Lecture 2

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors
in which they take place.
 Lecture 2
Class Lecture 13/9/2022

▪ Review of previous lecture

▪ Unsteady Sate Reactors With Heat Effects, Non
isothermal operation and adiabatic
▪ Case studies
▪ Ammonium Nitrate Explosion
▪ Monsanto Explosion
▪ T2 Laboratories Explosion

2
 Review: Multiple Steady States in CSTR
1
XA,EB
0.8
XA,MB
0.6
XA

0.4

0.2

0
0 100 200 300 400 500 600
T (K)
• Plot of XA,EB vs T and XA,MB vs T
• Intersections are the T and XA that satisfy both mass balance (MB) & energy
balance (EB) equations
• Each intersection is a steady state (temperature & conversion)
• Multiple sets of conditions are possible for the same reaction in the same
reactor with the same inlet conditions!
Review: Heat Removal Term R(T) & T0
Heat removed: R(T) Heat generated G(T)

 −r V   = UA Cp0FA0 Tc =  Ta + T0
Cp0 (1 +  )  T − TC  = −HRX  A  1+ 
 FA0 
R(T) line has slope of CP0(1+) R(T) =∞
=0
R(T)

Increase 
Increase T0 For Ta < T0
Ta T0 T

T When  increases from lowering

When T0 increases, slope stays
same & line shifts to right
FA0 or increasing heat exchange,
slope and x-intercept moves
Ta<T0: x-intercept shifts left as ↑
Ta>T0: x-intercept shifts right as ↑
=0, then TC=T0 =∞, then TC=Ta
 Review: CSTR Stability
 Ta + T0  = UA Cp0FA0 G(T) > R(T)
T =
R(T) c → T rises to
G(T) 1+ 
T=SS3 3
R(T) > G(T) → T R(T) > G(T)
→T falls to T=SS3
G(T) > R(T) falls to T=SS1 2
→ T rises to
T=SS1 Heat generated G(T)
Heat removed: R(T)
 −rA V 
1 Cp0 (1 +  )  T − TC  = −HRX  
 FA0 
T
• Magnitude of G(T) to R(T) curve determines if reactor T will rise or fall
• G(T) = R(T) intersection, equal rate of heat generation & removal, no change in T

• G(T) > R(T) (G(T) line above R(T) on graph): rate of heat generation > heat removal,
so reactor heats up until a steady state is reached
• R(T) > G(T) (R(T) line above G(T) on graph): rate of heat generation < heat removal,
so reactor cools off until a steady state is reached
 Unsteady State Nonisothermal
Reactor Design Q
Goal: develop EB for unsteady state reactor
Fin Fout

An open system (for example, CSTR) Hin Hout

W

dEsys n n
= Q − W +  FE
i i in −  FE
i i out
dt i=1 i=1
Rate of rate of heat Rate of work Rate of energy Rate of energy
accumulation flow from done by added to system leaving system
of energy in
= surroundings
- system on
+ by mass flow in - by mass flow
system to system surroundings out

dEsys dEsys
= 0 steady state  0 unsteady state
dt dt
 Change in System Energy with Time
dEsys n n
= Q − W +  FE
i i in −  FE
i i out
dt i=1 i=1
Energy of system is the sum of products of each species n
Esys =  NiEi
specific energy Ei & the moles of each species: i=1
n
Ei  Ui & Ui = (Hi − PVi ) so: → Esys =  Ni (Hi − PVi ) Differentiate wrt time
i=1
dEsys d n  dEsys n dHi n dNi d  n 
→ =   Ni (Hi − PVi )  → =  i
N +  i
H − P  i i
N V
dt dt i=1  dt i=1 dt i=1 dt dt  i=1 
Total V
dEsys n dHi n dNi d
→ =  Ni +  Hi − PV  For well-mixed reactor
dt i=1 dt i=1 dt dt with constant PV- variation
0
n n n dHi n dNi
Q − WS +  FH
i i −  FH
i i =  Ni +  Hi
i=1 in i=1 out i=1 dt i=1 dt
Total Energy Balance for unsteady state, constant PV
 Well-Mixed Reactors, Constant PV
Total Energy Balance for unsteady state
n n n dHi n dNi d
Q − WS +  FHi i −  FHi i =  Ni +  Hi − PV  = 0
i=1 in i=1 out i=1 dt i=1 dt dt

Special case: well-mixed reactors (e.g., batch, CSTR or semibatch) with constant
PV- variation in total P or V can be neglected
n n n dHi n dNi
→ Q − WS +  FH
i i −  FH
i i =  Ni +  Hi
i=1 in i=1 out i=1 dt i=1 dt
Total Energy Balance for unsteady state, constant PV

dHi T dHi dT
Evaluate recalling that Hi = H RX ( TR ) +  Cpi dT so =Cpi
dt T dt dt
R
n n n dT n dNi
→ Q − WS +  FH
i i −  FH
i i =  NiCpi +  Hi
i=1 in i=1 out i=1 dt i=1 dt
Need to put dNi/dt into terms that can be measured
 EB for Well-Mixed Reactors, PV=0
n n n dT n dNi
Q − WS +  FH
i i −  FH
i i =  NiCpi +  Hi
i=1 in i=1 out i=1 dt i=1 dt
From the mass balance:
Accumulation = In - Out + Gen
dNi dNi
= Fi0 − F i + i ( −rA ) V → = Fi0 − F i − irA V Substitute
dt dt
n n n dT n
→ Q − WS +  FHi i −  FH i i =  NiCpi +  Hi (Fi0 − F i − irA V )
i=1 in i=1 out i=1 dt i=1
n n n
dT n n n
→ Q − WS +  Fi0Hi0 −  FH i i =  NiCpi +  HiFi0 −  HiFi +   iHi ( −rA V )
i=1 i=1 i=1 dt i=1 i=1 i=1
Add SFiHi to both sides of equation:
n n dT n n
→ Q − WS +  Fi0Hi0 =  NiCpi +  HiFi0 +   iHi ( −rA V )
i=1 i=1 dt i=1 i=1
Substitute ΣiHi =H°RX(T): H°RX(T)
n dT n n
→ Q − WS +  Fi0Hi0 =  NiCpi +  HiFi0 + H RX ( T )( −rA V )
i=1 i=1 dt i=1
Simplified EB for Well-Mixed Reactors
n n dT n
Solve for dT/dt: Q − WS +  Fi0Hi0 =  NiCpi i i0 + H RX ( T )( −rA V )
+  HF
i=1 i=1 dt i=1
Bring SFi0Hi and H°RX(T) terms to other side of equation:
n n n dT
→ Q − WS +  Fi0Hi0 −  HFi i0 − H RX ( T )( −rA V ) =  NiCpi
i=1 i=1 i=1 dt

Factor SFi0Hi0 and SFi0Hi terms and divide by SNiCpi :

n
Energy balance for Q − WS −  Fi0 (Hi − Hi0 ) + H RX ( T )(rA V )
i=1 dT
unsteady state reactor n
=
dt
with phase change:  NiCpi
i=1

n
Energy balance for Q − WS −  Fi0Cpi ( T − Ti0 ) + H RX ( T )(rA V ) dT
i=1 =
unsteady state reactor n dt
without phase change:  NiCpi
i=1
 Unsteady State EB, Liquid-Phase Rxns
n
Q − WS −  Fi0 Cpi ( T − Ti0 ) + H RX ( T )(rA V )
i=1 dT
=
n dt
 NiCpi
i=1
For liquid-phase reactions, often Cp = SiCpi is so small it can be neglected
When Cp can be neglected, then:
n
 NiCpi = NA0 Cps where Cps = SiCpi is the heat capacity of the solution
i=1
If the feed is well-mixed, it is convenient to use:
SFi0 Cpi = FA0 Cps

Plug these equations and Ti0 = T0 into the EB gives:

Q − WS − FA 0 Cps ( T − Ti0 ) + H RX ( T )( rA V ) dT
=
NA0 Cps dt
This equation for the EB is simultaneously solved with the mass balance
(design eq) for unsteady state, nonisothermal reactor design
 Nonisothermal Batch Reactor Design
n
Q − WS −  Fi0Cpi ( T − Ti0 ) + H RX ( T )(rA V )
i=1 0 dT
n
=
dt
 NiCpi
i=1

No flow, so: Q − WS + H RX ( T )( rA V ) dT
→ =
n dt
 NiCpi
i=1
Ni0
Put the energy balance in Ni = NA0 ( i +  i X A ) where i = &  iCpi = CP
terms of XA: NA 0
Q − WS + H RX ( T )( rA V )dT
→ =
 n  dt
NA0   iCpi + Cp X A 
i=1 
Solve with the batch reactor design equation using an ODE solver (Polymath)
dXA
NA0 = −rA V
dt
 Adiabatic Nonisothermal Batch
Reactor Design
0 0
Q − WS + H RX ( T )(rA V ) dT
→ =
 n  dt
NA0   iCpi + Cp XA 
i=1 
In the case of no stirring work and adiabatic operation, WS =0 & Q = 0
H RX ( T )( rA V )
→ =
dT Substitute: H RX ( T )( rA V ) dT
n  dt  iCpi = Cps → =
NA0   iCpi + Cp X A  NA0 Cps + Cp X A  dt
i=1 
dT
Rearrange: → H RX ( T )( rA V ) = NA0 CpS + Cp X A 
dt
dX A
Substitute: H RX ( )
T = H RX ( R )
T +  Cp( T − TR) an d -N A0 = rA V
dt
dX A dT
→ −  H RX ( TR ) + Cp ( T − TR )  NA 0 = NA0 CpS + Cp X A 
  dt dt
dX dT
→ −  H RX ( TR ) + Cp ( T − TR )  A = CpS + Cp XA 
  dt dt
 dX dT
Solve for how XA −  H RX ( TR ) + Cp ( T − TR ) A = CpS + Cp XA 
changes with T   dt dt
→ −  H RX ( TR ) + Cp ( T − TR )  dX A = CpS + Cp X A  dT
 
Get like terms together:
XA dX A T −dT
→  = 
X A0 =0 CpS + Cp X A T H RX ( TR ) + Cp ( T − TR )
0
Integrate & solve for XA:
CpS ( T − T0 ) CpS ( T − T0 )
→ XA = → XA =
(
− H RX ( TR ) + Cp ( T − TR ) ) −HRX ( T )

Solving for T:
 −H RX ( T0 )  X A  −H RX ( T0 )  X A
T = T0 +   → T = T0 +  
Cps + X A Cp n
 iCpi + X A Cp
Heat capacity of soln (calculate Cps if not given) i=1
Solve with the batch reactor design equation using an ODE solver (Polymath)
XA
dX A
t = NA0 
0 −rA V
Ex. You are still the engineer of the CSTR in charge of the production of propylene
glycol.
A 1st order, liquid-phase, exothermic reaction A→B is run in a batch reactor. The
reactor is well-insulated, so no heat is lost to the surroundings. To control the
temperature, an inert liquid C is added to the reaction. The flow rate of C is adjusted
to keep T constant at 100 °F. What is the flow rate of C after 2h?
TC0 = 80 °F V0= 50 ft3 H°RX=-25000 Btu/lb mol
k(100 °F)= 1.2 x 10-4 s-1 Cp, (all components)= 0.5 Btu/lb mol °F
CA0= 0.5 lb mol/ft3
1. Solve design eq for comp as function of t
2. Solve EB for FC0 using that info & T=100 °F
This is essentially a semi-batch reactor since only C is fed into the reactor
dNA dX A
Design eq: = rA V Note, using NA0 = −rA V would complicate
dt d t
the calculation because V depends on t
Rate eq: -rA = kCA
dNA dNA
Combine: = −kC A V → = −kNA Rearrange and integrate for NA
dt dt
NA
dNA t  NA 
→  =  −kdt → ln   = −kt → NA = NA0 exp  −kt 
NA0 NA 0  NA0 
 A 1st order, liquid-phase, exothermic reaction A→B is run in a batch reactor. The
reactor is well-insulated, so no heat is lost to the surroundings. To control the
temperature, an inert liquid C is added to the reaction. The flow rate of C is adjusted
to keep T constant at 100 °F. What is the flow rate of C after 2h?
Use EB to find how the flow rate of C depends on the rxn (solve EB for FC0)
0 0
n
Q − WS −  Fi0 Cpi ( T − Ti0 ) + H RX ( T )(rA V )
dT i=1
=
dt n
0  NiCpi
i=1
n n
→ 0 = −  Fi0Cpi ( T − Ti0 ) + H RX ( T )(rA V ) →  Fi0 Cpi ( T − Ti0 ) = H RX ( T )( rA V )
i=1 i=1
C is the only species that flows, so: → FC0 CpC ( T − Ti0 ) = H RX ( T )( rA V )
rAV = -kCAV = -kNA where NA = NA0 exp  −kt 

(
→ FC0 CpC ( T − Ti0 ) = H RX ( T ) −kNA0 e−kt )
Isolate FC0: → FC0 =
(
H RX ( T ) −kNA0 e−kt )
CpC ( T − Ti0 )
A 1st order, liquid-phase, exothermic reaction A→B is run in a batch reactor. The
reactor is well-insulated, so no heat is lost to the surroundings. To control the
temperature, an inert liquid C is added to the reaction. The flow rate of C is adjusted
to keep T constant at 100 °F. What is the flow rate of C after 2h?
TC0 = 80 °F V0= 50 ft3 H°RX=-25000 Btu/lb mol
k(100 °F)= 1.2 x 10-4 s-1 Cp, (all components)= 0.5 Btu/lb mol °F
CA0= 0.5 lb mol/ft3

FC0 =
(
H RX ( T ) −kNA 0 e−kt ) NA0 = CA0 V0 = 0.5
lb mol
( )
50ft 3 = 25 lb mol
CpC ( T − Ti0 ) ft3

At 2h (7200s):
−25,000
Btu 
 −1.2  10−4 s−1 ( 25 lb mol ) e
( )
− 1.210−4 s−1 7200s 

lb mol  
FC0 =  
0.5
Btu
lb mol  F
(
100 F − 80 F )
lb mol
→ FC0 = 3.16
s
Instead of feeding coolant to the reactor, a solvent with a low boiling point is added
(component D). The solvent has a heat of vaporization of 1000 Btu/lb mol, and initially
25 lb mol of A are placed in the tank. The reactor is well-insulated. What is the rate of
solvent evaporation after 2 h if T is constant at 100 °F?
Additional info: k(100 °F)= 1.2 x 10-4 s-1 H°RX=-25000 Btu/lb mol
Still a semibatch reactor, where D is removed from the reactor
Use EB that accounts for a phase change:
0 0 n
Q − WS −  Fi0 (Hi0 − Hi ) + H RX ( T )(rA V ) Q̇=0
dT i=1
= n ẆS=0
dt
0  NiCpi
i=1

Clicker Question: Does dT/dt = 0?

a) Yes
b) No
Instead of feeding coolant to the reactor, a solvent with a low boiling point is added
(component D). The solvent has a heat of vaporization of 1000 Btu/lb mol, and initially
25 lb mol of A are placed in the tank. What is the rate of solvent evaporation after 2
h?
Additional info: k(100 °F)= 1.2 x 10-4 s-1 H°RX=-25000 Btu/lb mol
Still a semibatch reactor, where D is removed from the reactor
Use EB that accounts for a phase change:
0 0 n
Q − WS −  Fi0 (Hi0 − Hi ) + H RX ( T )(rA V ) Q̇=0
dT i=1
= n ẆS=0
dt
0  NiCpi dT/dt = 0
i=1
n D is the only species that ‘flows’, and
→  Fi0 (Hi0 − Hi ) = H RX ( T )( rA V )
i=1
rAV = -kNA0(exp[-kt]), so:

( )
→ FD0 (Hi0 − Hi ) = H RX ( T ) −kNA 0 e−kt → F =
(
H RX ( T ) −kNA0 e−kt )
D0
Hi0-Hi = heat of vap
(Hi0 − Hi )
Btu  0.00012
−25,000 − ( 25 lb mol) e−( 0.00012 s )7200s → F = 0.0316 lb mol
lbmol  s  D0
FD0 = s
1000Btu lb mol
 A liquid phase exothermic reaction A →B is carried out at 358K in a 0.2 m3 CSTR. The
coolant temperature is 273K and the heat transfer coefficient (U) is 7200 J/min·m2·K. What
is the heat exchange area required for steady state operation? Using this heat
exchange area, plot T vs t for reactor start-up.
CPA =CPS=20 J/g•K ẆS=0 CA0= 180 g/dm3 u0= 500 dm3/min T0= 313 K
r= 900 g/dm3 H°RX(T) = -2500 J/g E=94852 J/mol·K k(313K)= 1.1 min-1
a) Heat exchange area for steady state operation:
n
SS operation means Q − WS −  Fi0Cpi ( T − Ti0 ) + H RX ( T )(rA V )
that T is constant, so: dT i=1
= n
=0
dt
 NiCpi
i=1
n
→ Q − WS −  Fi0 Cpi ( T − Ti0 ) = −H RX ( T )( rA V )
i=1
Q̇=UA(Ta-T), ẆS=0, and A is only species that flows
→ UA ( Ta − T ) − FA0 CpA ( T − TA0 ) = −H RX ( T )( rA V )
Plug in rA = -kCA and solve for A
→ UA ( Ta − T ) − FA0CpA ( T − TA0 ) = −H RX ( T )( −kCA V )

−H RX ( T )( −kCA V ) + FA0CpA ( T − TA0 )

→A=
U ( Ta − T )
A liquid phase exothermic reaction A →B is carried out at 358K in a 0.2 m3 CSTR. The
coolant temperature is 273K and the heat transfer coefficient (U) is 7200 J/min·m2·K. What
is the heat exchange area required for steady state operation? Using this heat
exchange area, plot T vs t for reactor start-up.
CPA =CPS=20 J/g•K ẆS=0 CA0= 180 g/dm3 u0= 500 dm3/min T0= 313 K
r= 900 g/dm3 H°RX(T) = -2500 J/g E=94852 J/mol·K k(313K)= 1.1 min-1
Use material balance to determine steady state value of CA
FA0 − FA + rA V = 0 → CA0u0 − CAu0 − kCA V = 0 → CA0u0 = CAu0 + kCA V

CA0u0 1.1  94852J mol  1 1  107.4

→ = CA k ( 358K ) = exp   −  → k ( 358K ) =
u0 + kV min  8.314 J mol  K  313 358   min

CA =
(
180 g dm3 500 dm3 min ) → CA = 4.1g dm3
(
500 dm3 min + 107.4min−1 200dm3 )
−H RX ( T )( −kCA V ) + FA0 CpA ( T − TA0 )
Solve EB for A: A=
U ( Ta − T )

 g  dm3  3  1000dm
3  3
=  180  = 90000 g min  = 200dm
3  
FA0 500 V=0.2m 
 dm   min   3
 m 
 A liquid phase exothermic reaction A →B is carried out at 358K in a 0.2 m3 CSTR. The
coolant temperature is 273K and the heat transfer coefficient (U) is 7200 J/min·m2·K. What
is the heat exchange area required for steady state operation? Using this heat
exchange area, plot T vs t for reactor start-up.
CPA =CPS=20 J/g•K ẆS=0 CA0= 180 g/dm3 u0= 500 dm3/min T0= 313 K
r= 900 g/dm3 H°RX(T) = -2500 J/g E=94852 J/mol·K k(313K)= 1.1 min-1
Solve for heat exchange area at SS:
−H RX ( T )( −kCA V ) + FA 0 CpA ( T − TA 0 )
A=
U ( Ta − T )
FA0=90,000 g/min V=200 dm3
H°RX(T) = -2500 J/g k= 107.4 min-1 CA= 4.1 g/dm3 CPA =20 J/g•K
U= 7200 J/min·m2·K TA0= 313 K T= 358K Ta=273K
 J   107.4  g  3  g  J 
−  −2500   −  4.1
3
200dm +
  90000  20
  ( 358K − 313K )
→A= 
g  m in  dm    m in  g K 
 J 
 7 200  ( 273K − 358K )
 min m  K 
2

A=227.4 m2
Will use Polymath to plot T vs t for CSTR start-up (unsteady-state). Need
equations for dCA/dt, dT/dt, and k.
dNA dCA CA0 CA
Mass balance: = FA0 − FA + rA V → = − + rA
dt dt t t
dT UA ( Ta − T ) − FA0CpA ( T − Ti0 ) + H RX (rA V )
= n
dt
 Ni0Cps
i=1
CPs is in terms of mass (J/g·K), so FA0 & Ni0 must also be in terms of mass
FA0=90,000 g/min
Substitute ṁi0 for Ni0, & use r for the solution to calculate:
3 g 
mi0 = Vr → m = 200d m  9 0 0 → mi0 = 180,000g
3
i0 rA=-kCA
 dm 
Amount of gas leaving reactor (L7)
1.1  94852J mol  1 1  1.1 11408.7  1 1 
k= exp   −  → k= exp  K  − 
min  8.314J mol  K  313 T   min   313 T  
U= 7200 J/min·m2·K A=227.4m2 CA0=180g/dm3 t=V/u0 Ta=273K
HRX=-2500 J/g Ni0=mi0 V=200 dm3 CPs=20 J/g˙K u0=500 dm3 T0=313
Will use Polymath to plot T vs t for CSTR start-up (unsteady-state). Need
equations for dCA/dt, dT/dt, and k.
dCA CA0 CA 1.1 11408.7  1 1 
→ = − + rA k= exp   −  rA=-kCA
dt t t min  K  313 T  
dT UA ( Ta − T ) − FA0CpA ( T − Ti0 ) + H RX (rA V )
= mi0 = 180,000g
dt n
 Ni0Cps F =90,000 g/min
i=1 A0

U= 7200 J/min·m2·K A=227.4m2 CA0=180g/dm3 t=V/u0 Ta=273K

HRX=-2500 J/g Ni0=mi0 V=200 dm3 CPs=20 J/g˙K u0=500 dm3 T0=313
T (K)

t (min)

Reaches steady state at ~12 minutes

 The elementary, liquid phase, exothermic reaction A →B is carried out in a 2 m3
CSTR that is equipped with a heat jacket. Pure A enters the reactor at 60 mol/min and a
temperature of 310K. The coolant in the heat jacket is kept at 280 K. Provide all equations, all
constants, the initial time, and the final time that must be entered into Polymath in order to
plot temperature vs time for the first 20 min of reactor start-up. ΔHRX(TR) = -10,000 cal/mol
CPA = CPS =15 cal/mol·K CpB=15 cal/mol·K ẆS=0
E = 20,000 cal/mol k = 1 min-1 at 400 K UA= 3200 cal/min•K u0= 300 L/min
Need equations for how T changes with time, CA changes with time, & k changes with T.
n
Q − WS −  Fi0 Cpi ( T − Ti0 ) + H RX ( T )( rA V )
dT
dt
= i=1
n
WS = 0 (
Q = UA T - T
a )
 NiCpi
i=1
HRX ( T ) = H RX ( TR ) + CP ( T − TR ) CP = CPB − CPA → Cp = 15 − 15
b cal
=0
a mol  K
cal
→ H RX ( T ) = H RX ( TR ) + 0 → H RX ( )
T = −10,000
mol
n n n
F C i0 pi = FA 0 Cp,A + FB0 Cp,B FB0 = 0 →  Fi0 Cpi = FA0 Cp,A  NiCpi = NA0 Cps
i =1 i =1 i=1

Combine with EB: ( ) ( )

dT UA Ta - T − FA 0 Cp,A ( T − Ti0 ) + H RX TR rA V
=
dt NA0 Cps
The elementary, liquid phase, exothermic reaction A →B is carried out in a 2 m3
CSTR that is equipped with a heat jacket. Pure A enters the reactor at 60 mol/min and a
temperature of 310K. The coolant in the heat jacket is kept at 280 K. Provide all equations, all
constants, the initial time, and the final time that must be entered into Polymath in order to
plot temperature vs time for the first 20 min of reactor start-up. ΔHRX(TR) = -10,000 cal/mol
CPA = CPS =15 cal/mol·K CpB=15 cal/mol·K ẆS=0
E = 20,000 cal/mol k = 1 min-1 at 400 K UA= 3200 cal/min•K u0= 300 L/min
Need equations for how T changes with time, CA changes with time, & k changes with T.

H RX ( T ) = −10,000
cal
mol dT
= a ( )
UA T - T − FA 0 Cp,A ( T − Ti0 ) + H
RX
T r V
R A ( )
dt NA0 Cps
UA = 3200 Ta = 280
FA0 = 60 CPA = 15 Ti0 = 310 rA = kCA  20,000  1 1 
k = (1) exp   400 − T  
 1.987  
NA 0 FA 0 V u0 = 300
FA0 =
V
u0 → NA0 =
u0 CPS = 15 ( )
V = 2m3 1000L 1m3 → V = 2000

t (0) = 0 t ( f ) = 20 Use the mass balance to get eq for CA(t)

dNA dNA dCA CA0 CA
= FA0 − FA − rA V → = C u − C u − k C V → = − − kC A
dt dt
A0 0 A 0 A
dt t t
t = V u0 CA0 = FA 0 u0
 Unsteady State Energy Balance
n dÊ sys
n
Q − WS +  Fi 0 H i 0 −  Fi H i =
 
i =1 i =1 dt
Neglect

Using Ê sys = N E =  N (H − PV ) =  N H − PV
i i i i i i i

dE d N H dH dN
= = N = H
sys i i i i
i i
dt dt dt dt
dH i dT
= C Pi
dt dt
dN i
36
= −ui rA V + Fi 0 − Fi
dt
 Unsteady State Energy Balance

We obtain after some manipulation:

dT Q  −  F C (T − T ) + − H (T )(− r V )
 −W
= S i 0 Pi i0 Rx A

dt  NiCPi

Collecting terms with Q = UA(T − T)  =0

W
a S
and high coolant flow rates, and Fi 0 = FA 0 i

37
 Case 1 – Ammonium Nitrate Explosion

Massive blast at Terra plant kills four.

3
8
 Example 1: Safety in Chemical Reactors

H2O
 Ga
N2 O s
17%H2O
T0 = 200F 200°F P
mA0 = 310lb h Liquid
83%NH4NO3

510°F
X Ta0
NH4NO3
Ta
M  500 lb

NH4NO3 → N 2O + 2H 2O

3
9
 Example 1: Safety in Chemical Reactors

Only liquid A in the vat as the product gases N2O

and H2O escape immediately after being formed.

dT Q g − Q r
=
dt NACPA

Q g = (rAV )(H RxA )

Qr = FA0 C PA (T − T0 ) +  B (H B − H B 0 )+ UA(T − Ta )

4
0
 Unsteady State Energy Balance
dT Qg

 
     Qr

dt (H R x )(rA V ) − FA 0   i C Pi (T − T 0 ) + (U A (T − T a )
=
 Ni C Pi

Adiabatic

 (
Q r = FA 0 C PA (T − 660 ) +  W 1134 + C PW (T − 960 ) )
F A0 = 0

dT ( −H Rx )(−rAV) T
=
dt N i C P i
If the flow rate is shut off, the temperature t (min)
6 will rise (possibly to point of explosion!)
 Case 2 – Monsanto Chemical Company

 Keeping MBAs away from Chemical Reactors

 The process worked for 19 years before “they”

showed up!
 Why did they come?
 What did they want?

4
2
 Nitroanline Synthesis Reaction

NO2 NO2
Cl NH2

+ 2NH3 + NH4Cl

ONCB + Ammonia Nitroanaline + Ammonium

Chloride

4
3
 Nitroanline Synthesis Reaction
NH3 in H2O

ONCB

Autoclave
175 oC
~550 psi

NH3 Filter
O-Nitroaniline Separation Press
Product Stream

To Crystallizing Tanks

9 “fast” Orange
 Nitroanline Synthesis Reactor

Old
3 kmol ONCB
43 kmol Ammonia
100 kmol Water
V = 3.25 m3
45
 Same Nitroanline Synthesis Reaction
NO2 NO2
Cl NH2

+ 2NH3 + NH4Cl

ONCB + Ammonia Nitroanaline + Ammonium

Chloride

Batch Reactor, 24 hour reaction time

Management said: TRIPLE PRODUCTION

46
 MBA-Style:
Nitroanline Synthesis Reactor

New
9 kmol ONCB
33 kmol Ammonia
100 kmol Water
V = 5 m3
47
 Batch Reactor Energy Balance
Qg Qr
dT (rA V)(H rx ) − UA(T − T0 )
=
dt N A0 C pA + NB0 C pB + NW C pW

NCP = N A0 C pA + N B0 C pB + N W C pW

dT Qg − Qr
=
dt NCp

48
 Batch Reactor Energy Balance
dT Qg − Qr
=
dt NCp
The rate of “heat removed” is
   − UA 
c Pc (Ta1 − T)1− exp
Qr = m C   Equation (12 -13) p547
  mc C P 
  c 

For high coolant flow rates, mc , the maximum rate of heat removal is

Q r = UA( T − Ta )
The rate of “heat generated” is Q g = (rA V)H Rx = (− rA V)(− H Rx )
− rA = k1CA CB
Q g =k 1 C A C B (− H Rx )
14
 Batch Reactor Energy Balance
Recall dT Qr − Qg
=
dT NCPS
For isothermal operation at Qr = Qg, T = 448 K
Q g = k(448 K)C2A0 (1− X)( B − X )(− H Rx )
Qr = Qg
   − UA 
 cC Pc (Ta1 − T)1 − exp 
m   = (0.0001167)C 2A0 (1− X)
  mc C P 
  c 

Vary mc to keep “heat removed” equal to “heat generation”

15
Isothermal Operation for 45 minutes

At thetime the heatexchanger fail

X = 0.033,T = 448 K s
Qg = rAVH Rx = 3850 kcal / min

The maximum rate of removal at T = 448 K is

Qr = UA(T − Ta ) = 35.85(448 − 298) = 5378kcal / min

Qr  Qg Everything is OK
Adiabatic Operation for 10 minutes
t = 45 X = 0.033 T = 448K
min X = 0.0424 T = 468K
tQ= =
556591kcal / min
g
min
Qr = 6093kcal / min
Qg  Qr
dT Qg − Qr
= = 0.2C / min
dt NC p
Temperature-Time trajectory
dT Qq − Qr
= = 0.2 C / min
dt N Cp
oC

400
Temperature

Qr = 0 Cooling Restored
200 Isothermal
Operation
175
fuse

9:55 10:40 10:50 midnight 12:18

t=0
18
 Disk Rupture
The pressure relief disk should have ruptured when the temperature
reached 265°C (ca. 700 psi) but it did not.

If the disk had ruptured, the maximum mass flow rate out of the
reactor would have been 830 kg/min (2-in orifice to 1 atm).

Q r = m vap H vap + UA(T − Ta )

kcal
Q r = 449,000
min
kcal
Q g = 27,460
min
Q r  Q g

No explosion
 All the following three things must have
occurred for the explosion to happen

1. Tripled Production

2.Heat Exchange Failure

3.Relief Valve Failure

55
 Case 3 – Manufacture of Fuel Additive
methylcyclopentadiene manganese tricarbonyl (MCMT)

56
 Production of methylcyclopentadienyl manganese tricarbonyl (MCMT).
Step 1a. Reaction between methylcyclopentadiene (MCP) and sodium in a
solvent of diethylene glycol dimethyl ether (diglyme, C6H14O3) to
produce sodium methylcyclopentadiene and hydrogen gas:

Step 1b. At the end of Step 1a, MnCl2 is added to the reactor. It reacts with
sodium methylcyclopentadiene to produce manganese
dimethylcyclopentadiene and sodium chloride:

Step 1c. At the end of Step 1b, CO is added. The reaction between
manganese dimethylcyclopentadiene and carbon monoxide produces the
final product, methylcyclopentadienyl manganese tricarbonyl (MCMT), a fuel
additive.

57
 Only consider Step 1

Desired Reaction

Undesired Reaction of Dygline

Simplified Model

Let A = methycylcopentadiene, B = sodium, S = Solvent (diglyme), and D = H2.

These reactions are:

(1) A + B → C + 1/2 D (gas) −r1A = −r1B = k1ACACB

(2) S → 3 D (gas) + miscellaneous liquid and solid products −r2S =k2sCS

HRx1A = −45,400 J mol

HRx2S = −3.2 10 5 J mol

58
 Case 3 – Manufacture of Fuel Additive

59
 Case 3 – Manufacture of Fuel Additive

60
 Case 3 – Manufacture of Fuel Additive
(2) Rates
Laws:

Net Rates:

61 (3) Stoichiometry – Liquid Phase

 Case 3 – Manufacture of Fuel Additive
(4) Energy Balance:

=1.2610 7 J K

HRx1A = −45,400 J mol

HRx2S = −3.2 10 5 J mol

62
63