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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:

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

vs. X

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

5. Coolant Balance

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

3. Energy Balance

dE = dQ dW

rate of energy added to the system by mass flow

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:

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

i =1

H RX

(4) (5)

(6)

i0

i =1 n

(7)

H i = H i (TR ) + H Qi

o

(8)

o TR TR

TM

(9)

H Qi = C pi dT

T1 T o

T2

(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)

i =1

(13)

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

o

(14)

where H RX =

o

(15)

C p =

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

(16)

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.

H RX > C p (T - TR )

o

so X vs T is linear!!!

T=

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

o

C

i

pi

+ X C p

(19)

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.

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

(3) (4)

dFi

dV

H i = C pi dT

(5)

dT dH i = C pi dV dV

(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

F C

i

pi

dX - rA = dV FA0

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

10

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

mc

Tao

exothermic

dH c dT = Cp a dV dV

Tao

endothermic

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)

11

Exothermic Rxns:

Xe =

Kc 1 + Kc

Kc =

Kp ( RT )

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

12

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

Xe

Xeb

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

(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

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.

14

Consider:

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

CSTR

15

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

16

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:

Ta2

Ta:

where

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

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

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

i =1

dT = dV

F C

j=1 j

i =1 m

i : rxn j : species

pj

Ex:

Rxn 1 :

k1 A B k2 B C

CSTR

Q - W s + FA0

i =1

Q - W s + FA0

i =1

i n

i =1 q

UA(T a - T) + FA0

i =1 i =1

20

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