CHEE321:ChemicalReactionEngineering

Module:FunStuffwedidntcover andthinkingabouttheexam

Topic1:NotallReactorsareIdeal!
Dead zones (1) and short-circuiting (2) in CSTR or PFR

Velocity profiles (2) and (3) lead to deviations from ideal PFR behaviour

ComputationalFluidDynamics
tank diameter / 2 tank diameter / 3

From Jordan Pohn, Nov 2008

ComputationalFluidDynamics
CFD simulations provide velocity profiles as function of reactor geometry, impeller design and fluid properties These profiles can be used to identify dead zones, choose the position of the inlet and outlet streams, and to examine characteristic mixing times For ideal behaviour, mixing times should be short compared to time scale of reaction kinetics

CharacterizationofNonIdealReactors
Why ?
To model non-ideal hydrodynamics (mixing and flow) behaviour To understand how the non-ideality will impact reactor performance, i.e. what would be the reactant conversion in these real reactors.

How ?
Combine knowledge of Residence Time Distribution (RTD) and the already known concepts of ideal reactors to model the behavior of non-ideal reactors.

Fogler, Ch. 13

HowtoMeasureRTDs??

Feed

Effluent REACTOR

Tracer
Desirable Qualities of a Tracer easily detectable non-reactive non-absorptive or adsorptive physical properties similar to fluid

Detector

RTDCharacteristics Examples

Nearly plug-flow

Packed Bed Reactor with channeling

Models are available that use the actual RTD to calculate the effect of non-ideal mixing on conversion, temperature, etc...

RTDCharacteristics Examples

CSTR

CSTR with dead-zone & channeling

Topic2:PolymerReactionEngineering

Acrylic polymer

ABS PVC

PTFE

Water soluble polymers

SBR

Topic2:PolymerReactionEngineering
Complicating factors Many reactions occurring in parallel Polymer has a distribution of chain lengths Specialized modeling techniques are required Difficult to characterize product Viscosity increases by several orders of magnitude as monomers are converted to polymers Heat and mass transfer effects become important Heterogeneous (multiphase) processes are often used

RadicalPolymerizationKineticBalances
Initiation Termination I 2 f P1 Pn + Pm Dn+m Pn + Pm Dn + Dm
kt,d kt,c kd

Propagation

Pn + M Pn+1

kp

mon ktr Transfer to Monomer Pn + M Dn + P1

Transfer to Solvent

sol ktr Pn + S Dn + P1

P1
Initiation Propagation Term. by Disprop. Term. by Comb. Tr. to Monomer Tr. to Solvent
+k
sol

Pn (n>1)
-kp[M](Pn-Pn-1) -ktdPtotPn -ktcPtotPn -k
mon tr

Ptot = Pn
n =1

Dn

Dtot = Dn
n =1

+2fkd[I] -kp[M]P1 -ktdPtotP1 -ktcPtotP1

mon tr

+2fkd[I] -ktd(Ptot)2 -ktc(Ptot)

2

+ktdPtotPn +ktc Pm Pnm +k

m=1 mon tr n 1

+ktd(Ptot)2 +ktc(Ptot)2 + k tr [M]Ptot + k tr [S]Ptot

sol
mon

[M](Ptot-P1)

[M]Pn

[M]Pn

+ k tr [S] (Ptot-P1)

- k tr [S]Pn

sol

+ k tr [S]Pn

sol

PolymerMolecularWeightDistributions
Two polymers - same number average molecular weight (= 100 units)

Wt fraction of polymer

Living polymerization - Mw/Mn = 1.1

Conventional free radical polymerization - Mw/Mn = 2.0

10

102

103

104

Polymer chain length

ControllingReactorTemperatures: (Dealingwiththehighlyexothermiccharacterofpolymerization)

Whatwedidcover
Isothermal, Ideal Reactor (Single Reaction) Design
Mole Balance (Module-1,2) In Out + Con = Acc FA,in-FA,out+(rA)V = dCA/dt Rate Law (Module-1) (rA) = kCAn Design Algorithm (Module-2) 1. GMBE, 2. Rate Law 3. Stoich 4.Combine

Output
Reactor Volume Reaction Time Rate Constant

Analysis of Rate law (Module-5) Kinetics: How to obtain k and rxn order Multiple Reactions (Module-6) Selectivity, Yield

Conversion Product Composition

Non-Isothermal Reactor Design

(Module-3)

Output
Temperature Profile Heat Removal Heating Requirement

Energy Balance Heat Transfer Rate Equilibrium Reactions Multiple Steady State

dT/dz = ? Tin-Tout =?

Summary DesignEquationsofIdealReactors
Differential Equation
Batch

Algebraic Equation

Integral Equation
Nj

Remarks
Conc.changeswithtime butisuniformwithinthe reactor.Reactionrate varieswithtime. Conc.insidereactoris uniform.(rj)isconstant. Exitconc=concinside reactor.

dN j dt

(wellmixed)

= (rj )V

t=

N j0

dN j (rj )V

CSTR

(wellmixed atsteadystate)
PFR (steadystateflow; wellmixedradially)

V=

Fj 0 Fj ( rj )

dF j dV

= rj

Fj

V=

Fj 0

dFj ( rj )

Concentrationand hencereactionrates varyspatially(with length).

DesignEquationinTermsofConversion (limitingreactantA,singlereaction)
IDEAL REACTOR DIFFERENTIALALGEBRAIC INTEGRAL FORMFORMFORM

BATCH

N A0

dX A = ( rA )V dt

t = N A0

XA

dX A rAV

CSTR

V=

FA0 ( X A ) ( rA )

PFR

dX A FA0 = ( rA ) dV

V = FA0

XA

dX A rA

FA0 Basicidea:useplotof vs. X to calculate V ( rA )

PlugFlowReactor(PFR)

FA0 ( rA )

VPFR =

X PFR

FA0 dX rA

XPFR
ContinuousStirredTankReactor(CSTR)

FA0 ( rA )

VCSTR

FA0 =[ ] [ X CSTR ] (rA )

EvaluatedatX=XCSTR

XCSTR

GeneralAlgorithmforSolvingReactorProblems (SingleReaction,reversibleorirreversible)
1. 2.

GeneralMoleBalanceEquation(GMBE) RateLaws
Writedownratelawintermsoflimitingreactant

3.

Stoichiometry
relateconcentrationtovolumeandnumberofmoles(forbatch reactors)ortovolumetricflowrateandmolarflowrate(forflow reactor) Relatevolumeorvolumetricflowratetoconversion,pressureand temperature

4.

CombineandSolve
SubstituteratelawandstoichiometryintotheGMBE

SeeFoglerFigure4.1

StoichiometricTableforFlowReactors
Reaction:

c d C D A + B + b a a a

Define

i = Fi 0 / FA0

(LimitingreagentA)

Species

Feed Flow Rate (mol/s)

FA0 FB 0 = B FA0 FC 0 = C FA0 FD 0 = D FA0 FI 0 = I FA0 FT 0

Change within Reactor (mol/s)

( FA0 X A ) b ( FA0 X A ) a c ( FA0 X A ) a d ( FA0 X A ) a
-

Effluent Rate from Reactor (mol/s)

FA = FA0 (1 X A ) b FB = FA0 ( B X A ) a c FC = FA0 (C + X A ) a d FD = FA0 ( D + X A ) a FI = FI 0
FT = FT 0 + FA0 X A

A B C D I (inert) Total

FA0 X A

Batchreactorstoichiometric tablesaresimilar

CalculatingConcentrationforFlowReactors
ConcentrationinFlowReactors:

Fi Ci = v

Fromstoichiometry andmolebalances,wehaveFi =f(XA) Whatvalueofv (flowrate)shouldweuse? Liquidphasereactions (incompressible) Gasphasereactions (idealgas) v=v0

FT P0 T )( ) v = v0 ( FT 0 P T0

FT = FT 0 + FA0 X A
Forisothermal andisobaric reactors withnochangeinnumberofmoles(i.e.=0) v=v0

GeneralFormofEnergyBalance
W s

F1 , E1 F2 , E2 ... Fn , En

F1 , E1 F2 , E2 ... Fn , En

Q

W + Q

F E
i =1 i

i in

F E
i =1 i

i out

dE = dt
dE = dt

Energy Balance Equation in terms of Enthalpy

W + Q s
n W F Q s A0 i =1

F H
i =1 i
T

i in

FH
i =1 i

i out

Energy Balance Equation in terms of Conversion

dE i C pi dT ] [ FA0 X A H Rxn (T ) ] = dt T0

NonisothermalCSTRDesignatSteadyState
n UA(Ta T ) H Rxn (Tref ) + C p (T Tref ) X A = i C pi (T T0 ) FA0 i =1

combine with design equation: How can these be used?

V=

FA0 ( X A ) ( rA )

1. Specify XA, find V and T

http://www.engin.umich.edu/~cre/08chap/html/excd8-2.htm and class example

2. Specify T, find XA and V

http://www.engin.umich.edu/~cre/course/lectures/eight/second.htm

3. Specify V, find XA and T

The 3rd type of problem is the most challenging

Fogler 8.6: Figure 8-13 and Table 8-4 (p 525-526)

PFRwithHeatExchange
How do we solve non-isothermal PFR problems?

dT = dV

U a (Ta T ) i (rA ) H i (T )
i =1 i

F C
i =1

= g( X ,T )

pi

dFi = i (rA ) dV

or

dX FA0 = (rA ) dV

= f ( X ,T )

We need to solve the two differential equations simultaneously. Usually done numerically. (Cant be done in an exam.)

MultipleReactions:dontuseDesignEquationsin termsofConversion
IDEAL REACTOR DIFFERENTIAL FORM ALGEBRAIC FORM INTEGRAL FORM
XA

BATCH

N A0

CSTR

If you have multiple reactions: dX A t = N A0 )V+ B C = ( rAA dt and A + C D then the consumption/generation rates of FA0 ( X A ) V =not simply coupled A, B, C and D are

dX rAV

( rA )

PFR

FA0

Therefore, we need to write individual XA for all species in the dX equations dX A = (rA ) system. V = FA0

dV

rA

PBR

dX A = ( rA' ) FA0 dW

Write these in terms of molar quantities, not fractional conversions

W = FA0

XA

dX rA'

ModificationtotheCREAlgorithmforMultipleReactions
Fogler, 6.4

Molebalanceoneveryspecies(notintermsofconversion) RateLaw:NetRate ofreactionforeachspecies, e.g.,rA = ri wheresubscriptiindicatestheith reaction Stoichiometry a)LiquidPhase,incompressible:CA=NA/V=FA/v0 b)GasPhaseuse Variable volumetric flowrate; ideal gas Combine Moredifficult:setofalgebraicordifferentialequations forA,B,

EnergyBalancewithMultipleReactions
SteadystatePFR,SingleReaction
dT U a (Ta T ) + (rA ) (H rxn (T )) = n dV Fi C pi
i =1

SteadystatePFR,MultipleReaction(Nrxn)
N rxn

Rxn-i rate and heat of reaction specified in terms of reactant-j

dT = dV

U a (Ta T ) + (rij ) (H rxn ,ij (T ))

F C
i =1 i

i =1 n

pi

See Example 8-10

Fogler, 8.8.1

EnergyBalancewithMultipleReactions
SteadystateCSTR,SingleReaction
UA(Ta T ) FA0 [ H Rxn (T ) ] X A = FA0 i C pi (T T0 )
i =1 n

F (X ) but V = A 0 A ( rA )

UA(Ta T ) + [ H Rxn (T ) ] (rAV ) = FA0 i C pi (T T0 )

i =1

SteadystateCSTR,MultipleReaction(Nrxn)
N rxn i =1 n

Rxn-i rate and heat of reaction specified in terms of reactant-j

UA(Ta T ) + V rij H Rxn ,ij (T ) = FA0 i C pi (T T0 )

i =1

See Example 8-11

Fogler, 8.8.2

Selectivity and Yield

Desired Reaction: kD A D Undesired Reaction: kU A U and/or
kU2 U D

Instantaneous Selectivity Yield

SDU = YD = rD rU = Y D

Global
~ F SDU = D F U FD ND = FA0 FA NA0 NA

rD rA

What should be the criterion for designing the reactor ? Is it necessary that reactor operates such that minimum amount of undesired products are formed ?
FD
S E P A R A T O R

Total Cost

FA0

Reactor System

FA FD FU

FA

Cost

Fogler 6.1

FU

Reactant Conversion

MultipleReactions
AlgorithmforReactorDesignofMultipleReactions
MoleBalance NetRatesofReactions Stoichiometry Energybalances

AnalysesofParallelandSeriesReactions
Maximizingthereactoroperationforsinglereactantsystems Maximizingthereactoroperationfortworeactantsystems Considerationofselectivityandyield

NonelementaryReactionsandActiveIntermediateSpecies
Pseudosteadystatehypothesis Ratedetermining(ratecontrolling)step

Thefinalexam
Faculty: Course: Offered Jointly With: Date & Time: ENG CHEE321 N/A Dec 12 at 19:00 Dept: Section: Total: Location: CHEE 132 Bartlett Gym - Main Floor

Aids Allowed:

Datasheets Notebooks Math Tables Textbooks

YES YES YES YES

Photocopies Calculator Portable PC

YES YES - Sticker (GOLD) NO

QUEENS UNIVERSITY FACULTY OF APPLIED SCIENCE DEPARTMENT OF CHEMICAL ENGINEERING CHEE 321 FINAL EXAMINATION DECEMBER 2009 PROF. ROBIN HUTCHINSON INSTRUCTIONS:
This examination is THREE HOURS in length. The exam consists of 4 questions for a total of 100 marks. Please answer all questions. A gold sticker calculator is allowed. This is an open book/open notes exam. Values of the gas constant, conversion factors for units, and common integrals are found in the appendices of the course textbook. Answer all questions in the answer booklets provided. Put your student number on the front of all answer booklets. GOOD LUCK!

**PLEASE NOTE**
Proctors are unable to respond to queries about the interpretation of exam questions. Do your best to answer exam questions as written. The candidate is urged to submit with the answer paper a clear statement of any assumptions made if doubt exists as to the interpretation of any question that requires a written answer.

WhyDesignProjects?

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