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China's fluorine chemical industry has developed rapidly in recent years and has become a global producer and consumer of fluorine chemical products. At present, most fluorine products at home and abroad are produced from fluorspar as raw materials. However, fluorite is an important strategic resource. Countries all over the world attach great importance to the protection of fluorite resources and even import large amounts of them for storage. China has also gradually taken measures to protect fluorite resources. Since 2001, the country began to implement an export quota system for fluorspar exports, adopted a tariff increase to limit the export of fluorspar, and no longer issued new fluorspar mining licenses in 2003, which has made the production of hydrofluoric acid-enriched fluorspar increasingly tense. Under such circumstances, the development of fluorine chemicals can no longer rely entirely on fluorspar. How to make full use of the by-product fluorine resources of phosphate fertilizers has become a concern in the world.
Phosphorus and fluoride resources are worthy of attention According to experts, about 2% to 4% of fluorine in phosphate rock. The world's reserves of phosphorus resources are relatively large. Therefore, all countries in the world place great emphasis on the comprehensive utilization of fluorine resources in phosphate rock. The United States is a large country of phosphate ore, and 30% of its by-product fluorosilicic acid is used in the production of aluminum fluoride. Relevant experts believe that China's phosphorus resources ranks second in the world. Phosphorus ore is associated with a much larger fluorine resource than fluorite. The research, development, and comprehensive utilization of fluorine-silicic acid, a by-product of phosphate fertilizer, is not only beneficial to the fluorine environment of phosphate fertilizers. Pollution control, but also conducive to the protection of fluorite resources, kill two birds with one stone.
During the "10th Five-Year Plan" period, China's output of phosphate fertilizer increased by nearly 70%, surpassing the United States for the first time in the world. At the same time, the production of by-produced fluorosilicic acid also increased from 100,000 tons in 2000 to 330,000 tons in 2005, and is expected to increase to 500,000 tons in the “Eleventh Five-Year Plan†period. However, the utilization of phosphorus resources in China's phosphate fertilizers has not been given full attention. Even the preliminary problems of phosphorus fertilizer fluorine pollution have not been well resolved. Take the flake fluorosilicic acid as a byproduct, a considerable part of the market is returned to the production of phosphoric acid because of technical reasons. This not only results in the emission of fluorine exceeding the standard, but also results in the excessive fluorine content in the phosphorous gypsum produced by the phosphate fertilizer. This limits the use of phosphogypsum as a waste residue. Comprehensive utilization. Although at the beginning of the 1990s, phosphate fertilizer production enterprises in Guixi, Jiangxi, Luzhai, Guangxi, and Hongfu, Guizhou, respectively, imported four sets of fluorosilicic acid fluoride production equipment from abroad, but from a national perspective, the phosphorus resources of phosphorus Development and utilization are still in their infancy. The development and utilization of phosphorus fertilizer resources is imminent.
Mature technology is worth learning from. In China's current use of phosphate fertilizer by-products, there are some for the production of sodium fluoride, potassium fluorosilicate, cryolite, aluminum fluoride and other inorganic fluorine chemical products. Among the mature technologies are the following: The overflow of fluorine-containing gas is absorbed into fluorosilicic acid with water, most of it is processed into sodium fluorosilicate, and a small amount is processed into aluminum fluoride and sodium fluoride. There are also many process routes for the production of cryolite from the use of the by-product of the production of phosphoric acid as a byproduct of the production of fluoride. However, only the production of the cryolite has been officially put into operation in China. Only the sodium fluorosilicate method of cryogenic production of polyfluoride from Henan Jiaozuo Chemical Co., Ltd. has produced high quality products. The white carbon project has an annual output of 20,000 tons of cryolite and 6000 tons of white carbon black. This technology has not only won national invention patents, but has also been named "National High-tech Industrialization Demonstration Project". From the social use of resources, the technology has brought about qualitative changes and enhancements for many industries: First, it has opened up new "fluorine" resources. This technology has changed the domestic use of fluorspar to hydrofluoric acid to produce cryolite. The practice of using fluorine in sodium fluorosilicate as a fluorine resource to produce cryolite can save 30,000 tons of quality fluorspar per year for the country. Second, it fundamentally solves the pollution problem that has long constrained the development of phosphorus and compound fertilizer in China. The third is to promote the technical progress of the electrolytic aluminum industry. The polymer produced by this project is mainly used for electrolytic aluminum than cryolite, which not only saves soda ash, but also effectively improves its technical and economic indicators. The fourth is to achieve a new breakthrough in the production of white carbon black production technology in China.
The results of the new technology are worthy of attention. According to experts, in the future development of new technologies for the application of fluorine resources, the preparation of anhydrous hydrogen fluoride from fluorosilicic acid should be the best solution for the use of fluorine resources. The process routes are direct and indirect. Directly outside France, a test line with an annual output of 10,000 tons was built in Poland. China Hongfu Company signed a technology agreement with foreign countries in 2005 to build an annual production capacity of 20,000 tons of anhydrous hydrogen fluoride production plant, which is expected to be completed and put into production this year. The indirect process, “Wet-process phosphoric acid production of fluorosilicic acid to produce hydrofluoric acid†was publicly tendered in the Yunnan Science and Technology Department in 2004, and Yuntianhua Group and Tianjin Institute of Research and Design won the bid to work together to determine the ammonia process route. ,Complete the lab test; In 2005, in cooperation with Duoduo Chemical Industry Co., Ltd., completed the design and construction of 300 tons/year hydrofluoric acid (100%) pilot plant; in June 2006, the whole process was opened and the qualification was passed. The products have passed the field acceptance of experts; the next step will be to conduct a feasibility study of 20,000 tons of anhydrous hydrogen fluoride devices.
Relevant experts believe that the phosphorus resource of phosphorus fertilizer has broad prospects for development and extensive research and development space. The relevant units of production, research, and research must work together to increase resource utilization at both the elemental cycle and process engineering level so that the comprehensive utilization of resources can no longer be realized. Take a lot of precious fluorite resources and produce old low-level fluoride products. At the same time, the experts also reminded enterprises that the development of phosphorus resources for phosphorus fertilizers should also be carried out scientifically. Otherwise, the fluorine resources of phosphate fertilizers will not only fail to be recycled, but also cause more pollution and waste.
Phosphorus and fluoride resources are worthy of attention According to experts, about 2% to 4% of fluorine in phosphate rock. The world's reserves of phosphorus resources are relatively large. Therefore, all countries in the world place great emphasis on the comprehensive utilization of fluorine resources in phosphate rock. The United States is a large country of phosphate ore, and 30% of its by-product fluorosilicic acid is used in the production of aluminum fluoride. Relevant experts believe that China's phosphorus resources ranks second in the world. Phosphorus ore is associated with a much larger fluorine resource than fluorite. The research, development, and comprehensive utilization of fluorine-silicic acid, a by-product of phosphate fertilizer, is not only beneficial to the fluorine environment of phosphate fertilizers. Pollution control, but also conducive to the protection of fluorite resources, kill two birds with one stone.
During the "10th Five-Year Plan" period, China's output of phosphate fertilizer increased by nearly 70%, surpassing the United States for the first time in the world. At the same time, the production of by-produced fluorosilicic acid also increased from 100,000 tons in 2000 to 330,000 tons in 2005, and is expected to increase to 500,000 tons in the “Eleventh Five-Year Plan†period. However, the utilization of phosphorus resources in China's phosphate fertilizers has not been given full attention. Even the preliminary problems of phosphorus fertilizer fluorine pollution have not been well resolved. Take the flake fluorosilicic acid as a byproduct, a considerable part of the market is returned to the production of phosphoric acid because of technical reasons. This not only results in the emission of fluorine exceeding the standard, but also results in the excessive fluorine content in the phosphorous gypsum produced by the phosphate fertilizer. This limits the use of phosphogypsum as a waste residue. Comprehensive utilization. Although at the beginning of the 1990s, phosphate fertilizer production enterprises in Guixi, Jiangxi, Luzhai, Guangxi, and Hongfu, Guizhou, respectively, imported four sets of fluorosilicic acid fluoride production equipment from abroad, but from a national perspective, the phosphorus resources of phosphorus Development and utilization are still in their infancy. The development and utilization of phosphorus fertilizer resources is imminent.
Mature technology is worth learning from. In China's current use of phosphate fertilizer by-products, there are some for the production of sodium fluoride, potassium fluorosilicate, cryolite, aluminum fluoride and other inorganic fluorine chemical products. Among the mature technologies are the following: The overflow of fluorine-containing gas is absorbed into fluorosilicic acid with water, most of it is processed into sodium fluorosilicate, and a small amount is processed into aluminum fluoride and sodium fluoride. There are also many process routes for the production of cryolite from the use of the by-product of the production of phosphoric acid as a byproduct of the production of fluoride. However, only the production of the cryolite has been officially put into operation in China. Only the sodium fluorosilicate method of cryogenic production of polyfluoride from Henan Jiaozuo Chemical Co., Ltd. has produced high quality products. The white carbon project has an annual output of 20,000 tons of cryolite and 6000 tons of white carbon black. This technology has not only won national invention patents, but has also been named "National High-tech Industrialization Demonstration Project". From the social use of resources, the technology has brought about qualitative changes and enhancements for many industries: First, it has opened up new "fluorine" resources. This technology has changed the domestic use of fluorspar to hydrofluoric acid to produce cryolite. The practice of using fluorine in sodium fluorosilicate as a fluorine resource to produce cryolite can save 30,000 tons of quality fluorspar per year for the country. Second, it fundamentally solves the pollution problem that has long constrained the development of phosphorus and compound fertilizer in China. The third is to promote the technical progress of the electrolytic aluminum industry. The polymer produced by this project is mainly used for electrolytic aluminum than cryolite, which not only saves soda ash, but also effectively improves its technical and economic indicators. The fourth is to achieve a new breakthrough in the production of white carbon black production technology in China.
The results of the new technology are worthy of attention. According to experts, in the future development of new technologies for the application of fluorine resources, the preparation of anhydrous hydrogen fluoride from fluorosilicic acid should be the best solution for the use of fluorine resources. The process routes are direct and indirect. Directly outside France, a test line with an annual output of 10,000 tons was built in Poland. China Hongfu Company signed a technology agreement with foreign countries in 2005 to build an annual production capacity of 20,000 tons of anhydrous hydrogen fluoride production plant, which is expected to be completed and put into production this year. The indirect process, “Wet-process phosphoric acid production of fluorosilicic acid to produce hydrofluoric acid†was publicly tendered in the Yunnan Science and Technology Department in 2004, and Yuntianhua Group and Tianjin Institute of Research and Design won the bid to work together to determine the ammonia process route. ,Complete the lab test; In 2005, in cooperation with Duoduo Chemical Industry Co., Ltd., completed the design and construction of 300 tons/year hydrofluoric acid (100%) pilot plant; in June 2006, the whole process was opened and the qualification was passed. The products have passed the field acceptance of experts; the next step will be to conduct a feasibility study of 20,000 tons of anhydrous hydrogen fluoride devices.
Relevant experts believe that the phosphorus resource of phosphorus fertilizer has broad prospects for development and extensive research and development space. The relevant units of production, research, and research must work together to increase resource utilization at both the elemental cycle and process engineering level so that the comprehensive utilization of resources can no longer be realized. Take a lot of precious fluorite resources and produce old low-level fluoride products. At the same time, the experts also reminded enterprises that the development of phosphorus resources for phosphorus fertilizers should also be carried out scientifically. Otherwise, the fluorine resources of phosphate fertilizers will not only fail to be recycled, but also cause more pollution and waste.
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