The granulation process in palm oil mill effluent using calcium oxide-cement kiln dust (CaO-CKD) provides an attractive and cost effective treatment option. In this study the efficiency of CaO-CKD at doses of 1.5-20 g/l was tested in batch experiments and found that 10 g of CaO/l caused the greatest degradation of VFA, butyrate and acetate. An upflow anaerobic sludge blanket (UASB) reactor was operated continuously at 35°C for 150 days to investigate the effect of CaO-CKD on sludge granulation and methanogenesis during start-up. The treatment of POME emphasized the influence of varying organic loading rates (OLR). Up to 94.9% of COD was removed when the reactor was fed with the 15.5-65.5 g-CODg/l at an OLR of 4.5-12.5 kg-COD/m(3)d, suggesting the feasibility of using CaO in an UASB process to treat POME. The ratio of volatile solids/total solids (VS/TS) and volatile fatty acids in the anaerobic sludge in the UASB reactor decreased significantly after long-term operation due to the precipitation of calcium carbonate in the granules. Granulation and methanogenesis decreased with an increase in the influent CaO-CKD concentration.
Nanostructured hydrogenated carbon nitride (CNx:H) thin films were synthesized on a crystal silicon substrate at low deposition temperature by radio-frequency plasma-enhanced chemical vapor deposition (PECVD). Methane and nitrogen were the precursor gases used in this deposition process. The effects of N₂ to the total gas flow rate ratio on the formation of CNx:H nanostructures were investigated. Field-emission scanning electron microscopy (FESEM), Auger electron spectroscopy (AES), Raman scattering, and Fourier transform of infrared spectroscopies (FTIR) were used to characterize the films. The atomic nitrogen to carbon ratio and sp² bonds in the film structure showed a strong influence on its growth rate, and its overall structure is strongly influenced by even small changes in the N₂:(N₂ + CH₄) ratio. The formation of fibrous CNx:H nanorod structures occurs at ratios of 0.7 and 0.75, which also shows improved surface hydrophobic characteristic. Analysis showed that significant presence of isonitrile bonds in a more ordered film structure were important criteria contributing to the formation of vertically-aligned nanorods. The hydrophobicity of the CNx:H surface improved with the enhancement in the vertical alignment and uniformity in the distribution of the fibrous nanorod structures.
In this study, a two-stage domesticated shear-loop anaerobic contact stabilization (SLACS) system is introduced as a new reactor design to enhance methane productivity with significant reduction in hydrogen sulphide (H2S) synthesis. Due to the rich sulfate content in industrial wastewaters, the initial fermentation phase of anaerobic digestion is highly acidifying and often leads to severe performance losses, digester's instability, and even culture crash. The SLACS system functions as a dissimilatory sulfate reduction - methanogenic reactor consisting of two compartments, a shear-loop anaerobic bed (SLAB) unit and an anaerobic plug flow (APF) unit. The functional role of the SLAB unit is not limited to acidogenesis but also sulfidogenic processes, which curtails H2S generation in the APF unit (methanogenic stage). Experimental observations indicated that pH serves a critical role in the cohabitation of acidogenic and sulfidogenic microbes in the SLAB unit. Although acidogenesis was not influenced by pH within the range of 4.5-6.0, it is vital to stabilize the pH of this unit at 5.4 to establish a steady sulfate reduction of above 75%. The highest desulfurization achieved in this compartment was 88% under a hydraulic retention time (HRT) of 4 h. With an average methane productivity of 256 mL g-1 VS, the methanogenic performance of the two-stage domesticated SLACS system shows a 32% methanogenic proficiency higher than that of the one-stage digestion system. Microbial community structure within the system carried out via Next Generation Sequencing (NGS) provided qualitative data on the sludge's sulfidogenic and methanogenic performance.
Waste management can be regarded as a cross-cutting environmental 'mega-issue'. Sound waste management practices support the provision of basic needs for general health, such as clean air, clean water and safe supply of food. In addition, climate change mitigation efforts can be achieved through reduction of greenhouse gas emissions from waste management operations, such as landfills. Landfills generate landfill gas, especially methane, as a result of anaerobic degradation of the degradable components of municipal solid waste. Evaluating the mode of generation and collection of landfill gas has posted a challenge over time. Scientifically, landfill gas generation rates are presently estimated using numerical models. In this study the Intergovernmental Panel on Climate Change's Waste Model is used to estimate the methane generated from a Malaysian sanitary landfill. Key parameters of the model, which are the decay rate and degradable organic carbon, are analysed in two different approaches; the bulk waste approach and waste composition approach. The model is later validated using error function analysis and optimum decay rate, and degradable organic carbon for both approaches were also obtained. The best fitting values for the bulk waste approach are a decay rate of 0.08 y(-1) and degradable organic carbon value of 0.12; and for the waste composition approach the decay rate was found to be 0.09 y(-1) and degradable organic carbon value of 0.08. From this validation exercise, the estimated error was reduced by 81% and 69% for the bulk waste and waste composition approach, respectively. In conclusion, this type of modelling could constitute a sensible starting point for landfills to introduce careful planning for efficient gas recovery in individual landfills.
The livestock industry needs to use crop straws that are highly digestible to improve feed productivity and reduce ruminal methane emissions. Hence, this study aimed to use the ozonation and pelleting processes to enhance the digestibility and reduce the ruminal methane emissions of wheat straw enriched with two nitrogen sources (i.e., urea and heat-processed broiler litter). Various analyses were conducted on the pellets, including digestibility indicators, mechanical properties, surface chemistry functionalization, chemical-spectral-structural features, and energy requirements. For comparison, loose forms of the samples were also analyzed. The nitrogen-enriched ozonated wheat straw pellets had 43.06 % lower lignin, 28.30 % higher gas production for 24 h, 12.28 % higher metabolizable energy, 13.78 % higher in vitro organic matter digestibility for 24 h, and 28.81 % higher short-chain fatty acid content than the nitrogen-enriched loose sample. The reduction of methane emissions by rumen microorganisms of nitrogen-enriched wheat straw by ozonation, pelleting, and ozonation-pelleting totaled 89.15 %, 23.35 %, and 66.98 %, respectively. The ozonation process resulted in a 64 % increase in the particle density, a 5.5-time increase in the tensile strength, and a 75 % increase in the crushing energy of nitrogen-enriched wheat straw. In addition, ozone treatment could also reduce the specific and thermal energy consumption required in the pelleting process by 15.10 % and 7.61 %, respectively.
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.
Inhibition of Thymidine phosphorylase (TP) is continuously studied for the design and development of new drugs for the treatment of neoplastic diseases. As a part of our effort to identify TP inhibitors, we performed a structure-based virtual screening (SBVS) of our compound collection. Based on the insights gained from structures of virtual screening hits, a scaffold was designed using 1,3,4-oxadiazole as the basic structural feature and SAR studies were carried out for the optimization of this scaffold. Twenty-five novel bis-indole linked 1,3,4-oxadiazoles (7-31) were designed, synthesized and tested in vitro against E. coli TP (EcTP). Compound 7 emerged as potent TP inhibitor with an IC50 value of 3.50 ± 0.01 μM. Docking studies were carried out using GOLD software on thymidine phosphorylase from human (hTP) and E. coli (EcTP). Various hydrogen bonding, hydrophobic interactions, and π-π stacking were observed between designed molecules and the active site amino acid residues of the studied enzymes.
Optimization of thermo-alkaline disintegration of sewage sludge for enhanced biogas yield was carried out using response surface methodology (RSM) and Box-Behnken design of experiment. The individual linear and quadratic effects as well as the interactive effects of temperature, NaOH concentration and time on the degree of disintegration were investigated. The optimum degree of disintegration achieved was 61.45% at 88.50 °C, 2.29 M NaOH (24.23%w/w total solids) and 21 min retention time. Linear and quadratic effects of temperature are most significant in affecting the degree of disintegration. The coefficient of determination (R(2)) of 99.5% confirms that the model used in predicting the degree of disintegration process has a very good fitness with the experimental variables. The disintegrated sludge increased the biogas yield by 36%v/v compared to non-disintegrated sludge. The RSM with Box-Behnken design is an effective tool in predicting the optimum degree of disintegration of sewage sludge for increased biogas yield.
Chemical toxins and organic contaminants such as hydrocarbons and dyes are major global
contaminants with countless tones of those chemicals are created yearly with a significant
amount release to the environment. In this work we screen the ability of a molybdenum-reducing
bacterium isolated from contaminated soil to decolorize various azo and triphenyl methane dyes
independent of molybdenum reduction. Biochemical analysis resulted in a tentative identification
of the bacterium as Enterobacter sp. strain Zeid-6. The bacterium was able to decolorize the azo
dye Orange G. The bacterium reduces molybdate to Mo-blue optimally at pH between 5.5 and
8.0 and temperatures of between 30 and 37 oC. Other requirements include a phosphate
concentration of 5 mM and a molybdate concentration of 20 mM. The absorption spectrum of the
Mo-blue produced was similar to previous Mo-reducing bacterium, and closely resembles a
reduced phosphomolybdate. Molybdenum reduction was inhibited by copper, lead, mercury and
silver which showed 36.8, 16.9, 64.9 and 67.6% inhibition to Mo-reducing activity of
Enterobacter sp. strain Zeid-6, respectively. The resultant molybdenum blue spectrum closely
resembles the spectrum of molybdenum blue from the phosphate determination method. The
ability of this bacterium to detoxify molybdenum and decolorize azo dye makes this bacterium
an important tool for bioremediation.
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 rapid growth in the development of power generation and transportation sectors would result in an increase in the carbon dioxide (CO2) concentration in the atmosphere. As it will continue to play a vital role in meeting current and future needs, significant efforts have been made to address this problem. Over the past few years, extensive studies on the development of heterogeneous catalysts for CO2 methanation have been investigated and reported in the literatures. In this paper, a comprehensive overview of methanation research studies over lanthanide oxide catalysts has been reviewed. The utilisation of lanthanide oxides as CO2 methanation catalysts performed an outstanding result of CO2 conversion and improvised the conversion of acidity from CO2 gas to CH4 gas. The innovations of catalysts towards the reaction were discussed in details including the influence of preparation methods, the structure-activity relationships as well as the mechanism with the purpose of outlining the pathways for future development of the methanation process.
The increasing demands of natural gas pushes energy industries to explore the reservoirs contain high CO2 concentration
and impurities including heavy hydrocarbons. High efficiency of using membrane technology in CO2
-natural gas separation
has extended its potential application to offshore environment. Due to the limited studies related with the separation of
CO2
under offshore conditions, the present work has investigated the separation performance of a commercial membrane
in removing bulk CO2
from methane at elevated pressure condition. A wide range of offshore operating conditions
including pressure from 10 to 50 bar, CO2
concentration from 25 to 70% and temperature of 30o
C, 40o
C and 50o
C were
studied. High relative CO2 permeance and relative CO2
/CH4
selectivity were observed when the pressure and the CO2
concentration increased. This work, therefore substantial is to bridge the gap and facilitates the application of membrane
technology for offshore operating conditions.
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.
An anaerobic membrane bioreactor (AnMBR) was employed as primary treatment unit for anaerobic treatment of simulated wastewater to produce high effluent quality. A lab scale hollow fiber membrane was used to scrutinize the performance of AnMBR as a potential treatment system for simulated milk wastewater and analyze its energy recovery potential. The 15 L bioreactor was operated continuously at mesophilic conditions (35 °C) with a pH constant of 7.0. The membrane flux was in the range of 9.6-12.6 L/m2. h. The different organic loading rates (OLRs) of 1.61, 3.28, 5.01, and 8.38 g-COD/L/d, of simulated milk wastewater, were fed to the reactor and the biogas production rate was analyzed, respectively. The results revealed that the COD removal efficiencies of 99.54 ± 0.001% were achieved at the OLR of 5.01 gCOD/L/d. The highest methane yield was found to be at OLR of 1.61 gCOD/L/d at HRT of 30 d with the value of 0.33 ± 0.01 L-CH4/gCOD. Moreover, based on the analysis of energy balance in the AnMBR system, it was found that energy is positive at all the given HRTs. The net energy production (NEP) ranged from 2.594 to 3.268 kJ/gCOD, with a maximum NEP value of 3.268 kJ/gCOD at HRT 10 d HRT. Bioenergy recovery with the maximum energy ratio, of 4.237, was achieved with an HRT of 5 d. The study suggests a sizable energy saving with the anaerobic membrane process.
Lovastatin, a natural byproduct of some fungi, is able to inhibit HMG-CoA (3-hydroxy-3 methyl glutaryl CoA) reductase. This is a key enzyme involved in isoprenoid synthesis and essential for cell membrane formation in methanogenic Archaea. In this paper, experiments were designed to test the hypothesis that lovastatin secreted by Aspergillus terreus in fermented rice straw extracts (FRSE) can inhibit growth and CH4 production in Methanobrevibacter smithii (a test methanogen). By HPLC analysis, 75% of the total lovastatin in FRSE was in the active hydroxyacid form, and in vitro studies confirmed that this had a stronger effect in reducing both growth and CH4 production in M. smithii compared to commercial lovastatin. Transmission electron micrographs revealed distorted morphological divisions of lovastatin- and FRSE-treated M. smithii cells, supporting its role in blocking normal cell membrane synthesis. Real-time PCR confirmed that both commercial lovastatin and FRSE increased (P < 0.01) the expression of HMG-CoA reductase gene (hmg). In addition, expressions of other gene transcripts in M. smithii. with a key involvement in methanogenesis were also affected. Experimental confirmation that CH4 production is inhibited by lovastatin in A. terreus-fermented rice straw paves the way for its evaluation as a feed additive for mitigating CH4 production in ruminants.
Palm oil mill effluent (POME) is a highly polluting wastewater that pollutes the environment if discharged directly due to its high chemical oxygen demand (COD) and biochemical oxygen demand (BOD) concentration. Anaerobic digestion has been widely used for POME treatment with large emphasis placed on capturing the methane gas released as a product of this biodegradation treatment method. The anaerobic digestion method is recognized as a clean development mechanism (CDM) under the Kyoto protocol. Certified emission reduction (CER) can be obtained by using methane gas as a renewable energy. This review aims to discuss the various anaerobic treatments of POME and factors that influence the operation of anaerobic treatment. The POME treatment at both mesophilic and thermophilic temperature ranges are also analyzed.
A comprehensive exergoeconomic performance analysis of a municipal solid waste digestion plant integrated with a biogas genset was conducted throughout this study in order to highlight its bottlenecks for further improvements. Exergoeconomic performance parameters of each component of the plant were determined by solving exergy and cost balance equations based on Specific Exergy Costing (SPECO) approach. The analysis was conducted to reveal the cost structure of the plant based on actual operating information and economic data. The exergy unitary cost of two main products of the plant, i.e., bioelectricity and biofertilizer were determined at 26.27 and 2.27 USD/GJ, respectively. The genset showed the highest overall cost rate (101.27 USD/h) followed by digester (68.41 USD/h). Furthermore, the net bioelectricity amounted to 67.81% of the overall cost rate of the products, while this value was 32.19% for both liquid and dewatered digestates. According to the results obtained, efforts should mainly focus on enhancing the efficiency of the genset in order to boost the overall performance of the system exergoeconomically. In addition, minimizing the investment-related cost of the digester could also substantially enhance the exergoeconomic performance of the plant.
The performance of modified anaerobic inclining-baffled reactor (MAI-BR) treating recycled paper mill effluent (RPME) was investigated by varying the influent chemical oxygen demand (CODin) concentration from 1000 to 4000 mg/L, and the hydraulic retention time (HRT) from 3 to 1 day, corresponding to an organic loading rate increase from 0.33 to 4 g COD/L day. Throughout 126 days of operation, a maximum removal efficiency of up to 96% of chemical oxygen demand (COD) and 99% of biological oxygen demand, methane (CH4) yield of 0.259 L CH4/g COD, and a stable effluent pH of 6.5 were achieved. Furthermore, the compartmental performance showed that most of the organic substrates were removed in the initial two compartments, resulting in low pH and alkalinity levels and a high concentration of volatile fatty acids. Overall, the results showed that the MAI-BR successfully treated RPME, and the performance was affected by the variation of HRT more than the CODin.
Recycled paper mill effluent (RPME) consists of various organic and inorganic compounds. In this study, modified anaerobic hybrid baffled (MAHB) bioreactor has been successfully used to anaerobically digest RPME. The anaerobic digestion was investigated in relation to methane production rate, lignin removal, and chemical oxygen demand (COD) removal, with respect to organic loading rate (OLR) and hydraulic retention time (HRT). The analysis using kinetic study was carried out under mesophilic conditions (37 ± 2 °C) and influent COD concentrations (1000-4000 mg L-1), to prove its practicability towards RPME treatment. First-order kinetic model was used to clarify the behavior of RPME anaerobic digestion under different OLRs (0.14-4.00 g COD L-1 d-1) and HRT (1-7 d). The result shows that the highest COD removal efficiency and methane production rate were recorded to be 98.07% and 2.2223 L CH4 d-1, respectively. This result was further validated by evaluating the biokinetic coefficients (reaction rate constant (k) and maximum biogas production (ym)), which gave values of k = 0.57 d-1 and ym = 0.331 L d-1. This kinetic data concludes that MAHB presented satisfactory performance towards COD removal with relatively high methane production, which can be further utilized as on-site energy supply.
Recycled paper mill effluent (RPME) contains high levels of organic and solid compounds, causing operational problems for anaerobic biological treatment. In this study, a unique modified anaerobic inclining-baffled reactor (MAI-BR) has been developed to treat RPME at various initial chemical oxygen demand (COD) concentrations (1000-4000 mg/L) and hydraulic retention times (HRTs) (3 and 1 day). The COD removal efficiency was decreased from 96 to 83% when the organic loading rate (OLR) was increased from 0.33 to 4 g/L day. Throughout the study, a maximum methane yield of 0.25 L CH4/g COD was obtained, while the pH fluctuated in the range of 5.8 to 7.8. The reactor performance was influenced by the development and distribution of the microbial communities. Based on the next-generation sequencing (NGS) analysis, the microbial community represented a variety of bacterial phyla with significant homology to Euryarchaeota (43.06%), Planctomycetes (24.68%), Proteobacteria (21.58%), Acidobacteria (4.12%), Chloroflexi (3.14%), Firmicutes (1.12%), Bacteroidetes (1.02%), and others (1.28%). The NGS analysis showed that the microbial community was dominated by Methanosaeta concilii and Candidatus Kuenenia stuttgartiensis. This can be supported by the presence of filamentous and spherical microbes of different sizes. Additionally, methanogenic and anaerobic ammonium oxidation (ANAMMOX) microorganisms coexisted in all compartments, and these contributed to the overall degradation of substances in the RPME. Graphical abstract ᅟ.