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Solutions:

a) Conversion and heat duty for an isothermal reactor operating at 298 K.

Calculation of conversion for an isothermal reactor operating at 298 K:

Mass balance for A over CSTR gives FA0 FAf V ( rA ) exit

Since ( rA ) exit kC Af , we get v0C A0 v f C Af VkC Af , where v0 is the volumetric flow rate at

the inlet and v f is the volumetric flow rate at the exit.

Conversion is defined as x Af

FAf FA0

FA0

v f C Af v0C A0

v0C A0

Thus, the mass balance for A over the reactor becomes v0 x Af Vk (1 x Af ) , which gives

1 x Af

x Af

v

1

0

where V / v0 is the space time.

Vk k

k

1

1 k 1 1

k

-4 -1

Therefore, we get

x Af

(1.1)

We get k = 0.0988

Thus,

x Af

For the data given, we could start with equation (8.18) from the Lecture Note Set 8, which is

T 0C p (T f T0 ) FA0 x Af H R (@ T f )

Q in W shaft

m

in

Neglecting shaft work and using m T 0 v0 , the above equation can be reduced to

Q in v0 C p (T f T0 ) v0C A0 x Af H R (@ T f )

(1.2)

v C x H (@ 298)

Q

in

0 A0 Af

R

( 0.86 x 10 - 3 m 3 /s) ( 2.0 kmol/m3 ) (0.09) ( 167,500 kJ/kmol of A reacted )

25.9 kJ/s 26 kW

b) Conversion and reactor temperature for an adiabatic reactor with inlet temperature of 298

K.

(1.1) gives the mass balance where k is a function of temperature described by the Arrhenius Law as

E

k (T ) k 0 exp

.

RT

k ( 298)

1.7 10 4

E

k0

s -1

k ( 298) k 0 exp

which gives

E

41,870

exp

exp

298 R

298 R

298 8.314

Therefore,

1

1

E 1

41,870 1

4

k (T ) k (298) exp

1.7 10 exp

R T 298

8.314 T 298

-1

s

(1.3)

Heat balance given by (1.2) for an adiabatic case which negligible shaft work reduces to

v0 C p (T f T0 ) v0C A0 x Af H R (@ T f ) 0 .

Since an average specific heat capacity is assumed, from Lecture Note Set 8, we could see that the

heat of reaction can be taken to remain a constant. Therefore, we get

x Af

C p (T f T0 )

C A0 H R (@ T f )

(1050 kg/m3 ) (4.19 kJ/kg.K)(T f T0 ) K

( 2.0 kmol/m3 ) ( 167,500 kJ/kmol of A reacted )

(1050) (4.19)(T f T0 )

( 2.0) ( 167,500)

x Af 0.0131(T f T0 )

(1.4)

Plotting (1.1) [with k given by (1.3)] and (1.4) [with T0 = 298 K] in the same graph we get

T

298

300

302

k

0.00017

0.00019

0.000213

(x_Af)_mass balance

0.08994709

0.09960537

0.110028968

(x_Af)_heat balance

0

0.0262

0.0524

304

306

308

310

310.5

311

311.5

312

0.000237

0.000264

0.000294

0.000327

0.000336

0.000345

0.000354

0.000363

0.12124038

0.13325719

0.146091301

0.159748213

0.163290984

0.166885022

0.170530201

0.174226361

0.0786

0.1048

0.131

0.1572

0.16375

0.1703

0.17685

0.1834

The temperature is 310.5 K and the conversion is 0.163 for the adiabatic case.

c) Conversion and preheating temperature for an adiabatic reactor with a reactor

temperature of 363 K.

Mass balance would remain the same as (1.1), in which k must be calculated at the reactor

temperature of 363 K as

1 -1

41,870 1

-1

k (363) 1.7 10 4 exp

s 0.003505 s

8.314 363 298

k

1

x Af

1

1 k 1

(1.1) therefore gives

0.67

3

-1

0.581 x 10 s 0.003505 s

The inlet temperature can be calculated using the heat balance given by (1.4) as follows:

T0 T f

x Af

0.0131

363

0.67

311 .86 312 K

0.0131

Conversion is 0.67 and preheating temperature is 312 K for an adiabatic reactor with a

reactor temperature of 363 K.

d) Conversion and heat duty if the reactor is operated non-adiabatically without preheating

and at a temperature of 363 K.

Conversion is as the same as in case (c) since it is influenced by the reactor temperature which is the

same as in (c). Heat duty shall be calculated using (1.2) as follows:

1050 kg/m3 4.19 kJ/kg.K (363 298)K

3

Conversion is 0.67 and heat duty is 53 kW if the reactor is operated non-adiabatically without

preheating and at a temperature of 363 K.

Tabulating the results:

Part

Feed

Temperature,

T0 K

Reactor

Temperature,

Tf K

Conversion

of A attained,

x Af

Heat duty of

the reactor,

Q

in kW

a)

298

298

0.09

26

b)

298

310.5

0.163

c)

312

363

0.67

d)

298

363

0.67

53

Observations

For isothermal operation of CSTR

at 298 K, we reach only 9%

conversion of A, which is very low.

For adiabatic operation with feed

stream at 298 K, the reactor

temperature stabilizes at 310.5 and

conversion of A stabilizes at

16.3%, which is still low.

For adiabatic operation with

preheating feed stream to 312 K so

as to maintain the reactor

temperature at 363, conversion of

A stabilizes at 67%.

Heat required to heat the feed

stream from 298 K to 312 K is

given below.*

Without preheating the feed

stream, we could heat the reacting

mixture to 363K in a non-adiabatic

operation of the CSTR.

Conversion of A stabilizes at 67%

as in part (c).

Heat required to heat the reacting

mixture is the same as the heat

required to heat the feed stream

from 298 K to 312 K.

= v0 C p (312 298)

( 0.86 x 10-3 m 3 /s) (1050 kg/m3 ) (4.19 kJ/kg.K)(312 298) K

= 53 kW

2) This problem will be worked out using the notation used in Lecture Note Set 10.

Adsorption reaction can be written as

A( g ) S A S

k

Therefore, forward reaction rate equals the backward reaction rate. Hence we write the following:

kp ACv k C A S

(2.1)

k

S

Surface reaction A S A( g )

A2 ( g ) S is rate limiting, and therefore rate of production of A2 is

given as

rA2 rA S rA k S C A S p A

(2.2)

Since C AS in (2.2) is a variable, it must be converted to a constant. To do that, first we write the

site balance as

C t Cv C A S

(2.3)

k

k C

1

C t A S C A S 1 C A S

1 C A S

kp A

kp A

K A pA

where K A k / k is the adsorption equilibrium constant.

Eliminating C A S from (2.2) and (2.4), we get

k K C p2

pA S A t A

1 K A pA

1

1

K A pA

Ct

rA2 k S

Therefore the rate expression becomes,

2

k K C ( RT ) 2 C A

rA2 S A t

1 K A RTC A

(2.4)

X-OH + Y-H X-Y + H2O

An equimolar feed of liquid X-OH and Y-H at 25oC are fed to a CSTR.

At 25oC, where all four material species are liquids.

At 25oC, the heat of reaction Hrxn = -200 kJ/mole.

At 25oC, the heat capacity of each liquid-phase species is 4 kJ/(kg oC).

The molecular weight of X-OH is 150 g/mole, and the molecular weight of Y-H is 100 g/mole.

The temperature inside the reactor (T) is controlled by putting the reactor in thermal contact with a

fluid flowing over the outside of the reactor at temperature Ta.

To a good approximation, the heat transfer rate (Q, in watts) from the fluid flowing over the outside

the reactor to the contents of the reactor is given by the linear expression: Q = UA(Ta-T)

a) If the reaction is carried out with the reactor at steady-state at the inlet temperature of

25oC, is T greater than, less than, or equal to Ta?

For an exothermic reaction, to maintain the products at the same temperature as the reactants one

must remove heat. So T must be greater than Ta, i.e. Ta must be below room temperature (25oC).

b) When running the reactor at T = 25oC to 50% conversion, the productivity is unacceptably

low. To try to accelerate the reaction, it is decided to increase the steady-state reactor

temperature to T = 105oC. At this temperature, all of the H 2O formed evaporates, but the

other species are still liquids. The heat of vaporization of H 2O at 105oC is +40 kJ/mole.

When T = 105oC, the reaction runs to 50% conversion 10x faster than it did at 25 oC, so we

increase the flow rates until the reactor is making 10x as much product as it did at 25 oC

(still at 50% conversion). When we achieve the new steady-state high-productivity

operation at 105oC, will the magnitude of Q (i.e. |Q|) be larger, smaller, or the same as it

was when we were operating at 25oC? At this steady-state condition, is T greater than, less

than, or equal to Ta?

When running the reactor at T = 25 oC (i.e., isothermal conditions) to 50% conversion, the heat

requirment can be calculated as follows:

FA0 x Af H R (@ 298) ( FA0 mole/s) (0.5) ( 200 kJ/mole) -100 FA0 kW

When running the reactor at T = 105oC (i.e., non-isothermal conditions) to 50% conversion, the heat

required can be calculated as follows:

Q in non isothermal

Heat required to heat up X - OH stream from 25o C to 105o C

Heat required to heat up Y - H stream from 25o C to 105o C

Heat released by the reaction Heat required to vapourise the water produced in the reaction

Data provided states that the feed flow rate is 10 times more than the isothermal case and the

conversion remains 50%.

Q in non isothermal

(10 FA0 mole/s) ( 4 kJ/kg o C) (105 25) o C (10 FB 0 mole/s) ( 4 kJ/kg o C) (105 25) o C

(10 FA0 mole/s) ( x Af ) H R (@ 298) (10 FA0 mole/s) x Af ( heat of vapourization of water)

Q in non isothermal

(10 FA0 0.25 kg/s) ( 4 kJ/kg) (80) (10 FA0 0.10 kg/s) ( 4 kJ/kg) (80)

(10 FA0 mole/s) (0.5) ( 200 kJ/mole) (10 FA0 mole/s) (0.5) ( 40 kJ/mole)

10 ( 0.15 0.1) 4 80 1000 200 FA0 kW

800 1000 200 FA0 kW

0

Note that the heat released by the reaction balances the heat required to warm up the mixture and

evaporate the water. Therefore, T should approximately equal Ta.

In contrast, when we ran the reactor at 298 K, we had to remove heat at a rate of 200 kJ/kg.

c) Since operating hot improved our productivity, but conversion is still pretty low, the

operator tries to improve things by cranking up the temperature, preheating the inlet

streams to 185oC and increasing Ta. For good measure the operator simultaneously cranks

up the reactor pressure from 1 bar to 100 bar; at this high pressure all the species remain

as liquids. (The reactor is safe at this condition, and even up T = 300 oC.) Curiously, the

conversion and productivity of the reactor do not increase under these severe conditions,

instead they decrease. Propose an explanation for this experimental observation.

It is possible that we are running into equilibrium limitations on the reaction. For exothermic

reactions, Keq decreases with increasing temperature. So if we are equilibrium limited at high T, we

would expect the conversion to decrease as T increases. (Note that by increasing the pressure so

dramatically, the operator prevented most of the H2O from evaporating, hence the concentration of

H2O in the liquid phase is probably much higher now than it was in the 105 oC case where the water

evaporated; this contributes to the equilibrium limitation).

d) Your manager gives the operator who turned up the temperature (without doing any

calculations first) a formal reprimand, saying the operator is probably lucky that the

conversion went down instead of increasing. Why do you think the manager was happy

that conversion was low instead of increasing a lot?

Exothermic reactions can run away if T goes high enough, i.e. past a certain point, the steadystate conversion will suddenly jump from a low number to a very high conversion, releasing

essentially the whole exothermicity, and jumping the T to a temperature above the safety limits of

the reaction vessel. In the present case, if the reverse reaction were negligible the reaction would

release 800 kJ/kg, enough to increase the temperature inside the reactor by up to 200 degrees, so it

could have exceeded the T = 300oC safety limit. The results could have been fatal to the operators or

7

anyone else nearby. But fortunately in this case it was lucky that high conversion was not

achievable due to the small value of the equilibrium constant.

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