Summary - Design Equations of Ideal Reactors

Differential Equation Algebraic Equation Integral Equation

nj

Remarks
Conc. changes with time but is uniform within the reactor. Reaction rate varies with time. Conc. inside reactor is uniform. (rj) is constant. Exit conc = conc inside reactor.

Batch

dn j dt

= (r j )V

t=

n jO

(r )V
j

dn j

CSTR

V=

F jo F j (rj )

Fj

PFR

dF j dV

= rj

V=

F jO

dF j (rj )

Concentration and hence reaction rates vary spatially.

IdealIdeal-Reactor Design Equation Based on Mole Balance for SingleSingle-Reaction Systems

Basis of calculation
Consider the general reaction

aA + bB cC + dD
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.

Whats the limiting reactant?!!!

Definition of conversion
b c d A+ B C+ D a a a

How can we quantify how far the reaction proceeds to the right ??? How many moles of C are formed for every moles of A consumed ??? Convenient way is given!!! Conversion
batch reactor Moles of A reacted XA = Moles of A fed flow reactor XA = FA 0 FA FA 0 XA = N A0 N A N A0

Further Discussions on Conversion Maximum conversion for irreversible reactions

aA + bB cC + dD
For irreversible reactions, the maximum value of conversion, X, is that for complete conversion, i.e. X=1.0.

Maximum conversion for reversible reactions

aA + bB

cC + dD

For reversible reactions, the maximum value of conversion, X, is the equilibrium conversion, i.e. X=Xe.

Further Discussions on Conversion

Consider to example rate equations
rA = kC ACB
2 2 rA = kC ACB

rA =

k1C A k2 + KC A

Note that
rA = f (Concentration)

For only reaction occurring, Conc. can be expressed in term of X

We will discuss this issue in the later courses.

What is the relationship between X and rA ?

We need only -rA = f (X) and FA0 to design a variety of reactors ! The heart of the design of an ideal reactor: (-rA) as a function of conversion (concentration, partial pressure etc.) (We will discuss this issue in the later courses.)

Well develop the reactor design equation in term of conversion for single reaction system

Design eq. for batch reactor design

Consider to design equation of batch reactor
Where; (-rA) = moles A reacting / (unit volume) (time) V = Reactor volume, but really refers to the volume of fluid in reactor.

dnA dt = (rA )V

nA = nA0 (1 X A )

dnA0 (1 X A ) dt = (rA )V
nA0 dX A (rA )V

Design equation of batch reactor in conversion term

dt =

Or

nA 0

dX A = (rA )V dt

Integration form with t = 0 (XA=0) to t=t1 (XA=XA1)

X A1

t = nA0

dX A (rA )V

The longer the reactants are left in the reactor, the greater will be the conversion.

Design eq. for batch reactor design Batch:

n A0

dX = ( rA )V dt ? ?

The conversion is a function of the time the reactants spend in the reactor. We are interested in determining how long to leave the reactants in the reactor to achieve a certain conversion X.

-1/rA

dX Area = (rA ) t =0

V = t nA0

Design eq. for batch reactor design (For example)

We are planning to operate a batch reactor to convert A into R. This is a liquid reaction, the stoichiometry is A+R, and the rate of reaction is given in below Table. How long must we react each batch to achieve 90% conversion? The initial concentration of A is 2.0 M

Design eq. for batch reactor design (For example)

Specify problem: Determine time to achieve 90% conversion of the
bath reactor

Known
C A0 = 2.0 Mol/l

and

unknown

X = 0.9

Relation between rA and CA

V =? t =?

Basis: (1) Using A as the basis species

(2) Basis calculation based in 1 liter of batch reactor volume

Assumption: (1) Unsteady state operation

(2) Well-mixed condition (3) Constant volume (because of liquid reaction)

Design eq. for batch reactor design (For example)

25.00

0.9

t = C A0
I =

dX ( rA )
dX =? rA ) (

20.00 15.00

0.9

1/(-rA)

10.00 5.00

t = C A0 I

0.00 0.00 0.20 0.40 0.60 0.80 1.00

xi

Using numerical technique for integration to solve I

I = 14.87
t = 2.0 14.87 = 29.74 min

Numerical Evaluation of Integrals Integration with unequal segments Suitable for experimental data, in-equally space data points
I = f ( x)dx
a b

I h1

f ( x0 ) + f ( x1 ) f ( xn 1 ) + f ( xn ) f ( x1 ) + f ( x2 ) + h2 + ... + hn 2 2 2

where, f(x)
hi = ( xi xi 1 ) or the width of segments

xi

Relationship of molar/volumetric flowrate and molar/ concentration

The entering molar flow rate of species A, FA0 (mol/s), is just the product of the entering concentration, CA0 (mol/dm3), and the entering volumetric flow rate, v0 (dm3/s):
FA 0 = C A 0 v 0

For liquid system, CA0 is commonly given in terms of molarity, for molarity, example, CA0 = 2 mol/dm3 For gas system, CA0 can be calculated from the entering temperature and pressure using the ideal gas law or some other gas law. For an ideal gas law
CA0 = PA 0 y A 0 P0 = RT0 RT0 FA 0 = v 0 C A 0 = v 0 y A 0 P0 RT0

yA0 = entering mole fraction of A (-) P0 = entering total pressure (kPa) PA0 = yA0P0 = entering partial pressure of A (kPa) T0 = entering temperature (K) R = ideal gas constant (=8.314 kPadm3/molK)

Relationship of molar/volumetric flowrate and molar/ concentration

A gas of pure A at 830 kPa enters a reactor with a volumetric flow rate, v0, of 2 dm3/s at 500 K. Calculate the entering concentration of A, CA0, and the entering molar flow rate, FA0. Solution
C A0 = y A0 P0 (1)(830kPa) = = 0.20mol / dm3 RT0 (8.314dm3 kPa / mol K )(500 K )

FA0 = C A0 v0 = (0.2mol / dm3 )(2dm 3 / s ) = 0.4mol / s

This feed rate (FA0 = 0.4 mol/s) is in the range of that which is necessary to form several million pounds of product per year.

Design Equations for CSTR

Consider to design equation of CSTR reactor

FA 0 FA V= rA
FA = FA 0 (1 X)

FA0 FA

CA CA

CA

V=

FA 0 FA 0 (1 X ) rA

Because the reactor is perfectly mixed, the exit composition from the reactor is identical to the composition inside the reactor, and the rate of reaction is evaluated at the exit conditions.

V=

FA0 X (rA ) exit

Design Equations for PFR

PFR Design Equations FA dV FA +dF
b A+ B a l m L+ M a a

FA = FA 0 (1 X)
dFA = rA dV

dFA = FA 0 dX dFA = FA 0 dX

FA 0

dX = rA dV

differential form

V = FA 0

dX rA

integral form

Design Equations in Terms of Conversion

REACTOR DIFFERENETIAL FORM ALGEBRAIC FORM INTEGRAL FORM
X

BATCH

N AO

dX = ( rA )V dt

t = N AO
0

dX rAV

CSTR

V=

FAO ( X ) ( rA ) Exit

PFR

FAO

dX = ( rA ) dV

V = FAO
0

dX rA

Levenspiel Plots: Illustration of Reactor Sizing for Single-Reaction Systems

Octave Levenspiel

(PhD 1952): Octave Levenspiel also obtained an MS from Oregon State and served as a faculty member for 25 years until he retired in 1991. He published over 100 papers and proceedings, two of which have been listed as "Citation Classics." He was awarded 1977 American Institute of Chemical Engineers W.K. Lewis Award, the 1979 R.H. Wilhelm Award, and the 2003 Founders Award and Gold Medal, the highest honor given by the society. In 2000 he was inducted into the National Academy of Engineering. He also received two honorary doctorates , one from France.

He is considered to be one of the founders of Chemical Reaction Engineering.

SOURCE: http://engr.oregonstate.edu/oregonstater/fame/1998/che/octavelevenspiel.html

Levenspiel Plots: Sizing of CSTR

CSTR: We are interested in determining the size of the reactor to achieve a certain conversion X.
VCSTR
-1/rA Area =

[X ] = FA0 ( rA ) exit

1 X (rA )

Evaluate VCSTR by Levenspiel Plot

VCSTR = FA0 Area

Levenspiel Plots: Sizing of PFR

PFR: We are interested in determining the size of the reactor to achieve a certain conversion X.
1 dX (rA )
x = x PFR

VPFR =

x =0

FA0 dX rA

1 ( rA )

1 dX or Area = (rA )

X PFR

1 =0 (rA ) dX X

dX

Evaluate VPFR by Levenspiel Plot

XPFR

VPFR = FA0 Area

For example:
The isomerization reaction AB was carried out adiabatically in the liquid phase and the data in below table were obtained.
X (-rA) kmol/l.hr

0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.50 0.35 0.00

0.10 0.30 0.50 0.60 0.50 0.25 0.10 0.06 0.05 0.05 0.04

Calculate the volume of each of the reactors for an entering molar flow rate of species A of 50 kmol/hr. (a) Compare CSTR and PFR at 90% conversion (b) Compare CSTR and PFR volume at 65% conversion

For example:
CSTR: 90% conversion 90%
F X V = A0 ( rA ) exit
kmol l.hr V = 50 0.9 22.2 hr kmol

35.00 30.00 25.00

-1/rA

20.00 15.00 10.00 5.00 0.00 0.00 0.20 0.40 X 0.60 1/(-rA) 0.80 1.00 X

V = 1000 liter

PFR: 90% conversion 90%

V = FA0
X

dX ( rA ) 0
0.9

kmol dX V = 50 hr rA 0

V = 50 18.34 = 916.78 liter

0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.50 0.35 0.00

25.00 22.22 20.00 16.67 10.00 4.35 6.25 10.00 16.67 25.00 33.33

For example:
CSTR: 65% conversion 65%
V = FA 0 X ( rA )exit

35.00 30.00

-1/rA

25.00 20.00 15.00 10.00 5.00 0.00 0.00 0.20 0.40 0.60 X 0.80 1/(-rA) 1.00 X

km ol l .hr V = 50 0.65 6.25 hr km ol

V = 203 liter

PFR: 65% conversion 65%

V = FA0
X

dX ( rA ) 0
0.65

kmol V = 50 hr

dX rA

V = 50 15.07 = 753 liter

0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.50 0.35 0.00

25.00 22.22 20.00 16.67 10.00 4.35 6.25 10.00 16.67 25.00 33.33

Ideal Reactors in Series

- X1 at point i=1 is the conversion achieved in the CSTR - X2 at point i=2 is the total conversion achieved in at this point in the CSTR and the PFR - X3 is the total conversion achieved by all three reactors

For reactors in series, the conversion X is the total number of moles of A that have reacted up to that point per mole of A fed to the first reactor.
Total moles of A reacted up to point i Xi = Moles of A fed to the first reactor only be used when the feed stream only enters the first reactor in the series and there no side streams either fed or withdrawn.

Ideal Reactors in Series

CSTRs in Series
FA0 FA1 FA 2 X A1 X A2 rA1 rA 2

Reactor 1:
FA 0 FA1 + rA1V1 = 0

FA1 = FA 0 (1 X1 )

F V1 = A 0 X1 r A1

Reactor 2:
FA1 FA 2 + rA 2 V2 = 0

FA 2 = FA 0 (1 X 2 )

F V2 = A 0 (X 2 X1 ) r A2

Ideal Reactors in Series

CSTRs in Series: Levenspeil plot
-1/rA

VCSTR t = VCSTR 1 + VCSTR 2

F VCSTR 1 = A0 X 1 r A1 F VCSTR 2 = A0 ( X 2 X 1 ) r A2

-1/rA1 -1/rA2

X1

X2 X

1 1 V = FA0 X 1 + FA0 ( X 2 X 1 ) r r A1 A2

V = (FA0 AreaCSTR 1 ) + (FA0 AreaCSTR 2 )

***To achieve the same overall conversion, the total volume for two CSTRs in series is less than that required for one CSTR

Ideal Reactors in Series

CSTRs in Series (For Example)
For the two CSTRs in series, 60% conversion is achieved in the first reactor. What is the volume of each of the two reactors necessary to achieve 90% overall conversion of entering species A
X (-rA) kmol/l.hr

0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.50 0.35 0.00

0.10 0.30 0.50 0.60 0.50 0.25 0.10 0.06 0.05 0.05 0.04

Calculate the volume of each of the reactors for an entering molar flow rate of species A of 50 kmol/hr.

FA0 = 50kmol / hr

FA1 = FA0

FA 2 = FA0 X A 2 = 0.9

X A1 = 0.6

CSTRs in Series (For Example)

VCSTR t = VCSTR 1 + VCSTR 2 = 633.3
CSTR- 60% CSTR-1: 60% conversion
VCSTR 1 = FA 0 X 1 ( rA ) exit
35.00 30.00

VCSTR sin gle = 1000

liter

-1/rA

25.00 20.00 15.00 10.00 5.00 0.00 0.00

X

VCSTR 1 = 50

kmol l.hr 0.6 10 hr kmol

VCSTR 1 = 300 liter

0.20
1/(-rA)

0.40

0.60

0.80

1.00

CSTR- 90% CSTR-2: 90% conversion

VCSTR 2 = FA0 X 2 X1 ( rA )exit

VCSTR 2 = 50

kmol l.hr (0.9 0.6 ) 22.22 hr kmol

VCSTR 2 = 333.3 liter

0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.50 0.35 0.00

25.00 22.22 20.00 16.67 10.00 4.35 6.25 10.00 16.67 25.00 33.33

Ideal Reactors in Series

PFRs in Series

Vtotal = VPFR 1 + VPFR 2

=
X1 X2 dX dX FA0 + FA0 rA X 1 rA

It is immaterial whether you place two plug-flow reactors in series or have one continuous plug-flow reactor; the total reactor volume required to achieve the same conversion is identical.

Ideal Reactors in Series

PFRs in Series: Levenspeil plot
-1/rA

VPFR t = VPFR 1 + VPFR 2

VPFR 1 VPFR 2 VPFR 1 = FA0
VPFR 1 = FA0
X1 0

dX rA
dX rA

X2

X1

VPFR t =

X1

X2 dX dX FA0 + FA0 rA X 1 rA

VPFR t = (FA0 AreaPFR 1 ) + (FA0 AreaPFR 2 )

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

Ideal Reactors in Series

To achieve the same overall conversion, the total volume for two CSTRs in series is less than that required for one CSTR.

-1/rA

The overall conversion of two PFRs in series is the same -1/rA as one PFR with the same total volumn. CSTRs in series :A PFR can be modelled using a number of CSTR in series
useful in modelling catalyst decay in a packed-bed reactor modelling transit heat effects in PFRs.

Ideal Reactors in Series

Combined CSTRs and PFRs in Series CSTRCSTR-PFR in series

Vtotal = VCSTR + VPFR

VCSTR FA0 = r X1 A1
X2
2 X1 dX = FA0 ( r ) + FA0 ( r ) A A X1

VPFR = FA0

X1

dX rA

Vtotal

Ideal Reactors in Series

Combined CSTRs and PFRs in Series PFRPFR-CSTR in series

Vtotal = VPFR + VCSTR

VPFR = FA0
X1

dX rA

F VCSTR = A0 ( X 2 X 1 ) r A2

Vtotal

(X 2 X1 ) dX = FA0 + FA0 rA ( rA ) 0 2
X2

Ideal Reactors in Series

Combined CSTRs and PFRs in Series (For Example)
The isomerization of butane nC4H10iC4H10 was carried out adiabatically in the liquid phase and the data in below table were obtained. X 0 0.2 0.4 0.6 0.65 -rA [kmol/m3.hr] 39 53 59 38 25
It is real data for a real reaction carried out adiabatically, and the reactor scheme shown as below:

Calculate the volume of each of the reactors for an entering molar flow rate of n-butane of 50 kmol/hr.

Space Time & Residence Time

Time is of Essence

Two types of time-parameters are commonly used in chemical reaction engineering

space time residence time

Space time is often used as a scaling parameter in reactor design

Mole balance for flow reactor

Space time and space velocity of flow reactor
Reactor volume Actual Residence Time: The time actually spent by fluid inside the reactor.

Space time

Volumetric flow rate at entrance

** Sometime called mean resident time Space velocity

SV

0
V

LHSV - Liquid Hourly Space Velocity GHSV - Gas Hourly Space Velocity

** Measured at STP condition

Illustration of difference between space time () and residence time (tres) (t

The Pop Corn Example

Under what practical conditions do we expect space time = residence time ?

Class Assignment 2
(1)

(2)

Class Assignment 2 (3)

Class Assignment 2 (4)