Lecture 20
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In this Chapter
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In this Chapter
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Notes:
Unless the parameter values are zero or facilitates
manipulation, we typically don't substitute numerical
values for parameters in the combine step until the very
end.
In the majority of situations, analytical solutions to the
ordinary differential equations appearing in the
combine step are not possible.
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The time calculated from the batch reactor design equation is the
reaction time (i.e., tR) needed to achieve a given X for a given rxn in
a batch reactor with a given V.
It could be in the order of seconds, minutes, or hours.
The total cycle time in any batch operation is considerably longer
than the rxn time, tR. Why?
The total time to process a batch includes the time necessary to:
fill the reactor
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In some cases, the rxn time may be only a small fraction of the total
cycle time.
Typical cycle times for a batch polymerization process vary from 3 to
6 hours excluding the rxn time; the rxn time may vary between 5 and
60 hours.
As mentioned earlier, the rxn time in a batch reactor could be in the
order of seconds, minutes, or hours.
Usually, flow reactors are used for rxns with characteristic rxn times,
tR, of minutes or less.
However, there are cases where flow reactor are used to carry out
rxns with longer tR (e.g. heterogeneous rxns with mass transfer
limitations or of refractory reactants).
(lost)
Example 41:
Batch
(kinetics)
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Week 6  Lecture 21
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Design Problem 1:
(lost)
PFR
(lost)
(lost)
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FA0
Liquid Phase case: =0 rA kC A2 dV
rA
dX
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FA0
Gas Phase case: 0 rA kC A2 dV
rA
dX
Plot X along the length (volume) of the reactor for different values
of . Assume:
yA0 = 1
0/kCA0 = 2 L
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PFR
(lost)
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Solution:
m B 300 106 lb/y, X 0.8, T 1100K, P 6 atm
Data from literature: k = 0.072 s1 at 1000 K, Ea = 82 kcal/gmol
The algorithm for the CRE design problem is:
1. Mole balance
2. Rate law
3. Stoichiometry
4. Combine
5. Evaluate
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The concentration and conversion profiles down any one of the pipes
are shown above.
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Design Problem 2:
(lost)
(lost)
PBR
(lost)
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Here the channels are so small that P drop can limit the throughput and
conversion for gasphase reactions.
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dX
FA0  rA' rA' kC A2
dW
dX
Which implies that for isothermal operation: F1 (X , P )
dW
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Term 1 is dominant for laminar flow, while Term 2 is dominant for turbulent flow.
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Find = f(P).
From the continuity eq. From ideal gas law
(conservation of mass)
FT RT P
m m0 FT 0 T 0 P
0 FT 0 RT 0 P 0 0
00 FT T P0
0 FT 0 T 0 P
Substitute in Ergun Eq.
0 0 FT T P0
Simplifying yields
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W Ac Z (1  ) c or dW Ac (1  ) c dZ
where
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Upon substitution:
Notes:
when is ve, the P will be less than that for =0.
dX dP
F1 (X , P ) F2 (X , P )
dW dW
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Analytical Solution
Rearranging:
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Solution
L = 60 ft
.
m = 104.4 lbm/h T = 260C.
Pipe ID =1.61 in = 0.45 P0 = 10 atm.
Ac = 0.01414 ft2
.
G = m/Ac = 7383.3 lbm/h.ft2
Dp= in = 0.0208 ft gc = 4.17 x 108 lbm.ft/lbf.h2 For air (260oC & 10 atm)
What should be
the units of 0 ?
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P0
P P0 1  0.0155 z 0
0.5
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First, lets examine the effect of the pressure drop on the rxn:
No P
Second, lets discuss how the pressure drop affect our CRE algorithm.
Consider the 2nd order isothermal The algorithm for the CRE
design problem is:
gas phase rxn: A B, occurring in a PBR.
1. Mole balance, Design Eq.
Design Equation: 2. Rate Law
3. Stoichiometry (to find Ci)
Rate Law:
4. Combine (all of the above)
5. Evaluate
Stoichiometry:
Combine:
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Combine:
Reconsider the packed bed in Example 44 for the case where a secondorder rxn,
2A B + C, is taking place in 20 meters of a 1 schedule 40 pipe packed with catalyst.
The flow and packedbed conditions in the example remain the same except that they are
converted to metric units; that is:
P0 = 10 atm = 1013 kPa, T = T0 = 260oC, k = 12 m6/(kmol.kgcat.h)
CA0 = 0.1 kmol/m3, 0 = 7.15 m3/h, P parameter: 0 = 25.8 kPa/m
Reactor length: L = 20 m, Crosssectional area of the pipe: Ac = 0.0013 m2
Cat. particle size: Dp = 0.006 m, Solid catalyst density: c = 1923 kg/m3
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2A B + C
Solution
By substitution:
X = 0.82
2A B + C
P0 = 10 atm = 1013 kPa, T = T0 = 260oC, k = 12 m6/(kmol.kgcat.h)
CA0 = 0.1 kmol/m3, 0 = 7.15 m3/h, P parameter: 0 = 25.8 kPa/m
Reactor length: L = 20 m, Crosssectional area of the pipe: Ac = 0.0013 m2
Cat. particle size: Dp = 0.006 m, Solid catalyst density: c = 1923 kg/m3
Solution
By substitution:
X = 0.693
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Solution
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external diffusion of A
hydrodynamic
boundary
layer
external diffusion of A
internal diffusion of A
hydrodynamic
boundary
layer
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external diffusion of A
internal diffusion of A
adsorption of A
A + S AS bulk gas phase
hydrodynamic
boundary
layer
external diffusion of A
hydrodynamic
boundary
layer
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external diffusion of A
hydrodynamic
boundary
layer
external diffusion of A
hydrodynamic
boundary
layer
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hydrodynamic
boundary
layer
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Active site
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(2) the ratio of the heat transfer surface area to reactor volume
(catalyst weight) will be decreased, thereby making heat
transfer more difficult for highly exothermic and endothermic
rxns.
We now proceed to combine P with rxn in a PBR when we have
volume change with rxn & therefore cannot obtain an analytical
solution.
Design Problem 2:
(lost)
(lost)
PBR
(lost)
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Solution:
Design Equation:
Stoichiometry:
Combine:
Combine:
Evaluate:
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Combine:
Evaluate:
From Example 44, 0 = 0.0775 atm/ft; & Example 45, = 0.0166 lbm1
Evaluate:
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where,
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Is the mass velocity (mass flux), G, constant along the length of the
pipe?
Yes. Why?
How can I reduce the No. of variables in the above equation?
du G d
By replacing u with G/ and du/dL with  2
dL dL
By substitution:
2
dP G d 2fG 2

dL dL D
2
F T P dP G d 2fG 2
0 T 0 0 
FT T P0 dL dL D
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Recall Example 44 with 60 ft PBR where FT = FT0 & T = T0, the
calculated P was 73.5% (P0=10P=2.65 atm).
For the same flow conditions given in Example 44 for an unpacked
pipe with a length of up to 1000 ft, the P is less than 10%.
Hence, normally P for gases flowing through pipes without
packing can be neglected.
However, for high volumetric flow rates through microreactors, the
P may be significant.
Week 8  Lecture 29
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Design Problem 3:
(lost)
(lost)
(lost)
CSTR
C A0
X
rA exit
This equation applies to a single CSTR or to the first reactor
of CSTRs connected in series.
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This exercise is to show that starting from the design eq. we can
write: V = f(X), X = f(, k, CA0), V = f(Da), & CA = f( , k, CA0)
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CA1():
CA2():
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X
FA0
VS.
 rAi
 rA
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or . Compare to
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or
FA0 Xi
V
kCA0 1 Xi
Compare to the single large reactor D. Eq.:
FA0 X
V
kCA0 1  X
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Design Problem 3:
(lost)
(lost)
(lost)
CSTR
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It is desired to produce 200 million pounds per year of EG. The reactor
is to be operated isothermally. A 1 lbmol/ft3 solution of ethylene
oxide (EO) in water is fed to the reactor together with an equal
volumetric solution of water containing 0.9 wt% of the catalyst
H2SO2. The specific rxn rate constant is 0.311 min1 (will be
determined later in Example 41). The rate law is rA = kCA.
It is desired to produce 200 million pounds per year of EG. The reactor is to be
operated isothermally. A 1 lbmol/ft3 solution of ethylene oxide (EO) in water is fed
to the reactor together with an equal volumetric solution of water containing 0.9 wt%
of the catalyst H2SO2. The specific rxn rate constant is 0.311 min1 while the rate law
is rA = kCA.
CA0
0.5 lbmol/ft 3
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It is desired to produce 200 million pounds per year of EG. The reactor is to be
operated isothermally. A 1 lbmol/ft3 solution of ethylene oxide (EO) in water is fed
to the reactor together with an equal volumetric solution of water containing 0.9 wt%
of the catalyst H2SO2. The specific rxn rate constant is 0.311 min1 while the rate law
is rA = kCA.
 rA kCA
mC 200 106 lb/year
MM C 62 lb/lbmol
The algorithm for the CRE design problem is:
T Constant
1. Mole balance, Design Equation
C A01 1 lbmol/ft 3
2. Write Rate law
C A0 0.5 lbmol/ft 3 3. Stoichiometry (to find Cj)
4. Combine (all of the above)
FC 6.137 lbmol/min
5. Evaluate
FC 6.137 lbmol/min
FA 0 7.530 lbmol/min
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Consider the same feed characteristic: FA0 = 7.53 lbmol/min, CA0 = 0.5
lbmol/ft3
X 0.815
(c) If two 800gal (106.7ft3) reactors were arranged in series, what are
the corresponding Xs?
Consider the same feed characteristic: FA0 = 7.53 lbmol/min, CA0 = 0.5
lbmol/ft3
X 1 0.688
X 2 0.903
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X 1 0.688
X 2 0.903
X 0.815
1600gal SingeCSTR
X 1 0.688
X 2 0.903
X 0.815
800gal 2ndCSTR
1600gal SingeCSTR
800gal 1stCSTR
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The three reactors designed in examples 42, 43, & 46 can be
arranged to form a chemical plant to produce 200 MM lbm/year of
ethylene glycol from a feedstock of 402 MM lbm/year of ethane.
Read at Home
(lost)
(lost)
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(lost)
(lost)
(lost)
The operating costs include such costs as energy, labor, overhead, &
depreciation of equipment.
You will learn more about these costs & the process economics in
Chemical Plant Design course (CHENG 422).
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Ci or Fi
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A + 2B C
3. Stoichiometry
b)
4. Combine
5. Evaluate
c)
d)
(4)
&
(5)
where rA k AC AC B
are shown in this table:
Where are these equations
coming from?
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(lost)
Design Problem 4:
(lost)
(lost)
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Example 41
It is desired to design a CSTR to produce 200 million pounds of
ethylene glycol per year by hydrolyzing ethylene oxide. However,
before the design can be carried out, it is necessary to perform and
analyze a batch reactor experiment to determine the specific rxn
rate constant, k.
Because the reaction will be carried out isothermally, k will need to be
determined only at the rxn T of the CSTR. At high temperatures
there is a significant byproduct formation, while at temperatures
below 40C the rxn does not proceed at a significant rate;
consequently, a temperature of 55C has been chosen.
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Week 10  Lecture 33
3. Stoichiometry
rA' rB' rC' rD' 4. Combine
3 Eqns
a b c d 5. Evaluate
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Fig: Microreactors.
Ref: www.carbogenamcis.com
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Solution:
2NOCl 2NO + Cl2
2A 2B + C
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2. Rate law
rA = kCA2
k = 0.29*exp[E/R(1/T1/500)] where E = 24x103 cal/mol
3. Stoichiometry
Gas phase with T = T0 and P = P0
Relative Rates
Concentrations
4. Combine
Using Polymath
5. Evaluate
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Membrane Reactors
FA0  FA B
X A C
FA0
FB FA0 B B X
A C
B
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The dehydrogenation of propane is another reaction that has proven successful with a
membrane reactor:
and could take place on the catalyst side of an IMR or inside a CMR.
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CMR
X = 0.567
FA FC
FA
FC
FB
FB
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PFR
X = Xeq = 0.447
FA
FB & F C
Week 11  Lecture 37
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UnsteadyState Operations
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The general mole balance equation for the given system is:
dN A
FA0  FA rAV
dt
Conversion does not have any meaning in startup because one cannot
distinguish between the NA present due to unreacted A molecules &
these due to accumulation within the CSTR due to introduction of A.
Rewrite the balance equation in terms of concentration.
dC A AB
C A0  C A rA Feed Product
dt 0, CA0 , CA & CB
For most 1storder systems (not necessarily
1storder rxn), steady state is achieved in 4
to 5 times the systems time constant.
Startup of a constant volume CSTR
Example: Startup of a Constant Volume CSTR
Consider the first order liquid phase reaction that is carried out in a wellmixed reactor initially
filled with the solvent only. Assume the density of the reaction mixture remains constant during the
course of the reaction, i.e. = 0 & V = Vi.
Additional information: k = 0.311 min1, V = 213.3 L, CA0 = 0.500 mol/L, 0 = 15.34 L/min.
1. For the startup period, perform mole balances on A and B in terms of CA, CB, & other constants.
2. Use the derived ordinary differential equations to plot the concentrations of A & B as a function
of time.
3. Calculate the steady state values of CA, XA, and CB. Do both CA and CB achieve their steady state
values at the same time?
4. Determine the system order for both species by examining the obtained differential equations
and concentration profiles.
5. For the first order system(s), if any, determine:
I. the time constant, the steadystate gain, and the input (forcing function). Hint: rewrite the
differential mole balance in the standard form of a firstorder system.
II. the time necessary for the concentration to achieve 99% of its steady state value. Compare
that time with the time constant; is it reasonable for a first order system?
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Addition of a reactant
A+BC+D
Feed
CA0 & CB0
A+BC+D
4.10.2 Semibatch Reactors A+BC+D
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chlorination
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Undesired rxn:
How can we produce the most of our desired product and the least of
our undesired product?
By keeping the CA high and the CB low.
How can this achieved?
This can be achieved through the use of the semibatch reactor, which
is charged with pure A and to which B is fed slowly to A in the vat.
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Commercial Break
Now you are ready
to read this article:
Published in Chemical
Engineering Progress, An
AIChE Publication, CEP:
Mar 2001.
the conversion, X.
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For the considered reaction, rewrite the mole balance equations for
species A & B in terms of concentration.
Also find V(t)
A+BC
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C C + H2O 2 C
H3C O CH3 H3C OH
*Haji, Shaker; Erkey, Can. AN EXPERIMENT FOR UNDERGRADUATE LABORATORY KINETICS OF HYDROLYSIS OF ACETIC ANHYDRIDE BY IN
SITU FTIR SPECTROSCOPY. Chemical Engineering Education, winter 2005.
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where
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Therefore,
Solving for t:
Closure
Heat Effects
Isothermal Design
Stoichiometry
Rate Laws
Mole Balance
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Homework Solutions
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