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You are on page 1of 114

(CHE 471)

M.P. Dudukovic

Chemical Reaction Engineering Laboratory

(CREL),

Washington University, St. Louis, MO

ChE 471: LECTURE 4 Fall 2003

IDEAL REACTORS

One of the key goals of chemical reaction engineering is to quantify the relationship between

production rate, reactor size, reaction kinetics and selected operating conditions. This requires a

mathematical model of the system, which in turn rests on application of conservation laws to a

well-defined control volume of the reaction system and on use of appropriate constitutive

expressions for the reaction rates. The concepts of ideal reactors allow us to quantify reactor

performance as a function of its size and selected operating conditions.

To illustrate this useful concept we deal here with a single, homogeneous phase, single reaction

at constant temperature. We introduce then the ideal batch reactor, and two ideal continuous

flow reactors. In each case we apply the conservation of species mass principle which states

(Rate of Accumulation) = (Rate of Input) (Rate of Output) + (Rate of Generation) (2-1)

Equation (2-1) is applied to an appropriately selected control volume, the largest arbitrarily

selected volume of the system in which there are no gradients in composition.

The ideal batch reactor is assumed to be perfectly mixed. This implies that at a given moment in

time the concentration is uniform throughout the vessel. The volume, V in the development

below is assumed equal to the volume of the reaction mixture. This is then equal to the reactor

volume VR in case of gas phase reaction but not in case of liquids (V< VR, then). The batch

reactor can be an autoclave of V = const (Figure 2.1-a) and a constant pressure, P = const)

(Figure 2.1-b) vessel. The former is almost always encountered in practice.

a) To find a relationship between species concentration (reactant conversion) and time on

stream.

b) To relate reactor size and production rate.

1

Let us consider a single irreversible reaction A P with an n-th order irreversible rate of

reaction

RA = kC An (2-2)

At t = 0 a batch of volume V is filled with fluid of concentration CAo. Reaction is started (nAo=

CAoVo). Find how reactant conversion depends on reaction time? Also determine the production

rate as a function of reaction time.

dnA d(VCA )

0 0 + (RA V) = = (2-3)

dt dt

a) V = const b) P = const

2

In our case due to the fact that

j=1

j = 0 , V= const irrespective of the batch reactor type, so that

eq (2-3) becomes

dC A

= RA (2-4)

dt

dC n

A = ( RA ) = kC A ; t = 0 C A = CAo (2-5)

dt

CA

t

dC A 1 CAo dC A

dt = kC n = k C n (2-6)

o C A0 A CA A

2

CAo

t 1 C 1n

to= A

k 1 n CA

(2-7)

1

t0 =

k(1 n)

[C Ao C A ]

1n 1n

1n

C Ao

t=

k(1 n)

[

1 (1 x A ) ]

1n

(2-8a)

or

1

n1 [(1 x A ) 1]

1n

t= (2-8b)

k(n 1)CAo

Once order of reaction, n, is specified (as shown below for n=0, 1, 2, 1.5), the relation between t

and xA is readily found

n=0 n =1 n=2

CAo x A 1

t = ln

1 1 1 (2-9)

t= t= 1

k k 1 x A kC Ao 1 x A

1 1

n = 1.5; t= (1 x A ) 0.5 1

0.5k C Ao

mol FAo x A

FP =

S 1

(moles of P processed per batch)

FP = (2-10)

(reaction time + shut down time per batch)

C AoV x A C AoV x A

FP = = (2-11)

t + ts 1

n1 [

(1 x A ) ] + t s

1n

k(n 1)C Ao

NOTA BENE: Equation (2-11) is valid only for systems of constant density. Thus, it is valid

for all systems, gas or liquid, conducted in an autoclave at V = const (see

Figure 2-1a). It is also valid for gaseous systems with no change in the

3

number of moles ( j = 0) conducted in P = const. system at T = const

(Figure 2-1b).

The first equality in equation (2-11) gives the general result, the second equality presents the

result for an n-th order irreversible reaction with resect to reactant A.

To use this equation the shut down time, i.e. the time needed between batches, ts, must be

known. Consider now the following second order reaction with stoichiometry A = P.

mol

RA = 0.1CA

2

L min

a) Find the batch reactor volume needed to produce FP = 38 kmol/min if reactor shut down

time is 60 minutes and the desired conversion is 0.95. Initial reactant concentration is

CAo = 1 (mol L).

Using the right form of equation (2-9) for n = 2 we get the reaction time.

1 1 1

t= 1 = = 190.0(min)

0.1 1 1 0.95 1 0.95

FP (t + ts ) 1.38(190 + 60) 3

V= = = 10,000L = 10m

C Ao x A 1x0.95

b) What is the maximum production rate, FP, achievable in the above batch reactor of

volume V=10m3 if ts, T, CAo all are fixed at previous values.

CAoV x A 10 4 x A 10 3 x A

FP = = xA = x

1 xA 10 + 60 A

+6

+ t s 1 x 1 x

kC Ao 1 x A A A

2

3 x A (1 x A ) 3 xA xA

FP = 10 = 10

x A + 6(1 x A 6 5x A

4

This expression has a maximum which we can locate by differentiation

dFP

= 0 (1 2x A )(6 5x A ) + 5 (x A x 2A ) = 0

dx A

6 5x A 12x A + 10x 2A + 5x A 5x 2A = 0

2

6 12x A + 5x A = 0

6 36 30 6 6

x A1, 2 = = = 0.710

5 5

Clearly, the positive sign is not permissible as conversion cannot exceed unity. We need to

check whether the answer is a maximum or a minimum.

dFP

> 0 for x A < 0.710

dx A

dFP

< 0 for x A > 0.710

dx A

Maximum at xA = 0.710.

0.710 0.710 2 mol

FPmax = 10 3 = 84.0

6 5x0.710 min

84 38

An increase in productivity of x100 = 121% can be achieved at the expense of more

38

unreacted A to be recycled.

One must include the cost of separation into the real economic optimization.

2.2.1 Continuous Flow Stirred Tank Reactor (CFSTR or CSTR or STR)

The CSTR is assumed perfectly mixed, which implies that there are no spatial gradients of

composition throughout the reactor. Since the reactor operates at steady state, this implies that a

single value of species concentration is found in each point of the reactor at all times and this is

5

equal to the value in the outflow. The outflow stream is a true representative of the reaction

mixture in the reactor.

FAO FA = FAo (1 x A )

CA

C AO

What does the above idealization of the mixing pattern in a CSTR imply? It postulates that the

rate of mixing is instantaneous so that the feed looses its identify instantly and all the reaction

mixture is at the composition of the outlet. Practically this implies that the rate of mixing from

macroscopic level down to a molecular scale is orders of magnitude faster than the reaction rate

and is so fast in every point of the vessel.

Then the mass balance of eq (2-1) can be applied to the whole volume of the reactor recognizing

that at steady state the accumulation term is identically zero. Again, taking a simple example of

an irreversible reaction A P application of eq (2-1) to reactant A yields:

FAo FA + ((RA)V=0 (2-12)

Molar flow rate of unreacted A in the outflow by definition is given by FA = FAo (1-xA) = Q CAo

(1-xA). The production rate of P is given by

FP = (R A )V = (R P )V (2-13)

FAox A QoC Aox A

V= = (2-14)

(R A ) (R A )

6

Reactor space time is defined by

V C Aox A

= = (2-15)

Qo (R A )

Using stoichiometry we readily develop the relation between production rate, FP, and reactor

volume, V.

Let us consider again the example of our 2nd order reaction, A = P, with the rate below:

n 2 mol

R A = kC A = 0.1C A

L min

Find CSTR volume needed to process FP = 38 mol/min. Suppose we choose again xA = 0.95 for

our exit conversion.

FP = 0.1 C 2Ao (1-xA)2 V

FP 38 3

V= 2 2 = 2 = 152,000L = 152m

0.1C (1 x A )

Ao 0.1x1(1 0.95)

If we consider eq (2-13) it is clear that now the maximum production rate is obtained when the

reaction rate is the highest. That for n-th order reactions is at zero conversion. So the maximum

FP from VCSTR = 12,000 L is obtainable at xA = 0.

The penalty or this enormous production rate is that the product is at zero purity. Hence, the

separation costs would be enormous. The average rate in a CSTR is equal to the rate at exit

conditions.

( RA ) = ( R A ) exit = 0.1C 2Ao (1 x A )2exit = 0.1x1(1 0.95) 2 = 2.5 x10 4 ( mol / L min)

7

2.2.2 Plug Flow Reactor (PFR)

The main assumptions of the plug flow reactor are: i) perfect instantaneous mixing

perpendicular to flow, ii) no mixing in direction of flow

This implies piston like flow with the reaction rate and concentration that vary along reactor

C AO C AO

FAO FA = FAo (1 x A )

FAo dx A = ( R A )dV

Since there are now composition gradients in the direction of flow, the control volume is a

differential volume V to which eq (2-1) is applied. Let us again use the mass balance on

reactant A

FA V FA V + V + RA V = 0 (2-16)

FA + RA V = 0

FA

lim = (lim )( R A )

V 0 V V 0

dFA

= ( RA ) (2-17)

dV

so that

dx A

FAo = ( RA ) (2-18)

dV

V=0 xA = 0 (2-19)

8

Upon separation of variables in (eq 2-18) and integration:

V xA

dx A

dV = F (R

o

Ao

A )

(2-20)

o

Q o [(1 x A ) 1]

xA 1n

F dx A

V = Aon

kC Ao

= n1

(1 x A ) n kC Ao (n 1)

(2-21)

o

V 1

= = n 1

Qo kC Ao (n 1)

[(1 x A )1n 1] (2-22)

is now identical to the expression for reaction time t in the batch reactor.

For the example of the second order reaction used earlier we get

xA xA

dx A FAo 1

V = FAo 2 2 =

kC Ao 1 x A o

2

o

kC Ao (1 x A )

FAo 1 FAo xA

V= 2 1 x A 1 = kCAo

2 1 x A

kCAo

FAo = Qo CAo

V 1 xA

= = (Same as the expression for reaction time t in the batch reactor)

Qo kC Ao 1 x A

Let us consider our example of the second order reaction and find the PFR volume needed to

produce FP = 38 mol/min

mol

( RA ) = 0.1CA

2

L min

mol

when C Ao = 1 and desired conversion xA = 0.95.

L

From stoichiometry it follows that

FP

FAo x A = FP FAo =

xA

9

Substitution in the expression for reactor volume (eq (2-21)) we get:

FP xA FP

V= =

2

kCAo xA 1 x A kCAo

2

(1 x A )

38

V= = 7,600L = 7.6m3

0.1x1(1 0.95)

The maximum production rate from that volume can be obtained at zero conversion

FP = kC 2Ao (1 x A )V

FPmax = 0.1x1x7600 = 760mol / min

FAo x A FP 38 3 mol

Average rate in PFR RA = = = = 5.0x10

V V 7,600 min

mol

( RA ) entrance = 0.1C 2Ao = 0.1 = 10 1

L min

mol

( RA ) exit = 0.1C 2Ao (1 0.95)2 = 2.5x10 4

L min)

Clearly there is a big variation in the reaction rate between the entrance and exit of the plug flow

reactor (PFR).

Volumetric Reactor Productivity - RVP

FP

RP = (2-23)

V

For our 2nd order reaction example of stoichiometry A=P, RVP for the two continuous flow

reactors is:

FP 2

PFR RP = = kCAo (1 x A ) (2-24b)

V

10

For the same exit conversion

2

(R P )PFR kC Ao (1 x A ) 1

= 2 =

(RP ) CSTR kC Ao (1 x A )

At xA = 0.95

(RP ) PFR

= 20

(RP ) CSTR

This is why higher CSTR volume is needed.

At xA = 0 ( RP ) PFR = (RP )CSTR

There is no difference!

Let us consider another example to illustrate some important points.

Ex: 2A + 3B = P + S stoichiometry

mol

r = 0.1C A C B2 - rate of reaction

L min

mol

C Ao = 2 and x A = 0.95 - are the feed reactant concentration and desired conversion

L

FP = 10 mol/min is the desired production rate

Assume first that we will operate at stoichiometric ratio so that CBo = 3 (mol/L). The reaction

occurs in the liquid phase so that A = 0 . Find the needed reactor volume.

a) Batch (ts = 60 min)

b

RA = 0.2CAo (1 x A )(C Bo CAo x A )2

a

2

3

RA = 0.2C3Ao (1 x A ) (1 x A ) 2

2

2

3

RA = 0.2C3Ao (1 x A ) 3

2

11

Reaction time is:

xA

1 dx A

t=

3

2 (1 x )3

o A

0.2C 2Ao

2

xA xA

1 g dx 1 1 1

t=

0.2x2 2 a

(1 x) 3 =

1.8 2 (1 x )2

o o

1 1 1 1

t= 1 = 1

3.6 (1 x A ) 2

36 (1 0.95)

3

t = 110.83 min

1

C Ao x A V 0.95xV

FP = 2 = = 10

t + ts 110.83 + 60

170.83x10

V= = 1,798 L = 1.8m3

0.95

b) CSTR

FAo FP

= - from stoichiometry

2 1

V x

= A - basic design equation (2-14)

FAo R A

FAo x A 2 FP 2FP

V= = =

RA ( RA ) 0.2CA C 2B

FP FP

V= 2 = 2

C 3 3 3 3

3

0.1CAo (1 x A ) Bo x A 0.1C Ao (1 x A )

CAo 2 2

10 10 1 3

V= 3 = 3 = 4,444(L ) = 44.4 m

0.1 2 9(1 0.95) 1.8 0.05

2

3 3

( RA ) = ( R A ) exit = 0.2 xC Ao (1 x A ) exit

3

2

= 0.2x2x9(1-0.95)3 = 4.5 x10-4 (mol/L min)

12

c) PFR

2FP

FAo = - from stoichiometry

xA

Basic design equation (2-21)

xA xA

dx A dx

V = FAo = FAo 2

o R A o 3 3

0.2C Ao (1 x) (1 x )2

2

xA

2FP dx 100 xA dx

V= 2 =

(1 x )3 18x 0.95 o (1 x )3

3 3 o

0.2C Ao x

2 A

100 1 1

V= 1

18x0.95 2 (1 x A ) 2

50 1 3

= 2 1 = 1,167(L ) = 1.17 m

10 0.95 (1 0.95)

Now the rate, at stoichiometric feed ratio, along the PFR as a function of conversion is

2

3 3

R A = 0.2C (1 x A ) 3 = 3.6(1 x A ) 3

2 Ao

xA xA

2FP dx F dx

V=

3.6x A o (1 x) 3 = 1.8xP A (1 x)

o

3

Hence, the production rate from a given PFR volume as a function of conversion (at

stoichiometric feed rate) is

1.8x A V 3.6x A V

FPstoich = =

xA

1

(1dxx) 3 (1 x A ) 2 1

o

How much can we increase the production rate by doubling CBo to CBo = 6 (mol/L), i.e. by using

B in excess?

13

Now the rate as a function of conversion is:

2

C 3 3

2

R A = 0.2C (1 x A ) Bo

3

x A = 0.2x2 3 x (1 x )(2 x A )2

Ao

C Ao 2 2

R A = 3.6(1 x A )(2 x A )2

a) Batch

xA x

dx A 2 A dx

t = C Ao =

o

( RA ) 3.6 o (1 x)(2 x)2

A B + Cx A(2 x ) 2 + (B + Cx )(1 x )

+ 2 = 2

1 x (2 x ) (1 x )(2 x )

4 A 4 Ax + Ax 2 + B Bx + Cx Cx 2 = 1

4A+B=1 4A-3A=1 A=1

-4A-B+C=0 -3A-B-0 B=-3A B=-3

A-C=0 C=A = 1

dx dx x3

(1 x)(2 x) 2 = +

1 x (2 x)2

dx

xA

dx 2x 1

= 2 dx 2 dx

o

1 x (2 x) (2 x)

1 xA

= ln(1 x) + ln(2 x)

2 x o

1 1

= l n (1 x A )+ 0 + ln (2 x A ) ln 2 +

2 x A 2

2 xA 1 2 2 xA xA

= ln + 1 = ln

2(1 x A ) 2 2 x A 2(1 x A 2(2 x A )

1 2 x A xA

t= ln

1.8 2(1 x A 2(2 x A ) x

A = 0.95

t= ln = ln10.5

1.8 2x0.05 2x1.05 1.8 2.1

t = 1.055 min Batch ill advised at these conditions since ts >> t!

14

1

C Ao x A V 0.95x1,798 mol

FPnew =2 = = 27.97

t + ts 1.06 + 60 min

FP 27.97 10

100 = 100 = 179.7%

FPold 10

production rate of the batch reactor by 180%.

b) CSTR

2

RA = 3.6(1 x A )(2 x A )2 3.6(1 0.95)(2 0.95)

mol

RA = 3.6x0.05x1.052 = 0.19845

L min

R A 0.19845 mol

FPnew = R P V = V= 44,494 = 4,410

2 2 min

FP 4,410 10

100 = x100 = 44,000%

FPold 10

c) PFR

xA

dx

V = FAo

o

3.6(1 x)(2 x)2

Vx A 1.8x AV

FPnew xA = xA

2 dx dx

3.6 o (1 x)( x)

3 (1 x)(2 x) 3

o

1.8x A V

FPnew =

2 x A xA

ln

2(1 x A ) 2(2 x A )

1.8x0.95x1,167 1.8x0.95x1,167

FPnew = =

2 0.95 0.95 1.05 0.95

ln ln

2(1 0.95) 2(2 0.95) 0.1 2.10

FPnew = 1,051 mol / min

15

FP 1,051 10

x100 = x100 = 10,419%

FPold 10

C Bo C Ao = 2 (C Bo C Ao) stoich and at stoichiometric ratio of CBo/CAo = 3/2 for our example reaction.

For a PFR:

1.8x A V

2 xA xA 1

ln 1

FP(non stoich ) 2(1 x A 2(2 x A V (1 x A )2

= =

FP( stoich) 3.6x A 2 xA xA

1 2 ln

2

1 2(1 x A 2(2 x A )

(1 x A )

1

FP(non stoich) 1 199.5

= 0.05 2 = = 105.0

FP(stoich) 1.05 0.95 0.75 ln10.5 0.45228045

2 ln 2 ln10.5

2x 0.05 2x1.05 2.10

For a CSTR

FP(non stoich) 3.6(1 x A )(2 x A )2 (2 x A )2

= = =

FP(stoich) 3.6(1 x A ) 3 (1 x A )2

2 2

2 0.98 FP( nonstoich) 1.05

= = 212 = 441

1 0.98 FP 0.05

( stoich)

Let us examine the situation when the reaction just considered occurs at P = const, T = const in

the gaseous phase. Then due to stoichiometry we have

2B + 3B = P + S

j = 1 + 1 2 3 = 3

16

Consider stoichiometric feed of reactants at CBo/CAo =3/2.

2

y Ao = = 0.4 ( A ) = 2

5

j 0.4 (3)

A = y Ao = = 0.6

( A ) 2

CBo 3

xA

1 x A CAo 2

C A = C Ao CB = CAo

1 0.6x A 1 0.6x A

2

3 3 (1 x A )3 (1 x A )3

RA = 0.2xCAo 2 (1 0.6x )3 = 3.6 3

A (1 0.6x A )

CSTR

( RA )

FP = V

2

2FP 2x10(1 0.6x0.95)3

V= =

RA 3.6(1 0.95)3

10 (1 0.57)3

V= 3 = 44,444x0.433 = 3,534(L)

1.8 0.05

PFR

xA xA

dx A 2Fp (1 0.6x)3 dx

V = FAo = o 3.6(1 x)3

o

RA xA

x A = 0.95 0.95 3

F (1 0.6x)3 10 1 06x)

V= P

1.8x A

0

(1 x) 3 dx =

1.8x0.95

0

1 x

dx

V = 125.6(L)

17

2.4 Graphic Comparison of PFR and CSTR

V =

xA

FAo CSTR ( RA ) exit

V x Ao

dx A

=

FAo PFR o RA

The graphic representation of the above two design equations is represented below for an n-th

order reaction. Clearly, for fixed feed conditions and feed rate and for chosen desired conversion

the volume of the CSTR will always be larger than or equal to the PFR volume.

1

V

R A = area of box

FA o CSTR

V

= area under the curve

FA o PFR

xA

18

Ideal Reactors and Multiple Reactions

Isothermal Operation

(CHE 471)

M.P. Dudukovic

Chemical Reaction Engineering Laboratory

(CREL),

Washington University, St. Louis, MO

ChE 471 Lecture 6 October 2005

Isothermal Operation

Selection of a proper flow pattern is the key factor in achieving desired selectivities and yields in

multiple reactions. For every multiple reaction system of known stoichiometry it is possible to

determine a priori which limiting flow pattern complete backmixing (CSTR) or no mixing

(PFR) will yield superior yields or selectivities. The consideration of yields often is more

important than reactor size in choosing the preferred reactor flow pattern.

From Lecture 1 we know that all multiple reaction systems can be represented by a set of R

independent reactions among the S chemical species present in the system:

S

j=1

These stoichiometric relationships allow one to relate moles produced (or depleted) of each

species to the molar extents of the R reactions:

R

F j = F jo + ij X& i (1)

i =1

The rate of reaction of each species is given through the rates of the R independent reactions, ri, i

= 1,2,R.

R

Rj = ij ri (2)

i =1

Fjo Fj

Qo Q

V

The design equation (i.e., the mass balance for species j) can be written for R species, j =

1,2,3R:

R

Fjo Fj + ij riV = 0 (3)

i =1

for j = 1, 2,...R

1

ChE 471 Lecture 6 October 2005

If the reaction rate ri for each independent reaction i can be represented by an n-th order form, of

eq (4a)

S

ri = k i C j ij

(4a)

j =1

then at P = const, T = const, the rate of the i-th reaction, ri, can be represented in terms of molar

extents X& i of the reactions by:

ij

R

S

ij

F jo + ij X& i

ri = k i C tot

i =1

,o S R (4b)

j =1

Ftot ,o + ij X& i

j =1 i =1

where ij is the reaction order of reaction i with respect to species j, Ftot,o is the total initial

molar flow rate.

Substitution of equations (2) and (4b) into (3) results in set of R nonlinear equations in X& i .

Three types of problems described below arise:

a) Given the feed flow rates, reactor size V and rate forms for all reactions one can calculate

all the reaction extents X& i ' s and from equation (1) get the composition of the outlet

stream.

R S

Q = Qo 1 + ij X& i Ftot , o (5)

i =1 j =1

The exit volumetric flow rate can be computed and effluent concentrations calculated

Fj

Cj = (6)

Q

b) Given the feed molar flow rates and composition, and the desired partial composition of

the outflow, as well as the reaction rates, one can calculate the reactor size from equation

(3) and the composition of other species in the outflow.

c) Given molar feed rates and outflow molar flow rates for a given reactor size the rate of

reaction for each species can be found from equation (3).

2

ChE 471 Lecture 6 October 2005

Fjo Fj

Qo Q

V

The design equation (i.e. the differential mass balance for species j) can be written for R species

dF j R

= ij ri (7)

dV i =1

j = 1, 2, ...R

Using equations (1) and (4b) the above set of R first order differential equations can be

integrated simultaneously and solved for X& i ' s as functions of V.

a) Given the feed flow rate and composition, and the form of the reaction rates, one could

determine what volume V is required to attain the desired product distribution.

b) Given the feed and reactor volume and reaction rate forms, one can determine the exit

product distribution.

dn j R

= ij ri (8)

dt i =1

3

ChE 471 Lecture 6 October 2005

R

n j = n jo + ij X i (9)

i =1

For j = 1, 2, 3S

ij

R

s ij X i

ri = k i C joij 1 + i =1

(10)

n jo

j =1

s ij

R

ri = k i C jo + ij i (10a)

i =1

j =1

Xi

where i = (10b)

V

One can solve the set of R first order differential equations to calculate the product distribution in

time, or the desired time needed for a prescribed product distribution.

The above approach, while well suited for the computer, does not provide us with the insight as

to which flow pattern is better in a given process until we actually compute the answers for both

limiting cases.

In order to get better insight in the role of the flow pattern in product distribution in multiple

reactions we will consider some simple systems and use the notions of yields and selectivity.

A + B = R

parallel

C + D = P

A+ B = R

competitive

A + 2B = S

A + B = R

consecutive (series reactions)

R=S

A + B = R

mixed reactions

R+ B = S

4

ChE 471 Lecture 6 October 2005

R

P Rp ip ri

y = = R

i =1

{point (relative) yield

A RA r

iA ii =1

Point (relative) yield measures the ratio of the production rate of a desired product P and the rate

of disappearance of the key reactant A. Point yield is a function of composition and this varies

along a PFR reactor, varies in time in a batch reactor, and is a constant number in a CSTR.

P F FPo

Y = P {overall (relative) yield

A FAo FA

Overall (relative) yield gives the ratio of the overall product P produced and the total

consumption of reactant A.

P P

Y ( ) = y

A A

In a PFR the overall yield is the integral average of the point yield:

FAo

P 1 P

Y =

A FAo FA

FA

y dFA

A

Overall operational yield is also often used, defined as the number of moles of the desired

product produced per mole of key reactant fed to the system.

F F

@ = P Po

P

A FAo

@ = Y x A

P P

A A

5

ChE 471 Lecture 6 October 2005

FAo FA

xA =

FAO

None of the above yields has been normalized, i.e., their maximum theoretical value may be

more or less than one as dictated by stoichiometric coefficients.

P

y

P A

y =

A y P

max

A

P

where y max is obtained by assuming that only the reactions leading from A to R occur.

A

Point selectivity and overall selectivity measure the ratio of formation of the desired product and

one or more of the unwanted products, e.g.

P Rp F p F po

s = S=

U Ru Fu Fuo

A general rule:

P

dy

If > 0 PFR produces more P.

A

dC A

P

dy

If < 0 CSTR produces more P

A

dC A

P

If y is not a monotonic function of CA either reactor type may produce more P depending

A

on operating conditions. The case of monotonic point yield is illustrated below for the case with

A = 0.

P P

y y

A A

\ \ \ Area = Cp in PFR

Area = Cp in CSTR

CA CAo CA

CA CAo CA

6

ChE 471 Lecture 6 October 2005

R S

I. Liquid Systems or Gases With

i =1 j =1

ij =0

Competitive Reactions

a2A + b2B = s2S

r2 = k 2 C A 2 A C B 2 B

p1

P Rp p1 r1 a1

y = = =

A R A a1 r1 + a 2 r2 1 + a 2 r2

a1 r1

p1

P a1

y =

A 1 + a 2 k 2 C ( 2 A 1 A ) C ( 2 B 1 B )

A B

a1 k1

P p

y max = 1

A a1

P 1

y =

A 1 + 2 2 C ( 2 A 1 A ) C ( 2 B 1 B )

a k

A B

a1 k1

P

We want y to be as high as possible. This implies:

A

CSTR.

ii) if 2 A = 1A , 2 B < 1B , keep CB as high as possible. PFR is better than CSTR.

iii) if 2 A = 1A , 2 B > 1B , keep CB as low as possible. CSTR is better than PFR. Try

for yourself other combinations.

7

ChE 471 Lecture 6 October 2005

Example 1

2A = S RS = 0.5 C A2 (kmol/m3s)

Conversion of 98% is desired.

P Rp Rp 1

y = = =

A R A R p + 2 Rs 1 + C A

P P P

y max = 1 y = y

A A A

To keep point yield as high as possible, it is necessary to keep CA low everywhere. CSTR

will be better than PFR. Let us show this quantitatively.

a) CSTR

By setting the overall yield equal to the point yield we can solve for the exit concentration of

product P.

P Cp P 1

Y = = y =

A C Ao C A A 1+ CA

C Ao C A

Cp =

1+ CA

=

C Ao x A

=

1x0.98

1 + C Ao (1 x A ) 1 + 1 0.98

(

= 0.961 kmol / m 3 )

P Cp

Overall yield Y = = 0.980

A C Ao C A

@

P

Overall operational yield = 0.961

A

C Ao C A C Ao x A

= = = 48.0( s )

RA C Ao (1 x A ) + C Ao

2

(1 x A ) 2

8

ChE 471 Lecture 6 October 2005

b) PFR

C Ao C Ao

P dC A

Cp =

CA

y dC A =

A

1+ C

CA A

1 + C Ao 1+1

C p = ln = ln = 0.673(kmol / m )

3

1+ CA 1 + 1 0 . 98

P

Overall yield Y = 0.687

A

P

Overall operational yield @ = 0.673

A

C Ao C Ao

dC A dC A

Required reactor size =

CA

RA

=

CA

C A (1 + C A )

C Ao (1 + C A ) 1 + 1 0.98

= ln = ln = 3 .2 ( s )

C A (1 + C A ) (1 0.98)(1 + 1)

Plug flow reactor is considerably smaller but CSTR gives a better yield and higher

concentration of the desired product.

Example 2

A+A=S Rs = 0.5 C A2 (kmol/m3s)

Given FAo = FBo = 1 (kmol/s; CAo = CBo = 1 (kmol/m3) CPo = CSo = 0 and desired

P P P

conversion xA = 0.98, determine C p , Y ,@ , S and required reactor space time for

A A S

a) CSTR, b) PFR.

P R Rp CB 1

y = p = = =

A RA R p + 2 Rs CB + C A 1 + C A

CB

9

ChE 471 Lecture 6 October 2005

To maximize point yield one should keep the reactant concentration ratio CA/CB as low as

possible everywhere.

R

i =1

C A = C Ao 1 2 2

C P = C Po + 1

1

1 = C P C Po 2 = [C Ao C A C P ]

2

Now:

C B = C Ao 1 = C Bo C p

C S = C So + 2 = 0 +

1

2

[

C Ao C A C p ]

1

= [C Ao C A C Bo + C B ]

2

a) CSTR

P Cp P C Ao C p

Y = = y =

A C Ao C A A C Ao C p + C A

Solve for Cp

C p2 (C Ao _ C Bo )C p + C Bo (C Ao C A ) = 0

C Ao = C Bo = 1; C A = C Ao (1 x A ) = 1 0.98

C p2 2C p + 0.98 = 0

C p = 1 1 0.98= 0.859(kmol / m 3

C A = 0.02kmol / m 3

exit stream composition

C B = 0.141kmol / m 3

C S = 0.061kmol / m 3

P

Overall yield Y = 0.877

A

10

ChE 471 Lecture 6 October 2005

P

Overall operational yield @ = 0.859

A

P Cp

Overall selectivity S = = 14.2

S Cs

Required Reactor Size

C Bo C B C Ao C B 1 0.141

= = = = 306( s )

RB C AC B 0.02 x0.141

b) PFR

dF p Rp P

= = y

dFA RA A

dC p C Bo C p

=

dC A C Bo C p + C A

at C A = C Ao , C p = 0

Rearrange:

dC A CA

+ = 1

dC p C Bo C p

d CA 1

=

dC p C C C C

Bo p Bo p

at Cp = 0 CA = CAo

CA C C Bo C p

Ao = ln

C Ao C p C Bo C Bo

= 1 + ln(1 C p )(*)

CA

1 Cp

11

ChE 471 Lecture 6 October 2005

(C p ) = C p 0.98 (1 C p )ln(1 C p ) = 0

D (C p ) = 2 + ln(1 C p )

n +1

(C pn )

C =C n

Newton-Raphson Algorithm

D (C pn )

p p

This yields:

C p = 0.613 kmol / m 3

C A = 0.02 kmol / m 3

Exit stream composition

C B = 0.387 kmol / m 3

C s = 0.184 kmol / m 3

The last two concentrations above are evaluated using the stoichiometric relationship.

P

Overall yield Y = 0.626

A

P

Overall operational yield @ = 0.613

A

P

Overall selectivity S = 3.33

S

C Bo C

Bo =1

dC B dC B

=

CB

=

R B C B =0.387 C A C B

From (*)

[

C A = (1 C p ) 1 + ln(1 C p ) ]

From stoichiometry

C B = C Bo C p = 1 C p

Thus

C A = C B (1 + lnC B )

12

ChE 471 Lecture 6 October 2005

C Bo =1 1+ ln C

dC B Bo

e u

= = e u du

C B = 0.387 C B (1 + lnC B )

2

1+ ln C B

= 2.71{2.4679 0.2194} = 6.1( s )

where

e u

E1 ( z ) = du exponential integral

z

u

Dover Press, N.Y. 1964.

A+A=S

F

M B / A = Bo = 1

FAo

r2 = 0.5 CA2 (kmol/m3s)

Operational yield 0.859 0.613 0.950

Overall selectivity 14.2 3.3 63.0

Reactor space time 306 (s) 6.1 (s) 150 (s)

The last column of the above Table was computed based on an ideal reactor model shown below.

We have B entering a plug flow reactor while FAo is distributed from the side stream into the

reactor in such a manner that CA = 0.02 kmol/m3 everywhere in the reactor.

FAo

PFR

FBo

13

ChE 471 Lecture 6 October 2005

P CB 1

y = =

A CB + C A 1 + C A

CB

it is clear that one needs to keep CA low and CB high. With the constraint of FAo = FBo the above

ideal reactor accomplishes that requirement in an optimal manner.

Could such a porous wall reactor with plug flow be constructed? It depends on the nature of

the reaction mixture.

However, we learn from the above that with our choice of decision variables maximum

selectivity is 63, we can never do better than that! We also learn that a good reactor set up is a

cascade of CSTRs.

FAo

FBo

The total number of reactors used will depend on economics With 2 reactors we get selectivity

of over 20, with five we are close to optimum.

Examining the effect of decision variables we see that Cp increases with increased conversion of

A. For conversions larger than 0.98 the reactor volume becomes excessive.

If we took MB/A > 1 that would improve the yield and selectivity but at the expense of having to

recycle more unreacted B.

Let us ask the following question. How much excess B would we have to use in a PFR in order

Cp

to bring its overall selectivity to the level of a single CSTR i.e., S = = 14.2 at CAo = 1

Cs

(kmol/m3) and xA = 0.98. So the goal is to choose C Bo in order to get at the exit of plug flow:

Cp

= 14.2

Cs

From stoichiometry:

Cs =

1

2

[ ] 1

[ ] 1

[

C Ao C A C p = C Ao x A C p = 0.98 C p

2 2

]

14

ChE 471 Lecture 6 October 2005

2C p

= 14.2C p = 0.859(kmol / m 3 )

0.98 C p

C s = 0.061(kmol / m 3 )

CA C Cp

Ao = ln1

C Bo C p C Bo C Ao

The initial concentration of B is now the only unknown. Evaluate it by trial & error.

0.02 1 0.859

= ln1 gives

C Bo 0.859 C Bo C Bo

kmol

C Bo = 3.79

m3

Since CAo = l (kmol/m3), MB/A = 3.79 almost four times more B than A should be introduced

in the feed to get the selectivity in a PFR to the level of a CSTR.

Consecutive Reactions

aA = p1P

p2P = s S

b) promote production of the intermediate.

The first problem is trivial and can be reduced to a single reaction problem. Use the slowest

reaction in the sequence to design the reactor.

In order to maximize the production of intermediates PFR flow pattern is always superior to a

CSTR flow pattern.

15

ChE 471 Lecture 6 October 2005

P Rp p r p 2 r2 p p r

y = = 11 = 1 2 2

A RA a r1 a a r1

P p

y max = 1

A a

P p r p k C

y = 1 2 2 = 1 2 2 P

A p1 r1 p1 k1C A

One needs to keep CA high and Cp/CA low which is best accomplished in a PFR.

Example 1

A=P r1 = 1.0 CA (kmol/m3s) = 1

P=S r2 = 0.5 CP (kmol/m3s) = 1

Starting with CAo = 1 (kmol/m3) and CPo = Cso = 0 find the maximum attainable CP in

a) CSTR, b) PFR.

P C 0.5C P

C P = y (C Ao C A ) = A (C Ao C A )

A CA

Solve for CP

C A (C Ao C A )

CP =

0.5(C Ao + C A )

dC P

= 0 (C Ao 2C A )(C Ao + C A ) C A (C Ao C A ) = 0

dC A

C A2 + 2C Ao C A C Ao

2

=0

C Aopt = C Ao [ ]

2 1 = 0.414(kmol / m 3 )

0.414(1 0.414)

C Pmax = = 0.343(kmol / m 3 )

0.5(1 + 0.414)

C S = C Ao C A C P = 0.243kmol / m 3

P

Overall yield Y = 0.585

A

16

ChE 471 Lecture 6 October 2005

@ = 0.343

P

Operational yield

A

P

Overall selectivity S = 1.4

S

Required reactor space time:

= = = 1.4( s)

RA C Aopt 0.414

dC P P 0.5C P C A

= y =

dC A A CA

at CA = CAo, CP = 0

dC P 0.5 C p

= 1

dC A CA

d CP 1

==

dC A C A CA

CP

CA

[

= 2 C Ao C A ]

CP = 2 C A [C Ao CA ]

Find CA at the reactor exit by

dC P

= 0 C Ao 2 C A = 0

dC A

C Ao

C Aopt =

4

C Aopt = 0.25(kmol / m 3 )

[ ]

C Pmax = 2 0.25 1 0.25 = 0.5(kmol / m 3 )

C s = 1 0.5 0.25 = 0.25(kmol / m 3 )

P 2

Overall yield Y = = 0.667

A 3

@ = 0.5

P

Operational yield

A

17

ChE 471 Lecture 6 October 2005

P

Overall selectivity S = 2.0

A

C Ao

dC A C

=

C Aopt

CA

= ln Ao = ln4 = 2ln2 = 1.39( s)

C Aopt

The same results can be obtained by using the design equations (i.e. mass balance)for P & A.

CSTR

C Ao C A C Ao

= CA =

CA 1+

CP C A C Ao

= CP = =

C A 0.5C P 1 + 0.5 (1 + )(1 + 0.5 )

dC p

= 0 gives opt = 1.4( s ), etc.

d

PFR

dC A

= C A C A = C Ao e

d

= 0, C A = C Ao = 1

dC P

= C A 0.5C P

d

=0 CP = 0

d 0.5

(e C P ) = C Ao e e 0.5 = C Ao e 0.5

d

C P = 2(e 0.5 e )

dC P

= 0 opt = 2ln 2, etc.

d

18

ChE 471 Lecture 6 October 2005

Mixed Reactions

This is the most frequently encountered type of multiple reactions which can be viewed as a

combination of competitive and consecutive reactions. We can solve the problems involving

these reactions either by setting R design equations for R components or by utilizing the concept

of the point yield in simpler reaction schemes.

Example 1

2B + R = S Rs = k2 CB CR (kmol/m3min)

k1 = 10 k2 = 1 (m3/kmol min). R is the desired product. Find CR in a) CSTR, b) PFR, when CRo

= Cso = 0. Decision variable CAo = CBo = 1 (kmol/m3).

R R k C C k2CBCR 1 k2 CR

y = R = 1 A B = 1

A RA 2 k1 C A C B 2 k1 C A

k

C A 2 CR

R R k C C k2CBCR k1

y = R = 1 A B =

B R B k1 C A C B + 2 k 2 C B C R C + 2 k 2 C

A R

k1

R

The point yield y depends only on CR and CA and is simpler to use.

A

k

C A 2 CR

R k1

C R = y (C Ao C A ) = (C Ao C A )

A 2C A

C A (C Ao C A ) C (C C A )

CR = = A Ao

k k 1.9C A + 0.1C Ao

2 2 C A + 2 C Ao

k1 k1

dC R k 2 k k 2

= 0 2 2 C A + 2 2 C Ao C A 2 C Ao =0

dC A k1 k1 k1

19

ChE 471 Lecture 6 October 2005

C Ao

C Aopt =

k1

2 +1

k2

1

C Aopt = = 0.183(kmol / m 3 )

2 x10 + 1

0.183(1 0.183)

C Rmax = = 0.334 (kmol / m 3 )

1.9 x0.183 + 0.1

From stoichiometry

3 3

C B C Bo (C Ao C A ) + 2C R = 1 (1 0.183) + 2 x0.334

2 2

1 1

C S = (C Ao C A ) C R = (1 0183) 0.334

2 2

C B = 0.443(kmol / m ); C S = 0.0745(kmol / m 3 )

3

R R

Overall yield Y = 0.409; Y = 0.600

A B

@ = 0.334; @ = 0.334

R R

Operational yield

A B

R

Overall selectivity S = 4.48 = 4.5

S

C Ao C A 1 0.183

= = = 5.0(min)

2k1C A C B 2 x1x0.183 x0.443

dC R R 1 k C

= y = + 2 R

dC A A 2 2 k1 C A

C A = C Ao ,C R = 0

d k2 1 k2

C A 2 k1 C R = C A 2 k1

dC A 2

k2 k2

1

2 k1

C C C A C Ao

2 k1

CA CA

0.95 0.05

CR = Ao A

=

k 1 .9

2 2

k1

20

ChE 471 Lecture 6 October 2005

1

dC R k k2

1 2 k

= 0 C Aopt = 2 1

dC A 2 k1

1

= 0.0427(kmol / m 3 )

C Rmax = = 0.427(kmol / m 3 )

1.9

3

C B = 1 (1 0.0427) + 2 x0.427 = 0.418(kmol / m 3 )

2

1

CS = (1 0.0427) 0.427 = 0.0517(kmol / m 3 )

2

R R

Overall yield Y = 0.446; Y = 0.734

A B

@ = 0.427; @ = 0.427

R R

Operational yield

A B

R

Overall selectivity S = 8.27 = 8.3

S

C Ao

dC A

=

CA

2C A C B.

From stoichiometry

3

C B = C Bo (C Ao C A ) + 2C R

2

C A0.05 C A

CR =

1.9

21

ChE 471 Lecture 6 October 2005

C B = C Bo

3

(C Ao C A ) + 2 (C A0.05 C A )

2 1.9

2 2 0.05

C B = 1.5 C A + C A 0.5

1.9 1.9

C B = 0.447C A + 1.05C A0.05 0.5

1

dC A

= 0 .5 integrate numerically (2.759 min )

0.0427 0.447C + 1.05C A 0.5C A

2 1.05

A

Caution must be exercised when using the point yield concept and finding maximum

concentrations in mixed reactions. Sometimes formal answers will lie outside the

physically permissible range if the other reactant is rate limiting.

kmol kmol

CAo = 2 3 ; CBo = 1 3

m m

C Ao

C A opt = = 0.366(kmol / m 3 )

2 x10 + 1

0.366(2 0.366)

C Rmax = = 0.668(kmol / m 3 )

1.9 x0.366 + 0.2

However these values are not attainable since from stoichiometry it follows that:

3

C B = 1 (2 0.366) + 2 x0.668 = 0.115 < 0

2

This indicates that B is not introduced in sufficient amount to allow the reactions to proceed to

that point.

If CBo = 1.115 (kmol/m3) then the above CR max can be obtained (theoretically) at CB = 0 and that

would require an infinitely large reactor.

Thus the maximum reactor size that is allowed would determine CBmin . Say CBmin =0.01

(kmol/m3) (99% conversion of B).

22

ChE 471 Lecture 6 October 2005

4 2

C A = C Ao C R (C Bo C Bmin )

3 3

C A (C Ao C A )

CR =

1.9C A + 0.1C Ao

C A = 0.461(kmol / m 3 )

That yields: C R = 0.660(kmol / m 3 )

C S = 0.110(kmol / m 3 )

R R

Overall yield Y = 0.429; Y = 0.667

A B

@ = 0.330; @ = 0.660

R R

Operational yield

A B

R

Overall selectivity S = 6.0

S

Reactor space time:

2 0.461

= = 170min

2 x1x0.461x0.01

Same approach may be used but one needs to deal with X& i& extents rather than concentrations.

Use relationships from Lecture 1.

Summary

PFR promotes more reactions of higher order with respect to reactions of lower order.

CSTR favors reactions of lower order with respect to those of higher order.

In consecutive reactions better yields are achieved always in PFR than in a CSTR for an

intermediate product.

Remember: Optimizing overall yield does not necessarily lead to the same result as maximizing

the production rate (or concentration) of the desired product or as maximizing selectivity.

23

NONISOTHERMAL OPERATION OF

IDEAL REACTORS

Continuous Flow Stirred Tank Reactor

(CSTR)

(CHE 471)

M.P. Dudukovic

Chemical Reaction Engineering Laboratory

(CREL),

Washington University, St. Louis, MO

ChE 471 Fall 2005

LECTURE 7

Continuous Flow Stirred Tank Reactor (CSTR)

T V T

To To

Fj

or Fj

Fjo, Qo Fjo, Qo

V

Tmo Tm Tmo Tm

Figure 1: Schematic of CSTR with jacket and coil

Assumptions:

Homogeneous system

s

a) Single Reaction A

j =1

j j =0

b) Steady state

A CSTR is always assumed perfectly mixed so that the concentration of every species is uniform

throughout the reactor and equal to the concentration in the outflow. Due to assumption of perfect

mixing the temperature, T, throughout the reactor is uniform and equal to the temperature of the

outflow. The only difference between an isothermal CSTR treated previously and the general case

treated now, is that now we do not necessarily assume that reactor temperature, T, and feed temperature,

To, are equal.

1. Given feed composition and temperature, rate form and desired exit conversion and temperature find

the necessary reactor size to get the desired production rate and find the necessary heat duty for the

reactor.

2. Given feed conditions and flow rate and reactor size together with cooling or heating rates,

determine the composition and temperature of the effluent stream.

To solve either of the above two problems we need to use both a species mass balance on the system and

the energy balance.

s

A

j =1

j j =0 (1)

or

aA + bB = pP (1a)

1

ChE 471 Fall 2005

LECTURE 7

Suppose the reaction is practically irreversible and the rate of reaction, which is a function of

composition and temperature is given by:

kmol

r = k o e E / RT C A C B 3 (2)

1424 3 123 m s

Temperature n-th order reaction n= +

Dependence of the rate

For a single reaction we can always eliminate all concentrations in terms of conversion of the limiting

reactant A (Lecture 1).

For liquids

j C jo

C j = C Ao M j / A x A ;M j / A =

A C Ao

For gases

M j / A j xA

A To P

C j = C Ao

1 + A x A TPo

where

A = y Ao

j

( A )

For liquids

( + )

r = k o e E / RT C Ao (1 x A ) M B / A b x A (3a)

a

For gases

b

(1 x A ) M B / A x A

T a

r = k o e E / RT o C Ao ( + )

+

(3b)

T (1 + A x A ) +

2

ChE 471 Fall 2005

LECTURE 7

FAo FA + A rV = 0; F jo F j + j rV = 0

FAo x A = arV = 0

C Ao x A = ar (5)

X& = rV (5a)

where

V

=

Qo

The energy balance of course cannot contain a generation term (in absence of nuclear reactions) and

hence can be written as:

s

~ s

~

F

j =1

jo H jo F j H j + q& = 0

j =1

(6)

kmol j

F jo - molar flow rate of species j in the feed

s

kmol j

Fj - molar flow rate of species j in the outflow

s

~ J

H j - virtual partial molal enthalpy of species j in the outflow mixture

kmol j

~ J

H jo - virtual partial molal enthalpy of species j in the feed

kmol j

J

q& - rate of heat addition from the surroundings i.e from the jacket or coil to the

s

reaction mixture in the reactor

The energy balance given by equation (6) is not general in the sense that the following assumptions have

already been made in order to present it in that form:

3

ChE 471 Fall 2005

LECTURE 7

1. Potential energy changes are negligible with respect to internal energy changes.

2. Kinetic energy changes are negligible with respect to internal energy changes.

3. There is no shaft work involved i.e the only work term is the expansion (flow) work.

J

The virtual partial molal enthalpy, H j , is defined by:

mol j

s

~

m& tot H = F j H j

j =1

kg

m& tot - mass flow rate of the mixture

s

J

H - enthalpy per unit mass of the mixture

kg

In principle the virtual partial molal enthalpy can be evaluated by the following procedure (for gases):

H j (T , P, y j ) = H ofj + C * dT + [ H (T , P) H T , P] + [ H (T , P, y j ) H (T , P)]

T

~ *

~ jj ~ j ~ j ~ j ~ j

T*o

H - standard enthalpy of formation for species j at the pressure Po of standard state and temperature

~ f jo

o

C ~ f j*

dT - change in enthalpy of species j, if it behaved as an ideal gas, due to change in temperature

To

from standard state temperature T o to the temperature of interest T. C is the specific heat of j in ideal

~ p *j

gas state. In reality C pjo data for real gases obtained at atmospheric or lower pressures can be used.

C

*

H o+ f j*

dT = H ( T , P o ) enthalpy per mol of j for pure j, if it behaved like an ideal gas, at T and Po.

~ fj ~ j

To

Since enthalpy of an ideal gas does not depend on pressure this is also the enthalpy per kmol of j, if it

*

were an ideal gas, at T and P, H (T, P ).

~ j

*

H (T , P) H (T , P) = pressure correction factor i.e the difference between the enthalpy of j being a

~ j ~ j

*

real gas at T, P, ( H (T , P) and enthalpy of j being an ideal gas at T, P ( H (T , P) ).

~ j ~ j

4

ChE 471 Fall 2005

LECTURE 7

Frequently the pressure correction is read off appropriate charts and is given by:

H* H j

~ j ~

H j (T , P) H j (T , P) = Tcj

*

Tcj

~ ~

Tr ,Pr

Where

H* H

~ j ~ T

is the correction read off the charts at appropriate reduced temperature Tr = T and

j

T

cj cj

P

reduced pressure Pr =

pcj

Finally

H j (T, P, y j ) H j (T, P) = j is the correction factor which accounts for the nonideality of the

~ ~

mixture.

_________________________________________________________________________

For liquids (in a first approximation)

T

~

Hj =H o + C pj dT + j

~ fj

To

Gases:

a. ideal mixtures j = 0

b. ideal gas behavior H = H *j

~ ~

Liquids:

a. ideal mixture j =0

Now the energy balance of eq (6) based on the above assumption can be written as

5

ChE 471 Fall 2005

LECTURE 7

s T

F C

j =1

jo

~

pj dT + H rT X& = q& (7a)

To

s T

F C

j =1

j

~

pj dT + H rTo X& = q& (7b)

To

where

s s T

H rT = j H + j C p j dT

~ f jo

j =1 j =1 To

Finally, in preliminary reactor design we assume that the heat of reaction does not vary much with

temperature

H r const H rTo H rT

and that some mean value of the specific heat can be used

C

To ~

pj dT = C

~

pj (T To )

F

j =1

jo C

~

pj (T To ) + H r X& = q&

or

C p Q(To T ) + ( H r )X& + q& = 0 (8)

where

F x C Q x

X& = Ao A = Ao o A

( A ) ( A )

H r

H rA =

( A )

C p Q(To T ) + ( H r )C Ao Qo x A + q& = 0 A

(9)

or

C p Q(To T ) + (H r )rV + q = 0 (9a)

6

ChE 471 Fall 2005

LECTURE 7

This final form of the energy balance resulting from all of the above assumptions can be interpreted as a

heat balance i.e as rate of input of sensible heat by the flowing stream minus rate of output of sensible

heat by exit stream plus heat generated by reaction plus heat added from the surroundings must add to

zero.

In addition we now need an energy balance on the jacket or coil and a constitutive relationship for heat

transfer rate, q& .

For a jacket at steady state (assuming that the jacket is well mixed too)

m Qm C p (Tm Tm ) q= 0

m o

(10)

m , Qm C p - are density, volumetric flow rate and mean specific heat of the fluid flowing through the

m

jacket.

Tm exit jacket temperature.

Let

q& = UA(Tm T ) (11)

J

U o - overall heat transfer coefficient.

m3 Cs

From eq (10)

Tmo + mT

Tm = (12)

1+ m

where

UA

m =

m C pm Qm

dTm

= m (T Tm ) (13)

dz

7

ChE 471 Fall 2005

LECTURE 7

Tm ( z ) = T + e m z (Tmo T ) (14)

For an n-th order irreversible reaction G(T) always has a sigmoidal shape and at high temperatures tends

to a horizontal asymptote CAo.

Finally, in dimensionalized form the two equations that have to be solved simultaneously are:

C Ao x A = a r (15)

~

To T + A a r (T Tmo ) = 0 (16)

H r

A = A

C p

UA m C p Qm

= = m

for a jacketed reactor

1 + m m C p Qm + UA C pQ

m

=

m

(1 e m

) for a reactor with coil

UA UA

m = =

m C p m Qm C pQ

When we deal with problems of type 1, to find reactor size for given feed and product stream conditions

we use directly eq (15).

V CAo x A CAo x A

= = =

Qo ar RA

(

q& = C p Q(To T ) + H rA arV )

When we deal with problems of type 2 and try to find the operating conditions for a given reactor, then

we must solve eqs (15) and (16) simultaneously by trial and error for xA and T.

Sometimes we can solve explicitly for xA from eq (15) in terms of temperature xA = xA(T).

8

ChE 471 Fall 2005

LECTURE 7

To T + AarT (T Tmo ) = 0

rT indicates that the rate is now a function of temperature only since r (xA,T) = r (xA(T),T)

1+ To + Tmo

~ T ~ = ar

{ T = C Ao x A (15)

A A

123 G (T )

L (T )

Reactor operating temperature is given by the intersection of the straight line L(T) and curvilinear

function G(T).

For an n-th order irreversible reaction G(T) always has a sigmoidal shape and at high temperatures tends

to a horizontal asymptote C Ao .

For an endothermic reaction Hr > 0 A < 0 and line L has a negative slope.

L

C Ao

G

G

L C Ao x A

1+

slope =

C Ao x A A

T To + Tmo T

1+

i) L & G can intersect at most once and for a given set of parameters only one steady state exists.

ii) For a given reactor and flow rate, fixed , given feed, To, and heating medium feed temperature,

Tmo , and given heat transfer properties, , the more endothermic the reaction, the larger A and

the smaller the slope of the L line, therefore the lower the operating temperature and conversion.

iii) For a fixed reaction, feed flow rate and composition and given reactor, fixed G curve, an increase

in feed temperature moves the L-line to the right while its slope remains unchanged. Hence, the

operating T and xA are increased.

For an exothermic reaction Hr < 0 and A > 0. The L-line has a positive slope.

9

ChE 471 Fall 2005

LECTURE 7

C Ao x A 3

G

L

1+

2 slope =

C Ao x A

A

To + Tmo T T

1+

i) L & G can intersect sometimes at more than one place and for a given set of conditions, more

than one steady state may be possible.

ii) For fixed and reaction, fixed G, an increase in the feed temperature moves the L line to the

right increasing the operating T and xA. An increase in coolant Tmo has the same effect.

iii) For a fixed and reaction, fixed G, , an increase in heat removal, increase in , rotates the

A

L-line in the counterclockwise direction and moves the intercept at the abscissa to the left if

To > Tmo or to the right if Tmo > To .

For exothermic reactions it is important to calculate the adiabatic temperature rise and the maximum

adiabatic T .

= = (20)

To To

Now let us consider a number of simple illustrative examples.

Example 1.

Irreversible reaction A R

10

ChE 471 Fall 2005

LECTURE 7

mol

RA = e 25e 20,000 / RT CA

L min

mol

C Ao = 1 To = 350 K = 77 C

o o

L

cal

H R A = 100,000

mol A

cal

C p = 500( o )

LC

CSTR

a. Isothermal. Find reactor space time needed for xA = 0.9 at 350K and heat to be removed.

C Ao C A C Ao x A 1x0.9 0.9

= = = =

RA RA 25

20 , 000

1.987 x 300

0.0233

e e

= 38.59 = 36 min

q& = Q C p (T To ) + X&H R

X& = FAo x A = Q C Ao x A (H R A )

cal

q& = QC p (T To ) + QC Ao x A (H R A )

min

q& cal

= C p (T To ) + C Ao x A (H R A ) = 1x0.9( 100,00)0 = 90,000cal / L to be removed.

Q L

mol

Note that the reaction rate at 350K is only 0.0233

L min

b. Adiabatic

Q C p (T To ) = (H R A )QC Ao x A

( H )C

T = To +

RA Ao

xA

C p

100,000 x1

T = 350 + 0.9 = 530 K (257 o C )

500

11

ChE 471 Fall 2005

LECTURE 7

C Ao C A C Ao x A 1x0.9 0.9

= = = 25 20,000 / 1.987 x 530 =

RA RA e e 407

= 2.21x10 3 min = 0.133s

Note that at 530K the reaction rate has increased by orders of magnitude to

mol

R A = 407

Lmin

Nonisothermal

C Ao x A 0 .9 0 .9

= = = = 1.06 (min )

RA

20 , 000

0.849

e 25 e 1.987 x 400

q&

= C p (T To ) + C Ao x A ( H RA )

Q

= 500(400 350) + (90,000)

= 25,000 90,000 = 65,000cal / L

kmol

R A = 0.849

c min

Example 2

A well stirred bench scale reactor (CSTR) is used for a first order exothermic reaction A R

(practically irreversible) under the following conditions:

= 1.0(min)

CAo = 1.0(mol / liter) ; To = 350K

UA C Q

Tmo = 350K ; = 1.0 = m pm m

m C pm Qm + UA C p Q

K lit (H R A )

A = 200 =

mol C p

20, 000

mol

r = e 25e RT

CA

lit min

12

ChE 471 Fall 2005

LECTURE 7

b) How many steady states are possible under these conditions?

c) What is the maximum adiabatic temperature rise?

d) How would you change some of the operating conditions (Tmo, To, ) in order to operate at a unique

steady state of high conversion.

e) What start up program should one use in order to have the reactor settle in the steady state of high

conversion?

Solution

Solve simultaneously eqs (15) & (16)

C Ao x A = ar = k 0 e E1 / RT C Ao (1 x A ) (15)

k0 = e 25 E = 20,000 cal / mol

1+ To + Tmo

~ T ~ = a r = k 0 e E / RT C Ao (1 x A ) (16)

A A

k 0 e E / RT

xA =

1 + k 0 e E / RT

Substitute into eq (16)

1+ To + Tmo k o e E / RT C Ao

~ T ~ =

A A 1 + k 0 e E / RT

14442444 3 144 244 3

L G

20,000

exp

1+1 350 + 1x350 1.9877T

T = x1x1

200 200 20,000

1 + exp25

1.987T

20,000

exp25

1.987T

0.01T 3.5 = (*)

20,000

1 + exp25

1.987T

Solve * by trial and error for T. Then obtain the corresponding conversion by:

20,000

exp25

1.987T

xA = (**)

20,000

1 + exp25

1.987T

13

ChE 471 Fall 2005

LECTURE 7

Example 1

1

0.9

0.8

0.7

0.6

XA

0.5

0.4

0.3

0.2

0.1

0

320 340 360 380 400 420 440 460 480 500

Temperature, K

Figure 5 on next page shows the dramatic temperature excursions that the reactor can experience during

start-up before it settles to a steady state.

14

ChE 471 Fall 2005

LECTURE 7

Error!

15

ChE 471 Fall 2005

LECTURE 7

a) There are three intersections of the L and G line indicating 3 possible steady states.

T = 353K

(1)

x A = 0.03

T = 408K

(2)

x A = 0.576

T = 439K

(3)

x A = 0.886

c)

Tad max = To + Tad max = 550K!

d) Increase To or Tmo to bypass the lower bump in the curve. Increase if possible.

e) See attached Figure 5.

Reversible Reactions

temperature.

xA

xAe

II

III

I

T

Figure 6: Equilibrium conversion as function of temperature for endothermic reactions.

In region III the reaction can be considered practically irreversible. In region II xAe rises with

increase in T.

For endothermic reactions the maximum permissible temperature is always the optimal

temperature for maximizing conversion or production rate from a given CSTR.

16

ChE 471 Fall 2005

LECTURE 7

The net rate of an endothermic reaction at fixed composition always increases with increased

temperature.

s s

r = k10 e E1 / RT C j k 20 e E2 / RT C j

j j

j =1 j =1

since E1 > E 2

temperature.

xA

xAe

II

III

I

T

Figure 7: Equilibrium conversion as function of temperature for exothermic reactions.

xA

r = 0.01

r = 0.02

r=0

r = 0.04

0.06

T

Figure 8: Conversion temperature relation at fixed rates for exothermic reactions.

Now we notice that at fixed composition, fixed xA, the net rate of reaction has a maximum at a

certain temperature, Tm. Below that temperature the rate is lower and above it, it is lower. The

reason for this is that E1 < E2.

On the above diagram we can pass a line - - - called the locus of maximum rates or a Tm line.

For a given conversion the Tm line defines a temperature at which the rate is maximum and vice

versa at every T the line defines an xA a which the rate is maximum.

17

ChE 471 Fall 2005

LECTURE 7

We should always select To, Tmo, in such a manner as to make sure that we operate on the Tm

line.

r dx

= 0 from A =0

T

r

dT

aA+bB=pP

r = k10e E1 / RT CA CB k20 e E 2 / RT Cp

Assuming further that we deal with liquids and that CAo and CBo are given while Cpo = 0

p

(

x Ae ) p

p a b a

K c = C Ao b

(A)

a C Bo

(1 x Ae ) b

x Ae

C Ao a

Assuming an ideal solution

Gro

Kc = e RT

(B)

The given rate form, if it is to be viable in the vicinity of equilibrium, must satisfy the following

constraint:

Cp

q p

= Ca p b

CA CB eq CA CB

r

The locus of maximum rates i.e the Tm-line can be obtained by = 0 which results in

T

18

ChE 471 Fall 2005

LECTURE 7

( E 2 E1 ) / R

T = Tm = (C)

p

xA

k 20 E 2 a

ln CAo ( )

k E C b

10 1 (1 x A ) Bo x A

CAo a

For a desired conversion eq (C) gives the temperature Tm at which the rate is maximum.

Substituting that conversion and temperature into the equation for the rate produces the

maximum rate

Example 3 - CSTR

A R

Gro298 = 2,500cal / mol

H ro298 = 20,000cal / mol = const

C p = 2,000(cal / lit ) = const

12,500 1

k1 = 5110

x2 3 e RT (min )

8

k10

mol

C Ao = 2

lit

f) Find he optimal size CSTR necessary to achieve a production rate of FR=100 (mol/min)

at xA = 0.9. If the reactor is to be operated adiabatically find the necessary feed

temperature.

g) If the feed is available only a T = 298K how should one operate? Can one maintain the

desired production rate and conversion?

h) How should 2 CSTRs in series be operated to minimize the total reactor volume and

keep FR and xA at desired levels. Feed is at 298K, T = 350Kis not to be exceeded.

Solution

Gro298 2,500

K 298 = exp = exp = 68.2

1.987 x 298

RT

d ln K Hr

=

dT RT 2

H r 1 1

10.065

K T = K 298 e R 298 T

= 1.461x10 13 exp

T

19

ChE 471 Fall 2005

LECTURE 7

10,065

1.461x10 13 exp

x Ae =

KT

= T

1 + KT 10,065

1 + 1.461x10 13 exp

T

T 298 300 310 320 330 340 350 360 370 380

x Ae 0.986 0.982 0.949 0.870 0.720 0.512 0.311 0.169 0.094 0.045

Tm =

(E 2 E1 ) R

=

10,065

k E xA x

ln 20 2 30.51 + ln A

k10 E1 1 x A 1 xA

xA 0.94 0.95 0.9 0.85 0.8 0.6 0.4 0.2 0.1 0.01

Tm 287 301 308 312 316 326 334 346 356 388

Plot the equilibrium line, xAe, and the locus of maximum rates, Tm, in order to graphically

interpret some of the later results.

Tm

1

0.8

xA xAe

0.6

0.4

0.2

a. At x A = 0.9 T = Tm = 308K

12, 500 32, 500

r = 5 10 8 e 1.987 308

2 (1 0.9) 3.422 10 21 e 1.987 308

2 0.9

mol

r = 0.815

lit min

20

ChE 471 Fall 2005

LECTURE 7

100

= 1227 (lit )= 1.23 m 3

FR FR

V= = =

RR r 0.815

V = 1.23 m 3

H rA

To T + A (VA )r = 0 = = 10

Cp

To = T A CAo x A = 308 10 2 0.9 = 290K

For adiabatic operation the feed temperature would have to be 290K. The same result is

obtained graphically (--- adiabatic line).

(

q = Q C p To To =

1

) FR

CA o x A (

C p To To

1

)

100 cal

q = 2000 (298 290)= 8.889 10 5

2 0.9 min

To = 298K T = 308K

21

ChE 471 Fall 2005

LECTURE 7

q = Q C p (To T )+ ( H rA )CA o Q x A

C p (To T )+ ( H r ) FR

FR

q =

CA o x A

2000

(298 308) + 20,000 = 8.889 10 5

cal

q = 100

2 0.9 min

The cooling rate requirement is the same, as it should be as there is no work term in the energy

balance. But it is easier to remove heat from the higher reactor temperature.

iii) Operate adiabatically with the new feed temperature while maintaining the previous feed

100

rate FA o = ; FA o x A = FR

0.9

FAo 100

Qo = =

C Ao 1 .8

Now we must find the new operating point by a simultaneous solution of the species and

energy balance.

C Ao x A = r

~

To T + r = 0

Since we need adiabatic operation by combining the above two equations we get the

relationship between conversion and temperature

~ ~

T = To + r = To + C Ao x A

T = 298 + 10 2 x A = 20 [14.9 + x A ]

12, 500

32, 500

1.987 20 [14.9 + x A ] 1.987 20 (14.9 + x A ) 1227 1.8

2 x A = 5 10 e

8

2 (1 x A ) 3.4 10 e 21

100

314.5 817.8

14.9 + x A

11.043 10 (1 x A )e

9 14.9 + x A

6.810 x A e

21

xA = 0

22

ChE 471 Fall 2005

LECTURE 7

The purity (conversion) has been reduced somewhat from the required 90%.

r = 510 e 8 1.987 315.6

2 (10.88) 3.4 10 e

21 1.987 315.6

20.88

mol

r =0.0786

lit min

100 mol

FR = FAo x A = 0.88 = 97.8

0.9 min

iii) We could operate the reactor adiabatically with the new feed temperature and maintain (via

a controller) fixed exit composition at x A = 0.9 which would require adjusting the feed

rate.

Now

~

T = To + A C Ao x A = 298 + 20 1.8 = 316 K

x A = 0.9

12, 500 32, 500

r = 5 10 e

8 1.987 316

2 (1 0.9) 3.4 10 e 21 1.987 316

2 0.9

mol

r = 0.023

lit min

mol

FR = r V = 0.023 1227 = 28.2

min

This is too high a penalty to pay for maintaining purity i.e. keeping x A = 0.9 constant!

23

ChE 471 Fall 2005

LECTURE 7

C. For minimum total reactor size we must find the minimum of the following expression

1 + 2 x A1 0.9 x A1

= +

CA o rm1 rm f

12, 500 32, 500

rm1 = 10 e 9 1.987 Tm

(1 x ) 6.8 10

A1

21

e

1.987 Tm1

x A1

10,065

With Tm =

x A1

30.51 + ln

1 xA

1

d +

By taking 1 2

= 0 one gets by trial and error

d x A1 Ao

C

x A1 = 0.72 mol

rm1 = 0.5

Tm1 = 320 K lit min

FA o x A1 100 0.72

V1 = = = 160 liters

rm1 0.9 0.5

V2 =

(

FA o x A f x A1 )= 100 (0.9 0.72) = 244.5 lit

rm f 0.9 0.0818

24

ChE 471 Fall 2005

LECTURE 7

1

To = 298K 306 320 304 308

0.8

xA

q&1 V1 q& 2 V2

0.6 adiabatic adiabatic

0.4

0.2

To

100 cal

q&1 = Q C p (305.6 298) = 2000 (305.6 298) = 8.44 10 5

0 .9 2 min

700 cal

q& 2 = Q C p T = 2000 (320 304.4 ) = 1.73 10 6

0 .9 2 min

It should be noted that the above calculations can be made easier with a little analytical work to

obtain an expression for the maximum rate as a function of conversion. This is done by

substituting the Tm values

Tm =

(E 2 E1 ) R

k E xA

ln 20 2

k10 E1 1 x A

(R )A m = rm = k10e E1 R Tm

CA o (1 x A ) k 20 e E 2 R Tm

CA o x A

If we recall that e a ln b = e ln b = b a

a

We get:

E2 E2

( A)

E1

k E E 2 E1 k E E 2 E1 1 x E 2 E1

rm = k10 10 1 k20 10 1 CA o

k 20 E 2 k 20 E 2

E1

(E 2 E1 )

xA

25

ChE 471 Fall 2005

LECTURE 7

rm = 3.22 (1 x A )

1.625 0.625

xA

Another variation on the above problem is to have two equal size CSTRs in series. For

maximum production rate then under conditions 1 = 2 we must find x A1 that satisfies

x A1 x A 2 x A1

=

rm1 rm 2

In summary the following types of problems may be encountered:

~

I. Given V , Q, To , Tmo , Qm , , q& , find x A and T. This is equivalent to determining the

performance of an existing reactor or of one that is contemplated by design engineers.

In this case species mass balance and energy balance are solved simultaneously.

~

II. Given To , Tmo , , FR and x A determine the required V and desired operating T.

III. Production rate is specified. Exit conversion and temperature can be selected

together with V in order to optimize some profit function.

- transients in a CSTR

- control of a CSTR around an unstable steady state.

26

ChE 471 Fall 2005

LECTURE 7

One should keep in mind that yields and selectivities can be affected dramatically by the choice

of operating temperature when activation energies of various reactions are different.

a. Finding the optimum temperature for a desired product distribution irrespective of space

time requirements.

b. Finding an optimal temperature for a given reactor (given ) which maximizes the

production of the desired product.

v

j =1

ij Aj = 0 i = 1, 2, ...... R

F jo F j + v ij ri V = 0 (1)

j = 1, 2, ...... R

or

R

v [Xij i ri V ]= 0

i=1

and

(F )

s

~ ~

jo H jo F j H j + q& = 0 (2)

j =1

Equation (1) represents independent R species balances and eq (2) is the energy balance based on

assumptions of

b) negligible changes in potential and kinetic energy

27

ChE 471 Fall 2005

LECTURE 7

s To s T

jo ~ fj ~ p j j ~ fj ~ p j + q = 0

F H + C dT F H + C dT

j =1 T0 j =1 T0

s To s R T

F jo C~ dT v ij H~ fj + C~ p j dT ri V + q = 0

j =1 T pj j =1i=1 To

s To R

F C jo

~

dT v ij H ri V + q = 0

~ rTi

(2a)

j =1 T pj i=1

If we further assume e) constant heats of reaction and f) constant mean specific heats we get

R

C p Q (To T )+ ( H r ) ri V + q = 0

i

(2b)

i=1

28

ChE 471 Fall 2005

LECTURE 7

PROBLEMS

A R

= k1 C A k 2 C R (mol lit s )

k1 = exp 7

83,000

10 s

3

( )

1

RT

k 2 = exp 18

167,400

10 s

3

( )

1

RT

Note: the activation energies are given in (J/mol) use the value of the gas constant accordingly.

H r = 80,000 ( J mol )

C = 40 (J mol K )

~ p

1. The above reaction occurs in the liquid phase. The pressure is high enough so that the

liquid will not volatize in the permissible temperature operating range which is: 300 to

900K.

You have a V = 100 liters CSTR reactor. How would you operate this CSTR in order to

maximize the production rate of R?.

b) What are x A & T -operating conditions?

c) What is the heat duty for the system?

d) Sketch your system and location and heat duty of all heat exchangers, if any.

29

NONISOTHERMAL OPERATION OF

IDEAL REACTORS

Plug Flow Reactor

(CHE 471)

M.P. Dudukovic

Chemical Reaction Engineering Laboratory

(CREL),

Washington University, St. Louis, MO

ChE 471 Fall 2005

LECTURE 8

Plug Flow Reactor

To T To T

Fjo, Qo Fj

Tm,Qm Tm Tm Tmo

Assumptions:

1. Homogeneous System

2. Single Reaction

3. Steady State

1. Given desired production rate, conversion and kinetics and other parameters, determine the

required reactor size, heat duty and temperature profile.

2. Given reactor size, kinetics, etc., determine the composition of the exit stream.

s

A

j =1

j j =0 (1)

s s

E1 / RT j E 2 / RT j

r = k10e Cj k20 e Cj (2)

j =1 j =1

with

j

Mj / A x

A A To P

C j = CAo (3)

1 + A xA TPo

The mass balance in the reactor for species j can be written as:

dF j

= jr (4)

dV

v = 0 Fj = Fjo (4a)

1

ChE 471 Fall 2005

LECTURE 8

or

dx A

FAo = ( v A ) r = RA (4)

dV

V =0 xA = 0 (4a)

The energy balance based on (a) negligible changes in potential and kinetic energy and (b) no work

other than flow work is

d s

FjH j +

qv = 0 (5)

dV j =1

V = 0 F j H1 = F jo H jo (5a)

Based on further assumptions of (c) ideal mixtures and (d) ideal gases one gets:

s s

dF j

F j C H

dT

+ qv = 0 (6a)

~ pj dV j=1 ~ j dV

j=1

Using the idea of (e) mean specific heats which are constant and (f) constant heat of reaction, one gets

dT

(Q )C p + (H r )r + qv = 0 (6)

dV

Q =

mtot is the mass flow rate which is constant

J

qv is the rate of heat addition per unit reactor volume

m3 s

The simplest constitutive relationship for the rate of heat exchange is:

m2

av 3 - area for heat transfer per unit reactor volume

m

dx A

Fao + Ar = 0 (A)

dV

2

ChE 471 Fall 2005

LECTURE 8

qv

dT 647 48

QC p m (H r ) r + U av (T Tm ) = 0 (B)

dV

qv

647 48

dTm

mQm m C p m U av (Tm T) = 0 (C)

dV

and

du dp

G + +F = 0 (E)

dz dz

G = u - mass velocity

P = pressure

V

z= - axial distance

A

Q

u= - velocity

A

F frictional losses

Equation (E) is the momentum balance. However this equation is usually solved separately and a mean

pressure is selected for evaluation of gas concentrations in eq (3).

For gases the use of mass fractions, wj, and extent per unit mass, ' ' is recommended. (See lecture 1).

d ' '

G =r (8)

dz

dT

G = ' ' r + q'v' (9)

dz

3

ChE 471 Fall 2005

LECTURE 8

Hr qv

'' = ; q

''

v = (11)

Cp Cp

s

j =1

j

s m j T P 1

r = k10eE1 / RT

C joj 1 + j tot o s

F jo TPo 1 + M

j =1

j avo

j=1

s v j

mbot ' ' To P

j

j 1

Cjo 1 + j

E2 / RT

k20e (12)

j =1

Fjo TPo 1+ ( )

y Mavo ""

Mav o - average molecular weight at feed conditions

m Mj

tot

=

F jo w jo

d

=r (13)

d

dT

= r + qv (14)

d

= 0 ; = 0 ; T = To (15)

Hr qv Q' '

= ; qv = = v (16)

C p C p

s s

( ) ( )

j j

r = k10e E1 / RT

C jo + j k 20e E 2 / RT

C jo + j (17)

j =1 j =1

4

ChE 471 Fall 2005

LECTURE 8

z V

= = - residence time along the reactor.

u Q

From eqs (8) and (9) or (13) & (14) we can always get the following relationship between temperature

and extent

z

1 ''

G o

T = To + +

'' ''

qv dz (18a)

or

T = To + + qv d (18b)

o

For adiabatic operation (q'v' = 0, qv = 0 ) this yields the equation of the adiabatic line, i.e extent and

temperature satisfy the relationship below at any and every point of the reactor

T = To +

'' ''

(19a)

T = To + (19b)

The maximum fractional adiabatic temperature rise is given by the Prater number just like in the case of

a CSTR.

Tad max

= =

(Hr )CAo (20)

To ( A )To C p

Basic types of problems

a. T(z) = To isothermal reactor. Integrate (8) or (13) and find extent along the reactor. From

eq. (9) or (14) find the heat addition/removal requirement along the reactor and the overall

heat duty for the reactor.

b. T(z) specified. Integrate (8) or (13) find (z). Use (z) and T(z) in eq (9)or (14) to get qv (z)

a) Adiabatic operation. T = To + ' ' ' ' or T = To + . Substitute into eq (8) or (13) and

integrate

5

ChE 471 Fall 2005

LECTURE 8

b) Heat duty is prescribed. q'v' (z) or qv (z ) prescribed. Simultaneously integrate (8) or (9) or

substitute

z

1 ''

T = To + + qv dz into (8) and integrate.

'' ''

Go

qv = Uav (T Tm )

a) Tm = const. Integrate eqs (8) and (9) or eqs (13) and (14) simultaneously.

This is the case when reactor tubes are immersed in boiling medium or condensing medium.

dTm

Gm = m 'm (Tm T )

dz

Ua Q

m = vm Gm = m m

Cp m Am

Note: With cocurrent cooling a PFR can be kept isothermal with countercurrent cooling it cannot in the

case of n-th order reactions. Prove that for an exercise.

There is always a unique steady state in a PFR. Main problem with PFRs is:

parametric sensitivity and temperature runaway.

Classical example of temperature runaway presented by Bilous & Amundson (AIChE J., 2, 117 (1956).

6

ChE 471 Fall 2005

LECTURE 8

440

342.5

420

337.5

400

T

380

360

335

340 330

320

320

310

Tm = 300

300

0 10 20 30

A hot spot is formed due to a very small change in wall temperature. The system shows extreme

parameter sensitivity.

Reaction runaway is the phenomenon when a small change in feed concentration, temperature, flow rate

or in coolant temperature triggers a dramatic change in he temperature profile and leads to runaway

reactions and explosions. Exact criteria for runaways are difficult to develop.

Example 1

A reversible first order reaction (considered earlier in a CSTR) is now to be per formed in a PFR.

A R (liquid phase)

k1 = 5x10 8 e 12,500 / RT (min1 )

k 2 = 3.4x1021 e 32,500 / RT (min1 )

Hr = 20,000 cal / mol G298

o

= 2,500 cal / mol

C p 2,000 (cal / lit oC)

CAo = 2 (mol / lit)

7

ChE 471 Fall 2005

LECTURE 8

If the feed rate is Q = 100 (lit/min) and the PFR size is V = 1,500 (lit):

c) if the maximum permissible temperature is 80C determine the optimal temperature profile along

the reactor necessary to maximize exit conversion.

d) If the desired conversion is 85% find the minimum reactor volume and the desired heat removal

rate along the reactor. Permissible temperature range is 0 to 100C.

Solution

Ax

V dx

= = CAo A

Qo o

rA

rA = k1CA k 2 CR = CAo[k1 (1 x A ) k2 x A ]

rA = k1CAo1 x A A

x ( 1 x Ae ) k

sin ce k 2 = 1 =

(

k1 1 x Ae )

x Ae K x Ae

k1CAo K k1

(rA ) = (x Ae x A ) x Ae = =

x Ae 1 + K k1 + k2

(rA ) = (k1 + k2 )CAo (x Ae x A )

1

xA

1 x

dx A

= = ln

Ae

k1 + k 2 o x Ae x A k1 + k 2 x Ae x A

1

x A 1 exp(k1 (1 + ) )

K

k 1500

= x Ae 1 exp 1 = = 15 min

x Ae 100

8

ChE 471 Fall 2005

LECTURE 8

T K k1 xae xa

273 1494 0.0498 0.999 0.526

283 407 0.112 0.998 0.813

293 121 0.239 0.992 0.965

303 40 0.486 0.975 0.974

313 13.5 0.943 0.931 0.931

323 5.0 0.755 0.833 0.833

333 2.0 3.149 0.662 0.662

343 0.81 5.46 0.448 0.448

353 0.35 9.17 0.262 0.262

363 0.16 15.0 0.139 0.139

373 0.08 23.8 0.071 0.071

The reactor space time is so large that above 50C practically equilibrium conversion is obtained.

T = To + ACAo x A

HrA 20,000 lit oC

A = = = 10

C p 2,000 mol

CAo = 2

mol

lit

T = To + 20 x A

dx A

CAo = ( k1 + k 2 ) CAo( x Ae x A ) = k1CAo ( k1 + k 2 ) CAo x A

d

= 0 xA = 0

E / RT E / R( T + 20 x )

k1 = k10e 1 ad = k10 e 1 o A

E / R( T +20 x )

k 2 = k20 e 2 o A

K k1

x Ae = =

1 + K k1 + k 2

= k10 e 1 k10e + k20 e 2 o xA

d

=0 xA = 0

9

ChE 471 Fall 2005

LECTURE 8

dx A 8

12, 500

1.987( To +20 x A )

8

12, 500

1.987( To +20 x A ) 21

32,500

1.987( To +20 x A

= 5x10 e 5x10 e + 3.4x10 e xA

d

= 0 ; xA = 0

xA

dx

= 15 =

12, 500

1.987(To + 20 x )

12,500

1.987( To +20 x )

32,500

1.987( To +20 x )

o 8

5x10 e 5x10 e

8

+ 3.4x10 e

21

x

We find:

i) To = 0C = 273 K xA = 0.78

Tadiabatic = 15.7K = 16K T = 289 K

ii) To = 20C = 293 K xA = 0.94 = xAe

Tadiabatic = 18.8 = 19 K T = 292 K

c) In order to maximize conversion at given space time we should follow the line of maximum

rates.

( E 2 E1 / R) 10, 065

Tm = =

k 20 E 2 xA x

ln + ln 30.51 + ln A

k10 E1 1 xA 1 x A

Since maximum permissible temperature is 80C (353 K) we have to preheat the feed to 33 K, cool the

reactor and keep it isothermal a 353 K until the locus of maximum rate is reached and then run along the

locus of maximum rates.

The intersection of the isothermal line T = 353 K and the Tm line determines up to which point the

reactor has to be run isothermally.

10,065

T = 353 = Tm =

x

30.51+ l n A

1 x A

10,065 353x30.51

exp

353

xA = = 0.119

10,065 353x30.1

1+ exp

353

10

ChE 471 Fall 2005

LECTURE 8

1

0.119

dx 1 x Ae

= = ln

k1 + k2 o

(x Ae x A ) (k1 + k2 ) x Ae x A

1 0.262 = 0.017(min)

= ln

9.17(1+

1

) 0.262 0.119

0.35

The isothermal operation should occur in the very entry section of he reactor. After that the Tm line

should be followed.

12 ,500 32,500

dx A 1.987Tm 1.987Tm

= 5x108 e (1 x A ) 3.42x1021 e xA

d

10,065

Tm =

x

30.51 + ln A

1 x A

= 0.017 x A = 0.119

Desired result at = 15

Really one should preheat only to adiabatic line. Adiabatic line should end at T = 353 K, xA = 0.119.

Hence, the fluid must be preheated up to To = T ACAo x A = 353 20x0.119 = 350K

xA

x Ae

11

ChE 471 Fall 2005

LECTURE 8

xA

x Ae

xA

Tm

x Ae

Tmax

d) Permissible temperature range is 0C to 100C. We want minimum reactor size for xA = 0.85.

Preheat to 100C, run along the locus of maximum rates

x A = 0.85

dx

=

12 ,500

1.987Tm

12,500

1.987Tm

32, 500

1.987Tm

o 8

5x10 e 8

5x10 e + 3.4x10 e

21

x

10,065

with Tm =

x

30.51 + ln A

1 x A

= 1.8min Thus with Q = 100 lit/min we need only V = 160 liters

The desired temperature profile along the reactor is presented in the enclosed graph. The heat removal

per unit volume is

12

ChE 471 Fall 2005

LECTURE 8

q

= C p (To T ) + (H r )CAo x A

Q

= 2, 000(100 T ) + (20, 000x2)x A

This curve is also presented in the figure. The total heat density is:

q

= 2,000(100 70) + 40,000x0.85

Q tot

= 1.56x105 (cal / lit)

7

With Q = 100 lit/min qtot = 1.56x10 (cal / min)

For comparison, if cooling failed and reactor ran adiabatically with To = 100C one would get

s

A

j =1

ij j =0 i = 1,2,...R (1)

R

dFj

+ ij ri = 0 j = 1,2,...R (2)

dV i=1

or

R

dXi R

ij + ij ri = 0

i =1 dV i=1

(2a)

dX

i + ri = 0

dV

(

d Fj H j )+ q = 0 (3)

v

dV

V = 0 ; Fj = Fjo ( Xi = Xio ) ; H j = H jo

With the usual assumptions made about the energy balance (see the lecture on CSTR) one gets:

13

ChE 471 Fall 2005

LECTURE 8

( )

s R

dT

Fjo C + HrTi ri + qv = 0 (4)

~ pj dV i =1

j =1

dXi

+r = 0 i = 1,2...R (A)

dV i

( )

R

dT

C pQ + Hri ri + qv = 0 (B)

dV i=1

V = 0 ; Xi = Xio T = To

Q = const

s s

E1i / RT ij E2 i RT

ri = k i10e Cj ki 20e C j ij (C)

j =1 j=1

with

R

ij Xi

1+ i =1

T Fjo

C j = Cjo o (D)

o T

R s

ij Xi

1+ i =1 j=1

Fbot o

qv = Ua v (Tm T )

a) Tm= const

dTm

m mQm C p m qv = 0 (E)

dV

14

ChE 471 Fall 2005

LECTURE 8

Problems

A R

Consider the reaction introduced in he last lecture

R=k1CA-k2CR (mol/lit s)

83,700

k1 = exp 7 x10 3 (s-1)

RT

167, 400 -1

k2 exp18 10 (s )

3

RT

Hr = 80,000 (J / mol)

C = 40(J / mol K)

~ p

1. The above reaction occurs in liquid phase! Permissible temperature range of operation is 300 <T <

900 K.

Feed conditions:

You have a V = 100 liters PFR. How would you operate this reactor if the only objective is to

maximize the production rate of R.

c) What is the profile of heat addition or removal for every 10% of reactor volume.

d) What is the overall heat duty for the reactor and any heat exchangers preceding it.

The feed is 50%A, 50% inerts. Permissible temperature range is 250< T < 900 K. Pressure is

constant in the reactor. Gases start to condense below 250 K. Desired conversion is 85%.

15

ChE 471 Fall 2005

LECTURE 8

a) What reactor volume is needed if you operate along the locus of maximum rates?

3. For the above problem what would FR and xA be if you had a reactor (PFR) of V = 100 liters

available?

4. Suppose that the reactor can only be operated adiabatically and the desired conversion is 85%.

Minimize the required reactor size.

16

WALL COOLED TUBULAR

REACTORS: AVOIDANCE OF HOT

SPOTS

(CHE 471)

M.P. Dudukovic

Chemical Reaction Engineering Laboratory

(CREL),

Washington University, St. Louis, MO

ChE 471 Lecture 9 Fall 2005

The pioneering work of Bilous and Amundsen (AIChE J. 2, 117, 1956) showed that a plug flow

reactor (PFR) cooled from the wall can exhibit extreme parametric sensitivity to small changes in

the wall temperature or heat transfer parameters. Their observation is sketched in Figure 1

below:

1 300 oC

440

2 320 oC

420

3 330 oC

400

4 335 oC

380

5 337.5 oC

360 5

4

340

3

320 2

1

300

0 10 20 30

(s)

Temperature

Clearly a small variation in the wall temperature of 2.5 C (from 335C to 337.5 C) caused an

80C local rise in reactor temperature! This 'hot spot' generation can lead to reactor runaway for

many reasons. Undesirable reactions of high activation energy can take off at this elevated

temperature, vapor formation can cause increased pressure, rate of reaction may reach extreme

values, etc. Therefore, it is imperative to operate the wall cooled tubular reactor in such a

manner that it does not exhibit such extreme parametric sensitivity and, hence, is not prone to

runaway.

To identify the parameter space for safe operation one starts with the mass and energy balance

for the reactor. Assuming for simplicity, constant volumetric flow rate, Q = const., and a single

simple irreversible reaction, A products, the governing equations are:

dx A ( R A )

= (1)

d C Ao

1

ChE 471 Lecture 9 Fall 2005

Energy balance (assuming constant average physical properties and constant heat of reaction):

= (H rA )(RA ) Uav (T Tw )

dT

Cp (2)

d

= 0 x A = 0, T = To (2a)

=

V

(min ) is the space time measured from the reactor entrance as reactor internal

Q

volume V is also measured from the entrance.

mol

CAo 3 = molar feed concentration of A

m

( )

kg / m 3 = fluid density

C (J / kg K )

p

o

= mean specific heat of the reaction fluid

J

H rA = heat of reaction per mole of A

mol A

mol A

RA 3 = rate of reaction of A

m min

T(K) = temperature in kelvin

xA = conversion of A

J

U 2 = overall heat transfer coefficient

m K min

(

av m 2 / m 3 = ) 4

dt

= area for heat transfer per unit internal reactor volume

To (K) = inlet feed temperature

dt (m) = tube (reactor) diameter

To simplify the algebra, but without loss of generality of the result to be derived, we will take

To= Tw thus assuming the inlet and wall temperature to be the same.

We can now divide eq (2) by eq (1) and rearrange the result to get:

dT H rA CAo 4U (T To )

=

dt C p (RA )/ CAo

(3)

dx A Cp

2

ChE 471 Lecture 9 Fall 2005

Let us define the characteristic reaction time based on the value of the reaction rate at the feed

conditions of concentration and temperature:

C Ao C Ao

R = = (4)

( R A )o k o e E / RTo C Ao n

Here we have assumed for simplicity an n-th order irreversible reaction and ( R A )o means that

we evaluate the rate at feed conditions of concentrations and temperature.

We also have a characteristic heat transfer time:

dt C p

h = (5)

4U

R 4U CAo

=N= =

h (RA ) dt C p

(6)

o

and

=

(H )C rA Ao

(7)

C p To

dT T To

= To

(RA )/ (RA )o

(8)

dx A

This last expression contains the dimensionless rate of reaction, ( R A ) / ( R A )o , which for an n-

th order irreversible reaction can be written as:

(R ) = k e E / RT

CAn

E To

1

(1 x )

RTo T n

=e

A o

(R ) ke E / RTo n A (9)

A o o CAo

E

= (10)

RTo

T To

= (11)

To

Upon substitution of eqs (9), (10), (11) into equation (8) we get:

3

ChE 471 Lecture 9 Fall 2005

d

= / 1+ / (12)

e ( )

(1 x )

n

dx A

A

S = = (13)

d n / 1+ / )

= e (

/ 1+ / . )

(1 x A ) e ( (1 x A )

n

(14)

dx A

Since the term on the right hand side of eq (14) that multiplies the term in the brackets is always

positive the sign of the derivative of the dimensionless temperature with respect to conversion,

d

i.e sgn , depends on the terms in the brackets in eq (14). By taking the coolant temperature

dx A

d

Tc to be equal to the feed temperature To, we have assured that > 0 and temperature rises

dx A

with conversion. This is obvious by observing and plotting the terms in the brackets in eq (14).

Physically this tells us that if we try to cool an exothermic reaction with the coolant at feed

temperature, unless the characteristic heat transfer time is infinitesimal in comparison to

characteristic reaction time, i.e , or stated differently the heat removal rate is infinitely

faster than the heat generation rate by reaction at the feed (wall) temperature, then the reactor

temperature must rise with conversion. We can allow for this but we want to know what values

of parameters , , will keep that temperature rise within safe limits.

We can think of the first exponential term in the brackets of eq (14) as the heat generation term

by reaction and the second as the heat removal rate. Indeed heat generation term has an

Arrhenius dependence on temperature, heat removal rate is linear in temperature. Now the heat

generation term is difficult to plot as a function of dimensionless temperature because of the

presence of the (1-xA)n conversion dependent term. We would need to integrate eq (14), save

values of xA vs and then we could plot the terms in brackets of eq (14) against . However,

since we are interested in preventing excessive maximum temperatures in the reactor, we can

take a conservative approach by assuming the worst possible scenario. In the n-th order reaction

(n > 0) the rate of heat generation is being slowed down as conversion increases with as the

(1-xA)n term becomes smaller and smaller at increased conversion. The worst possible scenario

is then if the heat generation rate (and hence the rate of temperature rise) is not affected by

increased conversion. This is the case of zeroth order reaction.

For a conservative approach assume n = 0 and now consider the term in the brackets of eq (14)

4

ChE 471 Lecture 9 Fall 2005

F ( ) = e / (1+ / ) = y1 ( ) y 2 ( ) (15)

Clearly, as = 0, y1 (0) = 1; and as , y1 e and y1 is bounded. At the same time, as

= 0, y 2 (0) = 0; and as , y2 is unbounded. Thus, y1 ( ) is a sigmoidal (S-shape)

curve and y 2 ( ) is a straight line through the origin as shown in Figure 2.

Depending on the value of the ratio of the two dimensionless groups / the three scenarios

depicted in Figure 2 may occur.

1

y1 ( )

2 3

y 2 ( ) e

y1 ( )

1 , 2 ,3

are y 2 (0) for

decreasing

The three straight lines in Figure 2 represent y 2 ( ) at three different values of the parameter

/ . Please, recall that at / our y 2 ( ) would be a vertical line guaranteeing = 0 ,

i.e T = To = Tw. For the three scenarios depicted above

> > (16)

1 2 3

and the rate of cooling decreases as we go from case 1 to case 3. Also remember that the value

d

of at which y1 ( ) = y 2 ( ) signifies F ( ) = 0 i.e. = 0 and yields the maximum

dx A

temperature that is observed in the reactor at such conditions. So, in case of rapid heat removal

rate (Case 1) the maximum temperature max 1 is relatively small and of no concern. At the

5

ChE 471 Lecture 9 Fall 2005

certain lower value of heat transfer rate than in case 1, y 2 ( ) not only intersects but is a tangent

of y1 ( ) (Case 2). In this case the maximum temperature max 2 is still tolerable but any

further, even very small, decrease in / would lead to an excessive maximum temperature as

depicted in Case 3 where clearly max 3 is a hot spot to be avoided.

and

dy1 dy 2

for avoiding the hot spot (17b)

d max d max

This means that at the maximum temperature, max , the slope of the heat generation line, y1 ( ) ,

must be less than the slope of the heat removal line, y 2 ( ) . The condition at which the slopes

are equal corresponds to using the equality sign in eq (17b) and is illustrated by line 2 in Figure

2. This defines the maximum allowable maximum temperature max 2 . Beyond this point

excessive hot spots may arise.

e / (1+ / ) = (18a)

and

1

e / (1+ / ) (18b)

2

1 +

/(1+ / )

By eliminating e in equation (18b) in terms of , as per eq (18a), and by using the

equality sign in eq (18b), we can develop an equation for the maximum permissible temperature.

Do that for an exercise by solving the resulting quadratic equation for max . Substitution of the

result for max in the inequality of eq (18b) determines the parameter space that guarantees the

absence of hot spots. The result is not pretty looking.

To get a clear and easy formula to remember an approximate analytical solution is developed via

/(1+ / )

a conservative approach in which one replaces e by a rising exponential e . This is

' T

equivalent to replacing k=koe-E/RT, i.e the Arrhenius temperature dependence with k = k o e

'

dk dk '

and demanding that at T = To, k = k' and = at T = To i.e at that point of T = To both

dT dT

6

ChE 471 Lecture 9 Fall 2005

/(1+ / )

functions are equal and their derivatives are equal. Indeed e and e have the same value

and the same value of the first derivative at = 0 . In Figure 3 we sketch the approximation of

y1 = e /(1+ / ) with e

e

e (1 + ) y1

e

Figure 3: Approximation of the Arrhenius dependence of the rate constant with an exponential

function.

Since we are interested in limiting the max the two curves are pretty close for small . Clearly,

if we replaced y1 ( ) with e in Figure 2 we would lose the intersection with y 2 ( ) for Case 3

but this is not of concern since we are not interested in > max 2 , and for Case 2 the intersection

of y 2 ( ) with e is close to that of y 2 ( ) with y1 ( ) in Figure 2. The advantage of this

approximation is that the criteria of equations (17a) and (17b) applied to

y1 ( ) = e and y 2 ( ) = yield

e = (19a)

and

e (19b)

max = 1 (20)

7

ChE 471 Lecture 9 Fall 2005

Substitution of this into the inequality described by eq (19b) yields the parameter space that

guarantees absence of hot spots

e (21)

Replacing the above dimensionless quantifies in terms of actual physical variables we get from

eq (20) the maximum permissible temperature that can be tolerated in absence of hot spots

1

Tmax + 1To (22)

From eq (21) we get the conditions that the system parameters must satisfy to guarantee absence

of hot spots.

4 U R To2

e

(k oeE / RTo CAo

n

)

(H rA )E dt (23)

This equation is usually written in terms of tube diameter that will guarantee absence of hot spots

by providing sufficient heat transfer area per unit volume

4U RTo e1

2

dt (24)

E (H rA )k oeE / RTo CAo

n

Clearly, other permutations of eq (23) are possible. Given kinetic and reaction parameters, feed

temperature and tube diameter one can calculate the maximum permissible feed concentration

that guarantees safe operation, etc.

Approximate analysis, using the approximate exponential dependence of the rate constant, but

accounting for the effect of reactant depletion, is possible for an n-th order reaction and yields

the following result which is a little less conservative than equation (23).

e

(25)

1 + 2.703n 2 / 3 2 / 3

This result is due to Chandler Barkelew, Chem. Engr. Progress Symp. Ser. No. 25, Vol. 55, p. 37

(1959) and is one of the most useful expressions for nonisothermal tubular or batch reactors.

The graph showing the parameter space that is safe, based on Barkelew's and similar criteria, is

appended as Figure 3.

8

ChE 471 Lecture 9 Fall 2005

9

SAFE OPERATION OF TUBULAR (PFR)

ADIABATIC REACTORS

(CHE 471)

M.P. Dudukovic

Chemical Reaction Engineering Laboratory

(CREL),

Washington University, St. Louis, MO

ChE 471 Lecture 10 Fall 2005

In an exothermic reaction the temperature will continue to rise as one moves along a plug flow

reactor until all of the limiting reactant is exhausted. Schematically the adiabatic temperature

rise as a function of space time, measured from the reactor entrance, takes the form shown in

Figure 1.

Tad

Tinf

T0

exothermic reaction.

( )

H rA C Ao

Tad = To 1 + = To [1 + ] (1)

C p To

is often excessive for highly exothermic systems ( large) and needs to be avoided. In such

situations the old rule of thumb suggests that we should operate in such a way that the inflection

dT

point, i.e. the point of maximum temperature rise , is never reached. This implies that

d max

we operate with < * where * is the value of space time at which the inflection point

d 2T

2 = 0 occurs.

d

1

ChE 471 Lecture 10 Fall 2005

Let us now develop a convenient and simple formula for use by practicing engineers which

would guarantee safe operation. Consider an n-th order irreversible reaction:

R A = k o e E RT C Ao (1 x A )

n n

(2)

At adiabatic conditions temperature and conversion are related by the adiabatic line equation

T = To (1 + x A ) (3)

T To

= (4)

To

then conversion in Eq. (3) can be expressed in terms of dimensionless temperature as:

xA= (5)

where

= (6)

with

= E RTo (7)

obtained by using the adiabatic line eq (5) to replace conversion. The result is:

( R A )ad = ( R A )o e ( + )

1 (8)

( R A )o = k o e E RTo C Ao

n

(9)

Cp

dT

d

(

= H rA ) ( R )

A ad (10)

2

ChE 471 Lecture 10 Fall 2005

d

n

( + )

= e 1 (11)

d R

C Ao

R = (12)

( R A )o

The initial condition is

=0 =0 (13)

We can rewrite Eq. (11) in the most compact way by defining the Damkohler number as the ratio

of characteristic process time and reaction time, i.e.

( R A )o

Da = = (14)

R C Ao

d

n

( + )

= e 1 (15)

d (Da )

At Da = 0 =0 (16)

Now we want to have the reactor short enough (limit the conversion achievable) so that we can

d 2

keep the inflection point = 0 out of the reactor i.e. we do not let it occur in the reactor.

d 2

d 2

=0 (17)

d (Da )

2

inf =

2n

[ 2

]

+ 4n ( + ) 2n ; n 0 (18a)

3

ChE 471 Lecture 10 Fall 2005

The result for the zeroth order reaction, eq (18b), can be obtained by applying the LHospital rule

to eq (18a). A better approach is to notice that for n = 0 equation (15) indicates that

d d (Da ) > 0 always, so that there is no inflection point as the rate of temperature rise keeps

rising until all reactant is depleted. Then at x A = 1 , from eq (5) it follows that max = and

therefore Tmax = Tad .

We can integrate the differential equation (15) by separating the variables to obtain the critical

value of Da * and, hence, of *

Da * inf ( + )

e

Da = d (Da ) = d

*

(19)

n

1

0 0

Clearly for given values of parameters , , = , and reaction order n, we can evaluate inf

from eq (18a) and then calculate the value of Da * by numerically evaluating the integral in eq

(19).

Using then the definitions of Da and we get the criterion for safe operation Da < Da *

which can be expressed as:

k o e E RTo C Ao

n

( H ) E

rA

*

Da * (20)

R C p To

2

To get a convenient, easy to remember value of Da * , the following approximations are often

made. First, the Arrhenius dependence of the rate constant on temperature is replaced by an

exponential dependence, in effect

( + )

e e (21)

Substituting this approximation in eq (15) yields via eq (17) to a new approximate value of the

temperature at inflection point

n

e

(Da ) *

app = d = n e

eu

n u n du (23)

n

1

0

4

ChE 471 Lecture 10 Fall 2005

The final approximation (which is conservative in nature as it assumes the worst possible case of

zeroth order reaction) ignores the slowdown of the temperature rise due to the consumption of

the reactant, which is the same as taking n = 0 in eq (23).

This yields

(Da ) *

app , 0 = e e

u

du = e e u ( )

0

(24)

[e ]

0

= e

1 =1 e

=1 (for large enough )

Substituting this into eq (20) gives the conservative criterion for safe operation.

It is constructive to note that this same equation (20a) with time t replacing

k o e E RTo C Ao

n

( H ) E t *

<1

rA

(20a)

R C p To

2

is used to determine the so called time of no return or time to explosion in batch systems. This

time to inflection point t * may be very long for low To but becomes quite short if the system of

high activation energy is exposed to higher To . Hence, chemicals that may be safe to store at

25C may be explosion prone if exposed to 40 50C!

C Ao x A = ( R A ) (25)

The adiabatic equation relates conversion and temperature

T To

xA =

( )

H rA C Ao C p

(26)

n

1 ( + )

= e 1 (27)

Da n

let

G ( ) = e ( + )

1 (28a)

5

ChE 471 Lecture 10 Fall 2005

L ( ) =

1

(28b)

Da n

We know from before that G is a sigmoidal curve in and represents heat generated by reaction.

L is the heat removal rate (i.e., heat removed by sensible heat of the fluid that flows through the

CSTR).

We know that up to three intersections are possible between G and L lines. To avoid the

intersection leading to excessively high temperatures we must assure that intersections at low

temperatures are available. The last permissible operating condition is the one when line L is

also tangent to curve G as schematically shown in Figure 2.

1 2 3

G ( )

L( )

1 2 = * 3

While operating adiabatic temperatures at 1 and 2 are acceptable, 3 represents too large a

temperature jump. Hence, we must assure that the L line always intersects the G line at its lower

temperature branch. The critical point is reached when L is also tangent to the G line.

6

ChE 471 Lecture 10 Fall 2005

L=G (30)

dL dG

(31)

d d

Applying the above to eqs (28a) and (28b), and using the equality sign in eq (31), we get the

equation for the maximum permissible temperature max perm = * . The critical value of the space

time * can be obtained from the critical value of Da * , which in turn results from substituting

the expression for * into eq (30).

( + )

To get a simple, easy to remember expression, usually we again replace e with e . This

yields

* =

1 n + 1 ( n + 1) 4

2

(32)

2

The negative sign in front of the square root needs to be taken as we are interested in the lower of

the two temperatures at which the L line could be tangent to the curve G. Then equation (30)

yields:

n

*

(Da ) = 1 e

* *

*

(33)

app

Da * e 1 (34)

k 0 e E RTo C Ao

n

( H ) E e

rA 1

(35)

R C p To

2

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