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At least 289 records · Page 16

Effect on combined cycle efficiency of stack gas temperature constraints to avoid acid corrosion

To avoid condensation of sulfuric acid in the gas turbine exhaust when burning fuel oils contaning sulfur, the exhaust stack temperature and cold-end heat exchanger surfaces must be kept above the condensation temperature. Raising the exhaust stack temperature, however, results in lower combined cycle efficiency compared to that achievable by a combined cycle burning a sulfur-free fuel. The maximum difference in efficiency between the use of sulfur-free and fuels containing 0.8 percent sulfur is found to be less than one percentage point. The effect of using a ceramic thermal barrier coating (TBC) and a fuel containing sulfur is also evaluated. The combined-cycle efficiency gain using a TBC with a fuel containing sulfur compared to a sulfur-free fuel without TBC is 0.6 to 1.0 percentage points with air-cooled gas turbines and 1.6 to 1.8 percentage points with water-cooled gas turbines.

Nainiger, J. J.↗

Pretreatment of Bituminous Coal By-Products for the Hydrometallurgical Extraction of Rare Earth Elements

Low-temperature plasma (LTP) oxidation has been widely used to study the mineralogy of the mineral matter existing in coal sources. The current study investigated the potential of LTP oxidation as a pre-treatment method to improve rare earth element (REE) leachability from coal and its by-products. Representative density-fractionated samples of Baker and Fire Clay coarse refuse seam materials were ground to a top size of 180 µm and subjected to low-temperature plasma oxidation. Subsequently, the treated samples were leached at 1% w/v solids concentration and 75 °C for 5 h using (i) de-ionized (DI) water, (ii) 0.1 mol/L of ammonium sulfate, and (iii) 1.2 mol/L of sulfuric acid. It was determined that LTP treatment improved REE leaching characteristics, especially the leaching of heavy REEs (HREE), existing in the lighter density fractions of the Baker seam coarse refuse material. For instance, the HREE recovery for the 1.6 specific gravity (SG) float fraction increased from 8% to 33% using 0.1 mol/L of ammonium sulfate solution after 32 h of LTP treatment. This finding indicated that HREEs associated with the organic matter were released by the LTP treatment and adsorbed onto the surfaces of highly negative charged mineral matter and was exchanged with ammonium to allow their recovery. Similarly, when using 1.2 mol/L of sulfuric acid, the HREE recovery increased from 23% to 53% for the 1.6 SG float fraction. Interestingly, LTP oxidation did not provide significant improvement in REE recovery from the 2.2 sink density fractions, which was likely due to its lower organic content. No significant benefits were observed when treating the Fire Clay coarse refuse material, which was likely due to the lack of organic affinity and the difficult-to-leach REE minerals associated with the coal source such as monazite, xenotime, and zircon. Conversely, high-temperature oxidation within a temperature range of 600–750 °C significantly improved REE leaching characteristics for both coal sources. Improvement in REE recovery was due to decarbonization of the material, clay dehydroxylation and subsequent conversion of liberated REE-bearing minerals into a more leachable form. However, increasing the temperature above 800 °C decreased REE recovery due to the conversion of meta-kaolinite into mullite, which is chemically stable.

58 GEOSCIENCES↗

Physical and Optical/Radiative Properties of Arctic Aerosols: Potential Effects on Arctic Climate

We have determined the abundance of light-scattering sulfuric acid (H2SO4/H2O) and light-absorbing black carbon aerosol (BCA) in Spring 1992 in the Arctic atmosphere by airborne in situ sampling with impactors, and measured particle sizes and morphologies by scanning electron microscopy. The mass of BCA in the Arctic troposphere is one percent of the total aerosol, reduced to one part in 104 in the stratosphere. A Mie algorithm permits the calculation of the optical properties of the various aerosol components, and an algorithm developed by Ackerman and Toon and modified to serve our needs lets us calculate the optical effects of the black carbon aerosol that is mixed internally with the sulfuric acid aerosol. It follows that the effect of internally-mixed BCA on the aerosol scattering and absorption properties depends on its location within the droplet. BCA concentrated near the droplet surface has a greater effect on absorption of solar radiation than does the same amount of BCA located near its center. Single scatter albedos of the combined system are omega(sub 0)=1.0 in the post-Pinatubo Arctic stratosphere, and as low as 0.94 in the troposphere. The aerosol has the potential to regionally warm the Arctic earth-atmosphere system, because of the high surface albedo of the snow-covered Arctic.

Pueschel, R. F.↗

THF co-solvent pretreatment prevents lignin redeposition from interfering with enzymes yielding prolonged cellulase activity

Background: Conventional aqueous dilute sulfuric acid (DSA) pretreatment of lignocellulosic biomass facilitates hemicellulose solubilization and can improve subsequent enzymatic digestibility of cellulose to fermentable glucose. However, much of the lignin after DSA pretreatment either remains intact within the cell wall or readily redeposits back onto the biomass surface. This redeposited lignin has been shown to reduce enzyme activity and contribute to rapid enzyme deactivation, thus, necessitating significantly higher enzyme loadings than deemed economical for biofuel production from biomass. Results: In this study, we demonstrate how detrimental lignin redeposition on biomass surface after pretreatment can be prevented by employing Co-solvent Enhanced Lignocellulosic Fractionation (CELF) pretreatment that uses THF–water co-solvents with dilute sulfuric acid to solubilize lignin and overcome limitations of DSA pretreatment. We first find that enzymatic hydrolysis of CELF-pretreated switchgrass can sustain a high enzyme activity over incubation periods as long as 5 weeks with enzyme doses as low as 2 mg protein/g glucan to achieve 90% yield to glucose. A modified Ninhydrin-based protein assay revealed that the free-enzyme concentration in the hydrolysate liquor, related to enzyme activity, remained unchanged over long hydrolysis times. DSA-pretreated switchgrass, by contrast, had a 40% drop in free enzymes in solution during incubation, providing evidence of enzyme deactivation. Furthermore, measurements of enzyme adsorption per gram of lignin suggested that CELF prevented lignin redeposition onto the biomass surface, and the little lignin left in the solids was mostly integral to the original lignin–carbohydrate complex (LCC). Scanning electron micrographs and NMR characterization of lignin supported this observation. Conclusions: Enzymatic hydrolysis of solids from CELF pretreatment of switchgrass at low enzyme loadings was sustained for considerably longer times and reached higher conversions than for DSA solids. Analysis of solids following pretreatment and enzymatic hydrolysis showed that prolonged cellulase activity could be attributed to the limited lignin redeposition on the biomass surface making more enzymes available for hydrolysis of more accessible glucan.

09 BIOMASS FUELS↗

Radio occultation studies of the Venus atmosphere with the Magellan spacecraft. 2: Results from the October 1991 experiments

On October 5 and 6, 1991, three dual-frequency ingress radio occultation experiments were conducted at Venus during consecutive orbits of the Magellan spacecraft. The radio signals probed a region of the atmosphere near 65 deg N, with a solar zenith angle of 108 deg, reaching below 35 km at 3.6 cm, and below 34 km at 13 cm (above a mean radius of 6052 km). The high effective isotropic radiated power (EIRP) of the Magellan spacecraft and highly successful attitude maneuvers allowed these signals to probe deeper than any previous radio occultation experiment and also resulted in the most accurate thermal and sulfuric acid vapor abundance profiles ever obtained at Venus through radio occultation techniques. The performance of the spacecraft and the experiment design are discussed in an accompanying paper. Average electron density profiles retrieved from the data possess peaks between 2600 and 6000/cu cm, well below typical values of 10,000/cu cm retrieved in 1979 by Pioneer Venus at similar solar zenith angles. Other basic results include vertical profiles of temperature, pressure, and density in the neutral atmosphere, 13- and 3.6-cm absorpttivity, and H2SO4 (g) abundance below the main cloud layer. H2SO4 (g) becomes significant below 50 km, reaching peaks between 18 and 24 ppm near 39 km before dropping precipitously below 38 km. These sharp decreases confirm the thermal decomposition of sulfuric acid vapor below 39 km. Since the Venus atmosphere rotated approximately 10 deg between experiments, the data contain information about the horizontal variability of the atmosphere. All derived profiles exhibit significant variations from orbit to orbit, indicating the presence of dynamical processes between 33 and 200 km. In particular, the orbit-to-orbit variations in temperature and in H2SO4 (g) abundance appear to be correlated, suggesting that a common mechanism may be responsible for the observed spatial variations.

Jenkins, Jon M.↗

A numerical examination of the effect of sulfide dissolution on silicate weathering

Silicate weathering regulates climate on geological time scales as a net, climate-sensitive sink of atmospheric CO 2 . On the other hand, sulfuric acid produced through sulfide dissolution affects silicate weathering, diminishing its effectiveness as a climate regulator based on evidence from river chemistry. This study takes a theoretical approach to quantitatively examine the effect of sulfide dissolution, coupling a one-dimensional model of pyrite weathering to that of albite transformation to kaolinite. The coupled model reveals that when the reaction front of sulfide is deeper than that of silicates reacting with CO 2 , the silicate-weathering feedback on climate is not directly affected by sulfide dissolution, but only indirectly through oceanic processes such as reverse weathering and carbonate deposition. In turn, when sulfide dissolution occurs within zones of CO 2 -silicate reactions close to the surface, the feedback between climate and silicate weathering can be significantly weakened because sulfuric acid competes effectively with carbonic acid in mineral dissolution. As the depth of the sulfide reaction front can be changed by variations in water table depth, the latter feedback weakening could have occurred in concert with climate-change-driven water table fluctuations, amplifying atmospheric CO 2 variations during the Phanerozoic.

58 GEOSCIENCES↗

Satellite characterization of global stratospheric sulfate aerosols released by Tonga volcano

Large volcanic eruptions create an enhanced layer of sulfate aerosols in the stratosphere. These sulfuric acid droplets persist for many months, altering the climate and stratospheric chemistry. Sulfate aerosols scatter sunlight back to space, cooling the surface of the Earth and absorb outgoing thermal radiation, heating the stratosphere. The calculation of the climate impact of sulfate aerosols depends on their physical properties such as droplet size and chemical composition. These properties are not well known, and this uncertainty contributes to the errors in climate model predictions. Here we derive the first empirical formula that predicts the composition of stratospheric sulfate aerosols from volcanic eruptions from the air temperature and water vapor pressure. Measurements of atmospheric infrared transmittance of the Hunga Tonga-Hunga Ha'apai sulfate aerosol plume by the Atmospheric Chemistry Experiment (ACE) satellite were analyzed to determine composition (weight percent of sulfuric acid) and median particle radius. These data are supplemented by measurements of the Raikoke and Nabro eruptions. Our analysis allows the properties of volcanic aerosols in the stratosphere to be predicted reliably in atmospheric models.

P Bernath↗

Urine Pretreatment Configuration and Test Results for Space Applications

Pretreatment of urine using Oxone and sulfuric acid is baselined in the International Space Station (ISS) waste water reclamation system to control odors, fix urea and control microbial growth. In addition, pretreatment is recommended for long term flight use of urine collection and two phase separation to reduce or eliminate fouling of the associated hardware and plumbing with urine precipitates. This is important for ISS application because the amount of maintenance time for cleaning and repairing hardware must be minimized. This paper describes the development of a chemical pretreatment system based on solid tablet shapes which are positioned in the urine collection hose and are dissolved by the intrained urine at the proper ratio of pretreatment to urine. Building upon the prior success of the developed and tested solid Oxone tablet a trade study was completed to confirm if a similar approach, or alternative, would be appropriate for the sulfuric acid injection method. In addition, a recommended handling and packaging approach of the solid tablets for long term, safe and convenient use on ISS was addressed. Consequently, the solid tablet concept with suitable packaging was identified as the Urine Pretreat / Prefilter Assembly (UPPA). Testing of the UPPA configuration confirmed the disolution rates and ratios required by ISS were achieved. This testing included laboratory controlled methods as well as a 'real world' test evaluation that occurred during the 150 day Stage 10 Water Recovery Test (WRT) conducted at NASA Marshall Space Flight Center (MSFC).

Howard, Stanley G.↗

Pioneer-Venus radio occultation (ORO) data reduction: Profiles of 13 cm absorptivity

In order to characterize possible variations in the abundance and distribution of subcloud sulfuric acid vapor, 13 cm radio occultation signals from 23 orbits that occurred in late 1986 and 1987 (Season 10) and 7 orbits that occurred in 1979 (Season 1) were processed. The data were inverted via inverse Abel transform to produce 13 cm absorptivity profiles. Pressure and temperature profiles obtained with the Pioneer-Venus night probe and the northern probe were used along with the absorptivity profiles to infer upper limits for vertical profiles of the abundance of gaseous H2SO4. In addition to inverting the data, error bars were placed on the absorptivity profiles and H2SO4 abundance profiles using the standard propagation of errors. These error bars were developed by considering the effects of statistical errors only. The profiles show a distinct pattern with regard to latitude which is consistent with latitude variations observed in data obtained during the occultation seasons nos. 1 and 2. However, when compared with the earlier data, the recent occultation studies suggest that the amount of sulfuric acid vapor occurring at and below the main cloud layer may have decreased between early 1979 and late 1986.

Steffes, Paul G.↗

High-Throughput Analysis of Materials for Chemical Looping Processes

Chemical looping is a promising approach for improving the energy efficiency of many industrial chemical processes. However, a major limitation of modern chemical looping technologies is the lack of suitable active materials to mediate the involved subreactions. Identification of suitable materials has been historically limited by the scarcity of high-temperature (>600 °C) thermochemical data to evaluate candidate materials. An accuratethermodynamic approach is demonstrated here to rapidly identify active materials which is applicable to a wide variety of chemical looping chemistries. Application of this analysis to chemical looping combustion correctly classifies 17/17 experimentally studied redox materials by their viability and identifies over 1300 promising yet previously unstudied active materials. This approach is further demonstrated by analyzing redox pairs for mediating a novel chemical looping process for producing pure SO2 from raw sulfur and air which could provide a more efficient and lower emission route to sulfuric acid. 12 promising redox materials for this process are identified, two of which are supported by previous experimental studies of their individual oxidation and reduction reactions. This approach provides the necessary foundation for connecting process design with high-throughput material discovery to accelerate the innovation and development of a wide range of chemical looping technologies.

chemical looping↗

Acid anion electrolyte effects on platinum for oxygen and hydrogen electrocatalysis

Platinum is an important material with applications in oxygen and hydrogen electrocatalysis. To better understand how its activity can be modulated through electrolyte effects in the double layer microenvironment, herein we investigate the effects of different acid anions on platinum for the oxygen reduction/evolution reaction (ORR/OER) and hydrogen evolution/oxidation reaction (HER/HOR) in pH 1 electrolytes. Experimentally, we see the ORR activity trend of HClO 4 > HNO 3 > H 2 SO 4 , and the OER activity trend of HClO 4 > HNO 3 ~ H 2 SO 4 . HER/HOR performance is similar across all three electrolytes. Notably, we demonstrate that ORR performance can be improved 4-fold in nitric acid compared to in sulfuric acid. Assessing the potential-dependent role of relative anion competitive adsorption with density functional theory, we calculate unfavorable adsorption on Pt(111) for all the anions at HER/HOR conditions while under ORR/OER conditions ClO$^{-}_{4}$ binds the weakest followed by NO$^{-}_{3}$ and SO$^{2-}_{4}$. Our combined experimental-theoretical work highlights the importance of understanding the role of anions across a large potential range and reveals nitrate-like electrolyte microenvironments as interesting possible sulfonate alternatives to mitigate the catalyst poisoning effects of polymer membranes/ionomers in electrochemical systems. These findings help inform rational design approaches to further enhance catalyst activity via microenvironment engineering.

36 MATERIALS SCIENCE↗

Materials Data on SN8O13 by Materials Project

(N2)5(NO3)6(SO4)2 crystallizes in the monoclinic P2_1 space group. The structure is zero-dimensional and consists of ten ammonia molecules, six nitric acid molecules, and two sulfuric acid molecules.

36 MATERIALS SCIENCE↗

Materials Data on H16S(N3O5)2 by Materials Project

(NH4)4(NO3)2SO4 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of sixteen ammonium molecules, eight nitric acid molecules, and four sulfuric acid molecules.

36 MATERIALS SCIENCE↗

Materials Data on S(N3O5)2 by Materials Project

(N2)2(NO3)2SO4 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of sixteen ammonia molecules, eight nitric acid molecules, and four sulfuric acid molecules.

36 MATERIALS SCIENCE↗

Materials Data on H16S(N3O5)2 by Materials Project

(NH4)4(NO3)2SO4 is Silicon tetrafluoride-derived structured and crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of sixteen ammonium molecules, eight nitric acid molecules, and four sulfuric acid molecules.

36 MATERIALS SCIENCE↗

Synthesis of 2,4,8,10-tetroxaspiro5,5undecane

Pentaerythritol is converted to its diformal, 2,4,8,10-tetroxaspirol5.5undecane, by heating it to a temperature within the range of about 110 to 150 C, for a period of up to 10 minutes, in the presence of a slight excess of paraformaldehyde and of a catalytic quantity of an acid catalyst such as sulfuric acid. The reaction may be carried out in two steps, by forming first the monoformal, then the diformal. In any case, total reaction time is about 10 minutes, and yield of diformal are greater than 90%. Previous processes require hours or days, and often, tedious operating procedures.

Poshkus, A. C.↗

Formation of Smectite and Carbonate Minerals From Basaltic Glass on Early Mars

Intense aqueous alteration occurred on early Mars and left behind various secondary minerals. Physicochemical characteristics of ancient aquatic systems are still largely unknown, including why widespread smectite but limited carbonate deposits formed. Acidic events caused by sulfuric acid could permit smectite but inhibit carbonate formation on Mars. Gradual acid neutralization by basalts, however, develops conditions favorable for carbonate precipitation, leading to the coexistence of smectite and carbonates. The objectives of our work were to identify pH conditions and mineralogy of smectite and carbonate formed together from Mars analog basaltic glass.

T. S. Peretyazhko↗