Literature Review

Clean water is an essential necessity not only for humans alone, but also every other organism
in our vast ecosystem. Our Earth has an abundant supply of freshwater, but its quality has
deteriorated rapidly over the past several decades. Human activities such as deforestation,
industrialisation, urbanisation, excessive burning of fossil fuels and accidents have all
contributed to this cause. Clean water in a holistic view not only refers to clean supply of water
for daily activities such as cooking, washing, consumption or cleaning. It also means that water-
related ecosystems must be protected and preserved to avoid any forms of pollution, which
could endanger the organisms and eventually lead to extinction.

Oil spills are one of the major reasons behind water pollution in oceans, rivers or lakes.
Unfortunately, oil spills are a rather common occurrence globally. Every year, an estimated 5
million tonnes of oil is being transported all around the globe through marine routes, placing
the ocean and its residents in serious threat (Majeed, Adebayo & Hossain, 2012). The shocking
Deepwater Horizon oil spill in 2010 has raised consciousness all around the world regarding
oil spill clean-up technologies after witnessing the detrimental effects it has brought onto the
environment and its ecosystem, which regrettably still lingers until today (Chen, Ye, Zhang,
Jing & Lee, 2019). Clean and fresh water is vital for the survival and reproduction of aquatic
ecosystems. Therefore, various techniques and methods have been applied to clean up oil on
ocean water surfaces in the event of an oil spills. Among these methods are booms, skimmers,
in-situ burning or biodegradation of oil using microorganisms (Majeed et al., 2012). These
methods have proven to be useful, but they do not fare well in terms of economics and overall
sustainability.

Sorbents are also one of the methods employed to recover oil from oil spills. Sorbents are
materials that have a high affinity for oil and tend to repel water or also known as
hydrophobicity. (Anuzyte & Vaisis, 2018). Natural sorbents derived from agricultural wastes
like coconut coir, rice husks, banana pith, sugarcane and kapok fibres have lately been
receiving a lot of attention as one the of the viable options to recover oil spills. They are easily
obtainable, cheap, biodegradable and safe to deal with. Abdelwahab, Nasr and Thabet (2017)
have used chemically-treated palm oil fibre as a natural sorbent to adsorb different types of oil
such as used diesel, crude oil and vegetable oil in their studies. The palm fibre sorbents have
exhibited decent oil sorption capacities with simple treatment methods like alkali treatment.
Rice husks are example of agricultural wastes which are abundantly found in Malaysia, a rice-
producing country. Rice husks are hard, protective coverings of rice grains which are separated
from the grains during milling process and contain about 30-50 percent of carbon (Singh, 2018).
Rice husks ash is used in the manufacturing of bricks (Phonphuak and Chindaprasirt, 2015).
According to Singh, about 20% of the weight of rice comes from its husk. Rice husks has the
following composition, cellulose (50%), lignin (25%–30%), silica (15%–20%), and moisture
(10%–15%). It also has a relatively low bulk density which is reported to be 90-150 kg/m3.

Rice husks falls under the category of lignocellulose. Lignocellulose materials are known to
have high oil adsorption capacity, cost-effective, biodegradable and easily acquired (Yusof et
al., 2015). However, rice husks also tend to adsorb water which could make them sink in water.
Rice husks are able to absorb water from 5% to 16% of per unit weight (Mansaray & Ghaly,
1998). Therefore, mechanical or chemical modification methods may be required to resolve
this problem to make the product more effective in real-life use.
Theory

For our organic oil sorbent, it functions based on the theory of bulk absorption. When the
prototype is immersed in an oil-water mixture, the mercerized rice husks will then absorb the
oil until it is fully saturated. The saturated rice husks will then be squeezed to remove the
absorbed oil. Absorption of oil can be defined as the distribution of adsorbate (oil) through out
the body of the sorbent, which is the said mercerized rice husks (Bayat, Aghamiri & Vakili-
Nezhaad, 2005). It is important to note that absorption of oil is a function of bulk mass, not to
be confused with adsorption where it relies on the surface area of adsorbent. Therefore, it is
integral that we select an optimal design for our prototype to store as much sorbent material as
possible.

Mercerization treatment was chosen to increase the performance of the rice husks to absorb oil.
Mercerization refers to the alkalization of plant fibres with sodium hydroxide (NaOH) solution,
usually at a high concentration (Wong, McGowan, Bajwa & Bajwa, 2016). Plant fibres have
high number of free hydroxyl ions that can bond easily with water and oil. A good oil sorbent
should be oleophilic, which means that it favours oil and repels water. Hence, mercerization
should be able to increase the sorbent’s affinity for oil. The chemical equation of mercerization
treatment is attached as follows,

Fibre treatment methods like mercerization are able to modify the fibre surface, composition,
structure, dimension, morphology and mechanical properties (Wong et.al, 2016). Moreover,
NaOH treatment can wash away natural fats, waxes and even hemicellulose naturally found in
raw rice husks (Barzagan, Tan, Hui & McKay, 2013). According to Wong et.al, mercerization
of fibre increases it surface roughness, and in turn increases its surface area. This is good for
the absorption of the fibre as it increases the number of attachment sites.
Methodology

This chapter showcases the system of methods used in our project to achieve our goal of
completing our project.

6.1 Project Workflow

The figure below demonstrates the logic sequences of tasks in completing our project
6.2 Tools and software

Throughout our project, we have utilized several types of tools and softwares to facilitate us in
fabricating our prototype and then carry out testing on it. The machines, tools and softwares
will be detailed below.

6.2.1 Machine and tools for fabrication of prototype

No. Machine/tools Description

1. Drying oven To dry the processed coconut coir
fibre until its weight is constant
2. Conical flask To store the coconut coir fibre during
chemical treatment
3. Volumetric flask To prepare of chemical solutions of
different concentrations
4. Mechanical grinder To grind the fibres into fine granules
for increased surface area
5. Water bath machine To heat coir fibre during chemical
treatment
6. Electronic balance To measure the required amount of
chemicals and coir fibre

6.2.2 Machine and tools for testing of prototype

No. Machine/tools Description

1. Electronic balance To measure the weight of sorbent
before and after immersion in oil-
water mixture
2. Beakers To store water-oil mixture
3. Fourier Transform Infra-Red machine To identify functional groups present
in the sorbent

6.2.3 Software used in designing and documentation of prototype

No. Software Description

1. CATIA V5 To produce technical drawings of the
prototype
2. Microsoft Office Used for documentation of project
such as extended proposal, progress
reports and final report
3. Adobe Illustrator To design posters, presentation slides
and infographics
4. Adobe Premier Pro To edit and render videos for
presentation
Results and Discussion

In our initial stages of testing, we had purchased three different types of natural fibres which
are coconut coir fibre, rice husks and palm oil fibre. We then carried out the mercerization
treatment with 1M NaOH solution for these fibres and later performed an oil sorption capacity
test on all of them. The results of the test are presented below.

Oil Sorption Test for coconut coir, rice husks and oil
palm fibre
14
Oil sorption capacity (g of oil/ g of fibre)

9.03
12
8.86
10
7.71
8
6
4
2
0
Coconut coir Rice Husks Oil Palm Fibre
Types of fibre

Figure 1.1: Oil sorption test results for coir fibre, rice husks and oil palm fibre

Rice husks had the best oil sorption capacity performance at 10.23 g/g, which is then followed
by coconut coir at 8.86 g/g. Oil palm fibre had the lowest sorption capacity at 7.71 g/g.
Therefore, rice husks were ultimately selected as our oil sorbent material.
 Figure 1.2: Oil sorption capacity of rice husks under different concentrations of NaOH

Various concentrations of NaOH solution were used to treat the rice husks as shown in Figure
1.2. From our observation, the oil sorption capacity seemed to increase as the molarity of
sodium hydroxide used increases. We have tested several concentrations from 1M to 6M. The
values obtained from our tests are compared to the control unit which are the raw rice husks.
The oil sorption value for the rice husks exhibited an upward trend as the concentration
increases from 1M to 4M. Beyond 4M, oil sorption performance did not see any significant
improvement. Therefore, we have chosen to use 4M concentration of NaOH solution to treat
our rice husks.

Oil uptake vs Reaction temperature

12 11.68
11.5
Oil uotake capacity, g/g

11

10.5 10.3

10 9.74

9.5

8.5
25oC 90oC 100oC
Reaction temperature (Celcius)

Figure 1.3: Oil uptake versus different reaction temperatures

We have decided to test several temperatures for the mercerization treatment for our rice husks.
Based on literature review, we learned from some sources that mercerization for natural fibres
were either carried out at room temperature (25oC) or 90oC. Therefore, we have decided to use
these three different temperatures for our treatment. All of these three runs were carried out for
24 hours and with 4M concentration of NaOH solutions. From Figure 1.3, it can be observed
that mercerization at room temperature (25 oC) produced the lowest oil uptake capacity at 9.74
g/g and the second best is 10.3 g/g when done at 90oC. The best results were obtained when
the rice husks were treated at 100oC, yielding a value of 11.68 g/g.
As the reaction temperature increases, the greater the break down of the structure of the rice
husks. More extensive break downs also mean that the final yield of rice husks decreases. This
results in a lower bulk density, which can increase the oil sorption capacity.

Overall, rice husks are agricultural wastes which have a relatively high lignin content. Lignin
is responsible for the structural integrity, rigidity and resistance towards swelling of rice husks.
Alkali treatment is therefore crucial for the delignification process to take place, because it
helps to improve the degree of rice husks break down. According to Barzagan et.al (2013),
lignin can easily form hydrogen bonds with water. Therefore, this would affect the sorbent’s
ability to absorb oil. In this case, mercerization is crucial to break down lignin so that it will
not form any hydrogen bonds when the rice husks are immersed in an oil-water mixture.

The samples of mercerized rice husks were also sent for FTIR analysis at the Central Analytical
Laboratory. The results of the FTIR spectra of the raw and treated rice husks are presented
below.

100

99

98

97

96
%T

3337.98cm-1

95

94

93
1020.35cm-1

92
4000 3500 3000 2500 2000 1500 1000 550
cm-1

Figure 1.4: FTIR spectrum for raw rice husks

 100

98

96
3333.17cm-1
94

92

90 792.32cm-1
%T

88

86

84

82

80
1032.54cm-1
78
77
4000 3500 3000 2500 2000 1500 1000 550
cm-1

Figure 1.5: FTIR spectrum for mercerized rice husks

Referring to Figure 1.4, there is a major sharp peak observed at the wavenumber of 3337 cm-
1
. This indicates that there is strong hydrogen bonding from O-H bonds which are present in
the raw rice husks sample. This finding corresponds to several other literature sources which
also suggested that lignocellulose fibres like rice husks contain O-H bonds by nature. Another
sharp peak in the FTIR spectra of raw rice husks is found at wavenumber of 1020.5 cm-1. This
is most possibly due to Si-O stretching (He, Ikeda-Ohno, Boland & Waite, 2013). Untreated
rice husks contain high amounts of silica which is proven from the sharp peak detected. After
treatment with NaOH, silica in raw rice husks is leached away as sodium silicate (Barzagan
et.al, 2013).

As for the treated rice husks from Figure 1.5, a minor and broad peak was detected at a
wavenumber of 3333.61 cm-1. It can be inferred that only free hydroxyl groups are detected in
the treated sample and not O-H bonds. These free hydroxyl groups could be due to some minor
residual sodium hydroxide solution which were not washed away after the treatment. With no
O-H bonds detected, the hydrophobicity of the mercerized rice husks is expected to increase
significantly in relative to the untreated batch. Another peak which was not present in Figure
1.4 is detected at 792.32 cm-1 is due to the presence of Si-H bonds (Shen, Zhang & Zhu, 2008).

The sample calculations for our oil sorption test are presented below for reference.

Sample 1 (4M concentration, 100oC treatment)

Mass of dry husks = 0.7g
Mass of dry husk + net (initial) = 4.6 g
Mass of dry husk + net (final) = 12.9 g
 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 ℎ𝑢𝑠𝑘 + 𝑛𝑒𝑡 (𝑓𝑖𝑛𝑎𝑙) – 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 ℎ𝑢𝑠𝑘 + 𝑛𝑒𝑡 (𝑖𝑛𝑖𝑡𝑖𝑎𝑙)
Sorption capacity = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 ℎ𝑢𝑠𝑘𝑠

12.9 𝑔−4.6 𝑔
=
0.7 𝑔

= 11.68 g/g

Sample 2 (Untreated rice husks)

Mass of dry husks = 1.6g
Mass of dry husk + net (initial) = 5.1 g
Mass of dry husk + net (final) = 10.9 g
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 ℎ𝑢𝑠𝑘 + 𝑛𝑒𝑡 (𝑓𝑖𝑛𝑎𝑙) – 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 ℎ𝑢𝑠𝑘 + 𝑛𝑒𝑡 (𝑖𝑛𝑖𝑡𝑖𝑎𝑙)
Sorption capacity = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 ℎ𝑢𝑠𝑘𝑠

10.9 𝑔−5.1 𝑔
=
1.6 𝑔

= 3.63 g/g
From the results above, it is clearly evident that the oil sorption performance of rice husks has
increased tremendously after mercerization. The raw rice husks’ oil uptake was 3.63 g/g while
the sorption capacity of treated rice husks increased to 11.68 g/g. In summary, mercerization
which is a cheap and simple process has successfully converted rice husks with very little
commercial value into an eco-friendly and effective oil sorbent which could prove to be useful
in handling oil spills.
Recommendation

Despite our product has been proven to have increased oil sorption performance, there are still
several recommendations to be made in order to add more value to it. Firstly, we recommend
that other chemical processes like acetylation, esterification or pyrolysis can be carried out.
These processes require facilities which can be hard to find in our lab. Moreover, they also
require chemicals which are hard to acquire or exceed our budget. Given unlimited budget, we
would like to study new methods of treating the rice husks so that it can achieve comparable,
if not better results than synthetic polypropylene sorbents in the market today.

Next, we would also recommend that this product be considered for mass production in the
industry. Mercerization of rice husks is cheap, simple, effective and relatively safe. The cost of
producing alkali-treated rice husks is also low as it does not require high temperature or
pressure albeit being time-consuming. However, we believe the pros still outweigh the cons.
Therefore, this process has a huge potential to be expanded to a larger scale of production.

Lastly, we would also recommend that the used rice husks which are saturated with oil can be
used as biofuel or a source for silica. Rice husks saturated with oil have a high calorific content,
making it a decent choice as a source of fuel. In this case, rice husks have an advantage over
polypropylene sorbents which cannot be repurposed after it is spent. The liquid solution which
is normally discarded after the treatment of rice husks contains leached sodium silicate. This is
because raw rice husks have a high content of silica naturally. Therefore, further studies could
be done by us to extract silica from it which is a valuable compound for many sectors, the
semiconductor industry in particular.
 References (new sources)

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Sea Water by Sorbent Materials. Chemical Engineering & Technology,28(12), 1525-1528.

doi:10.1002/ceat.200407083

Bazargan, A., Tan, J., Hui, C. W., & Mckay, G. (2014). Utilization of rice husks for the

production of oil sorbent materials. Cellulose,21(3), 1679-1688. doi:10.1007/s10570-014-

0203-9

He, D., Ikeda-Ohno, A., Boland, D. D., & Waite, T. D. (2013). Synthesis and Characterization of

Antibacterial Silver Nanoparticle-Impregnated Rice Husks and Rice Husk

Ash. Environmental Science & Technology,47(10), 5276-5284. doi:10.1021/es303890y

Mansaray, K. G., & Ghaly, A. E. (1998). Thermogravimetric Analysis of Rice Husks in an Air

Atmosphere. Energy Sources,20(7), 653-663. doi:10.1080/00908319808970084

Shen, Q., Zhang, T., & Zhu, M. (2008). A comparison of the surface properties of lignin and

sulfonated lignins by FTIR spectroscopy and wicking technique. Colloids and Surfaces A:

Physicochemical and Engineering Aspects,320(1-3), 57-60.

doi:10.1016/j.colsurfa.2008.01.012

Singh, B. (2018). Rice husk ash. Waste and Supplementary Cementitious Materials in

Concrete,417-460. doi:10.1016/b978-0-08-102156-9.00013-4

Wong, C., Mcgowan, T., Bajwa, S. G., & Bajwa, D. S. (2016). Impact of Fiber Treatment on the

Oil Absorption Characteristics of Plant Fibers. BioResources,11(3).

doi:10.15376/biores.11.3.6452-6463