06 Process Selection 121 179

Technological Institute of the Philippines
PROCESS
SELECTION
121
PRODUCTION OF ANHYDROUS HYDROGEN FLUORIDE
Hydrogen fluoride is a chemical compound with the chemical formula HF. This
colorless gas or liquid is the principal industrial source of fluorine, often as
an aqueous solution called hydrofluoric acid, a colourless solution that is highly
corrosive, capable of dissolving many materials, especially oxides. Hydrogen fluoride
boils near room temperature, much higher than other hydrogen halides. Unlike other
hydrogen halides, HF is lighter than air.
Hydrogen fluoride has a number of properties that distinguish it from the

other hydrogen halides. It polymerizes, forming molecules such as H2 F2 and H6 F6 ; this
explains in part its relatively high boiling point. It is a relatively weak acid. It attacks
glass, reacting with the silica, SiO2 , to form the gas silicon tetrafluoride, SiF4 , and water;
this leaves the surface of the glass etched.
Hydrogen fluoride is produced commercially by heating purified fluorspar

(calcium fluoride) with concentrated sulfuric acid to produce the gas, which may be
condensed by cooling or dissolved in water. It is also produced by the reaction of a side-
product of the extraction of the fertilizer precursor phosphoric acid from various
minerals. The anhydrous compound hydrogen fluoride is more commonly used than its
aqueous solution, hydrofluoric acid.
Hydrogen fluoride is available commercially either in an anhydrous (water-free)

state or in water solutions of various concentrations. Because it attacks glass, it is usually
stored in steel tanks, cylinders, or drums, or, in small amounts, in plastic bottles.
Hydrogen fluoride is used in the production of aluminum and

chlorofluorocarbons, and in the glass etching and chemical industries. It is a precursor to
almost all fluorine compounds, including pharmaceuticals such as diverse materials such
as PTFE (Teflon), and elemental fluorine itself.
Hydrogen fluoride is primarily used to make fluorinated compounds such as

refrigerant gases and other fluorinated organic and inorganic compounds. It is also used
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by the petroleum refining industry as a catalyst in alkylation processes which boost the
octane content of gasoline fuels.
Hydrofluoric acid is used in the manufacture of elemental fluorine gas which in

turn is used to manufacture uranium hexafluoride sulfur hexafluoride, halogen fluorides
and emulsified perfluorochemicals. The organic fluoride, which utilizes the rest of the
available hydrofluoric acid are manufactured for production of various
chlorofluorocarbons
HF serves as a catalyst in alkylation processes in oil refineries. A component of

high-octane petrol (gasoline) called "alkylate" is generated in alkylation units that
combine C3 and C4 olefins and iso-butane to generate petrol (gasoline).
HF is a reactive solvent in the electrochemical fluorination of organic compounds. In this

approach, HF is oxidized in the presence of a hydrocarbon and the fluorine replaces CH
bonds with CF bonds. Perfluorinated carboxylic acids and sulfonic acids are produced in
this way.
Hydrogen fluoride is an important catalyst used in the majority of the

installed linear alkyl benzene production in the world. The process involves
dehydrogenation of n-paraffins to olefins, and subsequent reaction with benzene using
HF as catalyst. The largest consumers of hydrofluoric acids are fluorocarbon, which takes
up to 42% of the total consumption of HF and aluminum industries with 32%
consumption globally.
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PROCESS 1
CONTINUOUS PRODUCTION OF ANHYDROUS HYDROGEN FLUORIDE

FROM FLUORSPAR
PROCESS DESCRIPTION
The first part of the process is called Fluorspar Beneficiation and is described as
follows: metallurgical fluorspar ore is fed through a ball mill to reduce the particle size
from 30 mm to 0.044 mm (325 mesh). After this, it is classified using cross flow
classifier with addition of water to recover -325 mesh particles from coarse particles
(+325 mesh). For further purification, the ore is fed to a flotation unit using Oleic acid,
Soda ash and Sodium bisulfate as reagents. In this unit, separation of Calcium fluoride
with Silicon dioxide as final tailing is achieved. The pulp from the flotation cells usually
contains 20 percent solids (Beneficiation of Fluorspar ores, G.E. Allen et al 1965). The
mixture is then fed to a thickener to increase the concentration of solid to 50-60%. The
slurry thick solution is further dewatered up to 6% moisture using a rotary filter. To
achieve the acid grade fluorspar with a standard moisture content of 0.5%, the filtrate
must be dried in a standard drier at about 105 degrees Celsius. Acid grade fluorspar is
treated with concentrated sulfuric acid in a heated rotating steel kiln. The product is
formed according to the following reaction:
Main reaction: CaF2 + H2 SO4 CaSO4 + 2HF
Side reaction: SiO2 + 4HF SiF4 + 2H2 O
Over-all reaction: 2CaF2 + 2H2 SO4 + SiO2 2CaSO4 + SiF4 + 2H2 O
The reaction temperature is kept at 200-250C for 30 to 60 minutes. The gases are
passed into the acid scrubber at 121 degrees Celsius and the HF is absorbed together with
sulfuric acid since these two are soluble with each other.
Partial amount of gaseous HF and non-condensable SiF4 are again scrubbed out with
water at 140 degrees Celsius to form H2 SiF6 by the overall reaction:
3SiF4 + 2H2 O 2H2 SiF6 + SiO2
The absorbed sulfuric acid containing HF is pumped to a vaporizer at 93 degrees
Celsius and will go to a throttling valve before it enters a flash distillation column by
124
which it will be further purified. The distillation process is used to remove unwanted
impurities by heating the sulfuric acid and HF. The top product contains 99.99% HF with
principally small amount of sulfuric acid as impurity. The top product containing HF is
then condensed, thus producing a liquid product.
125
Figure 6.1.1. Process Flow Diagram of Process 1
126
I. SUSTAINABILITY
This process provides the important advantage of reliability in long term
continuous operation under remote control and economics in heat exchange which
lower the external energy requirements for heating and for cooling. The raw
materials of this process are readily available in the Philippines. The suppliers of
the raw materials can sustain the continuous production of Hydrogen Fluoride.
Availability of Raw Materials

The basic raw materials for the production of hydrogen fluoride from
fluorspar are acid-grade fluorspar and sulphuric acid. The chemical reaction that
generates the gaseous HF requires a source for CaF2 that is in highest purity as
possible. Acid-grade fluorspar refers to fluorspar ore that contains a minimum of
97% of CaF2 by weight.
i. Fluorspar Supply in the Philippines
Despite having the supply for acid-grade fluorspar in the Philippines

relatively scarce compared to other countries, a certain company in the
Philippines called Palcer Trading International or PTI Philippines offers a stable
supply for metallurgical fluorspar (fluorspar ore with around 80-85% of CaF2 by
weight). The table below shows the specifications of the above companys
fluorspar product.
Table 6.1.1 PTI Philippines Fluorspar Specifications

(Source: www.ptiphilippines.wordpress.com)
Specifications
CaF2 85% min.
SiO2 14% min.
Size 10-50 mm
127
Packing 1 MT bags containerized
20 MT per container
Another company that can supply metallurgical grade fluorspar in the Philippines
is MH Fair Bridge, Inc. with the following product specifications:
Table 6.1.2 MH Fair Bridge, Inc. Fluorspar Specifications

(Source: www.alibaba.com)
Specifications
CaF2 80% min.
SiO2 17% max.
Size 10-50 mm
Packing 1 MT jumbo bags
The supply and demand of fluorspar in the Philippines is shown below.
Projected Demand and Supply of Fluorspar

2,500,000
2,000,000
1,500,000
1,000,000
500,000
0
2016 2018 2020 2022 2024 2026 2028
Projected Demand (AGCM) Projected Supply (ASLM)
Figure 6.1.2 Projected Demand and Supply of Fluorspar
128
A process called Fluorspar Beneficiation (process of upgrading the grade of

fluorspar ore) will be implemented by HydroFluor Philippines in order to upgrade this
metallurgical-grade fluorspar supply to acid-grade fluorspar.
ii. Sulphuric Acid supply in the Philippines

The supply of Sulphuric Acid in the Philippines is quite large and many
manufacturing companies are producing this product in the country such as Emerald
Chemicals, Inc. (ECI), LMG Chemicals Corporation, Chemphil Manufacturing
Corporation, and so on.
The supply and demand of sulphuric acid in the Philippines is shown below:
30,000,000
25,000,000
20,000,000
15,000,000 Demand
Supply
10,000,000
5,000,000
0
2004 2006 2008 2010 2012 2014 2016
Figure 6.1.3 Demand and Supply of Sulfuric Acid
129
II. ECONOMICS
Exchange Rate: 1 USD = Php 49.419 (PRICES, 2016)
i. Cost of Raw Materials
Table 6.1.3 Market Price of Raw Materials

Sulphuric Acid 260 USD/Metric ton Php 12,848.94/ Metric ton
Fluorspar 380 USD/ Metric ton Php 18,779.22/ Metric ton
Total Php 31,628.16/ Metric ton
ii. Cost of Equipment
The estimated fixed capital cost required for the production of hydrogen
fluoride from fluorspar and sulfuric acid is computed using Lang method,
factor for fluids processing taken from Perrys Chemical Engineering
Handbook 8th ed.
Table 6.1.4 Process 1 Lang Method Factors

(Source: D.W. Green, R.H. Perry, Perrys Chemical) Engineers Handbook
Type of Plant 8th ed.)Lang factors
Fixed Capital Investment Total Capital Investment
Solid processing 4.0 4.7
Solid-fluid 4.3 5.0
processing
Fluid processing 5.0 6.0
130
Table 6.1.5 Typical factors for estimation of project fixed capital cost
(Source: Coulson and Richardson, Chemical Engineering Design, Volume 6)
Item Process Type

Fluid Fluids-solids Solids
1.Major Equipment PCE PCE PCE
f1 Equipment erection 0.4 0.45 0.50

f2 Piping 0.70 0.45 0.20
f3 Instrumentation 0.20 0.15 0.10
f4 Electrical 0.10 0.10 0.10
f5 Buildings, process 0.15 0.10 0.05
*f6Utilities 0.50 0.45 0.25
*f7Storages 0.15 0.20 0.25
*f8Site development 0.05 0.05 0.05
*f9 Ancillary buildings 0.15 0.20 0.30
2. Total Physical Plant

Cost (PPC) 3.40 3.15 2.80
PPC=PCE(1+f1 ++f9)
=PCE x
f10 Design and 0.30 0.25 0.20
Engineering
f11 Contractors fee 0.05 0.05 0.05
f12 Contingency 0.10 0.10 0.10
Fixed capital=PPC(1+
f10 + f11 + f12
=PPC x
131
Formula for the computation of Fixed Capital Cost was taken from Chemical
Engineering Design Volume 6 by Coulson and Richardson
Cf = fL Ce
Where:
Cf= fixed capital cost
Ce= total cost of all major equipment items
fL= the Lang factor, which depends on the type of process
Table 6.1.6 Fixed Capital Cost per Equipment
Equipment Qty. Equipment Cost Fixed Capital

Cost
Fluorspar Silo 1 $ 5,000.00 $ 21,500.00
Fluorspar Grinding Mill 1 $ 67,000.00 $ 288,100.00
Classifier 1 $ 20,000.00 $ 86,000.00

Flotation Cell 1 $ 20,000.00 $ 86,000.00
Thickener 1 $ 50,000.00 $ 215,000.00
Rotary Drum Filter 1 $ 3,000.00 $ 12,900.00

Rotary Drier 1 $ 3,000.00 $ 12,900.00
Rotatry kiln 1 $ 10,000.00 $ 43,000.00
Acid Scrubber 1 $ 7,000.00 $ 30,100.00

Water Scrubber 1 $ 5,000.00 $ 21,500
Heater 1 $ 20,000.00 $ 86,000.00
Flash Distillation Column 1 $ 50,000.00 $ 215,000.00

Condenser 1 $ 20,000.00 $ 86,000.00
HF Product Storage Tank 1 $ 11,000.00 $ 47,300.00
tank 2 $ 5,000.00 $ 21,500.00
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Oleum Tank 1 $ 5,000.00 $ 21,500.00

Total Purchase Cost of 22 $ 301,000.00 $ 1,294,300
Equipment
Total in Php 14,875,119 63,963,011.7
PPC Physical Plant Cost 185,492,733.9

FCC Fixed Capital Cost 259,689,827.5
WCC Working Capital Cost 12,984,491.37
TCI Total Capital Investment 272,674,318.9
TOTAL PHYSICAL PLANT COST (PPC)
PPC = PCE(1 + f1 + f2 + f3 + f4 + f5 + f6 + f7 )
PPC = 63,963,011.7(1 + 0.45 + 0.45 + 0.15 + 0.1 + 0.1 + 0.45 + 0.2)
PPC = 185,492,733.9
FIXED CAPITAL COST:
FCC = PCC(1 + f10 + f11 + f12 )
FCC = 185,492,733.9(1.40)
FCC = 259,689,827.5
WORKING CAPITAL COST (WCC):

WCC = FCC(0.05)
WCC = 259,689,827.5 (0.05)
WCC = 12,984,491.37
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TOTAL CAPITAL INVESTMENT (TCI):

TCI = FCC + WCC
TCI = 259,689,827.5 + 12,984,491.37
TCI = 272,674,318.9
OPERATING TIME, PLANT ATTAINMENT

7,920
(HRS/YR)
FIXED COSTS
Maintenance and Repairs 25,968,982.75
Operating Labor 120,036.69
Laboratory Cost 24,007.34
Engineering and Supervision 19,188,903.51
Plant Overheads 45,277,922.95
Local Taxes 51,937,965.5
Insurance 2,596,898.275
Patent/Royal Fees 2,596,898.275
TOTAL FIXED COST 147,711,615.3
VARIABLE COSTS
Raw Materials 31,628.16
Operating Materials 3,895,347.413
Utilities (Services) 5,950,047.6
TOTAL VARIABLE COSTS 9,877,023.173
Direct Production Cost 157,588,638.5

Sales Expense 31,517,727.69
General Overheads 47,276,591.54
Total Direct Cost 236,382,957.7
134
= + + , ,
FIXED COST:
Maintenance Cost = 0.10 (FCC)
Maintenance Cost = 0.10 (259,689,827.5 )
Maintenance Cost = 25,968,982.75
Operating Labor(OL)
Figure 6.1.4 Operating Labor Cost
0.5
N0 = (6.29 + 0.23 (16))
N0 = 3.157530681
OL = N0 (4.8)(operating time/yr)
OL = 120,036.69
Laboratory Cost(LC) = 10% 20% operating Labor = 120,036.69 (0.20)

= 24,007.34
Engineering and Supervision(ES) = PCE(0.30) = 63,963,011.7(0.30)

= 19,188,903.51
135
Plant Overheads(PO)
= Maintenance + Operating Labor + Engineering and Supervision
= 25,968,982.75 + 120,036.69 + 19,188,903.51
= 45,277,922.95
Local Tax(LT) = FCC(0.2) = 259,689,827.5(0.2) = 51,937,965.5

Insurance(I) = FCC(0.01) = 259,689,827.5 (0.01) = 2,596,898.275
Patent/Royal Fees(P/RF) = FCC(0.01) = 259,689,827.5 (0.01)
= 2,596,898.275
= MR + OL + LC + ES + PO + LT + I + P/RF
= , , .
VARIABLE COST:
Raw Materials = 31,628.16
Operating Materials = 15% Maintenance = 25,968,982.75(0.15)
= 3,895,347.413
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)
Utilities = 14,875,119(0.40) = 5,950,047.6
= Raw Material + Operating Materials + Utilities

= 9,877,023.173
Direct Production Cost (DPC) = FC + VC = 157,588,638.5
136
Sales Expense = (DPC)(0.2) = 157,588,638.5(0.2) = 31,517,727.69

General Overheads = (DPC)(0.3) = 157,588,638.5 (0.3) = 47,276,591.54
Subtotal DP = DPC + Sales Expense + General Overhead

= 157,588,638.5 + 31,517,727.69 + 47,276,591.54
= 236,382,957.7
= FC + VC + DPC = 315,177,277
III. MANUFACTURABILITY
For the continuous production of hydrogen fluoride from fluorspar and
sulfuric acid, fluorspar is beneficiated having means for floatation process to
produce a fluorspar enriched concentrate of acid-grade quality from fluorspar ores
contaminated with complex metallic salts. The mixing of sulfuric acid and spar
accelerates the subsequent reaction in the kiln, increasing plant capacity as much
as 30% for a given kiln size. In order to minimize energy consumption and
corrosion of the reactor, the reaction is carried out at the lowest possible
temperature resulting in good yields. 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 operations, an average
of 1 being the lowest difficulty in processing to 3 indicating the highest difficulty
in processing.
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Table 6.1.7 Overall Equipment List with corresponding phases involved for Process 1
Equipment # Equipment Tag Equipment Name Phases Involved

1 M-100 Ball Mill 1
2 S-100 Classifier 2
3 S-101 Flotation Cells 2
4 S-102 Thickener 2
5 S-103 Rotary Filter 2
6 S-106 Rotary Kiln 3
7 A-100 Acid Scrubber 2
8 A-101 Water Scrubber 2
9 S-106 Distillation 2
Column
10 T-100 AHF Storage Tank 1
11 T-101 H2SO4 Storage 1
Tank
12 E-100 Vaporizer 2
13 E-101 HF Condenser 2
14 N-100 Stream 1 1
Conveyor
15 N-101 Stream 3 1
Conveyor
16 P-100 Stream 5 Pump 1
138
24 T-102 Water Tank 1

25 T-103 Oleic Acid Tank 1
26 T-104 Soda Ash Tank 1
27 T-105 Sodium Bisulfite 1
Tank
28 T-106 Oleum Tank 1
29 T-107 Fluorspar Silo 1
Average 1.38
IV. PROCESS USAGE IN THE INDUSTRY

There are two local manufacturing companies using this process and these
are Atom Industrial Sales and Precision Foundry of the Philippines located in
Marikina city. The demand of this chemical is still at its peak because of its
widely used in the industry especially in petrochemical industry as a
component of superacids, considering that it is highly corrosive. It is also used
in household as cleanser others.
V. HUMAN AND EQUIPMENT SAFETY

i. Human Safety
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 and from the information in 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.
139
Table 6.1.8 Toxicity Level Scores of Raw Materials in Process 1
Measure Raw Materials
Fluorspar Sulfuric Acid
1. Severity of 2 4
Immediate Effects
2. Sensitization Level 3 2
3. Carcinogenicity 0 3
Level
4. Reproduce Toxicity 0 1
Level
5. Severity of Chronic 0 4
Effects
Subtotal 5 14
Total 19
Table 6.1.9 Basis of Toxicity Level Scores

(from MSDS Laguna Clay Company)
Criteria Raw Materials
Fluorspar Sulfuric Acid
1. Severity of Possibility of irritation Causes severe skin, eye and

Immediate Effects (silicosis) by ingestion, respiratory tract irritation
inhalation, eye and skin and burns. Harmful if
contacts. swallowed. May cause
140
permanent damage to the

digestive tract
2. Sensitization Level Possibility of Irritation Found to be sensitizer of

skin and eye
3. Carcinogenicity Calcium Carbonate; Carcinogenic to man,

Level calcium fluoride not a causing cancer of the larynx
carcinogen (the voice box).
4. Reproduce Non-mutagenic Slightly embryotoxic.

Toxicity Level
5. Severity of No known effects from Prolonged or repeated

Chronic Effects chronic exposure inhalation may affect
behavior muscle contraction
, urinary system kidney
damage, and cardiovascular
system, heart, and
respiratory system/lungs ,
teeth (dental discoloration,
erosion).
ii. Equipment Safety
Since this process deals with the manufacture of hydrogen fluoride present
in high concentrations or relatively pure form, the possibility of a large release of this
chemical is greater that what might exist in a process where hydrogen fluoride is
consumed as a reactant. Specific high hazard areas in the manufacturing process,
excluding bulk storage and transfer include the following:
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Reactor (kiln)
Acid scrubber
Condensers
Distillation Column
VI. ENVIRONMENTAL ASPECT

Aqueous effluents from washing and separation contain suspended solids which
are usually sent to settling ponds. Tailings from the floatation operation contain
both solids and the floatation agents. The latter materials are not necessarily toxic
but cause excessive growth of algae and bacteria. The by-product from the reactor
is calcium sulfate which can be neutralized with lime and is frequently discarded
(ground burial) although it can be sold as gypsum or used in the manufacture of
cements. The hot gases then go to a scrubbing column where washing acid
absorbs heat and impurities. A gaseous effluent of S02 and CO2 is vented to the
air. The amounts of these gases which are vented will vary with the purity of the
fluorspar used in the process.
142
PROCESS 2
PROCESS FOR PRODUCING ESSENTIALLY SILICON-FREE

HYDROFLUORIC ACID FROM HYDROFLUOSILICIC ACID
PROCESS DESCRIPTION
The 18% H2 SiF6 solution feed (stream 1), which is obtained as a by-product from the
manufacture of phosphate fertilizer, is pumped by P-100 and enters an absorption tower
A-100 with an operating temperature of 30 and at atmospheric pressure. The solution is
treated with a strong SiF4 gas (stream 2) which may be refluxed from a later stage in the
process. H2 SiF6 is formed in A-100 having approximately 30% concentration with the
precipitation of silica or silicic acid according to the formula:
(1) 3SiF4 + 2H2 O 2H2 SiF6 + SiO2
The SiO2 (stream 4) formed in the reaction at A-100 is filtered off. The H2 SiF6
solution (stream 3) is transported through P-101 to mixer M-100 at ambient temperature
and pressure where at least an equivalent amount of solid sodium fluoride (NaF) (stream
5) is added. The NaF may be recycled to mixer from a later stage of the process. The
following reaction takes place in a mixer:
(2) 2H2 SiF6 + 4NaF 2Na2 SiF6 +4HF
The slurry formed in the reaction (stream 6) are then pumped by P-102 and taken to
filter (S-100). At S-100, the precipitated Na2 SiF6 (stream 8) is separated from the HF
solution (stream 7) at atmospheric pressure and 30. The wet Na2 SiF6 (stream 8) is
taken from filter S-100 to dryer S-101 by P-103 where it is dried at atmospheric pressure
and 104 temperature. The HF gas and water vapor (stream 9) produced therein are led
from dryer S-101 to mixer M-200. The dried Na2 SiF6 (stream 10) is removed to furnace
E-100 where it is calcined at a temperature of 649 and at ambient pressure to
produce SiF4 (stream 11). This SiF4 gas (stream 11) passes C-101 and is refluxed through
a suitable cooler (E-101) operating at 30 and 1 atm to lower its temperature from
143
649 to 30. The cooled SiF4 gas (stream 2) is delivered to absorption tower A-100 by
a compressor C-100. The NaF (stream 26) which is produced is refluxed from the furnace
E-100 to the mixer M-100. The reaction taking place in furnace is:
(3) 2Na2 SiF6 + heat 4NaF + SiF4
The HF solutions (stream 7 and stream 9) are pumped by P-104 and P-105
respectively from filter S-100 and dryer S-101, and mixed in mixer M-200 with NaF
(steam 12) which may be refluxed from a later stage in the process. The reaction taking
place in mixer is:
(4) 4NaF + 4HF 4NaHF2
The NaHF2 (stream 13) is pumped by P-200 from mixer (M-200) in the form of a
slurry to a suitable filter (S-200) operating at ambient conditions. A 3-6% NaHF2 (stream
14) solution is obtained from filter (S-200). It may be discarded or used for other
purposes such as making 2Na2 SiF6 by the addition of H2 SiF6 . The precipitated NaHF2
(stream 15) is dried in dryer (S-201) at atmospheric pressure and 104 .If HF is desired,
the dry NaHF2 (stream 17) is taken to calciner (E-200) where it is calcined at a
temperature of 260 and atmospheric pressure to produce a gas containing
approximately 95% HF (stream 18) according to the following formula:
(5) 4NaHF2 + heat 4NaF + 4HF
The NaF (stream 28) may be recycled back to mixer (M-200). The approximately
95% HF gas (stream 17) passes a compressor C-200 may then be led to rectifier S-202
operating at ambient temperature and pressure which produces an anhydrous HF (stream
25) and an approximately 40% HF (stream 21). (United States Patent Office, E.A. Winter
1952).
144
Figure 6.2.1 Process Flow Diagram of Process 2
145
I. SUSTAINABILITY
This process employs hydrofluosilicic acid as the starting compound to
produce concentrated and/or anhydrous hydrogen fluoride (HF) and other by-
products.

Hydrofluosilicic acid ((H3O)2SiF6 or H2SiF6 in aqueous solution) is
produced as a by-product from the production of hydrogen fluoride (HF) in a
process where fluorspar is treated with sulfuric acid. It is also produced as a by-
product in plants processing superphosphate fertilizers (USGS 2015). Since
fluosilicic acid is a by-product from other processes, there are no alternative
production routes for which fluosilicic acid is the determining product. Its
production volume is fully dependent on the production volume of the
corresponding determining products (hydrogen fluoride and superphosphate
fertilizers) that drive these productions. Fluosilicic acid is formed by the reaction
of silicon tetrafluoride gas with water, as scrubbing liquid. This is to reduce the
emission of fluorine compounds before releasing it in the atmosphere. In the
Philippines, only Atlas Fertilizer Corporation manufactures superphosphate using
this process and produces 44,000 MT/year. This constitutes to almost 1,500
MT/year of fluosilicic acid need to be dispose or either sold for drinking water
fluorination, manufacture of aluminum fluoride of low bulk density, cryolite,
silicon tetrafluoride and other fluorosilicates. Therefore, we can conclude that the
supply of fluosilicic acid is insufficient to use for the production of Hydrogen
Fluoride. Also, the other raw materials such as sodium fluoride and silicon
tetrafluoride gas needed in this process are not locally available.
146
II. ECONOMICS
(Source: Alibaba.com)
Fluorosilicic 700 USD/Metric ton Php 33,390.00/ Metric ton

Acid
Sodium 750 USD/Metric ton Php 35,775.00/ Metric ton
Fluoride
Total Cost 1,450 USD/ Metric ton Php 69,165.00/ Metric ton
Estimated fixed capital cost that is needed to put up a plant that produces
Hydrogen Fluoride using Fluorosilicic Acid is calculated using the Lang
Method, factor for solids processing is 4.3 from Perrys Chemical Engineers
Handbook 8th ed.
Figure 6.2.2 Process 2 Lang Method Factors
147
Table 6.2.2 Purchase Cost of Equipment Items
Equipment Qty. Equipment Cost Fixed Capital
Cost
Filter 2 $ 200,000.00 $ 860,000.00
Dryer 2 $ 100,000.00 $ 430,000.00
Mixer 2 $ 76,000.00 $ 326,800.00
Cooler 1 $ 30,000.00 $ 129,000.00
Rectifying Column 1 $ 11,000.00 $ 47,300.00
Absorption Tower 1 $ 10,000.00 $ 43,000.00
Furnace 1 $ 80,000.00 $ 344,000.00
Calciner 1 $ 500,000.00 $ 2,150,000.00
HF Storage Tank 1 $ 11,000.00 $ 47,300.00
Fluosilicic Storage Tank 1 $ 20,000.00 $ 86,000.00
40% HF Storage Tank 1 $ 11,000.00 $ 47,300.00
Distillation Unit 1 $ 500,000.00 $ 2,150,000.00
Total Purchase Cost of 15 $ 1,549,000.00 $ 6,660,700.00
Equipment
Total in Php 73,066,330.00 314,185,219.00
TOTAL PHYSICAL PLANT 911,137,135.10

COST (PPC)
FIXED CAPITAL COST (FCC) 439,859,306.60
WORKING CAPITAL COST 21,992,965.33
TOTAL CAPITAL INVESTMENT 461,852,271.93
148
Figure 6.2.3 Typical factors for estimation of project fixed capital cost
PPC = PCE(1 + f1 + f2 + f3 + f4 + f5 + f6 + f7 )
PPC = 314,185,219.00 (1 + 0.45 + 0.45 + 0.15 + 0.1 + 0.1 + 0.45 + 0.2)
PPC = 911,137,135.10
FIXED CAPITAL COST:
FCC = PCC(1 + f10 + f11 + f12 )
FCC = 911,137,135.10 (1.40)
FCC = 439,859,306.60

WCC = FCC(0.05)
WCC = 439,859,306.60 (0.05)
149
WCC = 21,396,642.19

TCI = FCC + WCC
TCI = 439,859,306.60 + 21,396,642.19
TCI = 461,852,271.93
OPERATING TIME, PLANT ATTAINMENT

7,920
(HRS/YR)
Table 6.2.4 Fixed Cost for Process 2
FIXED COSTS
Maintenance and Repairs 39,587,337.59
Operating Labor 120,036.69
Laboratory Cost 23,161.70
Engineering and Supervision 21,919,899.00
Plant Overheads 43,139,091.30
Local Taxes 8,797,186.13
Insurance 4,398,593.07
Patent/Royal Fees 4,398,593.07
TOTAL FIXED COST 122,384,744.18
Table 6.2.5 Variable Cost for Process 2
VARIABLE COSTS
Operating Materials 5,938,100.64
Utilities (Services) 29,226,532.00
TOTAL VARIABLE COSTS 35,527,912.21
150
Table 6.2.6 Direct Production Cost for Process 2
Direct Production Cost 157,912,656.38

Sales Expense 31,582,531.28
General Overheads 47,373,796.92
Total Direct Cost 236,868,984.58
Annual Production Cost for Process 2
= + + 394,781,640.96
FIXED COST:
Maintenance and Repairs(MR) = Average process = 5 9% of fixed capital
MR = 439,859,306.60 (0.09) = 39,587,337.59
Operating Labor(OL)
0.5
N0 = (6.29 + 0.23 (16))
N0 = 3.157530681
OL = 120,036.69
151
Laboratory Cost(LC) = 10% 20% operating Labor = 120,036.69 (0.20)

= 24,007.34
Engineering and Supervision(ES) = PCE(0.30) = 73,066,330.00(0.30)

= 21,919,899.00
Plant Overheads(PO)
= Maintenance + Operating Labor + Engineering and Supervision
= 39,587,337.59 + 120,036.69 + 21,919,899.00
= 43,139,091.30
Local Tax(LT) = FCC(0.2) = 439,859,306.60 (0.2) = 8,797,186.13

Insurance(I) = FCC(0.01) = 439,859,306.60 (0.01) = 4,398,593.07
Patent/Royal Fees(P/RF) = FCC(0.01) = 439,859,306.60 (0.01)
= 4,398,593.07
= MR + OL + LC + ES + PO + LT + I + P/RF
FIXED COST = 122,384,744.18
VARIABLE COST:
Operating Materials = 15% Maintenance = 39,587,337.59 (0.15)
= 5,938,100.64
Utilities
Average services = 40%(Equipment Cost) = 29,226,532.00
= Raw Material + Operating Materials + Utilities
= 35,527,912.21
152

Sales Expense = (DPC)(0.2) = 157,912,656.38 (0.2) = 31,582,531.28
General Overheads = (DPC)(0.3) = 157,912,656.38 (0.3) = 47,373,796.92
Subtotal DP = DPC + Sales Expense + General Overhead + 157,912,656.38

+ 31,582,531.28 + 47,373,796.92 = 236,868,984.58
= FC + VC + DPC = 394,781,640.96
Product Yield:
A solution with approximately 80% HF can be fractionated to yield substantially

100% anhydrous HF and a liquid residue of 40-50% HF (Ernest A. Winter, 1952).
This process is the production of essentially silicon-free hydrofluoric acid
from hydrofluosilicic acid (H2 SiF6 ). H2 SiF6 is a by-product and is recovered from
waste gases generated in superphosphate manufacturing process. Two
disadvantages of this process are that a large volume of concentrated sulfuric
tetrafluoride is required per unit of fluosilicic acid and the splitting of the
fluosilicic acid must be carried out at relatively high temperatures. This can result
in severe corrosion of equipment. Colloidal silica is formed, which cannot be
filtered easily from sodium fluoride solution. If the pH of the second alkaline
aqueous slurry is greater than or equal to 9 or less than 7, a high percentage of the
formed silica is in solution, and thus cannot be separated from the sodium
fluoride. Furthermore, when the pH of the slurry is less than 7, the precipitated
silica is in the form of a difficult-to-filter gel. A review of this process also shows
that preparation of concentrated and/or anhydrous HF of high purity is not easy
and is quite expensive. 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
153
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 operations, an average of 1 being the lowest
difficulty in processing to 3 indicating the highest difficulty in processing.
Table 6.2.7 Equipment list for Process 2
Equipment # Equipment Equipment Name Phases Involved

Tag
2 A-100 Absorption Tower 3
4 M-100 Mixer 2
6 S-100 Filter 2
8 S-101 Dryer 2
9 E-100 Furnace 2
10 C-101 Compressor 1
11 E-101 Cooler 1
12 C-100 Compressor 1
15 M-200 Mixer 2
17 S-200 Filter 2
18 S-201 Dryer 2
19 E-200 Calciner 2
20 C-200 Calciner Gas 1
Compressor
154
21 S-202 Rectifying Column 2

22 E-201 Reboiler 2
23 T-201 40% HF Storage 1
Tank
24 E-202 Overhead Condenser 2
25 P-201 Reflux Pump (S23 1
Pump)
26 T-200 Anhydrous Hydrogen 1
Fluoride Storage
Tank
Average 1.73

There are no companies using this process in the Philippines. The two (2)
present companies are producing hydrogen fluoride from fluorspar ore using
sulfuric acid as the other raw material. The possible reason for this is the relative
unavailability of fluorosilicic acid in the Philippine market. Granted that there are
phosphate fertilizer manufacturers in the Philippines, the outlook for the market is
uncertain and the process involves more equipment as compared to the
conventional method (HF from fluorspar) for the recovery of certain intermediate
salts.
Another reason is due to difficulty of applying the material of construction

for larger sizes of a few key equipment. Some equipment that is used in the
process have to be custom made from special materials. Building these as large
single piece of equipment is expensive and increases the manufacturing time. This
prevents the construction of plants with capacities comparable to large single line
AHF plants (with fluorspar as raw material) of 53,000 ton/year (Dahlke, et al.,
2015).
155

i. Human Safety
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 and from the
information in Table 8 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 6.2.8 Toxicity Level Scores of Raw Materials

Fluorosilicic Acid Silicon Tetrafluoride
1. Severity of 4 4
Immediate Effects
2. Sensitization Level 2 3
3. Carcinogenicity 0 0
Level
4. Reproduce 0 0
Toxicity Level
5. Severity of 4 4
Chronic Effects
Subtotal 10 11
Total 21
156
Table 6.2.9 Toxicity analysis of Raw materials for Process 2
Criteria Raw Materials

Fluorosilicic Acid Silicon Tetrafluoride
1. Severity of Possibility of irritation Corrosive. May be fatal if
Immediate Effects (silicosis) by ingestion, inhaled. Depends on
inhalation, eye and skin Concentration and duration
contacts. (no experimental data yet).
Acute effects include:
coughing, shortness of
breath, headaches, vertigo,
chills and nausea.
2. Sensitization Level Irritant of the skin, eyes. Targets lungs, kidneys, liver,
Liquid or spray mist may blood, bones and teeth.
3. Carcinogenicity No data available Non-carcinogenic
Level
4. Reproduce No data available No data available
Toxicity Level Substance is toxic to the
lungs and mucous
membranes.
5. Severity of No known effects from Dental fluorosis, increased
Chronic Effects chronic exposure bone, serum and urinary
fluoride levels,
hypocalcemia, death.
157
Substances containing fluorine and silicon, which comprises dissociating

sodium silicofluoride into silicon fluoride and sodium fluoride obtaining
hydrofluosilicic acid to produce pure hydrofluoric acid and reform sodium
silicofluoride, releases large amount of emissions as evaluated in environmental
aspects. Specific high hazard areas in the manufacturing process, excluding bulk
storage and transfer include the following:
Absorption Tower
Furnace
Cooler
(2)Distillation Column
Calciner
Rectifier

This process imposes moderate level of exposure to risk and danger since
the processes and reactions involved are generally chemical and inorganic.
However, kilning may impose more explosive risks than the others. Emissions
involve SiF4 and HF gas (United States Patent E.A. Winter, 1952). The major
waste produced in this process is NaHF2 . This solid waste can pollute drinking
water and even affect human health.
158
PROCESS 3
SLURRY PROCESS FOR THE MANUFACTURE OF HDYROGEN

FLUORIDE
PROCESS DESCRIPTION
In carrying out the process of this invention in a continuous manner, 1 part of

77% through 200 mesh acid grade fluorspar (97 parts CaF2, 1 part SiO2, 1 part BaSO4
and 1 part CaCO3) is pre-mixed with 1.4 parts of 1,2,4-trichlorobenzene in M-100 and
charged as a slurry into reactor R-100. Simultaneously 99% sulfuric acid is fed to R-100
in the ratio of 2.1 parts of sulfuric acid to 1.6 parts of solid fluorspar (entering R-100 as
slurry). The reaction mass is continuously agitated and its temperature is maintained at
175C by external heat. The reaction mass is maintained at solids content of 1 part solids
(calculated as CaSO4) to 2.7 parts trichlorobenzene by introducing TCB as needed. While
maintaining the stoichiometric relationship, the reactants are added at such a rate that the
solid withdrawn from the bottom of R-100 is essentially CaSO4. Highest conversions of
the fluorspar to HF and CaSO4 are obtained when the residence time in the continuous
process is at least 0.5 hour or greater. (It should be noted that in general the finer the spar
the shorter is the residence time).
Main reaction: CaF2 + H2 SO4 CaSO4 + 2HF
Side reaction: SiO2 + 4HF SiF4 + 2H2 O
Over-all reaction: 2CaF2 + 2H2 SO4 + SiO2 2CaSO4 + SiF4 +

2H2 O
The vapor product, composed of 100 parts TCB, 17 parts HF, 0.6 part SiF 4, 0.7
part H2O and 0.04 part H2SO4, leaves R-100 at 175C and enters first scrubber A-100 and
then condenser E-100 where the bulk of the vaporized TCB condenses. Entrained solids
are removed in A-100 by scrubbing the vapor stream with the return flow from E-100;
the liquid returning to R-100 from E-100 through A-100 is essentially trichlorobenzene.
The vapor product leaving E-100 is at about 125 C and is composed of 100 parts HF, 70
159
parts TCB, 3.6 parts SiF4, 3.8 parts H2O, and 0.22 part H2SO4. In weak HF condenser
E-200, water is next removed as aqueous HF (1 part HF, 1.8 parts H 2O and 0.1 part
H2SO4) and the remaining TCB is also condensed. Separation of this two-phase
condensate takes place in decanter DC-200, the TCB being recycled to R-100. The vapor
stream, now consisting of 100 parts HF, 2.7 parts SiF4, and 0.5 part SO2, passes at 35C
to the anhydrous condenser E-201. Here the product is condensed to a liquid consisting of
100 parts HF, 0.5 part SO2 and a trace of sulfuric acid. Uncondensed gas (1 part HF and
2.6 parts SiF4) leaves E-201 at 5 C. After being contacted with water in absorber A-200
it is vented to the atmosphere.
The solid reaction products are continuously withdrawn as slurry in TCB from the
bottom of R-100 and sent to settler DC-300. In DC-300, liquid TCB is decanted from the
sludge. This recovered TCB is used to slurry more fluorspar and the excess over that
required for slurring is sent directly to R-100. Make-up TCB is added as required to keep
a constant inventory. The sludge is conveyed to dryer D-300 to vaporize its TCB content,
the TCB being returned to R-100. The residue is discharged from the D-300 at 250 C
and analyzes as 100 parts CaSO4, 1.8 parts CaF2, 0.26 part TCB, 2.65 parts H2SO4, 0.6
part BaSO4; a fluorspar conversion to HF of 98% is achieved. In general, the present
invention results in a fluorspar conversion to HF 92 to 99%, yields of HF are 90% and
above while the trichlorobenzene loss is estimated at 1 part per 100 parts of HF product.
It will be noted that the slurry of fluorspar in TCB charged to R-100 (1 part spar and 1.4
parts TCB) corresponds to about 41.7% of spar by weight of slurry. Although about 40
50% is preferred, from very dilute to 70% by weight of spar can be employed. It will also
be noted that the solid content as CaSO4, in the reactor is maintained at about 1 part per
2.7 parts TCB which corresponds to about 27% CaSO4, by weight throughout the
reaction mass. Higher percentagesup to 60% can be readily withdrawn from the
bottom of R-100 in a continuous manner. The reaction temperature can be varied from
100 to 200 C, with a temperature of at least 150 C preferred. (C. Y. Jesse, 1958)
160
Figure 6.3.1 Process Flow Diagram of Process 3
161
I. SUSTAINABILITY
This process proposed an easy and rapid way to produce hydrofluoric
acid at low temperatures in simplified equipment by incorporating the use of
inert diluent 1,2,4trichlorobenzene (TCB). The inert diluent serves as a heat
transfer agent for the reaction by allowing efficient mixing of reactants and
aiding dispersion of fluorspar solid particles. Raw materials are sulfuric acid
(H2SO4), acid-grade fluorspar and TCB. H2SO4 is readily available in the
market but the other two materials are not. It will be challenging to adopt this
process because of the raw materials availability.

The raw materials for this process include H2SO4, acid-grade fluorspar
and TCB. Availability of H2SO4 is presented below using local demand and
supply diagram but theres no data available for the other two raw materials
since both are not locally available which means that theres neither
manufacturer nor distributor in the country.
i. Sulfuric Acid
Supply of H2SO4 in the Philippines is quite large and many
manufacturing companies are producing this product in the country such as
Emerald Chemicals, Inc. (ECI), LMG Chemicals Corporation, Chemphil
Manufacturing Corporation, and etc. From fig. 3.1.1, it can be seen that the
supply of H2SO4 is relatively high as to compare with that of demand. Amount
of supply in the year 2014 is almost 20,000 tons per year while its demand is
just 2,000 tons per year. Therefore, supply of H2SO4 in the country is enough
to satisfy the need in the process.
162
30,000,000
25,000,000
20,000,000 19,749,558.49
15,000,000 Demand
Supply
10,000,000
5,000,000
1,698,033
0
2004 2006 2008 2010 2012 2014 2016
Fig. 6.3.2 Historical Supply and Demand of H2SO4 in the Philippines
i. Metallurgical-grade Fluorspar
Despite having the supply for acid-grade fluorspar in the Philippines

relatively scarce compared to other countries, a certain company in the
Philippines called Palcer Trading International or PTI Philippines offers a stable
supply for metallurgical fluorspar (fluorspar ore with around 80-85% of CaF2 by
weight). The table below shows the specifications of the above companys
fluorspar product.
Table 6.3.1 PTI Philippines Fluorspar Specifications

(Source: www.ptiphilippines.wordpress.com)
Specifications
CaF2 85% min.
SiO2 14% min.
Size 10-50 mm
163
Packing 1 MT bags containerized
20 MT per container
Another company that can supply metallurgical grade fluorspar in the Philippines
is MH Fair Bridge, Inc. with the following product specifications:
Table 6.3.2 MH Fair Bridge, Inc. Fluorspar Specifications

Specifications
CaF2 80% min.
(Source:
SiO2 www.alibaba.com)
17% max.
Size 10-50 mm
Packing 1 MT jumbo bags
The supply and demand of fluorspar in the Philippines is shown below.
Projected Demand and Supply of Fluorspar

2,500,000
2,000,000
1,500,000
1,000,000
500,000
0
2016 2018 2020 2022 2024 2026 2028
Projected Demand (AGCM) Projected Supply (ASLM)
Figure 6.3.3 Projected Demand and Supply of Fluorspar
164
A process called Fluorspar Beneficiation will be implemented by HydroFluor

Philippines in order to upgrade this metallurgical-grade fluorspar supply to acid-grade
fluorspar.
II. ECONOMICS

Sulphuric Acid 260 USD/Metric ton Php 12,848.94/ Metric

ton
Fluorspar 380 USD/ Metric ton Php 18,779.22/ Metric
ton
1,2,4- 2,500 USD/ Metric Php 117,925.00/ Metric
Trichlorobenzene ton ton
Estimated fixed capital cost that is needed to put up a plant that produces
Hydrogen Fluoride using Fluorosilicic Acid, Sulphuric Acid, and
Trichlorobenzene is calculated using the Lang Method, factor for solids
processing is 4.3 from Perrys Chemical Engineers Handbook 8th ed.
Figure 6.3.4 Process 3 Lang Method Factors
165
Table 6.3.5 Purchase Cost of Equipment Items
Equipment Qty. Equipment Cost Fixed Capital Cost
Sulfuric Acid Storage Tank 1 $ 11,000.00 $ 47,300.00
TCB Storage Tank 1 $ 11,000.00 $ 47,300.00
Fluorspar Storage Tank 1 $ 11,000.00 $ 47,300.00
Dryer 1 $ 50,000.00 $ 215,000.00
Reactor 1 $ 200,000.00 $ 860,000.00
Scrubber 1 $ 50,000.00 $ 215,000.00
Condenser 3 $ 60,000.00 $ 258,000.00
Decanter 1 $ 90,000.00 $ 387,000.00
Absorption Tower 1 $ 20,000.00 $ 86,000.00
Settler 1 $ 18,000.00 $ 77,400.00
Aqueous HF Storage Tank 1 $ 11,000.00 $ 47,300.00
HF Storage Tank 1 $ 11,000.00 $ 47,300.00
Pre-mixer of Fluorspar and 1 $ 11,000.00 $ 47,300.00

Slurry
Water Storage Tank 1 $ 11,000.00 $ 47,300.00
CaSO4 Residue Storage 1 $ 11,000.00 $ 47,300.00

Tank
Total Purchase Cost of 14 $576,000.00 $2,476,800.00
Equipment
Total in Php 27,169,920.00 116,830,656.00
166
TOTAL PHYSICAL PLANT COST , , .

(PPC)
FIXED CAPITAL COST (FCC) , , .
WORKING CAPITAL COST , , .
TOTAL CAPITAL INVESTMENT , , .
PPC = PCE(1 + f1 + f2 + f3 + f4 + f5 + f6 + f7 )
PPC = 116,830,656.00(1 + 0.45 + 0.45 + 0.15 + 0.1 + 0.1 + 0.45 + 0.2)
PPC = 338,808,902.4
FIXED CAPITAL COST:
FCC = PCC(1 + f10 + f11 + f12 )
FCC = 338,808,902.40 (1.40)
FCC = 474,332,463.40

WCC = FCC(0.05)
WCC = 474,332,463.40 (0.05)
WCC = 23,716,623.17

TCI = FCC + WCC
TCI = 474,332,463.40 + 23,716,623.17
TCI = 498,049,086.6
167
Figure 6.3.5 Typical factors for estimation of project fixed capital cost
OPERATING TIME, PLANT ATTAINMENT 7,920

(HRS/YR)
Table 6.3.6 Fixed Cost for Process 3
FIXED COSTS
Maintenance and Repairs , , .
Operating Labor , .
Laboratory Cost , .
Engineering and Supervision , , .
Plant Overheads , , .
Local Taxes , , .
Insurance , , .
Patent/Royal Fees , , .
168
TOTAL FIXED COST , , .

VARIABLE COSTS
Operating Materials , , .
Utilities (Services) , , .
TOTAL VARIABLE COSTS , , .
Direct Production Cost , , .

Sales Expense , , .
General Overheads , , .
Total Direct Cost , ,
= + + , , .
FIXED COST:
Maintenance and Repairs(MR) = Average process = 5 9% of fixed capital
MR = 474,332,463.40 (0.09) = 42,689,921.71
Operating Labor(OL)
169
0.5
N0 = (6.29 + 0.23 (11))
N0 = 3.083828789
OL = 117,234.84
Laboratory Cost(LC) = 10% 20% operating Labor
= 117,234.84 (0.20)
= 23,446.97
Engineering and Supervision(ES) = PCE(0.3)

= 27,169,920.00 (0.3)
= 8,150,976.00
Plant Overheads (PO)
= (Maintenance + Operating Labor + Engineering and Supervision) 0.7
= (42,689,921.71 + 117,234.84 + 8,150,976.00 ) 0.7
= 35,670,692.79
Local Tax(LT) = FCC(0.2)
= 474,332,463.40 (0.2)
= 94,866,492.68
Insurance(I) = FCC(0.01)
= 474,332,463.40 (0.01)
= 4,743,324.634
Patent/Royal Fees(P/RF) = FCC(0.01)
= 474,332,463.40 (0.01)
= 4,743,324.634
FIXED COST = MR + OL + LC + ES + PO + LT + I + P/RF

FIXED COST = 191,005,414.30
170
VARIABLE COST
Operating Materials = 15% Maintenance

= 42,689,921.71 (0.15)
= 6,403,488.257
Utilities
Average services = 40%(Equipment Cost) = 10,867,968.00
VARIABLE COST = Raw Material + Operating Materials + Utilities

= 17,801,531.02
Sales Expense = (DPC)(0.2) = 208,806,945.3 (0.2)
= 41,761,389.06
General Overheads = (DPC)(0.3) = 208,806,945.3 (0.3)
= 62,642,083.6
Sub total DPC = DPC + Sales Expense + General Overheads
= 208,806,945.3 + 41,761,389.06 + 62,642,083.6
= 313,210,418
= FC + VC + DPC = 522,017,363.3
171
The process is operating at mild conditions, so the tendency for equipment
damage is less. And theres a relatively high efficiency in heat transfer and mixing
of reactants due to the inert diluent, therefore, the design of equipment will just be
simple and less costly. But it is also observed that most of the equipment is for the
recovery of inert diluent which is more than that of the equipment required for the
product recovery, so theres a problem in the cost-effectiveness of this process
with regards to the over-all list of equipment that will be used in the process. List
of equipment shown in the table below shows the list of major equipment that are
required to run the plant. 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
operations, an average of 1 being the lowest difficulty in processing to 3
indicating the highest difficulty in processing.
Table 6.3.7 Phases Involved for Each Equipment
Equipment Equipment Equipment Name Phases

# Tag Involved
1 R-100 Reactor 3
2 A-100 Scrubber 3
3 E-100 TCB Condenser 2
4 T-100 Storage Tank of Sulfuric 1
Acid
5 T-101 Storage Tank of Fluorspar 1
6 T-102 Storage Tank of TCB 1
7 M-100 Pre-mixer of Fluorspar and 2
Slurry
8 E-200 Weak HF Condenser 2
172
9 DC-200 Weak HF Decanter 1

10 T-200 Storage Tank of Aqueous 1
HF
11 E-201 HF Condenser 2
12 T-201 Storage Tank of 1
Anhydrous HF
13 A-200 Absorber 2
14 T-202 Storage Tank of Water 1
15 DC-300 Settler 2
16 D-300 Dryer 2
17 T-300 Storage Tank of CaSO4 1
Residue
Average Number of Phases 1.65

There are no companies using this process in the Philippines. The two (2)
present companies are producing hydrogen fluoride from fluorspar ore using
sulfuric acid as the other raw material. Possible reason is the unavailability of
1,2,4-Trichlorobenzene (TCB) in the Philippines. Cost-effectiveness of this
process is doubtful because most of the equipment used are for the recovery of the
TCB alone and selling price of TCB is very high.

i. Human Safety
Toxicity level of raw materials is analyzed, which may be seen in table
3.5.1, which is based on table 3.5.2 which gives the corresponding health hazards
that it may cause to humans. Scores in table 3.5.1 was made by rating the level of
toxicity in table 3.5.2 by 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
173
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 6.3.8 Toxicity Level Scores of Raw Materials

Fluorspar Sulfuric TCB
Acid
1. Severity of Immediate 2 4 4
Effects
2. Sensitization Level 3 2 4
3. Carcinogenicity Level 0 3 0
4. Reproduce Toxicity Level 0 1 0
5. Severity of Chronic 0 4 4
Effects
Subtotal 5 14 12
Total 31
174
Table 6.3.9 Basis of Toxicity Level Scores

(from MSDS ScienceLab and Laguna Clay Company)
Fluorspar Sulfuric Acid TCB
1. Severity of Possibility of Causes severe Very hazardous in

Immediate Effects irritation skin, eye and case of ingestion,
(silicosis) by respiratory tract of inhalation.
ingestion, irritation and
inhalation, eye burns. Harmful if
and skin swallowed. May
contacts. cause permanent
damage to the
digestive tract
2. Sensitization Level Possibility of Found to be Extremely

Irritation sensitizer of skin hazardous in case
and eye of skin contact
(irritant,
permeator), of eye
contact (irritant).
3. Carcinogenicity Calcium Carcinogenic to Not listed as a
Level Carbonate; man, causing carcinogen by
calcium fluoride cancer of the ACGIH, IARC,
not a carcinogen larynx (the voice NTP, or CA
box). Prop 65.
4. Reproductive Non-mutagenic Slightly Not available

Toxicity Level embryotoxic.
5. Severity of No known Prolonged or Can cause

Chronic Effects effects from repeated gastrointestinal
chronic inhalation may disturbances.The
exposure affect behavior substance is toxic
muscle to blood, kidneys,
contraction , liver, upper
urinary system respiratory tract.
kidney damage,
and
cardiovascular
175
system, heart,
and respiratory
system/lungs ,
teeth (dental
discoloration,
erosion).
Presence of an inert diluent utilized to transfer heat in the reaction of sulfuric

acid caused specific high hazard areas in the manufacturing process; excluding
bulk storage and transfer include the following:
Reactor
Scrubber
(3) Condensers
Absorber

This process gives just a moderate hazard in the environment since the
gaseous products containing SiF4 and HF are first treated in a gas absorber in
order to abide with the rules regarding emission of hazardous gases.
176
Table 6.4.1. Summary Evaluation of the Three Processes
ATTRIBUTES Process 1: Process 2: Process 3:

Production of Process for Slurry Process for the
Hydrogen Fluoride Producing Manufacture of
from Fluorspar Essentially Silicon Hydrogen Fluoride
Free Hydrofluoric
Acid from
Hydrofluosilicic
Acid
ECONOMICS
Fixed Capital Cost 270,319,672.00 439,859,306.60 474,332,463.40
Annual Production 216,609,641.7 394,781,640.96 522,017,363.30
Cost
MANUFACTURABILITY
Efficiency Conversion levels at Conversion levels at Conversion levels at
about 90-98% about 90%; Molar about 92-99%; Molar
(Boscak); Molar Yield: 50% (E.A. yields 90%; (J.C.
yields 90% based on Winter, 1952) Yacoe, 1958 )
Fluorspar and 80%
on Sulfuric acid
(Kirk-Othmer,
Pinger)
Average Number of 1.38 1.73 1.65
Phases
(Solid, liquid, and gas are the
phases involved in processing.
The presence of more than 1
phase makes the process
more complex and would
translate to higher operation
cost. The average number of
phases indicates the number
of phases processed per
equipment, a lower value
would mean lower operation
cost. With 3 being the highest
177
and 1 as the lowest).
SUSTAINABILITY
Availability of Raw The supply of Insufficient supply The supply of
Materials fluorspar and sulfuric of fluorosilicic acid fluorspar and sulfuric
acid is sufficient in the Philippines. acid is sufficient
enough to satisfy the enough to satisfy the
requirements of the SiF4 and NaF are requirements of the
process. not locally process.
available.
1,2,4-
trichlorobenzene not
available in the
Philippines.
ENVIRONMENTAL ASPECT
Emission of Wastes The main wastes are The main wastes The main wastes are
SiF4 and HF. As per are SiO2 and NaHF2 SiF4 and HF. As per
R.A. 8749, contaminant of R.A. 8749, maximum
maximum allowable ground water allowable
concentration for HF systems. concentration for HF
and related fluorine and related fluorine
compounds is 50 compounds is 50
3
mg/normal m . mg/normal m3.
178
Table 6.4.2. Summary of Scores of the Evaluation of Three Processes
ATTRIBUTES Importance SCORE SCORE x Level OVERALL SCORE

Level
P1 P2 P3 P1 P2 P3 P1 P2 P3
ECONOMICS
FCC 5 5 3.07 2.85 25 15.36 14.25 25 14.54 12.31
APC 5 2.74 2.07 25 13.72 10.37
MANUFACTURABILITY
Efficiency 3 4.92 4.71 5 14.76 14.14 15 14.88 13.05 13.77
Average 5 3.99 4.18 15 11.96 12.54
Number of
Phases
SUSTAINABILITY
Availability 4 5 0 3.33 20 0 13.33 20 0 13.33
of Raw
Materials
ENVIRONMENTAL ASPECT
Emission of 3 5 5 5 15 15 15 15 15 15
Wastes
TOTAL 74.88 42.59 54.42
CONCLUSION
Table 4.2 shows the summary of scores for the evaluation of the three
processes. Based on the scores obtained, Process 1 which is Continuous Production of
Anhydrous Hydrogen Fluoride from Fluorspar is the most favorable compared to the
two processes discussed.
179

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Technological Institute of the Philippines

PRODUCTION OF ANHYDROUS HYDROGEN FLUORIDE

Hydrogen fluoride has a number of properties that distinguish it from the

Hydrogen fluoride is produced commercially by heating purified fluorspar

Hydrogen fluoride is available commercially either in an anhydrous (water-free)

Hydrogen fluoride is used in the production of aluminum and

Hydrogen fluoride is primarily used to make fluorinated compounds such as

Hydrofluoric acid is used in the manufacture of elemental fluorine gas which in

HF serves as a catalyst in alkylation processes in oil refineries. A component of

HF is a reactive solvent in the electrochemical fluorination of organic compounds. In this

Hydrogen fluoride is an important catalyst used in the majority of the

CONTINUOUS PRODUCTION OF ANHYDROUS HYDROGEN FLUORIDE

Figure 6.1.1. Process Flow Diagram of Process 1

Availability of Raw Materials

i. Fluorspar Supply in the Philippines

Despite having the supply for acid-grade fluorspar in the Philippines

Table 6.1.1 PTI Philippines Fluorspar Specifications

CaF2 85% min.

SiO2 14% min.

Packing 1 MT bags containerized

Table 6.1.2 MH Fair Bridge, Inc. Fluorspar Specifications

SiO2 17% max.

Packing 1 MT jumbo bags

The supply and demand of fluorspar in the Philippines is shown below.

Projected Demand and Supply of Fluorspar

Projected Demand (AGCM) Projected Supply (ASLM)

Figure 6.1.2 Projected Demand and Supply of Fluorspar

A process called Fluorspar Beneficiation (process of upgrading the grade of

ii. Sulphuric Acid supply in the Philippines

Figure 6.1.3 Demand and Supply of Sulfuric Acid

Table 6.1.3 Market Price of Raw Materials

Sulphuric Acid 260 USD/Metric ton Php 12,848.94/ Metric ton

Fluorspar 380 USD/ Metric ton Php 18,779.22/ Metric ton

Total Php 31,628.16/ Metric ton

ii. Cost of Equipment

Table 6.1.4 Process 1 Lang Method Factors

(Source: Coulson and Richardson, Chemical Engineering Design, Volume 6)

Item Process Type

f1 Equipment erection 0.4 0.45 0.50

2. Total Physical Plant

Cf= fixed capital cost

Ce= total cost of all major equipment items

fL= the Lang factor, which depends on the type of process

Table 6.1.6 Fixed Capital Cost per Equipment

Equipment Qty. Equipment Cost Fixed Capital

Classifier 1 $ 20,000.00 $ 86,000.00

Rotary Drum Filter 1 $ 3,000.00 $ 12,900.00

Acid Scrubber 1 $ 7,000.00 $ 30,100.00

Flash Distillation Column 1 $ 50,000.00 $ 215,000.00

tank 2 $ 5,000.00 $ 21,500.00

Oleum Tank 1 $ 5,000.00 $ 21,500.00

PPC Physical Plant Cost 185,492,733.9

TOTAL PHYSICAL PLANT COST (PPC)

PPC = 63,963,011.7(1 + 0.45 + 0.45 + 0.15 + 0.1 + 0.1 + 0.45 + 0.2)

FIXED CAPITAL COST:

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

WORKING CAPITAL COST (WCC):

TOTAL CAPITAL INVESTMENT (TCI):

OPERATING TIME, PLANT ATTAINMENT

Direct Production Cost 157,588,638.5

Maintenance Cost = 0.10 (FCC)

Maintenance Cost = 0.10 (259,689,827.5 )

Maintenance Cost = 25,968,982.75