Ch 8: Steady State Non-isothermal Reactor Design

Energy Balances, Rationale and Overview Calculate the volume necessary to achieve a conversion, X, in a PFR for a firstorder, exothermic reaction carried out adiabatically. For an adiabatic, exothermic reaction the temperature profile might look something like this:

The combined mole balance, rate law, and stoichiometry yield:

To solve this equation we need to relate X and T. We will use the Energy Balance to relate X and T. For example, for an adiabatic reaction, energy balance can be written in the form

, the

set X, then calculate T, -VA, and

, increment X, then plot

vs. X

1. Adiabatic (Q = 0); CSTR, PFR, Batch and PBR:

2. CSTR with heat exchanger, UA(Ta-T) and large coolant flow rate.

3 . PFR/PBR with heat exchange

3A. In terms of conversion, X

3B. In terms of molar flow rates, Fi

4. For Multiple Reactions

5. Coolant Balance

These are eqns we will use to solve rxn engineering problems with heat changes.

3. Energy Balance

Typical units for each term are J/s; i.e. Watts

Energy Balance 1st Law of Thermodynamics:

dE = dQ dW

(for a closed system)

Energy of the system

Heat flow to the system

Work done by the system on the surroundings

dE = Q W + Fin E in - Fout E out 123 dt

rate of energy added to the system by mass flow

{for an open system}

Evaluation of the Work Term:

W = Wf + Ws
flow
n

shaft
~

= Fi P V i
i =1 in

+ Fi P V i
i =1 out

+ Ws

Combining with

Hi = Ui + P Vi
n n

dE sys dt

= Q+ W s Fi H i in + Fi H i out
i =1 i =1

(1)

1. 2. 3. 4. 5. 6.

Replace Ei by Ei=Hi-PVi Express Hi in terms of enthalpies of formation and heat capacities Express Fi in terms of either conversion or rates of reaction Define HRX Define CP Manipulate so that the overall energy balance is either in terms of the Equations above 1.A, 1.B, 2, 3A, 3B, or 4 depending on the application

Step 1:
Substitute , and

into equation (1) to obtain the General Energy Balance Equation. General Energy Balance:

For steady state operation:

We need to put the above equation into a form that we can easily use to relate X and T in order to size reactors. To achieve this goal, we write the molar flow rates in terms of conversion and the enthalpies as a function of temperature. We now will "dissect" both Fi and Hi. Flow Rates, Fi For the generalized reaction:

(2) In general,

Fi = FA0 (i + i X)

where i =

Fi0 FA0

(3)

A = -1 B = -

b a

C =

c a

D =

d a

Then

H
i =1

i0

Fi0 - H i Fi = FA0 [(H A0 - H A ) + (H B0 - H B ) B ] + ...........

i =1

H RX

n n = FA0 [(H i0 - H i ) i ] - ( i H i ) FA0 X 1 4 2 43 i =1 i =1 H RX d c b = HD + HC - HB - HA a a a H i0 Fi H i = FA0 i (H i0 - H i ) - H RX (T) FA0 X

(4) (5)

(6)

i0

dE for st - st = 0; combining (1) and (6) : dt Q - W + FA0 i (H i0 - H i ) - H RX (T) FA0 X = 0

i =1 n

(7)

If a phase change takes place, it will be included in H RX .

Assuming no phase change:

H i = H i (TR ) + H Qi
o

(8)

Enthalpy of formation at TR (ref. temp.)

Change in enthalpy when T is changed from TR to T.

If there is a phase change:

H i = H i (TR ) + C ps,i dT + H mi (Tm ) + C pl,i dT

o TR TR

TM

(9)

H Qi = C pi dT
T1 T o

T2

(if no phase change)

(10)

H i = H i (TR ) + C pi dT
TR

(11)

Cp = i + i T + i T 2

H i H i0 =

Ti0

C
n

pi

dT = C pi [T - Ti0 ]

(12)

Substitute into (7) : Q - W + FA0

i =1

C pi [T - Ti0 ] - H RX (T) FA0 X = 0

(13)

Combine eqn (11) & (5)

H RX = H RX + C p (T - TR )
o

(14)

where H RX =
o

d c b o o o o H D (TR ) + H C (TR ) - H B (TR ) - H A (TR ) a a a

(15)

C p =

d c b C pD + C pC - C pB - C pA a a a

(16)

Combine (13) and (14)

Q - W + FA0 i C pi [T - Ti0 ] - H RX + C p (T - TR ) FA0 X = 0

o i =1

(17)

Adiabatic Operation:
Ws = 0 Q=0

X=

- HRX + Cp (T - TR )

C
i o

pi

(T - Tio )

]
for an exo. rxn why does X increase? This is from E balance, not mole balance.

for an exothermic, adiabatic rxn

H RX > C p (T - TR )
o

so X vs T is linear!!!

Adiabatic Tubular Reactor Rearrange (18):

T=

X - H RX + i C pi To + X C p TR
o

C
i

pi

+ X C p

(19)

Combine with differential mole balance:

FA0

dX = - rA (X, T) dV

(20)

To obtain T, X and concn profiles along the reactor! Use (19) to construct a table of T vs X. Obtain k(T) as a function of X -rA as a function of X. Look at Table 8-2A.

Steady State Tubular Reactor with Heat Exchange:

Q = U A (Ta - T) = Ua (Ta - T) V
FA0 To

assume Ws = 0
FAe Te

F H
i

F H
i

V+V

Q+ Fi H i

Fi H i

V + V

=0

(1)

The heat flow to the reactor Q Overall heat transfer coefficient (U) Heat exchange area (A) Difference between ambient temperature (Ta) and reactor temperature (T)

Q = U A (Ta - T) = Ua V (Ta - T)
A 4 = V D
Diameter of reactor

(2)

If V 0

Ua (Ta - T) = mole balance : diff. Eq' n (3) Ua (Ta - T) =

d (Fi H i ) dV dFi = ri = i (-rA ) dV H i - Fi dH i dV

(3) (4)

dFi
dV

H i = C pi dT
(5)

dT dH i = C pi dV dV

(6)

Combine (5) & (4) & (6)

dT Ua (Ta - T) = i H i (-rA ) - Fi C pi 1 4 2 43 dV
H RX

(7)

 Rearrange:
Heat generated removed 6 4 7 48 6 Heat 47 48 dT rA H RX Ua (T - Ta) = dV Fi Cpi

(8)

Fi = FA0 ( + i X)
Substitute into (8)

dT Ua (Ta - T) + rA H RX = dV FA0 ( i + i X + C p X )

{for a PFR}

Ua
for a PBR {dW = b dV}

dT = b dW

(Ta - T) + (rA ') H RX

F C
i

pi

These eqns will be coupled with mole balance eqns

dX - rA = dV FA0

Balance on the Coolant Heat Transfer Fluid:

Heat transfer fluid Tao

R2 R1

FA0, To
V V + V

Reactants

The fluid will keep the rxn temperature constant for endo/exo thermic rxns You might have A. Co current Flow B. Counter current Flow

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A. Co Current Flow The Energy Balance

Ta: coolant temperature mc, Hc mc, Hc

E in
V

- E out
V + V V

+ Q conduction = 0 + Ua (T - Ta) V = 0
V + V

FA, T
V

FA, T

mc Hc - mc Hc

V + V

Divide by V and take limit as V 0

mc

dH c + Ua (T - Ta) = 0 dV dTa Ua (T - Ta) = dV mc Cp

Tao

exothermic

dH c dT = Cp a dV dV

Tao

endothermic

B. Counter Current Flow

Ta2 Ta

FAo, To

T
V V + V

dTa Ua (Ta - T) = dV m c C pc

V=0

V = Vf

At the entrance X = 0; V = 0; Ta = Ta2 At the exit V = Vf; Ta = Tao The soln to the counter-current flow problem to find {T X} is a trial & error procedure. Assume a coolant temp at the entrance (Ta2) Solve ODEs to calculate X, T and Ta as a function of V: Find Ta(V = Vo)

If Ta (V = Vo ) - Ta2 < Ta (V = Vo ) = Ta2 Else assume another Ta2

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Equilibrium Conversion As T As T X X {For endothermic rxns} {For exothermic rxns}

Exothermic Rxns:

Xe =

Kc 1 + Kc

{1st order rxn}

From Le Chaltliers Law (Kc as T if H<0) exothermic

Kc =

Kp ( RT )

To find the max X in an exothermic rxn carried adiabatically:

Energy balance To1 >To Xe Xe1

Xe =

C pi (T - To )

H RXN (T )

if To is changed to To1 Xe as T
To1 Adabatic temperature

To

~ dlnK o H (T) H RXN (TR ) + C p (T - TR ) p RXN = = dT R T2 R T2 ~ if C 0 = p o 1 1 K (T ) = K (T ) exp H RXN (TR ) p 1 p 2 R T1 T2

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To increase the conversion in an exothermic rxn, use multiple reactors with interstate cooling:

Xe
Xeb

For Endothermic Rxn (you need heating)

Xe

Optimum Feed Temperature Adiabatic Reactor of fixed size Reversible & Exothermic Rxn
X

T = To -

H rx X C pA ;T

if H rx < 0 as X
2

350

500

600

T, K

As T

Xe

but the (-rA) decreases!

(so the conversion is achieved at the end of the reactor) So there must be an optimum temperature to achieve max X. Curve A: Rxn rate slow, rxn dictated by rate of rxn and reactor volume As T ,r ,X Curve B: Rxn rate very rapid. Virtual equilibrium reached in X dictated by equilibrium conversion

13

Adiabatic Rxn Algorithm Suppose 1. Choose X Calculate T

Calculate k Calculate T/To Calculate CA

Calculate CB

Calculate KC

Calculate -rA 2. Increment X and then repeat calculations. 3. When finished, plot vs. X or use some numerical technique to find V.

Levenspiel Plot for an exothermic, adiabatic reaction.

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Consider:

PFR Shaded area is the volume. For an exit conversion of 40% For an exit conversion of 70%

CSTR

Shaded area is the reactor volume. For an exit conversion of 70%

For an exit conversion of 40%

We see for 40% conversion very little volume is required. CSTR+PFR

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For an intermediate conversion of 40% and exit conversion of 70%

Looks like the best arrangement is a CSTR with a 40% conversion followed by a PFR up to 70% conversion.

Evaluating the Heat Exchanger Term

Energy transferred between the reactor and the coolant:

Assuming the temperature inside the CSTR, T, is spatially uniform:

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At high coolant flow rates the exponential term will be small, so we can expand the exponential term as a Taylor Series, where the terms of second order or greater are neglected, then:

Since the coolant flow rate is high, Ta1

Ta2

Ta:

Multiple Steady States (MSS)

where

Heat generated term

Heat removed term

17

R(T): Varying Entering Temperature R(T) Slope = Cpo (1+) Increase To T Vary non-adiabatic parameter : if you increase FA0 (molar flow rate) or decrease heat exch area then will decrease R(T) = = 0 decrease
Ta To

Ua = FA0 C p0 T + Ta Tc = 0 1+

G(T)
High E Low E

G(T)

G(T)

increasing T

For a first order rxn:

X=

k 1+ k

18

Ignition Extinction Curve: The point of intersection of G(T) and R(T) give Tst-st. By plotting Tst-st vs To, we obtain ignition extinction curve.

Upper st-st

As To

Tst-st

Lower st-st

Ignition temp Extinction temp

Runaway Rxns in a CSTR:

R(T), G(T)

Tc =

T0 + Ta 1+

Tc

T*

Tangency point

Trc = T * - Tc =
Reactor T

R T *2 E

if this diff. is exceeded, transition to the upper st st will occur. At this high temp, it is undesirable or even dangerous.

19

PFR

dT Ua (Ta - T) + (-rA )(-H Rxn (T)) = m dV Fi Cpi

i =1

(for a single rxn)

When q multiple rxns occur with m species:

dT = dV

Ua (Ta - T) + (-rij ) - H Rxn,ij (T)

F C
j=1 j

i =1 m

i : rxn j : species

pj

Ex:

Rxn 1 :
k1 A B k2 B C

dT Ua (Ta - T) + (-r1A )[- H Rxn,1A (T) ] + (-r2B )[- H Rxn,2B (T) ] = dV FA C pA + FB C pB + FC C pC

CSTR

Q - W s + FA0

i =1

C pi [T - T0 ] - [ H RXN (T) ] [rA V ] = 0

(for a single rxn)

When q multiple rxns take place

Q - W s + FA0

i =1

i n

C pi [T - T0 ] - V rij H RXN, ij (T) = 0

i =1 q

UA(T a - T) + FA0

i C pi [T - T0 ] - V rij H RXN, ij (T) = 0

i =1 i =1

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