Pub Date : 2024-06-26DOI: 10.1021/acs.iecr.4c01775
Sirisha Parvathaneni, Marcelo W. Andrade
In the iron and steel-making process, direct reduced iron (DRI) is the very first step that uses CO and H2 to reduce iron ore and therefore contributes to fewer CO2 emissions than the conventional blast furnace process. The CO and H2 required for the DRI process are generated from bottom-fired reformers with reformer tubes filled with catalyst particles and transported to the shaft furnace for iron-ore reduction. Therefore, the DRI reforming process plays an essential role in DRI production by supplying reducing gases of the desired composition, flow rate, and temperature. In the present work, a 3D computational fluid dynamics model is developed to simulate the industrial-scale DRI reforming process that includes the multicomponent gas mixture flow in reactor tubes and burners, heat transfer from burner to tubes due to combustion on the burner side, and reforming reactions in catalyst-filled tubes. The pressure drop on the tube side due to the presence of the catalyst is calculated through a porous media approach. Results show the formation of a long and narrow flame on the burner side due to combustion, which led to an increase in the temperature of the tube wall and at the tube center. This enabled endothermic reforming reactions on the tube side and resulted in the consumption of CH4 and H2O and the formation of CO and H2. The model predictions of tube outlet reformed gas temperature and composition and the temperature at different axial locations at the tube wall and center are in satisfactory agreement with ArcelorMittal’s plant data.
在炼铁和炼钢工艺中，直接还原铁（DRI）是使用 CO 和 H2 还原铁矿石的第一步，因此与传统的高炉工艺相比，其二氧化碳排放量更少。DRI 工艺所需的 CO 和 H2 由底部燃烧的转化炉产生，转化炉管内装满催化剂颗粒，然后输送到竖炉进行铁矿石还原。因此，DRI 重整工艺通过提供所需成分、流速和温度的还原气体，在 DRI 生产中发挥着至关重要的作用。在本研究中，开发了一个三维计算流体动力学模型来模拟工业规模的 DRI 重整过程，其中包括反应器管道和燃烧器中的多组分混合气体流动、燃烧器侧燃烧导致的燃烧器到管道的热量传递以及充满催化剂的管道中的重整反应。通过多孔介质方法计算了由于催化剂的存在而导致的管侧压降。结果表明，燃烧在燃烧器一侧形成狭长的火焰，导致管壁和管中心温度升高。这使得管侧发生内热重整反应，消耗 CH4 和 H2O，形成 CO 和 H2。模型预测的管出口重整气体温度和成分以及管壁和管中心不同轴向位置的温度与 ArcelorMittal 工厂的数据完全一致。
{"title":"CFD Modeling of the Industrial-Scale Bottom-Fired Direct Reduced Iron Reforming Process","authors":"Sirisha Parvathaneni, Marcelo W. Andrade","doi":"10.1021/acs.iecr.4c01775","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c01775","url":null,"abstract":"In the iron and steel-making process, direct reduced iron (DRI) is the very first step that uses CO and H<sub>2</sub> to reduce iron ore and therefore contributes to fewer CO<sub>2</sub> emissions than the conventional blast furnace process. The CO and H<sub>2</sub> required for the DRI process are generated from bottom-fired reformers with reformer tubes filled with catalyst particles and transported to the shaft furnace for iron-ore reduction. Therefore, the DRI reforming process plays an essential role in DRI production by supplying reducing gases of the desired composition, flow rate, and temperature. In the present work, a 3D computational fluid dynamics model is developed to simulate the industrial-scale DRI reforming process that includes the multicomponent gas mixture flow in reactor tubes and burners, heat transfer from burner to tubes due to combustion on the burner side, and reforming reactions in catalyst-filled tubes. The pressure drop on the tube side due to the presence of the catalyst is calculated through a porous media approach. Results show the formation of a long and narrow flame on the burner side due to combustion, which led to an increase in the temperature of the tube wall and at the tube center. This enabled endothermic reforming reactions on the tube side and resulted in the consumption of CH<sub>4</sub> and H<sub>2</sub>O and the formation of CO and H<sub>2</sub>. The model predictions of tube outlet reformed gas temperature and composition and the temperature at different axial locations at the tube wall and center are in satisfactory agreement with ArcelorMittal’s plant data.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462078","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 : 2024-06-26DOI: 10.1021/acs.iecr.4c00301
Stavros-Alexandros Theofanidis, Konstantinos Stergiou, Evangelos Delikonstantis, Georgios D. Stefanidis
A thorough cost analysis based on the conceptual process design of a two-step CO2-to-methanol synthesis route is performed, comprising CO2 hydrogenation in an electrified reverse water–gas shift (RWGS) reactor, followed by a conventional methanol synthesis reactor. In the former step, both thermal and nonthermal plasma reactors are considered, i.e., direct current (DC) arc and microwave (MW) plasma, respectively, and benchmarked against the conventional thermo-catalytic counterpart. It is found that employment of any type of plasma promotes higher CO2 conversions in the RWGS step than the conventional thermo-catalytic reactors (82–90 vs 61%), thereby higher single-pass methanol yields (24–27 vs 17%). This comes at the expense of higher electricity demand, which minorly affects the process economics since green H2 utilized in RWGS and methanol synthesis is the cost driver. The economic analysis shows that the current green H2 prices (2022 scenario) render the two-step CO2-to-methanol process economically unviable, regardless of the reactor technology used, attaining approximately a 4-fold higher levelized cost of methanol (LCOM), 1875–1900 €·ton–1, compared to the state-of-the-art route, i.e., syngas production through steam methane reforming (SMR) and coal gasification, followed by WGS and methanol synthesis reactors. However, the two-step CO2-to-methanol route could be viable for a long term (2050 scenario), driven by lower costs of electricity (10 €·MW h–1) and green H2 (1.0 €·kg–1) along with the avoided emission credits. This originates from the lower greenhouse gas (GHG) emissions that the two-step CO2-to-methanol route attains compared with the state-of-the-art. In the 2050 frame, plasma technologies are anticipated to be at least 45% more profitable than thermo-catalytic reactors, while the profitability of nonthermal plasmas will significantly improve if vacuum operation is avoided, mitigating the excessive compression energy demand and subsequently decreasing the operating cost.
{"title":"On the Electrification of CO2-Based Methanol Synthesis via a Reverse Water–Gas Shift: A Comparative Techno-Economic Assessment of Thermo-Catalytic and Plasma-Assisted Routes","authors":"Stavros-Alexandros Theofanidis, Konstantinos Stergiou, Evangelos Delikonstantis, Georgios D. Stefanidis","doi":"10.1021/acs.iecr.4c00301","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c00301","url":null,"abstract":"A thorough cost analysis based on the conceptual process design of a two-step CO<sub>2</sub>-to-methanol synthesis route is performed, comprising CO<sub>2</sub> hydrogenation in an electrified reverse water–gas shift (RWGS) reactor, followed by a conventional methanol synthesis reactor. In the former step, both thermal and nonthermal plasma reactors are considered, i.e., direct current (DC) arc and microwave (MW) plasma, respectively, and benchmarked against the conventional thermo-catalytic counterpart. It is found that employment of any type of plasma promotes higher CO<sub>2</sub> conversions in the RWGS step than the conventional thermo-catalytic reactors (82–90 vs 61%), thereby higher single-pass methanol yields (24–27 vs 17%). This comes at the expense of higher electricity demand, which minorly affects the process economics since green H<sub>2</sub> utilized in RWGS and methanol synthesis is the cost driver. The economic analysis shows that the current green H<sub>2</sub> prices (2022 scenario) render the two-step CO<sub>2</sub>-to-methanol process economically unviable, regardless of the reactor technology used, attaining approximately a 4-fold higher levelized cost of methanol (LCOM), 1875–1900 €·ton<sup>–1</sup>, compared to the state-of-the-art route, i.e., syngas production through steam methane reforming (SMR) and coal gasification, followed by WGS and methanol synthesis reactors. However, the two-step CO<sub>2</sub>-to-methanol route could be viable for a long term (2050 scenario), driven by lower costs of electricity (10 €·MW h<sup>–1</sup>) and green H<sub>2</sub> (1.0 €·kg<sup>–1</sup>) along with the avoided emission credits. This originates from the lower greenhouse gas (GHG) emissions that the two-step CO<sub>2</sub>-to-methanol route attains compared with the state-of-the-art. In the 2050 frame, plasma technologies are anticipated to be at least 45% more profitable than thermo-catalytic reactors, while the profitability of nonthermal plasmas will significantly improve if vacuum operation is avoided, mitigating the excessive compression energy demand and subsequently decreasing the operating cost.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462016","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 : 2024-06-26DOI: 10.1021/acs.iecr.4c00685
Mohammad Al-Harahsheh, Aiman Al-Rawajfeh, Raghad Al-Khatib
The purpose of carbon capture and sequestration (CCS) is to reduce CO2 emissions from the use of fossil fuel. In this article, the effect of seeding on the Dead Sea water (DSW) CO2 storage capacity was investigated. Three types of seed particles were used: rocks from the bottom of the DS, amorphous silica, and quartz sand; the influence of each type on the storage capacity of DSW toward CO2 was studied. When seeds were added to DSW during or after CO2 injection, different solid precipitates were formed depending on the seed type; with rock seeds collected from the DS basin, calcite and dolomite precipitates were formed, while aragonite, magnesite, and monohydrocalcite were precipitated when amorphous silica was used as seed. Quartz sand was used as received and also after acid washing; aragonite, magnesite, and monohydrocalcite were precipitated on the as-received sand, while no precipitate was observed on the acid-washed quartz sand. It was concluded that carbonate precipitation followed the crystal structure of the seed; the main condition for the overgrowth of one crystalline phase over another was crystal lattice compatibility. The crystal structure of the purified quartz was not found to be a good seed to the overgrowth of calcium or magnesium carbonate.
{"title":"Effect of Seeding on CO2 Storage in Brines: Case Study on Dead Sea Water","authors":"Mohammad Al-Harahsheh, Aiman Al-Rawajfeh, Raghad Al-Khatib","doi":"10.1021/acs.iecr.4c00685","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c00685","url":null,"abstract":"The purpose of carbon capture and sequestration (CCS) is to reduce CO<sub>2</sub> emissions from the use of fossil fuel. In this article, the effect of seeding on the Dead Sea water (DSW) CO<sub>2</sub> storage capacity was investigated. Three types of seed particles were used: rocks from the bottom of the DS, amorphous silica, and quartz sand; the influence of each type on the storage capacity of DSW toward CO<sub>2</sub> was studied. When seeds were added to DSW during or after CO<sub>2</sub> injection, different solid precipitates were formed depending on the seed type; with rock seeds collected from the DS basin, calcite and dolomite precipitates were formed, while aragonite, magnesite, and monohydrocalcite were precipitated when amorphous silica was used as seed. Quartz sand was used as received and also after acid washing; aragonite, magnesite, and monohydrocalcite were precipitated on the as-received sand, while no precipitate was observed on the acid-washed quartz sand. It was concluded that carbonate precipitation followed the crystal structure of the seed; the main condition for the overgrowth of one crystalline phase over another was crystal lattice compatibility. The crystal structure of the purified quartz was not found to be a good seed to the overgrowth of calcium or magnesium carbonate.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462128","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 : 2024-06-26DOI: 10.1021/acs.iecr.4c01937
Konstantin A. Tereshchenko, Daria A. Shiyan, Andrey A. Osipov, Vera P. Bondarenko, Nikolai V. Ulitin, Elina M. Sabitova, Anton V. Bekker, Yana L. Lyulinskaya, Nikolay A. Novikov, Natalia M. Nurullina, Svetlana N. Tuntseva, Tatyana L. Puchkova, Yaroslav O. Mezhuev, Kharlampii E. Kharlampidi, Sergey V. Kolesov
A kinetic model of the curing of methyl methacrylate adhesive (including nanocomposite methyl methacrylate adhesive) in the presence of the initiating systems “aryl peroxide + zirconocene dichloride” and “aryl hydroperoxide + zirconocene dichloride” is made. Computational experiments have been carried out which demonstrate the relationship of the curing rate with the curing temperature in the range of 323–343 K and with the ratio of the initial concentration of zirconocene dichloride to the initial concentration of the initiator [Mc]0/[I]0 for the following initiators: benzoyl peroxide (PB), ethylbenzene hydroperoxide (HPEB), and ethylbenzene hydroperoxide adduct with cadmium 2-ethyl hexanoate [HPEB·Cd(EH)2]. It is shown that in order to increase the curing rate of the adhesive, curing should be carried out at a higher temperature (343 K) and at a higher value of the ratio [Mc]0/[I]0 = 10 in the presence of the most rapidly decomposing initiator HPEB·Cd(EH)2. To increase the weight-average molecular weight of poly(methyl methacrylate), the proportion of syndiotactic triads in its composition, and consequently, to improve the adhesion strength and heat resistance of the adhesive joint, the curing of the adhesive must be carried out at the reduced temperature (323 K) and the reduced ratio of the [Mc]0/[I]0 = 0.1 in the presence of the least rapidly decomposing initiator HPEB.
{"title":"Kinetics of Methyl Methacrylate Polymerization in the Presence of Initiating Systems “Peroxide + Zirconocene Dichloride” When the Methyl Methacrylate Adhesive is Cured","authors":"Konstantin A. Tereshchenko, Daria A. Shiyan, Andrey A. Osipov, Vera P. Bondarenko, Nikolai V. Ulitin, Elina M. Sabitova, Anton V. Bekker, Yana L. Lyulinskaya, Nikolay A. Novikov, Natalia M. Nurullina, Svetlana N. Tuntseva, Tatyana L. Puchkova, Yaroslav O. Mezhuev, Kharlampii E. Kharlampidi, Sergey V. Kolesov","doi":"10.1021/acs.iecr.4c01937","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c01937","url":null,"abstract":"A kinetic model of the curing of methyl methacrylate adhesive (including nanocomposite methyl methacrylate adhesive) in the presence of the initiating systems “aryl peroxide + zirconocene dichloride” and “aryl hydroperoxide + zirconocene dichloride” is made. Computational experiments have been carried out which demonstrate the relationship of the curing rate with the curing temperature in the range of 323–343 K and with the ratio of the initial concentration of zirconocene dichloride to the initial concentration of the initiator [Mc]<sub>0</sub>/[<i>I</i>]<sub>0</sub> for the following initiators: benzoyl peroxide (PB), ethylbenzene hydroperoxide (HPEB), and ethylbenzene hydroperoxide adduct with cadmium 2-ethyl hexanoate [HPEB·Cd(EH)<sub>2</sub>]. It is shown that in order to increase the curing rate of the adhesive, curing should be carried out at a higher temperature (343 K) and at a higher value of the ratio [Mc]<sub>0</sub>/[<i>I</i>]<sub>0</sub> = 10 in the presence of the most rapidly decomposing initiator HPEB·Cd(EH)<sub>2</sub>. To increase the weight-average molecular weight of poly(methyl methacrylate), the proportion of syndiotactic triads in its composition, and consequently, to improve the adhesion strength and heat resistance of the adhesive joint, the curing of the adhesive must be carried out at the reduced temperature (323 K) and the reduced ratio of the [Mc]<sub>0</sub>/[<i>I</i>]<sub>0</sub> = 0.1 in the presence of the least rapidly decomposing initiator HPEB.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463559","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 : 2024-06-26DOI: 10.1021/acs.iecr.4c01129
Huaqing Li, Nan Tang, Jianing Cui, Haodong Yan, Shipeng Wen, Yan Shi, Weidong Wu
Fiber-reinforced rubber materials find extensive applications in tire manufacturing, hoses, conveyor belts, and various industrial sectors. Polyimide (PI) fibers offer superior fatigue resistance, tensile strength, modulus, and high-temperature durability compared to aramid fibers, positioning them as ideal substitutes in the belt layers of aircraft tire. To enhance the interfacial adhesion between polyimide fibers and rubber while minimizing the use of toxic and environmentally harmful materials, a novel eco-friendly carbon-reducing dipping system was devised. This system employs blocked diisocyanate and epoxy resin to activate PI fibers, and then uses a dipping solution, primarily composed of a blend of styrene–butadiene–vinylpyridine (VP) latex, lignin, tannic acid (TA), and glyoxal, to dip the fibers. This approach connects PI fibers and the rubber matrix through chemical bonds, thereby effectively enhancing the interfacial adhesion between the fibers and the rubber. The H pull-out force of the PI fiber cords treated by this system reached 179.6 N, with an average 180° peeling force of 14.7 N, and dynamic fatigue resistance exceeding 67,000 cycles, comparable to those achieved with the resorcinol-formaldehyde-latex (RFL) dipping system. These results indicate the efficacy of the developed system as a potential replacement for the RFL system. This research presents a sustainable and environmentally friendly approach to enhancing the interfacial adhesion of fiber-reinforced rubber composites, thereby contributing to the advancement of innovative high-performance fibers and biobased dipping system.
纤维增强橡胶材料广泛应用于轮胎制造、软管、传送带和各种工业领域。与芳纶纤维相比，聚酰亚胺（PI）纤维具有更高的抗疲劳性、拉伸强度、模量和高温耐久性，是飞机轮胎带束层的理想替代品。为了增强聚酰亚胺纤维与橡胶之间的界面粘合力，同时最大限度地减少有毒和对环境有害材料的使用，我们设计了一种新型的环保型减碳浸渍系统。该系统采用封端二异氰酸酯和环氧树脂活化聚酰亚胺纤维，然后使用主要由苯乙烯-丁二烯-乙烯基吡啶（VP）胶乳、木质素、单宁酸（TA）和乙二醛混合物组成的浸渍溶液对纤维进行浸渍。这种方法通过化学键将 PI 纤维与橡胶基体连接起来，从而有效增强了纤维与橡胶之间的界面粘附力。经该系统处理的涤纶纤维绳的 H 拔出力达到 179.6 N，平均 180° 剥离力为 14.7 N，动态抗疲劳性超过 67,000 次，与间苯二酚-甲醛-乳胶（RFL）浸渍系统的效果相当。这些结果表明，所开发的系统具有替代 RFL 系统的潜力。这项研究提出了一种可持续且环保的方法来增强纤维增强橡胶复合材料的界面粘附力，从而推动了创新型高性能纤维和生物基浸渍体系的发展。
{"title":"Lignin Biobased Eco-Friendly Dipping System for Polyimide Fiber and Its Interface Adhesive Mechanism with Rubber","authors":"Huaqing Li, Nan Tang, Jianing Cui, Haodong Yan, Shipeng Wen, Yan Shi, Weidong Wu","doi":"10.1021/acs.iecr.4c01129","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c01129","url":null,"abstract":"Fiber-reinforced rubber materials find extensive applications in tire manufacturing, hoses, conveyor belts, and various industrial sectors. Polyimide (PI) fibers offer superior fatigue resistance, tensile strength, modulus, and high-temperature durability compared to aramid fibers, positioning them as ideal substitutes in the belt layers of aircraft tire. To enhance the interfacial adhesion between polyimide fibers and rubber while minimizing the use of toxic and environmentally harmful materials, a novel eco-friendly carbon-reducing dipping system was devised. This system employs blocked diisocyanate and epoxy resin to activate PI fibers, and then uses a dipping solution, primarily composed of a blend of styrene–butadiene–vinylpyridine (VP) latex, lignin, tannic acid (TA), and glyoxal, to dip the fibers. This approach connects PI fibers and the rubber matrix through chemical bonds, thereby effectively enhancing the interfacial adhesion between the fibers and the rubber. The H pull-out force of the PI fiber cords treated by this system reached 179.6 N, with an average 180° peeling force of 14.7 N, and dynamic fatigue resistance exceeding 67,000 cycles, comparable to those achieved with the resorcinol-formaldehyde-latex (RFL) dipping system. These results indicate the efficacy of the developed system as a potential replacement for the RFL system. This research presents a sustainable and environmentally friendly approach to enhancing the interfacial adhesion of fiber-reinforced rubber composites, thereby contributing to the advancement of innovative high-performance fibers and biobased dipping system.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462076","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 : 2024-06-26DOI: 10.1021/acs.iecr.4c00747
A. Gil, I. Sancho-Sanz, S. A. Korili
In recent years, there has been a surge of interest in transforming biomass into fuel, driven by its potential as the only realistic renewable carbon resource. Several conversion methods have been explored to achieve this, including gasification for producing synthesis gas, fast pyrolysis or hydrothermal liquefaction for obtaining bio-oils, and hydrolysis for generating aqueous sugars. Bio-oils offer environmental benefits due to their lower CO2 emissions, but their direct use as fuels is hindered by limitations such as thermal instability, high viscosity and acidity, and low calorific value. Consequently, advancements in treatment methods are necessary before bio-oils can be used as direct fuels. This review focuses on the catalytic hydrotreatment of bio-oils, which has been shown to be an effective approach for the removal of heteroatoms at moderate temperatures (between 300 and 450 °C) but at high pressures (up to 20 MPa). Oxygenated compounds are transformed into H2O, and N and S are transformed into NH3 and H2S, respectively. The analysis examines how process temperature, residence time, hydrogen pressure, solvent selection, and type of catalyst influence the properties of the improved bio-oil. Mo/W sulfide-supported catalysts have been traditionally used as active phases in hydrotreatment processes, as the presence of S limits catalyst deactivation, while the presence of Ni or Co as promoters enhances hydrogenation reactions. New research trends are exploring alternative catalyst formulations, such as metal phosphides, carbides, nitrides, and mesoporous materials as supports with controlled acid-basic properties.
近年来，在生物质作为唯一现实的可再生碳资源的潜力推动下，人们对将生物质转化为燃料产生了浓厚的兴趣。为实现这一目标，人们探索了多种转化方法，包括生产合成气的气化法、获得生物油的快速热解或水热液化法以及生成水溶性糖的水解法。生物油的二氧化碳排放量较低，因此具有环境效益，但由于热不稳定性、高粘度和高酸度以及低热值等限制，生物油不能直接用作燃料。因此，在将生物油直接用作燃料之前，有必要改进处理方法。本综述重点介绍生物油的催化加氢处理，该方法已被证明是在中等温度（300 至 450 °C 之间）和高压（高达 20 兆帕）条件下去除杂原子的有效方法。含氧化合物转化为 H2O，N 和 S 分别转化为 NH3 和 H2S。分析研究了工艺温度、停留时间、氢气压力、溶剂选择和催化剂类型如何影响改良生物油的特性。Mo/W 硫化物支撑催化剂一直被用作加氢处理工艺中的活性相，因为 S 的存在可限制催化剂失活，而作为促进剂的 Ni 或 Co 的存在可增强加氢反应。新的研究趋势是探索其他催化剂配方，如金属磷化物、碳化物、氮化物和介孔材料作为具有可控酸碱特性的载体。
{"title":"Progress and Perspectives in the Catalytic Hydrotreatment of Bio-Oils: Effect of the Nature of the Metal Catalyst","authors":"A. Gil, I. Sancho-Sanz, S. A. Korili","doi":"10.1021/acs.iecr.4c00747","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c00747","url":null,"abstract":"In recent years, there has been a surge of interest in transforming biomass into fuel, driven by its potential as the only realistic renewable carbon resource. Several conversion methods have been explored to achieve this, including gasification for producing synthesis gas, fast pyrolysis or hydrothermal liquefaction for obtaining bio-oils, and hydrolysis for generating aqueous sugars. Bio-oils offer environmental benefits due to their lower CO<sub>2</sub> emissions, but their direct use as fuels is hindered by limitations such as thermal instability, high viscosity and acidity, and low calorific value. Consequently, advancements in treatment methods are necessary before bio-oils can be used as direct fuels. This review focuses on the catalytic hydrotreatment of bio-oils, which has been shown to be an effective approach for the removal of heteroatoms at moderate temperatures (between 300 and 450 °C) but at high pressures (up to 20 MPa). Oxygenated compounds are transformed into H<sub>2</sub>O, and N and S are transformed into NH<sub>3</sub> and H<sub>2</sub>S, respectively. The analysis examines how process temperature, residence time, hydrogen pressure, solvent selection, and type of catalyst influence the properties of the improved bio-oil. Mo/W sulfide-supported catalysts have been traditionally used as active phases in hydrotreatment processes, as the presence of S limits catalyst deactivation, while the presence of Ni or Co as promoters enhances hydrogenation reactions. New research trends are exploring alternative catalyst formulations, such as metal phosphides, carbides, nitrides, and mesoporous materials as supports with controlled acid-basic properties.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462101","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}
Particle stratification in spiral concentrators occurs due to the combined action of gravitational and centrifugal forces. Spiral flows have a free surface, shallow depths, and a transition from laminar to turbulent behavior. The current study investigates the comparisons of the flow field and bicomponent particle separation in high-gravity spirals with conventional coal spirals, often termed low-gravity spirals. A sensitive digital flow depth gauge is utilized to measure the fluid depth across the spiral trough. A high-speed motion camera is utilized to measure the free surface velocity via a tracer tracking approach. This flow visualization technique incorporates lycopodium powder as tracer particles to capture the free surface flow field on a dark background. Further, the two-phase flow is modeled for these designs by utilizing the volume of fluid model (VOF), incorporating the Reynolds stress model and RNG k–ε turbulence models. Comparisons were made on the flow patterns between high-gravity and low-gravity spirals, which differ in their trough profiles. High-gravity spiral concentrators exhibit greater depths, free surface velocities, secondary circulations, and turbulence intensities toward the outer edges compared to low-gravity spirals. The discrete phase model (DPM) is employed for particle tracking, thereby understanding particle segregation radially along the spiral trough. Performance data on bicomponent particle separation is presented to compare the separation effectiveness of high- and low-gravity spirals. Heavy mineral ore, such as chromite, is computationally tested with high- and low-gravity spirals, and it was found that low-gravity spirals are ineffective in achieving satisfactory particle separation. Also, the results demonstrate that each spiral has its own distinct size range for effectively separating particles. The DPM model predictions were validated against in-house experiments conducted with monocomponent silica material, and a reasonable match was found with the experimental data.
{"title":"Comparative Studies of Experimental and Numerical Investigations of Fluid Flow and Particle Separation of High-Gravity Spiral Concentrators","authors":"Prudhvinath Reddy Ankireddy, Purushotham Sudikondala, Narasimha Mangadoddy, Sunil Kumar Tripathy, Rama Murthy Yanamandra","doi":"10.1021/acs.iecr.4c00769","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c00769","url":null,"abstract":"Particle stratification in spiral concentrators occurs due to the combined action of gravitational and centrifugal forces. Spiral flows have a free surface, shallow depths, and a transition from laminar to turbulent behavior. The current study investigates the comparisons of the flow field and bicomponent particle separation in high-gravity spirals with conventional coal spirals, often termed low-gravity spirals. A sensitive digital flow depth gauge is utilized to measure the fluid depth across the spiral trough. A high-speed motion camera is utilized to measure the free surface velocity via a tracer tracking approach. This flow visualization technique incorporates lycopodium powder as tracer particles to capture the free surface flow field on a dark background. Further, the two-phase flow is modeled for these designs by utilizing the volume of fluid model (VOF), incorporating the Reynolds stress model and RNG <i>k</i>–ε turbulence models. Comparisons were made on the flow patterns between high-gravity and low-gravity spirals, which differ in their trough profiles. High-gravity spiral concentrators exhibit greater depths, free surface velocities, secondary circulations, and turbulence intensities toward the outer edges compared to low-gravity spirals. The discrete phase model (DPM) is employed for particle tracking, thereby understanding particle segregation radially along the spiral trough. Performance data on bicomponent particle separation is presented to compare the separation effectiveness of high- and low-gravity spirals. Heavy mineral ore, such as chromite, is computationally tested with high- and low-gravity spirals, and it was found that low-gravity spirals are ineffective in achieving satisfactory particle separation. Also, the results demonstrate that each spiral has its own distinct size range for effectively separating particles. The DPM model predictions were validated against in-house experiments conducted with monocomponent silica material, and a reasonable match was found with the experimental data.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141448859","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}
The concept of droplet microfluidics and droplet reactors is becoming popular in the chemical processing industry, especially to handle expensive specialty chemicals. The convective mixing within a single droplet or two coalescing droplets plays an important role during the reaction involving two-phase systems, which requires a good understanding of the internal fluid motion within the droplet. In this work, we study the flow field inside a liquid droplet falling through an immiscible liquid in a narrow-width rectangular vertical channel using particle image velocimetry (PIV). The droplet can be considered a representation of a midplane cutting through a spherical droplet. The effect of the size and release position of the droplet on the velocity field is examined. When the droplet is released at the center of the channel, a pair of symmetric counter-rotating vortices is observed inside the droplet. The vortices are positioned in the bottom half of the droplet and move toward its horizontal centerline as the diameter increases. However, when the droplet is released at an off-center position, the vortices are not symmetric. The terminal velocity of the droplet is observed to increase with an increase in droplet diameter, and therefore, coalescence occurs when a bigger droplet is released following a smaller one. The growth of the neck of the combined droplet with time and the velocity field at the neck are studied during coalescence.
{"title":"Velocity Field within Droplets Falling in Liquid Media inside a Rectangular Channel","authors":"Deepak Kumar Mishra, Raghvendra Gupta, Anugrah Singh","doi":"10.1021/acs.iecr.4c00727","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c00727","url":null,"abstract":"The concept of droplet microfluidics and droplet reactors is becoming popular in the chemical processing industry, especially to handle expensive specialty chemicals. The convective mixing within a single droplet or two coalescing droplets plays an important role during the reaction involving two-phase systems, which requires a good understanding of the internal fluid motion within the droplet. In this work, we study the flow field inside a liquid droplet falling through an immiscible liquid in a narrow-width rectangular vertical channel using particle image velocimetry (PIV). The droplet can be considered a representation of a midplane cutting through a spherical droplet. The effect of the size and release position of the droplet on the velocity field is examined. When the droplet is released at the center of the channel, a pair of symmetric counter-rotating vortices is observed inside the droplet. The vortices are positioned in the bottom half of the droplet and move toward its horizontal centerline as the diameter increases. However, when the droplet is released at an off-center position, the vortices are not symmetric. The terminal velocity of the droplet is observed to increase with an increase in droplet diameter, and therefore, coalescence occurs when a bigger droplet is released following a smaller one. The growth of the neck of the combined droplet with time and the velocity field at the neck are studied during coalescence.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462099","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 : 2024-06-25DOI: 10.1021/acs.iecr.4c00737
Ioannis Giannikopoulos, Alkiviadis Skouteris, David T. Allen, Michael Baldea, Mark A. Stadtherr
The contribution of renewable energy sources to the power generation portfolio has been increasing in recent years, offering new opportunities for chemical industry electrification and decarbonization. However, renewables often face challenges that may affect their optimal utilization. Wind and solar power generation are highly variable over time, which can lead to a mismatch between electricity output and demand. In this work, we aim to identify optimal ways of more efficiently using wind-generated power through the direct electrification of chemical manufacturing, specifically the replacement of fossil-based thermal heating with electricity-based heating. We implement a multiperiod, multiobjective optimization model formulated as a mixed-integer linear program (MILP). Profit and CO2-equivalent emissions are used as competing objectives in an effort to study the impact of variable renewable energy generation and how it can enable the shift toward lower carbon emissions in chemical manufacturing. The model’s capabilities are illustrated using a process network structure involving chemical processes that can use natural gas liquids as raw materials and a wind farm for power generation. The results demonstrate that the use of renewable electricity is impactful and, through thermal electrification, provides significant CO2 emissions reduction. The coproduction and sale of chemicals and renewable electricity are shown to further accelerate the adoption of process electrification, emphasizing the importance of sector coupling (manufacturing–power grid) in promoting decarbonization. As emission limits become stricter, a transition point is identified beyond which thermal electrification alone is insufficient to meet the emissions target, and reductions in production and/or changing the product mix is necessary to maintain an optimal profit.
{"title":"Thermal Electrification of Chemical Processes Using Renewable Energy: Economic and Decarbonization Impacts","authors":"Ioannis Giannikopoulos, Alkiviadis Skouteris, David T. Allen, Michael Baldea, Mark A. Stadtherr","doi":"10.1021/acs.iecr.4c00737","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c00737","url":null,"abstract":"The contribution of renewable energy sources to the power generation portfolio has been increasing in recent years, offering new opportunities for chemical industry electrification and decarbonization. However, renewables often face challenges that may affect their optimal utilization. Wind and solar power generation are highly variable over time, which can lead to a mismatch between electricity output and demand. In this work, we aim to identify optimal ways of more efficiently using wind-generated power through the direct electrification of chemical manufacturing, specifically the replacement of fossil-based thermal heating with electricity-based heating. We implement a multiperiod, multiobjective optimization model formulated as a mixed-integer linear program (MILP). Profit and CO<sub>2</sub>-equivalent emissions are used as competing objectives in an effort to study the impact of variable renewable energy generation and how it can enable the shift toward lower carbon emissions in chemical manufacturing. The model’s capabilities are illustrated using a process network structure involving chemical processes that can use natural gas liquids as raw materials and a wind farm for power generation. The results demonstrate that the use of renewable electricity is impactful and, through thermal electrification, provides significant CO<sub>2</sub> emissions reduction. The coproduction and sale of chemicals and renewable electricity are shown to further accelerate the adoption of process electrification, emphasizing the importance of sector coupling (manufacturing–power grid) in promoting decarbonization. As emission limits become stricter, a transition point is identified beyond which thermal electrification alone is insufficient to meet the emissions target, and reductions in production and/or changing the product mix is necessary to maintain an optimal profit.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141448826","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 : 2024-06-25DOI: 10.1021/acs.iecr.4c00541
Charles A. Ponge, Nathaniel P. Sheehan, David R. Corbin, Edward Peltier, Justin M. Hutchison, Mark B. Shiflett
Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants that are widespread throughout the environment. While traditional adsorbents such as activated carbon and ion exchange resins have been used to adsorb PFAS from water, the technologies may be limited to certain classes of PFAS compounds. As such, technologies that can address a range of PFAS compounds are needed. In this study, 70 zeolites and molecular sieves with 15 different frameworks and varying pore sizes, framework compositions, and silica–alumina ratios, were tested with 24 PFAS compounds, including perfluoroalkyl carboxylic acids (C4–C14), perfluoroalkanesulfonates (C4–C10), three fluorotelomer sulfonates, NMeFOSAA, FOSA, and NEtFOSAA. PFAS adsorption generally increased with increasing compound hydrophobicity and with molecular sieve ring size. Most β and Faujasite frameworks adsorbed >85% of C8 and larger PFAS compounds. However, β zeolites outperformed all other structures for the sorption of C4–C7 compounds. In addition to the molecular sieves, two calcined hydrotalcites, an aluminum oxide, a magnesium oxide, and an activated carbon were also tested for comparison. The hydrotalcites and activated carbon performed well, adsorbing >74 and >94% of all analytes, while the Al2O3 and MgO adsorbed 43 and 34% on average.
{"title":"Zeolites for Sorption of PFAS from Water","authors":"Charles A. Ponge, Nathaniel P. Sheehan, David R. Corbin, Edward Peltier, Justin M. Hutchison, Mark B. Shiflett","doi":"10.1021/acs.iecr.4c00541","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c00541","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants that are widespread throughout the environment. While traditional adsorbents such as activated carbon and ion exchange resins have been used to adsorb PFAS from water, the technologies may be limited to certain classes of PFAS compounds. As such, technologies that can address a range of PFAS compounds are needed. In this study, 70 zeolites and molecular sieves with 15 different frameworks and varying pore sizes, framework compositions, and silica–alumina ratios, were tested with 24 PFAS compounds, including perfluoroalkyl carboxylic acids (C4–C14), perfluoroalkanesulfonates (C4–C10), three fluorotelomer sulfonates, NMeFOSAA, FOSA, and NEtFOSAA. PFAS adsorption generally increased with increasing compound hydrophobicity and with molecular sieve ring size. Most β and Faujasite frameworks adsorbed >85% of C8 and larger PFAS compounds. However, β zeolites outperformed all other structures for the sorption of C4–C7 compounds. In addition to the molecular sieves, two calcined hydrotalcites, an aluminum oxide, a magnesium oxide, and an activated carbon were also tested for comparison. The hydrotalcites and activated carbon performed well, adsorbing >74 and >94% of all analytes, while the Al<sub>2</sub>O<sub>3</sub> and MgO adsorbed 43 and 34% on average.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462009","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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