Enhanced mono-aromatics production by the CH4-assisted pyrolysis of microalgae using Zn-based HZSM-5 catalysts.

This study presents the catalytic pyrolysis of microalgae, Chlorella vulgaris (C. vulgaris), using pure CH4 and H2-rich gas evolved from CH4 decomposition on three different HZSM-5 catalysts loaded with Zn, Ga, and Pt, aimed specifically at producing high-value mono-aromatics such as benzene, toluene, ethylbenzene, and xylene (BTEX). In comparison with that for the typical inert N2 environment, a pure CH4 environment increased the bio-oil yield from 32.4 wt% to 37.4 wt% probably due to hydrogen and methyl radical insertion in the bio-oil components. Furthermore, the addition of bimetals further increased bio-oil yield. For example, ZnPtHZ led to a bio-oil yield of 47.7 wt% in pure CH4. ZnGaHZ resulted in the maximum BTEX yield (6.68 wt%), which could be explained by CH4 activation, co-aromatization, and hydrodeoxygenation. The BTEX yield could be further increased to 7.62 wt% when pyrolysis was conducted in H2-rich gas evolved from CH4 decomposition over ZnGaHZ, as rates of aromatization and hydrodeoxygenation were relatively high under this condition. This study experimentally validated that the combination of ZnGaHZ and CH4 decomposition synergistically increases BTEX production using C. vulgaris.

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.

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.

Catalytic removal of 2-butanone with ozone over porous spent fluid catalytic cracking catalyst.

To remove harmful volatile organic compounds (VOCs) including 2-butanone (methyl ethyl ketone, MEK) emitted from various industrial plants is very important for the clean air. Also, it is worthwhile to recycle porous spent fluid catalytic cracking (SFCC) catalysts from various petroleum refineries in terms of reducing industrial waste and the reuse of discharged resources. Therefore, Mn and Mn-Cu added SFCC (Mn/SFCC and Mn-Cu/SFCC) catalysts were prepared to compare their catalytic efficiencies together with the SFCC catalyst in the ozonation of 2-butanone. Since the SFCC-based catalysts have a structure similar to that of zeolite Y (Y), the Mn-loaded zeolite Y catalyst (Mn/Y) was also prepared to compare its activity for the removal of 2-butanone and ozone to that of the SFCC-based ones at room temperature. Among the five catalysts of this study (Y, Mn/Y, SFCC, Mn/SFCC, and Mn-Cu/SFCC), the Mn-Cu/SFCC and Mn/SFCC catalysts showed the better catalytic decomposition activity than the others. The increased distributions of the Mn3+ species and the Ovacancy sites in Mn/SFCC and Mn-Cu/SFCC catalysts which could supply more available active sites for the 2-butanone and ozone removal would enhance the catalytic activity of them.

Mitigation of hazardous toluene via ozone-catalyzed oxidation using MnOx/Sawdust biochar catalyst.

This study investigated catalytic ozone oxidation using a sawdust char (SDW) catalyst to remove hazardous toluene emitted from the chemical industry. The catalyst properties were analyzed by proximate, ultimate, nitrogen adsorption-desorption isotherms, Fourier-transform infrared, and X-ray photoelectron spectroscopy analyses. In addition, hydrogen-temperature programmed reduction experiments were conducted to analyze the catalyst properties. The specific area and formation of micropores of SDC were improved by applying KOH treatment. MnOx/SDC-K3 exhibited a higher toluene removal efficiency of 89.7% after 100 min than MnOx supported on activated carbon (MnOx/AC) with a removal efficiency of 6.6%. The higher (Oads (adsorbed oxygen)+Ov(vacancy oxygen))/OL (lattice oxygen) and Mn3+/Mn4+ ratios of MnOx/SDC-K3 than those of MnOx/AC seemed to be important for the catalytic oxidation of toluene.

Valorization of hazardous COVID-19 mask waste while minimizing hazardous byproducts using catalytic gasification.

This study proposes a method to valorize hazardous waste such as used COVID-19 face mask via catalytic gasification over Ni-loaded ZSM-5 type zeolites. The 25% Ni was found as an optimal loading on ZSM-5 in terms of H2 production. Among different zeolites (ZSM-5(30), ZSM-5(80), ZSM-5(280), mesoporous (m)-ZSM-5(30), and HY(30)), 25% Ni/m-ZSM-5(30) led to the highest H2 selectivity (45.04 vol%), most likely because of the highest Ni dispersion on the m-ZSM-5(30) surface, high porosity, and acid site density of the m-ZSM-5(30). The content of N-containing species (e.g., caprolactum and nitriles) in the gasification product was also reduced, when steam was used as gasifying agent, which is the source of potentially hazardous air pollutants (e.g., NOx). The increase in the SiO2/Al2O3 ratio resulted in lower tar conversion and lower H2 generation. At comparable conditions, steam gasification of the mask led to ~15 vol% higher H2 selectivity than air gasification. Overall, the Ni-loaded zeolite catalyst can not only suppress the formation of hazardous substances but also enhance the production of hydrogen from the hazardous waste material such as COVID-19 mask waste.

Suppression of the hazardous substances in catalytically upgraded bio-heavy oil as a precautious measure for clean air pollution controls.

Bio-heavy oil (BHO) is a renewable fuel, but its efficient use is problematic because its combustion may emit hazardous air pollutants (e.g., polycyclic aromatic hydrocarbon (PAH) compounds, NOx, and SOx). Herein, catalytic fast pyrolysis over HZSM-5 zeolite was applied to upgrading BHO to drop-in fuel-range hydrocarbons with reduced contents of hazardous species such as PAH compounds and N- and S-containing species (NOx and SOx precursors). The effects of HZSM-5 desilication and linear low-density polyethylene (LLDPE) addition to the feedstock on hydrocarbon production were explored. The apparent activation energy for the thermal decomposition of BHO was up to 37.5% lowered by desilicated HZSM-5 (DeHZSM-5) compared with HZSM-5. Co-pyrolyzing LLDPE with BHO increased the content of drop-in fuel-range hydrocarbons and decreased the content of PAH compounds. The DeHZSM-5 was effective in producing drop-in fuel-range hydrocarbons from a mixture of BHO and LLDPE and suppressing the formation of N- and S-containing species and PAH compounds. The DeHZSM-5 enhanced the hydrocarbon production by up to 58.5% because of its enhanced porosity and high acid site density compared to its parent HZSM-5. This study experimentally validated that BHO can be upgraded to less hazardous fuel via catalytic fast co-pyrolysis with LLDPE over DeHZSM-5.

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.

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.

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.

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.

Kinetic Analysis for the Catalytic Pyrolysis of Wood Plastic Composite Over Al-MCM-41.

This study examined the catalytic effects of Al-MCM-41 on the pyrolysis of wood plastic composite via the thermogravimetric analysis (TGA) and model-free kinetic analysis. Al-MCM-41 containing nanopores, with a high BET surface area (633 m²/g) and acidity (SiO2/Al2O3:25), reduced the decomposition temperature of wood and plastic mixtures (PE and PP) in a wood-plastic composite. The average activation energy for the catalytic pyrolysis of wood plastic composite, which was calculated via a model-free kinetic analysis method (Ozawa) of TGA, was also lower at all conversions than those of non-catalytic pyrolysis. This suggests that the pores of Al-MCM-41 and its high cracking efficiency allow the effective diffusion of wood plastic composite components.

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.

Yellow Poplar Gasification Over Ni Silicate and Ni/Silica.

The activity of Ni silicates having different Ni/Si molar ratio (0.5 and 1) and Ni/silica were tested on biomass gasification. Ni silicate (Ni/Si= 0.5) and Ni/silica produced the higher gas yield than Ni silicate (Ni/Si = 1.0). The larger amount of H2 and CO were produced over Ni silicate (Ni/Si = 0.5) and Ni/silica compared those over Ni silicate (Ni/Si = 1.0). The catalysts were characterized using BET and XRD analysis. Ni silicate (Ni/Si = 0.5) showed promising activity for the production of syngas at higher temperature and can be employed in gasification.

In-Situ Catalytic Pyrolysis of Waste Lignin Over Desilicated Beta.

Desilicated Beta (DeBeta) was applied as the catalyst to the catalytic pyrolysis of waste lignin for the formation of aromatic hydrocarbon, and its performance was compared with that of the unmodified Beta. Large amounts of oxygen containing pyrolyzates were efficiently converted to stable aromatic hydrocarbons over both Beta and DeBeta catalysts. Compared to Beta, DeBeta exhibited the higher performance for the formation of aromatic hydrocarbons due to the enhanced diffusion efficiency through the mesopore.

H2 Production from Yellow Poplar Gasification Over Ni/Spent FCC.

Ni/spent FCC catalyst was applied as the catalyst on the catalytic pyrolysis and gasification of yellow poplar (YP). Larger amount of gas (CO, CO2, H2, C1~C4) was produced by applying Ni/spent FCC catalyst to the catalytic pyrolysis and gasification of YP. Ni/spent FCC catalyst also increased the selectivity of phenols and aromatic hydrocarbons in oil product during the pyrolysis and gasification of YP. Overall catalytic performance of Ni/spent FCC catalyst was similar level with that of Ni/γ-Al2O3, suggesting its potential use.

Catalytic Pyrolysis of Pinus densiflora Over Mesoporous Al2O3 Catalysts.

The thermal and catalytic pyrolysis of Pinus densiflora (P. densiflora) were performed to test the catalytic cracking efficiency of two mesoporous Al2O3 catalysts with different surface areas. Thermogravimetric analysis (TGA) of P. densiflora showed that the differential TG (DTG) peak heights obtained from catalytic pyrolysis were smaller than those of non-catalytic pyrolysis due to the conversion of the reaction intermediates to coke. Pyrolyzer-gas chromatography/mass spectrometry analysis/flame ionization detection (Py-GC/MS/FID) suggested that using the Al2O3 catalysts, the yields of phenols and levoglucosan decreased with a concomitant increase in the yields of aldehydes, alcohol, ketones, and furans. Between the two catalysts, Al2O3-B prepared by spray pyrolysis showed higher cracking efficiency than Al2O3-A prepared by hydrothermal method because of its larger surface area.

Catalytic Pyrolysis of Korean Pine (Pinus koraiensis) Nut Shell Over Mesoporous Al2O3.

The catalytic pyrolysis of waste Korean pine nut shell (KPNS) over mesoporous Al2O3 was investigated by thermogravimetric analysis (TGA) and pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS). TGA results showed that the thermal and catalytic pyrolysis of KPNS over mesoporous Al2O3 has the same decomposition temperature. On the other hand, the maximum decomposition for the catalytic pyrolysis of KPNS over commercial-Al2O3 shifted to a higher temperature. The Py-GC/MS results indicated that large amounts of oxygen-containing pyrolyzates, such as acids, furans, levoglucosan, and phenols, were produced by the non-catalytic pyrolysis of KPNS. These oxygen-containing pyrolyzates were upgraded efficiently into aromatic hydrocarbons by applying Al2O3 catalysts. Between the two Al2O3 catalysts, mesoporous Al2O3 showed better performance on the formation of aromatic hydrocarbons via the catalytic pyrolysis of KPNS than commercial Al2O3 because of its uniform larger pores.