ZrxMg1-xO supported cobalt catalysts for methane decomposition into COx-free hydrogen and carbon nanotubes

Zirconia-magnesia supported cobalt catalysts with various Zr/Mg atomic ratios were prepared and evaluated for non-oxidative catalytic decomposition of methane to produce CO_x-free hydrogen and carbon nanotube. The catalytic performance of the catalysts was performed in a continuous fixed bed flow reactor at 700°C under atmospheric pressure. The fresh and spent catalysts were characterized by XRD, TPR, BET, TEM, and Raman spectroscopy. The results showed that the change in Zr/Mg ratio of the mixed oxide support has a significant effect on the catalytic performance of the active Co metal. The catalyst 30%Co/Zr_0.8Mg_0.2 showed the highest activity and stability within the used series of catalysts with hydrogen yield reached up to 79%. Both Co/Mg_1.0 and Co/Zr_1.0 showed poor stability due to strong Co-Mg interaction and aggregation of Co species on Zr support, respectively. All catalysts produced mainly MWCNTs with different diameters depending on the Zr/Mg ratio. The outer diameter increased with increasing Zr content in the catalyst due to the enlargement of the particle size of cobalt as a result of aggregation.     

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.     

Visible light driven instantaneous photocatalytic degradation of aniline blue (AB) and methyl violet (MV) by strontium ferrite nanoparticles

Toxic organic dyes released into aquatic sources as a result of industrial activities pose a significant threat to the environment. The removal of such dyes from water sources is a challenging task in the context of environmental emergencies. In this present effort, the strontium ferrite nanoparticles were synthesized by coprecipitation followed by a calcination method and is applied for photocatalytic degradation of such organic dyes. The ferrite nanoparticles were characterized by FTIR, XRD, VSM, SEM-EDX, TEM, and HR-TEM studies. In the existence of H₂O₂ under visible light, the catalyst performs efficient degradation of aniline blue (AB) and methyl violet (MV) dyes in a remarkably short interval of time. The superparamagnetic performance of the catalyst was confirmed by VSM, and thus it can be easily recovered from the degraded dye by applying an external magnet. The Fenton mechanism justifies the elevated rate of photo degradation, which generates hydroxyl and perhydroxyl radicals in the progress of the reaction.     

Applicability of a continuous-flow system inner-coated with S-doped titania for the photocatalysis of dimethyl sulfide at low concentrations

The present study investigated the photocatalytic activity of an S-doped TiO₂ photocatalyst with regards to dimethyl sulfide degradation under visible-light irradiation, along with its deactivation and reactivation. The dimethyl sulfide conversion was between 85% and 93% for the lowest relative humidity range (10–20%) and close to 100% for the two higher relative humidity ranges (45–55% and 80–90%). The conversion was also close to 100% for the two lowest input concentrations (0.039 and 0.195 ppm), while it was between 91% and 96% at 3.9 ppm and between 85% and 90% at 7.9 ppm. In contrast to the input concentration dependences on conversion, the calculated degradation rates increased as input concentrations increased. The dimethyl sulfide conversion at low concentrations (≤0.39 ppm), which are associated with non-occupational inn occurring. However, catalyst deactivations were observed during the photocatalytic process whdoor air quality issues, was up to nearly 100% for long time periods (at least 603 h), without any significant catalyst deactivatioen higher concentrations (3.9 and 7.8 ppm) were used. The photocatalyst, reactivated by using two types of air (dried and humidified) under visible-light irradiation, did not regain all of its initial activities. Sulfate groups were qualitatively identified as the reaction products on the photocatalyst surface. In addition, gaseous byproducts, quantitatively determined, included dimethyl disulfide, methanol, and SO₂. It is noteworthy that the peak concentration of dimethyl disulfide (0.79 ppm = 790 ppb), generated over the photocatalytic process with the highest dimethyl sulfide input concentration, exceeded the odor threshold value of 0.1–3.6 ppb for dimethyl disulfide.     

Biohydrogen production by Clostridium butyricum and Rhodopseudomonas palustris in Co-cultures

This study evaluated biohydrogen production by co-culture of Clostridium butyricum and Rhodopseudomonas palustris. C. butyricum and R. palustris were grown separately and together as batch cultures. Hydrogen production, growth, NH₄-N, total volatile fatty acid production, and sucrose degradation were monitored. The hydrogen production of the co-culture produced 562 ml, R. palustris 426 ml, and C. butyricum 333 ml. The co-culture produced 2.16 mol H₂/mol sucrose, C. butyricum and R. palustris produced 1.77 and 1.64 mol H₂/mol sucrose, respectively. The co-culture was more efficient in the hydrogen production. Therefore, the co-culture is a good method for biohydrogen fermentation.     

Trapping and decomposing of color compounds from recycled water by TiO2 coated activated carbon

Five types of commercially available activated carbons (ACs) were coated with TiO₂ nanoparticles prepared using a sol–gel method. Color and trace organics remaining in the actual treated effluent were adsorbed by TiO₂ coated ACs. The absorbed organic compounds were then decomposed using a photocatalytic process, and the ACs were regenerated for reuse. The efficiency of the process was assessed by the characterization of true color and A₂₅₄ (the organics absorption at the wavelength of 254 nm) at the beginning and the end of the experiment. The effects of UV light source, UV irradiation time, hydrogen peroxide and ultrasound on the efficiency of photocatalytic regeneration were also investigated. Significant differences in the efficiency were observed between uncoated ACs and TiO₂ coated samples. Among the 5 types of ACs tested, AC-3, AC-4 and their coated ones achieved better efficiency in color and A₂₅₄ removal, with around 90% or more color and A₂₅₄ being removed within 1 h of treatment. The data obtained in this study also demonstrated that the photocatalytic process was effective for decomposing the adsorbed compounds and regenerating the spent TiO₂/AC-3. Finally, it was found that this regeneration process could be greatly enhanced with the assistance of H₂O₂ and ultrasound by reducing the required regeneration time.     

Biohythane production from pineapple peel using Methanosarcina mazei enhanced with palm oil mill effluent (POME) sludge in single-stage anaerobic digestion

Biohythane production via single-stage anaerobic digestion (AD) is an effective way for sustainable energy recovery from lignocellulosic biomass. In this paper, biohythane was produced through the AD process from pineapple peel waste substrate using purely cultured Methanosarcina mazei with the enhancement of palm oil mill effluent (POME) sludge as the inoculum. This study focuses on the effects of the lignocellulosic pre-treatment method, the addition of POME sludge into M. mazei culture medium as inoculum, and various operational conditions (food to microorganisms (F/M) ratios, temperature, pH) on gas production performances. The experimental results indicate that these parameters influenced the efficiency of biohythane production by producing the peak maximum biohythane production rate values (HPR_max) and (MPR_max), H₂:CH₄ = 1.93:0.67 L/L-d, and biohythane yield (HY) and (MY), H₂:CH₄ = 1.18:0.55 mL/L-substrate. This study demonstrates that biohythane gas (H₂ + CH₄ + CO₂) production from pineapple waste can be accelerated by M. mazei only with the enhancement of POME sludge through single-stage AD system under mesophilic batch process conditions.     

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.     

Techno-economic study of CO2 capture from natural gas based hydrogen plants

Canadian oil sands are considered to be the second largest oil reserves in the world. However, the upgrading of bitumen from oil sands to synthetic crude oil (SCO) requires nearly ten times more hydrogen (H₂) than conventional crude oils. The current H₂ demand for oil sands operations is met mostly by steam reforming of natural gas (SMR). The future expansion of oil sands operations is likely to quadruple the demand of H₂ for oil sand operations in the next decade.This paper presents modified process schemes that capture CO₂ at minimum energy penalty in modern SMR plants. The approach is to simulate a base case H₂ plant without CO₂ capture and then look for the best operating conditions that minimize the energy penalty associated with CO₂ capture while maximizing H₂ production. The two CO₂ capture schemes evaluated in this study include a membrane separation process and the monoethanolamine (MEA) absorption process. A low energy penalty is observed when there is lower CO₂ production and higher steam production. The process simulation results show that the H₂ plant with CO₂ capture has to be operated at lower steam to carbon ratio (S/C), higher inlet temperature of the SMR and lower inlet temperatures for the water gas-shift (WGS) converters to attain lowest energy penalty. Also it is observed that both CO₂ capture processes, the membrane process and the MEA absorption process, are comparable in terms of energy penalty and CO₂ avoided when both are operated at conditions where lowest energy penalty exists.     

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.     

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.     

Effect of oxygenated liquid additives on the urea based SNCR process

An experimental investigation was performed to study the effect of oxygenated liquid additives, H₂O₂, C₂H₅OH, C₂H₄(OH)₂ and C₃H₅(OH)₃ on NO_x removal from flue gases by the selective non-catalytic reduction (SNCR) process using urea as a reducing agent. Experiments were performed with a 150 kW pilot scale reactor in which a simulated flue gas was generated by the combustion of methane operating with 6% excess oxygen in flue gases. The desired levels of initial NO_x (500 ppm) were achieved by doping the fuel gas with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 800 to 1200 °C for the investigation of the effects of the process additives on the performance of aqueous urea DeNO_x. With H₂O₂ addition a downward shift of 150 °C in the peak reduction temperature from 1130 to 980 °C was observed during the experimentation, however, the peak reduction efficiency was reduced from 81 to 63% when no additive was used. The gradual addition of C₂H₅OH up to a molar ratio of 2.0 further impairs the peak NO_x reduction efficiency by reducing it to 50% but this is accompanied by a downward shift of 180 °C in the peak reduction temperature. Further exploration using C₂H₄(OH)₂ suggested that a 50% reduction could be attained for all the temperatures higher than 940 °C. The use of C₃H₅(OH)₃ as a secondary additive has a significant effect on the peak reduction efficiency that decreased to 40% the reductions were achievable at a much lower temperature of 800 °C showing a downward shift of 330 °C.     

Life cycle assessment of a pulverized coal power plant with post-combustion capture, transport and storage of CO2

In this study the methodology of life cycle assessment has been used to assess the environmental impacts of three pulverized coal fired electricity supply chains with and without carbon capture and storage (CCS) on a cradle to grave basis. The chain with CCS comprises post-combustion CO₂ capture with monoethanolamine, compression, transport by pipeline and storage in a geological reservoir. The two reference chains represent sub-critical and state-of-the-art ultra supercritical pulverized coal fired electricity generation. For the three chains we have constructed a detailed greenhouse gas (GHG) balance, and disclosed environmental trade-offs and co-benefits due to CO₂ capture, transport and storage. Results show that, due to CCS, the GHG emissions per kWh are reduced substantially to 243 g/kWh. This is a reduction of 78 and 71% compared to the sub-critical and state-of-the-art power plant, respectively. The removal of CO₂ is partially offset by increased GHG emissions in up- and downstream processes, to a small extent (0.7 g/kWh) caused by the CCS infrastructure. An environmental co-benefit is expected following from the deeper reduction of hydrogen fluoride and hydrogen chloride emissions. Most notable environmental trade-offs are the increase in human toxicity, ozone layer depletion and fresh water ecotoxicity potential for which the CCS chain is outperformed by both other chains. The state-of-the-art power plant without CCS also shows a better score for the eutrophication, acidification and photochemical oxidation potential despite the deeper reduction of SO_x and NO_x in the CCS power plant. These reductions are offset by increased emissions in the life cycle due to the energy penalty and a factor five increase in NH₃ emissions.     

Design and optimization of new La1−xCexNi1−yFeyO3 (x,y = 0–0.4) nano catalysts in dry reforming of methane

The paper reports the production of syngas from dry reforming of methane (DRM) over La_1?xCe_xNi_1?yFe_yO₃ (x, y = 0–0.4) perovskites. A series of La_1?xCe_xNi_1?yFe_yO₃ were designed by central composite design (CCD) and synthesized by a sol–gel auto combustion method. Artificial neural network (ANN) approach was used to determine the relationship between preparation and operational parameters on the performance of the catalysts in the DRM process. Nickel mole fraction, lanthanum mole fraction, calcination temperature, and reaction temperature were considered as input variables, and conversion of methane was considered as the output variable. An ANN model with nine neurons in the hidden layer was the suitable in predicting conversion of methane. The genetic algorithm (GA) was subsequently used to determine the optimal preparation condition for enhancing the conversion of methane. La_0.6Ce_0.4Ni_0.99Fe_0.01O₃ catalyst, calcined at 756°C was obtained to be the most active catalyst owing to the optimal composition of nickel and lanthanum in the catalyst formulation.     

Production of Fe2O3 from FeSO4·xH2O formed in galvanizing works

FeSO₄·xH₂O is generated in large amounts in galvanizing workshops. It can be reutilized by conversion to Fe₂O₃. In this study, the recovery of Fe₂O₃ from FeSO₄·xH₂O formed in the galvanizing process has been examined. The experimental work was carried out at various temperatures and times in the oxidizing medium. The reaction temperatures and times were selected as 450, 500, 550, 600, 650, 700, 800 and 900°C, and 15, 30, 45, 60, 90 and 120 minutes, respectively. In order to determine the amount of Fe₂O₃, a titrimetric method was applied. The reaction products were characterized by means of IR and XRD techniques.The extent of conversion is low at temperatures below 650°C. Almost all of the iron (II) sulfate in the original sample was converted to iron(III) oxide at 650°C (120 min), 700°C (90 min), 800°C (60 min) and 900°C (45 min).     

CO2 recycling by reaction with renewably-generated hydrogen

A laboratory-scale reactor system was built and operated to demonstrate the feasibility of catalytically reacting carbon dioxide (CO₂) with renewably-generated hydrogen (H₂) to produce methane (CH₄) according to the Sabatier reaction: CO₂ + 4H₂ → CH₄ + 2H₂O. A cylindrical reaction vessel packed with a commercial methanation catalyst (Haldor Topsøe PK-7R) was used. Renewable H₂ produced by electrolysis of water (from solar- and wind-generated electricity) was fed into the reactor along with a custom blend of 2% CO₂ in N₂, meant to represent a synthetic exhaust mixture. Reaction conditions of temperature, flow rates, and gas mixing ratios were varied to determine optimum performance. The extent of reaction was monitored by real-time measurement of CO₂ and CH₄. Maximum conversion of CO₂ occurred at 300–350 °C. Approximately 60% conversion of CO₂ was realized at a space velocity of about 10,000 h^?1 with a molar ratio of H₂/CO₂ of 4/1. Somewhat higher total CO₂ conversion was possible by increasing the H₂/CO₂ ratio, but the most efficient use of available H₂ occurs at a lower H₂/CO₂ ratio.     

Validation of a dynamic model of hydrogen permeation through Pd-based membranes

Pd-based membranes have been studied for pure hydrogen separation from syngas: in particular, a mathematical model of a Pd membrane for hydrogen separation has been developed.This model can be used in process and assessment studies of the parameters which characterize the mass transfer phenomena (such as: hydrogen permeability, surface coverage and limiting step). By coupling the permeation and water gas shift reaction kinetics, it can also be used to evaluate the performances of the membrane reactor. Further, it can be helpful to evaluate the best assembly and sizing of a H₂/CO₂ separation system.The model takes into account the kinetics of H₂ adsorption/desorption on Pd surface, the H₂ permeation into the palladium bulk and in the porous layer, and the kinetics of CO, CO₂, H₂O, O₂, H₂S competitive adsorption/desorption on Pd surface. It is also comprehensive of flux equations and bulk mass, momentum and energy balance.The results released by the model were compared to the experimental data during both the transient phase and the steady state conditions. A satisfactory agreement between model and experimental data was found.     

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.     

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.     

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.