Plant-based Calcium Silicate from Rice Husk Ash:

Green Adsorbent for Free fatty Acid Recovery from

Waste Frying Oil

by

Zainor Syahira Binti Zainal

(181472101)

A thesis submitted in fulfillment of the requirements for the degree of

Bachelor of Chemical Engineering Technology (Food Technology)

Faculty Chemical Engineering Technology

UNIVERSITI MALAYSIA PERLIS

2021
 UNIVERSITI MALAYSIA PERLIS

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 ACKNOWLEDGMENT

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 TABLE OF CONTENTS

PAGE

DECLARATION OF THESISi

TABLE OF CONTENTS

CHAPTER 1 : INTRODUCTION

1.1 Background study

1.2 Problem statement

1.3 Hypothesis

1.4 Research objectives

1.5 Scope of study

CHAPTER 2 : LITERATURE REVIEW

2.1 Frying

2.2 Waste Frying Oil (WFO)

2.3 Rice Husk and Rice Husk Ash (RHA)

2.4 Silicate derived from natural resources

2.5 Silicate as adsorbent

2.5.1 Magnesium silicate

2.5.2 Calcium silicate

2.6 Characteristic of silicate

2.6.1 Fourier transformed infrared (FTIR)

2.6.2 Scanning Electron Microscopy (SEM)

2.6.3 Energy Dispersive x-ray Spectroscopy (EDS)

iii
 2.6.4 X-ray diffraction (XRD)

2.7 Significant parameters affecting FFA adsorption in silicate

2.8 Conclusion

CHAPTER 3 : METHODOLOGY 30

CHAPTER 4 : EXPECTED RESULT Error! Bookmark not defined.

CHAPTER 5 : CONCLUSION Error! Bookmark not defined.

REFERENCES 53

APPENDIX A SAMPLE APPENDIX 1 62

APPENDIX B SAMPLE APPENDIX 2 63

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ABSTRAK

v
Click here to enter text.

ABSTRACT

vi
 CHAPTER 1 : INTRODUCTION

1.1 Background of Study

Much recent years has focused on the application of the rice husk (RH) due

to its versatile properties. Rice husks are essentially the hard protective shell of the

paddy grain, separated from the grain during the milling process (Singh, 2018). They

are composed of cellulose 28-36 %, crude fibre 34.5-45.9 % and ash 13.2-21.0 %

(Otaru, 2013). After separated from the grain, this RH is treated as the agricultural

wastes which were massively produced in African and Asian countries that consume

rice as their staple food, including China, Thailand, Cambodia, Indonesia, and Malaysia

(Lim et al., 2012).

Recent trends show that the Asia population had increased every year from

17.3 million in 2010 to 23.2 million in 2019 (Nepal & Paija, 2019). Such a population

has blown led to higher annual rice production to cope with the increasing demand

(Dawe, 2012). Consequently, such increment directly increases the accumulation of the

rice husk waste in the system.

With the gradual increase of rice production and the rice husk waste

accumulation, the mitigation of such waste to other potential and scientific applications

is much needed. Indeed, they had been commonly used in further potential and

scientific application due to their sustainability, available at almost no costs and

abundantly (Shen, 2017). Rice husk was well reported with its second lives in many

applications such as renewable energy storage and soil amendment (Singh, 2018). In

7
addition, when the carbon content in the rice husk is converted into carbon dioxide

(CO2), it had increased the calorific power of the rice husk (approximate 13–16MJ/kg)

and generates the heat used in steam engines and gasifiers to power rice mills and rice

dryer (An et al., 2010).

Other than the rice husk itself, the rice husk ash (RHA) generated through

the calcination of the rice husk was often studied as well. RHA is known as residue ash

generated after the calcination of RHA (Liu et al., 2016). The calcination time,

calcination temperature, and the composition of the RH will determine the characteristic

of the RHA (Bui et al., 2005). RHA's well-burnt is consisting of 90% amorphous silica,

5% carbon, and 2% kalium oxide (Singh, 2018). Therefore, the disposal of bulky RHA

could be a problem because a significant volume of RHA is handled as waste and

disposed of at landfill sites in some countries, resulting in air and water contamination

and airborne particles linked to human respiratory disease (A. Andersen et al., 2002).

But, due to higher silica content, the RHA can be used as filler, sweeping component,

abrasive agent, pozzolanic material and many more (Pode, 2016).

Although both RH and RHA have various functions in many applications,

both were often reported as effective adsorbent (Ahmaruzzaman & Gupta, 2011).

However, both showed different adsorption performance due to their additional silica

content (Mahvi et al., 2004). Typically, RH contains only around 30% of silica, while in

comparison, RHA contains more than 60% silica (Lee et al., 2017). It was well reported

that the higher silica content of the adsorbent provided a larger surface and a high

degree of porosity for the adsorption purpose, hence better adsorption performance

(McCarthy & Dyer, 2019).

8
 With these excellent adsorptive properties, RHA has been reported as an

excellent adsorbent for various adsorbates, including indigo carmine dye, lead, mercury,

cadmium (Cd2+), and zinc (Zn2+) metal cation, which commonly found in wastewater

(Shen et al., 2014) and also a free fatty acid, which commonly found in waste frying oil

(WFO) (X. Liu et al., 2016).

WFO is a form of domestic waste generated by cooking and frying food

with vegetable oil (Ortner et al., 2016). WFO have ecotoxic properties due to the

higher content of free fatty acid (FFA), polar materials and polymeric compounds

(Choe & Min, 2007). WFO disposal is a problem because disposal methods can

contaminate the environmental water (Kulkarni & Dalai, 2006). In addition, it can

contaminate the soil if spilt on the ground and clog the drains if poured into the kitchen

sink (Sanli et al., 2011).

Compared to many traditional methods, adsorption using RHA has proven to

be an excellent way to treat free fatty acid in WFO, offering significant advantages such

as cheapest, ease of availability, ease of operation, and performance, particularly from

an economic and environmental standpoint (Chua, 2008). Furthermore, , the functional

groups such as carboxyl, hydroxyl and amine groups, along with the silanol groups (Si-

OH) on the surface of RHA adsorbent, are favouring the FFA adsorption process from

the WFO (Schneider et al., 2019). Moreover, since RHA was reported to have a larger

pore size and high porous structure; it has increased the possibility of the FFA

molecules migrating into larger pores and getting adsorbed on the inner pore surface

RHA (Adam & Chua, 2004).

9
1.2 Problem statement

Commonly, the larger pore size of the RHA can be produced by pre-treating

the RHA with inorganic or organic acid before the combustion, such as hydrochloric

(HCl), sulfuric, phosphoric, and acetic acid (Chen et al., 2017). Generally, strong acid

such as HCl would accelerate the hydrolysis and decomposition of organic components

from the RHA, such as hemicellulose, cellulose and lignin (Bakar et al., 2016). In

addition, during the acid pre-treated, most of the metal impurities that are soluble in the

acid, including calcium (Ca), magnesium (Mg) and manganese (Mn), also would be

leached out from the RHA; thus, the silica purity would increase post calcination,

resulting in higher specific surface area of RHA (Chen et al., 2017). Furthermore, as the

organic components and metal impurities had been leach out, it had led to the opening

of the new pores and the enlargement of existing pores on the RHA, which increased

the total of adsorption sites on the RHA surface (Farook & Ravendran, 2000).

Despite, the acid pre-treated RHA showed acceptable free fatty acid

adsorption performance which according to Nattaporn & Porjai ( 2015) the maximum

free fatty acid removal percentages using HCl pre-treated RHA was only at 44%. It was

also reported that such observation was attributed to the pre-treated RHA could reduce

FFA from WFO lower than untreated RHA, which due to the simultaneously occurring

of oxidation and hydrolyzation reaction during heating of the frying oil with catalyzed

from the minimal acid residue in acids pre-treated RHA.

Other than oxidation and hydrolyzation reactions, the low adsorption

performance of HCl pre-treated RHA was also attributed to the high content of other

10
metal impurities such as potassium (K), sodium (Na) and phosphorous (P) which

remained in RHA (Rivas, 2016). These remaining impurities promoted the formation of

cristobalite and tridymite, affecting the structural transformation of silica from an

amorphous to crystalline state even at the optimum calcination temperature (Shinohara

& Kohyama, 2004). Due to such disturbance, the high extend of the crystalline phase in

the RHA resulted in lower FFA adsorption performance as the surface area of the

adsorbent was lowered (Kim et al., 2008).

To improve the FFA adsorption performance from the waste frying oil,

applying the high purity silicate extracted from the rice husk could be helpful. The

successful extraction of the highly purified silicate was possible by pretreating the RHA

in an alkaline solution such as sodium hydroxide, in which the soluble metal silicate

was produced, followed by the precipitation of the metal silicate using an alkaline metal

salt solution such as calcium hydroxide, magnesium chloride or magnesium nitrate

(Clowutimon et al., 2011).

The precipitation of alkaline metal silicate salts is essential to produce the

highly amorphous and purified silicate. On the other hand, metal cations from metal

alkalines, such as calcium (Ca2+) and magnesium (Mg2+) cations, can be adsorbed by

the colloidal particle surface during precipitation, neutralizing the negative surface

charge (Potapov, 2004). The alkaline metal silicate was precipitated by bridging bonds

between particle surfaces with the aid of a coagulating ion, resulting in colloidal silica

coagulation (Rashid et al., 2011). The silicate precipitated by these metal ions was

discovered to have a highly amorphous metal silicate structure, which essential in the

11
adsorption process due to its potentially larger surface area for adsorption (Potapov,

2004). Thus, it is predicted to improve the adsorption of FFA from WFO.

Commonly, the alkaline metal silicate salts precipitation was applied to

produce a highly purified silicate-based adsorbent such as magnesium silicate and

calcium silicate. Even though many studies were done on the adsorption performance

using silicate-based adsorbent derived from the rice husk, most of the study was only

focused on the magnesium silicate (Assawasaengrat et al., 2015). There are limited

numbers of researchers that focus the research on the adsorption performance of the

other types of a silicate-based adsorbent such as calcium silicate or strontium silicate,

especially in the adsorption of free fatty acid in the WFO. Saturated (SFA),

monounsaturated (MUFA), and also polyunsaturated fatty acids (PUFA) such as

palmitic acid (C16:0; 4.6%–20.0%), oleic acid (C18:1; 6.2%–71.1%), and linoleic acid

(C18:2; 1.6%–79%), respectively, were found predominant in WFO (Orsavova et al.,

2015).

For the calcium silicate, most of the studies observe the performance of this

adsorbent to adsorb the heavy metal, and the minor study had done to observe the

performance of this adsorbent to adsorb the FFA. For example, Lin et al. (1998)

observed that the adsorbent with the calcium silicate component, Hubersorb (HB600)

had the highest removal percentage of FFA from WFO, 84.5%, compared to other

adsorbents such as Silasorb, Britesorb, Purifoy, Frypowder, Activated Carbon, and

Magnesol. It was reported that the calcium silicate content of HB 600 gives the basic

properties such as tiny particle size and amorphous nature that made it enable to attract

acids and polar compounds.

12
 On the other hand, S. Liu et al. (2020) reported the adsorption of copper ions

(Cu2+) from the wastewater using calcium silicate hydrate. This study revealed that the

calcium silicate had an excellent adsorption performance. With more than 200 mg. g -1

Cu2+ ion adsorbed from the wastewater. Such adsorption was mainly attributed to the

largest specific surface area of the calcium silicate.

Such finding was further strengthened by the repeat of Wang et al. (2019),

who studied the morphology of the calcium silicate for high-capacity formaldehyde

adsorption. In the study, calcium silicate that was produced using the precipitation of

sodium silicate and calcium hydroxide was reported to have porous honeycomb-like

structured material with a highly porous structure with multi-peak pore size distribution

(macropores, mesopores, and micropores) and high specific surface area, which favored

the adsorption of formaldehyde. It was also reported that the multi-peak pore size

distribution had provided a large number of the mesopores and macropores in the

honeycomb-like structure, which composed of foil-like sheets that increase the contact

area between adsorbates and the material by providing multiple non-resistance

transmission channels for formaldehyde molecule diffusion. Meanwhile, the micropores

abound on foil-like sheets had provided a vast number of active sites for formaldehyde

adsorption.

According to Estrela & Holland (2003), calcium hydroxide that commonly

used in the production of calcium silicate, was the strong base. In the production of

calcium silicate calcium hydroxide was used as calcium oxide (CaO) source (Wang et

al., 2019). As the CaO reacts with the silicic acid content in the silicate, acid-base

13
neutralization and the release of excess water from the silicic acid make the surface of

the calcium hydroxide more alkaline was occurred (Liao & Senna, 1992). Hence,

Rashid et al. (2011) reported that the acid-base neutralization and the release of excess

water from the silicic acid had led to the dissolution of the silicate at the contact point in

the precipitation of calcium silicate. Thus, it was also reported these reactions had

produced the calcium silicate adsorbent at the amorphous state. The amorphous silicate

adsorbent will be generated a larger pore size of the adsorbent and enhanced diffusion

of larger molecules such as FFA into the adsorbent (Assawasaengrat et al., 2015).

By understanding the benefits and morphological of calcium silicate that

would influence its adsorption performance, this thesis will now focus on investigating

the FFA adsorption performance of the calcium silicate derived from the rice husk and

calcium hydroxide as the adsorbent.

1.3 Hypothesis

Through material characterization, the essential characteristics of the synthesized

calcium silicate can be identified by using Fourier transform infrared (FTIR), scanning electron

microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD).

From the FTIR analysis, the presence of the silicate and adsorbed water

from all of the synthesized calcium silicate is expected. It can be predicted that calcium

silicate that will be prepared under different concentrations of calcium hydroxide

mainly has two characteristic peaks -OH and Si-O (S. Liu et al., 2020). As the higher

concentration of calcium hydroxide will be used, the band of the synthesized calcium

14
silicate should be much broader and more complex in the spectra (Clowutimon et al.,

2011). The bands that are similar to the characteristic peaks of silicon tetrahedral with

Q1 and Q2 Si sites should be found, while characteristic peaks of silicon tetrahedral

with Q3 and Q4 Si sites should not be found (García-Lodeiro et al., 2008). Thus, it will

indicate that the silicate chains of calcium silicate have a single-chain structure (Wang

et al., 2019).

Next, the SEM analysis on the synthesized calcium silicate will show the

morphology of the calcium silicate in which the honeycomb-like structure with a more

significant number of open pores should be observed. As a higher concentration of

calcium hydroxide is used in the preparation of the calcium silicate, the particle size of

the calcium silicate should be decreased due to the enhancement of the gel network

structure that appears in the calcium silicate particles (S. Liu et al., 2020).

The EDS analysis on the synthesized silicate should show that it comprises

at least 80% silicon and 20% calcium. The calcium element in the synthesized calcium

silicate is expected to increase when a higher concentration of calcium hydroxide is

used.

The calcium silicate formed from the XRD analysis should maintain that

even a high concentration of calcium hydroxide is used in the amorphous phase. The

concentration of calcium hydroxide that will be used should not affect the phase of the

calcium because the main factors that affect the crystallinity of the adsorbent are

impurities such as phosphorus, zinc, and potassium (Rivas, 2016). Most of these

impurities in the adsorbent should be removed during the pre-treated HCl and

15
precipitation process. The amorphous phase of the silicate is essential to enhance the

pore size of the calcium silicate compare to the crystalline phase. Thus, the larger pore

size of the silicate can influence the higher adsorption of the FFA molecules from the

WFO.

In terms of the adsorption capacities and removal percentages of free fatty

acid from WFO, the calcium silicate derived from the RHA is hypothesized to be better

as compared to HCl pre-treated RHA due to the higher impurities removal efficiency in

the calcium silicate through the precipitation method (Rashid et al., 2011). The lower

amount of the impurities in the precipitated calcium silicate is hypothesized due to

chemical treatments with HCl, sodium hydroxide, and distilled water washing

(Clowutimon et al., 2011). Thus, the precipitation method is hypothesized to produce

calcium silicate with high specific area and porosity, leading to a better adsorption

performance than the HCl pre-treated RHA adsorbent.

Next, the significant parameters such as calcium silicate dosage, FFA

concentration, and adsorption temperature that influence the FFA adsorption using

calcium silicates will also be observed. It is hypothesized that at higher calcium silicate

dosage, the higher FFA adsorption capacity and removal efficiency due to higher acidic

sites will be formed for the FFA adsorption (Assawasaengrat et al., 2015). When

alternating the FFA concentration, the adsorption capacity and FFA removal are

hypothesized to reduce with increasing FFA concentration. In terms of adsorption

temperature, the adsorption capacity and the removal efficiency of free fatty acid is

hypothesized to be lower at higher adsorption temperature due to the increment

16
solubility of the FFA in aqueous solution, which will lead to desorption of the

molecules of the interface (Freitas et al., 2007).

1.4 Research Objectives

1.4.1 General Objectives

To observe the performance of calcium silicate as an adsorbent in the adsorption of free

fatty acid from the waste frying oil.

1.4.2 Specific Objectives

To achieve these goals, there are three objectives that need to be focused:

i. To synthesize and investigate the material characterization of the calcium

silicates derived from HCl pre-treated rice husk ash (RHA) of different

concentrations of calcium hydroxide.

ii. To compare and differentiate the free fatty acid (FFA) adsorption capacities and

removal percentages using the convectional HCl pre-treated RHA and the

derived calcium silicate.

iii. To evaluate the effect of significant parameters affecting the FFA adsorption

capacity and removal percentage on the best performs adsorbent.

17
1.5 Scope of the study

First, the preparation of the acid pre-treated RHA and calcium silicate will

be done. For the conventional HCl pre-treated RHA, the rice husk will be pre-treated

with 3M of HCl by using the boiling method before the calcination to form RHA. On

the other hand, the calcium silicate will be prepared using the sol-gel method with

different concentrations of calcium hydroxide. The concentrations of the calcium

silicate that will be used are 0.5, 1.0, and 1.5 M.

Then, the calcium silicates produce by these concentrations will be

undergoing characterization by Fourier transform infrared (FTIR), scanning electron

microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), and x-ray diffraction

(XRD) before the adsorption process occurs.

FTIR will be used to identify bands representing the stretching vibration

mode of O–H for water molecules, calcium oxide (Ca-O), and silicon oxide (Si-O)

groups containing each calcium silicate. KBr pellet technique will be used to prepare

the sample for analysis, where approximately 3mg calcium silicate sample will be

mixed with 30 mg of KBr before they are grounded and pressed to prepare the pellets.

Then, FTIR spectra of this sample will be obtained in the range of 400 to 4000 cm-1.

The SEM analysis will be used to observe the differences in terms of morphologies for

each of the precipitated calcium silicates. It will be operated at an acceleration voltage

of 30 kV with magnification at 1000x, 5000x, and 10000x. Next, the EDS analysis will

be used to analyze the elemental composition of the calcium silicates. It will be

operated at 10 kV of accelerating voltage. Lastly, XRD analysis will be observing the

18
crystallinity phase of the synthesized samples. The accelerating voltage that will be

used by XRD is 40 kV. The samples will be scanned from 10 to 90° 2θ, with a scanning

rate of 0.5°/min.

After characterization is done, calcium silicates produced by different

concentrations will be used in the free fatty acid (FFA) adsorption with the constant

concentration of FFA, which is 1 mmol/L. The adsorption performance between both

adsorbents will be compared. In addition, lauric acid, known as saturated fatty acid, will

be used as the FFA sample in this study. The lauric acid stock solution will be prepared

by using isooctane as the solvent. After that, calcium silicate that shows the highest

adsorption capacity and the removal efficiency of FFA will be used to further this study

on the significant parameters such as calcium silicate dosage, FFA concentration, and

adsorption temperature that will influence the FFA adsorption.

In this study, the adsorption performance test will be done using a water bath

with an agitator. Each batch experiment will be carried out at various adsorbent

dosages, FFA concentration, and the adsorption temperature to investigate their

respective significance effect and factor at one time. The range of the adsorbent dosage

used in the adsorption test is fixed at 2, 4, 6, 8, and 10 mg/L. For FFA concentration, 2,

3, 4, and 5mmol/L will be tested. Lastly, the adsorption temperature will be altered at

30, 40, 50, and 60 oC. On the other hand, a calcium silicate adsorbent that shows the best

adsorption performance will be compared with HCl pre-treated RHA.

The adsorption performance from the synthesized adsorbents will be

determined by using free fatty acid (FFA) adsorption capacity and free fatty acid (FFA)

19
removal percentage. The analysis of the residual of FFA left after adsorption for each

adsorbent will be done using the sodium hydroxide (NaOH) titration method. 0.05 M

NaOH solutions will be used as titrant to neutralize the sample that had done the

adsorption process. 1% w/v of phenolphthalein will use as an indicator for the titration.

The titration process will stop as the color of the analyte is change into pale pink for 30

seconds. The titration step will be repeated three times for each experiment in order to

get accurate results.

20
 CHAPTER 2 : LITERATURE REVIEW

2.1 Frying

Frying is a process used to improve food quality by heating it to high temperatures

in oil (Fellows, 2017). It enhances the sensory quality of food by producing aroma compounds,

a pleasing color, crust, and texture (Bognár, 1998). Since it involves heating edible oil or fat and

simply using the hot cooking oil for the food, frying is one of the fastest, oldest, and easiest

food preparation methods (Rossell, 2001).

On top of that, deep-fried and pan-fried are two types of frying methods that people

usually enjoy worldwide. These methods are fast and produce palatable foods with distinct

sensory properties, such as color, flavor, and texture (Soupas et al., 2007). In deep-fat frying,

the food is surrounded by frying fat or oil, in which a series of events occur within minutes,

including dehydration of the food surface, fat absorption, and flavor compound formation and

surface color growth (Dobarganes & Márquez-ruiz, 2000). Compared to deep-frying, pan-frying

food is surrounded by minimal cooking oil as the minimal amount of oil is used just enough to

lubricate the pan (Zhao et al., 2019).

In each frying method, frying oil such as palm oil, olive oil, and coconut oil

is the essential element for the process (Tee et al., 2018). Plant-based lipids like coconut

oil, palm oil, olive oil, canola oil, and lipid-based animal fats like butter and ghee are

popular sources of frying oil (Alias et al., 2018). In Asia, palm oil or Elaeis

guineensis remains one of the primary sources of frying oil, with 85% of the world's

palm oil production (Feo et al., 2020). It contains approximately 50% saturated fatty

21
acids (SFA) and 50% unsaturated fatty acids (UFA) as well as other phytonutrients,

including carotenoids and vitamin E (Absalome et al., 2020).

2.2 Waste frying oil

The process of frying food using oil extracted from plant or animal fats

produces the fried food and a by-product known as waste frying oil (Alias et al., 2018).

Waste frying oil (WFO) is known as spent oil that has been used for deep frying and no

longer fit for human consumption (Sikiru et al., 2019). The WFO comprises tridi-

glycerides and mono-glycerides containing long-chain fatty acids (primarily palmitic,

stearic, oleic, linoleic, linolenic, and behenic acids) and a variable proportion of free

fatty acids (FFA). Table 2.1 shows the summary of the typical FFA composition of

waste frying oil.

Table 2.1: Summary of typical FFA composition of waste frying oil

(M. Ali, 2015)
Fatty acid composition wt.%
Palmitic C 16:0 29.75
Stearic C 18:0 3.08
Oleic C 18:1 34.01
Linoleic C 18:2 11.16
Linolenic C 18:3 8.12
Arachidic C 20:0 10.98
Behenic C 22:0 2.06

In the frying process, the rich chemical components of the fried food are

subjected to many chemical and physical transformations such as increased viscosity

and darkening in color of the frying oil (Nayak et al., 2016), promoted by the high

temperature and exposure to air (Mannu et al., 2019). As they undergo chemical

reactions, increased particulate matter, and volume of total polar solids, polymeric

22
molecules were reported (Kulkarni & Dalai, 2006). In addition, due to the continuous

heating of the frying oil at the high temperature and the presence of the oxygen and

water moisture from the fried food, the degradation reaction such as hydrolysis, thermal

oxidation, and polymerization occurred (Choe & Min, 2007). It will be resulting in the

decomposition of the frying oil and lead to the formation of waste frying oil, WFO

(Chiou et al., 2009). This deterioration of the frying oil rendered it unsafe for human

consumption and posing significant health risks such as gastrointestinal problems and

even mutagenesis in humans (Panadare & Rathod, 2015).

Specifically, in hydrolysis, the ester linkages in the frying oil are attacked by

the water molecules, producing the triacylglycerols, FFA, monoglycerides, and

diglycerides (Sanli et al., 2011). As such, compared to the fresh frying oil, the content

of FFA in the waste frying oil is exceptionally high due to the repeated heating of the

oil and hence the repeating hydrolysis process (Panadare & Rathod, 2015). Meanwhile,

in thermal oxidation, triglyceride molecules in the frying oil undergo primary oxidation

to form the unstable lipid species, namely hydroperoxides, which decompose to form

secondary oxidation products comprising several volatile and non-volatile compounds

(Goswami et al., 2016). Most of these secondary oxidation products polymerize and

increase the oil’s viscosity, causing surface browning and darkening the oil forming

WFO (Dana & Saguy, 2001).

On top of that, in polymerization, the frying process produces high

molecular cyclic FFA monomers, triglycerides dimers, and oligomers at high

temperatures (Goswami et al., 2016). Many oxidative products such as hydroperoxides

and aldehydes are generated during the frying process, affecting the oil quality (Choe &

23
Min, 2007). Owing to the accelerated development of oxidized and polymerized liquid

species in the frying medium, oil consistency degrades as the frying time increases

(Goswami et al., 2016).

Statistically, 4.1 kg (9 pounds) of waste cooking oil was generated per

person per year (Patil et al., 2012). Today's world population was reported around 7

billion; thus, around 29 million tons of WFO were generated per year (Maddikeri et al.,

2012). More than 15 million tons of WFO generated from selected countries globally,

such as China, Malaysia, United States, and a few others, was reported (Math et al.,

2010). Table 2.2 shows the summary of the quantity of WFO produced in selected

countries.

Table 2.2: Summary of quantity of waste frying oil produces in selected countries
(Math et al., 2010)
Country Quantity (million tons)
China 4.5
Malaysia 0.5
United States 10.0
Taiwan 0.07
Europe 0.7-10
UK 0.2
Canada 0.12
Japan 0.45-0.57
Ireland 0.153

The unregulated disposal of waste frying oil has negative environmental

and economic consequences (Feo et al., 2020). Disposal of WFO had created a

significant challenge due to the dumping problems and possible pollution of the water

and land resources (Maddikeri et al., 2012). Every litre of oil leaked into natural water

reservoirs is said to pollute another 500 000 litres of water, as it primarily raises the

organic load on the water bodies and also forms a thin lipid layer over the water that

24
decreases the crucial dissolved oxygen concentration for the aquatic living plants and

creatures (Carlos et al., 2011). Furthermore, WFO improperly disposed of in the kitchen

sinks will solidify and clog sewer pipes (Sanli et al., 2011). Further degradation of the

WFO in sewer pipes can cause metal and concrete elements around the sewage

streamline to corrode(Refaat,2010).

2.3 Rice husk and rice husk ash

The majority of paddy rice varieties are made up of approximately 20% rice

husk (RH), 11% bran layers, and 69% starchy endosperm (Hossain et al., 2018). During

the paddy milling process, rice husk, the outermost layer of the paddy grain is separated

from the rice grains (Pode, 2016). The rice husk consists mainly of the organic

components such as hemicelluloses, cellulose, lignin and ash, and elemental

components such as carbon, hydrogen, nitrogen, silicon and oxygen (Sarangi et al.,

2009). The RH composition is influenced by a number of parameters, including rice

variety, fertiliser type, soil chemistry, and even production location (Javed et al., 2008).

Table 2.3 shows the summary of typical rice husk composition.

Table 2.3 Summary of typical rice husk composition

(Sarangi et al., 2009)
Constituents Composition (%)
Hemicellulose 24.3
Cellulose 34.4
Lignin 19.2
Ash 18.85
Carbon 37.05
Hydrogen 8.80
Nitrogen 11.06
Silicon 9.01
Oxygen 35.03

25
 Due to the rapid economic and population growth in many Asian and

African countries, the rice demand is expected to remain high in the coming decades

(Timmer et al., 2010). Thus, rice agricultural waste such as rice husk will continue to be

abundant and a burden to the society in the future (Pode, 2016). As the rice husk

becomes more extensive, most of the rice husk is either discarded or burned in open

spaces, causing serious environmental contamination and land degradation (Bakar et al.,

2016). As a way to control the environmental contamination caused by the rice husk,

many attempts have been made to utilize rice husk including as an alternative fuel for

energy production, as a raw material for the manufacturing of silica and silicon based

industrial chemicals as well as the raw material for the manufacturing of activated

carbon (Chungsangunsit et al., 2010).

Meanwhile, Babaso & Sharanagouda (2017) reported that due to the low

thermal conductivity of the air entrapped in the rice husk’s pores, more porous and

thermal insulated bricks could be made by incorporate a high percentage of rice husk

into the brick mixture, making porous fire brick structures more ideal for back up

insulation.

On The other hand, rice husk ash (RHA), the secondary product is massively

produced after the rice husk combustion during the electricity generation process (X.

Liu et al., 2016). According to Pode (2016), in the last few years, several Asian rice

millers and factories had begun to use the rice husk to generate electricity by

combustion. It is considered as a high-value industrial product since a tonne of rice

husk could generate about 800 kW of electric power due to its high calorific value (Lim

26
et al., 2012). Commonly, the RHA is typically deposited in the landfill (Bakar et al.,

2016). However, such deposition might lead to serious environmental contamination if

not managed properly, especially when the sheer amount of the RHA is overwhelming

(Chungsangunsit et al., 2010). Hence, the RHA that produced from the controlled

combustion of the rice husk must be otherwise utilized, as it may not only solve the

issue of the solid waste disposal, but it could also keep the environment free from the

pollution caused by this overwhelmingly available organic waste (Mahmud et al.,

2010).

Generally, RHA has three-layered structures: inner, outer and interface with

interstitial and honeycombed pores, which are the primary reason of the RHA’s high

chemical activity and large specific surface area (X. Liu et al., 2016). The RHA

produced can be used in many applications such as the synthesis of pozzolanic

materials, as the source of silica, as an adsorbent and many other uses (X. Liu et al.,

2016). Table 2.4 shows the summary of significant RHA application in various fields

that were reported in the literature recent years.

27
 Table 2.4: Summary of significant RHA application in various fields that were reported in the
literature recent years
Use of RHA Application References
Filler production Replacing the use of the high cost synthetic (Turmanova et al.,
addictive aerosol in a range of polymer 2012)
composite preparation.
Graphene Replacing silicon carbide that is used in the (Muramatsu et al.,
production production of graphene and paves the way 2014)
for large-scale, defect-free graphene
development.
Pozzolanic Use as the cement replacement in the (Pode, 2016)
materials concrete which can increase the corrosion
production resistance, durability properties of the
concrete and also improve its tensile
strength.
Soil conditioning Improves the strength and bearing ability (Muntohar, 2014)
of the expansive soil by reducing swelling.
Drug delivery Improved the method of making silica (Rajanna et al., 2014)
system aerogel micro particles (SAMs) that are
used in the drug delivery systems.
Adsorbent Used to adsorb heavy metals, oil, SO 2, and (Ahmaruzzaman &
free fatty acid which can also solve the Gupta, 2011)
environmental problem. (Feng et al., 2004)
(Mahvi et al., 2004)
(X. Liu et al., 2016)

Source of silica Use as excellent source for synthesizing (Hossain et al., 2018)
the high-grade amorphous silica.

2.4 Silicate derived from natural resources

Silicates are salts and esters of mono silicic acid (H 4 SiO4) with tetrahedral

arranged anions [SiO4]4- of variety configurations (Lührs & Geurtsen, 2009). Si2O67-

and SinO3n2n are some of the important example of the silicate configuration.

Most of the silicates have high silica content, contributing to good reactivity

and high efficiency of silicate performance, especially as an adsorbent (Lin et al.,

2020). Commonly, silicates derived from natural resources with well-defined

28
mesopores size distributions and broad surface areas have piqued interest due to their

possible applications in sensors, bioreactors, separations catalysis, and also adsorption

(Aboelenin et al., 2017).

The mesoporous silicates can be derived from many natural sources such as

diatomite ores (Wu et al., 2005), carbide slag (Fang et al., 2018), and carbide slag (Fang

et al., 2018). The produced mesoporous silicates demonstrated high surface area, and

when it well-dispersed with iron, it showed excellent adsorptivity on the adsorption of

methylene blue dye (Aboelenin et al., 2017). The silicate's derivation from another

natural resource that is silica-rich, red palygorskite clay, was relatively more eco-

friendly and required lower cost as the silicate with high stability and able to remove

antibiotic from the wastewater was produced from it (Wang et al., 2016). Meanwhile,

Özgül-Yücel et al. (2004) reported that the silicate could be derived from silica-rich

RHA. Silica-rich rice husk ash (RHA) can be achieved by thermal treatment at elevated

temperatures (Shen, 2017). The mesoporous silicate can be derived from the RHA by

precipitation of synthesized silicate from RHA with alkaline metal salts (Rashid et al.,

2011).

2.5 Silicate as adsorbent

The amorphous silica structure of silicate makes their adsorption ability

much stronger than that of crystalline silica because the amorphous state will provide

excellent properties of the silicate for the adsorption, such as high specific surface area

(Lin et al., 2020). Based on the literatures, among the reported synthetic adsorbent

produced, magnesium silicate and calcium silicate are some of the most studied

29
adsorbents with great ability to adsorb pollutant such as heavy metal from wastewater

(Shen et al., 2014). However, only limited studies had been done to show the FFA

adsorptive ability from WFO using these two adsorbents (Song et al., 1998).

2.5.1 Magnesium silicate

Florisil, Magnesol XL, and Mizukaife are some of the commercially available synthetic

magnesium silicate used for chemical analysis and chemical processing, such as the

regeneration of used frying oils (A. Krysztafkiewicz et al., 2007). Commonly,

magnesium silicate also can be produced by precipitated the silicate that derived from

natural resources and magnesium salt such as magnesium nitrate, magnesium sulphate

and magnesium chloride (Andrzej Krysztafkiewicz et al., 2004). The precipitation step

was essential to produce the relatively high BET specific surface area of the magnesium

silicate (Japir et al., 2017). It was found that the silicate precipitated by metal ions has

an amorphous structure of metal silicate (Potapov & Zhuravlev, 2005).

The different types of salts used in the production of magnesium silicate do not affect

their adsorption performance, especially the adsorption of FFA from WFO (Rashid et

al., 2011). Taspinar & Ozgul-Yucel (2008) reported that magnesium silicates produce

by using different magnesium salts, which are magnesium sulfate and magnesium

nitrate, had showed the same oleic acid adsorption capacity, which 57 mg oleic acid/ g

adsorbent.

Precisely, the adsorption performance of magnesium silicate was mainly depended on

the method and source of the silicate used to produce the magnesium silicate (Özgül-

30
Yücel et al., 2004). Magnesium silicate produce from the amorphous silicate has

resulted in small size particles and larger pore diameter, which enhanced diffusion of

larger molecules such as FFA (Assawasaengrat et al., 2015). Magnesium silicate

derived from a natural resource such as RHA was reported to have larger pore volume

and larger specific surface area since RHA was rich with amorphous silica

(Clowutimon et al., 2011). In a comparison, magnesium silicate derived from RHA had

showed a higher FFA adsorption which is 644 mg FFA/g adsorbent, compared to

commercial magnesium silicate, Magnesol XL, which adsorb 616 mg FFA/g adsorbent

(Assawasaengrat et al., 2015). Commercial magnesium silicate showed a lower FFA

adsorption capacity than magnesium silicate derived from RHA because it was

commonly produced in the semi-crystalline phase; thus, the fewer pore is used to adsorb

the FFA molecules can be generated (Wang et al., 2019).

As such, it can be concluding that RHA can be a good resource for synthesized

magnesium silicate. Magnesium silicate synthesized from RHA can be a promising

adsorbent for the FFA adsorption from WFO due to its high porosity, larger pore

diameter, and high specific surface area.

2.5.2 Calcium silicate

Calcium silicate is one of the efficient silicate-based adsorbent due to its

porosity structure (Wang et al., 2019). But, most of the researches were focused on the

adsorption of formaldehyde and heavy metals by using calcium silicate and limited

researches were done on the adsorption of FFA by using calcium silicate (S. Lin et al.,

1999).

31
 According to Song et al. (1998), calcium silicate was reported as an effective for

FFA adsorption with remarked efficiency as high as 84.5%. In that experiment, the

comparison of FFA adsorption from the WFO was done using nine different types of

commercial synthetic silicate adsorbents including Silasorb, Britesorb, HB600, Purim,

Frypowder, Activated Carbon, and Magnesol, as well as two commercially unavailable

adsorbents, Sorbead AF and Calsilite. It was found that the adsorbents with calcium

silicates component showed the highest FFA adsorption, which 85% for HB 600 and

followed with 59.91% for Silasorb, respectively. The highest percentage of FFA

adsorption by HB 600 could be attributed to the low amount of impurities, subsequently

high silica content in the adsorbent, its small particle size and also its amorphous nature,

which resulted in larger specific surface area and high porosity that can be contributed

to its exceptional adsorption performance (S. Lin et al., 1999).

The porosity of calcium silicate can be produced by precipitation process

between sodium silicate that derived from the natural sources and calcium salts such as

calcium acetate (S. Liu et al., 2020). Meanwhile, Wang et al.,(2019) reported that

calcium silicate that produced by precipitation between sodium silicate and calcium

hydroxide had well developed porosity and unique pore structure. In that study, it was

found that calcium silicate had consist of two type of pore structure which macropores,

type A and micropores, type B. These unique conical pore structures are favourable to

the movement and adsorption of larger molecules and provide the high capacity for the

adsorbent (Zhang et al., 2017) . Singh, (2018) reported that the highest macroporosity

were generated the higher specific surface area of the, thus it were enhanced the

adsorption of FFA molecules.

32
 Meanwhile, Ogata et al. (2019) investigated the adsorption capacity of the spent

calcium silicates that were commonly used as a food addictive in Japan (CAS30,

CAS60, and CAS90) in hope to improve the quality of edible waste oil. These calcium

silicates have different molar ratio of calcium to silica which are 1:3 (CAS30), 1:6

(CAS60) and 1:9 (CAS90) (Ogata et al., 2013). In the report, Acid Value (AV) showed

a positive correlation coefficient with a FFA removal. It was found that the highest

amount of silica in calcium silicates, CAS90 in this case, had the highest specific

surface area (187.47 m2/g) and subsequently the high FFA removal percentage, 23%.

Such phenomenon was attributed to the presence of the polar silanol (Si-OH) group and

the hydrophobic siloxane linkage (Si-O-Si) which had interacted with the acidic

compound in the edible oil (Bhattacharya et al., 2008). Hence, it was also concluded

that the amount and the purity of the silica would affect the adsorption performance

when the calcium silicate was used as adsorbent.

These can be concluding that calcium silicate can be a good adsorbent to

remove the FFA from the edible oil due to its macroporosity characteristic. The amount

of silica content in the calcium silicate is the most important factor for its adsorption

performance.

2.6 Materials characterizations

Characterization is important to provide the basis for a better understanding of

complex structure-properties applications relationships of the silicates (P. C. Lin et al.,

2014). Silicate characterization can be done by using Fourier transform infrared (FTIR),

33
scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), and

x-ray diffraction (XRD) before the adsorption process occurs. Other than these four

methods, the characterization of the silicates also can be done by other method such as

transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS),

Nuclear magnetic resonance (NMR) spectroscopy and more (Kaliva & Vamvakaki,

2010). Since in this study will be more focused on the morphology, amorphous, the

organic components and the elemental components of the silicate, the 4 methods which

are FTIR, SEM, EDS, and XRD techniques will be used.

2.6.1 Fourier transform infrared (FTIR)

FTIR analysis is a technique for identifying organic, inorganic, and polymeric

materials by scanning them with infrared light (Titus et al., 2019). In FTIR analysis, a

change in the material composition is indicated by the changes in the specific

absorption band pattern (Kaliva & Vamvakaki, 2010).

Kalapathy et al., (1999) observed and reported that the predominant absorbance

bands could be detected between 800 and 1400 cm-1 and it was attributed due to the

siloxane (Si-O-Si) in the silicate-based materials. The band around 600 cm -1 was also

detected due to the Si-O-Si bending vibration (Mostafa et al., 2009). In magnesium

silicate, the silica gel spectrum includes broad bands around 1970 cm −1 and 1864 cm−1

due to structural vibrations and there are no corresponding bands in the magnesium

silicate spectrum(Yates et al., 1997). Clowutimon et al. (2011) reported that the band

represented the vibration of siloxane bonding, Si-O-Si; in magnesium silicate from rice

husk was at 1075.2, 1028.41 and 1096 cm -1, respectively. In that study it was reported

34
the band of the synthesized magnesium silicate was much broader and more complex in

the spectra. The broadening was likely due to the random presence of magnesium in the

structure of magnesium silicate derived from rich husk (Yates et al., 1997). In calcium

silicate adsorbents, only one wide band with a strong intensity can be observed at 3445

cm−1, which is associated with the stretching vibration mode of O–H for water

molecules (Wang et al., 2019). The bands at 970 and 870 cm −1 were similar to the

characteristic peaks of silicon tetrahedral with Q1 and Q2 Si sites as well as the band at

1630 cm−1 is mainly ascribed to the bending vibration mode of O-H for water molecules

were also found on the calcium silicate (Estrela & Holland, 2003).

These can be concluding that as the magnesium silicate or calcium silicate are

being derived from the pure silicate or natural silicate, the main compound or group that

can be detected with FTIR analysis are siloxane group and also hydroxyl group due to

the silicic acid content that contain in these silicate-based adsorbents.

2.6.2 Scanning electron microscopy (SEM)

Scanning electron microscopy (SEM) is a surface-imaging technique that uses a

directed electron beam to scan the sample's surface and produce highresolution and high

magnification images (Kaliva & Vamvakaki, 2010). SEM has a resolution of up to 1nm

and a magnification of 400,000 X (Shanks, 2013). In SEM analysis, the sample's

surface must be chemically stable and grounded in order to minimize the accumulation

of electrostatic charge on the surface, which can be caused the electrostatically distorted

images(Salame et al., 2018). As such the surface of nonconductive samples are coated

35
with an ultrathin film of an electrically conducting material, such as Au, Au/Pd alloys,

and Pt (Barhoum et al., 2018).

The morphology of calcium silicate showed a porous honeycomb

structure with many open pore structure (Campopiano et al., 2014). The pore structure

on the calcium silicate surface had a large size within the range of 50-100 nm (Lin et

al., 2020). The backbone of the honeycomb structure of the calcium silicate was

composed of a large number of foil-like sheets (Guan et al., 2013). The sheets were

stacked via a side-to-edge or edge-to-edge contact, forming a porous honeycomb

structure with a large number of open pores (Wang et al., 2019). When the

concentration of the calcium salts in the calcium silicate produced increased, the gel

network structure were started to form and cause the particle size of the calcium silicate

decreased(S. Liu et al., 2021). The reduction of paricle size adsorbent were increased

the specific surface area of the adsorbent, thus enhanced tha adsorbtion of the FFA

molecules (Assawasaengrat et al., 2015).

2.6.3 Energy dispersive x-ray spectroscopy (EDS)

EDS can be used to detect the elemental composition that contained in the

silicate-based adsorbent (Titus et al., 2019). Using EDS analysis, Fang et al., (2018)

reported that the main element found in the silicate were silicon, (Si) and oxygen (O).

Commonly, for the typical silicate-based adsorbent, 52.2 %wt of Si and 47.8% wt of O

were presented in the EDS spectrum (Vos et al., 2014). Both of Si and O were

uniformly distributed on the sample surface, indicating the absence of other significant

elements or impurities (Saravanapavan & Hench, 2003).

36
2.6.4 X-ray diffraction (XRD) analysis

Since the wavelengths of X-ray (between 0.2 and 10nm) are equivalent to the

interatomic spacing of crystalline solids, X-ray diffraction (XRD) is commonly used to

observe the crystalline structure of the solid sample (Kaliva & Vamvakaki, 2010).

Generally, XRD determines the orientation of a single crystal or grain and the size and

shape of the small crystalline area by measuring the average spacing between layers or

rows of atoms (Salame et al., 2018).

Kalapathy & Proctor (2000) performed XRD analysis on the silicate extracted

from RHA at the setting of 40 kV acceleration voltages, 45 mA current, and scanned at

a rate 1.25o/min from 5 to 55o. They reported that the silicate extracted from the RHA

lacked of sharp peaks in the XRD pattern, indicated the absence of the crystalline

structure(Terzioglu & Yucel, 2012). Hence the silicate produced was in amorphous

state which means that the silicate were had the higher specific surface area and pore

volume which will lead to the more efficient adsorption performance (Liu et al., 2021).

The amorphous or crystalline structure of the silicate was dependent on the combustion

temperature of the RHA before the extraction process occurs (Deshmukh et al., 2012).

As the amorphous silica had been used to produce silicate-based adsorbent such as

magnesium silicate, the amorphous state of the adsorbent will maintain(Andrzej

Krysztafkiewicz et al., 2004).

37
2.7 Significant parameters affecting FFA adsorption

There are several significant parameters that affecting the adsorption of FFA on

the silicate which are adsorbent dosage, FFA concentration, adsorption temperature and

contact time.

2.7.1 Adsorbent dosage

The adsorbent dosage of silicates used will affect the FFA adsorption capacity.

There are two researchers that had done the study of effect of adsorbent dosage on the

FFA adsorption.

Firstly, according to Clowutimon et al., (2011), as the adsorbent dosage

increased the adsorption of FFA capacity were decreases. In that report, they had used

0.25g magnesium silicate as the lowest amount of adsorbent dosage and 2g of

magnesium silicate as the highest amount of adsorbent dosage. Generally, the

adsorption capacity of the adsorbates should increase as the adsorbent dosage increased

(Narachai et al., 2018). But different trend was reported in this study, where the lowest

adsorbent dosage had showed the highest FFA adsorption capacity and the highest

adsorbent dosage had showed the lowest FFA adsorption capacity. It was also reported

that this trend occurred due to the surplus amount of adsorbent that not reacted during

the adsorption process. The higher adsorbent dosage might cause the aggregation of

adsorbent during the adsorption process, which lead to the decrement of the adsorption

sites that available on the silicate (Alghamdi et al., 2019). This trend also might be

occurred because of the error that occur during the precipitation or silicate extraction

38
step, where the silicate-based does not well precipitated and extracted, thus the

generation of adsorption sites and pore structures were disturbed(Rashid et al., 2011).

Secondly, Assawasaengrat et al., (2015) reported that adsorbent dosage were

directly proportional with the FFA adsorption capacity. This study reported that the

highest adsorbent dosage, 3g had showed the highest FFA adsorption while the lowest

adsorbent dosage, 1g had showed the lowest FFA adsorption. As the higher amount of

adsorbent dosage used, the higher FFA adsorption capacity were resulted (Ciesielczyk

et al., 2007). This report were also reported that the higher adsorbent dosage used in the

adsorption of FFA were provide more adsorption site. The high adsorption site were

improved the FFA adsorption capacity from the WFO (Terzioglu & Yucel, 2012).

These can be conclude that the production step of the silicate-based adsorbent

must be handle carefully, in order to produce the most efficient adsorbent especially for

FFA adsorption. Then, the adsorption capacity should be directly proportional with

adsorbent dosage.

2.7.2 Adsorption temperature

The effect of adsorption temperature had been observed by Ogata et al., (2019).

In this study, the adsorption capacity of FFA by calcium silicate will increase as the

adsorption temperature increased, where the removal percentages of FFA are in the

ranges 12.1–19.9% at 80 °C and 22.3–32.2% at 100 °C. Different trend had been

reported by (Freitas et al., 2007) where the amount of fatty acid adsorbed on the

39
magnesium silicate and activated carbon decreased with the increase of temperature,

from 298 K to 323 K, at constant concentration.

Generally, different types of adsorption were influenced the adsorption

performance of the adsorbents at different temperature (Freitas et al., 2007). According

to Chua, (2008), the adsorption capacities of the adsorbents that adsorb FFA though

physisorption were decrease as the adsorption temperature increased because it

involved the weak van der Waals forces which weaken with a rise in the temperature.

Meanwhile, the adsorption capacities of the adsorbents that adsorb FFA though

chemisorption were increased as the adsorption temperature increased because

chemisorption involved the formation of chemical bonds involving activation energy

and like any other chemical reaction is favored by a rise in temperature. Calcium

silicate adsorbents was known as one of the example adsorbent that adsorb FFA

molecules through chemisorption (Ogata et al., 2018), and magnesium silicate

adsorbents was known as one of the example adsorbent that adsorb FFA molecules

through physisorption (Rashid et al., 2011).

These can be conclude that adsorption capacities of the adsorbent in different

adsorption temperatures is depend on the types of adsorption that will occur between

the adsorbent and adsorbates.

40
2.8 Review finding and highlight

In conclusion, the continuous heating of frying oil at a higher temperature can

cause the increment of FFA content in the oil and turn into WFO. When the higher FFA

content in the WFO was not treated competently, it will lead to severe human health

upon consumer and the serious environmental conditions. In order to address this issue,

the FFA content in the waste frying oil can be treated using the adsorption method since

it is known as one of the low-cost methods. It was reported that, the adsorption of FFA

could done using acid pre-treated rice husk or rice husk ash. However, the silicate-

based adsorbent was found to be more effective in the adsorption of FFA since it has a

layer specific surface area and lower amount of impurities. The precipitation method

could be used to produce the amorphous silicate-based adsorbent with large specific

surface area that might be useful in FFA adsorption. The higher amount of silica

content in the silicate-based adsorbent will lead to the higher adsorption of the FFA.

41
 CHAPTER 3: METHODOLOGY

3.1 Overall experimental works

This study investigates the adsorption of free fatty acid (FFA) on the calcium

silicate derived from rice husk ash (RHA). Firstly, the rice husk (RH) will be pre-

treated with HCl to remove impurities from the RH. Then, the RH will be washed with

distilled water until the effluent becomes neutral. The pre-treated RH will then be dried

and burnt in the furnace to produce RHA. After the RHA is produced, it will be used to

synthesize the calcium silicate by sol-gel method using different concentrations of

calcium hydroxide solution. The precipitated calcium silicate of different Ca(OH)2

concentration will be characterized using Fourier transform infrared (FTIR), scanning

electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), and x-ray

diffraction (XRD). As the characterization of calcium silicate is being observed, the

adsorption performance of calcium silicate will be measure and calculate by using FFA

adsorption capacity and removal percentage will be calculated. Then, the investigation

on the effect of significant parameters such as adsorbent dosage, FFA concentration,

and adsorption temperature will be conducted. The flow chart of the overall planned

experimental works was shown in figure 3.1:

42
Figure 3.1 Flow chart of experimental works.

43
3.2 Chemicals and materials

The chemicals and materials that will be used in this study are listed in Table

3.1.

Table 3.1: List of chemicals and materials needed

Chemicals Purity (%) Supplier Purpose of use
Calcium 96% KSFE, Malaysia Use as source of calcium
hydroxide oxide, CaO in calcium
silicate
Hydrochloric acid 37% Sigma-Aldrich, Use to pre- treat the RH in
Malaysia the pre-treatment process
Lauric acid 99% R&J Chemical Use to prepare the FFA
solution that will used as
adsorbates
Isooctane 99% Sigma- Aldrich, Use as solvent to dilute
Malaysia FFA
Phenolphthalein 98% Gouden, Use as pH indicator in the
Malaysia FFA neutralization
Sodium hydroxide 40% Sigma-Aldrich, Use to neutralize the FFA
Malaysia solution
Rice husk Dibuk, Perlis, Use as source of silica for
Malaysia calcium silicate production

44
 3.3 Equipment

The equipment that will be used and their respective purpose are listed in
Table 3.2

Table 3.2 List of equipment needed

Equipment Purpose
Analytical balance To measure the weight of the samples
Furnace For the calcination of the RH
Fourier transform infrared (FTIR) To identify the functional group that contain
calcium silicates
Energy dispersive x-ray spectroscopy (EDS) To identify the elemental composition of the
synthesized calcium silicate
Scanning electron microscopy (SEM) To analyse the morphology of the synthesized
calcium silicate
X-ray diffraction (XRD) To analyse the amorphous structure of
calcium silicate
Pippetes To transfer the FFA solution into the conical
flask
Oven To dry the samples
Water bath shaker To control the temperature and shake the
sample during the adsorption

3.4 Preparation of calcium silicate as adsorbent

3.4.1 Pre-treatment of RH

The rice husk used will be obtained from Dibuk, Pelis, Malaysia, and its acid

pre-treatment using HCl solution will be reported by Clowutimon et al. (2011). 10g rice

husk will be boiled at 100oC in 50 ml of 3M HCl for 3 hours, and then it will be washed

with distilled water until the pH of the washed water becomes neutral (pH=7). After

that, the RH will be dried in the oven for 100 oC for 12 hours, before it will be

45
combusted at 500oC for 2 hours, and the RHA will be obtained after the combustion

process is done.

3.4.2 Synthesis of calcium silicate

The RHA obtained from the calcination of the RH will be used to synthesis

the calcium silicate. The RHA will be ground and sieved to the particle sizes below 100

μm using mortar. 4.4g of RHA will be boiled with 1.6g of 0.05 M sodium hydroxide in

100 ml of water at 100°C until the solution volume drop to 50 ml. Then, 50 ml of the

remain solution will be reacted with 70 ml of 0.5M calcium hydroxide, Ca(OH) 2

solution at 95°C for 1 hour. The liquid mixture with precipitates will then be filtered

and washed three times with 50 ml of deionized water (Wang et al., 2019). The

precipitate will be dried at 100°C for 12 hours in the oven to obtain calcium silicate.

The calcium silicate produced using 0.5M Ca(OH)2 solution will be labelled as CS-0.5.

Calcium silicate adsorbent will also be produced by using different concentrations of

Ca(OH)2 solution, which is 1.0 M (CS-1) and 1.5 M (CS-1.5).

3.5 Material characterization

3.5.1 Fourier transform infrared spectroscopy (FTIR)

FTIR analysis with a potassium bromide, KBR technique will be used to

characterize the functional groups of synthesized calcium silicates. KBR needs to be

oC
dried at 110 for 12 h before the analysis to remove any adsorbed

46
moiture(Assawasaengrat et al., 2015). About 3mg of calcium silicate will be mixed with

30mg of potassium bromide, and this mixture will be ground together in a mortar. The

powder mixture will then be transferred into a sample barrel. About 13 tons of force for

will be applied the powder to form a pellet before the pellet is used for transmittance

infrared spectroscopic measurements. The range of FT-IR spectra measurement that

will be find between 4000-400 cm-1 while 10 scans with 4 cm-1 resolution will be

taken.. For all of the FTIR spectra measurements, the background spectra will be

obtained using the respective sample holders without the samples, and all of the FTIR

spectra will be automatically corrected for the background by using the software used

for data collection (Kalapathy & Proctor, 2000). This analysis will be done at the

Instrumentation Lab, Faculty of Chemical Engineering Technology, UniMAP.

3.5.2 Scanning electron microscopy (SEM)

SEM will be used to analyze the morphology of the synthesized calcium

silicates at 1000x, 5000x, and 10000x, magnifications. The calcium silicates will be

deposited on a sample holder with a double-stick conducting carbon tape, coated with

gold to improve the surface conductivity prior to analysis (Phuttawong et al., 2015).

The SEM will be performed at the accelerating voltage of 10.0 kV. This analysis will be

done at the school of Material Engineering, Faculty of Chemical Engineering

Technology, UniMAP.

47
3.5.3 Energy dispersive x-ray spectroscopy (EDS)

Compiled together with SEM, the EDS analysis will be used to analyze the

elemental compositions of the synthesize calcium silicates. A 10 kV accelerating will

be used to produce the X-rays emission onto the sample to measure the elemental

composition pressence in calcium silicate (Taheraslani & Gardeniers, 2019). This

analysis will be done at the school of Material Engineering, Faculty of Chemical

Engineering Technology, UniMAP.

3.5.5 X-ray diffraction (XRD)

XRD analysis will be used to reveal the main amorphous phases. The

analysis will be performed with Cu Kα radiation (λ = 1.5406 Å), with 40 kV and 45mA.

The sample will be scanned with the diffraction angle between 10 to 90 o, at a scanning

rate of 0.5°/min (Phuttawong et al., 2015). This analysis will be done at Centre of

Excellence for Frontier Materials Research, School of Materials Engineering, UniMAP.

3.6 Preparation of free fatty acid stock solution

Lauric acid will be used as stock free fatty acid throughout in this study. For

the preparation of the lauric acid stock solution, 0.1g of lauric acid will be dissolved in

isooctane and the solution will be made up into 500 ml. The concentration of the lauric

acid solution is 1 mmol/L. Then, these steps will be repeated by using 0.2g, 0.3g, 0.4g

48
and 0.5g of lauric acid for the preparation of lauric acid solution with the concentration

2 mmol/L, 3 mmol/L, 4 mmol/L and 5 mmol/L.

3.7 Adsorption of fatty acid by calcium silicate

For a typical free fatty acid adsorption experiment, 1g of CS-0.5 will be

weighed using an analytical balance. 1 ml of the stock fatty acid solution will be filled

into a 50 ml conical flask. 0.1g of the adsorbent will then be added into the conical flask

at the room temperature, and it will be placed in the shaker(Clowutimon et al., 2011).

The sample will be shaken for 180 rpm at 50 °C for 1 hour. After one hour, the mixture

will be filtered. 10 ml of supernatant will be pipetted in 10 ml of neutralized isoocatene,

and the mixture will then be titrated with 0.05 M NaOH and phenolphthalein as

indicators until the color of the mixture changes from colorless to pale pink for at least

30 seconds. As for the blank sample, 50 ml of the same fatty acid solution that is not

treated with the adsorbent will also be titrated with the same NaOH solution. Blank will

be used to determine the quantity of titrant required to reach the endpoint of the titration

(Taspinar & Ozgul-Yucel, 2008). The titration for the same experiment will be done at

least three times in order to get accurate results. The experiment will be repeated by

using CS-1, CS-1.5, and RHA.

The adsorption performances for each adsorbent will be observed and

compared by referring to their respective adsorption capacity and FFA percentage

removal. The adsorption capacity and percentage removal calculated by using Equation

3.1 and Equation 3.2 respectively:

49
 G
Adsorption capacity, C = N × M fatty acid × (Vo – V1) × (3.1)
1000

Where,

G is the amount of the adsorbent (g), N is the exact normality of the NaOH solution,

Mfatty acid is the molecular weight of fatty acid used, Vo(ml) is the volume of NaOH used

for blank titration of untreated fatty acid solution (ml), and V1 is the volume of NaOH

used for back titration of treated lauric acid solution (ml) (after adsorption).

Co−Ct
Percentage removal of FFA, %FFA = × 100 (3.2)
Ct

Where,

Co is initial concentration of solution (mg/L) and Ct is final concentration of solution

(mg/L).

3.8 Significant parameters studies

CS adsorbent that showed the highest FFA adsorption performance will be

used for further the investigation on the effect of significant parameters such as

adsorbent dosage, FFA concentration, and adsorption temperature to the adsorption

performance of the synthesized calcium silicate.

50
3.8.1 Adsorbent dosage

For the effect of the adsorbent dosage on the adsorption performance, 3ml of

fatty acid solution will be added with different amounts of CS adsorbent dosage, ie: 0.2,

0.4, 0.6, 0.8, and 1 g/L into a 50 ml conical flask. The sample will be placed in the

shaker, and it will be shaken for 180 rpm at 50 °C for 1 hour. At the end of the

experiment, the mixture will be filtered to separate the spent adsorbent and the

remaining solution to observe the amount of FFA remain in the solution after the

adsorption occurs. The amount of the FFA that remains in the solution can be

determined by using titration method. In the titration step, 10 ml of supernatant will be

pipetted in 10 ml of neutralized isoocatene, and the mixture will then be titrated with

0.05 M NaOH and phenolphthalein as indicators until the color of the mixture changes

from colorless to pale pink for at least 30 seconds.

3.8.2 FFA concentration

For the effect of FFA concentration on the adsorption performance, 3ml of

fatty acid solution with different concentrations, ie: 1, 2, 3, 4, and 5 mmol/L, will be

prepared with 0.6 g/L of CS adsorbent dosage into a 50 ml conical flask. The sample

will be placed in the shaker, and it will be shaken for 180 rpm at the mean temperature

which is 40 °C for 1 hour. After stirring is done, the mixture will be filtered to separate

the adsorbent and remaining solution. The FFA remaining in the solution will be

determine by using titration method, where 10 ml of supernatant will be pipetted in 10

ml of neutralized isoocatene, and the mixture will then be titrated with 0.05 M NaOH

51
and phenolphthalein as indicators until the color of the mixture changes from colorless

to pale pink for at least 30 seconds.

3.8.3 Adsorption temperature

For the effect of the adsorption temperature on the adsorption performance,

20ml of fatty acid solution will be added with 0.6 g/L of CS adsorbent dosage into a 50

ml conical flask. The sample will be placed in the shaker. The shaker will be set with

different temperature, ie: 30, 40, and 50 degrees Celcius. The speed and time of the

shaker will be remained constant at 180 rpm in 1 hour. After 1 hour, the mixture will be

filtered to separate the adsorbent and remaining solution. The FFA remaining in the

solution will be determine by using titration method, where 10 ml of supernatant will be

pipetted in 10 ml of neutralized isoocatene, and the mixture will then be titrated with

0.05 M NaOH and phenolphthalein as indicators until the color of the mixture changes

from colorless to pale pink for at least 30 seconds.

52
 CHAPTER 4: EXPECTED RESULT

The first objective of this study is to synthesize and investigate the material

characterization of the calcium silicates derived from HCl pre-treated rice husk ash

(RHA) of different concentrations of calcium hydroxide. The HCl pre-treated on the

RHA is expected can remove all the impurities and lead to the higher silica content of

the RHA after the calcination. The precipitation of sodium silicate derived from HCl

pre-treated with different concentrations of calcium hydroxide solution is expected to

produce the highly porous structure of the calcium silicates and can have excellent

performance in the FFA molecules adsorption.

For the characterization of the calcium silicate, from the FTIR analysis, the

presence of the silicate and adsorbed water from all of the synthesized calcium silicate

is expected. In the high-wavenumber region (4000 cm−1 to 3000 cm−1), the one wide

band with a vigorous intensity at 3445 cm−1, associated with the stretching vibration

mode of O–H for water molecules, is expected to be found. In the low-wavenumber

region (1500 cm−1 to 400 cm−1), the bands at 970, 870, and 652 cm−1 that attributed

to the symmetric stretching vibration and the bending vibration of Si-O groups are

expected to be found. The band at 455 cm-1 is attributed to the stretching vibration

mode of the Si-O group. The bands at 970 and 870 cm−1, similar to the characteristic

peaks of silicon tetrahedral with Q1 and Q2 Si sites, are expected to be found.

Meanwhile, in the SEM analysis, the porous honeycomb-like structure is likely

to produce many open pores, which will have a diameter of approximately 30- 100 nm

distributed on the surface. In the EDS analysis, silicon, oxygen, and calcium are

53
expected to be found with silicon to show the highest composition compared to oxygen

and calcium. In addition, as the calcium silicate will be derived from the high purity

RHA, it will be expected that calcium silicate adsorbents will maintain in the

amorphous phase.

Then, the second objective is to compare and differentiate the free fatty acid

(FFA) adsorption capacities and removal percentages using the convectional HCl pre-

treated RHA and the derived calcium silicate. Calcium silicate produces with 1.5 M

calcium hydroxide (CS-1.5) is expected to show the highest free fatty acid (FFA)

adsorption capacities and removal percentages compared to other calcium silicate

adsorbents used in this study. It is also expected that CS-1.5 will show higher free fatty

acid (FFA) adsorption capacities and removal percentages compare to convectional HCl

pre-treated RHA.

For the characterization of the calcium silicate, from the FTIR analysis, the

presence of the silicate and adsorbed water from all of the synthesized calcium silicate

is expected. In the high-wavenumber region (4000 cm −1 to 3000 cm−1), the one wide

band with solid intensity at 3445 cm −1, associated with the stretching vibration mode of

O–H for water molecules, is expected to be found. In the low-wavenumber region

(1500 cm−1 to 400 cm−1), the bands at 970, 870, and 652 cm −1 that attributed to the

symmetric stretching vibration and the bending vibration of Si-O groups are expected to

be found. The band at 455 cm -1 is attributed to the stretching vibration mode of the Si-O

group. The bands at 970 and 870 cm −1, similar to the characteristic peaks of silicon

tetrahedral with Q1 and Q2 Si sites, are expected to be found.

54
 Meanwhile, in the SEM analysis, the porous honeycomb-like structure is

expected to produce many open pores, which will have a diameter of approximately 30-

100 nm distributed on the surface. In the EDS analysis, silicon, oxygen, and calcium are

expected to be found with silicon to show the highest composition compared to oxygen

and calcium. In addition, as the calcium silicate will be derived from the high purity and

amorphous silica-rich RHA, it will be expected that calcium silicate adsorbents will

maintain in the amorphous phase.

The third objective is to evaluate the effect of significant parameters affecting

the FFA adsorption capacity and removal percentage on the best-performing adsorbent.

For the first parameter, which is adsorbent dosage, it is expected that at the highest

amount of adsorbent dosage, calcium silicate will show the highest adsorption

capacities since the higher amount of adsorbent dosage will provide more adsorption

sites. The second parameter is FFA concentration. It is expected that the adsorption

capacities of calcium silicate will be reduced as the FFA concentration increase due to

the lack of an adsorption site to adsorb the FFA molecules. The last parameter is

adsorption temperatures. Since calcium silicate will adsorb the FFA molecules through

the chemisorption, it is expected that the FFA adsorption capacities and removal

percentages by calcium silicate will increase as the temperature increase.

55
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 APPENDIX A
SAMPLE APPENDIX 1

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 APPENDIX B
SAMPLE APPENDIX 2

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