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Chemical Reaction Engineering

Introduction & Lecture 1

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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What is Chemical Reaction Engineering
(CRE) ?
Understanding how chemical reactors work lies at the heart of
almost every chemical processing operation.

Raw Separation Chemical Separation Products

material Process process Process By-products

Design of the reactor is no routine matter, and many

alternatives can be proposed for a process. Reactor design
uses information, knowledge and experience from a variety of
areas - thermodynamics, chemical kinetics, fluid mechanics,
heat and mass transfer, and economics.

CRE is the synthesis of all these factors with the aim of

properly designing and understanding the chemical reactor.
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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How do we design a chemical reactor?

Type & size

Maximize the space-time yield of the desired product

(productivity lb/hr/ft3)

Stoichiometry
Kinetics
Basic molar balances Reactor volume
Fluid dynamics

Use a lab-scale reactor to determine the kinetics!

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Reactor Design

Reaction
Stoichiometry
Kinetics: elementary vs non-elementary
Single vs multiple reactions

Reactor
Isothermal vs non-isothermal
Ideal vs nonideal
Steady-state vs nonsteady-state

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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What type of reactor(s) to use?

in
Continuously Stirred
Tank Reactor (CSTR)

out

Plug flow reactor (PFR)

Well-mixed batch reactor
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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What size reactor(s) to use?

Answers to this questions are based on the desired
conversion, selectivity and kinetics

Kinetics
Reactor type Conversion
& &
size Material & selectivity
energy
balances

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Chemical Reaction
• A detectable number of molecules have lost their identity
and assumed a new form by a change in the kind or number
of atoms in the compound and/or by a change in the atoms’
configuration
• Decomposition
• Combination
• Isomerization
• Rate of reaction
– How fast a number of moles of one chemical species are
being consumed to form another chemical species

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Rate Law for rj

• rA: the rate of formation of species A per unit volume [e.g., mol/m3•s]
• -rA: the rate of a consumption of species A per unit volume
A  B  products r A  kC A CB
1st order in A, 1st order in B, 2nd order overall
r A  kC A n nth order in A
k1C A
 rA  Michaelis-Menton: common in enzymatic reactions
1  k 2C A

rj depends on concentration and temperature:

 Ea 
 RT 
-rA  A e C
A Arrhenius dependence on temperature
A: pre-exponential factor E A : activation energy
R : ideal gas constant T:temperature

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Basic Molar Balance (BMB)

Fj0 Fj
Gj

System volume
Rate of Rate of Rate of
Rate of
flow of j - flow of j + generation of j - Rate of
decomposition =
into out of by chemical accumulation
of j
system system rxn

combine Nj: moles j in

system at time t
dN j
Fj  Fj  Gj 
0 dt
 mol   mol   mol  d
       mol 
 s   s   s  dt

in - out + generation = accumulation

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Basic Molar Balance (BMB)

Rate of Rate of Rate of
Rate of
flow of j - flow of j + generation of j - Rate of
decomposition =
into out of by chemical accumulation
of j
system system rxn
dN j
Fj  Fj  Gj 
0 dt
 mol   mol   mol  d
       mol 
 s   s   s  dt
If the system is uniform throughout its entire volume, then:
G j  rj V
Moles
Moles j
generated per
generated Volume
= unit time and
per unit time (m3)
volume
(mol/s)
(mol/s•m3)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Non-Uniform Generation
system
If rj varies with position (because
the temperature or concentration
DV
varies) then rj1 at location 1 is Rate is rj1
surrounded by a small subvolume within this Rate is rj2
DV within which the rate is uniform DV volume within this
m V volume
G j  lim  rjV   rjdV
m→∞ i1
DV→0

1
111
then G j     rj  x, y, z  dx dy dz
000
1 y
1 Plug in rj and integrate over x, y, and z
x

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Basic Molar Balance Equations

Fj0 Fj
Gj

System volume

In - Out +Generation = Accumulation

dN j
Fj0  F j G j 
dt
dN j
Fj0  F j rj V  uniform rate in V
dt
V dN j
Fj0  F j   rjdV  nonuniform rate in V
dt
Next time: Apply BME to ideal batch, CSTR, & PFR reactors
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Review of Frequently Encountered

Math Concepts

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Basic Math Review

1 p
 x n
e   a
q q p ln a
x n x  x

 
ln x y  y ln  x 
x
ln  x   ln  y   ln  
y
ln  x   ln  y   ln  xy 

Example: Problems that Contain Natural Logs

a
Solve for X: ln  bt  1  ln  x   ln  y 
b
a
b
ln  bt  1  ln  x   ln  y  
 ln  bt  1
a b
 x
 ln  
y

  x
x a b
ln  bt 1 a b ln    bt  1   y  bt  1
a b
x
e e y y

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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Review of Basic Integration

1 p
 x n q
x n x q
 xp

  b n 1 a n 1
b b b
1  n 1
n
For n≠1:  n dx   x dx   x  n  1  
 
ax a a n  1 n  1

b 1 b b
For n=1:  n dx      a  ln  b   ln  a   ln  a 
ln x 
ax  

t   1    1    c t  0 
5 dx t 5
Solve c  1  c
 2    dt        t  0 5  1 d  
for t: 1 x d0  x 1 d  

c c d
 0.2  1   t  0.8   t  0.8 t
d d c

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
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 k  dc  k  dc
Solve for c:   c      dt 
 1  k t
d  dt  1  k t
d  c
1t c dc
 k  dt   Do NOT move t or c outside of the integral
0 1  kd t c c 0

x dx x
From 1  ε is a
  ln  1   x  
Appendix A: 0 1   x  0 constant
t
1  c
k  ln  1  k d t    ln  c   c
kd 0 0

1 1 
 k  ln  1  k d t   ln  1  k d 0    ln  c   ln  c 0 
kd kd 0
k k  c 
 ln  k d t  1  ln  c   ln  c0   ln  k d t  1  ln  
kd kd  c0 
 k    c   k   k 
 ln k d t 1  ln   k ln d 
k t 1
c  ln k d t 1 
kd c   kd
 e    e  0   e d   c0 e   c
c0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.