Professional Documents
Culture Documents
Cheng 323 Chap 4
Cheng 323 Chap 4
CHENG 323 1
Dr. Shaker Haji, University of Bahrain
In this Chapter
In this Chapter
CHENG 323 2
Dr. Shaker Haji, University of Bahrain
CHENG 323 3
Dr. Shaker Haji, University of Bahrain
CHENG 323 4
Dr. Shaker Haji, University of Bahrain
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.
CHENG 323 5
Dr. Shaker Haji, University of Bahrain
CHENG 323 6
Dr. Shaker Haji, University of Bahrain
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
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).
CHENG 323 7
Dr. Shaker Haji, University of Bahrain
(lost)
Example 4-1:
Batch
(kinetics)
CHENG 323 8
Dr. Shaker Haji, University of Bahrain
CHENG 323 9
Dr. Shaker Haji, University of Bahrain
Design Problem 1:
(lost)
PFR
(lost)
(lost)
CHENG 323 10
Dr. Shaker Haji, University of Bahrain
dX
Liquid Phase case: =0 -rA kC A2 FA0
dV
- rA
CHENG 323 11
Dr. Shaker Haji, University of Bahrain
dX
Gas Phase case: 0 -rA kC A2 FA0
dV
- rA
Plot X along the length (volume) of the reactor for different values
of .
CHENG 323 12
Dr. Shaker Haji, University of Bahrain
X
= 0 (1+ X) 0.4
0.3
-0.5 A 0.5 B
0 A B
1 A 2 B
0.2
2 0.1
0
1.75 0 2 4 6 8 10
1.5 V, m3
-0.5 A 0.5 B When < 0 ( < 0),
0
/0
1 progresses, thus,
residence time
0.75
increases and ,
0.5 therefore, X
0 2 4 6 8 10 increases
V, m3
0.75 0 2 4 6 8 10
-0.5 A 0.5 B
V, m3
0 A B
CA/CA0
0.5 1 A 2 B
0.25
0
0 2 4 6 8 10
V, m3
CHENG 323 13
Dr. Shaker Haji, University of Bahrain
PFR
(lost)
CHENG 323 14
Dr. Shaker Haji, University of Bahrain
Solution:
m B 300 106 lb/y, X 0.8, T 1100K, P 6 atm
Data from literature: k = 0.072 s-1 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
CHENG 323 15
Dr. Shaker Haji, University of Bahrain
The concentration and conversion profiles down any one of the pipes
are shown above.
CHENG 323 16
Dr. Shaker Haji, University of Bahrain
Submit Homework
#5
one week from today
Design Problem 2:
(lost)
(lost)
PBR
(lost)
CHENG 323 17
Dr. Shaker Haji, University of Bahrain
CHENG 323 18
Dr. Shaker Haji, University of Bahrain
dX
FA0 - rA' -rA' kC A2
dW
dX
Which implies that for isothermal operation: F1 (X , P )
dW
CHENG 323 19
Dr. Shaker Haji, University of Bahrain
Term 1 is dominant for laminar flow, while Term 2 is dominant for turbulent flow.
CHENG 323 20
Dr. Shaker Haji, University of Bahrain
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
CHENG 323 21
Dr. Shaker Haji, University of Bahrain
W Ac Z (1 - ) c or dW Ac (1 - ) c dZ
where
CHENG 323 22
Dr. Shaker Haji, University of Bahrain
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
Conclusion:
Where y=P/P0
CHENG 323 23
Dr. Shaker Haji, University of Bahrain
Analytical Solution
Rearranging:
CHENG 323 24
Dr. Shaker Haji, University of Bahrain
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 unit of 0 ?
CHENG 323 25
Dr. Shaker Haji, University of Bahrain
P0
P P0 1 - 0.0155 z 0
0.5
CHENG 323 26
Dr. Shaker Haji, University of Bahrain
First, lets examine the effect of the pressure drop on the rxn:
Second, lets discuss how the pressure drop affect our CRE algorithm.
Consider the 2nd order isothermal The algorithm for the CRE design
problem is:
rxn: A B, occurring in a PBR.
1. Mole balance, Design Equation
Design Equation: 2. Rate Law
3. Stoichiometry (to find Cj)
Rate Law:
4. Combine (all of the above)
5. Evaluate
Stoichiometry:
Combine:
CHENG 323 27
Dr. Shaker Haji, University of Bahrain
Combine:
Reconsider the packed bed in Example 4-4 for the case where a second-order rxn,
2A B + C, is taking place in 20 meters of a 1 schedule 40 pipe packed with catalyst.
The flow and packed-bed conditions in the example remain the same except that they are
converted to SI 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, Cross-sectional area of the pipe: Ac = 0.0013 m2
Cat. particle size: Dp = 0.006 m, Solid catalyst density: c = 1923 kg/m3
CHENG 323 28
Dr. Shaker Haji, University of Bahrain
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, Cross-sectional 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
CHENG 323 29
Dr. Shaker Haji, University of Bahrain
Solution
CHENG 323 30
Dr. Shaker Haji, University of Bahrain
CHENG 323 31
Dr. Shaker Haji, University of Bahrain
(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.
CHENG 323 32
Dr. Shaker Haji, University of Bahrain
Design Problem 2:
(lost)
(lost)
PBR
(lost)
CHENG 323 33
Dr. Shaker Haji, University of Bahrain
Solution:
Design Equation:
Stoichiometry:
Combine:
CHENG 323 34
Dr. Shaker Haji, University of Bahrain
Combine:
Evaluate:
Combine:
Evaluate:
CHENG 323 35
Dr. Shaker Haji, University of Bahrain
From Example 4-4, 0 = 0.0775 atm/ft; & Example 4-5, = 0.0166 lbm-1
Evaluate:
CHENG 323 36
Dr. Shaker Haji, University of Bahrain
where,
CHENG 323 37
Dr. Shaker Haji, University of Bahrain
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
CHENG 323 38
Dr. Shaker Haji, University of Bahrain
2
FT 0 T 0 P dP G d 2fG 2
0 -
FT T P0 dL dL D
Recall Example 4-4 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 4-4 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.
CHENG 323 39
Dr. Shaker Haji, University of Bahrain
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.
CHENG 323 40
Dr. Shaker Haji, University of Bahrain
C A0
X
4.3.1 A single CSTR
-rA exit
CHENG 323 41
Dr. Shaker Haji, University of Bahrain
CA1():
CA2():
CHENG 323 42
Dr. Shaker Haji, University of Bahrain
CHENG 323 43
Dr. Shaker Haji, University of Bahrain
or . But also
CHENG 323 44
Dr. Shaker Haji, University of Bahrain
Design Problem 3:
(lost)
(lost)
(lost)
CSTR
CHENG 323 45
Dr. Shaker Haji, University of Bahrain
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 min-1 (will be
determined later in Example 4-1). The rate law is rA = kCA.
CHENG 323 46
Dr. Shaker Haji, University of Bahrain
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 min-1 while 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 min-1 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
CHENG 323 47
Dr. Shaker Haji, University of Bahrain
FC 6.137 lbmol/min
FA 0 7.530 lbmol/min
Consider the same feed characteristic: FA0 = 7.53 lbmol/min, CA0 = 0.5
lbmol/ft3
X 0.815
CHENG 323 48
Dr. Shaker Haji, University of Bahrain
(c) If two 800-gal (106.7-ft3) 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 0.68
X 2 0.9
The three reactors designed in examples 4-2, 4-3, & 4-6 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.
CHENG 323 49
Dr. Shaker Haji, University of Bahrain
(lost)
(lost)
(lost)
(lost)
(lost)
CHENG 323 50
Dr. Shaker Haji, University of Bahrain
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).
CHENG 323 51
Dr. Shaker Haji, University of Bahrain
Submit Homework
#6
one week from today
CHENG 323 52
Dr. Shaker Haji, University of Bahrain
4. Combine
5. Evaluate c)
d)
(4)
&
(5)
CHENG 323 53
Dr. Shaker Haji, University of Bahrain
where -rA k AC AC B
are shown in this table:
Where are these equations
coming from?
CHENG 323 54
Dr. Shaker Haji, University of Bahrain
(lost)
Design Problem 4:
(lost)
(lost)
Example 4-1
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 by-product formation, while at temperatures
below 40C the rxn does not proceed at a significant rate;
consequently, a temperature of 55C has been chosen.
CHENG 323 55
Dr. Shaker Haji, University of Bahrain
CHENG 323 56
Dr. Shaker Haji, University of Bahrain
C
ln A0 k t
CA
FYI only
t , min C c , M C A , M C A0 /C A ln (C A0 /C A) X
0 0 1 1 0 0.000
0.5 0.145 0.855 1.170 0.157 0.145
1 0.270 0.730 1.370 0.315 0.270
1.5 0.376 0.624 1.603 0.472 0.376
2 0.467 0.533 1.876 0.629 0.467
3 0.610 0.390 2.564 0.942 0.610
4 0.715 0.285 3.509 1.255 0.715
6 0.848 0.152 6.579 1.884 0.848
10 0.957 0.043 23.256 3.147 0.957
C A0 = 1 M
3.5
3 Y = 0.3145X - 0.0007
2.5 R = 1
ln(CA0/CA)
2
1.5
1
0.5
0
0 2 4 6 8 10 12
t, min
CHENG 323 57
Dr. Shaker Haji, University of Bahrain
.
Y = 0.9993e0.3145 X
R = 1
CA0/CA
10
1
0 2 4 6 8 10 12
t, min
Practical guidelines for reactor scale-up were recently given by Mukesh
and by Warsteel (see textbook for references)
3. Stoichiometry
-rA' -rB' rC' rD' 4. Combine
3 Eqns
a b c d 5. Evaluate
CHENG 323 58
Dr. Shaker Haji, University of Bahrain
CHENG 323 59
Dr. Shaker Haji, University of Bahrain
CHENG 323 60
Dr. Shaker Haji, University of Bahrain
CHENG 323 61
Dr. Shaker Haji, University of Bahrain
Fig: Microreactors.
Ref: www.carbogen-amcis.com
CHENG 323 62
Dr. Shaker Haji, University of Bahrain
Solution:
2NOCl 2NO + Cl2
2A 2B + C
CHENG 323 63
Dr. Shaker Haji, University of Bahrain
2. Rate law
-rA = kCA2
k = 0.29*exp[-E/R(1/T-1/500)] where E = 24x103 cal/mol
3. Stoichiometry
Gas phase with T = T0 and P = P0
Relative Rates
Concentrations
4. Combine
Using Polymath
5. Evaluate
CHENG 323 64
Dr. Shaker Haji, University of Bahrain
CHENG 323 65
Dr. Shaker Haji, University of Bahrain
CHENG 323 66
Dr. Shaker Haji, University of Bahrain
CHENG 323 67
Dr. Shaker Haji, University of Bahrain
CHENG 323 68
Dr. Shaker Haji, University of Bahrain
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.
CHENG 323 69
Dr. Shaker Haji, University of Bahrain
CMR
X = 0.567
CHENG 323 70
Dr. Shaker Haji, University of Bahrain
PFR
X = Xeq = 0.447
CHENG 323 71
Dr. Shaker Haji, University of Bahrain
= 0 & V = V0
CHENG 323 72
Dr. Shaker Haji, University of Bahrain
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.
Rewrite the balance equation in terms of concentration.
dC A AB
C A0 - C A rA Feed Product
dt 0, CA0 , CA & CB
Addition of a reactant
Feed
CA0 & CB0
CHENG 323 73
Dr. Shaker Haji, University of Bahrain
A+BC+D
4.10.2 Semibatch Reactors A+BC+D
CHENG 323 74
Dr. Shaker Haji, University of Bahrain
chlorination
Undesired rxn:
CHENG 323 75
Dr. Shaker Haji, University of Bahrain
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.
Commercial Break
Now you are ready
to read this article:
Published in Chemical
Engineering Progress, An
AIChE Publication, CEP:
Mar 2001.
CHENG 323 76
Dr. Shaker Haji, University of Bahrain
the conversion, X.
For the considered reaction, rewrite the mole balance equations for
species A & B in terms of concentration.
Also find V(t)
A+BC
CHENG 323 77
Dr. Shaker Haji, University of Bahrain
CHENG 323 78
Dr. Shaker Haji, University of Bahrain
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.
CHENG 323 79
Dr. Shaker Haji, University of Bahrain
CHENG 323 80
Dr. Shaker Haji, University of Bahrain
where
Therefore,
Solving for t:
CHENG 323 81
Dr. Shaker Haji, University of Bahrain
Closure
Heat Effects
Isothermal Design
Stoichiometry
Rate Laws
Mole Balance
Submit Homework
#7
one week from today
CHENG 323 82