SYNTHESIS OF BIO-SILICA FROM RICE HUSK FOR THE PRODUCTION OF

BIO-CEMENT.

A Process Engineering Project Report

Presented to the

Department of Chemical Engineering

Faculty of Mechanical and Chemical Engineering

College of Engineering

Kwame Nkrumah University of Science and Technology, Kumasi

By

AMO, JOYCE ABENA

ASAMOAH, GILBERT ADU

NYARKO, ELIZABETH

In Partial Fulfillment of the Requirements

for the Course

Process Engineering Project

April, 2021

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 ABSTRACT

The rice milling industry produces rice husk as a by-product . This potential waste is

largely composed of silica, which is a very essential mineral. Silica is often utilized in the

glass and ceramic industries, but it's combined effect in the production of biocement

cannot be understated. The production of bio-cement is thought to be environmentally

friendly. Using rice husk ash as a blend with Portland cement to produce bio-cement is

cost effective and results in a variety of desirable qualities, including chemical resistance

and increased acceptable strength. In this study, amorphous rice husk ash was produced

by combustion of rice husk at 650°C produces. The rice husk was treated with

hydrochloric acid before combustion to eliminate impurities and other alkali metals, as

well as to improve the surfactant content. The rice husk ash yield was calculated to be

19.3%. Characterization of the husk using Fourier Transform Infrared technique indicated

the presence of the siloxane and silanol groups. The biocement was analysed using

Fourier Transform Infrared which indicated the presence of siloxane and silanol

functional group at a wave length of 1075.43 cm-

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 ACKNOWLEDGEMENT

Our profound gratitude goes to the Almighty God who gave us the opportunity,

encouragement, strength and wisdom to accomplish this work. We are most grateful

to our supervisor, Dr. Boakye Patrick, for the comprehensive and constructive

guidance he gave to us towards the accomplishment of this project. We would also

like to express our sincere gratitude to GHACEM, Ghana, for providing us with

clinker and gypsum for this project. Our appreciation also goes to Master, Sintim

Ernest, the laboratory technician for the biotechnology laboratory, Chemical

Engineering laboratory, KNUST who provided a lot of guidance during this project.

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 TABLE OF CONTENTS

ABSTRACT ........................................................................................................................

ACKNOWLEDGEMENT ................................................................................................. i

LIST OF TABLES ............................................................................................................ v

LIST OF FIGURES ......................................................................................................... vi

CHAPTER ONE ............................................................................................................... 1

1.0 INTRODUCTION ................................................................................................. 1

1.1 Main Objective. .................................................................................................. 3

1.2 Specific Objective .............................................................................................. 3

CHAPTER TWO .............................................................................................................. 4

2.0 LITERATURE REVIEW....................................................................................... 4

2.1 Agricultural Biomass .......................................................................................... 4

2.1.1 Chemical composition of Agricultural biomass .......................................... 4

2.1.2 Silica in Plant biomass ................................................................................ 5

2.2 Rice ..................................................................................................................... 7

2.2.1 Rice Husk .................................................................................................... 7

2.3 CEMENT AND BIOCEMENT........................................................................ 11

2.4 RAW MATERIALS ......................................................................................... 16

2.5 SETTING AND HARDENING OF CEMENT ............................................... 17

2.6 POZZOLANIC MATERIALS ......................................................................... 19

2.6.1 RICE HUSK AS A POZZOLANIC MATERIAL .................................... 19

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 2.6.2 CHEMICAL COMPOSITION OF RHA .................................................. 21

2.6.3 PHYSICAL AND CHEMICAL ANALYSIS OF PORTLAND CEMENT

AND RICE HUSK. .................................................................................................. 22

CHAPTER THREE......................................................................................................... 26

3.0 METHODOLOGY............................................................................................... 26

3.1 Raw materials ................................................................................................... 26

3.2 Equipment needed ............................................................................................ 26

3.3 Chemicals Used ................................................................................................ 27

3.4 Moisture Content .............................................................................................. 27

3.5 Acid-Treatment of Rice Husk (Leaching) ........................................................ 28

3.6 Combustion of Rice Husk ................................................................................ 29

3.7 Production of bio-cement ................................................................................. 30

3.8 Flow diagram .................................................................................................... 33

CHAPTER FOUR ........................................................................................................... 34

4.0 RESULTS AND DISCUSSION .......................................................................... 34

4.1 Drying of rice husk ........................................................................................... 34

4.1.1 Moisture Content....................................................................................... 34

4.2 Leaching Of Rice Husk .................................................................................... 35

4.2.1 SEM analysis of rice husk ......................................................................... 36

4.2.2 Characterization of rice husk .................................................................... 38

4.3 Combustion ...................................................................................................... 40

4.4 Proximate analysis on rice husk ....................................................................... 41

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 4.5 FTIR on biocement ........................................................................................... 42

CHAPTER FIVE ............................................................................................................. 45

5.0 CONCLUSION AND RECOMMENDATION ................................................... 45

5.1 Conclusion ........................................................................................................ 45

5.2 Recommendations ............................................................................................ 45

REFERENCES................................................................................................................ 46

APPENDIX ..................................................................................................................... 53

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 LIST OF TABLES

Table I: Strength of bagasse ash-blended concrete ......................................................... 23

Table II: Splitting tensile and Chloride permeability of bagasse ash-blended concrete . 24

Table III. Raw materials and their sources...................................................................... 26

Table IV. Equipment used and their sources .................................................................. 26

Table V Ultimate and proximate analysis of rice husk .................................................. 27

Table VI Results from drying rice husk .......................................................................... 34

Table VIII. The yield of rice husk ash after 4 hours ....................................................... 40

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 LIST OF FIGURES

Figure I. Rice husk ............................................................................................................ 9

Figure II. Rice husk ash .................................................................................................. 11

Figure III a) The drying of rice husk; b) VWR Dry Line Oven ..................................... 28

Figure IV Leaching of Rice Husk ................................................................................... 29

Figure V. Rice Husk before combustion ......................................................................... 30

Figure VI a) Gypsum received b) Clinker received ....................................................... 30

Figure VII. a) the cutting mill b) interior of cutting mill............................................. 31

Figure VIII. After milling a) Clinker b) Gypsum ....................................................... 32

Figure IX: Flow diagram of Methodology. .................................................................... 33

Figure X. Fourier Transform Infrared on rice husk ........................................................ 35

Figure XI Fourier Transform Infrared on Leached rice husk ......................................... 36

Figure XII Morphology of (a) un-leached rice husk; (b) hydrochloric acid-leached rice

husk ................................................................................................................................. 36

Figure XIII Physical and Morphological Characterization for Untreated and HCl Treated

Rice Husk ........................................................................................................................ 38

Figure XIV. a) Rice Husk before drying b) Rice husk after drying ................................ 40

Figure XV: Proximate Analysis of Rice Husk ................................................................ 41

Figure XVI: FTIR on Biocement .................................................................................... 44

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 CHAPTER ONE

1.0 INTRODUCTION

Strong agricultural waste residues are abundant and can cause environmental disposal

issues due to odour production, pest attraction that can damage human health, and so on.

Because of this limitation, its use as a primary source of fuel and additive in the

construction industry has been extensively investigated. The production of Portland

cement is a resource exhausting, energy demanding process that liberates enormous

amounts of the greenhouse gas CO2 into the atmosphere (Sounthararajan, et al., 2013).

The decomposition of limestone and the combustion of fossil fuel in cement production

are the two sources that contribute to the release of CO2 into the atmosphere. The release

of CO2 from limestone in the production process are fairly constant and equate to

approximately 540 kg CO2 per tonne of clinker produced (Jonkers and Carr, 2012). With

increasing industrial activities, rapid growth in human populations, urbanization, and

increasing demand for cement around the world, it is important that solutions are

developed which reduce the undesirable effects of producing cement for construction

without negatively impacting the quality of the cement produced (Torres Agredo, et al.,

2014). The search for alternative cementitious building materials in cement production

has the potential to be a sustainable, cost effective and environmentally friendly solution.

Many kinds of biomass ash obtained from rice husk, sugarcane bagasse, corn cob, wood

waste, bamboo stem, and paper mill can be used as supplementary cementitious materials

(Zhang, et al., 2018). In view of the above mentioned, partial or total substitution of

Portland cement by pozzolanic binders such as sugarcane bagasse ash and rice husk ash

is the way forward.

Among agricultural residues, sugarcane bagasse ash (SCBA) has the highest silica

content. While sugar cane bagasse (SCB) has not yet been extensively studied in Ghana,

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several studies have been conducted on the production of silica gel as an adsorbent,

ceramic raw material, concrete additives, catalyst, cosmetics, paint, and other products

based on its properties. The amount of silica in bagasse varies depending on the

surrounding climate, the quality of the soil, the harvesting time, and the process involved.

Sugarcane, or Saccharum officinarum L., is a perennial grass with stalks, leaves, and

roots. The stalk contains the juice that is widely used to produce sugar. (Norsuraya, et al.,

2016)Ghana sugar cane production was at level of 153,670 tonnes in 2019, up from

152,981 tonnes previous year, this is a change of 0.45%. Typical raw materials in cement

production are limestone or chalk (CaCO3 ), sand (SiO2) , Al2O3 , iron ore (Fe2O3) and

gypsum (CaSO4). The cement industry produces about 5% of the global anthropogenic

carbon dioxide (CO2) emissions. Furthermore, cement's primary materials must be

extracted and processed on a large scale, as well as transported over long distances,

resulting in increased energy consumption, greenhouse gas emissions, and landscape

destruction. Cement is not a sustainable material in terms of its production cycle, from

mining to final disposal, and has a significant environmental impact. Substituting part of

the Portland cement with other cementitious materials such as bio-Silica is one way to

reduce CO2 emissions during cement production. Reactive silica is often used as an

additive in modern cement production to minimize clinker consumption and reduce CO2

emissions and increase cement quality.

The utilization of waste material provides a satisfactory solution to some of the

environmental concerns and problems associated with waste management. When

sugarcane bagasse is burned under controlled conditions, it gives ash having amorphous

silica which has pozzolanic properties (Chouhan, et al., 2019). Raw bagasse ash is

composed of mainly silica (60–75%), CaO, K2O, and other minor oxides including Al2O3,

Fe2O3, and SO3 (Cordeiro, et al., 2008). ASTM C 618 limits the loss on ignition (LOI) of

pozzolanic materials to less than 6% and by controlling the temperature and incineration

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time, LOI values less than 3% could be achieved for SCBA (Sounthararajan, et al., 2013)

(Norsuraya, et al., 2016) (Norsuraya, et al., 2016) (Acharya & Chaudhary, 2012)

(Wyman, et al., 2004). Hence sugarcane bagasse ash is a potential material for cement

production.

1.1 Main Objective.

• To produce rice husk ash for the production of biocement.

1.2 Specific Objective

• To determine the physical properties of the biocement

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 CHAPTER TWO

2.0 LITERATURE REVIEW

2.1 Agricultural Biomass

Agricultural biomass is a wide category of biomass that includes both the food-based and

non-food-based portions of crops (such as corn, sugarcane, and beets) (such as corn

stover; the leaves, stalks and cobs, orchards trimmings and rice husk). They are made up

of organic compounds like cellulose, lignin, and fibre, as well as small quantities of crude

protein, fat, and a variety of minerals like silica, alumina, and iron oxide. (Norsuraya, et

al., 2016). During growth, some plants absorb various minerals and silicates from the soil

and store them in their structures. Annually grown plants have higher proportions of

inorganic materials, especially silicates, than long-lived trees. Rice, sugarcane, wheat,

sunflower, and other plants with high silica concentrations are examples.

2.1.1 Chemical composition of Agricultural biomass

Cellulose, hemicellulose, lignin, water soluble carbohydrates, amino acids and aliphatic

acids, ether and alcohol-soluble constituents (e.g., fats, oils, waxes, resin, and several

pigments), and proteins make up the cell wall of plants. (Acharya & Chaudhary, 2012).

These elements contribute to the growth of plant biomass. Different plant groups have

different proportions of these constituents.

Cellulose, the most abundant polysaccharide on Earth, has a basic chemical composition:

D-glucose residues are connected by 1, 4-glycosidic bonds to form linear polymeric

chains of over 10000 glucose residues. The comprehensive intermolecular bonding

pattern of cellulose produces a crystalline despite its chemical simplicity. Cellulose, the

most abundant polysaccharide on the planet, has the following chemical formula: 1, 4-

glycosidic bonds bind D-glucose residues to form linear polymeric chains with over

10000 glucose residues. Despite its chemical simplicity, cellulose produces a crystallin
4
due to its extensive intermolecular bonding pattern. Lignins account for around a quarter

of all terrestrial biomass. Lignins are amorphous, three-dimensional polymers with a

complex structure. The lignin molecule in plants serves a variety of structural functions,

including acting as a glue between cellulose fibres. (Wyman, et al., 2004).

(Shafiei, et al., 2015). Hemicelluloses have a lower degree of polymerization than

cellulose (around 100-200), making them more vulnerable to chemical attack. They are

alkali soluble and acid hydrolysed easily. (Choi, 2019). Recycling of Agricultural

Biomass

Biomass recycling may be defined as a process of collecting, reprocessing, and recovering

certain biomass materials to produce new items. After collection, materials are segregated

and forwarded to facilities that process them to manufacture new products. Recycling is

the excellent option to resolve solid waste management issues. It transforms materials

into useful raw materials that would otherwise be discarded, resulting in a slew of

environmental, industrial, and social benefits. (Environment Protection 2011). The

environmental advantage of recycling lies in reduced energy consumption, reduced

pollution, conservation of natural resources, and extension of valuable landfill capacity,

which stimulate the development of greener technologies and prevent emissions of many

greenhouse gases and water pollutants. Possible economic benefit of waste prevention

includes reduced waste disposal fees as the waste is not usually disposed free of cost.

Recycling goods, on the other hand, will generate revenue through the sale of recyclable

materials.

2.1.2 Silica in Plant biomass

Silica is the second most abundant mineral in the earth's crust, but despite its abundance,

it is usually synthesized for use in technological applications, and it is one of the most

versatile inorganic chemical compounds. In industry, silica is used as a filler in

5
composites, electrical parts, catalysts, drug delivery systems, thermal insulators, and

rubber. Natural silica especially that found in agricultural waste can be used to substitute

commercial silica precursors as an alternative source. Rice husk, rice straw, corn cob, and

bagasse are examples of agricultural silica sources that have been studied and turned into

more useful items.

Silicon (Si) is found in nature in chemically mixed forms. Soil Si content varies greatly,

ranging from 1 to 45 percent dry weight. (Vázquez-Añón & Jenkins, 2007)ts absorption

by plants is allowed by its existence in the form of silicic acid [Si(OH)4], which

predominates at pH > 9. Silicic acid is present in soils in concentrations ranging from 0

to 6 in most cases. Plants deficient in Si are often structurally weaker and more vulnerable

to growth, development, and reproduction abnormalities, and it is the only nutrient that is

not harmful when collected in abundance. Phytoliths, or silica bodies, are produced when

Si is absorbed into the plant and fill the cell walls and lumina of some plant cells. (Currie

& Perry, 2007). The extent of its interaction with cell-wall components such as

polysaccharides, lignins, and proteins, however, is unknown. The cell-wall environment

is a complex matrix made up of cellulose and more complex polysaccharides including

hemicelluloses and pectin, the latter of which is rich in galacturonic acid residues that are

cross-linked by Ca ions. This environment is rich in biochemical compounds (Currie &

Perry, 2007) and initially (Tans, et al., 1990) proposed three methods of uptake: active,

passive and ejective. Where the concentration is in excess of 100–200 mg kg−1,

polycondensation reactions lead to: polymerization of monomers to form stable nuclei

with critical size; growth of nuclei to form spherical particles; and aggregation of particles

to form branched chains or structural motifs.

The surface negative charge of silica particles increases as they expand to 1–3 nm in size

(as seen in nature), and these particles interact with the local environment, such as the

plant cell wall. The concentration of silicic acid, temperature, pH, and the presence of

6
other ions, small molecules, and polymers all play a role in the process of silica

condensation, but the materials that form are often made up of SiO4 tetrahedra with

variable Si–O–Si bond angles and Si–O bond distances. On a one-nanometer scale, the

materials are amorphous. Silica from different organisms or precipitation conditions can

vary greatly in density, hardness, solubility, viscosity, and composition depending on the

reaction environment in which the mineral forms. (Currie & Perry, 2007)

2.2 Rice

Rice is the seed of the grass species Oryza sativa (Asian rice) or Oryza glaberrima

(African rice). It is a cereal crop. ( (Zheng, et al., 2016)Rice, a monocot, is normally

grown as an annual plant, although in tropical areas it can survive as a perennial. Rice is

produced in all regions of Ghana. This covers all the major ecological zones which

includes the Interior Savannah zone, the High Rain Forest zone, the Semi deciduous, Rain

Forest zone and the Coastal Savannah zone. Within each agro-ecological zone there are

different rice ecosystems. About 30% of Rice Bran produced is used for animal feeding.

The rest of the waste which includes, rice husk, rice bran and rice straw is burnt or left to

rot where milling takes place.

2.2.1 Rice Husk

Rice husk is a by-product of rice milling industry and represented 20% of the weight of

rice. Rice husk, a plant by-product, comprises about one fifth of the 500 Mt of rice

produced annually in the world (Habeeb & Fayyadh, 2009). Rice is cultivated in more

than 75 countries ( (Natarajan, et al., 1998)and over 97% of rice husk are generated in

developing countries ( (Armesto, et al., 2002)). According to United Nations Food and

Agricultural Organisation (FAO, 2008), the annual world rice production for 2007 was

estimated at 649.7 million tons. Rice husk is the outer covering of paddy and accounts for

7
14 – 35 wt%, depending on the variety, with an average of 20 wt% ( (Wamukonya &

Jenkins, 1995)). Almost 70% of the rice husks are not commercially used. According to

international estimates the rice demand by 2022 will grow up to 780 million tons. All

over the world the discharge of the husk accruing in the numerous rice mills causes a

serious environmental problem. This agricultural waste however has a significant

calorific value and a high percentage of amorphous silica. According to (PENG, 2006)

rice husk contains 80 per cent organic volatile materials and remaining 20 per cent silica.

In certain regions, husks are used as fuel for parboiling paddy in the rice mills. Rice husk

is an exceptional biomass. It is the coating on a seed or grain of rice. It is formed from

hard materials, including silica and lignin, to protect the seed during the growing season.

Rice husk is a renewable agricultural waste and a major source of amorphous silica (

(Norsuraya, et al., 2016)Rice husk in its loose form, is mostly used in energy production

such as combustion and gasification (the process of converting rice husk to synthesised

gas (syngas)).

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Figure I. Rice husk

2.3.2 Rice Husk Ash

Burning of rice husk generates rice husk ash (RHA) which is rich in silica and can be an

economically valuable raw material for production of biosilica (Kalapathy, et al., 2000).

The chemical composition of the RHA varies from rice husk to rice husk which may be

due to geographical and climatic conditions, type of rice and the quantity of fertilizer used

in the production cycle ( (Chandrasekhar, et al., 2003)). The physical properties and the

amount of carbon remaining in the ash depends on the combustion performance (i.e.

complete and incomplete combustion), feeding type, temperature, residence time.

Development of a simple low energy chemical method for producing pure silica should

lead to a variety of industrial applications for RHA.

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Amorphous silica from RHA can be extracted using low temperature alkali extraction;

the solubility of amorphous silica is very low at pH<10 and increases sharply pH>10.

This unique solubility behaviour enables silica to be extracted in pure form from RHA by

solubilizing under alkaline conditions and subsequently precipitating at a lower pH. This

low energy method based on alkaline solubilisation of amorphous silica could be more

cost effective compared to the current smelting method. The presence of silica in rice

husk has been discovered as far back as 1938 (Chandrasekhar, et al., 2003) while its

recovery potential had been realised since 1984 (Mansaray & Ghaly, 1997). It is

considered a good source of silica with the potential for large-scale production. Rice husk

contains silica in the range of 20 – 25 wt% as reported by (Real, et al., 1996) (Patel &

Shah, 2018). (1987), (Conradt, et al., 1992) and (Chauhan & Kumar, 2013)). The silica

(SiO2) in rice husk exists in the hydrated amorphous form like silica gel. Burning the

husk under controlled temperatures below 800°C can produce ash with silica mainly in

amorphous form.

However, burning of the ash at temperatures above 800°C produces crystalline silica as

reported by (Qing-ge, et al., 2004). Depending on the combustion technology and process

parameter RHA with a carbon content of 5% - 40 % can be produced. The other

components of the ash are amorphous silica and a small amount of crystalline silica.

Combusted at moderate temperature, the white ash obtained from rice husk contains

approximately 92 – 97 wt% amorphous silica (Lataye, et al., 2008) and (Chakraverty, et

al., 1988) and some number of metallic impurities that can be further removed by a simple

acid-leaching treatment. Other studies reported that rice husk ash contains very high silica

content such as (Sinyoung, et al., 2017) (87 – 97 wt% silica), (Kapur, 1985)(>95 wt%

silica), (Armesto, et al., 2002)) (87.7 wt% SiO2) and (Liou, 2004) (>90 wt% silica). It is

generally believed that in rice husk, silica is predominantly in inorganic linkages, but

10
some of the silica is also bonded covalently to the organic compounds. Characterizations

by Scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), X-ray

diffractometry (XRD) etc., suggest that silica is present all over, but is concentrated 4 on

protuberances and hairs (trichomes) on the outer epidermis, adjacent to the rice kernel

(Sharma, et al., 1984); (Krishnarao & Godkhindi, 1992).

When disposed of, rice husk occupies large areas, where it can self-burn, spreading the

ashes and causing damages to the environment.

It has good flow ability, normally available with 10 percent moisture content and the ash

contains fewer alkaline minerals, thereby it has a high ash sintering temperature. In fact,

it makes an excellent fuel although its calorific value is less than wood and other agro-

Figure II. Rice husk ash

2.3 CEMENT AND BIOCEMENT

A cement is a material which binds together solid bodies (aggregate) by hardening from

a plastic state. This includes organic polymer-based cements. An inorganic cement works

by forming a plastic paste upon the addition of water which sets and then progressively

increase in compressive strength by chemical reaction with the water called hydration. A

hydraulic cement is that which increases in strength even when stored under water after

setting (Bye, 2011)

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In building and civil engineering, due to the predominance of Portland cement, the major

components of which are tri- and di-calcium silicates, it is usually referred to simply as

cement (Bye, 2011). It is an expensive binder due to the high production cost resulting

from the high energy requirements of production process itself since the raw materials

such as limestone and clay are heated in a kiln at 1400-1450°C to form clinker, which is

then ground together with additives such as gypsum to obtain fine particles of Portland

cement. As a result, there has been a continuous rise in the cost of cement whereas natural

reserves of limestone are depleted. It has therefore become imperative to find partial

replacement for raw materials in portland clinker in the form of cheap inorganic materials

with cementitious properties such as natural pozzolans e.g., volcanic tuff ,sand and waste

products from industrial plants e.g., bagasse ash and rice husk ask (Rahman, et al., 2016).

Around 5% of global anthropogenic carbon dioxide (CO2) emissions come from the

cement industry. Cement demand is expected to rise at a rate of 4.7 percent per year,

resulting in increased CO2 emissions. The cement industry emits about 814-935 kg of

CO2 for every 1000 kg of cement produced (Metz, et al., 2007). The chemical

decomposition of limestone accounts for 40-50% of CO2 emissions, and fossil fuel

combustion is responsible for the remaining CO2 emissions (Initiative, 2002 (Van Oss &

Padovani, 2003); (Worrell, et al., 2001). In 2000, global cement production was about

1536.6 million tonnes and the associated CO2 emissions were estimated to be 1578.8 Mt

(Van Oss & Padovani, 2003). Cement plants account for 5% of global emissions of carbon

dioxide, the main cause of global warming (Worrell, et al., 2001). There are three

strategies to reduce CO2 emissions from the cement industry: (1) improve energy

efficiency, thus use less fossil fuel, (2) replace fossil fuel with renewable energy sources

such as biofuel and other biomass feedstocks, and (3) substitute part of Portland cement

with other cementitious materials such as bio-silica (Initiative, 2005). The third option is

what is applicable in this study using RHA and SCBA. Typical raw materials in cement

12
production are limestone or chalk (CaCO3), sand (SiO2), clay (SiO2, Al2O3, and

Fe2O3), iron ore (Fe2O3), and gypsum (CaSO4). Limestone and clay are crushed and

blended in a ratio of about 75% limestone to 15% clay, and pre-heated to drive off water

and decompose the limestone into lime and CO2. The material is then moved to a rotary

kiln, which heats up to 1450°C, fusing the calcium from the limestone with the silicon

from the clay to create calcium silicates (Ca3SiO5 and Ca2SiO4). To monitor setting, the

clinker is cooled, ground, and mixed with 5% gypsum ( (Bye, 2011); (Worrell, et al.,

2001)).

Biocement is one way to reduce CO2 emissions generated during cement production.

Biocement is a mixture of bio-silica and Portland cement made from the combustion of

organic waste. Biocement produces a strong cementing agent with less energy intensive

clinker and associated carbon emissions. Biocement production on a small scale in

tropical areas has shown that blending cement with bio-silica has environmental,

economic, and technical benefits. Reactive silica (amorphous silica with an average

particle size of less than 45 mm) is often used as an additive in modern cement production

to minimize clinker use and increase cement consistency. (Uchikawa, 2000). Successful

examples include fly ash collected from coal-fired power plants and silica fume produced

from silicone industry. Reactive silica can also be produced from combustion of organic

residues. It may also be used as a cement additive if the ash contains enough amorphous

silica with particle sizes smaller than 45 mm. Reactive silica formed in this manner is

often referred to as bio-silica due to its organic nature. Rice husks, sugar cane, and corn

cobs can all be used to make bio-silica. The final product is called biocement when bio-

silica residues are burned and then blended with Portland cement.

Bio-cement is a cement containing amorphous bio-silica (SiO2) generated from the

combustion of organic residues, which serve as pozzolanic materials and partial

replacements for Portland cement. There are two stages involved in the production of bio-
13
cement. The first stage involves the burning of organic residues to produce ash having

reactive bio-silica. In the second stage, the ash produced is blended with Portland cement

to produce bio-cement (Hosseini, et al., 2011). There have been many investigations

carried out which have focused on the use of agro-waste ash, by partially replacing 10–

30% of cement with agro-wastes to achieve high-strength concrete. Cement incorporating

agro-waste ash has shown a great performance in mortar and concrete, even under

exposure to a hydrochloric acid solution (He, et al., 2020)

By substituting the basic raw materials used in the manufacturing of Portland cement

(limestone and clay) with biomass such as sugarcane bagasse ash and rice husk ash a bio-

cement is produced without further depleting limited resources. There is no concern over

depletion of biomass supplies as it can be obtained from numerous sources making it a

renewable source of raw material and energy. The depletion of the landscape resulting

from the mining of limestone will also be avoided. Compared to the combustion of fossil

fuels or the decomposition of limestone which release carbon that has been stored for

millions of years, the burning of biomass does not contribute new CO2 into the

atmosphere. By replanting harvested biomass, a new growth cycle is created with absorb

the CO2 released into the atmosphere. This cyclical process ensures that no “new” CO2

will be released into the atmosphere (Jonkers & Carr, 2012). Several crops grown in

Ghana's temperate regions that have a high silicon concentration and calorific content

have also been discovered to have the potential to make biocement.

In addition, the combustion process can be integrated into energy production to

simultaneously gain the energy and the bio-silica ash.

Biocement has demonstrated environmental, economic, and technological advantages. It

decreases clinker consumption, as well as the energy and CO2 emissions associated with

it. The raw material used to make cement is now renewable. Because of the pozzolanic

14
reaction with bio-silica ash, the final concrete will perform better. Small scale biocement

production is underway in tropical areas, but has received little attention in Ghana.

Biocement is a self-healing substance used to make building structures more durable. It's

a calcium carbonate layer created by bacteria in the soil. The bacteria used in creating

Biocement are naturally occurring in almost all soils and limestone (or Calcite) making

up to a third of the earth crust. Biocement product is shipped as a dry powder to be mixed

in water. It fills the empty space between soil particles. The pozzolanic reaction is a

simple acid based reaction between Calcium hydroxide and SNICIC acid (H4SiO4 or

Si(OH)4). The pozzolanic reaction between amorphous biosilica and calcium hydroxide

must be optimized to produce Biocement with good mechanical and physical properties.

It is optimized when an amorphous (non –crystalline) silica form with high surface area

(particle less than 45 µm) is combined in the appropriate proportion with Al2O3 and Fe2O3

(at least 70% by weight). Ordinary cement is an energy-consuming construction material

with environmental unfriendly production. Biocement has many advantages compared to

an ordinary cement and it is more efficient. It can be used as an eco-construction material

since it consumes less energy and less CO2 emission in the production process than other

ordinary cement.

Comparative advantages of biocement over ordinary cement

1. Biocement is more efficient compared to an ordinary cement which use

temperature up to 1500°C in production process. It increases compressive strength

of mortar by up to 38%. It can also be used as eco-construction material since it

consumes less energy and less CO2 emission in the production process as

compared to other ordinary cement.

2. Biocement needs a much shorter time for production and the in-site process of

raw materials of bio-cement are produced at low temperature. It can

15
 3. Remediate cracks in building materials and monumental stones and regain

strength within 28days. Biocement also enhance the durability of bricks by

reducing their permeability and increasing compressive strength.

4. To make the process economical, microbial additives can be prepared by growing

cells using industrial by products such as lactose, liquor and corn steep liquor as

nutrient sources. The reduced permeability rates resulting from the microbial

additive will increase the concrete structures useful life.

2.4 RAW MATERIALS

Raw materials used for manufacturing of cement are found naturally in the earth’s crust.

It is made primarily from calcareous and argillaceous materials and gypsum. Calcareous

materials contain limestone or chalk while argillaceous materials comprise an oxide of

silica-alumina and iron. Both are found as clay or shale. Cement must be in line with the

strict building standards set for it. Also, the manufacturing process itself must be closely

monitored and controlled to obtain clinker and cement that meet these standards

(WBCSD, 2005).

Cement is made from an intermediate product called clinker. Clinker itself is a complex

mixture formed during high temperature reactions of limestone, clay, sand and iron. It

contains calcium oxide (CaO), aluminium oxide (Al2O3), silica dioxide (SiO2) and small

amounts of iron oxide (Fe2O3). These are formed by the transformation of minerals and

materials in the kiln. Calcium is provided mainly by raw materials such as limestone,

marl, or chalk. Silica, aluminium, and iron components, as well as other elements, are

provided by clay, shale, and other materials. The different kinds of raw materials needed

to achieve the required cement composition are ground and mixed to produce a

homogeneous blend processed in the kiln or fluidized bed (WBCSD, 2005)). Below are

the main constituents of cements and their role in the matrix

16
 • Lime

It is the main constituent used in cement manufacturing. It is responsible for

imparting the cementing property to cement. An excess quantity of lime causes

expansion and disintegration of the cement. Deficiency of lime causes decreased

strength and the cement sets quickly. If it is used in the right proportion, it makes

the cement strong. Thus, lime can drastically change the properties of cement (Alp

& Akin, 2013)

• Silica

This plays a major role in imparting strength to concrete. Silica undergoes a

chemical reaction with calcium to form dicalcium silicate (C2S) and tricalcium

silicates (C3S). Excess silica adds strength to cement but it prolongs the setting

time (Alp & Akin, 2013).

• Alumina

This forms complex compounds with silica and calcium to improve the setting

capacity of the cement. It acts as a flux and lowers the clinkering temperature. Use

of an excess amount of alumina quickens the setting time but reduces the strength

of cement (Alp & Akin, 2013)

• Iron Oxide

This is mainly responsible for giving cement its colour. The hardness and strength

of the cement are also improved to a certain extent. It helps in the fusion of raw

materials during the cement manufacturing process (Alp & Akin, 2013)

2.5 SETTING AND HARDENING OF CEMENT

Setting and Hardening of Cement Setting Process: The process of losing plasticity with

time and becoming dense, which is formed by mixing the cement and water. It happened

in two stage initial setting and final setting. Hardening Process: The process of forming
17
hardening cement paste, which loses plasticity and its strength increases with time.

Factors such as fineness and types of cement, blend of gypsum, age, water content,

temperature and humidity which influence setting and hardening of Portland cement.

Setting is important in concrete work to keep fresh concrete plastic for enough time which

helps the processes of transporting, casting, and compaction. There are four stage occurs

during setting of cement, First : when mixing cement with water, a rapid heat evolution,

lasting a few minutes, This heat evolution is probably due to the reaction of cement

compounds then, heat evolution ceases quickly. Second: this stage called “dormant

period” and last (1-4) hours. Also cement particles start to form initial layer of hydration

product. Bleeding and sedimentation appear in this stage. Third: Next heat evolution is

on account of dissolution of weak gel which formed first on surfaces of C3S crystals so

water will reach these surfaces and starts to form new gel. This stage last about 6 hours.

Forth: in this stage cement begin to harden and gain strength. False and flash Setting False

setting is the rapid development of rigidity in freshly mixed Portland cement paste,

mortar, or concrete occurs after few minutes of mixing cement with water without the

generation of much heat. It can be controlled by re-mixing without additional water or

strength loss. Causes of false setting are: 1. Drying of gypsum: when gypsum

(CaSO4.2H2O) gridding with hot clinker it loss 75% of its water and formed (CaSO4.1/2

H2O) and if temperature of clinker increase gypsum loss all water in its composition and

formed CaSO4. When water add to cement CaSO4 react causes rapid setting. 2. Bad

storage: alkalis in cement react with carbon dioxide forming Alkali carbonate which

reacts with calcium hydroxide forming CaCO3 causing setting of cement paste. 3.

Activate effective C3A exposed to humidity: during bad storage water adhere on cement

particles surface and during mixing these active surface combined rapidly with water

within minutes.

18
2.6 POZZOLANIC MATERIALS

Pozzolanic materials are characterized by mineral particle packing, whereby the

amorphous silica when in contact with water solubilizes and reacts with the Ca2+ ions

present in Ca(OH)2, forming hydrated hydroxide silicates analogous to those produced in

cement hydration reactions as shown in (Equation 1), where the high silica, alumina and

iron oxide content favors the pozzolanic activity of the ash.

Ca(OH)2 +H4SiO4 CaH2SiO4.2H2O (1)

The pozzolanic characteristics of a siliceous and aluminous compound is highly

dependent on the chemical composition, the amorphousness of the phases, and the

fineness. These variables depend mainly on the activation energy (600 o C and 800 o C)

(Ribeiro & Morelli, 2014). The pozzolanic reaction between amorphous bio-silica and

calcium hydroxide must be improved to produce bio-cement with good mechanical and

physical properties. It is improved or enhanced when an amorphous (non-crystalline)

silica form with high surface area (particle size less than 45 mm) is combined in the right

proportion of Al2O3 and Fe2O3 (at least 70% by weight) (ASTM, 2003) with Portland

cement clinker. The best pozzolanic properties are achieved when the combined mass of

SiO2, Al2O3, and Fe2O3 exceeds 70% (ASTM, 2003). By this standard, plant by-products

such as rice husk and sugarcane bagasse are excellent candidates for bio-cement

2.6.1 RICE HUSK AS A POZZOLANIC MATERIAL

The outer shell of rice grain, often called as rice husk, generated from the rice milling

industries is a well-known agro-industrial by-product in many parts of the world. Raw

rice husk (RRH) consists of about 40% cellulose, 30% lignin group and 20% silica. This

RRH is normally used as a fuel in the parboiling process in rice milling industries. On

combustion, the cellulose–lignin matrix of RRH burns away and leaves only a porous

19
silica skeleton. Therefore, RHA contains a large volume of silica. After grinding the

porous silica skeleton of rice husk a fine powder with high surface area, called rice husk

ash (RHA) is produced. Due to its high silica content, RHA is considered as a highly

reactive pozzolanic material in the production of concrete. The reactivity of RHA is

attributed to the high amorphous silica content and the very large surface area governed

by the porous structure of the particles. Highly reactive RHA is found when it is burnt

under controlled conditions. This RHA contains high silica content in the amorphous

form of silica up to 95% or even 100%. Its reactivity is also favored by increasing its

fineness. The pozzolanic reactivity of residual RHA can be improved by grinding up to

an appropriate particle size (Jamil, et al., 2013)

Rice husk is considered a good pozzolanic material due to its high silica content with

amorphous characteristics. Rice husk contains silica in the range of 20 -25 wt% (Real, et

al., 1996)et al., 1996). The silica (SiO2) which exists in the rice husk is present in the

hydrated form like silica gel. Upon thermal decomposition, followed by combustion of

the char, a highly porous and amorphous silica particulate mass is obtained (Kapur, 1985).

Combusted at optimised temperature (600°C and 700oC) the white ash obtained from rice

husk contains approximately 80 – 97 wt% amorphous silica and some number of metallic

oxides (Lataye, et al., 2008). Other studies also reported that rice husk ash contains very

high amorphous silica composition such as Liou, (2004) (>90 wt% silica) and Houston

(1972) (87 – 97 wt% silica). Using rice husk ash as a blend in Portland cement to produce

bio-cement is cost effective and yields several important properties such as resistance to

chemicals and enhanced acceptable strength. Addition of rice husk ash to Portland cement

not only enhances the early strength of concrete, but also forms a C-S-H (calcium silicate

hydrate) gel around the cement particles, increasing the density and reducing the porosity

of concrete. This may increase concrete strength and prevent cracking (Saraswathy &

Song, 2007)

20
(Ganesan, et al., 2008) reported that up to 30 % (by weight) of rice husk ash could be

mixed with Portland cement without adversely changing the strength and permeability

properties of the concrete. However, a blend with 20-25 % (weight) rice husk gave

maximum compressive and tensile strength of the concrete. These results show that rice

husk ash is appropriate pozzolanic material that yields concrete with enhanced strength

and permeability resistance (Saraswathy & Song, 2007)

2.6.2 CHEMICAL COMPOSITION OF RHA

Experimental results have shown that different samples of RHA had combined

percentages of silica (SiO2), Alumina (Al2O3) and ferric oxide (Fe2O3) of more than 70%

(85%). A requirement which a good pozzolan for the manufacture of blended cement

should meet. The requirement of ASTM C 618 for a combined SiO2 + Al2O3 + Fe2O3 of

more than 70% was also satisfied.

Chemical composition of different source of RHA

Chemical Percentage composition (%)

constituents Sample 1 Sample 2 Sample 3 Average

SiO2 81.04 86.51 78.87 82.14

Al2O3 1.80 0.61 1.61 1.34

Fe2O3 1.01 0.60 2.20 1.27

CaO 1.60 0.71 1.33 1.21

MgO 2.25 1.53 2.11 1.96

SO3 0.45 0.02 0.03 0.17

Na2O 0.16 0.05 0.21 0.14

K2O 2.35 1.89 2.03 2.09

P2O5 5.26 4.20 9.87 6.44

21
 S+A+F 83.85 87.72 82.68 84.75

Source: (Raheem & Kareem, 2017)

2.6.3 PHYSICAL AND CHEMICAL ANALYSIS OF PORTLAND CEMENT

AND RICE HUSK.

Amin, 2011 found out that the specific surface area of sugarcane bagasse ash is about

three times greater than that of cement. However, the density, specific gravity and the

mean particle size of cement are higher than those of the biomass ashes as compared in

table 2. Chemical composition analysis of Portland cement, rice husk and bagasse ash

indicate that the biomass ash has three times higher amorphous silica content than cement

as shown in table 1. The biomass ash also contains acceptable amount of Al2O3, Fe2O3,

and CaO which makes rice husk and sugar cane bagasse good pozzolanic cementitious

materials (Mondal, et al., 2011)

Physical property of High-Strength Portland cement and Rice Husk Ash

Material Bulk Sp. Fineness Specific Mean Appearance Colour Odour

Density gravity passing surface grain
(g/cm3) 45 µm area size
(m2/kg) (µm)
Portland 1.15 3.0 82 300 21 Powder Grey Odourless

cement

Rice 0.58 2.06 97 27400 7 Very fine Grey Odourless

husk ash powder black

Source: (Ramasamy, 2012)

22
• Compressive strength of concrete

The compressive strength of sugarcane bagasse ash-blended concrete samples are

compared in table 3. Comparison of the compressive strength of ash-blended concrete

data for 3,7, and 28 days of curing intervals indicates that the compressive strength of the

concrete increases with increasing bagasse ash content up to 10 % and then at 20 % and

achieves similar values to those of the control concrete samples. The compressive strength

obtained for 20% ash composition in 3 days is similar to 7 days compressive strength of

the control sample, whiles the strength at 28 days is greater. The relative increase in

compressive strength is 24.5% at 3 days curing time for 20% bagasse ash content in

concrete compared with control samples for all times of curing. Meanwhile, the relative

rise in strength at 7 and 28 days depreciates. This proves that concrete bagasse ash

composition of 20 % develops early compressive strength as compared with the blank

concrete samples. The silica content, amorphous phase, fineness, specific surface area,

degree of reactivity and the pozzolanic reaction of the reactive silica and calcium

hydroxide accounts for the early compressive strength of the bagasse ash-blended

concrete and the corresponding equivalent increase in compressive strength up to 20%.

The compressive strength reduces to a lesser value than the control concrete for 20% and

30% ash compositions. Consequently, the optimal value for ash-blended concrete seems

to be 20% ash content (Mondal, et al., 2011)

Table I: Strength of bagasse ash-blended concrete

Cement Compressive strength (MPa)

replacement (%) 3 days 7 days 28 days

0 20 27 36

5 22 30 42

23
 10 27 35 43

15 28 35 42

20 27 35 40

25 25 32 35

30 20 25 32

Source: (Mondal, et al., 2011)

• Splitting tensile strength

Table 4 shows the splitting tensile strength experimental values of bagasse ash-blended

concrete after 28 days of curing. There is general increase in splitting tensile strength for

samples containing up to 20% ash blends, whereas at 25% and 30% ash blends, the value

decreases. Clearly, 20% as blend is seem to be optimal level (Amin, 2011).

• Chloride penetration

Amin, 2011 reported that the total charge (coulombs) passing through bagasse ash-

blended concrete samples consistently decreased with equivalent increase in bagasse ash

content up to 25%. There is an increase at 30% ash blend; however less than the control

sample. The data as shown in table 4 clearly indicates that partial replacement of cement

with bagasse ash considerably decreases the chloride permeability of concrete.

Table II: Splitting tensile and Chloride permeability of bagasse ash-blended concrete

Cement Tensile strength Charges passed (coulombs)

replacement (%) of 28 days 28 days 90 days

(MPa)

0 4.5 2700 2500

5 4.9 2000 1600

24
 10 5 1900 1400

15 4.9 1300 1200

20 4.5 1200 1100

25 4 1100 1000

30 3 2100 2000

Source: (Mondal, et al., 2011)

25
 CHAPTER THREE

3.0 METHODOLOGY

3.1 Raw materials

Table III. Raw materials and their sources.

RAW MATERIALS SOURCES

Rice husk Tamale

3.2 Equipment needed

Table IV. Equipment used and their sources

Equipment Sources

Nabertherm furnace Chemical Engineering Laboratory

Volumetric flask Chemical Engineering Laboratory

VWR Oven Dry Line Chemical Engineering Laboratory

Furnace Chemical Engineering Laboratory

Crucibles Civil Engineering Laboratory

Analytical balance Chemical Engineering Laboratory

Platinum-ATR Central Laboratory

Cutting Mill Chemical Engineering

Earthenware Ceramics Laboratory

Sieve Chemical Engineering Laboratory

Beakers Chemical Engineering Laboratory

Heating mantle Chemical Engineering Laboratory

PH meter Chemical Engineering Laboratory

26
3.3 Chemicals Used

i. Hydrochloric Acid (HCl)

ii. Distilled water

Raw Material Preparation (Rice Husk)

The rice husk was washed and dried to remove dirt.

Analysis of Raw Materials

Ultimate and proximate analysis of rice husk

The ultimate and proximate analysis (on dry basis) of rice husk was determined by

Martínez et al., 2011 as shown in the table below:

Table V Ultimate and proximate analysis of rice husk

Ultimate % weight Proximate analysis % weight

analysis

Carbon 36.60 Volatile 57.70

Hydrogen 5.83 Residual moisture 9.30

Nitrogen 3.31 Ash 17.60

Oxygen 36.65 Fixed carbon 15.40

Sulfur 0.01 Higher heating value (MJ/kg) 14.61

Source: (Martínez et al., 2011)

3.4 Moisture Content

Two crucibles labelled B4 and C were weighed on an Electronic Balance and their masses

recorded.
27
Samples of rice husk were put into crucibles B4 and C respectively, weighed and their

masses recorded.

The crucibles are placed on a tray.

The VWR Dry Line Oven is set to a temperature of 105℃ and the trays together with the

crucibles were placed into the oven for 24 hours.

The crucibles were taken out of the oven after 24 hours and cooled for 5 minutes, weighed

and masses recorded.

The crucibles were placed into the oven for another hour at the same temperature. Drying

and weighing are repeated until a constant weight of the samples are obtained.

a) b)

Figure III a) The drying of rice husk; b) VWR Dry Line Oven

The moisture content of the raw material was calculated using equation (1):

(initial mass - final mass)

Moisture content = × 100……………(1)
initial mass

3.5 Acid-Treatment of Rice Husk (Leaching)

Acid pretreatment were done to remove alkali metals as well as other metal impurities in

rice husk using hydrochloric acid and deionized water.

1M HCl was prepared using distilled water.

28
1525 ml of HCL was added to 195 g of rice husk in a clean beaker and the mixture stirred.

The mixture was then placed on a burner and stirred continuously until there was a

uniform temperature of 60°C in the solution.

At 60°C, the stop clock was set for 45 minutes.

The process was repeated for the other 195 g of RH. After the leaching process, the

solution was filtered out and the residue was rinsed severally with distilled water to

remove excess acid content in the rice husk until cleaning fluid presented neutral. (Chen,

et al., 2017)

Figure IV Leaching of Rice Husk

3.6 Combustion of Rice Husk

390 g of rice husk was divided evenly and fed into seven earthen ware bowls and put into

the furnace at 650℃ for 6 hours to produce the ash.

29
 Figure V. Rice Husk before combustion

3.7 Production of bio-cement

5.04 kg each of gypsum and clinker were received. The gypsum received is greyish in

appearance and shiny.

a) b)

Figure VI a) Gypsum received b) Clinker received

Procedure

Due to the large sizes of the clinker and gypsum, they were first crushed manually to

reduce the particle sizes into appreciable size that can be milled.

The manually crushed raw materials are then milled in a cutter mill.

30
The milled raw materials are sieved to separate particles by sizes and get product within

specific size range.

The Rice Husk Ash was further reduced to smaller particle sizes by grinding in a mortar.

The grinded sample is sieved to obtain particle sizes less than 45 microns.

The ash produced is blended with the clinker and the gypsum in the ratio of 30%: 65%:

5%, respectively.

The mixture is collected and packaged into zip lock bags.

Figure VII. a) the cutting mill b) interior of cutting mill

31
Figure VIII. After milling a) Clinker b) Gypsum

32
3.8 Flow diagram

Raw material preparation

Combustion of raw materials

Grinding of clinker, gypsum and ash

Production of Concrete

Test For Properties Of Biocement

Figure IX: Flow diagram of Methodology.

33
 CHAPTER FOUR

4.0 RESULTS AND DISCUSSION

4.1 Drying of rice husk

Table VI Results from drying rice husk

Trays Mass of Tray + Mass of Sample Mass of % Moisture

Sample (g) before drying (g) sample after content
drying (g)
1 512.75 151.74 139.45 8.10

2 510.86 149.11 136.73 8.30

3 510.56 149.24 137.00 8.38

Total 450.09 413.18

4.1.1 Moisture Content

The raw materials were dried to constant weight in a VWR Dry line oven to determine

the moisture content present. The VWR dry line oven with natural convection is used for

thermal processes, heated storage and for convection drying applications with

temperatures up to 220°C. 450.09 g of the raw material was weighed on a Kern balance

and divided into 151.74 g, 149.11 g, and 149.24 g into trays 1, 2, 3 respectively. The

samples were dried in the oven at 105oC. Water boils at 100oC, at 105oC there would be

evaporation of moisture from the interior of the material to the surface, which is the initial

stage of drying. From the ideal gas law, hot vapour expands, becomes less dense and rises.

The ambient air contains moisture, hence there would be a temperature gradient which

would cause the heated moisture in the material to rise to equilibrate the ambient. After

24 hrs, the samples were taken out and weighed. The percentage moisture content was

calculated. The moisture content determines the extent at which drying occurs. The

moisture content is bigger when the mass is small.

34
4.2 Leaching Of Rice Husk

The function of acid pre-treatment in rice husk contains two aspects. One is to accelerate

the hydrolysis and dehydration of lignocellulose to monosaccharides by removing

hydrogen bonds or extractives. On the other hand, after polysaccharides converting to

monosaccharides, metal impurities bounding in organic matters easily expose and have

the chelate reaction with acids, released to acid leaching solutions. The forms of metal

impurities in rice husk normally may be classified into three categories: the water-soluble

part, the acid-leachable part and the residual. The Ca, Mg, and Mn are acid leachable and

are thereby leached from the rice husk.

Figure X. Fourier Transform Infrared on rice husk

The FTIR result on rice husk indicates the presence of silanol functional group at the

wavelenght of 1035.29 cm-1. Si-O-Si vibration is also shown at 785.55cm-1

35
Figure XI Fourier Transform Infrared on Leached rice husk

The FTIR result on rice husk indicates the presence of silanol functional group at the

wavelenght of 1054.60 cm-1. Si-O-Si vibration is also shown at 796.95cm-1

4.2.1 SEM analysis of rice husk

Figure XII Morphology of (a) un-leached rice husk; (b) hydrochloric acid-leached rice
husk

36
Source: (Bakar, et al., 2015)

The SEM analysis shows the morphology of outer surfaces of un-leached and acid-

leached rice husks. The outer surface of rice husk is uneven and highly roughened. After

acid leaching, a significant change in rice husk morphology can be seen. The surfaces of

un-leached rice husk showed greater degree of roughness than those that have been

leached with dilute acids, presumably due to the hydrolysis of some organic components

by the acids. (Bakar, et al., 2015)

37
4.2.2 Characterization of rice husk

Source: (Huabcharooen, et al., 2017)

Figure XIII Physical and Morphological Characterization for Untreated and HCl Treated
Rice Husk

The results of the physical and morphological characterization for the untreated and

treated RH are shown in the table above. The XRF and FTIR results indicated that silicon

dioxide was the main component of the RH and the remainder of the RH consisted of

38
various kinds of metal oxides. The silica remarkably increased after being treated with

HCl. The silica content was 77.2% for the untreated RH which became 90.6% after being

treated with HCl. This was because HCl was capable of removing metal oxides.

Most of the RH particles had average particle size of less than 40 µm, and the percentage

of the small particles increased after the addition of HCl. The surface area as well as the

pore size were found to increase after the RH has been treated with HCl. This was because

HCl has the ability to extract metal oxides in the RH, which made the fibres more spongy

and porous which in effect increased the surface area. (Huabcharooen, et al., 2017)

39
4.3 Combustion

Table VII. The yield of rice husk ash after 4 hours

Temperature (°C) Mass of Rice husk Mass of rice husk ash % yield of ash

(g) (g)

650 390 79.56 19.3

The combustion process gave a minimum yield of 19.3%. It gave a white amorphous

silica rice product.

a) b)

Figure XIV. a) Rice Husk before drying b) Rice husk after drying

40
4.4 Proximate analysis on rice husk

Rice Husk Proximate Analysis

120%

100%

80%

60%

40%

20%

0%

-20%

Moisture (%w/w) avg ash(%w/w)avg

volatiles (%w/w) avg fixed C (%w/w) avg

Figure XV: Proximate Analysis of Rice Husk

Figure XV shows the graphs for proximate analysis on rice husk. This shows us the bulk

compositions for both biomass. Rice husk had a moisture content of 3.56%. This indicates

that rice husk has absorptive capacity.

The volatile in rice husk was recorded at 79.83% this shows that there are lot of cellulose

fibers in rice husk, hence rice husk has more organic component in it. Ash content for

Rice husk was recorded at 19.53%. This indicates that rice husk has inorganic components

per gram of biomass.

41
4.5 FTIR on biocement

FTIR offers a quantitative and qualitative analysis for organic and inorganic samples.

Fourier transform Infrared Spectroscopy (FTIR) identifies chemical bonds in a molecule

by producing an infrared absorption spectrum. The spectra produce a profile of the

sample, a distinctive molecular fingerprint that can be used to screen and scan samples

for many different components. FTIR is an effective analytical instrument for detecting

functional groups and characterizing covalent bonding information. Infrared

spectroscopy has been a workhose technique for materials analysis in the laboratory for

oven seventy years. An infrared spectrum represents a fingerprint of a sample with

absorption peaks which corresponds to the frequencies of vibrations between the bonds

of the atoms making up the material. Because each different material is a unique

combination of atoms, no two compounds produce the exact same infrared spectrum.

Therefore, infrared spectroscopy can result in a positive identification (qualitative

analysis) of every different kind of material. In addition, the size of the peaks in the

spectrum is a direct indication of the amount of material present.

Fourier Transform Infrared (FT-IR) spectrometry was developed in order to overcome

the limitations encountered with dispersive instruments. The main difficulty was the slow

scanning process. A method for measuring all the infrared frequencies simultaneously,

rather than individually was needed. A solution was developed which employed a very

simple optical device called an interferometer. The interferometer produces a unique type

of signal which has all of the infrared frequencies “encoded” into it. The signal can be

measured very quickly, usually about one second or so. Thus, the time element per sample

is reduced to a matter of a few seconds rather than several minutes.

Most interferometers employ a beam splitter which takes the incoming infrared bean and

divides into two optical beams. One beam reflects off a flat mirror which is fixed in place.

42
The other beam reflects off a flat mirror which is on a mechanism which allows this mirror

to move a very short distance (typically a few millimetres) away from the beamsplitter.

The two beams reflect off their respective mirrors and are recombined when they meet

back at the beamsplitter. Because the path that one beam travels is a fixed length and the

other is constantly changing as its mirror moves, the signal which exits the interferometer

is the result of these two beams interfering with each other. The resulting signal is called

interogram which has the unique property that every data point (a function of the moving

mirror position) which makes up the signal has information about every infrared

frequency which comes from the source. This means that as the interferogram is

measured, all frequencies are being measured simultaneously. Thus, the use of the

interferometer results in extremely fast measurements. Because the analyst requires a

frequency spectrum (a plot of the intensity at each individual frequency) to make an

identification, the measured interferogram signal cannot be interpreted directly. A means

of ‘decoding’ the individual frequencies is required. This can be accomplished via a well-

known mathematical technique called the Fourier Transformation. This transformation is

performed by the computer which then represents the desired spectral information for

analysis.

43
Figure XVI: FTIR on Biocement

The FTIR results on biocement indicates the presence of silanol functional group at a

wavelength of 1075.43 cm-1

44
 CHAPTER FIVE

5.0 CONCLUSION AND RECOMMENDATION

5.1 Conclusion

The production of biocement using rice husk ash was successful. The rice husk used for

this work is widely available at Ejura, Ghana. This work has proven that, there is a great

scope for the exploitation of rice husk waste as resources; for the production of biocement

on an industrial scale in Ghana. The yield of biocement produced depended on the quality

and quantity of the ash, which in turn depended on the combustion temperature (to

produce either amorphous or crystalline silica). The biocement was characterised by

Fourier Transform Infrared which indicated the presence of the silanol group which

shown a close resemblance to the properties of a quality biocement.

5.2 Recommendations

1. It is recommended that the production of the biocement from rice husk should be

made commercial.

2. It is recommended that the necessary equipment for the tests such as XRF, XRD,

and ICP-MS be provided to estimate the elemental components of the biocement.

3. It is recommended that the necessary equipment for testing the physical properties

of such as soundness, setting times, strength and flow of the mortar mixer of the

biocement.

45
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 APPENDIX

Appendix 1. Sample Calculation

Appendix 1a.. Determination of moisture content of rice husk

Sample 1

Mass of empty crucible, W1 = 361.01 g

Mass of empty crucible + sample, W2 = 512.75 g

Mass of empty crucible + sample after drying, W3 = 500.46 g

𝑊 −𝑊
Equation 1. % Moisture content on dry basis = 𝑊2− 𝑊3
3 1

512.75 − 500.46
= × 100%
500.46 − 361.01

= 8.8%

Sample 2

Mass of empty crucible, W1 = 361.75 g

Mass of empty crucible + sample, W2 = 510.86 g

Mass of empty crucible + sample after drying, W3 = 498.48 g

𝑊 −𝑊
Equation 2. % Moisture content on dry basis = 𝑊2− 𝑊3
3 1

510.86 − 498.48
= × 100%
498.48 − 361.75

= 8.3%

Sample 3

Mass of empty crucible, W1 = 361.32 g

53
Mass of empty crucible + sample, W2 = 510.56 g

Mass of empty crucible + sample after drying, W3 = 498.5 g

𝑊 −𝑊
Equation 3. % Moisture content on dry basis = 𝑊2− 𝑊3
3 1

510.56 − 498.5
= × 100%
498.5 − 361.32

= 8.79%

8.8 +8.3 +8.79

Average % Moisture content = 3

= 8.63%

54