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Investigation and optimization of syngas generation during chemical looping gasification of municipal sludge using Fe/Al oxygen carrier 使用铁/铝氧载体对城市污泥进行化学循环气化过程中合成气生成的研究与优化
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-27 DOI: 10.1016/j.joei.2024.101844
Zewen An , Qihe Yuan , Hanqing Liang , Kun Wang , Xiaoying Yuan , Cuiping Wang , Qingjie Guo
To contribute to the reduction of carbon emissions, municipal sludge has to be utilized as a resource instead of being disposed of, especially since current sludge disposal methods encounter problems such as high dehydration energy consumption and secondary pollution. In this study, Fe/Al composite oxygen carriers (FOCs) were prepared using Al2O3 particles as carriers and Fe(NO3)3·9H2O as a precursor. Chemical looping gasification (CLG) of wet municipal sludge was conducted in a FOC-loaded fixed bed reactor, and the effect of reaction parameters and conditions on FOCs and syngas generation characteristics were analyzed by various methods. The results showed that the participation of water vapor in the gasification reaction significantly improved the hydrogen production rate of sludge gasification and avoided the over-reduction of the FOC. The vapor released from sludge significantly improved the thermal conversion efficiency of the sludge. Higher temperatures were conducive to the gasification reaction in the first stage, but when the reaction temperature reached 900 °C, the FOC slightly sintered, the reaction atmosphere was affected, and the hydrogen ratio in syngas started decreasing. Controlling the mixing ratio of FOC to sludge (O/H) was an important influencing factor for preparing high-quality syngas. When O/H was higher than 0.25, the quality of syngas decreased significantly. The conclusions obtained in this study can guide the selection of reaction conditions for the CLG of wet sludge using FOCs to prepare hydrogen-rich syngas.
为了减少碳排放,必须将市政污泥作为一种资源加以利用,而不是随意丢弃,尤其是目前的污泥处置方法存在脱水能耗高和二次污染等问题。本研究以 Al2O3 颗粒为载体,Fe(NO3)3-9H2O 为前驱体,制备了铁/铝复合氧载体(FOCs)。在装有 FOC 的固定床反应器中对湿市政污泥进行了化学循环气化(CLG),并采用多种方法分析了反应参数和条件对 FOCs 和合成气生成特性的影响。结果表明,水蒸气参与气化反应显著提高了污泥气化的产氢率,避免了 FOC 的过度还原。污泥释放出的水蒸气大大提高了污泥的热转化效率。在第一阶段,较高的温度有利于气化反应的进行,但当反应温度达到 900 ℃ 时,FOC 轻微烧结,反应气氛受到影响,合成气中的氢比例开始下降。控制 FOC 与污泥的混合比(O/H)是制备高质量合成气的重要影响因素。当 O/H 大于 0.25 时,合成气的质量明显下降。本研究得出的结论可指导利用 FOCs 制备富氢合成气的湿污泥 CLG 反应条件的选择。
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引用次数: 0
Study of the N2O formation mechanism in NOx-assisted heterogeneous catalytic combustion of soot in CeO2-based catalytic microchannel reactor 二氧化铈催化微通道反应器中氮氧化物辅助异相催化燃烧烟尘的 N2O 形成机理研究
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-26 DOI: 10.1016/j.joei.2024.101842
Zonglin Li , Pan Wang , Chengcheng Ao , Tong Yan , Lidong Zhang , Jianwen Cai , Haodong Meng
A CeO2-based catalytic microchannel reactor fixed-bed experiment was carried out to investigate the N2O formation in NOx-assisted catalytic combustion with fresh and hydrothermally aging catalysts during NOx-assisted heterogeneous catalytic combustion of soot. An evolved NOx-assisted soot catalytic combustion reaction mechanism was built to investigate N2O formation and key reaction pathways based on in situ Fourier Transform Infrared Spectroscopy (FTIR) diagnostics and destiny functional theory (DFT) computations. It was found that the temperature range of N2O formation was the same as the initiation temperature of soot catalytic combustion, while the significant catalytic activity of CeO2 catalyst induced a decrease in the temperature range of N2O formation. The CeO2 catalyst inhibited N2O formations from NOx-assisted soot catalytic combustion, while its inhibition effect was gradually weakened with the decrease of catalyst activities. The inhibitory effect of CeO2 on N2O was revealed in the reduction of CN formation rate in high temperatures. Fresh CeO2 catalyst increased the dominance in the CN formation reaction, reduced the CN production rate, and contributed to the decrease in the reaction rate of CNO oxidation by NO and NO2. The increase in the ratio of NOx to soot (β) was more sensitive to N2O formation than the ratio α (NO2 to NOx) and γ (O2 to NOx), led to a stronger inhibition of N2O formation.
基于 CeO2 的催化微通道反应器固定床实验研究了在 NOx 辅助异相催化燃烧烟尘过程中,新鲜催化剂和水热老化催化剂在 NOx 辅助催化燃烧过程中 N2O 的形成。基于原位傅立叶变换红外光谱(FTIR)诊断和命运函数理论(DFT)计算,建立了进化的氮氧化物辅助烟尘催化燃烧反应机理,以研究 N2O 的形成和关键反应途径。研究发现,N2O 的形成温度范围与烟尘催化燃烧的起始温度相同,而 CeO2 催化剂的显著催化活性导致 N2O 的形成温度范围减小。CeO2 催化剂可抑制 NOx 辅助烟尘催化燃烧中 N2O 的生成,但其抑制作用随催化剂活性的降低而逐渐减弱。CeO2 对 N2O 的抑制作用体现在高温下 CN 生成率的降低上。新的 CeO2 催化剂增加了 CN 生成反应的主导性,降低了 CN 的生成速率,并有助于降低 CNO 被 NO 和 NO2 氧化的反应速率。与α(NO2 与 NOx 的比率)和γ(O2 与 NOx 的比率)相比,NOx 与烟尘比率(β)的增加对 N2O 的形成更为敏感,从而导致对 N2O 形成的抑制作用更强。
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引用次数: 0
Assessment of performance and emission characteristics of CI engine using tyre pyrolysis oil and biodiesel blends by nano additives: An experimental study 通过纳米添加剂评估使用轮胎热解油和生物柴油混合物的 CI 发动机的性能和排放特性:实验研究
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-25 DOI: 10.1016/j.joei.2024.101825
Ajeet Kumar Prajapati , Shalu Yadav , Amit Kumar Gomey , Abhay Kumar Choubey , Rakesh Kumar
In the current study, the diesel engine performance, emission, and combustion have been investigated using tyre pyrolysis oil (TPO) and biodiesel blended with nano-additives. The effect of the blending ratio on fuel combustion and emission was evaluated. The tyre pyrolysis oil was derived from scrap tyres through the pyrolysis process and biodiesel was synthesized from used cooking oil (UCO) through the transesterification process. Moringa oleifera-derived strontium oxide (SrO) nanoparticles were mixed into the fuel to provide extra oxygen for better combustion. Three blended fuels were formulated as: a) 5 % biodiesel and 95 % TPO containing 50 ppm SrO nanoparticles (B5TPO95SrO50), b) 10 % biodiesel and 90 % TPO containing 100 ppm SrO nanoparticles (B10TPO90SrO100), c) 50 % TPO and 50 % biodiesel without nano-additives (B50TPO50). Among the blended fuels, B10TPO90SrO100 showed the best brake thermal efficiency at 31.4 % and a brake-specific fuel consumption of 0.21 kg/kWh at full load. The B5TPO95SrO50 blended fuel showed reduced emission parameters such as unburned hydrocarbon (HC), carbon monoxide (CO), and oxides of nitrogen (NOx) by 2.05 %, 8.30 %, and 18.00 %, respectively, as compared to the conventional diesel engine at an optimum engine load (27.9 Nm). Hence, waste tyre oil and UCO biodiesel blended with biogenic SrO nano additive can be considered a promising fuel for a sustainable environment.
在当前的研究中,使用轮胎热解油(TPO)和掺有纳米添加剂的生物柴油对柴油发动机的性能、排放和燃烧进行了研究。研究还评估了混合比例对燃料燃烧和排放的影响。轮胎热解油是通过热解工艺从废轮胎中提取的,而生物柴油则是通过酯交换工艺从废食用油中合成的。燃料中混入了从油杉中提取的纳米氧化锶(SrO)颗粒,以提供额外的氧气,从而改善燃烧。配制了三种混合燃料:a) 5 % 生物柴油和 95 % 热塑性烯烃,其中含有 50 ppm 的纳米氧化锶(B5TPO95SrO50);b) 10 % 生物柴油和 90 % 热塑性烯烃,其中含有 100 ppm 的纳米氧化锶(B10TPO90SrO100);c) 50 % 热塑性烯烃和 50 % 生物柴油,其中不含纳米添加剂(B50TPO50)。在混合燃料中,B10TPO90SrO100 的制动热效率最高,为 31.4%,满负荷时的制动油耗为 0.21 kg/kWh。与传统柴油发动机相比,B5TPO95SrO50 混合燃料在最佳发动机负荷(27.9 牛米)下的未燃碳氢化合物(HC)、一氧化碳(CO)和氮氧化物(NOx)等排放参数分别降低了 2.05 %、8.30 % 和 18.00 %。因此,废轮胎油和 UCO 生物柴油与生物源氧化锶纳米添加剂混合后,可被视为一种有前途的可持续环境燃料。
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引用次数: 0
Catalytic hydrothermal liquefaction of Azolla filiculoides into hydrocarbon rich bio-oil over a nickel catalyst in supercritical ethanol 镍催化剂在超临界乙醇中催化丝兰水热液化成富含碳氢化合物的生物油
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-23 DOI: 10.1016/j.joei.2024.101826
Yaoting Lin, Wei Zhou
Hydrothermal liquefaction (HTL) is one of the most promising thermochemical techniques for converting wet biomass into crude oil-like products (bio-oil). In this study, Catalytic hydrothermal liquefaction of Azolla filiculoides (AZ) was performed over a various loading of nickel (Ni) on magnesium oxide (MgO) catalyst for the higher and quality bio-oil production. The key operating parameters such as temperature, reaction holding time, amount of Ni on MgO supports catalyst, and reaction solvents were investigated in the presence of a hydrogen environment. There was a 12.8 wt% increase in bio-oil yield and a 6.3 wt% decrease in biochar yield with addition of 15 wt% Ni catalysts compared to the non-catalytic reaction bio-oil yield (44.0 wt%). Results confirmed the highest total bio-oil yield of 56.8 wt% was attained at 280 °C with the catalyst amount of 15 wt% at a residence time of 45 min. Gas chromatography-mass spectrometry (GC-MS), FT-IR, CHNS, TGA, and NMR analyses were performed on the bio-oil, identifying 32.8 % long-chain hydrocarbons (C12-C16) along with small amounts of alcohols, alkanes, and esters. The boiling point distribution revealed that bio-oil produced using the Ni/MgO catalyst contained a significantly higher proportion of diesel-range hydrocarbons (42.4 %). Furthermore, the bio-oil yield under ethanol solvent and Ni catalysts showed higher heating value (HHV) 42.2 MJ/kg. Overall in the presence of Ni hydrogenation efficient catalysts on MgO in the liquefaction reaction promoted the deoxygenation and hydrogenation reaction.
水热液化(HTL)是将湿生物质转化为类原油产品(生物油)的最有前途的热化学技术之一。在这项研究中,为了生产出更高质量的生物油,在氧化镁(MgO)催化剂上添加了不同含量的镍(Ni),对丝兰(AZ)进行了催化水热液化。在氢气环境下,对温度、反应保持时间、氧化镁载体催化剂上的镍含量和反应溶剂等关键操作参数进行了研究。与非催化反应生物油产量(44.0 wt%)相比,添加 15 wt% Ni 催化剂后,生物油产量增加了 12.8 wt%,生物炭产量减少了 6.3 wt%。结果证实,在 280 °C 温度下,催化剂用量为 15 wt%,停留时间为 45 分钟时,生物油总产量最高,达到 56.8 wt%。对生物油进行了气相色谱-质谱联用仪 (GC-MS)、傅立叶变换红外光谱 (FT-IR)、碳氢化合物分析仪 (CHNS)、热重分析仪 (TGA) 和核磁共振分析,确定了 32.8% 的长链碳氢化合物(C12-C16)以及少量的醇、烷和酯。沸点分布显示,使用 Ni/MgO 催化剂生产的生物油中柴油级碳氢化合物的比例明显更高(42.4%)。此外,在乙醇溶剂和镍催化剂作用下产生的生物油显示出更高的热值(HHV)42.2 MJ/kg。总之,在液化反应中,氧化镁上的镍加氢高效催化剂促进了脱氧和加氢反应。
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引用次数: 0
Fast co-pyrolysis characteristics of polyethylene terephthalate and epoxy resin from waste wind turbine blades 废弃风力涡轮机叶片中的聚对苯二甲酸乙二醇酯和环氧树脂的快速共热解特性
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-21 DOI: 10.1016/j.joei.2024.101841
Yong Yao , Yang Cao , Mumin Rao , Rui Shan , Jun Zhang
The present study systematically investigated the fast co-pyrolysis characteristics of epoxy resin and polyethylene terephthalate (PET) derived from waste wind turbine blades, with the aim of uncovering the possible synergistic effect in co-pyrolysis. The co-pyrolysis of epoxy resin and PET was beneficial to the formation of pyrolytic char, while the generation of small molecule gaseous products was restrained to a certain degree. The kinetic results revealed that the presence of epoxy resin dramatically reduced the energy barrier for PET decomposition into terephthalic acid (TPA) and vinyl benzoate via a cyclic transition state, finally resulting in an obvious reduction in the activation energy of the pyrolysis reaction. Remarkably, the activation energy for co-pyrolysis sharply decreased to around 150 kJ/mol at a low conversion rate. The co-pyrolysis presented a significant impact on the further transformation of primary pyrolysis products via decarboxylation, deoxygenation, decarbonylation, isomerization, and so on, thus contributing to the selective production of specified chemicals. Furthermore, the plausible reaction pathways and synergistic mechanisms between co-pyrolysis of epoxy resin and PET were discussed thoroughly.
本研究系统研究了从废弃风力涡轮机叶片中提取的环氧树脂和聚对苯二甲酸乙二酯(PET)的快速共热解特性,旨在揭示共热解过程中可能存在的协同效应。环氧树脂和聚对苯二甲酸乙二醇酯的共热解有利于热解炭的形成,而小分子气态产物的生成则受到一定程度的抑制。动力学结果表明,环氧树脂的存在大大降低了 PET 通过循环过渡态分解成对苯二甲酸(TPA)和苯甲酸乙烯酯的能障,最终导致热解反应的活化能明显降低。值得注意的是,在低转化率条件下,共热解的活化能急剧下降至 150 kJ/mol 左右。共热解对初级热解产物通过脱羧、脱氧、脱羰基、异构化等进一步转化产生了重大影响,从而有助于选择性地生产特定化学品。此外,还深入讨论了环氧树脂和 PET 共同热解的合理反应途径和协同机制。
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引用次数: 0
Experimental evaluation of municipal solid waste air-gasification in a pilot-scale reciprocating moving-grate furnace 中试规模往复式移动炉排炉中城市固体废物空气气化的实验评估
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-20 DOI: 10.1016/j.joei.2024.101833
Ao Bian , Ye Tian , Chao Zhang , Xiong Zhou , Wensheng Ma , Lian Hu , Liang Yuan
The increasing volume of municipal solid waste (MSW) worldwide presents significant environmental challenges, necessitating the development of efficient waste-to-energy (WtE) solutions. Among various thermochemical methods, gasification offers a promising approach for converting MSW into syngas, which can be utilized for energy generation. This study investigates the gasification characteristics of MSW in a pilot-scale reciprocating moving-grate furnace, focusing on the effect of key operating parameters such as equivalence ratio (ER), gasification temperature, and gasifying agent-staged ratio on gasification characteristics.
Seven experimental schemes were tested with varying lower heating values (LHV) of MSW (ranging from 6.98 to 15.1 MJ/kg) and throughputs (ranging from 0.77 to 1.67 tons per day) to assess the adaptability and stability of the moving-grate system under different conditions. The results indicate that an ER between 0.6 and 0.7, a gasification temperature of 760 °C, and a gasifying agent-staged ratio of 7:3 are optimal for achieving a maximum energy conversion efficiency of 71.6 %. It was observed that the LHV of syngas decreases when the gasification temperature exceeds 850 °C due to increased oxidation of light hydrocarbons. Moreover, the study highlights the influence of grate moving speed on residence time and reaction completeness, which are critical for optimizing syngas yield and quality.
The findings demonstrate that while the maximum energy conversion efficiency of the moving-grate system is lower than other reactor types, its lower capital and operating costs, due to the lack of dedicated feedstock pretreatment, make it a viable option for small-scale and pilot-scale applications. This study provides valuable insights into optimizing MSW gasification processes and underscores the potential of the moving-grate furnace for adaptable and cost-effective WtE applications. The novelty of this work lies in the comprehensive evaluation of the moving-grate gasification process under varied operating conditions, providing a foundation for future research on improving efficiency and reducing environmental impact in large-scale MSW management.
全球城市固体废物(MSW)数量的不断增加带来了巨大的环境挑战,因此有必要开发高效的废物变能源(WtE)解决方案。在各种热化学方法中,气化是将城市固体废物转化为合成气的一种有前途的方法,合成气可用于能源生产。本研究调查了 MSW 在中试规模往复式移动格栅炉中的气化特性,重点研究了等效比 (ER)、气化温度和气化剂阶段比等关键操作参数对气化特性的影响。在不同的 MSW 较低热值 (LHV) (从 6.98 到 15.1 MJ/kg)和吞吐量(从每天 0.77 到 1.67 吨)条件下测试了七种实验方案,以评估移动格栅系统在不同条件下的适应性和稳定性。结果表明,ER 值介于 0.6 和 0.7 之间、气化温度为 760 °C、气化剂分级比例为 7:3 是实现 71.6 % 最大能量转换效率的最佳条件。研究发现,当气化温度超过 850 ℃ 时,由于轻烃的氧化作用增加,合成气的 LHV 会降低。研究结果表明,虽然移动炉排系统的最大能量转换效率低于其他类型的反应器,但由于不需要专门的原料预处理,其资本和运营成本较低,因此是小规模和中试规模应用的可行选择。这项研究为优化 MSW 气化工艺提供了宝贵的见解,并强调了移动炉排炉在适应性强、成本效益高的 WtE 应用方面的潜力。这项工作的新颖之处在于在不同操作条件下对移动炉排气化过程进行了全面评估,为今后在大规模 MSW 管理中提高效率和减少环境影响的研究奠定了基础。
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引用次数: 0
Catalytic pyrolysis of wheat straw based on dual catalyst CaO/ZSM-5 with acid washing and torrefaction pretreatment to enhance aromatic yield in bio-oils 基于 CaO/ZSM-5 双催化剂的小麦秸秆催化热解与酸洗和预处理以提高生物油中的芳烃产量
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-19 DOI: 10.1016/j.joei.2024.101836
Chenyang Sun, Zhen Zhou, Hong Tian, Shan Cheng, Hengyu He, Binbin Chen
In this paper, the catalytic pyrolysis integrating combined pretreatment (acid washing and torrefaction) and dual catalysts was adopted to improve the quality of bio-oil and the selectivity of aromatic hydrocarbons. Combined pretreatment is a highly effective method to improve the quality of biomass feedstock. It was capable of the removal of alkali and alkaline earth metals from wheat straw, with a K removal rate of 97.79 %. Under the combined pretreatment, the aromatic hydrocarbon content in bio-oil increased to 68.8 % using the ZSM-5 catalyst alone. Compared with ZSM-5, CaO could remove part of the oxygenated functional groups and had a better acid removal effect, but the aromatic hydrocarbon yield was low to 7.95 %. After combined pretreatment using simulated aqueous phase bio-oil for acid washing, catalytic pyrolysis using CaO/ZSM-5 dual catalysts greatly enhanced the quality of the bio-oil. The oxygenated compounds content was reduced to 17.58 %, and the total hydrocarbon yield was increased to 82.42 %, especially the aromatic hydrocarbons yield was increased to 79.91 %, of which the monocyclic aromatic hydrocarbons were as high as 68.38 %, and the benzene, toluene, and xylene content reaching 49.39 %. Thus, integrating dual catalysts (CaO/ZSM-5) with combined pretreatment can effectively increase the aromatic yield for producing high-quality bio-oil.
本文采用联合预处理(酸洗和高温分解)和双催化剂的催化热解方法来提高生物油的质量和芳香烃的选择性。联合预处理是提高生物质原料质量的一种高效方法。它能够去除小麦秸秆中的碱金属和碱土金属,钾的去除率为 97.79%。在联合预处理中,单独使用 ZSM-5 催化剂,生物油中的芳香烃含量增加到 68.8%。与 ZSM-5 相比,CaO 可以去除部分含氧官能团,脱酸效果更好,但芳烃产率较低,仅为 7.95%。在使用模拟水相生物油进行酸洗的联合预处理后,使用 CaO/ZSM-5 双催化剂进行催化热解可大大提高生物油的质量。含氧化合物含量降低到 17.58%,总烃收率提高到 82.42%,尤其是芳香烃收率提高到 79.91%,其中单环芳香烃高达 68.38%,苯、甲苯和二甲苯含量达到 49.39%。因此,将双催化剂(CaO/ZSM-5)与联合预处理相结合,可有效提高生产优质生物油的芳烃产率。
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引用次数: 0
The impact of transition metals (Cr, Mn, and Co) on the performance of the 10%Ni/Al2O3-10%CeO2 catalysts in combined CO2 reforming and partial oxidation of methane 过渡金属(铬、锰和钴)对 10%Ni/Al2O3-10%CeO2 催化剂在二氧化碳重整和甲烷部分氧化联合反应中性能的影响
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-19 DOI: 10.1016/j.joei.2024.101834
Reza Babakouhi, Seyed Mehdi Alavi, Mehran Rezaei, Ehsan Akbari, Mohammad Varbar
This study explores the efficacy of Cr, Mn, and Co promoters in enhancing the performance of 10%Ni/Al2O3-10%CeO2 catalysts during methane combined reforming process, emphasizing improved metal dispersion and reduced carbon formation. The supports and catalysts were synthesized through mechanochemical and impregnation methods, respectively, and characterized using XRD, BET, TPR, TPO, and FESEM analyses. The synthesized catalysts exhibited a high BET surface area, ranging from 195 to 172 m2 g-1, along with a mesoporous structure characterized by pore sizes between 2 and 12 nm. The introduction of Cr significantly enhanced catalyst performance, resulting in 70.5 % CH4 and 69.1 % CO2 conversions in dry reforming. TPO analysis indicated reduced carbon deposition on promoted catalysts by enhancing Ni dispersion and carbon reactivity. The 10%Ni–3%Cr/Al2O3-10%CeO2 catalyst demonstrated stability over 440 min at 700 °C, achieving 84.9 % CH4 and 68.1 % CO2 conversions in combined reforming. The TPO analysis indicated an absence of carbon deposition on the catalyst surface during combined reforming, which was corroborated by the FESEM analysis. Furthermore, the influence of operating parameters on catalyst efficiency in both dry and combined reforming processes was investigated. As GHSV increased from 8000 to 24,000 ml/h.gcat, CH4 conversion declined in dry reforming and combined reforming, dropping from 77 % to 66 % and from 86 % to 84 %, respectively. Also, in both processes, increasing the oxidizer contents (CH4: CO2 from 2:1 to 1:2, CH4: CO2: O2 from 1:1:0 to 1:1:0.35) led to an increase in CH4 conversion, while CO2 conversion decreased.
本研究探讨了铬、锰和钴促进剂在甲烷联合重整过程中提高 10%Ni/Al2O3-10%CeO2 催化剂性能的功效,重点是改善金属分散和减少碳的形成。分别通过机械化学法和浸渍法合成了载体和催化剂,并使用 XRD、BET、TPR、TPO 和 FESEM 分析对其进行了表征。合成的催化剂具有较高的 BET 表面积,范围在 195 到 172 m2 g-1 之间,并具有介孔结构,孔径在 2 到 12 nm 之间。铬的引入大大提高了催化剂的性能,在干转化过程中,CH4 和 CO2 的转化率分别达到 70.5% 和 69.1%。TPO 分析表明,通过提高镍的分散性和碳的反应性,减少了碳在促进催化剂上的沉积。10%Ni-3%Cr/Al2O3-10%CeO2 催化剂在 700 °C 下稳定运行 440 分钟,在联合转化过程中实现了 84.9% 的 CH4 转化率和 68.1% 的 CO2 转化率。TPO 分析表明,在联合转化过程中催化剂表面没有碳沉积,FESEM 分析也证实了这一点。此外,还研究了干法转化和联合转化过程中操作参数对催化剂效率的影响。随着 GHSV 从 8000 ml/h.gcat 增加到 24000 ml/h.gcat,干转化和联合转化过程中的 CH4 转化率均有所下降,分别从 77% 降至 66%,从 86% 降至 84%。此外,在这两种工艺中,提高氧化剂含量(CH4:CO2 从 2:1 提高到 1:2,CH4:CO2:O2 从 1:1:0 提高到 1:1:0.35)可提高 CH4 转化率,而降低 CO2 转化率。
{"title":"The impact of transition metals (Cr, Mn, and Co) on the performance of the 10%Ni/Al2O3-10%CeO2 catalysts in combined CO2 reforming and partial oxidation of methane","authors":"Reza Babakouhi,&nbsp;Seyed Mehdi Alavi,&nbsp;Mehran Rezaei,&nbsp;Ehsan Akbari,&nbsp;Mohammad Varbar","doi":"10.1016/j.joei.2024.101834","DOIUrl":"10.1016/j.joei.2024.101834","url":null,"abstract":"<div><div>This study explores the efficacy of Cr, Mn, and Co promoters in enhancing the performance of 10%Ni/Al<sub>2</sub>O<sub>3</sub>-10%CeO<sub>2</sub> catalysts during methane combined reforming process, emphasizing improved metal dispersion and reduced carbon formation. The supports and catalysts were synthesized through mechanochemical and impregnation methods, respectively, and characterized using XRD, BET, TPR, TPO, and FESEM analyses. The synthesized catalysts exhibited a high BET surface area, ranging from 195 to 172 m<sup>2</sup> g<sup>-1</sup>, along with a mesoporous structure characterized by pore sizes between 2 and 12 nm. The introduction of Cr significantly enhanced catalyst performance, resulting in 70.5 % CH<sub>4</sub> and 69.1 % CO<sub>2</sub> conversions in dry reforming. TPO analysis indicated reduced carbon deposition on promoted catalysts by enhancing Ni dispersion and carbon reactivity. The 10%Ni–3%Cr/Al<sub>2</sub>O<sub>3</sub>-10%CeO<sub>2</sub> catalyst demonstrated stability over 440 min at 700 °C, achieving 84.9 % CH<sub>4</sub> and 68.1 % CO<sub>2</sub> conversions in combined reforming. The TPO analysis indicated an absence of carbon deposition on the catalyst surface during combined reforming, which was corroborated by the FESEM analysis. Furthermore, the influence of operating parameters on catalyst efficiency in both dry and combined reforming processes was investigated. As GHSV increased from 8000 to 24,000 ml/h.gcat, CH<sub>4</sub> conversion declined in dry reforming and combined reforming, dropping from 77 % to 66 % and from 86 % to 84 %, respectively. Also, in both processes, increasing the oxidizer contents (CH<sub>4</sub>: CO<sub>2</sub> from 2:1 to 1:2, CH<sub>4</sub>: CO<sub>2</sub>: O<sub>2</sub> from 1:1:0 to 1:1:0.35) led to an increase in CH<sub>4</sub> conversion, while CO<sub>2</sub> conversion decreased.</div></div>","PeriodicalId":17287,"journal":{"name":"Journal of The Energy Institute","volume":"117 ","pages":"Article 101834"},"PeriodicalIF":5.6,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142310463","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
Experimental study on the effects of co-firing mode and air staging on the ultra-low load combustion assisted by water electrolysis gas (HHO) in a pulverized coal furnace 煤粉炉中水电解气(HHO)辅助超低负荷燃烧的共燃模式和空气分级影响试验研究
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-19 DOI: 10.1016/j.joei.2024.101828
Yize Zhang , Qiwei Wu , Yifan Zhu , Xiao Kang , Bingjun Hou , Hao Zhou
Developing zero-carbon fuel (H2/NH3) co-firing technology with pulverized coal can improve the low-load flame instability and pollutant emissions of boilers during peak shaving. In this study, we propose to assist the low-load combustion of coal powder furnaces with the safer water electrolysis gas (HHO). To further optimize the combustion strategy, a one-dimensional furnace combustion system coupled with an HHO gas generation and transportation system was used to investigate the effects of injection methods and air staging on the flue gas emission and auxiliary combustion characteristics of the lignite load reduction process and ultra-low load. The results indicate that reducing the coal combustion load achieves carbon reduction and reduces actual CO2 emissions. The excess air coefficient increases, resulting in higher NOX and lower CO emissions. Air staging can control NOX and CO emissions during load shedding, with a 40.49 % reduction in NOX at 30 % load. Under ultra-low load, HHO-assisted combustion increases the oxygen concentration in the furnace, increasing NOX emissions, while SO2 decreases and then increases. However, the effect of HHO gas premixed mode (PM) on NOX generation is weaker than that of staged mode (SM). As the flow rate of HHO increases, HHO-SM promotes the conversion of CO to CO2 and reduces CO emissions, while CO emissions under PM remain at ∼10 ppm. Both HHO injection methods exhibit assisted combustion effects for ultra-low load operation. Due to the different effects of the two on the recirculation zone inside the combustion, the auxiliary combustion effect of PM is superior than that of SM. At 1800L/h HHO, the decrease in combustion instability coefficient (βT) of PM is 57.14 %, higher than that of SM. Air staging is beneficial for stable combustion under ultra-low load, but it can affect the auxiliary combustion of HHO gas. Under ultra-low load HHO co-firing conditions, 11%-OFA can also control NOX and CO emissions.
开发煤粉与零碳燃料(H2/NH3)共燃技术可改善锅炉在调峰期间的低负荷火焰不稳定性和污染物排放。在本研究中,我们建议使用更安全的水电解气体(HHO)来辅助煤粉炉的低负荷燃烧。为了进一步优化燃烧策略,我们利用一个与 HHO 气体生成和输送系统耦合的一维炉膛燃烧系统,研究了喷射方法和空气分段对褐煤减负荷过程和超低负荷时烟气排放和辅助燃烧特性的影响。结果表明,降低燃煤负荷可实现减碳,减少二氧化碳的实际排放量。过量空气系数增加,导致 NOX 增加,CO 排放减少。空气分级可控制减载过程中的 NOX 和 CO 排放,在 30% 负载时,NOX 可减少 40.49%。在超低负荷下,HHO 辅助燃烧增加了炉内氧气浓度,从而增加了 NOX 排放,而 SO2 则先减少后增加。然而,HHO 气体预混模式(PM)对 NOX 生成的影响弱于分段模式(SM)。随着 HHO 流量的增加,HHO-SM 会促进 CO 向 CO2 的转化并减少 CO 的排放,而 PM 下的 CO 排放则保持在 10 ppm 左右。两种 HHO 喷射方法在超低负荷运行时都表现出助燃效果。由于两者对燃烧内部再循环区的影响不同,PM 的辅助燃烧效果优于 SM。在 1800L/h HHO 条件下,PM 的燃烧不稳定系数(βT)下降率为 57.14%,高于 SM。空气分级有利于超低负荷下的稳定燃烧,但会影响 HHO 气体的辅助燃烧。在超低负荷 HHO 辅助燃烧条件下,11%-OFA 也能控制 NOX 和 CO 的排放。
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引用次数: 0
Study on fuel-N conversion mechanism of ammonia-coal co-firing at different combustion stages 不同燃烧阶段氨煤共烧的燃料-氮转化机理研究
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-19 DOI: 10.1016/j.joei.2024.101829
Ping Chen , Xiang Li , Huichun Wang , Mingyan Gu , Kun Luo , Jianren Fan

The co-combustion of ammonia and pulverized coal can effectively reduce the carbon emission of thermal power generation. However, ammonia, as a carbon-free fuel, is rich in large amounts of nitrogen, which increases the risk of high NOx emissions. Therefore, it is important to clarify the influence mechanism of ammonia on the NO formation of coal volatile-N and coal char-N in the co-combustion, and to reveal the N oxidation pathway in different combustion stages.

In this study, simulations were carried out on the CHEMKIN software to investigate the generation characteristics of NO and the transformation mechanism of fuel-N at different combustion stages of ammonia-coal co-firing. The study showed that ammonia-blending combustion promoted the release of coal volatiles and the oxidation to NO. In the total NO generation during the ammonia-coal co-firing, the proportion of NO produced by ammonia-coupled coal char combustion was very low. Compared with ammonia-coupled coal combustion, the amount of NO produced in ammonia-coupled coal volatile combustion was significantly reduced. Sensitivity analysis and rate of production (ROP) analysis indicated that the increase of H, OH, and O free radicals promoted the NO formation, and that NHi free radicals played an important role in the NO reduction. By analyzing the elementary path of NO generated from ammonia-coupled pulverized coal, coal volatiles and coal char combustion at 1400 °C and 10 % ammonia ratio, it can be seen that the main path of NO formation during ammonia-coupled coal volatiles combustion is VOL→HCN→NCO→NO, CHAR→NO, NH2→HNO→NO, compared with ammonia-coupled coal combustion. The proportion of NH2→NH→NO reaction paths decreased, while the proportion of NH2→N2, NCN→NCO→N2, and NH2→NNH→N2 reaction paths increased respectively, indicating that separation combustion promoted the reduction of NO by NHi free radicals while inhibiting the oxidation of N-containing components.

氨与煤粉共燃可有效减少火力发电的碳排放。然而,氨作为一种无碳燃料,富含大量的氮,增加了高氮氧化物排放的风险。因此,弄清氨在共燃过程中对煤挥发份-N 和煤炭-N 形成 NO 的影响机理,揭示不同燃烧阶段 N 的氧化途径具有重要意义。本研究利用 CHEMKIN 软件进行模拟,研究了氨煤共燃不同燃烧阶段 NO 的生成特征和燃料-N 的转化机理。研究表明,掺氨燃烧促进了煤挥发物的释放和氧化成 NO。在氨煤共烧过程中产生的 NO 总量中,氨耦合煤炭燃烧产生的 NO 所占比例很低。与氨耦合煤燃烧相比,氨耦合煤挥发燃烧产生的 NO 量明显减少。灵敏度分析和生成率(ROP)分析表明,H、OH 和 O 自由基的增加促进了 NO 的形成,而 NHi 自由基在 NO 的还原过程中发挥了重要作用。通过分析氨耦合煤粉、煤挥发物和煤焦在 1400 ℃、10%氨比条件下燃烧产生 NO 的基本路径,可以看出,与氨耦合煤燃烧相比,氨耦合煤挥发物燃烧过程中 NO 形成的主要路径是 VOL→HCN→NCO→NO、CHAR→NO、NH2→HNO→NO。NH2→NH→NO反应路径的比例下降,而NH2→N2、NCN→NCO→N2和NH2→NNH→N2反应路径的比例分别上升,表明分离燃烧促进了NHi自由基对NO的还原,同时抑制了含N成分的氧化。
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引用次数: 0
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Journal of The Energy Institute
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