Research history of zirconium

Discovery history of zirconium

ZrSiO4, a natural silicate containing zirconium, is called zircon or hyacinth. It is widely distributed in nature and has various beautiful colors from orange to red. It has been considered a gem since ancient times. It is said that the word zircon comes from Arabic zarq ū n. It's cinnabar, and it's also from Farsi Zargun, and it's gold. Hyacinth comes from the Greek word "lily". Sri Lanka, an island country in the Indian Ocean, is rich in zircon. Gemstones containing zirconium have been known as zircon in ancient times.

When German m.h.klaproth studied zircon in 1789, he found that it was co melted with sodium hydroxide, the coolant was dissolved with hydrochloric acid, potassium carbonate was added to the solution, precipitated, filtered and cleaned the precipitate, and then the precipitate was co boiled with sulfuric acid, and then the oxide of silicon was filtered out. The oxide of calcium, magnesium and aluminum was checked in the filter, but no precipitation was found after adding potassium carbonate to the solution, This precipitate is not soluble in lye like alumina, nor does it interact with acid like magnesium oxide. Klaproth believes that this precipitate is different from the previously known oxide and is composed of zirkonerde (zircon, German). Soon, French chemists de morueau and vauquelin both confirmed that m.h.klaproth's analysis is correct. The Latin name of this element is zirconium, and the symbol is Zr, which is translated into zirconium in China.

In 1808, h.davy in Britain used electric current to decompose zirconium compounds, but it was unsuccessful. In 1824, J.J.Berzelius in Sweden first reduced k2zrf6 with potassium to produce metallic zirconium, but it was not pure enough. The reaction formula was: k2zrf6+4k=zr+6kf. Na could also be used as reductant in this reaction. Until 1914, Lely and ham bruger, two researchers from a metal incandescent lamp manufacturing plant in Holland, used anhydrous zirconium tetrachloride and excess metallic sodium to put them into an empty ball, Pure zirconium metal was obtained by heating 500 ℃ with electric current.

Completely pure zirconium was prepared by the Dutch chemists Anton Eduard van Arkel and Jan Hendrik de Boer from the decomposition of zirconium tetraiodide (zri4) in 1925. Zirconium is mass produced by heating zirconium tetrachloride with magnesium.

Development history of zirconium in China

The development of China's zirconium industry is arduous and tortuous, but it has made great contributions to the development of the world's zirconium industry. The development of China's zirconium industry has gone through the following stages.

In the 1960s, China once produced hafnium free nuclear zirconium by carbon chlorination. At that time, there were Shanghai Red smelter, 901 plant and Jinzhou Ferroalloy Plant; At the same time, Shanghai Wuyi chemical plant, Beijing nonferrous metal smelting plant, Shuikoushan No. 6 plant and Henan Jiaozuo chemical plant produce zirconia by sulfuric acid method. As China's nuclear industry has not yet developed, zirconia has not been applied in industry, there are serious problems in production technology, product quality, environmental pollution, etc., and it is difficult to fund. Therefore, the scale of these plants has not been developed, most of them have been shut down, converted to production, closed down, and only a few of them have been retained, pending, and tested.

In the mid-1970s, the development of zirconia application abroad affected China. In particular, the application of zirconia in sanitary ceramics has promoted the development of zirconia. However, due to the original backward process technology, long process flow, poor product quality and serious environmental pollution, people were forced to carry out research on the improvement of zirconia production process. Later, NaOH sintering and HC1 decomposition processes applied in industry were established to produce zirconia, and Yixing Chemical Plant, the first plant to produce zirconia according to NaOH sintering process, was established in 1978. At the same time, a small production plant has been established in Huzhou. The product quality was relatively good at that time (in China), but the scale was relatively small. Because the application of zirconia in China was still very strange at that time, the sales volume was not very large.

Due to the complex production process of zirconium oxychloride and serious environmental pollution, in order to protect their own interests, developed countries almost removed this low profit, high energy consumption and high pollution early production process, and retained an efficient and pollution-free deep processing process. Therefore, almost all developed countries have stopped producing zirconium oxychloride and purchased zirconium oxychloride raw materials from abroad, which has promoted the development of China's zirconium industry. With the opening of China to the world market in 1980, zirconium oxychloride began to be exported, and the scale of Yixing Chemical plant developed rapidly. This may be a turning point in the development of China's zirconium industry. With the expansion of foreign trade, the varieties and output of zirconium chemicals have increased, and the enterprise benefits are good. Driven by interests, a number of new enterprises were developed in China at this time, and the production capacity increased, but the production capacity could not keep up with the production capacity.

By the 1990s, zircon sand from South Africa and Australia had entered China, and the quality, technological level and recovery rate of zirconium chemicals had been improved. At the same time, according to the requirements of foreign merchants, the types of zirconium chemicals have also expanded. Driven by interests, the number of manufacturers increased further, the supply of zircon sand was sufficient, and the price of raw materials fell. The export volume of zirconium oxychloride has soared, which has promoted the development of China's Zirconium chemical industry. However, due to poor information exchange and lack of communication among enterprises, domestic zirconium oxychloride manufacturers have increased too much, and enterprises compete with each other and press prices, resulting in price decline. At the same time, due to the sharp increase in production, technology and testing methods can not keep up, product quality has declined, and environmental pollution is serious. It is not conducive to the development of zirconium chemicals in China. The output in this period was about 20000T.

After 1990, the world market for zirconium chemicals expanded, and the demand for zirconium ceramic pigments and glazes increased significantly. Western countries have established many joint ventures in China to produce ceramic glazes, resulting in a substantial increase in the demand for ZrO. This has greatly stimulated the development of zirconium chemicals in China, with new factories swarming, and the production of the original enterprises increasing continuously. In China, the supply of zirconium chemicals exceeded demand for the first time, with an output of 40000-45000 tons. The price fell, and the efficiency of enterprises decreased significantly. In recent years, zirconium chemicals in China have made greater progress, but due to the shortage of zircon sand. The rise in the price of raw materials, the intensification of competition among enterprises, the low price of zirconium chemicals and the increase in inventory have led to difficulties for enterprises, even serious losses, and small factories on the verge of closure.

The output of zirconium chemicals in China is about 70000-75000 tons, and the inventory is 10000-15000 tons. There is a serious backlog of funds. Some factories are shutting down production, while others are expanding production. Therefore, the development of China's zirconium industry is not optimistic.