• Manganese: history and industry development

• History

• The first utilization of manganese can be dated back to the Stone Age. Men were already using manganese dioxide as a pigment for their cave paintings during the upper paleolithic period 17,000 years ago. Later in Ancient Greece, the presence of manganese in the iron ore used by the Spartans is a likely explanation as to why their steel weapons were superior to those of their enemies. Manganese has also long been used in glass-making. Egyptian and Roman glassmakers used manganese compounds to either add color to glass or remove color from it. The use as “glassmakers’ soap” continued through the Middle Ages until modern times and is evident in 14th-century glass from Venice.
• In the middle of 17th century, the German chemist Glauber obtained permanganate, the first usable manganese salt. By the mid-18th century, the Swedish chemist Carl Wilhelm Scheele used manganese dioxide to produce chlorine. The production of chlorine and hypochlorite containing bleaching agents was a large consumer of manganese ores. It was not until 1771 that manganese was recognized as an element by Scheele. Although he and other chemists were aware that manganese dioxide contained a new element, they were not able to isolate it. Johan Gottlieb Gahn, one of his collaborators, was the first to isolate an impure sample of manganese metal in 1774, by reducing the dioxide with carbon.

• Industry development

• At the beginning of the 19th century, both British and French scientists started to consider the use of manganese in steelmaking, with patents granted in the U.K. in 1799 and 1808. In 1816, a German researcher noticed that manganese increased the hardness of iron, without reducing its malleability or toughness. In 1826, Prieger in Germany produced a ferromanganese containing 80% manganese in a crucible. J.M. Heath produced metallic manganese in England in 1840. In 1841, Pourcel began industrial-scale production of spiegeleisen, a pig-iron containing a high percentage of manganese, and in 1875 he started the commercial production of ferromanganese with 65% manganese content. The major breakthrough in the use of manganese occurred in 1860. At that time, Sir Henry Bessemer was trying to develop the steelmaking process which was to bear his name. But he experienced difficulty with an excess of residual oxygen and sulphur in the steel. Robert Mushet suggested adding spiegeleisen after the blow to introduce both manganese and carbon and remove oxygen. This procedure made the Bessemer process possible, and thus paved the way for the modern steel industry.
• In 1866, Sir William Siemens patented the use of ferro-manganese in steelmaking so as to control the levels of phosphorus and sulphur. The demand for manganese dioxide increased because of the invention of the Leclanché cell in 1866 and the subsequent improvement of batteries containing manganese dioxide as a cathodic depolarizer. Manganese metal was first produced by an aluminothermic process in 1898. Some commercial production took place in the early 20th century. In 1912, manganese phosphating electrochemical conversion coatings for protecting firearms against rust and corrosion were patented in the United States, and have seen widespread use ever since. The development of electrolytic manganese began on a pilot scale in 1940 and the first commercial-sized plant was built fourteen years later in the USA.
• The history of manganese in the 20th century has seen a stream of new processes and metallurgical/chemical applications developed with a significant impact on markets. At present, nearly 90% of all of the manganese produced each year is used in the production of steel, and the rest is mainly used in the production of batteries and chemicals. According to USGS, world manganese mine production was estimated to be 17 million tonnes in 2013, an increase of 7.6% compared with 15.8 million tonnes in 2012. South Africa was the largest producer in 2013, followed by China and Australia.
• The future of the manganese industry will continue to depend on steel production, while other applications are likely to see impressive growth. In response to rising demand, manganese production will increase in the coming years, having recovered from the market downturn in 2009. New capacity in traditional producing countries, such as South Africa, Australia and China will see output of manganese ore, ferroalloys and EMM rise in the coming years as new projects enter the market to meet growing requirements, and high grade manganese ores from Africa, Australia and South America will be required to feed the ferroalloy smelters of Asia, where ores are typically low-grade and unsuitable for production of good quality manganese ferroalloys.

• The manganese industry in China

• China’s demand for manganese ore has been growing year by year because of the rapid development of the iron and steel industry. However, manganese resources in China are very low grade and domestic supply can’t satisfy demand, thus China’s imports of manganese ore have been increasing year by year. In 2010, imported manganese ore accounted for 55% of China’s total demand. In 2011, China imported 13 million tonnes (gross weight) manganese ore, up 12% from 2010. In 2012, China imported 11.38 million tonnes of manganese ore. The leading sources of Chinese manganese ore imports are Australia, South Africa, Gabon, Ghana and Brazil. Most of the imported manganese ores are blended with lower-grade domestic ore to produce manganese ferroalloys and metal.
• At present, China is the leading producer of manganese ferroalloys in the world, but it still has nominal imports of ferromanganese and silicomanganese. In 2011, China exported 30,800t of ferromanganese, 43% less than in 2010, and it also exported significantly less silicomanganese. China is also the leading producer of EMM in the world with about 162 companies. In 2011, China produced 1.48Mt of EMM, an increase of 7% from 2010, while EMM consumption in China that year was 1.34Mt, a 15% increase from the 2010 figure. China’s EMM production capacity in 2011 was estimated to be 2.4 Mt/yr, or 98% of the world total, and this excluded 198,000t/yr of capacity because of the permanent closure of 25 plants and revamp of 11 plants for environmental reasons. China exported about 162,000t of EMM in 2011, a decrease of 26% compared with 2010. In 2011, China was the leading producer of EMD in the world, with total output of 229,000t. This equated to 88% of the country’s annual production capacity, which was 260,000t. China’s share of the active world EMD production capacity in 2011 was about 61%.