A further study of the kinetics and optimization of the essential oil hydrodistillation from lavender flowers

Hydrodistillation has commonly been used to recover essential oil from various plant materials, including lavender (Lavandula officinalis) flowers. The main objectives of the present study were to model the kinetics of the lavender essential oil (LEO) hydrodistillation using a phenomenological model, to evaluate the statistical significance of the hydromodule and hydrodistillation time on LEO yield combining a 4² full factorial design with the response surface methodology, to model statistically LEO yield by multiple non-linear regression and to determine the optimal process conditions that provided the maximum LEO yield. The fast-essential oil distillation (washing stage) in the initial period and the slow diffusion stage until the saturation occurring simultaneously were observed, justifying the use of the phenomenological model. With increasing the hydromodule, the saturation LEO yield and the washable fraction of the LEO decreased while the washing and diffusion rate constants increased. Knowledge of the LEO oil yield and the hydrodistillation kinetics is important from the techno-economical point of view.     

A kinetic study of quicklime-catalyzed sunflower oil methanolysis

The quicklime-catalyzed sunflower oil methanolysis was studied at mild reaction conditions. Quicklime (calcined at 550 °C for 4 h) in amounts of 1.0, 2.5, 5.0 and 10.0% (based on the oil weight) and different molar ratios of methanol-to-oil (6:1, 12:1 and 18:1) were employed to investigate their influence on the methyl esters content and the kinetics of the methanolysis reaction. The optimal methanol-to-oil molar ratio and quicklime amount for achieving the highest fatty acid methyl esters content were established to be 12:1 and 5% (based on the oil weight), respectively. The sigmoidal kinetics of quicklime-catalyzed methanolysis reaction was described by a model which included the changing mechanism of the reaction and the triacylglycerols mass transfer limitation. The kinetic parameters were determined and correlated with the process variables. A good agreement between the kinetic model and the experimental data for all applied reaction conditions was observed.     

Enhanced extraction of essential oil from Cinnamomum cassia bark by ultrasound assisted hydrodistillation

Cinnamon essential oil with many bioactivities is an important raw material for the production of various chemicals,and the conventional hydrodistillation(HD) for cinnamon oil extraction always require a longer extraction time. In this work, ultrasound-assisted hydrodistillation extraction(UAHDE) technique was employed to enhance the extraction efficiency of essential oils from cinnamon barks. The parameters with significant effects on the essential oil extraction efficiency(ultrasound time, ultrasound power, extraction time, liquid–solid ratio) were optimized, and the proposed UAHDE was compared with the conventional HD extraction in terms of the extraction time, extraction yield, and physicochemical properties of extracted oils. Compared to the HD extraction, the UAHDE resulted in a shorter extraction time and a higher extraction yield. Using GC–MS analysis, the UAHDE provided more valuable essential oil with a high content of the vital trans-cinnamaldehyde compounds compared with the HD. Scanning electron micrograph(SEM) confirmed the efficiency of ultrasound irradiation for cinnamon oil extraction. In addition, the analysis of electric consumption and CO2 emission shows that the UAHDE process is a more economic and environment-friendly approach. Thus, UAHDE is an efficient and green technology for the cinnamon essential oil extraction, which could improve the quantity and quality of cinnamon oils.     

Kinetics of the base-catalyzed sunflower oil ethanolysis

The kinetics of the sunflower oil ethanolysis process using NaOH as a catalyst was studied at different reaction conditions. The reaction system was considered as a pseudo-homogeneous one with no mass transfer limitations. It was also assumed that the chemical reaction rate controlled the overall process kinetics. A simple kinetic model consisting of the irreversible second-order reaction followed by the reversible second-order reaction close to the completion of the ethanolysis reaction was used for the simulation of the triglyceride conversion and the fatty acid ethyl ester formation. The proposed kinetics model fitted the experimental data well.     

Assessing the kinetic model of hydro-distillation and chemical composition of Aquilaria malaccensis leaves essential oil

This study aimed to model the kinetic of hydro-distillation of Aquilaria malaccensis leaves oil in order to understand and optimize the extraction process. In addition, this study, for the first time, aimed to identify the chemical compositions of the A. malaccensis leave-oil. By assessing both first-order kinetic model and the model of simultaneous washing and diffusion, the result indicated that the model of simultaneous washing and diffusion better describes the hydro-distillation mechanism of the essential oil from A. malaccensis leaves.The optimum time, solid to liquid ratio, and the heating power for extracting the highest amount of essential oil were found to be around 3 h, 1:10(g·ml-1), and 300 W respectively. Yellow essential oil with a strong smell and a yield of 0.05 v/w was extracted by hydro-distillation Clevenger apparatus. Chemical compounds of the essential oil were analyzed using gas chromatography–mass spectroscopy(GC/MS), which resulted in identification of 42 compounds that constitute 93% of essential oil. Among the identified components,Pentadecanal(32.082%), 9-Octadecenal,(Z)(15.894%), and Tetradecanal(6.927%) were the major compounds.Considering the fact that all the identified major components possess pesticidal properties, A. malaccensis leaves can be regarded as a promising natural source for producing pesticides.     

Effect of extraction methods on kinetic,chemical composition and antibacterial activities of Tunisian Thymus vulgaris. L. essential oil

The present study aims to compare two innovative extraction techniques: microwave-assisted hydrodistillation (MAHD) and solvent-free microwave extraction (SFME) through traditional extraction techniques: hydrodistillation (HD) and steam distillation (SD) for their efficiency in the extraction of the volatile compounds from Tunisian Thymus vulgaris leaves; the kinetic, yield, composition and antibacterial activities of the essential oil were assessed in vitro. Results show that the essential oils extracted by microwaves were quantitatively (yield) similar to those obtained through the conventional methods, but qualitatively, essential oils analysed by gas chromatography–mass spectrometry (GC–MS) presented 17, 11, 11 and 8 compounds obtained through SFME, MAHD, SD and HD, respectively, mostly consisting of carvacrol (89.24–41.17%), followed by γ-terpinene (11.37–1.37%) and para-cymene (27.95–2.05%). The essential oils were screened for antibacterial activity against 5 microorganisms. All essential oils obtained by studied extraction methods showed the same resistance against Gram (?) and Gram (+) bacteria. The SFME method gave the best results: rapid kinetic of extraction (30 min vs. 35 min for MAHD, 120 min for SD, and 180 min for HD), less energy saving and cleanest process.     

A shrinking core model and empirical kinetic approaches in supercritical CO2 extraction of safflower seed oil

Utilization of supercritical CO₂ in safflower seed extraction was performed using a semi-batch extractor. Different extraction parameters, such as 40–60 MPa pressure, 323–347 K temperature, 20–76 min time, and 1–3 mL/min CO₂ flow rate were applied. A two-stage experimental design application was performed in order to maximize the oil yield. First of all, a 3² factorial design was applied to estimate the effect of the main factors and their interactions. The second part of the experimental design was improved and accelerated using the steepest ascent method. Optimum extraction parameters were determined to be 50 MPa pressure, 347 K temperature and 76 min time at a constant CO₂ flow rate (3 mL/min) according to the 2² design. Under these conditions, the oil yield obtained was 39.42%, comparable with Soxhlet extraction (40%) for 8 h. Shrinking core and empirical kinetic models were applied in order to generalize the extraction process. The predicted data was compatible with the experimental data.     

A novel process for extraction of tea oil from Camellia oleifera seed kernels by combination of microwave puffing and aqueous enzymatic oil extraction

The objective of this study was to extract the oil from Camellia oleifera seed kernels by aqueous enzymatic oil extraction (AEOE). We describe a novel process for extraction of tea oil preceded by tea saponin extraction from C. oleifera seed kernels. The extraction efficiency obtained with microwave‐assisted extraction (MAE) is very high, which the recovery yield is up to 83% in 30 s and the saponins in camellia seed kernels can be completely removed by the second MAE. Moreover, an important step in the process development has been the pretreatment by microwave puffing of camellia seed kernel residues followed by AEOE increased oil extraction yield from 53% to 95%, which will is comparable to hexane oil extraction yields from plant materials.     

Upgrading Siberian (Russia) crude oil by hydrodesulfurization in a slurry reactor: A kinetic study

Hydrodesulfurization (HDS) of sour crude oil is an effective way to address the corrosion problems in refineries, and is an economic way to process sour crude oil in an existing refinery built for sweet oil. In the current study, the HDS of Siberian crude oil was carried out in a slurry reactor. The Co–Mo, Ni–Mo, and Ni–W catalysts supported on γ-Al₂O₃ were compared at the temperature of 340 °C and the pressure of 4.5 MPa. The HDS activity follows the order of Co–Mo > Ni–Mo > Ni–W at a high concentration of H₂S, and the difference between Co–Mo and Ni–Mo becomes insignificant at a low concentration of H₂S. The influence of reaction temperature 320–360 °C and reaction pressure 3–5.5 MPa was investigated, and both play a positive role in the HDS reaction. A kinetic model over Ni–Mo/Al₂O₃ in the slurry reactor was established. The activation energy is estimated as 60.34 kJ·mol⁻¹; the orders of sulfur components and hydrogen partial pressure are 1.43 and 1.30, respectively. The kinetic parameters are compared with those in a trickle-bed reactor, implying that the mass transfer is greatly enhanced in the slurry reactor. The back mixing effect is present in the slurry reactor and can be reduced by a multi-stage design, which would lead to higher reactor efficiency in industrial application.     

A kinetic study of phospholipid extraction by degumming process in sunflower seed oil

During the refining process of vegetable oils (degumming), phospholipids are eliminated by thermal treatment with water (hydratable phospholipids, HP) and other degumming agents such as phosphoric acid, citric acid, or acid mixtures (nonhydratable phospholipids, NHP). Samples of pressed crude sunflower oils were degummed with water and acids, and the corresponding pellets (gums) and supernatant oils were obtained by centrifugation. During the water degumming process, a decrease of more than 98% in the phosphatidylcholine (PC) content was achieved in 5 min; phosphatidylethanolamine (PE) was the most difficult compound to be removed. Phosphatidylserine, phosphatidic acid, and phosphatidylinositol (PI) presented an intermediate behavior. The optimal contact time for quantitative extraction of the most important HP (PC, PI, and PE) in crude sunflower oils was 35 min. For acid treatments, a rapid elimination of the residual levels of PC was registered (5 min); the optimal contact times for the quantitative removal of the NHP were 35 min for phosphoric acid und acid mixture, and 25 min for citric acid. Taking into account that PE was the most difficult component to be removed, its level could be used as a monitor to evaluate the efficiency of the degumming process.     

A new approach to the kinetic modeling of the reaction of gaseous HCl with solid lime at low temperatures

The chemical reaction between gaseous HCl and solid Ca(OH)₂ has several applications, namely in the dry scrubbing of acid gases. The behavior of this reacting system in a laboratory-scale tubular reactor was simulated using the ‘grain model’ for the solid phase and a cascade of CSTRs for the gaseous phase. This model was applied to experimental data obtained in a previous study, at low temperatures (50-130°C) and high humidity level. The results show that the diffusion of the gaseous reactant through the product solid layer is the rate-limiting step for this reaction. In the first reacting moments, when no solid product has yet been formed, the reaction is limited by the total consumption of the gaseous reactant, indicating a very fast chemical reaction . These results were compared with those obtained by two other models used to describe the behavior of the gaseous phase: the ‘differential reactor model’ and the ‘average concentration model’. We show that the differential reactor model, which has been largely applied in published works about this and other similar reacting systems, is not adequate for modeling the reaction process, particularly in its initial phase.     

A new kinetic model for pyrolysis of Athabasca bitumen

Pyrolysis of bitumen is a key contributor to gas production in in situ combustion and in situ gasification recovery processes, yet a detailed reaction scheme, that includes a breakdown of products into the most abundant gas components, that is simple enough to be used in detailed thermal‐reactive simulation models, does not exist. Here, we present a novel reaction scheme for pyrolysis of Athabasca bitumen that was developed and calibrated against four experimental data sets (65 data points) over a temperature range from 130 to 422°C. The new model was then verified by comparing its thermogravimetric behaviour against published literature. © 2012 Canadian Society for Chemical Engineering     

A new twin-screw press design for oil extraction of dehulled sunflower seeds

Transport of material in a single-screw press depends mainly on friction between the material and the barrel’s inner surface and the screw surface during screw rotation. Thus, a solid core component, like seed hulls, is often necessary to produce the fraction. This sometimes causes excess frictional heat, large energy consumption and oil deterioration. Furthermore, if single-screw presses are not configured with breaker bars or other special equipment, they provide inadequate crushing and mixing. A twin-screw oil press can be expected to solve these problems because of the higher transportation force, similar to a gear pump, and better mixing and crushing at the twin-screw interface. A twin-screw press (screw diameter=136 mm, length/diameter=6.5, screw speed 15–100 rpm, feed rate=50–150 kg/h) was designed with partially intermeshing and counter-rotating screws and was tested on dehulled sunflower seed. The results were compared to a single-screw lab-scale press. Dehulled sun-flower seed (wt, 6.0%; oil, 58.6%) without pretreatments (crushing or cooking) gave 93.6% oil recovery with the twin-screw press, in contrast to 20% oil recovery with the single-screw press. The oil expressed with a twin-screw press had less foreign material than the oil from the single-screw press. Other properties of the oil were also good. Energy consumption of the twin-screw press was more efficient. All results suggested that oil production from dehulled sunflower seed with a twin-screw press is highly efficient.     

基于结构导向集总的废弃油脂催化裂化分子尺度动力学模型

利用结构导向集总与Monte Carlo模拟方法相结合构建了废弃油脂催化裂化反应的分子尺度动力学模型。模型选取17个结构向量表示废弃油脂分子,生成1000个原料分子表示废弃油脂原料,利用模拟退火算法对原料矩阵进行优化,同时针对废弃油脂体系的脱氧反应新增12条反应规则,利用Materials Studio 8.0软件求取其速率常数,完成动力学模型的构建。结果表明模型可以很好地对原料性质和产物分布进行预测,模拟值与实验值的绝对误差都在比较合理的范围内,说明求取的速率常数和编制的反应规则是合理的。     

A kinetic model for bleaching vegetable oils

Very little data and very few kinetic models are available describing and evaluating the performance of bleaching processes, earths, and equipment. This work presents a general kinetic model for the adsorption of pigments by adsorbent earths in several edible oils. It reports the kinetic parameters found for two bleaching earths (one developed in the laboratory and one commercial) for the clarification of soybean oil, as well as their activation energies. The proposed kinetic model is second order in the dimensionless pigment concentration and is in good agreement with our experimental data. A very simple mechanistic explanation based on adsorption/deactivation is offered to justify its application. We also present mathematical modeling based on balance equations to show how the kinetic parameters can be used for bleaching earths and for industrial equipment evaluation and design, such as for the transient fed-batch stirred bleaching vessel. The model seems appropriate to represent data under different operating conditions such as temperature and adsorbent load. The simulation shows that startup procedures are very important in the bleaching process—at least as important as the batch step, in which the oil color reaches its desired standard.     

A model investigation of the influence of particle shape on portland cement hydration

The NIST Virtual Cement and Concrete Testing Laboratory (VCCTL) is used to simulate the influence of particle shape on the hydration kinetics and setting of portland cement. Building on previous work in reconstructing particle shapes from real cements, real-shape particles are used to produce three-dimensional digitized cement paste microstructures, and the hydration of these microstructures is tracked using VCCTL. The degree of hydration and percolation of solids is monitored and compared to experimental data at several water-cement ratios. The simulations predict that shapes of particles influence cement hydration in two ways: the additional surface / volume ratio relative to spherical particles results in greater rates of hydration, and the anisometry in shape influences the degree of hydration at which the particles and hydration products percolate to form a stiff three-dimensional network.     

微波辐射柴油脱硫实验研究

采用微波辅助氧化反应的方法对辽河常二线柴油配制油样进行了脱硫实验，过氧化氢作氧化剂，可以把柴油中的含硫化合物有选择性地氧化成相应的具有很强极性的砜，根据相似相溶原理，这些砜因溶于剂相而从柴油中除去，从而降低了硫含量。实验过程中分别考察了氧化荆用量、剂油比、反应体系压力、氧化时间、微波功率等对柴油硫含量的影响。确定了实验室适宜的操作条件：剂油体积比为0．25：1，微波辐射压力为0．05MPa，微波功率为375w，辐射时间为6min，柴油的脱硫率为60％．而在无微波辐射的条件下，脱硫率仅为12％。     

A comprehensive mathematical model for the Fischer-Tropsch synthesis in well-mixed slurry reactors

A new product distribution quasi-steady-state model was proposed for the Fischer-Tropsch (FT) synthesis in slurry reactors, being applicable to their transient simulation. It may consider two chain propagation mechanisms or sites and the possibility of 1-olefin readsorption with secondary reactions, recovering the Anderson-Schulz-Flory (ASF) model, the two superimposed ASF model and the 1-olefin readsorption model as particular cases. The hydrocarbon compounds were lumped according to the number of carbon atoms in their molecules for the paraffin and 1-olefin families. The phases were assumed to be well mixed in the reactor and transient mass balances were performed for each component, allowing simulation of operation in constant liquid level and no liquid withdrawal conditions. A rigorous calculation of the vapor-liquid equilibrium (VLE) through cubic equations of state was used to describe the phase behavior. Rate expressions for the FT and the water gas shift reactions are taken from the literature and expressed in terms of fugacities. Simulation results showed that the inclusion of both the olefin readsorption and the two chain propagation mechanisms may explain the anomalies present in experimental hydrocarbon product distribution. Moreover, the effect of phase-equilibrium modeling on product distribution simulation was shown to be slightly important in the conditions analyzed. Compositional lumping schemes for the hydrocarbons were investigated to speed up the simulations. Results showed that lumping can speed up computations up to 250 times with negligible loss of accuracy.     

A study on the extraction of essential oil of Persian black cumin using static supercritical CO2 extraction,and comparison with hydro-distillation extraction method

The essential oil of Persian black cumin was extracted using static supercritical CO₂ technique at different temperatures, extraction times, and number of extractions. The composition of extracted oil was measured by GC-MS analysis and 25 components were identified. It was found that the oil recovery was reduced by increasing the temperature. Maximum recovery was achieved at two-step extraction that was about 49%. Both dissolution rate and solubility limited the oil recovery at the tested extraction conditions. The oxygenate components have less dissolution rate than the terpenes. The application of experimental data for design of an efficient dynamic extraction system was discussed.