Deacidification of black cumin seed oil by selective supercritical carbon dioxide extraction

The deacidification of high-acidity oils from Black cumin seeds (Nigella sativa) was investigated with supercritical carbon dioxide at two temperatures (40 and 60°C), pressures (15 and 20 MPa) and polarities (pure CO₂ and CO₂/10% MeOH). For pure CO₂ at a relatively low pressure (15 MPa) and relatively high temperature (60°C), the deacidification of a highacidity (37.7 wt% free fatty acid) oil to a low-acidity (7.8 wt% free fatty acid) oil was achieved. The free fatty acids were quantitatively (90 wt%) extracted from the oil and left the majority (77 wt%) of the valuable neutral oils in the seed to be recovered at a later stage by using a higher extraction pressure. By reducing the extraction temperature to 40°C, increasing the extraction pressure to 20 MPa, or increasing the polarity of the supercritical fluid via the addition of a methanol modifier, the selectivity of the extraction was significantly reduced; the amount of neutral oil that co-extracted with the free fatty acids was increased from 23 to 94 wt%.     

Comparison of the morphology and structure of WO3 nanomaterials synthesized by a sol-gel method followed by calcination or hydrothermal treatment

Tungsten (VI) oxide (WO₃) nanomaterials were synthesized by a sol-gel method using WCl₆ and C₂H₅OH as precursors followed by calcination or hydrothermal treatment. X-Ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) equipped with energy dispersive X-ray spectroscopy (EDX) were used to characterize the structure and morphology of the materials. There were significant differences between the WO₃ materials that were calcinated and those that were subjected to a hydrothermal process. The XRD results revealed that calcination temperatures of 300°C and 400°C gave hexagonal structures and temperatures of 500°C and 600°C gave monoclinic structures. The SEM images showed that an increase in calcination temperature led to a decrease in the WO₃ powder particle size. The TEM analysis showed that several nanoparticles agglomerated to form bigger clusters. The hydrothermal process produced hexagonal structures for holding times of 12, 16, and 20 h and monoclinic structures for a holding time of 24 h. The SEM results showed transparent rectangular particles which according to the TEM results originated from the aggregation of several nanotubes.     

Optical and mechanical properties of transparent alumina fabricated by high-pressure spark plasma sintering

Transparent alumina was fabricated from untreated commercial powder by high-pressure spark plasma sintering (HPSPS) at temperatures of 1000, 1050 and 1100 °C under pressures of 250-800 MPa. It was established that transparency strongly depends on the HPSPS parameters. At all temperatures, there was a certain point when increasing the pressure led to decreasing transparency. At 1100 °C, relatively high pressure led to excessive grain growth, as well as the formation of creep-induced porosity at the center of the samples. Hardness values decreased with pressure due to grain growth, correlated with the Hall-Petch relationship. The optimal combination of optical and mechanical properties (68% in-line transmittance at a wavelength of 640 nm and a hardness value of about 2300 HV2) was achieved after sintering at 1050 °C under 600 MPa.     

Fly Ash Porous Material using Geopolymerization Process for High Temperature Exposure

This paper presents the results of a study on the effect of temperature on geopolymers manufactured using pozzolanic materials (fly ash). In this paper, we report on our investigation of the performance of porous geopolymers made with fly ash after exposure to temperatures from 600 °C up to 1000 °C. The research methodology consisted of pozzolanic materials (fly ash) synthesized with a mixture of sodium hydroxide and sodium silicate solution as an alkaline activator. Foaming agent solution was added to geopolymer paste. The geopolymer paste samples were cured at 60 °C for one day and the geopolymers samples were sintered from 600 °C to 1000 °C to evaluate strength loss due to thermal damage. We also studied their phase formation and microstructure. The heated geopolymers samples were tested by compressive strength after three days. The results showed that the porous geopolymers exhibited strength increases after temperature exposure.     

Mutual Solubility Study in Supercritical Fluid Extraction of Tocopherols from Crude Palm Oil Using CO2 Solvent

In this article, the mutual solubility of tocopherols from crude palm oil was studied using carbon dioxide as a solvent at the temperatures of 80, 100 and 120 °C. Each sample from the phase equilibrium unit contained two parts. The liquid part was analyzed by gas chromatography (GC) in order to measure the tocopherol composition and, on the other hand, the vapor phase was conducted in an expansion vessel in order to measure the pressure increment during the expansion process. Two phase equilibrium data was calculated using the liquid phase composition and pressure increments during the expansion process. Results showed that the maximum solubility of tocopherols was around 2.27% at a temperature of 120 °C and at pressure of 5.44 MPa.     

Supercritical water oxidation treatment of humic acid as a model organic compound of landfill leachate

Landfill leachate is a complex and variable effluent, rich in organic and inorganic matters resistant to decomposition, and is an extreme pollutant. Humic acids (HA) are some of the most refractive substances in the leachates, which is the reason why they have been used as an organic model. The degradation of an HA solution through supercritical water oxidation (ScWO) was evaluated under a constant pressure of 22.5 MPa, temperatures from 400°C to 600°C, and reaction times from 15 to 60 seconds. The results showed that the most influential factor was temperature and it guided the operational conditions of the ScWO for the landfill leachate (22.5 MPa, 600°C, and 60 seconds). The landfill leachate treatment promoted high removal rates of true colour (87%), total dissolved solids (94%), nitrate (70%), and total phosphorus (96%). In addition, it removed 57% of the COD, which was similar to the HA removal rate (61%) under the same operational conditions. This indicates that HA are an adequate organic model for landfill leachates. The results suggest that ScWO is a clean and promising treatment technology that can be applied to landfills and can have even better results if used in combination with oxidizers and catalysts, or with the use of higher temperatures.     

Optical properties of vitrinite carbonized at different pressures

The effect of pressure on the optical properties of cokes from a medium volatile bituminous coal (carbon = 87.9 wt% daf), some carbonized at atmospheric pressure and others under hydraulic pressure (21–310 MPa), over temperatures ranging from 350 to 600 °C at 50 °C intervals, has been studied. The cokes formed at atmospheric pressure developed fine grained mosaics, while medium-flow type mosaics formed in coke carbonized under hydraulic pressure. The thermal decomposition stage began at lower temperatures with increasing hydraulic pressure, resulting in a prolonged devolatilization phase for coke formed at a pressure of 21 MPa. Hence the fluidity of samples carbonized under pressure decreases with increasing hydraulic pressure. Pressure promotes the optical anisotropy apparent from the level of bireflectance. The reflectance of coke formed at atmospheric pressure is higher than that of cokes carbonized under hydraulic pressure, perhaps due to the inhibitory effect of entrapped volatile matter during carbonization under hydraulic pressure. The morphological features of vitirinite carbonized under pressure resemble those of coals naturally affected by heat.     

Solubility of red pepper (C<Emphasis Type="Italic">apsicum annum</Emphasis>) oil in near- and supercritical carbon dioxide and quantification of capsaicin

Red pepper oil was extracted using near- and supercritical carbon dioxide. Extraction was carried out at pressures ranging from 10 to 35 MPa and temperatures from 30 to 60 °C, with a CO₂ flow rate of 24.01 g/min using a semi-continuous high-pressure extraction apparatus. The duration for extraction was 2 h. The highest oil yield was found at high pressure and temperature. The highest solubility of oil (1.18 mg/g of CO₂) was found at 35 MPa and 60 °C. The solubility data of red pepper oil in near- and supercritical CO₂ were fitted in Chrastil model. The fatty acid composition of red pepper oil was analyzed by gas chromatography (GC). Linoleic acid was found to be the major fatty acid in the oil. Capsaicin was quantified in different extracts by high performance liquid chromatography (HPLC). The highest capsaicin yield was found at 35 MPa and 60 °C.     

Nonsolvent coal hydrogenation at short contact time

Yields and properties of products on hydrogenation of Japanese and Australian coals have been studied using an autoclave equipped with a magnedrive device at temperatures of 500–600 °C and hydrogen pressure 4.9–14.7 MPa (gauge) in the absence of solvent. Optimum contact time, at which maximum extraction yield was observed, shifted from 15 s to a few seconds with increasing reaction temperature and hydrogen pressure. The extracts derived from both coals reveal similar structural parameters.     

Influence of pressure on stable carbon isotope ratio and production yield of coal-derived methane

Two immature coals have been pyrolyzed in confined gold reactors from 250 to 600 °C, but at different constant heating rates (2 and 20 K/h) and under different pressures (30 and 65 Mpa). Yields of coal-derived methane show significant differences under different pressures even with the same analytical procedure. Generally speaking, increasing pressure can result in an increasing yield of methane, even though the experiment did show a slight decrease at low temperatures (≤400 °C) with high heating rates. The range of activation energies for methane generation is obviously narrower at 65 Mpa than at 30 MPa.Under high pressure conditions of 65 MPa, methane relatively depleted in ¹³C would be induced at the major stage of methane generation. However, our kinetic modeling results show that isotope-specific kinetic parameters, activation energies and frequency factors of methane at high pressure are almost the same as those at low pressure. The isotope ratios for methane precursors in two coals studied were also similar to each other but with some variances under the two different pressure circumstances. The modeled δ¹³C of cumulative methane by using two pressure-based series of kinetic parameters under geological conditions at 2 K/Myr exhibits less differences, which manifests that the effect of pressure can be regarded as being negligible. The modeled δ¹³C values of instantaneously generated methane at two different pressures under geological conditions are, however, significantly distinctive, and this is especially the case at high maturation stage of coal.     

Solubility of α-Tocopheryl Succinate in Supercritical Carbon Dioxide Using Offline HPLC-MS/MS Analysis

The solubility of the vitamin E-related compound α-tocopheryl succinate in supercritical carbon dioxide was measured at pressures ranging from (15.0 to 30.0) MPa and temperatures of (40 and 50) °C using a simple microsampling type apparatus with a 100.5 μL sample loop to remove aliquots and collect them in ethanol for off line analysis. α-Tocopheryl succinate concentrations in the collected samples were measured using HPLC-MS/MS analysis. The solubility of α-tocopheryl succinate in supercritical carbon dioxide ranged from mole fractions of 0.28 × 10(-5) at 15.0 MPa and 50 °C to 2.56 × 10(-5) at 30.0 MPa and 50 °C.     

Enhancing the thermal robustness of an enzyme by directed evolution: least favorable starting points and inferior mutants can map superior evolutionary pathways

In a previous directed evolution study, the B-FIT approach to increasing the thermal robustness of proteins was introduced and applied to the lipase from Bacillus subtilis. It is based on the general concept of iterative saturation mutagenesis (ISM), according to which sites in an enzyme are subjected to saturation mutagenesis, the best hit of a given library is then used as a template for randomization at other sites, and the process is continued until the desired catalyst improvement has been achieved. The appropriate choice of the ISM sites is crucial; in the B-FIT method the criterion is residues characterized by highest B factors available from X-ray crystallography data. In the present study, B-FIT was employed in order to increase the thermal robustness of the epoxide hydrolase from Aspergillus niger. Several rounds of ISM resulted in the best variant showing a 21 °C increase in the T(60)(50) value, an 80-fold improvement in half-life at 60 °C, and a 44 kcal mol(-1) improvement in inactivation energy. Seven other variants were also evolved with moderate yet significant improvements; these were characterized by 10-14 °C increases in T(60)(50), 20-30-fold improvement in half-lives at 60 °C and 15-20 kcal mol(-1) elevations in activation energy. Unexpectedly, in the ISM process the best variants were obtained from essentially neutral or even inferior mutant parents, that is, when a given library contains no improved mutants. This constitutes a practical way to escape from what appear to be local minima ("dead ends") in the fitness landscape-a finding of notable significance in directed evolution.     

不同水针口径下的水辅助注射成型数值模拟

使用流体力学软件,对使用溢流法的三维120 °~150 °弯曲圆管件进行了水辅助注射成型可视化研究。分别改变水针口径尺寸、注水延迟时间、注水压力与熔体温度,分析其对制件内部水穿透行为的影响。结果表明,水针口直径为7 mm时,能显著增加制件的内部穿透长度并得到残余壁厚更薄的制件;受水针结构影响,注水延迟时间为1 s、注水压力为8 MPa、熔体温度为250 ℃时,水穿透长度最优能增长400 %,壁厚减少20 %;在注水延迟时间为1 s、注水压力为10 MPa、熔体温度为230 ℃时,穿透长度最大达到298 mm;注水延迟时间为1 s、注水压力为8 MPa、熔体温度为250 ℃时,比熔体温度为210 ℃和230 ℃的实验组受水针影响严重;缩短注水延迟时间、增加注水压力、升高熔体温度都能有效增大制件的中空率,成型出更薄的管件,但是水针对水辅助注射成型的影响不容忽视,其微小变化能极大地改变成型制件的内部型腔,有效提高水穿透行为的效率。     

深海玻纤增强柔性管截面结构设计及强度分析

在深海石油开采中,使用传统的钢制管道作为海底管道和立管,存在耐腐蚀性差、重量大以及柔性小等不足。热塑性玻纤增强柔性管具有重量轻、强度高、柔性好以及耐腐蚀性强等优点,逐步成为海洋管道发展的趋势。针对南海500 m海深油井使用玻纤增强柔性管进行增强层截面结构设计,依据DNVGL-RP-F119规范和美国船级社相关规范,针对柔性管增强层缠绕角度及缠绕层数,依据经验建立±30°~±75°缠绕角度和20层~40层缠绕层数的组合模型。利用ABAQUS有限元软件进行30 MPa内压、60 t拉力和5 MPa外压三种载荷工况下的强度分析,得到满足上述载荷工况的最优缠绕角度为±60°;再进行90MPa爆破压力及拉伸与外压组合工况下的强度校核,最后得到能够满足技术指标要求的增强层最优缠绕角度为±60°和最少缠绕层数为36层。     

Mechanical and chemical properties of metakaolin-based geopolymer exposed to elevated temperature

A method is presented to fabricate metakaolin-based geopolymers that are structurally and mechanically stable up to 600°C. The chemical environment of the geopolymers is characterized using thermogravimetric analysis and Fourier-transform infrared spectroscopy. Residual free water turned into steam and caused damage to the geopolymer when exposed to elevated temperatures. The curing temperature was increased from 80 to 120°C to remove water during the curing process. A correlation was drawn between the amount of Si-O-Al linkage formed and the position of fingerprint peaks in infrared spectra, providing a tool to evaluate the level of geopolymerization. Flexural and tensile properties of geopolymers fabricated using the optimized method were measured for no heat treatment and for exposure to elevated temperatures of 200, 400, and 600°C. The flexural strength was measured to be 10.80 ± 2.99 MPa at room temperature, 10.36 ± 0.64 MPa at 400°C, and 8.04 ± 1.60 MPa at 600°C. The flexural modulus is reported to be 13.09 ± 3.40 GPa at room temperature and 11.03 ± 0.53 GPa at 600°C. The flexural toughness decreased with increasing temperature. The tensile properties of the geopolymer were measured with direct tensile tests paired with an extensometer. The tensile strength decreased from 4.16 ± 2.08 MPa at room temperature to 3.13 ± 0.97 MPa at 400°C, and 2.75 ± 0.86 MPa at 600°C. The Young's modulus decreased from 45.38 ± 30.30 GPa at room temperature to 26.88 ± 6.65 GPa at 600°C. Both flexural and tensile tests have shown that the metakaolin-based geopolymers cured at 120°C is mechanically stable at temperatures up to 600°C.     

改性己二胺柔性固化剂的合成与性能研究

采用二官能度环氧树脂对己二胺进行改性,得到了一种含多段长亚甲基链段的柔性固化剂。利用红外光谱表征其基本结构,通过60℃下的在线红外检测以及不同温度下固化时间对力学强度影响的分析,初步确定了其最佳固化工艺条件为80℃×6h。通过热重分析法（TG）测试了不同固化剂用量的固化产物热稳定性,并采用差示扫描量热法（DSC）研究了该固化剂固化时放热状况,进一步得到并验证了前面工作的正确性。以环氧树脂E-44为主体树脂,分别对其固化物在-196℃、室温、60℃下的剪切强度、90°剥离强度进行探讨。当主体树脂与固化剂按1∶0.5质量比混合时,其在各温度下的拉伸剪切强度分别为16.84MPa、14.73MPa和13.52MPa,可满足实际应用的要求。     

Fly Ash-based Geopolymer Lightweight Concrete Using Foaming Agent

In this paper, we report the results of our investigation on the possibility of producing foam concrete by using a geopolymer system. Class C fly ash was mixed with an alkaline activator solution (a mixture of sodium silicate and NaOH), and foam was added to the geopolymeric mixture to produce lightweight concrete. The NaOH solution was prepared by dilute NaOH pellets with distilled water. The reactives were mixed to produce a homogeneous mixture, which was placed into a 50 mm mold and cured at two different curing temperatures (60 °C and room temperature), for 24 hours. After the curing process, the strengths of the samples were tested on days 1, 7, and 28. The water absorption, porosity, chemical composition, microstructure, XRD and FTIR analyses were studied. The results showed that the sample which was cured at 60 °C (LW2) produced the maximum compressive strength for all tests, (11.03 MPa, 17.59 MPa, and 18.19 MPa) for days 1, 7, and 28, respectively. Also, the water absorption and porosity of LW2 were reduced by 6.78% and 1.22% after 28 days, respectively. The SEM showed that the LW2 sample had a denser matrix than LW1. This was because LW2 was heat cured, which caused the geopolymerization rate to increase, producing a denser matrix. However for LW1, microcracks were present on the surface, which reduced the compressive strength and increased water absorption and porosity.     

N2气氛下温度和压力对煤热解的影响

研究煤热解的反应特性有助于提高煤热解的转化率和焦油收率并且能够改善焦油的品质。本文在固定床反应器上研究了N₂气氛中,不同压力和温度下的唐山烟煤热解反应,考察了温度和压力对热解失重率、热解气体组成及液相产物产率的影响规律。结果表明当热解压力由1MPa增加至3MPa时,唐山烟煤的失重率和焦油产率均先增加后降低,在2MPa时达到最大值。当温度低于600℃时,压力不影响CH₄、H₂和CO的收率,当温度超过600℃时,CH₄、H₂和CO的收率随热解压力的升高而降低。随着热解温度的升高,煤热解的失重率、水的产率以及CH₄、H₂的收率不断增大,焦油的收率和CO的收率先增大后降低,在2MPa下600℃时焦油的收率达最大值为9.23%。     

The effect of high pressure processing on the morphology of polyethylene films tested by differential scanning calorimetry and X‐ray diffraction and its influence on the permeability of the polymer

This study investigated the influence of high‐pressure processing on the morphology and permeability of low‐density polyethylene (LDPE) films used for food packaging. This was done by monitoring the crystallinity, melting temperature (T_m), and oxygen transmission rate (OTR) of the materials before and after the pressure treatments. A first set of pouches made from the LDPE films were filled with 95% ethanol then pressured at 200, 400, 600, and 800 MPa for 5 and 10 min at 25 and 75°C. The crystallinity and T_m of the films were measured using differential scanning calorimetry (DSC). X‐ray diffraction (XRD) was also used to determine the crystallinity. A second set of LDPE pouches were similarly made but a half of them were filled with 95% ethanol and the other half filled with distilled water. These second set of pouches were pressured at 200, 600, and 800 MPa then their OTR tested. Results of the DSC experiments showed that the T_m increased with increasing pressure intensity but the crystallinity changes were not detectible. The XRD method on the other hand, showed significant (P < 0.05) crystallinity increases with increasing pressure treatments. The gas permeability analyses showed decreasing OTR's with increasing high‐pressure intensity treatments. The OTR in the pouches filled with the 95% ethanol was slightly lower than that of the pouches filled with water. These findings allowed us to better anticipate the behavior of LDPE films used to package high‐pressure processed foods. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Extraction of potassium from K-feldspar via the CaCl2 calcination route☆

The extraction of potassium from K-feldspar via a calcium chloride calcination route was studied with a focus on the effects of the calcination atmosphere, calcination temperature and time, mass ratio of CaCl2 to K-feldspar ore and particle size of the K-feldspar ore. The results demonstrated that a competing high-temperature hydrolysis reaction of calcium chloride with moisture in a damp atmosphere occurred concurrently with the conversion reaction of K-feldspar with CaCl2, thus reducing the amount of potassium extracted. The conversion reaction started at approximately 600 °C and accelerated with increasing temperature. When the temperature rose above 900 °C, the extraction of potassium gradually decreased due to the volatilization of the product, KCl. As much as approximately 41%of the potassium was volatilized in 40 min at 1100 °C. The mass ratio of CaCl2/K-feldspar ore significantly affected the extraction. At a mass ratio of 1.15 and 900 °C, the potassium extraction reached 91%in 40 min, while the extraction was reduced to only 22%at the theoretical mass ratio of 0.2. Optimal process conditions are as follows:ore particle size of 50–75μm, tablet forming pressure of 3 MPa, dry nitrogen atmosphere, mass ratio of CaCl2/ore 1.15:1, calcination temperature of 900 °C, and calcination time of 40 min. The XRD analysis revealed that a complex phase transition of the product SiO2 was also accompanied by the con-version reaction of K-feldspar/CaCl2. The SiO2 product formed at the initial stage was in the quartz phase at 900 °C and was gradually transformed into cristobalite after 30 min.