Catalyst Deactivation

Book: Chemical Reaction Engineering, O. Levenspiel, 3rd Edition, Wiley and Sons (Chapter 21)
Chemical Engineering Kinetics, J. M. Smith, (Chapter 11), 2nd and 3rd Edition
Rate equation for deactivation from experiment
• Experimental devices for studying deactivating catalysts fall into two classes – those using a batch
of solids and those using a through flow of solids
• If deactivation is slow, a batch mode may be used whereas a continuous flow is required for a fast
reaction (rapid deactivation)

• The method for searching for a rate equation is analogous to that of homogeneous reactions –
starting with the simplest kinetic form and checking if it fits the data
• The main complication is the extra factor of activity
• Batch solid reactors are more commonly used and the type of reactors used depends on whether
the deactivation is concentration dependent or not
• If yes, a reactor in which CA is forced to stay unchanged with time is used. Other wise for
concentration independent reactions, any type of reactor can be used
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
Determining rate for independent deactivation – Batch solids
Here it is seen how to interpret experiments from the various batch-solids reactors and how to
manipulate the basic performance equations for these reactors by testing the fit for cases of
independent deactivation
−𝑟𝐴 = 𝑘𝐶𝐴 𝑎 First order reaction
𝑑𝑎
− = 𝑘𝑑 𝑎 First order, concentration independent deactivation
𝑑𝑡

Batch-solid, Batch – fluid

• The relation between changing gas concentration and time is determined
𝑑𝐶𝐴 𝑊 1 𝑑𝑁𝐴 𝑊 𝑊
− = − = −𝑟𝐴 = 𝑘𝐶𝐴 𝑎
𝑑𝑡 𝑉 𝑊 𝑑𝑡 𝑉 𝑉
𝑑𝑎
− = 𝑘𝑑 𝑎
𝑑𝑡
Integrating we have, 𝑎 = 𝑎𝑜 𝑒 −𝑘𝑑𝑡
For unit initial activity, 𝑎 = 𝑒 −𝑘𝑑𝑡
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
Replacing in above equation,
𝑑𝐶𝐴 𝑊
− = 𝑘𝐶𝐴 𝑒 −𝑘𝑑 𝑡
𝑑𝑡 𝑉
𝐶𝐴 𝑡
𝑑𝐶𝐴 𝑊
−න = 𝑘 න 𝑒 −𝑘𝑑 𝑡 𝑑𝑡
𝐶𝐴𝑜 𝐶𝐴 𝑉 0

𝐶𝐴𝑜 𝑊𝑘
𝑙𝑛 = 1 − 𝑒 −𝑘𝑑 𝑡
𝐶𝐴 𝑉𝑘𝑑
𝐶 𝑊𝑘
At 𝑡 = ∞, 𝑙𝑛 𝐶 𝐴𝑜 = 𝑉𝑘
𝐴∞ 𝑑

𝐶𝐴𝑜 𝐶 𝑊𝑘 𝑊𝑘 𝑊𝑘
Combining the we have, 𝑙𝑛 − 𝑙𝑛 𝐶 𝐴𝑜 = 𝑉𝑘 − 𝑉𝑘 𝑒 −𝑘𝑑 𝑡 − 𝑉𝑘
𝐶𝐴 𝐴∞ 𝑑 𝑑 𝑑

𝐶𝐴 𝑊𝑘 −𝑘 𝑡
𝑙𝑛 = 𝑒 𝑑
𝐶𝐴∞ 𝑉𝑘𝑑
𝐶𝐴 𝑊𝑘
𝑙𝑛 𝑙𝑛 𝐶 = 𝑙𝑛 − 𝑘𝑑 𝑡
𝐴∞ 𝑉𝑘𝑑

This type of reaction is used if the characteristic times for reaction and deactivation are of the same order of
magnitude
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
Batch-solid, Mixed constant flow of fluid (MFR)
𝑊𝐶𝐴𝑜 𝑊 𝐶𝐴𝑜 −𝐶𝐴
For MFR, 𝜏= = = Pseudo steady state assumption
𝐹𝐴𝑜 𝑣 𝑘𝐶𝐴 𝑎
Batch of solids – slow deactivation
𝐶𝐴𝑜
or, 𝑘𝜏𝑎 = −1
𝐶𝐴
𝐶𝐴𝑜
= 1 + 𝑘𝜏𝑎
𝐶𝐴

Now, 𝑎 = 𝑒 −𝑘𝑑𝑡 (derived earlier for independent deactivation)

𝐶𝐴𝑜
= 1 + 𝑘𝜏𝑒 −𝑘𝑑𝑡
𝐶𝐴
𝐶𝐴𝑜
𝑙𝑛 − 1 = 𝑙𝑛 𝑘𝜏 − 𝑘𝑑 𝑡
𝐶𝐴

Expression shows how reactant concentration at the outlet rises with time

BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur

Batch-solid, Mixed changing flow of fluid (to keep 𝑪𝑨 fixed)
𝐶𝐴𝑜
For steady flow in a MFR, 𝐶𝐴
= 1 + 𝑘𝜏𝑒 −𝑘𝑑 𝑡 Pseudo steady state assumption
(conditions change slowly enough for the
system to be at steady state at all times
To keep 𝐶𝐴 constant, the flow rate must be slowly changed with time
Flowrate is lowered as the catalyst deactivates
1 𝐶𝐴𝑜
− 1 = 𝜏𝑒 −𝑘𝑑 𝑡
𝑘 𝐶𝐴

𝐶𝐴𝑜 − 𝐶𝐴
𝑙𝑛 = 𝑙𝑛𝜏 − 𝑘𝑑 𝑡
𝑘𝐶𝐴
𝐶𝐴𝑜 − 𝐶𝐴
𝑙𝑛𝜏 = 𝑘𝑑 𝑡 + 𝑙𝑛
𝑘𝐶𝐴
If the deactivation kinetics are calculated for an independent deactivation condition, then there is no particular
advantage of using the above mode of variable flow as concentration does not influence deactivation

However, for other deactivation kinetics, this mode of operation helps to decouple the three factors –
concentration, temperature and activity and study them a pair at a time
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
Batch-solid, Plug constant flow of fluid (PFR)
𝑊 𝑑𝑋𝐴 𝑑𝑋𝐴 1 𝑑𝑋𝐴
For PFR, the performance equation is =‫׬‬ =‫׬‬ = ‫׬‬
𝐹𝐴𝑜 −𝑟𝐴 𝑘𝐶𝐴 𝑎 𝑘𝑎 𝐶𝐴

𝑊 1 𝑑𝑋𝐴 1 𝑋𝐴 𝑑𝑋𝐴 1
= න = න =− 𝑙𝑛 1 − 𝑋𝐴
𝐹𝐴𝑜 𝑘𝑎 𝐶𝐴 𝑘𝑎 0 1 − 𝑋𝐴 𝐶𝐴𝑜 𝑘𝐶𝐴𝑜 𝑎

𝑊 1 𝐶𝐴𝑜
= 𝑙𝑛
𝐹𝐴𝑜 𝑘𝐶𝐴𝑜 𝑎 𝐶𝐴
𝑊𝐶𝐴𝑜 1 𝐶𝐴𝑜
=𝜏= 𝑙𝑛
𝐹𝐴𝑜 𝑘𝑎 𝐶𝐴
1 𝐶𝐴𝑜
𝜏= 𝑙𝑛
𝑘𝑒 −𝑘𝑑 𝑡 𝐶𝐴
𝐶𝐴𝑜
𝑙𝑛 = 𝑘𝜏𝑒 −𝑘𝑑 𝑡
𝐶𝐴
𝐶𝐴𝑜
𝑙𝑛 𝑙𝑛 = 𝑙𝑛 𝑘𝜏 − 𝑘𝑑 𝑡
𝐶𝐴
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
Batch-solid, Plug changing flow of fluid (to keep 𝑪𝑨,𝒐𝒖𝒕 fixed)
1 𝐶𝐴𝑜
For steady flow in a PFR, 𝜏 = 𝑒 𝑘𝑑𝑡 𝑙𝑛
𝑘 𝐶𝐴
1 𝐶𝐴𝑜
𝑙𝑛𝜏 = 𝑘𝑑 𝑡 + 𝑙𝑛 𝑙𝑛
𝑘 𝐶𝐴

Example
A reaction 𝐴 → 𝐵 is 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 catalyst. What can you say about the rates of reaction and
deactivation? To keep the gas concentration in the reactor unchanged, the flow rate of reactant has to be lowered to
5% of the initial value
CAo = 1 mol/l t, time from start of run, h 0 1 2 3
Run 1
XA = 0.5 𝝉, gcat.min/l 1 𝒆 𝒆𝟐 𝒆𝟑

Run 2 CAo = 2 mol/l t, time from start of run, h 0 1 2 3

XA = 0.667 𝝉, gcat.min/l 2 𝟐𝒆 𝟐𝒆𝟐 𝟐𝒆𝟑
BM-CHE-S402-Chemical Reaction Engineering - II, UIET, CSJM University, Kanpur
 𝐶𝐴𝑜
For a MFR with changing flow (to keep 𝐶𝐴 fixed) and batch solids, = 1 + 𝑘𝜏𝑒 −𝑘𝑑 𝑡 and
𝐶𝐴
𝐶𝐴𝑜 −𝐶𝐴
𝑙𝑛𝜏 = 𝑘𝑑 𝑡 + 𝑙𝑛 3.5
𝑘𝐶𝐴 3

For Run 1 CAo = 1 mol/l t, 0 1 2 3

2.5
2

ln t
XA = 0.5 𝝉 1 𝒆 𝒆𝟐 𝒆𝟑 1.5
1

ln 𝝉 0 1 2 3 0.5
0
𝐶𝐴𝑜 −𝐶𝐴 𝐶𝐴𝑜 −𝐶𝐴 0 0.5 1 1.5 2 2.5 3 3.5
Intercept = 0 = 𝑙𝑛 , ∴ =1 t
𝑘𝐶𝐴 𝑘𝐶𝐴
1−0.5
𝐶𝐴𝑜 = 1 mol/l 𝐶𝐴 = 0.5mol/l , ∴ 𝑘= = 1 and slope = 𝑘𝑑 = 1
0.5
For Run 2 4
CAo = 2 mol/l t, 0 1 2 3 3.5
XA = 0.667 𝝉 2 𝟐𝒆 2𝒆𝟐 𝟐𝒆𝟑 3
2.5

ln 𝝉
2
ln 𝝉 0.693 1.693 2.693 3.693 1.5
1
𝐶𝐴𝑜 −𝐶𝐴 0.5
Intercept = 0.693 = 𝑙𝑛 , 𝐶𝐴𝑜 = 2 mol/l, 𝐶𝐴 = 0.666 mol/l , 0
𝑘𝐶𝐴 0 1 2 3 4
2−0.666 t
∴ 𝑘 = 0.666 𝑥 2 = 1 slope = 𝑘𝑑 = 1
𝒅𝒂
For both cases, 𝑘 = 1 and 𝑘𝑑 = 1 −𝒓𝑨 = 𝑪𝑨 𝒂 − 𝒅𝒕 = 𝒂