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At least 73 records · Page 4

Continuous recovery of high-purity Kraft lignin from black liquor via simultaneous, liquid-phase acidification and purification

Here, a key advantage of the Sequential Liquid-Lignin Recovery and Purification (SLRP) process for the recovery of lignin from Kraft black liquor is the precipitation of a solvated, “liquid-lignin” phase (vs. the typical solid) during the CO 2 acidification step. Here, we have discovered that this lignin can also be maintained in a solvated state during the H 2 SO 4 acidification step if aqueous acetic acid from the Aqueous Lignin Purification with Hot Agents (ALPHA) process is incorporated into the H 2 SO 4 solution. As the liquid-lignin is converted from its salt form at pH = 9.5 to its acid form at pH = 2.5, the lignin initially solvated with water becomes solvated and thus liquefied with the organic–water solution. Maintaining the lignin in a solvated liquid state has two advantages: (1) the entire SLRP + ALPHA process, from starting black liquor to final lignin product, can be operated continuously; and (2) mass transfer of metals impurities out of the liquid-lignin phase is significantly enhanced, resulting in both a cleaner Kraft lignin product (~2000 ppm Na and 0.5-1.0 % ash) and reduced water washing.

09 BIOMASS FUELS↗

Flume and single-pass washing systems for fresh-cut produce processing: Disinfection by-products evaluation

Free chlorine is widely used in fresh-cut produce washing to minimize microbial cross-contamination, but its application can also lead to the formation of harmful disinfection byproducts (DBPs). This study compared DBPs in process water and washed produce during commercial operation. Samples of shredded lettuce and diced cabbages washed in chlorinated water in the traditional double-flume wash and novel immersion-free single-pass wash systems were collected at multiple time points and locations from the processing lines. A suite of 33 conventional and emerging DBPs, including 4 trihalomethanes (THMs), 9 haloacetic acids (HAAs), 9 nitrogenous DBPs (N-DBPs), and 11 carbonaceous DBPs (C-DBPs), were investigated. Overall, N-DBPs and HAAs dominated the concentration of detected DBPs. Wash water in the flumes contained 7–111 folds higher DBP levels compared to that in the single-pass system, with the abundance of DBPs following the order of N-DBPs > HAAs > C-DBPs > THMs. DBPs were detected on washed produce, presenting primarily in the forms of N-DBPs and HAAs followed by C-DBPs and THMs. While higher levels of DBPs were detected in flume-washed produce, the final potable water rinse significantly reduced the DBP concentration in these products. The concentrations of THMs and HAAs on these washed products were used to estimate potential exposure via consumption of fresh-cut produce and the levels were below the daily allowable exposure for drinking water standard established by the U.S. Environmental Protection Agency. The detected high concentration and potential toxicity of N-DBPs indicate the need for further research. Here, the findings of this study advance the understanding of the formation and removal of DBPs during wash processes, and identify additional research opportunities for further reduction in DBPs and food safety improvement.

59 BASIC BIOLOGICAL SCIENCES↗

Adapting LEU-Modified Cintichem Process for Processing Up to 750 Grams of Uranium Targets

Argonne National Laboratory (Argonne) developed a low-enriched uranium (LEU)-modified Cintichem (LMC) process to enable production and purification of fission-produced molybdenum-99 (Mo-99) from LEU foil targets. This separation scheme starts with nitric acid (HNO 3 ) dissolution of irradiated LEU foil targets that yields an approximate final volume of 2 L. The dissolved uranium solution containing fission products, including Mo-99, is then treated by loading the solution on a titania-based recovery column to separate Mo-99 from bulk uranium. After several washing steps, Mo and other fission products are stripped from the titania column using sodium hydroxide (NaOH). The eluate is then acidified using nitric acid and subsequently processed for final purification using the LMC process. Uranium and most fission products are not adsorbed on the titania column but are eluted (i.e., removed using a solvent) during the wash steps; they can be purified and recycled into new uranium targets.

07 ISOTOPE AND RADIATION SOURCES↗

Desalting biocrude for improved downstream processing toward marine fuel application

Hydrothermal liquefaction of wet wastes (e.g., food waste and sewage sludge) offers a promising avenue for producing biocrude, but the resulting product is often contaminated with metals and water, impacting the biocrude upgrading steps to produce final fuel (e.g., jet and diesel). Here this study investigates the use of aqueous solutions of formic acid for desalting biocrudes and improving their quality. The results show that this approach significantly reduces both metal and water content, enabling mild hydrotreatment with reduced hydrogen consumption to further enhance the biocrude's quality. A preliminary technoeconomic analysis based on these experimental results shows that even without optimization, this washing process can yield biocrude with a minimum selling price of $1.87/GGE. Overall, our study demonstrates the potential for using dilute formic acid aqueous solutions to improve the quality of biocrudes, which can lead to more efficient and cost-effective conversion into biofuels.

09 BIOMASS FUELS↗

Development of a fully integrated analysis system for ions based on ion-selective optodes and centrifugal microfluidics

A fully integrated, miniaturized analysis system for ions based on a centrifugal microfluidics platform and ion-selective optode membranes is described. The microfluidic architecture is composed of channels, five solution reservoirs, a measuring chamber, and a waste reservoir manufactured onto a disk-shaped substrate of poly(methyl methacrylate). Ion-selective optode membranes, composed of plasticized poly(vinyl chloride) impregnated with an ionophore, a proton chromoionophore, and a lipophilic anionic additive, were cast, with a spin-on device, onto a support layer and then immobilized on the disk. Fluid propulsion is achieved by the centrifugal force that results from spinning the disk, while a system of valves is built onto the disk to control flow. These valves operate based on fluid properties and fluid/substrate interactions and are controlled by the angular frequency of rotation. With this system, we have been able to deliver calibrant solutions, washing buffers, or "test" solutions to the measuring chamber where the optode membrane is located. An analysis system based on a potassium-selective optode has been characterized. Results indicate that optodes immobilized on the platform demonstrate theoretical responses in an absorbance mode of measurement. Samples of unknown concentration can be quantified to within 3% error by fitting the response function for a given optode membrane using an acid (for measuring the signal for a fully protonated chromoionophore), a base (for fully deprotonated chromoionophore), and two standard solutions. Further, the ability to measure ion concentrations by employing one standard solution in conjunction with acid and base and with two standards alone were studied to delineate whether the current architecture could be simplified. Finally, the efficacy of incorporating washing steps into the calibration protocol was investigated.

NASA Discipline Life Sciences Technologies↗

Polymerization on the rocks: theoretical introduction

It is difficult if not impossible to synthesize long polymers of amino acids, nucleotides, etc., in homogeneous aqueous solution. We suggest that long polymers were synthesized on the surface of minerals in a prebiotic process analogous to solid-phase synthesis. Provided that the affinity of a mineral for an oligomer increases with the length of the oligomer, adsorption must become essentially irreversible for sufficiently long oligomers. Irreversibly adsorbed oligomers may be elongated indefinitely by repeated cycles in which the mineral with its adsorbed oligomers is first incubated with activated monomers and then washed free of deactivated monomer and side-products. We discuss in some detail the formation of oligomers of negatively-charged amino acids such as glutamic acid on anion-exchange minerals such as hydroxylapatite or illite. We show that the average length of adsorbed oligomers at steady state, n, depends on the balance between the rate of chain elongation and the rate of hydrolysis, and we derive a very approximate formula for n.

NASA Discipline Exobiology↗

SRNL Sludge Batch 10 Qualification SRAT and SME Off-Gas Results

Savannah River National Laboratory (SRNL) completed a small-scale demonstration of the Defense Waste Processing Facility (DWPF) Chemical Process Cell (CPC) utilizing the nitric-glycolic acid (NGA) flowsheet to support Sludge Batch 10 (SB10) qualification. The demonstration utilized a Tank 51 slurry sample washed by SRNL (with added H-canyon material). The purpose of this document is to report the observed off-gas results from the demonstration. With the NGA flowsheet, DWPF has a CPC hydrogen generation limit of 2.4×10 -2 lb/h. The peak observed rate was nearly 90 times less than that limit during SRNL testing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Chromium electrodes for REDOX cells

An improved electrode having a gold coating for use in the anode compartment of a REDOX cell is described. The anode fluid utilizes a chromic/chromous couple. A carbon felt is soaked in methanol, rinsed in water, dried and then heated in KOH after which it is again washed in deionized water and dried. The felt is then moistened with a methanol water solution containing chloroauric acid and is stored in a dark place while still in contact with the gold-containing solution. After all the gold-containing solution is absorbed in the felt, the latter is dried by heat and then heat treated at a substantially greater temperature. The felt is then suitable for use as an electrode and is wetted with water or up to two molar HCl prior to installation in a REDOX cell. The novelty of the invention lies in the use of KOH for cleaning the felt and the use of alcohol as a carrier for the gold together with the heat treating procedure.

Jalan, V.↗

Selective sulfur removal from semi-dry flue gas desulfurization coal fly ash for concrete and carbon dioxide capture applications

High-sulfur mixed fly ash residues from semi-dry flue gas desulfurization units in coal-fired power plants are unsuitable for use as supplementary cementitious material (SCM) for concrete production or carbon dioxide utilization. In this work, we explore the potential for upcycling a representative spray dry absorber ash (10.44 wt% SO 3 ) into concrete-SCM by selective sulfur removal via weak acid dissolution while simultaneously exploring the possibility for CO 2 capture. Towards this effort, parametric studies varying liquid-to-solid ratio, acidity, and CO 2 pressure were conducted in a batch reactor to establish the sulfur removal characteristics in de-ionized water, nitric acid, and carbonic acid, respectively. The dissolution studies show that the leaching of sulfur from calcium sulfite hemihydrate, which is the predominant S phase, is rapid and achieves a concentration plateau within 5 min, and subsequently, appears to be controlled by the primary mineral solubility. Here, preferential S removal was sufficient to meet SCM standards (e.g., 5.0 wt% as per ASTM C618) using all three washing solutions with 0.62–0.72 selectivity (S^), defined as the molar ratio of S to Ca in the leachate, for a raw fly ash with bulk S^ = 0.3. Acid dissolution with 1.43 meq/g of ash or under 5 atm CO 2 retained > 18 wt% CaO and other Si-, Al-rich phases in the fly ash. Based on the experimental findings, two sulfur removal schemes were suggested for either integration with CO 2 capture and utilization processes using flue gas or to produce fly ash for use as a SCM.

01 COAL, LIGNITE, AND PEAT↗

Method of treating the surface of a glass member

A method is described of treating a surface of a glass member intended to abut a transparent element for disrupting the light interference fringes formed between the surfaces. The method involves the steps of grinding the surface to form irregularities thereon; bathing the surface with an aqueous solution containing between substantially 41.3 percent and 45.7 percent by volume of sulfuric acid and between substantially 54.3 percent and 58.7 percent by volume of hydrofluoric acid for a time sufficient to polish the irregularities until the glass member is about 90 percent light transmissive; and washing the glass member with a liquid having a temperature substantially lower than the temperature of the aqueous solution for preventing further reaction between the aqueous solution and the surface.

Rice, S. H.↗

Quantification of urinary uric acid in the presence of thymol and thimerosal by high-performance liquid chromatography

A high-performance liquid chromatographic method was developed as an alternative to automated enzymatic analysis of uric acid in human urine preserved with thymol and/or thimerosal. Uric acid (tR = 10 min) and creatinine (tR = 5 min) were separated and quantified during isocratic elution (0.025 M acetate buffer, pH 4.5) from a mu Bondapak C18 column. The uric-acid peak was identified chemically by incubating urine samples with uricase. The thymol/thimerosal peak appeared at 31 min during the washing step and did not interfere with the analysis. We validated the high-performance liquid chromatographic method for linearity, precision and accuracy, and the results were found to be excellent.

NASA Discipline Regulatory Physiology↗

Vanadium metal-organic framework for selective adsorption

A permanently porous vanadium(II)-containing metal-organic framework (MOF) with vanadium(II) centers and methods for synthesis of such MOF frameworks are provided. Methods for using such compounds to selectively react with N2 over CH4 are provided. In the synthetic methods, a vanadium source, such as VY2(tmeda)2, where Y is a halogen and tmeda is N,N,N′,N′-tetramethylethane-1,2-diamine and a H2(ligand) are reacted in the presence of acid in a solvent at between 110° C. and 130° C. to form an intermediate product. The intermediate product is collected and washed with a washing agent, such as DMF and acetonitrile, and the vanadium(II) based MOF is activated by heating the washed intermediate product to at least 160° C. under dynamic vacuum.

Long, Jeffrey R.↗

IPE 7

A description is given of the collection and treatment of samples of Prochloron cells. The cells of Prochloron were obtained and prepared in the following way. Colonies of the symbiotic host, the giant didemnid ascidian Lissoclinum patella, were collected at low-tide level on reef-flat sand between Kamori Island and Koror, Palau, Western Caroline Islands. The animal colonies were taken, immersed in sea water, to an 8,000-litre holding tank and kept with constantly running sea water at 30 deg. Individual colonies were picked clean of contaminants, rinsed in sea water buffered with 40 nM or 100 mM Tris buffer at pH 8.4, and squeezed by hand to express the algal cells from the cloacal atria. The algae were received in about an equal volume of the same buffered sea water; this neutralized the acids liberated by the bruised ascidians and thereby maintained the Ph high enough to keep the algal cells green. The Prochloron cells were washed twice with buffered sea water and concentrated by centrifugation at about 50 g for 90 seconds. Microscopic examination revealed that contamination by animal host cells or bacteria was negligible (much less than 1%).

Source record↗

Reducing Organic Contamination in NASA JSC Astromaterial Curation Facility

Future robotic and human spaceflight missions to the Moon, Mars, asteroids and comets will require handling and storing astromaterial samples with minimal inorganic and organic contamination to preserve the scientific integrity of each sample. Much was learned from the rigorous attempts to minimize and monitor organic contamination during Apollo, but it was not adequate for current analytical requirements; thus [1]. OSIRIS-REx, Hayabusa-2, and future Mars sample return will require better protocols for reducing organic contamination. Future isolation con-tainment systems for astromaterials, possibly nitrogen enriched gloveboxes, must be able to reduce organic and inorganic cross-contamination. In 2012, a baseline study established the current state of organic cleanliness in gloveboxes used by NASA JSC astromaterials curation labs that could be used as a benchmark for future mission designs [2, 3]. After standard ultra-pure water (UPW) cleaning, the majority of organic contaminates found were hydrocarbons, plasticizers, silicones, and solvents. Hydro-carbons loads (> C7) ranged from 1.9 to 11.8 ng/cm2 for TD-GC-MS wafer exposure analyses and 5.0 to 19.5 ng/L for TD-GC-MS adsorbent tube exposure. Plasticizers included < 0.6 ng/cm2 of DBP, DEP, TXIB, and DIBP. Silicones included < 0.5 ng/cm2 of cyclo(Me2SiO)x (x = 6, 8, 9, 10) and siloxane. Solvents included < 1.0 ng/cm2 of 2-cyclohexen-1-one, 3,5,5-trimethyl- (Isopho-rone), N-formylpiperidine, and 2-(2-butoxyethoxy) ethanol. In addition, DBF, rubber/polymer additive was found at < 0.2 ng/cm2 and caprolactam, nylon-6 at < 0.6 ng/cm2. Reducing Organics: The Apollo program was the last sam-ple return mission to place high-level organic requirements and biological containment protocols on a curation facility. The high vacuum complex F-201 glovebox in the Lunar Receiving Labora-tory used ethyl alcohol (190 proof), 3:1 benzene/methanol (nano grade solution), and heat sterilization at 130degC for 48 hours to reduce organic contamination. In addition, both heat sterilization and peracetic acid sterilization were used in the atmospheric de-contamination (R) cabinets. Later, Lunar curation gloveboxes were degreased with a pressurized Freon 113 wash. Today, UPW has replaced Freon as the standard cleaning procedure, but does not have the degreasing solvency power of Freon. Future Cleaning Studies: Cleaning experiments are cur-rently being orchestrated to study how to degrease and reduce organics in a JSC curation glovebox lower than the established baseline. Several new chemicals in the industry have replaced traditional degreasing solvents such as Freon and others that are now federally restricted. However, these new suites of chemicals remain untested for lowering organics in curation gloveboxes. 3M's HFE-7100DL and DuPont's Vertrel XF are currently being tested as a replacement for Freon 113 as a degreaser at JSC cura-tion facilities. In addition, the use of UPW as a final rinse is be-ing tested, which presumably can maintain a lower total organic carbon load than the filtered purity of chemical solutions. References: [1] Allton J.H. et al. (2012) LPS XLIII, 2439; [2] Calaway M.

Calaway, M. J.↗

Studies on the behavior of ammonia and ammonium salts in the atmosphere (1) - Fractional collection of ammonia gas and particulate ammonium

Methods for the fractional collection of trace amounts of atmospheric ammonia gas and ammonium particles on a two staged glass fiber filter are summarized. A standard glass fiber filter washed with distilled water and dried at 120 to 130 C was used. A second filter was impregnated with a mixture of 3% boric acid and 25% glycerin solution. The blank of glass fiber filters impregnated with a mixture of the above solution was very low for ammonia, i.e. 0.06 micrograms in a filter of 47 mm in diameter. The mean concentrations of ammonia and ammonium in air at Kawasaki, a polluted area, were 7.6 and 2.3 micrograms cu m, and those at Sanriku, an unpolluted area 0.9 and 0.2 micrograms cu m, respectively. Ratios of concentration levels of ammonium to total ammonia in the atmosphere were 0.3 and 0.2 for the polluted and unpolluted areas, respectively. Ammonium salts in air at both areas were not correlated with relative humidity. Variations in time of ammonia concentrations and sources in surrounding areas are also considered.

Kiin, K.↗

Nanoscale Mg–B via Surfactant Ball Milling of MgB 2 : Morphology, Composition, and Improved Hydrogen Storage Properties

Metal borides have attracted the attention of researchers due to their useful physical properties and unique ability to form high hydrogen-capacity metal borohydrides. We demonstrate improved hydrogen storage properties of a nanoscale Mg–B material made by surfactant ball milling MgB 2 in a mixture of heptane, oleic acid, and oleylamine. Transmission electron microscopy data show that Mg–B nanoplatelets are produced with sizes ranging from 5 to 50 nm, which agglomerate upon ethanol washing to produce an agglomerated nanoscale Mg–B material of micron-sized particles with some surfactant still remaining. X-ray diffraction measurements reveal a two-component material where 32% of the solid is a strained crystalline solid maintaining the hexagonal structure with the remainder being amorphous. Fourier transform infrared shows that the oleate binds in a “bridge-bonding” fashion preferentially to magnesium rather than boron, which is confirmed by density functional theory calculations. The Mg–B nanoscale material is deficient in boron relative to bulk MgB 2 with a Mg–B ratio of ~1:0.75. The nanoscale MgB 0.75 material has a disrupted B–B ring network as indicated by X-ray absorption measurements. Hydrogenation experiments at 700 bar and 280 °C show that it partially hydrogenates at temperatures 100 °C below the threshold for bulk MgB 2 hydrogenation. In addition, upon heating to 200 °C, the H–H bond-breaking ability increases ~10-fold according to hydrogen–deuterium exchange experiments due to desorption of oleate at the surface. This behavior would make the nanoscale Mg–B material useful as an additive where rapid H–H bond breaking is needed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Parametric evaluation of a dual-layer dynamic hyperfiltration membrane for recovery of spacecraft wash water at elevated temperature

Performance data consisting of solute rejections and product flux have been measured, as dependent on the operational parameters. These parameters were pressure, 5,000,000 N/sq m (750 psia) to 7,000,000 N/sq m (1040 psia); temperature, 347 K (165 F) to 368 K (200 F); velocity, 1.6 m/s to 10 m/s; and concentration (up to 14x). Tests were carried out on analog wash water. Data taken include rejections of organic materials (TOC), ammonia, urea, and an assortment of ions. The membrane used was a dual-layer, polyacrylic acid over zirconium oxide, deposited in situ on a porcelain ceramic substrate.

Brandon, C. A.↗

Facile etching for single crystal cathode materials

A recycling and synthesis of charge material for secondary batteries generates single-crystal charge materials for producing batteries with greater charge cycle longevity. Charge material particles undergo a heating for fusing or enhancing grain boundaries between polycrystalline particles. The resulting, more well-defined grain boundaries are easily etched by a relatively weak mineral acid solution. The acid solution removes material at the grain boundaries to separate secondary particles into primary particles along the grain boundaries. The resulting single crystal (monocrystalline) charge material particles are washed and filtered, and typically re-sintered to accommodate any needed lithium (lithium carbonate), and result in a charge material with larger surface area, higher lithium diffusivity and lower cation ordering.

Wang, Yan↗