REACTOR DESIGN FIRST ORDER APPROXIMATION
-prediction of reactor performance, product
yields, etc.
-detailed discussion of kinetics, catalysis,
deactivation, mass transfer, etc.
REACTOR SIZING & COSTING
-estimate required volume: (1) from residence
time for non-catalytic reactors, (2) from catalyst space
velocity for packed bed catalytic reactors, (3) from
hydraulics and residence time for fluidized and slurry
reactors
-decide pressure vessel size and shape
-cost reactor shell as pressure vessel
-add extra costs for mixers, internals, etc.
REAL REACTOR DESIGN
-a lot more complicated than estimation of
reactor volume
-cost comes from reactor internals (mixers,
agitators, baffles, jackets, coils, external loops, and
catalyst handling)
-mixing and heat transfer performance are
difficult to model and understand, and have significant
effects on yield and purity.
IDEAL REACTORS (seldom attained but useful as approx)
CSTR (WMR)
-perfect mixing
-product and vessel contents are at
uniform T and concentration.
-material sees a distribution of
residence times.
PFR
-no axial mixing
-sharp residence time distribution
-matl flowing thru the reactor
experiences a profile of concentration and T.
REACTION KINETICS COMPLICATIONS
-seldom simple 1st or 2nd order rxns
-catalytic reactions mostly fitted with Langmuir-
Hinshelwood expressions (inhibition terms often
significant)
-mass transfer, mixing & equilibrium often limit
overall rate
-catalyst deactivation is often significant
-simple 1st order model usually adequate to
predict conversion but not for predicting by-product
yields or understanding catalyst behavior
MASS TRANSFER
-processes that often reduce the overall rate of
rxn to a slower rate than intrinsic kinetics
-limitations can occur (1) between phases V/L,
L/L, L/S, V/S, etc, (2) inside catalyst pores
-interphase transport strongly influenced by
interfacial area (particle, droplet or bubble size)
-we can often write as
=
where CA, concentration of the limiting reagent and keff,
is effective 1st order rate constant
-for an equilibrium reaction we have
= ( )
where CA*, equilibrium concentration
REACTOR HEAT BALANCE-design must account enthalpy
difference between feed and products, which come
from:
Heat of Reaction = ( )
Sensible Heat Change =
Latent Heat (from Phase Change) =
=
MIXING IN INDUSTRIAL REACTORS
Tubular Reactors
-almost always designed to be in turbulent flow
-static mixer usually placed immediately
downstream of any feed point to ensure reactor
contents are mixed quickly
-static mixers consists of baffles to iduce
turbulence
Stirred Reactors
-agitator consists of impeller mounted on shaft
driven by motor
-motor usually mounted above the reactor
-reactor contains baffles or internals to induce
turbulence and prevent swirling of contents
Impeller Types: Straight Blade, Pitched Blade,
Hydrofoil, Propeller (Turbine), Helical Ribbon, Anchor,
Rushton Turbine and Screw
Baffles
-baffles prevent liquid to swirl and
develop vortex
-usually 4 baffles are placed around the
perimeter (1/10 of diameter and located 1/20 of
diameter from wall
Impeller Reynolds Number
-can determine extent of mixing and
correlate power consumption and heat transfer to shell
2
-defined as =
where Da, agitator blade diameter, N agitator speed
(revs/s), density (kg/m3) and viscosity (Ns/m2)
Power Consumption, P (W or Nm/s)
-can be made into Np (dimensionless)
which can be correlated against Re
=
3 5
-for Re>103, power number is constant
and a function of impeller type (see Perrys)
 Non-Ideal Flow and Mixing
-simple correlations are adequate if (1)
dead zones cannot be tolerated because of purity,
safety, etc (2) reactor internals are complex (3) reaction
selectivity is very sensitive to mixing
-it is necessary to carry out more
sophisticated analysis of mixing using: (1)
computational fluid dynamics to model reactor (2)
physical modeling (cold flow) experiments and (3)
tomography methods to look at performance of real
reactor
COMPUTATIONAL FLUID DYNAMICS
-calculate mass, energy and momentum
balances discretely across 2D or 3D grid of points as a
function of time
-include effects of heat and mass transfer,
bubbles and suspended solids
-boundary conditions on grid are set up to
reflect reactor geometry
-results plotted as color coded pictures of
velocity, mass transfer coefficient, void fraction, shear,
etc., that let designers see where weak points of the
design to propose changes to the design geometry
REACTOR TOMOGRAPHY
-various methods used for non-invasive
examination of reactors in-situ (1) Cat Scanning(validate
MTO reactor catalyst distribution), Ultrasound, Gamma
Scanning (validate axial catalyst density profile) (2)
carried out by specialist contractors and not cheap
NON-ISOTHERMAL LIQUID PHASE REACTORS
-low heat duties achieved with a jacketed vessel
-intermediate duties require internal coil
(impacts mixing, fouling and cleaning)
-high duties require external heat exchange
circuit
ESTIMATING HEAT TRANSFER COEFFICIENT IN STIRRED
TANK REACTORS
-reactor side heat transfer coefficient depends
on rate of agitation, reactor internals and coil design
(case specific, detailed understanding requires CFD or
physical modeling)
-first approximation for jacket for design
purposes:
= Pr 0.33 hydraulics
where (from 19.8) range 0.36-1.4, range 0.5-0.75
typically 0.67, Re impeller Reynolds number and
Nu=hd/k where d is reactor internal diameter
NON-ISOTHERMAL VAPOR PHASE REACTORS
-heat transfer coefficients usually too low to use
jackets or internal coils
-external heating or cooling loops are common
-in endothermic processes, reaction is carried
out in a fired heater tube: (1) design is fired heater
design (2) allow extra residence time in radiant zone if
necessary
HOW WOULD YOU GET VAPOR TO REACT WITH
LIQUID?
SPARGED REACTORS
Sparger-a pipe with holes for bubbles to flow
out
-for smaller bubbles, porous pipe
diffuser can be used
-balance between bubble break-up and
coalescence is quickly established
-if small bubble size is to be maintained then
additional shear is needed
-designer must allow disengaging space at top
of reactor, or entrainment will be excessive
Sparger as Agitator
-if gas flow rate is large, then gas flow
can be used as primary means of agitation
-For agitating open tank full of water at
1atm the air rates are (Perrys):
Degree of agitation Liquid depth 9ft Liquid depth 3ft
Moderate 0.65 1.3
Complete 1.3 2.6
Violent 3.1 6.2
LIFT REACTORS AND LOOP REACTORS
-if sparger provides agitation, then baffle is
added to give better liquid circulation and ensure
mixing of feeds
-can be used for very large flow rates, where
liquid vapor is driven by the vapor flow
-equipment design governed by 2-phase flow
UOP/Paques Thiopaq Reactor
-biological desulfurization of gases with
oxidative regeneration of bugs using air
-reactor at AMOC in AI Iskandriyah has
six 2m downcomers inside shell
REACTION IN V-L CONTACTING COLUMNS
-trayed or packed columns can be used to
contact vapor and liquid for reaction
 -packing may be catalytically active or Advantages of Biological Systems
conventionally inert (1) Products can only be made by biological routes
-design similar to absorption columns, but must (2) Large molecules (protein) can be made
allow for enhancement of absorption due to reaction (3) Can be of very high selectivity for product
V-L REACTION KINETICS (4) Products are often very valuable
(Pharmaceutical ingredients)
(5) Selective conversion of biomass to chemicals
(6) Well established for food and beverage
processes
ENZYME CATALYSIS
-if liquid B is present in excess, we can assume
-enzymes are biocatalysts and can be isolated
rxn is pseudo-1st order in vapor A
from host cells (1) low cost enzymes are used once
= 2 1
-start by assuming reaction in bulk>>reaction in through (2) high cost enzymes are immobilized for
mass transfer film reuse
-enzymes are usually proteins, most are
= (, , )
thermally unstable and loses structure at >60C, usually
= = 1 ,
active only in water over restricted range of pH and onic
Solving: , = ( , strength
1 + )
1 , 1 -Michaelis-Menten equation (Enzyme Kinetics)
so rate of rxn (flux)= = ,
1 + 1 +
We can define 2 regimes: =
+
(1) k1<<akL, rate approx k1CA,i where R is reaction rate, C the substrate concentration
-aka slow kinetic regime and , are constants
-rxn rate occurs with concentration that would Immobilization
be predicted by phase equilibrium -enzymes are sometimes adsorbed onto a solid
-design insensitive to increase in area or encapsulated in a gel without losing structure and
(2) k1>>akL, rate approx akLCA,i can then be used in a conventional fixed-bed reactor
-aka slow mass transfer regime -if enzyme is larger than the product molecule,
-rxn rate occurs at rate set by mass transfer w/ it can be contained in the reactor using ultrafiltration or
zero concentration in bulk liquid nanofiltration
-design sensitive to increase in area CELL GROWTH AND METABOLISM
Cell Growth
-for either of the slow regimes to occur we need Rate can be limited by:
reaction to occur in the bulk liquid (1) availability of primary substrate
Reaction in film<<Reaction in bulk usually glucose, fructose, sucrose or
Ak1CA,i<<akL(CA,i-CA,inf) carbohydrates
If CA,inf is approx 0, and =D/kL, where D (2) availability of other metabolites
is diffusitivity vitamins, minerals, hormones, enzyme
1
2
1 cofactors

1 (3) availability of oxygen and mass
-we define Hatta number, = transfer properties

-Hatta number is ~1 or greater then we have (4) Inhibition or poisoning by products
fast or instantaneous regimes and the analysis is or byproducts such as butanol fermentation
more complicated limited to few % due to toxicity
(5) high temperature due to inadequate
BIOREACTOR DESIGN heat removal and heat transfer properties of
Bioreactors have requirements that add reaction system
complexity -all factors exacerbated at higher cell
-usually 3 pairs cells, water and air concentrations
-need sterile operation Cell Growth & Product Formation in Batch
-often need heat removal at ambient conditions Fermentation
I. Innoculation. Slow growth as cells adapt to new
environment
 II. Exponential Growth. Growth rate proportional
to cell mass
III. Slow Growth as substrate or other factors
begin to limit rate
IV. Stationary Phase: cell growth rate and death
rate are equal
V. Decline Phase: cells die or sporulate, often
caused by product build up
- intracellular product accumulation is slow at
first (not many cells)
-product accumulation continues even after live
cell count falls (dead cells still contain product)
Cell Growth Kinetics
-cell growth rate defined by
=
where x is concentration of cells (g/L), t is time (s) and
g is growth rate (s-1)
-cell growth rate usually has similar dependence
on substrate concentration to Michaelis-Menten
equation, Monod equation:
=
+
where s is substance concentration (g/L), Ks is a
constant and max is maximum growth rate (s-1)
-Substrate consumption must allow for cell
maintenance as well as growth
= ( + )
where mi is rate of consumption of substrate i to
maintain cell life, g of substrate/g cells, Yi is yield of
new cells on substrate i, g of cells/g substrate
Metabolism and Product Formation
Product formation rate in biological processes is
often not closely tied to rate of consumption of
substrate as
(1) product may be made by cells at
relatively low concentrations
(2) cell metabolic processes may not be
involved in product formation
-usually not straightforward to write a
stoichiometric equation linking product to substrate
-product formation and substrate consumption
are linked through dependence of both on live mass in
reactor
= pharmaceutical grade products
where pl is product l concentration (g/L), kl is production
rate of product l per unit mass of cells
Where should we operate?
Intracellular product batch process
-batch operation continues into Phase V to
maximize the product assay (increase reactor
productivity)
-not economical to go to absolute highest
product concentration
Intracellular product, continuous process
-if product is harvested from the cells, we need
a high rate of production of cells and operate toward
the upper end of phase 3
Extracellular product, continuous process
--if product can be recovered continuously or
cells can be recycled, we can maintain highest
productivity by operating in phase IV
CLEANING AND STERILIZATION
Biological Processes must maintain sterile
(aseptic) operation
-prevent infection of desired organisms
with invasive species
-prevent invasion of natural strains that
interbreed with desired organisms and cause loss of
desired strain properties
-prevent contamination of product with
py-products formed by invasive species
-prevent competition for substrate
between desired organism and invasive species
-ensure quality and safety of food and
Design must allow for cleaning and sterilization
between batches/runs
-production plants are usually designed
for cleaning in place (CIP) and sterilization in place (SIP)
 Continuous or fed-batch plants must have sterile -expansion valve shaft is potential
feeds contamination source
-applies to all feeds that could support Heat Exchange Feed Sterilization
life forms, particularly growth media Feed
Coolant
-including air: use high efficiency Holding coil
particulate air (HEPA) filters
Reactors and tanks are fitted with special spray Sterile product
nozzles for cleaning
Minimize dead-legs, branches, crevices and
other hard-to-clean areas
Minimize process fluid exposure to shaft seals Condensate Steam

on pumps, valves, instruments, etc. to prevent -uses less hot and cold utility
contaminant ingress -possibility of feed to product contamination in
Operate under pressure to prevent air leakage exchanger
in (unless biohazard is high) -mainly used in robust fermentations e.g.
Cleaning Policy brewing
-typically multiple steps to cleaning cycle STIRRED TANK FERMENTER DESIGN
(1) wash with HP water jets -most common reactor for biological rxns
(2) drain -can be batch or continuous
(3) wash with alkaline cleaning soln -available from pressure vessel manufacturers
(4) drain in std sizes
Size m3 .5 1.0 1.5 3 5 7.5 15 25 30
(5) rinse with tap water Size gal 150 300 400 800 1500 2000 4000 7000 8000
(6) drain -316L stainless steel, but other metals are
(7) wash with acidic cleaning soln available
(8) drain -relatively easy to scale up from lab scale
(9) rinse with tap water fermenters during process development: high
(10) drain familiarity
(11) rinse with deionized water Agitator
drive
(12) drain Growth medium feed M Air
-each wash step will be timed to ensure vessel
Coolant out Coolant in
is filled well above normal fill line
Sterilization Policy Foam breaker
-sterilization, also a reaction process. Cell death
typically 0th or 1st order, but since we require that all Steam in (during sterilization)
cells are killed, it is treated probabilistically Cooling coil
Baffle
-typically 15min at 120C or 3min at 135C
-SIP carried out by feeding LP steam and holding Agitator blade

for prescribed time. During cool-down only sterile air

should be admitted
Sparger
-feed sterilization can be challenging for Condensate out
thermally sensitive feeds such as vitamins need to Product out

provide some addtl feed to allow degradation Design of Stirred Tank Fermenters
Continuous Feed Sterilization 1. Decide operation mode: batch or continuous
Steam -even in continuous, several reactors may be
needed to alow for periodic cleaning and re-
Mixer Holding coil innoculation
Feed
To vacuum 2. Estimate productivity (probable experimentally)
-establish cell concentration, substrate feed
Expansion Flash cooler rate, product formation rate per unit volume
valve per unit time
-determine number of std reactors to achieve
Sterile product
desired production rate: assume vessel is 2/3
-holding coil has sufficient residence time at
full
high T
 3. Determine run length: batch time or average
length of continuous rxn
4. Determine run length: batch time or average
length og continuous run
5. Determine mass transfer rate and confirm = =
( + )
adequate aeration
Purity-concentration of desired component in
6. Determine heat transfer rate and confirm
the stream it was supposed to be in
adequate cooling
=
7. Determine times for draining, CIP, SIP, cool Impact of Separation Specifications
down, refilling -tighter specifications cost higher wrt purity of
8. Recalculate productivity allowing for non- recovery
operational time: revisit step 2 if necessary -final product must meet purity and is set by
OTHER BIOREACTORS ASTM, USP, etc
Shaftless Bioreactors -Recycles often have purity specifications to
-use ga flow to provide agitation of liquid protect catalyst from contaminants/poisons
-eliminates pump shaft seal as potential source -product not recovered is lost profit and
of contamination increase waste cost (separation recovery factors into
-design requires careful attention to hydraulics plant yield)
Off gas to
vapor recovery Vapor-Vapor Separations
(1) Membrane -based on differences in relative
Liquid feed Gas feed Off gas to
permeability of gases
Liquid feed vapor recovery -used for h2/CH4, CO2 removal, air separation
Gas feed (2) Absorption -using a liquid solvent in an absorber-
Draft tube stripper loop
Sparger -used for acid gases, drying, water wash
Liquid product Liquid product (3) Adsorption absorb components selectively on a
Gas loop Reactor Baffle tube reactor solid
UOP/Paques Thiopaq Reactor -regenerate sorbent by T swing (TSA) or P 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
2 Types of Adsorption
(1) Reversible -usually physisorption
-adsorbed component released by
decreasing P or increasing T
-sorbent can be regenerated and used
in multiple cycles, hence T swing adsorption (TSA) and P
swing adsorption (PSA)
(2) Irreversible usually chemisorption
-adsorbed component reacts
irreversibly with solid
-low concentrations can be achieved,
-biological desulfurization of gases with but solid is difficult to regenerate
oxidative regeneration of bugs using air -used for contaminant removal guard
-reactor at AMOC in Al Iskandriyah has six 2m beds
diameter downcomers inside shell Concentration Profiles during Adsorption
SEPARATION PROCESSES -concentration profile moves down the
Recovery-amount of desired component in the bed during adsorption
stream it is supposed to be in
 -at time tB breakthrough of adsorbed get better recovery and stream of product
component occurs and begins to appear in the outlet purity and 8,10,12,16 bed -fewer beds as no need to
gas plants equalize P
Irreversible Adsorption -application in hydrogen -Application in gas drying,
-2 guard beds can be used in parallel so purification, air separation volatile organic content
that when Bed 1 nears breakthrough the process flow capture, CO2 removal in
can be switched to Bed 2 cryo plants
-some adsorbent wasted as beds cant PSA CYCLE P equalization steps reduce the
be run close to breakthrough for fear of contaminant amount of gas lost during depressurization and improve
slippage recovery
Irreversible Adsorption: Lead-Lag Guard Bed -re-pressurization sone using product
System gas to improve purity
-alternative arrangement has beds in -some steps are co-current, some
series counter-current, to exploit concentration profiles in the
-when upstream bed reaches bed
breakthrough, downstream bed is still OK. Upstream -many different cycles have been
bed can be taken offline, reloaded and brought back invented
into downstream service, etc. PRELIMINARY DESIGN OF PSA UNITS
-Makes more efficient use of adsorbent (1) Delta loading across cycle depends on the
Guard Beds for Mercury Capture mercury occurs in adsorbent selected, the T of operation and P cycle use
natural gas and light oils isotherms to determine delta loading
-must be removed to protect equipment and (2) select number of beds ( more bed means
catalysts more equalization steps, higher recovery, higher purity)
Reversible Adsorption: Isotherms (3) select cycle time and time in adsorption
-reversible adsorption exploits changes step, ta

in loading with P or T (4) =




Bed loading factor=fraction of bed loaded at
end of adsorption stage ~0.8 to 0.9
(5) Size each bed as cyclindrical P vessel
(6) Add costs for valve skids, surge tank
(detailed design-need to consider mass transfer rates
-PSA: cycle between high and low P to and dynamics-much more complex analysis)
load and regenerate the adsorbent Membrane Separation thin membranes of polymer or
metal can be used to separate gases: (1) different
species diffuse through a thin membrane at different
rates (2) different gases have different solubility in
metal 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
-TSA: cycle between low and high T to -membranes have relatively low cost but cannot
load and regenerate the adsorbent obtain high purity or recovery
PSA and TSA Systems -membranes are widely used for bulk
PSA TSA separation of gases
-shorter cycle time (no -longer cycle time, Assymetric Membrane polymer membranes
heating and cooling), typically 60-200min usually cast as asymmentric membranes
typically 5-60min -additional equipment for -thin, dense, active layer supported on
-multiple beds needed for heating and cooling, often a thicker stronger porous layer
high recovery, purity (use uses a purge gas for regen -backing cloth is used in some cases as
P balancing and purge to as in steam, N2 or a slip support for active layer
 Hollow Fiber Membranes membranes are cast
as long thin fibers
-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 cast as sheets
-sheets glued back-to-back along edges
to form an envelope and attached to a perforated tube
-assembly is rolled up into a spiral-
wound module
Gas Separation Membranes SEM, TEM, STEM
can be used for microscopic analysis
-Asymmetric Structure (1) thin selective
skin (2) porous support layer
Membrane Flow Pattern integration of the flux
equation along the membrane depends on the flow
pattern
-ONLY FLAT SHEET MEMBRANES CAN BE USED
IN CROSS-FLOW MODE
-neither flat sheet nor hollow fiber membranes
can use a sweep gas
Membrane Process Performance membranes give low
recovery of permeate species (<95% often <90%)
-need to maintain high enough partial P on
retentate side to give a reasonable flux at unit outlet
-if outlet partial P is low, flux is low and area
required becomes large and costly
-unless selectivity is very high, membranes give
low purity on permeate side (<98% often <95%)
-membranes are used for bulk separations: (1)
air separation, hollow fiber (2) CO2 rejection from
natural gas, spiral wound (3) H2 recovery from mixtures
with methane, hollow fiber
Permeate Recycle permeate from 2nd module recycled
to feed in 1st module
-1st module can run under conditions that
maximize permeate purity (high selectivity) and we
dont have to worry about purity
-partial P of desired component in 1st module is
increased
Retentate Recycle retentate from 2nd module is
recycled to feed of 1st module
-permeate goes through 2 membranes in series,
final permeate purity is increased
-1st module can run at higher flux, lower
selectivity as it makes a rough separation
-extra compressor needed between the
membrane stages
Vapor Liquid Separations
Flash single stage thermal & phase eqm
Evaporation single stage removal of volatile
solute or solvent
Distillation multiple stage separation between
identified light key & heavy key components
Absorption removal of vapor component using
non-volatile solvent
Fractionation separation of multicomponent
mixture into fractions by boiling ranges, as in oil refining
Stripping multi stage removal of volatile solute
from solvent
Vapor -Liquid Flash Drums
-flash or knockout drums widely used in
chemical plants as (1) downstream of condensers and
coolers (2) upstream of compressors and between
compressor stages (3) as reflux drums on columns (4) 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 knockout drum unless a
demister is used
Vertical Flash Drums vessel diameter chosen to give
vapor velocity less than thermal velocity of drops
= 0.07[( )/ ]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
diameter 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
-typical assumption is about 2min between
alarm and trip, allow 10min of liquid residence time
below feed
-MIDPOINT OF NORMAL OPERATING BANF
SHOULD BE >DV/2 BELOW FEED POINT, SO IF 5min OF
LIQUID HOLDUP GIVES HEIGHT <DV/2, USE HALF A
DIAMETER TO THE MIDPOINT AND 5min 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 more complex than vertical drum
Liquid-Liquid Separations
Decanting single stage thermal & phase eqm
Mixer-Settler single theoretical stage
extraction process
-often 2 or 3 stages are still cheaper
than a column
Extraction multistage contacting of 2 liquid
phases
Membrane based on differences in relative
permeability of components
-membrane can be used to keep 2
solvents from mixing
Horizontal Decanter design similar to knockout drum
that allow droplets to settle and provide adequate
holdup for level control
-siphon takeoff 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
Distillation, precipitation, membranes,
extraction, crystallization, evaporation, ion exchange,
adsorption
Circulating Magma Crystallizer most widely sed
industrial scale crystallizer
-supersaturation can be achieved by
evaporation or cooling
-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 thru the
exchanger
-allows growth of larger and more regular
crystals (less shear)
-crystals are only agitated by circulating liquor
-can use cooling to achieve supersaturation
Industrial Chromatography very versatile separation
process particularly for (1) mixtures of close-boiling
compounds that are expensive to separate by
distillation or crystallization (2) thermally sensitive
compounds that cannot be distilled or crystallized
-many process variations have been developed
-high recovery >99% and 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 a pulse or batch of feed is
introduced into the column, then washed through using
an eluent
-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
(1) Solvent Gradient Chromatography-eluent
composition changed over time to change solute-
sorbent interaction and elute different species
(2) HPLC (high performance liquid
chromatography) stationary phase pore structure
excludes the product, so heavies come out first: gives
faster cycle time
(3) Gel permeation 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
--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 as good
sorbents (such as zeolites and gels) do not allow flow
well o suffer attrition
-instead, solids movement can be simulated
using a rotary valve or set of switching valves
 -UOP Sorbex process developed for separating
normal parrafins in 1960 and is now used for recovering
p-xylene from mixed xylenes and separating glucose
and fructose to make High Fructose Corn Syrup
-Simulated moving bed chromatography is
being used more widely in pharmaceutical separations
BOILING AND CONDENSING
Pool Boiling
- Agitation by bubbles and natural convection
- Occurs in kettle reboilers
Flow Boiling
- Agitation by bubbles and forced convection
- Occurs in thermosiphon reboilers
- High fluid velocity
Thermosiphon Reboilers
- If we set the reboiler below the liquid level in
the column sump then the static head drives
liquid into the reboiler
- The difference in density caused by vaporization
then sets up a circulation, limited by pressure
drop
- Typically design for about 25 to 33%
vaporization per pass
- Thermosiphon orientation can be vertical
(tubeside flow) or horizontal (shellside flow)
- Horizontal is usually cheaper, but vertical
handles dirty fluids better
Flow regime in Thermosiphon Tubes
- Different flow regimes occur as vapor/liquid
ratio increases
- Slug flow is undesirable as it causes noise and
vibration, but is also unavoidable in vertical
thermosiphons
- Annular flow is avoided by designing for <33%
vaporization
Kettle Reboilers
- More expensive than horizontal thermosiphon
a. Larger diameter shell for same duty
b. Additional liquid outlet nozzle allows for
blowdown
c. TEMA types are (A or B) K (T or U)
- often used as steam regenerator because of
built in separator for vapor and allowance for
blowdown
Stab-in Reboilers
- the tube bundle can sometimes be fitted inside
the column sump: this saves a shell
- this behavior is similar to kettle reboilers
- designer has to make sure there is enough
sump height to give good level control and
pump NPSH w/o exposing tubes
Boiling Heat Transfer Coefficient (HTC)
I. Natural Convection heat transfer
II. Nucleate boiling w/ agitation by bubbles
III. Nucleate boiling w/ unstable film
IV. Stable film boiling
V. Radiant heat transfer
- As delta T between wall and fluid increases, h
increases at first due to bubbles, but then vapor
blankets the surface and the heat transfer
coefficient falls
- For fired boilers this can lead to tube failure
- Avoiding film boiling by limiting design to
maximum critical flux
Enhancement of Boiling Heat Transfer: UOP High Flux
Tubing
- Porous boiling surface
- Coating thickness of 0.127mm 0.381mm
- Strong metallurgical bond
- Interconnecting channels or re-entrant sites
- Boiling performance ~ 10x greater than bare
tube
- Overall performance ~ 2-5x greater than bare
tube
High Flux Tube Products
- ID Coated (OD bare or fluted)
- OD Coated (ID Bare or Finned)
Applications of High Flux
- Reboilers
a. Thermosiphons (TEMA type H, J or X)
b. Kettles
c. Stab-in bundles
- Condensers (kettles)
a. Boiling refrigerant
Condensing Heat Transfer
- Important for condensers and heaters that use
condensing steam
- Condensing behavior also occurs in many heat
exchangers if a vapor is cooled below the dew
point
Two Types of Condenser
a. Total Condenser
- no incondensable materials in vapor phase
- heat transfer coefficient determined by thermal
resistances only
b. Partial Condenser
- Some vapor components dont condense
- HTC determined by thermal and mass transfer
resistances
- Therefore much lower h.t.c
- Condensing molecules (eg water) have to
diffuse thru noncondensibles (eg air)
- Diffusion resistance decreases coefficient (big
difference to size of exchanger)
 - Calculation of condensing coefficients is
complex, particularly when coupled with
diffusion resistances, usually done using HX
design programs
- need to design for accumulation of
noncondensibles even in total condensers
a. provide a vent at the top of the exchanger
b. manually vent as often as required by
experience
- to keep noncondensibles out of steam system,
boiler feed water is degassed by stream
stripping
Bundle Effects on Heat Transfer
- liquid condensate film
- tubes in bundle
- condensate draining from tubes above creates
constant rippling and turbulence which
improves condensing coefficient
- condensate draining from tubes above
increases condensate level on tubes below
which decreases condensing coefficient
Enhancement of Condensing Heat Transfer: UOP High
Cond Tubes
a. mechanical enhancement
- applied to tube OD
b. optimized fin profile
- modified fins
- high extended area
- improves condensate drainage
- minimized liquid condensate film thickness
Process Heaters and Coolers
- choice of heater depends on temp and heat
load
a. high T (>250 C) usually fired heater or hot
oil circuit (hot oil <400 C)
b. medium T (120-250) usually steam heater
c. low T(<120 C) usually condensate or
steam
d. fired heaters are also needed as heat
source for hot oil loops or steam systems
(boilers)
- choice of cooler depends on temp, climate and
economics
a. high temp recover heat by raising steam
or heating boiler feed water
b. cooling tower water or air cooling are used
for most cooling
c. refrigeration circuits are used for lowest
temp (<40 C)
Fired Heaters
- used for high temp heating
a. HP steam is usually 480 F (250 C)
b. Hot oil can be used up to 600F but still
needs a heater
- Heat comes from burning fuel like natural gas,
fuel oil, process off-gas
- Heat transfer by radiation as well as convection
- many design variations, but vertical cylindrical is
most common
Typical Cabin Heater (see pic)
- can be horizontal or U-tub
Large U-Tube Heater
- 4 cells in one box
- Common convection
- Smallest plot space for large fired heat duty
Typical Furnace Temp
a. Flame temp
- Depends on fuel composition, excess air ratio
and air preheat
b. Radiant exit or bridgewall temp
- Depends on tube temp and heat flux
c. Stack temp
- Depends on amount of convective heat
recovery
- Ultimately limited by acid gas dew point or
plume formation
Heat Distribution in Fired Heaters
- Usually assume 60% radiant heat, 25%
convective, 15% stack loss
- Process duty is often limited to radiant heat for
control reasons
Furnace Efficiency
=
=
- Furnace efficiency is increased by air preheat
and reduced by increased excess air
- Stack temp is limited by acid gas dew point (w/c
increases with higher water content or acid
content in the flue gas). Uses 250 F for natural
gas, 350F for fuel oil
- Typical overall furnace efficiency is about 85%
but not all of the useful heat is necessarily used
for process heating
Combustion Chemistry
- Methane burns according to: (eqn)
LHV = 21,502 Btu/lb = 191.8 kcal/mol
For 1 MMBtu we need 106/21502 = 46.5 lb
methane
- In practice, we typically use 5% to 20% excess
air to prevent formation of carbon monoxide
and soot formation
 Fired Heater Emissions
- Regulations limit emissions of NOx, Sox,
particulates, CO, metals, unburned hydrocarbon
- Fuel selection/pre-treatment controls S and
metals
- Excess air controls CO, HC and particulate
- NOx is hardest to control:
a. Excess air makes NOx worse
b. Flue gas recirculation to reduce flame
temperature
c. Special burner designs (staged air, staged
fuel)
d. Catalytic de-NOx can be used as expensive
last resort
Catalytic De-NOx
- Expensive
- Operates at 400-700F
- Used in retrofits when ultra-low NOx burners
cannot be used
- Coupled with air preheat system
Electric Heaters
- Pass fluid axially over high resistance wires
surrounded with MgO insulation and covered
with protective sheath
- Heat from wires transfers to fluid. Maximum
duty about 1MW
Advantages:
a. High temps (<1200F)
b. No cross-leakage
c. Excellent control, turndown
d. No site emissions
e. Good for cyclic operations (reduced thermal
cycling of metal surfaces)
Disadvantages:
a. Higher capital cost
b. Higher operating cost
c. Hazardous if not properly installed, operated
and maintained
d. Highly regulated
Steam Generators
- Most process heating is carried out using steam
generated in boilers- specialized fired heaters
- Boilers are sold as packaged units, usually rated
in Mlb/hr or boiler horsepower
- Two main types of packaged boiler: water-tube
and fired-tube. Both types are usually forced
draft
- Fuel can be natural gas. LPG, or any heating oil
- Design codes: ASME PBV Code Sxn 1 (high
pressure boilers for process and power
applications) or Sxn IV (low pressure steam and
hot water)
PROCESS SAFETY
1. Chemical Plant Hazards
Safety safe design and operation of facilities is of
paramount importance to every company that is
involved in the manufacture of fuels, chemicals, and
pharmaceuticals
Safety and Environment
- Processes must meet acceptable safety and
environmental performance standards because
it is required by law, the costs (human, social,
economic) of non-compliance can be
catastrophic, lax attitudes are reflected in
insurance premiums, stock prices, moral and
ethical obligations
Major Chemical Plant Safety Legislation
1. The Occupational Safety and Health Act
(OSHA); 29 U.S.C. 651 et seq (1970)
- Employers must provide a place of employment
free from recognized hazards to safety and
health, such as exposure to toxic chemicals,
excessive noise levels, mechanical dangers, heat
or cold stress, or unsanitary conditions
2. The Emergency Planning & Community Right-
To-Know Act (EPCRA); 42 U.S.C. 11011 et seq
(1986)
- To help local communities protect public health,
safety, and the environment from chemical
hazards
3. The Toxic Substances Control Act (TSCA); 15
U.S.C. s/s 2601 et seq. (1976)
- Allows EPA to track industrial chemicals and ban
their manufacture or import
Chemical Plant Hazards
- To design a safe process or product we need to
understand and mitigate the associated hazards
- Material hazards: toxicity, flammability,
incompatibility (corrosivity and reactivity)
- Process hazards: overpressure, explosions, loss
of containment, noise
Toxicity
- Almost every chemical is toxic if you get enough
of it
- Chemical plants tend to have large enough
amounts to cause serious concern for workers
and local residents
- Process design needs to consider
a. Elimination or substitution of the most
hazardous compounds
b. Prevention of releases
 c. Containment
d. Disposal (via effective collection or vent
systems)
e. Ventilation
f. Emergency procedures
Definitions:
a. Acute effects symptoms develop rapidly (ex.
Burns to skin after direct contact), normally the
result of short-term exposure
b. Chronic effect develop over a long period of
time (eg cancer), often but not always the result
of long-term exposure, chronic conditions
usually persist or recur frequently
c. LD50 lethal dose at which 50% of test animals
are killed, usually expressed in mg/kg body
mass, indicates acute effects only
d. TLV (threshold limit value) or permissible
exposure limit conc that is it believed the
average worker can safely be exposed to for 40
hr work week
Toxic Substance Control Act (TSCA)
- USEPAs version of the food and drug act
a. Allows EPA to regulate the 75000 chemical
substances used in industry (including
confidential materials)
b. TSCA requires extensive review before
approval is given by USEPA to manufacture
import and sell a new chemical in the USA
c. Under TSCA, USEPA can ban or restrict the
import, manufacture and use of any
chemical
d. Under TSCA, anyone has a right and
obligation to report info about new or
alleged health/environmental effects
caused by a chemical
- Section 5 of TSCA requires submitting a pre-
manufacture notice (PMN) to EPA 90 days
before manufacturing or importing any new
chemical
Flammability
- Requires three things: a sufficient amount of
fuel, sufficient amount of oxidant, a source of
ignition
- Possible ignition sources include:
a. Electrical equipment such as motors,
actuators usually specified as flame-proof
or non-sparking when fuels are present
b. Open flames from furnaces, incinerators
and flare stacks
c. Static electricity from any flow, hence pipes,
vessels, & flanges are always grounded
d. Miscellaneous sources include matches,
lighters, & mobile phones are usually
banned
Definitions:
a. Flash point the lowest temp at which the
material will ignite from an open flame, and
function of vapor pressure and flammability
limits
b. Autoignition temp temp at which the
substance ignites in air spontaneously,
indicates maximum temp the material can
be heated to in air (eg drying)
c. Flammability limits- highest and lowest conc
in air at normal temp and pressure (ntp) at
which a flame will propagate thru the
mixture and vary widely for different
materials
Flame Suppression
- Flame arrestors (flame traps) are specified on
vent lines of equipment that contains
flammable materials to prevent a flame from
propagating back from the vent
- Various proprietary designs are available
- Basic principle: provide high metal surface area
to act as a sink for heat and free radicals
Incompatibility
- Mixture of incompatible materials may undergo
violent reaction (exothermic, temp runaway)
such as acids and bases, acids and metals, fuels
and oxidants, free radicals initiators and
epoxides, peroxides, unsaturates
- Incompatibility with materials of construction
can lead to loss of containment such as
corrosion of vessels, internals, instruments and
softening of gaskets, seals, linings
- Materials incompatibility is one of the major
sources of incidents
Material Safety Data Sheets
- Must be provided to employees and customers
by law in the USA
- Contains info needed to begin analyzing
materials and process hazards
- Most contain a disclaimer stating that the user
should also make their own evaluation of
compatibility and fitness for use
- It includes chemical name, synonyms,
manufacturer contact info, composition,
summary of major hazards, flammability data,
NFPA ratings, OSHA PEL data, required PPE
Roles of MSDS in Process Design
- Always collect MSDS of all components used in
the process at as early a stage as possible:
 a. Sources: manufacturers, manus web sites,
libraries, etc
b. Because of disclaimers, it is worth checking
>1 source
- Use MSDS to improve intrinsic safety of process
to eliminate incompatible mixtures, substitute
less hazardous chemicals when possible (eg
toluene instead of benzene as solvent)
- Ensure that design meets regulatory
requirements such as vapor recovery, and other
emissions
Design for Materials Hazards
a. Substitution use something less toxic and
hazardous
b. Containment sound design of plant and
equipment, for ex use welded joints instead of
flanges
c. Prevention of releases by design of equipment
and disposal systems
d. Ventilation use open plant structure or
engineered ventilation systems
e. Disposal effective vent stacks and scrubbers
f. Provision of emergency equipment
PROCESS HAZARDS
Overpressure
- Occurs when mass, moles, or energy
accumulate in a contained volume (or space
with restricted ourflow)
- Rate of accumulation determines the pressure
rise
- Process controls may not be able to respond
quickly enough
- If pressure is not relieved by pressure safety
valve then outcomes could include: vessel
rupture, explosion, other loss of containment
Fire and Explosions
- A fire requires a flammable mixture and an
ignition source
- Fires in chemical plants can quickly lead to
damage to control systems and equipment,
causing overpressure, loss of containment and
explosions
- Fire protection guidelines are given in several
standards
- Legal requirements for fire protection are set by
OSHA
Source of Ignition
a. Sparking of electrical equipment motors,
actuators, lighting, electric heaters
b. Process flames furnaces, flare stacks,
incinerators, these should always be sited well
away from plant, usually upwind
c. Static electricity
d. Lightning
e. Vehicles (engines, electrical systems and
exhausts)
f. Portable electrical devices
g. Welding and cutting equipment
h. Miscellaneous sources (matches, lighters, etc
are usually banned)
Process Electrical Systems
- The use of electrical equipment in chemical
plants is regulated by law and by industry
design codes
- NFPA 70 defines classified areas in which
flammable materials may be present at high
enough conc to be ignitable specifically
precautions must be taken depending on the
classification and equipment must be designed
and installed in accordance with code
- Codes should be consulted before selecting
equipment for use in classified areas
- Codes also govern electrical maintenance work.
Companies usually have strict lock-out, tag-
out procedures to prevent electric shock
accidents
Explosions
- An explosion is the sudden, catastrophic release
of energy causing a pressure wave (blast wave)
- Can be caused by ignition of a flammable
mixture: liquid, vapor, solid (eg finely dispersed
dust)
- Can also be caused by release of thermal energy
such as boiler rupture, BLEVE (boiling liquid
expanding vapor explosion)
Definition:
Deflagration combustion zone propagates at
(subsonic) flame speed usually <30 m/s, pressure
wave generated usually <10 bar, Principal heating
mechanism is combustion
Detonation combustion zone propagates at
supersonic velocity 2000-3000 m/s, pressure wave
up tp 20 bar, principal heating mechanism is shock
compression, requires confinement or high-
intensity source, deflagration can turn into
detonation when propagating along a pipe
Expansion factor measure of the increase in
volume resulting from combustion, E = (molar
density of reagents)/(molar density of products),
maximum value of E is for adiabatic combustion
 Flame speed the rate of propagation of a flame
front thru a flammable mixture, with respect to a
fixed observer

Design Implications:
- Design to prevent explosions from happening
- Prevent formation of explosive mixtures
whenever possible, operate outside
flammability envelope
- Consider confined explosion as a pressure relief
scenario and ensure that PRV is sized to allow
adequate relief load to prevent detonation
- Use flame suppressors to prevent deflagration
from propagating into detonation

Process Hazards: Loss of Containment

- Primary means of protecting the public from
toxic chemicals is containment by the plant
itself
- Loss of containment can occur due to:
a. Pressure relief
b. Operator error (e.g. leaving a sample point
open)
c. Poor maintenance procedures such as
failure to drain and purge properly and
failure to put everything back together
properly
d. Leaks from degraded equipment such as
corrosion and damaged seals, gaskets
- Mostly operational issues but design may need
to provide for secondary containment if the
potential impact of a release is high

Process Hazards: Noise

- Chemical plants can be very noisy especially
compressors, turbines, motors and solids
handling
- Chronic effects include permanent damage to
hearing
- Sound is measured in decibels defined by:
()
= [ ]

- Ear protection should be required in areas

where noise > 80 dB
- Permanent damage can be cause by noise >85
dB