Industrial & Engineering Chemistry Research最新文献

{"title":"Environmental Aging of Polymers to Evaluate Their Potential for Remediating Natural Gas Pipelines","authors":"Mohammadjavad Haji Rezaei,&nbsp;Aiden Ferreira,&nbsp;Maile Campbell,&nbsp;Deepro Ghosh,&nbsp;Keven Alkhoury,&nbsp;Zakhar Lyakhovych,&nbsp;Edith Mathiowitz,&nbsp;Vikas Srivastava and Ryan Poling-Skutvik*,&nbsp;","doi":"10.1021/acs.iecr.5c02255","DOIUrl":"10.1021/acs.iecr.5c02255","url":null,"abstract":"<p >We assess the aging of polymeric materials in natural gas environments for potential applications in pipeline remediation as liner materials. Three commercially available polymers─high-density polyethylene (HDPE), Nylon-6/6 polyamide (PA), and polyvinylidene fluoride (PVDF)─are aged under accelerated conditions in a model natural gas environment of pure alkanes at 250 PSI and 90 ^°C for up to 30 days. The Young’s modulus and yield stress of these polymers remain unchanged within experimental error after exposure to the natural gas environment. Dynamic mechanical analysis, however, reveals drastic changes to polymer chain dynamics, with the activation energy for segmental relaxations reduced by up to 50%, corresponding to accelerated molecular motion. The environmental aging is confirmed through FTIR, which found an increase in the density of natural gas molecules within the polymer matrices. Additionally, these changes in the dynamics within polymeric solids are reversible; prolonged removal from the gas atmosphere resulted in the activation energies returning to near-initial values within 2 weeks. These observations suggest that this aging response is dominated by physical processes in which the polymers absorb natural gas molecules due to the increase in partial pressures, as opposed to a chemical mechanism in which the natural gas reacts irreversibly with the polymer chains. In applications for pipeline remediation, our results indicate that polymeric liners will provide sufficient mechanical rigidity but may suffer from accelerated rates of creep facilitated by the increase in local polymer dynamics.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17724–17731"},"PeriodicalIF":3.9,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.iecr.5c02255","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906653","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":"Solid-State Self-Assembly in Plasticized PVC/ABS Blends: Effects on Impact Strength and Dynamic Mechanical Properties","authors":"Masume Masudi,&nbsp; and ,&nbsp;Yousef Jahani*,&nbsp;","doi":"10.1021/acs.iecr.5c01486","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c01486","url":null,"abstract":"<p >In this study, plasticized poly(vinyl chloride)/acrylonitrile–butadiene–styrene (PVC/ABS) blend was prepared via melt mixing. The morphological evolution and its effects on the blend’s properties were investigated over time. Scanning electron microscopy (SEM) analysis revealed the formation of rod-like supramolecular structures, suggesting the self-assembly in the blend. The simultaneous effects of physical aging, molecular-level interactions in the grafted SAN shell, and plasticizer-induced mobility are critical for the development of the unique microstructures in this system. The size and number of the structures were influenced by the plasticizer content, increasing with time and temperature. The impact strength increased due to the formation of these structures, and for the PVC/ABS-75/25 blend, it increased from 19 to 44.5 kJ/m². Dynamic mechanical analysis (DMA) revealed partial miscibility in the blend. The glass transition temperature (<i>T</i>_g) of PB-<i>g</i>-SAN in ABS was slightly increased over time due to the formation of rod-like structures.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17677–17684"},"PeriodicalIF":3.9,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018367","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":"Crown Ether Confined in a 2D MXene Membrane for Mono-/Divalent Ion Separation","authors":"Xufan Zhou,&nbsp;Yaxin Zhang,&nbsp;Zhixu Chen,&nbsp;Shijin Zhao,&nbsp;Haonan Yang,&nbsp;Guozhen Liu*,&nbsp;Wenqi Ji,&nbsp;Yanan Guo,&nbsp;Gongping Liu* and Wanqin Jin,&nbsp;","doi":"10.1021/acs.iecr.5c02752","DOIUrl":"10.1021/acs.iecr.5c02752","url":null,"abstract":"<p >Mono-/divalent ion separation is a key and challenging industrial process. Two-dimensional (2D) material membranes are promising for molecular separation, while it remains a grand challenge to achieve high ion separation performance owing to the undesirable nanochannel microenvironment and small size difference of ions. Herein, we reported on the construction of the crown ether confined 2D MXene membrane for mono-/divalent ion separation. The introduction of crown ether finely tuned the interlayer spacing that facilitates ion dehydration and significantly enhanced the affinity toward monovalent ions. The resulting membrane exhibits a high monovalent ion permeation rate (0.85 mol·m^–2·h^–1 for K⁺ and 0.81 mol·m^–2·h^–1 for Li⁺) and mono-/divalent ion selectivity (39 for Li⁺/Mg²⁺ and 40.2 for K⁺/Mg²⁺). This performance is superior to the limits for the state-of-the-art membranes, showing great potential for ion separation.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17844–17852"},"PeriodicalIF":3.9,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906558","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 of the Performance Loss due to Catalyst Deactivation in Fixed- and Fluidized-Bed Reactors","authors":"M. Andrea Pappagallo,&nbsp;Tilman J. Schildhauer,&nbsp;Oliver Kröcher and Emanuele Moioli*,&nbsp;","doi":"10.1021/acs.iecr.5c02248","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02248","url":null,"abstract":"<p >A method to assess the impact of deactivation phenomena on the global performance of a catalytic reactor was developed. The methodology is applied here to the case of CO methanation, where the catalyst is subject to deactivation by coking. This method can be extended to other reactions and deactivation mechanisms. The method is based on the integration of a single differential equation to describe the activity of the catalyst and on the evaluation of the profiles in the reactor through consecutive steady states at progressively lower activity values. The model was applied successfully to both fixed- and fluidized-bed methanation, with small differences between the two cases. This model showed promising results in a case study, with a correct description of the decrease in the level of CO conversion due to coking. It also allowed us to observe the higher resistance to deactivation of fluidized-bed reactors compared to fixed-bed ones at similar conditions. The time needed to reach 25% conversion in fluidized-bed reactors was calculated to be 5 to 50 times higher compared to that in fixed-bed reactors. The model allows optimizing the reactor with respect to deactivation, acting on the reactor geometry, size, and operating conditions to achieve the best long-term performance.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17529–17542"},"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.5c02248","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018303","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":"Selective Oxidation of Methacrolein to Methacrylic Acid over Sb-Doped (NH4)H3PMo11VO40","authors":"Tianyu Guo,&nbsp;Lei Wang,&nbsp;Haitao Qian,&nbsp;Yuan Tian,&nbsp;Gang Wang,&nbsp;Jie Li and Chunshan Li*,&nbsp;","doi":"10.1021/acs.iecr.5c02100","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02100","url":null,"abstract":"<p >Selective oxidation of methacrolein (MAL) to methacrylic acid (MAA) is a pivotal step in the industrial production of methyl methacrylate (MMA). In this study, a series of Keggin-type ammonium phosphomolybdovanadate heteropoly acid (NH₄HPAV) catalysts with modification of Sb component were systematically investigated for their catalytic performance in MAL partial oxidation to MAA. Comprehensive physicochemical characterizations including XRD, FT-IR, Raman spectroscopy, NH₃-TPD, chemical titration, H₂-TPR, and XPS were employed to elucidate the structural and functional impact of Sb incorporation. The results indicated that the introduced Sb partially substituted protons in the secondary structure, leading to a decrease of surface Bro̷nsted acid sites and significant modulation of the redox behavior of molybdenum species. In addition, the incorporation of Sb component would also improve the MAL adsorption and MAA desorption abilities on the catalyst surface. A strong linear relationship was observed between the MAL conversion and reduction capacity of the molybdenum species, highlighting the critical role of redox properties enhanced by Sb. The optimized Sb-modified catalyst exhibited a 23.6% increase in MAL conversion, compared to the unmodified catalyst while maintaining comparable MAA selectivity.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 36","pages":"17485–17494"},"PeriodicalIF":3.9,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145018299","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":"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}