3.1 Chemistry & Separation 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.
Chemical Engineering Design

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 Chemical Engineering Design
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 y A  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
PSA TSA
• Shorter cycle time (no • Longer cycle time for heating
heating or cooling) and cooling of bed and vessel
– Typically 5 – 60 mins – Typically 60 – 200 mins
• Multiple beds needed for • Additional equipment needed
high recovery, purity for heating & cooling
– Use pressure balancing and – Often use a purge gas for regen,
purge to get better recovery e.g. steam, N2 or a slip-stream of
and purity product
– 8, 10, 12, 16 bed plants • Fewer beds (no need to
• Applications: hydrogen pressure equalize)
purification, air separation • Applications: gas drying, VOC
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
• 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 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
Enlarged cross section Membrane envelopes
Dense
Porous
Porous
Dense
Feed
Perforated tube Retentate
Permeate Permeate
• 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:
M i   pi , f  pi , p 
Pi 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
Feed
Countercurrent
• Integration of the flux
equation along the Permeate
membrane depends on
the flow pattern Retentate
Feed
• Note that only flat sheet Cocurrent
membranes can be used
in cross-flow mode Permeate
• Neither flat sheet nor Retentate
hollow fiber membranes Feed

Cross-flow
can use a sweep gas
Permeate Permeate
Retentate
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 don’t have to worry about recovery
• Second module can run under conditions that maximize recovery (high
flux) and we don’t 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

Membrane Modules
UOP Separex modules for rejecting CO2 from natural gas

Vapor-Liquid Separations
Flash Evaporation
Single stage thermal Single stage removal of
& phase eqbm volatile solute or solvent
See heat exchange lectures
Distillation Absorption
Multi-stage: see next lecture

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

UOP Sorbex Process
AC Adsorbent column
RV Rotary valve
EC Extract column
RC Raffinate column

Questions ?


3.1 Chemistry &amp; Separation I

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3.1 Chemistry &amp; Separation I

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CHAPTER 3

PROCESS DESIGN AND SAFETY

Chemical Engineering Design

Ability to explain and identify process design and safety.

Chemical Engineering Design

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

• Separation processes are needed for feed pretreatment,

© 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

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

Perforated tube Retentate

• Membranes are cast as sheets

  = membrane thickness (m),

• Proportionality constant is the permeability divided by

• Neither flat sheet nor Retentate

hollow fiber membranes Feed

© 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

UOP Separex modules for rejecting CO2 from natural gas

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

Multi-stage: see next lecture

• 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

• 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

3.1 Chemistry & Separation I

3.1 Chemistry & Separation I