Production of biodiesel via esterification of coffee waste-derived bio-oil using sulfonated catalysts.

Catalytic esterification of acid-rich coffee waste-derived bio-oil was performed using sulfonated metal oxide catalysts (Al2O3, MgO, ZrO2, and TiO2) and ethanol to produce fatty acid alkyl esters. The potential of the sulfonated catalysts for esterification decreased in the following order: Ti-SO4 > Zr-SO4 > Al-SO4 > Mg-SO4. Particularly, Ti-SO4 and Zr-SO4 resulted in 91.2 % (peak area %) and 85.2 % esters, respectively. This is attributed to the contributions of well-dispersed Brønsted acid sites created by -SO3H functional groups, additional Lewis acid sites formed by Ti and Zr oxides, and their appropriate pore size. Compared with HCl and H3PO4, the use of H2SO4 for TiO2 treatment significantly enhanced ester formation. When using Ti-SO4, increasing the catalyst-to-feedstock ratio (1/2 âˆ¼ 1/10) significantly increased the esters' selectivity (38.7 %∼94.7 %). Ethanol utilization caused a superior selectivity for esters than methanol, while the increasing temperature favored ester production. This study proposes an eco-friendly and practical method for biodiesel generation.

Recent advances in liquid fuel production from plastic waste via pyrolysis: Emphasis on polyolefins and polystyrene.

The management of plastic waste (PW) has become an indispensable worldwide issue because of the enhanced accumulation and environmental impacts of these waste materials. Thermo-catalytic pyrolysis has been proposed as an emerging technology for the valorization of PW into value-added liquid fuels. This review provides a comprehensive investigation of the latest advances in thermo-catalytic pyrolysis of PW for liquid fuel generation, by emphasizing polyethylene, polypropylene, and polystyrene. To this end, the current strategies of PW management are summarized. The various parameters affecting the thermal pyrolysis of PW (e.g., temperature, residence time, heating rate, pyrolysis medium, and plastic type) are discussed, highlighting their significant influence on feed reactivity, product yield, and carbon number distribution of the pyrolysis process. Optimizing these parameters in the pyrolysis process can ensure highly efficient energy recovery from PW. In comparison with non-catalytic PW pyrolysis, catalytic pyrolysis of PW is considered by discussing mechanisms, reaction pathways, and the performance of various catalysts. It is established that the introduction of either acid or base catalysts shifts PW pyrolysis from the conventional free radical mechanism towards the carbonium ion mechanism, altering its kinetics and pathways. This review also provides an overview of PW pyrolysis practicality for scaling up by describing techno-economic challenges and opportunities, environmental considerations, and presenting future outlooks in this field. Overall, via investigation of the recent research findings, this paper offers valuable insights into the potential of thermo-catalytic pyrolysis as an emerging strategy for PW management and the production of liquid fuels, while also highlighting avenues for further exploration and development.

Fractional condensation of bio-oil vapors from pyrolysis of various sawdust wastes in a bench-scale bubbling fluidized bed reactor.

The use of lignocellulosic waste as an energy source for substituting fossil fuels has attracted lots of attention, and pyrolysis has been established as an effective technology for this purpose. However, the utilization of bio-oil derived from non-catalytic pyrolysis faces certain constraints, making it impractical for direct application in advanced sectors. This study has focused on overcoming these challenges by employing fractional condensation of pyrolytic vapors at distinct temperatures. The potential of five types of sawdust for producing high-quality bio-oil through pyrolysis conducted with a bench-scale bubbling fluidized bed reactor was investigated for the first time. The highest yield of bio-oil (61.94 wt%) was produced using sample 3 (damaged timber). Remarkably, phenolic compounds were majorly gathered in the 1st and 2nd condensers at temperatures of 200 °C and 150 °C, respectively, attributing to their higher boiling points. Whereas, carboxylic acid, ketones, and furans were mainly collected in the 3rd (-5 °C) and 4th (-20 °C) condensers, having high water content in the range of 35.33%-65.09%. The separation of acidic nature compounds such as acetic acid in the 3rd and 4th was evidenced by its low pH in the range of 4-5, while the pH of liquid collected in the 1st and 2nd condensers exhibited higher pH (6-7). The well-separated bio-oil derived from biomass pyrolysis facilitates its wide usage in various applications, proposing a unique approach toward carbon neutrality. In particular, achieving efficient separation of phenolic compounds in bio-oil is important, as these compounds can undergo further upgrading to generate hydrocarbons and diesel fuel.

Production of light olefins and monocyclic aromatic hydrocarbons from the pyrolysis of waste plastic straws over high-silica zeolite-based catalysts.

Owing to the ever-increasing generation of plastic waste, the need to develop environmentally friendly disposal methods has increased. This study explored the potential of waste plastic straw to generate valuable light olefins and monocyclic aromatic hydrocarbons (MAHs) via catalytic pyrolysis using high-silica zeolite-based catalysts. HZSM-5 (SiO2/Al2O3:200) exhibited superior performance, yielding more light olefins (49.8 wt%) and a higher MAH content than Hbeta (300). This was attributed to the increased acidity and proper shape selectivity. HZSM-5 displayed better coking resistance (0.7 wt%) than Hbeta (4.4 wt%) by impeding secondary reactions, limiting coke precursor formation. The use of HZSM-5 (80) resulted in higher MAHs and lower light olefins than HZSM-5 (200) because of its higher acidity. Incorporation of Co into HZSM-5 (200) marginally lowered light olefin yield (to 44.0 wt%) while notably enhancing MAH production and boosting propene selectivity within the olefin composition. These observations are attributed to the well-balanced coexistence of Lewis and Brønsted acid sites, which stimulated the carbonium ion mechanism and induced H-transfer, cyclization, Diels-alder, and dehydrogenation reactions. The catalytic pyrolysis of plastic straw over high-silica and metal-loaded HZSM-5 catalysts has been suggested as an efficient and sustainable method for transforming plastic waste materials into valuable light olefins and MAHs.

Catalytic pyrolysis of harmful plastic waste to alleviate environmental impacts.

Wax is a detrimental byproduct of plastic waste pyrolysis causing challenges upon its release into the environment owing to persistence and potential toxicity. In this study, the valorization of wax materials through conversion into BTEX (i.e., benzene, toluene, ethylbenzene, and xylene) was achieved via catalytic pyrolysis using zeolite-based catalysts. The potential of two types of waxes, spent wax (SW), derived from the pyrolysis of plastic waste, and commercial paraffin wax (PW), for BTEX generation, was investigated. Using HZSM-5, higher yields of oil (54.9 wt%) and BTEX (18.2 wt%) were produced from the pyrolysis of SW compared to PW (32.3 and 14.1 wt%, respectively). This is due to the improved accessibility of lighter hydrocarbons in SW to Brønsted and Lewis acid sites in HZSM-5 micropores, promoting cracking, isomerization, cyclization, Diels-Alder, and dehydrogenation reactions. Further, the use of HZSM-5 resulted in significantly larger yields of oil and BTEX from SW pyrolysis compared to Hbeta and HY. This phenomenon is ascribed to the well-balanced distribution of Brønsted and Lewis acid sites and the identical geometric structure of HZSM-5 micropores and BTEX molecules. The addition of Ga to HZSM-5 further led to 2.24% and 28.30% enhancements in oil and BTEX yields, respectively, by adjusting the acidity of the catalyst through the introduction of new Lewis acid sites. The regeneration of the Ga/HZSM-5 catalyst by removing deposited coke on the spent catalyst under air partially recovered catalytic activity. This study not only offers an efficient transformation of undesirable wax into valuable fuels but also provides an environmentally promising solution, mitigating pollution, contributing to carbon capture, and promoting a healthier and more sustainable environment. It also suggests future research directions, including catalyst optimization and deactivation management, feedstock variability exploration, and techno-economic analyses for sustainable wax conversion into BTEX via catalytic pyrolysis.

Hydrogen production from hazardous petroleum sludge gasification over nickel-loaded porous ZSM-5 and Al2O3 catalysts under air condition.

In this study, the potential of petroleum sludge (PS) for hydrogen production via the gasification process was evaluated. For this purpose, nickel (Ni)-loaded ZSM-5 and γ-Al2O3 (Ni-ZS and Ni-Al) catalysts were prepared and employed for PS gasification in air condition. The effects of different supports, Ni loading content, and reaction temperatures on the production of hydrogen-rich syngas along with the stability and reusability of the best catalyst were investigated. Applying 5%Ni-ZS obtained more gas yield (68.09 wt%) and hydrogen selectivity (25.04 vol%) compared to those obtained by 5%Ni-Al mostly owing to weak metal-support interactions which led to the dominance of well-dispersed metallic Ni. At various Ni loading percentages, 10%Ni-ZS showed the highest catalytic efficiency, which increased both gas yield (70.92 wt%) and hydrogen selectivity (30.74 vol%). However, excessive Ni content (especially 20%) significantly reduced the gas yield and hydrogen selectivity because of limited accessibility of support's active sites, poor dispersion of Ni, and inappropriate acidity. Increasing the temperature promoted the gas yield and produced hydrogen, where the highest gas yield (73.18 wt%) and hydrogen selectivity (33.15 vol%) were obtained at 850 °C due to the endothermic nature of gasification reactions. The 10%Ni-ZS catalyst showed proper stability during three consecutive experiments at 850 °C. The spent catalyst was successfully regenerated without a significant reduction in activity or selectivity.

Thermocatalytic conversion of wood-plastic composite over HZSM-5 catalysts.

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.

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.

H2 generation from steam gasification of swine manure over nickel-loaded perovskite oxides catalysts.

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.

Valorization of biomass through gasification for green hydrogen generation: A comprehensive review.

Green and sustainable hydrogen from biomass gasification processes is one of the promising ways to alternate fossil fuels-based hydrogen production. First off, an overview of green hydrogen generation from biomass gasification processes is presented and the corresponding possible gasification reactions and the effect of respective experimental criteria are explained in detail. In addition, a comprehensive explanation of the catalytic effect on tar reduction and hydrogen generation via catalytic gasification is presented regarding the functional mechanisms of various types of catalysts. Furthermore, the commercialization aspects, the associated technical challenges and barriers, and the prospects of a biomass gasification process for green hydrogen generation are discussed. Finally, this comprehensive review provides the related advancements, challenges, and great insight of biomass gasification for the green hydrogen generation to realize a sustainable hydrogen society via biomass valorization.

Production of valuable chemicals through the catalytic pyrolysis of harmful oil sludge over metal-loaded HZSM-5 catalysts.

This research studied the catalytic pyrolysis of oil sludge (OS) over metal-loaded HZSM-5 catalysts, an eco-friendly and cost-effective technology to produce value-added aromatics such as benzene, toluene, ethylbenzene, and xylene (BTEXs). In particular, it evaluated the respective effects of the experimental parameters: the type and amount of the metal loaded, the reaction temperature, and the OS/catalyst ratio, on the BTEXs yield sequentially to achieve optimum conditions. This evaluation showed that the highest yields of the BTEXs (6.61 wt%) and other aromatics were achieved when Ni was incorporated into the HZSM-5 (Ni/HZSM-5) followed by the corresponding yields of Ga/HZSM-5 and Fe/HZSM-5, due to a better distribution of Ni on the support surface and an enhanced acidity strength of this catalyst. Further, increase in Ni loading (up to 10 wt% Ni/HZSM-5) increased the BTEXs yield to 13.48 wt%. However, the excessive Ni loading (15 wt% Ni/HZSM-5) resulted in a reduced BTEXs yield due to the blockage of the zeolite channels. Next, an increase in the reaction temperature from 500 °C to 600 °C increased the yield of the BTEXs and other aromatics. However, a further increase in the reaction temperature to 650 °C decreased slightly their yield because of the stimulating secondary reactions at high temperatures. The increase of catalyst amount (OS/catalyst of 1/3) also maximized the BTEXs yield (30.50 wt%).

Biochar application strategies for polycyclic aromatic hydrocarbons removal from soils.

Polycyclic aromatic hydrocarbons (PAHs) are known as a hazardous group of pollutants in the soil which causes many challenges to the environment. In this study, the potential of biochar (BC), as a carbonaceous material, is evaluated for the immobilization of PAHs in soils. For this purpose, various bonding mechanisms of BC and PAHs, and the strength of bonds are firstly described. Also, the effect of impressive criteria including BC physicochemical properties (such as surface area, porosity, particle size, polarity, aromaticity, functional group, etc., which are mostly the function of pyrolysis temperature), number of rings in PAHs, incubation time, and soil properties, on the extent and rate of PAHs immobilization by BC are explained. Then, the utilization of BC in collaboration with biological tools which simplifies further dissipation of PAHs in the soil is described considering detailed interactions among BC, microbes, and plants in the soil matrix. The co-effect of BC and biological remediation has been authenticated by previous studies. Moreover, recent technologies and challenges related to the application of BC in soil remediation are explained. The implementation of a combined BC-biological remediation method would provide excellent prospects for PAHs-contaminated soils.

Bioremediation strategies with biochar for polychlorinated biphenyls (PCBs)-contaminated soils: A review.

Polychlorinated biphenyls (PCBs) are hazardous organic contaminants threatening human health and environmental safety due to their toxicity and carcinogenicity. Biochar (BC) is an eco-friendly carbonaceous material that can extensively be utilized for the remediation of PCBs-contaminated soils. In the last decade, many studies reported that BC is beneficial for soil quality enhancement and agricultural productivity based on its physicochemical characteristics. In this review, the potential of BC application in PCBs-contaminated soils is elaborated as biological strategies (e.g., bioremediation and phytoremediation) and specific mechanisms are also comprehensively demonstrated. Further, the synergy effects of BC application on PCBs-contaminated soils are discussed, in view of eco-friendly, beneficial, and productive aspects.

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.

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.