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Production of Renewable p-Xylene from 2,5-Dimethylfuran and Ethylene over MWW Zeolite Catalysts 利用 MWW 沸石催化剂从 2,5-二甲基呋喃和乙烯生产可再生对二甲苯
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-19 DOI: 10.1021/acs.iecr.4c01610
Xinqiang Feng, Xiangcheng Li, Xiao Han, Hongyu Qu, Chuang Liu, Weimin Yang, Zhendong Wang
The production of biobased p-xylene (PX) from 2,5-dimethylfuran (DMF) and ethylene has gained more and more attention from the aspects of both the environmentally friendly route and practical application. Despite the catalytic activity of the reported catalysts, the design and synthesis of new zeolite-based catalysts with strong durability are extremely desirable but still remain a significant challenge. Herein, we report MWW-type zeolite as highly efficient catalysts for PX production. The lamellar structure and external hemicavities endow MWW zeolite with a favorable mass transfer performance. Al-MWW synthesized with the H3BO3 additive exhibits a remarkably higher PX selectivity than conventional MCM-22 due to its lower Brønsted/Lewis ratio of 2.0 and a less strong Brønsted acid proportion of 53%. The incorporation of heteroatoms into the zeolite can further regulate the Brønsted/Lewis acidity, and Ga/Al-MWW zeolite with a B/L ratio of 1.0 and the least strong Brønsted acid proportion of 43% was found to be the most efficient catalyst (PX selectivity of 80.3%). This work pushes ahead the knowledge of MWW-type zeolite catalysts for PX production, which would also be constructive for the development of new zeolite catalysts.
从 2,5 二甲基呋喃(DMF)和乙烯生产生物基对二甲苯(PX)的环保路线和实际应用两方面来看,该技术越来越受到关注。尽管已报道的催化剂具有较高的催化活性,但设计和合成具有较强耐久性的新型沸石基催化剂仍然是一个巨大的挑战。在此,我们报告了用于生产 PX 的高效催化剂 MWW 型沸石。片状结构和外部半腔赋予了 MWW 沸石良好的传质性能。与传统的 MCM-22 相比,使用 H3BO3 添加剂合成的 Al-MWW 具有更低的布氏/刘易斯比(2.0)和更低的布氏酸比例(53%),因此 PX 选择性明显更高。在沸石中加入杂原子可进一步调节布氏/刘易斯酸度,B/L 比为 1.0 且布氏酸比例最低(43%)的 Ga/Al-MWW 沸石被认为是最有效的催化剂(PX 选择性为 80.3%)。这项工作推动了人们对用于生产 PX 的 MWW 型沸石催化剂的认识,对新型沸石催化剂的开发也具有建设性意义。
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引用次数: 0
Ultrathin and Metal Ions-Free Polyionic Nanogel Coating Membrane for Efficient and Fast Oil-in-Water Emulsions Separation and Cr(VI) Removal: Adsorption Properties, Kinetics, and Mechanism 用于高效快速分离水包油型乳浊液和去除六价铬的超薄无金属离子聚阴离子纳米凝胶涂层膜:吸附特性、动力学和机理
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-19 DOI: 10.1021/acs.iecr.4c01873
Wenjie Luo, Yijian Zheng, Xuan Long, Rongtong Wang, Yuanhang Pi, Feipeng Jiao
The problem of oil fouling and the complex composition of oily wastewater are bottlenecks that urgently need to be addressed for the application of membrane separation technology in the field of oil–water separation. Therefore, ultrathin TA/SA/PEI polyionic nanogel coatings were constructed on hydrophobic PVDF membrane surfaces through surface grafting and dopamine-like self-polymerization reactions. The functional coated membranes (TSP-3) retain superhydrophilicity and underwater superoleophobicity, even in harsh environments such as strong acids, strong alkalis, various salt solutions, ultrasound, and abrasion. The TSP-3 membrane exhibited excellent separation efficiency (>99%) for a wide range of oil-in-water emulsions stabilized by surfactants, with virtually no deterioration in flux (>8014.70 ± 298.86 L·m–2·h–1·bar–1) over five dead-end cycle separations. The formation process of the oil film filter cake was also analyzed in crossflow mode. It was assumed that the accumulation of oil droplets on the membrane surface to form a film under certain conditions was beneficial to the membrane’s antioil fouling performance. Meanwhile, the TSP-3 membrane possessed high removal efficiency (96.13%) and recoverability for Cr(VI), and the phenolic hydroxyl groups could also reduce Cr(VI) to the lower toxicity Cr(III). Various adsorption kinetic and isotherm models were used to analyze the adsorption process, and the results fit well with the pseudo-second-order kinetic model (R2 = 0.99820) and the Langmuir model (R2 = 0.99986). This indicated that the adsorption of Cr(VI) by TSP-3 was monomolecular layer chemical adsorption on heterogeneous surfaces, and the adsorption was favorable (0 < RL < 1). Electrostatic attraction and hydrogen bonding were considered to play a key role in the adsorption of Cr(VI) by XPS characterization analysis and DFT theoretical calculations. This strategy provided a feasible approach for constructing ultrathin polyanionic nanogel membranes to achieve an antioil barrier, which could effectively and rapidly separate a wide range of oil-in-water emulsions stabilized by surfactants, while removing and reducing Cr(VI).
油污问题和含油废水的复杂成分是膜分离技术在油水分离领域应用急需解决的瓶颈。因此,通过表面接枝和多巴胺类自聚合反应,在疏水性 PVDF 膜表面构建了超薄 TA/SA/PEI 聚离子纳米凝胶涂层。即使在强酸、强碱、各种盐溶液、超声波和磨损等恶劣环境下,功能涂层膜(TSP-3)仍能保持超亲水性和水下超疏水性。TSP-3 膜对表面活性剂稳定的各种水包油型乳液具有极佳的分离效率(99%),在五个死循环分离过程中通量几乎没有下降(8014.70 ± 298.86 L-m-2-h-1-bar-1)。还在横流模式下分析了油膜滤饼的形成过程。据推测,在特定条件下,油滴在膜表面积聚成膜有利于膜的防油污性能。同时,TSP-3 膜对六价铬具有较高的去除率(96.13%)和回收率,酚羟基还能将六价铬还原成毒性较低的三(III)价铬。利用各种吸附动力学模型和等温线模型分析了吸附过程,结果与伪二阶动力学模型(R2 = 0.99820)和朗缪尔模型(R2 = 0.99986)十分吻合。这表明 TSP-3 对 Cr(VI) 的吸附是在异质表面上的单分子层化学吸附,吸附是有利的(0 < RL <1)。通过 XPS 表征分析和 DFT 理论计算,认为静电吸引和氢键在吸附六价铬的过程中起了关键作用。该策略为构建超薄聚阴离子纳米凝胶膜以实现抗油屏障提供了一种可行的方法,它可以有效、快速地分离各种由表面活性剂稳定的水包油乳液,同时去除和减少六价铬。
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引用次数: 0
Interfacial Auδ−–OV–Ti Structure Promoted C–H Bond Activation for Selective Oxidation of Fatty Alcohols to Fatty Acids 界面 Auδ--OV-Ti 结构促进 C-H 键活化,将脂肪醇选择性氧化为脂肪酸
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-18 DOI: 10.1021/acs.iecr.4c00986
Yu Su, Rong Fan, Jiabao Li, Yangxi Liu, Ziyuan Zheng, Xin Zhou, Xiang Feng, Yibin Liu, Hui Zhao, Xiaobo Chen, Xingong Zhang, Chaohe Yang, Hao Yan
Oxidation of fatty alcohols to fatty acids is still challenging due to the sluggish activation of the C–H bond over Au supported on reducible oxides with a coordination-saturated structure. Herein, we constructed an efficient interfacial Auδ−–OV–Ti structure by tuning the crystal forms of TiO2. Compared with TiO2-rutile exposed by (110) and (111) crystal facets, TiO2-anatase can exploit the defect (101) crystal facet to obtain rich oxygen vacancies (OV), inducing electron migration from TiO2-anatase support to Au species to form electron-rich Auδ− species. Specifically, the synergistic catalytic effect between the OV–Ti and Auδ− species greatly enhances the adsorption of alcohol and thereby overcomes sluggish activation of the C–H bond caused by the electron pushing effect triggered by long carbon chains. Consequently, the Au/TiO2-anatase catalyst shows excellent isooctyl alcohol conversion (69.5%) and isocaprylic acid selectivity (67.9%) under base-free conditions. The catalytic system is further extended to the oxidation of other fatty alcohols to fatty acids with excellent catalytic performance.
由于在配位饱和结构的可还原氧化物上支撑的 Au 上 C-H 键活化缓慢,因此将脂肪醇氧化成脂肪酸仍是一项挑战。在此,我们通过调整 TiO2 的晶体形态,构建了一种高效的界面 Auδ--OV-Ti 结构。与暴露于(110)和(111)晶面的TiO2-rutile相比,TiO2-anatase可利用缺陷(101)晶面获得丰富的氧空位(OV),诱导电子从TiO2-anatase支撑物迁移到金物种,形成富电子的Auδ-物种。具体来说,OV-Ti 和 Auδ- 物种之间的协同催化作用大大增强了对酒精的吸附,从而克服了长碳链引发的电子推动效应导致的 C-H 键活化迟缓。因此,Au/TiO2-anatase 催化剂在无碱条件下表现出优异的异辛醇转化率(69.5%)和异辛酸选择性(67.9%)。该催化体系还可进一步扩展到其他脂肪醇氧化成脂肪酸的过程中,并具有优异的催化性能。
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引用次数: 0
Acid-Catalytic Effect of Alcohol Dissociation on Pinacol Rearrangement in Hot Compressed Water 酒精解离对频哪醇在热压缩水中重排的酸催化效应
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-18 DOI: 10.1021/acs.iecr.4c01448
Shotaro Seki, Yoshito Oshima, Makoto Akizuki
The acid-catalytic effect of alcohol on pinacol rearrangement in hot compressed water was investigated at temperatures ranging from 210 to 270 °C and a pressure of 30 MPa. The reaction order in hot compressed water depended on the pH. Kinetic analysis was conducted based on the reaction pathway, including the dissociation of pinacol. The reaction was found to be mainly catalyzed by H+ produced from the dissociation of both water and pinacol. The kinetic analysis indicated that the dissociation constant of pinacol in hot compressed water was approximately 106 times higher than that in ambient water. Moreover, the acid-catalytic effect of pinacol increased with an increasing concentration and was greater than that of water.
在温度为 210 至 270 °C、压力为 30 兆帕的条件下,研究了酒精在热压缩水中对频哪醇重排的酸催化效应。热压缩水中的反应顺序取决于 pH 值。根据反应路径(包括频哪醇的解离)进行了动力学分析。研究发现,该反应主要由水和频哪醇解离产生的 H+ 催化。动力学分析表明,频哪醇在热压缩水中的解离常数是在环境水中的约 106 倍。此外,频哪醇的酸催化效应随着浓度的增加而增加,并且大于水的酸催化效应。
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引用次数: 0
Hydrogen Peroxide-Modified Biochars from Wetland Plants for Bisphenol A Removal in Water 湿地植物过氧化氢改性生物炭用于去除水中的双酚 A
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-18 DOI: 10.1021/acs.iecr.4c01179
Yue Zhao, Mo Yang, Kezhen Qi, Anzhong Peng, Jing Pan
In this study, hydrogen peroxide-modified biochars from wetland plants were synthesized and employed for aqueous bisphenol A (BPA) removal, which achieved equilibrium within 300 min. The adsorption trend increased with increasing initial BPA concentration or contact time before reaching adsorption equilibrium. The pseudo-second-order adsorption kinetic model and Langmuir adsorption isotherm model fitted well with the adsorption data. The maximum adsorption capacities of Phragmites australis and Typha orientalis biochar carbonized at 500 °C for 6 h and modified with 5% hydrogen peroxide reached 10.589 and 8.483 mg/g, respectively. The modification of hydrogen peroxide resulted in the highest specific surface area of 7.143 m2/g for P. australis and 9.848 m2/g for T. orientalis, thereby promoting the adsorption of BPA. Characterization showed that hydrogen peroxide increased micropore and mesopore volumes and micropore and mesopore surface areas of biochars, disrupted the microcrystalline structures, and reduced the regularity of biochars. The regeneration study demonstrated that the hydrogen peroxide-modified biochars exhibited reusability for up to five cycles, with a reduction in the BPA removal efficiency of 10.67% for P. australis biochar and 10.07% for T. orientalis biochar.
本研究从湿地植物中合成了过氧化氢改性生物炭,并将其用于去除水体中的双酚 A(BPA),在 300 分钟内达到了平衡。在达到吸附平衡之前,吸附趋势随着双酚 A 初始浓度或接触时间的增加而增加。伪二阶吸附动力学模型和 Langmuir 吸附等温线模型与吸附数据拟合良好。在 500 °C 下碳化 6 h 并用 5% 过氧化氢改性的黄葭和香蒲生物炭的最大吸附容量分别达到 10.589 和 8.483 mg/g。过氧化氢改性后的生物炭比表面积最高,奥氏蕨为 7.143 m2/g,东方香蒲为 9.848 m2/g,从而促进了对双酚 A 的吸附。表征结果表明,过氧化氢增加了生物炭的微孔和中孔体积以及微孔和中孔表面积,破坏了微晶结构,降低了生物炭的规整度。再生研究表明,过氧化氢改性的生物炭可重复使用长达五个周期,双酚 A 生物炭的双酚 A 去除率降低了 10.67%,东方褐藻生物炭的双酚 A 去除率降低了 10.07%。
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引用次数: 0
Energy-Efficient Design Sequences for the Purification of Styrene Monomer from the Pyrolysis Oil of Waste Polystyrene 从废聚苯乙烯热解油中提纯苯乙烯单体的节能设计序列
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-18 DOI: 10.1021/acs.iecr.4c01004
Donggun Kim, Yongbeom Shin, Minyong Lee, Jeongwoo Lee, Young-Joo Lee, Jae W. Lee
This study focuses on the energy-efficient separation process of styrene monomer, avoiding the formation of an azeotrope by using a vacuum distillation, derived from the pyrolysis of waste polystyrene (PS). The direct-indirect sequence, which positions the separation column of ethylbenzene and styrene monomer as the last step, exhibited a 30% reduction in the total utility consumption and a 37% reduction in the total annual cost compared to that of the direct-direct sequence that separates lighter components sequentially. A dividing wall column (DWC) configuration derived from the direct-indirect sequence showed the most significant reduction of 40% in utility consumption. However, when the feed capacity was low, the increased capital cost of DWC resulted in a total annual cost similar to that of the direct-indirect sequence. As the capacity of the entire distillation system increased, the reduction in the total operating cost of the DWC was amplified, indicating the advantages of using the DWC in high product throughputs from both energy and economic perspectives. Therefore, implementing the DWC in large-scale PS recycling processes demonstrates superior performance compared to the conventional distillation process, resulting in a more streamlined process with substantial energy savings and CO2 emissions.
本研究的重点是苯乙烯单体的节能分离工艺,通过使用真空蒸馏,避免形成共沸物,真空蒸馏源自废聚苯乙烯(PS)的热解。直接-间接流程将乙苯和苯乙烯单体的分离塔设置在最后一步,与按顺序分离轻组分的直接-间接流程相比,总功耗降低了 30%,年总成本降低了 37%。由直接-间接顺序衍生出的分壁柱(DWC)配置显示出最显著的效用消耗降低 40%。然而,当进料能力较低时,DWC 的资本成本增加,导致每年的总成本与直接-间接顺序相似。随着整个蒸馏系统能力的提高,DWC 总运行成本的降低幅度也在扩大,这表明从能源和经济角度来看,在产品产量高的情况下使用 DWC 具有优势。因此,与传统蒸馏工艺相比,在大规模 PS 回收工艺中使用 DWC 表现出更优越的性能,从而简化了工艺流程,节省了大量能源,减少了二氧化碳排放。
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引用次数: 0
Numerical Study on Mixing Behavior of a Self-Priming Venturi Mixer 自吸式文丘里混合器混合行为的数值研究
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-18 DOI: 10.1021/acs.iecr.4c00495
Mengjing Feng, Chengmin Gui, Zhigang Lei
A novel self-priming venturi mixer consists of a designed nozzle, and a conventional venturi mixer was proposed to enhance mixing quality by compressing the raw gas. Computational fluid dynamics technology was employed to study the flow characteristics of the fluid within the mixer, and the performance of the mixer under different structural parameters was evaluated by the entrained rate, pressure difference, and mixing quality. Besides, the relationship between the structural parameters of the mixer and the composition ratio at the outlet was clearly elucidated. The research results suggest that the energy loss is minimized when the nozzle outlet radius ranges from 0.8 to 1.2 cm. Furthermore, as the length-to-diameter ratio increases, the entrainment rate and pressure difference initially increase gradually and then stabilize. Additionally, a small length-to-diameter ratio and an excessively large diffusion angle may reduce the mixing uniformity of the venturi mixer.
提出了一种新型自吸式文丘里混合器,它由一个设计好的喷嘴和一个传统的文丘里混合器组成,通过压缩原料气体来提高混合质量。采用计算流体动力学技术研究了混合器内流体的流动特性,并通过夹带率、压差和混合质量评估了混合器在不同结构参数下的性能。此外,还清楚地阐明了混合器结构参数与出口成分比之间的关系。研究结果表明,当喷嘴出口半径在 0.8 至 1.2 厘米之间时,能量损失最小。此外,随着长径比的增大,夹带率和压差最初会逐渐增大,然后趋于稳定。此外,过小的长径比和过大的扩散角可能会降低文丘里管混合器的混合均匀度。
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引用次数: 0
Diels–Alder Reaction of Biofuran Derivatives and Cycloolefin for Directional Synthesis of Fused Ring Hydrocarbon High Density Jet Fuel 生物呋喃衍生物与环烯的 Diels-Alder 反应定向合成熔环烃高密度喷气燃料
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-18 DOI: 10.1021/acs.iecr.4c00808
Xianlong Liu, Yiting Zhao, Gewei Zhang, Chengxiang Shi, Lun Pan, Xiangwen Zhang, Ji-Jun Zou
Attention has been drawn to the potential of renewable biomass as an alternative to petroleum-based feedstocks for the synthesis of high-density fuels given the depletion of petroleum resources and critical environmental issues. In this study, fused ring high-density liquid fuel precursors were directionally synthesized from biofuran derivatives by the Diels–Alder reaction. The impact of different dienophiles on the Diels–Alder reaction of 2-methylfuran facilitated by zeolites was evaluated. The influences of the catalyst, reaction temperature, and reactant ratio on the reaction were explored. Moreover, this study emphasized the specific synthesis of high density fuels by examining the significant influence of the substrate structure on the Diels–Alder reaction. When preparing polycyclic structures through Diels–Alder reactions of furan derivatives, it is advisible to consider monosubstituted furan derivatives first due to their high electron density and suitable steric resistance. The insights gleaned from this study provide substantial guidance for selecting suitable feedstocks for fuel synthesis, further contributing to sustainable energy solutions.
鉴于石油资源的枯竭和严峻的环境问题,人们开始关注可再生生物质替代石油基原料合成高密度燃料的潜力。本研究利用 Diels-Alder 反应从生物呋喃衍生物定向合成了融合环高密度液体燃料前体。研究评估了不同亲二烯化合物对沸石促进 2-甲基呋喃的 Diels-Alder 反应的影响。研究还探讨了催化剂、反应温度和反应物比例对反应的影响。此外,本研究还通过考察底物结构对 Diels-Alder 反应的重要影响,强调了高密度燃料的特定合成。通过呋喃衍生物的 Diels-Alder 反应制备多环结构时,最好首先考虑单取代呋喃衍生物,因为它们具有高电子密度和适当的抗立体性。从本研究中获得的启示为选择合适的燃料合成原料提供了重要指导,进一步促进了可持续能源解决方案的发展。
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引用次数: 0
Preparation of Rare Earth Metal Doped with Co3O4 Composite Catalyst and Its Properties and Thermodynamics Studies on Tetracycline Degradation 掺杂稀土金属的 Co3O4 复合催化剂的制备及其在四环素降解过程中的性能和热力学研究
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-17 DOI: 10.1021/acs.iecr.4c00529
Tiantian Jin, Ziqian Zhu, Tanweer Zahra, Zhiheng Wu, Yunhong Chen, Xuhong Peng, Fanglue Zhou, Peizhu Zheng, Jian Fang, Jihua Zhao
Herein, we successfully synthesized a series of M-CoCoPBA, where M is the rare earth metal, by a chemical precipitation method and prepared M-Co3O4 by air pyrolysis with M-CoCoPBA as the precursor. The catalytic performance of M-Co3O4 as heterogeneous catalysts was studied for activating PMS to degrade tetracycline (TC), and it is noteworthy that Er-Co3O4 has the strongest catalytic activity. The degradation efficiency of TC in the Er-Co3O4/PMS system could reach 82% as a reaction time of 4 min at 25 °C, and the catalyst also has good cyclic stability after 5 cycles. The morphology and composition of the Co3O4 and Er-Co3O4 were systematically characterized by various techniques, and it is found that ErCoOx significantly enhanced the catalytic activity of PMS activation and TC degradation, owing to bigger surface area, more lattice defects, oxidation state of Co, and vacancy oxygen of the catalysts with Er doping, compared with CoOx. Free radical quenching and EPR experiments showed that singlet oxygen (1O2), SO4–•, and OH were generated in the ErCoOx/PMS system. The intermediate products and degradation pathway of TC by Er-Co3O4/PMS system were proposed according to the results of liquid chromatography–mass spectrometry. In addition, the kinetics of activating PMS to produce active substances by Co3O4 and Er-Co3O4 catalysts was systematically explored by using isothermal titration calorimetry (ITC) technology in the temperature range of 298.19–323.19 K, and the results indicate that Ea, ΔH, ΔS, and ΔG of Er-Co3O4 are all smaller than those of Co3O4 and demonstrate the inner mechanism of bigger rate constant and much higher catalytic property of Er-Co3O4.
在此,我们采用化学沉淀法成功合成了一系列M-CoCoPBA,其中M为稀土金属,并以M-CoCoPBA为前驱体,通过空气热解制备了M-Co3O4。研究了 M-Co3O4 作为异相催化剂活化 PMS 降解四环素(TC)的催化性能,值得注意的是 Er-Co3O4 的催化活性最强。在 Er-Co3O4/PMS 体系中,25 ℃ 下反应时间为 4 分钟,TC 的降解效率可达 82%,而且催化剂在 5 个循环后具有良好的循环稳定性。通过各种技术对 Co3O4 和 Er-Co3O4 的形貌和组成进行了系统表征,发现与 CoOx 相比,掺杂 Er 的催化剂具有更大的比表面积、更多的晶格缺陷、Co 的氧化态和空位氧,因此 ErCoOx 能显著提高 PMS 活化和 TC 降解的催化活性。自由基淬灭和 EPR 实验表明,在 ErCoOx/PMS 体系中产生了单线态氧(1O2)、SO4--和 -OH。根据液相色谱-质谱分析的结果,提出了 Er-Co3O4/PMS 系统降解 TC 的中间产物和途径。此外,利用等温滴定量热法(ITC)技术,在 298.结果表明,Er-Co3O4的Ea、ΔH⧧、ΔS⧧和ΔG⧧均小于Co3O4,说明Er-Co3O4具有更大的速率常数和更高的催化性能的内在机理。
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引用次数: 0
In Situ XAS Diagnostics of Reductive Hydroformylation Reaction in Segmented Flow Under Elevated Pressure and Temperature 高压高温下分段流中还原加氢甲酰化反应的原位 XAS 诊断技术
IF 4.2 3区 工程技术 Q2 ENGINEERING, CHEMICAL Pub Date : 2024-07-17 DOI: 10.1021/acs.iecr.4c01487
Mahmoud E. A. Eid, Dmitry N. Gorbunov, Viktor V. Shapovalov, Maria V. Nenasheva, Bogdan O. Protsenko, Evgeny Khramov, Aleksei N. Bulgakov, Sergey V. Abrosimov, Sergei V. Chapek, Alexander A. Guda, Alexander V. Soldatov
Homogeneous hydroformylation is an important industrial reaction for the production of aldehydes and alcohols. Rh metal complexes modified with tertiary amine ligands allow tandem one-pot reactions for converting olefins directly into alcohols, and more often, such reactions are performed in microfluidic flow regimes relevant to both academic research and industrial automatization. The reaction yield depends on the coordination of Rh atoms or the formation of Rh clusters; therefore, knowledge about the local atomic and electronic structure of active sites under industrial conditions is important. Rh K-edge X-ray absorption spectroscopy (XAS) is a unique tool to probe Rh coordination; however, to date, there have been no reports of the application of this methodology to hydroformylation in microfluidic biphasic flow. Our work demonstrates the experimental setup and transmission cell developed for segmented flow operando measurements. Quantitative analysis of XAS data was performed with the library of theoretical spectra computed for relevant monomeric, dimeric, and small cluster species. As found recently by EXAFS analysis for autoclave, we demonstrate that under segmented flow, the presence of amine species in the reaction prevents the formation of Rh clusters in favor of Rh dimers.
均相氢化甲酰化是生产醛类和醇类的重要工业反应。使用叔胺配体修饰的 Rh 金属配合物可以进行串联单锅反应,将烯烃直接转化为醇类,而且此类反应通常是在与学术研究和工业自动化相关的微流控条件下进行的。反应产率取决于 Rh 原子的配位或 Rh 团簇的形成;因此,了解工业条件下活性位点的局部原子和电子结构非常重要。Rh K 边 X 射线吸收光谱 (XAS) 是探测 Rh 配位的一种独特工具;然而,迄今为止,还没有将这种方法应用于微流体双相流中氢甲酰化的报道。我们的工作展示了为分段流操作测量而开发的实验装置和传输单元。利用为相关单体、二聚体和小团簇物种计算的理论光谱库,对 XAS 数据进行了定量分析。正如最近对高压釜的 EXAFS 分析所发现的那样,我们证明了在分段流下,反应中胺物种的存在会阻止 Rh 簇的形成,而有利于 Rh 二聚体的形成。
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引用次数: 0
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Industrial & Engineering Chemistry Research
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