Accepted Manuscript

Multi reaction apparent kinetic scheme for the pyrolysis of large size biomass particles
using macro-TGA

Rajeev Sharma, Pratik N. Sheth

PII: S0360-5442(18)30484-5
DOI: 10.1016/j.energy.2018.03.075
Reference: EGY 12533

To appear in: Energy

Received Date: 12 January 2018

Revised Date: 28 February 2018
Accepted Date: 14 March 2018

Please cite this article as: Sharma R, Sheth PN, Multi reaction apparent kinetic scheme for the pyrolysis
of large size biomass particles using macro-TGA, Energy (2018), doi: 10.1016/j.energy.2018.03.075.

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 ACCEPTED MANUSCRIPT

Multi reaction apparent kinetic scheme for the pyrolysis of large

size biomass particles using macro-TGA

Rajeev Sharmaa, Pratik N Shethb*

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a
Amity School of Engineering & Technology, Amity University Rajasthan, Jaipur.

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b
Department of Chemical Engineering,

Birla Institute of Technology and Science – Pilani, Pilani Campus, PILANI – 333 031

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Email: pratik@pilani.bits-pilani.ac.in, pnsheth@gmail.com

Tel: +91-1596-515636 (O), +91-9799212070 (M), Fax: +91-1596-244183

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*Corresponding Author
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ABSTRACT
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In the present study, the pyrolysis of biomass is proposed by one step multi reaction apparent
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model. It is expressed as parallel production of bio-oil, gases and charcoal. Macro TGA of
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Jatropha de-oiled cake is performed at temperatures ranging from 350 ˚C to 700 ˚C. The volatiles

released during pyrolysis exits from the top of the reactor and are cooled in a two-stage
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condenser followed by an ice trap. The weight reduction variation of the biomass with time,
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product yield and composition of non condensable gases are measured and used to develop the
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apparent kinetic model. The corresponding apparent kinetic parameters are estimated by

minimizing the square of the error between simulated values of residual weight fraction and

experimental values using non-traditional optimization technique logarithmic differential

evolution (LDE). The weight reduction with time suggests that the pyrolysis of de-oiled cake is

carried out in three stages. The maximum liquid yield obtained is 31.2% at 500 ˚C, which further

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decreases with an increase in temperature. The model predicted values of residual weight

fractions and yield of products are matching very well with the experimental data for all reactor

temperature.

Key words: Apparent kinetic model; Multi reaction kinetic scheme; Jatropha de-oiled cake;

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Pyrolysis; Product yields

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1. Introduction

The issue of low availability of fossil fuels and moderately growing awareness about the

environmental humiliation suggests that the renewable sources of energy would be major

supplier from the future perspective. Biomass fuels make no net contribution to the atmospheric

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CO2, if used sustainably with allowing re-grown [1]. Biomass can be processed into numerous

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ways depending upon its characteristics and the type of energy desired. The net energy available

from biomass upon combustion ranges from 8 MJ/kg for green wood to 20 MJ/kg for dried wood

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[2]. To utilize the solid biomass effectively and efficiently, thermo chemical conversion of solid

biomass to either bio-oil or charcoal or producer gas is essential. The pyrolysis and gasification

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are the two prominent processes which can be used for this purpose. Pyrolysis is the anaerobic
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thermal decomposition of biomass fuels i.e. devolatilization in the absence of oxygen. It involves

release of three kinds of products: charcoal, bio oil and non condensable gases. The yield of
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products depends on the chemical composition & size of biomass fuels and operating conditions
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of the pyrolysis reactor i.e. heating rate, final temperature and residence time of volatiles.
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Gasification is the process of converting the biomass into a combustible gas mixture by partial

oxidation of the biomass [3]. Various types of reactor configurations are used at pilot and
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commercial scale for the production of bio oil or producer gas. Those can be segregated into two

major categories: fixed bed and fluidized bed based reactors [4] [5]. For the successful operation
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of the pyrolyser or biomass gasifier, prediction of the rate of biomass devolatilization and yield
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of pyrolysis products is crucial. In general, the kinetics of biomass pyrolysis is developed by

conducting the thermo-gravimetric analysis (TGA) experiments. The experimental results of

weight loss characteristics of biomass are used to fit the kinetic model. The kinetic parameter

estimation is carried out by minimizing the sum of the square of the error between experimental

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and simulated values [6-9].

Different classes of mechanisms were proposed for the pyrolysis of wood and other

cellulosic materials. The models are classified into three categories: one-step global models, one-

stage multi-reaction models, and two-stage semi-global models [10]. Table 1 represents the

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various kinetic schemes along with kinetic parameters used. Bilbao et al. [11] utilized the one

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step global kinetic model and embedded into unsteady state heat transfer particle model for

predicting the influence of moisture content on the thermal decomposition of wood. Thurner and

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Mann [12] used one step multi reaction model to represent the kinetics of wood pyrolysis. Two

stage (primary and secondary stage) global multi reaction model is used by Chan et al. [13] and

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Di Blasi [14-15] in their modeling approach to represent the pyrolysis kinetics.
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Table 1 Kinetic parameters of various types of kinetic schemes

Sr Type of kinetic Kinetic model Kinetic parameters Reference

no. scheme

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Ki (s-1) E (kJ/mol)
1 One-step global 0.0000283 - Bilbao et al. [11]

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models ( T ≤ 563K )
Solid → Products
8.31 x 105 24.21

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(563 < T ≤ 673K )
0.0113 (T > 673K ) -

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2 one-stage multi- Solid → (products) i 8.607×105 88.6 Thurner and Mann

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reaction models where [12]
2.475×108 112.7
i = gases, tars and char
4.426×107

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106.5

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3 two-stage semi-global Solid → Gases1 1.3×108 140 Chan et al. [13]

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models Solid → Tars 1 2.0×108 133
Solid → Char1 1.08×107 121
Moisture → Water
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5.13×106 87.9
Tars 1 → Gases 2 + Char2 1.48×106 144
2.8×1019
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242.4 Di Blasi [14-15]

Biomass Active Biomass
Reaction 1 1.3×1010 150.5
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Reaction 2 Tar 3.28×1016 196.5

Active Biomass
Reaction 3 Char + Gases

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Biomass Component
K1 ( s −1 ) = A1 exp[(− D1 / T ) + ( L1 / T 2 )] Babu and Chaurasia
Reaction 1 Reaction 2 A1=3.28×10-5 , D1=17254.4 K and [16-21]
L1=-9061227 K2
(volatiles + gases)1 + (charcoal)1
K 2 ( s −1 ) = A2 exp[(− D2 / T ) + ( L2 / T 2 )]

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Reaction 3
(volatiles + gases)2 + (charcoal)2
A2=1.068×10-3 , D2=10224.4 K
L2=-6123081 K2

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K 3 ( s −1 ) = A3 exp(− E 3 / RT )
A3=5.7×105 , E3= 81 kJ/ mol

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168.4 51.965 Sadhukhan et. al.
13.2 45.96 [22-23]

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5.7×106 92.4

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4 One step apparent Solid → (Tars)1 + Char + CO + CO2 + H 2 + CH4 1.516×103 105 Di blasi [24-26] and
global kinetic model Tars 2 → (Tars)1 + H 2O + CO + CO2 + H 2 + CH 4 6 Patra et .al. [27]
4.28×10 107

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Solid → Products 5×10 6
120 Bonnefoy et. al. [28]

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Solid → Products 1.2×108 108.78 Roberts [29]

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In their later study [14] semi-global models proposed by other researchers[12-13, 30-32] of

cellulose and biomass pyrolysis have been compared in relation to conversion time and product

yields for a pure kinetic control. It is evident that the applicability of this kind of model is limited

and can be used only for small size (less than 1 mm) particles, which are undergoing kinetically

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controlled devolatilization. The pyrolysis of large size particles is controlled by heat and mass

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transfer within the particle. To predict the rate of devolatilization and yield of products for the

pyrolysis of large size particles, one has to develop the particle model and incorporate it into the

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reactor model. Many researchers such as Srivastava et. al. [33-34], Babu and Chaurasia [16-21]

and Sadhukhan et. al. [22-23] developed mathematical models to illustrate the pyrolysis of single

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biomass particle and large biomass particles. The kinetic model consists of both primary and
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secondary pyrolysis reactions while the heat transfer model includes diffusive, convective and

radioactive modes of heat transfer and temperature and mass loss were predicted. Few
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researchers [35-36] presented a combined transient single particle and fuel-bed model for the
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system involving pyrolysis as one of the process. The fuel-bed model is discretized, and mass,
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momentum and energy balances are solved for the entire system. Dou et al. [37] investigated the

kinetics of refuse plastic fuel (RPF) pyrolysis using a thermogravimetry analysis under
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isothermal conditions between 300 and 600 °C. A kinetic model was developed for examining

the effects of the surface chemical reaction and gas diffusion on the rate-limiting steps of RPF
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pyrolysis. It was reported that the rate of pyrolysis was controlled by a combination of the
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surface chemical reaction and gas diffusion through the solid. In their later study, Dou et al. [38]

applied the developed kinetic model for estimating the rates of hydrogen production and

reduction of Ni-based oxygen carriers (OCs) during chemical looping steam reforming (CLSR)

of ethanol. It was found that the rates of OCs reduction with ethanol were mainly controlled by

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surface chemical reaction and product layer diffusion.

The alternative to this approach is the development of apparent kinetic model [39-41] for

the pyrolysis process and use it without particle model development. To develop the apparent

kinetic model, conventional thermo-gravimetric analysis (TGA) results of biomass cannot be

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used. The pyrolysis of large size particle has to be carried out using macro-TGA experimental set

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up. Bonnefoy et. al. [28] conducted the pyrolysis experiments using beech wood (1 cm cube) as a

biomass. Measurements of weight loss and surface temperature were used to find the kinetic

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parameters of the one step global kinetic model. Although the developed model is an apparent

kinetic model, they have not done product quantification and characterization. Roberts [29] have

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proposed one stage single reaction apparent model for biomass pyrolysis. In their study, a
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comparison of various kinetic data for large sample is made. It is also mentioned that the kinetic

data developed using the experiments with small size samples of material are valid only under
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some conditions. In large samples, the effects of autocatalysis, secondary reactions, and physical
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structure may cause important modifications of the kinetics observed. Di blasi [24-26] and Patra
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et .al. [27] used one step apparent global kinetic model for wood devolatilization and predicted

the yield of tar, gas and charcoal in their respective study.

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The limitation of one step single reaction global kinetic model is the false prediction of

product yields variation with increase in the temperature. It predicts the continuous increase in
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the yields of bio oil, gas and charcoal with temperature, which is not observed experimentally. In
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reality, the yield of bio oil increases as the temperature increase till 550 - 600 ˚C and after that it

decreases as the cracking of volatile products takes place increasing the yield of gaseous

products. Hence, to predict the correct value of yield for various products, one or more step multi

reaction global kinetic model must be developed. In the present study, the thermal degradation of

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biomass is proposed by one step multi reaction global model. The degradation of biomass is

expressed as parallel production of volatiles, gases and charcoal. Macro thermo-gravimetric

analysis (TGA) of Jatropha de-oiled cake (biomass used in the present study) is performed using

laboratory macro TGA. The weight loss of the biomass, product yields and composition of non

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condensable gases are measured. These results are used to develop the apparent kinetic model.

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The model is simulated and corresponding global kinetic parameters are found. The developed

model could be an important contribution in the scientific literature to predict the pyrolysis

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process behavior and their product yields either for an independent operation or as a step/zone in

the gasification process operation. It can be further utilized for dynamic optimization for

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improving the performance of the system on a continuous basis.
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2. Kinetic model development and simulation
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2.1 Apparent kinetic model development

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In the present study, the kinetic model based on biomass degradation is proposed. Biomass gets
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decomposed by three parallel independent nth order reaction producing volatiles & gases and

charcoal. The kinetic model is described below:

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Reaction 3
Biomass a H2 + b CO + c CH4 + d CO2
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(Non condensable gases)

Reaction 1 Reaction 2 ( n3th order )
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Bio-oil Charcoal
th
( n order)
1 ( n2th order)

The kinetic equations for the mechanism, shown above are represented by equation (1).

ri = ki B ni (1)

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Where,

i bio-oil, non condensable gases and charcoal

ri rate of reaction for ithcomponent

ki kinetic constant of reaction for ithcomponent

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B concentration of biomass

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C concentration of charcoal

G concentration of non condensable gases

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V concentration of bio-oil

B, C, G and V are the function of reaction time. To find the kinetic parameters of the above-

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mentioned reactions, the square of the error between the experimental data of fixed bed of
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Jatropha de-oiled cake and model predicted values of residual weight fraction are minimized.

The residual weight fraction is defined as given by equation (2)

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Residual Weight Fraction (W) =

(Residual Weight ) (2)
(Initial Weight )
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To find the residual weight fraction theoretically, net rate of production of different species by
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reaction 1 & 2 in terms of rate of reactions are found. The residual weight fraction is calculated
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using equation (2).

W=B+C (3)
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Using equations (1) & (3), rate of change of biomass constituents are given by equation (4) and
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rate of production of charcoal is given by equation (6).

= (kV )B ni
dV
(4)
dt

= (k G )B ni
dG
(5)
dt

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= (k C )B ni
dC
(6)
dt

= −(k G + kV + k C )B ni
dB
(7)
dt

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So change of residual weight fraction with time [equation (8)] is obtained by addition of equation

(6) & equation (7).

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= −(k G + kV )B ni
dW
(8)
dt

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To find temperature (T) at a particular time (t), following equation [equation (9)] is used

T = (HR)t + T0 (9)

where
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T0 initial temperature

HR heating rate
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Differentiating equation (12) would result in

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dT = (HR)dt (10)
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Using equation (8) and equation (10), the relations of change of residual weight fraction with

temperature is found and given by equation (11).

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= −(k G + k V )B ni
dW 1
(11)
dT HR
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Using equation (7) and equation (10), the relation of change of biomass weight fraction with
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temperature is found and given by equation (12).

= −(k G + kV + k C )B n
dB 1
(12)
dt HR

Arrhenius relation of kinetic constants with temperature is given by equations (13 – 15)

respectively for reaction 1, reaction 2 and reaction 3.

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 − EG 
k G = AG exp  (13)
 RT 

 − EV 
kV = AV exp  (14)
 RT 

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 − EC 
k C = AC exp  (15)
 RT 

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The values of the frequency factor and activation energy of all reactions are found by minimizing

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the objective function as given by equation (16). For the minimization, all data points (n) of a

particular heating rate are considered to determine the kinetic parameters.

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F (AG , E G , AV , EV , AC , E C , ni ) = ∑ (Wtotal,exp, j − Wtotal, cal, j )
n
2
(16)
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j =1

Where,
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Wtotal,exp experimental value of the residual weight fraction

Wtotal,cal calculated value of the residual weight fraction (predicted from model)
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2.2 Simulation methodology

In our previous study [6-7], kinetic parameter estimation was carried out using logarithmic DE
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(LDE). Optimum kinetic parameters are found by minimizing the objective function using LDE.
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Differential evolution algorithm [42-44] of optimization was modified by including the

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logarithmic initialization (LIDE) and logarithmic mutation and named as logarithmic DE (LDE)

[8]. The key parameters of LDE are number of population (NP), crossover constant (CR) and

scaling factor (F). The values used in the present case are: NP – 200, CR – 0.9 and F – 0.5. The

limits of the activation energies and frequency factors are given below,

Limits of frequency factors (AG, AV&AC) = (1.0e+2, 1.0e+18)

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Limits of activation energy (EG) = (1.0e+04, 2.5e+05)

Limits of activation energy (EV) = (1.0e+05, 2.5e+05)

Limits of activation energy (EC) = (1.0e+05, 2.5e+05)

Limits of order of reaction (n) = (0, 2)

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To find the theoretical value of residual weight fraction (Wtotal), finite difference technique [45] is

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applied to equation (11) to equation (15) with the following initial conditions.

At time t=0

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T0 = 305 K; B = 1.0; C = 0.0; G=0; V=0; W = 1.0

3. Materials and methods

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3.1 Materials

The biomass (Jatropha de-oiled cake) used in the present study is the waste generated in
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Jatropha oil extraction industries. It is purchased from the supplier based at Gujrat, India.
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Jatropha de-oiled cake is pyrolyzed in a macro TGA experimental set up at different

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temperatures ranging from 400 – 700 ˚C for particle size varying from 0.25 mm to 25.4 mm.

Jatropha Curcas is famous as the major appropriate energy crop for producing the bio diesel. It
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can be used to retrieve land, as a hedgerow and/or as a commercial crop. The seed material

comprises of 41% shell and 59% kernel. The kernel consists of around 40–50% of oil[46].
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Biodiesel production from Jatropha seeds generates a large amount of superfluous de-oiled seed
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cake. Although the black gold is a vivid biodiesel feedstock, potential utilization or safe disposal

of huge amounts of seed cake by-product needs to be addressed. Jatropha curcas seed cake

cannot be used as cattle feed, unlike other oilseeds, largely because of the presence of toxic

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phorbol esters in it. Phorbol esters are recognized as main toxicants in cake, which could not be

demolished even by heating at 160 ˚C for 30 min [47].

De-oiled cake, a solid residue that was remaining after extraction of oil from seeds, contains

lignin and cellulose in different ratios. Additionally, due to continuous increasing demand of

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biodiesel, production of oil cakes has increased immensely and about 2 tons of oil cake is

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dumped as a waste for every ton of biodiesel production[48]. Large amount of de-oiled cake is

generated in form of a waste product during production of biodiesel from its seeds. The ultimate

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analysis of Jatropha de-oiled cake is carried out at Sigma Test and Research Centre, New Delhi,

India and shown in Table 2. The gross calorific value is found to be 17.7 MJ/kg using digital

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bomb calorimeter supplied by Popular Science Apparatus Workshops Pvt. Ltd.
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Table 2. Ultimate analysis of Jatropha de-oiled cake
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Property

C (% by mass) 53.39
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H (% by mass) 6.81
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O (% by mass) 29.27

N (% by mass) 0.45
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S (% by mass) 0.12

H/C Ratio 1.53

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Empirical formula CH1.53O0.4N0.007S0.0008

3.2 Experimental set up

The pyrolysis is conducted in the reactor as shown in figure 1. The weight loss is monitored for a

specific heating rate. It is the same as TGA but at a macro level. Hence, we used the term

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“macro-TGA” for the pyrolysis reactor. The macro TGA (pyrolysis reactor) is designed in lab

and fabricated by Indfurr Superheat Furnaces, Tamilnadu, India. The cylindrical stainless steel

reactor is having a diameter of 15.5 cm and a height of 30 cm, which is placed in an electric

furnace. The temperature controller unit is connected to the furnace, which governs the reactor

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temperature and also the heating rate. To provide the inert environment inside the reactor,

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nitrogen gas is purged continuously inside the reactor. The contents in the reactor are

continuously weighed during the pyrolysis run using the balance (Make: Shimadzu; Model No:

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TX2202L). The weight reduction data are continuously collected at rate of 2 data points/Sec and

the heating rate is 5 °C/min. Upon increasing the temperature, the biomass sample gets

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pyrolyzed and releases the volatiles. The volatiles along with inert nitrogen exits from the top of
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the reactor and are cooled in a two-stage condenser followed by an ice trap.
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Figure 1. Experimental Set-up Diagram

3.3 Methodology

3.3.1 Pyrolysis of biomass in macro TGA

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Pyrolysis is carried out at final temperatures of 350 to 700 ˚C in the interval of 50 ˚C with the

help of macro TGA. Its having an internal volume of 22.63 ltr (15.5 cm ID), which is heated

externally by an electric furnace and the temperature is measured by a thermocouple on the inner

side of the reactor. Experiment are carried out under sweeping gas i.e. nitrogen with a volumetric

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flow rate of 2 LPM and solid, gas and liquid product yields are deliberated. A fixed quantity (29

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grams) of Jatropha de-oiled cake is placed on the sample holder and nitrogen gas is purged for

10 min at a flow rate of 2 L/min to create an inert atmosphere. After that, the heating is started

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and the reactor temperature is increased from room temperature to the desired pyrolysis

temperature. The released volatiles leave the reactor and reach to the condenser. The pipeline

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conveying the volatiles components from macro TGA to condenser is also maintained at a
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temperature of 250 ˚C to restrict any kind of condensation of volatiles before condenser. The

volatiles are condensed to liquid products referred as bio-oil.

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3.3.2 GC analysis of non-condensable gas

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The gas chromatographic analysis of non-condensable gas is done using Shimadzu 2014 gas
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chromatography. The GC analysis shows the composition of gases (H2, CH4, CO and CO2) at

different time and at different temperature of reactor. The carbosphere column is equipped and
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Argon is used as a carrier gas with flow rate 8 ml/min. The operating conditions for GC such as

injection temperature, column temperature and thermal conductivity detector temperature are
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kept at 100 ˚C, 45 ˚C and 100 ˚C respectively. The gas samples are taken at every 50 ˚C interval
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and analysed using GC.

4. Results and discussion

4.1 Experimental results

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4.1.1 Effect of temperature on yield of products

Figure 2 shows the product yield distribution for the pyrolysis of Jatropha de-oiled cake carried

out at different temperatures. The liquid product obtained has a reddish-brown colour with an

irritant odour. The liquid yield is 18%, 25%, 29% at pyrolysis temperatures 350, 400 and 550 ˚C.

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The maximum liquid yield is 31.2% at 500 ˚C, which further decreases with an increase in

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temperature. The char yield gradually decreases from 48.25% to 31.8% with the increase in

temperature. The decrease in solid product yield with an increase in temperature could be either

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due to greater primary decomposition of de-oiled cake to primary volatiles at higher

temperatures or may be due to secondary degradation of the product of primary decomposition

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[49]. The gas yield initially shows a downfall and then increases with an increase in temperature.
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This may be certainly due to the secondary cracking of the pyrolysis vapours and char at high

temperatures, which may also lead to formation of some non-condensable gaseous products. The
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yield of products is shown in Figure 2.

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50
Gas Yield
Liquid Yield
Solid Yield

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40
Product Yield (%)

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30

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20

300 400 500

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0
Temperature ( C)

Figure 2. Product yield distribution of pyrolysis of Jatropha de-oiled cake

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Figure 3 (a), (b) and (c) show the product yield distribution for the pyrolysis of different particle
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size Jatropha de-oiled cake at different temperatures. It’s clearly shown that charcoal yield is

more for large size particle than the small size particle for the same final temperature of reactor.
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It is due to the fact that for the large particle size, the temperature within the particle would be
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much lower than that of the reactor. Hence, the lower temperature in the core of the particle leads

to low temp pyrolysis producing more charcoal and less yield of bio-oil and non-condensable
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gases. As the final temperature increases the charcoal yield is reduced for the same particle size.
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At the same time the yield of non-condensable gases increases with increase in the final

temperature of the reactor. However, for the bio oil, increment in the yield is observed for 550 ˚C

and reduction in yield for 700 ˚C. It is due to the secondary cracking of the volatiles into the

permanent gases. From figure 3, it can be seen that the difference between the charcoal yield, bio

oil yield and yield of non-condensable gases of 52-60 mesh size and 10-14 mesh size particle is

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small and same observation is made for 0.5 inch and 1 inch size particle. However, there is a

huge difference (13.3 %) in charcoal yield of 52-60 mesh size and 1 inch size particle at 400 ˚C

of reactor temperature. As the final temperature of reactor increases, this difference in the yield

is reduced up to a value of 3.5 %. The yield of non-condensable gases varies from 35.9 % to 41.4

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% and 25.6 % to 41 % for 52-60 mesh size and 1 inch particle size respectively.

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0.50

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Particle size 10-14 mesh
0.45 Particle size 52-60 mesh
Particle size 0.5 inch
Particle size 1.0 inch
0.40

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Oil Yield

0.35
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0.30
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0.25

0.20
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350 400 450 500 550 600 650 700 750

Final temperature (oC)

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(a)

0.50
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Particle size 10-14 mesh

0.45 Particle size 52-60 mesh
Particle size 0.5 inch
Particle size 1.0 inch
C

0.40
Charcoal yield
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0.35

0.30

0.25

0.20
350 400 450 500 550 600 650 700 750
o
Final temperature ( C)
(b)

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0.50
Particle size 10-14 mesh
Particle size 52-60 mesh
0.45 Particle size 0.5 inch

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Particle size 1.0 inch

0.40
Gas yield

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0.35

0.30

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0.25

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0.20
350 400 450 500 550 600 650 700 750

Final temperature (oC)

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(c)
Figure 3. Product yield distribution of pyrolysis of Jatropha de-oiled cake
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(a) Oil yield (b) Charcoal yield (c) Gas yield

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4.1.2 Macro TGA analysis of biomass

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Figure 4 shows the macro TGA of Jatropha de-oiled cake at a final reactor temperature of 700

˚C. Three stages are observed for the pyrolysis of de-oiled cake. The first stage is a pre-pyrolysis
EP

which occurs between 120 and 220 ˚C with a small weight loss releasing, this may be due to
C

some internal rearrangements, such as breakage of bond and formation of free radicals &
AC

carbonyl groups. For large size particle heat has to penetrate in the particle and it takes time to

diffuse till core of the particle. The mode of transfer of heat is diffusion but it’s slow due to

lower thermal diffusivity and large size of particle. As the particle gets heated, the volatile

releases and the onset of drop in weight fraction are observed [50]. The second stage displays

main pyrolysis process, during which a significant weight loss from the initially fed biomass is

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observed. This maximum weight loss takes place from 250 to 500 ˚C. In this stage, the weaker

chemical bonds and intermolecular associations are destroyed [51]. The further cleavage of C–H

and C–O bonds occur the last stage, i.e. continuous charcoal devolatilization, caused by [52].

Figure 4 shows the weight reduction with temperature for four different particle sizes of biomass

PT
for the final reactor temperature of 700 ˚C. Similar trends are observed for 400 ˚C and 550 ˚C.

RI
1.1

SC
1.0

0.9

0.8

U
Wt. fraction

0.7

0.6
AN
0.5

0.4
0.5 Inch particle size
M

0.3
1 Inch particle size
0.2 10-14 mesh particle size
52-60 mesh particle size
0.1
D

100 200 300 400 500 600 700

0
Temperature ( C)
TE

Figure 4. Macro Thermogravimetric Analysis of Jatropha de-oiled cake at 700 ˚C for

EP

different particle size.

C

It can be seen that the weight reduction till 300 ˚C is appreciable for large size particles (0.5 and
AC

1 inch size) in comparison to the smaller size particles (10-14 mesh and 52-60 mesh). The large

size particles observed early weight reduction in comparison to the smaller size particles. It is

due to the heat transfer effects in the reactor. The particles are placed in the cylindrical pan in the

reactor and get heated by radiation from top and by conduction through bottom and through

circular periphery. Due to high porosity of larger size particle bed, it receives the large amount of

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heat through radiation. Hence, its temperature gets increased and achieves high weight reduction

at low reactor temperature in comparison to the low porosity smaller size particle bed.

4.1.3 GC analysis of non condensable gas

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Figure 5 shows the composition variation of nitrogen free non-condensable gases at different

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temperature for various particle sizes. The major compounds characterized by GC analysis of

nitrogen free non condensable gas are H2, CH4, CO and CO2. It can be seen that the

SC
concentration of CO2 is minimum at 450 ˚C and remains almost constant. CH4 concentration is

least and almost constant for all temperatures. It is observed H2 concentration varies from 0.1 to

U
0.22 and slightly increases with increase in temperature. The CO concentration is decreasing
AN
with increase in temperature and varies from 0.25 to 0.12.
M

4.2 Simulation and kinetic parameter estimation

D

The kinetic parameters are established by minimizing the square of the error between
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experimental and theoretical residual weight fractions at different reactor temperature using

logarithmic differential evolution (LDE). LDE provides set of optimum kinetic parameters with
EP

minimum value of the objective function. Table 3 and 4 show the kinetic parameters of reaction

1 of bio-oil formation, reaction 2 of charcoal production and reaction 3 of non condensable gases
C

formation for various particle sizes. The stoichiometric coefficient of the each component of the
AC

non condensable gaseous mixture is estimated based on the time averaged value of the GC

analysis. Figures 6(a)-(d), 7(a)-(d) and 8(a)-(d) show that the model predicted values of residual

weight fractions are matching very well with the experimental data for all reactor temperature.

Figures 9 and 10 show the comparison of the predicted yield of oil, non-condensable gases and

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charcoal with experimental product yields for large particle of biomass (0.5 inch and 1.0 inch

particle size) and good agreement is found with experimental product yield data.

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0.7

RI
0.6 0.5 inch particle
H2
Gas composition

CO
0.5 CH4

SC
CO2
0.4 1 inch particle
H2
CO
0.3 CH4
CO2

U
0.2
AN
0.1

0.0
300 400 500 600 700
M

o
Temperature ( C)

Figure 5. Gas chromatographic analysis of non condensable gases (nitrogen free basis)
D
TE
C EP
AC

23
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Table-3 Estimated kinetic parameters for small size biomass pyrolysis.

Particle Size 10-14 mesh (1.4 to 2.0 mm) 52-60 mesh (0.25 to 0.3 mm)

Reactor Temp. (0C) 400 550 700 400 550 700

A0

PT
4.34E+02 3.72E+11 4.14E+04 1.02E+02 1.00E+02 4.53E+02
(min-1)
Kinetic
EV

RI
data for 6.42E+04 1.63E+05 8.64E+04 5.27E+04 5.80E+04 6.69E+04
Volatiles (J/ mol)

SC
Order of
1.55E+00 2.00E+00 2.00E+00 1.85E+00 2.00E+00 2.00E+00
Reaction

A0

U
1.00E+18 7.52E+09 5.93E+03 1.24E+07 3.35E+05 4.56E+02
(min-1)
AN
Kinetic
EC
data for 2.30E+05 1.44E+05 7.69E+04 1.01E+05 9.77E+04 6.76E+04
Char (J/ mol)
M

Order of
1.55E+00 2.00E+00 2.00E+00 1.85E+00 2.00E+00 2.00E+00
Reaction
D

A0
1.00E+18 1.00E+02 4.97E+04 5.32E+15 1.55E+08 2.62E+03
(min-1)
TE

EG
2.32E+05 5.87E+04 1.94E+05 1.94E+05 1.29E+05 7.46E+04
(J/ mol)
EP

Kinetic Order of
1.55E+00 2.00E+00 2.00E+00 1.85E+00 2.00E+00 2.00E+00
data for Reaction
Gas
C

a 0.2193 0.2206
AC

b 0.1743 0.1637

c 0.0445 0.0412

d 0.5619 0.5745

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Table-4 Estimated kinetic parameters for large size biomass pyrolysis.

Particle Size 1 inch 0.5 inch

Reactor Temp. (0C) 400 550 700 400 550 700

A0

PT
1.00E+02 1.23E+03 3.60E+02 7.08E+17 9.80E+03 1.21E+02
(min-1)
Kinetic
EV

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data for 5.48E+04 6.71E+04 5.95E+04 4.23E+04 7.62E+04 5.38E+04
Volatiles (J/ mol)

SC
Order of
1.74E+00 2.00E+00 2.00E+00 1.87E+00 2.00E+00 2.00E+00
Reaction

A0

U
6.14E+15 1.13E+05 3.89E+02 9.60E+11 1.17E+03 1.00E+02
(min-1)
AN
Kinetic
EC
data for 1.96E+05 8.71E+04 6.29E+04 1.57E+05 6.58E+04 5.60E+04
Char (J/ mol)
M

Order of
1.74E+00 2.00E+00 2.00E+00 1.87E+00 2.00E+00 2.00E+00
Reaction
D

A0
1.91E+17 2.46E+06 4.46E+15 1.01E+02 2.01E+03 3.64E+15
(min-1)
TE

EG
2.15E+05 1.02E+05 2.50E+05 5.55E+04 6.89E+04 2.50E+05
(J/ mol)
EP

Kinetic Order of
1.74E+00 2.00E+00 2.00E+00 1.87E+00 2.00E+00 2.00E+00
data for Reaction
Gas
C

a 0.1722 0.1749
AC

b 0.1580 0.1654

c 0.0445 0.0432

d 0.6252 0.6164

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1.1 1.1

1.0 1.0
(a) (b)
0.9 0.9

0.8 0.8
wt. fraction

wt. fraction
0.7 0.7

0.6 0.6

PT
0.5 0.5

0.4 Experimental fraction wt. 0.4 Experimental fraction wt.

Predicted fraction wt. Predicted fraction wt.
0.3 0.3

RI
0.2 0.2
100 200 300 400 100 200 300 400
0 0
Temperature ( C) Temperature ( C)

SC
1.1 1.1

1.0 (c) 1.0 (d)

0.9 0.9

U
0.8 0.8
wt. fraction

wt. fraction

0.7 0.7
AN
0.6 0.6

0.5 0.5

0.4 Experimental fraction wt. 0.4 Experimental fraction wt.

Predicted fraction wt. Predicted fraction wt.
0.3 0.3
M

0.2 0.2
100 200 300 400 100 200 300 400
0 0
Temperature ( C) Temperature ( C)
D

Figure 6. Comparison of Experimental and simulated residual weight fraction at 400 ˚C

TE

reactor temperature for particle size (a)1 inch (b) 0.5 inch

(c) 10-14 mesh (1.4 to 2.0 mm) (d) 52-60 mesh (0.25 to 0.3 mm)
C EP
AC

26
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1.1 1.1

1.0 1.0

0.9 (a) 0.9 (b)

0.8 0.8
wt. fraction

wt. fraction
0.7 0.7

0.6 0.6

PT
0.5 0.5

0.4 0.4

0.3 0.3
Experimental fraction wt. Experimental wt. fraction
0.2 Predicted fraction wt. 0.2 Predicted wt. fraction

RI
0.1 0.1
100 200 300 400 500 600 100 200 300 400 500 600
0 0
Temperature ( C) Temperature ( C)

SC
1.1 1.1

1.0 1.0
(c)
0.9 0.9
(d)

U
0.8 0.8
wt. fraction

0.7
wt. fraction 0.7

0.6 0.6
AN
0.5 0.5

0.4 0.4

0.3 0.3
Experimental fraction wt. Experimental fraction wt.
0.2 Predicted fraction wt. 0.2 Predicted fraction wt.
M

0.1 0.1
100 200 300 400 500 600 100 200 300 400 500 600
0 0
Temperature ( C) Temperature ( C)
D

Figure 7. Comparison of Experimental and simulated residual weight fraction at 550 ˚C

TE

reactor temperature for particle size (a)1 inch (b) 0.5 inch
EP

(c) 10-14 mesh (1.4 to 2.0 mm) (d) 52-60 mesh (0.25 to 0.3 mm)
C
AC

27
 ACCEPTED MANUSCRIPT

1.1 1.1

1.0 1.0

0.9 0.9

(a) (b)
0.8 0.8
wt. fraction

wt. fraction
0.7 0.7

0.6 0.6

PT
0.5 0.5

0.4 0.4

0.3 0.3
Experimental fraction wt. Experimental fraction wt.
0.2 Predicted fraction wt. 0.2
Predicted fraction wt.

RI
0.1 0.1
100 200 300 400 500 600 700 100 200 300 400 500 600 700
0 0
Temperature ( C) Temprature ( C)

SC
1.1 1.1

1.0 1.0
(c) (d)
0.9 0.9

U
0.8 0.8
wt. fraction

wt. fraction

0.7 0.7

0.6 0.6
AN
0.5 0.5

0.4 0.4

0.3 0.3
Experimental wt. fraction
Predicted wt. fraction Experimental fraction wt.
0.2 0.2
Predicted fraction wt.
M

0.1 0.1
100 200 300 400 500 600 700 100 200 300 400 500 600 700
0 0
Temprature ( C) Temprature ( C)
D

Figure 8. Comparison of Experimental and simulated residual weight fraction at 700 ˚C

TE

temperature for particle size (a)1 inch (b) 0.5 inch

(c) 10-14 mesh (1.4 to 2.0 mm) (d) 52-60 mesh (0.25 to 0.3 mm)
C EP
AC

28
 ACCEPTED MANUSCRIPT

0.8

Particle size 0.5 inch

0.7 Experimental Oil Yield
Predicted Oil Yield
Particle size 1.0 inch
0.6
Experimental Oil Yield

PT
Predicted Oil Yield
Oil yield

0.5

RI
0.4

0.3

SC
0.2
350 400 450 500 550 600 650 700
o
Temperature ( C)

U
AN
Figure 9. Comparison of Experimental and simulated oil yield at different reactor

temperatures for particle size 0.5 inch and 1 inch

M

0.8
D

Particle size 0.5 inch

0.7 Experimental Charcoal Yield
TE

Predicted Charcoal Yield

Particle size 1.0 inch
0.6 Experimental Charcoal Yield
Charcoal yield

Predicted Charcoal Yield

EP

0.5

0.4
C

0.3
AC

0.2
350 400 450 500 550 600 650 700
o
Temperature ( C)

Figure 10. Comparison of Experimental and simulated charcoal yield at different

reactor temperatures for particle size 0.5 inch and 1 inch

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0.8
Particle size 0.5 inch
Experimental Gas Yield
0.7 Predicted Gas Yield
Particle size 1.0 inch
Experimental Gas Yield
0.6
Predicted Gas Yield

PT
Gas yield

0.5

RI
0.4

0.3

SC
0.2
350 400 450 500 550 600 650 700
o
Temperature ( C)

U
AN
Figure 11. Comparison of Experimental and simulated gas yield at different reactor

temperatures for particle size 0.5 inch and 1 inch

M

Figures 9, 10 and 11 show the comparison of experimental and simulated product yield at

different reactor temperatures for particle size 0.5 inch and 1 inch respectively. It is observed that
D

the experimental bio oil yield varies from 26.25 % to 33.5 % for 0.5 inch particle and 28.1 % to
TE

32.2 % for 1 inch particle as the pyrolysis temperatures rise from 400 to 700 ˚C. The maximum

bio oil yield is 33.5% and 32.2 % at 550 ˚C for 0.5 inch and 1 inch particle respectively.
EP

However, the predicted or simulated bio oil yield varies from 29.5 % to 33.5 % and 24.82 % to
C

31.42 % respectively as the pyrolysis temperatures rise from 400 to 700 ˚C. The maximum bio
AC

oil yield is achieved at 550 ˚C. The experimental char yield gradually decreases from 46.17% to

22.76% with the increase in temperature. However the predicted or simulated charcoal yield

decreases from 45.22 % to 29.47 %. The experimental gas yield gradually increases from

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27.57% to 44.77% with the increase in temperature. However the predicted or simulated gas

yield increases from 25.2 % to 38.1 %.

5 Conclusions

In the present study, the thermal degradation of biomass is proposed by one step multi reaction

PT
apparent global kinetic model. The degradation of biomass is expressed as parallel production of

RI
bio-oil, non condensable gases and charcoal. Macro thermo-gravimetric analysis (TGA) of

Jatropha de-oiled cake (biomass used in the present study) is performed using laboratory macro

SC
TGA experimental setup. The weight loss of the biomass, product yields and composition of non

condensable gases are reported in the present study. It is found that the temperature has

U
significant effect on pyrolysis yields and conversion efficiencies. Based on the macro TGA
AN
studies, it is found that maximum weight loss of biomass is in the range of 250 – 500 ˚C and

most of the volatile products are also formed in the same range. The weight reduction with time
M

suggests that the pyrolysis of de-oiled cake is carried out in three stages. The maximum liquid
D

yield obtained is 31.2% at 500 ˚C, which further decreases with an increase in temperature.
TE

These results are used to develop the apparent kinetic model. The model is simulated and

corresponding global kinetic parameters are found. The model predicted values of residual
EP

weight fractions and yields of products are matching very well with the experimental data for all

reactor temperature.
C
AC

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Highlights

• Biomass pyrolysis is proposed by one step multi reaction apparent

kinetic model.

PT
• Macro TGA of biomass is performed at temperatures ranging from

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350 ˚C to 700 ˚C.

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• The apparent kinetic parameters are estimated using logarithmic
DE.

U
AN
• The simulated products’ yield is matching very well with the
experimental data.
M
D
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AC