Journal of Supercritical Fluids最新文献_第3页

Investigation of volatile organic compounds adsorption capacities and regeneration properties of silica aerogel particles 二氧化硅气凝胶颗粒对挥发性有机物的吸附性能及再生性能研究

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-20 DOI: 10.1016/j.supflu.2026.106905

Işık Sena Akgün , Ayça Tüter Semercioğlu , Emine Yapıcı , Berat Keçeci , Derin Aktaş , Gökhan Sır , Sevil Yücel

This study investigates the volatile organic compound adsorption and thermal regeneration properties of four different silica aerogels which were synthesized via supercritical carbon dioxide drying and spray drying using methyl ethyl ketone as a model indoor air pollutant. The goal was to assess the impact of structural properties (surface area, pore size, drying technique) and magnesium doping on both initial adsorption capacity and long-term reusability over 15 adsorption/desorption cycles. The silica aerogel dried with supercritical carbon dioxide, characterized by high BET surface area (976.7 ± 0.4 m²/g) and average pore size (11.7 ± 0.1 nm), exhibited the superior initial methyl ethyl ketone adsorption capacity compared to the spray-dried aerogels and commercial activated carbon. While magnesium doping did not significantly improve the initial uptake, it was associated with a more stable desorption performance. Regeneration temperature was found to be the dominant factor for performance retention. Increasing the regeneration temperature from 55°C to 130°C significantly mitigated capacity decline by enhancing methyl ethyl ketone desorption efficiency. Kinetic analysis revealed that methyl ethyl ketone adsorption on both the silica aerogel dried with supercritical carbon dioxide and commercial activated carbon was best described by the Pseudo-Second-Order model, suggesting a primary rate-limiting step involving surface adsorption. Overall, the silica aerogel dried with supercritical carbon dioxide sample demonstrated an initial adsorption capacity approximately 1.5 times higher than commercial activated carbon, proving that supercritically dried silica aerogels are highly promising, durable, and regenerable adsorbents for effective indoor volatile organic compound removal.

以甲基乙基酮为模型室内空气污染物，通过超临界二氧化碳干燥和喷雾干燥制备了四种不同的二氧化硅气凝胶，研究了其对挥发性有机物的吸附和热再生性能。目的是评估结构特性（表面积、孔径、干燥技术）和镁掺杂对初始吸附能力和15个吸附/解吸循环的长期可重用性的影响。超临界二氧化碳干燥的二氧化硅气凝胶具有较高的BET比表面积（976.7 ± 0.4 m2/g）和平均孔径（11.7 ± 0.1 nm），与喷雾干燥气凝胶和商业活性炭相比，具有更好的甲基乙基酮初始吸附能力。虽然镁掺杂并没有显著改善初始吸收，但它与更稳定的脱附性能有关。再生温度是影响性能保持的主要因素。将再生温度从55℃提高到130℃，通过提高甲基乙基酮的脱附效率，显著缓解了容量下降。动力学分析表明，甲基乙基酮在超临界二氧化碳和商用活性炭干燥的硅胶气凝胶上的吸附都可以用拟二级模型来描述，表明主要的限速步骤涉及表面吸附。总的来说，用超临界二氧化碳样品干燥的二氧化硅气凝胶的初始吸附能力大约是商用活性炭的1.5倍，证明了超临界干燥的二氧化硅气凝胶是一种非常有前途的、耐用的、可再生的吸附剂，可以有效地去除室内挥发性有机化合物。

{"title":"Investigation of volatile organic compounds adsorption capacities and regeneration properties of silica aerogel particles","authors":"Işık Sena Akgün , Ayça Tüter Semercioğlu , Emine Yapıcı , Berat Keçeci , Derin Aktaş , Gökhan Sır , Sevil Yücel","doi":"10.1016/j.supflu.2026.106905","DOIUrl":"10.1016/j.supflu.2026.106905","url":null,"abstract":"<div><div>This study investigates the volatile organic compound adsorption and thermal regeneration properties of four different silica aerogels which were synthesized via supercritical carbon dioxide drying and spray drying using methyl ethyl ketone as a model indoor air pollutant. The goal was to assess the impact of structural properties (surface area, pore size, drying technique) and magnesium doping on both initial adsorption capacity and long-term reusability over 15 adsorption/desorption cycles. The silica aerogel dried with supercritical carbon dioxide, characterized by high BET surface area (976.7 ± 0.4 m<sup>2</sup>/g) and average pore size (11.7 ± 0.1 nm), exhibited the superior initial methyl ethyl ketone adsorption capacity compared to the spray-dried aerogels and commercial activated carbon. While magnesium doping did not significantly improve the initial uptake, it was associated with a more stable desorption performance. Regeneration temperature was found to be the dominant factor for performance retention. Increasing the regeneration temperature from 55°C to 130°C significantly mitigated capacity decline by enhancing methyl ethyl ketone desorption efficiency. Kinetic analysis revealed that methyl ethyl ketone adsorption on both the silica aerogel dried with supercritical carbon dioxide and commercial activated carbon was best described by the Pseudo-Second-Order model, suggesting a primary rate-limiting step involving surface adsorption. Overall, the silica aerogel dried with supercritical carbon dioxide sample demonstrated an initial adsorption capacity approximately 1.5 times higher than commercial activated carbon, proving that supercritically dried silica aerogels are highly promising, durable, and regenerable adsorbents for effective indoor volatile organic compound removal.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106905"},"PeriodicalIF":4.4,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014440","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}

引用次数: 0

Construction and optimization of a low-pressure direct-fired semi-closed CO2 cycle based on the temperature rise patterns of working fluid compression 基于工质压缩温升规律的低压直燃半封闭CO2循环的构建与优化

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-19 DOI: 10.1016/j.supflu.2026.106902

Enhui Sun , Weiqi Zhang , Zhenyu Leng , Qinchai Chen , Jinliang Xu , Tai Wang , Zhiming Qin

Oxygen-enriched direct-combustion cycles hold significant potential for efficient carbon capture. However, mainstream technologies face inherent limitations regarding operating pressure and system complexity. The excessive temperature rise during working fluid compression remains a primary bottleneck in constructing these systems. Based on a thermodynamic analysis of gas compression processes, this study reveals an intrinsic correlation between compression temperature rise and the molecular degrees of freedom. Specifically, it is found that the compression temperature rise of triatomic gases (e.g., CO₂) is significantly lower than that of diatomic gas mixtures (such as air). Building on this theoretical insight, the feasibility of constructing a low-pressure, subcritical CO₂ direct-recuperative Brayton cycle (LPBC) is demonstrated. This approach breaks the conventional parameter selection paradigm for semi-closed Brayton cycles, greatly reducing the difficulty and complexity of system construction. To further unlock the potential of this cycle, direct-contact spray cooling is introduced to replace conventional intercooling. Numerical simulations demonstrate that this method achieves near-isothermal compression with a minimal pressure drop of only 20 Pa. Consequently, the optimized system (III-LPBC) achieves a thermal efficiency of 66.09 %, surpassing that of typical high-pressure cycles (63.43 %). This study not only provides a theoretical framework for working fluid selection based on molecular properties but also offers a novel technical pathway for constructing next-generation fossil fuel-based power generation systems that balance high efficiency, operational flexibility, and low-carbon emissions.

富氧直接燃烧循环具有有效碳捕获的巨大潜力。然而，主流技术在操作压力和系统复杂性方面存在固有的局限性。在工作流体压缩过程中过高的温升仍然是构建这些系统的主要瓶颈。通过对气体压缩过程的热力学分析，揭示了压缩温升与分子自由度之间的内在联系。具体来说，三原子气体（如CO2）的压缩温升明显低于双原子气体混合物（如空气）的压缩温升。基于这一理论见解，论证了构建低压、亚临界CO2直接回收布雷顿循环（LPBC）的可行性。该方法打破了传统的半封闭Brayton循环参数选择范式，大大降低了系统构建的难度和复杂性。为了进一步释放这一循环的潜力，引入了直接接触喷雾冷却来取代传统的中间冷却。数值模拟结果表明，该方法实现了近等温压缩，最小压降仅为20 Pa。因此，优化后的系统（III-LPBC）的热效率为66.09 %，超过了典型高压循环的热效率（63.43 %）。该研究不仅为基于分子特性的工作流体选择提供了理论框架，而且为构建高效、运行灵活性和低碳排放的下一代化石燃料发电系统提供了新的技术途径。

{"title":"Construction and optimization of a low-pressure direct-fired semi-closed CO2 cycle based on the temperature rise patterns of working fluid compression","authors":"Enhui Sun , Weiqi Zhang , Zhenyu Leng , Qinchai Chen , Jinliang Xu , Tai Wang , Zhiming Qin","doi":"10.1016/j.supflu.2026.106902","DOIUrl":"10.1016/j.supflu.2026.106902","url":null,"abstract":"<div><div>Oxygen-enriched direct-combustion cycles hold significant potential for efficient carbon capture. However, mainstream technologies face inherent limitations regarding operating pressure and system complexity. The excessive temperature rise during working fluid compression remains a primary bottleneck in constructing these systems. Based on a thermodynamic analysis of gas compression processes, this study reveals an intrinsic correlation between compression temperature rise and the molecular degrees of freedom. Specifically, it is found that the compression temperature rise of triatomic gases (e.g., CO<sub>2</sub>) is significantly lower than that of diatomic gas mixtures (such as air). Building on this theoretical insight, the feasibility of constructing a low-pressure, subcritical CO<sub>2</sub> direct-recuperative Brayton cycle (LPBC) is demonstrated. This approach breaks the conventional parameter selection paradigm for semi-closed Brayton cycles, greatly reducing the difficulty and complexity of system construction. To further unlock the potential of this cycle, direct-contact spray cooling is introduced to replace conventional intercooling. Numerical simulations demonstrate that this method achieves near-isothermal compression with a minimal pressure drop of only 20 Pa. Consequently, the optimized system (III-LPBC) achieves a thermal efficiency of 66.09 %, surpassing that of typical high-pressure cycles (63.43 %). This study not only provides a theoretical framework for working fluid selection based on molecular properties but also offers a novel technical pathway for constructing next-generation fossil fuel-based power generation systems that balance high efficiency, operational flexibility, and low-carbon emissions.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106902"},"PeriodicalIF":4.4,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146000779","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}

引用次数: 0

Estimation of critical curves by empirical and rigorous modelling methods: Case studies on n-alkane + dimethyl carbonate and n-alkane + chloroalkane 用经验和严格的建模方法估计临界曲线：以正烷烃+碳酸二甲酯和正烷烃+氯烷烃为例

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-18 DOI: 10.1016/j.supflu.2026.106900

Luis A. Roman , Gary A. Leeke

The determination of critical curves is important for the design of chemical processes. The accuracy of fast and rigorous methods for estimating the vapour-liquid critical curves of n-alkane + dimethyl carbonate, and n-alkane + chloroalkane binary systems is tested. The n-alkanes range from propane to n-decane, whereas the chloroalkanes are dichloromethane, 1,1-dichloroethane and 1,2-dichloroethane. The fast estimation methods evaluated are: the conformal solution theory (CM); the method of He et al. (2017); and the method of Tang et al. (2024). The rigorous methods studied are: the corresponding states principle (CSP) with the one-fluid van der Waals equation of state (vdW EoS); and the Heidemann-Khalil-Michelsen (HKM) method with the Peng-Robinson EoS. Despite the simplicity of the EoS, CSP provides the best correlations, resulting in overall average absolute relative errors (

AARE

) for temperature and pressure of

AARE T^{c} = 0.36 %

and

AARE p^{c} = 1.68 %

, respectively. CM is the only recommended fast method due to its scientific soundness and accuracy (

AARE T^{c} = 0.55 %

and AARE p^{c} = 5.10 %

). The methods of He and Tang exhibit parameter degeneracy, questioning their reliability. This work underscores the importance to reconsider CSP as a reliable method for estimating critical curves and presents, for the first time, the explicit equations required to apply this method using the VdW EoS.

临界曲线的确定对化工工艺设计具有重要意义。对正构烷烃+ 碳酸二甲酯和正构烷烃+ 氯烷烃二元体系汽液临界曲线的快速、严格估算方法的准确性进行了验证。正烷的范围从丙烷到正癸烷，而氯烷是二氯甲烷、1,1-二氯乙烷和1,2-二氯乙烷。评估的快速估计方法有：保角解理论（CM）；He et al. (2017)；和Tang et al.（2024）的方法。研究的严格方法是：对应状态原理（CSP）与单流体范德华斯状态方程（vdW EoS）；以及Heidemann-Khalil-Michelsen （HKM）方法与Peng-Robinson EoS。尽管EoS简单，但CSP提供了最好的相关性，导致AARETc和AAREpc的温度和压力的总体平均绝对相对误差（AARE）分别为0.36%和1.68%。CM法具有良好的科学性和准确性（AARETc=0.55%, aarepc =5.10%），是唯一推荐的快速检测方法。何和唐的方法表现出参数退化，质疑其可靠性。这项工作强调了重新考虑CSP作为估计临界曲线的可靠方法的重要性，并首次提出了使用VdW EoS应用该方法所需的显式方程。

{"title":"Estimation of critical curves by empirical and rigorous modelling methods: Case studies on n-alkane + dimethyl carbonate and n-alkane + chloroalkane","authors":"Luis A. Roman , Gary A. Leeke","doi":"10.1016/j.supflu.2026.106900","DOIUrl":"10.1016/j.supflu.2026.106900","url":null,"abstract":"<div><div>The determination of critical curves is important for the design of chemical processes. The accuracy of fast and rigorous methods for estimating the vapour-liquid critical curves of n-alkane + dimethyl carbonate, and n-alkane + chloroalkane binary systems is tested. The n-alkanes range from propane to n-decane, whereas the chloroalkanes are dichloromethane, 1,1-dichloroethane and 1,2-dichloroethane. The fast estimation methods evaluated are: the conformal solution theory (CM); the method of He et al. (2017); and the method of Tang et al. (2024). The rigorous methods studied are: the corresponding states principle (CSP) with the one-fluid van der Waals equation of state (vdW EoS); and the Heidemann-Khalil-Michelsen (HKM) method with the Peng-Robinson EoS. Despite the simplicity of the EoS, CSP provides the best correlations, resulting in overall average absolute relative errors (<span><math><mi>AARE</mi></math></span>) for temperature and pressure of <span><math><mrow><mi>AARE</mi><msup><mrow><mi>T</mi></mrow><mrow><mi>c</mi></mrow></msup><mo>=</mo><mn>0.36</mn><mo>%</mo></mrow></math></span> and <span><math><mrow><mi>AARE</mi><msup><mrow><mi>p</mi></mrow><mrow><mi>c</mi></mrow></msup><mo>=</mo><mn>1.68</mn><mo>%</mo></mrow></math></span>, respectively. CM is the only recommended fast method due to its scientific soundness and accuracy (<span><math><mrow><mi>AARE</mi><msup><mrow><mi>T</mi></mrow><mrow><mi>c</mi></mrow></msup><mo>=</mo><mn>0.55</mn><mo>%</mo></mrow></math></span> <span><math><mrow><mi>and</mi><mi>AARE</mi><msup><mrow><mi>p</mi></mrow><mrow><mi>c</mi></mrow></msup><mo>=</mo><mn>5.10</mn><mo>%</mo></mrow></math></span>). The methods of He and Tang exhibit parameter degeneracy, questioning their reliability. This work underscores the importance to reconsider CSP as a reliable method for estimating critical curves and presents, for the first time, the explicit equations required to apply this method using the VdW EoS.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106900"},"PeriodicalIF":4.4,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995408","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}

引用次数: 0

High-pressure extraction of marigold (Calendula officinalis); Evaluation of chemical composition, pharmacological and antitumor potential 高压提取万寿菊（Calendula officinalis）评价其化学成分、药理及抗肿瘤潜能

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-17 DOI: 10.1016/j.supflu.2026.106898

Mirjana Sulejmanović , Senka Vidović , Igor Jerković , Nataša Milić , Aleksandra Popović , Jelena Jeremić , Vanja Travičić , Stela Jokić , Krunoslav Aladić , Aleksandra Gavarić

The isolation of bioactive compounds from plants has gained significant attention due to their potential in developing novel health-promoting products. Among these, marigold (Calendula officinalis) is recognized for its antioxidant, hepatoprotective, and wound-healing properties. This study examined five marigold plant parts–petals (MP), calyxes (MC), calyxes with petals (MCP), stems (MS), and stems with calyxes and petals (MSCP)–extracted using supercritical carbon dioxide (scCO₂), an advanced technique that avoids toxic solvents and reduces extraction time compared to conventional methods. GC–MS analysis of the scCO₂ extracts revealed that sesquiterpenes were the predominant constituents, including δ-cadinene (19.13–26.96 %), γ-cadinene (9.62–12.92 %), t-muurolol (2.08–10.07 %), α-cadinol (1.42–5.81 %), and ledene (1.24–8.87 %). In addition, monoterpenes such as thymol (1.85–2.87 %), camphor (1.77–2.07 %), β-thujone (0.93–1.13 %), and carvacrol (0.58–1.25 %), as well as the alkane nonadecane (0.50–23.17 %), were also identified. The in vitro antitumor potential of MP, MC, and MS plant parts was evaluated in H4IIE hepatoma cells. Cell viability, morphological analysis, and colony formation assays demonstrated cytotoxic activity, with marigold calyxes showing the most pronounced effect. In addition, hepatoprotective properties were confirmed, further supporting the therapeutic relevance of marigold extracts. These findings suggest that sc-CO₂ extracts of marigold hold promise as potential antitumor agents. However, further preclinical and clinical studies are required to assess their safety, efficacy, and applicability in human therapy.

从植物中分离生物活性化合物因其在开发新型健康促进产品方面的潜力而受到广泛关注。其中，金盏花（Calendula officinalis）被认为具有抗氧化、保护肝脏和伤口愈合的特性。与传统的提取方法相比，超临界二氧化碳（scCO₂）技术避免了有毒溶剂，缩短了提取时间，研究了金盏花植物的5个部分——花瓣（MP）、花萼（MC）、花萼带花瓣（MCP）、茎（MS）、茎带花萼和花瓣（MSCP）。GC-MS分析表明，scCO₂提取物的主要成分为倍半萜类，包括δ-cadinene（19.13 ~ 26.96 %）、γ-cadinene（9.62 ~ 12.92 %）、t-muurolol（2.08 ~ 10.07 %）、α-cadinol（1.42 ~ 5.81 %）和ledene（1.24 ~ 8.87 %）。此外，还鉴定出百里香酚（1.85 ~ 2.87 %）、樟脑（1.77 ~ 2.07 %）、β-thujone（0.93 ~ 1.13 %）、香芹醇（0.58 ~ 1.25 %）等单萜类化合物，以及烷烃壬烷（0.50 ~ 23.17 %）。在H4IIE肝癌细胞中评价了MP、MC和MS植物部位的体外抗肿瘤作用。细胞活力、形态分析和集落形成分析显示细胞毒性活性，其中万寿菊花萼表现出最明显的效果。此外，还证实了万寿菊提取物的肝保护作用，进一步支持了万寿菊提取物的治疗相关性。这些发现表明，金盏花的sc-CO₂提取物有望成为潜在的抗肿瘤药物。然而，需要进一步的临床前和临床研究来评估它们在人类治疗中的安全性、有效性和适用性。

{"title":"High-pressure extraction of marigold (Calendula officinalis); Evaluation of chemical composition, pharmacological and antitumor potential","authors":"Mirjana Sulejmanović , Senka Vidović , Igor Jerković , Nataša Milić , Aleksandra Popović , Jelena Jeremić , Vanja Travičić , Stela Jokić , Krunoslav Aladić , Aleksandra Gavarić","doi":"10.1016/j.supflu.2026.106898","DOIUrl":"10.1016/j.supflu.2026.106898","url":null,"abstract":"<div><div>The isolation of bioactive compounds from plants has gained significant attention due to their potential in developing novel health-promoting products. Among these, marigold (<em>Calendula officinalis</em>) is recognized for its antioxidant, hepatoprotective, and wound-healing properties. This study examined five marigold plant parts–petals (MP), calyxes (MC), calyxes with petals (MCP), stems (MS), and stems with calyxes and petals (MSCP)–extracted using supercritical carbon dioxide (scCO₂), an advanced technique that avoids toxic solvents and reduces extraction time compared to conventional methods. GC–MS analysis of the scCO₂ extracts revealed that sesquiterpenes were the predominant constituents, including δ-cadinene (19.13–26.96 %), γ-cadinene (9.62–12.92 %), t-muurolol (2.08–10.07 %), α-cadinol (1.42–5.81 %), and ledene (1.24–8.87 %). In addition, monoterpenes such as thymol (1.85–2.87 %), camphor (1.77–2.07 %), β-thujone (0.93–1.13 %), and carvacrol (0.58–1.25 %), as well as the alkane nonadecane (0.50–23.17 %), were also identified. The in vitro antitumor potential of MP, MC, and MS plant parts was evaluated in H4IIE hepatoma cells. Cell viability, morphological analysis, and colony formation assays demonstrated cytotoxic activity, with marigold calyxes showing the most pronounced effect. In addition, hepatoprotective properties were confirmed, further supporting the therapeutic relevance of marigold extracts. These findings suggest that sc-CO₂ extracts of marigold hold promise as potential antitumor agents. However, further preclinical and clinical studies are required to assess their safety, efficacy, and applicability in human therapy.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106898"},"PeriodicalIF":4.4,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995409","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}

引用次数: 0

Phosphate-induced corrosion of nickel alloys in supercritical water: Mechanistic insights into passivation and accelerated corrosion at elevated temperatures 镍合金在超临界水中的磷酸盐诱导腐蚀：在高温下钝化和加速腐蚀的机理

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-17 DOI: 10.1016/j.supflu.2026.106901

Shaoming Ding , Yanhui Li , Wang Zhu , Limei Xing , Qibo Wang , Zhouyang Bai , Pengfei Gao , Fengxiao Hou

This study examines the corrosion behavior of Inconel 600 and Inconel 625 alloys in supercritical water environments containing phosphates, with a focus on the temperature-dependent effects of phosphate in both dissolved and molten states. At 400 °C, dissolved phosphate acts as a passivating agent, forming protective metal phosphate films that reduce corrosion. At 600 °C, the low solubility of phosphate causes it to precipitate into a molten state. This significantly accelerates corrosion by dissolving the protective oxide film and enhancing ion diffusion, increasing the film thickness from 0.16 μm to 0.675 μm. The higher Cr content in Inconel 625 resulted in an 65.9 % reduction in oxide thickness relative to Inconel 600, indicating enhanced oxidation resistance. The core theoretical innovation of this study lies in identifying the dual role of phosphate in alloy corrosion: acting as a passivating agent at lower temperatures and as a corrosion accelerator at higher temperatures. This study further clarifies the competitive relationship between phosphate and oxygen, the mechanism by which molten salts accelerate corrosion, and the synergistic molten corrosion effect of Na⁺. The findings provide valuable insights into corrosion protection strategies for supercritical water oxidation systems, contributing to the optimization of material design in extreme environments.

本研究考察了因科乃尔600和因科乃尔625合金在含磷酸盐的超临界水环境中的腐蚀行为，重点研究了磷酸盐在溶解和熔融状态下的温度依赖效应。在400°C时，溶解的磷酸盐作为钝化剂，形成保护性的金属磷酸盐膜，减少腐蚀。在600℃时，磷酸盐的低溶解度使其沉淀成熔融状态。通过溶解氧化保护膜和增强离子扩散，使氧化保护膜的厚度从0.16 μm增加到0.675 μm，从而显著加速腐蚀。与Inconel 600相比，较高的Cr含量使Inconel 625的氧化物厚度降低了65.9 %，表明其抗氧化性增强。本研究的核心理论创新在于确定了磷酸盐在合金腐蚀中的双重作用：低温时作为钝化剂，高温时作为腐蚀促进剂。本研究进一步阐明了磷酸盐与氧的竞争关系、熔盐加速腐蚀的机理以及Na⁺的协同熔蚀效应。这些发现为超临界水氧化系统的腐蚀防护策略提供了有价值的见解，有助于在极端环境下优化材料设计。

{"title":"Phosphate-induced corrosion of nickel alloys in supercritical water: Mechanistic insights into passivation and accelerated corrosion at elevated temperatures","authors":"Shaoming Ding , Yanhui Li , Wang Zhu , Limei Xing , Qibo Wang , Zhouyang Bai , Pengfei Gao , Fengxiao Hou","doi":"10.1016/j.supflu.2026.106901","DOIUrl":"10.1016/j.supflu.2026.106901","url":null,"abstract":"<div><div>This study examines the corrosion behavior of Inconel 600 and Inconel 625 alloys in supercritical water environments containing phosphates, with a focus on the temperature-dependent effects of phosphate in both dissolved and molten states. At 400 °C, dissolved phosphate acts as a passivating agent, forming protective metal phosphate films that reduce corrosion. At 600 °C, the low solubility of phosphate causes it to precipitate into a molten state. This significantly accelerates corrosion by dissolving the protective oxide film and enhancing ion diffusion, increasing the film thickness from 0.16 μm to 0.675 μm. The higher Cr content in Inconel 625 resulted in an 65.9 % reduction in oxide thickness relative to Inconel 600, indicating enhanced oxidation resistance. The core theoretical innovation of this study lies in identifying the dual role of phosphate in alloy corrosion: acting as a passivating agent at lower temperatures and as a corrosion accelerator at higher temperatures. This study further clarifies the competitive relationship between phosphate and oxygen, the mechanism by which molten salts accelerate corrosion, and the synergistic molten corrosion effect of Na⁺. The findings provide valuable insights into corrosion protection strategies for supercritical water oxidation systems, contributing to the optimization of material design in extreme environments.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106901"},"PeriodicalIF":4.4,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995407","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}

引用次数: 0

Dynamic performance comparison of supercritical CO₂ Brayton cycle layouts using an enhanced dynamic model 基于增强型动态模型的超临界co2 Brayton循环布局动态性能比较

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-16 DOI: 10.1016/j.supflu.2026.106896

Tariq Alsawy , Ramy H. Mohammed , Osama Mesalhy , Mohamed Abdelkareem

There is a growing interest in the supercritical CO₂ Brayton cycle (SCO₂BC) as a high-efficiency power generation technology across various energy sectors, including renewable energy. SCO₂BC dynamic modelling is key to grasp its performance, especially under off-design conditions such as fluctuating operating load. Numerous studies that compare the steady-state behavior of different SCO₂BC layouts are present. However, existing literature lacks in-depth analyses of transient responses of different SCO₂BC layouts with accuracy-improved turbomachinery performance-map. This research fills this gap by comparing four layouts: recuperated (RCU), recompression (RCOMP), reheat (RHT), intercool (INC), through dynamic simulations with accuracy-improved turbomachinery models. The transient responses of the key SCO₂BC cycle performance parameters are deeply investigated, offering novel insights into their transient behavior. An additional novelty of this work is the usage of corrected turbomachinery performance maps with improved prediction accuracy for the dynamic comparison. The study reveals that mass flow rate and compressor inlet conditions are most affected by a cooling water temperature disturbance (ColdT), while turbine inlet state is more sensitive to a heater temperature change (HotT). For all the studied layouts, net power responses are primarily driven by mass flow rate and turbine inlet temperature (TIT) for ColdT and HotT disturbances, respectively. Layout configurations (number and arrangement of turbomachines) influence transient response sensitivity. RCU and RHT layouts exhibit larger net power fluctuations for ColdT, while RCU and INC layouts show larger responses for HotT. The RCOMP is generally the most stable layout, while RHT and INC demonstrate conditional stability depending on the disturbance.

超临界二氧化碳布雷顿循环（SCO2BC）作为一种高效发电技术，在包括可再生能源在内的各个能源领域受到越来越多的关注。SCO2BC动态建模是掌握其性能的关键，特别是在非设计工况下，如运行负荷波动。目前有许多研究比较了不同SCO2BC布局的稳态行为。然而，现有文献缺乏利用精度改进的涡轮机械性能图对不同SCO2BC布局的瞬态响应进行深入分析。本研究通过采用改进精度的涡轮机械模型进行动态仿真，比较了四种布局：回热（RCU）、再压缩（RCOMP）、再热（RHT）、中冷（INC），填补了这一空白。深入研究了关键SCO2BC循环性能参数的瞬态响应，为其瞬态行为提供了新的见解。这项工作的另一个新颖之处是使用了校正的涡轮机械性能图，提高了动态比较的预测精度。研究表明，质量流量和压气机进口状态受冷却水温度扰动（ColdT）的影响最大，而涡轮进口状态受加热器温度变化（HotT）的影响更为敏感。对于所有研究的布局，净功率响应主要是由质量流量和涡轮进口温度（TIT）分别对ColdT和HotT扰动驱动。布局配置（涡轮的数量和排列）影响瞬态响应灵敏度。RCU和RHT布局对ColdT表现出较大的净功率波动，而RCU和INC布局对HotT表现出较大的响应。RCOMP通常是最稳定的布局，而RHT和INC则根据干扰表现出条件稳定性。

{"title":"Dynamic performance comparison of supercritical CO₂ Brayton cycle layouts using an enhanced dynamic model","authors":"Tariq Alsawy , Ramy H. Mohammed , Osama Mesalhy , Mohamed Abdelkareem","doi":"10.1016/j.supflu.2026.106896","DOIUrl":"10.1016/j.supflu.2026.106896","url":null,"abstract":"<div><div>There is a growing interest in the supercritical CO<sub>2</sub> Brayton cycle (SCO<sub>2</sub>BC) as a high-efficiency power generation technology across various energy sectors, including renewable energy. SCO<sub>2</sub>BC dynamic modelling is key to grasp its performance, especially under off-design conditions such as fluctuating operating load. Numerous studies that compare the steady-state behavior of different SCO<sub>2</sub>BC layouts are present. However, existing literature lacks in-depth analyses of transient responses of different SCO<sub>2</sub>BC layouts with accuracy-improved turbomachinery performance-map. This research fills this gap by comparing four layouts: recuperated (RCU), recompression (RCOMP), reheat (RHT), intercool (INC), through dynamic simulations with accuracy-improved turbomachinery models. The transient responses of the key SCO<sub>2</sub>BC cycle performance parameters are deeply investigated, offering novel insights into their transient behavior. An additional novelty of this work is the usage of corrected turbomachinery performance maps with improved prediction accuracy for the dynamic comparison. The study reveals that mass flow rate and compressor inlet conditions are most affected by a cooling water temperature disturbance (ColdT), while turbine inlet state is more sensitive to a heater temperature change (HotT). For all the studied layouts, net power responses are primarily driven by mass flow rate and turbine inlet temperature (TIT) for ColdT and HotT disturbances, respectively. Layout configurations (number and arrangement of turbomachines) influence transient response sensitivity. RCU and RHT layouts exhibit larger net power fluctuations for ColdT, while RCU and INC layouts show larger responses for HotT. The RCOMP is generally the most stable layout, while RHT and INC demonstrate conditional stability depending on the disturbance.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106896"},"PeriodicalIF":4.4,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995410","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}

引用次数: 0

Performance of convective heat transfer of supercritical CO2 in unilaterally heated rectangular channel 超临界CO2在单边加热矩形通道内的对流换热性能

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-16 DOI: 10.1016/j.supflu.2026.106895

Shang Mao , Shengli Zhang , Xuehong Wu , Yong Liu , Leigang Zhang , Cai Lv , Tao Zhou , Songzhen Tang

The utilization of supercritical CO₂ (sCO₂) for cooling aero-engine combustion chambers can effectively alleviate the hydrocarbon fuel slagging issue in hypersonic vehicles. Nevertheless, research on sCO₂ heat transfer and performance optimization in regenerative cooling channels under high heat flux unilateral heating conditions remains limited. Influence of heat flux, mass flux, operating pressure and heating position on the flow dynamics and heat transfer was numerically investigated. Results indicated that wall temperature (T_w) peak intensified with increase of heat flux and decrease of pressure and mass flux. Heat transfer deterioration (HTD) can be alleviated by elevating inlet temperature above the pseudo-critical temperature T_in>T_pc. Furthermore, temperature non-uniformity coefficient served as an effective predictor of heat sink performance of regenerative cooling channels. A lower coefficient indicated a higher heat sink utilization rate. Analysis revealed that turbulent kinetic energy within the boundary layer was primary factor governing heat transfer performance. Friction loss dominated and acceleration loss comprised approximately 1/4 of total pressure drop. Comparative assessment demonstrated that top heating led to the highest T_w, whereas side heating induced the greatest pressure drop. Finally, sinusoidal wavy channels were proposed, with amplitude A= 0.2 mm and period p = 4 mm exhibiting optimal flow and heat transfer capabilities for various heating position.

利用超临界CO2 （sCO2）冷却航空发动机燃烧室可以有效缓解高超声速飞行器烃类燃料结渣问题。然而，高热流密度单边加热条件下蓄热式冷却通道中sCO2的换热及性能优化研究仍然有限。数值研究了热流密度、质量通量、操作压力和加热位置对流动动力学和传热的影响。结果表明，壁面温度（Tw）峰值随热流密度的增大和压力、质量流密度的减小而增大。将进口温度提高到拟临界温度Tpc以上可以缓解换热恶化（HTD）。此外，温度非均匀性系数可以作为蓄热式冷却通道散热性能的有效预测因子。系数越低，表明热沉利用率越高。分析表明，边界层内的湍流动能是影响传热性能的主要因素。摩擦损失占主导地位，加速度损失约占总压降的1/4。对比分析表明，顶部加热导致的Tw最大，而侧面加热导致的压降最大。最后，提出了振幅A= 0.2 mm，周期p = 4 mm的正弦通道，在不同的加热位置表现出最佳的流动和换热能力。

{"title":"Performance of convective heat transfer of supercritical CO2 in unilaterally heated rectangular channel","authors":"Shang Mao , Shengli Zhang , Xuehong Wu , Yong Liu , Leigang Zhang , Cai Lv , Tao Zhou , Songzhen Tang","doi":"10.1016/j.supflu.2026.106895","DOIUrl":"10.1016/j.supflu.2026.106895","url":null,"abstract":"<div><div>The utilization of supercritical CO<sub>2</sub> (sCO<sub>2</sub>) for cooling aero-engine combustion chambers can effectively alleviate the hydrocarbon fuel slagging issue in hypersonic vehicles. Nevertheless, research on sCO<sub>2</sub> heat transfer and performance optimization in regenerative cooling channels under high heat flux unilateral heating conditions remains limited. Influence of heat flux, mass flux, operating pressure and heating position on the flow dynamics and heat transfer was numerically investigated. Results indicated that wall temperature (<em>T</em><sub>w</sub>) peak intensified with increase of heat flux and decrease of pressure and mass flux. Heat transfer deterioration (HTD) can be alleviated by elevating inlet temperature above the pseudo-critical temperature <em>T</em><sub>in</sub>><em>T</em><sub>pc</sub>. Furthermore, temperature non-uniformity coefficient served as an effective predictor of heat sink performance of regenerative cooling channels. A lower coefficient indicated a higher heat sink utilization rate. Analysis revealed that turbulent kinetic energy within the boundary layer was primary factor governing heat transfer performance. Friction loss dominated and acceleration loss comprised approximately 1/4 of total pressure drop. Comparative assessment demonstrated that top heating led to the highest <em>T</em><sub>w</sub>, whereas side heating induced the greatest pressure drop. Finally, sinusoidal wavy channels were proposed, with amplitude <em>A</em>= 0.2 mm and period <em>p</em> = 4 mm exhibiting optimal flow and heat transfer capabilities for various heating position.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106895"},"PeriodicalIF":4.4,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145981962","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}

引用次数: 0

Critical process thresholds in foam injection molding revealed by real-time visualization 泡沫注射成型关键工艺阈值的实时可视化研究

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-16 DOI: 10.1016/j.supflu.2026.106897

Ai Lin Hong , Chun Yang Chiu , Cheng Yi Kao , Chen-Yu Fang , Kiday Fiseha Gebremedhin , Shu Kai Yeh , Sen Yeu Yang , Chul B. Park

Foam injection molding (FIM) has remained largely empirical due to the opacity of molds preventing direct observation of foaming dynamics. This study establishes a visualization platform for systematic investigation of FIM processes, enabling future research across diverse polymer systems. Building upon established methodologies, this work successfully reproduces and validates previous findings while extending investigations to unexplored parameter regimes. A custom-designed mold with integrated optics and pressure sensors enabled simultaneous visual and pressure monitoring of polystyrene foaming with CO₂. Systematic experiments investigated both low-pressure (LPFIM) and high-pressure (HPFIM) FIM with core-back technology, demonstrating the platform’s capability to capture fundamental process-structure relationships across different processing modes. In LPFIM, an insufficient mold venting design can affect mold filling, with better mold filling achieved at lower injection speeds (50 cm³/s) compared to higher speeds (80 cm³/s). This finding contrasts with previous studies using optimized venting systems, underscoring the crucial role of mold design in achieving LPFIM success. In HPFIM with core-back, a critical transition was observed at 0.8 mm core-back distance, triggering cell density increases from < 60 cells/cm³ to > 4500 cells/cm³. An optimal core-back velocity of 33 mm/s was identified, with higher velocities causing pressure rebound and rapid gas consumption that suppress further nucleation. These fundamental insights provide qualitative guidelines for process optimization while establishing a robust research platform for future investigations across different polymer-blowing agent systems.

泡沫注射成型（FIM）仍然很大程度上是经验的，由于模具的不透明性阻止了泡沫动力学的直接观察。本研究为FIM过程的系统研究建立了一个可视化平台，使未来的研究跨越不同的聚合物体系成为可能。在既定方法的基础上，这项工作成功地再现和验证了以前的发现，同时将调查扩展到未探索的参数体系。定制设计的模具集成了光学和压力传感器，可以同时对含有二氧化碳的聚苯乙烯发泡进行视觉和压力监测。系统实验研究了低压（LPFIM）和高压（HPFIM） FIM的核心技术，证明了该平台能够捕捉不同加工模式下基本的工艺结构关系。在LPFIM中，不充分的模具排气设计会影响模具填充，与较高的注射速度（80 cm3/s）相比，较低的注射速度（50 cm3/s）可以实现更好的模具填充。这一发现与先前使用优化通风系统的研究形成对比，强调了模具设计在实现LPFIM成功中的关键作用。在具有核背的HPFIM中，在0.8 mm核背距离处观察到一个临界转变，触发细胞密度从<； 60个细胞/cm3增加到>； 4500个细胞/cm3。确定了最佳岩心回送速度为33 mm/s，较高的速度会导致压力反弹和快速的气体消耗，从而抑制进一步成核。这些基本见解为工艺优化提供了定性指导，同时为未来不同聚合物发泡剂系统的研究建立了一个强大的研究平台。

{"title":"Critical process thresholds in foam injection molding revealed by real-time visualization","authors":"Ai Lin Hong , Chun Yang Chiu , Cheng Yi Kao , Chen-Yu Fang , Kiday Fiseha Gebremedhin , Shu Kai Yeh , Sen Yeu Yang , Chul B. Park","doi":"10.1016/j.supflu.2026.106897","DOIUrl":"10.1016/j.supflu.2026.106897","url":null,"abstract":"<div><div>Foam injection molding (FIM) has remained largely empirical due to the opacity of molds preventing direct observation of foaming dynamics. This study establishes a visualization platform for systematic investigation of FIM processes, enabling future research across diverse polymer systems. Building upon established methodologies, this work successfully reproduces and validates previous findings while extending investigations to unexplored parameter regimes. A custom-designed mold with integrated optics and pressure sensors enabled simultaneous visual and pressure monitoring of polystyrene foaming with CO<sub>2</sub>. Systematic experiments investigated both low-pressure (LPFIM) and high-pressure (HPFIM) FIM with core-back technology, demonstrating the platform’s capability to capture fundamental process-structure relationships across different processing modes. In LPFIM, an insufficient mold venting design can affect mold filling, with better mold filling achieved at lower injection speeds (50 cm<sup>3</sup>/s) compared to higher speeds (80 cm<sup>3</sup>/s). This finding contrasts with previous studies using optimized venting systems, underscoring the crucial role of mold design in achieving LPFIM success. In HPFIM with core-back, a critical transition was observed at 0.8 mm core-back distance, triggering cell density increases from < 60 cells/cm<sup>3</sup> to > 4500 cells/cm<sup>3</sup>. An optimal core-back velocity of 33 mm/s was identified, with higher velocities causing pressure rebound and rapid gas consumption that suppress further nucleation. These fundamental insights provide qualitative guidelines for process optimization while establishing a robust research platform for future investigations across different polymer-blowing agent systems.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106897"},"PeriodicalIF":4.4,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995411","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}

引用次数: 0

Recovery of phytochemicals from cimin black grape seeds with sub/super-critical carbon dioxide extraction 亚/超临界二氧化碳萃取法回收亚红黑葡萄籽中的植物化学物质

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-15 DOI: 10.1016/j.supflu.2026.106894

Tunahan Engin , Eyyup Karaogul , Sümeyra Al Çiçek , Ayhan Çiğdem , Duried Alwazeer , Kairat Bekbayev , Galiya Abdilova , Bakytzhan Bolkenov

In this study, Sub/Super-Critical carbon dioxide (scCO₂) extraction and response surface methodology (RSM) were applied as mathematical modeling and optimization approaches for the recovery of phytochemicals from grape seeds. The optimal extraction conditions were determined as 80 bar pressure, 60 °C temperature, and 5 min time. The total phenolic content (TPC) of the extract obtained under these conditions was 91.86 mg GAE/100 mL extract. Antioxidant activity was determined as 13,100.3 µmol TE/100 mL extract using the DPPH method and 2 004.93 µmol TE/100 mL extract using the ABTS method. Catechin (200.997 mg/L) was the most concentrated phenolic, and chlorogenic acid was the lowest one in the extract. Additionally, the epicatechin content was 91.12 mg/L, and the total phenolic content, as determined by HPLC, was 291.84 mg/L extract. Pearson correlation analysis showed a high correlation between the results obtained and the experimental data. The results were confirmed by the color distributions in the heat map, clustering in the PCA analysis, and hierarchical analysis. These results confirm the success of the modeling and optimization. In conclusion, the pressure, temperature, and time parameters were found to be decisive for achieving high bioactivity. Sub/Super-critical extraction is an effective method for extracting bioactive compounds from agricultural by-products such as grape seeds, using a process that's both efficient and environmentally friendly.

本研究以亚/超临界二氧化碳（scCO₂）提取和响应面法（RSM）为数学建模和优化方法，对葡萄种子中植物化学物质的回收进行了研究。最佳提取条件为压力80 bar，温度60℃，时间5 min。在此条件下得到的提取物总酚含量为91.86 mg GAE/100 mL提取物。DPPH法测定其抗氧化活性为13,100.3µmol TE/100 mL， ABTS法测定其抗氧化活性为2 004.93µmol TE/100 mL。其中儿茶素含量最高（200.997 mg/L），绿原酸含量最低。表儿茶素含量为91.12 mg/L，总酚含量为291.84 mg/L。Pearson相关分析表明，所得结果与实验数据具有较高的相关性。结果通过热图中的颜色分布、PCA分析中的聚类和层次分析得到证实。这些结果证实了建模和优化的成功。总之，压力、温度和时间参数是获得高生物活性的决定性因素。亚/超临界萃取是一种从葡萄籽等农业副产品中提取生物活性化合物的有效方法，该方法既高效又环保。

{"title":"Recovery of phytochemicals from cimin black grape seeds with sub/super-critical carbon dioxide extraction","authors":"Tunahan Engin , Eyyup Karaogul , Sümeyra Al Çiçek , Ayhan Çiğdem , Duried Alwazeer , Kairat Bekbayev , Galiya Abdilova , Bakytzhan Bolkenov","doi":"10.1016/j.supflu.2026.106894","DOIUrl":"10.1016/j.supflu.2026.106894","url":null,"abstract":"<div><div>In this study, Sub/Super-Critical carbon dioxide (scCO₂) extraction and response surface methodology (RSM) were applied as mathematical modeling and optimization approaches for the recovery of phytochemicals from grape seeds. The optimal extraction conditions were determined as 80 bar pressure, 60 °C temperature, and 5 min time. The total phenolic content (TPC) of the extract obtained under these conditions was 91.86 mg GAE/100 mL extract. Antioxidant activity was determined as 13,100.3 µmol TE/100 mL extract using the DPPH method and 2 004.93 µmol TE/100 mL extract using the ABTS method. Catechin (200.997 mg/L) was the most concentrated phenolic, and chlorogenic acid was the lowest one in the extract. Additionally, the epicatechin content was 91.12 mg/L, and the total phenolic content, as determined by HPLC, was 291.84 mg/L extract. Pearson correlation analysis showed a high correlation between the results obtained and the experimental data. The results were confirmed by the color distributions in the heat map, clustering in the PCA analysis, and hierarchical analysis. These results confirm the success of the modeling and optimization. In conclusion, the pressure, temperature, and time parameters were found to be decisive for achieving high bioactivity. Sub/Super-critical extraction is an effective method for extracting bioactive compounds from agricultural by-products such as grape seeds, using a process that's both efficient and environmentally friendly.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106894"},"PeriodicalIF":4.4,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995412","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}

引用次数: 0

Solubility of supercritical CO2 in biopolymers PBAT and PHBV 超临界CO2在生物聚合物PBAT和PHBV中的溶解度

IF 4.4 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Journal of Supercritical Fluids

Pub Date : 2026-01-15 DOI: 10.1016/j.supflu.2026.106893

Friso G. Versteeg , Guilherme de M.R. Lima , Francesco Picchioni , Kevin M. van Geem , Pablo Druetta

As environmental concerns surrounding conventional plastics continue to grow, biodegradable alternatives such as polybutylene adipate terephthalate (PBAT) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) have been and are gaining attention as promising candidates for sustainable polymeric foams production. These bioplastics offer potential for use in environmentally friendly foaming processes, particularly when paired with supercritical carbon dioxide (scCO₂), a non-toxic and inert foaming agent. Understanding the solubility of CO₂ in these polymers is critical for optimizing the foaming conditions and material performance. In this work, the solubility of scCO₂ in PBAT and PHBV was experimentally determined over a temperature range of 373 K to 413 K and pressures up to 130 bar using a magnetic suspension balance (MSB). In order to interpret the results and estimate the degree of swelling, the Sanchez–Lacombe Equation of State (SL-EoS) was applied. Since the solubility of CO₂ can be influenced by the semi-crystalline nature of the polymers, a crystallinity correction was incorporated into the model to better reflect the interaction of CO₂ with the amorphous regions. This adjustment improved the agreement between experimental and calculated values, providing a more accurate representation of solubility behaviour. The developed model serves as a useful predictive tool for designing efficient and sustainable foaming processes using PBAT and PHBV.

随着传统塑料对环境的关注不断增加，生物可降解的替代品，如聚己二酸丁二酯（PBAT）和聚（3-羟基丁酸-co-3-羟基戊酸酯）（PHBV）作为可持续聚合物泡沫生产的有希望的候选者已经并且正在受到关注。这些生物塑料为环保发泡工艺提供了潜力，特别是当与超临界二氧化碳（scCO2）（一种无毒的惰性发泡剂）配对时。了解二氧化碳在这些聚合物中的溶解度对于优化发泡条件和材料性能至关重要。在这项工作中，使用磁悬浮天平（MSB）在温度范围为373 K至413 K和压力高达130 bar的情况下，实验测定了scCO2在PBAT和PHBV中的溶解度。为了解释结果并估计膨胀程度，采用了Sanchez-Lacombe状态方程（SL-EoS）。由于CO2的溶解度会受到聚合物半结晶性质的影响，因此在模型中加入了结晶度校正，以更好地反映CO2与非晶态区域的相互作用。这种调整改善了实验值和计算值之间的一致性，提供了更准确的溶解度行为表示。所建立的模型为设计高效、可持续的PBAT和PHBV发泡工艺提供了有用的预测工具。

{"title":"Solubility of supercritical CO2 in biopolymers PBAT and PHBV","authors":"Friso G. Versteeg , Guilherme de M.R. Lima , Francesco Picchioni , Kevin M. van Geem , Pablo Druetta","doi":"10.1016/j.supflu.2026.106893","DOIUrl":"10.1016/j.supflu.2026.106893","url":null,"abstract":"<div><div>As environmental concerns surrounding conventional plastics continue to grow, biodegradable alternatives such as polybutylene adipate terephthalate (PBAT) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) have been and are gaining attention as promising candidates for sustainable polymeric foams production. These bioplastics offer potential for use in environmentally friendly foaming processes, particularly when paired with supercritical carbon dioxide (scCO<sub>2</sub>), a non-toxic and inert foaming agent. Understanding the solubility of CO<sub>2</sub> in these polymers is critical for optimizing the foaming conditions and material performance. In this work, the solubility of scCO<sub>2</sub> in PBAT and PHBV was experimentally determined over a temperature range of 373 K to 413 K and pressures up to 130 bar using a magnetic suspension balance (MSB). In order to interpret the results and estimate the degree of swelling, the Sanchez–Lacombe Equation of State (SL-EoS) was applied. Since the solubility of CO<sub>2</sub> can be influenced by the semi-crystalline nature of the polymers, a crystallinity correction was incorporated into the model to better reflect the interaction of CO<sub>2</sub> with the amorphous regions. This adjustment improved the agreement between experimental and calculated values, providing a more accurate representation of solubility behaviour. The developed model serves as a useful predictive tool for designing efficient and sustainable foaming processes using PBAT and PHBV.</div></div>","PeriodicalId":17078,"journal":{"name":"Journal of Supercritical Fluids","volume":"232 ","pages":"Article 106893"},"PeriodicalIF":4.4,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145981961","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}

引用次数: 0