Search results for: methane low temperature total oxidation

Authors: Maryam Enteshari, Kooshan Nayebzadeh, Abdorreza Mohammadi

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In this study, the oxidative stability of soybean oil under different storage temperatures (4 and 25˚C) and during 6-month shelf-life was investigated by various analytical methods and headspace-liquid phase microextraction (HS-LPME) coupled to gas chromatography-mass spectrometry (GC-MS). Oxidation changes were monitored by analytical parameters consisted of acid value (AV), peroxide value (PV), p-Anisidine value (p-AV), thiobarbituric acid value (TBA), fatty acids profile, iodine value (IV), and oxidative stability index (OSI). In addition, concentrations of hexanal and heptanal as secondary volatile oxidation compounds were determined by HS-LPME/GC-MS technique. Rate of oxidation in soybean oil which stored at 25˚C was so higher. The AV, p-AV, and TBA were gradually increased during 6 months while the amount of unsaturated fatty acids, IV, and OSI decreased. Other parameters included concentrations of both hexanal and heptanal, and PV exhibited increasing trend during primitive months of storage; then, at the end of third and fourth months a sudden decrement was understood for the concentrations of hexanal and heptanal and the amount of PV, simultaneously. The latter parameters increased again until the end of shelf-time. As a result, the temperature and time were effective factors in oxidative stability of soybean oil. Also intensive correlations were found for soybean oil at 4 ˚C between AV and TBA (r2=0.96), PV and p-AV (r2=0.9), IV and TBA (-r2=0.9), and for soybean oil stored at 4˚C between p-AV and TBA (r2=0.99).

Keywords: headspace-liquid phase microextraction, oxidation, shelf-life, soybean oil

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Authors: Zhenghua Dai, Jianliang Xu, Fuchen Wang

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Non-catalyst partial oxidation technology has been widely used to produce syngas by reforming of hydrocarbon, including gas (natural gas, shale gas, refinery gas, coalbed gas, coke oven gas, pyrolysis gas, etc.) and liquid (residual oil, asphalt, deoiled asphalt, biomass oil, etc.). For natural gas non-catalyst partial oxidation, the H₂/CO(v/v) of syngas is about 1.8, which is agreed well with the request of FT synthesis. But for other process, such as carbonylation and glycol, the H₂/CO(v/v) should be close to 1 and 2 respectively. So the syngas composition of non-catalyst partial oxidation should be adjusted to satisfy the request of different chemical synthesis. That means a multi-reforming method by CO₂ and H₂O addition. The natural gas non-catalytic partial oxidation hot model was established. The effects of O₂/CH4 ratio, steam, and CO₂ on the syngas composition were studied. The results of the experiment indicate that the addition of CO₂ and steam into the reformer can be applied to change the syngas H₂/CO ratio. The reactor network model (RN model) was established according to the flow partition of industrial reformer and GRI-Mech 3.0. The RN model results agree well with the industrial data. The effects of steam, CO₂ on the syngas compositions were studied with the RN model.

Keywords: non-catalyst partial oxidation, natural gas, H₂/CO, CO₂ and H₂O addition, multi-reforming method

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Authors: Maryam Zarabian, Hector Guzman, Pedro Pereira-Almao, Abraham Fapojuwo

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Dry reforming of methane (DRM) has sparked significant industrial and scientific interest not only as a viable alternative for addressing the environmental concerns of two main contributors of the greenhouse effect, i.e., carbon dioxide (CO₂) and methane (CH₄), but also produces syngas, i.e., a mixture of hydrogen (H₂) and carbon monoxide (CO) utilized by a wide range of downstream processes as a feedstock for other chemical productions. In this study, we develop an AI-enable syngas production model to tackle the problem of achieving an equivalent H₂/CO ratio [1:1] with respect to the most efficient conversion. Firstly, the unsupervised density-based spatial clustering of applications with noise (DBSAN) algorithm removes outlier data points from the original experimental dataset. Then, random forest (RF) and deep neural network (DNN) models employ the error-free dataset to predict the DRM results. DNN models inherently would not be able to obtain accurate predictions without a huge dataset. To cope with this limitation, we employ reusing pre-trained layers’ approaches such as transfer learning and greedy layer-wise pretraining. Compared to the other deep models (i.e., pure deep model and transferred deep model), the greedy layer-wise pre-trained deep model provides the most accurate prediction as well as similar accuracy to the RF model with R² values 1.00, 0.999, 0.999, 0.999, 0.999, and 0.999 for the total outlet flow, H₂/CO ratio, H₂ yield, CO yield, CH₄ conversion, and CO₂ conversion outputs, respectively.

Keywords: artificial intelligence, dry reforming of methane, artificial neural network, deep learning, machine learning, transfer learning, greedy layer-wise pretraining

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Authors: Atena Naeimi, Asghar Amiri, Zahra Ghasemi

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A stable suspension of nanocomposite simple manganese(III) meso-tetraphenylporphyrin nanoaggregates and Ag was prepared by a host–guest procedure, in which ethanol and water are used as ‘green’ solvents. The oxidation of alcohols by tetrabutylammonium Peroxomonosulfate(TP) were efficiently enhanced with excellent selectivity under the influence of simple Mn(TPP)OAc (TPP = meso-tetraphenylporphyrin) nanoparticles. Enhanced stabilities and activities were achieved with nanostructured Mn catalysts compared to those of the individual counterparts in solution according to turnover numbers and UV/Vis studies. The title nanocatalyst facilitates a greener reaction because the reaction solvent is water and TP is safe to use. The efficiency of the oxidation system depends critically upon the steric hindrances and electronic structures of both nitrogen donor ligand sand porphyrin nanoparticles.

Keywords: oxidation, nanoaggregates, porphyrinoids, silver

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Authors: Radia Imane Fertout

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In recent years, the reaction of dry reforming of methane (DRM) has attracted much attention due to its environmental and industrial importance. Various catalysts, including Ni-based catalysts, have been investigated for the DRM. Doping Ni/Al₂O₃ by lanthanum and alkaline earth element may strongly influence solid-state reaction and increases the stability of catalysts due to the lower density and high basicity of these oxides. The effect of SrO on the activity and stability of Ni/Al₂O₃-La₂O₃ in dry reforming of methane was investigated. These catalysts have been prepared with the impregnation method, calcined in air at 450 and 650°C, then characterized by BET surface area, X-ray diffraction (XRD), and scanning electron microscopy (SEM) techniques and tested in DRM. The results showed that the addition of strontium to Ni/Al2O₃-La₂O₃ decreased the specific surface area. XRD results revealed the presence of different phases of Al₂O₃, La(OH)₃, La₂O₂CO₃, and SrCO₃. The catalytic evaluation results showed that adding SrO increased the catalytic activity and stability, that explained by the strong basicity of strontium. SEM analysis after the reaction indicates the formation of carbon over the spent catalyst and that the addition of strontium stabilized the surface of the catalyst.

Keywords: dry reforming of methane, Ni/Al₂O₃-La₂O₃ catalyst, strontium, nickel

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Authors: Ahmed A. Abdel-Khalek, Reham A. Mohamed

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The kinetics of oxidation of binary complex [CrIII(DMG)2(H2O)4 ]+ to Cr(VI) by periodate has been investigated spectrophotometrically where, [DMG= Dimethylglyoxime] at 370nm under pseudo first order reaction conditions in aqueous medium over 20- 40ºC range, PH 2-3, and I=0.07 mol dm-3. The reaction is first order with respect to both [IO4-] and Cr(III), and the reaction increased with PH increased. Thermodymanic activation parameters have been calculated. It is suggested that electron transfer proceeds through an inner sphere mechanism via coordination of IO4- to Cr (III). The reaction obeys the following rate law Rate= {k1 K5+ k2 K6 K2 } [Cr III (DMG)2(H2O)4 ]+ [H5IO6].

Keywords: chromium, dimethylglyoxime, kinetics, oxidation, periodate

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Authors: Michael Graz, Andrew Shearer, Gareth Evans

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Manipulation of rumen bacteria is receiving increasing attention as a way of controlling greenhouse gas (GHG) emissions that are generated by the agricultural sector. Feed supplementation in particular is one of the ways in which this drive is being addressed, in particular with reference to livestock-generated GHG emissions. A blend of naturally occurring chemical extracts obtained from garlic and bitter orange extracts has been identified as a natural, sustainable and non-antibiotic based way of reducing methane production by ruminant livestock. In the current study, the acceptability and impact of this blend of natural extracts on feed rations of beef cattle was trialed in vivo on a commercial farm in Europe. Initial findings have demonstrated acceptable palatability, with all animals accepting the feed supplement into their ration both when it was mixed into the total daily ration and when used as a part of their high energy rations. Measurement of the impact of this feed supplement on productivity weight gain and milk quality is ongoing. In conclusion, this field study confirmed the palatability of the combination of garlic and citrus extracts and hence pointed to possibility of the extract blend to improve digestion, enhance body energy retention and limit CH4 formation in relation to feed intake.

Keywords: citrus, garlic, methane reduction, palatability, ruminants

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Authors: A. V. Shelke, P. S. More

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This research aimed to study the kinetic reaction of reused cooking oil and to find the optimum condition of its process. The feedstock was collected from the street sellers and also prepared at laboratory. From this research, it is found that the kinetic reaction of reused sunflower oil (auto-oxidation) is obtained in terms of variation of the absorption coefficient of unexposed sunflower oil as 0.05 which is very close to that of exposed sunflower oil 0.075. At room temperature, the optimum intensity obtained from optical absorption spectroscopy study is 0.267 for unexposed sunflower oil and 0.194 for exposed sunflower oil. However, results indicated that FTIR spectroscopy is accurate and precise enough for such determination. Free Fatty Acid (FFA% = 026), acid ~53% and safonication ~%192 get reduce in exposed oil was investigated.

Keywords: friction, oxidation, sunflower oil, vegetable oils

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Authors: S. R. H. Baqri, T. Shahina, M. T. Hasan

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Pakistan is facing acute shortage of energy and looking for indigenous resources of the energy mix to meet the short fall. After the discovery of huge coal resources in Thar Desert of Sindh province, focus has shifted to coal power generation. The government of Pakistan has planned power generation of 20000 MW on coal by the year 2025. This target will be achieved by mining and power generation in Thar coal Field and on imported coal in different parts of Pakistan. Total indigenous coal production of around 3.0 million tons is being utilized in brick kilns, cement and sugar industry. Coal-based power generation is only limited to three units of 50 MW near Hyderabad from nearby Lakhra Coal field. The purpose of this presentation is to identify and redressal of issues of coal mining and utilization with reference to environmental hazards. Thar coal resource is estimated at 175 billion tons out of a total resource estimate of 184 billion tons in Pakistan. Coal of Pakistan is of Tertiary age (Palaeocene/Eocene) and classified from lignite to sub-bituminous category. Coal characterization has established three main pollutants such as Sulphur, Carbon dioxide and Methane besides some others associated with coal and rock types. The element Sulphur occurs in organic as well as inorganic forms associated with coals as free sulphur and as pyrite, gypsum, respectively. Carbon dioxide, methane and minerals are mostly associated with fractures, joints local faults, seatearth and roof rocks. The abandoned and working coal mines give kerosene odour due to escape of methane in the atmosphere. While the frozen methane/methane ices in organic matter rich sediments have also been reported from the Makran coastal and offshore areas. The Sulphur escapes into the atmosphere during mining and utilization of coal in industry. The natural erosional processes due to rivers, streams, lakes and coastal waves erode over lying sediments allowing pollutants to escape into air and water. Power plants emissions should be controlled through application of appropriate clean coal technology and need to be regularly monitored. Therefore, the systematic and scientific studies will be required to estimate the quantity of methane, carbon dioxide and sulphur at various sites such as abandoned and working coal mines, exploratory wells for coal, oil and gas. Pressure gauges on gas pipes connecting the coal-bearing horizons will be installed on surface to know the quantity of gas. The quality and quantity of gases will be examined according to the defined intervals of times. This will help to design and recommend the methods and procedures to stop the escape of gases into atmosphere. The element of Sulphur can be removed partially by gravity and chemical methods after grinding and before industrial utilization of coal.

Keywords: atmosphere, coal production, energy, pollutants

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Authors: Jaime Carpio-García, Elena Blanco-Fernández, Jorge Rodríguez-Hernández, Daniel Castro-Fresno

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Geosynthetic mechanical behavior vs temperature or vs aging has been widely studied independently during the last years, both in laboratory and in outdoor conditions. This paper studies this behavior deeper, considering that geosynthetics have to perform adequately at different outdoor temperatures once they have been subjected to a certain degree of aging, and also considering the different geosynthetic structures made of the same material. This combining effect has been not considered so far, and it is important to ensure the performance of geosynthetics, especially where high temperatures are expected. In order to fill this gap, six commercial geosynthetics with different internal structures made of polypropylene (PP), high density polyethylene (HDPE), bitumen and polyvinyl chloride (PVC), or even a combination of some of them have been mechanically tested at mild temperature (20ºC or 23ºC) and at warm temperature (45ºC) before and after specific exposition to air at standardized high temperature in order to simulate 25 years of aging due to oxidation. Besides, for 45ºC tests, an innovative heating system during test for high deformable specimens is proposed. The influence of the combining effect of aging, structure and temperature in the product behavior have been analyzed and discussed, concluding that internal structure is more influential than aging in the mechanical behavior of a geosynthetic versus temperature.

Keywords: geosynthetics, mechanical behavior, temperature, aging, internal structure

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Authors: Cenk Sezen, Turgay Partal

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North Sea Caspian Pattern Index (NCP) refers to an atmospheric teleconnection between the North Sea and North Caspian at the 500 hPa geopotential height level. The aim of this study is to search for effects of NCP on annual and seasonal mean temperature and also annual and seasonal precipitation totals in the Aegean region of Turkey. The study contains the data that consist of 46 years obtained from nine meteorological stations. To determine the relationship between NCP and the climatic parameters, firstly the Pearson correlation coefficient method was utilized. According to the results of the analysis, most of the stations in the region have a high negative correlation NCPI in all seasons, especially in the winter season in terms of annual and seasonal mean temperature (statistically at significant at the 90% level). Besides, high negative correlation values between NCPI and precipitation totals are observed during the winter season at the most of stations. Furthermore, the NCPI values were divided into two group as NCPI(-) and NCPI(+), and then mean temperature and precipitation total values, which are grouped according to the NCP(-) and NCP(+) phases, were determined as annual and seasonal. During the NCPI(-), higher mean temperature values are observed in all of seasons, particularly in the winter season compared to the mean temperature values under effect of NCP(+). Similarly, during the NCPI(-) in winter season precipitation total values have higher than the precipitation total values under the effect of NCP(+); however, in other seasons there no substantial changes were observed between the precipitation total values. As a result of this study, significant proof is obtained with regards to the influences of NCP on the temperature and precipitation regime in the Aegean region of Turkey.

Keywords: Aegean region, NCPI, precipitation, temperature

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Authors: Kgomotso Matobole, Pascal Mwenge, Tumisang Seodigeng

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The global urbanisation and worldwide economic growth have caused a high rate of food waste generation, resulting in environmental pollution. Food waste disposed on landfills decomposes to produce methane (CH₄), a greenhouse gas. Inadequate waste management practices contribute to food waste polluting the environment. Thus effective organic fraction of municipal solid waste (OFMSW) management and treatment are attracting widespread attention in many countries. This problem can be minimised by the employment of anaerobic digestion process, since food waste is rich in organic matter and highly biodegradable, resulting in energy generation and waste volume reduction. The current study investigated the Biomethane Potential (BMP) of the Vaal University of Technology canteen food waste using anaerobic digestion. Tests were performed on canteen food waste, as a substrate, with total solids (TS) of 22%, volatile solids (VS) of 21% and moisture content of 78%. The tests were performed in batch reactors, at a mesophilic temperature of 37 °C, with two different types of inoculum, primary and digested sludge. The resulting CH₄ yields for both food waste with digested sludge and primary sludge were equal, being 357 Nml/g VS. This indicated that food waste form this canteen is rich in organic and highly biodegradable. Hence it can be used as a substrate for the anaerobic digestion process. The food waste with digested sludge and primary sludge both fitted the first order kinetic model with k for primary sludge inoculated food waste being 0.278 day^-1 with R² of 0.98, whereas k for digested sludge inoculated food waste being 0.034 day^-1, with R² of 0.847.

Keywords: anaerobic digestion, biogas, bio-methane potential, food waste

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Authors: Hafizan Junoh, Kumaran Palanisamy, Yip Chan Heng, Pua Fei Ling

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This study investigates the influence of low temperature thermo-chemical pretreatment of organic food waste on the performance of COD solubilisation. Both temperature and alkaline agent were reported to have an effect on solubilizing any possible biomass including organic food waste. The three independent variables considered in this pretreatment were temperature (50-90oC), pretreatment time (30-120 minutes) and alkaline concentration, sodium hydroxide, NaOH (0.7-15 g/L). The optimal condition obtained were 90oC, 15 g/L NaOH for 2 hours. Solubilisation has potential in enhancing methane production by providing a high amount of soluble components at an early stage during anaerobic digestion.

Keywords: food waste, pretreatments, respond surface methodology, ANOVA, anaerobic digestion

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Authors: Dong Zhao

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Abstract—Extensive research on obtaining applicable room temperature superconductors meets the major barrier, and the record Tc of 135 K achieved via cuprate has been idling for decades. Even though, the accomplishment of higher Tc than the cuprate was made through pressurizing certain compounds composed of light elements, such as for the LaH10 and for the metallic hydrogen. Room temperature superconductivity under ambient pressure is still the preferred approach and is believed to be the ultimate solution for many applications. While racing to find the breakthrough method to achieve this room temperature Tc milestone in superconducting research, a report stated a discovery of a possible high-temperature superconductor, i.e., the thorium sulfide ThS. Apparently, ThS’s Tc can be at room temperature or even higher. This is because ThS revealed an unusual property of the ‘coexistence of high electrical conductivity and diamagnetism’. Noticed that this property of coexistence of high electrical conductivity and diamagnetism is in line with superconductors, meaning ThS is also at its superconducting state. Surprisingly, ThS owns the property of superconductivity at least at room temperature and under atmosphere pressure. Further study of the ThS’s electrical and magnetic properties in comparison with thorium di-iodide ThI2 concluded its molecular configuration as [Th4+(e-)2]S. This means the ThS’s cation is composed of a [Th4+(e-)2]2+ cation core. It is noticed that this cation core is built by an oxidation state +4 of thorium atom plus an electron pair on this thorium atom that resulted in an oxidation state +2 of this [Th4+(e-)2]2+ cation core. This special construction of [Th4+(e-)2]2+ cation core may lead to the ThS’s room temperature superconductivity because of this characteristic electron lone pair residing on the thorium atom. Since the study of thorium chemistry was carried out in the period of before 1970s. the exploration about ThS’s possible room temperature superconductivity would require resynthesizing ThS. This re-preparation of ThS will provide the sample and enable professionals to verify the ThS’s room temperature superconductivity. Regrettably, the current regulation prevents almost everyone from getting access to thorium metal or thorium compounds due to the radioactive nature of thorium-232 (Th-232), even though the radioactive level of Th-232 is extremely low with its half-life of 14.05 billion years. Consequently, further confirmation of ThS’s high-temperature superconductivity through experiments will be impossible unless the use of corresponding thorium metal and related thorium compounds can be deregulated. This deregulation would allow researchers to obtain the necessary starting materials for the study of ThS. Hopefully, the confirmation of ThS’s room temperature superconductivity can not only establish a method to obtain applicable superconductors but also to pave the way for fully understanding the mechanism of superconductivity.

Keywords: co-existence of high electrical conductivity and diamagnetism, electron pairing and electron lone pair, room temperature superconductivity, the special molecular configuration of thorium sulfide ThS

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Authors: Deepti Mishra, K. K Pant, Xiu Song Zhao, Muxina Konarova

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Catalytic transformation of simplest hydrocarbon methane into benzene and valuable chemicals over Mo/HZSM-5 has a great economic potential, however, it suffers serious hurdles due to the blockage in the micropores because of extensive coking at high temperature during methane dehydroaromatization (MDA). Under such conditions, it necessitates the design of micro/mesoporous ZSM-5, which has the advantages viz. uniform dispersibility of MoOx species, consequently the formation of active Mo sites in the micro/mesoporous channel and lower carbon deposition because of improved mass transfer rate within the hierarchical pores. In this study, we report a unique strategy to control the porous structures of ZSM-5 through a dual templating approach, utilizing C6 and C12 -surfactants as porogen. DFT studies were carried out to correlate the ZSM-5 framework development using the C6 and C12 surfactants with structure directing agent. The structural and morphological parameters of the synthesized ZSM-5 were explored in detail to determine the crystallinity, porosity, Si/Al ratio, particle shape, size, and acidic strength, which were further correlated with the physicochemical and catalytic properties of Mo modified HZSM-5 catalysts. After Mo incorporation, all the catalysts were tested for MDA reaction. From the activity test, it was observed that C6 surfactant-modified hierarchically porous Mo/HZSM-5(H) showed the highest benzene formation rate (1.5 μmol/gcat. s) and longer catalytic stability up to 270 min of reaction as compared to the conventional microporous Mo/HZSM-5(C). In contrary, C12 surfactant modified Mo/HZSM-5(D) is inferior towards MDA reaction (benzene formation rate: 0.5 μmol/gcat. s). We ascribed that the difference in MDA activity could be due to the hierarchically interconnected meso/microporous feature of Mo/HZSM-5(H) that precludes secondary reaction of coking from benzene and hence contributing substantial stability towards MDA reaction.

Keywords: hierarchical pores, Mo/HZSM-5, methane dehydroaromatization, coke deposition

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Authors: Zhao Bo

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The TiO2-Na2SO3 and SiO2-Na2SO3 nano-fluids were prepared using ultrasonic dispertion method without any surfactant addition to study the influence of nano-fluids on the mass transfer during forced sulfite oxidation in a thermostatic stirred tank, and the kinetic viscosity of nano-fluids was measured. The influence of temperature (30 ℃ ~ 50 ℃), solid loading of fine particle (0 Kg/m³~1.0 Kg/m³), stirring speed (50 r/min ~ 400 r/min), and particle size (10 nm~100 nm) on the average oxygen absorption rate were investigated in detail. Both TiO2 nano-particles and SiO2 nano-particles could remarkably improve the gas-liquid mass transfer. Oxygen absorption enhancement factor increases with the increase of solid loading of nano-particles to a critical value and then decreases with further increase of solid loading under 30℃. Oxygen absorption rate together with absorption enhancement factor increases with stirring speed. However, oxygen absorption enhancement factor decreases with the increase of temperature due to aggregation of nano-particles. Further inherent relationship between particle size, loading, surface area, viscosity, stirring speed, temperature, adsorption, desorption, and mass transfer was discussed in depth by analyzing the interaction mechanism.

Keywords: fine particles, nano-fluid, mass transfer enhancement, solid loading

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Authors: Yasam Palguna, Rajesh Korla

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The efficiency of thermally operated systems can be improved by increasing the operating temperature, thereby decreasing the fuel consumption and carbon footprint. Hence, there is a continuous need for replacing the existing materials with new alloys with higher temperature working capabilities. During the last decade, multi principal element alloys, commonly known as high entropy alloys are getting more attention because of their superior high temperature strength along with good high temperature corrosion and oxidation resistance, The present work focused on the microstructure and high temperature tensile behavior of Al0.2CoCrFeNiMo0.5 high entropy alloy (HEA). Wrought Al0.2CoCrFeNiMo0.5 high entropy alloy, produced by vacuum induction melting followed by thermomechanical processing, is tested in the temperature range of 200 to 900oC. It is exhibiting very good resistance to softening with increasing temperature up to 700oC, and thereafter there is a rapid decrease in the strength, especially beyond 800oC, which may be due to simultaneous occurrence of recrystallization and precipitate coarsening. Further, it is exhibiting superplastic kind of behavior with a uniform elongation of ~ 275 % at 900 oC temperature and 1 x 10-3 s-1 strain rate, which may be due to the presence of fine stable equi-axed grains. Strain rate sensitivity of 0.3 was observed, suggesting that solute drag dislocation glide might be the active mechanism during superplastic kind of deformation. Post deformation microstructure suggesting that cavitation at the sigma phase-matrix interface is the failure mechanism during high temperature deformation. Finally, high temperature properties of the present alloy will be compared with the contemporary high temperature materials such as ferritic, austenitic steels, and superalloys.

Keywords: high entropy alloy, high temperature deformation, super plasticity, post-deformation microstructures

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Authors: M. Diafi, M. Omari, B. Gasmi

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Perovskite-type La1−xCaxAlO3 were synthesized at 1000◦C by a co- precipitation method. The synthesized oxide powders were characterized by X-ray diffraction (XRD) and the oxide powders were produced in the form of films on pretreated Ni-supports by an oxide-slurry painting technique their electrocatalytic activities towards methanol oxidation in alkaline solutions at 25°C using cyclic voltammetry, chronoamperometry, and anodic Tafel polarization techniques. The oxide catalysts followed the rhombohedral hexagonal crystal geometry. The rate of electro-oxidation of methanol was found to increase with increasing substitution of La by Ca in the oxide matrix. The reaction indicated a Tafel slope of ~2.303RT/F, The electrochemical apparent activation energy (〖∆H〗_el^(°#)) was observed to decrease on increasing Ca content. The results point out the optimum electrode activity and stability of the Ca is x=0.6 of composition.

Keywords: electrocatalysis, oxygen evolution, perovskite-type La1−x Cax AlO3, methanol oxidation

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Authors: Brunno Vasques

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Due to the non-toxic nature and high performance in terms of vacuum specific impulse and density specific impulse, the combination of liquid oxygen and liquid methane have been identified as a promising option for future space vehicle systems. Applications requiring throttling capability include specific missions such as rendezvous, planetary landing and de-orbit as well as weapon systems. One key challenge in throttling liquid rocket engines is maintaining an adequate pressure drop across the injection elements, which is necessary to provide good propellant atomization and mixing as well as system stability. The potential scalability of pintle injectors, their great suitability to throttling and inherent combustion stability characteristics led to investigations using a variety of propellant combinations, including liquid oxygen and hydrogen and fluorine-oxygen and methane. Presented here are the preliminary performance and heat transfer information obtained during hot-fire testing of a pintle injector running on liquid oxygen and liquid methane propellants. The specific injector design selected for this purpose is a multi-configuration building block version with replaceable injection elements, providing flexibility to accommodate hardware modifications with minimum difficulty. On the basis of single point runs and the use of a copper/nickel segmented calorimetric combustion chamber and associated transient temperature measurement, the characteristic velocity efficiency, injector footprint and heat fluxes could be established for the first proposed pintle configuration as a function of injection velocity- and momentum-ratios. A description of the test-bench is presented as well as a discussion of irregularities encountered during testing, such as excessive heat flux into the pintle tip resulting from certain operating conditions.

Keywords: green propellants, hot-fire performance, rocket engine throttling, pintle injector

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Authors: S. Lekhavat, U. Srimongkoluk, P. Ratanachamnong, G. Laungsopapun

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Quercetin was encapsulated with whey protein and high methoxyl pectin by spray drying technique. Feed solution, consisting of 0.1875 0.125 and 0.0625 % w/w quercetin, respectively, was prepared and then sprays at outlet temperature of 70, 80 and 90 °C. Quercetin contents either in feed solution or in spray dried powder were determined by HPLC technique. Physicochemical properties such as viscosity and total soluble solid of feed solution as well as moisture content and water activity of spray dried powder were examined. Particle morphology was imaged using scanning electron microscope. The results showed that feed solution has total soluble solid and viscosity in range of 1.73-5.60 ºBrix and 2.58-8.15 cP, in that order. After spray drying, the moisture content and water activity value of powder are in range of 0.58-2.72 % and 0.18-0.31, respectively. Quercetin content in dried sample increased along with outlet drying temperature but decreased when total soluble solid increased. It was shown that particles are likely to shrivel when spray drying at high temperature. The suggested conditions for encapsulation of quercetin are feed solution with 0.0625 % (w/w) quercetin and spray drying at drying outlet temperature of 90°C.

Keywords: drying temperature, particle morphology, spray drying, quercetin

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Authors: Yu-Jen Shih, Juan-Zhang Lou

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Nitrogenous compounds, such as NH4+/NH3 and NO3-, have become important contaminants in water resources. Excessive concentration of NH3 leads to eutrophication, which poses a threat to aquatic organisms in the environment. Electrochemical oxidation emerged as a promising water treatment technology, offering advantages such as simplicity, small-scale operation, and minimal reliance on additional chemicals. In this study, a nickel-based metal-organic framework (Ni-MOF) was synthesized using 2-amino terephthalic acid (BDC-NH2) and nickel nitrate. The Ni-MOF was further carbonized as derived nickel oxide and nitrogen-carbon composite, Ni/NiOx/NC. The nickel oxide within the 2D porous carbon texture served as active sites for ammonia oxidation. Results of characterization showed that the Ni-MOF was a hexagonal and flaky nanoparticle. With increasing carbonization temperature, the nickel ions in the organic framework re-crystallized as NiO clusters on the surfaces of the 2D carbon. The electrochemical surface area of Ni/NiOx/NC significantly increased as to improve the efficiency of ammonia oxidation. The phase transition of Ni(OH)2⇌NiOOH at around +0.8 V was the primary mediator of electron transfer. Batch electrolysis was conducted under constant current and constant potential modes. The electrolysis parameters included pyrolysis temperatures, pH, current density, initial feed concentration, and electrode potential. The constant current batch experiments indicated that via carbonization at 800 °C, Ni/NiOx/NC(800) was able to decrease the ammonium nitrogen of 50 mg-N/L to below 1 ppm within 4 hours at a current density of 3 mA/cm2 and pH 11 with negligible oxygenated nitrogen formation. The constant potential experiments confirmed that N2 nitrogen selectivity was enhanced up to 90% at +0.8 V.

Keywords: electrochemical oxidation, nickel oxyhydroxide, metal-organic framework, ammonium, nitrate

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Authors: Robin Anderson, David Nisbet

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Nitrate, 3-nitro-1-propionic acid (NPA) and 3-nitro-1-propanol (NPOH) are biologically active chemicals that can accumulate naturally in rangeland grasses forages consumed by grazing cattle, sheep and goats. While toxic to livestock if accumulations and amounts consumed are high enough, particularly in animals having no recent exposure to the forages, these chemicals are known to be potent inhibitors of methane-producing bacteria inhabiting the rumen. Consequently, there is interest in examining their potential use as anti-methanogenic compounds to decrease methane emissions by grazing ruminants. Presently, rumen microbes, collected freshly from a cannulated Holstein cow maintained on 50:50 corn based concentrate:alfalfa diet were mixed (10 mL fluid) in 18 x 150 mm crimp top tubes with 0.5 of high nitrate-containing barley (Hordeum vulgare; containing 272 µmol nitrate per g forage dry matter), and NPA- or NPOH- containing milkvetch forages (Astragalus canadensis and Astragalus miser containing 80 and 174 soluble µmol NPA or NPOH/g forage dry matter respectively). Incubations containing 0.5 g alfalfa (Medicago sativa) were used as controls. Tubes (3 per each respective forage) were capped and incubated anaerobically (using oxygen free carbon dioxide) for 24 h at 39oC after which time amounts of total gas produced were measured via volume displacement and headspace samples were analyzed by gas chromatography to determine concentrations of hydrogen and methane. Fluid samples were analyzed by gas chromatography to measure accumulations of fermentation acids. A completely randomized analysis of variance revealed that the nitrate-containing barley and both the NPA- and the NPOH-containing milkvetches significantly decreased methane production, by > 50%, when compared to methane produced by populations incubated similarly with alfalfa (70.4 ± 3.6 µmol/ml incubation fluid). Accumulations of hydrogen, which are typically increased when methane production is inhibited, by incubations with the nitrate-containing barley and the NPA- and NPOH-containing milkvetches did not differ from accumulations observed in the alfalfa controls (0.09 ± 0.04 µmol/mL incubation fluid). Accumulations of fermentation acids produced in the incubations containing the high-nitrate barley and the NPA- and NPOH-containing milkvetches likewise did not differ from accumulations observed in incubations containing alfalfa (123.5 ± 10.8, 36.0 ± 3.0, 17.1 ± 1.5, 3.5 ± 0.3, 2.3 ± 0.2, 2.2 ± 0.2 µmol/mL incubation fluid for acetate, propionate, butyrate, valerate, isobutyrate, and isovalerate, respectively). This finding indicates the microbial populations did not compensate for the decreased methane production via compensatory changes in production of fermentative acids. Stoichiometric estimation of fermentation balance revealed that > 77% of reducing equivalents generated during fermentation of the forages were recovered in fermentation products and the recoveries did not differ between the alfalfa incubations and those with the high-nitrate barley or the NPA- or NPOH-containing milkvetches. Stoichiometric estimates of amounts of hexose fermented similarly did not differ between the nitrate-, NPA and NPOH-containing incubations and those with the alfalfa, averaging 99.6 ± 37.2 µmol hexose consumed/mL of incubation fluid. These results suggest that forages containing nitrate, NPA or NPOH may be useful to reduce methane emissions of grazing ruminants provided risks of toxicity can be effectively managed.

Keywords: nitrate, nitropropanol, nitropropionic acid, rumen methane emissions

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Authors: Vu H. N. Khue, Marian Pavelka, Georg Jocher, Jiří Dušek, Le T. Son, Bui T. An, Ho Q. Bang, Pham Q. Huong

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Agriculture is an important economic sector of Vietnam, the most popular of which is wet rice cultivation. These activities are also known as the main contributor to the national greenhouse gas. In order to understand more about greenhouse gas exchange in these activities and to investigate the factors influencing carbon cycling and sequestration in these types of ecosystems, since 2019, the first eddy covariance station has been installed in a paddy field in Long An province, Mekong Delta. The station was equipped with state-of-the-art equipment for CO₂ and CH₄ gas exchange and micrometeorology measurements. In this study, data from the station was processed following the ICOS recommendations (Integrated Carbon Observation System) standards for CO₂, while CH₄ was manually processed and gap-filled using a random forest model from methane-gapfill-ml, a machine learning package, as there is no standard method for CH₄ flux gap-filling yet. Finally, the carbon equivalent (Ce) balance based on CO₂ and CH₄ fluxes was estimated. The results show that in 2020, even though a new water management practice - alternate wetting and drying - was applied to reduce methane emissions, the paddy field released 928 g Cₑ.m⁻².yr⁻¹, and in 2021, it was reduced to 707 g Cₑ.m⁻².yr⁻¹. On a provincial level, rice cultivation activities in Long An, with a total area of 498,293 ha, released 4.6 million tons of Cₑ in 2020 and 3.5 million tons of Cₑ in 2021.

Keywords: eddy covariance, greenhouse gas, methane, rice cultivation, Mekong Delta

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Authors: Mohd Amran, Chan Yi Jing, Chong Chien Hwa

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Production of biogas from POME requires anaerobic digestion (AD), thus, anaerobic digester performance in biogas plants is crucial. As POME from different sources have varying characteristics due to different process flows in mills, there is no ideal treatment parameters for POME. Hence, different treatment plants alter different parameters in anaerobic digestion to achieve desired biogas production levels and to meet POME waste discharge limits. The objective of this study is to evaluate the performance of mesophilic anaerobic digestion in four different biogas plants in Malaysia. Aspects of POME pre-treatment efficiency, analysis of treated POME and AD’s bottom sludge characteristics, including several parameters like chemical oxygen demand (COD), biological oxygen demand (BOD), total solid (TS) removal in the effluent, pH and temperature changes, total biogas produced, the composition of biogas including methane (CH₄), carbon dioxide (CO₂), hydrogen sulfide (H₂S) and oxygen (O₂) were investigated. The effect of organic loading rate (OLR) and hydraulic retention time (HRT) on anaerobic digester performance is also evaluated. In pre-treatment, it is observed that BGP B has the lowest average outlet temperature of 40.41°C. All BGP shows a high-temperature fluctuation (36 to 49 0C) and good pH readings (minimum 6.7), leaving the pre-treatment facility before entering the AD.COD removal of POME is considered good, with an average of 78% and maximum removal of 85%. BGP C has the lowest average COD and TS content in treated POME, 13,313 mg/L, and 12,048 mg/L, respectively. However, it is observed that the treated POME leaving all ADs, still contains high-quality organic substances (COD between 12,000 to 19,000 mg/L) that might be able to digest further to produce more biogas. The biogas produced in all four BGPs varies due to different COD loads. BGP B has the highest amount of biogas produced, 378,874.7 Nm³/month, while BGP D has the lowest biogas production of 272,378.5 Nm³/month. Furthermore, the composition of biogas produced in all plants is well within literature values (CH4 between 55 to 65% and CO₂ between 32 to 36%).

Keywords: palm oil mill effluent, in-ground lagoon anaerobic digester, anaerobic digestion, biogas

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Authors: Masoumeh Moghbel

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Nowadays, carbon dioxide which is produced by human activities is considered as the main effective factor in the global warming occurrence. Regarding to the role of CO2 and its ability in trapping the heat, the main objective of this research is study the effect of atmospheric CO2 (which is recorded in Manaloa) on variations of temperature parameters (daily mean temperature, minimum temperature and maximum temperature) in 5 meteorological stations in Iran which were selected according to the latitude and altitude in 40 years statistical period. Firstly, the trend of temperature parameters was studied by Regression and none-graphical Man-Kendal methods. Then, relation between temperature variations and CO2 were studied by Correlation technique. Also, the impact of CO2 amount on temperature in different atmospheric levels (850 and 500 hpa) was analyzed. The results illustrated that correlation coefficient between temperature variations and CO2 in low latitudes and high altitudes is more significant rather than other regions. it is important to note that altitude as the one of the main geographic factor has limitation in affecting the temperature variations, so that correlation coefficient between these two parameters in 850 hpa (r=0.86) is more significant than 500 hpa (r = 0.62).

Keywords: altitude, atmospheric carbon dioxide, latitude, temperature variations

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Authors: Jean De Dieu Ayabagabo, Paul A.Onjoro, Karubiu P. Migwi, Marie C. Dusingize

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This study investigated the effects of feed on milk yield and quality through feed monitoring and quality assessment, and the consequent enteric methane gas emissions from smallholder dairy farms in drier areas of Rwanda, using the Tier II approach for four seasons in three zones, namely; Mayaga and peripheral Bugesera (MPB), Eastern Savanna and Central Bugesera (ESCB), and Eastern plateau (EP). The study was carried out using 186 dairy cows with a mean live weight of 292 Kg in three communal cowsheds. The milk quality analysis was carried out on 418 samples. Methane emission was estimated using prediction equations. Data collected were subjected to ANOVA. The dry matter intake was lower (p<0.05) in the long dry season (7.24 Kg), with the ESCB zone having the highest value of 9.10 Kg, explained by the practice of crop-livestock integration agriculture in that zone. The Dry matter digestibility varied between seasons and zones, ranging from 52.5 to 56.4% for seasons and from 51.9 to 57.5% for zones. The daily protein supply was higher (p<0.05) in the long rain season with 969 g. The mean daily milk production of lactating cows was 5.6 L with a lower value (p<0.05) during the long dry season (4.76 L), and the MPB zone having the lowest value of 4.65 L. The yearly milk production per cow was 1179 L. The milk fat varied from 3.79 to 5.49% with a seasonal and zone variation. No variation was observed with milk protein. The seasonal daily methane emission varied from 150 g for the long dry season to 174 g for the long rain season (p<0.05). The rain season had the highest methane emission as it is associated with high forage intake. The mean emission factor was 59.4 Kg of methane/year. The present EFs were higher than the default IPPC value of 41 Kg from developing countries in African, the Middle East, and other tropical regions livestock EFs using Tier I approach due to the higher live weight in the current study. The methane emission per unit of milk production was lower in the EP zone (46.8 g/L) due to the feed efficiency observed in that zone. Farmers should use high-quality feeds to increase the milk yield and reduce the methane gas produced per unit of milk. For an accurate assessment of the methane produced from dairy farms, there is a need for the use of the Life Cycle Assessment approach that considers all the sources of emissions.

Keywords: footprint, forage, girinka, tier

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Authors: Elnaz Akbari, Zolkafle Buntat

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Today, the use of carbon-based materials such as graphene, carbon nanotubes, etc. in various applications is being extensively studied by researchers in the field. One of such applications is using them in gas sensors. While analytical investigations on the physical and chemical properties of carbon nanomaterials are the focal points in the studies, the need for experimental measurements on various physical characteristics of these materials is deeply felt. In this work, a set of experiments has been conducted using arc discharge Methane decomposition attempting to obtain carbonaceous materials (C-strands) formed between graphite electrodes. The current-voltage (I-V) characteristics of the fabricated C-strands have been investigated in the presence and absence of two different gases, NO2 and CO2. The results reveal that the current passing through the carbon films increases when the concentrations of gases are increased from 200 to 800 ppm. This phenomenon is a result of conductance changes and can be employed in sensing applications such as gas sensors.

Keywords: carbonaceous materials, gas sensing, methane arc discharge decomposition, I-V characteristics

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Authors: Abdolreza Farhadian, Anh Phan, Zahra Taheri Rizi, Elaheh Sadeh

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The utilization of solidified gas technology based on hydrates exhibits considerable promise for carbon capture, storage, and natural gas transportation applications. The pivotal factor impeding the industrial implementation of hydrates lies in the need for efficient and non-foaming promoters. In this study, a biosurfactant with sulfonate, amide, and carboxyl groups (BS) was synthesized as a methane hydrate formation promoter, replicating the chemical characteristics of amino acids and sodium dodecyl sulfate (SDS). The synthesis of BS was achieved using an eco-friendly and three-step process. The first two steps were solvent-free, while a water-isopropanol mixture was utilized in the final step. High-pressure autoclave experiments demonstrated a significant enhancement in methane hydrate formation kinetics with low BS concentrations. 50 ppm of BS yielded a maximum water-to-hydrate conversion of 66.9%, equivalent to a storage capacity of 119.9 v/v in distilled water. With increasing BS concentration to 500 ppm, the conversion degree and storage capacity reached 97% and 162.6 v/v, respectively. Molecular dynamic simulation revealed that BS molecules acted as collectors for methane molecules, augmenting hydrate growth rate and increasing the number of hydrate cavities. Additionally, BS demonstrated a biodegradability exceeding 60% within 28 days. Toxicity assessments confirmed BS's biocompatibility, with cell viability above 70% for skin and lung cells at concentrations up to 160 and 80 µg/mL, respectively. BS showed significant potential as an environmentally friendly alternative to synthetic surfactants like SDS for methane storage. These findings suggest that the synthesis of effective, such as BS, holds promise for diverse applications, including seawater desalination, carbon capture, and gas storage.

Keywords: solidified methane, gas storage, gas hydrates, green surfactant, gas hydrate promoter, computational simulation, sustainability

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Authors: Imran Hanif, Amanda Persdotter, Sedigheh Bigdeli, Jesper Liske, Torbjorn Jonsson

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Renewable fuels such as biomass/waste for power production is an attractive alternative to fossil fuels in order to achieve a CO₂ -neutral power generation. However, the combustion results in the release of corrosive species. This puts high demands on the corrosion resistance of the alloys used in the boiler. Stainless steels containing nickel and/or nickel containing coatings are regarded as suitable corrosion resistance material especially in the superheater regions. However, the corrosive environment in the boiler caused by the presence of water vapour and reactive alkali very rapidly breaks down the primary protection, i.e., the Cr-rich oxide scale formed on stainless steels. The lifetime of the components, therefore, relies on the properties of the oxide scale formed after breakaway, i.e., the secondary protection. The aim of the current study is to investigate the role of varying nickel content (0–82%) on the high-temperature corrosion of model alloys with 18% Cr (Fe in balance) in the laboratory mimicking industrial conditions at 600°C. The influence of nickel is investigated on both the primary protection and especially the secondary protection, i.e., the scale formed after breakaway, during the oxidation/corrosion process in the dry O₂ (primary protection) and more aggressive environment such as H₂O, K₂CO₃ and KCl (secondary protection). All investigated alloys experience a very rapid loss of the primary protection, i.e., the Cr-rich (Cr, Fe)₂O₃, and the formation of secondary protection in the aggressive environments. The microstructural investigation showed that secondary protection of all alloys has a very similar microstructure in all more aggressive environments consisting of an outward growing iron oxide and inward growing spinel-oxide (Fe, Cr, Ni)₃O₄. The oxidation kinetics revealed that it is possible to influence the protectiveness of the scale formed after breakaway (secondary protection) through the amount of nickel in the alloy. The difference in oxidation kinetics of the secondary protection is linked to the microstructure and chemical composition of the complex spinel-oxide. The detailed microstructural investigations were carried out using the extensive analytical techniques such as electron back scattered diffraction (EBSD), energy dispersive X-rays spectroscopy (EDS) via the scanning and transmission electron microscopy techniques and results are compared with the thermodynamic calculations using the Thermo-Calc software.

Keywords: breakaway corrosion, EBSD, high-temperature oxidation, SEM, TEM

Procedia PDF Downloads 141

Authors: Amarachi Delight Onyemachi, Gregory Ikechukwu Onwuka

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The growing consumer trend for natural ingredients, functional foods with health benefits and the perceived risk of carcinogenesis associated with synthetic antioxidants have forced food manufacturers to look for alternatives for producing healthy and safe food. Herbs and spices are cheap, natural and harmless sources of antioxidants which can delay and prevent lipid oxidation of food products and also confer its unique organoleptic properties and health benefits to food products. The Nigerian climate has been proven to be conducive for the production of spices and herbs and is blessed bountifully with a wide range of them. Five selected Nigerian herbs and spices Piper guieense, Xylopia aethopica, Gongronema latifolium and Ocimum gratissimum were evaluated for their ability to act as radical scavengers. The spices were extracted with 80% ethanol and evaluated using total phenolic capacity (TPC), DPPH (1,1-diph diphenyl-2-picrylhydrazyl radical) ABTS (2,2’azinobis-(3-ethylbenzthiazoline-6-sulfonic acid)), total antioxidant capacity (TAC), reducing power (RP) assays. The TPC ranged from 5.33 µg GAE/mg (in Gongronema latifolium) to 15.55 µg GAE/mg (in Ocimum gratissimum). The DPPH and ABTS scavenging activity of the extracts ranged from 0.23-0.36 IC50 mg/ml and 2.32-7.25 Trolox equivalent % respectively. The TAC and RP of the extract ranged from 6.73-10.64 µg AAE/mg and 3.52-10.19 µg AAE/mg. The result of percentage yield of the extract ranged from as low as 9.94% in Gongronema latifolium and to as high as 23.85% in Xylopia aethopica. A very strong positive relationship existed between the total antioxidant capacity and total phenolic content of the tested herbs and spices (R2=0.96). All of the extracts exhibited different extent of strong antioxidant activity, high antioxidant activity was found in Ocimum gratissimum and Gongronema latifolium with the least. However, Gongronema latifolium possessed the highest total antioxidant capacity. These data confirm the appreciable antioxidant potentials and high phenolic content of Nigerian herbs and spices, thereby providing justification for their use in dishes and functional foods, prevention of cellular damage caused by free radicals and use as natural antioxidants in the food industry for prevention of lipid oxidation in food products. However, to utilize these natural antioxidants in food products, further analysis and studies of their behaviour in food systems at varying temperature, pH conditions and ionic concentrations should be carried out to displace the use of synthetic antioxidants like BHT and BHA.

Keywords: Antioxidant, free radicals, herbs, phenolic, spices

Procedia PDF Downloads 256