In-situ desulfurization using porous Ca-based materials for the oxy-CFB process: A computational study.

Within circulating fluidized bed (CFB) processes, gas and solid behaviors are mutually affected by operating conditions. Therefore, understanding the behaviors of gas and solid materials inside CFB processes is required for designing and operating those processes. In addition, in order to minimize the environmental impact, modeling to reduce pollutants such as SOx emitted from those processes is essential, and simulation reproduction is necessary for optimization, but little is known. In this study, the gas and solid behaviors in a pilot-scale circulating fluidized bed combustor were investigated by using computational particle fluid dynamics (CPFD) numerical simulation based on the multiphase particle-in-cell (MP-PIC) method under oxy-fuel combustion conditions. In particular, the combustion and in-situ desulfurization reactions simultaneously were considered in this CPFD model. Effect of fluidization number (ULS/Umf) was investigated through the comparison of particle circulation rates with regards to the loop seal flux plane and bed height in the standpipe. In addition, the effects of parameters (temperature, Ca/S molar ratio, and particle size distribution), sensitive indicators for the desulfurization efficiency of limestone, were confirmed. Based on the cycle of the thermodynamic equilibrium curve of limestone, it is suggested that direct and indirect desulfurization occur simultaneously under different operating conditions in CFB, creating an environment in which various reactions other than desulfurization can occur. Addition of the reaction equations (i.e., porosity, diffusion) to the established simple model minimizes uncertainty in the results. Furthermore, the model can be utilized to optimize in-situ desulfurization under oxy-CFB operating conditions.

Microalgae gasification over Ni loaded perovskites for enhanced biohydrogen generation.

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.

Production of biochar from crop residues and its application for biofuel production processes - An overview.

A sustainable carbon-neutral society is imperative for future generations, and biochars and biofuels are inevitable choice to achieve this goal. Crop residues (CR) such as sugarcane bagasse, corn stover, and rice husk are promising sustainable resources as a feedstock for biochars and biofuels. Extensive research has been conducted on CR-based biochar production not only in environmental remediation areas but also in application for biofuel production. Here, the distribution and resource potential of major crop residues are presented. The production of CR-biochar and its applications in biofuel production processes, focusing on the latest research are discussed. Finally, the challenges and areas of opportunity for future research in terms of CR supply, CR-biochar production, and CR-biochar utilization for biofuel production are proposed. Compared with other literature reviews, this study can serve as a guide for the establishment of sustainable, economical, commercial CR-based biorefineries.

Recent advances of thermochemical conversion processes for biorefinery.

Lignocellulosic biomass is one of the most promising renewable resources and can replace fossil fuels via various biorefinery processes. Through this study, we addressed and analyzed recent advances in the thermochemical conversion of various lignocellulosic biomasses. We summarized the operation conditions and results related to each thermochemical conversion processes such as pyrolysis (torrefaction), hydrothermal treatment, gasification and combustion. This review indicates that using thermochemical conversion processes in biorefineries is techno-economically feasible, easy, and effective compared with biological processes. The challenges experienced in thermochemical conversion processes are also presented in this study for better understanding the future of thermochemical conversion processes for biorefinery. With the aid of artificial intelligence and machine learning, we can reduce time-consumption and experimental work for bio-oil production and syngas production processes.

Hydrogen-rich gas production via steam gasification of food waste over basic oxides (MgO/CaO/SrO) promoted-Ni/Al2O3 catalysts.

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 advances of hybrid solar - Biomass thermo-chemical conversion systems.

Solar biomass hybridization is a promising energy technique for efficient utilization while mitigating the disadvantages associated with both biomass and solar energy source. In conventional concentrating solar power (CSP) systems, the contribution of solar energy is relatively low, merely supplementing the system with low/medium temperature air/steam. This paper aimed to emphasize the improvement of solar heat share, particularly in the topping cycle of the hybrid system. The solar aided processes, either directly generating superheated air/steam or direct gasification are thermodynamically favorable at very high temperatures, in excess of 800 °C. Unfortunately, this temperature is unattainable in conventional CSP systems using molten salt. Accordingly, the integration of solar power tower (SPT) with solid particle fluidized system in a beam down configuration has been proposed for the hybrid solar-biomass systems. Studies of such integration system presented challenges in terms of operating temperature, continuous supply/syngas production and scaling of reactor, particularly for circulating fluidized bed (CFB). The selection of solid particle and gas flow rate are among the governing parameters for high operating temperature and effective utilization of solar heat. The development of high temperature hybrid solar-biomass system is anticipated for higher solar-to-fuel conversion efficiencies, minimizing the direct combustion of biomass and reduce the emission of greenhouse gas (GHG) emissions.

Waste furniture gasification using rice husk based char catalysts for enhanced hydrogen generation.

Present study provides biohydrogen production methods from waste furniture via catalytic steam gasification with bio-char catalysts (raw char, KOH-activated char and steam-activated char). Total gas yield for the prepared chars was in the order of KOH-activated char > steam-activated char > raw char, whereas, H2 selectivity was in the sequence of raw char > steam-activated char > KOH-activated char. Though KOH-activated char showed the highest gas yield, highest H2 selectivity was obtained at the gasification experiment with raw char due to the large amount of Ca and K and its reasonable surface area (146.89 m2/g). Although the activation of raw biochar results in the increase of gas yield, it has the negative effect on H2 generation due to the removal of alkali and alkaline earth metals for the KOH activated char and steam-activated char. This study shows that raw bio-char could be a potential solution for eco-friendly hydrogen production.

Effect of eggshell- and homo-type Ni/Al2O3 catalysts on the pyrolysis of food waste under CO2 atmosphere.

This study highlights the potential of pyrolysis of food waste (FW) with Ni-based catalysts under CO2 atmosphere as an environmentally benign disposal technique. FW was pyrolyzed with homo-type Ni/Al2O3 (Ni-HO) or eggshell-type Ni/Al2O3 (Ni-EG) catalysts under flowing CO2 (50 mL/min) at temperatures from 500 to 700 °C for 1 h. A higher gas yield (42.05 wt%) and a lower condensable yield (36.28 wt%) were achieved for catalytic pyrolysis with Ni-EG than with Ni-HO (34.94 wt% and 40.06 wt%, respectively). In particular, the maximum volumetric content of H2 (21.48%) and CO (28.43%) and the lowest content of C2-C4 (19.22%) were obtained using the Ni-EG. The formation of cyclic species (e.g., benzene derivatives) in bio-oil was also effectively suppressed (24.87%) when the Ni-EG catalyst and CO2 medium were concurrently utilized for the FW pyrolysis. Accordingly, the simultaneous use of the Ni-EG catalyst and CO2 contributed to altering the carbon distribution of the pyrolytic products from condensable species to value-added gaseous products by facilitating ring-opening reactions and free radical mechanisms. This study should suggest that CO2-assisted catalytic pyrolysis over the Ni-EG catalyst would be an eco-friendly and sustainable strategy for disposal of FW which also provides a clean and high-quality source of energy.

Catalytic steam gasification of food waste using Ni-loaded rice husk derived biochar for hydrogen production.

The disposal of food waste (FW) is a major cause of environmental contamination. This study reports an environmentally friendly FW disposal method in the form of catalytic steam gasification using various types of Ni-loaded chars (untreated char, steam-treated char, and ZnCl2-treated char). The results were also compared with the gasification results from the Ni catalysts supported on commercial α-alumina (Ni/α-Al2O3). The Ni/steam-treated char showed the maximum hydrogen generation (0.471 mol/(g feedstock•g cat)) because of the high reducibility, high nickel dispersion, large amount of inherent K and Ca, and moderate surface area. The overall gas and H2 yield were observed in the following order: Ni/steam-treated char > Ni/ZnCl2 treated char > Ni/untreated char > Ni/α-Al2O3. Brunauer-Emmett-Teller analysis of various catalysts showed that the treated chars have a mesoporous structure, and the X-ray diffraction, X-ray fluorescence spectroscopy, scanning electron microscopy - energy dispersive spectroscopy showed that the presence of silica in the chars providing the stable support for the Ni loading and prevented coke formation. The chars obtained from biomass pretreatment could be a potential solution for preventing coke formation at high temperatures, thereby increasing the gas yield and enhancing hydrogen generation.

Biohydrogen production from catalytic conversion of food waste via steam and air gasification using eggshell- and homo-type Ni/Al2O3 catalysts.

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.

Catalytic conversion of cellulose over mesoporous Y zeolite.

Mesoporous Y zeolite (Meso-Y) was applied, for the first time, to the catalytic pyrolysis of cellulose which is a major constituent of lignocellulosic biomass, to produce high-quality bio-oil. A representative mesoporous catalyst Al-MCM-41 was also used to compare its catalytic activity with that of Meso-Y. Pyrolysis-gas chromatography/mass spectrometry was used for the experiments. Meso-Y, with higher acidity, led to larger yields of aromatics and furans with high value-added than Al-MCM-41, resulting in the production of bio-oil with higher quality. The effect of temperature on the catalytic pyrolysis was not significant within the range of 400-500 degrees C. When the Meso-Y to cellulose ratio was increased from 1/1 via 2/1 to 3/1, the deoxygenation efficiency increased, leading to increased yield of aromatics.

Catalytic pyrolysis of waste mandarin over nanoporous materials.

Catalytic pyrolysis of waste mandarin was performed using nanoporous catalysts. AI-MCM-41 and Meso-MFI, which had different acid characteristics, were used. In addition, the characteristics of Pt/Meso-MFI were compared with those of Meso-MFI. To analyze the characteristics of the catalyst samples, Brunauer-Emmett-Teller surface area, temperature programmed desorption of NH3, and N2 adsorption-desorption analyses were performed. In addition, pyrolysis gas chromatography/mass spectrometry was used to facilitate the direct analysis of the pyrolytic products. The products obtained from catalytic pyrolysis contained a greater amount of valuable components than did those obtained from non-catalytic pyrolysis, indicating that catalytic pyrolysis improved the quality of the bio-oil. Additionally, valuable products such as furan and aromatic compounds were produced in greater quantities when Meso-MFI was used. When Pt/Meso-MFI was used, the amounts of furan and aromatic compounds produced increased even further.

Catalytic pyrolysis of waste rice husk over mesoporous materials.

Catalytic fast pyrolysis of waste rice husk was carried out using pyrolysis-gas chromatography/mass spectrometry [Py-GC/MS]. Meso-MFI zeolite [Meso-MFI] was used as the catalyst. In addition, a 0.5-wt.% platinum [Pt] was ion-exchanged into Meso-MFI to examine the effect of Pt addition. Using a catalytic upgrading method, the activities of the catalysts were evaluated in terms of product composition and deoxygenation. The structure and acid site characteristics of the catalysts were analyzed by Brunauer-Emmett-Teller surface area measurement and NH3 temperature-programmed desorption analysis. Catalytic upgrading reduced the amount of oxygenates in the product vapor due to the cracking reaction of the catalysts. Levoglucosan, a polymeric oxygenate species, was completely decomposed without being detected. While the amount of heavy phenols was reduced by catalytic upgrading, the amount of light phenols was increased because of the catalytic cracking of heavy phenols into light phenols and aromatics. The amount of aromatics increased remarkably as a result of catalytic upgrading, which is attributed to the strong Brönsted acid sites and the shape selectivity of the Meso-MFI catalyst. The addition of Pt made the Meso-MFI catalyst even more active in deoxygenation and in the production of aromatics.

Catalytic pyrolysis of oilsand bitumen over nanoporous catalysts.

The catalytic cracking of oilsand bitumen was performed over nanoporous materials at atmospheric conditions. The yield of gas increased with application of nanoporous catalysts, with the catalytic conversion to gas highest for Meso-MFI. The cracking activity seemed to correlate with pore size rather than weak acidity or surface area.

Rapid estimation of triacylglycerol content of Chlorella sp. by thermogravimetric analysis.

A simple and reliable method based on thermogravimetric analysis has been developed for determining triacylglycerol content in Chlorella sp. KR-1. There are two decomposing steps during pyrolysis of the microalgal cells and the second step of weight loss may be attributed to degradation and volatilization of triacylglycerols. The second peak height in the temperature derivatives of weight loss increased with the triacylglycerol content of the microalgal cells and the peak was around 390 °C regardless of the triacylglycerol contents. Based on these findings, a linear equation for determining triacylglycerol content was derived. The proposed method gives satisfactory results, showing small variance and a good interpolation capability.

Co-pyrolysis characteristics of sawdust and coal blend in TGA and a fixed bed reactor.

Co-pyrolysis characteristics of sawdust and coal blend were determined in TGA and a fixed bed reactor. The yield and conversion of co-pyrolysis of sawdust and coal blend based on volatile matters are higher than those of the sum of sawdust and coal individually. Form TGA experiments, weight loss rate of sawdust and coal blend increases above 400 degrees C and additional weight loss was observed at 700 degrees C. In a fixed bed at isothermal condition, the synergy to produce more volatiles is appeared at 500-700 degrees C, and the maximum synergy exhibits with a sawdust blending ratio of 0.6 at 600 degrees C. The gas product yields remarkably increase at lower temperature range by reducing tar yield. The CO yield increases up to 26% at 400 degrees C and CH(4) yield increases up to 62% at 600 degrees C compared with the calculated value from the additive model.

Gasification of biodiesel by-product with air or oxygen to make syngas.

In the present study, gasification of biodiesel by-product, crude glycerin, was performed in an entrained flow gasifier. Gasification was conducted in a temperature range of 950-1500 degrees C and excess air ratio of 0.17-0.7 for air or oxygen as a gasification agent. From the results, syngas heating value, carbon conversion and cold gas efficiency of more than 2500 kcal/Nm(3), 92% and 65% were achieved, respectively. The H(2)/CO ratio of the product gas was varied from 1.25 to 0.7 with the excess air ratio and this gas composition was favorable for DME synthesis. The optimum excess air ratio for gasification of biodiesel by-product was evaluated to be an approximately 0.35-0.4. The present results indicate that crude glycerin can be utilized as a feedstock for gasification to make syngas.