Chapter 1 Introduction

1.1 History

A. J. Ballard is recognized as an inventor of bromine. In 1825, while investigating uses for the waste liquor from salt manufacture at Montpellier in France, Ballard observed that upon saturation with chlorine, the new red liquid could be obtained by distillation (1, 2).Having ascertained by repeated experiments the elementary nature of the new substance, Ballard reported his new discovery to the French Academy of Science suggesting the name of new element – ‘muride’. The academy nominated a committee, composed of L. N. Vaquelin, L. J. Thenard and L. J. Gay Lussac, who confirmed Ballard’s findings (3, 4) and suggested to name the new element ‘brome’ from the Greek word ‘bromos’ meaning ‘stink’ in agreement with its outstanding unpleasant smell.

It appears that the discovery of bromine was made almost simultaneously by few other chemists besides Ballard. Carl Lowing (1, 5) independently isolated bromine at Kreuznach, Germany in 1825 and was in the process of studying its properties when Ballard’s paper appeared. J.Von Liebig (6) also isolated bromine in the same period but labelled it as ‘chloro iodide’, was shocked at his inability to recognise in time the true nature of the substance obtained by him.

Bromine was the third of the halogen family to be discovered and separated, after chlorine in 1774 and Iodine in 1811.

Ballard himself, and many others, prepared and described compounds of bromine with sulfur, phosphorus, chlorine, iodine as well as hydrogen bromide, metallic bromides and bromates. Reactions of bromine with organic compounds such as acetic acid and ethanol are mentioned quite soon after the discovery of new element.

The atomic weight of bromine (7) found published in 1833 and its value being given as 78.392 (basis H = 1).

1.2 Occurrence

Bromine does not occur in nature as the free element but is found solely as the bromide. The first mineral to contain bromine was discovered in 1841 by Berthier; the mineral was apparently bromyrite (silver bromide). There are known only a few bromine compounds which may be considered as minerals in the strict meaning of the word. All of them consist wholly or partly of silver bromide, the least soluble bromine salt. The minerals are bromargyrite (Ag Br), embolite [Ag (Br, Cl)] and iodo embolite [Ag (Br, I)]. The importance of these bromine minerals is negligible as far as bromine manufacture is concerned.

Bromine also appears in variable amounts in the biosphere. The bromide concentration in terrestrial plant is about 7 ppm and in fresh water plants 22 ppm In the animal world, the highest bromide content is found in sea life, such as fish, sponges and crustaceans (1, 8).Many natural products containing organic bromine have been isolated such as dibromoindigo (Tyrian purple) from sea snails, bromoform from red algae and brominated phenols & diphenyl oxides from sponges & marine bacteria (9).

The bromide from weathered rocks are dissolved and transported into hydrosphere and are the most easily recoverable bromine. The concentration of bromine in ocean water is about 65 mg/l and varies in parallel with the concentration of other salts. The chlorine-bromine weight ratio in ocean water fluctuates a little around the value 292. Bromine in ocean water is in the state of bromide ion. Salines are a name often given to brines obtained in the manufacture of salt from sea water. Besides man made Salines there are Salines formed by nature. Such natural Salines owe their formation to special topographical & climatical conditions. The name bittern is also frequently used for Salines, but is seems better to have it reserved for more concentrated brines (>300 Be’) having about 2.0 – 2.5 gm/l bromine with other magnesium and potassium salts. The well brines are mostly natural but in many cases they have been created by pumping water into the salt layers which lie hundreds of meters below the surface. The Dead Sea (Israel) is the richest concentrate of bromide as compared with salt brines and ocean waters. The original bromine content is to the tune of 4 – 6 gm/l and after concentration it reaches as high as 12 – 13 gm/l bromine. The Elton Lake (USSR) has bromine content 0.63 – 2.25 gm/l. Searles Lake (USA) is another inland sea / lake having substantial total bromine content. The bromide ion content in Searles Lake is 0.85 gm/l. The occurrence of bromine in various sources (1, 3) is summarized in Table-1.

TABLE – 1

Bromine source Country / Location

Area Original content

gm/l

After concentration

gm/l Sea water - - 0.065 -Natural salines � Kharaghoda

(Rann of Kutch)

India (Indus Delta)

18000 km2 0.25 6.0

� Sebkha-el-melah

Tunisia (Mediterran-

ean Sea)

150 km2 2.5 6.8

� Kara-Bogaz Col

kaspian Sea 18000 km2 0.12 – 0.43 -

� Sakskoe Ozero (Ssassyksee)

Crimea, USSR

(Black Sea)

- 0.28 1.5 – 4.5

� Shivash Sea Crimea, USSR (Azov

Sea)

- 0.214 -

Brine wells � Michigan � Arkansas � Yakoutsk

USA USA USSR

---

2 – 44 – 56 – 7

---

Salt lakes � Dead Sea Israel - 4 – 6 12 – 13 � Elton Sea � Searles Lake

USSR USA

--

0.63 – 2.25 0.85

--

Mineral deposits (Wt %)

� Rock Salt - - 0.005 – 0.040 -� Sylvite - - 0.117– 0.300 - � Carnallite - - 0.155 – 0.334 - � Bischofit - - 0.467 - � Tachydrite - - 0.438 - � Hard Salt - - 0.05 – 0.20 -

The total bromine content in the crust of the earth has been estimated to be 1015- 1016 tons or 0.00016% bromine. 1.3 Manufacture

The first commercial production of bromine was from native salt brines in 1846 at Freeport, Pennsylvania by David Alter. The Dow process for extracting bromine from sea water began in 1934 near Wilmington, North Carolina. The development in the technology of bromine manufacture is well narrated by Jolles (3). As on date the hot or steaming out process and cold or blowing out process are in use world over. These processes are not discussed here at length. However, the process followed to recover bromine from industrial waste is narrated in its relevant section. 1.4 Properties

Bromine, Br [7726-95-6], Atomic No. 35, Atomic Wt. 79.916 (10, 11, 12), stable isotopes with mass number 79 (50.54%) & 81 (49.46%), Atomic radius 1.19 Ao, Ionic radius 1.96 Ao, is a diatomic with a normal valence -1. It is a dense, dark red fuming, heavy, highly corrosive and lachrymatory liquid. Its strong pungent odour is detectable at 1 ppm by volume in air. It is the only non-metallic element liquid at room temperature. The chemical properties of elemental bromine are well described by Ullmann (1) and Jolles (3).They are not described here but definitely they are used as a tool for the recovery of bromine and its compounds from industrial wastes. The physical properties of elemental bromine like boiling point & latent heat of vaporization (13), density (14), surface tension (15), viscosity micro poise (16), critical temperature (17), vapour pressure (18), specific heat (19), coefficient of thermal expansion (20), electrical conductivity (21), dielectric constant of liquid bromine (22), dielectric constant of bromine vapour (23), specific heat (24) etc are summarized in Table – 2.

TABLE - 2

Physical property Value � Freezing point oC -7.25 � Boiling point oC 58.78� Density gm/cc

0 oC15 oC20 oC

3.1875 3.1396 3.1226

25 oC30 oC

3.1055 3.0879

� Vapour density gm/l 0 oC ; 101.3 kPa

7.139

� Refractive index 20 oC25 oC

1.6083 1.6475

� Surface tension dynes/cm 0 oC20 oC25 oC50 oC

45.0 41.5 40.9 36.2

� Viscosity mm2 / s (= cst) of liquid bromine

20 oC30 oC40 oC50 oC

0.314 0.288 0.264 0.245

� Viscosity micro poise of gaseous bromine

12.8 oC65.7 oC99.7 oC139.7 oC179.7 oC220.3 oC

151.1 170.5 188.5 207.9 227.3 248.0

� Critical temperature oC 311� Critical pressure mPa (atm) 10.3 (102) � Critical volume ml/gm mole 144 � Vapour pressure p, mmHg

-7.3oC-5.0 oC

0 oC5.0 oC10.0 oC15.0 oC20.0 oC25.0 oC30.0 oC35.0 oC40.0 oC45.0 oC50.0 oC55.0 oC58.78 oC60.0 oC

44.0 50.5 65.9 85.3 109.0 138.0 173.0 214.0 264.0 324.0 392.0 472.0 564.0 670.0 760.0 793.0

� Specific heat at 1 – 45 oC / Cal / g / oC 0.1071� Coefficient of thermal expansion

at 0 – 30 oC 0.0011� Latent heat of vaporization

at boiling point, cal / gm

44.8 � Electrical conductivity

at 17.2 oC, ohm-1 cm-1 1.3 x 10-13 � Dielectric constant cgse of liquid

bromine 0 oC

24.7 oC3.336 3.1484

� Dielectric constant cgse of bromine vapour at 180 oC 1.0128

� Specific heat cal/gm/oC of gaseous bromine (up to 388 oC)

0.23

� Solubility in water g/100 gm water at 20 oC 3.5

� Solubility of water in bromine ppm at 25 oC 380

1.5 Quality specifications and testing

Typical industrial product specifications for bromine (25) are given in Table – 3.

TABLE – 3

Parameter Value � Bromine % by mass 98.5 min.� Chlorine (as Cl) % by mass 0.5 max.� Non volatile matter % by mass 0.05 max.� Iodine (as I) % by mass 0.05 max.� Sulfates (as SO4) % by mass 0.015 max.

1.6 Storage and transportation

Bromine is usually shipped in monel alloy drums constructed of 14 gaze metal and designed to contain 102 kgs of liquid bromine. Larger bulk shipments of bromine use lead or nickel lined tank cars or tank trucks. The latter must be filled to a minimum 98% of capacity before shipping to avoid inertia effect in transport. Storage tanks should be protected from moist air.

In India, bromine is packed in 1 ltr glass bottle that contains about 3.0 to 3.5 kg bromine /bottle. 6 Nos. of these glass bottles are then packed in a wooden crate with partitions and the empty space of the crate is filled with saw dust or any other material to absorb shocks while transportation.

For transferring bromine, plastic lined steel is a versatile material that combines chemical resistance with reinforced strength. Fluorinated plastics such as Kynar, Teflon, Kel F and Viton find wide spread use in equipment, valves, piping and gaskets. Nickel and monel alloys & haste alloy C may be used with dry bromine (less than 30 ppm water) but are severely attacked by wet bromine. Tantalum may be used with either wet or dry bromine

up to 150 o C. Steel and stainless steel usually are unsatisfactory. However, the use of steel is possible when nitric oxide is present to prevent corrosion. Chemical lead & glass lined steel are probably the most versatile & practical materials for general use in storing and handling bromine. For additional information, see industrial product brochure on bromine handling and shipping (26).

1.7 Toxic hazards

The chemical reactivity of elemental bromine with living matter presents serious hazards in handling on any scale. Careful attention must be given to the likelihood of prolonged exposure of operators to even very low concentrations of the vapour.

Effective decontaminants which should be at hand when bromine is handled are water, safety showers & eye wash fountains, anhydrous ammonia, saturated alkaline thiosulfate solution, lime slurry and dry soda ash. Oxygen as an addition to ammonia was found to be invaluable as an inhalant in severe cases.

1.8 Safety

Safe handling of bromine demands the following measures: rigorous avoidance of all contact of bromine with skin, eyes & clothing and adequate ventilation with all possible precautions against inhaling the vapours when significant quantities of bromine are to be handled. A good practice requires that goggles, face shield, gloves and plastic or rubber suit be worn and suitable gas masks are available. Preventive health measures and first aid procedures are given in product brochure (26).

1.9 Uses

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. Bromine products are well represented in such use areas as gasoline additives, flame retardants, agricultural chemicals, drilling fluids, photographic chemicals, sanitizers, dyes, pharmaceuticals, water disinfection, desizing of cotton, bleaching of pulp and paper, air conditioning absorption fluids, hair waving compositions and others.

1.10 Global scenario

With this general background in mind let us now switch over to the global scenario of bromine and its compounds in a last decade.

Estimated world production of bromine (27) in descending order and percentage of total for 2005 is given in Table- 4.

TABLE - 4

Country % of world bromine production estimated in the year 2005

United State of America 38.6 Israel 38.2 China 7.8 United Kingdom 6.4 Other countries including India 9.0

Total 100

Because of depleting reserves, distribution and economics, environmental constraints and the emergence of Israel as the world’s second ranked producer, the US portion of the world production had decreased steadily since 1973 when the United States produced 71% of world’s supply. World bromine annual plant capacities and sources (28, 29) as of December 31, 1999 & December 31, 2004 are given in Table- 5

TABLE – 5

Capacity (Thousand kilograms)

Country and Company or Plant

Location

As of 31.12.1999

As of 31.12.2004

Source

Azerbaijan � Neftechala

Bromine Plant

Baku 5000 4000 Underground brines

China � Laizhou Bromine

Works

Shandong 30000 43000 Underground brines

France � Atochem � Mines de Potasse

d’ Alsace S.A. � Albemarle

Port de Bouc Mulhouse Port de Bouc

13600 2300

--

--

15000

Sea water Bitterns of mined potash Sea water

India � Hindustan Salts

Ltd. � Mettur Chemicals

Ltd. � Tata Chemicals

Ltd.

Jaipur Mettur Dam Mithapur

Total of three Co.

1500

Total of three Co.

1500

Sea water Bitterns from salt production

Israel � Dead Sea

Bromine Co. Ltd.

Sdom

190000

190000

Bitterns of potash production from surface brines

Italy � Societa Azionaria

Industrial Bromo Italiana

Margherita di savoia

900

900

Sea water bittern from salt production

Japan � Toyo soda

manufacturing Co. Ltd.

Tokuyama

20000

20000

Sea water

Jordan � Jordan Bromine Co. Ltd.

Safi

--

50000

Bitterns of potash production from surface brines

Spain � Derivados del

etilo S.A. Villaricos 900 900 Sea water

Turkmenistan � Nebitag Iodine

Plant � Cheicken

Chemical Plant

Vyshka Balkan

3200

6400

3200

6400

Underground mines Underground mines

Ukraine � Perekopskry

Bromine Plant

Krasnoperckopsk

3000

3000

Underground mines

United Kingdom � Associated Octel

Co. Ltd.

Amlwch

30000

--

Sea water

United States of America � Albemarle Corp. Magnolia Plants

Satellite Plant � Great Lakes

Chemical Corp. Catesville Plant El Dorado Plant Marysville Plant Newell Plant

� The Dow

Chemical Co. Ludington Plant

Columbia County, Arkansas Union County, Arkansas

Union County Arkansas

Mason County Michigan

140000

--

Total of four plants

177000

20000

Total of two plants

148000

-- Total of

three plants 130000

9000

Well brines

Well brines

Well brines

Country wise estimated world bromine refinery production (27, 28, 30) (in thousand kilograms) is given in Table – 6.

TABLE - 6

Country 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005Azerbaijan 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000China 32700 41400 50100 40000 45000 42000 40000 42000 42000 43000 43000France 2260 2024 1974 1950 2000 2000 2000 2000 2000 2000 2000Germany - - - - - 500 500 500 500 500 500India 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500Israel 130000 160000 180000 185000 185000 210000 206000 206000 206000 206000 210000Italy 300 300 300 300 300 300 300 300 300 300 300Japan 15000 15000 20000 20000 20000 20000 20000 20000 20000 20000 20000Jordan - - - - - - - 5000 20000 20000 50000Spain 200 100 100 100 100 100 100 100 100 100 100Turkmenistan 100 102 130 150 150 150 150 150 150 150 150Ukraine 3500 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000UnitedKingdom

26200 30600 35600 30000 28000 32000 35000 35000 35000 35000 35000

United Statesof America

218000 227000 247000 230000 239000 228000 212000 222000 216000 222000 212000

Total 432000 483000 542000 514000 526000 542000 523000 540000 548000 556000 580000

Note: 1. World totals, US data and estimated data are rounded to no more than three significant digits, may not add to total shown.2. Table includes data available through April 20, 2000, for the years 1995 – 1999, through April 12, 2005, for the years 2000 –

2004 and through January-2006, for the year 2005.3. In addition to the countries listed, several other nations produce bromine, but output data were not reported, available general

information is inadequate to formulate reliable estimates of output levels.

Israel ranked second behind the United States in world bromine production. Approximately 90% of Israel’s production is for export, accounting for about 80% of international trade in bromine and bromine compounds to more than 100 countries. Exports from Israel were used to produce bromine compounds at a plant in the Netherlands for export to other countries.

1.11 World resources

Resources of bromine are virtually unlimited (30). The Dead Sea in the Middle East is estimated to contain 1 billion tons of bromine. Sea water contains about 65 parts per million of bromine or an estimated 100 trillion tons of bromine. Bromine is also recovered from sea water that has been evaporated to produce salt. The bromine content of underground water in Poland has been estimated to be 36 million tons.

1.12 World review of bromine compounds

European Union: The European Union (EU) directives on Waste Electrical and Electronic Equipment (WEEE) will require recycling of most electrical and electronics (E & E) equipment in Europe. Polymer producers of high impact polystyrene and acrylonitrate – butadiene – styrene are likely to be most affected because much of the E & E market is not accessible without the use of halogenated flame retardants (HFR), such as brominated flame retardants (BFR), because of fire safety demands. To ban the use of HFRs could require prohibitively large investments in new processing equipments owing to individual polymer reliance on BFRs to meet the desired fire safety standards. The directive required the separation of at least 4 kg of WEEE per inhabitant per year by December 31, 2006. The directive gave producers a clear guarantee that no individual EU member state will be able to introduce separate bans or restrictions on any substance other than those specified in the directive (31).

The EU directive on reduction of hazardous substances will take effect in 2006, mandating that electronics manufacturers switch to lead (Pb) free solder system. These systems typically run at temperatures between 30oC and 50oC, higher than traditional lead systems, forcing manufacturers to make internal components with higher thermal stability. Great Lakes announced that tests of 1-di bromo styrene flame retardant (FR) in electronics applications show superior results in lead-free solder systems (32).

Israel: Dead Sea Bromine Group (DSBG) is the world’s leading producer of elemental bromine and a leader in the development and supply of bromine compounds. DSBG consists of four divisions that include industrial chemicals, FR., Soil treatment and biocides. Its manufacturing facilities are located in Israel, China, Netherlands and United States. DSBG is a member of Israel Chemical Ltd., which includes Dead Sea Works, which controls potash and salt, and Rotem which controls fertilisers.

Japan: Great Lakes and Japan’s Teijin Chemicals planned a joint venture to be 50% owned by each company and head quartered in Japan. Great Lakes will be the exclusive marketer of the product that will be made in El Dorado, AR and Matsuyama Japan (33).

Jordan: At Safi, a bromine and derivatives and FR plant that produced bromine from the Dead Sea was leased by Jordan Bromine Co. Ltd. (A joint venture owned 50% by Arab Potash Co. and 50% by Albemarle) (34).

Tajikistan: In the south west of the country, there are accumulations of underground mineralised water with concentrations of boron, bromine, iodine, lithium and strontium. The Tut-Bulak deposit, 3.5 km east of Yavan and 13 Km from the Yavansk Chemical Combine, reported values of brines containing 168 ppm bromine. Technical evaluation of one cubic meter of the brines reported the possibility of 194 tons of iron bromide.

United States of America: The quantity of bromine sold or used in the United States from three companies operating in Arkansas & Michigan accounted for 100% of elemental bromine production. Arkansas, with six plants led the nation in bromine production and bromine was the leading mineral commodity in terms of value produced in the state. In Michigan, bromine is produced as a by product of magnesium compounds production. Three bromine companies in the United States accounted for more than 1/3 of world production. An US company’s subsidiary signed a joint venture agreement with a Jordanian company to build a bromine complex at Safi, Jordan. Construction, which began in 2000 and was completed in Oct 2002, included a 50,000 Tons / year bromine plant. A major domestic producer of bromine and bromine compounds is creating three technology centres that included bromine and bromination technology to help in emerging scientific fields. The centres are expected to add a long range dimension to new product development capability and expand its technology acquisition capability. The company acquired the bromine fine chemicals business of a French producer located at Port-de-Bouc.

1.13 Market outlook of bromine compounds

Flame retardants (FR): Bromine is used as a FR in plastics and also acts in synergy with many other materials to increase the overall effectiveness of the FR. It is estimated that about 50% of the consumption of the bromine is used in brominated FRs (BFR) chemicals commonly used in many domestic and industrial appliances and such equipment as computers, furnitures, insulation boards, mattresses, mobile phones, televisions and many others. About 90% of electrical and electronics appliances contain BFRs to increase their resistance to fire. BFR is also used in textile for upholstered furniture. Although usage fluctuates along with the overall cycles in the economy, assuming sustained economic growth, demand is expected to grow by 4% per year. The ban on and voluntary withdrawal of two poly brominated diphenyl ether compounds resulted in a decrease in demand for bromine between 2001 and 2004. Recycling efforts in Europe for BFRs plastics in electrical usages, which is easier to recycle than some other FRs compounds, may increase the demand for BFR products because they are thought to be more environmentally friendly, especially by countries concerned about recycling, such as Japan. Growth is expected to increase overall in BFRs as the consumer product safety commission (CPSC) approves fire safety standards for upholstered furniture in the United States and if higher flammability standards are voluntarily adopted for televisions in Europe.

Health care: A major use of bromine compounds is in the manufacture of bulk drugs and pharmaceuticals. Brominated substances are important ingredients of many over-the-counter and prescription drugs, including analgesics, antihistamines and sedatives. The use of bromine is expected to increase in antihistamines if pseudo ephedrine, a key ingredient in illegal methamphetamines, is made a prescription product. Some of the bromine drugs have proved effective in the treatment of cocaine addiction and pneumonia.

Dye stuffs: The introduction of halogen substituents in dyestuff molecules has a marked effect. This effect is often beneficial and in consequence bromine plays a very important role in the dyestuff industry. The presence of bromine in a dyestuff often produces a desirable shade change, usually more marked than with the corresponding chloro compound. Other desirable properties may also be conferred viz. decreased solubility or higher tinctorial value in the case of pigments. Intermediates containing bromine are used in many instances with the bromine playing an essential part either when contained in the final dyestuff or as a reactive site. The bromine used in various types of dyestuffs viz. Anthraquinone dyes, Indigoid and thioindigoid dyes, Azo dyes, phthalocyanine pigments, phthalein and other dyes.

Photography: Bromine compounds are used to make the light sensitive component of a photographic emulsion. Other bromine compounds are used in ingredients in photographic development. Recent developments in digital imaging can produce electronic prints and overhead transparencies without the need for wet processing film. This would appear to cause a decrease in bromine usage in colour film and film processing, however, 75% to 85% of all televised programmes seen during prime time are recorded on 35 mm motion picture film and then transferred to video tapes or laser disks for display, and the majority of feature films for movie theatre presentations are shot and printed on film, because film provides higher image resolution. As digital imaging technology improves and digital equipment and printers become more affordable in the next decade, future use of bromine in film processing may be limited to speciality film imaging.

Petroleum: Demand for bromine as a gasoline additive has declined since 1970s, when the Environmental Protection Agency (EPA) issued regulations to reduce and eliminate lead in automotive gasoline. In 1979, the amount of bromine sold for this application had reached a peak of 225 million kgs. The rapid decline to 141 million kgs in 1986 was a direct result of the limits on lead in leaded automotive gasoline.

The clean air act (CAA) requires mobile source, such as cars and trucks, to use the most effective technology possible to control emissions. Newer prototypes of the fuel cell that burn gasoline can double the mileages and decrease emissions by using unleaded gasoline or other nonbrominated fuels. However, bromine compounds are used as a constituent of antiknock fluid in leaded fuel is still in use in small aircraft, farm equipment and in third world countries.

Calcium bromide, zinc bromide and sodium bromide, collectively referred to as clear brine fluids (CBFs), are used in the oil and gas well drilling industry for high density, solids free completion, packer and work over fluids to reduce the likelihood of damage to the well bore and productive zone. The use of calcium bromide, zinc bromide and sodium bromide as CBFs as oil well completion & work over fluids has benefited in recent years from high gas and oil prices resulting from the increased demand for petroleum products. Increased demand for CBFs is expected to continue until alternative sources of fuel become available.

Agriculture: Bromine compounds are effective pesticides, used both as soil fumigants in agriculture, particularly fruit growing, and as a fumigant to prevent pests from attacking stored grain and other produce. Significant volumes of world trade in agriculture goods depend on the use of bromine compounds to ensure compliance with mandatory rules on quarantine. Bromine compounds are also used as intermediates to make other agriculture

chemicals. Analyses have shown that pesticide use varies from year to year depending on acreage, economics, pest problems, types of crop planted, weather and other factors.

Sanitary preparations: The growth potential remains high for bromine base biocides for use in industrial cooling systems because of environmental restrictions on chlorine and new alkaline base chemical treatment programmes. The most common bromine compound used in cooling waters are 1-bromo-3-chloro-5,5-dimethyl hydantoin and mixtures of sodium bromide and sodium hypochlorous acid. One of the major uses of bromine is as a water purifier / disinfectant as an alternative to chlorine. Brominated compounds are used for water treatment in indoor swimming pools, hot tubs and whirlpools. Bromine has been found to be safer than its substitutes in sanitary preparations because bromine has a higher biocidal activity level for the same volume of product. The use of bromine compounds is expected to continue increasing in the spa and hot tub sector and to increase as a gentler disinfectant compared with chlorine in swimming pools.

With this general introduction of bromine chemistry and its global scenario, let us now concentrate on the overall picture of Indian market.

1.14 Bromine related industries in India and their effluents

The major bromine producers in India are not only the ones mentioned above. It is because the others have not made available the information related to their activities on internet and consequently while compiling the data by the international compilers they are not included. It is also evident that the information related to the Indian industries, which are mentioned in above, is also not up to date. Again this is because an Indian industrialist, on an average, is not Techno savy on one hand and on the other hand, Indian Industries, like any other businesses, are family businesses and they believe in maintaining the business secrecy to the extent possible. No published data is available for Indian bromine manufacturers and to have a correct picture of the total quantum of bromine produced in India we have either to visit personally or to collect information through reliable sources or through communication. Information gathered in this way is compiled in Table-7

1.14.1 Bromine manufacturers in India

TABLE - 7

Company Location Capacity (ton)

Source

Tata Chemicals Ltd.

Mithapur (Gujarat) 1000 Sea water bittern from salt production

Saurashtra �Chemicals Ltd.

Porbandar (Gujarat) 750 Sea water bittern from salt production

Dhrangadhra �Chemicals Ltd.

Dhrangadhra (Gujarat) 300 Sea water bittern from salt production / Natural salines

Gujarat Heavy �Chemicals Ltd.

Sutrapada-Veraval (Gujarat)

750 Sea water bittern from salt production

Agrocel Ltd. �� Dhordo - Kutch (Gujarat)

2000 Natural salines

Solaris Chemtech Ltd. ��

Khavda-Kutch Singach-Jamnagar (both Gujarat)

10,000 Natural salines

Hindustan Salts Ltd.

Jaipur (Rajasthan) 2000 Sea water bittern from salt production/Natural salines/Sub soil well brines

Mettur Chemicals Ltd.

Mettur Dam (Tamil Nadu)

750 Sea water bittern from Salt production.

� Not in production �� For captive consumption only

Solaris Chemtech Limited is also commencing planned expenditure of Rs.120 Crores to increase production of bromine and speciality bromine chemicals. The bromine capacity will be increased from 10,000 tons/ annum to 24,000 tons/ annum and that of bromine chemicals from 5,500 tons/ annum to 21,000 tons/ annum over the next three year (35).

The discussion on global market scenario in a previous chapter vis-à-vis domestic production capacity compelled us to think that

� Whether there exists a demand supply gap of bromine and bromine chemicals in India?

� Where from these requirements are met? � What are the bromine chemicals that fall in demand supply gap criteria?

The following tables satisfy our quarries. Table 8, 9 and 10 gives the quantity of liquid bromine, sodium bromide and potassium bromide imported in India during the last decade (36). Table 8(a), 9(a) & 10 (a) represents the foreign exchange spent towards the quantity of liquid bromine, sodium bromide and potassium bromide imported in India during the last decade (36).

1.14.2 Liquid bromine imported in India (36)

TABLE - 8

QUANTITY IMPORTED IN KgsCOUNTRY 96-97 97-98 98-99 99-2000 2000-2001 2001-2002 2002-2003 2003-2004 2004-2005CHINA 41072 14691 24990 81559 76285 3500 - 8811 24934CYPRUS - - - - - 33000 - - -GERMANY - - 56340 - 1000 - 145 506 -HONG KONG 12287 - - - - - - - -ISRAEL 328920 973750 1740631 566130 1085126 815967 1256255 978134 674740ITALY 11000 - - - - - - - -JAPAN - 4739 - - 600 - - - 17440JORDAN - - - - - - 201500 603960 1914519NORWAY - - - - - 100 - - -ROMANIA - - - - - - - 69890 -RUSSIA 56360 77680 - - 22680 56700 170100 34680 -SINGAPORE 57020 - - - - 1134 - - 2100SPAIN - - - - 14500 - - - -SWITZERLAND - - - - - 157930 96000 - -UAE 18300 - - - 11340 11340 - - -U.K. 102380 1340 84020 11340 11340 193109 216080 585598 -UKRAINE 510880 158040 427640 378830 737739 660070 470219 766857 876373UNSPECIFIED - - - - 22340 - 34818 - 71434U.S.A. 617360 229800 35162 - 12940 59000 156808 135506 34880TOTAL 1755579 1460040 2368783 1037859 1995890 1991850 2601925 3183942 3616420

1.14.3 Foreign exchange spent towards liquid bromine imported in India (36)

TABLE - 8(a)

VALUE IN Rs.COUNTRY 96-97 97-98 98-99 99-2000 2000-2001 2001-2002 2002-2003 2003-2004 2004-2005CHINA 3662753 3249556 7687594 4560969 5384714 751371 - 1174747 1234846CYPRUS - - - - - 1971642 - - -GERMANY - - 2998815 - 54385 - 7848 17687 -HONG KONG 686326 - - - - - - - -ISRAEL 22644776 44607796 72469291 23611947 49013320 38542671 51039598 31216877 32522722ITALY 590961 - - - - - - - -JAPAN - 1806743 - - 127896 - - - 671637JORDAN - - - - - - 6246760 21050612 86222496NORWAY - - - - - 14271 - - -ROMANIA - - - - - - - 2253911 -RUSSIA 3099560 3517608 - - 1259014 2865278 8394396 1738741 -SINGAPORE 3224521 - - - - 612820 - - 139023SPAIN - - - - 716696 - - - -SWITZERLAND - - - - - 6624622 4114166 - -UAE 786849 - - - 638576 567891 - - -U.K. 5593607 433053 3857142 648434 624789 9501508 8357173 20213791 -UKRAINE 28550501 6038414 23577435 18347899 36688786 36532174 23626620 40206399 45969613UNSPECIFIED - - - - 1218790 - 1228882 - 1867952U.S.A. 37219769 14148680 3235686 - 744236 1867340 5827493 5298196 1326893TOTAL 106059623 73801850 113825963 47169249 96471202 99851588 108842936 123170961 169955182

1.14.4 Sodium bromide imported in India (36)

TABLE-9

QUANTITY IMPORTED IN KgsCOUNTRY 96-97 97-98 98-99 99-2000 2000-2001 2001-2002 2002-2003 2003-2004 2004-2005AUSTRALIA - - - - - - 8480 - -BELGIUM - - - - - - - - 30CHINA - - - - 86000 46000 85500 80910 73750FINLAND - 9000 - - 200 - - - -GERMANY - - - - - - 397 - 811IRELAND - - - 3200 - - - - -ISRAEL 5000 - 6150 9385 2000 20999 104998 63000 -JAPAN - - - - - 16500 - - -KOREA(SOUTH) - - - - 120 - - - -NETHERLANDS - - - - 200 - 10 40000 59480RUSSIA - - 80 - - - - - -SINGAPORE - - - - - - 1150 - -U.K. 199000 74000 80000 111599 60790 40040 37000 70010 39150U.S.A. - - - - - - 32 - 250TOTAL 204000 83000 86230 124184 149310 123539 237567 253920 173471

1.14.5 Foreign exchange spent towards sodium bromide imported in India (36)

TABLE-9(a)

VALUE IN Rs.COUNTRY 96-97 97-98 98-99 99-2000 2000-2001 2001-2002 2002-2003 2003-2004 2004-2005AUSTRALIA - - - - - - 270407 - -BELGIUM - - - - - - - - 1452CHINA - - - - 3818588 1978254 3737675 2866400 3432973FINLAND - 970460 - - 365908 - - - -GERMANY - - - - - - 173553 - 195590IRELAND - - - 207607 - - - - -ISRAEL 581760 - 346883 622821 138404 1020498 5020842 2624897 -JAPAN - - - - - 1296496 - - -KOREA(SOUTH) - - - - 285123 - - - -NETHERLANDS - - - - 368379 - 527 1174657 1069778RUSSIA - - 141808 - - - - - -SINGAPORE - - - - - - 121324 - -U.K. 8812733 5353977 4457166 5933951 3100704 4779077 1975317 2529106 1351481U.S.A. - - - - - - 22903 - 4649TOTAL 9394493 6324437 4945857 6764379 8077106 9074325 11322548 9195060 6055923

1.14.6 Potassium bromide imported in India (36)

TABLE-10

QUANTITY IMPORTED IN KgsCOUNTRY 96-97 97-98 98-99 99-2000 2000-2001 2001-2002 2002-2003 2003-2004 2004-2005BELGIUM - - - - - - - 4 -BRAZIL - 18000 165935 245225 100000 - - 358228 16772CHINA - - - - - - 5000 5000 28000GERMANY - - - - 950 - 543 48603 333JAPAN 2500 - 400 - - - - - -SPAIN - - - - - 10 - 1400 1000U.K. - 55 - - - - - - 11USA - - - - - - - - 120TOTAL 2500 18055 166335 245225 100950 10 5543 413235 46236

1.14.7 Foreign exchange spent towards potassium bromide imported in India (36)

TABLE-10(a)

VALUE IN Rs.COUNTRY 96-97 97-98 98-99 99-2000 2000-2001 2001-2002 2002-2003 2003-2004 2004-2005BELGIUM - - - - - - - 3636 -BRAZIL - 175892 1745050 2681011 1060909 - - 3583922 157549CHINA - - - - - - 253264 176927 1356358GERMANY - - - - 192391 - 495830 284601 205477JAPAN 753026 - 83631 - - - - - -SPAIN - - - - - 54817 - 78466 87325U.K. - 238110 - - - - - - 732USA - - - - - - - - 6902TOTAL 753026 414002 1828681 2681011 1253300 54817 749094 4127552 1814343

1.14.8 Analysis of data

It is apparent from the data that the imports of liquid bromine is fluctuating, even though it has recorded the percentile growth of about 100% during the period under review considering the year 96-97 as the base year. Similar fluctuations are also observed for the foreign exchange spent towards its imports. However, it is important to note that the value spent in terms of rupees shows a clear cut down ward trend from Rs. 60.41 / kg in the year 96-97 to Rs. 46.99 / kg in the year 04-05.

To the best of our knowledge imported bromine prices are to the tune of $ 0.7 to 0.9 / kg as compared to Indian bromine prices of about $ 1.2 to 1.3 / kg. This is because most of the Indian plants are based on the hot process. The feed bromine concentration is very low and hence large volumes are to be heated to about 125-150 °C. The fuel cost in this case is about Rs. 12-15 / kg. In hot process, while condensing bromine vapours, again Rs. 8-10 / kg cooling cost is added to that. In other words about Rs. 20-25 / Kg are an indirect cost which adds up to bromine manufacturing cost and thus makes it incompetitive. This could be avoided by concentrating the feed source with solar energy in open kyars like a salt farm. The cost for the same is likely to be Rs. 3 to 4 / kg only. However, though being quite promising, it is not in a purview of this work and hence not discussed here. One can think of it as an extension of this work.

The similar fluctuating trend is also seen in the case of sodium bromide. The import of sodium bromide shows a growth of about 25% in the year 2003-04 again considering the year 96-97 as the base year. Here too, the fluctuating down ward trend for the foreign exchange spent towards its import is clearly observed. The lowest import value is Rs. 36.21 / kg for the year 03-04 and is far below the manufacturing cost of sodium bromide in India. It is important to mention here that in the year 2004-05 the imports are low indicates the volatile fluctuating market.

In the case of potassium bromide from the import data as well as the foreign exchange spent towards its imports, it is very difficult to arrive at any definite conclusion. However, for many of the years during the period under review it has been dumped at a throw away prices.

Again, to the best of our knowledge, imported inorganic bromide prices fluctuates between $ 1 to 1.2 / Kg and that of organic bromide prices are more than $ 1.8 to 2.0 / Kg. One also has to remember that in the case of inorganic bromide, particularly potassium bromide, there exists a wide variations in quality starting from industrial grade viz. dyes and industrial chemical grade, pure bulk drug grade, photographic grade etc. to special quality grades viz. spectroscopic grade, fibre grade etc. The variation in the quality requirements directs the prices to fluctuate.

Apart from the above there are so many factors that affects the import statistics including the source availability (quantity and quality of raw materials available), the technical competence for its recovery, the politico-legal support available to the exporting country, the need and urgency of it by the importing country and many more. However, it can be safely concluded that there is a demand of these chemicals in India which can not be met by the Indian manufacturers as on date due to one or the other reasons mentioned above.

The foregoing discussion pause a severe threat to Indian manufacturers to compete in the global market. This situation compelled us to rethink the bromine and its chemistry in toto to come out with an economically viable solution.

Indian manufacturers have the installed capacity to produce about 15000 tons / annum of liquid bromine. Saurashtra Chemicals Ltd. and Dhrangadhra Chemicals Ltd. are closed as on date. The Solaris Chemtech Ltd’s plant after the expansion in installed capacity is commissioned only in the later part of last summer and has not achieved the production as per the installed capacity yet.

In the light of this, Indian manufacturers produce about ten thousand tons of bromine per annum and more or less the half quantity of bromine is being imported either as liquid bromine or as its compounds as on date. However, the finish goods produced and placed in the market by the bromine consuming industries, viz. pharmaceuticals, pesticides, disinfectants, dyes and other chemical sectors, do not reflect the above quantum. Where this bromine goes is a big survival question for the chemical industries in India. It is also seen in the foregoing discussion that Indian bromine and its compounds manufacturing industries are also not able to compete in the international market of liquid bromine and bromine compounds. Indian scientists need to address this problem for solution in context with global competitive market.

� Whether bromine or its compounds separate out during the process? � Whether they get mixed with the effluent streams? � Whether these effluent streams are being properly treated or not? � Where these treated effluents are finally disposed off? � What is the cost of effluent treatment? � Whether it is correct or only way of disposal? � Whether bromine can be recovered from these effluent streams? � Whether techno – economic process for recovery of bromine from effluent is

possible? � What should be techno economic aspect for recycle of bromine in industries?

There are many more such questions in front of Indian industries, either manufacturing or consuming bromine or bromine compounds. No systematic study has been carried out so far and no valid data available in this regard.

1.14.9 Classified reactions of bromine

If we look at the basic reactions of bromine manufacture and few of the classified reactions of bromine the answer to the above questions are clearly visible.

� Basic reactions of bromine manufacture.

2Br - + Cl2 2Cl - + Br2

3Br2 + 6NaOH NaBrO3 + 5NaBr + 3H2O

3Br2 + 3Na2CO3 NaBrO3 + 5NaBr + 3CO2

3Br2 + 8NH3 6NH4Br + N2

� Reactions with aliphatic compounds (37-44)

Catalyst R H + Br2 R Br + HBr

� Reactions with alcohols (45-47)

R OH (aq.) + 2Br2 RCOOR + 4HBr

� Reactions with aldehydes & ketones (48-49)

RCOR’ + Br2 R Br COR’ + HBr RCOCOR’ + Br2 + H2O RCOOH + R’COOH + 2HBr

� Reactions with carboxylic acids & derivatives (50-53)

PBr32RCH2COOH + Br2 RCH2COBr + RCHBrCOOH + HBr

PBr3(RCOOH) 2 + 2Br2 (RHBrCOOH) 2 + 2HBr R(COOR’)2 + Br2 2HBr (COOR’)2 + HBr RCONH2 + Br2 + 4KOH RNH2 + 2KBr + K2CO3 + 2H2O

� Reactions with nitriles (54-55)

R-CN + Br2 RBrCN + HBr (R)2CHCN + Br2 (R)2CBrCN + HBr

� Reactions with aromatic compounds (56-70)

ArH + Br2 ArBr + HBr RAr + Br2 RBrAr + HBr

� Reactions with phenols (71-72)

ArOH + 3Br2 Br3ArOH + 3HBr

� Reactions with aromatic amines (73-74)

ArNH2 + 3Br2 Br3ArNH2 + 3HBr ArN(R) 2 + 3Br2 Br3ArN(R) 2 HBr. Br2

ArNHCOCH3 + Br2 BrArNHCOCH3 + HBr

� Reactions with aromatic acids (75-81)

ArCOOH + Br2 BrArCOOH + HBr

� Reactions with aromatic ketones (82-83)

ArCOR + Br2 ArCORBr + HBr

� Reactions with aromatic ethers (84)

ArOR + Br2 BrArOR + HBr

� Reactions with heterocyclic compounds (85-91)

N N.Br2 N N

N

Br2

Br BrBr

N.Br2 .HBr.2H2O

Pyridine

Pyridine

Br2

Br2 HBr

S S

Thiophene

Br

O

O O

O

Br2HBr

Br

Dioxane

HBr

(aq)

The foregoing reactions clearly indicates that when bromine is being reacted, half of the bromine molecule takes part in the main reaction and the other half normally passes out as hydrobromic acid gas. This acidic gas in turn is being absorbed in an alkali to form alkali bromide having some lower boiling impurities of the main reaction. In other words only 50% of the bromine fed to the reaction is utilized in the reaction and the rest 50% goes out as effluent stream, normally referred by the bromine consumer as a by product. These typical reaction patterns disturb the bromine economics on a greater extent and make the Indian bromine compounds more costly in the global market.

In view to over come this hurdle one needs to brain storm and come out with a cyclic utilization pattern wherein the bromine passed out in an effluent stream is recovered and recycled. It is our humble efforts to work in this direction on an industrial scale.

1.14.10 Effluents as bromine feed source

Few of the following effluent streams are taken as the initial raw materials to manufacture bromine, sodium bromide, potassium bromide, potassium bromate and n-propyl bromide on an industrial scale. If we look at the range of finish products, it not only recover and recycle the bromine from effluent streams, but the value addition products viz. inorganic bromides, bromates and organic bromides are also manufactured from these effluent streams. To maintain the confidentiality of the generator of the effluent streams, the names of these industries are not given and instead they are given the code names of effluent-A, effluent-B and effluent-C. However, the chemistry of recovery and recycling is thoroughly discussed in preceding chapter.

TABLE - 11

EFFLUENT-A SPECIFICATION.

Physical appearance Yellow liquid Sodium bromide % by mass 18 + 1 %Sodium hydroxide % by mass 15 + 1 %Specific gravity 1.33 to 1.36 Organic content Feeble Balance Water

It is a waste stream from a pesticide industry located in southern belt of Gujarat. It is given as a sodium bromide aqueous solution at a throw away prices. The generation of this waste stream is 1 KL /day.

TABLE - 12

EFFLUENT-B SPECIFICATION.

Physical appearance Light milky hazy Sodium bromide % by mass 23 + 2 %Specific gravity 1.18-1.20 pH 2.5 Organic content Quarternary ammonium compound Balance Water

It is again a waste stream from a pesticide industry located in Saurashtra. It is also given as a sodium bromide aqueous solution at a throw away prices. However, this waste stream differs from a previous one. In the previous one while brominating the aromatic compound the so generated hydrobromic acid gas is being scrubbed in caustic solution. The acidic gas on its way to scrubber carries with it traces of lower boiling organic compound used as a solvent. In this case quarternary ammonium salt is generated in situ and because of it’s comparatively higher solubility in water, while separating out the product it passes out to effluent stream. The generation of this waste stream is about 1.5 KL / day.

TABLE-13

EFFLUENT-C SPECIFICATION.

Physical appearance Brown Sodium bromide % by mass 10 + 2 %Sodium Sulfate % by mass 27 + 2 %Specific gravity 1.35 pH Neutral Organic content Not given Balance Water

It is a waste stream from a pharmaceutical intermediate manufacturing unit located in the central part of Gujarat. They are using ethyl bromide as one of the raw material to attach ethyl moiety to drug intermediate. Here also the so liberated hydrobromic acid gas is

scrubbed into caustic solution and the excess alkalinity is being destroyed by the sulfuric acid. It is apparent from the specification given that there are opportunities in hydrobromic acid gas absorption. In view of maintaining the confidentiality of their product they are reluctant to give any more information. However, our objective is to recover and recycle bromine, no further queries were raised. The generation of this waste stream is to the tune of about 1.5 KL/day.

The preceding section will concentrate on techno – economical viability of recovery and recycling of bromine as liquid bromine or as its salts as a value added products viz. sodium bromide, potassium bromide, potassium bromate and n-propyl bromide.

1.15 Aim and significance of work

The main aim of this work is to provide an industrially advantageous eco-friendly process for recovering bromine and it's derivatives from industrial effluents to reduce over all pollution loads in the environment. Also, this work provides industrial processes for the bromine and its derivatives recovery which is safe, smooth and economically viable in operation. Last but not least the aim of this work is not only to resolve the survival problem of bromine manufacturing and consuming industries by recovering and recycling bromine and its derivatives from industrial effluent stream, but to provide anticipated benefits viz.

� Cheaper bromine availability. � Recovery of bromine likely to curtail bromine import. � Cost effective pollution and effluent management by parent industry. � Reduction in over all pollution load in the environment. � Promotion of entrepreneurship.

� Creating employment.