CH3080 Separations

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

Towler & Sinnott Chemical Engineering Design only. Do not copy Chemical Engineering Design
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
Tighter specifications lead to higher cost:
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 Absorption
permeability of gases Using a liquid solvent
Used for H2/CH4, CO2 removal, in an absorber-
stripper loop
air separation
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
t1 down the bed
t2
during adsorption
At time tB
breakthrough of
tB
the adsorbed
component
Distance down sorbent bed occurs and it
Purified gas A 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
T1
Partial pressure
p1
p2
m2 m1
Mass adsorbed (g/g sorbent)
Reversible adsorption exploits changes in loading with

pressure or temperature

T2
T2 > T1 Adsorb at (p1, T1) gives
T1 loading m1
Partial pressure
p1
Pressure Swing:
Decrease pressure to p2 and
p2
loading decreases to m2
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 Adsorb at (p1, T1) gives
T1 loading m1
Partial pressure
p1
Temperature Swing:
Increase Temperature to T2
p2
and loading decreases to m2
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
TSA
PSA
Longer cycle time for heating and
Shorter cycle time (no
cooling of bed and vessel
heating or cooling)
Typically 60 200 mins
Typically 5 60 mins
Multiple beds needed for Additional equipment needed for
high recovery, purity heating & cooling
Often use a purge gas for regen, e.g.
Use pressure balancing and
steam, N2 or a slip-stream of product
purge to get better recovery
and purity
Fewer beds (no need to pressure
equalize)
8, 10, 12, 16 bed plants
Applications: hydrogen Applications: gas drying, Volatile
purification, air separation Organic Content capture, CO2
removal in cryo plants

12-Bed PSA Unit
Surge Tank
Adsorber Vessels
Valve Skid
Source: UOP

PSA Cycle
A absorb
1,2,3 equalize
PP provide purge
Bed
D desorb
P purge
R repressure
From U.S. 4,381,189 Pressure Swing Adsorption System and Process

Time
Pressure equalization steps reduce the amount of gas lost during
depressurization and hence improve recovery
Re-pressurization 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 0.1 to 1.0

support 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-22
Membrane Flow Pattern
Countercurrent
Integration of the flux
equation along the
membrane depends on
the flow pattern
Note that only flat sheet Cocurrent
membranes can be used
in cross-flow mode
Neither flat sheet nor
hollow fiber membranes Cross-flow
can use a sweep gas

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
Retentate
Feed
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

Vapor-Liquid Separations
Flash Evaporation
Single stage thermal Single stage removal of
& phase eqbm volatile solute or solvent
Heat exchanger slides
Distillation Absorption
Multiple stage separation Removal of vapor
between identified light key component using
& heavy key components non-volatile solvent
Fractionation Stripping
Separation of Multi-stage removal
multicomponent of volatile solute
mixture into fractions by from solvent
boiling ranges (e.g. in oil
refining)
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 5 min of
so allow 10 minutes of liquid
liquid or Dv/2
residence time below feed
Normal operating band
But note: midpoint of normal
5 min of
operating band should be > Dv/2 LAL alarm
liquid
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.
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 Mixer-Settler
Single stage thermal Single theoretical stage
& phase eqbm extraction process
Often 2 or 3 stages are still
cheaper than a column
Extraction
Multi-stage Membrane
contacting of two Based on differences in relative
liquid phases permeability of components
Membrane can be used to keep
two solvents from mixing

Horizontal Decanter
Light Vent
liquid
Heavy
Feed liquid
Dispersion Drain
band
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 Membranes

(a.k.a. salting out) (Reverse osmosis)
Extraction Crystallization
Evaporation 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
Product
Eluent Feed Lights Heavies
Conc. of
dissolved
Metering pump material
in solvent
(discontinuous at A
operation)
tcycle
Time
Lights
Chromatography
column 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
Fresh
desorbent Zone
Height
I
hE
Extract
A II
S hF
Feed
B III
hR
Raffinate
IV
0
Concentration in liquid
Net desorbent Solids
recirculation
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


CH3080 Separations

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Separation Processes

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

Recovery: How much of the desired component made it

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

Purity: The concentration of desired component in the

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

Purity or Recovery (%)

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

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

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

Alternative arrangement has beds in series

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

Mass adsorbed (g/g sorbent)

Reversible adsorption exploits changes in loading with

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

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

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

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

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

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

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

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

Porous 0.1 to 1.0

Polymer membranes are usually cast as asymmetric membranes

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

Membranes are cast as long thin fibers

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

Membranes are cast as sheets

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

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

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

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

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

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

Flash or knockout drums are widely used in chemical plants:

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

Bigger area for settling + more space for liquid holdup

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

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

Design is similar to knockout drum: allow droplets to settle and

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

Used for L/L extraction of

Distillation Precipitation Membranes

Evaporation Ion Exchange Adsorption

You should have direct experience with many of these

Most widely used industrial

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

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

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

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

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

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

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

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