China's HF Industry Develops High-end Products and Broadens Sources of Raw Materials   

By Luo Yamin, Research Institute of Industrial Economics of CNCIC

Hydrogen fluoride (HF) is widely used in the chemical, nuclear power, petroleum, electronics and metallurgical industries. In organic synthesis, it can be used as a catalyst for alkylation, polymerization, condensation and isomerization. It is the basic raw material for the production of elemental fluorine, various fluorinated hydrocarbons and various inorganic fluorides. In the defense and energy industries, it is a raw material for the manufacture of uranium hexafluoride and is one of the raw materials for the production of rocket fuel and additives. Hydrofluoric acid is used in the manufacture of graphite and also used as a glass etching agent and metal cleaning agent. High-purity hydrofluoric acid is widely used as a strong acid-washing agent and a corrosive in the microelectronics industry.

1  Overcapacity appears in China

Industrially, HF is mostly produced from fluorite by the sulfuric acid converter method. Only a little of the HF on the market is produced from fluosilicic acid which exists in the exhaust gas of phosphoric acid production. In 2010, the world's total HF production capacity was 2.6 million t/a. Major HF manufacturers are Honeywell, DuPont, Solvay, and China's Yingpeng Chemical Group and Centralfluor Industries Corp (CFIC). Canada and Mexico also each have a large HF production capacity. After falling in 2009, global demand for HF rebounded in 2010, growing 15% year on year.
   Since 2005, China's HF production capacity has expanded rapidly. Many HF projects have been set up in various places throughout the country. Now, there are more than 50 HF producers in China. In 2010, they had a combined HF production capacity of about 1.39 million t/a, accounting for 54% of the world's total. In 2010, China's HF output was about 940 000 tons, up 12% year on year, but the average operating rate of HF plants was only 67%, so there is significant overcapacity. HF producers are mainly distributed in Southeast China, where there are high-grade fluorite resources. They are now beginning to move toward fluorite-rich places in Inner Mongolia. After several years of resource integration, CFIC has now become China's largest HF producer, and Yingpeng Chemical is the second largest. These large HF producers mostly own fluorite mines or are located nearby fluorite mines. At the same time, they also have refrigerant and downstream fluoro-product production facilities. Shandong Dongyue Chemical Co Ltd, Shanghai 3F New Material Co Ltd, Jiangsu Meilan Chemical Group Co Ltd, and Zhonghao Chenguang Research Institute of Chemical Industry have mastered advanced technology and extended their fluorine industrial chains from fluorinated hydrocarbons to fluorine rubber, fluorine resins, fluorine-containing fine chemicals and other high-end products.
   In China, HF is mainly used for the production of fluorinated hydrocarbons and fluorides. In 2010, these two areas accounted for 50% and 40% of China's total HF consumption, respectively. In the next five years, China's consumption of HF will continue to grow around 6% to 7% annually and will reach 1.08 million tons in 2015.
   Meanwhile, in those five years, China's HF overcapacity situation will not change much, and the average operating rate of HF plants will remain 60% to 70%. To rein the rapid expansion of domestic HF production capacity, the Chinese Ministry of Industry and Information Technology (MIIT) issued the "Access Conditions for Hydrogen Fluoride Industry" in February 2011, which stipulates that the total HF capacity of any new HF producer should be at least 50 000 t/a and the capacity of any new HF plant should be no less than 20 000 t/a. At the end of April 2011, MIIT released the "Guiding Catalogue for Restructuring of Fluorine Chemical Industry (2011) ," which stipulates that the construction of new HF plants should be restricted (except for electronic grade HF plants and supporting units of wet-process phosphoric acid production, and that hydrofluoric acid plants with a capacity of less than 5 000t/a should be eliminated.

2  Imports and exports constantly increase

From 2002 to 2010, China's import and export of HF (including hydrofluoric acid) both increased every year except 2009. In 2010, China imported only 2 000 tons of HF. But it exported 160 000 tons (equivalent to 300 000 tons of fluorite), up 48% year on year.
   In 2010, Japan was China's largest HF export destination and accounted for 46% of China's total HF exports, followed by China's Taiwan region (19%) and Korea (14%). The three countries and region have a strong production capacity of high-purity hydrofluoric acid. Due to their advanced electronics manufacturing industries, Japan and Taiwan are also major consumers of high-purity hydrofluoric acid. Japan, Taiwan and Korea accounted for 55%, 23% and14% of China's import of hydrofluoric acid, respectively.

3  Production capacity of high-purity hydrofluoric acid grows fast in China

High-purity hydrofluoric acid is one of key basic chemical materials for the manufacture of integrated circuits (ICs) and ultra large-scale ICs. It can be used together with nitric acid, acetic acid, hydrogen peroxide or ammonium hydroxide and is mainly used as cleaning and corrosive agents in the manufacture of IC chips and ULSI IC chips. It is also used in photovoltaic (PV) and LCD display industries. Its purity and cleanliness have significant impacts on the finished product ratio, electrical performance and reliability of ICs. Its product level is generally divided into four grades. Currently, about 10 producers in China can produce SEMI C1 - 7 grade (including MOS grade and BV-I- III grade) high-purity HF products, but very few can produce SEMI C8 - 12 grade (roughly equivalent to or higher than BV-III grade) HF products. In 2009, Juhua Group's Kaiheng Electronic Materials Co Ltd (Kaiheng) built a 6000 t/a high-purity hydrofluoric acid plant, which was China's first large-scale industrial installation making high-purity hydrofluoric acid. Since this plant was put into production, its product has been well received. In 2010, Shaowu Yongfei Chemical Co Ltd's 3000 t/a high-purity hydrofluoric acid plant was put into operation, which is China's second large-scale high-purity hydrofluoric acid producer. In January 2011, Zhejiang Lansol Fluorchem Co Ltd also put its 5000 t/a high-purity hydrofluoric acid project into operation.
   In 2005, China's consumer electronics industry consumed nearly 3000 tons of high-purity hydrofluoric acid, of which about 1550 tons was imported from abroad. In 2010, it consumed more than 5000 tons, of which nearly 2300 tons was imported. From 2005 to 2010, the average annual growth rate of domestic high-purity hydrofluoric acid consumption reached more than 10%.
   As of June 2011, China's electronic grade hydrofluoric acid production capacity had reached about 26 000 t/a. Currently, Yingpeng Chemical Group's Xuancheng Hengtai Chemical Technology Co Ltd, Fujian Fubao Tengda Chemical Co Ltd, Shaowu Huaxin Chemical Co Ltd and Suzhou Crystal Clear Chemical Co Ltd have electronic grade hydrofluoric acid projects under construction. Kaiheng continues to expand its electronic grade hydrofluoric acid capacity. A total electronic grade hydrofluoric acid capacity of more than 50 000 t/a is now under construction in China. Such fast expansion capacity aims mainly to seize foreign markets. Japan, the USA, EU and China's Taiwan are major consumer areas of high-purity hydrofluoric acid. Major high-purity hydrofluoric acid producers in China are listed in Table 1.

Table 1  Major high-purity hydrof