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At least 325 records · Page 18

Techno-economic assessment and life cycle assessment of three potential pathways for biomass liquefaction

Biomass liquefaction can enhance corn-stover slurry transportation by reducing yield stress and overall viscosity, easing biomass handling, especially for slurries at high solids loading (≥30 % (w/v). Implementing a liquefaction process at the front-end of the biorefinery could reduce downtime caused by equipment fouling. Furthermore, liquefaction reduces process complexity by transforming high fiber mass into a pumpable slurry. Three scenarios for liquefaction of corn stover pellets: enzyme process, enzyme mimetic process, and a combined process of enzyme and enzyme mimetic were assessed. The ideal process will have the best performance-to-cost ratio, with minimal impact on the environment. Techno-economic and life-cycle analyses were used to understand the economic and environmental effects of the three liquefaction scenarios and to determine if one or more can achieve cost parity. Here, results show that the enzyme process had the best performance in terms of cost and emissions (gCO 2 -equivalent/kg slurry)compared to the other scenarios.

09 BIOMASS FUELS↗

Pretreatments for the continuous production of pyrolytic sugar from lignocellulosic biomass

Fast pyrolysis of lignocellulosic biomass yields little sugar or anhydrosugars compared to pyrolysis of pure polysaccharides because naturally abundant alkali and alkaline earth metals (AAEM) in biomass catalyze the fragmentation of pyranose and furanose rings. Sugar yields can be increased dramatically by pretreating the biomass with sulfuric acid prior to pyrolysis, which passivates the catalytic activity of the metals by converting them into thermally stable salts. However, depolymerization of lignin in biomass also depends on the catalytic activity of AAEM. Thus, passivating AAEM has the unintended consequence of slowing the rate of depolymerization and volatilization of lignin, resulting in a transient melt phase that agglomerates and can foul pyrolysis reactors. Here, to overcome this problem, various non-alkali metal sulfates were tested as replacements for sulfuric acid. Iron in the form of ferrous sulfate proved the most effective in depolymerizing lignin without fragmenting pyranose rings. Conventional nitrogen-blown pyrolysis of ferrous sulfate pretreated corn stover achieved WHSV of 4 h –1 compared to only 0.6 h –1 for acid pretreated corn stover. Autothermal (air-blown) pyrolysis of ferrous sulfate pretreated corn stover showed even more dramatic improvement, increasing WHSV from 1 h –1 to 10 h –1 compared to acid pretreated corn stover under autothermal operation. Fermentable sugar yields from the pyrolysis of corn stover increased from 0.9 wt% to 11.8 wt% on a biomass basis, a 13-fold increase as a result of the ferrous sulfate pretreatment. These advantages combine to increase volumetric sugar productivity from 62 g L –1 h –1 for conventional pyrolysis of untreated corn stover to 2041 g L –1 h –1 for autothermal pyrolysis of ferrous sulfate treated corn stover.

09 BIOMASS FUELS↗

When SLIPS meets TIPS: An endogenous lubricant-infused surface by taking the diluent as the lubricant

Slippery lubricant-infused porous surfaces (SLIPSs) hold great promise in fields requiring adhesion resistance such as self-cleaning, anti-fouling, anti-icing, and anti-scaling. However, their road to practical application is still blocked by the complicated fabrication process and the restricted coating area. To address these challenges, we propose a new concept of endogenous SLIPS in which the porous structure grows from the solution coating of polypropylene/caprylyl methicone undergoing a thermally induced phase separation (TIPS) process. Caprylyl methicone serves as the diluent during TIPS as well as the lubricant in the SLIPS so that the coating can be fabricated in one step and unrestrictedly. Furthermore, the dissolution and phase separation mechanisms have been revealed by molecular dynamic simulation and in situ microscopic observation. Such SLIPSs exhibits impressive sliding property even for sticky and viscous liquids and exhibit extremely low ice adhesion in anti-icing tests.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Robust optimization of flexible diafiltration systems for critical mineral separations

This paper provides major contributions in expanding the literature for membrane process design with critical mineral recovery applications and showcasing the importance of robust design techniques for reducing risks of underperformance in such systems. Here, a membrane process flowsheet featuring PrOMMiS membrane models for recovering lithium/cobalt from spent batteries is showcased, uncertainty in membrane sieving and localized fouling are considered, and robust designs are obtained using the PyROS toolset. This paper is intended for a general audience of researchers working in critical minerals, membranes, and optimization related areas.

36 MATERIALS SCIENCE↗

Mechanical properties of water desalination and wastewater treatment membranes

Applications of membrane technology in water desalination and wastewater treatment have increased significantly in the past fewdecades due to itsmany advantages over otherwater treatment technologies.Water treatment membranes provide high flux and contaminant rejection ability and require good mechanical strength and durability. Thus, assessing the mechanical properties of water treatment membranes is critical not only to their design, but also for studying their failure mechanisms, including the surface damage, mechanical and chemical ageing, delamination and loss of dimensional stability of the membranes. The various experimental techniques to assess themechanical properties ofwastewater treatment and desalinationmembranes are reviewed. Uniaxial tensile test, bending test, dynamic mechanical analysis, nanoindentation and bursting tests are the most widely used mechanical characterization methods for water treatment membranes. Mechanical degradations induced by fouling, chemical cleaning as well as membrane delamination are then discussed. Moreover, in order to study the membranesmechanical responses under similar loading conditions, the stress-state of the membranes are analyzed and advanced mechanical testing approaches are proposed. Lastly, some perspectives are highlighted to study the structure-properties relationship for wastewater treatment and water desalination membranes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Novel graphene quantum dots (GQDs)-incorporated thin film composite (TFC) membranes for forward osmosis (FO) desalination

This paper reports a novel class of thin film composite (TFC) membranes for forward osmosis (FO) desalination. The TFC membranes were fabricated via interfacial polymerization (IP) of aqueous mixture of polyethyleneimine (PEI) and graphene quantum dots (GQDs) with organic solution of trimesoyl chloride (TMC) on modified polyacrylonitrile (PAN) ultrafiltration substrates. The chemical structures and morphologies of the synthesized GQDs and the GQDs-incorporated membranes were studied by various characterization techniques. The synthesized GQDs exhibited a narrow size distribution of 1.0–4.0 nm with an average size of 2.19 nm, and the thickness were one to three graphene layers. The results showed that GQDs nanoparticles were covalently bonded to the polyamide chains. The optimized TFC membrane with 0.050 wt% GQDs loading exhibited quite hydrophilic and neutrally charged membrane surface, along with an enhanced water flux of 12.9 L m –2 h –1 and a comparable reverse salt flux of 1.41 g m –2 h –1 when DI water and 0.5 M MgCl2 were used as the feed solution and the draw solution, respectively. Also, the optimized GQDs-incorporated TFC membrane presented an especially good anti-fouling performance. Furthermore, incorporating the novel graphene nanomaterial into polymer membranes may present its great potential application in desalination, purification and wastewater treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance of sweeping gas membrane distillation for treating produced water: Modeling and experiments

Membrane distillation (MD) has shown promise for desalination of produced water (PW), but there are very few studies reported on the performance of MD with real PW and the characteristics of the fouling and scaling in MD. Among different MD configurations, sweeping gas MD (SGMD) is the least studied configuration. Here we report the application of SGMD for treating high-salinity PW (123 g L -1 ). The SGMD operating conditions were first carefully optimized through pure water MD experiments by varying operating conditions. The flux evaluation was accompanied by a detailed Aspen Custom Modeler simulation based on the electrolyte-NRTL thermodynamic model to better understand the heat and mass transfer in the feed and permeate channel. Supported by experiments, modeling results confirmed the partial condensation of the vapor in the permeate channel. Furthermore, it was concluded that the saturation of the sweeping gas is controlling the overall mass transfer through the membrane. Selected membranes and optimized conditions were then used to conduct short-term and long-term performance tests with PW. In long-term MD test, the concentration of the PW increased by a factor of two (50% water recovery), while the membrane exhibited small flux decline. Elemental analysis showed that strontium and sodium were the major scalant compounds.

42 ENGINEERING↗

An experimental study on dehumidification and regeneration performance of a new nonporous membrane-based heat and mass exchanger using an ionic liquid desiccant

As a promising alternative to inefficient vapor-compression-based air conditioning, liquid desiccant dehumidification uses a liquid desiccant in contact with the humid air absorbing the moisture. However, it has not gained much market share due to the issues related to the carryover, corrosion, fouling, and crystallization of liquid desiccant. The research has developed a new membrane-based exchanger, which uses a non-corrosive ionic liquid desiccant and nonporous tubular membranes to address these issues. As the second generation of the prototype, the new exchanger was tested at various operating conditions. According to the experimental data, when it is used in the dehumidification loop, the new membrane-based exchanger achieves a specific vapor transportation rate of 778.6 g/(h–m 2 ) and an average water vapor flux of 0.316 g/(h-m 2 -Pa), which is a significant improvement compared with the previous designs using nonporous membranes. It also achieved a comparable or even better dehumidification performance compared with the dehumidifiers that use porous membrane and conventional liquid desiccants. However, the regeneration performance is not as good as its dehumidification. It is mainly caused by the high operating temperature required in the regeneration loop. The experimental data and findings provide first-hand experimental data and enhance the understanding of advanced membrane-based ionic liquid desiccant systems.

42 ENGINEERING↗

Modeling, control, and dynamic performance analysis of a reverse osmosis desalination plant integrated within hybrid energy systems

An RO (reverse osmosis) desalination plant is proposed as an effective, FLR (flexible load resource) to be integrated into HES (hybrid energy systems) to support various types of ancillary services to the electric grid, under variable operating conditions. To study the dynamic (transient) analysis of such system, among the various unit operations within HES, special attention is given here to the detailed dynamic modeling and control design of RO desalination process with a spiral-wound membrane module. The model incorporates key physical phenomena that have been investigated individually into a dynamic integrated model framework. In particular, the solution-diffusion model modified with the concentration polarization theory is applied to predict RO performance over a large range of operating conditions. Simulation results involving several case studies suggest that an RO desalination plant, acting as a FLR, can provide operational flexibility to participate in energy management at the utility scale by dynamically optimizing the use of excess electrical energy. Here, the incorporation of additional commodity (fresh water) produced from a FLR allows a broader range of HES operations for maximizing overall system performance and profitability. For the purpose of assessing the incorporation of health assessment into process operations, an online condition monitoring approach for RO membrane fouling supervision is addressed in the case study presented.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

A respiratory health survey of a subsurface smoldering landfill

Highlights: • A landfill subsurface smoldering event was not related to higher asthma prevalence. • Chronic obstructive pulmonary disease similar in exposed and comparison households. • Attacks of shortness of breath were strongly related to living near landfill event. • Pneumonia, sleep apnea, and bronchitis were reported more by landfill households. • Households near landfill perceive odors more often; very worried about environment. In late 2010, a subsurface smoldering event was detected in the Bridgeton Sanitary Landfill in St. Louis County, Missouri. This was followed by complaints from nearby residents of foul odors emanating from the landfill. In 2016 a health survey was conducted of residents near the landfill and, as a comparison, other regions of St. Louis County. The survey was a two-stage cluster sample, where the first stage was census blocks, and the second stage was households within the census blocks. The health survey, which was conducted by face-to-face interviews of residents both near the landfill and away from the landfill, focused mainly on respiratory symptoms and diseases such as asthma and chronic obstructive pulmonary disease. The differences in the prevalence of asthma (26.7%, 95% CI 19.8–34.1 landfill vs 24.7%, 95% CI 15.7–33.6 comparison) and COPD (13.7%, 95% CI 7.2–20.3 landfill vs 12.5%, 95% CI 6.4–18.7 comparison) between the two groups were not statistically significant. Landfill households reported significantly more “other respiratory conditions,” (17.6%, 95% CI 11.1–24.1 landfill vs 9.5%, 95% CI 4.8–14.3 comparison) and attacks of shortness of breath (33.9%, 95% CI 25.1–42.8 landfill vs 17.9%, 95% CI 12.3–23.5). Frequency of odor perceptions and level of worry about neighborhood environmental issues was higher among landfill households (p < 0.001). We conclude that the results do not support the hypothesis that people living near the Bridgeton Landfill have elevated respiratory or related illness compared to those people who live beyond the vicinity of the landfill.

60 APPLIED LIFE SCIENCES↗

Performance assessment of dilute-acid leaching to improve corn stover quality for thermochemical conversion

Lignocellulosic biomass is a sustainable energy source that can help meet the increasing demand for biofuels in the United States. However, the quality and availability of such feedstocks greatly affects their suitability for downstream conversion. This work reports the effects of dilute-acid leaching at various solid loadings, temperatures and acid loadings on the quality of a traditional biochemical feedstock, corn stover, as a potential feedstock for thermochemical conversions. At 5 wt% solids, dilute-acid leaching was observed to effectively remove 97.3% of the alkali metals and alkaline earth metals that can negatively affect degradation pathways during pyrolysis and result in greater yield of non-condensable gases. In addition, up to 98.4% of the chlorine and 88.8% of the phosphorus, which can cause equipment corrosion and foul upgrading catalysts, respectively, were removed. At 25°C in the absence of acid, only 6.8% of the alkali metals and alkaline earth metals were removed; however 88.0% of chloride was still removed. The ratio of alkaline/acidic ash species has been suggested to proportionately relate to slagging in biopower applications. The initial alkali/acid ratio of the ash species present in the untreated corn stover was 0.38 (significant slagging risk). At 5 wt% solids, this ratio was decreased to 0.18 (moderate slagging risk) at 0 wt% acid and 90°C, and was decreased to 0.07, 0.08 and 0.06 at 0.5 wt% acid at 25°C, 50°C and 90°C, respectively (little or no slagging risk). Increasing the acid loading to 1.0% only slightly decreased the measured alkali/acid ratio of remaining ash species. Lastly, the results presented here show that a water wash or dilute-acid preprocessing step can improve corn stover quality for pyrolysis, hydrothermal liquefaction and biopower.

09 BIOMASS FUELS↗

Bioleaching to produce clean loblolly pine for thermochemical conversion

Lignocellulosic biomass contains inorganic elements that could induce slagging, ash fouling, and emission of both corrosive and harmful gases during thermochemical conversion. Water leaching pretreatment can remove most of the water-soluble elements, while it has limited industrial applicability due to its ineffectiveness in removing water-insoluble elements. Bioleaching is an alternative pretreatment method which has not been fully studied. In this work, bioleaching by Aspergillus niger strains NRRL 2001, NRRL 3122, and NRRL 567 was conducted to pretreat loblolly pine biomass with added water. Further, the removal of inorganic elements (K, Ca, Mg, and S) by bioleaching with A. niger NRRL 2001 was compared with chemical leaching with citric acid, HCl, and NaOH. It was shown that the pH reduction during bioleaching greatly improved K and Mg leaching to the point comparable to acid leaching, whereas Ca was precipitated by oxalic acid produced by the fungus. Bioleaching was also conducted in manually separated needles and chips components of loblolly pine. Glucose was added at different levels to assist bioleaching. At higher glucose levels, gluconic acid and citric acid were produced during bioleaching, leading to the increase of K, Ca, and Mg removal rates by more than 35%, 180%, and 390%, respectively, from the feedstock as compared with water leaching. Overall, bioleaching greatly improved removal of K, Ca, Mg, but not S from loblolly pine feedstocks as compared with water leaching.

09 BIOMASS FUELS↗

Dual Rate Adaptive Control for an Industrial Heat Supply Process Using Signal Compensation Approach

The industrial heat supply process (HSP) is a highly nonlinear cascaded process which uses a steam valve opening as its control input, the steam flow-rate as its inner loop output and the supply water temperature as its outer loop output. The relationship between the heat exchange rate and the model parameters, such as steam density, entropy, and fouling correction factor and heat exchange efficiency are unknown and nonlinear. Moreover, these model parameters vary in line with steam pressure, ambient temperature and the residuals caused by the quality variations of the circulation water. When the steam pressure and the ambient temperature are of high values and are subjected to frequent external random disturbances, the supply water temperature and the steam flow-rate would interact with each other and fluctuate a lot. This is also true when the process exhibits unknown characteristic variations of the process dynamics caused by the unexpected changes of the heat exchange residuals. As a result, it is difficult to control the supply water temperature and the rates of changes of steam flow-rate well inside their targeted ranges. In this paper, a novel compensation signal based dual rate adaptive controller is developed by representing the unknown variations of dynamics as unmodeled dynamics. In the proposed controller design, such a compensation signal is constructed and added onto the control signal obtained from the linear deterministic model based feedback control design. Such a compensation signal aims at eliminating the unmodeled dynamics and the rate of changes of the currently sample unmodeled dynamics. A successful industrial application is carried out, where it has been shown that both the supply water temperature and the rate of the changes of the steam flow-rate can be controlled well inside their targeted ranges when the process is subjected to unknown variations of its dynamics.

Adaptive signal approacg↗

Development and evaluation of virtual refrigerant mass flow sensors for fault detection and diagnostics

Refrigerant mass flow rate is an important measurement for monitoring equipment performance and enabling fault detection and diagnostics. However, a traditional mass flow meter is expensive to purchase and install. A virtual refrigerant mass flow sensor (VRMF) uses a mathematical model to estimate flow rate using low-cost measurements and can potentially be implemented at low cost. This study evaluates three VRMFs for estimating refrigerant mass flow rate. The first model uses a compressor map that relates refrigerant flow rate to measurements of inlet and outlet pressure, and inlet temperature measurements. The second model uses an energy-balance method on the compressor that uses a compressor map for power consumption, which is relatively independent of compressor faults that influence mass flow rate. The third model is developed using an empirical correlation for an electronic expansion valve (EEV) based on an orifice equation. The three VRMFs are shown to work well in estimating refrigerant mass flow rate for various systems under fault-free conditions with less than 5% RMS error. Each of the three mass flow rate estimates can be utilized to diagnose and track the following faults: 1) loss of compressor performance, 2) fouled condenser or evaporator filter, 3) faulty expansion device, respectively. For example, a compressor refrigerant flow map model only provides an accurate estimation when the compressor operates normally. When a compressor is not delivering the expected flow due to a leaky suction or discharge valve or other internal fault, the energy-balance or EEV model can provide accurate flow estimates. In this paper, the flow differences provide an indication of loss of compressor performance and can be used for fault detection and diagnostics.

Kim, Woohyun↗

Surface energy of air fractionated corn stover

Despite decades of research, Integrated Biorefineries (IBRs) are still not commercially viable because of the long-standing, unresolved challenges related to biomass solids handling and transport (e.g., flowability and fouling), and pretreatment e.g., wettability and conversion). The compendium of challenges facing IBRs lead to operational reliability and time-on-stream estimates of 30%, yet economically viable IBRs require greater than 90% operational reliabilities. The performance of commercial solids handling operations is largely dependent on the fundamental thermodynamic property, surface energy. Combining surface area, thermogravimetric, and inverse gas chromatography analyses, we show the observed differences in surface energy (e.g., wettability and work of cohesion) for anatomically air fractionated corn ( Zea mays L.) stover. Furthermore, this study highlights the importance of understanding and tuning biomass surface energy to improve IBR solids handling and transport, and pretreatment operations.

09 BIOMASS FUELS↗

Chemical and physical characterization of aerosols from fast pyrolysis of biomass

Biomass fast pyrolysis vapors contain a significant quantity of persistent aerosols, which can impact downstream processing by e.g. fouling of surfaces and deposition on downstream catalysts. In this study, aerosol concentrations and size distributions were measured by an impactor in two pyrolysis systems, a bench-scale fluidized-bed pyrolyzer and a pilot-scale cyclone pyrolyzer. In both units, the mass-based mode aerosol diameter was approximately 1 um before aerosol collection devices in cooled vapors of 300-370 K but the number-based median was < 0.1 um. Aerosols < 1 um were formed and aerosols > 1 um deposited during cooling of pyrolysis vapors from 620 to 370 K in the fluidized-bed pyrolysis system. Here, the oil fraction collected from the aerosols constituted approximately 40 wt% of the total oils collected in both systems. Compared to the total collected oil, the oil fraction from the aerosols was enriched in lignin-derived components and anhydrosugars and had lower concentrations of low molecular weight cellulose derived oxygenates, such as hydroxyketones.

09 BIOMASS FUELS↗

Conventional and autothermal pyrolysis of corn stover: Overcoming the processing challenges of high-ash agricultural residues

The high ash content of agricultural residues and other kinds of herbaceous biomass makes it a challenging feedstock for fast pyrolysis to bio-oil. Using corn stover as a representative feedstock, this study investigates fast pyrolysis of high ash, herbaceous biomass in a pilot-scale fluidized bed reactor using both conventional, nitrogen-blown and autothermal, air-blown operation. Initial efforts to pyrolyze corn stover were challenged by bed fouling, which prevented steady reactor operation. Substitution of coarser bed material allowed operation at higher superficial velocities, which promoted attrition and elutriation of recalcitrant biochar particles from the reactor. This resulted in dramatic improvement in stable reactor operation for both conventional and autothermal pyrolysis with bio-oil yields among the highest reported for pyrolysis of corn stover. The oxygen-to-biomass equivalence ratio required for autothermal operation was 6.8%. Autothermal operation also resulted in significant process intensification, increasing corn stover throughput from 7.8 kg hr –1 to 21.9 kg hr –1 for this 8.9 cm diameter reactor. Air-blown, autothermal operation did not significantly reduce bio-oil yield despite the presence of partial oxidation reactions. In conclusion, carbon balances indicate carbon yields of biochar and aqueous, bio-oil light ends decreased by 18.5% and 4.7%, respectively, during autothermal pyrolysis compared to conventional pyrolysis while the more valuable, organic-rich heavy ends of the bio-oil were essentially preserved.

09 BIOMASS FUELS↗

Effects of the method of active site characterization for determining structure-sensitivity in Ag-catalyzed ethylene epoxidation

We report catalysts have been prepared on a low surface area α-Al 2 O 3 support used commercially for previous generation olefin epoxidation catalysts. Prescreening of the low surface area alumina (0.73 m 2 /g) indicated the absence of acid catalyzed isomerization of EO at an evaluation temperature of 210 °C. A 0.1 wt% Ag base material synthesized by incipient wetness impregnation of AgNO 3 was used as a base material for electroless deposition (ED) of additional Ag to increase particle sizes by controlled reduction of Ag + directly onto the preexisting Ag surface to form weight loadings between 0.3 and 5.0 wt% metal. A 12 wt% Ag/α-Al 2 O 3 using Ag 2 C 2 O 4 as the Ag precursor was also prepared to compare performance of the ED samples with a catalyst more typical of industrial formulations. Characterization by SEM, STEM, and hydrogen titration of oxygen precovered Ag characterized before and after catalytic evaluation indicated that microscopy is required to accurately represent distributions of Ag particle sizes, but H 2 titration of O-precovered Ag gives the best representation of active sites since it directly counts the number of Ag surface sites. Larger particles >100 nm are resistant to both Ag sintering and carbon foulant; TOF values were relatively insensitive to particle size with only a 2.2 × difference between the best and worst performing samples. Selectivity, which is not a function of TOF, shows the most significant structure sensitivity effect where particle sizes follow the trend 67 nm ≈ 92 nm (58% EO) < 157 nm (67% EO) < 211–542 nm (73% EO). The lower EO selectivities were also correlated with increased fouling for the smaller Ag sizes, suggesting that more strongly bound EO precursor(s) leads to combustion and CO 2 /H 2 O formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗