The hydrogenation of CO2 to methanol is one of the most industrially promising measures to solve the excessive emission of CO2, although the development of highly active methanol catalysts is still a challenge. Herein, different modification methods of citric acid in the Cu/ZrO2 catalyst system are compared, and the quantities and strengths of the basic sites of the catalysts could be adjusted by changing the modification method of citric acid. Using various characterization methods, it was found that introducing an appropriate amount of citric acid during the preparation of the support could form a complex with the zirconium dioxide precursor, which can significantly change the distribution of basic sites and the number of hydroxyl groups on the surface of the support. Moreover, the catalyst can generate more oxygen vacancies, enhance the interaction between the metal and the support, and significantly improve the adsorption and activation of the reaction gas. Compared with the unmodified catalyst, the space-time yield of methanol increases from 300 to 660 gMeOH·h–1·kgcat–1 under the reaction conditions of 260 °C and 3.0 MPa. This strategy and the experimental results provide a novel understanding of citric acid modification and the role of basic sites in the conversion of CO2 to methanol.
将 CO2 加氢转化为甲醇是解决 CO2 过度排放的最具工业前景的措施之一，但高活性甲醇催化剂的开发仍是一项挑战。本文比较了 Cu/ZrO2 催化剂体系中柠檬酸的不同改性方法，并通过改变柠檬酸的改性方法来调整催化剂碱性位点的数量和强度。通过各种表征方法发现，在制备载体时引入适量的柠檬酸可与二氧化锆前驱体形成络合物，从而显著改变载体表面碱性位点的分布和羟基的数量。此外，催化剂还能产生更多的氧空位，增强金属与载体之间的相互作用，显著提高反应气体的吸附和活化能力。与未改性催化剂相比，在 260 °C 和 3.0 MPa 的反应条件下，甲醇的时空产率从 300 gMeOH-h-1-kgcat-1 增加到 660 gMeOH-h-1-kgcat-1。这一策略和实验结果为柠檬酸改性以及碱性位点在二氧化碳转化为甲醇过程中的作用提供了新的认识。
{"title":"Role of Basic Sites on Cu/ZrO2 Catalysts Modified with Citric Acid in the Hydrogenation of CO2 to Methanol","authors":"Wenhua Dai, Xin Meng, Daoming Jin, Fan Xu, Dandan Yang, Zhong Xin","doi":"10.1021/acs.iecr.4c04074","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04074","url":null,"abstract":"The hydrogenation of CO<sub>2</sub> to methanol is one of the most industrially promising measures to solve the excessive emission of CO<sub>2</sub>, although the development of highly active methanol catalysts is still a challenge. Herein, different modification methods of citric acid in the Cu/ZrO<sub>2</sub> catalyst system are compared, and the quantities and strengths of the basic sites of the catalysts could be adjusted by changing the modification method of citric acid. Using various characterization methods, it was found that introducing an appropriate amount of citric acid during the preparation of the support could form a complex with the zirconium dioxide precursor, which can significantly change the distribution of basic sites and the number of hydroxyl groups on the surface of the support. Moreover, the catalyst can generate more oxygen vacancies, enhance the interaction between the metal and the support, and significantly improve the adsorption and activation of the reaction gas. Compared with the unmodified catalyst, the space-time yield of methanol increases from 300 to 660 g<sub>MeOH</sub>·h<sup>–1</sup>·kg<sub>cat</sub><sup>–1</sup> under the reaction conditions of 260 °C and 3.0 MPa. This strategy and the experimental results provide a novel understanding of citric acid modification and the role of basic sites in the conversion of CO<sub>2</sub> to methanol.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"19 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143517914","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}
Hydrogen emerges as a promising alternative to fossil fuels with its pollutant-free emissions, high energy density, versatility, and efficiency in generating power. In this study, photocatalytic hydrogen production from using 1000 ppm of model solution prepared with sucrose was investigated in the presence of Fe/g-C3N4 photocatalysts over Box–Behnken experimental design developed using the Minitab statistical software. The amount of hydrogen produced was optimized at different pH environments (3, 5, and 7) for 2 h reaction time with different amounts of metal loaded (10, 20, and 30 wt %), Fe/g-C3N4 (0.1, 0.2, and 0.3 g/L), and oxidant (H2O2; 0, 10, and 20 mM) concentrations. SEM, BET, XRD, FTIR, and PL analyses were employed for the characterization of synthesized photocatalysts. According to the response optimization, using Fe/g-C3N4, the optimal conditions for hydrogen production were found as 0.3 g/L catalyst loading, 18.8 mM H2O2, and 26.6% Fe loading by mass when the pH was 3 for the reaction medium. Furthermore, machine learning algorithms were employed to predict hydrogen evolution based on experimental parameters. Notably, ensemble models such as Voting Regressor combining the Bagging Regressor, Random Forest Regressor, LGBM Regressor, Extra Trees Regressor, XGB Regressor, and Gradient Boosting Regressor achieved superior performance with a mean squared error of 0.0068 and R-squared (R2) of 0.9895. This integrated approach demonstrates the efficacy of machine learning in optimizing photocatalytic hydrogen generation processes.
{"title":"Predictive Modeling of Photocatalytic Hydrogen Production: Integrating Experimental Insights with Machine Learning on Fe/g-C3N4 Catalysts","authors":"Bahriyenur Arabacı, Rezan Bakır, Ceren Orak, Aslı Yüksel","doi":"10.1021/acs.iecr.4c03919","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03919","url":null,"abstract":"Hydrogen emerges as a promising alternative to fossil fuels with its pollutant-free emissions, high energy density, versatility, and efficiency in generating power. In this study, photocatalytic hydrogen production from using 1000 ppm of model solution prepared with sucrose was investigated in the presence of Fe/g-C<sub>3</sub>N<sub>4</sub> photocatalysts over Box–Behnken experimental design developed using the Minitab statistical software. The amount of hydrogen produced was optimized at different pH environments (3, 5, and 7) for 2 h reaction time with different amounts of metal loaded (10, 20, and 30 wt %), Fe/g-C<sub>3</sub>N<sub>4</sub> (0.1, 0.2, and 0.3 g/L), and oxidant (H<sub>2</sub>O<sub>2</sub>; 0, 10, and 20 mM) concentrations. SEM, BET, XRD, FTIR, and PL analyses were employed for the characterization of synthesized photocatalysts. According to the response optimization, using Fe/g-C<sub>3</sub>N<sub>4</sub>, the optimal conditions for hydrogen production were found as 0.3 g/L catalyst loading, 18.8 mM H<sub>2</sub>O<sub>2</sub>, and 26.6% Fe loading by mass when the pH was 3 for the reaction medium. Furthermore, machine learning algorithms were employed to predict hydrogen evolution based on experimental parameters. Notably, ensemble models such as Voting Regressor combining the Bagging Regressor, Random Forest Regressor, LGBM Regressor, Extra Trees Regressor, XGB Regressor, and Gradient Boosting Regressor achieved superior performance with a mean squared error of 0.0068 and <i>R</i>-squared (<i>R</i><sup>2</sup>) of 0.9895. This integrated approach demonstrates the efficacy of machine learning in optimizing photocatalytic hydrogen generation processes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"84 3 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143517913","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}
This work investigates the coalescence and directional movement of microsized oil droplets on a fiber with a wettability gradient using numerical simulations. The volume of fluid (VOF) method and an improved dynamic contact angle model were employed to examine the effects of the wettability gradient on droplet coalescence and motion. The results indicate that as the wettability gradient increases, the droplet movement velocity accelerates, with a maximum velocity of approximately 0.2 m/s. The peak droplet velocity occurs when the trailing edge crosses the wettability transition, and the larger the contact angle on the high-contact angle side, the higher the velocity. The coalescence and self-propelled motion of micron-sized viscous droplets on fibers with wettability gradient occur in the low-Reynolds number regime. Dimensionless analysis shows that as the droplet-to-fiber diameter ratio increases, the velocity increases, but the rate of increase diminishes. The curvature of the fiber surface restricts droplet spreading, causing the maximum velocity to be 25–30% lower than that on a flat surface. During coalescence, microsized oil droplets release nearly 7–12% of their surface energy.
{"title":"Coalescence and Self-Propelled Dynamics of Micron-Sized Oil Droplets on a Fiber with Wettability Gradient","authors":"Zeming Fu, Huagen Wu, Yanling Xiong, Zhongxu Jiang, Wenjian Liu, Rongshan Zhang, Ziwen Xing","doi":"10.1021/acs.iecr.4c04031","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04031","url":null,"abstract":"This work investigates the coalescence and directional movement of microsized oil droplets on a fiber with a wettability gradient using numerical simulations. The volume of fluid (VOF) method and an improved dynamic contact angle model were employed to examine the effects of the wettability gradient on droplet coalescence and motion. The results indicate that as the wettability gradient increases, the droplet movement velocity accelerates, with a maximum velocity of approximately 0.2 m/s. The peak droplet velocity occurs when the trailing edge crosses the wettability transition, and the larger the contact angle on the high-contact angle side, the higher the velocity. The coalescence and self-propelled motion of micron-sized viscous droplets on fibers with wettability gradient occur in the low-Reynolds number regime. Dimensionless analysis shows that as the droplet-to-fiber diameter ratio increases, the velocity increases, but the rate of increase diminishes. The curvature of the fiber surface restricts droplet spreading, causing the maximum velocity to be 25–30% lower than that on a flat surface. During coalescence, microsized oil droplets release nearly 7–12% of their surface energy.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"28 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143517954","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 : 2025-02-27DOI: 10.1021/acs.iecr.4c04024
Mohammad Shohel, Nathan R. Bays, Jessica A. LaFond, Samantha M. Kruse, Zoe K. Bryant, Jenna A. Krawchuck, Perla A. Salinas, Jessica K. Román-Kustas, Mark J. Rigali, Andrew W. Knight, Ryan D. Davis, Jessica N. Kruichak
The establishment of the EPA’s new legally enforceable maximum levels for toxic per- and polyfluoroalkyl substances (PFAS) underscores the need for better remediation and low-level detection capabilities. With a unique porous structure and physicochemical properties, mesoporous carbon (MC) is a promising candidate as an adsorbent to capture PFAS and as a substrate to functionalize for improving selectivity and performance. Despite this potential, a comprehensive study with MC or their modification for the remediation and detection of PFAS is still lacking. Herein, we evaluated the adsorption, thermal stability, and preconcentration of perfluorooctanoic acid (PFOA) on three different MC materials: disordered carbon (DC) and two ordered carbons, CMK-3 and CMK-8. The MC materials were further successfully modified by functionalization with methyltrialkyl (C8–C10)ammonium (MTA). Adsorption isotherms for both functionalized and bare MC were constructed to understand the PFOA adsorption behavior. The adsorption capacity of MC ranged between 57.7 and 142.6 mg/g with the best performance observed for CMK-3. MTA functionalization of MC improved the PFOA adsorption capacity by 26–34% relative to bare MC. In addition, we demonstrated that the thermal degradation of PFOA may be improved using functionalized materials by inhibiting PFOA vaporization at temperatures insufficient for chemical decomposition. We also developed a method that used MC as a preconcentrator to analyze PFOA in a solution at a lower concentration.
{"title":"Mesoporous Carbons and their Modification with Aliphatic Quaternary Amines for Adsorption, Thermal Treatment, and Preconcentration of Perfluorooctanoic Acid (PFOA)","authors":"Mohammad Shohel, Nathan R. Bays, Jessica A. LaFond, Samantha M. Kruse, Zoe K. Bryant, Jenna A. Krawchuck, Perla A. Salinas, Jessica K. Román-Kustas, Mark J. Rigali, Andrew W. Knight, Ryan D. Davis, Jessica N. Kruichak","doi":"10.1021/acs.iecr.4c04024","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04024","url":null,"abstract":"The establishment of the EPA’s new legally enforceable maximum levels for toxic per- and polyfluoroalkyl substances (PFAS) underscores the need for better remediation and low-level detection capabilities. With a unique porous structure and physicochemical properties, mesoporous carbon (MC) is a promising candidate as an adsorbent to capture PFAS and as a substrate to functionalize for improving selectivity and performance. Despite this potential, a comprehensive study with MC or their modification for the remediation and detection of PFAS is still lacking. Herein, we evaluated the adsorption, thermal stability, and preconcentration of perfluorooctanoic acid (PFOA) on three different MC materials: disordered carbon (DC) and two ordered carbons, CMK-3 and CMK-8. The MC materials were further successfully modified by functionalization with methyltrialkyl (C<sub>8</sub>–C<sub>10</sub>)ammonium (MTA). Adsorption isotherms for both functionalized and bare MC were constructed to understand the PFOA adsorption behavior. The adsorption capacity of MC ranged between 57.7 and 142.6 mg/g with the best performance observed for CMK-3. MTA functionalization of MC improved the PFOA adsorption capacity by 26–34% relative to bare MC. In addition, we demonstrated that the thermal degradation of PFOA may be improved using functionalized materials by inhibiting PFOA vaporization at temperatures insufficient for chemical decomposition. We also developed a method that used MC as a preconcentrator to analyze PFOA in a solution at a lower concentration.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"28 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143517965","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 : 2025-02-27DOI: 10.1021/acs.iecr.4c04984
Yao Jiang, Dongdong Zheng, Kang Wang, Mingming Xu, Qi Wang, Peng Cui, Lin-Bing Sun
Porous polymer networks are considered potential candidates for CO2 capture, owing to their well-developed porosity and high stability. However, their further application is limited by the relatively low selectivity and unsatisfactory adsorption capacity. In this study, we fabricated a nitrogen-rich porous polymer network, denoted as NRPPN-1, with dense polytriazine and polytetrazine by polymerization of two monomers of melamine and 3,6-dichloro-1,2,4,5-tetrazine. The resulting NRPPN-1 exhibits an abundance of micropores and a high surface area of 668 m2·g–1. Experimental results demonstrate that NRPPN-1 has excellent CO2 adsorption capacity (181.2 mg·g–1) and adsorption selectivity (306.4) at 273 K and 100 kPa for CO2/N2 mixtures, which are corroborated by adsorption potential and breakthrough curve analysis. Moreover, computational simulations reveal that the abundant nitrogen-rich active sites in NRPPN-1 induce strong C···N interactions, which are responsible for the promoted selective capture of CO2 from CO2/N2 mixtures. The novel nitrogen-rich porous polymer network may serve as a promising candidate for the capture of CO2 from flue gas.
{"title":"Fabrication of a Nitrogen-Rich Porous Polymer Network with Dense Polytriazine and Polytetrazine for CO2 Capture","authors":"Yao Jiang, Dongdong Zheng, Kang Wang, Mingming Xu, Qi Wang, Peng Cui, Lin-Bing Sun","doi":"10.1021/acs.iecr.4c04984","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04984","url":null,"abstract":"Porous polymer networks are considered potential candidates for CO<sub>2</sub> capture, owing to their well-developed porosity and high stability. However, their further application is limited by the relatively low selectivity and unsatisfactory adsorption capacity. In this study, we fabricated a nitrogen-rich porous polymer network, denoted as NRPPN-1, with dense polytriazine and polytetrazine by polymerization of two monomers of melamine and 3,6-dichloro-1,2,4,5-tetrazine. The resulting NRPPN-1 exhibits an abundance of micropores and a high surface area of 668 m<sup>2</sup>·g<sup>–1</sup>. Experimental results demonstrate that NRPPN-1 has excellent CO<sub>2</sub> adsorption capacity (181.2 mg·g<sup>–1</sup>) and adsorption selectivity (306.4) at 273 K and 100 kPa for CO<sub>2</sub>/N<sub>2</sub> mixtures, which are corroborated by adsorption potential and breakthrough curve analysis. Moreover, computational simulations reveal that the abundant nitrogen-rich active sites in NRPPN-1 induce strong C···N interactions, which are responsible for the promoted selective capture of CO<sub>2</sub> from CO<sub>2</sub>/N<sub>2</sub> mixtures. The novel nitrogen-rich porous polymer network may serve as a promising candidate for the capture of CO<sub>2</sub> from flue gas.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"23 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143507352","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 : 2025-02-27DOI: 10.1021/acs.iecr.4c04144
Xiu-Ping Ding, Ya-Jie Mao, Jin-Feng Huang, Hao Lin
All-solid-state ionic conductive elastomers have attracted widespread attention in the application of flexible electronics due to their good ionic conductivity, high transparency, and solvent-free matrix, etc. In this work, a new type of all-solid-state ionic conductive elastomer film is fabricated through UV light processing of a photosensitive AUD/EAA-based prepolymer system loaded with a LiTFSI salt. The fabricated ionic conductive elastomer films exhibit very good mechanical properties. When adding 20 wt % of LiTFSI, a fracture elongation of 662%, a toughness of 34.92 KJ·m–3, and a tensile strength of 1.152 MPa are achieved, exhibiting strengthening and toughening. The films also have good electrical conductivity and high optical transmittance, i.e., up to 1.81 × 10–6 S/m and 91%, respectively. In addition, good multimodal sensing performances are demonstrated for the fabricated ionic conductive elastomer films. A strain-sensing sensitivity of GF = 1.01 within the strain range of 0–150% with high cyclic sensing stability is achieved, and excellent temperature-sensing and triboelectric-sensing performances are demonstrated. This work provides a facile approach for the development of highly stretchable and transparent ionic conductive elastomers toward applications in flexible electronic devices.
{"title":"Fabrication of a Flexible and Transparent All-Solid-State Ionic Conductive Elastomer and Its Sensing Properties","authors":"Xiu-Ping Ding, Ya-Jie Mao, Jin-Feng Huang, Hao Lin","doi":"10.1021/acs.iecr.4c04144","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04144","url":null,"abstract":"All-solid-state ionic conductive elastomers have attracted widespread attention in the application of flexible electronics due to their good ionic conductivity, high transparency, and solvent-free matrix, etc. In this work, a new type of all-solid-state ionic conductive elastomer film is fabricated through UV light processing of a photosensitive AUD/EAA-based prepolymer system loaded with a LiTFSI salt. The fabricated ionic conductive elastomer films exhibit very good mechanical properties. When adding 20 wt % of LiTFSI, a fracture elongation of 662%, a toughness of 34.92 KJ·m<sup>–3</sup>, and a tensile strength of 1.152 MPa are achieved, exhibiting strengthening and toughening. The films also have good electrical conductivity and high optical transmittance, i.e., up to 1.81 × 10<sup>–6</sup> S/m and 91%, respectively. In addition, good multimodal sensing performances are demonstrated for the fabricated ionic conductive elastomer films. A strain-sensing sensitivity of GF = 1.01 within the strain range of 0–150% with high cyclic sensing stability is achieved, and excellent temperature-sensing and triboelectric-sensing performances are demonstrated. This work provides a facile approach for the development of highly stretchable and transparent ionic conductive elastomers toward applications in flexible electronic devices.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"41 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143507435","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 : 2025-02-27DOI: 10.1021/acs.iecr.4c04229
Wing Ho Leung, Erin M. Leitao, Casparus Johannes Reinhard Verbeek
Reactive extrusion (REX) was used to synthesize an aromatic–aliphatic copolyester by copolymerizing poly(ethylene terephthalate) (PET) and polycaprolactone (PCL) as a novel PET recycling strategy. Critical design parameters were evaluated, including reaction kinetics, screw configuration, and processing conditions, to optimize the REX process in a co-rotating twin-screw extruder. By integrating kneading blocks with varying staggering angles, an optimized screw design was proposed to mitigate significant challenges such as short residence times, mixing inefficiencies, and barrel blockage caused by drastic changes in melt viscosity. Although the feed rate is more influential than screw speed in determining the residence time, controlling screw speed is crucial for optimizing the degree of fill and shear rate to promote transesterification. In addition, a minimum of 4 min of residence time is required. To reach equilibrium in an equimolar PET/PCL blend with 1.5 pph Ti(OBu)4, kneading blocks covering over 50% of the screw length, it was essential to achieve a degree of fill of 0.5, ensuring sufficient mixing efficiency in low-viscosity melts against gravitational effects. Copolymers synthesized from virgin PET and municipal PET waste sources exhibit comparable thermomechanical properties and backbone structures, demonstrating that hard-to-recycle PET can be upcycled by catalytic transesterification. This study provides valuable insights and advances the design of REX systems, especially in the context of depolymerization-driven chemical recycling that involves significant viscosity changes.
{"title":"Synthesis of a Novel Aromatic–Aliphatic Copolyester from Poly(ethylene terephthalate) Using Reactive Extrusion","authors":"Wing Ho Leung, Erin M. Leitao, Casparus Johannes Reinhard Verbeek","doi":"10.1021/acs.iecr.4c04229","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04229","url":null,"abstract":"Reactive extrusion (REX) was used to synthesize an aromatic–aliphatic copolyester by copolymerizing poly(ethylene terephthalate) (PET) and polycaprolactone (PCL) as a novel PET recycling strategy. Critical design parameters were evaluated, including reaction kinetics, screw configuration, and processing conditions, to optimize the REX process in a co-rotating twin-screw extruder. By integrating kneading blocks with varying staggering angles, an optimized screw design was proposed to mitigate significant challenges such as short residence times, mixing inefficiencies, and barrel blockage caused by drastic changes in melt viscosity. Although the feed rate is more influential than screw speed in determining the residence time, controlling screw speed is crucial for optimizing the degree of fill and shear rate to promote transesterification. In addition, a minimum of 4 min of residence time is required. To reach equilibrium in an equimolar PET/PCL blend with 1.5 pph Ti(OBu)<sub>4</sub>, kneading blocks covering over 50% of the screw length, it was essential to achieve a degree of fill of 0.5, ensuring sufficient mixing efficiency in low-viscosity melts against gravitational effects. Copolymers synthesized from virgin PET and municipal PET waste sources exhibit comparable thermomechanical properties and backbone structures, demonstrating that hard-to-recycle PET can be upcycled by catalytic transesterification. This study provides valuable insights and advances the design of REX systems, especially in the context of depolymerization-driven chemical recycling that involves significant viscosity changes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"30 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143517952","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 : 2025-02-26DOI: 10.1021/acs.iecr.4c03998
Jasper Ros, Nicholas Agon, David Louwagie, Oriol Gutiérrez-Sanchez, Arjen Huizinga, Paul Gravesteijn, Melvin Kruijne, Eirini Skylogianni, Peter van Os, Juliana Garcia Moretz-Sohn Monteiro
Carbon capture is an essential technology in the energy transition. Post-combustion carbon capture using amine solvents is the most advanced technology, with CESAR1, a mixture of 3 M 2-amino-2-methyl-1-propanol (AMP) and 1.5 M piperazine (PZ), currently being established as the state-of-the-art open solvent, for which an increasing amount of high-quality pilot results is becoming available. This study extends the amount of available CESAR1 solvent pilot data by discussing the results of two pilot campaigns conducted at a metal recycling facility (Umicore, Belgium) using a mobile CO2 capture plant (TNO’s miniplant). The campaigns captured CO2 from two flue gas sources: a blast furnace (804 h of operation) and a smelter (915 h of operation). This paper discusses the main results of both campaigns, including data for the accumulation of several relevant degradation products in the capture solvent. The stable operation and consistent degradation profiles observed in both campaigns display the strength of on-site, small-scale mobile pilot testing on real flue gases, which can derisk the implementation of a full-scale system on those specific flue gases. Additionally, the solvent degradation results of the Umicore campaigns are compared to two pilot campaigns described in the literature (the RWE and TCM campaigns), also using CESAR1 as the capture solvent. A novel methodology is proposed in this work to compare the solvent degradation results from pilots of different sizes. The results of this comparative analysis highlight the stability of the CESAR1 solvent, showing no sign of exponential degradation in any of the campaigns considered. Additionally, the role of NO2 in oxidative solvent degradation is further clarified, as during the smelter campaign, higher NO2 concentrations were reported (36.4 ppm on average) than for any of the other campaigns discussed in this study (0.5–2.35 ppm), and consequently, much higher solvent degradation rates were observed.
{"title":"CESAR1 Carbon Capture Pilot Campaigns at an Industrial Metal Recycling Site and Analysis of Solvent Degradation Behavior","authors":"Jasper Ros, Nicholas Agon, David Louwagie, Oriol Gutiérrez-Sanchez, Arjen Huizinga, Paul Gravesteijn, Melvin Kruijne, Eirini Skylogianni, Peter van Os, Juliana Garcia Moretz-Sohn Monteiro","doi":"10.1021/acs.iecr.4c03998","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03998","url":null,"abstract":"Carbon capture is an essential technology in the energy transition. Post-combustion carbon capture using amine solvents is the most advanced technology, with CESAR1, a mixture of 3 M 2-amino-2-methyl-1-propanol (AMP) and 1.5 M piperazine (PZ), currently being established as the state-of-the-art open solvent, for which an increasing amount of high-quality pilot results is becoming available. This study extends the amount of available CESAR1 solvent pilot data by discussing the results of two pilot campaigns conducted at a metal recycling facility (Umicore, Belgium) using a mobile CO<sub>2</sub> capture plant (TNO’s miniplant). The campaigns captured CO<sub>2</sub> from two flue gas sources: a blast furnace (804 h of operation) and a smelter (915 h of operation). This paper discusses the main results of both campaigns, including data for the accumulation of several relevant degradation products in the capture solvent. The stable operation and consistent degradation profiles observed in both campaigns display the strength of on-site, small-scale mobile pilot testing on real flue gases, which can derisk the implementation of a full-scale system on those specific flue gases. Additionally, the solvent degradation results of the Umicore campaigns are compared to two pilot campaigns described in the literature (the RWE and TCM campaigns), also using CESAR1 as the capture solvent. A novel methodology is proposed in this work to compare the solvent degradation results from pilots of different sizes. The results of this comparative analysis highlight the stability of the CESAR1 solvent, showing no sign of exponential degradation in any of the campaigns considered. Additionally, the role of NO<sub>2</sub> in oxidative solvent degradation is further clarified, as during the smelter campaign, higher NO<sub>2</sub> concentrations were reported (36.4 ppm on average) than for any of the other campaigns discussed in this study (0.5–2.35 ppm), and consequently, much higher solvent degradation rates were observed.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"28 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143507428","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 : 2025-02-26DOI: 10.1021/acs.iecr.4c04158
Ashkan Dargahi, Mark Duncan, Joel Runka, Ahmed Hammami, Tao Wen, Xiayu Wang, Weifeng Chen, Hani E. Naguib
High-density polyethylene (HDPE) is well known for its excellent moisture and chemical resistance, combined with a balance of ductility and strength, making it ideal for high-temperature, high-pressure applications. To enhance HDPE-based products under these conditions, improving barrier properties against greenhouse gases and increasing creep strength are essential. This study developed a graphene nanoplatelet (GNP)/HDPE nanocomposite with only 0.5 wt % GNP using a scalable melt-compounding method. By optimizing processing conditions and grafting GNP onto HDPE chains via maleic anhydride functional groups, significant improvements were achieved at 60 °C, including a 44.6% reduction in supercritical CO2 permeability, a 40.7% reduction in creep strain, and a 68.1% decrease in creep strain rate. Additionally, the onset degradation temperature increased by 25 °C, and the maximum weight loss rate improved by 54% compared to neat HDPE. Notably, these enhancements were achieved while maintaining elongation at break, with the GNP/HDPE nanocomposite exhibiting nearly 20% higher elongation at break than neat HDPE. Fourier transform infrared spectroscopy (FTIR) confirmed strong ester linkages between GNP and the polymer chain, resulting from a nucleophilic addition reaction that improved interfacial bonding and overall properties. This study offers a significant step toward more resilient and environmentally friendly engineering materials.
{"title":"Low-Concentration Graphene Nanoplatelet/HDPE Nanocomposites with Enhanced Dispersion and Interfacial Bonding for Improved CO2 Barrier and Mechanical Performance at Elevated Temperatures","authors":"Ashkan Dargahi, Mark Duncan, Joel Runka, Ahmed Hammami, Tao Wen, Xiayu Wang, Weifeng Chen, Hani E. Naguib","doi":"10.1021/acs.iecr.4c04158","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04158","url":null,"abstract":"High-density polyethylene (HDPE) is well known for its excellent moisture and chemical resistance, combined with a balance of ductility and strength, making it ideal for high-temperature, high-pressure applications. To enhance HDPE-based products under these conditions, improving barrier properties against greenhouse gases and increasing creep strength are essential. This study developed a graphene nanoplatelet (GNP)/HDPE nanocomposite with only 0.5 wt % GNP using a scalable melt-compounding method. By optimizing processing conditions and grafting GNP onto HDPE chains via maleic anhydride functional groups, significant improvements were achieved at 60 °C, including a 44.6% reduction in supercritical CO<sub>2</sub> permeability, a 40.7% reduction in creep strain, and a 68.1% decrease in creep strain rate. Additionally, the onset degradation temperature increased by 25 °C, and the maximum weight loss rate improved by 54% compared to neat HDPE. Notably, these enhancements were achieved while maintaining elongation at break, with the GNP/HDPE nanocomposite exhibiting nearly 20% higher elongation at break than neat HDPE. Fourier transform infrared spectroscopy (FTIR) confirmed strong ester linkages between GNP and the polymer chain, resulting from a nucleophilic addition reaction that improved interfacial bonding and overall properties. This study offers a significant step toward more resilient and environmentally friendly engineering materials.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"16 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495807","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 : 2025-02-26DOI: 10.1021/acs.iecr.4c03056
Jian Liu, William L. Kubic, Jr., Eric C. D. Tan, Jacob W. Dempsey, Pahola Thathiana Benavides, Sweta Balchandani, Hakan Olcay, Dupeng Liu, Ning Sun, Shailesh Dangwal, Blake N. Trusty, Syed Z. Islam, Ramesh R. Bhave
It is energy-intensive to separate dilute 2,3-butanediol (2,3-BDO) (<10 wt %) from the aqueous phase of fermentation broth for sustainable aviation fuel (SAF) using conventional distillation. Liquid–liquid extraction (LLE) using oleyl alcohol as a solvent in a membrane extractor to extract BDO from water can significantly reduce the energy cost and minimize the potential emulsion. In an Aspen Plus model simulation, 95.2% BDO recovery and 97.1% BDO purity have been achieved using this LLE method with solvent recovery and heat integration. The thermal energy cost was estimated to be 4.57 MJ/kg BDO, which is only about 16.8% of the lower heating value (LHV) of the BDO. This method consumes 81% less energy than the cascade distillation and reduces about $0.46/GGE (gasoline gallon equivalent) to the minimal fuel selling price. Meanwhile, the greenhouse gas (GHG) emission is 62% lower than petroleum-based jet fuel production and 34% less than using the cascade distillation.
{"title":"Techno-Economic Analysis and Life Cycle Assessment for the Separation of 2,3-Butanediol from Fermentation Broth Using Liquid–Liquid Extraction","authors":"Jian Liu, William L. Kubic, Jr., Eric C. D. Tan, Jacob W. Dempsey, Pahola Thathiana Benavides, Sweta Balchandani, Hakan Olcay, Dupeng Liu, Ning Sun, Shailesh Dangwal, Blake N. Trusty, Syed Z. Islam, Ramesh R. Bhave","doi":"10.1021/acs.iecr.4c03056","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03056","url":null,"abstract":"It is energy-intensive to separate dilute 2,3-butanediol (2,3-BDO) (<10 wt %) from the aqueous phase of fermentation broth for sustainable aviation fuel (SAF) using conventional distillation. Liquid–liquid extraction (LLE) using oleyl alcohol as a solvent in a membrane extractor to extract BDO from water can significantly reduce the energy cost and minimize the potential emulsion. In an Aspen Plus model simulation, 95.2% BDO recovery and 97.1% BDO purity have been achieved using this LLE method with solvent recovery and heat integration. The thermal energy cost was estimated to be 4.57 MJ/kg BDO, which is only about 16.8% of the lower heating value (LHV) of the BDO. This method consumes 81% less energy than the cascade distillation and reduces about $0.46/GGE (gasoline gallon equivalent) to the minimal fuel selling price. Meanwhile, the greenhouse gas (GHG) emission is 62% lower than petroleum-based jet fuel production and 34% less than using the cascade distillation.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"15 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143507427","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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