[Haichuan Chemical News] The first industrial plant for ammonia synthesis using iron-ruthenium cascade catalysis passes rigorous tests

This system was put into industrial operation for the first time through renovation and upgrading of Jiangsu Heyou Chemical’s existing 120,000 tons per year ammonia synthesis plant. The unit was successfully started up in July 2019, and has been in operation for over 6,000 hours to date. Operational data show that, compared to the original unit, the ammonia synthesis system of the upgraded new unit operates at a pressure of 12.7 MPa, which is 80% lower than that of the original unit; under conditions of a total column space velocity of 7463 h?, an inert gas content of 14.9 vol%, and a hydrogen-to-nitrogen ratio of 2.7, the ammonia yield reaches 14.5 vol%, representing an increase of over 35% ； The standard coal consumption per ton of ammonia raw material is 1,084 kgce, a reduction of 7.4% ； The power consumption per ton of ammonia is 1204 kW·h, a decrease of about 7.8% ； The steam generated as a by-product of ammonia production reached 992 kg, an increase of 48.3%. 　　 Experts say that this technology breaks the nearly 30-year technological monopoly held by American companies in the industrial use of ruthenium-based catalysts. By employing a new generation of Ruthenium-based catalysts and using an iron-ruthenium catalytic sequence, it significantly reduces the pressure and temperature required in the ammonia synthesis process, thereby effectively cutting energy and material consumption.

At present, China’s annual production of synthetic ammonia is 56 million tons, using traditional iron-based catalysts along with high-temperature and high-pressure reaction processes and equipment. This innovative technological breakthrough overcomes the technical barriers to reducing consumption and increasing efficiency in the ammonia synthesis industry, offering a new technical approach for achieving energy savings and reduced consumption in this sector. At the same time, ammonia is an efficient carrier for hydrogen energy; it can connect the traditional chemical industry with the hydrogen energy sector. It will play a vital role in facilitating the technological upgrading of China’s synthetic ammonia industry, and make significant contributions to achieving a diversified energy structure as well as ensuring food security and energy security. 　　 It is reported that the complete set of low-pressure isobaric ammonia synthesis reactors based on ruthenium-based ammonia synthesis catalysts has been included in the \"Guidance Catalogue for the Promotion and Application of First-of-Kind Major Technical Equipment (2019 Edition)\」issued by the Ministry of Industry and Information Technology at the end of 2019.

A breakthrough innovation has been achieved in synthetic ammonia technology in our country, breaking the technological monopoly held by American companies for nearly 30 years! Original by Li Wenzi, China Chemical Industry News, today

Major technical breakthrough achieved in China’s new ruthenium-based catalysts, Finance World, March 8, 2018 · Official account of Finance World website, top creators in the finance sector. According to reports from CNINFO (reporter Jiang Yuling), on March 7, the China Petroleum and Chemical Industry Federation organized an expert evaluation session; China’s first industrial demonstration plant for ammonia synthesis using Ruthenium-based catalysts under low temperature and pressure conditions (located in Suqian, Jiangsu) completed a 72-hour evaluation process. The evaluation and calibration expert group believes that China has made significant breakthroughs in the industrial application of ruthenium-based catalysts; this technology has broken the foreign technological monopoly that had persisted for nearly 30 years, laying the foundation for the transformation, upgrading, and high-quality development of China’s 55 million tons per year of traditional ammonia synthesis capacity. The expert calibration report indicates that ammonia synthesis plants with a capacity of 10,000 tons, utilizing the iron-ruthenium catalytic system, can achieve an estimated production increase of around 33.6% compared to similar domestic iron-based ammonia synthesis processes ； The comprehensive energy consumption per ton of ammonia is reduced by about 0.22 tons of standard coal, and each cubic meter of ruthenium catalyst enables an output of about 6 more tons of ammonia per day compared to iron-based catalysts. This indicates that the iron-ruthenium cascade catalytic system features \"three lows and one high\", that is, a high ammonia net yield can be achieved under conditions of low temperature, low pressure, and a low hydrogen-to-nitrogen ratio. Shu Xingtian, head of the calibration expert group and an academician of the Chinese Academy of Engineering, gave high praise to the calibration results. He said, “The traditional ammonia synthesis industry uses iron-based catalysts, which result in high reaction pressures, high temperatures, high energy consumption, and low efficiency.” The R&D team formed by Sanju Environmental Protection and Fuzhou University has made breakthroughs in high-activity, high-stability ruthenium-based catalysts as well as iron-ruthenium cascade catalysis technologies, which will enable leapfrog progress in China’s synthetic ammonia industry technology. ” Men Cungui, a senior engineer at the China Petroleum Consulting Center, said that currently, only KBR in the United States possesses the technology for the industrial use of ruthenium-based catalysts worldwide. China’s breakthroughs in ruthenium-based catalysts have broken the foreign technological monopoly that has persisted for nearly 30 years, providing critical technical support for the transformation and upgrading of China’s ammonia synthesis industry. According to China Securities Journal, China’s first 10,000-ton-class low-temperature and low-pressure ruthenium-based ammonia synthesis industrial demonstration plant was developed jointly by Beijing Sanju Environmental Protection New Materials Co., Ltd. and Fuzhou University, with construction entrusted to Jiangsu Heyou Chemical Co., Ltd.

Jiang Lilong, head of the R&D team and director of the **Engineering Research Center for Fertilizer Catalysts at Fuzhou University, told reporters that this technology was developed through more than 20 years of hard work by two generations of researchers. Through the deep integration of industry, academia, and research, Heyou Chemical has successfully carried out its first industrial demonstration on a scale of 10,000 tons. This approach shows great potential for cost reduction, efficiency improvement, and emission cuts. Taking an annual production volume of 180,000 tons of synthetic ammonia as an example, it will enable the company to save over 30 million yuan in energy costs each year, increase production capacity by more than 33.6%, and generate an additional output value of over 100 million yuan. China’s existing 55 million tons of synthetic ammonia production capacity will also undergo comprehensive technological upgrades and renovations. The reporter noted that the \"13th Five-Year Development Guidelines for Nitrogen Fertilizers\" issued by the China Nitrogen Fertilizer Industry Association clearly state that by 2020, China’s total nitrogen fertilizer production capacity should be kept at 61 million tons (in terms of pure content), with the capacity utilization rate rising to over 80% ； Vigorously develop high-efficiency, environmentally friendly and new types of nitrogen fertilizers with enhanced efficacy, and establish a number of ammonia synthesis production enterprises that reach world-class standards. The energy consumption levels of all ammonia synthesis enterprises meet the requirements set out in the \"Limits on Energy Consumption per Unit of Ammonia Production\" standards. Industry analysts believe that breakthroughs in catalyst technology are the key to achieving this goal. In terms of investment in upgraded equipment, the use of new ruthenium-based catalysts, improved overall efficiency, and the achievement of **specified emission reduction targets**, this technological breakthrough will bring a huge economic benefit of hundreds of billions to the traditional ammonia synthesis industry.

Ruthenium catalysts: Scientists call them new materials with the potential to “change the world”. Tech News First, September 5, 2017. Major amine compounds (derivatives of ammonia) are renowned for their excellent versatility and are important compounds in industry, used in the production of dyes, detergents, and drugs. Although many syntheses are improved using catalysts containing nickel, palladium, and platinum, few have successfully reduced the formation of secondary and tertiary amines and other unwanted by-products. Now, researchers at Tokyo Institute of Technology (Tokyo Tech) have developed a highly selective catalyst supported by ruthenium nanoparticles (Ru/Nb2O5). In a study published in the Journal of the American Chemical Society, the research team demonstrated that Ru/Nb2O5 can produce carbonyl compounds of ammonia (NH3) and hydrogen (H2), with the formation of by-products being negligible. This study compared the extent to which different catalysts can convert furfural into furfuryl alcohol. This reaction is one of the most useful methods for producing primary amines on an industrial scale. The Ru/Nb2O5 catalyst performed better than all other types of catalysts – notably, its yield reached 99% when ammonia was used in excess.

Even after three recycles, the Ru/Nb2O5 catalyst yielded consistent results, with a continuous yield exceeding 90%. The super-catalytic efficiency is attributed to the weak electron-donating property of ruthenium on the Nb2O5 surface. Scientists at the Materials and Structures Laboratory of Tokyo Institute of Technology studied how new catalysts can effectively break down biomass (in the form of glucose) into 25-2(aminoethyl)furan, a monomer used in production. Experiments conducted previously with nickel-based catalysts yielded a yield of around 50% for the glucose-derived compound (5-hydroxymethylfurfural), while the new catalysts used in combination with so-called ruthenium complexes achieved a yield of 93%. With almost no observed side products, Ru/Nb2O5 represents a major breakthrough in the clean, large-scale production of biomaterial-derived materials. Further research on these preliminary findings has already begun. By pushing the boundaries of material design, researchers say Ru/Nb2O5 can accelerate the production of eco-friendly plastics, rubbers, and heat-resistant aramid fibers. In the future, Ru/Nb2O5 catalysts may also influence the development of new anticancer drugs, antibacterial agents, pesticides, fertilizers, bio-oils, and biofuels.

USTC successfully develops ruthenium single-atom alloy catalysts, CGTN Anhui, April 16, 2019. According to Zhongan Online and the Zhongan News app, reporters learned from USTC that a research team led by Professor Wu Yuen has achieved a significant breakthrough in oxygen evolution catalysts through innovative manufacturing techniques, taking an important step forward in the industrialization of hydrogen production via water electrolysis. “A key aspect of the commercialization of hydrogen, known as the \"ultimate energy source,\" is the efficient and cost-effective production of hydrogen. Among them, electrolyzing water is one of the most promising methods for preparation. However, an efficient and inexpensive oxygen evolution catalyst, which is essential for the water electrolysis process, is one of the most difficult challenges at present; the commonly used commercial catalyst for oxygen evolution is iridium dioxide. The market price of iridium metal is 240–250 yuan per gram. Industrially, the cost of producing hydrogen by electrolyzing water using iridium dioxide is 33–38 yuan per kilogram, whereas the cost of gasoline required to produce the same amount of energy is 25–29 yuan. This is a major obstacle to the promotion of high-energy, clean, and inexpensive hydrogen energy. In contrast, ruthenium, another metal that can serve as a key catalyst element, has a market price of 19.5–20.5 yuan per gram. It is more abundant on Earth and therefore cheaper; its use in industry can effectively reduce the costs associated with hydrogen production, facilitating its wider adoption. Regrettably, in strong acidic and strongly oxidizing environments, ruthenium dioxide is easily oxidized to ruthenium tetroxide at high operating potentials, thereby losing its catalytic activity. The main reason is that the lattice oxygen in ruthenium dioxide participates in the evolution of the product oxygen. Therefore, developing a highly active and highly stable ruthenium single-atom catalyst is the most promising approach to solving the aforementioned problems.

Cover of Nature Catalysis April issue: In an acidic electrolyte environment, under an applied electric potential, water molecules adsorb onto the single-atom Ru active sites; catalyzed by this single-atom Ru, water is electrolyzed to produce oxygen.