Вы находитесь на странице: 1из 35
Azeotropic Distillation Methods Dr. Stathis Skouras, Gas Processing and LNG RDI Centre Trondheim, Statoil, Norway

Azeotropic Distillation Methods

Dr. Stathis Skouras, Gas Processing and LNG

RDI Centre Trondheim, Statoil, Norway

Schedule

Tuesday 1/12/2015:

09.45 12.30: Lecture - Natural Gas Processing

14.00 17.00: Available for questions/discussion at TTPL

Wednesday 2/2/2015

14.00 17.00: Available for questions/discussion at TTPL

Thursday 3/12/2015

11.45 14.30: Lecture - Azeotropic distillation methods

15.00 17.00: Available for questions/discussion at TTPL

Friday 4/12/2015

13:30 15.00: Available for questions/discussion at TTPL

for questions/discussion at TTPL Friday 4/12/2015 • 13:30 – 15.00: Available for questions/discussion at TTPL 2

Outline

Introduction

Importance and industrial relevance of azeotropic distillation

Main part

Theory: residue curve maps and distillation curve maps

How to make residue curve maps at Aspen Plus

Feasibility analysis of azeotropic distillation

Azeotropic distillation methods

Examples from the Oil & Gas Industry

Summary

3

azeotropic distillation − Azeotropic distillation methods − Examples from the Oil & Gas Industry • Summary

Importance and industrial relevance of

azeotropic distillation

Need for efficient recovery and recycle of organic solvents in chemical industry

Distillation is the most common unit operation in recovery processes because of its ability to produce high purity products

Most liquid mixtures of organic solvents form azeotropes that complicate the design of recovery processes

Azeotropes make separation impossible by normal distillation but can be also

utilised to separate mixtures not ordinarily separable by normal distillation

Azeotropic mixtures may often be effectively separated by distillation by adding a third component, called entrainer

Knowledge of the limitations and possibilities in azeotropic

distillation is a topic of great practical and industrial interest

4

of the limitations and possibilities in azeotropic distillation is a topic of great practical and industrial

Terminology

The methods and tools presented in this lecture also appply for:

Azeotropic mixtures, close boiling systems, low relative volatility systems

Original components A and B: The components that form the azeotrope and need

to be separated

Entrainer: A third component (E or C) added to enhance separation

Binary azeotrope: Azeotrope formed by two components

Ternary azeotrope: Azeotrope formed by three components

Homogeneous azeotrope: Azeotrope where the forming components are miscible

Heterogeneous azeotrope: Azeotrope where the forming components are immiscible

Minimum boiling azeotrope: Azeotrope with lower boiling point than its constituent components (most common)

Maximum boiling azeotrope: Azeotrope with higher boiling point than its constituent components (less common)

5

• Maximum boiling azeotrope: Azeotrope with higher boiling point than its constituent components (less common) 5

Theory: Residue curve maps (RCM) and distillation curve maps (DCM)

For ordinary multicomponent distillation determination of feasible schemes and column design is straightforward

McCabe-Thiele method and Fenske-Underwood- Gilliland equations are powerful tools

Azeotropic phase equilibrium diagrams such as

residue curve maps (RCM) or distillation curve

maps (DCM) are sometimes nicknamed the McCabe-Thiele of azeotropic distillation and provide insight and understanding

RCM or DCM sketched together with material

balance lines and operating lines are used to identify feasible distillation schemes and products

6

with material balance lines and operating lines are used to identify feasible distillation schemes and products
with material balance lines and operating lines are used to identify feasible distillation schemes and products

Residue curves

Consider the process of differential (open) distillation (Rayleigh distillation)

The component mass balance is written:

dx

i

dt

(

y

i

x

i

)

dW

Wdt

mass balance is written: dx i dt  ( y i  x i ) dW

and by considering the dimensionless time variable ξ (dξ=dV/W)

dx

d

i

x y

i

i

Integrating the above equation from any initial composition (x w 0 ) will generate a residue curve

The residue curve describes the change of the still pot composition with time (trajectory)

A (T A ) T A < T B < T C x W 0
A (T A )
T A < T B < T C
x W 0
Still pot
composition
trajectory
C (T
B (T B )
C )

7

with time (trajectory) A (T A ) T A < T B < T C x

Distillation curves

Consider the process of continuous distillation at

total reflux (45° line at McCabe-Thiele diagram)

Starting with a liquid composition at stage n (x i,n ) and by doing repeated phase equilibrium calculations (E-mapping) upwards we get:

x

i

y

i

x

i

y

i

,

n

E

n



y

i

,

n

,

,

n

n

x

i

,

n

1

E

n 1

1

 

, 1

n

x

i

,

n

y

i

2

,

n

1

By doing this from any initial composition (x 0 ) the distillation curve can be constructed

The distillation curve describes the change of the component composition along the column (trajectory)

8

Total reflux

(V = L = R)

Condenser V, y D L, x D Y i,n-1
Condenser
V, y D
L, x D
Y
i,n-1

Stage n-1

x i,n-1

y i,n

Stage n

x i,n
x i,n

Reboiler

x B

8 Total reflux (V = L = R) Condenser V, y D L, x D Y
8 Total reflux (V = L = R) Condenser V, y D L, x D Y

Singular points in RCM and DCM

Pure component vertices and azeotropes are singular points in the RCM and DCM

dx

d

i

x

i

y

i

0

The behaviour at the vicinity of singular points depends on the two eigenvalues

a) Stable node (

distillation. All residue curves end at this point - Both eigenvalues negative

b) Unstable node (

this point - Both eigenvalues negative b) Unstable node ( ): Point with the highest boiling

): Point with the highest boiling point Bottom product in

Point with the highest boiling point – Bottom product in ): Point with the lowest boiling

): Point with the lowest boiling point Top product in distillation.

All residue curves start at this point - Both eigenvalues positive

c) Saddles (

at this point - Both eigenvalues positive c) Saddles ( ): Point with an intermediate boiling

): Point with an intermediate boiling point Residue curves move

towards and then away from these points One positive and one negative eigenvalue

point – Residue curves move towards and then away from these points – One positive and

9

point – Residue curves move towards and then away from these points – One positive and

Relationship between residue curves and

distillation curves

Both are pure representations of the VLE and no

other information needed to construct them

Have the same topological structure and singular points

Distillation boundaries exist and split the composition space into distillation regions

DO NOT completely coincide to each other

BUT provide the same information and can be

equally used for feasibility analysis

10

Residue curve ------- Distillation curve
Residue curve
------- Distillation curve
the same information and can be equally used for feasibility analysis 10 Residue curve ------- Distillation

«Distillation synthesis» in Aspen Plus

«Distillation synthesis» in Aspen Plus 11
«Distillation synthesis» in Aspen Plus 11

‘‘Find azeotropes’’

‘‘Find azeotropes’’ 12
‘‘Find azeotropes’’ 12
‘‘Find azeotropes’’ 12

‘‘Continue to Aspen Plus Residue Curves’’

‘‘Continue to Aspen Plus Residue Curves’’ 13
‘‘Continue to Aspen Plus Residue Curves’’ 13

‘‘Residue curves’’

‘‘Residue curves’’ 14
‘‘Residue curves’’ 14

Feasibility analysis based on RCM and DCM

D, x D

F, z F
F, z F

B, x B

For a feasible separation the material

balances should be fulfilled:

F = D + B

F z F = D x D + B x B

x B
x B

x D

Feasibility rules

a) The top (x D ) and bottom (x B ) compositions must lie in a straight line through feed (z F )

b) The top (x D ) and bottom (x B ) compositions must lie on the same residue (distillation) curve

Products x D and x B must lie on the same distillation region

15

lie on the same residue (distillation) curve Products x D and x B must lie on

Feasibility analysis based on RCM and DCM

Zeotropic mixture

No distillation boundaries

Only one distillation region exists

No limitations regarding possible products independently of feed location

Direct split: The most volatile is taken at the first column

Indirect split: The less volatile is taken

at the first column

16

F F
F
F
The most volatile is taken at the first column Indirect split: The less volatile is taken

Feasibility analysis based on RCM and DCM

Azeotropic mixtures

One boundary exists (AzACAzAB)

Two distillation regions (I and II)

Different products for feed in regions I and II

Feed F 1 in Area I

o

AzAC as top product

o

Component A as bottom product

Feed F 2 in Area II

AzAC as top product

Component B as bottom product

17

C

A

F 1 AzAB AzAC F 2 B
F 1
AzAB
AzAC
F 2
B
• Feed F 2 in Area II • AzAC as top product • Component B as

Azeotropic distillation methods

1) Pressure swing distillation

No entrainer required

2) Homogeneous azeotropic (homoazeotropic) distillation

3) Heterogeneous azeotropic (heteroazeotropic) distillation

4) Extractive distillation

3) Heterogeneous azeotropic (heteroazeotropic) distillation 4) Extractive distillation Entrainer enhanced methods 18

Entrainer

enhanced

methods

18

3) Heterogeneous azeotropic (heteroazeotropic) distillation 4) Extractive distillation Entrainer enhanced methods 18

1) Pressure swing distillation

Principle: Overcome the azeotropic composition by changing the system pressure

Key factors: Azeotrope sensitive to pressure changes, recycle ratio

which increases costs

Application: Tetrahydrofuran/water *

increases costs • Application: Tetrahydrofuran/water * * Stichlmair and Fair, Distillation: Principles and

* Stichlmair and Fair, Distillation: Principles and practice, Wiley-VCH, (1998)

19

Application: Tetrahydrofuran/water * * Stichlmair and Fair, Distillation: Principles and practice, Wiley-VCH, (1998) 19

2) Homogeneous azeotropic distillation

Definition:

o

Entrainer completely miscible with the original components

o

Entrainer may (or not) form additional azeotropes with the original components

o

The distillation is carried out in a sequence of columns

Principle:

o

The addition of the entrainer results in a residue curve map promising for separation

o

Both original components must belong to the

same distillation region

20

F + E 1 2 1 E
F + E
1
2
1
E

2

for separation o Both original components must belong to the same distillation region 20 F +
for separation o Both original components must belong to the same distillation region 20 F +

Feasibility for homogeneous azeotropic distillation

Example Use of intermediate entrainer

Original components A and B form a min. Az AB

Components A and B belong to the same distillation region

Original feed (F) is close to the azeotrope Az AB

Total feed (F´) is a mix of fresh feed (F) and entrainer (E)

D 1 F´ A B AzAB=F
D 1
A
B
AzAB=F
• Component A is taken as bottom product in Column 1 D 1 • Component
• Component A is taken as bottom product in Column 1
D
1
• Component B is taken as top product in Column 2
F
• Entrainer (E) is recovered as bottom product in Column 2
1
2
• Entrainer (E) is recycled to Column 1
A
E
• Applicability of homoazeotropic distillation is limited
• Restrictive feasibility rules (intermediate entrainers are rare)
• Other distillation methods are preferably applied

B

feasibility rules (intermediate entrainers are rare) • Other distillation methods are preferably applied B 21

3) Heterogeneous azeotropic distillation

Definition:

o

Entrainer is immiscible and forms azeotrope with at least one of the original azeotropic components

The distillation is carried out in a combined column-

decanter column

is carried out in a combined column- decanter column o o Entrainer is recovered and recycled

o

o

Entrainer is recovered and recycled to the first column

Principle:

o

Liquid-liquid immiscibilities are used to overcome

azeotropic compositions

Distillation boundaries can be crossed by immiscibility

o

Applicability:

o

Widely used in the industry

o

One of the oldest methods of azeotropic distillation

22

o • Applicability: o Widely used in the industry o One of the oldest methods of

Classic example: Ethanol/water + benzene (E)

1) Preconcentrator

Aqueous feed dilute in EtOH (F1)

EtOH-Water azeotrope at top (D1)

Pure water at bottom (B1)

3) Entrainer recovery column

Aqueous phase from decanter is column feed

Pure water is taken at the bottom (B3)

Top product (D3) is close to the EtOH-water

azeotrope + some benzene left

2) Azeotropic column

Ternary heterogeneous azeotrope (A12E) at top

column • Ternary heterogeneous azeotrope (A12E) at top • Splits in two liquid phases in a

Splits in two liquid phases in a decanter

Benzene-rich phase is recycled at the top

Pure EtOH is taken at bottom (B2)

Benzene A12E 2 O
Benzene
A12E
2 O

H

EtOH

• Benzene-rich phase is recycled at the top • Pure EtOH is taken at bottom (B2)

4) Extractive distillation

Definition:

o

Heavy entrainer is used with high boiling point

o

Distillation is carried out in a two-feed column with a heavy entrainer added continously at the top

o

Entrainer is recovered in a second column

Principle:

o

The entrainer alters the relative volatility of the original components

o

The entrainer has a substantial higher affinity to

one of the original components and ‘‘extracts’’ it

downwards the azeotropic column

Applicability:

o Most widely used method in the industry

24

extracts ’’ it downwards the azeotropic column • Applicability: o Most widely used method in the
extracts ’’ it downwards the azeotropic column • Applicability: o Most widely used method in the

Feasibility and synthesis for extractive distillation

Pure component 1 (D1) is taken as top product from extractive column

• Entrainer “extracts” component 2 at the bottom (B1)

Entrainer recovery column separates entrainer from component 2

Pure entrainer (E) is recovered at bottom (B2) and used as reflux in extractive column

Rectifying section Rectifying section Binary feed (1 & 2) F Bottom section
Rectifying
section
Rectifying
section
Binary feed
(1 & 2)
F
Bottom
section

Bottom section

25

extractive column Rectifying section Rectifying section Binary feed (1 & 2) F Bottom section Bottom section

Examples from Oil & Gas CRAIER plant at Kårstø

A common azeotrope in oil and gas industry is the ethane / CO 2 azeotrope

CO 2 has a volatility between methane and ethane

CO 2 distributes between natural gas and NGL in a gas processing plant

between natural gas and NGL in a gas processing plant CO 2 C2 C1 C3 *
CO 2 C2 C1 C3
CO 2
C2
C1
C3

* Anette Kornberg, “Equation of State for the System CO2 and Ethane, Project report, NTNU, Dec. 2007

2 C2 C1 C3 * Anette Kornberg, “Equation of State for the System CO2 and Ethane,

CO 2 Removal and Increased Ethane Recovery (CRAIER)

CO 2 Removal and Increased Ethane Recovery (CRAIER) 27
CO 2 Removal and Increased Ethane Recovery (CRAIER) 27

CRAIER column

C 2 + CO 2 (+ C1) ~ 20 mol% CO 2
C 2 + CO 2 (+ C1)
~ 20 mol% CO 2

Az C 2 /CO 2 ~ 50 mol% CO 2

C 2 product (pure)

CRAIER column C 2 + CO 2 (+ C1) ~ 20 mol% CO 2 Az C

Examples from Oil & Gas Ryan Holmes process

Invented by Jim Ryan and Art Holmes*

Cryogenic distillation process for the removal of CO 2 from natural gas

Suitable for removing high CO 2 contents from natural gas

• Uses extractive distillation to ‘‘break’’ the CO 2 / C2 azeotrope

Uses Natural Gas Liquid (NGL) as entrainer, which is an internal product

of the process

Various configurations with 2, 3 and 4 columns

* A. S. Holmes, J. M. Ryan, Cryogenic distillation separation of acid gases from methane, US patent, 1982

and 4 columns * A. S. Holmes, J. M. Ryan, Cryogenic distillation separation of acid gases
Added entrainer De-C1 Extractive column Entrainer recovery column column C 2+ CO 2 /C 2+
Added
entrainer
De-C1
Extractive
column
Entrainer
recovery column
column
C 2+
CO 2 /C 2+
C 4+
Entrainer (C4+) recycle
De-C1 Extractive column Entrainer recovery column column C 2+ CO 2 /C 2+ C 4+ Entrainer

MTBE Production and Separation Unit

Azeo C4-MeOH + water (E) Feed C3 – C5+ MTBE methanol MeOH- water
Azeo
C4-MeOH
+ water (E)
Feed
C3 – C5+
MTBE
methanol
MeOH-
water

31

MTBE Production and Separation Unit Azeo C4-MeOH + water (E) Feed C3 – C5+ MTBE methanol

Process description

Feed to 1 st separation column

C3

C4 (with excess isobutylene)

C5+

Water

Methanol

First Column (Distillation Column)

Bottom: MTBE

Top: C4 methanol azeotrope

Second Column (Extraction Column)

Addition of water countercurrent to flow

Methanol has more affinity for water pass to aqueous phase

Top: Raffinate (C3,C4,C5+)

Bottom: Methanol/Water

Third Column (Distillation Column)

Top: methanol

Bottom: Water

32

(C3,C4,C5+) − Bottom: Methanol/Water • Third Column (Distillation Column) − Top: methanol − Bottom: Water 32

Summary

Separation of azeotropic mixtures is a topic of great practical and

industrial interest

Azeotropic mixtures are impossible to separate by ordinary distillation, but may be effectively be separated by adding a third

component, called entrainer

Residue curve maps (RCM) and distillation curve maps (DCM) are representations of the thermodynamic behavior (VLE and VLLE) of

azeotropic mixtures

RCM and DCM are used to identify feasible distillation schemes

33

behavior (VLE and VLLE) of azeotropic mixtures • RCM and DCM are used to identify feasible

Summary

Homogeneous azeotropic distillation

o

Only few RCM and DCM lead to feasible schemes

o

Limiting use in the industry

Heteroazeotropic distillation

o

Ordinary distillation combined with a decanter is used

o

Liquid-liquid immiscibilities are used to overcome azeotropic compositions

o

Method widely used in the industry

Extractive distillation

o

Heavy entrainer used that ‘‘extracts’’ one of the original components and

enhances separation

o

Broad range of feasible entrainers (no liquid-liquid immiscibility required)

o

The most widely used method in the industry

34

of feasible entrainers (no liquid-liquid immiscibility required) o The most widely used method in the industry
Presenters name: Dr. Stathis Skouras Presenters title: Principal Researcher E-mail: efss@statoil.com Tel: +47-97695962

Presenters name: Dr. Stathis Skouras Presenters title: Principal Researcher E-mail: efss@statoil.com Tel: +47-97695962

www.statoil.com

Dr. Stathis Skouras Presenters title: Principal Researcher E-mail: efss@statoil.com Tel: +47-97695962 www.statoil.com 35