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Chapter 3
Scope
CSTR constant density & SS y
single reaction Reversible reaction
Plug Flow 1/r plot concept Semi-batch reactors Variable density Reactors in series
CSTR in series PF + CSTR
CSTR
Continuous stirred tank reactor (CSTR) Composition is the same everywhere in the reactor and the exit pipe. Volume = V [L]
vo
CA
v
CA
Residence Time *
v Volumetric v-Volumetric flow rate [L/s] Exit and tank composition same
CSTR
Steady-state Single Reaction Constant Density Reaction
liquid or gases, no mole change, e.g. A+2B3C g , g , g
CSTR
Mass Balance: [Accumulation]=[Flow in]-[Flow out] +[Generation]
dN j dt
= F jo F j + V j r
Molar flow rates of species j
moles time
moles time
Fjo = voC jo
L s mole L
0= 0 = C jo C j + V j r v
C jo C j j
Batch
v = vo
Const. Vol Const Vol. Flow
0 = C jo C j + j r
dCj d
= jr
C jo C j = j r
=r
6
A products p
C Ao C A = r
A = 1
n r = kC A
C Ao = C A (1 + k ) C C A = Ao 1 + k
*
C Ao C A kC A
Concentration of B
r=kCA
Single Reaction, AB
C B = C Ao C A
C B = C Ao C A C B = C Ao
*
C Ao C + C Aok C Ao = Ao 1 + k 1 + k
C jo C j = j r
CA CA Ao = r
For 2nd order (n=2)
*
2 kC A + C A C Ao = 0
A A products d t
1 1 + 4k CA = C A0 2k
Find CA() or (CA)
9
C Ao C A = C Ao X C Ao X =
Ao
C A ( ) = C Ao (1 = C Ao 1 + k
k ) 1 + k
X = k (1 X ) => X + kX = k k 1 X X= = 1 + k k 1 X
(X) or X()
C B ( ) = C Ao X =
Cj()
10
Reversible Reactions
AB CB=0
r = k f C A kbC B
* *
r=
=
C Ao C A = r
C jo C j = j r
1+ kb CA = C A0 (k f + kb ) + 1
So, CA()
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Reversible Reactions
1+ 1+ kb CA = C A0 ( k f + kb ) + 1
C B = C A0 C A
= C Ao = = C Ao kb (kb + k f ) ( kb + k f ) C Ao k f ( k f + kb )
(the conc ratio = Keq when is large consistent)
12
As
*
C Ao (kb + k f ) C Ao kb
CB k f = C A kb
13
Residence Time
dz d = u
=
u (m/s) v (m3/s)
L V = u v
V (m3)
dz
L
14
Fj =vCj
Mass Balance on j
z+dz d
F j ( z ) F j ( z + dz ) + At dz j r = 0 At u C j ( z ) C j ( z + dz ) + At dz j r = 0
dC j jr dz = lim C j ( z ) C j ( z + dz ) dz dz 0 u dz z
F j ( z ) = vC j = uAt C j
Tube Area
dC j dz
= jr
d = d / u dz
dC j d
= jr
15
F j ( z ) F j ( z + dz ) + At dz j r = 0
Variable Cross-section (dV=Atdz) Cross section (dV A
F j (V ) F j (V + dV ) + dV j r = 0
lim
dv0
F j (V + dV ) F j (V ) dV
= jr
dF j
V V+dV
dV
= jr
16
dC j d
= jr
A V dC A = = vo C Ao r
dC A = r d dC A = d r
17
dC j d
dC A = k d CA 0
= jr
dC A = r d dC A = kC A d dC A = kd CA
CA
C Ao
ln
CA = k C Ao
C A = C A e k Ao
(looks like Batch but rather than t)
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C Ao C A = r
* *
C jo C j = j r
19
Exs. 3-1 & 3-3 PF versus CSTR (first order) Assuming PFTR
*
dC j d
= jr
C A = C Ao e k
u=
Exs. 3-2 & 3-4 (2nd Order) The reaction AB r=kCA2 occurs with 90% conversion. k=0.5 liter/mole-min, conversion If k=0 5 liter/mole-min CA0=2 moles/liter and v=4 liters/min, what residence time and reactor volume are required? Assuming CSTR
*
PFTR
dC j
CA
C Ao
dC A r
= jr
r=kCA2
C Ao
CA
VPF = 4 x9 = 36liters
10 times smaller than for CSTR
22
PFTR =
V L = v u
By using dt dz / u d We can convert Batch Reactor to PFTR Design equation: dC A dC A dC A u = = r a) Aproducts dt, dz PFTR dz dt d b) Const V z
Completely mixed inside 1 slice
23
C A = C Ao 1 + (n 1)kC t
nth order kinetics in a PFTR is same
n 1 1 /(1 n ) Ao
C A = C Ao 1 + ( n 1) kC
PFTR = tbatch
n 1 Ao
1 /(1 n )
24
PFTR = tbatch
1 A dC A 1 C 1 C = = ln A = ln A0 k C Ao C A k C A0 k C A
C A0 C A kC A
PF :
dC A = r d
CSTR =
CA = 1 X C A0 C A0 1 1 = 1 CA 1 X
X=(CA0-CA)/CA0
CSTR
PFTR
0.0 1.0 0.5 05 1.44 1 44 0.9 3.91 0.95 6.34 0.99 21.5 0.999 145 CSTR becomes very large compared to PFTR for high conversion for these kinetics.
26
- B t h or PFTR will give th same conversion Batch ill i the i - CSTR gives a lower conversion for the same reaction time (batch) or residence ti ti (b t h) id time ( (continuous) ti )
27
PFTR
C A0 C A = kC A0C A
CSTR
C A0 C A = 2 kC A
CSTR C A0 1 = = PFTR C A (1 X )
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29
30
1/r Plot
CSTR =
C Ao C A 1 [C Ao C A ] = r CA r CA
CA
Aproducts A = -1
PFTR = PFTR =
CA
C Ao
1 dC A r CA
dC j d
= jr
CSTR
C Ao
1 d (C A0 C A ) r CA
*
= ydx
PF
CSTR very inefficient for high X (For first order and other + n orders)
XA=0
XA=1
32
d(CA0-CA)=-dCA
r is monotonically decreasing for n (+) r is a horizontal line for n=0 r increases if n<0
PF <CSTR
CSTR PF
PF >CSTR
n= -1
33
Variable Density y
r = kC A
A3B
In constant pressure reactor and A and B are ideal gases and with no diluents present. 2 Density of fluid changes as reaction proceeds. At X=1, 3 moles of product for each mole of reactant formed. Volumetric flow rate out will be 3 times the flow rate into reactor. reactor
v = 3vo
In tubular reactor with constant diameter, the linear velocity is three times the inlet velocity:
u = 3uo
Previous equations do not describe these reactors since v v,, and u depend on conversion.
34
RT v=n P
Fj
X
0 = F jo F j + V j r
FA = FAo (1 X )
V X = FA0 A r X V X = FA0 r X
A = 1
36
A(g)3B(g)+C(g)
= j = 3 + 1 1 = 3
j
V FA0 X C A0 X = = = vo vo r r
37
V = FA0
0
r
X
A=-1
C A = C A0 (1 X A )
V dX A C X A = 1 A = C A0 C A0 vo r 0
=
FA = FA0 (1 X A ) dFA = FA0 dX A
V dC A = vo r C A0
CA
dX A =
dC A C A0
Const density
38
Ex. 3-6
A 2B + C
r=kCA2
Find the expression for the reactor volume V for specified and feed flow FAo for the reaction among ideal gases with no g g diluent in a CSTR and PFTR.
F A = F A 0 (1 X ) FB = 2 FA0 X FC = F A 0 X F = F A 0 (1 + 2 X )
VCSTR
FAo X (1 + 2 X ) 2 X = FAo = 2 r X kC Ao (1 X ) 2
dX d rX X =0 (1 + 2 X ) 2 =0 (1 X )2 dX X
X X
v = vo (1 + 2 X )
F0 = A2 kC Ao
FA0 2 kC Ao
9 4 X 9 + 12 ln(1 X ) + ( 1 X
39
Ex. 3-6
(1 + 2 X ) =0 (1 X )2 dX X
X 2
A 2B + C
4 x2-2x+14x2+4x+1 2x 1 4x 1 4x2- 8x+4 12x 3 12x-3
4 X 1 A B = + (1 X ) 2 (1 X ) (1 X ) 2 4 X 1 A(1 X ) + B = (1 X ) 2 (1 X ) 2 4 X 1 = A(1 X ) + B X = 1, X = 0, 3= B 1 = A + 3 => A = 4
40
= = =
X =0
X X
4+
12 X 3 dX 2 (1 X ) 4 X 1 dX 2 (1 X ) 3 4 +3 dX 2 (1 X ) (1 X )
4+3 4+3
X =0
X =0
9 = 4 X 9 + 12 ln(1 X ) + 1 X
Ex. 3-7
Find the reactor volume V required to obtain 90% conversion in the reaction among ideal gases in a CSTR and in a PFTR with no diluent for nB=2, 1 and with CA0= 2 moles/liter k=0 5 min-1, and vo= 4 moles/liter, k=0.5 liters/min. (high pressure reactor, p=49 atm).
nB = 2
FA = FA0 (1 X ) FB = 2 FA0 X FA + FB = FA0 (1 + X ) v = vo (1 + X )
CA = r=
41
Ex. 3-7
CSTR
F X (1 + X ) vo X (1 + X ) X = A0 = r X kC Ao (1 X ) k (1 X )
42
Ex. 3-7
PFTR
X
VPFTR
F dX = FAo = A0 r X kC Ao 0 vo k (1 + X ) (1 X ) dX 0
X X
-1 1
-x+1x
VPFTR = VPFTR
x1 x-1 +1
vo 1 1 dX = 1+ k 0 1 X (1 X ) v0 [ X 2 ln(1 X )] = 29.6liters k
43
VPFTR =
nB = 1
r = kC A = kC Ao (1 X )
= o
VCSTR = FA 0 v F X X X 4 0 .9 = A0 = o = = 72 liters r X kC Ao 1 X k 1 X 0 .5 0 .1
X X
VPFTR
F v dX dX 1 = FA0 = A0 = o ln = 8 ln 10 = 18.4 L r X kC Ao 0 1 X k 1 X 0
44
nB = 1 / 2
FB =
1 2
[AB]
FA = FA0 (1 X ) FA + FB = FA0 (1 1 2 X )
FA0 (1 X ) (1 X ) = CA Ao (1 1 2 X ) o (1 12 X ) (1 X ) (1 1 2 X )
= o (1 1 2 X )
VCSTR
r = kC A = kC Ao
VPF
F dX = FA0 = A0 r X kC A Ao 0
v (1 12 X ) dX = o [ ln(1 X ) + X ] 1 X 2k 0
X
45
[ [AB] ]
V is larger than with no density change if the reaction produces more moles ( B=2) b ti d l (n 2) because thi this dilutes the reactant, while V is smaller if the reaction reduces th number of moles ( B=1/2) ti d the b f l (n 1/2) nB 2
*
[ [AnBB] ]
*
r = kC A
46
47
48
In variable density reactions, the velocity changes with con ersion Changing P and T ith conversion. along reactor can also change v.
49
PFTRs in series
1 2
A Products
ith N
X0
X1
X2
XN-1
XN
1 PFTR:
V dX = = C A0 A vo r 0
Consider N plug flow reactors connected in series. Let X1, X2, XN be the fractional conversion of A leaving reactor 1,2,..N. Based on the material balance for ith reactor Xi Vi dX i = = C A0 v0 r X i 1
50
PFTRs in series
For N reactors in series
V FA0
=
*
dX dX dX + + ... + r X r r X0 X n1 1
X1
X2
Xn
If no change of composition of intermediate streams, then PFTRs in series is same as 1 large PFTR
V FA0
dX = r X0
51
Xn
C A0 C A1 = 1r C A1 = 1kC A1 C A1 C A 2 = 2 r C A 2 = 2 kC A 2
C A2 =
C A1
C A0 = (1 + k 1 )
C A0 C A1 = (1 + k 2 ) (1 + k 1 )( 1 + k 2 )
52
C A 1 C A = n r C A = n kC A An 1 An An An
C An = C A ( n 1 ) (1 + k n ) =
=1, n
53
C A0 (1 + k )
CSTR in Series
If each reactor has the same volume and they have the same residence time ( ) T t l residence ti Total id time
= = n
1
55
PFTR+CSTR
First order kinetics Solve the mass balance sequentially to find CA1 and then CA2. PFTR followed b CSTR f ll d by C A1 C A2 C Ao
C A2
C A1 = 1 + k 2
2
C A2 = C A0 k 1 C A1 e = 1 + k 2 1 + k 2
56
A1
= C
A 0
C A1
C A2
2
C A1 =
C A0 1 + k 1
C A0 e k 2 1 + k 1 For equal volume reactors (1=2) and first order kinetics, the expressions are identical for both configurations. So which reactor is first is inconsequential. i ti l C A 2 = C A1 e k 2 =
57
PFTR+CSTR
Usually use CSTR first (conversion low, CA high) then PFTR to minimize total reactor volume. volume
58
C An
C Ao = (1 + k n ) n
1 n
C An n = (1 + k n ) C Ao
C An C Ao = (1 + k n )
n C Ao n = C k An
1/ n
CSTR
ln
C A1 = k PF C A0 A0
59
1 = =
Ex. 3 8 Ex 3-8
2 2 = 2 = k
4 C Ao 4 = 4 = C k A
1/ 4
PF =
1 1 ln = 4 .6 0 .5 10
60
Ex. Ex 3-8
For n=1, we have single CSTR. as n to approach PFTR for which =4.61min Total Reactor volumes: n=1, V1=72 L, (=4 x 18) n=2, V2=34.6 L, (=4 x 8.65) n=3, V3=27.7 L, (=4 x 6.92) n=4, V4=24.9 L, (=4 x 6.22)
V = v
Autocatalytic Reactions
A B , r = kC A C B
R t of f Rate f forward reaction i enhanced b d ti is h d by concentration of a product. Can also be written by
A + B 2 B, r = kC AC B
Requires CB0 In CSTR CB0 In PF CB=0 at entry. 0. CSTR, 0, PF, entry
CA0 CB0=0 CAf CBf 0 (TANK reaction happens) CA0 CB0=0 CA0 CB0=0
62
Autocatalytic Reactions y
r C A = kC A C B = kC A (C A 0 + C B 0 C A ) Rate If CB0=0, 0
r = kC A (C A0 C A )
r versus CA0-CA is a parabola. PF requires time since r=0 at feed (pure A). CSTR is feasible.
63
Autocatalytic Reactions y
PFTR
=
dC A kC A (C A0 + CB 0 C A ) C A0
C CA
A V dC A = = vo C Ao r
A 1 1 1 = dC A + dC A k (C A0 + C B 0 ) C0 C A C A0 + C B 0 C A A
CA C + CB0 C A 1 ln l l ln A0 k (C A0 + C B 0 ) C A0 C A0 + C B 0 C A0
CB 0 CA 1 = ln k (C A0 + C B 0 ) C A0 C A0 + C B 0 C A
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Autocatalytic Reactions
Partial fractions
dC A = kC A (C A0 + C B 0 C A ) C A0
CA
A (C A 0 + C B 0 C A ) + BC A = 1 C A = 0, 1 + CB0 BC A = 1, A (C A 0 + C B 0 ) = 1,
Let A= Let B=
1 A B dC A dC A + k C0 C A C A0 + C B 0 C A A
C
CA
C A0
1 A A(C A0 + C B 0 C A ) + BC A = dC A k C A 0 C A [C A0 + C B 0 C A ]
C
C A = C A0 + C B 0 , 1 + CB0
C A0
A 1 1 1 = dC A + dC A CA k (C A0 + C B 0 ) C A 0 C A0 + C B 0 C A
65
Autocatalytic Reactions
CSTR
=
C A0 C A C A0 C A = r CA kC A (C A0 + C B 0 C A )
Reversible Reactions
Rate goes to 0 near . For PF and CSTR, as (1/r at ) rxn goes to . CSTR needs a longer (like irreversible reaction)
r=kCA
CSTR
r=kfCA-kbCB
PF
67
r = k f C A kb C B
For the reaction, find the residence times for 50% conversion in a CSTR and in a PFTR if kf=0.5 min-1, kb=0.1 min-1, CAO=2 moles/liter, v=4 liters/min, and CBo=0.
For the CSTR
*
68
PFTR = PFTR
CA
C Ao
dC A k f C A kb (C Ao C A )
k f C Ao 1 = ln k f + kb (k f + kb )C A kbC Ao
= 1 0 .5 2 ln = 1 .53 min 0 .6 0 .6 1 0 .1 2
69
PFTR
k f C Ao 1 ln l = k f + kb (k f + kb )C A kbC Ao
= 1 0.5 2 ln = ln() 0.6 0.6 0.2 0.1 2
= 0.08
70
so th t CA,eq=0.33 moles/liter, CB,eq=1.67 moles/liter, and that 0 33 l /lit 1 67 l /lit d the equilibrium conversion is 83%. This is the maximum conversion obtained for these kinetics in ki ti i any single reactor i l t
71
= F jjo F j + V j r
Constant Volume
dC A = oC A0 C A Vr V dt
72
Vol me V of reactor increases linearl with time Volume linearly ith We obtain
V = Vo + vot
dVC A dV dC A = CA +V = FAo + V j r dt dt dt C Avo + V dC A = C Ao vo + V j r dt
(Vo +t )
dC A = o (C A0 C A ) (Vo + vot )r dt
73
Solids processing
74
dC A = (C Ao C A ) r (C A ) dt
75
Replace the pure solvent with a brine (A) (CAi=0) CA0 is inlet concentration dC A CA is concentration within tank = (C Ao C A ) r (C A ) dt CAi is initial concentration within tank Let u=CA-CA0
dC A = (C Ao C A ) dt
t
ln
u ui
= ln
C A C A0 t = C Ai C A0
t
dC A 1 = dt C A0 C A 0 C Ai
du 1 = dt u 0 ui
u t
CA
C A C A0 =e C Ai C A0
C A = C A 0 [C A 0 C A ]e Ai
76
dC A = (C Ao C A ) kC A dt dC A dt d = C Ao C A kC A
u = C A (1 + k ) C A 0 du = (1 + k )dC A 1 du 1 + k 1 du dt = 1 + k u dC A =
77
dC A dt = C A0 C A (1 + k )
dt
u 1 + k = exp( )t ui
1 u t ln = 1 + k u i
C A (1 + k ) C A0 1 + k = exp( )t C Ai (1 + k ) C A0
1 + k
C A (1 + k ) = C A 0 [C A 0 C Ai (1 + k ) ]exp( (
C A0 [C A0 C Ai (1 + k )]exp( (1 + k ) 1 + k
)t
CA =
)t
At long times
CA =
C A0 (1 + k )
Solvent Replacement
e.g. A is salt g
CAo CA
C A = C A0 [C A0 C Ai ]e
CA
79
Transient in PFTR
A products
dV
CSTR
FA0 X = V A r FA0 X =V Ar
PFTR
dFA = Ar dV FA0 dX A = dV Ar
dC j d = jr
81
1 dN A = Ar V dt
Constant Density
dC j dt
= jr
C jo C j = j r
THE END
82