FYP Report - Sayali Chaudhari

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Nanyang Technological University, Singapore.
Innovative use of wastes for carbon capture
Chaudhari, Sayali Sujeet
2022
Chaudhari, S. S. (2022). Innovative use of wastes for carbon capture. Final Year Project
(FYP), Nanyang Technological University, Singapore. https://hdl.handle.net/10356/158819
https://hdl.handle.net/10356/158819
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INNOVATIVE USE OF WASTES FOR CARBON
CAPTURE
Chaudhari Sayali Sujeet
SCHOOL OF CIVIL AND ENVIRONMENTAL ENGINEERING

COLLEGE OF ENGINEERING
NANYANG TECHNOLOGICAL UNIVERSITY
2021/2022
1
INNOVATIVE USE OF WASTES FOR CARBON
CAPTURE
Submitted by:
Chaudhari Sayali Sujeet
SCHOOL OF CIVIL AND ENVIRONMENTAL ENGINEERING

COLLEGE OF ENGINEERING
NANYANG TECHNOLOGICAL UNIVERSITY
A Final Year Project presented to Nanyang Technological University

in partial fulfilment of the requirements for the
Degree of Bachelor of Engineering
2021/2022
2
Abstract
Carbon capture, utilization and storage (CCUS) is an important emissions reductions technology
that has gained much attention in the last decade, owing to its ability to contribute to guaranteed
large scale negative emissions. Incineration bottom ash (IBA) is a by-product generated during
the incineration of municipal solid waste (MSW) while seawater desalination brine is a by-product
generated during the seawater desalination process. Both are considered as wastes and currently
being disposed to the landfill (IBA) or to the sea (brine) without beneficial reuse or material
recovery. Nevertheless, both waste materials are found to have chemical compositions that are
potentially favourable for carbon capture and materials recovery. To contribute towards
Singapore’s aim of being net-zero in carbon emission by 2050, this study aims to utilize these
waste materials to determine whether a high yield of good quality products such as calcium
carbonates can be generated through carbonation. In this study, carbonation of different types of
wash water produced from applying different leachants was carried out. Wash water was mixed
with seawater and brine to generate alkaline residues, which were subsequently added back into
brine to determine its possible usage as an alkali source.
Carbonation results of different solutions throughout this study concluded that the P-alkalinity of
a solution has a strong correlation to the yield of carbonates formed. Upon mixing wash water
with seawater or brine, an alkaline residue was precipitated, and it has been established through
this study that it can be used as an alkali source for carbonation, as a replacement for a base
additive such as the commonly used NaOH. However, more research is required to optimize the
design parameters of this process for more efficient carbonation. Analysis of used water generated
during the experiments revealed that trace heavy metals such as Ba, Cu and Zn are present, along
with high amounts of chlorides and sulfates, which may require further treatment before
discharge. More research should be performed in the future to further reduce the concentration of
metal ions, chlorides and sulfates in the used water to make it suitable for discharge by avoiding
the negative environmental impacts associated. More research should also be performed to
increase confidence in stakeholders, such as plant owners, such that they will be more agreeable
to implementing CCUS technology once it is available commercially. At the same time, the
negative environmental impacts of discharging the waste products formed into Singapore’s
natural environment should also be assessed carefully and mitigated accordingly.
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Acknowledgements
This research paper would not have been possible without the kind help and support of many
individuals. I would like to express my utmost gratitude to the following individuals who have
supported and guided me throughout my final year project (FYP) journey while making it an
enriching and unforgettable learning experience.
My project supervisor, Associate Professor Grzegorz Lisak, Director of Residues and Resource
Reclamation Centre (R3C), for giving me the chance to pursue this project at Nanyang
Environment & Water Research Institute (NEWRI) and offering me constructive feedback at
every turn, as well as for his faith in my research potential.
My mentor, Dr Chan Wei Ping, for his constant support during this entire journey; for spending
long hours hunched over laptop screens with me, pushing me to dig deeper each time and guiding
me with such care and patience. Our meetings were vital in inspiring me to think outside the box,
from multiple perspectives to form a comprehensive study. I owe him a great debt of knowledge.
Mr Preston Tan, for his selfless and valuable support in the R3C laboratory at NEWRI; for
offering technical advice and spending so much time patiently training me in various equipment.
Without him, this project would not have been possible.
My family and friends, who have been my pillar of emotional support throughout this trying
journey. Thank you for your unconditional support in this very intense academic year and for
putting up with me choosing to spend long hours in the laboratory instead of in your company for
weeks on end.
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Table of Contents
Abstract ........................................................................................................................................ 3
Acknowledgements...................................................................................................................... 4
List of Figures .............................................................................................................................. 7
List of Tables ............................................................................................................................... 8
1. Introduction ......................................................................................................................... 9
1.1. Background ................................................................................................................... 9
1.2. Objectives.................................................................................................................... 10
1.3. Scope of Work ............................................................................................................ 10
2. Literature Review.............................................................................................................. 13
2.1. Carbon capture, utilisation and storage (CCUS) ......................................................... 13
2.2. Potential of alkaline industrial wastes for use in CCUS ............................................. 14
2.2.1. Properties of alkaline industrial wastes ............................................................... 14
2.2.2. Assessment of Singapore’s resources ................................................................. 16
2.3. Potential of brine for use in CCUS ............................................................................. 18
2.3.1. Environmental impacts of brine .......................................................................... 18
2.3.2. Chemical composition of brine ........................................................................... 18
2.4. Direct carbonation ....................................................................................................... 19
2.4.1. Direct aqueous carbonation (DAC) ..................................................................... 19
2.4.2. Gas-solid pathway ............................................................................................... 19
2.5. Indirect aqueous carbonation (IAC) ............................................................................ 20
2.5.1. Advantages and limitations of IAC ..................................................................... 20
2.6. Industrial applications of Mg, Ca carbonates and Mg(OH)2 ....................................... 21
3. Materials and Methods ..................................................................................................... 23
3.1. Materials...................................................................................................................... 23
3.2. Methods....................................................................................................................... 24
3.2.1. Washing of IBA .................................................................................................. 24
3.2.2. Generating Alkaline Residue .............................................................................. 24
3.2.3. Carbonation ......................................................................................................... 25
3.2.4. Characterisation testing ....................................................................................... 26
4. Results and Discussion ...................................................................................................... 28
4.1. Part 1: Results from washing with different leachants ................................................ 28
4.2. Part 1: Residues obtained from mixing W-1-DI with BR and SW ............................. 29
4.2.1. Formation of residues .......................................................................................... 29
4.2.2. Chemical composition of residues ...................................................................... 32
4.2.3. Yield of residues generated ................................................................................. 34
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4.3. Part 1: Changes in pH and EC during carbonation ..................................................... 34
4.4. Part 1: Relationship between P-alkalinity and yield of carbonates ............................. 36
4.5. Part 1: Results for carbonates formed during carbonation .......................................... 39
4.6. Part 2: Results from generation of alkaline residues ................................................... 41
4.6.1. Yield of alkaline residues .................................................................................... 41
4.6.2. Chemical properties of alkaline residues ............................................................ 41
4.7. Part 2: Results from adding residue back into BR ...................................................... 42
4.7.1. Alkalinity of mixed solutions (R1-R4)................................................................ 42
4.8. Part 2: Results from carbonation experiments ............................................................ 43
4.8.1. Change in pH and EC during carbonation .......................................................... 43
4.8.2. Yield of carbonates produced .............................................................................. 44
4.8.3. Chemical properties of carbonates ...................................................................... 45
4.9. Part 2: Quality of used water ....................................................................................... 47
4.9.1. Used water 1 generated pre-carbonation ............................................................. 47
4.9.2. Used water 2 generated post-carbonation ........................................................... 47
5. Conclusion.......................................................................................................................... 50
6. Recommendations ............................................................................................................. 52
6.1. Pre-treatment of IBA before washing ......................................................................... 52
6.2. Further studies on use of alkaline residue as an alkali source ..................................... 52
6.3. Thermodynamic modelling for establishing theoretical baseline ................................ 52
References .................................................................................................................................. 53
Appendices ................................................................................................................................. 55
Appendix A: Summary of solutions produced ........................................................................ 55
Appendix B: Elemental data for brine .................................................................................... 56
Appendix C: Elemental data for seawater ............................................................................... 57
Appendix D: Elemental data of wash water (W-1-DI) ........................................................... 58
Appendix E: Elemental data for mixed solution (50% W-1-DI + 50% BR) ........................... 59
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List of Figures
Figure 1: Overall experimental flow for Part 1 of study. ............................................................ 11
Figure 2: Overall experimental flow for Part 2 of study. ............................................................ 12
Figure 3: Depiction of different mineral carbonation pathways [10]. ......................................... 14
Figure 4: (a) F3 IBA (b) F4 IBA and (c) F5 IBA. ....................................................................... 23
Figure 5: IBA of diameter less than 4 mm. ................................................................................. 23
Figure 6: P-alkalinity of wash water from both rounds of washing ............................................ 28
Figure 7: White residues produced from mixing W-1-DI with BR/SW ..................................... 30
Figure 8: Mass of elements in residues generated from the mixing of 50% BR and 50% SW. .. 32
Figure 9: FTIR Spectra of residues generated from mixed solutions ......................................... 33
Figure 10: Change in yield of residues across three different mixtures. ..................................... 34
Figure 11: Changes in EC and [OH-] for (a)W-1-DI, (b) W-1-SW and (c) W-1-BR.................. 35
Figure 12: Changes in pH and EC for (a) W-1-DI, (b) W-1-SW and (c) W-1-BR ..................... 35
Figure 13: Change in total and recovered yield of carbonates over P-alkalinity for (a)W-1-DI,
(b) W-1-SW, (c) W-1-BR (d) Combined solutions ..................................................................... 37
Figure 14: Change in yield over P-alkalinity of W-1-DI mixed with (a) BR, (b) SW, (c) BR or
SW............................................................................................................................................... 38
Figure 15: Mass of elements present in F3 carbonates ............................................................... 39
Figure 16: FTIR Spectra of (a) Pure carbonates and carbonates produced from (b)W-1-DI,
(c)W-1-SW, (d) W-1-BR ............................................................................................................ 40
Figure 17: Yield of residues generated for mixed solutions ....................................................... 41
Figure 18: Mass of measured elements in residue ...................................................................... 41
Figure 19: XRD Spectra for residues in Part 2............................................................................ 42
Figure 20: Comparison of P-alkalinity of solutions R1 – R4 ...................................................... 42
Figure 21: Change in pH over time during carbonation.............................................................. 43
Figure 22: Change in EC over time during carbonation ............................................................. 43
Figure 23: Change in yield of carbonates over (a) Total residue added (b) P-alkalinity of
solution ........................................................................................................................................ 44
Figure 24: XRD Spectra for carbonates ...................................................................................... 45
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List of Tables
Table 1: Chemical composition of alkaline industrial wastes in UK and their theoretical CO2
uptake [12]. ................................................................................................................................. 15
Table 2: Physical Characteristics of IBA [17]. ........................................................................... 16
Table 3: Major and trace elements content in IBA [17]. ............................................................. 17
Table 4: Concentrations of major ions present in brine [19]....................................................... 18
Table 5: Comparison of solvent prices used for various raw materials [22]. .............................. 21
Table 6: Change in alkalinity of F3 and F4 solutions after mixing and filtration ....................... 31
Table 7: Comparison of dominant elements present in carbonates formed from carbonating the 4
mixed solutions ........................................................................................................................... 46
Table 8: Comparison of Used Water 1 quality (pre-carbonation) to NEA and PUB standards .. 48
Table 9: Comparison of Used Water 2 quality (post-carbonation) to NEA and PUB standards 49
Table 10: Summary of solutions produced in Part 1 and Part 2 .................................................. 55
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1. Introduction
1.1. Background
In the past decade, carbon dioxide (CO2) concentrations have increased steadily. According to a
report by the Intergovernmental Panel of Climate Change (IPCC), the concentration of CO2 in the
atmosphere is expected to reach an alarming 1200 parts per million (ppm) by 2100 [1]. As
countries around the globe recover from the COVID-19 pandemic, the global electricity demand
is set to increase by 28.6% by 2040. The industrial industry is responsible for the bulk of this
demand growth, followed by the commercial and services sector and then the residential sector.
40% of this additional demand is forecasted to be covered by fossil fuel-based electricity
generation [2]. The resulting increase in atmospheric CO2 concentrations will bring about more
frequent extreme weather events, and disasters such as floods, cyclones, and droughts which will
have significant impacts on human health and the environment. Thus, the urgent reduction of CO2
emissions is vital.
During the 2021 United Nations Climate Change Conference (COP26), many policymakers
around the world unanimously agreed on the need to drastically reduce emissions to keep global
warming at less than 2 degrees Celsius and pledged to explore new ways to close the current
emissions gap [3]. In an effort to align with the latest targets set at COP26, Singapore has
accelerated its climate ambitions by pledging to reach net zero emissions by 2050. To be able to
meet these targets and complement existing decarbonization efforts, the government has awarded
$55 million to support research, development and demonstration projects on low-carbon energy
technology solutions such as hydrogen, and carbon capture, utilisation and storage (CCUS) [4].
While carbon capture and storage (CCS) has been the subject of many research studies, CCUS
has been attracting more attention lately. This is because before CCS may be widely deployed in
geological formations, full-scale integrated demonstration projects and numerical simulations are
still needed to improve knowledge of long-term CO2 geological storage [5]. On the other hand,
through CCUS, CO2 can be used as a potentially recyclable material to generate products for
industrial applications and at the same time, reduce emissions. It can thus be harnessed as a raw
material for the material value chain [6]. In addition, advancement in creating and
implementing CCUS technologies in one sector may have significant spillover benefits in other
industries or applications, including technological learning, cost savings, and infrastructure
construction.
According to research done by McKinsey, in the next 10 years, CCUS could increase its CO2
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abatement capacity from 50 million tons per year (Mtpa) today, primarily for enhanced oil
recovery and beverage carbonation, to at least 500 Mtpa. This is equivalent to just over 1% of
current annual emissions [7]. Hence, despite the many complexities associated with this
technology, it is clear that CCUS has massive potential for large-scale CO2 abatement and is a
required step on the pathway to limiting global warming to 1.5 degrees Celsius above preindustrial
levels.
1.2. Objectives
The objective of this project is to develop a cost-effective integrated system for carbon capture
and storage with wastes by using incineration bottom ash (IBA) and seawater desalination brine
(brine). In Part 1 of this study, carbonation of different wash waters produced by using different
leachants, such as deionized water (DI), seawater (SW) and brine (BR) is carried out to assess the
yield and quality of carbonates produced. In addition, by mixing varying proportions of alkaline
wash water generated from washing of IBA with DI into the BR or SW, an alkaline residue is
found precipitated from the mixed solutions.
In Part 2 of this study, the possibility of re-adding this residue into brine for aqueous carbonation
is explored. The yield, composition and purity of carbonates produced will be analysed to
determine the feasibility of using the residues as a source of alkalinity for aqueous carbonation
and to determine whether this can be carried out on a larger scale to fulfil the commercial need
for high amounts of CO2 capture at a low cost.
1.3. Scope of Work

The scope of work includes:
i. Literature review on the existing landscape of CCUS and its processes.

ii. Carbonation of different types of wash water produced from applying
different leachants.
iii. Mixing wash water and brine in different proportions to investigate its effect
on the properties and yield of alkaline residue generated.
iv. Characterisation of alkaline residues generated from mixing experiments
v. Carbonation of brine containing varying masses of alkaline residue to study
its effect on the yield and purity of calcium carbonates produced.
vi. Carrying out elemental analysis of used water to be discarded pre- and post-
carbonation to verify its accordance with allowable limits for trade effluent
discharge to watercourse by NEA and requirements for discharge of trade
effluent into the public sewers by PUB.
10
A summary of the scope of work for Part 1 and Part 2 of this study is shown in the flow charts in
Error! Reference source not found. and Figure 2 respectively.
Figure 1: Overall experimental flow for Part 1 of study.
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Figure 2: Overall experimental flow for Part 2 of study.
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2. Literature Review
2.1. Carbon capture, utilisation and storage (CCUS)
CCUS is a term that refers to a wide range of technologies that can help achieve a variety of global
energy and climate goals. As power generation contributes to the highest proportion of CO2
generated compared to any other sector, developing CCUS technology for use at power plants is
deemed to be an attractive way to achieve stringent greenhouse gas reduction targets. This is
especially so in the current socio-political context where there are calls to stop new power plants
from being built unless they come fitted with systems that can capture CO2 emissions before they
are released into the environment [8].
In CCS, CO2 is usually first trapped from large point sources, such as power plants or industrial
facilities that run on fossil fuels or biomass. There are three main categories of carbon capture:
post-combustion carbon capture, pre-combustion carbon capture, and oxy-fuel combustion
systems [9]. Currently, the post-combustion carbon capture technique is the most widely adopted
method in existing power plants as it has the smallest impact on existing systems. While the
utilisation of CO2 captured from the exhaust streams of power plants for chemical applications
has not been carried out on an industrial level, it is now being widely discussed and many pilot
studies are in place to explore CCUS on a larger scale.
CO2 mineralisation is a common method used in CCUS. It is an acid-base reaction where calcium
and magnesium-containing minerals are reacted with CO2 to produce stable carbonates (CaCO3,
MgCO3). There are two possible processes for CO2 mineralisation: direct and indirect
carbonation. In direct carbonation, minerals in their original state or in slurry form react directly
with CO2. However, this process is found to have slow reaction kinetics, a low conversion rate
and the total reaction time is very long. Indirect carbonation, on the other hand, requires milder
reaction conditions and is able to generate purer by-products with a higher carbonation efficiency.
It involves extracting Ca or Mg from minerals followed by carbonation of the Ca or Mg in alkaline
conditions [10]. Figure 3Figure 3 shows the different methods of carbonation that are currently
being researched upon.
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Figure 3: Depiction of different mineral carbonation pathways [10].
2.2. Potential of alkaline industrial wastes for use in CCUS

2.2.1. Properties of alkaline industrial wastes
Alkaline waste materials are produced by a variety of industrial processes, including coal
combustion, cement production, iron and steel manufacturing as well as municipal solid waste
(MSW) incineration. While the mineral composition of these waste materials varies significantly,
they are distinguished by the presence of Na, Ca, or Mg oxides that quickly hydrate to generate
soluble hydroxides. There are also a wide range of Ca and Na silicate, aluminate and
aluminosilicate phases present that dissolve to generate alkalinity as well as a more stable form
of alkalinity in the form of Ca and Mg carbonates [11].
Based on Table 1, the efficiency of the carbonation process can be linked to the variations in
reactive calcium and magnesium oxides present in the starting material. Steel slag, CKD, biomass
ash, oil shale ash, AOD process slag, APC residue, and paper incinerator ash all have a high CaO
content (40–70%), resulting in a large potential CO2 uptake. So does MW IBA, however, the
presence of chlorides and sulfates appears to impede the carbonation procedure, resulting in a
lower CO2 uptake [12]. This could lead to a low yield in carbonates formed as well.
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Table 1: Chemical composition of alkaline industrial wastes in UK and their theoretical CO2 uptake [12].
Chemical composition (wt. %) Total CO2

CaO MgO Fe2O3 SiO2 Cl SO3 Na2O K2O uptake (wt. %)
Blastfurnace slag 15 - 41 8 - 11 0.5 - 0.9 34 - 36 1.4 0.6 20 - 44
Steel slag 34 - 55 1.5 - 10 0.8 8 0.3 0.1 29 - 52
AOD process slag 60.7 5.83 0.21 27.6 54
Cement Kiln Dust 34.5 - 46.2 1.5 - 2.1 2.9 16.4 22 0.5 4 - 5.8 30
Biomass and wood ash 24 - 46 8-9 1 - 1.3 5.17 0.63 - 3 0.5 14 - 21 50
Recycled concrete aggregate 15 - 24 2-3 0.1 0.2 6 - 22
Incinerator sewage sludge ash 9 - 37 3 5.6 40 0.3 0.7 2.3 15
MW incinerator bottom ash 32 - 53 2.8 1 - 7.9 4 - 30 19 27.9 2.2 - 5.7 0.8 - 2 25
Pulverised-fuel ash 1.3 - 10 1-3 13.8 56 4 0.5 0.1 6
Air pollution control residue 50 - 60 8 0.5 - 15 10 1.8 - 38 2-6 50 - 58
Papersludge Incineration ash 45 - 69 1.3 - 5.3 1 - 4.7 10 - 25 1-7 0-1 0-2 50
15
Due to their alkaline nature and the presence of heavy metals, the improper release of industrial
wastes due to poor waste management practices poses harmful effects on human health and the
environment. For example, when the leachate from the alkaline waste enters marine
environments, there is an increase in pH, chemical oxygen demand (COD), sulfate loadings and
metal concentrations observed which can smother macroinvertebrate communities and reduce the
amount of light passing through the water, thus harming marine animals and vegetation [11].
Studies have shown that mineral carbonation, dry or aqueous, can be used as a pre-treatment step
to improve the quality of such alkaline industrial wastes. This is because such a process essentially
mimics natural weathering processes. This includes reacting CO2 with primary ion-releasing
minerals such as hydrogen (H+), magnesium (Mg2+), and calcium (Ca2+) to produce carbonates
that can eventually be converted into a stable product [13]. Such stable products have been found
to have useful applications in the construction industry. For example, incineration ash can be used
to replace cement and fine/coarse aggregates when developing construction materials.
Consequently, mineral carbonation offers a two-fold reduction in CO2 emissions: direct reduction
by carbonation of alkaline industrial wastes and using the stable carbonates produced as a
replacement for conventional carbon-intensive products.
2.2.2. Assessment of Singapore’s resources

Singapore’s only waste landfill, Semakau landfill receives more than 2,000 tonnes of incineration
ash and non-incinerable waste every day. At this rate, Semakau landfill is expected to run out of
space by 2035 [14]. Currently, an estimated 1,500 tonnes of IBA is generated in Singapore each
day, and this figure is expected to hit 2,100 tonnes by 2023 [15]. It is vital to divert the incineration
ash and use it for other purposes. The Land Transport Authority (LTA) has previously tested and
approved the use of IBA in constructing road pavements since 2010 [16].
2.2.2.1. Physical properties of IBA

A study was carried out to examine the physical characteristics of IBA, as seen from Table 2.
Table 2: Physical Characteristics of IBA [17].
Physical characteristics of IBA

Dry bulk density 950 kg/m3
Specific gravity 1.5 - 2.4 t/m3
Moisture content 15% - 30%
Particle size distribution 0.02 - 10mm
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In addition, compaction, shear strength and cohesion tests were carried out, which revealed that
IBA has high strength and a well-graded particle size distribution, thereby making it suitable for
use in road bases and related earthworks [17].
2.2.2.2. Chemical properties of IBA

A review of the chemical properties of IBA was carried out (Table 3).
Table 3: Major and trace elements content in IBA [17].
Metals N Mean SD
Ag 2 18.6 25.9
As 12 23.8 56.7
B 6 42.52 6.16
Ba 2 1700 1838
Be - -
Cd 13 8.1 19.25
Co 8 69.1 113.9
Cr 13 420 883
Cu 12 1997 3259
Hg - - -
Mn 10 476 731
Mo 3 102.7 150.7
Ni 13 454 1170
Pb 12 1683 4037
Sb - - -
Se 4 2.57 4.96
Sn 8 50.2 133.3
Sr 2 543 647
Ti 8 8534 2414
TI - - -
V 9 127 86.1
Zn 12 1711 2683
CaO 11.07-27.82 P2O5 2.18-3.01
SiO2 31.00-49.23 TiO2 1.39
Al2O3 8.06-16.48 ZnO 0.66-0.95
Fe2O3 5.07-12.60 PbO 0.34
SO3 0.30-5.21 MnO 0.31
MgO 1.43-2.93 CuO 0.38-0.4
Na2O 2.79-5.76 Cl 0.06-4.87
K2O 0.72-1.54
N: the number of elements for data analysis

SD: Standard deviation
17
As seen from Table 3Table 3, IBA contains many metal oxides, such as CaO, MgO and Na2O.
Thus, in Singapore’s context, due to the abundance of IBA available and its favourable chemical
composition, it can be identified as a prime candidate for providing a source of minerals and
alkalinity during aqueous or slurry carbonation. In this process, its quality is improved, allowing
it to be used for construction purposes.
2.3. Potential of brine for use in CCUS

2.3.1. Environmental impacts of brine
Brine is produced as a by-product in the seawater desalination process. It is highly concentrated
saline water, which also contains residues of pretreatment chemicals and heavy metals as a result
of corrosion. After desalination, brine is usually discharged directly into the sea without any
further treatment. The reject brine can disrupt local seawater conditions, including temperature
and salinity, posing a serious hazard to marine life. Increased temperature can have an effect on
water quality processes, resulting in reduced dissolved oxygen concentrations, which are
necessary for aquatic life's survival [18]. Hence, it is critical to develop a method for de-
concentrating reject brines before disposal in order to limit their negative influence on the
environment. Carbonation of brine has been widely explored in research papers as a way to
mineralise the metal ions by reacting them with CO2 and precipitating out carbonated minerals
such as calcium carbonates, magnesium carbonates and hydromagnesites [19].
2.3.2. Chemical composition of brine

In a recent study, the brine from a seawater reverse osmosis (RO) method, used to supplement
industrial water in Korea, was analysed. Table 4Table 4 shows the major cations and ions present
in the ions, as measured by ICP-OES.
Table 4: Concentrations of major ions present in brine [19].
Ions Mg Ca Na K Cl SO4
Concentration
2226 714 17987 858 32220 4766
(mg/L)
As can be seen from Table 4Table 4, brine serves as a good source of Ca and Mg cations which
can eventually be separately precipitated as carbonates by designing a carbonation process.
However, the brine is also very rich in chlorides and sulfates, and the presence of such high
concentration of salts may hinder the carbonation process.
18
2.4. Direct carbonation
Direct carbonation can be carried out in two ways: in an aqueous solution or as a dry gas-solid
reaction.
2.4.1. Direct aqueous carbonation (DAC)

Direct aqueous carbonation takes place in a single reactor and entails three coexistent
mechanisms. Firstly, CO2 dissolves in water to form a mildly acidic environment with HCO3 − as
the dominant carbonate species:
𝐶𝑂2 (𝑔) + 𝐻2 𝑂(𝑙) → 𝐻2 𝐶𝑂3 (𝑎𝑞) → 𝐻 + (𝑎𝑞) + 𝐻𝐶𝑂3 − (𝑎𝑞)
Secondly, due to the drop in pH, there is leaching of Ca and Mg from the minerals. For example,
in industrial wastes containing Ca/Mg silicates:
2+
(𝐶𝑎⁄𝑀𝑔) 𝑠𝑖𝑙𝑖𝑐𝑎𝑡𝑒𝑠 (𝑠) + 2𝐻 + (𝑙) → (𝐶𝑎⁄𝑀𝑔) (𝑎𝑞) + 𝑆𝑖𝑂2 (𝑠) + 𝐻2 𝑂(𝑙)
Thirdly, precipitation of Ca and Mg carbonates occurs:

2+
(𝐶𝑎⁄𝑀𝑔) (𝑎𝑞) + 𝐻𝐶𝑂3 − (𝑎𝑞) → (𝐶𝑎⁄𝑀𝑔) 𝐶𝑂3 (𝑠) + 𝐻 + (𝑎𝑞)
It has been generally accepted that the second step is rate-limiting, which is why previous studies
have been focused on optimising the kinetics of silicate dissolution by altering operating
conditions such as pressure, temperature, CO2 concentration and solid to liquid ratio as well as
employing a variety of additives in the reaction [10]. In an economic evaluation done for DAC,
it was found that there is a need to concentrate research on mineral selection, reducing the amount
of electricity required by lowering the operating pressure and reducing amount of heat generated
in the process. These three key inputs were found to have the greatest effect on the DAC route’s
economic feasibility for large-scale projects [20].
2.4.2. Gas-solid pathway

This pathway involves the direct reaction of CO2 with solid minerals of alkaline waste:
(𝐶𝑎⁄𝑀𝑔) 𝑠𝑖𝑙𝑖𝑐𝑎𝑡𝑒𝑠 (𝑠) + 𝐶𝑂2 (𝑔) → (𝐶𝑎⁄𝑀𝑔) 𝐶𝑂3 (𝑠) + 𝑆𝑖𝑂2 (𝑠)
This method is quite straightforward and requires a simple process design. However, it is often
touted to be unsuitable for large-scale use due to its extremely slow carbonation reaction kinetics
and low conversion rates [10]. This route can instead be adopted to develop potential CO2
absorbing solids sorbents, such as calcined limestone [21].
19
2.5. Indirect aqueous carbonation (IAC)
2.5.1. Advantages and limitations of IAC
The indirect aqueous carbonation uses two separate aqueous steps: (a) extraction of Ca and Mg
from minerals and (b) carbonation of Ca and Mg in alkaline conditions. One advantage of this
pathway is that both steps can be optimised individually, and additional steps can be integrated if
necessary. Moreover, milder carbonation conditions are required compared to direct carbonation
and purer by-products can be obtained [10].
In DAC, the carbonic acid that is formed due to the dissolution of CO2 in water is insufficient for
leaching out the metal from the feedstock effectively and thus, this method often suffers from
slow dissolution kinetics. On the other hand, in IAC, the carbonation step occurs rapidly,
immediately after the dissolution of the reactive metal species and this process is usually
facilitated by a chemical additive. The IAC method is also able to generate carbonates of high
purity [21]. Acidic conditions are preferred for dissolution, while alkaline conditions are preferred
for carbonation. This difference in ideal reaction rates leads to the IAC having a narrow pH range,
or as it is often referred to, the pH swing process.
However, this method is also not without its challenges. In previous literature available, water,
ammonium salts, acids and chelating reagents have been used as solvents for indirect aqueous
carbonation. While the ability of acids to elute Ca and Mg from minerals is high, a large amount
of alkali reagent has to be added to increase the pH of the solution, which increases the overall
operating costs. Using other solvents may result in a high carbonation efficiency, eliminating the
requirement of alkali addition. However, this increases the cost of the solvents substantially. Table
5 shows the different solvent prices used in previous studies.
20
Table 5: Comparison of solvent prices used for various raw materials [22].
Solvent price ($-

Raw material Solvent S/L ratio
solvent/ton-waste)
Waste 0.5M NH4Cl 1:20 124
Cement 0.1M NH4Cl 1:20 249
Paper sludge 0.7M CH3COOH 1:25 690
0.7M HCl 1:25 576
0.3M NH4Cl 1:50 186
0.3M
Ash 1:50 1285
NH4CH3COO
0.3M sodium
1:50 2424
Citrate
Water 1:50 0
Waste 0.5M HCl 1:10 165
0.5M CH3COOH 1:10 195
Cement
0.5M NH4Cl 1:10 62
Steel slag 2.0M HCl 1:10 659
From Table 5Table 5, it can be seen that the solvent cost can go up to $2,400/ton-waste which
has impacts on the economic feasibility of this process. Thus, there is a need to find a replacement
for these solvents or avoid using them altogether to reduce the largest part of the production cost
significantly. Instead, other easy to obtain and low-cost reagents such as seawater or brine should
be explored instead.
Other challenges associated with IAC include the extra energy needed to evaporate the solvents
and chemical additives from the final products, co-leaching of impurities associated with the
chosen metal and a narrow pH swing [21].
2.6. Industrial applications of Mg, Ca carbonates and Mg(OH)2

The IAC method produces pre-dominantly CaCO3 and in some cases, MgCO3. IAC is able to
produce calcium carbonates with purity of up to 90%. By adding another step before carbonation
to remove impurities, precipitated calcium carbonates of a higher purity (98%) can be obtained.
Mixing the alkaline wash water produced from washing IBA with SW or BR also results in the
precipitation of Mg(OH)2. These by-products have many industrial applications.
Ca and Mg carbonates can be utilised in many industries including paper and paint fillers,
agriculture, pharmacy. It is most commonly used in the construction industry as construction
materials to replace conventional carbon-intensive products. In the chemical sector, precipitated
calcium carbonate (PCC) is used in the fields of plastics, rubber, papermaking, medicine,
21
coatings, and pesticide manufacturing [10]. Since PCC is chemically synthesised, the
manufacturing process can be controlled to obtain desirable particle sizes and shape of crystals,
allowing for unique polymer applications as well.
Mg(OH)2 is often used as antacids or laxative in a tablet form or a liquid suspension. Furthermore,
it is used commercially as a fire retardant because of its smoke supressing qualities. It can also be
administered to relieve canker sores or as a deodorant [23].
22
3. Materials and Methods
3.1. Materials
Incineration bottom ash (IBA) used in this study was obtained from REMEX Minerals Singapore
Pte Ltd. The IBA was sealed in a plastic container and stored to prevent absorption of moisture
from the surrounding air and minimize contamination. For Part 1 of this study, IBA was sieved
out according to three factions of sizes: F3 (1.0 – 4.0 mm), F4 (0.5 – 1.0 mm) and F5 (< 0.5 mm).
Sieving of IBA is important as the elemental composition of IBA has been found to vary
according to the size fractions. The Ca content increases, and the Si content decreases in IBA fine
fractions. Supporting this theory, when direct carbonation was carried out for unsieved and sieved
samples of less than 4 mm, the sieved sample’s CO2 uptake was nearly twice compared to the
unsieved sample [24].
(a) (b) (c)
Figure 4: (a) F3 IBA (b) F4 IBA and (c) F5 IBA.
For part 2 of this study, IBA of diameter less than 4 mm was sieved out using a standard sieve of
pore size 4 mm. This size fraction was used for all experiments in Part 2 (Figure 5).
Figure 5: IBA of diameter less than 4 mm.
23
3.2. Methods
3.2.1. Washing of IBA
For Part 1 of this study, IBA of sizes F3, F4 and F5 were washed with deionized water, seawater
and brine to produce wash water: W-1-DI, W-1-SW and W-1-BR respectively. A standardized
liquid to solid (L/S) ratio of 2 was used each time during washing. 500 g of F3/F4/F5 ash was
mixed with 1000 mL of leachant in a 2 L extractor bottle. During washing, the bottles were tightly
screwed and placed in a rotary agitation device where they rotated at 30 rpm for 1 hour at room
temperature. Subsequently, vacuum filtration using a 0.45 μm nylon membrane filter paper was
carried out to separate the alkaline wash water and the wet ash. The wet ash was oven-dried at a
temperature of 105oC for 24 hours. Then, Round 2 washing with deionized water was carried out
on the dried ashes to produce wash water W-2-DI-DI, W-2-BR-DI and W-2-SW-DI.
For Part 2 of this study, IBA of size less than 4.00 mm was washed with deionized water with an
L/S ratio of 4. 350 g of wash was mixed with 1400 ml of leachant in a 2 L extractor bottle.
For both parts of this study, the electrical conductivity (EC) and pH of the wash water produced
was measured and recorded to provide an indication of its physical and chemical properties.
3.2.2. Generating Alkaline Residue

In Part 1 of this study, W-1-DI was mixed with SW and BR in the following proportions by
volume:
i. S1: 25% W-1-DI + 75% BR
ii. S2: 25% W-1-DI + 75% SW
iii. S3: 50% W-1-DI + 50% BR
iv. S4: 50% W-1-DI + 50% SW
v. S5: 75% W-1-DI + 25% BR
vi. S6: 75% W-1-DI + 25% SW
Vacuum filtration was carried out using a 0.45 μm nylon filter paper to extract the solid residue
and filtrate (Used Water 1) separately.
In Part 2 of this study, W-1-DI was mixed with BR in the following proportions by volume:
i. M1: 25% W-1-DI + 75% BR
ii. M2: 50% W-1-DI + 50% BR
iii. M3: 75% W-1-DI + 25% BR
Due to difficult recovery of residues from vacuum filtration, an alternative method was used to
24
recover the residues in Part 2 of this study. The brine was added to wash water in the above-
mentioned proportion in 150 ml bottles. These bottles were placed in the centrifuge machine and
rotated at 800 rpm to allow the solid residues to settle. The used water forming the top layer was
thereafter discarded.
For both Part 1 and 2 of this study, the residues obtained were oven-dried at a temperature of
105oC for 24 hours. The mass of the residues generated from the various mixed solutions was
measured and recorded. Characterisation tests were carried out on the residues to determine its
chemical composition, as well as on the filtrate (Used Water 1 in Figure 2) to determine its
suitability for discharge according to aforementioned standards set by PUB and NEA (Section
1.3).
3.2.3. Carbonation
A 40 mL system was used for carbonation. To simulate actual flue gas composition, the gas
mixture used for carbonation experiments consisted of 15% CO2 (g) and 85% N2 (g). The flow
rate for CO2 and N2 was maintained at 60 ml/min and 340 ml/min respectively throughout the
experiments. All experiments were carried out at room temperature and pressure. The pH and EC
were measured periodically throughout the experiment and carbonation continued until pH 8.3
was achieved to avoid potential dissolution of carbonates at a lower pH.
In Part 1 of this study, solutions generated from both rounds of washing (W-1-DI, W-1-BR, W-
1-SW, W-2-DI-DI, W-2-BR-DI and W-2-SW-DI) were carbonated separately. Subsequently,
mixing of W-1-DI with SW and BR was carried out to produce S1 – S6 solutions. These solutions
were then carbonated separately as well.
In Part 2 of this study, W-1-DI was mixed with BR to produce M1 – M3 solutions. The residues
obtained from the subsequent filtration of these mixtures were combined and added back into
brine to form the following mixtures:
i. R1: 1.2 g of residue in 40 mL BR
ii. R2: 1.86 g of residue in 40 mL BR
iii. R3: 3.72 g of residue in 40 mL BR
iv. R4: 5.58 g of residue in 40 mL BR
A summary of all solutions used in this project can be formed in Appendix A: Summary of
solutions produced
25
Subsequently, vacuum filtration was carried out using a 0.45 μm nylon filter paper to separate the
carbonates formed and the filtrate (Used Water 2). Like the residues, the carbonates were also
oven-dried at 105oC for 24 hours. Characterisation testing was carried out on the carbonates to
determine its chemical composition and on the filtrate to determine its suitability for discharge
into Singapore’s watercourse.
3.2.4. Characterisation testing

It is necessary to characterize the solids formed during the experiments to confirm the true nature
and quality of the solid products obtainable; it is also important to ensure that the used water
generated during the experiments meets the local discharge criteria set by NEA and PUB.
Firstly, to analyse the residues and carbonates formed in the experiments, Fourier Transform
Infrared Spectroscopy (FTIR) and X-Ray Diffraction (XRD) was carried out. In FTIR, infrared
radiation is passed through a sample. Some radiation passes through the sample, producing a
spectrum that represents the ‘molecular fingerprint’ of the sample [25]. Thus, the spectra
generated allows for useful insights about the chemical composition and identity of the sample.
However, this technique is not quantitative in nature and thus needs to be supplemented by the
XRD. The XRD is a technique used to determine the crystallographic structure of a material by
exposing the samples to radiation and measuring the scattering angles and intensities of the X-
rays that leave the sample [26]. For XRD testing, the residues generated from S1 – S6 and M1 –
M3 were combined; and the carbonates produced from carbonation of R1 – R4 were combined.
The XRD results were used to corroborate the findings from FTIR and provide further insights
into the identity of the products formed.
Secondly, elemental testing using Inductively Coupled Plasma – Optical Emission Spectrometry
(ICP-OES), Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) and Ion
Chromatography (IC) was carried out for the following samples:
(a) Brine (BR)

(b) Seawater (SW)
(c) Wash water from both rounds of washing
(d) Solutions S1 – S6 and M1 – M3
(e) Carbonates
(f) Alkaline residue
(g) Used water 1 and 2
26
IC is used to measure the concentration of major anions such as chlorides, fluorides, sulfates,
nitrites and nitrates. The detection limit for chloride and sulfate, which are the main anions
measure in this project, is 0.5 parts per million (ppm) [27]. On the other hand, ICP-OES
determines the wavelength characteristics of excited atoms and ions. Conversely, ICP-MS uses
mass spectrometry to determine total element concentration. Generally, ICP-MS has a lower
detection limit of 0.1 parts per billion (ppb), while ICP-OES has a detection limit of 0.1 parts per
million (ppm) [28]. However, the actual detection limit typically depends on the element that is
being measured. Both ICP-OES and ICP-MS analyses are required, as each method has its own
limitations in terms of detecting specific elements. For example, ICP-OES cannot be used to
determine the presence of arsenic (Ar), mercury (Hg), or other heavy metals with extremely low
regulatory limits. On the other hand, in this project, ICP-MS cannot be used to determine the
concentrations of potassium (K), sodium (Na), calcium (Ca) and magnesium (Mg) in certain
samples because these elements are present in exceedingly high concentrations and could damage
the sensitive ICP-MS system.
27
4. Results and Discussion
4.1. Part 1: Results from washing with different leachants
CO3 2− , OH − and HCO3− ions contribute to the alkalinity of a solution. The phenolphthalein
alkalinity (P-alkalinity) of a solution can be measured by performing titration with an acid till the
endpoint of pH 8.3. The P-alkalinity of wash water generated from both rounds of washing was
calculated by performing titration using 0.1M of HCl solution.
From Error! Reference source not found.Error! Reference source not found., it can be seen
that one round of washing generally produces washing water with higher alkalinity, as compared
to two rounds. This indicates that the first round of washing is sufficient to extract most of the
alkalinity from the IBA. Washing IBA with DI water generates wash water with a higher
alkalinity of up to 1900 mg/L CaCO3, as compared to washing it with SW or BR.
Round 1 Washing
F3 (1.0 - 4.0)
2000
F4 (0.5 - 1.0)
F5 (< 0.5)
P-alkalinity (mg/L CaCO3)
1500
1000
500
0
W-1-DI W-1-SW W-1-BR
Round 2 Washing
F3 (1.0 - 4.0)
2000
F4 (0.5 - 1.0)
F5 (< 0.5)
1500
1000
500
0
W-2-DI-DI W-2-SW-DI W-2-BR-DI
Figure 6: P-alkalinity of wash water from both rounds of washing
28
There is no significant variation in the alkalinity of W-1-DI across the different size factions. As
a result, in Part 2 of this study, these fractions were combined and ash of size <4.00 mm was
washed once.
4.2. Part 1: Residues obtained from mixing W-1-DI with BR and SW

4.2.1. Formation of residues
When W-1-DI was mixed with SW or BR, a white residue was formed in the solution (Figure
7Figure 7). Vacuum filtration was carried out on the solution to extract the white residue. P-
alkalinity of the solutions before and after filtration was calculated by performing titration. Table
6Table 6 shows the changes in P-alkalinity of the solutions after mixing and after filtration. The
alkalinity measured after mixing was slightly lower than the estimated alkalinity. In F3’s case, an
average of 61% of the original alkalinity was retained after mixing. After filtration, a significant
amount, an average of 96% of alkalinity was removed. In F4’s case, an average of 88% of
alkalinity was retained after mixing and 96% of alkalinity was removed after filtration. The
significant drop in alkalinity after filtration suggests that the white residues formed after mixing
are alkaline in nature and could be hydroxides.
A previous study was done to examine pretreatment of seawater through precipitating softening,
using CO2 as the precipitator and NaOH as the alkali source. The initial solution contained Mg2+
and Ca2+ ions in the ratio of 3.02, which is comparable to the mixed solutions S1 used in Part 1
of this study, which has a ratio of 2.68. As NaOH was added, Mg(OH)2 was precipitated first
instead of Ca(OH)2, which is reasonable as the Ksp for Mg(OH)2 is smaller than that of Ca(OH)2
at room temperature. Ca2+ ions would only bond with OH- once enough OH- ions are introduced
by alkali source [29]. This supports the observation of white residues obtained after mixing and
suggests that its identity could be Mg(OH)2.
29
Figure 7: White residues produced from mixing W-1-DI with BR/SW
Since the white residues obtained are alkaline in nature, we foresee that the residues can be used
as a source of alkalinity in various industrial applications, as discussed in Section 2.6. One such
application could be to enhance the carbonation procedure and scale it up by reintroducing the
residues into brine as a much more economical source of alkalinity instead of W-1-DI. This
possibility is explored in Part 2 of this study.
30
Table 6: Change in alkalinity of F3 and F4 solutions after mixing and filtration.
P-Alkalinity (mg/L CaCO3)

Type of Retention Removal
Mixed solutions Before After
ash used Estimated after mixing (%) after filtration (%)
filtration filtration
25% W-1-DI + 75% BR 286 181 10 63 94
50% W-1-DI + 50% BR 573 300 11 52 96
75% W-1-DI + 25% BR 860 494 8 57 98
25% W-1-DI + 75% SW 287 181 5 63 97

F3
50% W-1-DI + 50% SW 573 381 6 66 98
75% W-1-DI + 25% SW 860 556 13 65 98
25% W-1-DI + 75% BR 448 413 20 92 95
50% W-1-DI + 50% BR 895 722 33 81 95
75% W-1-DI + 25% BR 1343 988 31 74 97
25% W-1-DI + 75% SW 448 413 28 92 93

F4
50% W-1-DI + 50% SW 895 881 26 98 97
75% W-1-DI + 25% SW 1343 1219 39 91 97
31
4.2.2. Chemical composition of residues
Elemental testing was carried out on the residues formed during mixing using ICP-OES. It was
found that the residues contained mainly Na+, Mg2+, and Ca2+ cations as well as Cl- and SO42-
anions (
50% SW
50% BR
1 10 100 1000 10000

Mass (mg/g residue)
SO4 Cl Na Mg K Ca Al
Figure 8
Figure 8).
Figure 8: Mass of elements in residues generated from the mixing of 50% BR and 50% SW.
FTIR was conducted on the residues and it was found that the residues consisted of hydroxides,
more specifically, Ca(OH)2 and Mg(OH)2 [30]. Figure 9Figure 9Error! Reference source not
found. shows the FTIR spectra obtained for the two sets of residues obtained after mixing W-1-
DI with SW and BR.
32
W-1-DI + SW Residue
3381 1632 1431

3697
1115
858
652
4000 3400 2800 2200 1600 1000 400
W-1-DI + BR Residue
3697
3391
1418
1630
1115
872
644
4000 3400 2800 2200 1600 1000 400
O-H Sulfate S-O

Structure O-H Bending
Stretching Stretch
1350 – 1450,
Wavelength (cm-1) 3300 – 3400 1140 – 1080
600 – 750
Figure 9: FTIR Spectra of residues generated from mixed solutions.
33
4.2.3. Yield of residues generated
It was observed that the yield of residues decreased as the percentage of W-1-DI added to the
mixture decreased (Figure 10Figure 10). This supports the hypothesis of the residues being
alkaline. Since the W-1-DI acts as the main source of alkalinity in the form of OH- ions, lesser
hydroxides would be expected to form as a smaller proportion of W-1-DI is added.
1.2
1 SW BR
Yield of residues (mg/mL)
0.8
0.6
0.4
0.2
0
25% 50% 75%
Percentage of BR/SW added
Figure 10: Change in yield of residues across three different mixtures.
4.3. Part 1: Changes in pH and EC during carbonation

The pH and EC of the 40 mL system was measured at periodic intervals throughout the
carbonation process. This was done to provide a visual indication of ion activity in the system.
Error! Reference source not found.Error! Reference source not found. shows the changes
in the pH and EC of F4 solutions during carbonation. During carbonation, as the pH of the solution
dropped, the measured EC dropped as well. A logarithmic curve was observed and after the
conversion of pH to concentration of OH- ions, a linear correlation was obtained. The decrease in
EC can be attributed to the formation of carbonates. Since the EC is a measure of the concentration
of ions in the system, as more carbonates are precipitated during carbonation, lesser free ions are
present in the system, explaining the drop in EC.
34
(a) W-1-DI (b) W-1-SW (c) W-1-BR
25 95 70
20
90 65
EC (mS/cm)
EC (mS/cm)
EC (mS/cm)
15
85 60
10
80 55
5
0 75 50
14 12 10 8 13 12 11 10 9 8 14 12 10 8
pH pH pH
Figure 12: Changes in pH and EC for (a) W-1-DI, (b) W-1-SW and (c) W-1-BR.
(a) (b) (c)
25 95 70
20
90 y = 0.2076x + 84.289 65
EC (mS/cm)
R² = 0.9463
EC (mS/cm)
EC (mS/cm)
15
85 60
10 y = 0.1386x + 13.621
R² = 0.9881
80 55 y = 0.1977x + 58.475
5
R² = 0.9806
0 75 50
50 40 30 20 10 0 10 8 6 4 2 0 25 20 15 10 5 0
[OH-] x 10-3 M [OH-] x 10-3 M [OH-] x 10-3 M
Figure 11: Changes in EC and [OH-] for (a)W-1-DI, (b) W-1-SW and (c) W-1-BR.
35
For carbonation of mixed solutions (S1 – S6), relatively stable EC values were observed over the
carbonation period. Similar to the findings described in previous study, the stable EC observed
can hence be explained by the formation of carbonates and dissolution of alkaline residues [29].
4.4. Part 1: Relationship between P-alkalinity and yield of carbonates

Figure 13 and Figure 14 depict how the total yield of carbonates produced changed when these
solutions of differing alkalinity underwent carbonation. For carbonation of Round 1 washing
solutions (Figure 13Figure 13), high R2 values of 0.80 – 0.97 were achieved, which suggests that
P-alkalinity is a good parameter to estimate the expected yield of carbonates produced during
carbonation. In addition, the correlation for individual types of wash water (W-1-DI, W-1-BR,
W-1-SW) is better than that of the combined data points, suggesting that P-alkalinity may be the
primary parameter for the carbonation process, but other factors such as the salt content of the
solutions may affect the yield.
For carbonation of mixed solutions (Figure 14Figure 14), a similar trend was observed where high
R2 values of 0.79 – 0.90 were obtained. In addition, the yield of carbonates produced increased
as the proportion of W-1-DI added increased. This is expected as the alkalinity of the mixed
solutions is contributed by the W-1-DI solution which provides OH- ions to make the pH more
favourable for the carbonation process.
36
(a) W-1-DI (b) W-1-SW
1600 Total 1600 Total
1400 Recovered 1400 y = 0.6955x + 15.992
y = 0.4694x + 36.112
Recovered R² = 0.9589
1200 R² = 0.9281 1200
Yield (mg/L)
Yield (mg/L)
1000 1000
800 800
600 600 y = 0.5328x - 23.107
400 400 R² = 0.8889
200 y = 0.3613x - 195.69 200
0 R² = 0.9357 0
0 500 1000 1500 2000 2500 0 500 1000 1500 2000 2500
P-Alkalinity (mg/L CaCO3) P-Alkalinity (mg/L CaCO3)
(c) W-1-BR (d) W-1-DI, W-1-SW and W-1-BR

1600 1600
Total y = 0.6774x + 257.16 Total
1400 1400
R² = 0.9748 Recovered
1200 Recovered 1200 y = 0.4857x + 226.98
Yield (mg/L)
Yield (mg/L)
1000 1000 R² = 0.7371
800 800
600 600
400 y = 0.5836x - 24.947 400 y = 0.3726x + 30.456
R² = 0.9999 R² = 0.6148
200 200
0 0
0 500 1000 1500 2000 0 500 1000 1500 2000 2500
P-Alkalinity (mg/L CaCO3) P-Alkalinity (mg/L CaCO3)
Figure 13: Change in total and recovered yield of carbonates over P-alkalinity for (a)W-1-DI, (b) W-1-SW, (c) W-1-BR (d) Combined solutions.
37
(a) W-1-DI + BR
1200
Total Yield
1000 Recovered Yield
Yield (mg/L)
800
y = 0.8712x - 8.8473
600 R² = 0.746
400
y = 0.7742x - 120.38
200
R² = 0.6812
0
0 200 400 600 800 1000 1200
(b) W-1-DI + SW
1200 Total Yield
Yield (mg/L)
800 y = 0.6016x + 129.73

R² = 0.7091
600
400
200 y = 0.4499x - 14.753

R² = 0.7248
0
0 200 400 600 800 1000 1200 1400
(c) W-1-DI + BR/SW

1200
Total Yield
Yield (mg/L)
800 y = 0.6974x + 77.091

R² = 0.7064
600
400
y = 0.5498x - 38.458
200 R² = 0.6136
0
0 200 400 600 800 1000 1200 1400
Figure 14: Change in yield over P-alkalinity of W-1-DI mixed with (a) BR, (b) SW, (c) BR or SW.
38
4.5. Part 1: Results for carbonates formed during carbonation
Elemental analysis and FTIR was carried out for carbonates precipitated during the aqueous
carbonation rection. From elemental testing using IPC-OES (Figure 15), Ca was identified to be
the dominant element. There are also other trace heavy metals present in the carbonates, such as
Cr, Ni, Pb, Ti and Ba.
F3 Round 1 carbonates
W-1-BR Al
Cr
Ni
W-1-SW
Pb
Ti
W-1-DI Ba
S
0 20000 40000 60000 80000 100000 120000 140000 Ca

Mass of elements (mg/kg carbonates)
Figure 15: Mass of elements present in F3 carbonates.
For FTIR analysis (Figure 16), the peaks obtained from FTIR spectra for pure calcium carbonates
were compared against those of the carbonates formed during the experiments. Calcium
carbonates are hence confirmed to be present in abundance [30]. There are also some impurities
present, which are identified to be sulfates. The carbonates generated from W-1-BR and W-1-SW
have a greater presence of these sulfate impurities as compared to those generated from W-1-DI.
39
CaCO3 W-1-DI
872
1393 872 1393
712 1078
712
4000 3400 2800 2200 1600 1000 400 4000 3400 2800 2200 1600 1000 400
-1
Wavelength (cm ) -1
Wavelength (cm )
W-1-SW W-1-BR
1132 872
1391 1142 872 1391
1082 1082
712
710
4000 3400 2800 2200 1600 1000 400 4000 3400 2800 2200 1600 1000 400
-1
Wavelength (cm ) -1
Wavelength (cm )
Structure Carbonate C-O Stretch Sulfate S-O stretch Carbonate C-O Out-of-plane bend
Wavelength (cm-1) 1510 – 1410 1140 – 1080 880 – 860
Figure 16: FTIR Spectra of (a) Pure carbonates and carbonates produced from (b)W-1-DI, (c)W-1-SW, (d) W-1-BR
40
4.6. Part 2: Results from generation of alkaline residues
4.6.1. Yield of alkaline residues
As can be seen from Figure 17, the yield of alkaline residues decreased as higher proportion of
brine (and a lesser proportion of W-1-DI) was used. These results are similar to those obtained in
Part 1 and confirm that the volume of alkaline wash water used is the main limiting factor for the
reaction involving the formation of the alkaline residue.
1.8
1.6
Yield of residues (mg/mL)
1.4
1.2
1
0.8
0.6
0.4
0.2
0
25% BR 50% BR 75% BR
Percentage of BR
Figure 17: Yield of residues generated for mixed solutions.
4.6.2. Chemical properties of alkaline residues

From characterisation testing, the dominant anions present were found to be SO42- and Cl- while
the dominant cations present were found to be Na+, Mg2+, K+, Ca2+ and Al3+. The chemical
composition of alkaline residues, found from elemental testing, is shown in Figure 18.
OH
75% Br SO4
Cl
Na
50% Br Mg
K
Ca
25% Br
Al
0 100 200 300 400 500 600

Mass of elements (mg/kg residues)
Figure 18: Mass of measured elements in residue.
41
From XRD analysis (Figure 19), the alkaline residues were found to contain mainly NaCl with
some KCl and CaSO4.12H2O. However, Mg(OH)2 was not detected indicating that it is potentially
present in amorphous form.
25% BR 1 1: Sodium Chloride (NaCl)

50% BR 2: Potassium Chloride (KCl)
75% BR 3: Calcium sulfate hydrate (CaSO4.12H2O)
3 3 2 3 1 1
0 5 10 15 20 25 30 35 40 45 50 55 60 65
2 Theta
Figure 19: XRD Spectra for residues in Part 2.
4.7. Part 2: Results from adding residue back into BR

4.7.1. Alkalinity of mixed solutions (R1-R4)
4000
3500
P-Alkalinity (mg/L CaCO3)
3000 y = 27235x - 794.57

R² = 0.8256
2500
2000
1500
1000
500
0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
Total residue added (g/mL)
Figure 20: Comparison of P-alkalinity of solutions R1 – R4.
As seen from Figure 20, a linear correlation is observed and a high R2 value of 0.82 is obtained.
The P-alkalinity of the solution increases linearly as the mass of residue added into the system
increases. This means that the mass of residue added can be used as a good parameter to estimate
the expected P-alkalinity of the solution to be carbonated.
42
4.8. Part 2: Results from carbonation experiments
4.8.1. Change in pH and EC during carbonation
The average carbonation period (time taken for the pH of the solution to reach 8.3) was 462.5
seconds. During the carbonation of Solutions R1 – R4, a fluctuating pH was observed (Figure
21), indicating that the alkaline residues kept precipitating and redissolving in the brine system,
causing the concentration of OH- to vary. This is supported by the EC trend (Figure 22). The EC
remained relatively stable throughout the carbonation experiments, indicating that the
concentration of ions in the solution remained constant to a large extent. Due to the fluctuating
pH, the carbonation experiments for solutions R1 – R4 took a significantly larger amount of time
than the experiments carried out in Part 1 for W-1-DI, W-1-BR, W-1-SW, W-2-DI-DI, W-2-BR-
DI and W-2-SW-DI.
9.20
1.20 g of residue
9.10
1.86 g of residue
9.00
3.72 g of residue
8.90
5.58 g of residue
8.80
pH
8.70
8.60
8.50
8.40
8.30
8.20
0 100 200 300 400 500 600
Time (s)
Figure 21: Change in pH over time during carbonation
170
160
150
140
EC
130 1.20 g of residue

120 1.86 g of residue
3.72 g of residue
110
5.58 g of residue
100
90
0 100 200 300 400 500 600
Time (s)
Figure 22: Change in EC over time during carbonation
43
4.8.2. Yield of carbonates produced
A linear correlation was found between the mass of residues added into the 40 mL BR system
and the yield of carbonates produced. A high R2 value of 0.99 was obtained for this relationship.
Similarly, a linear correlation was observed for the calculated P-alkalinity of the solutions and the
yield of carbonates produced (Figure 23). A moderately high R2 value of 0.78 was obtained for
this relationship. This corroborates the findings from Part 1 (Section 0), that the P-alkalinity of a
solution is a good parameter to estimate the yield of carbonates produced.
(a) 25000
20000 y = 5.0309x + 3934.6

R² = 0.7759
Yield (mg/L)
15000
y = 4.5767x + 3932.3
R² = 0.7569
10000
5000
Total Yield
0
0 500 1000 1500 2000 2500 3000 3500 4000
(b) 25000
20000 y = 160324x - 2143.7

R² = 0.9862
Yield (mg/L)
15000
y = 147377x - 1717.9
10000 R² = 0.9823
5000
Total Yield
Recovered Yield
0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
Total residue added (g/mL)
Figure 23: Change in yield of carbonates over (a) Total residue added (b) P-alkalinity of solution.
44
4.8.3. Chemical properties of carbonates
The chemical composition of carbonates formed after carbonation is shown in
45
Table 7. From the elemental testing, the dominant elements found were Mg, Ca and Al. It is
observed that carbonation was able to successfully remove NaCl to a large extent as the
concentration of Na and Cl in the carbonates dropped by a significant amount as compared to
their concentrations in solutions R1 – R4.
As can be seen from Figure 24, clear calcium carbonate peaks were obtained from XRD analysis.
Thus, it was confirmed that calcium carbonates were produced during carbonation. In addition,
XRD also detected peaks for the complex Magnesium Aluminium Carbonate Hydroxide Hydrate.
As elemental testing indicates that there is still a high concentration of Mg present in the
carbonates, it could be present in the form of this complex mineral.
1 1: Calcium Carbonate
2: Magnesium Aluminium Carbonate
Hydroxide Hydrate
2 1 1
1 1 1 1
2 2
2 1 1
1
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60
2 Theta
Figure 24: XRD Spectra for carbonates
46
Table 7: Comparison of dominant elements present in carbonates formed from carbonating the 4 mixed solutions.
Elements in carbonates (mg/kg)

Element R1 R2 R3 R4
Mean SD Mean SD Mean SD Mean SD
Al 43.19 0.589 36.90 0.347 32.01 0.335 43.95 0.118
Ba 0.55 0.003 0.59 0.063 9.63 0.009 8.84 0.012
Ca 24.62 0.503 20.25 0.060 42.77 0.456 49.52 0.206
Co 0.03 0.000 0.00 0.000 2.36 0.102 5.94 0.071
Cu 2.65 0.005 2.98 0.332 27.19 0.084 24.67 0.350
Fe 0.09 0.007 0.06 0.013 1.64 0.264 2.52 0.112
K 4.45 0.981 2.32 0.675 1.41 0.236 1.19 0.236
Mg 162.30 1.530 147.60 0.683 170.49 2.158 209.65 0.745
Na 2.72 0.181 1.73 0.286 1.72 0.121 2.20 0.047
Pb 0.22 0.009 0.26 0.026 3.22 0.027 2.85 0.067
Ti 0.09 0.020 0.08 0.010 1.33 0.028 1.34 0.118
Zn 0.96 0.081 0.86 0.078 12.18 0.184 19.22 0.931
Cl 12.57 1.442 12.80 0.893 17.88 0.641 25.33 0.864
SO4 33.55 1.268 35.19 1.365 30.83 2.176 48.60 1.032
SD: Standard Deviation

R1: 1.20 g of residue added in 40 mL BR
47
4.9. Part 2: Quality of used water
4.9.1. Used water 1 generated pre-carbonation
When vacuum filtration is carried out on the mixed solutions containing brine and wash water,
the filtrate obtained (Used water 1 from Figure 2) was sent for characterisation testing. Table 8
compares the elemental concentrations of the filtrate with allowable limits for trade effluent
discharge to watercourse stipulated by National Environment Agency (NEA) and water quality
requirements for trade effluent discharge into public sewer stipulated by PUB.
Mixing the W-1-DI with BR is successful in reducing the concentrations of metals such as Al, Ca
and K. However, the brine introduced into the system increases the chlorides, sulfates, Na and
Mg concentrations by a large amount.
From Table 8, it is observed that the concentrations of Ba, Cu and Zn exceed the allowable limits
by NEA while the chloride and sulfate concentrations exceed the allowable limits by PUB. Thus,
these solutions are not fit for discharge according to PUB and NEA standards.
4.9.2. Used water 2 generated post-carbonation

When vacuum filtration is carried out on Solutions R1 – R4 after carbonation, the filtrates (Used
water 2 from Figure 2) were collected separately for characterisation testing. Table 9 compares
the elemental concentrations of the filtrate with allowable limits set by NEA and PUB, similar to
Section 4.9.1.
Carbonation is successful in significantly lowering the concentrations of heavy metals such as Al,
Ba, and Hg which are contributed by W-1-DI. However, it does not manage to reduce Cu and Zn
by sufficient amounts in order to meet the discharge criteria set by NEA. Moreover, the high
chlorides and sulfates concentrations contributed by the addition of BR also remain a problem
when meeting PUB’s discharge criteria.
48
Table 8: Comparison of Used Water 1 quality (pre-carbonation) to NEA and PUB standards.
W-1-DI (mg/kg) 25% BR (mg/L) 50% BR (mg/L) 75% BR (mg/L) 100% BR (mg/L) NEA PUB
Element
Mean SD Mean SD Mean SD Mean SD Mean SD Limit Limit
Ag <0.8 - <0.1 - <0.1 - <0.1 - 0.1 5
Al 262.6 19.3 8.7 1.76 16.2 0.55 9.9 0.11 6.8 0.8
As <0.8 - <0.1 - <0.1 - <0.1 - 0.1 5
Ba 13.7 1.3 1.8 2.45 4.4 - 0.6 0.26 2 10
Ca 950 7 276.7 8.82 289.9 - 851.0 - 371 4
Cd <0.8 - <0.1 - <0.1 - <0.1 - 0.1 1
Cr <0.8 - <0.1 - <0.1 - <0.1 - 1 5
Cu 6.1 0.6 0.4 0.08 <0.1 - <0.1 - 0.1 5
Fe <0.8 - 2.9 4.27 3.5 2.73 < 0.4 0.85 10 50
K 1171 11 284.7 6.77 296.4 5.20 318.5 2.42 343 7
Mg <0.8 - 239.5 2.84 555.2 1.11 312.5 6.86 1242 10
Na 2058 2 2615.3 22.30 4760.0 6.77 6758.7 4.80 9926 42
Zn 5.3 1.0 3.7 2.83 8.3 52.00 3.1 143.63 5.9 3.7 1 10
Pb <0.8 - <0.1 - <0.1 - <0.1 - 0.1 5
Hg 0.6 0.1 <0.1 - <0.1 - <0.1 - 0.05 0.5
Ni <0.8 - <0.1 - <0.1 - <0.1 - 1 10
Se <0.8 - <0.1 - <0.1 - <0.1 - 0.5 10
Cl 9557 113 9174.7 110.41 17384.6 60.80 25733.9 226.31 31084 62 NA 1000
SO4- < 240 - 2000.5 100.96 2088.7 9.70 2932.6 22.86 4499 134 NA 1000
SD: Standard deviation, NA: Not applicable.
Bolded: Exceeds NEA limits, Bolded and underlined: Exceeds PUB limits.
49
Table 9: Comparison of Used Water 2 quality (post-carbonation) to NEA and PUB standards.
W-1-DI (mg/kg) BR (mg/L) R1 (mg/L) R2 (mg/L) R3 (mg/L) R4 (mg/L) NEA PUB

Element
Mean SD Mean SD Mean SD Mean SD Mean SD Mean SD Limit Limit
Ag <0.8 - <0.1 - <0.1 - <0.1 - <0.1 - <0.1 - 0.1 5
Al 262.6 19.3 6.8 0.8 24.1 1.97 24.6 0.9 16.7 0.7 19.9 1.9 - -
As <0.8 - <0.1 - <0.1 - <0.1 - <0.1 - <0.1 - 0.1 5
Ba 13.7 1.3 <0.1 - 0.7 0.21 0.8 0.0 0.8 0.1 0.8 0.0 2 10
Ca 950 7 371 4 1009.8 32.07 1182.1 16.7 1697.5 26.2 2037.1 59.7 - -
Cd <0.8 - <0.1 - <0.1 - <0.1 - <0.1 - <0.1 - 0.1 1
Cr <0.8 - <0.1 - <0.1 - <0.1 - <0.1 - <0.1 - 1 5
Cu 6.1 0.6 <0.1 - 0.7 0.04 1.1 0.1 2.5 0.2 3.7 0.3 0.1 5
Fe <0.8 - <0.1 - <0.1 - <0.1 - <0.1 - <0.1 - 10 50
Hg 0.6 0.1 <0.1 - <0.1 - <0.1 - <0.1 - <0.1 - 0.05 0.5
K 1171 11 343 7 1146.6 42.23 1400.3 14.0 2851.3 41.1 3926.7 90.4 - -
Mg <0.8 - 1242 10 3139.3 128.25 3434.0 52.6 4112.0 66.3 4990.0 128.9 - -
Na 2058 2 9926 42 23420.0 643.74 26393.3 257.2 33066.7 350.0 42540.0 1270.1 - -
Ni <0.8 - <0.1 - <0.1 - <0.1 - <0.1 - <0.1 - 1 10
Pb <0.8 - <0.1 - <0.1 - <0.1 - <0.1 - <0.1 - 0.1 5
Se <0.8 - <0.1 - <0.1 - <0.1 - <0.1 - <0.1 - 0.5 10
Ti <0.8 - <0.1 - 2.9 0.02 2.3 0.1 3.5 0.1 4.7 0.3 - -
Zn 5.3 1.0 5.9 3.7 4.8 0.13 4.9 0.1 3.5 0.3 3.7 0.0 1 10
Cl 9557 113 31084 62 41262.5 676.87 48743.8 79.9 66981.0 559.9 85333.6 824.9 NA 1000
2-
SO4 < 240 - 4499 134 5355.0 135.13 6200.0 64.3 7898.6 170.1 9213.4 315.9 NA 1000
SD: Standard deviation, NA: Not applicable
Bolded: Exceeds NEA limits, Bolded and underlined: Exceeds PUB limits.
50
5. Conclusion
The CCUS industry needs to meet three important conditions before large, commercial-scale
projects can become economically viable: (1) capture costs should decline, (2) CO2 becomes a
valuable raw material for existing or new products through innovation and technology and (3)
regulatory frameworks start providing incentives to account for CCUS costs [7]. This study
targeted the first two conditions by using IBA as a source of alkalinity in Part 1 and exploring the
use of Mg(OH)2 as a source of alkalinity in Part 2. Both are more economical alternatives to the
expensive solvents and extracting reagents available and used in the market today. Furthermore,
not only calcium carbonates, but alkaline residues were also found to be recovered through this
process, allowing for its widespread application in other industries as well.
In summary, the following conclusions were drawn:
i. One round of washing IBA with DI water, using an L/S ratio of 2 or 4 is sufficient to
generate wash water with high P-alkalinity, suitable for carbonation. The finer the
IBA, the higher the alkalinity generated from washing it.
ii. An alkaline residue is precipitated when W-1-DI is mixed with BR/SW. There is a
linear correlation between the yield of residues generated and the amount of alkaline
wash water added.
iii. During carbonation of Round 1 washing solutions, a linear correlation was obtained
between the EC of the solutions and the molar concentration of OH- ions present in
the system. However, for mixed solutions, EC remained constant throughout
carbonation, due to formation of carbonates and re-dissolution of residues in the
system.
iv. The products from the carbonation process are predominantly calcium carbonates, as
identified from elemental testing, FTIR and XRD analysis. Trace heavy metal
impurities such as Cr, Ni, Pb, Ti and Ba are also present.
v. A linear correlation is obtained for P-alkalinity of solution and yield of carbonates

produced. The P-alkalinity of a solution is a good parameter to estimate the expected
yield of carbonates.
51
vi. Reintroducing alkaline residues back into brine is able to produce mixtures (R1 – R4)
with high alkalinity suitable for carbonation. A strong linear correlation is obtained
between mass of residue added and P-alkalinity of the solution.
vii. Carbonation of such mixed solutions is able to successfully generate calcium

carbonates, along with a complex mineral Magnesium Aluminium Sulfate Hydroxide
Hydrate, as identified from the elemental testing, FTIR and XRD spectra.
viii. Carbonation of such mixed solutions (R1 – R4) is able to produce higher carbonate
yields as compared to those generated from W-1-DI, W-1-BR and W-1-SW.
ix. Used water 1 contains metals Ba, Cu and Zn which exceed NEA limits and it also
contains high chloride and sulfate concentrations which exceed PUB limits, hence it
is not suitable for direct discharge.
x. Used water 2 contains metals such as Cu and Zn which exceed NEA limits and it also
contains chloride and sulfate concentrations which exceed PUB limits, hence it is not
suitable for direct discharge.
Nevertheless, more research and planning required before such a technology can be applied on a
larger, industrial scale in Singapore. Detailed technological and economic evaluations need be
conducted to determine the feasibility of implementing such a technology at a plant site.
Furthermore, the potential unwillingness of plant owners to modify the existing system to include
CCUS technology should also be taken into consideration. More importantly, the third condition
mentioned earlier, the presence of a strong regulatory framework to support CCUS and ensure
standardization of its use across industries, is still not yet fulfilled. In Singapore, CCUS is still at
the exploratory stage, but with the current laser-sharp focus on climate change issues, and support
from the government for further research and development in this space, the potential for CCUS
in Singapore is indeed very high.
52
6. Recommendations
6.1. Pre-treatment of IBA before washing
As the Used Waters 1 and 2 were both found to be unsuitable for discharge according to the PUB
and NEA limits due to the presence of heavy metals such as Ba, Cu and Zn, pre-treatment of IBA
should be explored to assess if the IBA can be stabilized prior to washing. This will reduce the
concentration of these heavy metals in wash water and consequently in the Used Waters 1 and 2
as well, thus allowing it to meet the allowable limits for trade effluent discharge to watercourse
set by NEA. An example of such a stabilisation method could be chelation, which involves an
organic molecule, the chelating agent, incorporating a mineral ion or cation into a complex ring
structure [31].
6.2. Further studies on use of alkaline residue as an alkali source

There is currently extremely limited and preliminary research on the use of residues generated as
an alkali source for carbonation. The alkaline residue generated and applied in this study has low
solubility in water. Thus, future studies should focus on testing whether the residue can indeed be
used effectively as the source of hydroxides for the precipitation of calcium carbonates. Further
optimisation of the design system is also required to solve the issue of long carbonation reaction
times. This can be done by adjusting key parameters such as temperature, pressure, CO2 flowrate
and amount of residue added to the system.
6.3. Thermodynamic modelling for establishing theoretical baseline

The HSC Software can be used to form a theoretical baseline for the experiments. It provides
powerful calculation methods for examining the effects of various variables on an equilibrium
chemical system. When a user enters the raw materials, their amounts, and other process
parameters for almost any chemical process, the program will output the product's amounts. In
the Gibbs Energy Minimisation (GEM) module, calculations can also be repeated at stepwise
intervals over the range of raw material amounts or reaction temperatures in order to visualize the
effect of these process variables.
The processes of generating alkaline residues and carbonation can be simulated using the software
and the type of theoretical products formed as well as their yields should be compared with the
experimental products formed. This will help in experimental planning and further optimisation
of the design system.
53
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55
Appendices
Appendix A: Summary of solutions produced
Table 10: Summary of solutions produced in Part 1 and Part 2
Part 1
Wash water generated from washing IBA
Round 1 Wash Water:
with deionised water, brine and seawater at
W-1-DI, W-1-BR, W-1-SW
an L/S ratio of 2.
Wash water generated from washing Round 1
Round 2 Wash Water:
washed IBA with deionised water at an L/S
W-2-DI-DI, W-2-BR-DI, W-2-SW-DI
ratio of 2
Mixing Solutions:
(a) S1: 25% W-1-DI + 75% BR
(b) S2: 25% W-1-DI + 75% SW
Mixed solutions generated from mixing W-1-
(c) S3: 50% W-1-DI + 50% BR
DI with various proportions of BR and SW
(d) S4: 50% W-1-DI + 50% SW
(e) S5: 75% W-1-DI + 25% BR
(f) S6: 75% W-1-DI + 25% SW
Part 2
Mixing Solutions:
(a) M1: 25% W-1-DI + 75% BR Mixed solutions generated from mixing W-1-
(b) M2: 50% W-1-DI + 50% BR DI with 3 proportions of BR
(c) M3: 75% W-1-DI + 25% BR
Solutions for Carbonation:
(a) R1: 1.2 g of residue in 40 mL BR Final solutions for carbonation were prepared
(b) R2: 1.86 g of residue in 40 mL BR by reintroducing certain masses of the
(c) R3: 3.72 g of residue in 40 mL BR alkaline residues into a 40mL brine system.
(d) R4: 5.58 g of residue in 40 mL BR
56
Appendix B: Elemental data for brine
Sample Brine
As measured (µg/L), 4000X
As prepared (mg/L)
Elements dilution
Dup 1 Dup 2 Dup 3 Dup 1 Dup 2 Dup 3 Mean SD RSD%
Ag < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Al < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
As < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Ba < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Cd < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Co < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Cr < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Cu < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Fe < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Hg < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Mn < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Mo < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Ni < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Pb < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Sb < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Se < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Sn < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Ti < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Tl < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
V < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Zn 0.651 0.513 0.403 2.6 2.1 1.6 2.1 0.5 24
As measured (mg/L), 200X

As prepared (mg/L)
Elements dilution
Ca 1.719 1.752 1.749 344 350 350 348 4 1.0
K 1.572 1.58 1.604 314 316 321 317 3 1.1
Mg 5.751 5.799 5.763 1150 1160 1153 1154 5 0.4
Na 45.13 45.73 45.37 9026 9146 9074 9082 60 0.7

As prepared (mg/L)
Elements dilution
Dup1 Dup2 Dup3 Dup1 Dup2 Dup3 Mean SD %RSD
Cl 24.100 24.015 24.126 28920 28818 28951 28896 70 0.2
SO4 3.4897 3.4712 3.4954 4188 4165 4195 4183 15 0.4
57
Appendix C: Elemental data for seawater
Sample Seawater
As prepared (mg/L)
dilution
Elements
Ag < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Al < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
As < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Ba < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Cd < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Co < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Cr < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Cu < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Fe < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Hg < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Mn < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Mo < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Ni < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Pb < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Sb < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Se < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Sn < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Ti < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Tl < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
V < 0.1 < 0.1 < 0.1 <0.4 <0.4 <0.4 <0.4 - -
Zn 0.325 0.331 0.324 1.3 1.3 1.3 1.3 0.0 1

As prepared (mg/L)
dilution
Elements
Ca 2.158 2.147 2.15 432 429 430 430 1 0.3

K 1.77 1.772 1.778 354 354 356 355 1 0.2
Mg 6.888 6.884 6.876 1378 1377 1375 1377 1 0.1
Na 51.512 51.211 51.518 10302 10242 10304 10283 35 0.3

As prepared (mg/L)
Elements dilution
Cl 15.987 15.914 15.814 19185 19097 18977 19086 104 0.5

SO4 2.0450 2.0870 2.0687 2454 2504 2482 2480 25 1.0
58
Appendix D: Elemental data of wash water (W-1-DI)
Sample W-1-DI (L/S = 4)
Leachant DI Water
As measured (µg/L), 2000X Washing from dry IBA
As prepared (mg/kg)
Elements dilution (mg/kg)
Ag < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Al 34.467 30.063 33.954 275.7 240.5 271.6 262.6 19.3 7
As < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Ba 1.705 1.543 1.876 13.6 12.3 15.0 13.7 1.3 10
Cd < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Co < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Cr < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Cu 0.783 0.683 0.833 6.3 5.5 6.7 6.1 0.6 10
Fe < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Hg 0.092 0.081 0.067 0.7 0.6 0.5 0.6 0.1 16
Mg < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Mn < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Mo < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Ni < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Pb < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Sb < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Se < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Sn < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Ti 0.123 0.082 0.145 1.0 0.7 1.2 0.9 0.3 27
Tl < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
V < 0.1 < 0.1 < 0.1 <0.8 <0.8 <0.8 <0.8 - -
Zn 0.623 0.552 0.805 5.0 4.4 6.4 5.3 1.0 20
As measured (mg/L), 100X Washing from dry IBA

As prepared (mg/kg)
Ca 2.361 2.371 2.393 944 948 957 950 7 0.7
K 2.957 2.919 2.903 1183 1168 1161 1171 11 0.9
Na 5.141 5.149 5.143 2056 2060 2057 2058 2 0.1
As measured (mg/L), 600X Leaching from dry IBA

As prepared (mg/kg)
Cl 3.9396 3.9737 4.0331 9455 9537 9679 9557 113 1.2
SO4 < 0.1 < 0.1 < 0.1 < 240 < 240 < 240 < 240 - -
59
Appendix E: Elemental data for mixed solution (50% W-1-DI + 50% BR)
Sample 50% W-1-DI + 50% Br
As prepared (mg/L)
Elements dilution
Ag < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Al 3.887 4.136 4.113 15.5 16.5 16.5 16.2 0.6 3
As < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Ba < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Cd < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Co < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Cr < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Cu < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Fe 1.174 1.314 1.542 4.7 5.3 6.168 5.4 2.7 49
Hg < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Mn < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Mo < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Ni < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Pb < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Sb < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Se < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Sn < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Ti < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Tl < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
V < 0.1 < 0.1 < 0.1 < 0.4 < 0.4 < 0.4 - - -
Zn 1.8741 1.598 1.782 7.5 6.4 7.1 7.0 0.6 8

As prepared (mg/L)
Elements dilution
Ca 1.475 1.45 1.423 295 290 285 290 5 1.8
K 1.483 1.487 1.476 297 297 295 296 1 0.4
Mg 2.815 2.759 2.754 563 552 551 555 7 1.2
Na 23.800 24.060 23.540 4760 4812 4708 4760 52 1.1

As prepared (mg/L)
Elements dilution
Cl 14.5423 14.4763 14.4428 17451 17372 17331 17385 61 0.3
SO4 1.7479 1.7319 1.7418 2098 2078 2090 2089 10 0.5
60

FYP Report - Sayali Chaudhari

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Innovative use of wastes for carbon capture

Chaudhari, Sayali Sujeet

Downloaded on 11 Dec 2022 11:04:51 SGT

Chaudhari Sayali Sujeet

SCHOOL OF CIVIL AND ENVIRONMENTAL ENGINEERING

SCHOOL OF CIVIL AND ENVIRONMENTAL ENGINEERING

A Final Year Project presented to Nanyang Technological University

1.3. Scope of Work

i. Literature review on the existing landscape of CCUS and its processes.

Figure 1: Overall experimental flow for Part 1 of study.

2.2. Potential of alkaline industrial wastes for use in CCUS

Chemical composition (wt. %) Total CO2

2.2.2. Assessment of Singapore’s resources

2.2.2.1. Physical properties of IBA

Physical characteristics of IBA

2.2.2.2. Chemical properties of IBA

N: the number of elements for data analysis

2.3. Potential of brine for use in CCUS

2.3.2. Chemical composition of brine

2.4.1. Direct aqueous carbonation (DAC)

Thirdly, precipitation of Ca and Mg carbonates occurs:

2.4.2. Gas-solid pathway

Solvent price ($-

2.6. Industrial applications of Mg, Ca carbonates and Mg(OH)2

(a) (b) (c)

Figure 4: (a) F3 IBA (b) F4 IBA and (c) F5 IBA.

Figure 5: IBA of diameter less than 4 mm.

3.2.2. Generating Alkaline Residue

3.2.4. Characterisation testing

(a) Brine (BR)

Figure 6: P-alkalinity of wash water from both rounds of washing

4.2. Part 1: Residues obtained from mixing W-1-DI with BR and SW

P-Alkalinity (mg/L CaCO3)

25% W-1-DI + 75% BR 286 181 10 63 94

50% W-1-DI + 50% BR 573 300 11 52 96

75% W-1-DI + 25% BR 860 494 8 57 98

25% W-1-DI + 75% SW 287 181 5 63 97

75% W-1-DI + 25% SW 860 556 13 65 98

25% W-1-DI + 75% BR 448 413 20 92 95

50% W-1-DI + 50% BR 895 722 33 81 95

75% W-1-DI + 25% BR 1343 988 31 74 97

25% W-1-DI + 75% SW 448 413 28 92 93

75% W-1-DI + 25% SW 1343 1219 39 91 97

1 10 100 1000 10000

3381 1632 1431

4000 3400 2800 2200 1600 1000 400

4000 3400 2800 2200 1600 1000 400

O-H Sulfate S-O

Figure 9: FTIR Spectra of residues generated from mixed solutions.

Figure 10: Change in yield of residues across three different mixtures.

4.3. Part 1: Changes in pH and EC during carbonation

4.4. Part 1: Relationship between P-alkalinity and yield of carbonates

(c) W-1-BR (d) W-1-DI, W-1-SW and W-1-BR

800 y = 0.6016x + 129.73

200 y = 0.4499x - 14.753

(c) W-1-DI + BR/SW

800 y = 0.6974x + 77.091