Pressures Driving Change in Bromine Industry

By Zhang Miao, China National Chemical Information Centre

Poor in bromine resources, high import dependency

China is a country poor in bromine resources. The production of bromine in China is mainly concentrated in Bohai Bay Area, and the production in the northern coastal area of Weifang City accounts for more than 80% of the national total. At present, there are about 50 bromine producers with total capacity at 165 000 tons.
Over 98% of China’s bromine imports are from Israel and Jordan, and the rest are from the United States and Taiwan. Please refer to Table 1 for import & export situation during 2011 ~ 2016. The import dependency might be even higher in the future as the resources is reducing, the production cost is increasing and the pressure from environmental protection is growing.

Broad application areas

There are more than 200 brominated chemicals manufacturers in China, producing over 200 types of products, including flame retardants, pharmaceuticals and pharmaceutical intermediates, pesticides and pesticide intermediates, dyes and dye intermediates, refrigerants, water treatment agents, photographic materials, polymer materials, etc. Shandong is the major producing area of flame retardants, while brominated pesticides, pharmaceuticals and dyes products are mainly manufactured in Jiangsu and Zhejiang.
1. Brominated flame retardants. Being the largest bromine downstream industry, there are over 20 types of brominated flame retardants produced in China, with a total capacity of 100 000 tons. Major products are decabromodiphenyl ether, tetrabromobisphenol A, decabromodiphenyl ethane, tribromophenol, octabromobisphenol, HBCD, brominated epoxy resin, brominated polystyrene, and brominated polycarbonates. The development prospect of brominated flame retardants is very bright due to its excellent compatibility with polymer materials, its high efficiency and low cost. The demand for octaBDE, PBBs and PBDEs will decline as they are less environmental friendly. Decabromodiphenylethane, tetrabromobisphenol A, tetrabromobisphenol S, brominated epoxy resins, and dibromo pentylene glycol will grow rapidly. And decabromodiphenyl ether will still be banned.
2. Pharmaceuticals and pharmaceutical intermediates. China’s pharmaceutical industry needs nearly 40 kinds of bromine products, and major bromine consumers at present are dibromide, TMBA, TMP, carbamazepine, cimetidine, ethyl bromide and sodium bromide. Production enterprises are mainly located in Jiangsu, Zhejiang, and Shandong.
3. Dyes and dye intermediates. Bromine and some of its compounds can be used as intermediates in the production of indigo-based dyes and certain acidic dyes. Brominated dyes are usually high-grade dyes with high added value. There are about 20 bromine-consuming dye types in China, among which 6-bromo-2,4-dinitroaniline, 2,6-dibromo-p-nitroaniline and bromamine acid are the main consumers of bromine, and their capacities are at 5 000 to 10 000 tons/year. Other types like cyanide-6-bromoaniline and 2-cyano-4-nitro-6-bromoaniline have less demand for bromine.
4. Pesticides and pesticide intermediates. There are very few kinds of brominated pesticides, but brominated pesticides have low toxicity and no residues and are very effective and easy to decompose. They are developing very fast. Production enterprises of brominated pesticides are mainly located in Shanghai, Jiangsu and Zhejiang.
5. Inorganic bromide. Inorganic bromide products include bromine chloride, calcium bromide, zinc bromide, photosensitive materials (sodium bromide, potassium bromide, ammonium bromide), refrigerant (lithium bromide), sodium bromate, and potassium bromate. There are over 40 manufacturing enterprises in China.
6. Others. A large quantity of hydrogen bromide is generated as byproduct in the process of synthesis of organic bromides with bromine as raw material, with an estimated annual output of 50 000 tons, which has become secondary feedstock of bromine deep processing industry. Approximately 40% of these hydrogen bromides are turned into hydrobromic acid and used as a basic raw material for inorganic bromide products after purification. About 30% byproducts are used as a raw material for the production of bromine, and the other 30% are applied to produce organic bromides.

Constraints on bromine industry

Bromine industry development is restrained by policies and climate. As for policies, the collection of resource tax will significantly increase the production cost of bromine, which to some extent, will raise the prices of bromine. Meanwhile, bromine production is a high energy-consuming industry, subject to environmental protection policies.
Bromine is mainly produced from brominated brine (seawater) in China, and the climate has a great impact on the development of the bromine industry. The temperature in winter is low in China, so if only bromine is extracted, not only the brine will be wasted, but serious offshore pollution will be caused. Meanwhile, bromine production has to be stopped in typhoon season. And in flood season, the bromine content in brine decreases in Hebei, Tianjin and other coastal areas, and local producers (about 8% of the total capacity) are usually forced to shut down.

Future development

The homogenization of competition and the demand for high value-added products have propelled the bromine sector to gradually shift from resource-based to a refined industry.
The import dependency will still be high as there is unlikely to be a large increase in domestic supply.
In terms of demand, brominated flame retardants are still the largest consumer of bromine, but the growth is gradually slowing down. In the future, brominated flame retardants will be more refined, and high molecular brominated flame retardants, high performance inorganic flame retardants and bromine, and nitrogen and phosphorus compound flame retardants worth developing.
Brominated organic intermediates have become the new impetus of bromine industry. Most of the brominated pesticides such as insecticidal acaricide and fungicidal and herbicidal activities have low toxicity and no residues and are very effective and easy to decompose. They are developing rapidly. Bromomethane is gradually eliminated as they have been classified as ozone depleting substances. Demands for profenofos, bromine bacteria clear, bronopol, deltamethrin, and benzalkonium bromide have increased significantly. Brominated dyes and intermediates like aniline, bromine and anisole have good dyeing property and high added value, and can thus be used as high-grade dyes. Bromine-containing disinfectants have moderate performance and broad-spectrum efficiency, so this type of products like brominated hydroxy diphenyl ether, benzalkonium bromide, and chlorobrominated isocyanuric acid will grow. New bromine-containing materials such as alkyl bromides benzene, brominated biphenyl liquid crystal intermediates, brominated polystyrene flame retardants, brominated polystyrene hydantoin germicides and disinfectants all have excellent performance.
Inorganic bromides, such as sodium bromide, calcium bromide and zinc bromide, which are used in oilfield chemicals, will still have a large market for a long time. At the same time, most of the existing products are made from by-products of hydrobromic acid.
Traditional products such as bromine chloride, hydrobromic acid, bromate, bromopyridine and hydrogen bromide have stable market demands, but problems like product quality and packaging need to be addressed. For instance, the gas cylinder packaging of hydrogen bromide is restricting its market expansion. The market demands for a wide range of intermediates are growing, including industrial cleaning agents bromopropane, surfactants cetyl dimethyl benzyl ammonium bromide, flux bromide hydrazine, bromoacetophenone and m-dibromobenzene. However, their quality needs to be enhanced. Brominated pharmaceuticals like dibromoaldehyde, chloramphenicol, brominated acids and brominated esters take a large proportion of pharmaceuticals, and the adoption of advanced and environmental friendly technology is necessary to improve the production and quality.               

Table 1    China’s bromine import & export, 2011-2016                      Ton

    Import    Export    Import dependency
    Volume     Value (10 000 US$)    Volume    Value (10 000 US$)?    
2011    22 837    7 807.9    7    2.5    15.3
2012    26 270    7 131.9    0    0.1    18.1
2013    33 445    7 745.5    0    0.0    20.2
2014    34 664    8 051.8    104    25.6    20.6
2015    23 852    5 920.3    0    0    19.4
2016    37 186    11 019.7    0    0    22.5