725 0

Aji -3.8423 0

Bij -2829.07 -122.207

Bji 1511.49 -91.3266

Cij 0 0

Cji 0 0

Dij 0 0

Dji 0 0

Eij 0 0

Eji 0 0

Φ𝑖 𝑧 𝜃𝑖 𝜃 ′𝑗 𝜏𝑖𝑗 Φ𝑖
𝑙𝑛𝛾𝑖 = 𝑙𝑛 + 𝑞𝑖 𝑙𝑛 − 𝑞 ′ 𝑖 𝑙𝑛𝑡 ′ 𝑖 − 𝑞 ′ 𝑖 ∑ ′ + 𝑙𝑖 + 𝑞 ′ 𝑖 − ∑ 𝑥𝑗 𝑙𝑗
𝑥𝑖 2 Φ𝑖 𝑡𝑗 𝑥𝑖
𝑗 𝑗

𝑞𝑖 𝑥𝑖 𝑞 ′𝑖 𝑥𝑖 𝑟𝑖 𝑥𝑖
𝜃𝑖 = ; 𝑞𝑇 = ∑𝑘 𝑞𝑘 𝑥𝑘 ; 𝜃 ′ 𝑖 = ; 𝑞 ′ 𝑇 = ∑𝑘 𝑞 ′ 𝑘 𝑥𝑘 ; Φ𝑖 = ; 𝑟𝑇 = ∑𝑘 𝑟𝑘 𝑥𝑘
𝑞𝑇 𝑞 ′𝑇 𝑟𝑇

𝑧
𝑙𝑖 = (𝑟𝑖 − 𝑞𝑖 ) + 1 − 𝑟𝑖 ; 𝑡 ′ 𝑖 = ∑𝑘 𝜃 ′ 𝑘 𝜏𝑘𝑖 ; 𝜏𝑖𝑗 = 𝑒𝑥𝑝⁡(𝑎𝑖𝑗 + 𝑏𝑖𝑗 ⁄𝑇 + 𝑐𝑖𝑗 𝑙𝑛𝑇 + 𝑑𝑖𝑗 𝑇 + 𝑒𝑖𝑗 ⁄𝑇 2 ); 𝑧 = 10
2

*Corresponding author.

E-mail address: jssun2006@vip.163.com (J. Sun).

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 Table A2. NRTL binary interaction parameters for ACN/water/EG system

Component i ACN ACN Water

Component j Water EG EG

Aij -0.1164 0 0.3479

Aji 1.0567 0 -0.0567

Bij 256.459 536.542 34.8234

Bji 283.409 130.165 -147.137

Cij 0.3 0.3 0.3

Dij 0 0 0

Eij 0 0 0

Eji 0 0 0

Fij 0 0 0

Fji 0 0 0

∑𝑗 𝑥𝑗 𝜏𝑗𝑖 𝐺𝑗𝑖 𝑥𝑗 𝐺𝑖𝑗 ∑𝑚 𝑥𝑚 𝜏𝑚𝑗 𝐺𝑚𝑗

𝑙𝑛𝛾𝑖 = +∑ (𝜏𝑖𝑗 − )
∑𝑘 𝑥𝑘 𝐺𝑘𝑖 ∑
𝑗 𝑘 𝑥𝑘 𝐺𝑘𝑗 ∑𝑘 𝑥𝑘 𝐺𝑘𝑗
𝑏𝑖𝑗 𝑑𝑖𝑗
𝐺𝑖𝑗 = exp⁡(−𝑎𝑖𝑗 𝜏𝑖𝑗 ); 𝜏𝑖𝑗 = 𝑎𝑖𝑗 + + 𝑒𝑖𝑗 𝑙𝑛𝑇 + 𝑓𝑖𝑗 𝑇; 𝑎𝑖𝑗 = 𝑐𝑖𝑗 + ; 𝜏𝑖𝑖 = 0; 𝐺𝑖𝑖 = 1
𝑇 𝑇−273.15𝐾

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 Table A3. NRTL binary interaction parameters for IPA/water/DMSO system

Component i IPA IPA Water

Component j Water DMSO DMSO

Aij -1.3115 0 -1.2449

Aji 6.8284 0 1.7524

Bij 426.398 115.279 586.801

Bji -1483.46 -25.0123 -1130.22

Cij 0.3 0.3 0.3

Dij 0 0 0

Eij 0 0 0

Eji 0 0 0

Fij 0 0 0

Fji 0 0 0

∑𝑗 𝑥𝑗 𝜏𝑗𝑖 𝐺𝑗𝑖 𝑥𝑗 𝐺𝑖𝑗 ∑𝑚 𝑥𝑚 𝜏𝑚𝑗 𝐺𝑚𝑗

𝑙𝑛𝛾𝑖 = +∑ (𝜏𝑖𝑗 − )
∑𝑘 𝑥𝑘 𝐺𝑘𝑖 ∑
𝑗 𝑘 𝑥𝑘 𝐺𝑘𝑗 ∑𝑘 𝑥𝑘 𝐺𝑘𝑗
𝑏𝑖𝑗 𝑑𝑖𝑗
𝐺𝑖𝑗 = exp⁡(−𝑎𝑖𝑗 𝜏𝑖𝑗 ); 𝜏𝑖𝑗 = 𝑎𝑖𝑗 + + 𝑒𝑖𝑗 𝑙𝑛𝑇 + 𝑓𝑖𝑗 𝑇; 𝑎𝑖𝑗 = 𝑐𝑖𝑗 + ; 𝜏𝑖𝑖 = 0; 𝐺𝑖𝑖 = 1
𝑇 𝑇−273.15𝐾

2. Case study optimization parameters setting and results

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 To improve the optimization robustness, Design Spec/Vary option in Aspen Plus is used. The
following tables and figures show the Design Spec/Vary setting and Aspen Plus/MATLAB optimization
framework parameters setting. Besides, the GA optimization progress curves of TAC, capital cost, and
operating cost are also given (the best execution of each case). Note that the TAC is monotonously
decreased, while the operating and capital costs demonstrate a non-monotonous tendency.

2.1. n-Heptane/isobutanol system

Table A4. Design Spec/Vary setting in Aspen Plus: n-heptane/isobutanol system

Design specifications Target Vary Range

Mole purity of n-heptane in EDC 0.999 EDC reflux ratio RR1 [0.01, 1]
distillate
Mole purity of n-heptane in EDC 0.0001 EDC distillate flow rate D1 [48, 52] (kmol/h)
bottoms
Mole purity of isobutanol in SRC 0.999 SRC reflux ratio RR2 [0.1, 1]
distillate
Mole purity of NMP in SRC bottoms 0.9999 SRC distillate flow rate D2 [48, 52] (kmol/h)

Table A5. Aspen Plus/MATLAB optimization framework parameters setting: n-heptane/isobutanol system

Aspen Plus decision variable Lower boundary Upper boundary

D1 (kmol/h) 48 52
RR1 0.01 1
D2 (kmol/h) 48 52
RR2 0.1 1
Matlab GA decision variable Lower boundary Upper boundary

NT1 10 40
NF1 10 40
NFS 10 40
NT2 10 30
NF2 10 30
P1 (atm) 0.05 1
P2 (atm) 0.05 1
FS (kmol/h) 50 150
TS (°C) 50 100

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 Fig. A1. The GA optimization progress curve for n-heptane/isobutanol system

2.2. ACN/water system

Table A6. Design Spec/Vary setting in Aspen Plus: ACN/water system

Design specifications Target Vary Range

Mole purity of water in PCC bottoms 0.9999 PCC reflux ratio RR1 [0.01, 1]
Mole purity of ACN in EDC distillate 0.9999 EDC reflux ratio RR2 [0.01, 1]
Mole recovery of ACN in EDC 1e-5 EDC distillate flow rate D2 [80, 120] (kmol/h)
bottoms
Mole purity of water in SRC distillate 0.9999 SRC reflux ratio RR3 [0.01, 1]
Mole purity of EG in SRC bottoms 0.99999 SRC distillate flow rate D3 [5, 100] (kmol/h)

Table A7. Aspen Plus/MATLAB optimization framework parameters setting: ACN/water system

Aspen Plus Design Spec/Vary Lower boundary Upper boundary

RR1 0.01 1
D2 (kmol/h) 80 120
RR2 0.01 1
D3 (kmol/h) 5 100
RR3 0.01 1
Matlab GA decision variable Lower boundary Upper boundary

NT1 10 25
NF1 10 25
NT2 35 70
NFS 35 70
NF2 35 70
NT3 10 30
NF3 10 30
P1 (atm) 0.05 2

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P2 (atm) 0.05 2
P3 (atm) 0.05 2
D1 (kmol/h) 130 170
FS (kmol/h) 100 160
TS (°C) 50 100

Fig. A2. The GA optimization progress curve for ACN/water system

2.3. IPA/water system

Table A8. Design Spec/Vary setting in Aspen Plus: IPA/water system

Design specifications Target Vary Range

Mole purity of water in PCC bottoms 0.9999 PCC reflux ratio RR1 [0.01, 5]
Mole purity of IPA in EDC distillate 0.9999 EDC reflux ratio RR2 [0.01, 6]
Mole recovery of IPA in EDC 1e-5 EDC distillate flow rate D2 [20, 200] (kmol/h)
bottoms
Mole purity of water in SRC distillate 0.9999 SRC reflux ratio RR3 [0.01, 20]
Mole purity of DMSO in SRC 0.99999 SRC distillate flow rate D3 [5, 100] (kmol/h)
bottoms

Table A9. Aspen Plus/MATLAB optimization framework parameters setting: IPA/water system

Aspen Plus Design Spec/Vary Lower boundary Upper boundary

RR1 0.01 5
D2 (kmol/h) 20 200
RR2 0.01 6
D3 (kmol/h) 5 100
RR3 0.1 20

Matlab GA decision variable Lower boundary Upper boundary

NT1 20 35

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NF1 20 35
NT2 35 60
NFS 35 60
NF2 35 60
NT3 15 35
NF3 15 35
P1 (atm) 0.6 1
P2 (atm) 0.6 1
P3 (atm) 0.4 1
D1 (kmol/h) 70 77
FS (kmol/h) 50 100
TS (°C) 50 100

Fig. A3. The GA optimization progress curve for IPA/water system