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Fuel: A journal of fuel science
Butterworths
Fuel: A journal of fuel science

Butterworths

0016-2361

Fuel: A journal of fuel science/Journal Fuel: A journal of fuel scienceSCIISTP
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    Enhanced catalytic decomposition of methyl formate to carbon monoxide and methanol using palladium/activated carbon catalyst: Mechanistic insights and catalyst design considerations

    Shen W.Zhang X.Huang Y.Xu L....
    1.1-1.8页
    查看更多>>摘要:© 2024The catalytic decomposition of methyl formate into carbon monoxide and methanol offers a promising route to enhance the economic efficiency of coal-to-ethylene glycol technology. In this study, we investigated the performance of different supported palladium catalysts for methyl formate decomposition. Activated carbon emerged as a superior support, providing a large surface area and facilitating electron transfer, leading to enhanced catalytic activity. The 5 wt% Pd/AC catalyst exhibited a conversion rate of 96.11 % for methyl formate, with high selectivity towards carbon monoxide (95.05 %) and methanol (99.81 %) at 260 °C. The catalyst stability and effective Pd dispersion on Activated carbon were confirmed through SEM, TEM, XRD, FT-IR and H2-TPR analyses. Our findings highlight the potential of Pd/AC catalysts for efficient and selective methyl formate decomposition, with implications for high-purity carbon monoxide production and other catalytic processes.

    Insight into the micro-mechanism of hydrate-based methane storage from active ice

    Duan J.Zhong K.Jiang S.Chen D....
    1.1-1.10页
    查看更多>>摘要:© 2024 Elsevier LtdGas hydrate formation in active ice holds significant potential for solidified natural gas storage, while the deep understanding of its micro-mechanism is required for the futural application of such a technology. In this study, the kinetics and micro-properties of methane hydrate formation enhanced by active ice (porous ice containing an unfrozen solution layer of sodium dodecyl sulfate) were investigated via experiments and molecular dynamics (MD) simulations. Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray diffraction (XRD) differential scanning calorimetry (DSC) characterization, and in-situ visual observation confirmed the formation of sI methane hydrate in the active ice system and the occurrence of single-crystal hydrate, and also indicated the occurrence of active water near the surface of porous active ice during the active ice formation. A sensitivity analysis of the hydrate kinetics experiments suggested that temperature is the primary driver of rapid methane hydrate formation in the active ice system. The shortest induction time and t90 for hydrate formation were recorded at 5 s and 5.5 min, respectively. Furthermore, MD simulations indicated that the direct hydrate nucleation and growth in the active water, heat transfer from gas hydrate to ice, and the diffusion of active water (1.24 × 10-9 m2/s) and methane (7.10 × 10-8 m2/s) into the porous ice structure are the primary mechanism that enhances hydrate formation kinetics and methane storage capacity. This work provides an essential microscopic mechanism of the “active ice → active water → gas hydrate” circulation that contributes to the deep understanding and futural application of the efficient hydrate-based solidified methane storage in active ice system.

    An analytical framework to assess the chemical changes in polymer-modified bitumen upon natural and simulated ageing

    Werkovits S.Grothe H.Primerano K.Hofko B....
    1.1-1.9页
    查看更多>>摘要:© 2024 The AuthorsPolymers play a crucial role in modifying the mechanical and rheological properties of bituminous construction materials. One of the most employed polymers, particularly in road engineering, is styrene–butadiene–styrene (SBS). However, long-term interactions of the SBS composite mixture with solar radiation and atmospheric gases result in material deterioration. Despite its prevalent use, the specific contribution of the polymer in these processes remains insufficiently understood. To address this gap in knowledge, we developed an analytical framework to precisely determine the chemistry of SBS-modified bitumen. Unmodified and SBS-modified samples were aged according to different ageing procedures to analyse thermal and thermochemical influences. These samples were then compared to genuine samples obtained from construction sites/test fields. Infrared spectroscopy revealed the formation of carbonyls and sulfoxides during all ageing procedures. The highest increase was observed in the field-aged sample. High temperatures during laboratory ageing affected the sulfoxide formation, as decomposition became a limiting factor. Comparing unmodified and SBS-modified samples showed that the oxygen uptake was similar during all ageing procedures, indicating that the presence of SBS did not impact the oxidation susceptibility. Two-dimensional nuclear magnetic resonance (NMR) spectroscopy facilitated the quantification of SBS substructures, showing a loss of 21% olefinic and 25% allylic SBS groups during field ageing. Aromatic SBS structures remained unaffected. The addition of ozone and nitrogen dioxide led to a degradation of 5% olefinic and 10% allylic structures during thermochemical ageing, while the variations during thermal ageing were less than 3%. Field ageing did not alter the aromatic structures in the bitumen phase in the SBS-modified binder but revealed significant decreases in the unmodified sample. Diffusion-ordered NMR spectroscopy showed that the average molecular size of the polymer halved during field ageing. Multiple ageing cycles were required to replicate this trend in the laboratory. However, extending the ageing time and adding reactive oxygen species reduced the number of aromatic structures in the bitumen phase, while no alteration occurred in the field. This study introduces the most precise framework to evaluate the chemical state of SBS-modified binders. The developed framework can be applied to monitor degradation, determine the lifetime and validate ageing technologies.

    Microscopic influence mechanisms of pre-adsorbed polysaccharide on the nucleation and growth of methane hydrate on metal surface

    Luo R.Zhong K.Chen D.Wang L....
    1.1-1.11页
    查看更多>>摘要:© 2024Natural gas hydrate plugging in oil and gas pipelines leads to reduced delivery, equipment deterioration, and accidents. Corrosion alters the pipe surface, creating new sites for gas hydrate formation and increasing the risk of hydrate plugging. Microbiologically influenced corrosion (MIC) caused by biofilm adhesion is an important type of corrosion in offshore oil and gas pipelines. However, the influence of biofilm components on gas hydrate formation remains unclear. Molecular dynamics simulations were used to study how pre-adsorbed alginate (a representative biofilm component) on iron surface (steel pipe), effects the nucleation and growth of gas hydrate. Results demonstrated that the pre-adsorbed alginate inhibited hydrate nucleation by strongly adsorbing methane, causing it to aggregate within the alginate voids or form bubbles in solution. The reduced methane concentration in water and decreased spatial uniformity hindered the hydrate nucleation. However, the pre-adsorbed alginate promoted nearby hydrate seed growth by attracting methane to form a denser methane distribution locally. More methane molecules were then transported to seed cages, synergistically promoting hydrate seed growth. This study explores the microevolutionary mechanisms of gas hydrates effected by adsorbed biofilm polysaccharide on metal, providing insights into mitigating hydrate plugging caused by MIC in oil and gas pipelines.

    Facile electrodeposition of Iron-doped NiMo alloys as bifunctional electrocatalysts for alkaline overall water splitting

    Ren T.Chen Q.Tang C.Chen J....
    1.1-1.11页
    查看更多>>摘要:© 2024 Elsevier LtdNickel-molybdenum (NiMo) alloy has been widely used as electrode materials for alkaline hydrogen evolution reaction (HER). However, pristine NiMo alloy faces problem such as poor oxygen evolution reaction (OER) kinetics, molybdenum dissolution, and unsatisfactory durability. Careful incorporation of the appropriate foreign metallic element into the alloy has been shown to be an effective strategy for improving the electrocatalytic performance. Herein, iron (Fe) was doped into NiMo alloy by a facile electrodeposition process and used as bifunctional electrocatalysts for alkaline water splitting. XRD and TEM techniques confirm the successful doping of Fe. XPS and DFT calculations indicate that the Fe doping effectively modulates the electronic structure of the NiMo alloy, bringing the d-band centre closer to the Fermi energy level, which significantly optimize the adsorption/desorption of the OER/HER intermediates. As a result, the optimized sample, Fe0.2-NiMo, exhibits outstanding HER and OER performance with overpotentials of 85 mV and 269 mV at ± 10 mA cm−2, respectively. The two-electrode cell with Fe0.2-NiMo as both anode and cathode requires only 1.9 V to drive the overall water splitting at 500 mA cm−2, further demonstrating the huge potential of Fe0.2-NiMo for alkaline water splitting. Further studies show that the Fe0.2-NiMo suffers from phase transformation to NiFe(oxy)hydroxide as electrocatalytic active center for HER/OER and that the Fe doping can mitigate the dissolution of Mo to some extent independently of OER and HER.

    Anaerobic co-digestion of winery wastewater with sewage sludge for methane production: Complementary feedstocks and potential direct interspecies electron transfer

    Ma Z.Yu L.Wang Z.Liu R....
    1.1-1.11页
    查看更多>>摘要:© 2024 Elsevier LtdCombining winery wastewater (WW) with sewage sludge (SS) in anaerobic co-digestion (AcoD) presents a promising approach for effective waste management and enhanced energy recovery. This study aimed to evaluate the efficiency and changes in microbial communities during the AcoD of WW with SS at 35 °C, using a mix of batch and semi-continuous testing methods. In the batch experiments, the highest hydrolysis rate (0.19 day−1) and methane production (285.61 ± 4.83 mL/g VS) were achieved at a WW:SS ratio of 3:2, exceeding those of SS mono-digestion by 126 % and 113 %, respectively. Furthermore, the semi-continuous experiments revealed a significant 30.0 % boost in the electron transport system activity and a notable 25.8 % increase in coenzyme F420 activity within the AcoD of WW with SS. Microbial analysis illustrated that AcoD of WW with SS significantly enriched the prevalence of potential genera associated with direct interspecies electron transfer (DIET), such as Longilinea, Bellilinea (genus of Chloroflexi), Syntrophomonas, Pseudomonas, Methanosarcina, and Methanobacterium species. Additionally, semi-continuous experiments demonstrated that AcoD facilitated interspecies hydrogen transfer between syntrophic bacteria and hydrogenotrophic methanogens, resulting in increased methane yield. Co-digestion of WW with SS is a more economical strategy that significantly enhances the stability of microbial communities through the use of complementary feedstocks. These results may offer valuable guidance for the efficient resource utilization of co-digestion processes involving WW and SS.

    Development of polyols analogous to neopentyl glycol and trimethylolpropane for the production of oleic acid-based biolubricants

    Ramos Moreira D.Nery Ferreira E.Bezerra Mota Gomes Arruda T.Maria Pontes Silva Ricardo N....
    1.1-1.13页
    查看更多>>摘要:© 2024 Elsevier LtdVegetable oils and animal fats have been known and used as lubricants and fuels since ancient times. However, the chain structure of the triacylglycerols (TAGs) generate limitations that discourage the use of these raw materials as lubricants. As an alternative to improve the physicochemical and thermo-oxidative characteristics of natural oils, the use of polyols without the β-hydrogens in the triacylglycerols structure is an efficient solution for the production of biolubricants. In this context, a series of polyols, analogous to trimethylolpropane (TMP) and neopentyl glycol (NPG) was synthesised and applied in the synthesis of polyol esters based on oleic acid. These esters were prepared by homogeneous catalysis using p-toluenesulfonic acid (p-TSA) and are intended for use as biolubricants. The synthesised polyols were characterized by one and two-dimensional NMR. The derived polyol esters were purified and had their structure confirmed by 1H and 13C NMR, infrared spectroscopy, and mass spectrometry. The polyol esters showed high viscosity index (189 – 222), thermo-oxidative stability (Tonset between 258 and 285 °C), and low melting points (between –19.4 and –47.6 °C). Furthermore, polyol esters showed reduced friction coefficients (0.021 – 0.041) and scar wear diameter on the metallic surface (0.274 – 0.448 mm). In addition to the satisfactory results of thermal stability and lubricity, which suggest the potential of these molecules as lubricants, all molecules were considered environmentally safe when evaluated through the Zebrafish toxicity model.

    Catalytic co-pyrolysis of yellow poplar and HDPE using MOF-incorporated HY zeolite catalysts

    Ratthiwal J.Kongparakul S.Samart C.Chul L.B....
    1.1-1.10页
    查看更多>>摘要:© 2024 Elsevier LtdCatalytic co-pyrolysis of yellow poplar and high-density polypropylene (HDPE) was conducted using metal oxide on hydrogen y-type (HY) zeolite to selectively produce monoaromatic hydrocarbons. The reaction was investigated using a tandem micro-reactor connected to a gas chromatography–mass spectrometry (GC–MS) system, encompassing both in-situ and ex-situ studies. Fe oxide/HY and Cu oxide/HY catalysts, prepared via a metal–organic framework (MOF)-incorporated technique, demonstrated excellent metal dispersion and enhanced electron density. The Cu oxide/HY catalyst showed significant production of benzene, toluene, ethylbenzene, and xylene, reaching up to 28% in in-situ studies. Owing to its strong acid sites, this catalyst facilitated the formation of aromatic compounds. In ex-situ studies, furan and acetaldehyde were consumed through the Diels–Alder reaction. The increase in aromatic compounds was highlighted by a synergistic effect percentage as high as 175%. The mechanism of aromatic formation was elucidated through dealkylation, Diels–Alder, and aromatization reactions. The Cu oxide/HY catalyst, combined with the MOF-incorporated preparation technique presents a promising system for catalytic co-pyrolysis of biomass and HDPE. This approach will facilitate efficient and sustainable aromatic hydrocarbon production from renewable and plastic waste sources.

    Defect confinement in CuO/HZSM-5-T catalysts: A novel approach for enhancing stability in AsH3 catalytic oxidation

    Yang X.Zeng Z.Li Z.Zhang Y....
    1.1-1.9页
    查看更多>>摘要:© 2024The accumulation of arsenic-containing oxides is a critical factor in the reduced activity of catalysts for arsine (AsH3) removal. In this study, we successfully synthesized a hollow-structured molecular sieve support (HZ-T) for CuO loading (12CuO/HZ-T), significantly enhancing AsH3 catalytic oxidation efficiency and stability. The optimized catalyst (12CuO/HZ-T0.7-150-72) exhibited substantially higher AsH3 catalytic activity than the conventional catalyst (12CuO/HZ) at 100 and 140 °C, maintaining 100 % AsH3 removal for over 167 h at 140 °C. Systematic characterization revealed that the superior AsH3 catalytic performance of 12CuO/HZ-T0.7-150-72 is attributed to the confinement of active components within the support's cavities, addressing the rapid deactivation caused by arsenic-containing oxide coverage. Additionally, basic sites introduced by tetrapropylammonium hydroxide (TPAOH) treatment further promoted AsH3 removal efficiency.

    A novel dual-way inference modeling method for coal coking: Predicting H2 and CH4 concentrations in coke oven gas and inferring optimal reaction conditions

    Zhang, XiaoguoRen, DanniFu, XiaolanLu, Wei...
    1.1-1.12页
    查看更多>>摘要:Coal coking is an efficient and environmentally friendly technology for energy utilization that yields various industrial materials. However, the intricate nature of the coal coking reaction poses a challenge for chemical theories to fully capture and derive its reaction process. To address this challenge, a novel dual-way inference modeling method was proposed to simulate the coal coking process. This modeling method not only predicts H2 and CH4 concentrations, but also infers optimal operating conditions based on the desired H2 and CH4 concentrations. In this work, three representative machine learning methods (XGBoost, Random Forest, and ANN) are compared with dual-way inference modeling method, and the key factors affecting H2 and CH4 concentrations are thoroughly explored. The experimental results show that the primary factor influencing CH4 concentration is C, H2 concentration is predominantly affected by fixed carbon, while C plays the most important role for CH4 + H2. The dual-way inference modeling method achieved excellent performance in predicting H2 and CH4 concentrations and operating conditions. In the prediction task of H2, CH4, and H2 + CH4 concentrations, the coefficient of R2 achieved 0.9767, 0.9936, and 0.9851, respectively. The result for predicting coking temperature based on the desired H2 and CH4 concentrations indicate a positive correlation between coking temperature and both H2 and CH4 concentrations. In general, as coking temperature increases, the concentrations of both H2 and CH4 will increase.