Bromine manufacture

There are four principal steps in bromine production (/) oxidation of bromide to bromine (2) stripping bromine from the aqueous solution (3) separation of bromine from the vapor and (4) purification of the bromine. Most of the differences between the various bromine manufacturing processes are in the stripping step. 

Significant industrial demand for a more practical stabilized liquid bromine product has been known for several years. Until the invention and commercial development of STABREX, there was no practical means to overcome the inherent instability, volatility, and handling hazards of liquid bromine. The new technology solves several longstanding technical problems that bromine manufacturers tried, unsuccessfully, to overcome for 15 years. The practical use of STABREX stabilized liquid bromine and its... 

Bromine can be prepared in the laboratory by the action of sulfuric acid on a mixture of sodium bromide and manganese dioxide, in the apparatus shown in Figure 13-2. Until recently most of the bromine used coipmercially was made in this way, from sodium bromide and potassium bromide mined from the Stassfurt deposits in Germany, or from brines pumped from wells in the eastern and central United States. During the past twenty-fi e years there has occurred a very great increase in the amount of bromine manufactured, until at present over 10,000 tons a year is being made. 

CH3C(0)CH2Br. Colourless liquid which rapidly becomes violet in colour it is a powerful lachrymator b.p. 1367725 mm. Manufactured by treating aqueous propanone with bromine at 30-40 C it is usual to add sodium chlorate(V) to convert the hydro-bromic acid formed by the reaction back to bromine. It is not very stable and decomposes on standing. 

BrCHi CHjBr. A colourless liquid with a sweet odour, m.p. 10°C, b.p. 132°C. Manufactured by passing ethene through bromine or bromine and water at about 20 C. Chemical properties similar to those of 1,2-dichloroethane when heated with alkali hydroxides, vinyl bromide is formed. Used extensively in petrols to combine with the lead formed by the decomposition of lead tetraethyl, as a fumigant for stored products and as a nematocide. 

Bromine is used in the manufacture of many important organic compounds including 1,2-dibromoethane (ethylene dibromide), added to petrol to prevent lead deposition which occurs by decomposition of the anti-knock —lead tetraethyl bromomethane (methyl bromide), a fumigating agent, and several compounds used to reduce flammability of polyester plastics and epoxide resins. Silver(I) bromide is used extensively in the photographic industry... 

Most of the chlorine produced is used in the manufacture of chlorinated compounds for sanitation, pulp bleaching, disinfectants, and textile processing. Further use is in the manufacture of chlorates, chloroform, carbon tetrachloride, and in the extraction of bromine. 

Butynediol is principally used in pickling and plating baths. Smak amounts are used in the manufacture of brominated derivatives, useful as flame retardants. Itwas formerly used in awkd oat herbicide, Carbyne (Barban), 4-chloro-2-butynyl-A/-(3-chlorophenyl)carbamate [101-27-9] C H Cl2N02 (77). 

Numerous methods for the deterrnination of monomer purity, including procedures for the deterrnination of saponification equivalent and bromine number, specific gravity, refractive index, and color, are available from manufacturers (68—70). Concentrations of minor components are deterrnined by iodimetry or colorimetry for HQ or MEHQ, by the Kad-Eisher method for water, and by turbidity measurements for trace amounts of polymer. 

Flame letaidancy can be impaited to plastics by incorporating elements such as bromine, chlorine, antimony, tin, molybdenum, phosphoms, aluminum, and magnesium, either duriag the manufacture or when the plastics are compounded iato some useful product. Phosphoms, bromine, and chlorine are usually iacorporated as some organic compound. The other inorganic flame retardants are discussed hereia. 

The Brominated Flame Retardants Industry Panel (BFRIP) was formed ia 1985 within the Flame Retardant Chemicals Association (FRCA) to address such concerns about the use of decabromodiphenyl oxide. Siace 1990 the BFRIP has operated as a Chemical Self-Funded Technical Advocacy and Research (CHEMSTAR) panel within the Chemical Manufacturers Association (CMA) (64). As of 1993, members of BFRIP are Ak2o, Amerihaas (Dead Sea Bromine Group), Ethyl Corp., and Great Lakes Chemical. Siace its formation, BFRIP has presented updates to iadustry on a regular basis (65,66), and has pubhshed a summary of the available toxicity information on four of the largest volume brominated flame retardants (67,68) tetrabromo bisphenol A, pentabromodiphenyl oxide, octabromodiphenyl oxide, and decabromodiphenyl oxide. This information supplements that summarized ia Table 11. 

Flame-Retardant Filler. Demand has increased for Mg(OH)2 as a nonhalogenated, flame-retardant filler for thermoplastics used in the aerospace, microelectronics, and cable and wire manufacturing industries (90). Producers of nonhalogenated, flame retardant fillers include Kyowa, Aluisuisse-Lonza (Magnifin product line), Morton, and a Dead Sea Periclase/Dead Sea Bromine joint venture (91). 

Manufacture. The only current U.S. manufacturer of trimesic acid is Amoco Chemical Co. It is produced by oxidation of mesitylene (1,3,5-trimethylbenzene) via the Hquid-phase oxidation in acetic acid using the cobalt— manganese—bromine catalyst system (138). This is a variant of the system used to produce terephthaUc and isophthaUc acids as well as trimellitic anhydride. American Bio-Synthetics Corp. did produce it by batch oxidation of mesitylene with potassium permanganate. 

Manufacture. Ammonium bromide and Ammonium iodide are manufactured either by the reaction of ammonia with the corresponding hydrohahc acid or, more economically, by the reaction of ammonia with elemental bromine or iodine. In the latter reaction, an excess of ammonia must be used. 

U.S. sodium bromide demand accounts for 8—10% of total bromine production. In 1994 demand is estimated to have been 13,600—17,200 metric tons (5). At mid-1996, the price for technical-grade sodium bromide iu tmckload quantities was 1.54/kg ( 0.70/lb) (6). Manufacturers of sodium bromide iuclude Albemarle, Great Lakes Chemical, Rhc )ne-Poulenc, and Whittaker Corporation. 

Oxidation of sulfur dioxide in aqueous solution, as in clouds, can be catalyzed synergistically by iron and manganese (225). Ammonia can be used to scmb sulfur dioxide from gas streams in the presence of air. The product is largely ammonium sulfate formed by oxidation in the absence of any catalyst (226). The oxidation of SO2 catalyzed by nitrogen oxides was important in the eady processes for manufacture of sulfuric acid (qv). Sulfur dioxide reacts with chlorine or bromine forming sulfuryl chloride or bromide [507-16 ]. 

Commercial manufacture of methyl bromide is generally based on the reaction of hydrogen bromide with methanol. For laboratory preparation, the addition of sulfuric acid to sodium bromide and methanol has been used (80). Another method involves the treatment of bromine with a reducing agent, such as phosphoms or sulfur dioxide, to generate hydrogen bromide (81). 

In the manufacture of ethylene dibromide, gaseous ethylene is brought into contact with bromine by various methods, allowing for dissipation of the heat of reaction (100—102). Eree acids are neutralized and the product maybe fractionally distilled for purification. Typical specifications call for a clear Hquid with 99.5% purity min sp gr (25/25°C), 2.170—2.180 boiling range, 130.4—132.4°C APHA color, 200 max water, 200 ppm max acidity as HCl, 0.0004 wt % max and nonvolatile matter, 0.0050 wt % max. 

A good technical grade of carbon tetrachloride contains not more than the following amounts of impurities 1 ppm acidity as HCl, 1 ppm carbon disulfide if manufactured by carbon disulfide chlorination, 20 ppm bromine, 200 ppm water, and 150 ppm chloroform. The residue should not exceed 10 ppm on total evaporation. The product should give no acid reaction with bromophenol blue, and the starch iodine test should indicate the absence of free chlorine. 

Efforts to raise the alpha-selectivity have been made. Thus nitration of anthraquinone using nitrogen dioxide and ozone has been reported (17). l-Amino-4-bromoanthraquinone-2-sulfonic acid (bromamine acid) [116-81 -4] (8) is the most important intermediate for manufacturing reactive and acid dyes. Bromamine acid is manufactured from l-aminoanthraquinone-2-sulfonic acid [83-62-5] (19) by bromination in aqueous medium (18—20), or in concentrated sulfuric acid (21). l-Aminoanthraquinone-2-sulfonic acid is prepared from l-aminoanthraquinone by sulfonation in an inert, high boiling point organic solvent (22), or in oleum with sodium sulfate (23). 

This process was not acceptable for several reasons low yields, poor quaUty, and the high cost of bromine. Later, at BASF, a process was developed for the manufacture of ali2artn by the caustic fusion of anthraquinone-2-sulfonic acid (so-called silver salt) which was made by sulfonating anthraquinone with sulfuric acid. This process was patented in England on the 25th of June, 1869. One day later, W. Perkin appHed for a patent for the manufacture of ali2ariQ by a process almost identical to the German process except that the "silver salt" was prepared as follows ... 

In addition to being the most widely used disinfectant for water treatment, chlorine is extensively used in a variety of products, including paper products, dyestuffs, textiles, petroleum products, pharmaceuticals, antiseptics, insecticides, foodstuffs, solvents, paints, and other consumer products. Most chlorine produced is used in the manufacture of chlorinated compounds for sanitation, pulp bleaching, disinfectants, and textile processing. It is also used in the manufacture of chlorates, chloroform, and carbon tetrachloride and in the extraction of bromine. Among other past uses, chlorine served as a war gas during World War I. 

The next major bonded phase project was the development of the GBR resin, which stands for modified glucose bonded on both the backbone and the ring of basic PDVB gels. The manufacture of this product was ultimately achieved, as outlined later. The gel is first brominated, which places bromine atoms on both tertiary hydrogens of the PDVB. The brominated gel is then reacted with chlorosulfonic acid, and a specially treated reduced D-glucosamine is coupled to the gel. This process has the potential to covalently bond up to three sugar residues to each available divinylbenzene residue in the PDVB polymer. The exact reaction conditions used are proprietary however, the surface of the finished product is believed to look similar to Figs. 13.11 and 13.12. 

On September 6, 1987, the European Economic Community and the United States signed a phase-out agreement for the manufacture and use of specific refrigerants containing chlorine and bromine in the hydrocarbon molecule because of the effects on the atmosphere s ozone layer. ° See Reference 20, p. 18.1, for a more detailed history of this... 

Of major concern are the health and environmental impacts of the abundant chlorinated and brominated hydrocarbons (ref. 2). These materials have numerous industrial applications as pesticides, solvents, propellants, refrigerants, plastics, fire retardants and extinguishers, disinfectants for drinking water, pharmaceuticals and electronic chemicals. Many chemical manufacturers utilize chlorinated and brominated organics as intermediates. It is estimated, for instance, that almost 85 % of the pharmaceuticals produced in the world require chlorine at some stage of synthesis. 

For the organic contaminants, the required bromine product quality wilt also be site specific. If the catalytic oxidation unit is dedicated to a single bromination process, phase separation and drying may be the only purification required. Contaminants in the recovered bromine which are either the starting materials or products of the original bromination reaction should not present a problem if present in bromine recycled to the bromination reactor. In this case, the catalytic reactor would be operated to minimize the formation of undesirable brominated byproducts. For example, if phenol is present in the waste HBr from a tribromo-phenol manufacturing process, minor tribromophenol contamination of the bromine recycled to the reactor should not be a problem. Similarly, fluorobenzene in bromine recycled to a fluorobenzene bromination process should not present a problem. 

Manufacturers of brominated products are facing increasing economic, environmental and legislative pressure to improve their processing with respect to the effluent discharged. 

C21-0095. A company that manufactures photographic film generates 2550 L/day of aqueous waste containing 0.125 g/L of Br ions. To recover the bromine in the form of Bf2, the company bubbles CI2 gas through this waste. Calculate the volume of gas that is consumed daily if the gas is delivered at 1.05 atm and 21 °C. 

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