Industrial & Engineering Chemistry Research最新文献

{"title":"Comparison of Kinetic Models for Biogas Steam Reforming Reactor Design According to Complexity and the Heat of Reaction Effect","authors":"Rafael Belo Duarte*,&nbsp;Beatriz Viana Marques,&nbsp;Erick Alessandro Barbosa Vieira,&nbsp;João Lourenço Castagnari Willimann Pimenta and Luiz Mario de Matos Jorge*,&nbsp;","doi":"10.1021/acs.iecr.5c02336","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02336","url":null,"abstract":"<p >Biogas reforming is being considered an alternative source of hydrogen and synthesis gas for gas-to-liquid technologies. In this context, our focus is on the rapid design of pilot-scale reactors based on simple and robust kinetic models. Thus, we present an evaluation of kinetic models of NiMo₂C/Al₂O₃ for biogas steam reforming, sourced from sugar cane industrial residues, in Brazil. Comparing the NiMo₂C/Al₂O₃ to catalysts from the literature (Ni/Al₂O₃, Ni/MgO). The models’ complexity are taken into account according to the Akaike Information Criterion (AIC). Simple models are shown to be superior, with the simplest one being the best: a second-order power law model for CH₄ and zeroth-order for water, which was validated considering the effects of reactor total pressure, temperature and feed H₂O/CH₄ ratio. Within model comparison, it was included for the first time─to the best of our knowledge, the effect of temperature variation caused by the heat of the methane steam reforming and water–gas shift reactions. The inclusion of the energy balance in the parameter estimation step improved the quality of the kinetic fit, providing strong evidence that the isothermal operation assumption, often used in differential reactors, may not always be true. In such cases, it is possible to extract kinetic parameters by adding the energy balance to the kinetic model. Finally, the model is applied to the simulation of a pilot scale biogas steam reforming reactor.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17555–17571"},"PeriodicalIF":3.9,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.iecr.5c02336","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Primers as Adhesion Promoters for Heterogeneous Catalysis─Application to Novel Packings for Enzymatic Reactive Distillation","authors":"Nicolas Chaussard*,&nbsp;Pierre Bolteau,&nbsp;Sylvain Tap,&nbsp;Marie-Line Zanota,&nbsp;Clémence Nikitine and Pascal Fongarland,&nbsp;","doi":"10.1021/acs.iecr.5c02496","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02496","url":null,"abstract":"<p >Enzymatic reactive distillation (ERD) presents a compelling strategy for sustainable chemical processes, integrating reaction and separation steps with enzymatic biocatalysis. However, challenges persist in immobilizing biocatalysts like Candida antarctica lipase B (CALB) on distillation internals due to poor adhesion and limited mechanical stability of coatings on metallic structures. Only wire gauze packings have been investigated in ERDs so far due to these limitations. This study investigates the functionalization of novel distillation packings, such as 3D-printed Tetra Spline structures and open-cell aluminum foams, with the sol–gel dip-coating method. To overcome adhesion issues, a silane-based primer containing (3-glycidyloxypropyl)trimethoxysilane (GPTMS) was employed. The use of this primer significantly improved the adhesion between the xerogel and metallic structures, marking one of the first applications of this technique in the field of heterogeneous (bio)catalysis. The xerogel-coated packings were characterized structurally via X-ray tomography and SEM, and catalytic performances were investigated with the enantioselective transesterification of 2-pentanol and ethylbutyrate. A Langmuir–Hinshelwood kinetic model was successfully developed, demonstrating a mean absolute percentage error of 4.56%. Hydrodynamic and separation performances of the packings were also evaluated, with HETP values ranging from 0.21 to 0.3 m that further confirm their suitability for ERD applications.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17614–17627"},"PeriodicalIF":3.9,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solvent-Free Aerobic Oxidation of Toluene on High-Entropy (MnFeCuCoNi)3O4 Oxide Supported on Reduced Graphene Oxide","authors":"Seyedsaeed Mehrabi-Kalajahi*,&nbsp;Ahmad Ostovari Moghaddam*,&nbsp;Seyed Amir Hossein Vasigh,&nbsp;Fahimeh Hadavimoghaddam,&nbsp;Xueqiang Qi,&nbsp;Hassan Yousefi Bavili,&nbsp;Mikhail A. Varfolomeev,&nbsp;Behrouz Shaabani*,&nbsp;Iskander Vakhitov,&nbsp;Alexei Rozhenko and Andreu Cabot,&nbsp;","doi":"10.1021/acs.iecr.5c02227","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02227","url":null,"abstract":"<p >The growing demand for noble metal-free heterogeneous catalysts in selective, solvent-free oxidation reactions faces a persistent challenge: balancing high activity with practical scalability. Addressing this gap, we present a scalable route for the synthesis of the (MnFeCuCoNi)₃O₄ high-entropy oxide (HEO) catalyst and its composite with reduced graphene oxide (HEO-rGO). Comprehensive characterizations, including X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM, thermogravimetry analysis (TGA), confirmed the successful formation of a single-phase spinel HEO structure and their relatively uniform dispersion on the rGO matrix, minimizing aggregation and maximizing accessible active sites. The HEO–rGO composite demonstrates exceptional performance in the solvent-free aerobic oxidation of toluene, achieving conversions of 13.6% (1 atm) and 18.5% (10 atm) within 5 h, with remarkable selectivity for benzaldehyde (&gt;91 and 87%, respectively). These metrics rank among the highest reported values for noble metal-free systems. Mechanistic studies reveal that this activity stems from synergistic effects: (i) the multicationic HEO structure enhances lattice oxygen mobility, (ii) abundant oxygen vacancies facilitate reactant activation, and (iii) rGO promotes electron transfer and product desorption. Density functional theory (DFT) calculations further corroborate the critical role of oxygen vacancies in lowering the energy barrier for toluene oxidation. This work not only advances the design of high-entropy catalysts for selective oxidations but also provides a scalable, cost-effective strategy for converting toluene─an abundant petrochemical feedstock─into high-value benzaldehyde, with promising industrial applicability.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17495–17506"},"PeriodicalIF":3.9,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modeling and Parameter Estimation of Acrylate Radical Solution Polymerization under High-Temperature Semibatch Operating Conditions","authors":"Mahsa Esmaeilzadeh,&nbsp; and ,&nbsp;Robin A. Hutchinson*,&nbsp;","doi":"10.1021/acs.iecr.5c02197","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02197","url":null,"abstract":"<p >Understanding the kinetics of radical polymerization, especially under commercial high-temperature semibatch starved feed conditions, is a challenging task. This complexity is particularly pronounced for acrylate monomers, where the impact of secondary reactions on polymer properties and the polymerization rate becomes crucial. This study estimates kinetic coefficients for butyl acrylate (BA) homopolymerization, with a particular focus on the reaction network essential for predicting the macromonomer content. Incorporating chain-length-dependent termination kinetics into the model, the kinetic coefficients for backbiting, scission, termination, and transfer to solvent are estimated from available data. This refined model shows substantial improvements in predictions for not only macromonomer content but also critical variables such as weight-averaged molar masses, free monomer concentrations, and molar mass distributions. The same model and parameter estimation strategy is applied to better understand the significantly higher macromonomer and lower branched polymer content obtained when polymerizing isobornyl acrylate (iBoA) compared to BA. The estimated kinetic parameters, in particular the reduced rate coefficients for iBoA termination and for monomer addition to the midchain radical compared to those for BA, align with our understanding of these systems. This insight not only underscores the utility of precise parameter estimation in representing complex systems but also opens avenues for modeling a broader range of acrylate polymerization systems.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17514–17528"},"PeriodicalIF":3.9,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Deep Eutectic Solvent as a Working Fluid Pair in an Absorption Refrigeration System","authors":"Yangzheng Bao,&nbsp;Jin Yang,&nbsp;Junyi Ji,&nbsp;Kui Ma*,&nbsp;Hongjiao Li* and Bin Liang,&nbsp;","doi":"10.1021/acs.iecr.5c01794","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c01794","url":null,"abstract":"<p >Designing efficient working fluid pairs for absorption refrigeration systems (ARSs) driven by low-grade heat remains a significant challenge. Here, we introduce a deep eutectic solvent (DES) comprising methanol and choline chloride–urea (ChCl–UR) as the working fluid pair. The as-synthesized DES has a viscosity of up to 52.69 mm²/s. Hydrogen bonding was confirmed by infrared spectroscopy, and the network transformed to urea-bridged aggregates as the concentration of ChCl–UR increased. The equilibrium vapor pressure of methanol was maximumly reduced to 5.76 kPa at room temperature, corresponding to a cooling temperature of 278.15 K. A modified nonrandom two-liquid (NRTL) model successfully described the liquid–vapor equilibrium phenomenon with an average relative error of up to 6.10%. With the fluid pair of methanol to ChCl–UR of 1.31:1 (mol/mol), a single-effect ARS achieved a coefficient of performance (COP) greater than 0.8. Furthermore, in a compression-assisted ARS, the refrigeration temperature further decreased, improving the overall efficiency.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17933–17945"},"PeriodicalIF":3.9,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular Dynamics Analysis of Experimental Results for an Optimal Indium Oxide Dopant Concentration in Polyaniline for Effective Formaldehyde Sensing","authors":"Chandra Mouli R. Madhuranthakam*,&nbsp;Saientan Bag,&nbsp;Bhoomi H. Mavani and Alexander Penlidis*,&nbsp;","doi":"10.1021/acs.iecr.5c02102","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02102","url":null,"abstract":"<p >Polyaniline (PANI) doped with indium oxide (IO) is an excellent gas sensing material for detecting formaldehyde (F). It is proposed that an optimal weight percentage of IO exists in PANI composite that can exhibit higher sensitivity to F. To study the effect of the level of IO concentration in PANI, molecular dynamics (MD) simulations are performed. IO concentrations range from 0% (pure PANI) to 10% (w/w) in the PANI composite, and the corresponding weight percent of F penetrant loading is determined. A parabolic trend is observed where the sensitivity of PANI-IO sensing material reaches a maximum and then decreases with a further increase in dopant concentration. MD simulation trends agree with experimental results. The findings from this study are not only crucial for formaldehyde detection but can also be extended to the detection of other volatile organic compounds.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17477–17484"},"PeriodicalIF":3.9,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational Fluid Dynamics Simulations Applied to Polymerization Reactor Design: A Case Study of Tubular Loop Reactor","authors":"Ya-Nan Yang,&nbsp;Jian-Peng Han,&nbsp;Xi-Bao Zhang,&nbsp;He Lei* and Zheng-Hong Luo*,&nbsp;","doi":"10.1021/acs.iecr.5c02681","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02681","url":null,"abstract":"<p >The loop reactor for polyolefin production involves complex interactions between liquid–solid flow and polymerization reaction, which significantly influence the reactor’s overall performance. Computational fluid dynamics (CFD) offers valuable insights into these interactions, thereby aiding in the design of reactor configurations and operating parameters. In this study, a three-dimensional CFD model of a pilot-scale loop reactor is developed by integrating the Euler–Euler model, the kinetic theory of granular flow, and a simplified polymerization kinetics scheme. Specifically, a general procedure for reactor design based on CFD modeling is outlined, in which the uniformity index is used to assess the reactor’s performance. Based on this procedure, key configuration and operating parameters for the loop reactor are selected. The simulation results provide design recommendations for the loop reactor’s bend geometry, guide vanes, axial-flow pump speed, and jacket cooling water temperature. This study offers valuable insights and guidance for the design of general reactors.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17946–17957"},"PeriodicalIF":3.9,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergistically Enhancing Dispersibility and Thermoelectric Performance of Carbon Nanotubes by Biomass Carboxymethyl Cellulose","authors":"Ningjiang Hu,&nbsp;Jinsong Yang,&nbsp;Hui Li*,&nbsp;Han Zhang,&nbsp;Wenbo Wang,&nbsp;Jianhao Zhu,&nbsp;Yong Zhang* and Pengcheng Li*,&nbsp;","doi":"10.1021/acs.iecr.5c02529","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02529","url":null,"abstract":"<p >Single-walled carbon nanotubes (SWCNT) have unique potential in the fields of wearable devices and flexible thermoelectric (TE) materials. However, limited attention has been devoted to investigating the thermoelectric performance of CNT with natural cellulose. This study investigates the effects of carboxymethyl cellulose (CMC) with varying contents and degrees of substitution (DS) on the microstructure and thermoelectric performance of SWCNT. A significant interaction between the carboxylate groups and SWCNT leads to charge alterations within SWCNT, resulting in an elevated carrier concentration and improved dispersion of SWCNT. Consequently, when the CMC content was 20 wt % and the DS value was 0.7, the highest power factor of 336 μW m^–1 K^–2 was achieved, significantly surpassing that of pristine SWCNT. Moreover, the CMC/SWCNT film-based thermoelectric generator exhibits an output power of up to 284.7 nW under a temperature difference of 30 K and demonstrates stable temperature-sensing ability. This study paves the way for the development of high-performance TE materials for energy harvesting.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17759–17768"},"PeriodicalIF":3.9,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Organic-Free Preparation of Beta with Hierarchical Pores via a Potassium Carbonate-Assisted Method","authors":"Yunqi Hu,&nbsp;Chenyang Zhao,&nbsp;Zhaojun Liu,&nbsp;Honghai Liu,&nbsp;Hongjuan Zhao,&nbsp;Xinye Fan,&nbsp;Gen Li,&nbsp;Hong Meng and Hongtao Liu*,&nbsp;","doi":"10.1021/acs.iecr.5c02235","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02235","url":null,"abstract":"<p >Beta zeolite with micromesoporosity showed great application potential due to its hierarchical structure. However, this type of hierarchical zeolite was usually prepared in the presence of both an organic microtemplate and a meso-template, which limited its widespread application. In this investigation, a simple and entirely inorganic procedure to manipulate the micromesopore structure was reported. Herein, microporosity was induced by the presence of crystal seeds (CS), and mesoporosity was obtained via the introduction of potassium carbonate. The comprehensive characterization results exhibited that the obtained materials featured a high degree of crystallization and a much-enhanced mesoporosity structure (surface area of mesopores: 121.3 m²·g^–1 and mesoporosity volume: 0.15 cm³·g^–1). Moreover, this novel material showed greatly improved catalytic cracking properties toward heavy oil.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17507–17513"},"PeriodicalIF":3.9,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018337","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of Porous Sulfur-Doped Petroleum Coke-Derived Carbon Materials with Adjustable Interlayer Spacing via a Low-Temperature Sulfurization Strategy and Its Efficient Sodium Storage Mechanism","authors":"Yanlu Lv,&nbsp;Lin Yang* and Yanjun Zhong,&nbsp;","doi":"10.1021/acs.iecr.5c02280","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02280","url":null,"abstract":"<p >To address the limitations of sodium-ion battery (SIB) anodes, porous sulfur-doped carbon materials derived from petroleum coke (PC) were synthesized through a green, scalable approach involving low-temperature sulfidation and gradient carbonization. This approach enabled the simultaneous expansion of the interlayer spacing (<i>d</i>₀₀₂ = 0.373 nm for S-CY-850), and the construction of hierarchical pores (1–6 nm), achieved through thiophenic sulfur-induced lattice strain and <i>in situ</i> etching by CS₂/SO₂ evolution. The optimized S-CY-850 anode exhibited exceptional performance, including a high reversible capacity (420 mAh g^–1 at 0.5 A g^–1, representing a 5.38-fold improvement over undoped carbon), outstanding cycling stability (90.0% capacity retention after 2000 cycles), excellent rate capability (236.41 mAh g^–1 at 5.0 A g^–1), and an initial Coulombic efficiency (ICE) of 75.6%. This work presents a high-performance, low-cost anode solution for sodium-ion batteries (SIBs) derived from industrial byproducts, highlighting the synergistic effect of sulfur doping and microstructure modulation.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17732–17749"},"PeriodicalIF":3.9,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018314","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}