The proton exchange membrane fuel cell systems using methanolysis of sodium borohydride as a hydrogen source with cobalt catalysts

Constant hydrogen generation via a hydrogen generator is evaluated from the methanolysis of sodium borohydride (NaBH₄) using Co/Al₂O₃ and MnO_x/Al₂O₃ catalysts. Chemical borohydrides coupled with catalysts can be used for compact storage and to create efficient generation systems. Thus, we first report the catalytic activity of MnO_x/Al₂O₃, which is synthesized using the simple wet-impregnation method, for the methanolysis reaction. The results indicate that both catalysts can effectively accelerate the methanolysis reaction and provide constant hydrogen generation rates. Thus, we integrate this hydrogen generation system into a proton exchange membrane fuel cell stack (PEMFC) to determine whether it can be used as a portable power supply. As a result, this fuel cell system operates at 40 W for 1 hr using the hydrogen source supplied from the catalytic methanolysis reaction.     

Decomposition of NaBH4 with self-regeneration of carbon-supported CoCl2 catalyst

In this study, economically favorable CoCl₂ catalysts at four different amounts were supported on activated carbon (AC) for NaBH₄ dehydrogenation. Supported catalyst could achieve hydrogen release for 2,060 cycles, which is equivalent to 103 days of uninterrupted operation. Slow and continuous hydrogen release was observed in all experiments. Even 1 g of NaBH₄ can carry 1.2 L of hydrogen, and in hydrolysis process, it liberates 2.5 L of hydrogen that indicates the decomposition of water. EDX analysis and reverse burette measurements show that CoCl₂ could be homogeneously distributed on and permanently joined to the support surface. Kinetic investigation of the dehydrogenation reaction fits zero order kinetics, and activation energy was calculated to be 48 kJ/mol.     

Relationship between liquid depth and the acoustic generation of hydrogen: design aspect for large cavitational reactors with special focus on the role of the wave attenuation

Understanding the effect of the liquid depth (z) on the acoustic generation of hydrogen is highly required for designing large-scale sonoreactors for hydrogen production because acoustic cavitation is the central event that initiates sonochemical reactions. In this paper, we present a computational analysis of the liquid-depth effect on the generation of H₂ from a reactive acoustic bubble trapped in water irradiated with an attenuating sinusoidal ultrasound wave. The computations were made for different operating conditions of frequency (355–1000 kHz), acoustic intensity (1–5 W/cm²), and liquid temperature (10–30°C). The contribution of the acoustic wave attenuation on the overall effect of depth was appreciated for the different conditions. It was found that the acoustic generation of hydrogen diminished hardly with increasing depth up to z = 8 m, and the depth effect was strongly operating parameter-dependent. The sound wave attenuation played a crucial role in quenching H₂ yield, particularly at higher z. The reduction of the H₂ yield with depth was more pronounced at higher frequency (1000 kHz) and lower temperature (10°C) and acoustic intensity (1 W/cm²). The attenuation of the sound wave may contribute up to 100% in the overall reductive effect of depth toward H₂ production rate. This parameter could be imperatively included when studying all aspects of underwater acoustic cavitation.     

Effects of alkali promoters on the textural and catalytic properties of mesoporous Fe–Al–Cu catalysts for water gas shift reaction

Mesoporous Fe₂O₃–Al₂O₃–CuO catalysts promoted with alkali oxides were synthesized and used in water gas shift reaction (WGSR) at high temperatures for hydrogen purification. These chromium-free catalysts were characterized using nitrogen adsorption/desorption, hydrogen temperature programmed reduction, X-ray diffraction (XRD), and transmission electron microscopy techniques. The synthesized catalysts with narrow single-modal pore size distribution in mesopore region possessed high specific surface area. The catalytic results revealed that except Cs, the addition of other alkali promoters declined the catalytic activity. However, all catalysts showed higher catalytic performance than the conventional commercial catalyst. The results showed an optimum content of Cs promoter (3 wt.%) for the promoted Fe–Al–Cu catalyst (3 wt.% Cs-FAC), which exhibited the highest activity in WGSR at high temperature.     

Reforming of CO2-containing natural gas with steam in AC gliding arc discharge for hydrogen production

In this study, a low-temperature gliding arc discharge system was used to investigate the effects of steam content and operational parameters, i.e. total feed flow rate, applied voltage, and input frequency, on the reforming performance of CO₂-containing natural gas. The addition of steam less than 10% was found to enhance both selectivities for hydrogen and carbon monoxide with a significant reduction of power consumptions. The highest hydrogen selectivity and yield with the lowest power consumptions were achieved at a steam content of 10 mol%, a total feed flow rate of 100 cm³/min (corresponding to a very short residence time of 1.37 s), an applied voltage of 13.5 kV and an input frequency of 300 Hz. Under these optimum conditions, the oxidative dehydrogenation reactions to produce hydrogen were dominant with the minimum activities of all undesired reactions of cracking and coupling. Both of the short residence time (1.37 s) with a low bulk temperature (lower than 200°C) in the plasma zone under atmospheric pressure, indicate that the studied plasma reactor (gliding arc system) is superior to conventional catalytic reactors for reforming of natural gas.     

Synthesis and characterization of multi-walled carbon nanotubes from silkworm cocoons to use as the cathode material for Al-air battery

ABSTRACT

Carbon nanotubes have been synthesized by chemical vapor deposition at 850°C using silkworm cocoons as a precursor. The impregnation method with 3 wt% ferrocene as a catalyst was utilized for growth of carbon nanotubes. The flow rates of C₂H₂, H₂, and N₂ were fixed at 100, 150, and 350 ml/min, respectively. Morphology, microstructure and quality of the synthesized carbon nanotubes were investigated by scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy techniques. Results showed that the prepared carbon nanotubes were multiwalled and good graphitic quality. When used as the cathode material for aluminum-air battery, prepared carbon nanotubes cathode exhibited higher current density than commercial graphite cathode. Based on our study, there is a successful conversion of silkworm cocoons into value-added nanomaterial products, promoting the natural biotechnological materials.     

Dry reforming of methane over oil palm shell activated carbon and ZSM-5 supported cobalt catalysts

In this study, cobalt supported oil palm shell activated carbon (Co/OPS-AC) and ZSM-5 zeolite (Co/ZSM-5) catalysts have been prepared for dry reforming of methane. Cobalt ratios of 6.0 and 14.0 wt% were deposited via wet impregnation method to the OPS-AC and ZSM-5 catalysts. The catalysts were characterized by XRD, N₂ adsorption--desorption isotherms, BET surface area, SEM, FESEM-EDX, TPR-H₂, and TPD-NH₃. The dry reforming of methane was performed using a micro reactor system under the condition of 10,000 ml/h.g-cat, 3 atm, CH₄/CO₂ ratio of 1.2:1.0 and temperature range from 923 K to 1023 K. The gaseous products were analyzed by gas chromatography (GC) with thermal conductivity detector (TCD) and further quantified to determine the conversions of CH₄ and CO₂, and the yields of CO and H₂. Experimental results revealed both catalysts exhibited lower conversions of CO₂ and CH₄ with the increase in temperature from 923 K to 1023 K. The reduced conversions may be due to the formation of carboneous substance on the catalyst known as coking. Comparatively, Co/OPS-AC gave higher conversions of CO₂ and CH₄ as well as higher yields of H₂ and CO as it has a higher surface area than Co/ZSM-5 which subsequently rendered higher activity for the reforming of methane. With the increasing cobalt loadings and reaction temperature, OPS-AC(14) catalyst exhibited improved activity and H₂/CO ratio. Based on these results, cobalt supported OPS activated carbon catalyst was suggested to be more effective for CO₂ and CH₄ conversions.     

Promotional effect of transition metal doping on the properties of KF/CaO catalyst for biodiesel synthesis

A series of heterogeneous KF/CaO catalysts modified with transition metals (lanthanum, cerium, and zirconium) were prepared via wet impregnation method and applied to the trsansesterification process of waste cooking oil (WCO) as feedstock with methanol to biodiesel production. The structure, performance of the solid catalysts was characterized by X-ray diffraction (XRD), temperature programmed desorption of CO₂ (CO₂-TPD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The effect of methanol/oil molar ratio, ¹reaction time, reaction temperature, catalyst amount, and stability was investigated. The results showed that 10 wt% of lanthanum, cerium, and zirconium improved the catalytic activity of KF/CaO catalyst. The maximum catalytic activity using the lanthanum doping of 10wt% on KF/CaO catalyst was reached 98.7% under the optimal reaction condition of methanol/oil molar ratio of 12:1, reaction for 1 h at reaction temperature of 65°C, and 4% (wt/wt oil) catalyst amount. In addition, the FAME yield of KF/CaO/La catalyst remained higher than 95% after 10 cycles. The promotional effect of lanthanum doping could be attributed to the enhancement of the basicity strength of KF/CaO catalyst and block the leach of Ca²⁺ in the transesterification reaction.     

Transesterification of Pistacia chinensis seed oil using a porous cellulose-based magnetic heterogeneous catalyst

In the present work, a novel cellulose-based porous heterogeneous solid acid catalyst encapsulation of ferriferous oxide (Fe₃O₄) and sulfonated graphene (GO-SO₃H) into cellulose to form composite porous microspheres catalyst (GO-SO₃H/CM@Fe₃O₄)was synthesized and evaluated for biodiesel production from Pistacia chinensis seed oil. The SEM, EDS and FTIR analysis revealed that the catalyst GO-SO₃H/CM@Fe₃O₄ owned stronger active sites and GO-SO₃H dispersed well in porous surface and inside of cellulose support. Under the optimum conditions, microwave-assisted transesterification process was carried out with the best catalyst amount, i.e. 5 wt% GO-SO₃H/CM@Fe₃O₄ (weight ratio of GO-SO₃H/cellulose), and conversion yield reached 94%. The prepared catalyst could be easily separated from reaction solution by extra magnetic field and reclaimed at least five runs.     

Experimental Investigation of Convective Heat Transfer Coefficient of Various Agricultural Products Under Open Sun Drying

Abstract

In this article, the convective heat transfer coefficients of various agricultural products were investigated under open sun drying conditions. Data obtained from open sun drying experiments for eight agricultural products, namely, mulberry, strawberry, apple, garlic, potato, pumpkin, eggplant, and onion were used to determine values of convective heat transfer coefficient. The value of convective heat transfer coefficient was determined as 1.861 W/m²°C for mulberry, 6.691 W/m²°C for strawberry, 11.323 W/m²°C for apple, 1.136 W/m²°C for garlic, 8.224 W/m²°C for potato, 8.613 W/m²°C for pumpkin, 6.981 W/m²°C for eggplant, and 6.767 W/m²°C for onion. The experimental error in terms of percent uncertainty was also calculated.     

Effect of calcination temperature on the application of sodium zirconate solid base catalyst for biodiesel production from Jatropha curcas oil

Influence of catalyst calcination temperature on the catalyst characteristics and catalytic transesterification of Jatropha curcas oil for biodiesel production was studied by using sodium zirconate (Na₂ZrO₃) solid base catalyst. Na₂ZrO₃ catalysts were prepared by impregnation method followed by calcination at temperatures of 700, 800, and 900°C. The prepared catalysts were characterized by X-ray diffraction analysis, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy. Important parameters influencing the catalytic activity and fatty acid methyl ester yield were investigated. It was found that the increase in calcination temperature showed marked increase in activity due to the increased porosity and presence of tetragonal zirconia. Investigation of the reusability of the catalysts showed that the catalytic activity was retained even after five cycles of reaction.     

Renewable biofuel production from hydrocracking of soybean biodiesel with a commercial petroleum Ni-W catalyst

As a potential hydrocarbon production method, the hydrocracking of soybean biodiesel, using a commercial petroleum hydrocracking catalyst, was studied. Experiments were carried out in a 1,000 mL, high-pressure autoclave for 2–4 hr over the temperature range of 200–280°C under an initial hydrogen pressure of 10 MPa. Hydrocracking of soybean biodiesel produced n-paraffins in the C₈–C₁₇ boiling range, which includes both green gasoline and diesel. Both pressure and temperature play important roles in the transformation of soybean biodiesel. Hydrocarbons can be formed above 220°C with a liquid yield of 81.76%. The n-alkanes content of the liquid product reached 32.29% at 280°C, with 88.32% C₁₁–C₁₄ selectivity. In addition, hydrocracking results in many changes of catalyst such as physical properties, morphology, etc. For the used catalyst, the concentrations of Ni and C increased, and the pore channels were significantly reduced.     

Effect of Fenton pretreatment on anaerobic digestion of olive mill wastewater and olive mill solid waste in mesophilic conditions

The olive mill waste (OMW) generated from olive oil extraction process constitutes a major environmental concern owing to its high organic and mineral matters and acidic pH. Anaerobic digestion (AD) is a main treatment for reducing the organic matter and toxic substances contained in OMW and generating at the same time, energy in the form of biogas. AD of OMW that contains lignocellulose is limited by the rate of hydrolysis due to their recalcitrant structure. This study is devoted to the effect of Fenton process (FP) pretreatment on olive mill wastewater (OMSW) /olive mill solid waste (OMWW) co-digestion to improve their digestibility and in this way the biogas production. The FP pretreatment was performed in batch mode at 25°C, various H₂O₂/[Fe²⁺] ratios (100–1200), catalyst concentration ([Fe²⁺]) ranging from 0.25 to 2 mM, reaction time varying from 30 to150 min, and different pH (3–11). The best performance was obtained with H₂O₂/[Fe²⁺] = 1000, [Fe²⁺] = 1.5 mM, 120 min, and pH 3. Biochemical methane potential (BMP) tests conducted in batch wise digester and at mesophilic conditions (37 °C) showed that cumulative biogas and methane production were higher without FP treatment, and correspond to 699 and 416 mL/g VS, respectively. However, pre-treated OMSW results into an increase of 24% of methane yield. After 30 days of AD, the methane yield was 63%, 54%, and 48%, respectively, for OMSW treated without iron precipitation, with iron precipitation and untreated OMSW sample.     

Parametric analysis of water electrolysis by dual electrolytes and cells

In this study, sulfuric acid and potassium hydroxide are used as the electrolytes, separated by proton exchange membrane, to produce hydrogen. The effects of electrolyte concentrations, applied voltage, single or dual cells, and temperature on the hydrogen production rate and energy efficiency are investigated. Experimental results show that the amount of hydrogen production increases with voltage, and the dual electrolytes and cells can yield the best hydrogen production rate and energy efficiency. With 1-M KOH plus 1-M H₂SO₄ as electrolytes in separated cells, the highest hydrogen production rate is about 0.95 L/hr. Results also show that the rise of electrolyte temperature can significantly increase the hydrogen production rate up to 50%, and the energy efficiency up to 20%. Keeping a low PH value in cathodeand high anode PH value in anode indeed enhances the efficiency of hydrogen production rate.     

Nanocatalyzed biodiesel synthesis from the oily contents of Marine brown alga Dictyota dichotoma

This research article demonstrates biodiesel synthesis through the methanolysis of the oily contents (4.02 ± 0.27% w/w on dried basis) of Dictyota dichotoma collected from the coast of Hawksbay, Pakistan. The metal oxides (CaO, MgO, ZnO, and TiO₂) used as nanocatalysts were refluxed (5% K₂SO₄), calcinated (850 °C) and characterized by Atomic Force Microscopy (AFM) which produced 93.2% w/w FAME (biodiesel) at relatively mild condition (5% catalyst, 65 °C, 3 h, 18:1 molar ratio) using CaO. Whereas, MgO, ZnO, and TiO₂ produced 92.4%, 72.5%, and 31.8% w/w FAME, respectively at elevated condition (225 °C). Thus, CaO was considered to be the best catalyst among the others. This tri-phase reaction require continuous fast mixing and the yield depends on the reaction parameters like catalyst amount, temperature, reaction time and molar ratio (methanol: oil). The reusability of these heterogeneous catalysts simplified the purification step, reduced the waste generation and make the final product technically and economically viable.     

Transesterification of hazelnut oil by ultrasonic irradiation

Ultrasonic irradiation is considered an effective way to increase mass transfer between immiscible liquid–liquid phases in a heterogeneous system leading to faster transesterification and higher yield and saving excess methanol and catalyst. In this study, the transesteri?cation of hazelnut oil with methanol and ethanol was performed in the presence of potassium hydroxide or sodium methoxide as a catalyst using two types of ultrasonic irradiation with a probe (20 kHz, 200 W) and a bath (35 kHz, 400 W); a conventional production method was also used. The reaction time, alcohol:oil molar ratio, catalyst type (KOH or NaOCH₃), and catalyst amount (wt.% of oil) were studied as experimental parameters. The highest methyl ester conversion was obtained as 98.12% by using ultrasonic probe at a 5:1 methanol:oil molar ratio with KOH 1 wt.% of oil as catalyst in 20-min reaction time at autogenous temperature. The application of ultrasonic irradiation by using a probe decreased the level of energy consumption, showing that this method may be a promising alternative compared with the conventional production method.     

Optimization of pretreatment conditions for enhanced sugar release

Present investigation was done to evaluate various algal genera found in water bodies of Varanasi city. The potential of any biomass for biofuels (bioalcohols, biohydrogen, etc.) production depends on the quantity of extractable sugar present in it. Acid (H₂SO₄) and alkali (NaOH) pretreatment were performed, and H₂SO₄ was chosen due to its nearly double yield as compared with alkaline pretreatment. Response surface methodology was utilized for the optimization of operating parameters such as treatment temperature, time, and acid concentration. Sugar yield up to 0.33 g/g of dry biomass was obtained using cyanobacterial biomass of Lyngbya limnetica, at 100°C, 59.19 min, and H₂SO₄ concentration of 1.63 M.     

Demonstration of a high throughput on-board hydrogen generation reactor system using aluminum coil as fuel for a vehicle

A novel on-board hydrogen generation concept using Al coil with NaOH was investigated. The reaction rate was successfully controlled by introducing a pumping system for the NaOH solution. The time for the flow to develop fully was mainly dependent on the solution temperature, and the fastest start time recorded was 60 sec at a solution temperature of 70°C. The maximum H₂ generation rate was 200 L min^–1 with a prototype design of the on-board hydrogen generation system 1/8 times the size of a full-size reactor. The H₂ generation process coupled with the solution pumping system was simulated with three-dimensional fluid dynamic software, and the calculated H₂ flow and temperature rise of the system were validated with experimental data.     

Generation Performance of Gas-Feed Direct Methanol Fuel Cell

Abstract

The modification effect of Nafion on the generation performance at different temperatures and methanol concentrations was investigated. The direct methanol fuel cell performances and electrochemical properties of the DMFC system using as-received Nafion117, a modified Nafion membrane, and using the Nafion117 MEA preparation by spray treatment on the surface of each catalyst layer for conductivity improvement. The open circuit voltage using the modified Nafion membrane was higher than that using Nafion117 at the cell temperature of 343–383 K and methanol concentration of 1.5–10 kmol/m³. The spray treatment of MEA was effective and improved the short circuit current up to 461 mA/cm² at a 5 kmol/m³ methanol concentration in comparison with no treatment of MEA because of the low interfacial resistance. The power density of 75 mW/cm² (no treatment Nafion117 MEA:40 mW/cm²) was obtained. The method of the spray treatment was found to be very effective for the DMFC system. The cell performance of Nafion117 MEA increased with the methanol concentration because of the reduction of the concentration overvoltage.     

Improving the Synthesis Gas Quality in Catalytic Gasification of Rice Straw by an Integrated Hot-Gas Cleaning System

This research investigates an enhanced removal rate of tar and trace pollutants (e.g. hydrogen chloride and hydrogen sulfide, H₂S) in the gasification of rice straw, using an integrated in situ tar reduction and hot-gas cleaning technique. The gasification temperature was set at 900°C and equilibrium ratio (ER) was 0.30 in the gasifier. In the in situ tar reduction method, the catalyst, dolomite with an amended ratio of 0–15% was introduced to the gasifier. The integrated hot-gas cleaning system applied a multi-packed tower to remove the tar, sulfur and/or chlorine byproduct in syngas at 250°C. The packed materials composed of zeolite, calcined dolomite and activated carbon. The experimental results indicated that the tar concentration of syngas was approximately 20 g/kg. However, in catalytic gasification with 5% dolomite addition, the tar concentration reduced to 17 g/kg. The tar reduction efficiency was approximately 15% by an in situ dolomite addition. When applying the integrated hot-gas cleanup system, the tar was virtually eliminated. The total tar elimination rate was almost 100% and the cleaned syngas could be applied in other energy utilization equipment. On the other hand, the H₂S and HCl concentration were 101 ppmv and 991 ppmv, respectively. After the integrated syngas cleaning system, the H₂S and HCl were decreased to 7.9 ppmv and 410 ppmv with a removal efficiency of 92.1% and 58.6%, respectively. It can be concluded that combining the in situ method with the integrated syngas cleaning system can effectively reduce the amount of byproduct and enhance the syngas quality in the gasification of rice straw.