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Original Title: Ideal Reactors for a Single Reaction

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Batch Reactor

dXA

-rA=CA0 (constant volume)

dt

CA0 dXA

-rA= (volume varies)

1+dyAoXA dt

from these equations, given conversion vs. time (or some equivalent thereof) we can get

the rate law. Alternatively, the reactor can be designed (volume of reactor, time of

running for a given conversion) can be found given rate law.

Flow Reactors

t is space-time, the time required to process one reactor volume of feed at specified conditions, s is the space-

velocity, number of reactor volumes of feed at specified conditions that can be treated in unit time.

Example, space-time of 2 s means one reactor volume can be processed by given reactor in 2 s.

CA0V V

t= =

v0 Note that residence time, which for the case of flow reactors is the average amount of time

v0

spent by molecule inside the reactor is

V

t=

v . The two are equivalent only for constant density systems since in other cases the inlet and outlet

volumetric flow rate are different (expansion factor). A

Space-time is a design variable and its definition arises naturally out of the material balance for CSTRs and

PFRs. It is based on inlet flow and concentration conditions. It is important to note the conditions at which

space-time is defined.

CSTR:

FA0-FA=(-rA)V or

CA0XA

t= assuming the initial feed stream has unconverted A. If the feed is partially converted,

(-rA)

CA0(XA-XA0)

t=

(-rA)exit For constant density,

t = CA0-CA

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9/18/2017 Ideal Reactors for a Single Reaction

(-rA) Thus given any three of V,FA0,XA,(-rA) the other one can be easily calculated. Note that the

reaction rate is relatively easily obtained in this case as compared to Batch reactor data (no need

for differentiation here). Graphically, we can represent these equations as:

-rA=kCA so

CA0XA XA(1+dyAoXA)

t= =

kCA k(1-XA)

XA

kt = for constant density systems

1-XA

2. Second order reaction 2A- > Prodts

CA0XA XA(1+dyAoXA)2

t= =

kCA2 k(1-XA)2

XA

kCA0t = for constant density systems

(1-XA)2

The dimensionless group formed from k,t,CA0 is called the Damkohler number. Its

numerical value depends only on conversion for the case of isothermal CSTRs:

(1-XA) 1-XA

(1-XA)2 (1-XA)2

(1-XA)(M-XA) (1-XA)(M-XA)

(1-XA)n (1-XA)n

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Example Problems

CSTR, A- > R, aqueous solution of 100 mmol A/liter is fed to a 1 liter reactor. Outlet concentrations of A versus

flow rates are measured. Determine rate equation. Assume the reactant alone determines the rate.

v, l/min 1 6 24

CA, mmol/l 4 20 50

CA0-CA 96 80 50

-rA=24(min-1)CA

Note that in this case 'aqueous solution' gives us the hint that we are dealing with constant density system. Also,

in case the data did not look so perfect as above, we could have used graphical methods we know in order to

evaluate the reaction order and rate constant.

Ex. 5.4 L:

Plan to replace present CSTR with one having double the volume. For same aqueous feed (10 mol A/l) and same

feed rate find the new conversion. The reaction kinetics is given by : A- > R;-rA=kCA1.5 and the present

conversion is 70%.

2CA0v0XA1 CA0v0XA2

= since feed concentration and volumetric flow rate are unchanged.

kCA01.5(1-XA1) 1.5 kCA01.5(1-XA2)1.5

2XA1 XA2

1.5

=8.52=

(1-XA1) (1-XA2)1.5 Solving this non-linear equation, we get the new conversion to be 79.4%.

3. The kinetics of a 'simple isothermal homogeneous fluid reaction A + ... -> products' has been measured in a

CSTR by changing the residence time. (Separation method: the concentrations of the other components are kept

constant). The data is: CA,0 = 1 (mol/l)

Calculate: conversion of A, reaction rate r(A), reaction order concerning A, and rate constant.

Answer: The reaction is of second order and has a rate constant of 1 (l/mol sec)

-rA=FA0 dXA

or since FA0 is constant,

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dV

XAf dXA

t = CA0

0 (-rA)

C

Af dCA

t=-

C (-rA)

A0

Note that the equation describing the space-time for PFR is identical in form to the equation describing time in

batch reactor in case of constant density systems.

Example problems:

1. Derive the expression for a Damkohler number for PFR for first order reversible reaction A rR with

CR0/CA0=M and -rA=k1CA-k2CR and equilibrium conversion of XAe.

At equilbrium,

1-XAe M+rXAe

k1CA0( )=k2CA0( ) or

1+dyAoXAe 1+dyAoXAe

1-XAe

k2=k1( )

M+rXAe

XA (1+dyAoXA)dXA

t = CA0

0 k1CA0(1-XA)-k2CA0(M+rXA)

M+rXAe XA (1+dyAoXA)dXA

t=

k1 0 (1-XA)(M+rXAe)-(M+rXA)(1-XAe)

M+rXAe XA (1+dyAoXA)dXA

k1t =

M+r 0 XAe-XA

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9/18/2017 Ideal Reactors for a Single Reaction

M+rXAe XAe

k1t = (1+dyAoXA)ln( )-dyAoXA

M+r XAe-XA

Note that to solve PFR problems, integration is required, much like batch reactor systems.

E.g. 5.3 Levenspiel:

-rA=-rB/2=[(12.5l2/mol2/min)CACB2-(1.5min-1)CR]mol/l/min

is to take place in a 6 l steady-state mixed flow reactor. Two feed streams, one containing 2.8 mol A/l and the

other containing 1.6 mol B/l are to be introduced at equation volumetric flow rates into the reactor. 75%

conversion of the limiting reactant is desired. What should be the flow rate of each stream? Assume constant

density.

Solution:

When the feed streams are mixed, volume is 2 liters. The number of moles of A and B are 2.8 and 1.6 moles

respectively. Therefore

CA0=1.4mol/l

CB0=0.8mol/l

CR0=0

The limiting reactant in this case has to be B, based on the initial concentrations and the stoichiometric

coefficients.

CB=0.8mol/l(1-0.75)=0.2mol/l

CA=1.4-0.75*0.8/2=1.1mol/l

CR=0.3mol/l

Therefore,

-rA=0.1mol/l/min

-rB=2(-rA)=0.2mol/l/min

v0=(-rB)V/(CB0-CB)=2l/min

2. P4.3 Fogler: Zeroth order reaction A- > 3B, gas-phase, isothermal. Initial concentration of A is 2 mol/l, there

are 40% inerts in the feed. Specific rate constant is 0.1 mol/l/min and activation energy is 40kJ/mol. Final

conversion required is 80%. in case of flow reactors, the volumetric flow rate to be used is 2 l/min. Calculate

t=CA0XA/k=16min

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1 dNA

- =k and NA=NA0(1-XA) and V=V0(1+(3-1)*0.6XA)=V0(1+1.2XA)

V dt

So,

t= = ln(1+1.2XA)=11.2min

k 0 (1+1.2XA) 1.2k

V=FA0XA/k=v0CA0XA/k=32l

v0CA0 X

V= 0 AdXA=32l

k

Flow Reactors in Series:

Often, more than one reactor is used to perform the reaction. The merits and demerits of this can be analysed

fairly easily for simple reactions.

Consider two CSTRs in series. Inlet molar flow rate into the first reactor is FA0, the conversion out of the first

reactor is X1 and this is the feed into the second reactor. The exit flow rate and conversion are FAe and Xe

respectively. If the rate equation is known (or if a graph of 1/-ra vs. Xa is given), we can calculate the volumes

of the two CSTRs through our material balance equations:

1

V1=FA0( )X

-rA1 1

FA1-FAe+rAeV2=0 but FA1=FA0(1-X1) and FAe=FA0(1-Xe) therefore,

1

V2=FA0( )(Xe-X1)

-rAe Thus, knowing the rate of the reaction at conversions corresponding to X1 and Xe, the

volume of the reactors can be found. If we were to use one single CSTR for converting to Xe,with

everythingelse the same, the volume of this reactor would be

1

V=FA0( )X

-rAe e

We can see that V V1+V2. This is easy to figure out graphically. Note that the depending on

whether reaction is positive or negative order in the reactant, and depending the intermediate conversion

required, the sum of the volumes of two CSTRs in series could be less than or more than volume of one reactor

achieving all the conversion.

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dXA

V1=FA00X1 ;

(-rA)

dXA

V2=FA0X1Xe

(-rA) but in this case volume of a single reactor to achieve this conversion

dXA

V=FA00XAe =V1+V2

(-rA) and this fact is independent of the order of the reaction.

Other situations, such as CSTR followed by PFR and so on can be analysed in a similar manner through the use

of proper material balance equations.

Example problems.

Consider a first order reaction in a series of n CSTRs of same volume. Develop a relationship between final

conversion and Damkohler number

C0X1 X1

t1= = or

-r1 k(1-X1)

kt1

X1= and

1+kt1

C0

C1=

1+kt1 Mole balance on reactor 2:

F1-F2=v0(C1-C2)=(-r2V2) or

C1-C2

t2= or

kC2

C1 C0

C2= =

1+kt2 (1+kt1)(1+kt2) Extending to n-reactors, we get

C0

Cn=

(1+kt1)(1+kt2)...(1+ktn) If all reactors are of same size and have same volumetric flow rate,

C0

Cn=

(1+kt)n

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1

X=1-

(1+kt)n

Plotting X vs. Da, we find that when Da> >1, 90% conversion is achieved in 2-3 reactors.

Reactors in Parallel:

For reactors in parallel, V/FA0 is equal for each parallel stream, assuming no mixing occurs before the final

outlet. Two CSTRs in parallel:

V1=FA01XA/(-rA); V2=FA02XA/(-rA) so the total volume of the two reactors is V=FA0XA/(-rA). Clearly, this is

the volume we would have required of a SINGLE CSTR to get to the same conversion.

Recall that the same result was obtained for PFRs in series. Thus, for CSTRs in parallel and PFRs in series, we

can analyse by replacing the reactor network with one large reactor. Looking at this from the other angle, if we

replace two CSTRs in series with a large CSTR of volume equal to the sum of volumes of the two CSTRs, then

the conversion obtained will be different. Likewise for two PFRs in parallel.

On 24 Jan 2003, 11:41.

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