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Objectives: Define conversion and space time. Write the mole balances in terms of conversion for a batch reactor, CSTR, PFR, and PBR. Size reactors either alone or in series once given the molar flow rate of A, and the rate of reaction, -rA, as a function of conversion, X.

Conversion: Choose one of the reactants as the basis of calculation and relate the other species involved in the rxn to this basis. Space time: the time necessary to process one reactor volume of fluid based on entrance conditions (holding time or mean residence time)

1. Conversion Consider the general equation

aA + bB cC + dD A C

We will choose A as our basis of calculation.

b c d A+ B C + D a a a

The basis of calculation is most always the limiting reactant. The conversion of species A in a reaction is equal to the number of moles of A reacted per mole of A fed.

Batch

Flow

X=

( N A0 N A ) N A0

X=

(FA0 FA ) FA0

For irreversible reactions, the maximum value of conversion, X, is that for complete conversion, i.e. X = 1.0. For reversible reactions, the maximum value of conversion, X, is the equilibrium conversion, i.e. X = Xe.

= [N A 0 ]

[X ]

[1]

Now the # of moles of A that remain in the reactor after a time t, NA can be expressed in terms of NA0 and X;

[N A ] = [N A 0 ] [N A 0 X ]

N A = N A 0 (1 X )

[2]

dN A = rA V dt dN A = rA V dt

( prefect mixing )

[3]

For batch reactors, we are interested in determining how long to leave the reactants in the reactor to achieve a certain conversion X.

[4]

[5]

1 dN A d ( N A / V0 ) dC A = = V0 dt dt dt dC A = rA dt dt = N A 0 dX rA V

X

From [3]

Constant volume batch reactor From [5] Batch time, t, required to achieve a conversion X.

X

t = N A0

0

dX rA V

As t

Flow Reactor Design Equations: For continuous-flow systems, time usually increases with increasing reactor volume.

FA0 X =

Outlet flow rate

FA0 FA0 X = FA

inlet molar flow rate

F A = F A 0 (1 X ) FA0 = C

A0

v0

volume / time (volumetric flow rate, dm3/s)

moles /volume

For liquid systems, CA0 is usually given in terms of molarity (mol/dm3) For gas systems, CA0 can be calculated using gas laws.

Partial pressure

C A0 =

Entering molar flow rate is

PA 0 y P = A0 0 R T0 R T0

y P FA0 = v0 CA0 = v0 A0 0 R T0

yA0 P0 CA0 R T

= entering mole fraction of A = entering t t l pressure (kP ) t i total (kPa) = entering concn (mol/dm3) = 8.314 kPa dm3 / mol K = T(K)

A+

b c d B C+ D a a a

V =

Substitute for FA

FA0 FA rA

FA = FA 0 FA 0 X V = V = FA 0 ( FA 0 FA 0 X ) rA FA 0 X ( rA ) exit

dFA = FA0 dX

Substitute back:

dFA dX = FA 0 = rA dV dV

V = FA0

0

dX rA

3. Reactor Sizing Given rA as a function of conversion, -rA = f(X), one can size any type of reactor. We do this by constructing a Levenspiel Plot. Here we plot either FA0 / -rA or 1 / -rA as a function of X. For FA0 / -rA vs. X, the volume of a CSTR and the volume of a PFR can be represented as the shaded areas in the Levelspiel Plots shown below:

Levenspiel Plots

rA = k C A = k C A0 (1 X )

Specific rxn rate ( (function of T) ) initial concn

1 1 1 = rA k C A0 1 X

-1/rA

Example: Lets consider the isothermal gas-phase isomerization: AB X 0 0.1 0.2 0.4 0.6 0.7 0.8 08 [T = 500 K] [P = 830 kPa = 8.2 atm] initial charge was pure A -rA(mol/m3s) 0.45 0 45 0.37 0.30 0.195 0.113 0.079 0.05 0 05

Example: Lets consider the isothermal gas-phase isomerization: AB X 0 0.1 0.2 0.4 0.6 0.7 0.8 08 [T = 500 K] [P = 830 kPa = 8.2 atm] initial charge was pure A -rA(mol/m3s) 0.45 0 45 0.37 0.30 0.195 0.113 0.079 0.05 0 05 1 / -rA 2.22 2 22 2.70 3.33 5.13 8.85 12.7 20.0 20 0

Draw -1/rA vs X:

-1/rA

We can use this figure to size flow reactors for different entering molar flow rates. Keep in mind : 1. if a rxn is carried out isothermally, the rate is y, usually greatest at the start of the rxn, when the concn of reactant is greatest. (when x 0 -1/rA is small) 2. As x 1, rA 0 thus 1/-rA & V

An infinite reactor volume is needed to reach complete conversion. For reversible reactions (A B), the max X is the equilibrium conversion Xe. At equilibrium, rA 0. As X Xe, rA 0 thus 1/-rA & V An infinite reactor volume is needed to obtain Xe.

if FA0 = 0.4 mol/s, we can calculate [FA/-rA](m3) Plot FA0/-rA vs X obtain Levenspiel Plot! Example: Calculate volume to achieve 80 % conversion in CSTR.

For instance:

3.6 m3

CSTRs are usually used for liquid-phase rxns.

1.5 m3

4. Numerical Evaluation of Intergrals The integral to calculate the PFR volume can be evaluated using a method such as Simpsons One-Third Rule.

NOTE: The intervals (X) shown in the sketch are not drawn to scale. They should be equal.

Simpsons One-Third Rule is one of the most common numerical methods. It uses three data points. One numerical methods for evaluating integrals are: 1. Trapezoidal Rule (uses two data points) 2. Simpsons Three-Eighths Rule (uses four data points) 3. Five-Point Quadrature Formula

Trapezoidal Rule

f(x) f(x1) A2 f(x0) x0 h A1 x1

x1

x0

f ( x) dx = h [ f ( x ) + f ( x )]

0 1

A1 = f ( x0 ) h A2 = [ f ( x1 ) f ( x0 )] h 2 A = A1 + A2 f ( x1 ) f ( x0 ) = h f ( x0 ) + 2 2 h = [ f ( x0 ) + f ( x1 )] 2

x4

x0

f ( x) dx = 3 ( f

x0

+ 4 f1 + 2 f 2 + 4 f 3 + f 4 ) where

h=

x 4 x0 4

For N+1 points, where N is an integer.

xN

f ( x) dx =

3h ( f 0 + 3 f1 + 3 f 2 + 2 f 3 + 3 f 4 + 3 f 5 + 2 f 6 .....) 8

Example: Consider the liquid phase reaction; A Products which is to take place in a PFR. The following data was obtained in a batch reactor.

X -rA(mol/dm3s)

0 0.01

0.4 0.008

0.8 0.002

If the molar feed of A to the PFR is 2 mol/s, what PFR volume is necessary to achieve 80 % conversion under identical conditions as those under which the batch data was obtained?

10

PFR V = FA0

0

1 dX rA

X

PFR : V = FA0

dX X = FA0 3 rA 0

1 4 1 + + rA ( X = 0) rA ( X 1 ) rA ( X 2 )

PFR : V = FA0

0

0.8

11

dX = rA dV

0 .8 0.8

dX F Re arranging : V = FA0 = A0 dX rA 0 rA 0

Lets numerically evaluate the integral with trapezoidal rule

0.8

r

0

FA0

A

dX

f (X ) = f (X ) =

FA 0 rA FA 0 rA

= 0.89

X =0

= 8 .0

X = 0 .8

V=

With five point quadrature V = 2.165 m3

VCSTR > VPFR for the same conversion and rxn conditions. The reason is that CSTR always operates at lowest rxn rate. PFR starts at a high y p g rate, then gradually decreases to the exit rate.

12

Reactors in Series: The exit of one reactor is fed to the next one. Given rA as a function of conversion, one can design any sequence of reactors.

Xi =

Example: Using Levenspiel plots to calculate conversion from known reactor volumes.

Pure A is fed at a volumetric flow rate 1000 dm3/h and at a concentration of 0.005 mol/dm3 to an existing CSTR, which is connected in series to an existing tubular reactor. reactor If the volume of the CSTR is 1200 dm3 and the tubular reactor volume is 600 dm3, what are the intermediate and final conversions that can be achieved with the existing system? The reciprocal rate is plotted in the figure below as a function of conversion for the conditions at which the reaction is to be carried out.

13

Solution: By trial and error, we find that a conversion of 0.6 gives the appropriate CSTR volume of 1200 dm3.

Similarly for the PFR, through trial and error, we find that a conversion of 0.8 gives the appropriate PFR volume of 600 dm3.

14

Reactor 1: Mole Balance: FA0 FA1 + rA1 V1 = 0

FA0 FA1 X1 = 0.4 -rA1

Reactor 2:

-rA2 FA2 X1 = 0.8

Mole Balance: FA1 FA2 + rA2 V2 = 0 FA2 = FA0 FA0 X2 Combining [4] & [5]:

[4] [5]

V2 =

X = 0.4 X = 0.8

-FA0/rA

X 0.4 0.8

15

-FA0/rA

4 X

V PFR = VCSTR ,i

PFRs in Series

FA0 -rA1 FA1 X1 =0.4 -rA2

X2 X

i =1

FA2 X1 = 0.8

X

FA0

0

1 2 dX dX dX = FA0 + FA0 rA 0 rA X 1 rA

The overall conversion of two PFRs in series is the same as one PFR with the same total volume

Reactors in Series: CSTR PFR CSTR Using the data in the table, calculate the reactor volumes V1, V2 and V3 for the CSTR/PFR/CSTR reactors in series sequence along with the corresponding conversion.

16

F X V1 = A 0 r A1

at X = X1 = 0.4 the (FA0 / -rA1) = 300 dm3 V1 = (300 dm3) (0.4) = 120 dm3 The volume of the first CSTR is 120 dm3

dX rA = dV FA0

Rearranging and intergrating with limits when V = 0 when V = V2 X = X1 = 0.4 X = X2 = 0.7

0.7 FA0 F dX = A0 dX V = r r A A X1 0.4 X2

17

X =

V2 =

X 3

V2 = 0.15 300dm 3 + 4 (370dm 3 ) + 600dm 3 = 119dm 3 3

The volume of last CSTR is 180 dm3

18

Summary: CSTR X1 = 0.4 PFR X2 = 0 7 0.7 CSTR X3 = 0.8 V1 = 120 dm3 V2 = 119 dm3 V3 = 180 dm3

Reactor Sequencing Is there any differences between having a CSTR PFR system & PFR CSTR system? Which arrangement is best?

or

V1 V2 V3 V4

FA0

The choice of reactors depend on ; the Levenspiel plots relative reactor sizes.

X Adiabatic rxns

19

Space Time

The space time, tau, is obtained by dividing the reactor volume by the volumetric flow rate entering the reactor:

V v0

Space time is the time necessary to process one volume of reactor fluid at the entrance conditions. This is the time it takes for the amount of fluid that takes up the entire volume of the reactor to either completely enter or completely exit the reactor. It is also called holding time or mean residence time.

Example: v0 = 0.01 m3/s and V = 0.2 m3 = 0.2 m3 / 0.01 m3/s = 20 s It would take 20 s for the fluid at the entrance to move to the exit.

Typical space time for different reactors: Batch : 15 min 20 h (few kg/day 100,000 tons/year 280 tons/day) CSTR : 10 min 4 h Tubular: 0 5s 1h 0.5s (10 to 3 x 106 tons/yr) (50 to 5 x 106 tons/yr)

20

SV =

v0 1 = V

instead of using volumetric flow rate at the entrance, you use liquid hourly & gas hourly space velocities (LHSV, GHSV). v0 (for LHSV) is that of a liquid feed rate at 60F or 75F. v0 (for GHSV) is that of the one that measured at STP.

LHSV =

v0 liq V

GHSV =

v0 STP V

21

HW (due date: Feb 25): S l th prpblem i your own way. Solve the bl in

http://www.engin.umich.edu/~cre/web_mod/hippo/index.htm

Suggested problems from the web: htt // http://www.engin.umich.edu/~cre/ i i h d / / Additional Homework Problems at each chapter

Example: Consider cell as a reactor. The nutrient corn steep liquor enters the cell of the microorganism Penicillium chrysogenum and is decomposed to form such products as amino acids, RNA and DNA. Write an unsteady mass balance on (a) the corn steep liquor, (b) RNA, and (c) pencillin. Assume the cell is well mixed and that RNA remains inside the cell.

Penicillium chrysogenum

Out Penicillin

Assumption: Penicillin is produced in the stationary state. no cell growth & nutrients are used in making the product.

22

Assuming steady state for the rate of production of penicilin in the cells stationary state, dN p =0 dt F Fout F V = in V = out rp rp Similarity, for Corn Steep Liquor with FC = 0

V = FC 0 FC F = C0 rC rC

Summary

Batch Flow

X=

( N A0 N A ) N A0

X=

(FA0 FA ) FA0

For irreversible reactions, the maximum value of conversion, X, is that for complete conversion, i.e. X = 1.0. For reversible reactions, the maximum value of conversion, X, is the equilibrium conversion, i.e. X = Xe.

23

dX N A0 = rA V dt

V=

X

CSTR

V = FA0

0

dX rA

PFR

Reactors in series

Space time

V v0

24

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