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Crocker, Mark

Publications and source records attributed to Crocker, Mark.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Reductive Depolymerization of Lignin to Aromatic Compounds over Promoted Nickel Catalysts in Sub– and Supercritical Methanol

The use of γ-Al 2 O 3 -supported Ni catalysts promoted with either Cu or Fe was investigated for the reductive catalytic fractionation (RCF) of hybrid poplar in methanol at 200 and 250 °C. The effectiveness of lignin depolymerization was quantified in terms of the lignin oil production, the quantity and distribution of identifiable monomers present in the lignin oil, and the yield of residual solids. All of the Ni-based catalysts tested provided improved yields of lignin oil and monomers, along with reduced char formation, relative to blank (sans catalyst) runs. The highest monomer yield of 51 % was obtained at 250 °C over a 20 wt.% Ni-5 wt.% Cu/Al 2 O 3 catalyst, the improved performance obtained through Cu promotion being attributed to the ability of Cu to facilitate NiO reduction, resulting in an increased amount of Ni 0 on the catalyst surface and, consequently, improved hydrogenation activity. Finally, the main monomers formed were propanol-, propyl- and propenyl-substituted guaiacol and syringol, the S/G ratio of the products corresponding closely to that in the native lignin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Towards an Integrated Process for CO 2 Capture and Utilization: Cultivation of Scenedesmus acutus Using Gaseous CO 2 and NH 3

Integrating CO 2 scrubbing from flue gas with its utilization in algae cultivation represents a potential means of lowering the cost of CO 2 capture. Towards this goal, this study sought to assess the feasibility of using gaseous a CO 2 /NH 3 stream, derived from CO 2 capture using aqueous ammonia, as a C- and N-source for algae cultivation. Scenedesmus acutus was cultured in 800 mL photobioreactors using gaseous CO 2 /NH 3 in mole ratios varying from 7 to 18. Excellent growth of Scenedesmus acutus was observed, the average growth rate for CO 2 /NH 3 = 10 of 0.171 ± 0.015 g/L·day exceeding that obtained using 1% CO 2 /N 2 and urea as the N-source (0.099 ± 0.28 g/L·day). Under optimal growth conditions (CO 2 /NH 3 mole ratio of 10), CO 2 utilization ranged from 57% to 72%, while the NH 3 utilization was >90%. The CO 2 /NH 3 feed rate was also found to exert a significant effect on algae productivity, excessive feed rates leading to accumulation of NH 3 in the culture at concentrations that were toxic to the algae. Consequently, to avoid the toxic effects of high NH 3 concentrations (>2.0 mM), it proved necessary to balance the NH 3 supply with the algae growth rate so that excessive NH 3 accumulation was prevented. This indicates that for practical applications, a CO 2 /NH 3 feed control strategy would be required that takes into account the ammonium ion concentration in solution and the pH so as to avoid significant concentrations of free NH 3 . Furthermore, analysis of the harvested biomass revealed a high protein (≥ 47 wt%) and a low ash content (< 3.6 wt%), suggesting it would be well suited for use as animal feed or as a feedstock for the production of bioplastics.

03 NATURAL GAS↗
DOE OSTI2022

Effect of framework Al pairing on NO storage properties of Pd-CHA passive NOx adsorbers

For this study, three Pd/H-CHA samples were prepared containing 53.0%, 10.8% and 6.5% paired Al sites at near fixed Si/Al ratio and similar Pd loading. According to H 2 temperature-programmed reduction, Pd was present almost exclusively as isolated cations in the two samples containing the higher concentrations of paired Al sites, whereas in the other sample PdO was also present. Simulated lean cold start tests on the fresh samples conducted in a microflow reactor showed that the sample containing PdO stored the lowest amount of NOx. When tested with CO/H 2 , the sample containing 53.0% paired Al sites showed significantly better storage capacity than the other samples and deactivated less rapidly upon sequential tests. Experiments using lean gasoline engine exhaust revealed similar trends. This study showed that a high concentration of paired Al sites in Pd/H-CHA is beneficial for NOx storage capacity, thermal durability, and minimizing deactivation in the presence of CO/H 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cooperative Brønsted-Lewis acid sites created by phosphotungstic acid encapsulated metal–organic frameworks for selective glucose conversion to 5-hydroxymethylfurfural

Production of 5-hydroxymethylfurfural (HMF) from biomass-derived glucose has great potential for synthesis of renewable fuels and chemicals. Selective glucose conversion to 5-hydroxymethylfurfural requires a balance between Lewis and Brønsted acids for the cascade of glucose isomerization followed by fructose dehydration. A dual Brønsted-Lewis acid, phosphotungstic acid encapsulated MIL-101(Al)–NH 2 metal–organic frameworks (MOFs) was developed to catalyze the glucose dehydration reaction. The encapsulated catalysts had a high HMF selectivity of 58% at 44% glucose conversion at 120°C in [C 4 C 1 im]Cl. Phosphotungstic acid was uniformly dispersed in the MOF pores, which provided both Brønsted and Lewis acid sites for this cascade reaction. The Brønsted acidic phosphotungstic acid-encapsulated MOF catalyst was stable and recyclable at least four times. Here, these findings explain the effect of phosphotungstic acid location for maximizing the HMF selectivity and suggest a new approach for the design of bifunctional solid acid catalysts for selective HMF production from glucose. Moreover, the tunability of the acid properties of the encapsulated MOF catalysts provides opportunities for other biomass transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Development of Passive HC/NOx Trap Catalysts for Low Temperature Gasoline Applications

This project aimed to develop fundamental understanding of the chemistry of NO adsorption and reaction in Pd/zeolites so as to facilitate the rational design of passive NOx adsorber catalysts. The approach adopted combined both experimental and computational methods, which together allow a deeper understanding of the governing chemistry than the use of either method alone. The workflow began with Pd/H-CHA and Pd/H-BEA catalyst synthesis and characterization, in which the Si/Al ratio and Al siting were systematically varied. This was followed by catalyst evaluation using temperature-programed adsorption/desorption methods, as well as in situ spectroscopic measurements to probe the chemistry of NO adsorption. In parallel, the adsorption of NO and other relevant species (H 2 O, CO, HCs) was studied by means of quantum chemical calculations in order to rationalize the experimental data and provide additional insights. Catalyst aging studies were also performed with the aim of elucidating the mechanism of catalyst degradation. Finally, the insights gained in this project were applied to the preparation of an optimized HC/NOx adsorber catalyst, the performance of which was studied using exhaust gas from an engine dynamometer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Evaluation of near-ambient algal biomass fractionation conditions for bioproduct development

This contribution describes an algal fractionation scheme based on cell lysing and carbohydrate hydrolysis under acidic conditions, coupled with solvent extraction, that produces algal lipids, carbohydrates, and proteinaceous solid from partially dewatered algal biomass. Here, a design of experiments analysis was employed to identify the effect of fractionation conditions on the yields of the three product streams. By selection of appropriate conditions, the process can be steered from simple lipid extraction to near complete fractionation of the biomass. Lipid purification and upgrading were respectively achieved with a low-cost adsorbent and an inexpensive Ni-based catalyst that deoxygenated the lipids via decarboxylation/decarbonylation, an approach offering several advantages over the hydrodeoxygenation-based processes typically employed to convert lipids to hydrocarbons. The proteinaceous solids obtained were found to have much lower ash content as well as higher protein content relative to the untreated algae, enhancing the suitability of this material as a feedstock for the production of bioplastics.

09 BIOMASS FUELS↗
DOE OSTI2020

Algae-Based Beneficial Re-use of Carbon Emissions Using a Novel Photobioreactor: a Techno-Economic and Life Cycle Analysis

Despite the many advantages of microalgae, the feasibility of large-scale cultivation requires significant amounts of carbon dioxide (CO 2 ) to enable high growth rates. A synergistic union typically proposed for the supply of CO 2 is the coupling of algal cultivation with emissions from power plants. This study investigates the sustainability of a novel microalgae platform coupled with coal-based flue gas. The proposed system consists of a novel photobioreactor (PBR) for the production of biomass followed by a two-stage dewatering process. Here, a systems model, which quantifies the CO 2 and energy consumption of the proposed system, was developed and the minimum biomass selling price (MBSP) was determined by a techno-economic analysis (TEA). TEA results indicate that a facility with the capacity to capture 30% of the emissions from a 1 MW power plant requires a biomass production of 1280 metric tonnes per year, which when scaled to a nth of kind facility, can produce biomass at a MBSP of $2322 per tonne. The environmental impact of the proposed facility was determined by a life cycle assessment methodology and results indicate a carbon capture potential of 1.16 x 10 4 metric tons of CO 2 equivalent. In addition, an energy analysis indicates a desirable net energy ratio of 0.1, which is lower than conventional PBRs. Discussion focuses on the requirements to reduce biomass production cost, including research investment areas for increasing productivity while decreasing energy requirements.

09 BIOMASS FUELS↗
DOE OSTI2020

CO 2 to Bioplastics: Beneficial Re-use of Carbon Emissions from Coal-fired Power Plants using Microalgae

This project sought to address the technical and economic barriers to carbon dioxide (CO 2 ) capture and utilization using microalgae. Specifically, a dual photobioreactor (PBR)/open raceway pond (ORP) cultivation system was evaluated with respect to capital and operational costs, productivity, and culture health, and compared to an ORP-only cultivation system. In the dual (or “hybrid”) system, a cyclic flow PBR was used to provide inoculum for two open raceway ponds after each harvest, with the hypothesis that this PBR + pond system should result in improved performance compared to traditional raceway ponds. Two other raceway ponds were operated conventionally as a control, the experiments being performed at Duke Energy’s East Bend Station in northern KY using coal-derived flue gas as the CO 2 source. Although algae productivity achieved was mediocre due to the fact that the experiments had to be performed late in the growing season when climatic conditions were not optimal for high growth, the hybrid cultivation system showed a higher level of algae productivity (statistically significant) compared to the traditional ponds. In order to realize the maximum value of the algal biomass produced, fractionation of the biomass was examined. Bioplastic compounding and material characterization was subsequently performed using three feed stocks: whole biomass, lipid-extracted biomass and the proteinaceous residue from full fractionation. In general, the whole and lipid-extracted biomass gave similar results in terms of the properties of the resulting bioplastics, while the proteinaceous residue showed promise for the production of a polybutylene adipate terephthalate (PBAT) blend. Finally, sustainability assessment of a putative biorefinery system was conducted, including techno-economic and life cycle impact assessment. Nine different production scenarios were considered, comprising combinations of the three different biomass growth architectures (ORP, PBR and dual PBR-ORP systems) coupled with three different algae biomass processing pathways (drying only, lipid extraction and fractionation). Results show that the minimum selling price of the bioplastic feed stock (BPFS) is within the realm of economic competition with prices as low as $970 USD tonne -1 . Additionally, life cycle impact assessment results indicate drastic improvements in performance of the produced BPFS, with reductions in greenhouse gas emissions ranging between 67 and 116% compared to a petroleum based plastic feedstock.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2019

Pd-promoted WO 3 -ZrO 2 for low temperature NOx storage

Pd-promoted ZrO 2 and WO 3 -ZrO 2 (W-Zr) were investigated for low temperature NOx adsorption and release. Pd-promoted W-Zr exhibited high NOx storage efficiency at short storage times, subsequently releasing ~95% of the stored NOx upon thermal ramping to 350 °C. DRIFTS studies demonstrated that Pd increased nitrate formation relative to nitrite during NOx storage on both Pd-Zr and Pd-W-Zr. Moreover, Pd sites on Pd-W-Zr played a major role in NOx storage, the ad-species being readily removed by 350 °C. From NO- and CO-DRIFTS data, it is inferred that Pd on the acidic W-Zr support was present as mainly cationic species, and was therefore able to adsorb NO, whereas on ZrO 2 Pd was not able to directly store NOx. Co-feeding CO with NO resulted in increased NOx storage capacity for Pd-W-Zr, which on the basis of DRIFTS measurements is attributed to the formation of Pd 2+ (CO)(NO) complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Beneficial re-use of industrial CO 2 emissions using microalgae: Demonstration assessment and biomass characterization

Here, a novel cyclic flow photobioreactor, designed for the capture and recycle of CO 2 using microalgae, was deployed at a coal-fired power plant. Scenedesmus acutus was cultured continuously for a four-month period, during which a biomass productivity of 0.1 - 0.2 g L -1 day -1 was observed. Samples taken for DNA sequencing showed a strong correlation between the composition of the culture and environmental conditions. Dry and liquid biomass samples and the industrial fertilizers used for preparation of the nutrient medium were analyzed to determine the presence of heavy metals (As, Cd, Hg, Se) and results were compared with standardized and/or regulated maximum contaminant levels (MCLs) for metals in several possible algae derived products. Concentrations of the metals in dry algae biomass were consistent with the incorporation of metals from the supplied nutrients.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Gold-catalyzed conversion of lignin to low molecular weight aromatics

A heterogeneous catalyst system, employing Au nanoparticles (NPs) and Li–Al (1:2) layered double hydroxide (LDH) as support, showed excellent activity in aerobic oxidation of the benzylic alcohol group in β-O-4 linked lignin model dimers to the corresponding carbonyl products using molecular oxygen under atmospheric pressure. The synergistic effect between Au NPs and the basic Li–Al LDH support induces further reaction of the oxidized model compounds, facilitating facile cleavage of the β-O-4 linkage. Extension to oxidation of γ-valerolactone (GVL) extracted lignin and kraft lignin using Au/Li–Al LDH under similar conditions produced a range of aromatic monomers in high yield. Hydrolysis of the Au/Li–Al LDH oxidized lignin was found to increase the degree of lignin depolymerization, with monomer yields reaching 40% for GVL extracted lignin. According to these results, the Au/Li–Al LDH + O 2 catalyst system shows potential to be an environmentally friendly means of depolymerizing lignin to low molecular weight aromatics under mild conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Understanding Lignin Fractionation and Characterization from Engineered Switchgrass Treated by an Aqueous Ionic Liquid

Aqueous ionic liquids (ILs) have received increasing interest because of their high efficacy in fractionating and pretreating lignocellulosic biomass while at the same time mitigating several challenges associated with IL pretreatment such as IL viscosity, gel formation during pretreatment, and the energy consumption and costs associated with IL recycling. This paper investigated the fate of lignin, its structural and compositional changes, and the impact of lignin modification on the deconstruction of cell wall compounds during aqueous IL (10% w/w cholinium lysinate) pretreatment of wild-type and engineered switchgrass. The 4CL genotype resulting from silencing of 4-coumarate:coenzyme A ligase gene (Pv4CL1) had a lower lignin content, relatively higher amount of hydroxycinnamates, and higher S/G ratio and appeared to be less recalcitrant to IL pretreatment likely due to the lower degree of lignin branching and more readily lignin solubilization. The results further demonstrated over 80% of lignin dissolution from switchgrass into the liquid fraction under mild conditions while the remaining solids were highly digestible by cellulases. The soluble lignin underwent partial depolymerization to a molecular weight around 500–1000 Da. 1 H– 13 C HSQC NMR results demonstrated that the variations in lignin compositions led to different modes of lignin dissolution and depolymerization during pretreatment of engineered switchgrass. Finally, these results provide insights into the impact of lignin manipulation on biomass fractionation and lignin depolymerization and lead to possible ways toward developing a more selective and efficient lignin valorization process based on aqueous IL pretreatment technology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

A Microalgae-Based Platform for the Beneficial Re-use of Carbon Dioxide Emissions from Power Plants

This project sought to address the technical and economic barriers to carbon dioxide capture and utilization using microalgae. Operating data were collected in 2016 and 2017 during cultivation of Scenedesmus acutus at Duke Energy’s East Bend Station – a coal-fired power plant located in northern Kentucky – using flue gas as the CO 2 source. Algae were grown in a 1200 L “cyclic flow” photobioreactor (PBR) designed by the University of Kentucky. A key finding was that the harvested algae contained only very low concentrations of heavy metals (As, Cd, Hg, Se), consistent with heavy metals incorporation from the supplied nutrients. This indicates that algal biomass produced from coal-derived flue gas would be suitable for a variety of applications, including the production of bioplastics, use as fertilizer, etc. A lifecycle assessment showed that the UK-designed PBR employed in this work qualifies as a net CO 2 capture technology. Indeed, over a 30-year period, net CO 2 capture would equate to 43% of the targeted amount, i.e., the amount captured from the supplied flue gas. A techno-economic analysis indicated that the minimum production cost of Scenedesmus acutus biomass in the US is in the order of 875 USD/ton, excluding the cost of capital. While this figure is not too dissimilar to values reported for open raceway ponds in similar scenarios, it emphasizes that for current cultivation technology any pathway to economic viability will require applications for which algal boimass can be sold at prices in excess of 1,000 USD/ton. Currently, such applications represent relatively small markets, such as pigments (e.g., astaxanthin) and nutraceuticals (ω-3 unsaturated fatty acids), as well as nutritional supplements (whole algae) for human consumption and for use in pet food. Consequently, the commercialization of large-scale algae-based CO 2 capture and utilization will require the development of new technologies to reduce the cost of algae production and/or the development of new, high-value applications for algal biomass. One of the more promising applications for algal biomass is in the production of bioplastics. In this work, the potential for the algae grown in the East Bend PBR for the production of bioplastic with adequate mechanical properties was clearly shown. Positive features of the produced biomass included a high protein content and a composition that was generally more homogeneous than biomass grown in open ponds (in which many species may be present). The best candidate for further review, after incorporation into ethylene-vinyl acetate, was a lipid and sugar extracted material, which showed the highest extension values with comparable load values to other UK-derived samples. It also demonstrated extension benefits against the Algix Bloom product (currently offered commercially), even though it contained agglomerates which generally exert a negative effect on mechanical properties. This leads to speculation that with enhanced milling that exists on the commercial scale, the sugar and fat extracted product may be even more competitive. This, in turn, points to the need for additional work in order to assess the properties of such optimized algae-based plastics and the price point they can command.

09 BIOMASS FUELS↗