Chemical Reaction Engineering

Lecture 3

Lecturer : 郭修伯
This course focuses on “isothermal ideal reactor design”.
 Design equations
• Batch:
– The conversion is a function of the time the
reactants spend in the reactor.
– We are interested in determining how long to leave
the reactants in the reactor to achieve a certain
conversion X.
dX
N A0   rAV
dt ?
?
 Design equations
• CSTR:
– We are interested in determining the size of the
reactor to achieve a certain conversion X.

X
FA0   rA
V ? -1/rA
?

X
 Design equations
• PFR:
– We are interested in determining the size of the
reactor to achieve a certain conversion X.

dX
FA0  rA
dV ?
?
-1/rA PBR

dX
Generally, the isothermal tubular reactor volume FA0   rA
is smaller than the CSTR for the same conversion dW
X
 Isothermal reactor design
• Design procedure
– mole balance
– rate laws
– stoichiometry
– combination of the above three procedures and
solve ODE
– obtain the volume/reaction time for the reactor
Do not forget to add some other time required!
 Reactor design
• Batch:
– constant volume, well-mixed
• CSTR:
– constant volumetric flow rate
 Damköhler number
 rA0V rate of reaction at entrance " A reaction rate"
Da   
FA0 entering flow rate of A " A convection rate"

– ratio of the rate of reaction of A to the rate of convective

transport of A at the entrance to the reactor
– estimation of the degree of conversion in a continuous reactor
• First order irreversible rxn:  rA0V kC A0V
Da    k
• Second order irreversible rxn: FA0 v0C A0
 r V
– Da = 0.1 ~ X = 10% ; Da = 10.0Da~ X =A0 90% kC 2
A 0V
  kC A0
FA0 v0C A0
Example, const.-V, batch, 2nd order rxn, isothermal
dX
• mole balance N A0  rAV
dt
• rate laws  rA  kC A2
• Stoichiometry C A  C A0 (1  X )
• combination dX
 kC A0 1  X 
2

dt

t 1 X dX 1 X
0 dt  kC A0  1  X  2 t ( )
kC A0 1  X
0

+ some additional time for filling, heating, …etc.

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 reaction rate constant, k. Because the
reaction will be carried out isothermally, the specific reaction rate will need
to be determined only at the reaction temperature of the CSTR. At high
temperature there is a significant by-product formation, while at temperature
below 40C the reaction does not proceed at a significant rate; consequently,
a temperature of 55C has been chosen. Because the water is usually present
in excess, its concentration may be considered constant during the course of
the reaction. In the laboratory experiment, 500 ml of a 2 M solution of
ethylene oxide in water was mixed with 500 ml of water containing 0.9 wt%
sulfuric acid, which is a catalyst. The temperature was maintained at 55C.
The concentration of ethylene glycol was recorded as a function of time,
determine the specific reaction rate at 55C.
 A  B  C
catalyst

Because water is present in such excess, the concentration of water at any

time t is virtually the same as the initial concentration and the rate law is
independent of the concentration of H2O. (CB≈CB0)
The reaction is first-order in ethylene oxide:
Batch design equation:

Rate law:
Stoichiometry no volume change, V=V0

Combination
 ?

A  B catalyst
 C

slope = -k = -0.311 min-1

Example, liquid phase CSTR, 1st order rxn, isothermal
FA0 X v0C A0 X V C A0 X
V  or   
• mole balance  rA  rA v0  rA
• rate laws  rA  kC A
• Stoichiometry C A  C A0 (1  X )
• combination 1 X  C A0
   or C A 
k 1 X  1  k
Da
or X
1  Da
Example, liquid phase CSTR, 2nd order rxn, isothermal
FA0 X v0C A0 X
V 
• mole balance  rA  rA
• rate laws  rA  kC A2

• Stoichiometry C A  C A0 (1  X )
• combination V
v0C A0 X 1  2kC A0   1  4kC A0
2 or X 
kC A0 1  X 
2
2kC A0
V X
or   
v0 kC A0 1  X  2

or X  1  2 Da   1  4 Da
2 Da
 CA0
CA1
CA2
CSTRs in series, 1st order rxn, isothermal
FA1 X FA1  FA 2 v0  C A1  C A 2 
V  
• mole balance  rA 2  rA 2  rA 2

• rate laws  rA 2  k 2C A 2

• Stoichiometry C A2  C A1 (1  X )
C A1 C A0 C A0
• combination C A2   
1   2 k 2 1   2 k 2 1   1k1  1  k  2
C A0 C A0
... C An  
1  k  1  Da  n
n

1
X  1 C An  C A0 (1  X )
1  k  n
 FA01
FA0
FA02 CSTRs in parallel, isothermal
.
.  Xi 
Vi  FA0i  
• mole balance   rAi 
same T, V, v
X 1  X 2  ...  X n  X
 rA1   rA 2  ...  rAn   rA

V FA0  X 
total volume   
total molar flow rate n n   rA 

FA0 X
V
 rA
 CSTRs in series
• constant flow rate
• conversion as a function of the number of tanks
in series Two equal-sized CSTRs in series will
give a higher conversion than two CSTRs in
parallel of the same size when the reaction
order is greater than zero.
 CSTRs in parallel
• constant conversion and rate of reaction in each tank
• The sum of the volume of the tanks equals the total volume of a
single large CSTR.
• The conversion achieved in any one of the reactors in parallel is
identical to what would be achieved if the reactant were fed in
one stream to one large reactor of volume V.
• Considering the degree of mixing and the room required, a large
tank might not be appropriate.
Example 4-2 Close to 12.2 billion metric tons of ethylene glycol (EG) were
produced in 2000, which ranked it the twenty-sixth most produced chemical in the
nation that year on a total pound basis. About one-half of the ethylene glycol is used
for antifreeze while the other half is used in the manufacture of polyesters. In the
polyester category, 88% was used for fibers and 12% for the manufacture of bottles
and films. The 2004 selling price for ethylene glycol was $0.28 per pound. It is
desired to produce 200 million pounds per year of EG. The reactor is to be operated
isothermally. A 1 lb mol/ft3 solution of ethylene oxide (EO) in water is fed to the
reactor (shown in Figure E4-2.1) together with an equal volumetric solution of water
containing 0.9 wt% of the catalyst H2SO4. The specific reaction rate constant is
0.311 min-1, as determined in Example 4-1.

A  B  Ccatalyst

The specified ethylene glycol (EG) production rate:

(a) If 80% conversion is to be achieved, determine the necessary CSTR volume.
A  B catalyst
 C
CSTR Design equation ：

Rate law ：
Stoichiometry ：

Combination
:
(b) If two 800-gal reactors were arranged in parallel, what is the corresponding
conversion?
CSTR Design equation ：

Rate law ：
Stoichiometry ：

Combination:

The conversion exiting each of the CSTRs in parallel is 81%.

(c) If two 800-gal reactor were arranged in series, what is the corresponding conversion?

The two equal-sized CSTRs in series will give a higher conversion than two
CSTRs in parallel of the same size when the reaction order is greater than zero.
 PFR
• Gas-phase reactions are carried out primarily in tubular
reactors where the flow is generally turbulent.
• Assuming no dispersion and there are no radial
gradients in either temperature, velocity, or
concentration.
• Should be aware of the change of the volume.

N.B.
The majority of gas-phase reactions are catalyzed by passing the reactant through
a packed bed of catalyst particles.
PFR, 2nd order rxn, liquid phase, isothermal
dX No pressure drop X dX
V  FA0 
FA0   rA 0 r
• mole balance dV No heat exchange A

• rate laws  rA  kC A2

• Stoichiometry C A  C A0 (1  X )
FA0 X dX v0C A0  X 
• combination V   2  
kC A2 0 0 1  X  kC A0  1  X 
2

kC A0 Da2
or X  
1  kC A0 1  Da2

Damköhler number for 2nd-order reaction

 PFR, 2nd order rxn, gas phase, isothermal
No pressure drop X dX
dX V  FA0 
FA0  rA
• mole balance dV No heat exchange
0 r
A

• rate laws  rA  kC A2
FA FA FA0 (1  X ) (1  X )
• Stoichiometry C A     C A0
v v0 (1  X ) v0 (1  X ) (1  X )

 1  X 
X
2

• combination V  FA0 0 kC A2 0 1  X  2 dX

v0   
1  X 
2
V 2 (1   ) ln(1  X )   X 
2

kC A0  1 X 
Example 4-3 Ethylene ranks fourth in the Unite States in total pounds of chemicals
produced each year, and it is the number one organic chemical produced each year.
Over 50 billion pounds were produced in 2000, and it sold for $0.27 per pound.
Sixty-five percent of the ethylene produced is used in the manufacture of fabricated
plastics, 20% for ethylene oxide, 16% for ethylene dichloride and ethylene glycol,
5% for fibers, and 5% for solvents.
Determine the plug-flow reactor volume necessary to produce 300 million pounds of
ethylene a year from cracking a feed stream of pure ethane. The reaction is
irreversible and follows an elementary rate law. We want to achieve 80% conversion
of ethane, operating the reactor isothermally at 1100 K at a pressure of 6 atm.
C2 H 6  C2 H 4  H 2 A BC k  0.072s1
@ 
1000K
The activation energy is 82 kcal/g mol.
The molar flow rate of ethylene (B):
PFR design equation ：

Rate law (elementary)

：
Stoichiometry ：

Combination:
(b) It was decided to use a bank of 2-in. schedule 80 pipes in parallel that are
40 ft in length. For pipe schedule 80, the cross-section are, Ac, is 0.0205 ft2.
The number of pipes necessary is
 Pressure drop in reactors
• In gas-phase reactions, the concentration of the
reacting species is proportional to the total pressure
and proper accounting for the effects of pressure drop
on the reaction system can be a key factor in the
success or failure of the reactor operation (e.g. PBR).
• When accounting for the effects of pressure drop, the
differential form of the mole balance must be used.
 PBR, 2nd order rxn, gas phase, isothermal
dX
FA0  rA '
• mole balance dW
• rate laws  rA '  kC 2
A

• Stoichiometry C j  C A0 ( j  v j X )  P  T0 CA 

C A0 (1  X )  P  T0
 
1  X   P0  T 1  X   P0  T
2 2
• combination dX  C A0 (1  X )  P
FA0  k   
dW  1  X   P0 
2 2
dX kC A0  1  X   P  dX
or       f ( X , P)
dW v0  1  X   P0  dW
What is the relationship between X and P? If PBR: Ergun equation
 Ergun equation
• Pressure drop in a porous bed:
Dominant for turbulent flow
dP G  1    150(1   )  
  3    1.75G 
dz g c D p     Dp 
Dominant for laminar flow
constant mass flow rate
v   0 v0 P0  T  FT
v  v0  
P  T0  FT 0

dP G  1    150(1   )   1 P0  T  FT
  3    1.75G   
dz gc Dp     Dp   0 P  T0  FT 0
 Ergun equation (cont.)
dP G  1    150(1   )   1 P0  T  FT
  3    1.75G   
dz gc Dp     Dp   0 P  T0  FT 0
Pressure drop in terms of Catalyst weight:
W  1    AC z   c
2 0

AC  C (1   ) P0
G  1    150(1   )  
0   3    1.75G 
0 gc Dp     Dp 
dP  T P0  FT  dP  T P0
    (1  X )
dW 2 T0 P / P0  FT 0  FT  FT 0  FA0X dW 2 T0 P / P0
 Gas phase, PBR with pressure change
2 2
dX kC A0  1  X   P 
    
dW v0  1  X   P0 
Solve simultaneously!
dP  T P0
 (1  X )
dW 2 T0 P / P0

Some special cases in the textbook!...

 Pressure drop in pipes without packing
dP du 2 fG 2 G  u d  G 
 G  dP  2 fG 2

dL dL D  G  
dL dL D
constant mass flow rate
v   0 v0
P0  T  FT
v  v0  
P  T0  FT 0
isothermal
FT  FT 0  FA0X
P02  P 2 2 P0  L P0  integrate P dP dP 2 fG 2
G  2 f  ln  0  G2  0
2 0  D P  f~const. P0 dL PdL D
 A B
PBR, 2nd order rxn, gas phase, isothermal
dX
• mole balance FA0 dW  rA '
• rate laws  rA '  kC A2
• Stoichiometry C  C A0 (1  X )  P  T0 dP    T P0 (1  X )
A
1  X   P0  T dW 2 T0 P / P0

C AC A0 (1  X ) 1  W 
• combination dX kC A2 0
 1  X  2 1   W 
dW FA0
1  1   (2v0 ) / kC A  X /(1  X )
W

 Spherical packed-bed reactors
• When small catalyst pellets are required, the pressure drop can be
significant, and thus the conversion decreases.
• One type of reactor that minimises pressure drop and is also
inexpensive to build is the spherical reactor, called an
ultraformer.
• Spherical reactor: the cross-sectional area and the weight of
catalyst are functions of the position.
• In addition to the higher conversion, the spherical reactor has the
economic benefit of reducing the pumping and compression cost
because of higher pressure at the exit.
 Mole balance and rate laws
• Concentration = f (conversion) We have done!
• There are a number of instances when it is much
more convenient to work in terms of the number of
moles (Ni) or molar flow rates (Fi) rather than
conversion.
– Membrane reactors and multiple reactions taking place in
the gas phase are two such cases where molar low rates
rather than conversion are preferred.
– Concentration = f (molar flow rate)
 Algorithm - liquid phase
• Liquid phase
– For liquid-phase reactions in which there is no
volume change, concentration is the preferred
variable.
– We have only to specify the parameter values for the
system (CA0, vo, etc.) and for the rate law to solve the
coupled ODEs for either PFR, PBR, or batch
reactors, or to solve the coupled algebraic equations
for a CSTR.
 Liquid phase – mole balance
aA  bB  cC  dD
Rector Mole Balance (A) Mole Balance (B)
Batch dC A
 rA
dC B b
 rA
dt dt a
CSTR v0  C A0  C A  v0  C B 0  C B 
V  V 
 rA  (b / a ) rA
PFR v0
dC A
 rA v0
dC B
 rA
b
dV dV a

PBR v0
dC A
 rA ' v0
dC B b
 rA '
dW dW a
 Algorithm - gas phase
• Gas phase
– For gas-phase reactions in which there is volume
change, molar flow rate is the preferred variable.
– The total molar flow rate is given as the sum of the
flow rate of the individual species.
– A mole balance on each species has to be specified.
 Gas phase – mole balance
aA  bB  cC  dD

Rector Mole Balance (A) Mole Balance (B)

Batch dN A
 rAV
dN B b
 rA
dt dt a
CSTR FA0  FA FB 0  FB
V  V 
 rA  b rA
a
PFR dFA
 rA
dFB b
 rA
dV dV a

PBR dFA
 rA '
dFB b
 rA '
dW dW a
 PBR, gas phase, isothermal, no ΔP
dFA
• mole balance  rA '
dW
• rate laws  rA  kC A C B

• Stoichiometry C  C FA  P  T0 dP  TP0 FT

FT  P0  T
A T0
dW 2 T0 FT 0
FT  FA  FB  FC  FD  FI
 
• combination dFA     FA   FB 
 k A ' CTo    
dW  FT   FT 

Solve
 Microreactors
• High surface area-to-volume ratio
• Reduce or eliminates heat and mass transfer
resistances
• Shorter residence times & narrower residence
time distributions
• Production of lab-on-a-chip, chemical sensors
• Assume PFR or in laminar flow
 Thermodynamically limited rxns
• Catalytic membrane reactors can be used to increase
the yield of reactions that are highly reversible over the
temperature range of interest.
• The membrane can either provide a barrier to certain
components, while being permeable to others, prevent
certain components such as particulates from
contacting the catalyst, or contain reactive sites and be
a catalyst in itself.
 Membrane reactors
• The membrane reactor is another technique for driving
reversible reactions to the right in order to achieve very high
conversion.
• These high conversions can be achieved by having one of
the reaction products diffuse out of a semipermeable
membrane surrounding the reacting mixtures.
• Two main types
– inert membrane reactor with catalyst pellets on the feed side
(IMRCF)
– Catalytic membrane reactor (CMR)
 Startup of a CSTR
• Determine the time necessary to reach steady-
state operation:
– Conversion does not have any meaning in the
startup

– Use concentration rather than conversion as the

variable in the balance equations.
 CSTR, 1st order rxn, liquid phase
dN A const. .V dC A
• mole balance FA0  FA  rAV  C A0  C A  rA  
dt   V v dt
0

• rate laws  rA  kC A

• combination dC A 1  k C A0
 CA 
dt  
t=0
C A0   t 
C A  C A0 CA  1  exp  (1  k )  
1  k    
t = ts 
t s  4.6
C A  0.99C AS 1  k
steady-state concentration
 Semi-batch reactors
• When unwanted side reactions occur at high concentration of
reactant B, or the reaction is highly exothermic. Examples of
reactions:
– ammonolysis
B
– chlorination
– hydrolysis
A
• Reactive distillation: Carrying out the two operations, reaction
and distallation in a single unit results in lower capital and
operating costs.
– acetylation reaction
– esterfication reaction (remove water) A C

+B
 Semi-batch reactor
• Write the reactor equations in terms of
concentration / numer of moles of each species
• Write the mass balance of the vessel
• Write the rate laws

C B
O.D.E solver
+B A
 A B  C
B
Semi-batch, liquid phase
A dN A
0  0  rAV 
• mole balance (A) dt
• mole balance (B) dN B
FB 0  0  rBV 
dt
d  V   0  
• V is not a constant  0v0  0  0  dt V  V0  v0t
(overall mole balance)
dC A v0
 rA - C A
• combine dt V
…..
dCB v0  C B 0  C B 
 rB 
dt V
Example 4-9 The production of methyl bromide is an irreversible liquid-phase
reaction that follows an elementary law. The reaction
CNBr+CH3NH2CH3Br+NCNH2 is carried out isothermally in a semibatch reactor.
An aqueous solution of methyl amine (B) at a concentration of 0.025 mol/dm3 is to
fed at rate of 0.05 dm3/s to an aqueous solution of bromine cyanide (A) contained in
a glass-lined reactor. The initial volume of fluid in a vat is to be 5 dm3 with a
bromine cyanide concentration of 0.05 mol/dm3. The specific reaction rate constant
is k = 2.2 dm3/smol. Solve for the concentration of bromine cyanide and methyl
bromide and the rate of reaction as a function of time.
Semi-batch reactor design equation:

Rate law:
Combination:

where
 Recycle reactors
• They are used when the reaction is autocatalytic, or when it is
necessary to maintain nearly isothermal operation of the reactor
or to promote a certain selectivity.
• They are used extensively in bio-chemical operations.
Xs Xo

R, recycle parameter

• Two conversions: the overall conversion X0 and the conversion

per pass Xs