REGSOLexpert: Entrainer Selection Tool for waste solvent recovery by batch distillation processes

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 Acrylonitrile [S] Water [SN] Acetonitrile [SN] LLVE Heteroazeotrope [UN]E + B Vapour line A + B xD xO YTope xE 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0

Entrainer TB (°C) Process Rejection Acetic acid 118 1.87 BED 1, 3 Allyl alcohol 97 1.23 BED 1, 2, 3 Aliphatic Alcohols 96 - 118 1.50 BED 3

Water 100 398 HBED - n-Butyl acetate 126 .5 0.11 BED 3 Furfural 161. 4 0.42 BED 1, 2, 3 Pyridine 115.2 0.52 BED 1, 2, 3 Nitrobenzene 210.6 0.05 BED 1, 2, 3 4-methyl-2-pentanone 116.7 0.18 BED 2, 3

Methyl cyclohexane 101 0.02 HBED 2, 3

Chloroform (A)

61.1°C

+

Methanol (B)

64.5°C

+

Water (E)

100°C

REGSOLexpert : Entrainer Selection Tool for Waste Solvent

Recovery by Batch Distillation Processes

RODRIGUEZ DONIS Ivonne, GERBAUD Vincent, BAUDOUIN Olivier, JOULIA Xavier

ivonne.rdguez@infomed.sld.cu; Vincent.Gerbaud@ensiacet.fr

Objective

:

General procedure to systematize the search of several alternatives enabling the separation of non-ideal binary mixtures such as

pressure-swing distillation, azeotropic and extractive distillation.

Objective:

General procedure to systematize the search of several alternatives enabling the separation of non-ideal binary mixtures such as

pressure-swing distillation, azeotropic and extractive distillation.

REGSOLexpert

 A wizard computer tool including 224 feasibility rules, and 326 batch azeotropic and extractive distillation processes.

 Systematic checking for each entrainer candidate for determining its feasibility to be used in rectifying or stripping batch column.

 A list of potential homogeneous and heterogeneous entrainers

E

in an optimal time for separating

A

and

B

as any industrial mixture.

Strategy for solvent recovery by distillation

3 – Column configuration

REGSOLexpert software algorithm

Extractive Distillation (HEBD)

Extractive Distillation (HEBD)

excellent agreement

20 mol/hr 150 W N= 45 yTOP

F

E

D

Extractive Section

A

+

B

20 moles 25°C

(1 toxic, 2 pollution, 3 cost)  A



 A



 B



 B



1 - Selecting Entrainer

with RegSolExpert®

-0.9914 0.9690 Water Chloroform Methanol purity recovery 98.0% 89.6% -0.9988 0.9906 0.9957 91.6% 95.1% -0.9914 0.9690 Water Chloroform Methanol purity recovery 98.0% 89.6% -0.9988 0.9906 0.9957 91.6% 95.1% - A



 A



 B



 B



= 0.19

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 xD

Decanter Tie Line AB=1 xP

Top Destination Region:XTOP Methanol (B) 64.5°C [S] Water (E) 100.0°C [SN] azeoAE 56.3°C [S] azeoAB53.3°C [S] Chloroform (A) 61.1°C [ SN ] azeoABE 53.1 °C [UN] LLVE LLE (25°C) Vapour Line

2 - Residue Curve Map

USE:

Extraction of bioactive substances from biological sources

TMIN Azeotrope: T = 53.5 °C, XA

= 0.65

4 – Simulation vs Experiments

: heat up 12 min : R  FE = 0 120 min : R  FE = 20 100 min : R = 1.4 (-D) FE = 20 60 min R = 10 (-D) FE = 20 20 min : E-B separation FE = 0 R = 1.5 250 min 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 Methanol (B) [S] azeoAE [S] azeoAB[S] xS2

Water (E) [SN] Chloroform (A)

[SN] R = 1.4 xS2exp x’S3Exp x x’s2 xs3 xs4 x’s3 XD=XII R xS2Exp azeoABE[UN] YTOP Column x profile xtop Initial charge  xS1  R   = 10 S4Exp 

Industrial Applications

Brabant Industry case:

Cyclopentanone

(130.6°C) –

Propylene Glycol Monomethyl ether

(146°C)

Heterogeneous Azeotropic Distillation (HABD)

Heterogeneous Azeotropic Distillation (HABD)

Acetonitrile (A)

81°C

+

Water (B)

100°C

+

Heterogeneous (E)

USE:

Liquid chromatography separation in pharmaceutical Industry

TMIN Azeotrope: T = 77 °C, XA

= 0.67

1 - Selecting Heterogeneous Entrainer

with RegSolExpert®

Initial List: 55 candidates from several chemical families (DIPPR database)

Heterogeneous

E

:

Acrylonitrile

and

Chloroform

form unstable heteroazeotrope with H

2

0

2 - Residue Curve Map

and

3 – Column configuration

Chloroform [S] Acetonitrile [SN] Heteroazeotrope [UN] Water [SN] A + B E + B LLVE Vapour line xE xD YTope xO

D, xD

T = 25°C V = 70 mL 12.2 mol, xO N.= 50 150 W

4 – Simulation vs Experiments

0.92 0.93 0.94 0.95 0.96 0.97 0.98 0.99 1 1.01 0 0.1 0.20.30.4 0.50.60.7 0.80.9 1 Total Press ure (atm )

xA 0 20 40 60 80 100 120 140 T (° C )

2– (x

A(azeot)

, T

azeot

) vs P

A

+

B

x

A=0.996 T=93.1°C X (mass) A 130.5 0.6 B 146 0.3287 isopropanol 82.3 0.0353 Water 100 0.02 volatil impurity n-methyl pyrrolidone 204.3 0.016 heavy

impurity TB (°C) Components A [sn] B [sn] isopropanol [s] Water [sn] Homogeneous [UN] [S] Heterogeneous [S] Heterogeneous [S] volatil impurity

A,

x

AD 10 mol, xAmass=0.6 N.= 50 1500 W

P= 0.3 atm

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0.000.200.400.600.801.001.201.401.601.802.00 0.98 0.981 0.982 0.983 0.984 0.985 0.986 0.987 0.988 0.989 0.99 0.991 0.992 0.993 0.994 0.995 0.996 0.997 0.998 0.999

3- Column Configuration

4- Simulation

ProSim Batch

1- Mixture analysis

XADdistillate XASstill XAD(average) =0.9951 Recovery yield (A)= 92.5% XAS Time (h) xAmolar

Chloroform Acrylonitrile (* experimental values)

Aqueous Phase x_{Recovery=97.8%}Water=0.9996 x_{Recovery=92.6%}Water=0.947 *x_{*Recovery=89 %}Water=0.946

Entrainer Phase xE=0.9990 Recovery=81% xE=0.712 Recovery=72% *xE=0.6916 *Recovery=69%

Final Still xacetonitrile= 0.9945

Recovery= 99.2 % xacetonitrile= 0.992 Recovery= 95.6% *xacetonitrile= 0.995 *Recovery= 91.8% B A b c a d e f f e d AB<1.5 c f e

Pressure Swing Distillation

Pressure Swing Distillation

Mixture AB: Determination AB azeotrope or AB ideal _a heterogeneous

b

homogeneous



AB<1.5

Pressure swing distillation c

xazeot  constant, Tboiling<30°C

1- Chose entrainer candidates Ei for d e f

Computation azeotropes: AEi, BEi, ABEi

2- Residue curve map of ABEi

Topological stability: A, B, Ei, AB, AEi, BEi, ABEi

3- Feasibility rule cheking

Not match

match

4 - Batch distillation sequences 5- Simulation + Economic evaluation

CONCLUSIONS

Heterogeneous entrainers have a more privileged position than homogeneous. Higher number of ternary diagram match with feasible rules

Pressure swing distillation is a privileged option. It doesn’t involve additional entrainer. Simple performance in one or two batch distillation column operating at different pressures.

Heterogeneous entrainers in HABD: little amount of entrainer, separatrix can be crossed by the still path, simplest batch distillation sequence, more flexible reflux policy (entrainer-rich phase or both decanted phases)

Heterogeneous entrainers in HEBD: Complex ternary residue curves are feasibles, withdrawal of saddle binary heterazeotrope at the column top by feeding E at the top of the column , more flexible reflux policy as HABD Water seems a promising candidate for treatment organic wastes by HEBD and HABD. cheap, non toxic, non pollutant