Carbon-Negative Biofuel Production.

Achievement of the 1.5 °C limit for global temperature increase relies on the large-scale deployment of carbon dioxide removal (CDR) technologies. In this article, we explore two CDR technologies: soil carbon sequestration (SCS), and carbon capture and storage (CCS) integrated with cellulosic biofuel production. These CDR technologies are applied as part of decentralized biorefinery systems processing corn stover and unfertilized switchgrass grown in riparian zones in the Midwestern United States. Cover crops grown on corn-producing lands are chosen from the SCS approach, and biogenic CO2 in biorefineries is captured, transported by pipeline, and injected into saline aquifers. The decentralized biorefinery system using SCS, CCS, or both can produce carbon-negative cellulosic biofuels (≤-22.2 gCO2 MJ-1). Meanwhile, biofuel selling prices increase by 15-45% due to CDR costs. Economic incentives (e.g., cover crop incentives and/or a CO2 tax credit) can mitigate price increases caused by CDR technologies. A combination of different CDR technologies in decentralized biorefinery systems is the most efficient method for greenhouse gas (GHG) mitigation, and its total GHG mitigation potential in the Midwest is 0.16 GtCO2 year-1.

Real-Time Vehicle Motion Detection and Motion Altering for Connected Vehicle: Algorithm Design and Practical Applications.

Real-time capturing of vehicle motion is the foundation of connected vehicles (CV) and safe driving. This study develops a novel vehicle motion detection system (VMDS) that detects lane-change, turning, acceleration, and deceleration using mobile sensors, that is, global positioning system (GPS) and inertial ones in real-time. To capture a large amount of real-time vehicle state data from multiple sensors, we develop a dynamic time warping based algorithm combined with principal component analysis (PCA). Further, the designed algorithm is trained and evaluated on both urban roads and highway using an Android platform. The aim of the algorithm is to alert adjacent drivers, especially distracted drivers, of potential crash risks. Our evaluation results based on driving traces, covering over 4000 miles, conclude that VMDS is able to detect lane-change and turning with an average precision over 76% and speed, acceleration, and brake with an average precision over 91% under the given testing data dataset 1 and 4. Finally, the alerting tests are conducted with a simulator vehicle, estimating the effect of alerting back or front vehicle the surrounding vehicles' motion. Nearly two seconds are gained for drivers to make a safe operation. As is expected, with the help of VMDS, distracted driving decreases and driving safety improves.

Centrifuge separation effect on bacterial indicator reduction in dairy manure.

Centrifugation is a commonly applied separation method for manure processing on large farms to separate solids and nutrients. Pathogen reduction is also an important consideration for managing manure. Appropriate treatment reduces risks from pathogen exposure when manure is used as soil amendments or the processed liquid stream is recycled to flush the barn. This study investigated the effects of centrifugation and polymer addition on bacterial indicator removal from the liquid fraction of manure slurries. Farm samples were taken from a manure centrifuge processing system. There were negligible changes of quantified pathogen indicator concentrations in the low-solids centrate compared to the influent slurry. To study if possible improvements could be made to the system, lab scale experiments were performed investigating a range of g-forces and flocculating polymer addition. The results demonstrated that polymer addition had a negligible effect on the indicator bacteria levels when centrifuged at high g forces. However, the higher g force centrifugation was capable of reducing bacterial indicator levels up to two-log10 in the liquid stream of the manure, although at speeds higher than typical centrifuge operations currently used for manure processing applications. This study suggests manure centrifuge equipment could be redesigned to provide pathogen reduction to meet emerging issues, such as zoonotic pathogen control.

Spatially explicit methodology for coordinated manure management in shared watersheds.

Increased clustering and consolidation of livestock production systems has been linked to adverse impacts on water quality. This study presents a methodology to optimize manure management within a hydrologic region to minimize agricultural phosphorus (P) loss associated with winter manure application. Spatial and non-spatial data representing livestock, crop, soil, terrain and hydrography were compiled to determine manure P production rates, crop P uptake, existing manure storage capabilities, and transportation distances. Field slope, hydrologic soil group (HSG), and proximity to waterbodies were used to classify crop fields according to their runoff risk for winter-applied manure. We use these data to construct a comprehensive optimization model that identifies optimal location, size, and transportation strategy to achieve environmental and economic goals. The environmental goal was the minimization of daily hauling of manure to environmentally sensitive crop fields, i.e., those classified as high P-loss fields, whereas the economic goal was the minimization of the transportation costs across the entire study area. A case study encompassing two contiguous 10-digit hydrologic unit subwatersheds (HUC-10) in South Central Wisconsin, USA was developed to demonstrate the proposed methodology. Additionally, scenarios representing different management decisions (storage facility maximum volume, and project capital) and production conditions (increased milk production and 20-year future projection) were analyzed to determine their impact on optimal decisions.

Use of cationic polymers to reduce pathogen levels during dairy manure separation.

Various separation technologies are used to deal with the enormous amounts of animal waste that large livestock operations generate. When the recycled waste stream is land applied, it is essential to lower the pathogen load to safeguard the health of livestock and humans. We investigated whether cationic polymers, used as a flocculent in the solid/liquid separation process, could reduce the pathogen indicator load in the animal waste stream. The effects of low charge density cationic polyacrylamide (CPAM) and high charge density cationic polydicyandiamide (PDCD) were investigated. Results demonstrated that CPAM was more effective than PDCD for manure coagulation and flocculation, while PDCD was more effective than CPAM in reducing the pathogen indicator loads. However, their combined use, CPAM followed by PDCD, resulted in both improved solids separation and pathogen indicator reduction.

Potential for Electrified Vehicles to Contribute to U.S. Petroleum and Climate Goals and Implications for Advanced Biofuels.

To examine the national fuel and emissions impacts from increasingly electrified light-duty transportation, we reconstructed the vehicle technology portfolios from two national vehicle studies. Using these vehicle portfolios, we normalized assumptions and examined sensitivity around the rates of electrified vehicle penetration, travel demand growth, and electricity decarbonization. We further examined the impact of substituting low-carbon advanced cellulosic biofuels in place of petroleum. Twenty-seven scenarios were benchmarked against a 50% petroleum-reduction target and an 80% GHG-reduction target. We found that with high rates of electrification (40% of miles traveled) the petroleum-reduction benchmark could be satisfied, even with high travel demand growth. The same highly electrified scenarios, however, could not satisfy 80% GHG-reduction targets, even assuming 80% decarbonized electricity and no growth in travel demand. Regardless of precise consumer vehicle preferences, emissions are a function of the total reliance on electricity versus liquid fuels and the corresponding greenhouse gas intensities of both. We found that at a relatively high rate of electrification (40% of miles and 26% by fuel), an 80% GHG reduction could only be achieved with significant quantities of low-carbon liquid fuel in cases with low or moderate travel demand growth.

Production of Biomass-Derived p-Hydroxybenzamide: Synthesis of p-Aminophenol and Paracetamol.

As we work to transition the modern society that is based on non-renewable chemical feedstocks to a post-modern society built around renewable sources of energy, fuels, and chemicals, there is a need to identify the renewable resources and processes for converting them to platform chemicals. Herein, we explore a strategy for utilizing the p-hydroxybenzoate in biomass feedstocks (e. g., poplar and palm trees) and converting it into a portfolio of commodity chemicals. The targeted bio-derived product in the first processing stage is p-hydroxybenzamide produced from p-hydroxybenzoate esters found in the plant. In the second stage a continuous reaction process converts the p-hydroxybenzamide to p-aminophenol via the Hofmann rearrangement and recovers the unreacted p-hydroxybenzamide. In the third stage the p-aminophenol can be acetylated to form paracetamol, which is readily isolated by liquid/liquid extraction at >95 % purity and an overall p-hydroxybenzamide-to-paracetamol process yield of ~90 %. We explore how utilization of protecting groups alters the challenges in this process and expands the portfolio of possible products to include p-(methoxymethoxy)aniline and N-acetyl-p-(methoxymethoxy)aniline. These target compounds could become value-added renewably-sourced platform chemicals that could be used to produce biodegradable plastics, pigments, and pharmaceuticals.

Techno-economic analysis and life cycle assessment of cellulose nanocrystals production from wood pulp.

Cellulose nanocrystals (CNCs) are biobased materials with many desirable properties such as high aspect ratio, mechanical strength, crystalline nature, and biodegradability. This study developed a commercial-scale process model of CNC production from wood pulp using sulfuric acid treatment and evaluated its techno-economic and environmental performance with and without acid recovery. The results indicated that CNC produced with acid recovery process was financially more profitable with higher project net present values than without acid recovery process but required higher capital which resulted in a longer payback period and lower return on invested capital. The estimated minimum selling prices of CNC produced with and without acid recovery were $4.69/kg and $4.89/kg, respectively. The global warming (GW) impacts of 1 kg CNC production with and without acid recovery were 11.39 and 11.18 kgCO2eq, respectively, showing that higher steam use and consequently more fossil fuels were needed in the acid recovery process.

Planning methodology for anaerobic digestion systems on animal production facilities under uncertainty.

Anaerobic digestion (AD) reduces GHG emission and facilitates renewable energy generation. The slow rate of adoption of this technology is often attributed to economic and technical considerations. Collaboration of two or more dairy farms into a centralized AD system can improve the process economics through economies of scale. However, uncertainties related to the process parameters and the scope/scale of the collaborative implementation impede its adoption. This study presents techno-economic optimization model as a design aid to determine ideal location, capacity, and participation level (cluster size) that maximize economic return on a cooperative digester. This study employs a probabilistic approach to overcome uncertainty regarding project parameters such as manure biomethane potential (BMP), project capital, and electricity sale price. Two case studies based on dairy production regions in Wisconsin were developed to test the model and demonstrate its capabilities. Herd sizes and spatial distribution in a given region were found to be critical factors in determining the viability of digestion projects in general, and collaborative digestion systems in particular. The number of simulation runs needed to capture the probability of profitable AD facility establishment was less than 1000 for both case studies assessed. Electricity sale price and biomethane potential of feedstock utilized were found to be the most restrictive to the feasibility of AD adoption. Changing the optimization objective function, to adopting maximization, favored the formation of collaborative AD facilities for both case studies evaluated.

Sustainable feedstock for bioethanol production: Impact of spatial resolution on the design of a sustainable biomass supply-chain.

This study assesses the role of spatial-resolution and spatial-variations in environmental impacts estimation and decision-making for corn-stover harvesting to produce biofuels. Geospatial corn-stover yields and environmental impacts [global warming potential (GWP), eutrophication, and soil-loss] dataset for two study areas in Wisconsin and Michigan were generated through Environmental Policy Integrated Climate (EPIC) model and aggregated at different spatial-resolutions (i.e., 100; 1000; 10,000 ha). For each spatial-resolution, decision-making was accomplished using an optimization routine to minimize different environmental impacts associated with harvesting stover to meet varied biomass demands. The results of the study showed that selective harvesting at higher-resolution (or lower-aggregation level) can result in significantly lower environmental impacts, especially at low stover demand levels. Additionally, the increased spatial resolution had more impact in minimizing the environmental impacts of corn stover harvest under a more variable landscape such as terrains and its influences are more pronounced for soil-loss and eutrophication potential compared to GWP.

Assessing the Viability of Recovery of Hydroxycinnamic Acids from Lignocellulosic Biorefinery Alkaline Pretreatment Waste Streams.

Invited for this month's cover is the research team from the D.O.E. Great Lake Bioenergy Research Center (GLBRC) at the University of Wisconsin-Madison. The cover image shows how a diverse team with expertise in many different fields works together in an integrated fashion to address complex problems. Only when the whole system, from field to the liquid fuels and co-products, is assessed, can we identify the key parameters needed to design an economically viable biorefinery-based economy. Cover art by Chelsea Mamott. The Full Paper itself is available at 10.1002/cssc.201903345.

Assessing the Viability of Recovery of Hydroxycinnamic Acids from Lignocellulosic Biorefinery Alkaline Pretreatment Waste Streams.

The hydroxycinnamic acids p-coumaric acid (pCA) and ferulic acid (FA) add diversity to the portfolio of products produced by using grass-fed lignocellulosic biorefineries. The level of lignin-bound pCA in Zea mays was modified by the alteration of p-coumaroyl-CoA monolignol transferase expression. The biomass was processed in a lab-scale alkaline-pretreatment biorefinery process and the data were used for a baseline technoeconomic analysis to determine where to direct future research efforts to couple plant design to biomass utilization processes. It is concluded that future plant engineering efforts should focus on strategies that ramp up accumulation of one type of hydroxycinnamate (pCA or FA) predominantly and suppress that of the other. Technoeconomic analysis indicates that target extraction titers of one hydroxycinnamic acid need to be >50 g kg-1 biomass, at least five times higher than observed titers for the impure pCA/FA product mixture from wild-type maize. The technical challenge for process engineers is to develop a viable process that requires more than 80 % reduction of the isolation costs.

Hydrogen bonding impact on chitosan plasticization.

The use of chitosan natural polymers to replace synthetic polymers is of interest as part of the green materials movement. However, a major challenge of using chitosan material is its rigid and brittle nature associated primarily with its intra- and inter-molecular hydrogen bonds creating a hydrogen bond network. Plasticizers are able to make chitosan flexible, hypothetically by destroying its hydrogen bond networks. Herein, we showed the importance and complicated nature of the chitosan's hydrogen bond network with respect to its flexibility, through a comparative study of glycerol and ionic liquids plasticizers. The results demonstrated that glycerol's hydrogen bonding was able to disrupt the chitosan's hydrogen bond network resulting in a flexible film, but ionic liquids, even with their very strong hydrogen bonding, were not able to plasticize chitosan. This result suggested that the plasticization phenomenon was more complicated than hydrogen bond disruption. A molecular level study by quantum chemistry calculation showed that the efficiency of glycerol as chitosan plasticizer was due to its single hydrogen bonding site, which breaks down the chitosan hydrogen bonding networks, and leave hydrophobic C-H ending groups to limit the formation of inter molecular hydrogen bonds.

Improved levulinic acid production from agri-residue biomass in biphasic solvent system through synergistic catalytic effect of acid and products.

In this study, levulinic acid (LA) was produced from rice straw biomass in co-solvent biphasic reactor system consisting of hydrochloric acid and dichloromethane organic solvent. The modified protocol achieved a 15% wt LA yield through the synergistic effect of acid and acidic products (auto-catalysis) and the designed system allowed facile recovery of LA to the organic phase. Further purification of the resulting extractant was achieved through traditional column chromatography, which yielded a high purity LA product while recovering ∼85% wt. Upon charcoal treatment of the resultant fraction generated an industrial grade target molecule of ∼99% purity with ∼95% wt recovery. The system allows the solvent to be easily recovered, in excess of 90%, which was shown to be able to be recycled up to 5 runs without significant loss of final product concentrations. Overall, this system points to a method to significantly reduce manufacturing cost during large-scale LA preparation.

Chemical Pulping Advantages of Zip-lignin Hybrid Poplar.

Hybrid poplar genetically engineered to possess chemically labile ester linkages in its lignin backbone (zip-lignin hybrid poplar) was examined to determine if the strategic lignin modifications would enhance chemical pulping efficiencies. Kraft pulping of zip-lignin and wild-type hybrid poplar was performed in lab-scale reactors under conditions of varying severity by altering time, temperature and chemical charge. The resulting pulps were analyzed for yield, residual lignin content, and cellulose DP (degree of polymerization), as well as changes in carbohydrates and lignin structure. Statistical models of pulping were created, and the pulp bleaching and physical properties evaluated. Under identical cooking conditions, compared to wild-type, the zip-lignin hybrid poplar showed extended delignification, confirming the zip-lignin effect. Additionally, yield and carbohydrate content of the ensuing pulps were slightly elevated, as was the cellulose DP for zip-lignin poplar pulp, although differences in residual lignin between zip-lignin and wild-type poplar were not detected. Statistical prediction models facilitated comparisons between pulping conditions that resulted in identical delignification, with the zip-lignin poplar needing milder cooking conditions and resulting in higher pulp yield (up to 1.41 % gain). Bleaching and physical properties were subsequently equivalent between the samples with slight chemical savings realized in the zip-lignin samples due to the enhanced delignification.

Increasing the revenue from lignocellulosic biomass: Maximizing feedstock utilization.

The production of renewable chemicals and biofuels must be cost- and performance- competitive with petroleum-derived equivalents to be widely accepted by markets and society. We propose a biomass conversion strategy that maximizes the conversion of lignocellulosic biomass (up to 80% of the biomass to useful products) into high-value products that can be commercialized, providing the opportunity for successful translation to an economically viable commercial process. Our fractionation method preserves the value of all three primary components: (i) cellulose, which is converted into dissolving pulp for fibers and chemicals production; (ii) hemicellulose, which is converted into furfural (a building block chemical); and (iii) lignin, which is converted into carbon products (carbon foam, fibers, or battery anodes), together producing revenues of more than $500 per dry metric ton of biomass. Once de-risked, our technology can be extended to produce other renewable chemicals and biofuels.

Integrated two-stage chemically processing of rice straw cellulose to butyl levulinate.

A two-stage reaction system was developed to synthesize butyl levulinate (BL), a derivative chemical of levulinic acid, from agricultural residue (rice straw). A single reactor was employed during the first processing stage for the conversion of rice straw cellulose to levulinic acid (LA) in a novel co-solvent system consisting of dilute phosphoric acid and tetrahydrofuran. The highest yield of 10.8% wt. LA concentration (i.e., ∼42% of theoretical LA yield) with intermediate residuals concentration of 1.5% wt. glucose and 0.5% wt. 5-hydroxymethylfurfural (5-HMF) on dry weight basis of biomass was obtained at modest reaction conditions. During subsequent esterification reaction, approximately 7.8% wt. BL yield (at 89% conversion yield) was achieved from the solvent extracted precipitate containing majorly LA and residual 5-HMF in the presence of 0.5M sulfuric acid using n-butanol. Based on comparative esterification results obtained using commercial chemicals (LA and 5-HMF), apparently 5-HMF exhibited ∼8% wt. BL yield through direct synthesis in the presence of sulfuric acid using n-butanol under the same specified reaction conditions. Alongside, effectiveness of co-solvent treatment on rice straw for potential fermentable sugar release (glucose) was investigated by subjecting the respective post-reaction solid residues to enzymatic digestion using cellulase and yielded highest of 11% wt. per wt. solids (27% wt. glucose conversion efficiency), amongst solid residues underwent different processing conditions.

Monolignol ferulate conjugates are naturally incorporated into plant lignins.

Angiosperms represent most of the terrestrial plants and are the primary research focus for the conversion of biomass to liquid fuels and coproducts. Lignin limits our access to fibers and represents a large fraction of the chemical energy stored in plant cell walls. Recently, the incorporation of monolignol ferulates into lignin polymers was accomplished via the engineering of an exotic transferase into commercially relevant poplar. We report that various angiosperm species might have convergently evolved to natively produce lignins that incorporate monolignol ferulate conjugates. We show that this activity may be accomplished by a BAHD feruloyl-coenzyme A monolignol transferase, OsFMT1 (AT5), in rice and its orthologs in other monocots.

Mechanism of improved cellulosic bio-ethanol production from alfalfa stems via ambient-temperature acid pretreatment.

Model compounds and recalcitrant biomass were studied to elucidate the mechanism of ambient-temperature acid pretreatment of cellulosic biomass for bio-ethanol production. Pure cellulose, a pure hemicellulose and alfalfa stems were pretreated with sulfuric acid under ambient temperature with varied acid loading and time. Changes in water-soluble carbohydrates (WSCs) and chemical components of substrates were determined, and ethanol production via simultaneous saccharification and fermentation (SSF) was studied. The results showed significant amount of WSCs formed, and the WSCs increased with increasing acid loading and pretreatment time. The ethanol yields from pure cellulose were primarily affected by the added ash. Acid loading showed significant positive effect on ethanol production from alfalfa stems, whereas pretreatment time showed much weaker positive effect. However, non-significant amounts of WSCs were removed by washing of dried substrates. It was hypothesized to be because the WSCs adsorbed onto bulk substrates during the freeze-drying step, as supported by experimental results.

Validation of lignocellulosic biomass carbohydrates determination via acid hydrolysis.

This work studied the two-step acid hydrolysis for determining carbohydrates in lignocellulosic biomass. Estimation of sugar loss based on acid hydrolyzed sugar standards or analysis of sugar derivatives was investigated. Four model substrates (starch, holocellulose, filter paper and cotton) and three levels of acid/material ratios (7.8, 10.3 and 15.4, v/w) were studied to demonstrate the range of test artifacts. The method for carbohydrates estimation based on acid hydrolyzed sugar standards having the most satisfactory carbohydrate recovery and relative standard deviation. Raw material and the acid/material ratio both had significant effect on carbohydrate hydrolysis, suggesting the acid to have impacts beyond a catalyst in the hydrolysis. Following optimal procedures, we were able to reach a carbohydrate recovery of 96% with a relative standard deviation less than 3%. The carbohydrates recovery lower than 100% was likely due to the incomplete hydrolysis of substrates, which was supported by scanning electron microscope (SEM) images.