Pub Date : 2024-10-28DOI: 10.1016/j.ces.2024.120880
Shirong Sun , Erhu Li , Xuliang Lin , Xueqing Qiu
Efficient biomass fractionation is key to enhancing the productivity and profitability of biorefining but faces challenges such as strong carbon–carbon bonds in lignin and irreversible condensation reactions during extraction. In this study, hydroxyl-containing nucleophilic reagents are integrated into acidic deep eutectic solvents (DESs) for wheat straw pretreatment, achieving over 74.3 % lignin removal and 94.3 % cellulose retention. This method preserves more than 98.6 % of the β–O–4 linkages in lignin, and the nucleophilic reagents, introduced in-situ at the benzylic position of lignin, act as both a surfactant on cellulose and a stabilizer for isolated lignin. This dual functionality enhances enzymatic hydrolysis, resulting in 75.3 wt% glucose and 51.0 wt% xylose yields. Additionally, the pyrolysis yield of methoxy-deficient monophenols increases from 27.7 wt% to 38.6 wt%. This approach effectively addresses key challenges in biomass fractionation, improving carbon efficiency and facilitating the full valorization of lignocellulose.
{"title":"Elevating monosaccharides and monophenols production from wheat straw components via in-situ tailored lignin with deep eutectic solvents","authors":"Shirong Sun , Erhu Li , Xuliang Lin , Xueqing Qiu","doi":"10.1016/j.ces.2024.120880","DOIUrl":"10.1016/j.ces.2024.120880","url":null,"abstract":"<div><div>Efficient biomass fractionation is key to enhancing the productivity and profitability of biorefining but faces challenges such as strong carbon–carbon bonds in lignin and irreversible condensation reactions during extraction. In this study, hydroxyl-containing nucleophilic reagents are integrated into acidic deep eutectic solvents (DESs) for wheat straw pretreatment, achieving over 74.3 % lignin removal and 94.3 % cellulose retention. This method preserves more than 98.6 % of the <em>β</em>–O–4 linkages in lignin, and the nucleophilic reagents, introduced <em>in-situ</em> at the benzylic position of lignin, act as both a surfactant on cellulose and a stabilizer for isolated lignin. This dual functionality enhances enzymatic hydrolysis, resulting in 75.3 wt% glucose and 51.0 wt% xylose yields. Additionally, the pyrolysis yield of methoxy-deficient monophenols increases from 27.7 wt% to 38.6 wt%. This approach effectively addresses key challenges in biomass fractionation, improving carbon efficiency and facilitating the full valorization of lignocellulose.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120880"},"PeriodicalIF":4.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520240","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2024-10-28DOI: 10.1016/j.ces.2024.120863
Peng Zhang , Fan Yang , Xuedong Zhu , Weizhong Zheng
In this work, a kind of ZSM-5 zeolite with one-dimensional fins growing along the [010] direction has been successfully synthesized utilizing both tetrapropylammonium hydroxide (TPAOH) and tetramethylammonium hydroxide (TMAOH) as co-templates. With the aid of molecular dynamic simulations and a series of experimental evidences, the formation mechanism of the one-dimensional feature is determined to arise from the synergic effects between TPA+ and TMA+. Two TPA+ and three TMA+ would co-exist in a unit MFI cell at a certain crystallization period depending on the composition of zeolite and precursor, and this configuration ensures a minimum stabilization energy required for the growth along [010] direction. Investigations manifest these needle-like fins with diameters of ca. 60 nm could function as pseudo nano crystals and introduce additional pores ranging from 10 to 90 nm, which effectively promotes the diffusion capability and substantially improves the catalytic performance in propane aromatization.
{"title":"Unveiling the generation of mesoporous MFI zeolites with one-dimensional fins in the assistance from small quaternary ammonium cation and its application in propane aromatization","authors":"Peng Zhang , Fan Yang , Xuedong Zhu , Weizhong Zheng","doi":"10.1016/j.ces.2024.120863","DOIUrl":"10.1016/j.ces.2024.120863","url":null,"abstract":"<div><div>In this work, a kind of ZSM-5 zeolite with one-dimensional fins growing along the [010] direction has been successfully synthesized utilizing both tetrapropylammonium hydroxide (TPAOH) and tetramethylammonium hydroxide (TMAOH) as co-templates. With the aid of molecular dynamic simulations and a series of experimental evidences, the formation mechanism of the one-dimensional feature is determined to arise from the synergic effects between TPA<sup>+</sup> and TMA<sup>+</sup>. Two TPA<sup>+</sup> and three TMA<sup>+</sup> would co-exist in a unit <strong>MFI</strong> cell at a certain crystallization period depending on the composition of zeolite and precursor, and this configuration ensures a minimum stabilization energy required for the growth along [010] direction. Investigations manifest these needle-like fins with diameters of <em>ca.</em> 60 nm could function as pseudo nano crystals and introduce additional pores ranging from 10 to 90 nm, which effectively promotes the diffusion capability and substantially improves the catalytic performance in propane aromatization.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120863"},"PeriodicalIF":4.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2024-10-28DOI: 10.1016/j.ces.2024.120874
Anthony G. Dixon
The pseudo homogeneous 2D fixed bed heat transfer model is used for fixed bed reactor simulation and design. The two parameters are estimated by one of two main approaches. Method 2 uses the bed centerline temperature and the exit mixing-cup temperature. Method 4 uses radial temperature profile measurements at the exits of progressively longer beds. Particle-resolved computational fluid dynamics (PRCFD) is used to simulate heat transfer in a bed of spheres with tube-to-particle diameter ratio to determine whether the methods give the same parameter values. Method 2 and variations gave underestimated values of if the mixing-cup temperature was low by 1 K. For Method 4 fitted to long enough bed depths, good estimates of the parameters were obtained. A new version of Method 2 is proposed, which retains the advantages of measuring only axial profiles, while avoiding the sensitivity problems of estimation from single temperature measurements.
{"title":"Fixed bed heat transfer parameter estimation –a new look at an old problem","authors":"Anthony G. Dixon","doi":"10.1016/j.ces.2024.120874","DOIUrl":"10.1016/j.ces.2024.120874","url":null,"abstract":"<div><div>The pseudo homogeneous 2D <span><math><mrow><msub><mi>k</mi><mi>r</mi></msub><mo>-</mo><msub><mi>h</mi><mi>w</mi></msub></mrow></math></span> fixed bed heat transfer model is used for fixed bed reactor simulation and design. The two parameters are estimated by one of two main approaches. Method 2 uses the bed centerline temperature and the exit mixing-cup temperature. Method 4 uses radial temperature profile measurements at the exits of progressively longer beds. Particle-resolved computational fluid dynamics (PRCFD) is used to simulate heat transfer in a bed of spheres with tube-to-particle diameter ratio <span><math><mrow><mi>N</mi><mo>=</mo><mn>6</mn></mrow></math></span> to determine whether the methods give the same parameter values. Method 2 and variations gave underestimated values of <span><math><mrow><msub><mi>h</mi><mi>w</mi></msub></mrow></math></span> if the mixing-cup temperature was low by 1 K. For Method 4 fitted to long enough bed depths, good estimates of the parameters were obtained. A new version of Method 2 is proposed, which retains the advantages of measuring only axial profiles, while avoiding the sensitivity problems of estimation from single temperature measurements.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120874"},"PeriodicalIF":4.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2024-10-28DOI: 10.1016/j.ces.2024.120873
Sofia P. Brandão , Margarida S.C.A. Brito , António A. Ferreira , Ricardo J. Santos
Flow regimes in two planar reactors with Smooth Periodic Constrictions, commonly used as Oscillatory Flow Reactors (OFRs), are characterized by Computational Fluid Dynamics (CFD) and Planar Laser Induced Fluorescence (PLIF) without applying the typical external oscillation to the flow. The unforced flow frequencies were identified by spectral Fourier analysis. Three different flow regimes were identified: steady/stratified laminar at low Reynolds numbers, unsteady laminar at intermediate Re, and turbulent flow at high Re. The CFD model was validated by comparison with the PLIF experimental results. A dual-double cascade, a 2D turbulence phenomenon, was detected, emphasizing the significant role of dynamic vortices’ formation in the reactors’ flow. Additionally, the geometric parameters, such as the reactor’s depth and constriction to the chamber’s width ratio, have shown a great impact on onsetting a dynamic flow. These results provide insights into the mixing mechanisms and dominant scales of the unforced flow, establishing the basis for future optimization of oscillatory parameters in OFRs.
{"title":"Unforced flow regimes in planar baffled reactors with Smooth Periodic Constrictions","authors":"Sofia P. Brandão , Margarida S.C.A. Brito , António A. Ferreira , Ricardo J. Santos","doi":"10.1016/j.ces.2024.120873","DOIUrl":"10.1016/j.ces.2024.120873","url":null,"abstract":"<div><div>Flow regimes in two planar reactors with Smooth Periodic Constrictions, commonly used as Oscillatory Flow Reactors (OFRs), are characterized by Computational Fluid Dynamics (CFD) and Planar Laser Induced Fluorescence (PLIF) without applying the typical external oscillation to the flow. The unforced flow frequencies were identified by spectral Fourier analysis. Three different flow regimes were identified: steady/stratified laminar at low Reynolds numbers, unsteady laminar at intermediate Re, and turbulent flow at high Re. The CFD model was validated by comparison with the PLIF experimental results. A dual-double cascade, a 2D turbulence phenomenon, was detected, emphasizing the significant role of dynamic vortices’ formation in the reactors’ flow. Additionally, the geometric parameters, such as the reactor’s depth and constriction to the chamber’s width ratio, have shown a great impact on onsetting a dynamic flow. These results provide insights into the mixing mechanisms and dominant scales of the unforced flow, establishing the basis for future optimization of oscillatory parameters in OFRs.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120873"},"PeriodicalIF":4.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-28DOI: 10.1016/j.ces.2024.120877
Wenlei Fan , Wei Qin , Chi Ma , Jinghui Li , Yafei Guo , Yujie Li , Lichun Ma , Tianlong Deng
Cesium (Cs) contamination, particularly from nuclear waste, poses significant environmental and health risks due to its high solubility and mobility in water. The development of effective adsorbent materials to remove Cs+ contamination from wastewater is crucial. In this study, we designed and investigated a series of open-framework metal-sulfur ion-exchange materials (KMSnS, where M = Co, Mg, Nb, Zn) using density functional theory (DFT). The goal was to identify materials with high affinity for cesium ions. DFT calculations revealed that among the studied materials, KNbSnS exhibits superior affinity for Cs+, and its adsorption mechanism was thoroughly examined from a microscopic perspective, including adsorption spontaneity. KNbSnS was successfully synthesized through a hydrothermal method and applied to simulated wastewater treatment to evaluate its practical performance. The synthesized material demonstrated outstanding adsorption capacity, with a maximum value of 457.58 mg·g−1. More importantly, KNbSnS maintained its high performance over 10 adsorption–desorption cycles, making it a promising candidate for sustainable cesium ion removal in real-world applications. This research not only provides a theoretical and experimental basis for the development of KNbSnS as a cesium ion adsorbent but also highlights its potential for large-scale applications in wastewater treatment, particularly in mitigating radioactive contamination. The results have significant implications for environmental protection, particularly in the context of nuclear waste management and the remediation of contaminated water bodies.
{"title":"Highly efficient Cesium ion adsorption using KNbSnS: A DFT-guided approach for wastewater treatment","authors":"Wenlei Fan , Wei Qin , Chi Ma , Jinghui Li , Yafei Guo , Yujie Li , Lichun Ma , Tianlong Deng","doi":"10.1016/j.ces.2024.120877","DOIUrl":"10.1016/j.ces.2024.120877","url":null,"abstract":"<div><div>Cesium (Cs) contamination, particularly from nuclear waste, poses significant environmental and health risks due to its high solubility and mobility in water. The development of effective adsorbent materials to remove Cs<sup>+</sup> contamination from wastewater is crucial. In this study, we designed and investigated a series of open-framework metal-sulfur ion-exchange materials (KMSnS, where M = Co, Mg, Nb, Zn) using density functional theory (DFT). The goal was to identify materials with high affinity for cesium ions. DFT calculations revealed that among the studied materials, KNbSnS exhibits superior affinity for Cs<sup>+</sup>, and its adsorption mechanism was thoroughly examined from a microscopic perspective, including adsorption spontaneity. KNbSnS was successfully synthesized through a hydrothermal method and applied to simulated wastewater treatment to evaluate its practical performance. The synthesized material demonstrated outstanding adsorption capacity, with a maximum value of 457.58 mg·g<sup>−1</sup>. More importantly, KNbSnS maintained its high performance over 10 adsorption–desorption cycles, making it a promising candidate for sustainable cesium ion removal in real-world applications. This research not only provides a theoretical and experimental basis for the development of KNbSnS as a cesium ion adsorbent but also highlights its potential for large-scale applications in wastewater treatment, particularly in mitigating radioactive contamination. The results have significant implications for environmental protection, particularly in the context of nuclear waste management and the remediation of contaminated water bodies.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120877"},"PeriodicalIF":4.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The steam methane reforming (SMR) process has been instrumental in industrial hydrogen production, despite its high carbon footprint. The direct capture of CO2 from its flue gas remains a challenge. In this study, we propose a hybrid SMR process integrated with the NET Power Cycle (NPC) to repurpose exhausted CO2 and produce supercritical CO2 directly. To simulate the conventional SMR process, we developed mathematical and machine-learning models to predict hydrogen production. The integration of heat between the SMR and NPC units led to 40 % reduction in natural gas consumption, while the energy required for CO2 capture was reduced by 54 %. The optimization of the SMR-NPC process was conducted using the genetic algorithm (GA), resulting in low direct CO2 emissions of 0.6 kg-CO2/kg-H2 and levelized cost of hydrogen (LCOH) of $3.39/kg-H2. The novel process proposed in this study offers an efficient means to enhance both the economic and environmental performance of industrial hydrogen production.
{"title":"Performance analysis of a novel SMR process integrated with the oxy-combustion power cycle for clean hydrogen production","authors":"Guang Miao, Leizhao Zheng, Cuiting Yang, Guoqing Li, Jing Xiao","doi":"10.1016/j.ces.2024.120861","DOIUrl":"10.1016/j.ces.2024.120861","url":null,"abstract":"<div><div>The steam methane reforming (SMR) process has been instrumental in industrial hydrogen production, despite its high carbon footprint. The direct capture of CO<sub>2</sub> from its flue gas remains a challenge. In this study, we propose a hybrid SMR process integrated with the NET Power Cycle (NPC) to repurpose exhausted CO<sub>2</sub> and produce supercritical CO<sub>2</sub> directly. To simulate the conventional SMR process, we developed mathematical and machine-learning models to predict hydrogen production. The integration of heat between the SMR and NPC units led to 40 % reduction in natural gas consumption, while the energy required for CO<sub>2</sub> capture was reduced by 54 %. The optimization of the SMR-NPC process was conducted using the genetic algorithm (GA), resulting in low direct CO<sub>2</sub> emissions of 0.6 kg-CO<sub>2</sub>/kg-H<sub>2</sub> and levelized cost of hydrogen (LCOH) of $3.39/kg-H<sub>2</sub>. The novel process proposed in this study offers an efficient means to enhance both the economic and environmental performance of industrial hydrogen production.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120861"},"PeriodicalIF":4.1,"publicationDate":"2024-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2024-10-24DOI: 10.1016/j.ces.2024.120843
Ajibola A. Bayode , Stephen Sunday Emmanuel , Saheed O. Sanni , Fatima Lakhdar , Lin Fu , Jianping Shang , Hua-Jun Shawn Fan
The rise in globalization and industrialization has led to an increase in population, increasing improperly treated discharge containing dyes, pharmaceuticals, pesticides etc in the water bodies. This has led to the need to remove these contaminants from water sources. The NiFe@BBAL adsorbent was developed and analyzed using various techniques such as FTIR, XRD, SEM, and XPS. The effectiveness of the NiFe@BBAL in adsorbing Ciprofloxacin (CIP) and metronidazole (MET) in water was tested. The adsorption of CIP and MET, both individually and in mixtures, was studied. The kinetic sorption experiments showed that the adsorption followed a pseudo-second-order model, with a higher R2 of 0.9934 for MET compared to 0.9916 for CIP. This suggests that the rate-limiting step is chemisorption. The primary adsorption mechanisms for both CIP and MET were hydrogen bonding, hydrophobic interactions, and electrostatic interactions, while CIP also involved electrostatic and metal complexation interactions. The NiFe@BBAL effluent showed no toxic effects on bacteria, indicating that no harmful material was leached in the effluent. The NiFe@BBAL demonstrated excellent performance and stability in removing 97.64% CIP and 97.62% MET in single contaminant experiments, and 57.33% CIP and 70.69% MET in cocktail mixture experiments. This can be attributed to the smaller structure of MET compared to CIP, allowing it better access to the active site, leading to higher adsorption. Furthermore, the repeated use of the adsorbent proved to be stable in the removal of CIP and MET over five cycles, demonstrating that the material is sustainable and suitable for large-scale experiments.
{"title":"Biogenic fabrication of spinel nickel ferrite imprinted on Bifurcaria bifurcata Macro-Alga activated carbon for the adsorption of ciprofloxacin and metronidazole","authors":"Ajibola A. Bayode , Stephen Sunday Emmanuel , Saheed O. Sanni , Fatima Lakhdar , Lin Fu , Jianping Shang , Hua-Jun Shawn Fan","doi":"10.1016/j.ces.2024.120843","DOIUrl":"10.1016/j.ces.2024.120843","url":null,"abstract":"<div><div>The rise in globalization and industrialization has led to an increase in population, increasing improperly treated discharge containing dyes, pharmaceuticals, pesticides etc in the water bodies. This has led to the need to remove these contaminants from water sources. The NiFe@BBAL adsorbent was developed and analyzed using various techniques such as FTIR, XRD, SEM, and XPS. The effectiveness of the NiFe@BBAL in adsorbing Ciprofloxacin (CIP) and metronidazole (MET) in water was tested. The adsorption of CIP and MET, both individually and in mixtures, was studied. The kinetic sorption experiments showed that the adsorption followed a pseudo-second-order model, with a higher R<sup>2</sup> of 0.9934 for MET compared to 0.9916 for CIP. This suggests that the rate-limiting step is chemisorption. The primary adsorption mechanisms for both CIP and MET were hydrogen bonding, hydrophobic interactions, and electrostatic interactions, while CIP also involved electrostatic and metal complexation interactions. The NiFe@BBAL effluent showed no toxic effects on bacteria, indicating that no harmful material was leached in the effluent. The NiFe@BBAL demonstrated excellent performance and stability in removing 97.64% CIP and 97.62% MET in single contaminant experiments, and 57.33% CIP and 70.69% MET in cocktail mixture experiments. This can be attributed to the smaller structure of MET compared to CIP, allowing it better access to the active site, leading to higher adsorption. Furthermore, the repeated use of the adsorbent proved to be stable in the removal of CIP and MET over five cycles, demonstrating that the material is sustainable and suitable for large-scale experiments.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120843"},"PeriodicalIF":4.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489105","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Efficient separation of magnesium and lithium is essential for the extraction of lithium resources from salt-lake brines. However, the current membrane separation technologies are challenged by the membrane permeability-selectivity trade-off. Herein, we demonstrated a facile and practical approach to fabricate crown ether-functionalized polymeric membranes with excellent Li+/Mg2+ separation performance by incorporating 12-crown-4 rings into the cellulose triacetate polymer network. The tightly and regularly arranged polymer chains anchored the crown ether rings firmly in the membrane structure, thereby facilitating the formation of stable and highly selective cation transport channels inside the membrane. As a result, the prepared membrane achieved an ultrahigh Li+/Mg2+ separation factor of ∼872 and Li+ flux of 22.6 μmol m−2 s−1, which was much superior to that of commercial CIMS and reported membrane separation technologies. The good long-term stability of the fabricated membrane is promising for achieving efficient magnesium-lithium separation in large-scale industrial applications.
{"title":"Facile design of a crown ether-functionalized polymeric membrane for highly efficient lithium and magnesium separation during electrodialysis","authors":"Baoying Wang, Ruirui Li, Zhenzhen Cui, Zihao Wang, Weicheng Fu, Junying Yan, Chenxiao Jiang, Liang Wu, Tongwen Xu, Yaoming Wang","doi":"10.1016/j.ces.2024.120865","DOIUrl":"10.1016/j.ces.2024.120865","url":null,"abstract":"<div><div>Efficient separation of magnesium and lithium is essential for the extraction of lithium resources from salt-lake brines. However, the current membrane separation technologies are challenged by the membrane permeability-selectivity trade-off. Herein, we demonstrated a facile and practical approach to fabricate crown ether-functionalized polymeric membranes with excellent Li<sup>+</sup>/Mg<sup>2+</sup> separation performance by incorporating 12-crown-4 rings into the cellulose triacetate polymer network. The tightly and regularly arranged polymer chains anchored the crown ether rings firmly in the membrane structure, thereby facilitating the formation of stable and highly selective cation transport channels inside the membrane. As a result, the prepared membrane achieved an ultrahigh Li<sup>+</sup>/Mg<sup>2+</sup> separation factor of ∼872 and Li<sup>+</sup> flux of 22.6 μmol m<sup>−2</sup> s<sup>−1</sup>, which was much superior to that of commercial CIMS and reported membrane separation technologies. The good long-term stability of the fabricated membrane is promising for achieving efficient magnesium-lithium separation in large-scale industrial applications.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120865"},"PeriodicalIF":4.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489317","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
<div><div>Carbon capture and storage (CCS) has been a popular strategy to mitigate climate change and has attracted significant attention from both industry and academia. CO<sub>2</sub> can be stored in the form of CO<sub>2</sub> hydrate in deeper locations in an ocean, which makes it a potential option for CO<sub>2</sub> sequestration. Dissolved salts in the ocean brine can significantly affect the dissociation pressure of CO<sub>2</sub> hydrate. Sulfate salts are one of the most common salt species in the oceanic brine. Although various experimental studies have been conducted to investigate the phase behavior of CO<sub>2</sub> hydrate in brine, few studies focus on the effect of sulfate salts on the dissociation pressure of CO<sub>2</sub> hydrate. In this study, we build an in-house experimental setup to investigate the effect of monovalent and divalent sulfate salts on the dissociation pressure of CO<sub>2</sub> hydrate. The dissociation pressure of CO<sub>2</sub> hydrate in Na<sub>2</sub>SO<sub>4</sub>, K<sub>2</sub>SO<sub>4</sub>, MgSO<sub>4</sub>, and CuSO<sub>4</sub> aqueous solutions is measured using the isochoric pressure search method at different concentrations over the temperature range of 274.36 – 282.15 K and the pressure range of 1.50 – 4.03 MPa. A hybrid methodology incorporating the Soave-Redlich-Kwong Equation of State (SRK EOS), the van der Waals-Platteeuw (vdW-P) model, and the Pitzer model is applied to predict the dissociation pressure of CO<sub>2</sub> in sulfate solutions. In addition, the dissociation enthalpies of CO<sub>2</sub> hydrate in these sulfate solutions are calculated using the Clausius-Clapeyron equation based on the measured dissociation points. The experimental results show that the dissociation pressure of CO<sub>2</sub> hydrate in Na<sub>2</sub>SO<sub>4</sub>, K<sub>2</sub>SO<sub>4</sub>, and MgSO<sub>4</sub> solutions is higher than that in pure water, and the dissociation pressure of CO<sub>2</sub> hydrate in sulfate solutions increases with an increasing salt concentration. Conversely, CuSO<sub>4</sub> barely affects the dissociation pressure of CO<sub>2</sub> hydrate, which is mainly attributed to the lower molar concentration of the ions compared with the other salt solutions and the ion specificity of Cu<sup>2+</sup>. The prediction results are in alignment with the experimental data measured in this study, which proves the feasibility of the thermodynamic model in predicting the dissociation pressure of CO<sub>2</sub> hydrate in sulfate solutions. Additionally, the calculated dissociation enthalpies of CO<sub>2</sub> hydrate show a dependence on both temperature and salt concentration. It is also revealed that Cu<sup>2+</sup> exhibits ion specificity in affecting the dissociation enthalpy of CO<sub>2</sub> hydrate, likely due to its more distinct ability to impact the cage occupancy of CO<sub>2</sub> hydrate than the other ions. These findings enhance our understanding of the impact of sulfate sal
碳捕集与封存（CCS）一直是减缓气候变化的热门战略，并引起了工业界和学术界的极大关注。二氧化碳可以以二氧化碳水合物的形式储存在海洋深处，这使其成为二氧化碳封存的潜在选择。海洋盐水中的溶解盐会严重影响二氧化碳水合物的解离压力。硫酸盐是海洋盐水中最常见的盐类之一。虽然已经开展了各种实验研究来探讨二氧化碳水合物在盐水中的相行为，但很少有研究关注硫酸盐盐对二氧化碳水合物解离压力的影响。在本研究中，我们建立了一个内部实验装置来研究一价和二价硫酸盐对 CO2 水合物解离压力的影响。在温度范围为 274.36-282.15 K 和压力范围为 1.50-4.03 MPa 的条件下，采用等时压力搜索法测量了 Na2SO4、K2SO4、MgSO4 和 CuSO4 水溶液中二氧化碳水合物的解离压力。该方法结合了Soave-Redlich-Kwong状态方程（SRK EOS）、范德华-普拉蒂奥乌（vdW-P）模型和皮策模型，用于预测硫酸盐溶液中二氧化碳的解离压力。此外，还根据测得的解离点，使用克劳修斯-克拉皮隆方程计算了这些硫酸盐溶液中二氧化碳水合物的解离焓。实验结果表明，Na2SO4、K2SO4 和 MgSO4 溶液中二氧化碳水合物的解离压高于纯水中的解离压，而且随着盐浓度的增加，硫酸盐溶液中二氧化碳水合物的解离压也会增加。相反，CuSO4 几乎不影响 CO2 水合物的解离压，这主要是因为与其他盐溶液相比，CuSO4 的离子摩尔浓度较低，而且 Cu2+ 具有离子特异性。预测结果与本研究测量的实验数据一致，这证明了热力学模型预测硫酸盐溶液中 CO2 水合物解离压的可行性。此外，计算得出的 CO2 水合物解离焓与温度和盐浓度都有关系。研究还发现，Cu2+ 在影响 CO2 水合物解离焓方面表现出离子特异性，这可能是由于与其他离子相比，Cu2+ 对 CO2 水合物的笼占位具有独特的影响能力。这些发现加深了我们对硫酸盐对二氧化碳水合物解离行为的影响的理解，并为二氧化碳封存提供了宝贵的见解。
{"title":"Experimental measurements and thermodynamic modeling of dissociation pressure of CO2 hydrate in sulfate solutions","authors":"Ying Zhou , Zhuo Chen , Yu Wei , Nobuo Maeda , Huazhou Li","doi":"10.1016/j.ces.2024.120823","DOIUrl":"10.1016/j.ces.2024.120823","url":null,"abstract":"<div><div>Carbon capture and storage (CCS) has been a popular strategy to mitigate climate change and has attracted significant attention from both industry and academia. CO<sub>2</sub> can be stored in the form of CO<sub>2</sub> hydrate in deeper locations in an ocean, which makes it a potential option for CO<sub>2</sub> sequestration. Dissolved salts in the ocean brine can significantly affect the dissociation pressure of CO<sub>2</sub> hydrate. Sulfate salts are one of the most common salt species in the oceanic brine. Although various experimental studies have been conducted to investigate the phase behavior of CO<sub>2</sub> hydrate in brine, few studies focus on the effect of sulfate salts on the dissociation pressure of CO<sub>2</sub> hydrate. In this study, we build an in-house experimental setup to investigate the effect of monovalent and divalent sulfate salts on the dissociation pressure of CO<sub>2</sub> hydrate. The dissociation pressure of CO<sub>2</sub> hydrate in Na<sub>2</sub>SO<sub>4</sub>, K<sub>2</sub>SO<sub>4</sub>, MgSO<sub>4</sub>, and CuSO<sub>4</sub> aqueous solutions is measured using the isochoric pressure search method at different concentrations over the temperature range of 274.36 – 282.15 K and the pressure range of 1.50 – 4.03 MPa. A hybrid methodology incorporating the Soave-Redlich-Kwong Equation of State (SRK EOS), the van der Waals-Platteeuw (vdW-P) model, and the Pitzer model is applied to predict the dissociation pressure of CO<sub>2</sub> in sulfate solutions. In addition, the dissociation enthalpies of CO<sub>2</sub> hydrate in these sulfate solutions are calculated using the Clausius-Clapeyron equation based on the measured dissociation points. The experimental results show that the dissociation pressure of CO<sub>2</sub> hydrate in Na<sub>2</sub>SO<sub>4</sub>, K<sub>2</sub>SO<sub>4</sub>, and MgSO<sub>4</sub> solutions is higher than that in pure water, and the dissociation pressure of CO<sub>2</sub> hydrate in sulfate solutions increases with an increasing salt concentration. Conversely, CuSO<sub>4</sub> barely affects the dissociation pressure of CO<sub>2</sub> hydrate, which is mainly attributed to the lower molar concentration of the ions compared with the other salt solutions and the ion specificity of Cu<sup>2+</sup>. The prediction results are in alignment with the experimental data measured in this study, which proves the feasibility of the thermodynamic model in predicting the dissociation pressure of CO<sub>2</sub> hydrate in sulfate solutions. Additionally, the calculated dissociation enthalpies of CO<sub>2</sub> hydrate show a dependence on both temperature and salt concentration. It is also revealed that Cu<sup>2+</sup> exhibits ion specificity in affecting the dissociation enthalpy of CO<sub>2</sub> hydrate, likely due to its more distinct ability to impact the cage occupancy of CO<sub>2</sub> hydrate than the other ions. These findings enhance our understanding of the impact of sulfate sal","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120823"},"PeriodicalIF":4.1,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-23DOI: 10.1016/j.ces.2024.120862
Ana Paula Fagundes , Eduardo Guilherme Cividini Neiva , Lizandra Maria Zimmermann , Natan Padoin , Cíntia Soares , Humberto Gracher Riella
3D printing is a fast-growing technology with benefits like rapid prototyping and versatile design capabilities. However, Fused Deposition Modeling (FDM) needs improvement due to limited material options. This study proposes a method for producing photocatalytic prototypes using 3D printing/FDM, focusing on environmental applications like contaminant degradation. Key steps included filament production through melt and solution mixing, defining geometries, 3D printing functional prototypes, and characterizing materials chemically, thermally, microscopically, and mechanically. The photocatalytic capacity was evaluated via tetracycline degradation, showing 45–60% efficiency for ZnO filaments and up to 65% for TiO2 filaments. ZnO-functionalized parts maintained 80% removal capacity after 10 reuse cycles without activation, indicating reduced leaching and photo corrosion. This study advances 3D printing/FDM research for environmental applications, providing a methodology for producing effective photocatalytic prototypes.
三维打印是一项快速发展的技术，具有快速原型制作和多功能设计等优点。然而，由于材料选择有限，熔融沉积建模（FDM）需要改进。本研究提出了一种利用 3D 打印/FDM 制作光催化原型的方法，重点关注污染物降解等环境应用。关键步骤包括通过熔融和溶液混合生产长丝、确定几何形状、3D 打印功能原型，以及对材料进行化学、热学、显微和机械表征。通过四环素降解评估了光催化能力，结果显示氧化锌丝的光催化效率为 45-60%，二氧化钛丝的光催化效率高达 65%。氧化锌功能化部件在 10 次重复使用后仍能保持 80% 的去除能力，无需活化，这表明沥滤和光腐蚀现象有所减少。这项研究为生产有效的光催化原型提供了一种方法，推动了环境应用领域的 3D 打印/FDM 研究。
{"title":"Melting and solution mixing in the production of photocatalytic filaments for 3D printing","authors":"Ana Paula Fagundes , Eduardo Guilherme Cividini Neiva , Lizandra Maria Zimmermann , Natan Padoin , Cíntia Soares , Humberto Gracher Riella","doi":"10.1016/j.ces.2024.120862","DOIUrl":"10.1016/j.ces.2024.120862","url":null,"abstract":"<div><div>3D printing is a fast-growing technology with benefits like rapid prototyping and versatile design capabilities. However, Fused Deposition Modeling (FDM) needs improvement due to limited material options. This study proposes a method for producing photocatalytic prototypes using 3D printing/FDM, focusing on environmental applications like contaminant degradation. Key steps included filament production through melt and solution mixing, defining geometries, 3D printing functional prototypes, and characterizing materials chemically, thermally, microscopically, and mechanically. The photocatalytic capacity was evaluated via tetracycline degradation, showing 45–60% efficiency for ZnO filaments and up to 65% for TiO<sub>2</sub> filaments. ZnO-functionalized parts maintained 80% removal capacity after 10 reuse cycles without activation, indicating reduced leaching and photo corrosion. This study advances 3D printing/FDM research for environmental applications, providing a methodology for producing effective photocatalytic prototypes.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"302 ","pages":"Article 120862"},"PeriodicalIF":4.1,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488152","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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