Promoting Effect of Ball Milling on the Functionalization and Catalytic Performance of Carbon Nanotubes in Glycerol Etherification.

A facile and eco-friendly approach using in situ-generated 4-benzenediazonium sulfonate (BDS) was applied to prepare highly functionalized carbon nanotubes (CNTs). The effectiveness of this functionalization was additionally enhanced by a green and short-time ball milling process applied beforehand. The obtained BDS-modified CNTs presented significant activity in glycerol etherification, producing tert-butyl glycerol ethers, which are considered promising fuel additives. Excellent results of ~56% glycerol conversion and ~10% yield of higher-substituted tert-butyl glycerol ethers were obtained within just 1 h of reaction at 120 °C using a low catalyst loading of only 2.5 wt.%. Furthermore, the sulfonated CNTs were reusable over several reaction cycles, with only a minor decrease in activity. Additionally, the sample activity could be restored by a simple regeneration approach. Finally, a clear correlation was found between the content of -SO3H groups on the surface of CNTs and the catalytic performances of these materials in glycerol etherification. Improved interaction between functionalized ball-milled CNTs and the reactants was also suggested to positively affect the activity of these catalysts in the tested process.

Facile Synthesis of Stable Cerium Dioxide Sols in Nonpolar Solvents.

A method is proposed for the preparation of stable sols of nanocrystalline cerium dioxide in nonpolar solvents, based on surface modification of CeO2 nanoparticles obtained by thermal hydrolysis of concentrated aqueous solutions of ammonium cerium(IV) nitrate with residues of 2-ethylhexanoic and octanoic acids. The synthesis was carried out at temperatures below 100 °C and did not require the use of expensive and toxic reagents. An assessment of the radical-scavenging properties of the obtained sols using the superoxide anion-radical neutralization model revealed that they demonstrate notable antioxidant activity. The results obtained indicate the potential of the nanoscale cerium dioxide sols in nonpolar solvents to be used for creating nanobiomaterials possessing antioxidant properties.

Emissions from a Diesel Engine using Fe-based Fuel Additives and a Sintered Metal Filtration System.

A series of laboratory tests were conducted to assess the effects of Fe-containing fuel additives on aerosols emitted by a diesel engine retrofitted with a sintered metal filter (SMF) system. Emission measurements performed upstream and downstream of the SMF system were compared, for cases when the engine was fueled with neat ultralow sulfur diesel (ULSD) and with ULSD treated with two formulations of additives containing Fe-based catalysts. The effects were assessed for four steady-state engine operating conditions and one transient cycle. The results showed that the SMF system reduced the average total number and surface area concentrations of aerosols by more than 100-fold. The total mass and elemental carbon results confirmed that the SMF system was indeed very effective in the removal of diesel aerosols. When added at the recommended concentrations (30 p.p.m. of iron), the tested additives had minor adverse impacts on the number, surface area, and mass concentrations of filter-out (FOut) aerosols. For one of the test cases, the additives may have contributed to measurable concentrations of engine-out (EOut) nucleation mode aerosols. The additives had only a minor impact on the concentration and size distribution of volatile and semi-volatile FOut aerosols. Metal analysis showed that the introduction of Fe with the additives substantially increased Fe concentration in the EOut, but the SMF system was effective in removal of Fe-containing aerosols. The FOut Fe concentrations for all three tested fuels were found to be much lower than the corresponding EOut Fe concentrations for the case of untreated ULSD fuel. The results support recommendations that these additives should not be used in diesel engines unless they are equipped with exhaust filtration systems. Since the tested SMF system was found to be very efficient in removing Fe introduced by the additives, the use of these additives should not result in a measurable increase in emissions of de novo generated Fe-containing aerosols. The findings from this study should promote a better understanding of the benefits and challenges of using sintered metal systems and fuel additives to control the exposure of underground miners and other workers to diesel aerosols and gases.

Health assessment of gasoline and fuel oxygenate vapors: generation and characterization of test materials.

In compliance with the Clean Air Act regulations for fuel and fuel additive registration, the petroleum industry, additive manufacturers, and oxygenate manufacturers have conducted comparative toxicology testing on evaporative emissions of gasoline alone and gasoline containing fuel oxygenates. To mimic real world exposures, a generation method was developed that produced test material similar in composition to the re-fueling vapor from an automotive fuel tank at near maximum in-use temperatures. Gasoline vapor was generated by a single-step distillation from a 1000-gallon glass-lined kettle wherein approximately 15-23% of the starting material was slowly vaporized, separated, condensed and recovered as test article. This fraction was termed vapor condensate (VC) and was prepared for each of the seven test materials, namely: baseline gasoline alone (BGVC), or gasoline plus an ether (G/MTBE, G/ETBE, G/TAME, or G/DIPE), or gasoline plus an alcohol (G/EtOH or G/TBA). The VC test articles were used for the inhalation toxicology studies described in the accompanying series of papers in this journal. These studies included evaluations of subchronic toxicity, neurotoxicity, immunotoxicity, genotoxicity, reproductive and developmental toxicity. Results of these studies will be used for comparative risk assessments of gasoline and gasoline/oxygenate blends by the US Environmental Protection Agency.

Validation of effect of composite additive on optimized combustion characteristics of CI engine using AHP and GRA method.

The primary focus of this study is the validation of composite additives with the help of additional optimization methods and the analysis of its effect on the combustion characteristics of compression ignition (CI) engines. Previous work on the identification of the correct multi additive combination by Taguchi and the TOPSIS optimization method has shown substantial improvements in the performance and emission characteristics of CI engines. The same work was extended using the GRA Optimization method with the Multi-Criteria Decision-Making (MCDM) optimization technique known as the Analytic Hierarchy Process (AHP) to validate the optimization results from the previous optimization work. Remarkably, all optimization methods yielded consistent results, pointing to the superiority of the composite additive sample 'D8EH6E4 hence supporting the outcome of previous work. Subsequent testing and comparison of this novel composite additive with baseline diesel fuel for combustion characteristics analysis demonstrated notable improvements in combustion parameters, including a 25 % reduction in the rate of pressure rise, an 18 % decrease in net heat release rate, and a 6 % decrease in mean gas temperature.

Exploring alternative fuel solutions: lemon grass oil biodiesel blend with dibutyl ether additive for VCR diesel engines - an experimental analysis.

There has been an intense surge in interest in the search for alternative sources of petroleum fuels in the modern world as a result of the inflation of fuel prices and the historic supply gap. When compared to petroleum fuels, biodiesel is becoming an increasingly valuable option due to the fact that it produces less emissions and provides the almost same amount of energy. In point of fact, the prime aim of this work is to explore the possibility of utilizing biodiesel derived from lemongrass oil and including dibutyl ether as an additive for the test diesel engine operating on varied compression ratios. The findings showed that the best operating settings are a 17.5 compression ratio with a blend of 30% biodiesel and 70% diesel fuel. At greater loads, brake thermal efficiency is lower than that of diesel engines. Lower loads result in lower specific fuel usage. Mechanical efficiency at higher loads is highest in the B30 blend, but emission metrics such as CO, CO2, HC, and NOx were reduced with the inclusion of an additive, though HC rose with higher loads of lemongrass oil biodiesel blends. When compared to the B30 biodiesel blend with various composition additives, the B30 + 4% additive has the highest efficiency at the fourth load in terms of both brake power and mechanical efficiency.

Kinetics and thermodynamics studies of nickel manganite nanoparticle as photocatalyst and fuel additive.

In this study, nickel manganite (NiMn2O4) nanoparticles were prepared using a hydrothermal method and examined its potential as a photocatalyst for the Acid Green 25 (AG-25) dye degradation. The nanoparticles were subjected to structural analysis using X-ray diffraction (XRD) and morphological analysis using scanning electron microscopy (SEM). The study examined the kinetics and thermodynamics of degradation processes that are catalyzed by photocatalysis. To ascertain their effect on dye degradation, several parameters, such as catalyst dose, H2O2 concentration, and temperature, were investigated. With a temperature of 315 K in a pseudo-first-order kinetic reaction, a 0.3 M H2O2 concentration, 0.05 mg/mL catalyst dose, and a promising removal efficiency of 96 % was achieved by the NiMn2O4 NPs in 40 min. Thermodynamic analysis revealed the spontaneous and entropy-driven nature of catalytic degradation, progressing favorably at elevated temperatures. Additionally, the NiMn2O4 NPs were applied as a fuel additive to analyze its influence on combustion and the physical characteristics of the modified fuel. The modified fuel demonstrated exceptional catalytic efficiency, emphasizing the potential of the NiMn2O4 NPs as an effective additive.

Nanostructured Solid/Liquid Acid Catalysts for Glycerol Esterification: The Key to Convert Liability into Assets.

Owing to the growing concerns about the dwindling fossil fuel reserves, increasing energy demand, and climate emergency, it is imperative to develop and deploy sustainable energy technologies to ensure future energy supply and to transition to the net-zero world. In this context, there is great potential in the biorefinery concept for supplying drop in biofuels in the form of biodiesel. Biodiesel as a fuel can certainly bridge the gap where electrification or the use of hydrogen is not feasible, for instance, in heavy vehicles and in the farm and marine transportation sectors. However, the biodiesel industry also generates a large amount of crude glycerol as the by-product. Due to the presence of several impurities, crude glycerol may not be a suitable feedstock for all high-value products derived from glycerol, but it fits well with glycerol esterification for producing glycerol acetins, which have numerous applications. This review critically looks at the processes using nanostructured solid/liquid acid catalysts for glycerol esterification, including the economic viability of the scale-up. The homogeneous catalysts reviewed herein include mineral acids and Brønsted acidic ionic liquids, such as SO3H-functionalized and heteropoly acid based ionic liquids. The heterogeneous catalysts reviewed herein include solid acid catalysts such as metal oxides, ion-exchange resins, zeolites, and supported heteropoly acid-based catalysts. Furthermore, the techno-economic analysis studies have shown the process to be highly profitable, confirming the viability of glycerol esterification as a potential tool for economic value addition to the biorefinery industry.

Urinary biomonitoring of fuel ether oxygenates using a needle trap device packed with a novel molecularly imprinted polymer surface modified Zeolite Y.

This study introduces an innovative needle trap device (NTD) featuring a molecularly imprinted polymer (MIP) surface-modified Zeolite Y. The developed NTD was integrated with gas chromatography-flame ionization detector (GC-FID) and employed for analysis of fuel ether oxygenates (methyl tert­butyl ether, MTBE, ethyl tert­butyl ether, ETBE, and tert­butyl formate, TBF) in urine samples. To optimize the key experimental variables including extraction temperature, extraction time, salt concentration, and stirring speed, a central composite design-response surface methodology (CCD-RSM) was employed. The optimal values for extraction in the study were found to be 51.2 °C extraction temperature, 46.2 min extraction time, 27 % salt concentration, and 620 rpm stirring speed. Under the optimized conditions, the calibration curves demonstrated excellent linearity within the range of 0.1-100 µg L-1, with correlation coefficients (R2) exceeding 0.99. The limits of detection (LODs) for MTBE, ETBE, and TBF were obtained 0.06, 0.08, and 0.09 µg L-1, respectively. Moreover, the limits of quantification (LOQs) for MTBE, ETBE, and TBF were obtained 0.18, 0.24, and 0.27 µg L-1, respectively. The enrichment factor was also found to be in the range of 98-129.The NTD-GC-FID procedure demonstrated a high extraction efficiency, making it a promising tool for urinary biomonitoring of fuel ether oxygenates with improved sensitivity and selectivity compared to current methods.

Unraveling the Nanosheet Zeolite-Catalyzed Combustion of Aluminum Nanoparticles-Doped exo-Tetrahydrodicyclopentadiene (JP-10) Energetic Fuel.

Nanosheet MFI zeolites (Zeolite Socony Mobil, five) have grown in popularity in cracking catalysis considering their tunability in porous topologies, acidic sites, and sheet thickness, thus allowing them to selectively adsorb molecules of specific sizes, shapes, and polarities, resulting in improved cracking performance for a specific fuel. Five different MFI zeolites in the form of a mesoporous nanosheet structure with a controlled concentration of acidic sites denoted as NSMFI(y), where y is Si/Al ratio, have been synthesized. The effects of the relative acidity content of these NSMFI(y) samples on the zeolite-catalyzed combustion of aluminum nanoparticles (AlNPs)-aided exo-tetrahydrodicyclopentadiene (JP-10) mixed energetic fuel droplets levitated in an oxygen-argon atmosphere were investigated using time-resolved imaging (optical and thermal infrared) and spectroscopic techniques (UV-vis and FTIR). The addition of 1.0 wt % of NSMFI(y) zeolites to AlNPs-JP-10 fluid fuel results in critically reduced ignition delays (9 ± 2 ms), elevated ignition temperatures (2800 ± 170 K), and prolonged burning times (60 ± 10 ms) with an enhanced combustion efficiency. The NSMFI(y) zeolites, which possess high acidity and significant mesoporosity, play a crucial role in improving the combustion efficiency by effectively catalyzing the chemical activation of JP-10 and prolonging the burning of the igniting droplet. The NSMFI (60) variant with the highest acidic site content achieved a maximum combustion efficiency of 80 ± 6%. A comprehensive catalytic combustion mechanism has been elucidated based on the detected reactive intermediates such as hydroxyl radical (OH) and aluminum monoxide (AlO). These findings will help to critically advance the development of next-generation, sustainable, and innovative mixed nanofluid fuels.

The combined effect of acetone and ZnO with diesel-biodiesel blends on the performance, combustion and emission characteristics of diesel engine.

In this experimental study, the performance, combustion and emission analysis of the combined effect of acetone and Zinc Oxide (ZnO) dispersed diesel-biodiesel (B20) blends were done in four-stroke, single-cylinder and water-cooled diesel engine. ZnO was synthesized by the solvothermal method using cow urine as a solvent and reducing agent. The synthesized ZnO was characterized by X-ray diffraction (XRD) and Scanning Electron Microscope (SEM). The biodiesel was produced from waste cooking oil through a trans-esterification process. The synthesized ZnO was dispersed in 10, 20 and 30 ppm with diesel-biodiesel blend along with 10% of acetone to form B20A10Zn10, B20A10Zn20 and B20A10Zn30 test fuels. The experimental results show that adding acetone and ZnO with diesel-biodiesel blend tends to promising physiochemical properties of the test fuels and produced better results in performance and emission. The test fuel, B20A10Zn30, gave a better outcome than all other fuels and recorded a 0.4% increase in Brake Thermal Efficiency (BTE), while there was an 8% increase in Brake Specific Fuel Consumption (BSFC). Compared to diesel, the emissions, such as Carbon Monoxide (CO), Unburned Hydrocarbon (UHC), Oxides of Nitrogen (NOx), and smoke, were 7.97%, 20%, 1.8% and 1.49% lower than the conventional diesel.

Exhaust emissions from diesel engines fueled by different blends with the addition of nanomodifiers and hydrotreated vegetable oil HVO.

Diesel emissions have a significant impact on the atmosphere, contributing to air pollution, smog and global warming. As a result, diesel exhaust is dangerous to human health. While emissions reduction efforts have often focused on changing engine design or improving aftertreatment, diesel fuel modifications can also play an important role in improving engine efficiency and reducing exhaust emissions. The aim of this work was to examine the potential for emissions reductions under real-world conditions when employing fuel additives. Three different additives were examined, consisting of hydrotreated vegetable oil (HVO) and two commercial additives containing nanoparticles of cerium dioxide and ferrocene. HVO was selected as a renewable fuel, an alternative to commonly used biodiesels with competitive advantages. The new European driving cycle (NEDC) procedure was used to measure emissions of regulated compounds: carbon monoxide, nitrogen oxides, hydrocarbons and particulates (by mass and number) from an 11-year-old passenger car equipped with a diesel engine powered by fuel blends. The fuel blends prepared met the quality requirements for diesel fuel. The results obtained confirm that the application of both HVO and nano-additives to diesel can achieve a significant reduction of carbon monoxide (52%) and hydrocarbon (47%) emissions compared to the B7 base fuel. Particulate emissions (up to 10% by mass of particulates and 7% by number of particulates) were found to be best reduced by adding nanoparticles of cerium dioxide to the B7 fuel (with 30% HVO), while the best results in reducing nitrogen oxide emissions were obtained by adding ferrocene nanoparticles to the B7 fuel with 30% HVO.

A Review on the Catalytic Acetalization of Bio-renewable Glycerol to Fuel Additives.

The last 20 years have seen an unprecedented breakthrough in the biodiesel industry worldwide leads to abundance of glycerol. Therefore, the economic utilization of glycerol to various value-added chemicals is vital for the sustainability of the biodiesel industry. One of the promising processes is acetalization of glycerol to acetals and ketals for applications as fuel additives. These products could be obtained by acid-catalyzed reaction of glycerol with aldehydes and ketones. Application of different supported heterogeneous catalysts such as zeolites, heteropoly acids, metal-based and acid-exchange resins have been evaluated comprehensively in this field. In this review, the glycerol acetalization has been reported, focusing on innovative and potential technologies for sustainable production of solketal. In addition, the impacts of various parameters such as application of different reactants, reaction temperature, water removal, utilization of crude-glycerol on catalytic activity in both batch and continuous processes are discussed. The outcomes of this research will therefore significantly improve the technology required in tomorrow's bio-refineries. This review provides spectacular opportunities for us to use such renewables and will consequently benefit the industry, environment and economy.

Role of fuel additives on reduction of NOX emission from a diesel engine powered by camphor oil biofuel.

The present study intends to explore the effect of the addition of fuel additives with camphor oil (CMO) on the characteristics of a twin-cylinder compression ignition (CI) engine. The lower viscosity and boiling point of CMO when compared to diesel could improve the fuel atomization, evaporation, and air/fuel mixing process. However, the lower cetane index of CMO limits its use as a drop in fuel for diesel in CI engine. In general, NOX emission increases for less viscous and low cetane (LVLC) fuels due to pronounced premixed combustion phase. To improve the ignition characteristics and decrease NOX emissions, fuel additives such as diglyme (DGE)-a cetane enhancer, cumene (CU)-an antioxidant, and eugenol (EU) and acetone (A)-bio-additives, are added 10% by volume with CMO. The engine used for the experimentation is a twin-cylinder tractor engine that runs at a constant speed of 1500 rpm. The engine was operated with diesel initially to attain warm-up condition, which facilitates the operation of neat CMO. At full load condition, brake thermal efficiency (BTE) for CMO is higher (29.6%) than that of diesel (28.1%), while NOX emission is increased by 9.4%. With DGE10 (10% DGE + 90% CMO), the ignition characteristics of CMO are improved and BTE is increased to 31.7% at full load condition. With EU10 (10% EU + 90% CMO) and A10 (10% A + 90% CMO), NOX emission is decreased by 24.6 and 17.8% when compared to diesel, while BTE is comparable to diesel. While HC and CO emission decreased for DGE10 and CU10, they increased for EU10 and A10 when compared to baseline diesel and CMO.

Vapor intrusion risk of lead scavengers 1,2-dibromoethane (EDB) and 1,2-dichloroethane (DCA).

Vapor intrusion of synthetic fuel additives represented a critical yet still neglected problem at sites impacted by petroleum fuel releases. This study used an advanced numerical model to simulate the vapor intrusion risk of lead scavengers 1,2-dibromoethane (ethylene dibromide, EDB) and 1,2-dichloroethane (DCA) under different site conditions. We found that simulated EDB and DCA indoor air concentrations can exceed USEPA screening level (4.7 × 10(-3) µg/m(3) for EDB and 1.1 × 10(-1) µg/m(3) for DCA) if the source concentration is high enough (is still within the concentration range found at leaking UST site). To evaluate the chance that vapor intrusion of EDB might exceed the USEPA screening levels for indoor air, the simulation results were compared to the distribution of EDB at leaking UST sites in the US. If there is no degradation of EDB or only abiotic degradation of EDB, from 15% to 37% of leaking UST sites might exceed the USEPA screening level. This study supports the statements made by USEPA in the Petroleum Vapor Intrusion (PVI) Guidance that the screening criteria for petroleum hydrocarbon may not provide sufficient protectiveness for fuel releases containing EDB and DCA. Based on a thorough literature review, we also compiled previous published data on the EDB and DCA groundwater source concentrations and their degradation rates. These data are valuable in evaluating EDB and DCA vapor intrusion risk. In addition, a set of refined attenuation factors based on site-specific information (e.g., soil types, source depths, and degradation rates) were provided for establishing site-specific screening criteria for EDB and DCA. Overall, this study points out that lead scavengers EDB and DCA may cause vapor intrusion problems. As more field data of EDB and DCA become available, we recommend that USEPA consider including these data in the existing PVI database and possibly revising the PVI Guidance as necessary.