1C14 Project Study

PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila

College of Engineering and Technology
Department of Chemical Engineering
GEOPOLYMERIZATION OF CERAMIC TILE WASTE,

COAL FLY-ASH AND SPENT BLEACHING EARTH FOR
THE PRODUCTION OF SODIUM
ALUMINOSILICATE MONOLITHS
MACASIL, Renzo C.
REDUBLO, Anne Paulinne P.
SANTOS, Amabelle C.
TORRES, Clark Ivan V.
______________________________
Engr. April Anne S. Tigue
__________________________ ___________________________
Dr. Denvert C. Pangayao Engr. Milagros R. Cabangon
Geopolymerization of Ceramic Tile Waste, Coal Fly Ash, and Spent Bleaching
Earth for the Production of Sodium Aluminosilicate Monoliths Project Study 1
R.C. Macasil, A.P.P. Redublo, A.C.Santos, C.I.V.Torres
BACKGROUND OF THE STUDY

Geopolymerization is an innovative technology that can utilize raw
materials rich in alumina and silica to produce new materials characterized by
three-dimensional polymeric structures called geopolymers. (Panias, D.D., 2016)
Sodium aluminosilicate monolith is a geopolymer that can be used as concrete in
building and construction materials (Provis, J.L. & van Deventer, J.S.J., 2014)
Moreover, it has the greatest potential to replace zeolite adsorbent in removing
heavy metal from wastewater (Ariffin, N., et.al, 2017) Furthermore, this can be
applied in high temperature applications such as furnace linings, fire resistant
coatings, thermal insulation and wall panels (Bernal, S.A., et.al, 2014) According
to Philippine Statistics Authority, the demand of sodium aluminosilicate monolith
amounted to 12,182,230 kg in 2017.
In the production of sodium aluminosilicate monolith, materials rich in

alumina and silica are reacted and formed by alkaline activation at slightly higher
than room temperature (Nguyen, G.H., et.al, 2015) Industrial by-products such as
ceramic tile wastes (CTW), coal fly ash (CFA), and spent bleaching earth (SBE)
shows great potential for silica and alumina sources.
According to Department of Trade and Industry in 2017, only 65% of the

total CTW generated is recycled, leaving 22,235.29 tons of CTW for disposal. Also,
based on the report of Department of Energy, the Philippines generated
168,650.20 metric tons of CFA in producing 46,847,274 MWh of electricity
generation in 2017. Moreover, the spent bleaching earth generated is equal to 0.5
to 1% of the total vegetable oil production (Surhatini et al, 2011). Since the Food
and Agriculture Organization (2017) stated that the vegetable oil produced in the
Philippines is 1,781,000 tons, this signifies that an average, 13,357.50 tons of SBE was
generated in the same year. In addition, Smallwood, N.J. (2011) claimed that 35%
(4,675.125tons) of the SBE is used in the formulation of animal feed blocks and
pellets, leaving 8,682.375 tons of SBE with no significant channel of utilization.
In order to develop a process to utilize CTW, CFA, and SBE to produce

valuable product, the composition of these were analyzed. Based on several
studies, CTW consists of 18.29% alumina and 63.29% silica, CFA has 40-60% silica
and 20-30% alumina, and SBE comprises of 82.16% silica and 2.84% alumina.
(Anwar, A, et.al, 2015; Pace, M.L, et.al, 2011; Moshi, A.P., 2017)
To utilize these wastes generated from various industries in producing a

product with a large range of application, the researchers initiated the study
“Geopolymerization of Ceramic Tile Wastes, Coal Fly Ash, and Spent Bleaching
Earth for the Production of Sodium Aluminosilicate Monoliths”.
STATEMENT OF THE PROBLEM

Based on the report of the Philippine Statistics Authority (2017), the demand
for sodium aluminosilicate monoliths increased by 83.36% from 2012 to 2017. This is
because of the increasing usage of this material in construction and infrastructure
industry. In order to meet the demand for this valuable material, the proponents
developed a method to produce sodium aluminosilicate monoliths through
geopolymerization of coal fly ash, ceramic tile wastes and spent bleaching earth.
Coal fly ash is an industrial by-product derived from coal combustion in

thermal power plants. According to Department of Energy (2018), coal-fired
power plants has remained the dominant energy source in the Philippines with a
share of 35.4% or 8,049 megawatts (MW), and it will continue to increase to over
55% by 2027. In 2017, the total generation of coal fly ash amounted to 168,650.20
metric tons.
This by-product has minimaly utilized as an additive in cement (Rivera, D.,

2017) and largely being disposed in the landfills near the power plant. In addition
to the issue of increasing need for landfill area, coal ash disposal poses the threat
of the contamination of surface waters and groundwater from its heavy metal
and mineral contents and poses harmful effects on the residents living near the
power plant (Santillo, D., 2012)
The most recent incident caused by coal fly ash is the ash fall happened in
Limay, Bataan last January 2017 due to the abandoned ash stockpiles from the
coal fired power plant of Petron-SCPC. This incident caused several residents to
fall ill. The incident also caused soil discoloration around the vicinity of the power
plant due to the presence of heavy metals percolated from the coal fly ash
(DENR-EMB, 2017).
In a similar incident happened in 2013 in Iloilo, in which due to typhoon

Yolanda, the fly ash was blown coming from a 135-megawatt coal fired power
plant operated by the Palm Concepcion Power Corporation. This caused an ash
clouding and most residents experienced heavy breathing and irritated skin
(Burgos, 2017).
Considering these incidents caused by coal fly ash and as generation

quantities are increasing in line with construction of new coal-fired power plants,
large-scale utilizations are also necessary to alleviate disposal issues. One way to
utilize this material is through production of sodium aluminosilicate monoliths
through geopolymerization process since coal fly ash has an average silica (SiO2)
content ranging between 40-60% and alumina (Al 2O3) content between 20-30%.
In addition, spent bleaching earth is combined with coal fly ash, because
of its high generation in the Philippines and it has no significant utilization. The spent
bleaching earth is highly susceptible to spontaneous combustion due to the 20%
to 40% by weight (Lim, W.S. et al, 2013) of oil entrained in it. According to Mecpro
(2012), spent bleaching earth is usually disposed of in landfills or waste dumps
which can cause environmental hazards, since it is prone to catching fire, besides
polluting the ground water. Handling and disposing of spent earth is a fire risk, an
operating expense, and a source of environmental regulatory concerns (DENR,
2018).
Furthermore, ceramic tile waste is also added because of its high

generation and good alumina and silica content. Ceramic Tile Waste is a non-
hazardous material, but its non-biodegradability poses a problem because these
wastes will remain in the environment for hundreds, perhaps thousands, of years.
These non-decaying waste materials, combined with a growing consumer
population, has resulted in a waste disposal crisis (Bhavin & Bhatt, 2016).
In an attempt to solve the aforementioned issues, the researchers proposed

the study entitled, “Geopolymerization of Ceramic Tile Waste, Coal Fly Ash, Spent
Bleaching Earth for the Production of Sodium Aluminosilicate Monoliths”.
OBJECTIVES OF THE STUDY

A. General Objective
To produce sodium aluminosilicate monolith through geopolymerization of
pretreated spent bleaching earth, ceramic tile waste, and coal fly ash.
B. Specific Objectives
This study aims to achieve the following specific objectives:
To produce sodium aluminosilicate monolith that will conform to the
properties of the standard and existing product shown in Table 1.1
Table 1.1 Standard and Existing Properties of Sodium Aluminosilicate Monolith
PARAMETER STANDARD EXISTING PROPOSED

Density
<1680 [1] 700-1600 [2] 1310
(kg/m3)
FOR CONSTRUCTION:
Compressive
>11.70 [1] 10-15 [2] 12.4
Strength (MPa)
FOR ADSORBENT:
Porosity 15-25% 17.03%
Freundlich
0.06 - 0.09 0.07
Constant
Adsorption
1-10 1.63
Intensity
SEM Image -
[2]
Source: (1) ASTM C90-14, Kalaw, et.al, 2016

(2) AAC Lightweight Block Corporation
(3) K. Vijai 1 , R. Kumutha and B. G. Vishnuram, 2010
To develop an experimental method and come up with the optimum

operating conditions that would produce sodium aluminosilicate monolith
with optimum yield.
To determine the market feasibility of sodium aluminosilicate monolith

through the analysis of projected demand and supply and developing
marketing strategies, that would enable the product to penetrate the
market.
To design a detailed manufacturing process of sodium aluminosilicate

monolith production with the corresponding equipment, piping system,
instrumentation, and process control, safety procedure, and wastewater
treatment facility.
To assess the economic feasibility of manufacturing sodium aluminosilicate

monolith by determining total capital investment, total production cost,
source of funding, profitability, breakeven point, rate of return, and payout
period of the company.
SIGNIFICANCE OF THE STUDY

The study titled “Geopolymerization of Ceramic tile waste, Coal fly ash, and
Spent Bleaching Earth for the Production of Sodium Aluminosilicate Monoliths” will
impart significance to the following sectors of the society:
To the Researchers in the Chemical Engineering Field
This study will provide constructive data and information for both
undergraduates and researchers who are interested in studying the
potential of Coal Fly Ash, Ceramic Tile Waste and Spent Bleaching Earth as
raw materials and the manufacturing process of aluminosilicate monoliths.
Moreover the undergraduates and the researchers will be able to apply
their understanding on the theories and principles which will lead to
developing a more applicable, practical and economical process in
producing Sodium Aluminosilicate Monolith out of various materials.
To the Ceramic Tile Manufacturers, Oil Industry and Coal fired Power Plant
The utilization of Ceramic Tile Waste, Spent Bleaching Earth and Coal
Fly ash will generate value added income for the Ceramic Tile
Manufacturers, Oil Industry and Coal Fired Power Plant. The parties can sell
the by-products to the potential manufacturers of geopolymer.
To the Country
This study will provide a new channel of utilization for ceramic tile
waste, coal fly ash and spent bleaching earth that will improve the diversity
of the market for raw materials. This will also decrease the country’s
dependency on imported raw materials and provide a prospect area in
the labor market.
SCOPE AND LIMITATIONS

The study aimed to produce sodium aluminosilicate monolith from ceramic
tile waste, coal fly ash and spent bleaching earth through pretreatment of the raw
materials (size reduction for ceramic tile waste and leaching for spent bleaching
earth), geopolymerization, blowing and curing. It covers the market study of the
product, experimental, economic study and industrial design of the process, as
well as the different unit operations involved in the production of sodium
aluminosilicate monolith from ceramic tile waste, coal fly ash and spent bleaching
earth. The industrial-scale material and energy balances, unit operations and
processes involved are taken into consideration in the design of different
appropriate equipment to produce the sodium aluminosilicate monolith, which
conforms to the standard properties of the product. The data and assumptions
based from the experiment are also considered in the design calculations for each
equipment. The piping system of process, hot water, chilled water and steam, as
well as the instrumentation and process control are also indicated.
Information and statistical data regarding the main raw material were
gathered from the SEM-Calaca Power Plant (coal fly ash), Mariwasa Siam
Corporation (ceramic tile waste), and San Pablo Manufacturing Corporation
(spent bleaching earth). Furthermore, the data for the product was gathered from
the Foreign Trade Statistics Division of the Philippine Statistics Authority (PSA)
located in Quezon City. The properties of sodium aluminosilicate monolith were
obtained from Department of Trade and Industry- Bureau of Product Standards.
For the experimental study, it is done on a laboratory scale only and errors
as well as deviations from the study are expected. Factorial design of experiment
was used to determine the suitable set of parameters that will give the highest
value of compressive strength. The raw materials are gathered from the SEM-
Calaca Power Plant (coal fly ash), Mariwasa Siam Corporation (ceramic tile
waste), and San Pablo Manufacturing Corporation (spent bleaching earth). The
reagents were purchased from Alysons’ Chemical Enterprises and RB Chemodities

Marketing. The experiment was performed at PLDTSFH-CHE-LAB.
The testing of the raw materials was conducted by Department of

Agriculture – Bureau of Animal Industry (Chemical and Feed Analysis Section) for
the proximate analysis of spent bleaching earth. On the other hand, the raw
materials are characterized by Intertek Minerals Philippines using X-ray
fluorescence to determine its elemental composition. Also, the raw materials and
intermediates were tested using Fourier-transform infrared spectroscopy (FTIR) at
De La Salle University in order to verify that the desired reactions took place. Lastly,
the product was tested by SGS Philippines for its tensile strength and elongation at
break and Nanotech Analytical Services and Training Corporation for the surface
topography.
The optimum parameters were determined during the experimental study.

Then, analyses of the demand and supply of the product were performed, data
was collected from 2012 to 2017 and the value for the succeeding years up to
2024 was determined using different projection methods for the marketability.
Also, the design of different equipment for unit operations and processes involved
in the study were dependent on the results of the experimental study.
Likewise, the economic aspect of the study accounted the costs involved
in the whole operation of the proposed manufacturing plant. Financial statements
were also included to check the availability of finances, expected rate of return,
and the product selling price to ensure the profit of the company.
REVIEW OF RELATED LITERATURE

Sodium aluminosilicate monolith, as shown in Figure 2.1, is a geopolymer
material which has been foamed to achieve lightweight and good thermal
insulating property that can compete with traditional inorganic porous materials.
Figure 2.1. Sodium Aluminosilicate Monoliths
It possesses excellent physicochemical and mechanical properties,

including low density, high strength, thermal stability, and improved resistance to
acids and the action of fire. as well as the good ability to immobilize toxic metals
(Ducman V. & Korat L., 2016). Its physical and chemical properties are summarized
in Table 2.1.
Table 2.1 Standard and Existing Properties of Sodium Aluminosilicate Monolith
PARAMETER STANDARD EXISTING PROPOSED

Density
<1680 [1] 700-1600 [2] 1310
(kg/m3)
FOR CONSTRUCTION:
Compressive
>11.70 [1] 10-15 [2] 12.4
Strength (MPa)
FOR ADSORBENT:
Porosity 15-25% 17.03%
Freundlich
0.06 - 0.09 0.07
Constant
Adsorption
1-10 1.63
Intensity
SEM Image -
[2]
Source: (1) ASTM C90-14, Kalaw, et.al, 2016

(2) AAC Lightweight Block Corporation
(3) K. Vijai 1 , R. Kumutha and B. G. Vishnuram, 2010
It is considered as today’s emerging material as the world is rapidly going
through industrialization. Since their production is mainly based on waste materials,
their accelerated use could contribute significantly to the achievement of
environmental goals, including the lowering of the CO2 footprint of the
construction industry.
USES AND APPLICATIONS OF SODIUM ALUMINOSILICATE MONOLITH
Building & Construction Materials

Sodium aluminosilicate monolith is used to make concrete, which
have been used for the construction of houses, garages, and other
structures including high-rise buildings. (Provis, J.L. & van Deventer, J.S.J.,
2014).
Insulator
The inorganic framework of sodium aluminosilicate monolith leads to
excellent thermal stability, which enables these materials to be used in high
temperature applications such as furnace linings, fire resistant coatings,
thermal insulation and wall panels. (Bernal, S.A., et.al, 2014)
Lightweight Materials Production

It can be used as lightweight concrete roof deck, lightweight wall
and floor panel partitions, and lightweight concrete blocks. (Bernal, S.A.,
et.al, 2014)
Adsorbent
Sodium aluminosilicate monoliths has the greatest potential to
replace zeolite adsorbent in removing heavy metal from wastewater since
they have similar amorphous structure constituted by SiO 4 and AlO4
tetrahedra (Ariffin, N., et.al, 2017)
Fiber Reinforcing
It is used to improve performance by raising the tensile strength and
the fracture toughness, and enhancing the ductility and durability of the
final product. (Provis, J.L. & van Deventer, J.S.J., 2014)
With these applications, this indicates that there is a high marketability for
geopolymer (sodium aluminosilicate monolith) production. In fact, there has been
an increase in its importation (or local demand) while its exportation (or local
supply) remains low. According to Philippines reported by Philippine Statistics
Authority, the demand of sodium aluminosilicate monolith grew continuously from
5,185,311 kg in 2012 to 12,182,230 kg in 2017.
The Philippine Market Demand and Supply of Sodium aluminosilicate

monolith is summarized in Table 2.2. The data was taken from Philippine Statistics
Authority.
Table 2.2 Philippine Market Demand and Supply of Sodium Aluminosilicate Monolith
Year Demand (kg) Supply (kg)

2012 5,875,746.00 605,480.00
2013 5,185,311.00 618,185.00
2014 6,276,757.00 617,977.00
2015 7,906,793.00 545,144.00
2016 9,423,086.00 269,396.00
2017 12,182,230.00 179,379.00
Source: Philippine Statistics Authority, 2018
It can be seen in Table 2.12 that there is a continuous increasing trend for
the demand of sodium aluminosilicate monolith in the Philippines. This high
demand is linked to the construction and infrastructure industry of the Philippines

which grew up to a rate of 12% in 2015 (Philippine National Statistical Coordination
Board, 2016). As for the pricing, sodium aluminosilicate monolith is said to cost
around Php 1200.00 per cubic meter and Php 140 per kilogram according to
Henan Botai Chemical Building Materials Co., Ltd.
In this study, the sodium aluminosilicate monolith was produced through

geeopolymerization of pretreated spent bleaching earth, ceramic tile waste, and
coal fly ash as shown below.
Figure 2.5 Sodium Aluminosilicate Production through Geopolymerization
First, SBE was leached to remove 20-30% residual oil using isopropanol, then
it is filtered through a filter paper to separate the spent isopropanol containing
residual oil from the SBE cake, which was ground and sieved using 250µm Mesh to
increase the surface area for reaction. Also, CTW was ground and sieved using
the same mesh size as SBE. The SBE, CTW, and CFA were mixed continuously, and
added with an alkali activator which is a mixture of sodium silicate and sodium
hydroxide, to initiate geopolymerization reaction. The resulting paste was added
with hydrogen peroxide, which gives a porous and lightweight sodium
aluminosilicate monolith.
In the chosen process, preliminary treatment is necessary to the raw

materials to remove the impurities and to achieve the optimum particle size to be
used in the process. Coal fly ash were not pre-treated due to it has a fine particle
size. On the other hand, ceramic tile waste underwent size reduction to achieve
the same particle size of coal fly ash. Furthermore, spent bleaching earth
underwent leaching process to remove residual oil.
Leaching
The first unit operation to treat the spent bleaching earth is leaching.
Leaching is a process for the separation of one or more components through
intimate contact with a second immiscible liquid called a solvent. When some of
the original substances are solids, the process is called leaching. (Couper,
Chemical Process Equipment: Selection and Design) According to Khalil, N.M
(2013), spent bleaching earth has 20-30% residual oil which will be leached using
an organic solvent to separate it from the solid material.
In choosing the suitable solvent to be used in this process, the substance

should be non-polar, has a low latent heat and a high selectivity among other
solvents (S. P. Jeevan Kumar, 2017). Oil and fats from oil bearing materials exhibit
high soulbility in solvents like n-hexane, toluene, and petroleum ether.
After the pre-treatment process, coal fly ash, ground ceramic tile waste
and treated spent bleaching earth were blended having a pre-determined mass
ratio. Then it underwent the process of geopolymerization.
Geopolymerization
Geopolymerization is an innovative technology that can utilize solid raw
materials rich in alumina and silica to produce new materials characterized by
three-dimensional polymeric structures called geopolymers. (Panias, D.D., 2016) In
the production of sodium aluminosilicate monolith, materials rich in alumina and
silica are reacted and formed by alkaline activation at slightly higher than room
temperature (Nguyen, G.H., et.al, 2015)
Figure 2.6. Geopolymerization Reaction
The mechanism involves the dissolution of Al and Si in the alkali medium,

transportation (orientation) of dissolved species, followed by a polycondensation,
forming a 3D network of silico-aluminate structures. According to Davidovits, these
structures can be of three types: poly(sialate) (–Si–O–Al–O–), poly(sialate– siloxo)
(Si–O–Al–O–Si–O) and poly(sialate–disiloxo) (Si– O–Al–O–Si–O–Si–O). The setting
(hardening) of geopolymer is believed to be due to the polycondensation of
hydrolyzed aluminate and silicate species (De Silva, 2007). In addition, Glukhovsky
(1967), proposed a step-by-step mechanisim of geopolymerization:
First Stage: “Destruction Coagulation”
Figure 2.7. Destruction Coagulation
The -OH ions as shown in Figure 2.7, initiate the rupture of the Si–O–Si bonds.
This takes place by the action of the OH– redistributing the electron density around
the silicon atom and rendering the Si–O–Si bond more susceptible to rupture. The
appearance of Si–O––Na+ bonds hinders the reverse reaction from forming
siloxane bonds. These alkaline silicates may also take part in ion exchange
reactions with divalent ions to form ∫Si–O–Ca–OH type complexes.
The –Si–O–Na+ complexes, which are stable in alkaline media, create

conditions suitable for the transport of the reacting structural units and the
development of the coagulated structure. Therefore, the cation catalyses these
reactions, maintaining the ionic force needed to destroy the covalent bonds and
thereby participating in the conversion of the bonds destroyed into a colloidal
phase.
Second Stage: “Coagulation - Condesation”
Figure 2.8. Coagulation - Condensation
For the second stage, the enhanced contact among the disaggregated
products, made by accumulation, forms a coagulated structure where
polycondensation takes place.
The condensability of silicic acid rises with high pH values, at which it is

slightly dissociated or in a molecular state. Therefore, at pH > 7, the disaggregation
of the Si-O-Si bond gives rise to a hydroxylated complex, Si(OH)4, which condenses
to form a new Si–O–Si bond and generate the dimers as shown in Figure 2.8.
This reaction is catalysed by the OH– ion. The clusters formed by the
polymerisation of orthosilicic acid may grow in all directions, generating colloidal
particles. Aluminate also participates in these polymerisation reactions,
substituting isomorphously for silicate tetrahedra. While the alkaline metal
catalyses destruction in the first stage, in the following two it is a structural
component.
Third Stage: “Condensation - Crystallization”
Like the appearance of microparticles

resulting from the condensed structure, the
presence of particles in the initial solid phase
prompts the precipitation of products whose
composition is determined by the mineralogical
and chemical composition of the initial phase, the
nature of the alkaline component and hardening
conditions.
Furthermore, Duxson et. al. (2007), discussed

the mechanism of the geopolymerization reaction.
The findings resulted to a simultaneous processes as
shown linearly in Figure 2.9.
Initially, the contact between the solid

particles and the alkaline solution causes the
vitreous/amorphous component of these particles
to dissolve (this is the mechanism that governs the Figure 2. 9 Geopolymerization
dissolution of solid particles in the early stages), Mechanism
releasing aluminates and silicates as monomers.
These monomers inter-react to form dimers, which in turn react with other
monomers to form trimers, tetramers and so on. When the solution reaches
saturation an aluminosilicate gel precipitates. Initially this is an aluminium-rich gel
(denominated Gel I, an intermediate reaction product). As the reaction
progresses, more Si-O groups in the initial solid source dissolve, increasing the silicon
concentration in the medium and gradually raising the proportion of silicon in the
zeolite precursor gel (Gel 2).
According to Fernandez-Jimenez et.al. (2006), the structural reorganisation

processes determine the final composition of the polymer as well as pore
microstructure and distribution in the material, which are critical factors in the
development of many physical properties of the resulting product.
Blowing
After the minerals have been alkali activated, the blowing process is to
follow whereas, the reaction between the Al metal powder and alkaline activator
proceeds quickly, during the reaction releases hydrogen. The blowing agent is
thermodynamically unstable and therefore can be easily decomposed to water
and oxygen gas.
Figure 2.10. Blowing Process
Through the process presented above, sodium aluminosilicate monolith

can be produced by using the geopolymerization process. Since
geopolymerization requires materials possessing a significant amount of silica and
alumina, ceramic tile wastes, coal fly ash and spent bleaching earth were used.
Ceramic tile waste, as shown in Figure 2.11, is a solid waste generated from
ceramic industry that is caused either by the process or human error. According
to Jacob, E. (2017), 15-30% of the daily production of ceramic industry become
waste amounting to thousands of tons of ceramic tile waste generated annually.
Figure 2.11. Ceramic tile wastes
According to Department of Trade and Industry, the ceramic tile industry

produces 30 million square meters annually or 360,000 tons of ceramic tiles per
annum. However 15% of the daily production of ceramic tiles become waste and
according to the ceramic arts network only 65% of these wastes were recyclable
leaving 22,235.29 tons of ceramic tile waste for disposal.
The first factor to be considered for the raw material is its silica and alumina
content. In order to develop a process to utilize ceramic tile waste to produce
valuable product, the composition of ceramic tile waste was analyzed. The
average chemical composition of ceramic tile waste and other possible sources
is shown in Table 2.4.
Table 2.4. Comparison of Possible Sources of Alumina for Geopolymerization
CERAMIC TILE
COMPOSITION BRICK WASTE[1] META KAOLIN[1]
WASTE[2]
Al2O3 10.64% 41.46% 18.29%
SiO2 58.00% 54.34% 63.29%
Fe2O3 4.82% 0.86% 4.32%
SO3 1.78% - 0.10%
CaO 15.80% 0.09% 4.46%
MgO 3.88% 0.18% 0.72%
TiO2 0.55% 1.70% 1.17%
Sources: [1] Fusco, O., et.al,2014; [2] Anwar, A, et.al, 2015
As depicted in Table 2.4, it can be observed that ceramic tile waste is

composed mainly of silica, followed by alumina. This shows that ceramic tile waste
has great potential as raw material in production of geopolymer monoliths since
high rich Alumina-Silica materials are needed to produce three-dimensional
aluminosilicate complex (Akbari et al., 2015)
In addition, ceramic tile waste has the highest SiO2 content of 63.29%,
followed by metakaolin. This is the main reason why among the three, ceramic tile
waste was chosen as the source of raw material for geopolymerization. Also
despite of metakaolin having a higher alumina content compare to ceramic tile
waste, ceramic tile waste was chosen because metakaolin has already been
used as a filler or reinforcement in cement. On the other hand, the ceramic tile
waste is considered as an industrial by product and there is hardly any practical

application. (Anwar, A, et.al, 2015).
In addition, ceramic tile waste can be obtained from the following ceramic
tile processing plants in the Philippines as shown in Table 2.5:
Table 2.5. Possible Sources of Ceramic tile waste
Company Name Location

Brgy. San Antonio, Santo Tomas
Mariwasa Siam Ceramics Inc.
Batangas, Philippines
Formosa Ceramic Tiles Manufacturing Quezon Road, San Isidro, San Simon,
Corp. Pampanga
Unit 201, Prestige Tower, F. Ortigas Jr.
Eurotiles Industrial Corporation
Road, Ortigas Center, Pasig City
Lepanto Ceramics Inc. Makiling, Calamba City 4027 Laguna
In this study, the ceramic tile waste were generated from Mariwasa Siam
Ceramics Incorporated. Another raw material used in this study is the coal fly ash
as shown in Figure 2.12.
Figure 2.12. Coal Fly Ash
It is a coal combustion product that is composed of the particulates (fine

particles of burned fuel) that are driven out of coal-fired boilers together with the
flue gases. Fly ash is generally captured by electrostatic precipitators or other
particle filtration equipment before the flue gases reach the chimneys.
The first consideration in choosing this raw material is its silica and
alumina content. Depending upon the source and composition of the coal being
burned, the components of fly ash vary considerably, but all fly ash includes
substantial amounts of silicon dioxide (SiO2) (both amorphous and crystalline),
aluminium oxide (Al 2O3) and calcium oxide (CaO), the main mineral compounds
in coal-bearing rock strata. The average chemical composition of coal fly ash is
shown below depending on different coal types.
Table 2.6. Chemical Composition of Coal Fly Ash from Different Coal Types
Components Bituminous Sub-bituminous Lignite

SiO2 20-60 40-60 15-45
Al2O3 5-35 20-30 10-25
Fe2O3 10-40 4-10 4-15
CaO 1-12 5-30 15-40
MgO 0-5 1-6 3-10
Na2O 0-4 0-2 0-10
K2O 0-4 0-2 0-6
SO3 0-3 0-4 0-4
LOI 0-15 0-3 0-5
Table 2.6 shows that sub bituminous coal can give a higher percentage of
silica and alumina from fly ash produced from its combustion or burning process.
Whereas, these hazardous wastes with high silica and alumina content can
undergo the process of geopolymerization and can be turn into Sodium
Aluminosilicate Monoliths that is of higher quality than the usual adsorbents that
are being produced in the market.
Other possible sources of silica and alumina are compared to that of the
coal fly ash. These materials such as the boiler slag, known as the bottom ash, and
sugarcane bagasse ash were considered and presented in Table 2.7.
Table 2.7. Comparison of Coal Fly Ash, Boiler Slag, Sugarcane Bagasse Ash
Composition Coal Fly Ash Boiler Slag Sugarcane Bagasse Ash

SiO2 40-60 46.87 78.34
Al2O3 20-30 18.8 8.55
Fe2O3 4-10 5.9 3.61
CaO 5-30 17.8 2.15
MgO 1-6 4.0 3-10
Na2O 0-2 1.3 0.12
K2O 0-2 0.3 3.46
SO3 0-4 - 0-4
LOI 0-3 - 0.42
As presented in Table 2.7. It can be observed that the sugarcane bagasse

ash has the highest amount of silica but it has a low amount of alumina in
comparison to the coal fly ash and boiler slag, hence it is not selected. On the
other hand, the boiler slag, which is the bottom ash, is not selected as the raw
material because according to Hanania et al (2015), boiler slag is rather used as
a construction filler rather than a material for geopolymerization.
Another consideration is the availability of the raw material. Coal fly ash is
the most voluminous and well-known constituent which makes up more than half
of the coal leftovers (Palmer, 2015). The country generated 168,650.20 metric tons
of coal fly ash for the year 2017 in producing 46,847,274 MWh of electricity
generation (Department of Energy, 2018). Moreover, due to the country’s main
dependence on coal as source of electricity, generation and release of these
undesirable pollutants into the environment grow as its disposal are not advisable
to be used and poses harmful effects.
Furthermore, although there are adverse effects on utilization of coal as an
energy source, the country still depends on it to meet the demand for electricity.
According to the Power Statistics Report of DOE for 2017, the country’s electricity
consumption gained by an average of 3.93% and is expected to continue to grow
up to 5% for the year 2020-2022. Therefore, new ventures in constructing 23 new

coal fired power plants is targeted to be established by the year 2020
(Saulon,2017). In line with this projection in mind, it is expected that more waste will
be generated as more coal power plants are to be established.
From the coal power plants, coal fly ash is being disposed in landfills near
the power plant however, they are considered undesirable for it poses harmful
effects. (Breen, 2009). This is supported by an incident happened last January
2017, in which the regional office of the Environmental Management Bureau (EMB)
in Central Luzon has ordered Petron Corp. to stop any activity inside its coal-fired
power plant in Limay, Bataan because the abandoned ash stockpiles caused ash
fall within the localities that has reportedly caused several residents to fall ill.
Similarly, in 2013 fly ash was blown coming from a 135-megawatt coal fired
power plant operated by the Palm Concepcion Power Corporation in Iloilo. This
caused an ash clouding and most residents experienced heavy breathing and
irritated skin (Burgos, 2017).
In addition, the worst impact caused by the scattering of the fly ash was soil
discoloration. The agricultural soil around the vicinity of the power plant which was
originally brownish has turned to white because of coal ash. This was most
probably due to the presence of heavy metals percolated from the coal fly ash.
The agriculture food supply has also been covered with this coal ash. Therefore, in
this study, the coal fly ash will be used as a raw material. The location and the
capacity of each power plant which can be a source of the raw material are
shown in Table 2.8.
Table 2.8. Existing Coal Fired Power Plants in Luzon Grid
Facility Name Installed Capacity, MW

Anda 83.7
APEC 52.0
Calaca 300.0
Mariveles 345.0
Masinloc 344.0
Pagbilao 382.0
Quezon Power 511.0
Petron-SCPC 150.0
SLPGC 150.0
SLTEC Puting Bato 135.0
Sual 647.0
UPPC 30.0
In this study, coal fly ash were gathered from Pozzolanic Philippines Inc.,
which is a sister company of SEM- Calaca Power Plant. Lastly, spent bleaching
earth is used as a raw material in this study. Spent bleaching earth (SBE), as shown
in Figure 2.13, is a solid waste generated in vegetable oil industry. During the
refining process, bleaching earth is used to remove color, phospholipids, residue
gums, oxidized products and any trace metals from the oil. These colored
pigments are trapped and absorbed in the bleaching earth, thus transforming the
originally whitish earth to dark grey, which is the generated spent SBE. SBE is
considered as an industrial by-product as there is hardly any practical application
for it. (Kheang, N., et.al, 2010)
Figure 2.13. Spent Bleaching Earth
Based on several studies, SBE contains 20-40% residual oil (Lim, W.S., et.al,
2013), 1.94% moisture content, and 65.39% ash (Moshi, A.P., 2017). Moreover, the
total ash or mineral content of SBE constitutes 82.16% silicon dioxide, 2.84%
aluminum oxide, and others, as shown in Table 2.9. According to Provis, J.L. & van
Deventer, J.S.J., (2014), material with high silicon dioxide content has the great
potential as raw material in the production of sodium aluminosilicate monoliths.
Table 2.9 Comparison of Possible Sources of Silica
Source: Quesada, D.E, 2015
Based on Table 2.9, clays and spent filtration earth (SFE) which is also a by-
product in vegetable oil refineries are possible candidates as feedstock in
geopolymer monolith production. However, among the three materials, spent
bleaching earth has the highest silicon dioxide content. Also, it is noticeable that
the calcium oxide in clays and SFE are higher than that of SBE. Based on the study
of Wang, D.L., et.al. (2009), the compressive strengths of geopolymers with high
calcium oxide decreases with curing time and temperature.
Another consideration is the generation of spent bleaching earth in the

Philippines. According to Suhartini, S., et.al (2011), the amount of spent bleaching
earth generated is 0.5-1% of the total production of vegetable oil. In the
Philippines, 1,781,000 tons of vegetable oil is produced in 2017. (Food and
Agriculture Organization, 2017). Thus, at an average, 13,357.50 tons of spent
bleaching earth is generated in the Philippines. According to Smallwood, N.J.
(2011), 35% (4,675.125tons) of the SBE is used in the formulation of animal feed
blocks and pellets, leaving 8,682.375 tons of SBE with no significant channel of
utilization. Spent bleaching earth can be obtained from vegetable oil (coconut
oil, palm oil, soybean oil) refineries. Some of the possible sources of spent
bleaching earth in the Philippines are as follows:
Table 2.10. Possible Sources of Spent Bleaching Earth
Company Name Location Type of Vegetable Oil

Malabon Soap and
Luna II St. Malabon, Metro
Oil Industrial Coconut Oil
Manila
Company
9TH Ave., Taguig, Metro Soya oil, Corn oil, Canola
NutriAsia, Inc
Manila oil, Palm oil
Caloocan Industrial
Trans-Asia Philippines Subdivision, Bano Kaybiga, Coconut Oil
Caloocan City
Mt. Makiling 63 Barangay Mamatid,
Palm Oil, Coconut oil
Coconut Oil Mill Cabuyao City Laguna
San Pablo
Unichem Road, Bauan, Soya Oil, Coconut Oil,
Manufacturing
Batangas Corn Oil
Corporation
Queens Best
Cooking Oil and Purok 3, Landayan Street, San
Coconut Oil
Marketing Pedro, Laguna
Corporation
REVIEW OF RELATED STUDIES

Geopolymers are inorganic polymers formed from the alkaline activation
of amorphous alumino-silicate materials resulting in a three-dimensional polymeric
network. Ceramic tile waste, coal fly ash and spent bleaching earth were used
to produce sodium aluminosilicate monoliths. Prior to the geopolymerization
process, preliminary treatment for each of the raw materials are conducted.
The particle size of ceramic tile waste were reduced to acieve a uniform
particle size with coal fly ash and spent bleaching earth. In a study conducted by
Sun et. al (2013), 30 micrometers is the optimum particle size of ceramic tile waste.
On the other hand, for coal fly ash, the optimum particle size to be used for coal
fly ash is 250 micrometer (Kalaw et.al, 2016). In a similar study conducted by
Promentilla et. al. (2018), a particle size of 90 micrometers was usedd. Therefore,
the proponents of this study used 30 micrometer particle size for ceramic tile waste
and 90-250 micrometer for coal fly ash.
For the spent bleaching earth, since it contains residual oil, it underwent
the process of leaching. The recovery of oil from spent bleaching earth includes
a contact with organic solvents. According to Bird (2002), the solvent to be used
should not be reactive with the bleaching earth and can dissolve the oil such as
n-hexane, toluene, acetone, isopropanol and xylene at a temperature between
35 to 50 degrees Celsius. In addition, the optimum time for the process is 50 minutes
(Manan, 2017). In this study, the proponents used n-Hexane, isopropanol and
acetone as solvents , in temperatures between 40 to 60 degrees Celsius and time
between 30 to 60 minutes.
After the preliminary treatment, the raw materials are mixed in portions
using Scheffe-based model to determine the mix proportions and to obtain the
optimum mix conditions of a CFA-CTW-SBE ternary mix geopolymer for a target
application requiring low thermal conductivity, high adsorption uptake and
medium medium strength structural material (Kalaw, 2016).
The ratio of the CFA-CTW-SBE mixture and the alkali activator is also varied
based on the studies of Ho et. al (2018), Promentilla et. al (2017) and Kalaw et. al
(2016). Sodium silicate, sodium hydroxide and sodium aluminate are used as alkali
activators in the process. The ratio of the alkali activator is also determined. After
the geopolymerization process, blowing or the decomposition reaction of blowing
agent is conducted to increase the porosity of the monoliths. In this study,
hydrogen peroxide is used as a blowing agent varying its from 0.75% H 2O2 to
3.00% H2O2 (Labrincha et.al. , 2017). The mixture will be moulded in a circular and
rectangular mold having a size of 50 x 50 x 50 mm and cured and dried.
SUMMARY OF REVIEW OF RELATED STUDIES
Title of the Study,

Author/s, Summary of Study Relevant Information Obtained
Year of Publication
The overall performance of a geopolymer can
be determined by considering several properties
such as:
1. Mechanical Properties
This work presents a systematic
a. Compressive Strength
method that integrates the
statistical design of experiment, (ASTM C109/C109M)
multiple response optimization b. Volumetric Weight
Optimizing Geopolymer-Based
technique and analytic (ASTM C55-99)
Material for Industrial
hierarchy process for product c. Water Absorption
Application with Analytic
design of geopolymer-based
1 Hierarchy Process and Multi- (ASTM C140)
materials. The method is
Response Surface Analysis 2. Thermal Properties
demonstrated using a case
study involving a geopolymer a. Thermal Conductivity
Sumabat, A., et.al, 2015
from a ternary blend of red (ASTM C332)
mud, b. Volumetric Shrinkage
rice hull ash, and (ASTM C210-95)
diatomaceous earth.
3. Sustainability Criteria
a. Production Cost
b. Embodied energy (includes
transportation of the raw material)
Mechanical and Thermal In this study, mechanical and Analysis of raw materials should be done such
2 Properties of Geopolymers from thermal properties of as:
Mixtures of Coal Ash and Rice geopolymers formed from 1. Particle size (μm) using diffractometer
Geopolymerization of Ceramic Tile Waste, Coal Fly Ash, and Spent Bleaching Earth for the Production of Sodium
Aluminosilicate Monoliths Project Study 30
Hull Ash using Water Glass mixtures of coal bottom ash 2. Surface area
Solution as Activator (CBA), rice hull ash (RHA), coal 3. Density (kg/m3)
fly ash (CFA), with sodium 4. Chemical composition (using X-ray
Kalaw, M.E., et.al, 2015 silicate solution as activator
fluorescence dispersive or XRF analysis)
were 31valuated.
Alkali Activator used: Sodium Silicate
Synthesis of a one-part Sieve Size: Mesh no. 4
geopolymer system for soil
stabilizer using fly ash and Sodium Silicate
3
volcanic ash Alkali Activator used: Sodium Hydroxide
Sodium Aluminate
Tigue, A.A.S, et.al, 2017
Grinding Time: 30 minutes
Mesh Size: 90 µm- mesh
 highest value of
Development of Geopolymer-
This study focuses on utilization compressive
Based Materials Indicator after
of coal bottom ash (CBA) and strength
from Coal Bottom Ash and Rice geopolymerization:
riche husk ash (RHA) to
4 Husk Ash  lowest value of
produce geopolymer – based
with Sodium Silicate Solutions water absorption
materials using sodium silicate
solution as an alkali activator Optimum ratio
Promentila, M.A.B, et.al., 2018
(CBA:RHA:WGS) 35:35:30 by % weight
Mould Size: 50x50x50 mm
Curing Temperature: room temperature
Investigation on mixture design This study presents a one-part Drying Temperature of
105°C
of one-part geopolymer from geopolymer system from coal Sludge/Mud:
5
fly ash and water treatment fly ash and water treatment Solid sodium
sludge sludge. Formulation of the Alkali Activator used:
hydroxide (NaOH),
proportion of geopolymer sodium aluminate

Ho, V., et.al., 2018 precursors with the two solid (NaAlO2)
alkali activators was Mixing Time: 10-30 minutes
conducted using statistical
Mold Size: 50x50x50 mm
mixture design. Effects of each
components as well as Curing Temperature: room temperature
interactions between them 18.9% sludge
were evaluated by step-wise Optimum ratio 76.1% fly ash
regression analysis. 5.0% NaOH.
In this study, geopolymer Mesh Size of coal ash: 250 µm- mesh
samples were formed from the Mold Size: 50x50x100 mm
Optimizing and Characterizing
mixture of coal ash, using both 85% CFA
Geopolymers from Ternary
coal fly ash (CFA) and coal Optimum ratio: 10% CBA
Blend of Philippine Coal Fly Ash,
bottom ash (CBA), and rice hull
6 Coal Bottom Ash and Rice Hull 5% RHA
ash (RHA). The mechanical,
Ash 80% (w/w) 12 M NaOH
thermal and Alkali Activator used
microstructural properties of 20% (w/w) sodium
Kalaw, M.E., et.al, 2016 and ratio:
the geopolymers formed were silicate
analyzed. Mixture Design: Scheffe-based Model
Waste ceramic was activated

Synthesis and thermal behavior
by alkali hydroxides and/or Grinding Time: 45 minutes
of geopolymer-type material
sodium/potassium silicate
7 from waste ceramic
solutions to synthesize
geopolymer-type material in
Sun, Z., et.al, 2013 Particle Size: 30 µm
this study.
The vegetable residual oil from

8 Solvent: n-Hexane
waste spent bleaching earth is
Recovery of Vegetable Oil from extracted through Soxhlet

Spent Bleaching Earth: Stateof- extraction with n-Hexane. Time: 50 minutes
the-Art
and Prospect for Process
Intensification
Temperature: 35 to 60ºC
Manan, Z., et.al, 2017
Biomass fly ash geopolymer Geopolymer adsorbents are
monoliths for effective experimentally used for a
methylene blue removal from controlled model of methylene Hydrogen Peroxide
9 0.75% to 3.00%
wastewaters blue to determine its feasibility Concenration:
to adsorb the contaminants in
Labrincha et. al, 2017 water.

1C14 Project Study

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PAMANTASAN NG LUNGSOD NG MAYNILA

University of the City of Manila

GEOPOLYMERIZATION OF CERAMIC TILE WASTE,

BACKGROUND OF THE STUDY

In the production of sodium aluminosilicate monolith, materials rich in

According to Department of Trade and Industry in 2017, only 65% of the

In order to develop a process to utilize CTW, CFA, and SBE to produce

To utilize these wastes generated from various industries in producing a

STATEMENT OF THE PROBLEM

Coal fly ash is an industrial by-product derived from coal combustion in

This by-product has minimaly utilized as an additive in cement (Rivera, D.,

In a similar incident happened in 2013 in Iloilo, in which due to typhoon

Considering these incidents caused by coal fly ash and as generation

Furthermore, ceramic tile waste is also added because of its high

In an attempt to solve the aforementioned issues, the researchers proposed

OBJECTIVES OF THE STUDY

Table 1.1 Standard and Existing Properties of Sodium Aluminosilicate Monolith

PARAMETER STANDARD EXISTING PROPOSED

Source: (1) ASTM C90-14, Kalaw, et.al, 2016

To develop an experimental method and come up with the optimum

To determine the market feasibility of sodium aluminosilicate monolith

To design a detailed manufacturing process of sodium aluminosilicate

To assess the economic feasibility of manufacturing sodium aluminosilicate

SIGNIFICANCE OF THE STUDY

To the Researchers in the Chemical Engineering Field

SCOPE AND LIMITATIONS

reagents were purchased from Alysons’ Chemical Enterprises and RB Chemodities

The testing of the raw materials was conducted by Department of

The optimum parameters were determined during the experimental study.

REVIEW OF RELATED LITERATURE

Figure 2.1. Sodium Aluminosilicate Monoliths

It possesses excellent physicochemical and mechanical properties,

Table 2.1 Standard and Existing Properties of Sodium Aluminosilicate Monolith

PARAMETER STANDARD EXISTING PROPOSED

Source: (1) ASTM C90-14, Kalaw, et.al, 2016

USES AND APPLICATIONS OF SODIUM ALUMINOSILICATE MONOLITH

Building & Construction Materials

Lightweight Materials Production

The Philippine Market Demand and Supply of Sodium aluminosilicate

Year Demand (kg) Supply (kg)

demand is linked to the construction and infrastructure industry of the Philippines

In this study, the sodium aluminosilicate monolith was produced through

Figure 2.5 Sodium Aluminosilicate Production through Geopolymerization

In the chosen process, preliminary treatment is necessary to the raw

In choosing the suitable solvent to be used in this process, the substance

Figure 2.6. Geopolymerization Reaction

The mechanism involves the dissolution of Al and Si in the alkali medium,

First Stage: “Destruction Coagulation”

Figure 2.7. Destruction Coagulation

The –Si–O–Na+ complexes, which are stable in alkaline media, create

Second Stage: “Coagulation - Condesation”

Figure 2.8. Coagulation - Condensation

The condensability of silicic acid rises with high pH values, at which it is

Third Stage: “Condensation - Crystallization”

Like the appearance of microparticles

Furthermore, Duxson et. al. (2007), discussed

Initially, the contact between the solid

releasing aluminates and silicates as monomers.

According to Fernandez-Jimenez et.al. (2006), the structural reorganisation

Figure 2.10. Blowing Process

Through the process presented above, sodium aluminosilicate monolith

Figure 2.11. Ceramic tile wastes

According to Department of Trade and Industry, the ceramic tile industry

As depicted in Table 2.4, it can be observed that ceramic tile waste is