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Reactor Design
Technological
n n n
Maximum possible product in minimum time Desired quantity in minimum time Maximum possible product in desired time Maximize profit
Economic
n
Market
n n
Raw materials availability quality and quantity Demand for the product Safety Pollution control Thermodynamics Stoichiometry Kinetics
Society/Legislative
n n
Technological
n n n
of reactor
Tubular, Fixed Bed, Stirred tank, Fluidized bed Mass Flow: Batch, Continuous, Semibatch Energy: Isothermal, Adiabatic, Co/counter current
Mode
q q
Process
q
Intensification
+ ( Flux j ) = R j t z
+ ( uC j + J j ) = R j t z
M jC j + u M jC j + M j J j = M j R j t j j z j j f + ( u f ) = 0 t x
dN j dt
= Fj 0 F je + R j
= qmj
T T 2T 4 + us e 2 + qh = U (Tr T ) C jCPj z z dt j t
( Dej,r , C j ) 1 Y rX ( X ,Y ) = r r (e,r , T )
Psuedohomogenous model
qmj = R j qh = H i ri
i
h f av (T Ts ) = H i ri
i
K g av (C j C js ) = R j (C js , Ts )
C 'j r
r=R
av = R j ( C j )
qh = i ( H i ) ri
i
Concentration
10
20
30
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Time (min)
340 320 300 2.0 1.5 1.0 0.5 0.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Residence time
1/rate
4 2 0 0.0
0.5
1.0
1.5
2.0
C10-C1
0.8 0.6
Xeq
Adiabatic
Rate
0.1
0.01 0.0
0.2
0.4
0.6
0.8
100 1.0 10
conversion
1/rate
0.2
0.4
0.6
0.8
1.0
conversion
Optimal temperature
500 0.9 450
0.8
400
0.7
350 300
0.6
Extent
0.5
250
0.4
200 150
0.3
0.2
100
0.1
50
450
500
550
600
650
700
Temperature K
Ethylene demands polyethylene, ethylene oxide, ethylene glycol 20 million tons per annum Main Reaction C2 H6 C2 H4 + H2 increase in number of moles so steam as inert Endothermic reaction - H 34.5 kcal/mol, high temperature for high equilibrium conversions, increasing temperatures along the length of the reactor Side reactions higher conversion yield of side products higher
Indian Institute of Science
2C2 H6 C3 H8 + CH 4
Balances
mass energy dF j
d t2 = Rj dz 4
d t2 q( z ) d t + ( H i )ri 4 i
dT 1 = dz F jC pj
j
dp 2 f du momentum = + f u2 + f u dz d t rb i dz RT F j F' 1 j u= = A A p
Hydrogenation of oil
Major demand margarine, shortenings, vanaspati Vegetable oils mixture of triglycerides - glycerol and fatty acids Fatty acids saturated (S) , monosaturated (cis, R1 and trans, R2) and diunsaturated (B). Hydrogenation to reduce odor or color, improve stability and increase melting point. Product requirements some polyunsaturated (health) and R2 ( consistency and higher melting points)
Reactions
r1 r4 C , r5 r6 CH 2
1/ 2 H2
Balances
dC j
mass
dt k Lav CH 2 , g CH 2 ,s = RH 2 C j , CH 2 ,s
= Rj
j = B, R1 , R2 , M
) )
dCH 2 ,b
dt 0 = k S aS CH 2 ,b CH 2 ,s + RH 2
= k L a v C H 2 , g C H 2 ,b k S a S C H 2 ,b C H 2 , s
1 1 1 = + k L av k L av k S a S
Q = V ( Hi )ri = AKU (T Tr )
i
Ammonia synthesis
Major
demand Fertilizer, chemicals, explosives, polyamides, pharmaceuticals; 150 million tons per annum Main reaction
1 3 N 2 + H 2 ! NH 3 , !H 298 K = "45.7 kJ / mol "1 2 2
High
1.0 0.9
1.0
0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 500
1
P = 300 atm
(A)
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0
(B)
200 100 50
10 3
600
700
800
900
100
200
300
Temperature (K)
Pressure (Atm)
catalyst
Reactor simulation
0.7 0.6
mol fraction
H2 NH3
temperature
0.5
N2
860 840 820 800 780 760 740 720 700 680
Length (m)
Length (m)
120 100 80
rate at bulk conditions observed rate
rate
60 40 20 0 0 1 2 3 4 5
Length (m)
Optimal temperature
500 0.9 450
0.8
400
0.7
350 300
0.6
Extent
0.5
250
0.4
200 150
0.3
0.2
100
0.1
50
450
500
550
600
650
700
Temperature K
Conversion
500
600
700
800
900
Temperature
Ammonia Autothermal
300 250 200
Tfeed K
500
600
700
800
900
1000
400 400
500
600
700
800
900
1000
Ttop
Ttop K
Ammonia Autothermal
800 750
0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0
Conversion
700
Conversion
r=0 r/ T=0
600
650
700
750
800
850
900
Length
Temperature
Process intensification
Strategy
of reduction in physical size of a chemical plant while achieving given objective 30 40 years old concept, reinvented in last decade due to intense competition, scarce resources and stricter environmental norms Multifunctional reactive systems several functions are designed to occur simultaneously. Major drive in refining and petrochemicals sector
Type A at catalyst level Type B at interphase transport level Type C at intra-reactor level separations/heat transfer Type D inter-reactor level by combining two reactor operation with solids recirculation.
number Conversion of parafins, cyclo parafins and napthenes to aromatics and branced paraffins. Reactions involved dehydrogenation, cyclization and isomerization Pt/SiO2 catalyst
GAS ENTRANCE
DRAFT TUBE
SUSPENDING IMPELLER
transfer reaction in heat exchanger Momentum transfer radial flow reactors Mass transfer reactive- distillation, absorption
gas flow rates ammonia synthesis, styrene from ethylbenzene, flue gas treatments
conversion in equilibrium limited reaction, prevent undesirable reaction, increase rate of product inhibited reactions
H = 803 kJ / mol
Length
840
Temperature
Length
partial pressure
temperature
700
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Length
Length
0.020
Partial pressure
Sensitive
Insensitive
640
650
660
temperature
q < p2 / 4 1,2 = 1, 2
'' < 0
q > p2 / 4 1,2 = i
<0
q=det (A)
q = p2 / 4
q > p2 / 4 1,2 = i
>0
2
q < p2 / 4 1,2 = 1, 2
1 > 0, 1 > 2
p=tr (A)
Stability analysis
A
state X=0 is said to be stable when given e>0, there exists a d>0 (0<d<e) such that if ||X (0)||<d then ||X(t)|| < e for all t>0 A state X=0 is said to be asymptotically attractive when given m>0, such that if ||X(0)|| <m then lim (t) ||X(t)|| =0 A state is asymptotically stable when stable and asymptotically attractive. A state is marginally stable when stable but not asymptotically attractive
Indian Institute of Science
Examples
x2 ( y x ) + y5 dx = dt 1 + x 2 + y 2 + ( x 2 + y 2 )2 y2 ( y 2x) dy = dt 1 + x 2 + y 2 + ( x 2 + y 2 )2
1.0 0.8 0.6 0.4 0.2 0.0 0.0 0.2 0.4 0.6 0.8 1.0
dx =y dt dy = x dt
1.2 1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.2-1.0-0.8-0.6-0.4-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
D=determinant(A)
T /4-D=0
T=trace(A)
Indian Institute of Science
D=determinant(A)
Unstable node
= 0.1 D = 0.00971, T = 0.988
45 40 35 30 25 20 15 10 -50 0 50 100 150 200 250 300 350 0.10 0.08 0.06
T /4-D=0
= 0.0099,0.9782
T=trace(A)
alpha
beta
0.04 0.02 0.00 -50 0 50 100 150 200 250 300 350
Time
Time
beta
alpha
Unstable focus
= 0.5 D = 0.248, T = 0.751
350 300 250 200 3.0 2.5 2.0
D=determinant(A)
T /4-D=0
= 0.3756 0.3276i
beta
1.5 1.0 0.5
T=trace(A)
alpha
150 100 50 0 -50 -50 0 50100 200 300 400 500 600 700 150 250 350 450 550 650 750
0.0 -50
50
100
150
200
250
300
350
Time
Time
beta
beta
1.5
10 8 6 4 2 0 -2 -4 -6 -8 -10
10 12 14 16 18 20
alpha
alpha
D=determinant(A)
Stable focus
= 2.0 D = 3.99, T = 2.98 = -1.4900 1.3288i
0.80 0.75 0.70 2.1 2.0 1.9 1.8
T /4-D=0
T=trace(A)
alpha
beta
0 50 100 150 200 250 300 350
1.7 1.6 1.5 1.4 -50 0 50 100 150 200 250 300 350
Time
Time
1.7 1.6 1.5 1.4 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80
alpha
1.8
beta
0.1 0.0 -2 0 2 4 6 8 10
alpha
alpha
D=determinant(A)
Stable node
= 2.5 D = 6.23, T = -5.21
0.65 0.60 2.5 2.4 2.3 0.55 0.50 0.45 0.40 -50 0 50 100 150 200 250 300 350
T /4-D=0
= -3.3614, -1.8525
T=trace(A)
alpha
beta
2.2 2.1 2.0 1.9 1.8 -50 0 50 100 150 200 250 300 350
Time
Time
beta
2.2 2.1 2.0 1.9 1.8 0.40 0.45 0.50 0.55 0.60 0.65
alpha
D=determinant(A)
Limit cycle
= 1.005
1.6 1.4 1.2
T /4-D=0
D = 1.01, T = 0
1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7
= 1.003i
T=trace(A)
alpha
1.0 0.8 0.6 -50 0 50 100 150 200 250 300 350
beta
-50
50
100
150
200
250
300
350
Time
Time
1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.8 1.0 1.2 1.4 1.6
beta
alpha
Adiabatic CSTR
100 80
Heat generation Heat removal =60 s =10 s = 100 s
rate
60 40 20 0 0 1
conversion
conversion temperature 2
0 40 80 120 160 200 0
residence time
Temperature
Conversion
If, we know precisely what is happening within the vessel, thus, if we have a complete velocity distribution map for the fluid in the vessel, then we should, in principle, be able to predict the behavior of a vessel as a reactor. Unfortunately, this approach is impractical, even in today s computer age. Levenspiel, Chemical Reaction Engineering, 1999. Mobil Adds Million-Dollar Benefits by Using Flow Simulation to Optimize Refinery Units, Greg Muldowney, Mobil Technology Company, 2007
Anaerobic digestion
Complex polymers
Fermentative B.
HYDROLYSIS and ACIDOGENESIS
Monomers
20 76
Acidogenic B.
Acetogenic B.
Acetate
METHANOGENESIS
52
24
CO2 + H2
28
72
CH4 + CO2
CH +H O
Biogas out
1
0.15
Gas
0.15
1.2
Waste water in
y
1.4
Contour plot for liquid velocity (m/s) (with Packed bed) Indian Institute of Science
PIV experiments
Experimental verification
Contours of X-direction mean velocity (inlet NRe=7660) (a)experimental and (b ) Simulation results without packed bed
Experimental verification
Contours of X-direction mean velocity (inlet NRe=500) (a)experimental and (b ) Simulation results with packed bed
Fraction of material in exit stream which has age between t and t+dt
Cumulative
q
Internal
q
dF (t ) F (t ) = E (t ')dt ' or = E (t ), dt 0
Fraction of material within vessel which has age between t and t+dt t
residence time
t = tE (t )dt
0
Variance
= t t E (t )dt
2 0
( )
2
Skewness
s = t t E (t )dt
3 0
( )
3/ 2
Example
0.20 0.15
1.0 0.8
E(t)
F(t)
t
0.20 0.15 0.10 0.05 0.00
t
0.8 0.6
t E(t)
0 2 4 6 8 10 12 14
I(t)
10
12
14
integral
t 0
Pulse
input
E (t ) = Ce (t )
C (t ) dt
e 0
Step
input
F (t ) = Ce (t ) C0
Indian Institute of Science
1 E (t ) = exp ( t )
PFR
E (t ) = (t ), F (t ) = H (t )
PFR-CSTR
or CSTR-PFR
0
t <p
E (t ) = 1 t p exp t p s s
Indian Institute of Science
of the reaction the RTD of fluid in the reactor the earliness or lateness of fluid mixing in the reactor whether the fluid is a micro or macro fluid
C/C0
10
k C0
in the reactor Micromixing description of how molecules of different ages interaction with each other
q
Complete segregation all molecules of same age group remain together until they exit the reactor Complete micromixing molecules of different age group are completely mixed
the
earliness or lateness of fluid mixing in the reactor whether the fluid is a micro or macro fluid
Indian Institute of Science
segregation
Cs = C (t ) E (t )dt
0
Model
dC = R(C ) C (0) = C0 dt dCs = C (t ) E (t ) Cs (0) = 0 dt Cs = C (t ) E (t )dt
0
z t= t ( 0, ) z ( 0,1) z 1 dC R (C ) = dz (1 z )2 dCs E ( z 1 z ) = C 2 dz (1 z )
dC dC dz 2 dc = = (1 z ) dt dz dt dz
mixedness
dC E ( ) = R(C ) (C10 C ) d 1 F ( )
C ( = 0) = C10
0.4
maximum mixedness complete segregation 2 CSTRs
C/C0
k C0
1.0
Concentration
CA (r=1m) CB CA (r=100m) CB
0.4
CAe
1000
10000
r( m)
10
in - series
N N t n1 nt E (t ) = exp ( N 1)! N
2 =
1 N
dispersion model
1 1 = 1 (1 e Pe ) Pe Pe
2
RTD
7
10
6
1 2 3 4
5 4
500
dispersion model
4 2
E(t)
E(t)
3 2 1
0 5 40
0 0.0
0.5
1.0
1.5
2.0
Transient in PFR
1.0 0.8 0.6
: :
2.5
0.2
0.4
0.6
0.8
1.0
Compartment models
Example
1.0 0.8
1.0 0.8
ConversionA
1 CSTR 2 CSTR
YieldB
0.6
1 CSTR 2 CSTR
0.8
1.0
0.0 0.0
0.2
0.4
0.6
0.8
1.0
0.6
'
0.5 0.4
0.1
0 .1
1
0
0.1 11 0 0 100
10
0 300
310
320
330
340
350
360
370
380
Temperature