LECTURE 6:

SEPARATION SYSTEM-PART 2
Dr. Agus Arsad
 Group Working Session

• Reactor effluent consist of hydrogen, toluene,

methane, benzene and diphenyl. Design alternative
sequences for 5 component system.

• Assume volatility:
Hydrogen>methane>benzene>toluene>diphenyl
Number of Alternative Sequences for
Ordinary Distillation
Number of Number of possible
components sequences
2 1
3 2
4 5
5 14
6 42
7 132
8 429
9 1,430
10 4,862

Ns = [2(P-1)]!/P!(P-1)!
 Sequencing of Distillation 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.
Ex. 1-Specification for Butenes Recovery
 Design for Butenes Recovery System

100-tray column
C3 & 1-Butene in
distillate

Propane and
1-Butene recovery
Pentane
withdrawn as n-C4 and 2-C4=s
bottoms cannot be
separated by
ordinary
distillation
(=1.03), so 96%
2-C4=s withdrawn as furfural is added
distillate. Furfural is as an extractive
recovered as agent (  1.17).
bottoms and recycled n-C4 withdrawn as
to C-4 distillate.
 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)
 the introduction into the system of a second fluid phase (MSA
– mass separating agent). This must be subsequently
removed.
 the addition of a solid phase upon which adsorption can
occur
 the placement of a membrane barrier
 Common Industrial Separation Methods

Separatio Phase of Separatio Developed Separatio

n Method the feed n agent or added n principle
phase
Equilibrium L and/or V Pressure V or L difference
reduction or
flash in volatility
heat transfer
Distillation L and/or V Heat transfer V or L difference
or shaft work
in volatility
Gas V Liquid L difference
absorbent
Absorption in volatility
Stripping L Vapor V difference
stripping
in volatility
agent
Extractive L and/or V Liquid solvent V and L difference
and heat
Distillation in volatility
transfer
Azeotropic L and/or V Liquid V and L difference
entrainer and
Distillation in volatility
heat transfer
Ex. 2 – Sequences for 4-component
separation
 Scoping & Screening
Optimal Sequencing of Separator

The number of alternatives may be reduced by way of

 Practical Constraints (e.g. safety, product purity

and operability)
 Heuristics (past experiences, observations - to
reduce capital & operating costs)
 Vapour Flowrate
 Practical Constraints

General Heuristics for safety and operability

Remove Corrosive and Hazardous Components Early
 avoids expensive handling costs - e.g. stainless steel
columns throughout)
 the more columns a corrosive component passes through,
the more expensive will be the distillation train

Remove Reactive or Heat Sensitive Components Early

 Reactive components change separation problems- e.g.
monomers foul reboilers due to polymerization @ high Ts
 Heat sensitive materials requires costly vacuum columns

Webster’s definition - Heuristic: (from Greek heuriskin to discover) serving to guide,

discover or Reveal: Valuable for empirical research but unproved or incapable of prove…
 Practical Constraints (con’t)

Operability and Product Quality Constraints

Remove products or recycle streams as distillates, particularly

if they are recycled to a packed bed reactor
 avoids contamination of the product or recycle stream with
heavy materials, rust etc.
 avoids accumulation of contaminant in the process
 sometimes to avoid product contamination by additives that
may be used to inhibit polymerization
 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. The reboiler duty is not
excessive.
 Identifying the Best Sequence Using
Heuristics

For simple columns (one top, one bottom stream);

Heuristics for column sequencing

 Most plentiful first
 Lightest first
 High-purity separations last
 Difficult separations last
 Favour Equimolar split
 Aim high, rather than low
 Use internal species for indirect separation
 Class Exercise

Design a sequence of
ordinary distillation
columns to meet the
given specifications.
Class Exercise – Possible Solution
Costing as a factor of consideration
 (A/B…)I, (…E/F)I, (…B/C…)I, (A/C…)I , (…C/B…)II, and (…C/D…)II

1st Branch of Sequences

Sequence Cost, $/yr

1-5-16-28 900,200
1-5-17-29 872,400
1-6-18 1,127,400
1-7-19-30 878,000
1-7-20 1,095,600

Species
Propane A
1-Butene B
n-Butane C
trans-2-Butene D
cis-2-Butene E
n-Pentane F
 (A/B…)I, (…E/F)I, (…B/C…)I, (A/C…)I , (…C/B…)II, and (…C/D…)II

2nd Branch of Sequences

Sequence Cost, $/yr

2-(8,9-21) 888,200
2-(8,10-22) 860,400

Species
Propane A
1-Butene B
n-Butane C
trans-2-Butene D
cis-2-Butene E
n-Pentane F
 (A/B…)I, (…E/F)I, (…B/C…)I, (A/C…)I , (…C/B…)II, and (…C/D…)II

3rd Branch of Sequences

Sequence Cost, $/yr

3-11-23-31 878,200
3-11-24 1,095,700
3-12-(25,26) 867,400
3-13-27 1,080,100

Species
Propane A
1-Butene B
n-Butane C
trans-2-Butene D
cis-2-Butene E
n-Pentane F
 (A/B…)I, (…E/F)I, (…B/C…)I, (A/C…)I , (…C/B…)II, and (…C/D…)II

4th Branch of Sequences

Sequence Cost, $/yr

4-14-15 1,115,200

Species
Propane A
1-Butene B
n-Butane C
trans-2-Butene D
cis-2-Butene E
n-Pentane F
 Lowest Cost Sequence

Sequence Cost, $/yr

2-(8,10-22) 860,400
 Example 3 (Example 1 Revisited)

Species b.pt.(C) Tc (C) Pc, (MPa)

Propane A -42.1 97.7 4.17
1-Butene B -6.3 146.4 3.94
n-Butane C -0.5 152.0 3.73
trans-2-Butene D 0.9 155.4 4.12
cis-2-Butene E 3.7 161.4 4.02
n-Pentane F 36.1 196.3 3.31

 For T = 2 (OD and ED), and P = 4, NS = 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.
 Example 3 (Example 1 Revisited)

Adjacent Binary Pair ij at 65.5 oC

Propane/1-Butene (A/B) 2.45
1-Butene/n-Butane (B/C) 1.18
n-Butane/trans-2-Butene (C/D) 1.03
cis-2-Butene/n-Pentane (E/F) 2.50
 Splits A/B and E/F should be by OD only (  2.5)
 Split C/D is infeasible by OD ( = 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 C/B = 1.17. Also, split (C/D)II with  = 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…)II
 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 systematic B&B methods to
determine an optimal sequence of distillation-type
separations..
 Quantative Measure:Most Plentiful First
Separation Sequence Total Load

1 1
2 3
1 2 2 D1 + 2D2 + 3D3 + 3D4
3 3 3 4
4 4 4

2
1 1 2
3 D1 + 3D2 + 3D3 + 2D4
2 2 2 3
3 3 4
4 4

1
2 2 2D1 + 2D2 + 2D3 + 2D4
1
3 2 3
3
3 4 4
4
 Most Plentiful First
Separation Sequence Total Load
1
1
2 2
1 3D1 + 3D2 + 2D3 + D4
2 3
1
3
4 2
3 4
4 1
1 2
2 2
1 3 2D1 + 3D2 + 3D3 + D4
3 3
5 2
3 4
4
Sequence Total Load
1 9D
OR, use vapour flowrate approach 2 9D
(see later) 3 8D
4 9D
5 9D
 Direct Sequence

A (60)
A (60) B (60)
B (60) B
C (180) C
C (180)

Separation Load for Direct Sequence

= A + 2B + 2C

= 60 + 2(60) + 2(180) = 540 units

 Indirect Sequence

A (60)

A
B B (60)
A (60)
B (60)
C (180)
C (180)

Separation Load for Indirect Sequence

Indirect sequence
= C + 2A + 2B More favourable !

= 1(180) + 2(60) + 2(60) = 420 units

 Working Session Separation Synthesis
Heuristics

• Three hundred kmols of a ternary mixture A, B and C in

0.2:0.2:0.6 proportion needed to be separated into pure
components (assume ideal or sharp separation that could
recover each of the component in pure form)

• Synthesise every possible separation sequence to recover the

pure components A and C. What type of sequences are
these?

• Use any of the available heuristics to screen among the

sequences synthesised, and identify the better sequence (hint:
assume the heat load is directly proportional to the
components’ feed rates, and do not use the vapour flowrate
approach)
 Difficult Separation Last
Separation Sequence Total Difficulty

1 1
2 2 D  D2  D3  D4  D2  D3  D4  D3  D4 
1 3  
1

2  12  23  34
3
3 3
4 4
4 4
2
1 1 2
load
2 2 2 3 3
3 3 4
D  D2  D3  D4  D2  D3  D2  D3  D4 
 
1

4 4  12  23  34

1 Sep difficulty
1
1 2 2 D  D2  D1  D2  D3  D4  D3  D4 
 
1

3 2 3  12  23  34
3
3 4 4
4
 Difficult Separation Last

Separation Sequence Total Difficulty

1
1
4 2 2 D  D2  D1  D2  D3  D1  D2  D3  D4 
1 1
 
2 3  12  23  34
1
3
2
3 4
4
1 D  D2  D3  D2  D3  D1  D2  D3  D4 
 
1
1 2  12  23  34
2 2
1 3
3 3
5 2
3 4 • Assume D1=D2=D3=D4=D5=D;
4
• Assume 12=34=;
and 23=/3
 Difficult Separation Last

Sequence Total Difficulty

Least Difficult 1 D D
4  9  2   (15)
 

2 D D
4  6  3  (13)
 

Most Difficult 3 D D
2  12  2   (16)
 
D D
4 2  9  4  (15)
 
D D
3  6  4  (13)
Least Difficult 5  
 Aim to Separate at High T,
Rather than Low T
 All other things being equal, avoid
150 excursions in T and P, but aim high,
rather than low
Relative Cost/Btu

Cooling
100
Heating

50

-150 Room 400°F

Temperature
Cost of temperature excursions from [Rudd 72]
All other things being equal, during distillation, sequences that
remove the components one by one in column overheads
should be favored
Eg. Ethylene and Propylene manufacture - use heuristics
1. Difficult separation lasts. BP propane (-420C) and propylene
(-480C) are very close. C3 splitter is for last. The next most
difficult is ethane (-880C) and ethylene (-1040C). C2 splitter also
in a last position
2. Favor overhead removal. To get to last separation, material
more volatile and less volatile than C2 and C3 must first be
removed. First distillation, remove the most volatile component,
hydrogen (BP -2530C) and methane (-1610C).
3. Remove valuable product as distillate. To ensure product purity
and avoid inclusion of colored material, C2 and C3 as top
products.
 Typical Distillation Sequence for
Light Olefin Manufacturing

No Component BP (0C)
1. 18% H2 -253
2. 15% CH4 -161
3. 24% C2H4 -104
4. 15% C2H6 -88
5. 14% C3H6 -48
6. 6% C3H8 -42
7. 8% heavies, C4 -1

1 1
2 3
2 3
3 4 4
3 5
4
4 5
5 5
5 6 6
6 6
6
7 7 7
7
 Light Olefin Product Separation -
Lightest First -
H2,C1 C2-,C20 C2 ,
[BP°C]
18% Hydrogen; H2 [-253]
Pressurized
15% Methane; C1 [-161] columns are
24% Ethylene; C2- [-104] DM used to T
DM SP
15% Ethane; C20 [-88]
14% Propylene; C3- [-48]
6% Propane; C30 [-42]
8% Heavies; C4+ [-1] C20 C3-
C2-,C20,C3-,C30,C4+ C3-,C30

DP SP
DM = Demethanizer C3-,C30,C4+
DP = Depropanizer
SP = Splitter
C4+ C30
 Limitations

• Conflicts - e.g. When the most plentiful is the heaviest ‡

• When operating variables are altered (e.g. when conversion
is altered, the most plentiful component may become the least plentiful)
• Applicable to simple columns (single feed stream, 1 top, 1 bottom
prods.)

‡ Literature on resolving heuristics conflicts, and detailed sequencing heuristics

• Seader and Westerberg, AIChE J. 77
• Nishida and Stephanopolous AIChE J. 81
• Malone et al. AIChE J. 85
 Vapour Flowrate Approach (1)

 Fv Q Oper
Cost
 Fv Dc Capital
Cost
Favour sequence with the lowest vapour flowrate
Vapour flowrate estimation

V = D(1 + R)
Define RF = R/Rmin
V = D(1 + RFRmin) (1)

1
 Vapour Flowrate Approach (2)

(Use Underwood Eqn to calculate Rmin)

Underwood Equation: ~ 0 - Assuming sharp

1 xDLK x separation and LK
Rmin = -  DHK and LLK o.head
-1 xFLK xFHK

1 F
Rmin =
-1 D (2)

2
 Vapour Flowrate Approach (3)

Combine (1) and (2), (Vapor Flowrate and Rmin Equations):

V=D 1 + RF F
-1 D

V = (FA + FB + ..... + FLK) + (FA + FB .... + FLK + FHK + ...+ FNC) RF

-1
Distillate Feed
 Example: Vapour Flowrate Approach

The table below gives the data for a ternary separation of benzene, toluene
and ethyl benzene. Using the vapour flowrate equation, determine whether
direct or indirect sequence should be used.

Component Flowrate Relative Relative

(kmol/h) volatility volatility
between
adja. comps.

Benzene 269 3.53

1.96
Toluene 282 1.80
1.80
Ethyl Benzene 57 1.0

RF=1.1
 Solution: Vapour Flowrate Approach

For the direct sequence

S V = 269 + (269 + 282 + 57) 1.1 + 282 + (282 + 57) 1.1

(1.96 -1) (1.8 -1)
269
= 965.7 + 748.1
0
= 1713.8 kmol/h
0
0
269
282
282
0
57

0
0
57
For the indirect sequence

S V = (269 + 282) + (269 + 282 + 57) 1.1 + 269 + (269 + 282) 1.1
(1.8 -1) (1.96 -1)
269
= 1387 + 900.4 0
= 2287.4 kmol/h 0

269
282 0
57 282
0 0
Hence, the direct sequence 0
should be used 57
 Working Session SS1:
Separation Synthesis 1

A stream is to be separated of Methane (bp –161ºC), benzene (bp 80ºC),

toluene (bp 110ºC) and orthoxylene (bp 144ºC) of a composition of ,
respectively, 0.50, 0.10, 0.10, 0.30. What sequence of boiling-point
exploitations will probably lead to the most economic separation?

(a) Use the heuristic approach

(b) Verify your answer in (a) using the vapour flowrate approach
Given
Relative volatility 3.70, 2.5, 1.7 and 1.0
RF = 1.1
 Quiz 4124: Separation Synthesis 2

Methanolamine can be produced as follows:

H2C – CH2 + NH3  NH2CH2CH2OH

O
Ehtylene Ammonia Methanolamine (MEA)
Oxide (EO)

MEA + EO  NH(CH2CH2CH2OH)2
(DEA)

DEA + EO  N(CH2CH2OH)3
(TEA)
 Quiz 4124: Separation Synthesis 2
(cont’)

Assuming that
· EO is fully converted
· some NH3 is unconverted
· reactor effluent contains equal amount of NH3, MEA, DEA and TEA
· separation by distillation is desirable
· the boiling point order is according to NH3 << MEA << DEA << TEA

Using only the assumption provided, generate all possible distillation

sequences, and, determine the sequence that would give rise to the
lowest separation load using a short-cut approach. (Hint: You neither
need the Antoine Equation nor the relative volatility)
 Why distillation?

Advantages of distillation

• Able to handle a large and a wide range of throughputs

• Able to handle a wide range of feed concentrations
• Able to produce a high product purity
 Why not distillation?

 Separation of low molecular weight materials

 Separation of high molecular weight, heat sensitive materials
 Separation of components with a low concentration
 Separation of different classes of components
 Separation of mixtures with low relative volatility or which exhibit
azeotropic behaviour
 Separation of volatile liquid from non-volatile components
 Separation of mixtures of condensible and non-condensible
components
 Packed or Plate Column?

Factors dependent upon the system

• If system has a foaming tendency, check packed; if not, both

• If system contains solid or sludges, check plate; if not, both
• If the constituents are corrosive fluids, check packed; if not, both
• If system has heat of solution difficulties check plate, if not, both
• If operation is intermittent,check plate; if not both
• If the system is small (column < 2 ft) check packed; if not, both
• If system is temperature sensitive, check packed; if not, both
• If system has close boiling components, check packed; if not, both
• If system is viscuous, check packed; if not, both
 Packed or Plate Column?

Factors dependent upon the flow regime in the column

• If resistance to mass transfer is controlled by gas phase, check packed;

if controlled by liquid phase, check plate; if no phase is controlling,
check both
• If system requires wide variations in liquid and/or gas rates, check plate;
if not, both
• If liquid holdup is undesirable, check packed; if not, both
• If column DP is to be kept low, check packed; if not, both
 Packed or Plate Column?

Factors dependent upon the physical nature of the column

• If frequent cleaning is expected, check plate; if not, both

• If weight is critical, check plate; if not, both
• If side streams are to be employed, check plate; if not both
• If diameter of column < 2ft, check packed; if not, both
• If overhead clearance is critical, check packed; if not both.
• If floor space is critical, check plate; if not both.
 Alternatives to Distillation

Alternatives to Distillation

 Extraction
 Extractive Distillation
 Azeotropic Distillation
 Reactive Distillation
 Crystallization
 Adsorption
 Reaction
 Membrane Separation
 Extraction
5 B

B+S C
7
3 2
B+C 6
S 1
C (+ B) 4
6 5 2
B 3 S
1
4
B+C C+S C
7
(+ B)
Refer R.E. Treybal on
the use of liquid extraction
 Extractive Distillation

S B A

A+B azeotrope
C1
A+B C1
C2
B
S
S B S
C2
e.g., A = Ethanol
B = H2 O mix
S = Ethylene Glycol split
 Azeotropic Distillation

ABS Ternary
heterogeneous
azeotrope

A+B
azeotrope A+B
C1 C2 azeotrope

A
A C3
B
e.g., A = Ethanol
B = H2 O B
S = Benzene
 Reactive Distillation
B(meta-xylene)
S

B
C1
C
C2

C+S
C (para-xylene)
 Add an entrainer to react with one component in a mixture that is
difficult to separate (e.g. xylene isomers)
 B, C = meta- & para-xylenes:  = 1.03
 S = Organometallic, e.g. sodium cumene; C (para) reacts with S; B:CS ~ 30
 Separation greatly simplified, but, problems in handling sodium cumene
 Important alternative if a simpler to handle entariners can be found