Journal of The Energy Institute最新文献

{"title":"Chemical reaction kinetics simulation study on heterogeneous reactions of nitrogen oxides generation characteristics during coal-biomass co-firing in fluidized bed boiler","authors":"Shi'en Liu,&nbsp;Pengbo Zhao,&nbsp;Liangxu Dai,&nbsp;Ke Liu,&nbsp;Jiamiao Liu,&nbsp;Yingchao Nie,&nbsp;Chang'an Wang,&nbsp;Defu Che","doi":"10.1016/j.joei.2025.102395","DOIUrl":"10.1016/j.joei.2025.102395","url":null,"abstract":"<div><div>Coal-biomass co-firing in fluidized bed boilers is a critical technology for the clean energy transition, but predicting and controlling its nitrogen oxide emissions remains challenging. Existing simulation studies often directly simplified coal into light gases, overlooking the differences between gas-solid heterogeneous reactions and homogeneous reactions. To address this limitation, a new heterogeneous reaction model for coal-biomass co-combustion in fluidized bed boiler was proposed. The model integrates char-related heterogeneous reactions, and reveals the multiple roles of char as both a primary combustion component and a significant NO_<em>x</em> reductant. The sensitivity analysis combined with rate-of-production (ROP) kinetics modeling was conducted to investigate the influences of multiple factors on the microscopic mechanisms for nitrogen oxides formation. The findings reveal that biomass co-firing reduces nitrogen oxide emissions. This is mainly attributed to the reductive atmosphere created by volatile substances in biomass fuel, which, alongside the direct reduction by char, inhibits NO formation. Increasing the primary air ratio rises NO_<em>x</em> emissions, while N₂O emissions exhibit a downward trend, reflecting the shifting balance between homogeneous oxidation and heterogeneous reduction pathways on char surfaces. The implementation of fuel-staging strategies contributes to reducing nitrogen oxide emissions. The sensitivity and ROP analyses indicate that the reductive free radicals have an impact on nitrogen oxides formation. The HNO radical could be a crucial intermediate for the net production of NO, while the N₂O mainly originates from both the homogeneous reduction of NO_<em>x</em> by NCO, and relevant heterogeneous routes. As more wheat straw is introduced into the dilute phase zone, the increased hydrocarbon content leads to the influence of CH_<em>i</em> and its oxygen-containing derivatives on nitrogen oxides generation. These findings, obtained under typical fluidized bed conditions (∼850 °C and air atmosphere), offer a theoretical foundation for optimizing NO_<em>x</em> control strategies in practical fluidized bed boilers utilizing coal-biomass co-firing, thereby contributing to the efficient and clean combustion processes.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102395"},"PeriodicalIF":6.2,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614630","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}

{"title":"Pyrolysis behaviors of coal under NH3-blending conditions and combustion kinetics of co-pyrolyzed char","authors":"Renjie Zou,&nbsp;Wencong Qiu,&nbsp;Guangqian Luo,&nbsp;Mingda Li,&nbsp;Yi Xiao,&nbsp;Chunhui Sun,&nbsp;Tianyu Zhao,&nbsp;Haoyu Zhang,&nbsp;Jinfeng Zhou,&nbsp;Xian Li,&nbsp;Hong Yao","doi":"10.1016/j.joei.2025.102401","DOIUrl":"10.1016/j.joei.2025.102401","url":null,"abstract":"<div><div>The retrofitting of traditional coal-fired power plants with ammonia co-combustion technology has the potential for rapidly reducing CO₂ emissions. This study investigated the pyrolysis behaviors of coal under NH₃-blending conditions and the combustion kinetics of co-pyrolyzed char. It was found that NH₃ inhibited the release of CO₂ and H₂ during the pyrolysis of coal. NH₃ and its fragments interacted with the char and caused the migration of hydrogen and nitrogen elements to the char. The formation of additional micropores in the co-pyrolyzed coal char resulted in an enhanced specific surface area. Combustion kinetics experiments were conducted using a micro-fluidized bed coupled with a mass spectrometer (MFB-MS). The early-stage reaction rate of the co-pyrolyzed char exhibited a notable increase. At pyrolysis temperatures of 900–1000 °C, the combustion reactivity of the co-pyrolyzed char was higher than that of the sole-pyrolyzed char. However, the promotion of NH₃ on the ordering of the carbon skeleton structure increased at 1200 °C, resulting in a reduction in char reactivity. The char pyrolyzed with a 5 % NH₃ concentration exhibited the optimal combustion reactivity. The activation energies of the co-pyrolyzed char ranged from 100.24 to 129.37 kJ/mol, which decreased by 9.41–38.98 kJ/mol compared with that of sole-pyrolyzed char.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102401"},"PeriodicalIF":6.2,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786497","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}

{"title":"Strategic pretreatment tailoring biomass catalytic pyrolysis: Unraveling the synergy between physicochemical modification and reaction kinetics for sustainable biofuel production","authors":"Yongfei Li ,&nbsp;Nan An ,&nbsp;Hui Cao ,&nbsp;Zhibing Shen ,&nbsp;Yang Song ,&nbsp;Ying Tang","doi":"10.1016/j.joei.2025.102388","DOIUrl":"10.1016/j.joei.2025.102388","url":null,"abstract":"<div><div>Developing efficient biomass catalytic pyrolysis is pivotal for sustainable energy, yet recalcitrant lignocellulose structure hinders conversion efficiency. This study innovatively evaluates three chemical pretreatments (HNO₃, NaOH, H₂O₂) on diverse feedstocks (orange peels, walnut shells, wheat straw, wood chips, <em>Firmiana simplex</em> leaves) to elucidate their catalytic effects on pyrolysis behavior and kinetics. Through systematic characterization (elemental analysis, TG-DTG) and kinetic-thermodynamic modeling (Coats-Redfern method), we demonstrate that pretreatment selectively modifies biomass composition, thereby optimizing pyrolysis pathways. Based on the above research, we have obtained the following results: HNO₃ pretreatment maximizes hemicellulose/cellulose decomposition (up to 96.02 % weight loss for wood chips), reducing activation energy (Ea) by 49 % for wheat straw (60.32 → 30.80 kJ/mol) and lowering pyrolysis onset temperatures via glycosidic bond cleavage. NaOH treatment preferentially delignifies herbaceous biomass (wheat straw lignin removal: 35 %↑), increasing Ea by 21.5 % due to enhanced cellulose exposure, yet significantly boosts bio-oil precursor yield in active pyrolysis (200–400 °C). H₂O₂ oxidation promotes lignin depolymerization, shifting DTG peaks to lower temperatures (ΔT = −40 °C for walnut shells) and improving reaction entropy (ΔS↑ 25 % for <em>Firmiana simplex</em> leaves), facilitating volatile release. Thermodynamic analyses confirm reduced enthalpy (ΔH↓ 53.6 % for HNO₃-treated wheat straw) and Gibbs free energy (ΔG↓ 1.6 % for orange peels), indicating energetically favorable pyrolysis. Crucially, pretreatment reshapes biomass porosity and functional groups, augmenting catalytic accessibility during thermoconversion. This work provides a mechanistic framework for selecting pretreatment-catalysis synergies, advancing biomass valorization toward carbon–neutral energy. Our findings directly inform the design of integrated biorefineries for high-yield biofuel production, aligning with circular economy goals.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102388"},"PeriodicalIF":6.2,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614515","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}

{"title":"Experimental study on the combustion characteristics and pollutant properties of coal/ammonia/biomass co-combustion based on a 90 kW one-dimensional furnace","authors":"Jingwen Liu,&nbsp;Kunquan He,&nbsp;Qiwei Wu,&nbsp;Hao Zhou","doi":"10.1016/j.joei.2025.102389","DOIUrl":"10.1016/j.joei.2025.102389","url":null,"abstract":"<div><div>One of the core paths to reduce carbon emissions globally is to promote the low-carbon transition of the traditional coal power industry, in which the co-firing of coal with zero-carbon fuels (e.g., biomass, ammonia) for power generation has become a key technology direction. This study conducted an experimental study of biomass and bituminous coal/ammonia at different co-firing ratios based on a 90 kW one-dimensional combustion furnace. The effects of different biomass proportions (0 %–30 %) on combustion temperature, flue gas composition, unburned carbon, and fly ash characteristics of coal and coal/ammonia ratio of 4:1 co-firing system were investigated. The study found that the addition of biomass in coal and coal/ammonia co-firing systems led to an increase in furnace temperature, while combustion stability exhibited slight fluctuations but remained within an acceptable range. As the biomass co-firing ratio increased from 0 % to 30 %, NO_x concentrations decreased from 429.6 ppm to 263.1 ppm in the coal-biomass system, and from 465.8 ppm to 395.0 ppm in the coal-ammonia-biomass system. Concurrently, SO₂ emissions exhibited a declining trend across both fuel combinations. The fuel burnout characteristics were improved. The particle size of fly ash decreased after the co-combustion of pulverized coal and ammonia, and the addition of biomass could improve this phenomenon, but it was more prone to ash and slagging. An investigation into the effect of air staging on pollutant emissions revealed that the coal/ammonia/biomass mixture achieved the lowest NO_x emissions at a 20 % air staging ratio. This study establishes the feasibility of coal/ammonia/biomass co-combustion, supplying supporting data for reducing both pollutant and carbon emissions from coal-fired units.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102389"},"PeriodicalIF":6.2,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614631","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}

{"title":"Experimental investigation into the spray interaction and combustion characteristics of biodiesel/methanol dual-fuel sprays","authors":"Xiaolong Chang ,&nbsp;Jianbing Gao ,&nbsp;Zhenbin Chen ,&nbsp;Xiaochen Wang ,&nbsp;Haibin He ,&nbsp;Jie Wu ,&nbsp;Erjiang Hu","doi":"10.1016/j.joei.2025.102396","DOIUrl":"10.1016/j.joei.2025.102396","url":null,"abstract":"<div><div>This study presents the first systematic optical investigation of spray interaction and combustion characteristics in biodiesel/methanol dual-fuel direct injection system, conducted in a constant‐volume combustion chamber using Schlieren imaging. Individual biodiesel and methanol spray behaviors were first compared under non‐reactive conditions at injection pressures of 60, 80, and 100 MPa, revealing that biodiesel sprays exhibit longer penetration and narrower cone angles, whereas methanol sprays show finer atomization and wider dispersion. Dual‐spray collision and combustion characteristics were then analyzed by varying injection intervals (Δ<em>t</em>) and sequencing. Results indicate that increasing Δ<em>t</em> reduces spray penetration at 60 MPa while enhancing it at 100 MPa. Maximum spray area and lateral dispersion occurs at <em>Δt</em> = 1.0 ms; beyond this, spatial decoupling limits atomization efficiency. The collision length decreases with increasing Δ<em>t</em>, while collision width peaks at <em>Δt</em> = 1.0 ms. Methanol-first injection induced localized cooling due to its high latent heat, delaying biodiesel evaporation. In contrast, biodiesel-first injection produced a more cohesive initial spray, followed by rapid methanol dispersion, enhancing overall mixing and spray area. At 100 MPa, longer Δ<em>t</em> reduces spray overlap and interaction, while shorter intervals facilitate greater jet convergence and larger spray areas. Ignition consistently initiates at the spray interaction region, with flame morphology and luminosity strongly influenced by injection strategies. Methanol‐first strategies facilitates early ignition but suppresses subsequent biodiesel ignition due to the evaporative cooling, whereas biodiesel‐first strategies yield higher overall flame luminosity due to soot formation. This work provides new quantitative insights into how injection parameters affects dual-spray collision and combustion performance, offering practical guidance for optimizing injection strategies in renewable dual-fuel engines.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102396"},"PeriodicalIF":6.2,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614518","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}

{"title":"Upgrading of pyrolysis tire-derived oil through fractional condensation and subsequent oxidative desulphurisation","authors":"Adam J. Stander,&nbsp;Marisana A. Masha,&nbsp;George M. Teke,&nbsp;Somayeh Farzad,&nbsp;Johannes H. Knoetze,&nbsp;Cara E. Schwarz,&nbsp;Johann F. Görgens","doi":"10.1016/j.joei.2025.102394","DOIUrl":"10.1016/j.joei.2025.102394","url":null,"abstract":"<div><div>Pyrolysis of waste tire rubber produces three crude products: tire-derived oil (TDO), pyrolysis char and pyrolysis gas. While char and gas have diverse functional applications, crude TDO typically does not meet specifications for premium commercial fuel, due to its low quality and chemical heterogeneity. Hence, this study upgraded TDO to higher-quality fractions through a combination of thermal-desulphurization, fractional condensation of hot pyrolysis volatiles into three TDO fractions, and oxidative desulphurization (ODS). Key findings showed significant fractionation was achieved in the boiling point range of a typical crude TDO (54.41–246.23 °C), thereby separating from each other the light-cut (48.99–77.32 °C), medium-cut (74.98–225.25 °C), and heavy-cut (133.12–288.75 °C) fractions. The heaviest TDO fraction met all marine bunker oil specifications, except for sulphur content, while the medium TDO fraction met commercial diesel specifications except for flash point and sulphur content. The lightest TDO fraction would require several upgrading steps to meet the specifications of naphtha, kerosene and/or gasoline. Further decreases of 55, 62 and 48 % in the sulphur contents of the heavy, medium and light TDO fractions, respectively, could be achieved by a typical ODS combined with solvent extraction. However, further development of these processes for sulphur removal is required to meet specific commercial fuel standards.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102394"},"PeriodicalIF":6.2,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681399","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}

{"title":"Deciphering PM10 formation in high-sodium coal gasification: Synergistic effects of mineral vaporization and fragmentation","authors":"Lei Huang ,&nbsp;Lingxue Kong ,&nbsp;Guanghui Zhang ,&nbsp;Tiantian Ma ,&nbsp;Xiaojun Xuan ,&nbsp;Jin Bai ,&nbsp;Wen Li","doi":"10.1016/j.joei.2025.102387","DOIUrl":"10.1016/j.joei.2025.102387","url":null,"abstract":"<div><div>This study elucidates the dual mechanisms governing PM₁₀ formation during high-sodium coal gasification through integrated experimental and modeling approaches. Utilizing a flat-flame burner reactor at 1200–1400 °C, we systematically investigated temperature-dependent particle morphology evolution and chemical speciation. The bimodal particle size distribution revealed distinct formation pathways: ultrafine particles (&lt;0.154 μm) predominantly originated from vaporization-nucleation of alkali/refractory elements, while larger particulates (0.154–10 μm) stemmed from mineral fragmentation. Elevated temperatures (Δ200 °C) enhanced Na/Si/Ca vaporization by 7.2/165/243-fold respectively, correlating with 178 % PM_0.05 yield increase. Notably, H₂-mediated reduction dominated Si/Ca/Mg release (53–68 %), contrasting with CO-driven Fe volatilization (66 %). The developed multiscale model incorporating char conversion kinetics, mineral thermodynamics, and aerosol dynamics successfully predicted particulate yields and particle size distribution transitions. These findings provide critical insights for optimizing gasifier operations to mitigate PM emissions in high-sodium coal utilization.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102387"},"PeriodicalIF":6.2,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614516","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}

{"title":"Rice straw derived silica rich ash catalyst for efficient hydrothermal liquefaction of rice straw to value added chemicals","authors":"Bijoy Biswas ,&nbsp;Mridusmita Dutta ,&nbsp;Shivani Thakur ,&nbsp;Yogalakshmi Kadapakkam Nandabalan ,&nbsp;Sandeep Kumar ,&nbsp;Rawel Singh","doi":"10.1016/j.joei.2025.102393","DOIUrl":"10.1016/j.joei.2025.102393","url":null,"abstract":"<div><div>In this study, hydrothermal liquefaction (HTL) of rice straw (RS) an abundant agricultural waste was carried out to produce bio-oil. Silica (SiO₂)-rich ash derived from RS was used as a catalyst. Different reaction parameters such as reaction temperatures (230–270 °C), residence times (15–45 min), catalytic dosage (5–15 wt%) and different solvents such as water (H₂O), Ethanol (EtOH), water-ethanol (H₂O-EtOH), water-methanol (H₂O-MeOH), and water-isopropyl alcohol (H₂O-IPA) solvent mixtures were employed. In non-catalytic HTL, the highest bio-oil yield (52.5 wt%) was obtained using an H₂O-EtOH solvent mixture compared to H₂O (14.75 wt%), EtOH (25.2 wt%), H₂O-MeOH (45.7 wt%), and H₂O-IPA (51.2 wt%) at temperature 250 °C for 30 min of reaction time. Using a SiO₂-rich ash catalyst further improved the bio-oil yield to 59.16 wt% at 250 °C for 30 min under the H₂O-EtOH solvent system. Catalytic HTL bio-oil showed a high content of phenolics (24.12 %), ketones/aldehydes (22.12 %), and hydrocarbons (18.61 %). The hydrogenation reaction was promoted in the presence of catalyst and the higher phenolic and hydrocarbon content was found in the catalytic bio-oil. The bio-oil obtained under catalytic conditions exhibited lower oxygen content (30.6 wt%) and a higher heating value (26.61 MJ/kg) compared to bio-oil obtained under non-catalytic reactions. This study highlights the potential of SiO₂ rich ash catalysts from RS biomass for producing quality bio-oil.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102393"},"PeriodicalIF":6.2,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614628","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}

{"title":"Effect of nitrogen-containing functional groups on the oxidation characteristics of polycyclic aromatic hydrocarbons: A combined study of ReaxFF MD simulations and quantum chemical calculations","authors":"Qingyang Liu,&nbsp;Haoye Liu,&nbsp;Tianyou Wang","doi":"10.1016/j.joei.2025.102391","DOIUrl":"10.1016/j.joei.2025.102391","url":null,"abstract":"<div><div>In this study, the effect of nitrogen-containing functional groups introduced by nitrogen-containing species on the oxidation characteristics of polycyclic aromatic hydrocarbons (PAHs) was explored with reactive force field molecule dynamics (ReaxFF MD) simulations and quantum chemical calculations. The results of oxidation degrees indicate nitrogen-containing functional groups promote the oxidation of PAHs to varying extents. The evolution of the number of aromatic rings further demonstrates that nitrogen-containing functional groups accelerate oxidative cleavage of aromatic rings into chain molecules more effectively than isoelectronic hydrocarbon functional groups. Reaction mechanism analysis indicates that nitrogen-containing functional groups have higher reactivity, making them more likely to react with O₂ and active radicals (O and OH radicals). Energy barrier analysis shows that the energy barrier for the H-abstraction by O₂ involving the amino group is lower than that of isoelectronic hydrocarbon functional groups. Meanwhile, the amino group lowers the energy barriers for both H-abstraction and O-addition reactions on the aromatic ring, greatly reducing the difficulty for active radicals to attack the aromatic ring. Overall, nitrogen-containing functional groups affect the oxidation characteristics of PAHs through two main effects: (1) Nitrogen-containing functional groups exhibit high reactivity, making them prone to rapid oxidation reactions with O₂ and active radicals; (2) Nitrogen-containing functional groups reduce the energy barriers of key oxidation reactions involving the aromatic ring, or maintain it at a lower level, facilitating the attack of active radicals on the aromatic rings. The synergistic effect of these two factors makes PAHs with nitrogen-containing functional groups more susceptible to oxidation.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102391"},"PeriodicalIF":6.2,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614596","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}

{"title":"Oxidation of n-heptane under CO2/O2: Quantum chemistry and SVUV-PIMS experiment","authors":"Yongfeng Liu ,&nbsp;Yuanchao Shao ,&nbsp;Jiahao Zhang ,&nbsp;Shengzhuo Yao ,&nbsp;Zhandong Wang ,&nbsp;Bin Guan ,&nbsp;Zijian Zhou ,&nbsp;Hua Sun","doi":"10.1016/j.joei.2025.102398","DOIUrl":"10.1016/j.joei.2025.102398","url":null,"abstract":"<div><div>To investigate the oxidation of n-heptane (C₇H₁₆) under CO₂/O₂ atmosphere, an oxidation model (COO model) is developed using quantum chemistry and Synchrotron Vacuum Ultraviolet Photoionization Mass Spectrometry (SVUV-PIMS) technology. Electrostatic potential (ESP) and Fukui-function analyses identify reaction sites for CO₂ with OH, H, CH₃, and CH₂ radicals and reveal reaction pathways. Oxidation experiment of C₇H₁₆ under CO₂/O₂ atmosphere is conducted using a jet-stirred reactor (JSR) developed with SVUV-PIMS, and the oxidation products at an equivalence ratio of 2/3, temperature range of 700–1000 K, and 1 atm are quantitatively analyzed. The results show that the COO model is applicable for the oxidation of C₇H₁₆ under CO₂/O₂ atmosphere, with a maximum error of 8.9 % in the oxidation of C₇H₁₆. A total of 29 oxidation products are identified, with C₂H₄ having the highest peak molar fraction of 1.7 × 10⁻². The Negative Temperature Coefficient (NTC) region for C₇H₁₆ oxidation under CO₂/O₂ atmosphere is delayed by 125 K compared to O₂, with the maximum reaction rate occurring at 750 K. CO₂ primarily inhibits the formation of OH and other radicals before 800 K and also reacts minimally with radicals such as OH, H, CH₃, and CH₂, thereby delaying the NTC temperature region of C₇H₁₆. In the reaction pathways CO₂+H→CO + OH and CO₂+OH→CO + HO₂, the highest intermediate energies are 1.75 kcal/mol higher and 73.17 kcal/mol lower than the reactants, respectively. In the pathways CO₂+CH₃→CO + H₂O + CH and CO₂+CH₂→CH₂O + CO, the highest intermediate energies are 147.65 kcal/mol higher and 64.13 kcal/mol lower than the reactants.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"124 ","pages":"Article 102398"},"PeriodicalIF":6.2,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614633","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}