AIChE JournalPub Date : 2025-05-20DOI: 10.1002/aic.18914
Qi Lu, Lili Tong, Xiaolei Guo, Kang Xue, Li Wang, Chengxiang Shi, Ruijie Gao, Ji-Jun Zou, Xiangwen Zhang, Lun Pan
{"title":"Mechanism of norbornadiene dimerization promotion by Co-species-modified alkali-treated zeolite","authors":"Qi Lu, Lili Tong, Xiaolei Guo, Kang Xue, Li Wang, Chengxiang Shi, Ruijie Gao, Ji-Jun Zou, Xiangwen Zhang, Lun Pan","doi":"10.1002/aic.18914","DOIUrl":"https://doi.org/10.1002/aic.18914","url":null,"abstract":"Norbornadiene (NBD) dimer is one of the most important high-energy-density fuels for aerospace propulsion, but it is difficult to synthesize with high efficiency. Herein, we fabricated nano-cobalt loaded alkali-treated HY zeolite, which significantly promotes the NBD dimerization reaction with a conversion of 73.5% and a selectivity of 84.7%, which is a 20% higher yield than previously reported catalysts. The characterizations confirm that the mild alkali treatment expands the zeolite pore size, providing more reaction space and enhancing the NBD conversion. The <i>in situ</i> Fourier-transform infrared spectra demonstrate that alkali-treated zeolites can adsorb more NBD, and the incorporation of Co species enhances the adsorption of double bonds to form a stable transition state with a three-center two-electron configuration, thereby promoting the reaction. The dimerization product after hydrogenation has a high density (1.06 g/mL at 20°C) and high volumetric neat heat of combustion (45.3 MJ/L), which is very promising for practical application.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"234 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144097627","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}
{"title":"Versatile and dense sites in an interpenetrated adsorbent for one-step ethylene separation from quaternary gas-mixtures","authors":"Yong Zeng, Hao Wang, Yanan Wang, Xing Liu, Shuangqing Shang, Zhenglong Zhu, Cheng Liu, Hanting Xiong, Jingwen Chen, Zhenyu Zhou, Shixia Chen, Shuguang Deng, Jun Wang","doi":"10.1002/aic.18892","DOIUrl":"https://doi.org/10.1002/aic.18892","url":null,"abstract":"One-step purification of ethylene (C<sub>2</sub>H<sub>4</sub>) from complex crude C<sub>2</sub>H<sub>4</sub> products containing acetylene (C<sub>2</sub>H<sub>2</sub>), ethane (C<sub>2</sub>H<sub>6</sub>), and carbon dioxide (CO<sub>2</sub>) impurities is highly critical and desirable. Herein, we customize the pore environments with versatile and dense adsorption sites in a novel interpenetrated adsorbent, Zn-mtz-ina, to simultaneously remove C<sub>2</sub>H<sub>2</sub>, CO<sub>2</sub>, and C<sub>2</sub>H<sub>6</sub> from C<sub>2</sub>H<sub>4</sub>. As a result, Zn-mtz-ina exhibits benchmark adsorption capacity for C<sub>2</sub>H<sub>2</sub> (3.01 mmol g<sup>−1</sup>) and IAST selectivity for C<sub>2</sub>H<sub>2</sub>/C<sub>2</sub>H<sub>4</sub> (4.7), along with a low C<sub>2</sub>H<sub>4</sub> uptake (1.60 mmol g<sup>−1</sup>) among reported similar adsorbents. Dynamic breakthrough experiments confirm the direct production of polymer-grade C<sub>2</sub>H<sub>4</sub> (>99.9%) from a C<sub>2</sub>H<sub>2</sub>/C<sub>2</sub>H<sub>6</sub>/CO<sub>2</sub>/C<sub>2</sub>H<sub>4</sub> (1/33/33/33, <i>v/v/v/v</i>) gas mixture with a high productivity of 0.36 mmol g<sup>−1</sup> under ambient conditions. The underlying separation mechanisms and guest–host interactions are elucidated through gas-loaded single crystal analysis, density functional theory calculations, and visualized Hirshfeld surface analysis.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"25 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144088119","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}
AIChE JournalPub Date : 2025-05-19DOI: 10.1002/aic.18899
Zhipeng Xiong, Huihuang Xia, Ji Xu, Chunjiang Liu, Wei Ge
{"title":"A dual–grid approach for CFD–DEM simulation of gas–solid heat transfer","authors":"Zhipeng Xiong, Huihuang Xia, Ji Xu, Chunjiang Liu, Wei Ge","doi":"10.1002/aic.18899","DOIUrl":"https://doi.org/10.1002/aic.18899","url":null,"abstract":"Gas–solid fluidized beds are widely used in industrial processes. Accurate and efficient simulations of the gas–solid flow dynamics and transfer are crucial for improving the design, scale–up, and optimization of the reactors. For this purpose, a dual–grid computational fluid dynamics and discrete element method (CFD–DEM) approach is developed to study the gas–solid heat transfer. The proposed approach uses both coarse and fine grids, where the gas velocity and pressure on the coarse grid are solved by the complete Navier–Stokes equations, while the gas velocity on the fine grid is predicted by solving the simplified Navier–Stokes equations. The predicted mass flux at the face center is then corrected by solving the velocity potential equation, and the energy conservation equation is solved on the fine grid. Results show that the proposed dual–grid approach can produce comparable results with the fine–grid CFD–DEM simulations and achieve at most 65.1 times speedup.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"45 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087950","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}
AIChE JournalPub Date : 2025-05-16DOI: 10.1002/aic.18888
Yash Barhate, Daniel J. Laky, Daniel Casas‐Orozco, Gintaras V. Reklaitis, Zoltan K. Nagy
{"title":"Hybrid rule‐based and optimization‐driven framework for the synthesis of end‐to‐end optimal pharmaceutical processes","authors":"Yash Barhate, Daniel J. Laky, Daniel Casas‐Orozco, Gintaras V. Reklaitis, Zoltan K. Nagy","doi":"10.1002/aic.18888","DOIUrl":"https://doi.org/10.1002/aic.18888","url":null,"abstract":"The modernization of pharmaceutical manufacturing is driving a shift from traditional batch processing to continuous alternatives. Synthesizing end‐to‐end optimal (E2EO) manufacturing routes is crucial for the pharmaceutical industry, especially when considering multiple operating modes—such as batch, continuous, or hybrid (containing both batch and continuous steps). A major challenge is the ability to compare these manufacturing alternatives across different operating modes, hindering optimal superstructure synthesis. To bridge this gap, this study introduces a hierarchical framework for the synthesis of E2EO manufacturing routes, employing a hybrid rule‐based and optimization‐driven approach. This method optimizes flowsheets modeled using PharmaPy through a simulation‐optimization technique with modest computational requirements. The effectiveness of the proposed framework is demonstrated through a case study on the manufacturing of the cancer therapy drug Lomustine. Two distinct manufacturing scenarios are analyzed to generate E2EO manufacturing campaigns tailored to the specific chemistries and process configurations, considering process efficiency and sustainable manufacturing.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"42 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066007","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}
{"title":"Boosting Faradaic efficiency in anodic chlorination: Strategies from electrode modification to device development","authors":"Tao Shen, Yuanbo Xu, Yibo Zhao, Chengjun Jiang, Yifeng Lai, Zeng Hong, Chao Qian, Shaodong Zhou","doi":"10.1002/aic.18880","DOIUrl":"https://doi.org/10.1002/aic.18880","url":null,"abstract":"Anodic electrochemical reactions in aqueous solutions often suffer from low Faradaic efficiency (FE) due to the competing oxygen evolution reaction (OER). To address this issue, the modification of carbon paper (CP) electrode is coupled with a membrane-free biphasic electrochemical device. Scanning electron microscopy (SEM) and water contact angle measurements confirmed the hydrophobic properties of the modified CPs. The <i>in situ</i> infrared (IR) spectroscopy and molecular dynamics (MD) simulation demonstrated that the hydrophobic surface repels water at the electrode interface, significantly reducing its local concentration. The biphasic electrochemical device is promoted by surfactants. Transmission electron microscope (TEM) and dynamic light scattering (DLS) confirmed the formation of reverse micelles in the organic layer, which encapsulates water-soluble reactants to enhance mass transfer. Through pulsed square-wave potentials, this combined strategy increased the FE by 2.4 times for the formation of chlorobenzene. The applicability of the proposed strategy toward various aryl chlorides has been justified.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"141 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066069","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}
AIChE JournalPub Date : 2025-05-13DOI: 10.1002/aic.18903
Lixia Li, Zhechao Huang, Menghao Jiang, Jinxing Long
{"title":"Selective hydrodeoxygenation of lignin to 4-ethylcyclohexanol catalyzed by Cu–Ni/MgCrOx spinel","authors":"Lixia Li, Zhechao Huang, Menghao Jiang, Jinxing Long","doi":"10.1002/aic.18903","DOIUrl":"https://doi.org/10.1002/aic.18903","url":null,"abstract":"A novel approach is proposed for producing 4-ethylcyclohexanol, a versatile petrochemical in the polymer industry, from the renewable lignin in the presence of Cu–Ni/MgCrO<sub><i>x</i></sub> spinel catalysts. Under the synergistic effect between the Ni<sup>0</sup>, Cu,<sup>+</sup> and the balanced acidic and basic properties of MgO and MgCr<sub>2</sub>O<sub>4</sub>, an exceptional yield of monomer (30.1 wt%) with 59.5% selectivity of 4-ethylcyclohexanol (yield of 17.9 wt%) was achieved when the depolymerization of bamboo lignin was performed with Cu<sub>6</sub>Ni<sub>20</sub>/MgCr<sub>0.5</sub>O<sub><i>x</i></sub> (Cr:Mg = 0.5). Catalyst characterization illustrated that the formation of MgCr<sub>2</sub>O<sub>4</sub> spinel, which restrained the generation of NiMgO<sub>2</sub> solid solution and increased the concentration of Ni<sup>0</sup> species, along with the surface electron effect between Ni<sup>0</sup> and Cu<sup>+</sup>, contributes to this superior hydrodeoxygenation performance of lignin. Mechanistic investigation further demonstrated that the conversion of lignin to 4-ethylcyclohexanol involves a tandem process of C<sub><i>β</i></sub>–O bonds cleavage, demethoxylation, and saturated hydrogenation. Therefore, this work provides new insights on lignin utilization.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"13 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940245","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}
AIChE JournalPub Date : 2025-05-13DOI: 10.1002/aic.18884
Jiali Chen, Feixue Han, Hui Xing, Xuejing Yang, Yi-Fan Han
{"title":"Kinetic and mechanism study of removing strontium ions from aqueous solution by graphene oxide/hydroxyapatite composites","authors":"Jiali Chen, Feixue Han, Hui Xing, Xuejing Yang, Yi-Fan Han","doi":"10.1002/aic.18884","DOIUrl":"https://doi.org/10.1002/aic.18884","url":null,"abstract":"Strontium (Sr) is a primary radioactive substance that should be prioritized for removal from nuclear wastewater and hospital radioactive water. An efficient graphene oxide/hydroxyapatite adsorbent (GO/HAp) was investigated for the rapid adsorption of Sr<sup>2+</sup>. Herein, a kinetic and mechanism study of this system was implemented, and the morphology and structure of as-prepared composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman, Fourier transforming infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The adsorption kinetics and equilibrium data followed the pseudo-second-order kinetic model and Freundlich isotherm model. Sr<sup>2+</sup> adsorption was further analyzed by adjusting the HAp ratio, adsorbent dosage, initial Sr<sup>2+</sup> concentration, solution pH, Ca source, and coexisting ions. The removal efficiency and adsorption capacity were up to 100%, about 109.39 mg/g. The immobilization of Sr<sup>2+</sup> was attributed to synergizing the adsorption characteristics of GO and HAp. Due to the remarkable adsorption performance, GO/HAp composites show great potential for practical applications in the treatment of nuclide-containing wastewater.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"20 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940395","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}
AIChE JournalPub Date : 2025-05-13DOI: 10.1002/aic.18896
Xiuzhen Ye, Wentao Tang
{"title":"Process Resilience under Optimal Data Injection Attacks","authors":"Xiuzhen Ye, Wentao Tang","doi":"10.1002/aic.18896","DOIUrl":"https://doi.org/10.1002/aic.18896","url":null,"abstract":"In this article, we study the resilience of process systems in an <i>information-theoretic framework</i>, from the perspective of an attacker capable of optimally constructing data injection attacks. The attack aims to distract the stationary distributions of process variables and stay stealthy, simultaneously. The problem is formulated as designing a multivariate Gaussian distribution to maximize the Kullback-Leibler divergence between the stationary distributions of states and state estimates under attacks and without attacks, while minimizing that between the distributions of sensor measurements. When the attacker has limited access to sensors, sparse attacks are proposed by incorporating a sparsity constraint. We conduct theoretical analysis on the convexity of the attack construction problem and present a greedy algorithm, which enables systematic assessment of measurement vulnerability, thereby offering insights into the inherent resilience of process systems. We numerically evaluate the performance of proposed constructions on a two-reactor process.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"8 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143945824","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}
AIChE JournalPub Date : 2025-05-13DOI: 10.1002/aic.18897
Kai Zhang, Hao-Lin Cheng, Yang Wang, Yang Liu, Zhi-Wei Xing, Peng Tan, Yao Nian, You Han, Lin-Bing Sun
{"title":"Converting metal–organic polyhedra to Pd single atoms on graphene for efficient selective semi-hydrogenation of alkynes","authors":"Kai Zhang, Hao-Lin Cheng, Yang Wang, Yang Liu, Zhi-Wei Xing, Peng Tan, Yao Nian, You Han, Lin-Bing Sun","doi":"10.1002/aic.18897","DOIUrl":"https://doi.org/10.1002/aic.18897","url":null,"abstract":"Selective hydrogenation of alkynes to alkenes is pivotal in the chemical industry. Pd-containing materials have been proven to be effective catalysts, while balancing the activity-selectivity trade-off remains a significant challenge. Here we report the fabrication of Pd single atoms from the conversion of metal–organic polyhedra (MOPs) for the first time. The MOP (M<sub>6</sub>L<sub>4</sub>), constructed from Pd salt and N-containing ligand, can interact with the graphene support via π-electron coupling, leading to well dispersion of MOP molecules. In subsequent thermal treatment, Pd is anchored by N-doped graphene formed in situ, producing single Pd atoms (denoted as Pd<sub>1</sub>/G). The obtained Pd<sub>1</sub>/G catalyst exhibits excellent activity (100% conversion) and styrene selectivity (94%) in the semi-hydrogenation of phenylacetylene under mild conditions (298 K, 1 bar H<sub>2</sub>). Such performance is much superior to the counterpart catalyst Pd/G with Pd nanoparticles and the commercial Lindlar catalyst and is among the best of the reported catalysts for phenylacetylene semi-hydrogenation.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"67 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940246","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}
AIChE JournalPub Date : 2025-05-12DOI: 10.1002/aic.18885
Jia Xiong, Qiang Sun, Hongxia Gao, Zhiwu Liang
{"title":"Advancing efficient green CO2 capture with hydrothermally recyclable Zr(HPO4)2 catalysts: Experimental and DFT insights","authors":"Jia Xiong, Qiang Sun, Hongxia Gao, Zhiwu Liang","doi":"10.1002/aic.18885","DOIUrl":"https://doi.org/10.1002/aic.18885","url":null,"abstract":"Catalytic amine–based solution regeneration has attracted considerable attention due to its potential to reduce energy consumption in carbon dioxide (CO<sub>2</sub>) separation. However, the limited catalytic activity and cycling stability of catalysts under high–temperature alkaline conditions hinder their industrial application. Herein, zirconium hydrogenphosphate (ZrHP) catalysts, featuring abundant acidic sites, were first utilized for amine solution regeneration. By leveraging its proton donation and acceptance mechanism, efficient monoethanolamine solution regeneration was achieved. The ZrHP–4 catalyst demonstrated a 526% increase in the instantaneous CO<sub>2</sub> desorption rate compared to the non–catalytic test, reducing the relative heat duty by 48%. Moreover, ZrHP–4 exhibited remarkable stability over 10 cycles without requiring regeneration. Density functional theory calculations revealed that ZrHP promotes CO<sub>2</sub> desorption by elongating the C—N bond of carbamate and lowering the proton transfer energy barrier. Therefore, this study offers novel insights into the design and mechanistic understanding of efficient and stable catalysts for amine solution regeneration.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"124 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940247","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}