Showing papers in "Journal of The Energy Institute in 2020"

Utilization of lignin: A sustainable and eco-friendly approach

Abstract: The use of renewable carbon sources as a substitute for fossil resources is an extensively essential and fascinating research area for addressing the current issues related to climate and future fuel requirements. The utilization of lignocellulosic biomasses as a source for renewable fuel/chemicals/mesoporous biochar derivative is gaining considerable attention due to the neutral carbon cycle. The cellulose and hemicellulose are highly utilized components of biomass, and on the other hand, lignin is a plentiful, under-utilized component of the lignocellulosic biomass in 2G ethanol and paper industry. Significant researchers have contributed towards lignin valorization, with a central goal of the production and upgradation of phenolic, unstable, acidic and oxygen-containing bio-oil to valuable chemicals or fuel grade hydrocarbons. This review is aimed to present the lignin valorization potential from pretreatment of biomass as an initial step to the final process, i.e., lignin bio-oil upgradation with mechanistic pathways. The review offers the source, structure, composition of various lignocellulosic biomasses, followed by a discussion of various pre-treatment techniques for biomass depolymerization. Different thermochemical approaches for bio-oil production from dry and wet biomasses are highlighted with emphasis on pyrolysis and liquefaction. The physical, chemical properties of lignin bio-oil and different upgradation methods for bio-oil as well as its model compounds are thoroughly discussed. It also addresses the related activity, selectivity, stability of numerous catalysts with reaction pathways and kinetics in a broad manner. The challenges and future research opportunities of lignin valorization are discussed in an attempt to place lignin as a feedstock for the generation of valuable chemical and fuel grade hydrocarbons.

Biomass thermochemical conversion: A review on tar elimination from biomass catalytic gasification

Abstract: Biomass is promising renewable energy because of the possibility of value-added fuels production from biomass thermochemical conversion. Among the thermochemical conversion technology, gasification could produce the H2-rich syngas then into value-added chemicals via F-T (Fischer-Tropsch) synthesis. However, a variety of difficulties, such as tar formation, reactors impediment, complex tar cracked mechanism, etc. make it difficult to develop for further application. This paper sheds light on the developments of biomass thermochemical conversion, tar classifications, tar formation, and elimination methods. Secondly, we provide a comprehensive the state-of-the-art technologies for tar elimination, and we introduce some advanced high activity catalysts. Furthermore, many represent tar models were employed for explanation of the tar-cracked pathway, and real tar-cracked mechanism was proposed. Following this, some operational conditions and effective gasified models were concluded to give an instruction for biomass catalytic gasification.

NOX emissions of compression ignition engines fueled with various biodiesel blends: A review

Abstract: There are some challenges about NOX emissions exhausted from diesel engines fueled with biodiesel. Due to increasingly stringent emission regulations, the different methods such as varying the engine operating parameters, treatment with antioxidant additive and blending fuels have been adapted to reduce emissions of biodiesel combustion. One of the effective methods is the combustion of dual or blending fuels. Various fuels such as gasoline, hydrogen, natural gas, biogas, different types of alcohols and also fuel additives have been used to reduce biodiesel disadvantages. This study reviews the potential of the different fuels as an additive in biodiesel fuel in correspond to reduce NOX emissions. The general reduction of NOX has been observed with the presence of gasoline, biogas and alcohols in biodiesel blends. The reduction of NOX in biodiesel-hydrogen, biodiesel-diesel or biodiesel–CNG combustion has not been observed through all engine conditions. Moreover the retarding injection timing, the lower injection pressure, EGR higher than 30% can result in the reduced NOX emissions. However it seems the decrease in NOX emissions can be achieved by the use of most fuels in blending with biodiesel under all engine operating conditions, if only the proper injection parameters and blending proportions of fuels are set.

TGA and kinetic study of different torrefaction conditions of wood biomass under air and oxy-fuel combustion atmospheres

Abstract: Combustion and oxy-fuel combustion characteristics of torrefied pine wood chips were investigated by Thermogravimetric Analysis (TGA). Three torrefaction temperatures (250, 300, and 350 °C) and two residence times (15 and 30 min) were considered. Experiments were carried out at three heating rates of 10, 20, and 40 °C/min. The isoconversional kinetic methods of FWO, KAS, and Friedman were employed to estimate the activation energies. The assessment of uncertainty in obtaining the activation energy values was also considered. The obtained results indicated that due to torrefaction, the O/C and H/C atomic ratios decreased, resulting the 300oC-30 min and 350oC-15 min torrefied biomass to be completely embedded in lignite region in van-Krevelen's diagram. Oxy-fuel combustion affected the decomposition of cellulose and lignin components of biomass while the impact on the hemicellulose component was negligible. The kinetic analysis revealed that with the evolution of conversion degree, the activation energy values increased during hemicellulose degradation, remained approximately constant during cellulose decomposition and showed a sharp decrease for lignin decomposition. The activation energy trends were comparable in both air and oxy-fuel combustion conditions, however slight changes in activation energy values were noticed. The highest activation energy value was obtained for 250oC-30 min torrefied biomass at 183.40 kJ/mol and the lowest value was 72.93 kJ/mol for 350oC-15 min biomass. The uncertainty values related to FWO method were lower than KAS and Friedman methods. The uncertainty values for FWO and KAS methods were at the range of 5–15%.

A TG-FTIR investigation on the co-pyrolysis of the waste HDPE, PP, PS and PET under high heating conditions

Abstract: The present study relates to the investigation of degradation of polymers such as HDPE, PP, PS and PET individually and in mixed forms. Eleven different mixture combinations were analyzed via TG Analysis to determine their degradation behavior individually and in mixed forms. FTIR analysis of the raw polymers was performed to investigate the presence of different functional groups in the sample. Online TG-FTIR analysis was performed to investigate the functional groups present in the volatiles fractions during single component pyrolysis and the interaction of polymers during co-pyrolysis was analyzed, compared and reported. Also, a real-world post consumer mixed waste was also analyzed and compared. During the co-pyrolysis of HDPE with PP and PS, the degradation of PP was delayed whereas PS reduced the degradation temperature of HDPE. In the case of degradation of PS with PP and PET, the increase in degradation temperature was reported whereas, in the case of PET and HDPE mixture, the degradation temperature of HDPE was reduced. During the interaction of PP and PET mixed degradation, PET degradation temperature was delayed. During the FTIR analysis a large amount of alkanes, alkenes, aromatics groups were observed during the degradation of HDPE, PP and PS whereas in case of PET the presence of oxygenated groups is observed. During the mixed degradation, the presence of PET in the sample caused the formation of oxygenated groups by reducing the absorption intensity of other groups or by disappearing the groups. Compounds such as benzoic acid, CO and CO2 was detected during the degradation of PET whereas in other polymers a large amount of methane or methylene group is observed. Overall during the degradation of mixed polymer mixture presence of PET played a vital role in the formation of light gas fractions. Even though a numerous investigation on co-pyrolysis of polymers were available, there is still not sufficient information of interaction of polymers with each other, especially with PET. This article attempts to fill this gap.

Energy, exergy and emission analysis on a DI single cylinder diesel engine using pyrolytic waste plastic oil diesel blend

Abstract: Depletion of fossil fuels and stringent emission norms focus attention to discover an evitable source of alternative fuel in order to attribute a significant compensation on conventional fuels. Besides, waste management policies encourage the valorization of different wastes for the production of alternative fuels in order to reduce the challenges of waste management. In this context, pyrolysis has become an emerging trend to convert different wastes into alternate fuel and suitable to be used as a substitute fuel for CI engines. The current investigation provides a sustainable and feasible solution for waste plastic management by widening the gap between global plastic production and plastic waste generation. It investigates the performance and emission of a single cylinder DI four stroke diesel engine using waste plastic oil (WPO) derived from pyrolysis of waste plastics using Zeolite-A as catalyst. Engine load tests have been conducted taking waste plastic oil and subsequently a blend of waste plastic oil by 10%, 20%, and 30% in volume proportions with diesel as fuel. The performance of the test engine in terms of brake thermal efficiency is found marginally higher and brake specific fuel consumption comparatively lowest for 20% WPO-diesel blend than pure diesel. The NOx and HC emission is found lower under low load condition and became higher by increasing the load as compared to diesel. Fuel exergy was significantly increasing after blending of WPO with pure diesel, but exergetic efficiency of the blended fuels followed the reverse trend. However, increase in load of the engine improved the exergetic efficiency. The 20% WPO–diesel blended fuel is found suitable to be used as an alternative fuel for diesel engine.

Pyrolysis kinetics behaviour and thermal pyrolysis of Samanea saman seeds towards the production of renewable fuel

Abstract: The present study addresses pyrolysis behaviour and potential of Samanea saman seeds (SS) towards its bioenergy potential using thermogravimetric analyzer and in a cylindrical pyrolyzer (semi-batch reactor). Pyrolysis kinetic behaviour of biomass was carried out using Kissinger, Distributed Activation Energy Model (DAEM) and Miura-Maki-Integral method (MMI) while thermal pyrolysis was carried out in a cylindrical shaped semi-batch reactor. Kinetic results confirmed that the average activation energy was found 118.24 kJ mol−1, 168.70 kJ mol−1, and 97.87 kJ mol−1 for Kissinger, DAEM, and MMI model respectively. Further, thermal pyrolysis of SS biomass yielded 44.20 wt% yield of pyrolytic liquid (31.20 wt% pyrolytic oil/organic oil and 13 wt% aqueous fraction). Characterization results of pyrolytic oil showed the presence of higher viscosity (86.01 cSt), higher oxygen content (33.11%), and lower ash content (0.46 wt%) and gross heating value. FTIR analysis confirmed mainly the presence of aromatics, acid, alkene, water, and protein impurities. Gas Chromatography (GC) results declared, an increase in hydrocarbon and hydrogen gas with an increase in temperature while reduced the generation of CO and CO2. Further, GC-MS analysis of pyrolytic oil revealed the presence of higher acids (19.46%), phenols (11.01%) ethers (11.12%) and ester (7.33%) which is a potent source of oxygenated compounds. Characterization results of biochar showed the presence of higher gross heating value (23.14 MJ kg), carbon content (62.66%), volatile matter (34.15%) and lower moisture (5.14%) and BET surface area (8.20 m2 g−1). Combining these results, it can be suggested that SS biomass has the potential to produce renewable fuel and chemicals, while biochar can be used for various applications.

Activated carbon synthesis from tangerine peel and its use in hydrogen storage

Abstract: Activated carbon samples were synthesized by chemical and physical activations of tangerine peel The activated carbons were characterized via using Fourier Transform Infrared-Attenuated Total Reflectance spectroscopy (FTIR-ATR), Scanning Electron Microscopy (SEM), Brunauer-Emmett-Teller (BET), Differential Thermal Analysis-Thermogravimetry (DTA/TG) techniques It was found that the activated carbon samples were porous, and their surface areas were increased by treating with the various concentrations of ZnCl2 and KOH After the formation of activated carbons, they turned into a structure that was formed from carbon atoms, and their residual amounts decreased In addition, the hydrogen storage capacities of the activated carbon samples were measured in different pressures at 77 and 298 K using the Hiden IMI PSI instrument The results, confirmed that the hydrogen storage capacities of the activated carbons were higher at the cryogenic temperatures, and higher hydrogen storage capacity were observed by the increasing concentrations of activation agents in the synthesized activated carbons The activated carbons synthesized by ZnCl2 had higher hydrogen storage capacity than those by KOH

Catalytic pyrolysis of pinewood over ZSM-5 and CaO for aromatic hydrocarbon: Analytical Py-GC/MS study

Abstract: A higher amount of oxygenates is the main constraint for higher yield and quality of aromatics in catalytic pyrolysis while a study of hydrocarbon production with a balance of reactive species lies importance in the catalytic upgrading of pyrolytic vapor. Catalytic pyrolysis of pinewood sawdust over acidic (ZSM-5) and basic (CaO) catalyst was conducted by means of Py-GC/MS to evaluate the effect of biomass to catalyst loading ratio on aromatic hydrocarbon production. Catalytic pyrolysis with four different biomass to catalyst ratios (0.25:1, 0.5:1, 1:1, and 2:1) and non-catalytic pyrolysis were conducted. It has been obtained that ZSM-5 showed better catalytic activity in terms of a high fraction of aromatic hydrocarbon. The ZSM-5 catalyst showed a potential on the aromatization as the yield of aromatic hydrocarbon was increased with a higher amount of ZSM-5 catalyst and the highest yield of aromatics (42.19 wt %) was observed for biomass to catalyst ratio of 0.25:1. On the other hand, basic CaO catalyst was not selective to aromatic hydrocarbon from pinewood sawdust but explored high deacidification reaction in pyrolytic vapor compared to ZSM-5 catalyst, whereas non-catalytic pyrolysis resulted in acidic species (13.45 wt %) and phenolics (46.5 wt %). Based on the results, ZSM-5 catalyst can only be suggested for catalytic pyrolysis of pinewood sawdust for aromatic hydrocarbon production.

TG-FTIR and Py-GC/MS study of the pyrolysis mechanism and composition of volatiles from flash pyrolysis of PVC

Abstract: To facilitate the reuse and recycling of polyvinyl chloride (PVC) to achieve sustainable development and new industrialization, the composition and mechanism of formation of volatiles during the flash pyrolysis of PVC were studied by thermogravimetry-Fourier transform infrared (TG-FTIR) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). TG and derivative thermogravimetry (DTG) analyses indicated two main degradation stages during flash pyrolysis of PVC, namely dehydrochlorination of PVC and decomposition of dechlorinated-PVC. Simultaneously, the FTIR results revealed that the main functional groups in the pyrolysis process were H–Cl, -C-Cl, C–H, C H, and aromatic groups. The relative content of main volatiles was determined by Py-GC/MS, and decreased in the following order: aromatics > alkenes > hydrogen chloride (HCl) > chlorinated hydrocarbons. Specifically, the relative content of aromatics was as high as 76.790–81.809%, while that of HCl was in the range of 3.016–3.096%. The carbon number distribution and the relative content of main products obtained from the flash pyrolysis of PVC at different final temperatures were also analysed. According to the experimental results, the mechanism of formation of the main volatiles based on free-radical reactions was deduced in detail. Therefore, this study provides further details for deepening the understanding of the PVC pyrolysis process.

Hydrothermal liquefaction of macroalgae: Influence of zeolites based catalyst on products

Abstract: Hydrothermal liquefaction (HTL) of Ulva prolifera macroalgae (UP) was carried out in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different weight percentage (10–20 wt%) at 260–300 °C for 15–45 min. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite, and Mordenite in the conversion of Ulva prolifera showed that is affected by properties of zeolites. Maximum bio-oil yield for non-catalytic liquefaction was 16.6 wt% at 280 °C for 15 min. The bio-oil yield increased to 29.3 wt% with ZSM-5 catalyst (15.0 wt%) at 280 °C. The chemical components and functional groups present in the bio-oils are identified by GC-MS, FT-IR, 1H-NMR, and elemental analysis techniques. Higher heating value (HHV) of bio-oil (32.2–34.8 MJ/kg) obtained when catalyst was used compared to the non-catalytic reaction (21.2 MJ/kg). The higher de-oxygenation occurred in the case of ZSM-5 catalytic liquefaction reaction compared to the other catalyst such as Y-zeolite and mordenite. The maximum percentage of the aromatic proton was observed in bio-oil of ZSM-5 (29.7%) catalyzed reaction and minimum (1.4%) was observed in the non-catalyst reaction bio-oil. The use of zeolites catalyst during the liquefaction, the oxygen content in the bio-oil reduced to 17.7%. Aqueous phase analysis exposed that presence of valuables nutrients.

Experimental investigation on gasification characteristics of polycarbonate (PC) microplastics in supercritical water

Abstract: In order to solve the problem of marine microplastics and realize the harmless resource utilization of plastics, the gasification experiments of polycarbonate (PC) microplastics were carried out in supercritical water and a novel seawater gasification of microplastic experiment was investigated. In this paper, the effects of different operating conditions (temperature, time, feedstock concentration, pressure) on gasification performance were discussed. The gasification kinetic of microplastics in supercritical water was calculated. The experimental results showed that the increase in gasification temperature and time enhanced the cracking reaction and free radical reaction of the microplastics to increase the gasification efficiency, while the reduction in feedstock concentration improved the gasification efficiency by increasing the gasification level of unit feedstock. The change in pressure had no significant effect on gasification due to the fact that the properties of the supercritical water were not significantly changed. It was found that the valuable results that all alkali metal salts in seawater promote hydrogen conversion, while in terms of carbon conversion, only KCl, CaCl2, NaHCO3 and seawater had a significant catalytic effect on the gasification. Seawater gasification of microplastics was a potential resource utilization method. Finally, it was considered that the PC plastic gasification conformed to the random nucleation and subsequent growth model (n = 3), and the reaction activation energy was 230.45 kJ/mol, which was smaller than that of traditional pyrolysis.

Formation mechanism of HCN and NH3 during indole pyrolysis: A theoretical DFT study

Abstract: Coal is a major contributor to the global emission of nitrogen oxides. The NOx formation during coal utilisation typically derives from thermal decomposition of N-containing compounds pyrrole, which usually combines with an aromatic ring in the form of indole. NH3 and HCN are common precursors of NOx from the decomposition of N-containing compounds. In this study, possible pathways of indole pyrolysis to form HCN and NH3 are investigated using the density functional theory (DFT) method. Calculation results indicate that indole pyrolysis has two type of possible initial reactions, which are internal hydrogen transfer and hydrogen homolysis reaction, respectively. The initial reaction mode of indole has a great impact on the subsequent pyrolysis pathway. Additionally, it is shown that indole can produce two nitrogen-containing products, i.e. HCN and NH3. Five pathways will result in the formation of HCN (path-1, path-3, path-a, path-b, path-c), and another two pathways will lead to the NH3 (path-2, path-4). Furthermore, among all the reaction mechanisms of indole pyrolysis, the path-1 is the optimal reaction pathway. During which, indole is converted to a diradical intermediate, then the intermediate undergoes a synergy ring-opening transition state to form a new intermediate. Afterwards, the new intermediate decomposes into CN by homolysis of the C–C bond.

CO2 methanation in the presence of methane: catalysts design and effect of methane concentration in the reaction mixture

Abstract: The work in this paper evidences the viability of producing synthetic natural gas (SNG) via the methanation reaction tackling two fundamental challenges on methanation catalysis (i) the development of advanced catalysts able to achieve high CO2 conversion and high methane yields and (ii) the unexplored effect of residual methane on the methanation stream. Both challenges have been successfully addressed using Ni/CeO2-ZrO2 catalysts promoted with Mn and Co. Mn does not seem to be a good promoter while Co prevents carbon deposition and secondary reactions. In fact, our Co-doped sample reached high levels of CO2 conversion and CH4 selectivity, especially at low reaction temperatures. In addition, this catalyst exhibits excellent catalytic behaviour when methane is introduced into the gas mixture, indicating its feasibility for further study to be conducted in realistic flue gases environments and methanation units with recycling loops. Furthermore, when methane is introduced in the reactant mixture, the Ni-Co/CeO2-ZrO2 sample is very stable maintaining high levels of conversion and selectivity. Overall our Co-doped catalyst can deliver high purity synthetic natural gas for long-term runs, promising results for gas-phase CO2 conversion units.

Physicochemical and structural characterization of biochar derived from the pyrolysis of biosolids, cattle manure and spent coffee grounds

Abstract: In the framework of circular economy, the need of new feedstock materials for the production of alternative new products is of high priority. Biowastes such as manure, sewage sludge (biosolids, BS) and food-waste are used as raw materials for the production of biochar. The present study aims at characterizing biochars produced from three distinct biowastes (i) manure from cattle waste (manure-derived biochar; MDB), (ii) biosolids (BS) from a conventional Urban Wastewater Treatment Plant (UWTP) (biosolids-derived biochar; BDB), and (iii) spent coffee grounds (SCG)-derived biochar (SCGDB). Samples were slowly pyrolyzed in a small-scale kiln with a capacity of 20–24 kg. The samples were heated under nitrogen atmosphere at approximately 6–7 °C min−1 up to the desired temperature (550 °C) and held for 1.5h. The physicochemical characterization of biochars showed the production of alkaline materials with similarities and variations in their characteristics, which depend to the type of feedstock used. The surface area of the raw materials was considerably low (

Experimental investigation on ignition and burnout characteristics of semi-coke and bituminous coal blends

Abstract: Ignition and burnout characteristics of semi-coke and bituminous coal blends were investigated by thermogravimetric analyzer and drop tube furnace. The results showed that the ignitability index and the comprehensive combustion characteristic index of the blends decrease as the blending proportion of semi-coke increases, but the average activation energy of the blends increases gradually. Ignition mode of bituminous coal is changed from homogeneous to hetero-homogeneous ignition with the increasing of semi-coke content in the blends. When the mixing proportion of semi-coke is lower than 45%, the burnout rate is lower than the weighted value in the early stage of combustion and gradually higher than the weighted value with the development of combustion process. However, the burnout is always lower than the weighted value to mix with 67% semi-coke. Increasing furnace temperature from 850 °C to 1050 °C can improve the mid-term reaction process, alleviate the negative effects of semi-coke on the co-combustion process and increase the burnout rate. So less than 45% semi-coke blending ratio and increasing furnace temperature are recommended for semi-coke and bituminous coal co-combustion.

Non-catalytic and catalytic pyrolysis of Ulva prolifera macroalgae for production of quality bio-oil

Abstract: Pyrolysis of Ulva prolifera macroalgae (UM), an aquatic biomass, was carried out in a fixed-bed reactor in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different catalyst to biomass ratio. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite and Mordenite catalyst in the conversion of UM showed that is affected by properties of zeolites. Bio-oil yield was increased in the presence of Y-Zeolite while decreased with ZSM-5 and Mordenite catalyst. Maximum bio-oil yield for non-catalytic pyrolysis was (38.5 wt%) and with Y-Zeolite catalyst (41.3 wt%) was obtained at 400 °C respectively. All catalyst showed a higher gas yield. The higher gas yield might be attributed to that catalytic pyrolysis did the secondary cracking of pyrolytic volatiles and promoted the larger small molecules. The chemical components and functional groups present in the pyrolytic bio-oils are identified by GC–MS, FT-IR, 1H-NMR and elemental analysis techniques. Phenol observed very less percentage in the case of non-catalytic pyrolysis bio-oil (9.9%), whereas catalytic pyrolysis bio-oil showed a higher percentage (16.1%). The higher amount of oxygen present in raw biomass reduced significantly when used catalyst due to the oxygen reacts with carbon and produce (CO and CO2) and water.

Effects of ash composition and ash stack heights on soot deposition and oxidation processes in catalytic diesel particulate filter

Abstract: In order to provide the theorical basis for regeneration strategy and solid catalytic reaction of catalytic diesel particulate filter (CDPF), the effects of ash composition and ash stack heights on soot deposition and oxidation processes in CDPF are investigated. The MgO ash nanoparticles have an inert effect on soot oxidation process through a series of thermogravimetric experiments. Based on the visualized single-channel bench, the influence of ash stack height on the soot deposition and regeneration processes is studied. The deposition process of soot particles on the CDPF slice without ash is divided into three stages, including depth filtration, transitional filtration and soot cake formation stages. When the ash stack height is 15 μm, there are only transitional filtration and soot cake formation stages. Then, only soot cake formation stage remains when the height increases to 30 μm. During the regeneration process, the pressure drop mainly has three linear decline stages, the oxidation rates of which are 0.77, 1.78 and 0.54 Pa/s, respectively. When the ash stack height increases from 0 to 30 μm, the oxidation rate of soot layer during Ⅱ-regeneration stage decreases from 1.78 to 0.51 Pa/s. The oxidation rate is 0.51 Pa/s at 30 μm ash stack height, which is close to the 0.55 Pa/s oxidation rate of the clean DPF sample. Consequently, around 30 μm ash stack height is the limit distance of back-diffusion of active oxygen molecules, which leads to the failure of the CDPF catalytic layer.

Microwave pyrolysis of polystyrene and polypropylene mixtures using different activated carbon from biomass

Abstract: In this study, microwave pyrolysis was experimented with mixed types of plastic waste. Two different plastic wastes polystyrene waste (PSW) and polypropylene waste (PPW) were used as feedstock. Carbon and activated carbon were synthesized from different biomass; rice husk (RH), corn husk (CH) and coconut sheath (CS) respectively which are used as microwave susceptors. The effect of impregnation on product yields was studied. Microwave pyrolysis at 900 W and with a polymer to an absorbent ratio of 10:1, produced the highest oil yield of 84.30 wt% when coconut sheath activated carbon (CSAC) was used as an absorbent. The reaction time was 10 min for the complete decomposition of polymer mixtures. Oil properties were determined and a high calorific value of 46.87 MJ kg−1 was obtained. These properties were compared to conventional fuel properties and the product oil has a density of 0.76 g ml−1 and viscosity of 2.4 cSt which is an equivalent fraction obtained to that of gasoline. Product oil has a styrene recovery of 67.58% from microwave pyrolysis. The results demonstrate that, microwave pyrolysis has a great potential for energy recovery from mixed plastic waste and the use of agricultural residues as absorbents enhanced the production efficiency of the process.

Characterization and evaluation of mesoporous high surface area promoted Ni- Al2O3 catalysts in CO2 methanation

Abstract: In this research, mesoporous high surface area Ni-Al2O3 catalysts promoted with different transition metals (Cr, Fe, Mn, Cu, and Co) were synthesized via ultrasound-assisted co-precipitation method and their performance was explored in CO2 methanation process. The promoters can affect the textural and catalytic properties of the Ni-Al2O3 catalysts to some extent. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed reduction with hydrogen (H2-TPR), and N2 adsorption-desorption (BET) were used for the characterization of the prepared samples. From the BET results, it was found that the incorporation of 5 wt% of the promoter into Ni-Al2O3 catalysts caused a decrease in the surface area, NiAl2O4 crystalline size and an increase in the mean pore diameter and total pore volume. Among the samples, the catalyst modified by Mn, exhibited the higher catalytic activity and selectivity towards CH4, especially at low temperatures (200–350 °C). These results could be explained by highest Ni active sites dispersion of this catalyst and enhancement of the catalyst reducibility at the low temperatures. The effect of Mn content was also evaluated and the results revealed that the Ni-Al2O3 sample modified with 3 wt% Mn with the highest BET surface area and the lowest crystalline size possessed the best catalytic performance. To further investigate the influence of ultrasonic irradiation, the optimal catalyst was prepared with a conventional co-precipitation method and its textural and catalytic properties were compared with those obtained for the catalyst prepared with the ultrasonic assisted coprecipitation method. Also, 25Ni-3Mn-Al2O3 catalyst showed a stable performance at 350 °C for 10 h in the CO2 methanation reaction.

Boron-doped Ni/SBA-15 catalysts with enhanced coke resistance and catalytic performance for dry reforming of methane

Abstract: Nickel-based heterogeneous catalysts have shown promising results in many industrial-scale catalytic reforming processes and hydrocarbon reforming reactions such as dry reforming of methane (DRM). However, it is also reported that Ni-based catalysts generally show less resistance to the carbonaceous deposition, which ultimately causes their rapid deactivation during the reaction. One possible solution to improve the coke resistance is the addition of a promoter to the catalyst, which has shown successful results to reduce the coke formation. Therefore, this study also aimed to prepare boron-promoted Ni-based catalysts and investigate their efficiency for DRM reactions. A series of different catalysts with 10% nickel and x% boron (x: 1%, 2%, 3%, and 5%) were prepared by using an ordered mesoporous silica as a support and tested in DRM. The results demonstrated that boron-promoted Ni/SBA-15 catalysts obtained significant catalytic activity for CH4 and CO2 conversions. Meanwhile, it was noticed that a lower concentration of boron (1 and 2%) was more favourable to achieve higher catalytic activity, whereas the higher concentration (3% and 5%) resulted in a comparatively lower conversion for CH4 and CO2. Evidently, the higher activity of 2% B-promoted catalyst was ascribed to the synergistic effect of high surface area and lower crystallite size that greatly improved the active sites accessibility. Moreover, the results confirmed 14% carbon deposition on unpromoted (NS) catalyst and it was reduced to 1.3% for 2% boron-promoted catalyst owing to the presence of B-OH species on catalyst surface.

Development and evaluation of magnetic iron-carbon sorbents for mercury removal in coal combustion flue gas

Abstract: In order to get a cost effective and recyclable sorbent for mercury removal, a series of magnetic iron-carbon (Fe–C-x) sorbents was developed by co-precipitation. The physical and chemical properties of obtained sorbents were evaluated through various characterization methods. According to the results, Fe3O4 precipitate on carbon weakens the surface properties, but mercury removal performance in simulated flue gas is excellent. For flue gas components, HCl promotes mercury oxidation and adsorption on sorbents, O2 has limited effect on mercury removal and SO2 plays an inhibitive role. NO could enhance mercury oxidation with O2 existence because of the generation of NO2, which could react with Hg0 through heterogeneous reaction over iron-carbon surface. Besides, effects of temperature and regeneration performance were further researched under simulated flue gas. Apart from higher temperature will decompose mercury compounds and cause the removal efficiency decrease, Fe–C-3 sorbent shows excellent Hg0 removal performance at the temperature window of 100–200 °C. Exceptional regeneration performance on Hg0 removal indicates that spent sorbent could be regenerated.

Gasification of torrefied oil palm biomass in a fixed-bed reactor: effects of gasifying agents on product characteristics

Abstract: Gasification represents an attractive pathway to generate fuel gas (i.e., syngas (H2 and CO) and hydrocarbons) from oil palm biomass in Malaysia. Torrefaction is introduced here to enhance the oil palm biomass properties prior to gasification. In this work, the effect of torrefaction on the gasification of three oil palm biomass, i.e., empty fruit bunches (EFB), mesocarp fibres (MF), and palm kernel shells (PKS) are evaluated. Two gasifying agents were used, i.e., CO2 and steam. The syngas lower heating values (LHVsyngas) for CO2 gasification and steam gasification were in the range of 0.35–1.67 MJ m−3 and 1.61–2.22 MJ m−3, respectively. Compared with EFB and MF, PKS is more effective for fuel gas production as indicated by the more dominant emission of light hydrocarbons (CH4, C2H4, and C2H6) in PKS case. Gasification efficiency was examined using carbon conversion efficiency (CCE) and cold gas efficiency (CGE). CCE ranges between 4% and 55.1% for CO2 gasification while CGE varies between 4.8% and 46.2% and 27.6% and 62.9% for CO2 gasification and steam gasification, respectively. Our results showed that higher concentration of gasifying agent promotes higher carbon conversion and that steam gasification provides higher thermal efficiency (CGE) compared to CO2 gasification.

Distributed power generation via gasification of biomass and municipal solid waste: A review

Abstract: The access to electricity has increased worldwide, growing from 60 million additional consumers per year in 2000–2012 to 100 million per year in 2012–2016. Despite this growth, approximately 675 million people will still lack access to electricity in 2030, indicating that electricity demand will continue to increase. Unfortunately, traditional large fossil power technologies based on coal, oil and natural gas lead to a major concern in tackling worldwide carbon dioxide emissions, and nuclear power remains unpopular due to public safety concerns. Distributed power generation utilizing CO2-neutral sources, such as gasification of biomass and municipal solid wastes (MSW), can play an important role in meeting the world energy demand in a sustainable way. This review focuses on the recent technology developments on seven power generation technologies (i.e. internal combustion engine, gas turbine, micro gas turbine, steam turbine, Stirling engine, organic rankine cycle generator, and fuel cell) suitable for distributed power applications with capability of independent operation using syngas derived from gasification of biomass and MSW. Technology selection guidelines is discussed based on criteria, including hardware modification required, size inflexibility, sensitivity to syngas contaminants, operational uncertainty, efficiency, lifetime, fast ramp up/down capability, controls and capital cost. Major challenges facing further development and commercialization of these power generation technologies are discussed.

1-hexene isomerization over bimetallic M-Mo-ZSM-5 (M: Fe, Co, Ni) zeolite catalysts: Effects of transition metals addition on the catalytic performance

Abstract: The aim of this study is to investigate the promotional effect of Fe–Mo, Co–Mo, and Ni–Mo bimetallic additives on the activity and stability of H-ZSM-5 zeolite for isomerization of 1-hexene. The catalysts were synthesized by wet-impregnation method and characterized by XRD, FTIR, BET, ICP-AES, HRSEM-EDS, HRTEM, H2-TPR, NH3-TPD, and pyridine-DRIFT analysis. The isomerization of 1-hexene was carried out in a micro-scale system under the conditions: T = 250 °C, P = 4.0 MPa, FR = 0.1 ml/min, WHSV = 1 h−1. The conversion of 1-hexene over the 4 g bed of catalyst was in the range of 95–97% after 74 h time-on-stream with cis-3-hexene and cis-2-hexene as the principal products. It was shown that the appearance of the new strong Lewis acid sites, decreases the ratio of Bronsted/Lewis acid sites. Increase of the weak Lewis acid sites in the 2.5 wt%Ni2.5 wt%Mo-ZSM-5 catalyst facilitated the isomerization of 1-hexene and showed higher C6 olefin selectivity (48.4 mol%), research octane number (99.7), and bromine number (148.3) than other studied catalysts.

Effect of pore structure on CO2 gasification reactivity of biomass chars under high-temperature pyrolysis

Abstract: The CO2 gasification reactivity of pine sawdust chars (PS char) obtained from the different high-temperature pyrolysis is studied based on non-isothermal thermogravimetric method. Results show that the order of gasification reactivity is PS char-1073 > PS char-1273 > PS char-1473. Under the effect of high-temperature pyrolysis, the surface structure of biomass char is gradually destroyed and the pore structure parameters of specific surface area, total pore volume and average pore diameter increase. By means of the N2 adsorption-desorption isotherms, it is seen that biomass char has more micro- and mesoporous at higher pyrolysis temperature. Besides, the PS char-1073 mostly has rich closed cylinder pores and parallel plate pores, and the PS char-1273 and PS char-1473 have plentiful open cylinder pores and parallel plate pores. An increase of pyrolysis temperature contributes to the development of porosity and improves diffusion path, which promotes the gasification reactivity. But, its effect on the decline of active site hinders the gasification reactivity. What's more, the kinetic model of distributed activation energy model (DAEM) is applied to calculate activation energy and pre-exponential factor with the integral and differential methods. The calculation results of integral method is more accurate and precise because the differential method is more sensitive than integral method for experimental noise. There is a compensation effect in the CO2 gasification process.

Enhanced dry reforming of methane over mesostructured fibrous Ni/MFI zeolite: Influence of preparation methods

Abstract: Dry reforming of methane is acknowledged to be an environmentally benign route for conversion of CO2 and CH4 into syngas (CO and H2). Herein, unique mesostructured fibrous MFI support was synthesized by microemulsion method, and Ni incorporation via double solvent, physical mixing and wetness impregnation methods. Results revealed wetness impregnation catalyst had the highest activity and stability. Activation energy of reactants showed a reliance on acidity, where moderate acidity impeded deactivation by CH4 cracking. Furthermore, degree of catalyst deactivation was negligible compared to what is attainable on conventional zeolite catalysts. Thus, fibrous morphology, microscopic dispersion and moderate acidity played a positive role in boosting reactants accessibility to active Ni sites which results in preservation of activity under the harsh conditions of DRM process.

Co-gasification of palm kernel shell and polystyrene plastic: Effect of different operating conditions

Abstract: Palm kernel shell (PKS) biomass has great potential for power generation via gasification as it contains high energy content. However, abundant it may be, the source of PKS is scattered throughout the country, thus the consistency of feedstock supply may be hard to maintain. Co-gasifying with another source, such as plastics, can be seen as one of a solution to mitigate the supply chain problem. Polystyrene (PS) plastics have potential as a plastic feedstock because of its high domestic and industrial usage. As PS is also hard to recycle, using PS as a co feedstock for gasification is a way for PS waste management. However, the study on the performance of air co-gasification of PKS and PS has not been done before. It is essential to investigate the performance before it is utilized in the real world. In this work, the performance co-gasification of PKS and PS with different operating conditions was investigated. The gasification experiment was done in an electrically heated downdraft gasifier with a diameter of 8 cm. The reaction temperature was varied from 700 to 900 °C, with the equivalence ratio varied from 0.07 to 0.27. The PS weight percentage of the total feedstock was varied from 0 to 30 wt%. It was found that the vol% of CO and H2 on the producer gas increased with temperature while reducing the vol% of CO2 and CH4. HHV and the amount of gas produced were also increasing with increasing temperature. Increasing ER reduced the HHV of the gas but increased the amount of gas produced. Adding more PS to the feedstock blend increased the percentage of the produced gas at 900 °C, however, at the lower temperature of 800 °C, the percentage of gas produced decreased with increasing PS wt%.

Integrated production of aromatic amines, aromatic hydrocarbon and N-heterocyclic bio-char from catalytic pyrolysis of biomass impregnated with ammonia sources over Zn/HZSM-5 catalyst

Abstract: By introducing exogenous nitrogen during biomass pyrolysis under nitrogen-rich conditions, high-value nitrogen-containing products, i.e., nitrogen-rich char and oil may be produced. Based on the cogeneration of high-value nitrogen products from biomass, biomass nitrogen-enriched pyrolysis was performed in a fixed bed with different sources and contents of ammonia. The yields, composition and characteristics of the products were investigated. Moreover, the formation mechanism of N-containing species was explored in depth for the pyrolysis and catalytic pyrolysis with HZSM-5 and Zn/HZSM-5 catalysts via elemental analysis, XPS, FTIR and BET. The results showed that ammonia impregnation could promote a Maillard reaction, reduce the content of small aldehydes and ketones, and produce a nitrogen-enriched bio-oil. The contents of N-containing species and phenolic substances in the pyrolysis oil of biomass impregnated with 10% urea reached 15.66% and 56.69%, respectively. Moreover, the nitrogen on the coke surface after pretreatment was mainly composed of C N, C N and N COO functional groups. The bio-char generated abundant pyridinic-N, pyrrolic-N, quaternary-N, and pyridone-N oxides. The presence of urea introduced many alkaline N-containing functional groups on the surface of the bio-char and promoted the transformation of nitrogen from amides and imides to heterocyclic nitrogen with higher thermal stability. Furthermore, Zn was an excellent catalyst for the Maillard reaction, and the Zn/HZSM-5 catalyst had a higher selectivity for aromatic hydrocarbons (96.98% for biomass and 86.48% for urea/biomass) and N-containing heterocyclic compounds, such as indoles (6.16% for biomass and 13.51% for urea/biomass). Additionally, the coke content decreased, and the catalyst deactivation decreased.

A comprehensive study on NOx emission and fuel nitrogen conversion of solid biomass in bubbling fluidized beds under staged combustion

Abstract: Despite the relatively low emissions in fluidized-bed combustion, NOx emission for biomass combustion is still a major concern because of increasingly stricter regulations. To realize NOx emission behavior in fluidized beds comprehensively, the effects of bed temperature, excess oxygen, staged combustion, and flue gas recirculation (FGR) are investigated in this study. In particular, three different types of operation are applied in staged combustion to find out the key parameter. The results indicate that NOx emissions increase with both bed temperature and excess oxygen, in which the influence of excess oxygen is greater than the other. Lowering bed temperature by water addition seems to be able to simultaneously reduce NOx emission and agglomerate formation, especially for fuels with high nitrogen content, but the pros and cons should be considered. The results in staged combustion infer that the residence time is much more critical than the stoichiometry in the bed. As for FGR, its impact appears to depend on the type of fuel. The correlation between NOx emission behavior and fuel characteristics is also scrutinized; it is concluded that the fuel-N conversion to NOx is essentially related to some features of fuels.