Pub Date : 2026-02-01DOI: 10.1021/acs.iecr.5c03896
Fangfang Zhao,Jun Tang,Ruiming Zhou,Xiaowen Zhang,Dejian Yan,Zhenpan Chen,Kuiyi You,He’an Luo
A new stable inorganic bonded Lewis acid catalyst ((FeCl2)2-SiO3) was synthesized and applied for the liquid-phase catalytic nitration of benzene with NO2 to nitrobenzene in the presence of molecular oxygen. The results demonstrate that the inorganic bonded 10% (FeCl2)2-SiO3 catalyst showed excellent catalytic performance with 98.5% benzene conversion and 99.6% selectivity to nitrobenzene at 50 °C. Moreover, the catalyst maintained a high nitrobenzene yield after five cycles of reuse without significant deactivation. Characterization by XRD, XPS, UV–vis, FT-IR, and SEM consistently confirmed the successful bonding of FeCl3 onto the silica support. Theoretical calculations further confirm that the Si–O–FeCl2 sites in (FeCl2)2-SiO3 serve as the active catalytic sites in the nitration. A possible reaction mechanism for the nitration process was proposed. Oxygen promotes the activation of NO2, while the Lewis acid sites contribute to the stabilization of NO3–. This synergy facilitates the formation of a stable electrophilic reagent, thereby significantly enhancing the reaction efficiency. This work provides a mild, efficient, safe, and eco-friendly approach for highly selective preparation of nitrobenzene with promising potential for industrial application.
{"title":"Mild and Efficient Catalytic Nitration of Benzene with NO2 to Nitrobenzene Promoted by Molecular Oxygen over Inorganic Bonded (FeCl2)2-SiO3","authors":"Fangfang Zhao,Jun Tang,Ruiming Zhou,Xiaowen Zhang,Dejian Yan,Zhenpan Chen,Kuiyi You,He’an Luo","doi":"10.1021/acs.iecr.5c03896","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03896","url":null,"abstract":"A new stable inorganic bonded Lewis acid catalyst ((FeCl2)2-SiO3) was synthesized and applied for the liquid-phase catalytic nitration of benzene with NO2 to nitrobenzene in the presence of molecular oxygen. The results demonstrate that the inorganic bonded 10% (FeCl2)2-SiO3 catalyst showed excellent catalytic performance with 98.5% benzene conversion and 99.6% selectivity to nitrobenzene at 50 °C. Moreover, the catalyst maintained a high nitrobenzene yield after five cycles of reuse without significant deactivation. Characterization by XRD, XPS, UV–vis, FT-IR, and SEM consistently confirmed the successful bonding of FeCl3 onto the silica support. Theoretical calculations further confirm that the Si–O–FeCl2 sites in (FeCl2)2-SiO3 serve as the active catalytic sites in the nitration. A possible reaction mechanism for the nitration process was proposed. Oxygen promotes the activation of NO2, while the Lewis acid sites contribute to the stabilization of NO3–. This synergy facilitates the formation of a stable electrophilic reagent, thereby significantly enhancing the reaction efficiency. This work provides a mild, efficient, safe, and eco-friendly approach for highly selective preparation of nitrobenzene with promising potential for industrial application.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"42 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097921","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}
Rapid shrinkage of silicone rubber (MVQ) foam after fast depressurization of supercritical carbon dioxide (scCO2) greatly restricts its practical application. Herein, an innovative strategy, i.e., immediate in situ post-cross-linking in high-pressure CO2, was developed. By investigating the effects of saturated temperature on pre-cross-linking density, as well as foaming temperature, foaming pressure, and post-cross-linking pressure on the diffusion coefficient (D), activation energy (Ea), and enthalpy (ΔH) of the cross-linking reaction, it was found that this strategy accelerated the cross-linking of MVQ and effectively inhibited the shrinkage of foam. Under optimal foaming conditions, the foam with an expansion ratio of 6.7, a porosity of 89.4%, and a density of 0.17 g/cm3 was successfully obtained. This high-expansion foam exhibited good resilience and could be used to prepare a simple sensor, with stable output currents of 0.15–0.25 μA under various touch ways, showing great potential in the field of intelligent sensors.
{"title":"Development of MVQ Foam by scCO2: High Expansion, Excellent Elasticity, and Potential Use in Intelligent Sensors","authors":"Jian Yang, Wu Guo, Shibing Bai, Dawei Xu, Li Li, Zhenhong Huang","doi":"10.1021/acs.iecr.5c04361","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04361","url":null,"abstract":"Rapid shrinkage of silicone rubber (MVQ) foam after fast depressurization of supercritical carbon dioxide (scCO<sub>2</sub>) greatly restricts its practical application. Herein, an innovative strategy, i.e., immediate in situ post-cross-linking in high-pressure CO<sub>2</sub>, was developed. By investigating the effects of saturated temperature on pre-cross-linking density, as well as foaming temperature, foaming pressure, and post-cross-linking pressure on the diffusion coefficient (<i>D</i>), activation energy (<i>E</i><sub>a</sub>), and enthalpy (Δ<i>H</i>) of the cross-linking reaction, it was found that this strategy accelerated the cross-linking of MVQ and effectively inhibited the shrinkage of foam. Under optimal foaming conditions, the foam with an expansion ratio of 6.7, a porosity of 89.4%, and a density of 0.17 g/cm<sup>3</sup> was successfully obtained. This high-expansion foam exhibited good resilience and could be used to prepare a simple sensor, with stable output currents of 0.15–0.25 μA under various touch ways, showing great potential in the field of intelligent sensors.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"41 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098332","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}
Biomass utilization produces large amounts of wastewater contaminated with phenolic and organic compounds, posing a major challenge for purification and resource recovery. To address this, the development of highly active, hydrothermally stable non-noble-metal catalysts is essential for applying aqueous-phase reforming (APR) to valorize this waste stream and produce sustainable hydrogen. In this work, a carbon-encapsulated nickel catalyst with a high metal loading (36.7 wt %), excellent dispersion, and small nickel particle size (∼5 nm) was prepared via pyrolysis. The coordination between amino functional groups in chitosan and nickel ions facilitated the homogeneous dispersion of the chitosan-nickel precursor. Pyrolysis resulted in the nickel nanoparticles being embedded well within a nitrogen-doped carbon (NC) matrix, which effectively inhibited particle agglomeration and improved hydrothermal stability. Catalytic performance tests revealed that the Ni@NC-350 catalyst achieved a phenol conversion of over 90% and a hydrogen selectivity of nearly 85%. Notably, after six consecutive APR cycles, no significant aggregation or deactivation of nickel nanoparticles was observed, indicating excellent hydrothermal stability. This study thus provides a robust and highly stable Ni-based catalyst, demonstrating promising application potential in the efficient treatment of phenol-containing organic wastewater with simultaneous hydrogen production.
{"title":"Engineering a Hydrothermally Stable Ni@NC Catalyst for Efficient Hydrogen Production from Aqueous-Phase Reforming of Biomass Wastewater","authors":"Yiyuan Zhou, Anqi Wang, Hui Luo, Mingge Li, Fucheng Chen, Xin Li, Qingwei Meng, Tiejun Wang","doi":"10.1021/acs.iecr.5c04527","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04527","url":null,"abstract":"Biomass utilization produces large amounts of wastewater contaminated with phenolic and organic compounds, posing a major challenge for purification and resource recovery. To address this, the development of highly active, hydrothermally stable non-noble-metal catalysts is essential for applying aqueous-phase reforming (APR) to valorize this waste stream and produce sustainable hydrogen. In this work, a carbon-encapsulated nickel catalyst with a high metal loading (36.7 wt %), excellent dispersion, and small nickel particle size (∼5 nm) was prepared via pyrolysis. The coordination between amino functional groups in chitosan and nickel ions facilitated the homogeneous dispersion of the chitosan-nickel precursor. Pyrolysis resulted in the nickel nanoparticles being embedded well within a nitrogen-doped carbon (NC) matrix, which effectively inhibited particle agglomeration and improved hydrothermal stability. Catalytic performance tests revealed that the Ni@NC-350 catalyst achieved a phenol conversion of over 90% and a hydrogen selectivity of nearly 85%. Notably, after six consecutive APR cycles, no significant aggregation or deactivation of nickel nanoparticles was observed, indicating excellent hydrothermal stability. This study thus provides a robust and highly stable Ni-based catalyst, demonstrating promising application potential in the efficient treatment of phenol-containing organic wastewater with simultaneous hydrogen production.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"55 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089663","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}
Pub Date : 2026-01-31DOI: 10.1021/acs.iecr.5c04936
Hidetaka Tobita
A new polymerization model for network formation that takes into account conformation-dependent intramolecular cross-linking is proposed. The pendant double bonds present in an active polymer are distinguished by their graph distance from the active center. The conformation of the chain between the active center and the pendant double bonds is assumed to be Gaussian. The proposed model is applied to miniemulsion vinyl/divinyl copolymerization, where the three-dimensional (3D) size of the resulting network polymer can be measured. The simulations consider both conventional free-radical polymerization (FRP) and ideal living polymerizations. The model can explain one of key differences between FRP and living polymerization: in FRP, the pendant double bonds are consumed from the very beginning of polymerization, whereas in living polymerization, this behavior does not occur. A large number of small rings are formed by the intramolecular cross-linking, and the dimensions of network polymers formed are larger than those of randomly cross-linked homogeneous networks at the same cycle rank level. The model proposed here predicts a larger three-dimensional size than the model that does not distinguish pendant double bonds by their location. The present model challenges the development of size- and structure-dependent polymerization kinetics, aiming to overcome the limitations of classical chemical kinetics.
{"title":"Modeling of Network Formation with Conformation-Dependent Intramolecular Cross-Linking in Vinyl/Divinyl Copolymerization","authors":"Hidetaka Tobita","doi":"10.1021/acs.iecr.5c04936","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04936","url":null,"abstract":"A new polymerization model for network formation that takes into account conformation-dependent intramolecular cross-linking is proposed. The pendant double bonds present in an active polymer are distinguished by their graph distance from the active center. The conformation of the chain between the active center and the pendant double bonds is assumed to be Gaussian. The proposed model is applied to miniemulsion vinyl/divinyl copolymerization, where the three-dimensional (3D) size of the resulting network polymer can be measured. The simulations consider both conventional free-radical polymerization (FRP) and ideal living polymerizations. The model can explain one of key differences between FRP and living polymerization: in FRP, the pendant double bonds are consumed from the very beginning of polymerization, whereas in living polymerization, this behavior does not occur. A large number of small rings are formed by the intramolecular cross-linking, and the dimensions of network polymers formed are larger than those of randomly cross-linked homogeneous networks at the same cycle rank level. The model proposed here predicts a larger three-dimensional size than the model that does not distinguish pendant double bonds by their location. The present model challenges the development of size- and structure-dependent polymerization kinetics, aiming to overcome the limitations of classical chemical kinetics.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"83 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089664","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}
Pub Date : 2026-01-31DOI: 10.1021/acs.iecr.5c04103
Thalita Fernandes, Antonio Araujo
This work introduces a framework for systematically determining the sample size required to build accurate metamodels in Automated Machine Learning (AutoML) pipelines. The method employs a feedback control strategy that favors simple regression models when sufficient, using nonlinear models only when necessary. At each iteration, an adaptive sequential design of experiment techniques decides the number and placement of new samples, minimizing costly queries to the underlying process. All generated data sets are fully reused across iterations, ensuring efficiency and convergence until predefined error-based stopping criteria are satisfied. The framework contributes three innovations: (i) a proportional feedback controller to adaptively reduce error, (ii) a steady-state detection mechanism to stop training when no further improvement occurs, and (iii) an inclusive multiresponse strategy that simultaneously leverages all available data. Inspired by Process Systems Engineering, the approach is validated on benchmark cases, demonstrating an efficient, accurate metamodel construction with minimal computational cost.
{"title":"A Process Systems Engineering Framework for Adaptive Sample Size Determination in AutoML Pipelines","authors":"Thalita Fernandes, Antonio Araujo","doi":"10.1021/acs.iecr.5c04103","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04103","url":null,"abstract":"This work introduces a framework for systematically determining the sample size required to build accurate metamodels in Automated Machine Learning (AutoML) pipelines. The method employs a feedback control strategy that favors simple regression models when sufficient, using nonlinear models only when necessary. At each iteration, an adaptive sequential design of experiment techniques decides the number and placement of new samples, minimizing costly queries to the underlying process. All generated data sets are fully reused across iterations, ensuring efficiency and convergence until predefined error-based stopping criteria are satisfied. The framework contributes three innovations: (i) a proportional feedback controller to adaptively reduce error, (ii) a steady-state detection mechanism to stop training when no further improvement occurs, and (iii) an inclusive multiresponse strategy that simultaneously leverages all available data. Inspired by Process Systems Engineering, the approach is validated on benchmark cases, demonstrating an efficient, accurate metamodel construction with minimal computational cost.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"94 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101997","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}
Pub Date : 2026-01-30DOI: 10.1021/acs.iecr.5c04814
Aitor Barquero, Miren Aguirre, Jurgen Scheerder
Waterborne acrylic polymer dispersions are typically produced via emulsion polymerization by using low molar mass surfactants. While these surfactants ensure dispersion stability, they negatively affect coating properties, such as water resistance, adhesion, haze formation, and barrier performance. A promising alternative is polymeric surfactants. Properly designed, polymeric surfactants prevent leaching and associated issues while enhancing coating performance. This review begins by explaining the use of polymeric surfactants, followed by an overview of their types and the polymerization methods employed─primarily bulk, solution, and emulsion polymerization. Then, polymeric surfactants synthesized through emulsion polymerization will be described, and their role in subsequent emulsion processes for waterborne binder production will be discussed. Additionally, the review examines coating morphology and presents examples of industrial applications, including coatings for printing and packaging.
{"title":"Waterborne Random Copolymers as Polymeric Surfactants for Emulsion Polymerization","authors":"Aitor Barquero, Miren Aguirre, Jurgen Scheerder","doi":"10.1021/acs.iecr.5c04814","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04814","url":null,"abstract":"Waterborne acrylic polymer dispersions are typically produced via emulsion polymerization by using low molar mass surfactants. While these surfactants ensure dispersion stability, they negatively affect coating properties, such as water resistance, adhesion, haze formation, and barrier performance. A promising alternative is polymeric surfactants. Properly designed, polymeric surfactants prevent leaching and associated issues while enhancing coating performance. This review begins by explaining the use of polymeric surfactants, followed by an overview of their types and the polymerization methods employed─primarily bulk, solution, and emulsion polymerization. Then, polymeric surfactants synthesized through emulsion polymerization will be described, and their role in subsequent emulsion processes for waterborne binder production will be discussed. Additionally, the review examines coating morphology and presents examples of industrial applications, including coatings for printing and packaging.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"83 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089677","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}
Nanomaterial-functionalized tubular ceramic membranes have emerged as a new generation of advanced separation platforms that integrate the mechanical robustness and chemical stability of ceramics with the tunable selectivity and multifunctionality of nanomaterials. This review comprehensively summarizes recent advances in their fabrication, surface modification, and performance enhancement, with emphasis on scalable fabrication strategies such as extrusion, freeze casting, and various coating or infiltration techniques. A wide range of nanomaterials─including metal–organic frameworks (MOFs), metal oxides, carbon-based nanostructures, and core–shell composites─have been employed to endow membranes with tailored adsorption, electrostatic, and size-selective transport properties. The review uniquely addresses key gaps in the existing literature, particularly the limited focus on tubular membrane configurations, which are industrially favored due to their superior mechanical integrity and ease of modular integration. A distinct contribution of this review is its structured analysis of performance enhancement, followed by a critical discussion on the paramount challenges of coating uniformity, interfacial adhesion, and long-term stability─aspects often overlooked yet crucial for practical deployment. The review concludes by synthesizing these insights to provide a clear roadmap for developing the next generation of scalable, durable, and sustainable tubular ceramic membranes for water purification and resource recovery.
{"title":"Nanomaterial-Functionalized Tubular Ceramic Membranes: Design, Fabrication, and Prospects for Sustainable Separation","authors":"Zunaira Maqsood, Haonan Wu, Ningyuan Wang, Yanan Gao, Hui Hu, Huijuan Guo, Qian Ma, Lijuan Shi, Qun Yi","doi":"10.1021/acs.iecr.5c04344","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04344","url":null,"abstract":"Nanomaterial-functionalized tubular ceramic membranes have emerged as a new generation of advanced separation platforms that integrate the mechanical robustness and chemical stability of ceramics with the tunable selectivity and multifunctionality of nanomaterials. This review comprehensively summarizes recent advances in their fabrication, surface modification, and performance enhancement, with emphasis on scalable fabrication strategies such as extrusion, freeze casting, and various coating or infiltration techniques. A wide range of nanomaterials─including metal–organic frameworks (MOFs), metal oxides, carbon-based nanostructures, and core–shell composites─have been employed to endow membranes with tailored adsorption, electrostatic, and size-selective transport properties. The review uniquely addresses key gaps in the existing literature, particularly the limited focus on tubular membrane configurations, which are industrially favored due to their superior mechanical integrity and ease of modular integration. A distinct contribution of this review is its structured analysis of performance enhancement, followed by a critical discussion on the paramount challenges of coating uniformity, interfacial adhesion, and long-term stability─aspects often overlooked yet crucial for practical deployment. The review concludes by synthesizing these insights to provide a clear roadmap for developing the next generation of scalable, durable, and sustainable tubular ceramic membranes for water purification and resource recovery.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"120 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089666","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}
Pub Date : 2026-01-30DOI: 10.1021/acs.iecr.5c03303
Paulo R. Wohlfahrt, Harald Gröger
ε-Caprolactone (termed typically as only caprolactone) is an important industrial commodity chemical, produced in quantities of tens of thousands of tons annually, and is valued for its biodegradable properties. Despite this large scale application, its production still relies on petrochemical sources. The conventional synthesis route involves the Baeyer–Villiger oxidation (BVO) of cyclohexanone under aqueous conditions, which presents significant challenges. Due to caprolactone’s high water solubility, the process requires an energy-intensive product workup. In this study, we present a fully solvent-free process for caprolactone production, starting from biobased phenol and achieving high conversions and efficiencies. The process begins with the selective hydrogenation of phenol to cyclohexanone using a palladium catalyst under solvent-free conditions, reaching conversions of 99% and selectivities of up to 78%. After simple removal of the heterogeneous catalyst and isolation of the ketone (80% isolated yield), cyclohexanone then is converted to caprolactone by combining it with the industrial autoxidation of aliphatic aldehydes to carboxylic acids in a noncatalytic process. Notably, the production of carboxylic acids such as butyric, isobutyric, or valeric acid exceeds several hundred thousand tons per year, thus making this coupling of the two oxidation processes highly valuable. Accordingly, this approach combines two major value-creating processes without the need for additional reagents and under fully solvent-free conditions. By implementing an aldehyde dosing strategy, the fraction of aldehyde contributing to caprolactone formation increased from 5% under nondosing conditions to 30%, reaching a final conversion of 13% of cyclohexanone. The final product is isolated by straightforward fractional vacuum distillation, a standard technique in the chemical industry, achieving a total mass balance of 95% and an isolated yield of caprolactone of 72% relative to the maximum of 13%. Notably, no side product formation was observed during the BVO reaction, owing to the mild reaction conditions (50 °C). In contrast, industrial processes can produce side products (particularly 6-hydroxyhexanoic acid) at levels of up to 15% of the final product, significantly lowering the process efficiency and sustainability.
{"title":"Efficient Combination of Two Industrial Processes for Sustainable Production of ε-Caprolactone","authors":"Paulo R. Wohlfahrt, Harald Gröger","doi":"10.1021/acs.iecr.5c03303","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03303","url":null,"abstract":"ε-Caprolactone (termed typically as only caprolactone) is an important industrial commodity chemical, produced in quantities of tens of thousands of tons annually, and is valued for its biodegradable properties. Despite this large scale application, its production still relies on petrochemical sources. The conventional synthesis route involves the Baeyer–Villiger oxidation (BVO) of cyclohexanone under aqueous conditions, which presents significant challenges. Due to caprolactone’s high water solubility, the process requires an energy-intensive product workup. In this study, we present a fully solvent-free process for caprolactone production, starting from biobased phenol and achieving high conversions and efficiencies. The process begins with the selective hydrogenation of phenol to cyclohexanone using a palladium catalyst under solvent-free conditions, reaching conversions of 99% and selectivities of up to 78%. After simple removal of the heterogeneous catalyst and isolation of the ketone (80% isolated yield), cyclohexanone then is converted to caprolactone by combining it with the industrial autoxidation of aliphatic aldehydes to carboxylic acids in a noncatalytic process. Notably, the production of carboxylic acids such as butyric, isobutyric, or valeric acid exceeds several hundred thousand tons per year, thus making this coupling of the two oxidation processes highly valuable. Accordingly, this approach combines two major value-creating processes without the need for additional reagents and under fully solvent-free conditions. By implementing an aldehyde dosing strategy, the fraction of aldehyde contributing to caprolactone formation increased from 5% under nondosing conditions to 30%, reaching a final conversion of 13% of cyclohexanone. The final product is isolated by straightforward fractional vacuum distillation, a standard technique in the chemical industry, achieving a total mass balance of 95% and an isolated yield of caprolactone of 72% relative to the maximum of 13%. Notably, no side product formation was observed during the BVO reaction, owing to the mild reaction conditions (50 °C). In contrast, industrial processes can produce side products (particularly 6-hydroxyhexanoic acid) at levels of up to 15% of the final product, significantly lowering the process efficiency and sustainability.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"14 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089676","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}
Efficient resource utilization of coal gasification coarse slag (CGCS) is critical for ecological sustainability and industrial economics. A low-cost, high-performance catalyst loaded with cerium-manganese oxide (CeO2–MnO2/CGCS) was prepared via an impregnation-hydrothermal synthesis. The catalytic ozonation activity of CeO2–MnO2/CGCS was evaluated based on the removal rate of chemical oxygen demand (COD) for both simulated and actual coal chemical wastewater. For simulated wastewater, the COD removal rates of phenol-, naphthalene-, and benzofuran-containing wastewater were 81.2%, 58.9% and 56.6%, respectively, with the existence of CeO2–MnO2/CGCS, and the COD removal rate of mixed simulated wastewater containing the above compounds reached 66.3%. When CeO2–MnO2/CGCS was applied to actual coal chemical wastewater, the COD decreased from 200 to 36.5 mg/L with a removal rate of 81.7%. In comparison, the COD removal rate using a commercial catalyst was 72.9%, indicating the potential industrial application of CeO2–MnO2/CGCS. Furthermore, it was demonstrated that hydroxyl radicals (·OH) are the key reactive substances in the degradation of organics by adding a free radical scavenger (5,5-dimethyl-1-pyrroline-N-oxide) into the catalytic ozonation degradation of phenol-containing wastewater. Meanwhile, the mechanism of catalytic ozonation degradation of organics in coal chemical wastewater using CeO2–MnO2/CGCS as the catalyst is also proposed.
{"title":"CeO2- and MnO2-Loaded Coal Gasification Coarse Slag Catalytic Ozonation for Degradation of Refractory Organics in Coal Chemical Wastewater","authors":"Yang-Yang Xu, Xing Fan, Hai-Xu Zou, Yu Wang, Shan-Zhao Feng, Xiao-Yan He, Xiang Bai, Yierxiati Dilixiati, Guligena Pidamaimaiti, Xian-Yong Wei","doi":"10.1021/acs.iecr.5c04146","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04146","url":null,"abstract":"Efficient resource utilization of coal gasification coarse slag (CGCS) is critical for ecological sustainability and industrial economics. A low-cost, high-performance catalyst loaded with cerium-manganese oxide (CeO<sub>2</sub>–MnO<sub>2</sub>/CGCS) was prepared via an impregnation-hydrothermal synthesis. The catalytic ozonation activity of CeO<sub>2</sub>–MnO<sub>2</sub>/CGCS was evaluated based on the removal rate of chemical oxygen demand (COD) for both simulated and actual coal chemical wastewater. For simulated wastewater, the COD removal rates of phenol-, naphthalene-, and benzofuran-containing wastewater were 81.2%, 58.9% and 56.6%, respectively, with the existence of CeO<sub>2</sub>–MnO<sub>2</sub>/CGCS, and the COD removal rate of mixed simulated wastewater containing the above compounds reached 66.3%. When CeO<sub>2</sub>–MnO<sub>2</sub>/CGCS was applied to actual coal chemical wastewater, the COD decreased from 200 to 36.5 mg/L with a removal rate of 81.7%. In comparison, the COD removal rate using a commercial catalyst was 72.9%, indicating the potential industrial application of CeO<sub>2</sub>–MnO<sub>2</sub>/CGCS. Furthermore, it was demonstrated that hydroxyl radicals (·OH) are the key reactive substances in the degradation of organics by adding a free radical scavenger (5,5-dimethyl-1-pyrroline-<i>N</i>-oxide) into the catalytic ozonation degradation of phenol-containing wastewater. Meanwhile, the mechanism of catalytic ozonation degradation of organics in coal chemical wastewater using CeO<sub>2</sub>–MnO<sub>2</sub>/CGCS as the catalyst is also proposed.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"30 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089665","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}
Roughness plays an important role in scaling on reverse osmosis (RO) membranes, yet the underlying mechanisms remain unclear. Here, we investigate the scaling behavior of three polyamide composite RO membranes (RO-L, RO-M, and RO-H) with systematically varied surface roughness. By tracking scaling evolution and introducing a wetting factor, f(θ), we elucidate how the surface microstructure regulates heterogeneous nucleation. Membranes with lower f(θ) values exhibited a delayed scaling onset (flux decline <20%), attributed to a larger effective filtration area and enhanced local turbulence that suppressed early gypsum deposition. However, their ridge-like structures also led to more irreversible scaling. Notably, f(θ) showed a stronger correlation with scaling propensity than average roughness (Ra), highlighting wetting characteristics as a more reliable descriptor.
{"title":"Wetting-Governed Heterogeneous Nucleation on Corrugated Reverse Osmosis Membranes: f(θ) Outperforms Ra as a Predictor of Scaling","authors":"Yuxuan Yi, Rui Bai, Zhen-Liang Xu, Liang Cheng, Yong-Jian Tang","doi":"10.1021/acs.iecr.5c03402","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03402","url":null,"abstract":"Roughness plays an important role in scaling on reverse osmosis (RO) membranes, yet the underlying mechanisms remain unclear. Here, we investigate the scaling behavior of three polyamide composite RO membranes (RO-L, RO-M, and RO-H) with systematically varied surface roughness. By tracking scaling evolution and introducing a wetting factor, <i>f</i>(θ), we elucidate how the surface microstructure regulates heterogeneous nucleation. Membranes with lower <i>f</i>(θ) values exhibited a delayed scaling onset (flux decline <20%), attributed to a larger effective filtration area and enhanced local turbulence that suppressed early gypsum deposition. However, their ridge-like structures also led to more irreversible scaling. Notably, <i>f</i>(θ) showed a stronger correlation with scaling propensity than average roughness (Ra), highlighting wetting characteristics as a more reliable descriptor.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"8 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089667","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}
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