Trials of bioremediation on a beach affected by the heavy oil spill of the Prestige

The objective of this study was to assess the efficiency of several bioremediation products in accelerating the in situ biodegradation of the heavy fuel oil spill of the Prestige. Trials of bioremediation were conducted in sand, rocks and granite tiles on the beach of Sorrizo (A Coruña, NW Spain) that was polluted by the spill. Neither the added microorganisms nor the nutrients significantly enhanced the degradation rate of the fuel oil in rocks, granite tiles or sand. PAH degradation up to 80% was determined in sand and tiles. In tiles the oxygen content of the residual oil increased from 1.6% up to 8% in 90 days, which could be explained by the accumulation of products coming from the partial oxidation of the hydrocarbons. Eighteen months after the spill, the rocks of the beach were still coated by a black layer of weathered fuel oil. For this reason an oleophilic product, sunflower biodiesel was tested on a rock. The application of biodiesel accelerated the gradually clean-up of the polluted surface and could also accelerate the degradation of the residual oil.     

Facile synthesis of layered sodium disilicates as efficient and recoverable nanocatalysts for biodiesel production from rapeseed oil

In this study, α, β and δ phases of layered sodium disilicates were synthesized and used as heterogeneous catalysts for transesterification of rapeseed oil with methanol to methyl esters (biodiesel). The catalysts were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) technique, Fourier transform infrared spectroscopy (FT-IR), N₂ adsorption-desorption, and thermogravimetric analysis (TGA-DTA). δ-Na₂Si₂O₅ showed better catalytic efficiency than the other two phases of sodium disilicate, and showed excellent activity at the optimized conditions. The transesterification conditions, such as the catalyst dosage, molar ratio of methanol to oil, reaction temperature and reaction time were investigated. The results revealed that with a catalyst loading of 4?wt%, methanol to oil ratio of 30:1, reaction temperature of 65?°C and reaction time of 3?h, conversion of biodiesel reached 97.8%.     

Preparation of H-oleoyl-carboxymethyl-chitosan and the function as a coagulation agent for residual oil in aqueous system

In this study, H-form oleoyl-carboxymethyl-chitosan (H-O-CMCS) was prepared as a coagulation agent to clean up the residual oil from the waste-water of oil extraction (WWOE). The Fourier transform infrared (FTIR) spectra confirmed the formation of an amide linkage between amino groups of carboxymethyl chitosan (CMCS) and carboxyl groups of oleic acid. The adsorption capacities of four absorbents (H-O-CMCS, chitosan, activated carbon and polyaluminium chloride (PAC)) for the residual oil were investigated. Compared with chitosan, activated carbon and PAC, H-O-CMCS was more effective in removing the residual oil from WWOE, which could successfully wash up almost 99% of residual oil from WWOE at the dosage of 0.2 g/L, the mixing time of 3 min, 500 rpm, and a broader range of pH (the system temperature ⩽ 45°C). In similar conditions, comparatively, chitosan, activated carbon and PAC could wash 90%, 82% and 92% of residual oil from WWOE, respectively.     

The influence of the age of biodiesel and heating oil with 10 % biodiesel on the resistance of sealing materials at different temperatures

The objective of this research was to determine the resistance of frequently used sealing materials such as fluorocarbon rubber (FKM), fluorosilicone rubber (FVMQ), silicone rubber (VMQ), ethylene‐propylene‐diene rubber (EPDM), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), butyl rubber (IIR), acrylonitrile butadiene rubber (NBR), polyester urethane rubber (PUR) and polyamide (PA) in non‐aged/aged biodiesel and heating oil with 10 % biodiesel at 20 °C, 40 °C and 70 °C. Mass, tensile properties and shore hardness A/D (for polyamide) of the test specimens were determined before and after the exposure for 84/42 days in the aged and non‐aged fuels of different age. Biodiesel fuels are easily oxidized and contain acids and water. The sealing materials: acrylonitrile butadiene rubber, butyl rubber, chloroprene rubber, chlorosulfonated polyethylene and ethylene‐propylene‐diene rubber and were generally not resistant to biodiesel and heating oil with 10 % biodiesel. Fluorocarbon rubber, fluorosilicone rubber and polyamide were the most resistant materials in all tested fuels up to 70 °C. The degree of damage to the sealing materials increased with higher test temperatures and the age of the fuels.     

超声波应用于稠油降黏的实验研究

稠油在我国已探明的储量中占比50%以上,而它的高密度、高黏度等特征使得其开采和运输的难度极大,因此,稠油降黏意义重大。超声波技术在稠油降黏的应用中已取得了一定的成效,但尚未得到现场大规模应用。为探究超声波在稠油降黏过程中的作用规律,基于室内实验设计了包括超声波发生器、流变仪、电子天平、恒温水浴等仪器组成的超声稠油降黏评价测试平台。在测试平台上,观测了超声波发生器的电功率、超声作用时间以及油样初始黏度对稠油降黏效果的影响。结果表明,只有在一定的条件下,超声波技术在稠油降黏中的应用才能取得较好的效果,说明了超声波技术对于稠油降黏以及油井的增产增注具有适用性。目前看来,超声波降黏技术在油田现场实际井中的应用及其降黏机理还需进一步深入的研究。     

Optimization and sensitivity study of biodiesel synthesis from Jojoba oil using mixed-integer programming

Jojoba oil-based biodiesel is promising alternative fuel due to its versatile properties. Renewable transportation fuels are considered as promising alternatives to conventional fuels. The physical and chemical properties of these fuels enabled them to be used in modern internal combustion engines; this makes them attractive for use as direct replacements or as additives of fossil fuels. Jojoba oil is extracted from Jojoba seeds, and it is an excellent feedstock for biodiesel after the transesterification process. The plant is highly adaptable to harsh weather including salty water, desert, and hot temperatures; thus, it can be grown in Saudi Arabia. This research work comprises a detailed optimization study of biodiesel production from Jojoba oil using mixed-integer programming. golden section search method was used for the optimization and sensitivity study was conducted for reaction time and temperature. The result shows that 54.1 minutes and 47.5 °C are the optimized reaction time and temperature to produce biodiesel which is considerably low as compared to previous studies.     

Evaluation of multiblock NIR/MIR PLS predictive models to detect adulteration of diesel/biodiesel blends by vegetal oil

This work investigates the potential of using simultaneously near infrared (NIR) and mid infrared (MIR) spectroscopy for the quantification of vegetable oil in diesel/biodiesel blends. The two spectral ranges were used separately with PLS regressions. To combine the two pieces of information, first a concatenated matrix was used and then H-PLS and S-PLS models were constructed. The models were compared in term of prediction errors (RMSEP). The results obtained in NIR spectroscopy were better than the ones obtained with MIR spectroscopy (considering the influence of the pretreatment and of the selected variables range). The multiblock methodology seems to be of great interest in quantitative analysis with the simultaneous use of information from the MIR and NIR spectroscopy.     

Modification of FAU zeolite as an active heterogeneous catalyst for biodiesel production and theoretical considerations for kinetic modeling

In this work, a high purity FAU-type zeolite catalyst was prepared from shale rock and modified as a heterogeneous efficient catalyst for biodiesel production from sunflower oil. The characterization properties for both of the prepared catalysts were determined using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDAX), Brunauer–Emmett–Teller (BET), and Fourier-transform infrared spectroscopy (FTIR). The incipient wetness impregnation method was adopted for loading the catalyst with three base precursors: NaOH, KOH, and Ca(OH)3. Different factors affecting transesterification reaction onto modified Na-K-Ca-FAU zeolite were investigated such as; temperature (35, 45, 55, and 65 °C), catalyst concentrations (2, 3,4, 5, and 6 wt%) and the molar ratio of methanol to sunflower oil (3:1, 6:1, 9:1 and 12:1). The optimum conditions of transesterification reactions were obtained for reaction time (4 h) and agitation rate (700 rpm) in a batch reactor at 65 °C reaction temperature, 5% catalyst concentration, and a 9:1 M ratio of methanol to oil. The experimental results showed that the conversion of triglyceride in sunflower oil to fatty acid methyl ester (FIME) increased from 48.62 to 91.6% when the FAU zeolite was loaded with 15 wt% of the three bases. The properties of the produced biodiesel were evaluated within the standard performance ASTM D-6751. This study shows that the three base precursors (i.e., NaOH, KOH, and Ca(OH)3) were successfully loaded onto support FAU zeolite and functioned as excellent catalysts for biodiesel production. Theoretical considerations for kinetic modeling in the heterogeneous transesterification reaction were investigated using MATLAB programming. The experimental and theoretical considerations for kinetic modeling were fitted well.     

Genetic Manipulation of Non-Classic Oilseed Plants for Enhancement of Their Potential as a Biofactory for Triacylglycerol Production

Global demand for vegetable oil is anticipated to double by 2030. The current vegetable oil production platforms, including oil palm and temperate oilseeds, are unlikely to produce such an expansion. Therefore, the exploration of novel vegetable oil sources has become increasingly important in order to make up this future vegetable oil shortfall. Triacylglycerol (TAG), as the dominant form of vegetable oil, has recently attracted immense interest in terms of being produced in plant vegetative tissues via genetic engineering technologies. Multidiscipline-based “-omics” studies are increasingly enhancing our understanding of plant lipid biochemistry and metabolism. As a result, the identification of biochemical pathways and the annotation of key genes contributing to fatty acid biosynthesis and to lipid assembly and turnover have been effectively updated. In recent years, there has been a rapid development in the genetic enhancement of TAG accumulation in high-biomass plant vegetative tissues and oilseeds through the genetic manipulation of the key genes and regulators involved in TAG biosynthesis. In this review, current genetic engineering strategies ranging from single-gene manipulation to multigene stacking aimed at increasing plant biomass TAG accumulation are summarized. New directions and suggestions for plant oil production that may help to further alleviate the potential shortage of edible oil and biodiesel are discussed.     

Synthesis of CaOSiO2 compounds and their testing as heterogeneous catalysts for transesterification of sunflower oil

The powder mixtures of calcium oxide (CaO) and silica gel (SiO₂) in molar ratios of 1:1, 1.5:1, 2:1 and 3:1 were mechanochemically treated with the addition of water, and were subsequently calcined with a goal of synthesizing CaSiO_3, Ca₃Si₂O₇, Ca₂SiO₄ compounds and CaO/Ca₂SiO₄ two-phase mixture. The prepared materials were characterized by XRD, FTIR, SEM/EDS, particle size laser diffraction (PSLD), UV–vis diffuse reflectance spectroscopy (DRS), N₂ adsorption/desorption isotherms, Hammett indicator for basic strength and volumetric analysis for free CaO content. The catalytic activity of calcium silicates with different Ca/Si ratios was tested in the transesterification of triacylglycerols (sunflower oil) with methanol. Samples obtained with initial composition 2CaO·SiO₂ and 3CaO·SiO₂ calcined at 700?°C, and 3CaO·SiO₂ calcined at 900?°C had high catalytic activity, resulting with triacylglycerols conversion and fatty acids methyl ester formation (FAME or biodiesel) above 96%. The activity of these samples can be attributed to the existence of free CaO defined by CaO/Ca₂SiO₄ complex mixture. The effect of different amount of catalyst used for transesterification (0.2–2?wt%) was analyzed using the most active catalyst i.e. 3CaO·SiO₂ calcined at 700?°C as well as possibility of its reuse for biodiesel synthesis. It was also found that CaSiO₃, Ca₃Si₂O₇ and Ca₂SiO₄, phases did not possess catalytic activity.     

Airborne mercury pollution from a large oil spill accident on the west coast of Korea

Atmospheric mercury pollution was recognized after a large oil spill on the west coast of Korea on 7 December 2007. In this study, the concentrations of gaseous elemental mercury (GEM: Hg(0)) in air were measured both shortly after the oil spill ( approximately 100h) and 1month after the accident near the accident site. When the Hg concentration levels were compared between two seashore sites and two parallel sites offshore, the values tend to decrease further offshore. The unusual rise in Hg concentration levels observed on the seashore area shortly after the accident (mean of 16.4+/-9.85ngm(-3)) dropped dramatically after 1month with active cleanup activities (2.99+/-1.40ngm(-3)). Because of the connection between crude oil and Hg (one of the major impurities), the unusual rise in the atmospheric Hg after the oil spill can be explained by the active evasion of Hg from the spilled crude oil. Although Hg levels determined a few days after the accident did not exceed the reference exposure limits (REL) proposed by several agencies, the early build-up of elemental mercury level due to the oil spill might have exerted certain impacts on the surrounding environments.     

Oligoesters and polyesters produced by the curing of sunflower oil epoxidized biodiesel with cis-cyclohexane dicarboxylic anhydride: Synthesis and characterization

Oligoesters and polyesters produced from sunflower oil biodiesel were synthesized and characterized. The polymers were obtained through the reaction of fatty acid methyl epoxy esters (EE) with cis-1,2-cyclohexane dicarboxylic anhydride (CH) and triethylamine (TEA) as initiator. Some reactions were conducted by adding small amounts of 1,4-butanediol diglycidyl ether (BDGE). The intermediate products of the synthesis process, including sunflower oil, methyl ester, epoxidised methyl esters, and the oligoesters and polyesters produced, were followed by Fourier Transform Infrared Spectroscopy and ¹H and ¹³C nuclear magnetic resonance. The products obtained from the curing of the epoxidised esters with different compositions present similar chemical structures; however, they still depend on the amount of the epoxy resin BDGE that was added in the polymerization reaction. Thermoplastic materials with molecular weights (MW) starting at 3800 g/mol and reaching very high MWs, resulted in cross linked polymers. The thermal behaviour of the different products was investigated using differential scanning calorimetry and thermogravimetric analyses. The presence of BDGE in the structure of the materials increases the bonding capacity, resulting in higher molecular weight materials, which present good thermal stability.     

一种可用于重油降粘的大功率超声换能器设计

基于夹心式压电换能器基本原理,设计了一种可用于井口重油降粘和高凝油降凝的工业规模应用的大功率压电超声换能器,其工作频率为16.86 kHz,输入电功率为500 W,可在100℃高温环境下长时间连续工作。首先根据工作环境需要设计了换能器模型,结合等效电路法和传输矩阵法,计算了换能器满足谐振频率条件的各部分参数;通过有限元仿真软件ANSYS对换能器进行了模态分析和谐响应分析,确定了换能器的最佳工作模态和工作频率。根据仿真模型,制作了工程样机,通过阻抗分析仪测得其实际的工作频率与仿真结果的误差为0.5%。这种大功率压电超声换能器有望在重油降粘以及超声处理工业中得到规模化应用。     

重质渣油沥青树脂的耐热性

利用纯芳烃原料和重质渣油研制的沥青树脂具有优良的耐热性。从C C键的离解能来看,沥青树脂的热裂解温度较高。通过测定溶解度、软化点及沥青树脂的固化,考察了实验室合成的沥青树脂各阶段的基本物理性能以及C阶沥青树脂的耐热性,初步探讨了耐热性与分子结构之间的相关性。结果表明B阶树脂具有良好的溶解性;苯甲醛(BA)系B阶沥青树脂硬化成C阶沥青树脂的温度较高,C阶沥青树脂的收率亦高;C阶沥青树脂具有较优异的耐热性,特别是高温阶段的耐热性优于聚酰亚胺。     

超重油降粘中超声波作用的研究

以委内瑞拉超重油和新疆风城超重油为研究对象,进行了超声辅助降粘的研究。在实验中,制备了两类四种实验样品:分别掺入20%和30%柴油的两种委内瑞拉超重油样品、在O/W降粘体系下制备的委内瑞拉超重油样品和风城超重油样品。使用频率为18 k Hz的超声变幅杆和24 k Hz的超声清洗槽对上述四种实验样品进行超声处理,结果表明:1)对掺入20%和30%柴油的委内瑞拉超重油,经过超声处理的超重油样品在20℃时粘度分别增高了25%和15%以上;2)在O/W降粘体系超重油降粘中,风城超重油样品经过超声作用后,在20℃粘度降低了25%以上,而降粘剂的使用量可减少20%,超声辅助降粘效果明显;3)在O/W降粘体系超重油降粘中,委内瑞拉超重油样品经过超声处理后,在14℃时,超声处理过的样品的粘度降低不高于25%,在高于这一温度的情况下则未观察到明显的粘度降低。文中对上述实验结果产生的原因进行了定性的分析。     

V-W-Mo-Cu催化剂作用下生物质醇解重油加氢精制研究

生物质醇解产生的重油降低了生物油品质。为此,本文考察了V-W-Mo-Cu催化剂作用下重油的加氢精制。结果表明,在330℃以上该催化剂才表现出加氢反应活性,在450℃时轻油产率最高可到93%。延长加氢反应时间有利于重油低温下的聚合反应和高温下的裂解反应;同时,只有在6 MPa以上的初始氢压下才能饱和裂解片段,从而提高重油加氢所得的轻油产率。轻油的气相色谱-质谱联用仪(GCMS)分析结果表明,催化加氢使重油大分子裂解生成1-甲基-2-乙基苯、丁基苯、1-乙基-3-乙烯基苯和苯酚等小分子的芳烃和酚类物质。然而,加氢后催化剂的红外分析结果表明,重油同时发生了聚合反应,生成含有多种含氧官能团的大分子芳烃或酚类聚合物。经过550℃焙烧后,催化剂重复使用5次,轻油产率仍有70%。     

含氮化合物修饰的超细无机硼酸盐润滑油添加剂的结构和性能

本文对含N化合物修饰的超细无机硼酸盐润滑油添加剂的形貌、组成、结构进行了分析表征;并考察了其抗氧化性能和防腐、防锈性能.     

正交法探讨均相碱催化制备生物柴油的优化条件

以菜籽油为原料,甲醇钠为催化剂,二异丙醚为共溶剂,通过酯交换法制取生物柴油,并考察了醇油摩尔比、催化剂用量、共溶剂用量、反应时间和温度对生物柴油产率的影响.通过正交试验得出菜籽油与甲醇酯交换反应的最优条件为:醇油比为6:1,甲醇钠催化剂用量为油重的1.2%,共溶剂与油的摩尔比为1.2 :1,反应温度60℃,反应时间80min,低速120r/min搅拌强度下,转化率达到96.45%.制得的生物柴油各理化指标均符合美国和德国生物柴油测试标准.     

Preparation of H-oleoyl-carboxymethyl-chitosan and the function as a coagulation agent for residual oil in aqueous system

In this study, H-form oleoyl-carboxymethyl-chitosan (H-O-CMCS) was prepared as a coagulation agent to clean up the residual oil from the waste-water of oil extraction (WWOE). The Fourier transform infrared (FTIR) spectra confirmed the formation of an amide linkage between amino groups of carboxymethyl chitosan (CMCS) and carboxyl groups of oleic acid. The adsorption capacities of four absorbents (H-O-CMCS, chitosan, activated carbon and polyaluminium chloride (PAC)) for the residual oil were investigated. Compared with chitosan, activated carbon and PAC, H-O-CMCS was more effective in removing the residual oil from WWOE, which could successfully wash up almost 99% of residual oil from WWOE at the dosage of 0.2 g/L, the mixing time of 3 min, 500 rpm, and a broader range of pH (the system temperature ≤45°C). In similar conditions, comparatively, chitosan, activated carbon and PAC could wash 90%, 82% and 92% of residual oil from WWOE, respectively.     

碳纤维及原丝用油剂研发及应用

介绍了聚丙烯腈基碳纤维及原丝用油剂的种类及其特性,论述了氨基改性硅油等几种碳纤维及原丝用主要油剂的研发进展。简述了国内碳纤维及其原丝用油剂的供需现状。讨论了国内外碳纤维专用油剂的发展趋势。