Metal–organic frameworks (MOFs) have demonstrated exceptional performance for challenging gas separations, yet their practical implementation requires transformation from fine powders into mechanically robust shaped bodies. Here, we report the successful shaping of scalable Cu(OH)INA, a benchmark ultramicroporous MOF for acetylene/ethylene (C2H2/C2H4) separation, into pellets via wet granulation using organic binders. Among four hydroxyl-rich binders evaluated (hydroxypropyl cellulose, hydroxyethyl cellulose, poly(vinyl butyral), and sodium alginate), hydroxyethyl cellulose (HEC) at 3 wt % loading proved optimal, forming robust “solid bridges” between MOF crystals through hydrogen bonding interactions. The resulting Cu(OH)INA@3%HEC pellets (2–3 mm diameter) retained the parent MOF’s crystallinity and thermal stability while exhibiting excellent mechanical integrity, with <1.5% breakage after 1440 min of abrasion testing. Remarkably, the shaped pellets maintained high C2H2 adsorption capacity (66.0 cm3 cm–3 at 298 K, 1 bar) and enhanced IAST selectivity (53 vs 46 for powder) for C2H2/C2H4 (1:99, v/v) mixtures. Dynamic breakthrough experiments confirmed effective separation performance, achieving polymer-grade ethylene purity with consistent C2H2 retention across multiple regeneration cycles under industrially relevant conditions (298–313 K, varied flow rates).
{"title":"Shaping of a Scalable MOF for Efficient C2H2/C2H4 Separation","authors":"Qiancheng Chen, Wei Luo, Xin Zhang, Zhi-Wei Zhai, Xuefeng Bai, Yan-Long Zhao, Muzi Li, Yu Zhang, Zhang-Ye Han, Jian-Rong Li","doi":"10.1021/acs.iecr.5c04802","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04802","url":null,"abstract":"Metal–organic frameworks (MOFs) have demonstrated exceptional performance for challenging gas separations, yet their practical implementation requires transformation from fine powders into mechanically robust shaped bodies. Here, we report the successful shaping of scalable Cu(OH)INA, a benchmark ultramicroporous MOF for acetylene/ethylene (C<sub>2</sub>H<sub>2</sub>/C<sub>2</sub>H<sub>4</sub>) separation, into pellets via wet granulation using organic binders. Among four hydroxyl-rich binders evaluated (hydroxypropyl cellulose, hydroxyethyl cellulose, poly(vinyl butyral), and sodium alginate), hydroxyethyl cellulose (HEC) at 3 wt % loading proved optimal, forming robust “solid bridges” between MOF crystals through hydrogen bonding interactions. The resulting Cu(OH)INA@3%HEC pellets (2–3 mm diameter) retained the parent MOF’s crystallinity and thermal stability while exhibiting excellent mechanical integrity, with <1.5% breakage after 1440 min of abrasion testing. Remarkably, the shaped pellets maintained high C<sub>2</sub>H<sub>2</sub> adsorption capacity (66.0 cm<sup>3</sup> cm<sup>–3</sup> at 298 K, 1 bar) and enhanced IAST selectivity (53 vs 46 for powder) for C<sub>2</sub>H<sub>2</sub>/C<sub>2</sub>H<sub>4</sub> (1:99, v/v) mixtures. Dynamic breakthrough experiments confirmed effective separation performance, achieving polymer-grade ethylene purity with consistent C<sub>2</sub>H<sub>2</sub> retention across multiple regeneration cycles under industrially relevant conditions (298–313 K, varied flow rates).","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"272 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070539","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 : 2026-01-29DOI: 10.1021/acs.iecr.5c04511
Lu Ji, Fang Li, Xiaoshu Ding, Dongsheng Zhang, Xinqiang Zhao, Yanji Wang
The coupling of aqueous-phase reforming of methanol (APRM) with nitrobenzene hydrogenation offers a potentially safe and atom-economical route to aniline. This work developed an efficient Pd–Cu/γ-Al2O3 catalyst, with 98.9% nitrobenzene conversion and 92.9% aniline selectivity. Characterization results reveal that this higher activity is attributed to the Pd–Cu alloy formation, which enriches the Cu+ and Pd0 species and the number of strong base sites. The Cu+/Pd0 synergy enhanced methanol adsorption and decomposition, while the strong base sites facilitated water activation, thereby accelerating the APRM to supply more in situ hydrogen for nitrobenzene hydrogenation. DFT results further confirmed that the Pd–Cu alloy formation can lower the energy barriers in key steps. Based on the identification of the byproducts, the reaction mechanism for this coupled system was proposed. Pd–Cu/γ-Al2O3 catalyst can be easily regenerated by calcination and reduction, without significant loss of catalytic activity after 3 consecutive cycles. It also exhibited broad substrate applicability for various nitroarenes.
{"title":"A Novel Catalyst and the Catalytic Mechanism for Aqueous-Phase Reforming of Methanol Coupling with Nitrobenzene Hydrogenation to Aniline","authors":"Lu Ji, Fang Li, Xiaoshu Ding, Dongsheng Zhang, Xinqiang Zhao, Yanji Wang","doi":"10.1021/acs.iecr.5c04511","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04511","url":null,"abstract":"The coupling of aqueous-phase reforming of methanol (APRM) with nitrobenzene hydrogenation offers a potentially safe and atom-economical route to aniline. This work developed an efficient Pd–Cu/γ-Al<sub>2</sub>O<sub>3</sub> catalyst, with 98.9% nitrobenzene conversion and 92.9% aniline selectivity. Characterization results reveal that this higher activity is attributed to the Pd–Cu alloy formation, which enriches the Cu<sup>+</sup> and Pd<sup>0</sup> species and the number of strong base sites. The Cu<sup>+</sup>/Pd<sup>0</sup> synergy enhanced methanol adsorption and decomposition, while the strong base sites facilitated water activation, thereby accelerating the APRM to supply more in situ hydrogen for nitrobenzene hydrogenation. DFT results further confirmed that the Pd–Cu alloy formation can lower the energy barriers in key steps. Based on the identification of the byproducts, the reaction mechanism for this coupled system was proposed. Pd–Cu/γ-Al<sub>2</sub>O<sub>3</sub> catalyst can be easily regenerated by calcination and reduction, without significant loss of catalytic activity after 3 consecutive cycles. It also exhibited broad substrate applicability for various nitroarenes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"184 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089760","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 : 2026-01-29DOI: 10.1021/acs.iecr.5c04316
Abdulazez Alzhrani, Cynthia J. Jameson, Sohail Murad
Separation and recovery of nitrous oxide (N2O) from nitric acid tail gases is a pressing environmental challenge due to the dual role of N2O as a potent greenhouse gas and as the leading ozone-depleting substance. While catalytic destruction is the current industrial practice, it often lacks selectivity and generates secondary emissions, overlooking the added value of recovering N2O as a chemical feedstock. In this work, we employ atomistic nonequilibrium Molecular Dynamics (MD) simulations to investigate the selective retention and transport of N2O in zeolitic membranes. Three zeolite types all-silica Linde Type A (LTA), all-silica CDO-type zeolite, and calcium-exchanged Linde Type A (Ca-LTA, Si/Al = 1.0) were examined, and our results show that Ca-LTA exhibits superior recovery performance. Simulations were conducted across a wide range of temperatures (300–600 K) and pressures (100–932 atm) for equimolar binary, ternary, and quaternary mixtures, as well as five cases closely matching industrial gas composition (N2 mole fraction ≈ 0.4–0.8), providing direct insight into realistic operating conditions. Our results demonstrate that Ca-LTA retains N2O through strong interactions with Ca2+, while N2, NO, and NO2 permeate more readily. N2O permeation was negligible under most conditions, but trace breakthrough appeared in equimolar binary mixtures at 500 K, in ternary and quaternary mixtures at 450 K, and under industrial-like feeds with N2 mole fraction = 0.8 at 400 K, where only very few molecules of N2O permeated. In contrast, NO exhibited the highest mobility, while N2 and NO2 showed modest to intermediate permeability, both increasing systematically with temperature. Importantly, our results capture the experimentally observed transport behavior of pure gases in Ca-LTA membranes, and also predict the separation factors (SF), permeability, diffusion coefficients, and adsorption/permeation selectivity. Finally, our results provide the first molecular-level predictions for binary, ternary, quaternary, and industrial-composition mixtures in the absence of experimental data. Together, these findings establish Ca-LTA as a robust recovery medium for N2O, maintaining high selectivity across diverse feed compositions, ranging from simple gases to industrial-like mixtures, and aligning with experimental expectations for zeolitic membranes.
{"title":"Understanding Separation Mechanisms and Recovery of Nitrous Oxide (N2O) from Nitric Acid Plant Tail Gases Using Computational Molecular Modeling","authors":"Abdulazez Alzhrani, Cynthia J. Jameson, Sohail Murad","doi":"10.1021/acs.iecr.5c04316","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04316","url":null,"abstract":"Separation and recovery of nitrous oxide (N<sub>2</sub>O) from nitric acid tail gases is a pressing environmental challenge due to the dual role of N<sub>2</sub>O as a potent greenhouse gas and as the leading ozone-depleting substance. While catalytic destruction is the current industrial practice, it often lacks selectivity and generates secondary emissions, overlooking the added value of recovering N<sub>2</sub>O as a chemical feedstock. In this work, we employ atomistic nonequilibrium Molecular Dynamics (MD) simulations to investigate the selective retention and transport of N<sub>2</sub>O in zeolitic membranes. Three zeolite types all-silica Linde Type A (LTA), all-silica CDO-type zeolite, and calcium-exchanged Linde Type A (Ca-LTA, Si/Al = 1.0) were examined, and our results show that Ca-LTA exhibits superior recovery performance. Simulations were conducted across a wide range of temperatures (300–600 K) and pressures (100–932 atm) for equimolar binary, ternary, and quaternary mixtures, as well as five cases closely matching industrial gas composition (N<sub>2</sub> mole fraction ≈ 0.4–0.8), providing direct insight into realistic operating conditions. Our results demonstrate that Ca-LTA retains N<sub>2</sub>O through strong interactions with Ca<sup>2+</sup>, while N<sub>2</sub>, NO, and NO<sub>2</sub> permeate more readily. N<sub>2</sub>O permeation was negligible under most conditions, but trace breakthrough appeared in equimolar binary mixtures at 500 K, in ternary and quaternary mixtures at 450 K, and under industrial-like feeds with N<sub>2</sub> mole fraction = 0.8 at 400 K, where only very few molecules of N<sub>2</sub>O permeated. In contrast, NO exhibited the highest mobility, while N<sub>2</sub> and NO<sub>2</sub> showed modest to intermediate permeability, both increasing systematically with temperature. Importantly, our results capture the experimentally observed transport behavior of pure gases in Ca-LTA membranes, and also predict the separation factors (SF), permeability, diffusion coefficients, and adsorption/permeation selectivity. Finally, our results provide the first molecular-level predictions for binary, ternary, quaternary, and industrial-composition mixtures in the absence of experimental data. Together, these findings establish Ca-LTA as a robust recovery medium for N<sub>2</sub>O, maintaining high selectivity across diverse feed compositions, ranging from simple gases to industrial-like mixtures, and aligning with experimental expectations for zeolitic membranes.","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":"146089679","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 : 2026-01-29DOI: 10.1021/acs.iecr.5c04371
Gita Firouzan, Mohammad Hossein Rasoulifard, Mir Saeed Seyed Dorraji, Ismael Hajimiri
The increasing occurrence of emerging pharmaceutical pollutants in aquatic environments poses serious ecological and public health concerns, including the proliferation of antibiotic-resistant bacteria. This study introduces a novel and energy-efficient approach employing Controlled Pulsed Illumination (CPI) to enhance the performance of UV-based advanced oxidation processes (AOPs) for pollutant degradation. The effects of pulse periods and duty cycles on the trade-off between removal efficiency and energy consumption are systematically evaluated, with energy performance expressed as electrical energy per order (EEO, kWh m–3.order–1). A comparative assessment of three treatment pathways, namely, persulfate alone (PS), UVA irradiation alone, and their combination (UVA/PS), confirms the superior reactivity of the hybrid system. Under optimized CPI conditions (75% duty cycle, 100 ms pulse period), the hybrid UVA/PS process achieved a 55.87 ± 2.65% removal efficiency within 60 min while reducing EEO from 1034.36 to 760.37 kWh m–3.order–1. Degradation kinetics followed a pseudo-first-order model, indicating mechanistic consistency across configurations. Optimized pulsed irradiation reduces radical recombination, thereby improving the effective utilization of reactive species. These findings highlight the practical potential of pulsed irradiation for optimizing AOP performance and introduce a paradoxical illumination strategy, inspired by Parrondo’s paradox, to destabilize persistent pharmaceutical pollutants. Overall, this work paves the way for sustainable and energy-efficient water treatment technologies with practical applicability.
水生环境中越来越多的新出现的药物污染物引起了严重的生态和公共卫生问题，包括耐抗生素细菌的扩散。本研究介绍了一种新型的节能方法，利用可控脉冲照明（CPI）来提高基于紫外线的高级氧化工艺（AOPs）的污染物降解性能。系统地评估了脉冲周期和占空比对去除效率和能耗之间权衡的影响，能量性能表示为每阶电能（EEO, kWh m-3.order-1）。通过对过硫酸盐单独（PS）、UVA单独照射及其组合（UVA/PS）三种处理途径的比较评估，证实了混合体系的优越反应性。在优化的CPI条件下（75%占空比，100 ms脉冲周期），UVA/PS混合工艺在60 min内的去除率达到55.87±2.65%，同时将EEO从1034.36降低到760.37 kWh m - 3.订单- 1。降解动力学遵循伪一阶模型，表明不同构型的机制一致性。优化的脉冲辐照减少了自由基的重组，从而提高了活性物质的有效利用。这些发现突出了脉冲照射在优化AOP性能方面的实际潜力，并引入了一种受Parrondo悖论启发的悖论照明策略，以破坏持久性药物污染物的稳定性。总的来说，这项工作为可持续和节能的水处理技术铺平了道路，具有实用性。
{"title":"Engineering a Pulsed UVA-LED/Persulfate System Guided by Parrondo’s Paradox for Efficient Degradation of Emerging Pharmaceutical Pollutants and Electrical Energy Optimization","authors":"Gita Firouzan, Mohammad Hossein Rasoulifard, Mir Saeed Seyed Dorraji, Ismael Hajimiri","doi":"10.1021/acs.iecr.5c04371","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04371","url":null,"abstract":"The increasing occurrence of emerging pharmaceutical pollutants in aquatic environments poses serious ecological and public health concerns, including the proliferation of antibiotic-resistant bacteria. This study introduces a novel and energy-efficient approach employing Controlled Pulsed Illumination (CPI) to enhance the performance of UV-based advanced oxidation processes (AOPs) for pollutant degradation. The effects of pulse periods and duty cycles on the trade-off between removal efficiency and energy consumption are systematically evaluated, with energy performance expressed as electrical energy per order (<i>E</i><sub>EO</sub>, kWh m<sup>–3</sup>.order<sup>–1</sup>). A comparative assessment of three treatment pathways, namely, persulfate alone (PS), UVA irradiation alone, and their combination (UVA/PS), confirms the superior reactivity of the hybrid system. Under optimized CPI conditions (75% duty cycle, 100 ms pulse period), the hybrid UVA/PS process achieved a 55.87 ± 2.65% removal efficiency within 60 min while reducing <i>E</i><sub>EO</sub> from 1034.36 to 760.37 kWh m<sup>–3</sup>.order<sup>–1</sup>. Degradation kinetics followed a pseudo-first-order model, indicating mechanistic consistency across configurations. Optimized pulsed irradiation reduces radical recombination, thereby improving the effective utilization of reactive species. These findings highlight the practical potential of pulsed irradiation for optimizing AOP performance and introduce a paradoxical illumination strategy, inspired by Parrondo’s paradox, to destabilize persistent pharmaceutical pollutants. Overall, this work paves the way for sustainable and energy-efficient water treatment technologies with practical applicability.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"58 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089680","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}
The targeted recovery of lithium from end-of-life lithium-ion batteries (LIBs) is essential for sustainable resource cycling. However, existing methods often produce low-concentration lithium leachates contaminated with extraneous metal ions, complicating subsequent purification and lithium reclamation. Here, we report a hydrazine-assisted hydrothermal reduction process that enables a highly efficient and selective lithium extraction. Thermodynamic and experimental analyses confirm a lithium recovery rate of 99.06% from LiMn2O4 with selectivity over 99%. Mechanistic studies reveal that hydrazine disrupts the spinel structure via the attack on lattice oxygen, generating oxygen vacancies and facilitating preferential Li release over stronger-bonded Mn ions, ultimately forming a Mn3O4 precipitate. This process yields a high-purity lithium solution (>0.6 mol·L–1) that is directly convertible to battery-grade Li2CO3. Notably, nitrogen from hydrazine is predominantly converted into environmentally benign N2, with residual ammonia nitrogen as low as 26.5 mg·L–1 in the effluent. Comparative analysis shows our method achieves a superior lithium concentration of 4.58 g·L–1, leading to a 37.8% reduction in carbon footprint and 35.6% improvement in economic efficiency relative to conventional routes. The strategy also proves to be effective for LiCoO2 and LiNi1/3Co1/3Mn1/3O2, underscoring its potential as a scalable, impurity-free, and environmentally compatible route for closed-loop battery recycling.
{"title":"Direct Generation of High-Purity Lithium Solution from Spent Lithium-Ion Batteries via an Impurity-Free Hydrazine-Assisted Hydrothermal Route","authors":"Rou Tan, Shuangjie Lin, Yuxiang Hong, Junming Hong, Jiefeng Xiao","doi":"10.1021/acs.iecr.5c04821","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04821","url":null,"abstract":"The targeted recovery of lithium from end-of-life lithium-ion batteries (LIBs) is essential for sustainable resource cycling. However, existing methods often produce low-concentration lithium leachates contaminated with extraneous metal ions, complicating subsequent purification and lithium reclamation. Here, we report a hydrazine-assisted hydrothermal reduction process that enables a highly efficient and selective lithium extraction. Thermodynamic and experimental analyses confirm a lithium recovery rate of 99.06% from LiMn<sub>2</sub>O<sub>4</sub> with selectivity over 99%. Mechanistic studies reveal that hydrazine disrupts the spinel structure via the attack on lattice oxygen, generating oxygen vacancies and facilitating preferential Li release over stronger-bonded Mn ions, ultimately forming a Mn<sub>3</sub>O<sub>4</sub> precipitate. This process yields a high-purity lithium solution (>0.6 mol·L<sup>–1</sup>) that is directly convertible to battery-grade Li<sub>2</sub>CO<sub>3</sub>. Notably, nitrogen from hydrazine is predominantly converted into environmentally benign N<sub>2</sub>, with residual ammonia nitrogen as low as 26.5 mg·L<sup>–1</sup> in the effluent. Comparative analysis shows our method achieves a superior lithium concentration of 4.58 g·L<sup>–1</sup>, leading to a 37.8% reduction in carbon footprint and 35.6% improvement in economic efficiency relative to conventional routes. The strategy also proves to be effective for LiCoO<sub>2</sub> and LiNi<sub>1/3</sub>Co<sub>1/3</sub>Mn<sub>1/3</sub>O<sub>2</sub>, underscoring its potential as a scalable, impurity-free, and environmentally compatible route for closed-loop battery recycling.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"180 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089695","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 : 2026-01-29DOI: 10.1021/acs.iecr.5c04397
Yumei Yong, Weidong Bi, Xinpeng Nie, Shihao Ding, Zhonghuo Deng, Zhengye Lu, Wenqiang Lu, Chao Yang
Due to insufficient research on the detachment of bubbles and sub-bubbles caused by contact angle hysteresis, the paper focuses on accurately describing the bubble−particle detachment evolution. Based on a two-dimensional extended phase-field lattice Boltzmann (LB) model, the improved unidirectional interpolation algorithm and corresponding contact angle hysteresis scheme ensure to simulate the bubble−particle detachment with contact angle hysteresis on curved boundaries. Two benchmark cases are conducted to validate the phase-field LB model. Then, we simulate that the bubble is detached from the particle under the condition of different hysteresis windows, initial contact angles, and detachment forces. The effects of contact angle hysteresis on the bubble−particle detachment process and trapped sub-bubble are explored. The advancing angle in the hysteresis window inhibits bubble detachment, and the volume of the trapped sub-bubbles becomes larger. The contact angle hysteresis may weaken the effects of the receding angle and initial contact angle. The detachment force accelerates the process of bubble detachment, and the volume of the sub-bubble shows a tendency to first expand and then shrink. Large bubbles are easily detached, but the role works in a small range. The results provide guidance to control the sub-bubble size and bubble−particle detachment process.
{"title":"The Effect of Contact Angle Hysteresis on the Bubble−Particle Detachment and Trapped Sub-bubble by an Extended Phase-Field Lattice Boltzmann Model","authors":"Yumei Yong, Weidong Bi, Xinpeng Nie, Shihao Ding, Zhonghuo Deng, Zhengye Lu, Wenqiang Lu, Chao Yang","doi":"10.1021/acs.iecr.5c04397","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04397","url":null,"abstract":"Due to insufficient research on the detachment of bubbles and sub-bubbles caused by contact angle hysteresis, the paper focuses on accurately describing the bubble−particle detachment evolution. Based on a two-dimensional extended phase-field lattice Boltzmann (LB) model, the improved unidirectional interpolation algorithm and corresponding contact angle hysteresis scheme ensure to simulate the bubble−particle detachment with contact angle hysteresis on curved boundaries. Two benchmark cases are conducted to validate the phase-field LB model. Then, we simulate that the bubble is detached from the particle under the condition of different hysteresis windows, initial contact angles, and detachment forces. The effects of contact angle hysteresis on the bubble−particle detachment process and trapped sub-bubble are explored. The advancing angle in the hysteresis window inhibits bubble detachment, and the volume of the trapped sub-bubbles becomes larger. The contact angle hysteresis may weaken the effects of the receding angle and initial contact angle. The detachment force accelerates the process of bubble detachment, and the volume of the sub-bubble shows a tendency to first expand and then shrink. Large bubbles are easily detached, but the role works in a small range. The results provide guidance to control the sub-bubble size and bubble−particle detachment process.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"55 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070534","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}
The design and development of porous carbons and their supported Ni-based catalysts, characterized by high activity, stability, and low cost, remain challenging in green chemical processes. In this study, petroleum pitch (PP) and biomass pitch (BP) were employed as inexpensive carbon sources, with polyacrylonitrile (PAN) serving as a texture-modifying agent, to prepare modified carbons (MCs). Porous modified carbons (PMCs) with tailored pore sizes and distributions were comparatively prepared using a nanoscale CaCO3 template and a steam activation method. The results show that pitch-based MCs with a hybrid texture can be produced by mixing 50 wt % PAN with PP or BP, followed by thermal polymerization at 400 °C and carbonization at 600 °C. Steam activation at 800 °C for 1 h enhances pore formation in hybrid MCs derived from PAN-BP compared to those derived from PAN–PP, due to differences in the molecular structures of PP and BP. In contrast, the CaCO3 template method primarily produces mesopores and macropores, whereas steam activation generates abundant micropores and mesopores in PMCs, thereby creating ideal conditions for high-quality catalyst supports. The resulting 10 wt % Ni/PMCBP catalysts demonstrate an impressive phenol conversion of 99.4% and a cyclohexanol selectivity of 94.1% after reaction at 180 °C for 2 h, outperforming reference Ni-based catalysts. Additionally, the catalytic performance of phenol hydrogenation is significantly influenced by Ni particle size, which is closely related to the texture and pore characteristics of the carbon supports. This research provides valuable insights into the rational design of PMCs as effective supports for advanced catalytic applications.
{"title":"Tailoring the Hybrid Texture and Pore Structure of Pitch-Based Carbon to Disperse and Support Ni Nanoparticles for Efficient Phenol Hydrogenation","authors":"Tiantian Li, Zhepeng Zhao, Marcos Millan, Xiangyi Long, Zhengwei Cui, Guanming Yuan","doi":"10.1021/acs.iecr.5c04030","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04030","url":null,"abstract":"The design and development of porous carbons and their supported Ni-based catalysts, characterized by high activity, stability, and low cost, remain challenging in green chemical processes. In this study, petroleum pitch (PP) and biomass pitch (BP) were employed as inexpensive carbon sources, with polyacrylonitrile (PAN) serving as a texture-modifying agent, to prepare modified carbons (MCs). Porous modified carbons (PMCs) with tailored pore sizes and distributions were comparatively prepared using a nanoscale CaCO<sub>3</sub> template and a steam activation method. The results show that pitch-based MCs with a hybrid texture can be produced by mixing 50 wt % PAN with PP or BP, followed by thermal polymerization at 400 °C and carbonization at 600 °C. Steam activation at 800 °C for 1 h enhances pore formation in hybrid MCs derived from PAN-BP compared to those derived from PAN–PP, due to differences in the molecular structures of PP and BP. In contrast, the CaCO<sub>3</sub> template method primarily produces mesopores and macropores, whereas steam activation generates abundant micropores and mesopores in PMCs, thereby creating ideal conditions for high-quality catalyst supports. The resulting 10 wt % Ni/PMC<sub>BP</sub> catalysts demonstrate an impressive phenol conversion of 99.4% and a cyclohexanol selectivity of 94.1% after reaction at 180 °C for 2 h, outperforming reference Ni-based catalysts. Additionally, the catalytic performance of phenol hydrogenation is significantly influenced by Ni particle size, which is closely related to the texture and pore characteristics of the carbon supports. This research provides valuable insights into the rational design of PMCs as effective supports for advanced catalytic applications.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"33 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070535","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 : 2026-01-29DOI: 10.1021/acs.iecr.5c04775
Anurag Singh, Mohan Yama, Jaya Rawat, Anurag S. Rathore
This study presents a sustainable process for the production of L-lactic acid from rice straw, an abundant agricultural residue. Rice straw was subjected to dilute acid pretreatment, followed by enzymatic hydrolysis to convert cellulose into glucose, which was subsequently fermented to produce lactic acid. An integrated process for in situ lactic acid removal during high cell density fermentation using nonsterile resin was studied. A systematic approach was adopted to study the adsorption characteristics of the resin and the impact of impurities present in the fermentation broth on the resin performance to improve the yield and purity of the lactic acid in downstream processing. An overall process yield of 77% and purity of 89% were achieved, representing a 39% improvement over conventional pH strategies, with 94% reduction in salt generation compared to conventional precipitation methods and productivity of 1.19 g/(L h), superior to recent literature values of 0.329–0.430 g/(L h).
{"title":"Production and Purification of Lactic Acid from Rice Straw Using an Integrated Fermentation and Adsorption System","authors":"Anurag Singh, Mohan Yama, Jaya Rawat, Anurag S. Rathore","doi":"10.1021/acs.iecr.5c04775","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04775","url":null,"abstract":"This study presents a sustainable process for the production of L-lactic acid from rice straw, an abundant agricultural residue. Rice straw was subjected to dilute acid pretreatment, followed by enzymatic hydrolysis to convert cellulose into glucose, which was subsequently fermented to produce lactic acid. An integrated process for in situ lactic acid removal during high cell density fermentation using nonsterile resin was studied. A systematic approach was adopted to study the adsorption characteristics of the resin and the impact of impurities present in the fermentation broth on the resin performance to improve the yield and purity of the lactic acid in downstream processing. An overall process yield of 77% and purity of 89% were achieved, representing a 39% improvement over conventional pH strategies, with 94% reduction in salt generation compared to conventional precipitation methods and productivity of 1.19 g/(L h), superior to recent literature values of 0.329–0.430 g/(L h).","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"5 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070536","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 : 2026-01-28DOI: 10.1021/acs.iecr.5c05047
Mengyu Wang, Xiangfei Chen, Yadong Lv, Yajiang Huang, Guangxian Li
Products of natural rubber/carbon black (NR/CB) nanocomposites, such as aircraft tire tread rubber, often face the alternating effects of high-speed sliding friction and thermo-oxidative aging during service. This study simulated the severe service conditions of the tread rubber. It was found that the initial thermo-oxidative aging alternated the cross-linking structure and mechanical properties of NR nanocomposites, leading to a nonmonotonic change in their subsequent wear behavior. Furthermore, the initial structural damage induced by strong sliding friction on the rubber surface accelerated subsequent thermo-oxidative aging, changing the competition between post-cross-linking and degradation reactions. The findings of this study are expected to deepen understanding of the factors and mechanisms affecting the safety of aircraft tire tread rubber under complex servicing conditions.
{"title":"Interactions between Thermal Oxidation and Sliding Friction on the Aging and Wear Behavior of Natural Rubber Nanocomposites","authors":"Mengyu Wang, Xiangfei Chen, Yadong Lv, Yajiang Huang, Guangxian Li","doi":"10.1021/acs.iecr.5c05047","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c05047","url":null,"abstract":"Products of natural rubber/carbon black (NR/CB) nanocomposites, such as aircraft tire tread rubber, often face the alternating effects of high-speed sliding friction and thermo-oxidative aging during service. This study simulated the severe service conditions of the tread rubber. It was found that the initial thermo-oxidative aging alternated the cross-linking structure and mechanical properties of NR nanocomposites, leading to a nonmonotonic change in their subsequent wear behavior. Furthermore, the initial structural damage induced by strong sliding friction on the rubber surface accelerated subsequent thermo-oxidative aging, changing the competition between post-cross-linking and degradation reactions. The findings of this study are expected to deepen understanding of the factors and mechanisms affecting the safety of aircraft tire tread rubber under complex servicing conditions.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"55 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056951","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 : 2026-01-28DOI: 10.1021/acs.iecr.5c04671
Junyuan Zhu, Ling Zhang, Chunzhong Li
In response to growing demands for environmentally friendly flame-retardant materials, this study develops a novel waterborne polyurethane (WPU) by incorporating the reactive phosphaphenanthrene-based compound DOPO-HQ into the polymer backbone. The modified WPUs, denoted as P-WPUx, exhibit significantly enhanced flame retardancy without appreciably compromising mechanical performance. With only 3 wt % DOPO-HQ loading, P-WPU3 achieves an LOI of 35.35%, satisfies the UL-94 V-0 requirement, and retains mechanical robustness with 33.0 MPa tensile strength and 737.8% elongation. Comprehensive analyses confirm that DOPO-HQ operates via a dual-phase mechanism: scavenging free radicals within the gas phase while simultaneously facilitating carbonaceous layer development in the condensed phase. These findings underscore the potential of molecularly integrated phosphorus-containing modifiers in the design of high-performance, sustainable flame-retardant WPU materials.
{"title":"Enhanced Flame Retardancy and Mechanical Properties of Waterborne Polyurethane via a DOPO-Based Reactive Flame Retardant","authors":"Junyuan Zhu, Ling Zhang, Chunzhong Li","doi":"10.1021/acs.iecr.5c04671","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04671","url":null,"abstract":"In response to growing demands for environmentally friendly flame-retardant materials, this study develops a novel waterborne polyurethane (WPU) by incorporating the reactive phosphaphenanthrene-based compound DOPO-HQ into the polymer backbone. The modified WPUs, denoted as P-WPUx, exhibit significantly enhanced flame retardancy without appreciably compromising mechanical performance. With only 3 wt % DOPO-HQ loading, P-WPU3 achieves an LOI of 35.35%, satisfies the UL-94 V-0 requirement, and retains mechanical robustness with 33.0 MPa tensile strength and 737.8% elongation. Comprehensive analyses confirm that DOPO-HQ operates via a dual-phase mechanism: scavenging free radicals within the gas phase while simultaneously facilitating carbonaceous layer development in the condensed phase. These findings underscore the potential of molecularly integrated phosphorus-containing modifiers in the design of high-performance, sustainable flame-retardant WPU materials.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"180 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070542","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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