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CHAPTER 3
METHODS

In this chapter, all the methods used in this study is described in detail. The
method can be divided into five sections, namely, production of the charcoal briquette,
proximate analysis of the calamansi charcoal briquettes, physical parameter analysis,
thermal properties analysis, and comparative cost analysis. The quality of the
briquettes was then compared with a literature value, and if the literature value is not
available, it was compared with a reference sample. All procedures are patterned from
the accredited standard methods. Otherwise, the procedures were adapted from
available reliable journals.

3.1 Production of Calamansi Waste Charcoal Briquettes (CWCB)

The first step in the production of the charcoal briquettes was the collection of
calamansi waste from a local calamansi juice factory. The collected samples were
freshly squeezed from the factory and were combined as one. From this, the three
replicate samples were taken for laboratory analysis. The treatment of these peels is
described in the subsequent sections.

3.1.1 Preparation and Carbonization of Calamansi Waste Biomass

The wet calamansi waste biomass was weighed and sun-dried for 3 days.
After sund-drying the weight of the dried calamansi waste was taken. The moisture
content of the of the freshly squeezed calamansi was then calculated using the
equation ___. The moisture content of the dried calamansi was obtained from the
before the production of the briquettes. The moisture content of the dried sample was
calculated using equation___. This was then carbonized using the method of Ycaza
and Barre.74 The samples were divided into 3 portions of 2 kilograms. This served as
the replicate samples. For every replicate, three trials were conducted per analysis.
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The preweighed calamansi waste samples were placed on the metal grill
situated above the fire in the lower chamber and were allowed to combust. This was
then ignited using a blowtorch. Once white smoke was seen, the apparatus was sealed
off using the lid of the grill. This was done to starve the set-up of oxygen to prevent
the samples to burn completely. This process allows the thermal decomposition of the
sample leading to carbonization. The set-up was kept covered for 3 minutes, ensuring
maximum carbonization of the calamansi waste samples. After the elapsed time, the
carbonized calamansi samples were transferred into a cast iron chamber then covered
immediately, as the carbonized samples at this point have ample thermal energy to
continue carbonization and thermal decomposition. The samples were left inside until
the chamber reached room temperature. The carbonized samples were weighed and
transferred into plastic bags for analysis. The yield of carbonized samples was
calculated using equation _____.

3.1.2 Size Reduction of Carbonized Calamansi Waste

The carbonized calamansi samples were subjected to size reduction using Foss
Tecator 1093 Cyclotec Sample Mill to ensure particle uniformity of the charcoal
briquettes.12 Prior to grinding the carbonized calamansi samples, manual crushing into
3-millimeter pieces to prevent the machine from being overloaded and overheated.
The milled carbonized charcoal was stored into plastic containers until further use.
The reference sample, coconut shell charcoal was pulverized using a coffee grinder
instead of the mill used for the samples.

3.1.3 Preparation and Determination of Optimal Binder Concentration and

Preparation Temperature

The determination of the effective concentration of the binder was determined

by testing the binding efficiency of the briquette using the drop test. Different starch-
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to-water ratios were used in the determination of the most efficient yet cost-effective
binder concentration. This mixture was homogenized using a magnetic stirrer. In a
separate experiment, the most effective binder preparation temperature was
determined. The most effective binder concentration and temperature was used
throughout the production process in this study.
3.1.4 Production of Charcoal Briquettes

In the production of the calamansi charcoal briquettes, the starch binder

previously prepared was mixed with the pulverized carbonized sample. The binder
charcoal mixture consisted of 100 grams fine charcoal powder and the 100 grams
binder mixture to produce the briquettes. These were mixed in a container until the
binder and charcoal become uniform in nature. The resulting mixture was fitted into
the mold of the mechanical briquette machine. The lever of the briquette machine was
lowered to press the mixture inside the mold. Once pressed, the briquettes were
removed from the mold and left to sun dry for 1 week. The dried briquettes were
stored in a metal tray for the subsequent analysis. Three trials were done for the three
replicates. This same process was repeated for the reference coconut charcoal
briquettes.

3.2 Proximate Analysis and Sulfur Content Determination

The proximate analysis of the calamansi biomass charcoal briquettes and coconut
charcoal reference briquettes were outsourced for analysis in conjunction with the
Department of Energy ERTLS (Energy and Testing Laboratory Services) Division.
The methods found in this section are presented as described by the testing laboratory.

To comply with ERTLS sample analysis requirements prior to sending the

samples, the 250 grams briquette samples were ground and sieved into a 100-mesh
ASTM calibrated sieve (with ERTLS requiring a minimum of 60-mesh sieving for
analysis). Sampling was conducted through a random sampling method then pooled
together per replicate.
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3.2.1 Moisture Content

The moisture content determination of the calamansi charcoal briquettes and

coconut charcoal reference briquettes follow the ISO 5068-1983 standards. A clean
and dry empty weighing dish was weighed to the nearest 0.001g. An even layer of 1 to
2 g of sample was distributed on the dish and was heated in a nitrogen-purged oven,
pre-heated at 105 to 110 °C for 3 hours or until constant mass is obtained at the
nearest 0.001 gram. After this, the dish with the dried sample is covered immediately
and was allowed to cool for 20 minutes. The mass was then reobtained at the nearest
0.001 gram, with the results are expressed in the following Equation 1.2:

Equation 1.2

where Mad is the moisture content expressed in mass fraction percent, m1 is the mass of
weighing dish and its lid, m2 is the mass of weighing dish, lid and sample before
heating, m3 is the mass of weighing dish, lid and sample after heating, all expressed in
grams.

3.2.3 Volatile Matter Content

The volatile matter content determination of the calamansi charcoal briquette

and the coconut reference charcoal briquette follow ISO 562:2010 standards. A
furnace was set to 900 °C ± 5 °C, with this temperature maintained for 7 minutes.
Empty crucibles and their lids were placed inside the furnace for this allotted time, and
once the time has elapsed, the empty crucibles and lids were allowed to cool to room
temperature on a thick metal plate.
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Once cooled, 1 g ± 0.1 g of sample was placed inside the crucible. The lid was
replaced on top, and the crucible is to be tapped on a clean hard surface until the test
portion forms a layer of even thickness on the bottom of the crucible.
The crucibles were placed inside the furnace once more at the same
temperature and left for approximately 7 min ± 5 s. Once the elapsed time has been
reached, the crucibles containing the samples were removed and allowed to cool until
they reached room temperature. The crucibles were weighed to the nearest 0.1 mg,
with results in terms of percent mass fraction expressed by Equation 1.3:

Equation 1.3

where V is the volatile matter content in mass fraction percent, m 1 is the mass of
empty crucible and its lid, m2 is the mass of crucible, lid and sample before heating, m 3
is the mass of crucible, lid and sample after heating, and ω H2O is the moisture, all
expressed in grams.

3.2.4 Ash Content

The ash content determination of the calamansi charcoal briquette and coconut
charcoal reference briquettes follows ISO 1171:2010 standards. A clean, dry heating
dish is weighed to the nearest 0.1 mg, afterwards an even layer of sample material is
dispensed evenly on the dish and reweighed. If the dish is porcelain or silica in
composition, the dishes are to be preheated to 815 °C ± 10 °C for 15 minutes, then left
to cool to room temperature.

Otherwise, the dish containing the sample was placed inside the furnace at
room temperature, raising the temperature evenly to 500 °C over a period of 60
minutes. Once the initial 500 degrees has been reached, this temperature is to be
sustained for 30 minutes, with an exception for brown coals in that the holding period
is for a full hour. Once done, the temperature of the furnace is to be increased to the
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target temperature of 815 °C ± 10 °C, and once this temperature is reached, it is to be

sustained for another 60 minutes. This is the incineration period in which the sample
decomposes to ash.

Once this time has elapsed, the dish containing the sample is removed from the
furnace and set aside on a thick metal plate for 10 minutes. Afterwards, the dish is to
be transferred to a desiccator or other closed container without desiccant to cool until
room temperature. The sample is weighed to the nearest 0.1 mg, and the result is
expressed as a percentage mass fraction given by Equation 1.4:

Equation 1.4

where m1 is the mass of weighing dish and its lid, m 2 is the mass of dish and sample
before heating, m3 is the mass of weighing dish and ash after heating, all expressed in
grams.

3.2.5 Fixed Carbon Content

The fixed carbon content determination of the calamansi charcoal briquette and
coconut charcoal reference briquettes follow ISO 17246:2010 standards, which is
expressed as a percentage mass fraction given by Equation 1.5:

Equation 1.5

where Mad is the moisture content, Aad is the ash content, and Vad is the volatile
matter content.

3.2.6 Sulfur Content

The sulfur content determination of the calamansi charcoal briquette and coconut
charcoal reference briquettes follow ASTM D 4239 -17 Method A standards which
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can be described as follows: A sample is combusted at a minimum temperature of

1350 °C under high oxygen flow in a furnace. This primary combustion ensures that
all other species decompose into mainly their simple oxides, with a focus on the
formation of gaseous sulfur dioxide (SO2). Moisture and particulates are filtered out
of the resulting gas stream.

The now purified gas then passes through a cell equipped with an infrared
detector, with the SO2 molecules selectively absorbing infrared radiation at a specific
wavelength. As the gas traverses this cell, this absorption reduces the amount of
infrared energy reaching the detector with a filter eliminating all other infrared
wavelengths that do not correspond to the infrared frequency given by sulfur dioxide.
The decrease in infrared energy directly correlates to the SO 2 concentration in the gas
stream with the detector operating in a dual mode, using the same cell for both
reference and measurement.

3.4 Physical Properties Test

The physical properties test of the calamansi charcoal briquettes and reference
coconut charcoal briquettes include compressive strength, impact resistance index and
bulk density. The sampling was done randomly per replicate method resulting in three
trials per replicate.

3.4.1 Compressive Strength

The measurement of the compressive strength was done by first obtaining

samples across replicates through random sampling method. Once the samples were
procured, a ZMF-500 500N Digital Force Gauge Dynamometer was used to measure
the compressive strength of the briquettes. The area of the tip of the instrument was
first measured. Once measured, the briquette was placed on a flat platform.
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The instrument was lowered on the circular top of the briquette, with the tip
facing downwards with the instrument pressed on to the briquette top until the
briquette displayed linear vertical cracks, signifying failure of structural integrity.
This equivalent force, in newtons, is divided by the area of the instrument tip to obtain
a pressure value in units of kilograms per square centimeter. This process was
repeated for the reference coconut briquettes.

The compressive strength was calculated as show in Equation 1.6.

F Equation 1.6
P=
A

Where P= pressure in N/Cm2, F = force in N, and A= area in cm2.

3.2.2 Impact Resistance Index

The produced calamansi charcoal and reference coconut briquettes were

subjected to friability testing by using the impact resistance index and its bulk density
to be also calculated, as described by Tesfaye et. al. 73 and Ycaza and Barre.74 For the
impact resistance index, 5 briquettes are to be bound together and dropped from a
height of 5 meters. The impact resistance is then calculated as shown in Equation 1.7.

N
IRI = ×100 Equation 1.7
n

Where IRI = Impact Resistance Index, N= number of drops, n=number of fines

generated.

3.2.3 Bulk Density

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The bulk density of the produced calamansi charcoal and reference coconut
briquette was determined using Equation 1.8, described by Tesfaye et. al. 73, with the
volume of the briquette to be calculated using the geometric formula for calculating
the volume of cylinder, and the mass of the briquette will be measured using an
analytical balance.

Ms Equation 1.8
BD= [% ]
Vs

Where BD=bulk density of the briquette in %, M s=mass of briquette sample in grams

and Vs = volume of briquette sample in cc.

3.5 Thermal Properties Analysis

For the thermal properties analysis of both the calamansi charcoal and
reference coconut briquettes the kindling, boiling, and burning time were used as the
main parameters. The kindling time and burning time was measured simply by how
long the briquettes take to be burned and how long the entire briquette burns
respectively.74 For the boiling time, this is determined by boiling 200mL of distilled
water using a boiling pot, and the time it takes for the water to boil after kindling time
is recorded as the boiling time. 74 Approximately 100 grams of briquettes were used
for the thermal analysis, with random sampling using sampling method across three
replicates, resulting in three trials per replicate.

3.5.1 Calorific Value

The calorific value determination of the calamansi charcoal briquette and

coconut charcoal reference briquettes follows the ASTM D5865-13 standards, which
can be described as follows: 0.8 to 1.2 grams of benzoic acid was first weighed out.
Then, the bomb chamber was rinsed with water then filled with 1.0mL of water before
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assembly, with the fuse measured and installed afterwards. Oxygen was admitted into
the bomb at consistent pressures of 2 to 3 MPa.

The calorimeter was filled with water at a temperature not more than 2 °C
below room temperature. The bomb was then placed in the calorimeter, and the
temperature was checked for 30 seconds to ensure a stable start for the calorimetry.
Once stable, the charge was fired, and the temperature rise recorded. The calorimeter
was allowed to cool down. After the benzoic acid run, the same procedure was
repeated for the actual samples and was repeated for 3 successive runs.

Depending on calorimeter type (adiabatic or isoperibol), measurements are

taken either at 0.01 and 0.001 °C when reaching final stabilization temperature or per
minute respectively. After calorimetry, the bomb is then depressurized, and the
remaining sample inside the bomb chamber discarded. Corrections to the calorific
value were done depending on which heteroatom groups present in the sample are
seen as interferents in the calorific value determination.

3.5 Statistical Treatment of Data in Comparative Analysis

The comparative analysis of the produced briquette was made with commercially
available coconut charcoal fuel added into the same binder matrix and shaped into the
same briquette to ensure uniformity. Proximate analysis, physical properties, calorific
value, kindling time, boiling time, and burning time are the parameters to be tested for
the comparative analysis.63-65, 74

For the statistical treatment of data, the standard of 95% confidence interval is
utilized, and ANOVA as the tool used to measure if there is a significant difference
between the average of replicate means between the two groups if the calamansi
charcoal briquette is comparable to coconut reference charcoal briquettes in terms of
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physical and thermal properties , as well as comparison of means using bar
graphs.63,65
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The means of each replicate was used as the data to be subjected for ANOVA;
to determine if there is a significant difference between the two groups, the p-value of
the ANOVA analysis is the main parameter to be used in determining this. If the p-
value is less than or equal to α, this means that there is a significant difference
between the means of the two groups. Meanwhile if p-value is greater than α, then the
means of the two groups are not statistically different.73 Cost analysis of the briquette
production was calculated by considering labor, sundry charges, and raw materials
cost74 for total number of briquettes produced.71