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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
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
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
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
H VR
VR T VR 1 pT
P T ,n j 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
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 VRT i
dt i 1 dt
P T ,n j
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
NR
dT
Isothermal m cPVR 0 VR r H k rV ,k Q
reactor dt k 1
Adiabatic dT NR
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
Calculate X1(t),T(t).
Example
Acetic anhydride reacts with water
Data
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
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
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
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
0.8 f1(T)
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:
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
VR = 2 m3 To = 310 K
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
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
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
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:
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 1m3 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)
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 1m3 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.