02 - 21 - 2018 - ChE Plant Design - Synthetic Zeolite From Coal Fly Ash (CFA)

CHAPTER 1:
Introduction
Zeolites are hydrate, microporous aluminosilicates of group IA and IIA elements [6,15].
They are of the tectosilicate type with a three-dimensional framework of interconnected
tetrahedra, comprising mostly of aluminum, silicon and oxygen atoms [14]. The crystalline
structure is built from [AlO4]5- and [SiO4]4- bonded together such that all four oxygen atoms
located at the corners of each tetrahedron shared with adjacent tetrahedral crystals. The
oxygen atom is oriented in such a way that the framework develops void and pore between
the tetrahedra in the form of cages and channels.
Zeolites have a significant number of intermolecular cavities and channels due to their
structural configuration [15]. The transfer of matter between inter-crystalline spaces is made
possible because of the molecular dimensions of zeolites. The crystalline lattice structure of
zeolites consists of exceptional lattice stability by virtue of which they facilitate considerable
freedom of ion-exchange and reversible dehydration [14]. New cations, water molecules and
small organic molecules can be accommodated. Depending on the chemical composition and
the crystalline structure of zeolites, ions and molecules in the cages are loosely bound so that
they can be removed or exchanged without destroying the zeolitic framework.
Zeolites were first discovered by A.F. Cronsted, a Swedish scientist, in 1756; however,
their molecular sieve applications remained untouched until the mid-1920s and a lack of
development for commercial use of natural zeolites remained for some time more [14,20].
Researchers later focused their attention to the synthesis of zeolites using pure chemicals and
minerals present in natural sources or their by-products like fly ash.
Applications of zeolites and molecular sieves in the past several decades showed a growth
in petroleum refining applications with emphasis on resin cracking and octane enhancement.
The use of zeolite catalysts in the production of organic (fine) chemicals appeared as a major
new direction. Zeolites in detergents as a replacement for phosphates became the single
largest volume use for synthetic zeolites worldwide [6].
Coal fly ash is an industrial by-product generated from the combustion of coal. It is
mainly composed of some oxides derived from inorganic compounds that remain after
combustion [18]. The main components of fly ash are silica (SiO2), alumina (Al2O3), ferrous
oxide (Fe2O3), calcium oxide (CaO) and some unburned carbon.
1
The suitability of using fly ash is determined mainly by its mineral and chemical
composition, which is dependent on the type of combustion coal, furnace and combustion
conditions [7]. Based on its chemical components, the fly ash obtained can be one of two
classes. The first is class F, which is a low-calcium ash, and the second is class C, which is a
high-calcium ash.
Fly ash is primarily used in the concrete and cement manufacturing industries, as well as
ceramic applications, additives for the immobilization of industrial wastes and of water
treatment wastes, land stabilization in mining areas, sorbents for flue gas desulfurization,
filter material in the construction of roads, embankments and structural fill [5]. Fly ash and
volcanic material, a precursor of natural zeolites, share similar composition. Due to the high
silicon and aluminum content, high levels of reactive or amorphous phases, small particle
size, low cost and wide availability of fly ash, it is also used in the synthesis of zeolites.
Silicon and aluminum are the main components of zeolites.
The amount of fly ash generated by coal-based thermal power plants has been increasing
at an alarming rate throughout the world [18]. Its disposal has become a pressing issue. In the
Philippines, coal-fired power plants contribute 35% and 37% to the total installed and
dependable capacity or 5444 MW and 5230 MW, respectively [3]. In the Visayas region, coal-
fired power plants represent 31.5% and 35.7% of the total installed and dependable capacity
or 1054 MW and 1050 MW, respectively [3]. Saptasco (2009) reported that the annual
production of coal fly ash in the Philippines in 2009 was 300,000 tons. Approximately 20%
of the total production is attributed to coal-fired plants in the Visayas region.
On the average 95% of the fly ash generated is disposed in ash dams and ponds [4]. The
construction and maintenance of these dams requires large plots of land, which after being
fully utilized for fly ash disposal can be difficult to rehabilitate and use for other purposes
such as farming. This is due to the slow release of toxic elements from coal as well as
changes in the soil pH from the release of calcium oxide.
The synthetic zeolites market is projected to reach USD 16.28 billion by 2022, at a
CAGR of 3.6% between 2017 and 2022 [2]. This growth can be attributed to the increasing
demand for FCC catalysts, rising demand from the detergent industry, and growing market
for VOC adsorbents. Growth in the detergents and catalyst applications has led to the rising
demand for synthetic zeolites in the Asia-Pacific region [2].
The plant design presented is for the production of zeolite A, which is also known as
Linde Type A. This type of zeolite is used as a builder in detergent powders and tablets for
water softening in the washing process [13]. Zeolite A is also used as catalysts and molecular
sieves. The synthesis method chosen and utilized is the fusion assisted method.
2
CHAPTER 2:
Process Selection
The Analytical Hierarchy Process (AHP) was used in the selection of the method to be
used for the synthesis of zeolites. This quantitative method, which is a theory of measurement
through pairwise comparisons, was introduced by Thomas L. Saaty in 1980. In this method,
comparisons are made using a scale of absolute judgments that represents how much more
one element dominates another with respect to a given attribute [23]. A set of evaluation
criteria and a set of alternative options among which the best decision is to be made were
considered.
Table 2.1 Selection of Method for Synthesis of Zeolites

Level 1 GOAL Producing synthetic zeolites
1. Cost
2. Environmental impact
Level 2 CRITERIA 3. Health and safety
4. Sustainability
5. Yield
1. Two-Step Method
Level 3 ALTERNATIVES
2. Fusion Assisted Method
In the synthesis of zeolites, two principal methods have been successfully employed [3].
These are the Two-Step Method and the Fusion Assisted Method. Selection was done
quantitatively and the two methods were compared. Table 2.1 above shows the three levels
undertaken to compare and choose between the two methods. The criteria chosen for the
selection are cost, environmental impact, health and safety, sustainability¸ and yield. Using
AHP the criteria were given weights or priorities. A summary and definition of each criteria
are provided in Table 2.2.
3
Table 2.2 Criteria for Selection of Method for Zeolite Synthesis
Criteria Weight (%) Description
This refers to the amount of capital to be
spent to carry out the synthesis of the
Cost 8.707 selected type or types of zeolite. The cost
should be at minimum while providing the
maximum profit for the company.
This refers to the effects consequential to the
Environmental Impact 30.091 operation of the plant. The environmental
impact should be manageable and minimal.
This refers to the effects that the plant
operation has on the health and safety of the
workers and the people of the community in
Health and Safety 29.424
which the plant operates. The effects on
health and safety should be minimal (or non-
existent if possible) and manageable.
This refers to the aspect of plant operation
that utilizes renewable sources for raw
materials, and minimizes, if not avoids, use
Sustainability 29.424
and depletion of natural resources in the
synthesis of zeolites. Plant operations should
be both sustainable and profitable.
This refers to the amount obtained from a
process or reaction relative to the theoretical
maximum amount obtainable. The method
Yield 3.298 chosen should provide the maximum
possible while giving the maximum profit,
and minimum adverse effect on the
environment, health and safety.
The criteria for the selection of the synthesis method are presented in Table 2.2 above.
The weight is given in percentile. Detailed calculations following the steps for the analytical
hierarchy process are presented in Appendix A.
4
Table 2.3 Comparison of Two Methods of Synthesis
Method of Description
Advantages Disadvantages
Synthesis
This method is costlier.
A mixed-phase zeolite
This method is product is produced.
followed from This method produces
Two-Step Method
the traditional more “pure” zeolites. This method has a
one-step process. time-consuming pre-
hydrothermal
treatment step (aging
step).
The coal fly ash
(CFA) is fused
with sodium This method has an
The zeolite product
Fusion Assisted hydroxide at a energy-intensive
obtained has a pure
Method high temperature fusion step operating
(single) phase.
prior to at 550 °C.
hydrothermal
treatment.
Table 2.4 Summary

Health
Environmental Sustainabilit
Cost and Yield Overall
Impact y
Safety Priorit
Criteria y
0.08707 0.30091 0.29424 0.29424 0.03298
Weights
Two-
Step 0.500 0.500 0.500 0.200 0.875 0.42883
Method
Fusion
Assisted 0.500 0.500 0.500 0.800 0.125 0.58063
Method
5
CHAPTER 3:
Basis of Design
3.1 Description of the Design

The plant is designed to produce zeolite A (Linde Type A). The main raw material
used is coal fly ash obtained from coal-based thermal power plants in Cebu. The
synthesis method utilized is the fusion assisted method improved and optimized by Du
Plessis (2014) based on the work done by Musyoka (2012). The energy-intensive
fusion step at 550 °C was replaced with a sonochemical treatment.
The sonochemical treatment involves exposure to high intensity ultrasonic waves

in the presence of a chemical. Formation of vapor bubbles is caused a low pressure in
the wave. The bubbles collapse violently causing a highly intense cavitation effect.
The cavitation effect is used to dissolve the components of fly ash.
3.2 Description of the Process

The method selected involves four processes: sonochemical treatment, extraction,
hydrothermal treatment, and zeolite recovery and washing. The process flowchart and
the process flow diagram are shown in Figures 3.1 and 3.2, respectively.
Fly ash is mixed with sodium hydroxide (NaOH) in a plastic sonication container.
The resulting mixture is then subjected to sonication at 100% amplitude using a 600-
watt sonicator for10 minutes. The sonicated slurry is filtered and left to cool at room
temperature. The silicon-aluminum ratio is adjusted by adding 0.59 M sodium
aluminate solution in a volume ratio of 5:2 (clear solution: sodium aluminate
solution).
The adjusted filtrate is then subjected to a static hydrothermal treatment in an

oven at 90 °C for 120 minutes. The products obtained are separated by filtration. The
zeolite product is washed and then dried at 80 °C in an oven. The dried zeolite
products are crushed and stored in airtight containers.
6
Sodium Washing
Ash Aluminate Water
Fused
Ash Zeolite
Sonochemical Filtration Hydrothermal Zeolite Recovery
Treatment Treatment and Washing Supernatant
Waste
vv v
NaOH Solid Waste Recovered

Washing
Water Water
Vapor
Figure 3.1 Process Flowchart for the Modified Fusion Assisted Method of Zeolite Synthesis
7
Figure 3.2 Process Flow Diagram for the Modified Fusion Assisted Method of Zeolite Synthesis
8
3.3 Basic Assumptions
3.3.1 Plant Capacity
The plant is designed to operate 8 hours a day for 6 days a week for 52
weeks per year. This translates to 312 days or 2,496 hours of operation
annually. The plant is designed to accept 200 metric tons of coal fly ash per
day or 62,400 metric tons per year. The annual production is expected to be
17,628.70 metric tons or approximately 352,574 sacks of zeolite A.
3.3.2 Plant Location and Layout
Two coal-fired power plants are currently operating in Cebu. The first is
the 203.80-megawatt Naga Power Plant Complex in Naga City, which is
operated by KEPCO-SPC (Salcon Power Corporation). The second is the 246-
megawatt clean coal-fired power plant in Toledo City owned and operated by
Cebu Energy Development Corporation. A third power plant owned by
Therma Visayas, Inc. in Bato, Toledo City with an installed capacity of 340
megawatts will become operational in 2018.
The zeolite plant is to be built along the Naga-Uling Road, which is a

highway that runs from Naga City to Toledo City. This location is strategically
located between the two cities where the coal-fired power plants are operating.
Coal Fly Ash (CFA) can be easily transported from the power plants to the
zeolite plant. The road is wide and mostly flat over the stretch of its course.
There is sufficient distance between residential communities and the plant,
making the area suitable for the operation of the zeolite plant. An aerial view
of the selected site is shown in Figure 3.3.
The site will occupy a plot of land with a total area of 20,000.00 square
meters (2.00 hectares). The area was chosen mostly due to its distance from
the nearest residential community, which is approximately one kilometer, and
to the nearest river, which is right next to the property. The distance from the
nearest community will allow the plant to operate freely while adhering to
strict environmental rules and regulations set by both the management and the
government. A river can also be found next to the proposed plant location.
A steel fence is to be built around the property. The main material of

construction shall be steel (steel bars and steel mesh). Concrete posts shall be
used to hold the fence together. Between the entrance and the exit will be a
guard house.
9
Figure 3.3 Plant Location
The plant building is classified as type V, as defined in the building code of

the Philippines. The building shall be fire-resistive. The structural elements
shall be of steel, iron, concrete and masonry construction. Walls, ceilings and
partitions shall be of incombustible fire-resistive construction.
The occupancy classification of the plant building is group G – division 1,

as defined in the building code of the Philippines. This classification stems
from the intended use of the building, which will handle and store hazardous
and flammable material.
10
Figure 3.4 Plant Layout
11
3.3.3 Battery Limits
The battery limits of the design refer to the scope of the design. The inside
battery limits and the outside battery limits are summarized in Table 3.1
below. The aspects of the project that will be discussed thoroughly are listed
under the inside battery limits column while those that will not be tackled or
those that will just be slightly talked about or referenced to are given in the
outside battery limits column.
Table 3.1 Battery Limits

Inside Battery Limits Outside Battery Limits
 the overall mass and energy  wastewater treatment facility
balances design
 the component mass and energy  materials recovery facility design

balances
 packaging, handling and storage
 processes involved design of the product
 plant layout and design  organizational structure of the

company
 plant location
 shareholder structure of the
 chemical and mechanical designs company
of the equipment
 sources of funds for the company
 economic analysis
 safety management
 thermodynamic properties of
substances
 process control
 mass and energy balances
 waste management
 market study
12
3.4 Economic Margin of the Design
3.4.1 Market Study
Rapid urbanization, increasing population, and changing lifestyles have
resulted in the rising demand for phosphate-free detergents in the Asia-Pacific
region, in turn, leading to the increasing demand for synthetic zeolites [2]. The
Asia-Pacific region ranked second in terms of oil refining capacity in the
world. This has led to the increasing demand for FCC and hydrocracking
catalysts in the region. Growth in the detergents and catalyst applications has
led to the rising demand for synthetic zeolites in the Asia-Pacific region.
Asia Pacific has been the leading consumer of synthetic zeolites in and
since 2013, and is likely to remain in the lead for the coming years [10]. A huge
scope of growth is present in the global synthetic zeolites market in the
application segment of detergents. Governments, environment agencies, and a
growing number of environment conscious consumers have been supporting
the use of specialty zeolites over phosphates in detergents, due to the harmful
effects the latter can have on the environment.
Research and Markets (2017), a business research firm, reported that the
synthetic zeolites market is expected to reach USD 16.28 billion by the year
2022. The CAGR or the compound annual growth rate between 2017 and
2022 is projected to be 3.6%. The firm further reported that this growth can be
attributed to the increasing demand for FCC catalysts, rising demand from the
detergent industry, and growing market for VOC adsorbents.
The outlook remains positive despite a mature detergents market in Europe

and diminishing crude oil reserves. While zeolite X (Linde Type X) is expected
to have the highest CAGR growth during the forecast period, zeolite A (Linde
Type A) will still remain one of the most in-demand types of synthetic zeolite
due to its use as a builder for detergents (as an alternative to phosphates) and
as a tablet for water softening in the washing process. Like zeolite X, zeolite A
can also be used as catalysts and as molecular sieves.
Research and Markets (2017) also reported that based on application, the
adsorbents segment is projected to grow at the highest CAGR during the
forecast period. It also reported that the Asia-Pacific region is expected to be
the fastest-growing synthetic zeolites market.
13
CHAPTER 4:
Thermodynamic Properties
CHAPTER 4:
Thermodynamic Properties
4.1 Physical and Chemical Properties of Pure Substances
Table 4.1 Physical Properties of Pure Substances

Molecula
Components Boiling
r Specific
Odo Point
Chemical Structural Form Color
r Weight Gravity
Name Formula (°C)
(g/mol)
Coal Fly - Solid Gray - - - -
Ash
H–O–H Liqui Colorles Odor 18.02 1 100
Water d s less
Sodium Solid White Odor 81.969 1.5 1650

less
Aluminat (Pow
e eder)
Solid White Odor 39.997 2.13 1388
NaOH
less
Solid - - 284 0.17 - -
Zeolite A
0.45
14
Table 4.2 Composition of Coal Fly Ash
Components Composition (%)
Aluminum Oxide 31.51
Calcium Oxide 3.76
Iron (III) Oxide 4.94
Magnesium Oxide 1.18
Potassium Oxide 0.47
Silicon Dioxide 55.44
Sodium Oxide 0.04
Sulfur Trioxide 0.06
Manganese(II) Oxide 0.03
Titanium Dioxide 1.11
Phosphorus Pentoxide 0.30
Silicon Dioxide/Aluminum Oxide 1.76
Loss on Ignition 1.22
Table 4.3 Composition of Zeolite A

Components Composition (%)
Silicon 19.6
Aluminum 21.6
Iron 0.3
Sodium 4.8
Potassium 21.2
Titanium 0.2
Sulfur 74
Barium 2.4
Zinc 3.6
Table 4.4 Solubility of Substances
15
Solubility Per 100 Parts
Substances
Cold Water Hot Water Other Reagents
Insoluble Insoluble Difficult solubility
Aluminum Oxide in mineral acids
and strong alkali
Calcium Oxide Forms Ca(OH)2 - Soluble in glycerol
Insoluble Insoluble Soluble in diluted

Iron (III) Oxide
acid
Insoluble Insoluble Soluble in acids

Magnesium Oxide and ammonium
salt solutions
Reacts forming Reacts forming Soluble in EtOH,
Potassium Oxide
KOH KOH ether
Silicon Dioxide Insoluble Insoluble -
Sodium Oxide Reacts violently to Reacts violently to Reacts with

form NaOH form NaOH ethanol
Reacts to give Reacts to give -

Sulfur Trioxide
sulfuric acid sulfuric acid
Manganese(II) Insoluble Insoluble Soluble in acid

Oxide
Insoluble Insoluble Dissolves slowly
in hydrofluoric
Titanium Dioxide acid and in hot
concentrated
sulphuric acid.
Phosphorus exothermic exothermic Soluble in Sulfuric
Pentoxide hydrolysis hydrolysis acid
16
Figure 4.1 Duhring lines for aqueous solution of Sodium Hydroxide
17
Figure 4.2 Enthalpy concentration chart for the system NaOH water
18
4.2 Heat Capacity of Substances
Table 4.5 Heat Capacity of Coal Fly Ash Components
Chemical Heat Capacity at constant pressure Range of

Chemical Name State Uncertainty, %
Formula (T=K; 0 oC= 273.15K ), cal/(mol*K) temperature, K
Aluminum Oxide Al2O3 crystal 22.08 + 0.008971T - 522500/T2 273-1973 3

Calcium Oxide CaO crystal 10.00 + 0.00484T - 108000/T2 273-1173 2
Iron (III) Oxide Fe2O3 crystal 24.73 + 0.01604T - 423400/T2 273-1097 2
Magnesium Oxide MgO crystal 10.86 + 0.001197T - 208700/T2 273-2073 2
Potassium Oxide K2O crystal - - -
c, quartz, α (10.87 + 0.008712T - 241200/T2 ) 273-848 1
c, quartz, β (10.95 + 0.00550T) 848-1873 3.5

Silicon Dioxide SiO2
c, cristobalite, α (3.65 + 0.0240T ) 273-523 2.5
c, cristobalite, β (17.09 + 0.000454T - 897200/T2) 523-1973 2
Manganese(II)
MnO crystal 7.43 + 0.01038T - 0.00000362/T2 273-1923 -
Oxide
Titanium Dioxide TiO2 crystal 11.81 + 0.00754T - 41900/T2 273-713 3
Phosphorus
P4O10 crystal 15.72 + 0.1092T 273-631 2
Pentoxide
Table 4.6 Heat Capacity of Other Substances
19
Cp at Tmax*1E-05
Chemical Formula
Cp at Tmin*1E-05
Chemical Name
Tmax (K)
Tmin(K)
C1 C2 C3 C4 C5
Water H2O 276370 -2090.1 8.125 -0.014116 9.3701E-06 273.16 0.7615 533.15 0.8939
Cp= C1 + C2T + C3T2 + C4T3 + C5T4
20
4.3 Thermodynamic Properties of Substances
Saturation Properties for Steam - Temperature Table (0.01°C - 150°C)
Table 4.7 Thermodynamic Properties of Water
Volume Energy Enthalpy Entropy

Temperature Pressure
(m3/kg) (kJ/kg) (kJ/kg) (kJ/kg.K)
°C MPa vf vg uf ug hf hfg hg sf sfg sg
0.01 0.00061 0.00100 205.99 0 2374.9 0.001 2500.9 2500.9 0 9.1555 9.1555
5 0.00087 0.00100 147.01 21.02 2381.8 21.0 2489.1 2510.1 0.0763 8.9485 9.0248
10 0.00123 0.00100 106.30 42.02 2388.6 42.0 2477.2 2519.2 0.1511 8.7487 8.8998
15 0.00171 0.00100 77.875 62.98 2395.5 63.0 2465.3 2528.3 0.2245 8.5558 8.7803
20 0.00234 0.00100 57.757 83.91 2402.3 83.9 2453.5 2537.4 0.2965 8.3695 8.6660
25 0.00317 0.00100 43.337 104.83 2409.1 104.8 2441.7 2546.5 0.3672 8.1894 8.5566
30 0.00425 0.00100 32.878 125.73 2415.9 125.7 2429.8 2555.5 0.4368 8.0152 8.4520
35 0.00563 0.00101 25.205 146.63 2422.7 146.6 2417.9 2564.5 0.5051 7.8466 8.3517
40 0.00739 0.00101 19.515 167.53 2429.4 167.5 2406.0 2573.5 0.5724 7.6831 8.2555
45 0.00960 0.00101 15.252 188.43 2436.1 188.4 2394.0 2582.4 0.6386 7.5247 8.1633
21
50 0.01235 0.00101 12.027 209.33 2442.7 209.3 2382.0 2591.3 0.7038 7.3710 8.0748
55 0.01576 0.00102 9.5643 230.24 2449.3 230.3 2369.8 2600.1 0.7680 7.2218 7.9898
60 0.01995 0.00102 7.6672 251.16 2455.9 251.2 2357.6 2608.8 0.8313 7.0768 7.9081
65 0.02504 0.00102 6.1935 272.09 2462.4 272.1 2345.4 2617.5 0.8937 6.9359 7.8296
70 0.03120 0.00102 5.0395 293.03 2468.9 293.2 2333.0 2626.1 0.9551 6.7989 7.7540
75 0.03860 0.00103 4.1289 313.99 2475.2 314.0 2320.6 2634.6 1.0158 6.6654 7.6812
80 0.04741 0.00103 3.4052 334.96 2481.6 335.0 2308.0 2643.0 1.0756 6.5355 7.6111
85 0.05787 0.00103 2.8258 355.95 2487.8 356.0 2295.3 2651.3 1.1346 6.4088 7.5434
90 0.07018 0.00104 2.3591 376.97 2494.0 377.0 2282.5 2659.5 1.1929 6.2852 7.4781
95 0.08461 0.00104 1.9806 398.00 2500.0 398.1 2269.5 2667.6 1.2504 6.1647 7.4151
100 0.10142 0.00104 1.6718 419.06 2506.0 419.2 2256.4 2675.6 1.3072 6.0469 7.3541
110 0.14338 0.00105 1.2093 461.26 2517.7 461.4 2229.7 2691.1 1.4188 5.8193 7.2381
120 0.19867 0.00106 0.8912 503.60 2528.9 503.8 2202.1 2705.9 1.5279 5.6012 7.1291
130 0.27028 0.00107 0.66800 546.09 2539.5 546.4 2173.7 2720.1 1.6346 5.3918 7.0264
140 0.36154 0.00108 0.50845 588.77 2549.6 589.2 2144.2 2733.4 1.7392 5.1901 6.9293
150 0.47616 0.00109 0.39245 631.66 2559.1 632.2 2113.7 2745.9 1.8418 4.9953 6.8371
22
23
CHAPTER 5:
Process Structure and Description
5.1 Criteria and Selection
In the selection of equipment for the plant, the Analytical Hierarchy Process
(AHP) was once again used. The criteria or the main factors considered are the cost,
safety, operability, and environmental compliance. Each criterion is briefly described
in Table 5.1 below.
Table 5.1 Criteria for Equipment Selection

Criteria Weight (%) Description
This refers to the capital cost of the equipment,
the maintenance cost, the operational cost, and
Cost 4.97
other costs related or incidental to the purchase
and operation of the equipment.
This refers to the features of the equipment that
Safety 16.98 minimize or eliminate hazards to workers with
access to or in contact with the equipment.
This refers to the reliability and compatibility of
the equipment to the process chosen. This also
Operability 12.40
refers to the ease in using or operating the
equipment.
This refers to how the functions, construction,
and operation of the equipment comply with the
Environmental
65.66 requirements and standards set by the
Compliance
Department of Environment and Natural
Resources (DENR).
24
5.2 Selection of Sonication Equipment
Table 5.2 Comparison of Different Types of Sonication Equipment

Ultrasonic Probe Cell Ultrasonic Homogenizer
Criteria
Sonicator Sonicator
high capital cost, and high high capital cost, and high
Cost
operating cost operating cost
sonication done within an sonication done without
enclosure; focused and an enclosure; workers can
uniform ultrasonic power be directly exposed to
Safety
input equipment during
sonication; low intensity
sonication
allows full control over low reproducibility of
sonication parameters; results; minimal control
Operability
has reproducible results over sonication
parameters
Environmental low waste production high waste production
Compliance
Table 5.3 Selection of Sonication Equipment

Ultrasonic Probe Cell Ultrasonic Homogenizer
Criteria
Sonicator Sonicator
Cost 0.0249 0.0249
Safety 0.1133 0.0565
Operability 0.0992 0.0298
Environmental
0.3283 0.3283
Compliance
TOTAL 0.5657 0.4345
25
5.3 Selection of Filtration Equipment
Table 5.4 Comparison of Different Types of Filtration Equipment

Rotary Drum Vacuum
Criteria Bed Filter
Filter
low maintenance and high capital cost; low
Cost operation costs, and low maintenance cost; low
capital cost operating cost
low noise production;
low noise production and workers may be exposed
Safety
less vibration to moving mechanical
parts
This is the simplest type
of filter. Operation is also
simple. Water is
introduced at the top. The Simple and convenient
Operability
water spreads out through operation
the filter medium and the
clarified liquid is drawn
out at the bottom.
Environmental Backwashing is needed. Low wastewater
Compliance Wastewater is produced. production
Table 5.5 Selection of Filtration Equipment

Rotary Vacuum-Drum
Criteria Bed Filter
Filter
Cost 0.0331 0.0166
Safety 0.0849 0.0849
Environmental
0.1097 0.5469
Compliance
TOTAL 0.2525 0.7476
26
5.4 Selection of Equipment for Hydrothermal Treatment
Table 5.6 Comparison of Equipment for Hydrothermal Treatment

Criteria Heating Tank Hot-Air oven
lower capital cost; lower higher capital cost; higher
Cost
minimal worker contact constant worker contact
Safety
with equipment with equipment
simple and convenient Containers for adjusted
operation; continuous filtrate constantly filled
Operability
operation and emptied by worker;
batch operation
low energy consumption higher energy
Environmental
consumption and
Compliance
manpower resources
Table 5.7 Selection of Equipment for Hydrothermal Treatment

Criteria Heating Tank Hot-Air Oven
Cost 0.0414 0.0083
Safety 0.1358 0.0340
Environmental
0.4380 0.2186
Compliance
TOTAL 0.7254 0.2747
27
5.5 Selection of Dryer
Table 5.8 Comparison of Different Types of Dryer

Criteria Tunnel Dryer Rotary Dryer
medium to high capital Medium to high capital
Cost
cost; lower operating cost cost; higher operating cost
Safety minimal worker contact minimal worker contact
simple operation; minimal simple operation; damage
Operability damage to zeolite product to zeolite product may be
greater
Environmental medium to high energy medium to high energy
Compliance consumption consumption
Table 5.9 Selection of Dryer

Criteria Tunnel Dryer Rotary Dryer
Cost 0.0398 0.0099
Safety 0.0849 0.0849
Environmental
0.3283 0.3283
Compliance
TOTAL 0.5563 0.4438
28
5.6 Selection of Crushing Equipment
Table 5.10 Comparison of Different Types of Crushing Equipment

Criteria Ball Mill Roller Mill
lower capital cost; lower higher capital cost; lower
Cost
machine guarding needed machine guarding needed
Safety
for moving parts for moving parts
simple operation versatile; can be used for
Operability a wide range of
application
higher energy lower energy
Environmental
consumption; 32.50 – consumption; 17.20 –
Compliance
39.20 Kwh per ton of feed 22.20 Kwh per ton of feed
Table 5.11 Selection of Sonication Equipment

Criteria Ball Mill Roller Mill
Cost 0.0249 0.0249
Safety 0.1133 0.0565
Environmental
0.3283 0.3283
Compliance
TOTAL 0.5492 0.4510
29
CHAPTER 6:
Heat and Mass Balances
Table 6.1 Summary of Heat and Mass Balances

IN OUT
Plant Equipment Equipment Plant
EQUIPMENT
Mass Mass Mass Mass
Heat Heat Stream IDENTIFICATION Stream Heat Heat
(tons/day (tons/day (tons/day (tons/day
(kW) (kW) Number Number (kW) (kW)
) ) ) )
200 200 1
- 3,562 Mixing Tank 3 1,306.103 3,562 - -
1,106.103 1106.103 2
- - 1,306.103 8,407 4 Sonicator 5 1,306.103 8,407 - -
Rotary Vacuum- 7 998.103 - - -
- - 1,306.103 - 6
Drum Filter 8 308 - - -
- - 998.103 9
3,562 Mixing Tank 11 1,425.862 3,562 - -
- - 427.759 10
- - 1,425.862 10,861.3 12 Heating Tank 13 1,425.862 10,861.3 - -
- - 1,425.862 - 14 Rotary Vacuum- 16 67.713 - - -
- - 11,210.76 - 15 Drum Filter 17 12.568.91 - - -
19 11.211 - -
- - 67.713 878.60 18 Tunnel Dryer 878.60
20 56.502 - -
- - 56.502 - 21 Ball Mill 22 56.502 - 56.502 -
30
CHAPTER 7:
Process and Equipment Design
7.1 Sonication Equipment
Table 7.1 Specifications for Ultrasonic Probe Cell Sonicator

EQUIPMENT NUMBER : M01
NAME : Ultrasonic Probe Cell Sonicator
General Data
: Agitates coal fly ash and NaOH
Service
through sound waves
Type : Large-volume sonicator
Number of Equipment :6
Operation : Batch
Position : Vertical
Material of Construction : Stainless steel
Process Conditions
Stream Details Feed Product Outlet
Stream Number 01a 01b
Pressure (Pa) 101325 101325
Temperature (K) 298.15 298.15
Construction Details
Sonication Vessel Generator
Thickness mm 6.0000 Length m 1.0000
Diameter m 1.3030 Width m 1.0000
Height m 3.0000 Height m 1.5000
Volume m3 4.000 Wire Length m 10.0000
Enclosure Probe Cell
Height m 6.0000
Length m 3.0000
Width m 4.0000
Length m 4.0000
Tip Diameter m 0.2303
Volume m3
Thickness mm 48.000
Aperture Inner Top Diameter m 0.2606
m 0.0254
Diameter
Aperture Outer
m 0.0508
Diameter
31
7.2 Filtration Equipment
Table 7.2 Specifications for Rotary Vacuum-Drum Filter

NAME : Rotary Vacuum-Drum Filter
General Data
Service : Rotary Filter
Type : Rotary Vacuum
Operation : Continuous
Position : Horizontal
Process Conditions
Stream Number 02a 02b
Pressure (Pa) 50000 50000
Drum Trough
Diameter m 2.0000 Diameter m 5.0000
Length m 4.0000 Length m 5.0000
Blade Filtrate Collection Tank
Thickness mm 12.0000 Diameter m 1.0000
Width m 0.5000 Length m 5.0000
Length m 4.0000 Volume m3 2.20
Filter Cake Collection Tank Feed Tank
Diameter m 1.0000 Diameter m 1.3030
Length m 5.0000 Height m 3.0000
32
7.3 Mixing Tank
Table 7.3 Specifications for Heating Tank

NAME : Agitated Mixing Tank
General Data
Service : Mixer
Type : Agitated tank with baffles
Number of Tanks : 12
Operation : Batch
Position : Vertical
H/Dt Ratio : 1.0000
L/Da : 0.2500
C/Dt : 0.3333
J/Dt : 0.0833
Dd/Da : 0.6667
Da/Dt : 0.3333
W/Da : 0.2000
Material of Construction : Stainless Steel
Process Conditions
Stream Number 03
Pressure (Pa) 101325 101325
Tank Impeller
Diameter m 3.0000 Da m 1.5000
Height m 3.0000 Dd m 1.0000
L m 0.3750
W m 0.3000
Baffles Motor
J (Width) m 0.3000 Power hp 5.0000
Height m 2.8000
33
7.4 Heating Tank
Table 7.4 Specifications for Heating Tank

NAME : Heating Tank
General Data
Service : Provides for extraction of Si/Al
Number of Tanks :6
Operation : Batch
Position : Vertical
Power :
Material of Construction : Stainless Steel
Process Conditions
Stream Number 04
Pressure (Pa) 101325 101325
Tank
Thickness mm 48.0000
Diameter m 1.3030
Height m 3.0000
Volume m3 4.0000
34
7.5 Dryer
Table 7.5 Specifications for Tunnel Dryer

NAME : Tunnel Dryer
General Data
Service : Dryer
Speed : 5 m/hr
Height of Dryer :2m
Length of Dryer : 10 m
Width of Dryer : 2m
Process Conditions
Stream Number 06
Pressure (Pa) 101325 101325
7.6 Crushing Equipment
Table 7.6 Specifications for Ball Mill

NAME : Ball Mill
General Data
Service : Crusher
Type : Fine crusher
Peripheral Speeds : 3.3 m/s, 2.0 m/s, 1.3 m/s
Ball Diameters : 125 mm, 90 mm, 64 mm
Process Conditions
Stream Number 07
Pressure (Pa) 101325 101325
35
CHAPTER 8:
Process Control
An essential part of the operation of the plant involves process control. For reasons of
safety and specification there is a necessity to keep flows, pressures, temperatures and
compositions within certain limits in all the processes. Automatic control is employed to
avoid the need for a human operator to continuously monitor the controlled variables. In
addition to this, the controlled variables may fluctuate too rapidly and frequently for manual
adjustment to suffice.
A feedback control system is utilized in the equipment design. A combination of feedback

and feedforward controllers was not opted due to its time- and capital-intensive nature.
Unmeasured disturbances are corrected using feedback control. The parallel form of PID
(proportional-integral-derivative) control without a derivative filter is used. A block diagram
for this is presented in Figure 8.1 below.
E(s) P’(s)
Kc
Figure 8.1 Block Diagram of the Parallel Form of PID Control
36
37
8.1 Sonication Equipment
The original fusion step in the fusion-assisted method of zeolite synthesis

developed by Musyoka et al (2009) was replaced with a sonochemical treatment
optimized by Du Plessis (2014). The new step was chosen because of its lower energy
consumption and application in industrial production of Zeolite A. Process control is
used to control the temperature of the liquid being sonicated to avoid causing damage
to the slurry produced after sonication. This is done by controlling the power input to
the ultrasonic probe cell sonicator. The temperature of the liquid is measured and
adjustments are made to the power input when the temperature exceeds 100 °C.
Table 8.1 Process Control Variables

Controlled Variable Temperature of Liquid inside the Vessel
Manipulated Variable Power Input
Type of Controller PID
Table 8.2 Process Control Diagram for Ultrasonic Probe Cell Sonicator
38
8.2 Filtration Equipment
The rotary vacuum-drum filter is used twice in the production of zeolite A. The
first time is after the sonichemical treatment. The slurry produced is passed through
the filter to separate the solid waste from the liquid. After hydrothermal treatment, the
filter is used to separate the zeolite product from the supernatant waste. A PID
controller is used to control the level of the liquid inside the trough to ensure that the
rotating drum has a submergence of 33 percent. This is done by adjusting the
volumetric flowrate of the inlet.

Controlled Variable Liquid Level
Manipulated Variable Inlet Volumetric Flowrate
Table 8.3 Process Control Diagram for Rotary Vacuum-Drum Filter

39
8.3 Mixing Tank
Mixing tanks are used twice in the production of zeolite A. The first time is in the
materials preparation step right before sonochemical treatment. The class F coal fly
ash is mixed with 5 M sodium hydroxide solution. The second time is after the slurry
from the sonicator is filtered. The filtrate is transferred into a mixing tank where the
Si/Al ratio is adjusted by adding 0.59 M sodium aluminate solution. The level of the
liquid inside the mixing tank is controlled by adjusting the inlet volumetric flowrate.

Controlled Variable Liquid Level in the Tank
Manipulated Variable Outlet Volumetric Flowrate
Table 8.4 Process Control Diagram for Mixing Tank
40
8.4 Heating Tank
The hydrothermal treatment was optimized by Du Plessis (2014). The optimal

hydrothermal time is two hours at 90 °C. This is the most important step in the
production of zeolite A and it is essential that the temperature be kept constant at 90
°C to minimize, if not prevent, the production hydroxy sodalite, which is more stable
but less useful than zeolite A. The temperature is measured and the power input to the
heating is adjusted.

Controlled Variable Temperature of the Liquid
Table 8.5 Process Control Diagram for Heating Tank
41
8.5 Heating Tank
The hydrothermal treatment was optimized by Du Plessis (2014). The optimal

hydrothermal time is two hours at 90 °C. In addition to controlling the temperature of
the liquid inside the tank, the liquid level is also controlled by adjusting the inlet
volumetric flowrate.

Controlled Variable Liquid Level in the Heating Tank
Manipulated Variable Inlet Volumetric Flowrate
Table 8.6 Process Control Diagram for Heating Tank
42
8.6 Dryer
After the zeolite product is separated from the supernatant waste and washed, it is
sent to a tunnel dryer to remove the adhering moisture. The wet zeolite product is
dried at 90 °C for 30 minutes in a tunnel dryer. The temperature is controlled by
manipulating or adjusting the power input to the tunnel dryer.

Controlled Variable Drying Temperature
Table 8.7 Process Control Diagram for Tunnel Dryer
43
8.7 Crushing Equipment
The mean particle size of zeolites ranges from 0.150 to 1.800 microns. To ensure
that the desired particle size is obtained a multivariable control is used in the
operation of the ball mill. This will prevent the violation of input and output
constraints, and prevents excessive movement of manipulated variables. Two
important factors that affect the particle size of the product from a ball mill are the
rate of feed and the speed of rotation of mill. With high rates of feed, less size
reduction is effected since the material is in the mill for a shorter time. The speed of
rotation determines how much crushing action is obtained.

Controlled Variables Particle Size
Manipulated Variables Rate of Feed, Speed of Rotation of Mill
Table 8.8 Process Control Diagram for Ball Mill
44
CHAPTER 9:
Process Waste and Waste Management
9.1 Sources of Waste

The two most well‐known routes for fly ash conversion to zeolite are the fusion
with sodium hydroxide process developed by Shigemoto et al. and a two‐step process
developed by Hollman et al. Wastewater is produced from both processes coming
from the supernatant liquid and washing water.
The wastewaters from both processes contain toxic and hazardous elements. Solid
waste is produced only from the extraction step of the fusion assisted process. No
solid waste is produced from the two-step process. There is no air pollutants produced
from both processes. However, the feeding of the coal fly ash, if not handled well,
may pose a spread of harmful air particulates.
9.1.1 Sources of Air Pollutants

There are no air pollutants produced in the process of synthesizing zeolites
from coal fly ash. Only, if feeding the coal fly ash is not contained, the spread
of ash dusts is inevitable. Ash dusts, if inhaled, may cause conditions such as
lung cancer, asthma and many others are typical diseases attributed to fly ash
inhalation.
9.1.2 Sources of Solid Waste

Solid waste is produced only in the fusion assisted process. The solid
waste comes from the extraction step. 100% of Ce, Co, Cu and Y from the
coal fly ash is usually found in the solid waste. Also nearing 100%
concentration in the solids are Fe, Mn, Mg, Ca, Ti, Ba, Rb and Sr.
9.1.3 Sources of Wastewater

Wastewater from the production of zeolites from coal fly ash comes from
the supernatant liquid produced after the hydrothermal treatment and the
washing water used for the zeolite at the final stage. In the supernatant waste,
large fractions of the Si, Al and Na are found from the fusion assisted process
resulting in a great loss of these elements that are supposedly for the
production of zeolites. Phosphorous and Vanadium are also concentrated in the
supernatant waste from both processes.
45
9.1.4 Sources of Toxic and Hazardous Waste
Toxic and hazardous elements are found in the wastewater from the zeolite
production. Supernatant liquid from the two-step process contains
considerable amount of Pb, Nb and Al and traces of As and Hg. Greater levels
of Hg are found in the washing wastewater. From the fusion assisted process,
the supernatant waste includes the toxic element Ba. Other toxic elements such
as As, Hg, Pb, Rb and Al are also found in the supernatant and washing water
waste. Of particular concern is the large fraction of lead (42.1%) reporting to
the washing water waste. Niobium (41.8%) is found in the washing water
waste, as opposed to the 16.2% of the 2-step process. This element forms part
of the list of rare earth elements (REE) and its extraction from the liquid could
yield promising benefits.
9.2 Air Pollution Control and Abatement

In feeding the coal fly ash, some particles may spread in the air, thus pollution
control measure should be in place. Baghouse is an inexpensive and practical way of
containing air pollutants. A fabric filter, sometimes referred to as a baghouse, utilizes
fabric filtration to remove particles from the contaminated gas stream by depositing
the particles on fabric material. In general, fabric filters are capable of collection
efficiencies greater than 99 percent.
9.3 Solid Waste Management

The solid waste from the process of zeolite and wastewater treatment sludge are
solidified by adding solidification agents to the waste. Solidification is done to
prevent leakage of the hazardous waste, making it compact and easier to handle.
Solidified waste is then sent to the sanitary landfill for disposal.
9.4 Wastewater Management

The wastewater is processed in two steps. The first step employs sedimentation
which allows the solid particles to settle and accumulate at the bottom of the tank. In
the second step, metal salts are added to the waste water to generate larger flocks from
small particles and heavy metals thus allowing the removal of pollutants more
convenient. Part of the treated wastewater is reused in the plant and part of the
wastewater is released to the river after testing if the wastewater meets the DENR
standard.
9.5 Toxic and Hazardous Waste Management

Toxic and hazardous wastes are incorporated in the solid waste and wastewater
treatment.
46
CHAPTER 10:
Process Safety and Safety Management
Process Safety is defined as a disciplined framework for managing the integrity of

operating systems and processes handling hazardous substances by applying good design
principles, engineering, and operating practices. It deals with the prevention and control of
incidents that have the potential to release hazardous materials or energy.
In the establishment of chemical plants hazardous materials that can endanger the
people and the environment can be emitted. Hence, it is necessary in every plant to have
process safety and safety management in its production facility to ensure proper production
and to ensure the welfare of the personnel. In this design, the Occupational Safety and Health
Standards are the used to determine the possible hazards that can occur in a plant.
The Material Safety Data Sheet provides a good estimation on knowing the toxicity of
the materials involved in the production. A material can be considered hazardous due to its
toxicity, reactivity, flammability and corrosivity.
Process Safety is a disciplined framework for managing the integrity of operating

systems and processes handling hazardous substances by applying good design principles,
engineering, and operating practices. It deals with the prevention and control of incidents that
have the potential to release hazardous materials or energy. Thus, it is necessary in every
plant to have process safety and safety management in its production facility to ensure proper
production and to ensure the welfare of the personnel. In this design, the Occupational Safety
and Health Standards are the used to determine the possible hazards that can occur in a plant.
10.1 Workplace Classification

The Occupational Safety and Health Standards under Rule 1010 gives the
criteria wherein a workplace can be said to be hazardous. According to section
1013(A) under the said rule, a workplace can be considered hazardous if the nature of
work exposes the workers to dangerous environmental elements, contaminants or
work conditions including ionizing radiation, chemicals, fire, flammable substances,
noxious components and the like. By this, the plant is classified as a hazardous
workplace since during the process of production certain chemicals like zeolites and
sodium hydroxide are encountered by the workers which can be dangerous to them.
47
10.2 Training of Personnel in Occupational Safety and Health (OSH)
The appointed supervisor or technical personnel of the plant must undergo
training programs prescribed by the Bureau of Working Conditions in order for the
personnel to increase one’s competence and to be able to carry out the provisions in
the OSH Standards. These provisions require the incorporation into the training
programs of the latest trends, practices and technology in Occupational Safety and
Health.
The supervisor or technical personnel who took the required training programs
shall be appointed safety man. The required number of the appointed safety man
depends on the number of workers employed and the type of workplace. Rule 1030,
section 1033(A) of the Occupational Safety and Health Standards indicates that for
every 200 workers and below one (1) part-time safety man is required, for over 200 to
1000 workers one (1) full-time safety man is required and for every 1000 workers one
(1) full-time safety man is required in a hazardous workplace.
The employment of a full-time safety man may not be required if the employer
enters into a written contract with a qualified safety consultant. A qualified safety
consultant is qualified shall mean one who has been a safety and health practitioner
for at least five (5) years and has taken the necessary training prescribed by the
Bureau of Working Conditions. However, safety practitioners with at least ten (10)
years of experience in all fields of Occupational Safety and Health may not be
required to undergo the required training provided they can secure a certification from
the Bureau. All safety consultants are accredited by the Bureau of Working
Conditions.
10.3 Premises of Establishments

Building premises in the plant have adequate fire emergency or danger sign
and safety instructions of standard colors and sizes are visible at all times. Other
visible signs that are needed to direct the driver of the motorized vehicle are properly
positioned within the compound. Adequate comfort rooms and lavatories separate for
female and male workers are provided. Adequate dressing rooms for female workers
and locker rooms for male workers are also provided.
All the buildings within the plant premises are structurally safe and sound to
prevent their collapse. The roofs are constructed to withstand strong winds and
typhoons. The foundations are of sufficient strength to sustain safely the loads for
which they are designed for. Good Housekeeping is maintained at all times
throughout the building premises, machines, regular waste disposal, operations,
storage and filling materials.
48
The workrooms in the building are at least 2.7 meters in height from the floor
to the ceiling and the maximum number of persons employed in a workroom does not
exceed the one person per 11.5 cubic meters stated in Rule 1062 of the OSH space
requirements. Enough spaces are also observed between the equipment and
machinery so as to allow normal operations and to provide passageways for
maintenance and repair personnel.
Surfaces of stairways, ramps, elevator platforms and similar places within the
building premises are constructed to provide a safe walking condition to any person
and are provided with non-slip walkway surface. The stairway floor openings are
guarded with permanent railings on all exposed sides to provide protection. The
standard railings are at least 1 meter from the floor level to the upper surface of the
top rail and have posts not more than 2 meters apart as per stated in Rule 1064 of the
OSH construction of railings.
All stairs, platforms and landings within the building premises are of sufficient
strength to sustain safely a load of not less than 490 kg/m2 with a factor of safety of
four. The constructed stairways follow within the standard of Rule 1065 of OSH
standards which says that stairs shall not be less than 1.10 meters in width and a
height of not more than 3.6 meters.
Roadways for automobiles, tractors or other vehicles provided within the

premises are constructed with good wearing surfaces and of adequate width.
Regulations covering the use of driveways for entry and exit, speed limits, space
allotments and methods of parking are provided and are strictly enforced where
parking space is provided for automobiles. Gates are constructed within the perimeter
of the premises and are separated to entrance and exit gates provided for pedestrian,
vehicular and railroad traffic.
10.4 Occupational Health and Occupational Control

In a processing plant, it is necessary that the working environment for the
personnel is well maintained and controlled to ensure the safety and health of the
workers. The working environment measured in the plant includes the temperature,
humidity, pressure, illumination, ventilation, and noise levels in indoor or outdoor
areas.
Under Rule 1070 of the Occupational Safety and Health Standards, certain
provisions regarding the threshold limit values for toxic and carcinogenic substances
and physical agents are established in the working environment. Threshold Limit
Values refer to airborne concentration of substances and represent conditions under
which it is believed that nearly all workers may be repeatedly exposed daily without
49
adverse effect. The Threshold limit values refers to the time weighted concentrations
for an 8-hour workday and a total of forty-eight (48) hours work of exposure per
week.
The threshold limit values for airborne contaminants and for noise exposure are
presented in a table under the said rule and are followed accordingly in the plant.
Natural or artificial lighting is provided in places where people may pass by in the
plant. Skylights and windows are placed and spaced so that daylight conditions are
fairly uniform over the working area and when daylight fails or for area where the
daylight illumination is insufficient artificial lighting is provided.
Emergency lighting system is also provided in all important stairways, exits,

workplaces and passages in the plant for emergency purposes. In the workrooms,
suitable atmospheric conditions are maintained by natural or artificial means to avoid
insufficient air supply, stagnant or vitiated air, harmful drafts, excessive heat or cold,
sudden variations in temperature, and where practicable, excessive humidity or
dryness and objectionable odors.
In the work areas inside the plant, the temperature suitable for the type of work
performed are maintained in enclosed workplaces and such temperature are increased
or decreased and the degree of humidity varied in accordance with the kind of work.
All of these measures are followed and implemented accordingly in the plant to
provide comfortable and healthy conditions and to promote and maintain the health of
the workers.
50
10.5 Fire and Explosion Index (FEI) Assessment
Table 10.1 FEI Assessment for Ultrasonic Probe Cell Sonicator
AREA/COUNTRY: LOCATION: DATE:
Philippines Naga City, Cebu January 20, 2018
SITE: MANUFACTURING UNIT: PROCESSING UNIT:

Uling, Naga City, Cebu Zeolite A Ultrasonic Probe Cell Sonicator
PREPARED BY APPROVED BY
Balbino, Geraldine Dellosa, Vienel May Engr. Vera Marie Lanaria
Calambro, Neljan Nicolas Sanchez, Maria Sancha REVIEWED BY
Cañete, Julianne Christine Santos, Juhlian Cosca, Anna
May CIT-U, DENR
MATERIALS IN PROCESSING UNIT
coal fly ash, aqueous solution of sodium hydroxide
BASIC MATERIAL/S FOR
STATE OF OPERATION
MATERIAL FACTOR (MF)
Normal
Design Startup Shutdown 16
Operation
General Process Hazards Penalty Factor Penalty Factor
Range Used
Base Factor 1.00 1.00
A. Exothermic Chemical Reactions 0.30 to 1.25 0.3
B. Endothermic Processes 0.20 to 0.40 -
C. Material Handling and Transfer 0.25 to 1.05 -
D. Enclosed or Indoor Process Units 0.25 to 0.90 0.5
E. Access 0.20 to 0.35 -
F. Drainage and Spill Control 0.25 to 0.50 -
General Process Hazards Factor (F1) 1.8
Special Process Hazards
A. Toxic Material/s 0.20 to 0.80 0.2
B. Sub-Atmospheric Pressure 0.50 -
C. Operation In or Near Flammable Range
1. Tank Farms Storage Flammable Liquids 0.50 -
2. Process Upset or Purge Failure 0.30 -
3. Always in Flammable Range 0.60 -
D. Dust Explosion 0.25 to 2.00 1.25
E. Pressure (Operating Pressure in kPa: 101.325) -
F. Low Temperature 0.20 to 0.30 -
G. Quantity of Flammable / Unstable Material (in kg)
1. Liquids of Gases in Process -
2. Liquids or Gases in Storage -
3. Combustible Solids in Storage -
H. Corrosion or Erosion 0.10 to 0.75 0.20
I. Leakage (joints and packing) 0.10 to 1.50 -
J. Use of Fired Equipment -
K. Hot Oil Heat Exchange 0.15 to 1.15 -
L. Rotating Equipment 0.50 -
Special Process Hazards Factor (F2) 2.65
Process Unit Hazards Factor (F1 x F2 = F3) 4.77
Fire and Explosion Index (F3 x MF = FEI) 76.32
51
Table 10.2 FEI Assessment for Rotary Vacuum-Drum Filter

Uling, Naga City, Cebu Zeolite A Rotary Vacuum-Drum Filter
May CIT-U, DENR
Zeolite
STATE OF OPERATION
Normal
Operation
General Process Hazards
A. Exothermic Chemical Reactions 0.30 to 1.25 -
D. Enclosed or Indoor Process Units 0.25 to 0.90 -
E. Access 0.20 to 0.35 -
B. Sub-Atmospheric Pressure 0.50 0.5
D. Dust Explosion 0.25 to 2.00 -
E. Pressure (Operating Pressure in kPa: 101.325)
G. Quantity of Flammable / Unstable Material (in kg) -
I. Leakage (joints and packing) 0.10 to 1.50 0.1
L. Rotating Equipment 0.50 0.5
Fire and Explosion Index (F3 x MF = FEI) 35
52
Table 10.3 FEI Assessment for Mixing Tank

Uling, Naga City, Cebu Zeolite A Mixing Tank
May CIT-U, DENR
STATE OF OPERATION
Normal
Operation
E. Access 0.20 to 0.35 -
53
Table 10.4 FEI Assessment for Heating Tank

Uling, Naga City, Cebu Zeolite A Heating Tank
May CIT-U, DENR
STATE OF OPERATION
Normal
Operation
A. Exothermic Chemical Reactions 0.30 to 1.25 0.3
C. Material Handling and Transfer 0.25 to 1.05 0.5
E. Access 0.20 to 0.35 -
12. Always in Flammable Range 0.60 0.8
54
Table 10.5 FEI Assessment for Tunnel Dryer

Uling, Naga City, Cebu Zeolite A Tunnel Dryer
May CIT-U, DENR
STATE OF OPERATION
Normal
Operation
C. Material Handling and Transfer 0.25 to 1.05 0.5
E. Access 0.20 to 0.35 -
12. Always in Flammable Range 0.60 0.8
55
Table 10.6 FEI Assessment for Ball Mill

Uling, Naga City, Cebu Zeolite A Ball Mill
May CIT-U, DENR
STATE OF OPERATION
Normal
Operation
E. Access 0.20 to 0.35 -
56
Table 10.7 FEI Assessment for the Washing Step (Part of Rotary Drum Filter)

Uling, Naga City, Cebu Zeolite A Washing (Part of Rotary Filter)
Cañete, Julianne Christine Santos, Juhlian Cosca, Anna May
CIT-U, DENR
BASIC MATERIAL/S FOR MATERIAL
STATE OF OPERATION
FACTOR (MF)
Normal
Operation
E. Access 0.20 to 0.35 -
E. Pressure (Operating Pressure in kPa: 101.325) -
G. Quantity of Flammable / Unstable Material (in kg) -
57
10.6 Hazard and Operability (HAZOP) Study
A Hazard and Operability (HAZOP) study is a structured and systematic examination
of a planned or existing process or operation in order to identify and evaluate
problems that may represent a risk to personnel or equipment, or prevent efficient
operation. It involves a qualitative technique based on guide words.
Table 10.8 HAZOP Analysis for Sonication Equipment

VESSEL Sonicator
Intention: to agitate the slurry
Guide Word Deviation Cause Consequences Actions
NO FLOW Power failure; Delayed Check
sudden failure production electrical
in electrical system, secure
system power
generator
PART OF COMPOSITION Not enough Poorly mixed, Enforce proper
vibration of uneven control
sound concentration
of product

VESSEL Rotary Drum Vacuum Filter
Intentions: removes particulates or suspended solids from mixture
NO NO FLOW Vacuum pump Product required Inspect
fails, clog will not be met design of the
vacuum/ filter, vacuum,
drum stops regular
rotating inspection of
pipes
MORE MORE FLOW Incorrect filter Impurities, solid Use an
media used, filter particles will clog appropriate
damaged up the pipes filter media
LESS FLOW Partially blocked Slow flow of Clean the
filter media filtrate filter and
check
operating
lines
58
VESSEL Oven
Intention: used for hydrothermal treatment
MORE TEMPERATURE Excessive flow Drastic change in Temperature
of dry air crystals must be
controlled
and
monitored
PART OF COMPOSITION Low heat Most of the Add
applied filtrate did not sufficient
crystallize amount of
heat
Table 10.11 HAZOP Analysis for Filter

VESSEL Washer
Intention: washes other impurities leaving pure zeolites
MORE FLOW Broken water Some crystals are Check valves
valves also washed of for damages
LESS LESS FLOW Clogged and Insufficient flow of Do proper
leaked water maintenance
operating line
Table 10.12 HAZOP Analysis for Oven

VESSEL Dryer
Intention: removes moisture from the zeolites
MORE TEMPERATURE Uncontrolled Low moisture Maintain
heat applied content of temperature to
crystals a specified level
LESS LESS FLOW Gas valve are High moisture Repair must be
not properly content of done ahead of
closed, gas crystals time, regular
leak checking of
valve and gas
pipes
Table 10.13 HAZOP Analysis for Washer
59
VESSEL Ball mill
Intention: refine crystal size
PART OF COMPOSITION Low contact of Size of crystals Increase
particles did not meet performance of
the standards the ball mill
AS WELL AS SIZE Control system Very refined Apply safety
failure crystals measures on
control
Table 10.14 HAZOP Analysis for Dryer

VESSEL Mixing Tank
Intention: to mix thoroughly the mixture
LESS LEVEL Control valve Insufficient Proper
failure supply of the maintenance
feed
PART OF COMPOSITION Inefficient The product is Regularly
performance of not well mixed check
agitator agitator
60
CHAPTER 11:
Economy
11.1 Investment Costs
Table 11.1 Summary of Investment Costs

Investment Cost in PHILIPPINE PESOS
Land Acquisition 20,000,000.00
Paving of Roads and Other Surfaces 15,750,000.00
Construction of Building
Piping System
172,380,000.00
Plumbing
Electricals
Office Equipment and Supplies 1,000,000.00
Production Equipment 175,000,000.00
Wastewater Treatment Facility 15,000,000.00
Solid Waste Management Facility 10,000,000.00
Safety Equipment / PPE 5,000,000.00
Furniture 1,000,000.00
Trucks 30,000,000.00
Storage Equipment 10,000,000.00
Quality Control / Laboratory Equipment 5,000,000.00
Materials Preparation Equipment 5,000,000.00
Others / Contingency Fund 46,513,000
TOTAL 511,643,000.00
11.2 Operating and Maintenance Costs
Table 11.2 Summary of Operating and Maintenance Costs

Cost Cost in PHILIPPINE PESOS
Energy Consumption 542,798,530.60
Manpower 17,160,000.00
Depreciation Cost 40,061,700.00
OTHERS 49,979,769.40
TOTAL 3,150,000,000.00
61
11.3 Economic Feasibility
11.3.1 Annual Income
Table 11.3 Summary of Gross Annual Income
Annual Production 17,628,700 kg
Weight Per Sack 50 kg
Number of Sacks 352,574
Selling Price Per Sack PhP 9,500.00
Gross Annual Income PhP 3,349,453,000.00
11.3.2 Net Income

Table 11.4 Summary of Net Annual Income
Operating and Maintenance Costs PhP 650,000,000.00
Cost of Raw Materials PhP 2,500,000,000.00
Taxes (30 %) PhP 59,835,900.00
Net Annual Income PhP 139,617,100.00
11.3.3 Return on Investment

Total Investment Cost PhP 511,643,000.00
Payback Period 3.66 years
11.3.4 Break-even Period

Cost of Raw Materials PhP 2,500,000,000.00
Operating and Maintenance Costs PhP 650,000,000.00
Selling Price Per Sack PhP 9.500.00
Number of Sacks Produced 352,574
Break-Even Quantity 331,579
62
4000
3500
Cost and Income (in millions)
3000
2500
2000
1500
1000
500
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
Production (in million/s of 50-kg sacks)
Break-Even Point
Figure 11.1 Break-Even Chart
11.3.5 Profit Margin

Profit Margin 4.17 %
11.3.6 Economic Margin

The economic margin of a company or project serves to create a measure
of its economic profitability. It also serves to clear the distortion made due to
structure of capital, life of the asset, and off-balance sheet items. Economic
63
margin addresses the four main drivers for corporate performance and
enterprise value, which are profitability, competition, growth and cost of
capital. Companies with high excess returns are likely to attract competition,
leading to a shorter competitive advantage period in the valuation of the
company.

Operations-Based Cash Flow PhP 179,678,800.00
Capital Charge PhP 40,061,700.00
Inflation-Adjusted Capital PhP 511,643,000.00
Economic Margin 27.29 %
64
CHAPTER 12:
Conclusion and Recommendations
The plant was designed to be environment-friendly, economically viable, energy-efficient

and productive. Zeolite A, one of the most economically important types of synthetic zeolites,
is produced using coal fly ash sourced from coal-based thermal power plants in Cebu. An
annual production of 352,574 sacks or approximately 17,628.70 metric tons of zeolite A can
be expected from an annual requirement of 62,400 tons of class F coal fly ash.
Mass and energy balances, and economic analyses were done based on the work done by
Du Plessis (2014) and the report of -Research and Markets-, a business research firm, which
cited an optimistic growth in the demand for synthetic zeolites, especially in the detergents
industry which continues to substitute phosphates with synthetic zeolites.
The Analytical Hierarchy Process, a quantitative method for decision making, was used in
the selection of the zeolite synthesis method and in the selection of equipment for the plant.
Coal fly ash, the main raw material for the synthesis of zeolite A, can be obtained from power
plants at minimal cost.
The process selection was done based on cost, yield, environmental impact, health and
safety, and sustainability. Importance was given to the last three criteria, which carry a
combined weight of almost 90 percent.
Four criteria or factors were considered in the selection of equipment for the plant. These
are cost, safety, operability, and environmental compliance. The last criterion carries the most
weight with a value close to two-thirds of the total rating or about 66 percent.
It is recommended that the process and equipment design be re-evaluated. Further

research and development can be done to improve the yield of the process and the efficiency
of the equipment. The payback period was computed to be 3.66 years. The computations for
the economic viability of the plant design were based on prices obtained from online sources
for retailers.
It is recommended that new suppliers for the equipment and the raw materials be found to
reduce production and equipment costs. It is also recommended that, as part of due diligence,
the other costs, including building construction and land acquisition costs, be reviewed since
they are merely estimates based on online sources.
65
REFERENCES
[1] Brassell, James & Ojumu, Tunde & Petrik, Leslie. (2016). Upscaling of Zeolite
Synthesis from Coal Fly Ash Waste: Current Status and Future Outlook.
10.5772/63792.
[2] Department of Energy. Retrieved from https://www.doe.gov.ph
[3] Du Plessis, P.W. (2014). Process Design for the Up-Scale Zeolite Synthesis from
South African Coal Fly Ash. Cape Peninsula University of Technology, Cape Town,
South Africa
[4] Du Plessis, P.W., Ojumu, T.V., Fatoba, O.O., Akinyeye, R.O., Petrik, L.F. (2014).
Distributional Fate of Elements during the Synthesis of zeolites from South African
Coal Fly Ash. Cape Peninsula University of Technology, Cape Town, South Africa
[5] Ferrarini, S.F., Cardoso, A.M., Paprocki, A., & Pires, M. (2016). Integrated Synthesis
of Zeolites Using Coal Fly Ash: Element Distribution in the Products, Washing Waters
and Effluent. Journal of the Brazilian Chemical Society, 27(11), 2034-2045
[6] Flanigen, E.M., Broach, R.W., & Wilson, S.T. (2010). Zeolites in Industrial
Separation and Catalysis. In S. Kulprathipanja (Ed.), Zeolites in Industrial Separation
and Catalysis. Weinheim: WILEY-VCH Verlag GmbH & Co. KGaA
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[7] Franus, W., Wdowin, M., & Franus, M. (2014). Synthesis and Characterization of
Zeolites Prepared from Industrial Fly Ash. Environmental Monitoring and
Assessment, 186, 5721-5729
[8] Fukasawa, T., Horigome, A., Tsu, T., Karisma, A.D., Maeda, N., Huang, A., & Fukui,
K. (2017). Utilization of Incineration Fly Ash from Biomass Power Plants for Zeolite
Synthesis from Coal Fly Ash by Hydrothermal Treatment. Fuel Processing
Technology, 167(1), 92-98
[9] Fukasawa, T., Karisma, A.D., Shibata, D., Huang, A., & Fukui, K. (2017). Synthesis
of Zeolite from Coal Fly Ash by Microwave Hydrothermal Treatment with
Pulverization Process. Advanced Powder Technology, 28(3), 798-804
[10] Global Synthetic Zeolite Market: Manufacturers Focus on Contruction, Adsorbents
after Conquering Detergents Industry. Retrieved from
https://www.transparencymarketresearch.com/pressrelease/synthetic-zeolites-
markey.htm
[11] Global Synthetic Zeolites (Zeolite A, Zeolite Y, Zeolite X, Zeolite Zsm-5) Market
2017-2022 - Research and Markets. (2017, June 10). Retrieved from
https://www.businesswire.com/news/home/20170710005806/en/Global-Synthetic-
Zeolites-Zeolite-Zeolite-Zeolite-Zeolite.
[12] Global Zeolites Market Size, Market Share, Application Analysis, Regional Outlook,
Growth Trends, Key Players, Competitive Strategies and Forecasts, 2017 to 2025.
(2017, August). Retrieved from
67
https://www.researchandmarkets.com/reports/4431757/global-zeolites-market-size-
market-share#rela4
[13] Human and Environmental Risk Assessment in Ingredients of European Household
Cleaning Products. Retrieved from https://www.heraproject.com/files/8-f-be8d7cff-
a805-0020-23f16e4b786891e8.pdf
[14] Jha, B., Singh, D.N. (2016). Fly Ash Zeolites. Retrieved from
http://www.springer.com/978-981-10-1402-4
[15] Jin, X., Ji, N., Song, C., Ma, D., Yan, G., & Liu, Q. (2015). Synthesis of CHA Zeolite
Using Low Cost Coal Fly Ash. Procedia Engineering, 121, 961-966
[16] Klamrassamee, T., Pavasant, P., & Laosiripojana, N. (2010). Synthesis of Zeolite from
Coal Fly Ash: Its Application as Water Sorbent. Engineering Journal, 14(1), 37-44
[17] Molina, A. & Poole, C. (2004). A Comparative Study Using Two Methods to Produce
Zolites from Fly Ash. Minerals Engineering, 17(2), 167-173
[18] Ojha, K., Pradhan, N.C., & Samanta, A.N. (2004). Zeolite from Fly Ash: Synthesis
and Characterization. Bulletin of Materials Science, 27(6), 555-564
[19] Ozdemir, O.D., & Piskin, S. (2017). A Novel Synthesis Method of Zeolite X from
Coal Fly Ash: Alkaline Fusion Followed by Ultrasonic-Assisted Synthesis Method.
Waste and Biomass Valorization, 1-12
68
[20] Patel, K. & K Srivastava, V. (2014). Recent Advances in the Synthesis of Zeolite from
Fly Ash.
[21] Querol, X., Umaña, J.C., Plana, F., Alastuey, A., Lopez-Soler, A., Medinaceli, A.,
Valero, A., Domingo, M.J., & Garcia-Rojo, E. (1999). Synthesis of Zeolites from Fly
Ash in a Pilot Scale: Examples of Potential Environmental Applications
[22] Ruen-ngam, D., Rungsuk, D., Apiratikul, R., & Pavasant P. (2009). Zeolite Formation
from Coal Fly Ash and Its Adsorption Potential. Journal of the Air & Waste
Management Association, 59(10), 1140-1147
[23] Saaty, T.L. (2008). Decision Making with the Analytic Hierarchy Process.
International Journal of Services Sciences, 1(1), 83-98
[24] SAPTASCO. Fly Ash: An Ancient Materials for Modern Day Challenges. Retrieved
from https://www.map-abcdf.com.ph/documents/presentations/AgribusinessFood%
20Processing%20and%20Manufacturing/P-20090901.pdf
[25] Shaila, K., Nisha, D., Pralhad, P., & Deepa P. (2015). Zeolite Synthesis Strategies
from Coal Fly Ash: A Comprehensive Review of Literature. International Research
Journal of Environmental Sciences, 4(3), 93-99
[26] Sherman, J.D. (1999). Synthetic Zeolites and Other Microporous Oxide Molecular
Sieves. Proceedings of the National Academy of Sciences, 96, 3471-3478
69
[27] Sing, D.N., & Koshy, N. (2016). Fly Ash Zeolites for Water Treatment Applications.
Journal of Environmental Chemical Engineering, 4(2), 1460-1472
[28] Solanki, P., Gupta, V., & Kulshrestha R. (2010). Synthesis of Zeolite from Fly Ash
and Removal of Heavy Metal Ions from Newly Synthesized Zeolite. E-Journal of
Chemistry, 7(4), 1200-1205
[29] Synthetic Zeolites Market by Type (Zeolite A, Zeolite Y, Zeolite X, Zeolite Zsm-5),
Application (Detergents, Catalysts, Adsorbents), and Region - Global Forecast to
2022. (2017, June). Retrieved from
https://www.researchandmarkets.com/research/ptnjzr/synthetic
[30] Types and Structure of Synthetic Zeolites (Molecular Sieve). (n.d.). Retrieved from
https://kntgroup.ru/en/about_zeolites/types_and_struture
[31] Yu, J., Yang, Y., Chen, W., Xu, D., Guo, H., Li, K., & Liu, H. (2016). The Synthesis
and Application of Zeolitic Material from Fly Ash by One-Pot Method at Low
Temperature. Green Energy & Environment, 1, 166-171
[32] Zeolites Structure and Types. (n.d.). Retrieved from https://www.lenntech.pl/zeolites-
structure-types.htm
[33] Zeolites. (n.d.). Retrieved from https://www.lenntech.com/zeolites.htm
70
APPENDIX A
Analytical Hierarchy Process (AHP)
The selection process is structured as a hierarchy. The criteria to be used and the
alternatives are evaluated and the criteria priorities obtained are measured with respect to
each other. Cells in comparison matrices will have a value from the numeric scale shown in
Table A.1 below. This is to reflect relative preference in each of the compared pairs.
Table A.1 Pairwise Comparison Scale

Verbal Judgment Numeric Value
9
Extremely Important
8
7
Very Strongly More Important
6
5
Strongly More Important
4
3
Moderately More Important
2
Equally Important 1
Table A.2 Selection of Method for Synthesis of Zeolites (Comparison Matrix)

Environmenta Health and Sustainabilit
Cost Yield
l Impact Safety y
Cost 1 1/8 1/7 1/4 6
Environmental
8 1 1 1 8
Impact
Health and
7 1 1 1 7
Safety
Sustainability 4 1 1 1 7
Yield 1/6 1/8 1/7 1/7 1
SUM 20.167 3.250 3.286 3.3929 29.00
71
Table A.3 Selection of Method for Synthesis of Zeolites (Normalized Data)
Environmental Health
Cost Sustainability Yield
Impact and Safety
Cost 0.0496 0.0385 0.0435 0.0737 0.2069
Environmental
0.3967 0.3077 0.3043 0.2947 0.2759
Impact
Health and
0.3471 0.3077 0.3043 0.2947 0.2414
Safety
Sustainability 0.1983 0.3077 0.3043 0.2947 0.2414
Yield 0.0083 0.0385 0.0435 0.0421 0.0345
Table A.4 Selection of Method for Synthesis of Zeolites (Calculation of Priorities)

Health
Environmental
Cost and Sustainability Yield Priority
Impact
Safety
Cost 0.0496 0.0385 0.0435 0.0737 0.2069 0.08242
Environmental
0.3967 0.3077 0.3043 0.2947 0.2759 0.31587
Impact
Health and
0.3471 0.3077 0.3043 0.2947 0.2414 0.29905
Safety
Sustainability 0.1983 0.3077 0.3043 0.2947 0.2414 0.26930
Yield 0.0083 0.0385 0.0435 0.0421 0.0345 0.03336
1.00000
Table A.5 Consistency Index

Health
Environmental Sustainabilit Weighte
Cost and Yield
Impact y d Sum
Safety
0.0824 0.2990 0.0333
Weight 0.31587 0.26930 ---
2 5 6
Cost 0.0824 0.0395 0.0427 0.0673 0.2002 0.4321
Environmental
0.6594 0.3159 0.2991 0.2693 0.2669 1.8105
Impact
Health and
0.5770 0.3159 0.2991 0.2693 0.2335 1.6947
Safety
Sustainability 0.3297 0.3159 0.2991 0.2693 0.2335 1.4474
Yield 0.0137 0.0395 0.0427 0.0385 0.0334 0.1678
72
Table A.6 Determination of Lambda_max
Weighted Sum Priority Quotient
0.4321 0.08242 5.2426
1.8105 0.31587 5.7317
1.6947 0.29905 5.6668
1.4474 0.26930 5.3747
0.1678 0.03336 5.0294
SUM 27.0452
Lambda_max 5.4090
Table A.7 Determination of Consistency Index (CI) and Consistency Ratio (CR)
Lambda_max 5.4090
CI 0.1023
CR 0.0913
Table A.8 Comparison with Respect to Cost (Method of Synthesis)

Cost Two-Step Process Fusion Assisted Method
Two-Step Process 1 1
Fusion Assisted Method 1 1
Sum 2 2
Table A.9 Preference with Respect to Cost (Method of Synthesis)

Cost Two-Step Process Fusion Assisted Method Priority
Two-Step Process 0.500 0.500 0.500
Fusion Assisted
0.500 0.500 0.500
Method
Table A.10 Results with Respect to Cost (Method of Synthesis)

Cost Two-Step Process Fusion Assisted Method Priority
Two-Step Process 1 1 0.500
73
Fusion Assisted
1 1 0.500
Method
Table A.11 Comparison with Respect to Environmental Impact (Method of Synthesis)
Environmental Impact Two-Step Process Fusion Assisted Method
Sum 2 2
Table A.12 Preference with Respect to Environmental Impact (Method of Synthesis)

Environmental
Two-Step Process Fusion Assisted Method Priority
Impact
Fusion Assisted
0.500 0.500 0.500
Method
Table A.13 Results with Respect to Environmental Impact (Method of Synthesis)

Environmental
Two-Step Process Fusion Assisted Method Priority
Impact
Fusion Assisted
1 1 0.500
Method
Table A.14 Comparison with Respect to Health and Safety (Method of Synthesis)
Health and Safety Two-Step Process Fusion Assisted Method
Sum 2 2
Table A.15 Preference with Respect to Health and Safety (Method of Synthesis)
Health and Safety Two-Step Process Fusion Assisted Method Priority
Fusion Assisted
0.500 0.500 0.500
Method
74
Table A.16 Results with Respect to Health and Safety (Method of Synthesis)
Health and Safety Two-Step Process Fusion Assisted Method Priority
Fusion Assisted
1 1 0.500
Method
Table A.17 Comparison with Respect to Sustainability (Method of Synthesis)

Sustainability Two-Step Process Fusion Assisted Method
Two-Step Process 1 1/4
Sum 5 1.25
Table A.18 Preference with Respect to Sustainability (Method of Synthesis)

Sustainability Two-Step Process Fusion Assisted Method Priority
Fusion Assisted
0.800 0.800 0.800
Method
Table A.19 Results with Respect to Sustainability (Method of Synthesis)

Sustainability Two-Step Process Fusion Assisted Method Priority
Two-Step Process 1 1/4 0.200
Fusion Assisted
4 1 0.800
Method
Table A.20 Comparison with Respect to Yield (Method of Synthesis)

Yield Two-Step Process Fusion Assisted Method
Fusion Assisted Method 1/7 1
Table A.21 Preference with Respect to Yield (Method of Synthesis)
75
Yield Two-Step Process Fusion Assisted Method Priority
Fusion Assisted
0.125 0.125 0.125
Method
Table A.22 Results with Respect to Yield (Method of Synthesis)
Yield Two-Step Process Fusion Assisted Method Priority
Fusion Assisted
1/7 1 0.125
Method
Table A.23 Local Priorities as a Base

Cost Yield
l Impact Safety y
Two-Step
0.500 0.500 0.500 0.200 0.875
Process
Fusion
Assisted 0.500 0.500 0.500 0.800 0.125
Method
Table A.24 Weighing of Priorities

Cost Yield
l Impact Safety y
Criteria
0.08242 0.31587 0.29905 0.26930 0.03336
Weights
Two-Step
0.500 0.500 0.500 0.200 0.875
Process
Fusion
Assisted 0.500 0.500 0.500 0.800 0.125
Method
Table A.25 Calculation of Overall Priorities

Health
Impact y
Safety Priorit
Criteria y
0.08242 0.31587 0.29905 0.26930 0.03336
Weights
Two-
Step 0.04121 0.15794 0.14953 0.05386 0.02919 0.43173
Process
Fusion 0.04121 0.15794 0.14953 0.21544 0.00417 0.56826
76
Assisted
Method
Table A.26 Summary

Health
Impact y
Safety Priorit
Criteria y
0.08242 0.31587 0.29905 0.26930 0.03336
Weights
Two-
Step 0.500 0.500 0.500 0.200 0.875 0.43173
Process
Fusion
Assisted 0.500 0.500 0.500 0.800 0.125 0.56826
Method
77
APPENDIX B
AHP Computations for Chapter 5
Determination of Criteria Weights

Table B.1 Pairwise Comparisons
Environmental
Cost Safety Operability
Compliance
Cost 1 1/6 1/3 1/8
Safety 6 1 1 1/6
Operability 3 1 1 1/7
Environmental
8 6 7 1
Compliance
Column Sum 18 8.1667 9.3333 1.4345
Table B.2 Normalized Matrix

Row
Environmental
Cost Safety Operability Average
Compliance
s
Cost 0.0556 0.0204 0.0357 0.0871 0.0497
Safety 0.3333 0.1224 0.1071 0.1162 0.1698
Operability 0.1667 0.1224 0.1071 0.0996 0.1240
Environmental
0.4444 0.7347 0.7500 0.6971 0.6566
Compliance
Table B.3 Consistency Index

Environmental Weighte
Compliance d Sum
Weight 0.0497 0.1698 0.1240 0.6566 ---
Cost 0.0497 0.0283 0.0413 0.0821 0.2014
Safety 0.2982 0.1698 0.1240 0.1094 0.7014
Operability 0.1491 0.1698 0.1240 0.0938 0.5366
Environmental
0.3976 1.0187 0.8677 0.6566 2.9406
Compliance
78
Table B.4 Determination of Lambda-max
Weighted Sum Priority Quotient
0.2014 0.0497 4.0518
0.7014 0.1698 4.1312
0.5366 0.1240 4.3291
2.9406 0.6566 4.4788
SUM 16.9909
Lambda-max 4.2477
Table B.5 Determination of Consistency Index (CI) and Consistency Ratio (CR)
Lambda-max 4.2477
CI 0.0826
CR 0.0918
Selection of Sonication Equipment
Table B.6 Comparison with Respect to Cost

Ultrasonic Probe Cell
Cost Ultrasonic Bath Sonicator
Sonicator
1 1
Sonicator
Ultrasonic Bath Sonicator 1 1
Sum 2 2
Table B.7 Preference with Respect to Cost

Ultrasonic Probe Cell Ultrasonic Bath
Cost Priority
Sonicator Sonicator
Ultrasonic Probe
0.500 0.500 0.500
Cell Sonicator
Ultrasonic Bath
0.500 0.500 0.500
Sonicator
79
Table B.8 Results with Respect to Cost
Cost Priority
Sonicator Sonicator
Ultrasonic Probe
1 1 0.500
Cell Sonicator
Ultrasonic Bath
1 1 0.500
Sonicator
Table B.9 Comparison with Respect to Safety

Safety Ultrasonic Bath Sonicator
Sonicator
1 2
Sonicator
Ultrasonic Bath Sonicator 1/2 1
Sum 1.500 3
Table B.10 Preference with Respect to Safety

Safety Priority
Sonicator Sonicator
Ultrasonic Probe
0.667 0.667 0.667
Cell Sonicator
Ultrasonic Bath
0.333 0.333 0.333
Sonicator
Table B.11 Results with Respect to Safety

Safety Priority
Sonicator Sonicator
Ultrasonic Probe
1 2 0.667
Cell Sonicator
Ultrasonic Bath
1/2 1 0.333
Sonicator
80
Table B.12 Comparison with Respect to Operability
Operability Ultrasonic Bath Sonicator
Sonicator
1 4
Sonicator
Ultrasonic Bath Sonicator 1/4 1
Sum 1.250 5
Table B.13 Preference with Respect to Operability

Operability Priority
Sonicator Sonicator
Ultrasonic Probe
0.800 0.800 0.800
Cell Sonicator
Ultrasonic Bath
0.200 0.200 0.200
Sonicator
Table B.14 Results with Respect to Operability

Sonicator Sonicator
Ultrasonic Probe
1 4 0.800
Cell Sonicator
Ultrasonic Bath
1/4 1 0.200
Sonicator
Table B.15 Comparison with Respect to Environmental Compliance

Environmental Compliance Ultrasonic Bath Sonicator
Sonicator
1 1
Sonicator
Ultrasonic Bath Sonicator 1 1
Sum 2 2
81
Table B.16 Preference with Respect to Environmental Compliance
Environmental Ultrasonic Probe Cell Ultrasonic Bath
Priority
Compliance Sonicator Sonicator
Ultrasonic Probe
0.500 0.500 0.500
Cell Sonicator
Ultrasonic Bath
0.500 0.500 0.500
Sonicator
Table B.17 Results with Respect to Environmental Compliance

Sonicator Sonicator
Ultrasonic Probe
1 1 0.500
Cell Sonicator
Ultrasonic Bath
1 1 0.500
Sonicator
Table B.18 Local Priorities as a Base

Environmental
Compliance
Ultrasonic
Probe Cell 0.500 0.667 0.800 0.500
Sonicator
Ultrasonic
0.500 0.333 0.200 0.500
Bath Sonicator
Table B.19 Weighing of Priorities

Environmental
Compliance
Criteria
0.0497 0.1698 0.1240 0.6566
Weights
Ultrasonic
Probe Cell 0.500 0.667 0.800 0.500
Sonicator
Ultrasonic
0.500 0.333 0.200 0.500
Bath Sonicator
82
Table B.20 Calculation of Overall Priorities
Environmental
Compliance Overall
Criteria Priority
0.0497 0.1698 0.1240 0.6566
Weights
Ultrasonic
Probe Cell 0.0249 0.1133 0.0992 0.3283 0.5657
Sonicator
Ultrasonic
Bath 0.0249 0.0565 0.0248 0.3283 0.4345
Sonicator
Table B.21 Summary

Environmental
Compliance Overall
Criteria Priority
0.0497 0.1698 0.1240 0.6566
Weights
Ultrasonic
Probe Cell 0.500 0.667 0.800 0.500 0.5657
Sonicator
Ultrasonic
Bath 0.500 0.333 0.200 0.500 0.4345
Sonicator
Selection of Filtration Equipment

Cost Rotary Vacuum-Drum Filter Bed Filter
Rotary Vacuum-Drum Filter 1 1/2
Bed Filter 2 1
Sum 3 1.500
83
Rotary Vacuum-Drum
Cost Bed Filter Priority
Filter
Rotary Vacuum-
0.333 0.333 0.333
Drum Filter
Bed Filter 0.667 0.667 0.667
Table B.24 Results with Respect to Cost (Method of Synthesis)

Rotary Vacuum-Drum
Filter
Rotary Vacuum-
1 1/2 0.333
Drum Filter
Bed Filter 2 1 0.667

Safety Rotary Vacuum-Drum Filter Bed Filter
Rotary Vacuum-Drum Filter 1 1
Bed Filter 1 1
Sum 2 2

Rotary Vacuum-Drum
Safety Bed Filter Priority
Filter
Rotary Vacuum-
0.500 0.500 0.500
Drum Filter
Bed Filter 0.500 0.500 0.500

Rotary Vacuum-Drum
Filter
Rotary Vacuum-
1 1 0.500
Drum Filter
Bed Filter 1 1 0.500
84
Operability Rotary Vacuum-Drum Filter Bed Filter
Bed Filter 1/4 1
Sum 1.250 5

Rotary Vacuum-Drum
Operability Bed Filter Priority
Filter
Rotary Vacuum-
0.800 0.800 0.800
Drum Filter
Bed Filter 0.200 0.200 0.200

Rotary Vacuum-Drum
Operability Bed Filter Priority
Filter
Rotary Vacuum-
1 4 0.800
Drum Filter
Bed Filter 1/4 1 0.200

Environmental Compliance Rotary Vacuum-Drum Filter Bed Filter
Bed Filter 1/5 1
Sum 1.200 6

Environmental Rotary Vacuum-Drum
Bed Filter Priority
Compliance Filter
Rotary Vacuum-
0.833 0.833 0.833
Drum Filter
Bed Filter 0.167 0.167 0.167
85
Environmental Rotary Vacuum-Drum
Bed Filter Priority
Compliance Filter
Rotary Vacuum-
1 5 0.833
Drum Filter
Bed Filter 1/5 1 0.167

Environmental
Compliance
Rotary
Vacuum-Drum 0.333 0.500 0.800 0.833
Filter
Bed Filter 0.667 0.500 0.200 0.167

Environmental
Compliance
Criteria
0.0497 0.1698 0.1240 0.6566
Weights
Rotary
Vacuum-Drum 0.333 0.500 0.800 0.833
Filter
Bed Filter 0.667 0.500 0.200 0.167

Environmental
Compliance Overall
Criteria Priority
0.0497 0.1698 0.1240 0.6566
Weights
Rotary
Vacuum- 0.0166 0.0849 0.0992 0.5469 0.7476
Drum Filter
Bed Filter 0.0331 0.0849 0.0248 0.1097 0.2525
86
Table B.37 Summary
Environmental
Compliance Overall
Criteria Priority
0.0497 0.1698 0.1240 0.6566
Weights
Rotary
Vacuum- 0.333 0.500 0.800 0.833 0.7476
Drum Filter
Bed Filter 0.667 0.500 0.200 0.167 0.2525
Selection of Equipment for Hydrothermal Treatment

Cost Heating Tank Hot-Air Oven
Heating Tank 1 5
Hot-Air Oven 1/5 1
Sum 1.200 6

Cost Heating Tank Hot-Air Oven Priority
Heating Tank 0.833 0.833 0.833
Hot-Air Oven 0.167 0.167 0.167

Cost Heating Tank Hot-Air Oven Priority
Heating Tank 1 5 0.833
Hot-Air Oven 1/5 1 0.167
87
Safety Heating Tank Hot-Air Oven
Heating Tank 1 4
Hot-Air Oven 1/4 1
Sum 1.250 5

Safety Heating Tank Hot-Air Oven Priority
Heating Tank 0.800 0.800 0.800
Hot-Air Oven 0.200 0.200 0.200


Heating Tank 1 8
Hot-Air Oven 1/8 1
Sum 1.125 9

Heating Tank 0.889 0.889 0.889
Hot-Air Oven 0.111 0.111 0.111

88
Heating Tank 1 2
Hot-Air Oven 1/2 1
Sum 1.500 3

Heating Tank 0.667 0.667 0.667
Hot-Air Oven 0.333 0.333 0.333


Environmental
Compliance
Heating Tank 0.833 0.800 0.889 0.667
Hot-Air Oven 0.167 0.200 0.111 0.333

Environmental
Compliance
Criteria
0.0497 0.1698 0.1240 0.6566
Weights
Heating Tank 0.833 0.800 0.889 0.667
Hot-Air Oven 0.167 0.200 0.111 0.333
89
Environmental
Compliance Overall
Criteria Priority
0.0497 0.1698 0.1240 0.6566
Weights
Heating
0.0414 0.1358 0.1102 0.4380 0.7254
Tank
Hot-Air
0.0083 0.0340 0.0138 0.2186 0.2747
Oven
Table B.53 Summary

Environmental
Compliance Overall
Criteria Priority
0.0497 0.1698 0.1240 0.6566
Weights
Heating
0.833 0.800 0.889 0.667 0.7254
Tank
Hot-Air
0.167 0.200 0.111 0.333 0.2747
Oven
Selection of Dryer

Cost Tunnel Dryer Rotary Dryer
Tunnel Dryer 1 4
Rotary Dryer 1/4 1
Sum 1.250 5

Cost Tunnel Dryer Rotary Dryer Priority
Tunnel Dryer 0.800 0.800 0.800
Rotary Dryer 0.200 0.200 0.200
90
Cost Tunnel Dryer Rotary Dryer Priority
Tunnel Dryer 1 4 0.800
Rotary Dryer 1/4 1 0.200

Safety Tunnel Dryer Rotary Dryer
Tunnel Dryer 1 1
Rotary Dryer 1 1
Sum 2 2

Safety Tunnel Dryer Rotary Dryer Priority
Tunnel Dryer 0.500 0.500 0.500
Rotary Dryer 0.500 0.500 0.500

Safety Tunnel Dryer Rotary Dryer Priority
Rotary Dryer 1 1 0.500

Operability Tunnel Dryer Rotary Dryer
Tunnel Dryer 1 5
Rotary Dryer 1/5 1
Sum 1.200 6

Operability Tunnel Dryer Rotary Dryer Priority
Tunnel Dryer 0.833 0.833 0.833
Rotary Dryer 0.167 0.167 0.167
91
Operability Tunnel Dryer Rotary Dryer Priority
Rotary Dryer 1/5 1 0.167

Environmental Compliance Tunnel Dryer Rotary Dryer
Tunnel Dryer 1 1
Rotary Dryer 1 1
Sum 2 2

Environmental
Tunnel Dryer Rotary Dryer Priority
Compliance
Tunnel Dryer 0.500 0.500 0.500
Rotary Dryer 0.500 0.500 0.500

Environmental
Tunnel Dryer Rotary Dryer Priority
Compliance
Rotary Dryer 1 1 0.500

Environmental
Compliance
Tunnel Dryer 0.800 0.500 0.833 0.500
Rotary Dryer 0.200 0.500 0.167 0.500
92
Environmental
Compliance
Criteria
0.0497 0.1698 0.1240 0.6566
Weights
Tunnel Dryer 0.800 0.500 0.833 0.500
Rotary Dryer 0.200 0.500 0.167 0.500

Environmental
Compliance Overall
Criteria Priority
0.0497 0.1698 0.1240 0.6566
Weights
Tunnel
0.0398 0.0849 0.1033 0.3283 0.5563
Dryer
Rotary
0.0099 0.0849 0.0207 0.3283 0.4438
Dryer
Table B.69 Summary

Environmental
Compliance Overall
Criteria Priority
0.0497 0.1698 0.1240 0.6566
Weights
Tunnel
0.800 0.500 0.833 0.800 0.5563
Dryer
Rotary
0.200 0.500 0.167 0.200 0.4438
Dryer
Selection of Crushing Equipment

Cost Ball Mill Roller Mill
Ball Mill 1 1
Roller Mill 1 1
Sum 2 2
93
Cost Ball Mill Roller Mill Priority
Ball Mill 0.500 0.500 0.500
Roller Mill 0.500 0.500 0.500

Ball Mill 0.500 0.500 0.500
Roller Mill 0.500 0.500 0.500

Safety Ball Mill Roller Mill
Ball Mill 1 2
Roller Mill 1/2 1
Sum 1.500 3

Ball Mill 0.667 0.667 0.667
Roller Mill 0.333 0.333 0.333

Ball Mill 1 2 0.667
Roller Mill 1/2 1 0.333

Operability Ball Mill Roller Mill
Ball Mill 1 2
Roller Mill 1/2 1
Sum 1.500 3
94
Operability Ball Mill Roller Mill Priority
Ball Mill 0.667 0.667 0.667
Roller Mill 0.333 0.333 0.333

Operability Ball Mill Roller Mill Priority
Ball Mill 1 2 0.667
Roller Mill 1/2 1 0.333

Environmental
Ball Mill Roller Mill
Compliance
Ball Mill 1 1
Roller Mill 1 1
Sum 2 2

Environmental
Ball Mill Roller Mill Priority
Compliance
Ball Mill 0.500 0.500 0.500
Roller Mill 0.500 0.500 0.500

Environmental
Ball Mill Roller Mill Priority
Compliance
Ball Mill 1 1 0.500
Roller Mill 1 1 0.500
95
Environmental
Compliance
Ball Mill 0.500 0.667 0.667 0.500
Roller Mill 0.500 0.333 0.333 0.500

Environmental
Compliance
Criterial
0.0497 0.1698 0.1240 0.6566
Weights
Ball Mill 0.500 0.667 0.667 0.500
Roller Mill 0.500 0.333 0.333 0.500

Environmental
Compliance Overall
Criterial Priority
0.0497 0.1698 0.1240 0.6566
Weights
Ball Mill 0.0249 0.1133 0.0827 0.3283 0.5492
Roller Mill 0.0249 0.0565 0.0413 0.3283 0.4510
Table B.85 Summary

Environmental
Compliance Overall
Criterial Priority
0.0497 0.1698 0.1240 0.6566
Weights
Ball Mill 0.500 0.667 0.667 0.500 0.5492
Roller Mill 0.500 0.333 0.333 0.500 0.4510
96
APPENDIX C
Heat and Mass Balances
Figure C.1 Energy Balance Over Mixing Tank
Basis: 1 day = 20,800 seconds

∆ H NaOH + ∆ H CFA =3,562kW
Solutions:
200,000 kg
a) For ∆ H NaOH = wt NaOH = x 100 =18.08
1,106,103.2864 kg
From Enthalpy – concentration diagram: ∆ H (kJ/ kg solution) from (20°C to
40°C)
kJ kJ
∆ H= ( 170−80 ) =90
kg kg
kJ
Therefore, ∆ H NaOH =90 ( 1,106,103.2864 kg ) ( 40−20 ) ° C=99,549,295 kJ
kg
99,549,295 kJ
∆ H NaOH = =3,456.57 kW
28,800 s
kJ
b) For ∆ H CFA Cp (CFA at 30 °C) =0.7595
kg °C
kJ
Therefore, ∆ H CFA =0.7595 ( 200,000 kg )( 40−20 ) ° C=3,038,000kJ
kg ° C
3,038,000 kJ
∆ H CFA = =105.486 kW
28,800 s
∆ H ¿ (mixing tank )=3456.57 kW + 105.486 kW=3,562kW
97
Coal Fly Ash
200,000 kg
(125,000 L)
Slurry
SONICATOR 1,306,103.286 kg
(1,125,000 L)
NaOH solution
1,106,103.286 kg
(1,000,000 L)
Figure C.2 Material Balance Over Sonicator
Density of Coal Fly Ash = 1.60 kg / L

Density of Sodium Hydroxide Solution = 2.13 kg / L
Volume of Coal Fly Ash = 200,000 kg * 1 L / 1.60 kg = 125,000 L
Normality of Sodium Hydroxide Solution = 5 M or 5 moles / L

Weight of Sodium Hydroxide = 1,000,000 L * 5 moles / L * 0.040 kg / moles
Weight of Sodium Hydroxide = 200,000 kg
Volume of Sodium Hydroxide = 200,000 kg * 1 L / 2.13 kg = 93,896.71362 L
Volume of Water = 1,000,000 L – 93,896.71362 L = 906,103.2864 L

Weight of NaOH Solution = 906,103.2864 kg + 200,000.0000 kg = 1,106,103.2860 kg
Weight of Slurry = 1,306,103.2860 kg
98
Figure C.3 Energy Balance Over Sonicator

∆ H NaOH + ∆ H CFA =8,407 kW
Solutions:
200,000 kg
a) For ∆ H NaOH = wt NaOH = x 100 =18.08
1,106,103.2864 kg
From Enthalpy – concentration diagram: ∆ H (kJ/ kg solution) from (40°C to
100°C)
kJ kJ
∆ H= ( 380−170 ) =210
kg kg
kJ
Therefore, ∆ H NaOH =210 (1,106,103.2864 kg ) ( 100−40 ) ° C=232,281,690.1 kJ
kg
232,281,690.1kJ
∆ H NaOH = =8,065.3365 kW
28,800 s
kJ
b) For ∆ H CFA Cp (CFA at 70 °C) =0.82
kg °C
kJ
Therefore, ∆ H CFA =0.82 ( 200,000 kg ) ( 100−40 ) ° C=9,840,000kJ
kg ° C
9,840,000 kJ
∆ H CFA = =341.67 kW
28,800 s
∆ H ¿ (sonicator )=8,065.3365 kW +341.67 kW =8,407 kW
99
Filtrate
998, 103.2864 kg
ROTARY
Slurry VACUUM
1,306,103.2864 kg DRUM
FILTER Solid Waste
308,000 kg
Figure C.4 Material Balance Over Rotary Vacuum Drum Filter
Mass balance:
In = Out (assuming steady-state operation)
kg slurry = kg filtrate + kg solid waste

1,306,103.2864 = 998,103.2864 kg + 308,000 kg
1,306,103.2864 kg = 1,306,103.2864 kg
100
Filtrate
998, 103.2864 kg
Adjusted
MIXING Filtrate
Sodium TANK
Aluminate 1,425,861.838 kg
Solution
427, 758.5513 kg
Figure C.5 Material Balance Over Mixing Tank
Mass balance:
kg filtrate + kg sodium aluminate solution = kg adjusted filtrate

998,103.2864 kg + 427,758.5513 kg = 1,425,861.838 kg
1,425,861.838 kg = 1,425,861.838 kg
Density of sodium aluminate solution = 1.50 kg / L

Volume of sodium aluminate solution = 427,758.5513 / 1.50
Volume of sodium aluminate solution = 285,172.3675 L
Assumption: density of filtrate = density of water at 25 °C = 1 kg / L

Volume of filtrate = 998,103.2864 L
101
Zeolite Product
Adjusted +
HEATING Supernatant
Filtrate
TANK Waste
1,425,861.838 kg
1,425,861.838 kg
Figure C.6 Material Balance Over Hot-Air Oven
Mass balance:
kg adjusted filtrate = kg zeolite product and supernatant waste

1,425,861.838 kg = 1,425,861.838
102
Figure C.7 Energy Balance Over Tunnel Dryer
Assumptions:
1) Adjusted Filtrate is only a mixture of H2O and NaAlO2 since the filtrate only
has roughly 9% solids (CFA and NaOH).

2) Since the adjusted filtrate is assumed to be just a mixture of H2O and NaAlO2,
only their masses are considered to calculate the specific heat of the mixture.
Solution:
kJ
∆ H Mixture=3.134 ( 1,425,861.838 kg ) ( 90−20 ) ° C=312,805,570 kJ
kg ° C
312,805,570 kJ
∆ H Mixture= =10,861.3 kW
28,800 s
10,861.3 kW
Wash Water
η ( oven ) = x 100 =45
11,210,762.33 kg
24,000 kW
Zeolite Product ROTARY Zeolite Product

+ VACUUM +
Supernatant DRUM Adhering Wash
Waste FILTER Water
1,425,861.838 kg 67,713.00448 kg
103
Waste Liquid
12,568,911.17 kg
Figure C.8 Material Balance Over Rotary Vacuum Drum Filter
Mass balance:
kg zeolite product and supernatant waste + kg wash water = In

kg zeolite product and adhering wash water + waste liquid = Out
In = Out
1,425,861.838 kg + 11,210,762.33 kg = 67,713.00448 kg + 12,568,911.17 kg
12,636,624.17 kg = 12,636,624.17 kg
104
SPECIFIC HEATS
For CFA:
Molecular Weight (kg/kgmol)
Al2O3 = 101.96 (31.51%)
SiO2 = 60.08 (55.44%)
Fe2O3 = 154.60 (4.94%)
CaO = 56.0774 (3.76%)
rest = 4.35% | 95.65%
From Thermodynamic properties section of our paper
For Mixing Tank

Average Temperature at 30°C (20°C to 40°C) therefore, CP (CFA at
30°C)
CP (kJ/kg °C): Al2O3 = 0.785 0.785(0.3151)
SiO2 = 0.7585 0.7585(0.5544)
Fe2O3 = 0.6534 0.6534(0.0494)
CaO = 0.768 0.768(0.0376)
rest is assumed = 0.70 0.70(0.0435)
CP = 0.7595 kJ/kg °C
For Sonicator
Average Temperature at 70°C (40°C to 100°C) therefore, CP (CFA at
70°C)
CP (kJ/kg °C): Al2O3 = 0.85 0.85(0.3151)
SiO2 = 0.823 0.823 (0.5544)
Fe2O3 = 0.698 0.698(0.0494)
CaO = 0.802 0.802(0.0376)
rest is assumed = 0.75 0.75(0.0435)
CP = 0.82 kJ/kg °C
For Adjusted Filtrate

CP (kJ/kg °C): H2O (68%) = 4.186 NaAlO2 (32%) = 4.186
CP (Adjusted Filtrate) = 4.186(0.68) + 4.186(0.32) =3.134 kJ/kg °C
Mass CFA & NAoH = 92,000 kg is not included
H2O = 906,103,2864 kg (68%)
105
NaAlO2 = 427,758.5513 kg (32%) Therefore, Cp mixture =3.134
kJ
kg °C
Adjusted Filtrate (mixture) = 1,333,861.838 kg
106
Water Vapor
11,210.76233 kg
Zeolite Product
+ Dried Zeolite
Adhering Wash DRYER Product
Water 56,502.24215 kg
67,713.00448 kg
Figure C.9 Material Balance Over Dryer
Mass balance:
kg zeolite product and adhering wash water = kg water vapor + kg dried zeolite product
67,713.00448 kg = 11,210.76233 kg + 56,502.24215 kg
67,713.00448 kg = 67,713.00448 kg
107
Figure C.10 Energy Balance Over Tunnel Dryer
Solution:
∆ H wash vapor =m τ v
kJ
(
∆ H wash vapor =11,210,762.33 kg 22.57
kg )
=25 , 302,620.58 kJ
25 , 302,620.58 kJ
∆ H wash vapor = =878.6 kW
28,800 s
108
Dried Crushed
Zeolite Product BALL MILL Zeolite Product
56,502.24215 kg 56,502.24215 kg
Figure C.11 Material Balance Over Ball Mill
Mass balance:
Assumption: no losses during operation of ball mill
kg dried zeolite product = kg crushed zeolite product

56,502.24215 kg = 56,502.24215 kg
109
APPENDIX D
Economy
I. Investment Costs
Table D.1 Summary of Investment Costs

Investment Cost in PHILIPPINE PESOS
total land area = 20,000 m2
Land Acquisition
20,000 m2 * 1000 / m2 = 20,000,000.00
area of roads = 6,425 m2
area of parking lots = 1,450 m2
Paving of Roads and Other Surfaces total area = 7,875 m2
7,875 m2 * 2000 / m2 = 15,750,000.00
Construction of Building
Piping System total floor area = 7,800 m2
Plumbing 7,800 * 22,100 / m2 = 172,380,000.00
Electricals
Office Equipment and Supplies Estimated cost = 1,000,000.00
Please see Table D.2 for detailed
Production Equipment
computation.
Wastewater Treatment Facility Estimated cost = 15,000,000.00
Solid Waste Management Facility Estimated cost = 10,000,000.00
Safety Equipment / PPE Estimated cost = 5,000,000.00
Furniture Estimated cost = 1,000,000.00
number of trucks = 20
Trucks
20 * 1,500,000 / truck = 30,000,000.00
Storage Equipment Estimated cost = 10,000,000.00
Quality Control / Laboratory Equipment Estimated cost = 5,000,000.00
Materials Preparation Equipment Estimated cost = 5,000,000.00
sub-total = 465,130,000.00
Others / Contingency Fund
465,130,000.00 * 0.10 = 46,513,000.00
TOTAL 511,643,000.00
Table D.2 Cost of Production Equipment*
110
Equipment Quantity Unit Cost (PhP) Total Cost (PhP)
Sonicator 6 5,000,000.00 30,000,000.00
Rotary Drum
6 13,000,000.00 78,000,000.00
Vacuum Filter
Mixing Tank 12 1,000,000.00 12,000,000.00
Heating Tank 6 3,000,000.00 18,000,000.00
Tunnel Dryer 2 10,000,000.00 20,000,000.00
Ball Mill 2 8,500,000.00 17,000,000.00
TOTAL ----
* Estimates obtained from Alibaba and Amazon.com
II. Operating and Maintenance Costs

Cost of electricity per kWh = PhP 12.50
Annual electricity / energy consumption = 43,423,882.45 kWh
Cost of energy consumption = 43,423,882.45 kWh * 12.50 per kWh
Cost of energy consumption = 542,798,530.60
The plant will operate 8 hours a day for 6 days a week for 52 weeks each year. This
means that the plant will operate for 2,496 hours or 312 days a year.
Cost of manpower = 100 employees * PhP 500 per day per employee * 312 days per year
Cost of manpower = 15,600,000.00 per year
We will add 10 % for other benefits and bonuses.
Final cost of manpower = 15,600,000.00 * 1.10

Final cost of manpower = 17,160,000.00
The cost of depreciation is computed using the straight-line method. The cost of land
acquisition and the contingency fund are not included in the computation. The useful life
is assumed to be ten years and the salvage value 10 % of the first cost.
Annual cost of depreciation = (445,130,000.00 * 0.90) / 10

Annual cost of depreciation = 40,061,700.00
III. Economic Feasibility
111
Annual Income
Gross annual income = number of 50-kg sacks produced * selling price per sack
Gross annual income = 352,574 sacks * 9,500 per sack
Gross annual income = 3,349,453,000.00
Net Income
Net income = gross annual income – (operating & maintenance costs + cost of materials)
Net income = 3,349,453,000.00 – (650,000,000.00 + 2,500,000,000.00)
Net income = 139,617,100.00
Return on Investment
Profit margin = (net annual income / gross annual income) * 100
Profit margin = (139,617,100.00 / 3,349,453,000.00) * 100
Profit margin = 4.1684 %
Break-Even Period
Fixed costs = cost of manpower + depreciation cost + others
Fixed costs = 17,160,000.00 + 40,061,700.00 + 49,979,769.40
Fixed costs = 107,201,469.40
Variable costs = 542,798,530.60 + 2,500,000,000.00

Variable costs = 3,042,798,531.00
Variable cost per sack = 3,042,798,531.00 / 352,574

Variable cost per sack = 8630.240831
Economic Margin (EM)
112
EM = (operations-based cash flow – capital charge) / inflation adjusted capital
Operations-based cash flow = net income + depreciation & amortization + after-tax
interest rate + rental expense adjusted net interest + R&D
expense +/ – nonrecurring items
Operations-based cash flow = 139,617,100.00 + 40,061,700.00 + 0 + 0 + 0 +/ – 0
Operations-based cash flow = 179,678,800.00
Capital charge = return on and return of capital that captures company-specific economic
circumstances
Capital charge = 40,061,700.00
Inflation adjusted investment capital = total assets + accumulated depreciation + gross

plant inflation adjustment + capitalized operating rentals +
capitalized R&D – net debt current liabilities + revaluations
Inflation adjusted investment capital = 511,643,000.00
EM = (179,678,800.00 – 40,061,700.00) / 511,643,000.00

EM = 0.2729 (or 27.29 %)
113
APPENDIX E
Process Safety Guide Words
Table F.1 Ratings for DOW FEI

DOW FEI Degree of Hazard
1-60 Light
61-96 Moderate
97-127 Intermediate
128-158 Heavy
159 and above Severe
Table F.2 List of Guide Words

Guide Words Meaning Remarks
No part of the intentions is
the completer negation of
No or Not achieved and nothing else
intentions
happens.
These refer to the quantities
More and properties such as flow
quantitative increase or
rates and temperatures, as
decrease
Less well as activities like “heat”
and “react”.
All the design and operating
intentions are achieved
As Well As a qualitative increase
together with some
additional activity.
Only some of the intentions
Part of a qualitative decrease
are achieved; some are not.
This is mostly applicable to
the logical opposite of
Reverse activities. It can also be
intentions
applied to substances.
No part of the original
intention is achieved,
Other Than complete substitution
something quite different
happens.
114
APPENDIX F
Process Equipment Design
DESIGNED BY DRAWING NO.

Balbino, GIB CHE 522-V1-0001
Cañete, JC
TITLE
Calambro, N
Cosca, AM PROBE CELL
Dellosa, VM
MATERIAL OF CONSTRUCTION
Sanchez, MS
Santos, JV STAINLESS STEEL
Figure F.1 Drawing for Probe Cell
115
Cañete, JC
TITLE
Calambro, N
Cosca, AM SONICATION CONTROLLER
Dellosa, VM
Sanchez, MS
Figure F.2 Drawing for Sonication Controller
116
Cañete, JC
TITLE
Calambro, N
Cosca, AM SONICATION ENCLOSURE
Dellosa, VM
Sanchez, MS
Figure F.3 Drawing for Sonication Enclosure
117
Cañete, JC
TITLE
Calambro, N
Cosca, AM SONICATION VESSEL
Dellosa, VM
Sanchez, MS
Figure F.4 Drawing for Sonication Vessel
118
Cañete, JC
TITLE
Calambro, N
Cosca, AM MIXING TANK
Dellosa, VM
Sanchez, MS
Figure F.5 Drawing for Mixing Tank
119
Cañete, JC
TITLE
Calambro, N
Cosca, AM HEATING TANK (a)
Dellosa, VM
Sanchez, MS
Figure F.6 Drawing for Heating Tank (Exterior)
120
Cañete, JC
TITLE
Calambro, N
Cosca, AM HEATING TANK (b)
Dellosa, VM
Sanchez, MS
Figure F.7 Drawing for Heating Tank (Interior)
121
Cañete, JC
TITLE
Calambro, N
Cosca, AM TUNNEL DRYER (a)
Dellosa, VM
Sanchez, MS
Figure F.8 Drawing for Tunnel Dryer (Exterior)
122
Cañete, JC
TITLE
Calambro, N
Cosca, AM TUNNEL DRYER (b)
Dellosa, VM
Sanchez, MS
Figure F.9 Drawing for Tunnel Dryer (Interior)
123

Cañete, JC TITLE
Calambro, N
Cosca, AM
ROTARY VACUUM DRUM
Dellosa, VM FILTER (a)
Sanchez, MS MATERIAL OF CONSTRUCTION
Santos, JV
STAINLESS STEEL
Figure F.10 Drawing for Rotary Vacuum-Dum Filter (Exterior)
124

Cañete, JC TITLE
Calambro, N
Cosca, AM
ROTARY VACUUM DRUM
Dellosa, VM FILTER (a)
Sanchez, MS MATERIAL OF CONSTRUCTION
Santos, JV
STAINLESS STEEL
Figure F.11 Drawing for Rotary Vacuum-Dum Filter (Interior)
125
Cañete, JC
TITLE
Calambro, N
Cosca, AM BALL MILL (a)
Dellosa, VM
Sanchez, MS
Figure F.12 Drawing for Ball Mill (Exterior)
126
Cañete, JC
TITLE
Calambro, N
Cosca, AM BALL MILL (b)
Dellosa, VM
Sanchez, MS
Figure F.13 Drawing for Ball Mill (Interior)
127
APPENDIX G
Figure G.1 First Floor Plan for the Administration Building
128
Figure G.2 Second Floor Plan for the Administration Building
129
130

02 - 21 - 2018 - ChE Plant Design - Synthetic Zeolite From Coal Fly Ash (CFA)

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02 - 21 - 2018 - ChE Plant Design - Synthetic Zeolite From Coal Fly Ash (CFA)

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CHAPTER 1:

Table 2.1 Selection of Method for Synthesis of Zeolites

Table 2.4 Summary

3.1 Description of the Design

The sonochemical treatment involves exposure to high intensity ultrasonic waves

3.2 Description of the Process

The adjusted filtrate is then subjected to a static hydrothermal treatment in an

NaOH Solid Waste Recovered

3.3.2 Plant Location and Layout

The zeolite plant is to be built along the Naga-Uling Road, which is a

A steel fence is to be built around the property. The main material of

The plant building is classified as type V, as defined in the building code of

The occupancy classification of the plant building is group G – division 1,

Table 3.1 Battery Limits

 the component mass and energy  materials recovery facility design

 plant layout and design  organizational structure of the

 mass and energy balances

The outlook remains positive despite a mature detergents market in Europe

4.1 Physical and Chemical Properties of Pure Substances

Table 4.1 Physical Properties of Pure Substances

Sodium Solid White Odor 81.969 1.5 1650

Table 4.3 Composition of Zeolite A

Table 4.4 Solubility of Substances

Insoluble Insoluble Soluble in diluted

Insoluble Insoluble Soluble in acids

Sodium Oxide Reacts violently to Reacts violently to Reacts with

Reacts to give Reacts to give -

Manganese(II) Insoluble Insoluble Soluble in acid

Table 4.5 Heat Capacity of Coal Fly Ash Components

Chemical Heat Capacity at constant pressure Range of

Aluminum Oxide Al2O3 crystal 22.08 + 0.008971T - 522500/T2 273-1973 3

c, quartz, α (10.87 + 0.008712T - 241200/T2 ) 273-848 1

c, quartz, β (10.95 + 0.00550T) 848-1873 3.5

Saturation Properties for Steam - Temperature Table (0.01°C - 150°C)

Table 4.7 Thermodynamic Properties of Water

Volume Energy Enthalpy Entropy

°C MPa vf vg uf ug hf hfg hg sf sfg sg

Process Structure and Description

5.1 Criteria and Selection

Table 5.1 Criteria for Equipment Selection

Table 5.2 Comparison of Different Types of Sonication Equipment

Table 5.3 Selection of Sonication Equipment

Table 5.4 Comparison of Different Types of Filtration Equipment

Table 5.5 Selection of Filtration Equipment

Table 5.6 Comparison of Equipment for Hydrothermal Treatment

Table 5.7 Selection of Equipment for Hydrothermal Treatment

Table 5.8 Comparison of Different Types of Dryer

Table 5.9 Selection of Dryer

Table 5.10 Comparison of Different Types of Crushing Equipment

Table 5.11 Selection of Sonication Equipment

Heat and Mass Balances

Table 6.1 Summary of Heat and Mass Balances

Process and Equipment Design

7.1 Sonication Equipment

Table 7.1 Specifications for Ultrasonic Probe Cell Sonicator

Table 7.2 Specifications for Rotary Vacuum-Drum Filter

Table 7.3 Specifications for Heating Tank

Table 7.4 Specifications for Heating Tank

Table 7.5 Specifications for Tunnel Dryer

7.6 Crushing Equipment

Table 7.6 Specifications for Ball Mill

A feedback control system is utilized in the equipment design. A combination of feedback

Figure 8.1 Block Diagram of the Parallel Form of PID Control