Q3 Energy

燃料化学学报

Pub Date : 2024-11-01 DOI: 10.1016/S1872-5813(24)60470-6

Yan YANG , Taochenxi GE , Yanan JIANG , Xian ZHANG , Yuan LIU

Macroporous catalysts often exhibit excellent mass and heat transfer properties, which can reduce pressure drop and mitigate hot spot formation during the reaction process. Addressing the issues of the active component sintering due to the strong exothermicity of CO₂ methanation and the demand for operation at high space velocities, in this work, a nickel-based catalyst with high surface area and large pore size and pore volume was prepared by in-situ growth of NiMgAl layered double hydroxide (NiMgAl-LDH) precursors on the surface of macroporous Al₂O₃. The effects of calcination temperature, reduction temperature, and space velocity on the catalyst structure and reaction performance were investigated. The results demonstrate that the catalyst phase composition can be controlled by adjusting the calcination temperature, while the reduction degree of Ni is regulated by altering the reduction temperature, which are effective in inhibiting the sintering of Ni, increasing the number of active Ni⁰ sites, and then enhancing the catalytic activity of Ni-MgO/Al₂O₃. By conducting the calcination of NiMgAl-LDH precursor at 400 °C and subsequent reduction at 650 °C, the resulted Ni-MgO/Al₂O₃ catalyst shows the highest active Ni surface area and exhibits the highest CO₂ conversion and CH₄ selectivity in the CO₂ methanation, suggesting that the surface area of metal nickel is a crucial factor for the catalytic performance of Ni-MgO/Al₂O₃. Furthermore, the Ni-MgO/Al₂O₃ catalyst performs well at a high space velocity of WHSV = 80000 mL/(g·h) and a good stability at 550 °C, where the CO₂ conversion and CH₄ selectivity keep at 54% and 79%, respectively.

大孔催化剂通常具有优异的传质和传热性能，可在反应过程中减少压降并缓解热点的形成。针对 CO2 甲烷化放热性强导致活性组分烧结以及需要在高空间速度下运行的问题，本研究通过在大孔 Al2O3 表面原位生长 NiMgAl 层状双氢氧化物（NiMgAl-LDH）前驱体，制备了一种具有高比表面积、大孔径和孔体积的镍基催化剂。研究了煅烧温度、还原温度和空间速度对催化剂结构和反应性能的影响。结果表明，通过调节煅烧温度可以控制催化剂的相组成，而通过改变还原温度可以调节 Ni 的还原程度，从而有效抑制 Ni 的烧结，增加活性 Ni0 位点的数量，进而提高 Ni-MgO/Al2O3 的催化活性。通过在 400 °C 下煅烧 NiMgAl-LDH 前驱体，然后在 650 °C 下还原，得到的 Ni-MgO/Al2O3 催化剂显示出最高的活性 Ni 表面积，在 CO2 甲烷化中表现出最高的 CO2 转化率和 CH4 选择性，这表明金属镍的表面积是 Ni-MgO/Al2O3 催化性能的关键因素。此外，Ni-MgO/Al2O3 催化剂在 WHSV = 80000 mL/(g-h) 的高空间速度下性能良好，在 550 °C 下稳定性良好，二氧化碳转化率和甲烷选择性分别保持在 54% 和 79%。

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引用次数: 0

Low-vanadium and high-activity SCR catalyst for low-temperature denitrification: Influence of vanadium precursor and surface vanadium concentration 用于低温脱硝的低钒高活性 SCR 催化剂：钒前驱体和表面钒浓度的影响

Q3 Energy

燃料化学学报

Pub Date : 2024-11-01 DOI: 10.1016/S1872-5813(24)60467-6

Xi TIAN , Peng YE , Qilong WU , Shangchao XIONG , Lina GAN , Jianjun CHEN

Nitrogen oxides (NO_x), as the main pollutants of air pollution, cause serious harm to the ecological environment and human health. SCR technology is widely used as the most effective method for treating NO_x. The core of SCR technology is SCR catalyst. The reaction temperature of traditional commercial catalysts is difficult to reach the optimal operating temperature range, so expanding the temperature window of V₂O₅/TiO₂ catalysts to the low-temperature region while reducing vanadium loading is a key issue to be solved. A series of V₂O₅/TiO₂ catalysts with different vanadium precursors and different vanadium loadings were prepared by solid-phase synthesis method. The physicochemical properties of the catalyst were analyzed by X-ray diffraction, X-ray photoelectron spectroscopy, temperature programmed desorption of ammonia and temperature programmed reduction of hydrogen. The denitrification activity of the catalyst was evaluated in a fixed bed reactor. The catalysts prepared with vanadyl oxalate (VOC₂O₄·xH₂O) and vanadyl acetylacetonate (VO(acac)₂) as vanadium precursors with a vanadium loading of 5% exhibited the highest denitrification activity, with a stable NO_x conversion of 100% within the temperature range of 200–350 °. Compared with the catalysts prepared with ammonium metavanadate (NH₄VO₃) and vanadyl sulfate (VOSO₄·xH₂O) as the vanadium precursors, the maximum activity temperature of VOC₂O₄-V5Ti and VO(acac)₂-V5Ti shifted towards the low-temperature region by about 150 °. Furthermore, the denitrification activity of catalyst with a low vanadium content (1%) prepared using VO(acac)₂ precursor was even higher than that of catalyst with a high vanadium content (6%) prepared using NH₄VO₃ precursor. Using VOC₂O₄ and VO(acac)₂ as vanadium precursors could effectively regulate the active sites and polymeric states on the catalysts, and promote the interaction of V atoms with different valence states to form more reductive V species (V⁴⁺), thus exhibiting excellent SCR reactivity. This study provided an effective method for the preparation of low-vanadium and high-activity denitrification catalysts at low temperatures.

氮氧化物（NOx）作为大气污染的主要污染物，对生态环境和人类健康造成严重危害。选择性催化还原（SCR）技术作为处理氮氧化物最有效的方法被广泛应用。SCR 技术的核心是 SCR 催化剂。传统商用催化剂的反应温度很难达到最佳工作温度范围，因此在降低钒负载的同时，将 V2O5/TiO2 催化剂的温度窗口扩大到低温区域是亟待解决的关键问题。本研究采用固相合成法制备了一系列不同钒前驱体和不同钒负载量的 V2O5/TiO2 催化剂。通过 X 射线衍射、X 射线光电子能谱、氨的温程解吸和氢的温程还原分析了催化剂的理化性质。在固定床反应器中对催化剂的脱硝活性进行了评估。以草酸钒（VOC2O4-xH2O）和乙酰丙酮酸钒（VO(acac)2）为钒前体制备的催化剂（钒负载量为 5%）脱硝活性最高，在 200-350 ° 的温度范围内氮氧化物转化率稳定在 100%。与以偏钒酸铵（NH4VO3）和硫酸钒（VOSO4-xH2O）为钒前体制备的催化剂相比，VOC2O4-V5Ti 和 VO（acac）2-V5Ti 的最高活性温度向低温区移动了约 150 °。此外，使用 VO(acac)2 前驱体制备的低钒含量（1%）催化剂的脱硝活性甚至高于使用 NH4VO3 前驱体制备的高钒含量（6%）催化剂。使用 VOC2O4 和 VO(acac)2 作为钒前驱体，可以有效调节催化剂上的活性位点和聚合态，促进不同价态的钒原子相互作用，形成还原性更强的钒物种（V4+），从而表现出优异的 SCR 反应活性。该研究为低温制备低钒高活性脱硝催化剂提供了一种有效的方法。

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引用次数: 0

Direct liquefaction behavior of Shenhua Shangwan coal under CO containing atmosphere 神华上湾煤在含 CO 大气环境下的直接液化行为

Q3 Energy

燃料化学学报

Pub Date : 2024-10-01 DOI: 10.1016/S1872-5813(24)60451-2

TANG Bowen, ZHANG Rui, LIU Haiyun, JIN Lijun, HU Haoquan

Direct coal liquefaction (DCL) under CO or syngas atmosphere is beneficial to reduce the cost of hydrogen production. Effects of CO on liquefaction process of Shangwan coal were investigated by comparing the liquefaction behavior in three atmospheres of CO, H_2, and N₂. Then, effects of different CO/H₂ ratios and catalysts on the liquefaction process in syngas were investigated. The results indicated that the oil yield under CO atmosphere reached 43.1%, which was 4.2% lower than that under H₂, but 10.2% higher than that under N₂. The liquefaction performance was further improved by adding the Shenhua 863 catalyst. It is analyzed that CO promoted liquefaction in two ways: water-gas shift reaction and the reaction between CO and organic structures of coal. Through characterization of the products by GC-MS and FT-IR, it was found that CO makes benzenes, aliphatics, and oxygen-containing compounds in liquefied oil simultaneously increased. The effect on functional groups and free radicals concentration in the solid products was not obvious. The experimental results under syngas showed that the highest oil yield, 57.4%, can be obtained in DCL with 20% CO syngas, and further improved by increasing moisture content of coal appropriately. In addition, the Shenhua 863 catalyst had a good catalytic effect on the liquefaction process and also water-gas shift reaction.

在 CO 或合成气气氛下进行煤直接液化（DCL）有利于降低制氢成本。通过比较 CO、H2 和 N2 三种气氛下的液化行为，研究了 CO 对上湾煤液化过程的影响。然后，研究了不同 CO/H2 比率和催化剂对合成气液化过程的影响。结果表明，CO气氛下的产油率达到43.1%，比H2气氛下低4.2%，但比N2气氛下高10.2%。加入神华 863 催化剂后，液化性能进一步提高。据分析，CO 促进液化的方式有两种：水煤气变换反应和 CO 与煤的有机结构反应。通过 GC-MS 和 FT-IR 对产物的表征发现，CO 使液化油中的苯类、脂肪族和含氧化合物同时增加。对固体产物中官能团和自由基浓度的影响并不明显。合成气条件下的实验结果表明，在使用 20% CO 合成气的 DCL 中，可获得最高的出油率（57.4%），并可通过适当提高煤的含水率进一步提高出油率。此外，神华 863 催化剂对液化过程和水煤气变换反应均有良好的催化效果。

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引用次数: 0

Mechanism of methanol synthesis from CO2 hydrogenation over Rh16/In2O3 catalysts: A combined study on density functional theory and microkinetic modeling Rh16/In2O3 催化剂氢化 CO2 合成甲醇的机理：密度泛函理论与微动力学模型的结合研究

Q3 Energy

燃料化学学报

Pub Date : 2024-10-01 DOI: 10.1016/S1872-5813(24)60460-3

WANG Yuning , GONG Jiesong , ZHOU Jiabin , CHEN Zhiyuan , TIAN Dong , NA Wei , GAO Wengui

In this study, the hydrogenation of carbon dioxide (CO₂) to methanol (CH₃OH) over Rh₁₆/In₂O₃ catalyst was studied through Density Functional Theory (DFT) and microdynamics modeling. The spontaneous dissociation mechanisms of H₂ and CO₂ adsorption at the Rh₁₆/In₂O₃ interface were investigated. The oxygen vacancies in In₂O₃ enhanced the adsorption process. Bader charge analysis revealed a marginal positive charge on Rh₁₆, elucidating the critical insights into the electronic characteristics and catalytic activity. The study established the RWGS+CO-Hydro pathway as the predominant mechanism for methanol synthesis, characterized by a sequential transformation of intermediates: CO₂*→COOH*→CO*+OH*→HCO*→CH₂O*→CH₂OH*→CH₃OH*. Furthermore, Degree of Reaction Rate Control (DRC) analysis conducted in the range of 373–873 K and 10^–2 to 10³ bar identified two principal kinetic phenomena: at lower temperature and higher pressure, the conversion of CO* + H* to HCO* significantly impacted the overall reaction rate. Conversely, at higher temperature, the step from CH₂O* + H* to CH₃O* was dominate.

本研究通过密度泛函理论（DFT）和微动力学建模研究了二氧化碳（CO2）在 Rh16/In2O3 催化剂上加氢转化为甲醇（CH3OH）的过程。研究了 Rh16/In2O3 界面吸附 H2 和 CO2 的自发解离机制。In2O3 中的氧空位增强了吸附过程。Bader 电荷分析揭示了 Rh16 上的边际正电荷，阐明了其电子特性和催化活性的重要见解。研究确定了 RWGS+CO-Hydro 途径是甲醇合成的主要机制，其特点是中间产物的顺序转化：CO2*→COOH*→CO*+OH*→HCO*→CH2O*→CH2OH*→CH3OH*.此外，在 373-873 K 和 10-2-103 bar 范围内进行的反应速率控制度（DRC）分析确定了两种主要的动力学现象：在较低温度和较高压力下，CO* + H* 向 HCO* 的转化对整体反应速率有显著影响。相反，在较高温度下，从 CH2O* + H* 到 CH3O* 的步骤占主导地位。

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引用次数: 0

Hydrogen production via steam reforming of methanol on Cu/ZnO/Al2O3 catalysts: Effects of Al2O3 precursors 在 Cu/ZnO/Al2O3 催化剂上通过甲醇蒸汽转化制氢：Al2O3 前驱体的影响

Q3 Energy

燃料化学学报

Pub Date : 2024-10-01 DOI: 10.1016/S1872-5813(24)60459-7

HUANG Min , BO Qifei , LI Juan , QIAO Jingxuan , YUAN Shanliang , ZHANG Biao , CHEN Honglin , JIANG Yi

A series of Cu/ZnO/Al₂O₃ catalysts were prepared by co-precipitation method. This research focuses on investigating the influence of different Al₂O₃ precursors on the catalyst structure through thorough structural characterization techniques. Additionally, the catalytic performance of these catalysts in methanol reforming for hydrogen production was systematically evaluated. The results indicate that the simultaneous co-precipitation of Al³⁺ with Cu²⁺ and Zn²⁺ leads to partial substitution of Cu-Zn in the basic carbonates by Al³⁺. This substitution forms a hydrotalcite-like structure and strengthens Zn-Al interactions. On the contrary, after the co-precipitation of Cu²⁺ and Zn²⁺, introducing the Al₂O₃ precursor has a positive effect on eliminating the adverse effects of Al³⁺ on Cu-Zn substitution in basic carbonates. This process promotes the Cu-ZnO interaction, facilitates the dispersion of CuO species, and enhances the reducibility of catalysts. It also improves the dispersion of Cu on the surface, and ultimately enhanced the catalytic activity. Notably, the catalyst prepared using pseudo-boehmite as the Al₂O₃ precursor exhibited the highest activity. Under the conditions of a H₂O/CH₃OH molar ratio of 1.2 and a reaction temperature of 493 K, methanol conversion reached 94.8%, and the H₂ space-time yield was 97.5 mol/(kg·h). The catalyst activity remained relatively stable after continuous operation for 25 h. Even after being heat-treated at 723 K for 10 h, the activity loss of the catalyst was only 5.37%.

通过共沉淀法制备了一系列 Cu/ZnO/Al2O3 催化剂。本研究的重点是通过全面的结构表征技术研究不同 Al2O3 前驱体对催化剂结构的影响。此外，还系统评估了这些催化剂在甲醇重整制氢过程中的催化性能。结果表明，Al3+ 与 Cu2+ 和 Zn2+ 同时共沉淀会导致碱式碳酸盐中的 Cu-Zn 被 Al3+ 部分取代。这种置换形成了类似水滑石的结构，并加强了 Zn-Al 的相互作用。相反，在 Cu2+ 和 Zn2+ 共沉淀后，引入 Al2O3 前驱体对消除 Al3+ 对碱性碳酸盐中 Cu-Zn 取代的不利影响有积极作用。这一过程促进了 Cu-ZnO 的相互作用，有利于 CuO 物种的分散，并提高了催化剂的还原性。它还改善了 Cu 在表面的分散，最终提高了催化活性。值得注意的是，用假沸石作为 Al2O3 前驱体制备的催化剂活性最高。在 H2O/CH3OH 摩尔比为 1.2 和反应温度为 493 K 的条件下，甲醇转化率达到 94.8%，H2 时空产率为 97.5 mol/（kg-h）。即使在 723 K 温度下加热 10 小时，催化剂的活性损失也仅为 5.37%。

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引用次数: 0

Cr-MIL-101 derived nano Cr2O3 for highly efficient dehydrogenation of n-hexane 提取自 Cr-MIL-101 的纳米 Cr2O3 用于正己烷的高效脱氢反应

Q3 Energy

燃料化学学报

Pub Date : 2024-10-01 DOI: 10.1016/S1872-5813(24)60458-5

LI Xiuyi, SHEN Haowei, XU Jiale, LI Chunyi

Nano Cr₂O₃ (n-Cr₂O₃) was prepared by the thermolysis of the mesoporous Cr-MIL-101, and its catalytic performance for n-hexane dehydrogenation was investigated and compared with Cr₂O₃ obtained by traditional method. It is found that dehydrogenation of n-hexane on n-Cr₂O₃ catalyst can produce n-hexenes and benzene efficiently, and the catalytic performance is related to the calcination temperature. The optimal n-hexane conversion can be obtained on n-Cr₂O₃ calcinated under 600 °C, is 40.6%, and the selectivities to n-hexenes and benzene are 20.1% and 69.3%, respectively. The conversion of n-hexane for n-Cr₂O₃ catalyst is decreased with calcination temperature increase, while the catalyst stability in dehydrogenation reaction is enhanced. n-Hexane conversion of p-Cr₂O₃-1 (obtained by precipitation method) and p-Cr₂O₃-2 (calcinating Cr(NO₃)·9H₂O directly) catalysts are very low (<7.5%), and their specific activity for n-hexane dehydrogenation are 1.5 and 1.7 g/(m²·h) respectively, lower than that of n-Cr₂O₃-600 (2.0 g/(m²·h)). The results of BET, XRD, TEM and FT-IR reveal that n-Cr₂O₃ is the nanoparticles with large specific surface area that more dehydrogenation active sites are exposed, while p-Cr₂O₃ is the large particles with extremely low surface area that few dehydrogenation active sites are presented. By contrast, industrial Cr₂O₃/Al₂O₃ catalyst possesses the highest specific activity of 2.4 g/(m²·h) due to the dispersion effect of Al₂O₃. Therefore, highly catalytic activity of n-Cr₂O₃ for n-hexane dehydrogenation is attributed to the unique properties of small particle, large specific surface area and more exposed active sites. This work not only explains the high dehydrogenation activity of nano-Cr₂O₃ derived by Cr-MIL-101, but also provides guidance for the precise design and synthesis of high-performance CrO_x-based catalyst for the dehydrogenation of alkanes.

通过热解介孔 Cr-MIL-101 制备了纳米 Cr2O3（n-Cr2O3），研究了其对正己烷脱氢的催化性能，并与传统方法制备的 Cr2O3 进行了比较。研究发现，正己烷在 n-Cr2O3 催化剂上脱氢可高效生成正己烯和苯，且催化性能与煅烧温度有关。在 600 °C 下煅烧的 n-Cr2O3 可获得 40.6% 的最佳正己烷转化率，对正己烯和苯的选择性分别为 20.1% 和 69.3%。n-Cr2O3 催化剂的正己烷转化率随煅烧温度的升高而降低，但催化剂在脱氢反应中的稳定性却有所提高。p-Cr2O3-1（通过沉淀法获得）和 p-Cr2O3-2（直接煅烧 Cr(NO3)-9H2O）催化剂的正己烷转化率很低（7.5%），其正己烷脱氢比活度分别为 1.5 和 1.7 g/（m2-h），低于 n-Cr2O3-600（2.0 g/（m2-h））。BET、XRD、TEM 和 FT-IR 的研究结果表明，n-Cr2O3 是比表面积大的纳米颗粒，暴露出较多的脱氢活性位点，而 p-Cr2O3 是比表面积极低的大颗粒，呈现出较少的脱氢活性位点。相比之下，由于 Al2O3 的分散效应，工业 Cr2O3/Al2O3 催化剂的比活度最高，达到 2.4 g/（m2-h）。因此，正氯化铬在正己烷脱氢过程中的高催化活性归因于其颗粒小、比表面积大和活性位点暴露多的独特性质。这项工作不仅解释了由 Cr-MIL-101 衍生的纳米 Cr2O3 的高脱氢活性，还为精确设计和合成用于烷烃脱氢的高性能 CrOx 基催化剂提供了指导。

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引用次数: 0

Effect of the RhnNin alloy cluster size on the catalytic performance of RhnNin/TiO2 in the conversion of syngas to ethanol RhnNin 合金团簇尺寸对 RhnNin/TiO2 在合成气转化为乙醇过程中催化性能的影响

Q3 Energy

燃料化学学报

Pub Date : 2024-10-01 DOI: 10.1016/S1872-5813(24)60454-8

ZHANG Jingjing , LING Lixia , MA Caiping , ZHANG Riguang , WANG Baojun

The direct conversion of syngas to ethanol on the Rh_nNi_n/TiO₂ (n = 1, 2, 3, 4) catalyst has been investigated by using the density functional theory (DFT) and micro-kinetic methods, in order to elucidate the regulatory mechanism of Rh_nNi_n alloy cluster size-induced metal-support interaction on the catalytic performance of Rh_nNi_n/TiO₂ in the ethanol synthesis. The results indicate that Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ can significantly enhance the conversion of CO and the formation of C–C bond and meanwhile inhibit the generation of methane. Rh₁Ni₁/TiO₂ exhibits the highest ethanol production activity and relative selectivity. The electronic property analysis results suggest that Ni atoms on the alloy clusters and Ti and O atoms on the supports transfer the most charge to the Rh atoms on the Rh₁Ni₁/TiO₂ catalyst, which displays the strongest Rh-Ni interaction on the alloy clusters as well as the strongest interaction between the alloy clusters and the TiO₂ support, endowing Rh₁Ni₁/TiO₂ with the highest catalytic activity. In addition, the Ab-initio molecular dynamics (AIMD) simulations at 525 K show that the Rh₁Ni₁/TiO₂ catalyst has high thermal stability.

利用密度泛函理论（DFT）和微观动力学方法研究了RhnNin/TiO2（n = 1, 2, 3, 4）催化剂将合成气直接转化为乙醇的过程，以阐明RhnNin合金团簇尺寸诱导的金属-支撑相互作用对RhnNin/TiO2在乙醇合成过程中催化性能的调控机制。结果表明，Rh1Ni1/TiO2 和 Rh3Ni3/TiO2 能显著提高 CO 的转化率和 C-C 键的形成，同时抑制甲烷的生成。Rh1Ni1/TiO2 的乙醇生产活性和相对选择性最高。电子性质分析结果表明，Rh1Ni1/TiO2 催化剂中合金团簇上的 Ni 原子以及载体上的 Ti 原子和 O 原子将最多的电荷转移给 Rh 原子，合金团簇上的 Rh-Ni 相互作用最强，合金团簇与 TiO2 载体之间的相互作用也最强，从而赋予 Rh1Ni1/TiO2 最高的催化活性。此外，在 525 K 下进行的 Ab-initio 分子动力学（AIMD）模拟表明，Rh1Ni1/TiO2 催化剂具有很高的热稳定性。

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引用次数: 0

A thermodynamic consideration on the synthesis of methane from CO, CO2, and their mixture by hydrogenation 通过加氢从一氧化碳、二氧化碳及其混合物合成甲烷的热力学研究

Q3 Energy

燃料化学学报

Pub Date : 2024-10-01 DOI: 10.1016/S1872-5813(24)60449-4

WANG Han , GUO Shujia , QIN Zhangfeng , LI Zhikai , WANG Guofu , DONG Mei , FAN Weibin , WANG Jianguo

The synthesis of methane from CO and CO₂ by hydrogenation is now considered as a promising route in effectively storing hydrogen energy as well as sustainably producing fuels and chemicals, while many reaction details involved in such processes, in particular for the hydrogenation of the CO and CO₂ mixture, are not yet adequately understood. As a supplement to our previous works on the hydrogenation of CO and CO₂ into alcohols and hydrocarbons, a thermodynamic consideration is made in this work to evaluate the potential and limit for the synthesis of methane from CO, CO₂, and their mixture in particular. The results consolidate that in comparison with single CO or CO₂, their mixture is probably more credible in practice for the production of methane by hydrogenation, where the overall C-based methane yield can be used as the major index to evaluate the process efficiency. The hydrogenation of CO shows a higher equilibrium yield of methane than the hydrogenation of CO₂, while the overall C-based equilibrium yield of methane for the hydrogenation of the CO and CO₂ mixture just lies in between and decreases almost lineally with the increase of the CO₂/(CO+CO₂) molar ratio in the feed, despite the great change in the equilibrium conversions of CO and CO₂ with the feed composition. Nevertheless, an adequate overall C-based equilibrium yield of methane (> 85%) can be achieved at a temperature lower than 400 °C and a pressure higher than 0.1 MPa for the stoichiometric hydrogenation of CO, CO₂, or their mixture whichever. These results should be beneficial to the design of more efficient catalysts and processes for the hydrogenation of CO/CO₂ to methane.

目前，通过加氢从一氧化碳和二氧化碳合成甲烷被认为是有效储存氢能以及可持续生产燃料和化学品的一条很有前途的途径，但人们对此类过程中涉及的许多反应细节，特别是一氧化碳和二氧化碳混合物的加氢反应，还没有充分的了解。作为对我们之前关于将 CO 和 CO2 加氢转化为酒精和碳氢化合物的研究的补充，本研究从热力学角度评估了从 CO、CO2，特别是它们的混合物合成甲烷的潜力和极限。结果表明，与单一的一氧化碳或二氧化碳相比，它们的混合物在通过氢化生产甲烷的实践中可能更可靠，其中以 C 为基础的甲烷总产量可作为评估工艺效率的主要指标。CO 的氢化比 CO2 的氢化显示出更高的甲烷平衡产率，而 CO 和 CO2 混合物氢化的整体 C 基甲烷平衡产率仅介于两者之间，并且随着进料中 CO2/（CO+CO2）摩尔比的增加而几乎直线下降，尽管 CO 和 CO2 的平衡转化率随进料成分的变化而发生很大变化。不过，在温度低于 400 °C 和压力高于 0.1 MPa 的条件下，对 CO、CO2 或它们的混合物进行化学计量加氢，可以获得足够的以 C 为基础的甲烷总平衡产率（85%）。这些结果将有助于设计更高效的催化剂和工艺，将 CO/CO2 加氢转化为甲烷。

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引用次数: 0

Corrosion behavior of co-gasification slag of furfural residue and coal on alumina-silica refractories 糠醛渣和煤在氧化铝-二氧化硅耐火材料上的共气化渣腐蚀行为

Q3 Energy

燃料化学学报

Pub Date : 2024-10-01 DOI: 10.1016/S1872-5813(24)60461-5

MA Xiaotong , WANG Zhigang , LU Hao , LIU Wei , WANG Yanxia , ZHAO Jiangshan , SUN Lingmin , YAN Jingchong , ZHUANG Shujuan , LI Huaizhu , KONG Lingxue

Gasification of furfural residue with coal can realize its efficient and clean utilization. But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory. Two gasification coals with different silica alumina ratio and a furfural residue were selected in the study. The effects of furfural residue additions on corrosion of silica brick, corundum brick, high alumina brick and mullite brick were investigated by using XRD, SEM-EDS and Factsage Software, and the corrosion mechanism was analyzed. With increasing furfural residue addition, the permeability of the slags to high-aluminium-bearing refractories first decreases and then increases, while the permeability on silica brick shows a slight decrease trend. Leucite (KAlSi₂O₆) with high-melting temperature is generated from the reaction of K₂O and SiO₂ in slag with Al₂O₃ in refractories after furfural residue is added, which hinders the infiltration of slag in refractories. Kaliophilite (KAlSiO₄) of low-melting point is formed when K₂O content increases, and this contributes to the infiltration of slag in refractories. The acid-base reaction between slag and silica brick is distinctly occurred, more slag reacts with SiO₂ in the silicon brick, resulting in a decrease in the amount of slag infiltrating into the silicon brick as furfural residue is added. The corrosion of silica brick is mainly caused by the acid-base reaction, while the corrosion of three alumina based refractory bricks of corundum, mullite and high alumina brick is determined by slag infiltration. A linear correlation between the percolation rate and slag viscosity is established, the slag permeability increases with decreasing viscosity, resulting in stronger permeability for the high Si/Al ratio slag with lower viscosity.

糠醛渣与煤一起气化可以实现糠醛渣的高效清洁利用。但糠醛渣中碱金属含量高，易造成气化炉耐火材料腐蚀。本研究选择了两种不同硅铝比的气化煤和一种糠醛渣。利用 XRD、SEM-EDS 和 Factsage 软件研究了糠醛渣添加量对硅砖、刚玉砖、高铝砖和莫来石砖腐蚀的影响，并分析了腐蚀机理。随着糠醛残渣添加量的增加，炉渣对高铝耐火材料的渗透率先降低后升高，而对硅砖的渗透率则呈轻微下降趋势。加入糠醛渣后，炉渣中的 K2O 和 SiO2 与耐火材料中的 Al2O3 反应生成了熔融温度较高的褐铁矿（KAlSi2O6），阻碍了炉渣在耐火材料中的渗透。当 K2O 含量增加时，会形成低熔点的 Kaliophilite（KAlSiO4），这有助于炉渣在耐火材料中的渗透。炉渣与硅砖之间发生明显的酸碱反应，更多的炉渣与硅砖中的 SiO2 发生反应，导致渗入硅砖中的炉渣量随着糠醛渣的加入而减少。硅砖的腐蚀主要是由酸碱反应引起的，而刚玉砖、莫来石砖和高铝砖这三种氧化铝基耐火砖的腐蚀则是由炉渣渗入决定的。渗流率与炉渣粘度之间呈线性关系，炉渣渗透性随粘度的降低而增加，粘度较低的高硅/铝比炉渣的渗透性更强。

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引用次数: 0

Investigating the coking performance of ethylene residue pitch components 研究乙烯残渣沥青成分的结焦性能

Q3 Energy

燃料化学学报

Pub Date : 2024-09-01 DOI: 10.1016/S1872-5813(24)60453-4

ZHANG Tongtong , ZHU Huihui , ZHU Yaming , HU Chaoshuai , LÜ Jun , CHENG Junxia , BAI Yonghui , ZHAO Xuefei

Ethylene residue pitch (ETP, the heavy component in ethylene residue tar) is widely used as a preferred raw material for preparing petroleum-based artificial carbon materials characterized by high carbon content, high aromaticity, and low heteroatom (S, N) content. To investigate the coking properties of ETP, eight components of ETP (four soluble and four insoluble components) were obtained via extraction and separation using methanol, n-butanol, n-hexane, and dimethyl sulfoxide as solvents. The thermal conversion (temperature = 500 °C) and carbonization treatment (temperature =1400 °C) were carried out on each pitch component. The basic physical properties of ETP components were observed using infrared spectroscopy, thermogravimetric analysis, and ¹H-NMR. The microstructure of the petroleum-based pitch coke was studied using polarizing microscopy, X-ray single crystal diffraction (XRD), Raman spectroscopy, and scanning electron microscopy. The aromaticity of the insoluble components in ETP was slightly higher than that of soluble components, and the insoluble components had slightly fewer branching chains than those in soluble components. The microstrength of the ETP coke obtained using insoluble components was higher than that obtained using soluble components, and the true density of ETP coke HS-C was as high as 2.0554 g/cm³.

乙烯渣沥青（ETP，乙烯渣焦油中的重组分）被广泛用作制备石油基人工碳材料的首选原料，其特点是含碳量高、芳香度高、杂原子（S、N）含量低。为了研究 ETP 的焦化特性，我们以甲醇、正丁醇、正己烷和二甲亚砜为溶剂，通过萃取和分离得到了 ETP 的八种成分（四种可溶成分和四种不溶成分）。对每种沥青成分进行了热转化（温度 = 500 ℃）和碳化处理（温度 = 1400 ℃）。使用红外光谱、热重分析和 1H-NMR 观察了 ETP 成分的基本物理性质。使用偏光显微镜、X 射线单晶衍射 (XRD)、拉曼光谱和扫描电子显微镜研究了石油基沥青焦炭的微观结构。ETP 中不溶性成分的芳香度略高于可溶性成分，不溶性成分的支链略少于可溶性成分。使用不溶性成分获得的 ETP 焦炭的微强度高于使用可溶性成分获得的 ETP 焦炭的微强度，ETP 焦炭 HS-C 的真实密度高达 2.0554 g/cm3。

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