Synthesis of 5-hydroxymethylfurfural and furfural in 1,4-dioxane versus acetone: Comparing reaction performance and solvent recyclability parameters
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering topics
Park, Sunkyu
Publications and source records attributed to Park, Sunkyu.
Technoeconomic Analysis of Kraft Pulp Mill Integration with an Advanced Nuclear Reactor
This study focuses on post-combustion capture and oxy-fuel combustion for the boilers at the mill, as well as steam integration with the nuclear power plant. The primary goal of the research outlined in this report is to design, analyze, and document the integration of industrial-scale HTGR with a reference Kraft Pulp Mill. The purpose is to deliver reliable, cost-effective, and sustainable clean energy alternatives while reducing CO2 emissions. Specifically, this study focuses on 6 different scenarios that include carbon capture equipment and some of them use nuclear power to meet the heat and electricity needs of the reference plant. Also, 2 of these scenarios are created while also producing clean hydrogen through integrated High-Temperature Steam Electrolysis (HTSE). This report offers a detailed techno-economic assessment of different scenarios for a Kraft Pulp Mill, including an analysis of tax credits (section 45V, 45Q, and 48E) provided by the Inflation Reduction Act (IRA) of 2022. The evaluation explores the potential economic benefits and challenges of incorporating different configurations, including nuclear energy, into Kraft Pulp Mill operations, with particular attention to energy efficiency, economic implications, and environmental impact. By assessing both the technical feasibility and economic viability, this analysis aims to identify existing gaps and propose solutions for the successful implementation of nuclear integration. The findings are intended to provide valuable insights for stakeholders considering the adoption of advanced nuclear reactors in the pulp and paper industries.
08 HYDROGEN↗
Catalytic graphitization of pyrolysis oil for anode application in lithium-ion batteries
The overwhelming demand for lithium-ion batteries necessitates a sustainable and environment-friendly production of graphite anode materials. Catalytic graphitization of pyrolysis oil is promising for mass-scale production of biographite.
25 ENERGY STORAGE↗
Kinetic assessment of pulp mill-derived lime mud calcination in high CO 2 atmosphere
The chemical pulping of biomass involves the recycling of calcium through the calcination of lime mud, which is mostly comprised of calcium carbonate (CaCO 3 ). Lime mud decomposes under elevated temperatures to generate calcium oxide (CaO) and carbon dioxide (CO 2 ), the kinetics of which are strongly influenced by the CO 2 partial pressure and temperature. Oxy-fuel combustion and electrified lime kilns for lime mud calcination are intriguing methods to decarbonize this highly polluting operation within the biomass pulping industry. However, the high CO 2 concentration in oxy-fuel and electrified calcination processes alters the kinetics and overall reactivity of lime mud. For the first time, a model-fitting method is used to determine the kinetic parameters for lime mud calcination under a wide range of temperatures (550 °C–1250 °C) and under different concentrations of CO2 (0 %, 15 %, 50 %, and 90 %). A kinetic model is developed that accurately predicts the reaction rates as a function of temperature and CO 2 concentration. The apparent activation of energy for lime mud calcination is elevated under a high CO 2 environment. Relative to inert gas (N 2 , Ar), the temperature window for calcination is much smaller under high CO 2 environments. The presence of Na in lime mud does not seem to affect calcination under a high CO 2 environment. Finally, particle size variation does not have a significant effect on calcination under a high CO 2 environment.
09 BIOMASS FUELS↗
Phenolic Resin Derived Hard Carbon Anode for Sodium-Ion Batteries: A Review
Sodium-ion batteries are complementary to lithium-ion batteries for grid-scale energy storage applications due to lower cost, safety, and potential for sustainable supply chains. The past decade has witnessed enormous research efforts in developing hard carbon anode materials for sodium-ion batteries. Phenolic resins have received significant attention as hard carbon precursors due to their high carbon yield, highly cross-linked structure, low cost, mature technology, and excellent electrochemical performance of corresponding hard carbon anode. This Review exclusively highlights the state-of-the-art preparation of hard carbon from phenolic resins, and the electrochemical performance in sodium-ion batteries. Cross-linked resins are prepared from three phenolic monomers (phenol, resorcinol, and phloroglucinol) to produce hard carbon. The effects of carbonization temperature on the microstructure, and electrochemical properties of hard carbon have been summarized here. Hard carbon formation, and sodium storage mechanisms have been briefly outlined. Finally, this Review provides an industrial perspective on hard carbon production at scale.
aromatic compounds↗
Life-Cycle Assessment of Sustainable Aviation Fuel Derived from Paper Sludge
Converting waste paper sludge to sustainable aviation fuel (SAF) offers a circular economy strategy to decarbonize the aviation sector. Here, this study develops a life-cycle assessment (LCA) for converting high-ash paper sludge to SAF in the U.S. using a catalytic sugar upgrading system that consists of ash removal, enzymatic hydrolysis, dehydration, aldol condensation, and hydroprocessing. The LCA is coupled with a process simulation for an industrial-scale biorefinery based on experimental data. We quantified the carbon intensity as 35.7–41.8 gCO 2 eq MJ –1 SAF (–636 to –584 gCO 2 eq per dry kg paper sludge) with acetone as a solvent, renewable fuel, and biobased chemicals; this is further reduced to 5.1–11.1 gCO 2 eq MJ –1 (–925 to –873 gCO 2 eq per dry kg paper sludge) if ash is recycled and used for substituting cement. Converting 1 dry kg paper sludge to SAF with acetone, renewable fuel, and biobased chemicals (–925 to –584 gCO 2 eq) is more climate beneficial than landfilling without landfill gas recovery (791 gCO 2 eq) and with landfill gas recovery (–294 gCO 2 eq). More than 330 million gallons of SAF can be produced annually (>4 million dry t paper sludge/year in the U.S.), resulting in a reduction of 2–7 million tCO 2 eq.
09 BIOMASS FUELS↗
Techno-economic analysis of biomass value-added processing informed by pilot scale de-ashing of paper sludge feedstock
Paper sludge biomass represents an underutilized feedstock rich in pulped and processed cellulose which is currently a waste stream with significant disposal cost to industry for landfilling services. Effective fractionation of the cellulose from paper sludge presents an opportunity to yield cellulose as feedstock for value-added processes. A novel approach to cellulose fractionation is the sidehill screening system, herein studied at the pilot-plant scale. Composition analysis determined ash removal and carbohydrate retention of both sidehill and high-performance benchtop screening systems. Sidehill screening resulted in greater carbohydrates retention relative to benchtop screening (90% vs 66%) and similar ash removal (95% vs 98%). Techno-economic analysis for production of sugar syrup yielded a minimum selling price of $331/metric ton of sugar syrup including disposal savings, significantly less than a commercial sugar syrup without fractionation. Furthermore, sensitivity analysis showed that screening conditions played a significant role in economic feasibility for cellulosic yield and downstream processes.
09 BIOMASS FUELS↗
Scale-Up of a Two-Stage Cu-Catalyzed Alkaline-Oxidative Pretreatment of Hybrid Poplar
A two-stage alkaline-oxidative pretreatment of hybrid poplar was investigated at scale (20 L reactor volume) with the goals of understanding how reaction conditions as well as interstage mechanical refining impact downstream process responses. The pretreatment comprises a first stage of alkaline delignification (alkaline pre-extraction) followed by a second delignification stage employing Cu-catalyzed alkaline hydrogen peroxide with supplemental O 2 (O 2 -enhanced Cu-AHP). Increasing pre-extraction severity (i.e., temperature and alkali loading) and pre-treatment oxidation (increasing H 2 O 2 loading) were found to increase mass and lignin solubilization in each stage. Lignin recovered from the first stage was subjected to oxidative depolymerization and led to aromatic monomer yields as high as 23.0% by mass. As a result, lignins recovered from the second stage Cu-AHP pretreatment liquors were shown to exhibit aliphatic hydroxyl contents more than six-fold higher than for a typical hardwood kraft lignin, indicating these lignins could serve as a biobased polyol for a range of polyurethane applications.
09 BIOMASS FUELS↗
Sustainable Li-ion anode material from Fe-catalyzed graphitization of paper waste
We report a novel method for the conversion of paper towel waste to biographite anode material is developed and optimized for use in Li-ion batteries. The surge in demand for Li-ion battery anode materials coupled with the unsustainable and inefficient methods of producing battery-grade graphite necessitate alternative carbon feedstocks and graphitization technologies. Paper waste (PW) is identified as a suitable carbon feedstock for iron-catalyzed graphitization due to its sustainability, low cost, low ash content, and ample supply for the intended end use. A Box Behnken experimental design for statistical optimization is pursued for untreated and pre-carbonized PW with factors of temperature (1100-1300 °C), hold time (1-5 h), and iron catalyst loading (0.5-1.5x fixed carbon content) with biographite crystal size as the primary response variable. Temperature and iron catalyst loading are found to be significant factors, whereas hold time is found to be insignificant. Reversible capacities of the biographite anodes are found to be 340-355 mAh g-1 with 99% capacity retention over 100 cycles, indicating good electrochemical performance relative to commercial graphite anodes. The initial Coulombic efficiency of untreated and pre-carbonized biographites, however, are 77% and 75%, respectively, suggesting parasitic reactions including electrolyte decomposition.
25 ENERGY STORAGE↗
Catalytic Graphitization of Biocarbon for Lithium‐Ion Anodes: A Minireview
Abstract The demand for electrochemical energy storage is increasing rapidly due to a combination of decreasing costs in renewable electricity, governmental policies promoting electrification, and a desire by the public to decrease CO 2 emissions. Lithium‐ion batteries are the leading form of electrochemical energy storage for electric vehicles and the electrical grid. Lithium‐ion cell anodes are mostly made of graphite, which is derived from geographically constrained, non‐renewable resources using energy‐intensive and highly polluting processes. Thus, there is a desire to innovate technologies that utilize abundant, affordable, and renewable carbonaceous materials for the sustainable production of graphite anodes under relatively mild process conditions. This review highlights novel attempts to realize the aforementioned benefits through innovative technologies that convert biocarbon resources, including lignocellulose, into high quality graphite for use in lithium‐ion anodes.
25 ENERGY STORAGE↗
Green Needle Coke Production from Pyrolysis Biocrude toward Bio-based Anode Material Manufacture: Biochar Fines Addition Effect as “Physical Template” on the Crystalline Order
Here, a new method for producing green needle coke (GNC) is developed by replacing the “heavy fraction” of petroleum pitch delayed coking with fast pyrolysis biocrude. A series of alternative biocrude distillation, carbonization, and calcination conditions were investigated to determine the influence of these processing parameters onto the crystalline structure of the resulting graphitized material. For the first time, the addition of biochar fines was found to serve as a “physical template” to increase the graphitic nature of the final product. During the initial biocrude carbonization (350–450 °C), volatile compounds are released, and aromatics in pyrolysis biocrude experience condensation, resulting in GNC solids with carbon contents above 95 wt % and some early lamellar structure. In the second stage of the thermal process (25–1500 °C), there are additional thermal decomposition reactions with an increase in the aromatic nature of the graphitized solid. It was found that systematic addition of biochar fines induces a nucleating effect during the GNC development. Thermogravimetric analysis suggests that biochar fines promote polycondensation reactions by modifying the biopitch structure and molecular weight, while elemental analysis (CHN) shows a reduction in both H/C and O/C ratios which are consistent with the increase in aromaticity and removal of oxygenated compounds as thermal treatment evolves. The effects of different bio-based pitch materials (after distillation) and GNC intermediates were evaluated by pyrolysis-gas chromatography mass spectrometry and Fourier transform infrared, displaying slight changes on product yields and quality. X-ray diffraction patterns taken after graphitization evidence an increase in the graphitic order with the addition of biochar fines. Transmittance electron microscopy depicts an improvement on graphitic morphology as biochar fine content increases. The use of biochar fines showed a significant increase in graphitic ordering at addition levels above 0.01 wt %. These results show that thermally treated biocrude/biochar fine systems can produce graphitic structures (hard carbon-like) that might be suitable for the manufacture of sodium-ion batteries.
09 BIOMASS FUELS↗
Catalytic Upgrading of Carbohydrates in Waste Streams to Hydrocarbons: Paper Sludge to Fuel Project (PStF)
This research, funded by the Department of Energy Bioenergy Technologies Office (DOE BETO), aims to understand the barriers and assess opportunities for transforming carbohydrates in paper sludge, a solid lignocellulosic residue from the pulp and paper industry. The goal is to turn the paper sludge into a liquid hydrocarbon product that can be blended into jet fuel, both economically and sustainably. Research groups at North Carolina State University, National Renewable Energy Laboratory, and Yale University collaborated synergistically, leveraging their expertise in pulp and paper operations, biomass deconstruction, and catalytic upgrading to propose a pathway that efficiently captures the energy in paper sludge. Findings from this study could potentially contribute to advancing biomass conversion technologies, aligning with the efforts of the U.S. DOE BETO. This report documents the experimental and simulation results of a biochemical and catalytic pathway designed to transform paper sludge into a liquid hydrocarbon product. The process involves a sequence of seven steps, including ash removal, carbohydrate enzymatic hydrolysis, sugar dehydration, solvent recovery, aldol-condensation between furans and ketone, hydrogenation, and hydrodeoxygenation to obtain a hydrocarbon blend in the ~C10 range. The experimental efforts from the initiation of the project were guided by techno-economic analysis (TEA) and sensitivity analysis results including around seventy-eight operational parameters. This methodology facilitated the efficient use of resources over time. This study relies on detailed process simulations and TEA to determine the minimum fuel selling price (MFSP) for the hydrocarbon fuel product. Preliminary TEA results led to the evaluation of eight case studies considering alternative dehydration co-solvents, operational settings, and biorefinery layouts. Finally, the life cycle assessment of twenty-eight scenarios, comparing various dehydration co-solvents, fuel sources, chemical feedstock sources, side product utilization, and other process settings, was conducted. Landfilling scenarios with and without landfill gas recovery were also estimated, analyzed, and compared.
09 BIOMASS FUELS↗
Carbon Anode Material from Biomass Pyrolysis Oil
Lithium-ion batteries (LIB) are an important component of electric vehicles and sodium-ion batteries (SIB) are an attractive alternative for grid electric storage. We are investigating a novel approach to synthesizing the carbon anode materials for these batteries from biomass pyrolysis oil as part of conversion processes to produce biofuels. Graphite is used as anode material in LIB and is exclusively produced from petroleum residue or mined mineral carbon. We have synthesized drop-in graphite by coking the heavy residual oil from the distillation of catalytic fast pyrolysis oil and by catalytic graphitizing raw pyrolysis oil. XRD and Raman spectroscopies were used to verify the production of high purity crystalline graphite. Figure 1 shows typical XRD spectra of the bio-graphite compared to commercial material as well as the charge/discharge cycle. Graphite particle sizes and morphologies were adjusted to improve performance using jet milling and carbon coating. The bio-graphite delivered a high capacity (335 mAh/g) when tested in a graphite half-cell. Full cell coin cell experiments were also conducted to verify the observations from half-cell testing. The high value of graphite (>$9/kg) can positively impact the economics of biofuels production and can be an important part of a future circular carbon economy. We have also investigated synthesizing hard carbon from pyrolysis oil for use as anode material in SIB. These batteries are not commercially mature but have great promise in grid storage and use earth abundant elements. We have demonstrated that pyrolysis oil can be used to synthesize hard carbon, which was subsequently be used in SIB experiments. This material achieved a sodium-ion capacity of 250 mAh/g and a first cycle efficiency of 78%, with opportunities to further optimize this performance from optimizing the composition of the pyrolysis oil to shaping the hard carbon particles. As with graphite, hard carbon is a high value (> $10/kg) material that could facilitate biofuels production.
BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
Effect of ash in paper sludge on enzymatic hydrolysis
The valorization of paper sludge is a high-potential process to develop renewable fuels and chemicals, which can be integrated with pulp and paper mills. Calcium carbonate is the main ash component in sludge, which plays a role in buffering pH and potentially lowering the conversion during enzymatic hydrolysis. Therefore, it is important to investigate the effect of ash on sugar yields and examine pH change to introduce efficient and economical enzymatic hydrolysis of sludge. Carbohydrate conversion was enhanced when the ash was removed by fractionation. On the other hand, the highest sugar recovery was obtained when the sludge contained 20% ash content. The pH change during enzymatic hydrolysis was influenced by ash and explained why sludge-derived hydrolysate showed lower carbohydrate conversion. Therefore, a high shear process with the increased acid amount is suggested to prohibit the negative effect of ash and enhance the accessibility of cellulase to fibers. Finally, this study highlights the feasibility of using wet waste streams generated by the paper industry.
09 BIOMASS FUELS↗
Next Generation Logistics Systems for Delivering Optimal Biomass Feedstocks to Biorefining Industries in the Southeastern U.S.
The diverse portfolio of biomass sources that is available in the Southeastern U.S., including a significant supply of pine “residue”, represents a valuable strategic position for the region. Through blends formulated based on critical properties, this project will take full advantage of the range in biomass properties afforded by the portfolio to produce a consistent, high-performance feedstock for the industry, while lowering cost. Key developments being targeted to enable this potential include whole-tree transport to a state-of-the-art merchandising depot that will further access biomass from ongoing, forest industry operations. The approach will more effectively utilize the tree and distribute cost, while minimizing in-woods contamination of the woody biomass component. To implement this vision, information on the chemical composition and changes that are induced during multiple preprocessing steps (size reduction, moisture removal, densification, etc.) is needed. New NIR sensor technology will be developed for online monitoring of important biomass properties. The data will be incorporated into a statistical process control platform to improve process efficiency and meet required specifications. Advanced process models are being developed to inform the techno-economic and life-cycle assessment of the program’s impact. The new system will ultimately reduce operational risks from supply chain disruptions, and allow operation of larger-scale biorefineries.
09 BIOMASS FUELS↗
Dynamic life-cycle carbon analysis for fast pyrolysis biofuel produced from pine residues: implications of carbon temporal effects
Abstract Background Woody biomass has been considered as a promising feedstock for biofuel production via thermochemical conversion technologies such as fast pyrolysis. Extensive Life Cycle Assessment studies have been completed to evaluate the carbon intensity of woody biomass-derived biofuels via fast pyrolysis. However, most studies assumed that woody biomass such as forest residues is a carbon–neutral feedstock like annual crops, despite a distinctive timeframe it takes to grow woody biomass. Besides, few studies have investigated the impacts of forest dynamics and the temporal effects of carbon on the overall carbon intensity of woody-derived biofuels. This study addressed such gaps by developing a life-cycle carbon analysis framework integrating dynamic modeling for forest and biorefinery systems with a time-based discounted Global Warming Potential (GWP) method developed in this work. The framework analyzed dynamic carbon and energy flows of a supply chain for biofuel production from pine residues via fast pyrolysis. Results The mean carbon intensity of biofuel given by Monte Carlo simulation across three pine growth cases ranges from 40.8–41.2 g CO 2 e MJ −1 (static method) to 51.0–65.2 g CO 2 e MJ −1 (using the time-based discounted GWP method) when combusting biochar for energy recovery. If biochar is utilized as soil amendment, the carbon intensity reduces to 19.0–19.7 g CO 2 e MJ −1 (static method) and 29.6–43.4 g CO 2 e MJ −1 in the time-based method. Forest growth and yields (controlled by forest management strategies) show more significant impacts on biofuel carbon intensity when the temporal effect of carbon is taken into consideration. Variation in forest operations and management (e.g., energy consumption of thinning and harvesting), on the other hand, has little impact on the biofuel carbon intensity. Conclusions The carbon temporal effect, particularly the time lag of carbon sequestration during pine growth, has direct impacts on the carbon intensity of biofuels produced from pine residues from a stand-level pine growth and management point of view. The carbon implications are also significantly impacted by the assumptions of biochar end-of-life cases and forest management strategies.
09 BIOMASS FUELS↗