Industrial & Engineering Chemistry Research最新文献

{"title":"Permeation Network Model for the Swelling of Water-in-Oil-in-Water (W/O/W) Emulsions","authors":"Gesse Roure, Robert H. Davis","doi":"10.1021/acs.iecr.4c02588","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02588","url":null,"abstract":"Fast agglomeration by emulsion binders was recently developed as an alternative to froth flotation. It involves mixing an aqueous particle suspension with a saltwater-in-oil emulsion that swells due to osmosis and captures nearby hydrophobic particles. We previously developed a model by considering the binary interactions between single droplets and particles. In practical situations, however, particles collide with droplet agglomerates, resulting in osmotic flux being limited by the permeation of water across the oil layers between droplets. In this paper, we propose a simple network model for permeation-dominated swelling kinetics. It considers spherical saltwater droplets packed inside a spherical oil droplet. The agglomerate is generated and relaxed using a swelling Monte Carlo algorithm, which gives rise to a dynamic permeation network with water permeation between the neighboring droplets. For smaller droplets, the salt concentration is similar to the concentration-boundary-layer profiles from the effective-diffusion model. The agglomerate swelling displays a fast expansion behavior followed by the agglomerate radius increasing with the square root of time for longer times. Lower volume fractions and larger droplets result in slower growth and greater sensitivity to changes in the microstructure.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"30 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832676","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":"Two-Step Continuous Synthesis of Cabozantinib in a Microreactor: Mechanism and Kinetics Research of EDCI/HOBt-Mediated Amidation","authors":"Qilin Xu, Jingli Dai, Fucheng Zhu, Yongjun Zang, Guosi Li, Chaoyue Sun, Fengxia An, Dong Liu, Yidong Zhong, Maoliang Liao","doi":"10.1021/acs.iecr.4c04100","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04100","url":null,"abstract":"Cabozantinib (<b>CBT</b>) is a small-molecule pharmaceutical approved for the treatment of medullary thyroid cancer, advanced renal cell carcinoma, and hepatocellular carcinoma. The two-step amidation starting with 1,1-cyclopropanedicarboxylic acid (<b>CBT-1</b>) is a large-scale synthetic route for <b>CBT</b>, but the existing processes suffered from highly toxic reagents, low yields, and long reaction times. In this work, a two-step cascaded flow process was developed to synthesize <b>CBT</b> in a microreactor. In the first amidation step, CDI was determined as the coupling reagent to generate 1-(4-fluorophenylaminoformyl) cyclopropane carboxylic acid (<b>CBT-3</b>) with a yield of 97.5% after optimizing the operating conditions. Then, EDCI/HOBt were screened as the coupling reagents to obtain <b>CBT</b> in the second amidation step, and the possible reaction paths and intrinsic kinetics were revealed in the microreactor. The result indicated that the formation of ion pairs between <b>CBT-3</b> and EDCI was the rate-determining step in the whole reaction process. In the end, the two amidation reactions were cascaded in a microreactor, and <b>CBT</b> was synthesized with a total reaction yield of 96.1% in 35 min. The scale-up of the developed microchemical system showed that the productivity of <b>CBT</b> can achieve about 5.3 g/h. Compared with the existing processes, milder reagents/conditions were used, and the innovative approach of continuous synthesis can provide an efficient and alternative method for the production of <b>CBT</b>.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"246 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832738","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":"Experimental Investigation of Solid Formation under CO2 Liquefaction Conditions for Ship Transport at 7 and 16 Bar with Water Content up to 300 ppm","authors":"Asmira Delic, Xiaoyun Li, Stian Trædal, Knut Maråk, Thor Mejdell, Kai Hjarbo, David Berstad, Hans Georg Jacob Stang","doi":"10.1021/acs.iecr.4c03556","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03556","url":null,"abstract":"Ship-based transport of CO₂ is crucial in developing a carbon capture and storage (CCS) infrastructure. Lowering the ship transport pressure of liquid CO₂ from the conventional 14–18 to 7 bar increases the vessel-based transport capacity, leading to significant cost reductions. However, this reduction in pressure necessitates stringent water dew point control measures to prevent the formation of ice and CO₂ hydrates, which could block pipelines and equipment. The capital and energy demands of complete dehydration of CO₂ increase the CAPEX and the OPEX of the system. It is therefore important to know the limits for water content in the CO₂ stream and the consequences if this system cannot reach the dehydration specification due to operational upsets. This study experimentally investigated possible solid formation under CO₂ liquefaction for ship transport conditions at 16 and 7 bar, containing varying water concentrations. Using a CO₂ stream from a postcombustion amine-based capture plant to represent a realistic CO₂ composition, five tests were conducted at different liquefaction pressures and water contents. The experimental results were compared to the hydrate equilibrium predictions for pure CO₂. It was found that, for low-pressure CO₂ liquefaction with 200 ppm water, signs of solid formation started to occur at about 6.7 bar, which led to complete blocking of the filter over the course of approximately 1 h as the pressure was further reduced to 6.5 bar. This is clearly above the triple point pressure, so the solids that formed were most likely hydrates. For low-pressure CO₂ liquefaction with 100 ppm of water operating very close to the triple point and the hydrate formation area, there was no increase in the pressure drop across the filter. For medium-pressure CO₂ liquefaction at 16 bar, no indication of solid formation was observed with a water content of 200 and 300 ppm. These findings show the effects of exceeding the current water specification during liquefaction of low- and medium-pressure CO₂ for ship transport.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"10 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832733","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":"Viscosity of Binary Liquid Mixtures: A Comparative Analysis of Mixing Rules","authors":"Mario Ramírez-de-Santiago","doi":"10.1021/acs.iecr.4c03240","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03240","url":null,"abstract":"Modeling the viscosity of binary liquid mixtures (η_<i>m</i>) presents significant challenges due to the complex molecular interactions and the potential for nonmonotonic behavior. A total of 22 viscosity models were evaluated, with ln(η_<i>m</i>) expressed as the sum of an ideal component and a deviation term (δ), using the Arrhenius model as a reference. Based on the extensive experimental data, a classification scheme was developed to categorize η_<i>m</i> and δ into six distinct trend types, thereby aiding in the selection of the most suitable model. For each category, both η_<i>m</i> and δ were computed using all 22 models and compared to experimental results. The Ramírez de Santiago model, along with models incorporating one or more fitting parameters, demonstrated strong performance for monotonic mixtures (type I). For mixtures exhibiting nonmonotonic behavior, polynomial models, such as the Heric–Brewer, Legendre, and Redlich–Kister models, provided the best fit. The optimal polynomial degree was determined through leave-one-out cross-validation. This study offers a systematic approach for selecting the most accurate viscosity model for binary liquid mixtures.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"145 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816386","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":"Comparative Study of Polyethylene, Polypropylene, and Polyolefins Silyl Ether-Based Vitrimers","authors":"Subhaprad Ash, Rishi Sharma, Muhammad Rabnawaz","doi":"10.1021/acs.iecr.4c04006","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04006","url":null,"abstract":"Polyolefins (POs), which constitute over 50% of all plastics, predominantly end up in landfills. To date, there have been no reports on mixtures of PO vitrimers. This study reports the successful synthesis of PO vitrimers from a mixture of 27.7% high-density polyethylene (HDPE), 36.3% linear low-density polyethylene (LLDPE)/low-density polyethylene (LDPE), and 36.0% polypropylene (PP), which is similar to that of Municipal Solid Waste (MSW). This is achieved by using silyl ether-based chemistry, both with and without nitroxides. Additionally, these PO vitrimers are compared with individual vitrimers made of HDPE, LDPE, LLDPE, and PP, as well as vitrimers made from PE blends (comprising HDPE, LLDPE, and LDPE). All vitrimers were prepared via melt extrusion. Their cross-linking density, storage modulus, tensile properties, and reprocessability were assessed. For PO vitrimers, a storage modulus of 0.61 MPa was achieved, indicating a cross-linked network while also maintaining complete melt reprocessability. This study not only provides fundamental insights but also presents a sustainable pathway for recycling PEs and POs into useful materials, hence helping to minimize waste.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"91 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816392","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":"Designing Isothermal Natural Convection Dominated Electrochemical Cells: Experimental Validation","authors":"Md. Aslam Ansari, Shaswat Srivastava, Sanjeev Kumar","doi":"10.1021/acs.iecr.4c03694","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03694","url":null,"abstract":"Deposition/dissolution redox reactions in electrochemical cells, such as soluble lead redox batteries, induce strong natural convection flow in the electrolyte. The Rayleigh number range encountered in these systems where the flow field is set up due to concentration-gradient-driven density gradients is uncommon in thermal systems, by virtue of naturally large values of Schmidt number, as compared to Prandtl number. In this work, we report the first direct PIV measurements of natural convection electrolyte solutions for soluble lead redox chemistry cells and compare them with the predictions of the existing models. We directly test the assumption of 2-dimensional flow by experimenting with low aspect ratio cells of different cell widths. A comparison of the model-predicted individual electrode potentials with measurements carried out in this work shows the adequacy of the fitted parameters, which have remained unchanged after their introduction in the context of a flow-through battery. We further tested the model by comparing predictions for several new configurations with experimental measurements. The new configurations include tall cells, cells with significant electrode gaps, cells provided with extra space at the top or below the active zone between electrodes, and intermittent mixing between charge and discharge. The new configurations bring further insights into how the multiple physics interact in soluble lead redox chemistry-based cells. Our measurements of cell potential profiles validate the model predictions in all cases.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"12 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816387","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":"Investigation on the Mechanism of Efficient Removal of Phosphorus and Fluorine Impurities from Phosphogypsum by an In Situ Recrystallization Purification Method","authors":"Daping Chen, Jinbao Song, Jupei Xia, Binbin He, Qiongbo Zhou, Yidong Hou, Yunxiang Nie, Yi Mei","doi":"10.1021/acs.iecr.4c03674","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03674","url":null,"abstract":"Phosphogypsum, a solid waste produced in the wet phosphoric acid process, can lead to severe environmental pollution. Recently, the resource utilization of phosphogypsum as a raw material for cement retarders and other products has received widespread attention, but it is limited by the high cost of purifying impurities, such as phosphorus and fluorine, contained in phosphogypsum. Herein, a novel method for purifying phosphorus and fluorine in phosphogypsum by in situ recrystallization was developed and has been employed in industrial application successfully. Further, the purification process parameters and mechanism were investigated based on a series of characterizations. The experimental results indicate that the removal efficiencies of phosphorus and fluorine achieve 86.4% and 95.71% under the optimized conditions, respectively. Significantly, during the recrystallization and washing process of fresh phosphogypsum, CaSO₄·0.5H₂O dissolves and then transforms into larger rhombic CaSO₄·2H₂O particles. Meanwhile, the impurities, such as water-soluble phosphorus ([H₃PO₄, H₂PO₄^–, HPO₄^2–, and Ca(H₂PO₄)₂), eutectic phosphorus (CaHPO₄·2H₂O), and water-soluble fluorine (F^–, Na₂SiF₆, and K₂SiF₆), carried in fresh phosphogypsum are transferred from the solid phase to the liquid phase, thereby achieving purification of phosphogypsum. This research offers robust theoretical backing and practical guidance for the effective purification of phosphogypsum.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"19 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816388","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":"Revealing the Role of Ammonia in the Rapid Crystallization Kinetics for Ni-Rich Hydroxide Precursors via Microreactors","authors":"Manqi Tang, Lang Qiu, Yuting Deng, Mengke Zhang, Fuqiren Guo, Qi Pang, Benhe Zhong, Yang Song, Xiaodong Guo","doi":"10.1021/acs.iecr.4c03700","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03700","url":null,"abstract":"The morphology and microstructure of precursors are the key to the preparation of high-quality NCM cathodes due to their inheritance relationship. However, a large amount of sulfate exists in the precursors, to the detriment of the electrochemical performance of the Ni-rich cathode materials. Herein, an effective method for sulfate reduction was proposed for the synthesis of Ni_0.90Co_0.05Mn_0.05(OH)₂ precursor by adding 0.24 M ammonia in the microreactor. The less sulfate in the Ni(OH)₂ with ammonia system is attributed to the higher formation energy of sulfate adsorption (<i>E</i>_{Ni(OH)₂-am-SO₄^2–} = 7.483 eV vs <i>E</i>_{Ni(OH)₂-SO₄^2–} = 3.451 eV). The results demonstrated that ammonia can promote the growth of primary particles (81.5 nm) and reduce the content of impurity sulfate from 0.80 to 0.28% in the precursors. Moreover, the prepared cathode materials exhibit a high specific capacity of 190.4 mAh g^–1 at 1C and superior Li⁺ diffusion coefficients. This study sheds light on the role of ammonia in rapid coprecipitation and provides guidance for the rapid synthesis process of Ni-rich cathodes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"22 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816396","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":"Isoamylene Dimerization over Mesoporous Y Zeolites","authors":"Yuehua Xiao, Chengtao Wang, Jiale Xiao, Hangjie Li, Zhengxing Cui, Yeqing Wang, Liang Wang, Feng-Shou Xiao","doi":"10.1021/acs.iecr.4c03390","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03390","url":null,"abstract":"Oligomerization of alkenes is a promising way for production of high-quality and eco-friendly liquid fuels, where zeolite catalysts are critical. In the zeolite catalysts, mass transfer and accessibility in the reaction are normally influenced by intrinsic micropores of zeolites, in particular, bulky or branched molecules are employed. Here, we report isoamylene (2-methyl-2-butene) dimerization over mesoporous HY zeolites obtained by facile NaOH treatments. These mesoporous HY zeolites exhibited high activity and good stability for the isoamylene dimerization compared with untreated HY zeolite. Powder XRD patterns, N₂ physisorption, SEM, TEM, NMR, FTIR, and NH₃-TPD techniques were used to characterize the porosity and acidity of the zeolites. These results showed that mass transfer and accessibility to the acid sites of the guest molecules are the key factors for the improvement of catalytic performances.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"5 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816472","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":"DFT Studies on the Influence of the Substituted Central Atom on Molybdenum-Based Heteropolyanions Used for the Catalytic Oxidation of Methacrolein to Methacrylic Acid","authors":"Yuan Tian, Hanwen Yan, Lili Wang, Junfeng Teng, Shuguang Xiang, Guoliang Zhang, Chunshan Li, Jie Li","doi":"10.1021/acs.iecr.4c03442","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03442","url":null,"abstract":"Heteropolyacids have been used as efficient and sustainable catalysts for the selective oxidation of methacrolein (MAL) to methacrylic acid (MAA) in recent years due to their adjustable structure. Herein, the influence of the substituted central atom (X = Al, Ga, Si, Ge, As, and S) on the structural and electronic properties of primary molybdenum-based heteropolyanions was studied. The density functional theory results indicated that the bridge oxygen of the heteropolyanion was more prone to breakage than the terminal oxygen. The interaction between MAL and catalytic sites of the molybdenum-based heteropolyanion having different central atoms and the corresponding adsorption energies were calculated. The reaction mechanism of MAL oxidation catalyzed by the heteropolyanion was systematically studied, which included the activation of the carbonyl group, hydrogen transfer, and generation of ester-based intermediates, formation of a carboxyl structure, and oxygen activation. The first step of carbonyl group activation is confirmed as the rate-determining step of this reaction. As a result, a linear relationship was discovered between the activation barrier of the rate-determining step and the lowest unoccupied molecular orbital (LUMO) of the heteropolyanion as the LUMO energy reflected the redox potential, which indicated that an increase in the LUMO energy would lead to poor catalytic performance. In addition, the activation energy of the rate-determining step would decrease in positive proportion to the ratio of the negative charge of the heteropolyanion to the electronegativity of the central atom. This correlation result indicated that the reactivity of the heteropolyanion could be predicted by calculating the negative charge and electronegativity. These findings would provide theoretical insights into the heteropolyanion at the molecular level and assist in the modification of the heteropolyacid structure to improve the catalytic performance.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"40 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809894","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}