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1. BROMINE
1.
PRODUCT CHARACTERISTICS
Bromine Occurrence:
Sea water
Inland seas
Kharaghoda, Indian Ocean
Sassyksee, Black Sea
Shebhka el Melah, Tunisia
Salt lakes
Dead Sea, Israel
Ellon Sea, USSR
Searles Lake, Calif (USA)
Brine wells
Michigan (USA)
Arkansas, (USA)
Yakutsk, Siberia, USSR
Mineral salt deposits
Tachydrite
Rock salt
Sylvite
Carnallite
Bischofit
Hard salt
Original content, g/L
0.065
After concentration, g/L.
0.25
0.28
2.5
6
1.5 to 4.5
6.8
12 to 13
4 to 6
0.63 to 2.25
0.85
2 to 3
4 to 5
6 to 7 (CaCl2 solution)
wt%
0.438
0.005 to 0.040
0.117 to 0.300
0.155 to 0.0334
0.467
0.05 to 0.20
The Dead Sea is one of the richest sources, containing nearly 4 grams per litre of
Bromine at the surface and up to 6 grams per litre 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 litre.
Product details
Appearance
Odour
Colour
Dense, dark red, fuming, highly corrosive and
lacrimatory liquid.
Its strong pungent odour is detectable at 1
ppm by volume in air.
The colour of bromine varies with
temperature (yellow orange at 20 K, orange
red, red brown, to almost black at its melting
point).
Liquid bromine is always dark red, whereas
bromine vapours are usually orange to red
brown.
Specification
Description - The material shall be in the form of reddish-brown fuming liquid.
Requirements for Bromine, Technical
Sl. No.
1.
2.
3.
4.
5.
6.
Characteristics
Relative density* at 27/27 C, Min
Bromine, Percent by mass, Min.
Chlorine (as Cl), percent by mass Max.
Non-Volatile matter, percent by mass, Max.
Iodine (as I), percent by mass, Max
Sulphates, (as SO4), percent by mass, Max.
Requirement
3.092**
99.5
0.3
0.05
0.05
0.015
*
Relative density is the term adopted by ISO for specific gravity with water as
reference substance.
**
The relative density determined at any temperature within the range 15 to 30 C
can be adjusted to 27/27 deg C using the correction factor +0.0034 for every degree
Celsius fall and -0.034 for every degree Celsius rise in temperature.
Packing: The material shall be packed in glass bottles with lead caps or ground glass
stoppered bottles sealed with an inert material. These bottles shall then be packed in
expanded mica, diatomaceous silica or other inert absorbent. For larger packing,
homogeneously lead-lined mild steel drums or monel metal drums conforming to the
rules can be used.
2.
PRODUCT APPLICATIONS
The primary use of elemental Bromine is in the manufacture of Bromine compounds that
have chemical and biological activity, high density or fire retarding and extinguishing
properties.
Other applications of Bromine directly or as its compounds are given below.
*
*
*
In Pharmaceuticals
In Pesticides, In Dyes and Photography
In Sanitary preparations
*
Water disinfection
*
De sizing of cotton
*
Hair waving compounds
*
Absorption fluids
*
In some perfumes
*
Air conditioning
*
Ore flotation and drilling fluids
*
Zinc bromide storage batteries are used as load leveling devices in electric
utilities.
*
In the manufacture of Purified Terephthalic Acid.
The important downstream products of Bromine and its applications is given below :
Bromo Compounds
Major Applications
*.
Potassium Bromide
In Photography, Medicine, as Heat
stabilizer in Nylon, Brominating agent.
*.
Ammonium Bromide
Preparation of Photographic
products, Industrial water systems,
Paper Mills
*.
Sodium Bromide
Preparation of Photographic Products,
Brominating agent, Oilfield
chemicals, Waste water treatment,
Pharmaceuticals.
*.
Hydrogen Bromide/
Hydrobromic acid
Source of Bromine in industrial
Synthesis.
*.
Isopropyl Bromide/
N-propyl bromide
Intermediate for Pharmaceuticals,
Insecticides, Quaternary Ammonium
Compounds, Flavours and fragrances.
*.
N-Butyl Bromide
Intermediate for Pharmaceuticals,
Insecticides, Quaternary Ammonium
Compounds and Pigments.
*.
Ethylene di bromide
As fumigant and an important
constituent of Ethyl petrol used as
a motor fuel.
Ethylene dibromide finds use as
an agricultural fumigant but this
use in the United States is now
prohibited because of ground water
contamination.
Some minor fumigation uses are
allowed to continue, but the
predominant volume of Ethylene
dibromide used in soil fumigation
will cease.
*.
Ethyl bromide
Used in the manufacture of
Pharmaceutical like Vitamin A etc.,
in flame retardants, refrigerant.
*.
Potassium Bromide
Baking and Brewing processes.
*.
Methyl Bromide
As fumigant for soil fumigation and
for space fumigation to control
insects in stored products.
*.
Methylene bromide
In the manufacture of pesticides.
3.
IMPORTS
Around 2500 tonnes per annum.
4.
EXPORTS
Nil
5.
INDIAN MANUFACTURERS
*
*
*
*
*
DCW Limited, Mumbai
Tata Chemicals Ltd.Mumbai
Ballarpur Industries Ltd.,Karnataka
Chemplast Sanmar Ltd.,Tamil Nadu
South India Bromine and Allied Chemicals (P) Ltd.,Tamil Nadu
6.
DEMAND SUPPLY TRENDS
Demand level
:
Around 3250 tonnes per annum
Indian requirements are largely met by imports.
Estimated growth rate in demand: 6 to 7% per annum
7.
MANUFACTURING PROCESS AND TECHNOLOGY DEVELOPMENT
The process of manufacture of Bromine from Sea Bitterns is given below :The bittern is acidified with Sulphuric acid to a pH of 3.5 and pre-heated to 85 to 90 deg
C. The hot bittern is run through a tall granite tower packed with raschig rings while low
pressure stress and a 10% excess of the theoretical chlorine are introduced slightly above
the bottom of the tower and made to pass in counter current direction at suitable rates.
MgBr2 + Cl2 > MgCl2 + Br2
The Bromine is liberated in vapour form which is condensed in a tantalum condenser
along with steam and some chlorine and then taken to the gravity separator, where
Bromine and water layer are separated.
Manufacturing Process of Bromine (Developments in the process routes).
The first economically successful recovery of Bromine directly from the sea was carried
out near Wilmington, North Carolina (USA), using an air-blowing process originally
developed for brine operations by H.H. Dow, USA.
The use of air rather than steam has been preferred, because the cost of steam to heat
ocean water, with its Bromine content of only about 65 mg/litre. would be prohibitive.
Another process for the recovery of Bromine from sea water was developed on a
commercial scale by Ethyl Corporation in the US. The process involved the treatment of
seawater with chlorine and aniline and collection of the precipitated Tri bromo aniline.
Current bromine production methods are based on modified Kubierschky or steaming out
processes and the Dow chemicals blowing out process.
Technology Developments
Bromine producers have formed the Bromine Science and Environmental Forum to tout
the safety and value of bromine products, including bromine based flame retardants.
The group says that it will sponsor research on bromine compounds to evaluate health
and environmental effects. It will also "act as the industry's global voice" on
environmental issues and seek to ensure that scientific information on its products is
advanced and more widely understood." The group consists of Albemarle, Dead Sea
Bromine, Great Lakes Chemicals, Elf atochem and Tosoh.
8.
GLOBAL SCENARIO
Global demand
Present Global demand for Bromine is estimated to be around 500,000 tonnes per annum.
The annual growth rate in demand is estimated to be around 3% per year.
World Producers:
United States is the major world producer of Bromine, followed by Israel.
Israel has been able to increase its production substantially from 23,000 tonnes in 1976 to
around 2,00,000 tonnes per annum at present, due to the availability of the richest source
of Bromine i.e., Dead Sea Brine and its concentrates and the process innovations brought
about by the technologists.
Global outlook
Recovery of Bromine form seawater is mainly done in US, erstwhile USSR, Italy and
Japan.
Phasing out of methyl bromide and ethylene bromide has forced bromine production to
diversify into new markets.
Still the largest end-use for bromine compounds, flame retardants account for 30% of
world bromine consumption.
About 45% of this is consumed in the US, with 31% in western Europe and 14% in
Japan. By 2000 the brominated flame retardants market is predicted to have grown by 8%
per year, with Asia leading the way.
Aside from flame retardants, several major producers are developing their fine chemicals
capabilities for bromine to meet the demand from the pharmaceutical industry. During
the mid-1990s, a number of anti-hypertension drugs were introduced using bromotoluene
as an intermediate in manufacture. Another intermediate, bromethoxy naphthalene, is
important in making naproxen, an anti-inflammatory that came off-patent in 1997.
Other promising new sectors for bromine include swimming pool disinfectants, industrial
water treatment, air conditioning absorption systems and precious metal leaching.
9.
RECOMMENDATIONS
Generally, the facilities for manufacturing Bromine are located near the source of
availability of natural brines or bitterns containing usable levels of Bromine.
Keeping the availability of the source of bromine in view, the project for the manufacture
of Bromine can be favourably considered in TamilNadu.
Manufacturers with Organic Bromine compounds production facilities near their
bromine-producing plants have lower production costs than non-bromine producers
because Bromine shipping and handling costs are minimized and by product inorganic
bromides can be readily processed to recover bromine values.
Recommended capacity
300 tonnes per annum
Estimated project cost
Rs.700 lakhs