Shuyuan Fan, Xiaodong Hong, Zuwei Liao, Congjing Ren, Yao Yang, Jingdai Wang, Yongrong Yang
Constrained black-box optimization (CBBO) has become increasingly popular in process optimization. Algorithms often encounter difficulties in balancing feasibility and optimality, with some even failing to find feasible solutions. This article introduces an adaptive sampling Bayesian optimization algorithm (ASBO) to solve CBBO problems effectively. The developed infill sampling criterion introduces an adaptive acquisition function to facilitate multistage optimization. The three stages consist of exploring feasible solutions, balancing feasibility and optimality, and optimizing. Furthermore, a hybrid method is proposed for complex problems. A gradient-based optimizer (GBO) aids in constructing the posterior distribution, thereby enhancing the identification of feasible regions. Additionally, four auxiliary strategies are developed to enhance stability and accelerate convergence in simulation-based optimization. The effectiveness of the proposed algorithm is validated through three benchmark problems and two process optimization cases. Comparative analysis against state-of-the-art algorithms demonstrates better iteration efficiency of ASBO algorithms.
{"title":"Adaptive sampling Bayesian algorithm for constrained black-box optimization problems","authors":"Shuyuan Fan, Xiaodong Hong, Zuwei Liao, Congjing Ren, Yao Yang, Jingdai Wang, Yongrong Yang","doi":"10.1002/aic.18715","DOIUrl":"https://doi.org/10.1002/aic.18715","url":null,"abstract":"Constrained black-box optimization (CBBO) has become increasingly popular in process optimization. Algorithms often encounter difficulties in balancing feasibility and optimality, with some even failing to find feasible solutions. This article introduces an adaptive sampling Bayesian optimization algorithm (ASBO) to solve CBBO problems effectively. The developed infill sampling criterion introduces an adaptive acquisition function to facilitate multistage optimization. The three stages consist of exploring feasible solutions, balancing feasibility and optimality, and optimizing. Furthermore, a hybrid method is proposed for complex problems. A gradient-based optimizer (GBO) aids in constructing the posterior distribution, thereby enhancing the identification of feasible regions. Additionally, four auxiliary strategies are developed to enhance stability and accelerate convergence in simulation-based optimization. The effectiveness of the proposed algorithm is validated through three benchmark problems and two process optimization cases. Comparative analysis against state-of-the-art algorithms demonstrates better iteration efficiency of ASBO algorithms.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"34 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917653","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}
Producing battery-grade lithium hydroxide (LiOH) from lithium salts is essential for high-performance lithium-ion batteries. Traditional causticization methods, which involve metathesis reactions between lithium salts (such as Li2CO3, Li2SO4, or LiCl) and bases (such as Ca(OH)2, NaOH, or Ba(OH)2), often result in low concentrations of LiOH and significant lithium loss dragged by CaCO3/Na2SO4/BaSO4 as solid waste. To address these challenges, we developed the “electro-metathesis” membrane reactor, which integrates the metathesis reaction with an electro-membrane system based on ion-distillation technology. This technology enhances the causticization process by regulating ion migration through ion exchange membranes and blocking impurity ions stage by stage, improving lithium recovery to 84.4% and achieving high-purity (99.6%) LiOH products. Furthermore, the process cost is 3.32 $/kg LiOH, which is lower than traditional causticization processes. This research highlights the advantages of the “electro-metathesis” membrane reactor in process efficiency, product quality, and cost management, showing strong potential for industrial applications.
{"title":"An electro-metathesis membrane reactor for directly producing LiOH with purity exceeding 99.5%","authors":"Xiao Liu, Guangzhong Cao, Songhui Wang, Weixiang Shan, Tianle Gu, Zhaoming Liu, Chenxiao Jiang, Tongwen Xu","doi":"10.1002/aic.18705","DOIUrl":"https://doi.org/10.1002/aic.18705","url":null,"abstract":"Producing battery-grade lithium hydroxide (LiOH) from lithium salts is essential for high-performance lithium-ion batteries. Traditional causticization methods, which involve metathesis reactions between lithium salts (such as Li<sub>2</sub>CO<sub>3</sub>, Li<sub>2</sub>SO<sub>4</sub>, or LiCl) and bases (such as Ca(OH)<sub>2</sub>, NaOH, or Ba(OH)<sub>2</sub>), often result in low concentrations of LiOH and significant lithium loss dragged by CaCO<sub>3</sub>/Na<sub>2</sub>SO<sub>4</sub>/BaSO<sub>4</sub> as solid waste. To address these challenges, we developed the “electro-metathesis” membrane reactor, which integrates the metathesis reaction with an electro-membrane system based on ion-distillation technology. This technology enhances the causticization process by regulating ion migration through ion exchange membranes and blocking impurity ions stage by stage, improving lithium recovery to 84.4% and achieving high-purity (99.6%) LiOH products. Furthermore, the process cost is 3.32 $/kg LiOH, which is lower than traditional causticization processes. This research highlights the advantages of the “electro-metathesis” membrane reactor in process efficiency, product quality, and cost management, showing strong potential for industrial applications.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"44 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905571","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}
Bin Wu, Lin Chen, Yanchun Fan, Huidong Zheng, Fuweng Zhang
This study investigates the turbulent two-phase dispersion of toluene-water in micro-impinging jet (MIJ) mixers using both experimental and numerical methods. We employ computational fluid dynamics combined with the population balance model (CFD-PBM) to predict the mean droplet size (d32) and droplet size distribution (DSD). The numerical predictions align well with the experimental results. The liquid–liquid dispersion in the MIJ mixer is a two-step process, each step governed by the velocity ratio (r) and Reynolds number (Rej), respectively. By increasing the volume flow rate (Q) and r, or by reducing the diameter of the outlet orifice of mixing chamber (Do), the dispersion process can be intensified. This leads to the production of smaller droplets with a narrow DSD within a millisecond timeframe. Additionally, we propose a correlation for d32 that accurately describes the two-step dispersion process of the mixer, providing a reliable guide for the design and optimization of liquid–liquid systems.
{"title":"Experimental study and numerical simulation of liquid–liquid dispersions in micro-impinging jet mixers","authors":"Bin Wu, Lin Chen, Yanchun Fan, Huidong Zheng, Fuweng Zhang","doi":"10.1002/aic.18720","DOIUrl":"https://doi.org/10.1002/aic.18720","url":null,"abstract":"This study investigates the turbulent two-phase dispersion of toluene-water in micro-impinging jet (MIJ) mixers using both experimental and numerical methods. We employ computational fluid dynamics combined with the population balance model (CFD-PBM) to predict the mean droplet size (<i>d</i><sub>32</sub>) and droplet size distribution (DSD). The numerical predictions align well with the experimental results. The liquid–liquid dispersion in the MIJ mixer is a two-step process, each step governed by the velocity ratio (<i>r</i>) and Reynolds number (<i>Re</i><sub>j</sub>), respectively. By increasing the volume flow rate (<i>Q</i>) and <i>r</i>, or by reducing the diameter of the outlet orifice of mixing chamber (<i>D</i><sub>o</sub>), the dispersion process can be intensified. This leads to the production of smaller droplets with a narrow DSD within a millisecond timeframe. Additionally, we propose a correlation for <i>d</i><sub>32</sub> that accurately describes the two-step dispersion process of the mixer, providing a reliable guide for the design and optimization of liquid–liquid systems.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"36 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902127","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}
Dong Lin, Xiuhui Zheng, Ze Zong, Yang Xu, Qiuming He, Zhe Ma, De Chen, Chaohe Yang, Xiang Feng
Comprehensive mechanistic explorations and profound understandings of the interactions between water molecules and active intermediates harbors tremendous significance in the field of zeolite catalysis. Herein, we envision a strategy to accelerate alkene epoxidation reactions (e.g., 1-pentene, 1-hexene, cyclohexene, cyclooctene) with preformed H2O2 inside confined channels of Ti-beta by water molecules. Combined with in situ UV–vis, kinetic experiments, and DFT calculations, it is found that keen control of water molecules could effectively enhance H2O2 adsorption and stabilize crucial oxygen intermediates (Ti-OOH) by hydrogen bonding interactions. As a result, the yields of corresponding epoxides increased up to 20.5%. However, excessive water clusters construct a dense and robust hydrogen-bond network, blocking the activation of reactants and further epoxidation over Ti sites. This finding not only sheds new light on the mechanism of water-accelerated reaction, but also opens up new opportunities to enhance the efficiency of industrial epoxidation reactions involving H2O2.
{"title":"Confined water accelerated alkene epoxidation inside channels of Ti-beta zeolite","authors":"Dong Lin, Xiuhui Zheng, Ze Zong, Yang Xu, Qiuming He, Zhe Ma, De Chen, Chaohe Yang, Xiang Feng","doi":"10.1002/aic.18726","DOIUrl":"https://doi.org/10.1002/aic.18726","url":null,"abstract":"Comprehensive mechanistic explorations and profound understandings of the interactions between water molecules and active intermediates harbors tremendous significance in the field of zeolite catalysis. Herein, we envision a strategy to accelerate alkene epoxidation reactions (e.g., 1-pentene, 1-hexene, cyclohexene, cyclooctene) with preformed H<sub>2</sub>O<sub>2</sub> inside confined channels of Ti-beta by water molecules. Combined with <i>in situ</i> UV–vis, kinetic experiments, and DFT calculations, it is found that keen control of water molecules could effectively enhance H<sub>2</sub>O<sub>2</sub> adsorption and stabilize crucial oxygen intermediates (Ti-OOH) by hydrogen bonding interactions. As a result, the yields of corresponding epoxides increased up to 20.5%. However, excessive water clusters construct a dense and robust hydrogen-bond network, blocking the activation of reactants and further epoxidation over Ti sites. This finding not only sheds new light on the mechanism of water-accelerated reaction, but also opens up new opportunities to enhance the efficiency of industrial epoxidation reactions involving H<sub>2</sub>O<sub>2</sub>.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"114 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888552","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}
Dalia N. Dorantes-Landa, Alberto Hernandez-Aguirre, Luis Ricardez-Sandoval, Sergio Huerta-Ochoa, Carlos O. Castillo-Araiza
This work develops an approach to identify the suitable representative volume (unit cell) that captures fluid dynamics in beds packed with spheres or cylinders with a dt/dp ≤ 10, by describing radial void fraction and velocity profiles at particle Reynolds numbers between 5 and 100. Rigid-body simulations were used to construct synthetic packings, while velocity profiles were obtained from particle-resolved simulations. This methodology, rooted in the similitude of fluid dynamics between beds of different lengths, determines the minimum length (or number of particles in a bed) required for the unit cell to accurately describe the void fraction and velocity profiles. Defining such a unit cell for fluid dynamics not only reduces computational effort but also opens avenues for its use in multiscale techniques to develop reliable pseudo-continuous models, which is currently the bottleneck in the design and optimization of wall-cooled packed-bed reactors in industrial scenarios.
{"title":"A systematic approach to defining a unit cell for fluid dynamics in packed beds with low tube-to-particle diameter ratio","authors":"Dalia N. Dorantes-Landa, Alberto Hernandez-Aguirre, Luis Ricardez-Sandoval, Sergio Huerta-Ochoa, Carlos O. Castillo-Araiza","doi":"10.1002/aic.18707","DOIUrl":"https://doi.org/10.1002/aic.18707","url":null,"abstract":"This work develops an approach to identify the suitable representative volume (unit cell) that captures fluid dynamics in beds packed with spheres or cylinders with a <i>d</i><sub>t</sub>/<i>d</i><sub>p</sub> ≤ 10, by describing radial void fraction and velocity profiles at particle Reynolds numbers between 5 and 100. Rigid-body simulations were used to construct synthetic packings, while velocity profiles were obtained from particle-resolved simulations. This methodology, rooted in the similitude of fluid dynamics between beds of different lengths, determines the minimum length (or number of particles in a bed) required for the unit cell to accurately describe the void fraction and velocity profiles. Defining such a unit cell for fluid dynamics not only reduces computational effort but also opens avenues for its use in multiscale techniques to develop reliable pseudo-continuous models, which is currently the bottleneck in the design and optimization of wall-cooled packed-bed reactors in industrial scenarios.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"14 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887182","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}
Currently, bipolar membrane electrodialysis (BMED) is recognized as an eco-friendly technique to recycle lithium from waste lithium-ion batteries. However, the application of ordinary bipolar membranes has the disadvantage of unsatisfactory product purity due to undesired ion leakage. Herein, we proposed isolation chamber bipolar membrane electrodialysis (ICBMED) to inhibit coion migration, thereby increasing the purity of the regenerated acid and alkali. The experimental results indicate that 97.7%–99.3% of the LiOH generated by the ICBMED using domestic membranes was generated, which is much greater than the 85.7%–94.4% obtained without an isolation chamber. The total cost of the ICBMED for LiOH production with inexpensive domestic membranes was 1.65$/kg-LiOH (US) at 400 A/m2, which is lower than the cost of 1.91$/kg-LiOH (US) for flagship membranes with identical product quality. BMED with an isolation chamber provides a viable solution for acid–base production by balancing product quality and cost.
{"title":"Bipolar membrane electrodialysis with isolation chamber enables high-purity LiOH production with ordinary membranes","authors":"Duyi He, Weicheng Fu, Zihao Wang, Junying Yan, Huangying Wang, Ruirui Li, Baoying Wang, Xiaochun Chen, Yaoming Wang, Tongwen Xu","doi":"10.1002/aic.18674","DOIUrl":"https://doi.org/10.1002/aic.18674","url":null,"abstract":"Currently, bipolar membrane electrodialysis (BMED) is recognized as an eco-friendly technique to recycle lithium from waste lithium-ion batteries. However, the application of ordinary bipolar membranes has the disadvantage of unsatisfactory product purity due to undesired ion leakage. Herein, we proposed isolation chamber bipolar membrane electrodialysis (ICBMED) to inhibit coion migration, thereby increasing the purity of the regenerated acid and alkali. The experimental results indicate that 97.7%–99.3% of the LiOH generated by the ICBMED using domestic membranes was generated, which is much greater than the 85.7%–94.4% obtained without an isolation chamber. The total cost of the ICBMED for LiOH production with inexpensive domestic membranes was 1.65$/kg-LiOH (US) at 400 A/m<sup>2</sup>, which is lower than the cost of 1.91$/kg-LiOH (US) for flagship membranes with identical product quality. BMED with an isolation chamber provides a viable solution for acid–base production by balancing product quality and cost.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"202 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880176","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}
Porous membranes, a type of material widely used in nanofiltration, are confronted with the limitation that the influence of channel–molecule interactions on transport behaviors has yet been investigated in detail. Herein, covalent organic framework membranes with adjustable pore sizes (⁓ 2.5 nm and ⁓ 1.2 nm) and chemical groups (−F, −OH, and −CO−) were prepared by interfacial polymerization. We demonstrate that strong channel–molecule attraction induces the formation of stable solvent layers along nanochannel walls, which protect central molecules from the attraction of chemical groups. Significantly, stable solvent layers permit fast transport of ethanol (245.6 L m−2 h−1 bar−1) with reactive black (RB) rejection of 96%. Likely, for membranes with weak channel–molecule attraction, no solvent layers are formed and molecules also transport smoothly. Interestingly, membranes that exhibit moderate channel–molecule attraction exert metastable solvent layers, thus displaying high transport resistance. This hindrance effect on molecule transport becomes more pronounced in smaller nanochannels.
多孔膜是一种广泛应用于纳滤的材料，但由于通道-分子相互作用对其传输行为的影响尚未得到详细的研究，因此存在一定的局限性。本文采用界面聚合法制备了孔径可调（⁓2.5 nm和⁓1.2 nm）、化学基团可调（−F、−OH和−CO−）的共价有机骨架膜。我们证明了强大的通道-分子吸引力诱导沿纳米通道壁形成稳定的溶剂层，从而保护中心分子免受化学基团的吸引。值得注意的是，稳定的溶剂层允许乙醇快速运输（245.6 L m−2 h−1 bar−1），活性黑（RB）的去除率为96%。很可能，对于具有弱通道-分子吸引力的膜，没有形成溶剂层，分子也能顺利运输。有趣的是，表现出适度通道-分子吸引力的膜施加亚稳溶剂层，从而表现出高的运输阻力。在更小的纳米通道中，这种对分子运输的阻碍作用变得更加明显。
{"title":"Channel–molecule attraction mediated molecule transport in confined nanochannels of COF membranes for nanofiltration","authors":"Ruilong Li, Yongjian Yang, Jingjing Chen, Chongchong Chen, Wenpeng Li, Xiaoli Wu, Jingtao Wang","doi":"10.1002/aic.18719","DOIUrl":"https://doi.org/10.1002/aic.18719","url":null,"abstract":"Porous membranes, a type of material widely used in nanofiltration, are confronted with the limitation that the influence of channel–molecule interactions on transport behaviors has yet been investigated in detail. Herein, covalent organic framework membranes with adjustable pore sizes (⁓ 2.5 nm and ⁓ 1.2 nm) and chemical groups (−F, −OH, and −CO−) were prepared by interfacial polymerization. We demonstrate that strong channel–molecule attraction induces the formation of stable solvent layers along nanochannel walls, which protect central molecules from the attraction of chemical groups. Significantly, stable solvent layers permit fast transport of ethanol (245.6 L m<sup>−2</sup> h<sup>−1</sup> bar<sup>−1</sup>) with reactive black (RB) rejection of 96%. Likely, for membranes with weak channel–molecule attraction, no solvent layers are formed and molecules also transport smoothly. Interestingly, membranes that exhibit moderate channel–molecule attraction exert metastable solvent layers, thus displaying high transport resistance. This hindrance effect on molecule transport becomes more pronounced in smaller nanochannels.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"65 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880175","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}
Yan Zhang, Hai Liu, Ruoyu Hu, Yan Zhou, Shuai Wang, Jianguang Qi, Yinglong Wang, Zhaoyou Zhu, Guoxuan Li
A novel phospho-based hydrophobic deep eutectic solvents (HDESs) is proposed to selectively extract valuable metals from waste lithium-ion batteries (LIBs). Under the optimized extraction conditions, the single-stage extraction efficiency of HDES [TOP][Lid] for Co2+ and Ni2+ were 98.5% and 83.9%, and HDES [TBP][Lid] for Co2+ and Ni2+ were 96.0% and 82.9%, and Li+ was enriched in the extract. FT-IR, 1H NMR, and ESP analysis confirmed the hydrogen bond between HBD and HBA. The metal ion extraction mechanism by HDESs was analyzed based on quantum chemistry (QC) and molecular dynamics (MD). The extraction mechanism at the molecular level is that electrostatic and coordination interactions between transition metal ions and HDESs dominate the extraction of metal ions (Co2+ and Ni2+). The interaction intensity with HDESs was stronger than that between Li+ and HDESs.
{"title":"Extraction of valuable metals from waste Li-ion batteries by deep eutectic solvent: Experimental and mechanism analysis","authors":"Yan Zhang, Hai Liu, Ruoyu Hu, Yan Zhou, Shuai Wang, Jianguang Qi, Yinglong Wang, Zhaoyou Zhu, Guoxuan Li","doi":"10.1002/aic.18714","DOIUrl":"https://doi.org/10.1002/aic.18714","url":null,"abstract":"A novel phospho-based hydrophobic deep eutectic solvents (HDESs) is proposed to selectively extract valuable metals from waste lithium-ion batteries (LIBs). Under the optimized extraction conditions, the single-stage extraction efficiency of HDES [TOP][Lid] for Co<sup>2+</sup> and Ni<sup>2+</sup> were 98.5% and 83.9%, and HDES [TBP][Lid] for Co<sup>2+</sup> and Ni<sup>2+</sup> were 96.0% and 82.9%, and Li<sup>+</sup> was enriched in the extract. FT-IR, <sup>1</sup>H NMR, and ESP analysis confirmed the hydrogen bond between HBD and HBA. The metal ion extraction mechanism by HDESs was analyzed based on quantum chemistry (QC) and molecular dynamics (MD). The extraction mechanism at the molecular level is that electrostatic and coordination interactions between transition metal ions and HDESs dominate the extraction of metal ions (Co<sup>2+</sup> and Ni<sup>2+</sup>). The interaction intensity with HDESs was stronger than that between Li<sup>+</sup> and HDESs.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"25 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880240","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}
Acceptorless dehydrogenation of biomass-alcohol provides an appealing route for co-producing green H2 and high-value chemicals. However, the sluggish H species binding step severely inhibits reaction equilibrium and cause C-C cleavage. Herein, we propose a unique directional H spillover strategy driven by controlling electron transport direction via constructing Au-O-Cu-O-Mg/Al interfacial structure, to allow H species transfer from O-H dehydrogenation Cu2+ site to C-H dehydrogenation Au site to promote H2 formation. The structure that each Cu precisely terminated by Mg/Al is inherited from layered double hydroxides with orderly dispersed atom arrangement. Comprehensive studies substantiate that the unreducible Mg2+/Al3+ blocks electron transfer toward support, whereas Au-O-Cu electronic interaction drives H spillover from the support to Au. The Au/CuMgAl catalyst demonstrated unprecedentedly high glycerol dehydrogenation activity, showing 3–10 times turnover frequency (1.18 × 104 h−1) than other biomass-derived H2 formation system, co-producing lactic acid with selectivity up to 98.8%.
生物质醇的无受体脱氢为绿色H2和高价值化学品的联产提供了一条有吸引力的途径。然而，缓慢的H结合步骤严重抑制了反应平衡，导致C-C裂解。本文提出了一种独特的定向H溢出策略，通过构建Au- o - cu - o - mg /Al界面结构来控制电子传递方向，使H从O-H脱氢Cu2+位点转移到C-H脱氢Au位点，促进H2的形成。每个Cu被Mg/Al精确终止的结构继承自有序分散原子排列的层状双氧水。综合研究证实，不可还原的Mg2+/Al3+阻止了电子向载体的转移，而Au- o - cu电子相互作用则驱动H从载体向Au的溢出。Au/CuMgAl催化剂表现出前所未有的高甘油脱氢活性，其转换频率（1.18 × 104 h−1）是其他生物质生成H2体系的3-10倍，共产乳酸的选择性高达98.8%。
{"title":"Carbon-zero co-production of hydrogen and chemicals boosted by directional hydrogen spillover via terminated interface","authors":"Xuanlin Guo, Huifang Wu, Yang Zhao, Lirong Zheng, Qian Wang, Dianqing Li, Junting Feng","doi":"10.1002/aic.18713","DOIUrl":"https://doi.org/10.1002/aic.18713","url":null,"abstract":"Acceptorless dehydrogenation of biomass-alcohol provides an appealing route for co-producing green H<sub>2</sub> and high-value chemicals. However, the sluggish H species binding step severely inhibits reaction equilibrium and cause C-C cleavage. Herein, we propose a unique directional H spillover strategy driven by controlling electron transport direction via constructing Au-O-Cu-O-Mg/Al interfacial structure, to allow H species transfer from O-H dehydrogenation Cu<sup>2+</sup> site to C-H dehydrogenation Au site to promote H<sub>2</sub> formation. The structure that each Cu precisely terminated by Mg/Al is inherited from layered double hydroxides with orderly dispersed atom arrangement. Comprehensive studies substantiate that the unreducible Mg<sup>2+</sup>/Al<sup>3+</sup> blocks electron transfer toward support, whereas Au-O-Cu electronic interaction drives H spillover from the support to Au. The Au/CuMgAl catalyst demonstrated unprecedentedly high glycerol dehydrogenation activity, showing 3–10 times turnover frequency (1.18 × 10<sup>4</sup> h<sup>−1</sup>) than other biomass-derived H<sub>2</sub> formation system, co-producing lactic acid with selectivity up to 98.8%.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"2 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874865","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}
Yiming Xu, Fujun Li, Yun Zou, Jinzhe Cao, Shengyang Tao
Many rapid and strongly exothermic reactions have transitioned to continuous flow reactors for safety considerations. However, data from batch calorimeters often fall short in guiding these processes due to substantial differences in transfer characteristics, and the adiabatic components of calorimeters significantly escalate equipment costs and dimensions. Inspired by the human body's thermoregulatory mechanism, we developed the Dynamic Tracking Reference Continuous Calorimeter (DTRCC). This novel device enables rapid and precise calorimetry in continuous‐flow reactions under nonadiabatic conditions and variable external temperatures. The measurement time can be reduced to 110 s with a low difference of 0.5%. The DTRCC proves versatile across various reaction types, including nitrification and photoreaction. It can also determine solutions' heat capacity and reactions' selectivity according to calorimetry. Implementing the DTRCC provides crucial data that enhance the design and optimization of continuous flow reactors, significantly boosting chemical process safety and efficiency.
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