Process Selection (232-305) PDF

Technological Institute of the Philippines
PROCESS
SELECTION
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INTRODUCTION
Calcium chloride is an inorganic compound,

a salt with the chemical formula CaCl2. It is a
colorless crystalline solid at room temperature,
highly soluble in water. The ability of CaCl 2 to
attract water – because it is a hygroscopic material –
makes it a highly effective dust suppressant when
applied to the surface of gravel roads. It is also an
effective stabilizing agent in gravel road bases and
in mixtures of road base gravel and pulverized Figure 6.1.1: Calcium chloride powder as
typically placed on the market (Wikipedia)
asphalt created during the full-depth reclamation
process. In these applications, calcium chloride also attracts moisture from the air (and
retained moisture applied during construction and maintenance operations) to bind fine
and coarse gravel particles together, preventing road degradation. The hygroscopic
properties of calcium chloride, as well as the material’s deliquescent and exothermic
properties, are highly beneficial for quickly melting ice on sidewalks and steps. Ice
melter speed of action is determined by how easily the deicing agent dissolves when
exposed to snow or ice to form a brine solution. The brine lowers the freezing point of
water to melt additional snow and ice on contact.
By attracting moisture from its surroundings, CaCl 2 speeds up the creation of
brine compared to rock salt and other ice melt materials. Also contributing to the rapid
formation of brine is calcium chloride’s deliquescence – the material’s tendency to
dissolve by absorbing moisture from the air under very cold conditions when the surface
of ice is relatively dry. Finally calcium chloride releases considerable heat when
dissolved in water. This exothermic reaction contributes to faster ice melting at colder
temperatures than rock salt and other products which must draw heat from their
surroundings to dissolve and form brine.
Similarly, liquid calcium chloride is applied to pre-wet rock salt and abrasive
materials used to keep highways safe and open for traffic during and after winter storms.
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Prewetting rock salt with calcium chloride provides salt with the moisture it needs to
form liquid brine and initiate melting, particularly when temperatures drop below the
effective working range of straight rock salt. The beneficial properties of calcium
chloride are also used to improve a wide range of other products and processes including
oil and gas exploration and production, food processing, production of concrete, and
formulation of animal feeds.
Calcium chloride is produced in commercial quantities by several processes: (1)
the reaction of hydrochloric acid with calcium carbonate, (2) the reaction of calcium
hydroxide with ammonium chloride in Solvay (synthetic) soda ash production, and (3)
refining of natural brines. To choose the optimum process to produce Calcium Chloride,
we have considered these criteria: sustainability, economics, manufacturability, safety,
and environmental impact.
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Hydrochloric acid at 33% w/w solution is delivered to the reactor (R-01) to react
with limestone powder (CaCO3, 100 mesh) at 80 ℃ with 99% purity to produce CaCl2,
water and carbon dioxide.
CaCO3 + 2HCl → CaCl2 + CO2 + H2 O
Then the solution leaving the reactor shall be about 40% w/w of calcium chloride,
with a solid dispersed phase of limestone. The slurry is fed to a hydrocyclone (H-01)
where the limestone is separated and recycled to the reactor. The high purity carbon
dioxide being produced in the reaction is condensed to separate water vapor from carbon
dioxide. The carbon dioxide is compressed to liquid phase using a CO2 compressor and
stored in a pressurized tank. The liquor of calcium chloride leaving the hydrocyclone is
fed to the neutralization tank (T-06) where the excess hydrochloric acid neutralization
takes place by adding a suspension of 10% lime solution. The neutralization process has a
detention time of 20 minutes in order to completely convert hydrochloric acid to calcium
chloride, and to dissolve soluble solids. The liquor exiting the neutralization tank is
delivered to a clarifier. In this equipment the residual suspended solids, mostly limestone
is settled. The overflow is to be brought to a filter press (F-01) to further remove
limestone particles. After filtration, the filtrate is stored in a buffer tank (T-07) for further
purification by means of evaporation (E-01), concentrating the solution to 55% CaCl 2.
The solution then undergoes drying operation via spray dryer (D-01) yielding 94% w/w
CaCl2 powder. The powder exiting the spray dryer is sent to a vibrating screen to separate
the CaCl2 particles to prepare for packaging.
The 10% w/w lime solution used in neutralization is produced in a lime

generation tank (T-04) by mixing 99% calcium hydroxide powder, and water. The
solution produced is stored in a tank (T-05) and ready for consumption.
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Figure 6.1.2: Process Flow Diagram of Process 1: Production of Calcium Chloride via
Limestone – Hydrochloric Acid Process
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I. SUSTAINABILITY
i. Availability of Raw Materials
The raw materials limestone, hydrochloric acid, calcium hydroxide,
and sodium hydroxide are all locally available in the Philippines.
Some of the companies that produce or supply these materials are:
Table 6.1.1: Suppliers of Raw Materials for Process 1
Raw Materials Suppliers

 Tayabas Lime
Industries
 Apex Mining Co., Inc.
 Benguet Corporationm
 Cmv Lime Industries
Limestone powder Corp.
 Dizon Copper-Silver
Mining Corp.
 Guanzon Lime
Development
Company Inc.
 Rnm Dunamics
Philippines, Inc.
 Emerald Chemicals
Hydrochloric acid
Inc.
 International Chemical
Industries
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 Mabuhay Vinyl Corp
 Panay Mineral
Resource Corp.
 HR Gillamac Mining
and Industrial
Corporation
Calcium Hydroxide powder  H.T Mining Products
Resources Corp.
 Hyper Kem and
Machineries Inc.
 Topline Marketing
Corp.
To have a continuous production of Calcium Chloride via Limestone – Hydrochloric

Acid Process, we have to look at the supply of raw materials for process 1 in the
Philippines. The raw materials should have a stable supply to support the production of
Calcium Chloride.
a. Limestone Supply in the Philippines

The historical demand and supply of limestone from the year 2007 to 2016
is presented below. The supply data were derived from the local production
through quarrying or mining in different locations in the Philippines. The said
data were reported in Philippine production for mineral commodities by United
States Geological Survey. A part of supply consists of the import volume from the
international market which was supplying through distribution or trading
companies. The demand data were derived from the local consumption of
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limestone which is mainly used in cement industry. The exportation volume was
treated as an addition to demand for international market consumption that was
treated as a market driver for local production of limestone. The historical data
sets for cement production in the Philippines were based on the data reported by
the Cement Manufacturers’ Association of the Philippines Inc. (CeMAP). The
estimation of the limestone content percentage (88%) in commercial cement was
based on information acquired from British Geological Survey. The trade data
such us importation and exportation volume were acquired from United Nations
Commodity Trade (UN comtrade) statistics database.
Table 6.1.2: Historical Demand and Supply of Limestone [Philippine

Production for Mineral Commodities by USGS, CeMAP, British Geological
Survey, UNCOMTRADE database]
Year Supply ('000MT) Demand ('000
2007 26419 MT)
12438
2008 31528 12455
2009 33090 13616
2010 35540 14345
2011 42527 14475
2012 53714 17061
2013 73359 18467
2014 77665 19629
2015 78990 21585
2016 80445 18640
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90000
80000
70000
Net Weight ('000 MT)
60000
50000
40000 Supply ('000MT)
30000 Demand ('000 MT)
20000
10000
0
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Year
Figure 6.1.3: Graphical Representation of Supply and Demand of Limestone
b. Calcium Hydroxide Supply in the Philippines

The historical demand and supply of calcium hydroxide from the year
2007 to 2016 is presented below. The supply data were derived from the local
production through manufacturing and mining in different locations in the
Philippines. The said data were reported in Philippine production for mineral
commodities by United States Geological Survey. A part of supply consists of the
import volume from the international market which was supplying through
distribution or trading companies. The demand data were derived from the local
consumption of calcium hydroxide which is mainly used in wastewater/sludge
treatment and as raw material for the production of ammonia. The data used for
deriving demand was presented in an article published by Mogol et. Al.
(Wastewater production in the Philippines) and fertilizer production data was
reported by the Bureau of Agriculture Statistics (BAS). The exportation volume
was treated as an addition demand for international market consumption that was
treated as a market driver for local production of calcium hydroxide. The trade
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data such us importation and exportation volume were acquired from United
Nations Commodity Trade (UN comtrade) statistics database.
Table 6.1.3: Historical Demand and Supply of Calcium Hydroxide [Philippine

Production for Mineral Commodities by USGS, BAS, UNCOMTRADE database]
Year Supply (MT) Demand (MT)

2007 3875 6362
2008 4391 4984
2009 4434 4754
2010 4668 4754
2011 6104 6592
2012 6797 5352
2013 6885 5489
2014 7997 5627
2015 8056 5765
2016 9359 5903
10000
9000
8000
Net Weight (MT)
7000
6000
5000
Supply (MT)
4000
3000 Demand (MT)
2000
1000
0
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Year
Figure 6.1.4: Graphical Representation of Supply and Demand of Calcium

Hydroxide
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c. Supply of Hydrochloric Acid in the Philippines

The historical demand and supply of hydrochloric acid from the year 2007 to
2016 is presented below. The supply data were derived from the local producers or
manufacturers in the Philippines. The said data were estimated from hydrochloric
acid manufacturing companies’ plant capacity and annual sales report that was
presented in the Security and exchange commission (SEC) database. A part of supply
consists of the import volume from the international market which was supplying
through distribution or trading companies. The demand data were derived from the
local consumption of hydrochloric acid which is mainly used in vinyl chloride
manufacturing as a raw material and in steel industry as steel pickling medium. The
consumption data were estimated through analysis of the annual sales report of the
PVC manufacturing companies and estimation of hydrochloric acid usage in the
annual consumption of steel that was reported by Philippine Iron and Steel institute
(PISI), Bureau of Customs (BOC) and Department of Trade and Industry (DTI). The
exportation volume was treated as an addition demand for international market
consumption that was treated as a market driver for local production of hydrochloric
acid. The trade data such us importation and exportation volume were acquired from
United Nations Commodity Trade (UN comtrade) statistics database.
Table 6.1.4: Historical Demand and Supply of Hydrochloric acid [SEC database,
PISI, BOC, DTI, UNCOMTRADE]
2007 35674 24302

2008 33637 26605
2009 22695 22014
2010 32303 28650
2011 21195 30544
2012 25674 26102
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2013 35129 28508

2014 23806 32250
2015 26845 22769
2016 37531 22725
40000
35000
30000
Net Weight (MT)
25000
20000
Supply (MT)
15000 Demand (MT)
10000
5000
0
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Year
Figure 6.1.5: Graphical Representation of Supply and Demand of

Hydrochloric Acid
II. ECONOMICS:
Exchange Rate: 1 USD = Php 50.5837
i. Equipment Cost:
Equipment fixed capital cost that is needed to put up a plant that produces
Calcium Chloride via Limestone – Hydrochloric Acid Process is calculated using the
Lang Method from Perry’s Chemical Engineers’ Handbook 8th ed. These Lang
factors depend on the type of processing per equipment. Solid processing factor is
applied to equipment which only processes solids such as crushers, ball mills,
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screener, etc. Solid-fluid processing factor is applied to equipment which processes

solids and fluids such as solid-liquid separation equipment – examples are leaching
equipment, filters, sedimentation equipment, etc. Fluid processing factor is for
equipment which only processes fluids such as distillation columns, absorption
column, etc. These factors are multiplied in equipment costs resulting to Equipment
Fixed Capital Cost.
Table 6.1.5: Lang Factors (Green & Perry, 2008)
Lang Factors
Type of Plant
Fixed capital investment Total capital investment
Solid processing 4.0 4.7
Solid-fluid processing 4.3 5.0
Fluid processing 5.0 6.0
Adapted from M. S. Peters, K. D. Timmerhaus, and R. West, Plant Design and Economics for
Chemical Engineers, 5th ed., McGraw-Hill, New York, 2004.
Table 6.1.6: Equipment Cost for Process 1 (www.alibaba.com)
Equipment Qty. Equipment Cost Fixed Capital Cost

HCl Surge Tank 1 $ 6,000.00 $ 6,000.00
Reactor 1 $ 30,000.00 $ 30,000.00
Hydrocyclone 1 $ 5,500.00 $ 5,500.00
Holding Tank 1 $ 2,000.00 $ 2,000.00
Neutralization Tank 1 $ 5,000.00 $ 5,000.00
Lime Generation Tank 1 $ 5,000.00 $ 5,000.00
Lime Solution Storage Tank 1 $ 1,000.00 $ 1,000.00
Clarifier 1 $ 2,500.00 $ 2,500.00
Filter Press 1 $ 3,000.00 $ 3,000.00
Buffer Tank 1 $ 1,000.00 $ 1,000.00
Evaporator 1 $ 20,000.00 $ 20,000.00
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Spray Dryer 1 $ 10,000.00 $ 10,000.00

Vibrating Screen 1 $ 8,000.00 $ 8,000.00
Total Number of Equipment 13
Total Purchase Cost of USD $101,000.00 $434,300.00
Equipment
PHP ₱5,108,953.70 ₱21,968,500.91
(PCE)
ii. Project Cost

Project fixed capital cost that is needed to put up a plant that produces Calcium Chloride
via Limestone – Hydrochloric Acid Process is calculated using Table 1.7 from Chemical
Engineering Design: Chemical Engineering, Volume 6. These factors depend on the type
of processing that is involved in your whole process. Fluid Process Type factors are
applied to a process which involves fluid processing only. Fluids-Solids Process Type
factors are applied to a process which involves both solid and fluid processing. Solids
Process Type factors are applied to a process which involves solid processing only.
Table 6.1.7: Estimation of Project Fixed Capital Cost (Sinnot, 2005)
Typical Factors for Estimation of Project Fixed Capital Cost

Process Type
Item
Fluids Fluids-solids Solids
1. Major equipment, total purchase cost PCE PCE PCE
ƒ1 Equipment erection 0.4 0.45 0.50
ƒ2 Piping 0.70 0.45 0.20
ƒ3 Instrumentation 0.20 0.15 0.10
ƒ4 Electrical 0.10 0.10 0.10
ƒ5 Building, process 0.15 0.10 0.05
*ƒ6 Utilities 0.50 0.45 0.25
*ƒ7 Storages 0.15 0.20 0.25
*ƒ8 Site development 0.05 0.05 0.05
*ƒ9 Ancillary building 0.15 0.20 0.30
2. Total physical plant cost (PPC)
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𝐏𝐏𝐂 = 𝐏𝐂𝐄(𝟏 + ƒ𝟏 + ⋯ + ƒ𝟗 )
= 𝐏𝐂𝐄 𝐱 3.40 3.15 2.80
ƒ10 Design and Engineering 0.30 0.25 0.20
ƒ11 Contractor’s fee 0.05 0.05 0.05
ƒ12 Contingency 0.10 0.10 0.10
𝐅𝐢𝐱𝐞𝐝 𝐜𝐚𝐩𝐢𝐭𝐚𝐥 = 𝐏𝐏𝐂 (𝟏(𝟏 + ƒ𝟏𝟎 + ƒ𝟏𝟏 + ƒ𝟏𝟐 )

= 𝐏𝐂𝐄 𝐱 1.45 1.40 1.35
*Omitted for minor extensions or additions to existing sites
TOTAL PHYSICAL PLANT COST ₱63,708,652.64

(PPC)COST (FCC)
FIXED CAPITAL ₱89,192,113.69
WORKING CAPITAL COST ₱4,459,605.68
TOTAL CAPITAL INVESTMENT ₱93,651,719.38
TOTAL PHYSICAL PLANT COST (PPC):
PPC = PCE(1 + f1 + f2 + f3 + f4 + f5 + f6 + f7 )
PPC = ₱21,968,500.91 (1 + 0.45 + 0.45 + 0.15 + 0.1 + 0.1 + 0.45 + 0.2)
PPC = ₱63,708,652.64
FIXED CAPITAL COST:
FCC = PCC(1 + f10 + f11 + f12 )
FCC = ₱63,708,652.64 (1.40)
FCC = ₱89,192,113.69
WORKING CAPITAL COST (WCC):

WCC = FCC(0.05)
WCC = ₱89,192,113.69 (0.05)
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WCC = ₱4,459,605.68
TOTAL CAPITAL INVESTMENT (TCI):

TCI = FCC + WCC
TCI = ₱89,192,113.69 + ₱4,459,605.68
TCI = ₱93,651,719.38
Total capital investment refers to a plant’s acquisition of capital assets or fixed
assets such as machinery that is expected to be productive over many years.
iii. Production Cost

An estimate of the operating costs, the cost of producing the product, is
needed to judge the viability of a project, and to make choices between possible
alternative processing schemes. These costs can be estimated using Figure 1.5
from Chemical Engineering Design Volume 6. Fixed operating cost is the costs
that do not vary with production rate. These are the bills that have to be paid
whatever the quantity produced. While variable costs are dependent on the
amount of product produced.
Figure 6.1.6: Costing and Project Evaluation (Coulson and Richardson)
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FIXED COSTS
Maintenance and Repairs ₱8,919,211.37
Operating Labor ₱8,919,211.37
Laboratory Cost ₱2,051,418.61
Supervision ₱1,783,842.27
Plant Overheads ₱4,459,605.68
Capital Charges ₱8,919,211.37
Local Taxes ₱1,783,842.27
Insurance ₱891,921.14
Royalties ₱891,921.14
TOTAL FIXED COST ₱38,620,185.23
FIXED COST:
Maintenance and Repairs(MR) = Average process = 5 − 10% of fixed capital
MR = ₱89,192,113.69 (0.10) = ₱8,919,211.37
Operating Labor(OL) = 5 − 10% of fixed capital
OL = ₱89,192,113.69 (0.10) = ₱8,919,211.37
Laboratory Cost(LC) = 20 − 23% operating Labor
= ₱8,919,211.37 (0.23)
= ₱2,051,418.61
Supervision(S) = 20% operating Labor

= ₱8,919,211.37 (0.20)
= ₱1,783,842.27
Plant Overheads(PO) = 50% operating Labor
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= ₱8,919,211.37 (0.50)
= ₱4,459,605.68
Capital Charges (CC) = FCC(0.1)
= ₱89,192,113.69 (0.1)
= ₱8,919,211.37
Insurance(I) = FCC(0.01)
= ₱89,192,113.69 (0.01)
= ₱891,921.14
Local Taxes (LT) = FCC(0.02)
= ₱89,192,113.69 (0.02)
= ₱1,783,842.27
Royalties (R) = FCC(0.01)
= ₱89,192,113.69 (0.01)
= ₱891,921.14
FIXED COST = MR + OL + LC + ES + PO + CC + I + LT + R
𝐅𝐈𝐗𝐄𝐃 𝐂𝐎𝐒𝐓 = ₱𝟑𝟖, 𝟔𝟐𝟎, 𝟏𝟖𝟓. 𝟐𝟑
VARIABLE COSTS
Raw Materials ₱81,186,838.50
Miscellaneous Materials ₱891,921.14
Utilities (Services) ₱2,043,581.48
TOTAL VARIABLE ₱84,122,341.12
COSTS
VARIABLE COST:
The operating time is used to calculate the cost of raw materials in a year.
HRS/YR 7,200
OPERATING TIME, PLANT ATTAINMENT
DAYS/YR 300
250
Raw Material Cost:
Table 6.1.8: Raw Material Cost for Process 1 (www.alibaba.com)
Raw Material Cost

Limestone powder (99.5% 120 USD/Metric ton ₱6,070.04 / Metric ton
purity)
33% w/w Hydrochloric acid 200 USD/ Metric ton ₱10,116.74 / Metric ton
Calcium Hydroxide powder 215 USD/ Metric ton ₱10,875.50 / Metric ton
tons ₱10,116.74 tons

Raw Materials = 10 (300 days) ( ) + 10 (300 days)
day ton day
₱10,875.50 tons ₱6,070.04
( ) + 10 (300 days) ( )
ton day ton
= ₱81,186,838.50
Miscellaneous Materials = 10% Maintenance
= ₱8,919,211.37 (0.10)
= ₱891,921.14
Utilities:
Service facilities include such as utilities for supplying steam, water, power, compressed
air, and fuel in an industrial plant. Waste disposal, fire protection, and miscellaneous
service items also are included under the general heading of service facilities cost. The
total cost for service facilities in chemical plants may be determined as amounts
equivalent to percentages of the purchased equipment cost
Average services = 40%(Equipment Cost)
= ₱5,108,953.70 (0.40)
= ₱2,043,581.48
VARIABLE COST = Raw Material + Miscellaneous Materials + Utilities
𝐕𝐀𝐑𝐈𝐀𝐁𝐋𝐄 𝐂𝐎𝐒𝐓 = ₱𝟖𝟒, 𝟏𝟐𝟐, 𝟑𝟒𝟏. 𝟏𝟐
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Direct Production Cost ₱122,742,526.35

Sales Expense ₱24,548,505.27
General Overheads ₱36,822,757.90
TOTAL DIRECT COST ₱184,113,789.52
𝐀𝐧𝐧𝐮𝐚𝐥 𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐢𝐨𝐧 𝐂𝐨𝐬𝐭 = 𝐅𝐂 + 𝐕𝐂 + 𝐃𝐏𝐂 ₱306,856,315.87
Direct Production Cost (DPC) = FC + VC = ₱122,742,526.35
Sales Expense = (DPC)(0.2) = ₱24,548,505.27
General Overheads = (DPC)(0.3) = ₱36,822,757.90
Sub − total DPC = DPC + Sales Expense + General Overheads
= ₱122,742,526.35 + ₱24,548,505.27 + ₱36,822,757.90
𝐒𝐮𝐛 − 𝐭𝐨𝐭𝐚𝐥 𝐃𝐏𝐂 = ₱𝟐𝟐𝟖, 𝟐𝟒𝟎, 𝟗𝟗𝟐. 𝟕𝟎
Annual Production Cost = FC + VC + DPC
𝐀𝐧𝐧𝐮𝐚𝐥 𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐢𝐨𝐧 𝐂𝐨𝐬𝐭 = ₱𝟑𝟎𝟔, 𝟖𝟓𝟔, 𝟑𝟏𝟓. 𝟖𝟕
III. MANUFACTURABILITY:
For the continuous production of calcium chloride, limestone and hydrochloric acid are
reacted in a continuous stirred tank reactor. Upon reacting, it will produce a slurry of
calcium chloride, limestone, and water. It will also produce carbon dioxide. The slurry is
fed to a hydrocyclone to separate the calcium chloride solution from limestone particles
which will be recycled back to the reactor. The calcium chloride solution is fed to the
neutralization tank and pH is adjusted by adding lime solution with continuous stirring.
Upon clarification, the solution undergoes press filtration to remove remaining limestone
particles. The effluent from filter press is then transferred to a buffer tank before it is fed
to a triple-effect evaporator to concentrate the solution to 55% w/w. After evaporation,
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the concentrated calcium chloride solution undergoes spray drying to produce 94% w/w
calcium chloride granules. The calcium chloride powder produces by the spray dryer will
be screened using a vibrating sieve tray. The energy requirement in this process is not
high; therefore, this process is energy efficient and the process does not require any
specialized and complicated equipment. The list of equipment shown in the table below
shows the list of major equipment that are required to run the plant and most of them
does not require high maintenance and are easy to operate. The phases involved in each
equipment are quantified from single phase (1) to triple phase (3). The average number of
phases indicates the complexity of the equipment and the average phases involved in the
process is calculated to reflect the complexity of the entire process in terms of equipment
operations, an average of 1 being the lowest difficulty in processing to 3 indicating the
highest difficulty in processing.
Table 6.1.9: Average phases involved in Process 1
Equipment Tag Equipment Phases Involved

Name
HCl Surge Tank T-01 1
CaCO3 Silo T-02 1
Holding Tank T-03 2
Lime Generation T-04 2

Tank
Lime Storage Tank T-05 1
Neutralization Tank T-06 1
Buffer Tank T-07 1
CSTR R-01 3
Vibrating Screen S-01 1
Hydrocyclone H-01 2
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Spray Dryer D-01 2
Evaporator E-01 2
Clarifier C-01 2
Filter Press F-01 2
Total Phases/Number of Equipment 1.6
IV. SAFETY
i. Toxicity of Raw Materials

Toxicity level of raw materials is analyzed, which may be seen in the table
below, based on the corresponding health hazards that it may cause to
humans. Basis for attaining the level of toxicity was in the following table,
which explains in detail the health hazards of the raw materials from the
information in the table. Health hazard rating was made taking 0 - for minimal
hazard and no significant risk to health,1- slight hazard or minor reversible
injury possible, 2 - moderate hazard temporary or minor injury may occur, 3 -
serious hazard major injury likely unless prompt action is taken and medical
treatment given, 4 - severe hazard, life-threatening, major of permanent
damage may result from single or repeated exposures.
Table 6.1.10: Toxicity Level Scores of Raw Materials in Process 1

Raw Materials
Measure 30% w/w Limestone Calcium

Hydrochloric Powder (99.5% Hydroxide
Acid purity) Powder
Severity of 2 1 2
Immediate Effects
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Sensitization Level 2 0 2
Carcinogenicity 0 0 0
Level
Reproduce Toxicity 0 0 0
Level
Severity of Chronic 3 3 3
Effects
Subtotal 7 4 7
Total 18
Table 6.1.11: Basis of Toxicity Level Scores in Process 1

Raw Materials
Criteria 30% w/w Limestone Powder Calcium Hydroxide
Hydrochloric Acid (99.5% purity) Powder
Hazardous in case
Very hazardous in of eye contact.
case of skin Slightly hazardous
Severity of Corrosive to eyes
contact, of eye in case of skin
Immediate Effects and skin.
contact, of contact, of
ingestion ingestion, of
inhalation
Sensitization Level Slightly hazardous Not classified Hazardous
Carcinogenicity
Classified 3 Not classified Not classified
Level
Reproduce Toxicity
Not classified Not classified Not classified
Level
May produce Can produce eye
Severity of Chronic The substance may
general irritation, local skin
Effects be toxic to kidneys.
deterioration of destruction (or
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health by an dermatitis), and

accumulation in varying degree of
one or many human respiratory
organs. irritation or lung
damage.
V. ENVIRONMENTAL IMPACT:
In the reaction of limestone and hydrochloric acid, carbon dioxide is
produced. This gas cannot be vented directly to the atmosphere due to regulations
of carbon dioxide emission. This gas will be treated in a packed column absorber
with sodium hydroxide solution as the contacting fluid to reduce the carbon
dioxide concentration in the exiting gas. Limestone is not a known health hazard.
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257
The Solvay Process also known as the ammonia-soda process, developed in 1861, is
the world's major industrial process for the production of sodium carbonate (NaCO3),
or soda ash. The steps in the Solvay Process are:
i. Brine Purification
ii. Limestone Burning and Lime Slaking
iii. Ammonia Absorption
iv. Sodium Hydrogen Carbonate Formation
v. Sodium Carbonate Formation
vi. Ammonia Recovery
The overall reaction can be regarded as between calcium carbonate and sodium chloride
(3):
Brine from seawater is purified to remove magnesium, calcium and iron ions. To remove
calcium sulfate, magnesium and iron salts sodium carbonate and sodium hydroxide are
added. It is concentrated by evaporation to at least 30%. Impurities such as calcium,
magnesium and iron are collected as precipitants by this reaction:
Ca2+(aq) + CO32-(aq) → CaCO3(s)
Mg2+(aq) + 2OH-(aq) → Mg(OH)2(s)
Fe3+(aq) + 3OH-(aq) → Fe(OH)3(s)
Following the precipitation reaction brine solution is then filtered and passed through an
ammonia tower to dissolve ammonia. Kilns are fed with a limestone/coke mixture with a
ratio of 13:1 by mass. The heat of combustion raises the temperature of the kiln and the
limestone decomposes:
From it, both carbon dioxide for the carbonation stage and calcium oxide for the
distillative recovery of ammonia are produced by calcination with coke. The consumption
258
of 95% pure limestone varies between 1100-1200 kg/ 1000 kg sodium carbonate. The
best calcination temperature for the burning of limestone and coke lies between 1050-
1100℃. The gas CO2 contents of 40-42 vol% can be obtained. The hot, dust- laden gas is
cooled and washed direct contact with water. It then passes to the CO 2 compressor from
which it is delivered to the carbonation (Solvay Tower) stage.
In the absorption stage, ammonia together with the recycle gas from distillation that
contains ammonia and carbon dioxide is absorbed by purified brine. The ammoniacal
brine obtained contains 85- 90 kg/m3 NH3 and 40-50 kg/m3 CO2. The NaCl content is
reduced from 300 g/L to 260 g/L due to the increase in the specific volume of the liquor
caused by the addition of ammonia and by dilution with water.
The ammoniated brine from the ammonia tower is passed down through the Solvay
Tower while carbon dioxide from the lime kiln and from calcination stage passed up it.
The Solvay Tower is tall and contains a set of mushroom-shaped baffles to slow down
and break up the liquid flow so that the carbon dioxide can be efficiently absorbed by the
solution. Carbon dioxide, on dissolving, reacts with the dissolved ammonia to form
ammonium hydrogencarbonate:
The solution now contains ions Na+ (aq), Cl- (aq), NH4+ (aq) and HCO3- (aq). Of the four
substances which could be formed by the different combinations of these ions, sodium
hydrogencarbonate (NaHCO3) is the least soluble. It precipitates as a solid in the lower
part of the tower.
The suspension of bicarbonate in mother liquor leaves the carbonation stage at 30℃.
Bicarbonate is generally separated from the mother liquor in continuous rotary drum
filter. Crude bicarbonate has the following approximate composition: 75.6% NaHCO 3;
6.9% Na2CO3; 3.4% NH4HCO3; 0.4% NaCl + NH4Cl; 13.7% H2O. Calcination of 1 ton
of crude bicarbonate yield 520- 560 kg of soda ash. The sodium bicarbonate is heated in
259
rotating calciner at 160 - 230℃ so that it decomposes to sodium carbonate, water and
carbon dioxide:
These are heated either externally with oil, gas, or coal or internally with steam, which
passes through heating tubes in the calciner countercurrent to the flow of solid material.
Gases extracted from the calciners contain CO2, NH3, H2O and some leakage air. Before
this gas is used in the carbonation stage, it is cooled and washed with brine and water
until it’s free of ammonia. The condensate produced at this point is fed to the ammonia
recovery stage. In this thermal decomposition, a sodium carbonate- sodium bicarbonate,
which limits the yield to 85- 88%. The product of the process, anhydrous sodium
carbonate, is obtained as a fine white powder known as light sodium carbonate.
The last two stages, are concerned with the regeneration of ammonia from ammonium
chloride. The quicklime is slaked with excess water giving milk of lime:
Quicklime (CaO) from the kiln is reacted with cooling water which has a temperature of
50- 65℃ in a horizontal rotating drum to produce a suspension of Ca(OH) 2 in water. The
CaO content of the milk of lime can reach 5.5 mol/L. Before milk of lime is used in the
distillative recovery of ammonia, coarse sand and unburnt limestone are removed by
sieves, mixed with new limestone and recycled to the kiln. In the distillation column the
ammonia content of the liquor is lowered to 0.5 kg/ ton of sodium carbonate by steam
treatment. Distillation gas, which contains NH3 and CO2 is cooled to 55- 60℃.
The ammonia is thus recovered, and recycled in the ammonia absorber. Calcium chloride
is the only by-product of the whole process.
In the recovery of ammonia by distillation with milk of lime, an end liquor is produced at
boiling point. This liquor has the following approximate composition: 120-180g/L CaCl2,
1.0-1.7g/L Ca(OH)2, 50-75g/L NaCl, 1.0-1.5g/L CaSO4 and 20-30g/L suspended solids.
260
Figure 6.2.1 Process Flow Diagram of Process 2: Production of Calcium Chloride via Solvay Process
261
I. SUSTAINABILITY
The raw materials limestone, hydrochloric acid, calcium hydroxide,
and sodium hydroxide are all locally available in the Philippines.
Some of the companies that produce or supply these materials are:
Table 6.2.1: Companies that produces or supplies raw materials for Process 2
Coke  Alfa Laval Philippines,

Limestone  Inc.
Tayabas Lime Industries
 Apex Mining Co., Inc.
 Benguet Corporationm
 Cmv Lime Industries Corp
 Dizon Copper-Silver
Mining Corp.
 Guanzon Lime
Development Company
Inc.
Ammonia Gas  Air Liquide Philippines
 Pems Technology Inc.
 The Linde Group
 Marubeni Philippines,
Corp.
262
NaOH  Neco Philippines, Inc.
To have a continuous production of Calcium Chloride via Solvay Process, we

have to look at the supply of raw materials for process 2 in the Philippines. The raw
materials should have a stable supply to support the production of Calcium Chloride.
a. Limestone Supply in the Philippines

The historical demand and supply of limestone from the year 2007 to 2016
through quarrying or mining in different locations in the Philippines. The said
data were reported in Philippine production for mineral commodities by United
States Geological Survey. A part of supply consists of the import volume from the
companies. The demand data were derived from the local consumption of
limestone which is mainly used in cement industry. The exportation volume was
treated as an addition to demand for international market consumption that was
treated as a market driver for local production of limestone. The historical data
sets for cement production in the Philippines were based on the data reported by
the Cement Manufacturers’ Association of the Philippines Inc. (CeMAP). The
estimation of the limestone content percentage (88%) in commercial cement was
based on information acquired from British Geological Survey. The trade data
such us importation and exportation volume were acquired from United Nations
Commodity Trade (UN comtrade) statistics database.
Table 6.2.2: Historical Demand and Supply of Limestone [Philippine

Production for Mineral Commodities by USGS, CeMAP, British Geological
Survey, UNCOMTRADE database]
Year Supply ('000MT) Demand ('000

2007 26419 MT)
12438
263
2008 31528 12455

2009 33090 13616
2010 35540 14345
2011 42527 14475
2012 53714 17061
2013 73359 18467
2014 77665 19629
2015 78990 21585
2016 80445 18640
90000
80000
70000
60000
50000
40000 Supply ('000MT)
30000 Demand ('000 MT)
20000
10000
0
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Year
Figure 6.2.2: Graphical Representation of Supply and Demand of

Limestone
a. Ammonia Supply in the Philippines

The historical demand and supply of ammonia from the year 2007 to 2016
264
through chemical manufacturing in the form of fertilizer and in industrial

grade form (gas, anhydrous or in liquid solution). The said data were reported
by the Bureau of Agriculture Statistics (BAS). A part of supply consists of the
import volume from the international market which was supplying through
distribution or trading companies. The demand data were derived from the
local consumption of ammonia which is mainly used in nitrogen oxide
effluent treatment in power generation plants and as fertilizer for a wide range
of different crops. The data used for deriving demand was presented in Food
and Agriculture Organization (FAO) statistics database for fertilizer
consumption data and the coal consumption data was acquired from the
Department of Energy (DOE) coal statistics. The exportation volume was
treated as an addition demand for international market consumption or
demand that was treated as a market driver for local production of ammonia.
The trade data such us importation and exportation volume were acquired
from United Nations Commodity Trade (UN comtrade) statistics database.
Table 6.2.3: Historical Demand and Supply of Ammonia [BAS, FAO-Stat, DOE,
UNCOMTRADE database]
Year Supply ('000 MT) Demand ('000

2007 284 MT)
107
2008 148 84
2009 198 86
2010 209 125
2011 314 103
2012 190 105
2013 215 110
2014 110 116
2015 123 121
2016 133 127
265
350
300
250
200
150 Supply ('000 MT)

Demand ('000 MT)
100
50
0
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Year
Figure 6.2.3: Graphical Representation of Supply and Demand of Ammonia
II. ECONOMICS:
i. Equipment Cost:
Lang Factors
Type of Plant
Calcium Chloride via Solvay Process is calculated using the Lang Method from Perry’s
266
Chemical Engineers’ Handbook 8th ed. These Lang factors depend on the type of
processing per equipment. Solid processing factor is applied to equipment which only
processes solids such as crushers, ball mills, screener, etc. Solid-fluid processing factor
is applied to equipment which processes solids and fluids such as solid-liquid separation
equipment – examples are leaching equipment, filters, sedimentation equipment, etc.
Fluid processing factor is for equipment which only processes fluids such as distillation
columns, absorption column, etc. These factors are multiplied in equipment costs
resulting to Equipment Fixed Capital Cost.
Equipment Qty. Equipment Cost Fixed Capital

Ammonia Gas Storage Tank 1 $10,000.00 Cost
$43,000.00
Sodium Carbonate Storage 1 $2,500.00 $10,750.00
Tank Chloride
Aqueous Calcium 1 $4,450.00 $19,135.00
Storage
Brine Tank
Evaporator 1 $20,000.00 $86,000.00
Settling Filter 1 $12,000.00 $103,200.00
Absorption Tower 1 $19,000.00 $81,700.00
Solvay Tower 1 $32,500.00 $139,750.00
Screen 1 $3,000.00 $182,747.85
Lime Kiln 1 $50,500.00 $217,150.00
Lime Slaker 1 $8,600.00 $49,450.00
Rotary Calciner 1 $38,000.00 $163,400.00
Gas Scrubber 4 $80,000.00 $344,000.00
Cooler 2 $40,000.00 $172,000.00
Rotary Drum Filter 1 $13,695.65 $58,891.30
Compressor 1 $10,400.00 $44,720.00
Flash Vessel 1 $35,000.00 $150,500.00
Distillation Column 1 $69,000.00 $296,700.00
Total Number of 21
Equipment
267
Total Purchase Cost of USD $448,645.65 $1,929,176.30

Equipment
PHP ₱ 22,694,156.97 ₱ 97,584,874.95
(PCE)
ii. Project Cost

Project fixed capital cost that is needed to put up a plant that produces
Calcium Chloride via Solvay Process is calculated using Table 2.6 from Chemical
Engineering Design: Chemical Engineering, Volume 6. These factors depend on
the type of processing that is involved in your whole process. Fluid Process Type
factors are applied to a process which involves fluids processing only. Fluids-
Solids Process Type factors are applied to a process which involves both solids
and fluids processing. Solids Process Type factors are applied to a process which
involves solids processing only.
Table 6.2.6: Estimation of Fixed Capital Cost (Sinnot, 2005)
Table 4. Typical Factors for Estimation of Project Fixed Capital Cost

Process Type
Item
1. Major equipment, total purchase cost PCE PCE PCE
ƒ2 Piping 0.70 0.45 0.20
ƒ4 Electrical 0.10 0.10 0.10
*ƒ6 Utilities 0.50 0.45 0.25
*ƒ7 Storages 0.15 0.20 0.25
0.30
*ƒ9 Ancillary building 0.15 0.20
2 Total physical plant cost (PPC)

𝐏𝐏𝐂 = 𝐏𝐂𝐄(𝟏 + ƒ𝟏 + ⋯ + ƒ𝟗 )
= 𝐏𝐂𝐄 𝐱 3.40 3.15 2.80
268

= 𝐏𝐂𝐄 𝐱 1.45 1.40 1.35

(PPC)COST (FCC)
FIXED CAPITAL ₱396,194,592.31
TOTAL PHYSICAL PLANT COST (PPC)
PPC = PCE(1 + f1 + f2 + f3 + f4 + f5 + f6 + f7 )
PPC = ₱97,584,874.95 (1 + 0.45 + 0.45 + 0.15 + 0.1 + 0.1 + 0.45 + 0.2)
PPC = ₱282,996,137.36
FIXED CAPITAL COST:
FCC = PCC(1 + f10 + f11 + f12 )
FCC = ₱282,996,137.36 (1.40)
FCC = ₱396,194,592.31

WCC = FCC(0.05)
WCC = ₱396,194,592.31 (0.05)
WCC = ₱19,809,729.62
269

TCI = FCC + WCC
TCI = ₱396,194,592.31 + ₱19,809,729.62
TCI = ₱416,004,321.93
Total capital investment refers to a plant’s acquisition of capital assets or fixed assets
such as machinery that is expected to be productive over many years.

An estimate of the operating costs, the cost of producing the product, is needed to judge
the viability of a project, and to make choices between possible alternative processing
schemes. These costs can be estimated using Figure 2.4 from Chemical Engineering
Design Volume 6. Fixed operating cost is the costs that do not vary with production rate.
These are the bills that have to be paid whatever the quantity produced. While variable
costs are dependent on the amount of product produced.
270
FIXED COSTS
Insurance ₱3,961,945.92
Patent/Royal Fees ₱3,961,945.92
FIXED COST:
Maintenance and Repairs(MR) = Average process = 5 − 10% of fixed capital
MR = ₱396,194,592.31 (0.10) = ₱39,619,459.23
Operating Labor(OL) = 5 − 10% of fixed capital
OL = ₱396,194,592.31 (0.10) = ₱39,619,459.23
Laboratory Cost(LC) = 20 − 23% operating Labor
= ₱39,619,459.23 (0.23)
= ₱9,112,457.62
Supervision(ES) = 20% operating Labor

= ₱39,619,459.23 (0.20)
= ₱7,923,891.85
Plant Overheads(PO) = 50% operating Labor
271
= ₱39,619,459.23(0.50)
= ₱19,809,729.62
Capital Charges (CC) = FCC(0.1)
= ₱396,194,592.31 (0.1)
= ₱39,619,459.23
Insurance(I) = FCC(0.01)
= ₱396,194,592.31 (0.01)
= ₱3,961,945.92
Local Taxes (LT) = FCC(0.02)
= ₱396,194,592.31 (0.02)
= ₱7,923,891.85
Royalties (R) = FCC(0.01)
= ₱396,194,592.31 (0.01)
= ₱3,961,945.92
FIXED COST = MR + OL + LC + ES + PO + CC + I + LT + R
𝐅𝐈𝐗𝐄𝐃 𝐂𝐎𝐒𝐓 = ₱𝟏𝟕𝟏, 𝟓𝟓𝟐, 𝟐𝟓𝟖. 𝟒𝟕
VARIABLE COSTS
Miscellaneous Materials ₱3,961,945.92
TOTAL VARIABLE COSTS ₱318,514,573.01
VARIABLE COST:
The operating time is used to calculate the cost of raw materials in a year.
HRS/YR 7,200
DAYS/YR 300
272
i. Raw Material Cost:

Table 6.2.7: Raw Material Cost for Process 2
Raw Materials Cost

Coke 400 USD/Metric ton ₱ 20,233.48 /Metric
Limestone 510 USD/Metric ton ₱ 25,797.69/Metric
ton ton
Ammonia Gas 920 USD/Metric ton ₱46,537.00/Metric ton
NaOH 570 USD/Metric ton ₱28,832.709/ Metric
ton
tons ₱20,233.48 tons
Raw Materials = 10 (300 days) ( ) + 10 (300 days)
day ton day
₱25,797.69 tons ₱46,537.00
( ) + 10 (300 days) ( )
ton day ton
tons 28832.709
+ 10 (300 days) ( )
day ton
= ₱364,202,640.00
Miscellaneous Materials = 10% Maintenance
= ₱39,619,459.23 (0.10)
= ₱3,961,945.92
Utilities:
Service facilities include such as utilities for supplying steam, water, power, compressed
air, and fuel in an industrial plant. Waste disposal, fire protection, and miscellaneous
service items also are included under the general heading of service facilities cost. The
total cost for service facilities in chemical plants may be determined as amounts
equivalent to percentages of the purchased equipment cost
Average services = 40%(Equipment Cost)

= ₱22,694156.979 (0.40)
= ₱9,077,662.79
273
VARIABLE COST = Raw Material + Miscellaneous Materials + Utilities

𝐕𝐀𝐑𝐈𝐀𝐁𝐋𝐄 𝐂𝐎𝐒𝐓 = ₱𝟑𝟕𝟕, 𝟐𝟒𝟐, 𝟐𝟒𝟖. 𝟕𝟏

𝐀𝐧𝐧𝐮𝐚𝐥 𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐢𝐨𝐧 𝐂𝐨𝐬𝐭 = 𝐅𝐂 + 𝐕𝐂 + 𝐃𝐏𝐂 ₱1,463,036,927.95
Direct Production Cost (DPC) = FC + VC = ₱548,794,507.18
Sales Expense = (DPC)(0.2) = ₱109,758,901.44
General Overheads = (DPC)(0.3) = ₱164,638,352.15
Sub − total DPC = DPC + Sales Expense + General Overheads
= ₱548,794,507.18 + ₱109,758,901.44 + ₱164,638,352.15
𝐒𝐮𝐛 − 𝐭𝐨𝐭𝐚𝐥 𝐃𝐏𝐂 = ₱𝟖𝟐𝟑, 𝟏𝟗𝟏, 𝟕𝟔𝟎. 𝟕𝟕
Annual Production Cost = FC + VC + DPC
𝐀𝐧𝐧𝐮𝐚𝐥 𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐢𝐨𝐧 𝐂𝐨𝐬𝐭 = ₱𝟏, 𝟑𝟕𝟏, 𝟗𝟖𝟔, 𝟐𝟔𝟕. 𝟗𝟓
The principal byproduct of the Solvay process is calcium chloride (CaCl2) in aqueous
solution. The process has other waste and byproducts as well. Not all of the limestone
that is calcined is converted to quicklime and carbon dioxide (in reaction II); the residual
calcium carbonate and other components of the limestone become wastes. In addition, the
salt brine used by the process is usually purified to remove magnesium and calcium ions,
typically to form carbonates; otherwise, these impurities would lead to scale in the
274
various reaction vessels and towers. These carbonates are additional waste products. A
little this can be sold for use in refrigeration, curing concrete and as a suspension in oil
drilling. The energy requirement in this process is not high; therefore, this process is
energy efficient and the process does not require any specialized and complicated
equipment. The list of equipment shown in the table below shows the list of major
equipment that are required to run the plant and most of them does not require high
maintenance and are easy to operate. The phases involved in each equipment are
quantified from single phase (1) to triple phase (3). The average number of phases
indicates the complexity of the equipment and the average phases involved in the process
is calculated to reflect the complexity of the whole process in terms of equipment
Table 6.2.8: Average of phases involved in Process 2
Equipment Tag Equipment Phases Involved

Name
Ammonia Gas ST-01 1
Storage Tank
Sodium Carbonate ST-02 1
Storage Tank
Aqueous Calcium ST-03 1
Chloride Storage
Tank
Brine Evaporator E-01 2
Settling Tower F-01 2
Absorption Tower A-01 2
Solvay Tower CT-01 3
Screen SC-01 1
Lime Kiln K-01 2
275
Lime Slaker SL-01 2

Rotary Calciner CL-01 2
Gas Scrubber S-01 2
Gas Scrubber S-02 2
Gas Scrubber S-03 2
Gas Scrubber S-04 2
Cooler C-01 1
Cooler C-02 1
Rotary Drum Filter F-02 1
Compressor CM-01 1
Flash Vessel FV-01 2
Distillation Column DC-01 3
IV. SAFETY

276

Raw Materials
Sodium
Measure Natural Ammonia
Limestone Coke Hydroxide
Brine Gas
Powder
Severity of
Immediate 1 1 4 1 3
Effects
Sensitization
0 0 0 0 2
Level
Carcinogenicity
0 4 0 0 0
Level
Reproduce
0 0 0 0 0
Toxicity Level
Severity of
0 4 3 3 3
Chronic Effects
Subtotal 1 9 7 4 8
Total 29

Raw Materials
Sodium
Criteria Natural Ammonia
Limestone Coke Hydroxide
Brine Gas
Powder
May cause May cause Very
Severity of
skin and May cause Fatal if eye and hazardous
Immediate
eye skin and inhaled respiratory in case of
Effects
irritation eye tract skin
277
irritation irritation contact,

eye
contact,
ingestion,
and
inhalation.
Sensitization Not Not Not Not Very
Level classified classified classified Classified hazardous
Respirable
crystalline
silica has
been
Not listed
Carcinogenicity classified Not Not Not
as
Level by IARC classified classified available
carcinogen
and NTP as
a known
human
carcinogen
Not
Not
expected to
Reproduce Not expected to Not Not
be a skin or
Toxicity Level classified be acutely classified classified
respiratory
toxic
sensitizer
Repeated Can
May cause May cause chronic produce
damage to severe inhalation eye
Severity of Not
organs burns and exposure irritation,
Chronic Effects classified
(lungs, eye may cause local skin
kidneys) damage impaired destruction
lung (or
278
function dermatitis),
and
varying
degree of
respiratory
irritation or
lung
damage.
In the process of burning of limestone with coke, carbon dioxide is produced.
This gas is used in the carbonation stage of the process and the excess carbon
dioxide can be supplied to other consumers. Since the byproduct of this process
is the product that we need, there is no problem in disposing it because it can be
subjected into purification process to achieve high purity calcium chloride.
279
280
In the production of Calcium Chloride, brine derived from production well is

chlorinated to remove bromines. Bromine is removed by displacement of the brine ions
using chlorine:
Cl 2 (g) + 2Br − → 2Cl−aq + Br 2 (g)
Two layers are formed in the separator. The heavy lower layer is the bromine. The
lighter, upper layer is the aqueous layer. The aqueous layer is the magnesium-chloride
containing brine. Magnesium is removed by adding dolime, CaO·MgO, and water to the
precipitator reactor which causes magnesium to precipitate in the form of magnesium
hydroxide, Mg(OH)2 by the reaction:
CaO ∙ MgO + 2H2 O → Ca(OH)2 + Mg(OH) 2
Ca(OH)2 + Mg(OH) 2 + MgCl2 → 2Mg(OH) 2 + CaCl2
The precipitated magnesium hydroxide will be settled and disposed. To produce

solid calcium chloride, the undiluted CaCl 2 filtrate is evaporated to 40-50% CaCl2 in
triple effect evaporators. The first effect was of a forced circulation type with an external
heat exchanger. The second and third effects were of the calandria type, with an agitator
to increase the flow rate through its internal heat exchanger tubes. Above this
concentration, the large boiling point rise of the liquor and its high viscosity make
multiple-stage vacuum evaporation difficult. NaCl precipitates from the CaCl 2 solution
when the concentration of calcium chloride is increased during the evaporation of water.
After the crystalized salts have been removed, this solution is further concentrated to 55-
65% CaCl2 in a single-effect evaporator. For the production of 74-78% CaCl2 flakes,
some of this concentration was sent to heated pans below large rotary drums. The cooled
drums were dipped into the hot solution, causing some of the calcium chloride to cool
and freeze on the drums’ outer surface as the drums rotated. The calcium dehydrate solids
were then scraped off on the other side before the drum dipped into the pan again. The
thin flakes that were formed dropped into the top of a very large multi-tray dryer. In the
281
top two-thirds of the dryer, the flakes were contacted by hot flue gas, and in the lower
third they were cooled by air. To produce 94% CaCl2 solid product, a portion of the
concentrated liquid was sprayed into the dryer and directly heated by very hot flue gas.
Solids were removed from the dryer, cooled and screened to the desired particle size,
while the exhaust gas was scrubbed and then vented. The oversize was crushed and
returned to the screen, while the fines were recycled back to the heated pan of the flaker.
282
Figure 6.3.1: Process Flow Diagram of Process 3: Production of Calcium Chloride from Natural Brine
283
I. SUSTAINABILITY
The raw materials dolime and chlorine are all locally available in the
Philippines. Some of the companies that produce or supply these
materials are:
Table 6.3.1: Suppliers of raw materials for Process 3

 Fortune Cement Corp.
 Holcim Philippines Inc.
 Solid Cement Corp.
 APO Cement Corp.
 Rizal Cement Corp.
 Lafayette Mining Ltd.
 Glencore International
Dolime
 Lepanto Consolidated Mining Co.
 Philex Mining Corp.
 Philippine Mining Development
Corp.
 Hinatuan Mining Corp.
 TVI Resources Development
Philippines Inc.
 Mabuhay Vinyl Corp.
 Crown Asia Chemicals Corp.
Chlorine  Air Liquide Philippines
 International Chemical Industries

Inc.
284
To have a continuous production of Calcium Chloride from Natural Brine, we have to

look at the supply of raw materials for process 3 in the Philippines. The raw materials
should have a stable supply to support the production of Calcium Chloride.
a. Supply of Dolime in the Philippines

The historical demand and supply of dolime from the year 2007 to 2016 is
presented below. The supply data were derived from the local production through
mining in different locations in the Philippines. The said data were reported in
Philippine production for mineral commodities by United States Geological
Survey. A part of supply consists of the import volume from the international
market which was supplying through distribution or trading companies. The
demand data were derived from the local consumption of dolime which is mainly
used is concrete production as one of its components. The data used for deriving
demand was presented in Cement Manufacturers’ Association of the Philippines
Inc. (CeMAP) as the government expenditures for cement (and for concrete
production). The exportation volume was treated as an addition demand for
international market consumption that was treated as a market driver for local
production of dolime. The trade data such us importation and exportation volume
were acquired from United Nations Commodity Trade (UN comtrade) statistics
database.
Table 6.3.2: Historical Demand and Supply of Dolime [Philippine Production for
Mineral Commodities by USGS, CeMAP, UNCOMTRADE database]

2007 1096138 1374053
2008 1152326 1538199
2009 1178920 2025740
2010 1262839 2353387
2011 1433701 2143535
285
2012 1628131 2290356

2013 2613493 2146568
2014 2984777 1222268
2015 2997269 1335007
2016 3012736 934643
3500000
3000000
2500000
Net Weight (MT)
2000000
1500000 Supply (MT)

Demand (MT)
1000000
500000
0
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Year
Figure 6.3.2: Graphical Representation of Supply and Demand of Dolime
a. Supply of Chlorine in the Philippines

The historical demand and supply of ammonia from the year 2007 to 2016
is presented below. The production (local supply) and consumption (local
demand) data were acquired from the National Statistics Office (NSO)– Public
Reference Unit. A part of supply consists of the import volume from the
companies. The exportation volume was treated as an addition demand for
international market consumption or demand that was treated as a market driver
for local production of chlorine. The trade data such us importation and
exportation volume were acquired from United Nations Commodity Trade (UN
comtrade) statistics database.
286
Table 6.3.3: Historical Demand and Supply of Ammonia [NSO – Public Reference
Unit, UNCOMTRADE database]

2007 5532 16617
2008 9205 20982
2009 6983 5548
2010 9950 18664
2011 12316 20809
2012 14109 25723
2013 13755 7805
2014 9380 22671
2015 8364 22151
2016 12210 23589
30000
25000
Net Weight (MT)
20000
15000
Supply (MT)
10000 Demand (MT)
5000
0
2007 2008 2009 2010 2011 2012 2013 2014 2015 2016
Year
Figure 6.3.3: Graphical Representation of Supply and Demand of Chlorine
287
II. ECONOMICS:
i. Equipment Cost:
Calcium Chloride from Natural Brine is calculated using the Lang Method from
Perry’s Chemical Engineers’ Handbook 8th ed. These Lang factors depend on the
type of processing per equipment. Solid processing factor is applied to equipment
which only processes solids such as crushers, ball mills, screener, etc. Solid-fluid
processing factor is applied to equipment which processes solids and fluids such as
solid-liquid separation equipment – examples are leaching equipment, filters,
sedimentation equipment, etc. Fluid processing factor is for equipment which only
processes fluids such as distillation columns, absorption column, etc. These factors
are multiplied in equipment costs resulting to Equipment Fixed Capital Cost.
Lang Factors
Type of Plant
Equipment Qty. Equipment Cost Fixed Capital Cost

Chlorine Storage Tank 1 $3,000.00 $12,900.00
Dolime Storage Tank 1 $8,000.00 $34,400.00
Water Storage Tank 1 $1,000.00 $4,300.00
CaCl2 Storage Tank 1 $1,000.00 $4,300.00
288
Separator 1 $3,300.00 $14,190.00

Screen 1 $3,000.00 $12,900.00
Crusher 1 $10,000.00 $43,000.00
Settling Filter 1 $12,000.00 $51,600.00
Evaporator 4 $80,000.00 $344,000.00
Scrubber 1 $20,000.00 $86,000.00
Heat Exchanger 1 $10,000.00 $43,000.00
Conveyor 1 $1,000.00 $4,300.00
Flaker 1 $20,000.00 $86,000.00
Dolime Slaker 1 $8,600.00 $36,980.00
Precipitator Reactor 1 $30,000.00 $129,000.00
Dryer 1 $10,000.00 $43,000.00
Total Number of Equipment 19
Total Purchase Cost of USD $220,900.00 $949,870.00
Equipment
PHP ₱11,173,939.33 ₱48,047,939.12
(PCE)
ii. Project Cost

Project fixed capital cost that is needed to put up a plant that produces
Calcium Chloride is calculated using Table 3.7 from Chemical Engineering Design:
Chemical Engineering, Volume 6. These factors depend on the type of processing that
is involved in your whole process. Fluid Process Type factors are applied to a process
which involves fluids processing only. Fluids-Solids Process Type factors are applied
to a process which involves both solids and fluids processing. Solids Process Type
factors are applied to a process which involves solids processing only.
289
Table 6.3.6: Estimation of Fixed Capital Cost (Sinnot, 2005)
Table 4. Typical Factors for Estimation of Project Fixed Capital Cost

Process Type
Item
Major equipment, total purchase cost PCE PCE PCE
ƒ2 Piping 0.70 0.45 0.20
ƒ4 Electrical 0.10 0.10 0.10
*ƒ6 Utilities 0.50 0.45 0.25
*ƒ7 Storages 0.15 0.20 0.25
*ƒ9 Ancillary building 0.15 0.20 0.30
3. Total physical plant cost (PPC)
𝐏𝐏𝐂 = 𝐏𝐂𝐄(𝟏 + ƒ𝟏 + ⋯ + ƒ𝟗 )
= 𝐏𝐂𝐄 𝐱 3.40 3.15 2.80
= 𝐏𝐂𝐄 𝐱 1.45 1.40 1.35

FIXED CAPITAL
(PPC)COST (FCC) ₱195,074,632.82
290
TOTAL PHYSICAL PLANT COST (PPC)
PPC = PCE(1 + f1 + f2 + f3 + f4 + f5 + f6 + f7 )
PPC = ₱48,047,939.12 (1 + 0.45 + 0.45 + 0.15 + 0.1 + 0.1 + 0.45 + 0.2)
PPC = ₱139,339,023.45
FIXED CAPITAL COST:
FCC = PCC(1 + f10 + f11 + f12 )
FCC = ₱139,339,023.45 (1.40)
FCC = ₱195,074,632.82

WCC = FCC(0.05)
WCC = ₱195,074,632.82 (0.05)
WCC = ₱9,753,731.64

TCI = FCC + WCC
TCI = ₱195,074,632.82 + ₱9,753,731.64
TCI = ₱204,828,364.46
Total capital investment refers to a plant’s acquisition of capital assets or fixed assets
such as machinery that is expected to be productive over many years.

An estimate of the operating costs, the cost of producing the product, is
needed to judge the viability of a project, and to make choices between possible
alternative processing schemes. These costs can be estimated using Figure 3.4 from
Chemical Engineering Design Volume 6. Fixed operating cost is the costs that do not
vary with production rate. These are the bills that have to be paid whatever the
291
quantity produced. While variable costs are dependent on the amount of product
produced.
FIXED COSTS
Insurance ₱1,950,746.33
Royalties ₱1,950,746.33
292
FIXED COST:
𝑀𝑎𝑖𝑛𝑡𝑒𝑛𝑎𝑛𝑐𝑒 𝑎𝑛𝑑 𝑅𝑒𝑝𝑎𝑖𝑟𝑠(𝑀𝑅) = 𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 = 5 − 10% 𝑜𝑓 𝑓𝑖𝑥𝑒𝑑 𝑐𝑎𝑝𝑖𝑡𝑎𝑙
𝑀𝑅 = ₱195,074,632.82 (0.10) = ₱19,507,463.28
𝑂𝑝𝑒𝑟𝑎𝑡𝑖𝑛𝑔 𝐿𝑎𝑏𝑜𝑟(𝑂𝐿) = 5 − 10% 𝑜𝑓 𝑓𝑖𝑥𝑒𝑑 𝑐𝑎𝑝𝑖𝑡𝑎𝑙
𝑂𝐿 = ₱195,074,632.82 (0.10) = ₱19,507,463.28
𝐿𝑎𝑏𝑜𝑟𝑎𝑡𝑜𝑟𝑦 𝐶𝑜𝑠𝑡(𝐿𝐶 ) = 20 − 23% 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑛𝑔 𝐿𝑎𝑏𝑜𝑟
= ₱19,507,463.28 (0.23)
= ₱4,486,716.55
𝑆𝑢𝑝𝑒𝑟𝑣𝑖𝑠𝑖𝑜𝑛(𝑆) = 20% 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑛𝑔 𝐿𝑎𝑏𝑜𝑟

= ₱19,507,463.28 (0.20)
= ₱3,901,492.66
𝑃𝑙𝑎𝑛𝑡 𝑂𝑣𝑒𝑟ℎ𝑒𝑎𝑑𝑠(𝑃𝑂) = 50% 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑛𝑔 L𝑎𝑏𝑜𝑟
= ₱19,507,463.28 (0.50)
= ₱9,753,731.64
𝐶𝑎𝑝𝑖𝑡𝑎𝑙 𝐶ℎ𝑎𝑟𝑔𝑒𝑠 (𝐶𝐶) = 𝐹𝐶𝐶(0.1)
= ₱195,074,632.82 (0.10)
= ₱19,507,463.28
𝐼𝑛𝑠𝑢𝑟𝑎𝑛𝑐𝑒(𝐼) = 𝐹𝐶𝐶(0.01)
= ₱195,074,632.82 (0.01)
= ₱1,950,746.33
𝐿𝑜𝑐𝑎𝑙 𝑇𝑎𝑥𝑒𝑠 (𝐿𝑇) = 𝐹𝐶𝐶(0.02)

= ₱195,074,632.82 (0.02)
= ₱3,901,492.66
𝑅𝑜𝑦𝑎𝑙𝑡𝑖𝑒𝑠 (𝑅) = 𝐹𝐶𝐶(0.01)
= ₱195,074,632.82 (0.10)
293
= ₱1,950,746.33
𝐹𝐼𝑋𝐸𝐷 𝐶𝑂𝑆𝑇 = 𝑀𝑅 + 𝑂𝐿 + 𝐿𝐶 + 𝑆 + 𝑃𝑂 + 𝐶𝐶 + 𝐼 + 𝐿𝑇 + 𝑅
𝑭𝑰𝑿𝑬𝑫 𝑪𝑶𝑺𝑻 = ₱𝟖𝟒, 𝟒𝟔𝟕, 𝟑𝟏𝟔. 𝟎𝟏
VARIABLE COSTS
Miscellaneous Materials ₱1,950,746.33
TOTAL VARIABLE COSTS ₱156,653,911.06
VARIABLE COST:
HRS/YR 7,200
DAYS/YR 300
i. Raw Material Cost:

Table 6.3.7: Raw Material Cost for Process 3
Raw Material Cost
Chlorine 600 USD/Metric ton ₱ 30,350.22 / Metric

ton
Dolime 300 USD/ Metric ton ₱ 15,175.11/ Metric ton
𝑅𝑎𝑤 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙𝑠
𝑡𝑜𝑛𝑠 ₱30,350.22
= 10 (300 𝑑𝑎𝑦𝑠) ( )
𝑑𝑎𝑦 𝑡𝑜𝑛
𝑡𝑜𝑛𝑠 ₱15,175.11
+ 10 (300 𝑑𝑎𝑦𝑠) ( )
𝑑𝑎𝑦 𝑡𝑜𝑛
294
= ₱136,575,990.00
𝑀𝑖𝑠𝑐𝑒𝑙𝑙𝑎𝑛𝑒𝑜𝑢𝑠 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙𝑠 = 10% 𝑀𝑎𝑖𝑛𝑡𝑒𝑛𝑎𝑛𝑐𝑒
= ₱19,507,463.28 (0.10)
= ₱1,950,746.33
𝑈𝑡𝑖𝑙𝑖𝑡𝑖𝑒𝑠:
Service facilities include such as utilities for supplying steam, water, power,
compressed air, and fuel in an industrial plant. Waste disposal, fire protection, and
miscellaneous service items also are included under the general heading of service
facilities cost. The total cost for service facilities in chemical plants may be determined as
amounts equivalent to percentages of the purchased equipment cost
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑠𝑒𝑟𝑣𝑖𝑐𝑒𝑠 = 40%(𝐸𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡 𝐶𝑜𝑠𝑡)

= ₱11,173,939.33 (0.40)
= ₱4,469,575.73
𝑉𝐴𝑅𝐼𝐴𝐵𝐿𝐸 𝐶𝑂𝑆𝑇 = 𝑅𝑎𝑤 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 + 𝑀𝑖𝑠𝑐𝑒𝑙𝑙𝑎𝑛𝑒𝑜𝑢𝑠 𝑀𝑎𝑡𝑒𝑟𝑖𝑎l𝑠 + 𝑈𝑡𝑖𝑙𝑖𝑡𝑖𝑒𝑠

𝑽𝑨𝑹𝑰𝑨𝑩𝑳𝑬 𝑪𝑶𝑺𝑻 = ₱𝟏𝟒𝟐, 𝟗𝟗𝟔, 𝟑𝟏𝟐. 𝟎𝟔

𝑨𝒏𝒏𝒖𝒂𝒍 𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒊𝒐𝒏 𝑪𝒐𝒔𝒕 = 𝑭𝑪 + 𝑽𝑪 + 𝑫𝑷𝑪 ₱602,803,067.68
𝐷𝑖𝑟𝑒𝑐𝑡 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝐶𝑜𝑠𝑡 (𝐷𝑃𝐶) = 𝐹𝐶 + 𝑉𝐶 = ₱227,463,628.07

𝑆𝑎𝑙𝑒𝑠 𝐸𝑥𝑝𝑒𝑛𝑠𝑒 = (𝐷𝑃𝐶)(0.2) = ₱45,492,725.61
𝐺𝑒𝑛𝑒𝑟𝑎𝑙 𝑂𝑣𝑒𝑟ℎ𝑒𝑎𝑑𝑠 = (𝐷𝑃𝐶)(0.3) = ₱68,239,088.42
295
𝑆𝑢𝑏 − 𝑡𝑜𝑡𝑎𝑙 𝐷𝑃𝐶 = 𝐷𝑃𝐶 + 𝑆𝑎𝑙𝑒𝑠 𝐸𝑥𝑝𝑒𝑛𝑠𝑒 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑙 𝑂𝑣𝑒𝑟ℎ𝑒𝑎𝑑𝑠
= ₱227,463,628.07 + ₱45,492,725.61 + ₱68,239,088.42
𝑺𝒖𝒃 − 𝒕𝒐𝒕𝒂𝒍 𝑫𝑷𝑪 = ₱𝟑𝟒𝟏, 𝟏𝟗𝟓, 𝟒𝟒𝟐. 𝟏𝟏
𝐴𝑛𝑛𝑢𝑎𝑙 Production Cost = FC + VC + DPC
𝐀𝐧𝐧𝐮𝐚𝐥 𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐢𝐨𝐧 𝐂𝐨𝐬𝐭 = ₱𝟓𝟔𝟖, 𝟔𝟓𝟗, 𝟎𝟕𝟎. 𝟏𝟖
For the continuous production of calcium chloride from natural brine, separation of
bromine and magnesium is needed. The addition of chlorine and dolomite in the process
achieves the separation of bromine and magnesium leaving calcium chloride-sodium
chloride solution. After evaporation, sodium chloride is then precipitated leaving calcium
chloride to be purified and granulated. The energy requirement in this process is not high;
therefore, this process is energy efficient and the process does not require any specialized
and complicated equipment. The list of equipment shown in the table below shows the
list of major equipment that are required to run the plant and most of them does not
require high maintenance and are easy to operate. The phases involved in each equipment
are quantified from single phase (1) to triple phase (3). The average number of phases
indicates the complexity of the equipment and the average phases involved in the process
is calculated to reflect the complexity of the whole process in terms of equipment
Table 6.3.8: Average of phases involved in Process 3
Equipment Tag Equipment Name Phases Involved
Chlorine Storage Tank T-01 1
Dolime Storage Tank T-02 1
Water Storage Tank T-03 1
296
CaCl2 Storage Tank T-04 1
Separator S-01 2
Screen S-03 1
Crusher S-04 1
Dolime Slaker M-01 2
Precipitator Reactor R-01 1
Dryer E-07 2
Settling Filter S-02 2
Heat Exchanger E-01 2
Conveyor F-01 1
Flaker E-06 2
Evaporator E-02 2
Evaporator E-03 2
Evaporator E-04 2
Scrubber C-01 2
Evaporator E-05 2
IV. SAFETY

297

Raw Materials
Measure
Natural Brine Chlorine Dolomite
Severity of
1 4 1
Immediate Effects
Sensitization Level 0 0 0
Carcinogenicity
0 0 4
Level
Reproduce Toxicity
0 2 0
Level
Severity of Chronic
0 3 3
Effects
Subtotal 1 9 8
Total 18
Raw Materials
Criteria
Natural Brine Chlorine Dolomite
Severity of May cause skin and Fatal if inhaled May cause skin and
Immediate Effects eye irritation eye irritation
Sensitization Level Not classified Not classified Not known
298
Respirable
crystalline silica
has been classified
by IARC and NTP
Carcinogenicity Not listed as as a known human
Not classified
Level carcinogen carcinogen, and
classified by
ACGIH as a
suspected human
carcinogen.
May cause Not expected to be
Reproduce
Not classified respiratory a reproductive
Toxicity Level
irritation hazard.
Causes severe skin May cause damage
Severity of
Not classified burns and eye to organs (lungs,
Chronic Effects
damage kidneys)
In the separation process, the by-product bromine is a toxic and corrosive

material. It can be therefore dangerous to handle without taking appropriate
precautions: Prevent further leakage or spillages if safe to do so, do not let this
product enter drains, and discharge into the environment must be avoided.
Magnesium hydroxide must be kept in suitable closed containers for disposal.
must be kept in suitable closed containers for disposal. Prevent this waste from
reaching drains, sewer or waterway. This should not be released into the
environment. Sodium chloride, another byproduct is restricted to be discharge to
sewer systems or environment due to ions that can be absorbed by plants or by
299
animals ingesting water containing salt thus requiring containment and proper
disposal of water. This should also not be released into the environment.
SUMMARY OF THE CRITERIA FOR PROCESS SELECTION
Selection of the appropriate process is an important decision. To be able to make

the best choice among the proposed processes, the following criteria are considered:
Table 6.3.11: Summary of the Criteria for Process Selection
Process 1
Process 2 Process 3
Criteria (via Limestone-

(via Solvay (From Natural
Hydrochloric
Process) Brine)
Process)
ECONOMICS
Total Capital Total Capital
Total Capital Investment is Investment is
Investment is dependent on dependent on
dependent on equipment cost. equipment cost.
equipment cost. Process 2 has 21 Process 3 has 19
Process 1 has 13 equipment. The most equipment. The most
equipment. The most expensive equipment expensive equipment
Total Capital expensive equipment are: Brine Evaporator, are: Crusher,
Investment are: Reactor, Settling Filter, Evaporator, Scrubber,
Evaporator, and Spray Absorption Tower, Flaker, and
Dryer The total Solvay Tower, Lime Precipitator Reactor.
capital investment of Kiln, Rotary Calciner, The total capital
this process is Gas Scrubber, Cooler, investment of this
₱93,651,719.38 Flash Vessel, and process is
Distillation Column. ₱204,828,364.46
300
The total capital

investment of this
process is
₱416,004,321.93
Annual Production Annual Production
Annual Production
Cost is dependent on Cost is dependent on
Cost is dependent on
Fixed Cost, Variable Fixed Cost, Variable
Fixed Cost, Variable
Cost and Direct Cost and Direct
Cost and Direct
Production Cost. Production Cost.
Production Cost.
Variable cost is Variable cost is
Variable cost is
dependent on the cost dependent on the cost
dependent on the cost
of raw materials. of raw materials.
of raw materials.
Fixed Cost was Fixed Cost was
Fixed Cost was
Annual derived on the bills derived on the bills
derived on the bills
Production Cost paid regardless of the paid regardless of the
paid regardless of the
quantity produced. quantity produced.
quantity produced.
The raw materials in The raw materials in
The raw materials in
Process 1 are Process 2 are coke,
Process3 are brine,
limestone, HCl, and limestone, ammonia
dolime and chlorine.
CaOH. The annual gas, and NaOH. The
The annual production
production cost of annual production
cost of Process 3 is
Process 1 is cost of Process 2 is
₱568,659,070.18
₱306,856,315.87 ₱1,371,986,267.95
MANUFACTURABILITY
The purity of the

The purity of the The purity of the
product produced in
product produced in product produced in
the Production of
the Production of the Production of
% Purity Calcium Chloride via
Calcium Chloride via Calcium Chloride
Limestone-
Solvay Process is at Form Natural Brine is
Hydrochloric Process
63% at 94%
is at 94%
301
The average phases The average phases The average phases

involved in Process involved in Process involved in Process
1 is 1.6. The 2 is 1.71. The 3 is 1.5. The
presence of more presence of more presence of more
than one phase than one phase than one phase
indicates the indicates the indicates the
complexity of the complexity of the complexity of the
equipment. These equipment. These equipment. These
phases are phases are phases are
considered in considered in considered in
Average
solving operating solving operating solving operating
Number of
parameters. The parameters. The parameters. The
Phases
higher the phase, the higher the phase, the higher the phase, the
more difficult the more difficult the more difficult the
process is. An process is. An process is. An
average of 1 being average of 1 being average of 1 being
the lowest difficulty the lowest difficulty the lowest difficulty
in processing to 3 in processing to 3 in processing to 3
indicating the indicating the indicating the
highest difficulty in highest difficulty in highest difficulty in
processing. processing. processing.
SAFETY
The raw materials in The raw materials in
The raw materials in
Process 1 are 33% Process 2 are
Process 3 are
w/w Hydrochloric Natural Brine,
Natural Brine,
Acid, Limestone Limestone,
Toxicity Level of Chlorine, and
Powder (99.5% Ammonia Gas,
Raw Materials Dolomite Process 3
purity), and Calcium Coke, and Sodium
had a total toxicity
Hydroxide Powder. Hydroxide Powder.
level of 18.
Process 1 had a total Process 2 had a total
302
toxicity level of 18. toxicity level of 29.

SUSTAINABILITY
Raw materials for Raw materials for Raw materials for
this process is this process is this process is
Availability of locally available and locally available and locally available and
Raw Materials has a steady supply has a steady supply has a steady supply
gaining a score of 5 gaining a score of 5 gaining a score of 5
ENVIRONMENTAL IMPACT
The main wastes are The main wastes are

Magnesium Bromine,
Hydroxide,
Magnesium
Calcium, and Iron.
The main wastes are Hydroxide, and
Magnesium
small amounts of NaCl. Bromine is
Hydroxide generally very toxic to aquatic
limestone and CO2.
has no adverse
Limestone has no life. Magnesium
conditions
harmful effect to the Hydroxide generally
anticipated, but may
environment. While has no adverse
require compliance conditions
CO2 discharge to
Environmental with governmental
atmosphere in large anticipated, but may
Impact restrictions and
quantities should be require compliance
permitting
avoided. The safe with governmental
requirements prior
concentration levels restrictions and
to release. Calcium,
of carbon dioxide permitting
when emitted is a
must be below 1 requirements prior
flammable solid
percent. to release. NaCl is
that, in contact with reactive with
water, emits oxidizing agents,
flammable gases.
metals, acids, has
And lastly, Iron has acute toxicity to
303
acute oral toxicity to animals.

animals, possibly
hazardous short
term degradation
products are not
likely. However,
long term
degradation
products may
arise.
304
SCORING: The scores are evaluated from the attributes that will determine the optimum
process. The highest score given is 5. The score will be multiplied to the level of
importance to attain the overall score.
Table 6.3.12: Summary of Scores of the Evaluation of Three Processes
Importance SCORE SCORE * Level OVERALL SCORE

ATTRIBUTES
Level P1 P2 P3 P1 P2 P3 P1 P2 P3
ECONOMICS
TCI 5 1.126 2.286 25 5.628 11.431

5 25 5.610 12.460
APC 5 1.118 2.698 25 5.591 13.490
MANUFACTURABILITY
Purity 5 3.351 5 20 13.40 20

Average
4 19.38 15.50 20
Number of 4.69 4.4 5 18.75 17.60 20
Phases
SAFETY
Toxicity Level
of Raw 3 5 3.105 5 15 9.315 15 15 9.350 15
Materials
SUSTAINABILITY
Availability of
2 5 5 5 10 10 10 10 10 10
Raw Material
ENVIRONMENTAL IMPACT
Emission of
1 5 3.335 3.335 5 3.335 3.335 5 1.670 1.670
Wastes
TOTAL 74.38 42.13 59.13
Conclusion
Based on the scores obtained, Process 1 which is Production of Calcium
Chloride via Limestone – Hydrochloric Acid Process is the most favorable compared to
the two processes discussed. It has the cheapest economic cost, the highest efficiency, the
process which has the most favorable safety, one of the process that is most sustainable,
and the process that is most environment-friendly.
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Technological Institute of the Philippines

Calcium chloride is an inorganic compound,

The 10% w/w lime solution used in neutralization is produced in a lime

Table 6.1.1: Suppliers of Raw Materials for Process 1

Raw Materials Suppliers

 Mabuhay Vinyl Corp

Calcium Hydroxide powder  H.T Mining Products

 Hyper Kem and

To have a continuous production of Calcium Chloride via Limestone – Hydrochloric

a. Limestone Supply in the Philippines

Table 6.1.2: Historical Demand and Supply of Limestone [Philippine

40000 Supply ('000MT)

30000 Demand ('000 MT)

Figure 6.1.3: Graphical Representation of Supply and Demand of Limestone

b. Calcium Hydroxide Supply in the Philippines

Table 6.1.3: Historical Demand and Supply of Calcium Hydroxide [Philippine

Year Supply (MT) Demand (MT)

Figure 6.1.4: Graphical Representation of Supply and Demand of Calcium

c. Supply of Hydrochloric Acid in the Philippines

Year Supply (MT) Demand (MT)

2007 35674 24302

2013 35129 28508

Figure 6.1.5: Graphical Representation of Supply and Demand of

screener, etc. Solid-fluid processing factor is applied to equipment which processes

Table 6.1.5: Lang Factors (Green & Perry, 2008)

Table 6.1.6: Equipment Cost for Process 1 (www.alibaba.com)

Equipment Qty. Equipment Cost Fixed Capital Cost

Spray Dryer 1 $ 10,000.00 $ 10,000.00

ii. Project Cost

Table 6.1.7: Estimation of Project Fixed Capital Cost (Sinnot, 2005)

Typical Factors for Estimation of Project Fixed Capital Cost

𝐅𝐢𝐱𝐞𝐝 𝐜𝐚𝐩𝐢𝐭𝐚𝐥 = 𝐏𝐏𝐂 (𝟏(𝟏 + ƒ𝟏𝟎 + ƒ𝟏𝟏 + ƒ𝟏𝟐 )

TOTAL PHYSICAL PLANT COST ₱63,708,652.64

TOTAL PHYSICAL PLANT COST (PPC):

PPC = ₱21,968,500.91 (1 + 0.45 + 0.45 + 0.15 + 0.1 + 0.1 + 0.45 + 0.2)

FIXED CAPITAL COST:

FCC = PCC(1 + f10 + f11 + f12 )

FCC = ₱63,708,652.64 (1.40)

WORKING CAPITAL COST (WCC):

TOTAL CAPITAL INVESTMENT (TCI):

iii. Production Cost

Figure 6.1.6: Costing and Project Evaluation (Coulson and Richardson)

Maintenance and Repairs(MR) = Average process = 5 − 10% of fixed capital

MR = ₱89,192,113.69 (0.10) = ₱8,919,211.37

Operating Labor(OL) = 5 − 10% of fixed capital

OL = ₱89,192,113.69 (0.10) = ₱8,919,211.37

Laboratory Cost(LC) = 20 − 23% operating Labor

Supervision(S) = 20% operating Labor

Plant Overheads(PO) = 50% operating Labor

Raw Material Cost:

Table 6.1.8: Raw Material Cost for Process 1 (www.alibaba.com)

Raw Material Cost

tons ₱10,116.74 tons

𝐕𝐀𝐑𝐈𝐀𝐁𝐋𝐄 𝐂𝐎𝐒𝐓 = ₱𝟖𝟒, 𝟏𝟐𝟐, 𝟑𝟒𝟏. 𝟏𝟐

Direct Production Cost ₱122,742,526.35

𝐀𝐧𝐧𝐮𝐚𝐥 𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐢𝐨𝐧 𝐂𝐨𝐬𝐭 = 𝐅𝐂 + 𝐕𝐂 + 𝐃𝐏𝐂 ₱306,856,315.87

Direct Production Cost (DPC) = FC + VC = ₱122,742,526.35

Sales Expense = (DPC)(0.2) = ₱24,548,505.27

General Overheads = (DPC)(0.3) = ₱36,822,757.90

Sub − total DPC = DPC + Sales Expense + General Overheads

= ₱122,742,526.35 + ₱24,548,505.27 + ₱36,822,757.90

𝐒𝐮𝐛 − 𝐭𝐨𝐭𝐚𝐥 𝐃𝐏𝐂 = ₱𝟐𝟐𝟖, 𝟐𝟒𝟎, 𝟗𝟗𝟐. 𝟕𝟎

Annual Production Cost = FC + VC + DPC