Cold Plasma Treatment of Soybean Oil with Hydrogen Gas

High-voltage atmospheric cold plasma (HVACP) treatment generates reactive gas species that induce inter- and intramolecular reactions in soybean oil. The goal of this study is to analyze the effect of HVACP treatment on the chemical structure of soybean oil in a hydrogen gas environment at atmospheric pressure. HVACP was used to treat soybean oil (15 g) for up to 6 hours by triplicate. Plasma-generated reactive gas species interact with the sample, producing three distinct fractions identified as a liquid, gel, and solid. Fatty acid profile, Fourier-transform infrared spectroscopy, proton and carbon nuclear magnetic resonance, size-exclusion chromatography, thermal properties, and peroxide value were used to characterize the chemical structure. Results indicated a lower content of polyunsaturated fatty acids, increased content of saturated fatty acids, and the presence of isomers. An insoluble portion was observed in the solid fraction and increased with treatment time up to 42% in the 6-h treated samples. Plasma species may cause two main reactions: polymerization and hydrogenation.     

Application of thermal ultrasound-assisted liquid–liquid micro-extraction coupled with HPLC-UV for rapid determination of synthetic phenolic antioxidants in edible oils

A simple, fast, and reliable liquid–liquid micro-extraction (LLME) method assisted by thermal ultrasound approach was developed for simultaneous determination of synthetic phenolic antioxidants (SPAs) in edible oils by high-performance liquid chromatography equipped with ultraviolet detector (HPLC-UV). The synthetic antioxidants were propyl gallate (PG), butylated hydroxyanisole (BHA), tert-butylhydroquinone (TBHQ), and butylated hydroxyltoluene (BHT). The best extraction conditions were observed were methanol/acetonitrile (1:1, v/v) as the solvent, ultrasound at 4 min, and a temperature of 40°C. The linearity of the calibration curves for the optimum conditions were R² > 0.989 for all of the SPAs in a range from 1–200 μg ml⁻¹. Relative standard deviation (RSD %) for five analysis was in range of 2.83% to 4.21%. Limit of detection (LOD) and limit of quantification (LOQ) were obtained in range of 0.012–0.06 and 0.04–0.2 μg g⁻¹, respectively. With regard to recovery, a range of 91%–116% was calculated for the spiked edible oils.     

A gas chromatography–mass spectrometry method for the detection of chlorpyrifos contamination in palm-based fatty acids

Chlorpyrifos is a Malaysian Pesticide Board-approved organophosphate insecticide, which may become concentrated during fractionation. The objective of this project was to develop and validate a method to detect and quantify chlorpyrifos in food-grade fatty acids ingredients, e.g. caprylic-capric acid mixture and oleic acid (OLA) used to synthesize triacylglyceride based food additives and in the cosmetic industry. A selective ion monitoring gas chromatography–mass spectrometry method with a matrix-matched calibration curve calibration was selected. The method involved the direct injection of chlorpyrifos spiked into the fatty acids matrix. The percentage recoveries at spiking levels of 0.5, 0.75, 2.5, and 4.0 μg g⁻¹ of chlorpyrifos in OLA and caprylic-capric acid ranged from 85.7%–101.1% to 97.2%–112%, respectively, with a relative standard deviation of within 11%. The intra-day and inter-day precision were deemed acceptable as indicated by an relative SD value of within 10%. A good linear relationship with a coefficient of correlation >0.99 for the matrix-matched calibration was achieved between 0.5 and 5 μg g⁻¹. The limit of detection and limit of quantification corresponded to 0.5 μg g⁻¹ for OLA and 0.55 μg g⁻¹ for caprylic-capric acid.     

Improving the cold flow properties of biodiesel from waste cooking oil by ternary blending with bio-based alcohols and diesel from direct coal liquefaction

The utilization and popularization of biodiesel are always limited by its poor cold flow properties. Both bio-based alcohol and diesel from direct coal liquefaction (DDCL) has potential to enhance the cold flow properties of biodiesel. In this study, ternary blends of waste cooking oil biodiesel (BWCO) with DDCL and bio-based ethanol (ET) or 1-butanol (BT) were conducted to improve the cold flow properties of biodiesel. The pour point (PP), cold filter plugging point (CFPP), and cloud point (CP) of BWCO-ET, BWCO-BT, and BWCO-DDCL binary blends, and BWCO-ET-DDCL and BWCO-BT-DDCL ternary blends were comparatively assessed. Ternary phase diagrams were also applied to analyze the blending effect of the three components on the cold flow properties of biodiesel. Results showed that both DDCL, ET, and BT can remarkably enhance the cold flow properties of BWCO. When the ternary blends contain 20 vol.% BWCO and less than 40 vol.% ET or BT, DDCL together with ET or BT exerted positive effects on enhancing the low-temperature flow properties of BWCO, especially on the CP and CFPP. For ternary blends in 20:10:70 blending ratio, BWCO-BT-DDCL exhibited the lowest PP, CFPP, and CP of −23, −19, and −17°C, respectively. The crystallization behavior and crystal morphology of blended fuels are also observed via a polarizing optical microscope, and find that DDCL together with BT in biodiesel can effectively retard the aggregation of large crystals and inhibit crystals growth.     

Effect of special structure of clam shell powder on structure and properties of castor oil-based composites

Castor oil (CO) is an environmentally friendly renewable green resource and ideal alternative to petroleum resources. The preparation of high strength and high toughness castor oil-based polyurethane prepolymer (COPU) composites has significant applications such as supporting material and engineering plastic sheet. In this study, unmodified clam shell powder (CSP) with a unique CaCO₃-proteoglycan structure was used as a filler to prepare compatible reinforced COPU composite materials. Investigation of the mechanical properties revealed that the elastic modulus of the composite COPU reinforced with 50 wt% of CSP had increased to 5859.0 ± 8.4 MPa representing 187.77% to obtain stiffer and stronger material over pure COPU (2036.6 ± 196.9 MPa). Moreover, the scanning electron microscopy, thermogravimetric analysis and contact angle results demonstrated that the reinforced COPU composites have better compatibility, thermal stability, and water resistance than pure COPU. This work will promote the application prospects of CO-based polyurethane.     

Poly(vinylidene fluoride) with zinc oxide and carbon nanotubes applied to pressure sheath layers in oil and gas pipelines

In this work, PVDF composites containing 0.2% (m/m) of carbon nanotubes (MWCNTs), PVDF with 5.0% (m/m) of zinc oxide (ZnO), and composites containing both particles in the same contents in the matrix were melt processed in a mini-extruder machine with double screws, using the counter-rotation mode. Composites were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), dynamic-mechanical analysis (DMA), and contact angle tests (CA). The samples presented the predominance of the α phase, with an increased degree of crystallinity as well as an increase in dimensional stability by incorporating both fillers, showing a synergistic effect between these particles, as shown on FTIR, DSC, and XRD results. SEM images showed a good dispersion of high aspect ratio particles. In general, DMA and TGA analysis showed that composites had not decreased their thermal and mechanical performance when compared to neat PVDF. Results of CA analysis showed an increase in the hydrophobicity of the sample containing MWCNTs. Permeability tests were also performed using a differential pressure system, combining high temperature and pressure, obtaining permeability measures and time lag. This work presents an alternative of composite materials, suggesting its application in the internal pressure sheath layers of oil and gas flexible pipes.     

生物原油炼制： 副产物内循环及水热自催化

利用高温高压条件模拟石油生成的生物质水热液化技术可用于制备生物原油,以替代日益枯竭的石油资源,然而副产物处置问题制约了其可持续发展。解决该问题的方法首先是通过水热定向催化调控减少副产物,然后集成各种技术将副产物尽可能原位资源化。基于此并依据生物炼制的思想,本文对一种集成几种水热技术炼制生物原油的模式进行了讨论。依据生物质水热液化副产物的特性,通过对固体产物水热合成制备催化剂、水相产物回用产生有机酸、气体产物分离或彻底氧化后水热还原生产有机酸等,可实现副产物内循环并强化自催化生成生物原油。指出该模式符合绿色化工的理念,对于加快规模化生产可替代石油的生物原油、缓解能源危机具有重要的参考意义。     

流化催化裂化油浆综合利用的分析

流化催化裂化（FCC）油浆外甩量通常超过5%,需要脱固处理得到澄清油再利用。本文分析得出了向延迟焦化、溶剂脱沥青、减压蒸馏、加氢等重质油加工装置直接掺炼,局限性较大;利用减压蒸馏、溶剂抽提、超临界流体萃取等工艺,对澄清油“掐头去尾”,分离组分可生产针状焦、环保橡胶填充油、沥青树脂以及碳素纤维等高附加值产品。油浆组分通过延迟焦化制备针状焦,是工业化应用主体方向,但国内产品质量与国外尚有很大差距;油浆制备环保橡胶填充油,在降低环保橡胶油多环芳烃（PCA）和8种危害性稠环芳烃（PAHs）分别至3%和10mg/kg以下的同时,必须提高芳碳率（C_A）值至10%以上来保持橡胶相容性,其收率及生产成本是工业化应用推广的制约因素。     

基于聚丙烯无纺布与耗氧传感器的泄漏乳化油的监测

利用聚丙烯无纺布（polypropylene non-woven fabric,PP NWF）和耗氧传感器结合来构建一个乳化油监测探头。PP NWF是一种超疏水吸油材料,可以快速吸附乳化油污,利用该性能,本监测探头先用PP NWF富集乳化油污,再用探头对材料中的氧含量进行监测,从而达到乳化油监测的目的。本文通过监测不同种类的乳化油（表面活性剂为吐温80的正己烷乳化油、石油醚乳化油、甲苯乳化油及表面活性剂为司班80的正己烷乳化油、石油醚乳化油、甲苯乳化油）来验证其可行性。结果表明：该监测探头可以监测到不同乳化条件下的乳化油,并且能监测到不同种类的乳化油。其中监测甲苯乳化油时响应时间最短,可以在6s内监测到该油污。固定PP NWF时的耗氧传感器探头的最低检测限为1.27g/L,监测效率较未固定PP NWF时提高了近8倍。综上,固定PP NWF的耗氧传感器探头可以作为海洋乳化油监测重要的一个系统,对海洋乳化油泄漏事故进行在线实时监测,可以快速准确提供早期溢油预警。     

聚乳酸/聚氨酯复合多孔材料制备及吸油性能研究

以聚乳酸（PLA）为基体,添加不同含量聚氨酯（TPU）熔融共混制备具有不同相形态的PLA/TPU共混物,基于超临界二氧化碳（scCO₂）微孔发泡工艺,研究不同发泡温度下PLA/TPU复合多孔材料泡孔结构、发泡倍率和开孔率对样品吸油性能的影响。结果表明,随着TPU含量从10 %（质量分数,下同）增加到50 %,共混物从典型的“海?岛”相形态转变为部分共连续相形态,PLA基体黏弹性提升,结晶能力下降;PLA70组分发泡后泡孔结构更为均匀,随着发泡温度的增加,泡孔尺寸和发泡倍率先增大后减小,在94 ℃发泡温度下发泡样品发泡倍率达到29.1倍,最大开孔率75 %;TPU的加入显著增加了PLA基体的弹性回复能力,94 ℃发泡温度下的发泡样品具有最大的抗压强度,永久形变量最小;针对硅油和环己烷的吸油测试发现对硅油的吸油量大于环己烷,发泡材料的吸油量与发泡倍率和开孔率的乘积成正比,针对硅油单次最大吸油量为10.4 g/g。