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Soal Chapter 21

The document provides experimental data from several runs of catalytic reactions with deactivating catalysts. It includes conversions (XA) at different times and reactor conditions like reactant concentrations (CAo), catalyst loading (rl), for determining rate expressions for the reactions and deactivation processes. The data shows how catalyst activity and thus conversion decreases over time, indicating progressive deactivation. Rate equations would need to be developed to represent the reaction and deactivation kinetics for each system based on the trends in conversion values with changing conditions and time.

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21-096 Kharisma Theresia Adelina ButarButar
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262 views5 pages

Soal Chapter 21

The document provides experimental data from several runs of catalytic reactions with deactivating catalysts. It includes conversions (XA) at different times and reactor conditions like reactant concentrations (CAo), catalyst loading (rl), for determining rate expressions for the reactions and deactivation processes. The data shows how catalyst activity and thus conversion decreases over time, indicating progressive deactivation. Rate equations would need to be developed to represent the reaction and deactivation kinetics for each system based on the trends in conversion values with changing conditions and time.

Uploaded by

21-096 Kharisma Theresia Adelina ButarButar
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Problems 495

From Fig. E21.2 we find by graphical integration that for the 120-day period,
XA,,,,,, = 0.99, X, ,, = 0.20 for

d = 0 the mean conversion FA= 0.96


d = 1the mean conversion X, = 0.73
d = 2 the mean conversion FA= 0.40
d = 3 the mean conversion XA= 0.30

I It also clearly shows how different is the progress of the reaction with the different
orders of deactivation.

REFERENCES

Levenspiel, O., J. Catal., 25, 265 (1972).


, Chemical Reactor Omnibook, OSU Bookstores, Corvallis, OR, 1996.
Szepe, S., Ph.D. Thesis, Illinois Institute of Technology, 1966; also see Szepe, S., and 0 .
Levenspiel, Chem. Eng. Sci., 23, 881 (1968); "Catalyst Deactivation," p. 265, Fourth
European Symposium on Chemical Reaction Engineering, Brussels, September 1968,
Pergamon, London, 1971.

PROBLEMS

The kinetics of a particular catalytic reaction A +R are studied at temperature


T in a basket reactor (batch-solids and mixed flow of gas) in which the gas
composition is kept unchanged, despite deactivation of the catalyst. What can
you say about the rates of reaction and deactivation from the results of the
following runs? Note, to keep the gas concentration in the reactor unchanged
the flow rate of reactant had to be lowered to about 5% of the initial value.

21.1. . . . Run 1
CAo= 1mollliter
XA= 0.5
t, time from start of run, hr
rl, gm cat. minlliter 1 0 1 2 3
1 e e2 e3

Run 2
CAo= 2 mollliter t, hr
XA= 0.667 rl, gm cat. minlliter l 2 o 2e l 2e2z 2e3
3

21.2. . . . Run 1
CAo= 2 mollliter t, hr
XA= 0.5 rl, gm.min/liter
496 Chapter 21 Deactivating Catalysts

Run 2
C, = 20 mollliter t, hr
XA = 0.8 TI,gm.min/liter

21.3. In an automobile's catalytic converter, CO and hydrocarbons present in


the exhaust gases are oxidized. Unfortunately the effectiveness of these
units decreases with use. The phenomenon was studied by Summers and
Hegedus in J. Catalysis, 51, 185 (1978) by means of an accelerated aging
test on a palladium impregnated porous pellet packed bed converter.
From the reported data on hydrocarbon conversion shown below, develop
an expression to represent the deactivation rate of this catalyst.

This problem was prepared by Dennis Timberlake.

21.4. A recycle reactor with very high recycle ratio is used to study the kinetics
of a particular irreversible catalytic reaction, A --+ R. For a constant flow
rate of feed (7' = 2 kg. seclliter) the following data are obtained:
Time after start of operation, hr
XA 1 1
0.889
2
0.865
4
0.804
The progressive drop in conversion suggests that the catalyst deactivates
with use. Find rate equations for the reaction and for the deactivation
which fit these data.

21.5. The reversible catalytic reaction

proceeds with decaying catalyst in a batch reactor (batch-solids, batch-


fluid). What can you say of the kinetics of reaction and deactivation from
the following data:

21.6. The following data on an irreversible reaction are obtained with decaying
catalyst in a batch reactor (batch-solids, batch-fluid) What can you say
about the kinetics

21.7. With fresh catalyst the packed bed reactor is run at 600K. Four weeks
later when the temperature reaches 800K the reactor is shut down to
reactivate the catalyst. In addition, at any instant the reactor is isothermal.
Problems 497

Assuming optimal operations what is the activity of the catalyst at the


time of reactivation.
Data: The rate of reaction with fresh catalyst is

The rate of deactivation is unknown.

Our reaction A - t R proceeds isothermally in a packed bed of large,


slowly deactivating catalyst particles and is performing well in the strong
pore diffusion regime. With fresh pellets conversion is 88%; however,
after 250 days conversion drops to 64%. How long can we run the reactor
before conversion drops to

It has been suggested that we replace these large particles with very small
particles so as to operate wholly in the diffusion-free regime and thus use
less catalyst for the same conversions. How long a run time can we expect
before the conversion drops from 88% to 64% if the catalyst is used in

21.9. . . . a packed bed reactor?


21.10. . . . a fluidized solids reactor (assume mixed flow of fluid)?

21.11. Under conditions of strong pore diffusion the reaction A --+ R proceeds
at 700°C on a slowly deactivating catalyst by a first-order rate

-ra = 0.030 CAa, [mollgm min]

Deactivation is caused by strong absorption of unavoidable and irremov-


able trace impurities in the feed, giving third-order deactivation kinetics,
or

We plan to feed a packed bed reactor (W = 10 kg) with u = 100 liters1


min of fresh A at 8 atm and 700°C until the catalyst activity drops to 10%
of the fresh catalyst, then regenerate the catalyst and repeat the cycle,
(a) What is the run time for this operation?
(b) What is the mean conversion for the run?

21.12. In catalytic dehydrogenation of hydrocarbons the catalyst activity decays


with use because of carbon deposition on the active surfaces. Let us study
this process in a specific system.
498 Chapter 21 Deactivating Catalysts

A gaseous feed (10% C, HI, - 90% inerts, ?T = 1 atm, T = 555°C) flows


(7'= 1.1 kg. hr/m3) through a packed bed of alumina-chromia catalyst.
The butane decomposes by a first-order reaction

C,HIo4 C,H,-carbon
\
other gases

and the behavior with time is as follows:

Examination of the 0.55-mm pellets shows the same extent of carbon


deposition at the entrance and the exit of the reactor, suggesting concentra-
tion independent deactivation. Develop rate equations for reaction and
deactivation.
This problem was devised from the information given by Kunugita et
al., J. Chem. Eng. (Japan), 2, 75 (1969).

The enzyme catalase effectively decomposes hydrogen peroxide

H202- catalase 1
H 2 0 + - 0,
2

and the kinetics of this reaction are to be evaluated from an experiment


in which dilute H202flows through a packed bed of kieselguhr particles
impregnated with immobilized enzyme.
From the following data, reported by Krishnaswamy and Kitterell,
AZChE J., 28, 273 (1982), develop rate expressions to represent this
decomposition, both in the diffusion free regime and in the strong pore
diffusion regime, for the catalyst at hand. Note that the conversion de-
creases with time in all runs showing that the catalyst deactivates with use.

21.13. . . . run E (modified)


Elapsed Time, hr XA
0
1.25
r1 = 4100 kg cat. s/m3 2.0
zp = 72 2 3.0
p, = 630 kg/m3 cat 4.25
Se= 5 X 10-lo m3/m cat. s 5.0
6.0
7.0
Problems 499

21.14. . . . run B

Elapsed Time, hr XA
0.25 0.57
1.O 0.475
T' =
-
4560 kg cat. s/m3 2.0 0.39
d, 1.45 X 10-3m
= 3.0 0.30
p, = 630 kg/m3 cat 4.0 0.23
9, = 5 X 10-lo m3/m cat. s 5.0 0.186
6.0 0.14
7.0 0.115

21.15. At 730K the isomerization of A to R (rearrangement of atoms in the


molecule) proceeds on a slowly deactivating catalyst with a second-order
rate

- r i = k'Cia = 200 Cia, [mol Alhr .gm cat]

Since reactant and product molecules are similar in structure, deactivation


is caused by both A and R. With diffusional effects absent, the rate of
deactivation is found to be

We plan to operate a packed bed reactor containing W = 1 metric ton


of catalyst for 12 days using a steady feed of pure A, FA,= 5 kmollhr at
730 K and 3 atm (CAo= 0.05 mollliter).
(a) First evaluate -da/dt, d , and then the general expression for 1 - XA.
(b) What is the conversion at the start of the run?
(c) What is the conversion at the end of the run?
(d) What is the average conversion over the 12-day run?

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