3.3 Separations-Part I

CHAPTER 3
PROCESS DESIGN AND SAFETY

3.1 Safety
3.2 Case study on process design and safety
3.3 Chemistry and separations
3.4 Unit ratio material balance
3.5 Detailed flow sheet
Chemical Engineering Design
Course Outcome
Ability to explain and identify process design and safety.
3.3 CHEMISTRY &

SEPARATION
PART I
2012 G.P. Towler / UOP. For educational use in conjunction with

Towler & Sinnott Chemical Engineering Design only. Do not copy
Separation Processes
Separation processes are needed for feed pretreatment,
product recovery and waste processing
Most separations are based on moving a component from
one phase to another and then segregating the two phases
Driven by activity gradient as phases try to reach equilibrium
Affected by rates of mass transfer and heat transfer

Separation Specifications
P, yA, yB
Product enriched in A
F, zA, zB
R, xA, xB
Recovery: How much of the desired component made it
to the stream it was supposed to be in:
P yA
P yA
Recovery of A
F z A P yA R xA

Separation Specifications
P, yA, yB
Product enriched in A
F, zA, zB
R, xA, xB
Purity: The concentration of desired component in the
stream it was supposed to be in:
Purity of A in product = yA

Impact of Separation Specifications

Cost
Tighter specifications lead to higher cost:
90
99
99.9
99.99
Purity or Recovery (%)
Final product must meet purity specifications

Set by ASTM, USP, etc.
Recycles sometimes have purity specifications

e.g. to protect catalyst from contaminants or poisons
Product that is not recovered is lost profit and also increased waste
cost: separation recovery factors into plant yield
Vapor-Vapor Separations
Membrane
Based on differences in relative
permeability of gases
Used for H2/CH4, CO2 removal,
air separation
Absorption
Using a liquid solvent
in an absorberstripper loop
Used for acid gases,
drying, water wash
Adsorption
Adsorb components selectively on a solid
Regenerate sorbent by temperature swing
(TSA) or pressure swing (PSA)
Used for air separation, H2/CH4, most
separations involving low concentrations
Adsorption
One component from vapor phase preferentially adsorbs onto
the surface of a solid adsorbent
Two types of adsorption:
Reversible:
Usually physisorption
Adsorbed component can be released by decreasing pressure or increasing
temperature
Sorbent can be regenerated and used in multiple cycles, hence temperature-swing
adsorption (TSA) and pressure-swing adsorption (PSA)
Irreversible:
Usually chemisorption
Adsorbed component usually reacts irreversibly with solid
Low concentrations can be achieved, but solid is difficult to regenerate
Used for contaminant removal guard beds

Concentration Profiles During

Adsorption
Gas mixture A + B
Concentration of B on sorbent
Concentration
profile moves
down the bed
during adsorption
t1
t2
tB
Distance down sorbent bed

Purified gas A

At time tB
breakthrough of
the adsorbed
component
occurs and it
begins to appear
in the outlet gas
Irreversible Adsorption
Feed
= open valve
= closed valve
Product
Two guard beds can be used in parallel so that when Bed 1

nears breakthrough the process flow can be switched to Bed 2
Some adsorbent will be wasted, as beds cannot be run close
to breakthrough for fear of contaminant slippage

Irreversible Adsorption: Lead-Lag

Guard Bed System
Feed
= open valve
= closed valve
Product
Alternative arrangement has beds in series

When upstream bed reaches breakthrough, downstream bed is still OK.
Upstream bed can be taken offline, reloaded and brought back into
downstream service, etc.
Makes more efficient use of adsorbent
Guard Beds for Mercury Capture

Mercury occurs in
natural gas and
light oils
It must be
removed to
protect
equipment and
catalysts
Source: UOP
Reversible Adsorption: Isotherms

T2
T2 > T1
Partial pressure
T1
p1
p2
m2
m1
Mass adsorbed (g/g sorbent)
Reversible adsorption exploits changes in loading with

pressure or temperature

T2
T2 > T1
Partial pressure
T1
Adsorb at (p1, T1) gives

loading m1
p1
Pressure Swing:
Decrease pressure to p2 and
loading decreases to m2
p2
m2
m1
Delta loading = m1 m2
(kg/kg sorbent)
PSA: cycle between high and low pressure to load and

regenerate the adsorbent

T2
T2 > T1
Partial pressure
T1
Adsorb at (p1, T1) gives

loading m1
p1
Temperature Swing:
Increase Temperature to T2
and loading decreases to m2
p2
m2
m1
Delta loading = m1 m2
(kg/kg sorbent)
TSA: cycle between low and high temperature to load

and regenerate the adsorbent
PSA and TSA Systems

PSA
Shorter cycle time (no
heating or cooling)
Typically 5 60 mins
Multiple beds needed for

high recovery, purity
Use pressure balancing and
purge to get better recovery
and purity
8, 10, 12, 16 bed plants
Applications: hydrogen
purification, air separation

TSA
Longer cycle time for heating
and cooling of bed and vessel
Typically 60 200 mins
Additional equipment needed

for heating & cooling
Often use a purge gas for regen,
e.g. steam, N2 or a slip-stream of
product
Fewer beds (no need to

pressure equalize)
Applications: gas drying, VOC
capture, CO2 removal in cryo
plants
12-Bed PSA Unit

Surge Tank
Adsorber Vessels
Valve Skid
Source: UOP
PSA Cycle
Bed
A
1,2,3
PP
D
P
R
Time
absorb
equalize
provide purge
desorb
purge
repressure
From U.S. 4,381,189 Pressure Swing Adsorption System and Process
Pressure equalization steps reduce the amount of gas lost during

depressurization and hence improve recovery
Repressurization is done using product gas to improve purity
Some steps are co-current, some counter-current, to exploit
concentration profiles in the bed
Many different cycles have been invented see patent literature for
examples
Preliminary Design of PSA Units

1. Delta loading across cycle depends on the adsorbent selected, the
temperature of operation and the pressure cycle use isotherms to
determine delta loading
2. Select number of beds (more beds = more equalization steps, higher
recovery, higher purity)
3. Select cycle time and time in adsorption step, ta
4.
Mass of adsorbent per bed Mass flow rate of adsorbed component
ta
delta loading bed loading factor
5. Size each bed as a cylindrical pressure vessel
Bed loading factor = fraction of bed loaded at end of adsorption stage ~ 0.8 to 0.9
6. Add costs for valve skids, surge tank
(Detailed design need to consider mass transfer rates and dynamics
much more complex analysis)

Membrane Separation
Thin membranes of polymer or metal can be used to separate
gases:
Different species diffuse through a thin membrane at different rates:
Different gases have different solubility in metal or polymer
Permeate passes through the membrane and becomes

enriched in faster or more soluble species
Retentate does not pass through membrane and becomes
enriched in slower or less soluble species
Membranes have relatively low cost, but cannot obtain high
purity or recovery
Membranes are therefore widely used for bulk separation of
gases
Asymmetric Membrane
Dense
layer
0.1 to 1.0 m
Porous
support
0.1 to 1.0
mm
(not to scale)
Polymer membranes are usually cast as asymmetric membranes

Thin, dense, active layer is supported on a thicker stronger porous layer
Backing cloth is used in some cases as support for active layer

Hollow Fiber Membranes

Feed
One hollow fiber (of

thousands)
Permeate
Potting
Retentate
Membrane cross
section
Membranes are cast as long thin fibers

A bundle of fibers is set into a resin (potting) that effectively forms a
tubesheet
Feed is fed shell-side and permeate withdrawn from inside the fibers

Flat Sheet (Spiral Wound) Membranes
Membranes are cast as sheets

Sheets are glued back-to-back along edges to form an
envelope and attached to a perforated tube
The assembly is then rolled up into a spiral-wound module
Gas Separation Membranes

SEM, TEM, STEM can be used for
microscopic analysis
Note asymmetric structure
Thin selective skin
Porous support layer

UOP 5565M-25
Membrane Flux and Permeability

Flux of species i through the membrane is proportional to
partial pressure gradient:
Pi
M i pi , f pi , p
Mi = molar flux of component i (mol/m2.s),

Pi = permeability of membrane for omponent i (mol/m.s.bar),
= membrane thickness (m),
pi,f = local partial pressure of component i on feed side (bar),
pi,p = local partial pressure of component i on permeate side (bar)
Proportionality constant is the permeability divided by

membrane thickness
Ratio of permeabilities of two species is the selectivity of
the membrane for species i relative to species j
Pi
S ij
Pj
Membrane Flow Pattern

Integration of the flux
equation along the
membrane depends on
the flow pattern
Note that only flat sheet
membranes can be used
in cross-flow mode
Neither flat sheet nor
hollow fiber membranes
can use a sweep gas

Countercurrent
Cocurrent
Cross-flow
Membrane Process Performance

Membranes usually give low recovery of permeate species
(<95%, often <90%)
Need to maintain a high enough partial pressure on retentate side
to give a reasonable flux at the outlet of the unit
If outlet partial pressure is low, flux is low and area required
becomes large and costly
Unless the selectivity is very high, membranes usually give

low purity on permeate side (<98%, often <95%)
Hence membranes are used for bulk separations:
Air separation (hollow fiber)
CO2 rejection from natural gas (spiral wound)
H2 recovery from mixtures with methane (hollow fiber)
Permeate Recycle
Retentate
Feed
Permeate
Permeate from 2nd module is recycled to feed of 1st module

First module can now run under conditions that maximize permeate
purity (high selectivity) and we dont have to worry about recovery
Second module can run under conditions that maximize recovery (high
flux) and we dont have to worry about purity
Partial pressure of desired component in 1st module is increased

Retentate Recycle
Feed
Retentate
Permeate
Retentate from 2nd module is recycled to feed of 1st module

Permeate now goes through two membranes in series, so final permeate
purity is increased
First module can run at higher flux, lower selectivity as it makes a rough
separation
An extra compressor is needed between the membrane stages

Membrane Modules
UOP Separex
modules for rejecting CO2 from natural gas

Vapor-Liquid Separations
Flash
Single stage thermal
& phase eqbm
Evaporation
Single stage removal of
volatile solute or solvent
Distillation
Multiple stage separation
between identified light key
& heavy key components
Fractionation
Separation of
multicomponent
mixture into fractions by
boiling ranges (e.g. in oil
refining)

Absorption
Removal of vapor
component using
non-volatile solvent
Stripping
Multi-stage removal
of volatile solute
from solvent
Multi-stage: see next lecture
See heat exchange lectures
Vapor-Liquid Flash Drums
Flash or knockout drums are widely used in chemical plants:

Downstream of condensers and coolers
Upstream of compressors and between compressor stages
As reflux drums on columns
In relief systems
Design function is to separate liquid drops from vapor and

prevent vapor blowing out into liquid-filled lines by
maintaining liquid level control
There will usually be ~1 to 2% liquid entrainment in the
vapor from a knockout drum unless a demister is used.
Vertical Flash Drum
Vessel diameter is chosen to give

vapor velocity that is less than
terminal velocity of drops
ut 0.07[(L v)/v]1/2
Use 0.15 ut if there is no demister

Allow 1 diameter above feed and
at least 0.6 diameters below feed
for settling, also allow 0.4
diameters for demister
Height of liquid depends on level
control

Liquid Level Control Bands

Level control needs to allow for some natural variation
in liquid level due to splashing, etc.
Alarms must not be set too close to normal operating
level or they will be a nuisance (& will be ignored)
Operators need time to respond to alarms before
shutdown
A typical assumption is about 2
LAHH shutdown trip
minutes between alarm and trip,
LAH alarm
so allow 10 minutes of liquid
residence time below feed
Normal operating band
But note: midpoint of normal
operating band should be > Dv/2
LAL alarm
below feed point, so if 5 mins of
LALL shutdown trip
liquid holdup gives height < Dv/2,
use half a diameter to the
midpoint and 5 min holdup below.
5 min of
liquid or Dv/2
5 min of
liquid
Horizontal Flash Drum
Bigger area for settling + more space for liquid holdup

Trade-off is higher plot space and stronger foundations needed to support vessel
Often used when process control demands some liquid inventory, e.g. reflux
drums
Design is more complex than vertical drum see Ch16
Liquid-Liquid Separations
Decanting
Single stage thermal
& phase eqbm
Extraction
Multi-stage
contacting of two
liquid phases

Mixer-Settler
Single theoretical stage
extraction process
Often 2 or 3 stages are still
cheaper than a column
Membrane
Based on differences in relative
permeability of components
Membrane can be used to keep
two solvents from mixing
Horizontal Decanter
Light
liquid
Vent
Heavy
liquid
Feed
Dispersion
band
Drain
Design is similar to knockout drum: allow droplets to settle and

provide adequate holdup for level control see Chapter 16
Siphon take-off can control level without instruments if densities are
constant

Multistage Extraction: Sulfolane

Process
Used for L/L extraction of

benzene and toluene from
gasoline using sulfolane solvent
Recovery of Components from

Liquid Solutions
How many methods can you think of?
Distillation
Precipitation
(a.k.a. salting out)
Extraction
Evaporation
Membranes
(Reverse osmosis)
Crystallization
Ion Exchange
Adsorption
(Chromatography)
You should have direct experience with many of these

in Organic Chem and Unit Ops labs!
Circulating Magma Crystallizer
Most widely used industrial

scale crystallizer
Supersaturation can be
achieved by evaporation or
cooling (figure shows
evaporative type)
Usually designed in
consultation with a vendor
Cost correlates with heat
transfer area as most of the
metal is in the heat
exchanger

Oslo Crystallizer
Only the liquor circulates

through the exchanger
Allows growth of larger
and more regular
crystals (less shear)
Crystals are only
agitated by circulating
liquor
Figure shows
evaporative type, but
can also use cooling to
achieve supersaturation

Industrial Chromatography
Chromatography is a very versatile separation process,
particularly for
Mixtures of close-boiling compounds that are expensive to separate
by distillation or crystallization (e.g. xylenes, glucose-fructose)
Thermally sensitive compounds that cannot be distilled or crystallized
(many biological products, natural extracts, flavors, etc.)
Many process variations have been developed

High recovery (>99%) and high purity (>99.9%) can be
achieved
Cost depends on process scheme and whether sorbent
(stationary phase) and eluent (mobile phase) can be reused
For quality control reasons used sorbent and eluent are often
discarded in the pharmaceutical industry
Batch Chromatography
Eluent
Feed
Metering pump
(discontinuous
operation)
Conc. of
dissolved
material
in solvent
at A
Lights
Product
Time
Chromatography
column
Heavies
tcycle
Lights
Product
A
Heavies
A pulse or batch of feed is introduced into the column, then washed through using an eluent
The fraction that contains the desired product is retained and the rest discarded
If sorbent cost is low, sorbent may be discarded instead of eluting heavies

Variations on Batch Chromatography
Solvent gradient chromatography

Eluent composition is changed over time to change solute-sorbent
interaction and elute different species
HPLC (high performance liquid chromatography)

High pressure pumps and long packed columns of sorbent
Gel permeation chromatography

Stationary phase pore structure excludes the product, so heavies come out
first: gives faster cycle time
Affinity chromatography
Highly specific interaction between solute and sorbent, e.g. antibody-antigen
Example: Protein A chromatography for recovery of monoclonal antibodies
Affinity chromatography is one of the most widely used methods in
recovering large biologically derived molecules

Continuous Countercurrent
Chromatography
Zone
Height
Fresh
desorbent
I
hE
Extract
Feed
II
III
hF
hR
Raffinate
IV
0
Net desorbent
Solids
recirculation
Concentration in liquid
If solids move then more strongly adsorbed component A can be separated from less strongly adsorbed B

Countercurrent Chromatography
Continuous movement of solids is difficult to accomplish
Good sorbents such as zeolites and gels do not flow well or suffer
attrition
Instead, solids movement can be simulated using a rotary

valve or set of switching valves
UOP Sorbex process
Developed for separating normal paraffins in 1960s
Now mostly used for recovering p-xylene from mixed xylenes and
separating glucose and fructose to make High Fructose Corn
Syrup
Simulated Moving Bed chromatography is now being

used more widely in pharmaceutical separations
UOP Sorbex Process
AC
RV
EC
RC
Adsorbent column
Rotary valve
Extract column
Raffinate column
Questions ?


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CHAPTER 3

PROCESS DESIGN AND SAFETY

Chemical Engineering Design

Chemical Engineering Design

3.3 CHEMISTRY &

2012 G.P. Towler / UOP. For educational use in conjunction with

Chemical Engineering Design

2012 G.P. Towler / UOP. For educational use in conjunction with

Chemical Engineering Design

2012 G.P. Towler / UOP. For educational use in conjunction with

Chemical Engineering Design

2012 G.P. Towler / UOP. For educational use in conjunction with

Chemical Engineering Design

Impact of Separation Specifications

Tighter specifications lead to higher cost:

Purity or Recovery (%)

Final product must meet purity specifications

Recycles sometimes have purity specifications

Chemical Engineering Design

Chemical Engineering Design

2012 G.P. Towler / UOP. For educational use in conjunction with

Chemical Engineering Design

Concentration Profiles During

Distance down sorbent bed

2012 G.P. Towler / UOP. For educational use in conjunction with

Two guard beds can be used in parallel so that when Bed 1

2012 G.P. Towler / UOP. For educational use in conjunction with

Chemical Engineering Design

Irreversible Adsorption: Lead-Lag

Alternative arrangement has beds in series

Chemical Engineering Design

Guard Beds for Mercury Capture

Chemical Engineering Design

Reversible Adsorption: Isotherms

Mass adsorbed (g/g sorbent)

Reversible adsorption exploits changes in loading with

Chemical Engineering Design

Reversible Adsorption: Isotherms

Adsorb at (p1, T1) gives

Mass adsorbed (g/g sorbent)

PSA: cycle between high and low pressure to load and

Chemical Engineering Design

Reversible Adsorption: Isotherms

Adsorb at (p1, T1) gives

Mass adsorbed (g/g sorbent)

TSA: cycle between low and high temperature to load

Chemical Engineering Design

PSA and TSA Systems

Multiple beds needed for

2012 G.P. Towler / UOP. For educational use in conjunction with

Additional equipment needed

Fewer beds (no need to

12-Bed PSA Unit

Chemical Engineering Design

From U.S. 4,381,189 Pressure Swing Adsorption System and Process

Pressure equalization steps reduce the amount of gas lost during

Chemical Engineering Design

Preliminary Design of PSA Units

Mass of adsorbent per bed Mass flow rate of adsorbed component

2012 G.P. Towler / UOP. For educational use in conjunction with

Chemical Engineering Design

Permeate passes through the membrane and becomes

Chemical Engineering Design