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CHENG 323 Dr Shaker Haji

CHENG 322 1

Dr. Shaker Haji, University of Bahrain 3/29/2012

In this Chapter

because most rxns are not carried out isothermally.

We will derive user friendly Energy Balance Equation & apply it to

the following cases:

Adiabatic

Heat Exchange with Constant Ta (ambient/coolant T)

Heat Exchange with Variable Ta Co-current Flow

Heat Exchange with Variable Ta Counter Current Flow

8.1 Rationale

CA

CHENG 322 2

Dr. Shaker Haji, University of Bahrain 3/29/2012

8.1 Rationale

Through mole balance, rate law, stoichiometry:

dX dP

F1 (X , P ,T ) F2 (X , P )

dW dW

dT

What else is needed? F3 (X ,T )

dW

How is it obtained?

The Law of Conservation of Energy

physics.

What does is state?

Energy can neither be created nor destroyed, it can only be

transformed from one form to another.

Because energy is conserved:

Accumulation = Input Output

This eq. is valid whether the system involves a chemical rxn

or not!

CHENG 322 3

Dr. Shaker Haji, University of Bahrain 3/29/2012

The 's signify that Q & W are not exact differentials of a state function.

E is the total energy of the system

For an open system, the energy balance for the case of one

species entering and leaving (e.g. J/s):

system that has n species, each entering and leaving the

system at their respective Fi & Ei, is

Equation

CHENG 322 4

Dr. Shaker Haji, University of Bahrain 3/29/2012

and other work, W s.

W s , shaft work, include stirring (CSTR), rotation (gas

turbine), and also electrical heating.

Flow work is work that is necessary to get the mass into and

out of the system.

For example, when shear stresses are absent, we write

Ei = Ui + PEi + KEi

Therefore, Ei + PVi = Ui + PEi + KEi + PVi or?

= Hi + PEi + KEi

In almost all chemical reactor situations, the KE & PE terms

are negligible in comparison with the other terms.

CHENG 322 5

Dr. Shaker Haji, University of Bahrain 3/29/2012

to Obtain the Heat of Reaction

CHENG 322 6

Dr. Shaker Haji, University of Bahrain 3/29/2012

By substitution:

Its called the Heat of Reaction at temperature T, Hrxn

Therefore,

to Obtain the Heat of Reaction

Does this Eq. account for the phase change within the reactor?

Yes, through (Hi0 Hi).

Thus, If a phase change takes place during the course of a

reaction, this form of the energy balance must be used

n

FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W

i 1

CHENG 322 7

Dr. Shaker Haji, University of Bahrain 3/29/2012

ideal & nonideal)?

No, because we are neglecting any enthalpy changes resulting

from mixing.

We simply assumed that the partial molar enthalpies are equal to

the molar enthalpies of the pure components.

n

FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W

i 1

For the extreme case, where the reactants are at the solid phase

@ T0 and the products are the gaseous phase @ T:

(Hi Hi 0) = CPl

T0 i

T

(Hi Hi 0) = C Pi dT ; If CPi is constant, then: (Hi Hi 0) = CPi (TT0)

T0

CHENG 322 8

Dr. Shaker Haji, University of Bahrain 3/29/2012

n

FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W

i 1

Hrxn(T ) i.Hi(T ) or

In general:

H rxn

o

(T R )

This Eq. gives the heat of rxn at any T in terms of the standard heat

of rxn (1 bar) at a reference T (usually 298 K) & the CP term.

Techniques for determining Hrxn at P above 1 bar can be found

elsewhere.

However, for the rxn of H2 & N2 at 400oC, it was shown that Hrxn

increased by only 6% as P was raised from 1 atm to 200 atm!

CHENG 322 9

Dr. Shaker Haji, University of Bahrain 3/29/2012

n

FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W s

i 1

n

FA0 i C P i T i T i 0 (FA0 X ) H rxn

o

(T R ) C P T T R Q W s

i 1

In most systems:

Work is neglected

All reactants enter at the same temperature (T0 ), so is the case for the

leaving products (T ).

o

(T R ) C P T T R Q

capacities.

This Eq. can be used to relate T to X and then proceed with the CRE

algorithm.

However, unless the rxn is carried out adiabatically, this Eq. is still

difficult to evaluate! Why?

Because in nonadiabatic reactors, the heat exchanged with the system

varies along the length of the reactor.

This problem does not occur in adiabatic reactors, which are

frequently found in industry.

Therefore, the adiabatic reactors will be analyzed first.

CHENG 322 10

Dr. Shaker Haji, University of Bahrain 3/29/2012

Calculate the heat of reaction for the synthesis of NH3 from H2 & N2 at

150oC in kcal/mol of N2 reacted and also in kcal/mol of H2 reacted.

Additional information:

CP of gases: NH3: 8.92, N2: 6.984, and H2: 6.992 cal/mol.K.

CP of liquid NH3: 30.0 cal/mol.K.

Hvap of NH3: 5.581 kcal/mol at Tn = 33.4oC.

Hof (25oC) of NH3: 11,020 cal/mol.

Solution

N2 + 3H2 2NH3 H rxn (T ) H rxn

o

(TR ) CP T TR

Horxn (150oC) = 22,040 + (10.12)(125K) = 22,040 1,265

=23.31 kcal/mol N2 = 7.77 kcal/mol H2

reactors?

Reactions in industry are frequently carried out

adiabatically with heating or cooling provided either

upstream or downstream.

Consequently, analyzing and sizing adiabatic reactors is

an important task.

CHENG 322 11

Dr. Shaker Haji, University of Bahrain 3/29/2012

o

(T R ) C P T T R Q W

of an adiabatic PFR using a thermocouple!

reactor.

Feed in stoichiometric ratio, T0=500oC CP = 10.12 cal/mol

0.2

XEB = X 0.15

calculated

through energy 0.1

XEB

balance

0.05

Almost linear

relationship 0

500 550 600 650 700

T (oC) @ adiabatic PFR exit

CHENG 322 12

Dr. Shaker Haji, University of Bahrain 3/29/2012

Balance Eq. and the one in Thermo I & II textbook?

n

FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W s

i 1

o

(T R ) C P T T R Q W

CHENG 322 13

Dr. Shaker Haji, University of Bahrain 3/29/2012

Isobutane is a valuable product that is used in the manufacture of gasoline

additives. For example, isobutane can be further reacted to form iso-

octane. The 2004 selling price of n-butane was 72 cents per gallon, while

the price of isobutane was 89 cents per gallon.

The rxn is to be carried out adiabatically in the liquid phase under high

pressure using essentially trace amounts of a liquid catalyst which gives a

specific reaction rate of 31.1 h1 at 360 K.

Calculate the PFR and CSTR volumes necessary to process 100,000 gal/day

(163 kmol/h) of a feedstock containing 90 mol% n-butane & 10 mol%

i-pentane (inert). Also calculate the equilibrium conversion in the reactor.

The feed enters at 330 K.

CHENG 322 14

Dr. Shaker Haji, University of Bahrain 3/29/2012

Information:

liquid phase rxn, Q = 0, k = 31.1 h1 at 360 K, T0 = 330 K

FA0 = 0.9X163 = 146.7 kmol/h Feed: 90% A, 10 % inert (mol)

Additional Information:

Solution

Solution

1. Mole balance: PFR: CSTR:

2. Rate law: ,

From energy balance:

FA0 i C P i T T 0 (FA0 X ) H rxn

o

(T R ) C P T T R Q W

Therefore, T T 0 H rxn

o

X C i Pi

CHENG 322 15

Dr. Shaker Haji, University of Bahrain 3/29/2012

3. Stoichiometry:

4. Combine:

Yes, then evaluate as much parameters as possible.

How do you find equilibrium conversion?

CBe CA0 X e

From K C KC

C Ae CA0 (1 X e )

Hand Calculation

T T 0 H rxn

o

X C

i Pi

CHENG 322 16

Dr. Shaker Haji, University of Bahrain 3/29/2012

Hand Calculation

Make sure that the requested X is not greater than Xe.

Its better to ask for X in relative to Xe, such as 0.95Xe.

For 40% X, VCSTR < VPFR (VCSTR = 1, VPFR = 1.15 m3)

Computer Calculation

CHENG 322 17

Dr. Shaker Haji, University of Bahrain 3/29/2012

added or removed through the cylindrical walls of the reactor.

Again, we shall assume that there are no radial gradients in the

reactor.

The heat flux through the wall

of the reactor is:

Q U A (T a T )

U a (T a T )V

SI Units:

U [J/(s m 2 K)], U A [J/(s K)]

U a [J/(s m3 K)]

For the shown system, carry out an energy balance on the volume V.

CHENG 322 18

Dr. Shaker Haji, University of Bahrain 3/29/2012

For membrane reactors and multiple reactions (Non-isothermal

reactor with heat exchange).

recall that W = b.V

CHENG 322 19

Dr. Shaker Haji, University of Bahrain 3/29/2012

isomerization of n-butane process discussed in Example 8-3.

The T in thiss case will raise to 360 K at the reactor exit. At this T, a P

of 1.5 MPa is generated (Vapor Pressure) which is greater than the

rupture pressure of the glass vessel being used.

So what do you suggest?

suggested to:

1. Use partially insulated tubular reactors instead of the insulated ones

2. Lower the Feed T

Fortunately, there is a bank of ten partially insulated (U.a = 5000

kJ/h.m3.K) tubular reactors each 6 m3 over in the storage shed

available for use. We are also going to lower the entering

temperature to 310 K.

The reactors are cooled by natural convection where average ambient

T in this tropical location is assumed to be 37C. The T in any of the

reactors cannot rise above 325 K. Plot X, Xe, T, and the reaction

rate along the length of the reactor. Does the temperature rise

above 325 K?

Solution

CHENG 322 20

Dr. Shaker Haji, University of Bahrain 3/29/2012

Does the

temperature rise

above 325 K?

usually called?

coolant for exothermic rxns

When the heat transfer fluid maintains a constant T & when it does not?

If the flow rate of the heat transfer fluid is sufficiently high with

respect to the heat exchanged with the reacting mixture, then the heat

transfer fluid temperature will be constant.

Otherwise, T of heat transfer fluid (Ta) will vary along the

length of the reactor.

Derive a differential equation for Ta wrt to V.

CHENG 322 21

Dr. Shaker Haji, University of Bahrain 3/29/2012

Case A: Co-Current Flow:

Assume cooling case:

, from CP definition:

manufacturing facility, states that one of the key steps is the

vapor-phase cracking of acetone to ketene and methane:

that specific reaction rate can be expressed by

34222

k 8.19733 10 e 14 T

where k is in s1 and T is in K.

(37.6 mol/s) in a tubular reactor. The reactor consists of a bank of

1000 1-inch schedule 40 tubes (ID=2.66 cm) arranged in parallel

where each tube is 90 cm long (V = 5x104 m3).

CHENG 322 22

Dr. Shaker Haji, University of Bahrain 3/29/2012

CASE 1: The reactor is operated isothermally (calculate the Q required

to maintain this operation).

CASE 2: The reactor is operated adiabatically.

CASE 3: The reactor is surrounded by a heat exchanger where the heat-

transfer coefficient is 110 J/m2.s.K, and the T of the heating medium, Ta,

is constant at 1250 K.

CASE 4: The heat exchanger in Case 3 now has a variable Ta. The

reactant and the heating medium flow in the same direction.

CASE 5: Same as Case 4, but the reactant and the heating medium flow

in opposite directions.

In the last two cases, air (CPair = 34.5 J/mol.K) at a rate of 0.11 mol/s

with Ta0 = 1250 K is available for heating.

The inlet T & P are the same for all cases at 1035 K & 162 kPa,

respectively.

Horxn(298K)= 80.77 kJ/mol; CPA= 163, CPB= 83, & CPC= 71 J/mol.K.

Plot X, rA, T, & Ta along the length of the reactor.

Case 1:

Isothermal Operation

Conversion

(Xexit=0.50)

Rate of Reaction

Temperature

CHENG 322 23

Dr. Shaker Haji, University of Bahrain 3/29/2012

Case 2:

Adiabatic Operation

Conversion

(Xexit=0.16)

Rate of Reaction

Temperature

Case 3:

With Heat Exchange

Constant Ta

Conversion

(Xexit=0.57)

Rate of Reaction

Temperatures

CHENG 322 24

Dr. Shaker Haji, University of Bahrain 3/29/2012

Case 4:

With Heat Exchange

Variable Ta, Co-Current Flow

Conversion

(Xexit=0.35)

Rate of Reaction

Temperatures

Case 5:

With Heat Exchange

Variable Ta

Counter Current Flow

Conversion

(Xexit=0.30)

Rate of Reaction

Temperatures

CHENG 322 25

Dr. Shaker Haji, University of Bahrain 3/29/2012

The highest is the equilibrium conversion.

In terms of reaction Temperature & heat exchange:

How Xe can be increased for endothermic reactions?

How Xe can be increased for exothermic reactions?

Exothermic Reaction

CHENG 322 26

Dr. Shaker Haji, University of Bahrain 3/29/2012

Through the equilibrium constant & stoichiometry.

E.g., consider the 1st-order liquid phase rxn carried out in a PFR:

K C (T )

Therefore, X e

1 K C (T )

But whats the value of T inside the reactor? How do I calculate it?

T is obtained from the energy balance on an adiabatic reactor:

or

K C (T )

Equilibrium Constant Definition: Xe

1 K C (T )

Energy Balance:

You solve these two Eqs. simultaneously to find the adiabatic T &

adiabatic Xe.

It can be solved:

analytically

using a solver

graphically

CHENG 322 27

Dr. Shaker Haji, University of Bahrain 3/29/2012

1. make a plot of equilibrium conversion as a function of temperature.

2. Determine the adiabatic equilibrium temperature and conversion

when pure A is fed to the reactor at a temperature of 300 K.

Solution:

CHENG 322 28

Dr. Shaker Haji, University of Bahrain 3/29/2012

CHENG 322 29

Dr. Shaker Haji, University of Bahrain 3/29/2012

Consultation time!

Case: being limited by equilibrium conversion. rxn: A B

very fast, how can the max. achievable

conversion (Xe) be increased?

By:

1. Changing the reactor type/operation mode (e.g. reactive

distillation).

2. Adding heat exchanger to the reactor (cooling in this case).

3. Changing the feed temperature (lower T0 in this case).

Consultation time!

Case: being limited by equilibrium conversion.

Changing the reactor type/operation mode.

What if other reactor types are not suitable!

But rxns in industry are frequently carried out adiabatically!!

CHENG 322 30

Dr. Shaker Haji, University of Bahrain 3/29/2012

Any guess how the XEB(T ) plot would look like?

Interstage Cooling

CHENG 322 31

Dr. Shaker Haji, University of Bahrain 3/29/2012

Endothermic Reaction

Interstage Heating

CHENG 322 32

Dr. Shaker Haji, University of Bahrain 3/29/2012

Consultation time!

Case: being limited by equilibrium conversion.

Changing the reactor type/operation mode.

What if other reactor types are not suitable!!

Adding heat exchanger to the reactor.

But rxns in industry are frequently carried out adiabatically!!

Changing the feed temperature (e.g. for exothermic rxn, use low T0)

But lower feed temperatures will result in lower kinetics & therfore lower X !!

Investigate what happens as the feed temperature is varied for a

reversible and exothermic rxn.

Example:

AB

A

= 0

CHENG 322 33

Dr. Shaker Haji, University of Bahrain 3/29/2012

(e.g. reversible exothermic rxn)

(e.g. reversible exothermic rxn)

X will continue to increase with increasing T0 until Xe is approached.

Further increases in T0 for this exothermic rxn will only decrease the X

due to the decreasing Xe.

This optimum T0 is shown here:

CHENG 322 34

Dr. Shaker Haji, University of Bahrain 3/29/2012

(page 490)

what is the optimum T0 that lead to the highest X in a 2.6 m3-PFR?

Solution:

Optimum T0 = 333 K

Exit conditions @

optimum T0:

T = 364 K

X = 0.7085

Notes:

X is the conversion at the exit.

Xe is calculated based on

the exit T.

CHENG 322 35

Dr. Shaker Haji, University of Bahrain 3/29/2012

How does the X varies along the reactor for the optimum T0 case ?

Notes:

X is the local conversion

Xe is calculated based on the local temperature.

How does the X varies along the reactor for the optimum T0 case ?

K C (T )

Xe

Which equations 1 K C (T )

were used to

plot these

two curves?

dX rA

dV FA0

Notes:

X is the local conversion

Xe is calculated based on the local temperature.

CHENG 322 36

Dr. Shaker Haji, University of Bahrain 3/29/2012

For the adiabatic isomerization of n-butane, n-C4H10 i-C4H10 , in a 2.6 m3 PFR:

1. Plot the equilibrium conversion as a function of temperature.

K C (T )

Xe

1 K C (T )

For the isomerization of n-butane rxn, n-C4H10 i-C4H10 ,

Zoom in (100 600 K).

CHENG 322 37

Dr. Shaker Haji, University of Bahrain 3/29/2012

Zoomed in (100 600 K).

2. On the same Fig, show the effect of X on the adiabatic temperature, for different T0.

CHENG 322 38

Dr. Shaker Haji, University of Bahrain 3/29/2012

3. On the same Fig, show the effect of X on the adiabatic temperature, for different T0.

A

= 0

Zoom in more (200 400 K) and use closer values of T0.

CHENG 322 39

Dr. Shaker Haji, University of Bahrain 3/29/2012

3. Use thermodynamics & kinetics to obtain all of the above for the 3 chosen T0.

Xe=0.8

X=Xe=0.71

X=0.07

X=Xe=0.69

4. Conclusion Using Thermodynamics & Kinetics Using Only

Together Thermodynamics

Adiabatic PFR, V = 2.6 m3 Adiabatic Equilibrium

Xe=0.8

@ T=303 K T & X Calculations

T0 T X Xe Te Xe

Feed T Exit T X @ Exit Xe @ Exit T Adiabatic Adiabatic

X=0.07

T=303 K

Equilib. T Equilib. X

300 K 303 K 0.07 0.8 332.7 K 0.75

333 K 364 K 0.71 0.71 364 K 0.71

X=Xe=0.71

T= 364 K 350 K 380 K 0.69 0.69 380 K 0.69

Te=332.7 K, Xe=0.75

Te=364 K, Xe=0.71

Te=380 K, Xe=0.69

X=Xe=0.69

T=380 K

CHENG 322 40

Dr. Shaker Haji, University of Bahrain 3/29/2012

about energy balance?

To calculate Q required to maintain the reactor at the desired T.

To calculate T that will be reached within the reactor in case it

was operated with a known Q (e.g. adiabatically).

In conclusion, to calculate two variables out of X, V, & T should

one is specified.

o

(T R ) C P T T R Q W

CHENG 322 41

Dr. Shaker Haji, University of Bahrain 3/29/2012

o

(T R ) C P T T R Q W

FA0X = rAV

How do we calculate Q exchanged with the reactor? (Hint: heat

transfer course)

Q mcC Pc T a 2 T a1

In case of high coolant flow rate

(Ta2 Ta1= Ta), Q is calculated by:

Q UA T a T

To calculate Ta2:

Qreactor = Qcoolant , therefore,

CHENG 322 42

Dr. Shaker Haji, University of Bahrain 3/29/2012

X (E.B.) T, T k, k rA, rA & X (M.B.) V

T (E.B.) X, T k, k rA, rA & X (M.B.) V

Solve E.B. & M.B. Equations X&T

CHENG 322 43

Dr. Shaker Haji, University of Bahrain 3/29/2012

Over 800 million pounds of propylene glycol were produced in 2004 and the

selling price was approximately $0.68 per pound. Propylene glycol makes up

about 25% of the major derivatives of propylene oxide. The reaction takes

place readily at room temperature when catalyzed by sulfuric acid.

glycol by this method. Unfortunately, the reactor is beginning to leak, and you

must replace it; you told your boss several times that sulfuric acid was

corrosive and that mild steel was a poor material for construction. There is a

nice-looking overflow CSTR of 300-gal capacity standing idle; it is glass-

lined; and you would like to use it.

01 02 01

CHENG 322 44

Dr. Shaker Haji, University of Bahrain 3/29/2012

Feed process variables are as follows: conditions You are feeding 2500

lbm/h (43.04 Ibmol/h) of propylene oxide (P.O.) to the reactor. The feed

stream consists of (1) an equivolumetric mixture of P.O. (46.62 ft3/h) and

methanol (46.62 ft3/h), and (2) water containig 0.1 wt % H2S04. The

volumetric flow rate of waterRON

rate of water is 233.1 ftqlh, uhich is 2.5 times the methanol-PO. Row rate. The

cornspanding

moIar feed rates of methanol and water are 71.87 and 802.8 Ib mol/h,

respectively. The

water-propylene oxide-methanol mixture undergoes a slight decrease in

volume upon mixing

You are the engineer in charge of an adiabatic CSTR producing propylene

glycol by this method. Unfortunately, the reactor is beginning to leak, and you

must replace it; you told your boss several times that sulfuric acid was

corrosive and that mild steel was a poor material for construction. There is a

nice-looking

Solution: overflow CSTR of 300-gal capacity standing idle; it is glass-

lined; and you would like to use it.

T(oF) T(oR) k H

o

rxn(T) X MB X EB

75 535 0.97 -36449 0.11 0.00

83 542 1.47 -36501.5 0.15 0.08

90 550 2.22 -36554 0.21 0.17

87 546.9 1.91 -36534.63 0.19 0.14

95 554 2.86 -36587.13 0.26 0.22

102 562 4.24 -36639.63 0.34 0.30

112 572.1 7.09 -36710.66 0.47 0.41

120 580 10.25 -36763.16 0.56 0.49

127 587 14.68 -36815.66 0.64 0.57

135 595 20.84 -36868.16 0.72 0.65

142 602 29.33 -36920.66 0.78 0.74

140 599.3 25.92 -36901.5 0.76 0.71

147 607 36.28 -36954 0.82 0.79

153 613 47.65 -36997.54 0.85 0.85

165 625 79.23 -37081.17 0.91 0.98

CHENG 322 45

Dr. Shaker Haji, University of Bahrain 3/29/2012

oxide discussed in Example 8-8. The cooling coil has 40 ft2 of

cooling surface and the cooling water flow rate inside the coil is

sufficiently large that a constant coolant temperature of 85F can

be maintained. A typical overall heat-transfer coefficient for such a

coil is 100 Btu/h.ft2.F. Will the reactor satisfy the previous

constraint of 125F maximum temperature if the cooling coil is

used?

Solution:

CHENG 322 46

Dr. Shaker Haji, University of Bahrain 3/29/2012

Solution:

Mole Balance:

Energy Balance:

Production of Propylene Glycol in an Adiabatic CSTR

Find the steady-state X & T inside the CSTR.

CHENG 322 47

Dr. Shaker Haji, University of Bahrain 3/29/2012

Production of Propylene Glycol in an Adiabatic CSTR

T(oF) T(oR) k H

o

rxn(T) X MB X EB G (T ) R(T )

70 530 0.72 -36414 0.08 0.00 2977 0

78 537 1.11 -36466.5 0.12 0.08 4390 3024

85 544 1.65 -36515.5 0.17 0.16 6142 5847

87 546.9 1.91 -36534.63 0.19 0.19 6949 6949

95 554 2.86 -36587.13 0.26 0.27 9517 9974

102 562 4.24 -36639.63 0.34 0.35 12544 12998

112 572.1 7.09 -36710.66 0.47 0.47 17090 17090

120 580 10.25 -36763.16 0.56 0.55 20493 20115

127 587 14.68 -36815.66 0.64 0.63 23688 23139

135 595 20.84 -36868.16 0.72 0.71 26516 26164

142 602 29.33 -36920.66 0.78 0.79 28902 29188

140 599.3 25.92 -36901.5 0.76 0.76 28085 28085

147 607 36.28 -36954 0.82 0.84 30184 31109

153 613 47.65 -36997.54 0.85 0.91 31601 33617

165 625 79.23 -37081.17 0.91 1.04 33627 38435

CHENG 322 48

Dr. Shaker Haji, University of Bahrain 3/29/2012

o

(T R ) C P T T R Q W

Where

or Q UA T a T when T a1 T a 2

Rewrite the above Eq. so that the heat generation term (i.e. the heat

released term) is on the right hand side.

C T

i Pi T 0 Q / FA0 X (H rxn (T ))

or

C T

i Pi T 0 Q / FA0 (rAV / FA0 ) (H rxn (T ))

Heat-Generated Term: G (T ) X MB (H rxn )

CHENG 322 49

Dr. Shaker Haji, University of Bahrain 3/29/2012

C T

i Pi T 0 Q / FA0 X (H rxn (T ))

G (T ) R (T )

Production of Propylene Glycol in an Adiabatic CSTR

T(oF) T(oR) k H

o

rxn(T) X MB X EB G (T ) R(T )

70 530 0.72 -36414 0.08 0.00 2977 0

78 537 1.11 -36466.5 0.12 0.08 4390 3024

85 544 1.65 -36515.5 0.17 0.16 6142 5847

87 546.9 1.91 -36534.63 0.19 0.19 6949 6949

95 554 2.86 -36587.13 0.26 0.27 9517 9974

102 562 4.24 -36639.63 0.34 0.35 12544 12998

112 572.1 7.09 -36710.66 0.47 0.47 17090 17090

120 580 10.25 -36763.16 0.56 0.55 20493 20115

127 587 14.68 -36815.66 0.64 0.63 23688 23139

135 595 20.84 -36868.16 0.72 0.71 26516 26164

142 602 29.33 -36920.66 0.78 0.79 28902 29188

140 599.3 25.92 -36901.5 0.76 0.76 28085 28085

147 607 36.28 -36954 0.82 0.84 30184 31109

153 613 47.65 -36997.54 0.85 0.91 31601 33617

165 625 79.23 -37081.17 0.91 1.04 33627 38435

CHENG 322 50

Dr. Shaker Haji, University of Bahrain 3/29/2012

CHENG 322 51

Dr. Shaker Haji, University of Bahrain 3/29/2012

8.7.3 Ignition-Extinction

and record the steady states

temperatures (TS).

Both the mole and energy

balances are satisfied at the

points of intersection or

tangency.

Then plot TS vs. T0.

8.7.3 Ignition-Extinction

while T02 is called the

extinction T.

We must exceed a

certain T0 to operate at

the upper steady state

where the T & X are

higher.

CHENG 322 52

Dr. Shaker Haji, University of Bahrain 3/29/2012

sufficiently high that it is undesirable or even dangerous to operate

at this condition.

For example, at the higher Ts, secondary rxns can take place, or as

in the case of propylene glycol (Examples 8-8 & 8-9), evaporation

of the reacting materials can occur.

The ignition temperature occurs at the point of tangency of heat

removed curve to the heat-generated curve.

If we move slightly off point of tangency as shown in Figure 8-24,

then runaway is said to occurred

Test Yourself

represents G(T)? Multiple Steady States in an Adiabatic CSTR

30,000

Calculate Hrxn. 25,000

G(T ) & R(T ) (kJ/mol)

reactor steady state Ts? 5,000

before the ignition and 540 550 560 570 580 590 600

T(K)

extinction Ts?

CHENG 322 53

Dr. Shaker Haji, University of Bahrain 3/29/2012

Most reacting systems involve more than one reaction and do not

operate isothermally.

This section is one of the most important sections of the book.

taking place in a PFR.

Lets do that by starting from the energy balance for a single

reaction taking place in a PFR:

or

CHENG 322 54

Dr. Shaker Haji, University of Bahrain 3/29/2012

single reaction

CHENG 322 55

Dr. Shaker Haji, University of Bahrain 3/29/2012

concentration of 0.1 mol/l. Determine the temperature and flow rate

profiles down the reactor.

species):

CHENG 322 56

Dr. Shaker Haji, University of Bahrain 3/29/2012

=0

X (E.B.) T, T k, k rA, rA & X (M.B.) V

T (E.B.) X, T k, k rA, rA & X (M.B.) V

Solve E.B. & M.B. Equations X&T

CHENG 322 57

Dr. Shaker Haji, University of Bahrain 3/29/2012

1 2

A B C

take place in a 10-liter CSTR. What are the effluent concentrations for

a case where: 0 = 1000 L/min, CA0 = 0.3 mol/L, & T0 = 283 K ?

Solution

V is specified

Calculate T & X (CA, CB, CC)

Calculation

T&X

Graphical Solution

V is specified

Calculate T & X (CA, CB, CC)

Calculation

T&X

plot the two equations (E.B. & M.B) combine the two equations then

independently plot the two sides (RHS & LHS)

CHENG 322 58

Dr. Shaker Haji, University of Bahrain 3/29/2012

1

A B

2

Example 8-11 Multiple Reactions in a CSTR B C

Assume T; Calculate k,

G (T ) R (T ) CA, CB, r1A, r2B, G & R

obtained form

mole balance:

1 2

A B C

10

Note: = = = 0.01 , is this a realistic value?

0 1000

CHENG 322 59

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