Cracking Reactions Research Articles

Promotion of manganese on Fe-based catalyst for the production of carbon nanotubes (CNTs) from plastics

Manganese (Mn) is an effective promoter of Fe-based catalysts to increase the production of carbon nanotubes (CNTs) from waste plastics but suffers from the lack of insights into how Mn affects the catalytic performance of CNTs production. Herein, we systematically investigate the promotion mechanism of Mn in Fe-based catalysts by varying the adding order of Mn and Fe during one or two-step impregnation methods. The results show that α-(Fe1-xMnx)2O3 is formed and uniformly distributed in Fe crystals when Mn and Fe are simultaneously added by the one-step impregnation method ((Mn + Fe)/MgO), resulting in the highest gas (66.3 mmol/gplastic), and CNTs (235 mg/gplastic) yields. While α-(Fe1-xMnx)2O3 in FeMn/MgO (Fe is added first and followed by Mn by two-step impregnation method) exhibited a poor distribution resulting in reduced gas and CNTs yields compared to (Mn + Fe)/MgO. For MnFe/MgO prepared by the two-step impregnation method and Mn is added first, the formed α-(Fe1-xMnx)2O3 is entirely not inserted into Fe crystals, and the corresponding catalyst exhibits lower gas and CNTs yields. The best catalytic performance of (Mn + Fe)/MgO is owing to the well-dispersed α-(Fe1-xMnx)2O3, which increases the carbon solubility capacity of the Fe crystals and regulates the equilibrium of carbon dissolution and precipitation, promoting the thermal cracking and carbon formation reactions, thereby improving the catalytic performance of CNTs and gas production.

Trace Selenium Doping for Improving the Reaction Kinetics of ZnS Cathode for Aqueous Zn-S Batteries.

Aqueous Zinc-sulfur (Zn-S) batteries are promising for the field of energy storage due to their low cost, high theoretical capacity, and safety. However, the large volume expansion and the inherently poor conductivity of sulfur would result in electrode cracking and sluggish reaction kinetics, limiting the practical application of Zn-S batteries. Herein, commercial zinc sulfide (ZnS) is employed instead of S as cathode and proposed a doping modification strategy to solve the above problems. The designed ZnS0.93Se0.07 cathode shows good cycle stability and much-improved reaction kinetics, which is due to the smaller bandgap of ZnS0.93Se0.07 (1.40eV) compared to ZnS (1.86eV). As a result, the obtained ZnS0.93Se0.07 cathode exhibits a high specific capacity of 552 mAh g-1 (1672.6 mAh g-1 based on S) at 0.1 A g-1 and 330 mAh g-1 (1000 mAh g-1 based on S) at 2 A g-1. Moreover, the ZnS0.93Se0.07 cathode can provide a high areal capacity of 3.8 mAh cm-2 at a high mass loading of 10mg cm-2 and limited electrolyte (4µL mg-1). This work provides a simple and effective cathode modification strategy, which is conducive to promoting the practical application of Zn-S batteries.

Catalytic Cracking of Oily Sludge using Nickel Metal Catalyst Embedded in Silica Derived from Adsorbent in a Gas Process Plant

Abstract. One of the Oily Sludge (OS) recycling methods is through catalytic cracking. This process involves the reaction breaking down large molecules into smaller ones with the help of a catalyst. Nickel (Ni) metal is often used as a catalyst because it can increase fuel liquid yield while reducing the coke formation. To enhance its performance, Ni metal can be embedded in a carrier material like Silica to form the Ni-Silica catalyst. In this research, OS sourced from a Gas Process Plant is treated with catalytic cracking using Ni-Silica, where the Silica used is derived from an Adsorbent activated with NaOH. Optimization of the cracking conditions is carried out using Response Surface Methodology (RSM) with a Box-Behnken design. The optimized cracking reaction conditions include temperature (713 K, 723 K, and 733 K), time (50 min, 60 min, and 70 min), and catalyst-to-OS ratio of 1:5, 1:6, and 1:7. Statistical analysis indicates that the relationship between the reaction condition variables and the Oil Liquid Product (OLP) falls into the moderate category, as shown by the coefficient of determination (R²) of 0.5. The calculated F-value for the deviation from the mathematical model is smaller than the F-Table value (9.2) at both 5% and 1% significance levels, with a value of 0.6. This indicates that the mathematical model generated can be accepted as the mathematical model within the range of reaction conditions in this study. Calculus analysis reveals that the optimum reaction conditions are a temperature of 717.34 K, a time of 58.58 min, and a catalyst-to-OS ratio of 1:6, 15. Canonical analysis indicates that for OLP, λ1= [-12.38], λ2= [-2.27], and λ3= [4.50], where lambda values indicate that the most sensitive response surface parameter for OLP is temperature, followed by the catalyst-to-sample ratio, and the least sensitive is reaction time. Keywords: Catalytic Cracking, Ni Metal, OS, RSM, Silica

Study on H3PO4-activated carbon catalytic co-pyrolysis of bamboo and LDPE to poly-generation syngas and aromatics at low temperature

Biomass-derived carbon activated by H3PO4 was adopted to catalytic co-pyrolysis of bamboo and low-density polyethylene (LDPE) to produce syngas and aromatics on a fixed bed reactor. Effects of LDPE ratio in the feedstock, catalytic co-pyrolysis temperature and ratio of catalyst to feedstock on the yields and compositions of the products were investigated. The increase of LDPE ratio in liquid first improved and then reduced the relative content of aromatics, while it showed a positive effect on the yield and the H2/CO ratio of gas. 500℃ was an optimum temperature, under which the relative content of aromatics in liquid kept higher, meanwhile, avoided the undesirable polymerization reactions of monocyclic aromatics. At the same time, the content of H2 in gas reached a maximum (59.3%), which was in favor of poly-generation. H3PO4-activated carbon catalyst (H3PO4-ACC) with abundant functional groups on surface catalyzed cracking, hydrodeoxygenation, cyclization and aromatization reactions so as to facilitate the generation of aromatics. Non-condensable gas was dry reformed on P-ACC at the expense of CO2, CH4 and CO to generate char and H2. When the reaction condition was at a LDPE ratio of 50%, a catalyst/feedstock ratio of 2:1 and at 500℃, the relative content of aromatics in liqiud was 81.65% and the proportion of syngas component in gas was 79.73%. The volume ratio of H2/CO approached to 3:1 in gas under this condition. H3PO4-ACC catalytic co-pyrolysis of bamboo and LDPE could obtain high quality gas and liquid products at a relative low reaction temperature, which provided a new research idea on high-value application of biomass and waste plastics.

Pyrolytic Conversion of Waste High-Density Polyethylene to Wax: Temperature Optimization and Characterization of Wax

The formation of wax from waste high-density polyethylene by thermal decomposition through pyrolysis is examined in this work. To get wax from waste high-density polyethylene, the thermal cracking reaction is run in a semi-batch pyrolysis reactor at 550 °C, 600 °C, and 650 °C. The yield percentage, melting point, specific gravity, and penetration degree of wax varied depending on the temperature. At 600 °C, waste high-density polyethylene yielded the highest wax output (87.25%) with a 0.7768 specific gravity, a 59 °C melting point, and an 81.8 mm penetration degree. The fourier transform infrared spectroscopy (FTIR) analysis concluded the presence of aliphatic hydrocarbon compounds (alkane, alkene, alcohol, and cycloalkane), which is also confirmed by gas chromatography-mass spectrometry (GC-MS) analysis. The innovation in this study lies in the systematic exploration and optimization of temperature conditions for wax production from waste high-density polyethylene (HDPE) bottles.

Kinetic analysis of monomolecular cracking of normal Alkanes (C4[sbnd]C6) over Brønsted Acid site of Zeolitic type catalyst with energetic evaluation of transition states using Quantum-Chemical modeling

The work aims to determine the kinetic parameters of reactions for production of light olefins via catalytic cracking reactions of C4–C6 n-alkanes based on the energy characteristics of the transition state using quantum chemical calculations. Cracking reactions of C4–C6 n-alkanes proceed via protolytic mechanism on the Brønsted acid sites of zeolite-containing catalysts. For kinetic studies in this work, the thermochemical parameters of the intermediate stages, including hydrocarbon adsorption and transition state were determined, then the activation energies and rate constants were determined over the temperature range of catalytic cracking process from 773 to 903 K (500–630 °C).The results showed that DFT method in combination with B3LYP and ωB97X-D functionals, and 3–21 G basis demonstrated quite high accuracy in determining thermochemical parameters, including enthalpy, entropy and Gibbs free energy at both energetic levels of adsorption and transition state. Then, modeling continued by calculations of activation energies and rate constants of reactions. Obtained kinetic parameters made it possible to determine the reactivity of hydrocarbons with different chain length. It was obtained that the rate constants of butane cracking reactions with the formation of ethylene are 54–90 times higher than the formation of propylene. The rate constants of pentane cracking reactions with the formation of butylene are on average 5 times higher than the formation of propylene. The rate constants for hexane cracking reactions with the formation of butylene are 2.9–3.7 times higher compared to the formation of propylene.

Catalytic pyrolysis of pine needles using metal functionalized spent adsorbent derived catalysts: Kinetics, thermodynamics and prediction modelling using artificial neural network (ANN) approach

The current study was indented towards the evaluation of synergism of spent aluminum hydroxide nanoparticle (AHNP) adsorbent derived catalysts in the degradation of pine (Pinus roxburghii) needles through kinetics and thermodynamics analysis. Distinct kinetic (such as activation energy and pre-exponential factors) and thermodynamic (such as entropy, enthalpy, and Gibbs free energy) parameters were estimated through isoconversional (OFA and KAS) models. The study also aimed to envisage the reaction mechanism for all the distinct processes via Criado z master plots. Results illustrated the significant impact of all the different AHNP-derived catalysts in easing up the biomass degradation process. The KAS method evaluated the average activation energy for non-catalytic degradation as 130.01 kJ/mol, while the values changed to 120.95, 121.69, 125.99, 148.47 and 127.37 kJ/mol for Ni/AO, Fe/AO, Cu/AO, Zn/AO and Mo/AO catalyzed degradation, respectively. Amongst all, nickel (Ni/AO) and iron-doped (Fe/AO) catalysts brought the highest reduction in activation energy owing to the provision of strong acidic sites, high specific surface area, and better metal dispersion; subsequently leading to the increased rate of molecular scission and cracking reactions. Values of pre-exponential factor and thermodynamic parameter also displayed the positive impact of catalysts in terms of lowering down the molecular collisions, enthalpy, and disorderness of the system. Furthermore, artificial neural network (ANN) was also employed for the prediction of the biomass degradation where high regression (∼0.99) as well as low mean squared error (<10−5) illustrated the accurate prediction of complex biomass degradation by the ANN technique. Thus, the waste AHNP-derived catalysts have significant potential to be employed for the catalytic pyrolysis of pine needles together with aiding the cost-competitiveness, environmental sustainability, and renewability of the process.

Hydrothermally Ce modified HZSM-5 zeolite enhancing its strong acidity and Brønsted/Lewis acid ratio: Stably boosting ethylene/propylene ratio for cracking n-heptane

Modulating zeolite acidity by conventional metal impregnation is a challenge in preparing hydrocarbon cracking catalyst, which often eliminates its intrinsic strong acidity, resulting in reduced the hydrocarbon conversion capacity and low light olefins (C2=-C4=) yield. Here, the Ce/HZ5-HM and CeO2/HZ5-HM catalysts were readily prepared by hydrothermally modifying HZSM-5 zeolite (HZ5) with cerium salts (Ce3+) and cerium oxide (CeO2), respectively. Comparatively, Ce/HZ5-IW catalyst was obtained by modifying HZ5 with Ce3+ using the incipient wetness impregnation. It is revealed that, compared to HZ5, Ce/HZ5-HM and CeO2/HZ5-HM catalysts have an increased ratio of strong/weak (S/W) acid and Brønsted/Lewis (B/L) acid, while Ce/HZ5-IW sample has reduced strong acidity. Further, the Ce/HZ5-HM exhibits higher acid strength, acid density, and B/L value than that of CeO2/HZ5-HM sample. When applied to cracking n-heptane reaction, compared with HZ5 and Ce/HZ5-IW, heptane conversion and ethylene yield on Ce/HZ5-HM and CeO2/HZ5-HM catalysts increase by 6–11 % and 7–9 %, yielding the ratio of ethylene/propylene (E/P) more than 1. Moreover, Ce/HZ5-HM and CeO2/HZ5-HM catalysts perform a lifetime of 117 h and 150 h, with four-to-five times longer than that of HZ5 zeolite (∼29 h) and Ce/HZ5-IW catalyst (∼39 h). The characterization results demonstrate that, adopting hydrothermal method ensures more Ce3+ interacting with the silanol groups in Ce/HZ5-HM, generating the new Brønsted acid sites and makes CeOx species incorporating into the hydroxyl nest of zeolite, which can heal the defective sites and improve stabilization of acidity and framework structure of zeolite. Therefore, the above two catalysts can highlight the monomolecular cracking reaction, low coke deposit rate, long catalytic stability.

The impact of indium and manganese modifiers on the catalytic properties of zinc-alumina propane dehydrogenation catalysts

Supported zinc-containing catalysts are considered as a viable alternative to the currently-deployed Cr-based (toxic) and Pt-based (costly) catalysts of alkane dehydrogenation, as reflected also in the increased number of reports related to the Zn-based catalysts in recent years. Here, we present a study of alumina-supported Zn-In and Zn-Mn propane dehydrogenation (PDH) catalysts prepared by the tailored methods. Specifically, the introduction of zinc relied on the chemical vapor deposition (CVD, using Zn vapor) onto alumina or alumina-supported indium or manganese materials, the latter two prepared by the impregnation of alumina with aqueous solutions of the respective metal nitrates followed by the calcination and hydrogen treatment. Alternatively, both zinc and indium were introduced by the co-impregnation of alumina with aqueous zinc and indium nitrates. The PDH tests revealed that the “dilution” of the active Zn2+ surface sites with In+ cations lead to a significant improvement in the catalytic performance, i.e., the introduction of In+ increased propene selectivity and attenuated the undesirable cracking and hydrogenolysis side reactions as well as decreased coke formation. In contrast, Mn2+ cations improved the catalytic properties of Zn2+ surface sites to a lesser extent than In+ cations. All prepared catalysts were characterized by DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy of the adsorbed CO and H2 probe molecules. It was found that surface In+ and Mn2+ cations affect Zn2+ sites (electronic and geometric effect), which can be assessed from the position of the IR bands of zinc hydridespecies, formed due to the heterolytic hydrogen dissociation on the Zn2+ active sites. The effect of In and Mn dopants also was confirmed by the molecular DFT simulation.

Prediction of sulfur compounds and total sulfur contents in catalytic cracking products of hydrotreated and non-hydrotreated feeds

Relevance. The lack of a reliable mathematical model suitable for predicting the yield and quality of products in catalytic cracking units, with an assessment of the environmental indicators of fuel fractions when changing the hydrocarbon composition and distribution of sulfur compounds in the process feedstock, as well as the possibility of involving highly sulfur-containing oil streams in processing on existing catalytic cracking units. Aim. To develop and apply a mathematical model of the catalytic cracking to predict the content of sulfur compounds and total sulfur in the products during the processing of hydrotreated and non-hydrotreated petroleum feedstocks. Methods. A complex of experimental methods, including liquid and gas chromatography to determine the composition of the feedstock and the distribution of sulfur compounds in the feedstock and catalytic cracking products, methods of quantum chemical modeling of reactions involving sulfur compounds, as well as numerical methods for processing and solving systems of differential equations. Quantum chemical modeling methods were used to study the thermodynamic parameters of catalytic cracking reactions involving sulfur-containing compounds. Results. The authors have developed and implemented in software a mathematical model of catalytic cracking involving hydrocarbons C1–C40+ and sulfur compounds (thiophenes C0–C4, alkylbenzothiophenes C0–C6, C0–C3 dibenzothiophenes, and C4–dibenzothiophene-benzonaphthothiophenes). The model aims to predict the yield and composition of process products, as well as the environmental indicators of motor fuels. Thermodynamic and kinetic parameters of catalytic cracking reactions were determined using quantum chemical modeling methods and solving the inverse kinetic problem.

Assessment of Performance and Deactivation Resistance of Catalysts in the Pyrolysis of Polyethylene and Post‐Consumer Polyolefin Waste

AbstractIn the present work, the catalyst performances of USY and REY zeolites and MgO, ZnO, and MgxAlOy oxides are investigated in the pyrolysis of virgin high‐density polyethylene (HDPE) and of post‐consumer polyolefin waste. The influence of operation parameters and catalyst deactivation resistance over four reaction cycles are evaluated. The results indicate that basic oxides do not show relevant cracking activity, so that the only identified effect for these catalysts is the production of liquid products with higher contents of paraffins when compared to thermal pyrolysis. Among the evaluated oxides, MgxAlOy is the most active and resistant to deactivation. The zeolites promote cracking and secondary reactions of isomerization, cyclization, and aromatization. Particularly, USY promotes the production of higher‐quality oils and shows higher deactivation resistance, when compared to REY. Additionally, a significant loss of catalyst activity is identified in reactions conducted with post‐consumer polyolefin wastes. However, increase in rates of coke formation and the presence of contaminants (such as halogens and metals) are not detected in the catalysts after the reactions.

Conversion of Biomass-Derived Tars in a Fluidized Catalytic Post-Gasification Process

The present study deals with the development, characterization, and performance of a Ni-based catalyst over a ceria-doped alumina support as a post-gasification step, in the conversion of biomass-derived tars. The catalysts were prepared using the incipient wetness technique and characterized chemically and physically using NH3-TPD, CO2-TPD, H2-TPR, XRD, Pyridine-FTIR, N2 physisorption, and H2-Pulse Chemisorption. It was observed that the 5 wt% CeO2 reduced the strong and very strong acid sites of the alumina support and helped with the dispersion of nickel. It was noticed that the nickel crystallite sizes and metal dispersion remained unchanged as the nickel loading increased. The performance of the catalysts was studied in a mini-fluidized CREC Riser Simulator at different temperatures and reaction times. The selected tar surrogate was 2-methoxy-4-methylphenol, given its functional group similarities with lignin-derived tars. A H2/CO2 gas blend was used to emulate the syngas at post-gasification conditions. The obtained tar surrogate conversion was higher than 75%, regardless of the reaction conditions. Furthermore, the catalysts used in this research provided an enhancement in the syngas product composition when compared to that observed in the thermal experiments. The presence of hydrocarbons greater than CH4 (C1+) was reduced at 525 °C, from 96 ± 3% with no catalyst, to 85 ± 2% with catalyst and steam, to 68 ± 4% with catalyst and steam-H2/CO2. Thus, the catalyst that we developed promoted tar cracking, tar reforming, and water-gas shift reactions, with a H2/CO ratio higher than 3.8, providing a syngas suitable for alcohol synthesis.

Study on effects of ethylene or acetylene addition on the stability of ammonia laminar diffusion flame by optical diagnostics and chemical kinetics

Improvement of ammonia combustion characteristics by carbon-based combustion promoters is currently emphasized, but the impact of carbon‑carbon multi-bond structure on ammonia combustion characteristics and reaction mechanisms has not been sufficiently investigated. In order to investigate the mechanism of molecular structures (C=C and C≡C) of combustion promoters on the stability of ammonia flames, the flame morphology, flame structure, NH3-H2 cracking, and C-N cross-reaction of ammonia/ethylene and ammonia/acetylene laminar diffusion flame are investigated based on a Gu¨lder burner by utilizing high-speed photography, planar laser-induced fluorescence (PLIF) and laser spontaneous Raman scattering (SRS) techniques. The results show that acetylene addition is more effective than ethylene to improve the flame stability. Combined with the flame structure analysis, it is shown that C=C mainly enhances the low-temperature reaction stage intensity of laminar flame, while C≡C can both enhance the intensity of low-temperature and high-temperature reaction stages, thereby enhancing the flame combustion exothermic process. Besides, C=C mainly strengthens the exothermic reactions in the upstream of the flame whereas C≡C can strengthen the exothermic reactions in the upstream and downstream of the flame simultaneously. Investigation of the NH3-H2 cracking reactions reveals that C≡C promotes H2 generation mainly by increasing NH3→H2 cracking, whereas C=C promotes H2 generation mainly by increasing NH2→H2 and NH→H cracking, hence improving the flame stability. Further analysis through the reaction flows revels that C=C acts mainly on H-containing species HCN/HNCO whereas C≡C mainly acts on non-H-containing species CN/NCO to influence the reaction pathways, but C-N cross-reaction does not play an important role in the characteristics of ammonia composite combustion (ACC).

An Experimental Study and Numerical Simulation Analysis of Thermal Oxidation Characteristics Based on Kinetic Parameters in Heavy Oil Reservoirs

In situ combustion (ISC), an efficient and economical method for enhancing heavy oil recovery in high-pressure, high-viscosity, and thermally challenged reservoirs, relies on the kinetics of crude oil oxidation. Despite an increased focus on kinetic models, there is a gap in understanding how oxidation kinetic parameters impact ISC effectiveness in heavy oil reservoirs. This study addresses this by selecting heavy oil samples from the G Block in the Liaohe oilfield and the M Block in the Huabei oilfield and conducting ramped temperature oxidation (RTO), pressure differential scanning calorimetry (PDSC), and thermogravimetric analysis (TGA) experiments. RTO detailed the thermal conversion process, categorizing oxidation into low-temperature oxidation (LTO), fuel deposition (FD), and high-temperature oxidation (HTO) stages. PDSC and TGA provided thermal characteristics and kinetic parameters. The feasibility of fire flooding was evaluated. Using CMG-STARS, an ISC model was established to analyze the impact of kinetic parameter changes. Activation energy significantly affected coke combustion, while the pre-exponential factor had a notable impact on cracking reactions. The recommended values for activation energy and the pre-exponential factor are provided. This study not only guides fire flooding experiments but also supports field engineering practices, particularly for in situ combustion in heavy oil reservoirs.

Predicting Rate Constants of Alkane Cracking Reactions Using Machine Learning.

Calculating the thermal rate constants of elementary combustion reactions is of great importance in theoretical chemistry. Machine learning has become a powerful, data-driven method for predicting rate constants nowadays. Recently, the molecular similarity combined with the topological indices were proposed to represent the hydrogen abstraction reactions of alkane [J. Chem. Inf. Model. 2023, 63, 5097-5106], which are, however, not applicable to alkane cracking reactions, another important class of combustion reactions, due to the cleavage of the C-C bond. In this work, a new feature selection scheme is proposed to describe both bimolecular and unimolecular cracking reactions. Molecular descriptors are elaborately selected individually for both reactants and products from those generated by the open-source software RDKit. Machine learning models combined with these molecular descriptors are proven to have the ability to accurately predict rate constants of both the hydrogen abstraction reactions of alkanes by CH3 and the alkane cracking reactions. The average deviation of the XGB-FNN model for prediction is around 60% for the hydrogen abstraction reactions of alkanes and 100% for the alkane cracking reactions. It is expected that the descriptors proposed in this work can be applied to build machine learning models for other reactions.

Construction of diverse hollow MFI zeolites through regulating the micropore filling agents

Constructing hollow structure into microporous zeolites can improve the accessibility of acid sites located at the inner part and the diffusion property. Hence, the development of an efficient synthesis strategy to acquire zeolites with tunable hollow structures and acidity has attracted much attention. In this work, an innovative tandem synthesis route was proposed to prepare MFI zeolites with diverse hollow structure while maintaining solid yields exceeding 90 %. The substitution of ethanol molecules, which previously occupied the micropores, with tetrapropylammonium cations was proved to be the key factor to construct hollow structure. And a crystallization-driven particle dissolution mechanism was proposed. The dimension of the hollow cavity, particle size, and Si/Al ratio can be flexibly regulated. Interestingly, hollow MFI samples featuring the common cavity structure, “eye-like” cavity structure, or double-cavity structure can be directly synthesized by controlling the dissolution of core parts. In the 1-butene catalytic cracking reactions, a much higher conversion of 67.2 % was acquired over hollow ZSM-5 compared with that over conventional ZSM-5 (35.8 %) after 64 h of reaction. This improvement can be attributed to the eightfold increase of diffusivity in hollow ZSM-5. This facile and efficient synthesis method endows accurate regulation of the hollow structure, which is meaningful for both fundamental research and industrial applications of hollow zeolites.

Waste-derived catalysts for tar cracking in hot syngas cleaning

Catalytic tar cracking is a promising technique for hot syngas cleaning unit in gasification plants because it can preserve tars chemical energy, so increasing the syngas heating value. The cost associated with catalyst preparation is a key issue, together with its deactivation induced by coke deposition. Iron is a cheap and frequently used catalyst, which can also be found in some industrial wastes. The study aims to assess the catalytic efficiency for tar cracking of two waste-derived materials (red mud and sewage sludge) having high content of iron. The catalysts were supported on spheres of γ-Al2O3, and their efficiency was compared to that of a pure iron catalyst. The role of support was investigated by testing pure red mud, with and without the support. A series of long-term tests using naphthalene as tar model compound were carried out under different values of process temperatures (750 °C-800 °C) and steam concentrations (0 %-7.5 %). The waste derived catalysts showed lower hydrogen yields compared to pure iron catalyst, due to their lower content of iron. On the other hand, the conversion efficiencies of all the tested catalysts resulted rather similar, since the Alkali and Alkaline-Earth Metallic species present on the surface of waste-derived catalyst help in preventing coke deposition. The iron oxidation state appears to play an important role, with reduced iron more active than its oxidised form in the tar cracking reactions. This indicates the importance of tuning steam concentration to keep constant the reduced state of iron while limiting coke deposition.

Boosting propane dehydrogenation performance over the highly dispersed Co(Ⅱ) sites on ultra-high silica ZSM-5 zeolite

Propane dehydrogenation (PDH) has emerged as an effective way to address the problem of propylene production gap in recent years. However, industrial catalysts are challenged by the scarcity of Pt and toxicity of CrOx. Herein, a series of Co-based catalysts supported on MFI type zeolites with various Si/Al ratios were synthesized by regulating the acid sites to alleviate side reactions. The catalyst Co/ZSM-5-1500 exhibits the superior PDH performance due to the highest proportion of Co(Ⅱ) active sites. The initial C3H6 formation rate is 6.5 mmol g−1cat h−1, along with good long-term stability across three cycles. The Brønsted acid sites over ZSM-5-40 are prone to catalyzing side reactions of cracking and coke deposition to decrease propylene selectivity and stability. This work demonstrates that Co species supported on high silica ZSM-5 zeolite via impregnation method is favorable to generate the highly dispersed Co(Ⅱ) species on the surface of zeolites, and the Co(Ⅱ) species are responsible for excellent PDH performance.

Deciphering the Pivotal Reaction Conditions for Hydrogen Production from Tar Catalytic Cracking by Perovskite

The catalytic cracking of pyrolysis gasification tar into H2 has garnered significant attention due to its exceptional conversion efficiency. In this study, the effects of pollutant concentration, residence time, weight hourly space velocity (WHSV), and reaction temperature on the hydrogen performance of LaFe0.5Ni0.5O3 perovskite were comprehensively investigated. Results revealed that moderate pollutant concentration (0.3 g/L), low-medium residence time (250 SCCM), and low WHSV (0.24 gtoluene/(gcat·h)) facilitated efficient interaction between LaFe0.5Ni0.5O3 and toluene, thus achieving high hydrogen production. An increase in reaction temperature had minimal effect on the hourly hydrogen production above 700 °C but caused a significant increase in methane production. Additionally, the effects of oxygen evolution reactions, methane reactions, and methane catalytic cracking reactions of perovskite induced by different reaction conditions on tar cracking products were discussed in detail. Compared to previous reports, the biggest advantages of this system were that the hydrogen production per gram of tar was as high as 1.002 L/g, and the highest hydrogen content in gas-phase products reached 93.5%, which can maintain for approximately 6 h. Finally, LaFe0.5Ni0.5O3 showed good thermal stability, long-term stability, and catalyst reactivation potential.

Effects of mild acid pre-treatment on the co-pyrolysis behaviour of biosolids and wheat straw

Co-pyrolysis of biosolids (BS) and wheat straw (WS), as well as their treated variants, was performed in a fluidised bed reactor at 500 ℃. Under mild acid pre-treatment conditions (3% H2SO4 and 25 ℃), demineralisation was the dominating effect of pre-treatment on BS, while it was hemicellulose hydrolysis for WS. Consequently, the co-pyrolysis of raw biosolids (RBS) or treated biosolids (TBS) with raw wheat straw (RWS) or treated wheat straw (TWS) had varying effects on product distribution and product compositions. The co-pyrolysis of RBS+RWS gave the lowest bio-oil yield (36.3 wt%) and highest gas yield (23.1 wt%). In contrast, the highest bio-oil yield (45.8 wt%) and lowest gas yield (14.4 wt%) occurred during the co-pyrolysis of TBS+TWS. The degree of synergy in product distribution was strongest in TBS+RWS followed by RBS+RWS and was weakest in TBS+TWS, demonstrating the catalytic effect of inherent minerals on organic matter devolatilisation and char cracking reactions during co-pyrolysis. Biosolids pre-treatment alone performed competitively with BS co-pyrolysis alone with respect to enhancement in biochar properties producing biochar having 15–18 MJ/kg calorific value, 43–51 wt% carbon content, 0.7–1.0 fuel ratio, ⁓30% organic matter retention, and 27–41 wt% ash content. However, combining BS co-pyrolysis and pre-treatment gave the lowest reduction in biochar total heavy metal concentration. Furthermore, bio-oil compositions were influenced by pre-treatment and/or co-pyrolysis, increasing the yield (area%) of phenols to 25.4%, furans to 24.8%, anhydrosugars to 7.8%, and aromatic hydrocarbons to 20.6%. Lastly, pre-treatment alone weakened gas production while co-pyrolysis combined with pre-treatment impacted the pyrolysis gas profile, switching between light hydrocarbons and carbon oxides (CO and CO2). Overall, co-pyrolysis and pre-treatment can each be a standalone strategy for enhancing BS pyrolysis; however, their combination produced greater synergy for generating high value products.