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Study on the condensation behavior of KCl vapor on wall surfaces under pressurized condition 加压条件下KCl蒸气在壁面上的凝结行为研究
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-05 DOI: 10.1016/j.fuproc.2025.108373
Yanjie Qi , Bo Wei , Kunpeng Liu , Jianjiang Wang , Shan Wang , Lijuan Chen , Rui Ma
As a pivotal renewable energy source, biomass energy suffers from ash deposition induced by KCl condensation during thermal conversion, which impairs its efficient utilization; yet pressure's impact on KCl condensation remains unclear. Here, the effects of pressure on KCl vaporization and condensation were investigated via a pressurized experimental system, thermodynamic calculations, and characterization techniques including scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Results showed that pressure significantly affected solid KCl's vaporization temperature: at 0.1 MPa, KCl began to vaporize at 725 °C and fully vaporized at 1300 °C, while at 1.4 MPa, these temperatures increased to 900 °C and 1700 °C, respectively. Similarly, gaseous KCl's condensation temperature rose with pressure, with solid KCl precipitating at approximately 1200 °C under 0.1 MPa and 1700 °C under 1.4 MPa. At 1000 °C, increasing pressure reduced KCl's vaporization rate from 52.0 % (0.1 MPa) to 35.2 % (1.4 MPa) and made condensation products smaller, more uniform-the average size fell from 5.89 ± 1.74 μm (0.1 MPa) to 1.20 ± 0.49 μm (1.4 MPa). XRD analysis indicated that pressure minimally influenced KCl's crystal structure but significantly altered the intensity and width of diffraction peaks. This study proposes a KCl condensation mechanism under different pressures and temperatures, providing a basis for addressing ash deposition and slagging in biomass thermal conversion.
生物质能作为一种重要的可再生能源,在热转化过程中存在KCl凝结导致的灰沉积,影响了其高效利用;但压力对KCl冷凝的影响仍不清楚。本文通过加压实验系统、热力学计算以及扫描电子显微镜-能谱(SEM-EDS)和x射线衍射(XRD)等表征技术,研究了压力对KCl蒸发和冷凝的影响。结果表明,压力对固态KCl的汽化温度有显著影响,在0.1 MPa时,KCl在725℃开始汽化,在1300℃完全汽化,而在1.4 MPa时,这两个温度分别升高到900℃和1700℃。同样,气态KCl的冷凝温度也随着压力的升高而升高,在0.1 MPa和1.4 MPa下,固态KCl的冷凝温度分别为1200℃和1700℃。在1000℃时,KCl的蒸发速率由52.0% (0.1 MPa)降至35.2% (1.4 MPa),缩合产物体积更小、更均匀,平均尺寸由5.89±1.74 μm (0.1 MPa)降至1.20±0.49 μm (1.4 MPa)。XRD分析表明,压力对KCl晶体结构的影响很小,但对衍射峰的强度和宽度有显著影响。本研究提出了不同压力和温度下的KCl缩聚机理,为解决生物质热转化过程中的结灰结渣问题提供了依据。
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引用次数: 0
The uneven distribution characteristics of minerals in Zhundong high iron coal and its influence on the slagging process 准东高铁煤矿物不均匀分布特征及其对结渣过程的影响
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-05 DOI: 10.1016/j.fuproc.2025.108372
Kunpeng Liu , Bo Wei , Shan Wang , Jianjiang Wang , Shihai Wang , Xinyi Ma , Lijuan Chen , Xian Li
Due to the influence of the special coal formation environment, the distribution of minerals in coal was not uniform, especially for the Zhundong high iron coal. The impact of this uneven distribution on slagging formation during coal combustion process was still unclear. In this study, three types of Zhundong coal with varying iron contents were selected, the coal and ash characteristics of different density fractions were analyzed after density fractionation. The minerals transformation characteristics of coal ash were also calculated by Factsage. The results showed that the density distributions of the three coal samples differ significantly. HSQ and JJM was primarily concentrated in below 1.4 g/cm3 and 1.4–1.5 g/cm3 two density fractions, but the proportion of >1.6 g/cm3 fraction of JJM was higher than that of HSQ. While the mass distribution of WCW across density ranges showed minor differences. The ash characteristics also exhibited significant differences across the density fractions. As coal density increases, the Na and Ca contents decreased, whereas the Si and Al contents gradually increased, and the Fe content increased substantially. This was particularly evident in JJM coal, where the iron content in the JJM4 ash exceeded 55 %. In the ash of low-density fractions, Na and Ca mainly existed in the form of Na2SO4 and CaSO4, while they mainly existed in the form of combined with Si and Al in the ash of high-density fractions. Besides, Fe2O3 was rich in the ash of high-density fractions, especially in the JJM, which can cause severe slagging and fouling problems under reducing atmosphere. The research results contribute to a deeper understanding of the uneven deposition behavior during Zhundong high iron coal combustion process.
受特殊成煤环境的影响,煤中矿物分布不均匀,尤其是准东高铁煤。这种不均匀分布对煤燃烧过程中结渣形成的影响尚不清楚。本研究选取了三种不同含铁量的准东煤,对不同密度分馏后的煤和灰分特性进行了分析。利用Factsage计算了煤灰的矿物转化特征。结果表明,三种煤样的密度分布差异显著。HSQ和JJM主要集中在1.4 g/cm3以下和1.4 - 1.5 g/cm3以下两个密度馏分,但JJM >;1.6 g/cm3馏分所占比例高于HSQ。而WCW在不同密度范围内的质量分布差异较小。不同密度组分的灰分特征也存在显著差异。随着煤密度的增加,Na和Ca含量降低,Si和Al含量逐渐增加,Fe含量大幅增加。这在JJM煤中尤为明显,JJM4灰分中的铁含量超过55%。在低密度馏分灰分中,Na和Ca主要以Na2SO4和CaSO4的形式存在,而在高密度馏分灰分中,Na和Ca主要以与Si和Al结合的形式存在。此外,高密度馏分灰分中含有丰富的Fe2O3,特别是在JJM中,在还原气氛下会造成严重的结渣和结垢问题。研究结果有助于深入了解准东高铁煤燃烧过程中的不均匀沉积行为。
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引用次数: 0
Enhanced steam and sulfur resistance of Ni-based catalysts in LPG steam reforming via trace pt-induced hydrogen spillover 镍基催化剂在微量铂致氢外溢液化石油气蒸汽重整中的抗蒸汽和抗硫性能
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-05 DOI: 10.1016/j.fuproc.2025.108371
Yi Lin , Yulong Wang , Hongxiang Huang , Feng Wang , Zaixing Wang , Shi Jiang , Xiaoqin Liu , Yu Guo
This study focuses on a Pt-promoted Ni/NiAl (Ni/NiO-Al2O3) catalyst for butane steam reforming, designed to overcome hydrothermal oxidation and sulfur poisoning in Ni-based systems. A series of Ni/Al (Ni/Al2O3) and Ni/NiO-Al2O3 catalysts, with and without Pt modification, were synthesized and systematically evaluated under severe reforming conditions. Compared with conventional Ni/Al, Ni/NiAl exhibited stronger metal-support interaction through NiAl2O4 formation but suffered rapid deactivation in steam-rich and sulfur-containing atmospheres. Incorporating 0.5 wt% Pt markedly improved stability, maintaining high activity and hydrogen selectivity during both steam and H2S exposure. Characterization by XRD, TEM, H2-TPR, and XPS revealed that Pt induces a synergistic protection mechanism, in which hydrogen spillover dynamically regenerates oxidized Ni species and weakens NiS interactions. This effect reduces sulfur coverage on active Ni sites, preserving highly dispersed metallic Ni0. Time-resolved outlet gas analysis further indicated that sulfur preferentially deactivates reforming sites, followed by progressive inhibition of the water-gas shift reaction via a COS-mediated pathway. The catalyst demonstrated excellent stability under 5 ppm H2S at 850 °C, confirming the dual protective role of Pt against oxidation and sulfur poisoning. These findings provide mechanistic insights and design principles for robust, regenerable Ni-based catalysts tailored for distributed hydrogen production from LPG.
本文研究了一种用于丁烷蒸汽重整的pt促进Ni/NiAl (Ni/NiO-Al2O3)催化剂,旨在克服Ni基体系中的水热氧化和硫中毒。合成了一系列Ni/Al (Ni/Al2O3)和Ni/NiO-Al2O3催化剂,并在苛刻的重整条件下进行了系统的评价。与传统的Ni/Al相比,Ni/NiAl通过NiAl2O4的形成表现出更强的金属-载体相互作用,但在富蒸汽和含硫气氛中迅速失活。加入0.5 wt% Pt显著提高了稳定性,在蒸汽和H2S暴露下保持高活性和氢选择性。XRD、TEM、H2-TPR和XPS表征表明,Pt诱导了一种协同保护机制,在该机制中,氢溢出动态地再生氧化的Ni,并减弱了Ni的相互作用。这种效应减少了活性Ni位点上的硫覆盖,保留了高度分散的金属Ni0。时间分辨出口气体分析进一步表明,硫优先使重整位点失活,随后通过cos介导的途径逐步抑制水煤气转移反应。该催化剂在850℃下5ppm H2S条件下表现出优异的稳定性,证实了Pt对氧化和硫中毒的双重保护作用。这些发现为稳健的、可再生的镍基催化剂提供了机理见解和设计原则,这些催化剂专为分布式液化石油气制氢而设计。
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引用次数: 0
Evolution characteristics and mechanisms of molecular structures of shale Kerogen during structural deformation 构造变形过程中页岩干酪根分子结构演化特征及机制
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-05 DOI: 10.1016/j.fuproc.2025.108374
Li Fengli , Jiang Bo , Cheng Guoxi
Revealing the impact of tectonic stresses on shale kerogen molecules sheds light on the evolution mechanisms of shale organic matter. In this study, we first extracted shale kerogen samples from the undeformed and tectonically deformed shale (TDS) and then investigated how shale kerogen molecular structures respond to structural deformation by combining Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The result showed that structural deformation reduced the complexity and branching degree of molecular structures by promoting the breaking of aliphatic side chains and increased the aromaticity and structural order of kerogen molecules by enhancing condensation of aromatic rings. Additionally, shale kerogen displayed a relative enrichment of carbon by removing oxygen-, nitrogen-, and sulfur-containing functional groups. The removal of oxygen-containing functional groups was the most significant, showing a trend of “C-O bonds within aliphatic functional groups > C-O bonds within aromatic functional groups > C=O bonds within functional groups”. In general, the evolution of kerogen molecular structures caused by brittle and ductile deformation followed largely consistent patterns. However, the influence of ductile deformation was much more significant and pronounced than that of brittle deformation, and weak brittle deformation had little impact on kerogen molecular structures.
揭示构造应力对页岩干酪根分子的影响有助于揭示页岩有机质的演化机制。本研究首先从未变形和构造变形的页岩(TDS)中提取页岩干酪根样品,然后结合傅里叶变换红外光谱(FTIR)、拉曼光谱(Raman spectroscopy)和x射线光电子能谱(XPS)研究页岩干酪根分子结构对结构变形的响应。结果表明,结构变形通过促进脂肪侧链的断裂降低了分子结构的复杂性和分支度,通过促进芳烃环的缩聚提高了干酪根分子的芳香性和结构有序度。此外,页岩干酪根通过去除含氧、含氮和含硫官能团表现出碳的相对富集。含氧官能团的去除最为显著,呈现出“脂肪族官能团内C-O键>;芳香官能团内C-O键>;官能团内C=O键”的趋势。总的来说,由脆性变形和韧性变形引起的干酪根分子结构的演化遵循基本一致的模式。而延性变形对干酪根分子结构的影响远比脆性变形显著,弱脆性变形对干酪根分子结构的影响较小。
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引用次数: 0
Improvement of particulate matter emission from biomass pellet fuel combustion by adding pulping effluent during preparation 制备过程中加入制浆废液改善生物质颗粒燃料燃烧中颗粒物排放
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-05 DOI: 10.1016/j.fuproc.2025.108369
Zhaoxiang Liu , Guihua Yang , Yu Xue , Kai Zhang , Peng Gan , Kefeng Liu , Lingsong Meng , Peihua Zhu
Low particulate matter(PM) emissions are a research hotspot pursued in biomass fuel fields. Herein, pulping effluent, an industrial byproduct of the pulping industry, was employed to prepare biomass pellet fuel by combining with reed residue through biomass densification technology. The pyrolysis behavior of pellet fuel particle size and concentration of PM emissions, as well as the composition of solid residual after combustion were investigated to study the influence mechanism of pulping effluent on PM emissions. Results showed that the organic component in pulping effluent can act as adhesive to endow pellet fuel with high density, which effectively enhanced the mechanical properties of pellet fuel by 46 % and notably reduced the concentration and size of PM emission by hindering the discharge of alkaline metals. Meanwhile, the mineral in pulping effluent diminished the production of PM pollutants via limiting the conversion of alkaline metals to PM. The concentration of PM emissions of pellet fuel at 10 % pulping effluent addition was 0.15 mg/g, significantly lower than that of pellet fuel without pulping effluent(4.05 mg/g), representing a 96 % reduction. The beneficial effect of pulping effluent addition on the discharge of PM pollutants can provide a new approach to construct high-performance biomass-based pellet fuels.
低颗粒物(PM)排放是生物质燃料领域的研究热点。本文以制浆工业副产品制浆废水为原料,通过生物质致密化技术,与芦苇渣结合制备生物质颗粒燃料。研究了颗粒燃料的热解行为、颗粒大小和PM排放浓度以及燃烧后固体残留物的组成,研究了制浆废水对PM排放的影响机理。结果表明,制浆废水中的有机成分可以作为粘合剂赋予颗粒燃料高密度,有效提高颗粒燃料的力学性能46%,并通过阻碍碱金属的排放显著降低PM排放浓度和粒径。同时,制浆废水中的矿物通过限制碱金属向PM的转化,减少了PM污染物的产生。添加10%制浆废水的颗粒燃料的PM排放浓度为0.15 mg/g,显著低于未添加制浆废水的颗粒燃料(4.05 mg/g),减少了96%。制浆废液添加对PM污染物排放的有利影响为构建高性能生物质颗粒燃料提供了新的途径。
{"title":"Improvement of particulate matter emission from biomass pellet fuel combustion by adding pulping effluent during preparation","authors":"Zhaoxiang Liu ,&nbsp;Guihua Yang ,&nbsp;Yu Xue ,&nbsp;Kai Zhang ,&nbsp;Peng Gan ,&nbsp;Kefeng Liu ,&nbsp;Lingsong Meng ,&nbsp;Peihua Zhu","doi":"10.1016/j.fuproc.2025.108369","DOIUrl":"10.1016/j.fuproc.2025.108369","url":null,"abstract":"<div><div>Low particulate matter(PM) emissions are a research hotspot pursued in biomass fuel fields. Herein, pulping effluent, an industrial byproduct of the pulping industry, was employed to prepare biomass pellet fuel by combining with reed residue through biomass densification technology. The pyrolysis behavior of pellet fuel particle size and concentration of PM emissions, as well as the composition of solid residual after combustion were investigated to study the influence mechanism of pulping effluent on PM emissions. Results showed that the organic component in pulping effluent can act as adhesive to endow pellet fuel with high density, which effectively enhanced the mechanical properties of pellet fuel by 46 % and notably reduced the concentration and size of PM emission by hindering the discharge of alkaline metals. Meanwhile, the mineral in pulping effluent diminished the production of PM pollutants via limiting the conversion of alkaline metals to PM. The concentration of PM emissions of pellet fuel at 10 % pulping effluent addition was 0.15 mg/g, significantly lower than that of pellet fuel without pulping effluent(4.05 mg/g), representing a 96 % reduction. The beneficial effect of pulping effluent addition on the discharge of PM pollutants can provide a new approach to construct high-performance biomass-based pellet fuels.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"280 ","pages":"Article 108369"},"PeriodicalIF":7.7,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Study on the influence of particle size and heating rate on pyrolysis characteristics and kinetics of Xinjiang high-chlorine coal 粒度和升温速率对新疆高氯煤热解特性及动力学的影响研究
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-05 DOI: 10.1016/j.fuproc.2025.108376
Xiangyong Zheng , Feng Wang , Jianjiang Wang , Bo Wei , Kunpeng Liu , Shan Wang , Rui Ma , Lijuan Chen , Maierhaba Abudoureheman
Xinjiang high‑chlorine coal has abundant reserves, but its high chlorine content causes slagging, ash deposition and equipment corrosion during pyrolysis, limiting its large-scale utilization. This study investigated the effects of particle size (54–200 μm) and heating rate (10–30 °C/min) on the pyrolysis characteristics and kinetics of Shaerhu coal (SEH) using TG-DTG analysis, the Coats-Redfern method and model-free methods. SEH pyrolysis involved three stages, with weight loss peaks near 100 °C, 450 °C and 715 °C. SHE's peak mass loss rate temperature was 10–30 °C lower than other low-rank coals. Larger particles significantly increased the weight loss rate, peaking at 0.1164 %/°C for 150–200 μm. Higher heating rates shifted DTG curves upper right, reduced mass loss rates and increased thermal hysteresis. C-R method indicated that in Stage I, higher heating rates raised activation energy (E). In Stage II, particle size influenced E more than heating rate. In Stage III, larger particles had lower E (19.51–34.09 kJ·mol−1 reduction from 54–76 to 150–200 μm). Model-free methods showed consistent E trends, but generally Friedman > FWO > KAS. A notable E decrease occurred at 0.8 conversion for 54–76 μm particles, while 150–200 μm particles declined gradually from 220 kJ·mol-‍1 after 0.4 conversion.
新疆高氯煤储量丰富,但高氯煤在热解过程中会产生结渣、结灰和设备腐蚀等问题,限制了其规模化利用。采用TG-DTG法、Coats-Redfern法和无模型法研究了粒径(54 ~ 200 μm)和升温速率(10 ~ 30°C/min)对沙尔湖煤(SEH)热解特性和动力学的影响。SEH热解分为三个阶段,失重峰分别在100℃、450℃和715℃附近。SHE的最大失重速率温度比其他低阶煤低10 ~ 30℃。较大的颗粒显著增加了失重速率,在150 ~ 200 μm范围内失重速率达到0.1164 %/°C。较高的升温速率使DTG曲线右上方偏移,降低了质量损失率,增加了热滞后。C-R法表明,在第一阶段,较高的加热速率提高了活化能(E)。在第二阶段,粒径对E的影响大于升温速率。在第三阶段,颗粒越大,E值越低(从54 ~ 76 μm降低到150 ~ 200 μm, E值降低19.51 ~ 34.09 kJ·mol−1)。无模型方法显示出一致的E趋势,但一般为Friedman >; two >; KAS。转化率为0.8时,54 ~ 76 μm颗粒的E值显著降低,而转化率为0.4时,150 ~ 200 μm颗粒的E值从220 kJ·mol-‍1逐渐下降。
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引用次数: 0
Effects of flame arrester on H2-Air detonation under different initial pressure propagation in the T-shaped pipeline 阻火器对t型管道中不同初始压力传播下h2 -空气爆轰的影响
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-05 DOI: 10.1016/j.fuproc.2025.108375
Lianzhuo Zhang, Xiaoyang Liu, Xingqing Yan, Jianliang Yu
Experimentally investigated stoichiometric hydrogen-air mixture detonation propagation under initial pressures from 30 kPa to 100 kPa in a T-shaped pipeline. The numerical simulation revealed the detonation wave propagation mechanism in the flame arrester chamber. The velocity and dynamic pressure were obtained as the aspect ratio (L/h) of flame-arresting elements increased from 60 to 600. The results show that detonation under initial pressure below 70 kPa will quench in L/h > 120, but re-detonation happens in L/h < 120. The detonation attenuation is enhanced with L/h increases and initial pressure decreases; the attenuation intensity increases sharply when 180 < L/h < 300 and decreases when L/h > 300. The flame passing through the flame arrester will propagate into bifurcated pipes, with attenuation in the horizontal pipe more significant than in the vertical pipe. As the L/h increases, the flame attenuation when passing the T-junction intensifies when L/h < 120 and diminishes when L/h > 180, and the flame accelerates when L/h is 60. The flame arrester's outlet velocity becomes the most significant factor determining the flame attenuation in the T-junction.
实验研究了初始压力为30 ~ 100 kPa的t型管道中氢气-空气混合爆轰传播的化学计量学。数值模拟揭示了爆震波在阻火器腔内的传播机理。当阻焰元件展弦比(L/h)从60增加到600时,得到了阻焰元件的速度和动压力。结果表明:在初始压力低于70 kPa时,爆轰在L/h >; 120内淬灭,在L/h <; 120内发生再爆轰;爆轰衰减随L/h的增大和初始压力的减小而增强;当180 <; L/h <; 300时衰减强度急剧增大,当L/h >; 300时衰减强度减小。通过阻火器的火焰会传播到分叉的管道中,在水平管道中的衰减比在垂直管道中的衰减更显著。随着L/h的增大,当L/h <; 120时火焰通过t型结衰减加剧,当L/h >; 180时衰减减弱,当L/h为60时火焰加速。阻火器出口速度成为决定t型结火焰衰减的最重要因素。
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引用次数: 0
CexFeyO catalysts for efficient char-CO2 gasification: Tuning oxygen vacancies and redox properties 高效炭- co2气化的cefeyo催化剂:调整氧空位和氧化还原性能
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-05 DOI: 10.1016/j.fuproc.2025.108378
Yinglu Zhang , Yun Hao , Weiwei Wu , Ruijie Liang , Shihao Lv , Wenran Gao , Zhiliang Wu , Yan Chen , Shu Zhang
This study investigates the catalytic mechanisms and performance of CexFeyO catalysts in the CO2 gasification of straw char. A series of CexFeyO catalysts were synthesized via a hydrothermal method, and systematically evaluated in a fixed-bed reactor. Physicochemical characterization revealed a four-stage phase evolution (single CeO2, CeO2-dominant, CeO2-Fe2O3 composite, and Fe2O3-dominant phases), each one with distinct electronic and structural properties directly governing gasification activity. Gasification tests demonstrated strong composition dependence, with different activity trends in the Ce-rich and Fe-rich regimes. In the Ce-rich regime, catalytic activity first increased and then declined as Fe doping rose, with Ce0.7Fe0.3 catalyst showing the highest reactivity (c(CO)/c(CO2) = 0.53). In contrast, in the Fe-rich range, Ce0.2Fe0.8 catalyst achieved the best performance (c(CO)/c(CO2) = 0.71). Further investigations showed that annealing time had little effect on catalytic activity, while NaBH4 reduction-etching improved performance at high concentrations, with 16 mL of NaBH4-treated catalyst (Ce0.8Fe0.2-16Re) demonstrating the highest activity. Residual char analyses confirms that Ce-rich catalysts promote oxygen-vacancy redox cycles leading to pore collapse, while Fe-rich catalysts rely on Fe redox cycling to induce mesopore formation. Therefore, this study elucidates the structure-activity relationship of CexFeyO catalysts and highlights defect engineering as a viable strategy for developing efficient, low-cost catalysts for solid waste gasification.
研究了cefeyo催化剂在秸秆炭CO2气化过程中的催化机理和性能。采用水热法合成了一系列cefeyo催化剂,并在固定床反应器上进行了系统评价。物理化学表征显示了四个阶段的相演化(单一CeO2相、CeO2-优势相、CeO2- fe2o3复合相和fe2o3 -优势相),每个阶段都具有不同的电子和结构性质,直接控制气化活性。气化试验显示出强烈的组分依赖性,在富ce和富fe状态下具有不同的活性趋势。在富ce区,随着Fe掺杂量的增加,催化活性先上升后下降,Ce0.7Fe0.3催化剂的反应活性最高(c(CO)/c(CO2) = 0.53)。相反,在富铁范围内,Ce0.2Fe0.8催化剂的性能最好(c(CO)/c(CO2) = 0.71)。进一步的研究表明,退火时间对催化活性影响不大,而NaBH4还原蚀刻在高浓度下提高了催化活性,其中16 mL NaBH4处理的催化剂(Ce0.8Fe0.2-16Re)表现出最高的活性。残炭分析证实富ce催化剂促进氧空位氧化还原循环导致孔隙坍塌,而富Fe催化剂则依靠Fe氧化还原循环诱导介孔形成。因此,本研究阐明了cefeyo催化剂的构效关系,并强调缺陷工程是开发高效、低成本固体废物气化催化剂的可行策略。
{"title":"CexFeyO catalysts for efficient char-CO2 gasification: Tuning oxygen vacancies and redox properties","authors":"Yinglu Zhang ,&nbsp;Yun Hao ,&nbsp;Weiwei Wu ,&nbsp;Ruijie Liang ,&nbsp;Shihao Lv ,&nbsp;Wenran Gao ,&nbsp;Zhiliang Wu ,&nbsp;Yan Chen ,&nbsp;Shu Zhang","doi":"10.1016/j.fuproc.2025.108378","DOIUrl":"10.1016/j.fuproc.2025.108378","url":null,"abstract":"<div><div>This study investigates the catalytic mechanisms and performance of Ce<sub>x</sub>Fe<sub>y</sub>O catalysts in the CO<sub>2</sub> gasification of straw char. A series of Ce<sub>x</sub>Fe<sub>y</sub>O catalysts were synthesized via a hydrothermal method, and systematically evaluated in a fixed-bed reactor. Physicochemical characterization revealed a four-stage phase evolution (single CeO<sub>2</sub>, CeO<sub>2</sub>-dominant, CeO<sub>2</sub>-Fe<sub>2</sub>O<sub>3</sub> composite, and Fe<sub>2</sub>O<sub>3</sub>-dominant phases), each one with distinct electronic and structural properties directly governing gasification activity. Gasification tests demonstrated strong composition dependence, with different activity trends in the Ce-rich and Fe-rich regimes. In the Ce-rich regime, catalytic activity first increased and then declined as Fe doping rose, with Ce<sub>0.7</sub>Fe<sub>0.3</sub> catalyst showing the highest reactivity (c(CO)/c(CO<sub>2</sub>) = 0.53). In contrast, in the Fe-rich range, Ce<sub>0.2</sub>Fe<sub>0.8</sub> catalyst achieved the best performance (c(CO)/c(CO<sub>2</sub>) = 0.71). Further investigations showed that annealing time had little effect on catalytic activity, while NaBH<sub>4</sub> reduction-etching improved performance at high concentrations, with 16 mL of NaBH<sub>4</sub>-treated catalyst (Ce<sub>0.8</sub>Fe<sub>0.2</sub>-16<sub>Re</sub>) demonstrating the highest activity. Residual char analyses confirms that Ce-rich catalysts promote oxygen-vacancy redox cycles leading to pore collapse, while Fe-rich catalysts rely on Fe redox cycling to induce mesopore formation. Therefore, this study elucidates the structure-activity relationship of Ce<sub>x</sub>Fe<sub>y</sub>O catalysts and highlights defect engineering as a viable strategy for developing efficient, low-cost catalysts for solid waste gasification.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"280 ","pages":"Article 108378"},"PeriodicalIF":7.7,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis of imidazolium based gemini surfactants with ultralow critical micelle concentration for chemical enhanced oil recovery process 超低临界胶束浓度咪唑基gemini表面活性剂的合成
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-11-21 DOI: 10.1016/j.fuproc.2025.108363
Ghazal Hoseintabar , Mostafa Lashkarbolooki , Turaj Behrouz
A novel imidazolium-based ionic liquid ([HC14Im]Br) and two gemini cationic surfactants with different spacers constructed based on this ionic liquid (IL) monomer, abbreviated to [HC14Im-S-HC14Im]Br2, where S represents the spacer including propane 2-bromoacetate S1 (C7H10O4Br2) and hydroxypropane 2-bromoacetate S2 (C7H10O5Br2), were designed and synthesized. The characterization results confirm the structure of obtained surfactants. The results also confirmed that both GSs have higher surface activities compared to the conventional monomeric ionic liquid. Based on the surface tension of surfactant solutions (γ) and interfacial tensions (IFTs) of crude oil/surfactant solutions (σ), the effect of the hydroxyl functional group in the spacer on CMC, the γ and γ at the CMC point, and surface activities were evaluated. The lowest CMC value with high surface activity was achieved for [HC14Im-S-HC14Im]Br2 gemini surfactant with the spacer of C7H10O5Br2 (CMC = 1.4 × 10−6 mol/L based on SFT measurement and CMC = 3.13 × 10−6 mol/L based on IFT measurement). Ultralow IFT value after CMC point (σ < 0.1 mN/m) and wettability alteration toward neutral (θ = 88° at 4.64 × 10−7 mol/L) and water-wet (θ = 55° at 1.16× 10−7 mol/L) states lead to outstanding spreading coefficient and capillary number improvements.
设计并合成了一种新型咪唑离子液体([HC14Im]Br)和基于该离子液体(IL)单体构建的两种具有不同间隔剂的gemini阳离子表面活性剂,简称[HC14Im-S-HC14Im]Br2,其中S为间隔剂,包括2-溴乙酸丙烷S1 (C7H10O4Br2)和2-溴乙酸羟丙烷S2 (C7H10O5Br2)。表征结果证实了所得表面活性剂的结构。结果还证实,与传统的单体离子液体相比,这两种GSs具有更高的表面活性。基于表面活性剂溶液的表面张力(γ)和原油/表面活性剂溶液的界面张力(IFTs) (σ),评价了隔离剂中羟基官能团对CMC、CMC点的γ和γ以及表面活性的影响。以C7H10O5Br2为间隔剂的[HC14Im-S-HC14Im]Br2 gemini表面活性剂获得了具有较高表面活性的最低CMC值(SFT测量CMC = 1.4 × 10−6 mol/L, IFT测量CMC = 3.13 × 10−6 mol/L)。CMC点后的超低IFT值(σ < 0.1 mN/m)和润湿性向中性(4.64 × 10−7 mol/L时θ = 88°)和水湿(1.16× 10−7 mol/L时θ = 55°)转变,显著提高了扩散系数和毛细数。
{"title":"Synthesis of imidazolium based gemini surfactants with ultralow critical micelle concentration for chemical enhanced oil recovery process","authors":"Ghazal Hoseintabar ,&nbsp;Mostafa Lashkarbolooki ,&nbsp;Turaj Behrouz","doi":"10.1016/j.fuproc.2025.108363","DOIUrl":"10.1016/j.fuproc.2025.108363","url":null,"abstract":"<div><div>A novel imidazolium-based ionic liquid ([HC<sub>14</sub>Im]Br) and two gemini cationic surfactants with different spacers constructed based on this ionic liquid (IL) monomer, abbreviated to [HC<sub>14</sub>Im-S-HC<sub>14</sub>Im]Br<sub>2</sub>, where S represents the spacer including propane 2-bromoacetate S1 (C<sub>7</sub>H<sub>10</sub>O<sub>4</sub>Br<sub>2</sub>) and hydroxypropane 2-bromoacetate S2 (C<sub>7</sub>H<sub>10</sub>O<sub>5</sub>Br<sub>2</sub>), were designed and synthesized. The characterization results confirm the structure of obtained surfactants. The results also confirmed that both GSs have higher surface activities compared to the conventional monomeric ionic liquid. Based on the surface tension of surfactant solutions (<em>γ)</em> and interfacial tensions (IFTs) of crude oil/surfactant solutions (σ), the effect of the hydroxyl functional group in the spacer on CMC, the <em>γ</em> and <em>γ</em> at the CMC point, and surface activities were evaluated. The lowest CMC value with high surface activity was achieved for [HC<sub>14</sub>Im-S-HC<sub>14</sub>Im]Br<sub>2</sub> gemini surfactant with the spacer of C<sub>7</sub>H<sub>10</sub>O<sub>5</sub>Br<sub>2</sub> (CMC = 1.4 × 10<sup>−6</sup> mol/L based on SFT measurement and CMC = 3.13 × 10<sup>−6</sup> mol/L based on IFT measurement). Ultralow IFT value after CMC point (σ &lt; 0.1 mN/m) and wettability alteration toward neutral (θ = 88° at 4.64 × 10<sup>−7</sup> mol/L) and water-wet (θ = 55° at 1.16× 10<sup>−7</sup> mol/L) states lead to outstanding spreading coefficient and capillary number improvements.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"280 ","pages":"Article 108363"},"PeriodicalIF":7.7,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145570659","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Selective hydrodeoxygenation of BHET using bimetallic Pt–Sn/γ-Al2O3 catalysts: Catalyst design, reaction pathway, and performance evaluation Pt-Sn /γ-Al2O3双金属催化剂选择性加氢脱氧BHET:催化剂设计、反应途径及性能评价
IF 7.7 2区 工程技术 Q1 CHEMISTRY, APPLIED Pub Date : 2025-11-19 DOI: 10.1016/j.fuproc.2025.108367
Syarif Hidayat , Jeonghun Han , Jinsoo Kim , Hyun Tae Hwang , Xinxing Zhou , Jong In Choi , Haoxing Zhang , Do-Young Hong , Jeong-Myeong Ha , Seung-Soo Kim
In this research, bis(2-hydroxyethyl) terephthalate (BHET), an essential monomer obtained from the glycolysis of PET, served as a model compound for hydrodeoxygenation (HDO) over bimetallic Pt-Sn/γ-Al2O3 catalysts within a fixed-bed reactor at atmospheric pressure. A series of catalysts with varying Pt/Sn ratios (Pt7Sn3, Pt7.5Sn2.5, Pt8Sn2, and Pt8.5Sn1.5) were prepared via incipient wetness impregnation method and extensively characterized using XRD, BET, H2-TPR, NH₃-TPD, SEM-EDX, and XPS. Among the formulations, Pt7.5Sn2.5 exhibited optimal performance, achieving complete BHET conversion (100 %) and a deoxygenation degree of 94 % at 400 °C, with high selectivity toward benzene (40.56 %), toluene (7.59 %), and ethylbenzene (45.42 %). This superior activity is attributed to the synergistic interaction between Pt and Sn, which promotes efficient CO bond cleavage while minimizing over‑hydrogenation and cracking. Temperature studies revealed 400 °C to be the most favorable temperature for hydrocarbon selectivity and minimal gas-phase carbon loss, while 5 h time on stream testing confirmed catalyst with minimal coke formation. Reaction pathway analysis showed that BHET deoxygenation proceeded via benzoic acid and benzaldehyde intermediates. This study highlights the potential of PtSn catalysts to enable the mild and efficient deoxygenation of PET-derived compounds, promoting the sustainable upcycling of polyester waste. The proposed strategy provides a scalable and practical route for the chemical recycling of PET, contributing to a circular economy in plastic waste management.
在本研究中,从PET糖醇解中获得的重要单体-对苯二甲酸双(2-羟乙基)酯(BHET)在常压固定床反应器中作为双金属Pt-Sn/γ-Al2O3催化剂上加氢脱氧(HDO)的模型化合物。采用初湿浸渍法制备了不同Pt/Sn比的Pt7Sn3、Pt7.5Sn2.5、Pt8Sn2和Pt8.5Sn1.5催化剂,并用XRD、BET、H2-TPR、NH₃-TPD、SEM-EDX和XPS对其进行了表征。其中,Pt7.5Sn2.5表现出最优的性能,在400℃下实现了完全的bet转化率(100%)和94%的脱氧度,对苯(40.56%)、甲苯(7.59%)和乙苯(45.42%)具有较高的选择性。这种优异的活性归因于Pt和Sn之间的协同作用,促进了CO键的有效裂解,同时最大限度地减少了过氢化和裂解。温度研究表明,400°C是对烃类选择性和最小气相碳损失最有利的温度,而5 h的流上测试证实催化剂具有最小的焦炭形成。反应途径分析表明,BHET是通过苯甲酸和苯甲醛中间体进行脱氧的。本研究强调了PtSn催化剂的潜力,使pet衍生化合物能够温和有效地脱氧,促进聚酯废物的可持续升级回收。提出的战略为PET的化学回收提供了一条可扩展和实用的途径,有助于塑料废物管理的循环经济。
{"title":"Selective hydrodeoxygenation of BHET using bimetallic Pt–Sn/γ-Al2O3 catalysts: Catalyst design, reaction pathway, and performance evaluation","authors":"Syarif Hidayat ,&nbsp;Jeonghun Han ,&nbsp;Jinsoo Kim ,&nbsp;Hyun Tae Hwang ,&nbsp;Xinxing Zhou ,&nbsp;Jong In Choi ,&nbsp;Haoxing Zhang ,&nbsp;Do-Young Hong ,&nbsp;Jeong-Myeong Ha ,&nbsp;Seung-Soo Kim","doi":"10.1016/j.fuproc.2025.108367","DOIUrl":"10.1016/j.fuproc.2025.108367","url":null,"abstract":"<div><div>In this research, bis(2-hydroxyethyl) terephthalate (BHET), an essential monomer obtained from the glycolysis of PET, served as a model compound for hydrodeoxygenation (HDO) over bimetallic Pt-Sn/γ-Al<sub>2</sub>O<sub>3</sub> catalysts within a fixed-bed reactor at atmospheric pressure. A series of catalysts with varying Pt/Sn ratios (Pt7Sn3, Pt7.5Sn2.5, Pt8Sn2, and Pt8.5Sn1.5) were prepared via incipient wetness impregnation method and extensively characterized using XRD, BET, H<sub>2</sub>-TPR, NH₃-TPD, SEM-EDX, and XPS. Among the formulations, Pt7.5Sn2.5 exhibited optimal performance, achieving complete BHET conversion (100 %) and a deoxygenation degree of 94 % at 400 °C, with high selectivity toward benzene (40.56 %), toluene (7.59 %), and ethylbenzene (45.42 %). This superior activity is attributed to the synergistic interaction between Pt and Sn, which promotes efficient C<img>O bond cleavage while minimizing over‑hydrogenation and cracking. Temperature studies revealed 400 °C to be the most favorable temperature for hydrocarbon selectivity and minimal gas-phase carbon loss, while 5 h time on stream testing confirmed catalyst with minimal coke formation. Reaction pathway analysis showed that BHET deoxygenation proceeded via benzoic acid and benzaldehyde intermediates. This study highlights the potential of Pt<img>Sn catalysts to enable the mild and efficient deoxygenation of PET-derived compounds, promoting the sustainable upcycling of polyester waste. The proposed strategy provides a scalable and practical route for the chemical recycling of PET, contributing to a circular economy in plastic waste management.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"280 ","pages":"Article 108367"},"PeriodicalIF":7.7,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145570647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Fuel Processing Technology
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