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At least 19 records

Supercritical waste oxidation of aqueous wastes

For aqueous wastes containing 1 to 20 wt% organics, supercritical water oxidation is less costly than controlled incineration or activated carbon treatment and far more efficient than wet oxidation. Above the critical temperature (374 C) and pressure (218 atm) of water, organic materials and gases are completely miscible with water. In supercritical water oxidation, organics, air and water are brought together in a mixture at 250 atm and temperatures above 400 C. Organic oxidation is initiated spontaneously at these conditions. The heat of combustion is released within the fluid and results in a rise in temperature 600 to 650 C. Under these conditions, organics are destroyed rapidly with efficiencies in excess of 99.999%. Heteroatoms are oxidized to acids, which can be precipitated out as salts by adding a base to the feed. Examples are given for process configurations to treat aqueous wastes with 10 and 2 wt% organics.

Modell, M.↗

Nutrient Capture from Aqueous Waste and Photocontrolled Fertilizer Delivery to Tomato Plants Using Fe(III)–Polysaccharide Hydrogels

Inexpensive and sustainable methods are needed to reclaim nutrients from agricultural waste solutions for use as a fertilizer while decreasing nutrient runoff. Fe(III)–polysaccharide hydrogels are able to flocculate solids and absorb nutrients in liquid animal waste from Confined Animal Feeding Operations (CAFOs). Fe(III)–alginate beads absorbed 0.05 mg g –1 NH 4 + and NO 3 - from 100 ppm solutions at pH = 7, with > 80% phosphate uptake and ~30% uptake of ammonium and nitrate. Ammonium uptake from a raw manure solution (1420 ppm NH 4 + ) showed a significant 0.7 mg g –1 uptake. Tomato plant trials carried out with Fe(III)–alginate hydrogel beads in greenhouse conditions showed controlled nutrient delivery for the plants compared to fertilizer solution with the same nutrient content. Plants showed an uptake of Fe from the gel beads, and Fe(III)–alginate hydrogel beads promoted root growth of the plants. The plants treated with nutrient-loaded Fe(III)–alginate hydrogels yielded comparable tomato harvest to plants treated with the conventional fertilizer solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of Technologies for Destruction of LDR Organics in Hanford Tank Waste

Aqueous Hanford tank wastes contain soluble organics and some tanks contain small amounts (<100 mg/L) of organics that are regulated under the Land Disposal Restrictions (LDR) portions of the Resource Conservation and Recovery Act (RCRA). Most of these organics can be removed by evaporation, but some are not. Methods to destroy/remove organics that are regulated by the LDR section of the RCRA and that are not removed by evaporation may be needed if ambient temperature waste treatment processes are used to immobilize aqueous Hanford tank wastes. To identify viable and compatible organic removal or destruction pretreatment methods an evaluation was performed by a team of researchers. The team utilized a Systems Engineering Approach that examines all aspects of the technology, based on information available in the literature and the experience of the team members. That evaluation led to recommendations by the team to perform testing on technologies to determine efficacy in destroying organics in Hanford tank waste liquids. The primary technologies recommended are chemical oxidants, including permanganate, peroxymonosulfate or peroxydisulfate (PMS/PDS), hydrogen peroxide, and ozone. Ultraviolet light irradiation of the stream with a solid catalyst sorbent is also recommended for testing. A generalized description of the test program is also included.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electrocatalytic Valorization into H2 and Hydrocarbons of an Aqueous Stream Derived from Hydrothermal Liquefaction

Electrocatalytic oxidation is an attractive process for valorizing the carbon and removal of nitrogen present in the aqueous waste streams at ambient conditions. Here, we evaluated the electrocatalytic oxidation as a function of applied potential over a commercial Pt electrode of aqueous waste stream generated via hydrothermal liquefaction. We validated the conversion of quantifiable carbon (e.g., carboxylic acids, alpha hydroxyacids, alcohols, ketones, amides) and unquantifiable carbon as well as nitrogen removal. The unquantifiable carbon was valorized to quantifiable short chain organic molecules (e.g., acetic). Model studies showed that carboxylic acids, alcohol and ketones converted following (non-) Kolbe chemistry. Amides and alpha hydroxyacids formed carboxylic acids that subsequently converted via (non-) Kolbe chemistry. Ammonia was oxidized into N2. The reaction rate varied for each molecule family with carboxylic acids and ammonia having the highest reaction rates. The main reaction products from the electrocatalytic oxidation at the anode were volatile, short chain hydrocarbons (i.e., olefins, paraffins) and CO generated via Kolbe chemistry, while H2 was generated at the cathode. The parallel denitrification, valorization of carbon, and H2 generation of the aqueous waste can replace and simplify the current unit operations used in a commercial hydrothermal liquefaction process. The high operation potential required to drive the electrocatalytic reaction is responsible for high operation costs; however, they can be either partially subsidized with sale of excess H2 at the current DOE goal of $2/kg H2. Thus, the present work shows how electrocatalytic oxidation can be used to valorize aqueous waste streams into volatile hydrocarbons and H2.

Electrocatalytic oxidation, Aqueous waste valoriza↗

Supercritical Water Oxidation and a Preliminary Concept for Lunar Application

Abstract: Water is a critical resource for crewed space exploration missions and reclamation of aqueous waste streams presents the only long-term viable option. Although early Artemis missions are considering water as part of the payload manifest, it would be extremely advantageous if follow-on missions were supplied—either in total or in part—by a reclamation technology that would operate autonomously between missions. An attractive technology is currently under ongoing research at NASA Glenn Research Center (GRC) that employs a Supercritical Water Oxidation (SCWO) process to destroy all hydrocarbons in the waste stream. Testing of an aqueous waste stream simulant, typical of what is generated on the International Space Station (ISS), has shown reductions in Total Organic Carbon (TOC) of greater than 99% with reactor residence times less than 30 s. Recent effort has been directed toward developing a conceptual design based on the current tubular reactor used in the evaluation of the conversion of SCWO. This conceptual design along with the results of recent SCWO conversion experiments will be presented. Recent design enhancements to achieve shorter residence times along with “production simulation” tests will be presented. The diagnostics used in assessing the extent of the waste conversion include a total organic carbon (TOC) analysis, Raman analyses, and measurements of pH, turbidity, and conductivity. Results obtained from the modified reactor configuration will also be compared to those of the Phase I configuration presented in earlier work.

SCWO↗

Development of a Sulfur Tolerant CHG Process (CRADA 442) (Final Report)

The Pacific Northwest Laboratory (PNNL) has developed the Catalytic Hydrothermal Gasification (CHG) technology, which can convert low-value organics dispersed in aqueous streams, such as the aqueous phase byproduct from hydrothermal liquefaction (HTL) of wet wastes, to a mixture of methane, H 2 , and CO 2 . The current CHG catalyst, ruthenium (Ru) on a graphite substrate, was selected for its effectiveness as a reducing catalyst. However, the target waste aqueous feedstock, the HTL aqueous phase from wet wastes, such as sewage sludge, contains a fair amount of sulfur in both organic and inorganic forms. Like many other reduced metal catalysts, Ru is deactivated or poisoned by exposure to sulfur, among other contaminants. In general, a deactivated Ru catalyst cannot be reactivated or restored except by removing and returning it for remanufacturing. Therefore, there is an urgent need for a sulfur-resistant catalyst to enable CHG processing of the HTL aqueous waste stream. PNNL, with support from SoCalGas CRADA, has developed a sulfur resistant CHG catalyst and demonstrated a stable CHG process for converting HTL aqueous phases from wet wastes. Here, we report the major accomplishments of the project: • We have demonstrated that sulfided Ru based catalysts is stable during CHG of HTL aqueous waste stream, with a requirement of activity improvement. • We have developed a new catalyst, with 0.5-2 wt.% Ru loading, showing better activity compared to the baseline 6.7 wt.% RuSx/C catalyst. • With the new catalysts, the single-pass COD reduction is approximately 60% and two-pass COD reduction can reach approximately 85%. • The process is robust in terms of being effective across a wide range of organic species in the feedstock. • Techno-economic analysis was conducted to evaluate the economic impact of catalyst advancement and identify further improvement requirements. This type of catalyst shows great potential to be efficient and robust for CHG with low catalyst cost.

03 NATURAL GAS↗

Glass formulation and lab-scale testing of glasses designed for in-can Melter and in-container Vitrification of high-assay low-enriched uranium aqueous polishing Raffinate waste

Glasses were designed for processing a nuclear waste from aqueous polishing of high-assay low-enriched uranium using either In-Can Melter (ICM) or GeoMelt® In-Container Vitrification™ (ICV) technologies, which operate at temperatures of T p ≤ 1100 °C and T p ≤ 1450 °C, respectively. Due to the different operating conditions, the melt and glass properties were optimized differently for each technology. Each glass was designed to optimize for maximum waste loading while simultaneously satisfying processing (e.g., crystallization, viscosity, and conductivity) and product quality (e.g., durability, hazard characteristic, and crystal content) constraints. Here, the raffinate waste contains high nitric acid (4 M) and low total solids (9 g·L -1 ) concentrations. Feed preparation processes were tested to facilitate concentration and nitrate destruction/removal while controlling redox of the melter feed. A successful feed process including sugar addition and spray-drying was performed to generate an adequate melter feed for ICV processing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Green hydrogen from microalgal liquefaction byproducts with ammonia recovery and effluent recycle for developing circular processes

Hydrothermal liquefaction is a promising technology for microalgae-based biofuel production. However, hydrothermal liquefaction’s aqueous wastes have little established reuse, and contain significant fractions of toxic ammoniacal nitrogen. Careful reuse of this waste can assure microalgae-based biofuels are produced with less environmental impact and larger energy efficiency. Microbial electrolysis cells were investigated to valorize this waste product by converting the leftover organics into hydrogen and remove ammonia. Waste hydrothermal liquefaction aqueous phase from two microalgal strains, Tetraselmis sp. and Chlorella sp. were used as feedstocks for hydrogen production in microbial electrolysis cells. Chlorella and Tetraselmis aqueous phase-fed microbial electrolysis cells reach an average current density of 5.1 ± 0.19 A/m 2 and 3.8 ± 0.08 A/m 2 . Compound removal rates and mass removal percentages were also investigated for each feedstock. Additionally, acetic acid, propionic acid, ethanol, and glycerol were effectively removed from the aqueous byproduct. Further, microbial electrolysis cells separated up to 34.3% of ammoniacal nitrogen present in the aqueous phase. Charge transfer analysis indicated that proton transfer, not ammonium transfer, contributed to the majority of the hydrogen production in the cathode. Finally, the microbial electrolysis cell effluent was reused to grow the same microalgal strains, leading to the development of a circular biofuel production system. Microalgae regrowth studies using microbial electrolysis cell effluent showed nearly complete removal of total organic carbon, but significantly less removal of total nitrogen. Tetraselmis sp. growth occurred with the Tetraselmis-derived MEC effluent, however, the control medium without effluent produced the most growth. These findings support the possibility of a circular biofuel framework using MECs, but additional constraints, including the removal of inorganic contaminants, are necessary to realize the circular processes.

09 BIOMASS FUELS↗

Results for the First Quarter Calendar Year 2021 Tank 50 Salt Solution Sample

Tank 50 aqueous waste is analyzed on a quarterly basis and the results are compared to the Waste Acceptance Criteria (WAC) of the Z-Area Saltstone Production Facility (SPF). The information from this characterization will be used by Savannah River Remediation (SRR) for the transfer of aqueous waste from Tank 50 to SPF, where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF WAC Limits and Targets. A memorandum reporting the average Cs-137 value and comparison to WAC Limits has been previously issued.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Bioconversion of Thermochemical Intermediates

Thermochemical (TC) biofuels production via both pyrolysis and hydrothermal liquefaction produces aqueous waste streams, typically with organic compounds at concentrations of -50-100 g/L. These streams represent a wastewater treatment cost and carbon loss for the TC biorefinery, but the concentration range for these compounds is ideal for bioconversion. To that end, the Bioconversion of Thermochemical Intermediates (BTI) project is developing advanced analytics and engineered microbes to convert these waste streams to co-products, with the overall aim of improving the economics and carbon conversion efficiency of TC biorefining. To date, we have primarily focused on development of advanced analytical chemistry approaches to fully characterize TC aqueous streams and engineering of Pseudomonas putida for conversion of non-conventional substrates, including methylated phenolics, cyclic ketones, furans, and C1-C3 light oxygenates, into atom-efficient products. Two primary challenges are the rapid deployment of aqueous-compatible analytics to changing upstream conditions and dealing with the toxicity of the feed streams to engineered microbes. The project efforts have resulted in engineered strains of P. putida able to consume 90% of the organic compounds in aqueous waste streams from catalytic fast pyrolysis, more than 300-fold toxicity tolerance improvements in P. putida, and carbon closures exceeding 90% for TC wastewater streams across multiple processing technologies.

BASIC BIOLOGICAL SCIENCES,BIOMASS FUELS↗

Selective permeation up a chemical potential gradient to enable an unusual solvent purification modality

The need for energy-efficient recovery of organic solutes from aqueous streams is becoming more urgent as chemical manufacturing transitions toward nonconventional and bio-based feedstocks and processes. In addition to this, many aqueous waste streams contain recalcitrant organic contaminants, such as pharmaceuticals, industrial solvents, and personal care products, that must be removed prior to reuse. We observe that rigid carbon membrane materials can remove and concentrate organic contaminants via an unusual liquid-phase membrane permeation modality. Surprisingly, detailed thermodynamic calculations on the chemical potential of the organic contaminant reveal that the organic species has a higher chemical potential on the permeate side of the membrane than on the feed side of the membrane. This unusual observation challenges conventional membrane transport theory that posits that all permeating species move from high chemical potential states to lower chemical potential states. Based on experimental measurements, we hypothesize that the organic is concentrated in the membrane relative to water via favorable binding interactions between the organic and the carbon membrane. The concentrated organic is then swept through the membrane via the bulk flow of water in a modality known as “sorp-vection.” We highlight via simplified nonequilibrium thermodynamic models that this “uphill” chemical potential permeation of the organic does not result in second-law violations and can be deduced via measurements of the organic and water sorption and diffusion rates into the carbon membrane. Moreover, this work identifies the need to consider such nonidealities when incorporating unique, rigid materials for the separations of aqueous waste streams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solidification of REDC Organics and Airborne Release Fraction Measurements

The Radiochemical Engineering Development Center (REDC) generates various liquid organic wastes from processing irradiated targets to recover heavy elements. In the past, these organics were discharged to the Oak Ridge National Laboratory (ORNL) liquid low-level waste (LLLW) system, along with the aqueous waste. Because of a reduction in aqueous LLLW from other ORNL generators and an increase in the radionuclide concentration, particularly 238 Pu, in the organic waste stream, the organics can no longer be discharged to the LLLW system. The plan is to solidify the liquid organic waste for disposal as solid debris waste. The documented safety analysis for REDC uses an airborne release fraction of 5 x 10 -4 with a respirable fraction of 0.2 for plutonium and other actinides from packaged solid debris waste during a fire scenario, for an overall airborne release fraction/respirable fraction of 10 -4 . Solidifying the organic liquids, either by using PM-199 Organoclay ® or by grouting, would produce solid waste forms with no free liquid, which should qualify for disposal at the Waste Isolation Pilot Plant. The use of Organoclay would be much simpler to implement inside a hot cell. Granular Organoclay can be added to the organic waste solutions until there is a dry layer on top of the liquid and then allowed to cure for a few hours. Grouting the liquids would require using multiple ingredients and mixing steps. Both methods produced waste forms that trapped cerium, as a surrogate for plutonium, inside the waste, with airborne release fractions during fire scenario tests of well below the 10 -4 limit.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solidification of REDC Organics For Disposal As Solid Waste

The Radiochemical Engineering Development Center (REDC) generates various liquid organic wastes from processing irradiated targets to recover heavy elements. In the past, these organics were discharged to the Oak Ridge National Laboratory (ORNL) liquid low-level waste (LLLW) system, along with the aqueous waste. Because of a reduction in aqueous LLLW from other ORNL generators and an increase in the radionuclide concentration, particularly 238 Pu, in the REDC organic waste stream, the organics can no longer be discharged to the LLLW system. The plan is to solidify the liquid organic waste for disposal as solid waste. Solidifying the organic liquids using PM-199 Organoclay ® would produce solid waste forms with no free liquid, which should qualify for disposal at the Waste Isolation Pilot Plant. Granular Organoclay can be added to the organic waste solutions until there is a dry layer on top of the liquid and then allowed to cure for a few hours to produce a solid wasteform.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Biosorption of copper from aqueous solutions utilizing agricultural wastes

Abstract The purpose of this study was to determine the copper (Cu) biosorption capacities of several agricultural wastes from aqueous solutions. Samples of agricultural wastes were tested unaltered and after hydrochloric acid (HCl) treatment. Additional parameters tested include sample dose, contact time, particle size, mixing temperature, and the concentrations and pH of the Cu solutions. Desorption studies were performed to determine if the removed Cu could be recovered. In addition, tests were conducted to determine if the agricultural waste samples (AWS) could be reused for additional Cu biosorption cycles. The results of this study demonstrate a wide range of Cu biosorption proficiencies ranging from 0% to 100% removal. The parameters that resulted in higher Cu removal include higher pH and lower Cu solution concentration. Desorption results showed a 58% to 86% Cu recovery rate. Three of the five reused AWS were effective at removing Cu during subsequent trials. Therefore, these AWS types can be reused for additional Cu biosorption cycles. Hence, it is possible that using those AWS for metal treatment could reduce hazardous waste disposal inefficiencies and costs by avoiding disposing of spent AWS following each Cu biosorption cycle.

Rizzuti, Anthony M.↗

Lyophilization for Water Recovery From Solid Waste

This abstract describes the development of a solid waste treatment system designed for a near term human exploration mission. The technology being developed is an energy- efficient lyophilization technique that recovers water from spacecraft solid waste. In the lyophilization process water in an aqueous waste is frozen and then sublimed, resulting in the separation of the waste into a dried solid material and liquid water. This technology is ideally suited to applications where water recovery rates approaching 100% are desirable but production of CO, is not. Water contained within solid wastes accounts for approximately 3% of the total water balance. If 100% closure of the water loop is desired the water contained within this waste would need to be recovered. To facilitate operation in microgravity thermoelectric heat pumps have be used in place of traditional fluid cycle heat pumps. A mathematical model of a thermoelectric lyophilizer has been developed and used to generate energy use and processing rate parameters. The results of laboratory investigations and discussions with ALS program management have been used to iteratively arrive at a prototype design. This design address operational limitations which were identified in the laboratory studies and handling and health concerns raised by ALS program management. The current prototype design is capable of integration into the ISS Waste Collection System.

Flynn, Michael↗

October 2025 Semiannual Composite Salt Waste Processing Facility Decontaminated Salt Solution Toxicity Characteristic Leaching Procedure Results

The aqueous waste from the Salt Waste Processing Facility is sampled semiannually for transfers to the Saltstone Disposal Facility. Salt solution is treated at the Saltstone Production Facility and disposed of in the Saltstone Disposal Facility. Per request of customer, X-TTR-Z-00027, Revision 0, one Saltstone Processing Facility Decontaminated Salt Solution and Z area premix material for the October 2025 semiannual Toxicity Characteristic Leaching Procedure sample. The sample contained 60:40 (by weight) of slag and fly ash (referred to as the “Cement-Free grout sample”). Results from the technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request prepared by Savannah River Mission Completion. At 51 days cured, the Saltstone sample was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure. The October 2025 Semiannual Cement-Free grout sample met 61 79.268.48 requirements for a non-hazardous waste form with respect to the Resource Conservation and Recovery Act metals and Underlying Hazardous Constituents and met the Saltstone Production Facility Waste Acceptance Criteria that was in effect at the time of the sample collection at the Salt Waste Processing Facility.

Hsieh, Madison [Savannah River National Laboratory↗

Lyophilization -Solid Waste Treatment

This paper discusses the development of a solid waste treatment system that has been designed for a Mars transit exploration mission. The technology described is an energy-efficient lyophilization technique that is designed to recover water from spacecraft solid wastes. Candidate wastes include feces, concentrated brines from water processors, and other solid wastes that contain free water. The system is designed to operate as a stand-alone process or to be integrated into the International Space Station Waste Collection System. In the lyophilization process, water in an aqueous waste is frozen and then sublimed, separating the waste into a dried solid material and liquid water. The sublimed water is then condensed in a solid ice phase and then melted to generate a liquid product. In the subject system the waste solids are contained within a 0.2 micron bio-guard bag and after drying are removed from the system and stored in a secondary container. This technology is ideally suited to applications such as the Mars Reference Mission, where water recovery rates approaching 100% are desirable but production of CO2 is not. The system is designed to minimize power consumption through the use of thermoelectric heat pumps. The results of preliminary testing of a prototype system and testing of the final configuration are provided. A mathematical model of the system is also described.

Litwiller, Eric↗