Catalytic co-pyrolysis (CCP) of spent coffee ground (SCG) and cellulose over HZSM-5 and HY was characterized thermogravimetrically, and a catalytic pyrolysis of two samples was conducted using a tandem micro reactor that directly connected with gas chromatography-mass spectrometry. To access the more fundamental investigations on CCP, the effects of the zeolite pore structure, reaction temperature, in-situ/ex-situ reaction mode, catalyst to feedstock ratio, and the SCG and cellulose mixing ratio were experimentally evaluated. The temperature showing the highest thermal degradation rate of cellulose with SCG slightly delayed due to the interactions during the thermolysis of two samples. HZSM-5 in reference to HY produced more aromatic hydrocarbons from CCP. With respect to the reaction temperature, the formation of aromatic hydrocarbons increased with the pyrolytic temperature. Moreover, the in-situ/ex-situ reaction mode, catalyst/feedstock, and cellulose/SCG ratio were optimized to improve the aromatic hydrocarbon yield.
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.
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.
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.
Recent studies show that fast hydropyrolysis (i.e., pyrolysis under hydrogen atmosphere operating at a rapid heating rate) is a promising technology for the conversion of biomass into liquid fuels (e.g., bio-oil and C4+ hydrocarbons). This pyrolysis approach is reported to be more effective than conventional fast pyrolysis in producing aromatic hydrocarbons and also lowering the oxygen content of the bio-oil obtained compared to hydrodeoxygenation (a common bio-oil upgrading method). Based on current literature, various non-catalytic and catalytic fast hydropyrolysis processes are reviewed and discussed. Efforts to combine fast hydropyrolysis and hydrotreatment process are also highlighted. Points to be considered for future research into fast hydropyrolysis and pending challenges are also discussed.
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.
Steam and air gasification with 5 wt% Ni/Al2O3 eggshell (Ni-EG) and homo (Ni-H) catalysts were performed for the first time to produce biohydrogen from food waste. The steam gasification produced comparably higher gas yield than air gasification. In non-catalytic experiments, steam gasification generated a higher volume percent of H2, whereas more CO, CO2, CH4, and C2-C4 were produced in air gasification. Ni-EG demonstrated higher potential to obtain H2-rich gases with a low C2-C4 content compared to that obtained by Ni-H, particularly in steam gasification at 800 °C, which produced gaseous products with 59.48 vol% H2. The long-term activity of both catalysts in steam gasification was evaluated, and Ni-EG exhibited higher stability than Ni-H. The ideal distribution of Ni species on the outer region of γ-Al2O3 pellets in Ni-EG resulted in higher activity, stability, and selectivity than Ni-H in both steam and air gasification.
Improving the sustainability and cost-effectiveness of biochar production is crucial to meet increased global market demand. Here, we developed a single-step microwave steam activation (STMSA) as a simplified yet efficient method to produce microwave activated biochar (MAB) from waste palm shell (WPS). The STMSA recorded a higher heating rate (70 °C/min) and higher conversion (45 wt%) of WPS into highly microporous MAB (micropore surface area of 679.22 m2/g) in contrast with the conventional heating approach (≤ 12-17 wt%). The MAB was then applied as biosorbent for hazardous landfill leachate (LL) treatment and the adsorption performance was compared with commercial activated carbon under different pH, adsorbent quantity, adsorbate concentrations, and contact times. The MAB demonstrated high adsorption capacity, achieving maximum adsorption efficiency at 595 mg/g and 65 % removal of chemical oxygen demand (COD) with 0.4 g/L of adsorbent amount under optimal acidic conditions (pH ≈ 2-3) after 24 h of contact time. The Freundlich isotherm and pseudo second-order kinetic models were well-fitted to explain the equilibrium adsorption and kinetics. The results indicate the viability of STMSA as a fast and efficient approach to produce activated biochar as a biosorbent for the treatment of hazardous landfill leachate.
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.
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.
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.
This study presented a novel methodology to predict microalgae chlorophyll content from colour models using linear regression and artificial neural network. The analysis was performed using SPSS software. Type of extractant solvents and image indexes were used as the input data for the artificial neural network calculation. The findings revealed that the regression model was highly significant, with high R2 of 0.58 and RSME of 3.16, making it a useful tool for predicting the chlorophyll concentration. Simultaneously, artificial neural network model with R2 of 0.66 and low RMSE of 2.36 proved to be more accurate than regression model. The model which fitted to the experimental data indicated that acetone was a suitable extraction solvent. In comparison to the cyan-magenta-yellow-black model in image analysis, the red-greenblue model offered a better correlation. In short, the estimation of chlorophyll concentration using prediction models are rapid, more efficient, and less expensive.