SEQUENCING OF SEPARATION TRAINS

Ref: Seider, Seader and Lewin (2004),

Chapter 7
4 - Separation Trains
 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 those costs associated with the
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. However, more
commonly, the feed mixture involves more than two
components, involving more complex separation systems

4 - Separation Trains
 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.

4 - Separation Trains
Example 1. Specification for Butenes Recovery

4 - Separation Trains
 Design for Butenes Recovery System

100-tray
column C3 & 1-
Butene in
distillate
Propane and
1-Butene
Pentane
recovery
n-C4 and 2-
withdrawn as
bottoms C4=s cannot be
separated by
ordinary
distillation
(α=1.03), so
2-C4=s withdrawn
96% furfural is
as distillate.
added as an
Furfural is
extractive
recovered as
agent (α →
bottoms and
1.17).
recycled to C-4 4 - Separation Trains
n-C4 withdrawn
 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)
agent
the introduction into the system of a second fluid phase ( MSA –
mass separating agent).
agent This must be subsequently removed.
the addition of a solid phase upon which adsorption can occur
(MSA)
MSA
the placement of a membrane barrier (ESA)

4 - Separation Trains
Common Industrial Separation Methods

4 - Separation Trains
Common Industrial Sep.Methods (Cont’d)

4 - Separation Trains
Common Industrial Sep.Methods (Cont’d)

4 - Separation Trains
 Selecting Separation Method (1)
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, cryogenic distillation , absorption,
adsorption, gas permeation (membranes), desublimation
Liquid: partial vaporization, distillation, stripping, extractive
distillation, azeo-distillation, LL extraction, crystallization ,
adsorption, membrane separation (dialysis, reverse osmosis,
ultrafiltration and pervaporation), supercritical extraction
Solid: if slurry →filtration, if wet → drying, if dry →leaching
4 - Separation Trains
 Selecting Separation Method (2)
The separation factor,
factor SF, defines the degree of separation
achievable between two key components of he feed. This factor,
for the separation of component 1 from component 2 between
phases I and II, for a single stage of contacting,
contacting is defined as:

C 1I / C 2I C = composition
SF = variable, I, II = (7
II II
C 1 /C 2 phases rich in .1
components 1 and
SF is generally limited by thermodynamic 2.
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 equilibriums
ratios (K-values) as:
y1 / x 1 K 1 ⎛ P1 ⎞
SF = = = α1,2 ⎜ = s for ideal L and V ⎟⎟
⎜ (7.2
y2 / x 2 K 2 P
⎝ 2 ⎠ ,3)
4 - Separation Trains
 Selecting Separation Method (3)
For vapor-liquid separation operations that use an MSA that
causes the formation of a non-ideal liquid solution (e.g.
extractive distillation):
γ1L P1s
SF = α1,2 = (7
γ2L P2s
.5
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:
γ1II / γ 2II
SF = β1,2 = I I
(7
γ1 / γ 2 .6
)
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.
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 Relative volatilities for equal cost separators

Ref: Souders
(1964)
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 Sequencing of Ordinary Distillation Columns

Use a sequence of ordinary distillation (OD) columns to

separate a multicomponent mixture provided:
α in each column is > 1.05.
The reboiler duty is not excessive.
The tower pressure does not cause the mixture to approach the T C
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.
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Algorithm to Select Pressure and Condenser Type

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 Number of Sequences for Ordinary Distillation

Equation for number of different sequences of P − 1

ordinary distillation (OD) columns, NS, to produce P
products: [2( P − 1)]!
Ns = (7
P ! ( P − 1)!
.9
)

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Example 2 – Sequences for 4-component separation

4 - Separation Trains
Example 2 – Sequences for 4-component separation

4 - Separation Trains
 Identifying the Best Sequences 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.

4 - Separation Trains
 Class Exercise

Design a sequence of
ordinary distillation
columns to meet the
given specifications.

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Class Exercise – Possible Solution

Guided by Heuristic 4,
the first column in
position to separate the
key components with
the greatest SF.

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 Complex Columns for Ternary Mixtures
In some cases, complex rather than simple distillation columns should
be considered when developing a separation sequence.

Ref: Tedder and Rudd

(1978)
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 Regions of Optimality
As shown below, optimal regions for the various configurations
depend on the feed composition and the ease-of-separation index:
ESI = αAB/
αBC

ESI ≤ ESI >

1.6 1.6 4 - Separation Trains
 Sequencing of V-L Separation Systems
When simple distillation is not practical for all separators in
a multicomponent mixture separation system, other types of
separators must be employed and the order of volatility or
other separation index may be different for each type.

If they are all two-product separators and if T equals the

number of different types, then the number of possible
sequences is now given by:
N sT = T P −1N s (7.
10)
For example, if P = 3, and ordinary distillation, extractive
distillation with either solvent I or solvent II, and LL
extraction with solvent III are to be considered, then T =
4, and applying Eqns (7.9) and (7.10) gives 32 possible
sequences (for ordinary distillation alone, NS = 2).
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 Example 3 (Example 1 Revisited)

For T = 2 (OD and ED), and P = 4, N S = 40.

However, since 1-Butene must also be separated (why?), P = 5,
and NS = 224.
Clearly, it would be helpful to reduce the number of sequences
that need to be analyzed.
Need to eliminate infeasible separations, and enforce OD for
separations with acceptable volatilities.
4 - Separation Trains
 Example 3 (Example 1 Revisited)

Splits A/B and E/F should be by OD only (α ≈ 2.5)

Split C/D is infeasible by OD (α = 1.03). Split B/C is feasible,
but an alternative method may be more attractive.
Use of 96% furfural as a solvent for ED increases volatilities of
paraffins to olefins, causing a reversal in volatility between 1-
Butene and n-Butane, altering separation order to ACBDEF, and
giving αC/B = 1.17. Also, split (C/D)II with α = 1.7, should be used
instead of OD.
Thus, splits to be considered, with all others forbidden, are:
(A/B…)I, (…E/F)I, (…B/C…)I, (A/C…)I , (…C/B…)II, and (…C/D…)Trains
4 - Separation II
 Estimating Annualized Cost, CA
For each separation, CA is estimated assuming 99 mol %
recovery of light key and heavy key in distillate and bottom,
respectively. The following steps are followed:
1. 1. Set distillate and bottoms column pressures using
1. Estimate number of stages, feed stage and initial guess of reflux
ratio (R = 1.2 Rmin) by using a short-cut distillation method (e.g.,
DSTWU in Aspen plus).
2. Select tray spacing (typically 2 ft.) and calculate column height, H
(assume an overall efficiency equal to 75%).
3. Estimate reboiler duty, condenser duty and column diameter by a
rigorous distillation method (e.g., RadFrac in Aspen plus)
4. Estimate installed cost of tower (see Chapter 16).
5. Size and cost ancillary equipment (condenser, reboiler, reflux
drum). Sum total capital investment, CTCI.
6. Compute annual cost of heating and cooling utilities (CCOS).
7. Compute CA assuming ROI (typically r = 0.33). CA = CCOS + r CTCI
4 - Separation Trains
 (A/B…)I, (…E/F)I, (…B/C…)I, (A/C…)I , (…C/B…)II, and
1st Branch of Sequences (…C/D…)II

4 - Separation Trains
 (A/B…)I, (…E/F)I, (…B/C…)I, (A/C…)I , (…C/B…)II, and
2nd Branch of Sequences (…C/D…)II

4 - Separation Trains
 (A/B…)I, (…E/F)I, (…B/C…)I, (A/C…)I , (…C/B…)II, and
3rd Branch of Sequences (…C/D…)II

4 - Separation Trains
 (A/B…)I, (…E/F)I, (…B/C…)I, (A/C…)I , (…C/B…)II, and
4th Branch of Sequences (…C/D…)II

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Lowest Cost Sequence

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 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.

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:

Set distillate and bottoms column pressures using

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

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

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

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)

4 - Separation Trains
 Example 4
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

4 - Separation Trains
 Example 4
A=isobutane, B= n-butane, C=isopentane, D= n-
pentane

4 - Separation Trains
 Separation Trains - Summary
On completing 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 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.
Next week: Azeotropic Distillation

4 - Separation Trains