Price of Pyridine Kept Rising in China
Year:2013 ISSUE:11
COLUMN:ORGANICS
Click:194    DateTime:Nov.06,2013
Price of Pyridine Kept Rising in China

By Shen Guiying, the Consulting Department of China National Chemical Information Center

Pyridine is mainly used to synthesize the herbicides paraquat and diquat, and the insecticide chlorpyrifos. It is also used in the pharmaceutical and new materials sectors. In industrial production, paraquat and diquat are synthesized using only pyridine as raw material. There are two industrialized chlorpyrifos production technologies – the pyridine route and the non-pyridine route. Pesticide production is the main consumption sector for pyridine.
1. Price of pyridine has risen for six months
Since September 2012, the price of pyridine has increased constantly.  The price of pyridine climbed from RMB26 500 per ton in September 2012 to RMB32 000 per ton in March 2013, a rise of over 20%.
Since 2000, China’s production scale of pyridine has expanded continually. As of early 2013, the total capacity to make pyridine in China reached 88 thousand t/a. In 2012, China’s output of pyridine reached around 30 thousand tons, and the net import volume was 17 thousand tons. With the growth of both the capacity and the import volume, the price of pyridine has declined in recent years. It reached a high of RMB55 000 per ton in January 2008, and decreased to RMB38 000 per ton, RMB30 000 per ton and RMB26 000 per ton, respectively, in January 2010, January 2012 and August 2012.
The lower price of pyridine has narrowed the profit margin of pyridine production enterprises. Three new pyridine units that were being built in 2011 have still not gone into normal production. On September 21, 2012, the Ministry of Commerce announced a new dumping investigation of pyridine imported from India and Japan. The recent price rise of pyridine coincides with the conduct of the dumping investigation. In view of the rising price, the operating rate of domestic pyridine units is expected to increase to a certain extent.
2. Joys and Worries in the Market Prospect
Pyridine is one of the "chips" for the synthesis of fourth generation heterocyclic pesticides. Mature industrial varieties of pesticides include paraquat, diquat and chlorpyrifos. Many new varieties being developed and studied also contain the structure of pyridine rings.
The clean technologies for making chlorpyrifos need pyridine. Chlorpyrifos, which is synthesized using sodium 3,5,6-trichloropyridin-2-olate and diethylthiophosphoryl chloride  as raw materials, is one of the three best-selling insecticides worldwide, and has also become the main substitute for five highly toxic insecticides – methamidophos, parathion, methyl parathion, monocrotophos and dimecron – that China has prohibited for use since 2007. According to statistics of CCPIA, China’s output of chlorpyrifos was 41.9 thousand tons in 2011. There are two production processes of sodium 3,5,6-trichloropyridin-2-olate. One is the pyridine route – through chlorination, pyridine can be made into tetrachloropyridine, which is further reacted to get sodium 3,5,6-trichloropyridin-2-olate. Another is the cyclization route – using trichloroacetyl chloride and acrylonitrile as raw materials, sodium 3,5,6-trichloropyridin-2-olate can be synthesized through a cyclization reaction. Foreign companies use the pyridine route, while domestic producers mostly use cyclization route.
Unfortunately, the cyclization process also produces serious pollution. Moreover, making one ton of chlorpyrifos this way can discharge 3-6 tons of wastewater. The pyridine method is relatively clean, with zero wastewater emission. National requirements for clean production of chlorpyrifos will promote the development of the pyridine market. In the interest of saving energy and reducing emissions, the high-pollution process will be eliminated, opening a bigger market for pyridine. At present, many enterprises in Shandong, Zhejiang and Jiangsu provinces are turning attention to making chlorpyrifos from pyridine.
Downstream, some new fields have recently expanded the pyridine market. In addition to tetrachloropyridine as an important intermediate in the synthesis of chlorpyrifos, 2,3-dichloropyridine has become an important pesticide intermediate and can be used for synthesis of chlorantraniliprole. Chlorantraniliprole is insecticide developed by DuPont of the United States. DuPont's Rynaxypyr (20% chlorantraniliprole) won the most creative chemistry prize in BCPC International Plant Protection Congress on October 16, 2007. The prize is awarded to chemical pesticides that have made outstanding contributions to the world's ecological wellbeing. In recent years, the market volume of chlorantraniliprole has increased rapidly, and the manufacture of chlorantraniliprole has become a new pyridine market worthy of attention.
Directional chlorination and fluorination technologies for pyridine and its derivatives have been designated as encouraged projects during the Twelfth Five-Year Plan (covering 2011 to 2015). On February 3, 2012, the Ministry of Industry and Information Technology formally announced the Twelfth Five-Year Plan for the Petrochemical Industry, stating that China’s petrochemical industry should
?vigorously promote technological progress
?promote original innovation, integrated innovation
?strengthen basic research that has  great significance to sustainable development
?strengthen basic technology research according to the national science and technology program (special), and make breakthroughs in a number of core, common and key technologies including the directional chlorination and fluorination technologies for pyridine and its derivatives.
At the same time, the Ministry of Industry and Information Technology officially announced the Twelfth Five-Year Plan for the Pesticide Industry, stating that the industry should improve the ability of technological innovation and focus on the development of directional chlorination and fluorination technologies for pyridine and its derivatives.
After 2016, paraquat may exist in the Chinese market.  At present, paraquat products, which consume the largest amount of pyridine in the domestic market, are being restricted. China has terminated the registration of paraquat aqueous solution. On April 24, 2012, the Ministry of Agriculture, the Ministry of Industry and Information Technology and the General Administration of Quality, Supervision, Inspection and Quarantine jointly released announcement No.1745, canceling the registration and licensing for producing paraquat aqueous solution, stopping the production of paraquat aqueous solution, retaining the overseas registration for export of paraquat aqueous solution by paraquat technical enterprises and allowing the production of paraquat aqueous solution for export from July 1, 2014, and stopping the domestic sale and use of paraquat aqueous solution from July 1, 2016. Aqueous solution is the only commercial formulation of paraquat. It has been used for around 50 years.
The development of new formulations for paraquat will play a decisive role for the market. Researchers in paraquat enterprises and related institutes are striving to develop alternative formulation products that are relatively safe before paraquat aqueous solution exits pesticide registration market. Judging from the current situation, R&D is mainly concentrated in the water-soluble adhesive formulations and soluble granules. However, there are some technical problems, and users’ acceptance of the new formulations needs to be monitored after they enter the market.
The market prospects of paraquat, as the largest pyridine downstream product, will be uncertain after 2016, adding to the uncertainties in the future market development of pyridine.
3. Conclusion
Pesticide manufacture is the largest consumption sector for pyridine and offers support for the large-scale development of pyridine. Applications in the pharmaceutical and new materials sectors are new pyridine markets worthy of attention. In the new market, pyridine mostly has a high added value. For example, brightness-enhancement film for light sources can be produced using high purity pyridine as a solvent. The large-scale development of pyridine in China has provided a sufficient raw material guarantee for the market and offered an opportunity for extensive development of downstream sectors. The future market of pyridine looks favorable.