Comprehensive Examination

Microkinetic Modelling of Catalytic

Reactions and Applications

A S Russel(20102261)
Supervisor: Dr. Goutam Deo
Indian Institute of Technology, Kanpur
June 2021

1
 Pioneers in Microkinetic Modelling

Michel Boudart James Dumesic Dionisios Vlachos

Stanford UW Madison University of
Delaware
2
 Introduction Inputs required
1 Kinetics, Types of rate equation,
Microkinetic modelling,
2 Thermodynamics, Stoichiometric
and thermodynamic consistency,
Assumptions
Site density

Methodology Solving DAEs

3 Surface coverage, rates, continuity 4 Implicit Euler method, Step size
control

CO Oxidation results
5 Kinetic parameters, Sensitivity, Non
isothermal

3
Chemical reaction kinetics
• Investigate rate during chemical process
• Propose catalytic mechanisms

A+B D
A+D U

D
A+B
U
4
 Types of rate equation N2 + 3H2 ↔ 2NH3

N2 + 2* ↔ N2* [1]
• Power Law model −𝑟𝐴 = 𝑘𝐶𝐴𝑚 𝐶𝐵𝑛 N2* + * ↔ 2N*
H2 + 2* ↔ 2H*
• Fractional function 𝑘𝐶𝐴𝑎 𝐶𝐵𝑏 N* + H* ↔ NH2* + *
−𝑟𝐴 = NH2* + H* ↔ NH3* + *
1 + 𝐾𝐴 𝐶𝐴 𝛼 + 𝐾𝐵 𝐶𝐵 𝛽 … 𝑑
NH3* ↔ NH3 + *

[2]

[1] Dumesic et. al., J. Catal., 1989, 116,119-129

5
[2] Anderson et. al., Front. Chem., 2019, 7:202
 Microkinetic modelling
• No a priori assumptions on RDS or MARI
• Utilize experimental and theoretical surface studies
• Complex reaction mechanisms simulated
• computationally realised in CHEMKIN, cantera[3] and DETCHEM
etc.
What does it tell us?
• Rates of catalytic reactions
• kinetically relevant steps.
• How kinetic parameters are
controlled by catalyst
• And more

[3] Goodwin D.G. et al, Cantera, Version 2.1.0; Caltech: Pasadena, CA, USA, 2013. 6
Mean Field Approximation

• Adsorbed species are distributed randomly

• No interaction between the adsorbed species
• State of catalytic surface described by temperature T and coverages
𝜃𝑖

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 𝑠𝑖𝑡𝑒𝑠 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑

𝜃=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 𝑠𝑖𝑡𝑒𝑠 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒

7
Thermodynamic analysis of CO oxidation
Gibbs minimization method

𝑁 𝑁
𝑜
𝑀𝑖𝑛𝑖𝑚𝑖𝑧𝑒 𝑛𝐺 = ෍ 𝑛𝑖 𝐺𝑖 = ෍ 𝑛𝑖 ∆𝐺𝑓,𝑖 + 𝑅𝑇 ln(𝑦𝑖 𝑃
𝑖=1 𝑖=1

𝑆𝑢𝑏𝑗𝑒𝑐𝑡 𝑡𝑜 𝑐𝑜𝑛𝑠𝑡𝑟𝑎𝑖𝑛𝑡𝑠 𝑛𝐶𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑛𝐶𝑓𝑖𝑛𝑎𝑙 , 𝑛𝑂𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑛𝑂𝑓𝑖𝑛𝑎𝑙 , 𝑛𝑁𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑛𝑁𝑓𝑖𝑛𝑎𝑙

𝑦𝑖 ≥ 10−12

𝐺𝑖𝑣𝑒𝑛 𝑇 = 350 𝑡𝑜 550𝐾 & 𝑃 = 1𝑎𝑡𝑚

8
Temperature effects on equilibrium partial pressure
2CO + O2↔2CO2

9
 Thermodynamic and Stoichiometric consistency
Stoichiometric number(σ): number of times elementary step repeated to get
overall reaction.
Elementary reactions σi Elementary reactions σi
CO + * ↔ CO* [4] X2 N2 + 2* ↔ N2* [1] X1
O2 + 2* ↔ 2O* X1 N2* + * ↔ 2N* X1
CO* + O*↔ CO2*+ * X2 H2 + 2* ↔ 2H* X2
CO2*↔ CO2 + * X2 N* + H* ↔ NH2* + * X2
NH2* + H* ↔ NH3* + * X3
Overall: NH3* ↔ NH3 + * X3
2CO + O2 ↔ 2CO2
Overall:
𝑟𝑖 = 𝜎𝑖 𝑟𝑛𝑒𝑡 N2 + 3H2 ↔ 2 NH3
10
[4] Boudart et. al., M. Surf. Sci., 1981, 102, 151
Condition for thermodynamic consistency:

Equilibrium constant wrt concentration Kc and pressure Kp

𝑘𝑓 (𝑇) ∆𝑅 𝐺(𝑇)
𝐾𝑐 𝑇 = 𝐾𝑝 𝑇 = 𝑒𝑥𝑝 −
𝑘𝑟 (𝑇) 𝑅𝑇

Factor to convert 2 eqm constants:

𝐾𝑐 (𝑇) ∆𝑛
𝐹𝑐ൗ𝑝 = = 𝑅𝑇
𝐾𝑝 (𝑇)

𝑘𝑓 (𝑇) ∆𝑅 𝐺(𝑇)
= 𝐹𝑐ൗ𝑝 . 𝑒𝑥𝑝 −
𝑘𝑟 (𝑇) 𝑅𝑇
11
 Some practical challenges:
• Finding of σi is challenging in mechanisms with multiple parallel paths[5]
• Most large kinetic models written as steady state relation for reaction
intermediates only.
𝑘𝑓 (𝑇) ∆𝑅 𝐺(𝑇)
= 𝐹𝑐ൗ𝑝 . 𝑒𝑥𝑝 −
𝑘𝑟 (𝑇) 𝑅𝑇

Popular strategies:
• Estimate RHS and find kr[6]
• Calculate LHS and see if ∆𝑅 𝐺 𝑇 values are reasonable [7]

Developing Thermodynamically consistent mechanisms is an

ongoing problem in catalytic reaction kinetics
[5] Dumesic et. al., Annu. Rev. Chem. Biomol. Eng., 2018, 9:413-50
[6] Vlachos group, J. Phys. Chem. B, 2005, 109, 16819-16835
12
[7] Deutschmann group, Catalysts, 2015, 5, 871-904
Catalyst specific inputs
Total surface area: 1 1 𝐶−1 𝑃
• N2 adsorption isotherm @-196oC = +
𝑉 𝑃𝑜 /𝑃 − 1 𝑉𝑚 𝐶 𝑉𝑚 𝐶 𝑃𝑜
• Multipoint BET method
• All the samples were degassed at 150oC
for 6 h before adsorption
𝑉𝑚 𝑁𝐴 𝑚2
𝑆𝑔 = 𝛼 = 94
Active site density: 𝑉 𝑔
• H2-chemisorption on the reduced catalysts
• stoichiometry of Ni:H is 1 [7,8]
𝑎𝑐𝑡𝑖𝑣𝑒 𝑠𝑖𝑡𝑒𝑠
𝑁𝑠 = 𝐹𝑠 ∗ 𝑁𝑚 = 1.54 ∗ 1019
𝑚2
Bulk density: To calculate length of reactor

[8] C. H. Bartholomew et.al., J. Catal., 1980, 65, 390–401

[9] T Wang et.al., Nanoscale, 2016, 8, 10177 13
Methodology for Microkinetic modelling
• Plug flow reactor was modelled as a linear chain of steady state PFRs
• The gas entering the first reactor had the required inlet composition.
• For subsequent reactors, inlet is the outlet of the preceding reactor.
• Axial diffusion was neglected and isothermal condition assumed
• plug flow reactor was simulated by integrating each reactor to steady-state
sequentially.

Inlet PFR Outlet

....
PFR split into n number of smaller PFRs 14
 Equations to be solved
𝑁𝑔 𝑁𝑠
𝜐𝑖𝑗 𝜐𝑖𝑘
𝑟𝑖 = 𝑘𝑖 ෑ 𝑐𝑗 ෑ 𝑠𝑘
𝜕𝜃𝑘
= ෍ 𝜐𝑖𝑘 𝑟𝑖 𝑗=1 𝑘=1
𝜕𝑡 Surface
𝑖
Coverage Rate
𝜃∗ = 1 − ෍ 𝜃𝑘 DAE
𝑘
Continuity &
species balance
PFR
Inlet Outlet 𝑑 𝜌𝑢 𝑁𝑔
= 𝑎𝑣 σ𝑖=1 𝑠ሶ𝑖 𝑀𝑖
𝑑𝑧
concentration

𝑁𝑔
𝑑 𝑌𝑖
𝜌𝑢 + 𝑌𝑖 𝑎𝑣 ෍ 𝑠ሶ𝑖 𝑀𝑖 = 𝑀𝑖 𝑎𝑣 𝑠ሶ𝑖 + 𝑀𝑖 𝜔ሶ 𝑖
𝑑𝑧
𝑖=1
15
Axial distance
Surface coverage CO Oxidation
CO + * ↔ CO*
O2 + 2* ↔ 2O*
𝜃∗ = 1 − 𝜃𝑐𝑜 − 𝜃𝑜 − 𝜃𝐶𝑂2
CO* + O*↔ CO2*+ *
CO2*↔ CO2 + *
𝑑𝜃𝑐𝑜
= 𝑘1 𝐶𝐶𝑂 𝜃∗ Γ − 𝑘2 𝜃𝑐𝑜 Γ − 𝑘5 𝜃𝐶𝑂 𝜃𝑂∗ Γ 2 + 𝑘6 𝜃𝐶𝑂2 𝜃∗ Γ 2
𝑑𝑡
𝑑𝜃𝑜
= 2 𝑘3 𝐶𝑂2 𝜃2∗ Γ 2 − 2 𝑘4 𝜃2∗ Γ 2 − 𝑘5 𝜃𝐶𝑂 𝜃𝑂∗ Γ 2 + 𝑘6 𝜃𝐶𝑂2 𝜃∗ Γ 2
𝑑𝑡
𝑑𝜃𝐶𝑂2
= 𝑘5 𝜃𝐶𝑂 𝜃∗ Γ 2 − 𝑘6 𝜃𝐶𝑂2 𝜃∗ Γ 2 − 𝑘7 𝜃𝐶𝑂2 Γ + 𝑘8 𝐶𝐶𝑂2 𝜃∗ Γ
𝑑𝑡

16
 Kc in terms of partition function
−𝐸𝑚
𝑁 𝑁𝑖 𝑒𝑥𝑝 𝐾 𝑇
𝑞𝑖 𝑖
𝑞𝑖 𝑒 𝑃𝑚 = 𝐵
−𝐸𝑚
Canonical partition function 𝑄 𝑇, 𝑉, 𝑁 =ෑ ≈ෑ σ𝑚 exp
𝑁𝑖 ! 𝑁𝑖 𝐾𝐵 𝑇
𝑖 𝑖

𝜕𝐴 𝜕𝑙𝑛𝑄 𝑞𝑖
Calculate chemical potential 𝜇𝑖 = = −𝐾𝐵 𝑇 = −𝐾𝐵 𝑇𝑙𝑛
𝜕𝑁𝑖 𝜕𝑁𝑖 𝑁𝑖
Applying in reaction 𝑞𝑖
equilibrium condition ෍ 𝜈𝑖 𝜇𝑖 = 0; −𝐾𝐵 𝑇 ෍ 𝜈𝑖 𝑙𝑛 =0
𝑁𝑖
𝑖 𝑖

Exponentiating and
rearranging ෑ 𝑁𝑖 𝜈𝑖 = ෑ 𝑞𝑖 𝜈𝑖 ;
𝑖 𝑖
[10]
𝑞𝑖 𝜈𝑖
𝐾𝑐 = ෑ 𝐶𝑖 𝜈𝑖 =ෑ
𝑉
[10] M. Scott Shell, Thermodynamics and statistical mechanics : 𝑖 𝑖
17
an integrated approach (2015)
 Rate constants

𝐾𝐵 𝑇 −Δ𝐺𝑓𝑇𝑆
Eyring equation 𝑘𝑓 = exp 1
ℎ 𝐾𝐵 𝑇
𝑞𝑖 𝜈𝑖
Free energy in terms of ∆𝐺𝑓𝑇𝑆 = −𝐾𝐵 𝑇𝑙𝑛 + 𝑈 𝑇𝑆 (2)
partition functions
𝑉

Combining (1) and (2)

𝑄𝑇𝑆 𝐾𝐵 𝑇 −𝑈 𝑇𝑆
𝑘𝑓 = 𝜅 𝐼𝑆 exp
𝑄 ℎ 𝐾𝐵 𝑇
[10]

𝑄 = 𝑄𝑡𝑟𝑎𝑛 ∗ 𝑄𝑣𝑖𝑏 ∗ 𝑄𝑟𝑜𝑡 ∗ 𝑄𝑒𝑙

[10] M. Scott Shell, Thermodynamics and statistical mechanics : 18

an integrated approach (2015)
 𝑁𝑔 𝑁𝑠
Rates 𝜐𝑖𝑗 𝜐𝑖𝑘
𝑟𝑖 = 𝑘𝑖 ෑ 𝑐𝑗 ෑ 𝑠𝑘
𝑗=1 𝑘=1
Partition function Formula
Translational 𝐿 2𝜋𝑚𝐾𝐵 𝑇/ℎ
Vibrational 1/(1 − 𝑒 −ℎ𝜈/𝐾𝐵 𝑇 ) 𝑄𝑇𝑆 𝐾𝐵 𝑇 −𝑈 𝑇𝑆
𝑘𝑓 = 𝜅 𝐼𝑆 exp
Rotational (8𝜋 2 𝐼𝐾𝐵 𝑇 )/ℎ2 𝑄 ℎ 𝐾𝐵 𝑇

𝐾𝐵 𝑇 −𝐸𝐴𝑖
𝑘𝑖,𝑠𝑢𝑟𝑓 = 𝑒𝑥𝑝
𝑅𝑇 ℎ 𝐾𝐵 𝑇
𝑘𝑖,𝑎𝑑𝑠 = 𝑠𝑜,𝑖
2𝜋𝑚𝑖 𝑁𝑠
𝛽𝑖
−𝐸𝐴𝑖 −𝜀𝑘𝑖 𝜃𝑘
𝑘𝑖,𝑠𝑢𝑟𝑓 = 𝐴𝑖 𝑇 𝑒𝑥𝑝 ෑ 𝑒𝑥𝑝
𝐻𝑒𝑟𝑡𝑧 − 𝐾𝑛𝑢𝑑𝑠𝑒𝑛 𝑎𝑑𝑠𝑜𝑟𝑝𝑡𝑖𝑜𝑛 𝑅𝑇 𝑅𝑇
𝑘=1
𝑀𝑜𝑑𝑖𝑓𝑖𝑒𝑑 𝐴𝑟𝑟ℎ𝑒𝑛𝑖𝑢𝑠 𝑇𝑦𝑝𝑒 19
 Sticking Coefficient
[11]
𝑆𝑜,𝑖 = 𝑆𝑙𝑜𝑝𝑒 𝑎𝑡 𝑜𝑟𝑖𝑔𝑖𝑛

Number of atoms adsorbed

Number of adsorbate atoms exposed

• Surface dosed with supersonic beam of molecular methane

• Surface kept at 500K to enable hydrogen atoms to desorb instantaneously
• Coverage calculated using Auger electron spectroscopy
[11] Larsen, J.H. and Chorkendorff, I. (1999) ‘From fundamental studies of reactivity
20
on single crystals to the design of catalysts’. Surface Science Reports
 Solving Differential algebraic equations CO Oxidation
• Consider CO oxidation example CO + * ↔ CO*
• We want steady state surface coverage O2 + 2* ↔ 2O*
• Given partial pressure of reactants at inlet CO* + O*↔ CO2*+ *
• Given initial surface coverage CO2*↔ CO2 + *
𝑑𝜃𝐶𝑂
𝑑𝑡 𝑘1 𝐶𝐶𝑂 𝜃∗ Γ − 𝑘2 𝜃𝑐𝑜 𝜃∗ Γ 2 − 𝑘5 𝜃𝐶𝑂 𝜃𝑂∗ Γ 2 + 𝑘6 𝜃𝐶𝑂2 𝜃∗ Γ 2
𝑑𝜃𝑂
= 2 𝑘3 𝐶𝑂2 𝜃2∗ Γ 2 − 2 𝑘4 𝜃2∗ Γ 2 − 𝑘5 𝜃𝐶𝑂 𝜃𝑂∗ Γ 2 + 𝑘6 𝜃𝐶𝑂2 𝜃∗ Γ 2
𝑑𝑡
𝑑𝜃𝐶𝑂2 𝑘5 𝜃𝐶𝑂 𝜃∗ Γ 2 − 𝑘6 𝜃𝐶𝑂2 𝜃∗ Γ 2 − 𝑘7 𝜃𝐶𝑂2 Γ + 𝑘8 𝐶𝐶𝑂2 𝜃∗ Γ
𝑑𝑡
𝜃𝐶𝑂 𝑃𝐶𝑂
𝜃∗ = 1 − 𝜃𝑐𝑜 − 𝜃𝑜 − 𝜃𝐶𝑂2 Given 𝜃𝑂 and 𝑃𝑂2
𝜃𝐶𝑂2 𝑃𝐶𝑂2
𝑡0 =0 @ 𝑖𝑛𝑙𝑒𝑡 21
Implicit Euler method 𝑓 𝑥𝑖 − 𝑓 𝑥𝑖−1
′
𝑓 𝑥𝑖 = +𝑂 ℎ
ℎ
𝑦𝑖+1 = 𝑦𝑖 + ℎ 𝑓 𝑥𝑖+1 , 𝑦𝑖+1 𝑓 𝑥𝑖−2 − 4𝑓 𝑥𝑖−1 + 3𝑓 𝑥𝑖
𝑓 ′ 𝑥𝑖 = + 𝑂 ℎ2
ℎ
• AKA backward differencing scheme
• Variable step size variable order method utilized

𝜃𝐶𝑂 𝜃𝐶𝑂 𝑘1 𝐶𝐶𝑂 𝜃∗ Γ − 𝑘2 𝜃𝑐𝑜 Γ − 𝑘5 𝜃𝐶𝑂 𝜃𝑂∗ Γ 2 + 𝑘6 𝜃𝐶𝑂2 𝜃∗ Γ 2

𝜃𝑂 = 𝜃𝑂 + 𝑑𝑡 2 𝑘3 𝐶𝑂2 𝜃2∗ Γ 2 − 2 𝑘4 𝜃2∗ Γ 2 − 𝑘5 𝜃𝐶𝑂 𝜃𝑂∗ Γ 2 + 𝑘6 𝜃𝐶𝑂2 𝜃∗ Γ 2
𝜃𝐶𝑂2 𝜃𝐶𝑂2 𝑘 𝜃
5 𝐶𝑂 ∗𝜃 Γ 2−𝑘 𝜃
6 𝐶𝑂2 ∗𝜃 Γ 2−𝑘 𝜃
7 𝐶𝑂2 Γ + 𝑘8 𝐶𝐶𝑂2 𝜃∗ Γ
𝑡𝑖+1 𝑡𝑖 𝑡𝑖+1

(𝑘+1) (𝑘) (𝑘)

𝑦𝑖+1 = 𝑦𝑖+1 + ℎ 𝑓 𝑥𝑖+1 , 𝑦𝑖+1

• Iterations need to be done at every step of integration

22
Step size control:
𝑦𝑛+1 obtained using both ℎ and ℎ /2 and error between 2 estimates calculated
ℎ𝑛
𝐸𝑛 = 𝑦𝑛+1 − 𝑦𝑛+1 ℎ𝑛
2
𝐸𝑛,𝑖
𝑞 = 𝑀𝑎𝑥
𝜀
If 𝑞 >1 => estimate is unacceptable and smaller step size to be used
If 𝑞 <1 => estimate is acceptable
Inlet Outlet
PFR

....
23
PFR split into n number of smaller PFRs
CO Oxidation results @200oC

Partial pressure of gases and surface coverage with contact time; Reaction condition, Temperature
= 200oC, Pressure: 1 atm, Partial pressure at inlet, CO:0.5, O2=0.1, N2=remaining[self generated]
24
Kinetic parameters
• Overall reaction orders and apparent activation energy
• ni : reaction order with respect to species i
• Eapp : Apparent activation energy
• 𝑃𝑖 : partial pressure of component i
• 𝑟 : rate of disappearance of CO

𝜕 𝑙𝑛 𝑟
𝑛𝑖 = 𝑃𝑖 Parameters Calculated value@
𝜕𝑃𝑖
𝜕 𝑙𝑛 𝑟 200oC
𝑎𝑝𝑝 2
𝐸𝑎𝑐𝑡 = 𝑅𝑇 Eapp 76.31 KJ/mol
𝜕𝑇
𝑛𝐶𝑂 1.11
𝑛𝑂2 0.58
25
 Sensitivity Analysis
• Significant reactions can be found in a large mechanism
• Ski : Sensitivity coefficient
𝑝𝑖 𝜕𝑦𝑘
𝑆𝑘𝑖 =
𝑦𝑘 𝜕𝑝𝑖
• Change in concentration (y) when the value of rate constant (p) is
perturbed by ~5% of its original value while keeping the other
variables constant.
• Effect of temperature on sensitivity analysis also checked.
For CO Oxidation at 200oC
CO + * ↔ CO*
O2 + 2* ↔ 2O*
CO* + O*↔ CO2*+ * (possible RDS)
CO2*↔ CO2 + * 26
 Fractional rate equation
• Partial equilibrium factor showed:
• Adsorption reaction are quasi equilibrated
• Surface reaction is irreversible
• Sensitivity analysis showed surface reaction is rate determining step
• Surface coverage analysis showed CO* is MARI

𝑟𝑓
𝑃𝐸𝐹 =
𝑟𝑓 + 𝑟𝑏
𝑘5 𝐾1 𝑃𝐶𝑂 𝐾2 𝑃𝑂2
≈ 0.5 (𝑄𝑢𝑎𝑠𝑖 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑎𝑡𝑒𝑑) 𝑟= 2
1 + 𝐾1 𝑃𝐶𝑂 + 𝐾2 𝑃𝑂2
≈ 1 (𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒)

27
Summary
• Inputs required and methodology behind microkinetic modelling was
explained
• Microkinetic modelling was performed on a 8 step reaction
mechanism for CO oxidation
• Results from microkinetic analysis was used to derive a rate equation
for CO oxidation over Ni catalyst.

28
References
[1] Dumesic et. al., J. Catal., 1989, 116,119-129
[2] Anderson et. al., Front. Chem., 2019, 7:202
[3] Goodwin D.G. et al, Cantera, Version 2.1.0; Caltech: Pasadena, CA, USA, 2013.
[4] Boudart et. al., M. Surf. Sci., 1981, 102, 151
[5] Dumesic et. al., Annu. Rev. Chem. Biomol. Eng., 2018, 9:413-50
[6] Vlachos group, J. Phys. Chem. B, 2005, 109, 16819-16835
[7] Deutschmann group, Catalysts, 2015, 5, 871-904
[8] C. H. Bartholomew et.al., J. Catal., 1980, 65, 390–401
[9] T Wang et.al., Nanoscale, 2016, 8, 10177
[10] M. Scott Shell, Thermodynamics and statistical mechanics : an integrated approach (2015)
[11] Larsen, J.H. and Chorkendorff, I. (1999) ‘From fundamental studies of reactivity
on single crystals to the design of catalysts’. Surface Science Reports

Picture References
Slide 4: Explosion Rocks Louisiana Chemical Plant – WSJ (Visited June 2021)
Slide 4: Control Engineering | EC: SIMATIC PCS 7 Version 8 (Visited June 2021)
Slide 13: Quantachrome Instruments (Visited June 2021) 29