Pub Date : 2025-04-09DOI: 10.1021/acs.iecr.5c00109
Yun Wu, Hang Chen, Ren Wang, Xingfu Song
The sylvite flotation production in western China still faces the issue of deteriorating efficiency in winter due to the low temperature. Based on the understanding of the molecular mechanism, an ether amine reagent was proposed for replacing the traditional composition of octadecylamine and 2-oil. The introduction of ether groups was determined to be effective for low temperature operation by decreasing the freezing point. The hydrogen bonds between ether groups and water molecules improved the foaming performance, which was verified by the froth experiments. Further molecular dynamics investigation showed that the ether diamine with a short carbon chain was more efficient for KCl separation, since it had two active groups and stronger penetration into the water for capturing the KCl particles. At a concentration as low as 2.5 × 10–4 mol/L, the reagent achieved a KCl recovery of 93.66% at 0 °C, with a KCl grade of 80.48% in the flotation product.
{"title":"A Novel Ether Amine Reagent for the Low-Temperature Flotation Separation of KCl","authors":"Yun Wu, Hang Chen, Ren Wang, Xingfu Song","doi":"10.1021/acs.iecr.5c00109","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00109","url":null,"abstract":"The sylvite flotation production in western China still faces the issue of deteriorating efficiency in winter due to the low temperature. Based on the understanding of the molecular mechanism, an ether amine reagent was proposed for replacing the traditional composition of octadecylamine and 2-oil. The introduction of ether groups was determined to be effective for low temperature operation by decreasing the freezing point. The hydrogen bonds between ether groups and water molecules improved the foaming performance, which was verified by the froth experiments. Further molecular dynamics investigation showed that the ether diamine with a short carbon chain was more efficient for KCl separation, since it had two active groups and stronger penetration into the water for capturing the KCl particles. At a concentration as low as 2.5 × 10<sup>–4</sup> mol/L, the reagent achieved a KCl recovery of 93.66% at 0 °C, with a KCl grade of 80.48% in the flotation product.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"7 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806402","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-09DOI: 10.1021/acs.iecr.5c00324
Gisele Azimi, Maziar E. Sauber, Sicheng Li
This study investigates the technoeconomic feasibility of utilizing supercritical fluid extraction (SCFE) with supercritical CO2 and a tributyl phosphate–nitric acid (TBP-HNO3) adduct for recovering rare earth elements (REEs) from the complex zircon-rich mineral concentrate. A detailed technoeconomic analysis (TEA) framework is employed, integrating mass and energy balance calculations, economic modeling, scenario evaluation, and sensitivity analysis. The research aims to establish the economic viability and scalability of SCFE technology as a sustainable alternative to conventional extraction methods. The study focused on an industrial-scale facility in Ontario, Canada, equipped with a 4000 L SCFE reactors. Key findings included first-year operational expenditures approaching 3 million USD and total capital expenditures of 13.7 million to 14.6 million USD. Revenue from the extracted REEs varied, with the highest returns associated with high-value elements such as terbium and dysprosium. Sensitivity analysis highlights that the profitability of the process is most sensitive to REE prices, particularly for Nd2O3, Dy2O3, and Tb4O7, followed by reagent costs and utility expenses. Payback periods ranged from 6.9 years in the optimal scenario to 12.8 years in less favorable configurations. This study demonstrates the potential of SCFE as a viable technology for REE recovery, emphasizing the importance of feedstock optimization, cost-effective reagent usage, and scalability.
{"title":"Technoeconomic Analysis of the Supercritical Fluid Extraction Process for the Extraction of Rare Earth Elements from Ores","authors":"Gisele Azimi, Maziar E. Sauber, Sicheng Li","doi":"10.1021/acs.iecr.5c00324","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00324","url":null,"abstract":"This study investigates the technoeconomic feasibility of utilizing supercritical fluid extraction (SCFE) with supercritical CO<sub>2</sub> and a tributyl phosphate–nitric acid (TBP-HNO<sub>3</sub>) adduct for recovering rare earth elements (REEs) from the complex zircon-rich mineral concentrate. A detailed technoeconomic analysis (TEA) framework is employed, integrating mass and energy balance calculations, economic modeling, scenario evaluation, and sensitivity analysis. The research aims to establish the economic viability and scalability of SCFE technology as a sustainable alternative to conventional extraction methods. The study focused on an industrial-scale facility in Ontario, Canada, equipped with a 4000 L SCFE reactors. Key findings included first-year operational expenditures approaching 3 million USD and total capital expenditures of 13.7 million to 14.6 million USD. Revenue from the extracted REEs varied, with the highest returns associated with high-value elements such as terbium and dysprosium. Sensitivity analysis highlights that the profitability of the process is most sensitive to REE prices, particularly for Nd<sub>2</sub>O<sub>3</sub>, Dy<sub>2</sub>O<sub>3</sub>, and Tb<sub>4</sub>O<sub>7</sub>, followed by reagent costs and utility expenses. Payback periods ranged from 6.9 years in the optimal scenario to 12.8 years in less favorable configurations. This study demonstrates the potential of SCFE as a viable technology for REE recovery, emphasizing the importance of feedstock optimization, cost-effective reagent usage, and scalability.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"37 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806404","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}
Ethylene is mostly produced by the naphtha steam cracking (NSC) process, which has a higher cracking temperature, higher energy consumption, and strict requirements for raw materials. The targeted catalytic cracking to olefins (TCO) presents a new reaction pathway for ethylene production. The combined process of TCO and bioethanol dehydration reaction reduces methane yield by 16.51% and improves the utilization of carbon/hydrogen atoms by 23.67%/25.08% with the ethylene yield of 44.56%. Also, the reaction temperature of TCO/bioethanol dehydration reaction (670–740 °C/400 °C) is lower than that of NSC (750–900 °C). Especially, the AHZ-C catalyst with weak acid sites and increased distance between the acid sites blocked the protonation process of ethylene and improved the ethylene selectivity in the bioethanol dehydration reaction. The combination of TCO and ethanol dehydration reaction may be one of the effective technologies for producing ethylene.
{"title":"Increased Ethylene Production by the Combination Technology of Targeted Catalytic Cracking to Olefins and Dehydration of Bioethanol Reaction","authors":"Ruilin Wang, Wenjie Yang, Youhao Xu, Xingtian Shu, Yongrui Wang, Yibin Luo, Enhui Xing, Ying Ouyang, Lina Zhou, Weixin Huang, Yunxing Bai","doi":"10.1021/acs.iecr.4c04659","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04659","url":null,"abstract":"Ethylene is mostly produced by the naphtha steam cracking (NSC) process, which has a higher cracking temperature, higher energy consumption, and strict requirements for raw materials. The targeted catalytic cracking to olefins (TCO) presents a new reaction pathway for ethylene production. The combined process of TCO and bioethanol dehydration reaction reduces methane yield by 16.51% and improves the utilization of carbon/hydrogen atoms by 23.67%/25.08% with the ethylene yield of 44.56%. Also, the reaction temperature of TCO/bioethanol dehydration reaction (670–740 °C/400 °C) is lower than that of NSC (750–900 °C). Especially, the AHZ-C catalyst with weak acid sites and increased distance between the acid sites blocked the protonation process of ethylene and improved the ethylene selectivity in the bioethanol dehydration reaction. The combination of TCO and ethanol dehydration reaction may be one of the effective technologies for producing ethylene.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"25 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-09DOI: 10.1021/acs.iecr.5c00689
Nan Hu, Jinbiao Zhang, Shengfang Yuan, Yatao Zhang, Qunsheng Li
Extractive distillation in separating multiazeotropic systems is generally considered a challenge due to the difficulty in finding entrainers that can simultaneously alter multiple azeotropic points. This study proposes a method that leverages intermolecular forces between nonkey components (autoextractive components) and key components. This allows for the separation of an n component mixture into n–1 components or fewer, along with at least one pure component, without the need for additional entrainers. The operating condition for the autoextractive effect is explicitly defined as when the ratio of the autoextractive component to its azeotropic component exceeds the ratio of its azeotropic composition, enabling the separation of the third component without the need for additional autoextractive components. Using the example of the ternary azeotropic system ethyl acetate (A)–ethanol (B)–toluene (C), this study details how to achieve the separation of azeotropic mixtures through the autoextractive effect and entrainer (E). Two novel separation sequences, C/B/A/E and C/A/B/E, have been developed based on the autoextractive effect. These sequences are more readily accepted when the ratio of the autoextractive component to its azeotropic component exceeds its azeotropic composition in the feed.
{"title":"Design of Extractive Distillation Considering the Effect of Feed Components on the Separation of Multiazeotropic Systems","authors":"Nan Hu, Jinbiao Zhang, Shengfang Yuan, Yatao Zhang, Qunsheng Li","doi":"10.1021/acs.iecr.5c00689","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00689","url":null,"abstract":"Extractive distillation in separating multiazeotropic systems is generally considered a challenge due to the difficulty in finding entrainers that can simultaneously alter multiple azeotropic points. This study proposes a method that leverages intermolecular forces between nonkey components (autoextractive components) and key components. This allows for the separation of an <i>n</i> component mixture into <i>n</i>–1 components or fewer, along with at least one pure component, without the need for additional entrainers. The operating condition for the autoextractive effect is explicitly defined as when the ratio of the autoextractive component to its azeotropic component exceeds the ratio of its azeotropic composition, enabling the separation of the third component without the need for additional autoextractive components. Using the example of the ternary azeotropic system ethyl acetate (A)–ethanol (B)–toluene (C), this study details how to achieve the separation of azeotropic mixtures through the autoextractive effect and entrainer (E). Two novel separation sequences, C/B/A/E and C/A/B/E, have been developed based on the autoextractive effect. These sequences are more readily accepted when the ratio of the autoextractive component to its azeotropic component exceeds its azeotropic composition in the feed.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"31 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806406","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-09DOI: 10.1021/acs.iecr.4c04765
Manjusha C. Padole, Abhijeet Raj
Cement industries contribute significantly to greenhouse gas emissions, including nitrogen oxides (NOx) that pose serious risks to respiratory health and the environment and require effective reduction strategies. This study explores the potential of hydrogen cyanide (HCN) released from spent pot lining (SPL) during its cocombustion with coal in a cement kiln as an effective reducing agent to mitigate NO2 emissions from the plant. A detailed reaction mechanism for the interactions of HCN, HNC, and CN with NO2 is developed to form several possible products, including N2. The study employs a CBS-QB3 composite method and density functional theory (uB3LYP/6–311++G(d,p)) as tools for quantum chemical calculations to analyze the elementary reactions, optimize the structures of intermediate species and transition states, and determine their reaction energetics. The reaction kinetics of all the elementary steps are determined using transition state theory and RRKM methods to determine the preferred reactions among the competing channels. Through reactor simulations using the developed reaction mechanism, the possibility of NO2 reduction by HCN and the most preferred pathway for it are reported. It is found that HCN is highly effective in reducing NO and NO2 to N2 under cement kiln conditions. The results suggest that the utilization of SPL in cement plants together with coal can reduce both coal requirements and NOx emission from the plant.
{"title":"NO2 Reduction by HCN, HNC, and CN during Cofiring of Spent Pot Lining in Cement Plant: A DFT and Reaction Kinetics Study","authors":"Manjusha C. Padole, Abhijeet Raj","doi":"10.1021/acs.iecr.4c04765","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04765","url":null,"abstract":"Cement industries contribute significantly to greenhouse gas emissions, including nitrogen oxides (NO<sub><i>x</i></sub>) that pose serious risks to respiratory health and the environment and require effective reduction strategies. This study explores the potential of hydrogen cyanide (HCN) released from spent pot lining (SPL) during its cocombustion with coal in a cement kiln as an effective reducing agent to mitigate NO<sub>2</sub> emissions from the plant. A detailed reaction mechanism for the interactions of HCN, HNC, and CN with NO<sub>2</sub> is developed to form several possible products, including N<sub>2</sub>. The study employs a CBS-QB3 composite method and density functional theory (uB3LYP/6–311++G(d,p)) as tools for quantum chemical calculations to analyze the elementary reactions, optimize the structures of intermediate species and transition states, and determine their reaction energetics. The reaction kinetics of all the elementary steps are determined using transition state theory and RRKM methods to determine the preferred reactions among the competing channels. Through reactor simulations using the developed reaction mechanism, the possibility of NO<sub>2</sub> reduction by HCN and the most preferred pathway for it are reported. It is found that HCN is highly effective in reducing NO and NO<sub>2</sub> to N<sub>2</sub> under cement kiln conditions. The results suggest that the utilization of SPL in cement plants together with coal can reduce both coal requirements and NO<sub><i>x</i></sub> emission from the plant.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"58 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806401","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}
Mo doping optimizes the electronic structure of ReS2. MoxRe(1–x)S2/MoS2 alloy heterojunction exhibits more favorable application prospects in photodetection due to its higher electrical conductivity than ReS2/MoS2 heterojunction. However, alloy heterojunctions are difficult to prepare controllably using conventional vapor-phase chemical vapor deposition (CVD), and the heterojunction growth mechanism remains unclear. Here, a vapor–liquid–solid temperature-gradient process is proposed to grow alloy heterojunctions within predeposited molten Mo precursor droplets. The sulfuration reaction between Re diffusing into the droplet and Mo atoms facilitates the formation of alloy structures. The growth temperatures TRe and TMo in the temperature-gradient significantly affect the growth patterns and morphology evolution of the heterojunction. The MoS2 morphology in vertical alloy heterojunctions becomes triangular as the growth temperature increases. The dimension of the top MoxRe(1–x)S2 alloy is positively correlated with the Re diffusion concentration. Moreover, lateral alloy heterojunctions and single alloys are formed at lower and higher growth temperature differences between TRe and TMo, respectively. These results provide a controllable strategy for the synthesis of isotropic/anisotropic van der Waals TMDC heterojunctions.
{"title":"Investigation of 1T′ MoxRe(1–x)S2/2H MoS2 Heterojunction Morphology Evolution through Vapor–Liquid–Solid Growth Mechanism by Temperature-Gradient CVD","authors":"Tong Cheng, Qi-Bo Wang, Qin-Qin Xu, Zhen-Hua Han, Jian-Zhong Yin","doi":"10.1021/acs.iecr.5c00302","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00302","url":null,"abstract":"Mo doping optimizes the electronic structure of ReS<sub>2</sub>. Mo<sub><i>x</i></sub>Re<sub>(1–<i>x</i>)</sub>S<sub>2</sub>/MoS<sub>2</sub> alloy heterojunction exhibits more favorable application prospects in photodetection due to its higher electrical conductivity than ReS<sub>2</sub>/MoS<sub>2</sub> heterojunction. However, alloy heterojunctions are difficult to prepare controllably using conventional vapor-phase chemical vapor deposition (CVD), and the heterojunction growth mechanism remains unclear. Here, a vapor–liquid–solid temperature-gradient process is proposed to grow alloy heterojunctions within predeposited molten Mo precursor droplets. The sulfuration reaction between Re diffusing into the droplet and Mo atoms facilitates the formation of alloy structures. The growth temperatures <i>T</i><sub>Re</sub> and <i>T</i><sub>Mo</sub> in the temperature-gradient significantly affect the growth patterns and morphology evolution of the heterojunction. The MoS<sub>2</sub> morphology in vertical alloy heterojunctions becomes triangular as the growth temperature increases. The dimension of the top Mo<sub><i>x</i></sub>Re<sub>(1–<i>x</i>)</sub>S<sub>2</sub> alloy is positively correlated with the Re diffusion concentration. Moreover, lateral alloy heterojunctions and single alloys are formed at lower and higher growth temperature differences between <i>T</i><sub>Re</sub> and <i>T</i><sub>Mo</sub>, respectively. These results provide a controllable strategy for the synthesis of isotropic/anisotropic van der Waals TMDC heterojunctions.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798515","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-08DOI: 10.1021/acs.iecr.5c00489
Xinyi Liu, Zhaoyuan He, Ziyi Huang, Chunrong Tian, Xiaowen Zhao, Lin Ye
In order to protect electronic components from high-temperature impact and also dissipate accumulated heat during use, thermoplastic polyurethane (TPU)-based unidirectional thermal conductive foam with a gradient structure was assembled layer by layer and subsequent scCO2 foaming. Polydopamine (PDA) coating layer was first introduced to the surfaces of boron nitride (BN) with carbon nanotubes (CNTs) as bridging (PBC) through π–π stacking and hydrogen bonding interaction, leading to a high intercalation ratio of TPU molecules between BN layers. The in-plane thermal conductivity (TC) of TPU/60wt%PBC sample reached as high as 4.68 W·m–1·K–1 due to horizontal alignment of uniformly dispersed BN sheets, and excellent flexibility and foldability were also exhibited. Besides, PBC particles were selectively distributed in hard domain (HD), while with increasing TPU hardness and HD region ratio, the effective concentration of PBC in HD decreased, resulting in a drop of TC. Moreover, with increasing PBC content in each layer of TPU/PBC assembled foam, due to decreasing cell size, increasing apparent density, and formation of interconnected 3D thermal conductive network, the in-plane TC of each layer increased gradually and even reached 2.39 W·m–1·K–1 for TPU/40wt%PBC foam layer, resulting in a gradient distribution of cell structure and thermal conductivity. The assembled foam exhibited a tightly integrated structure with blurred interfaces between each layer, and unidirectional thermal conductivity was confirmed by infrared thermography.
{"title":"Construction of Thermoplastic Polyurethane-Based Unidirectional Thermal Conductive Foam with a Gradient Structure","authors":"Xinyi Liu, Zhaoyuan He, Ziyi Huang, Chunrong Tian, Xiaowen Zhao, Lin Ye","doi":"10.1021/acs.iecr.5c00489","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00489","url":null,"abstract":"In order to protect electronic components from high-temperature impact and also dissipate accumulated heat during use, thermoplastic polyurethane (TPU)-based unidirectional thermal conductive foam with a gradient structure was assembled layer by layer and subsequent scCO<sub>2</sub> foaming. Polydopamine (PDA) coating layer was first introduced to the surfaces of boron nitride (BN) with carbon nanotubes (CNTs) as bridging (PBC) through π–π stacking and hydrogen bonding interaction, leading to a high intercalation ratio of TPU molecules between BN layers. The in-plane thermal conductivity (TC) of TPU/60wt%PBC sample reached as high as 4.68 W·m<sup>–1</sup>·K<sup>–1</sup> due to horizontal alignment of uniformly dispersed BN sheets, and excellent flexibility and foldability were also exhibited. Besides, PBC particles were selectively distributed in hard domain (HD), while with increasing TPU hardness and HD region ratio, the effective concentration of PBC in HD decreased, resulting in a drop of TC. Moreover, with increasing PBC content in each layer of TPU/PBC assembled foam, due to decreasing cell size, increasing apparent density, and formation of interconnected 3D thermal conductive network, the in-plane TC of each layer increased gradually and even reached 2.39 W·m<sup>–1</sup>·K<sup>–1</sup> for TPU/40wt%PBC foam layer, resulting in a gradient distribution of cell structure and thermal conductivity. The assembled foam exhibited a tightly integrated structure with blurred interfaces between each layer, and unidirectional thermal conductivity was confirmed by infrared thermography.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"31 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-08DOI: 10.1021/acs.iecr.5c00624
Chengyin Lin, Yongyuan Deng, Yuankai Lin, Jun Li, Junling Tu, Riyang Shu
Hydrodeoxygenation (HDO) represents a highly efficient refining pathway to convert lignin-derived phenolic compounds for the production of hydrocarbon fuels, and the selection of a suitable catalyst is pivotal for a high reaction efficiency. In this study, we introduce a novel highly dispersed Pt/Al2O3–TiO2 composite catalyst that is prepared via a photochemical reduction method and employ it for the HDO of lignin-derived phenolic compounds. The catalyst demonstrates a good HDO performance, achieving complete conversion of guaiacol at 260 °C with cyclohexane selectivity of 99.9%. Catalyst characterization results reveal that the Pt/Al2O3–TiO2 catalyst exhibits a high Pt metal dispersion. Besides, the composite support synergistically combines the properties of Al2O3 and TiO2 components, resulting in a high specific surface area, moderate acidity, and abundant oxygen vacancy. These factors facilitate the provision of numerous active metal sites and acid sites those are essential for the HDO reaction. Moreover, the Pt/Al2O3–TiO2 catalyst also shows a high activity on the HDO of various other phenolic compounds. When applied to the upgrading of lignin oil, the catalyst significantly increases the hydrocarbon content from 18.9% to 92.2%, concurrently reducing the oxygen content and substantially increasing the hydrogen content of the lignin oil. The calorific value is significantly enhanced, underscoring the potential of the Pt/Al2O3–TiO2 composite catalyst to upgrade lignin-derived phenolic compounds into high-quality hydrocarbon liquid fuels.
{"title":"Hydrodeoxygenation of Lignin-Derived Phenolic Compounds over Highly Dispersed Pt/Al2O3–TiO2 Composite Catalyst","authors":"Chengyin Lin, Yongyuan Deng, Yuankai Lin, Jun Li, Junling Tu, Riyang Shu","doi":"10.1021/acs.iecr.5c00624","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00624","url":null,"abstract":"Hydrodeoxygenation (HDO) represents a highly efficient refining pathway to convert lignin-derived phenolic compounds for the production of hydrocarbon fuels, and the selection of a suitable catalyst is pivotal for a high reaction efficiency. In this study, we introduce a novel highly dispersed Pt/Al<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> composite catalyst that is prepared via a photochemical reduction method and employ it for the HDO of lignin-derived phenolic compounds. The catalyst demonstrates a good HDO performance, achieving complete conversion of guaiacol at 260 °C with cyclohexane selectivity of 99.9%. Catalyst characterization results reveal that the Pt/Al<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> catalyst exhibits a high Pt metal dispersion. Besides, the composite support synergistically combines the properties of Al<sub>2</sub>O<sub>3</sub> and TiO<sub>2</sub> components, resulting in a high specific surface area, moderate acidity, and abundant oxygen vacancy. These factors facilitate the provision of numerous active metal sites and acid sites those are essential for the HDO reaction. Moreover, the Pt/Al<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> catalyst also shows a high activity on the HDO of various other phenolic compounds. When applied to the upgrading of lignin oil, the catalyst significantly increases the hydrocarbon content from 18.9% to 92.2%, concurrently reducing the oxygen content and substantially increasing the hydrogen content of the lignin oil. The calorific value is significantly enhanced, underscoring the potential of the Pt/Al<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> composite catalyst to upgrade lignin-derived phenolic compounds into high-quality hydrocarbon liquid fuels.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"56 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798518","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}
Continuous reactors serve as a core component in commercial hydrothermal liquefaction systems, enabling high-capacity biocrude production from sludge. To optimize the reactor configuration and operation conditions, HTL kinetics of sludge were coupled with computational fluid dynamics and finite element methods. The proposed model was used to explore the distributions of biocrude yield, temperature, and stress. With a total length of 0.5 m, the upward-flow serpentine reactor, 325 °C, an inner diameter of 20 mm, and an inlet velocity of 0.0009 m·s–1 provided the highest biocrude yield of 34.39 wt %. Stress concentrations at the bends were observed in the serpentine reactor. Increasing the bending diameter from 14 to 24 mm reduced the maximum equivalent stress from 136.22 to 113.86 MPa, allowing the application of inexpensive stainless steel as the reactor material. The coupled model also provides insights into optimizing the length of a pilot-scale reactor.
{"title":"Numerical Simulation of Hydrothermal Liquefaction of Sludge in Continuous Reactors: Integration of Kinetics, Fluid Dynamics, and Stress Analyses","authors":"Lili Qian, Chenzheng Ma, Wei Huang, Hao Chen, Shuang Wang, Heng Gu","doi":"10.1021/acs.iecr.4c03708","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03708","url":null,"abstract":"Continuous reactors serve as a core component in commercial hydrothermal liquefaction systems, enabling high-capacity biocrude production from sludge. To optimize the reactor configuration and operation conditions, HTL kinetics of sludge were coupled with computational fluid dynamics and finite element methods. The proposed model was used to explore the distributions of biocrude yield, temperature, and stress. With a total length of 0.5 m, the upward-flow serpentine reactor, 325 °C, an inner diameter of 20 mm, and an inlet velocity of 0.0009 m·s<sup>–1</sup> provided the highest biocrude yield of 34.39 wt %. Stress concentrations at the bends were observed in the serpentine reactor. Increasing the bending diameter from 14 to 24 mm reduced the maximum equivalent stress from 136.22 to 113.86 MPa, allowing the application of inexpensive stainless steel as the reactor material. The coupled model also provides insights into optimizing the length of a pilot-scale reactor.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"242 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798511","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}
In this study, a series of puffball carbon-supported catalysts were synthesized to facilitate the hydrodeoxygenation (HDO) of the lignin model compound vanillin (VAN) into 2-methoxy-4-methylphenol (MMP). The Co-ZIF/BC catalyst, prepared by loading ZIF-67 onto puffball carbon support, achieved a VAN conversion rate of 96.28% and a selectivity of 86.57% for MMP under reaction conditions of 240 °C and 1.5 MPa of H2 for 4 h. Based on the characterization results, it was found that the Co-ZIF/BC catalyst exhibited high crystal defects, a large specific surface area, and mesopore volume, as well as strong Lewis acid sites. Additionally, the Co–N bonds formed between Co nanoparticles and nitrogen increased the electron density on the catalyst surface. The abundant surface Co0 species enhanced hydrogen adsorption and dissociation, providing more active sites, which facilitated the activation of reactants and improved the efficiency of the catalytic reaction. The use of abundant and low-cost puffball materials in the preparation of the Co-ZIF/BC catalyst not only reduced production costs but also supported the sustainability of the catalytic process, aligning with the principles of green chemistry.
{"title":"Metal–Organic Frameworks and Biomass: Mutual Partners on Designing Environmentally Friendly Catalysts for Catalytic Conversion of Lignin-Derived Substances","authors":"Changyong Li, Mengqing Zhou, Yun Zheng, Shengchun Hu, Liangliang Zhang, Changzhou Chen, Jianchun Jiang","doi":"10.1021/acs.iecr.5c00201","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00201","url":null,"abstract":"In this study, a series of puffball carbon-supported catalysts were synthesized to facilitate the hydrodeoxygenation (HDO) of the lignin model compound vanillin (VAN) into 2-methoxy-4-methylphenol (MMP). The Co-ZIF/BC catalyst, prepared by loading ZIF-67 onto puffball carbon support, achieved a VAN conversion rate of 96.28% and a selectivity of 86.57% for MMP under reaction conditions of 240 °C and 1.5 MPa of H<sub>2</sub> for 4 h. Based on the characterization results, it was found that the Co-ZIF/BC catalyst exhibited high crystal defects, a large specific surface area, and mesopore volume, as well as strong Lewis acid sites. Additionally, the Co–N bonds formed between Co nanoparticles and nitrogen increased the electron density on the catalyst surface. The abundant surface Co<sup>0</sup> species enhanced hydrogen adsorption and dissociation, providing more active sites, which facilitated the activation of reactants and improved the efficiency of the catalytic reaction. The use of abundant and low-cost puffball materials in the preparation of the Co-ZIF/BC catalyst not only reduced production costs but also supported the sustainability of the catalytic process, aligning with the principles of green chemistry.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"65 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806407","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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