Synthesis of

Separation Trains
Introduction

 Feed separation system may be required to purify the reactor feed(s) by

removing catalyst poisons and inert species, especially when they present
as a significant percentage of feed.
 Effluent separation system, which follow the reactor system and is almost
always required, to recovers unconverted reactant for recycle back to
reactor system, and separates and purifies product and byproducts.
 Whenever separations are too difficult, purge streams are used to prevent
build-up of certain species in recycle streams.
 The major capital and operating costs of a process will be those costs
associated with the separation equipment, rather than chemical reactors.
General flowsheet for a process with one reactor system.
Phase Separation of Reactor Effluent

 Reactor effluent may be a heterogeneous mixture, but often is a

homogeneous mixture.
 For the latter case, it is often advantageous to manipulate temperature
and/or pressure to obtain a partial separation of the components by
forming a heterogeneous mixture of two or more phases, where phase
equilibrium is attained.
 The exiting phase is either
o Recycled back to reactor
o Purge out from system
o Sent to further separation
o Sent for storage (product, byproduct)
 Following phase separation, the individual (vapor, liquid, solid, slurry)
streams are sent to individual separation system.
 For binary mixture, separation task is possible to be accomplished in just one
piece of equipment.
 However, if the feed mixture involves more than 2 components, a
separation system involve a number of unit operation in which the
separations are sequenced, with each unit separating its feed into two
effluents streams of different composition.
 The separation in each unit is made between two components designated
as key components for that particular unit.
 Each effluent is either a final product or feed to another separation device.
 Design of multicomponent separation system can be complex as it
involves:
o Selection of separation methods
o Sequencing of separation unit
Examples of phase-separation devices.
Process
flowsheet
showing
separate
separation
systems with
reactor-
system and
separation-
system
recycles.
 Separation of a feed mixture into streams of differing chemical
compositions is achieved by forcing individual species into different spatial
locations.
 This is accomplished by any one or combination of following techniques:
I. Creation by heat transfer, shaft work, or pressure reduction of a second
phase.
II. Introduction of second phase into system.
III. Addition of solid phase on which selective adsorption occur.
IV. Placement of a selective membrane barrier.
 In first technique, no other chemicals are added to feed mixture and
separation is achieved by heat transfer (energy-separating agent, ESA),
which cause the formation of second phase. The components are
separated by difference in volatility.
 In second technique, a second phase is added to the separation unit in the
form of solvent (mass-separating agent, MSA) that selectively dissolve or
alters the volatility of certain species in the mixture. An additional
separation step is usually required to recover the solvent for recycle.
 The third technique involves addition of solid particles/adsorbent (MSA) that
selectively adsorb certain species of the mixture. Subsequently, the
particles must be treated by another separation method to recover the
adsorbed species and regenerate the adsorbent for further use.
 The fourth technique imposes a barrier that allow the permeation of some
species over others. A mechanical energy (pressure difference, ESA) loss
accompanies the permeation.
 For all 4 techniques, mass transfer controls the rate of migration of species
from one phase to another, which limited by the thermodynamic
equilibrium between phases.
 Except for the 4th technique, the exiting phases do not approach
equilibrium, but separation occur strictly because of difference in the rate
of permeation through the membrane.
Criteria for Selection of Separation
Methods
 The development of a separation process requires the selection of :
 Separation method
o ESA and/or MSA
o Separation equipment
o The optimal arrangement/sequencing of equipment
o The optimal operating conditions (T & P)

Criterion 1: Phase condition of the feed

 The phase condition of the feed is always the first to be considered
 Whether the feed is a vapor, liquid or slurries/wet cakes/dry solids
 Vapor feeds: Partial condensation, Distillation under cryogenic
condition, Gas adsorption, Gas absorption, Gas permeation with a
membrane, Desublimation
 Liquid feeds: Flash or partial vaporization, Distillation, Stripping,
Extractive distillation, Azeotropic distillation, Liquid-liquid extraction,
Crystallization, Liquid adsorption, Reverse osmosis, ultrafiltration and
pervaporation with a membrane, Supercritical extraction
 Slurries, Wet Cakes, and Dry Solids: Slurry – filtration, centrifugation,
Wet cake – drying, Dry solid – leaching
Criterion 2: Separation factor
 Second consideration is the separation factor, which can be
achieved by the particular separation method for the separation
between two key components of the feed.
 Separating factor for separation of key component 1 from key
component 2 between phase I and phase II for single stage of
contacting is defined as:
𝐶1𝐼 /𝐶2𝐼
𝑆𝐹 = 𝐼𝐼 𝐼𝐼
𝐶1 /𝐶2
where Cij is a composition (mass fraction, mole fraction, or
concentration) of component j in phase I
 For effective separation, larger value of SF is desired.
 Value of SF is limited by thermodynamic equilibrium.
 Distillation process
o Using mole fraction as composition variable, and letting phase I as
vapor, phase II be liquid
o The limiting value of SF is given in term of vapor and liquid
equilibrium ration (K-values) by
𝑦1/ 𝑦2 𝑦1 /𝑥1 𝐾1
𝑆𝐹 = = = = 𝛼1,2
𝑥1 /𝑥2 𝑦2 /𝑥2 𝐾2
o where α1,2 is the relative volatility
 Liquid-liquid Extraction
o SF for LLE is referred to as relative electivity, β:
𝛾1𝐼𝐼 /𝛾2𝐼𝐼
𝑆𝐹 = 𝐼 𝐼𝐼 = 𝛽1,2
𝛾1 /𝛾1
o where phase II is usually MSA-rich phase and component 1 is more
selective for MSA-rich phase than component 2.
o In general, MSA for LLE and extractive distillation are selected
according their ease of recovery and to achieve large value of SF.
 Absorption or Stripping
o Unless value of SF ≥ 10, these operations cannot achieve sharp
separation between two components.
o These operation are widely used for preliminary or partial
separations where the separation of one key component is sharp,
but only a partial separation for the other key component
𝑛𝑖𝐼
o Recovery factor, 𝑅𝐹 =
𝑛𝑖𝐹

o where n is mole/mass, I is the product rich in I, and F is the feed.

 Adsorption
o Separation factor for adsorption depend on either difference in rate of
adsorption or adsorption equilibrium
o Concentrations are those at equilibrium with adsorbent and in the bulk fluid
external to the adsorbent particle.

 Membrane separation
o SF is governed by relative rate of mass transfer in term of permeabilities
rather than by equilibrium consideration.
𝑃𝑀1
𝑆𝐹 =
𝑃𝑀2
o where PMi is the permeability of species i.
o membrane separation should be considered as alternative to adsorption
process
 When seeking a desirable SF, avoid conditions:
o Extreme temperature that require refrigeration or damage heat-sensitive
materials
o Pressures that require compression or vacuum
o MSA concentrations that require expensive mean to recover MSA

 In general, employing ESA are economically feasible than MSA.

 At low value of SF (1.05 < SF < 1.10), ordinary distillation still the economic
choice.
 If only a trace/small amount of one component is present in a mixture,
adsorption/absorption/ stripping process is preferred.
Criterion 3: Reason for separation
 Final consideration in the selection of a separation method is the reason for
separation.
 Possible reason:
I. purification of a species or group of species
II. removal of undesired constituent,
III. recovery of constituent for subsequent processing or removal.
Sequencing of Ordinary Distillation for
Separation of Nearly Ideal Liquid Mixture
 Multicomponent mixtures are often separated into more than two
products, which may require a sequence of two or more separators.
 For nearly ideal feeds, the most economical sequence will often include
only ordinary distillation column provided that the following conditions hold:
I. The relative volatility between the two selected key components for separation
in each column is higher than 1.05.
II. The reboiler duty is not excessive.
III. The tower pressure does not cause the mixture to approach its critical
temperature.
IV. The overhead vapor can be at least partially condensed at the column pressure
to provide reflux without excessive refrigeration requirement.
V. The bottoms temperature at the lower pressure is not so high that chemical
decomposition occurs.
VI. Azeotropes do not prevent the desired separation
VII. Column pressure drop is tolerable, particularly if operation is under vacuum.
 Initial consideration is usually given to a sequence of ordinary distillation
columns, where a single feed is separated into two product stream,
distillate and bottom.
 Even if a sequence of ordinary distillation column is used, not all columns
able to give nearly pure products.
 It takes a sequence of two ordinary distillation columns to separate a
mixture into three products, and so on.
 Heuristics for determining Favorable Sequence
1. Remove thermally unstable, corrosive, or chemically reactive components
early in the sequence
2. Remove final products one-by-one as distillates, following the direct
sequence ranked by relative volatility/boiling point.
3. Sequence separation points to remove, early in the sequence, those
components of greatest molar % in the feed.
4. Sequence separation point in order of decreasing relative volatility so that
the most difficult splits are made in the absent of the other components.
5. Sequence separation points to leave last those separations that give the
highest purity product.
6. Sequence separation points that favor near equimolar amounts of distillate
and bottoms in each column.

 Heuristics 2-6 are consistent with observations about the effect of the
nonkey components on the separation of two key components.
 These nonkey components can increase the reflux and boilup
requirements, which in turn, increase column diameter, number of trays
and rebolier heat duty