Faculty of Engineering

Department of Chemical
Engineering

Dry Flue Gas Desulphurisation

Sorbent synthesis

Student Name : Mellisa Z Ncube

Student Number : N0161145V
Supervisor : Ms S Bhebhe
2020-2021
Abstract
Dry flue gas desulphurisation Coal fly ash-conditioned sorbents were prepared by hydration coal fly
ash and Ca(OH) 2 at 100⁰C with different raw material ratios from 1:3, 5:3, 9:3 and 15:3 and hydration
time ranging from 60 to 240 minutes. Prior to sorbent preparation, the fly ash was characterised with
X-ray fluorescence analysis and loss on ignition tests to determine the chemical composition of fly ash.
The main constituents of the fly ash were found to be SiO 2 (51%), Al 2 O3 (28%) and Fe 2 O3 (10%). The
loss on ignition was 8%. The resultant sorbents were characterised by Ca(OH) 2 conversion, a
quantitative expression of the extent of the pozzolanic reaction between fly ash and Ca(OH) 2. The
Ca(OH) 2 conversion was influenced by the hydration period as well as the initial raw material ratio.
The highest conversion of 74.78% was obtained for fly ash: Ca(OH) 2 ratio of 15:3 with 240 minutes( 4
hours) of hydration time. The sorbents were then tested for desulphurisation activity with the extent
of desulphurisation quantified as the amount of sulphate ions in the product solids. The highest
desulphurisation activity was obtained for fly ash: Ca(OH) 2 ratio of 5:3 and hydration time of
240minutes. The desulphurisation activity of the CFA-conditioned sorbent was then compared with
that of the commercial hydrated lime. The results showed that the CFA conditioned sorbent exhibited
higher desulphurisation activity ( 1.19675 × 10−3 mol/l ) compared to0.8559 × 10−3 mol/l
for the commercial hydrated lime sorbent. The Ca(OH) 2 conversion, initial raw material ratio and
hydration time have been determined to be the most important parameters which affect sorbent
performance during dry flue gas desulphurisation.

i
Dedication
This research project is dedicated to my beloved parents, Mr Mbeji Ncube and Mrs Sipho Ncube, who
continually provide their moral, emotional, spiritual and financial support.

ii
Acknowledgements
The completion of this work could not have been possible without the assistance of so many people
whose names may not all be mentioned. Their contributions are sincerely appreciated and grate fully
acknowledged. However, I would like to express my deep appreciation and indebtedness particularly
to my supervisor, Miss Siboniwe Bhebhe, for her invaluable advice, continuous support and
encouragement during the course of my research project.

I would also like to acknowledge Miss Lawrencia Tshuma and Eng. Sokesimbone Ncube for their
assistance during my experimental work. I am thankful to the National University of Science and
Technology for providing me with the necessary facilities to conduct my research. I am also grateful
to Eng. Munyaradzi Makudo and to the ZPC Hwange expansion project family for their assistance in
this work. To my friends, Nicolete Mapepa, Prioress Nyoni, ridget Mushava and Duduzile Selome, I am
truly grateful. Special mention goes to my brother and mentor, Eng. Zibusiso Lubimbi, for his support
and advice throughout my academic career.

Most importantly, I would like to express my deepest gratitude to GOD, the author of wisdom and
knowledge.

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Contents
Abstract ........................................................................................................................................ i
Dedication.................................................................................................................................... ii
Acknowledgements ..................................................................................................................... iii
1.0 Introduction...................................................................................................................... 1
1.1 Introduction .................................................................................................................. 1
1.2 Theoretical Background.................................................................................................. 2
1.3 Statement of the problem .............................................................................................. 5
1.4 Justification of the study ................................................................................................ 5
1.5 Main objective:.............................................................................................................. 6
1.5.1 Specific Objectives.................................................................................................. 6
1.6 Research design/ Methodology ...................................................................................... 6
2.0 Literature Review .............................................................................................................. 8
2.1 Introduction .................................................................................................................. 8
2.2 Dry FGD Process Overview ............................................................................................. 9
2.2.1 Sorbent Injection systems ....................................................................................... 9
2.2.2 Dry FGD advantages and disadvantages ................................................................. 14
2.3 Commercially Available sorbents for dry FGD ................................................................ 15
2.4 Coal fly ash.................................................................................................................. 16
2.4.1 Coal fly ash Properties .......................................................................................... 16
2.5 CFA- conditioned sorbent............................................................................................. 18
2.5.1 Fly ash-conditioned sorbent preparation variables ................................................. 20
3.0 Methodology................................................................................................................... 23
3.1 Objectives of the experiments ...................................................................................... 23
3.2 Equipment and chemicals utilised ................................................................................. 23
3.3 Procedure ................................................................................................................... 24
3.3.1 Fly ash preparation............................................................................................... 25
3.3.2 Fly Ash hydration.................................................................................................. 27
3.3.3 Sorbent Preparation ............................................................................................. 28
3.3.4 Determination of extent of hydration .................................................................... 28
3.3.5 Desulphurisation activity test ................................................................................ 29
4.0 Results and discussion ..................................................................................................... 31
4.1 CFA characterisation .................................................................................................... 31
4.1.1 XRF Analysis results: ............................................................................................. 31
4.1.2 CFA Loss on Ignition Results .................................................................................. 31
4.1.3 Sieve Analysis Results ........................................................................................... 33

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 4.2 Fly ash hydration results............................................................................................... 34
4.3 Sorbent preparation results .......................................................................................... 36
4.4 Ca(OH)2 conversion results ........................................................................................... 37
4.5 Desulphurisation activity results ................................................................................... 39
4.6 Summary and conclusions ............................................................................................ 42
5.0 Conclusion and Recommendations ................................................................................... 44
5.1 Conclusion................................................................................................................... 44
5.2 Recommendations....................................................................................................... 45
6.0 References ...................................................................................................................... 46
Appendix.................................................................................................................................... 50

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List of figures
Figure 1.1 classification of SOx emission reduction technologies (Hanif and Ibrahim, 2020) ............. 2
Figure 1.2 SEM micrograph of a coal fly ash sample (Lee et al., 2006)............................................. 4
Figure 2.1 SO2 emission from different anthropogenic sources (Taylor et al., 2010) .......................... 8
Figure 2.2 Sorbent injection locations (Glier and Rubin, 2013) ...................................................... 10
Figure 2.3 Schematic of Furnace Sorbent Injection (FSI) system (Taylor et al., no date) .................. 11
Figure 2.4 Schematic of Duct Sorbent Injection (DSI) system (Taylor et al., no date) ...................... 13
Figure 2.5 Schematic of circulating fluidised bed system (Muzio and Often, 2012) ......................... 14
Figure 2.6 Ash pond site for disposal of fly and bottom ash ........................................................... 17
Figure 2.7 Morphology of coal fly ash particles (Asokan, Saxena and Asolekar, 2005).................... 18
Figure 2.8 Particle morphology of hydrated sorbent vs. commonly used industrial sorbent.
(Ahmaruzzaman and Gupta, 2012)............................................................................................... 20
Figure 3.1 Laboratory furnace ..................................................................................................... 26
Figure 3.2 Mechanical sieve shaker.............................................................................................. 27
Figure 4.1 Loss on ignition results for different fly ash samples ..................................................... 31
Figure 4.2 fly ash samples prior to heating in furnace .................................................................... 32
Figure 4.3 fly ash samples after heating in furnace ........................................................................ 32
Figure 4.4 Particle size distribution of fly ash ............................................................................... 33
Figure 4.5 effect of hydration time on pH of fly ash hydration solution .......................................... 34
Figure 4.6 Effect of particle size on pH of fly ash hydration solution.............................................. 35
Figure 4.7 CFA/Ca(OH)2 sorbent................................................................................................. 36
Figure 4.8 Effect of hydration time on CA(OH)2 conversion .......................................................... 37
Figure 4.9 effect of CFA/Ca(OH)2 raw material ratio on Ca(OH)2 conversion ................................. 38
Figure 4.10 Effect of CFA:Ca(OH)2 raw material ratio on desulphurisation activity ........................ 39
Figure 4.11 effect of hydration time on desulphurisation activity .................................................. 40
Figure 4.12 Effect of Ca(OH)2 conversion on desulphurisation activity .......................................... 41
Figure 4.13 Desulphurisation activity for CFA conditioned sorbent an commercial lime sorbent ...... 42

List of Tables
Table 2.2.1 Advantages and disadvantages of dry FGD process (Asokan, Saxena and Asolekar, 2005)
.................................................................................................................................................. 14
Table 2.2.2 typical properties of commercially available sorbents (Muzio and Often, 2012) ............. 16
Table 2.2.3 fly ash compositions from seven different studies (Ogenga et al, 2008)......................... 18
Table 2.2.4 Important properties and preparation parameters for CFA utilisation in sorbent preparation
.................................................................................................................................................. 20
Table 3.1 Materials and methods ................................................................................................. 23
Table 3.2 Fly ash hydration results ............................................................................................... 27
Table 3.3 CFA/Ca(OH)2 raw material ratios ................................................................................. 28
Table 4.1 XRF analysis results .................................................................................................... 31
Table A. 1 Loss on ignition results 50

Table A. 2 Sieve analysis results .................................................................................................. 50

Table A. 3 CFA Hydration results ................................................................................................ 51
Table A. 4 Titration with 0.5M EDTA results ............................................................................... 51
Table A. 5 Ca(OH)2 Conversion.................................................................................................. 54
Table A. 6 Indirect titration results ............................................................................................... 55
Table A. 7 Desulphurisation activity results .................................................................................. 58

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Table A. 8 Desulphurisation activity results for commercial hydrated lime sorbent ......................... 59

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1.0 Introduction
1.1 Introduction
Energy consumption has increased with the rapid increase in population and economic growth
(Yao et al., 2015). This has necessitated an increase in the setting up of large coal-fired thermal
power plants to cater for the demand for electric power generation requirements. The world is
highly reliant on fossil fuels for meeting electricity generation requirements. The use of coal
as a major source fuel is expected to increase due to its abundance and price stability, as such,
emissions control of gaseous pollutant products of coal combustion is of paramount importance
(Gadonneix et al., 2010).

For a developing country like Zimbabwe, which heavily relies on coal as an energy source for
power generation, pulverised coal combustion will remain the major combustion technology.
As a result, production of rapidly increasing waste streams as well as emission of gaseous
pollutants remains a significant environmental and economic problem that has resulted in a
global waste disposal crisis.

The detrimental environmental and health effects of sulphur dioxide released from coal
combustion in thermal power plants have led to national and international legislation to limit
the emission of sulphur dioxide. To this end, various flue gas desulphurisation (FGD)
technologies have been widely used to adhere to the stringent environmental regulations on
SOx emissions.

A majority of the SO x removal techniques have been established on the utilisation of calcium-
based materials such as limestone in wet FGD and lime in dry FGD processes. Recent studies
have focussed on the dry and semi dry FGD whose major sorbent is hydrated lime which has
the problem of low sorbent utilisation (Ash, 2008). Improving the utilisation of lime, that is,
sorbent performance, in dry and semi dry FGD systems is one of the major current challe nges
that researchers are faced with. According to (Renedo and Ferna, 2002), sorbents obtained by
conditioning lime with a siliceous material such as coal fly ash lead to a remarkably higher
conversion of calcium compared to those using hydrated lime only.

Coal fly ash (CFA), which accounts for about 80% of solid coal combustion residual, has a
high silica content and is viable for improving sorbent utilisation (Reshma, Scholar and
Technology, 2013). According to (Lee and Koon, 2009), hydration of calcium based sorbents
with fly ash produces a porous sorbent with a high specific surface area. The high specific
surface area provides more area for sulphur dioxide capture in the new sorbent. Previous work
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by (Environ, Peterson and Rochelle, 1988) showed that the desulphurisation activity of the fly
ash conditioned sorbents is influenced by its composition and structural properties, as such, a
better and comprehensive understanding of these effects will assist in the preparation of
sorbents with enhanced SO 2 capture capacity for dry sorbent technologies.

This study seeks to investigate the effect of sorbent utilising CFA as a source of silica on dry
FGD sorbent SO 2 capture capacity. It additionally centres on the hydration process and the
conditions which are likely to affect the performance of the product sorbent material during
hydration.

1.2 Theoretical Background

Technologies for SO x emissions reduction are generally divided into pre-combustion,
combustion and post- combustion technologies, as displayed by figure 1.1

Pre-combustion
•Involves processes such as desulphurisation of the fuel and coal gasification or
liquefaction.

combustion
•Includes combusting coal and limestone mixtures

Post-combustion
•wherein flue gas from coal combustion is put into contact with an alkaline
component (usually limestone or lime containing products)

Figure 1.1 classification of SOx emission reduction technologies (Hanif and Ibrahim, 2020)

The most commonly utilised technology is FGD which is applied post coal combustion. FGD
can be categorised by water usage; that is, wet scrubbing, semi-dry and dry scrubbing. The
wet FGD process using calcium carbonate as an absorbent is the most commonly utilised FGD
technology in many commercial plants.

Almost all commercial FGD processes are based on the fact that SO 2 and SO 3 are acidic and
so can be separated from the flue gases by a reaction with a suitable alkaline sorbent such as
limestone (CaCO 3 ), CaO and hydrated or slacked lime (Ca(OH)2 ) (Lin, Shih and Liu, 2003a)

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The sorbents react with SO x in the flue gas to produce a combination of sulphite and sulphate
salts.

Wet FGD processes involve bringing the flue gas into contact with the sorbent either as a
solution or a slurry in a separate wet scrubber. The SO x in the flue gas then dissolves in the
water to produce a dilute acidic solution which then reacts and is neutralised by the alkaline
sorbent producing sulphite and sulphate salts that precipitate out of solution depending on the
relative solubility of the various salts present (Hanif and Ibrahim, 2020).

The dry and semi dry FGD processes involve bringing the sorbent into contact with the flue
gas by either injecting or spraying it into the flue gas stream or by passing the gas through the
dry sorbent in a separate vessel (Muzio and Often, 2012). The aim is to facilitate direct reaction
of the SO 2 and SO 3 gases with the solid sorbent to produce the corresponding sulphate and
sulphite salts. Dry FGD systems generally do not need process water and inevitably, do not
produce a wastewater discharge stream. The dry processes either consume no water or a
minimal amount (if the sorbent requires hydrating during preparation) or the flue gas requires
to be humidified to improve performance (Carpenter, 2012).

The effectiveness of the dry and semi dry FGD processes is dependent on sorbent utilisa tio n
which is related to the physical properties of the sorbent such as surface area (Ahmaruzza ma n
and Gupta, 2012). Sorbents from lime sources have the problem of low solvent utilisation. A
lot of research on improving the performance of lime sorbents have focussed on increasing the
surface area utilising additives. Inorganic hydroscopic salts such calcium chlorides and sodium
nitrates can amplify sorbent performance (Garea, Viguri and Irabien, 1997).

Reacting CaO/Ca(OH)2 with fly ash, zeolites, rice husk ash or other pozzolanic materials has
shown sorbent performance and reactivity improvement (Lee et al., 2005) Pozzolanic material
primarily constitute of Aluminous and siliceous materials which react with Ca(OH) 2 to produce
complex hydrous calcium alumina silicates that have high porosity and surface area which
promotes reactivity of the sorbent. CFA generated from coal combustion is mainly composed
of SiO 2 , Al2 O3 , Fe2 O 3 and CaO and exhibits high alkalinity (depending on the sulphur content
of the coal). Typical SEM micrograph for CFA shows that typical CFA is spherical in nature
(fig 1.2) with a relatively smooth surface while CFA/ Ca(OH)2 appear to have an irregular foil-
like shape, while some were plate-like and sphere-like. The shape causes the particles to cohere
to form a porous structure thus creating a larger surface area as shown by figure 5.2 (Lin, Shih
and Liu, 2003a)

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The appreciable content of porous amorphous SiO 2 and Al2 O3 in fly ash can be utilised in
absorbing SOx acid gases either by chemical or physical absorption.

Figure 1.2 SEM micrograph of a coal fly ash sample (Lee et al., 2006)

Figure 1.2 SEM micrograph of a Ca(OH)2/fly ash (weight ratio 70/30) sorbent (Lin, Shih and
Liu, 2003b)

Studies by (Ishizuka et al., 2000) have shown that the utilisation of calcium of CFA/ Ca(OH) 2
prepared by hydration at ambient temperature was nearly three times higher than with

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commercially hydrated Ca(OH)2 alone. Calcium utilisation increased with increase in the
amount of fly ash up to a certain value which depends on the composition of the CFA.

1.3 Statement of the problem

In order to mitigate the adverse environmental and health effects of SOx emissions from coal-
fired thermal power plants, various technologies aimed at SOx pollutants capture are being
developed with wet FGD being the most utilised. However, although wet FGD has high SOx
collection efficiency (98%), there are several environmental concerns with regards to its use
such as consumption of large quantities of water and generation of a waste water product that
requires treatment before disposal (Zhai et al., 2017). According to (Kitat, 1995), wet FGD is
the second largest consumer of water in thermal power plants. Research has shown that the per
capita availability of water is reducing, as such competition between agricultural, urban /
domestic and industrial use demand for water is most likely to intensify (Carpenter, 2012).
Subsequently, there is a consensus on the need to develop more sustainable alternatives for SO x
capture aimed at reducing water usage in FGD systems such as utilising various hydrated lime
or limestone sources as dry sorbents for SO x capture. The major drawback with dry sorbents is
low sorbent utilisation which is attributed to relatively lower surface area and pore size for
absorption (Ash, 2008). Improving the utilisation of lime, that is, sorbent performance, in dry
and semi dry FGD systems is one of the major current challenges that researchers are faced
with.

1.4 Justification of the study

The market for FGD technology is anticipated to grow in the next 10 years as power plants
install FGD systems or upgrade their existing systems in order to meet stricter SO x emissio n
levels (Carpenter, 2012). A lot of studies have been directed at dry type flue gas
desulphurisation on account of its environmental friendliness and low cost of installation with
focus on preparation of high performance sorbents to reduce use of water (Ishizuka et al.,
2000). Studies have shown that use of sorbents obtained through hydration of lime with sources
of silica such as fly ash results in significantly higher conversion of calcium in terms of the
number of moles of sulphur dioxide per mole of calcium in the sorbent (Renedo, 2003).
Zimbabwean thermal power plants use sub-bituminous coal as a source of fuel which has a
high silica content (40-60%) (Ishizuka et al., 2000). Use of fly ash as a siliceous source for
absorbents in dry-type or semi dry FGD is advantageous for both economic and environme nta l
reasons because fly ash is the most voluminous waste from coal fired power plants and is
therefore readily available (Caso et al., 2005). The efficient recycling of wastes and by-

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products, and their proper management are significant aspects for the sustainability of power
plants. As the world is moving towards adopting environmentally sustainable practices, dry
type FGD can be considered to be an ideal choice for controlling sulphur dioxide emission and
an environmentally- friendly method for reuse of CFA.

1.5 Main objective :

To investigate the use of coal fly ash for production of high performance sorbent for use in dry
type flue gas desulphurisation (FGD).

1.5.1 Specific Objectives

1. To determine the influence of particle size distribution and hydration
time on pH of the hydration solution.
2. To prepare CFA-conditioned sorbent utilising different hydration
time periods and CFA: Ca(OH)2 raw material ratio.
3. To determine the influence of hydration time and CFA: Ca(OH) 2 raw
material ratio on the extent of the pozzolanic reaction (Ca(OH)2
conversion) between CFA and Ca(OH)2 of the CFA conditio ned
sorbents.
4. To determine the influence of hydration time and Ca(OH)2
conversion on the desulphurisation activity of the CFA conditio ned
sorbents.
5. To compare the desulphurisation activity of CFA conditio ned
sorbent and commercial hydrated lime sorbent.

1.6 Research design/ Methodology

This research project incorporated data from experimental procedures as well as reviews of
various sources of literature on the subject so as to meet the aims and objectives of the study.

CFA samples were provided by ZPC HEP and experiments to analyse the influence of particle
size distribution, hydration time and CFA concentration on the pH of the hydration solutio n
were conducted.

Titration experiments were conducted to measure Ca(OH)2 / CaO/ CaCO 3 conversion (Calcium
utilisation) so as to obtain a quantitative expression of the extent of the pozzolanic reaction
during sorbent preparation.

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Lastly, desulphurisation activity tests were cconducted to serve as an indication of the sorbent
activity as influenced by the sorbent preparation variables (hydration time, raw material ratio
and Ca(OH)2 conversion.

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2.0 Literature Review
2.1 Introduction
Industrial operations are required to reduce air pollutant emissions in compliance with stringe nt
regulations mandated by environmental and health regulatory bodies like the Environme nta l
Management Agency, EMA. One of the main targets to be reduced are SO x gases. The
combustion of coal from power generation is one of the major sources of anthropogenic
emission of sulphur. According to (Foo et al., 2011), a 600MW capacity coal fired power plant,
burning coal containing 1.2% sulphur releases 1783m3 /hour (NTP) S02 with a typical flue gas
composition of 350ppm S02 , 125ppm N0, 5.2% O 2 , 13% CO and 7.8% H2 O. The distributio n
of sulphur dioxide emission from different anthropogenic sources is presented in figure 2.1.

% emission

6.8
2.6
3.5

13.6

69.7

Electricity utility fuel combustion Industrial fuel combustion Metal processing

Other fuel combustion All other sources

Figure 2.1 SO2 emission from different anthropogenic sources (Taylor et al., 2010)

A number of factors determine the extent to which sulphur oxides are emitted through fossil
fuel combustion. These factors include the particular unit operations employed during
combustion of the fossil fuels, the control system utilised for SO x emission control as well as
the sulphur content of the fossil fuel (Zhou et al., 2009). Generally, low sulphur coals have less
than 1% sulphur content. The inorganic sulphur content in coal is typically in the range of 0.01
to 2% whereas organic sulphur content is usually in the range of 0.03-7.6% of the total sulphur
content in coal. Electricity generation from coal fired power plants is the major global
contributor of SO x emission (Muzio and Often, 2012). For developing countries like Zimbabwe
which heavily rely on coal as a major source of energy, SO x emissions are expected to increase
as coal utilisation increases.

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A number of different SO x emission reduction technologies have been developed with a
majority of these technologies emanating from the utilisation of calcium based sorbents such
as limestone and lime. Limestone is utilised in wet scrubbing whilst hydrated lime is typically
used for dry and semi dry FGD processes (Foo et al., 2011). The drawbacks such as large water
consumption and need for waste water treatment which are associated with wet scrubbing, have
resulted in a lot of research efforts prioritising the more environmentally- friendly dry and semi
dry processes whose sorbents have the challenge of low sorbent utilisation (Richardson et al.,
2013)
Improvement of newer flue gas desulfurization technologies is continually advancing, with the
primary objective of accomplishing high desulfurization efficiency usually obtained through
wet FGD method and decreasing or eliminating the production of waste and by-products
typically acquired with wet scrubbing. Research by (Taylor, 2007) has demonstrated that
significantly higher calcium utilisation can be achieved by making use of sorbents prepared by
conditioning of calcium based sorbents such as lime, with various sources of silica such as rice
husk and coal fly ash. However, the difficult preparation conditions such as long hydration and
drying time tend to complicate the scale up of the sorbent preparation system for enginee r ing
applications. As such, there is need to improve sorbent preparation for commercial use of high
activity sorbent to meet SO x removal capability in relation to production costs.

2.2 Dry FGD Process Overview

Dry FGD processes have been in commercial use for more than 20 years. The dry processes
were initially employed for SO x emissions control on small units which burn low sulphur coals
(circumstances in which wet scrubbing would not be cost effective) (Richardson et al., 2013).
Dry FGD is an alternative to wet scrubbing and has been developed into multi pollutant (S0 x ,
HCl, HF and Hg) removal technologies that have received wide application in coal fired power
plants and iron and steel sintering plants (Zhai et al., 2017). Studies have shown that dry
sorbent injection removes SO 3 more effectively than wet scrubbing (Garea, Viguri and Irabien,
1997). Generally, process water is usually not required for dry sorbent injection, however a
minimal amount may be required for hydrating the sorbent or humidifying the flue gas to
improve the process performance. Water may also be required for sorbent preparation. The two
common methods utilised in dry FGD processes are direct sorbent injection, which
pneumatically injects dry sorbent into the flue gas duct, and spray system which injects
atomised sorbent slurry into a separate vessel. Both processes produce a final dry product(Lin,
Shih and Liu, 2003a).Direct sorbent injection systems will be the main focus for this research.
2.2.1 Sorbent Injection systems
There are various sorbent injection systems in practice. All the systems generally involve
pneumatically transporting the dry powdered sorbent to injection lances. The dry solid product
is then collected in a particulate control device which is usually either an electrostat ic
precipitator (ESP) or fabric filter baghouse together with CFA. It has been reported in literature
that fabric filter baghouses achieve greater SO x collection efficiency compared to ESPs due to
the filter cake on the bags which allows for longer residence time for the flue gas and powdered
sorbent to interact (Tsuchiai et al., 2000). In a bid to increase sorbent utilisation, some systems
undergo sorbent recirculation and whereas others are once through.
A good injection system is of paramount importance for ensuring adequate mixing and contact
of SOx gases and the sorbent. The injection nozzle and lance design determine the injectio n

9
dispersion efficiency (Muzio and Often, 2012)The desired level of SO x control influences the
type of sorbent as well as the injection location. Typical injection locations in a power plant
unit are presented in figure 2.2

Figure 2.2 Sorbent injection locations (Glier and Rubin, 2013)

There are four types of sorbent injection systems which will be discussed in this study, namely:
 Furnace sorbent injection;
 Economiser sorbent injection;
 Duct sorbent injection;
 Circulating fluidised bed system

2.2.1.1 Furnace sorbent injection (FSI) system

FSI systems are the simplest and cheapest dry FGD technology. FSI is best suited for small
(< 300𝑀𝑊power plants) in which low to medium sulphur coals are used. Dry sorbent is
directly injected into the section of the furnace in which temperature is between 950⁰C and
1000⁰C (Carpenter, 2012). These high temperatures in the furnace have the advantage of
sometimes decomposing the sorbent, rendering it a porous solid which results in a higher
surface area for reaction with SOx to form calcium sulphate. Moreover, uniform distributio n
of the sorbent across the furnace, sorbent particle size (the finer the sorbent the higher the
activity), together with adequate residence time are critical for sorbent performance. The
products and remaining unreacted sorbent are then separated from the flue gas the particula te
collector system (Hall et al., 2012)

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Sorbents that have been studied for this particular sorbent injection technology are mainly
limestone, naturally occurring dolomite as well as lime. The following two-step reactions take
place:
Thermal decomposition of the sorbents to produce CaO:
For limestone
𝐶𝑎(𝐶𝑂)3 → 𝐶𝑎𝑂 + 𝐶𝑂2
For calcium hydroxide:
𝐶𝑎(𝑂𝐻)2 → 𝐶𝑎𝑂 + 𝐻2 𝑂
Lastly, Sulphation reaction of resultant CaO with SO 2 pollutant:
1
𝐶𝑎𝑂 + 𝑆𝑂2 + 𝑂 → 𝐶𝑎𝑆𝑂4
2 2

Figure 2.3 Schematic of Furnace Sorbent Injection (FSI) system (Taylor et al., no date)

Some FSI systems utilise finely pulverised limestone instead of hydrated lime and a humidifier
is attached downstream of the furnace so as to humidify the flue gas to enhance SO x removal.
2.2.1.2 Economiser sorbent injection systems
For this particular sorbent injection technology, sorbent injection into the flue gas takes place
close to the economiser inlet of the fire-utility boiler which typically has temperatures ranging

11
from 300-650⁰C. The commonly utilised sorbent for ESI is hydrated lime which has an
optimum temperature range of 500 to 570⁰C for 𝑆𝑂2 capture (Hall et al., 2012). The following
reaction takes place:
𝐶𝑎(𝑂𝐻)2 + 𝑆𝑂2 → 𝐶𝑎𝑆𝑂3 + 𝐻2 𝑂
SO2 is captured by reacting directly with hydrated lime to form CaSO 3 whilst in suspension in
the flue gas as it passes through the economiser. Calcium sulphite formation must however,
contend with the reaction between the plentiful CO 2 (from combustion) with the sorbent to
produce CaCO 3 .
The temperatures are not high enough to decompose Ca(OH) 2 , as such, approximately 10% of
the Ca(OH)2 will decompose to produce the more reactive CaO which reacts with SO x to form
CaSO 3 and some CaSO 4 . Sulphite formation dominates at temperatures below 550⁰C, however
with increase in temperature, dehydration of Ca(OH)2 increases and carbonation and
dehydration begin to dominate at the expense of sulphite formation (Lin and Shih, 2003).
Moreover, efficiency of SO x capture may be enhanced by injecting water into the duct work
between air preheaters and the existing particulate collector with the objective of hydrating any
unreacted calcium oxide which would have been formed from the decomposition of lime.
Laboratory experiments by (Zhai et al., 2017) demonstrated that spent sorbent can be
reactivated by hydrating with small amounts of water at between 100-200⁰C and then
recirculated to improve SOx capture by improving calcium utilisation to up to 30% compared
to the stream activated sorbent which had a calcium utilisation of up to 22%. According to
studies by (Ash, 2008) SOx collection efficiency of up to 80% can be obtained with ESI
systems.
2.2.1.3 Duct sorbent injection system
DSI systems are used to capture SOx pollutants directly from the flue gas duct between the air
preheater and particulate collector. The DSI system is currently in commercial use and
depending on the sorbent used, has been shown to capture not only SOx pollutants but HCL,
HF and Hg (Tsuchiai et al., 2000) DSI. The process entails uniformly injecting fine dry sorbent(
usually hydrated lime, sometimes sodium bicarbonate) into the flue gas duct at temperatures
usually between 120-180⁰C, such that the reaction with acidic SOx gases occurs within the
duct work and the resultant solid product is collected downstream in either an ESP or baghouse.
A dedicated absorber vessel is not required for DSI and the systems are simple, easy to operate
and the lower temperatures enable a wider range of sorbents to be utilised
Unreacted sorbent from the particulate collector can be recirculated to increase sorbent
utilisation. 50-60% SOx capture can be achieved with hydrated lime, whereas 80% capture is
possible with sodium bicarbonate, however sodium bicarbonate is expensive (H Yoon, 1989)
The Advanced silicate (ADVACATE) DSI system is an advanced version of duct spray. It
involves hydrating fresh CaO and mixing in one step with recycled solids to produce a highly
reactive non-crystalline calcium-silicate slurry with approximately 30% by weight of solids.
The slurry is then injected into a duct downstream of the air preheater to obtain 90% or more
of SO 2 capture (Hall et al., 2012)

12
Figure 2.4 Schematic of Duct Sorbent Injection (DSI) system (Taylor et al., no date)

2.2.1.4 Circulating Fluidized Bed (CBF)

This a semi dry process that is carried out in a dedicated reaction chamber placed down stream
of an air preheater (figure 2.5) and makes use of dry sorbent to reduce SO 2 emissions from flue
gas streams. An operation close to saturation temperature is required, for this reason, water is
added into the bed. Removal efficiencies of up to 97% can be achieved at Ca/S molar ratio of
1.2-1.5 (Ohenoja, Pesonen and Yliniemi, 2020)
Fresh sorbent and gas humidifying water are added to flue gas on the diverging wall of the
diverging venturi section of the CBF. Flue gas passes into the CBF reactor from the bottom
and the flows upwards through a venturi section to enter into an upper cylindrical vessel who
height is designed to cater for the mass of bed material so as to accomplish the required
residence time of approximately 3 seconds (Muzio and Often, 2012)
The reaction that take place in the CBF include:
𝐶𝑎(𝑂𝐻)2 + 𝑆𝑂2 ↔ 𝐶𝑎𝑆𝑂3 . 12𝐻2 𝑂 + 12𝐻2 𝑂
𝐶𝑎(𝑂𝐻)2 + 𝑆𝑂2 + 12𝑂2 + 𝐻2 𝑂 ↔ 𝐶𝑎𝑆𝑂4 . 𝐻2 𝑂
CFB systems have good mass transfer conditions form gas to solid phase as a result of intima te
mixing of solids with the gas and the high slip velocity between the two phases.

13
Figure 2.5 Schematic of circulating fluidised bed system (Muzio and Often, 2012)

2.2.2 Dry FGD advantages and disadvantages

Dry FGD systems have the followings advantages and disadvantages when compared to wet
limestone FGD technology.
Table 2.2.1 Advantages and disadvantages of dry FGD process (Asokan, Saxena and Asolekar,
2005)

Advantages
Cheaper unlined carbon steel can be used in
place of line carbon steel or solid alloy
construction which is required for wet FGD
which has a highly corrosive environment.
Generally, the capital cost for units less than
300 MW, the capital cost is lower than for
wet FG.
Disadvantages
For units larger than 300MW multiple
modules will be required resulting in large
inlet and outlet ductwork and damper
combinations. In this case, the wet FGD
process would be cheaper to install.

Dry scrubbing has lower pumping Dry process requires the use of relatively
requirements as well as overall power more expensive reagents which have to be
consumption. stored in steel and concrete silos, unlike
limestone-based wet FGD systems.

14
 The waste CaSO 3 and Ca(OH)2 produced
can be easily handled by conventional
pneumatic flash equipment.
Waste produced is suitable and stable for
landfilling purposes and can be disposed of
concurrently with fly ash.
A large volume of waste with little uses due
to its properties is produced whereas wet
FGD systems can produce industrial grade
gypsum.
Concurrent disposal of fly ash and the waste
solids precludes commercial sale of fly ash
for reuse in various applications such a
manufacture of bricks.

Dry FGD systems generally have lower
pressure drop across the absorber compared
to wet FGD absorbers.
Lower sorbent utilisation compared to wet
limestone systems. The stoichiometric ratio
for lime is higher than the limestone
stoichiometric ratio to achieve comparable
SO2 removals.

Sorbent injection processes use less

equipment compared to the wet FGD
system and consequently has lower
operations and maintenance costs.

Dry FGD systems are capable of capturing a

high percentage of gaseous mercury present
in the flue gas, provided the mercury is in
the oxidized form.
Liquid waste is not generated from dry FGD
systems unlike wet limestone systems which
produce a liquid waste stream which may
require the installation of a waste water
treatment plant to treat the liquid waste prior
to waste disposal. The waste treatment
system produces a small volume of waste
with high content of toxic metals including
mercury that must be disposed of in a
landfill.

2.3 Commercially Available sorbents for dry FGD

Several sorbents are commercially available for dry FGD technologies ranging from calcium-
magnesium- or sodium-based sorbent materials. The composition of each sorbent varies,
consequently the desulphurisation efficiency is dependent on the nature of the alkaline sorbent.
The choice of sorbent depends upon the type of FGD process to be implemented. According to
(Lee et al., 2005) it is important that the desulphurisation product formed is thermally stable at
the furnace temperature as thus has a direct effect on the efficiency of sulphur removal. Alkali
earth metals such as magnesium, calcium, barium and strontium produce sulphates that are
table at elevated temperatures (Hall et al., 2012). Calcium based sorbents are the most abundant

15
and least expensive and therefore widely used. Table 2.2 shows the typical chemical and
physical properties of several calcium based commercially available sorbents.
The performance of these sorbents relies on the interaction of their chemical and physical
properties as well as the thermal environment to which they are injected (Ahmaruzzaman and
Gupta, 2012)
Table 2.2.2 typical properties of commercially available sorbents (Muzio and Often, 2012)

Type Formula Chemical analysis wt% Physical properties

Theoretical Actual Particle Surface
Ca Mg Ca Mg size/um are/m2/g
Limestone CaCO3 40 0 37- 0.4- 7.0-13 1-6
40 .5
Dolomite CaCO3MgCO3 22 13 21- 11- 12-37 0.5 – 1.0
25 12
High Ca(OH)2 54 0 49- 0.2- 2-4 12-21
Calcium 52 1.4
Hydrate
Dolomite Ca(0H)2MgO(Atmospheric 36 22 28- 18- 14-20 10-21
hydrate hydrated dolomite) 30 19
Ca(OH)2Mg(OH)2 30 18 29- 16- 1-4 19-20
(Pressure hydrated 30 18
dolomite)
For the purposes of this research work, Ca(OH)2 sorbent will be investigate as it the most
widely used sorbent for dry FGD because of its high calcium content and relatively higher
surface areas compared to the other commercial sorbents as shown on the table above. (Renedo,
2003)
2.4 Coal fly ash
CFA is a siliceous material that consists largely of silica. Several studies have shown that CFA
is a viable siliceous material that is applicable for preparation of highly active porous sorbent
for dry FGD (Ahmaruzzaman and Gupta, 2012).
2.4.1 Coal fly ash Properties
CFA is one of the products of coal combustion. It is a heterogeneous material which is
composed of fine particulates. CFA is carried out in the flue gas and is typically collected from
the flue gas by either fabric filters or electrostatic precipitators. Coal fly ash is usually disposed
as slurry in landfills or ash ponds (figure 2.6) together with bottom ash.

16
Figure 2.6 Ash pond site for disposal of fly and bottom ash

The physical and chemical properties of CFA influence its properties which in turn determine
its applications for reuse as well as disposal options. The properties of CFA depend on the type
of coal, the combustion conditions and several other factors. Average particle size of CFA is
typically 20µm with a low to medium bulk density ranging between 0.54-0.86 g/cm and high
surface area between 300-500m2 /kg (Kikuchi, 1999) The apparent colour of the CFA particles
is influenced by the unburnt carbon and iron content. The pH values of CFA varies from 1.2 to
12.5, with a majority of the ashes being alkaline (Asokan, Saxena and Asolekar, 2005).
The Ca/S molar ratio in the ash determines the pH of the ash-water system during hydration,
albeit other minor alkalis and alkaline earth cations also contribute to the pH value (Lee et al.,
2005)
Investigations into the micromorphology of CFA particles have reported that the majority of
the particles are spherical in shape with solid spheres, cenospheres and irregular shaped debris
as well as unburnt carbon (figure 2.7). CFA particles are generally hydrophilic. The
microstructure of CFA has been shown to influence its sorption characteristics (Telesca et al.,
2013)

17
Figure 2.7 Morphology of coal fly ash particles (Asokan, Saxena and Asolekar, 2005)

Fly ash is a pozzolanic material whose primary components (accounting for about 87%) are
silica, alumina, calcium oxide and iron oxides with smaller amounts of sulphur, alkalis,
magnesium and trace quantities of a number of other elements. The composition of fly ash
varies depending on the coal type. Typical fly ash composition from 7 different studies is
presented in table 2.3.
Table 2.2.3 fly ash compositions from seven different studies (Ogenga et al, 2008)

SiO2 % Ca0% Al2 O3 Fe 2 O3 MgO TiO2 K2 O Na2 O

1 32.83 30.35 13.34 5.61 4.51 - 1.37 2.15
2 48.45 16.56 17.30 5.60 2.95 - 2.90 2.57
3 21.04 51.02 7.310 3.01 3.09 - 0.85 1.48
4 59.00 1.60 26.70 - 0.90 1.30 5.50 1.20
5 60.00 3.00 20.00 4.70 1.00 - 1.10 -
6 49.26 1.91 30.24 6.92 0.85 - 2.44 0.64
7 30.30 2.50 47.20 9.60 1.91 2.20 3.00 1.70

2.5 CFA- conditioned sorbent

It has been cited in literature that the amorphous silica in the fly ash can react with hydrated
lime in the presence of water, to produce calcium silicate hydrates (xCaO.SiO r.yHrO), which
results in sorbents with higher specific surface area (figure 2.8) (Karatepe, Meriçboyu and
Küçükbayrak, 2016)

18
CFA can react with the hydroxides of alkali metals as well as alkali earth metals in the presence
of water. This pozzolanic reaction can take place at ambient temperatures and can be expressed
by the following equations:
𝐶𝑎(𝑂𝐻)2 + 𝑆𝑖𝑂2 + 𝐻2 𝑂 → (𝐶𝑎𝑂)𝑥 (𝑆𝑖𝑂2 )𝑦 (𝐻2 𝑂)𝑧

(Calcium silicate hydrates)

𝐶𝑎(𝑂𝐻)2 + 𝑆𝑖𝑂2 + 𝐴𝑙 2 𝑂3 → (𝐶𝑎𝑂)𝑥 (𝐴𝑙2 𝑂3 )𝑦 (𝐻2 𝑂)𝑧

(Calcium aluminate hydrates)

𝐶𝑎(𝑂𝐻)2 + 𝑆𝑖𝑂2 + 𝐴𝑙 2 𝑂3 + 𝐻2 𝑂 → (𝐶𝑎𝑂)𝑥 (𝑆𝑖𝑂2 )𝑦 (𝐴𝑙2 𝑂3 )𝑧 (𝐻2 𝑂)𝑤

(Calcium aluminate silicate hydrates)

𝐶𝑎(𝑂𝐻)2 + 𝑆𝑂3 + 𝐴𝑙 2 𝑂3 + 𝐻2 𝑂 → (𝐶𝑎𝑂)𝑥 (𝐶𝑎𝑆𝑂3 )𝑦 (𝐴𝑙2 𝑂3 )𝑧 (𝐻2 𝑂)𝑤

(Calcium aluminate calcium sulphate hydrates)

According to (Taylor et al., 2014), the products of the pozzolanic reaction are mostly poorly
crystallised and have a very high surface area. This reaction first proceeds by dissolution of
vitreous phase silica and/or alumina by alkaline water. Kinetic studies have shown that this
reaction is the rate limiting step. The calcium aluminate and silicates form and precipitate on
the surface of the CFA(Ishizuka et al., 2000). Studies by (Lin and Shih, 2003) showed that
the surface area of the CFA conditioned sorbent and its accessible alkalinity greatly affect the
sorbent’s reactivity towards SO 2.
(Lin, Shih and Liu, 2003b) showed that SiO 2 present in the fly ash (quartz or amorphous), CaO
content and particle size influence the sorbent surface area. However, studies by (Renedo and
Ferna, 2002) showed that sorbent activity does not seem to be influenced by the chemica l
species which constitute the sorbents. The important parameters and properties of CFA which
make it applicable for sorbent conditioning are summarised in table 2.4

19
Figure 2.8 Particle morphology of hydrated sorbent vs. commonly used industrial sorbent.
(Ahmaruzzaman and Gupta, 2012)

Table 2.2.4 Important properties and preparation parameters for CFA utilisation in sorbent
preparation

CFA Property Process parameters

Specific surface area Reaction temperature
Si/Ca molar ratio Presence of moisture and pressure
Unburned carbon content Gas flow rate and CFA loading
Unburned carbon surface area Flue gas composition
Column height
Chemical treatment.

2.5.1 Fly ash-conditioned sorbent preparation variables

Sorbent preparation conditions are important because they influence the physical and chemica l
properties of the sorbent which in turn affect performance of the conditioned sorbent (Ishizuka
et al., 2000). It is essential that these variables are optimised so as to produce a sorbent with
the best chemical and physical properties which will enhance its utilisation and SOx removal
efficiency (Renedo, 2003). Generally, higher sulphur removal efficiency correlates with higher
sorbent surface area, to that end, the main aim in sorbent synthesis is to increase sorbent surface
area by optimising the hydration conditions (Lee et al., 2006).
20
 2.5.1.1 Hydration Temperature
Most chemical reactions are influenced by temperature changes. (Foo et al., 2011)
demonstrated the temperature, pressure and the water to solids ratio are not individua lly
significant but their crossed influences are. The studies showed that the highest value for the
specific surface are of the conditioned sorbent corresponded to sorbents prepared at 170⁰C,
with hydrated lime to fly ash ratio of 3:1 and hydration time of 4 hours as well as lowest solids
ratio. It was cited in literature that high temperature, together with other variables contributed
to the increase in surface area of the sorbents formed (Lin and Shih, 2003). Research on
hydration variables on Ca(OH)2 /fly ash sorbent utilisation reported that longer mixing time as
well as higher temperatures produce sorbent with higher activity (Ogenga et al, 2008)
2.5.1.2 Hydration time
Most researchers concur that longer hydration time result in larger surface area of the resultant
sorbent which translates to improved sorbent utilisation. Studies by (Lin, Shih and Liu, 2003a)
demonstrated increase in surface with increase in hydration time. Dissolved calcium content
in the slurry filtrate after hydration varied inversely with hydration time and fly
ash/Ca(OH), weight ratio. The specific surface area of sorbents conditioned under varying
hydration times were found to increase with the hydration time. According to (Richardson et
al., 2013) hydration parameters that positively affect the resultant sorbent’s surface area are
hydration time and quantity of fly ash and Ca(OH)2 used. The values of these variables obtained
in the research had limitations of long hydration periods (32 hours) which may not be
applicable in practice due to practical constraints and economic considerations hence the need
to optimize these variables so as to obtain practical hydration periods.
2.5.1.3 Calcium-based sorbent/Fly ash ratio
Different studies have reported different optimal ratios for preparation of high performance
sorbents. For hydrated lime, the performance of fly ash conditioned sorbent increases as the
ratio of Ca(OH)2 /fly decreases ( ash weight ratio reduction) . Studies by (Lin, Shih and Liu,
2003b) which were conducted to optimise surface area of the conditioned sorbent,
demonstrated that a ratio of CFA:CaSO 4 of 1:2.3 produced a maximum surface are of
62.2m2 /g. On the other hand, (Lau, Lee and Mohamed, 2011) reported a ratio of 3:17 of CFA
to Ca(OH)2 yielded the highest local maximum surface area of 257.6m2 /g. The quantity of
calcium silicate hydrates together with the microstructure of the conditioned sorbent,
remained almost the same during the period of the hydration time of between 25 min to
l6 h showing that the effect of hydration time on the surface area was small.
2.5.1.4 Additives
Amorphous silica in CFA reacts with hydrated lime in the presence of water to produce calcium
silicate hydrates which are more reactive towards SOx than the unconditioned sorbents. It has
been reported by (Ogenga et al, 2008), that the controlling step of the CFA and hydrated lime
reaction is the dissolution rate of alumina and/or silica from the vitreous phase into the aqueous
phase. Increasing temperature, reaction time and addition of additives have been shown to
accelerate the reaction rate. According to (Carpenter, 2012), the addition of CaSO 4 enhances
formation of calcium silicate by subduing the crystal growth of Ca(OH)2 which promotes the
sorbent conditioning to produce hydrated products. The presence of CaSO 4 buffers the solutio n
by maintaining high calcium levels during the hydration process. As a result, the formation of
calcium silicates is accelerated as calcium reacts with dissolved silica. However, studies by
(Ishizuka et al., 2000), reported that while the desulphurisation activity was higher than that of

21
Ca(OH)2 alone, adding CaSO 4 resulted in poor performance with regards to SO 2 capture for
sorbents conditioned with CFA.

22
3.0 Methodology
Experiments were carried out for the investigation of the influence of hydration time and
particle size distribution on the pH of CFA hydration solution so as to provide a basis for using
CFA conditioned absorbent. The relationship between preparation variables and Calcium
hydroxide conversion was then investigated to provide a quantitative expression of the exte nt
of the pozzolanic reaction. Moreover, the desulphurisation activity of the CFA conditio ned
sorbent was tested and compared with that of commercial hydrated lime sorbent.

3.1 Objectives of the experiments

1. To determine the chemical composition of CFA using X-Ray fluorescence
2. To determine the influence of hydration time and particle size distribution on the pH of
the CFA hydration solution.
3. To prepare solid CFA-conditioned sorbent from hydrated lime using differe nt
preparation hydration periods as well as initial CFA/Ca(OH) 2 raw material ratios.
4. To determine the extent of calcium conversion of the fly ash hydrated sorbents.
5. To determine the influence of hydration time, Ca(OH)2 conversion and CFA: Ca(OH)2
raw material ratio on sorbent desulphurisation activity.
6. To compare the desulphurisation activity of CFA-conditioned sorbent with commercia l
hydrated lime sorbent.

3.2 Equipment and chemicals utilised

Table 3.1 Materials and methods

Equipment and apparatus Chemicals

Oven Calcium hydroxide
Furnace Calcium carbonate
Desiccator Calcium oxide
Mechanical Sieve Concentrated sulphuric acid
Laboratory balance Coal Fly Ash
250ml beaker EDTA
pH meter Hydrochloric acid
0.45micron filter mesh Barium chloride
250ml Conical flask Eriochrome black T indicator
Rubber stopper Barium chloride
Motor and pestle Sodium thiosulphate

23
 Stopwatch
Pipette
Burette
Graduated volumetric flask
Measuring cylinder
Suction bulb
Tripod stand
Mercury Thermometer
Stirrer analytical balance

3.3 Procedure
CFA was supplied by ZPC Hwange power station. The chemical composition of CFA is the
basis for its application in synthesis of high activity dry FGD sorbents. X-ray fluoresce nce
(XRF) analysis was used to determine the chemical composition of the fly ash. This was
followed by determination of the loss on ignition of the fly ash to express its unburnt carbon
content.

The investigation of the utilisation of CFA and Ca(OH) 2 for preparation of high performance
sorbent was carried out by first investigating fly ash hydration. The basis for reuse of CFA as
reagent for silica enhanced sorbent is its ability to increase sorbent utilisation through the
pozzolanic reaction between CFA and Calcium based sorbent in the presence of water to form
highly hydrated and reactive CaO.SiO 2 .Al2 O3 .H2 O systems. (Ahmaruzzaman and Gupta,
2012).

The fly ash hydration experiment was then followed by solid sorbent preparation using
different ratios of CFA: Ca(OH)2 sorbent as well as hydration time period. Calcium conversion
was calculated for the sorbents in a bid to establish a quantitative expression of the extent of
the pozzolanic reaction between the fly ash and Ca(OH) 2 . The effect of the variations in
preparation procedures on the extent of the pozzolanic reaction between CFA with Ca(OH)2
was also investigated.

Moreover, desulphurisation activity of the solid sorbents was investigated to compare the
influence of hydration time and Ca(OH)2 ratio on the desulphurisation performance of the solid
CFA conditioned sorbents as well as compare its performance to that of the commercia l
hydrated lime sorbent

24
3.3.1 Fly ash preparation
The rationale for investigating the influence of hydration time and particle size distribution on
fly ash hydration was to confirm the influence of these parameters on the CFA hydration
solution pH. It is documented in literature that the reactivity of hydrated fly ash/Ca(OH) 2
sorbent towards SO 2 depends mainly on surface area and accessible alkalinity, the pH value of
the hydration solution therefore plays an important role in the desulphurisation behaviour of
the hydrated sorbent (Karatepe, Meriçboyu and Küçükbayrak, 2016).

3.3.1.1 CFA Characterisation

The chemical composition of CFA is the basis for its applicatio n in synthesis of high activity
dry FGD sorbents. X-ray fluorescence (XRF) analysis was used to determine the chemica l
composition of the fly ash.

This was followed by determination of the loss on ignition (LOI) of the fly ash to express its
unburnt carbon content. Five samples of fly ash were weighed in crucibles and then placed in
a dry oven at 110⁰C for 1 hour to remove moisture. The five CFA samples were then placed in
a furnace at 650⁰C for 2 hours (fig 3.1). After that, the fly ash samples were removed from the
furnace, cooled in a desiccator at room temperature and then weighed again using an analytic a l
balance. The loss on ignition was then calculated using the formula:

𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑎𝑚𝑝𝑙𝑒 − 𝐹𝑖𝑛𝑎𝑙 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑎𝑚𝑝𝑙𝑒

𝐿𝑂𝐼 = × 100%
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑎𝑚𝑙𝑒

25
Figure 3.1 Laboratory furnace

3.3.1.2 Sieving.
A mechanical sieve (Fig 3.2) was used to obtain CFA of different size ranges and also to assist
in detecting and removing large none CFA particles which could contaminate the samples.

26
Figure 3.2 Mechanical sieve shaker

3.3.2 Fly Ash hydration

Hydration experiments were carried out on the CFA obtained from the sieving experiment with
5 different particle size distribution (obtained from the sieving procedure), so as to confirm the
influence of particle size distribution and hydration time on the hydration of the fly ash
solutions. 20 gram samples of fly ash with different size distributions were weighed and added
into a 200ml beaker. 100ml of water was added to each batch to prepare the fly ash solutio n.
The mixtures were stirred with a magnetic stirrer at 250rpm for a period of 2 hours. The pH
was measured for each mixture after 30 minute intervals. The values obtained were tabulated
as shown on table 3.2.

Table 3.2 Fly ash hydration results

Particle Batch 1 Batch 2 Batch 3 Batch 4

size Hydration pH Hydration pH Hydration pH Hydration pH
distribution time Time Time Time
of CFA

27
 d1
d2
d3
d4
d5

3.3.3 Sorbent Preparation

The aim of CFA-conditioned sorbent synthesis was to maximise the sorbent surface area and
calcium utilisation by optimising hydration conditions. According to (Lee et al., 2005) calcium
utilisation is a function of period of hydrothermal treatment of the absorbent prepared by
different procedures.

The sorbents were prepared using CFA provided by ZPC HEP together with reagent grade
Ca(OH)2 powder using the water hydration method. Varying the amounts of CFA and Ca(OH)2
depending on the CFA/Ca(OH)2 (table 3.3) was added to water at 90⁰C. A water to solids ratio
of 5:1 was maintained for all the samples that were prepared. The preparation conditions of the
sorbent such as amount of starting materials was selected according to an optimisation study
by (Lee et al., 2005). The slurry temperature was maintained at 90⁰C for 1-4 hours and the
mouth of the conical flask was plugged with a rubber stopper to prevent water loss and carbon
dioxide interference. Samples were withdrawn at different hydration times (1 hour intervals)
for each of the batches and then filtered with a 0.45micron filter. The sorbents were then dried
in an oven at 110⁰C and then crushed to powder using a pestle and mortar.

Table 3.3 CFA/Ca(OH)2 raw material ratios

CFA/Calcium based Mass of CFA/g Mass of Ca(OH)2 /g

sorbent ratio
1/3 37.5 75.2
5/3 93.75 56.25
9/3 112.5 37.5
15/3 125 25

3.3.4 Determination of extent of hydration

The products formed by reaction of Ca(OH)2 with fly ash were dissolved by adding the
prepared solid to 0.1 M HCl and stirring for five minutes with a magnetic stirrer. After filtra tio n

28
of the mixture using 0.45micron filter paper, the solid cake was discarded and the filtrate, with
the dissolved products of the reaction, was analysed by titration with ethylene diamine tetra
acetic acid (EDTA) for Calcium ions.

The Ca(OH)2 that remains unreacted in the prepared sorbent was obtained and Ca(OH)2
conversion was calculated as:

𝐶𝑎( 𝑂𝐻) 2 𝑢𝑠𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑝𝑟𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑟𝑏𝑒𝑛𝑡 −𝐶𝑎( 𝑂𝐻) 2 𝑎𝑓𝑡𝑒𝑟 ℎ𝑦𝑑𝑟𝑎𝑡𝑖𝑜𝑛
𝐶𝑎(𝑂𝐻)2 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 % = ×
𝐶𝑎( 𝑂𝐻) 2 𝑢𝑠𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑝𝑟𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑖𝑑

100%

3.3.5 Desulphurisation activity test

On account of unavailability of sophisticated equipment which can simulate the conditions in
in-duct sorbent injection post coal combustion at elevated temperatures, the desulphurisa tio n
activity test was conducted only to serve as an indication of the sorbent activity as influe nced
by the sorbent preparation conditions (hydration time, raw material ratio and Ca(OH)2
conversion). SO 2 gas was generated by reacting concentrated H2 SO 4 with copper pieces
according to the equation:

𝐶𝑢(𝑠) + 2𝐻2 𝑆𝑂4 (𝑙 ) → 𝐶𝑢𝑆𝑂4 (𝑎𝑞) + 2𝐻2 𝑂(𝑙 ) + 𝑆𝑂2 (𝑔)

Concentrated sulphuric acid was reacted with small copper pieces in an Erlenmeyer flask with
a rubber stopper to produce SO 2 gas which was then conveyed into a second Erlenmeyer flask
containing 20g of the CFA-conditioned sorbents which is heated using a hot plate at 80⁰C. The
SO2 and sorbent were left to contact for 2 hours with intermittent shaking of the flask every 20
minutes to enhance gas-solid contact.

The absorption of SO 2 by the solid sorbent has been reported in literature to produce CaSO4
(Renedo and Ferna, 2002). To quantify the extent of desulphurisation, the concentration of
sulphate ions was determined by an indirect titration with EDTA. The sample was first
dissolved in 0.1M HCl and then filtered. The residue was discarded and the filtrated was then
titrated with excess 0.5M BaCl2, stirred for an hour on a hot plate at 80⁰C and then cooled and
set aside for 24 hours to precipitate sulphate ions as BaSO 4. According to (Belle-oudry, 2008),
the precipitation requires at least 24 hours to come to completion. After the 24 hours, a known
volume of the liquid sample was then titrated with 0.5M EDTA to determine the concentratio n
of excess barium ions which will have not reacted. The concentration of sulphate ions in the
sample was then calculated using the equation below:

29
 (𝑇𝑜𝑡𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑎𝑑𝑑𝑒𝑑 𝐵𝑎2+ ) − (𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑒𝑥𝑐𝑒𝑠𝑠 𝐵𝑎2+ )
𝑆𝑂42 − 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 =
𝑉𝑆𝑂42−

The same procedure was repeated for commercial lime sorbent.

30
4.0 Results and discussion
4.1 CFA characterisation
4.1.1 XRF Analysis results:
The XRF analysis results are presented in table 4.1 below.

Table 4.1 XRF analysis results

Component Composition/%
Al2 O3 29.80
CaO 0.89
Fe 2 O3 10.8
MgO 0.29
SiO2 54.33
SO3 0.40
The results for XRF analysis of CFA showing the main components of interest in this study
are presented in table 4.1 above. As displayed in the table the main constituents of CFA are
silica (SiO 2 ), alumina (AL2 O3 ) and ferric oxide (Fe2 O3 ), constituting 94.94% by composition
of the CFA. The calcium content in the fly ash is very low, with only 0.89%.

4.1.2 CFA Loss on Ignition Results

LOI/%
9
8
7
6
5
LOI/%

4
3
2
1
0
A B C D E
Sample

Figure 4.1 Loss on ignition results for different fly ash samples

31
Figure 4.1 shows the graph of loss on ignition for 5 samples of the CFA. The loss on ignitio n
values for the samples range from 7.452575 to 9.364294%, with an average of 8.260438 %. The
loss on ignition values are shown in table A1 (Appendix). The loss in mass, however, cannot
only be attributed to the combustion of unburnt carbon content, as CFA usually contains several
contaminants which are also volatised upon heating in the furnace, resulting in decrease in
mass of the samples.

Figure 4.2 fly ash samples prior to heating in furnace

Figure 4.3 fly ash samples after heating in furnace

The CFA samples were initially a darker shade of grey (figure 4.2) prior to heating in the
furnace. The colour of the samples changed to a lighter shade of grey as shown in figure 4.3.
The colour change in the samples after heating in the furnace is as a result of combustion of
unburnt carbon content in the fly ash samples. The initial darker colour can be attributed to

32
high unburnt carbon content which is indicated by the relatively high loss on ignitio n
percentages presented in figure 4.1.

4.1.3 Sieve Analysis Results

Particle size distribution

120

100
Cumul ative % Pa ssing

80

60

40

20

0
0 50 100 150 200 250 300 350 400
Si eve arperture size/µm

Figure 4.4 Particle size distribution of fly ash

The graph in Figure 4.4 shows that approximately 74.74% (by mass) of the sample pass through
the 180µm sieve. The size range obtained from the sieving experiment confirmed that CFA is
predominantly made up of fine particles. This size range, coupled with the spherical shape of
CFA, improves the fluidity of CFA which contributes to its pozzolanic activity. This means
that it will react with calcium hydroxide at ambient temperatures and in the presence of water
(Ahmaruzzaman and Gupta, 2012).

33
4.2 Fly ash hydration results
11

10.5

10

9.5

9
pH

8.5

7.5

6.5

6
0 20 40 60 80 100 120 140 160
Hydration time/mns

d1= 355µm d2= 300µm d3=180µm d4= 120µm d5 = 90µm

Figure 4.5 effect of hydration time on pH of fly ash hydration solution

The graph in figure 4.5 shows the influence of hydration time for different particle sizes on pH
of the CFA hydration solution. As hydration time increased, (first 90 minutes for d3 -d5 and first
120 minutes for d1 -d2 ), so the pH of the CFA hydration solution. This was followed by a
declining stage (approximately 30 minutes), in which the pH of the hydration solutio n
decreased. After the declining stage, pH of the solutions either increased or decreased by a
small margin compared to the first two stages. The maximum pH for the solution with smaller
sized particles (d3-d5) was reached after 90 minutes of stirring time whereas that of the larger
sized particles (d1-d2) was reached much later (120-150minutes). As shown in the graph, the
pH of the solution eventually started to decrease as hydration time increased.

CFA predominantly contains SiO 2 , Al2 O 3 , Fe2 O3 , and CaO. The pH of the hydration solutio n
increases with hydration time during the initial stages of CFA hydration owing to the fact that
the rate of CFA alkali oxides dissolution in the water would be very high leading to an increase
in the pH value of the solutions. However, with increase in hydration time, a decrease in pH is

34
exhibited due to the slowing of the alkali oxides dissolution facilitated by decrease in OH- ion
concentration in the solution as SiO 3 and Al2 O3 start to consume the hydroxide ions as they
react to form calcium silicate and calcium aluminate (Richardson et al., 2013).

11

10.5

10

9.5

9
pH

8.5

7.5

6.5

6
0 50 100 150 200 250 300 350 400
particle size/µm

HT=30mins HT= 60mins HT=90mins HT= 120mins HT= 150mins

Figure 4.6 Effect of particle size on pH of fly ash hydration solution

The graph in figure 4.6 above depicts the influence of particle size on CFA hydration solutio n
pH. The hydration time was held constant for each sample, with only the particle size being
varied. As it can be seen from the graphs, the pH value increased with increase in particle size.
90µm diameter particles exhibited the highest pH for all the graphs with differing hydration
periods. The maximum pH reached was 9.9 for 90µm sized particles with 90 minutes of
hydration time. The minimum pH was 7.3 for 355µm sized particles with 30 minutes of
hydration time.

The pH of the hydration solution increased with decrease in particle size of the CFA particles
owing to the large surface area in relation to volume ratio of the smaller sized particles which
accelerates the rate of dissolution. Smaller sized particles ensure more contact between the
particles by exposing more of the surface of the particles to the water for dissolution. It should
also be noted that the influence of particle size on the surface area of smaller particles is limited
as CFA particles have micropores which facilitate infiltration of water molecules within the

35
particle effecting accelerated dissolution rate (Lee and Koon, 2009). This was exhibited by
similar pH behaviour of the smaller sized particles (d3 –d5 ).

Since preparation of high activity sorbents from fly ash is based on the silica content of fly ash
as well as its accessible alkalinity, the particle size range of CFA of 90-180µm was selected
for subsequent sorbent preparation as this size range exhibited highest alkalinity.

4.3 Sorbent preparation results

Figure 4.7 CFA/Ca(OH)2 sorbent

Figure 4.7 above show the appearance of the CFA hydrated sorbent after drying in an oven for
1 hour and prior to crushing. The solid sorbents had variations in colour depending on the raw
material ratio of CFA to Ca(OH)2 which was added. The sorbents prepared with the highest
CFA ratio had a darker colour compared to the ones with less CFA added.

36
4.4 Ca(OH)2 conversion results
80

75

70
Ca(OH)2 Conversion/%

CFA/Ca(OH)2 g/g = 0.33

65
CFA/Ca(OH)2 g/g = 1.67
CFA/Ca(OH)2 g/g = 5
CFA/Ca(OH)2 g/g = 3
60

55

50
0 50 100 150 200 250 300
hydration time/mins

Figure 4.8 Effect of hydration time on CA(OH)2 conversion

The graph in figure 4.8 displays the influence of hydration time on Ca(OH)2 expressed as a
plot of Ca(OH)2 conversion versus hydration time. As depicted in the graphs, there was a
general increase in the Ca(OH)2 conversion for all initial raw material ratios with increase in
hydration time. The highest conversion was 74.78% for sorbent prepared with the highest CFA:
Ca(OH)2 g/g raw material ratio (15:3) with 180 minutes of hydration time. The lowest
conversion (59%), was for sorbent prepared with raw material ratio of 5:3 with a hydration
time of 60 minutes. Further increase in hydration time, that is greater than 180 minutes, showed
a less profound increase in Ca(OH)2 conversion, as shown by the relatively smaller increase in
Ca(OH)2 conversion of 70.5 to 70.65% for CFA:Ca(OH)2 ratio =5(9:3) and 67.15 to 68.35%
for CFA:Ca(OH)2 ratio =0.33 (1:3) for hydration time greater than 180 minutes.

37
 Hydration period = 240mins
75

74

73
Ca(OH)2 conversion/%

72

71

70

69

68
0 1 2 3 4 5 6
CFA:Ca(OH)2/ g/g

Figure 4.9 effect of CFA/Ca(OH)2 raw material ratio on Ca(OH)2 conversion

The influence of raw material ratio on Ca(OH)2 is also presented in the graph in figure 4.9,
which displays the change in conversion with increase in raw material ratio for the sorbents
prepared with 240 minutes of hydration time. The Ca(OH)2 conversion increased with increase
in raw material ratio.

It is worth noting that according to (Liu, Shih and Lin, 2002), silica dissolution from CFA is
the rate limiting step in the pozzolanic reaction of Ca(OH)2 with CFA. As such, the reaction
rate increased as the concentration of SiO 2 increased in the reaction mixture. This explains the
increase in Ca(OH)2 conversion with raw material ratio. Thus for CFA: Ca(OH)2 ratios of 9:3
and 15:3 the highest conversion was achieved as compared to CFA: Ca(OH)2 ratios of 1:3 and
5:3.

38
4.5 Desulphurisation activity results
1.21

1.2

1.19

1.18
SO42- concnetration/ 10-3 mol /l

1.17
HT= 60mins
1.16
HT= 120mins

1.15 HT= 180mins

HT= 240mins
1.14

1.13

1.12

1.11
0.00 1.00 2.00 3.00 4.00 5.00 6.00
CFA/Ca(OH)2 ratio/g/g

Figure 4.10 Effect of CFA:Ca(OH)2 raw material ratio on desulphurisation activity

The desulphurisation activity of the prepared sorbent was expressed by the concentration of
sulphate ions in the sulphation reaction between SO 2 and the prepared sorbent. The influe nce
of raw material CFA: Ca(OH)2 ratio on the desulphurisation activity is presented in figure 4.10.
The results showed that the extent of desulphurisation initially increased and then decreased
with increase in CFA: Ca(OH)2 ratio. The maximum extent of desulphurisation, with a
concentration of 1.19675 × 10−3 𝑚𝑜𝑙/𝑙 concentration of SO 4 2- , was encountered for the
sorbent prepared with CFA: Ca(OH)2 ratio of 5:3 and 240 minutes of hydration time. The
minimum extent of desulphurisation, with a concentration of 1.12175 × 10−3 𝑚𝑜𝑙/𝑙
concentration of SO 4 2- , was encountered for the sorbent prepared with CFA: Ca(OH)2 ratio of
9:3 amd120 minutes of hydration time. For the sorbents which were prepared with 120 and 180
minutes of hydration time, the graphs had two stages- wherein the first stage was marked by a
decrease in SO 4 2- ion concentration in the products with increase in CFA: Ca(OH)2 raw material
ratio, followed by a second stage in which there was an increase in in SO 4 2- ion concentratio n
in the products with increase in CFA: Ca(OH)2 raw material ratio.

39
The initial increase in SO 4 2- ion concentration in the product solids was marked by an increase
in calcium hydroxide conversion (which means more of the calcium-alumina-silicate complex
is formed which enhances the desulphurisation process), with increase in CFA: Ca(OH)2 ratio
during sorbent preparation. However, as the CFA:Ca(OH) 2 ratio was further increased, the
SO4 2- ion concentration in the product solids decreased due to the presence of high quantity of
unreacted CFA present as the sorbent would be a mixture of reacted and unreacted products.

1.22

1.2

1.18
SO 4 2- concentration/10 -3 mol/l

1.16
CFA/Ca(OH)2 ratio= 0.33
CFA/Ca(OH)2 ratio= 1.67
1.14 CFA/Ca(OH)2 ratio= 3
CFA/Ca(OH)2 ratio= 5

1.12

1.1

1.08
60 120 180 240
Hydration time/ minutes

Figure 4.11 effect of hydration time on desulphurisation activity

The graph in figure 4.11 presents the influence of sorbent preparation hydration time on the
activity of the sorbent. The highest SO 4 2-ions concentration in the products occurred after a
hydration period of 180 minutes. The longer the hydration time during sorbent preparation, the
more time for the pozzolanic reaction to progress and produce products with higher surface
area which increases sorbent utilisation (Taylor et al., no date).

40
 1.2

1.19
SO42 concentration/10-3 mol/L

1.18

1.17

1.16

1.15

1.14
55 57 59 61 63 65 67 69 71 73
Ca(OH)2 conversion/%

Figure 4.12 Effect of Ca(OH)2 conversion on desulphurisation activity

The graph in figure 4.12 displays the influence of Ca(OH)2 conversion on the concentration of
SO4 2- ions which is produced during the desulphurisation process for the sorbent prepare with
CFA:Ca(OH)2 ratio. The increase in conversion resulted in an increase in the concentration of
SO4 2- ions, with the maximum concentration of1.1968 × 10−3 𝑚𝑜𝑙/𝑙 for Ca(OH)2 conversio n
of 70.5%. A higher Ca(OH)2 conversion means that more hydrated and reactive
CaO.SiO 2 .Al2 03 .H2 0 systems which result in increased reactivity, producing higher
concentration of SO 4 2- ions in the solid products after the desulphurisation activity tests.

41
 1.3

1.2
SO42- concentration/10-3mol/l

1.1

0.9

0.8

0.7
0 50 100 150 200 250 300
Hydration time/mins

CFA hydrated sorbent Commercial lime sorbent

Figure 4.13 Desulphurisation activity for CFA conditioned sorbent an commercial lime
sorbent

The graph in figure 4.13 above shows the difference in SO 4 2-ions concentration in the products
of the CFA conditioned sorbent and hydrated lime alone. The graph for CFA conditio ned
sorbent had higher SO 4 2-ions concentration in the products as compared to that of the
commercial lime sorbent. The difference was as a result of conditioning of hydrated lime with
CFA results in the formation of calcium-alumina-silicates with enhance surface area and pore
volume, this improves the utilisation of calcium in the sorbent for the removal of S02 . The
highest SO 4 2-ions concentration for the commercial hydrated lime sorbent was0.8559 ×
10−3 𝑚𝑜𝑙/𝑙. The smaller surface area in relation to volume of the commercial lime sorbent
results in reduced activity towards the S0 2 gas. During desulphurisation, the sorbent particles
capture SO 2 gas at the surface, while the inner surface remains unreacted (Telesca et al., 2013).
However, for CFA conditioned sorbent, the hydrated CaO.SiO 2 .Al2 03 .H2 0 systems had a larger
surface area which enables enhanced contact between SO 2 gas and the sorbent.

4.6 Summary and conclusions

The experimental results presented in this work focused more on the reaction of CFA with
Ca(OH)2 and less on the reaction of the prepared solid sorbent with SO 2 . The reactivity of the
42
prepared solid towards SO 2 was determined to serve as an indication of the extent of reaction
of CFA with Ca(OH)2 using different preparation conditions as well as to compare
desulphurisation activity of the CFA hydrated sorbent and commercial sorbent.

Water hydration of CFA with Ca(OH)2 was carried out under mild reaction conditions(
Temperature maintained at 100⁰C) to produce hydrated CFA/Ca(OH)2 sorbent with improved
reactivity towards SO 2 . In order to enhance sorbent performance, preparation variables such as
CFA:Ca(OH)2 raw material ratio and hydration time were varied and their influence on the
extent of pozzolanic reaction (quantified as Ca(OH)2 conversion) and desulphurisation activity
were determined.

The first step, after CFA characterisation was to study the influence of CFA particle size on
CFA hydration. The particle size of CFA influences the accessible alkalinity (pH) of the fly
ash hydration solution which enhances the hydration process. Smaller sized particles have a
larger surface area which enhances dissolution of the fly ash components which participate in
the pozzolanic reaction between CFA and Ca(OH)2 . Fly ash particle size ranging from 90-
125µm, exhibited the highest pH and were thus used as the raw material for sorbent preparation.

The extent of the pozzolanic reaction between CFA and Ca(OH)2 was quantified as Ca(OH)2
conversion, which gave an indication of the amount of Ca(OH)2 which is converted to calcium
silicates during hydration. The results showed that conversion increased with increase in
CFA:Ca(OH)2 ratio, reaching a maximum of 74.78% for CFA:Ca(OH)2 = 15:3. Ca(OH)2
conversion also increased with increase in hydration time, however the results also showed that
this increase, although initially profound, slowed down with further increase in hydration time
after the first 180 minutes.

The desulphurisation activity results of the sorbents prepared with different raw material ratios
showed that Ca(OH)2 conversion and CFA:Ca(OH)2 ratio have a strong influence on the
activity of the CFA conditioned sorbents. CFA/Ca(OH)2 sorbent with CFA:Ca(OH)2 ratio of
5:3, 180 minutes of hydration time and 70.5% Ca(OH)2 conversion had the highest
desulphurisation activity expresses as 1.19675 × 10−3 𝑚𝑜𝑙/𝑙 of SO 4 2- ions in the product
solid.

43
5.0 Conclusion and Recommendations
5.1 Conclusion
CFA conditioned sorbent can be used to replace dry FGD commercial sorbents such as
limestone, lime and dolomite which are currently in use and have low SO 2 efficiency compared
to wet FGD systems. According to various literature studied in this research study, the reaction
of CFA with Ca(OH)2 produces hydrated calcium-silicate complexes of the general formula
xCaO.SiO 2 .yH2 O and CaO.SiO 2 .Al2 03 .H2 0 which have a larger surface area in relation to
volume and greater reactivity towards SO 2 .

CFA is used a source of amorphous silica and alumina which reacts with the Ca(OH)2 to
produce calcium and alumina silicates which play a role in the physical and chemica l
absorption of SO 2 gas from flue gas. The rate of dissolution of CFA in water is strongly
influenced by the particle size as shown by the fly ash hydration experiments which reveal that
pH of CFA hydration solution increases with decrease in CFA particle size. Decrease in particle
size results in increased alkalinity of the fly ash solution as a larger surface area of the CFA
particles is availed for contact with water (increased rate of dissolution). However, the particle
size of the fly ash should not be too fine as that would reduce permeability of the sorbent to
SO2 gas during desulphurisation. CFA hydration experiments show that particle size range of
90-125µm is the optimum particle size for use in sorbent preparation.

The extent of the pozzolanic reaction between CFA was quantified as Ca(OH)2 conversion,
which is an indication of the amount of Ca(OH)2 which reacts with the components of CFA to
form the calcium silicates. A maximum Ca(OH)2 conversion of 74.78% is achieved for the
highest initial raw material ratio of CFA:Ca(OH)2 = 15:3 and hydration time of 240 minutes.
This indicates the strong influence sorbent preparation variables, that is, hydration time and
initial CFA:Ca(OH)2 raw material ratio; have on the extent of the pozzolanic reaction between
CFA Ca(OH)2 . This work shows that while the hydration time initially has a strong influe nce
on the reaction, the effect of hydration time on Ca(OH)2 conversion becomes less pronounced
with further increase in hydration time ( beyond 180 minutes). At the early stages of CFA and
Ca(OH)2 hydration, there is rapid dissolution of both reactants. This facilitates the accelerated
progression of the pozzolanic reaction to form the hydrated calcium silicates and alumina -
calcium silicate complexes. However with prolonged hydration time the rate of dissolutio n
slows and the quantity of product hydrated calcium-alumina silicates only increases by a small
margin.

44
The extent of desulphurisation is noted by observing the concentration SO 4 2- ion in the product
solids. This study shows that the extent of desulphurisation is strongly influenced by Ca(OH)2
conversion and initial CFA: Ca(OH)2 raw material ratio. This influence is characterised by an
initial increase in the extent of desulphurisation with increase in CFA: Ca(OH)2 ratio. However,
further increase in CFA: Ca(OH)2 beyond 9:3, results in reduced sorbent activity. Sorbents
prepared with high CFA: Ca(OH)2 raw material ratio exhibit higher Ca(OH)2 , which indicates
a higher quantity of the reactive xCaO.SiO 2 .yH2 O and CaO.SiO 2 .Al2 03 .H2 0 systems. The
increase in surface area generated by the formation of hydrated calcium silicates results in
improved SO 2 capture. However, the presence of high quantity of unreacted CFA in the sorbent
for higher CFA:Ca(OH)2 ratio, results in decreased reactivity of the sorbent as some of the fly
ash particles would be covering the surface of the reactive species of the sorbent. Ca(OH)2
conversion as well as CFA:Ca(OH)2 raw material ratio parameters can be used to predict
sorbent behaviour in the desulphurisation reaction.

CFA conditioned sorbent exhibits higher desulphurisation activity compared to the commercia l
lime sorbent tested at the same conditions. The lower surface area of the commercial sorbent
results in lower desulphurisation performance as compared to the more reactive
CaO.SiO 2 .Al2 03 .H2 0 systems which possess higher surface area and pore volume.

This study shows that factors affecting the dissolution of the solids as well as the formation of
the reactive species ( xCaO.SiO 2 .yH2 O and CaO.SiO 2 .Al2 03 .H2 0 systems); are the major
parameters which influence the subsequent SO 2 capture activity of the resultant sorbent.

5.2 Recommendations
Analysis of desulphurisation should be conducted in a CFB reactor which not only provides
long sorbent residence time but also enables intense gas–solid interaction for optimum reactor
conditions for CFA/Ca(OH)2 sorbent to achieve higher performance.

An investigation into the kinetic modelling of the desulphurisation process using the prevailing
conditions in coal powered power plants and furnaces as the development of a kinetic model is
essential for predicting the desulphurisation reactor performance under various modes of
operation.

Characterisation of the CFA/Ca(OH)2 sorbent physical and chemical properties such as

Brunauer-Emmet-Teller (BET) surface area, morphology of the CFA/Ca(OH) 2 sorbent
utilising Scanning electron micrographs as well as chemical analysis of the CFA/Ca(OH) 2
sorbent using XRF analysis.

45
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49
Appendix
Table A. 1 Loss on ignition results

Mass of Initial Mass/g Final Mass/g Loss on

crucible Mass of Mass of CFA Mass of Mass of CFA Ignition/%
crucible + crucible + CFA
CFA
108.391 111.343 2.952 111.107 2.716 7.99458
104.14 106.861 2.721 106.634 2.494 8.342521
102.749 105.642 2.893 105.403 2.654 8.26132
94.042 96.802 2.76 96.573 2.531 8.297101
106.812 109.439 2.627 109.232 2.42 7.879711

Sample calculation:
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑎𝑚𝑝𝑙𝑒 − 𝐹𝑖𝑛𝑎𝑙 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑎𝑚𝑝𝑙𝑒
𝐿𝑂𝐼 =
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑎𝑚𝑙𝑒

2.952 − 2.377
= × 100%
2.952

= 19.47832%

Sieve analysis:

Table A. 2 Sieve analysis results

Aperture Mass retained/g % retained Cumulative % Cumulative %

size/µm retained passing

355 0.172 0.310699 0.310699 99.6893

300 0.982 1.773876 2.084575 97.91542
180 12.829 23.17419 25.25877 74.74123
125 17.764 32.08873 57.3475 42.6525
90 23.612 42.6525 100 0
Total 55.359
Sample Calculation:

𝑟𝑒𝑡𝑎𝑖𝑛𝑒𝑑
𝑚𝑎𝑠𝑠 𝑔
% 𝑟𝑒𝑡𝑎𝑖𝑛𝑒𝑑 = × 100%
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠

50
 0.172
= × 100%
55.359

= 0.310699%

CFA Hydration results:

Table A. 3 CFA Hydration results

Particle Batch 1 Batch 2 Batch 3 Batch 4 Batch 5

size Hydration Hydration Hydration Hydration Hydration
distribution time= time= time= time= time =
of CFA/ µm 30mins 60mins 90mins 120mins 150mins
pH pH pH pH pH
d1=355 7.3 7.8 8.3 8.1 8
d2=300 7.7 8.1 9 8.7 8.5
d3=180 7.9 8.3 9.2 8.9 9
d4=125 8.3 8.8 9.7 9.7 9.5
d5=90 8.6 8.9 9.9 9.6 9.5

Ca(OH)2 conversion results:

Table A. 4 Titration with 0.5M EDTA results

Hydration time = 60 minutes

Sample 1: 1 2 3
CFA/Ca(OH)2 Initial burette reading 3.4 10.4 17.4
=1:3 Final burette reading 10.4 17.4 24.5
Volume of titre used 7 7 7.1
Mean volume of titre used 7.03
Sample 2: Initial burette reading 2.0 10.2 18.5
CFA/Ca(OH)2 Final burette reading 10.3 18.3 26.6
=5:3 Volume of titre used 8.4 8.1 8.1
Mean volume of titre used 8.2
Sample 3: Initial burette reading 1.6 8.2 15
CFA/Ca(OH)2 Final burette reading 8.1 14.6 21.5
= 15:3 Volume of titre used 6.5 6.4 6.5

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 Mean volume of titre used 6.47
Sample 4 Initial burette reading 3.5 10.3 17.3
CFA/Ca(OH)2 Final burette reading 10.3 17.3 24.4
= 9:3 Volume of titre used 6.8 7.0 7.1
Mean volume of titre used 6.97

Hydration time =120 minutes

Sample 1: 1 2 3
CFA/Ca(OH)2 Initial burette reading 3.4 10.4 17.4
=1:3 Final burette reading 10.4 17.0 24.0
Volume of titre used 7 6.6 6.6
Mean volume of titre used 6.73
Sample 2: Initial burette reading 3.9 10.4 17.1
CFA/Ca(OH)2 Final burette reading 10.4 16.9 23.4
=5:3 Volume of titre used 6.5 6.5 6.3
Mean volume of titre used 6.43
Sample 3: Initial burette reading 2.3 8.4 14.5
CFA/Ca(OH)2 Final burette reading 8.4 14.4 20.3
= 15:3 Volume of titre used 6.1 6 5.8
Mean volume of titre used 5.97
Sample 4 Initial burette reading 1.0 7.2 13.5
CFA/Ca(OH)2 Final burette reading 7.1 13.4 19.6
= 9:3 Volume of titre used 6.1 6.2 6.2
Mean volume of titre used 6.17

Hydration time =180 minutes

Sample 1: 1 2 3
CFA/Ca(OH)2 Initial burette reading 3.4 10.4 17.4
=1:3 Final burette reading 10 17.1 24.0
Volume of titre used 6.6 6.7 6.6
Mean volume of titre used 6.57
Sample 2: Initial burette reading 2.7 8.8 14.6

52
 CFA/Ca(OH)2 Final burette reading 8.8 14.6 2o.3
=5:3 Volume of titre used 6.1 5.8 5.7
Mean volume of titre used 5.87
Sample 3: Initial burette reading 4.9 10.6 16.0
CFA/Ca(OH)2 Final burette reading 10.5 15.9 21.3
= 15:3 Volume of titre used 5.6 5.3 5.3
Mean volume of titre used 5.4
Sample 4 Initial burette reading 1.6 7.5 13.5
CFA/Ca(OH)2 Final burette reading 7.5 13.5 19.3
= 9:3 Volume of titre used 5.9 6.0 5.8
Mean volume of titre used 5.9

Hydration time =240 minutes

Sample 1: 1 2 3
CFA/Ca(OH)2 Initial burette reading 3.8 10.4 17.0
=1:3 Final burette reading 10.3 16.7 23.5
Volume of titre used 6.5 6.3 6.2
Mean volume of titre used 6.33
Sample 2: Initial burette reading 2.7 8.7 14.5
CFA/Ca(OH)2 Final burette reading 8.7 14.5 20.3
=5:3 Volume of titre used 6.0 5.8 5.8
Mean volume of titre used 5.9
Sample 3: Initial burette reading 3.1 8.3 13.5
CFA/Ca(OH)2 Final burette reading 8.2 13.5 18.5
= 15:3 Volume of titre used 5.1 5.2 5.0
Mean volume of titre used 5.1
Sample 4 Initial burette reading 2.0 8.0 14.0
CFA/Ca(OH)2 Final burette reading 8.0 13.8 19.8
= 9:3 Volume of titre used 6.0 5.8 5.8
Mean volume of titre used 5.87

Sample calculation: Determination of Concentration of unreacted Ca2+:

53
Complexometric titration is used to determine the unreacted calcium composition in the sorbent
samples. EDTA forms a complex with calcium ions. According to the reaction:

𝐸𝐷𝑇𝐴4− + 𝐶𝑎2+ → (𝐶𝑎 − 𝐸𝐷𝑇𝐴)2−

Stoichiometric ratio of Ca2+ : EDTA is:

𝐶𝑎2+ : 𝐸𝐷𝑇𝐴 = 1: 1

𝑛 (𝐸𝐷𝑇𝐴) = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 × 𝑣𝑜𝑙𝑢𝑚𝑒

𝑚𝑜𝑙
= 0.5 × (7.03 × 10−3 )𝐿
𝐿

= 0.003515𝑚𝑜𝑙

Thus, 𝑛(𝐶𝑎2+ ) = 𝑛(𝐸𝐷𝑇𝐴) = 0.003515𝑚𝑜𝑙

∴ 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝐶𝑎 = 𝑛(𝐶𝑎2+ ) × 𝑀𝑟(𝐶𝑎) × 𝑑𝑖𝑙𝑢𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑖𝑜

250
= 0.003515𝑚𝑜𝑙 × 40𝑔/𝑚𝑜𝑙 ×
20

= 1.7575𝑔

Calcium hydroxide conversion:

𝐶𝑎(𝑂𝐻)2 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 %
𝐶𝑎(𝑂𝐻)2 𝑢𝑠𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑝𝑟𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑟𝑏𝑒𝑛𝑡 − 𝐶𝑎(𝑂𝐻)2 𝑎𝑓𝑡𝑒𝑟 ℎ𝑦𝑑𝑟𝑎𝑡𝑖𝑜𝑛
= × 100%
𝐶𝑎(𝑂𝐻)2 𝑢𝑠𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑝𝑟𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑖𝑑

5𝑔 − 1.7575𝑔
= × 100%
5𝑔

= 64.85%

Table A. 5 Ca(OH)2 Conversion

Hydration CFA/Ca(OH)2 mean volume of mass of unreacted Calcium

time/h ratio titre/10-3 L Calcium/g conversion/%
1 1.3 7.03 1.7575 64.85
5.3 8.2 2.05 59
15.3 6.47 1.6175 67.65
9.3 6.97 1.7425 65.15

54
 2 1.3 6.73 1.6825 66.35
5.3 6.43 1.6075 67.85
15.3 5.97 1.4925 70.15
9.3 6.17 1.5425 69.15
3 1.3 6.57 1.6425 67.15
5.3 5.87 1.4675 70.65
15.3 5.4 1.2608 74.784
9.3 5.9 1.475 70.5
4 1.3 6.33 1.5825 68.35
5.3 5.9 1.475 70.5
15.3 5.1 1.275 74.5
9.3 5.87 1.4675 70.65

Desulphurisation results:

SO4 2- ions concentration in desulphurisation product solids determined indirectly by first

precipitating BASO 4 followed by titration of excess Ba2+ with EDTA

Table A. 6 Indirect titration results

Hydration time= 1 hour

Sample 1: 1 2 3
CFA/Ca(OH)2 Initial burette reading 1.6 6.0 10.1
=1:3 Final burette reading 5.6 10.1 14.2
Volume of titre used 4.0 4.1 4.1
Mean volume of titre used 4.06
Sample 2: Initial burette reading 14.2 18.4 22.5
CFA/Ca(OH)2 Final burette reading 18.4 22.5 26.6
=5:3 Volume of titre used 4.2 4.1 4.1
Mean volume of titre used 4.13
Sample 3: Initial burette reading 2.4 7.4 12.3
CFA/Ca(OH)2 Final burette reading 7.4 12.3 17.2
= 15:3 Volume of titre used 5.0 4.9 4.9
Mean volume of titre used 4.93

55
Sample 4 Initial burette reading 17.5 22.2 27
CFA/Ca(OH)2 Final burette reading 22.2 26.8 31.6
= 9:3 Volume of titre used 4.7 4.6 4.6
Mean volume of titre used 4.67

Hydration time= 2 hour

Sample 1: 1 2 3
CFA/Ca(OH)2 Initial burette reading 3.4 7.1 11.0
=1:3 Final burette reading 7.1 11.0 14.9
Volume of titre used 3.7 3.9 3.9
Mean volume of titre used 3.83
Sample 2: Initial burette reading 15 19.1 23.1
CFA/Ca(OH)2 Final burette reading 19.1 23.1 27.2
=5:3 Volume of titre used 4.1 4.0 4.1
Mean volume of titre used 4.01
Sample 3: Initial burette reading 2.7 7.1 11.2
CFA/Ca(OH)2 Final burette reading 7.1 11.2 15.3
= 15:3 Volume of titre used 4.4 4.1 4.1
Mean volume of titre used 4.2
Sample 4 Initial burette reading 15.3 20.6 25.7
CFA/Ca(OH)2 Final burette reading 20.6 25.7 30.7
= 9:3 Volume of titre used 5.3 5.1 5.0
Mean volume of titre used 5.13

Hydration time = 3 hours

Sample 1: 1 2 3
CFA/Ca(OH)2 Initial burette reading 3.9 7.3 10.6
=1:3 Final burette reading 7.3 10.6 13.7
Volume of titre used 3.4 3.3 3.1
Mean volume of titre used 3.27
Sample 2: Initial burette reading 13.7 16.6 19.6
Final burette reading 16.6 19.6 22.7

56
CFA/Ca(OH)2 Volume of titre used 2.9 3.0 3.1
=5:3 Mean volume of titre used 3.0
Sample 3: Initial burette reading 5.8 9.6 13.3
CFA/Ca(OH)2 Final burette reading 9.6 13.3 16.9
= 15:3 Volume of titre used 3.8 3.7 3.6
Mean volume of titre used 3.7
Sample 4 Initial burette reading 16.9 21.1 25.1
CFA/Ca(OH)2 Final burette reading 21.1 25.1 29.1
= 9:3 Volume of titre used 4.2 4.0 4.0
Mean volume of titre used 4.07

Hydration time = 4
Sample 1: 1 2 3
CFA/Ca(OH)2 Initial burette reading 1.7 4.4 6.8
=1:3 Final burette reading 4.4 6.8 9.2
Volume of titre used 2.7 2.4 2.4
Mean volume of titre used 2.5
Sample 2: Initial burette reading 9.2 11.4 13.5
CFA/Ca(OH)2 Final burette reading 11.4 13.5 15.6
=5:3 Volume of titre used 2.2 2.1 2.1
Mean volume of titre used 2.13
Sample 3: Initial burette reading 15.6 19.7 23.7
CFA/Ca(OH)2 Final burette reading 19.7 23.7 27.7
= 15:3 Volume of titre used 4.1 4.0 4.0
Mean volume of titre used 4.03
Sample 4 Initial burette reading 1.5 5.2 9.0
CFA/Ca(OH)2 Final burette reading 5.2 9.0 12.8
= 9:3 Volume of titre used 3.7 3.8 3.8
Mean volume of titre used 3.77

57
Table A. 7 Desulphurisation activity results
Hydration CFA/Ca(OH) 2 Mean volume of Number of moles Sulphate ions
time/mins ratio/g/g titre/ 10-3L of excess 𝑩𝒂𝟐+/ concentration/ 𝟏𝟎−𝟑𝒎𝒐𝒍/
𝟏𝟎−𝟑𝒎𝒐𝒍 𝒍

60 0.33 4.06 2.03 1.1485

1.67 4.13 2.065 1.14675

3 4.67 2.355 1.13225

5 4.93 2.465 1.12675
120 0.33 3.83 1.915 1.15425
1.67 4.01 2.005 1.14975
3 5.13 2.565 1.12175
5 4.2 2.1 1.145
180 0.33 3.27 1.635 1.16825
1.67 3 1.5 1.175

3 4.07 2.035 1.14825

5 3.7 1.85 1.1575
240 0.33 2.5 1.25 1.1875
1.67 2.13 1.065 1.19675
3 3.77 1.885 1.15575
5 4.03 2.015 1.14925

(𝑇𝑜𝑡𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑎𝑑𝑑𝑒𝑑 𝐵𝑎2+ ) − (𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑒𝑥𝑐𝑒𝑠𝑠 𝐵𝑎2+ )

𝑆𝑂42 − 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 =
𝑉𝑆𝑂42−

(25 × 10−3 )𝑚𝑜𝑙 − (2.03 × 10−3 )𝑚𝑜𝑙

=
20 × 10−3 𝑙

= 1.1485 × 10−3 𝑚𝑜𝑙/𝑙

58
Commercial lime desulphurisation results:

Table A. 8 Desulphurisation activity results for commercial hydrated lime sorbent

Mean volume of titre/103L Number of moles of excess Concentration of SO42-
𝑩𝒂𝟐+/𝟏𝟎−𝟑𝒎𝒐𝒍 𝟏𝟎−𝟑𝒎𝒐𝒍/𝒍
7.983 3.9915 0.84034
7.587 3.7935 0.84826
7.203 3.6015 0.85594
7.205 3.6025 0.8559

59