Biochar production from invasive species biomass discarded as waste was studied in a fixed bed reactor pyrolysis system under different temperature conditions for value-added applications. Prior to pyrolysis, the biomass feedstock was characterized by proximate, ultimate, and heating value analyses, while the biomass decomposition behavior was examined by thermogravimetric analysis. The heating values of the feedstock biomass ranged from 18.65 to 20.65 MJ/kg, whereas the volatile matter, fixed carbon, and ash content were 61.54-72.04 wt %, 19.27-26.61 wt % and 1.51-1.86 wt %, respectively. The elemental composition of carbon, hydrogen, and oxygen in the samples was reported to be in the range of 47.41-48.47 wt %, 5.50-5.88 wt % and 46.10-45.18 wt %, respectively, while the nitrogen and sulphur content in the biomass samples were at very low concentrations, making it more useful for valorization from environmental aspects. The biochar yields were reported in the range of 45.36-58.35 wt %, 28.63-44.38 wt % and 22.68-29.42 wt % at a pyrolysis temperature of 400 °C, 500 °C, and 600 °C, respectively. The biochars were characterized from ultimate analysis, heating value, energy densification ratio, energy yield, pH, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy and energy dispersive X-ray spectrometry (SEM and EDX), to evaluate their potential for value-added applications. The carbon content, heating value, energy densification ratio, and the porosity of the biochars improved with the increase in pyrolysis temperature, while the energy yield, hydrogen, oxygen, and nitrogen content of the biochars decreased. This study revealed the potential of the valorization of underutilized discarded biomass of invasive species via a pyrolysis process to produce biochar for value-added applications.
In an effort to seek a new technical platform for disposal of drinking water treatment sludge (DWTS: alum sludge), pyrolysis of DWTS was mainly investigated in this study. To establish a more sustainable thermolytic platform for DWTS, this study particularly employed CO2 as reactive gas medium. Thus, this study laid great emphasis on elucidating the mechanistic roles of CO2 during the thermolysis of DWTS. A series of the TGA tests of DWTS in CO2 in reference to N2 revealed no occurrence of the heterogeneous reaction between CO2 and the sample surface of DWTS. As such, at the temperature regime before initiating the Boudouard reaction (i.e., ≥700 °C), the mass decay patterns of DWTS in N2 and CO2 were nearly identical. However, the gaseous effluents from lab-scale pyrolysis of DWTS in CO2 in reference to N2 were different. In sum, the homogeneous reactions between CO2 and volatile matters (VMs) evolved from the thermolysis of DWTS led to the enhanced generation of CO. Also, CO2 suppressed dehydrogenation of VMs. Such the genuine mechanistic roles of CO2 in the thermolysis of DWTS subsequently led to the compositional modifications of the chemical species in pyrolytic oil. Furthermore, the biochar composite was obtained as byproduct of pyrolysis of DWTS. Considering that the high content of Al2O3 and Fe-species in the biochar composite imparts a strong affinity for As(V), the practical use of the biochar composite as a sorptive material for arsenic (V) was evaluated at the fundamental levels. This work reported that adsorption of As(V) onto the biochar composite followed the pseudo-second order model and the Freundlich isotherm model.
An innovative approach was developed by incorporating high-pressure CO2 into the separate hydrolysis-fermentation of aspen leftover branches, aiming to enhance the bioethanol production efficiency. The high-pressure CO2 significantly increased the 72-h enzymatic hydrolysis yield of converting aspen into glucose from 53.8% to 82.9%. The hydrolysis process was performed with low enzyme loading (10 FPU g-1 glucan) with the aim of reducing the cost of fuel bioethanol production. The ethanol yield from fermentation of the hydrolyzed glucose using yeast (Saccharomyces cerevisiae) was 8.7 g L-1, showing increment of 10% compared with the glucose control. Techno-economic analysis indicated that the energy consumption of fuel bioethanol production from aspen branch chips was reduced by 35% and the production cost was cut 44% to 0.615 USD L-1, when 68 atm CO2 was introduced into the process. These results furtherly emphasized the low carbon footprint of this sustainable energy production approach.
Air gasification of the Wood-Plastic Composite (WPC) was performed over Ni-loaded HZSM-5 catalysts to generate H2-rich gas. Increasing SiO2/Al2O3 ratio (SAR) of HZSM-5 adversely affected catalytic activity, where the highest gas yield (51.38 wt%) and H2 selectivity (27.01 vol%) were acquired using 20 %Ni/HZSM-5(30) than those produced over 20 %Ni/HZSM-5(80) and 20 %Ni/HZSM-5(280). Reducing SAR was also favorably conducive to increasing the acyclic at the expense of cyclic compounds in oil products. These phenomena are attributed to enhanced acid strength and Ni dispersion of 20 %Ni/HZSM-5(30) catalyst. Moreover, catalytic activity in the terms of gas yield and H2 selectivity enhanced with growing Ni loading to 20 %. Also, the addition of promoters (Cu and Ca) to 20 %Ni/HZSM-5(30) boosted the catalytic efficiency for H2-rich gas generation. Raising temperature indicated a positive relevance with the gas yield and H2 selectivity. WPC valorization via gasification technology would be an outstanding outlook in the terms of a waste-to-energy platform.
Biofuels have become an attractive energy source because of the growing energy demand and environmental issues faced by fossil fuel consumption. Algal biomass, particularly microalgae, has excellent potential as feedstock to be converted to bio-oil, biochar, and combustible syngas via thermochemical conversion processes. Third-generation biofuels from microalgal feedstock are the promising option, followed by the first-generation and second-generation biofuels. This paper provides a review of the applications of thermochemical conversion techniques for biofuel production from algal biomass, comprising pyrolysis, gasification, liquefaction, and combustion processes. The progress in the thermochemical conversion of algal biomass is summarized, emphasizing the application of pyrolysis for its benefits over other processes. The review also encompasses the challenges and perspectives associated with the valorization of microalgae to biofuels ascertaining the potential opportunities and possibilities of extending the research into this area.
A total of 422 Mycobacterium tuberculosis isolates from eight countries were subjected to IS6110 and IS1081 DNA fingerprinting by means of restriction fragment analysis to characterize M. tuberculosis strains from each country. Chinese, Mongolian, Hong Kong, Filipino, and Korean isolates had comparatively more copies of IS6110 (proportion with eight or more copies; 95% +/- 5%), while Thai, Malaysian, and Vietnamese isolates had fewer copies (proportion with eight or more copies, 60% +/- 4%). We found a number of novel IS1081 types in this study. One IS1081 type was present in 56% of Filipino isolates, had a specific 6.6-kb PvuII fragment in its IS6110 DNA fingerprint, and was termed the "Filipino family." The IS1081 types of Thai isolates had interposing characteristics between the characteristics of northeastern Asian and southeastern Asian IS1081 types. A 1.3-kb single-copy IS6110 fragment was found only in Vietnamese M. tuberculosis isolates. Although M. tuberculosis isolates from each country had comparatively similar characteristics depending on the classification factor, each country's isolates showed characteristic DNA fingerprints and differed slightly from the isolates from the other countries in either the mode number of IS6110 copies or the distribution of IS1081 types.
The global economy is threatened by the depletion of fossil resources and fluctuations in fossil fuel prices, and thus it is necessary to exploit sustainable energy sources. Carbon-neutral fuels including bio-oil obtained from biomass pyrolysis can act as alternatives to fossil fuels. Co-pyrolysis of lignocellulosic biomass and plastic is efficient to upgrade the quality of bio-oil because plastic facilitates deoxygenation. However, catalysts are required to produce bio-oil that is suitable for potential use as transportation fuel. This review presents an overview of recent advances in catalytic co-pyrolysis of biomass and plastic from the perspective of chemistry, catalyst, and feedstock pretreatment. Additionally, this review introduces not only recent research results of acid catalysts for catalytic co-pyrolysis, but also recent approaches that utilize base catalysts. Future research directions are suggested for commercially feasible co-pyrolysis process.
Rapid growth of aquatic weeds in treatment pond poses undesirable challenge to shellfish aquaculture, requiring the farmers to dispose these weeds on a regular basis. This article reviews the potential and application of various aquatic weeds for generation of biofuels using recent thermochemical technologies (torrefaction, hydrothermal carbonization/liquefaction, pyrolysis, gasification). The influence of key operational parameters for optimising the aquatic weed conversion efficiency was discussed, including the advantages, drawbacks and techno-economic aspects of the thermochemical technologies, and their viability for large-scale application. Via extensive study in small and large scale operation, and the economic benefits derived, pyrolysis is identified as a promising thermochemical technology for aquatic weed conversion. The perspectives, challenges and future directions in thermochemical conversion of aquatic weeds to biofuels were also reviewed. This review provides useful information to promote circular economy by integrating shellfish aquaculture with thermochemical biorefinery of aquatic weeds rather than disposing them in landfills.
The fast pyrolysis of waste lignin derived from biobutanol production process was performed to determine the optimal pyrolysis conditions and pyrolysis product properties. Four types of pyrolysis reactors, e.g.: micro-scale pyrolyzer-gas chromatography/mass spectrometry, lab and bench scale fixed bed (FB) reactors, and bench scale rotary kiln (RK) reactor, were employed to compare the pyrolysis reaction conditions and product properties obtained from different reactors. The yields of char, oil, and gas obtained from lab scale and bench scale reactor were almost similar compared to FB reactor. RK reactor produced desirable bio-oil with much reduced yield of poly aromatic hydrocarbons (cancer precursor) due to its higher cracking reaction efficiency. In addition, char agglomeration and foaming of lignin pyrolysis were greatly restricted by using RK reactor compared to the FB reactor.
Oxidation of o-xylene was performed using alkaline battery-based catalyst doped with platinum to investigate the properties and activities. O-xylene was selected as the model of volatile organic compound (VOC) in this work. Physicochemical properties of the selected catalysts were characterized by FE/TEM (field emission transmission electron microscopy), BET (Brunauer-Emmett-Teller) analysis, XRD (X-ray powder diffraction), SEM/EDX (scanning electron microscopy/energy dispersive X-ray spectroscopy), and H2-TPR (hydrogen temperature programmed reduction). Major elements of the spent alkaline battery-based catalyst treated with sulfuric acid solution [SAB (400) catalyst] were manganese, zinc, iron, oxygen, carbon, chlorine, aluminum, sodium, silicon, and potassium. Increasing the doping amount of platinum on SAB (400) catalyst from 0.1 to 1 wt% increased particle size of platinum and lowered the temperature of TPR (TTP) for SAB (400) catalyst. Better redox properties were achieved with an increase in the o-xylene conversion according to the doping amount of platinum. When GHSV (gas hourly space velocity) was 40,000 h-1, o-xylene was oxidized completely over SAB (400) catalyst and 1.0 wt% Pt/SAB(400) catalyst at temperatures of 400 °C and 280 °C, respectively.
Biochar was produced by the pyrolysis of Kraft lignin at 600 °C followed by modification with CO2 at 700 and 800 °C and impregnation with FeOx. The physicochemical properties and arsenic (V) adsorption performance of biochar were evaluated. The characteristics of the lignin biochar before and after CO2 modification and FeOx impregnation were analyzed using the following methods: proximate and ultimate analysis, specific surface area (Brunauer-Emmett-Teller (BET) surface area), porosity, scanning electron microscopy and energy dispersive spectroscopy mapping, Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. The specific surface area and porosity of biochar were improved significantly after CO2 modification. However, impregnation of FeOx in CO2-modified biochar showed a 50%-60% decrease of BET surface area and porosity due to pore blocking of FeOx. The batch adsorption of arsenic (V) showed that FeOx-LC-800 (FeOx impregnation lignin char modified with CO2 at 800 °C) had the highest adsorption efficiency among the biochars tested because of its highest Fe-O intensity and large surface area. The Langmuir adsorption model was suitable for the curve fitting arsenic (V) adsorption. The theoretical equilibrium adsorption amount (qe) was calculated to be 6.8 mg/g using a pseudo-second-order kinetic model.
Microwave-steam activation (MSA), an innovative pyrolysis approach combining the use of microwave heating and steam activation, was investigated for its potential production of high grade activated carbon (AC) from waste palm shell (WPS) for methylene blue removal. MSA was performed via pyrolytic carbonization of WPS to produce biochar as the first step followed by steam activation of the biochar using microwave heating to form AC. Optimum yield and adsorption efficiency of methylene blue were obtained using response surface methodology involving several key process parameters. The resulting AC was characterized for its porous characteristics, surface morphology, proximate analysis and elemental compositions. MSA provided a high activation temperature above 500 °C with short process time of 15 min and rapid heating rate (≤150 °C/min). The results from optimization showed that one gram of AC produced from steam activation under 10 min of microwave heating at 550 °C can remove up to 38.5 mg of methylene blue. The AC showed a high and uniform surface porosity consisting high fixed carbon (73 wt%), micropore and BET surface area of 763.1 and 570.8 m2/g respectively, hence suggesting the great potential of MSA as a promising approach to produce high grade adsorbent for dye removal.
Used baby diaper consists of a combination of decomposable cellulose, non-biodegradable plastic materials (e.g. polyolefins) and super-absorbent polymer materials, thus making it difficult to be sorted and separated for recycling. Microwave pyrolysis was examined for its potential as an approach to transform used baby diapers into value-added products. Influence of the key operating parameters comprising process temperature and microwave power were investigated. The pyrolysis showed a rapid heating process (up to 43 °C/min of heating rate) and quick reaction time (20-40 min) in valorizing the used diapers to generate pyrolysis products comprising up to 43 wt% production of liquid oil, 29 wt% gases and 28 wt% char product. Microwave power and operating temperature were observed to have impacts on the heating rate, process time, production and characteristics of the liquid oil and solid char. The liquid oil contained alkanes, alkenes and esters that can potentially be used as chemical additives, cosmetic products and fuel. The solid char contained high carbon, low nitrogen and free of sulphur, thus showing potential for use as adsorbents and soil additives. These observations demonstrate that microwave pyrolysis has great prospect in transforming used baby diaper into liquid oil and char products that can be utilised in several applications.
Microwave co-pyrolysis was examined as an approach for simultaneous reduction and treatment of environmentally hazardous hospital plastic waste (HPW), lignocellulosic (palm kernel shell, PKS) and triglycerides (waste vegetable oil, WVO) biowaste as co-feedstock. The co-pyrolysis demonstrated faster heating rate (16-43 °C/min) compared to microwave pyrolysis of single feedstock (9-17 °C/min). Microwave co-pyrolysis of HPW/WVO performed at 1:1 ratio produced a higher yield (80.5 wt%) of hydrocarbon liquid fuel compared to HPW/PKS (78.2 wt%). The liquid oil possessed a low nitrogen content (< 4 wt%) and free of sulfur that could reduce the release of hazardous pollutants during its use as fuel in combustion. In particular, the liquid oil obtained from co-pyrolysis of HPW/WVO has low oxygenated compounds (< 16%) leading to reduction in generation of potentially hazardous sludge or problematic acidic tar during oil storage. Insignificant amount of benzene derivatives (< 1%) was also found in the liquid oil, indicating the desirable feature of this pyrolysis approach to suppress the formation of toxic polycyclic aromatic hydrocarbons (PAHs). Microwave co-pyrolysis of HPW/WVO improved the yield and properties of liquid oil for potential use as a cleaner fuel, whereas the liquid oil from co-pyrolysis of HPW/PKS is applicable in the synthesis of phenolic resin.
Microalgae are drawing attentions among researchers for their biorefinery use or value-added products. The high production rate of biomasses produced are attractive for conversion into volatile biochar. Torrefaction, pyrolysis and hydrothermal carbonization are the recommended thermochemical conversion techniques that could produce microalgal-based biochar with desirable physiochemical properties such as high surface area and pore volume, abundant surface functional groups, as well as functionality such as high adsorption capacity. The characterizations of the biochar significantly influence the mechanisms in adsorption of pollutants from wastewaters. Specific adsorption of the organic and inorganic pollutants from the effluent are reviewed to examine the adsorption capacity and efficiency of biochar derived from different microalgae species. Last but not least, future remarks over the challenges and improvements are discussed accordingly. Overall, this review would discuss the synthesis, characterization and application of the microalgal-based biochar in wastewater.
Steam gasification of microalgae upon perovskite oxide-supported nickel (Ni) catalysts was carried out for H2-rich gas production. Ni-perovskite oxide catalysts with partial substitution of B in perovskite structures (Ni/CaZrO3, Ni/Ca(Zr0.8Ti0.2)O3, and Ni/Ca(Zr0.6Ti0.4)O3) were synthesized and compared with those of the Ni/Al2O3 catalyst. The perovskite oxide supports improved Ni dispersion by reducing the particle size and strengthening the Ni-support interaction. Higher gas yields and H2 selectivity were obtained using Ni-perovskite oxide catalysts rather than Ni/Al2O3. In particular, Ni/Ca(Zr0.8Ti0.2)O3 showed the highest activity and selectivity for H2 production because of the synergetic effect of metallic Ni and elements present in the perovskite structures caused by high catalytic activity coupled with enhanced oxygen mobility. Moreover, increasing the temperature promoted the yield of gas and H2 content. Overall, considering the outstanding advantages of perovskite oxides as supports for Ni catalysts is a promising prospect for H2 production via gasification technology.
Dearomatization through photocatalytic oxidation is a swiftly rising phenolic compounds removal technology that works at trifling operations requirements with a special emphasis on the generation of nontoxic products. The study aims to develop a LaVO4/MCM-48 nanocomposite that was prepared via a hydrothermally approach assisting the employment of an MCM-48 matrix, which was then utilized for phenol degradation processes. Various techniques including UV-Vis DRS, FTIR, PL, Raman, TEM, and BET analyses are employed to characterize the developed photocatalyst. The developed photocatalyst presented remarkable characteristics, especially increased light photon utilization, and reduced recombination rate leading to enhanced visible-light-driven photodegradation performance owing to the improved specific surface area, specific porosities, and <2 eV narrow energy bandgap. The LaVO4/MCM-48 nanocomposite was experienced on aqueous phenol solution having 20 mg/L concentration under visible-light exposure, demonstrating exceptional performance in photodegradation up to 99.28%, comparatively higher than pure LaVO4. The conducted kinetic measurements revealed good accordance with pseudo first-order. A possible reaction mechanism for photocatalytic degradation was also predicted. The as-synthesized LaVO4/MCM-48 nanocomposite presented excellent stability and recyclability.
Food waste, a renewable resource, was converted to H2-rich gas via a catalytic steam gasification process. The effects of basic oxides (MgO, CaO, and SrO) with 10 wt% Ni/Al2O3 on the gasification properties of food waste were investigated using a U-shaped gasifier. All catalysts prepared by the precipitation method were analyzed by X-ray diffraction, H2-temperature-programmed reduction, NH3-temperature-programmed desorption, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The Ni/Al2O3 catalyst was reduced incompletely, and low nickel concentrations were detected on the surface of the alumina. The basic oxides minimized the number of acid sites and suppressed the formation of nickel-aluminate (NiAlxOy) phase in catalyst. In addition, the basic oxides shifted nickel-aluminate reduction reaction to lower temperatures. It resulted in enhancing nickel concentration on the catalyst surface and increasing gas yield and hydrogen selectivity. The low gas yield of the Ni/Al2O3 catalyst was attributed to the low nickel concentration on the surface. The maximum gas yield (66.0 wt%) and hydrogen selectivity (63.8 vol%) of the 10 wt% SrO- 10 wt% Ni/Al2O3 catalyst correlated with the highly dispersed nickel on the surface and low acidity. Furthermore, coke deposition during steam gasification varied with the surface acidity of the catalysts and less coke was formed on 10 wt% SrO- 10 wt% Ni/Al2O3 due to efficient tar cracking. This study showed that the steam gasification efficiency of the Ni/Al2O3 catalyst could be improved significantly by the addition of SrO.
Household food waste (FW) was converted into biohydrogen-rich gas via steam gasification over Ni and bimetallic Ni (Cu-Ni and Co-Ni) catalysts supported on mesoporous SBA-15. The effect of catalyst method on steam gasification efficiency of each catalyst was investigated using incipient wetness impregnation, deposition precipitation, and ethylenediaminetetraacetic acid metal complex impregnation methods. H2-TPR confirmed the synergistic interaction of the dopants (Co and Cu) and Ni. Furthermore, XRD and HR-TEM revealed that the size of the Ni particle varied depending on the method of catalyst synthesis, confirming the formation of solid solutions in Co- or Cu-doped Ni/SBA-15 catalysts due to dopant insertion into the Ni. Notably, the exceptional activity of the Cu-Ni/SBA-15-EMC catalyst in FW steam gasification was attributed to the fine distribution of the concise Ni nanoparticles (9 nm), which resulted in the highest hydrogen selectivity (62 vol%), gas yield (73.6 wt%). Likewise, Cu-Ni solid solution decreased coke to 0.08 wt%.
In this study, nickel-loaded perovskite oxides catalysts were synthesized via the impregnation of 10%Ni on XTiO3 (X = Ce, Sr, La, Ba, Ca, and Fe) supports and employed in the catalytic steam gasification of swine manure to produce H2-rich syngas for the first time. The synthesized catalysts were characterized using BET, H2-TPR, XRD, HR-TEM, and EDX analysis. Briefly, using perovskite supports resulted in the production of ultrafine catalyst nanoparticles with a uniform dispersion of Ni particles. According to the catalytic activity test, the gas yield showed the increment as 10% Ni/LaTiO3 < 10% Ni/FeTiO3 < 10% Ni/CeTiO3 < 10% Ni/BaTiO3 < 10% Ni/SrTiO3 < 10% Ni/CaTiO3. Meanwhile, zero coke formation was achieved due to the oxygen mobility of prepared catalysts. Also, the increase in the H2 production for the applied catalysts was in the sequence as 10% Ni/CeTiO3 < 10% Ni/FeTiO3 < 10% Ni/LaTiO3 < 10% Ni/BaTiO3 < 10% Ni/SrTiO3 < 10% Ni/CaTiO3. The maximum H2 selectivity (∼48 vol%) obtained by10% Ni/CaTiO3 was probably due to the synergistic effect of Ni and Ti on enhancing the water-gas shift reaction, and Ca on creating the maximum oxygen mobility compared to other alkaline earth metals doped at the A place of perovskite. Overall, this study provides a suitable solution for enhanced H2 production through steam gasification of swine manure along with suggesting the appropriate supports to prevent Ni deactivation by lowering coke formation at the same time.