【Ten Years of Great Progress in Chemical Technology】Successful Application of Hydrogenation Catalysts for C4 Fractions at the Petrochemical Research Institute from 2011 to 2023
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Ten years of rapid development in chemical technology – praise for China’s prosperity and strength. This is just a starting point; more participation from everyone will make things even more lively. HaiChuan becomes even better with your involvement; we welcome everyone to join in the forum discussions. The fragrance of rice flowers in August ------------------------------------------- On August 3, 2023, news came from China National Petroleum Corporation: the highly active and selective non-precious metal alloy catalyst for the selective hydrogenation of C4 fractions, developed by the Research Institute of Petrochemicals under CNPC (hereinafter referred to as the Research Institute), has been in stable operation at Guangdong Petrochemical’s 600,000-ton/year alkylation plant for nearly 6 months. This catalyst has enabled the development of a demonstration technology for the selective hydrogenation of alkylation feedstocks containing coked C4 compounds, thereby significantly reducing the costs associated with the pre-treatment of such feedstocks. The selection of hydrogenation as the key step in the alkylation process for alkylating feedstocks containing butene is aimed at removing butadiene from the feedstock, thereby reducing acid consumption during alkylation and the dry point of the alkylated oil. At the same time, it helps to minimize the loss of monoolefins, thus increasing the yield of the alkylated oil. Currently, the hydrogenation catalysts used for the alkylation of carbon tetracontane-containing raw materials in both domestic and international industries are all precious metal palladium catalysts. Although they exhibit excellent hydrogenation activity and selectivity, they have weak resistance to poisoning. Trace impurities in the raw materials, such as arsenic and amines, can cause the palladium catalyst to become deactivated rapidly, severely affecting the normal operation of the equipment. At the same time, precious metal prices have remained high in recent years, with palladium catalysts costing 2 million yuan per ton, thereby imposing substantial costs on enterprises. The design feed composition of the alkylation unit at Guangdong Petrochemical contains about 35% coker tetrahydrocarbons, and impurities such as sulfides, basic nitrogen compounds, and coke dust, which are difficult to remove from coker tetrahydrocarbons, can significantly affect the hydrogenation activity of palladium catalysts. Industrial application practices by domestic enterprises have shown that once coking tetrahydrocarbons are mixed into alkylating feedstocks containing carbon tetrahydrocarbons, conventional precious metal palladium catalysts will rapidly become poisoned and deactivated. The palladium catalysts specified in the original process package design failed to meet the technical requirements, and palladium catalyst suppliers both domestically and internationally withdrew from the public bidding process organized by Guangdong Petrochemical, leaving the facility without any available catalysts. To address the critical hydrogenation technology issue related to raw material selection for the alkylation unit at Guangdong Petrochemical, the Petrochemical Research Institute and Guangdong Petrochemical jointly undertook the major technical field test project titled \"Industrial Demonstration of Highly Selective Non-precious Metal Catalysts for the Selective Hydrogenation of C4 Fractions.\" To address the issues of weak impurity resistance and high cost associated with traditional palladium catalysts, the Petrochemical Research Institute, guided by theoretical calculations, developed an active phase made of a non-precious metal multialloy. By leveraging the geometric properties of the alloy as well as electronic synergistic effects, it was possible to effectively control the selectivity for butadiene hydrogenation as well as the catalyst’s impurity resistance, thereby overcoming the technical challenge of insufficient selectivity for butadiene hydrogenation in non-precious metal catalysts. Ultimately, within 6 months they developed an impurity-resistant, low-cost non-precious metal alloy catalyst for the selective hydrogenation of carbon tetrafraction, suitable for the original operating conditions. Its overall performance was on par with that of palladium catalysts, while the cost was reduced by over 70%, enabling it to serve as a seamless substitute for palladium catalysts. On February 14, the catalyst was successfully used in the initial feeding of the newly built 600,000 tons per year alkylation unit at Guangdong Petrochemical, and industrial calibration was completed. The calibration results show that the butadiene content in the hydrogenated product is no higher than 100 ppm, and the yield of monoenes is no less than 100%. Currently, this catalyst exhibits good hydrogenation activity, high selectivity for single alkenes, and strong resistance to impurities, laying a solid foundation for the ‘stable, efficient, and optimal’ operation of this facility.
【Ten Years of Great Progress in Chemical Technology】The first integrated demonstration project for the hydrogen energy industry operating in isolated mode from 2011 to 2023. https://bbs.hcbbs.com/thread-4657635-1-1.html (Source: Haichuan Chemical Industry Forum)
To date, the non-precious metal alloy catalyst PDB-03 for selective hydrogenation of C4 fractions, independently developed by the Research Institute of Petroleum and Petrochemicals, China National Petroleum Corporation, has been operating stably in the alkylation unit at Guangdong Petrochemical for 6 months, and industrial calibration has been completed. The results showed that the average content of butadiene in the hydrogenated product was 100 ppm, and the average yield of monoolefins was 101.5%. The specifications of the hydrogenated product far exceeded the requirements specified in the contract. The PDB-03 catalyst features good hydrogenation activity, high selectivity for monoolefins, strong resistance to impurities, and low cost. The highly active and selective non-precious metal alloy catalyst for the selective hydrogenation of C4 fractions, developed originally by the Petrochemical Research Institute, has undergone successful industrial testing. This catalyst fills a technical gap in China and constitutes a demonstration technology for the selective hydrogenation of alkylation feedstocks containing coked C4 compounds; it can significantly reduce the costs associated with the pretreatment of such feedstocks, which is of great significance for reducing costs and improving efficiency in domestic alkylation plants.
The choice of hydrogenation as the treatment method for C4 feedstocks is a key step in the alkylation process. Its purpose is to remove butadiene from the feedstocks, thereby reducing acid consumption during alkylation as well as the dry point of the alkylated oil, while simultaneously minimizing the loss of monoolefins in order to increase the yield of alkylated oil. Currently, the hydrogenation catalysts used for the industrial processing of C4 feedstocks at home and abroad are all precious metal palladium catalysts. The design feed composition of the alkylation units at Guangdong Petrochemical contains about 35% coker tetrahydrocarbons. Impurities in these coker tetrahydrocarbons, such as sulfides, basic nitrogen compounds, and coke dust, which are difficult to remove, can significantly impair the hydrogenation activity of palladium catalysts. Industrial practice by domestic companies shows that once coker tetrahydrocarbons are mixed into the feedstock, traditional precious metal palladium catalysts will quickly become poisoned and lose their functionality. Therefore, the palladium catalysts specified in the original process package design failed to meet the technical requirements, and palladium catalyst suppliers both domestically and internationally withdrew from the public bidding process organized by Guangdong Petrochemical, leaving the facility without any available catalysts.
To address the critical hydrogenation technology issue related to raw material selection for the alkylation unit at Guangdong Petrochemical, the Petrochemical Research Institute and Guangdong Petrochemical jointly undertook the major technical field test project titled \"Industrial Demonstration of Highly Selective Non-precious Metal Catalysts for Selective Hydrogenation of C4 Fractions.\" The Lanzhou Center of the Petrochemical Research Institute took on this task in a time of crisis and faced the challenges head-on. Guided by catalyst theory design, and building on a platform for hydrogenation catalyst research and development that spans over 60 years, it successfully developed the PDB-03 catalyst – an impurity-resistant, low-cost non-precious metal alloy catalyst suitable for the original operating conditions – within 6 months. The cost of this catalyst is more than 70% lower than that of palladium catalysts. At the same time, Guangdong Petrochemical is committed to innovation and daring to break new ground; by bringing together its most skilled professionals, and with strong support from its New Materials in Refining and Chemical Processing branch, it collaborated with the Petrochemical Research Institute to launch a project aimed at conducting the first industrial-scale tests of this catalyst. This demonstrates the confidence and determination of China’s petroleum refining and chemical processing technicians to achieve high levels of technological self-reliance. On February 14, 2023, the PDB-03 catalyst was successfully used in the first feeding operation of the alkylation unit at Guangdong Petrochemical. It has been operating stably for nearly 6 months now, laying a solid foundation for the unit’s safe, stable, long-term, full-capacity, and high-performance operation.
【Ten Years of Great Progress in Chemical Technology】Breakthroughs achieved in ultra-deep desulfurization and refining technologies for light hydrocarbons from 2012 to 2023 https://bbs.hcbbs.com/thread-4675312-1-1.html (Source: Haichuan Chemical Industry Forum Website)