CHAPTER I

PROJECT CONCEPTION-LITERATURE REVIEW

1.1 Process Background

1.1.1 Introduction

Bromine (from Gr. Bromos, meaning "stench"), is a chemical element in the

periodic table that has the symbol Br and atomic number 35. A halogen element,
bromine is a red volatile liquid at room temperature which has a reactivity between
chlorine and iodine. Bromine is so similar in its chemical properties to chlorine, with
which it is almost invariably associated, that it was not recognized as a separate
element until 1826, when it was discovered and isolated by the French chemist
Antoine Jérôme Balard. This element is harmful to human tissue in a liquid state and
its vapour irritates eyes and throat.
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Figure 1.1 The Table of Elements

Bromine is the only liquid nonmetallic element at room temperature. It is a

heavy, mobile, reddish-brown liquid, that evaporates easily at standard temperature
and pressures in a red vapor (its color resembles nitrogen dioxide) that has a strong
disagreeable odor. A halogen, bromine resembles chlorine chemically but is less
active (it is more active than iodine however).

Figure 1.2 Bromine

Bromine is highly reactive and is a powerful oxidizing agent in the presence

of water. It reacts vigorously with amines, alkenes and phenols as well as aliphatic
and aromatic hydrocarbons, ketones and acids (these are brominated by either
 3

addition or substitution). With many of the metals and elements, anhydrous bromine
is less reactive than wet bromine; however, dry bromine reacts vigorously with
aluminium, titanium, mercury as well as alkaline earth and alkaline metals.

1.1.2 Physical and Chemical Properties of Bromine

Bromine is widely distributed in nature. It melts at -7.25° C (18.95° F), boils

at 58.78° C (137.8° F), and has a specific gravity of 3.10; the atomic weight of the
element is 79.90. Bromine is slightly soluble in water, 100 parts of the latter
dissolving about 4 parts of bromine when cold or 3 parts when hot; at temperatures
below 7° C (44° F) it forms with water a solid, reddish hydrate, Br 2·10H2O. In the
presence of alkalies, bromine reacts chemically with water to yield a mixture of
hydrobromic acid (HBr), and hypobromous acid (HOBr). Bromine is very soluble in
a wide variety of organic solvents, such as alcohol, ether, chloroform, and carbon
disulfide. It reacts chemically with many compounds and metallic elements and is
slightly less active than chlorine.

The physical and chemical properties of bromine is shown as in Table 1.1.

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Table 1.1 : Physical and Chemical Properties of Bromine

selenium – bromine – krypton

Cl
Br
I  
 
 

General
Name, Symbol, Number bromine, Br, 35
Series halogens
Group, Period, Block 17 (VIIA), 4, p
Atomic weight 79.904 amu
Density, Hardness 3119 kg/m3 (300 K), NA

Gas: red-brown
Appearance solid: metallic luster

Physical properties
solid at STP, liquid at
State of matter
room temp (nonmagnetic)
Melting point 265.8 K (19 °F)
Boiling point 332 K (138 °F)
Molar volume 19.78 ×10-6 m3/mol
Chemical properties
Heat of vaporization 15.438 kJ/mol
Heat of fusion 5.286 kJ/mol
Vapor pressure 5800 Pa at 280.1 K
Specific heat capacity 480 J/(kg*K)
Thermal conductivity 0.122 W/(m*K)
 5

1.1.3 Discovery and History

The discovery of the bromine is credited to Antoine Balard in 1826 in the

course of studying the mother liquor remaining after the crystallization of salt from
the water of the Montpellier salt-marshes, which is rich in the magnesium bromide.
Balard was attracted by the intense yellow coloration which developed when chlorine
water was added to the liquor; ether-extraction followed by treatment with potassium
hydroxide destroyed the colour, while the residue was shown, when heated with
manganse dioxide and sulphuric acid, to produce red fumes which condensed to a
dark brown liquid with an unpleasant smell.

There is no question but that the element had been isolated by Joss and by
Liebig prior to Balard’s discovery; however, neither of these investigators recognized
the true nature of their product, Joss mistaking it for selenium and Liebig for iodine
chloride. On the other hand, Balard was unquestionably the first to appreciate the
elemental nature of the aterial and its relation to chlorine and iodine. The substance
was first called muride, but the name bromine-from Greek, a stench was prefered
later.

Bromine was not produced in quantity until 1860.

1.1.4 Occurrence
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Bromine does not occur in nature as a free element, but is found in bromide
compounds. It was formerly a by-product of the production of common salt or of
potassium from brines rich in bromides. Elemental bromine can be prepared from
bromides by treatment with manganese dioxide or sodium chlorate. Increasing
demand has led to the production of bromine from seawater, which contains on the
average 65 parts of bromine per million.

The largest natural source of bromine is the sea; out of a total average salinity
of about 34%, sea water contains approximately 19% chlorine, mainly as sodium
chloride though with smaller amounts of other chlorides, 0.0065% bromine
(representing a chlorine:bromine mass ratio of nearly 300:1) and 5x10-8% iodine.

The bromine occurrence from natural source is shown in Table 1.2 and Table
1.3.

Table 1.2 : Natural Source of Bromine in Sea

Original content, g/L After concentration,

g/L.

Sea water 0.065

Inland seas
Kharaghoda, Indian Ocean 0.25 6
Sassyksee, Black Sea 0.28 1.5 to 4.5
Shebhka el Melah, Tunisia 2.5 6.8

Salt lakes 12 to 13 

Dead Sea, Israel 4 to 6
Ellon Sea, USSR 0.63 to 2.25
Searles Lake, Calif (USA) 0.85

Brine wells
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Michigan (USA) 2 to 3
Arkansas, (USA) 4 to 5
Yakutsk, Siberia, USSR 6 to 7 (CaCl2 solution)

Table 1.3 : Bromine in Other Natural Source

Mineral salt deposits wt%

Tachydrite 0.438

Rock salt 0.005 to 0.040

Sylvite 0.117 to 0.300

Carnallite 0.155 to 0.0334

Bischofit 0.467

Hard salt 0.05 to 0.20

The Dead Sea is one of the richest sources, containing nearly 4 grams per liter
of bromine at the surface and up to 6 grams per liter at deeper levels. 

The most important source of bromine today is brine wells, which is the
principal source in the United States. The richest brines are found in Arkansas and
Michigan in USA, with bromine content ranging from 2 to 5 grams per
liter. Approximately 500 million kilograms ($350 million USD) of bromine are
produced per year (2001) worldwide with the United States and Israel being the
primary producers.

1.1.5 Formation of Bromine

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In an analogous manner, bromine is liberated from hydrogen bromide, metal

bromides or solutions of these by oxidation with reagents such as manganese dioxide,
nitric acid or bromates. The Deacon Process of air-oxidation is applicable to the
conversion of hydrogen bromide to bromine, as is electrochemical oxidation of
bromide ions. But the only methods of importance for the manufacture of bromine
are based on the oxidation of bromide-containing solutions by chlorine.

2Br - + Cl2 Br2 + 2Cl-

1.1.6 Applications

Elemental bromine is used to manufacture a wide variety of bromine

compounds used in industry and agriculture.

(i) Traditionally the largest use of bromine was in the production of

1,2-dibromoethane which in turn was used as a gasoline anti-knock
agent for leaded gasolines before they were largely phased out due to
environmental considerations.
(ii) Manufacture of fire-extinguishing agents, e.g. CH2ClBr and CF2Br2
and of flame retardants for incorporation in polymers such as
polystyrene, e.g. CH2Br[CHBr]2CH2Br, BrCl2C·CCl2Br,
pentabromochlorocyclohexane and
tetrabromoisopropylidenebisphenol.
(iii) The production of organic derivatives such as methyl bromide,
ethylene dibromide and bromochloropropanes for insect control, as
space and soil fumigants and fungicides.
(iv) Formation of industrial organic intermediates, dyestuffs, medical
chemicals and solvents, e.g. bromoanthraquinomers, bromopthaleins,
CF3CHBrCl (‘halothane’) and mercurochrome.
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(v) One of the major uses of bromine is a water purifier/disinfectant, as an

alternative to chlorine. Brominated compounds are used for water
treatment in swimming pools and hot tubs and are also used to control
algae and bacterial growth in industrial processes.
(vi) Production of organic liquids of high density for gauge fluids and
gravity separations processes, e.g. CBr4, CHBr3, CH2Br2,
Br2CH·CHBr2, BrCH2CH2Br and C6H5Br.
(vii) Production of inorganic bromides and bromates: AgBr, central to
photography; alkali bromides used as mild sedatives; with aqueous
hypochlorite bromide gives a solution containing hydrobromide useful
for bleaching and for desizing cotton; hydrogen bromide, used as a
ctalyst, e.g. in alkylation reactions; bromates, used as oxidants for
improving the baking quality of wheat flour, in certain hair-wave
preparations, and during the malting process in the brewing industry.
(viii) A key use of bromine compounds is in the manufacture of
pharmaceuticals. Brominated substances are important ingredients of
many over-the-counter and prescription drugs, including analgesics,
sedatives, and antihistamines. Some of the drugs have also proved
effective in the treatment of pneumonia, and cocaine addiction.
Currently, pharmaceuticals, that use bromine compounds in their
manufacture, are undergoing trials for treatment of Alzheimer’s
disease, and new generations of anti-cancer and AIDS drugs.
(ix) Bromine is used to make brominated vegetable oil, which is used as
an emulsifier in many citrus-flavored soft drinks.

1.1.7 Sensitivity Data

Elemental bromine is a strong irritant and in concentrated form, will produce

painful blisters on exposed skin and especially mucous membranes. Lacrimation
occurs at less than 1 ppm and respiratory damage occurs at 10 ppm. Even low
 10

concentrations of bromine vapor (from 10 ppm) can affect breathing and inhalation
of significant amounts of bromine can seriously damage the respiratory system.
Liquid bromine penetrates the tissue rapidly and produces eruptions, irritations, and
painful injuries which heal slowly. Irritating concentration is 2.10 mg/cu m.
Accordingly, one should always wear safety goggles and ensure adequate
ventilation when handling bromine.

1.1.8 Health Effects of Bromine

Bromine is a naturally occurring element that can be found in many inorganic

substances. Humans however, have many years ago started the introduction of
organic bromines in the environment. Theses are all of them compounds that are not
natural and can cause serious harm to human health and the environment.

Humans can absorb organic bromines through the skin, with food and during
breathing. Organic bromines are widely used as sprays to kill insects and other
unwanted pests. But they are not only poisonous to the animals that they are used
against, but also to larger animals. In many cases they are poisonous to humans, too.

The most important health effects that can be caused by bromine-containing

organic contaminants are malfunctioning of the nervous system and disturbances in
genetic materials. But organic bromines can also cause damage to organs such as
liver, kidneys, lungs and milt and they can cause stomach and gastrointestinal
malfunctioning. Some forms of organic bromines, such as ethylene bromine, can
even cause cancer.
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Inorganic bromines are found in nature, but whereas they occur naturally
humans have added too much through the years. Through food and drinking water
humans absorb high doses of inorganic bromines. These bromines can damage the
nervous system and the thyroid gland.

1.1.9 Environmental Effects of Bromine

Organic bromines are often applied as disinfecting and protecting agents, due
to their damaging effects on microorganisms. When they are applied in greenhouses
and on farmland they can easily rinse off to surface water, which has very negative
health effects on daphnia, fishes, lobsters and algae.

Organic bromines are also damaging to mammals, especially when they

accumulate in the bodies of their preys. The most important effects on animals are
nerve damage and next to that DNA damage, which can also enhance the chances of
development of cancer.

The uptake of organic bromine takes place through food, through breathing
and through the skin.

Organic bromines are not very biodegradable; when they are decomposed
inorganic bromines will consist. These can damage the nerve system when high
doses are absorbed.

It has occurred in the past that organic bromines ended up in the food of
cattle. Thousands of cows and pigs had to be killed in order to prevent contagion of
humans. The cattle suffered from symptoms such as liver damage, loss of sight and
depletion of growth, decrease of immunity, decreasing milk production and sterility
and malformed children.
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Escape of bromine into workplace air is main toxic hazard during production.
The most common cause of bromism (a condition associated with excessive tissue
levels of bromide ions) is the abuse of bromide containing patent medicines, although
occupational exposure and ingestion of well water with high bromide levels may also
lead to the onset of the condition.

1.2 Market Survey

1.2.1 Global Scenario

1.2.1.1 Global Demand

The present global demand for bromine is estimated to be around annual

500,000 ton per annum. The annual growth rate in demand is estimated to be around
3% per year.

The Table 1.4 below shows the demand of bromine in Unites State.

Table 1.4 : Demand of Bromine in United State

Year Demand for Bromine (million pounds)

1996 494

1997 545
 13

1998 510

1999 525

2000 515

2001 480

2003 527

Demand of Bromine

550
Demand (millions of

540
530
pounds)

520
510
500
490
480
470
1994 1996 1998 2000 2002 2004
Year

Figure 1.3 Demand of Bromine in United State

1.2.1.2 Producers of Bromine

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Three large companies, the Great Lake Chemical Corporation and the
Albermarle Corporation in America, and the Dead Sea Bromine Group in Israel, are
responsible for about 80 % of the world production of bromine. Extraction in the
USA is from brines, while in Israel extraction is from the Dead Sea.

The leading producers of brominated flame retardants and their market shares
are shown in Table 1.5.

Table 1.5 : Leading Producers of Brominated Flame Retardants

Producers Market Share

Great Lakes Chemical Corp. 31%

Albemarle Corp. 23%

Dead Sea Bromine Co. Ltd 22%

Others 24%

International distribution of bromine production for 2000 was estimated to be

as shown in Figure 1.4.
 15

Distribution of Bromine Production

for 2000

United State
5% 6%
9% Israel
45%
China
United Kingdom
35%
Others

Figure 1.4 Distribution of Bromine Production for 2000

The Great Lake Chemical Corporation has plants in the USA and England,
the Albermarle Corporation has plants in the USA, France and Jordan. The Dead Sea
Bromine Group has plants in Israel, Holland and China. Trade in flame retardants is
on an international scale, and there are many companies involved in the handling of
flame retardants.

Albemarle operates two plants at the Magnolia site. Albemarle is nearing the
completion of a joint-venture bromines complex under construction at Safi, Jordan.
The project, called Jordan Bromine Co. Ltd., is half owned by Albemarle. The JV
includes a 50,000-metric-ton-per-year bromine plant, scheduled to start-up in
December. Also included are units for tetrabromobisphenol-A (TBBA) and calcium
bromide.

Great Lakes Chemical has three plants at El Dorado: South Plant, 125 million
pounds; Central Plant, 80 million pounds; and the Newell Plant, 55 million pounds.
The Newell Plant, however, is presently idled due to economic conditions in the
 16

industry. Great Lakes has another 88 million pounds of bromine capacity at Amlwch,
Wales.

Tetra Technologies (The Woodlands, Tex.) takes all of coproduct bromine

produced at Dow Chemical’s calcium and magnesium operations at Ludington,
Mich. Tetra consumes this in the production of bromine derivatives.

Ambar Chemical ceased production at their 30 million-pound capacity plant

in Manistee, Mich., in 2000.

1.2.1.3 Production of Bromine

United State is the major world producer of bromine followed by Israel.

Three bromine companies accounted for 64% of world production. Two of these
companies are located in the United States and accounted for about 94% of U.S.
production. Legislation during the 1970’s and 1980’s reduced the traditional demand
for bromine as a gasoline additive and in agriculture, but new end uses in specialized
flame retardant chemicals have demanded increasing amounts of bromine.

Israel is the second largest producer of bromine in the world and the largest
producer of elemental bromine. Approximately 90% of production was for export,
accounting for about 80% of international trade in bromine and bromine compounds
to more than 100 countries. A company produced bromine from Dead Sea bromine-
rich brines after production of potash. Exports of elemental bromine are produced
into compounds at a wholly owned plant in the Netherlands. Israel has been able to
increase its production substantially from 23,000 ton in 1976 to around 200,000 ton
 17

per annum at present due to the avaibility of the rich source of bromine, i.e., Dead
Sea Brine and its concentrates and the process innovations brought about by the
technologies.

Table 1.6 shows the capacity of production of several producer in year 2002.

Table 1.6 : Capacity of Production

Producers Capacity*

Albemarle, Magnolia, Ark. 310

Dow Chemical, Ludington, Mich. 25

Great Lakes Chemical, El Dorado, Ark. 260

Great Lakes Chemical, Marysville, Ark. 130

Total 725

*Millions of pounds per year of elemental bromine (2002). Commercial production is

by heating sodium bromide containing brines and oxidizing to elemental form with
chlorine. Crude bromine is then stripped from solution with either steam or air.

Table 1.7 shows the world production (ton/year) of bromine according to the
land in world.

Table 1.7 : World Production (ton/year) of Bromine

Land 1996 1997 1998 1999 2000

Azerbajdzan 2 000 2 000 2 000 2 000 2 000

China 41 400 50 100 40 000 42 000 45 000

France 2 000 2000 2 000 2 000 2 000

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India 1 500 1 500 1 500 1 500 1 500

Israel 160 000 180 000 185 000 185 000 185 000

Italiy 300 300 300 300 300

Japan 15 000 20 000 20 000 20 000 20 000

Spain 100 100 100 100 100

Turkmenistan 100 150 150 150 150

Ukraine 3 000 3 000 3 000 3 000 3 000

Great Britain 30 600 35 600 35 900 55 000 55 000

USA 227 000 247 000 230 000 239 000 228 000

Total 483 000 542 000 520 000 550 000 542 000
1.2.2 Malaysia Scenario

In Malaysia, there are no bromine producers or manufacturers in present.

There is one manufacturer of flame retardant at Kuala Lumpur (malaysiaexport.com).

Celcure Chemicals (M) Sdn Bhd

Address: Lot 28 Kepong Industrial Area,
Taman Kepong,
52100 Kuala Lumpur, Malaysia
Products: Wood Preservatives, Flame Retardents, Fire Blankets

1.2.3 Price of Bromine

From year 1996 to 2000, the price of bromine is $ 0.61 per pound. The price
of bromine is increased in year 2004 in which it increase to $0.61 per pound. In 2004,
 19

the price of bromine increases and reaches $ 0.68 per pound. The Table 5 shows the
trend of the bromine price according to year.

Table 1.8 : Price of Bromine

Year List Price ($/Pound)

1996 0.61

1997 0.61

1998 0.61

1999 0.61

2000 0.61

2001 0.64

2004 0.68

1.2.4 Consumption of Bromine

The flame retardants market will continue to account for the largest share of
derivatives demand through 2003 as brominated hydrocarbon flame retardants
continue to replace chlorinated compounds based on performance advantages and
better environmental profiles. In the biocides market, both sodium bromide and
brominated hydantoins will enjoy above-average growth as they continue to replace
chlorinated products in both residential and industries applications.

Other bromine derivatives, which include a variety of smaller-volume

compounds used in a number of diverse market, will in the aggregate increase at the
 20

fastest rate as they find growing demand in applications such as pharmaceuticals,

organic synthesis, solvents and cleaners.

Primary uses of bromine compounds were in flame retardants (46%), drilling

fluids (20%), brominated pesticides (mostly methyl bromide) (9%), water-treatment
chemicals (9%), photographic chemicals and dyes (5%), pharmaceutical (4%), rubber
additives (2%) and miscellaneous (5%).

Uses of Bromine
Flame retardants

Drilling fluids

Brominated pesticides
4%2% 5%
5% Water treament chemicals
9% 46%
Photographic chemicals and
9%
dyes
20%
Pharmaceuticals

Rubber additives

Miscellaneous

Figure 1.5 Uses of Bromine

According to national studies in Denmark and Sweden, the electrical and

electronic products are responsible for the greatest influx (around 70%) of
brominated flame retardants into these countries. According to the Bromine Science
and Environmental Forum, 56 % of production goes to the electric and electronic
sector.

The estimated usage (in ton) of the most common brominated flame
retardants of year 1999 and 2001, shown by continent:
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Table 1.9 : Usage (ton) of Brominated Flame Retardants in Year 1999

USA Europe Asia Total

58.665 30.860 114.800 204.325

28.71% 15.10% 56.18% 100%

Table 1.10 : Usage (ton) of Brominated Flame Retardants in Year 2001

USA Europe Asia Rest of World Total

53.900 29.460 117.950 2.430 203.790

26.45% 14.46% 57.88% 1.19% 100%

The brominated flame retardants market is grown by 8% per year, with Asia
leading the way.

Brominated flame retardants are used mainly in circuit boards and casing for
computers and televisions. They are also used in rigid insulation materials and in
textiles.

The majority of all flame retardants that are manufactured are used in plastic
materials. Besides cables and electricity distribution items such as switches,
IT/telecom products, household appliances, and audio/video equipment account for
over 85 % of all plastic usage. Flame retardant treated plastic is used chiefly in
computers, televisions and video equipment.

In Western Europe alone, about 2.7 million tons of plastic were consumed in
the electrical and electronics sectors during the year 2000. This is the equivalent of
 22

an increase of 25 % compared with 1995. It is estimated that 12 % of all plastic used

in this sector has been treated with flame retardants.

Distribution of brominated flame retardants per sector is shown in Figure 1.6.

Distribution of Brominated Flame

Retardants Per Sector

Elektronics

7% 6% Buildings and
constructions
31% 56% Textiles

Transport

Figure 1.6 Distribution of Brominated Flame Retardants Per Sector

According to a report in 1999 by the Nature Conservancy Board, 80-90 % of

all plastic waste from the electronics industry contains flame retardants based on
bromine or chlorine.

1.2.5 Strength
 23

Calcium, zinc and sodium bromides are used by the oil and gas drilling
industry for high-density, clear drilling completion fluids. Bromine-based completion
fluids are used for both offshore and onshore drilling. Demand is currently increasing
with deeper wells being produced and the increase in crude oil prices this year.

Bromine-based biocides are finding increasing use in industrial cooling water

treatment programs. Growth is due to environmental restrictions on chlorine and new
alkaline-based treatment protocols that reduce corrosion. These require biocide
activity at higher pH where chlorine is not effective, but bromine performs.

1.2.6 Weakness

Bromine consumption in flame-retardants has decline in demand over the past

couple of years because of the recessionary economy. This sector is both the largest
market for bromine and the largest source of coproducts methyl bromide (from
tetrabromobisphenol A [TBBPA]) and hydrobromic acid (from decabromodiphenyl
oxide and others). Bromine based flame retardant demand will remain depressed
until growth returns to the polymer applications they serve; largely associated with
consumer electronics.

The fumigant methyl bromide is currently the major bromine-containing

pesticide used in the United States. Its use as a pesticide is currently being phased out
both in the United States and all other developed countries, since atmospheric
scientists have concluded that use of methyl bromide contributes to the destruction of
the ozone layer. Complete phase out of methyl bromide is scheduled for 2005, with
certain quarantine and emergency uses exempted.
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1.2.7 World Resources

Resources of bromine are virtually unlimited. The Dead Sea in the Middle
East is estimated to contain 1 billion tons of bromine. Seawater contains about 65
parts per million of bromine or an estimated 100 trillion tons. The bromine content of
underground water in Poland has been estimated at 36 million tons.

1.2.8 Outlook

1.2.8.1 Fire Retardant

Bromine is a reactive flame retardant in that it enters into chemical reactions

with the components of the systems in which it is used. In addition, bromine acts as a
synergist with many other fire-retardant materials and so increases the effectiveness
of the fire retardant. A new nonbrominated material, a precursor to polybenzoxazole
(PBO), which is a polyhydroxyamide that upon heating is converted to PBO, could
limit flammability. This could have a major negative effect upon the use of BFRs,
especially in airplanes, prisons, submarines, and ships (Chemical & Engineering
News, 1999b).
 25

1.2.8.2 Sanitary Preparations

Bromine was used in indoor swimming pools, hot tubs, and whirlpools. The
sanitary preparation field is an area where bromine is safer than its substitutes,
because bromine has a higher biocidal activity level for the same amount of product.
Growth areas are in the pulp and paper industry, cooling towers, and Government-
regulated food-washing applications. Albemarle reported double-digit sales growth
of brominated biocides as it replaced chlorine and other products in a variety of
applications (McCoy, 1998).

1.2.8.3 Petroleum

Demand for bromine as a gasoline additive has declined each year since the
EPA issued regulations in the 1970s to reduce and eliminate lead in automotive
gasoline. In 1979, the amount of bromine sold for this application reached a peak of
225 Mkg. The rapid decline to 141 Mkg in 1986 was a direct result of the limits on
lead in leaded automotive gasoline. The European Community continued discussions
to reduce lead levels in gasoline. Bromine in petroleum additives was expected to
continue to decline over the long term. Federal laws enacted to encourage alternative
forms of power in automotive engines are likely to have a depressive effect on
bromine demand. The CAA requires mobile sources, such as cars and trucks, to use
the most effective technology possible to control emissions. Electric cars were on the
market in California. Newer prototypes of the fuel cell that burns gasoline can double
the mileage and thereby decrease emissions by using unleaded gasoline.
 26

1.2.8.4 Other Uses

Use of calcium, sodium, and zinc bromides in well-completion fluids

decreased during the 1980s as the domestic petroleum industry suffered a severe
recession. In 1997, however, the oil-services sector posted another strong
performance. About 95% of calcium bromide produced was used as an oil and gas
completion fluid. Oilfield chemicals used in drilling, completion and workover, and
production operations remained significantly more profitable internationally than in
the United States. With the cutback of petroleum supplies internationally and the
rising cost of energy for automobiles and heating, usage is expected to increase as
new domestic wells are drilled and existing wells are serviced to become more
productive.

1.2.9 Substitutes

Chlorine and iodine may be substituted for bromine in a few chemical

reactions and for sanitation purposes. Aniline and some of its derivatives, methanol,
ethanol, and gasoline-grade tertiary butyl alcohol are effective nonlead substitutes for
ethylene dibromide and lead in gasoline in some cars. There are no comparable
substitutes for bromine in various oil and gas well completion and packer
applications. Alumina, magnesium hydroxide, organic chlorine compounds and
phosphorus compounds can be substituted for bromine as fire retardants in some
uses.

1.3 Project Feasibility Study

 27

The section of the report will aim to provide information to justify the
feasibility of constructing and operating the proposed the bromine production plant in
Malaysia. The importance of the preliminary analysis for a project feasibility study is
obvious because the analysis may determine the suitability, viability and feasibility
of a project to be implemented. The study involves potential market of product,
economic aspect, safety, environmental impact, policies and regulations and the
availability of raw material.

1.3.1 Potential Market of Product

Demand for bromine is led by its use in brominated flame retardants. Demand
for brominated flame retardants increased at an average annual growth rate of 8%
with Asia leading the way. 46% of the bromine was used in flame retardants. In year
2001, the total consumption of bromine for brominated flame retardants reached
203.790 tons. The present global demand for bromine is estimated to be around
annual 500,000 tons per annum. The annual growth rate in demand is estimated to be
around 3% per year. Besides, bromine are used in other industries and shown in
Table 1.11.

Table 1.11 : Usage of Bromine According to the Percentage

Type Percentage (%)

Flame retardants 46
Drilling fluids 20
Brominated pesticides 9
Water-treatment chemicals 9
Photographic chemicals and dyes 5
 28

Pharmaceutical 4
Rubber additives 2
Miscellaneous 5

1.3.2 Economic Potential

2HBr (aq) + Cl2 (g) 2HCl (aq) + Br2 (l)

EP = (value of products) – (raw materials costs)

= (1kmole x RM 5.7/kg x 159.83kg/kmole) – [ (RM 3.42/kg x 2 kmole
x 80.92kg/kmole) + (1kmole x RM 0.57/kg x 70.91 kg/kmole) ]
= R M 317 /kg

1.3.3 Safety Aspects

Studies must be carried out to detect and prevent potential hazards such as
fires, explosion or the release of toxic substances.

Both bromine liquid and vapor are corrosive to all body tissues and may
cause serious burns. Excessive inhalation of vapors may be very irritating and
damaging to the respiratory tract and lungs.

Bromine not combustible, but is a strong oxidizer and its heat of reaction with
reducing agents or combustibles may cause ignition. It is highly toxic and dense
 29

fumes are emitted when heated. Vapors can flow along surfaces to low lying areas.
Bromine not considered being an explosion hazard.

Bromine should store in cool dry area, out of direct sunlight and separate
from combustible, organic or other readily oxidizable materials. Keep above 20ºF to
prevent freezing but avoid heating above atmospheric temperatures as vapor pressure
increase could rupture container. Containers of bromine may be hazardous when
empty since they retain product residues (vapors, liquid).

Bromine is stable under ordinary conditions of use and storage. Bromine will
react with steam or water to produce toxic and corrosive fumes of hypobromous acid
and hydrogen bromide. It attacks most metals, reacting violently with aluminum,
titanium, mercury and potassium. It is incompatible with reducing agents,
combustibles, and many organic chemicals.

1.3.4 Government Support

The Malaysia government is encouraging the transfer of the technology from

foreign developed countries to Malaysia in line with the government’s policy. This
project will be aimed not just to obtain technology from abroad but also to train up
the local professional work force to meet the future demand. That is why we are
confident to secure firm government support for the project.

The government is providing incentives and large area of industrial estate

with excellent facilities to facilitate the rapid growth of the Malaysia chemical and
petrochemical industry. Based on the brief study conducted, we strongly believe that
 30

50,000 MT/Y bromine is feasible and has a great potential in Malaysia as well in
Asia.

1.3.5 Environmental Impact

Beside the economic aspect, market and government support, environment

also plays role in determination reaction path. Treatment of the plant’s emission is
needed as to comply with the regulatory limits. The study of pollution generated by
the plant must be carried out. In order to eliminate this problem, the process that will
generate the least environmental impact, will be chosen. Therefore the cost of
treating waste product can be reduced.

1.3.6 Conclusion

From the aspects that mentioned above, it can be conclude that the process
plant for the production of bromine is feasible due to its market, economy potential
and the encouragement from government. However, the handling of the raw material
(hydrobromic acid and chlorine), product (bromine and hydrochloric acid) and waste
must be in proper way for safety purpose in the plant and reduce the impact to the
environment.
 31

1.4 Site Study

The objective of this chapter is to present an overview of the initial feasibility

study of the bromine plant to ensure the suggested 50,000 MT/year of bromine plant
is feasible and promising in term of economics location, environmental impacts and
safety of the plant. The main aspect covered here includes the plant location, plant
layout and selection of a suitable plant site based on the site alternative being
considered. This is very important because the characteristics of a site location will
have a market effect on the success or otherwise of commercial venture.

There are three major site locations that we have taken into consideration:
a)Tanjung Langsat, Johor
b)Gebeng Industrial Estate (Phase IV), Pahang
c)Telok Kalong, Terengganu

1.4.1 Overview and Comparison of the Site Location

In order to select the best site location, the same criterions or factors are
considered. Each aspect should be analyzed and every collected data was examined.
Some potential locations should be identified and proper selection must be done in
order to obtain the most profitable and suitable location.

For a good production of Bromine in a long-term period, the site location can
affect the plant capital cost, operational cost, market price and the most important
thing the company profitability. In order to choose the best location for this project, a
few selection factors have been listed as in Table 1.12.
 32

Table 1.12 : Factors in Selecting Site Location

Primary Factor Specific Factor

a)Raw material supply a)Transportation
b)Market b)Site characteristic
c)Water supply c)Labor
d)Fuel and power supply d)Taxes
e)Climate e)Regulatory laws
f) Dispose of waste
g)Government incentives
h)Safety
i) Community factor

a) An attractive government incentive

Incentive is among the advantages provided by the government in order to

attract people to invest in that specified location. The feasibility of the plant
would be better when the incentive offered by the government is better.

b) Reasonable land price

Another factor to consider is the land cost (land price). The cost of land
depends on the location of the property and may vary between a rural district and
a highly industrial area. However the land cost does not decrease with time.

c) Raw material availability

 33

Raw material availability must be considered because sometimes there are

more than one or two reactants that can be used to convert into desired product.
The selection of suitable raw materials can lead to higher conversion of desired
products and less byproducts. However the price of such raw materials may be
very expensive. The other option is to use cheaper raw material but they may not
be resulting as high conversion into desired products as the expensive raw
materials. In addition, it will be necessary to increase the cost for separation
process to purity the final product. Therefore it is vital identify the locations of
raw material sources. By choosing a site close to the raw materials, the
transportation costs can be reduced.

d) Marketing area

The marketing area also plays an important role in the selection of the plant
site location. The location of market areas or intermediate distribution centre
affects the cost of products distribution and the time required for shipping.
Proximity to the major markets is an important consideration in the selection of a
plant site, because the buyer usually finds it advantageous to purchase from
nearby sources.

e) Sources of power (electricity) and water

The plant will run smoothly with good power and water supply. The sources
of power and water reservoir from nearby area will ensure the requirement of
power and water supply.

f) Land characteristic
 34

The land characteristic (geographical factors) at the proposed plant site

should be examined carefully. Sufficient suitable land must be available for the
proposed plant for the future expansion. A suitable land should be ideally flat,
well drained and have suitable load-bearing characteristic such as for piling or
other special foundation. The characteristics of the short-listed site locations are
mainly the same.
g) Transport facilities

For import and export purpose, it is important to ensure that there is a land
and water transportation network in the surrounding area of the plant. A few
selections transportation facilities have been listed as below:
i) Road transportation
ii) Sea transportation
iii) Air transportation

h) Climate

The climate, especially the extreme weathers can have an influence on the
economic operation of the plant. For instance, cold climate will result in the need
to construct protective shelters around the process equipments whereas at high
temperatures, cooling and air conditioning equipments are required which both
will increase the cost significantly. Therefore it is very important to study this
factor when selecting a plant site.

Weather condition is influenced by the Northeast and Southwest monsoon:

i) Wind
Generally light wind. The predominant wind direction from
November to March is from the North. From May to September, the
predominant wind is from the South. During inter monsoon month of
 35

April to October, the wind direction is variable with speeds below 8

m/sec. On the average wind is calm about 40% of the time.
ii) Rainfall
Annual rainfall is about 2500 mm. Most rainfall is around the month
of March and September. For the east coast part of peninsular
Malaysia, rain falls heavily during the monsoon season, which is from
end of September to early January.
iii) Temperature
Daily temperature varies from 25 to 27 degree Celsius. The mean
maximum is about 32°C, while the minimum is about 21°C.

i) Local community

Community factors can have an effect on the proposed plant because at

different locations, local community may have different characters and facilities.
Full consideration must be given to the safe location of the plant so that it does
not impose a significant additional risk to the community.

j) Man power availability

The availability of labor type and supply in the vicinity of a proposed plant
site must be examined. Skilled construction workers will usually be brought in
from outside the site area but there should be an adequate pool of unskilled labor
available locally and labor suitable for training to operate the plant.

k) Safety and environmental impact

 36

All industrial plants especially chemical plants will produce waste products.
The site selected should have satisfactory and efficient disposal system for plant
wastes or effluents such as the drainage systems and dumping sites. Each
individual plant has to treat their waste disposal according to standard and
procedure of Department of Environment (DOE). Water discharge has to be
treated before channeled to open drains. Each plant also has to obtain approval
for site suitability from Department Of Environment before commencement of
operation. Therefore it is important to choose a location that will secure a smooth
operation for the plant and gives low impact on the environment.

1.4.2 Detailed Description on Several Strategic Location

The manufacture of bromine can be classified as a chemical project. So this

chemical industry must be located in a special zone provided by the government. By
virtue of the factors stated above, there is three main locations have been proposed.
The sites are:
a) Gebeng Industrial Area (Phase IV), Pahang
b) Teluk Kalong Industrial Area, Terengganu
c) Tanjung Langsat Industrial Area, Johor

1.4.2.1 Gebeng Industrial Estate, Pahang

Gebeng Industrial Estate has grown rapidly within 20 years, propels Pahang’s
potential area as regional integrated petrochemical Centre. It is located 25 km from
Kuantan Town.
 37

A third phase scanning some 2500 acres is also planned, where another 60%
will be designated for petrochemical industries, which will eventually experience
further expansion with addiction of another phase, consisting of 6000 acres.

The price per meter square in Gebeng Phase IV Industrial Estate is RM 2.00-
9.00 per feet square. The price is cheap and advantage of saving the cost land. State
Government has started to upgrade the infrastructures around the area mainly its
transportation facilities. This includes the development of railway link connecting
Kuantan Port-Gebeng-Kerteh. This is to ensure import and export activities running
smoothly.

1.4.2.2 Teluk Kalong Industrial Estate, Terengganu

Teluk Kalong is also classified as chemical and petrochemical industrial area.

This area is proposed for petrochemical and heavy industry. The distance from
Kemaman Town is only about 9.6 km.The developer of Teluk Kalong is Perbadanan
Memajukan Iktisad Negeri Terengganu (PMINT). The price of the land is in the
range of RM45.00 to RM60.00 per feet square and the area still available is about
167.46 hectares.

In terms of water supply and electricity, this area is supplied with water from
Bukit Sah, Seberang Tayor, Sungai Cherol and Kemasik. That supply is about 8172
m3/day. For electricity, the suppliers are the Paka Power Plant (900MW), IPP YTL
Power Generation Sdn. Bhd. (600MW) and Tasik Kenyir Hydroelectric Power
(400MW).
 38

1.4.2.3 Tanjung Langsat Industrial Estate, Johor

Tanjung Langsat Industrial area seems to be a potential area because these

areas become the creating new age industrial nucleus. Tanjung Langsat Industrial
area is located in the southern region of the Johor State bounded by the Straits of
Johor in the South and the Johor river basin in the East. Its’ location is about 45 km
from Johor Bahru, 8 km from Johor port and 46 km from Singapore. The types of
industry preferred are light, medium and heavy size industry. The total available
industrial lands are 1071.2 hectares with the selling price of RM10.00 - RM12.00 per
feet square.

A network of well-planned highways and railway, an airport and seaport

serves Tanjung Langsat. The facilities that are available in the port area include six
berths with a maximum depth of 13 meters to cater for containers, general and dry
bulk cargoes. The special jetty also build for handling liquid cargo and a hazardous
cargo jetty to handle the fuel oil and chemicals furthermore, there is a ferry terminal
with daily departure to Singapore and Batam. The construction of a new port in
Tanjung Langsat covering an area of 763 acres and 14 meters depth is already in
progress. All transport operators provide services for shippers in the free zone.
Warehouse facilities are available in the port.

There are 2 main utilities available utilities in Tanjung Langsat:

i. Water supply
ii. Electrical supply
 39

High quality water with an excellent reliable supply is available with a total
capacity of 24.0 MG per day. The flow rate pressure of water supply is between 0.04-
30 liter/second. The water supply can be obtained Sungai Buloh and Sungai Layang
reservoirs from Syarikat Air Johor (SAJ). In term of electricity, there is Sultan
Iskandar Power Station in Pasir Gudang.
In term of transportation, an easy-to-accessed network of well-planned
highways and railways serves Tanjung Langsat. Besides, Tanjung Langsat is near to
Senai International Airport(50km) and 60km from Changi Airport and just 8km from
Johor Port at Pasir Gudang.

The labor salary around Tanjung Langsat area is quite high due to the
competition with industries in Singapore. Locals prefer to work in Singapore due to
their high salary rate in Singapore dollars and the currency rate itself.
 40

Table 1.13 : Comparison of short-listed of the potential site location

Gebeng Tanjung Langsat, Teluk Kalong,

Selection
(Phase IV), Pahang Johor Terengganu
Criteria

 Pahang State  Johor State Economic  Perbadanan Iktisad

Developer
Development Development Negeri Terengganu
Corporation (PSDC) Corporation (JCORP) (PMINT)
 Perbadanan Tempatan
Pasir Gudang (PBTG)
Area Still 1400 Hectares 1071.2 Hectares 167.46 Hectares
Available 3 2 1
Land Price 2.00-9.00 10.00-12.00 45.00-60.00
(RM per feet
square) 3 2 1
Raw Material  Shandong Yuncheng  Shandong Yuncheng  Shandong Yuncheng
Supplier [9] Sanxing Chem. Ind. Co Sanxing Chem. Ind. Co Sanxing Chem. Ind. Co
Ltd-China Ltd-China Ltd-China
 Maser(M) Sdn Bhd.KL  Maser(M) Sdn Bhd.KL  Maser(M) Sdn Bhd.KL
1 3 3 3
Distance from  25 km from Kuantan  45 km from Johor  9.6 km from
Nearest Town Town Bharu Kemaman Town
 46 km from
Singapore
1 1 2
Types of  Chemical and plastic  Light, medium and  Chemical
 41

Industries [13]  Petro-chemical heavy industry  Petro-chemical

 Sea related industry
3 2 3

Road Facilities  Federal Road  Pasir Gudang to Kim  Federal Road (Kuala
(Kuantan-Kerteh- Kim River Terengganu-Kerteh-
Kuala Tereng-ganu)  Bridge over Kim Telok Kalong-
 Federal Road Kim River Gebeng-Kuantan-
(Kuantan-Segamat)  Bridge to Johor Kuala Lumpur)
 Federal Road River
(Kuantan-Karak-  North-South
Kuala Lumpur) Highway (Bukit
Kayu Hitam to
Singapore)
 Highway from Pasir
Gudang-Tanjung
Kupang-Tuas,
Singapore
2 3 1
Airport  Kuantan Airport  50 km from Senai  Kuala Terengganu
Facilities  Kerteh Airport International Airport Airport
 KLIA  60 km from Changi  Kerteh Airport
International Airport,  Kuantan Airport
Singapore  KLIA
2 1 2
Seaport  5 km from Kuantan  8 km from Johor Port  Kemaman Port
Port (Pasir Gudang)  Kerteh Minor Port
 Kemaman Port  Tanjung Pelepas Port  Kuantan Port
 Kerteh Minor Port
2 3 3
Railway  Kuantan Port-  Butterworth-Pasir Not available
Gebeng-Kerteh Gudang-Singapore
2 2 0
Electricity  Paka Power Plant  Sultan Iskandar  Paka Power Plant
 IPP YTL Power Power Station  IPP YTL Power
Generation Sdn. Bhd. Generation Sdn.
 Tasik Kenyir Hydro-  IPP YTL Power Bhd.
Electric Generation Sdn.  Tasik Kenyir Hydro-
Bhd. electric
3
2 3
Water Supply  32 MGD  Syarikat Air Johor d) Bukit Sah
 42

Supply(Semambu  Loji Air Sungai e) Sungai Cherol

Water Treatment Layang f) Kemasik
Plant)  Sungai Buloh g) Seberang Tayor
 2 MGD and 1.5 (Capacity: 24 MGD)
MGD reservoirs at
Bukit Penggorak
 0.5 MGD and 1.0
MGD reservoirs at
Bukit Merah
2 1 2

Resident Area  Kuantan  Pasir Gudang  Kerteh

 Kempas  Paka
2 3 3
Human Training facilities such as: Training facilities such as: Training facilities such as:
Resources  Universiti Teknologi  Universiti Teknologi  Universiti Teknologi
Malaysia, Indera Malaysia, Skudai MARA
Mahkota  Universiti Teknologi  Institut Latihan
 Institut Latihan MARA, Segamat Perindustri-an
Perindustrian  Politeknik Pasir  Universiti Putra
 Politeknik Sultan Gudang Malaysia
Ahmad Shah  Institut Latihan  TATI
(POLISAS) PerindustrianPasir
 Universiti Islam Gudang
Antarabangsa (UIA)  Johor Skills
 Institut Kemajuan Development Center
Ikhtisas Pahang (JSDEC)
(IKIP)  Johor Technovation
Park

2 2 2

Package  Pioneer Status (tax  Pioneer Status  Special Land

Incentives exemption at (Investment Tax Premium
from State statutory income Allowance,  Discounts on Land
Government level for 5 years) Reinvestment Premium
[13]  Investment Tax Allowance)  Differed Payment for
Allowance (ITA of  Incentives for Export Land Premium
60% on qualifying Credit Refinancing  Pioneer Status
capital expenditure (ERC) Scheme  Investment Tax
incurred within a  Incentives for R&D Allowance
period of 5 years)  Incentives for  Import Duty on Raw
 Incentives for Training Tariff Materials
Strategic Projects Protection  Infrastructure
(Pioneer Status with  Exemption from Allowance
tax exemption at Import Duty on Direct  Second Round
statutory income level Raw Materials/ Pioneer Status or ITA
for 10 years, ITA of Components
100% in qualifying  Exemption from
capital expenditure Import Duty on Direct
 43

incurred within a and Sales Tax on

period of 10 years Machinery and
Equipment
 Incentives for the
Storage Treatment
and Disposal of Toxic
and Hazardous Waste
3 3 2

Other  Peninsular Gas  Peninsular Gas  Peninsular Gas

Facilities Utilization Network Utilization Network Utilization Network
(PGU) (PGU) (PGU)
 Free Trade Zone
1 2 1

Total 34 32 29

1.4.3 Conclusion

According to overview for the selected location, a site will be selected depend
on location (strategic for marketing), incentive of the state government and facilities
in the site area or location.

After having analysed all the information, we decide to choose Gebeng

Industrial Area as our base for Bromine plant. There are so many reasons why we
choose Gebeng Industrial Area for our location. The reasons for choosing Gebeng
Industrial Area for our location are:
i. Land price in Gebeng is cheaper than Tanjung Langsat and Teluk
Kalung. It’s about RM 2.00-RM9.00 per ft2.
 44

ii. The Pahang State Government, with full cooperation from the Federal
Government, has major development plan to develop Pahang
becoming an industrial forerunner, especially in field of chemical and
petrochemical.
iii. Investment Tax Allowance (ITA of 60% on qualifying capital
expenditure incurred within a period of 5 years)
iv. In infrastructure aspect, Pahang state always-upgrading existing and
developing new infrastructure and supporting industries to further
enhance it’s petrochemical development. These include: -

 Construction of roads;
 Increase accessibility to and from the Gebeng estate;
 A railways link is scheduled to connect Kuantan Port-Gebeng-
Kemaman port- Kerteh and Tuk Arun in Terengganu.
 Additional facilities such common piperacks for transporting
liquefied and gaseous chemical will also be built between
Gebeng and Kuantan.

The Kuantan Port , which is one of the international ports in Malaysia , give
advantages and convenient to investor that they do not have problems dealing with
exportation and importation purposes. On the other hand, it is easier to access raw
material from Kuantan Port rather than Pasir Gudang Port and Kemaman Port.

1.4.4 Site Layout

Site layout for the plant consists of the process units involved, which is
located in the main plant and other auxiliary building. The layout, which refers to
 45

each department, must be arranged in order to give maximum efficiency and

minimum cost for operating the plant. The principle factors to be considered are:

a)Process requirements
b)Economic considerations
c)Construction and operating cost
d)Convenience of operation
e)Convenience of maintenance
f) Appearance
g)Safety and emergency considerations
h)Future expansions

1.4.4.1 Proposed Bromine Production Plant Site Layout

Site layout for the plant consists of the process unit involved, located in the
main plant and other auxiliary buildings. The layout refer to each department that
must be arranged in the good arrangement in order to give the maximum cost for the
operating plant. The main principles involve in the site layout are:

a)Process and economic considerations

b)Constructions, operations and maintenance
c)Safety and comfort ability

The auxiliary building and service required on the site, in addition the main
process units include:

a)Offices for administration

b)Storage of raw material and product
 46

c)Plant area
d)Laboratories for process control
e)Tank farm and warehouse
f) Maintenance workshop
g)Utilities-Waste treatment plant, chemical waste
h)Fire station
i) Parking lot
j) Security guard
k)Canteen
l) Future expansion
 47

Parking

Parking
Parking Lot

Parking
Lot

Lot

Lot
Administration
Department

Office &
Canteen
Security

Security
Toil
Surau
et
u

Utility Plant
Warehouse
Chemical

Plant Area

Fire Future
Station Tank
Farm
expansion

Expansion

Figure 1.7 Proposed Plant Layout

1.5 Detailed Consideration of Selected Process

 48

The process selected for this project is continuous process for preparing
bromine. The raw materials required for this process are aqueous hydrobromic acid
solutions and chlorine. Both materials need to be purchased. Aqueous hydrobromic
acid solutions can be purchased from a few companies mostly located in China and
India. The suppliers available are Shandong Tianyi Chemicals Co. Ltd,Sanxing
Chemical Industry Co. Ltd and Shandong Ocean Chemical Industry Co. Ltd from
China. Similarly happened to chlorine but fortunately, there is one local company
which can supply this material. In this project, aqueous hydrobromic acid solutions
will be purchased from Shandong Yuncheng Sanxiang Chemical Industry Co., Ltd.,
which is located in China whereas chlorine from Maser (M) SDN BHD, which is
located in Kuala Lumpur.

The equipments used in this process are reactor, flash, decantor, distillation
column, heat exchanger, mixer and divider. The chlorine reacts practically
instantaneously with the acid solutions inside the reactor to produce hydrochloric
acid and bromine. The flash is used to separate chlorine in vapor form from the liquid
bromine and aqueous acids. The bromine separates from the acid solutions by the
decanter.Then, it is purified by distillation column.

The EP is calculated based on the pathway and also the prices of the raw
material. The formula for EP equals the value of product minus the raw material
costs. The prices of the products, raw materials and the calculation are shown below.

Molecular
Price
Component Weight Source
(US$)
(kg/kmole)
Hydrobromic Acid
80.92 RM 3.42 / kg www.e1.greatlakes
(48%)
Chlorine 70.91 RM 0.57 / kg www.chemsource.com

Hydrochloric Acid 36.47 $ 4.8 per litre www.chemsource.com

 49

Bromine 159.83 RM 5.70 / kg www.e1.greatlakes

2HBr (aq) + Cl2 (g) 2HCl (aq) + Br2 (aq)

Basis : 2 kmol HBr = 1 kmol Cl2 = 2 kmol HCl = 1 kmol Br2

EP = (value of products) – (raw materials costs)

= (1kmole x RM 5.7/kg x 159.83kg/kmole) – [ (RM 3.42/kg x 2 kmole
x 80.92kg/kmole) + (1kmole x RM 0.57/kg x 70.91 kg/kmole) ]
= R M 317 /kg

1.6 Physical and Chemical Properties

Bromine is the only liquid nonmetallic element. It is a heavy, mobile, reddish-

brown liquid, volatilizing readily at room temperature to a red vapor with a strong
disagreeable odor, resembling chlorine, and having a very irritating effect on the eyes
and throat; it is readily soluble in water or carbon disulfide, forming a red solution, is
less active than chlorine but more so than iodine; it unites readily with many
elements and has a bleaching action; when spilled on the skin it produces painful
sores.

1.6.1 Properties of Bromine

 50

Table 1.14 : Physical and Chemical properties of Bromine

PROPERTY VALUE &

DESCRIPTION
Formula Br2
CAS Reg. No 7726956
Molecular weight 159.82
Normal freezing point, oC -7.2
Normal boiling point, oC 58.8
Critical temperature, K 584.15
Critical pressure, bar 102.8
Critical volume, m3/mol 0.000135
Liquid density, kg/m3 3104.2988
Reference temperature for liquid density, oC 25
Heat of vaporization at normal boiling point, J/mol 31000
Standard enthalpy of formation of vapour at 298 K, kJ/mol 30.91
Standard Gibbs energy of formation of vapour at 298 K, 0
kJ/mol
Constant in the ideal gas heat capacity equation, A 38.52723
Constant in the ideal gas heat capacity equation, B -1.976835
Constant in the ideal gas heat capacity equation, C 1.526107
Constant in the ideal gas heat capacity equation, D -0.198398
Constant in the Antoine equation, A 6.38719
Constant in the Antoine equation, B 1347.20693
Constant in the Antoine equation, C -32.32405
Minimum temperature for Antoine constant, oC 70
Maximum temperature for Antoine constant, oC 10

1.6.2 Properties of Chlorine

 51

Table 1.15 : Physical and Chemical properties of Chlorine

PROPERTY VALUE &

DESCRIPTION
Formula Cl2
CAS Reg. No 7782505
Molecular weight 70.906
Normal freezing point, oC -101.0
Normal boiling point, oC -34.5
Critical temperature, K 417.0
Critical pressure, bar 77.0
Critical volume, m3/mol 0.124
Liquid density, kg/m3 1563
Reference temperature for liquid density, oC -34
Heat of vaporization at normal boiling point, J/mol 20432
Standard enthalpy of formation of vapour at 298 K, kJ/mol 0
Standard Gibbs energy of formation of vapour at 298 K, 0
kJ/mol
Constant in the ideal gas heat capacity equation, A 26.929
Constant in the ideal gas heat capacity equation, B 3.383E-02
Constant in the ideal gas heat capacity equation, C -3.869E-05
Constant in the ideal gas heat capacity equation, D 1.547E-08
Constant in the Antoine equation, A 6.72173
Constant in the Antoine equation, B 1268.37969
Constant in the Antoine equation, C 32.01879
Minimum temperature for Antoine constant, oC -101
Maximum temperature for Antoine constant, oC -9

1.6.3 Properties of Hydrochloric acid

Table 1.16 : Physical and Chemical properties of Hydrochloric acid

 52

PROPERTY VALUE &

DESCRIPTION
Formula HCl
CAS Reg. No 7647010
Molecular weight 36.461
Normal freezing point, oC -114.2
Normal boiling point, oC 80
Critical temperature, K 324.6
Critical pressure, bar 83.1
Critical volume, m3/mol 0.081
Liquid density, kg/m3 1.1593
Reference temperature for liquid density, oC 20
Heat of vaporization at normal boiling point, J/mol 16161
Standard enthalpy of formation of vapour at 298 K, kJ/mol -92.36
Standard Gibbs energy of formation of vapour at 298 K, -95.33
kJ/mol
Constant in the ideal gas heat capacity equation, A 30.291
Constant in the ideal gas heat capacity equation, B -7.201E-03
Constant in the ideal gas heat capacity equation, C 1.246E-05
Constant in the ideal gas heat capacity equation, D -3.897E-09
Constant in the Antoine equation, A 16.5040
Constant in the Antoine equation, B 1714.25
Constant in the Antoine equation, C -14.45
Minimum temperature for Antoine constant, oC -136
Maximum temperature for Antoine constant, oC -73

1.6.4 Properties of Hydrobromic acid

Table 1.17: Physical and Chemical properties of Hydro Bromide acid

 53

PROPERTY VALUE &

DESCRIPTION
Formula HBr
CAS Reg. No 10035106
Molecular weight 80.912
Normal freezing point, oC -11
Normal boiling point, oC 122
Critical temperature, K 363.15
Critical pressure, bar 84.6
Critical volume, m3/mol 0.0001
Liquid density, kg/m3 27.985
Reference temperature for liquid density, oC -88
Heat of vaporization at normal boiling point, J/mol
Standard enthalpy of formation of vapour at 298 K, kJ/mol -36.23
Standard Gibbs energy of formation of vapour at 298 K,
kJ/mol
Constant in the ideal gas heat capacity equation, A 0.2912E-5
Constant in the ideal gas heat capacity equation, B 0.0953E-5
Constant in the ideal gas heat capacity equation, C 2.1420E-3
Constant in the ideal gas heat capacity equation, D 0.0157E-5
Constant in the Antoine equation, A 4.70822
Constant in the Antoine equation, B 1562.264
Constant in the Antoine equation, C 0.628
Minimum temperature for Antoine constant, oC -38.7
Maximum temperature for Antoine constant, oC -66.4

1.7 Reviews and Screening of Alternative Processes

1.7.1 Introduction
 54

There are many available methods to produce bromine commercially. The

main 5 alternatives possible routes are as follows:

i) Synthesis From Continuous process

ii) Synthesis From continuous two-stage vacuum process
(Conventional Method)
iii) Synthesis From continuous two-stage vacuum process
(New Invention)
iv) Synthesis From Aqueous Hydrobromic Acid Solution
( New Invention)
v) Synthesis From Aqueous Hydrobromic Acid Solution
(Coventional Method)

Bromine, Br2, usually occurs in the hydrosphere mainly as soluble bromide

salts. The first commercial bromine production from salt brines was in 1846 at
Pennsylvania. Most of the commercial production of bromine comes from seawater
using extraction process or the Dow process. The seawater is treated with chlorine,
which will converts sodium bromide into free bromine ( NaBr 2 + Cl2 = NaCl2 + Br2 ).
The richest source of Br2 in the world is found in the Dead Sea brines, which contain
up to 12 g/L of bromine.

Currently there are few different synthesis or methods of processing bromine

such as continuous process by simultaneously feeding an aqueous solution of
bromide and chlorine gas into top of a contact tower, continuous two-stage vacuum
process which divides into conventional and present invention method and finally is
the preparation of bromine from aqueous hydrobromic acid solutions conventionally.
1.7.2 Synthesis From Continuous Process

Bromine is continuously produced by simultaneously feeding an aqueous

solution of bromide or hydrobromic acid and chlorine gas into the top of a contact
tower whish is separated into an upper reaction section and a lower distillation
 55

section, having a gas outlet port there between; and feeding steam from the bottom of
the tower whereby free bromine formed in the upper reaction port section and free
bromine distilled from the lower distillation tower section are recovered through said
bromine outlet port, wherein the aqueous solution containing bromide or
hydrobromic acid is heated at lower than 80C in the reaction column and the
solution is heated to higher than 90C in the distillation column. The reaction for this
process is shown below;

2HBr (aq) + Cl2 (g) → 2HCl (aq) + Br2 (g)

In the present invention, the bromine forming portion of the reaction is

separated from the lower, or steam distillation portion, by a bromine outlet which is
situated at the middle plate of a multiple contact tower. The chlorinating reaction is
effected at a relatively lower temperature. Since bromine has a relatively high
specific gravity, it rises only to the extent of the middle section of the tower. This
process thus enables the use of a smaller contact tower since the distillation section
of the tower is separated from the reaction of the tower so that the tower resistance is
low. Thus a lower pressure and lower quantity of steam is necessary.

There are many potential of using this reactive distillation in this bromine
production process. The advantages are listed below:
i) Improves selectivity
ii) Reduce raw material usage and byproducts prevent pollution
iii) Reduce energy use
iv) Able to handle difficult separations
v) Overall high recovery of products.

1.7.3 Synthesis From Continuous Two-Stage Vacuum Process (Conventional

 56

Method)

This method uses brine containing bromide as the raw material. The reaction
are as follow; NaBr2 + Cl2 → NaCl2 + Br2. This conventional is also known as the
“Kubierscky’s distillation method“, where a bromide solution is fed counter-
currently in a contact tower made of granite or similar material. Chlorine gas is then
fed into reaction section of the tower, and contacts the bromide solution whish is fed
from the top of the column. Bromine, which is produced by this reaction is distilled
from the top of the tower by the introduction of steam from the bottom of the tower
and then recovered.

Bromine recovery by this method requires a significant amount of steam for

preheating the inlet brine to bring to boiling to allow the gaseous bromine produced
by the oxidation reaction with the chlorine to be stripped from the solution. The
amount of steam required depends upon the temperature of the brine entering the
contact tower and the operating pressure. A chlorination step involving the
conversion of bromide to bromine can be accomplished at low temperatures but the
brine must be heated up to 110C in a conventional atmospheric steaming out tower
in order to steam strip the bromine from the bromide depleted brine after the reaction
has taken place. The bromide depleted brine from the tower bottoms is then
neutralized and returned to the formation by deep well injection. This bromide-
depleted brine stream typically contains 100-200ppm of unreacted bromide and
bromine and also excess chlorine which is lost thus reducing the overall efficiency of
the tower. Contact towers operated at atmospheric pressure are traditionally made of
granite where it is very sensitive to over pressuring during process upsets which
frequently occur during normal tower operation and may result in granite breakage or
gasket damage and potentially could cause the entire tower to collapse.

1.7.4 Synthesis From Continuous Two-Stage Vacuum Process (New Invention)

 57

The present invention relates to a highly efficient two-stage continuous

process for the extraction of bromine from bromine-containing brine at
subatmospheric pressure whereby bromide containing brine is contacted with
chlorine to obtain free bromine. More particularly, The present invention is directed
to a process for the extraction of bromine utilizing chlorine and steam distillation by
a two-stage subatmospheric or vacuum operation to recover the bromine thus formed
from the original bromide-containing brine with a significant reduction in chlorine
and steam requirements than that required with the conventional steaming out towers.
The invention especially relates to the use of a two-stage arrangement employing a
contact tower at subatmospheric pressure from 0.41 to 0.82 atm and reduced
temperature to enhance steam, bromine and chlorine recovery and reduce chlorine
consumption in the contact tower by reducing any side reaction effects. The
subatmospheric pressure operation of the two stages also reduces the operating
temperature of process which will reduces side reaction effects and thus
neutralization requirements prior to disposal of waste brine.

1.7.5 Synthesis From Aqueous Hydrobromic Acid Solution (New Invention)

Pure liquid bromine is produced directly from an acidic aqueous bromide

mother liquor by reacting it with about 80 to 90% of the amount of chlorine
stoichiometrically equivalent to the bromide present in the whole supplied mother
liquor and collecting the liquid bromine which separates out of solution; the
remaining mother liquor free from liquid bromine is steam distilled in the presence of
sufficient chlorine to convert the rest bromide to bromine and to condense crude
liquid bromine which is purified by washing with sufficient fresh mother liquor.
Production capacity is increased by 20% compared to conventional process in which
all the bromine is submitted to steam distillation.
 58

The reaction shown as follows;

2HBr (aq) + Cl2 (g) → 2HCl (aq) + Br2 (g)

The instant invention provides an overall process incorporating acid method

for producing a fraction of pure liquid bromine, said process being a method for
preparing bromine from aqueous bromide mother liquor comprising of steps of;
i) reacting mother liquor with about 80% to 90% of the amount of chlorine
stoichiometrically equivalent to the bromide present in the whole supplied liquor to
produce pure liquid bromine and bromine dissolved in the mother liquor,
ii) separating substantially all the pure liquid bromine from the mother liquor,
iii) steam distilling the separated mother liquor in the presence of excess
chlorine to convert all the remaining bromide to bromine and condensing crude
liquid bromine, and
iv) washing the crude liquid bromine with sufficient fresh mother liquor to
lower the chlorine content of the bromine.

The liquid bromine produced in this manner has been found to be practically
free of chlorine and to meet all the usual specifications commercially required of
pure liquid bromine. This permits its direct transmittal to storage for shipment
without further purification. This also effects a decrease of up to 20% or more in the
quantity of bromine treated in the purifier. Another advantage is that it permits
increasing the overall bromine production of an installation without consumption of
additional steam and without increasing the dimensions of the steaming-out tower.
The equipment used for the procedure of this invention must be made from materials,
such as ceramics which is resistant to wet bromine and aqueous hydrobromic acid
solution. Quartz or pyrex vessels or pyrex-lined towers are conveniently used.
Although glass and tile piping have been used extensively, connections of
polytetrafluoroethylene are particularly advantageous.
 59

1.7.6 Synthesis From Aqueous Hydrobromic Acid Solution (Coventional

Method)

Conventionally, it has not been considered practicable to pre-chlorinate with

more than about two-thirds of the stoichiometric quantity of chlorine necessary to
convert all the bromide in the mother to bromine. Otherwise, liquid bromine will
separates out and contaminates the system. The process is aimed at keeping bromine
in either the dissolved or the vapor state until it is condensed after the steaming out
tower. The pre-chlorination process provides a head-start to making elemental
bromine available, but the complete conversion by chlorine of bromine to bromide is
not accomplished until the temperature of the reactants is around 100°C in the
steaming-out tower. At this point, it is the practice to use chlorine in an amount such
that the total chlorine used is in slight excess of stoichiometric , about 1% in excess if
compared to synthesis of bromine through new invention.

The reaction shown as follows;

2HBr (aq) + Cl2 (g) → 2HCl (aq) + Br2 (g)

Pure liquid bromine is obtained from this mother liquor by the action of
chlorine in three stages. The first “pre-chlorination” step, the mother liquor is treated
with only part of the amount stoichiometrically required to convert all the bromide
therein to bromine, this first amount being limited to less than the amount which
would result in separation of any liquid bromine, being thus no greater than sufficient
to form a saturated solution of bromine in the mother liquor. The second step which
is the extraction or steaming-out process, the pre-chlorinated mother liquor is
simultaneously treated with the remainder of the chlorine required to convert the
bromide to bromine, together with steam to effect steam distillation of the total
bromine.
 60

The final step is purification process where the bromine condensed from the
steam distillation is treated with an additional small amount of mother liquor, about 5
to 10% based on the initial weight used thereof.

The operation of the process between the pre-chlorination and steaming-out

steps has accordingly been directed toward strict avoidance of forming any liquid
phase of bromine in the pipes connecting the two stages, particularly in the hydraulic
guard or trap provided to keep the vapor phase of the steaming-out tower free of
liquid bromine. The steaming-out tower for the second conventional step operates in
the vapor state at close to 100°C. The stream from the pre-chlorination step
comprising a solution of bromine in hydrobromic acid mother liquor, enters the top
of the steaming-out tower while the second charge of chlorine and the steam enter s
at the bottom. It is advantageous for the steaming-out tower to have a large capacity,
exemplarily 3 or 4 times the volume of the pre-chlorination tower.

Then the mixture of water vapor and bromine vapor leaving the top of the
steaming-out tower is then condensed and the liquid bromine and hot aqueous acid
are separated, such as by decantation or separator from each other. The hot aqueous
acid is then recycled to the steaming-out tower. The liquid bromine must be purified
from small quantities of chlorine resulting from the use of an excess of chlorine to
ensure complete conversion of all bromide. The excess chlorine must be eliminate to
meet commercial specification and this achieved wherein the bromine is washed in a
“purification tower” with exemplarily a 5 to 10% aliquot of the starting hydrobromic
acid mother liquor.

1.7.7 Environmental Effect of Process

 61

In the synthesis of bromine, the raw material used and products form may
exert effect to human and environment. Table 1.18 shows the toxicity effects data
regarding to each component that may involve in the synthesis of the bromine. Table
1.19 shows the overall effect of synthesis process to environment.

Table 1.18 : Toxicity Effects Data

SUBSTANCE REMARKS
 May cause sore throat , vomitting and
Hydrobromic Acid ( HBr ) burns.
 Sharp choking odour
 Stable under ordinary conditions of use
and storage
 Eyes: Causes burns, redness and pain
 Inhalation: Irritating to respiratory
system and cause coughing and death.
 Skin: cause discoloration and pain.

 Skin, eye and respiratory irritant

Sodium Bromide ( NaBr2 )  Prolonged exposure may lead to bromide
rashes

 Ingestion: When ingested, hydrochloric

Hydrogen Chloride (HCl ) acid is corrosive to the tissues with which
it comes in contact.
 Eyes: Eye contact results in severe
irritation and painful burns of the eyes
and eyelids. If material isnot removed by
copious irrigation with water at room
temperature visual impairment ortotal
loss of vision could result.
 Skin: Skin contact causes severe burns
unless the hydrochloric acid is washed
off immediately. .
 Inhalation: Corrosive and irritating to
respiratory tract; inhalation results in
coughing, choking, and/orinflammation
of the respiratory tract.

Bromine (Br2)  Inhalation: corrosive to all body tissues

and may cause serious burns. Others are
headache, abdominal pain and cough
 Ingestion: corrosive, sore throat and
vomiting.
 Skin: skin discoloration, blistering and
 62

slow healing ulcers

 Eyes: corrosive. Can cause blurred
vision, redness, pain and eye damage.

Chlorine (Cl2)  Inhalation: May be fatal if inhaled

 Skin: skin irritation and cause burns
 Eyes: irritation and tearing of the eyes.

Table 1.19 : Overall Review of Synthesis Process to Environment

Synthesis Effects On Enviromental

 May cause choking odour in process enviroment

From aqueous HBr solutions
(new invention)
Conventional Method
(Kubierscky distillation method)
due to excess chlorine usage
 Hydrobromic acid should be avoided from
contacting materials such as fluorine gas, ammonia
and metals in processing area.
 Hot aqueous acid recycled to steaming tower is very
corrosive and must be treated if being disposed to
nature.
 Fatality may occur if chlorine is exposed to the
processing enviroment without any protection
measures.
 Using excess chlorine may cause explosion with
other combustibles material which will burn in
chlorine as they do in oxygen.
 The exothermic vapor-liquid reaction between
chlorine and bromide containing solution may give
great impact to working enviroment since the entire
tower temperature is so high.

 Fatality may occur if chlorine is exposed to the

processing enviroment for longer period.
 Sodium chloride produced as a by-product must not
Continuous two-stage vacuum be decomposed simply because it may emit toxic
process fumes when heated to decomposition.
(new method)
 63

 May cause choking odour in process enviroment

 Leakage in bromine outlet port connecting to a
lower packed distillation section may cause serious
problem to the process equipment because of its
Continuous process corosivity.

 May cause choking odour in process enviroment

due to chlorine usage
 Hot aqueous acid recycled to steaming tower is very
From aqueous HBr solutions corrosive and must be treated if being disposed to
(conventionally) nature.

1.7.8 Summary of Alternative Processes

Table 1.20 shows the summary of the alternative process and the selection of
the process.
 64
Table 1.20 : Summary of Alternative Process

Economic
Reaction Conversion
Synthesis Disadvantages Advantages Potential Raw Material
Raw Material Conditions For Equipment
( %) (RM/kmol)

 Probability of  Production capacity  Ceramics

forming liquid increased by 20% than (resistant to wet
bromine)
phase of bromine in conventional method
 Quartz/pyrex
the pipes  Direct transmittal to vessel towers
15°C to 30°C
Complete connecting the two storage for shipment
From aqueous (prechlorinatio)
Hydrobromic acid conversion of stages (maybe without further
HBr solutions RM 317/kg
and Chlorine gas bromine <2%) purification (reduce
(New Invention) 100°C (steaming
(>>97%)  Liquid bromine cost)
out tower)
might separate out
and contaminates
the system due to
excess chlorine.
 Need more  Bromine recovery is -RM 10470  Granite for
Conventional Atmospheric towers is
chlorine/steam high but not very pure. /kg
Method pressure sensitive to
NaBr2 (Brine) and 90 to 95 requirements
(Kubierscky over
(1.0 – 1.02 atm)
Chlorine achieved  Low overall pressuring.
distillation
efficiency of tower  Cause gasket
method) 108°C to 110°C damage and
tower breakage
 65
 Excess chlorine is
lost

Economic
Reaction Conversion Raw Material
Synthesis Raw Material Disadvantages Advantages Potential
Conditions ( %) For Equipment
(RM/kmol)

Sub-  Difficulty in  80% reduction in  Fiberglass

Continuous atmospheric maintaining sub- energy usage reinforced
two-stage Pressure atmospheric  Reduction in plastics like
NaBr2 (Brine) 97 to 98 -RM 10470
vacuum (0.41 - 0.82 pressure within chlorine (12%) vinylester for
and Chlorine achieved /kg
process atm) stages  Lower maintenance towers
(new method) cost
82°C to 99°C
 Must have good  Use of smaller
maintenance to contact tower size
80°C for ensure no  Lower steam
Continuous reaction blockage in the requirement
Hydrobromic
Bromine section and gas outlet port.  Lower pressure
acid and >99 achieved RM 317/kg _
process 90°C for needed
Chlorine gas
distillation  Using Reactive
section Distillation gives
good recovery of
bromine.
From aqueous Complete  Purification  Avoid forming
Hydrobromic 100°C process must be liquid phase of
HBr solutions conversion of
acid and (steaming out supervised bromine in the pipes RM 317/kg _
(Conventionall bromine
Chlorine gas tower) closely in order connecting the two
y) (>>98%)
66
to produce a stages (maybe <2%)
much pure liquid  High purity of
bromine bromine produced
 67

1.7.8.1 Summary of The Chosen Process – The Continuous Bromine Process

Production of bromine using this continuous process gives more advantages

than any other stated process path. The main reason for choosing this process is
because it has a higher economical potential than Kubierscky’s distillation method
and continuous two-stage vacuum process. The second important feature of this
process is the application of reactive distillation column whereby it gives a high
recovery of bromine (>99%), improves selectivity, reduce the amount of raw material
itself and also it prevents any production of byproducts. The divided section in the
reactive distillation column to upper reaction column and lower distillation column
gives a better separation process.

If compared to other two processes which gives a same economic potential

value, this continuous process requires lower steam supply and lower pressure
needed, which means it will reduce the operating cost in general. Therefore, this
continuous bromine process is more reliable than other bromine synthesis processes.