In the past three years, it has saved nearly RMB 400 million in raw material costs for domestic 1-hexene users, and also reduced the price of 1-hexene products in the international market by about 30%. This is the new catalytic system and complete process technology of ethylene trimerization 1-hexene which won the second prize of National Technology Invention in 2015.
The project completion unit of the Sinopec Yanshan Petrochemical Science and Technology Department said: "Yanshan Petrochemical's unremitting efforts over the past 10 years have broken the high price monopoly of foreign manufacturers on 1-hexene, making China the world's first to own the technology and realize the industry. One of the two countries, at the same time, has mastered and possessed 18 core patents and proprietary technologies with independent intellectual property rights, which greatly enhanced the market competitiveness of China's polyolefin products."
Comonomer foreign high degree of monopoly upgrade dragged the hind legs polyethylene
As a comonomer for the production of high value-added polyethylene, 1-hexene is widely used in polymer materials, fine chemicals and pharmaceuticals. It is an important α-olefin product, mainly used for the copolymerization of high value-added polyethylene. monomer. The polyethylene produced by the product has the advantages of high tensile strength, impact resistance, tear resistance, puncture resistance and high light transmission, and is particularly suitable for producing packaging films, agricultural films and large-diameter pipes. As the market demand for film and tube materials increases, the use of 1-hexene is increasing. However, until the end of the last century, there was no 1-hexene production technology in China, and the products were completely dependent on high-priced imports. Moreover, foreign manufacturers have always imposed high-price monopoly on 1-hexene, which seriously restricted the development and production of high value-added products in China's polyolefin industry. .
In 1997, Sinopec initiated the research and development of a complete set of 1-hexene industrial technology for ethylene selective trimerization, and Yanshan Petrochemical undertakes exploratory research. According to the researchers of Yanshan Petrochemical, the selective trimerization of ethylene 1-hexene is a major discovery in the 1970s. It has attracted more than ten multinational companies from all over the world to conduct follow-up research in this field. The selectivity of olefins is only 60-70%, and it has failed with more polymer by-products. Only a US company has taken the lead in making a major breakthrough. Faced with strict foreign patent protection and cruel competition pressure, Yanshan Petrochemical researchers, starting from zero without a technical reserve, searched for documents and checked data, and decided to theoretically carry out innovation and surpass.
Researchers have carried out in-depth research on the technical factors such as the catalytic system, reaction mechanism and reactor form which have important influences on the synthesis of 1-hexene, and innovatively proposed the "three-coordinate" catalytic mechanism for traditional polyethylene catalysts. The concept of "placeholder". By adding a preferred occupancy agent to the catalytic system, the 1-hexene reaction selectivity is increased from 70% to over 93%, thereby achieving the first major technological breakthrough in catalyst selectivity. Researchers also found that the feed sequence of the catalytic system components has a significant impact on the reactivity and product purity, and from the mechanism to optimize, and finally developed a preparation process that can significantly improve the catalytic activity. In just over 4 years, Yanshan Petrochemical has achieved a major breakthrough in the preparation technology of 1-hexene, which has made the catalytic reaction performance a qualitative leap, and the reactivity and product purity have reached the world-class level. Technical advantages and conditions.
Technology developed one day earlier one day less troubled production enterprises
Yanshan Petrochemical researchers believe that: "Research and development work is not only higher than the technical level, but also faster than the industrialization speed. Our 1-hexene technology is developed one day later, China's polyethylene production enterprises will have to bear a high price for one day. The problem of olefins, the process of upgrading polyethylene products will be delayed."
In order to realize the industrialization of 1-hexene preparation technology as soon as possible, in 2003, the “50 million tons/year 1-hexene industrial development†scientific and technological research project was led by Yanshan Petrochemical, which established basic and applied research, engineering design and environmental protection research. And the joint research and development team of industry, academia and research, which is composed of enterprises with future equipment construction and production. From the success of the pilot test, to the completion of the 500-ton/year full-scale pilot-scale amplification device, to the successful completion of the first domestic 50,000-ton/year 1-hexene industrial plant, a successful start, yielding qualified products, and It took less than 5 years to put on the market.
The project research team has jointly tackled more than a dozen topics such as catalyst optimization, reactor development, and control process optimization, and has solved many major technical problems such as polymer plugging, process optimization, and self-control scheme. Especially by establishing mass transfer and heat transfer models under ultra-high Reynolds number, designing reactors with specific shapes and structures, reducing the formation of by-products; achieving a smooth control of the device by creating a uniquely designed control method Operation; through the development of proprietary technology, solved the problem of wall hanging and removal of by-product polymers, etc., and finally the industrial application of 1-hexene production technology has been successful.
After testing, the selectivity of Yanshan Petrochemical 1-hexene product is greater than 93%, and the product purity is greater than 9.2%.
It has made a major breakthrough in organic raw material costs polyethylene province of four hundred million years
Experts commented that Yanshan Petrochemical's ethylene trimerization 1-hexene new catalytic system and complete set of process technology achievements as a national key technology innovation project, keeping up with the development process of international peers, breaking the long-term high price monopoly of foreign countries. The main quality indicators and economic and technical indicators of its products have reached and exceeded the level of international similar products and devices, and it is another major scientific and technological innovation in the field of organic chemical raw material preparation in China.
According to statistics, after the implementation of the project results, Yanshan Petrochemical 1-hexene plant has produced more than 100,000 tons of products, and has been applied by many enterprises in Guangzhou, Shandong, Tianjin and other places, and has occupied more than 90% of the domestic market. Forced imports of high-priced 1-hexene products gradually withdrew from the Chinese market. In the past three years, the project has saved nearly RMB 400 million in raw material costs for domestic 1-hexene users, greatly improving the market competitiveness of downstream manufacturers. At the same time, as a comonomer, domestic 1-hexene has produced a series of high-performance polyethylene products of different grades, which contributed to the upgrading of polyethylene. At present, Yanhua 1-hexene products have been exported to South Korea, Malaysia, the Philippines and other countries, so the price of 1-hexene products in the international market has dropped by about 30%.
Experts said that the successful development of China's 1-hexene complete technology and the commissioning of 50,000 tons/year of equipment have filled another gap in domestic fine chemical products, effectively promoting high-performance polyethylene products in domestic industry, agriculture and building materials. The application of the field has significant economic and social benefits. In addition, the invention of the technology enriches the catalytic theory, promotes the development of new technologies for selective preparation of α-olefins, forms a research platform for related technologies, and cultivates talents and innovation teams.
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