Pub Date : 2025-11-08DOI: 10.1016/j.joei.2025.102370
Xiawen Yu, Zhenxing Bu, Quantian Li, Jianfen Li
This study aims to develop an efficient hydrogen production route by enhancing nickel-based catalysts for biomass pyrolysis toward syngas. To this end, a series of Pr-modified ZrO2-supported nickel catalysts were synthesized and compared with unmodified Ni/ZrO2 counterparts. The catalysts were systematically characterized to elucidate morphological and compositional changes induced by Pr doping. Evaluation of catalytic performance revealed a 29 % increase in hydrogen yield for the Pr-doped catalysts relative to the undoped system. Under optimized conditions—including a pyrolysis temperature of 900 °C, pyrolysis time of 30 min, calcination temperature of 500 °C, Ni loading of 5 wt%, and a Zr/Pr molar ratio of 8:2—the Pr-doped Ni/ZrO2 catalyst achieved a maximum H2 yield of 0.7359 L/g and exhibited remarkable catalytic stability. The enhancement in performance is mainly ascribed to the role of Pr doping, which not only stabilizes the ZrO2 support but also modulates the acid–base properties of the catalyst, thereby improving Ni dispersion and reinforcing the antioxidant capacity of the system. These combined effects contribute to highly efficient hydrogen production during biomass pyrolysis.
{"title":"Boosting hydrogen production in biomass pyrolysis via Pr - doped Ni/ZrO2 catalysts","authors":"Xiawen Yu, Zhenxing Bu, Quantian Li, Jianfen Li","doi":"10.1016/j.joei.2025.102370","DOIUrl":"10.1016/j.joei.2025.102370","url":null,"abstract":"<div><div>This study aims to develop an efficient hydrogen production route by enhancing nickel-based catalysts for biomass pyrolysis toward syngas. To this end, a series of Pr-modified ZrO<sub>2</sub>-supported nickel catalysts were synthesized and compared with unmodified Ni/ZrO<sub>2</sub> counterparts. The catalysts were systematically characterized to elucidate morphological and compositional changes induced by Pr doping. Evaluation of catalytic performance revealed a 29 % increase in hydrogen yield for the Pr-doped catalysts relative to the undoped system. Under optimized conditions—including a pyrolysis temperature of 900 °C, pyrolysis time of 30 min, calcination temperature of 500 °C, Ni loading of 5 wt%, and a Zr/Pr molar ratio of 8:2—the Pr-doped Ni/ZrO<sub>2</sub> catalyst achieved a maximum H<sub>2</sub> yield of 0.7359 L/g and exhibited remarkable catalytic stability. The enhancement in performance is mainly ascribed to the role of Pr doping, which not only stabilizes the ZrO<sub>2</sub> support but also modulates the acid–base properties of the catalyst, thereby improving Ni dispersion and reinforcing the antioxidant capacity of the system. These combined effects contribute to highly efficient hydrogen production during biomass pyrolysis.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102370"},"PeriodicalIF":6.2,"publicationDate":"2025-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517261","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}
Pub Date : 2025-11-07DOI: 10.1016/j.joei.2025.102369
Kun Li, Leming Cheng, Qifeng Yu, Weiguo Zhang
Co-firing of NH3 with coal became an interesting topic due to the issues of carbon dioxide emissions. The reactivity variations of NH3 with CO, as well as the formation of NO and N2O under H2O-free and H2O-containing condition is one of the important aspects during the coal and NH3 co-firing process. In this work, experimental and kinetic studies were conducted on the co-oxidation of CO and NH3 in a plug flow reactor to investigate these characteristics. Influencing parameters including temperature, initial CO and H2O concentration were examined. Results indicates that the onset temperature of NH3 decreases and the formation of NO and N2O increases with increasing initial CO concertation under H2O-free conditions. The presence of NH3 inhibits CO conversion due to their competition for OH. Under H2O-containing conditions, H2O reduces the onset temperature of the CO-NH3 co-oxidation and promotes CO burnout under both fuel-lean and fuel-rich conditions. Meanwhile, H2O inhibits NO formation while N2O generation was enhanced. This is attributed to increased OH level through the reactions H2O + O = 2OH and H2O + H = OH + H2, along with reduced concentrations of O and H radicals. These changes enhance CO reactivity in the early stages and alters NO formation pathway. The decrease in O radical suppresses the NH2 → HNO → NO pathway, while the increase in OH radical promotes NH2 to NH conversion. It enhances the NH2 → NH → NO and NH2 → NH → HNO → NO pathways. Additionally, the increased NH radical concentration favors the NH2 → NH → N2O pathway, which contributes to increased N2O yields.
由于二氧化碳排放的问题，NH3与煤共烧成为一个有趣的话题。无水和含水条件下NH3与CO的反应性变化以及NO和N2O的生成是煤与NH3共烧过程的重要方面之一。在这项工作中，通过实验和动力学研究在塞流反应器中CO和NH3共氧化来研究这些特性。考察了温度、CO初始浓度和H2O初始浓度等参数的影响。结果表明：在无h2o条件下，随着初始CO浓度的增加，NH3的起始温度降低，NO和N2O的生成增加；NH3的存在抑制了CO的转化，因为它们竞争OH。在含水条件下，H2O降低了CO- nh3共氧化的起始温度，促进了贫燃料和富燃料条件下CO的燃尽。同时，H2O抑制NO的生成，促进N2O的生成。这是由于H2O + O = 2OH和H2O + H = OH + H2反应增加了OH水平，同时O和H自由基浓度降低。这些变化在早期阶段增强了CO的反应性，改变了NO的形成途径。O自由基的减少抑制NH2→HNO→NO途径，而OH自由基的增加促进NH2到NH的转化。增强NH2→NH→NO和NH2→NH→HNO→NO通路。此外，NH自由基浓度的增加有利于NH2→NH→N2O途径，这有助于提高N2O产率。
{"title":"Experimental study and kinetic analysis of the role of H2O on CO-NH3 Co-oxidation in a plug flow reactor","authors":"Kun Li, Leming Cheng, Qifeng Yu, Weiguo Zhang","doi":"10.1016/j.joei.2025.102369","DOIUrl":"10.1016/j.joei.2025.102369","url":null,"abstract":"<div><div>Co-firing of NH<sub>3</sub> with coal became an interesting topic due to the issues of carbon dioxide emissions. The reactivity variations of NH<sub>3</sub> with CO, as well as the formation of NO and N<sub>2</sub>O under H<sub>2</sub>O-free and H<sub>2</sub>O-containing condition is one of the important aspects during the coal and NH<sub>3</sub> co-firing process. In this work, experimental and kinetic studies were conducted on the co-oxidation of CO and NH<sub>3</sub> in a plug flow reactor to investigate these characteristics. Influencing parameters including temperature, initial CO and H<sub>2</sub>O concentration were examined. Results indicates that the onset temperature of NH<sub>3</sub> decreases and the formation of NO and N<sub>2</sub>O increases with increasing initial CO concertation under H<sub>2</sub>O-free conditions. The presence of NH<sub>3</sub> inhibits CO conversion due to their competition for OH. Under H<sub>2</sub>O-containing conditions, H<sub>2</sub>O reduces the onset temperature of the CO-NH<sub>3</sub> co-oxidation and promotes CO burnout under both fuel-lean and fuel-rich conditions. Meanwhile, H<sub>2</sub>O inhibits NO formation while N<sub>2</sub>O generation was enhanced. This is attributed to increased OH level through the reactions H<sub>2</sub>O + O = 2OH and H<sub>2</sub>O + H = OH + H<sub>2</sub>, along with reduced concentrations of O and H radicals. These changes enhance CO reactivity in the early stages and alters NO formation pathway. The decrease in O radical suppresses the NH<sub>2</sub> → HNO → NO pathway, while the increase in OH radical promotes NH<sub>2</sub> to NH conversion. It enhances the NH<sub>2</sub> → NH → NO and NH<sub>2</sub> → NH → HNO → NO pathways. Additionally, the increased NH radical concentration favors the NH<sub>2</sub> → NH → N<sub>2</sub>O pathway, which contributes to increased N<sub>2</sub>O yields.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102369"},"PeriodicalIF":6.2,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517262","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}
Pub Date : 2025-11-07DOI: 10.1016/j.joei.2025.102361
Yu Fang , Jiquan Luo , Zhulian Li , Junnan Zhan , Kai Liu , Qibin Liu
Chemical looping reforming (CLR) offers a promising approach for low-carbon hydrogen production by integrating fuel conversion with inherent CO2 separation. In this study, iron-based oxygen carriers doped with nickel and copper were synthesized to improve reactivity and cyclic stability. Structural characterization via X-ray diffractometer (XRD) and energy-dispersive X-ray spectrometer (SEM/EDS) confirmed the formation of active phases including NiFe2O4 and CuFe2O4, which have homogeneous elemental dispersion and nanostructured morphologies. Temperature programmed reduction experiments in TGA revealed that Ni doping enhances reaction rates, while copper doping lowers the reduction temperature. Among the synthesized carriers, 1 wt%Cu–20NiFe exhibited the best overall performance in terms of methane conversion (82.45 %), hydrogen yield (74.40 mL/gOC), and carbon monoxide yield (22.04 mL/gOC) at 600 °C. Steam-assisted CLR experiments show that water significantly improved H2 production, and appropriate steam flow could maximize hydrogen yield while suppressing carbon deposition. Long-term redox cycling (200 cycles) verified the structural integrity and oxygen transfer stability of 1 wt%Cu–20NiFe. X-ray photoelectron spectroscopy (XPS) analyses across different reaction stages confirmed the cyclic migration of lattice oxygen and complete regeneration of the oxygen carrier. This work demonstrates that micro-doped Cu in Ni–Fe-based oxygen carriers effectively enhances CLR hydrogen production, providing a foundation for further scale-up and integration in chemical looping hydrogen systems.
{"title":"Development of a copper doped iron-based oxygen carrier for hydrogen production via mid-temperature chemical looping","authors":"Yu Fang , Jiquan Luo , Zhulian Li , Junnan Zhan , Kai Liu , Qibin Liu","doi":"10.1016/j.joei.2025.102361","DOIUrl":"10.1016/j.joei.2025.102361","url":null,"abstract":"<div><div>Chemical looping reforming (CLR) offers a promising approach for low-carbon hydrogen production by integrating fuel conversion with inherent CO<sub>2</sub> separation. In this study, iron-based oxygen carriers doped with nickel and copper were synthesized to improve reactivity and cyclic stability. Structural characterization via X-ray diffractometer (XRD) and energy-dispersive X-ray spectrometer (SEM/EDS) confirmed the formation of active phases including NiFe<sub>2</sub>O<sub>4</sub> and CuFe<sub>2</sub>O<sub>4</sub>, which have homogeneous elemental dispersion and nanostructured morphologies. Temperature programmed reduction experiments in TGA revealed that Ni doping enhances reaction rates, while copper doping lowers the reduction temperature. Among the synthesized carriers, 1 wt%Cu–20NiFe exhibited the best overall performance in terms of methane conversion (82.45 %), hydrogen yield (74.40 mL/g<sub>OC</sub>), and carbon monoxide yield (22.04 mL/g<sub>OC</sub>) at 600 °C. Steam-assisted CLR experiments show that water significantly improved H<sub>2</sub> production, and appropriate steam flow could maximize hydrogen yield while suppressing carbon deposition. Long-term redox cycling (200 cycles) verified the structural integrity and oxygen transfer stability of 1 wt%Cu–20NiFe. X-ray photoelectron spectroscopy (XPS) analyses across different reaction stages confirmed the cyclic migration of lattice oxygen and complete regeneration of the oxygen carrier. This work demonstrates that micro-doped Cu in Ni–Fe-based oxygen carriers effectively enhances CLR hydrogen production, providing a foundation for further scale-up and integration in chemical looping hydrogen systems.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102361"},"PeriodicalIF":6.2,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681402","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}
Pub Date : 2025-11-07DOI: 10.1016/j.joei.2025.102366
Ziwen Zhao, Hong Tian, Zhengye Chen, Zhangjun Huang, Shan Cheng, Siying Liu
This study employed torrefied wheat straw (260 °C) as feedstock to synthesize a bifunctional metal-modified composite zeolite catalyst through alkali treatment (NaOH), dual metal loading (Fe and Ni), and hierarchical MCM-41 construction. Catalytically assisted pyrolysis behaviour was investigated using a tube furnace and Py-GC/MS system, evaluating the effects of pyrolysis temperature and catalyst/feedstock mixing ratio on product distribution and bio-oil composition. Results indicate that at a catalyst/feedstock ratio of 3:2, bio-oil yield peaked at 28.41 % at 500 °C, concurrently achieving a maximum monocyclic aromatic content of 66.36 %. Elevating pyrolysis temperature promoted aromatic formation while significantly suppressing oxygenated compounds; notably, phenolic components decreased by 13.94 % at 500 °C, indicating the 1Ni1FeHR@M catalyst's potent deoxygenation capability. Further optimization of the catalyst/feedstock blending ratio revealed that a 3:2 ratio yielded the highest combined bio-oil and monocyclic aromatic hydrocarbon production (18.62 %), confirming this catalytic strategy effectively shifts the product distribution towards higher-value hydrocarbon fuels.
{"title":"Upgrading of bio-oil from torrefied wheat straw over Fe-Ni modified HZSM-5@MCM-41: Influence of pyrolysis temperature and catalyst-feedstock ratio","authors":"Ziwen Zhao, Hong Tian, Zhengye Chen, Zhangjun Huang, Shan Cheng, Siying Liu","doi":"10.1016/j.joei.2025.102366","DOIUrl":"10.1016/j.joei.2025.102366","url":null,"abstract":"<div><div>This study employed torrefied wheat straw (260 °C) as feedstock to synthesize a bifunctional metal-modified composite zeolite catalyst through alkali treatment (NaOH), dual metal loading (Fe and Ni), and hierarchical MCM-41 construction. Catalytically assisted pyrolysis behaviour was investigated using a tube furnace and Py-GC/MS system, evaluating the effects of pyrolysis temperature and catalyst/feedstock mixing ratio on product distribution and bio-oil composition. Results indicate that at a catalyst/feedstock ratio of 3:2, bio-oil yield peaked at 28.41 % at 500 °C, concurrently achieving a maximum monocyclic aromatic content of 66.36 %. Elevating pyrolysis temperature promoted aromatic formation while significantly suppressing oxygenated compounds; notably, phenolic components decreased by 13.94 % at 500 °C, indicating the 1Ni1FeHR@M catalyst's potent deoxygenation capability. Further optimization of the catalyst/feedstock blending ratio revealed that a 3:2 ratio yielded the highest combined bio-oil and monocyclic aromatic hydrocarbon production (18.62 %), confirming this catalytic strategy effectively shifts the product distribution towards higher-value hydrocarbon fuels.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102366"},"PeriodicalIF":6.2,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517313","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}
Pub Date : 2025-11-07DOI: 10.1016/j.joei.2025.102368
Xiao-Yu Zhang , Wen-Lin Li , Zhi-Hao Ma , Sheng Li , Wei-Wei Yan , Li Li , Xing-Shun Cong , Xian-Yong Wei , Zhi-Xin Li
The reverse water-gas shift (RWGS) reaction represents a critical pathway for CO2 valorization into syngas for Fischer-Tropsch synthesis and renewable energy storage. Although Co-based catalysts offer an economical and efficient solution, their application is affected by CO2 methanation reaction and carbon deposition, resulting in limitations that are difficult to balance between activity, selectivity and stability. This work provides an effective approach to enhance the RWGS reaction performance over Co-based supported catalysts through Y2O3 morphology engineering (nanoplates/NP, nanorods/NR, nanospheres/NS). Remarkably, Co/Y2O3-NR catalyst demonstrates exceptional, CO2 conversion (57.1 %), CO selectivity (99.3 %) and stability compared to Co/Y2O3-NP and Co/Y2O3-NS catalysts at 600 °C. Systematic characterization reveals that Y2O3-NR exhibits optimal Co dispersion, moderate metal-support interaction and preferential CO2 adsorption, resulting in its outstanding catalytic activity. Crucially, spatially segregated carbon deposition preserves active sites across Co/Y2O3 catalysts, enhancing the catalytic stability. These findings establish Y2O3 morphology engineering as an exemplary support material and provide mechanistic insights for designing high-performance Co-based supported catalysts in RWGS reaction via morphological engineering.
{"title":"Morphology engineering of support oxides boosted the catalytic performance over Co/Y2O3 catalysts in reverse water-gas shift reaction","authors":"Xiao-Yu Zhang , Wen-Lin Li , Zhi-Hao Ma , Sheng Li , Wei-Wei Yan , Li Li , Xing-Shun Cong , Xian-Yong Wei , Zhi-Xin Li","doi":"10.1016/j.joei.2025.102368","DOIUrl":"10.1016/j.joei.2025.102368","url":null,"abstract":"<div><div>The reverse water-gas shift (RWGS) reaction represents a critical pathway for CO<sub>2</sub> valorization into syngas for Fischer-Tropsch synthesis and renewable energy storage. Although Co-based catalysts offer an economical and efficient solution, their application is affected by CO<sub>2</sub> methanation reaction and carbon deposition, resulting in limitations that are difficult to balance between activity, selectivity and stability. This work provides an effective approach to enhance the RWGS reaction performance over Co-based supported catalysts through Y<sub>2</sub>O<sub>3</sub> morphology engineering (nanoplates/NP, nanorods/NR, nanospheres/NS). Remarkably, Co/Y<sub>2</sub>O<sub>3</sub>-NR catalyst demonstrates exceptional, CO<sub>2</sub> conversion (57.1 %), CO selectivity (99.3 %) and stability compared to Co/Y<sub>2</sub>O<sub>3</sub>-NP and Co/Y<sub>2</sub>O<sub>3</sub>-NS catalysts at 600 °C. Systematic characterization reveals that Y<sub>2</sub>O<sub>3</sub>-NR exhibits optimal Co dispersion, moderate metal-support interaction and preferential CO<sub>2</sub> adsorption, resulting in its outstanding catalytic activity. Crucially, spatially segregated carbon deposition preserves active sites across Co/Y<sub>2</sub>O<sub>3</sub> catalysts, enhancing the catalytic stability. These findings establish Y<sub>2</sub>O<sub>3</sub> morphology engineering as an exemplary support material and provide mechanistic insights for designing high-performance Co-based supported catalysts in RWGS reaction <em>via</em> morphological engineering.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102368"},"PeriodicalIF":6.2,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517257","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}
Pub Date : 2025-11-07DOI: 10.1016/j.joei.2025.102362
Jiawei Wu , Zhiwei Wang , Na Guo , Mengju Zhang , Zaifeng Li , Shuhua Yang , Tingzhou Lei
The catalytic co-pyrolysis of biomass and plastic waste is one of highly effective approaches for the production of hydrocarbons. However, the yield of hydrocarbons is still very low. The combination of CaO and ZSM-5 can improve the quality of hydrocarbon fuels. CaO/ZSM-5 catalyst was prepared by wet impregnation method. Material characterizations such as FTIR, XRD and SEM were carried out to examine the CaO/ZSM-5 catalyst. Catalytic co-pyrolysis experiments were conducted on pinewood and polypropylene (PP) using Py-GC/MS. The pyrolysis temperature was 500–700 °C. The sample mass was 0.1 ± 0.01 mg. During the pyrolysis of pinewood alone, the addition of CaO increased the yields of aldehydes, ketones, furans, aromatic hydrocarbons and aliphatic hydrocarbons, and decreased the yields of phenols, esters, acids, alcohols and N-compounds compared with that without catalysts. The addition of ZSM-5 decreased the yield of phenols and increased the yield of aromatic hydrocarbons. CaO/ZSM-5 can increase the yield of hydrocarbons, the order of influencing factors from high to low on hydrocarbons production was blend ratio of CaO to ZSM-5 > temperature > reaction time > blend ratio of raw material to catalyst. With the sufficient CaO loading, oxygen-containing compounds can be converted into to hydrocarbons. The yield of aliphatic hydrocarbon first increased and then decreased with the increasing of CaO loading. When pinewood: PP: CaO/ZSM-5 = 1:1:5, the highest yields of aliphatic hydrocarbons and aromatic hydrocarbons were 90.91 % and 5.05 %. It can reduce the discarding of plastic and the burning of biomass. These results provide some practical insights on hydrocarbons production from mixtures of pinewood and polypropylene using co-pyrolysis technology. The composition of liquid phase products in the co-pyrolysis of Pinewood and PP is relatively complex. How to efficiently separate and purify the high value-added chemicals and fuels is a research direction for the next step.
{"title":"Towards enhanced hydrocarbons from catalytic co-pyrolysis of pinewood and polypropylene with CaO/ZSM-5","authors":"Jiawei Wu , Zhiwei Wang , Na Guo , Mengju Zhang , Zaifeng Li , Shuhua Yang , Tingzhou Lei","doi":"10.1016/j.joei.2025.102362","DOIUrl":"10.1016/j.joei.2025.102362","url":null,"abstract":"<div><div>The catalytic co-pyrolysis of biomass and plastic waste is one of highly effective approaches for the production of hydrocarbons. However, the yield of hydrocarbons is still very low. The combination of CaO and ZSM-5 can improve the quality of hydrocarbon fuels. CaO/ZSM-5 catalyst was prepared by wet impregnation method. Material characterizations such as FTIR, XRD and SEM were carried out to examine the CaO/ZSM-5 catalyst. Catalytic co-pyrolysis experiments were conducted on pinewood and polypropylene (PP) using Py-GC/MS. The pyrolysis temperature was 500–700 °C. The sample mass was 0.1 ± 0.01 mg. During the pyrolysis of pinewood alone, the addition of CaO increased the yields of aldehydes, ketones, furans, aromatic hydrocarbons and aliphatic hydrocarbons, and decreased the yields of phenols, esters, acids, alcohols and N-compounds compared with that without catalysts. The addition of ZSM-5 decreased the yield of phenols and increased the yield of aromatic hydrocarbons. CaO/ZSM-5 can increase the yield of hydrocarbons, the order of influencing factors from high to low on hydrocarbons production was blend ratio of CaO to ZSM-5 > temperature > reaction time > blend ratio of raw material to catalyst. With the sufficient CaO loading, oxygen-containing compounds can be converted into to hydrocarbons. The yield of aliphatic hydrocarbon first increased and then decreased with the increasing of CaO loading. When pinewood: PP: CaO/ZSM-5 = 1:1:5, the highest yields of aliphatic hydrocarbons and aromatic hydrocarbons were 90.91 % and 5.05 %. It can reduce the discarding of plastic and the burning of biomass. These results provide some practical insights on hydrocarbons production from mixtures of pinewood and polypropylene using co-pyrolysis technology. The composition of liquid phase products in the co-pyrolysis of Pinewood and PP is relatively complex. How to efficiently separate and purify the high value-added chemicals and fuels is a research direction for the next step.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102362"},"PeriodicalIF":6.2,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517263","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}
The investigation of low-energy consumption and environmentally friendly solid adsorbents has emerged as one of the key research directions for carbon capture. This study demonstrates the successful development of a structurally tunable “three-level" lignin-based hierarchical porous carbon (HPC) material, featuring ultra-micro, micro-, and mesoporous structures, for efficient CO2 capture. Subsequently, fractal theory was applied to an in-depth analysis of the adjusting the ratio of templating agent (F127) and activator (KOH) could effectively modulate the ultra-micro, micro-, and meso-porous in lignin-based HPC. Various kinetic models were used to characterize the CO2 adsorption mechanism and the adsorption rate of lignin adsorbents under dynamic conditions. Most importantly, this study compares lignin-based HPC (MC1.5-K3) with conventional activated porous carbon (MIC-K3) and mesoporous carbon (MC1.5), highlighting the advantages of the “three-level" pore structure, that the combination of ultra-micro, micro-, and mesoporous is not a simple superposition but has a synergistic enhancement effect. The availability of mesoporous channels not only facilitates mass transfer and diffusion rate of CO2 within the particles but also increases the maximum number of ultra-microporous and microporous. Because the KOH activator successfully enters the particle interior through the mesoporous channels, it effectively etches the mesoporous walls to form additional adsorption sites. Additionally, comparing MC1.5-K3 with MIC-K3, it was found that HPC retains more surface functional groups. These factors collectively enhance the CO2 adsorption performance of lignin-based HPC. Under ambient conditions (30 °C, 1 bar), MC1.5-K3 achieved a static CO2 uptake of 3.26 mmol/g and a dynamic adsorption of 2.9 mmol/g, and has low adsorption heat, along with excellent cycling stability. Therefore, lignin-based HPC successfully incorporated abundant microporous, especially ultra-microporous adsorption sites, mesoporous transport channels, and surface functional groups, which significantly promoted CO2 adsorption. In summary, green HPC based on lignin shows great potential as an efficient solid adsorbent for carbon capture.
{"title":"Adjustable ultra-micro, micro-, and mesopores in lignin-based hierarchical porous carbon for CO2 adsorption","authors":"Zhaoming Li, Zhikai Wang, Xu Yang, Honghong Lyu, Boxiong Shen","doi":"10.1016/j.joei.2025.102363","DOIUrl":"10.1016/j.joei.2025.102363","url":null,"abstract":"<div><div>The investigation of low-energy consumption and environmentally friendly solid adsorbents has emerged as one of the key research directions for carbon capture. This study demonstrates the successful development of a structurally tunable “three-level\" lignin-based hierarchical porous carbon (HPC) material, featuring ultra-micro, micro-, and mesoporous structures, for efficient CO<sub>2</sub> capture. Subsequently, fractal theory was applied to an in-depth analysis of the adjusting the ratio of templating agent (F127) and activator (KOH) could effectively modulate the ultra-micro, micro-, and meso-porous in lignin-based HPC. Various kinetic models were used to characterize the CO<sub>2</sub> adsorption mechanism and the adsorption rate of lignin adsorbents under dynamic conditions. Most importantly, this study compares lignin-based HPC (MC1.5-K3) with conventional activated porous carbon (MIC-K3) and mesoporous carbon (MC1.5), highlighting the advantages of the “three-level\" pore structure, that the combination of ultra-micro, micro-, and mesoporous is not a simple superposition but has a synergistic enhancement effect. The availability of mesoporous channels not only facilitates mass transfer and diffusion rate of CO<sub>2</sub> within the particles but also increases the maximum number of ultra-microporous and microporous. Because the KOH activator successfully enters the particle interior through the mesoporous channels, it effectively etches the mesoporous walls to form additional adsorption sites. Additionally, comparing MC1.5-K3 with MIC-K3, it was found that HPC retains more surface functional groups. These factors collectively enhance the CO<sub>2</sub> adsorption performance of lignin-based HPC. Under ambient conditions (30 °C, 1 bar), MC1.5-K3 achieved a static CO<sub>2</sub> uptake of 3.26 mmol/g and a dynamic adsorption of 2.9 mmol/g, and has low adsorption heat, along with excellent cycling stability. Therefore, lignin-based HPC successfully incorporated abundant microporous, especially ultra-microporous adsorption sites, mesoporous transport channels, and surface functional groups, which significantly promoted CO<sub>2</sub> adsorption. In summary, green HPC based on lignin shows great potential as an efficient solid adsorbent for carbon capture.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102363"},"PeriodicalIF":6.2,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517230","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}
Pub Date : 2025-11-07DOI: 10.1016/j.joei.2025.102367
Longfei Wang , Yuanjun Tang , Guoneng Li , Jun Dong , Yao Fang , Wenwen Guo , Chao Ye
This study systematically investigates the effects of Fe-loading on the pyrolysis behavior of three key biomass components: cellulose, xylan, and lignin. Complementary analytical techniques, thermogravimetric analysis (TGA), thermogravimetry-mass spectrometry (TG-MS), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), were utilized to assess the impact of Fe-loading on: (i) pyrolysis characteristics, (ii) the combined pyrolysis index (CPI), (iii) small-molecule gas evolution, and (iv) tar product distribution. Results demonstrate that the loading of Fe(NO3)3 significantly reduced the initial pyrolysis temperatures of cellulose and xylan by ∼140 °C and ∼62 °C, respectively, resulting in 58 % and 37 % decreases in CPI values. Conversely, lignin exhibited a 111 % CPI increase under Fe loading conditions, attributable to accelerated aryl-ether bond cleavage. The presence of Fe enhanced CO2 evolution while suppressing H2O and CO generation in cellulose/xylan conditions. In contrast, it promoted CH4, H2, CO, and CO2 evolution during lignin pyrolysis. Py-GC/MS analysis indicated that the presence of Fe drives aromatization through deoxygenation pathways while inhibiting ring-opening depolymerization, consequently shifting tar composition toward higher-carbon-number aromatic hydrocarbons. The findings can serve as a valuable reference for the application and promotion of the high-value valorization of waste biomass.
{"title":"Synergistic effects of Fe-loading on pyrolysis characteristics of cellulose, xylan, and lignin: TG, TG-MS, and Py-GC/MS analysis","authors":"Longfei Wang , Yuanjun Tang , Guoneng Li , Jun Dong , Yao Fang , Wenwen Guo , Chao Ye","doi":"10.1016/j.joei.2025.102367","DOIUrl":"10.1016/j.joei.2025.102367","url":null,"abstract":"<div><div>This study systematically investigates the effects of Fe-loading on the pyrolysis behavior of three key biomass components: <em>cellulose</em>, <em>xylan</em>, and <em>lignin</em>. Complementary analytical techniques, thermogravimetric analysis (TGA), thermogravimetry-mass spectrometry (TG-MS), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), were utilized to assess the impact of Fe-loading on: (<em>i</em>) pyrolysis characteristics, (<em>ii</em>) the combined pyrolysis index (<em>CPI</em>), (<em>iii</em>) small-molecule gas evolution, and (<em>iv</em>) tar product distribution. Results demonstrate that the loading of Fe(NO<sub>3</sub>)<sub>3</sub> significantly reduced the initial pyrolysis temperatures of <em>cellulose</em> and <em>xylan</em> by ∼140 °C and ∼62 °C, respectively, resulting in 58 % and 37 % decreases in <em>CPI</em> values. Conversely, <em>lignin</em> exhibited a 111 % <em>CPI</em> increase under Fe loading conditions, attributable to accelerated aryl-ether bond cleavage. The presence of Fe enhanced CO<sub>2</sub> evolution while suppressing H<sub>2</sub>O and CO generation in <em>cellulose</em>/<em>xylan</em> conditions. In contrast, it promoted CH<sub>4</sub>, H<sub>2</sub>, CO, and CO<sub>2</sub> evolution during <em>lignin</em> pyrolysis. Py-GC/MS analysis indicated that the presence of Fe drives aromatization through deoxygenation pathways while inhibiting ring-opening depolymerization, consequently shifting tar composition toward higher-carbon-number aromatic hydrocarbons. The findings can serve as a valuable reference for the application and promotion of the high-value valorization of waste biomass.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102367"},"PeriodicalIF":6.2,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517256","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}
Pub Date : 2025-11-07DOI: 10.1016/j.joei.2025.102365
Dong Ye , Jingyi Feng , Jiahui Liu , Kai Zhu , Li Sun , Ruitang Guo
A series of WO3-modified CeOx-CrOx catalysts were synthesized via co-precipitation and systematically evaluated for selective catalytic reduction (SCR) performance. The optimal catalyst, with a W/(Ce + Cr) molar ratio of 0.8, demonstrated exceptional activity, achieving >90 % NOx conversion and >90 % N2 selectivity across a broad temperature window (150–350 °C) under a high gas hourly space velocity (GHSV) of 200,000 mL g−1 h−1. This performance significantly surpassed that of the unmodified CeOx-CrOx reference catalyst, which only maintained >90 % NOx conversion and N2 selectivity within a narrower range (150–200 °C). The enhanced catalytic performance was attributed to the introduction of WO3, which generated abundant surface Lewis acid sites, thereby improving NH3 adsorption capacity. Furthermore, the formation of metal tungstate species stabilized Cr3+ and Ce3+, disrupting redox cycling between the cations with higher and lower oxidation numbers. This stabilization reduced both the abundance and reducibility of high-valence metal cations and chemisorbed oxygen species, endowing the WO3-modified catalysts with balanced oxidative capacity to activate adsorbed NH3 while effectively suppressing its excessive oxidation to NOx and over-activation to -NH (a key intermediate in N2O formation). Consequently, the WO3-promoted catalysts exhibited both an expanded operational temperature window and enhanced N2 selectivity. Additionally, the catalysts demonstrated robust resistance to SO2 and H2O poisoning, providing critical insights into the optimization of CeOx-CrOx-based SCR catalysts and paving the way for their potential industrial implementation.
{"title":"Effectively broadening the operational temperature window of the CeOx-CrOx SCR catalyst by modifying WO3","authors":"Dong Ye , Jingyi Feng , Jiahui Liu , Kai Zhu , Li Sun , Ruitang Guo","doi":"10.1016/j.joei.2025.102365","DOIUrl":"10.1016/j.joei.2025.102365","url":null,"abstract":"<div><div>A series of WO<sub>3</sub>-modified CeO<sub><em>x</em></sub>-CrO<sub><em>x</em></sub> catalysts were synthesized via co-precipitation and systematically evaluated for selective catalytic reduction (SCR) performance. The optimal catalyst, with a W/(Ce + Cr) molar ratio of 0.8, demonstrated exceptional activity, achieving >90 % NO<sub><em>x</em></sub> conversion and >90 % N<sub>2</sub> selectivity across a broad temperature window (150–350 °C) under a high gas hourly space velocity (GHSV) of 200,000 mL g<sup>−1</sup> h<sup>−1</sup>. This performance significantly surpassed that of the unmodified CeO<sub><em>x</em></sub>-CrO<sub><em>x</em></sub> reference catalyst, which only maintained >90 % NO<sub><em>x</em></sub> conversion and N<sub>2</sub> selectivity within a narrower range (150–200 °C). The enhanced catalytic performance was attributed to the introduction of WO<sub>3</sub>, which generated abundant surface Lewis acid sites, thereby improving NH<sub>3</sub> adsorption capacity. Furthermore, the formation of metal tungstate species stabilized Cr<sup>3+</sup> and Ce<sup>3+</sup>, disrupting redox cycling between the cations with higher and lower oxidation numbers. This stabilization reduced both the abundance and reducibility of high-valence metal cations and chemisorbed oxygen species, endowing the WO<sub>3</sub>-modified catalysts with balanced oxidative capacity to activate adsorbed NH<sub>3</sub> while effectively suppressing its excessive oxidation to NO<sub><em>x</em></sub> and over-activation to -NH (a key intermediate in N<sub>2</sub>O formation). Consequently, the WO<sub>3</sub>-promoted catalysts exhibited both an expanded operational temperature window and enhanced N<sub>2</sub> selectivity. Additionally, the catalysts demonstrated robust resistance to SO<sub>2</sub> and H<sub>2</sub>O poisoning, providing critical insights into the optimization of CeO<sub><em>x</em></sub>-CrO<sub><em>x</em></sub>-based SCR catalysts and paving the way for their potential industrial implementation.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102365"},"PeriodicalIF":6.2,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517260","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}
Pub Date : 2025-10-30DOI: 10.1016/j.joei.2025.102355
Georg Daurer , Stefan Schwarz , Joshua Slawatycki , Martin Demuth , Christian Gaber , Christoph Hochenauer
The application of OH* chemiluminescence diagnostics is becoming increasingly prevalent in the combustion characterization of hydrogen. As the current literature is lacking a systematic study of OH* chemiluminescence in non-premixed turbulent natural gas (NG) and hydrogen (H2) flames, the present work was designed to address this research gap. Therefore, extensive experiments were performed on a semi-industrial burner operating at 50–100 kW in NG/H2–Air/O2 combustion modes, which were complemented by comprehensive numerical simulations, including 1D laminar counterflow diffusion flamelet calculations and full 3D CFD simulations of the semi-industrial furnace setup. In this way, an OH* chemistry model is presented that accurately predicts the global reaction zone characteristics and their difference between CH4 and H2 in air-fired and oxygen-fired flames. The comprehensive numerical approach, in conjunction with the subsequent study of different operating conditions, yielded novel insights into both combustion modeling and the underlying thermochemical phenomena, providing an essential contribution to the transition of the thermal energy sector towards hydrogen as an alternative carbon-free fuel.
{"title":"OH* chemiluminescence in non-premixed industrial natural gas/hydrogen flames under air-fuel and oxy-fuel conditions: Kinetics modeling and experimental validation","authors":"Georg Daurer , Stefan Schwarz , Joshua Slawatycki , Martin Demuth , Christian Gaber , Christoph Hochenauer","doi":"10.1016/j.joei.2025.102355","DOIUrl":"10.1016/j.joei.2025.102355","url":null,"abstract":"<div><div>The application of OH* chemiluminescence diagnostics is becoming increasingly prevalent in the combustion characterization of hydrogen. As the current literature is lacking a systematic study of OH* chemiluminescence in non-premixed turbulent natural gas (NG) and hydrogen (H<sub>2</sub>) flames, the present work was designed to address this research gap. Therefore, extensive experiments were performed on a semi-industrial burner operating at 50–100 kW in NG/H<sub>2</sub>–Air/O<sub>2</sub> combustion modes, which were complemented by comprehensive numerical simulations, including 1D laminar counterflow diffusion flamelet calculations and full 3D CFD simulations of the semi-industrial furnace setup. In this way, an OH* chemistry model is presented that accurately predicts the global reaction zone characteristics and their difference between CH<sub>4</sub> and H<sub>2</sub> in air-fired and oxygen-fired flames. The comprehensive numerical approach, in conjunction with the subsequent study of different operating conditions, yielded novel insights into both combustion modeling and the underlying thermochemical phenomena, providing an essential contribution to the transition of the thermal energy sector towards hydrogen as an alternative carbon-free fuel.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102355"},"PeriodicalIF":6.2,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145418671","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}
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