A Brief History Of Manganese Research

A brief history of discovery

The earliest use of manganese dates back to the Stone Age. As early as 17,000 years ago, manganese oxide (pylurite) was used as a pigment in cave paintings by people in the late Paleolithic period, and later in the weapons used by the ancient Greek Spartans. The ancient Egyptians and Romans used manganese ore to decolorize or dye glass.

Although pyrolusite has been used by people for a long time, until the 1870s, Western chemists still believed that pyrolusite was a mineral containing tin, zinc and cobalt. In the late 18th century, the Swedish chemist T.O. Bergman studied pyrolusite, believing it to be a new metal oxide, and tried to isolate the metal without success. The Swedish chemist Scheler also did not extract the metal from the pyrolusite, so he turned to his friend and Bergman's assistant, Gunn. In 1774, Gann used Scheler's purified pyrolusite powder and charcoal to heat in a crucible for one hour to obtain a button-shaped metal manganese block [1], which Bergman named manganese.

Development history abroad

In the early 19th century [2], British and French scientists began to study the application of manganese in steel making, and it was recognized in Britain in 1799 and 1808, respectively. In 1816, a German researcher discovered that manganese increases the hardness of iron without reducing its ductility and toughness. In 1826, Piege of Germany made manganese steel with 80% manganese in a crucible. In 1840, J.M. Hitz produced manganese metal in England. In 1841, Passa began the industrial-scale production of mirror iron. In 1875, Passa began commercial production of ferromanganese with a manganese content of 65%.

In 1860, there was a major breakthrough in the application of manganese. Bessemer was trying his best to develop the steel-making process named after him, but he encountered a problem - too much oxygen and sulfur remained in the steel. This problem was solved by Mahit in 1856, who suggested that Bessemer add mirror iron (ferromanganese with lower manganese content) to molten steel for sulfur removal. The birth of Bessemer method marks the evolution from the "iron age" to the "steel age" in the early industrial revolution, which is of epoch-making significance in the history of metallurgical development.

In 1866, William Siemens applied for a patent for the use of ferromanganese to control the content of phosphorus and sulfur in the steelmaking process. In 1868, Leclanché produced the first dry battery, which was later improved. The battery used manganese dioxide as a cathode depolarizer for dry batteries. The application of manganese in the battery field drove the growth of manganese dioxide demand. After 1875, European countries began to use blast furnaces to produce mirror iron containing 15% to 30% of manganese and ferromanganese containing up to 80% of manganese. In 1890, the process of producing ferromanganese by electric furnace was born, and in 1898, the method of producing metal manganese by aluminothermic method appeared, and the electric furnace desiliconization refining method was also used to produce low-carbon ferromanganese. In 1939, the production of metal manganese by electrolysis began. With the continuous improvement of technology, the annual output of manganese is also increasing. According to the data released by the US Geological Survey in 2015, the global manganese ore production in 2013 was about 18 million tons. The consumption field of manganese is also expanding, in addition to being mostly used in the field of steel, it is also widely used in batteries, chemical industry, electronics, agriculture, medicine and other fields [3] .

Domestic development history

The geological prospecting of manganese ore in my country began in 1886 [4], and manganese ore was first discovered in Xingguo Prefecture (now Yangxin) in Hubei in 1890. After the founding of New China, large-scale manganese ore geological exploration began. By the end of 2012, there were 213 mining areas with proven reserves in my country.

The mining of manganese mines in my country began in 1890. At that time, Hubei Yangxin manganese mines were mined, but they were soon stopped due to poor quality. After more than 100 years of development, my country has formed a relatively complete system in manganese ore mining, beneficiation, smelting, deep processing and comprehensive utilization, and the output of manganese ore is also increasing.

In addition, with the rapid development of my country's iron and steel, electronic batteries and other industries, the consumption of manganese has surged. However, my country's manganese ore has more lean ore and less rich ore, which cannot meet the domestic demand for manganese resources, resulting in the import of manganese ore from 1983. Since the beginning of the year, it has increased year by year, and my country has also become the world's main importer of manganese ore. In 2010, China imported 11.6 million tons (calculated in dry tons) of manganese ore, accounting for 58% of the world's total trade volume (20 million tons). In 2011, my country's manganese ore imports were 12.97 million tons, an increase of 12.1% over 2010, a record high for my country's annual imports. In 2012, my country imported 11.38 million tons of manganese ore [5] .

The manganese ore imported into my country mainly comes from Australia, Gabon, Ghana, South Africa, Brazil, India, Myanmar, Eastern Europe and other countries and regions. With the continuous development of my country's manganese industry, my country's manganese products have also begun to be exported. Japan, the Netherlands, South Korea, the United States, Russia, Ukraine, India, Bangladesh, North Korea, Thailand and other countries are the main export destinations of my country's manganese products. In recent years, due to the large domestic demand for manganese resources, the weak international market, and the influence of the government's taxation on related manganese products, the export volume of manganese products in my country has declined. In 2012, the cumulative export volume of manganese products (manganese peach, etc.) in my country was 87,705.052 tons, a year-on-year decrease of 17%. In 2013, the imported manganese ore was 16.608 million tons, a year-on-year increase of 34.29%, and the import value was US$3,191.716 million, a year-on-year increase of 46%. Compared with 2012, my country's imported manganese ore in 2013 can be said to increase in both volume and price. This is due to the continuous increase in the rigid demand for manganese alloys due to the increase in my country's crude steel production, and the increase in output in major manganese ore producing countries such as South Africa and the increased investment in the Chinese market.

In recent years, the problems in the development of my country's manganese industry have become more and more prominent. For example, manganese ore is mainly produced by small and medium-sized mining areas, with low mining utilization rate and low recovery rate. Backwardness, serious environmental pollution, unreasonable industrial layout structure, overcapacity, and high dependence on foreign ores all restrict the development of my country's manganese industry.

In 2013, various national policies on environmental protection and elimination of outdated production capacity were introduced [6], which was intended to regulate the output of steel and electrolytic manganese. The production capacity of electrolytic manganese is seriously excessive, and the situation of oversupply of output is tense. Although the overcapacity of electrolytic manganese may be reduced under normal government regulation, it will take a certain transitional time. In order to solve these problems, my country's manganese-related enterprises should pay close attention to the domestic and international markets, adjust the import volume and output of manganese ore in a timely manner, give play to the positive role of industry federations, and enhance the right to speak in the international market price. Relevant departments should also encourage and guide enterprises to implement the strategy of going global, increase overseas investment and construction of factories, and ensure the supply of manganese ore market in my country. In addition, relevant state departments should also integrate manganese ore resources, ban illegal mining, eliminate small mines with low efficiency, raise the threshold for industry access, increase the concentration of exploration and mining, increase investment in new processes and equipment, and continue to implement energy conservation. Emission reduction work to promote the healthy development of related industries.