kinetic model

动力学模型
  • 文章类型: Journal Article
    为了有效地利用红松种子鳞片的资源,一种林业废物,对提取的严格研究,净化,稳定性,并对来自这些种子鳞片的原花青素进行了自由基清除能力。动力学模型表明,在超声条件下,原花青素含量在0.5h内达到2.66mg/g。最佳储存参数包括黑暗,4°C,和pH4。混合物的聚合度以及高,低聚合物组分的聚合度分别为4.89,7.42和3.07,低聚合物组分表现出最高的自由基清除活性。通过HPLC-QE-MS/MS,1HNMR,和FT-IR分析,我们鉴定了原花青素B1,原花青素B2,(-)-表儿茶素,和聚合三聚体酯。红松原花青素具有较高的分子量,复杂的内部分子结构,和值得称赞的稳定性,结晶需要升高的温度。因此,来自红松种子鳞片的原花青素已成为非常有前途的新型天然抗氧化剂。
    To efficiently harness resources from Pinus koraiensis seed scales, a type of forestry waste, rigorous studies on the extraction, purification, stability, and free radical scavenging capacity of the proanthocyanidins derived from these seed scales were conducted. Kinetic models showed that under ultrasonic conditions, the proanthocyanidins content reached 2.66 mg/g within 0.5 h. The optimal storage parameters include darkness, 4 °C, and pH 4. The degrees of polymerization of the mixture and the high- and low-polymer components were 4.89, 7.42 and 3.07, respectively, with the low-polymer component exhibiting the highest radical scavenging activity. Through HPLC-QE-MS/MS, 1H NMR, and FT-IR analyses, we identified proanthocyanidin B1, proanthocyanidin B2, (-)-epicatechin, and polymeric trimer esters. The Pinus koraiensis proanthocyanidins exhibited a high molecular weight, a complex internal molecular structure, and commendable stability, with crystallization requiring elevated temperatures. Therefore, the proanthocyanidins from Pinus koraiensis seed scales have emerged as highly promising novel natural antioxidants.
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  • 文章类型: Journal Article
    反应动力学的研究是商业工艺设计中最关键的方面之一。目前的研究调查了使用钙钛矿催化剂的费托合成动力学。通过热溶胶-凝胶技术制备了LaFe0.7Co0.3O3钙钛矿催化剂,并使用BET进行了表征,XRD,SEM,和H2-TPR技术。根据操作条件(例如H2/CO:1-2,压力:10-20barg,温度:240-300°C,和GHSV:30001/h),在固定床反应器中进行了费-托反应动力学(CO转化)。使用Langmuir-Hinshelwood-Hougen-Watson(LHHW)理论的框架,得出了18个CO转化的动力学表达式,并逐一拟合实验数据,确定最佳条件。相关性来自实验数据,并使用LHHW形式进行了很好的拟合(根据烯醇机制,一氧化碳和解离的氢原子在催化剂表面吸附并反应)-rCO=kpbCOPCO(bH2PH2)0.5/(1+bCOPCO+(bH2PH2)0.5)2。最后,在各种操作条件下,根据Arrhenius方程确定了最佳动力学模型的活化能。钙钛矿催化剂的活化能在240-300°C的温度下约为106.25kJ/mol,压力10-20barg,和H2/CO比1-2,其低于其他类型的催化剂。因此,催化剂在高温下活化,表现出稳定的性能,没有任何温度失控和焦化问题。
    The investigation of the reaction\'s kinetics is one of the most crucial aspects of the design of a commercial process. The current research investigates the kinetics of Fischer-Tropsch synthesis using a perovskite catalyst. The LaFe0.7 Co0.3 O3 perovskite catalyst was prepared via the thermal sol-gel technique and characterized using BET, XRD, SEM, and H2-TPR techniques. According to operating conditions (e.g. H2/CO: 1-2, pressure: 10-20 barg, temperature: 240-300 °C, and GHSV: 3000 1/h), Fischer-Tropsch reaction kinetics (CO conversion) were carried out in a fixed-bed reactor. Using the framework of Langmuir-Hinshelwood-Hougen-Watson (LHHW) theories, 18 kinetic expressions for CO conversion were derived, and all were fitted to experimental data one by one to determine the optimum condition. The correlation was derived from experimental data and well-fitted using LHHW form (according to the enol mechanism, carbon monoxide and dissociated hydrogen atoms are adsorbed and reacted on the surface of the catalyst) -rCO = kpbCOPCO(bH2PH2)0.5/(1 + bCOPCO + (bH2PH2)0.5)2. Finally, the activation energy of the optimum kinetic model was determined with respect to the Arrhenius equation under various operating conditions. The activation energy of perovskite catalyst is about 106.25 kJ/mol at temperatures 240-300 °C, pressures 10-20 barg, and H2/CO ratios 1-2, which is lower than other types of catalyst. Therefore, the catalyst was activated at a high temperature and demonstrated stable performance without any temperature runaway and coking issues.
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  • 文章类型: Journal Article
    在这项工作中,开发了一种用于从甘油中生产琥珀酸的琥珀酸A.sucdinogenes发酵的生物工艺,采用循环的连续生物反应器。此外,构建了一个新的生物过程模型,基于现有的双底物限制模型,通过一系列操作参数的实验结果进行了验证。该模型用于成功预测连续发酵过程的动力学,随后用于优化研究以计算最佳条件。稀释率,回流速率和进料甘油浓度,最大限度地提高生物琥珀酸的生产率。此外,计算了最佳体积生产率和甘油转化率组合的帕累托前沿。最大容积生产率为0.518g/L/h,是在最佳计算条件下实现的,经过实验验证。这是迄今为止报道的最高生物琥珀酸生产率,对于这样一个连续的生物过程。
    In this work, a bioprocess for the fermentation of A. succinogenes for the production of succinic acid from glycerol was developed, employing a continuous bioreactor with recycle. Moreover, a new bioprocess model was constructed, based on an existing double substrate limitation model, which was validated with experimental results for a range of operating parameters. The model was used to successfully predict the dynamics of the continuous fermentation process and was subsequently employed in optimisation studies to compute the optimal conditions, dilution rate, reflux rate and feed glycerol concentration, that maximise the productivity of bio-succinic acid. In addition, a Pareto front for optimal volumetric productivity and glycerol conversion combinations was computed. Maximum volumetric productivity of 0.518 g/L/h, was achieved at the optimal computed conditions, which were experimentally validated. This is the highest bio-succinic acid productivity reported so far, for such a continuous bioprocess.
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  • 文章类型: Journal Article
    现代人在日常生活中花在汽车上的时间越来越多,而且车内甲醛的污染可能直接影响人们的身体健康。太阳能热催化氧化技术是净化汽车甲醛的一种潜在方法。以改性共沉淀法制备MnOx-CeO2为主要催化剂,和基本特征(SEM,N2吸附,H2-TPR,UV-可见吸光度)也进行了详细分析。建立了模拟汽车环境中甲醛的太阳能光热催化作用的实验研究。结果表明,实验箱内温度越高(56.7±0.2°C,62.6±0.2°C,68.2±0.2°C),催化降解甲醛效果越好(甲醛降解率:76.2%,78.3%,82.1%)。随着初始甲醛浓度的增加(200ppb,500ppb,1000ppb),催化效果先升高后降低(甲醛降解率:63%,78.3%,70.6%)。随着负载比(10g/m2,20g/m2,40g/m2)的增加,催化效果逐渐上升,甲醛降解率为62.8%,78.3%,和81.1%,分别。根据Eley-Rideal(ER)模型的表达式,Langmuir-Hinshelwood(LH)模型,和Mars-VanKrevelen(MVK)模型,对实验结果进行了拟合和验证,并且发现ER模型具有很高的拟合度。更适合在实验舱中解释MnOx-CeO2催化剂对甲醛的催化机理,其中甲醛处于吸附状态,氧气处于气相。启示:从目前的研究现状来看,车辆已经成为人们不可或缺的出行方式,车内空气质量不容乐观。大多数车辆普遍存在甲醛超标的现象。车内甲醛的特点是持续释放,尤其是在炎热的夏天,车内温度在太阳辐射下急剧上升。此时,甲醛浓度超标4到5倍,这会对乘客的健康造成巨大损害。为了改善车内空气质量,必须采用正确的净化技术来降解甲醛。这种情况带来的问题是如何有效地利用车内太阳辐射和高温来降解车内甲醛。因此,本研究利用热催化氧化技术对夏季汽车高温环境中甲醛进行催化降解。选择的催化剂是MnOx-CeO2,主要是因为氧化锰(MnOx)本身是过渡金属氧化物中挥发性有机化合物(TCO)最有效的催化剂,CeO2具有优异的储氧释放能力和氧化活性,这有助于提高MnOx的活性。最后,温度的影响,对实验中甲醛的初始浓度和催化剂的负载量进行了探索,并分析了MnOx-CeO2催化剂热催化氧化甲醛的动力学模型,为今后该研究在实践中的应用提供技术支持。
    Modern people spend more and more time in cars in their daily lives, and the pollution of formaldehyde in the car may directly affect people\'s health. Thermal catalytic oxidation technology by solar light is a potential way to purify formaldehyde in cars. MnOx-CeO2 was prepared by the modified co-precipitation method as the main catalyst, and the basic characteristic (SEM, N2 adsorption, H2-TPR, UV-visible absorbance) were also analyzed in detail. The experimental study was set up to simulate the solar photothermal catalysis of formaldehyde in-car environment. The results showed that the higher the temperature in the experimental box (56.7 ± 0.2°C, 62.6 ± 0.2°C, 68.2 ± 0.2°C), the better the formaldehyde degradation by catalytic effect (formaldehyde degradation percentage: 76.2%, 78.3%, 82.1%). With increase of the initial formaldehyde concentration (200 ppb, 500 ppb, 1000 ppb), the catalytic effect first increased and then decreased (formaldehyde degradation percentage: 63%, 78.3%, 70.6%). The catalytic effect risen gradually with the increase of load ratio (10g/m2, 20g/m2, and 40g/m2), and the formaldehyde degradation percentages were 62.8%, 78.3%, and 81.1%, respectively. According to the expressions of the Eley-Rideal (ER) model, the Langmuir-Hinshelwood (LH) model, and the Mars-Van Krevelen (MVK) model, the experimental results were fitted and verified, and it was found that the ER model had a high degree of fit. It is more suitable to explain the catalytic mechanism of formaldehyde by MnOx-CeO2 catalyst in the experimental cabin, where formaldehyde is in the adsorption state and oxygen is in the gas phase.Implications: Judging from the current research status, vehicles have become an indispensable mode of travel for people, and the air quality in the vehicle is not optimistic. Most vehicles generally have the phenomenon of excessive formaldehyde. The characteristic of formaldehyde in the car is the continuous release, especially in the hot summer, the temperature inside the car rises sharply under the sun radiation. At this time, the formaldehyde concentration exceeds the standard by 4 to 5 times, which can cause great damage to the health of the passengers. In order to improve the air quality in the car, it is necessary to adopt the correct purification technology to degrade formaldehyde. The problem brought by this situation is how to effectively use solar radiation and high temperature in the car to degrade formaldehyde in the car. Therefore, this study uses the thermal catalytic oxidation technology to catalyze the degradation of formaldehyde in the high temperature environment of the car in summer. The selected catalyst is MnOx-CeO2, mainly because manganese oxide (MnOx) itself is the most effective catalyst for volatile organic compounds (TCO) among transition metal oxides, and CeO2 has excellent oxygen storage and release capacity and Oxidation activity, which helps to improve the activity of MnOx. Finally, the effects of temperature, initial concentration of formaldehyde and catalyst loading on the experiment were explored, and the kinetic model of thermal catalytic oxidation of formaldehyde with MnOx-CeO2 catalyst was analyzed to provide technical support for the future application of this research in practice.
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  • 文章类型: Journal Article
    The parameterization of kinetic models requires measurement of fluxes and/or metabolite levels for a base strain and a few genetic perturbations thereof. Unlike stoichiometric models that are mostly invariant to the specific strain, it remains unclear whether kinetic models constructed for different strains of the same species have similar or significantly different kinetic parameters. This important question underpins the applicability range and prediction limits of kinetic reconstructions. To this end, herein we parameterize two separate large-scale kinetic models using K-FIT with genome-wide coverage corresponding to two distinct strains of Saccharomyces cerevisiae: CEN.PK 113-7D strain (model k-sacce306-CENPK), and growth-deficient BY4741 (isogenic to S288c; model k-sacce306-BY4741). The metabolic network for each model contains 306 reactions, 230 metabolites, and 119 substrate-level regulatory interactions. The two models (for CEN.PK and BY4741) recapitulate, within one standard deviation, 77% and 75% of the fitted dataset fluxes, respectively, determined by 13C metabolic flux analysis for wild-type and eight single-gene knockout mutants of each strain. Strain-specific kinetic parameterization results indicate that key enzymes in the TCA cycle, glycolysis, and arginine and proline metabolism drive the metabolic differences between these two strains of S. cerevisiae. Our results suggest that although kinetic models cannot be readily used across strains as stoichiometric models, they can capture species-specific information through the kinetic parameterization process.
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  • 文章类型: Journal Article
    在本研究中,使用硫酸吸附结晶紫(CV)染料,活化了来自绿藻植物茎的生物质。研究了CV染料的吸附操作,考虑了pH等变量的影响,初始染料浓度,时间,吸附剂用量,和温度。伪二阶方程最适合动力学研究。热力学参数,如活化能(9.56kJ/mol),吉布斯能量变化(81.43至96.7kJ/mol),焓变(6.89kJ/mol),计算了熵变(-254.4J/molK)。响应面法估计在pH(4.902)下,吸附剂用量(8.33g/L),染料浓度(82.30ppm),和温度(300.13K)染料去除97.53%是可能的。FTIR,SEM,XRD,BJH,和BET确认吸附操作。吸附剂可有效重复使用3次循环。最适合吸附操作的Langmuir等温线用于设计用于大规模操作的理论单级间歇吸附器。
    In the present study, biomass from the Chromolaena odorata plant\'s stem was activated using sulfuric acid to adsorb crystal violet (CV) dye. The adsorption operation of CV dye was studied considering the effect of variables like pH, initial dye concentration, time, adsorbent dosage, and temperature. The pseudo-second-order equation best fitted the kinetic study. The thermodynamic parameters such as activation energy (9.56 kJ/mol), change in Gibbs energy (81.43 to 96.7 kJ/mol), enthalpy change (6.89 kJ/mol), and entropy change (-254.4 J/mol K) were calculated. Response surface methodology estimated that at pH (4.902), adsorbent dosage (8.33 g/L), dye concentration (82.30 ppm), and temperature (300.13 K) dye removal of 97.53% is possible. FTIR, SEM, XRD, BJH, and BET confirmed adsorption operation. The adsorbent can be reused for 3 cycles effectively. Langmuir isotherm which best fitted the adsorption operation was used for designing a theoretical single-stage batch adsorber for large-scale operation.
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  • 文章类型: Journal Article
    利用湿法烟气脱硝技术,提出了控制烟气氮氧化物排放的创新策略。使用环糊精(CD)作为添加剂促进亚硫酸盐吸收剂对NO2的吸收。与亚硫酸盐溶液(59.12%)的吸收相比,使用CD的瞬时吸收效率提高到94.57%。此外,48小时的连续吸收表明CD的循环利用。CD的有利作用归因于促进整个NO2吸收-溶解过程的限制步骤,该过程包括水溶性和气液传质。此外,我们提出了CD/亚硫酸盐混合溶液吸收NO2的潜在机理,其中添加剂的有利作用与其对气相和液相的两亲行为有关。此外,根据不同的操作条件,建立了描述气液转移速率和宏观吸收速率的动力学模型。该模型解释了动力学方面的吸收改进,为实际应用提供了理论指导。
    An innovative strategy to control nitrogen oxide emission from flue gas was developed using the wet flue gas denitrification technology. The use of cyclodextrin (CD) as an additive facilitated NO2 absorption by the sulfite absorbent. Compared with absorption by a sulfite solution (59.12%), the instantaneous absorption efficiencies employing CD improved to 94.57%. Moreover, 48 h of continuous absorption indicated cyclic utilization of CD. The favorable role of CD was ascribed to facilitating the limiting step for the entire NO2 absorption-dissolution process which included both water solubility and gas-liquid mass transfer. Furthermore, we propose a potential mechanism of CD/sulfite mixed solution absorbing NO2, among which the favorable role of the additive is related to its amphiphilic behavior toward gas and liquid phases. Additionally, a kinetic model describing the rates of gas-liquid transfer and macro absorption was established based on various operating conditions. This model explains the absorption improvement in the kinetic aspect and provides theoretical guidance for practical applications.
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  • 文章类型: Journal Article
    Eversa®Transform2.0脂肪酶用作生物柴油(脂肪酸甲酯-FAME)合成的生物催化剂,由于其热稳定性和成本效益,已成为有趣的研究目标。在这些研究中,研究了有关导致令人满意的产率的反应条件的数据。然而,动力学和热力学参数考虑这种酶是稀缺的。本文介绍了Eversa®Transform2.0介导的加氢酯化到FAME合成的动力学和热力学参数的估计。对不同的甲醇进行了动力学研究,水和脂肪酶负荷在不同的温度。通过热力学模型调整的参数表明,水解在整个加氢酯化反应速率中起决定性作用,并且酯化反应是吸热的(ΔHe=38.98kJ/mol)。增加温度有利于酶复合物的形成,特别是酶-甲醇抑制复合物。统计分析表明,该模型没有过度参数化,置信区间小表示估计参数的可靠性好。
    Eversa® Transform 2.0 lipase used as biocatalyst to biodiesel (fatty acid methyl esters - FAME) synthesis has been the target of interesting studies due to its thermostability and cost-effectiveness. In these researches, data about reaction conditions that result in satisfactory yields were investigated. Nevertheless, kinetic and thermodynamic parameters considering this enzyme are scarce. This paper presents an estimation of kinetic and thermodynamic parameters for the Eversa® Transform 2.0-mediated hydroesterification to FAME synthesis. Kinetic studies were performed for different methanol, water and lipase loads in distinct temperatures. Parameters adjusted by the thermodynamic model indicate that the hydrolysis is decisive in the overall hydroesterification reaction rate and the esterification reaction is endothermic (ΔHe = 38.98 kJ/mol). Formation of enzymatic complexes is favored by increasing the temperature, especially the enzyme-methanol inhibition complex. Statistical analysis showed that the model was not overparameterized, and the small confidence interval indicated good reliability of the estimated parameters.
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  • 文章类型: Journal Article
    淀粉的体外消化率是人类营养研究中的常见分析,通常包括在特定条件下通过α-淀粉酶进行淀粉的水解。类似的体外测定也用于其他研究领域,可以使用不同的方法。总的来说,天然淀粉的体外水解是所有这些方法之间的桥梁。在这篇文献综述中,我们在最近的出版物中研究了淀粉分解测定法的使用,这些出版物研究了复杂的淀粉结构-淀粉分解关系。本综述分为两部分:(1)对影响淀粉水解的因素的简要回顾;(2)对2016-2020年期间出版物中使用的实验设计和方法的系统回顾。后者报道了淀粉材料,调查的因素,淀粉水解动力学和数据分析技术的表征。这篇综述表明,主要的研究策略有利于通过结晶度最常描述的一些淀粉样品之间的比较,颗粒类型,直链淀粉和链长分布具有显著特征。该策略旨在通过关注特定特征来规避淀粉消化机制的多因素方面。一种替代策略依赖于计算方法,如多变量统计分析和机器学习技术,以破译每个因素对淀粉分解的作用。虽然承诺解决复杂性,有限的计算方法的使用可以解释为小尺寸的实验数据集在大多数出版物。这篇综述表明,已经有了生产更大数据集的关键步骤,特别是快速水解测定的推广和大多数分析结果的定量方法的发展。
    In vitro digestibility of starch is a common analysis in human nutrition research, and generally consists of performing the hydrolysis of starch by α-amylase in specific conditions. Similar in vitro assays are also used in other research fields, where different methods can be used. Overall, the in vitro hydrolysis of native starch is a bridge between all of these methods. In this literature review, we examine the use of amylolysis assays in recent publications investigating the complex starch structure-amylolysis relation. This review is divided in two parts: (1) a brief review of the factors influencing the hydrolysis of starch and (2) a systematic review of the experimental designs and methods used in publications for the period 2016-2020. The latter reports on starch materials, factors investigated, characterization of the starch hydrolysis kinetics and data analysis techniques. This review shows that the dominant research strategy favors the comparison between a few starch samples most frequently described through crystallinity, granule type, amylose and chain length distribution with marked characteristics. This strategy aims at circumventing the multifactorial aspect of the starch digestion mechanism by focusing on specific features. An alternative strategy relies on computational approaches such as multivariate statistical analysis and machine learning techniques to decipher the role of each factor on amylolysis. While promising to address complexity, the limited use of a computational approach can be explained by the small size of the experimental datasets in most publications. This review shows that key steps towards the production of larger datasets are already available, in particular the generalization of rapid hydrolysis assays and the development of quantification approaches for most analytical results.
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  • 文章类型: Journal Article
    螺旋藻已被认为是全球对抗营养不良的有希望的食品补充剂来源。许多研究表明了它的免疫活性,在生长期吸收二氧化碳的能力,和抗氧化潜力。众所周知的理论生物量动力学模型棚能够对微藻的快速生长进行定性分析。在这方面,我们考虑了八种流行的生物质模型:Monod,霍尔丹,Andrews&Noack,Teissier,Hinshelwood,Yano&Koga,韦伯和,Aiba模型包括数值模拟中的分析研究。此外,在这项研究中,我们通过合并著名的Hinshelwood和Yano&Koga模型建立了一个新的生物量生长数学模型。我们探索了最合适的螺旋藻生长模型,以最大程度地减少八种生物量动力学模型中高估和低估的生长趋势。我们的研究结果表明,微藻的生物量生长和底物随着时间的推移而减少,并将这些结果与可用的实验数据进行了比较。结果呈现较高的R2值(0.9862),RSS的低值(0.0813),AIC(-9.7277),与流行的八种研究模型相比,BIC(-8.2148)暗示与所研究的螺旋藻生长数据显着拟合。
    Spirulina platensis has been considered a promising source of food supplement to combat malnutrition worldwide. Numerous investigations have stated its immune activity, ability to absorb CO2 during the growth period, and antioxidant potential. Well-known theoretical biomass kinetic model sheds are capable of qualitative analysis of the fast microalgae growth. In this regard, we considered eight popular biomass models: Monod, Haldane, Andrews & Noack, Teissier, Hinshelwood, Yano & Koga, Webb and, Aiba model comprising analytical investigation within the numerical simulation. Besides, in this study, we establish a new mathematical biomass growth model by merging the well-known Hinshelwood and Yano & Koga models. We explored the most suitable Spirulina growth model to minimize the overstated and understated growth trends in the assorted eight biomass kinetic models. Our findings show microalgae biomass growth and substrate diminishes along with time, and these results were compared with available experimental data. Results present a high value of R2(0.9862), a low value of RSS (0.0813), AIC (-9.7277), and BIC (-8.2148) implied significantly fitted with the investigated data for the growth of Spirulina platensis compared with popular eight studied models.
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