Sequencing Separation

Trains

Sequencing Separation Trains

Priyank Khirsariya
Assistant Professor
Department of Chemical
Engineering
V.V.P. engineering college, Rajkot.
 Process Design/Retrofit
Steps

Assess Primitive
Problem

Detailed Process Plant-wide

Synthesis Development Controllability
-Algorithmic of Base-case Assessment
Methods

PART II
Detailed Design,
Equipment sizing, Cap.
Cost Estimation,
Profitability Analysis,
Optimization
Algorithmic Methods
 Introduction
• Almost all chemical processes require the separation of
chemical species (components), to:
 Purify a reactor feed
 Recover unreacted species for recycle to a reactor
 Separate and purify the products from a reactor

• Frequently, the major investment and operating costs of

a process will be associated with separation equipment

• For a binary mixture, it may be possible to select a

separation method that can accomplish the separation
task in just one piece of equipment.

• More commonly, the feed mixture involves more than

two components, involving more complex separation
systems.
 Objectives

 Be familiar with the more widely used

industrial separation methods and their
basis for separation.

 Understand the concept of the separation

factor and be able to select appropriate
separation methods for liquid mixtures.
 Instructional Objectives
When you have finished studying this unit, you should:
 Be familiar with the more widely used industrial separation
methods and their basis for separation.
 Understand the concept of the separation factor and be able
to select appropriate separation methods for vapor and liquid
mixtures.
 Understand how distillation columns are sequenced and how
to apply heuristics to narrow the search for a near-optimal
sequence.
 Be able to apply algorithmic methods to determine an
optimal sequence of distillation-type separations.
Example: Butenes Recovery
 Example: Butenes Recovery

100-tray column
C3 & 1-Butene in
distillate

Propane and
1-Butene
Pentane recovery
withdrawn as n-C4 and 2-C4=s
bottoms cannot be
separated by
ordinary
distillation
(=1.03), so 96%
2-C4=s withdrawn furfural is added
as distillate. as an extractive
Furfural is agent (  1.17).
recovered as n-C4 withdrawn
bottoms and as distillate.
recycled to C-4
 Separation is Energy
Intensive
• Unlike the spontaneous mixing of chemical species, the
separation of a mixture of chemicals requires an
expenditure of some form of energy

• Separation of a feed mixture into streams of differing

chemical composition is achieved by forcing the different
species into different spatial locations, by one or a
combination of four common industrial techniques:
 The creation by heat transfer, shaft work, or pressure
reduction of a second phase that is immiscible with the feed
phase (ESA – energy separating agent)
 Introduction into the system of a second fluid phase (MSA –
mass separating agent). This must be subsequently removed.
 Addition of a solid phase upon which adsorption can occur
 Placement of a membrane barrier
Common Separation
Methods
Common Separation
Methods
Common Separation
Methods
 Separation Method
Selection
• The development of a separation process requires the
selection of:
 Separation methods
 ESAs and/or MSAs
 Separation equipment
 Optimal arrangement or sequencing of the equipment
 Optimal operating temperature and pressure for the equipment

• Selection of separation method depends on feed

condition:
• Vapor Partial condensation, distillation, absorption,
adsorption, gas permeation (membranes)
• Liquid Distillation, stripping, LL extraction, supercritical
extraction, crystallization, adsorption, and dialysis or reverse
osmosis (membranes)
• Solid If wet  drying, if dry  leaching
 Separation Method
Selection
• The separation factor, SF, defines the degree of
separation achievable between two key components of
the feed. This factor, for separation of component 1
from component 2 between phases I & II, for a single
stage of contacting, is:
C = composition variable,
C 1I / C 2I
SF  I, II = phases rich in (8.1)
C 1II / C 2II components 1 and 2.

• SF is generally limited by thermodynamic equilibrium. For

example, in the case of distillation, using mole fractions as
the composition variable and letting phase I be the vapor
and phase II be the liquid, the limiting value of SF is given
in terms of vapor-liquid equilibrium ratios (K-values) as:

y 1 / x 1 K1 P1 s
SF    1 , 2  s  for ideal L and V  (8.2), (8.3)
y 2 / x 2 K2 P2
 Separation Method
Selection
• For vapor-liquid separation operations that use an MSA
that causes the formation of a non-ideal liquid solution
(e.g. extractive distillation):
1LP1 s
SF  1,2  (8.5)
2LP2s
• If the MSA is used to create two liquid phases, such as in
liquid-liquid extraction, the SF is referred to as the
relative selectivity, β , where:
1II /  2II
SF  1,2  (8.6)
1I /  2I

• In general, MSAs for extractive distillation and liquid-liquid

extraction are selected according to their ease of recovery
for recycle and to achieve relatively large values of SF.
 Equal Cost Separators

Liquid-Liquid Extraction
should NOT be used
when α for ordinary
distillation is greater
than 3.2

Extractive distillation
should NOT be used
when α for ordinary
distillation is
greater than 2

Ref: Souders (1964)

 Summary – Separation
Trains
On completion of this part, you should:

 Be familiar with the more widely used industrial

separation methods and their basis for separation.

 Understand the concept of the separation factor

and be able to select appropriate separation
methods for liquid mixtures.
 Objectives

 Understand how distillation columns are sequenced

and how to apply heuristics to narrow the search
for a near-optimal sequence.

 Be able to apply systematic methods to determine

an optimal sequence of distillation-type
separations.
 Sequencing OD Columns
• Use a sequence of ordinary distillation (OD) columns to
separate a multicomponent mixture provided:

  in each column is > 1.05.

 The reboiler duty is not excessive.
 The tower pressure does not cause the mixture to
approach the TC of the mixture.
 Column pressure drop is tolerable, particularly if
operation is under vacuum.
 The overhead vapor can be at least partially condensed at
the column pressure to provide reflux without excessive
refrigeration requirements.
 The bottoms temperature for the tower pressure is not so
high that chemical decomposition occurs.
 Azeotropes do not prevent the desired separation.
Pressure/Condenser
Algorithm
 Number of Sequences of Ordinary Distillation Columns

• Number of different sequences of P –1 ordinary distillation

(OD) columns, NS, to produce P products:

[2(P  1)]!
Ns 
P ! (P  1)!

P # of Separators Ns
2 1 1
3 2 2
4 3 5
5 4 14
6 5 42
7 6 132
8 7 429
Thomson and King Formula
Example: 4 Components
Example: 4 Components
 Best Sequence using
•
Heuristics
The following guidelines are often used to reduce the number
of OD sequences that need to be studied in detail:

 Remove thermally unstable, corrosive, or chemically reactive

components early in the sequence.
 Remove final products one-by-one as distillates (the direct
sequence).
 Sequence separation points to remove, early in the sequence,
those components of greatest molar percentage in the feed.
 Sequence separation points in the order of decreasing relative
volatility so that the most difficult splits are made in the
absence of other components.
 Sequence separation points to leave last those separations that
give the highest purity products.
 Sequence separation points that favor near equimolar amounts
of distillate and bottoms in each column. The reboiler duty
should not be excessive.
 Class Exercise

Design a
sequence of
ordinary
distillation
columns to meet
the given
specifications.
Exercise – Possible Solution

Guided by Heuristic 4, the first

column in position to separate
the key components with the
greatest SF.

 Sequence separation points in the order

of decreasing relative volatility so that the
most difficult splits are made in the
absence of other components.
 Exercise – Possible Solution

 = 1.5

 = 3.6  = 2.8

 = 1.35
 Marginal vapor rate

Chemical Engineering Department

20th Jan 2011 L. D. College of Engineering
Marginal vapor rates for possible five sequences

Chemical Engineering Department

20th Jan 2011 L. D. College of Engineering
 Marginal Vapor Rate Method

When the number of products is more than four, using the annualized
cost method is very difficult and time-consuming. One of the less rigorous
method for OD that can produce good results is Marginal Vapor Rate
(MV) that proposed by Modi and Westerberg (1992).

 The difference in costs between the separation in the absence of

nonkey components and the separation in the presence of nonkey
components, defined as Marginal Annualized Cost (MAC).
 A good approximation of MAC is the MV, which is the corresponding
difference in molar vapor rate passing up the column. The sequence
with the minimum sum of column MVs is selected.
 Vapor rate is a good measure of cost because it is a major factor in
determining column diameter, reboiler and condenser areas, and
reboiler and condenser duties.

31 4 - Separation Trains
 Estimating Marginal Vapor Rate, MV
 For each separation, MV is estimated assuming feed at bubble
point and 99.9 mol % recovery of light key and heavy key in
distillate and bottom, respectively. The following steps are followed:

1. Set distillate and bottoms column pressures using

2. Estimate distillate rate (D), by using a short-cut distillation method

(e.g., DSTWU in Aspen plus with R=1.2 Rmin).

3. Calculate the up column vapor rate as V=D(R+1).

4. Calculate the MV (The difference in vapor rate between the

separation in the absence of nonkey components and the
separation in the presence of nonkey components)
 Example
 Use the marginal vapor rate (MV) method to determine a
sequence for the hydrocarbon specified in the figure, except:
1. Ignore the given temperature and pressure of the feed
2. Assume a recovery of 99.9% in each column
 Example 4
A=isobutane, B= n-butane, C=isopentane, D= n-pentane
 Minimum and Marginal vapor flow
Underwood's method for minimum vapor flow

Marginal vapor flow calculation

(a simplified formula)
5 components Alcohol Mixture

Marginal vapor flows

Total Marginal vapor flows
Possible Sequences
 Complex Columns
• In some cases, complex rather than simple distillation columns
should be considered when developing a separation sequence.

Ref: Tedder and Rudd (1978)

 Regions of Optimality
• As shown below, optimal regions for the various configurations
depend on the feed composition and the ease-of-separation
index (ESI):

ESI = AB/ BC

ESI  1.6 ESI  1.6

 Introduction
• Separation sequences are complicated by the presence
of azeotropes, often involving mixtures of oxygenated
organic compounds:
 Alcohols
 Ketones
 Ethers
 Acids
 Water

• In these cases, distillation boundaries limit the

product compositions of a column to lie within a
bounded region.

• This prevents the removal of certain species in high

concentrations.
 Objectives

 Be able to sketch the residue curves on a ternary

phase diagram

 Be able to define the range of possible product

compositions using distillation, given the feed
composition and the ternary phase diagram
Basics: The Lever Rule
Basics: Ternary Phase
Diagrams

0.2 TBA

0.65 DTBP

0.2 DTBP

0.15 H2O
Basics: Ternary Phase
Diagrams

0.2 TBA

0.2 DTBP

0.6 H2O
 Homogeneous Azeotropes
1:4
At equilibrium:
_ V _ L

f  f
j j

y P  x f
j
V

j j j j
L

yP  xP
1 1 1
s

yP  xP
2 2 2
s

P  x P  x P  x P  (1  x )P
1 1
s

2 2
s

1 1
s

1 2
s

 P  (P  P ) x
2
s

1
s

2
s

At fixed temperature
Homogeneous Azeotropes
2:4

Example – Phase diagrams for

benzene-toluene mixture at 90 oC
 Homogeneous Azeotropes
3:4
yP  x P S

For non-ideal mixtures, the 1 1 1 1

activity coefficients are yP  x P

2 2 2 2
S

different from unity: P  x  P  (1  x )  P

s s

1 1 1 1 2 2

If   1 the mixture has a minimum-boiling

i minimum
azeotrope

Example – Phase diagrams for Isopropyl ether-Isopropyl

alcohol
 Homogeneous Azeotropes
4:4
yP  x P S

For non-ideal mixtures, the 1 1 1 1

activity coefficients are yP  x P

2 2 2 2
S

different from unity: P  x  P  (1  x )  P

s s

1 1 1 1 2 2

If   1 the mixture has a maximum-boiling

i maximum
azeotrope

Example – Phase diagrams for Acetone-Chloroform

 Heterogeneous Azeotropes

For a minimum-boiling azeotrope with large deviation

i
 1(
from Raoult’s law ), phase splitting may occur
and a minimum-boiling heterogeneous azeotrope
forms, having a vapor phase in equilibrium with two
liquid phases.

Homogeneous Azeotrope Heterogeneous Azeotrope

 Residue Curves 1:3

Simple Distillation

Mass balance on species j:

Lx  ( L ) y  (L  L )( x  x ), j  1,K , C  1
j j j j

As L  0:
Lx  y dL  Lx  Ldx  x dL  dLdx , j  1,K , C  1
j j j j j j

dx
Rearranging: j
 x  y  x (1  K {T, P, x, y })
dL / L
j j j j 


dx j
  x y
dt
j j
 Residue Curves 2:3
• Residue Curves  Liquid Compositions at Total
Reflux
dx
j
  x y
dt
j j

Residue curves
for zeotropic
system Residue curves
for Azeotropic
system
 Residue Curves 3:3
• Residue Curves  Liquid Compositions at Total Reflux

Species balance on top n-1 trays:

L x  Dx  V y
n 1 n 1 D n n

Approximation for liquid phase:

dx
 x x
n

dh
n n 1

Substituting:
dx V D
n
 x  y  x n

dh L L
n n D

n 1 n 1
Rectifying section of
distillation column At total reflux, D = 0 and Vn = Ln-1
dx
 x y
n

dh
n n
 Sketching Residue Curves
 Plot pure components on vertices
along with Tb
 Plot all azeotropes on diagram along
with their Tb
 Plot residue curves connecting all
azeotropes, azeotropes & vertices,
and finally vertices & vertices with
arrow heads pointing towards
increasing boiling point temperatures
 Plot additional residue curves that
“arch” towards intermediate
temperatures on the way to the end
point

dx
j
  x y
dt
j j
 Product Compositions
• For zeotropic systems
Regions
– L: Lowest boiling component, I: Intermediate boiling component, H: Highest boiling component, F: Feed composition

Pure L
distillate

Pure H
bottoms
 Product Compositions
• For azeotropic systems
Regions
– Shaded regions: Feasible distillate and bottoms product compositions

Three binary azeotropes

Two binary azeotropes
and one ternary
azeotrope
 Summary – Non-ideal
Thermo
On completion of this part, you should:

 Be able to sketch the residue curves on a ternary

phase diagram

 Be able to define the range of possible product

compositions using distillation, given the feed
composition and the ternary phase diagram
Separation systems for Gas mixtures
Process for producing inorganic salt crystals
Separation systems for solid mixtures