ChE 471 LECTURE 8

Fall 2005

NONISOTHERMAL OPERATION OF IDEAL REACTORS Plug Flow Reactor

To Fjo, Qo Tm,Qm Tm T Fj Tm Tmo T

To

Assumptions: 1. 2. 3. Homogeneous System Single Reaction Steady State

Two types of problems: 1. 2. Given desired production rate, conversion and kinetics and other parameters, determine the required reactor size, heat duty and temperature profile. Given reactor size, kinetics, etc., determine the composition of the exit stream.

Let us consider a single reaction

s

"! A
j j =1

=0

(1)

with the rate given by

s s $j % " E 2 / RT # C j " k 20e # Cj j j =1 j =1

r = k10e

" E1 / RT

(2)

with
! C j = CAo M j /A "

#j xA To P #A 1 + $A x A TPo

(3)

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

dF j = " jr dV

(4) (4a) 1

v = 0 F j = F jo
!

or

ChE 471 LECTURE 8

Fall 2005

FAo

dx A = ("v A ) r = "RA dV
xA = 0

(4) (4a)

V =0

! The energy balance based on (a) negligible changes in potential and kinetic energy and (b) no work other than flow work is !

"

' d $ s v = 0 & F H # j j) )+q dV & % j =1 (

(5a)

(5)

1 = F jo H jo V = 0 FjH

!
!

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

"# F j C
j =1

~ pj

s dF j dT v = 0 " #H +q ~ dV j =1 j dV

(6a)

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

"(Q#)C p

dT v = 0 + ("$H r ) r + q dV

(6)

tot is the mass flow rate which is constant Q" = m

!
!

" J % v $ 3 ' is the rate of heat addition per unit reactor volume q # m s&

The simplest constitutive relationship for the rate of heat exchange is:
!
v = Uav (Tm " T ) q

(7)

" m2 % av $ 3 ' - area for heat transfer per unit reactor volume ! #m &

The equations to be solved simultaneously are:

!

dx A + "Ar = 0 dV v #q !# " # $ dT Q" C p m # (#$H r ) r + U av (T # Tm ) = 0 dV Fao !

2

(A) (B)

ChE 471 LECTURE 8

Fall 2005

!Qm " m C p m

#$ % dTm "$ # U av (Tm # T ) = 0 dV

v #q

(C)

V = 0; xA = 0; T = To, , (Tm = Tmo for cocurrent flow)

! V = V; (T = T for countercurrent flow) m mo

and
G du dp + +F =0 dz dz

(D)

(E)

G = "u - mass velocity

!

P = pressure

z=

V - axial distance A Q - velocity A

u= !

A cross sectional reactor area

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). The equations can then be written as:
G d" '' =r dz

(8)

G
!

dT = " '' r + q'' v dz

(9) (10) (11)

z=0
!

" '' = 0, T = To
#$H r Cp ; q'' v = qv Cp

" '' =

ChE 471 LECTURE 8

Fall 2005

where the rate is expressed by:

s

%j / 2. j =1 s 4 ' *$ j 1 T P m 1 $ " E1 / RT 1 4 j tot '' o r = k10e # C jo ) s )1 + % j F & , , 1 TP 4 jo + o 1 + .% j M av o & --4 j =1 ( 1 0 3 j =1 v s $ 1- j ' * j .T P m 1 $ bot '' 0 o 3 "k 20e" E 2 / RT # C joj ) )1 + % j F & , , 0 TP "" ( jo + / o 1 + - y M av o & 3 2 j =1

( )

(12)

M av o - average molecular weight at feed conditions

! m tot = GA mass flow rate

!
!

tot M j m = F jo w jo
wjo mass faction of j in the feed.

For liquids one can write

d" =r d# dT v = #r + q d"

(13)

(14) (15) (16)

" = 0 ; # = 0 ; T = To
!
!

= #$H r " %C p

'' qv Qv v = ; q = %C p %

where the rate is given by

!
r = k10e
" E1 / RT

s s &j 'j " E 2 / RT # (C jo + $ j% ) " k 20e # (C jo + $ j% ) j =1 j =1

(17)

"=
!

z V = - residence time along the reactor. u Q

ChE 471 LECTURE 8

Fall 2005

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

T = To + " ''# '' +

or

1 G

$ q dz
o

'' v

(18a)

# + % q v d$ T = To + "
o

(18b)

v = 0 ) this yields the equation of the adiabatic line, i.e extent and For adiabatic operation (q'v' = 0, q temperature satisfy the relationship below at any and every point of the reactor

T = To + " ''# '' # T = To + " ! !

(19a) (19b)

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

"Tad max To

=# =

($"H r )CAo ($% A )To & C p

(20)

Basic types of problems

! 1. The temperature in the reactor is prescribed

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

b.

2. The heat addition (removal) rate is prescribed a) Adiabatic operation. T = To + ! ' '" ' ' integrate

or T = To + !" . Substitute into eq (8) or (13) and

b)

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

1 T = To + " # + G
'' ''

$ q dz into (8) and integrate.

o

'' v

ChE 471 LECTURE 8

Fall 2005

3. Rate of heat addition (removal) controlled by another equation

v = Uav (T " Tm ) q

a) b)

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. ! ! by equations (A) to (E). Tm determined with T and

Gm

dTm = !" 'm (Tm # T ) dz

"m =

Uav m C pm

Gm =

Qm $ 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: hot spot formation parametric sensitivity and temperature runaway. Classical example of temperature runaway presented by Bilous & Amundson (AIChE J., 2, 117 (1956)). PFR cooled from the wall t constant Tm = Twall.
440
342.5

420 337.5 400

T
380

360 335 340 330 320 320 Tm = 300 300 0 10 20 30 310

!
6

ChE 471 LECTURE 8

Fall 2005

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. Approximate criteria are given on the enclosed graph. Example 1 A reversible first order reaction (considered earlier in a CSTR) is now to be per formed in a PFR.
" R (liquid phase) # k1 = 5 x10 8 e"12,500 / RT (min"1 ) A !

k2 = 3.4 x10 21 e"32,500 / RT (min"1 )

o #H r = "20,000 cal / mol #G298 = "2,500 cal / mol

$C p " 2,000 (cal / lit !C )

CAo = 2 ( mol / lit )

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

find final conversion in an isothermal reactor operated at 0, 10, 20, 100C determine conversion in an adiabatic reactor if the feed is at i) 0C, ii) 20C, if the maximum permissible temperature is 80C determine the optimal temperature profile along the reactor necessary to maximize exit conversion. 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.

b) c) d)

Solution a) For an isothermal reactor only the mass balance has to be solved
A V dx "= = CAo $ A Qo o # rA "rA = k1CA " k 2CR = CAo [ k1 (1 " x A ) " k 2 x A ] # x (1 " x Ae ) & k1 k1 (1 " x Ae ) "rA = k1CAo%1 " x A " A ( since k 2 = = x Ae K x Ae $ ' kC K k1 (" rA ) = 1 Ao ( x Ae " x A ) x Ae = = x Ae 1 + K k1 + k2

! !
!
!

ChE 471 LECTURE 8

Fall 2005

(" rA ) = ( k1 + k 2 )CAo ( x Ae " x A ) xA % x Ae ( 1 dx A 1 "= = !n' * $ k1 + k 2 o x Ae # x A k1 + k 2 & x Ae # x A ) !

Solve for conversion

!
$ 1 ' x A " &1 " exp(" k1 (1 + )# )) % K ( $ * "k -' 1500 = x Ae &1 " exp, 1 # /) #= = 15 min 100 + x Ae .( %

We get the following results: T ! 273 283 293 303 313 323 333 343 353 363 373 K 1494 407 121 40 13.5 5.0 2.0 0.81 0.35 0.16 0.08 k1 0.0498 0.112 0.239 0.486 0.943 0.755 3.149 5.46 9.17 15.0 23.8 xae 0.999 0.998 0.992 0.975 0.931 0.833 0.662 0.448 0.262 0.139 0.071 xa 0.526 0.813 0.965 0.974 0.931 0.833 0.662 0.448 0.262 0.139 0.071 Same as equilibrium conversion The reactor space time is so large that above 50C practically equilibrium conversion is obtained. a) The adiabatic operating line is
C x T = To + " A Ao A & ! ) = #$H rA = 20,000 = 10( lit C + " A %C p 2,000 ' mol * & mol ) CAo = 2( + ' lit * T = To + 20 x A

ChE 471 LECTURE 8

Fall 2005

Substitute this relationship into the mass balance and integrate:

dx A = ( k1 + k 2 )CAo ( x Ae # x A ) = k1CAo # ( k1 + k 2 )CAo x A d" " = 0 xA = 0 CAo ! !

k1 = k10e E1 / RTad = k10e" E1 / R (To + 20 x A ) k2 = k 20e" E 2 / R (To + 20 x A )

x Ae = K k1 = 1 + K k1 + k 2

!
!

Thus integrate numerically

dx A #E / R T = k10e# E1 / RT (To + 20 x A ) # k10e 1 ( o+20 xA ) + k 20e# E 2 / R (To + 20 x A ) x A ; " = 0 d"

xA = 0

12,500 12,500 32,500 $ ' # # # dx A 21 1.987(To + 20 x A )x A ; " = 0 ; x A = 0 = 5 x10 8 e 1.987(To + 20 x A ) # &5 x10 8 e 1.987(To + 20 x A ) + 3.4 x 10 e ! d" & ) % (

Desired result is obtained at ! = 15.

! Alternatively we could solve by trial and error the following integral:

xA

" = 15 =

*
o

dx 5 x10 e
12,500 # 8 1.987(To + 20 x ) 12,500 32,500 $ ' # # 8 1.987(To + 20 x ) 21 1.987(To + 20 x ) )x # &5 x10 e + 3.4 x10 e & ) % (

We find:

i) ii)
! c)

To = 0C = 273 K xA = 0.78 "Tadiabatic = 15.7K = 16K T = 289 K To = 20C = 293 K xA = 0.94 = xAe "Tadiabatic = 18.8 = 19K T = 292K

To maximize conversion at given space time we should follow the line of maximum rates.
! Tm =

( E 2 " E1 / R) 10,065 = # x & k E x !n 20 2 + !n A 30.51 + !n% 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.

ChE 471 LECTURE 8

Fall 2005

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.
T = 353 = Tm = 10,065 # x & 30.51 + !n% A ( $1 " x A '

#10,065 " 353 x 30.51& exp % ( $ ' 353 xA = = 0.119 #10,065 " 353 x 30.1& 1 + exp% ( $ ' 353
% x Ae ( 1 0.119 dx 1 "= = !n' * $ k1 + k 2 o ( x Ae # x A ) ( k1 + k 2 ) & x Ae # x A )

At 80C (353 K) from the table given earlier

!

"=

$ ' 0.262 !n& ) = 0.017(min) 1 9.17(1 + ) % 0.262 # 0.119 ( 0.35 1

The isothermal operation should occur in the very entry section of he reactor. After that the Tm line should be followed.
# # dx A = 5 x10 8 e 1.987Tm (1 # x A ) # 3.42 x10 21 e 1.987Tm x A d" 10,065 Tm = $ x ' 30.51 + !n& A ) %1 # x A ( " = 0.017 x A = 0.119 12,500 32,500

! !

Desired result at ! = 15 xA=0.988 Texit = 288K

Really one should preheat only to adiabatic line. Adiabatic line should end at T = 353 K, xA = 0.119. C x = 353 ! 20 x 0.119 = 350 K Hence, the fluid must be preheated up to To = T ! " A Ao A

10

ChE 471 LECTURE 8

Fall 2005

The graphical representation of parts (a-c) has the following form:

xA

x Ae

a.

Isothermal. Solid lines are operating lines for ! = 15 min

!

xA

!
x Ae

b.

Adiabatic. Adiabatic line with ! = 15

!
xA
Tm

x Ae

Tmax

c. d)

Operating along the locus of maximum rates

!

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

11

ChE 471 LECTURE 8

Fall 2005

x A = 0.85

"=

*
o

dx 5 x10 e
12,500 # 8 1.987Tm

$ &5 x10 e & %

12,500 # 8 1.987Tm

+ 3.4 x10 e

21

32,500 1.987Tm

' )x ) (

10,065 # x & 30.51 + !n% A ( $1 " x A ' ! " = 1.8min Thus with Q = 100 lit/min we need only V = 160 liters

with

Tm =

The desired temperature profile along the reactor is presented in the enclosed graph. The heat removal ! per unit volume is

q = #C p (To " T ) + ("$H r )CAo x A Q = 2,000(100 " T ) + (20,000 x 2) x A "

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

#q & "% ( = 2,000(100 " 70) + 40,000 x 0.85 $ Q ' tot = 1.56 x10 5 (cal / lit )

With Q = 100 lit/min

tot = 1.56 x10 7 (cal /min) "q

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

! T = 126 ! C x A adiabatic = 0.068, exit

The adiabatic temperature profile is shown also on the enclosed figure.
!

12

ChE 471 LECTURE 8

Fall 2005

Extension to Multiple Reactions

s

#"
j =1

ij

Aj = 0

i = 1,2,...R

(1)

dF j R " + $# ij ri = 0 dV i=1
or
R

j = 1,2,...R

(2)

i R dX "$# ij + $# ij ri = 0 dV i=1 i= 1 dX " i + ri = 0 dV

(2a)

"

j) d( F j H dV

v = 0 +q

(3)

i = X io ) ; H j =H jo V = 0 ; F j = F jo ( X

!
!

With the usual assumptions made about the energy balance (see the lecture on CSTR) one gets:
dT R v = 0 "# F jo C + # ("$H rTi )ri + q ~ p j dV j =1 i= 1
s

(4)

The equations to be solved for a set of multiple reactions are:

! " i dX + ri = 0 dV i = 1,2...R

(A)

! !
with
!

dT R v = 0 + % ("$H ri ) ri + q dV i=1 i = X io T = To V =0 ; X "Q = const s s $ ij % " E1 i / RT " E 2 i RT ri = ki10e # C j " k i 20e # C j ij j =1 j =1 "# C p Q

(B)

(C)

13

ChE 471 LECTURE 8

Fall 2005

R % ( ' # X $ ij i * ' 1 + i=1 * ' * F jo "T C j = C jo o ' * R s " oT ' i * $ $# ij X ' * i= 1 j =1 '1 + * Fbot o ) &

(D)

v is: The constitutive relationship for q

!

v = U a v (Tm " T ) q
a) Tm= const

b) Tm is governed by another D.E.

! " m Qm C p m

dTm v = 0 #q dV

(E)

V = 0 Tm = Tmo (cocurrent flow)

V=V Problems

Tm = Tmo (countercurrent flow)

" R #

Consider the reaction introduced in the last lecture A R=k1CA-k2CR (mol/lit s)

# 83,700 & 3 k1 = exp% 7 " ( x10 (s-1) $ RT ' # 167,400 & 3 k2 exp%18 " ( ) 10 (s-1) $ RT '
"H r = #80,000 ( J / mol) C = 40( J / mol K )
~ p

!
! 1.

(Activation energies given in joules)

The above reaction occurs in liquid phase! Permissible temp range of operation is 300<T<900 K. Feed conditions: Qo = 100 (lit/s) ; To = 300 K ; CAo = 1(mol/lit)

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. 14

ChE 471 LECTURE 8

Fall 2005

a) b) c) d) e) 2.

What is maximum FR. What are final x A and "T . What is the profile of heat addition or removal for every 10% of reactor volume.
! What is the overall heat duty for the reactor and any heat exchangers preceding it.

Sketch your system.

The above reaction occurs in gas phase. The gas feed ate is
Qo = 100( lit / s) at To = 300K , Po = 24.6 atm

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%. a) b) c) 3. 4. What reactor volume is needed if you operate along the locus of maximum rates? What is the distribution of heat duty along the reactor? What is the production rate of R?

For the above problem what would FR and xA be if you had a reactor (PFR) of V = 100 liters available? Suppose that the reactor can only be operated adiabatically and the desired conversion is 85%. Minimize the required reactor size. a) b) c) What reactor type do you recommend? What feed temperature would you use? What is the heat duty?

15