NO Oxidation by Activated Carbon Catalysts: Impact of Carbon Characteristics, Pressure, and the Presence of Water.

Nitric oxide can be removed from flue gas by catalytic oxidation of NO to NO2, followed by dissolution of NO2 in water. The work presented here includes catalytic NO oxidation by activated carbons (ACs) at atmospheric and elevated pressures under dry and wet conditions at ambient temperature. The AC samples had different physicochemical characteristics including surface areas of ∼400-1600 m2/g and micropore volumes of ∼0.2-0.6 cm3/g while having different surface chemistries. Dry tests indicated that introducing nitrogen functionalities or coating with pyrolytic carbon could enhance the catalytic activity of AC for NO oxidation. Nitric oxide concentration profiles from the oxidation experiments under dry conditions showed maximum values after 5-15.5 h of testing and a steady-state condition after ∼12-30 h and that a major release of NO2 began after reaching the maximum values in the NO concentration. Adsorption profiles showed a high rate of NO x adsorption during the early hours of these experiments, and this rate decreased almost exponentially to a near-zero value. A near-complete catalytic conversion was achieved for NO oxidation at 120 psig under dry conditions, substantially higher than the 62% value of the noncatalytic NO oxidation at 217 psig. The wet trickle-bed experiments revealed that an inert packing material with a high external surface was a more suitable option than the ACs for NO oxidation in a wet trickle-bed system, even for ACs that exhibited high catalytic reactivity under dry conditions. Noncatalytic NO oxidation in the trickle-bed system was enhanced by the higher gas-liquid contact surface of the packing material for NO2 dissolution in water. Complete wetting of the hydrophilic AC or the presence of water vapor in the gas in contact with the surface of the superhydrophobic AC could eliminate or drastically reduce the catalytic activity of the AC for NO oxidation.

Utilization of Water Utility Lime Sludge for Flue Gas Desulfurization in Coal-Fired Power Plants: Part III. Testing at a Higher Scale and Assessment of Selected Potential Operational Issues.

The feasibility of lime sludge utilization for flue gas desulfurization was evaluated by continuing the previous laboratory-scale studies at a higher scale and investigating two potential operational issues, namely viscosity and metal corrosion. Two lime sludge samples and a baseline limestone sample, which were previously characterized and tested for SO2 capture from a simulated flue gas at a laboratory scale, were first tested at a 10-fold scale with a simulated flue gas, and then tested with a slipstream of flue gas from a coal-fired power plant. The tested lime sludge and limestone slurries reduced the SO2 concentration of the simulated flue gas from 2000 to <1 ppm, and they demonstrated similar Hg reemission profiles. Field-testing results revealed that the limestone and lime sludge slurries reduced the SO2 concentration of the flue gas from ~1500 to <1 ppm. These experiments confirmed our previous smaller scale laboratory results that lime sludge can function as a suitable substitute for limestone for SO2 removal from the flue gas of coal-fired power plants without negatively affecting Hg reemission. Two operational issues, namely viscosity and metal corrosion, were investigated to evaluate practical issues in the transition from limestone to lime sludge at power plants. Results of Marsh funnel viscosity experiments conducted at different solids contents and temperatures indicated the limestone and lime sludge slurries and their gypsum counterparts had similar flow characteristics. Carbon-steel, stainless-steel, and Hastelloy coupons were tested for corrosion by lime sludge and limestone slurries. Both stainless steel and Hastelloy were resistive to corrosion in slurries made from lime sludge or limestone samples or their gypsum counterparts. A considerable but similar amount of corrosion was observed for carbon-steel coupons exposed to lime sludge and limestone slurries. Adding 5000 ppm of Cl- to slurries considerably increased the corrosion rate of carbon steel.

Recent Advances in Graphene Oxide Membranes for Gas Separation Applications.

Graphene oxide (GO) can dramatically enhance the gas separation performance of membrane technologies beyond the limits of conventional membrane materials in terms of both permeability and selectivity. Graphene oxide membranes can allow extremely high fluxes because of their ultimate thinness and unique layered structure. In addition, their high selectivity is due to the molecular sieving or diffusion effect resulting from their narrow pore size distribution or their unique surface chemistry. In the first part of this review, we briefly discuss different mechanisms of gas transport through membranes, with an emphasis on the proposed mechanisms for gas separation by GO membranes. In the second part, we review the methods for GO membrane preparation and characterization. In the third part, we provide a critical review of the literature on the application of different types of GO membranes for CO2, H2, and hydrocarbon separation. Finally, we provide recommendations for the development of high-performance GO membranes for gas separation applications.

The Impact of Methylenetetrahydrofolate Reductase (MTHFR) Sperm Methylation and Variants on Semen Parameters and the Chance of Recurrent Pregnancy Loss in the Couple.

BACKGROUND: Recurrent pregnancy loss (RPL) defined as three or more consecutive spontaneous miscarriages before the 20th week of gestation is caused by different factors including genetic and epigenetic background. However the involvement of paternal background on RPL is an interesting novel argument, which is not well studied. The main focus of the present study was to investigate for the association of paternal methylenetetrahydrofolate reductase (MTHFR) epigenotypes with sperm parameters and RPL. Moreover, the frequency of two of MTHFR Single Nucleotide Polymorphisms (SNPs) in males was assessed. METHODS: This is a case-control study. Methylation Specific PCR (MSP) was used to evaluate the methylation status of MTHFR promoter on sperm DNA of 25 male partners of RPL and 25 male partners of non-RPL couples. PCR-RFLP method was used to analyze 1,298 A>C (rs1801131) and 677 C>T (rs1801133) polymorphisms. RESULTS: No significant difference was observed in frequency of methylated MTHFR epigenotype between RPL and non-RPL males. Furthermore, methylated MTHFR epigenotype was more frequent (but not statistically significant) among men with abnormal sperm parameters compared to normal-sperm men. Among studied polymorphisms, only the mutated allele of C677T showed statistically higher prevalence among RPL males. CONCLUSIONS: Although our results do not establish any connection between MTHFR epigenotypes and RPL they do highlight the impact of C677T in the pathology.

Utilization of Water Utility Lime Sludge for Flue Gas Desulfurization in Coal-Fired Power Plants: Part I. Supply-Demand Evaluation and Life Cycle Assessment.

The feasibility of lime-softening sludge utilization for flue gas desulfurization in coal-fired power plants was evaluated through a supply-demand analysis and a life cycle assessment (LCA). To evaluate the demand and supply of lime sludge to replace limestone on a national scale, the annual amount of lime sludge generated by water treatment utilities in the United States was estimated and compared with the annual amount of limestone used by coal-fired power utilities. To evaluate the environmental sustainability of reusing lime sludge in power plants, an LCA study was performed in which the environmental impact and water footprint of the proposed approach were quantified and these results were compared with the conventional approaches for limestone mining, grinding, and transportation to power plants and lime sludge disposal in landfills. Water utilities across the United States are currently generating approximately 3.2 million tons of lime sludge per year at an estimated disposal cost of approximately US$90 million, whereas power utilities are using approximately 6.3 million tons of limestone per year. The potential savings that would result from partial replacement of limestone with lime sludge was estimated to be approximately US$97 million per year. The LCA study showed that the environmental impact of lime sludge utilization in power plants under different scenarios was 2 orders of magnitude lower than that of the landfill disposal option. Furthermore, the water footprint for lime sludge reuse in power plants was almost negligible compared with that of the conventional approaches of disposing of lime sludge at water utilities or using limestone at power utilities.

Utilization of Water Utility Lime Sludge for Flue Gas Desulfurization in Coal-Fired Power Plants: Part II. Lime Sludge Characterization and Mercury Reemission.

The feasibility of utilizing lime sludge in the flue gas desulfurization process of coal-fired power plants was evaluated through laboratory-scale studies. Eight lime sludge samples, collected from various water treatment plants, and a high-purity limestone sample were extensively characterized and tested for their ability to capture SO2 from a simulated flue gas, while investigating the mercury reemission profiles during the scrubbing process. The reactivity of lime sludge samples for acid neutralization was significantly higher than the reactivity of the tested limestone sample. At doses less than that of the limestone sample, the lime sludge materials reduced the SO2 concentration from 2,000 to <0.5 ppm. The residual lime, higher surface area, and more accessible pores in lime sludge samples were the major factors contributing to their higher reactivity. Concentrations of several elements including B, Mg, Mn, Fe, Cu, Zn, As, Sr, and Ba in some of the tested lime sludge samples were considerably higher than those elements in the limestone. However, no significant leaching of these elements into the scrubber solutions was observed. To investigate mercury reemission during the scrubbing process, ionic mercury was introduced into the simulated slurry and mercury reemission was monitored continuously. Results showed that compared with the limestone sample, the lime sludge samples tested had lower or similar cumulative mercury reemissions. However, different lime sludge samples showed different emission profiles. No conclusive correlation between the composition or trace element content of lime sludge samples and their mercury reemission could be identified. This result was likely due to the oxidative condition of the scrubbing process, which prohibited the reducing species from transforming the ionic mercury into elemental mercury.

Life cycle assessment of treatment and handling options for a highly saline brine extracted from a potential CO2 storage site.

Carbon dioxide (CO2) injection in deep saline aquifers is a promising option for CO2 geological sequestration. However, brine extraction may be necessary to control the anticipated increase in reservoir pressure resulting from CO2 injection. The extracted brines usually have elevated concentrations of total dissolved solids (TDS) and other contaminants and require proper handling or treatment. Different options for the handling or treatment of a high-TDS brine extracted from a potential CO2 sequestration site (Mt. Simon Sandstone, Illinois, USA) are evaluated here through a life cycle assessment (LCA) study. The objective of this LCA study is to evaluate the environmental impact (EI) of various treatment or disposal options, namely, deep well disposal (Case 1); near-zero liquid discharge (ZLD) treatment followed by disposal of salt and brine by-products (Case 2); and near-ZLD treatment assuming beneficial use of the treatment by-products (Case 3). Results indicate that energy use is the dominant factor determining the overall EI. Because of the high energy consumption, desalination of the pretreated brine (Cases 2 and 3) results in the highest EI. Consequently, the overall EI of desalination cases falls mainly into two EI categories: global warming potential and resources-fossil fuels. Deep well disposal has the least EI when the EI of brine injection into deep formations is not included. The overall freshwater consumption associated with different life cycle stages of the selected disposal or treatment options is 0.6-1.8 m3 of freshwater for every 1.0 m3 of brine input. The freshwater consumption balance is 0.6 m3 for every 1.0 m3 of brine input for Case 3 when desalination by-products are utilized for beneficial uses.

Spectroscopic investigation of the wettability of multilayer graphene using highly ordered pyrolytic graphite as a model material.

We report the intrinsic water contact angle (WCA) of multilayer graphene, explore different methods of cleaning multilayer graphene, and evaluate the efficiency of those methods on the basis of spectroscopic analysis. Highly ordered pyrolytic graphite (HOPG) was used as a model material system to study the wettability of the multilayer graphene surface by WCA measurements. A WCA value of 45° ± 3° was measured for a clean HOPG surface, which can serve as the intrinsic WCA for multilayer graphene. A 1 min plasma treatment (100 W) decreased the WCA to 6°, owing to the creation of surface defects and functionalization by oxygen-containing groups. Molecular dynamics simulations of water droplets on the HOPG surface with or without the oxygen-containing defect sites confirmed the experimental results. Heat treatment at near atmospheric pressure and wet chemical cleaning methods using hydrofluoric acid and chloroform did not change the WCA significantly. Low-pressure, high-temperature annealing under argon and hydrogen reduced the WCA to 54°, close to the intrinsic WCA of HOPG. Raman spectroscopy and atomic force microscopy did not show any significant change for the HOPG surface after this treatment, confirming low-pressure, high-temperature annealing as an effective technique to clean multilayer graphene without damaging the surface. Time-of-flight secondary ion mass spectrometry indicated the existence of hydrocarbon species on the surface of the HOPG sample that was exposed to air for <5 min and the absence of these impurities in the bulk. X-ray photoelectron spectroscopy analyses of the sample surfaces after the different cleaning techniques were performed to correlate the WCA to the surface chemistry. X-ray photoelectron spectroscopy results revealed that the WCA value changed drastically, depending on the amounts of oxygen-containing and hydrocarbon-containing groups on the surface.

Exploring molecular sieve capabilities of activated carbon fibers to reduce the impact of NOM preloading on trichloroethylene adsorption.

Adsorption of trichloroethylene (TCE) by two activated carbon fibers (ACFs) and two granular activated carbons (GACs) preloaded with hydrophobic and transphilic fractions of natural organic matter (NOM) was examined. ACF10, the most microporous activated carbon used in this study, had over 90% of its pore volume in pores smaller than 10 A. It also had the highest volume in pores 5-8 A, which is the optimum pore size region for TCE adsorption, among the four activated carbons. Adsorption of NOM fractions by ACF10 was, in general, negligible. Therefore, ACF10, functioning as a molecular sieve during preloading, exhibited the least NOM uptake for each fraction, and subsequently the highest TCE adsorption. The other three sorbents had wider pore size distributions, including high volumes in pores larger than 10 A, where NOM molecules can adsorb. As a result, they showed a higher degree of uptake for all NOM fractions, and subsequently lower adsorption capacities for TCE, as compared to ACF10. The results obtained in this study showed that understanding the interplay between the optimum pore size region for the adsorption of target synthetic organic contaminant (SOC) and the pore size region for the adsorption of NOM molecules is important for controlling NOM-SOC competitions. Experiments with different NOM fractions indicated that the degree of NOM loading is important in terms of preloading effects; however the waythatthe carbon pores are filled and loaded by different NOM fractions can be different and may create an additional negative impact on TCE adsorption.

The effect of the physical and chemical characteristics of activated carbons on the adsorption energy and affinity coefficient of Dubinin equation.

The dependency of adsorption energy (E) and affinity coefficient (beta) of Dubinin equations (Dubinin-Radushkevich (DR) or Dubinin-Astakhov (DA)) on surface chemistry and porosity of activated carbons was investigated by analyzing adsorption of nitrogen, benzene, trichloroethylene (TCE), and water vapor by several surface-modified activated carbons and carbon fibers. For all studied nonpolar adsorbates, carbons with smaller average micropores showed higher adsorption energies independent of their surface chemistry. For water vapor, carbons with higher surface polarities showed higher adsorption energies due to specific adsorbate-adsorbent interactions. Adsorption energies increased with decreasing average micropore widths. betaN2,DR for different carbons were observed to vary in the 0.292-0.539 range. Carbons with higher degrees of mesoporosity had higher betaN2,DR values, while no dependency was observed between betaN2,DR and surface chemistry. A comparison of DR and DA cases indicates that: (1) the average value of betaN2,DA is considerably above the classical value of this parameter; and (2) the range of betaN2,DA values were smaller compared to betaN2,DR, despite a wide range of mesoporosity of carbons examined. Obtained beta(TCE,DR) values varied in the 0.952-1.243 range, with an average value of 1.085+/-0.083, independent of surface chemistry or porosity of activated carbons. A similar result was observed for beta(TCE,DA). betaH2O,DR values of different granular and fibrous activated carbons changed in the range of 0.081-0.271. They depended more on the carbon surface chemistry and less on the porosity. A similar result was obtained when DA equation was considered.

Adsorption of dissolved natural organic matter by modified activated carbons.

Adsorption of dissolved natural organic matter (DOM) by virgin and modified granular activated carbons (GACs) was studied. DOM samples were obtained from two water treatment plants before (i.e., raw water) and after coagulation/flocculation/sedimentation processes (i.e., treated water). A granular activated carbon (GAC) was modified by high temperature helium or ammonia treatment, or iron impregnation followed by high temperature ammonia treatment. Two activated carbon fibers (ACFs) were also used, with no modification, to examine the effect of carbon porosity on DOM adsorption. Size exclusion chromatography (SEC) and specific ultraviolet absorbance (SUVA(254)) were employed to characterize the DOMs before and after adsorption. Iron-impregnated (HDFe) and ammonia-treated (HDN) activated carbons showed significantly higher DOM uptakes than the virgin GAC. The enhanced DOM uptake by HDFe was due to the presence of iron species on the carbon surface. The higher uptake of HDN was attributed to the enlarged carbon pores and basic surface created during ammonia treatment. The SEC and SUVA(254) results showed no specific selectivity in the removal of different DOM components as a result of carbon modification. The removal of DOM from both raw and treated waters was negligible by ACF10, having 96% of its surface area in pores smaller than 1 nm. Small molecular weight (MW) DOM components were preferentially removed by ACF20H, having 33% of its surface area in 1--3 nm pores. DOM components with MWs larger than 1600, 2000, and 2700 Da of Charleston raw, Charleston-treated, and Spartanburg-treated waters, respectively, were excluded from the pores of ACF20H. In contrast to carbon fibers, DOM components from entire MW range were removed from waters by virgin and modified GACs.

Trichloroethylene adsorption by fibrous and granular activated carbons: aqueous phase, gas phase, and water vapor adsorption studies.

The important adsorption components involved in the removal of trichloroethylene (TCE) by fibrous and granular activated carbons from aqueous solutions were systematically examined. Namely, adsorption of TCE itself (i.e., TCE vapor isotherms), water molecules (i.e., water vapor isotherms), and TCE in water (i.e., TCE aqueous phase isotherms) were studied, side-by-side, using 20 well-characterized surface-modified activated carbons. The results showed that TCE molecular size and geometry, activated carbon surface hydrophilicity, pore volume, and pore size distribution in micropores control adsorption of TCE at relatively dilute aqueous solutions. TCE adsorption increased as the carbon surface hydrophilicity decreased and the pore volume in micropores of less than 10 A, especially in the 5-8 A range, increased. TCE molecules appeared to access deep regions of carbon micropores due to their flat geometry. The results indicated that characteristics of both adsorbate (i.e., the molecular structure, size, and geometry) and activated carbon (surface hydrophilicity, pore volume, and pore size distribution of micropores) control adsorption of synthetic organic compounds from water and wastewaters. The important micropore size region for a target compound adsorption depends on its size and geometry.

Adsorption of oxygen by heat-treated granular and fibrous activated carbons.

Three granular and one fibrous activated carbon with different physicochemical characteristics were subjected to heat treatment at 900 degrees C under vacuum or hydrogen flow. Subsequently, oxygen chemi- and physisorption isotherms were volumetrically obtained at 34 degrees C. Oxygen sorption experiments showed lower amounts of oxygen uptake by the H(2)-treated than by the vacuum-treated carbons, indicating that H(2) treatment effectively stabilized the surfaces of various carbons tested in this study. At low pressures, from approximately 0.001 to approximately 5 mmHg, adsorption of oxygen was governed by irreversible chemisorption, which was well described by the Langmuir equation. At higher pressures oxygen uptake occurred as a result of physisorption, which was in agreement with Henry's law. Kinetic studies showed that oxygen chemisorption was affected by both carbon surface chemistry and porosity. The results indicated that oxygen chemisorption initially started in the mesopore region from the high energetic sites without any mass transfer limitation; thus a constant oxygen uptake rate was observed. Once the majority of these sites were utilized, chemisorption proceeded toward the less energetic sites in mesopores as well as all the sites located in micropores. As a result, an exponential decrease in the oxygen uptake rate was observed.