1

CHAPTER 4

4 RESULTS AND DISCUSSION

4.1 Catalyst Characterisation

4.1.1 Total Acid Density
In this works, back titration method was used to measure the total acid density of all
catalysts. The catalytic performance and stability of the catalyst is always connected
to its acid site density. The acid density is contributed dominantly by the presence of
hydrophilic function group (SO3 H- ) that enhanced the accessibility of methanol to
triglycerides and free fatty acids (Shu et al., 2010). Hence, higher total acid density
was always decoupled with higher FAME yield. Therefore, total acid density test can
be used to determine the optimum pretreatment parameter of catalysts. However,
there might some experimental errors such as inconsistency of back titration. To
verify the result, biodiesel characterisation by gas chromatography (GC) was done to
determine the FAME yield and the results was discussed in section X. Table X
showed the total acid density of catalysts derived from EFB, POF and CC that were
impregnated with both H3 PO4 and KOH activating agents.

: Total Acid density of Catalysts Derived from Different Biomass

Total Acid Density (mmol/g)
Catalyst Derived from Biomass KOH 𝐇𝟑 𝐏𝐎𝟒
Corn Cob (CC) 2.18 1.16
Empty Fruit Brunch (EFB) 3.14 2.46
Palm Oil Frond (OPF) 3.66 1.74

The results showed that catalyst derived from POF with KOH as activating
agent had highest acid density whereas catalysts derived from CC had lowest acid
density among three biomasses. This indicated that POF had highest potential to be
used as carbon precursor to synthesis heterogeneous catalyst for biodiesel production.
From the table, we can also see that the catalyst impregnated with KOH has higher
acid density as compared to H3 PO4 . Therefore, KOH was considered as a better
activating agent as compared to H3 PO4 . However, Arneli et al. reported that H3 PO4
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was more effective than KOH in activated carbon production because can open the
porous pores and increase the surface area of activated carbon (Arneli et al., 2017).
The deviation of results might due to the high concentration of H3 PO4 was used in
her experiment, thereby, a higher catalytic performance of catalyst was obtained.
According to Utama et al. (2016), KOH was reported as common activating agent
that produce mesoporous and microporous carbons. Therefore, KOH was chosen as
optimum activating agents to undergo subsequent parts of the experiment.
Therefore, OPF that was blended and sieved into three different sizes, was
used to synthesis catalysts. The total acid density for three biomass sizes was shown
in Error! Reference source not found. and the corresponding trend was plotted in
Figure 4.1. From the figure, the total acid density decreased with increasing biomass
size from 300μm to 2mm. This can be explained by smaller size of OPF has higher
surface area exposed to the activating agent thus resulting in higher porosity on the
surface of activated carbon. Then, more SO3 H- incorporated on the catalyst surface
which causes an increase in acid density. From the results, we can conclude that OPF
with 300μm was the optimum size to achieve a better catalytic performance.

Total Acid Density of Catalyst Derived from Different Biomass Size

Size of OPF Total Acid Density (mmol/g)
300μm 4.92
1mm 3.16
2mm 2.94
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Total Acid density (mmol/g)

5

0
0 0.5 1 1.5 2 2.5
Size of Oil Palm Frond (mm)

Figure 4.1: Graph of Total Acid Density of Catalysts Derived from Different
Biomass Sizes

The total acid density of catalysts synthesized at different carbonisation temperature

was tabulated in Error! Reference source not found. and corresponding trend was
shown in
Figure 4.2. The results revealed that CAT600 has highest acid density at 6.24mmol/g
as compared to CAT400 and CAT800. When the carbonisation temperature was
increased from 400℃ to 600℃, the acid density increased sharply. However, the acid
density showed a slightly decreasing trend when the temperature was further
increased to 800 ℃ . This might due to the sintering effect of catalyst at high
temperature, in which the increasing of pore density that causes the agglomeration of
pore together, thus leading to a decrease in chances of SO3 H- group incorporates on
the surface area of catalyst (Gaber et al., 2013). As a result, acid density decreased as
carbonisation temperature was further increased.

Total Acid Density of Catalysts Synthesized at Different Carbonisation Temperature

Catalyst Samples Carbonisation Temperature Total Acid Density
(℃ ) (mmol/g)
CAT400 400 3.36
CAT600 600 6.24
CAT800 800 5.92
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Total Acid Density (mmol/g)

6
5
4
3
2
1
0
0 200 400 600 800 1000
Carbonisation Temperature (ºC)

Figure 4.2: Graph of Total Acid Density of Catalysts Synthesized at Different

Carbonisation Temperature

The optimum carbonisation condition at 600 ℃ was selected to further study

impregnation ratio parameter. Table X showed the total acid density of catalysts
synthesized using different impregnation ratio of biomass to activating agent. Figure
4.3 depicted an increasing trend of acid density when the impregnation ratio was
increased from 1:0.5 to 1:1.5. As the impregnation ratio was increased, there was
collapsing of larger pores and development of smaller micropores began. These
micropores increased the surface area of the activated carbon, more SO3 H- group
attached on the surface will lead to higher acid density. Hussein et al. (2001) claimed
that extremely high impregnation ratio will not increase the surface area of activated
carbon but detrimental to the micropore structure. Hence, the optimum impregnation
ratio of 1:1.5 was chosen and used in the following parts of parameter studies.

Total Acid Density of Catalysts Synthesis using Different Impregnation Ratio

Catalyst Samples Impregnation Ratio Total Acid density
(OPF:KOH) (mmol/g)
CAT0.5 1:0.5 5.60
CAT1.0 1:1.0 6.24
CAT1.5 1:1.5 6.94
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Total Acid Density (mmol/g)

7
6
5
4
3
2
1
0
0 0.5 1 1.5 2
Impregnation Ratio (OFP:KOH)

Figure 4.3: Graph of Total Acid Density of Catalysts Synthesised using

Different Impregnation Ratio

Table X depicted the total acid density of catalysts synthesized at different

impregnation temperature. Trend of total acid density corresponding to impregnation
temperature was plotted in Figure X. From the graph, the total acid density increased
with increasing impregnation temperature. This is because higher impregnation
temperature can promote the formation of final porous structure of activated carbon
that provided template for the incorporation of SO3 H- group on the surface, which
gave rise to higher acid density.

Total Acid Density of Catalysts Synthesised at Different Impregnation Temperature

Catalyst Samples Impregnation Temperature Total Acid Density

(℃ ) (mmol/g)
CAT50 50 5.70
CAT70 70 6.24
CAT90 90 6.46
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6.6

Total Acid Density (mmol/g)

6.4
6.2
6
5.8
5.6
5.4
5.2
5
0 20 40 60 80 100
Impregnation Temperature (ºC)

Graph of Total Acid Density of Catalysts Synthesised at Different Impregnation

Temperature
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4.1.2 Scanning Electron Microscope (SEM)

Scanning Electron Microscope was used to investigate the surface morphology and
the structure properties of raw OPF, impregnated OPF, carbonised OPF and
sulfonated catalysts. Figure X showed the surface morphology of raw oil palm frond
without any pretreatment. It can be seen that the lignocellulosic structure of the OPF
was surround with natural plant wax, pectin and impurities. In general,
lignocellulosic structure was composed of hemicellulose, cellulose and lignin. Palm
frond is mainly composed of hemicellulose and lignin. Polymer chains of
hemicellulose with short branches and the amorphous morphology can be obviously
seen on raw OPF. Before pretreatment of raw OPF, a smooth and flat surface that
was unfavourable for the attachment of SO3 H- group was found.

SEM Image of Raw Oil Palm Frond Before pretreatment at Magnification of 2000X
and 3000X

Figure X illustrated the SEM image of OPF after impregnation with KOH
activating agent. According to Swatloki et al. (2001), the lignocellulosic structure of
biomass would be greatly affected by the chemical activation. From the figure, there
was swelling of OPF and the lignin or hemicellulose structures was disrupted.
Besides, the linkage between the hemicellulose was broken down. The mesoporous
structure began to develop and internal surface area exposed was found to be
increased. After impregnation, we can observed that the KOH has significantly
increase the porosity of the OPF.
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SEM Image of OPF After Impregnation With KOH at Magnification of 2000X and
3000X.
Other than that, the effect of carbonisation process on impregnated OPF can
be seen from Figure X. After carbonisation of OPF, the lignocellulosic structure was
completely transformed into carbon structure with number of visible pores. From the
figure, we can observe the development of micropores which raised the specific
surface area and acted as a site for the embedment of sulfonic group. This verified
that it was a promising catalyst for biodiesel production.

SEM Image of OPF After Carbonisation at Magnification of 2000X and 3000X.

Figure X showed the SEM image of activated carbon after sulfonation process.
However, the surface morphology had no significant changes after sulfonation but
there was some sulfuric acid attached on the micropores. In addition, the micropores
of activated carbon was slightly enlarged, thereby, enhancing the accessibility of
methanol to large FFA molecules within the micropores. By sulfonating the activated
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carbon with concentrated sulfuric acid, a promising catalyst can be generated and
implemented in biodiesel production.

SEM Image of OPF After Sulfonation at Magnification of 2000X and 3000X.

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4.1.3 Energy Dispersive X-ray Spectrometer (EDX)

Energy Dispersive X-ray Spectrometer (EDX) was used to detect the elements
prosent in the raw OPF, impregnated OPF, activated carbon and sulfonated carbon
catalyst. Table X illustrated the elements compoistion, in atomic percentage, present
on the surface of each sample.

Surface Elemental Composition of Samples

Elemental Composition (At%)
Samples C O S K
Raw OPF 60.63 39.16 0.08 0.12
Impregnated OPF 58.15 40.55 0.17 1.1
Activated Carbon 91.64 7.64 0.17 0.55
Sulfonated Carbon Catalyst 81.51 16.97 1.46 0.06

From the Table X, raw OPF was originally composed highest percentage of
carbon at 60.63%, followed by oxygen at 39.16% and negligible amount of
potassium and sulphur. The high percentage of carbon in the OPF causing it became
a potential carbon precursor to produce activated carbon for biodiesel production.
The presence of sulphur and potassium might due to the impurities or minerals from
soil.

After impregnation, the percentage of potassium increased from 0.12% to

1.1%. The increase of potassium elements was due to the dispersion of potassium
element on the surface of OPF. This was because the OPF was properly washed with
acetic acid and distilled water after impregnation. The potassium dispersed on the
surface was neutralised by the acid during washing. However, this does not affect the
porosity of the surface. The others elements such as carbon and oxygen did not show
significant changes after impregnation.

Furthermore, there was a sharp increase in carbon percentage from 58.15% to

91.64% after carbonisation. Carbonisation is a crucial step to synthesis activated
carbon with porous surface structure. The significant increase in carbon content
indicated the formation porous carbon framework which would definitely enhance
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the catalytic erformance. Meanwhile, the oxygen percentage experienced a

decreasing trend from 40.55% to 7.64%. During carbonisation, the oxygen might be
consumed by impregnated OPF to form activated carbon.

Sulfonation is process in which the OPF functionalised with sulfonic acid

group. From the result, the percentage of sulfur increased from 0.17% to 1.46%. This
indicated that the sulfonic acid group was successfully incorporated on the surface of
the active carbon, forming a heterogenous catalyst.
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4.1.4 Thermogravimetric Analysis (TGA)

The novel carbon catalysts showed excellent thermal stability under oxygen-free
conditions which is comparable to the previously reported sulfonated carbon
catalysts.17-19,23 Overall, the catalytic materials obtained by method 1
demonstrated high operational stability and were suitable for applications at
operating temperatures (Tmax) close to 240 C (Table 3.3). The TGA patterns of
sulfonated carbons show two distinctive weight loss regions (Figure 3.4): the first,
more rapid loss occurred between 0-130 C which was attributed to loss of water and
free moisture adsorbed on the catalyst surface and the second weight loss region
occurred at 240-380 C; the 6-8% weight loss in this region was attributed to the
removal of –SO3H groups, as this region was absent in the non-sulfonated materials.
Following the 2nd region, weight loss continued but at a much slower rate which
could be attributed to further the –SO3H loss with graphitization. To summarize,
sulfonation lowered the onset of thermal decomposition due to incorporation of –
SO3H groups on carbon surface.23 Further, the description of the influence of the
raw material on the thermal stability of these materials can be found in the
publication [I]. In contrast, the lower Tmax values of the catalysts obtained by
method 3 could be accredited to the partially carbonized and functionalized carbon
structures produced by hydrothermal carbonization.
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4.1.5 Fourier Transform Infrared Spectroscopy (FTIR)

Fourier Transform Infrared Spectroscopy (FTIR) was implemented to evaluate the
functional group present on the sample. In this works, FTIR analysis functioned with
wavenumber range of to determine the function group on the raw OPF, impregnated
OPF, activated carbon and sulfonated carbon catalyst. In fact, the dominant purpose
of this test is to verify the acidic group on the catalyst. Chellappan et al. claimed that
some functional group such as -OH, -COOH and -SO3H must be detected in a
heterogeneous catalyst. Table X showed the infrared stretching frequency ranges for
different functional group.
Functional Groups Frequency Range (cm−1 )
O-H stretch 2800-3600
C=O stretch 1500-1800
C=C stretch 1600
O=S=O stretch 1100-1200
-SO3H stretch 1296
C-S stretch 670-715

Raw OPF Impregnated OPF

100

95

90
Tranmittance

85

80

75

70
4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wave Number
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Activated Carbon Sulfonated Carbon Catalyst

100
98
96
94

Axis Title
92
90
88
86
84
82
4000 3600 3200 2800 2400 2000 1600 1200 800 400
Axis Title

Fourier
According to Lambert (1989), SO3H group in sulfonic acids is represented by
wavenumbers 1040 to 1080 cm-1 with SO3 symmetric stretch and wavelength 1155
to 1245 cm-1 with S=O stretch. Then, the wavenumber of 2400 to 3100 cm-1 is
related to the –OH in carboxylic acids of H bonded OH stretch. Ezebor, et al. (2014)
reported that wavenumber at around 1600 and 1700 cm-1 are indicating the C=C
aromatic stretching and C=O stretching vibrations respectively.

demonstrated the existence of sulfonic group and its successful incorporation onto
the carbon matrix of WBPAC。 Since concentrated sulfuric acid was used as the
sulfonating agent, aliphatic groups of CH2 or CH3 can be oxidised to carboxylic acid
groups, enhancing the total acid density of the fabricated catalysts (Sandouqa, Al-
Hamamre and Asfar, 2018).
- This proved that the active sites were well established on the surface of the
sulfonated solid acid catalysts.
The stretching mode of conjugated C=C bond at 1600 cm-1 was attributable to the
aromatic ring formed as a result of incomplete carbonisation of carbonaceous
materials. Therefore, a more rigid carbon material was formed. The stretching
vibration of hydroxyl group was not obvious in both samples but its presence would
enhance the catalytic performance of the synthesised catalysts (Shuit and Tan, 2014).
According to Figure 4.6, all catalysts calcined at different temperatures show an
obvious stretching vibration of aromatic ring C=C at wavelength around 1580 cm-1
which had same observation as Konwar et al., (2015). This stretching was due to the
incomplete carbonisation of carbon material and form polycyclic aromatic carbon
sheet with phenolic group (Mo et al., 2008).
-which indicated the presence of sulfonic group on catalyst (Thomas, n.d.).
while, FT-IR and XPS analysis confirmed the presence of –COOH, –OH,
33 phosphate and –SO3H /–PhSO3H functionalities on the surface of novel catalysts
and resembled sulfonated carbon catalysts reported in earlier work
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Figure -5 showed the FT-IR spectra of EFB activated carbon which was observed at
wavenumber in the range of 4000-400 nm. The presence of a peak at 3404 cm-1 was
assigned as stretching vibration oh O-H in hydroxyl groups. A weak peak at 1691
cm-1 was ascribed as stretching vibration of C=O groups. This band disappeared at
increasing temperatures. The strong band at 1564 cm-1 was attributed to C=C
stretching in aromatic rings which was almost disappeared as increased temperatures.
The bands at 1442 and 1383 cm-1 were ascribed to C=O and C-O stretching
vibration, respectively in carbonyl, ester and carboxylate groups. The bands at 1079
cm-1 were ascribed to C-O stretching vibrations in hydroxyl groups, and shows a
stronger intensity at higher temperatures15. The presences of bands around 874 –
752 cm-1 were assigned to C-H out-of-plane deformation vibration of C–H groups
located at the edges of benzene derivate which were lesser intensities at higher
temperatures16, 17. The FTIR studies of the surface functional groups revealed that
the activated carbons proved more oxygen functional groups at higher temperatures
As can be seen in Fig. 5, the FT-IR spectrum confirms the presence of characteristic
functional groups in the catalyst, which are responsible for esterification and trans-
esterification reactions. The strong and broad peak around 3600–2800 cm1 is
attributed to the OH functional group, shown in each sample, which is attributed to
alcoholic and phenolic OH groups. Also, the peak at around 1800–1500 cm1 is in the
carbonyl/carboxyl region. Conspicuous sharp peaks at around 2916–2800 cm1 are
antisymmetric and symmetric vibrations of CH groups of the raw sample [33]. The
strong peak at around 1712 cm1 and the sharp strong stretching at around 1230–1120
cm1 are assigned to symmetric and asymmetric stretching vibrations of SO3H
[10,34], which are normally observed in catalysts produced after sulfonation of
incompletely carbonized biomass. The presence of these important functional groups
in the used catalysts is observed after the second cycle of usage
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