Industrial & Engineering Chemistry Research最新文献

{"title":"Chemical Recycling of End-of-Life Tires Using Catalytic Pyrolysis: Effects of Catalysts and Process Conditions toward the Production of a Highly Aromatic Pyrolysis Oil","authors":"Stylianos D. Stefanidis, Eleni Pachatouridou, Eleni Heracleous, Angelos A. Lappas, Iacovos A. Vasalos","doi":"10.1021/acs.iecr.5c02163","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02163","url":null,"abstract":"End-of-life tires (ELTs) represent both an environmental challenge and an opportunity as an untapped resource for materials and energy recovery. This work demonstrates the catalytic pyrolysis of ELTs using equilibrium FCC catalysts with varying metal contamination levels and ZSM-5 catalyst additives to produce highly aromatic oils with considerable promise for direct application. The investigation employed a systematic approach, screening catalysts in a batch reactor followed by validation in a continuous process development unit. The produced oils were characterized by quantitative methods to determine aromatic hydrocarbon yields and catalyst selectivity. Results showed strong agreement between the two setups with equilibrium FCC catalysts achieving 48 wt % oil yields containing up to 87 wt % aromatic hydrocarbons. Ni contamination on the catalyst shifted selectivity from monoaromatic to polyaromatic hydrocarbons and increased the overall aromaticity, rendering the oil attractive as a feedstock to produce carbon black and as a source of BTX and aromatic fuel additives.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"18 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140855","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":"The Effect of Diffusion Limitations on the NH3–SCR Process over a Shaped Fe-Modified Clinoptilolite Catalyst","authors":"Magdalena Saramok, Katarzyna Antoniak-Jurak, Monika Ruszak, Bogdan Samojeden, Monika Motak, Marek Inger","doi":"10.1021/acs.iecr.5c03158","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03158","url":null,"abstract":"Research was carried out on the catalytic effect of Fe-modified clinoptilolite in the selective catalytic NO_<i>x</i> reduction by NH₃ (NH₃–SCR) in the real tail gas stream, taken from the Łukasiewicz – INS pilot plant for testing the ammonia oxidation process. To obtain a catalyst with the desired textural parameters and increase the acidity of a zeolite and the content of Fe³⁺ active sites, clinoptilolite was modified with iron using a two-stage method, including dealumination and wet impregnation. Catalytic tests were performed over the shaped Fe-modified clinoptilolite to study the effect of diffusion limitations on the overall NH₃–SCR reaction rate. The effectiveness factor of the catalyst shaped into pellets was determined based on the Weisz modulus. It was found that diffusion limitations influence the rate of the contact process to a greater extent, the larger the size of the shaped catalyst body. The contact process over the pellets 5.0 mm in diameter and 4.8 mm high occurred in the diffusion regime, and the diffusion limitations were influenced more by Knudsen diffusion than by molecular diffusion. Simulation calculations of the <i></i><math display=\"inline\"><msub><mi>X</mi><mrow><msub><mrow><mi>NO</mi></mrow><mrow><mi>x</mi></mrow></msub></mrow></msub><mo>=</mo><mi>f</mi><mo>(</mo><mi>T</mi><mo>,</mo><mi>τ</mi><mo>)</mo></math> relationship were performed for various sizes of the catalyst pellets. It was found that the temperature had an insignificant effect on the shaped catalyst’s performance within the considered “temperature window”. The pellet size and contact time proved to be significantly more critical for achieving high conversion.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"94 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145153639","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":"Physics-Informed Neural Network with NSGA II and Levenberg–Marquardt Method for Kinetic Modeling in Heavy Oil Hydrocracking","authors":"Shahla Alizadeh, Souvik Ta, Ajay K. Ray, Lakshminarayanan Samavedham","doi":"10.1021/acs.iecr.5c02581","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02581","url":null,"abstract":"Accurately modeling reaction kinetics in heavy oil hydrocracking is essential for optimizing reactor performance and improving product distribution predictions. This study proposes a novel hybrid framework that integrates a physics-informed neural network (PINN) with nondominated sorting genetic algorithm II (NSGA-II) and Levenberg–Marquardt (LM) optimization method to achieve fast and accurate estimation of kinetic parameters. Unlike conventional approaches, the proposed method combines global and local search: NSGA-II generates high-quality initial parameter estimates, while LM efficiently refines them, ensuring convergence within 300 epochs. This hybrid framework leverages a neural network to model time-evolving behavior, while a Runge–Kutta–based solver enforces reaction kinetics, enabling robust kinetic parameter estimation under physical constraints. Four kinetic models previously proposed in hydrocracking research were implemented as physics constraints and systematically evaluated using the PINN framework. Among them, the most detailed, referred to here as model 4, emerged as the most comprehensive and accurate, capturing all major saturates, aromatics, resins, and asphaltenes (SARA) conversions and byproduct formation (gas and coke). Building upon this, a refined 10-parameter kinetic model was proposed by excluding three low-sensitivity reaction parameters. The simplified model preserved all dominant pathways and demonstrated excellent predictive accuracy across four temperatures (360–400 °C), total error (data + physics MSE on mass fractions) was on the order of 10^–3 to 10^–2 across training, validation, and testing, with <i>R</i>² between 0.93 and 0.99. To prevent overfitting and improve generalization, early stopping and a 20% dropout strategy were employed. This study presents a novel application of a hybrid PINN framework that integrates a multiobjective evolutionary algorithm with numerical optimization for kinetic modeling in heavy oil hydrocracking. By embedding physical constraints into the learning process, the framework offers a scalable, interpretable, and accurate approach for estimating reaction parameters and capturing the dynamic behavior of the hydrocracking process.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"4 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140848","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":"Amino Acids: Critical Oxidation Products in CO2 Capture by Aqueous Piperazine","authors":"Fred Closmann, Cameron S. Carter, Gary T. Rochelle, Fahad Alshehri","doi":"10.1021/acs.iecr.4c03927","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03927","url":null,"abstract":"CO₂ capture by aqueous piperazine (PZ) or other amines must address the degradation of the amine by reaction with oxygen from the flue gas. Ammonia, ethylenediamine (EDA), formate, and oxopiperazine (OPZ) have previously been quantified as important degradation products of PZ. In this work, a quadrupole time-of-flight mass spectrometer (QTOF-MS) coupled to a high-performance liquid chromatograph (HPLC) detected six amino acids and their lactams and amides with PZ. These six amino acids were identified and quantified using anion chromatography with pulsed amperometric detection (PAD). Samples were hydrolyzed to amides with NaOH to allow analysis of the total amino acids. The hydrolyzed amino acids included aminoethylglycine (AEG), piperazineacetic acid (PZAA), glycine (GLY), and 3-oxopiperazineacetic acid (3OPZA), the lactam of ethylenediaminediacetic acid. The total amino acids in hydrolyzed pilot campaign samples were present at concentrations (140 mmol/kg), which likely enhanced the effective solubility of Fe²⁺/Fe³⁺ and increased the rate of PZ oxidation.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"42 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140575","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":"Lithium Nitride-rich Li Protection Layer via Facile Lewis Acid–Base Reaction for Li Metal Batteries","authors":"Seokjun Kim, Taehyeong Kim, Wonjin Oh, Jinhyung Kim, Chanho Lee, Wooseop Jo, Junghyun Choi, Dongsoo Lee, Seho Sun","doi":"10.1021/acs.iecr.5c02132","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02132","url":null,"abstract":"In this study, we present a scalable approach for forming a lithium nitride (Li₃N)-rich protection layer on Li metal, enabling practical applications for high-energy-density lithium metal (Li) batteries. This protection layer is developed through a simple Lewis acid–base reaction involving the direct contact of Li metal with xylylenediamine. This method employs a two-step solution coating process. First, the native oxide layer on the Li surface is removed via chemical polishing. Then, the Li₃N protection layer is coated onto the polished Li metal (Li₃N@Li). This ensures an effective chemical reaction between Li metal and xylylenediamine, leading to a robust protection layer. The Li nucleation and growth behavior of Li₃N@Li shows a dendrite-free morphology with dense and compact properties. Electrochemical evaluations in Li||Li symmetric cells demonstrate dendrite-free Li deposition at 0.5 mA cm^–2 for a capacity of 2 mA h cm^–2. Additionally, pairing the protected Li anode with a LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode achieves an areal capacity of 5 mA h cm^–2. The resulting Li||NCM full cells exhibit stable cycling stability with 78.5% capacity retention and an average Coulombic efficiency of 99.8% for over 100 cycles. This work provides insights into the practical realization of high-energy-density Li metal batteries, offering a scalable solution for developing protection layers on Li metal anodes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"73 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140576","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":"Physics-Based Dynamic Modeling of Top-Fired Steam Methane Reforming Furnaces Integrating a Simplified Radiation Model","authors":"Zahra Moein kia, Ehsan Vafa, Fathollah Farhadi","doi":"10.1021/acs.iecr.5c02638","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02638","url":null,"abstract":"A dynamic, physics-based model has been developed for steam methane reformers (SMRs) with conventional geometries to enable real-time optimization and control, offering a flexible framework adaptable to complex geometries and different operational conditions. Unlike computational fluid dynamics (CFD) models, this approach reduces computation time, making it ideal for online monitoring. The model divides the reformer into zones with uniform temperature and composition, formulating mass, energy, and momentum balances for each zone. Radiative heat transfer is analyzed using the Hottel-zone method with simplified exchange area calculations. Validation against steady-state experimental data confirms the model’s accuracy, with minor deviations linked to exchange area calculations. The quantitative assessment yielded a root mean squared error (RMSE) of 0.0156 for the hydrogen mole fraction and 24.84 K for the tube outer wall temperature, calculated with respect to the averaged profiles across cross sections along the furnace height. By solving nonlinear differential-algebraic equations (DAEs) dynamically, the model predicts temperature, composition, and pressure profiles of process and combustion gases, plus tube wall temperature. It captures transient behaviors, with time constants of 46, 40, and 24 min for process gas composition changes, flow reduction, and burner failure, respectively. Dynamic interactions between reformer subsystems are emphasized, as temperature fluctuations in one burner or tube row affect adjacent rows. The model supports dynamic balancing by maintaining safe tube wall temperatures during disturbances, enabling targeted fuel redistribution to reduce temperature nonuniformities, increase allowable operating temperatures, and improve reformer efficiency.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"22 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140579","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 Multi-Stage Graph Neural Network–Physics-Informed Neural Network (GNN–PINN) Framework for Thermodynamic Property Prediction","authors":"Jinyoung Park, Ruth M. Muthoka, Sunghyun Jang, Yongjin Lee","doi":"10.1021/acs.iecr.5c02302","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02302","url":null,"abstract":"Accurately predicting thermodynamic properties across various conditions remains a critical challenge, particularly in scenarios involving sparse data or complex molecular interactions. This study proposes a multistage hybrid modeling framework that integrates Graph Neural Networks (GNN) and Physics-Informed Neural Networks (PINN) to predict essential thermodynamic properties, including enthalpy and entropy, for pure substances under various conditions. The model is developed in three distinct stages. First, a GNN encoder captures atomic-level interactions (both bonded and nonbonded) from molecular structures, generating structurally enriched molecular embeddings while leveraging critical constants and reduced state variables through a masking strategy that enables learning from single-phase data sets. Second, a regression submodel utilizes these embeddings to accurately predict saturation pressure (<i>P</i>^sat) from molecular structure and temperature, modeling phase equilibrium behavior. Finally, the third stage employs PINN-based fine-tuning, embedding thermodynamic constraints─such as Gibbs free energy equality at phase equilibrium and enthalpy–entropy coupling─as penalties in the loss function to enforce thermodynamic consistency. This integrated GNN–PINN approach accurately predicts vapor- and liquid-phase enthalpies, entropies, and saturation pressures, maintaining robust performance even at equilibrium conditions. The model offers a physically consistent and reliable method for predicting thermodynamic properties, effectively capturing complex molecular interactions while adhering to fundamental physical laws.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"63 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140578","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":"Tungsten-Modulated Ru/ZrO2 Catalysts Promote Selective Hydrogenation of Phthalide to Hexahydrophthalide: Synergistic Effects of Metal–Support Interaction and Acidic Characteristics","authors":"Yuhang Gong, Zi Lin, Songyin Yu, Changhai Liang, Chuang Li","doi":"10.1021/acs.iecr.5c02785","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02785","url":null,"abstract":"The development of chemically recyclable polyester derived from lactone ring-opening polymerization monomer hexahydrophthalide offers a promising solution to the plastic pollution issue. The selective hydrogenation of phthalide to hexahydrophthalide is a green atom-economy route; however, the selective hydrogenation of the benzene ring in phthalide containing different functional groups is a significant challenge. In this work, a series of W-modified Ru/ZrO₂ catalysts were prepared via impregnation followed by liquid-phase reduction, and the effect of tungsten loading on catalytic performance was systematically evaluated for the hydrogenation of phthalide. Under 4 MPa H₂ and 180 °C, the conversion of phthalide and the selectivity of hexahydrophthalide reach 98.6% and 80.4% on the Ru/15WZr catalysts, respectively. Compared to the Ru/ZrO₂, it has a relatively low activation energy (51.49 kJ/mol) and excellent catalytic stability, with 110 h of catalytic performance remaining basically unchanged. The introduction of W species enhances the interaction between Ru and the support, generating an electron-deficient Ru^δ+ structure and abundant acidic sites. This leads to the directional activation and hydrogenation of the aromatic ring of phthalide, thereby improving the selectivity of hexahydrophthalide. This work not only provides fundamental insights into the design of efficient hydrogenation catalysts but also establishes a versatile strategy for converting phthalide to recyclable lactones through precise control of the active sites.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"647 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140580","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":"Biomethane and CO2-Based Biorefinery: Process Concept and Operability Analysis","authors":"Giuliana V. G. Lesak, Marcos L. Corazza, Luiz Fernando de Lima Luz, Jr., Fernando V. Lima","doi":"10.1021/acs.iecr.5c02143","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02143","url":null,"abstract":"The climate crisis, along with the need to improve human living standards and preserve the environment, is driving the demand for processes that are sustainable in terms of emissions, heat demand, electricity sources, water usage, and food supply. Developing such processes requires renewable and sufficient raw materials, heat, power, and complex mass and heat integration schemes. In this context, a process for synthetic hydrocarbon production from biomethane with power cogeneration is proposed. Biomethane is used as a raw material for the process and for the power plant, while CO₂ is fed to the process in similar mass proportions to biomethane. By this process, including steam methane reforming, reverse water–gas shift, and Fischer–Tropsch synthesis (FTS) reactions, it is possible to obtain 29.3 tons/h (1048 m³/day) of synthetic liquid fuels. The process is self-sufficient in terms of water and power, and it provides a considerable amount of excess heat for byproduct generation, showing itself as a promising alternative for sustainable fuel production. Operability analyses are performed for the first time in the literature on simulations of FTS plants to assess the effect of key process input variables on the simulation convergence and process output regions. A set of 26 inequality constraints that describe the feasible input region for the process is obtained, which can be used for future optimization. The proposed approach enhances the process understanding and represents an important step forward to allow hard-to-converge flowsheet optimizations of complex and highly integrated process models.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"53 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140577","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":"Theoretical Development of the Composite Absorbent for Maleic Anhydride Production: Insights from COSMO-RS, VLE Experiments, and Process Simulation","authors":"Mingmei Wang, Junyang Liu, Bin He, Ruixia Liu, Ruiyi Yan, Fuwei Li, Hong Zhao, Erqiang Wang, Zengxi Li","doi":"10.1021/acs.iecr.5c01925","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c01925","url":null,"abstract":"Maleic anhydride, produced via <i>n</i>-butane oxidation, is typically selectively absorbed from the water-rich reaction gas stream by organic solvents, but the process is challenged by the inherent conflict between hydrophobicity of solvents and their affinity for maleic anhydride. Herein, a composite absorbent strategy was proposed based on the COSMO-RS model, vapor–liquid equilibrium experiments, and process simulation, demonstrating that the addition of 20 wt % sulfolane to dibutyl phthalate effectively balances hydrophobicity and absorption capacity. As a result, the absorbent consumption, desorption energy demand, and exergy loss were reduced by 40%, 27%, and 38%, respectively. Microscopic insights from σ-profiles and molecular surface electrostatic potential distribution maps revealed that the enhanced absorption capacity arises from an increased frequency of complementary polar interactions between solvents and solutes. The methodology holds broader implications for optimizing solvents in extractants and absorbents, particularly those acting on polar solute systems.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"18 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140581","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}