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Chbi502 Chapter 4
Chbi502 Chapter 4
3. Stoichiometry
4. Combine
5. Evaluate
The Evaluate Step can be carried out
A. Graphically (Plots)
B. Numerically (Quadrature Formulas)
C. Analytically (Integral tables)
D. Using Software Packages
1
Elementary gas phase reaction in different reactor types
CSTR
The elementary gas phase reaction 2A + B → C
takes place in a CSTR at constant temperature (500 K) and constant pressure
(16.4 atm). The feed is equal molar in A and B. x = 0.9, k= 10dm6/mol2s
VCSTR =?
Mole balance
Rate Law
Derivation
2
Combine
Evaluate
Rate Law
3
Combine
V=227 dm3
Deriving CA and CB
4
And if the feed is equal molar, then:
Mole Balance
Rate Law
Stoichiometry
Combine
5
Parameter Evaluation CAo=0.2, k=10 dm6/mol2 s,
6
Scale – Up of Liquid – Phase Batch Reactor Data to Design of a CSTR:
Scale – Up a lab experiment to pilot – plant operation of full – scale
production. Find k from experimental data and use it to design a full – scale
flow reactor.
Batch Operation:
Liquid phase: (density change is small → V = V0)
Gas phase with constant volume V = V0.
1 ⎛ dN A ⎞
⋅⎜ ⎟ = rA
V ⎝ dt ⎠
1 ⎛ dN A ⎞ 1 dN A dN A / V0 dC A
⋅⎜ ⎟= ⋅ = = = rA
V ⎝ dt ⎠ V0 dt dt dt
A→B
dX [1]
N A0 ⋅ = −rA ⋅ V0
dt
[2]
− rA = k ⋅ C A
2
C A = C A0 ⋅ (1 − X ) [3]
Combine [1], [2] and [3];
dX
= k ⋅ C A0 ⋅ (1 − X ) 2
dt
Rearrange: dX
= k ⋅ C A0 ⋅ dt
(1 − X ) 2
@ t = 0; X = 0; T = T0 (isothermal) → k → constant
⎛ X ⎞
t X
1 dX 1
∫t =
0
k ⋅ C A0 ∫ (1 − X )
0
2
⇒ t= ⋅⎜ ⎟
k ⋅ C A0 ⎝ 1 − X ⎠
7
It is important to know the reaction time, tR, to achieve a certain
conversion.
Flow reactors use characteristic rxn times, tR.
The time for a total cycle is much longer than tR, as one must account for
the time to fill (tF), heat (th) and clean (tC).
t = tf + th + tC + tR
Design of Continuous Stirred Tank Reactors
CSTRs are usually used for liquid phase rxns:
FA0 ⋅ X v0 ⋅ C A0 ⋅ X
V= = [1] (Design Eq’n for CSTR)
(− rA ) exit − rA
Divide by v0: V C A0 ⋅ X [2]
τ= =
v0 − rA
Volumetric flow rate
A single CSTR:
First order irreversible rxn:
1 ⎛ X ⎞
τ = ⋅⎜ ⎟ [5]
k ⎝1− X ⎠
τ ⋅k [6]
X=
1+τ ⋅ k
C A0
Combine [4] and [6] CA =
1+τ ⋅ k
rxn Damköhler #,
Da: a dimensionless # that for a first order rxn
says the degree of conversion that can be achieved in cont. flow reactor.
8
− rA0 ⋅V rate of rxn of A
Da = :
FA0 rate of convective transport of A t =0
− rA0 ⋅ V k ⋅ C A0 ⋅V
2
Da = = = τ ⋅ k ⋅ C A0
FA0 v0 ⋅ C A0
Da
X= First order liq-phase rxn (Eq’n [6])
1 + Da
CSTRs in Series
CA1, X1
9
If both reactors are of equal size, (τ 1 = τ 2 = τ )
and operate at the same T (k1 = k2 = k)
C A0
C A2 =
(1 + τ ⋅ k ) 2
for n equal sized CSTR system
C A0 C A0
C An = =
(1 + τ ⋅ k ) n
(1 + Da) n
CSTRs in Parallel:
Equal sized reactors are placed in parallel rather than in series:
FA01 FA02 FA03 FA0n
X1 X2 X3 Xn
V FA0 ⎛ X i ⎞ X
= .⎜ ⎟ = FA0 ⋅ [4]
n n ⎜⎝ − rAi ⎟⎠ − rA
10
Example: 2nd order rxn, v = v0, CA = CA0 (1-X); FA0 X = v0 CA0 X
Combine –rA = k CA2 and V = FA0 X / -rA
FA0 ⋅ X v0 ⋅ C A0 ⋅ X
V= =
k ⋅ CA k ⋅ C A0 ⋅ (1 − X ) 2
2 2
Divide by v0:
V X
τ= =
v0 k ⋅ C A0 ⋅ (1 − X ) 2
(1 + 2 ⋅τ ⋅ k ⋅ C A0 ) − (1 + 2 ⋅τ ⋅ k ⋅ C A0 ) 2 − (2 ⋅τ ⋅ k ⋅ C A0 ) 2
X=
2 ⋅τ ⋅ k ⋅ C A0
(1 + 2 ⋅ Da) − 1 + 4 Da
X= Since τ ⋅ k ⋅ C A0 = Da
2 ⋅ Da for a second order rxn.
Mole Balance
Rate Law
11
Combine
Evaluate at X = 0.9,
V = 1125 dm3
Space Time
12
Applying the algorithm to the above reaction occuring in Batch, CSTR, PFR
13
3. Reversible Reaction
To determine the conversion or reactor volume for reversible
reactions, one must first calculate the maximum conversion that can
be achieved at the isothermal reaction temperature, which is the
equilibrium conversion. (See Example 3-8 in the text for additional
coverage of equilibrium conversion in isothermal reactor design.)
Equilibrium Conversion, Xe
Xe = 0.89
X = 0.8Xe = 0.711
14
Deriving The Equilibrium Constant (KC) and Equilibrium
Conversion (Xe) for a Non-Constant Volume System:
The reversible reaction:
which takes place in gas phase PFR. Since gas phase reactions almost
always involve volume changes, we will have to account for volume
changes in our calculations. The equilibrium constant, KC, for this
reaction is:
15
Batch Reactor With a Reversible Reaction
Initially 77% N2, 15% O2, 8% inerts are fed to a batch reactor where 80%
of the equilibrium conversion (Xe = 0.02) is reached in 151 µ s. What is
the specific reaction rate constant k1?
Additional Information
16
For 80% of equilibrium conversion X = 0.8 Xe = 0.016
17
Tubular Reactors:
Gas-phase rxns are usually carried out in tubular reactors where the gas
is generally turbulent.
Reactants Products
dX
Design Eq’n: FA0 ⋅ = − rA
dV
In the absence of pressure drop or heat exchange, integral form of the
design equation is used:
X
dX
V = FA0 ⋅ ∫
0
− rA
Mole Balance
Must use the differential form of the mole balance to separate variables:
Rate Law
Second order in A and irreversible:
18
Stoichiometry
Isothermal, T = T0
Combine
Ergun Equation
P = pressure (kPa) • •
Ergun, S., 1952. Fluid flow through packed columns. Chemical Engineering Progress 48, pp. 89–94.
19
Variable Density
Catalyst Weight
Then
Since ⎛ F ⎞
FT = FT 0 + FA0δX = FT 0 ⎜⎜1 + A0 δX ⎟⎟
⎝ FT 0 ⎠
FT ⎛ F ⎞
= 1+ ε ⋅ X ⎜⎜ ε = y A0 ⋅ δ = A0 ⋅ δ ⎟⎟
FT 0 ⎝ FT 0 ⎠
20
when ε<0; ∆P will be less than ε = 0.
when ε>0; ∆P will be greater than ε = 0.
Isothermal Operation
Recall that
Notice that
The two expressions are coupled ordinary differential equations. We can solve
them simultaneously using an ODE solver such as Polymath. For the special
case of isothermal operation and epsilon = 0, we can obtain an analytical
solution.
dy
2y ⋅ = −α
dW
y = 1 ( P = P0 ) @ W = 0
y 2 = 1 − α ⋅W
21
Combine
Solve
For gas phase reactions, as the pressure drop increases, the concentration
decreases, resulting in a decreased rate of reaction, hence a lower
conversion when compared to a reactor without a pressure drop.
22
Pressure Drop in Pipes:
Pressure drop for gases flowing through pipes without packing can be
neglected. For flow in pipes, ∆P is given by:
dP du 2 ⋅ f ⋅ G 2
= −G ⋅ −
dL dL g⋅D
Where
G = ρ u (g/cm3s) = mass velocity is constant along L.
u = average velocity of gas, cm/s.
f = fanning friction factor
f = fnc (Re, pipe roughness
P ⎡ 4 ⋅ f ⋅ G 2 ⋅V ⎤
= ⎢1 − ⎥ = (1 − α pV )
1/ 2
P0 ⎣ ρ 0 ⋅ P0 ⋅ AC ⋅ D ⎦
Example p 187
23
Optimum Particle Diameter
Cross-sectional area
24
Increasing the particle diameter descreases the pressure drop and increases
the rate and conversion.
However, there is a competing effect. The specific reaction rate decreases as the
particle size increases, therefore so deos the conversion.
k ∼ 1/Dp
25
The larger the particle, the more time it takes the reactant to get in and out
of the catalyst particle. For a given catalyst weight, there is a greater
external surgace area for smaller particles than larger particles. Therefore,
there are more entry ways into the catalyst particle.
Turbulent Flow
26
Compare Case 1 and Case 2:
For example, Case 1 might be our current situation and Case 2 might be
the parameters we want to change to.
Laminar Flow
A. Membrane reactors
B. Multiple reaction
Liquids: Use concentrations, i.e., CA
27
1. For the elementary liquid phase reaction carried out in a
CSTR, where V, vo, CAo, k, and Kc are given and the feed is pure A, the
combined mole balance, rate laws, and stoichiometry are:
28
• Microreactors
Are characterized by their high surface area to volume ratios (due to many
micro-tubes and channels). Dchannel = 100µm, Lch= 2 cm
They are used for highly exothermis rxns, for rxns with toxic or explosive
intermediates. ALso,i for the productions of speciality chemicalsi
combinatorial chemical screening, chemical sensors.
29
Membrane Reactors
Membrane reactors can be used to achieve conversions greater than the original
equilibrium value. These higher conversions are the result of Le Chatelier's
Principle; you can remove one of the reaction products and drive the reaction to
the right. To accomplish this, a membrane that is permeable to that reaction
product, but is impermeable to all other species, is placed around the reacting
mixture.
Mole Balances
Rate Laws
30
Stoichiometry
Isothermal, no pressure drop
Parameters
Solve Polymath
3. Semibatch Reactors
Semibatch reactors can be very effective in maximizing selectivity in liquid
phase reactions.
A + B ⎯⎯→
kD
D ( product )
A + B ⎯⎯→
kU
U (undesired )
rD = k D ⋅ C A ⋅ C B
2
rU = kU ⋅ C A ⋅ C B
2
kD ⋅ C A
Selectivity ( D / U ) =
kU ⋅ C B
The reactant that starts in the reactor is always the limiting reactant
31
Three Forms of the Mole Balance Applied to Semibatch Reactors
dX − rA
=
dV FA0
⎧⎪⎡ (1 − X ) ⎤ ⎡ C A0 ⋅ X
2
⎤ ⎫⎪
rA = − k ⎨⎢C A0 ⋅ ⎥ −⎢ ⎥⎬
⎪⎩⎣ 1 + ε ⋅ X ⎦ ⎣ 2(1 + εX ) ⋅ K C ⎦ ⎪⎭
32
Example: Elementary Irreversible Reaction
Consider the following irreversible elementary reaction
-rA = kCACB
The combined mole balance, rate law, and stoichiometry may be written
in terms of number of moles, conversion, and/or concentrati
Polymath Equations
33
Equilibrium Conversion in Semibatch Reactors with Reversible
Reactions
Consider the following reversible reaction:
Everything is the same as for the irreversible case, except for the rate law
Where:
34
function f=volume(V,x)
Ca0=0.2;
Kc=100;
Fa0=5;
k=2;
epsilon=-0.5;
ra=k*(((Ca0*(1-x(1))/(1+epsilon*x(1)))^2)-
(Ca0*x(1)/(2*Kc*(1+epsilon*x(1)))));
f(1)=ra/Fa0;
0.9
0.8
0.7
0.6
conversion
0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250 300 350 400 450 500
Volume
35
function f = packedbed(W,x)
alpha = 0.0002;
k = 10;
epsilon = -0.5;
FA0=2.5;
CA0 = 0.2;
f = zeros(2,1);
CA = (CA0*(1-x(1))*x(2))/(1 + epsilon*x(1));
ra = k*(CA.^2);
f(1) = ra / FA0;
f(2) = -alpha*(1 + epsilon*x(1))/(2*x(2));
1.001
0.999
0.998
y
0.997
0.996
0.995
0.994
0 10 20 30 40 50 60 70 80 90 100
W , kg
0.9
0.8
0.7
0.6
0.5
X
0.4
0.3
0.2
0.1
0
0 10 20 30 40 50 60 70 80 90 100
W , kg
36
Combining mole balances, rate laws and
stoichiometry
37
Pressure Drop in Packed Bed Reactors
Ergun Equation
P = pressure (kPa) • •
Ergun, S., 1952. Fluid flow through packed columns. Chemical Engineering Progress 48, pp. 89–94.
For gas phase reactions, as the pressure drop increases, the concentration
decreases, resulting in a decreased rate of reaction, hence a lower
conversion when compared to a reactor without a pressure drop.
38
Part 2: Mole Balances in terms of Conc’n & Molar Flow Rates
In some cases, it is more convenient to deal with number of moles or molar flow rates
rather than conversion.
Membrane reactors and multiple rxns taking place in gas phase are examples.
Microreactors with multiple reactions
39