Search Results (70)

In wet flue gas desulfurization and denitrification processes, nitrite accumulation inhibits denitrification efficiency and induces secondary pollution due to its acidic disproportionation. This study developed a Mn-modified ZSM-5 zeolite catalyst, achieving efficient resource conversion of nitrite in nitrogen-containing wastewater through an O₃ + Mn/ZSM-5 catalytic system. Mn/ZSM-5 catalysts with varying SiO₂/Al₂O₃ ratios (prepared by wet impregnation) were characterized by BET, XRD, and XPS. Experimental results demonstrated that Mn/ZSM-5 (SiO₂/Al₂O₃ = 400) exhibited a larger specific surface area, enhanced adsorption capacity, abundant surface Mn³⁺/Mn⁴⁺ species, hydroxyl oxygen species, and chemisorbed oxygen, leading to superior oxidation capability and catalytic activity. Under the optimized conditions of reaction temperature = 40 °C, initial pH = 4, Mn/ZSM-5 dosage = 1 g/L, and O₃ concentration = 100 ppm, the $\mathrm{N}{\mathrm{O}}_2^{-}$ oxidation efficiency reached 94.33%. Repeated tests confirmed that the Mn/ZSM-5 catalyst exhibited excellent stability and wide operational adaptability. The synergistic effect between Mn species and the zeolite support significantly improved ozone utilization efficiency. The O₃ + Mn/ZSM-5 system required less ozone while maintaining high oxidation efficiency, demonstrating better cost-effectiveness. Mechanism studies revealed that the conversion pathway of $\mathrm{N}{\mathrm{O}}_2^{-}$ followed a dual-path catalytic mechanism combining direct ozonation and free radical chain reactions. Practical spray tests confirmed that coupling the Mn/ZSM-5 system with ozone oxidation flue gas denitrification achieved over 95% removal of liquid-phase $\mathrm{N}{\mathrm{O}}_2^{-}$ byproducts without compromising the synergistic removal efficiency of NO_x/SO₂. This study provided an efficient catalytic solution for industrial wastewater treatment and the resource utilization of flue gas denitrification byproducts. Full article

Platinum was supported on ZSM5 at loadings from 0.1 to 1 wt% and tested for the Selective Catalytic Reduction of NO with H₂ under excess O₂ in a fixed bed reactor to address the issue of NO_x emission abatement from H₂-fueled internal combustion engines avoiding the additional devices for urea storage and injection. To reduce the undesired NO oxidation to NO₂, which is activated by platinum at T > 200 °C, the 0.1%Pt/ZSM5 catalyst was further promoted with sodium. 5 wt% loading of Na strongly inhibited the NO oxidation while giving only a limited impact on the H₂-SCR activity. Unpromoted and Na-promoted catalysts were characterized by XRD, SEM/EDX, N₂ physisorption, and NH₃-TPD to investigate the morphological, structural, and acid properties; H₂ pulse chemisorption and DRIFTS of CO chemisorption were used to investigate the nature of Pt active species. Steady-state and transient operando DRIFTS experiments under NO+H₂+O₂ flow were employed to identify the adsorbed NO_x species interacting with H₂, and reaction intermediates as a function of the reaction conditions. The formation of ammonium intermediates via the reduction of surface nitrate species, playing a key role in H₂-SCR catalyzed by 0.1Pt/ZSM5, was preserved at low Na load whilst NO₂ formation was largely inhibited. Full article

This study focuses on the production and characterization of activated carbons derived from the carbonaceous residue obtained through the catalytic pyrolysis of waste tires. A catalytic pyrolysis process was conducted at 450 °C and 575 °C, employing two zeolitic catalysts, the commercial ZSM-5 and a synthesized zeolite (PZ2), developed from natural pozzolan, which played a key role in the pyrolysis performance and the quality of the resulting carbons. After pyrolysis, the solid residues were chemically activated using KOH to improve their porous structure and surface characteristics. Comprehensive characterization was carried out, including textural properties (BET surface area and porosity) and morphological (SEM) analysis of the activated carbons, as well as crystallinity evaluation (XRD) of the zeolitic catalysts. The BET surface areas of activated carbons PZ2-T1-AK and PZ2-T2-AK reached 608.65 m²/g and 624.37 m²/g, respectively, values that surpass those reported for similar materials under comparable activation conditions. The developed porous structure suggests strong potential for applications in adsorption processes, including pollutant removal. These findings demonstrate the effectiveness of zeolite-catalyzed pyrolysis, particularly using PZ2, as a sustainable strategy for transforming tire waste into high-performance adsorbent materials. This approach supports circular economy principles through innovative waste valorization and offers a promising solution to an environmental challenge. Full article

The formation of unstable solid electrolyte interphases (SEIs) on the surface of lithium metal anodes poses a significant barrier to the commercialization of lithium metal batteries (LMBs). Rational modulation of solvation structures within the electrolytes emerged as one of the most effective strategies to enhance interfacial stability in LMBs; however, this approach often compromises the structural stability of the bulk electrolyte. Herein, we present an innovative method that improves interface stability without adversely affecting the bulk electrolyte’s structural stability. By employing ZSM molecular sieves as efficient ion channels on the lithium metal anode surface—termed ZSM electrolytes—a more aggregated solvation structure is induced at the lithium metal interface, resulting in an anion-rich interphase. This anion-enriched environment promotes the formation of an SEI derived from anions, thereby enhancing the stability of the lithium metal interface. Consequently, Li||Cu cells utilizing the ZSM electrolyte achieve an average coulombic efficiency (CE) of 98.76% over 700 h. Moreover, LiFePO₄||Li batteries exhibit stable cycling performance exceeding 900 cycles at a current density of 1 C. This design strategy offers robust support for effective interfacial regulation in lithium metal batteries. Full article

The hydro-upgrading reaction behavior of model compound 1-hexene and FCC middle gasoline was investigated using a fixed-bed hydrogenation microreactor with a prepared La-Ni-Zn/H-ZSM-5 catalyst. The catalyst was prepared by wetness impregnation method, using hydrothermal treated H-ZSM-5 zeolite blended with alumina as the support, and La, Ni, Zn as the active metals. The reaction tests were carried out at 300–380 °C, 1.0 MPa, 1.5–3.0 h⁻¹ (LSHV), and 300:1 v/v (H₂/oil). Analyzing the changes in hydrocarbon components before and after hydro-upgrading elucidated the mechanistic pathways of olefin hydroisomerization and hydroaromatization. Based on these findings, a seven-lump kinetic model was established for the FCC middle gasoline hydro-upgrading process. Given the diversity and complexity of reaction products, they were grouped into seven lumps: normal paraffins, isoparaffins, linear olefins, branched olefins, cycloolefins, naphthenes, and aromatics. Kinetic parameters were estimated using the Levenberg–Marquardt algorithm and validated against experimental data. The results showed that the conversion of naphthenes to aromatics exhibited the highest activation energy and pre-exponential factor, resulting in the largest reaction rate increase within the 320–380 °C range. The model accurately predicted the product yields of FCC gasoline hydro-upgrading, with a relative error of less than 5%. These findings provide valuable guidance for the optimization, design, and operation of FCC gasoline hydro-upgrading units, as well as for catalyst development, with the aim of improving process efficiency and fuel quality. Full article

Methane and carbon dioxide, the primary contributors to global warming, are now at critical levels, threatening the extinction of numerous organisms on our planet. In this regard, dry reforming of methane reactions have gained considerable attention because of the conversion capacity of CH₄ and CO₂ into synthetic/energy-important syngas (H₂ and CO). Herein, a molecular sieve (CBV3024E; SiO₂/Al₂O₃ = 30) with ZSM-8-type pore architect, is utilized as the support for the active site of Ni and Ce promoters. Catalysts are characterized by surface area and porosity, X-ray diffraction study, Raman and infrared spectroscopy, thermogravimetry analysis, and temperature-programmed reduction/desorption techniques. A total of 2 wt.% ceria is added over 5Ni/CBV3024E to induce the optimum connectivity of aluminum in the silicate framework. NiO residing in these porous cages are mostly under “prominent interaction with support” which is reduced easily into metallic Ni as the active sites for DRM reactions. The active sites over 5Ni2Ce/CBV3024E remain stable during the DRM reaction and achieve ~58% H₂ yield after 300 min TOS at 42,000 mL/(g_cat.h) GHSV and ~70% H₂ yield after 20 h at 26,000 mL/(g_cat.h) GHSV. The high activity after a longer time stream justifies using CBV3024E molecular sieves as the support and ceria as the promoter for Ni-based catalyst towards the DRM reaction. Full article

The aim of this work was to investigate the hydrocracking of algae oil derived from Spirulina Platensis species catalyzed with bi-component nickel-zirconia catalysts supported onto different carriers (BEA, ZSM-5 and Al₂O₃) in an autoclave at 320 °C for 2 h with a hydrogen pressure of 75 bar. All catalysts were prepared using the wet co-impregnation method and were characterized by H₂-TPR, XRD, NH₃-TPD, BET and SEM-EDS. Before reactions, catalysts were calcined at 600 °C for 4 h in a muffle furnace, then reduced with 5%H₂-95%Ar reducing mixture at 500 °C, 600 °C or 700 °C for 2 h. The obtained products were analyzed and identified by HPLC and GC-MS techniques. In addition to the investigation of the support effect, the influence of the reduction temperature of catalytic systems on the catalytic activity and selectivity of the products was also examined. The activity results show that Ni-Zr systems supported on zeolites exhibited high conversion of algal oil. A gradual decrease in conversion was observed when increasing the reduction temperature of the catalyst (from 500 °C to 600 °C and 700 °C) for BEA zeolite catalysts. The reaction products contain hydrocarbons from C₇ to C₃₃ (for zeolite-supported catalysts) and C₃₆ (for systems on Al₂O₃). The identified hydrocarbons mainly belong to the gasoil fraction (C₁₄–C₂₂). In the research, the best catalyst for the algal oil hydrocracking reaction was found to be the 5%Ni-5%Zr/BEA system reduced at 600 °C, which exhibited the second highest algal oil conversion (94.0%). The differences in catalytic activity that occur are due to the differences in the specific surface area among the supports and to differences in the acidity of the catalyst surface depending on the reduction temperature. Full article

Glycerol transesterification with diethyl carbonate (DEC) using catalysts with different porosities as support for CaO was performed, seeking the evaluation of how textural properties influence glycerol conversion and product selectivity. A total of 20% CaO was supported on ZSM-5, K-10, MCM-41, SiO₂, and γ-Al₂O₃. Catalysts showed a well-dispersed active phase of CaO in all the supports and no changes in the support crystalline structure were noticed. Reactions were performed in dimethyl sulfoxide (DMSO), 10 wt.% of catalyst in relation to glycerol, at 130 °C, and 1:3 glycerol/DEC molar ratio. According to our results, the higher the pore volume and pore size, the higher the glycerol conversion. On the other hand, concerning selectivity, higher glycerol carbonate selectivities were reached when strong basic sites were present. A total of 86% glycerol conversion and 91% glycerol carbonate selectivity were found using 60% CaO supported on γ-Al₂O₃ after 5 h of reaction. Full article

In this study, we assessed the quantity, strength, and acidity of zeolite composites comprising Silicalite-1 grown on ZSM-5 crystals using a combination of infrared (IR) and solid-state nuclear magnetic resonance (NMR) spectroscopy. The composites were created through the direct growth of Silicalite-1 crystals on ZSM-5 (P_ZSM-5), either with or without the organic structure-directing agent (OSDA) introduced into the ZSM-5 channels (samples: H_ZSM-5_Sil1 and TPA_ZSM-5_Sil1). The results revealed that Silicalite-1 grew differently when the ZSM-5 core was in the H⁺ form (empty pores) compared to when the OSDA was still present in the sample. This distinction was evident in the textural properties, with a decrease in the micropore surface area and an increase in the external surface area in the H_ZSM-5_Sil1 compared to the parent sample. The TPA_ZSM-5_Sil1 composite exhibited characteristics similar to the parent zeolite. These findings were further supported by ²⁹Si NMR, which revealed a comparable local order for the parent (P_ZSM-5) and TPA_ZSM-5_Sil1 samples, along with a broadening of the Q⁴ peak for the H_ZSM-5_Sil1 composite. Additionally, the acid sites were preserved in the TPA_ZSM-5_Sil1 composite, while in the H⁺-form core, the concentration of Brønsted acid sites significantly decreased. This reduction in isolated Brønsted acid sites was further corroborated by ¹H NMR. Full article

This work determines the deactivation mechanisms of Cu/ZSM-5 catalysts used for the conversion of 2,3-butanediol to butene as part of an alcohol-to-jet route. The deactivation of the catalyst, reflected by a drop in the rate of the limiting hydrogenation step by over 90% in 24 h at a weight hourly space velocity of 5.92 h⁻¹, proceeds via both the agglomeration of copper particles and the obstruction of copper surfaces due to carbonaceous deposits, although the former has less impact on the decrease in the hydrogenation rate. To reduce the detrimental effect of carbonaceous deposits on catalytic activity, ZMS-5 is modified through desilication of the HZSM-5 support with NaOH and CsOH solutions to generate a hierarchical structure with mesopores. The catalyst with the CsOH-treated support generates the highest overall yield of desired olefin products and experiences the slowest deactivation. This is a result of the lower Brønsted acidity and larger mesopores found in the CsOH-treated catalyst, leading to the slower formation of carbonaceous deposits and the faster diffusion of their precursors out of the pores. Full article

Commercial NH₄-Beta and Na-ZSM-5 zeolites were fluorinated with different amounts of NH₄F and using different procedures (room temperature, conventional refluxing, microwave refluxing). Samples were characterized by XRD, N₂ physisorption, FTIR, ¹H NMR, SEM-EDS, and TGA of adsorbed cyclohexylamine. An increase in the concentration of NH₄F led to fluorinated zeolites with higher surface areas and slightly lower amounts of Brønsted acid sites due to some dealumination. Fluorination by conventional or microwave refluxing at shorter times did not dealuminate ZSM-5, resulting in the formation of higher particle sizes. Ni/fluorinated beta catalysts were more active than Ni/fluorinated ZSM-5 catalysts for the hydrodeoxygenation of guaiacol at 180 °C and 15 bar of H₂ for 1 h due to their higher amount of acid sites. The appropriate proportion of metallic and Brønsted acid centers allowed for the selective obtention of cyclohexane (58%) for the Ni supported on beta fluorinated with NH₄F 0.1 M catalyst. The combination of this fluorinated beta to a Ni/ordered mesoporous carbon catalyst significantly boosted its selectivity to cyclohexane from 0 to 65%. Fluorinated ZSM-5 samples, although having stronger Brønsted acid sites, as observed by ¹H NMR, they had lower amounts, leading to higher selectivity to cyclohexanol when used as catalytic supports. Full article

It is important to develop effective strategies for enhancing the removal capacity of aromatic volatile organic compounds (VOCs) by modifying conventional porous adsorbents. In this study, a novel HZSM-5 zeolite-supported sulfonic acid (ZSM−OSO₃H) was prepared through ClSO₃H modification in dichloromethane and employed for the elimination of gaseous o-xylene. The ClSO₃H modification enables the bonding of −OSO₃H groups onto the HZSM-5 support, achieving a loading of 8.25 mmol·g⁻¹ and leading to a degradation in both crystallinity and textural structure. Within an active temperature range of 110–145 °C, ZSM−OSO₃H can efficiently remove o-xylene through a novel reactive adsorption mechanism, exhibiting a removal rate exceeding 98% and reaching a maximum breakthrough adsorption capacity of 264.7 mg. The adsorbed o-xylene derivative is identified as 3,4-dimethylbenzenesulfonic acid. ZSM−OSO₃H demonstrates superior adsorption performance for o-xylene along with excellent recyclability. These findings suggest that ClSO₃H sulfonation offers a promising approach for modifying various types of zeolites to enhance both the elimination and resource conversion of aromatic VOCs. Full article

Membrane-based pervaporation (PV) for organic solvent dehydration is of great significance in the chemical and petrochemical industries. In this work, high-aluminum ZSM-5 zeolite membranes were synthesized by a fluoride-assisted secondary growth on α-alumina tubular supports using mordenite framework inverted (MFI) nanoseeds (~110 nm) and a template-free synthesis solution with a low Si/Al ratio of 10. Characterization by XRD, EDX, and SEM revealed that the prepared membrane was a pure-phase ZSM-5 zeolite membrane with a Si/Al ratio of 3.8 and a thickness of 2.8 µm. Subsequently, two categories of PV performance parameters (i.e., flux versus separation factor and permeance versus selectivity) were used to systematically examine the effects of operating conditions on the PV dehydration performance of different organic solvents (methanol, ethanol, n-propanol, and isopropanol), and their PV mechanisms were explored. Employing permeance and selectivity effectively disentangles the influence of operating conditions on PV performance, thereby elucidating the inherent contribution of membranes to separation performance. The results show that the mass transfer during PV dehydration of organic solvents was mainly dominated by the adsorption–diffusion mechanism. Furthermore, the diffusion of highly polar water and methanol molecules within membrane pores had a strong mutual slowing-down effect, resulting in significantly lower permeance than other binary systems. However, the mass transfer process for water/low-polar organic solvent (ethanol, n-propanol, and isopropanol) mixtures was mainly controlled by competitive adsorption caused by affinity differences. In addition, the high-aluminum ZSM-5 zeolite membrane exhibited superior PV dehydration performance for water/isopropanol mixtures. Full article

Barium and iridium supported on Zeolite Socony Mobil-5 (ZSM-5) are efficient catalysts for the selective catalytic reduction of nitric oxide by carbon monoxide (CO-SCR), with enhanced cyclic stability. The introduction of Ba hindered the oxidation of metallic Ir active species and enabled Ir to maintain an active metallic state, thereby preventing a decrease in catalytic activity in the CO-SCR reaction. Moreover, the Ba modification increased the NO adsorption of the catalyst, further improving the catalytic activity. Owing to the better anti-oxidation ability of Ir⁰ in IrBa0.2/ZSM-5(27) than in Ir/ZSM-5(27), IrBa0.2/ZSM-5(27) showed better stability than Ir/ZSM-5(27). Considering that all samples in the present study were tested to simulate actual flue gases (such as sintering flue gas and coke oven flue gas), NH₃ was introduced into the reaction system to serve as an extra reductant for NO_x. The NO_x conversion to N₂ (77.1%) was substantially improved using the NH₃-CO-SCR system. The proposed catalysts and reaction systems are promising alternatives for treating flue gas, which contains considerable amounts of NO_x and CO in oxygen-enriched environments. Full article

The gas-to-liquid (GTL) process is a catalytic technology for achieving carbon neutrality during fuel production. Fischer–Tropsch synthesis (FTS), a core step in this process, converts synthesis gas (CO + H₂) to high-value hydrocarbon products. This study synthesized a chabazite-shaped zeolite and a Co/γ-alumina catalyst by using conventional hydrothermal and wet impregnation methods, respectively. Hybrid FTS catalysts were then prepared by mixing the Co/γ-alumina catalyst with supports, including the synthesized and commercial zeolites alone and mixed at various ratios. The effects of these zeolites on the FTS conversion and selectivity were investigated. Additionally, the physicochemical properties of the supports and prepared catalysts were analyzed. The bifunctional hybrid catalyst performance was evaluated in a fixed-bed reactor, and the FTS products were analyzed using online and offline gas chromatography. The hybrid catalysts produced lighter hydrocarbons than the Co/γ-alumina catalyst alone. Meanwhile, heavy hydrocarbons produced over the Co/γ-alumina catalyst were hydrocracked at the acid sites of the silicoaluminophosphate zeolite (SAPO-34) to yield lighter, fuel-range hydrocarbons. Cobalt-based hybrid FTS catalysts were also investigated to determine the optimum support ratio for high carbon conversion and C₅₊ selectivity. The hybrid catalyst supported on SAPO-34:ZSM-5 (2:8) exhibited the highest CO conversion and favorable C₅₊ selectivity. Full article