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REACTOR DESIGN FIRST ORDER APPROXIMATION

-prediction of reactor performance, product -we can often write as


yields, etc. =
-detailed discussion of kinetics, catalysis, where CA, concentration of the limiting reagent and keff,
deactivation, mass transfer, etc. is effective 1st order rate constant
REACTOR SIZING & COSTING -for an equilibrium reaction we have
-estimate required volume: (1) from residence = ( )
time for non-catalytic reactors, (2) from catalyst space where CA*, equilibrium concentration
velocity for packed bed catalytic reactors, (3) from REACTOR HEAT BALANCE-design must account enthalpy
hydraulics and residence time for fluidized and slurry difference between feed and products, which come
reactors from:
-decide pressure vessel size and shape Heat of Reaction = ( )
-cost reactor shell as pressure vessel Sensible Heat Change =
-add extra costs for mixers, internals, etc. Latent Heat (from Phase Change) =
REAL REACTOR DESIGN =
-a lot more complicated than estimation of MIXING IN INDUSTRIAL REACTORS
reactor volume Tubular Reactors
-cost comes from reactor internals (mixers, -almost always designed to be in turbulent flow
agitators, baffles, jackets, coils, external loops, and -static mixer usually placed immediately
catalyst handling) downstream of any feed point to ensure reactor
-mixing and heat transfer performance are contents are mixed quickly
difficult to model and understand, and have significant -static mixers consists of baffles to iduce
effects on yield and purity. turbulence
IDEAL REACTORS (seldom attained but useful as approx) Stirred Reactors
CSTR (WMR) -agitator consists of impeller mounted on shaft
-perfect mixing driven by motor
-product and vessel contents are at -motor usually mounted above the reactor
uniform T and concentration. -reactor contains baffles or internals to induce
-material sees a distribution of turbulence and prevent swirling of contents
residence times. Impeller Types: Straight Blade, Pitched Blade,
PFR Hydrofoil, Propeller (Turbine), Helical Ribbon, Anchor,
-no axial mixing Rushton Turbine and Screw
-sharp residence time distribution Baffles
-matl flowing thru the reactor -baffles prevent liquid to swirl and
experiences a profile of concentration and T. develop vortex
REACTION KINETICS COMPLICATIONS -usually 4 baffles are placed around the
-seldom simple 1st or 2nd order rxns perimeter (1/10 of diameter and located 1/20 of
-catalytic reactions mostly fitted with Langmuir- diameter from wall
Hinshelwood expressions (inhibition terms often Impeller Reynolds Number
significant) -can determine extent of mixing and
-mass transfer, mixing & equilibrium often limit correlate power consumption and heat transfer to shell
overall rate 2
-defined as =
-catalyst deactivation is often significant
-simple 1st order model usually adequate to where Da, agitator blade diameter, N agitator speed
predict conversion but not for predicting by-product (revs/s), density (kg/m3) and viscosity (Ns/m2)
yields or understanding catalyst behavior Power Consumption, P (W or Nm/s)
MASS TRANSFER -can be made into Np (dimensionless)
-processes that often reduce the overall rate of which can be correlated against Re
rxn to a slower rate than intrinsic kinetics
=
-limitations can occur (1) between phases V/L, 3 5
L/L, L/S, V/S, etc, (2) inside catalyst pores -for Re>103, power number is constant
-interphase transport strongly influenced by and a function of impeller type (see Perrys)
interfacial area (particle, droplet or bubble size)
Non-Ideal Flow and Mixing design (2) allow extra residence time in radiant zone if
-simple correlations are adequate if (1) necessary
dead zones cannot be tolerated because of purity, HOW WOULD YOU GET VAPOR TO REACT WITH
safety, etc (2) reactor internals are complex (3) reaction LIQUID?
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 SPARGED REACTORS
-boundary conditions on grid are set up to Sparger-a pipe with holes for bubbles to flow
reflect reactor geometry out
-results plotted as color coded pictures of -for smaller bubbles, porous pipe
velocity, mass transfer coefficient, void fraction, shear, diffuser can be used
etc., that let designers see where weak points of the -balance between bubble break-up and
design to propose changes to the design geometry coalescence is quickly established
REACTOR TOMOGRAPHY -if small bubble size is to be maintained then
-various methods used for non-invasive additional shear is needed
examination of reactors in-situ (1) Cat Scanning(validate -designer must allow disengaging space at top
MTO reactor catalyst distribution), Ultrasound, Gamma of reactor, or entrainment will be excessive
Scanning (validate axial catalyst density profile) (2) Sparger as Agitator
carried out by specialist contractors and not cheap -if gas flow rate is large, then gas flow
NON-ISOTHERMAL LIQUID PHASE REACTORS can be used as primary means of agitation
-low heat duties achieved with a jacketed vessel -For agitating open tank full of water at
-intermediate duties require internal coil 1atm the air rates are (Perrys):
(impacts mixing, fouling and cleaning) Degree of agitation Liquid depth 9ft Liquid depth 3ft
-high duties require external heat exchange Moderate 0.65 1.3
circuit Complete 1.3 2.6
ESTIMATING HEAT TRANSFER COEFFICIENT IN STIRRED Violent 3.1 6.2
TANK REACTORS LIFT REACTORS AND LOOP REACTORS
-reactor side heat transfer coefficient depends -if sparger provides agitation, then baffle is
on rate of agitation, reactor internals and coil design added to give better liquid circulation and ensure
(case specific, detailed understanding requires CFD or mixing of feeds
physical modeling) -can be used for very large flow rates, where
-first approximation for jacket for design liquid vapor is driven by the vapor flow
purposes: -equipment design governed by 2-phase flow
= Pr 0.33 hydraulics
where (from 19.8) range 0.36-1.4, range 0.5-0.75 UOP/Paques Thiopaq Reactor
typically 0.67, Re impeller Reynolds number and -biological desulfurization of gases with
Nu=hd/k where d is reactor internal diameter oxidative regeneration of bugs using air
NON-ISOTHERMAL VAPOR PHASE REACTORS -reactor at AMOC in AI Iskandriyah has
-heat transfer coefficients usually too low to use six 2m downcomers inside shell
jackets or internal coils REACTION IN V-L CONTACTING COLUMNS
-external heating or cooling loops are common -trayed or packed columns can be used to
-in endothermic processes, reaction is carried contact vapor and liquid for reaction
out in a fired heater tube: (1) design is fired heater
-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 Where should we operate?
to cell mass Intracellular product batch process
III. Slow Growth as substrate or other factors -batch operation continues into Phase V to
begin to limit rate maximize the product assay (increase reactor
IV. Stationary Phase: cell growth rate and death productivity)
rate are equal -not economical to go to absolute highest
V. Decline Phase: cells die or sporulate, often product concentration
caused by product build up Intracellular product, continuous process
-if product is harvested from the cells, we need
- intracellular product accumulation is slow at a high rate of production of cells and operate toward
first (not many cells) the upper end of phase 3
-product accumulation continues even after live Extracellular product, continuous process
cell count falls (dead cells still contain product) --if product can be recovered continuously or
Cell Growth Kinetics cells can be recycled, we can maintain highest
-cell growth rate defined by productivity by operating in phase IV

=

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 CLEANING AND STERILIZATION
often not closely tied to rate of consumption of Biological Processes must maintain sterile
substrate as (aseptic) operation
(1) product may be made by cells at -prevent infection of desired organisms
relatively low concentrations with invasive species
(2) cell metabolic processes may not be -prevent invasion of natural strains that
involved in product formation interbreed with desired organisms and cause loss of
-usually not straightforward to write a desired strain properties
stoichiometric equation linking product to substrate -prevent contamination of product with
-product formation and substrate consumption py-products formed by invasive species
are linked through dependence of both on live mass in -prevent competition for substrate
reactor between desired organism and invasive species
-ensure quality and safety of food and
= pharmaceutical grade products

where pl is product l concentration (g/L), kl is production Design must allow for cleaning and sterilization
rate of product l per unit mass of cells 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 Evaporation single stage removal of volatile
as long thin fibers solute or solvent
-bundle of fibers is set into a resin Distillation multiple stage separation between
(potting) that effectively forms a tubesheet identified light key & heavy key components
-feed is fed shell-side and permeate Absorption removal of vapor component using
withdrawn from inside the fibers non-volatile solvent
Flat Sheet (spiral Wound) Membranes Fractionation separation of multicomponent
membranes cast as sheets mixture into fractions by boiling ranges, as in oil refining
-sheets glued back-to-back along edges Stripping multi stage removal of volatile solute
to form an envelope and attached to a perforated tube from solvent
-assembly is rolled up into a spiral- Vapor -Liquid Flash Drums
wound module -flash or knockout drums widely used in
Gas Separation Membranes SEM, TEM, STEM chemical plants as (1) downstream of condensers and
can be used for microscopic analysis coolers (2) upstream of compressors and between
-Asymmetric Structure (1) thin selective compressor stages (3) as reflux drums on columns (4) in
skin (2) porous support layer relief systems
Membrane Flow Pattern integration of the flux -design function is to separate liquid drops from
equation along the membrane depends on the flow vapor and prevent vapor blowing out into liquid-filled
pattern lines by maintaining liquid level control
-ONLY FLAT SHEET MEMBRANES CAN BE USED -there will usually be ~1 to 2% liquid
IN CROSS-FLOW MODE entrainment in the vapor from knockout drum unless a
-neither flat sheet nor hollow fiber membranes demister is used
can use a sweep gas Vertical Flash Drums vessel diameter chosen to give
Membrane Process Performance membranes give low vapor velocity less than thermal velocity of drops
recovery of permeate species (<95% often <90%) = 0.07[( )/ ]1/2
-need to maintain high enough partial P on -use 0.15 ut if there is no demister
retentate side to give a reasonable flux at unit outlet -allow 1 diameter above feed and at least 0.6
-if outlet partial P is low, flux is low and area diameters below feed for settling, also allow 0.4
required becomes large and costly diameter for demister
-unless selectivity is very high, membranes give -height of liquid depends on level control
low purity on permeate side (<98% often <95%) Liquid Level Control Bands level control needs to allow
-membranes are used for bulk separations: (1) for some natural variation in liquid level due to
air separation, hollow fiber (2) CO2 rejection from splashing, etc
natural gas, spiral wound (3) H2 recovery from mixtures -alarms must not be set too close to normal
with methane, hollow fiber operating level or they will be a nuisance (& will be
Permeate Recycle permeate from 2nd module recycled ignored)
to feed in 1st module -operators need time to respond to alarms
-1st module can run under conditions that before shutdown
maximize permeate purity (high selectivity) and we -typical assumption is about 2min between
dont have to worry about purity alarm and trip, allow 10min of liquid residence time
-partial P of desired component in 1st module is below feed
increased -MIDPOINT OF NORMAL OPERATING BANF
Retentate Recycle retentate from 2nd module is SHOULD BE >DV/2 BELOW FEED POINT, SO IF 5min OF
recycled to feed of 1st module LIQUID HOLDUP GIVES HEIGHT <DV/2, USE HALF A
-permeate goes through 2 membranes in series, DIAMETER TO THE MIDPOINT AND 5min HOLDUP
final permeate purity is increased BELOW
-1st module can run at higher flux, lower Horizontal Flash Drum bigger area for settling + more
selectivity as it makes a rough separation space for liquid holdup
-extra compressor needed between the -trade-off is higher plot space and stronger
membrane stages foundations needed to support vessel
Vapor Liquid Separations -often used when process control demands
Flash single stage thermal & phase eqm some liquid inventory, e.g. reflux drums
-design more complex than vertical drum
Liquid-Liquid Separations distillation or crystallization (2) thermally sensitive
Decanting single stage thermal & phase eqm compounds that cannot be distilled or crystallized
Mixer-Settler single theoretical stage -many process variations have been developed
extraction process -high recovery >99% and purity >99.9% can be
-often 2 or 3 stages are still cheaper achieved
than a column Cost depends on process scheme and whether
Extraction multistage contacting of 2 liquid sorbent (stationary phase) and eluent (mobile phase)
phases can be reused for quality control reasons used sorbent
Membrane based on differences in relative and eluent are often discarded in the pharmaceutical
permeability of components industry
-membrane can be used to keep 2 Batch Chromatography a pulse or batch of feed is
solvents from mixing introduced into the column, then washed through using
Horizontal Decanter design similar to knockout drum an eluent
that allow droplets to settle and provide adequate -fraction that contains the desired product is
holdup for level control retained and the rest discarded
-siphon takeoff can control level without -if sorbent cost is low, sorbent may be
instruments if densities are constant discarded instead of eluting heavies
Multistage Extraction: Sulfolane Process 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
-used for L/L extraction of benzene and toluene -affinity chromatography is one of the
from gasoline using sulfolane solvent most widely used methods in recovering large
Recovery of Components from Liquid Solutions biologically derived molecules
Distillation, precipitation, membranes, Continuous Countercurrent Chromatography
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
--if solids move then more strongly adsorbed
-allows growth of larger and more regular
component A can be separated from less strongly
crystals (less shear)
adsorbed B
-crystals are only agitated by circulating liquor
Countercurrent Chromatography continuous
-can use cooling to achieve supersaturation
movement of solids is difficult to accomplish as good
Industrial Chromatography very versatile separation
sorbents (such as zeolites and gels) do not allow flow
process particularly for (1) mixtures of close-boiling
well o suffer attrition
compounds that are expensive to separate by
-instead, solids movement can be simulated
using a rotary valve or set of switching valves
-UOP Sorbex process developed for separating II. Nucleate boiling w/ agitation by bubbles
normal parrafins in 1960 and is now used for recovering III. Nucleate boiling w/ unstable film
p-xylene from mixed xylenes and separating glucose IV. Stable film boiling
and fructose to make High Fructose Corn Syrup V. Radiant heat transfer
-Simulated moving bed chromatography is - As delta T between wall and fluid increases, h
being used more widely in pharmaceutical separations increases at first due to bubbles, but then vapor
BOILING AND CONDENSING blankets the surface and the heat transfer
Pool Boiling coefficient falls
- Agitation by bubbles and natural convection - For fired boilers this can lead to tube failure
- Occurs in kettle reboilers - Avoiding film boiling by limiting design to
Flow Boiling maximum critical flux
- Agitation by bubbles and forced convection Enhancement of Boiling Heat Transfer: UOP High Flux
- Occurs in thermosiphon reboilers Tubing
- High fluid velocity - Porous boiling surface
Thermosiphon Reboilers - Coating thickness of 0.127mm 0.381mm
- If we set the reboiler below the liquid level in - Strong metallurgical bond
the column sump then the static head drives - Interconnecting channels or re-entrant sites
liquid into the reboiler - Boiling performance ~ 10x greater than bare
- The difference in density caused by vaporization tube
then sets up a circulation, limited by pressure - Overall performance ~ 2-5x greater than bare
drop tube
- Typically design for about 25 to 33% High Flux Tube Products
vaporization per pass - ID Coated (OD bare or fluted)
- Thermosiphon orientation can be vertical - OD Coated (ID Bare or Finned)
(tubeside flow) or horizontal (shellside flow)
- Horizontal is usually cheaper, but vertical Applications of High Flux
handles dirty fluids better - Reboilers
Flow regime in Thermosiphon Tubes a. Thermosiphons (TEMA type H, J or X)
- Different flow regimes occur as vapor/liquid b. Kettles
ratio increases c. Stab-in bundles
- Slug flow is undesirable as it causes noise and - Condensers (kettles)
vibration, but is also unavoidable in vertical a. Boiling refrigerant
thermosiphons Condensing Heat Transfer
- Annular flow is avoided by designing for <33% - Important for condensers and heaters that use
vaporization condensing steam
Kettle Reboilers - Condensing behavior also occurs in many heat
- More expensive than horizontal thermosiphon exchangers if a vapor is cooled below the dew
a. Larger diameter shell for same duty point
b. Additional liquid outlet nozzle allows for Two Types of Condenser
blowdown a. Total Condenser
c. TEMA types are (A or B) K (T or U) - no incondensable materials in vapor phase
- often used as steam regenerator because of - heat transfer coefficient determined by thermal
built in separator for vapor and allowance for resistances only
blowdown b. Partial Condenser
Stab-in Reboilers - Some vapor components dont condense
- the tube bundle can sometimes be fitted inside - HTC determined by thermal and mass transfer
the column sump: this saves a shell resistances
- this behavior is similar to kettle reboilers - Therefore much lower h.t.c
- designer has to make sure there is enough - Condensing molecules (eg water) have to
sump height to give good level control and diffuse thru noncondensibles (eg air)
pump NPSH w/o exposing tubes - Diffusion resistance decreases coefficient (big
Boiling Heat Transfer Coefficient (HTC) difference to size of exchanger)
I. Natural Convection heat transfer
- Calculation of condensing coefficients is b. Hot oil can be used up to 600F but still
complex, particularly when coupled with needs a heater
diffusion resistances, usually done using HX - Heat comes from burning fuel like natural gas,
design programs fuel oil, process off-gas
- need to design for accumulation of - Heat transfer by radiation as well as convection
noncondensibles even in total condensers - many design variations, but vertical cylindrical is
a. provide a vent at the top of the exchanger most common
b. manually vent as often as required by Typical Cabin Heater (see pic)
experience - can be horizontal or U-tub
- to keep noncondensibles out of steam system, Large U-Tube Heater
boiler feed water is degassed by stream - 4 cells in one box
stripping - Common convection
Bundle Effects on Heat Transfer - Smallest plot space for large fired heat duty
- liquid condensate film Typical Furnace Temp
- tubes in bundle a. Flame temp
- condensate draining from tubes above creates - Depends on fuel composition, excess air ratio
constant rippling and turbulence which and air preheat
improves condensing coefficient b. Radiant exit or bridgewall temp
- condensate draining from tubes above - Depends on tube temp and heat flux
increases condensate level on tubes below c. Stack temp
which decreases condensing coefficient - Depends on amount of convective heat
Enhancement of Condensing Heat Transfer: UOP High recovery
Cond Tubes - Ultimately limited by acid gas dew point or
a. mechanical enhancement plume formation
- applied to tube OD Heat Distribution in Fired Heaters
b. optimized fin profile - Usually assume 60% radiant heat, 25%
- modified fins convective, 15% stack loss
- high extended area - Process duty is often limited to radiant heat for
- improves condensate drainage control reasons
- minimized liquid condensate film thickness Furnace Efficiency
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) - Furnace efficiency is increased by air preheat
b. medium T (120-250) usually steam heater and reduced by increased excess air
c. low T(<120 C) usually condensate or - Stack temp is limited by acid gas dew point (w/c
steam increases with higher water content or acid
d. fired heaters are also needed as heat content in the flue gas). Uses 250 F for natural
source for hot oil loops or steam systems gas, 350F for fuel oil
(boilers) - Typical overall furnace efficiency is about 85%
- choice of cooler depends on temp, climate and but not all of the useful heat is necessarily used
economics for process heating
a. high temp recover heat by raising steam Combustion Chemistry
or heating boiler feed water - Methane burns according to: (eqn)
b. cooling tower water or air cooling are used LHV = 21,502 Btu/lb = 191.8 kcal/mol
for most cooling For 1 MMBtu we need 106/21502 = 46.5 lb
c. refrigeration circuits are used for lowest methane
temp (<40 C) - In practice, we typically use 5% to 20% excess
Fired Heaters air to prevent formation of carbon monoxide
- used for high temp heating and soot formation
a. HP steam is usually 480 F (250 C)
Fired Heater Emissions PROCESS SAFETY
- Regulations limit emissions of NOx, Sox, 1. Chemical Plant Hazards
particulates, CO, metals, unburned hydrocarbon
- Fuel selection/pre-treatment controls S and Safety safe design and operation of facilities is of
metals paramount importance to every company that is
- Excess air controls CO, HC and particulate involved in the manufacture of fuels, chemicals, and
- NOx is hardest to control: pharmaceuticals
a. Excess air makes NOx worse
b. Flue gas recirculation to reduce flame Safety and Environment
temperature - Processes must meet acceptable safety and
c. Special burner designs (staged air, staged environmental performance standards because
fuel) it is required by law, the costs (human, social,
d. Catalytic de-NOx can be used as expensive economic) of non-compliance can be
last resort catastrophic, lax attitudes are reflected in
Catalytic De-NOx insurance premiums, stock prices, moral and
- Expensive ethical obligations
- Operates at 400-700F
- Used in retrofits when ultra-low NOx burners
cannot be used Major Chemical Plant Safety Legislation
- Coupled with air preheat system 1. The Occupational Safety and Health Act
Electric Heaters (OSHA); 29 U.S.C. 651 et seq (1970)
- Pass fluid axially over high resistance wires - Employers must provide a place of employment
surrounded with MgO insulation and covered free from recognized hazards to safety and
with protective sheath health, such as exposure to toxic chemicals,
- Heat from wires transfers to fluid. Maximum excessive noise levels, mechanical dangers, heat
duty about 1MW or cold stress, or unsanitary conditions
Advantages: 2. The Emergency Planning & Community Right-
a. High temps (<1200F) To-Know Act (EPCRA); 42 U.S.C. 11011 et seq
b. No cross-leakage (1986)
c. Excellent control, turndown - To help local communities protect public health,
d. No site emissions safety, and the environment from chemical
e. Good for cyclic operations (reduced thermal hazards
cycling of metal surfaces) 3. The Toxic Substances Control Act (TSCA); 15
Disadvantages: U.S.C. s/s 2601 et seq. (1976)
a. Higher capital cost - Allows EPA to track industrial chemicals and ban
b. Higher operating cost their manufacture or import
c. Hazardous if not properly installed, operated Chemical Plant Hazards
and maintained - To design a safe process or product we need to
d. Highly regulated understand and mitigate the associated hazards
Steam Generators - Material hazards: toxicity, flammability,
- Most process heating is carried out using steam incompatibility (corrosivity and reactivity)
generated in boilers- specialized fired heaters - Process hazards: overpressure, explosions, loss
- Boilers are sold as packaged units, usually rated of containment, noise
in Mlb/hr or boiler horsepower Toxicity
- Two main types of packaged boiler: water-tube - Almost every chemical is toxic if you get enough
and fired-tube. Both types are usually forced of it
draft - Chemical plants tend to have large enough
- Fuel can be natural gas. LPG, or any heating oil amounts to cause serious concern for workers
- Design codes: ASME PBV Code Sxn 1 (high and local residents
pressure boilers for process and power - Process design needs to consider
applications) or Sxn IV (low pressure steam and a. Elimination or substitution of the most
hot water) hazardous compounds
b. Prevention of releases
c. Containment d. Miscellaneous sources include matches,
d. Disposal (via effective collection or vent lighters, & mobile phones are usually
systems) banned
e. Ventilation Definitions:
f. Emergency procedures a. Flash point the lowest temp at which the
material will ignite from an open flame, and
Definitions: function of vapor pressure and flammability
a. Acute effects symptoms develop rapidly (ex. limits
Burns to skin after direct contact), normally the b. Autoignition temp temp at which the
result of short-term exposure substance ignites in air spontaneously,
b. Chronic effect develop over a long period of indicates maximum temp the material can
time (eg cancer), often but not always the result be heated to in air (eg drying)
of long-term exposure, chronic conditions c. Flammability limits- highest and lowest conc
usually persist or recur frequently in air at normal temp and pressure (ntp) at
c. LD50 lethal dose at which 50% of test animals which a flame will propagate thru the
are killed, usually expressed in mg/kg body mixture and vary widely for different
mass, indicates acute effects only materials
d. TLV (threshold limit value) or permissible Flame Suppression
exposure limit conc that is it believed the - Flame arrestors (flame traps) are specified on
average worker can safely be exposed to for 40 vent lines of equipment that contains
hr work week flammable materials to prevent a flame from
Toxic Substance Control Act (TSCA) propagating back from the vent
- USEPAs version of the food and drug act - Various proprietary designs are available
a. Allows EPA to regulate the 75000 chemical - Basic principle: provide high metal surface area
substances used in industry (including to act as a sink for heat and free radicals
confidential materials) Incompatibility
b. TSCA requires extensive review before - Mixture of incompatible materials may undergo
approval is given by USEPA to manufacture violent reaction (exothermic, temp runaway)
import and sell a new chemical in the USA such as acids and bases, acids and metals, fuels
c. Under TSCA, USEPA can ban or restrict the and oxidants, free radicals initiators and
import, manufacture and use of any epoxides, peroxides, unsaturates
chemical - Incompatibility with materials of construction
d. Under TSCA, anyone has a right and can lead to loss of containment such as
obligation to report info about new or corrosion of vessels, internals, instruments and
alleged health/environmental effects softening of gaskets, seals, linings
caused by a chemical - Materials incompatibility is one of the major
- Section 5 of TSCA requires submitting a pre- sources of incidents
manufacture notice (PMN) to EPA 90 days Material Safety Data Sheets
before manufacturing or importing any new - Must be provided to employees and customers
chemical by law in the USA
Flammability - Contains info needed to begin analyzing
- Requires three things: a sufficient amount of materials and process hazards
fuel, sufficient amount of oxidant, a source of - Most contain a disclaimer stating that the user
ignition should also make their own evaluation of
- Possible ignition sources include: compatibility and fitness for use
a. Electrical equipment such as motors, - It includes chemical name, synonyms,
actuators usually specified as flame-proof manufacturer contact info, composition,
or non-sparking when fuels are present summary of major hazards, flammability data,
b. Open flames from furnaces, incinerators NFPA ratings, OSHA PEL data, required PPE
and flare stacks Roles of MSDS in Process Design
c. Static electricity from any flow, hence pipes, - Always collect MSDS of all components used in
vessels, & flanges are always grounded the process at as early a stage as possible:
a. Sources: manufacturers, manus web sites, c. Static electricity
libraries, etc d. Lightning
b. Because of disclaimers, it is worth checking e. Vehicles (engines, electrical systems and
>1 source exhausts)
- Use MSDS to improve intrinsic safety of process f. Portable electrical devices
to eliminate incompatible mixtures, substitute g. Welding and cutting equipment
less hazardous chemicals when possible (eg h. Miscellaneous sources (matches, lighters, etc
toluene instead of benzene as solvent) are usually banned)
- Ensure that design meets regulatory Process Electrical Systems
requirements such as vapor recovery, and other - The use of electrical equipment in chemical
emissions plants is regulated by law and by industry
Design for Materials Hazards design codes
a. Substitution use something less toxic and - NFPA 70 defines classified areas in which
hazardous flammable materials may be present at high
b. Containment sound design of plant and enough conc to be ignitable specifically
equipment, for ex use welded joints instead of precautions must be taken depending on the
flanges classification and equipment must be designed
c. Prevention of releases by design of equipment and installed in accordance with code
and disposal systems - Codes should be consulted before selecting
d. Ventilation use open plant structure or equipment for use in classified areas
engineered ventilation systems - Codes also govern electrical maintenance work.
e. Disposal effective vent stacks and scrubbers Companies usually have strict lock-out, tag-
f. Provision of emergency equipment out procedures to prevent electric shock
accidents
PROCESS HAZARDS Explosions
Overpressure - An explosion is the sudden, catastrophic release
- Occurs when mass, moles, or energy of energy causing a pressure wave (blast wave)
accumulate in a contained volume (or space - Can be caused by ignition of a flammable
with restricted ourflow) mixture: liquid, vapor, solid (eg finely dispersed
- Rate of accumulation determines the pressure dust)
rise - Can also be caused by release of thermal energy
- Process controls may not be able to respond such as boiler rupture, BLEVE (boiling liquid
quickly enough expanding vapor explosion)
- If pressure is not relieved by pressure safety Definition:
valve then outcomes could include: vessel Deflagration combustion zone propagates at
rupture, explosion, other loss of containment (subsonic) flame speed usually <30 m/s, pressure
Fire and Explosions wave generated usually <10 bar, Principal heating
- A fire requires a flammable mixture and an mechanism is combustion
ignition source
- Fires in chemical plants can quickly lead to Detonation combustion zone propagates at
damage to control systems and equipment, supersonic velocity 2000-3000 m/s, pressure wave
causing overpressure, loss of containment and up tp 20 bar, principal heating mechanism is shock
explosions compression, requires confinement or high-
- Fire protection guidelines are given in several intensity source, deflagration can turn into
standards detonation when propagating along a pipe
- Legal requirements for fire protection are set by
OSHA Expansion factor measure of the increase in
Source of Ignition volume resulting from combustion, E = (molar
a. Sparking of electrical equipment motors, density of reagents)/(molar density of products),
actuators, lighting, electric heaters maximum value of E is for adiabatic combustion
b. Process flames furnaces, flare stacks,
incinerators, these should always be sited well
away from plant, usually upwind
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