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At least 19 records

CO2 upgrading into bioproducts using a two-step abiotic–biotic system

The valorization of CO2 to chemicals beyond C1-2 products is receiving significant interest; however, the direct electrosynthesis of Cn molecules (n > 4) remains a challenge. Here, we present a two-step abiotic-biotic system for upgrading CO2 into the biopolymer, poly(3-hydroxybutyrate). In the electrolysis system, CO2 is converted into C2 oxygenates using a Cu-Ag tandem electrocatalyst. The electrolysis process generates a liquid stream containing ~ 200 mM acetate in a bio-compatible electrolyte. This electrosynthesized acetate is then fed to a bioreactor, where the substrate is upgraded by Cupriavidus necator to biopolymer with a maximum rate of 32 ± 3.5 mg L-1 h-1. We further demonstrate the purification of the resulting biopolymer into a powder. The high productivity of the abiotic-biotic system demonstrates its feasibility for sustainable chemical manufacturing.

CO2 upgrading↗

Combining CO2 Electrolysis with Biological Upgrading to Fuels and Chemicals: Turning Waste into Fuels

The utilization of flue gas-derived CO2 presents an opportunity to enhance carbon utilization in the bioethanol industry, contributing to the production of valuable products. In the context of a 90 million-gallon-per-year corn ethanol plant generating approximately 30 tons per hour of 99% pure CO2, a collaborative effort involving six national laboratories has been established. This initiative, known as the CO2 Reduction and Upgrading for e-Fuels (CO2RUe) Consortium, is funded by the Department of Energy's BioEnergy Technologies Office (BETO). The primary objective of the CO2RUe Consortium is to explore innovative approaches to harness CO2 as a valuable feedstock. This interdisciplinary consortium integrates electrochemistry with biological upgrading techniques, aiming to yield sustainable, value-added products and aviation fuels. The presentation will delve into the recent advancements in the realms of electrochemistry and biological upgrading, with a specific focus on formic acid and CO. Additionally, the talk will include an analysis of future electricity grid scenarios, technoeconomic evaluations, and life-cycle assessments. These assessments aim to provide a comprehensive understanding of the impacts of various conversion pathways on both cost and carbon intensity. The CO2RUe Consortium is at the forefront of steering the development of economically favorable and sustainable processes for CO2 utilization. The presentation will showcase the consortium's progress in driving the advancement of technology and processes, emphasizing the economic viability and sustainability of CO2 utilization within the broader context of the bioethanol industry.

biological upgrading↗

Integration of CO2 Electrolysis with Microbial Syngas Upgrading to Rewire the Carbon Economy

This project has worked towards demonstrating and understanding the conversion of waste CO2 into value added fuels and chemicals. If successful, our proposed technology will incentivize CO2 capture and can add carbon efficiency to biorefineries. We have integrated two conversion technologies to demonstrate a novel approach of combining electrolytic CO2 reduction with biocatalytic CO upgrading. Industrial partners 3M and Dioxide Materials have recently demonstrated electrolytic conversion of CO2 and water to syngas using inexpensive renewable energy. Concurrently, supporting partner Lanzatech has demonstrated industrial scale CO fermentation using steel mill waste CO as a substrate. This presentation will highlight the investment BETO has made to establish a CO2 electrolysis test station and CO fermentation at NREL. We will also discuss the process of increasing the size of the electrolyzers to meet fermentation needs, along with the investigation into the affect CO2 concentration and contaminates have on electrolyzer efficiency, lifetime, and specificity. Additionally, we have begun to examine the downstream impact of electrolyzer off-gas CO:H2 ratios have on the metabolism of C. autoethanologen. Experimental results along input from our industrial partners have led to a baseline techno-economic and life cycle analyses. These results enabled the identification of key cost drivers and carbon intensity of the process. We have used these metrics to identify technology gaps to iteratively inform the process optimization and potential deployment siting to achieve economically viable, sustainable conversion of biopower-derived flue gases to fuels and chemical intermediates.

bioenergy↗

CO2 Valorization via Rewiring Carbon Metabolic Network

Energizing the world sustainably requires revolutionizing the way we harness natural resources. New renewable technologies include the microbiological upgrading of CO2, the primary greenhouse gas that causes climate change. This project aims to develop a new bioeconomy by taking up CO2 and converting it into high-value products using an autotrophic microbe. Specifically, the team constructed an acetogenic bacterium, Clostridium ljungdahlii, and developed gas fermentation processes that convert syngas (CO2/H2/CO) to the platform compound 3-hydroxybutyrate (3HB). The project has achieved several key successes, including the design and construction of 3HB genes in the gas-fermenting bacterium, the identification of a native 3HB pathway, the conversion of syngas to 3HB through strain engineering, and the improvement of the conversion through rational and iterative strain development. The optimized strain has achieved industry-relevant production rates (0.1 g/L/h) and titers (9.2 g/L), and sustained continuous gas fermentation for 3HB production for > 50 days in a bench-top gas bioreactor. The project has both industrial and scientific implications, including the exploitation of host microbes and processes to improve industrial-scale production of value-added compounds from CO2, and the promotion of gas fermentation technology. The team is also strengthening R&D synergies with other teams and industrial partners in the CO2 consortium, developing cutting-edge approaches for rapid and rational engineering of gas-fermenting hosts, and dissecting the thermodynamics and kinetics of processes for biological syngas valorization. So far, one patent application and one research article have resulted from this work, and the team anticipates additional significant outcomes from this project.

3-hydroxybutyrate↗

Adaptive Laboratory Evolution for Enhanced Performance of Cupriavidus necator on Formic Acid

The need to decarbonize our economy is becoming ever more pressing. CO2, can be electrochemically reduced to formic acid, a soluble C1 molecule that can be used to store carbon and energy. Cupriavidus necator H16, a soil bacterium, capable of consuming and growing on formic acid as its sole carbon source, is well positioned to upgrade CO2-derived formic acid into value added chemicals such as sustainable aviation fuel. To improve the performance of C. necator on formic acid adaptive laboratory evolution (ALE), a proven tool for improving microbial fitness, has been conducted using continuous pH-stat bioreactors. The system works on the basis that consumption of formic acid raises the pH and triggers the addition of more formic acid to maintain the pH at 6.7, such that formic acid is provided at the same rate as it is consumed. This system has been coupled with level control to achieve continuous fermentation where cells acquiring mutations that improve growth on formic acid become more abundant in the population, from which they can be isolate and characterized. This configuration where the dilution rate is controlled by pH-stat has been found to seek out a dilution rate that matches the exponential growth rate of the organism. During developmental experiments it was discovered that formic acid accumulated to inhibitory levels. It was determined that the nitrogen source, ammonium hydroxide, must be tailored to the carbon consumption to avoid formic acid accumulation. ALE has run in three lineages for 2000+ hours and 300+ generations. Growth of evolved isolates derived from all lineages will be evaluated on formic acid and those with improved growth rates or biomass yield will be subjected to whole genome sequencing to identify potentially causative mutations. These mutations will be evaluated individually and in combination to identify those that improve growth on formic acid.

adaptive laboratory evolution↗

Adaptive Laboratory Evolution for Enhanced Performance of Cupriavidus Necator on Formic Acid

The threat of global warming, driven by rising carbon emissions, highlights the need to decarbonize our economy. This requires innovative solutions for managing carbon waste and its effective utilization. One promising method for CO2 capture and sequestration is the electrochemical reduction of CO2 to formic acid, a soluble C1 molecule that can be used to store carbon and energy, and as a feedstock for biological conversion. Cupriavidus necator H16, a soil bacterium capable of consuming and growing on formic acid as its sole carbon and energy source, is well positioned to upgrade CO2-derived formic acid into platform chemicals and fuel precursors. To improve the performance of C. necator on formic acid, adaptive laboratory evolution (ALE), a proven tool for improving microbial fitness, has been conducted using continuous pH-stat bioreactors. The system works on the basis that consumption of formic acid raises the pH and triggers the addition of more formic acid to maintain the pH (in this case 6.7), such that formic acid is provided at the same rate as it is consumed. This system has been coupled with level control to achieve continuous fermentation where cells acquiring mutations that improve growth on formic acid become more abundant in the population, from which they can be isolated and characterized. During developmental experiments it was discovered that formic acid accumulated to inhibitory levels. It was determined that the nitrogen source, ammonium hydroxide, must be tailored to the carbon consumption to avoid formic acid accumulation. The ALE ran in three lineages for approximately 3000 hours and more than 500 generations. Evolved isolates obtained from each lineage demonstrated an increase in growth rate in conjunction with improve formate utilization compared to the parental strain when evaluated in pH-stat bioreactors. The isolates with improved performance were then subjected to whole genome sequencing to identify potentially causative mutations. Mutations in several key genes across different lineages have been found and will be evaluated individually and in combination to identify those that improve growth on formic acid. Incorporating these mutations into production strains has the potential to greatly improve formic acid conversion and further industrial decarbonization.

adaptive laboratory evolution↗

ALSSAT Version 6.0

Advanced Life Support Sizing Analysis Tool (ALSSAT) at the time of this reporting has been updated to version 6.0. A previous version was described in Tool for Sizing Analysis of the Advanced Life Support System (MSC- 23506), NASA Tech Briefs, Vol. 29, No. 12 (December 2005), page 43. To recapitulate: ALSSAT is a computer program for sizing and analyzing designs of environmental-control and life-support systems for spacecraft and surface habitats to be involved in exploration of Mars and the Moon. Of particular interest for analysis by ALSSAT are conceptual designs of advanced life-support (ALS) subsystems that utilize physicochemical and biological processes to recycle air and water and process human wastes to reduce the need of resource resupply. ALSSAT is a means of investigating combinations of such subsystems technologies featuring various alternative conceptual designs and thereby assisting in determining which combination is most cost-effective. ALSSAT version 6.0 has been improved over previous versions in several respects, including the following additions: an interface for reading sizing data from an ALS database, computational models of a redundant regenerative CO2 and Moisture Removal Amine Swing Beds (CAMRAS) for CO2 removal, upgrade of the Temperature & Humidity Control's Common Cabin Air Assembly to a detailed sizing model, and upgrade of the Food-management subsystem.

Yeh, Hue-Hsia↗

Upgrading Biogas through in situ Conversion of Carbon Dioxide to Biomethane in Anaerobic Digesters

Organic waste streams generated by wastewater treatment plants, agricultural operations, and food processing industries represent an important yet underutilized opportunity for renewable energy production in the United States. Through anaerobic digestion, these waste streams can produce biogas, a mixture primarily composed of methane (CH4) and carbon dioxide (CO2), that can be upgraded to pipeline-quality natural gas. However, most existing upgrading technologies remove CO2 from biogas rather than utilizing it, leaving a significant portion of the potential energy unused. This project investigates a novel biological upgrading approach that converts CO2 into additional CH4 by supplying hydrogen (H2) to specialized microorganisms capable of performing hydrogenotrophic methanation. The main challenges associated with biological biogas upgrading are related to hydrogen supply, gas-liquid mass transfer, and process stability. First, due to the high cost of hydrogen gas, it is preferable that H2 be produced on-site using renewable energy sources such as wind or solar power. Second, hydrogen has low solubility in liquids, which limits its availability to microorganisms and requires strategies to improve gas dissolution and transfer within the reactor. Third, process inhibition may occur as a result of increased pH caused by CO2 consumption or elevated H2 partial pressure, both of which can negatively affect methanogenic activity. Although research in these areas has advanced during the course of this project, these challenges have not yet been fully resolved. To date, the biological systems that have achieved the highest methane concentrations are typically ex-situ reactors, where operational conditions can be more easily controlled. For this reason, the findings of the present project remain highly relevant. The project goal was to develop an innovative system that can accomplish biogas upgrading via biological conversion of CO2 to CH4, in a novel hybrid approach that combines the advantages of both in-situ and ex-situ systems. The proposed system employs a three-phase upflow anaerobic bioreactor with H2 delivery through a gas-permeable membrane, enabling efficient hydrogen transfer and microbial conversion. Under optimized operating conditions, the system achieved 99% H2 consumption and 90% CO2 conversion. A subsequent gas cleaning stage was implemented to further improve gas quality and meet target purity standards. The upgraded gas composition reached 97.7% CH4, 2.2% CO2, and 0.97% O2, while H2S concentrations remained below detection limits. In addition, a flue gas-driven inorganic thermoelectric generator (TEG) system was designed and experimentally validated as a potential source of electricity for H2 production. The system consisted of six TEG modules connected in series and achieved an open-circuit voltage of 4.5 V and a maximum power output of 224 mW at a temperature difference of approximately 53.5 °C, demonstrating effective conversion of waste heat into electrical power under simulated flue gas conditions. Finally, a comprehensive techno-economic analysis was completed to evaluate the capital and operating costs associated with the proposed system. The results provide important insights to guide future scale-up, optimization, and potential deployment of integrated biological biogas upgrading technologies.

09 BIOMASS FUELS↗

BETO 2021 Peer Review - Overview of the Chemical Catalysis for Bioenergy Consortium

Catalysis plays a central role in converting biomass and carbon-rich waste feedstocks into fuels and chemicals; however, critical catalysis challenges exist that are limiting commercialization of emerging bioenergy technologies. By leveraging unique U.S. Department of Energy National Laboratory capabilities and expertise, the Chemical Catalysis for Bioenergy consortium seeks to overcome these catalysis challenges and accelerate the catalyst and process development cycle. The foundation of the consortium consists of an integrated and collaborative portfolio of catalytic technologies and enabling capabilities, which positions ChemCatBio to address both technology-specific and overarching catalysis challenges across the development cycle from discovery to scale-up. The core catalysis projects target technological advancements for specific conversion processes, such as catalytic upgrading of biochemical process intermediates, catalytic fast pyrolysis, C1 and C2 upgrading, and electrochemical CO2 reduction, while the enabling technologies provide access to world-class capabilities and expertise in computational modeling, materials synthesis, advanced in situ and in operando catalyst characterization, and catalyst design tools.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Integrating CO2 Electrolysis with Gas Fermentation to Produce Valuable Fuels and Chemicals

Many industrial activities squander CO2, decreasing process yield. We envision a future where this waste carbon is instead captured, upgraded, and valorized directly at the point of emission. Within the CO2 Reduction and Upgrading Consortium (a collaboration of seven US national laboratories and industrial partners), we are pursuing this goal by developing and de-risking new technologies for low temperature CO2 electrolysis, coupled with biological upgrading of intermediates into more valuable compounds. One such process involves electrocatalytic reduction of CO2 to generate carbon monoxide (CO). As both a carbon and energy source, CO represents an attractive feedstock for microbial upgrading by certain syngas-fermenting species, such as the autotrophic bacterium Clostridium autoethanogenum. Our team has developed new genetic tools and optimized cultivation techniques to enhance C. autoethanogenum as a platform host for the biological conversion of syngas into value-added products. For example, we have created novel CRISPR-based genetic engineering techniques to build new, genome-reduced, platform strains of C. autoethanogenum with improved growth rates. Further, we ve introduced heterologous biochemical pathways into C. autoethanogenum to enable the production of high-value compounds from syngas, such as the isoprenoid precursor mevalonic acid. With the tools of electrochemistry and synthetic biology, there is virtually no limit to the spectrum of products that could be sustainably manufactured from CO2.

09 BIOMASS FUELS↗

Multistep catalytic abiotic CO2 conversion to sugars through C1 intermediates

Carbon dioxide (CO2) to multicarbon (Cn) upgrading for commodity chemicals, fuel production, or artificial food synthesis using renewable energy input is a golden target for researchers in sustainable carbon emission reduction. Here, we explore and analyze a flexible modular roadmap for the task, utilizing sequential electro-, photo-, and organocatalysis to develop a strategy for CO2 conversion using the key and elusive formaldehyde precursor of interest for sugar generation. We study the electrochemical carbon dioxide reduction reaction to methanol in a flow cell and its discontinuous photooxidation to formaldehyde (PMOR) with excellent selectivity. Utilizing a highly active N-heterocyclic carbene catalyst enables tunable generation of C4-C6 aldoses without undesirable byproducts, with carbon conversion yield reaching 60 to 80% for desired pentose, tetrose, and triose product mixtures and over 20% for hexose. This approach presents a roadmap for CO2 valorization, aiming to bridge carbon waste streams with sustainable sugar synthesis and opening broad avenues for green chemical production.

CO2 valorization↗

Recent Progress in Electrochemical Upgrading of Bio-Oil Model Compounds and Bio-Oils to Renewable Fuels and Platform Chemicals

Sustainable production of renewable carbon-based fuels and chemicals remains a necessary but immense challenge in the fight against climate change. Bio-oil derived from lignocellulosic biomass requires energy-intense upgrading to produce usable fuels or chemicals. Traditional upgrading methods such as hydrodeoxygenation (HDO) require high temperatures (200–400 °C) and 200 bar of external hydrogen. Electrochemical hydrogenation (ECH), on the other hand, operates at low temperatures (<80 °C), ambient pressure, and does not require an external hydrogen source. These environmental and economically favorable conditions make ECH a promising alternative to conventional thermochemical upgrading processes. ECH combines renewable electricity with biomass conversion and harnesses intermediately generated electricity to produce drop-in biofuels. This review aims to summarize recent studies on bio-oil upgrading using ECH focusing on the development of novel catalytic materials and factors impacting ECH efficiency and products. Here, electrode design, reaction temperature, applied overpotential, and electrolytes are analyzed for their impacts on overall ECH performance. We find that through careful reaction optimization and electrode design, ECH reactions can be tailored to be efficient and selective for the production of renewable fuels and chemicals. Preliminary economic and environmental assessments have shown that ECH can be viable alternative to convention upgrading technologies with the potential to reduce CO2 emissions by 3 times compared to thermochemical upgrading. While the field of electrochemical upgrading of bio-oil has additional challenges before commercialization, this review finds ECH a promising avenue to produce renewable carbon-based drop-in biofuels. Finally, based on the analyses presented in this review, directions for future research areas and optimization are suggested.

09 BIOMASS FUELS↗