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High-pressure phase equilibrium for carbon dioxide solubility with biofuels: Experimental and thermodynamic insights in 2,5-dimethylfuran and methyl levulinate 生物燃料中二氧化碳溶解度的高压相平衡:2,5-二甲基呋喃和乙酰丙酸甲酯的实验和热力学见解
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-13 DOI: 10.1016/j.supflu.2024.106378

The solubility of carbon dioxide in two solvents, 2,5-dimethylfuran and methyl levulinate, were measured to high pressure, up to 9.1 MPa, at three different temperatures (283.15, 303.15 and 323.15) K. The new data were measured using both the isothermal synthetic technique and the variable volume synthetic method. Two methods were utilised to provide a level of data validation. The uncertainties in the measured data were critically estimated. The experimental phase equilibrium data were modeled using the Peng-Robinson equation of state and the Wong-Sandler mixing rule with a single set of binary interaction parameters for each system. The data indicated that the solubility of carbon dioxide in both 2,5-dimethylfuran and methyl levulinate at high pressures was relatively low, suggesting a low capacity of these biofuels to dissolve carbon dioxide at high pressure.

在三种不同温度(283.15、303.15 和 323.15)K 下测量了二氧化碳在 2,5-二甲基呋喃和乙酰丙酸甲酯两种溶剂中的高压溶解度,最高可达 9.1 兆帕。使用这两种方法提供了一定程度的数据验证。对测量数据的不确定性进行了严格估算。使用彭-罗宾逊状态方程和黄-桑德勒混合规则对实验相平衡数据进行建模,每个系统使用一组二元相互作用参数。数据表明,在高压下二氧化碳在 2,5-二甲基呋喃和乙酰丙酸甲酯中的溶解度相对较低,这表明这些生物燃料在高压下溶解二氧化碳的能力较低。
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引用次数: 0
Enhancing anti-diabetic activity and reducing cytotoxicity of T. crispa extracts through sustainable approach of pressurized hot water extraction and micelle-mediated separation 通过加压热水萃取和胶束介导分离的可持续方法提高酥树蕨提取物的抗糖尿病活性并降低其细胞毒性
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-13 DOI: 10.1016/j.supflu.2024.106377

In this study, pressurized hot water extraction (PHWE) was evaluated for the recovery of anti-diabetic borapetoside C (BPC) from T. crispa stems. The maximum BPC extraction efficiency obtained at 100 ˚C, 2.5 MPa and 5.0 mL/min was considerably higher than that obtained by the conventional methods. Under optimized conditions, one-site kinetic desorption model could most accurately describe the PHWE behavior, suggesting an intra-particle diffusion-controlled mechanism. The undesirable compounds in the extract were further removed by micelle-mediated separation (MMS), in which Tween 80 was added, followed by NaCl addition and slight temperature increase to induce phase separation. At the most suitable MMS condition, with 0.028 mM Tween 80, 0.4 M NaCl, at 85 ˚C, the majority (87 %) of BPC could be recovered in the aqueous phase after 40 min. After MMS, the resulting extract exhibited low cytotoxicity against L6 and HepG2 cells while maintaining significant α-glucosidase and α-amylase inhibition activities.

本研究评估了加压热水萃取法(PHWE)从酥树茎中回收抗糖尿病的硼磷酯 C(BPC)的效果。在 100 ˚C、2.5 MPa 和 5.0 mL/min 条件下获得的最大 BPC 提取效率大大高于传统方法。在优化条件下,单位点动力学解吸模型能最准确地描述 PHWE 的行为,表明这是一种粒子内扩散控制机制。通过胶束介导分离(MMS)进一步去除提取物中的不良化合物,在此过程中加入吐温80,然后加入NaCl并略微升温以诱导相分离。在最合适的 MMS 条件下(0.028 mM Tween 80,0.4 M NaCl,85 ˚C),40 分钟后,水相中大部分(87%)的 BPC 得以回收。经 MMS 处理后,所得提取物对 L6 和 HepG2 细胞的细胞毒性较低,但仍具有显著的 α-葡萄糖苷酶和 α-淀粉酶抑制活性。
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引用次数: 0
Study of potassium deactivation rule in supercritical water gasification of coal with K2CO3 as catalyst 以 K2CO3 为催化剂的超临界水煤气化过程中钾失活规律研究
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-12 DOI: 10.1016/j.supflu.2024.106375

K2CO3 has a good catalytic effect in supercritical water gasification (SCWG) of coal. However, researchers have mainly focused on the effects of coal gasification, while the potassium mass transfer process has rarely been studied. Herein, the distribution pattern of potassium during the SCWG of coal and the factors influencing potassium deactivation were experimentally obtained. Through the detection and analysis of the residues after the SCWG of coal, it is found that potassium only exists in the forms of liquid and solid and the potassium in the residue exists in the form of insoluble potassium silica alumina, which does not have a catalytic effect. At a high reaction temperature, the reaction time is longer, and when the silica–aluminum content in coal is higher, the potassium deactivate rate is also higher. The molar contents of potassium and aluminum in the coal gasification residue are linearly correlated, with a ratio of approximately 1:1. Reducing the aluminum content in coal can effectively reduce potassium deactivation. In the SCWG of the Hebi coal, the deactivation rate of potassium reduced from 80.88 % to 17.75 % after acid washing. In the SCWG of the ash-free coal, the carbon gasification efficiency (CE) and potassium content in the liquid were above 95 % after each experiment, there was no deactivation of potassium, and the residual potassium solution remained catalytically effective after the SCWG of the ash-free coal.

K2CO3 在煤的超临界水气化(SCWG)中具有良好的催化作用。然而,研究人员主要关注煤的气化效果,而对钾的传质过程研究甚少。本文通过实验获得了煤在超临界水气化过程中钾的分布规律以及影响钾失活的因素。通过对煤炭超临界水分解后残留物的检测和分析,发现钾只以液态和固态两种形式存在,残留物中的钾以不溶性硅铝钾的形式存在,不具有催化作用。反应温度越高,反应时间越长,煤中硅铝含量越高,钾的失活率也越高。煤气化残渣中钾和铝的摩尔含量呈线性相关,比例约为 1:1。降低煤中铝的含量可以有效减少钾的失活。在鹤壁煤的 SCWG 中,酸洗后钾的失活率从 80.88% 降至 17.75%。在无灰份煤的SCWG中,每次实验后的碳气化效率(CE)和液体中的钾含量都在95%以上,钾没有失活,残留的钾溶液在无灰份煤的SCWG后仍然有效。
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引用次数: 0
Density and viscosity of orange peel oil saturated with pressurized CO2 加压二氧化碳饱和橙皮油的密度和粘度
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-08 DOI: 10.1016/j.supflu.2024.106373

In this work, we measure the density and viscosity of CO2 saturated orange peel oil liquid mixtures under moderated pressure for the purpose of supercritical process engineering design. A high-pressure falling weight viscometer is used to measure the viscosity of saturated liquid mixtures of orange oil + CO2 at different temperatures (293 K to 333 K) and saturated pressures (2 MPa to 10.3 MPa). An important variation of viscosity (0.35.10−3 Pa.s to 1.10 10−3 Pa.s) is reported in the range of operating conditions. Results show the operating temperature influences the viscosity of both the pure oil and the CO2-saturated oily substrates. The new viscosity data correlates with a simple Arrhenius modified type model.

在这项工作中,我们测量了二氧化碳饱和橘皮油液体混合物在适度压力下的密度和粘度,目的是进行超临界工艺工程设计。我们使用高压失重式粘度计测量了橘子油 + CO2 饱和液体混合物在不同温度(293 K 至 333 K)和饱和压力(2 MPa 至 10.3 MPa)下的粘度。据报告,在工作条件范围内,粘度的变化很大(0.35.10-3 Pa.s 至 1.10 10-3 Pa.s)。结果表明,工作温度会影响纯油和二氧化碳饱和油基的粘度。新的粘度数据与简单的阿伦尼斯改进型模型相关。
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引用次数: 0
Ultrasound pretreatment combined with supercritical CO2 extraction of Costus spicatus leaf extract 超声波预处理与超临界二氧化碳萃取相结合的木贼叶提取物
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-07 DOI: 10.1016/j.supflu.2024.106372

This work aimed to obtain extracts from Costus spicatus leaves through ultrasonic pretreatment in supercritical CO2 extraction (UAE+SFE). A central composite design was used to evaluate the influence of temperature (36–64 °C), pressure (8–20 MPa), and cosolvent (0–20 %w) in terms of overall yield and chemical composition. Morphology using scanning electron micrograph (SEM), total phenolic content, content of total flavonoid, antioxidant (DPPH and ABTS), and antibacterial activities were evaluated. UAE+SFE showed a more notable overall yield, with 6.97 %. In the SEM, the sample treated with UAE+SFE significantly impacted tissue structures, improving the selectivity of SFE regarding linolenic acid, leading to a maximum composition value of 62.5 % area according to GC-MS. Furthermore, the UAE+SFE extract exhibited strong antimicrobial activity compared to the extract obtained by the SFE technique. Based on the pioneering results, the bioactives obtained are promising and interesting for application in the cosmetic, pharmaceutical, and food industries.

本研究旨在通过超临界二氧化碳萃取(UAE+SFE)中的超声波预处理从树叶中获得提取物。采用中心复合设计评估了温度(36-64 °C)、压力(8-20 MPa)和助溶剂(0-20 %w)对总收率和化学成分的影响。使用扫描电子显微镜(SEM)对其形态、总酚含量、总黄酮含量、抗氧化性(DPPH 和 ABTS)和抗菌活性进行了评估。UAE+SFE 的总收率较高,为 6.97%。在扫描电子显微镜下,用 UAE+SFE 处理过的样品对组织结构产生了显著影响,提高了 SFE 对亚麻酸的选择性,从而使 GC-MS 显示的最大成分值达到 62.5 %。此外,与通过 SFE 技术获得的提取物相比,UAE+SFE 提取物具有很强的抗菌活性。基于这些开创性的结果,所获得的生物活性物质有望在化妆品、制药和食品行业中得到应用。
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引用次数: 0
Effect of mild subcritical fluid treatment on meat quality of farmed large yellow croakers 温和亚临界流体处理对养殖大黄鱼肉质的影响
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-05 DOI: 10.1016/j.supflu.2024.106370

Farmed large yellow croaker fish have stronger fishy smell and less tender texture than wild-caught ones, mostly caused by the high fat accumulation from aquaculture feeding patterns. To improve the commercial value of fillets, this study investigated a mild subcritical fluid treatment with subcritical butane (SBE) and dimethyl ether (SDME). Changes in the chemical compositions, volatile flavor compounds (VFCs) and protein denaturation were determined for 1–5 h treatments. The results showed 24 % and 44 % defatting levels under SBE and SDME treatment, respectively. GC-MS showed that SDME could induce a significant reduction of total VFC content, especially for the dominant aldehydes. There was less n-nonanal (14.65–40.13 mg/kg) and octanal content (1.67–7.21 mg/kg), no detection of trans, trans-2,4-decadienal in the SDME treated samples in comparison to those treated with SBE. The results showed that SDME treatment for 3 h had the best defatting effect, good deodorization effect and less degradation of fish protein.

与野生捕捞的大黄鱼相比,养殖的大黄鱼腥味更重、肉质更不鲜嫩,这主要是由于水产养殖投喂模式造成的高脂肪积累所致。为了提高鱼片的商业价值,本研究采用亚临界丁烷(SBE)和二甲醚(SDME)进行了温和的亚临界流体处理。测定了处理 1-5 小时后化学成分、挥发性风味化合物(VFCs)和蛋白质变性的变化。结果显示,SBE 和 SDME 处理的脱脂程度分别为 24% 和 44%。气相色谱-质谱(GC-MS)显示,SDME 能显著降低 VFC 的总含量,尤其是主要的醛类。与使用 SBE 处理的样品相比,SDME 处理的样品中正壬醛(14.65-40.13 毫克/千克)和辛醛(1.67-7.21 毫克/千克)含量较少,没有检测到反式、反式-2,4-癸二烯醛。结果表明,SDME 处理 3 小时的脱脂效果最好,除臭效果好,鱼肉蛋白质降解较少。
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引用次数: 0
Investigation of supercritical CO2 corrosion behavior of X80 carbon steel in pipelines: An in situ experimental and DFT study 管道中 X80 碳钢的超临界二氧化碳腐蚀行为研究:现场实验和 DFT 研究
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-05 DOI: 10.1016/j.supflu.2024.106371

The electrochemical corrosion behavior of X80 carbon steel was investigated in a supercritical CO2 (sCO2) environment at 60 ℃ and 9 MPa, by in-situ experiments and density functional theory (DFT) calculations, revealing the corrosion mechanism. For in situ electrochemical measurements, two novel CO2-rich and H2O-rich cells were developed to replace the traditional three-electrode cell. Electrochemical impedance spectroscopy revealed distinct differences in the corrosion behavior between CO2-rich and H2O-rich environments during the later stages of testing. In H2O-rich environments, as corrosion time increased, the corrosion product layer gradually changed from porous to dense, eventually forming a protective layer. In CO2-rich environments, corrosion occurs mainly in areas where water condenses to form FeCO3. Simultaneously, microscopic calculations provided evidence for the three-step sCO2 hydrolysis mechanism and the formation of FeCO3 products.

通过原位实验和密度泛函理论(DFT)计算,研究了 X80 碳钢在 60 ℃ 和 9 MPa 的超临界 CO(sCO)环境中的电化学腐蚀行为,揭示了腐蚀机理。为进行原位电化学测量,开发了两种新型富含 CO 和 HO 的电池,以取代传统的三电极电池。电化学阻抗光谱显示,在测试的后期阶段,富含 CO 和富含 HO 环境中的腐蚀行为存在明显差异。在富含 HO 的环境中,随着腐蚀时间的延长,腐蚀产物层逐渐从多孔变为致密,最终形成保护层。在富含 CO 的环境中,腐蚀主要发生在水冷凝形成 FeCO 的区域。同时,微观计算为三步 sCO 水解机制和 FeCO 产物的形成提供了证据。
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引用次数: 0
Solubility of supercritical CO2 in polystyrene 超临界二氧化碳在聚苯乙烯中的溶解度
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-08-03 DOI: 10.1016/j.supflu.2024.106374

Expanded polystyrene (ePS) plays an important role in the food packaging industry. However, the foaming process is environmentally unfriendly. A sustainable alternative is dissolving supercritical CO2 (scCO2) in the polystyrene (PS) matrix. Most studies so far were performed at temperatures above the PS glass transition temperature; however, a more general temperature window is desirable. In this work, the solubility of scCO2 in polystyrene was measured at 323 K, 343 K, 363 K and 383 K and pressure up to 130 bar using a magnetic suspension balance (MSB). It was concluded that the solubility of CO2 in PS decreases with temperature and increases with pressure. The Sanchez-Lacombe Equation of State was utilized to estimate the degree of swelling. The model developed was able to derive the experimentally determined solubilities after correction for the swelling. The interaction parameter, k12, turned out to be only a function of temperature. With these results the solubility and swelling of PS in scCO2 can be more accurately assessed for different temperatures and pressures.

发泡聚苯乙烯(ePS)在食品包装行业发挥着重要作用。然而,发泡工艺并不环保。一种可持续的替代方法是在聚苯乙烯(PS)基质中溶解超临界 CO(scCO)。迄今为止,大多数研究都是在高于 PS 玻璃转化温度的条件下进行的;然而,我们需要一个更宽泛的温度窗口。在这项工作中,使用磁悬浮天平 (MSB) 在 323 K、343 K、363 K 和 383 K 以及高达 130 bar 的压力下测量了 scCO 在聚苯乙烯中的溶解度。结果表明,一氧化碳在聚苯乙烯中的溶解度随温度升高而降低,随压力升高而升高。利用 Sanchez-Lacombe 状态方程估算了溶胀程度。在对溶胀进行修正后,所建立的模型能够推导出实验测定的溶解度。结果表明,相互作用参数 k 只是温度的函数。有了这些结果,就可以更准确地评估 PS 在不同温度和压力下在 scCO 中的溶解度和溶胀度。
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引用次数: 0
Optimization of supercritical carbon dioxide pretreatment of Flaveria bidentis leaves prior extraction of sulfated flavonoids with subcritical water 在用亚临界水提取硫酸化黄酮类化合物之前,优化用超临界二氧化碳预处理黄花菜叶的方法
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-26 DOI: 10.1016/j.supflu.2024.106349

Flaveria bidentis is an invasive plant containing Sulfated Flavonoids (SFs) with therapeutic potential. The extraction of these compounds would add value to the biomass generated during weeding. This work reports the optimization of the pretreatment of F. bidentis leaves with supercritical CO2 (P-SC-CO2) prior extraction of these compounds using subcritical water extraction. The combined effect of different levels of the three factors on P-SC-CO2, Time, Pressure and Depressurization rate, was investigated with Response Surface Methodology. The optimal pretreatment conditions were as follows: Time = 30 min, Pressure = 30 MPa and Depressurization rate = 2 kg CO2/h. Under these conditions, 72.45 ± 0.99 mg of totals SFs/100 g of leaves was recovered, practically doubling total SFs extraction yield in the absence of pretreatment. In addition, the structural damage caused by P-SC-CO2 on the leaves was detected using Scanning Electron Microscopy.

黄花菜是一种入侵植物,含有具有治疗潜力的硫酸黄酮类化合物(SFs)。提取这些化合物将增加除草过程中产生的生物质的价值。本研究报告了在使用亚临界水萃取法萃取这些化合物之前,用超临界二氧化碳(P-SC-CO2)对双子叶植物叶片进行预处理的优化方法。采用响应面法研究了时间、压力和减压率这三个因素对 P-SC-CO2 不同水平的综合影响。最佳预处理条件如下时间 = 30 分钟,压力 = 30 兆帕,减压率 = 2 千克二氧化碳/小时。在这些条件下,每 100 克叶片可回收 72.45 ± 0.99 毫克的总 SFs,实际上是未进行预处理时总 SFs 提取率的两倍。此外,还利用扫描电子显微镜检测了 P-SC-CO2 对叶片结构造成的破坏。
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引用次数: 0
Compressed n-propane extraction of umari pulp oil: A rich Amazon source of β-carotene and omega-9 压缩正丙烷萃取乌玛里果肉油:亚马逊河流域β-胡萝卜素和欧米伽-9的丰富来源
IF 3.4 3区 工程技术 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-26 DOI: 10.1016/j.supflu.2024.106369

Compressed n-propane extraction (CPE) was applied to umari fruit (Poraqueiba sericea Tul.) pulp to obtain an oil rich in high added-value components. CPE was performed at different temperatures and flow rate, which was compared to conventional extraction (Soxhlet). The oils were analyzed for global yields, fatty acid composition, β-carotene content, antioxidant activity, total phenolics content (TPC) total flavonoids (TF), and thermal behavior. The highest extraction yield (29.2 wt%) was obtained with CPE at 80 °C and 3 mL.min−1, being higher than that obtained by Soxhlet. The flow rate variation had a significant effect (p < 0.05) on the oil extraction yield, while the temperature had a negative effect. The umari oil obtained by CPE emerges as a rich source of oleic acid (omega-9) and β-carotene (vitamin A precursor), with potential to be applied in various industrial segments and inserted into the Amazon bioeconomy scenario.

对乌梅果(Poraqueiba sericea Tul.)果肉进行压缩正丙烷萃取(CPE),以获得富含高附加值成分的油脂。正丙烷萃取在不同的温度和流速下进行,并与传统萃取(索氏提取法)进行了比较。对油的总产量、脂肪酸组成、β-胡萝卜素含量、抗氧化活性、总酚含量(TPC)、总黄酮含量(TF)和热行为进行了分析。CPE 在 80 °C 和 3 mL.min-1 条件下的提取率最高(29.2 wt%),高于索氏提取法。流速变化对萃取率有显著影响(p < 0.05),而温度则有负面影响。通过 CPE 获得的乌玛里油含有丰富的油酸(omega-9)和 β-胡萝卜素(维生素 A 前体),具有应用于各种工业领域并融入亚马逊生物经济情景的潜力。
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引用次数: 0
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Journal of Supercritical Fluids
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