Fluorite deep processing to produce fluororubber

2022-07-23
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Fluorite deep processing to produce fluororubber

fluororubber is a synthetic rubber containing fluorine atoms. It has excellent high temperature resistance, oil resistance, acid and alkali resistance and a variety of chemical media. It also has excellent vacuum performance, good electrical performance and excellent mechanical performance. It is an indispensable and excellent material for modern aviation, rocket, aerospace, ship, automobile and petrochemical industry. The incomparable performance of fluororubber is being used more and more widely, and its demand is increasing. The prospect of producing fluororubber from fluorite mineral resources is extremely broad

production and development status of fluororubber at home and abroad

fluororubber is a synthetic polymer elastomer, that is, it contains fluorine atoms on the carbon atoms of the main or side chains of rubber molecules. The earliest fluororubber is poly-2-fluoro-1.3-butadiene and its copolymers with styrene, propylene, etc. produced by DuPont company in 1948. However, its performance is not better than that of neoprene and shall not be lower than that of B2 grade nitrile rubber. Moreover, it is expensive and has no actual industrial value. In the late 1950s, Thiokol company of the United States developed a kind of binary nitroso fluororubber with good low temperature performance and strong oxidizer resistance (N2O4), and fluororubber began to enter practical industrial application. Since then, with the technological progress, various new fluororubbers have been developed

China began to develop fluororubber in 1958, and its main varieties are polyolefin fluororubber, such as 23, 26, 246 and nitroso fluororubber; Later, relatively new varieties of tetrapropyl fluororubber, perfluoroether rubber, fluorinated phosphorus rubber and fluorosilicone rubber were developed. The square level with an accuracy of no less than 0.1/1000 was first used in the field of military industry and aviation, and has been gradually extended to the field of civil industry, especially the automotive industry (accounting for 70%)

at present, the manufacturers in China include Chenguang and Dongyue, and the research and development department also includes Shanghai organic fluorine materials research institute. The production suppliers of imported fluororubber include DuPont of the United States, 3M of the United States, Daikin of Japan and Solvay of Europe. At present, the global production of fluororubber is about 30000 tons/year, increasing by nearly 8% year by year. There are more than 50 varieties, and they are still emerging. For example, the fluorinated phosphor clear rubber newly developed in the United States has a temperature resistance range of -55 ℃_ 230 ℃, fluororubber can withstand temperature up to 300 ℃, and short-term temperature up to 400 ℃. In recent years, the average annual growth rate of domestic fluororubber consumption is as high as 5%. In 2006, the demand was 6600 tons/year, and it is expected to rise to 10000 tons/year in 2010. However, the domestic production capacity is far from meeting the demand, so it still relies on imports (the main importing countries are the United States, Italy and Russia). The main manufacturers are Jiangsu Meilan and Sichuan Chenguang, with a total production capacity of only 2600 tons/year and a single variety (mainly type 26). In recent years, as a high-tech product, fluororubber has been recognized as a national key development and support industry. Fluororubber is also a high value-added product, more than 10 times higher than the price of rubber

due to the rapid development of China's automobile industry (second only to the United States, ranking second in the world), and the continuous improvement of the market requirements for automobile reliability and safety, the market demand for fluororubber has been greatly stimulated. At present, the domestic 60_ 70% of fluororubber is used in the automotive industry. Its consumption increased from 300 to 3000 tons per year during the Tenth Five Year Plan period, and is now approaching 10000 tons per year

high value deep processing of fluorite

fluorite is CaF2, which is a non renewable resource. China is rich in fluorite resources, with reserves of 130 million tons, accounting for 2/3 of the world's reserves. Since 1999, the state has taken a series of measures to protect fluorite, such as restricting export quotas, abolishing export tax rebates and increasing export tariffs (by 15%). Therefore, the fluorine chemical industry should be a unique industry in China. In recent years, the international fluorine chemical industry has been transferred to China, so its annual growth rate is more than 15%. Among them, fluorine resin has entered the mature stage, while fluorine rubber is in the rapid growth stage, and other fluorine-containing fine chemicals are also more extensive. In particular, the high interest rate of fluororubber has remained unchanged for many years

with the development of fluorine chemical industry, China has exported 1.3 million tons of fluorite every year since the 1990s, which once caused excessive disorderly mining and a large number of exports, and severely damaged resources. Since then, the export volume has dropped to 500000 tons per year due to the inclusion in the catalogue of prohibited processing trade. However, there are policies at the top and Countermeasures at the bottom. Foreign investors have invested and set up factories in China to produce low-end hydrofluoric acid for re export (the annual export is equivalent to 300000 tons). With smuggling, the export of fluorite has not decreased

fluorite is mainly produced in Jiangxi, Zhejiang, Fujian, Anhui, Hebei and Liaoning. Twenty years ago, Zhejiang was complacent about the export of fluorite, but now it has to import fluorite from other provinces. At present, the domestic hydrofluoric acid has been seriously surplus, and the export of hydrofluoric acid will soon be subject to protective restrictions. In addition, the demand for fluorite in China's own development is also large. By 2010, the total demand will reach 2million tons/year, so it is urgent to develop downstream products of fluorochemical industry. For example, a ton of hydrofluoric acid requires five tons of fluorite. The current market price of hydrofluoric acid is 4600 yuan/ton, the price of high-grade imported electronic grade anhydrous hydrofluoric acid is 40000 yuan, and the price of high-grade fluororubber is as high as 30_ 400000 yuan/ton. Therefore, it is very uneconomical to export a large amount of fluorite or hydrofluoric acid. In less than 30 years, China's proven fluorite reserves will soon be exhausted

it can be seen from the above that starting from fluorite, with the increase of processing depth, the added value of the product increases by geometric multiples. For example, the price of fluorite is only a few hundred yuan, the price of anhydrous hydrofluoric acid is thousands of yuan, the price of polytetrafluoroethylene is tens of thousands of yuan, while the price of fluororubber is hundreds of thousands of yuan, and the price of fluorine-containing fine chemicals can be as high as millions of yuan (mostly imported). Among them, China's new material industry with a capacity of 30000 will pay more attention to the sustainable development of tons/year, the domestic demand is only 20000 tons/year, and the excess will lead to bargain competition, Daikin Co., Ltd. of Japan invested 1.33 billion yuan in the construction of polytetrafluoroethylene in Changshu, Jiangsu Province. When completed, the total production capacity will reach 40000 tons/year, and the profit decline is inevitable. Therefore, some Chinese companies that produce primary fluorine monomers have lost money. The high price of fluororubber and the protection measures of fluorite bring opportunities for the development of fluororubber in China

2003, the production capacity of fluororubber in China was only 25000 tons, and the product was single (only 26 fluororubber), but the demand increased at the rate of 3%. At present, perfluoroether, metafluorohexene, phosphine fluororubber and fluororubber without vulcanization, which are urgently needed in China, need to be imported. In the international last year, the consumption was mainly distributed in the United States, Europe and Japan (42%, 28.8% and 12.5% respectively). As China is a large country in fluorite production and export, due to export restrictions, foreign investors have entered China with joint ventures, sole proprietorships and acquisitions. After Daikin of Japan entered Changshu, other multinational companies have also come to China

however, the current pattern of investment competition is: the upstream products are highly competitive. Among them, anhydrous hydrofluoric acid has matured and expanded rapidly. The former has a production capacity of more than 150000 tons, and the supply exceeds the demand. However, a large number of high-end fluorine chemical products are blank. By actively seeking introduction and cooperation, we can realize product upgrading and lead the original resource competition to deep processing competition by taking advantage of the opportunity of foreign fluorination workers' transfer to China when they reach a specified deformation value

at the same time, in China, Shanghai organic fluorine materials research institute and Sichuan Chenguang Institute are high-tech research institutes integrating research, development and production, which can produce and develop fluororubber and fluorochemical fine product production lines. Its core technology is the monomer preparation of organic fluorine materials, the polymerization and post-treatment technology of organic fluorine materials. Its level is in the middle and late 1990s abroad, leading its domestic counterparts. It can upgrade products for enterprises, avoid the fierce competition of low-end products, and obtain high added value and high profits. There are four major categories of leading products studied: fluoropolymers, fluoro fine chemicals, fluororefrigerants and CFCs substitutes. It belongs to perfluorooctanoic acid of fluorochemical industry and is mainly used as dispersant for fluoropolymer production. Its new production base in Shanghai Caojing Chemical Industry Zone in 2005 covers an area of 200 mu, with an investment of 350million yuan to produce fluorine-containing fine chemicals and special fluorine-containing polymers. The main problems at present are that it has no fluorite resources, the investment and construction scale are small, and the production and labor costs are relatively high

in addition, Zhejiang Juhua Co., Ltd. mainly produces fluorine monomers and their polymers, including the related technology development of fluorine-containing fine chemicals. It is the most complete production enterprise in the domestic fluorine chemical industry, and its fluorine chemical products and production capacity rank first in the country

conclusion

to sum up, using abundant fluorite and hydrofluoric acid raw materials to attract investment and production of fluorine monomer and fluorine rubber is a high profit way to get rich

for example, from hydrofluoric acid to fluororubber, the first step is to add metafluorohexene + hexafluoropropylene → fluororubber with binary structure. Tetrafluoroethylene is also required for ternary structure, and these monomers can be bought on the market

theorists have always paid attention to: should we do it; And doers pay attention to whether they can do it or not. Fluorite can be used to produce fluororubber. Why not? The key is "consciousness should enter the state". (end)

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