The valorization of lignin to replace phenol is significant in the production of phenolic resins. However, a great challenge is to produce lignin-based resin (LR) with a suitable viscosity and high substitution rate of lignin to phenol. In this study, LRs were produced using hardwood technical lignin derived from the pulping industry. Structural analysis of the LRs indicated that the unsubstituted para and ortho carbon atoms of the aromatic ring influenced the curing temperature and activation energy of the resins. The curing kinetics and thermal decomposition study implied that urea and methylene groups in cured LRs were significant factors that affected the thermal stability negatively. The prepared LRs showed desirable features if used as adhesives to make plywood. This is the first approach in which a substitution rate of up to 65 % is achieved for low-reactive-site hardwood lignin, which provides a solution to the challenge of the simultaneous realization of the high addition of lignin and the adaptive viscosity of resins.
A series of bimetallic catalysts containing nickel supported over MgO-ZrO2 were tested for activity in the dry reforming of carbon dioxide. A nickel-cobalt bimetallic catalyst gave the best performance in terms of conversion and coke resistance from a range of Ni-X bimetallic catalysts, X=Ca, K, Ba, La, and Ce. The nitrogen-adsorption and hydrogen-chemisorption studies showed the Ni-Co bimetallic supported catalyst to have good surface area with high metal dispersion. This contributed to the high catalytic activity, in terms of conversion activity and stability of the catalyst, at an equimolar methane/carbon dioxide feed ratio. The kinetics of methane dry reforming are studied in a fixed-bed reactor over an Ni-Co bimetallic catalyst in the temperature range 700-800 °C by varying the partial pressures of CH4 and CO2. The experimental data were analyzed based on the proposed reaction mechanism using the Langmuir-Hinshelwood kinetic model. The activation energies for methane and carbon dioxide consumption were estimated at 52.9 and 48.1 kJ mol(-1), respectively. The lower value of CO2 activation energy compared to the activation energy of CH4 indicated a higher reaction rate of CO2, which owes to the strong basicity of nanocrystalline support, MgO-ZrO2.
Dry reforming of methane (DRM) is one of the more promising methods for syngas (synthetic gas) production and co-utilization of methane and carbon dioxide, which are the main greenhouse gases. Magnesium is commonly applied in a Ni-based catalyst in DRM to improve catalyst performance and inhibit carbon deposition. The aim of this review is to gain better insight into recent developments on the use of Mg as a support or promoter for DRM catalysts. Its high basicity and high thermal stability make Mg suitable for introduction into the highly endothermic reaction of DRM. The introduction of Mg as a support or promoter for Ni-based catalysts allows for good metal dispersion on the catalyst surface, which consequently facilitates high catalytic activity and low catalyst deactivation. The mechanism of DRM and carbon formation and reduction are reviewed. This work further explores how different constraints, such as the synthesis method, metal loading, pretreatment, and operating conditions, influence the dry reforming reactions and product yields. In this review, different strategies for enhancing catalytic activity and the effect of metal dispersion on Mg-containing oxide catalysts are highlighted.
The ideal conditions for anaerobic digestion experiments with biochar addition are challenging to thoroughly study due to different experimental purposes. Therefore, three tree-based machine learning models were developed to depict the intricate connection between biochar properties and anaerobic digestion. For the methane yield and maximum methane production rate, the gradient boosting decision tree produced R2 values of 0.84 and 0.69, respectively. According to feature analysis, digestion time and particle size had a substantial impact on the methane yield and production rate, respectively. When particle sizes were in the range of 0.3-0.5 mm and the specific surface area was approximately 290 m2/g, corresponding to a range of O content (>31%) and biochar addition (>20 g/L), the maximum promotion of methane yield and maximum methane production rate were attained. Therefore, this study presents new insights into the effects of biochar on anaerobic digestion through tree-based machine learning.
In this research, sago mill effluent was treated using anaerobic sequencing batch reactor (ASBR). Seven HRT from 10 to 1.5 days were tested to evaluate the methane production from sago mill effluent. The findings revealed the highest methane production rate was found at 1.288 L CH4/L reactor. d under HRT of 2 days The results showed that COD removals decreased from 70% to 47% as HRT was reduced from 10 to 2 days. The HRT 1.5 days was found critical for the studied system, which leads to decreased in methane production, yield and COD removal. Overall, ASBR was capable to treat sago mill effluent in producing methane by means of anaerobic digestion.
In the current scenario, alternative energy sources are the need of the hour. Organic wastes having a larger fraction of biodegradable constituents present a sustainable bioenergy source. It has been reported that the calorific value of biogas generated by anaerobic digestion (AD) is 21-25 MJ/m3 with the treatment which makes it an excellent replacement of natural gas and fossil fuels and can reduce more than 80% greenhouse gas emission to the surroundings. However, there are some limitations associated with the AD process for instance ammonia build-up at the first stage reduces the rate of hydrolysis of biomass, whereas, in the last stage it interferes with methane formation. Owing to special physicochemical properties such as high activity, high reactive surface area, and high specificity, tailor-made conductive nanoparticles can improve the performance of the AD process. In the AD process, H2 is used as an electron carrier, referred as mediated interspecies electron transfer (MIET). Due to the diffusion limitation of these electron carriers, the MIET efficiency is relatively low that limits the methanogenesis. Direct interspecies electron transfer (DIET), which enables direct cell-to-cell electron transport between bacteria and methanogen, has been considered an alternative efficient approach to MIET that creates metabolically favorable conditions and results in faster conversion of organic acids and alcohols into methane. This paper discusses in detail the application of conductive nanoparticles to enhance the AD process efficiency. Interaction between microbes in anaerobic conditions for electron transfer with the help of CNPs is discussed. Application of a variety of conductive nanomaterials as an additive is discussed with their potential biogas production and treatment enhancement in the anaerobic digestion process.
An alternative method was proposed to optimize the treatment process of palm oil mill effluent (POME) in an effort to address the poor removal efficiencies in terms of the chemical and biological oxygen demand (COD and BOD), total suspended solids (TSS) as well as oil and grease (O&G) content in treated POME along with many environmental issues associated with the existing POME treatment process. The elimination of the cooling ponds and the insertion of a dewatering device in the treatment process were recommended. The dewatering device should enhance the anaerobic digestion process by conferring a means of control on the digesters' load. The objective of this study is to identify the optimum solid: liquid ratio (total solids (TS) content) that would generate the maximum amount of biogas with better methane purity consistently throughout the anaerobic digestion of POME, all while improving the treated effluent quality. It was established that a 40S:60L (4.02% TS) was the best performing solid loading in terms of biogas production and methane yield as well as COD, BOD, TSS, and O&G removal efficiencies. Meanwhile, at higher solid loadings, the biogas production is inhibited due to poor transport and mass transfer. It is also speculated that sulfate-reducing bacteria tended to inhibit the biogas production based on the significantly elevated H2S concentration recorded for the 75S:25L and the 100S loadings.
Influence of the labile organic fraction (LOF) on anaerobic digestion of food waste was investigated in different S/I ratio of 0.33, 0.5, 1.0, 2.0 and 4.0g-VSsubstrate/g-VSinoculum. Two types of substrate, standard food waste (Substrate 1) and standard food waste with the supernatant (containing LOF) removed (Substrate 2) were used. Highest methane yield of 435ml-CH4g-VS(-1) in Substrate 1 was observed in the lowest S/I ratio, while the methane yield of the other S/I ratios were 38-73% lower than the highest yield due to acidification. The methane yields in Substrate 2 were relatively stable in all S/I conditions, although the maximum methane yield was low compared with Substrate 1. These results showed that LOF in food waste causes acidification, but also contributes to high methane yields, suggesting that low S/I ratio (<0.33) is required to obtain a reliable methane yield from food waste compared to other organic substrates.
We report the use of a new precursor as active agents to promote the growth of carbon nanotubes (CNT) in methane ambient using a simple thermal chemical vapour deposition method. The agents consist of ammonia and methanol mixed at different ratios and was found to enhance the growth of CNTs. The optimum methanol to ammonia ratio was found to be 8 to 5, whereby longer and denser CNTs were produced compared to other ratios. The result was found otherwise when the experiment was done solely in methane ambient. In addition, CNT growth on substrates coated with double layer Ni catalyst was improved in terms of quality and density compared to a single coated substrates. This finding is supported by Raman spectrometry analysis.
A synthesis is presented of sampling work conducted under a UK government-funded Darwin Initiative grant undertaken predominantly within the Danum Valley Conservation Area (DVCA), Sabah, East Malaysia. The project concerned the assemblage structure, gas physiology and landscape gas fluxes of termites in pristine and two ages of secondary, dipterocarp forest. The DVCA termite fauna is typical of the Sunda region, dominated by Termes-group soil-feeders and Nasutitermitinae. Selective logging appears to have relatively little effect on termite assemblages, although soil-feeding termites may be moderately affected by this level of disturbance. Species composition changes, but to a small extent when considered against the background level of compositional differences within the Sunda region. Physiologically the assemblage is very like others that have been studied, although there are some species that do not fit on the expected body size-metabolic rate curve. As elsewhere, soil-feeders and soil-wood interface-feeders tend to produce more methane. As with the termite assemblage characteristics, gross gas and energy fluxes do not differ significantly between logged and unlogged sites. Although gross methane fluxes are high, all the soils at DVCA were methane sinks, suggesting that methane oxidation by methanotrophic bacteria was a more important process than methane production by gut archaea. This implies that methane production by termites in South-East Asia is not contributing significantly to the observed increase in levels of methane production worldwide. Biomass density, species richness, clade complement and energy flow were much lower at DVCA than at a directly comparable site in southern Cameroon. This is probably due to the different biogeographical histories of the areas.
We report the synthesis and biological evaluation of two new series of 2-amino-6-benzyl-4-phenyl-4,6-dihydrobenzo[c]pyrano[2,3-e][1,2]thiazine-3‑carbonitrile 5,5-dioxides and 2-amino-6-methyl-4-phenyl-4,6-dihydrobenzo[c]pyrano[2,3-e][1,2]thiazine-3‑carbonitrile 5,5-dioxides. The synthetic methodology involves a multistep reaction starting with methyl anthranilate which was coupled with methane sulfonyl chloride. The product of the reaction was subjected to N-benzylation and N-methylation reactions followed by ring closure with sodium hydride resulting in the formation of respective 2,1-benzothiazine 2,2-dioxides. These 2,1-benzothiazine precursors were subjected to multicomponent reaction with malononitrile and substituted benzaldehydes for the synthesis of two new series of pyranobenzothiazines (6a-r and 7a-r). The synthesized compounds were screened as selective inhibitors of monoamine oxidase A and monoamine oxidase B. The in vitro results suggested that compound 6d and 7q are the selective inhibitors of monoamine oxidase A, however, the selective and potent inhibitors of monoamine oxidase B included compounds 6h and 7r. Moreover, some dual inhibitors were noticed like 7l having more inhibitory activity towards both the isozymes. Moreover, the binding modes of the selective and potent inhibitors of monoamine oxidase A and B were investigated by molecular docking analysis. The results suggested that the synthetic derivatives may be potential towards the monoamine oxidase isozymes.
Synthesis and anticancer studies of three symmetrically and non-symmetrically substituted silver(I)-N-Heterocyclic carbene complexes of type [(NHC)2-Ag]PF6 (7-9) and their respective (ligands) benzimidazolium salts (4-6) are described herein. Compound 5 and Ag-NHC-complex 7 were characterized by the single crystal X-ray diffraction technique. Structural studies for 7 showed that the silver(I) center has linear C-Ag-C coordination geometry (180.00(10)o). Other azolium and Ag-NHC analogues were confirmed by H1 and C13-NMR spectroscopy. The synthesized analogues were biologically characterized for in vitro anticancer activity against three cancer cell lines including human colorectal cancer (HCT 116), breast cancer (MCF-7), and erythromyeloblastoid leukemia (K-562) cell lines and in terms of in vivo acute oral toxicity (IAOT) in view of agility and body weight of female rats. In vitro anticancer activity showed the values of IC50 in range 0.31-17.9 μM in case of K-562 and HCT-116 cancer cell lines and 15.1-35.2 μM in case of MCF-7 while taking commercially known anticancer agents 5-fluorouracil, tamoxifen, and betulinic acid which have IC50 values 5.2, 5.5, and 17.0 μM, respectively. In vivo study revealed vigor and agility of all test animals which explores the biocompatibility and non-toxicity of the test analogues.
A series of four benzimidazolium based nitrile-functionalized mononuclear-Ag(I)-N-heterocyclic carbene and binuclear-Ag(I)-N-heterocyclic carbene (Ag(I)-NHC) hexafluorophosphate complexes (5b-8b) were synthesized by reacting the corresponding hexafluorophosphate salts (1b-4b) with Ag2O in acetonitrile, respectively. These compounds were characterized by 1H NMR, 13C NMR, IR, UV-visible spectroscopic techniques, elemental analyses and molar conductivity. Additionally, 8b was structurally characterized by single crystal X-ray diffraction technique. Preliminary in vitro antibacterial evaluation was conducted for all the compounds against two standard bacteria; gram-positive (Staphylococcus aureus) and gram-negative (Escherichia coli) bacterial strains. Most of the Ag(I)-NHC complexes (5b-8b) showed moderate to good antibacterial activity with MIC values in the range of 12.5-100 μg/mL. Especially, compound 8b exhibited promising anti-Staphylococcus aureus activity with a low MIC value (12.5 μg/mL). However, all the hexafluorophosphate salts (1b-4b) were inactive against the bacteria strains. The preliminary interactive investigation revealed that the most active compound, 8b, could effectively intercalate into DNA to form 8b-DNA complex which shows a better binding ability for DNA (Kb = 3.627 × 106) than the complexes 5b-7b (2.177 × 106, 8.672 × 105 and 6.665 × 105, respectively). Nuclease activity of the complexes on plasmid DNA and Aedes albopictus genomic DNA was time-dependent, although minimal. The complexes were larvicidal to the mosquito, with 5b, 6b and 8b being highly active. Developmental progression from the larval to the adult stage was affected by the complexes, progressively being toxic to the insect's development with increasing concentration. These indicate the potential use of these complexes as control agents against bacteria and the dengue mosquito Ae. albopictus.
The influence of an anionic surfactant, a cationic surfactant, and salinity on adsorbed methane (CH4) in shale was assessed and modeled in a series of systematically designed experiments. Two cases were investigated. In case 1, the crushed Marcellus shale samples were allowed to react with anionic sodium dodecyl sulfate (SDS) and brine. In case 2, another set of crushed Marcellus shale samples were treated with cetyltrimethylammonium bromide (CTAB) and brine. The surfactant concentration and salinity of brine were varied following the Box-Behnken experimental design. CH4 adsorption was then assessed volumetrically in the treated shale at varying pressures (1-50 bar) and a constant temperature of 30 °C using a pressure equilibrium cell. Mathematical analysis of the experimental data yielded two separate models, which expressed the amount of adsorbed CH4 as a function of SDS/CTAB concentration, salinity, and pressure. In case 1, the highest amount of adsorbed CH4 was about 1 mmol/g. Such an amount was achieved at 50 bar, provided that the SDS concentration is kept close to its critical micelle concentration (CMC), which is 0.2 wt %, and salinity is in the range of 0.1-20 ppt. However, in case 2, the maximum amount of adsorbed CH4 was just 0.3 mmol/g. This value was obtained at 50 bar and high salinity (∼75 ppt) when the CTAB concentration was above the CMC (>0.029 wt %). The findings provide researchers with insights that can help in optimizing the ratio of salinity and surfactant concentration used in shale gas fracturing fluid.
Microbial electrolysis cells (MECs) are perceived as a potential and promising innovative biotechnological tool that can convert carbon-rich waste biomass or wastewater into hydrogen (H2) or other value-added chemicals. Undesired methane (CH4) producing H2 sinks, including methanogens, is a serious challenge faced by MECs to achieve high-rate H2 production. Methanogens can consume H2 to produce CH4 in MECs, which has led to a drop of H2 production efficiency, H2 production rate (HPR) and also a low percentage of H2 in the produced biogas. Organized inference related to the interactions of microbes and potential processes has assisted in understanding approaches and concepts for inhibiting the growth of methanogens and profitable scale up design. Thus, here in we review the current developments and also the improvements constituted for the reduction of microbial H2 losses to methanogens. Firstly, the greatest challenge in achieving practical applications of MECs; undesirable microorganisms (methanogens) growth and various studied techniques for eliminating and reducing methanogens activities in MECs were discussed. Additionally, this extensive review also considers prospects for stimulating future research that could help to achieve more information and would provide the focus and path towards MECs as well as their possibilities for simultaneously generating H2 and waste remediation.
Waste furniture boards (WFBs) contain hazardous formaldehyde and volatile organic compounds when left unmanaged or improperly disposed through landfilling and open burning. In this study, pyrolysis was examined as a disposal and recovery approach to convert three types of WFBs (i.e., particleboard, plywood, and fiberboard) into value-added chemicals using thermogravimetric analysis coupled with Fourier-transform infrared spectrometry (TG-FTIR) and pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS). TG-FTIR analysis shows that pyrolysis performed at an optimum temperature of 250-550 °C produced volatile products mainly consisting of carbon dioxide, carbon monoxide, and light hydrocarbons, such as methane. Py-GC/MS shows that pyrolysis at different final temperatures and heating rates recovered mainly phenols (25.9-54.7%) for potential use as additives in gasoline, colorants, and food. The calorific value of WFBs ranged from 16 to 18 MJ/kg but the WFBs showed high H/C (1.7-1.8) and O/C (0.8-1.0) ratios that provide low chemical energy during combustion. This result indicates that WFBs are not recommended to be burned directly as fuel, however, they can be pyrolyzed and converted into solid pyrolytic products such as biochar with improved properties for fuel application. Hazardous components, such as cyclopropylmethanol, were removed and converted into value-added compounds, such as 1,4:3,6-dianhydro-d-glucopyranose, for use in pharmaceuticals. These results show that the pyrolysis of WFBs at high temperature and low heating rate is a promising feature to produce value-added chemicals and reduce the formation of harmful chemical species. Thus, the release of hazardous formaldehyde and greenhouse gases into the environment is redirected.
Unsymmetrically substituted sterically tuned Pd(II)–NHC complexes of the general formula [PdCl2(NHC)2] (NHC = 1-allyl-3-methylimidazolin-2-ylidene, 7; 1-allyl-3-butylimidazol-2-ylidene, 8; 1-benzyl-3-butyl imidazolin-2-ylidene, 9) were prepared through transmetallation from their corresponding Ag(I)–NHC complexes. The Pd complexes were structurally characterized by different spectroscopic and X-ray diffraction methods. Complexes 7 and 9 adopted a trans–anti arrangement of the NHC ligands, whereas complex 8 adopted a cis–syn arrangement. Preliminary antibiogram studies using Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria showed that Ag(I)–NHC complexes demonstrate higher activity compared with Pd(I)–NHC complexes. Furthermore, Pd(II)–NHC complexes were evaluated for their anticancer potential using the human colorectal cancer cell line. A higher anticancer activity was observed for complexes 8 and 9, with 26.5 and 6.6 mM IC50 values, respectively.
Thermophilic treatment of palm oil mill effluent (POME) was studied in a novel integrated anaerobic-aerobic bioreactor (IAAB). The IAAB was subjected to a program of steady-state operation over a range of organic loading rate (OLR)s, up to 30 g COD/L day in order to evaluate its treatment capacity. The thermophilic IAAB achieved high chemical oxygen demand (COD), biochemical oxygen demand (BOD) and total suspended solids (TSS) removal efficiencies of more than 99% for OLR up to 18.5 g COD/L day. High methane yield of 0.32 LCH(4) (STP)/g COD(removed) with compliance of the final treated effluent to the discharge limit were achieved. This is higher than that of the mesophilic system due to the higher maximum specific growth rate (μ(max)) of the thermophilic microorganisms. Besides, coupling the model of Grau second order model (anaerobic system) with the model of Monod (aerobic system) will completely define the IAAB system.
Energy is widely used in industry for heating and cooling, with natural gas (NG) being the largest primary energy source in Malaysia, closely followed by coal. Renewable energy, such as biogas upgrading to biomethane, could cut the use of fossil fuels by supplementing NG usage due to their similar physicochemical and thermochemical characteristics. Biogas production plants in Malaysia are more commonly seen in waste-to-energy scenarios, with the technology anaerobic digestion, and their deployment is supported via feed-in tariffs (FiT) for power generation. Other potential applications such as the conversion of biogas into biomethane, injection into the natural gas grid or transportation through a virtual pipeline may still need further technical development. This paper presents spatial techno economic optimisation modelling using BeWhere to determine decentralised biomethane production plants using feedstock from multiple sources of biogas, including palm oil mill effluent (POME), food waste, cattle manure and chicken manure. This model considered potential configurations and sizes of the biomethane plants, the transportation of biomethane using a virtual pipeline (at 250 psig) and demand in one of the states in Malaysia, namely Johor. It was found that two to four biomethane plants with capacities ranging between 125 and 700 m3/h were located in densely populated areas or heavier industrial consumers when the carbon tax was implemented at 167.71 EUR/tCO2 (800 MYR/tCO2). Sensitivity analysis suggested that biomethane production increases with the increasing country renewable energy share target to beyond 2080 MW. It is recommended that specific policy regulations and Feed-in Tariff (FiT) mechanisms are used to expand the biomethane market share in the country.
Information on temporal and spatial variations in soil greenhouse gas (GHG) fluxes from tropical peat forests is essential to predict the influence of climate change and estimate the effects of land use on global warming and the carbon (C) cycle. To obtain such basic information, soil carbon dioxide (CO2) and methane (CH4) fluxes, together with soil physicochemical properties and environmental variables, were measured at three major forest types in the Maludam National Park, Sarawak, Malaysia, for eight years, and their relationships were analyzed. Annual soil CO2 fluxes ranged from 860 to 1450 g C m⁻2 yr⁻1 without overall significant differences between the three forest sites, while soil CH4 fluxes, 1.2-10.8 g C m⁻2 yr⁻1, differed. Differences in GHG fluxes between dry and rainy seasons were not necessarily significant, corresponding to the extent of seasonal variation in groundwater level (GWL). The lack of significant differences in soil CO2 fluxes between the three sites could be attributed to set-off between the negative and positive effects of the decomposability of soil organic matter as estimated by pyrophosphate solubility index (PSI) and GWL. The impact of El-Niño on annual CO2 flux also varied between the sites. The variation in soil CH4 fluxes from the three sites was enhanced by variations in temperature, GWL, PSI, and soil iron (Fe) content. A positive correlation was observed between the annual CH4 flux and GWL at only one site, and the influence of soil properties was more pronounced at the site with the lowest GWL and the highest PSI. Variation in annual CH4 fluxes was controlled more strongly by temperature where GWL was the highest and GWL and plant growth fluctuations were the least. Inter-annual variations in soil CO2 and CH4 fluxes confirmed the importance of long-term monitoring of these at multiple sites supporting different forest types.