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At least 163 records · Page 9

Performance study of single undoped CsI crystals for the Mu2e experiment

The Mu2e experiment at Fermilab aims to measure the neutrinoless muon-to-electron conversion, which is a charged-lepton flavor-violating process. The goal of the experiment is to reach a single event sensitivity of 2.5 × 10 -17 , to set an upper limit on the muon conversion rate at 6.7 × 10 -17 in a three-year run. For this purpose, the Mu2e detector is designed to identify electrons from muon conversion and reduce the background to a negligible level. It consists of a low-mass straw tracker and a pure CsI crystal calorimeter. In this paper, the performance of undoped CsI single crystal is reported. Crystals from many vendors have been characterized by determining their Light Yield (LY) and Longitudinal Response Uniformity (LRU), when read with a UV extended PMT, and their time resolution when coupled to a silicon photomultiplier. The crystals show a LY of ~100 photoelectrons per MeV when wrapped with Tyvek and coupled to the PMT without optical grease. The LRU is well represented by a linear slope that is on average 0.6%/cm. Both measurements have been performed using a 22 Na source. The timing performance has been evaluated exploiting cosmic rays, with MPPC readout. A timing resolution lower than 400 ps has been achieved (at ~20 MeV, which is the energy released by a minimum ionizing particle in the crystal).

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Anaerobic Digestion and Combined Heat and Power Study (Final Technical Report)

One of the underlying objectives of this study is to recover the untapped energy in wastewater biomass. Some national statistics worth considering include: (1) 5% of the electrical energy demand in the US is used to treat municipal wastewater; (2) This carbon rich wastewater is an untapped energy resource; (3) Only 10% of wastewater treatment plants (>5mgd) recover energy; (4) Wastewater treatment plants have the potential to produce > 575 MW of energy nationwide; and (5) Wastewater treatment plants have the potential to capture an additional 175 MW of energy from waste Fats, Oils and Grease. The WSSC conducted this study to determine the feasibility of utilizing anaerobic digestion and combined heat and power (AD/CHP) and/or biosolids gasification and drying facilities to produce and utilize renewable digester biogas. Digester gas is considered a renewable energy source and can be used in place of fossil fuels to reduce greenhouse gas emissions. The project focus includes: (1) Converting wastewater Biomass to Electricity; (2) Using innovative technologies to Maximize Energy Recovery; and (3) Enhancing the Environment by reducing nutrient load to waterways (Chesapeake Bay), Sanitary Sewer Overflows (by reducing FOG in sewers) and Greenhouse Gas Emissions. The study consisted of these four tasks: (1) Technology screening and alternative shortlisting, answering the question 'what are the most viable and cost effective technical approaches by which to recover and reuse energy from biosolids while reducing disposal volume?'; (2) Energy recovery and disposal reduction potential verification, answering the question 'how much energy can be recovered from biosolids?'; (3) Economic environmental and community benefit analysis, answering the question 'what are the potential economic, environmental and community benefits/impacts of each approach?'; and (4) Recommend the best plan and develop a concept design.

03 NATURAL GAS↗

SHINE Vacuum Pump Test Verification

Normetex pumps used world-wide for tritium service are no longer available. DOE and other researchers worldwide have spent significant funds characterizing this pump. Identification of alternate pumps is required for performance and compatibility with tritium gas. Many of the pumps that could be used to meet the functional performance requirements (e.g. pressure and flow conditions) of the Normetex pump have features that include the use of polymers or oils and greases that are not directly compatible with tritium service. This study assembles a test system to determine the flow characteristics for candidate alternate pumps. These tests are critical to the movement of tritium through the SHINE Tritium Purification System (TPS).

07 ISOTOPE AND RADIATION SOURCES↗

Innovative Water Management Technology to Reduce Environmental Impacts of Produced Water

Clemson University with Chevron as an industry partner developed and applied treatment technology using constructed wetland systems to decrease targeted constituents in simulated and actual produced waters to achieve reuse criteria and discharge limits. Pilot-scale and demonstration constructed wetland treatment system (CWTS) experiments led to design strategies for treating a variety of constituents of concern (COCs) in produced waters including divalent metals, metalloids, oil and grease, and ammonia. Targeted biogeochemical pathways for treatment of COCs in pilot-scale CWTS experiments included divalent metal sulfide precipitation through dissimilatory sulfate reduction, metal precipitation through oxidation, reduction of selenite to insoluble elemental selenium, aerobic biodegradation of oil, nitrification of ammonia to nitrate, denitrification of nitrate to nitrogen gas, separation of oil using an oilwater separator, and sorption of ammonia to zeolite. Treatment performance results indicated that CWTSs can be designed and built to promote specific environmental and geochemical conditions in order for targeted biogeochemical pathways to operate. The demonstration system successfully achieved consistent removal extents even while inflow concentrations of COCs in the produced water differed by orders of magnitude. Design strategies used in the pilot-scale and demonstration CWTSs to promote specific conditions that can be applied to designing full-scale CWTSs include plant and soil selection, water-depth selection, addition of amendments, and hydraulic retention time (HRT). These strategies allow conditions within a CWTS to be modified to achieve ranges necessary for the preferred biogeochemical treatment pathways. In the case of renovating a produced water containing COCs that require different biogeochemical pathways for treatment, a CWTS can be designed with sequential cells that promote different conditions. For example, the pilot-scale CWTS for post-reverse osmosis produced water was designed to promote oxidizing conditions within the first wetland cell for nitrification of ammonia, and the subsequent three cells were designed to promote reducing conditions for denitrification of nitrate. By incorporating multiple wetland cells in a CWTS, the conditions within each cell can be modified for removal of specific COCs. In addition, a CWTS designed with multiple cells allows for convenient sample collection points so that biogeochemical conditions of individual cells can be monitored and performance evaluated. Removal rate coefficients determined from the pilot-scale CWTS experiments and confirmed by the demonstration system can be used to calculate HRTs required to treat COCs in full-scale CWTSs. The calculated HRTs can then be used to determine the surface area or "footprint" of a full-size CWTS for a given inflow rate of produced water.

54 ENVIRONMENTAL SCIENCES↗

High Flux FRC Facility for the Stability, Confinement and ITER Divertor Studies

The TCS (Translation, Confinement, & Sustainment) program was begun on 7 August, 1996 to renew basic studies of the Field Reversed Configuration (FRC). The program made use of the old LSX (Large s Experiment) device, which was constructed at STI during the period from 1986 to 1990, but only operated for one year due to a DOE decision at the time to focus exclusively on the tokamak configuration. LSX was transferred to the University of Washington in 1992 and modified (LSX/mod) to perform Tokamak Refueling by Accelerated Plasmoids (TRAP) experiments. The TRAP program was funded from 7 August, 1992 until 6 August, 1996, but was utilized for an additional year while TCS was being constructed. During the first TCS funding period TCS was completed and initial experiments were begun. A large multi-megawatt RF power supply was built by Los Alamos National Laboratory (LANL) for use with a Rotating Magnetic Field (RMF) system, and LANL has been a continuing participant in our experimental program. A smaller prototype facility, called the Star Thrust Experiment (STX) was also built and operated in this period, partly with NASA funding, before TCS came on-line. A final report for this construction period was submitted in September 2000. A first renewal period (2.5 years) provided operating funds for the period between July 7, 2000 and January 6, 2003. A great deal of progress was made in understanding the use of RMF to both form and sustain FRCs during this period. The principal result of the experimental program was the formation of quasi steady-state (as long as RMF power was available) FRCs with densities in the 1-3x10 19 m -3 range. However, the plasma temperature (T e or T i ) was limited to sub-25 eV, except transiently during start-up, by the rapid accumulation of impurities. This is not surprising since TCS was only designed to demonstrate RMF flux build-up and was not provided with either fueling capabilities or modern vacuum conditioning technology. (The unplanned for long time steady-state operation was due entirely to recycling.) TCS employed a multi-section quartz vacuum vessel with greased “O”-ring seals. A final report for this second funding period was submitted in May of 2003.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

PILOT TESTING: PRETREATMENT OPTIONS TO ALLOW RE-USE OF FRAC FLOWBACK AND PRODUCED BRINE FOR GAS SHALE RESOURCE DEVELOPMENT

The goal of the A&M DOE NETL Project No. DE-FE0000847 was to develop a mobile, multifunctional water treatment capability designed specifically for “pre-treatment” of field waste brine. The project consisted of constructing s mobile “field laboratory” incorporating new technology for treating high salinity produced water and using the lab to conduct a side-by-side comparison between this new technology and that already existing in field operations. A series of four field trials were performed utilizing the mobile unit to demonstrate the effectiveness of different technology suitable for use with high salinity flow back brines and produced water. The design of the mobile unit was based on previous and current work at the Texas A&M Separation Sciences Pilot Plant. The several treatment techniques which have been found to be successful in both pilot plant and field tests had been tested to incorporate into a single multifunctional process train. Eight different components were evaluated during the trials, two types of oil and grease removal, one BTEX removal step, three micro-filters, and two different nanofilters. The performance of each technique was measured by its separation efficiency, power consumption, and ability to withstand fouling. The field trials were a success. Four different field brines were evaluated in the first trial in New York. Over 16,000 gallons of brine were processed. Using a power cost of $.10 per kWh, media pretreatment power use averaged $0.004 per barrel, solids removal $.04 per barrel and brine “softening” $.84 per barrel. Total power cost was approximately $1.00 per barrel of fluid treated. In Pennsylvania, brines collected from frac ponds were tested in two additional trials. Each of the brines was converted to an oil-free, solids-free brine with no biological activity. Brines were stable over time and would be good candidates for use as a make-up fluid in a subsequent fracturing fluid design. Reports on all of the field trials and subcontractor research have been summarized in this Final Report. Individual field trial reports and research reports are contained in the companion volume titled “Appendices”

Burnett, David↗

Environmental Baseline Survey for Proposed Land Use Permit Modification for Expansion of the Dynamic Explosive Test Site (DETS) 9940 Main Complex Parking Lot.

The approach was to perform a document search, supplemented by a visual site inspection, to identify potential environmental contamination associated with the property. Factors evaluated included hazardous substances; petroleum products and derivatives; environmental restoration sites; areas of concern; storage tanks; oil/water separators; grease traps; wash racks; waste tanks; pesticides; military munitions/ordnance; medical or bio-hazardous waste; radioactive waste; solid/municipal waste; indoor air quality; groundwater; wastewater treatment, collection, and disposal/discharge; drinking water quality; utilities; asbestos; polychlorinated biphenyls (PCBs); radon; lead-based paint; cultural resources; floodplains; and natural/biological resources.

54 ENVIRONMENTAL SCIENCES↗

Supplemental Environmental Baseline Survey for Proposed Land Use Permit Modification for Expansion of the Dynamic Explosive Test Site (DETS) 9940 Main Complex Parking Lot

The “subject property” is comprised of a parcel of land within the Kirtland Military Reservation, Bernalillo County, New Mexico, as shown on the map in Appendix B of this document. The land requirement for the parking lot addition to the 9940 Main Complex is approximately 2.7 acres. The scope of this Supplemental Environmental Baseline Survey (SEBS) is for the parking lot addition land transfer only. For details on the original 9940 Main Complex see Environmental Baseline Survey, Land Use Permit Request for the 9940 Complex PERM/0-KI-00-0001, August 21, 2003, and for details on the 9940 Complex Expansion see Environmental Baseline Survey, Proposed Land Use Permit Expansion for 9940 DETS Complex, June 24, 2009. The 2.7-acre parcel of land for the new parking lot, which is the subject of this EBS (also referred to as the “subject property”), is adjacent to the southwest boundary of the original 12.3- acre 9940 Main Complex. No testing is known to have taken place on the subject property site. The only activity known to have taken place was the burial of overhead utility lines in 2014. Adjacent to the subject property, the 9940 Main Complex was originally a 12.3-acre site used by the Department of Energy (DOE) under a land use permit from the United States Air Force (USAF). Historical use of the site, dating from 1964, included arming, fusing, and firing of explosives and testing of explosives systems components. In the late 1970s and early 1980s experiments at the 9940 Main Complex shifted toward reactor safety issues. From 1983 to 1988, fuel coolant interaction (FCI) experiments were conducted, as were experiments with conventional high explosives (HE). Today, the land is used for training of the Nuclear Emergency Response community and for research on energetic materials. In 2009, the original complex was expanded to include four additional 20-acre areas: 9940 Training South, 9940 Training East, T-Range 6, and Training West Landing Zone. The proposed use of the subject property is for the purpose of adding a parking lot to serve the increase in customer vehicles that is occurring as the 9940 Main Complex is more heavily utilized, and as the 2009 Expansion areas come online as operational training facilities. The subject property would be used only for parking, not for testing or training activities. The parking lot would have a gravel surface. Current and future work at the 9940 Main Complex involves arming, fuzing, and firing of explosives and the testing of explosive systems components in both terrestrial and aquatic settings. It also involves specialized training activities for a variety of first responder customers, both DOE and non-DOE agencies. The approach was to perform a document search, supplemented by a visual site inspection, to identify potential environmental contamination associated with the property. Factors evaluated included hazardous substances; petroleum products and derivatives; environmental restoration sites; areas of concern; storage tanks; oil/water separators; grease traps; wash racks; waste tanks; pesticides; military munitions/ordnance; medical or bio-hazardous waste; radioactive waste; solid/municipal waste; indoor air quality; groundwater; wastewater treatment, collection, and disposal/discharge; drinking water quality; utilities; asbestos; polychlorinated biphenyls (PCBs); radon; lead-based paint; cultural resources; floodplains; and natural/biological resources. Each of these factors is evaluated separately in Section 5, Findings for Subject Property. The property categorization for this subject property would be considered Category 1- “An area or real property where no storage, release, or disposal of hazardous substances or petroleum products or their derivatives has occurred into the environment or structures or disposed on the subject property (including no migration of these substances from adjacent properties).” There appears to be sufficient information to categorize the subject property and it appears that no further effort needs to be made to obtain additional information. There are no findings of an adverse nature on the subject property itself or from adjacent properties. It is recommended that the proposed transfer of the subject property from the USAF to DOE proceed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Community Anaerobic Digester: Powered by Students and Driving Practical Applications

The Vermont Tech Community Anaerobic Digester (VTCAD) was conceived and funded by a partnership of educational, agricultural, waste management and environmental groups to create a living laboratory demonstrating the value of recycling nutrients, renewable energy and agricultural co-products from organic wastes. VTCAD was constructed on the Randolph Center, Vermont campus of Vermont Tech, a public college offering engineering technology, agricultural, renewable energy education and workforce training. With funding from the U.S. Department of Energy (DOE), the Vermont State Colleges and others, construction was completed in early 2014 and the facility has been operational since April 2014. At full power, VTCAD uses 16,000 gallons of manure and organic residuals to produce 8,880 kilowatt hours (kWh) of electricity per day, ‘waste’ heat that will be used to heat four campus buildings, bedding material for the college dairy herds and recycled nutrients used as crop fertilizer. VTCAD uses a mixture of manure from co-managed farms and organic residuals collected from the community. Feedstock materials include brewery residuals, the glycerol by-product of biodiesel production from waste cooking oil, grease trap waste, and waste paper and, soon, locally collected pre- and post-consumer food residuals.

09 BIOMASS FUELS↗

Conceptual Biorefinery Design and Research Targeted for 2022: Hydrothermal Liquefacation Processing of Wet Waste to Fuels

The Department of Energy Bioenergy Technologies Office (BETO) invests in research and development of new pathways for commercially viable conversion of biomass into drop-in ready transportation fuels, fuel blendstocks and products. The primary emphasis has been on terrestrial and algae feedstocks, but more recently BETO has begun to explore the potential of wet wastes for biofuel production, with focus on wastewater residuals, manure, food waste, and fats, oils and grease. A recent resource analysis estimates that 77 million dry tons per year of these wastes are generated annually, 65% of which are underutilized for any beneficial purpose. Approximately 14 million dry tons of the total resource is wastewater residuals (sludge and biosolids) generated at the nation’s wastewater treatment plants (WWTPs). Conversion of this resource into transportation fuels could significantly contribute to the creation of a new domestic bioenergy and bioproduct industry, while providing an economically and environmentally sustainable alternative for current waste disposal practices. Hydrothermal liquefaction (HTL) is a process that uses hot, pressurized water in the condensed phase to convert biomass to a thermally stable oil product, also known as “biocrude”, which can then be thermo-catalytically upgraded to hydrocarbon fuel blendstocks. HTL is conceptually simple, has a high carbon efficiency, and can be applied to a wide range of wet feedstocks at similar processing conditions. The purpose of this report is to document the conceptual design, economics and supporting data for a sludge-to-fuel pathway via HTL and biocrude upgrading. The configuration includes a HTL plant that is co-located with a WWTP and a larger scale biocrude upgrading plant for production of hydrocarbon fuel blendstocks. Experimental data from bench scale testing of a 1:1 mixture of primary:secondary sludges are used to establish the economic and technical assumptions for the analysis. The design represents a goal case for the pathway, targeting performance that is anticipated to be achievable by 2022 with further research and development. The year 2022 is BETO’s target year for verification of hydrocarbon biofuel pathways. As this analysis represents a goal case, assumed values of several design parameters represent improvements in the technology relative to what has currently been demonstrated in the laboratory. While HTL is fairly well developed and may therefore be ready for commercialization prior to 2022, there are specific advancements addressed in this analysis that are necessary to enhance performance compared to what has been demonstrated to date. In addition, an important aspect to the pathway is the upgrading of biocrude to fuel blendstock, an area that has received much less attention and requires significant research to validate the goal case performance parameters. The estimated plant gate minimum fuel selling price for fuel blendstock from sludge HTL and upgrading is $3.46/gasoline gallon equivalent (gge). This price is within the tolerance (+$0.49/gge) of BETO’s $3/gge programmatic cost target and illustrates that fuel blendstocks generated from HTL of sludge and centralized biocrude upgrading have the potential to be competitive with fossil fuels. This analysis illustrates the feasibility of HTL for point-of-generation conversion of waste feedstock at a scale 1/20th that of the standard lignocellulosic biorefinery scale typically used in BETO design cases. The relevance of this work reaches beyond wastewater treatment sludge to lay the groundwork for application to other distributed wet wastes and blends that together represent a significant resource of underutilized biomass.

09 BIOMASS FUELS↗

Magnetostrictive Cold Spray Sensor Feasibility Assessment

Ultrasound sensors and inspection systems are frequently used to generate acoustic waves in metal structures capable of detecting and characterizing cracks, pits, erosion, inclusions, weld anomalies, and other material and structural features. One significant problem with piezoelectric transducers is the difficulty to achieve good coupling between the transducer and the surface being examined. This is particularly true in harsh conditions with high temperatures, cyclical hot and cold temperatures, highly radioactive fields found near nuclear reactors or spent nuclear fuel, caustic or corrosive fluids, and other extreme environmental conditions, as well as in long-term monitoring applications where repair or replacement of the sensor is difficult or expensive. Typically, coupling between the surface and the transducer is achieved with water, gel, grease, viscous shear coupling material, or pressure, which might not be possible or appropriate for long-term applications in which the impedance -matching materials wear away, evaporate, or simply stop functioning due to changes in surface conditions. Fluid couplings can evaporate or drain away from the transducer-substrate interface; glue- based couplings may foul or fail and are notoriously unreliable at high temperatures and in radioactive environments. This work explores the behavior of a magnetostrictive cold-spray patch that is metallurgically bonded to a stainless steel inspection target surface, and compares it to the performance of a standard adhesively-bonded ferrous-cobalt magnetostrictive strip solution. Cold-spray is a coating process where 10 –100 micron diameter powdered metal is accelerated to Mach 2 to Mach 3 (2–3 × speed of sound) and impacted on the surface to be coated. Each powder particle forms a kinetic bond with the substrate or other coating particles to produce a metallurgically bonded layer. If the powder is nickel or cobalt with high magnetostrictive coefficients, this surface can serve as the base of a magnetostrictive sensor suitable for crack or pitting-damage inspection and monitoring that is not subject to temporal or environmental degradation.

47 OTHER INSTRUMENTATION↗

Analysis of Gas Samples Taken from the High Burnup Demonstration Cask

The High Burn-Up Demonstration Project was recently initiated by the Department of Energy (DOE) to evaluate the effects of fuel drying and long term dry storage on high burn-up spent nuclear fuel. As part of the project, samples of the He backfill gas were collected 5 hours, 5 days, and 12 days after completion of drying. The samples provide information on the state of the fuel at closure, and on the environment within the cask. At Sandia National Laboratories, the samples were analyzed by gamma-ray spectroscopy to quantify fission product gases and by gas mass spectrometry to quantify bulk and trace gases; water content was measured via humidity probe. Gamma-ray spectroscopy results indicated no detectible 85 Kr, indicating no failed fuel rods were present after drying. Mass spectrometry indicated build-up of CO 2 to 930 ppmv over two weeks, attributed to oxidation of organic compounds (possibly vacuum grease or vacuum pump oil) within the cask. H 2 , generated by either radiolysis or metal corrosion, also increased up to —500 ppmv. Water contents in the cask were higher than anticipated, increasing to —17,400 ppmv ±10% after 12 days. Measuring water content proved challenging, and possible improvements to the method for future analyses are proposed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Catalytic Upgrading of Thermochemical Intermediates to Hydrocarbons (Final Report)

A lot of activity in catalytic pyrolysis and hydroprocessing occurred in the past 10-15 years with notable successes and failures; however, very little technical information is available in the open literature from pilot-scale studies such as those performed in this project. Besides, the next step along the technology commercialization pathway is to scale-up the catalytic biomass pyrolysis process, integrate this technology with a hydroprocessing unit, and demonstrate the long-term operation and performance of the integrated process; notably, these were achieved in this project. RTI International has developed a single-step catalytic biomass pyrolysis process to produce a hydrocarbon-rich bio-crude intermediate. This bio-crude is more thermally stable and has lower oxygen content than conventional biomass fast pyrolysis oil, so it can be effectively and efficiently upgraded with traditional hydroprocessing technology to produce gasoline and diesel. Our partner, Haldor Topsøe, has developed a strategy for hydroprocessing bio-crude intermediates based on extensive catalyst and process development in support of converting vegetable oils and waste greases into high-quality diesel fuel. The goal of the originally proposed project was to demonstrate an advanced biofuels technology that integrates a catalytic biomass pyrolysis step and a hydroprocessing step to produce infrastructure-compatible biofuels. The specific technical goals of this project were 1) to optimize the catalytic biomass pyrolysis process to achieve high degree of deoxygenation, while maximizing the bio-crude production, 2) improve bio-crude thermal stability, 3) evaluate the impact of bio-crude quality in the hydroprocessing step, 4) minimize hydrogen demand of the integrated process, and 5) maximize biofuels yields. This project showed that it is technically feasible to use non-zeolitic solid acid catalyst to consistently generate bio-crude with 20% oxygen content and that these liquids can be effectively hydrotreated into low oxygen fuel blendstocks. The reproducibility of the small-scale pyrolysis yields at the 1 tonne/day scale is an achievement worth noting and the effect of pyrolysis temperature on biocrude yields and quality was investigated at the pilot scale. Additionally, advanced analytical techniques were used to analyze bio-crude to investigate the effect of process conditions and feedstock on the concentration and speciation of oxygen-containing compounds. Insights into the impact of oxygen content and oxygen speciation on bio-crdue upgrading were also sought. Clearly, more successful upgrading correlated with bio-crudes with lower oxygen content. This was most evident when partially upgraded bio-crude with 55-90% less oxygen compared to the starting bio-crude was blended with straight run diesel and hydrotreated without any noticeable increase in pressure drop across the reactor or any measurable loss of hydrodenitrification (HDN) activity. Minimizing hydrogen demand while maximizing biofuels yield are the desired outcomes for the integrated process. In summary, several technical challenges remain before catalytic biomass pyrolysis becomes a commercial reality, most notably bio-crude yields and quality still need to be improved. The integrated catalytic biomass pyrolysis hydroprocessing scheme being developed produces intermediates that can be refined for use as drop-in hydrocarbon replacement fuels. From a technology perspective, this advanced biofuel technology produces liquid transportation fuels that can leverage capital expenditures in the existing petroleum refining and distribution infrastructure. From a business perspective, this technology does not face potential market limitations as other nonhydrocarbon biofuels caused by oxygenated blending limitations and fuel certification for light-duty vehicle applications.

09 BIOMASS FUELS↗

FLC Notable Technology Award Oleo-Furan Surfactant

It’s a well-kept secret that laundry detergents are harmful to the environment. The important chemical in laundry detergent, called a surfactant. Surfactants are the workhorses of laundry detergent and soaps, and they're attracted to things like grease on your hands and dirt in your clothes to wash them away. Surfactants are used in everything from shampoo, hand soap, laundry detergent, and cosmetics. Many current surfactants are made from petroleum feedstock. These petroleum-derived building blocks come with a big carbon footprint. As the need for greener feedstock alternatives for synthesizing surfactants became obvious, manufacturers turned to natural oils, such as palm kernel and coconut oil. However, these oils are costly, particularly in areas where they are not domestically produced, and using them for surfactant synthesis competes with the food supply chain. Surfactants deactivate and do not work in hard water. Hard water is common - 85% of the U.S. water supply is considered hard because of the presence of small metal ions. These metal ions cover the surfactants making them useless. To solve this problem, many manufacturers add chemicals called chelators to bind the metal ions and make the water less hard, enhancing the effectiveness of the laundry detergent. However, this solution leads to more problems, including increased cost of detergent production and a large output of environmentally harmful chemicals. There remains a strong need for effective laundry detergents that do not negatively impact the environment and are available to consumers at an affordable cost. The American Cleaning Institute (ACI), a surfactant manufacturer organizing body, is emphasizing commitment to developing bio-renewable alternatives to current surfactants in laundry detergents. That’s why chemists at SIRONIX Renewables partnered with Los Alamos National Laboratory to further develop Oleo-furan surfactants (OFS). OFS are a new class of non-toxic, non-irritating surfactants for laundry detergent. It is the only surfactant that performs effectively in cold and hard water without chelators to bind the metal ions in hard water. OFS can be produced readily from sustainable, bio-derived molecules. They are multi-functional molecules - performing the role of a surfactant and a chelator in one - and are completely bio-degradable. OFS does not rely on petroleum feedstock and is synthesized from non-food, bio-renewable cellulosic feedstock. OFS solves each of the pertinent problems facing detergents and our environment today.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resource Recovery and Environmental Protection in Wyoming’s Greater Green River Basin Using Selective Nanostructured Membranes (Final Report)

Produced water (PW) represents a sizable waste stream that is co-generated with oil and natural gas production. In 2021 Wyoming ranked 8th and 9th, respectively in domestic oil and natural gas production. In 2017 Wyoming ranked as the 4th highest generator of PW in the U.S, accounting for 7% of the total volume generated. In the context of being the 3rd most arid state in the U.S., the value of water reuse becomes obvious. PW reuse, and resource recovery, in any form requires some level of treatment to remove particulates, residual (free, dispersed) hydrocarbons, organics, and salts. The level of treatment depends on the requirements of the reuse, or resource recovery, application. PW management systems in Wyoming employ in order of volume of PW managed the following management strategies: reinjection for enhanced oil recovery, surface discharge, deep well injection, evaporation ponds (impoundments), and commercial management/treatment. Complicating treatment efforts are the relatively high concentrations of organics (natural and synthetic), dispersed/free hydrocarbons, benzene-toluene-ethylbenzene, and xylenes (BTEX) compounds, biologicals, salts, and minerals. Hydrocarbons (dispersed/dissolved crude oils) and BTEX compounds, as well as synthetic organics, present economic and environmental concerns. The former represents lost revenue, while the latter results in negative environmental impacts like emissions from surface impoundments. The overall objective of this proposal was to synthesize superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes for selectively concentrating and then separating BTEX compounds and oil and grease (O&G) from PW originating from the Greater Green River Basin (GGRB) in Wyoming. Three specific research aims were pursued to accomplish this overall objective. This final report details the development of the superhydrophobic and superhydrophilic membranes, as well as the design of the membrane module prototypes specifically. The technoeconomic assessment is separately reported in another document. 1. Aim #1 – Material optimization and performance evaluation of superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes made by electrospinning/spraying. 2. Aim #2 – Design and construction of cross-flow membrane modules for selectively concentrating and then separating BTEX/oil from GGRB produced water. 3. Aim #3 – Techno-economic assessment of BTEX/oil recovery, and clean water production, using superhydrophilic/oleophobic and superhydrophobic/oleophilic membrane separation for GGRB PW. Superhydrophobic membranes were synthesized by electrospinning poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers onto polyester (PET) substrates and electrospraying nano-carbon black/PVDF-HFP onto the nanofibrous layer. These membranes were characterized by high (>8000 liters per square meter per hour per bar (LMH/bar)) permeance values for pure hydrocarbon phases and a high hydrocarbon selectivity (>96%) when treating GGRB PW. All results were obtained when operating the membrane in a crossflow configuration representative of actual field operating conditions. Solvent/oil properties, specifically viscosity and total surface energy/tension, affected permeance across the membrane, which resulted in light mineral oil (394 LMH/bar) and o-xylene (1834 LMH/bar) being characterized by lower permeance values in the pure phase tests. Mixed phase fluxes between 40 to 80 LMH were obtained for the PW when operating the membrane at a feed pressure of 0.3 bar. Flux decreased as the mixed phase concentration in the feed decreased pointing to the importance of maximizing the collision efficiency between the emulsion and the membrane surface and maximizing the emulsion concentration in the feed and the turbulence within the feed channel. These tests demonstrated that the superhydrophobic membranes developed here are a viable hydrocarbon recovery method for GGRB PWs and should be pursued for testing in pilot-scale trials. Superhydrophilic membranes were successfully synthesized via electrospinning/spraying using polyacrylonitrile (PAN) nanofibers as a base nanofibrous matrix. Integration of polyaniline (PANI) into the nanofibrous matrix produced a superior membrane, for water filtration applications, relative to PAN alone and reduced graphene oxide (RGO) when integrated into the nanofibrous matrix. This conclusion was based on the PANI-PAN resistance to flux loss (fouling) when treating model solvent/oil solutions representative of GGRB PWs and field collected PW from the GGRB. The synthesized PAN membranes outperformed a commercially available PAN membrane designed for oil/water separation. This finding indicates that the surface chemical and physical characteristics of the electrospun membranes presents improved properties for filtration of challenging waters like GGRB PWs. The electrospun membranes therefore show promise overall as a substitute for conventionally polymerized membranes in PW treatment applications. The PANI-PAN membrane specifically presents superior performance characteristics for concentration O&G prior to treatment by the hydrocarbon recovery membrane and producing high-quality filtrate for reuse and/or additional treatment (desalination).

02 PETROLEUM↗

Cryo-GCMS Outgassing Screening: Thermal Filler Materials

A study was conducted to investigate the outgassing characteristics of four thermal filler materials. The purpose of this screening was to identify any outgassing products that might be considered reactive, specifically compounds that could result in corrosion in the systems where these materials are used. A range of compounds was observed in the sample headspaces, though most do not stand out as being known reactive species of concern. However, several halogenated compounds and sulfurous compounds- classes compounds known to facilitate corrosion reactions under certain conditions- were observed in low concentrations. The TFLEX 760 exhibited the highest total outgassing, while the GR130 had the lowest. Therm-a-Gap75 and the Si thermal grease exhibited very similar outgassing profiles. It is difficult to predict the extent to which any given compound observed in an analysis of this type might pose a risk in an actual system; factors such as temperature, system geometry, concentration, and gas conductance all play a role in the kinetics governing chemical reactions. It is recommended that the results of these analyses are shared with pertinent materials SMEs familiar with the system(s) in question to evaluate potential risks.

36 MATERIALS SCIENCE↗

Rheology of a Wet Waste Feedstock

The current study provides rheological characterization of a representative HTL feedstock, Wet Waste Feedstock # 22 (WW22), as a function of HTL-prototypic temperature and shear rates. Feed WW22 is derived from a regionally representative blend of food, waste water sludges, and FOG (fats, oils, and greases). Rheological characterization of WW22 as a function of temperature provides, in part, key information for development and economic assessment of HTL wet waste slurry handling and heating operations, which may facilitate improved design rigor and optimization of HTL unit operations.

09 BIOMASS FUELS↗