EXRTRACTION AND

CHARACTERIZATION OF NANO

BASED SILICON-OXIDE FROM

RICE HUSK

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 1 INTRODUCTION

1.1 Background of Study

According to Statista (2022) approximately 510 million tons of rice paddies is produced each

year with Nigeria accounting for over 2 million tons of produced rice annually. Rice husk

(RH) an agro-waste described as a natural sheath that form and cover the grains of rice. The

husk is formed from hard materials including opaline, silica, lignin, cellulose, and hemi

celluloses which are referred as lignocelluloses. Rice husk is a by-product of rice production

with about 20-25% weight of rice being contributed by rice husk (Balamurugan et al., 2012).

In Nigeria, little to no interest or attention has been given to the proper utilization and

application of agricultural waste. As a result, agricultural waste such as Rice husk end up as

refuse piles and heaps in disposed areas thereby constituting an environmental nuisance. An

example is the dispersal of these rice husks by wind to contaminate the environment

especially during the dry season (Harmattan).

Although Rice husk may regarded as agricultural waste, the burning of rice husk generates

rice husk ash which is rich in silica and can be an economically valuable raw material for

production of natural silica. The presence of hydrated amorphous silica in rice husk makes

rice husk a commodity of extreme industrial importance (Olawale et al., 2012).

Rice husk when burnt at low temperature below 700oC produces amorphous silica, while

crystalline silica is produced at temperatures above 700oC. Rice husk ash is a major source of

silicon dioxide. The ashes contain about 80% to 95% silicon dioxide and have low thermal

conductivity and low mechanical properties. The ashes are also resistant to chemical etching

and have high melting point of 1440oC. Crystallization in rice husk ash begins at temperature
above 500oC; below this temperature rice husk ash is purely amorphous. The chemical

properties of rice husk ash vary from one region to another. This variation is due to the

condition under which rice is grown. These conditions include climate, soil, paddy (rice)

variety and use of fertilizers (Onojah, 2013)

The use of silicone fertilizers in the field of agriculture that is environmentally friendly can

be done by utilizing natural silicon obtained from rice hull ash from the residual of brick

combustion [4]. Rice hull ash not only contain SiO2 of 87-97% but it also 1% N and 2% K

nutrients [5]. In general, the distribution of silicone fertilizers can improve plant

physiological functions and increase plant resistance to pests, diseases [6]. Distribution of

rice hull ash with its silicone content significantly affects the growth rate of tomato plant and

suppresses pests and diseases [7]. Fulfillment of plant needs for Si nutrients will improve the

plant's natural protection system against diseases, insects and bad weather conditions [8].

Sufficient Si supply to cerealia provides good harvest because the addition of Si can increase

strength and resilience of the cell, thus the use of silica fertilizers derived from rice hull ash

can make the plant resistance from pest problem [10].

1.2 Problem Statement

Rice husk and rice husk ash (RHA) are known sources of considerable levels of high quality

silica, which has several industrial applications (Ugheoke et al., 2013). However, the

extraction of silica at industrial level consists of several mechanical, physical, chemical, and

energy-intensive thermal processes carried out at elevated temperatures and in the presence of

large amounts of acids, generating significant volumes of effluents (Haus et al., 2012). In this

sense, Ma et al.3 highlight the fact that the conventional silica production method is based on

the reaction between sodium carbonate and quartz at high temperatures. After sodium silicate

is formed, silica is precipitated in a reaction with sulfuric acid. But this method also
consumes high levels of energy and produces large amounts of liquid effluents and

greenhouse gases.

There are various methods to prepare silica nanoparticles. Adam et al. [20] synthesized

spherical nanosilica from agricultural biomass as RH via the sol–gel method. The resulting

silica particles were shown to be agglomerates with an average dimension of 15 to 91 nm. Jal

et al. [21] synthesized nanosilica via the precipitation method, and the resulting nanosilica

were found to have a particle size of 50 nm in dimension. However, the sol–gel technique

[19,21-23] is the most common method for silica synthesis. It involves simultaneous

hydrolysis and condensation reaction. In this process, a sol of sodium silicate or silicon

alkoxide or halide gets converted into a polymeric network of gel. During silica synthesis by

sol–gel process under certain conditions like restriction of gel growth, silica gets precipitated.

In such preparation, the steps involved are coagulation and precipitation from silica solution.

In the present investigation, we have focused our effort on preparing stable nanosilica from

sodium silicate which was synthesized from Vietnamese rice husk using the sol–gel

technique.

1.3 Aim and Objectives

This study aims to extract silica and prepare nano-silica particles from rice husk ash.

The objectives are to:

1. To prepare rice husk ash from rice husk

2. To extract silica from processed rice husk ash

3. To extract nano-silica from rice husk ash

1.4 Scope of Study

The scope of this research covers the modelling of temperature and pressure hydrate

formation parameters from a deep water offshore field to develop a hydrate formation

predictive model capable of identifying hydrate formation conditions before they pose a

threat. The study would also develop a software package that can be integrated into a

computer system for real life applications.

1.5 Significance of Research

This study would provide insight and vital information on the application of AI and big data

analysis for real-time well surveillance and its application in preventing Hydrate formation

This study also hopes to create and implement an integrated and intelligent system capable of

analyzing the big data, detecting and reporting anomalies and take action in time to prevent

any inherent hydrate formation problems that may arise.

 2 LITERATURE REVIEW

2.1 Rice Husk

Rice husk (RH) is a by-product of rice production which contributes about 20-25 wt % of the

total dry weight of paddy rice. (Cabane et al., 2012; Yu et al., 2009; Chang et al., 2002)

According to Statista (2022) approximately 510 million tons of rice paddies is produced each

year with Nigeria accounting for over 2 million tons of produced rice annually. The

utilization of RH has been limited because of their tough and abrasive nature, low nutritive

value, and low bulk density (Efremova, 2012; Fang et al., 2004; Houston, 1972) Most times

rice husk are usually disposed through disposal approaches such as open field burning, which

results in waste of energy, air pollution, and greenhouse gas emission (Lim et al., 2012)

The main components in RH are lignin, cellulose, and hemicellulose, which are generally

named lignocellulose. RH also contains ca. 15 to 28 wt % of silica. (Martin 1938; Chiew and

Cheong, 2011; Chen et al., 2013) The high content of silica in RH presents opportunities for

the preparation of value-added silicon based materials. Since the 1970s, various silicon based

materials, including silica, silicon carbide, silicon nitride, silicon tetrachloride, zeolite, and

silicates, have been successfully synthesized using RH as the silicon source. (Sun and Gong,

2001) However, this field of research has been significantly advanced and expanded in the

past decade spurred by the global attention on sustainable and renewable resources. A review

of the advancement in the synthesis of silicon based materials from RH biomass in the past

ten years is necessary to define future prospects of this field.

2.2 Structure and Components of Rice Husk (RH)

It was not until 1938 that the existence of silica in RH was discovered (Martin 1938) and are

known to be used by plants for protection and also to improve drought tolerance and disease

resistance. (Suraporniboon et al., 2008) Rice plants absorb silica in the form of soluble silicic

acid, Si(OH)4, which enters the root of rice from the surrounding soil. Little is known about

the mechanism that allows for high silicon uptake. After silicic acid is absorbed, it is

transported to the stelai, sheaths, and leaves of the rice plant. (Bryant et al., 2011) Through

evaporation and polymerization, Si(OH)4 becomes concentrated into SiO2nH2O. This

prompts the formation of cellulose/silica composite membrane. It is commonly believed that

some of the silica in RH is bonded to organic compounds but so far few details are available.

(Zemnukhova and Nikolenko, 2011; Chen et al., 20121) Characterization of RH, including X-

ray diffraction, infrared spectroscopy, thermal analysis, and scanning electron microscopy,

reveal that the highest concentration of silica is found on unbroken dome-like protrusions of

the outer epidermis layer. (Park et al., 2003) High concentrations of silica in RH can also be

found on hairs called trichomes on both the inner and outer epidermis and in-between

epidermal cells. (Shim and Kwon, 2012) However, the content of silica in RH dependents on

climate, soil composition, and rice variety.

2.3 Silica

Silica plays an important role as ingredients in food, pesticides, and personal care products;

as fillers in plastics, rubbers, and coatings; and as starting materials for semiconductors,

silicates, and ceramics. (Glasser, 1986; Uhrlandt, 2006) Recently, silica has also been

explored for biomedical applications. (Slowing et al., 2007) The application and value of

silica are highly depending on its crystallinity and micro-structure. Crystalline silica is the

most abundant material in the earth’s crust, but its application is limited mainly owing to its
low reactivity. (Glasser, 1986; Uhrlandt, 2006) Amorphous silica with high surface area is

important to many key chemical applications, including absorbents, thermal insulators, and

catalyst supports. (Gurav et al., 2010) High quality amorphous silica is mainly produced

through a multi-step process starting from the carbon thermal reduction of raw natural silica,

sand. The process is associated with high temperature, high pressure, and strong acidity,

which is energy intensive and eco-hazardous. (Rosch et al., 2000) To minimize the above

issues, and meet the extensive and increasing demand on silica for widespread applications, it

is necessary to seek an economical, eco-friendly, and sustainable approach to prepare high

quality silica.

2.3.1 Sources of Silica

Silica can be synthesized chemically from synthetic materials or obtained from natural

sources. Tetra-ethyl-ortho-silicate (TEOS), whose chemical structure is given in Figure 1.2, is

the most commercially used chemical in silica production. The reason of being used of this

material is the high size control of the final product and being easy of production. In addition,

silanes are used both in production and surface functionalization of silica (Murray et al.,

2010).

Figure 1.2 Chemical structure of TEOS (Acros organics)

In the past, studies on the production of silica from agricultural waste have used more than

one method (Adam et al., 2011; Bergna and Roberts, 2006; Jal et al., 2004). Bark of the

plants and the agricultural wastes such as rice husk (RH), sugar cane and peanut shells have

become cheap raw material used in silica production. RH contains %71-87 by mass of

organic structures such as cellulose and lignin and %13-29 by mass of inorganic elements

(Okutani et al., 2009). That is why it is most preferred natural source in silica production.

2.3.2 Application Fields of Silica

Silica particles in various sizes have many uses. These uses can be customized as catalyst,

drug delivery, dental applications, tissue engineering, gene therapy and molecular imaging by

reducing the silica particle size to Nano level (An et al., 2010; Chen et al., 2017; Gutowska et

al., 2001; Liou and Yang. 2011; Yener and Helvacı, 2015; Zulkifli et al., 2013). The Nano

silica to be produced from rice husk ash (RHA) is thought to be very useful in some

application areas. It can be seen in the literature that the production of Nano-silica, which is

necessary for the production of biomaterials in biological application field, from rice husk ash

is so little (Chen et al., 2017). The Nano-sized silica granules that will be extracted from rice

husk by appropriate method are thought to solve the environmental and economic problems

that arise when the old production methods are applied (Tolba et al., 2015).

2.4 Synthesis of Silicon from Rice Husk Ash

Rice husk is a waste by-product of the rice milling industry. It constitutes about 20% the

weight of a harvested rice paddy and the mineral ash content of the rice husks ranges between

15-30% of which 87-97% is amorphous silica depending on the combustion technique and

conditions employed [4], [6],[21], [22] The rice plant has high amorphous silica content

because it naturally absorbs from the soil and transports silicon in the form of silicic acid to
its outer surfaces. The silicic acid on reaching the outer surfaces of the rice plant becomes

concentrated due to evaporation and is subsequently polymerized into silica cellulose

membrane [23]. Because of this natural selectivity, the rice plant limits the uptake of heavy

metallic elements that are found in large concentration in other cheap sources of silica such as

quartz, bentonite and diatomaceous earth. A typical proximate analysis of rice husk is shown

in Table 3.1

Table 3. 1 Typical proximate analysis of rice husks[21]

Moisture 6%

Ash 16.92%

Volatiles 51.98%

Fixed Carbon 25.10%

The main industrial uses of rice husk ash (RHA) are as a pozzolan in the cement and concrete

industry and as an insulator in the steel industry. The synthesis of silicon from RHA has to

date remained as a laboratory curiosity. Singh and Dindhaw [23] reported obtaining silicon of

6N (99.9999%) purity by reducing white rice husk ash with magnesium at temperature of 800

o C followed by several successive acid (mixtures of HF, H2SO4 and HCl) leaching

treatments. The reduction was also investigated at temperatures of 850 and 900 o C. The

silica in their rice husk fired beyond 800 oC was observed to have attained some degree of

crystalinity. They also suggested the possibility of obtaining silicon of similar purity by

directly smelting the purified amorphous silica with carbonaceous reductants in electric

furnace followed by leaching with acids and repeating the smelting and leaching for about

nine times. The authors however did not disclose the method used to analyze their silicon to

the 6N purity.
Amick et al. [25] also patented a process for producing rice husk silica with adjusted silica to

carbon ratio for direct reduction into high purity silicon with no addition of carbonaceous

reductants. The method as described by Amick et al. comprise of leaching rice husk in

semiconductor grade hydrochloric acid followed by pyrolysis of the leached husk at 900 o C

in an atmosphere of 1% anhydrous HCl/Ar gas stream for a period of about one hour. The

pyrolyzed rice husk which has a carbon -to -silica ratio of 4:1 is further processed in a

conventional fluid bed combuster with Ar/CO2 atmosphere at a temperature of 950 o C to

obtain stoichiometric carbon -to- silica ratio of 2:1. Reduction of the ash so produced at a

temperature of 1900 o C reportedly yielded silicon with total impurity less than 75 ppm. The

boron and phosphorus content were reported to be less than 10 ppm each.

Subsequently, Hunt et al. [26] investigated the possibility of producing high purity silicon

from rice husk by purifying the rice husk silica according to the method of Amick et al,

followed by pelletizing and reduction in a modified electric arc furnace. The pelletizing was

carried using carbon black as a reductant and sucrose as a binder. The authors concluded that

purified RHA could be a potential silica source for solar grade silicon production.

Bose et al. [22] subjected powdered silicon obtained by magnesium reduction of rice husk

ash at a temperature of 600-650 o C to melting and directional solidification and found that

boron was the active impurity in the polycrystalline silicon ingot obtained. They determined

the minority carrier life time of their polycrystalline silicon material to be of the order of 1-

5µs and concluded that to be promising for photovoltaic applications. A minimum carrier

lifetime requirement for efficient solar cells fabricated from multicrystalline silicon wafers is

however estimated as 25 µs [2].

The magnesium reduction of rice husk ash has also been investigated by Banerjee et al. [27]

and by Ikram and Akther [10]. Banerjee et al reduced acid leached rice husk ash by

intimately mixing the ash with magnesium powder and firing the powdered mixture in a

sealed graphite crucible in a muffle furnace. The reaction product was successively leached in

mineral acids (HCl, H2SO4, and HF) in a Teflon beaker. A spectrochemical analysis of the

final silicon product showed a high boron content of 20-200ppm as well as high magnesium

(50-1000ppm) and aluminum (10-200 ppm). They attributed the contamination of the silicon

to the use of laboratory grade magnesium and also from glassware. In comparison with the

silica produced by Singh and Dhindaw, Barnerjee et al. reported the silica had attained some

degree of crystalinity when produced from roasting of husk at temperatures between 500-600

o C.

Following a similar approach but with 4N purity magnesium, Ikram and Akhter reported

silicon of 99.95% purity with Boron content of approximately 2ppm.The process steps

followed by Ikram and Akhter [10] , comprise boiling rice husk in 1:10 HCl and distilled

water for 15 minutes, burning of the acid treated husk in air to obtain black ash, firing of the

black ash in a muffle furnace to obtain white ash, leaching of the white RHA in dilute HCl ,

reduction of the leached white RHA with magnesium of 4N purity followed by sequential

leaching with HCl, HF and a mixture of HF and H2SO4.

Contrary to the report by Banerjee et al and in agreement with Singh and Dhindaw, these

authors reported that no crystalinity was observed in the RHA produced at 620 o C. Only the

RHA fired to 900 o C had attained significant crystallinity with reflections or sharp peaks of

different phases of SiO2 in their XRD pattern. They concluded that the silicon can be

upgraded to solar grade silicon by conventional refining methods.

Calciothermic reduction of purified rice husk ash was reported by Mishra et al.[28] They

mixed a stoichiometric composition of granular calcium and purified rice husk silica and

subsequently fired the powdered mixture in a sealed sillimanite crucible in a muffle furnace

at temperature of about 720 o C. The reduction product was milled to fine powder and

successively leached with concentrated nitric acid (HNO3) and hydrofluoric (HF) acid to

obtain silicon of 99.9% purity with a boron content of 10 ppm. They suggested that the use of

MgO coated crucibles and high purity reagent can lead to producing solar grade silicon by

this method.
 3 METHODOLOGY

The term rice husk ash (RHA) has been adopted to describe various products after various

thermal treatments of RH. In this study, we define RHA as the product from non-controlled

burning of non-treated RH. RHA contains incompletely burned organic components and a

mixture of crystalline and amorphous silica. The products from controlled calcination of RH

or from treated RH are referred to as RH silica, which typically contains a very low level of

impurities compared to that of RHA.

Riveros and Garza4 discussed the fact that, compared with other silica sources like sand,

bentonite, and diatomaceous earth rice husk has very small amounts of contaminants that

affect performance in applications requiring high purity, as in the manufacture of solar

panels, for instance. Therefore, rice husk is an important source of silica and solar-grade

silicon. Jung et al.5 also claims that rice husk has exclusive nanoporous silica layers, which

have developed throughout years of natural evolution of the plant. This is why producing

highly reactive silica from rice husk is a simple process with several advantages, compared

with conventional production methods6 . High purity is required in several applications of

silica. Silica is a basic raw material widely used in the semiconductors, ceramics, polymers,
and materials industries. This silica is usually produced from quartz fused at high

temperatures, which affords to obtain ultrapure polycrystalline silicon and silicon hydride. In

addition to environmental and economic advantages, low-energy, simpler methods to obtain

pure silica create opportunities for the development of new industrial applications of RHA7
 4 METHODOLOGY

4.1 Preparation of Rice Husk Ash

Rice Husk collection and transportation would be done from Lag-Rice rice mill at Agege,

Lagos state, Nigeria.

Rice husk would be washed thoroughly with water to remove the soluble particles, dust, and

other contaminants present,

It would then be dried in an air oven at about 110°C for 24 hours.

4.2 Acid Treatment

Weighted grams of Rice Husk Ash would be dispersed in HCl 1N in a mixing ratio of 1gram

to 6ml

4.3 Thermal treatment

Samples would be burned inside a programmable furnace at an optimal temperature of 700°C

for 6 hours.

4.4 Silica extraction

1. A sample of 2.5 g RHA would be stirred in a 250 mL, 0.5N sodium hydroxide

solution.

2. The solution would then be heated in a covered beaker by stirring constantly and was

allowed to stand at room temperature then filtered.

Nanosilica preparation

1. HCl would be added until neutralized.

2. The precipitate silica would be washed repeatedly with warm, deionized water and

then centrifuged with speed 5000 rpm within 10mins repeated in 3 times.

3. The product is dried at 110°C for 24 hours in the oven and crystallization in a

programmable furnace at 450oC in 1 hour.

4. Then crushed them to collect nanosilica.