Single reactions in Continuous Isothermal Reactions

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Single reactions in Continuous Isothermal Reactions

Attribution Non-Commercial (BY-NC)

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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

2

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 = F jjo F j + V j r

*

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

C jo C j = j r

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

For any order

n r = kC A

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

Use A as the limiting reactant with stoichiometric coefficient = -1 (n=1) r=kC n A System is at constant density X varies from 0 to 1 C ( ) = C (1 X )

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()

11

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

Liquid flows down a tube completely unmixed. Same residence time for all molecules Assumptions

Constant Diameter Steady state Constant Density Single reaction

13

Residence Time

dz d = u

=

u (m/s) v (m3/s)

L V = u v

V (m3)

dz

L

14

Fjo = voCjo

u= v 4v = At D 2

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

Constant Diameter

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

A products

For reactant species A, A=-1

dC j d

= jr

A V dC A = = vo C Ao r

dC A = r d dC A = d r

17

For reactant species A (r=kCA) (r kC

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)

18

The reaction AB, r=kCA, occurs with 90% conversion. If k 0.5 min-1, CA0=2 moles/liter, and v=4 liters/min, k=0.5 2 v 4 what residence time and reactor volume will be required? How long a 2-cm diameter tube would be 2 cm required for this conversion and what would be the fluid velocity?

Assuming CSTR

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=

20

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

*

21

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

In PFTR, time t that a molecule spends in the reactor is z/u. Time for molecule to leave reactor is L/u. Residence time in a constant-density, constant crosssection PFTR

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

(Constant Density)

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

(FIRST order irreversible reactions with constant density)

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

25

C A0 C A C / C 1 CSTR VCSTR X = = = A0 A = PFTR VPFTR C A ln(C A0 / C A ) ln(C A0 / C A ) (1 X ) ln[1 /(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

(FIRST order irreversible reactions with constant density) AB

- 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

Difference between PF and CSTR becomes larger as the order of reaction becomes larger. r=kCA2

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 )

28

12.00 Tau_CST TR/Tau_PF F 10.00 8.00 6.00 4.00 2.00 0.00 0 0.2 0.4 X 0.6 0.8 1 n=2 n=1

29

0th order the sizes required for a given conversion are the same. Negative order the CSTR requires a smaller volume. Not true for non-isothermal. Positive order the CSTR requires a larger volume

30

(FIRST order irreversible reactions with constant density) Batch Reactor Size for a given conversion Simplicity and cost Continuous operation Large throughput Cleanout On-line analysis Product certification + + + + CSTR + + + + + PFTR + + + + 31

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

A(g)3B(g) (g) (g) r=kCA2

RT v=n P

35

Mass Balance At steady-state steady state

dN j dt = F jo F j + V j r

Fjo

X

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

V X = FA0 r X

A products No inert

e.g.

A(g)3B(g)+C(g)

= j = 3 + 1 1 = 3

j

V FA0 X C A0 X = = = vo vo r r

37

For variable density and cross-sectional area. Mass Balance Fj( ) z (z) z+dz Similarity of PF and CSTR (one is integral form) X F j ( z ) F j ( z + dz ) + At dz j r = 0 dX A

Fj(z+dz)

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

r = kC A

CSTR

F X (1 + X ) vo X (1 + X ) X = A0 = r X kC Ao (1 X ) k (1 X )

42

Ex. 3-7

r = kC A

(1 + X ) (1 X ) dX 0

X

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 =

C A0 = FA0

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

FA0 X

CA =

[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

X

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

Fig 3-6,

47

Analogy between batch reactor and PFTR not valid when density varies with conversion. (Cannot use the dtd when density changes) Constant-density used normally as an approximation when:

Equal moles of reactants and products Liquids Batch * Dil t d gases Diluted Constant Estimations

Variable PF

48

Reactor residence time defined based on the inlet conditions V *

ST = vo vo 1 = V ST SV =

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 2 C A3 = 3 r C A3 = 3kC A3

C A3 = C A0 C A2 = (1 + k 3 ) (1 + k 1 )( 1 + k 2 )( 1 + k 3 )

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

C An = (1 + k n ) n

54

CSTR =

C Ao C A 1 [C Ao C A ] = r CA r CA

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

CSTR followed by PFTR

1

C A0

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

The reaction AB, r=kCA occurs in n equal volume CSTRs in CSTR i series, each with residence ti i h ith id time ( ) with () ith 90% overall conversion. If k=0.5/min, CA0=2 moles/liter, and v=4liters/min, what residence ti l /lit d 4lit / i h t id times and reactor volumes will be required for n=1,2, and 4?

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

61

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

64

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 )

66

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

AB

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

For the PFTR

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

For this reaction calculate the residence time for 90% conversion in a CSTR and in a PFTR C Ao C A CSTR = k f C A kb (C Ao C A )

= 2.0 0.2 = ( ) 0.5 0.2 0.1(2.0 0.2)

= 0.10 0.18

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

For this reaction calculate the residence time for 90% conversion in a CSTR and in a PFTR = in either reactor. We go beyond the equilibrium conversion, which i i hi h is

kf kb = C B ,eq C A,eq = C Ao C A,eq C A,eq =5

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

Small-volume production Assume spatially uniform

dN j dt

Fjo Fj

= F jjo F j + V j r

Constant Volume

dC A = oC A0 C A Vr V dt

72

A may be added continuously but nothing removed to give dN j

dt = F jo F j + V j r

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

Bioreactors

Solids processing

74

During startup and shutdown g p Mass-balance equation for species A A Assume reactor volume and fl t l d flow rate are t constant and density is unchanged A = 1

dN A = F Ao F A Vr (C A ) dt d dC A V = v (C Ao C A ) Vr (C A ) dt

CSTR MASS BALANCE

dC A = (C Ao C A ) r (C A ) dt

75

Solvent replacement (No Reaction)

Initially t=0

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

t

C A = C A 0 [C A 0 C A ]e Ai

76

Tank initially filled with pure solvent. At t=0, feed switched to concentration CA0 that reacts with r=kCA

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 )

1 1 + k du u = ui

u

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 )

78

Solvent Replacement

e.g. A is salt g

CAo CA

C A = C A0 [C A0 C Ai ]e

CA = C A0 (1 + k )

CA

79

Transient in PFTR

A products

dV

dN A = F (V ) F (V + dV ) r dV dt dC A d (C AV ) dV = CA + dV = F (V ) F (V + dV ) r dV dt dt dt dC A dV = F (V ) F (V + dV ) r dV dt d C A F = r t V C A C = u A r t V

80

Batch

Variable Density

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

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