Project Code T5

Developing Model For TGA Analysis Of Biomass

Bachelor of Technology
in
Mechanical Department
by
Ishvar Honrao 2015ME20734
Mayank Mahawar 2015ME10658

Date: 09/18

Under the supervision of Examiner

Prof. P M V Subbarao Prof. M R Ravi

……………….
………...……
.…………….. ……………….

Department of Mechanical Engineering

September 2018
Abstract
Biomass consists mainly of three major components hemicellulose, cellulose, and lignin
together with trace amount of extractives and minerals. Biomass energy uses organic matter such
as wood or plants for creating heat, generating electricity and producing green oil for cars.
Differences in chemical structures of biomass components lead to different chemical reactivities,
making the relative composition in cellulose, hemi- celluloses and lignin in the biomass a crucial
factor for process design.

The pyrolysis characteristics of the three components are first analyzed, and the process
of biomass pyrolysis is divided into four ranges according to the temperatures specified by
individual components[2]. The main aim of this project is to obtain the lignin, hemicellulose and
a-cellulose contents in biomass. We are using a new method called thermogravimetric analysis .
This is an alternative method for biomass analysis that is faster, easier to use and less expensive
than existing techniques and methods with comparable or enhanced accuracy. Also we are
concerned with the kinetics of the thermal decomposition of a different types of biomass . It
contains kinetic analysis of TGA data using a variety of approaches. Kinetic parameters like
activation energy (E) and pre-exponential factor (A) obtained from the this study.
1. Introduction

The major chemical components of lignocellulosic biomass are cellulose, hemicellulose

and lignin. Normally, cellulose, hemicellulose, and lignin cover 40-60, 20-40, and 10-25 weight
% of biomass materials respectively. The chemical differences between these components
directly influence their chemical reactivities. This is why the knowledge of the total amount of
each component is crucial to foresee the efficiency of a biomass conversion process. Knowing
accurately the chemical composition of complex lignocellulosic biomass is getting increasing
importance for enabling process commercialization converting biomass into green fuels or
valuable chemicals. For this purpose there are numerous wet chemical processes based on the
fractionation of biomass sample. These chemical methods are highly accurate but these methods
cannot be applied in a commercial setting because they are expensive and time consuming. So
we use Thermogravimetry analysis (TGA) . By using this we can understand suitability for
gasification of biomass. Kinetic parameters like activation energy (E) and pre-exponential factor
(A) to be obtained from the TGA study. These parameters provide good information on thermal
degradation and peak temperature during pyrolysis of the biomass. TGA can quantitatively
resolve complex mixtures because of the characteristic thermal decomposition temperature of
each component the pyrolytic decomposition of woody plant tissues in inert atmospheres occurs
at mild temperatures for hemicelluloses followed by cellulose and finally lignin .The
combination of TGA and differential thermogravimetric analyses (DTG) allows obtaining the
lignin content and particularly its influence during the combustion process. Finally, cellulose and
lignin contents of pulp and paper have been determined by TGA especially in the description of
the biomass pyrolysis leading unfortunately to high errors on hemicelluloses contents. In view of
these studies, TGA turns out to be a powerful tool for these analytical purposes. TGA is
alternative method for biomass analysis that is faster, easier to use and less expensive than
existing techniques and methods with comparable or enhanced accuracy.
2. Literature Survey

Determination of biomass compositions was mainly carried out in two industrial sectors:
the wood and the food industry. Both have developed their own experimental procedures to
quantify the amount of a-cellulose, hemi- celluloses and lignin. Especially in wood industry
sector wet chemical method is used to determining the composition. In this method different
chemical are used according to the component property. This method is most accurate but more
expensive than TGA because of this is not used in other sector.

Numerous studies based on one or all the three components (i.e. hemicellulose, cellulose,
and lignin ). Several have focused on developing kinetic models for predicting the behaviour of
biomass pyrolysis. Kinetic parameters like activation energy (E) and pre-exponential factor (A)
to be obtained from different methods. Some of the studies indicated that it is important to
distinguish the behaviour of the three components for a better understanding of the biomass
pyrolysis process. Generally, biomass pyrolysis proceeds through a series of complex reactions.
At low heating rates (<100 °C/min), biomass materials decompose in well-described stages of
moisture evolution, hemicellulose decomposition and cellulose decomposition, while lignin is
decomposed very slowly and at a minor level. In some of the papers the overall rate of biomass
pyrolysis was considered as a sum of the individual rates of the three components.

Some experimental or computing approaches for determining the contents of the three
components in natural biomass have been established. But these methods require several
extractive steps and are generally time consuming. So the TGA is used for the thermal
degradation of sample. TGA is determine the amounts of the three main components in the
biomass and also the weight loss of the biomass specific temperature ranges.

Some research on the gasification of all three main components of biomass to evaluate
and compare their hydrogen production and also understand their gasification processes. two-
stage reaction system has been used employing various nickel-based catalysts. Gas concentration
(CO, H2, CO, CO2 and CH4) was analysed for the produced non-condensed gases. Oil by-
products were analysed by gas chromatography/mass spectrometry (GC/MS). In this paper they
shown that Lignin generates the highest residue fraction(52%).
3. Objectives

3.1 Problem definition

The TGA method analysis is time saving method as compared to the traditional chemical
method. The focus was on development of an numerical analysis model of TGA/ DTG for
accurate prediction of biomass composition. A broadly applicable model will empower to use the
model with similar algorithm to implement in other areas such as polymer estimation.

3.2 Objective

To develop a multi-gaussian deconvolution model based on gaussian mixture model

algorithm on DTG curve from the TGA analysis data which will be then trained using Artificial
Neural Networks for robust performance on variety of sample.

The steps followed are sequentially explained as below:

1. The characterization and chemical analysis of biomass samples gives an accurate(almost)

estimation of the biomass sample albeit at the cost of time, for which TGA was an time &
cost saving alternative.
2. The first model developed was a weighted difference method for which DTG peaks were
mapped onto TGA curve for estimation of composition.
3. Implementation of GMM model using MATLAB curve-fit toolbox
4. Training using Neural Net toolbox in MATLAB for increasing robustness.
5. Validation of the model on other biomass components.
6. Thermal analysis performed in an inert atmosphere the TGA and DTG curves of the
samples were compared.
7. MATLAB mathematical methods to be used to extract kinetic parameters of pyrolysis.

3.3 Methodology

The TG analysis is carried out on thermogravimetric analyser . In this experiment Nitrogen

is selected as the purge gas. The flow rate of nitrogen, desired end temperature and heating rate
is set accordingly. Before filling the alumina pan with sample, pan weight is calibrated to zero.
The sample to be analysed is filled in the pan and its initial weight is recorded. Then, the
equipment is made to run. The progress of the run is observed through the monitor connected to
the equipment. Once the run is done, the furnace is cooled with the help of purge gas. Then TGA
is switched off and purge gas is cut off. Before each trial temperature calibration of the device is
performed by measuring the melting point of aluminium metal piece.
3.4 Gantt Chart

Flow chart 1: GMM Deconvolution Method Flow chart 2: TGA Peak Mapping Method
4.Work Progress:
4.1 Study of Kinetic Modelling for TGA by Differential Method

This is one of the methods used to obtain the pyrolysis kinetic parameters from the
Thermogravimetric data. The kinetics of most reactions under non-isothermal conditions can be
summarized by the following general equation.
da
= kf (a ) …. (1)
dt
α = (m - mi)/ (mf - mi)
Here α is the conversion fraction of the mass reacted in time t relative to the final mass
k - Rate constant
æ-Eö
k = A expç ÷ …. (2)
è RT ø
The heating rate was assumed to be constant and linear. Hence, the expression for heating rate is
as follows:
dT
bº …. (3)
dt

Combination of equation 1 and 2 gives

da
E
-
= Af (a )e RT …. (4)
dt

Substituting for “dt” using equation 3 gives

da A
E
-
= f (a )e RT …. (5)
dT b

Thus equation 5, if rearranged, gives

da
E
A -
= e RT dT …. (6)
f (a ) b

Equation 6 is the basic equation of the TGA curve when it is integrated. If the form of the
function f(α) is known, integration of the left-hand side of the equation is straightforward. The
integration limits are between the initial and final temperature of the reaction and are between
 α = 0 and α = 1. The values of E and A have a marked influence on the temperature range over
which the TGA curve is observed, but they do not significantly influence the shape of the curve.
However, the kinetic mechanism, the form of f(α), determines the shape of the curve. For a first
order reaction, f(α) may be expressed as
æ 1-a ö
f (a ) = çç ÷÷ …. (7)
è1- X C ø

Substituting for f(α) from equation 7 into equation 4 gives

da æ 1 - a ö - RTE
=ç ÷÷ Ae …. (8)
dt çè 1 - X C ø

æ m - mi ö æ m / mi - 1 ö
Now, a = ç ÷=ç ÷ …. (9)
çm -m ÷ ç X -1 ÷
è f i ø è C ø
$
where X" = $% , is called char fraction, by stoichiometry of the decomposition reaction.
&

Taking a natural logarithm of equation 8 yields:

æ da ö éæ 1 - a ö ù E
lnç ÷ = lnêçç ÷÷ Aú - …. (10)
è dt ø ëè 1 - X C ø û RT

Apparent activation energy, E, is determined from the relationship between ln(dα/dt) and
1/T from Eq. (10). Thus, a family of parallel straight lines of slope –E/R can be obtained, from
which the apparent activation energy (E) corresponding to the selected conversion can be
obtained.

4.2 Multi-Gaussian-distributed DTG model:

Thermal decompositions of samples (cellulose, hemicellulose and lignin) were observed in terms
of the overall mass loss by using a thermogravimetric analyser[4] .
Table 1 : Initial data
Material Temperature Heating Rate
Range (in) ( K/min)
Pine 293.55 - 1068.01 10
Pine 302.81 - 1064.11 15
Pine 292.667 - 1061.019 20
Millet 305.15 - 1066.37 10
 Sweet Cane 303.10 - 1066.37 10

When experiments were performed under N2 atmosphere, nitrogen was continuously passed
into the furnace at a flow rate of 100 mL/min . As for experiments under CO2 atmosphere, CO2
and N2 were both used as the purge gas at a flow rate of 80 mL min1 for CO2 and 20 mL min1
for N2.

k0 is the pre-frequency factor , Beta is the heating rate

In order to estimate the values of kinetic parameters, the activation energy distribution is
generally assumed by a Gaussian distribution with mean activation energy E0 and standard
deviation sigma as shown below:
4.3 Results and discussion

Figure 1: DTG Curves for different heating rates

Figure 2: GMM Deconvolution Method Output

 Figure 3: Sweet Cane DTG and TGA Curve

Figure 4: Peak Mapping Method for two Savitzky-Golay filter strength.

 As already stated, biomass is composed of three major components such as cellulose,
hemicellulose and lignin. Each component undergoes degradation at different rates based on
their elemental composition. Hence, the same kinetic parameters cannot be used to predict the
thermal behaviour of the samples throughout its thermal transition. It is thus critical to identify
the degradation temperature range of individual components and to apply the kinetic parameter
for each component. The TGA–DTG curves of Pine, Millet and Sweet Cane are shown in the
Figures. In all the curves, two distinct endotherms are observed. As illustrated in Figures .
thermal decomposition of samples is divided into two regions. The region within the ambit of the
first endotherm is considered as region 1. Region 2 corresponds to the region after the first
endotherm. whereas region 1 due to the degradation of hemicellulose–cellulose components.
region 2 literally corresponds to the decomposition of lignin and inorganics present in the
samples The thermal degradation of lignin is considered intricate because of its complex
structure. During the decomposition of biomass, hemicellulose–cellulose degrades first followed
by lignin. As hemicellulose and cellulose often degrades at a very close temperature range, they
undergo degradation simultaneously and their degradation regions often overlap with each other.
Hence, for the hemicellulose and cellulose degradation two distinct endotherms cannot be
obtained in the DTG curve

Figure 1: Experiment setup Figure 2: Schematic diagram of the pyrolysis of biomass

 5. Conclusions and further work

1) It was noticed from the TGA curves of ‘Pine’ that the mass loss occurs in three stages and
the curve shifts to the right for higher heating rates.
2) Differential Thermogravimetric Analysis curves for ‘Pine’ shows a major mass loss peak,
followed by a second mass loss peak, which is small as compared to the first mass loss
peak. The first DTGA peaks is due to the decomposition of cellulose and hemicellulose in
the temperature range of 570-620K. The second DTGA peaks are wide and flat; it is due to
the decomposition of lignin at temperatures above 630 K.
3) The maximum peak temperatures for first and second DTGA peaks for ‘Pine’ were
observed in the range of 575 to 630K and 630 to 660K respectively. Whereas for Sweet
Cane, the maximum peak temperatures were observed in the range of 560 to 620K and
670K respectively.
4) In the case of Sugar cane the difference in peak temperatures for Cellulose, Hemicellulose
and Lignin is comparable so the results are more accurate.
5) Next steps involves the determination of The kinetic parameters (activation energy, pre-
exponential factor and order of reaction) for dehydration of cellulose, hemi-cellulose and
lignin.
6. References

1) Paul T. Williams , “Pyrolysis/gasification of cellulose, hemicellulose and lignin for hydrogen

production in the presence of various nickel-based catalysts” Energy Research Institute,
University of Leeds, Leeds, LS2 9JT, UK

2) Haiping Yang,Rong Yan , “In-Depth Investigation of Biomass Pyrolysis Based on Three Major
Components: Hemicellulose, Cellulose and Lignin” , National Laboratory of Coal Combustion,
Huazhong University of Science and Technology, Wuhan

3) A. Saddawi,† J. M. Jones,*,† A. Williams, “Kinetics of the Thermal Decomposition of

Biomass” Energy and Resources Research Institute UK.

4) Jinzhi Zhang, Tianju Chen, “Multi-Gaussian-DAEM-reaction model for thermal

decompositions of cellulose, hemicellulose and lignin: Comparison of N2 and CO2 atmosphere
”. University of Chinese Academy of Sciences, Beijing 100049, China

5) Marion Carrier , Anne Loppinet-Serani , “Thermogravimetric analysis as a new method to

determine the lignocellulosic composition of biomass”. 33608 Pessac Cedex, France.

6) Blasi, C. D.; Signorelli, G.; Russo, C. D.; Rea, G. Ind. Eng. Chem. Res. 1999, 38, 2216-2224.

7) Rao, T. R.; Sharma, A. Energy 1998, 23, 973-978.