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PROSIMPLUS APPLICATION EXAMPLE

HETEROGENEOUS AZEOTROPIC DISTILLATION

EXAMPLE PURPOSE
This example illustrates a high purity separation process of an azeotropic mixture (ethanol-water) through heterogeneous azeotropic distillation. This process includes three-phase (liquid-liquid-vapor) distillation columns. Additionally these rigorous three-phase multi-stage separation modules are part of a recycling stream, demonstrating the efficiency of ProSimPlus convergence methods. Specifications are set on output streams in order to insure the required purity. This example illustrates the way to set "non-standard" specifications in the multi-stage separation modules. It also shows the capability to use several thermodynamic models in the same flowsheet (or different set of parameters for the same model): here a specific model is used for the decanter in order to properly model the demixion phenomena.

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CORRESPONDING PROSIMPLUS FILE .

E05_HeteroAzeotropicDistillation.pmp3

Reader is reminded that this use case is only an example and should not be used for other purposes. Although this example is based on actual case it may not be considered as typical nor are the data used always the most accurate available. ProSim shall have no responsibility or liability for damages arising out of or related to the use of the results of calculations based on this example.

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TABLE OF CONTENTS

1.

PROCESS MODELING 1.1. 1.2. 1.3. 1.4. 1.5. 1.6. Process description Specifications Components Thermodynamic model Operating conditions "Hints and Tips"

3 3 6 6 6 7 8 9 9 10 10 12

2.

RESULTS 2.1. 2.2. 2.3. Comments on results Mass and energy balances Composition profiles

3.

REFERENCES

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1. PROCESS MODELING
1.1. Process description

As shown by the equilibrium diagram below (generated for instance with mixture property calculation service in ProSimPlus), the ethanol-water binary mixture is particularly difficult to separate due to the presence of an azeotropic point and the very low relative volatility of the two components on the pure ethanol side.

ETHANOL

1.0

0.9

Vapor fractions (Bubble - Molar) : ETHANOL

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0 0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Mixture (Molar) : ETHANOL

Heterogeneous azeotropic distillation is generally used to separate non-ideal mixtures. This technique utilizes an entrainer (also called liquid separating agents) to form a ternary azeotrope with minimum boiling temperature. In addition, the presence of this entrainer must create a demixion zone which will make it possible to overcome the traditional distillation borders. The ternary diagram of the system water/ethanol/cyclohexane at atmospheric pressure shown below (this diagram was generated with ProSimPlus).

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Thermodynamic analysis of the ternary system water / ethanol / cyclohexane

The analysis of this diagram reveals the presence of 3 binary azeotropes (represented by triangles on the ternary diagram). The temperature of each one of these azeotropes is lower than the bubble temperatures of the mixture pure substances. In addition, the three components form a ternary azeotrope (represented by a circle on the ternary diagram) which temperature is lower than the bubble temperatures of the pure substances and than the temperatures of binary azeotropes. Consequently, the ternary azeotrope is an unstable node, the binary azeotropes are saddles points and the pure substances are the stable nodes of the system. The ternary diagram breaks up into three zones, separated by borders that cannot be crossed by traditional distillation. This means that in a column fed with a given mixture of these three components, one of the three pure substances (depending on the zone in which is located the feed) is obtained at the bottom of the column, a mixture close to ternary azeotrope is obtained at the top of the column.

It should be noted that the borders of distillation calculated by the software are curved and not linear. The demixion area, represented by hatched surface, was calculated at 25 C with binary interaction parameters regres sed from experimental data of ternary liquid-liquid equilibrium.

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The principle process flowsheet for the separation of binary mixture considered is as follows:

Process flowsheet of heterogeneous azeotropic distillation

The total feed of the column (C101) must be located in the area that makes it possible to obtain the ethanol at the bottom of the column (area delimited by the points pure ethanol - binary azeotrope water-ethanol - ternary azeotrope - binary azeotrope cyclohexane-ethanol). The vapor distillate of this column is condensed in a cooler heater (E101, from stream C02) and sub-cooled so as to increase demixion effect. This stream is sent in a decanter (D101, from stream C05), the light phase leaving this equipment (organic phase rich in ethanol) constitutes the reflux flow of the column (stream C07) and the heavy phase (aqueous phase) feeds the second column (C102, stream C06) which will make it possible to purify water and to recycle the entrainer.

The following ternary diagram illustrates the analysis of the mass balances obtained by the simulation and presented in the paragraphs hereafter. The total feed of the first column, made up of the feed of the process and the recycling stream of entrainer, is located on the operating line of the first column.

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Analysis of simulation results

1.2.

Specifications

The process specifications are as follow: At the bottom of column C101, ethanol must have a purity of 99.99% mass At the bottom of column C102, ethanol must have a purity of 99.99% mass.

1.3.

Components

Components taken into account in the simulation are taken from the ProSimPlus standard database: Water Ethanol Cyclohexane

1.4.

Thermodynamic model

The thermodynamic model used for this process is based on an activity coefficient approach. NRTL [1] has been the selected model. At the decanter level, the NRTL thermodynamic model is also selected, but in this case specific binary interaction parameters are used. These binary interaction parameters are regressed using liquid liquid equilibrium data in order to have satisfactory model of the liquid-liquid equilibria.

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1.5.

Operating conditions
Process feed Parameters Total flowrate (kg/h) Mass fraction Water Ethanol Temperature ( C) Pressure (atm) 0.065 0.935 20 1.05 Value 330

Column C101 Operating parameters Type of column Number of theoretical stages Feed stage C01 Feed stage C04 Feed stage C09 Feed stage C07 Top pressure (atm) Pressure drop in the column (atm) Vapour distillate flowrate (kmol/hr) for a feed flowrate of 1 kmol/hr Condenser duty (W) Solution type Value Three-phase distillation 45 14 1 17 14 1 0.15 0.88 0.0 Two-phase and then three-phase

Additional specifications for column C101: Specification 1: Mass fraction Product type Bottom liquid product Component Ethanol Value 0.999999 Phase Liq. Type Mass. Action Vapour distillate flowrate

Heat exchanger E101 Operating parameters Type Output temperature ( C) Value Cooler/heater 45

Decanter D101

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Operating parameters Temperature ( C) Pressure (atm)

Value 45 1

Column C102 Operating parameters Type of column Type of condenser Number of theoretical stages Feed stage C08 Pressure Top (atm) Solution type Value Three phase distillation total 25 7 1.01 Two-phase and then three-phase

Additional specifications for column C102: Specifications 1: Product type Component Water Value 0.9999 Phase Liq. Type Mass. Action Liquid distillate flowrate

Mass fraction Bottom liquid product

Splitter V101 Operating parameters Splitting rate for stream C04 Value 50%

1.6.

"Hints and Tips"

This process includes a recycling stream which must take into account the fact that the feed stream does not contain entrainer (cyclohexane) and that the columns are three-phase columns. This increases the complexity of the convergence. ProSimPlus only requires initialization of one stream. In this case, only stream C03 has been initializd. This makes it possible to calculate the decanter, then the distillation column C102 and then the distillation column C101. Initialization parameters do not require being close to the solution. The following values were used: Temperature: 45 C Pressure: 1 atm Flowrate: 2 740 Kg/h Mass composition: Water: 7% - Ethanol: 17 % - Cyclohexane: 86 %

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2. RESULTS
2.1. Comments on results

Convergence of both columns is reached at the first try and the recycling loop convergence is reached in very few calculations. It is to be noted that resulting flowrate and composition of stream C03 are relatively far from the values given as initialization.
Partial molar flowrates of stream: C03
Molar flow rate (kmol/h) 25 20 16,63 15 10 5 0 C03 4,43 24,74

WATER

ETHANOL

CYCLOHEXANE

Total molar flowrate = 45,80kmol/h

It is possible to reach the required purities (in particular for the ethanol production) with this process configuration and the proposed operating parameters. The loss in entrainer is very low and very few ethanol is lost. At the first column (C101), only the two first top stages are three-phase stages (a phase immiscibility is detected). The reboiler duty is 421 444 Kcal/hr.

At the second column (C102), there is no immiscibility phase detected by the stability phase tests performed. However the heat duty to be supplied at the reboiler is higher than for column C101: about 700 000 Kcal/hr.

The entrainer recycling flowrate (stream C09) is equivalent to the process feed flowrate.

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2.2.

Mass and energy balances

This document presents only the most relevant stream results. In ProSimPlus, mass and energy balances are provided for every stream. Results are also available at the unit operation level (result tab in the configuration window).

Streams From To Partial flowrates WATER ETHANOL CYCLOHEXANE Total flowrate Mass fractions WATER ETHANOL CYCLOHEXANE Physical state Temperature Pressure Enthalpy Vapour fraction

C01 Process Feed C101 kg/h 21.45 308.55 0 330.00 0.064 0.935 0 Liquid 20.0 1.04 -80050

C04 DC01 C101 kg/h 39.91 383.05 1041.19 1464.16 0.027 0.26 0.71 Liquid 44.99 0.99 -187395.44

C06 C101 Process Outlet 2 kg/h 3.93E-5 308.54 0.000262 308.54 1.27E-7 0.999 8.72E-7 Liquid 81.90 1.15 -55132.37

C10 C102 Process Outlet 2 kg/h 21.45 0.0021 0 21.45 0.9999 0.0001 0 Liquid 100.28 1.01 -10884.8

kg/h

C atm kcal/h

2.3.

Composition profiles

Composition profiles can be accessed after the simulation in each column configuration window, in the Profiles tab. Double clicking on the profile will generate the corresponding graph. Here, only the liquid-mole fractions is shown for the three columns.

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Column C101
C101 - Vapor mass-fractions

Mass-fraction 1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0 0 10 20 Stage 30 40 50

WATER

ETHANOL

CYCLOHEXANE

Vapor mass-fractions profile in the column

Column C102
C102 - Vapor mass-fractions

Mass-fraction 1.0 0.9

0.8 0.7

0.6 0.5 0.4

0.3 0.2

0.1 0.0 1 2 3 4 5 6 7 8 9 10 11 12 13 Stage 14 15 16 17 18 19 20 21 22 23 24 25

WATER

ETHANOL

CYCLOHEXANE

Vapor mass-fractions profile in the column

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3. REFERENCES
[1] Renon H., J.M. Prausnitz, "Local compositions in thermodynamic excess functions for liquid mixtures" A.I.Ch.E. J., 14,3, 135-144 (1968)

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