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Research Advances in Environmental Chemistry: Sustainability and Sustainable Technologies
01:00pm - 04:00pm USA / Canada - Pacific - April 5, 2021
Slawo Lomnicki, Organizer, Presider
Track: [ENVR] Division of Environmental Chemistry
Division/Committee: [ENVR] Division of Environmental Chemistry

This symposium is open to all papers on environmental chemistry or environmental engineering that may be beyond the focus of the specific topics addressed in other ENVR symposia.

Monday
Dairy manure as soil amendment: The good, the bad and the ugly
01:00pm - 01:20pm USA / Canada - Pacific - April 5, 2021
Track: [ENVR] Division of Environmental Chemistry
The rapid increase in concentrated animal feeding operations in South Idaho brought the need for utilization of large amounts of dairy manure. Application of manure to agricultural fields as soil amendment can provide the benefit of increased plant nutrients and organic carbon, and potentially result in the improvement of soil health and mitigation of carbon emission by closing the loop in nitrogen cycling. At the same time, manure can be a source of organic and inorganic contaminants. Here we present results from the bench-to-field lysimeter study on the release of contaminants from dairy manure under typical application and irrigation regime. Intact soil core lysimeters (10 cm diameter, 0.6 m length) were sampled by a tractor-mounted hydraulic soil probe with PVC tubing liners and used for bench scale transport experiment. While field sampling was carried out using passive lysimeters silicon carbide porous cups (2×6 cm, -90 kPa bubbling pressure). For field and laboratory experiments, a representative composted manure was used containing up to 30.7, 9.0, and 47.7 g of N, P, and K per kg of manure, respectively, with the highest potential N:P:K value of the tested samples was equivalent to a fertilizer value of 3:2:6. Manure samples also contained several potential contaminants such as hormones, phytoestrogens, antibiotics, and other veterinary drugs. While phytoestrogens were present in manure in highest amounts relative to all other detected contaminants, once manure was applied they were mitigated by soil and not detected in ground water. Antibiotics and hormones were two groups of contaminants that were consistently present in both bench and field scale lysimeters with concentrations up to 0.02 µg. In addition, groundwater collected from manure applied fields contained elevated sulfate and nitrate concentrations as compared to groundwater collected from synthetic fertilizer applied plots.
Monday
The saturated activated carbon fiber (ACF) was regenerated by electro-peroxymonosulfate (E-PMS) process to desorb phenol (PN) from ACF, as well as mineralizing the contaminants in the regeneration solution simultaneously. After the regeneration process, 81.90% of TOC in ACF was removed, and the desorbed PN in the regeneration solution was only 4.11% of [PN]0. Compared with conventional electrochemical (E-Pt), PMS alone and E-PDS regeneration processes, E-PMS regeneration achieved the highest regeneration efficiency and the lowest energy consumption. Further study proved that reactive oxygen species oxidation played a major role in E-PMS process, and the relative contribution of hydroxyl radical, sulfate radical, and singlet oxygen was calculated subsequently. In addition, the migration of main intermediates and oxidation of ACF during the regeneration process were measured. Sample characterization of SEM, BET, Roman, FT-IR, and XRD suggested that ACF was protected under the action of cathode field polarization. The regeneration efficiency of ACF could be improved from 75.69% to 82.53% with PMS three-intervallic dosing. Moreover, ACF could maintain the regeneration efficiency of about 60% after 10 cycles, and the concentration of PN in the solution remained low throughout the cycles. The results indicated that E-PMS process was an efficient and environmentally friendly method for the regeneration of ACF.

Monday
The increased toxicity potential associated with waste solvents can hardly be overstated. The use of conventional waste disposal techniques such as incineration, onsite and offsite disposal have been explored; however, these traditional waste disposal approaches tend to increase the overall carbon and ecological footprints. Solvent recovery methods present a better alternative to these conventional approaches to improve industrial processes’ circularity. Emergy is one way to quantify the sustainability of an industrial process. It is defined as the amount of available energy (exergy) of one kind that is directly and indirectly used up in transformations to make a product. Different energy flow type into a process needs to be converted into a solar energy equivalent, termed as solar emjoules (sej). This emjoules sets the basis for all emergy calculations. Another metric that presents a good basis for sustainability analysis is the sustainable process index (SPI), which estimates the total area needed by a process to produce a unit of product. The choice of area as the basis for calculation is based on the idea that solar energy is the real long-term input with its utilization bound to the planet’s limited surface area. Thus, SPI represents the area needed by the process to provide one unit of product, while emergy helps to account for all the work done by nature and the human-economy in the production process. Due to the common denominator of solar energy and the use of several interrelated indices in the estimation of SPI and emergy, only one metric is insufficient to present a comprehensive sustainability analysis for a process. Therefore, to offer a holistic view of sustainability for a process, it is essential to integrate both SPI and emergy. In this work, a superstructure-based solvent recovery framework has been developed that considers multiple separation technologies simultaneously to recover waste solvents. We integrated mathematical models that consider the SPI, Emergy, and Economics of the recovery pathway. We then formulated a multi-objective problem that seeks to minimize all three metrics simultaneously. Our results indicate that solvent recovery presents a good alternative to conventional waste solvent disposal techniques such as incineration. Additionally, the integrated SPI-emergy analysis offers an approach to quantify the environment’s role in absorbing and processing pollution.
Monday
Polyolefin plastics are materials manufactured and used at a global scale, necessitating an effective recycling solution. Pyrolysis has significant potential as a technology for polyolefin recycling, but fundamental knowledge of the process chemistry is limited. To elucidate the chemistry of polymer decomposition and measure the intrinsic reaction kinetics of plastic pyrolysis, an experimental system is needed which is capable of operating absent transport limitations and on sufficiently short time scales. To this end, a new Pulse-Heated Analysis of Solid Reactions (PHASR) system was developed for the study of polyolefin pyrolysis. The new PHASR system operates under conditions which enable the measurement of polyolefin pyrolysis product evolution (e.g., propylene, butylene) under isothermal conditions with millisecond time-scale resolution. A Visual PHASR system was also developed for the visualization of polyolefin pyrolysis via high-speed photography, enabling the observation of reaction phenomena. As polypropylene (PP) is one of the most widely produced plastics, it is critical to understand the kinetic behavior of PP pyrolysis for the development of industrial recycling solutions as part of a circular economy. As such, it is of interest to use the PHASR method to measure the intrinsic kinetics of PP pyrolysis. This work demonstrates the application of PHASR to PP, presenting kinetic results and observed reaction phenomena.
Monday
Intermission
02:20pm - 02:30pm USA / Canada - Pacific - April 5, 2021
Track: [ENVR] Division of Environmental Chemistry

Monday
Semi-continuous anaerobic digestion (AD) of sewage sludge with hydrothermal (HT) pretreatment have emerged as a sustainable technique for energy and nutrient recovery. Both AD and HT treatments impose significant impacts on the reclamation/recycling of phosphorous (P). Yet, the speciation evolution of P as well as involved reaction mechanisms during combined semi-continuous AD with HT pretreatment of sewage sludge still remain unclear. This study investigates the evolution and mineralization of P in sewage sludge during combined semi-continuous AD with HT pretreatment using complementary chemical extraction and X-ray spectroscopy characterizations. For raw sludge with high molar ratio of Mg/Fe (5.9), HT did not induce the formation of struvite in the hydrochars. Struvite was observed during the subsequent AD of low temperature (90 and 125 °C) HT slurries due to the reaction of Mg-phosphate phases with extensive NH4+ at pH > 7. For HT slurries produced at 155 °C, the pH was always below 7 during the subsequent AD process, preventing struvite precipitation in the AD solids. The results from this study suggest that pH plays important roles in controlling P mineralogy during AD and HT treatments of sludges. This work also provides insights into the reaction mechanisms during HT-AD treatments of sludges and can help evaluate the nutrient recycling and reclamation options for sludges.
Monday
In 2016, the DOE estimated the United States has 205 million tons of available biomass waste that include algae, forestry, agricultural, and municipal waste. These waste streams are often uncollected or underutilized. One common thermochemical processing method capable of converting a wide variety of organic residues into a value-added product is hydrothermal carbonization (HTC). HTC converts wet substrates at operating temperatures ranging between 150 – 280 °C and autogenous pressures to form a hydrochar product with applications in soil amendment, metal absorbent, and solid fuel. HTC has been broadly applied in thousands of published studies that evaluate the effectiveness of HTC using a subset of feedstocks and/or operating conditions. Similarly, the hydrochar products have been selectively characterized based on desired properties of the application. To date, connections between HTC studies have been limited to direct comparisons on results that have similar operating conditions and/or feedstocks. Therefore, we perform a meta-analysis on current HTC work in conjunction with experimental runs to assess the dependency of feedstock and process conditions on HTC performance.
Our meta-analysis model evaluates over 100 datasets from HTC runs using miscanthus, cellulose, rice husk, and wheat straw. The HTC performance and corresponding hydrochar properties are considered with a confidence level on their dependency to the HTC operating temperature, reactor volume, reaction time, and reactor stirring. Hydrochar properties considered in the meta-analysis include elemental content, higher heating value, and proximate composition. Meta-analysis trends are experimentally assessed using miscanthus, food waste and brewer’s spent grain under HTC conditions between 190 – 250 °C and two differently sized reactors. Experimental HTC runs revealed synergistic effects when combining waste feedstocks. In addition, HTC runs using food waste produced different in hydrochar yields when performed in reactors of different size. This study reveals important considerations in comparing and evaluating HTC performance with other studies.

Monday
Reverse electrodialysis (RED) enabling sustainable wastewater management for harvesting blue energy and fertigation
03:10pm - 03:30pm USA / Canada - Pacific - April 5, 2021
Track: [ENVR] Division of Environmental Chemistry
When it comes to the water-energy nexus, harnessing blue energy is vital with today’s energy-demanding processes and technologies. In this context, the reverse electrodialysis (RED) process is a thriving process that is serving as a potentially viable external energy source for many energy intensive processes such as membrane distillation (MD), electrodialysis (ED), capacitive deionization (CDI), etc. RED utilizes the Gibbs free energy of mixing two solutions of different salinities - salinity gradient energy (SGD) - and converts it into usable electrical energy. Hence, it is crucial to develop RED systems with an appropriate low concentration (LC) and high concentration (HC) solution pairs to maximize the extractable power density and at the same time make use of various disposable industrial effluent streams. Herein, this work explores using a compact RED system that converts the chemical potential energy of mixing ammonia-based industrial wastewater stream (LC) with a high effluent salinity brine stream (HC) into viable electrical energy. Simultaneously, the resultant brackish water level stream of this mixing process is properly diluted and used for fertigation to increase the sustainability of the process. As such, mixing those wastewater streams will eliminate the unadvisable disposal of high salinity brine directly back into the sea. The wastage of ammonia-rich wastewater can enhance agricultural productivity. The influence of concentrate and dilute stream concentrations, compositions and flowrates on acquired power density and energy recovery were investigated and gave maximum power density of 1.3 Wm-2 in the tested RED cell, which is comparable with power densities achieved with conventional NaCl based solutions in the same system (2.0 Wm-2). Additionally, the impact of changing the number of ion exchange membrane pairs, amount of external load added, and recyclability of wastewater streams was studied and optimized to amplify the osmotically generated power and subsequently obtain the maximum power density from it, and also to increase the extent of wastewater dilution to reach brackish water levels suitable for irrigation.
Monday
Photocatalytic CO2 reduction with potassium doped iron oxide
03:30pm - 03:50pm USA / Canada - Pacific - April 5, 2021
Track: [ENVR] Division of Environmental Chemistry
Photocatalysis by metal doped semiconductor is attracting major attention to enable the reduction of CO2(g) in the presence of water vapor as a hole scavenger. Such technology has the potential to produce chemical feedstock and simultaneously minimize environmental pollution. Potassium doped iron oxide (α-Fe2O3) of varying potassium compositions (100 Fe:x K, 0 ≤ x ≤ 5) are synthesized using incipient wetness impregnation method. The structure, composition, and properties of the catalysts are investigated by X-ray diffraction, nitrogen adsorption-desorption experiments, DSC, TGA, and multiple spectroscopies, including: DRUV-vis, FTIR, Raman, ICP-AES, XPS and UPS, TEM with EDS and SAED. UV-visible light (λ ≥ 295 nm) excited the catalysts uniformly deposited in a cylindrical photoreactor in presence of pure CO2 or air (400 ppm CO2), both under a saturated water vapor atmosphere. The maximum production of CO(g) (RCO = 0.5836 μmol gcat-1 h-1 in pure CO2 and RCO = 0.4267 μmol gcat-1 h-1 in air) quantified by GC-TCD-FID corresponds to 100Fe:1K photocatalyst. The surface doped potassium photocatalyst enhances the photocatalytic efficiency by creating a more negative conduction band than the CO2/CO reduction potential as supported by UPS and DRUV-vis spectroscopies. The photoreduction mechanism and also the effects of scavenger species will be reported.
Monday
Virtual Networking & Discussion
03:50pm - 04:00pm USA / Canada - Pacific - April 5, 2021
Track: [ENVR] Division of Environmental Chemistry

I&EC General Papers :  
05:00pm - 07:15pm USA / Canada - Pacific - April 8, 2021
John Clegg, Organizer; Anna Ivashko, Organizer; June Kowalski, Organizer, Presider
Track: [I&EC] Division of Industrial and Engineering Chemistry
Division/Committee: [I&EC] Division of Industrial and Engineering Chemistry
Thursday
Computational framework for the techno-economic feasibility analysis of monoclonal antibody purification platforms
05:00pm - 05:15pm USA / Canada - Pacific - April 8, 2021
Track: [I&EC] Division of Industrial and Engineering Chemistry
This presentation will discuss the development of a computational framework for evaluating the performance of continuous antibody purification processes. Monoclonal antibodies (mAbs) are used to treat chronic conditions including immunological disorders, cardiovascular diseases, many forms of cancer, and recently COVID-19. This last application highlights the need for flexible production processes capable of responding to sudden increases in demand. Improved cell lines and perfusion technologies have shifted the capacity and economic constraints of mAbs production towards the downstream process (DSP). Continuous purification platforms and membrane chromatography are process alternatives that have the potential to increase the capacity and the profitability of the production process. In this regard, the technoeconomic feasibility of an industrial-scale DSP featuring these technologies must be evaluated. The computational framework developed for this purpose is used to simulate batch, two-column simulated moving bed, and three-column periodic countercurrent chromatography membrane capture platforms. We first validate the capture model with experimental equilibrium isotherm data and dynamic breakthrough curves. We then incorporate the performance results from this model in an Intelligen SuperPro Designer process simulation and calculate key performance indicators of these operations (productivity, COG and capacity). The framework allows us to compare process alternatives by considering the physical phenomena involved in membrane chromatography, the scheduling for the different production platforms, and the economic factors in a context of large-scale industrial production.
Thursday
Development of asset management methods for water treatment utilities
05:15pm - 05:30pm USA / Canada - Pacific - April 8, 2021
Track: [I&EC] Division of Industrial and Engineering Chemistry
Water treatment networks are a key facility in any municipality for the proper treatment of waste. If these treatment systems are to fail, there would be dire environmental consequences as large amounts of undesired waste would accumulate in the ecosystem. Many facilities in the United States have outdated or old assets, making water management facilities concerned about system malfunctions. The current solution to these malfunctions is to use a reactionary (wait-watch-act) or subjective approach for asset management, because of the absence of a definitive objective-based management method. The problem with a subjective approach is that an action is only taken when a failure occurs. Once an issue arises, significant amounts of manpower and capital are needed to access and repair the asset failures, and, at the same time, it is important to minimize any negative impacts on the surrounding environment. Thus, the reactionary approach leads to large amounts of capital loss and negative impacts as significant amounts of wastewater can be released before treatment. To this end, if we can design an asset evaluation and failure prediction system, the relative economic and negative impacts can be minimized significantly.
Thus, we present an objective-based asset management approach that can be employed by the Wastewater Treatment Utilities, such as the ACUA (Atlantic County Utilities Authority), to minimize potential failures, environmental hazards, and financial expenditures. By using concepts from engineering, mathematics, and statistics, each asset is simultaneously analyzed, compared, and ranked using machine learning in programming platforms such as Google Colaboratory™. The analysis consists of evaluating the existing asset data, its characteristics such as its location, installation year, construction materials, dimensions, and subsequent development of correlations for risk analysis and failure probabilities.
This analysis, coupled with historic data from an industrial partner, provides enough information to make a valid assessment of when and how the assets will fail. This assessment provides an accurate rating for potential asset failures and presents the probable corrective actions and maintenance schedules that can manage the existing wastewater treatment facility and its network of pipelines and pumping stations effectively and minimize the impacts of asset failures.

Thursday
Troger's base based poly (Benzocrown ethers)s for CO2 and H2 gas separation
05:30pm - 05:45pm USA / Canada - Pacific - April 8, 2021
Track: [I&EC] Division of Industrial and Engineering Chemistry
In a groundbreaking work of discovering dibenzo-18-crown-6 (DB18C6) by Pederson in 1967, DB18C6 has been used for many applications such as a receptor in supramolecular chemistry, host in host-guest chemistry, and copolymer in gas-separation applications. In this work, we will show Tröger’s base- based dibenzo crown ether polymer used for gas- separation applications. Tröger’s base- based dibenzo crown ether polymer was synthesized from trans diamino DB18C6. The synthesized polymer was characterized by NMR, GPC, MALDI. The membrane was cast and gas separation data were obtained for different gases i.e H2, CO2, CH4, O2. In this work, improved gas permeability selectivity was developed for CO2/N2; H2/N2; CH4/N2. Synthetic route to obtain Tröger’s base- based dibenzo crown ether and its selectivity of H2 and CO2 versus other gases data will be presented.
Thursday
The COVID-19 pandemic placed a tremendous strain on global supply chains including those for producing hand sanitizer and surface disinfectants. Prior to the outbreak of COVID-19, annual world production of hand sanitizer was 300,000 L. Increased demand for these products led to erosion of the supply chain for the components of these products. The growth in demand led to the introduction of interim government regulations to ease the shortages. The immediate need for disinfectant products necessitated a local, low-cost adaptation of existing industry to produce hand and surface sanitizers, which included the permittance of “technical-grade” ethanol for inclusion in sanitizer products. A fuel ethanol production plant was evaluated, and processes were developed to upgrade and purify ethanol for hand sanitizer without the need for additional infrastructure. The ethanol was characterized according to United States Pharmacopoeia (USP) monograph and the process upgrades were selected and optimized to address non-compliant parameters (e.g. ozone treatment, treatment of hard water, and mechanical filtering). Health Canada issued permits for the ingredients, and formulated sanitizer products were available to the public within 2 months to address shortages. Meanwhile, purification processes were further improved, and within 8 months the ethanol met food quality compliance (e.g. Food Chemicals Codex). This local, sustainable, and scalable ethanol refining process is transferable to other ethanol plants and has long-term implications for emergency response planning and reduces the need for long-distance transport of ethanol.
Thursday
Intermission
06:00pm - 06:15pm USA / Canada - Pacific - April 8, 2021
Track: [I&EC] Division of Industrial and Engineering Chemistry

Thursday
Synthesis and properties of asymmetric and symmetric secondary alcohols: A substituted glycerol derived green solvent
06:15pm - 06:30pm USA / Canada - Pacific - April 8, 2021
Track: [I&EC] Division of Industrial and Engineering Chemistry
A series of symmetric and asymmetric secondary alcohols carrying glycerol skeleton were synthesized from epichlorohydrin and corresponding alcohols. These small molecules can be used for CO2 absorption and has potential to serve as reaction solvent. They are also able to be easily transferred into ketones and tri-ethers. Furthermore, as functional groups, they allow to be incorporated into ionic liquids and polymers as well. Synthetic routes via reaction of alcohol and other glycerol moiety and its characterization will be discussed. Furthermore, it’s application in CO2 absorption will be discussed in the presentation.
Thursday
Molecular insight into the mass transport mechanism of CO2 in the interfacial ionic liquids
06:30pm - 06:45pm USA / Canada - Pacific - April 8, 2021
Yanlei Wang, Presenter
Track: [I&EC] Division of Industrial and Engineering Chemistry
The transport behavior of CO2 in the ionic liquids (ILs)-electrode interface is revealed via the joint molecular dynamics simulation and thermodynamic analysis method. Combining the hopping mechanism within the interfacial region and the self-diffusive behavior in bulk, a hopping-diffusion model is developed to evaluate the transport performance of CO2. The effective transport efficiency of CO2 transporting across interfacial ILs could be predicted based on the hopping-diffusion model, showing the faster transport feature of CO2 in [Emim][BF4]. Meanwhile, the enhanced antisymmetric stretching mode and entropy decrease of CO2 in various ILs interface are identified, demonstrating [Emm245im][BF4] possesses the biggest thermodynamic advantage in terms of reducing the entropy cost. As both fast mass transport and small entropy cost can enhance the performance of ILs, the detailed correlation between the transport process and thermodynamic information would help to clarify the molecular mechanism of ILs/CO2-electrode interface in the specific electrochemical applications.
Thursday
Fucntionalized organo-silica materials for trace collection of phosphate and nitrate
06:45pm - 07:00pm USA / Canada - Pacific - April 8, 2021
Track: [I&EC] Division of Industrial and Engineering Chemistry
Nitrates and phosphates exist naturally but are present in elevated concentrations in many areas primarily due to agriculture; these elevated concentrations are concerning for human and environmental health. A variety of methods are being investigated and utilized for removing nitrate and phosphate from water systems, we have focused on functionalized silica-based sorbent materials. We have designed, synthesized, and characterized a set of silica-based functionalized materials for removal of these unwanted compounds from natural waters. These materials are multifunctional, having been functionalized with both amine groups as well as electron deficient aromatics. We chose amine groups because they are known to non-selectively bind anions from natural waters. Electron deficient arene rings were selected due to their ability to form anion-π interactions with the target anion; anion-π binding has shown preference to nitrate in some examples. A series of ligands containing electron deficient arene rings have been incorporated onto the silica surface using Cab-o-sil® as the silica base. Performance testing is ongoing, but initial results are promising.
Thursday
Previous work from this group utilized a HYSYS simulator to predict the performance of an ethylene oxidative dehydrogenation (ODH) production facility using alternative diluents and separation technology not currently used in the standard industrial process [1-4]. This work has investigated the development of membrane-based separation technology for the production of ethylene for the oxidative dehydrogenation (ODH) reaction of ethane using a HYSYS simulator with MEMCAL extension software in concert with economic and safety analyses. The application of polymer-membrane separation and non-cryogenic distillation alternatives, such as bottom-flash, heat-pump assisted and low-temperature distillation, were simulated and evaluated individually and in-tandem with membrane separation. The effects of alternative diluents, process flammability issues, and economic analysis results have been reported. Current investigations seek to apply these findings to new processes for the production of C3-based olefins from paraffins namely polypropylene production and propylene oxide manufacturing from propane ODH. This work will discuss recent process design / simulation results with updated economic feasibility analyses, flammability safety findings and alternative process technologies.