Antimony is a metalloid element, English name Antimony, element symbol: Sb, belongs to the VA group, atomic number 51, relative atomic weight 121.75, density 6.684 g/cm³, melting point 630.74 ℃, boiling point 1750 ℃. Antimony is a brittle and lustrous silver-white solid, poisonous, with unique thermal shrinkage and cold expansion properties, and no ductility. Antimony is not oxidized by air at room temperature, but can react with concentrated nitric acid. The content of antimony in the earth's crust is 0.0001%. Currently, up to 120 types of antimony-containing minerals are known, but only 10 types are of industrial importance. With the development of science and technology, antimony has found wide application in the production of various flame retardants, alloys, ceramics, glass, pigments, semiconductor components, medicine and the chemical industry.
History and development of antimony
[Brief history of the discovery of antimony]
Man began to use antimony more than 3000 BC. Antimony trisulfide was used as an eyeshadow powder as early as 3100 BC. in pre-dynastic Egypt. A fragment of an antimony vase dating from 3000 BC was found at Teloch (modern Iraq) in Chaldea. Antimony-plated bronzes found in Egypt also date from 2500–2200 BC. Small pieces of antimony were discovered in Hungary around the 18th century BC, but this metal was little known for a long time. Yellow lead antimonate was also found in the glaze of decorative bricks in the 6th and 7th centuries BC. In the Middle Ages, antimony was used to make lead type and as a laxative. In 1777, the German mining officer Bowen discovered natural antimony in Siebenbürgen, burned antimonite and turned it into oxide, and then reduced it with carbon to obtain metallic antimony.
【History of antimony】
In 1556, the German metallurgist G. Agricola described in his book a method for obtaining antimony sulfide by smelting ore, but at that time he mistook antimony sulfide for antimony. In 1604, the German B. Valentine described a method for extracting antimony and antimony sulphide. In the 18th century, the roasting method was used to smelt antimony. It wasn't until 1896 that people got electrolytic antimony. After 1930, the method of smelting antimony ore in a blast furnace became an important method for the production of antimony metal. During the 1960s and 1970s, various volatilization smelting and volatilization roasting methods were developed.
As the production process for antimony is constantly being improved, the output of antimony is also steadily increasing. In 2011, the world production of antimony metal was 178,000 tons, and in 2012 - 180,000 tons. Currently, the main antimony producing countries in the world are China, South Africa, Bolivia, Russia and Tajikistan. The annual antimony production of these five countries accounts for more than 90% of the world antimony production, and China is the largest antimony producer. producer. The main antimony consumer countries (regions) in the world include the USA, China, Europe, Japan and Southeast Asia. The main areas of antimony consumption are flame retardants, battery alloys, catalysts and glass brighteners, among which flame retardants account for about 60% of the total antimony consumption.
【Development history and current situation of the antimony industry in my country】
History of antimony development in my country
China is one of the countries that discovered and used antimony earlier in the world, but at that time, antimony was called "Lianxi", and it was recorded in "Han Shihuozhi" and "Historical Records".
At the end of the Ming Dynasty (1541), the world's largest antimony mine, Hunan Sikuanshan (now part of the city of Lengshuijiang, Hunan Province), was opened in China. 16 years later (1890), antimony was discovered only after tests. Jishan Plant, founded in the 23rd year of Guangxu (1897), was the first antimony refinery in Xiguangshan, which started "tin smelting" in China during the era of antimony production. In 1908, Hunan Huachang introduced the evaporation roasting method from France and began using this method to smelt antimony. In the decades since 1908, China's antimony production often accounted for more than 50% of the world's total production, while Xikuangshan's antimony production accounted for 36.6% of world production from 1912 to 1935, which is 60. 9% of the total volume of the country. In 1942, Wang Chunyu, a well-known Chinese non-ferrous metallurgist and one of the first antimony metallurgy specialists in the world, and American Hodson jointly obtained a patent for melting smelting - gas reduction smelting.
After the founding of New China, large-scale geological surveys andantimony ores, and blast furnaces were developed for volatilization and smelting of antimony sulfide concentrate. From 1990 to the present, the development of antimony ores in my country can be roughly divided into three stages. The first stage was 1990-1996. During this period, my country's economy developed rapidly and the need for resources was great, which opened up opportunities for the development of antimony ores. The second stage lasted from 1997 to 2003. The development of antimony mines at this stage was in a period of decline, mainly due to the influence of the domestic and international economic situation, such as the real estate bubble in my country in 1996 and the financial crisis in Asia. crisis of 1998. Since 2004, the development of antimony ores in my country has entered a new stage of overexploitation.
Statistics of antimony production in my country in recent years
As the world's largest producer of antimony, my country produced 132,000 tons of antimony concentrate (volume of metal) in 2012. In 2012, my country's antimony and antimony products were exported to 37 countries and regions, and exports to the United States, Hong Kong, Taiwan, Japan, and the Netherlands accounted for 84% of my country's total exports. In 2013, the production of metallic antimony amounted to 124,755 tons. In 2014, China's production of antimony metal reached 135,500 tons.
Problems in the development of the antimony industry in my country
With the continuous development of the antimony industry in my country, the problems that exist in the antimony industry are becoming more and more prominent. For example, with the constant overexploitation of antimony ore resources in my country, the rate of consumption of antimony ore reserves far exceeds the growth rate of exploitable reserves, and the recoverable reserves decrease year by year, and the reserve base becomes insufficient.
The antimony mines in my country also face problems such as low production capacity, serious waste of resources, backward technology and unsustainable production structure. In order to protect resources and promote the healthy and sustainable development of the antimony industry, in 1991, the State Council issued the "Notice on the Listing of Ionic Rare Earth Minerals Tungsten, Tin and Antimony in the List of Special Minerals for National Protective Mining" and included antimony in the list. as a national protected mineral for the first time Exploitation of specific minerals. Since 2009, the Ministry of Lands and Resources has also introduced full control over the mining and management of antimony mines across the country and has clarified the direction of limiting mining and production, thereby controlling the supply of antimony at the source. In 2013, the total benchmark production of antimony ore (amount of metal) was 98,000 tons, of which the main production rate was 75,360 tons, and the complex utilization rate was 22,640 tons. However, Minzem and Resources stated that in 2014total production of antimony ore will not be issued.
Use and application of antimony
【Application of antimony】
Antimony trisulfide has been used as an eyeshadow powder since pre-dynastic Egypt in 3100 BC. Antimony-plated bronzes found in Egypt also date from 2500–2200 BC. China is one of the countries that discovered and used antimony earlier in the world. With the development of science and technology, antimony has found wide application in the production of various flame retardants, alloys, ceramics, glass, pigments, semiconductor components, medicine and the chemical industry. Among them, antimony used in the production of fire retardants accounts for about 60% of the total consumption of antimony, antimony consumed in the production of alloy materials in batteries, plain bearings and welding agents is about 20%, and consumption in other aspects is about 20%.
The main use of antimony is the use of its oxide (antimony trioxide) in the production of refractory materials. The process by which antimony trioxide forms antimony halides retards combustion. In addition to halogenated polymer flame retardants, antimony trioxide is almost always used with halide flame retardants. These flame retardants are often used in children's clothing, toys, aircraft and car seat covers, etc., and are also widely used as additives to polyester resins in the production of fiberglass composites (commonly known as FRP) such as engine covers for lightweight aircraft. .
Antimony is a poor conductor of electricity and heat, is not easily oxidized at room temperature, and is corrosion resistant. Therefore, the main function of antimony in alloys is to increase hardness, and it is often used as a hardener for metals or alloys. Antimony-containing lead-based alloys are corrosion resistant and are the preferred choice for electrode plates for transport and marine batteries, chemical pumps, chemical pipelines and cable sheaths; antimony alloys with tin, aluminum and copper have high strength and are extremely wear resistant. Excellent material for overlays and gears.
Antimony is also used in biology and medicine. For example, antimony is used as an emetic, and antimony potassium tartrate (commonly known as cream of tartar) was once used as a drug to treat schistosomiasis and was gradually replaced by praziquantel. Antimony and its compounds are also used in various veterinary drugs, for example, antumarine (lithium antimony thiomalate) is used as a skin conditioner in ruminants.
High-purity antimony and antimony metal compounds (indium-antimony, silver-antimony, gallium-antimony, etc.) are also ideal materials for the production of semiconductors and thermoelectric devices. Antimony is often used as a dopant for ultra-high conductivity n-type silicon wafers. This material is used to make diodes, infrared detectors, and Hall effect elements, while indium antimonide is used to make mid-infrared detectors.
Antimony is not only a stabilizer and catalyst for the production of polyethylene terephthalate, but also a clarifier to remove microscopic bubbles in glass, mainly used in the production of TV screens.
Antimony white is an excellent white pigment, a filler in the enamel, ceramic and rubber industries, as well as a common raw material in the paint, glass, textile and chemical industries. Antimony White can also be used as a flame retardant coating for synthetic fibers, building materials, protective films, power circuit components, high temperature insulation materials and automotive interiors.
Untreated antimony has a low flash point and is used as a component in detonators and safety matches, as well as in the manufacture of smoke agents.
Antimony is also used in the manufacture of bullets and tracer bullets; Sb-124 is used with beryllium in neutron sources; Antimony sulfides have been shown to stabilize the coefficient of friction of automotive brake pad materials.
Scheme of application of antimony-based products