Temperature-Pressure Swing Process for Reactive Carbon Capture and Conversion to Methanol: Techno-Economic Analysis and Life Cycle Assessment.

A model was developed to conduct techno-economic analysis (TEA) and life cycle assessment (LCA) for reactive carbon capture (RCC) and conversion of carbon dioxide (CO2) to methanol. This RCC process is compared to a baseline commercialized flue gas CO2 hydrogenation process. An ASPEN model was combined with existing TEA and LCA models into a larger TEA/LCA framework in Python. From preliminary experimental data, the model found a levelized cost of $0.79/kg methanol for the baseline process and $0.99/kg for the RCC process. The cradle-to-gate carbon intensity of the baseline process was 0.50 kg-CO2e/kg-methanol, compared to 0.55 kg-CO2e/kg-methanol for the RCC process. However, water consumption for RCC (10.21 kg-H2O/kg-methanol) is greatly reduced compared to the baseline (12.89 kg-H2O/kg-methanol). Future improvements in hydrogen electrolysis costs will benefit the RCC. A target H2/methanol mass ratio of 0.26 was developed for RCC laboratory experiments to reduce methanol cost below the baseline. If a ratio of 0.24 can be achieved, a levelized cost of $0.76/kg methanol is projected, with a carbon intensity of 0.42 kg-CO2e/kg-methanol.

Impact of Mechanical Refining Conditions on the Energy Consumption, Enzymatic Digestibility, and Economics of Sugar Production from Corn Stover.

Reducing the energy intensity of the mechanical refining-based pretreatment process for producing lignocellulosic-derived sugars without significantly affecting enzymatic hydrolysis sugar yields is challenging. This work investigated the impact of different refining conditions on energy consumption, enzymatic sugar yields, minimum sugar selling price, and environmental impacts for the conversion of corn stover to sugars. A positive proportionate correlation between specific energy consumption and enzymatic sugar yields was observed when changing the refiner plate gap was changed, which agrees with other reported works. However, the correlation between specific energy consumption and enzymatic sugar yields is not straightforward when the rotational speed and refiner plate design change. We observed that, for a corn stover material with low consistency disc refining, specific energy consumption decreased by >50% by decreasing the rotation speed without affecting enzymatic sugar yields. By changing refiner plate designs, a 45% reduction in specific energy consumption could be achieved without affecting the glucose yield, albeit still with a detrimental impact on the xylose yield. Our high-fidelity disc refining model was able to predict the energy consumption for different refiner plate geometry designs and operating conditions. Techno-economic and life-cycle analyses indicate that the plate design and operating conditions have a direct impact on overall process power consumption and sugar yields, with sugar yields strongly dictating the minimum sugar selling price, the life cycle greenhouse gas emissions, and fossil energy consumption. To minimize the environmental impact and maximize process economics, optimization of the mechanical refining process should target maintaining high sugar yields, while lowering refining energy consumption.

Lignin conversion to ß-ketoadipic acid by Pseudomonas putida via metabolic engineering and bioprocess development.

Bioconversion of a heterogeneous mixture of lignin-related aromatic compounds (LRCs) to a single product via microbial biocatalysts is a promising approach to valorize lignin. Here, Pseudomonas putida KT2440 was engineered to convert mixed p-coumaroyl- and coniferyl-type LRCs to ß-ketoadipic acid, a precursor for performance-advantaged polymers. Expression of enzymes mediating aromatic O-demethylation, hydroxylation, and ring-opening steps was tuned, and a global regulator was deleted. ß-ketoadipate titers of 44.5 and 25 grams per liter and productivities of 1.15 and 0.66 grams per liter per hour were achieved from model LRCs and corn stover-derived LRCs, respectively, the latter representing an overall yield of 0.10 grams per gram corn stover-derived lignin. Technoeconomic analysis of the bioprocess and downstream processing predicted a ß-ketoadipate minimum selling price of $2.01 per kilogram, which is cost competitive with fossil carbon-derived adipic acid ($1.10 to 1.80 per kilogram). Overall, this work achieved bioproduction metrics with economic relevance for conversion of lignin-derived streams into a performance-advantaged bioproduct.

Comparing Life-Cycle Emissions of Biofuels for Marine Applications: Hydrothermal Liquefaction of Wet Wastes, Pyrolysis of Wood, Fischer-Tropsch Synthesis of Landfill Gas, and Solvolysis of Wood.

Recent restrictions on marine fuel sulfur content and a heightened regulatory focus on maritime decarbonization are driving the deployment of low-carbon and low-sulfur alternative fuels for maritime transport. In this study, we quantified the life-cycle greenhouse gas and sulfur oxide emissions of several novel marine biofuel candidates and benchmarked the results against the emissions reduction targets set by the International Maritime Organization. A total of 11 biofuel pathways via four conversion processes are considered, including (1) biocrudes derived from hydrothermal liquefaction of wastewater sludge and manure, (2) bio-oils from catalytic fast pyrolysis of woody biomass, (3) diesel via Fischer-Tropsch synthesis of landfill gas, and (4) lignin ethanol oil from reductive catalytic fractionation of poplar. Our analysis reveals that marine biofuels' life-cycle greenhouse gas emissions range from -60 to 56 gCO2e MJ-1, representing a 41-163% reduction compared with conventional low-sulfur fuel oil, thus demonstrating a considerable potential for decarbonizing the maritime sector. Due to the net-negative carbon emissions from their life cycles, all waste-based pathways showed over 100% greenhouse gas reduction potential with respect to low-sulfur fuel oil. However, while most biofuel feedstocks have a naturally occurring low-sulfur content, the waste feedstocks considered here have higher sulfur content, requiring hydrotreating prior to use as a marine fuel. Combining the break-even price estimates from a published techno-economic analysis, which was performed concurrently with this study, the marginal greenhouse gas abatement cost was estimated to range from -$120 to $370 tCO2e-1 across the pathways considered. Lower marginal greenhouse gas abatement costs were associated with waste-based pathways, while higher marginal greenhouse gas abatement costs were associated with the other biomass-based pathways. Except for lignin ethanol oil, all candidates show the potential to be competitive with a carbon credit of $200 tCO2e-1 in 2016 dollars, which is within the range of prices recently received in connection with California's low-carbon fuel standard.

Emission factors of industrial boilers burning biomass-derived fuels.

Boilers are combustion devices that provide process heat and are integral to many industrial facilities. Historically, outside of the pulp and paper industry, most boilers burned fossil fuels, although interest in decarbonization has been leading to an increased use of renewable fuels in boilers. These boilers, including those in the biorefineries, are often large sources of air pollutant emissions, and the characterization of these emissions is critical to obtaining air permits and ensuring protection of the surrounding air quality. Several industrial boilers and new biorefineries allow utilization of biomass-derived fuels (e.g. wastewater sludge, lignin, etc.) produced during their operation as a fuel for the boiler to meet process energy needs. However, there is limited empirical data on emission factors for the burning of unconventional fuels, such as solid-gas mixtures containing biomass residues. To fill this gap, we carry out a comprehensive data survey, collecting information on emission factors for boilers burning either a single or a mixture of solid and gaseous biomass-derived fuels. We review multiple hard-to-obtain and unconventional data sources, such as air permit applications, stack test data, and industry-sponsored data collection efforts, to compile emission factors for biomass-derived fuels. We then compare this data with wood residue emission factors from the U.S. Environmental Protection Agency's AP-42 emission factor database. Our results indicate that the emission factors for boilers burning unconventional fuels vary widely depending on the fuel composition, boiler type, and fuel characteristics. Overall, we find that median emission factors of selected biomass-derived fuels are typically lower than those of wood residue boilers in AP-42. The information collected herein could be useful to permitting agencies and industries utilizing boilers who may want to reduce the carbon impact of their facilities by combusting biomass-derived wastes for process energy needs, for more accurate emission estimation for permitting.Implications: Emission factors are often used for air permitting, specifically for emission estimation purposes. This study carries out a comprehensive data survey of emission factors burning unconventional biomass-derived fuels from underutilized sources such as air permits, stack test data, and industry-led efforts, and compare the results to EPA's wood residue emission factor database. The results from this study can be used can be used by multiple stakeholders such as air permitting agencies, industries burning biomass-derived fuels, and biorefineries, that utilize more advanced boiler technologies. The findings can help mitigate risks to industry owners and operators and helps to avoid delays in obtaining the required air permits that arise due to inappropriate emission estimates in permit applications.

Techno-economic Analysis of Sustainable Biofuels for Marine Transportation.

Renewable, low-carbon biofuels offer the potential opportunity to decarbonize marine transportation. This paper presents a comparative techno-economic analysis and process sustainability assessment of four conversion pathways: (1) hydrothermal liquefaction (HTL) of wet wastes such as sewage sludge and manure; (2) fast pyrolysis of woody biomass; (3) landfill gas Fischer-Tropsch synthesis; and (4) lignin-ethanol oil from the lignocellulosic ethanol biorefinery utilizing reductive catalytic fractionation. These alternative marine biofuels have a modeled minimum fuel selling price between $1.68 and $3.98 per heavy fuel oil gallon equivalent in 2016 U.S. dollars based on a mature plant assessment. The selected pathways also exhibit good process sustainability performance in terms of water intensity compared to the petroleum refineries. Further, the O and S contents of the biofuels vary widely. While the non-HTL biofuels exhibit negligible S content, the raw biocrudes via HTL pathways from sludge and manure show relatively high S contents (>0.5 wt %). Partial or full hydrotreatment can effectively lower the biocrude S content. Additionally, co-feeding with other low-sulfur wet wastes such as food waste can provide another option to produce raw biocrude with lower S content to meet the target with further hydrotreatment. This study indicates that biofuels could be a cost-effective fuel option for the marine sector. Marine biofuels derived from various feedstocks and conversion technologies could mitigate marine biofuel adoption risk in terms of feedstock availability and biorefinery economics.

Techno-economic assessment for the production of algal fuels and value-added products: opportunities for high-protein microalgae conversion.

BACKGROUND: Microalgae possess numerous advantages for use as a feedstock in producing renewable fuels and products, with techno-economic analysis (TEA) frequently used to highlight the economic potential and technical challenges of utilizing this biomass in a biorefinery context. However, many historical TEA studies have focused on the conversion of biomass with elevated levels of carbohydrates and lipids and lower levels of protein, incurring substantial burdens on the ability to achieve high cultivation productivity rates relative to nutrient-replete, high-protein biomass. Given a strong dependence of algal biomass production costs on cultivation productivity, further TEA assessment is needed to understand the economic potential for utilizing potentially lower-cost but lower-quality, high-protein microalgae for biorefinery conversion. RESULTS: In this work, we conduct rigorous TEA modeling to assess the economic viability of two conceptual technology pathways for processing proteinaceous algae into a suite of fuels and products. One approach, termed mild oxidative treatment and upgrading (MOTU), makes use of a series of thermo-catalytic operations to upgrade solubilized proteins and carbohydrates to hydrocarbon fuels, while another alternative focuses on the biological conversion of those substrates to oxygenated fuels in the form of mixed alcohols (MA). Both pathways rely on the production of polyurethanes from unsaturated fatty acids and valorization of unconverted solids for use as a material for synthesizing bioplastics. The assessment found similar, albeit slightly higher fuel yields and lower costs for the MA pathway, translating to a residual solids selling price of $899/ton for MA versus $1033/ton for MOTU as would be required to support a $2.50/gallon gasoline equivalent (GGE) fuel selling price. A variation of the MA pathway including subsequent upgrading of the mixed alcohols to hydrocarbon fuels (MAU) reflected a required solids selling price of $975/ton. CONCLUSION: The slight advantages observed for the MA pathway are partially attributed to a boundary that stops at oxygenated fuels versus fungible drop-in hydrocarbon fuels through a more complex MOTU configuration, with more comparable results obtained for the MAU scenario. In either case, it was shown that an integrated algal biorefinery can be economical through optimal strategies to utilize and valorize all fractions of the biomass.

Biofuel Options for Marine Applications: Technoeconomic and Life-Cycle Analyses.

This study performed technoeconomic and life-cycle analyses to assess the economic feasibility and emission benefits and tradeoffs of various biofuel production pathways as an alternative to conventional marine fuels. We analyzed production pathways for (1) Fischer-Tropsch diesel from biomass and cofeeding biomass with natural gas or coal, (2) renewable diesel via hydroprocessed esters and fatty acids from yellow grease and cofeeding yellow grease with heavy oil, and (3) bio-oil via fast pyrolysis of low-ash woody feedstock. We also developed a new version of the Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET) marine fuel module for the estimation of life-cycle greenhouse gas (GHG) and criteria air pollutant (CAP) emissions of conventional and biobased marine fuels. The alternative fuels considered have a minimum fuel selling price between 2.36 and 4.58 $/heavy fuel oil gallon equivalent (HFOGE), and all exhibit improved life-cycle GHG emissions compared to heavy fuel oil (HFO), with reductions ranging from 40 to 93%. The alternative fuels also exhibit reductions in sulfur oxides and particulate matter emissions. Additionally, when compared with marine gas oil and liquified natural gas, they perform favorably across most emission categories except for cases where carbon and sulfur emissions are increased by the cofed fossil feedstocks. The pyrolysis bio-oil offers the most promising marginal CO2 abatement cost at less than $100/tonne CO2e for HFO prices >$1.09/HFOGE followed by Fischer-Tropsch diesel from biomass and natural gas pathways, which fall below $100/tonne CO2e for HFO prices >$2.25/HFOGE. Pathways that cofeed fossil feedstocks with biomass do not perform as well for marginal CO2 abatement cost, particularly at low HFO prices. This study indicates that biofuels could be a cost-effective means of reducing GHG, sulfur oxide, and particulate matter emissions from the maritime shipping industry and that cofeeding biomass with natural gas could be a practical approach to smooth a transition to biofuels by reducing alternative fuel costs while still lowering GHG emissions, although marginal CO2 abatement costs are less favorable for the fossil cofeed pathways.

Applying Environmental Release Inventories and Indicators to the Evaluation of Chemical Manufacturing Processes in Early Stage Development.

As manufacturing processes are developed through the early stages of technology readiness, various assessments can be used to evaluate their performance. Performance indicators describe processes by transforming attributes into scores that represent desirable objectives. One type of assessment is obtained by determining the life cycle inventories of inputs and outputs for processes. For a functional unit of product, the user finds the resources used and the releases to the environment, which can be compared to results for similar processes and/or combined with other processes in the life cycle. In this work, an expanded range of process inputs and releases is modeled, including forklift/loader, fugitive, storage, boiler, and cooling tower emissions. A generic scenario approach for the cooling tower releases provides a first approximation of emission and wastewater flows. These inventory values are used in performance indicators that can be placed on a scale between fixed best- and worst-case limits with the GREENSCOPE methodology, thus allowing comparisons across various technologies. The processes of interest are two conversion pathways for producing cellulosic ethanol from biomass via thermochemical and biochemical routes. The results can be used in risk assessments, decision making, evaluation of research, and in spurring future technology development.

Renewable acrylonitrile production.

Acrylonitrile (ACN) is a petroleum-derived compound used in resins, polymers, acrylics, and carbon fiber. We present a process for renewable ACN production using 3-hydroxypropionic acid (3-HP), which can be produced microbially from sugars. The process achieves ACN molar yields exceeding 90% from ethyl 3-hydroxypropanoate (ethyl 3-HP) via dehydration and nitrilation with ammonia over an inexpensive titanium dioxide solid acid catalyst. We further describe an integrated process modeled at scale that is based on this chemistry and achieves near-quantitative ACN yields (98 ± 2%) from ethyl acrylate. This endothermic approach eliminates runaway reaction hazards and achieves higher yields than the standard propylene ammoxidation process. Avoidance of hydrogen cyanide as a by-product also improves process safety and mitigates product handling requirements.