6.

Energy balance on chemical reactors

Most of reactions are not carried out isothermally

BATCH or CSTR heated (cooled) reactors

Inlet
tubing Coolant
outlet
Reaction
Mixer mixture
Double
shell
Coolant Outlet Internal
inlet tubing heat
exchanger
 The balance of total energy involves:
Internal energy
mechanical energy (kinetic energy)
potential energy
R.B.Bird, W.E.Stewart, E.N.Lightfoot :
.... Transport Phenomena, 2nd Edition,
J.Wiley&Sons, N.Y. 2007

Transformation of various kinds of energy

Balance of total energy

Input x Output
Input x Output of total energy
of total energy by convective
by molecular flux flux
Rate of change
of total energy

Work done
E  U  Ekin  E p Work done
by molecular by external
interactions forces
Main reason to study energy balances : assesment of
temperature of reacting system (reactor)
Application of the 1st law of thermodynamics on the open homogeneous reacting
system
Rate of work done on surroundings [W]
Heat flux [W]

E   eV dV
VR

Single phase
reacting
system

eo,e1 – specific total energy of inlet (outlet) streams [J/mol]

VR – volume of reaction mixture [m3]
 dE
 Fo eo  F1e1  Q  W
dt
eo , e1  molar energies of inlet and outlet streams [J/mol]

Rate of work Wdone by the reacting system on the

surroundings consists of:

• Flow work of inlet stream(s) Vo Po  FoVmo Po

• Flow work of outlet stream(s) V1 P1   FV
1 m1 P1

• Work provided by stirrer Ws

dVR
• Work done by volume change P
dt
• Work done by electric, magnetic fields W f

dE dVR
 Fo  eo  Vmo Po   F1  e1  Vm1P1   Q  P  Ws  W f
dt dt
 Neglecting potential and kinetic energies (E  U ), we have

dU dVR
 Fo hmo  F1hm1  Q  P  Ws  W f
dt dt
hmo , hm1  molar enthalpies of inlet and outlet streams [J/mol]

If Ws  0,W f  0

dU dVR
 Fo hmo  F1hm1  Q  P
dt dt
From enthalpy definition

dH dU dP dV dH dP
  VR P R  VR  Fo hmo  F1hm1  Q
dt dt dt dt dt dt
 Introducing partial molar enthalpies of species

N
Fo hmo   Fi o H io
i 1
N
F1hm1   Fi H i
i 1

We have finally

N N
dH dP
 VR   Fi H i   Fi H i  Q
o o

dt dt i 1 i 1
 BATCH reactor

dH dP
 VR Q
dt dt
Enthalpy is a function of temperature, pressure and composition

Total heat capacity [J/K] Partial molar enthalpy [J/mol]

 H   H  N
 H 
dH    dT    dP     dni
 T  P ,n j  P T ,n j i 1  ni T , P , n
j i

 H  N
 H  N
 CP dT    dP   H i dni  mVR cP dT    dP   H i dni
 P T ,n j i 1  P T ,n j i 1

Molar density [mol/m3 ] Molar heat capacity [J/mol/K]

 We know that (from thermodynamics)

 H    VR  
   VR  T     VR 1   pT 
 P T ,n j   T  P ,n j 

where the coefficient of isobaric expansion is defined as

1  VR 
p   
VR  T  P ,n j

and we obtain

 VR 1   pT 
dH dT dP N dn
 m cPVR   Hi i
dt dt dt i 1 dt
dni
Finally by substitution of in the energy balance of the batch reactor
dt
NR
dni
 VR  ki rV ,k
N
dT dP dni
mcPVR   pVRT   Hi Q dt
dt dt i 1 dt k 1
Using definition of the enthalpy of k-th reaction

N
 r H k   ki H i
i 1

we have
NR
dT dP
m cPVR   pVRT  VR    r H k  rV ,k  Q
dt dt k 1

Isobaric reactor ( dP  0 )
dt
NR
dT
m cPVR  VR    r H k  rV ,k  Q
dt k 1

VR  f (t ) we need state equation !

Homework 8: Energy balance of ideal gas isobaric batch reactor

 dVR
Isochoric reactor (  0)
dt
dT NR
 p 
mVR cV  VR    r H k   T Vk rV ,k  Q
dt k 1  T 
P  f (t )
the coefficient of isobaric expansion the coefficient of isothermal compressibility
1  VR  1  VR 
p    T    
VR  T  P ,n j VR  P T
the volume variation due to k-th chemical reaction
N
 V 
Vk   kiVi , where Vi    is the partial molar volume of species i
i 1  ni T , p ,n ji
the specific heat capacity at constant volume
 P   VR   P  p
2

CV  CP  T      C  TVR    C  TV
 T V ,n j  T  P ,n j
P
 T V ,n j
p P R
T
Variation of the pressure can be derived from total differential of volume
  V  dT N dni 
  T  P ,n dt 
 R   Vi 
dP  i 1 dt   p dT 1 N
dni
   V
j

 VR  T dt VRT i
dt i 1 dt
 
 P T ,n j

Homework 9: Energy balance of ideal gas isochoric batch reactor

Summary of energy balance of BATCH reactor

NR
dT
dP
0
m cPVR  VR    r H k  rV ,k  Q
dt dt k 1

VR  f (t )

dT NR
 p 
dVR mVR cV  VR    r H k   T Vk rV ,k  Q
0 dt k 1  T 
dt
P  f (t )

NR
dT
mcPVR  VR    r H k  rV ,k  Q
If  p  0, c p  cV dt k 1
liquid (condensed) systems
Rate of change Rate of heat generation Rate of heat
of reaction mixture by chemical reactions loss (input)
enthalpy
Heat flux : Q   S (T  T )
H e

  the overall (global) heat transfer coefficient [W.m 2 .K 1 ]

S H  the heat exchange area [m2 ]
Te  temperature of external cooling (heating) fluid
Limiting cases

NR
dT
Isothermal m cPVR  0  VR    r H k  rV ,k  Q
reactor dt k 1

Adiabatic dT NR

reactor Q  0  m c pVR  VR    r H k  rV ,k 

dt k 1
Example
Adiabatic reactor with 1 reaction, constant heat capacities

Energy balance on adiabatic BATCH reactor

dT
 m c pVR  VR   r H  rV
dt
Molar balance of key component
dc j dX j
 c oj   j rV
dt dt
N
 mVR  n, c p   yi c pi
i 1

N N N  i o 
 mVR c p  n yi c pi   ni c pi    nio  n X c 
i 1 i 1

i 1   j j j  pi
noj X j n oj X j
 n c    c     n c  
N N N
o o
c p
i 1
i pi
j i 1
i pi
i 1
i pi
j
Assuming that c pi  const  c p  const
y oj   r H (To )  X j
T  To   To   j X j
 N

 v j  yi c pi  y j c p X j 
o o

 i 1 
y oj   r H (To ) 
j  the adiabatice rise of temperature
 N

 vj

y c
i 1
o
i pi  y oj c p X j 

Trajectories of T(t) and Xj(t)

Xj = 1
Exothermal reaction
T(t)
Xj(t) r H  0
Xj(t)

y oj   r H (To ) 
j 
 N

T(t)  vj

y c
i 1
o
i pi  y oj c p X j 


To

t
Homework 10
The reversible reaction

A1 + A2  A3

is carried out adiabatically in a constant-volume BATCH reactor. The

kinetic equation is
r  k f c11/2c1/2
2  kb c3

k f (373 K)=2x103 s 1 E1  100 kJ/mol

kb (373 K)=3x105 s 1 E 2  150 kJ/mol

Initial conditions and thermodynamic data

c1o  0.1 mol/dm3 c p1  25 J/mol/K
c2o  0.125 mol/dm3 c p 2  25 J/mol/K
 r H 298
o
 40 kJ/mol c p 3  40 J/mol/K T o = 373K

Calculate X1(t),T(t).
 Example
Acetic anhydride reacts with water

(CH3CO)2O + H2O  2CH3COOH

in a BATCH reactor of constant volume of 100 l. Kinetics of

reaction is given by
46500

rV  2.14 10 e
7 RT
c1 mol.m3 .min 1

Data

c1o  0.3 mol.l-1 , c pM  3.8 kJ.kg -1.K -1 , H r  209kJ.mol 1 ,  =1070 kg.m 3

c pi
.SH =200W.K 1 Te  T o  300 K, c p  0, c pM   wio c pMi , c pMi 
i Mi
wio  initial mass fractions, c pMi - mass heat capacities (kJ.kg -1.K -1 ), M i - molar weight (kg.mol 1 )
R  8.31446 J.mol 1.K 1

In neglecting variation of heat capacities with temperature,

calculate T(t) and X1(t) for an non-adiabatic and adiabatic case.
By numerical integration we get
dT 1   46500  
  0.1 209E3  2.14E7xexp -  300  (1  X )  200  (300-T) 
dt (1070  3.8E3  0.1)   (8.31446  T ) 
1

dX 1  46500 
 2.14E7  exp -  (1  X 1 )
dt  (8.31446  T ) 

316 1.20

314 1.00
T [K]
X1
312 0.80

310 0.60

308 0.40

306 0.20

304 0.00
0 10 20 30 40 50 60

t [min]
Continuous (perfectly) stirred reactor (CSTR)
Energy balance on CSTR
dH dP N o o N
 VR   Fi H i   Fi H i  Q
dt dt i 1 i 1

Total differential of enthalpy

 VR 1   pT 
dH dT dP N dn
  m cPVR   Hi i 
dt dt dt i 1 dt
dP N o o N
 VR   Fi H i   Fi H i  Q
dt i 1 i 1

Molar balance on CSTR

NR
dni
 Fi  Fi  VR  ki rV ,k ,
o
i  1, N
dt k 1
 We get

dT dP N  o NR

m cPVR   pTVR   H i  Fi  Fi  VR  ki rV ,k   Enthalpy
dt dt i 1  k 1  change for
N N
  Fi H   Fi H i  Q
o
i
o k-th reaction
N
 r H k   ki H i
i 1 i 1

i 1

NR
dT dP
m cPVR  VR pT  VR    r H k rV ,k 
dt dt k 1

  Fi o  H io  H i   Q
N

i 1 dP
0
dt
The CSTR usually works at constant pressure (no pressure drop)

  Q   ST (Tm  T )
NR N
dT
mcPVR  VR    r H k rV ,k + Fi o H io  H i  Q
dt k 1 i 1
Steady state

dT dni
 0
dt dt

 
NR N
VR    r H k rV ,k + Fi o H io  H i  Q  0
k 1 i 1

Assuming ideal mixture, i.e. H i  H i , we have

T
H  H i  H  H i    c pi dT
i
o
i
o

To
T
 r H k   r H    c p  dT
o
k
To
k
Molar and enthalpy
balances give
 c   
N

p k c
ki pi N+1 unknown
i 1
variables T, Fi
 T  T
VR     r H k    c p  dT rV ,k   Fi  c pi dT  Q  0
NR N
o o
 k 
k 1
 To  i 1 To

NR
Fi  Fi  VR  ki rV ,k  0,
o
i  1, N
k 1
N+1 unknown variables in N+1 non linear algebraic equations

Gi T , F1 , F2 ,....FN   0, i  1, N  1

Issues:
• multiple solutions
• slow convergence (divergence)
Example
Adiabatic CSTR with 1 reaction, constant heat capacities

   r   F c
N N
VR  r H  c p T  T o o
V i
o
pi (T  T )  F (T  T ) yio c pi
o o o

i 1 i 1

Fjo X j
F X j  VR j rV  0  rV 
o

VR  j
j

  H 
y oj X j

N
 (T  T ) yio c pi
2 nonlinear algebraic equations for
o
 c p T  T o o
unknown T and Xj
j
r
i 1

T T  o   H  y
r
o o
j Xj

N
j y c
i 1
o
i pi  c p y oj X j

 To  j X j cf. adiabatic const.-volume BATCH

 Multiple steady states of adiabatic CSTR (exothermal reaction)

Fjo X j + j rV ( X j , T )VR =0  X j  f1 (T)

0.8 f1(T)

0.6 Steady state 1

f2(T)
Xj

Steady state 2
0.4

0.2
Steady state 3

0
310 330 350 370 390
T (K)

T  To   j X j  X j  f 2 (T )
 Example
You are to consider an irreversible gas-phase reaction in an adiabatic CSTR at constant pressure (101 kPa).
The gas phase reaction is:
CO(g) + 3 H2(g)  CH4(g) + H2O(g)

rV  kcCO
Ea 1 1
k  0.001exp[ (  )] min 1
R T 298
Ea  10 kcal/mol

The feed to the CSTR consists of CO and H2 at the following (stoichiometric) concentrations:

CCO(in) = 0.0102 mol/liter CH2(in) = 0.0306 mol/liter

The heat of reaction at 298 K is equal to –49.0 kcal/mol.
The heat capacities of CO, H2, CH4 and H2O are all constant and are equal to 7 cal/mol/K.
The temperature of the feed stream is equal to 298 K, the pressure is equal to 101 kPa, the volumetric flow
rate of feed is 8 liter/min and volume of reactor is 0.5 l. The gas mixture behaves as ideal gas.

A. Use the energy and molar balance to calculate the CO conversion and temperature of the effluent stream
from the adiabatic CSTR.
B. Calculate the composition in molar fraction of the outlet stream.
C. Calculate the volume of the adiabatic CSTR required to achieve the desired CO fractional conversion equal
to 0.99.
 1

0.9
Molar balance of CO
VR P k (T ) X (2  X 1 )
 g (T )  1
RT 2 F1 o
1  X1
0.8
(2  g )  4  g 2
X1 
2
0.7 Adiabatic enthalpy balance
N
1 y c o
i pi (T  T o )
0.6 X1  i 1

  H  y
r
o o
1  c p y1o (T  T o )

X1(T)
0.5

0.4
3 steady states
0.3

0.2

0.1

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500
T/K
Remarks:
 Unrealistic temperature of the 3rd steady state  backward
reaction will occur
 The 2nd steady state is unstable  carefull temperature control
has to be used
 The dynamic behavior of reactor should be studied
Homework 11

Determine steady states of adiabatic CSTR in which the exothermal liquid state reaction takes place

A1  A2
Reaction rate:

rV = A.exp(-E/RT).cA1 (kmol/m3/s)

Data

A = 5.1017 s-1 E = 132.3 kJ/mol

VR = 2 m3 To = 310 K

 = 800 kg.m-3 cAo1  2kmol / m3

V o  3.33 l/s C po  4.19 kJ.kg-1. K -1

H r ,298  100 kJ / mol
 Balance of enthalpy on Plug Flow Reactor (PFR)

v
N N

F
i 1
i Hi F i Hi
VR i 1 VR VR
 H 
 
 t VR

z z + z VR  S R z
VR VR + VR
Q
 H  dP N N

   VR   Fi H i   Fi H i  Q
 t VR dt i 1 VR i 1 VR VR

in the steady state

N N
d  N  dQ
0=  Fi H i   Fi H i  Q    Fi H i 
i 1 VR i 1 VR VR
dVR  i 1  dVR
ideal mixture  H i (T , P, composition)  hi (T )
N
 dFi dhi (T )  N  NR dhi (T ) dT 
 
i 1  dVR
hi (T )  Fi     ki V ,k i

dVR  i 1  k 1
 r h (T )  Fi
dT dVR 

NR
dT N dQ
   r H k rV ,k   F c
i pi 
k 1 dV R i 1 dVR
NR N Circular cross
dFi dQ dS
  ki rV ,k  h  r H k
ki i   (Te  T ) t section
dVR k 1 i 1 dVR dVR
dT  NR
1 4  dSt  d R dz
 N     r H k  rV ,k  (Te  T )  
 k 1  d R2
 i pi
dVR dR dVR
F c  dz
i 1 4
dT  d R2  NR 4 
 N     r H k  rV ,k  (Te  T ) 
4 Fi c pi  k 1 
dz dR
i 1
 One reaction, constant heat capacity of reaction mixture.
Profiles of conversion and temperature are given by following
equations: N N

dT  d R2  4   Fc i p ,i   Fyi c p ,i 
 (H r )rV  Te  T  i 1 i 1
dz 4 F o c pM
o
 d R  N

dX j

 .d  j
2
R
r ( X j ,T ) 
 .d  j2
R
r ( X j ,T )
F o
 i p,i c pM
y o

i 1
c  F o o

o V o V
dz 4 Fj 4 Fj

z  0, T  To , X j  0

Limiting cases  
dT 4 4
1.Isothermal  0  (H r )rV  Te  T   (H r )rV   Te  T 
reactor
dz  dR  dR
T  To
2.Adiabatic dT  d R2 Fjo (H r ) dX j
reactor  o o  (H r )rV  
dz 4 F c pM  j F o c pM
o
dz
y oj (H r )
T  To  Xj
j c o
pM
 One reaction, constant heat capacity of species.
Profiles of conversion and temperature are given by following
equations:
dFi  dFj
  i rV  i
dT  dR
2
 4   j dVR
 (H r )rV  Te  T 
dVR
dz  N y o  dR  Fjo  Fj
4 F   yi c p ,i 
o o
c p X j 
j Xj 
Fjo
 i 1 j 
i 
Fi  Fi o   F j  Fjo    i F jo X j
dX j  .d R2  j  .d R2  j j j
 rV ( X j , T )  rV ( X j , T ) N N  o i o 
dz 4 Fjo 4 Fjo    p ,i  F  F X 
 i  j j j 
F c
i p ,i c
i 1 i 1  
N y oj 
z  0, T  To , X j  0  F   yi c p ,i 
o o
c p X j 
 i 1 j 

Limiting cases dT  4  4
1.Isothermal
 0  (H r )rV  Te  T   (H r )rV   Te  T 
dz  dR  dR
reactor T  To
 2.Adiabatic reactor

dT  d R2 Fjo (H r ) dX j
 (H r )rV   
dz N y o  N y o  dz
4 F   yi c p ,i 
o o
c p X j 
j
 j F   yi c p ,i 
o o
c p X j 
j

 i 1 j   i 1 j 



y oj  r H o  c p (T  T o ) dX j 
 N
 dz
 j


i 1
y o
c
i p ,i  y o
j c p X j

T Xj
dT dX j
  y j  r H  c p (T  T )
o o o

    y c N

o
 y oj c p X j 
o 0
T
j i p ,i
 i 1 
y oj ( r H o ) X j
T To  N
Cf. adiabatic BATCH and CSTR
j  i p,i j c p X j
y o

i 1
c  y o
 Exercise: reactor for oxidation of SO2 to SO3

„hot“ point
Numerical method:
• Euler method 700
Conversion of 1
SO2
0.9
„Stiff“ solvers 600
0.8
MATLAB
500 0.7
www.netlib.org
www.athenavisual.c 400
Temperature
0.6

om T [oC] 0.5 XSO2 [-]

300
http://wxmaxima.so 0.4

urceforge.net/wiki/i 200 0.3

ndex.php/Main_Pag 0.2

e 100
0.1

0 0
0.0 0.2 0.4 0.6 0.8 1.0
V [m3]
 Balance of mechanical energy in PFR
Profile of overall pressure (P(z))

dR

P(0) P( z )

z=0 z

VR=0 VR

Bernoulli equation

P(0)  P( z ) z 2 f
 v density of fluid(kg/m3)
f dR
 friction coefficient(-)
dP f 2   f (Re,  w / d R )
  v
dz dR
v fluid mean velocity
 Catalytic PFR
Profile of pressure is calculated using Ergun equation:

 f 1   b  o  f 1 b o 2
2
dP
   
2
  150 2 v  1.75 v  A  v o
 A  v o

dz dp  b3 f
d p  b3
f 1 f f 2 f f

 f - fluid dynamic viscosity (Pa.s)

 f - fluid density (kg/m3)

v of - superficial fluid mean velocity (m/s)

 b - bed porosity (-)

d p - catalyst particle diameter (m)

PFR model for one reaction with constant heat capacity of reaction
mixture

dT  d R2  4 
 (H r )rV  Te  T 
dz 4 F o c pM
o
 dR 
dX j  .d R2  j  .d R2  j
 r ( X j ,T ) 
o V
r ( X j ,T )
o V
dz 4 Fj 4 Fj
dP
  
   A1 f v of  A2  f v of
2

dz 

z  0, T  To , X j  0, P  Po
Example
A gas phase reaction between butadiene and ethylene is conducted in a PFR, producing cyclohexene:

C4H6(g) + C2H4(g)  C6H10(g)

A1 + A2  A3

The feed contains equimolar amounts of each reactant at 525 oC and the total pressure of 101 kPa.
The enthalpy of reaction at inlet temperature is -115 kJ/mol and reaction is second-order:

rV  k (T )c1c2
 115148.9 
k (T )  3.2 104 exp   (mol 1m3 s 1 )
 RT 

Assuming the process is adiabatic and isobaric, determine the volume of reactor and the residence time
for 25 % conversion of butadiene.

Data:
Mean heat capacities of components are as follows (supposing that heat capacities are constant
in given range of temperature)

cp1 = 150 J.mol-1.K-1, cp2 = 80 J.mol-1.K-1, cp3 = 250 J.mol-1.K-1

Project 15
A gas phase reaction between butadiene and ethylene is conducted in a PFR, producing cyclohexene:

C4H6(g) + C2H4(g)  C6H10(g)

A1 + A2  A3

The feed contains equimolar amounts of each reactant at 525 oC and the total pressure of 101 kPa.
The enthalpy of reaction at inlet temperature is -115 kJ/mol and reaction is second-order:

rV  k (T )c1c2
 115148.9 
k (T )  3.2 104 exp   (mol 1m3 s 1 )
 RT 
1. Calculate temperature and conversion profiles in adiabatic PFR.
2. Assuming the process is adiabatic and isobaric, determine the volume of reactor and the residence time
for 25 % conversion of butadiene.

Data:
Heat capacities of components will be taken from open resources [1,2]
1. http://webbook.nist.gov/chemistry/
2. B. E. Poling, J.M.Prausnitz, J.P.O’Connell, The Properties of Gases and Liquids, Fifth Edition,
McGraw-Hill, N.Y. 2001.