Optimization of low-grade coal and refuse-derived fuel blends for improved co-combustion behavior in coal-fired power plants.

This study is aimed at utilizing three waste materials, i.e., solid refuse fuel (SRF), tire derived fuel (TDF), and sludge derived fuel (SDF), as eco-friendly alternatives to coal-only combustion in co-firing power plants. The contribution of waste materials is limited to ≤5% in the composition of the mixed fuel (coal + waste materials). Statistical experimental design and response surface methodology are employed to investigate the effect of mixed fuel composition (SRF, TDF, and SDF) on gross calorific value (GCV) and ash fusion temperature (AFT). A quadratic model is developed and statistically verified to apprehend mixed fuel constituents' individual and combined effects on GCV and AFT. Constrained optimization of fuel blend, i.e., GCV >1,250 kcal/kg and AFT >1,200 °C, using the polynomial models projected the fuel-blend containing 95% coal with 3.84% SRF, 0.35% TDF, and 0.81% SDF. The observed GCV of 5,307 kcal/kg and AFT of 1225 °C for the optimized blend were within 1% of the model predicted values, thereby establishing the robustness of the models. The findings from this study can foster sustainable economic development and zero CO2 emission objectives by optimizing the utilization of waste materials without compromising the GCV and AFT of the mixed fuels in coal-fired power plants.

Optimization of tetracycline removal from water by iron-coated pine-bark biochar.

We synthesized iron-coated pine-bark biochar (Fe-PBB) and determined the optimal conditions for removing the antibiotic tetracycline from water. The Fe-PBB was synthesized by depositing iron oxide on pyrolyzed pine-bark waste via a facile co-precipitation method. Characterization (SEM, EDX, and TGA) showed successful deposition of a mass of approximately 27% (w/w) iron on the PBB to synthesize Fe-PBB. Fe-PBB exhibited five times higher adsorption capacity (~ 10 mg/g) for tetracycline compared with PBB. The effects of initial tetracycline concentration, pH, temperature, and Fe-PBB dose on the adsorption removal of tetracycline from water were systematically investigated and optimized using a statistical experimental design and response surface methodology. The empirical relationship between the experimental factors and tetracycline removal was modeled, statistically validated through the analysis of variance, and used to predict the optimal conditions for adsorption removal of tetracycline. We found that ≥ 95% of the tetracycline can be removed at a tetracycline concentration of 1 mg/L, pH of 7, temperature of 50 °C, and a Fe-PBB dose of 2 g/L. The adsorption isotherm modeling study suggests that the adsorption of tetracycline can be attributed to the pore filling phenomenon and multilayer adsorption on the Fe-PBB. A thermodynamics study showed that the adsorption occurs spontaneously with an endothermic reaction.

Optimized removal of hexavalent chromium from water using spent tea leaves treated with ascorbic acid.

Spent tea leaves were functionalized with ascorbic acid to obtain treated tea waste (t-TW) to encourage the adsorption of hexavalent chromium from water. The adsorption removal of Cr(VI) was systematically investigated as a function of four experimental factors: pH (2-12), initial Cr(VI) concentration (1-100 mg L-1), t-TW dosage (0-4 g L-1), and temperature (10-50 °C) by following a statistical experimental design. A central composite rotatable experimental design based on a response surface methodology was used to establish an empirical model that assessed the individual and combined effects of factors on adsorptive removal of Cr(VI). The model was experimentally verified and statistically validated then used to predict optimal adsorption removal of Cr(VI) from water. At optimized conditions, ≥ 99% of 1 mg L-1 Cr(VI) can be removed by 4 g L-1 t-TW at a pH of 9. The adsorptive mechanism was assessed by conducting kinetics and equilibrium studies. The adsorption of Cr(VI) by t-TW followed a pseudo-second-order kinetics model (k2 = 0.001 g mg-1 h-1) and could be described by Langmuir and Temkin isotherms, indicating monolayer adsorption and predominantly adsorbate-adsorbent interactions. The t-TW exhibited a competitive Cr(VI) adsorption capacity of 232.2 mg g-1 compared with the other low-cost adsorbents. These results support the utilization of tea waste for the removal of hazardous metal contaminants from aqueous systems.

Production and characterization of cost-effective magnetic pine bark biochar and its application to remove tetracycline from water.

Low-cost adsorbent, pine bark biochar (PBB) from the forest residue, was produced and applied to remove tetracycline (TC) from aqueous solution via adsorption pathway. The PBB, hence obtained, was modified using aqueous ferric and ferrous ion solutions to obtain magnetic pine bark biochar (M-PBB). Batch adsorption experiments were conducted to examine the adsorption of TC by PBB and M-PBB in the variation of pH, contact time, dosage, and temperature. The adsorbents were characterized by SEM/EDX, TGA, and pHpzc. The adsorption mechanism was evaluated by fitting Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich (D-R) isotherms model. Also, the experimental data were analyzed by kinetics models (pseudo-first-order, pseudo-second-order, intra-particle diffusion, and Elovich) and thermodynamics. The maximum adsorption capacity (qm) of M-PBB was 15.3 mg/g from the experiment at pH 6. A high correlation coefficient (R2 ≈ 0.9) of Freundlich isotherm postulated multi-layer adsorption of TC on M-PBB at pH 6. The kinetic studies showed that the pseudo-first-order was more suitable for representing the adsorption of TC molecules on the surface. The thermodynamic analysis was showed that the adsorption process is favorable, spontaneous, and endothermic at studied temperatures. M-PBB demonstrated a potential for removal of TC from water as a low-cost and convenient adsorbent.

Experimental modeling and optimization for the reduction of hexavalent chromium in aqueous solutions using ascorbic acid.

In this study, we investigated the reduction of toxic Cr(VI) to less toxic Cr(III) using ascorbic acid in various aqueous solutions: deionized water, synthetic soft water, synthetic hard water, and real tap water. The experiments were performed using a statistical experimental design. Response surface methodology (RSM) was used to correlate Cr(VI) reduction (response variable) with experimental parameters such as initial Cr(VI) concentration, humic acid concentration, and ascorbic acid dosage. The empirical model obtained from the experiments was used to estimate and optimize the quantity of ascorbic acid required for the reduction of ≥ 99% Cr(VI) in water. The optimized dosages of ascorbic acid were predicted and experimentally validated for > 99.5% reduction of Cr(VI) (1, 10, 20, and 100 mg/L) in the solutions. Even a solution containing an initial Cr(VI) concentration of 100 mg/L was reduced in concentration ≥ 99.9% with optimal dosage of ascorbic acid (500 mg/L) in the presence of 20 mg/L humic acid. Moreover, the reaction kinetics (kobs-Cr(VI) = 0.71 mM-1 s-1) were sufficient to reduce the ≥ 99.9% Cr(VI) in 20 min. This study sheds new light on the effect of ascorbic acid on Cr(VI) reduction, and provides knowledge fundamental to optimize treatment of Cr(VI) contaminated water to environmentally acceptable endpoints.

Deep Eutectic Solvent Assisted Dispersion of Carbon Nanotubes in Water.

Deep Eutectic Solvents (DESs) are emerging as a promising medium for many chemical processes. They can be used to observe specific properties required for nanomaterials' applications. Controlled CO2 adsorption requires disaggregation of carbon nanotubes into smaller bundles which can be accomplished by dispersing them in aqueous DES system. In this study, response surface methodology (RSM) was adopted to examine the impacts of three important factors on the dispersion of single walled carbon nanotubes (SWNTs) in Choline Chloride-Glycerol (ChCl-Gly) DES; (i) ChCl-Gly (mass% in water), (ii) sonication energy input (J/mL), and (iii) SWNTs' concentration (mg/L). The net negative surface charge of ChCl-Gly, a "green solvent," provided superior dispersion of inherently negatively charged SWNTs in water via electrostatic repulsion. The impacts of the dispersion factors were quantified by the average aggregate diameter (nm) and polydispersity (polydispersity index, PDI) of SWNTs in aqueous-DES systems. Models were developed, experimentally verified, and statistically validated to map the impacts of these factors and to obtain optimized dispersions. The optimized dispersions, characterized by the small (<100 nm) and uniform (<0.1 PDI) SWNTs' aggregates, were achieved at lower sonication energy costs which can have promising implications across many nano-manufacturing fields. The dispersion/aggregation mechanism was proposed using COSMO-RS (based on equilibrium thermodynamics and quantum chemistry) modeling of ChCl-Gly and zeta potential measurements of SWNTs. This understanding will help create optimally sustainable and economically feasible DES-nanomaterial dispersions.

Ultrasonic Synthesis of Carbon Nanotube-Titanium Dioxide Composites: Process Optimization via Response Surface Methodology.

In this study, the central composite design of response surface methodology was applied to optimize the ultrasonic synthesis of multiwalled carbon nanotube-titanium dioxide (MWNT-TiO2) composites. Twenty composites were prepared by adjusting three parameters (MWNT concentration in water, sonication to disperse/exfoliate MWNTs in water, and sonication to attach TiO2 onto MWNTs) at five levels. On the basis of the experimental design, semiempirical expressions were developed, analyzed, statistically assessed, and subsequently applied to predict the impact of the studied parameters on composite synthesis. The composite synthesis process was optimized to capture the experimental conditions favoring the highest productivity (i.e., MWNT-TiO2 formation or percent TiO2 attachment) utilizing minimal resources. The synthesis process optimization results showed that, to make a MWNT-TiO2 composite in 10 mL of water, 23.2 mg (∼99% of 23.4 mg) of TiO2 can be attached to 2.6 mg of MWNTs. This process requires only 727 J sonication energy, of which 592 J is invested to exfoliate MWNTs (Sonication 1) and 135 J to attach TiO2 (Sonication 2) to MWNTs. Finally, the optimally synthesized composite was extensively characterized using SEM, surface area and porosity analysis, TGA, and ζ-potential analysis/DLS. Also, this composite was tested for stability under variable pH and solvent polarity. The approach developed in this study could be used to optimize the synthesis process of other similar composites.

Optimization of Carbon Nanotube Dispersions in Water Using Response Surface Methodology.

The aim of this work was to demonstrate an optimization methodology to reliably obtain stable macrodispersions (i.e., for ≥24 h) of carbon nanotubes in water using sonication. Response surface methodology (RSM) was utilized to assess and optimize the sonication parameters for the process. The studied input parameters were (i) sonication time (duration), (ii) amplitude (of vibration), and (iii) pulse-on/off (duration) of the sonicator. The analyzed responses were mean diameter and size distribution of multiwalled carbon nanotube (MWNT) aggregates in water, which were measured by the dynamic light scattering technique. A semiempirical model was developed and statistically tested to estimate the magnitude of sonicator parameters required to obtain specified MWNT macrodispersions (i.e., aggregates' mean diameter and distribution) in water. The results showed that MWNT aggregates of 2 ± 0.5 µm can be obtained by optimizing sonicator parameters to a sonication time of 89 s, amplitude of 144 µm, and pulse-on/off cycle of 44/30 s. These process settings for 100 mg/L MWNTs in a 30 mL aliquot of deionized water would consume 863 J/mL of sonication energy. Contrary to the popular belief, "sonication time" and/or "sonication energy input" were not found to be proportional to the degree of dispersion of MWNTs in water. This might be the reason for the frequent disparity and nonreproducibility of sonication results reported in scientific literature, especially for dispersing nanomaterials in a number of different systems. The amplitude of vibration was noted to be the most sensitive parameter affecting MWNT aggregates' diameter and distribution in water. The characterization of MWNTs was performed using electron microscopy, surface area analyzer, thermogravimetric analyzer, and zeta potential analyzer. This study can be helpful in evaluating sonication dispersion of particulate matter in other incompressible fluids such as graphene dispersion in organic solvents.

Using multi-walled carbon nanotubes (MWNTs) for oilfield produced water treatment with environmentally acceptable endpoints.

In this study, multi-walled carbon nanotubes (MWNTs) were employed to remove benzene, toluene, ethylbenzene, and xylenes (BTEX) from low and high salinity water pre-equilibrated with crude oil. The treatment endpoint of crude oil-contaminated water is often controlled by BTEX compounds owing to their higher aqueous solubility and human-health toxicity compared to other hydrocarbons. The MWNT sorbent was extensively characterized and the depletion of the organic sorbate from the produced water was monitored by gas chromatography-mass spectrometry (GC-MS) and total organic carbon (TOC) analyses. The equilibrium sorptive removal of BTEX followed the order: ethylbenzene/o-xylene > m-xylene > toluene > benzene in the presence of other competing organics in produced water. Sorption mechanisms were explored through the application of a variety of kinetics and equilibrium models. Pseudo 2(nd) order kinetics and Freundlich equilibrium models were the best at describing BTEX removal from produced water. Hydrophobic interactions between the MWNTs and BTEX, as well as the physical characteristics of the sorbate molecules, were regarded as primary factors responsible for regulating competitive adsorption. Salinity played a critical role in limiting sorptive removal, with BTEX and total organic carbon (TOC) removal falling by 27% and 25%, respectively, upon the introduction of saline conditions. Results suggest that MWNTs are effective in removing risk-driving BTEX compounds from low-salinity oilfield produced water.

Photo-regenerable multi-walled carbon nanotube membranes for the removal of pharmaceutical micropollutants from water.

Pharmaceutical micropollutants fall in the category of "emerging contaminants" in water because of their prevalence and persistence in the aqueous environment, and because of a poor understanding of their low-dose exposure effects on human and animal populations. In this study, photo-regenerable multiwalled carbon nanotube membranes with variable water permeabilities were produced by embedding hierarchical TiO2 structures (having porous, spherical morphology) onto a pre-deposited bed of multi-walled carbon nanotubes (MWNTs) using a modified sol-gel technique. These MWNT-TiO2 composites and their constituent materials were characterized by analytical electron microscopy, surface charge measurement, thermogravimetric analysis, and hydrophobicity determination. The adsorption removal potential of MWNT-TiO2 membranes was demonstrated for three representative pharmaceuticals: acetaminophen, carbamazepine and ibuprofen. The peak initial removal percentages of the pharmaceuticals by the MWNT-TiO2 membranes were 80%, 45%, and 24% for carbamazepine, ibuprofen, and acetaminophen, respectively. The ability of the membranes to be regenerated, once they were saturated with the pharmaceutical compounds, was verified by repeating the adsorption removal experiment on the same membranes after exposure to UV light at 254 nm. Peak removal efficiencies after regeneration were 55%, 32%, and 19% for carbamazepine, ibuprofen, and acetaminophen, respectively, indicating some loss in sorptive capacity upon regeneration. Furthermore, the effect of pH on adsorption of ibuprofen, the pharmaceutical that attained the highest mass loading on the sorbent at equilibrium saturation, was studied and its mechanism of adsorption was proposed at pH below pKa.

Ultrasonication study for suspending single-walled carbon nanotubes in water.

A systematic calorimetry-based technique was developed to standardize single-walled carbon nanotube (SWNT) dispersion protocol. Simple calorimetric experiments were performed to benchmark the performance of the ultra-dismembrator. Temperature profiles for the sonication period were utilized to estimate energy input to the system. Energy loss profile was generated for the ultradismembrator in use and a calibration relationship was formulated that could standardize the sonication process. The standardized protocol was used to prepare aqueous SWNT suspensions-sonicating SWNTs in a varied range of input energy (18-100 kJ) in water. SWNT mass fractions suspended for each energy input was accurately measured and the suspended SWNT samples were characterized for morphology, surface potential, cluster size and structure, and chemical functionality using high resolution transmission electron microscopy (HRTEM), electrophoresis, dynamic and static light scattering (DLS/SLS), and Raman spectroscopy. The study demonstrated that suspended mass of SWNTs increased up to 18 kJ of energy input with no further increase upon continued energy input. The physicochemical properties showed similar trend for energy input. The aggregate cluster size, surface potential behavior, as well as the Raman defect properties plateaued after the initial energy input. The significant changes observed were limited to morphological properties, i.e., shorter length, debundled, and sharp edged SWNTs and fractal cluster formation (lower D(f)) with increased input energy.

Removal of bisphenol A and 17α-ethinyl estradiol from landfill leachate using single-walled carbon nanotubes.

In this study, the adsorption of bisphenol A (BPA) and 17α-ethinyl estradiol (EE2) from landfill leachate onto single-walled carbon nanotubes (SWCNTs) was investigated. Different leachate solutions were prepared by altering the pH, ionic strength, and dissolved organic carbon (DOC) in the solutions to mimic the varying water conditions that occur in leachate during the various stages of waste decomposition. The youngest and oldest leachate solutions contained varying DOC and background chemistry and were represented by leachate Type A (pH = 5.0; DOC = 2500 mg/L; conductivity = 12,500 µS/cm; [Ca(2+)] = 1200 mg/L; [Mg(2+)] = 470 mg/L) and Type E (pH = 7.5; DOC = 250 mg/L; conductivity = 3250 µS/cm; [Ca(2+)] = 60 mg/L; [Mg(2+)] = 180 mg/L). These solutions were subsequently combined in different ratios to produce intermediate solutions, labeled B-D, to replicate time-dependent changes in leachate composition. Overall, a larger fraction of EE2 was removed as compared to BPA, consistent with its higher log K(OW) value. The total removal of BPA and EE2 decreased in older leachate solutions, with the adsorptive capacity of SWCNTs decreasing in the order of leachate Type A > Type B > Type C > Type D > Type E. An increase in the pH from 3.5 to 11 decreased the adsorption of BPA by 22% in young leachate and by 10% in old leachate. The changes in pH did not affect the adsorption of EE2 in the young leachate, but did reduce adsorption by 32% in the old leachate. Adjusting the ionic strength using Na(+) did not significantly impact adsorption, while increasing the concentration of Ca(2+) resulted in a 12% increase in the adsorption of BPA and a 19% increase in the adsorption of EE2. DOC was revealed to be the most influential parameter in this study. In the presence of hydrophilic DOC, represented by glucose in this study, adsorption of the endocrine disrupting compounds (EDCs) onto the SWCNTs was not affected. In the absence of SWCNTs, hydrophobic DOC (i.e., humic acid) adsorbed 15-20% of BPA and EE2. However, when the humic acid and SWCNTs were both present, the overall adsorptive capacity of the SWCNTs was reduced. Hydrophobic (π-π electron donor-acceptor) interactions between the EDCs and the constituents in the leachate, as well as interactions between the SWCNTs and the EDCs, are proposed as potential adsorption mechanisms for BPA and EE2 onto SWCNTs.