The commercialization of CO2 utilization technology to produce formic acid is imminent
Development of a CCU process for formic acid production with both economic and environmental viability. Expected to expedite the commercialization of CCU through the world's largest-scale demonstration.
NATIONAL RESEARCH COUNCIL OF SCIENCE & TECHNOLOGY
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FLOWCHART OF THE PROCESS (ABOVE) FOR PRODUCING FORMIC ACID THROUGH THE CONVERSION OF NEWLY DEVELOPED CARBON DIOXIDE (CO2) USING CARBON CAPTURE & UTILIZATION (CCU), AND PILOT-SCALE PROCESS VERIFICATION DATA (BELOW).
view moreCREDIT: KOREA INSTITUTE OF SCIENCE AND TECHNOLOGY
CCU (Carbon Capture & Utilization), which captures CO2 and converts it into useful compounds, is crucial for rapidly transitioning to a carbon-neutral society. While CCS (Carbon Capture & Storage), which only involves CO2 storage, has entered the initial commercialization stage due to its relatively simple process and low operational costs, CCU has only been explored at the research level due to the complexity of conversion processes and high production costs of compounds.
Dr. Lee Ung's team at the Clean Energy Research Center of the Korea Institute of Science and Technology (KIST, Director Oh Sang Rok) announced the development of a novel CCU process that converts CO2 into formic acid. Formic acid, an organic acid, is a high-value compound used in various industries such as leather, food, and pharmaceuticals. Currently formic acid retains a large market consuming around one million tons annually, which is expected to grow in the future owing to its potential use as a hydrogen carrier. Moreover, it has a higher production efficiency compared to other CCU-based chemicals, as it can be produced from a single CO2 molecule.
The research team selected 1-methylpyrrolidine, which exhibited the highest CO2 conversion rate among various amines mediating formic acid production reactions, and optimized the operating temperature and pressure of the reactor containing a ruthenium (Ru)-based catalyst, thereby increasing the CO2 conversion rate to over twice the current level of 38%. Furthermore, to address the excessive energy consumption and formic acid decomposition issues during CO2 separation from air or exhaust gases and formic acid purification, the team developed a simultaneous capture-conversion process that directly converts CO2 captured within the amine without separating it. As a result, they significantly reduced the formic acid production cost from around $790 per ton to $490 per ton while mitigating CO2 emissions, compared to conventional formic acid production.
To evaluate the commercialization potential of the developed formic acid production process, the research team constructed the world's largest pilot plant capable of producing 10 kg of formic acid per day. Previous CCU studies were conducted on a small scale in laboratories and did not consider the product purification process required for large-scale production. However, the research team developed processes and materials to minimize corrosion and formic acid decomposition, and optimized operating conditions that led to successful production of formic acid with a purity exceeding 92%.
The team plans to complete a 100 kg per day pilot plant by 2025 and conduct process verification, aiming for commercialization by 2030. Success in process verification with the 100 kg pilot plant is expected to enable transportation and sales to demand companies.
Dr. Lee Ung stated, "Through this research, we have confirmed the commercialization potential of our process that converts CO2 to formic acid, which is a huge breakthrough considering that most CCU technologies are being conducted at lab-scale." He further expressed his intention to contribute to achieving the country's carbon neutrality goal by accelerating the commercialization of CCU. .
A depiction of the pilot-scale demonstration process in operation. It consists of a reaction section, separation section, recycling, and vacuum systems, enabling stable continuous operation and enhancing commercialization potential.
CREDIT
Korea Institute of Science and Technology
KIST was established in 1966 as the first government-funded research institute in Korea. KIST now strives to solve national and social challenges and secure growth engines through leading and innovative research. For more information, please visit KIST’s website at https://eng.kist.re.kr/
This research was supported by the Ministry of Science and ICT (Minister Lee Jong-Ho) as part of KIST's major projects and the Carbon-to-X project(2020M3H7A1098271). The research results were published in the latest issue of the international journal "Joule" (IF 39.8, JCR top 0.9%).
JOURNAL
Joule
ARTICLE TITLE
Accelerating the net-zero economy with CO2-hydrogenated formic acid production: Process development and pilot plant demonstration
Nanoparticle catalysts convert carbon dioxide to carbon monoxide to make useful compounds
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THE IMAGE TO THE LEFT DEPICTS Β-MO2C NANOPARTICLES SUPPORTED ON SIO2 (Β-MO2C/SIO2). THE GRAPH ON THE RIGHT REPRESENTS THE INCREASED CATALYTIC ACTIVITY OF Β-MO2C/SIO2 IN CO PRODUCTION RATE IN THE RWGS REACTION COMPARED TO BULK Β-MO2C, REPRESENTED BY THE BLACK BAR. EACH BAR REPRESENTS A DIFFERENT PERCENTAGE OF MO2C LOADING WEIGHT BASED ON THE MASS OF THE SIO2 SUPPORT. CATALYTIC ACTIVITY FOR THIS DATA WAS MEASURED AT 400°C.
view moreCREDIT: CARBON FUTURE, TSINGHUA UNIVERSITY PRESS
As a greenhouse gas, carbon dioxide (CO2) contributes to climate change as it accumulates in the atmosphere. One way to reduce the amount of unwanted CO2 in the atmosphere is to convert the gas into a useful carbon product that can be used to generate valuable compounds. A recent study attached nanoparticle of beta phase molybdenum carbide (β-Mo2C) catalysts on a silicon dioxide (SiO2) support to speed the conversion of CO2 into more useful carbon monoxide (CO) gas.
CO2 is a very stable molecule, which makes conversion of the greenhouse gas into other molecules challenging. Catalysts can be used in chemical reactions to lower the amount of energy required to form or break chemical bonds and are used in the reverse water gas shift (RWGS) reaction to convert CO2 and hydrogen gas (H2) into CO and water (H2O). Importantly, the CO gas produced by the reaction is called syngas, or synthesis gas, when combined with H2 and can be used as a carbon source to create other important compounds.
Traditional catalysts in the RWGS reaction are made from precious metals, including platinum (Pt), palladium (Pd) and gold (Au), limiting the cost efficiency of the reaction. Because of this, new catalyst materials and formation methods are developed to increase the practicality of the RWGS reaction as a means of lowering atmospheric CO2 and generating syngas.
In order to address the cost issues of traditional RWGS catalysts, a team of researchers from the University of Illinois in Urbana-Champaign studied the formation and catalytic activity of cheaper nanoparticle β-Mo2C catalysts on a SiO2 support to determine if the lower-cost catalyst could enhance activity levels of β-Mo2C with a silica oxide support in the RWGS reaction.
The team published their study in Carbon Future on April 30.
“Society is moving towards a carbon-neutral economy. Carbon dioxide is a greenhouse gas, thus any technology that can break down the carbon-oxide bond in this molecule and turn carbon into a value-added chemical could be of great interest. One important C1 chemical is carbon monoxide, which is an essential feedstock to produce a range of products, such as synthetic fuels and vitamin A,” said Hong Yang, Alkire chair professor in the Department of Chemical and Biomolecular Engineering at the University of Illinois at Urbana-Champaign and senior author of the paper.
Specifically, the researchers synthesized β-Mo2C nanoparticle catalysts absorbed onto a SiO2 support (β-Mo2C/SiO2). The amorphous structure of the SiO2 support was critical for nanoparticle formation, activity and stability of the β-Mo2C/SiO2 catalyst. The team additionally tested cesium (Ce), magnesium (Mg), titanium (Ti) and aluminum (Al) oxides as potential supports, but catalyst on SiO2 produced the best catalyst formation at the temperature of 650°C.
“It appears the disordered nature of amorphous silica, which behaves like glue to catalyst nanoparticles, is a key factor of our success in achieving high metal loading and the corresponding high activity,” said Siying Yu, graduate student in the Department of Chemical and Biomolecular Engineering at the University of Illinois at Urbana-Champaign and co-author of the paper.
Importantly, the SiO2 catalyst support structure improves the catalytic activity of β-Mo2C 8-fold compared to bulk β-Mo2C. Even with improved catalytic activity, the β-Mo2C/SiO2 catalyst demonstrated high CO conversion and increased stability compared to bulk β-Mo2C in RWGS reactions.
“A major discovery of our work is a new process for producing high metal-loading catalysts made of molybdenum carbide nanoparticles. Such metal carbide catalysts are developed for converting carbon dioxide into carbon oxide at high production rate and selectivity,” said Andrew Kuhn, former graduate student in the Department of Chemical and Biomolecular Engineering at the University of Illinois at Urbana-Champaign and first author of the paper.
The researchers performed their study under reaction conditions that favored conversion to CO gas, with a H2:CO2 ratio equal to 1:1. This ratio differs from the more commonly tested ratio of less than 3:1. Reactions were also performed at temperatures between 300 to 600°C. Under these conditions, the team produced more concentrated CO, which is more efficient for downstream compound synthesis.
The team sees this research as a launching point for other catalysts that leverage support structures to increase activity. “Our ability to synthesize phase-pure metal carbide nanomaterials at high loading opens the door for the development of new catalysts for the process of CO2 utilization,” said Yang. “I hope through in-depth study of the synthesis-structure-property relationship of this catalyst we will soon be able to uncover new important applications for value-added conversion of CO2 and the sustainable development of our economy.”
Other contributors include Rachel Park, Di Gao and Cheng Zhang from the Department of Chemical and Biomolecular Engineering at the University of Illinois at Urbana-Champaign in Urbana, Illinois; and Yuanhui Zhang from the Department of Agricultural and Biological Engineering at the University of Illinois at Urbana-Champaign.
This research was supported by the University of Illinois, Urbana-Champaign start-up fund.
About Carbon Future
Carbon Future is an open access, peer-reviewed and international interdisciplinary journal, published by Tsinghua University Press and exclusively available via SciOpen. Carbon Future reports carbon-related materials and processes, including catalysis, energy conversion and storage, as well as low carbon emission process and engineering. Carbon Future will publish Research Articles, Reviews, Minireviews, Highlights, Perspectives, and News and Views from all aspects concerned with carbon. Carbon Future will publish articles that focus on, but not limited to, the following areas: carbon-related or -derived materials, carbon-related catalysis and fundamentals, low carbon-related energy conversion and storage, low carbon emission chemical processes.
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JOURNAL
Carbon Future
ARTICLE TITLE
Valorization of carbon dioxide into C1 product via reverse water gas shift reaction using oxide-supported molybdenum carbides
ARTICLE PUBLICATION DATE
30-Apr-2024
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