Andrea Lucia Hidalgo Rocha Thesis

TRANSFORMATION OF ALUMINOSILICATE
MATERIALS INTO HIGH VALUE ZEOLITES
Andrea Lucia Hidalgo Rocha

BEng (EnvEng)
Submitted in fulfilment of the requirements for the degree of
Doctor of Philosophy
School of Mechanical, Medical and Process Engineering

Faculty of Engineering
Queensland University of Technology
2023
Keywords
Acid treatment, Artificial Neural Network, Cancrinite, Cation-exchange
capacity, Hydrothermal, Lithium, Machine Learning, Mother liquor, Natural zeolite,
Quench Method, Spodumene, Thermal Activation, Waste recycling, Zeolite synthesis
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Abstract
Zeolites are essential materials in various industries and applications due to their
unique chemical and physical properties. They find extensive use in areas such as
catalysis, adsorption, detergents, agriculture, construction, renewable fuels, industrial
chemistry, water treatment, and antiseptics. Traditionally they are made from alkaline
solutions of sodium silicate and sodium aluminate in the presence of an organic
template. However, in recent years, there has been growing interest in developing
sustainable methods for synthesizing zeolites using waste materials. While such efforts
hold significant promise, they are also beset by several challenges. In particular,
impurities present in waste materials can exacerbate the difficulties involved in
synthesizing zeolites, and the process of recycling mining waste in particular is
restricted by the energy-intensive nature of existing methods and their limited
scalability for widespread industrial implementation.
The first method discussed in this research is the synthesis of zeolite LTA from waste
spodumene leachate residue (SLR) from the lithium industry. Following the activation
of SLR, two distinct products were generated: a silica-rich mother liquor and
cancrinite. Subsequently, as a next step in the process, zeolite LTA was formed using
the silica-rich mother liquor resulting from the activation of SLR through the
application of alkaline solutions at a temperature of 240 oC. The mother liquor was
doped with sodium aluminate to ensure a Si/Al molar ratio = 1 was present. This
mixture was subjected to hydrothermal synthesis at 80 oC and ultimately produced
high-purity material. It is noted that the various impurities present in the waste
precipitated and as a consequence were mixed with the solid cancrinite.
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However, the production of cancrinite posed a challenge as it has little inherent value.
One approach was to dissolve the cancrinite with hydrochloric acid to make active
aluminium and silica species which could be subsequently neutralized with NaOH.
Zeolite LTA was then synthesized by hydrothermal reaction. However, the presence
of sodium chloride in this process was problematic, as it impacted the recycling of the
mother liquor and wash water, and ultimately resulted in the generation of wastewater.
Thus, alternative methods for cancrinite utilization were necessary.
The next method presented in this study, successfully addressed the issues encountered
in the first method. The process involved the conversion of natural zeolite waste
powder into two products, namely zeolite LTA and lanthanum-loaded cancrinite. The
high silica content in natural zeolites promoted the formation of zeolite LTA (i.e.,
mother liquor containing substantially more silicates than when using SLR) and
reduced the amount of cancrinite to be dealt with. Notably, the quality of the zeolite
LTA was not only of high crystallinity but also relatively pure. Doping of the
cancrinite powder with lanthanum species resulted in an acceptable method for
removing phosphate species from water and wastewater resources. Although the initial
performance of the cancrinite-based sorbent was encouraging, it is recommended that
future studies focus on improving the physical properties of the sorbent material.
Despite the success of the previous processes in producing high purity zeolites, there
was still scoped to reduce the activation temperature and to avoid making two
products. The "Quench Method" for zeolite LTA synthesis was discovered. The
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approach was to activate the waste in the first stage using high molarity NaOH
solutions (which normally end up making cancrinite and sodalite). Then at a key point
in time, addition of sodium aluminate solution occurred which quenched the activation
process and created conditions suitable for making zeolite LTA. Notably, the addition
of a slight excess of aluminium in the solution further improved the zeolite synthesis
process. The Quench Method has the potential to transform lithium industry waste as
activation occurs at only 100 oC.
To further optimize the proposed method for zeolite synthesis, the use of continuous
reactors is recommended. However, one of the primary challenges in employing such
reactors for this purpose is the issue of viscosity. As the reaction progresses, the
presence of solids in the mixture increases, resulting in increased viscosity, which can
cause problems such as reactor clogging, uneven heat distribution, and difficulties in
controlling the reaction conditions. To address this issue, a combination of a
continuous and a batch reactor has been considered, with the former used solely for
the activation phase to obtain active Si and Al species, while ensuring fast quenching
before reaching the next reactor.
By integrating Industry 4.0 principles, particularly machine learning, with continuous
reactors for zeolite synthesis, several benefits can be achieved. Incorporating machine
learning algorithms can significantly enhance the optimization of zeolite synthesis in
continuous reactors, resulting in reduced production time and costs, improved product
quality, and minimized waste. These algorithms can analyse real-time data collected
from sensors and other sources to dynamically adjust the operating parameters of the
reactor, such as temperature, pressure, and flow rate, thereby maximizing the
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efficiency of the synthesis process. Additionally, machine learning algorithms can
predict potential issues and provide early warnings, allowing for timely corrective
actions to be taken, minimizing downtime, and reducing the need for manual
intervention, which is often time-consuming and prone to human error. Therefore, this
study also addressed the need for a clean dataset to facilitate machine learning in
zeolite synthesis.
Developing suitable datasets is particularly challenging when comparing zeolite
synthesis parameters between different laboratories, which can negatively affect the
accuracy of machine learning predictions. To overcome this, researchers must
establish their own database, which involves conducting multiple experiments and is
time-consuming. Zeolite LTA serves as an excellent case study due to its well-
established synthesis process. This study identified critical factors, including limited
use of quantitative X-ray diffraction (XRD) methods in published literature, the lack
of reporting of the mass balance of processes, and the impact of vessel dimensions and
design on the synthesis process. Recommendations include pre-heating of reactant
solutions to minimize variation in reaction temperature and avoiding agitation of the
reactant mixture to improve the quality of zeolite LTA.
In the final part of this thesis, the dataset created was tested using a progressive
machine learning methodology to identify the relationship between zeolite synthesis
descriptors and evaluate the potential for machine learning to predict the quantitative
output of synthesis routes. The hypothesis was that applying statistics and machine
learning principles may enable pre-evaluation and increase zeolite yield and
performance. Chapter 7 shows the application of various machine learning algorithms
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to zeolite LTA synthesis data, including linear regression, ridge regression, regression
tree, random forest, XGBoost, and artificial neural network models. Using artificial
neural networks resulted in 85 % accuracy in predicting the zeolite synthesis process.
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Table of Contents
Keywords ................................................................................................................ 1
Abstract .................................................................................................................. 2
Table of Contents ..................................................................................................... 7
List of Figures .......................................................................................................... 9
List of Tables ......................................................................................................... 13
List of Abbreviations............................................................................................... 15
Acknowledgements ................................................................................................. 17
List of Publications ................................................................................................. 18
Chapter 1: Introduction .......................................................................................1
Background ............................................................................................................. 1
Research Problem ..................................................................................................... 2
Research Aims and Objectives .................................................................................... 3
Thesis Outline .......................................................................................................... 4
Chapter 2: Literature Review...............................................................................7
Lithium in Australia .................................................................................................. 7
Lithium Mining Process............................................................................................. 7
Spodumene Leachate Residue (SLR) ........................................................................... 9
Natural Zeolites mining ........................................................................................... 10
Low silica zeolites from alumino-silicate waste ........................................................... 11
Zeolite Synthesis .................................................................................................... 12
Zeolite synthesis methods ........................................................................................ 15
Industry 4.0............................................................................................................ 20
Machine Learning ................................................................................................... 21
Key insights ........................................................................................................... 25
Chapter 3: Feasibility of Zeolite LTA Synthesis from Spodumene Leachate
Residue via Cancrinite Formation......................................................................26
Abstract ................................................................................................................ 26
Introduction ........................................................................................................... 27
Materials and Methods ............................................................................................ 32
Results and Discussion ............................................................................................ 39
Conclusions ........................................................................................................... 66
Key Insights........................................................................................................... 68
Chapter 4: Transformation of natural zeolite powder to synthetic zeolite LTA
for water softening and lanthanum coated cancrinite for phosphate removal. ..70
Abstract:................................................................................................................ 70
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Introduction ........................................................................................................... 71
Materials and Methods............................................................................................. 75
Results and Discussion ............................................................................................ 81
Conclusions ........................................................................................................... 96
Key Insights ........................................................................................................... 97
Chapter 5: “One Pot” Synthesis of Zeolites: Activation of Spodumene Leachate
Residue using a New Quench Method ............................................................... 98
Abstract................................................................................................................. 98
Introduction ........................................................................................................... 99
Materials and Methods........................................................................................... 104
Results and Discussion .......................................................................................... 109
Conclusions ......................................................................................................... 130
Key Insights ......................................................................................................... 131
Chapter 6: Factors which Influence Development of Robust Data Sets for
Machine Learning and Statistical Analysis of Zeolite Synthesis ..................... 133
Abstract............................................................................................................... 133
Introduction ......................................................................................................... 134
Material Characterization ....................................................................................... 139
Solution Analysis .................................................................................................. 140
Conclusions ......................................................................................................... 170
Key Insights ......................................................................................................... 172
Chapter 7: Evaluation and application of machine learning principles to Zeolite
LTA synthesis .................................................................................................. 173
Abstract............................................................................................................... 175
Introduction ......................................................................................................... 176
Conclusions ......................................................................................................... 211
Chapter 8: Conclusions and Future Work ...................................................... 213
Conclusions ......................................................................................................... 213
Future Work......................................................................................................... 216
Bibliography .................................................................................................... 218
Appendices ....................................................................................................... 235
Appendix A ......................................................................................................... 235
Appendix B.......................................................................................................... 245
Appendix C.......................................................................................................... 246
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List of Figures
Figure 1: Process flow diagram for making both cancrinite and zeolite LTA from
Spodumene Leachate Residue ............................................................. 33
Figure 2: Process flow diagram for the synthesis of zeolite LTA from Spodumene
Leachate Residue via cancrinite formation; Additional NaAlO 2
added to the feed stream to the high temperature hydrothermal
reactor. ............................................................................................ 35
Figure 3. Process flow diagram for the synthesis of zeolite LTA from Spodumene
Leachate Residue via cancrinite formation; Additional NaAlO 2
added to the cancrinite product. ........................................................... 36
Figure 4. Influence of time and NaOH molarity upon cancrinite synthesis from
SLR at 150 and 200 ℃ a) Crystalline cancrinite, b) non-Diffracting
material. Uncertainties were calculated with a 95% confidence
interval. ........................................................................................... 39
Figure 5: SEM images of solid material created by NaOH treatment of SLR at
temperatures of 150 and 240 o C ........................................................... 43
Figure 6: Process flow diagram including stream tables for (1) conversion of SLR
to cancrinite and (2) SLR mother liquor to zeolite LTA ........................... 47
Figure 7: SEM images of the zeolite product after hydrothermal reaction of mother
liquor modified by water and sodium aluminate addition; Reaction
temperature 80 o C; Time = 2 to 5 hours................................................. 50
Figure 8: Process flow for cancrinite synthesis from a starting mixture containing
SLR, NaOH, water and sodium aluminate; one hour at 240 o C in
hydrothermal reactor. ......................................................................... 52
Figure 9. SEM images of solid material made from cancrinite: four hours reaction
time; agitation 100 rpm; reaction temperature 80 ℃; dissolution of
cancrinite with either 2 or 3 M HCl followed by neutralization. ................ 54
Figure 10: Influence of HCl molarity on Al and Si active species formation from
cancrinite/sodium aluminate................................................................ 55
Figure 11.SEM images of zeolite LTA: Influence of different HCl concentrations
on zeolite LTA synthesis at 4 h, 80 ℃ and neutralized with 4 M
NaOH solution: Cancrinite/NaAlO2 dissolved in (a) 2 M HCl and (b)
3M HCl. .......................................................................................... 57
Figure 12: XRD determination of % of crystalline zeolite LTA in solid product as a
function of NaOH molarity used in the neutralization stage: reaction
temperature 80 o C; reaction time 4 h; Si/Al = 0.57 .................................. 57
Figure 13. Influence of NaOH molarity in the neutralization stage prior to the
formation of zeolite LTA. ................................................................... 59
Figure 14. Influence of different HCl concentrations on Zeolite LTA synthesis
using different Si/Al ratios, synthesis at 4 h, 80℃ and neutralized
with 4M NaOH solution. .................................................................... 61
Figure 15. Influence of synthesis time on zeolite LTA synthesis: reaction
temperature 80℃; 0.57 Si/Al ratio; and 100 rpm agitation........................ 62
Figure 16. Process flow diagram including stream tables for conversion of
cancrinite to zeolite LTA .................................................................... 65
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Figure 17: Concept for transformation of natural zeolite powder to synthetic zeolite
LTA and lanthanum coated cancrinite. ..................................................77
Figure 18. Active Si in the mother liquor (%) and solids recovery (g) at different
NaOH molarities ...............................................................................82
Figure 19: SEM images of solids formed after natural zeolite activation using 6 M
and 10 M NaOH: reaction temperature = 240 o C; reaction time = 1 h;
10,000x magnification. .......................................................................84
Figure 20. Mass balance for activation of natural zeolite powder using 6 M NaOH
at 240 o C for one hour followed by hydrothermal synthesis of zeolite
LTA at 80 o C for 4 h ..........................................................................88
Figure 21: Influence of synthesis time upon zeolite LTA synthesis: 80 o C, 150 rpm
and SiO2 /Al2 O3 =2.81..........................................................................90
Figure 22: Zeolite LTA SiO2 /Al2 O3 =1.90; Na2 O/SiO2 =5.11; H2 O/Na2O= 4.82, 4-
hour synthesis and 80 o C.....................................................................92
Figure 23: Equilibrium isotherms for phosphate sorption on lanthanum modified
cancrinite: Langmuir (top), Freundlich (middle) and Aranovich-
Donohue models (bottom)...................................................................94
Figure 24: Release of ions into solution as a function of from cancrinite mass
during phosphate equilibrium tests .......................................................95
Figure 25: Illustration of the “Quench” concept for making zeolite from waste
aluminosilicate materials................................................................... 103
Figure 26: SEM imaging and particle size of SLR .................................................... 110
Figure 27: Active Si and Al species in (a) mother liquor and (b) solid as a function
of NaOH molarity and contact time at 25 o C ........................................ 112
Figure 28: Active Si & Al species from SLR as a function of temperature (75℃),
NaOH molarity, and contact time. ...................................................... 113
Figure 29: Active species from SLR as a function of temperature (100 ℃), with
different NaOH molarity and contact time ........................................... 117
Figure 30: XRD analysis of active solid phase formed from reaction of SLR with
NaOH solution at 100 ℃; function of NaOH molarity and contact
time. .............................................................................................. 118
Figure 31. Active species from SLR as a function of temperature (150℃), NaOH
molarity and contact time.................................................................. 120
Figure 32. XRD analysis of active solid phase formed from reaction of SLR with
NaOH solution at 150 ℃; function of NaOH molarity and contact
time. .............................................................................................. 121
Figure 33: a) XRD and b) SEM image of the zeolite product produced by
hydrothermal reaction of non-activated SLR with with NaOH in a
sodium aluminate solution at 80 o C for 4 h: SiO2 /Al2 O3 ratio = 0.95 ........ 122
Figure 34. Influence of SLR activation temperature upon Zeolite LTA synthesis: 20
g SLR, 19.17 g NaOH, 5.33 g NaAlO2 , 80 ℃ synthesis temperature,
3.95 M NaOH ................................................................................. 124
Figure 35. Importance of hydrothermal synthesis reaction time at 80 o C for SLR
activated at 100 o C........................................................................... 125
Figure 36: SEM images of solid zeolite product formed as a function of time after
hydrothermal reaction using 3.95 M NaOH and Si/Al ratio = 0.95........... 126
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Figure 37. SEM images of solid zeolite product formed after hydrothermal reaction
using 3.95 M NaOH and Si/Al ratio = 0.83 and 3-hour synthesis time ..... 128
Figure 38. Zeolite synthesis at 80 o C as a function of reaction time: SiO2 /Al2 O3
ratio = 0.83..................................................................................... 129
Figure 39: Quantitative XRD patterns for Zeolite LTA: SiO 2 /Al2 O3 = 2; Na2 O/SiO2
= 2.5; H2 O/SiO2 = 15 to 35; Temperature = 80 o C: Note that
trendlines are only a visual aid........................................................... 143
Figure 40: SEM images of zeolite made at 80 o C as a function of time: SiO2 /Al2 O3
= 2; Na2 O/SiO2 = 2.5 and H2 O/Na2 O = 15 or 35 as indicated.................. 147
Figure 41: Mass balance for the synthesis of zeolite L .............................................. 149
Figure 42. Heating profile of vessel in heated incubator at 80 o C. Aluminosilicate
gel conditions: SiO2 /Al2 O3 = 2; Na2 O/SiO2 = 2.5, H2 O/ Na2 O = 42.......... 152
Figure 43. Quantitative XRD patterns for Zeolite LTA: SiO 2 /Al2 O3 = 2; Na2 O/SiO2
= 2.5; H2 O/SiO2 = 15 to 35; Temperature = 80 ℃, pre-heated
samples to 80℃; Reaction Time = 3 h; Reactant mixture stirred at
100 rpm ......................................................................................... 155
Figure 44. Quantitative XRD data for Zeolite LTA: SiO 2 /Al2 O3 = 2; Na2 O/SiO2 =
2.5; H2 O/SiO2 =25 to 30; Reaction Temperature = 80 ℃; pre-heated
samples at 80 ℃; Reaction Time = 3 h; No stirring ............................... 159
Figure 45. Quantitative XRD patterns for Zeolite LTA: SiO 2 /Al2 O3 = 2; Na2 O/SiO2
= 2; H2 O/ SiO2 = 20 to 30; Temperature = 80 ℃ - pre-heated samples
at 80℃........................................................................................... 161
Figure 46. Formation of zeolite LTA crystal over time at 80 o C with preheated
samples; H2 O/Na = 30, Na2 O/SiO2 = 2, SiO2 /Al2 O3 = 2.......................... 165
Figure 47. Particle Sizing for zeolite LTA: SiO 2 /Al2 O3 = 2; Na2 O/SiO2 = 2;
H2 O/Na2 O = 20 to 30; temperature = 80 ℃ - pre-heated samples at
80 ℃............................................................................................. 166
Figure 48: Histogram showing citations of publications with the keywords
"machine learning AND zeolite", "neural network AND zeolite", and
"principal component analysis AND zeolite". ...................................... 177
Figure 49. Visualisation of the different neural network structures (ANN left, DNN
right). ............................................................................................ 179
Figure 50. Knowledge discovery process. ............................................................... 182
Figure 51. Progression and application of machine learning techniques according to
complexity. .................................................................................... 183
Figure 52. Zeolite synthesis products for gel composition of SiO 2 /Al2 O3 = 2,
Na2 O/SiO2 = 2.5 and H2 O/Na2 O = 30; reaction temperature 80 o C............ 190
Figure 53. Zeolite synthesis products as a function of reaction time for gel
composition of SiO2 /Al2 O3 = 2, Na2 O/SiO2 = 2 and H2 O/Na2 O = 20 to
30; reaction temperature 80 o C........................................................... 191
Figure 54. SEM images of zeolite synthesis products as a function of reaction time
for gel composition of SiO2 /Al2 O3 = 2, Na2 O/SiO2 = 2 and H2 O/Na2 O
= 30; reaction temperature 80 o C. ....................................................... 193
Figure 55. Correlation of machine learning variables using hierarchical clustering
methods. ........................................................................................ 195
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Figure 56. (a) Variance explained by principal components (b) principal
component coefficients. .................................................................... 196
Figure 57. Biplot comparison of principal components 1, 2, 3 and 4. ........................... 198
Figure 58. Linear and ridge regression feature importance from input synthesis
variables......................................................................................... 200
Figure 59. Regression tree and random forest feature importance for input synthesis
variables......................................................................................... 203
Figure 60. XGBoost testing results using input synthesis variables (results from the
training and testing runs that resulted in the greatest model
accuracy)........................................................................................ 204
Figure 61. ANN model results using input synthesis variables (results from the
training and testing runs that resulted in the greatest model
accuracy)........................................................................................ 207
Figure 62. (a) Comparison of machine learning model results (average R^2 value)
(b) Comparison of approaches to zeolite product analysis through
ANN models (average R^2 value) ...................................................... 209
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List of Tables
Table 1. XRD analysis of solid products resultant from SLR activation at 240 o C as
a function of NaOH molarity and reaction time ...................................... 43
Table 2. XRD results after the mother liquor recycling process. ................................... 48
Table 3. XRD data for zeolite LTA synthesis from cancrinite: four hours reaction
time; agitation 100 rpm; reaction temperature 80 ℃; dissolution of
cancrinite with either 2 or 3 M HCl followed by neutralization. ................ 53
Table 4. Quantitative XRD analysis of zeolite LTA: Impact of cancrinite/sodium
aluminate acid treatment conditions ..................................................... 56
Table 5. XRD analysis of zeolite LTA activated at 2M HCl and synthesised at a
reaction temperature 80℃; 0.57 Si/Al ratio; and 100 rpm agitation. ........... 62
Table 6: Mass balance for zeolite LTA formation by conversion of cancrinite ................ 63
Table 7: XRF analysis of natural zeolite powder ........................................................ 75
Table 8. Solid materials obtained after natural zeolite powder activation at 240 o C
and one hour synthesis. ...................................................................... 83
Table 9. Mother liquor composition as a function of storage time and NaOH
molarity: natural zeolite activation at 240 o C for 1 h................................ 86
Table 10: XRF analysis of solid product from activation of natural zeolite with 6 M
NaOH at 240 o C for one hour .............................................................. 89
Table 11. XRD determination of percentage of crystalline zeolite LTA in solid
product as a function of synthesis time: reaction temperature 80 ◦C;
SiO2 /Al2 O3 = 2.................................................................................. 90
Table 12. XRF analysis of zeolite LTA made from natural zeolite powder. .................... 91
Table 13. XRF analysis of SLR............................................................................. 109
Table 14. Quantitative XRD analysis of SLR .......................................................... 110
Table 15: Quantitative XRD data for SLR activated with NaOH at 75 o C..................... 114
Table 16. XRF analysis of solid product from Zeolite LTA synthesis using SLR
activated at 100 o C........................................................................... 127
Table 17: Summary of quantitative XRD analysis of zeolite samples made at 80 o C;
SiO2 /Al2 O3 = 2; Na2 O/SiO2 = 2.5 and H2 O/Na2 O = 15 to 35; stirring
100 rpm ......................................................................................... 144
Table 18. Summary of quantitative XRD patterns for Zeolite LTA: SiO 2 /Al2 O3 = 2;
Na2 O/SiO2 = 2.5; H2 O/ Na2 O = 15 to 35; Temperature = 80 ℃,
Agitation 100 rpm, pre-heated gel at 80℃ before synthesis .................. 156
Table 19. Summary of quantitative XRD patterns for Zeolite LTA with pre-heated
and non-stirring samples: SiO2 /Al2 O3 = 2; Na2 O/SiO2 = 2.5; H2 O/
Na2 O = 20 to 30; Temperature = 80 ℃................................................ 160
samples and non-stirring: SiO2 /Al2 O3 = 2; Na2 O/SiO2 = 2; H2 O/ SiO2
= 20 to 30; Temperature = 80 ℃........................................................ 162
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Table 21. Summary of particle sizing analysis for Zeolite LTA with pre-heated
samples and no-stirring: SiO2 /Al2 O3 = 2; Na2 O/SiO2 = 2; H2 O/ SiO2
= 20 to 30; Temperature = 80 ℃........................................................ 167
Table 22. Machine learning input variables. ............................................................ 188
Table 23. Training and testing results for linear and ridge regression. .......................... 199
Table 24. Training and testing results for tree-based models....................................... 201
Table 25. Training and testing results for ANN models (Ackley, Rege, & Saxena,
2003). ............................................................................................ 206
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List of Abbreviations
Al – Aluminium
ANN- Artificial Neural Network
CEC – Calcium Exchange Capacity
Chorine- Cl
DNNs- Deep Neural Networks
HCAS- High Concentration Alkali Solution
HCl- hydrochloric acid
HEU- Heulandite
ICP-OES- Inductive Coupled Plasma-Optical Emission Spectrometer
La- Lanthanum
LOI- Loss on ignition
LTA- Linde type A zeolite
mEq- Milliequivalent
ML- Machine Learning
NaOH- Sodium Hydroxide
NZ- Natural Zeolite
OSDA- Organic Structure Directing Agents
PCA- Principal Component Analysis
QSP- Quasi-Solid Phase Activation Process
xv
SEM- Scanning Electron Microscopy
Si- Silica
SLR- Spodumene Leachate Residue
USY- Ultra-stable Y
XRD- X-ray Diffraction
XRF- X-ray Fluorescence
xvi
Acknowledgements
Firstly. I would like to express my gratitude and appreciation to my supervisory team:
Prof. Graeme Millar, Prof. Richi Nayak and Dr. John Outram for providing help and
support through my PhD journey. I am thankful for the scholarships provided by
Queensland University of Technology. This research was supported by QUT
Scholarship funding. I would like to acknowledge the Central Analytical Research
Facility (CARF) team for their help and the School of Mechanical, Medical and
Process Engineering as well as the Faculty of Engineering.
I would like to extend my gratitude to the excellent lab team I was part of for their
significant help during my candidature, Dr Josefine Probst, Dr Gabriel Colledge, Dr
Cameron Johnston and MSc Richard Freeney.
I would like to acknowledge professional editor, Sue Nielsen, who provided
copyediting and proofreading services, according to the guidelines laid out in the
university-endorsed national “Guidelines for editing research theses”.
I am very grateful for the enormous support of my family, who have always been my
strength and my friends who were with me and provided their invaluable moral support
and company during my PhD.
And last but not least, I would like to thank my fiancé and soon to be husband, Daniel,
who proofread this thesis even when he never understood my research. Thank you, my
love, for always keeping things going.
xvii
List of Publications
B. Conroy, R. Nayak, A.L. Hidalgo, and G.J. Millar. (2022) “Evaluation and
Application of Machine Learning Principles to Zeolite LTA Synthesis.” Microporous
and Mesoporous Materials 335 (Chapter 7).
DOI: https://doi.org/10.1016/j.micromeso.2022.111802
xviii
Chapter 1: Introduction
The mining industry generates significant amounts of waste material daily as part of
the mineral refining process. Disposing of this waste material in landfill sites is not
environmentally, socially, or politically acceptable. Therefore, the transformation and
optimization of waste materials into valuable products is crucial for promoting
sustainability in the mining industry. One promising solution is production of green
zeolites, which can add value to aluminosilicate waste materials.
The aim of this research is to develop an innovative approach to repurpose
aluminosilicate waste materials, such as SLR and natural zeolite powder, into synthetic
zeolites, by optimizing the activation of SLR and synthesizing zeolite LTA. The
incorporation of machine learning algorithms can significantly enhance the
optimization of zeolite synthesis in continuous reactors, leading to reduced production
time and costs, improved product quality, and minimized waste. However, creating a
robust dataset for machine learning in zeolite synthesis presents challenges, and
researchers must establish their own database for zeolite synthesis, despite the time -
consuming nature of this process.
Background
The mining industry is critical for Australia’s economy; in December 2021 the
Australian Department of Industry, Science, Energy and Resources highlighted the
vital role of the mining industry for the recovery of the Australian economy after the
COVID-19 pandemic. This estimated importance will be supported by Australia’s
Chapter 1: Introduction 1
critical mining materials such as iron ore, coal, gold, copper and the rising exports of
lithium and nickel (battery minerals).
Lithium demand has rapidly grown in the last two decades as it has become vital for
the development of industrial products, particularly batteries for electric vehicles,
hybrid vehicles and portable electronic devices (Meng, et al., 2021). Currently,
Australia is the largest producer of lithium in the world with mines located mainly in
Western Australia (Maxwell & Mora, 2019). This rapidly increasing demand for
lithium is producing tonnes of industrial waste material, which has been stored in
landfills.
Zeolite mining in Australia is still relatively small in scale but is expected to grow
(Victoria State Government, 2023). This projected growth is poised to bring about a
significant surge in waste generation.
Research Problem
The Australian mining industry contributes to 75% of the country's exports, which
impacts significantly on Australia's flourishing economy. Nevertheless, an increase in
mining activity also increases in the amount of waste material produced daily. There
is a large benefit in investigating different methods to use these waste materials which
are, as of writing, mostly disposed in landfills. It is estimated that one tonne of lithium
carbonate generates approximately 9-10 tonnes of lithium slag (D.Chen et al., 2012;
Z-h. He, et al., 2017).
Furthermore, natural zeolite deposits generate a waste material (ultrafine powder) after
the crushing step. This by-product represents a loss in production, a liability and a
potential hazard (Zijun et al. 2021). These waste materials are mainly composed of Al
and Si, which can be used as raw materials to generate higher value products such as
zeolites.
Currently, there has been limited research on the conversion of mining wastes into
valuable zeolites. This is largely due to the challenges posed by impurities in the
material, which can adversely affect the quality of the final product, as well as by the
high cost of activation. Accordingly, this thesis investigates various methods for
activating and synthesizing zeolites from waste materials, while also assessing the
potential of machine learning approaches for optimizing zeolite synthesis.
Research Aims and Objectives
This project has a twofold aim: firstly, to explore novel and environmentally
sustainable synthesis methods for producing high-quality zeolites from a variety of
waste materials; and secondly, to develop algorithms that leverage machine learning
approaches to enhance our understanding of zeolite synthesis. The project seeks to
contribute to the growing field of sustainable materials science and to advance the
application of artificial intelligence in the zeolite community. The following research
objectives were identified and addressed:
1 To develop and optimise a process to use the waste material and transform it into
synthetic minerals.
2 To create a novel process to transform lithium mining waste into zeolite LTA that
can be scaled up to industry, avoiding a fusion step.
3 To explore the potential of using natural zeolites to transform them into synthetic
zeolite LTA using the mother liquor rich in silica after zeolite activation.
4 To study the effect of different variables in zeolite synthesis to develop a robust
data set for machine learning applications.
Thesis Outline
This thesis is presented by monograph, with a total of eight chapters. Chapter 1
introduces the research, emphasising the background, research problems, aim, and
objectives. In Chapter 2, a comprehensive literature review is presented to identify
gaps in the research, such as the limited studies that have considered using Spodumene
Leachate Residue (SLR) and Natural zeolite powder as raw materials for zeolite
synthesis, as well as the challenges of applying machine learning to zeolite science.
Chapter 3 explores the feasibility of synthesising zeolite LTA from SLR via cancrinite
formation, in which the waste material is converted into cancrinite and then
reprocessed under relatively mild conditions. The cancrinite method minimises waste
of resources by recycling the mother liquor after waste material activation and zeolite
synthesis. In Chapter 4, the cancrinite method is further studied by investigating the
activation of the mother liquor using ultra-fine natural zeolite powder instead of SLR,
to maximise the use of different mining waste materials. This chapter also
demonstrates the efficacy of this methodology with different aluminosilicate materials.
Chapter 5 investigates a novel process to transform lithium mining waste into synthetic
zeolite LTA using a new quench method, representing an alternative synthesis method
that does not require a fusion step and presents green credentials such as lower
activation temperatures, solvent that can be reused in the process, and minimum water
loss. Chapters 3 to 5 detail green and sustainable alternatives to traditional synthesis
methods.
To enhance the benefits of the methodologies presented in previous chapters, machine
learning is employed to manage the large amount of data. Chapter 6 develops a robust
dataset for zeolite LTA to evaluate machine learning principles for zeolite synthesis.
In Chapter 7, different machine learning algorithms are applied to identify the
relationship between zeolite synthesis variables. Notably, the most accurate algorithm
is the artificial neural network model, with an accuracy of over 80%. However, the
accuracy of the model can be further improved by increasing the network size,
demonstrating that advanced deep learning models should be considered.
Chapter 8 serves as the concluding chapter of this thesis, summarizing the key
contributions and findings. Additionally, it outlines potential directions for future
research. The concluding section offers valuable insights into the main outcomes
derived from the study and provides suggestions for further investigation.
Furthermore, the last chapter features appendices that provide supplementary
information for a comprehensive understanding of the research. Appendix A offers
extra analysis and results, expanding upon the findings presented in Chapter 3. It
delves deeper into the data collected, providing readers with a more in-depth analysis
and supporting evidence. Appendix B showcases a continuous reactor prototype,
which serves as a tangible application of the research conducted in Chapter 5. Lastly,
Appendix C includes supplementary information related to Chapter 7, providing
further elucidation and analysis of the discussed topics. It offers additional insights,
supporting the arguments and conclusions presented in the main body of the thesis.
Chapter 2: Literature Review
Lithium in Australia
Australia is a significant global producer of lithium, which is experiencing growing
demand due to the increasing need for mobile electronics and electric vehicles.
(Courtney et al., 2017). Lithium and its compounds have historically been used in
application such as batteries, lubricating greases, pharmaceuticals (Choubey et al,
2016; Collins, et al. 2020; G. Han, et al, 2018; Z. Liu, Zhu, et al., 2019; Sun, et al.
2014), glass, ceramics, metallurgy (P. Meshram et al. 2014) and other industries. High
capacity lithium batteries are strong candidates for a feasible solution for energy
storage for the electrical power grid and they are already needed for the accumulation
of green energy (V. Flexer et al., 2018); and commonly used power sources for electric
vehicles (Setoudeh et al. 2020). This means there will most likely be a strong increase
in the demand for lithium in the coming years (Setoudeh et al., 2020).
Lithium Mining Process
Lithium is extracted mainly from hard rock ores (lithium minerals such as spodumene,
petalite and lepidolite) (Han et al., 2018) and aqueous resources such as lithium rich
brines or salt lakes ( Flexer et al., 2018). At present, the majority of lithium production
around the world belongs to: six mineral operations in Australia, two brine operations
each in Argentina and Chile, and one brine and one mineral operation in China (USGS,
2020), placing Australia as the world’s largest producer of lithium (Flexer et al., 2018;
Vikström et al. . 2013). Spodumene is the favoured resource, as lepidolite comprises
of high fluorine content, while petalite, which is generally used for glass, also has high
fluorine content (Vikström et al., 2013).
Chapter 2: Literature Review 7

The continuously increasing demand for lithium and its high economic importance
(Choubey et al., 2016) will require new paths for sustainable exploitation of this
element. Extraction of lithium from spodumene generates waste material called
lithium slag or spodumene leachate residue. There are various processes to extract
lithium from minerals such as the following.
Alkaline Process
For the alkaline process, spodumene or lepidolite ore concentrates are ground and
calcined with limestone between 825-1050 °C. Then, the calcined product is crushed,
milled, and treated with water to yield lithium hydroxide, which can be converted to
lithium chloride by reaction with hydrochloric acid. The lithium recovery by this
method is approximately 85–90 % (P. Meshram et al., 2014).
Acid Process
Yan et al. (2012) reported a novel technique to extract lithium from lepidolite, which
consisted of sulfation roasting of lepidolite followed by water leaching; reaching a
lithium extraction efficiency of 98.9 % and obtaining 99.9% purity of LiCO3. The
optimum parameters were: de-fluorination temperature of 860 °C; de-fluorination time
of 30 min; milling time of 100 min; leaching temperature of 150 °C; leaching time of
60 minutes and liquid-to-solid ratio of 4:1 (Yan et al., 2012).
Due to its exceptional effectiveness, the sulfuric acid method has emerged as the
primary technique for extracting lithium carbonate from spodumene. First, α-
spodumene is transformed into the more reactive β-spodumene by roasting at 1070–

1100 °C (Y. Chen et al., 2011). Then, the calcined material is mixed with sulfuric acid
and roasted at 250 °C followed by a water leaching process to yield a solution of
lithium sulfate. Lithium carbonate can be recovered after the addition of sodium
carbonate to the solution, pH adjustment, purification and evaporation (P. Meshram et
al., 2014). The results show that the purity obtained of lithium carbonate can reach up
to 99.6% (Y. Chen et al., 2011). This method is still the most popular in the industry
due to its high extraction efficiency, relatively low costs, maturity of technology and
low economic cost to start-up (Izidoro et al., 2019).
It is important to mention that in the sulfuric process for each tonne of processed
mineral, 0.95 tons of acid residue is produced (Rosales et al., 2016). Indeed, one tonne
of lithium carbonate generates approximately 9-10 tonnes of lithium slag (D. Chen et
al., 2012; Z-h. He et al., 2017). This situation shows that Li is the only product
recovered from β-spodumene and Si, and Al remains as a waste (Rosales et al., 2016).
Yiren et al., (2019) predicted that the discharge of lithium slag would reach 1,200,000
tonnes/annum. For this reason, it is crucial to develop an efficient way to recycle
lithium slag in order to save the natural resources and protect the environment (Shan
et al., 2018).
Spodumene Leachate Residue (SLR)
The aluminosilicate based waste product from hard rock refining is generically termed
“lithium slag”, and more specifically spodumene leachate residue (SLR), if from a
spodumene source, which has the general chemical formula of AlxSixOx (Zampori et
al., 2012). SLR is the solid waste of spodumene after high temperature roasting and
leaching. Han et al. (2018) reported the composition of the SLR used in their research,

showing that it was mainly composed of SiO 2 and Al2O3 with a total content of 97.91%
for both of them. A large amount of SLR is stored outside in landfills, which poses a
severe threat to the environment ( Chen et al., 2012). SLR is mainly used as cement
clinker, in concrete, as a raw material for ceramic glazed tiles and in activated clays
(G. Han et al., 2018). However, the utilisation rate is about 10% (Beushausen et al.,
2012). It is thus important to start using lithium slag efficiently to reduce/avoid
pollution and waste of resources. Currently, research using SLR as a resource has
focused on recovering lithium (G. Han et al., 2018), even when the main composition
of SLR is aluminosilicates.
Natural Zeolites mining
Natural zeolites are porous minerals, found in geological deposits such as sedimentary
and volcanic rocks (Guarino Bertholini, 2016). There are multiple applications for
these materials such as ion exchange materials for water and wastewater treatment
(Millar, Couperthwaite et al., 2016), ammonium exchange (Millar, Winnett, et al.,
2016), removal of heavy metals from waste water (Rodríguez-Iznaga, et al. , 2018),
removal of bacteria from filters (Ivankovic et al., 2019), and as a resource for
transforming them into higher value products (Wruck et al., 2021).
Mining a natural zeolite deposit usually involves crushing, grinding and fractionation
(screening into size classes or hydro-classification) (Yusupov et al. , 2000). However,
after the crushing step, a non-marketable natural zeolite ultrafine powder is created
(<50 µm). This material currently represents a loss in the process and an economic
liability due the costs of storage and disposal as well as a potential health hazard due
the small particles in the air (Zijun et al., 2021).

Ultrafine powder from natural zeolite is considered a waste material and it is important
to find efficient methods to use it. Natural zeolite is high in Si and Al, materials that
can be used for industry purposes.
Low silica zeolites from alumino-silicate waste
The literature on the use of alumino-silicate waste has a primary focus on the
production of low silica zeolites, such as Zeolite LTA or faujasite (Poole, Prijatama,
& Rice, 2000). For example, Mahima Kumar et al. (2020), synthesized LTA Zeolite
from raw fly ash (without calcination or acid treatment) by using fusion with alkali
and hydrothermal synthesis. Moreover, Izidoro et al. (2019), used the waste of iron
mine tailing dam as raw material to produce Zeolite LTA; this synthesis was carried
out with a fusion step followed by a conventional hydrothermal reaction.
Zeolite LTA
Zeolite LTA is characterised by the formula Na +12(H2O)27)8 (Al12Si12O48)8 which
corresponds to its most common hydrated sodium form (Drioli & Giorno, 2016). It has
a cubic crystal structure with a lattice parameter of 12.32 Å and 3-dimensional network
involving spherical cavities of 4.2 Å in diameter. Zeolite LTA is well known in the
industry due to use in laundry detergents (S. U. Meshram et al. 2014). It can be used
as a substitute of sodium tripolyphosphate (STP), which has been banned in many
countries (Ayele, Pérez-Pariente, Chebude, & Díaz, 2016a). STP has been identified
as the main cause of eutrophication and this problem can be solved by replacing the
phosphate based compounds for a greener option such as zeolite LTA (Rayalu et al.,
2001). Zeolite LTA has also been used in different industrial processes such as
dehydration of bio-ethanol (Sato et al., 2008), heavy metals removal (Jamil et al. 2010)

and desalination of radioactive solutions (Malekpour et al. 2008). For this reason,
zeolite LTA is by far the most commonly produced synthetic zeolite, making up 73%
of global production (Ayele, Pérez-Pariente, Chebude, & Díaz, 2016a).
Zeolite LTA can also be used in the healthcare industry. When it is exchanged with
silver ions it can be used as an antimicrobial material (Collins et al., 2020; Y. Zhang
et al., 2009). It has also been proven that the use of a silver zeolite-impregnated
umbilical catheter is effective in decreasing the risk of developing a catheter-related
bloodstream infection (CRBSI) in preterm infants (Bertini et al., 2013) .
Synthesis of zeolite LTA has been successfully performed using different low cost
natural/waste materials such as bentonite (H. Ma et al., 2010), kaolinite (Johnson &
Arshad, 2014; Rios et al.,2009), fly ash (Rayalu et al., 2001), sugarcane bagasse ash
(Moisés et al., 2013), clay (García et al., 2015) and lithium slag (B. Wang et al., 2022;
Huang et al., 2023).
Zeolite Synthesis
Waste aluminosilicate and naturally occurring aluminosilicates, such as clay, can be
transformed into higher value products such as zeolites. Zeolites are typically
microporous or mesoporous with the general composition: Mx/n (AlO2) x (SiO2) y ∙ zH2O
where M is the cation that compensates for the negatively charged framework, n is the
cation valency, y/x is the Si/Al ratio, and z is the water content. Zeolites are employed
commercially for application such as catalysis, gas separation, and sorbents (Müller et
al., 2015; Whiting et al., 2019), adsorption of greenhouse gasses (Müller et al., 2015;

Xu et al., 2019), ion exchange (Müller et al., 2015; Zhang et al., 2015) and as molecular
sieves for separation of compounds (Fakin, Ristić, Mavrodinova, & Zabukovec Logar,
2015; Klumpp, Zeng, Al-Thabaiti, Weber, & Schwieger, 2016). In recent years, a need
has developed to create green synthesis methods for zeolites ( Liu et al., 2014; Pan,
Wu, & Yip, 2019). Hence, efforts have been made to reduce the use of organic
structure directing agents (OSDA’s) which are potentially toxic. The synthesis of
zeolites under organotemplate-free conditions has been proven successful, avoiding
the combustion of OSDAs and the generation of liquid wastes and harmful gases;
which means this practice can be consider as environmental friendly synthesis (Y.
Wang, Wu, Meng, & Xiao, 2017). Y. Ji, Wang, Xie, & Xiao (2015) demonstrated that
the organotemplate-free synthesis was possible using a seed-directed synthesis where
it was suggested as a third zeolite structure-directing agent.
Avoid solvent consumption.

It has been demonstrated that zeolite synthesis under solvent-free conditions can be
successfully performed by mixing, grinding, and heating starting solid materials. Wu
et al. (Wu et al., 2018), indicated exceptional advantages of this method, including the
development of hierarchical micro-, meso- and macrostructures, fast synthesis at
higher temperatures, and construction of a novel catalytic system for encapsulation of
metal nanoparticles and metal oxide particles within zeolite crystals synergistically.
The combination of organotemplate-free synthesis with a solvent-free methodology
has the potential to develop a more environmentally friendly synthesis, however
minimal research has been conducted in this field.

Utilise waste alumina-silicate resources.
Industrial wastes with Si and Al as main components can be used as raw material for
zeolite synthesis. Kuroki, et al., (2019), successfully synthesised zeolite X and zeolite
LTA from crushed stone and aluminium ash by two hydrothermal treatments at low
temperature (>150℃). Selective synthesis of zeolite X and A was accomplished by
controlling the acid treatment conditions. As mentioned previously, the current
approaches with waste resources have been increasing and more waste material is
being used for the synthesis of zeolites, in order to reduce contamination, costs and
save natural resources. However, there is a lack of studies on what can be used as
starting material for zeolite synthesis. SLR is a waste alumina-silicate material and
therefore it does not easily form into zeolites (T. Li et al., 2012). Therefore, an
activation strategy may be required; with one of the simplest approaches being heating
at elevated temperatures. Heat treatment in order to improve the properties of SLR has
been studied in relation to construction industry utilisation (Z. Liu, Wang et al., 2019).
Minimise energy consumption.
Majdinasab et al. (2019) proved that the conversion of waste glass into zeolites can
be achieved using a hydrothermal reaction and microwave heating for an effective and
rapid conversion of the waste glass to zeolites with a relative crystallinity of 60%. Due
to the high-energy efficiency, superheated conditions can considerably reduce the
crystallisation time from numerous hours to minutes.
All these applications show the need to develop new techniques that allow industry to
use their waste materials in a more environmentally friendly way. Zeolite market
demand is growing and so is the demand for synthetic zeolites. This project will focus

on the use of SLR for zeolite synthesis using the “one-pot” technique, which will allow
not only the use waste materials, but also minimize the consumption of resources.
Zeolite synthesis methods
High Concentration Alkali Solution (HCAS) Activation

T. Li et al. (2012), explained how to activate natural alumina-silicate minerals without
the involvement of inorganic chemicals (aluminium and silicon) in order to transform
them into zeolite Y. To perform this method, the selection of at least two suitable
natural mineral sources was required; in this case kaolinite (which contain high levels
of alumina and silica), and diatomite (rich in silica) were chosen. The activation of
the minerals, where the inert alumina-silicate (kaolinite) was treated with a high
concentration alkali solution (HCAS) activation method, while the mineral in the non-
crystalline state (diatomite) was activated by the normal thermal activation method.
This research proved that the purity of the synthetic zeolite Y was comparable to a
commercial sample and highlighted that all the impurities originally existing in the
material remained in the mother liquid. It also revealed that even at 200℃ (normal
thermal activation performs at 800 ℃) HCAS activation can successfully destroy the
structure of kaolin and other alumina-silicate minerals and generate higher contents of
active alumina and silica which created higher reactivity for zeolite synthesis. The
material balance assessment analysis illustrated that 97.4% and 64.2% of kaolinite and
diatomite respectively were transformed into zeolite. Finally, it was proven that this
method compared to the conventional synthesis has numerous advantages such as
reduction of solid and water discharges, CO2 emissions, and energy consumption (T.Li
et al., 2012).

Quasi-Solid Phase Activation Process (QSP)
Yang et al. (2017) described how to activate kaolin under relatively mild conditions
in order to make it amenable for conversion into zeolite LTA and zeolite Y. Initially,
kaolin was kneaded with some sodium hydroxide and then water was added.
Subsequently, this material was extruded into shapes 1.5 mm in diameter and 2 to 3
cm in length. The extrudate was finally heated to between 60 and 100 ℃ for 30
minutes in a belt type calcination oven. This new methodology was termed Quasi-
Solid Phase Activation Process (QSP). The principal advantages relative to the HCAS
approach were:
 Lower activation temperature.
 Less water required.
 Continuous processing (as opposed to batch for HCAS)
 Reduced energy consumption.
The superior effectiveness of the QSP approach to the HCAS methodology was
illustrated for hydrothermal synthesis of both zeolite LTA and zeolite Y.
Alkali fusion synthesis

Ayele et al. (2016b) applied alkali fusion synthesis for the activation of raw kaolin by
combining 1.25g of raw kaolin with 1.5g of NaOH for 30 minutes, afterwards the mix
was calcined at 600℃ for 1 hour in a furnace. Once the fused product was ready, it
was ground in a mortar and mixed with 12.5mL of ultrapure distilled water at 50℃ for
1 hour. For crystallisation, the samples were heated using water baths under static
conditions at 100℃ for three hours. They achieved an optimum crystallinity of 84%.

This research also compared alkali fusion synthesis against the conventional
hydrothermal method and proved that alkali fusion was the best method in terms of
time, energy cost, and product quality and it also allowed the use of low-grade virgin
kaolin without purification, whereas the conventional method needs a purified raw
kaolin to achieve a good quality zeolite.
Zijun et al. (2021) used ultrafine natural zeolite powder to make zeolite W by thermally
activating the material, followed by a fusion step to combine the natural zeolite with
potassium hydroxide. After that, the mixture was combined with aluminium
hydroxide, potassium hydroxide and water and synthetized at 150 oC and 16 hours.
The material made showed a cation exchange capacity of 324meq/100 g indicating
potential for ammonium uptake.
Wruck et al. (2021) investigated the impact of a pre-activation of natural zeolite upon
zeolite LTA synthesis, using natural zeolite samples from three different deposits.
However, the study showed that all the samples lost their cation exchange capacity
after being heated at elevated temperatures, so an alternative activation was used
(alkali fusion). Fusion activation resulted in a significant increase in zeolite LTA, and
it was reported that the product resulting from hydrothermal synthesis was formed of
85% crystalline zeolite LTA.
One-pot synthesis
‘One pot’ synthesis method for waste-to-zeolite processes is not only simple but a
greener option from the scientific point of view since it effectively eliminates the

fusion step (X. Ji et al., 2018). The dissolution of silica in sodium hydroxide is widely
reported, but the detailed mechanism is poorly understood. Dissolution of amorphous
silica can be expressed as:
𝒙(𝑺𝒊𝑶𝟐) + 𝟐𝑯𝟐 𝑶 ↔ (𝒙 − 𝟏)(𝑺𝒊𝑶𝟐) + 𝑺𝒊(𝑶𝑯)𝟒
Equation 1. Dissolution of amorphous silica
There is some literature pertaining to the use of sodium hydroxide leaching for Li
extraction However, little focus has been given to the structure changes of the solid
residues and, indeed, the kinetics of spodumene dissolution, even though this method
is more convenient, simple and environmentally benign than the conventional one (X.
Ji et al., 2018), further investigation needs to be done to explain the mechanisms of the
crystal phase and understand the optimum conditions for zeolite synthesis.
Green methods
The use of green techniques for zeolite synthesis is essential for promoting
sustainability and reducing environmental impact. However, there are still some
challenges that need to be addressed. For instance, the optimization of resource
utilization is crucial to minimize the environmental impact of zeolite synthesis. This
can be achieved by developing methods that reduce the consumption of energy, water,
and raw materials.
The conventional hydrothermal synthesis of zeolites is an exigent challenge from the
green chemistry standpoint because it depends on the use of organic templates which

are removed at the end of the process by calcination, or extracted using organic
solvents which produce several risks to the environment including the emission of
green gases during the combustion of toxic organic templates (Pan et al., 2019).
According to Pan et al. (2019), the green synthesis of zeolites can be classified in four
main categories:
 Synthetic methods which avoid the use of a template or use a recyclable or
renewable template,
 Synthetic methods that use sustainable resources,
 Solvent-free methods
 Facile synthesis methods.
As demonstrated through the aforementioned methods, researchers have attempted to
develop novel techniques to promote environmentally friendly zeolite synthesis. The
integration of various green methods requires further investigation to optimize
resource utilization and minimize environmental impact. One of the green techniques
that not yet mentioned is the application of ultrasound pre-treatment for zeolite
synthesis (Reinoso et al., 2018). Reinoso et al. (2018) synthetized faujasite without
using any OSDAs, at low temperature (30 °C for the aging pre-treatment and 100 °C
for the hydrothermal treatment) and applying ultrasound-assisted aging. This was
accomplished in two stages, aging step, and hydrothermal treatment, obtaining a pure,
well-crystalised faujasite with small crystal size (38 nm).
Despite the progress made in the development of green methods for zeolite synthesis,
there are still some remaining gaps that need to be addressed. For instance, there is a
need to optimize the efficiency of these methods to make them more cost-effective and

practical for industrial-scale production. Additionally, there is a need to develop more
comprehensive and standardized methods for evaluating the environmental impact of
zeolite synthesis. This will help to ensure that the methods developed are truly
sustainable and environmentally friendly.
Industry 4.0
The concept of Industry 4.0 involves the technological innovation of automation,
control and information technology applied to manufacturing process (Machado &
Paulo, 2020). It is focused on smart procedures, processes, and products (smart
production). This means there is direct communication between equipment, labour,
and resources (Heng, 2020).
The Industry 4.0 principles are considered a new industrial stage where many
emerging technologies are converging to enable digital solutions (Frank et al 2019). It
depends on the implementation of digital technologies to collect and analyse real-time
data to provide useful information to the manufacturing system (Frank et al., 2019).
According to Frank et al. (2019), Industry 4.0 technologies can be distributed into two
layers: “front-end technologies” which are focused on operational and market needs,
and the “base technologies” that supply connectivity and intelligence for the first layer
to then be a complete integrated manufacturing system.
The base technologies support all the “Smart”. They are constituted by the information
and communication technologies (ICT). The combination of IoT (Internet of Things)

and Cloud allows various equipment to be connected, gathering a massive amount of
data (big data storage) (Lu, 2017). Big data combined with analytics, such as machine
learning, is considered a strong alternative or contender for shaping the future and
playing a crucial role in driving the fourth industrial revolution (Frank et al., 2019) .
In 2017 a cooperation agreement with Germany’s Platform Industry 4.0 was signed to
provide a boost to Australia’s economic competitiveness (Australian-Government ,
2020). This agreement explores the framework and principles for adopting Industry
4.0 in the country and prepares for the transition to smart factories. One of the priority
growth sectors where these new technologies are/will be likely to be implemented is
the mining industry. Currently, the government has invested approximately $2.4
billion in growing Australia’s research to support a stronger and smarter economy and
$29.9 million to develop artificial intelligent and machine learning (Australian-
Government, 2020).
It is important to recognise that the lithium mining sector in Australia has not been
focused on the efficient management of the waste material it produces, but Industry
4.0 technologies could be applied to transform these materials.
Machine Learning
Machine learning is a quickly growing technical discipline combining statistics,
computer science and a variety of fields concerned with decision making under
uncertainty and continuing automatic improvements (Jordan & Mitchell, 2020).
Unlike traditional computational approaches where the computer operates under a

hard-coded algorithm written by a specialist (Butler et al., 2018), ML gives us the
opportunity to develop algorithms which are able to generate predictions without being
explicitly programmed (Sen et al., 2018) (output) by assessing a portion of given data
(input) (Butler et al, 2018). Additionally, ML algorithms are able to learn from their
inputs to customize their services to the needs required (Jordan & Mitchell, 2020). ML
gives us the opportunity to accelerate the process of materials discovery and
optimisation (Evans & Coudert, 2017), but before setting up the algorithms it is
important to make sure how the dataset is going to be managed in every stage of the
process (i.e., data collection, data representation, data procession, choice of a learning
algorithm, and model optimisation).
Current applications of Machine Learning in zeolite synthesis.
Preparation of zeolites is usually defined by several connected variables which are still
reliant on trial-and-error methods. In the past decade ML methods have evolved to
solve complex problems including nonlinear or significantly combinatorial processes
that traditional methodologies cannot solve ( Moliner et al,, 2019). ML methods have
already proved to be useful tools in different fields such as chemistry, biochemicals,
drug design, computational biology (Carr, Lach-hab, Yang, Vaisman, & Blaisten-
Barojas, 2009), water desalination (Al-Shayji & Liu, 2002), and reverse and forward
osmosis (Cabrera et al., 2017; Jawad et al., 2020).
Considering the extensive and interconnected areas of zeolite synthesis, the use of ML
is exceptionally timely for enhancing zeolite synthesis. The complex space of zeolite
synthesis requires drawing inferences from partial and imperfect information, for
which ML methods are very well-suited, to replace the intuition-based methods used
for experimentation (Moliner, Y. Roman-Leshkov, et al., 2019).

ML clustering analysis has proved that there are three groups of zeolites with the HEU
(heulandite) topology, S. Yang et al. (2010) used machine learning clustering analysis
of crystallography data of zeolite crystals. Before this study it was understood that the
heulandite family was divided into two mineral groups: heulandite (HEU-h) and
clinoptilolite (HEU-c). Their research proposed a new group based on the expectation–
maximization algorithm, HEU-m. It confirmed the existence of an intermediate group
between HEU-h and HEU-c.
Jensen et al. (2019) applied a machine learning approach to zeolite synthesis using
automatic literature data extraction for germanium-containing zeolites. To achieve
this, they trained two algorithms (random forest regression and decision tree model)
using data from a learning Python library, sci-kit. As a result, they developed an
automatic data extraction pipeline that localises, extracts, and formats synthesis data
for germanium containing zeolite predicting resulting zeolites topology.
Moliner et al. (2019) applied ML techniques to zeolite synthesis developing new
useful tools in significant machine learning areas such as data mining, generating large
amounts of data using High-Throughput (HT) platforms for synthesis and
characterisation. The enhancement of HT zeolite synthesis systems increased the
number of experiments and variables that can be analysed simultaneously and at the
same time all this information formed part of the development of data mining
techniques making it able to analyse the large quantity of data generated every time.
They used artificial neural networks (ANNs) to predict the internal relationships
between different synthesis variables and once this technique was properly trained the

genetic algorithms (Gas) were used to successfully guide experimental design,
improving catalytic behaviour of Ti-silicates. Clustering using k-Means helped the
data classification in this research; the analysis used diffraction patterns to distribute
the data into three groups, proving that this technique has been found useful to identify
pure phases in mixed systems. Finally, this research illustrates the need for new ML
friendly representation of crystal structures, because the standard representation has
been developed for human understanding which will not be optimal for ML algorithms
(Moliner, et al., 2019).
This literature review shows us that analysing our data through machine learning
approaches can help future investigations to develop and improve zeolite synthesis
routes. It has also presented a new way to use our “unsuccessful” data, feeding the ML
algorithms with them to achieve the output expected. To date, there is no research
related to the use of machine learning focused on mining waste reuse. This represents
a great opportunity in the field of zeolites but also to help with the reduction of mining
waste material that, as previously mentioned, is causing environmental problems.
The use of machine learning in the zeolites field is challenging; one of the main
obstacles that this project has faced is the amount of data generated during the first
years of the research, since the efficacy of ML is constrained by the quantity and
quality of data (Moliner et al., 2019). However, possible approaches to zeolite
synthesis can be tested with just small data sets. Moreover, the lack of research into
zeolite synthesis from waste materials and the incomplete understanding of the
synthesis/crystallisation is a challenge that the project addresses. However, using a

continuous system with real time measurements will help to improve the
understanding of the process.
Key insights
This chapter presented a comprehensive literature review of research on the
significance of recycling mining waste in Australia. With mining extraction generating
significant amounts of waste material, and decreasing landfill capacity, the need for
new methods has become increasingly crucial. Previous studies indicate that only 10%
of mining waste is reused, and hence recycling this material into high value products
such as zeolites can not only mitigate environmental problems but also provide
financially viable options for the mining industry.
Lithium slag and natural zeolites are significant waste products that predominantly
contain silica and aluminium, offering potential for recycling. However, current
methods are energy-intensive and pose significant scaling-up challenges for industrial
implementation. Therefore, there is a pressing need to develop new methodologies that
enable efficient transformation using green methods and that are easier to scale up for
industry.
In the next chapter, an activation technique will be developed to transform mining
waste materials into zeolitic products, utilizing the multi-step process to synthesize
zeolite LTA from mother liquor and solid product.

Chapter 3: Feasibility of Zeolite LTA Synthesis from Spodumene Leachate
Residue via Cancrinite Formation
Abstract
Waste materials such as Spodumene Leachate Residue (SLR) from lithium ores are increasing
in volume due to higher demand for lithium batteries. Transformation of SLR into higher value
zeolite LTA is of interest if the critical problem of low cost SLR activation can be solved.
Therefore, this study made zeolite LTA via a cancrinite phase. Preferred conditions for making
cancrinite involved heating SLR at 240 oC for one hour in 7 M sodium hydroxide (NaOH). In
one approach, the silicate rich mother liquor was mixed with sodium aluminate (NaAlO2) and
water to adjust NaOH molarity to form zeolite LTA (68 wt %). Alternatively, a process
wherein NaAlO2 was added to adjust the silica to alumina ratio to 2 in the starting mixture was
found to produce low quality cancrinite (26.5 wt% cancrinite, 13 wt% sodalite and 59 wt%
amorphous). Improvements were observed when a mixture of cancrinite and NaAlO 2
underwent acid dissolution to extract available Si and Al, followed by neutralization and
subsequent hydrothermal reaction. Notably 2 M hydrochloric acid (HCl) was preferred for the
acid dissolution step and neutralization of the acidic solution was best with 4 M NaOH. The
zeolite LTA content was highest (63.1 wt%) when aluminium content in the reactant mixture
was greatest. The inherent excess of aluminium present in the mother liquor and wash water
may be recycled along with residual NaOH. However, the presence of excess sodium chloride
may inhibit recycling of mother liquor/wash water and thus the economics may not be
attractive.
Chapter 3: Feasibility of Zeolite LTA Synthesis from Spodumene Leachate Residue via Cancrinite Formation 26
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Key Words: spodumene; zeolite; cancrinite; lithium; waste
Introduction
Lithium demand is projected to increase substantially in the next few years due primarily to
the growth in demand for batteries for electric vehicles and renewable energy storage
(Dessemond et al., 2019). Notably, lithium is mainly sourced from either hard rock deposits
such as spodumene (LiAlSi2O6) or lithium brines ( Flexer et al., 2018). Currently, hard rock is
the largest source of lithium for commercial use, with Australia supplying >50 % of market
needs (Hao et al., 2017). In Australia, the lithium sources are located in Western Australia and
mined by various companies (Karrech et al., 2020).
Despite the economic and social benefits of lithium mining there exists a challenge in terms of
the waste produced when lithium is extracted from ore bodies. Typically, lithium ores such as
α-spodumene are initially roasted at high temperatures to make the more reactive β-spodumene
phase and then leached using sulfuric acid (P. Meshram et al., 2014). The residual
aluminosilicate waste material is termed lithium slag or spodumene leachate residue (SLR)
(HAlSi2O6). This material is produced at a ratio of approximately 10 tonnes of lithium residue
for every one tonne of lithium carbonate made (Z-h. He et al). At present, only a small fraction
of SLR finds use in applications such as ceramic glazed tiles, concrete, or cement clinker (G.
Han et al., 2018). Hence, there is a need to find innovative means to recycle this waste stream
into valuable products.
As SLR is mainly comprised of aluminosilicate materials, it is logical to examine whether this
waste can be used as a resource for making higher value products such as zeolites (X. Wang et
al., 2021). Synthetic zeolites are mainly aluminosilicate-based minerals and employed in
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applications including catalysis (Weitkamp, 2000), molecular sieving (Davis, 1991), gas
separation (Kosinov et al., 2016), green chemistry (H. Li et al., 2016), water/wastewater
treatment (Koshy & Singh, 2016), and laundry detergents (Fruijtier-Pölloth, 2009).
Commercially, zeolite LTA (Na 12Al12SiO48.28H2O) is manufactured in the greatest volume as
it is primarily employed in detergent formulations to soften water (El-Nahas et al., 2020) and
for drying of natural gas (Shirazian & Ashrafizadeh, 2015).
Traditionally, many zeolites are made via an aluminosilicate gel which is formed by
appropriate mixing of alkaline solutions of sodium silicate and sodium aluminate followed by
hydrothermal synthesis for several minutes to hours ( Cundy & Cox, 2005). The recovered
“wet cake” is subsequently washed and dried in the oven ( Probst et al., 2021). In contrast,
making zeolite LTA from wastes such as SLR is more demanding as an additional
aluminosilicate depolymerisation step is required to enhance the reactivity of the waste material
(Collins et al., 2020). Activation strategies include thermal treatment at elevated temperatures
(H. Liu et al., 2014), solid alkali fusion (Ayele et al., 2016b), high concentration alkali solutions
(HCAS) (T. Li,et al., 2012) and the quasi-solid phase activation process (J. Yang et al., 2017).
Activation of clay materials including kaolin, rectorite, illite, and montmorillonite has been
accomplished by the HCAS method (T. Li et al., 2012; Liu et al., 2015; Yue et al., 2014; Y.
Yue et al., 2015). This approach uses high molarity solutions of sodium hydroxide (for
example 15 M) at temperatures in the range 200 to 250 oC for several hours to produce zeolite
P and zeolite Y. However, the HCAS strategy is not industrially viable due to problems such
as evaporation of large amounts of water during the heating stage and consequently excessive
energy consumption (H. Liu et al., 2015). An alternative activation approach was developed
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by J. Yang et al. (2017) and termed Quasi-Solid Phase Activation Process (QSP). In this case,
kaolin was kneaded with sodium hydroxide pellets and minimal amounts of water; and then
extruded. The extrudates were subsequently heated in the range 60 to 100 oC for 30 minutes
in a belt type calcination oven. Yue et al. (2020) demonstrated, using the QSP approach, that
>95 % depolymerisation of the rectorite was obtained by heating at 170 oC for 1 h.
Subsequently ZSM-5 zeolite was made after reaction at 70 oC for three hours. The principal
advantages relative to the HCAS approach were: (1) lower activation temperature; (2) less
water required; (3) continuous processing (as opposed to batch for HCAS); and (4) reduced
energy consumption. However, the QSP process has the disadvantage that it needs to evaporate
water at significant cost from recycled sodium hydroxide mother liquor to form the solid
sodium hydroxide used in the initial kneading phase. If excess sodium hydroxide in the mother
liquor is not reused, then the economics can become unfavourable (Ghrear et al., 2020).
With regard to SLR activation and the ensuing synthesis of value added products, the formation
of FAU/LTA zeolites has been reported by . Lin, Zhuang, Cui, Wang, and Yao (2015). The
basic strategy was to initially activate SLR by heating with NaOH at a moderate temperature
followed by mixing with water and heating at elevated temperature for 9 h. Notably, not only
was 48 % of the mother liquor recycled to the initial activation stage but also the zeolite
composition changed markedly depending upon the order of aluminium addition. The
synthesis of nano-kaolinite and xonotlite (6CaO.6SiO 2.H2O) from SLR has also been described
(X. Wang et al., 2021). A hydroxycancrinite intermediate phase was formed by heating SLR
and 6 M NaOH at 220 oC for four hours. As a result of heating the hydroxycancrinite in nitric
acid at 260 oC for 24 h, kaolinite was synthetised. It is noted that an undesirable sodium nitrate
waste stream was created by this approach.
`
The high silicate containing mother liquor produced from the SLR to cancrinite process was
reacted with lime under hydrothermal conditions for two hours to make hydrated calcium
silicate. A second hydrothermal stage was then employed to make xonotlite by heating at 260
oC for 12 h. The initial growth of cancrinite and subsequent reaction to form zeolite materials
has also been reported in studies of kaolin/quartz to zeolite Y (X. Wang & Nguyen, 2016).
The fundamental premise of activation of waste aluminosilicates to form cancrinite has merit
in that it operates at significantly lower temperature than an alkali fusion approach (Ayele et
al., 2016b). However, there remain several gaps in the process knowledge. For example the
study by X. Wang et al. (2021) made products from SLR which may not have a substantial
market in key lithium producing countries such as Australia. Secondly, the extensive use of
high temperature conditions (e.g., heating calcium hydroxide at 900 oC for 2 h) could result in
a process which is prohibitively expensive. The generation of a waste sodium nitrate solution
is also not desirable. Additionally, the presence of salt in the neutralization stage may promote
or inhibit zeolite formation. Nevertheless, previous studies of transforming SLR into value
added products confirm that strategies such as mother liquor recycling and cancrinite formation
are of interest.
Therefore, the aim of the study described in this chapter was to determine the feasibility of
converting SLR to zeolite LTA via a cancrinite intermediate phase. The hypothesis was that if
SLR processing was better understood then zeolite synthesis may be made more cost effective.
The research questions to support this hypothesis were: (1) Can pure zeolites be made from a
dual process? (2) How can the formation of high-quality cancrinite be achieved when
additional aluminium species are added to the feed mixture? (3) What factors influence the
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formation of cancrinite? (4) What are the optimal conditions for the acid dissolution and
neutralization steps in the process of synthesizing zeolite LTA from the cancrinite/sodium
aluminate mixture? (5) How do different acid and alkali concentrations affect the quality of the
final product?
The activation of SLR and subsequent zeolite synthesis were conducted at bench scale to prove
the concept in this investigation. Comprehensive analysis of both solid and aqueous streams
was completed to determine product quality and understand the chemistry. A process flow
diagram was created which included mass balance and zeolite yields. Zeolite LTA was
targeted, as it is the largest volume zeolite synthesised by industry due to its use by the detergent
and gas industries.
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Materials and Methods
Spodumene Leachate Residue and Chemicals

The Spodumene Leachate Residue (SLR) for this study was supplied from a lithium mine in
Western Australia. Analysis by X-ray Fluorescence indicated that the main species present
were SiO2 (66.6 wt%) and Al2O3 (23.7 wt%) (Supplementary Table 1). Quantitative X-ray
diffraction suggested the major components were Hydrogen Aluminium Silicon Oxide (46.9
wt%), quartz (3.93 wt%), lithium sulfate (0.30 wt%) and non-diffracting/unidentified material
(48.86 wt%) (Supplementary Table 2). The particle size of the SLR ranged between 0.76 and
240 µm with a d50 = 47.61 µm and a d90 = 153.02 µm (Supplementary Figure 1). The SLR
grains were relatively featureless (Supplementary Figure 1). Sodium aluminate (NaAlO2) was
purchased from Sigma-Aldrich. Hydrochloric acid (HCl; 32 wt %) and sodium hydroxide
(NaOH; extra pure micro-pearls & 40 wt% solution) were procured as an analytical reagent
(AR) grade from ChemSupply.
Synthesis of Zeolite LTA from Spodumene Leachate Residue

Three general pathways to making zeolite LTA from SLR via a cancrinite stage were
investigated. In Process 1 two crystalline products were made (zeolite LTA and cancrinite)
(Figure 1), whereas Process 2 further reacted cancrinite produced from the high temperature
hydrothermal activation stage to make zeolite LTA. Notably, additional NaAlO2 was added to
the high temperature hydrothermal reactor to adjust the SiO 2/Al2O3 ratio to 2 (Figure 2).
Finally, Process 3 was a variation of Process 2 wherein the additional NaAlO 2 was mixed with
the cancrinite product in contrast to the high temperature activation stage (Figure 3).
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Process 1
The aim of this stage was to determine the impact of sodium hydroxide molarity (4 to 10 M),
temperature (100 to 240 ℃), and reaction time (1 to 24 hours) upon the transformation of SLR
to cancrinite. SLR (10 g) was mixed with NaOH (1.917 g NaOH/g SLR), and deionized water
added to adjust NaOH molarity. For reactions at 100 and 150 oC this latter mixture was placed
into a Berghof BR100 High Pressure Reactor. For reactions at higher temperatures (200 and
240 oC) samples were placed in a PTFE lined 100 mL acid digestion vessel (Amar Equipment
PVT Ltd., India) and subsequently located in a rotary oven (KLJX Homogeneous reactor). In
this case the volume of the samples was adjusted to accommodate the reduced equipment
capacity by mixing 5 g of SLR, sodium hydroxide (1.917 g NaOH/g SLR) and deionized water
to control NaOH molarity.
Figure 1: Process flow diagram for making both cancrinite and zeolite LTA from Spodumene
Leachate Residue
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All reactant mixtures were agitated at 100 rpm and hydrothermal reaction time was defined as
the time after reaching the set temperature. Each reaction allowed for 60 minutes cooling
before collecting the product slurry. After the reaction was complete the mother liquor and the
solid were separated using an Allegra X-30 Centrifuge. The wet cake was washed with 240
mL of deionised water to reduce pH (pH 11 to 11.5) and finally dried in an oven at 105 ℃
overnight. Once the preferred synthesis conditions for cancrinite were obtained, larger
volumes of this material were made using a 1 L hydrothermal reactor (Amar Equipment, India).
In this case, SLR (60 g), NaOH (115.02 g) and deionized water (410.82 g) were reacted at 240
℃, with agitation (100 rpm) for 1 h.
The resultant mother liquor was then modified by addition of NaAlO 2 to adjust the SiO2/Al2O 3
ratio to 2 along with sufficient water to adjust the sodium hydroxide molarity to 4 M. Zeolite
synthesis was performed by placing sealed containers in a New Brunswick Innova 42R
Incubator for four hours at 80 ℃ while being agitated at 100 rpm. When the synthesis was
complete the slurry was centrifuged to recover the solid product, which was washed multiple
times with deionized water to reduce pH from 14 to 11. During each cycle 30 mL of water was
used. Once the preferred pH was obtained, the slurry (wet cake) was weighed and dried in an
oven at 105 ℃ overnight. The mother liquor from the zeolite synthesis stage was recycled to
the initial high temperature activation stage.
Process 2
The high temperature activation stage was conducted similarly to the corresponding approach
in Process 1. The main difference was the addition of 31.8 g of sodium aluminate along with
SLR (10 g), NaOH (1.917 g /g SLR), and deionized water to adjust NaOH molarity.
`
Cancrinite dissolution trials involved addition of cancrinite (1 g) and hydrochloric acid
solutions (10 mL) of the desired molarity (1, 2, 3, 4, 5, 6, 7, 8 M) into a 50 mL centrifuge tube.
The solution was agitated with a rotary tube mixer for 15 min. Subsequently the samples were
syringe filtered and mother liquor was collected for analysis to determine the presence of major
cations in solution. All experiments were performed in triplicate. Cancrinite (2 g) was added
to a centrifuge tube wherein HCl (20 mL) was added to dissolve the cancrinite. This solution
was then neutralised with varying concentrations of NaOH solution (20 mL). Zeolite synthesis
was performed as described in Process 1.
Figure 2: Process flow diagram for the synthesis of zeolite LTA from Spodumene Leachate
Residue via cancrinite formation; Additional NaAlO 2 added to the feed stream to the high
temperature hydrothermal reactor.
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Process 3
A variation of Process 2 involved addition of sodium aluminate to the cancrinite product
instead of during the hydrothermal activation stage (Figure 3).
Figure 3. Process flow diagram for the synthesis of zeolite LTA from Spodumene Leachate
Residue via cancrinite formation; Additional NaAlO 2 added to the cancrinite product.
By adding the extra sodium aluminate directly to the cancrinite produced from high
temperature hydrothermal reaction, it was possible to synthesise zeolite from the silica species
present in the mother liquor, as in Process 1.
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Solution Analysis
Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES)

The concentration of sodium, aluminium and silicon from the acid dissolution step and zeolite
synthesis (mother liquor) was determined using a Perkin Elmer Optima 8300 DV ICP-OES
spectrometer. Prior to analysis the samples were filtered through a syringe filter and diluted to
1:100 and 1:1000 with 2% nitric acid (diluent) using a Hamilton auto-diluter.
Ion Chromatography (IC)

Solutions were syringe filtered prior to analysis and diluted using Milli-Q water in a Hamilton
auto-diluter. Chloride analysis was completed using a Dionex ICS-2100 ion chromatography
system. The flow rate used for the suppressed ion chromatographic method was 1.0 mL/min
with an eluent strength of 28.0 mM KOH and an injection volume of 25.0 mL. The elution time
was 10 minutes with a chloride retention time of 3.16 min. The instrument was connected to a
Dionex ICS AS-DV autosampler.
Solid Characterization
Quantitative X-ray Diffraction (XRD)

A PANalytical X’PertPro powder diffractometer was used to identify the crystalline phases in
the final products. The samples were initially mixed with 10 wt% corundum standard powder
(Al2O3). The sample (0.45 g) and standard (0.05 g) were micronized in a McCrone micronizing
mill with 15 mL ethanol; and dried in an oven for four hours at 40 ℃. Dried samples were
collected, and front pressed into sample holders. To identify the product phases JEdit and
TOPAS software were used. The reference patterns for zeolite LTA were obtained from Breck
et al., 1956) and atomic parameters were cross-referenced from PDF entry 04-017-3644.
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X-ray Fluorescence (XRF)
PANalytical WROXI software application and a PANalytical AXIOS 1.5 kW Wavelength
Dispersive XRF spectrometer were used to determine the elemental quantification of the solid
products. Solid samples (1 g) were mixed with lithium tetraborate: lithium metaborate (50:50)
with 0.05% li-Iodate (9 g) and heated at 1050 ℃ to form a fused glass disc.
Scanning Electron Microscopy (SEM)

Shape and size of zeolite crystals were observed using a JEOL 7001F Scanning Electron
Microscope. The accelerating voltage employed was 5 kV, with a probe current of 10 A at a
magnification between 4000 and 10000x. Each sample was prepared on carbon stamps and
coated with platinum prior to observation.
Particle Size Distribution

A Malvern Mastersizer 3000 instrument equipped with dispersion chamber, ultrasound and
automatic cleaning was used to determine the particle size of the Spodumene Leachate Residue.
Powder was added along with deionized water into the dispersion chamber to reach 15%
obscuration with sonication. Measurements were repeated five times for 30 s and the reference
material used for the program was zeolite LTA.
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Results and Discussion
Process 1: Synthesis of Cancrinite and Zeolite LTA from SLR
Synthesis of Cancrinite from SLR and Sodium Hydroxide Aqueous Solution

The first stage investigated the impact of reaction temperature (100 to 240°C), NaOH molarity
(4, 5, 7, 10 and 14 M) and reaction time (1, 15 and 24 h) upon cancrinite formation (Figure 4).
100
1h Synthesis 100
wt% Crystalline Cancrinite
1h Synthesis
24h Synthesis
24h Synthesis
80
wt% Non-Diffracting
80
60 60
40 40
20 20
0
0 4 6 8 10 12 14
4 6 8 10 12 14
NaOH Molarity
NaOH Molarity
wt% Crystalline Cancrinite wt% non-Diffracting/unidentified

Reaction Temperature = 150 oC
100
1h Synthesis 100
1h Synthesis
15hrs Synthesis 15h Synthesis
80 24hrs Synthesis
wt% Non-Diffracting
80 24h Synthesis
60 60
40 40
20 20
0
0
4 6 8 10 12 14
4 6 8 10 12 14
NaOH Molarity
NaOH Molarity
wt% Crystalline Cancrinite wt% non-Diffracting/unidentified

Reaction Temperature = 200 oC
Figure 4. Influence of time and NaOH molarity upon cancrinite synthesis from SLR at 150 and
200 ℃ a) Crystalline cancrinite, b) non-Diffracting material. Uncertainties were calculated with
a 95% confidence interval.
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Reaction at 100 oC with 10 M NaOH solution for 24 hours produced crystalline cancrinite
(Na6Ca1.5(CO3)1.5(Si6Al6O24).2H2O) at 10.4 wt %; in addition to a dominant non-diffracting
fraction of 74.2 wt%, sodalite (9.8 wt%), and quartz (SiO 2) (3.9 wt%) and a small amount of
zeolite LTA (1.7 wt%) (Supplementary Table 3). Murukutti and Jena (2022) indicated that
extended reaction of coal fly ash at 100 oC promoted the transition from zeolite LTA to
hydroxysodalite. It is noted that the XRD pattern for cancrinite was best fitted to the pattern
for Na6Ca1.5(CO3)1.5(Si6Al6O24). However, from the XRF analysis (
Supplementary Table 6) it was apparent that the amount of calcium present in the cancrinite
material was substantially less than the quantity of Si or Al present (oxide mass ratios relative
to CaO of 90 and 32, respectively). Studies of coal fly ash conversion to zeolitic materials
suggested that cancrinite with the formula (Na 8Al6Si6O24(OH)2.2H2O) was formed when
activating fly ash with sodium carbonate at 200 oC for 20 hours (Murukutti & Jena, 2022).
Notably, XRD is a phase analysis technique, not a chemical one. Thus, the results derived
from modelling can match phases or specific crystal structures to patterns with a certain degree
of confidence based on the pattern intensity, the position (Bragg angle or interplanar spacing) ,
and intensities of the diffraction maxima (peaks) (H. Khan et al., 2020). In this case the samples
fitted to a cancrinite pattern with extra Ca because the match was focused on specific structural
details where all members have the same structure. In order to determine the chemical structure
of the material it is important to support XRD results with XRF/elemental results.
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The data recorded for activation of SLR at 100 oC suggested that conditions were not sufficient
to fully transform the starting mixture to the more thermodynamically stable cancrinite phase
( Hackbarth et al., 1999). This conclusion was supported by reports that cancrinite synthesis
from kaolinite or coal fly ash was observed at significantly higher temperatures such as 200 oC
(Murukutti & Jena, 2022; Wernert et al., 2020) or 250 ℃ (Selim et al., 2018).
Therefore, the reaction temperature was increased to 150 oC while using 4 to 10 M NaOH
solutions. After one hour at 150 oC, the formation of cancrinite in greater amounts (20 wt %)
was observed when compared to the 100 oC analogues (Figure 4). Moreover, there was a
distinct trend whereupon increasing NaOH molarity promoted cancrinite synthesis. See Figure
3. Process flow diagram for the synthesis of zeolite LTA from Spodumene Leachate Residue
via cancrinite formation; Additional NaAlO2 added to the cancrinite . Increasing the reaction
time to 24 hours promoted the formation of cancrinite, with 79 wt% identified when reacted in
10 M NaOH. Even at the lower NaOH molarity of 4 M, the amount of cancrinite recorded was
63 wt%. It was noted that when cancrinite was synthesised, corresponding decreases in the
presence of non-diffracting material (Figure 3) and quartz were evident. Sodalite formation
appeared to be inhibited, especially if reaction occurred for 24 hours (Supplementary Table 4),
which was in accord with previous literature (Murukutti & Jena, 2022). This behaviour was
consistent with sodalite being an intermediate phase transformed to the more
thermodynamically stable cancrinite under high molarity and temperature conditions
(Limlamthong et al., 2021).
Based upon the data acquired at reaction temperatures of 100 and 150 oC it was postulated that
not only NaOH molarities >10 M promote cancrinite formation but also that at higher reaction
temperatures the formation of cancrinite may be accelerated (Figure 3). Accordingly, using
five M NaOH solutions for 1 hour at 200 oC enhanced cancrinite synthesis (38 wt %). As
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reaction time increased to 15 and then 24 hours the cancrinite phase was raised to 42 and 68
wt%, respectively. Further increasing the NaOH molarity to 7 M initially promoted the
formation of cancrinite (44 wt%) after one hour of reaction but a slight inhibition of cancrinite
formation was observed when the reaction time was extended (relative to 5M NaOH). Use of
10 M NaOH solutions generally improved the cancrinite formation up to 71 wt% after 24 hours
reaction. However, the appearance of sodalite was noted at this molarity. and clearly, when
using 14 M NaOH, the presence of cancrinite was substantially reduced. Simultaneously the
presence of non-diffracting species and sodalite was enhanced (Supplementary Table 5).
Overall, activation times of 24 hours may not be practical due to excessive energy costs; thus,
the reaction temperature was further elevated to 240 oC while fixing the reaction time as one
hour. In addition, the NaOH molarity was adjusted to either 7 or 10 M with the aim of
promoting cancrinite formation (Table 1). With 10 M NaOH solutions a dominant non-
diffracting component was detected. Concurrently a small amount of cancrinite crystals (15
wt%) was formed. Indeed, the major crystalline phase was identified to be sodalite. In
contrast, reacting SLR at 240 ℃ for one hour with 7 M NaOH substantially increased cancrinite
content to 87.2 wt%.
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Table 1. XRD analysis of solid products resultant from SLR activation at 240 oC as a function
of NaOH molarity and reaction time
10M NaOH 7M NaOH
Phase 1 hour synthesis 1 hour synthesis (wt%)
(wt%)
Crystalline Quartz (%) 0.0 0.5
Crystalline Cancrinite (%) 15.0 87.2
Crystalline Sodalite (%) 17.60 0.2
Crystalline Zeolite LTA (%) 1.3 2.8
Non-Diffracting/unidentified (%) 66.1 9.3
Hackbarth, et al. (1999) found that at elevated temperatures such as 200 oC, increasing the
NaOH molarity from 12 to 16 M resulted in transformation of cancrinite to sodalite. It is
therefore probable that at a temperature of 240 oC the NaOH molarity would further need to be
reduced. Scanning electron microscope (SEM) images of samples synthesised at 150 and 240
oC showed the presence of needle shaped cancrinite crystals in each instance (Figure 5) (Deng
et al., 2006).
a) 150 o C, 10 M NaOH and 24 hours b) 240 oC, 7 M NaOH and 1 hour

Figure 5: SEM images of solid material created by NaOH treatment of SLR at temperatures
of 150 and 240 oC
As indicated above, the energy consumption is important in terms of engineering optimizat ion
of the SLR to cancrinite method. Thus, energy demand for cancrinite synthesis at 240 oC for
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one hour (7 M NaOH, 87.2 wt%) was compared with SLR activation at 150 oC for 24 hours
(10 M NaOH, 79 wt%) using temperature data acquired every minute during heating and
cooling periods. Equation 1 (Luscombe, 2018) was employed to estimate the heat energy input
per minute, using the measured temperature at that step compared to the initial temperature.
Thus, a range of average heat energy values per minute for each time step was generated. The
median of these values allowed calculation of the energy added per minute when the reactor
was heated to reaction temperature.
Equation 2. Heat Energy 𝑸/𝒕 = 𝒎 ∗ 𝑪𝒑 ∗ 𝒅𝑻/𝒕
Where Q is the heat energy (J), m is the mass (g), Cp is the heat capacity (J/kg. K), dT is the
change in temperature (K), and t is the time (s). Once the vessel reached reaction temperature,
the temperature was maintained for the specified reaction time prior to cooling, when reaction
was completed. To estimate the heat losses in the system, and therefore the energy required to
hold the temperature for the set time, a similar approach was taken using the data during the
cool down period. Once again, heat energy was calculated per minute and a median value was
taken, which was the heat loss through the vessel due to radiation. The total heat required was
calculated using Equation 3 (Luscombe, 2018). The heating cycle to reach the required
activation temperature was considered as well as the time that the reaction temperature was
held (24 hours or 1 hour).
Equation 3. Total Energy Required 𝑸𝑻𝒐𝒕𝒂𝒍 = 𝑸𝑰𝒏 ∗ 𝒕𝑯𝒆𝒂𝒕 + 𝑸𝑳𝒐𝒔𝒔𝒆𝒔 ∗ 𝒕𝑯𝒐𝒍𝒅
The results of this calculation revealed that heating the sample at 150 oC for 24 hours consumed
3.7 times more energy than activation at 240 oC for one hour (Supplementary Figure 4).
Additional benefits of using the shorter reaction time included greater throughput which may
translate to reductions in capital expenditure through smaller equipment requirements.
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Subsequently, using the optimized SLR activation procedure of 240 oC and 7 M NaOH for 1
h, bulk material was produced in 1 L hydrothermal reactors to provide sufficient material for
the remaining tests in this study. The average amount of crystalline cancrinite observed in the
solid product after 5 repetitions was 87 ± 5 wt%.
Mass Balance for Synthesis of Cancrinite from SLR and Sodium Hydroxide Aqueous
Solution
As the activation conditions for SLR to cancrinite have been determined, this situation allowed
a mass balance calculation to identify important criteria such as mother liquor composition and
process yields of cancrinite (Figure 6). The process illustrated was for heating the starting
mixture at 240 oC with 7 M NaOH for one hour. In terms of overall mass balance between the
starting materials and solid/liquid products, 100 % mass balance for Si (18.7 g), Al (7.5 g) and
Na was obtained (66.1 g), whereas a slight discrepancy was noted for the water content (Inlet
410.8 g and outlet 402.1 g). This data suggested that water losses may have occurred during
processes such as centrifuging the sample after hydrothermal reaction to collect solids and
mother liquor.
More specifically the mother liquor and wash water analysis revealed that a total of 9.1 g of Si
had reacted to form the solid product, whereas 9.6 g had unreacted. On this basis the
SiO2/Al2O3 molar ratio of the cancrinite was reduced to 2.32 (c.f. starting value of 4.8 for SLR).
XRF analysis of the cancrinite product (
`
Supplementary Table 6) similarly estimated a SiO2/Al2O3 molar ratio of 2.5. X. Wang et al.
(2021) also found that cancrinite made from alkali activation with NaOH produced cancrinite
with a SiO2/Al2O3 molar ratio of 2.62. It is noted that the difference in the product composition
(Na9(CO3)1.5 (Si6 Al6 O24).2H2O) and the XRD database pattern
(Na6Ca1.5(CO3)1.5(Si6Al6O24).2H2O) was substitution of sodium ions for calcium ions (which
were not available when SLR was activated with NaOH). Carbonate-cancrinite was more
probable than hydroxy-cancrinite as the measured Loss on Ignition (LOI) of 9.5 wt% was closer
to Na9 Al6 Si6 O24 (CO3 )1.5 . 2H2 O (LOI = 7.5 wt%) rather than (Na8Al6Si6O24(OH)2.2H2O) (LOI
= 3.5 wt%).
Consequently, the stoichiometric conversion of SLR to cancrinite was approximated as shown
in Equation 4
Equation 4: 𝟑 𝑯𝟐 𝑨𝒍 𝟐𝑺𝒊𝟒.𝟓𝑶𝟏𝟑.𝟏. 𝟓𝑯𝟐 𝑶 + 𝟐𝟒 𝑵𝒂𝑶𝑯 + 𝟏. 𝟓 𝑪𝑶𝟐 →

𝑵𝒂𝟗 𝑨𝒍 𝟔 𝑺𝒊 𝟔 𝑶𝟐𝟒(𝑪𝑶𝟑 )𝟏.𝟓.𝟐𝑯𝟐 𝑶 (𝒔 ) + 𝟕. 𝟓 𝑵𝒂𝟐 𝑺𝒊𝑶𝟐(𝑶𝑯)𝟐 (𝒂𝒒) + 𝟏𝟎 𝑯𝟐 𝑶
`
Figure 6: Process flow diagram including stream tables for (1) conversion of SLR to cancrinite and (2) SLR mother liquor to zeolite LTA
`
The conversion represented in Equation 3 has a theoretical yield of 48.8 g of cancrinite and 47 g of
dissolved silicate from 60 g of SLR material. The mass balance reported in Figure 6 shows a mass
yield of 50.16 g of cancrinite which represented a 103 % yield (essentially 100 % as inherent errors
in measurement were involved). The theoretical yield of 9.4 g of dissolved silicon matched with the
observed silicon amount of 9.59 g in the mother liquor/wash water. The agreement between the mass
balance and the theoretical yield indicated that Equation 3 was a good approximation of the process.
Synthesis of Zeolite LTA from Recycled Mother Liquor after Cancrinite Synthesis
After cancrinite synthesis, an excess of 20.5 g/L dissolved active silicon species was found in the
mother liquor as well as an excess of NaOH. Upon addition of water to adjust the NaOH molarity (4
M) and sodium aluminate to adjust the SiO 2/Al2O3 ratio to 2, an aluminosilicate gel was rapidly
formed, which was then heated in an incubator at 80 oC. XRD results in Table 2 revealed that zeolite
LTA was formed with negligible by-products such as quartz, cancrinite or sodalite detected.
Table 2. XRD results after the mother liquor recycling process.

XRD phases (wt%) 2-hour synthesis 3-hour synthesis 5-hour synthesis
Quartz 0.2 0.1 0.2
Cancrinite 0.0 0.1 0.0
Sodalite 0.0 0.0 0.0
Zeolite LTA 63.7 67.8 68.9
Non-diffracting 36.1 32.0 31.1
SEM images confirmed the appearance of zeolite LTA rounded cubes (Figure 7). Bronić, Palčić,
Subotić, Itani, and Valtchev (2012) also reported the presence of zeolite LTA crystals with truncated
edges. Similarly, Basaldella, Kikot, and Tara (1997) intimated that when using SiO2/Al2O3 ratios in
the starting mixture between 1.48 and 1.99 the final zeolite LTA product was cubic with bevelled
edges. To obtain cubes with sharp edges it was necessary to increase the SiO 2/Al2O3 ratio to >2.18.
The effect on LTA nucleation is due to the change in the overall concentration of the species present
in solution, which is higher when more concentrated NaOH is used to neutralize it, as suggested in
the context of promoting crystal formation, accelerating nucleation, and influencing the crystal
growth mechanism.
The success of the mother liquor modification and subsequent synthesis of zeolite LTA was
consistent with published studies of other zeolite synthesis approaches. For example . C. Liu et al.,
(1998) showed that after zeolite crystallization the mother liquor contained sodium silicate species.
In this case, aluminium sulfate was added, which in turn reacted with the active silicon species in the
mother liquor to form an aluminosilicate gel. Zeolite Y was subsequently synthesised, with the caveat
that the presence of zeolite crystals in the mother liquor (>2 wt%) may compromise the quality of the
zeolite product.
`
Reaction time
2 hours 3 hours 5 hours
4,000x 4,000x 4,000x
10,000x 10,000x 10,000x

Figure 7: SEM images of the zeolite product after hydrothermal reaction of mother liquor modified
by water and sodium aluminate addition; Reaction temperature 80 oC; Time = 2 to 5 hours
This study of transforming SLR to cancrinite and zeolite LTA products indicates a key aspect of its
success appears to be the value of the cancrinite. Investigations of cancrinite applications describe
the potential for cancrinite to be used as a sorbent for heavy metal ions such as Pb (II) and Cu (II)
ions when added to contaminated soils (Zheng et al., 2021). Similarly, Wernert et al. (2020)
described the successful use of cancrinite to remove Cd (II) and Pb (II) species from water.
Alternatively, Đặng et al., (2021) indicated that cancrinite catalysed the transesterification reaction
of palm oils and soybean with methanol to make biodiesel. Hence, the dual product approach
described in this study may have merit and is worthy of further exploration.
`
Process 2: Synthesis of Zeolite LTA from SLR via Cancrinite Formation
Addition of NaAlO2 to the SLR Activation Mixture

As indicated in the mass balance for synthesis of cancrinite from SLR and sodium hydroxide aqueous
solution, it was apparent that the mother liquor comprised of unreacted sodium silicate species. To
recycle the mother liquor, it is necessary to remove the dissolved silicate species as these will
accumulate over time. One strategy was to add additional sodium aluminate along with the SLR and
NaOH to create a mixture with SiO2/Al2O3 ratio = 2. (Equation 5).
Equation 5: 𝟐 𝑯𝟐 𝑨𝒍𝟐 𝑺𝒊𝟒.𝟓 𝑶𝟏𝟑. 𝟏. 𝟓𝑯𝟐 𝑶 + 𝟖. 𝟓 𝑵𝒂𝑶𝑯 + 𝟓 𝑵𝒂𝑨𝒍𝑶𝟐 + 𝟐. 𝟐𝟓 𝑪𝑶𝟐 →

𝟏. 𝟓 𝑵𝒂𝟗 𝑨𝒍𝟔 𝑺𝒊𝟔 𝑶𝟐𝟒 (𝑪𝑶𝟑 )𝟏.𝟓 .𝟐𝑯𝟐 𝑶 (𝒔) + 𝟔. 𝟐𝟓 𝑯𝟐 𝑶
In practice, it was necessary to add sodium hydroxide solution in excess of stoichiometric amounts
to a prescribed value which promotes cancrinite formation (Equation 6).
Equation 6: 𝟐 𝐇𝟐 𝐀𝐥 𝟐𝐒𝐢𝟒.𝟓 𝐎𝟏𝟑 .𝟏. 𝟓𝐇𝟐 𝐎 + 𝟒𝟎 𝐍𝐚𝐎𝐇 + 𝟓 𝐍𝐚𝐀𝐥𝐎𝟐 + 𝟐. 𝟐𝟓 𝐂𝐎𝟐 + 𝟑𝟏𝟒 𝐇𝟐 𝐎

→ 𝟏. 𝟓 𝐍𝐚𝟗 𝐀𝐥𝟔 𝐒𝐢𝟔 𝐎𝟐𝟒 (𝐂𝐎𝟑 )𝟏.𝟓.𝟐𝐇𝟐 𝐎 (𝐬) + 𝟑𝟏. 𝟓 𝐍𝐚𝐎𝐇
+ 𝟑𝟐𝟎. 𝟐𝟓 𝐇𝟐 𝐎
Figure 8 shows the collected data when additional aluminate was added to the synthesis mixture in
order to adjust SiO2/Al2O3 ratio to 2.
`
Figure 8: Process flow for cancrinite synthesis from a starting mixture containing SLR, NaOH,
water and sodium aluminate; one hour at 240 oC in hydrothermal reactor.
The solid product resultant from SLR activation at 240 oC for one hour was composed of 26.5 %
cancrinite, 13 wt% sodalite and 59 wt% amorphous (as measured by quantitative XRD). In accord
with the presence of extra soluble aluminium species the amount of silica found in the mother liquor
was substantially less than the case when additional aluminium was not present (ca. 0.64 g compared
to 6.67 g, respectively). However, despite the increased reaction of dissolved silicates with aluminate
species, this process did not enhance the presence of crystalline cancrinite. Inspection of SEM images
for the solid product (Figure 8) revealed that the presence of the cancrinite pillars was significantly
less than observed when additional aluminium was present (Figure 6).
`
The underlying reason for the inhibition of cancrinite formation was not evident. One hypothesis
was that an excess of silicate species may needed to promote cancrinite growth. This suggestion was
consistent with the well-known synthesis of zeolite X which typically is made using a SiO 2/Al2O 3
ratio in the synthesis gel of 2.9 to 3.8 (whereas the product zeolite had a SiO2/Al2O3 ratio of
approximately 2.5) (Ahmadon et al., 2018; X. Zhang et al., 2013).
Transformation of Cancrinite to Zeolite LTA

Given that carbonate-cancrinite (Na9 Al6 Si6 O24 (CO3 )1.5 . 2H2 O) has a SiO2/Al2O3 ratio of 2 it was
pertinent to examine if acid dissolution followed by neutralization and hydrothermal synthesis
produced zeolite LTA (Figure 3). Table 3 shows that only minor amounts of zeolite LTA were
present in the solid product along with the non-diffracting major product. Use of higher acid
concentrations appeared to be detrimental to zeolite LTA formation.
Table 3. XRD data for zeolite LTA synthesis from cancrinite: four hours reaction time; agitation 100
rpm; reaction temperature 80 ℃; dissolution of cancrinite with either 2 or 3 M HCl followed by
neutralization.
Phase (wt%) Dissolved at 2M HCl Dissolved at 3M HCl
Quartz 0.1 0.1
Cancrinite 1.8 1.2
Sodalite 0.0 0.0
Zeolite LTA 14.9 4.9
Non-diffracting 83.3 93.8
SEM images corroborated XRD data as the presence of cubic zeolite LTA crystals was not prevalent
(Figure 9).
`
2 M HCl 3 M HCl
Figure 9. SEM images of solid material made from cancrinite: four hours reaction time; agitation
100 rpm; reaction temperature 80 ℃; dissolution of cancrinite with either 2 or 3 M HCl followed by
neutralization.
Addition of NaAlO2 to the Cancrinite Product

Based upon the analysis above one idea to promote the formation of zeolite LTA was the introduction
of excess aluminium species. This practice is used in the zeolite industry wherein the most common
SiO2/Al2O3 ratio appears to be 1.8 ± 0.2 ( Kettinger et al., 1979). In theory, the presence of excess
aluminium species minimizes the formation of by-products.
Acid Dissolution of Cancrinite to Make Active Al and Si species.
As seen above in “Transformation of Cancrinite to Zeolite LTA” the molarity of HCl employed
to create active aluminium and silica species from cancrinite was important. Therefore, the influence
of hydrochloric acid concentration was investigated by contacting cancrinite (1 g) and additional
sodium aluminate (initially set to SiO 2/Al2O3 ratio = 1.14) with 10 mL of hydrochloric acid (HCl) at
different molarities. Figure 10 shows the theoretical maximum amount of Si and Al in solution if the
cancrinite was totally dissolved. Substantial dissolution of cancrinite occurred when using 2 to 4 M
HCl (maximum value of 97 and 89 % aluminium and silica active species). Under the highly acidic
`
conditions, the active species in solution are reported to be (Al(H2O)6)3+ and H4SiO4 (J.-Q. Wang
et al., 2016). The scope to reduce the HCL concentration was not possible as formation of active
species was limited at a HCl molarity of 1 M. Notably, J.-Q. Wang et al. (2016) reported that
hydroxycancrinite made from kaolin became XRD amorphous after using 0.2 M HCl in a timeframe
of 30 minutes. This observation may indicate that another factor which is potentially important is the
solid/liquid ratio when adding acid to an aluminosilicate material (Jiang et al., 2012).
100 100
Si Active species (%)

Al Active species (%)
90 90
80 80
70 70
60 60
50 50
0 1 2 3 4 5 0 1 2 3 4 5
HCl Molarity (M) HCl Molarity (M)
Figure 10: Influence of HCl molarity on Al and Si active species formation from cancrinite/sodium
aluminate
Although the acid dissolution stage created active silica and aluminium species, it was apparent that
the addition of HCl also made NaCl. As discussed in the following sections, this salt production may
represent a significant financial and environmental problem when making zeolites from SLR.
Neutralization of Acidic Solution of Active Al and Si Species Followed by Zeolite Synthesis
To initiate zeolite formation, an acid neutralization stage was completed to promote homogeneous
gel formation. NaOH (10 mL per gram of cancrinite) at the desired molarity was added into the acid
solution whereupon an aluminosilicate gel was apparent. This gel was then reacted under agitation
conditions (100 rpm) at 80 ℃ for various synthesis times to form zeolite LTA.
`
According to Krongkrachang et al., (2019) the presence of chloride ions in the reaction interfered
with zeolite crystallization. Therefore, only dissolution of cancrinite/NaAlO2 with 2 and 3 M HCl
was studied in relation to the impact of subsequent neutralization and ultimately, zeolite LTA
formation. Table 4 reveals a similar trend in zeolite LTA quality (i.e., reduction in zeolite LTA
amount when higher molarity acid was employed in the cancrinite dissolution stage) to the situation
where no additional NaAlO2 was added to the cancrinite. Notably the highest amount of crystalline
zeolite LTA was 63.1 wt% using the 2 M HCl solution, and only 35.7 wt% when 3 M HCl was
employed in the activation step.
Table 4. Quantitative XRD analysis of zeolite LTA: Impact of cancrinite/sodium aluminate acid
treatment conditions
wt%
Sample names
Quartz Cancrinite Zeolite LTA Non-Diffracting
Cancrinite dissolved in 2M HCl 0.2 4.7 63.1 32.0
Cancrinite dissolved in 3M HCl 0.3 6.1 35.7 58.0
Further information was acquired by application of Scanning Electron Microscopy to image the
zeolite products outlined in Table 4 (Figure 11). Dissolution of cancrinite with 2 M HCl followed by
neutralization using 4M NaOH and hydrothermal synthesis at 80 oC, clearly produced cubic zeolite
LTA crystals (approximately 1 to 1.5 micron in size). In contrast, use of 3 M HCl inhibited zeolite
LTA formation (Figure 11). This observation agrees with Garcia et al., (2018) who noted that the
presence of NaCl suppressed zeolite P formation.
`
a) Cancrinite dissolved in 2M HCl b) Cancrinite dissolved in 3M HCl
Figure 11.SEM images of zeolite LTA: Influence of different HCl concentrations on zeolite LTA
synthesis at 4 h, 80 ℃ and neutralized with 4 M NaOH solution: Cancrinite/NaAlO 2 dissolved in (a)
2 M HCl and (b) 3M HCl.
From the results shown in Table 4 it was pertinent to investigate the influence of sodium hydroxide
molarity upon zeolite LTA growth, as this factor may be important in controlling zeolite formation.
Tests were conducted wherein the cancrinite was activated using a 2 M HCl solution, then neutralized
by varying NaOH molarities, and finally hydrothermally reacted at 80 oC for four hours (Figure 12).
100 100
wt% Crystalline Zeolite LTA
wt% Non-Diffracting
80 80
60 60
40 40
20 20
0
0
2 3 4 5 6 7 8
2 3 4 5 6 7 8
NaOH Molarity (M)
NaOH Molarity (M)
Figure 12: XRD determination of % of crystalline zeolite LTA in solid product as a function of
NaOH molarity used in the neutralization stage: reaction temperature 80 oC; reaction time 4 h;
Si/Al = 0.57
`
Figure 12 shows that zeolite LTA synthesis rapidly intensified when raising the NaOH molarity
above 2 M; and peaked when using 4M NaOH (63 ± 5%). The solid products formed at higher NaOH
molarities plateaued in terms of zeolite LTA content. As zeolite LTA was formed, the amount of
amorphous material detected reduced in abundance. Some cancrinite was also present in amounts
ranging from 3 to 8 wt %. Due to the relatively small zeolite LTA size quantitative XRD analysis
may have been comprised by line broadening and/or a zeolite with significant amount of defects in
the structure (Raić et al., 2020; Strachowski et al., 2022). Further insight into the impact of sodium
hydroxide concentration is shown in Figure 13. Use of 2 M NaOH evidently did not promote zeolite
crystallization as the material appeared highly amorphous. Whereas the 3 M NaOH solution
promoted crystallization of cubic zeolite LTA, although the presence of less developed cubes was
evident. When neutralizing the acid activated cancrinite with either 4 or 5 M NaOH the formation of
cubic zeolite LTA was widespread.
`
Neutralized in 2M NaOH Neutralized in 3M NaOH
Neutralized in 4M NaOH Neutralized in 5M NaOH
Figure 13. Influence of NaOH molarity in the neutralization stage prior to the formation of zeolite
LTA.
Impact of SiO 2/Al2O3 Molar Ratio upon Zeolite LTA Synthesis

As indicated previously, when making zeolite LTA commercially the SiO2/Al2O3 ratio is often less
that the value of 2 (1.8 ± 0.2) ( Kettinger et al., 1979). The silica/alumina ratio significantly influences
the crystallinity and properties of zeolite LTA. Higher silica/alumina ratios yield more ordered and
crystalline structures, impacting ion exchange capacity, catalytic activity, thermal stability, and
suitability for specific applications (Derouane, 1992).
`
In a previous section (Addition of NaAlO2 to cancrinite product) the SiO2/Al2O3 ratio was 1.14, thus
it was of interest to study higher values of SiO2/Al2O3 (up to a value of 2). Figure 14 showed that
increasing the SiO2/Al2O3 ratio decreased the amount of crystalline zeolite LTA. Simultaneously the
presence of amorphous material correspondingly increased.
The cancrinite impurity phase was favoured at lower values of SiO 2/Al2O3. Ameh et al., (2017)
examined the impact of sodium aluminate addition to fused coal fly ash in relation to subsequent
hydrothermal synthesis of zeolite LTA. It was found that the crystallinity and purity of zeolite LTA
was promoted when the SiO2/Al2O3 ratio was deceased from 2.14 to 1.02. Zhang et al. (2013) also
observed the formation of zeolite X from hydrogels at SiO2/Al2O3 = 3.5 to 1.5 and zeolite LTA at
SiO2/Al2O3 = 1.0 to 0.5. Mechanistically it was postulated that the low silica concentrations
constrained the building units to be double four membered rings which favoured zeolite LTA growth.
`
100
Dissolved in 2M HCl
wt% Crystalline Zeolite LTA

Dissolved in 3M HCl
80
60
40
20
0
1.2 1.4 1.6 1.8 2.0
SiO2/Al2O3 ratio
100 100
Dissolved in 2M HCl Dissolved in 2M HCl
Dissolved in 3M HCl wt% non-diffracting Dissolved in 3M HCl

80 80
60 60
40 40
20
20
0
0
1.2 1.4 1.6 1.8 2.0
1.2 1.4 1.6 1.8 2.0
SiO2/Al2O3 ratio
SiO2/Al2O3 ratio
Figure 14. Influence of different HCl concentrations on Zeolite LTA synthesis using different Si/Al
ratios, synthesis at 4 h, 80℃ and neutralized with 4M NaOH solution.
The Influence of Hydrothermal Synthesis Time upon Zeolite LTA Formation

Ideally, the synthesis time for zeolite LTA should be relatively short in order to lower production
costs. Figure 15 illustrates the relationship between the amount of crystalline zeolite LTA detected
by XRD analysis as a function of reaction time. After two hours 44.2 % of the solid product was
estimated to be crystalline zeolite LTA. Increasing the reaction to four hours resulted in greater
amounts of zeolite LTA (63.1 wt%) formed; albeit extending the time further did not reveal any
process benefits. One negative aspect was the identification of cancrinite (Table 5) in the range 5 to
8 wt%.
`
100
Zeolite LTA
Non-diffracting
80
wt% Crystalline
60
40
20
0
2 3 4 5 6
Time (hrs)
Figure 15. Influence of synthesis time on zeolite LTA synthesis: reaction temperature 80℃; 0.57
Si/Al ratio; and 100 rpm agitation
Supplementary Figure 5 shows that after two hours reaction there was a mixture of phases present
and that extending the reaction time to four hours correspondingly increased the presence of cubic
zeolite LTA crystals. Thus, there was a good correlation between the XRD data (
Table 5) and SEM images (Supplementary Figure 5).
Table 5. XRD analysis of zeolite LTA activated at 2M HCl and synthesised at a reaction
temperature 80℃; 0.57 Si/Al ratio; and 100 rpm agitation.
Wt%
Zeolite Non-
Synthesis time (h) Quartz Cancrinite Sodalite
LTA Diffracting
2 0.1 7.1 0.0 44.2 48.7
3 0.0 6.8 0.0 55.8 37.4
4 0.2 4.7 0.0 63.1 32.0
5 0.1 7.9 0.0 54.4 37.6
6 0.1 8.1 0.0 57.1 34.7
`
Mass Balance of the Activation of Cancrinite, Neutralization and Zeolite Synthesis
The question thus arising was the fate of the excess aluminium species added. Due to Lowenstein’s
rule, it is not possible to have Al-O-Al pairs in a zeolite lattice which means that the lowest
SiO2/Al2O3 ratio in the zeolite LTA framework is two. Consequently, the mass balance of the
conversion of cancrinite/sodium aluminate to zeolite LTA was examined (Figure 16). In the acid
dissolution stage, it was evident that not only was the creation of active aluminium and silica species
high (98.4 & 94.4 %, respectively) but also substantial amounts of chloride ions in solution were
present (1.41 g). In relation to the synthesis parameters the molar ratios of the reactants were:
SiO2/Al2O3 = 1.07; Na2O/SiO2 = 4.99; H2O/Na2O = 35.94. These feed ratios were calculated after
correction of sodium ions associated with the chloride ions in solution. Hydrothermal synthesis at 80
oC for four hours produced a wet cake which was 46.5 wt% solids. After drying the solid material,
analysis indicated that the SiO2/Al 2O3 ratio of the zeolite LTA was 1.92. This value was in excellent
agreement with the theoretical formula for zeolite LTA of Na12((AlO2)12(SiO2)12)·27H2O and
supported by the data shown in Figure 13 and Figure 14.
The mother liquor contained minimal silica species (0.005 g) which was in accord with the excess of
aluminium employed in the zeolite synthesis stage to ensure maximum reaction of silica species. In
contrast a significant amount of dissolved aluminium species was present (0.21 g), as was sodium
ions (1.854 g), and chloride ions (1.02 g). Subtraction of sodium ions associated with dissolved
chloride revealed that 1.191 g of sodium ions were probably present as sodium hydroxide. Notably
the first washing stage of the wet cake contained a significant amount of dissolved aluminium,
sodium, and chloride ions. Table 6 illustrates the overall mass balance for the cancrinite to zeolite
LTA route. Within experimental error all elements were satisfactorily accounted for.
Table 6: Mass balance for zeolite LTA formation by conversion of cancrinite
`
Mass (g)
Feed Mix Dry Solid Mother Liquor Wash Water Balance
Si 0.34 0.33 0 0.01 0
Al 0.61 0.33 0.21 0.08 -0.01
Na 3.69 0.14 1.85 1.7 0
Cl 1.41 0 1.02 0.38 0.01
A final comment is made in terms of the practical aspects of this new route for transforming SLR to
a valuable zeolite (Figure 16). Usually, recycling of mother liquor from the hydrothermal stage is
necessary to recover expensive sodium hydroxide (Pastorello & Troglia, 1987). However, the use of
acid to dissolve the cancrinite inherently means that sodium chloride is made. If, in the process
described in this study, the mother liquor was recycled, then salts may accumulate and ultimately
create a waste stream. The synthesis method is gaining complexity and thus may not be able to
compete with conventional zeolite LTA synthesis.
`
Figure 16. Process flow diagram including stream tables for conversion of cancrinite to zeolite LTA
`
Conclusions
Zeolite LTA has been successfully synthesized from waste spodumene leachate residue (SLR)
produced during lithium mining from hard rock. Conversion of SLR initially to a cancrinite
intermediate was demonstrated and subsequent acidification, neutralization and hydrothermal
synthesis completed.
The first process involved creation of dual products, namely zeolite LTA and cancrinite. In this
instance, advantage was taken of the fact that the mother liquor contained a high level of active
silicate species. Addition of sodium aluminate to the mother liquor followed by hydrothermal
synthesis created high quality zeolite LTA. A critical issue was the value attributed to cancrinite
which may have use for heavy metal removal, biofuels production, or agriculture.
A second strategy was to add additional aluminium species to the feed mixture to promote cancrinite
formation by reaction with the excess silica species resultant from the fact that SLR had a SiO2/Al2O 3
= 4. However, it was challenging to produce high quality cancrinite by this method, and this was
attributed to a possible need to have an excess of silica species present to drive cancrinite formation.
A third strategy involved use of a cancrinite/sodium aluminate mixture which was then dissolved in
acid, neutralized with NaOH, and hydrothermally reacted. High quality zeolite LTA was formed by
using 2 M HCl and 4 M NaOH for the acid dissolution and neutralization steps. Addition of extra
sodium aluminate to lower the SiO2/Al2O3 to <1 improved zeolite LTA quality. Mass balancing
revealed that the excess aluminium species were in the mother liquor and wash water.
`
The presence of active aluminium species and sodium hydroxide was beneficial if reused in the
synthesis process. However, the presence of sodium chloride was proposed to be problematic in
terms of interference with zeolite synthesis and enrichment in the mother liquor/wash water which
ultimately created a wastewater.
In conclusion, the cancrinite intermediate route for making zeolite LTA is technically feasible if
conditions are chosen carefully. Future research should address the feasibility of Process 1 in greater
detail, especially in terms of cancrinite application and process economics. Determination of a cost-
effective means to remove/recover sodium chloride for Process 3 would also be valuable.
`
Key Insights
This chapter demonstrated the successful synthesis of zeolite LTA from waste spodumene leachate
residue (SLR) through a multi-step process involving the creation of a cancrinite intermediate.
Following the activation process, two products were obtained, the mother liquor and cancrinite. The
addition of sodium aluminate to the mother liquor, followed by hydrothermal synthesis, produced
high-quality zeolite LTA. This is a noteworthy achievement, as a high-purity material can be
produced through this route, with all impurities remaining in the solid product (cancrinite), while the
mother liquor consists mainly of pure silicon species.
However, the production of cancrinite proved to be challenging, requiring additional aluminium
species for its formation. Hydrochloric acid was utilized to dissolve the cancrinite and obtain active
aluminium and silica species, followed by neutralization with NaOH and hydrothermal reaction to
form zeolite LTA. Nonetheless, the presence of sodium chloride was problematic, interfering with
zeolite synthesis and increasing the complexity of the process to recycle mother liquor and washing
water, ultimately leading to wastewater generation. Thus, further research is necessary to identify
alternative methods for cancrinite utilization that do not necessitate the presence of hydrochloric acid.
The next chapter focuses on the improvement of this method. In order to further optimize and improve
the synthesis of zeolite LTA from waste spodumene leachate residue, several areas of research can
be explored. One potential avenue is the investigation of high silica waste materials as a means to
improve the efficiency of the method. The high levels of active silicate species present in the mother
liquor make waste materials with high silica content an attractive option, as they could lead to the
formation of a high purity solution while reducing the production of cancrinite.
`
Another promising area for future research is the exploration of alternative methods for cancrinite
use that do not require the presence of hydrochloric acid. A possible solution would be to investigate
the use of cancrinite as a raw material for other processes, such as phosphate absorption. This would
provide a sustainable solution for the disposal of waste materials, while also reducing the overall
complexity of the process and minimizing the generation of wastewater. These potential
improvements could have a significant impact on the commercial viability of the process and
contribute to a more sustainable approach to waste management.
`
Chapter 4: Transformation of natural zeolite powder to synthetic zeolite LTA
for water softening and lanthanum coated cancrinite for phosphate removal.
Abstract:
Mining of natural zeolite results in the formation of a powdered waste material which has limited
commercial value due to a combination of processing challenges and low purity. Therefore, a new
approach was taken to transform the powder into synthetic zeolite LTA and lanthanum supported on
cancrinite. Cancrinite was initially made by hydrothermal synthesis of zeolite with sodium hydroxide
solution at 240 oC. Importantly, use of 6 M NaOH solutions was necessary to reduce the amount
cancrinite present and promote the presence of silicates in solution. The resultant mother liquor was
composed of Si, Al, and Na while the bulk of the remaining impurities remained in the solid
cancrinite. Hydrothermal synthesis of the mother liquor with added sodium aluminate to adjust the
Si/Al ratio produced zeolite LTA crystals (95.5 wt%). The reaction time was preferred to be > three
hours under the applied conditions. Value was added to the cancrinite product by coating with
lanthanum chloride to make 25 g of lanthanum per kg of cancrinite. Subsequently phosphate species
were removed from solution (99 % reduction). Future research should focus on the development of
improved lanthanum doped cancrinite formulations and expand the testing to include solutions with
phosphate and multiple competing anions.
Key Words: zeolite, waste material, hydrothermal activation, mother liquor
Chapter 4: Transformation of natural zeolite powder to synthetic zeolite LTA for water softening and lanthanum coated
cancrinite for phosphate removal. 70
`
Introduction
Natural zeolites are widely used for applications such as molecular sieving (Eroglu et al., 2017),
catalysis (Hwang et al., 2002), cation exchange and sorption (Smith, 1985; S. Wang & Peng, 2010),
wastewater treatment (Rodríguez-Iznaga et al., 2018), and wound healing (Y. Li et al., 2012). In
terms of processing the natural zeolite deposits, the stages involved: (1) blasting to free the rocks;
(2) crushing; (3) fractionation; (4) washing; and (5) packaging (Yusupov et al., 2000). Consumer
demand is typically for crushed rocks in the size range 1 to 4 mm. Notably, there is limited industry
requirement for finer zeolite particles produced from the crushing step with most investigations of
natural zeolite conducted in the size range 0.5 to 3 mm (Zijun et al., 2021). Thus, a waste material is
generated with a particle size smaller than 100 µm. This powder not only represents a financial loss
in the process but also is a health hazard on site due the susceptibility of the small particles to be
inhaled (Hnizdo & Vallyathan, 2003; Steenland & Ward, 2014; Zijun et al., 2021).
One approach to the natural zeolite powder waste issue is the conversion of natural zeolite to value
added zeolites. For example, Zijun et al. (2021) used natural zeolite powder to synthetize zeolite
W. A high temperature alkali fusion stage was initially required to activate the natural zeolite powder.
Subsequently, aluminium hydroxide, potassium hydroxide and water were added to the activated
solid material and hydrothermal synthesis completed at 150 oC for 16 h. The material zeolite W
product exhibited a high capacity for ammonium exchange from water (324 meq/100 g). Despite the
success in making zeolite W, this study was probably not economic due to the costly fusion process.
Wruck et al. (2021) studied the influence of natural zeolite deposit upon activation of natural zeolite
and resultant synthesis of Zeolite LTA. Although the natural zeolite samples exhibited different
thermal stability, the quality of the final zeolite LTA product made via an alkali fusion process was
not significantly impacted (ca. 85 wt% zeolite LTA).
`
Avoidance of the need for high temperature alkali fusion has been described by J.-Q. Wang et al.
(2016) who transformed kaolin and quartz into zeolite Y using hydrothermal alkaline activation
(HAA). The procedure was to heat a mixture of kaolin, quartz, and high molarity sodium hydroxide
solution at 240 oC to form hydroxycancrinite. The hydroxycancrinite was unstable in the acid
solution and as such degraded to form active aluminium and silicate species when contacted with
HCl. Finally, sodium hydroxide was added to form a gel which was then reacted at 90 oC under
appropriate conditions to make zeolite Y. One claimed advantage of this hydroxycancrinite
intermediate process was that the purity of the zeolite Y was improved. A similar approach was also
reported by the same authors in a study regarding transformation of kaolin to zeolite LTA (J.-Q.
Wang et al., 2014). The conventional high temperature activation of kaolin to metakaolin was
replaced by hydrothermal alkaline activation and then the cancrinite phase was acid dissolved,
neutralised, and reacted to make zeolite LTA. However, there was no discussion of the potential
problem relating to the formation of sodium chloride during the NaOH neutralization step.
X. Wang et al. (2021) described the need to value add aluminosilicate-based lithium slag produced
during the extraction of lithium from hard rock ore bodies. Notably, for every tonne of lithium
carbonate made, eight to ten tonnes of waste were created. These authors suggested a strategy
wherein lithium slag was hydrothermally treated at temperatures in the range 220 to 240 oC to produce
a solid hydroxycancrinite and a silicate rich mother liquor. The hydroxycancrinite was subsequently
reacted at elevated temperatures with nitric acid solution to make kaolinite. In addition, the mother
liquor was reacted at 260 oC with calcium oxide to form xonotlite (6CaO⋅6SiO2⋅H2O). The question
thus arose whether the outlined approach for recovering valuable materials from lithium slag
treatment could be transferred and improved for upgrading of natural zeolite waste powder.
`
In terms of material composition, the lithium slag was characterized by a SiO2/Al2O3 ratio = 4.26 (X.
Wang et al., 2021), while natural zeolite has a SiO 2/Al2O3 ratio up to 9.88 (Wruck et al., 2021).
Moreover, natural zeolites invariably comprise of a range of phases such as mordenite, quartz,
clinoptilolite, stilbite, sanidine, and heulandite, and impurities such as iron, calcium, potassium, and
magnesium (Wruck et al., 2021; Zijun et al., 2021).
To avoid the formation of sodium chloride contamination in the mother liquor it was postulated that
instead of acid dissolving the cancrinite, the cancrinite would be better used as a support for an active
coating. A major environmental problem is the presence of excess amounts of phosphates in water
and wastewater (Hinesly & Jones, 1990; Kassem et al., 2022). Instead of depleting phosphate rock
deposits, the removal and recovery of phosphate species from wastewater also offers the advantage
of sustainability. (T. Zhang et al., 2010). Commercially lanthanum coated bentonite has been
employed to control the phosphate species in lakes (Y. Han et al., 2022; Waajen et al., 2016).
Notably, lanthanum has a strong affinity for phosphate species (S. Dong et al., 2017). There are
successful studies showing the efficiency of the coated materials with lanthanum to remove
phosphates, for instance J. He et al. (2015) coated nanorods with lanthanum as an antimicrobia l
solution for drinking water security. Whereas,. L. Zhang et al. (2011), coated activated carbon fibres
with lanthanum oxide and obtained 97.6 % phosphate removal.
Therefore, the aim of this study was to activate natural zeolite powder at relatively low temperatures
to form cancrinite and highly alkaline, silica rich, mother liquor. Value adding of cancrinite by
coating with lanthanum species was targeted for phosphate removal from wastewater. In turn, zeolite
LTA synthesis from mother liquor made use of excess silicates and alkali such as NaOH plus the
addition of sodium aluminate. The hypothesis was that if natural zeolite powder can be activated to
`
form cancrinite and mother liquor then two valuable products can be made for agricultural purposes
and the synthetic zeolite market. Research questions addressed included: (1) What are the preferred
conditions for natural zeolite activation? (2) How to minimize the amount of cancrinite present and
maximise zeolite LTA? (3) What is the composition of the mother liquor and is the presence of
impurities reduced? (4) Does the reaction time significantly influence zeolite LTA formation? and
(5) What is the performance of lanthanum doped cancrinite for phosphate removal from aqueous
solutions? The basic methodology involved bench scale hydrothermal synthesis of cancrinite from
natural zeolite powder.
`
Natural Zeolite and Chemicals

Natural zeolite was supplied by Zeolite Australia with a particle size of 7.16 μm. The elemental
composition as inferred by X-ray Fluorescence indicated that the Si/Al ratio was greater than 4.
Table 7: XRF analysis of natural zeolite powder

Mass % (Dry Basis)
Oxide Natural Zeolite Oxide Natural Zeolite
Na2O 1.49 Mn2O3 0.12
Al2O3 12.54 Fe2O3 1.98
SiO2 71.08 NiO 0.01
MgO 0.58 SrO 0.03
P 2O 5 0.06 ZrO2 0.04
SO3 0.04 BaO 0.04
K2O 1.75 HfO2 0.01
CaO 3.32 PbO 0.05
TiO2 0.21 Sum 99.89
Quantitative X-ray diffraction (XRD) analysis indicated the presence of 14.0 wt% quartz, 1.9 wt%
cancrinite, 11.3 wt% sanidine, 41.1 wt% heulandite, 11.0 wt% mordenite, and 20.7 wt% non-
diffracting/amorphous material. Sodium aluminate (NaAlO 2) and lanthanum chloride hexahydrate
(LaCl3.6H2O) were purchased from Sigma-Aldrich and sodium hydroxide (NaOH; extra pure micro-
pearls) was procured as an analytical reagent (AR) grade from ChemSupply.
`
Transformation of Natural Zeolites to Synthetic Zeolites
Natural Zeolite Activation
In the activation stage, 600 g of natural zeolite powder was initially mixed with NaOH (1.917 g
NaOH/g natural zeolite) and deionized water to control sodium hydroxide molarity. The mixture was
then placed in a PTFE lined 1000 mL acid digestion vessel (Amar Equipment, India) at 240 ℃ for
one hour. After the activation period two products were separated from using an Allegra X-30
centrifuge: solid product (hydroxycancrinite) and supernatant (mother liquor rich in active silicate
species and sodium hydroxide).
Zeolite LTA Synthesis from Mother Liquor

A SiO2/Al2O3 ratio = 2 was achieved by adding extra NaAlO 2 solution along with sufficient water to
adjust the sodium hydroxide molarity to 4 M. This mixture produced aluminosilicate gels that were
placed in sealed containers in a New Brunswick Innova 42R Incubator at 80 ℃ for four hours and
100 rpm. When the zeolite synthesis was completed, the final product was centrifuged to recover the
zeolite slurry. Then, the “wet cake” was washed with deionized water to reduce pH from 14 to 11.
(30 mL of deionized water was used every cycle). After the preferred pH was reached, the zeolite
slurry was weighed, and dried in an oven at 105 ℃ overnight.
Cancrinite Coating with Lanthanum

Cancrinite (1 g) was accurately weighed into a 50 mL centrifuge tube and mixed with 4 mL of a
lanthanum chloride (LaCl3.6H2O) solution which had a molarity of 1, 2, and 3 M. The solution was
agitated for 24 hours on a rotary stirrer wheel. The mixture was then centrifuged, and the supernatant
collected, solid washed with deionised water, and dried in an oven at 105 °C overnight. The overall
transformation of natural zeolite to zeolite LTA/lanthanum loaded cancrinite is shown in Figure 17.
`
Figure 17: Concept for transformation of natural zeolite powder to synthetic zeolite LTA and
lanthanum coated cancrinite.
Phosphate Sorption Isotherms on Modified Cancrinite

Samples of modified cancrinite with masses between 0.1 and 2.5 g were added to twelve 250 mL
Nalgene bottles along with a 200 mL aqueous solution of anhydrous sodium phosphate dibasic
(Na2HPO4) at 100 mg/L phosphate concentration. The samples were then placed in a Innova 42R,
New Brunswick Scientific shaking incubator at 25℃ and agitated at 150 RPM. The samples were
stirred for 24 hours to guarantee that equilibrium was obtained. The samples were filtered through a
syringe filter and diluted to 1:10 with Milli-Q water to analyse the solution. All the samples were
completed in duplicates to ensure the accuracy of the data.
The equilibrium isotherms for phosphate sorption on lanthanum modified cancrinite were modelled
using the Langmuir, Freundlich, and Aranovich-Donohue models.
`
The Langmuir equation, where: Csolution is the dissolved K concentration in soil solution (mgKL -
1), Csolid is the soil sorbed K concentration (mgKkg-1), km is the K adsorption maximum (mgKkg-
1) and kα is the affinity constant (LmgK -1) (C. Wang et al., 2017)
∁ 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 𝟏 ∁ 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
= +
∁ 𝒔𝒐𝒍𝒊𝒅 𝐤𝐦 ∗ 𝐤𝛂 𝒌𝒎
Equation 7. Langmuir equation
The Freundlich equation, where kf is the Freundlich constant (mgKkg-1) and C solid and C solution
were defined earlier (C. Wang et al., 2017)
𝑪𝒔𝒐𝒍𝒊𝒅 = 𝒌𝒇 ∗ 𝑪 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏𝟏/𝒏
Equation 8. Freundlich equation
The Aranovich-Donohue equation, where q is the adsorbed concentration, c is the aqueous
concentration, km and kα are the Langimuir constants and Ka and nA are fitting parameters (Chu &
Hashim, 2023)
𝒌𝒎 ∗ 𝒌𝜶
𝒒=
(𝟏 + 𝒌𝜶)(𝟏 − 𝒌𝑨𝒄) 𝒏𝑨
Equation 9. Aranovich-Donohue equation
Solution Analysis
Inductively Coupled Plasma - Optical Emission Spectroscopy (ICP-OES)

A Perkin Elmer Optima 8300 DV ICP-OES spectrometer was used to determine the composition of
dissolved ions in the mother liquor (especially Si, Al, and Na). Before the analysis, the samples were
Chapter 4: Transformation of natural zeolite powder to synthetic zeolite LTA for water s oftening and lanthanum coated
`
filtered through a syringe filter and diluted to 1:100 and 1:1000 with 2% nitric acid (diluent) using a
Hamilton auto-diluter.
Ion Chromatography (IC)

A Dionex ICS-2100 integrated ion chromatography system was used to complete phosphate
quantification. The system was equipped with a conductivity detector and a potassium hydroxide
eluent generator. The conditions for the suppressed ion chromatographic method were eluent
strength of 28.00 mM KOH, flow rate of 1.00 mL/min, injection volume of 25.00 ml, column
temperature of 30 °C, cell temperature of 35 °C, elution time of 10 minutes and operating pressure
of 2000 psi. Multi-element standards were prepared in-house to calibrate this method. Samples were
diluted with Milli-Q water and syringe filtered prior to analysis.

Powder X-ray diffraction patterns were collected using a PANalytical X’PertPro powder
diffractometer. The internal standard used to identify the crystalline phases in the solid products
consisted of corundum. Typically, the zeolite samples were mixed with 10 wt% corundum standard
powder (Al2O3). The samples (1.8 g) and standard (0.2 g) were micronized for five minutes in a
McCrone micronizing mill with 15 mL ethanol; and dried in an oven at 40 ℃ for four hours. Dried
samples were back pressed into sample holders. To identify the material phases JEdit software and
TOPAS were used. The reference patterns for zeolite LTA were obtained from Breck et al. (Breck
et al., 1956) and atomic parameters were cross-referenced from PDF entry 04-016-9920.
`
The PANalytical Wide Ranging Oxide Calibration (WROXI) method was used to determine the
elemental quantification of the solid products. Solid samples (1 g) were mixed with lithium
tetraborate: lithium metaborate (50:50) with 0.05 % li-Iodate (9 g) and heated at 1050 ℃ to form a
fused glass disc.

The morphology of the samples was observed using a JEOL 7001F Scanning Electron Microscope.
The accelerating voltage employed was 5 kV, with a probe current of 8 A at a magnification between
4,000 and 10,000 x. Each sample was prepared on carbon stamps and coated with five nm of platinum
prior to observation to reduce charging across the surface.
`
Hydrothermal Activation of Natural Zeolite Powder

The first stage determined the impact of the sodium hydroxide molarity upon cancrinite
formation. Tests were conducted at a reaction temperature of 240 ℃ and one hour synthesis
time. The starting mixture was described by a SiO 2/Al2O3 ratio = 9.59, and Na 2O/SiO2 ratio
=1.33. The NaOH molarity ranged from 10 M (H 2O/Na2O=21.17), 8 M (H2O/Na2O=25.40), 6
M (H2O/Na2O=32.45), 5 M (H2O/Na2O=38.08) and 4 M (H2O/Na2O=46.54). The amount of
active Si species in solution was dependent upon the NaOH molarity. Alkaline solutions
increase the solubility of silicate minerals and these can form soluble complexes such as silicate
ions (SiO32-), leading to greater silicon dissolution. This phenomenon is a result of enhanced
mineral solubility and complex formation in alkaline conditions (D’Elia et al., 2018).
The highest amount of Si species (73 % of total Si present) in the mother liquor was found
when using 6 M NaOH Figure 2. Whereas higher molarities such as 10 M NaOH contained
substantially less active Si species (35 %). Y. Liu et al. (2021) also concluded that the preferred
molarity of the NaOH solution was 6 M when using microwave heating to convert potassic
rocks to cancrinite. However, in this example a reaction time of two hours at 200 oC was
recommended.
Chapter 4: T ransformation of natural zeolite powder to synthetic zeolite LT A for water softening and lanthanum coated
cancrinite for phosphate removal
81
Figure 18. Active Si in the mother liquor (%) and solids recovery (g) at different NaOH
molarities
Quantitative XRD was used to elucidate the dependence of NaOH molarity upon creation of
active Si species in solution (Table 8).
82
Table 8. Solid materials obtained after natural zeolite powder activation at 240 oC and one hour synthesis.
Quantitative XRD Analysis (wt %)

NaOH
Molarity Solid (g) Quartz Cancrinite Sanidine Heulandite Mordenite Amorphous
(M)
10 41.3 10.26 10.26 6.58 0.00 0.10 72.81
8 30.8 12.63 7.95 9.66 2.59 0.00 66.04
6 16.7 0.46 71.10 1.03 0.53 0.06 26.82
5 27.1 0.45 74.17 0.30 1.21 1.54 22.34
4 14.6 0.43 51.49 0.00 1.30 2.08 44.70
Chapter 4: T ransformation of natural zeolite powder to synthetic zeolite LT A for water softening and lanthanum coated cancrinite for phosphate removal 83
After the activation process it was apparent that the mass of solid collected was highest when
cancrinite formation was not favoured (8 and 10 M NaOH). Indeed, the smallest quantity of
solid was obtained when using 6 M NaOH (16.7 g). When using 8 and 10 M NaOH solutions
the solid was comprised of relatively small amounts of cancrinite (7.95 and 10.26 wt%,
respectively) and comparably large amounts of quartz (12.63 & 10.26, respectively), sanidine
(9.66 and 6.58 wt%, respectively), and non-diffracting material (66.04 and 72.81 wt%,
respectively).
Further analysis of the solid products shown in Table 8 was completed using SEM (Figure 19).
Activation of the natural zeolite powder with 6 M NaOH solution promoted growth of
cancrinite crystals as evidenced by the characteristic rod-like shape ( Buhl & Petrov, 2021). In
contrast, activation with 10 M solutions produced material which was more heterogeneous in
appearance, decorated with small amounts of cancrinite, and exhibited ill-defined elongated
plate like materials.
Activation with 6 M NaOH Activation with 10 M NaOH
Figure 19: SEM images of solids formed after natural zeolite activation using 6 M and 10 M
NaOH: reaction temperature = 240 oC; reaction time = 1 h; 10,000x magnification.
84
According to Hermeler et al. (1991) increasing the NaOH concentration produced an
intermediate phase besides cancrinite and sodalite. This intermediate phase was described as
cubic natrodavyne ( Buhl, 1991; Hermeler et al., 1991). The difference between cancrinite and
this intermediate compound is the crystal structure, while cancrinite exhibits a 3-dimensiona l
framework this new compound shows one-dimensional positional disorder. The results also
agreed with previous studies that transformed aluminosilicate waste materials (coal fly ash,
kaolin, and raw muscovite) to higher value products, where cancrinite was reported to form at
temperatures higher than 200 ℃ (Mahima, et al., 2020; Murukutti & Jena, 2022; Selim et al.,
2018; Wernert et al., 2020). Furthermore, Hackbarth et al. (1999), reported that to avoid the
formation of by-products (especially sodalite) during cancrinite synthesis the temperature
should not remain below 200 ℃.
Stability of Mother Liquor Solution

The previous section described how to activate natural zeolite to make in addition to solid
material a solution comprising of sodium hydroxide and dissolved silica species (mother
liquor). For practical purposes it is necessary to understand if the mother liquor is stable or
not. Depending upon the answer, either fresh mother liquor had to be made for each experiment
or larger volumes could be stored and used as required. Therefore, mother liquor was stored
in polypropylene bottles and preserved in a fridge for a period up to 25 days (Table 9).
Importantly, the solutions, whether at 4 or 5 M NaOH, displayed a remarkable degree of
stability with no evidence to indicate formation of precipitates. This observation was consistent
with high pH values between 13 and 14 which preserved the dissolved silicates in the mother
liquor (Krauskopf, 1956).
85
Table 9. Mother liquor composition as a function of storage time and NaOH molarity: natural
zeolite activation at 240 oC for 1 h.
4M NaOH 5 M NaOH
SAMPLE COLLECTION
Al (g) Si (g) Na (g) Al (g) Si (g) Na (g)
Activation (Day 0) 0.06 10.80 50.42 0.06 10.96 48.25
Day 3 0.06 11.12 50.36 0.06 11.27 47.89
Day 4 0.06 11.14 48.94 0.06 11.53 45.61
Day 11 0.06 11.00 47.76 0.06 11.51 44.95
Day 18 0.06 11.04 47.52 0.06 11.53 46.33
Day 25 0.06 10.90 46.78 0.06 11.27 44.76
Mass Balance for Synthesis of Zeolite LTA from Natural Zeolite Powder
Examination of the mass balance for the transformation of natural zeolite powder to zeolite
LTA was completed to understand the chemistry and process engineering involved (Figure 20).
Overall, a mass balance was recorded with: Si in and Si out 18.9 g; Al in and Al out 3.9 g; Na
in and Na out 66.8 g, and water in and water out 528 g. After the activation stage, it was evident
that the highest amount of dissolved Si species was in the mother liquor (13.90 g, which was
74 % of the total Si present). In contrast, only a minor amount of Al ions was present in the
mother liquor (0.09 g). The molar ratios for the activation parameters were: SiO2/Al2O3 = 9.31;
Na2O/SiO2 = 2.16; and H2O/Na2O = 20.19. Hydrothermal activation at 240 oC for one hour at
100 rpm produced 72.91 g of zeolite slurry. After drying the slurry, the final product was a
solid with 71.10 wt% cancrinite crystals. The first washing step of the zeolite slurry contained
1.84 g Si and 1.64 g Al (which can be reused in the next activation batch).
86
Zeolite LTA synthesis conditions were: SiO2/Al2O3 = 2.81; Na2O/SiO2 = 4.94; and H2O/Na2O
= 14.59. Reaction temperature was 80 oC and reaction time was four hours. Then the conditions
for zeolite LTA were adjusted by adding extra sodium aluminate (28.60 g) and water (282.50
g) to reduce NaOH molarity. After the synthesis the mass balance showed that the amount of
aluminium in the process was not enough to complete the zeolite synthesis since the excess of
Si in the supernatant was 6.93 g and 2.91 g Al.
87
Figure 20. Mass balance for activation of natural zeolite powder using 6 M NaOH at 240 oC for one hour followed by hydrothermal synthesis of
zeolite LTA at 80 oC for 4 h
Chapter 4: T ransformation of natural zeolite powder to synthetic zeolite LT A for water softening and lanthanum coated cancrinite for phosphate removal 88
Table 10 shows the XRF analysis of the cancrinite after the hydrothermal activation at 240 oC and
one hour. The results showed that most natural zeolite impurities remained in the solid product
(cancrinite) after the activation stage.
Table 10: XRF analysis of solid product from activation of natural zeolite with 6 M NaOH at 240 oC
for one hour
Oxide Mass % (Dry Basis) Oxide Mass % (Dry Basis)
Na2O 19.88 Mn2O3 0.01
Al2O3 24.56 Fe2O3 0.00
SiO2 40.47 NiO 0.00
MgO 0.58 SrO 0.02
P 2O5 0.06 ZrO2 0.04
SO3 0.04 BaO 0.04
K2O 0.18 HfO2 0.01
CaO 3.30 PbO 0.03
TiO2 0.16 Sum 100
Zeolite LTA Synthesis from Mother Liquor
The synthesis recipe was SiO2/Al2O3 = 2.81; Na2O/SiO2 = 4.94; and H2O/Na2O = 14.59. The reaction
temperature was 80 oC and the sample was agitated at 150 rpm. Figure 21 indicates that the zeolite
LTA cubic crystals were not prevalent in the SEM images recorded for the sample which was reacted
for two hours. Indeed, the presence of a more disordered phase was noted. In contrast, extending
the reaction time to three hours promoted the formation of zeolite LTA as evidenced by the more
well-defined zeolite LTA material. The quantitative XRD data in Table 11 supports the conclusions
from inspection of the SEM images in Figure 21.
Chapter 4: T ransformation of natural zeolite powder to synthetic zeolite LT A for water softening and lanthanum coated cancrinite
for phosphate removal 89
After two hours, less than half of the material was transformed into zeolite LTA (47.4 wt%).
However, increasing the reaction time to three hours resulted in almost double the amount of zeolite
shown at two hours (83.8 wt%). It was also noted that further increasing the time did not present any
extra benefits as the amount of material and the crystalline % stayed stable for up to five hours.
Synthesis time: 2h Synthesis time: 3h

Figure 21: Influence of synthesis time upon zeolite LTA synthesis: 80 oC, 150 rpm and
SiO2/Al2O3=2.81
Table 11. XRD determination of percentage of crystalline zeolite LTA in solid product as a function
of synthesis time: reaction temperature 80 ◦C; SiO 2/Al2O3 = 2
SYNTHESIS XRD ANALYSIS
Zeolite Zeolite
Time Dry Quartz Cancrinite Sodalite
LTA g /g LTA Amorphous%
(hrs) solid (g) wt% wt% wt%
NZ wt%
2 30.90 0.52 0.15 0.00 0.04 47.42 52.39
3 43.40 0.72 0.30 0.00 0.01 83.84 15.85
4 42.95 0.72 0.32 0.00 0.00 82.88 16.81
5 43.60 0.73 0.03 0.00 0.00 80.87 18.80
Table 12 shows the XRF analysis of the natural zeolite powder and how the impurities have moved
after the activation stage to the cancrinite material while the zeolite LTA synthetized from the mother
liqueur (after activation) was relatively pure: K 2O=0.28%; TiO2=0.05%, Mn2O3=0.05% ;
Fe2O3=0.22% and PbO=0.02%.
Table 12. XRF analysis of zeolite LTA made from natural zeolite powder.
Mass % (Dry Basis)
Oxide Zeolite LTA Oxide Zeolite LTA
Na2O 17.60 Mn2O3 0.05
Al2O3 28.55 Fe2O3 0.22
SiO2 34.19 NiO 0.00
MgO 0.00 SrO 0.00
P 2O 5 0.00 ZrO2 0.00
SO3 0.00 BaO 0.00
K2O 0.28 HfO2 0.00
CaO 0.00 PbO 0.02
TiO2 0.05 Sum 101.7
Influence of SiO 2/Al2O3 Molar Ratio upon Zeolite LTA Synthesis

Table 11 indicates that the wt% zeolite made was ≤83.8 wt%. Therefore, the challenge was to increase
the amount of zeolite LTA formed. Reducing the SiO2/Al2O3 ratio to slightly less than two should
drive the zeolite LTA formation due to the excess of aluminium present compared to stoichiometric
values (Rozhkovskaya et al., 2021). Figure 22: Zeolite LTA SiO2/Al2O3=1.90; Na2O/SiO2=5.11;
H2O/Na2O= 4.82, 4-hour synthesis and 80 oC represents the SEM image of a zeolite LTA made with
SiO2/Al2O3 = 1.90; Na2O/SiO2 = 5.11; H2O/Na2O = 14.82; four hours synthesis 80oC and 150 rpm.
Figure 22: Zeolite LTA SiO2/Al2O3=1.90; Na2O/SiO2=5.11; H2O/Na2O= 4.82, 4-hour synthesis and
80 oC
The SEM images suggested that an abundance of zeolite LTA was produced. This finding was
consistent with the XRD analysis which showed that the sample was now composed of 95.5 wt%
zeolite LTA, with only 0.28 wt% cancrinite, 0.04 wt% sodalite, 0.03 wt% quartz. and 4.11 wt%
amorphous content. For every 60 g of natural zeolite, 62.85 g of zeolite LTA was produced.
Phosphate Sorption on Cancrinite
Synthesis of Lanthanum Doped Cancrinite

The wet impregnation route was chosen to contact aqueous solutions of lanthanum chloride with the
cancrinite sample. The molarity of La 3+ ions was adjusted in the range 1 to 3 M at a constant solution
volume of 4 mL. The wt% of lanthanum on the cancrinite was determined to be 5.25 ± 0.15, 6.5 ±
0.3 and 11 ± 0.8 for initial lanthanum molarities of 1, 2 & 4, respectively.
Sorption Equilibrium Isotherms of Phosphate on Lanthanum Modified Cancrinite
The sorption capacity of cancrinite and cancrinite coated with lanthanum were investigated using
solutions comprised of 126 mg/L of phosphate species at 30 oC. When no coating was present on the
cancrinite material the uptake of phosphate ions from solution was zero. . Xiaotian et al., (2022)
reported that phosphate sorption on cancrinite present in red mud waste from bauxite refining is
relatively low. Indeed, increasing the cancrinite surface wettability was beneficial to enhancing
phosphate species uptake. In contrast, introduction of a lanthanum coating promoted phosphate
uptake (Figure 23). The most used isotherm models (Langmuir and Freundlich) did not satisfactorily
fit the recorded equilibrium data as the sum of errors squared (ERRSQ) value was 372 and 406,
respectively. A superior data fit was obtained when the Aranovich Donohue model was used
(ERRSQ = 74). This finding suggested that more than one sorption site for phosphate species on
lanthanum modified cancrinite is available (Millar, Couperthwaite et al., 2017). A recent study by
Y. Yang et al. (2021) supports this view as data was acquired which indicated that both monolayer
and multi-layer sorption processes occurred when using lanthanum doped ZSM-5 zeolite to
selectively recover phosphate from wastewater. For the Aranovich Donohue model the maximum
loading of phosphate species was predicted to be 19.8 mg/g of coated cancrinite, the “n” value was
0.12 and the Langmuir equilibrium coefficient (K L) was 3.23 L/mg.
Figure 23: Equilibrium isotherms for phosphate sorption on lanthanum modified cancrinite:
Langmuir (top), Freundlich (middle) and Aranovich-Donohue models (bottom)
The solutions after the equilibration process were also analysed for the presence of lanthanum ions
in the supernatant (Figure 24). For all the samples no lanthanum species were recorded which
suggested that the coatings were relatively stable. However, there was a linear trend in increasing
sodium ions in solution as a function of greater solid mass used in the isotherm tests. In addition,
smaller amounts of silicon species were steadily released until 1.5 g of cancrinite sorbent was added.
Higher solid mass content resulted in the gradual decrease in silicates emitted into solution.
Figure 24: Release of ions into solution as a function of from cancrinite mass during phosphate
equilibrium tests
Conclusions
This study successfully converted natural zeolite waste powder into two products which potentially
represent higher value; zeolite LTA and lanthanum loaded cancrinite. Activation of the natural
zeolite was achieved at relatively mild conditions. Additionally, the molarity of the NaOH used was
critical to produce the greatest amount of zeolite LTA. Employment of high pH solutions promoted
the deposition of precipitates in the cancrinite phase.
As the mother liquor from cancrinite formation was relatively pure, the quality of the zeolite LTA
produced from hydrothermal synthesis was increased. This discovery solved previous issues where
the removal of impurities was challenging, such as when acid washing is applied. The new approach
outlined also avoided problems in previous approaches wherein acid was used to dissolve cancrinite
as this resulted in a sodium chloride waste stream.
Cancrinite as a waste product causes problems of sustainability and economic viability. Thus, doping
of the cancrinite powder was chosen as it was useful for removing phosphate species from water and
wastewater resources. The initial performance of the cancrinite based sorbent was acceptable and
worthy of future studies to enhance the physical properties of the sorbent material. Expansion of the
zeolite manufacturing process to other high silica content waste resources is also suggested.
Key Insights
This chapter has successfully converted natural zeolite waste powder into two higher value products:
zeolite LTA and lanthanum-loaded cancrinite. The quality of the zeolite LTA produced through
hydrothermal synthesis was improved by obtaining relatively pure mother liquor from the activation
of the waste material. This discovery has addressed previous challenges by avoiding the use of
hydrochloric acid, which produced a non-sustainable and economically unviable sodium chloride
waste stream. Doping of the cancrinite powder was found to be useful in removing phosphate species
from water and wastewater resources. The initial performance of the cancrinite-based sorbent was
promising, and future studies aimed at enhancing the physical properties of the sorbent material are
suggested. The expansion of the zeolite manufacturing process to other high silica content waste
resources is also recommended. However, the efficiency of this method is limited to high silica
materials, and the process can be more complex than other methods, making it challenging to
implement on an industrial scale.
Therefore, the next chapter will focus on developing a simpler method to activate aluminosilicate
waste material that has the potential to be scaled up for industry. The next method needs to adjust the
reaction conditions to prevent the formation of cancrinite, potentially simplifying the process and
reducing the production of waste materials. Additionally, the new method has identified specific
optimal conditions for activation, including NaOH molarity, activation temperature, and quenching
time. This level of control has the potential to lead to more consistent and reproducible results, which
are essential for industrial-scale production.
Chapter 5: “One Pot” Synthesis of Zeolites: Activation of Spodumene
Leachate Residue using a New Quench Method
Abstract
Increasing demand for lithium has also increased the production of waste materials. The
aluminosilicate-based waste product from hard rock refining is generically termed “lithium
slag” or spodumene leachate residue (SLR) if spodumene was the mineral source. The
hypothesis was that if an economical approach was devised for the synthesis of zeolites from
waste or natural aluminosilicates then uptake of “green” zeolites by industry may be
accelerated. This study has successfully addressed the optimization of SLR activation and
zeolite LTA synthesis from the activated material using a novel one-pot process, named the
“Quench Method”. The activation of SLR was completed as a function of temperature (25 to
150◦ C), sodium hydroxide concentration (2 to 14 M), and time (10 to 1440 min) where 100◦ C,
10M NaOH and 60 minutes contact time were the preferred conditions. After activation, the
sodium hydroxide molarity and Si/Al ratio were adjusted for optimal zeolite synthesis
conditions. Si/Al ratio of 0.95 at 80◦ C and four hours synthesis resulted in 56 wt% Crystalline
zeolite LTA, although Si/Al ratio of 0.85 at 80◦ C and three hours resulted in a similar amount
of crystalline zeolite LTA (52 wt%) proving that the synthesis was improved by adding an
excess of aluminium in the solution. This study successfully validated the concept of using a
quench method to initially activate waste aluminosilicate materials (such as SLR) and then
adjust reaction conditions to form valuable zeolite products such as zeolite LTA. Future studies
should focus on the development of continuous hydrothermal reactors which can more rapidly
decrease the reaction temperature and molarity to improve control of the zeolite LTA synthesis.
Key Words: spodumene leachate residue; zeolite; activation; lithium; slag
Chapter 5: “One Pot” Synthesis of Zeolites: Activation of Spodumene Leachate Residue using a Ne w Quench
Method 98
Introduction
Lithium and its compounds have been historically used in diverse application such as batteries,
lubricating greases, pharmaceuticals, glass, ceramics, and metallurgy (Choubey et al., 2016;
Collins et al., 2020; G. Han et al., 2018; Z. Liu, Zhu et al., 2019; P. Meshram et al., 2014; Sun
et al., 2014). For example, high-capacity lithium batteries are already prevalent in mobile
devices and are strong candidates for renewable energy storage ( Flexer et al., 2018).
Substantial growth of lithium battery use is expected as demand for electric vehicles increases
(Setoudeh et al., 2020). Lithium is mainly extracted from hard rock ores (lithium minerals such
as spodumene, petalite and lepidolite) (G. Han et al., 2018) and aqueous resources such as
lithium rich brines or salt lakes ( Flexer et al., 2018). At present, the majority of lithium
production around the world belongs to: six mineral operations in Australia, two brine
operations each in Argentina and Chile, and one brine and one mineral operation in China
(USGS, 2020). Indeed, Australia is currently the world’s largest producer of lithium ( Flexer
et al., 2018; Vikström et al., 2013). Spodumene is the favoured resource for processing into
lithium, as lepidolite and petalite typically contain a high fluoride content High fluoride content
in lepidolite and petalite increases operational costs, poses environmental challenges, and limits
market demand, affecting the profitability of lithium processing. (Vikström et al., 2013).
With increasing demand for lithium there is also increased production of waste materials. The
aluminosilicate based waste product from hard rock refining is generically termed “lithium
slag” or spodumene leachate residue (SLR) if spodumene was the mineral source (Zampori et
al., 2012). SLR is the solid waste formed after: (1) heat treatment at high temperatures to
transform α spodumene to the more active ß spodumene; and (2) leaching with sulfuric acid to
recover lithium ions.
Chapter 5: “One Pot” Synthesis of Zeolites: Activation of Spodumene Leachate Residue using a New Quench
Method 99
The general formula for SLR is HAlSi2O6 and as this material is commonly stored outdoors
there is a possibility of environmental damage due to its high alkalinity and potential for
leaching of heavy metals into the surrounding soil and water sources. It may also take up
valuable land space and contribute to visual pollution (D. Chen et al., 2012). Consequently,
SLR has been used as cement clinker in concrete, as a raw material for ceramic glazed tiles ,
and in activated clays (G. Han et al., 2018). However, the utilisation rate is only about 10 %
(Beushausen et al., 2012) which means there is a clear need to discover alternate uses for SLR.
Use of SLR to make synthetic zeolites is one possible avenue of research as this approach
makes use of the high aluminosilicate content of SLR. Zeolites are typically microporous or
mesoporous with the general composition: Mx/n (AlO2) x (SiO2) y ∙ zH2O where M is the cation
that compensates the negatively charged framework, n is the cation valency, y/x is the Si/Al
ratio, and z is the water content. Zeolite A or LTA is the zeolite used primarily by industry on
a mass basis (making up 73 % of global production (Ayele et al., 2016a)) due primarily to its
use in laundry detergents as a water softener (S. U. Meshram et al., 2014).
The concept of transforming waste and naturally occurring aluminosilicates into higher value
products such as zeolites has been studied in recent years in relation to the development of
green synthesis methods (H. Liu et al., 2014; Pan et al., 2019). Notably, due to the poor
reactivity of waste or natural aluminosilicates an additional activation stage is commonly
applied. For example, thermal treatment of SLR has been studied in relation to construction
industry utilisation (Z. Liu et al., 2019). It was discovered that the amorphous content increased
from ca. 17 to 51 % upon heating at 700 oC for two hours. Whereas,. Zhuang, et al. (2014)
reported that hydroxide dissolution followed by hydrothermal synthesis produced a zeolite
Method 100
LTA/Faujasite mixture from lithium slag. Lin et al. (2015) added that it was necessary to
recycle the waste solution (“mother liquor”) when synthesising zeolites from lithium slag due
to economic considerations. Fusion pre-treatment of aluminosilicate waste materials to
activate the silica and alumina species is commonly used. The basic idea is to heat a mixture
of waste and sodium hydroxide at temperatures above the melting point of NaOH for several
hours. Hence, D. Chen et al. (2012) fused lithium slag with sodium hydroxide at 600 oC for
four hours and then aged and hydrothermally reacted the resultant solid at 95 oC for eight hours
to make zeolites.
The need for activation of waste materials appears to be a key difference compared to
commercial zeolite synthesis wherein aluminosilicate gels are created from soluble silicates
and aluminates. Therefore, efforts have focussed on developing low cost means of activating
waste and natural aluminosilicates. Fusion with NaOH is viewed as too expensive to be
relevant to industry (Ojumu et al., 2016). Consequently, a novel process was developed, which
involved the activation of rectorite and kaolin clay through a method known as “High
Concentration Alkali Solution” (HCAS) (T. Li et al., 2012; H. Liu et al., 2015; Yue et al.,
2014; Yue et al., 2015). The basis of this approach was hydrothermal reaction of the clay with
high molarity (ca. 15 M) NaOH solutions at temperatures of 200 oC or higher. The resultant
solid was then separated from the solution and reacted under appropriate conditions to make
zeolites such as LTA, ZSM-5 and USY. The critical insight was that a depolymerizat ion-
polymerisation strategy was necessary to make quality zeolites.
H. Liu et al. (2019) compared thermal, alkali fusion and HCAS activated rectorite upon the
synthesis of Ti-ZSM-5 zeolite. It was found that titanium species were partially incorporated
Method 101
in the lattice framework of the zeolite when employing the alkali fusion or HCAS methods
whereas with thermal activation only extra-framework titania was recorded. Consequently, the
catalytic activity of the titanium incorporated ZSM-5 was greater for 1-octene
hydroisomerization and aromatization.
Miao et al. (2016) described the transformation of potassic rocks to low sodium zeolite X
(LSX) using the sub-molten salt approach. A mixture of powdered potassic rock, potassium
hydroxide, and water was heated with agitation in the temperature range 180 and 200 °C for
up to seven hours. The mass concentration of KOH was critical, with a value of 75 %
recommended, as the resultant product exhibited only peaks in the X-ray diffraction (XRD)
patterns ascribed to potassium hydroxide. J. Yang et al. (2017) more recently described how
to activate kaolin under relatively mild conditions in order to make them amenable for
conversion into zeolite LTA and zeolite Y. These authors indicated that the HCAS method
developed in their research group was not amenable to industry use. Therefore, a new strategy
termed Quasi-Solid Phase Activation Process (QSP) was developed. Initially, kaolin was
kneaded with sodium hydroxide and then a small fraction of water was added. Subsequently,
this material was extruded into shapes 1.5 mm in diameter and 2 to 3 cm in length. The
extrudate was finally heated to the required temperature in a belt type calcination oven. The
principal advantages relative to the HCAS approach were: (1) lower activation temperature;
(2) less water required; (3) continuous processing (as opposed to batch for HCAS); and (4)
reduced energy consumption. Yue et al., 2020) demonstrated that >95 % depolymerisation of
the rectorite was obtained by heating at 170 oC for one hour.
Method 102
Despite the advances in activation approaches it was evident that an ideal ‘One pot’ synthesis
method for waste-to-zeolite synthesis was missing (X. Ji et al., 2018). Consequently, this study
was based upon the innovative idea of initially activating the SLR using a relatively high
concentration of NaOH at a particular temperature for a certain time. Then additional water
was added to rapidly lower the NaOH molarity and control reaction temperature (Figure 25).
Therefore, the aim of this study was to: (1) discover SLR activation conditions which produce
high amounts of active silica and alumina; (2) adjust synthesis conditions by water addition in
order to make crystalline zeolite LTA. The hypothesis was: “If an economical approach to
synthesis of zeolites from waste or natural aluminosilicates then uptake of “green” zeolites by
industry may be accelerated”. Research questions addressed to support the hypothesis
included: (1) Which temperature and molarity of NaOH are preferred for the activation of SLR?
(2) What is the quality and yield of Zeolite LTA from activated SLR? (3) It is possible to
optimize the bench-scale synthesis of zeolite LTA from SLR powder, which was performed,
and extensive characterization of the activated product and zeolite was completed.
Figure 25: Illustration of the “Quench” concept for making zeolite from waste aluminosilicate
materials.
Method 103
Spodumene Leachate Residue & Chemicals

The SLR used for this study came from a lithium mining operation in Western Australia.
Sodium hydroxide (NaOH) (40 wt%) solution, sodium hydroxide extra pure micro-pearls and
hydrochloric acid (32 wt%) were purchased from ChemSupply Australia as analytical reagent
(AR) grade. Sodium aluminate (NaAlO 2) was purchased from Sigma-Aldrich.
Activation of Spodumene Leachate Residue (SLR)

Activating SLR for zeolite synthesis boosts reactivity and removes impurities, preparing SLR
for effective zeolite formation and influencing the quality of the final product. The activation
behaviour of SLR was ascertained as a function of temperature (25 to 150 ℃), sodium
hydroxide concentration (2 to 14 M), and time (10 to 1440 min). Room temperature SLR
dissolution trials involved addition of SLR (1 g) and 5 mL of sodium hydroxide (40% w/v)
solution at the desired molarity into 50 mL centrifuge tubes. This mixture was then activated
on a rotary tube mixer for up to 24 h. Activation at 75 oC was completed using a heating block
(HACH DRB 200), by mixing 1 g of SLR and 5 mL of sodium hydroxide (40% w/v solution)
in 10 mL tubes at the desired molarity. Samples were collected at various intervals from an
activation time of 10 minutes to 24 hours. The 100 ℃ activation tests were similarly completed
using 4 to 10 M NaOH solution which was prepared by addition of 1 g of SLR with 1.92 NaOH
g extra pure micro-pearls and deionised water. At the highest temperature of 150 oC a Teflon
lined Berghof BR100 High Pressure Reactor was utilized for the activation step. In this case,
samples were prepared using 20 g of SLR, 100 mL of sodium hydroxide (40% w/v solution)
and sufficient water to make the desired molarity. Notably, heating the high pressure reactor
to 150 oC took 50 minutes and cooling of the reactor to ambient temperature required another
60 minutes. Hence all reaction times in this vessel were assumed to be timed at 150 oC (and
Method 104
not the total heating time including the ramp up phase). Each test was completed in duplicate
to ensure the veracity of the data. After the end of the activation process the samples were
filtered in order to collect the solid phase and the mother liquor. The supernatant for all samples
were collected and appropriately diluted for analysis using inductively coupled plasma optical
emission spectroscopy (ICP-OES). The solid products from this alkaline activation step were
characterised using XRD analysis.
Determination of active alumina and silica species in the solid product was achieved by acid
dissolution using the methodology described by Wang et al. (J.-Q. Wang et al., 2014). Solid
samples were initially oven dried at 105 oC to reduce the water content then 0.05 g of fused
product was mixed with 5 mL of 2 M HCl in a 50 mL centrifuge tube and agitated on a rotary
wheel for 30 min. The supernatant was subsequently diluted and analysed by ICP -OES. The
total amount of active Si and Al species was a combination of those detected in the solid and
liquid phases (Equation 10 & Equation 11).
𝑨𝒍 𝒊𝒏 𝒔𝒐𝒍𝒊𝒅 (𝒈) +𝑨𝒍 𝒊𝒏 𝒎𝒐𝒕𝒉𝒆𝒓 𝒍𝒊𝒒𝒖𝒐𝒓 (𝒈)

Equation 10: 𝑻𝒐𝒕𝒂𝒍 𝑨𝒄𝒕𝒊𝒗𝒆 𝑨𝒍 (%) = ∗ 𝟏𝟎𝟎
𝑨𝒍 𝒊𝒏 𝑺𝑳𝑹 (𝒈)
𝑺𝒊 𝒊𝒏 𝒔𝒐𝒍𝒊𝒅 ( 𝒈) +𝑺𝒊 𝒊𝒏 𝒎𝒐𝒕𝒉𝒆𝒓 𝒍𝒊𝒒𝒖𝒐𝒓 (𝒈)

Equation 11: 𝑻𝒐𝒕𝒂𝒍 𝑨𝒄𝒕𝒊𝒗𝒆 𝑺𝒊 (%) = ∗ 𝟏𝟎𝟎
𝑺𝒊 𝒊𝒏 𝑺𝑳𝑹 (𝒈)
Method 105
Conversion of Activated Spodumene Leachate Residue to Zeolite LTA
Activation of SLR accompanied by subsequent zeolite synthesis was performed using a
Berghof BR100 High Pressure Reactor at either 100 or 150oC. SLR (10 g), NaOH (19.17 g)
and sufficient deionized water to control molarity (7 or 10 M) was added to the reactor.
The SLR was thus activated as a function of time (1 to 18 hours) at the desired temperature.
After SLR activation was completed the solution/slurry was reduced in both temperature (to
80 oC) and NaOH molarity (3.95 M). One constraint was that the time to reduce reactor
temperature from 100 to 80 ℃ in the same reactor was approximately 40 minutes for each
sample. Temperature was monitored with a thermocouple connected to the reactor panel
controller. Meanwhile a solution of deionized water with NaAlO2 (5.33 g) was prepared to
adjust the molarity of the synthesis and SiO 2/Al2O3 ratios for zeolite LTA. The solution was
heated at 80 ℃ and agitated at 100 rpm in a New Brunswick Innova 42R Incubator for four
hours.
Once the temperature of the solution containing the activated SLR decreased to 80 ℃, the
reactor was opened, and the pre-heated solution of water and sodium aluminate rapidly added
to the slurry. Then the reactor was re-sealed and maintained at 80℃ for the desired synthesis
time while stirring at 100 rpm. After the reaction was completed, the product was separated
by using a centrifuge. The mother liquor was collected and analysed using ICP-OES. The solid
product was washed with deionised water to reduce the pH and remove the free chemicals in
the product. Six washing cycles were completed using 120 mL of water for each cycle. After
the washing step the wet cake was weighed and dried in the oven at 105 °C. Then the dried
powder was characterised using Quantitative X-ray Diffraction (XRD), X-ray Fluorescence
(XRF) and Scanning Electron Microscopy (SEM). Equation 12 shows the stoichiometric
Method 106
reaction to produce zeolite LTA from SLR and sodium aluminate. Hence, the theoretical yield
of zeolite LTA was calculated to be 1.78 kg for every 1 kg of SLR used.
Equation 12: 8 𝑯𝟐 𝑨𝒍 𝟐𝑺𝒊 𝟒.𝟓𝑶𝟏𝟑.𝟎. 𝟓 𝑯𝟐 𝑶 + 𝟐𝟎 𝑵𝒂𝑨𝒍𝑶𝟐 + 𝟑𝟒 𝑯𝟐 𝑶 + 𝟏𝟔 𝑵𝒂𝑶𝑯 →
𝟑 𝑵𝒂𝟏𝟐 𝑨𝒍𝟏𝟐 𝑺𝒊𝟏𝟐 𝑶𝟒𝟖. 𝟏𝟖𝑯𝟐 𝑶
Elemental quantitation of the solid products was carried out using a PANalytical AXIOS 1.5
kW Wavelength Dispersive XRF spectrometer and PANalytical WROXI software application.
Powdered samples were prepared as a fused glass disc with a standard composition of 50:50
lithium tetraborate: lithium metaborate with 0.05 % li-Iodate. Loss of Ignition (LOI) was
determined by heating solid samples at 1050 ˚C for two hours.

Crystalline phases in the solid products were obtained using a PANalytical X’PertPro powder
diffractometer. Powdered zeolite samples were mixed with 10 wt% of corundum standard
(1.800 g (±0.004) and 0.200 g (±0.004), respectively). Samples and standard were micronized
and homogenized with zirconia in a McCrone micronizing mill and dried in an oven for four
hours; prior to creating a pressed powder. To analyse the product phases TOPAS (V6, Bruker)
and JEdit software were used.
Method 107
To observe the shape and size of the zeolite products a JEOL 7001F Scanning Electron
Microscope was used. The samples were prepared on carbon stamps, and then coated in
platinum. The accelerating voltage was 5 kV.
Solution Analysis
The mother liquor and acid dissolution samples were analysed using a Perkin Elmer Optima
8300 DV ICP-OES spectrometer to primarily determine the concentrations of aluminium,
silicon, and sodium. Dilution of the samples was conducted in a Hamilton auto-diluter using
2% nitric acid as diluent.
Method 108
Characterization of Spodumene Leachate Residue

The elemental composition of SLR is displayed in Table 13, as measured by X-ray fluorescence
(XRF).
Table 13. XRF analysis of SLR

SiO2 66.276 P 2O5 0.008

Al2O3 25.005 SO3 1.681
Fe2O3 0.624 Cr2O3 0.05
Na2O 0.118 NiO 0.007
K2O 0.276 ZnO 0.005
MgO 0.127 PbO 0.005
CaO 0.063 BaO 0.006
TiO2 0.019 Mn3O4 0.133
LOI 4.985
From the XRF data it was concluded that the bulk formula for the SLR was 2 H2 Al2 Si4.5 O13.0.5
H2O. Quantitative X-ray Diffraction (XRD) analysis of SLR revealed the sample to be
primarily Hydrogen Aluminium Silicon Oxide and non-diffracting material (Table 13The
slightly higher Si value derived from the XRF data may be related to the presence of quartz.
The small amount of lithium sulfate presumably arose as a residual of the lithium extraction
process using sulfuric acid.
Method 109
Table 14. Quantitative XRD analysis of SLR
Phase SLR delta Wt%
Hydrogen Aluminium Silicon Oxide 31.92
Quartz 3.85
Lithium Sulfate 0.19
Non-diffracting/unidentified 64.04
Sum 100
Scanning Electron Microscopy (SEM) images supported the XRD data in that the material
appeared random in size and shape (Figure 26). In terms of particle size, SLR comprised of
relatively small grains with a particle size range between 0.71 and 48 (µm); with a d50 = 11.9
(µm).
10
8
Volume Density (%)
0
0.01 1 100 10000
Size Classes (μm)
SEM Image Particle Size Distribution
Figure 26: SEM imaging and particle size of SLR
Method 110
Activation of SLR Material
Creation of Active Silica and Alumina Species from SLR

A baseline study was conducted wherein the activation of SLR was completed at ambient
temperature using 2 to 14 M NaOH solutions. In general, increasing the NaOH molarity and
contact time promoted activation of both Si and Al species (Figure 27). This observation
agreed with previously published data relating to dissolution of fly ash (Kuenzel & Ranjbar,
2019). Regarding the active species in the solid phase, the interpretation of the mother liquor
data indicated that 10 and 14 M solutions favoured the activation of SLR. Overall, the
activation process was relatively slow with only 14.2 and 14.74 % of Si and Al activated after
24 hours.
Method 111
Active Si Species in Mother Liquor at 25℃ Active Al Species in Mother Liquor at 25℃
16 16
2M NaOH 2M NaOH
Si Active Species (%)
14
Al Active Species (%)

3M NaOH
14 3M NaOH
12 4M NaOH 4M NaOH
12 10M NaOH
10M NaOH
10 14 M NaOH 10 14M NaOH
8 8
6 6
4 4
2 2
0
0
0 5 10 15 20 25
0 5 10 15 20 25
Activation time (hrs)
Active Si Species in Solid at 25℃ Active Al Species in Solid at 25℃
16 16
Al Active species (%)

14
Si Active species (%)
14
12 12
10 10
8 8
6 6
4 4
10M NaOH 2 10M NaOH
2 14M NaOH 14M NaOH
0
0
0 5 10 15 20 25
0 5 10 15 20 25
Activation Time (hrs)
ActivationTime (hrs)
Figure 27: Active Si and Al species in (a) mother liquor and (b) solid as a function of NaOH
molarity and contact time at 25 oC
Therefore, the activation temperature was raised to 75 ℃; whereupon a substantial increase in
both active Si and Al species was apparent (Figure 28). In general, as the molarity of NaOH
increased from 2 to 14 M the formation of active Si and Al species was not only greater but
also the activation rate was higher. Reaction time had a significant impact when using lower
molarity NaOH solutions but minimal impact when using 10 or 14 M NaOH solutions.
Additionally, it appeared that use of either 10 or 14 M NaOH solutions activated the SLR to
approximately the same extent (ca. 76 and 80 % for Si and Al, respectively).
Method 112
Total Si Active Species Total Al Active Species
100 100

80 80
2M NaOH 2M NaOH
60 3M NaOH 3M NaOH
4M NaOH
60
4M NaOH
10M NaOH 10M NaOH
40 14M NaOH 14M NaOH
40
20 20
0 0
0 5 10 15 20 25 0 5 10 15 20 25
Si Active Species in mother liquor Al Active Species in mother liquor
100 100
2M NaOH
2M NaOH
3M NaOH 3M NaOH
80 4M NaOH 80
4M NaOH
10M NaOH 10M NaOH
14M NaOH
60 60 14M NaOH
40 40
20 20
0 0
0 5 10 15 20 25 0 5 10 15 20 25
Activation time (hrs) Activation time (hrs)

Si Active Species in solid Al Active Species in solid
100 100
2M NaOH
3M NaOH
80 4M NaOH 80
10M NaOH
14M NaOH 2M NaOH
60 60 3M NaOH
4M NaOH
10M NaOH
40 40 14M NaOH
20 20
0 0
0 5 10 15 20 25 0 5 10 15 20 25
Figure 28: Active Si & Al species from SLR as a function of temperature (75℃), NaOH
molarity, and contact time.
Method 113
The active species of aluminium were identified to reside mainly in the solid phase. In contrast,
the distribution of active Si species was approximately equal between the solid and liquid
phases. To gain a deeper insight as to the activation behaviour at 75 oC, the corresponding
quantitative XRD data for the solid phase was examined (Table 15).
Table 15: Quantitative XRD data for SLR activated with NaOH at 75 oC
NaOH Reaction Wt %
Concentration Time
Zeolite Non-
(M) Quartz Cancrinite Sodalite Zeolite X
(min) LTA diffracting
3 1080 2.10 0.75 0.19 0.64 0.78 95.54
3 1440 8.16 11.19 6.27 1.31 0.80 72.28
4 1080 2.49 0.38 0.92 1.03 4.82 90.36

4 1440 3.15 0.00 0.00 4.33 9.96 82.56
10 10 2.06 2.74 5.91 0.31 0.00 88.98

10 30 2.11 4.16 11.74 0.54 0.01 81.43
10 1080 2.08 8.21 15.83 0.73 0.17 72.98
10 1440 1.93 19.26 12.37 1.59 0.08 64.77
14.3 10 2.22 2.91 3.91 0.54 0.00 90.41

14.3 30 2.42 7.27 11.63 0.78 0.00 77.90
14.3 1080 2.63 18.57 15.62 0.81 0.06 62.30
14.3 1440 1.66 24.47 13.65 1.10 0.16 58.96
Regardless of the NaOH molarity used the general trend was a diminution in the presence of
non-diffracting material as the activation time was increased. For the low molarity NaOH
solutions (3 and 4 M) the appearance of crystalline phases was not significant until after 1440
Method 114
minutes of activation. Alternatively, when 10 or 14 M NaOH solutions were employed, the
appearance of sodalite (Na8Al6Si6O24(OH)2) and cancrinite (Na 8Al6Si6O24(OH)2.2H2O) was
recorded. The cancrinite amount increased with activation time; whereas growth of sodalite
occurred during the first 1080 minutes but diminished after that time. This outlined behaviour
was in accord with the knowledge that sodalite can be transformed into the more stable
cancrinite. P. Zhang, et al. (2019) indicated that the formation of cancrinite occurred via initial
creation of an amorphous phase which transformed into zeolite LTA, then sodalite, and
ultimately cancrinite. Factors which accelerated the production of cancrinite included
increasing reaction time (X. Liu et al., , 2013), higher reaction temperature (Esaifan et al.,
2019), and elevated alkalinity levels (Wernert et al., 2020). As an example, Esaifan et al.
(2019) indicated that use of ≥ 10 M NaOH solutions when activating kaolin resulted in
cancrinite formation. Alternatively, these authors outlined that lower molarity NaOH solutions
(≤ 4 M) promoted formation of zeolite LTA, zeolite P and analcime.
Notably, the fact that active aluminium species resided mainly in the solid phase suggested
that NaAl(OH)4 (which is formed in alkaline, aqueous solutions) was barely present; and that
the active aluminium was probably part of an aluminosilicate material. Yue et al. (2020)
extensively characterized the solid products resultant from activation of rectorite clay using a
quasi-solid phase strategy. Analytical techniques included X-ray diffraction, solid state NMR,
infrared spectroscopy, Raman spectroscopy, Scanning Electron Microscopy (SEM) and X-ray
photoelectron spectroscopy (XPS). A multitude of species were detected including
Na6Al6Si6O24, Na4Al4Si6O20, Na4Al4Si4O16, Na4Al4Si5O18, and NaOH. Ultimately the
depolymerization process formed various monomers (Na 4SiO4 and NaAlO2), dimeric silica
(Na6Si2O7) and silica chains (Na 2SiO3). From Table 15 it was additionally shown that a
Method 115
fraction of the Al species were present in both hydroxysodalite (Na 8(Al6Si6O24(OH)2.nH2O)
and cancrinite (Na 6Al6Si6O24(OH)2.2H2O) material.
On the basis that the Si/Al molar ratio in the SLR was 2.25, it was deduced that approximately
half of the Si present was residing in the mother liquor. Based upon the study of Yue et al.,
2020) monomeric Na4SiO4 (Equation 13) or dimeric Na6Si2O7 (Equation 14) were considered
as the final reactive forms of silica formed when depolymerizing aluminosilicates.
Equation 13:
2 𝐻2 𝐴𝑙2𝑆𝑖4.5 𝑂13 . 1.5𝐻2 𝑂 + 40 𝑁𝑎𝑂𝐻 → 9 𝑁𝑎 4 𝑆𝑖𝑂4 + 4 𝑁𝑎𝐴𝑙𝑂2 + 25 𝐻2 𝑂
Equation 14:
4 𝐻2 𝐴𝑙2 𝑆𝑖4.5 𝑂13 . 1.5𝐻2 𝑂 + 62 𝑁𝑎𝑂𝐻 → 9 𝑁𝑎 6 𝑆𝑖2 𝑂7 + 8 𝑁𝑎𝐴𝑙𝑂2 + 41 𝐻2 𝑂
Due to the outlined increase in activation of SLR when using a temperature of 75 oC, it was of
interest to examine whether a higher temperature of 100 oC was beneficial (Figure 29).
Method 116
100 100

80 80
60
60
40
40 20 4M NaOH
4M NaOH 5M NaOH
5M NaOH 7M NaOH
7M NaOH 10M NaOH
10M NaOH
20 0
0 5 10 15 20 25 0 5 10 15 20 25
100 14
4M NaOH
12
5M NaOH
80 7M NaOH
10M NaOH
10
60 8
40 6
4
20 4M NaOH
5M NaOH 2
7M NaOH
10M NaOH
0 0
0 5 10 15 20 25 0 5 10 15 20 25
100 100
80 80
60 60
40 40
20 4M NaOH 20 4M NaOH
5M NaOH
5M NaOH 7M NaOH
7M NaOH 10M NaOH
10M NaOH
0 0
0 5 10 15 20 25 0 5 10 15 20 25
Figure 29: Active species from SLR as a function of temperature (100 ℃), with different
NaOH molarity and contact time
Method 117
The higher activation temperature notably improved the extent of active Si formation compared
to lower temperature data; albeit the use of NaOH molarity < 7 M still required 24 hours to
achieve almost complete Si activation. XRD analysis suggested that there was a clear trend of
increasing cancrinite formation not only as a function of the NaOH molarity but also when the
contact time was longer (Figure 30).
wt% Crystalline Cancrinite wt% Crystalline Sodalite
100 100
4M NaOH 4M NaOH
wt% Crystalline Sodalite

5M NaOH
5M NaOH
7M NaOH
80 7M NaOH
10M NaOH 80 10M NaOH
60 60
40 40
20 20
0 0
0 5 10 15 20 25 0 5 10 15 20 25
wt% Crystalline Zeolite LTA Non-diffracting/unidentified
100
Non-Diffracting/unidentified %
100
wt% Crystalline Zeolite A
4M NaOH 4M NaOH
5M NaOH 5M NaOH
80 7M NaOH
10M NaOH 80 7M NaOH
10M NaOH
60
60
40
40
20
20
0
0
0 5 10 15 20 25 0 5 10 15 20 25
Figure 30: XRD analysis of active solid phase formed from reaction of SLR with NaOH
solution at 100 ℃; function of NaOH molarity and contact time.
Method 118
For example, for the 10 M NaOH solution the amount of cancrinite formed increased from 10.3
to 48.0 wt% as the contact time progressed from 10 to 360 minutes, and it improved to 67%
after 24 hours. Simultaneously, the presence of sodalite diminished from 18.8 to 12.9 wt% and
the detection of non-diffracting species decreased from 67.5 to 35.3 wt%. A minor zeolite
LTA phase was also identified which grew from 0.8 to 2.2 wt % with increasing contact time.
Cancrinite is the most stable phase formed when converting aluminosilicate gels to mixtures
of sodalite, zeolite LTA, and zeolite X (Ríos et al., 2009). Notably, Stewart (1941) indicated
that cancrinite is actually unstable in acid solutions and thus can, in theory, be classified as
“reactive”.
Further heating of SLR at 150 ℃ with a 10 M NaOH solution resulted in a reduction in
formation of active Si species after a one-hour contact time (ca. 5%) (Figure 31). Extension of
the reaction time only resulted in a slight decrease in active Si content. Similarly, use of 3 M
NaOH under similar conditions not only produced fewer active Si species, but also increasing
the contact time actually inhibited formation of active species.
XRD analysis (Figure 32) indicated that the amount of cancrinite increased with alkali
concentration and not with contact time. For example, the 10 M NaOH sample increased the
percentage of cancrinite in the first hour from 16 to 53%, before the amount stabilised until the
last contact time (18 hours); while the 3M NaOH sample remained stable at approximately 7%
until the four-hour mark. Subsequently, the amount of cancrinite significantly increased to
16.5%. The data in Figure 31 suggests that the stabilisation of cancrinite in the samples was
due a deficit of aluminium which agreed with the total amount of active species (Al in mother
liquor + Al in solid product) in the sample.
Method 119
100 100
3M NaOH
3M NaOH
90 10M NaOH

10M NaOH
80
80
70 60
60 40
50
20
40
30 0
0 5 10 15 20 25 0 5 10 15 20 25
100 100
3M NaOH
3M NaOH
10M NaOH
80 80
10M NaOH
60 60
40 40
20 20
0 0
0 5 10 15 20 25 0 5 10 15 20 25
100 100
3M NaOH
10M NaOH
80 80
60 60
40 40
3M NaOH
20 20 10M NaOH
0 0
0 5 10 15 20 25 0 5 10 15 20 25
Figure 31. Active species from SLR as a function of temperature (150℃), NaOH molarity
and contact time
Method 120
100 100
3M NaOH

10M NaOH
3M NaOH
80 80 10M NaOH
60 60
40 40
20 20
0 0
0 5 10 15 20 25 0 5 10 15 20 25
wt% Crystalline Zeolite LTA Non-diffracting/unidentified
100 100
Non-Diffracting/unidentified %
wt% Crystalline Zeolite A
3M NaOH
80 3M NaOH
10M NaOH
90 10M NaOH
60 80
70
40
60
20
50
0
40
30
0 5 10 15 20 25
0 5 10 15 20 25
Figure 32. XRD analysis of active solid phase formed from reaction of SLR with NaOH
solution at 150 ℃; function of NaOH molarity and contact time.
Method 121
Zeolite Synthesis after SLR Activation
Zeolite Synthesis without Pre-activation of SLR
In order to determine the baseline transformation of SLR to zeolite products an
experiment was conducted wherein SLR was reacted with an NaOH solution into
which had been added sodium aluminate in order to adjust the SiO 2/Al2O3 ratio to 0.95
(Figure 33).
a)
b)
Phase Wt%
Quartz 1.41
Cancrinite 2.55
Sodalite 1.22
Zeolite LTA 31.92
Non-diffracting 62.90
Figure 33: a) XRD and b) SEM image of the zeolite product produced by hydrothermal
reaction of non-activated SLR with with NaOH in a sodium aluminate solution at 80
oC for 4 h: SiO /Al O ratio = 0.95
2 2 3
The XRD analysis indicated that directly converting SLR to zeolite LTA is
challenging. Indeed, the dominant product was non-diffracting in character, and there
were also significant amounts of zeolite LTA and a minor fraction of sodalite detected.
Figure 33 also shows an SEM image of the solid product which comprised of two
distinct crystal types. In agreement with the XRD data, sodalite was evidenced by the
characteristic “thread-ball” or “urchin” shape (Daramola et a., 2017) and cubic
crystals ascribed to the presence of zeolite LTA were apparent.
Chapter 5: “One Pot” Synthesis of Zeolites: Activation of Spodumene Leachate Residue using a New
Quench Method 122
The sodalite and zeolite LTA materials appeared to be growing out of a relatively
featureless aluminosilicate phase. This conclusion has also been reported by Andaç et
al. (2005) who demonstrated that before zeolite crystal growth, an amorphous phase
forms with the sodium aluminosilicate solution (Andaç et al., 2005).
Pre-activation of SLR with 10 M NaOH at 100 or 150 oC Prior to Synthesis of

Zeolite LTA
The influence of two activation temperatures (100 and 150 oC) upon the quality of
zeolite were evaluated according to XRD analysis (Figure 34). It was apparent that
zeolite LTA was predominantly synthesised from SLR activated at 100 oC. Moreover,
a reaction period of four hours resulted in greater formation of zeolite LTA (54 wt%)
compared to when reaction was conducted for 17 hours (25.6 wt%). Extended reaction
times reduced the presence of zeolite LTA and promoted the growth of cancrinite and
non-diffracting material. Regardless of the reaction time, when using the 100 oC
activated SLR, minimal sodalite was detected. When 150 oC activated SLR was
hydrothermally treated, the solid product was comprised mainly of cancrinite and non-
diffracting material. Increasing the reaction time from 4 to 17 hours notably enhanced
the production of cancrinite (43.2 to 55.4 wt%) and decreased the presence of non-
diffracting material (39.2 to 32.1 wt%).
Quench Method 123
SLR Pre-activation Temperature
100 ℃ 150 ℃
70 70
Cancrinite
Cancrinite
Zeolite LTA
60 Non-Diffracting 60 Zeolite LTA
Non-Diffracting
wt% Crystalline
wt% Crystalline
50 50
40 40
30 30
20 20
10 10
0 0
4h 17h 4h 17h
Synthesis time (hrs) Synthesis time (hrs)
Figure 34. Influence of SLR activation temperature upon Zeolite LTA synthesis: 20 g
SLR, 19.17 g NaOH, 5.33 g NaAlO 2, 80 ℃ synthesis temperature, 3.95 M NaOH
Hence, a closer inspection of the zeolite products made using 100 oC activated SLR
was completed; in order to ascertain the optimum reaction time at 80 oC. Figure 34
shows that a four-hour reaction time was indeed the best condition for making zeolite
LTA. The growth of zeolite LTA inversely correlated with the amount of non-
diffracting material identified, as in Figure 35
Quench Method 124
wt% Crystalline Zeolite LTA wt% Non-Diffracting/unidentified
wy% Crystalline Zeolite LTA

80 80
70
wt% Non-Diffracting
60 60
50
40 40
30
20
20
10
0
0 2 4 6 8 10 12 14 16 18 0
0 2 4 6 8 10 12 14 16 18
Synthesis time (hrs)
Synthesis Time (hrs)
80 80

60 60
40 40
20 20
0 0
0 2 4 6 8 10 12 14 16 18 0 2 4 6 8 10 12 14 16 18
Figure 35. Importance of hydrothermal synthesis reaction time at 80 oC for SLR

activated at 100 oC
Sodalite was present in limited amounts throughout the synthesis period and
remarkably constant in value. In contrast, cancrinite was at the highest level (17.1
wt%) during the initial stage of the synthesis reaction and decreased to a relatively
stable value of ca 6.6%.
Scanning electron microscopy (SEM) images were also gathered in order to provide
deeper insight into the transformation of activated SLR into zeolite products (Figure
36). After one hour of hydrothermal synthesis the solid agglomerated product was not
only roughly spherical but also in the size range of 3 to 4 microns. Numerous globular
materials decorated the surface of the spheres.
Quench Method 125
1h 2h
3h 4h
6h 18h
Figure 36: SEM images of solid zeolite product formed as a function of time after
hydrothermal reaction using 3.95 M NaOH and Si/Al ratio = 0.95
Increasing the reaction time to two hours induced a loss of the majority of spherical
structures and growth of a platelet material.
Quench Method 126
The first evidence for formation of cubic crystals of zeolite LTA was also observed;
albeit their presence was not common. After three hours of reaction the formation of
cubic zeolite LTA crystals significantly increased. Concomitantly the amount of
platelet material decreased. After four hours reaction the solid product was seen to be
almost entirely comprised of zeolite LTA crystals (Figure 36).
As the reaction time was further extended to six hours the presence of zeolite LTA
crystals was diminished, and growth of spherical material promoted. After 18 hours
reaction the degradation of zeolite LTA was clearly evident; as was the formation of
larger, relatively featureless agglomerates which were accompanied by the
aforementioned spherical material.
Finally, XRF analysis was used to determine the composition of the zeolite product
made using a temperature of 80 oC for four hours (
Table 16).
Table 16. XRF analysis of solid product from Zeolite LTA synthesis using SLR
activated at 100 oC
Oxide Mass % (Dry Basis) Oxide Mass % (Dry
Basis)
SiO2 36.72 P2O5 0.00
Al2O3 29.43 SO3 1.026
Fe 2O3 0.279 Cr2O3 0.018
Na2O 19.53 NiO 0.002
K2O 0.074 ZnO 0.00
MgO 0.055 PbO 0.008
CaO 0.02 BaO 0.002
TiO2 0.037 Mn3O4 0.064
LOI 13.5
Quench Method 127
The molar SiO2/Al2O3 ratio was 2.11 and the general composition was
Na13.1Al12.0Si12.7O50.1.15.6 H2O.
Pre-activation of SLR with 10 M NaOH at 100 oC Prior to Synthesis of Zeolite

LTA with SiO2/Al2O3 ratio of 1.9 in the Feed Mixture
Figure 37. SEM images of solid zeolite product formed after hydrothermal reaction
using 3.95 M NaOH and Si/Al ratio = 0.83 and 3-hour synthesis time
Since
Table 16 indicated that an excess of Si was present in the zeolite product, the amount
of NaAlO2 added to the synthesis mixture was adjusted to provide a slight excess of
aluminium species. Commercially, zeolite LTA is often made using excess aluminium
in order to guide the synthesis to zeolite LTA (Ameh et al., 2017). Figure 37 indicates
that the additional aluminium accelerated the formation of zeolite LTA as maximum
zeolite LTA content was noted after three hours of reaction (52.0 wt%) instead of four
(56.0 wt%). However, the amount of zeolite LTA in the solid product was not
increased.
Quench Method 128
60
wt% Crystalline 50
40
30 wt% Crystalline Cancrinite

20 wt% Crystalline Zeolite LTA
wt% Non-Diffracting/unidentified
10
0
2.0 2.5 3.0 3.5 4.0
Figure 38. Zeolite synthesis at 80 oC as a function of reaction time: SiO 2/Al2O3 ratio
= 0.83
These results showed that zeolite LTA synthesis is not only affected by the reaction
time but also by Si/Al content. For example, at three hours of reaction and an Si/Al
ratio of 0.95, 30.97wt% zeolite LTA was obtained whereas using the same reaction
time but increasing the aluminium content to an Si/Al ratio of 0.85, 52.0 wt% was
obtained. This conclusion agreed with previous research reported by Ameh et al.
(2017), who demonstrated that a decrease of Si/Al ratio in zeolite LTA synthesis has
a direct proportionality on the crystal size of the final product. Furthermore, it was
proved that crystallinity and framework structure can be improved or compromised by
slightly adjusting the aluminium content in the solution (Ameh et al., 2017).
Quench Method 129
Conclusions
This study successfully validated the concept of using a quench method to initially
activate waste aluminosilicate materials (such as SLR) and then adjust reaction
conditions to form valuable zeolite products such as zeolite LTA.
Activation of SLR was dependent primality on two factors, molarity of the sodium
hydroxide and activation temperature. Testing revealed that an NaOH molarity of 10
M and a reaction temperature of 100 oC for no more than 1 hour was optimal.
Lowering the activation temperature reduced the activation rate which was not
desirable due to energy costs associated with heating the activation mixture. Whereas
use of higher activation temperatures favoured the formation of cancrinite as did higher
alkali molarities. Significantly, high temperature fusion processes usually reported in
zeolite literature are not required.
After quenching the reactant solution to reduce temperature, decrease NaOH molarity
and adjust SiO2/Al2O3 ratio; zeolite LTA was synthesised as verified by XRD patterns
and SEM images. The identification of substantial amounts of non-diffracting material
using quantitative XRD was not consistent with SEM images which revealed that
samples were highly crystalline.
Future studies should focus on development of continuous hydrothermal reactors
which can more rapidly decrease the reaction temperature and molarity to improve
control of the zeolite LTA synthesis.
Quench Method 130
Key Insights
This chapter presented an innovative solution that not only reduces waste but also
fosters a sustainable approach towards the production of valuable zeolites. By
optimizing the activation of SLR and synthesizing zeolite LTA using the "Quench
Method", this study successfully demonstrates the feasibility of converting waste
materials into valuable products. The activation of SLR involved varying the
temperature, sodium hydroxide concentration, and time of the process. Subsequently,
zeolite LTA synthesis was achieved by fine-tuning the sodium hydroxide molarity and
Si/Al ratio. The addition of a slight excess of aluminium in the solution further
improved the synthesis process. The results of this study hold promise for promoting
sustainability in the lithium industry by repurposing waste materials into high value
zeolites.
In order to optimize the method proposed, the utilization of continuous reactors has
been recommended. Nonetheless, one of the main challenges encountered in the
employment of continuous reactors for zeolite synthesis is the issue of viscosity. As
the synthesis progresses, the concentration of the reaction mixture increases, which in
turn causes the viscosity of the mixture to rise. This can lead to issues such as reactor
clogging, uneven heat distribution, and difficulties in controlling the reaction
conditions (Z. Liu, Zhu,et al., 2019). Nevertheless, this issue has been resolved in the
design by employing a combination of a continuous reactor and a batch reactor (see
Supplementary Figure 6). Specifically, the continuous reactor will be solely utilized
for the activation phase to obtain active Si and Al species while being capable of faster
quenching before it reaches the next reactor. By incorporating Industry 4.0 principles,
Quench Method 131
notably machine learning, in conjunction with continuous reactors for zeolite
synthesis, several benefits can be derived.
The incorporation of machine learning algorithms can significantly enhance the
optimization of zeolite synthesis in continuous reactors, leading to reduced production
time and costs, improved product quality, and minimized waste. These algorithms can
analyse real-time data collected from sensors and other sources to dynamically adjust
the operating parameters of the reactor, including temperature, pressure, and flow rate.
This approach can effectively maximize the efficiency of the synthesis process.
Moreover, the predictive capabilities of machine learning algorithms can anticipate
potential problems and provide early warnings, enabling timely corrective actions to
be taken, thereby reducing downtime, and minimizing the need for manual
intervention, which is often time-consuming and prone to human error.
The chapter of this research focuses on the development of a robust dataset for machine
learning in zeolite synthesis. that study illustrates the difficulties encountered in
creating appropriate datasets for machine learning in the synthesis of zeolite LTA.
Comparing zeolite synthesis parameters between different laboratories is inherently
challenging, which can impair the accuracy of predictions generated by machine
learning. Thus, researchers must establish their own database for zeolite synthesis,
despite the time-consuming nature of this process which necessitates conducting
numerous experiments. Zeolite LTA is an exemplary case study for this chapter due to
its well-established synthesis process.
Quench Method 132
Chapter 6: Factors which Influence Development of Robust Data Sets for
Machine Learning and Statistical Analysis of Zeolite Synthesis
Abstract
Machine learning is an important part of zeolite science which relies upon a reliable and
comprehensive dataset. However, there exist experimental challenges for zeolite researchers to
create suitable datasets and avoid problems associated with the use of contradictory data. This study
illustrates the situation using zeolite LTA synthesis as an example. First, quantitative X-ray
diffraction (XRD) was preferred to qualitative data as it accounted for non-diffracting material.
Secondly, an accurate mass balance was required since a substantial amount of valuable chemicals
were in the mother liquor and the wash water. Zeolite synthesis data from various hydrothermal
reactor configurations was shown to significantly influence zeolite LTA synthesis. The heat transfer
behaviour of the reactors was of relevance as this controlled heating rates, actual reaction
temperatures and cool down periods. Pre-heating of the zeolite synthesis mixtures was a potential
means of mitigating variation in zeolite synthesis, as it minimised variations in the heating up time.
The influence of stirring or static conditions while the reactants were converted to zeolite product
was another factor which altered zeolite product quality. Static conditions were favourable in terms
of zeolite properties but industrially this may not be an option as the larger vessels involved require
stirring to maintain homogeneity. In summary, it is inherently problematic to compare zeolite
synthesis parameters between laboratories. This latter finding also makes it difficult to use web
crawling approaches to mine data as the collected information is biased. Nevertheless, addressing
the issues allows meaningful results in a researcher’s laboratory.
Key Words: zeolite LTA; synthesis; machine learning; quantitative XRD; statistics
Chapter 6: Factors which Influence Development of Robust Data Sets for Machine Learning and Statistical Analysis of
Zeolite Synthesis 133
Introduction
Recent years have witnessed the growth of machine learning and statistical analysis of zeolite
synthesis and structural types (Conterosito et al., 2020; Gaillac et al., 2020; Jensen et al., 2019;
Moliner, et al., 2019; Muraoka, et al, 2019; S. Yang et al., 2010). For example Moliner, et al. (2019)
described the use of principal component analysis (PCA) to dimensionally reduce powder X-ray
Diffraction (XRD) patterns to three structural principal components, when studying the synthesis of
ITQ-21 and ITQ-30 zeolites. As an outcome, predictions were made regarding the composition of
the zeolites and the degree of crystalline material present. Alternatively, Jensen et al. (2019)
demonstrated the ability of a Generative Neural Network to discover new organic structure directing
agents which could be employed to make novel zeolite structures. Likewise, S. Ma et al. (2020)
used machine learning approaches to develop improved zeolite synthesis strategies. Due to the ability
of machine learning to work with big data there is potential to accelerate the use of high throughput
methods in zeolite science (Gaillac et al., 2020; Moliner, et al., 2019; Raccuglia et al., 2016; Serra et
al., 2007).
Despite the identified potential for machine learning approaches there is an issue with respect to
access to reliable training data, and ensuring that the model is not over-fitted to the training data
(Selvaratnam & Koodali, 2021). As such fundamental criteria to be satisfied, include provision of
clean data sets (Shahzad et al., 2017). For example, when examining zeolite synthesis, the data
should be repeatable, consider all the experimental variables, and be precise. In practice, data sets
tend to be too small, although there are indications as to how to manage small datasets in material
science (Y. Zhang & Ling, 2018a).
There also appear to be issues with the experimental data collected. For example, interpretation of
X-ray Diffraction (XRD) data is a point of debate in terms of generating a quality data set. XRD is
the most common method for determining zeolite product quality, but most publications use only
qualitative XRD methods and not quantitative XRD analysis. Qualitative XRD compares the relative
area of reflections ascribed to crystalline peaks for each phase present and does not account for non -
diffracting/amorphous content (J.-Q. Wang et al., 2014). Alternatively, quantitative X-ray diffraction
(qXRD) involves the addition of an internal standard which subsequently allows the speciation of a
sample including any amorphous/non-diffracting material present (Längauer et al., 2021).
Accordingly, Gougazeh and Buhl (2014) described the use of Rietveld analysis using TOPAS
software to determine the amount of zeolite LTA, hydroxysodalite, quartz and non-diffracting
material in a material made from hydrothermal reaction of clay.
In terms of zeolite synthesis, the literature rarely indicates the zeolite yield when studying synthesis
conditions. For example, numerous publications show they have made a zeolite based upon XRD
patterns (Jafari et al., 2014; J.-Q. Wang et al., 2014); but no mention of the overall process yield is
made (Yu et al., 2018). This situation makes it difficult to construct a mass balance, and in some
instances determine how to recycle alkali solutions, dissolved aluminium, or dissolved silicates.
There are also problems relating to how comparable data is between different laboratories. For
instance, many studies make zeolites in PTFE lined hydrothermal vessels which are inherently
problematic in that the sample does not rapidly heat when placed in an oven (Hang Chau et al., 2000;
Johnson & Arshad, 2014; Katsuki et al., 2005). Indeed, due to variables such as vessel
volume/geometry, thickness of steel wall, and use of PTFE liner or not, the actual reaction
temperature achieved and time to do so, makes it difficult when trying to understand synthesis data.
Hence, in industry the starting solutions are often pre-heated to the reaction temperature to create a
more robust and economical process (Kettinger, Laudone, & Pierce, 1979).
A new approach to improving heating characteristics is the use of continuous reactors where a tubular
reactor is rapidly heated in for example a pre-heated oil bath (Z. Liu, Wang et al., 2019).
To illustrate the challenges relating to quality data sets this study focussed on zeolite LTA
(Na12((AlO2)12(SiO2)12)·27H2O) as this zeolite remains important due to large scale use in
applications such as laundry detergents (Collins et al., 2020). From an industry perspective the focus
is to make zeolite LTA with the highest yield, optimal physical properties, and with minimal cost.
Notably, the economics for zeolite LTA production have not been addressed in published literature
to any significant extent. Hong et al. (2017) reported a cost study based upon fusion of coal fly ash
followed by hydrothermal synthesis of zeolite LTA. Such a process was suggested to have a positive
net present value (NPV) and payback in ca. seven years. Overarching these technical objectives was
the need to also be environmentally responsible and minimize waste streams (Casci, 2005; Fawer et
al., 1998).
Zeolite LTA synthesis is a well-researched area with many papers published in the academic
literature. However, the primary focus has been in relation to zeolite synthesis chemistry whereas
process engineering aspects have been not addressed in detail. The economics of zeolite LTA
manufacture relates to factors such as price/consumption of raw materials (especially sodium
hydroxide), utilities demand, process design, reaction time and temperature, capital expenditure,
labour and maintenance requirements, and disposal costs for waste streams. A mass balance of the
reactants and products is required as the basis of process design.
Another issue that is often neglected is the composition of the mother liquor recovered when the
zeolite slurry is separated into solid and liquid fractions. Recycling of excess sodium hydroxide to
the initial mixing stage is critical in terms of making the process viable (Bauer, 2008).
Zeolite LTA has an inherent problem since it produces a highly alkaline solution when added to
water. Extensive washing is often required ( Hong, Maneerung, Koh, Sibudjing, & Wang, 2017) and
this situation can result in an imbalance in water demand/use for the production unit. Consequently,
some companies evaporate a portion of the water in the mother liquor and then reuse this water in the
washing stage (Deabriges, 1982). Following the washing stage zeolite LTA is typically spray dried
to form a uniform powder. Depending upon the application for the zeolite LTA material it may also
be shaped into extrudates or spherical beads (Bingre, Louis, & Nguyen, 2018). Common binders
include clay, pseudoboehmite, and water glass. The mixed product is then calcined at high
temperature to improve both mechanical and textural properties (Bingre et al., 2018).
Ultimately this situation means that optimization of the entire zeolite synthesis process is often not
completed, and the quality of data required for machine learning is flawed. Therefore, the aim of this
study was to develop strategies to improve zeolite LTA synthesis data which could subsequently be
used in machine learning. The hypothesis was that “if process engineering and machine learning
approaches are combined then this may result in more economical, higher quality and
environmentally sustainable synthesis of zeolite LTA”. Research questions which addressed the
hypothesis included: (1) Does quantitative XRD provide superior data when characterizing zeolites?
(2) What is the advantage of ensuring that a mass balance is reported when making synthetic zeolites?
(3) What is the variability of zeolite physical characteristics if made using the same conditions in
different hydrothermal reactor vessels? (4) Can pre-heating of reactant solutions facilitate the growth
of more uniform zeolite powder? (5) Do stirring or static conditions favour superior zeolite synthesis?
Various hypothermal vessels were employed to synthesise zeolite LTA using a range of synthesis
variables including: SiO2/Al2O3 ratio; H2O/Na2O ratio; Na2O/SiO2 ratio; reaction temperature; and
reaction time. Ultimately this study was designed to prepare zeolite researchers to maximise machine
learning outcomes for zeolite synthesis strategies; by understanding that need for data quality.
Chemicals
Sodium aluminate (NaAlO2), sodium metasilicate pentahydrate (Na 2SiO3•5H2O), and NaOH (extra
pure micro- pearls) were purchased from Chem-Supply, Australia as analytical reagent grade (AR).
Zeolite LTA Synthesis

For the samples at room temperature, sodium hydroxide was dissolved at ambient temperature in de-
ionised water. Then the sodium metasilicate was added to the sodium hydroxide solution. In a
separate container the sodium aluminate was dissolved into an equivalent amount of de-ionised water.
Ideally, the volumes of the aluminate and silicate solutions should be approximately the same to
encourage homogeneous mixing. The two solutions were rapidly combined into a 125 mL Nalgene
bottle and vigorously stirred for 30 seconds; to again promote uniformity of the resultant gel. The
mixture was then aged at ambient temperature for 0.5 h. After aging the Nalgene bottle was placed
in an incubator (Innova 43R, New Brunswick) at 80 oC for the synthesis period.
For the pre-heated feed mixture, sodium hydroxide pearls and sodium metasilicate were dissolved in
deionized water located in a stainless-steel beaker. This mixture was then heated to 80 ℃. In a
second beaker a solution of deionized water and sodium aluminate was heated to 80℃. Once both
solutions reached reaction temperature, they were combined into a 125 mL Nalgene bottle in which
an aluminosilicate gel rapidly formed. Then, the reactant mixture was placed in an incubator at 80℃
and agitated at 100 rpm for a specific synthesis time. Note that after forming the gels both samples
(stirred and static) were shaken in the bottles to destroy the gel structure before going into the
synthesis reactor.
Once zeolite synthesis was completed, the samples were removed from the incubator and centrifuged
to separate the mother liquor from the solid product. After the removal of the mother liquor the solid
product was washed until the pH was ≤11. The product was then dried and crushed at which point it
was stored in a sealed vessel. In terms of precursor conditions, the H2O/SiO2 molar ratio was varied
between 15 and 35 which was in accord with the comprehensive study by Kostinko (1985) which
suggested this was the preferred range for zeolite LTA formation.
Material Characterization
X-ray fluorescence (XRF)

A wavelength dispersive X-ray fluorescence (PANalytical Axios WD-XRF) instrument was
employed to record the zeolite composition. First 1 g of zeolite powder was placed in a 95/5 % Pt/Au
crucible. Then 10 g of vitreous 50:50 lithium tetraborate: lithium metaborate flux was introduced.
The samples were subsequently placed in the fusion equipment (TheOx, Claisse Scientific) for 20
minutes at 1050 °C. The resultant glass discs were analysed and a value for the Loss on Fusion (LOF)
was estimated.
X-ray diffraction (XRD)

X-ray diffraction (XRD) traces were acquired using a Panalytical X'Pert wide angle X-ray
diffractometer with Co Kα radiation (1.7903 Å). XRD patterns were collected every 0.02° in the
range of 5 to 90° 2θ using a rate of 30 seconds per step. Quantitative XRD analysis was conducted
by introduction of a 10 wt% corundum internal standard. XRD data was interpreted by TOPAS v5
software which used the Rietveld method. The reference patterns for zeolite LTA were referenced
from PDF-4 entry 04-016-9920.
A JEOL 7001F Scanning Electron Microscope (SEM) imaged the zeolite materials. Zeolite samples
were prepared by placing on carbon tape and coating with platinum. An accelerating voltage of 5 kV
and probe current of 8 was employed.

Particle size distribution of the zeolite product was acquired using a Mastersizer 3000 instrument
(Malvern Panalytical, UK). The powders were mixed with deionized water and ultrasonicated for a
time of 30 minutes.
Solution Analysis
Inductively Coupled Plasma - Optical Emission Spectroscopy (ICP-OES)

Solutions were filtered with a 0.45 µm syringe filter and analysed by Inductively Coupled Plasma
Optical Emission Spectroscopy (ICP-OES). Appropriate standards were used to calibrate the
machine.
pH and Conductivity
The solution pH was determined using a labCHEM-CP benchtop from TPS (Australia). Regular
calibration was enacted using standard buffer solutions (pH 4, 7 and 10) supplied by Rowe Scientific,
Australia.
The Use of Quantitative and/or Qualitative XRD

The application of X-ray diffraction to characterize zeolite products is ubiquitous.
There are a range of approaches which generate data which range from qualitative to
quantitative. For example, qualitative XRD simply identifies the crystalline phases
present and indicates if the materials are in trace, minor, or major amounts. The next
level of detail is semi-quantitative wherein not only is the crystalline phase identified
but also a relative percentage of each mineral is provided (derived from application of
the normalized reference intensity ratio). Semi-quantitative analysis can also suggest
what the amorphous/non-diffracting amount is in the sample. Spiking the sample can
result in more accurate data interpretation. In theory, the preferred XRD analysis
method is quantitative in nature. The basis of this technique is to incorporate an
internal standard such as corundum and then complete Rietveld analysis. However,
quantitative XRD requires more complex sample preparation, and more in-depth
analysis (Shams et al., 2021). Inherent to machine learning is the need for accurate
data input, hence it appears necessary to focus on quantitative XRD analysis of zeolite
samples.
Figure 39 shows the quantitative XRD data recorded for the solid products made at 80
oC using a gel composition of SiO 2/Al2O3 = 2; Na2O/SiO2 = 2.5 and H2O/Na2O = 15
to 35 as a function of reaction time. A trend which was common to all H 2O/Na2O
values employed was a clear maximum in zeolite LTA content as a function of reaction
time. The time at which this maximum zeolite LTA content was identified was greater
as the H2O/Na2O ratio was increased, with the optimal synthesis time identified at 4
hours. In addition, the formation of impurity phases such as cancrinite and sodalite
was observed, especially when the H 2O/Na2O ratio was 15 (Table 17). As indicated by
Chapter 6: Factors which Influence Development of Robust Data Sets for Machine Learning and
Statistical Analysis of Zeolite Synthesis 141
Roland (1989) sodalite is a known impurity phase when reaction conditions are sub-
optimal. Similarly, Buhl (2016) reported creation of both sodalite and cancrinite as
by-products when performing autothermal synthesis of zeolite LTA. Cancrinite is
regarded as the thermodynamically most stable species in the Na 2O-SiO2-Al2O3-H2O
system (Peng et al., 2018).
A study by Kostinko (1982) addressed the relationship of synthesis variables when
making zeolite LTA, X and Y. It was shown that careful control of reaction conditions
was required to avoid making mixed phases of either zeolite LTA and hydroxysodalite
or zeolite LTA and zeolite X. An H2O/Na2O ratio of 25 was claimed to produce
relatively pure zeolite LTA within a one-hour reaction time at 100 oC (SiO2/Al2O3 =
2; Na2O/SiO2 = 2.4). Accordingly, in Table 17 it is also evident sodalite and cancrinite
formation formed when using high molarity alkali solutions (H 2O/Na2O < 20).
100 100
Zeolite LTA Zeolite LTA
Non-diffracting Non-diffracting
80 80
wt% Crystalline
wt% Crystalline
60
60
40
40
20
20
0
0 1 2 3 4 5
1 2 3 4 5
Time (hrs)
Time (hrs) H2O/ Na2O = 20
H2O/Na2O = 15
100 100
Zeolite LTA
Non-diffracting
80 80
wt% Crystalline
wt% Crystalline
60 60
Zeolite LTA
Non-diffracting
40 40
20
20
0
0 1 2 3 4 5
1 2 3 4 5
Time (hrs)
Time (hrs)
H2O/ Na2O = 30
H2O/Na2O = 25
100
80
wt% Crystalline
60
Zeolite LTA
Non-diffracting
40
20
0
1 2 3 4 5
Time (hrs)
H2O/ Na2O = 35
Figure 39: Quantitative XRD patterns for Zeolite LTA: SiO2/Al2O3 = 2; Na2O/SiO2 =
2.5; H2O/SiO2 = 15 to 35; Temperature = 80 oC: Note that trendlines are only a
visual aid.
Notably the maximum amount of crystalline zeolite LTA estimated from quantitative
XRD analysis was 90.24 wt% (when H 2O/Na2O ratio = 35). In comparison, qualitative
XRD analysis appeared to overestimate the amount of crystalline zeolite LTA present
(Table 17).
Table 17: Summary of quantitative XRD analysis of zeolite samples made at 80 oC;
SiO2/Al2O3 = 2; Na2O/SiO2 = 2.5 and H2O/Na2O = 15 to 35; stirring 100 rpm
wt% Zeolite
wt%
Reaction wt% wt% wt% Non- LTA
H2O/Na2O Zeolite
Time (h) Cancrinite Sodalite diffracting (Qualitative
LTA
XRD)
15 1 0.00 0.02 64 35.85 99.92
15 2 1.8 1.06 59 38.46 95.26
15 3 4.37 4.99 34 56.44 78.51
15 4 5.63 7.37 21 65.55 62.12
15 5 5.03 5.42 20 69.15 66.13
20 1 0.00 0.00 38.15 61.68 99.56

20 2 0.00 0.19 68.85 30.88 99.61
20 3 0.30 0.48 75.26 23.88 98.87
20 4 1.15 1.36 60.09 37.38 95.98
20 5 1.29 2.53 49.53 46.64 92.82
25 1 0.18 0.00 8.82 90.94 97.35

25 2 0.02 0.00 77.75 22.17 99.90
25 3 0.00 0.01 73.28 26.63 99.88
25 4 0.09 0.00 79.72 20.13 99.81
25 5 0.05 0.12 56.62 43.15 99.58
30 1 0.10 0.05 26.64 73.18 99.33

30 3 0.07 0.02 79.40 20.41 99.77
30 4 0.06 0.01 82.87 16.97 99.81
30 5 0.00 0.00 79.27 20.58 99.81
35 1 0.14 0.01 30.01 69.83 99.47

35 2 0.00 0.00 54.39 45.14 99.14
35 3 0.00 0.04 84.74 14.92 99.59
35 4 0.08 0.02 90.24 9.46 99.66
35 5 0.00 0.00 78.51 21.09 99.48
Notably, with the quantitative XRD method the data was consistent with the general
formation of zeolites presented by (Cundy & Cox (2005). For example, in Figure 39
when the H2O/Na2O ratio was 35, the initial induction/nucleation period was evident
wherein the initial zeolite growth occurs. Increasing reaction time further promoted
zeolite LTA crystal growth until a maximum amount of crystalline zeolite LTA is
present. Finally, the metastability of zeolite LTA was apparent for reaction time >
four hours when amorphous material was forming at the expense of zeolite LTA. In
contrast, the qualitative data did not agree with accepted zeolite synthesis theory due
to the lack of insight into the amount of amorphous/non-diffracting material present.
It is noted that previous literature has reported relatively high levels of
unidentified/amorphous material when making zeolite from waste aluminosilicates.
For example, . Längauer et al. (2021) estimated the amorphous/unidentified content of
zeolites when synthesised from coal fly ash to be in the range of 55 wt%.
SEM images confirmed the appearance of zeolite LTA in the samples (Figure 40). For
the sample prepared at H2O/Na2O = 15, initially after one hour of reaction the presence
of sub-micron sized crystals was observed as part of a larger cluster. Extension of the
reaction time broke up the clusters and the presence of well-defined crystals lessened.
By five hours of reaction the material present was not only relatively amorphous in
appearance but highly dispersed. In contrast, SEM images recorded when the
H2O/Na2O ratio was increased to 35 indicated a different pattern of behaviour. After
one hour the sample appeared to lack distinct crystals with the material best
characterized as amorphous in character. However, lengthening of the reaction time
to three hours promoted the growth of cubic zeolite LTA crystals out of an amorphous
mass. The distinctive cubic crystals of zeolite LTA became more abundant after five
hours of reaction and became relatively well dispersed. The particles were visually
estimated to range from 0.25 to 2 microns. The trends observed in the SEM images
correlated well with the quantitative XRD analysis but did not agree with the results
of qualitative XRD analysis (Table 17 & Figure 39).
H2O/Na2O = 15 H2O/Na2O = 35
1 hour
3 hours
5 hours
Figure 40: SEM images of zeolite made at 80 oC as a function of time: SiO 2/Al2O3 =
2; Na2O/SiO2 = 2.5 and H2O/Na2O = 15 or 35 as indicated
Mass Balance for Zeolite LTA Synthesis

A mass balance for the synthesis of zeolite LTA at 80 oC for four hours (SiO2/Al2O3 =
2; Na2O/SiO2 = 2 and H2O/Na2O = 30) is shown in Figure 41. To facilitate
examination of the mass balance for zeolite LTA synthesis the ideal stoichiometric
equation is shown in Equation 15.
Equation 15: 𝟏𝟐 𝑵𝒂𝟐 𝑺𝒊𝑶𝟑. 𝟓 𝑯𝟐 𝑶 + 𝟏𝟐 𝑵𝒂𝑨𝒍 𝑶𝟐 →

𝑵𝒂𝟏𝟐 𝑨𝒍𝟏𝟐𝑺𝒊𝟏𝟐 𝑶𝟒𝟖.𝟐𝟕𝑯𝟐 𝑶 + 𝟐𝟒 𝑵𝒂𝑶𝑯 + 𝟐𝟏 𝑯𝟐 𝑶
Alternatively, the actual experimental conditions which relate to the molar oxide ratios
presented above, are illustrated in Equation 16.
Equation 16: 𝟓 𝑵𝒂𝟐 𝑺𝒊𝑶𝟑. 𝟓 𝑯𝟐 𝑶 + 𝟓 𝑵𝒂𝑨𝒍𝑶𝟐 + 𝟓 𝑵𝒂𝑶𝑯 + 𝟐𝟕𝟐. 𝟓 𝑯𝟐 𝑶 →

𝟎. 𝟒𝟏𝟕 𝑵𝒂𝟏𝟐 𝑨𝒍𝟏𝟐 𝑺𝒊𝟏𝟐 𝑶𝟒𝟖 . 𝟐𝟕𝑯𝟐 𝑶 + 𝟏𝟓 𝑵𝒂𝑶𝑯 + 𝟐𝟖𝟏. 𝟓 𝑯𝟐 𝑶
In terms of a general mass balance for the synthesis process the total input was 110.1
g which was balanced by the product streams: (1) mother liquor; (2) wet zeolite cake;
and (3) material lost to the washing stage. The predicted mass of zeolite LTA formed
was 11.1 g if all starting aluminium and silicon species in the initial gel had been
completely transformed. However, the actual zeolite LTA product mass was 8.40 g.
When consideration of the composition of the washing stage and mother liquor were
considered, the value of 8.40 g was optimal when the aluminium and silicon losses
were accounted for.
The mother liquor did not contain major amounts of aluminium and silicon species,
but it did comprise of substantial quantities of sodium (presumably from the presence
of excess sodium hydroxide as suggested in Equation 16). Such large volumes of
sodium hydroxide represent a notable cost to zeolite producers and thus industry
usually recycles mother liquor to the synthesis stage.
For example, Deabriges (1982) described the necessity to recycle both mother liquor
and wash water to recover valuable chemicals. Notably, these streams were heated to
vaporize excess water which was not required for the zeolite synthesis stage. This
vaporized water could then be condensed and reused for washing purposes to reduce
overall water consumption. It was thus apparent that in terms of using machine
learning to maximise the efficiency of zeolite synthesis that collection of mother liquor
analysis data was critical.
Sodium Metasilicate Pentahydrate
g mol
Mass 12.94 0.06
0 2.93 0.18 Mother Liquor (ML)
Si 1.71 0.06 Mass 78.77 g
Na 2.80 0.12 68.5 mL
H2O 5.49 0.30 Si 1495 mg/L
Al 788.7 mg/L
Solid NaOH Na 68020 mg/L
g mol
Mass 4.88 0.12 g mol
O 1.95 0.12 Si 0.10 0.004
Na 2.80 0.12 Aluminosilicate Gel Al 0.05 0.002
H 0.12 0.12 g mol Na 4.66 0.203
Mass 110.10
Water Added to NaOH O 6.83 0.43 Water Mass Loss Washing 7.99 g
g mol Si 1.71 0.06 Incubator - 80oC- 4h
Mass 43.64 2.42 Al 1.65 0.06 Hydrothermal synthesis-100 Slurry Washing Solution
Na 7.01 0.31 RPM g mol
Sodium Aluminate H2O 92.77 5.15 Si 0.29 0.01
Mass 5 g Al 0.35 0.01
g mol Wet Cake Na 1.85 0.08
Na 1.40 0.06 23.34 g
Al 1.65 0.06
O 1.95 0.12
Dried Solid Residue
Water Added to Sodium Aluminate Mass 8.34 g
g mol
Mass 43.64 2.42 g mol
Si 1.32 0.047
Mass Balance Major Cations Al 1.24 0.046
Inlet (g) Outlet (g) Outlet Total (g) Na 0.50 0.022
ML Washing Solid
Si 1.71 0.1 0.29 1.32 1.71
Al 1.65 0.05 0.35 1.24 1.64
Na 7.01 4.66 1.85 0.5 7.01
Figure 41: Mass balance for the synthesis of zeolite LTA
Chapter 6: Factors which Influence Development of Robust Data Sets for Machine Learning and Statistical Analysis of Zeolite S ynthesis 149
Nevertheless, most zeolite synthesis publications have not analysed the mother liquor,
or indeed described the impact of mother liquor recycling upon not only product
quality but also process economics. Recently, Probst et al., (2022b) showed that
mother liquor recycling when making zeolite N improved the growth of the zeolite
phase due probably to the presence of seeds in the reactant mixture. The
technoeconomics of zeolite N synthesis was also recently shown to be unfavourable if
mother liquor was not recycled (Probst et al., 2022a). In addition, these authors
reported that it was also desirable to recover the first stage wash water as it contained
dissolved silicon and aluminium species in amounts worthy of reusing. This
observation was also in accord with the above mentioned study by Deabriges (1982)
and the data shown in Figure 41 in this investigation.
Influence of Reactor Design upon Zeolite Synthesis

Figure 42 illustrates the temperature profiles when using either a reaction vessel placed
in a heated incubator or a hydrothermal reactor vessel. The reactant mixture did not
achieve the set-point of 80 oC until 2.5 hours after placing the reactor vessel into the
incubator. In contrast, when using the heated hydrothermal reactor, the reaction
temperature overshot the target value of 80 oC, then eventually stabilized at 80 oC after
1.6 hours. The presence of overheating in teflon lined batch reactors is viewed as a
critical factor which should be monitored or at least modelled (Deneyer et al., 2020).
However, most zeolite synthesis publications simply state that they placed the
hydrothermal vessel in a heated oven. For example, Xiao-Yong et al., (2016) used a
teflon lined stainless steel pressure vessel which was placed in an oven at 100 oC for
one hour to convert reactive aluminosilicate gel to zeolite LTA.
As no monitoring of the temperature within the pressure vessel was conducted it was
unknown what the actual temperature profile during reaction was. It is noted that at a
hydrothermal reaction temperature of 100 oC, formation of hydroxysodalite was
promoted (Burriesci et al., 1984). Therefore it is reasonable to assume the actual
reaction temperature in the study by (Xiao-Yong et al. (2016) was most likely lower
than 100 oC.
SEM images indicated that the solid collected after hydrothermal reaction in the
incubator comprised of relatively small, cubic crystals (≤ 1 microns) (Figure 42).
Whereas the zeolite LTA crystals were mostly larger (ca. 2 microns) when made in the
Berghof hydrothermal reactor. It was noted that zeolite formed in the Berghof reactor
was less uniform in size compared to the zeolite sample prepared in the heated
incubator.
Aluminosilica gel Temperature ( oC)
Aluminosilica gel Temperature ( oC)

100 100
80 80
60 60
40 40
20 20
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Reaction Time (hrs) Reaction Time (hrs)
a) Incubator (b) Berghof Hydrothermal Reactor
(c) Zeolite synthesis in the incubator (d) Zeolite synthesis in the Berghof
after 3 hrs synthesis- 75 wt% reactor after 3 hrs synthesis- 98
zeolite LTA wt% zeolite LTA
Figure 42. Heating profile of vessel in heated incubator at 80 oC. Aluminosilicate gel
conditions: SiO2/Al2O3 = 2; Na2O/SiO2 = 2.5, H2O/ Na2O = 42
For both zeolite LTA products, the amount of crystalline zeolite LTA was estimated
to be 75 and 98 wt% for incubator and Berghof reactors, respectively. Ju et al., ,
(2006) examined the variation in characteristics when zeolite LTA was made in either
a conventional teflon lined, a stainless-steel reactor vessel, or a continuous
microreactor. In terms of zeolite particle size, the smallest particles were obtained
when using the microchannel reactor. Deneyer et al. (2020) discussed the mechanism
for zeolite synthesis wherein at lower reaction temperatures the number of nuclei
present was relatively high.
In turn this situation led to formation of small zeolite particles. Conversely, at higher
reaction temperatures where fewer nuclei were generated the average particle size was
increased. The data shown in Figure 42 was consistent with the interpretation of
Deneyer et al. (2020) in that the temperature in the incubated samples was in general
lower that the corresponding temperature in the Berghof hydrothermal reactor.
Impact of Pre-Heating Reactants Prior to Zeolite Synthesis

As outlined in the previous section, various types of hydrothermal vessels have been
used to synthesise zeolites. This situation is inherently problematic in terms of
comparing results from different research groups. One approach to reducing the
problem of differing reactor geometry was to pre-heat the feed solutions prior to
introduction to the hydrothermal reactor (Kettinger et al., 1979). Consequently, both
sodium aluminate and sodium silicate solutions were heated to 80 oC prior to mixing
in the reactor vessel (in this case, the heated incubator). Figure 43 shows that using
H2O/Na2O = 15 resulted in some zeolite LTA formation but also cancrinite and
sodalite contaminants (Table 20). The corresponding SEM image also suggested that
a lack of zeolite LTA was present as minimal “cubes” were observed (Figure 43).
In addition, the SEM image displayed a heterogeneous material which presumably was
a mixture of amorphous matter, cancrinite and sodalite. This result contrasted with the
64.1 to 20.4 wt % zeolite LTA identified in Table 17 after 1 to five hours of reaction
when the feed solutions were not pre-heated, respectively. Pre-heating the aluminate
and silicate solutions accelerated the formation of sodalite, cancrinite and non-
diffracting material at the expense of the metastable zeolite LTA. Hence, use of low
values of H2O/Na2O in the reactant gel combined with pre-heating dictated that the
zeolite synthesis reaction needed to be terminated rapidly. This conclusion was
supported by industry practice where zeolite can be synthesised in only 5 minutes (
Kettinger et al., 1979).
For the zeolite synthesised with H 2O/Na2O = 25, pre-heating of the precursor solutions
promoted the formation of zeolite LTA (c.f. Table 17 to Table 20). The amount of
crystalline LTA was in the range of 73 to 80 wt% when the precursor solutions were
not pre-heated, whereas when the solutions were pre-heated to 80 oC the amount of
crystalline zeolite LTA was in the range 79 to 90 wt %. There was also no evidence
of zeolite LTA degradation after six hours of reaction for the pre-heated samples
(which contrasted with the data in Table 17). Increasing the H2O/Na2O ratio in the
precursor material to 35 along with synthesising zeolite using pre-heated solutions was
conducted. It was noted that the after two hours reaction for the pre-heated sample the
amount of crystalline zeolite LTA was only 11.44 wt % (Table 20) which contrasted
with the corresponding material made with no preheating (Table 17) where zeolite
LTA was 54.39 wt%. Even with longer reaction times the value for crystalline zeolite
LTA was always less than the value for non-preheated samples. In general, these
results agreed with Pina et al, (2004), who pre-heated solutions between 60 and 65 oC
to produce greater amounts of crystalline zeolites.
100
Zeolite LTA
80
Non-diffracting
wt% Crystalline 60
40
20
0
1 2 3 4 5 6
Time (hrs)
H2 O/Na2 O = 15 H2 O/Na2 O = 15; 46% Zeolite LTA
100
80
wt% Crystalline
60
Zeolite LTA
40 Non-diffracting
20
0
1 2 3 4 5 6
Time (hrs)
H2 O/Na2 O = 25 H2 O/Na2 O = 25; 86% Zeolite LTA
100
80
wt% Crystalline
60
Zeolite LTA
40 Non-diffracting
20
0
1 2 3 4 5 6
Time (hrs)
H2 O/ Na2 O = 35 H2 O/Na2 O = 35; 44% Zeolite LTA
Figure 43. Quantitative XRD patterns for Zeolite LTA: SiO2/Al2O3 = 2; Na2O/SiO2 =
2.5; H2O/SiO2 = 15 to 35; Temperature = 80 ℃, pre-heated samples to 80℃; Reaction
Time = 3 h; Reactant mixture stirred at 100 rpm
Table 18. Summary of quantitative XRD patterns for Zeolite LTA: SiO 2/Al2O3 = 2;
Na2O/SiO2 = 2.5; H2O/ Na2O = 15 to 35; Temperature = 80 ℃, Agitation 100 rpm,
pre-heated gel at 80℃ before synthesis
H2O/ wt%
Tim wt% wt% wt%
Na2 Zeolite
e (h) Cancrinite Sodalite Amorphous
O LTA
15 1 6.87 5.85 21.73 65.46
15 2 8.10 10.90 44.07 36.80
15 3 6.41 12.36 46.28 34.70
15 4 7.81 12.97 51.16 27.97
15 5 7.43 13.24 47.54 31.64
15 6 7.79 11.05 38.96 42.14
20 1 0.27 0.27 86.59 12.83

20 2 0.82 0.73 81.11 17.28
20 3 8.89 7.73 61.60 21.48
20 4 1.64 2.10 66.23 29.90
20 5 1.79 3.40 63.29 31.50
20 6 1.83 4.07 63.41 30.60
25 1 0.52 0.00 18.57 80.91

25 2 0.00 0.00 78.80 20.99
25 3 0.00 0.06 86.10 13.66
25 4 0.07 0.16 79.28 20.21
25 5 0.03 0.17 87.48 12.18
25 6 0.06 0.27 89.57 9.88
30 1 0.23 0.06 20.41 79.29

30 2 0.15 0.00 68.65 31.15
30 3 0.00 0.01 90.16 9.59
30 4 0.00 0.00 88.84 10.97
30 5 0.00 0.00 84.44 15.24
30 6 0.02 0.02 87.96 11.74
35 1 0.09 0.01 22.59 77.30

35 2 0.43 0.00 11.44 88.14
35 3 0.13 0.00 43.67 56.15
35 4 0.00 0.00 72.83 26.68
35 5 0.00 0.00 84.59 14.74
35 6 0.00 0.00 84.66 14.96
Although it was evident that a complex relationship existed among the various
synthesis variables, machine learning approaches offer a potential means to
comprehend the solution chemistry involved.
Importance of Agitation During Hydrothermal Zeolite Synthesis
Four modes of agitation have been described during the synthesis of zeolites (Deneyer
et al., 2020). The first option is to not stir the reactant mixture. Alternatively,
conventional stirring of the reactor can be achieved by placement of a stirrer shaft
vertically in the hydrothermal synthesis vessel. It is noted that various stirrer
configurations are employed to homogenize solutions (Casci, 2005). In a laboratory
setting reactor vessels can also be shaken or tumbled (Yu et al., 2018). In this study
the incubator employed a shaker plate upon which the sample bottles were placed.
Additionally, the reaction mixture was rotated around the central axis of a reactor
vessel. As indicated by Casci (2005), industry mostly conducts zeolite synthesis by
stirring the reactant mixture.
It was essential to analyse the variations in the collected data while synthesizing zeolite
LTA using pre-heated feed solutions and without stirring. (Figure 44). In this example
the feed conditions were pre-heating to 80 oC; SiO2/Al2O3 = 2; Na2O/SiO2 = 2.5;
H2O/SiO2 = 20 to 30; synthesis temperature = 80 oC; reaction time = three hours; no
stirring of reaction mixture. Comparison of the results obtained with the stirred
samples (Table 20) to the static ones (Table 21), revealed that the samples made using
static conditions produced a similar or higher amount of zeolite LTA. Indeed,
especially after a two-hour synthesis period all the samples consisted of > 90 wt%
crystalline zeolite LTA.
The influence of stirring reactant solutions or leaving them static has often been
reported to be a critical factor in making high quality zeolites. For example, Hagio et
al. (2021) found that use of static synthesis conditions facilitated the growth of EAB-
type zeolite in a matter of hours when precisely controlling reaction temperature. In
contrast, previous efforts to synthesise EAB-type zeolite all required many days to
react when employing agitated reactant mixtures. Alternatively, Kubota et al. (2000)
discovered that only with agitated conditions was it possible to make CFI-type zeolite.
It was also noted that when the H2O/Na2O ratio increased from 25 to 30 the shape of
the crystalline zeolite LTA changed from cubes with sharp edges to rounded cubes,
morphology of zeolite crystals changes depending on the synthesis conditions (Bronić
et al., 2012; Zhan, Li, Zhang, Han, & Chen, 2013). Ideal morphology of zeolite LTA
crystals has been described as a sharp edge cube (Zhan et al., 2013). However, Ayele,
et al. (2016a) reported the importance of using cubes with rounded corners as
detergents because of the incrustation of textiles when zeolite LTA with sharp edges
was used. Y. Liu, et al. (2021) produced zeolite LTA with rounded corners using a
microwave hydrothermal method, and they suggested that the high Ca 2+ ion exchange
(335.6 mg CaCO3 g-1) was due the cubic morphology with rounded edges.
100
80
wt% Crystalline
60
Zeolite LTA
Non-diffracting
40
20
0
1 2 3 4 5
Time (hrs)
H2O/Na2O = 25 98.6% Zeolite LTA
100
80
wt% Crystalline
60
Zeolite LTA
40 Non-diffracting
20
0
1 2 3 4 5
Time (hrs)
H2O/Na2O = 30 98.5 Zeolite LTA
Figure 44. Quantitative XRD data for Zeolite LTA: SiO 2/Al2O3 = 2; Na2O/SiO2 = 2.5;
H2O/SiO2 =25 to 30; Reaction Temperature = 80 ℃; pre-heated samples at 80 ℃;
Reaction Time = 3 h; No stirring
Table 19. Summary of quantitative XRD patterns for Zeolite LTA with pre-heated and
non-stirring samples: SiO2/Al2O3 = 2; Na2O/SiO2 = 2.5; H2O/ Na2O = 20 to 30;
Temperature = 80 ℃
wt% wt% wt% wt%

H2O/Na2O Time (h)
Cancrinite Sodalite Zeolite LTA Amorphous
25 1 0.05 0.02 55.85 43.98
25 2 0.35 0.04 97.94 1.63
25 3 0.14 0.04 98.59 1.21
25 4 0.34 0.03 96.88 2.69
25 5 0.11 0.06 96.10 3.66
30 1 0.29 0.04 37.60 62.05

30 2 0.09 0.02 90.35 9.48
30 3 0.07 0.05 98.53 1.22
30 4 0.02 0.06 98.67 1.17
30 5 0.00 0.05 96.26 3.60
Influence of Stirring Methodology as a Function of Varying Na2O/SiO2 and

H2O/Na2O Ratio upon Zeolite LTA Synthesis
Based upon the findings in the previous section where the H2O/Na2O ratio was mainly
changed, it was pertinent to determine if the stirring methodology during zeolite LTA
synthesis was dependent on the Na 2O/SiO2 and H2O/Na2O ratios in the gel
composition. In the first instance the H 2O/Na2O ratio was varied from 20 to 30 and the
Na2O/SiO2 ratio was adjusted to= 2 instead of 2.5). The synthesis temperature was
maintained at 80 oC (pre-heated experiments) and the SiO 2/Al2O3 ratio was 2.
100 100
Crystalline Zeolite LTA%
Crystalline Zeolite LTA%

80 80
60 60
40 40
H2O/Na2O=20 H2O/Na2O=20
20 20
0 1 2 3 4 0 1 2 3 4
Time (hrs) Time (hrs)
Na2O/SiO2=2 - Stirring Na2O/SiO2 = 2- No-Stirring
Figure 45. Quantitative XRD patterns for Zeolite LTA: SiO 2/Al2O3 = 2; Na2O/SiO2 =
2; H2O/ SiO2 = 20 to 30; Temperature = 80 ℃ - pre-heated samples at 80℃
In terms of the solid products formed the only two phases identified were zeolite LTA
and amorphous/non-diffracting material (Table 20). The impact of the water content
in the zeolite made using Na 2O/SiO2 = 2 was significant, regardless of stirring or not
stirring the feed mixture (Figure 45). When H2O/Na2O = 20 the amount of zeolite
LTA decreased as the reaction time was increased from the optimal value of one hour.
This situation was presumably representative of the metastable state of zeolite LTA
under the experimental conditions. In this regard, the stirred solution promoted the
degradation of zeolite LTA compared to the non-stirred solution. Use of stirred and
non-stirred samples when H2O/SiO2 = 25 produced distinct changes in the rate of
zeolite formation. After one hour synthesis at 80 oC the non-stirred reactor produced
a product which was 85 wt% zeolite LTA [Figure 7]. In contrast, the stirred reactant
solution resulted in a significant inhibition of zeolite growth (only 20 wt % zeolite
LTA) due to the solution agitation.
samples and non-stirring: SiO2/Al2O3 = 2; Na2O/SiO2 = 2; H2O/ SiO2 = 20 to 30;
wt%
Synthesis Stirring wt% wt% wt%
H2 O/Na2 O Zeolite
Time (h) (rpm) Cancrinite Sodalite Amorphous
LTA
20 1 100 0.08 0.07 87.42 12.35
20 2 100 0.33 0.55 81.35 17.62
20 3 100 0.42 0.97 75.01 23.55
20 4 100 0.61 1.38 66.62 31.27
25 1 100 0.28 0.00 19.98 79.64

25 2 100 0.00 0.00 86.81 13.09
25 3 100 0.00 0.00 82.23 14.55
25 4 100 0.02 0.01 85.66 14.15
30 1 100 0.33 0.00 5.68 93.96

30 2 100 0.55 0.00 30.25 69.15
30 3 100 0.00 0.01 94.37 5.36
30 4 100 0.00 0.04 96.47 3.22
20 1 0 0.02 0.05 90.31 9.54

20 2 0 0.11 0.05 94.96 4.81
20 3 0 0.12 0.73 84.59 14.40
20 4 0 0.25 1.79 69.63 28.14
25 1 0 0.00 0.03 85.08 14.64

25 2 0 0.00 0.05 93.90 5.95
25 3 0 0.00 0.03 91.05 8.76
25 4 0 0.07 0.00 95.83 3.95
30 1 0 0.54 0.00 15.31 83.97

30 2 0 0.00 0.06 39.86 60.08
30 3 0 0.18 0.09 100.00 0.00
30 4 0 0.07 0.04 97.10 2.65
Samples with H2O/Na2O = 30 needed at least three hours to reach 94 wt% and 100
wt% zeolite LTA crystals for stirring and static samples, respectively. Whether stirred
or non-stirred solutions were employed, the zeolite LTA content was highest for the
H2O: SiO2 ratio was 30.
Figure 46 shows SEM images between stirred and non-stirred samples when the ratio
of H2O/SiO2 was 30. In the initial stages of reaction, the product was clearly a mixture
of non-diffracting and crystalline material (in accord with Table 20). After three hours
of reaction both the stirred and non-stirred samples exhibited the dominant presence
of crystalline zeolite LTA (Figure 46). When stirring was applied during the reaction
to make zeolites the size and shape of the stirred sample was evident.
Indeed, the zeolite crystals were not only larger but also formed of sharp edges. This
observation was in agreement with Andaç et al. (2005) and Palcic et al., (2012), who
mentioned the benefit of agitation for the formation of zeolite phases and crystal
growth. In contrast, when the synthesis mixture was not stirred the zeolite LTA was
smaller in size and comprised of rounded edges on the crystals. When comparing the
data in Table 19 with Table 20, the reduction of Na2O/SiO2 to 2 appeared to mainly
inhibit the growth of zeolite LTA at short reaction times of one to two hours.

When used as a detergent builder several physical properties of zeolite LTA are
important. The particle size distribution is critical in relation to zeolite LTA
effectiveness to soften water. If the zeolite crystals are > 10 microns then the rate of
calcium/magnesium ion exchange is limited by diffusion considerations (Pastorello &
Troglia, 1987). In addition, these larger zeolite grains may deposit on clothing and/or
cause problems with blocking of pipes in laundry machines. Alternatively, zeolite
LTA with a particle size < 1 micron may promote matting of clothing material due to
excessive permeation into the fabric.
Figure 47 shows the light scattering data for the zeolite LTA samples illustrated in
Table 20 and Figure 46. In general, two features were present, namely a broad
distribution assigned to amorphous and/or agglomerated material, or a sharp profile at
lower size classes which presumably corresponded to the formation of crystalline
zeolite LTA. Development of zeolite LTA crystals was promoted using static
solutions in agreement with the data in Figure 45 and Table 20. The broadening
observed even with the samples with the highest crystallinity suggested that the zeolite
LTA crystals were aggregated. For example, Table 21 shows that for the zeolite LTA
made using H2O/Na2O =30 and no stirring for four hours, that 90 % of the particles
were less than 11.2 microns and 50 % were less than 5.4 microns. In relation to its use
as a detergent, in the zeolite LTA only 10 % of zeolite crystals were less than one
micron in size.
STIRRING 100 rpm NO-STIRRING
1h Synthesis - 5.7% Zeolite LTA 1h Synthesis -15.3% Zeolite LTA
2h Synthesis - 30.3% Zeolite LTA 2h Synthesis - 39.9% Zeolite LTA
3h Synthesis - 94.4% Zeolite LTA 3h Synthesis - 100% Zeolite LTA
4h Synthesis - 96.5% Zeolite LTA 4h Synthesis - 97.1% Zeolite LTA

Figure 46. Formation of zeolite LTA crystal over time at 80 oC with preheated samples;
H2O/Na = 30, Na 2O/SiO2 = 2, SiO2/Al2O3 = 2
8 8
1h Synthesis 1h Synthesis
2hrs Synthesis 2hrs Synthesis
Volume Density (%)
Volume Density (%)

6 6
4 4
2 2
0
0
0 20 40 60 80 100 120
0 20 40 60 80 100 120
Size Classes (um)
Size Classes (um)
H2O/Na2O=20 - 100 rpm H2O/Na2O=20 – 0 rpm
8 8
Volume Density (%)
Volume Density (%)
6 6
4 4
2 2
0
0
0 20 40 60 80 100 120
0 20 40 60 80 100 120
Size Classes (um)
Size Classes (um)
H2O/Na2O=25 – 100 rpm H2O/Na2O=25 – 0 rpm
8 8
1h Synthesis
1h Synthesis 2hrs Synthesis
Volume Density (%)
4hrs Synthesis 6
Volume Density (%)
4
4
2
2
0
0 0 20 40 60 80 100 120
0 20 40 60 80 100 120
Size Classes (um)
Size Classes (um)
H2O/Na2O=30 – 100 rpm H2O/Na2O=30 – 0 rpm
Figure 47. Particle Sizing for zeolite LTA: SiO 2/Al2O3 = 2; Na2O/SiO2 = 2; H2O/Na2O
= 20 to 30; temperature = 80 ℃ - pre-heated samples at 80 ℃
Table 21. Summary of particle sizing analysis for Zeolite LTA with pre-heated
samples and no-stirring: SiO2/Al2O3 = 2; Na2O/SiO2 = 2; H2O/ SiO2 = 20 to 30;
Stirring Reaction Time Particle Sizing Volume Density
H2 O/Na2 O
(RPM) (hours) Dx (10) Dx (50) Dx (90)
20 100 1 0.69 5.89 26.7
20 100 2 0.91 8.80 33.7
20 100 3 0.84 9.84 38.2
20 100 4 1.47 14.1 46.7
25 100 1 7.26 30.9 74.6
25 100 2 1.05 10.4 42.6
25 100 3 2.38 13.7 39.5
25 100 4 0.86 6.76 21.1
30 100 1 10.1 26.6 56.3
30 100 2 8.29 28.6 62.0
30 100 3 1.28 7.31 25.9
30 100 4 1.01 5.18 15.8
20 0 1 0.63 4.50 33.8
20 0 2 0.66 6.61 35.2
20 0 3 0.94 14.7 57.7
20 0 4 1.05 8.99 37.2
25 0 1 1.17 11.7 46.8
25 0 2 0.98 7.43 30.1
25 0 3 0.85 6.56 32.1
25 0 4 0.87 4.02 11.2
30 0 1 10.3 28.6 61.2
30 0 2 9.49 29.7 68.7
30 0 3 0.72 3.24 16.7
30 0 4 1.02 4.52 11.2
Therefore, the inclusion of zeolite particle sizing data appears to be amenable to
machine learning approaches if a range of particle sixing volume density values are
employed.
Machine Learning Insights
In terms of machine learning data sets, one approach involves automated extraction of
relevant data from published journals (Kim et al., 2017). The fundamental strategy is
to convert human readable text to machine-readable text using a combination of trained
machine learning and natural language extraction algorithms. When applied to
relevant articles a database is compiled which can then be filtered to give materials
synthesis guidance. For example, Jensen et al. (2019) extracted data relevant to
germanium containing zeolites. The machine learning approach successfully
illustrated the relationship between zeolite synthesis parameters and the framework
density of germanium containing zeolites. However, it was also evident that there was
considerable scatter in the data points mined from a range of publications. This
observation is supported by the results of this study which has revealed the difficulties
in trying to use data from other research organizations.
Thus, when trying to optimize zeolite synthesis using machine learning methods an
inherent challenge is the need to work with small data sets (Y. Zhang & Ling, 2018).
Automated extraction of data from published sources can significantly expand the data
set size but the downside is that errors in the data can occur due to all the reasons
illustrated in this investigation. Moreover, collection of all the necessary data to
improve the machine learning model is often not performed by the researchers.
Adjiman et al. (2021) highlighted the need to integrate process engineering concepts
in the macroscale to fundamental science at the nanoscale. This study for example
examined the macroscale impact of stirring or not stirring solutions. Despite the
favourable synthesis of zeolite LTA with no stirring during hydrothermal treatment
process, constraints evolve on the macroscale in terms of keeping the vessel contents
homogeneous in character.
Application of the data in this study to a machine learning investigation of zeolite LTA
synthesis has subsequently been shown to be informative (Conroy et al., 2022). The
data set was interrogated by a range of machine learning algorithms from the basic to
more advanced: linear regression, ridge regression, regression tree, random forest,
XGBoost and artificial neural network (ANN) models. Simpler models were
characterized by an R2 value of approximately 0.5 whereas tree-based models
increased R2 to between 0,6 and 0.7 R2. However, use of an ANN model was highly
successful as shown by the R2 value of 0.84. Although the data suggested that a deep
neural network (DNN) approach may further improve the fitting accuracy, the
learnings from the small data set agreed with known chemistry of zeolite LTA
synthesis.
Conclusions
This study has shown that it is challenging to create data sets for synthesis of zeolite
LTA which are suitable for machine learning. A critical method for zeolite
characterization is XRD yet the number of publications using quantitative XRD
methods is very limited. It is acknowledged that a greater amount of effort is required
to obtain quantitative XRD patterns due to the need for an internal standard and more
complex data processing. However, data science methods need comprehensive
structural information if credible predictions are to be made.
Mass balance of processes is fundamental to the chemistry of zeolite synthesis and this
approach ultimately provides more extensive data to interpret. The fate of unreacted
species such as sodium hydroxide is not only important for process economics but also
for promotion of subsequent zeolite synthesis.
A key hindrance to data uniformity is the influence of the dimensions and design of
hydrothermal vessels upon zeolite synthesis. Researchers need to be aware that
heating rates, sample temperature profiles (lower/high temperatures than targeted) and
cooling rates all vary between reactor types. This fact makes it difficult to compare
data with that reported in other publications by different research teams.
Pre-heating of reactant solutions is recommended to minimize the variation in reaction
temperature upon zeolite synthesis. Although reported in industry this suggestion has
not been widely adopted in the research literature.
No agitation of the reactant mixture under hydrothermal synthesis conditions was
shown to increase the quality of zeolite LTA. However, when scaling-up zeolite
production it is usually necessary to stir the large vessels involved to enhance
homogeneity of the solutions or slurry.
Subsequent application of machine learning principles validated the usefulness of even
a small dataset in predicting zeolite synthesis outcomes. Therefore, it is recommended
that researchers should capture more data during zeolite synthesis and follow the
lessons from this study.
Key Insights
This chapter has emphasized the challenges involved in creating suitable datasets for
machine learning in the synthesis of zeolite LTA and proposes solutions to address
these challenges. The limited use of quantitative X-ray diffraction (XRD) methods in
published literature, the lack of reporting of the mass balance of processes, and the
impact of vessel dimensions and design on the synthesis process are identified as
critical factors that need to be considered. The chapter recommends pre-heating of
reactant solutions to minimize variation in reaction temperature and avoiding agitation
of the reactant mixture to improve the quality of zeolite LTA. Comparing zeolite
synthesis parameters between laboratories is inherently difficult, and using web
crawling approaches to mine data is impractical due to bias in the collected
information. However, addressing these issues can lead to meaningful results in a
researcher's laboratory.
The next chapter will test the dataset created in this chapter using a progressive
machine learning methodology. The aim is to identify the relationship between zeolite
synthesis descriptors and evaluate the potential for machine learning to predict the
quantitative output of synthesis routes. The hypothesis is that by applying statistics
and machine learning principles, it may be possible to enable pre-evaluation and
increase zeolite yield and performance. The chapter will apply various machine
learning algorithms to zeolite LTA synthesis data, including linear regression, ridge
regression, regression tree, random forest, XGBoost, and artificial neural network
models.
Chapter 7: Evaluation and application of machine learning
principles to Zeolite LTA synthesis
Bethany Conroy1, Richi Nayak2, Andrea Lucia Hidalgo Rocha 1, and Graeme J.
Millar1
1. School of Mechanical, Medical & Process Engineering, Science and
Engineering Faculty, Queensland University of Technology (QUT),
Brisbane, Queensland, Australia.
2. School of Computer Science, Faculty of Science, Queensland University of
Technology (QUT), Brisbane, Queensland, 4000, Australia
* Corresponding author. E-mail: graeme.millar@qut.edu.au
Published (2022): Microporous and Mesoporous Materials, Volume 335.

DOI: https://doi.org/10.1016/j.micromeso.2022.111802
This chapter is a copy of the journal paper published.
Chapter 7: Evaluation and application of machine learning principles to Zeolite LTA synthesis
173
Statement of Contribution of Co-Authors for Thesis by Published Papers
The authors listed above have certified that:
They meet the criteria for authorship in that they have participated in the conception,
execution, or interpretation, of at least that part of the publication in their field of
expertise.
They take public responsibility for their part of the publication, except for the
responsible author who accepts overall responsibility for the publication.
There are no other authors of the publication according to these criteria.
Potential conflicts of interest have been disclosed to (a) granting bodies, (b) the editor
or publisher of journals or other publications, and (c) the head of the responsible
academic unit, and
They agree to the use of the publication in the student’s thesis and its publication on
the QUT’s ePrints site consistent with any limitations set by publisher requirements.
Title of the publication:
Evaluation and application of machine learning principles to Zeolite LTA
synthesis
Status of the publication: Published
174
Abstract
A progressive machine learning methodology was utilised to not only identify the
relationship between zeolite synthesis descriptors but also evaluate the potential for
machine learning to predict the quantitative output of synthesis routes. The hypothesis
was if statistics and machine learning principles are applied, then it may enable pre-
evaluation and result in potential increases to zeolite yield and performance. Various
machine learning algorithms were applied to zeolite LTA synthesis data, including
linear regression, ridge regression, regression tree, random forest, XGBoost and
artificial neural network models. Major findings included the use of input synthesis
variables and the product yield for model training. Additionally, the use of both
quantitative and qualitative X-ray diffraction (XRD) data was required to accurately
determine product composition ("hybrid XRD" approach). Models, including linear
regression, ridge regression and regression trees, returned R2 values less than 0.5
indicating the complexity inherent with the problem. Embedded tree-based models,
including random forest and XGBoost, resulted in testing accuracies equal to R2
=0.620 and R2 = 0.700, respectively. An ANN model achieved the highest accuracy
among all machine learning algorithms of R2 = 0.84. Notably, this model was the most
accurate because it exploited non-linear and complex relationships within a
multidimensional and intercorrelated dataset such as that obtained from zeolite
synthesis. Despite reaching an accuracy greater than 80%, the ANN model accuracy
continued to increase by increasing the network size, indicating that advanced deep
learning models should be considered as part of future work.
Keywords: Zeolite Synthesis; Artificial Neural Network; Data; Machine Learning;

Principal Component Analysis.
175
Introduction
Zeolites are used in many industrial applications, including petroleum refining
(Alkhlel & de Lasa, 2018), water treatment ( Millar, Couperthwaite, et al., 2016; Wen
et al., 2018), gas adsorption (Poursaeidesfahani et al., 2019), agriculture (Nakhli, et
al., 2017), animal feed additives (Valpotic, 2017) and green chemistry (Y. Li, Li, &
Yu, 2017; Lima et al., 2019). At present, over 200 natural and synthetic zeolite
structures have been recorded, with zeolite LTA, X, USY, mordenite, Beta and ZSM-
5 being the most widely used (Collins, et al. 2020). The synthetic zeolite market is
projected to grow by 2.6 % between 2018 and 2023 to reach a value of USD 5.9 million
per annum (Y. Dong, Lin, & He, 2017).
Numerous factors impact the zeolite synthesis mechanism, product quality, yield, and
performance (Cundy & Cox, 2005). Thus, zeolite synthesis is an increasingly
complicated, multidimensional problem (Moliner et al., 2019). Machine learning is
of increasing interest to the zeolite community as it employs mathematical models that
learn from past data to extract patterns and intervariable relationships within a dataset
(Figure 48). The ability to map intricate behaviours (semi-)autonomously using
machine learning enables the materials science field to progress in the absence of
comprehensive knowledge of advanced mechanisms (Moliner et al., 2019).
176
Figure 48: Histogram showing citations of publications with the keywords "machine
learning AND zeolite", "neural network AND zeolite", and "principal component
analysis AND zeolite".
Current research relating to machine learning and zeolite science includes
characterisation and structure discovery for petrochemical cracking and gas adsorption
(Xiao et al., 2020). Another example is the study by Jensen et al., (2019) which
utilised data mining techniques to extract and compile a database of zeolite synthesis
routes. Zeolite literature has often used machine learning to predict the ideal physical
characteristics of zeolites but has not yet predicted the synthesis routes required to
obtain these characteristics (Jensen et al., 2019; Moliner et al., 2019; Muraoka, Sada,
Miyazaki, Chaikittisilp, & Okubo, 2019; Xiao et al., 2020). Studies have used
machine learning algorithms to understand relationships between the synthesis
descriptors to predict the qualitative rather than the quantitative output (Jensen et al.,
2019; Moliner et al., 2019; Muraoka et al., 2019; Xiao et al., 2020).
177
Understanding the data, intervariable relationships, and correlations is paramount in
multidimensional problems. Principal Component Analysis (PCA) is an unsupervised
machine learning technique that utilises statistical methodologies to reduce
dimensionality (Jolliffe, 2002). PCA identifies variables of high and low influence in
a dataset through projection analysis, allowing the removal of redundant features to
improve learning efficiency and reduce computational cost (Jolliffe, 2002). For
example, Conterosito et al. (2020) utilised PCA and correlation analysis on parameters
obtained from Rietveld refinement to heighten relationships present in the CO 2/Xe
sorption data on Zeolite Y .
For systems modelled using regression machine learning, the use of regression trees
and random forest models to predict the physical properties of synthesised zeolites has
been documented. Jensen et al. (2019) used literature extracted data to develop a
random forest regression model that predicted the zeolite framework density from
features including the Silicon, Germanium, Aluminium, Hydroxide, and water content,
as well as reaction time and temperature. The study found the model accuracy to be
R 2 = 0.7 (Jensen et al., 2019). Alternatively, (Muraoka et al. (2019) trained
classification models to predict the resultant zeolite using the same dataset, including
the framework density. The results showed that the Extreme Gradient Boosting
(XGBoost) model outperformed all other models with a 75 to 80 % test accuracy
(Muraoka et al., 2019). In contrast, Moliner et al. (2019) utilised Artificial Neural
Networks (ANN) to predict internal relationships between the zeolite synthesis
descriptors. However, each publication lacks transparency when reporting how these
models have been constructed, trained, and tested to obtain these results.
178
Artificial Neural Networks (ANN) (Figure 49) are non-linear systems that model
complex multidimensional relationships through a series of nodes and connections
reminiscent of a biological brain (Moliner et al., 2019). While ANNs have been used
previously in zeolite science, as shown by Moliner et al. (2019), few studies have
ventured further in model complexity, for example, applying advanced deep learning
techniques. Deep Neural Networks (DNN) provide a greater ability to solve complex
problems and identify hidden patterns and relationships within multivariate datasets
using multiple network layers between the input and output (Figure 49). While the
tools required to implement DNN are available, the lack of sufficient data in zeolite
synthesis applications raises the question of whether DNN should be applied.
Figure 49. Visualisation of the different neural network structures (ANN left, DNN
right).
Zeolite LTA (Na12 [(AlO2 )12 (SiO2 )12 ] ⋅ 27H2 O is widely used in industry (Collins et
al., 2020) and obtained by hydrothermal synthesis of aluminosilicate gels (Cundy &
Cox, 2005).
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Fundamental synthesis parameters which impact the formation of zeolite LTA include
the SiO2 /Al2 O3, Na2 O/SiO2 , H2 O/Na2 O molar ratio, reaction time and temperature
(De Silva et al., 2007). In addition, a range of operational factors impact the plant
performance and physical characteristics of zeolite LTA such as: identity of
silica/aluminium sources; pre-heating of reactants; order/rate of mixing of reactants;
aging of the gel; vessel configuration/size; heating ramp rate to attain reaction
temperature; impact of mother liquor recycling; cooling rate of zeolite sludge product;
and washing stage to remove unreacted species and reduce solution pH (Collins et al.,
2020). Ultimately, the best synthesis approach and associated manufacturing plant
design should produce zeolites of the highest quality (purity; particle size), greatest
amount (yield), and at the lowest cost (minimise utility and chemical consumption;
optimal plant design). Environmental aspects are also important, especially
wastewater production in the zeolite synthesis process.
The complexity of zeolite LTA synthesis combined with the substantial literature on
this topic suggests that it may be an ideal test case to demonstrate the methodology,
outcomes, and benefits of employing a machine learning approach. At present, there
are some excellent publications that have used machine learning to identify synthesis
conditions to make zeolites (Moliner et al., 2019). Yet, the relationship between
synthesis descriptors and the product zeolite remains a challenge ( Muraoka et al.,
2019). Therefore, the aim of this study was to apply machine learning principles to
zeolite LTA synthesis to enable the pre-evaluation and testing of zeolite synthesis
routes. A key outcome was improved approaches to model development and training,
which enable the development of high performing machine learning models.
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The hypothesis was: "If machine learning principles can be applied to zeolite LTA
synthesis, then it may be used to predict the success of laboratory synthesis routes
enabling pre-evaluation and potential increases to zeolite yield and performance of
zeolite products." This study addressed the following research questions to support this
hypothesis: (1) Is the zeolite synthesis data sufficiently robust for machine learning
applications? (2) Which experimental variables should be included when developing
machine learning algorithms? (3) Can a feature transformation technique simplify the
data, or are the transformed factors too intercorrelated? (4) What is the preferred
machine learning approach which can be most accurately applied to zeolite LTA
synthesis? In terms of methodology, a dataset comprising of 25 features and 130
instances was generated at laboratory scale for zeolite LTA synthesis.
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Machine Learning
The goal of machine learning is to predict the output of the zeolite synthesis system
using the input attributes. The application of machine learning to zeolite LTA synthesis
followed the knowledge discovery process depicted in Figure 50.
Figure 50. Knowledge discovery process.
The application of machine learning used a development pipeline, which followed the
logical progression and application of varying machine learning techniques according
to complexity from PCA, linear regression, tree-based models to ANN. PCA is an
unsupervised machine learning technique. All other techniques applied to the data
formed part of a supervised machine learning approach governed by the relationship
f (x) = y in a continuous space. In f(x) = y, x is a vector populated with input values
corresponding to those of the zeolite synthesis system, and y is the continuous output
of the system, the zeolite yield. The underlying machine learning task is learning the
function f according to the algorithm used based on the training data in the form of
(x, y).
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Progression of Machine Learning Technique Application
A progressive approach to applying machine learning models to the zeolite synthesis
data was taken to better understand the complexity of the zeolite synthesis system. As
a result, various machine learning models were developed following the logical
progression and application of machine learning techniques according to complexity,
as shown in Figure 51.
PCA Linear Regression Regression Tree & Artificial Neural

Random Forest Networks
• Exploratory • Basic machine • Produce a • Enable hidden

statistics and learning models decison tree patterns and
analysis used to based correlations to
technique. determine the predictive be identified.
• Used to baseline error. model. • Ability to train
understand • Enables • The models use and re-train
correlations assessment of cross-validation models. The
and data suitability to optimise models
distributions for further parameters and continuously
present in the regression avoid learn and
data. machine overfitting. improve.
learning. • Application of
gradient
boosting using
XGBoost.
Figure 51. Progression and application of machine learning techniques according to

complexity.
Utilising a progressive approach enabled observations about the progression of
machine learning accuracy with model complexity to be quantified. It is conjectured
that if the machine learning accuracy no longer increases with increasing model
complexity, then at this point, the complexity of the machine learning model and the
zeolite synthesis problem are equal. Significantly, the transparency of each machine
learning model reduces with increasing complexity. Leading up to ANN, the ability
to view model parameters and understand the feature importance of each model greatly
reduces.
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Principal Component Analysis
PCA uses the intercorrelation of variables to find a new set of uncorrelated variables
with reduced dimensionality termed principal components (PC) (Corma et al.,2005).
PCA was used to achieve a lower-dimensional representation of the zeolite synthesis
data while preserving relationships and correlations present in the original dataset with
minimal information loss (Jolliffe, 2002).
PCA was applied to gain a greater understanding of multidimensional data by
visualising it in a space of reduced dimensionality. PCA was performed on
standardised data to ensure scaling differences between variables did not influence
observed patterns and trends. The PCA algorithm was implemented by following the
equations derived in the supplementary documentation. MATLAB functions were
used to implement PCA, including standardising data and calculating the singular
value decomposition (SVD). In addition, MATLAB was used to visualise the variance
explained, PC coefficients and projection onto the PC.
Initialising the Data, Training and Test Sets

Before implementing and training the machine learning models, the zeolite synthesis
data was imported into Python. The data was split into training and test datasets using
the scikit-learn (sklearn) package, ensuring the models were always tested and
evaluated on unseen data (Pedregosa et al., 2011). The data was split such that 80 %
was used for training and validation and 20 % for testing. Continuous features in the
dataset were standardised prior to training the models.
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Linear, Ridge, Regression Tree , and Random Forest Regression Models
The sklearn package was used to implement the linear regression, ridge regression,
regression tree and random forest models in Python (Pedregosa et al., 2011). Ten-fold
cross-validation was used to train the models and optimise the hyperparameters
through a grid search of the candidate values presented in the supplementary
documentation. The models were trained using the sklearn fit estimator. For ridge
regression, cross-validation was applied to obtain the optimal alpha parameters. The
random forest regressor utilised bagging to create multiple regression trees combined
to give the random forest.
XGBoost
The XGBoost package was used to implement an XGBoost regression model in Python
(T. Chen & Guestrin). Ten-fold cross-validation was used to train the model and
optimise the hyperparameters through a grid search of the candidate values presented
in the supplementary documentation. The model was trained using the fit estimator.
Artificial Neural Network

The ANN models have been implemented in two ways using sklearn and PyTorch.
One model utilised the multilayer perceptron (MLP) regressor through the sklearn
neural network package (Pedregosa et al., 2011). Another model implemented ANN
using Skorch and the Adam optimiser from PyTorch (Paszke et al., 2019), assisted by
various sklearn functions from the model selection and pre-processing packages
(Pedregosa et al., 2011). The MLP regressor was implemented using ten-fold cross-
validation to train the model and optimise the hyperparameters through a grid search
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of the candidate values presented in the supplementary documentation. The network
was trained using the sklearn fit estimator by minimising the cost function.
The manual implementation of ANN in PyTorch provided greater control over the
model architecture. The model utilised 10-fold cross-validation during training,
introducing a third data split for validation. The model was trained and optimised
using the Adam optimiser from PyTorch. For each iteration within a cross-validation
fold, the model carried out forward propagation training by calculating the training and
validation losses and checked for convergence to the tolerance value as part of the
early stopping criteria. Finally, the model applied backpropagation to optimise the
model weights. At the end of cross-validation, the best model and associated weights
were returned for prediction and testing of the neural network.
Approaches to Model Evaluation

After training, the predict method from sklearn was utilised to determine the predicted
feature values ŷ. The true and predicted values were compared to evaluate the model
accuracy. All models were evaluated using the coefficient of determination,
R 2Through the sklearn metrics package (Pedregosa et al., 2011). The R 2 value
represented the proportion of variance from the original data explained by the
independent variables predicted by the machine learning model. The R 2 metric
provided an indication of the model's fit to the original data and, therefore, how well
novel features were likely to be predicted by the model through the proportion of
explained variance. The sklearn metrics package r2_score function used Equation 17,
1
where: y̅ = ∑ni=1 yi.
n
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∑𝐧 ̂ 𝐢) 𝟐
𝐢=𝟏( 𝐲𝐢−𝐲
Equation 17: 𝐑 𝟐 (𝐲, 𝐲̂) = 𝟏 − ∑𝐧 ( ̅)𝟐
𝐢=𝟏 𝐲𝐢−𝐲
The models were trained, tested, and evaluated five times using a different train/test
split such that the average R 2 value with a ± tolerance relative to the minimum and
maximum R 2 value was obtained. The R 2 values for each individual training and
testing run are provided in the supplementary documentation.
Input Variables Selection and Zeolite LTA Synthesis Data

A clean dataset with sufficient instances of data was required to train the machine
learning models successfully. A dataset consisting of 25 features and 130 instances
was obtained from the laboratory synthesis of zeolite LTA from aluminosilicate gels.
An initial gel was created and subsequently reacted hydrothermally at 80 oC. Given
the number of features, the data is multidimensional and requires refining before
training. The "hybrid 10" (see Section “Synthesis of Zeolite LTA from Aluminosilicate
Gels”, below) data was used to train the machine learning models to predict the success
of various zeolite LTA synthesis routes as mass yield or wt% of zeolite LTA. To
prevent false predicting variables from dominating the models, all output product
values were removed from the dataset. The variables included in the input data are
displayed in Table 22.
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Table 22. Machine learning input variables.
Variable Units Minimum Maximum Average
Water g 16.19 46.39 29.63
Sodium Silicate g 7.45 12.95 11.46
𝑵𝒂𝑶𝑯 g 2.44 4.89 4.43
Water Temperature ℃ 21.00 77.00 48.81
𝑵𝒂𝟐 𝑶/𝑺𝒊𝑶𝟐 Molar 2.00 2.50 2.41
Ratio
𝑯𝟐 𝑶/𝑵𝒂𝟐 𝑶 Molar 15.00 42.00 26.46
Ratio
Aging Time h 0.00 0.50 0.23
Stirring Speed RPM 0.00 100.00 33.08
Reaction Time h 0.50 6.00 3.06
Zeolite LTA g 0.00 8.93 5.70
Zeolite Characterization
X-Ray Diffraction (XRD)
A Panalytical X'Pert wide-angle X-ray diffractometer equipped with Co Kα radiation
(1.7903 Å) was employed to determine the components of the zeolite product. Every
0.02° XRD traces were recorded over the range of 5 to 90° 2θ (30 seconds per step).
Quantitative XRD analysis was achieved by implementing a 10 wt% corundum
internal standard. Quantitative XRD data was analysed by TOPAS v5 software using
the Rietveld method. Qualitative XRD analysis simply compared the relative intensity
of peaks due to crystalline components present in the zeolite sample.
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The presence of zeolite LTA and amorphous material was determined by a JEOL
7001F Scanning Electron Microscope (SEM). Zeolite samples for SEM analysis were
arranged by placement on carbon tape followed by platinum coating. Images were
acquired by using an accelerating voltage of 5 kV.
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Synthesis of Zeolite LTA from Aluminosilicate Gels

Figure 52 illustrates the general chemistry of zeolite LTA manufacturing and the
impact of synthesis parameters, particularly reaction time. It is noted that the figures
below represent a small subset of the larger database of experimental data used for
machine learning. Using a gel composition of SiO2 /Al2 O3 = 2, Na2 O/SiO2 = 2.5 and
H2 O/Na2 O = 30, zeolite LTA was synthesised at a reaction temperature of 80 ℃
(Figure 52). Quantitative XRD data indicated that there was an initial induction period
where the product was primarily amorphous/unidentified. However, once the reaction
time was increased to two hours, the amount of crystalline zeolite LTA rapidly
increased to approximately 70 wt%. Correspondingly, the amorphous/unidentif ied
content decreased in harmony with the general zeolite growth stages shown in
Supplementary Figure 7
Figure 52. Zeolite synthesis products for gel composition of SiO2/Al2O3= 2,

Na2O/SiO2= 2.5 and H2O/Na2O = 30; reaction temperature 80 oC.
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The maximum zeolite LTA content of ca. 70 wt% was significantly less than expected
compared to previous literature, which reported amounts of crystalline zeolite LTA as
high as 99 wt% (Deabriges, 1982). Therefore, the H2 O/SiO2 ratio was varied while
keeping all other parameters constant to determine if the amount of zeolite LTA could
be improved (Figure 53).
Figure 53. Zeolite synthesis products as a function of reaction time for gel composition
of SiO2/Al2O3 = 2, Na2O/SiO2= 2 and H2O/Na2O = 20 to 30; reaction temperature 80
oC.
It was observed that lower H2 O/Na2 O values accelerated the formation of zeolite
LTA, albeit at H2 O/Na2 O = 20, the metastability of zeolite LTA was noted as the
amorphous/unidentified content increased with reaction time. Regardless of the
H2 O/Na2 O molar ratios, the crystalline amount of zeolite LTA did not grow higher
than 75 wt%. Consequently, SEM imaging was performed to investigate the reason
for the limited zeolite LTA formation (Figure 54).
After one hour of synthesis, SEM imaging revealed a mixture of amorphous material
and some zeolite LTA (cubic crystals). This data agreed with the quantitative XRD
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data in that 2.7 wt% zeolite LTA was detected. Increasing the reaction time to two
hours promoted the formation of zeolite LTA as numerous crystals of relatively small
size (< 1 micron), and the quantitative XRD results suggested that the quantity of
crystalline zeolite LTA was 21 wt%. The quantitative XRD results may have under-
reported the zeolite LTA content due to line broadening, which is particularly
prevalent as zeolite particle size decreases (Raic et al., 2020; Strachowski et al., 2021).
In turn, this leads to the Rietveld analysis erroneously predicting the presence of
amorphous and un-identified materials. Accordingly, as shown in Figure 53, optimal
zeolite LTA formation occurred at a reaction time of three hours for a H2 O/Na2 O ratio
of 30. Quantitative XRD suggested that at 3- and 4-hours reaction time, 71 and 72
wt% zeolite LTA was present. However, the presence of significant amounts of
amorphous material was absent in the SEM images.
Consequently, a qualitative XRD approach which is common in the zeolite literature
and does not account for non-diffracting species was applied to the data. Results
indicated a quantity of crystalline zeolite LTA of 99 wt% for the 3- and 4-hour
synthesis times with a H2 O/Na2 O ratio of 30 as shown in Figure 53.
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1h synthesis - 2.7 % Zeolite LTA 2h synthesis – 21 % Zeolite LTA
3h synthesis – 71 % Zeolite LTA 4h synthesis – 72 % Zeolite LTA
Figure 54. SEM images of zeolite synthesis products as a function of reaction time
for gel composition of SiO2/Al2O3 = 2, Na2O/SiO2= 2 and H2O/Na2O = 30; reaction
temperature 80 oC.
When applying machine learning, the quality of the input data is important, especially
when using relatively small datasets (Y. Zhang & Ling, 2018). In theory, quantitative
XRD analysis should provide more accurate data for machine learning (Hanson et al.,
2021).
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However, as can be seen from Figure 52, Figure 53 and Figure 54, quantitative and
qualitative XRD analysis were both required to explain the experimental data.
Therefore, a new idea was developed to integrate both quantitative and qualitative
XRD approaches. In the early stages of zeolite LTA synthesis, a quantitative XRD
method is required to account for the presence of amorphous species. On the other
hand, at higher levels of zeolite LTA formation, the use of qualitative XRD seems
appropriate as the presence of amorphous and other non-diffracting material was
expected to be minimal. This new methodology for interpretation of XRD data in
relation to use with machine learning studies has been termed a "hybrid XRD
approach". The remaining challenge is to specify at which point in the zeolite growth
curve quantitative and qualitative XRD methods should be applied to generate the most
accurate dataset. Thus, data analysis was employed in situations where the crystalline
content of zeolite LTA was < 10, < 20 and < 40 wt%. For example, a "hybrid 10"
approach (i.e., crystalline zeolite content < 10 wt%) was initially utilised to provide
data for machine learning techniques to determine the most suitable model for zeolite
LTA synthesis.
Application of Chemometrics to Zeolite LTA Synthesis Data

Following the progression of machine learning technique application, PCA was
conducted and applied to the selected zeolite LTA synthesis data. The correlation
between chosen variables for machine learning is shown in Figure 55.
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Figure 55. Correlation of machine learning variables using hierarchical clustering
methods.
From Figure 55, the highest correlation was observed between the following variables:
(1) NaOH and Na2 O/SiO2 with a correlation value of 1; ( Millar, Couperthwaite, et
al., 2016) water and H2 O/Na2 O with a correlation value of 0.95; and water temperature
and aging time with a correlation value of -0.98 (Wen et al., 2018). The relationships
between NaOH, Na2 O/SiO2 and water, H2 O/Na2 O were expected results given the
relationship between input chemicals to the system and the calculated ratios that
influence zeolite synthesis. The similarity of the NaOH and Na2 O/SiO2 correlations in
Figure 55 revealed that one is a redundant variable. Given the importance of the
Na2 O/SiO2 ratio demonstrated in literature (De Silva et al., 2007) NaOH was removed
from the dataset. Other trends of interest included the correlation between the stirring
speed, sodium silicate and aging time.
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While there were some clear correlations indicated by correlation values close to one
and negative one, all other variables indicated some level of intercorrelation. Most of
the variables had a correlation value greater than |0.2|. Given the multidimensiona lit y
and collinearity of the zeolite synthesis data, PCA was utilised to obtain a lower-
dimensional representation of the data. This situation enabled simpler data
visualisation to identify trends and develop a greater understanding of the data. The
PCA returned nine components equal to the number of variables in the machine
learning dataset. The importance of each PC was determined by visualising each PC's
variance, as shown in Figure 56a.
(a) (b)
Figure 56. (a) Variance explained by principal components (b) principal component
coefficients.
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From Figure 56a, the first five PCs explained greater than 90 % of the variance in the
data. The first four PCs explained greater than 85 %, with PC 1 explaining 40 % of
the variance and PC 2, 3 and 4 explaining 20, 14 and 11 %, respectively. PCs 5 to 10
each explained less than 10 % of the data. This result suggested that only 4 out of 10
PCs significantly influenced the patterns observed in the data. Therefore, PC 1, 2, 3
and 4 were retained for further analysis. The constituents of the first four PC are
visualised in Figure 9b.
Figure 56b showed that each variable contributed at least in part to the first four PCs.
This conclusion affirmed trends observed within the correlation plot and confirmed
the high degree of intercorrelation and multi-collinearity in the data. The coefficients
also confirmed that the variables retained for machine learning all, to a degree,
influenced the result of a zeolite synthesis route.
The relationship between the first four PCs were also visualised in Figure 57 as a
biplot. The biplot displays vectors representing each variable that point away from the
origin to the value assigned by PCA. The plot visualised the values assigned to each
of the PCs for each dataset area. When analysing the biplot, the factors considered
included the length of the vectors and the angle between vectors. The length of the
vector evaluated the representation of the variable by the plot and vice-versa. Longer
vectors indicated a greater representation. Additionally, the size of the angle in
between vectors indicated the correlation. Small angles represented a strong positive
correlation, 90-degree angles indicated no correlation, and 180-degree angles implied
a negative correlation.
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Figure 57. Biplot comparison of principal components 1, 2, 3 and 4.
The variables labelled in Figure 57 corresponded to the largest coefficients in the first
four PCs. Visualisation of PC 1 and PC 2 revealed a negative correlation between
water temperature and water mass and no correlation between water temperature and
stirring speed. For zeolite LTA mass, the reaction time and sodium silicate displayed
a near-perfect correlation. Given that the machine learning models predict the zeolite
LTA mass yield, a greater dependency on the input chemicals to the system rather than
the ratios was expected. The amount of water, sodium silicate, and sodium hydroxide
added to the system provided the machine learning model with an indication of the
system's mass balance, which assisted with predicting the resultant zeolite mass yield.
The synthesis routes conducted as part of the data collection have a constant NaAlO2
value of 5 g and SiO2 /Al2 O ratio of 2. In machine learning, variables with constant
values are excluded from the analysis. Therefore, the values of NaAlO2 and
SiO2 /Al2 O variables do not influence the predictions unless they have a varied,
continuous value. Therefore, the machine learning prediction is limited by the sodium
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silicate input synthesis descriptor. Nevertheless, the results from the PCA indicated
that the selected input variables for machine learning were all critical when modelling
the zeolite synthesis system. Furthermore, key relationships identified from past
publications, including reaction time, sodium silicate and the resulting zeolite LTA
mass (Silva et al., 2007), also held for the current dataset, indicating the robustness
and suitability of the data for further machine learning evaluation.
Application of Linear and Ridge Regression to Zeolite LTA Synthesis Data

To evaluate the baseline error of the machine learning, linear and ridge regression
models were trained using the zeolite synthesis data. The results from the training and
testing of the models are displayed numerically in Table 23.
Table 23. Training and testing results for linear and ridge regression.
Model Training 𝐑 𝟐 Testing 𝐑 𝟐
Linear Regression 0.368 ± 0.009 0.339 ± 0.019
Ridge Regression 0.372 ± 0.011 0.340 ± 0.018
The results from Table 23 demonstrated that both the linear and ridge regression
models do not accurately represent the zeolite synthesis system. The training and
testing R 2 values revealed that the models were not overfitting, which must be closely
monitored when modelling systems characterised by small datasets (Y. Zhang & Ling,
2018). Based on these results, it was pertinent to view the feature importance to
identify the variables that the models relied upon to make the predictions.
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As shown in Figure 58, the linear and ridge regression results were highly dependent
on the Na2 O/SiO2 ratio. Given the intercorrelation and multi-collinearity observed
between the input synthesis descriptors, the model was expected to depend on multiple
variables from the zeolite synthesis system. However, this result confirmed, along with
the poor model accuracy, that linear and ridge regression models failed to learn the
complex relationship inherent in the zeolite synthesis system.
Figure 58. Linear and ridge regression feature importance from input synthesis
variables.
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The accuracy of the linear and ridge regression models (R 2 value) was less than 0.6,
which indicated the need for more advanced machine learning models.
Application of Tree -Based Models to Zeolite LTA Synthesis

More advanced models that can learn non-linear relationships with tree-based
architectures, including regression trees, random forests and XGBoost, were trained
using the zeolite synthesis data.
Table 24. Training and testing results for tree-based models.

Model Training 𝐑 𝟐 Testing 𝐑 𝟐
Regression Tree 0.423 ± 0.012 0.385 ± 0.023
Random Forest 0.686 ± 0.018 0.620 ± 0.019
XGBoost 0.741 ± 0.007 0.700 ± 0.007
As shown in Table 24, as the complexity of the applied machine learning mode l
increased, accuracy improved. The similarity between the training and testing R 2
values confirmed that the models were not overfitting. This result was achieved by
pruning the trees generated in each of the above models, where parts of the tree were
removed to prevent it from growing to its full depth. In tree-based models, overfitting
occurs when the model is designed to perfectly fit all samples in the training dataset
(Praagman, 1985). This situation happens when the tree is allowed to grow without
constraining the number of splits, samples at each tree leaf, and the maximum depth
(Praagman, 1985). The models are most prone to overfitting when a given tree is
particularly deep. Therefore, hyperparameter tuning was conducted.
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The models were restricted to depths between 5 and 10, the minimum number of
samples at each split and the minimum number of samples at each leaf as 10 and 5,
respectively. By limiting the tree growth to these parameters, the testing results in
Table 24 were maximised without overfitting the model. The models could achieve
training accuracies of greater than 90%; however, the extent to which the regression
tree, random forest, and XGBoost models were overfitting made those models and
their results invalid. Constraining the tree's growth prevented overfitting;
nevertheless, the accuracy was also significantly reduced.
An example of the regression tree trained for the zeolite synthesis system is displayed
in Supplementary Figure 8. The feature importance is shown in Figure 59. The results
from the regression tree and random forest displayed a greater dependence on a variety
of input zeolite synthesis descriptors. The results were corroborated by trends in the
PCA biplot, which showed the variables with the greatest correlation to zeolite LTA
mass yield as sodium silicate and reaction time (Figure 57).
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Figure 59. Regression tree and random forest feature importance for input synthesis
variables.
The random forest displayed a more balanced feature importance across the dataset.
However, this observation was attributed to the number of estimators in the model.
In addition to applying regression trees and random forests to the zeolite synthesis
data, XGBoost was investigated. XGBoost is a tree-based machine learning technique
that applies gradient boosting to regression trees. The results from the XGBoost model
are shown in Figure 60.
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Figure 60. XGBoost testing results using input synthesis variables (results from the
training and testing runs that resulted in the greatest model accuracy).
While the results demonstrated significant improvement from the standard regression
tree model, the XGBoost algorithm did not model the zeolite synthesis system to the
desired accuracy. The balanced feature importance of the XGBoost model confirmed
the multi-collinearity and intercorrelation of all variables within the dataset. The
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results from the feature importance again demonstrated the importance of reaction time
and sodium silicate synthesis descriptors when predicting the output zeolite yield
(Figure 60).
Despite providing a better representation of the entire system, the regression tree,
random forest, and XGBoost models predicted results with reduced accuracy (ranging
between 42 to 74%), confirming the complexity of the zeolite LTA synthesis system.
Application of ANN to Zeolite LTA Synthesis

ANN suffers from significant variation between models due to the dependence on
many weight parameters during learning. Therefore, in this study, two different ANN
models have been developed, one with Python's sklearn package and the other with
the PyTorch package and accompanying hyper-parameter tuning tools from the Skorch
package. The results from the sklearn ANN and PyTorch ANN implementation were
used to validate each other. The sklearn model utilised grid search methodologies for
hyperparameter tuning and implementation of cross-validation during training.
Alternatively, the PyTorch model implemented an ANN model constructed using
PyTorch descriptors. For hyperparameter tuning, the Skorch library was employed,
enabling the use of grid search methodologies. Both the models had the same
architecture and very similar hyperparameters. However, the PyTorch implementation
provided the added advantage of greater control over the model architecture and cross-
validation results.
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Given the complexity of the data and ANN techniques combined with the limited
dataset, additional steps were taken to prevent the model from overfitting. These
included limiting the number of layers and neurons in the model, limiting the number
of iterations, controlling the learning rate, and conducting cross-validation. Both
models were constructed with an input layer, two hidden layers and an output layer,
all using the ReLU activation function. The results from training and testing the ANN
models are displayed numerically in Table 25.
Table 25. Training and testing results for ANN models (Ackley, Rege, & Saxena,
2003).
ANN Model Training 𝑹𝟐 Testing 𝑹𝟐
sklearn 0.887 ± 0.010 0.840 ± 0.016
PyTorch 0.847 ± 0.012 0.835 ± 0.012
The results in Table 25 confirmed that the ANN models were not overfitting, as
confirmed by the similarity between the model training and testing R 2 values. The
results from model training and testing of the ANN models are shown in Figure 61
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Figure 61. ANN model results using input synthesis variables (results from the
training and testing runs that resulted in the greatest model accuracy).
Both the PyTorch and sklearn ANN models predicted the zeolite yield with the highest
level of accuracy observed in this study (84 - 85 %). The convergence of the training
and validation curves confirmed that the model was not overfitting (Supplementary
Figure 9). In addition, the hyperparameter tuning of the models reduced overfitting
such that the training accuracy exhibited a high degree of similarity to the testing
accuracy. Unlike previous models, the hidden element in the ANN model architecture
meant the feature importance was not obtainable. Thus, there was a trade-off between
the accuracy and transparency of the ANN model. However, from the previous
visualisations of feature importance, it was clear that as the model complexity
increased, the model's dependence on the input synthesis descriptors became more
balanced. Thus, it was expected that this trend was true for the ANN models, given
the higher accuracy obtained by the models. Therefore, it is assumed that the feature
importance obtained for the XGBoost model in Figure 60 may be similar for the ANN
models.
207
Discussion: Model Comparison
Figure 62a shows a trend of increasing training and testing accuracy with model
complexity. The reappearance of sodium silicate and reaction time synthesis variables
from the PCA through to the feature importance reinforced the machine learning
results and data quality. The lesser performance of XGBoost in comparison to ANN
models was of interest as recent developments in gradient boosting algorithms often
return accuracies greater than those obtained through ANN (T. Chen & Guestrin).
However, it is critical to understand the data structure and relationships when
comparing the accuracy of XGBoost to ANN. XGBoost outperforms ANN, where
sequential relationships exist within a dataset (Pedregosa et al., 2011). In contrast,
given the interconnected nodes and layers, ANNs more accurately model multiple
independent relationships and data exhibiting multi-collinearity (Van Dyke Parunak,
1998). As shown through PCA, the multi-collinearity of the zeolite synthesis data
supported the existence of parallel relationships in the dataset. Hence, this situation
explained why the ANN modelled the system with greater accuracy than XGBoost
(and other tree-based model architectures).
208
Figure 62. (a) Comparison of machine learning model results (average R^2 value) (b)
Comparison of approaches to zeolite product analysis through ANN models (average
R^2 value)
From this study, the ANN modelled the zeolite synthesis system with the highest
accuracy. To confirm the validity of the hybrid data approach and the selection of the
hybrid 10 dataset, the ANN models were trained using various qualitative, quantitative,
hybrid 10, hybrid 20 and hybrid 40 datasets. The sklearn model was trained using the
varying datasets but with the same hyperparameters and training/testing split to
facilitate comparison (Figure 62b).
When modelled using ANN, the quantitative XRD data analysis approach provided
the least accurate representation of the zeolite synthesis system. This outcome was in
accord with the SEM images, which showed that the extent of zeolite crystals present
was not accounted for in the quantitative analysis approach. Moreover, the
quantitative dataset returned overfitted results when training the ANN model. The
qualitative XRD approach was computationally the most accurate despite errors
previously identified. However, further analysis of the zeolite LTA wt% distribution
209
within the qualitative data revealed the problems with the qualitative XRD method.
The distribution of data between 0 and 100 wt% was heavily skewed in the negative
direction, with 80% of the data lying between 80 and 100 wt%, of which 77% of the
qualitative data fell between 90 and 100 wt% zeolite LTA. Therefore, when predicting
the amount of zeolite LTA produced using the qualitative data, most of the predicted
results were between 90 and 100 wt%. Thus, the model incorrectly learned that most
of the zeolite synthesis routes in the qualitative data were successful.
Of the hybrid approaches, "hybrid 10" produced the most accurate model, thus
validating the understanding that the ambiguous cases of zeolite product analysis
occurred at the beginning of zeolite growth. Notably, the "hybrid 40" dataset also
overfitted the training model data. The new hybrid data strategy has developed a better
dataset for zeolite synthesis evaluation. Notably, theoretical understanding of the
zeolite growth curve combined with machine learning has proven to deliver new levels
of accuracy in practical applications. The results from the machine learning
application demonstrate that without a robust and high-quality dataset, the machine
learning models cannot be expected to accurately model complex systems.
210
Conclusions
This study met the primary aim of this study by successfully applying statistics and
machine learning principles to zeolite LTA synthesis. In addition, the hypothesis that
machine learning may predict preferred zeolite synthesis strategies was supported.
Indeed, the new modelling strategies have the potential to pre-evaluate synthesis routes
for a wide range of zeolite synthesis problems to optimise yield and performance.
Creation of a robust dataset was of primary importance as there were not only many
variables to consider but also a high degree of intercorrelation and multi-collinearit y
in the data. Management of the dataset was consequently of importance. For example,
a combination of quantitative and qualitative X-ray diffraction data was required to
determine the presence of crystalline and amorphous/non-diffracting material.
Quantitative XRD was able to identify amorphous/non-diffracting material. Whereas
qualitative XRD analysis was necessary when the synthesis was more progressed.
Consequently, a "hybrid" XRD analysis method was preferred. This dataset
interpretation strategy was innovative and resulted from the machine learning
approach. However, it was critical to only include the input synthesis variables.
Inclusion of output synthesis descriptors other than the zeolite yield resulted in false
predicting of the machine learning results. The application of PCA enabled
visualization of the higher dimensional data. Nevertheless, the component coefficients
revealed that each variable contributed in some way to the first four PCs.
The linear regression, ridge regression and tree-based models all returned R 2 values
less than 0.7 indicating that these machine learning models cannot accurately model
211
the zeolite synthesis system. The ANN approach modelled the system to the highest
accuracy of R2 of 0.84. The similarity of the training and testing results confirmed that
the models were not overfitting, an issue that must be closely monitored when
modelling systems characterised by small datasets. In terms of ANN performance, the
"hybrid 10" dataset produced the most accurate model; thus, validating that the
ambiguous cases of zeolite product analysis occurred at the beginning of the zeolite
growth curve. Thus, for this investigation the preferred model was the Artificial
Neural Network.
Future research should focus on adding complexity to the data, including modelling
the zeolite mother liquor, which would enable material economies to be optimised.
The additional complexity may require Deep Neural Networks (DNN) to achieve
higher testing accuracy. Alternate advanced machine learning techniques, including
Generative Adversarial Networks (GAN) and physics-informed GAN (PI-GAN), may
also be beneficial.
212
Chapter 8: Conclusions and Future Work
Conclusions
The aim of this research was to establish a low cost, scalable, and environmentally
sustainable process for converting aluminosilicate waste materials into high-value
zeolite products. As such, various waste activation methodologies using a combination
of alkali dissolution, temperature, and time of exposure were investigated. The
resultant active material was then used to make synthetic zeolite LTA as this is the
largest volume zeolite used today. Integration of machine learning was completed in
order to further optimize the conversion of waste aluminosilicate materials to zeolite
LTA. In particular, the need for clean and robust datasets was demonstrated.
The first research approach involved activation of aluminosilicate waste from the
lithium industry (spodumene leachate residue (SLR)). Two products were
subsequently made from the activated material: (1) cancrinite (which could be further
modified to make zeolite LTA by acid dissolution, neutralization, and hydrothermal
reaction) and (2) zeolite LTA made from hydrothermal reaction of mother liquor to
which sodium aluminate was added to create an Si/Al ratio = 1. The preferred
activation temperature was 240°C and the time required for activation was one hour.
Notably these conditions were probably more cost effective than previously reported
conditions (such as 150°C for 24 hours) as the overall power consumption was
substantially lower. It is essential for both economic and environmental reasons that
cancrinite is either employed, as for example, a sorbent for water treatment, or
converted to another material. For example, conversion of cancrinite to zeolite LTA
Chapter 8: Conclusions and Future Work 213

via acid dissolution, NaOH neuralization was not deemed to be feasible due to
additional cost to recover or remove sodium chloride generated in this process.
Chapter 4 presented the findings of research objective 2, wherein the potential of
natural zeolite waste conversion to two products (cancrinite and zeolite LTA) was
studied. As natural zeolite waste contains a higher silica content than SLR (ca. 4.8:1
Si/Al ratio compared to Si/Al ratio =2 for SLR) this material should produce relatively
more zeolite LTA compared to cancrinite (thus limiting the amount of this material
formed). The natural zeolite waste was again activated at 240°C for one-hour. A key
finding was the fact that 6M NaOH was necessary to promote dissolution of active Si
in the mother liquor. As predicted, a smaller amount of cancrinite was created, and
significantly, a range of impurities in the initial natural zeolite were mixed in with the
cancrinite as they were not soluble under the activation conditions. The resultant
zeolite LTA exhibited 95.54 wt% crystallinity. Moreover, lanthanum impregnated
cancrinite was shown to remove phosphates from water (achieving 99% removal
efficiency).
Despite the success of the two-product approach, it was still desirable to develop a
method which activated wastes and only produced one product. Thus, the third
research objective concerned discovery of a novel Quench Method for transforming
SLR into zeolite LTA. The activation of the waste material was carried out at low
temperature (100°C), using 10 M NaOH for 60 minutes.
The key insight was that the activation solution had to be quenched by rapid addition
of water and control of temperature to change the reaction conditions to promote

zeolite LTA synthesis. Consequently, prevention of the formation of undesirable by-
products, such as cancrinite or sodalite was minimised. The Quench approach appears
relatively low cost due to use of only 100 oC to activate the SLR waste.
The fourth research objective was addressed in Chapters 6 and 7, which focused on
the application of machine learning methods to advance zeolite synthesis. The
implementation of machine learning approaches for zeolite synthesis is not trivial as
inherently small data sets are employed which makes statistical analysis difficult.
Consequently, “web crawlers” to extract data to increase the data set size are often
used. However, this study revealed the pitfalls of using data from other research
groups. For example, it was found that utilizing identical recipes in different reactors
resulted in significant differences in the final product. Other criteria investigated
included pre-heated samples, use of stirred or static conditions, availability of
comprehensive process data (including mass balance) and zeolite yields. In all cases,
these latter criteria were not commonly addressed in the literature. Hence, use of data
from other researchers to facilitate machine learning was probably quality deficient.
Consequently, this study created a clean data set of information collected only in our
laboratory. Despite the small size (ca. 85 tests) of the data set, the use of statistical
and machine learning principles was successful in identifying that artificial neural
networks were at least 85 % accurate in predicting zeolite synthesis outputs.
In conclusion, this study pioneered the development of both a two-product and a
Quench process to activate various aluminosilicate wastes more effectively.

Both processes significantly reduce the cost of activation based upon the power
consumed during the activation procedure. In addition, both methods concomitantly
removed the majority of impurity phases present. Integration of machine learning
principles with the novel activation processes may further improve zeolite LTA
synthesis.
Future Work
Despite the success of the study, further work is required to enhance the technology
readiness level (TRL).
Firstly, the use of cancrinite for sorption applications needs to be developed further.
Key information required includes: (1) Coating of the cancrinite with either lanthanum
salts or alternate species such as iron which have been shown to sorb phosphate species
from water; (2) Determination of doped cancrinite performance (kinetics; equilibr ia;
column studies); (3) Extrusion and beading of cancrinite powders into industry
relevant forms; (4) Physical robustness (crush strength, attrition rates).
Secondly, the use of a continuous reactor to activate the aluminosilicate is sensible in
terms of controlling the quenching rate when using the Quench Method. A prototype
of the Quench Methods needs to be bult and tested to ensure performance is optimal.
(Appendix A).
Lastly, it is recommended to continue increasing the complexity of the database for
machine learning activities to enable a more efficient process. While the Artificial

Neural Network (ANN) was the preferred model for this research, increasing data
complexity may enable higher testing accuracy through Deep Neural Networks (DNN)
or more advanced machine learning techniques.

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Appendices
Appendix A
Supplementary data for Chapter 3: Feasibility of Zeolite LTA Synthesis from

Spodumene Leachate Residue via Cancrinite Formation
Supplementary Table 1 XRF analysis of SLR

SiO2 66.64 P2O5 0.04
Al 2O3 23.7 SO3 0.30
Fe 2O3 1.61 Cr2O3 0.03
Na2O 0.52 NiO 0.01
K2O 0.56 ZnO 0.01
MgO 0.99 PbO 0.01
CaO 0.74 BaO 0.06
TiO2 0.04 Mn3O4 0.17
LOI 5.12
Appendices 235
Supplementary Table 2 Quantitative XRD analysis of SLR
Phase SLR wt%
Hydrogen Aluminium Silicon Oxide 46.91
Quartz 3.93
Lithium Sulfate 0.30
Non-diffracting/unidentified 48.86
Sum 100
Supplementary Table 3 Crystalline cancrinite content of the products formed after

hydrothermal treatment of SLR material at 100℃
Phase wt% Crystalline
Quartz 3.97
Cancrinite 10.37
Sodalite 9.83
Zeolite LTA 1.69
Non-diffracting 74.24
Appendices 236
Reaction NaOH Quartz Non-
Cancrinite% Sodalite% ZeoliteA%
time (hrs) molarity % diffracting%
1 4 4.82 14.44 5.33 2.57 72.84
1 5 5.18 14.06 7.38 1.92 71.46
1 7 3.48 18.75 8.58 2.08 67.11
1 10 2.25 26.38 7.73 2.04 61.60
24 4 0.30 63.39 0.47 3.25 32.59
24 5 0.16 65.26 0.54 3.15 30.89
24 7 0.14 68.34 0.71 3.29 27.52
24 10 0.07 78.63 8.79 3.09 9.42
Appendices 237
Reaction NaOH Quartz Non-
Cancrinite% Sodalite% ZeoliteA%
time (hrs) molarity % diffracting%
1 5 0.72 37.93 1.25 3.16 56.94
1 7 0.30 43.89 1.56 4.30 49.96
1 10 0.00 50.97 5.51 2.69 40.84
1 14 0.00 14.61 10.48 1.89 73.03
15 5 0.34 42.42 1.19 3.63 52.42
15 7 0.21 41.49 1.48 3.62 53.20
15 10 0.38 37.72 2.49 3.16 56.26
15 14 0.00 21.11 15.76 0.11 63.01
24 4 0.13 67.78 0.15 3.57 28.38
24 5 0.08 70.69 0.00 3.68 25.55
24 7 0.03 66.91 0.13 3.38 29.55
24 10 0.16 70.59 0.14 3.40 25.72
Appendices 238
Supplementary Table 6 XRF analysis of Cancrinite
SiO2 38.822 P2O5 0.035
Al 2O3 25.802 SO3 0.354
Fe 2O3 1.59 Cr2O3 0.034
Na2O 23.572 NiO 0.024
K2O 0.049 ZnO 0.007
MgO 1.024 PbO 0.013
CaO 0.767 BaO 0.051
TiO2 0.051 Mn3O4 0.146
LOI 9.48
Supplementary Table 7 XRF analysis of Zeolite LTA, activated at 2M HCl and

synthetised at 4M NaOH, 4 hours synthesis at 80℃
SiO2 32.963 P2O5 0.012
Al 2O3 28.787 SO3 0.112
Fe 2O3 1.236 Cr2O3 0.022
Na2O 17.311 NiO 0.021
K2O 0.024 ZnO 0.006
MgO 0.77 Mn3O4 0.112
CaO 0.595 Cl 0.089
TiO2 0.023
LOI 17.9
Appendices 239
5
Volume Density (%)

3
0
0 100 200 300 400 500
Size Classes (um)
a) SEM Image b) Particle Size Distribution
Supplementary Figure 1 a) SEM imaging and b) particle size of SLR
100 100
1h Synthesis 1h Syntesis
80 80
wt% Non-Diffracting
60 60
40 40
20 20
0 0
4 6 8 10 4 6 8 10
NaOH Molarity NaOH Molarity
wt% Crystalline Cancrinite (a) wt% Non-Diffracting/unidentified (b)
100 100
wt% Crystalline Quartz
80 80
60 60
40
40
20
20
0
0 4 6 8 10
4 6 8 10
NaOH Molarity
NaOH Molarity
wt% Crystalline Sodalite (c) wt% Crystalline Quartz (d)
Supplementary Figure 2 Influence of time and NaOH molarity in Cancrinite

synthesis from SLR at 150℃ a) Crystalline cancrinite, b) non-Diffracting material, c)
Crystalline Sodalite and d) Crystalline Quartz
Appendices 240
100 100
1h Synthesis 1h Syntesis
15hrs Synthesis 15 hrs Syntesis

24hrs Synthesis 24 hrs Syntesis
80 80
wt% Non-Diffracting
60 60
40 40
20 20
0 0
4 6 8 10 12 14 4 6 8 10 12 14
NaOH Molarity NaOH Molarity
wt% Crystalline Cancrinite (a) wt% non-Diffracting/unidentified (b)
100 100
24hrs Synthesis
24hrs Synthesis
wt% Crystalline Quartz

80 80
60 60
40
40
20
20
0
0 4 6 8 10
4 6 8 10 12 14
NaOH Molarity
NaOH Molarity
wt% Crystalline Sodalite wt% Crystalline Quartz
Supplementary Figure 3 Influence of time and NaOH molarity in Cancrinite

synthesis from SLR at 200C, a) Crystalline cancrinite, b) non-Diffracting material, c)
Crystalline Sodalite, d) Crystalline Quartz
Appendices 241
Supplementary Figure 4 Energy required to produce cancrinite at 240°C and 1 hour
synthesis (Reactor1) vs energy required to produce cancrinite at 150 °C and 24 hours
synthesis.
Appendices 242
2 hours synthesis
4,000x 8,000x
3 hours synthesis
4,000x 8,000x
4 hours synthesis
4,000x 8,000x
5 hours synthesis
Appendices 243
4,000x 8,000x
6 hours synthesis
4,000x 8,000x
Supplementary Figure 5. SEM images of zeolite LTA after hydrothermal reaction
from dissolved cancrinite, reaction temperature 80℃, time= 2 to 6 hours
Appendices 244
Appendix B
Supplementary data for Chapter 5: Quench Method
Supplementary Figure 6. Flow diagram of Continuous Reactor Prototype
Appendices 245
Appendix C
Supplementary data for Chapter 7: Evaluation and application of machine

learning principles to Zeolite LTA synthesis
Supplementary Table 8. Candidate values for linear regression hyperparameters.

Fit Intercept True, False 2 candidates
Normalise True, False 2 candidates
Copy X True, False 2 candidates
Supplementary Table 9. Candidate values for ridge regression hyperparameters.

Fit Intercept True, False 2 candidates
Normalise True, False 2 candidates
Copy X True, False 2 candidates
Alpha −10
1 × 10 , … , 1 400 candidates
Supplementary Table 10. Candidate values for regression tree hyperparameters.

Maximum Tree Depth 5, 6, 7, 8, 9, 10 6 candidates
Minimum Samples Required to Split
5, …, 15 10 candidates
Internal Node
Minimum Samples Required at a Leaf Node 5, …, 15 10 candidates
Maximum Number of Features to Consider
Auto, Sqrt, Log2 3 candidates
when Evaluating Best Split
5, 10, 15, 20, 25,
Maximum Number of Leaf Nodes 6 candidates
30
Supplementary Table 11. Candidate values for random forest hyperparameters.

Number of Trees 10, 50, 100 3 candidates
Maximum Tree Depth None, 1, …, 10 11 candidates
Minimum Samples Required to Split
Internal Node
Minimum Samples Required at a Leaf Node 5, …, 15 10 candidates
Maximum Number of Features to Consider
Auto, Sqrt, Log2 3 candidates
when Evaluating Best Split
5, 10, 15, 20, 25,
Maximum Number of Leaf Nodes 6 candidates
30
Supplementary Table 12. Candidate values for XGBoost hyperparameters.

Number of Trees 10, 50, 100 3 candidates
Appendices 246
Maximum Tree Depth None, 1, …, 10 11 candidates
0.0001, 0.001,
Learning Rate 3 candidates
0.01
Gamma (minimum loss reduction required to
0, 0.5, 1, 5, 15,
make a further partition on a leaf node of the 6 candidates
20
tree)
Minimum Child Weight (minimum sum of
instance weight needed in a child)
Subsample (subsample ratio of the training
0.5, …, 1.0 5 candidates
instances)
Column Sample by Tree (subsample ratio of
0.1, …, 0.5 5 candidates
columns when constructing each tree)
Alpha (regularisation term) 0.1, …, 1.0 10 candidates
Lambda (regularisation term) 0.1, …, 1.0 10 candidates
Supplementary Table 13. Candidate values for sci-kit learn ANN hyperparameters.
Hidden Layer 1 5, …, 30 25 candidates
Activation Identity, Logistic, Tanh, ReLU 4 candidates
Solver IBFGS, SGD, Adam 3 candidates
Alpha 0.0001, 0.001, 0.01 3 candidates
Learning Rate 0.0001, …, 0.01 Continuous
Number of Iterations 100, 500, 1000, 1500, 2000 5 candidates
Supplementary Table 14. Candidate values for PyTorch ANN hyperparameters.

Learning Rate 0.0001, …, 0.01 Continuous
100, 500, 1000, 1500,
Number of Iterations 5 candidates
2000
Appendices 247
Supplementary Table 15. Complete training and testing results reported as R^2
values. The results from each trial were obtained from a different training and testing
data split.
Average
Trial 1 Trial 2 Trial 3 Trial 4 Trial 5
Value
𝟎. 𝟑𝟔𝟖
Train 0.377 0.367 0.359 0.373 0.364
Linear ± 𝟎. 𝟎𝟎𝟗
Regression 𝟎. 𝟑𝟑𝟗
Test 0.320 0.359 0.323 0.343 0.350
± 𝟎. 𝟎𝟏𝟗
𝟎. 𝟑𝟕𝟐
Train 0.371 0.361 0.363 0.383 0.381
Ridge ± 𝟎. 𝟎𝟏𝟏
Regression 𝟎. 𝟑𝟒𝟎
Test 0.322 0.358 0.347 0.326 0.345
± 𝟎. 𝟎𝟏𝟖
𝟎. 𝟒𝟐𝟑
Train 0.411 0.417 0.435 0.422 0.431
Regression ± 𝟎. 𝟎𝟏𝟐
Tree 𝟎. 𝟑𝟖𝟓
Test 0.408 0.367 0.405 0.362 0.381
± 𝟎. 𝟎𝟐𝟑
𝟎. 𝟔𝟖𝟔
Train 0.677 0.681 0.698 0.704 0.668
Random ± 𝟎. 𝟎𝟏𝟖
Forest 𝟎. 𝟔𝟐𝟎
Test 0.639 0.632 0.608 0.601 0.618
± 𝟎. 𝟎𝟏𝟗
𝟎. 𝟕𝟒𝟏
Train 0.748 0.740 0.737 0.734 0.745
± 𝟎. 𝟎𝟎𝟕
XGBoost
𝟎. 𝟕𝟎𝟎
Test 0.707 0.697 0.693 0.700 0.705
± 𝟎. 𝟎𝟎𝟕
𝟎. 𝟖𝟖𝟕
Train 0.897 0.877 0.880 0.886 0.894
ANN ± 𝟎. 𝟎𝟏𝟎
(sklearn) 𝟎. 𝟖𝟒𝟎
Test 0.856 0.825 0.824 0.852 0.843
± 𝟎. 𝟎𝟏𝟔
𝟎. 𝟖𝟒𝟕
Train 0.859 0.848 0.842 0.835 0.852
ANN ± 𝟎. 𝟎𝟏𝟐
(PyTorch) 𝟎. 𝟖𝟑𝟓
Test 0.847 0.842 0.824 0.823 0.837
± 𝟎. 𝟎𝟏𝟐
Appendices 248
Supplementary Figure 7. Zeolite growth curve displaying the relationship between
nucleation and crystal growth rates and their contribution to the overall crystal
growth curve.
Supplementary Figure 8. Example of a regression tree trained for the zeolite LTA
synthesis system where “value” represents the predicted variable, the zeolite yield.
Appendices 249
Supplementary Figure 9. Learning curves for PyTorch ANN. The convergence of the
training and validation curves confirmed that the model is not overfitting.
Background Theory
The multidisciplinary nature of this study necessitates the need for background theory
on machine learning. The goal is to ensure all readers understand the machine learning
algorithms applied in the study. The following section provides derivations and
analysis of machine learning algorithms before the methodology describes the
application of the algorithms.
Principal Component Analysis
In a standard setting, PCA is applied to a space of N observations or instances of data
x1 , x2 , … , xN ∈ ℝM where each observation consists of M features or dimensions. PCA
selects a number n and obtains an n-dimensional representation such that
b1 , b2 , … , bN ∈ ℝn where n ≤ M and 𝐛i represents the observation 𝐱 i in a reduced
dimensionality space (M. A. Khan et al., 2019).
Appendices 250
To transform the vector 𝐱 to an n ≤ M-dimensional space, each observation
represented by 𝐛i is defined as the projection of 𝐱 i onto 𝐕 where 𝐕 is an orthonormal
basis v1 , … , v n of an n-dimensional subspace. The mean is subtracted from each
observation to ensure the projection is invariant under constant addition (M. A. Khan
et al., 2019). Supplementary Algorithm 1 provides the general format of the PCA
algorithm.
Supplementary Algorithm 1. PCA general algorithm

1
Mean calculation: 𝒎 = ∑𝑁𝑖=1 𝒙 𝑖
𝑁
̃ 𝑖 = 𝒙𝑖 − 𝒎 where 𝑥̃𝑖 is stored in an 𝑁 × 𝑀 matrix 𝑋̃

Subtract the mean: 𝒙
Projection: 𝒃𝑇𝑖 = ̃
𝒙𝑇𝑖 𝑽 where 𝑽 = (𝑣1 𝑣2 … 𝑣𝑛 )
When selecting the projection matrix 𝐕, the degree to which the projected observations
are spread out is measured by the variance of b1 , … , bN scaled by a factor of N −1 where
1
b̅ = ∑N
i=1 bi (Jolliffe, 2002).
N
𝐍 𝐍
𝟏 𝟐 𝟐
𝐖 = 𝐍 × 𝐕𝐚𝐫𝐢𝐚𝐧𝐜𝐞 [𝐛𝟏 , … , 𝐛𝐧 ] = 𝐍 ∑(𝐛𝐢 − 𝐛̅ ) = ∑(𝐛𝐢 − 𝐛̅)
𝐍
𝐢=𝟏 𝐢=𝟏
Supplementary Equation 1
The goal of PCA is to select 𝐯1 as the vector that maximises the spread of the projected
data: 𝐯1 = arg max

T
W where 𝐯1 is normalised. The solution to the maximisation
v v=1
̃T 𝐗
problem comes about by defining the matrix 𝐒 = 𝐗 ̃ and introducing the Lagrangian
multiplier λ to maximise the Lagrangian2. The solution to the maximisation problem
involves the selection of 𝐯1 , … , 𝐯n as the n orthonormal eigenvectors of 𝐒 with the n
largest eigenvalues using singular value decomposition (SVD) (Jolliffe, 2002).
Appendices 251
SVD computes the following three matrices for an N × M input:
σ1 0 ⋯ 0
0 σ2 0
⋮ ⋱ ⋮
∑= 0 0 ⋯ σM , 𝐔 = [u1 u2 ⋯ uN ], 𝐕 = [v1 v2 ⋯ vM ]
0 0 ⋯ 0
⋮ ⋮ ⋮
[0 0 ⋯ 0 ]
SVD computes the matrices in Supplementary Equation 2 such that 𝐔 ∑ 𝐕 T = 𝐗 and
𝐕 T 𝐕 = 𝐈, 𝐔 T 𝐔 = 𝐈 and σ1 ≥ σ2 ≥ ⋯ ≥ σM are the singular values of 𝐗. The above
conditions reveal that the columns of 𝐕 are orthonormal (Jolliffe, 2002). Computing
𝐕 T 𝐯i reveals the following:
v1T v1T vi 0
⋮ ⋮ ⋮
𝐕 T 𝐯i = v iT v i = viT vi = 1 = ei
⋮ ⋮ ⋮
T
[v M ] T
[vM vi] [0 ]
Supplementary Equation 4 demonstrates the following:
T T T
(𝐗 T 𝐗)𝐯i = (𝐕 ∑ 𝐔 T 𝐔 ∑ 𝐕 T ) 𝐯i = 𝐕 ∑ ∑ 𝐞i = 𝐕σ2i ei = σ2i 𝐯i
Inferred from Supplementary Equation 4 is the relationship of 𝐯i . Each value of 𝐯i is
an eigenvector of 𝐗 T 𝐗 with an eigenvalue of σ2i . Relating this to the previous definition
of 𝐕n reveals that the first n columns of 𝐕 are the first n eigenvectors. The projection
Appendices 252
of a single observation 𝐱 Ti onto a subspace spanned by the first n PC is written as 𝐛Ti =
̃𝐕n.
𝐱 Ti 𝐕n or alternatively 𝐁 = 𝐗
The vectors 𝐛i in matrix, 𝐁 correspond to the coordination of the vector 𝐱 i when
projected onto an n-dimensional subspace. Variance explained by the PC is utilised to
determine the correspondence of 𝐛i = [bi1 bi2 ⋯ bin ]T to vectors in the original
space. The projected coordinates in the original space are 𝐱 ′i = bi1 𝐯1 + ⋯ + bin 𝐯n =
̃𝐕n 𝐕nT for all observations (Jolliffe, 2002).

𝐕n 𝐛i or 𝐗 ′ = (𝐕n 𝐁T )T = 𝐗
̃𝐕𝐕 T = 𝐗
Exploring the case of n = M and 𝐕n = 𝐕 obtains the relationship 𝐗 ′ = 𝐗 ̃𝐈 =
̃. This relationship dictates that no information is lost if all M principal directions are
𝐗
̃
applied to the projection. In this case, the projected matrix 𝐁 is still different from 𝐗
but corresponds to a direct rotation of all observations in M directions. When
̃ is rotated back without any information loss (Jolliffe, 2002).

translating back to 𝐗′, 𝐗
̃ will lose information if n < M. All

However, in practice, the reconstructed matrix 𝐗
̃, which is orthogonal to the space 𝐕n, is lost because those directions

variability of 𝐗
are projected away (Jolliffe, 2002). The variance explained is computed from the
Frobenius norm to determine how much information is retained in a reconstruction of
n PC.
‖𝐗 ′ ‖2F
Variance Explained = 2
̃‖
‖𝐗 F
Appendices 253
Using the relationship ‖𝐗‖2F = trace(𝐗 T 𝐗) and exploiting relationships in SVD
provides the formula for the variance explained by the n first PC.
∑ni=1 σ 2i
Variance Explained = M 2
∑i=1 σ i
When applying the SVD and computing the variance explained, the PCA algorithm
becomes:
Supplementary Algorithm 2. PCA with SVD and variance explained.

1
Mean calculation: 𝒎 = ∑𝑁𝑖=1 𝒙 𝑖
𝑁
Subtract the Mean: 𝒙

̃ 𝑖 = 𝒙𝑖 − 𝒎
𝑥̃ 𝑖𝑗 1
Standardise the data: 𝑥̃ 𝑖𝑗 = , where 𝑠𝑘 = √ ∑𝑁 ̃ 2𝑖𝑘
𝑖=1 𝑥
𝑠𝑘 𝑁−1
Compute the SVD: 𝑼 ∑ 𝑽𝑇 = 𝑿
̃ 𝑽𝑛
Project the observations onto a subspace as 𝒃𝑇𝑖 = 𝒙𝑇𝑖 𝑽𝑛 or 𝑩 = 𝑿
∑𝑛 𝜎𝑖2
Calculate the variance explained: ∑𝑖=1
𝑀 2
𝑖=1 𝜎𝑖
Linear Regression
Linear regression models the output prediction as a linear combination of all input
features where the M features are parameterised by weight coefficients, w and input
variables 𝐱 = ( x1 , … , xM ) T (Howard, 2007).
Appendices 254
y (𝐱, 𝐰) = w0 + w1 x1 + ⋯ + wM xM
The regression model extends to problems with multiple input features by considering
linear combinations of fixed nonlinear functions where ϕj (𝐱) is defined as a basis
function. Limiting the index j to a value of M − 1, the total number of parameters
considered in the model will be equal to M (Howard, 2007).
M−1
y (𝐱, 𝐰) = w0 + ∑ wj ϕj (𝐱)
j=0
The term w0 considers the fixed offset of a dataset as the bias parameter (Howard,
2007). The inclusion of an additional basis function, ϕ0 (𝐱) = 1, is convenient in that
the model becomes:
M−1
y (𝐱, 𝐰) = ∑ wj ϕj (𝐱)
j=0
Supplementary Equation 9 is simplified by the addition of the following vectorized
terms.
w0 1
w1 ϕ1 (𝐱)
𝐰 = [ ⋮ ], 𝛟 = [ ]
⋮
wM−1 ϕM−1 (𝐱)
Appendices 255
Combining Supplementary Equation 9 and Supplementary Equation 10, the
model becomes:
y (𝐱, 𝐰) = 𝐰 T 𝛟(𝐱)
To solve the linear regression problem, the least-squares approach is applied. The
resulting cost function becomes an optimisation problem to minimise the function with
respect to model parameters (Howard, 2007; Van Houwelingen, 2004).
N N
1 2 1 2
ℰ M (w) = ∑ (y n − y(𝐱 n ,𝐰)) = ∑(y n − 𝐰 T 𝛟(𝐱n ))
N N
n=1 n=1
To solve the cost function, the partial derivative of ℰ is obtained with respect to w
(Howard, 2007; Van Houwelingen, 2004).
N N
∂ℰ M 2 2
= ∑ yn 𝛟(𝐱n) T − [∑ 𝛟(𝐱 n)𝛟(𝐱 n)T ]𝐰 T
∂wn N N
n=1 n=1
The gradient of the function is then:

∂ℰ
∂w1 2 2
(
∇ℰ M w = ) ⋮ = yn𝛟(𝐱 n)T − (𝛟(𝐱 n )𝛟(𝐱n )T )𝐰 T
∂ℰ N N
(∂wM )
The optimal weights are found by setting the gradient function to zero, which returns
Supplementary Equation 15 (Howard, 2007; Van Houwelingen, 2004).
Appendices 256
−1
̃T 𝐗
𝐰 ∗ = (𝐗 ̃) ̃
𝐗T 𝐲
̃ is defined as the design matrix where the elements

In Supplementary Equation 15, 𝐗
̃ nj = ϕj (𝐱 n) resulting in the construction of the following matrix

are given by X
(Howard, 2007).
ϕ0 (𝐱1 ) ϕ1 ( 𝐱1 ) ⋯ ϕM−1(𝐱1 )
̃ = ( ϕ0 (𝐱 2 ) ϕ1 (𝐱 2 ) ⋯
𝐗
ϕM−1 (𝐱 2)
)
⋮ ⋮ ⋱ ⋮
ϕ0 (𝐱 N ) ϕ1 (𝐱 N ) ⋯ ϕM−1 (𝐱 N)
Ridge Regression
The application of ridge regression builds upon the standard linear model in
Supplementary Equation 9. However, it introduces regularisation as a general
approach for managing model complexity. Ridge regression utilises least-squares
regularisation with the standard linear model, which takes the following form
(Howard, 2007).
ℰ M(𝐰) + λℰ W (𝐰)
Within linear regression, two potential issues can occur:
̃ T𝐗
𝐗 ̃ is unable to be inverted as a result of N ≤ M or the presence of many
̃.
linearly dependent rows in 𝐗
M is large relative to N, and the model overfits.
Appendices 257
To solve these issues, regularisation alters the cost function to have a stronger
preference for small weights by applying parameter shrinkage (Howard, 2007; Van
Houwelingen, 2004). To ensure the constant term in the regression model is not
affected by the regularisation, the cost function is considered as:
N
1 2 λ
ℰ λ (𝐰) = ∑(yn − 𝐰 T 𝛟(𝐱 n)) + 𝐰 T 𝐰
N N
n=1
The magnitude of the weights is affected by the scaling of X, and therefore,
standardisation is applied according to Supplementary Equation 19.
N N
Xij − uj 1 1 2
̂
X ij = , uj = ∑ Xkj , ŝj = √ ∑(Xij − uj )
ŝ j N N−1
i=1 i=1
Supplementary Equation 20 displays the resulting cost function where λ ‖𝐰‖2 is the
regularisation term and λ is the regularisation constant (Howard, 2007).
2
̂𝐰‖ + λ‖𝐰‖2 , λ ≥ 0
ℰ λ (𝐰) = ‖𝐲 − 𝐗
To solve the ridge regression problem, the derivative is set to zero, which then provides
the formula for the optimal weights, 𝐰 ∗ (Howard, 2007).
dℰ λ 2
̂ T (𝐲 − 𝐗
= −𝐗 ̂ 𝐰) + 2𝐰
dw
Appendices 258
𝐰 ∗ = arg min ℰ λ (𝐰) = (𝐗 ̂ + λ𝐈)−1 𝐗
̂T𝐗 ̂T𝐲
w
6.4 Regression Trees
The goal of regression trees is the same as linear and ridge regression, predicting a
continuous output value y i based on input features xi . Hunt’s algorithm, displayed in
Supplementary Algorithm 3, is used to construct regression trees. Hunt’s algorithm
requires the following parameters (Praagman, 1985):
Initial tree T containing the root node.
Dr , the data associated with the current tree branch, initially the complete dataset.
Supplementary Algorithm 3. Regression tree.

if the stop criterion is met:
Add a leaf node to the tree, which assigns every observation the mean value
of the node in Dr :
1
y(r) = ∑ yi
N (r)
i∈r
else
Try different splits of Dr , compute the impurity for each split using the sum
of squares impurity measure and select the split Dr = Dv1 , ⋯ , Dvk with the
highest purity gain. Recursively call the method on Dv1 , ⋯ , Dvk.
end
Appendices 259
The model evaluates each new split by computing the average sum of squares error
∑i∈vyi
between the observation y i and the mean value y(v ) = (5).
N(v)
1 2
I(v) = ∑(yi − y(v))
N(v )
i∈v
The model then applies Hunt’s algorithm. The stopping criteria occurs when the
impurity falls below a specified value.
Random Forest
Before introducing random forests, it is important to understand the concept of
bagging. Bagging begins with a dataset D of size N, which selects T new datasets
D1 , ⋯ , DT of size N ′ ≤ N by randomly subsampling D. When N ′ = N, each Dt is
sampled by N randomly selected points from the original data D with replacement. The
same points may occur many times in each Dt . The regression model is trained on each
T dataset to produce T different regressors combined to give a single regression model
(Breiman, 2001). This concept is explained visually in Supplementary Figure 10
Appendices 260
Supplementary Figure 10. Combining regression trees to form a random forest using
bagging.
Random forests are an application of bagging to regression trees. The original data is
used to produce T datasets. The standard regression tree algorithm is trained on each
sampled dataset to produce combined predictors using Supplementary Equation
24(Breiman, 2001).
T
1
y = ∑ f t (x)
T
t=1
Regression trees often select the same split at each iteration creating trees of high
correlation. To avoid this, each step of Hunt’s algorithm should only consider splits
from m < M of the features selected randomly from all M features to produce less
correlated trees (Breiman, 2001).
XGBoost
XGBoost is a tree-based model that applies gradient boosting to regression trees to
achieve greater accuracy and faster computation time. XGBoost uses optimised
Appendices 261
gradient boosting through parallel processing, tree-pruning, and regularisation to avoid
overfitting and bias within machine learning models (T. Chen & Guestrin).
XGBoost build trees by minimising the following loss function:
1
ℒ (ϕ) = ∑ l(ŷ i ,yi ) + ∑ Ω (f k ) where Ω(f) = γT + λ‖w‖2
2
i k
The term ∑i l(ŷi ,y i ) represents the loss function, commonly mean squared error,
calculated from the true and predicted values. The term ∑k Ω(f k ) contains the
regularisation function used to reduce the predictions insensitivity to individua l
observations which, can be adjusted to prevent overfitting. The omega term also
includes the leaf weights w, terminal nodes or leaves in a tree T and the user parameter,
γ, used to encourage tree pruning (T. Chen & Guestrin).
The goal is to find an optimised output value for the leaf to minimise Supplementary
Equation 25. The equation for weight optimisation is written below with the
corresponding loss function.
− ∑i∈Ij g i
wj∗ =
− ∑i∈Ij hi + λ
2
T
1 (− ∑i∈Ij g i )
ℒ̃ ( t)(q) = − ∑ + γT
2 − ∑i∈Ij hi + λ
j=1
Appendices 262
The computational time to enumerate through all the possible tree structures q
necessitates an alternative algorithm. A greedy algorithm starts from a single leaf and
adds branches to the tree over several iterations. In this algorithm, IL and IR are the
instance sets of the left and right nodes after the split. The loss reduction after the split
is given by the following equation by letting I = IL ∪ IR (T. Chen & Guestrin). This
formula is used in practice to evaluate the split candidates (T. Chen & Guestrin).
2 2
1 (− ∑i∈IL g i ) (− ∑i∈IR g i ) (− ∑i∈I g i )2
ℒsplit = [ + − ]−γ
2 − ∑i∈IL hi + λ − ∑i∈IR hi + λ − ∑i∈I hi + λ
Artificial Neural Network
ANNs consist of information processing units called neurons connected to other
neurons by weighted connections. The neurons are organised in layers that feed to each
other. Information in the network is processed sequentially. First, the input vector is
given to the input layer and passed through the neural network layers and activation of
each neuron. Next, the activation is propagated through one or more hidden layers to
the output layer, consisting of neurons corresponding to coordinates of the output
vector. This process completes a forward pass through the network (Van Dyke
Parunak, 1998).
The forward pass of a neural network builds upon the standard linear model in
Supplementary Equation 9; however, where the function f (∙) is the identity for
regression.
Appendices 263
M
y (𝐱, 𝐰) = f ( ∑ wj ϕj (𝐱))
j=1
The model is extended so the basis functions ϕj (x) are dependent on model parameters
which are adjusted with the weight coefficients throughout the model training (Van
Dyke Parunak, 1998). Like linear regression, neural networks use basis functions that
are a linear combination of all inputs where the combination coefficients are adaptive
parameters (Van Dyke Parunak, 1998). The basic neural network model is described
as a series of functional transformations. In this model, M is the number of neurons in
the input layer, and D is the neurons in the output layer (Van Dyke Parunak, 1998).
The neural network becomes a mapping of f: ℝM → ℝD which maps x to y = f(x). The
input processing unit or neuron for a neural network is described in Supplementary
Equation 30 for M linear combinations of input variables x1 , … , xD .
D
(1) ( 1)
aj = ∑ wij xi + wj0
i=1
The subscript (M. A. Khan et al., 2019) indicates the current layer of the network and
(1)
the parameters associated with that layer. Here, the term wij corresponds to the
(1)
layer’s weights during the term wj0 corresponds to the biases of the neural network
layer (Howard, 2007). The quantity aj is a unit of activation. In a neural network, aj is
transformed by a differentiable nonlinear activation function h(∙) (Howard, 2007).
Appendices 264
zj = h (aj )
The values from Supplementary Equation 31 correspond to the output of the hidden
units within a network. Similarly, the general linear model can be applied to give the
output unit activation of a neural network where k = 1, … , K and K are the number of
outputs (Van Dyke Parunak, 1998).
M
(2) ( 2)
ak = ∑ wkj zj + wk0
j=1
As represented by the subscripts, Supplementary Equation 32 corresponds to the
second layer of a neural network. The output unit activations are transformed to give
the output of the network, yk (Van Dyke Parunak, 1998). The activation function for
the output unit is the identity such that:
yk = ak
When combining the layers of the network from Supplementary Equation 30and
Supplementary Equation 32, the overall function becomes (Van Dyke Parunak, 1998):
M D
(2) ( ) ( ) ( )
y k (𝐱, 𝐰) = (∑ wkj h (∑ wij1 xi 1 2
+ wj0 ) + wk0 )
j=1 i=1
Supplementary Equation 34 is evaluated through forward propagation. However,
similar to linear regression, an additional input variable defined as x0 = 1 is included
Appendices 265
so the bias parameters become integrated into the weight parameters such that the
overall function simplifies to (Van Dyke Parunak, 1998):
M D
( 2) ( 1)
yk (𝐱, 𝐰) = (∑ wkj h (∑ wij xi ))
j=0 i=0
The solution to the neural network is very similar to both linear and ridge regression.
Given a training set of input vectors 𝐱 n and a corresponding set of target vectors 𝐭 n for
n = 1, … , N the network is trained by minimising the cost function (Van Dyke
Parunak, 1998).
N
1
ℰ (𝐰) = ∑‖𝐲 (𝐱 N ,𝐰) − 𝐭 n‖2
N
n=1
𝐰 ∗ = arg min ℰ (𝐰)

w
Once again, the optimal weights are found by obtaining the gradient function and
setting it to zero. This can be achieved through backpropagation, the message passing
scheme that sends information back and forth through the network (Van Dyke
Parunak, 1998). The backpropagation algorithm consists of two stages, the feed-
forward stage discussed previously and the backpropagation stage, where the
prediction error is computed, and the error is propagated backwards to adjust the
weights. The backpropagation algorithm uses deterministic optimisation to minimise
the squared error sum through the gradient descent method which, requires the
Appendices 266
computation of the activation function’s partial derivatives with respect to the network
weights (Van Dyke Parunak, 1998).
Supplementary Equation 38shows the evaluation of the cost function for each point
within the training set:
ℰ (𝐰) = ∑ ∇ℰ n(𝐰)
n=1
The problem then becomes evaluating the gradient ∇ℰ n (𝐰). The derivative of ℰ (𝐰)
is dependent on the weight wji via the summed input aj to unit j (Pineda, 1987; Van
Dyke Parunak, 1998)
∂En ∂En ∂aj

=
∂wji ∂ai ∂wji
∂En ∂aj
Where = δj referred to as errors and, knowing that aj = ∑i wji zi, = zi (Pineda,
∂ai ∂w ji
1987; Van Dyke Parunak, 1998)With this understanding, the equations are combined
to obtain:
∂En
= δj zi
∂wji
Supplementary Equation 40 explains that the derivative required to solve the
minimisation problem is obtained by multiplying the value for δ at the output of the
Appendices 267
weight by z for the input of the weight (Pineda, 1987; Van Dyke Parunak, 1998). The
calculation of δ at the output is simply:
δk = y k − t k
To obtain δ for the hidden units, partial derivatives are applied again (Pineda, 1987;
Van Dyke Parunak, 1998).
∂En ∂En ∂ak

δj ≡ =∑
∂ai ∂ak ∂aj
k
This equation passes over all units k to which information and connections are
received from unit j. The backpropagation formula is then obtained through
substitution (Pineda, 1987; Van Dyke Parunak, 1998).
δj = h′ (aj ) ∑ wkj δk
k
The backpropagation formula demonstrates the ability to obtain the value for δ from a
particular hidden unit by the propagation of δ values backwards from values higher
ranked in the network (Pineda, 1987; Van Dyke Parunak, 1998).
The general training method for a neural network with backpropagation is displa yed
in Supplementary Algorithm 4
Appendices 268
Supplementary Algorithm 4. General neural network training method.
Provide an input vector 𝐱 n to the network and apply forward propagation
using aj = ∑i wji zi to find the activation of all hidden and output units.
Evaluate δk for all output units using δk = y k − t k.
Apply backpropagation using δj = h′ (aj ) ∑k wkj δk to obtain the δj value
for each hidden unit present in the neural network.
∂En
Evaluate the derivative by = δj zi and utilise to solve the minimisat ion
∂w ji
problem for the network weights.
Various activation functions can be utilised in model training and development for a
neural network. The common activation functions for neural networks are shown in
Supplementary Figure 11.
Supplementary Figure 11. Neural network activation functions.
For each function in Supplementary Figure 11, the basic information processing ability
is similar; however, when training the model, the choice of activation function
becomes important as the gradients will differ in magnitude (Pineda, 1987; Van Dyke
Appendices 269
Parunak, 1998). Additionally, as part of the weight optimisation, different optimisers
are available, including:
Limited-memory Broyden–Fletcher–Goldfarb–Shanno Optimiser
Stochastic Gradient Descent
Adam Optimiser
Cross-Validation and Hyperparameter Tuning
To train the machine learning models, cross-validation and hyperparameter tuning are
used to increase the model accuracy. Cross-validation uses part of the data to fit the
model and part to test the model. This is desirable in cases like the zeolite synthesis
problem, with a small dataset limiting the ability to set aside a validation dataset (Van
Houwelingen, 2004).
K-fold cross-validation splits the data into K roughly equal-sized sets of data. For the
kth partition, the model fits the other K − 1 parts of the data. The prediction error is
calculated for the fitted model when predicting the kth part of the data. Cross-
validation calculates the estimated prediction error where κ: [1, … , N] → (1, … K) is an
indexing function that indicates the partition to which observation i is allocated by
randomisation and ̂f −k (x) is the fitted function computed without the kth partition
(Van Houwelingen, 2004).
N
1
CV (̂f ) = ∑ L(yi , ̂f −κ(i)(xi))
N
i=1
Appendices 270
For a model characterised by a tuning parameter, α, the cross-validation prediction
error is:
N
1
CV (̂f ,α) = ∑ L(y i, ̂f −κ(i) (xi , α))
N
i=1
Validation of Machine Learning Models
Before applying machine learning to the zeolite synthesis data, the machine learning
models were validated against a validation dataset to prove the accuracy and reliabilit y
of the model results.
The machine learning models developed for application in zeolite synthesis use
regression algorithms. The goal of machine learning is to predict the zeolite yield based
on synthesis descriptors and conditions. Therefore, a dataset with similar machine
learning goals was obtained to validate the models. The wine quality dataset has been
widely used in regression and classification machine learning (Cortez et al., 2009).
The data consists of physicochemical information about red and white wine samples.
When used in regression-based machine learning, the physicochemical parameters and
processing conditions are used to predict the quality of a wine sample (Cortez et al.,
2009). The wine quality dataset has similar machine learning goals to the zeolite
synthesis data; therefore, it is the most suitable dataset for validating the models.
The models were validated by comparing the developed model results with published
literature values. The results from the model validation are presented numerically in
Appendices 271
Supplementary Table 16. While the accuracy of the models differed slightly from the
published values, this was attributed to differing model architectures and expected
variation in the results from individual training runs, testing runs, and hyperparameter
tuning.
Supplementary Table 16. Model validation results.

Developed Published Model Error
Model Type Source
Model Accuracy Accuracy Metric
Linear (Gupta,
0.3630 0.3606 𝑅2
Regression 2018)
(Dahal et al,
Ridge Regression 0.3949 0.3869 MSE
2021)
( Dahal et al
Regression Tree 0.3790 0.3741 MSE
2021)
(Mahima et
Random Forest 0.3716 0.4000 MSE
al, 2020)
( Dahal et al
0.3990 0.4000 MSE
2021)
(Caballero,
sklearn ANN
Jojoa, &
0.4938 0.51 MAE
Percybrooks,
2020)
( Dahal et al
PyTorch ANN 0.3968 0.4000 MSE
2021)
(Caballero
0.4989 0.51 MAE
et al., 2020)
The results from the model validation are presented visually in Supplementary Figure
12. Published literature models reported both training and testing results using a
variety of error and accuracy metrics. While it is ideal to use the R 2 value for regression
problems, not all published studies reported this value. The error is presented in terms
of MSE for the testing data for consistency and comparison. Additionally, for the ANN
models, the mean absolute error (MAE) is provided in Supplementary Table 9.
Comparable values in the literature for the linear regression model were only available
Appendices 272
as an R 2 value and therefore are reported in Supplementary Table 9 but not in
Supplementary Figure 12.
Supplementary Figure 12. Machine learning error comparison with published model
data.
The results in Supplementary Table 16 and Supplementary Figure 12 prove the
accuracy and validity of the machine learning models developed in this study. In
addition, there is a high level of correlation between the developed and the published
model error values, therefore, validating the machine learning models for use on the
zeolite LTA synthesis data.
Appendices 273

Andrea Lucia Hidalgo Rocha Thesis

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Andrea Lucia Hidalgo Rocha Thesis

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TRANSFORMATION OF ALUMINOSILICATE

MATERIALS INTO HIGH VALUE ZEOLITES

Andrea Lucia Hidalgo Rocha

Submitted in fulfilment of the requirements for the degree of

School of Mechanical, Medical and Process Engineering

Queensland University of Technology

Acid treatment, Artificial Neural Network, Cancrinite, Cation-exchange

capacity, Hydrothermal, Lithium, Machine Learning, Mother liquor, Natural zeolite,

Quench Method, Spodumene, Thermal Activation, Waste recycling, Zeolite synthesis

catalysis, adsorption, detergents, agriculture, construction, renewable fuels, industrial

solutions of sodium silicate and sodium aluminate in the presence of an organic

impurities present in waste materials can exacerbate the difficulties involved in

synthesizing zeolites, and the process of recycling mining waste in particular is

restricted by the energy-intensive nature of existing methods and their limited

scalability for widespread industrial implementation.

mixture was subjected to hydrothermal synthesis at 80 oC and ultimately produced

precipitated and as a consequence were mixed with the solid cancrinite.

Thus, alternative methods for cancrinite utilization were necessary.

cancrinite powder with lanthanum species resulted in an acceptable method for

performance of the cancrinite-based sorbent was encouraging, it is recommended that

activation occurs at only 100 oC.

reactors is recommended. However, one of the primary challenges in employing such

controlling the reaction conditions. To address this issue, a combination of a

before reaching the next reactor.

By integrating Industry 4.0 principles, particularly machine learning, with continuous

learning algorithms can significantly enhance the optimization of zeolite synthesis in

Developing suitable datasets is particularly challenging when comparing zeolite

accuracy of machine learning predictions. To overcome this, researchers must

design on the synthesis process. Recommendations include pre-heating of reactant

solutions to minimize variation in reaction temperature and avoiding agitation of the

reactant mixture to improve the quality of zeolite LTA.

machine learning methodology to identify the relationship between zeolite synthesis

performance. Chapter 7 shows the application of various machine learning algorithms

neural networks resulted in 85 % accuracy in predicting the zeolite synthesis process.

ANN- Artificial Neural Network

CEC – Calcium Exchange Capacity

DNNs- Deep Neural Networks

HCAS- High Concentration Alkali Solution

HCl- hydrochloric acid

ICP-OES- Inductive Coupled Plasma-Optical Emission Spectrometer

LOI- Loss on ignition

LTA- Linde type A zeolite

ML- Machine Learning

NaOH- Sodium Hydroxide

NZ- Natural Zeolite

OSDA- Organic Structure Directing Agents

PCA- Principal Component Analysis

QSP- Quasi-Solid Phase Activation Process

SLR- Spodumene Leachate Residue

XRD- X-ray Diffraction

XRF- X-ray Fluorescence

Firstly. I would like to express my gratitude and appreciation to my supervisory team:

support through my PhD journey. I am thankful for the scholarships provided by

Queensland University of Technology. This research was supported by QUT

Scholarship funding. I would like to acknowledge the Central Analytical Research

Process Engineering as well as the Faculty of Engineering.

significant help during my candidature, Dr Josefine Probst, Dr Gabriel Colledge, Dr

Cameron Johnston and MSc Richard Freeney.

I would like to acknowledge professional editor, Sue Nielsen, who provided

university-endorsed national “Guidelines for editing research theses”.

and company during my PhD.

love, for always keeping things going.

Application of Machine Learning Principles to Zeolite LTA Synthesis.” Microporous