Introduction to the combustion reactions

- revisiting reaction kinetics

Dr. Kawnish Kirtania

Department of Chemical Engineering, BUET

2023

1
 HHV, LHV and gge

Individual student task

What is the LHV of C14H30 if the HHV is 43 MJ/kg?

What is the ash free LHV of the fuel if the ash content
is 5%?

Gasoline lower heating value is 42 MJ/kg, the density

is 740 kg/m3
Gasoline price 2.8 $/gallon,
If a liquid fuel has a lower heating value of 28 MJ/kg
and can be sold at a price of 2 $/gallon (0.65 $/kg).
What is the price of the fuel per gallon gasoline
equivalent (gge)?

Kawnish Kirtania 2
 Organic phase reactions

Solid decomposition
Fuel → 𝐶ℎ𝑎𝑟 𝑠 + 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒𝑠 𝑔 + 𝑊𝑎𝑡𝑒𝑟 (𝑔)
Gas-solid reactions
𝐶 𝑠 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔
2𝐶 𝑠 + 𝑂2 𝑔 → 2𝐶𝑂 𝑔
𝐶 𝑠 + 𝐶𝑂2 𝑔 → 2𝐶𝑂 𝑔
𝐶 𝑠 + 𝐻2 𝑂 𝑔 → 𝐶𝑂 𝑔 + 𝐻2 𝑔
Gas-gas reactions
2𝐻2 𝑔 + 𝑂2 𝑔 → 2𝐻2 𝑂 𝑔
2𝐶𝑂 𝑔 + 𝑂2 𝑔 → 2𝐶𝑂2 𝑔
2𝐶𝐻4 𝑔 + 𝑂2 𝑔 → 2𝐶𝑂 𝑔 + 4𝐻2
𝐶 𝑠 + 2𝐻2 𝑔 → 𝐶𝐻4 𝑔
𝐶𝑂 𝑔 + 𝐻2 𝑂 𝑔 ↔ 𝐶𝑂2 𝑔 + 𝐻2 𝑔
𝐶𝐻4 𝑔 + 𝐻2 𝑂 𝑔 ↔ 𝐶𝑂 𝑔 + 3𝐻2 𝑔
Kawnish Kirtania 3
 Organic phase reactions

Solid decomposition
Fuel → 𝐶ℎ𝑎𝑟 𝑠 + 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒𝑠 𝑔 + 𝑊𝑎𝑡𝑒𝑟 (𝑔)
Gas-solid reactions
𝐶 𝑠 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔
2𝐶 𝑠 + 𝑂2 𝑔 → 2𝐶𝑂 𝑔
𝐶 𝑠 + 𝐶𝑂2 𝑔 → 2𝐶𝑂 𝑔
𝐶 𝑠 + 𝐻2 𝑂 𝑔 → 𝐶𝑂 𝑔 + 𝐻2 𝑔
Gas-gas reactions
2𝐻2 𝑔 + 𝑂2 𝑔 → 2𝐻2 𝑂 𝑔
2𝐶𝑂 𝑔 + 𝑂2 𝑔 → 2𝐶𝑂2 𝑔
2𝐶𝐻4 𝑔 + 𝑂2 𝑔 → 2𝐶𝑂 𝑔 + 4𝐻2
𝐶 𝑠 + 2𝐻2 𝑔 → 𝐶𝐻4 𝑔
𝐶𝑂 𝑔 + 𝐻2 𝑂 𝑔 ↔ 𝐶𝑂2 𝑔 + 𝐻2 𝑔
𝐶𝐻4 𝑔 + 𝐻2 𝑂 𝑔 ↔ 𝐶𝑂 𝑔 + 3𝐻2 𝑔
Kawnish Kirtania 4
 Appearance of Char

Kawnish Kirtania Source: Umeki et al., Ind. Eng. Chem. Res., 2012, 51 (43), pp 13973–13979 5
 Appearance of char

Kawnish Kirtania 6
 Reactions involved in every step

Reaction rate = k (Cg, T) f (x)

dx/dt= k (Cg, T) f (x)

k = ko e-E/RT Arrhenius equation

k = kc Cgn

What is this f(x) ?

Kawnish Kirtania 7
 Gas solid reactions

Solid decomposition
Fuel → 𝐶ℎ𝑎𝑟 𝑠 + 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒𝑠 𝑔 + 𝑊𝑎𝑡𝑒𝑟 (𝑔)
Gas-solid reactions
𝐶 𝑠 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔
2𝐶 𝑠 + 𝑂2 𝑔 → 2𝐶𝑂 𝑔
𝐶 𝑠 + 𝐶𝑂2 𝑔 → 2𝐶𝑂 𝑔
𝐶 𝑠 + 𝐻2 𝑂 𝑔 → 𝐶𝑂 𝑔 + 𝐻2 𝑔
Gas-gas reactions
2𝐻2 𝑔 + 𝑂2 𝑔 → 2𝐻2 𝑂 𝑔
2𝐶𝑂 𝑔 + 𝑂2 𝑔 → 2𝐶𝑂2 𝑔
2𝐶𝐻4 𝑔 + 𝑂2 𝑔 → 2𝐶𝑂 𝑔 + 4𝐻2
𝐶 𝑠 + 2𝐻2 𝑔 → 𝐶𝐻4 𝑔
𝐶𝑂 𝑔 + 𝐻2 𝑂 𝑔 ↔ 𝐶𝑂2 𝑔 + 𝐻2 𝑔
𝐶𝐻4 𝑔 + 𝐻2 𝑂 𝑔 ↔ 𝐶𝑂 𝑔 + 3𝐻2 𝑔
Kawnish Kirtania 8
 f(x) for gas-solid reactions

*Ishida M., and Wen C. Y., 1971, Chemical Engineering Science, 26, pp. 1031–1041.
**Szekely J., and Evans J. W., 1970, Chemical Engineering Science, 25(6), pp. 1091–1107.
***Bhatia S. K., and Perlmutter D. D., 1980, AIChE Journal, 26(3), pp. 379–386.

Kawnish Kirtania 9
 Integrate and linearize

Task for students in groups..

2/3 students per group

Integrate and linearize the equations to make an equation of

straight line passing through ORIGIN

Order of groups – VM, GM and RPM

Kawnish Kirtania 10
 How it looks!

Kawnish Kirtania Source: Kirtania and Bhattacharya, ACS Sust. Chem. Eng. 3, 2015, 365-373 11
 Arrhenius plot

Kawnish Kirtania 12
 Does this model work?

Kawnish Kirtania 13
 Comparison of the models

Biomass
Char At 700o C
Random pore model (RPM) R2(VM)=0.94
R2(GM)=0.97
Grain model (GM)
R2(RPM)=0.99

At 750o C
R2(VM)=0.89
Volumetric model (VM)
R2(GM)=0.93
R2(RPM)=0.96

At 800o C
R2(VM)=0.93
R2(GM)=0.96
R2(RPM)=0.99

Kawnish Kirtania 14
 Other graphs
Reaction rate vs. conversion

Kawnish Kirtania Source: Yuan et al., Energy Fuels 25, 2011, 2314-2321 15
 Effect of reactant concentration

Kawnish Kirtania Source: Kirtania, K. and Bhattacharya, S., 2015, ACS Sust. Chem. & Eng., 3 (2), pp 365–373. 16
 Diffusion effect in char conversion

Kawnish Kirtania Source: Kim et al., Applied Energy 129, 2014, 299-307 17
 Reaction zones

Kawnish Kirtania Source: Kim et al., Applied Energy 129, 2014, 299-307 18
 How do we know there are diffusional effects?

Kawnish Kirtania Source: Kirtania, K. and Bhattacharya, S., 2015, ACS Sust. Chem. & Eng., 3 (2), pp 365–373. 19
 Reactivity

Very similar to dx/dt, except it is normalized with respect to

instantaneous conversion

Ri = (-1/xi) (dx/dt)

or,

Ri = (-1/wi) (dw/dt)

Kawnish Kirtania 20
 Reactivity vs. time (at constant temperature)

Kawnish Kirtania 21
 Reality

• Several reactant gases are reacting at the same time with the
solid

• So far we have discussed only reaction with one gas reacting with
the solid

• Experimental data for each gas will give the necessary modelling
parameters

• Then by combining those parameters the model can predict a

realistic atmosphere in a reactor

Kawnish Kirtania 22
 Solid decomposition

Solid decomposition
Fuel → 𝐶ℎ𝑎𝑟 𝑠 + 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒𝑠 𝑔 + 𝑊𝑎𝑡𝑒𝑟 (𝑔)
Gas-solid reactions
𝐶 𝑠 + 𝑂2 𝑔 → 𝐶𝑂2 𝑔
2𝐶 𝑠 + 𝑂2 𝑔 → 2𝐶𝑂 𝑔
𝐶 𝑠 + 𝐶𝑂2 𝑔 → 2𝐶𝑂 𝑔
𝐶 𝑠 + 𝐻2 𝑂 𝑔 → 𝐶𝑂 𝑔 + 𝐻2 𝑔
Gas-gas reactions
2𝐻2 𝑔 + 𝑂2 𝑔 → 2𝐻2 𝑂 𝑔
2𝐶𝑂 𝑔 + 𝑂2 𝑔 → 2𝐶𝑂2 𝑔
2𝐶𝐻4 𝑔 + 𝑂2 𝑔 → 2𝐶𝑂 𝑔 + 4𝐻2
𝐶 𝑠 + 2𝐻2 𝑔 → 𝐶𝐻4 𝑔
𝐶𝑂 𝑔 + 𝐻2 𝑂 𝑔 ↔ 𝐶𝑂2 𝑔 + 𝐻2 𝑔
𝐶𝐻4 𝑔 + 𝐻2 𝑂 𝑔 ↔ 𝐶𝑂 𝑔 + 3𝐻2 𝑔
Kawnish Kirtania 23
 Solid decomposition

Not same as char conversion

Thousands of reactions are happening at the same time

How to deal with it?

Solid to gas reaction is dealing with one major reactant reacting

with several gas species

Here solid decomposes in several compounds…..

Kawnish Kirtania 24
 Gaussian distribution

Kawnish Kirtania 25
 Gaussian distribution

1
Standard deviation, σ = σ𝑁 (𝐸 − 𝑚𝑒𝑎𝑛𝐸)2
1−𝑁 1

(𝐸−𝑚𝑒𝑎𝑛𝐸)2
1 −
Gaussian distribution, f(E) = 𝑒 2𝜎2
2𝜋𝜎 2

Kawnish Kirtania 26
 Gaussian distribution
f(E)

𝜎 𝜎 𝜎 𝜎 𝜎 𝜎

Activation Energy, E
Activation energy is varying with conversion, x
Kawnish Kirtania 27
 Derivation with distribution of activation energy

Whiteboard

∞ 𝑡
𝑥 = 1 − න exp − න 𝑘𝑑𝑡 𝑓 𝐸 𝑑𝐸
0 0

Kawnish Kirtania 28
 An algorithm for DAEM (pyrolysis kinetics)

Pyrolysis of Coal and Algae (experimental results)

Source:
Kawnish Kirtania 1. K. Kirtania, S. Bhattacharya, Bioresource Technology 107, 476–481 (2012). 29
2. K. Kirtania, S. Bhattacharya, Biomass and Bioenergy, 1–8 (2013).
 An algorithm for DAEM (pyrolysis kinetics)

Prediction of experimental results (50:50 blend) by the algorithm

Kawnish Kirtania Source: K. Kirtania, S. Bhattacharya, Biomass and Bioenergy, 1–8 (2013). 30
 An algorithm for DAEM (pyrolysis kinetics)

Prediction of experimental results (for 70:30 blend) by the algorithm

Kawnish Kirtania Source: K. Kirtania, S. Bhattacharya, Biomass and Bioenergy, 1–8 (2013). 31
 Estimated activation energy spread

Activation energy distribution

Kawnish Kirtania Source: K. Kirtania, S. Bhattacharya, Biomass and Bioenergy, 1–8 (2013). 32
 Questions?

End of Lecture

You can always ask by

e-mail: kkdwip@che.buet.ac.bd

Kawnish Kirtania 33