Modification of thermal and oxidative properties of biodiesel produced from vegetable oils

Trans esterification of three vegetable oils, sunflower oil, linseed oil and mixed oils as; sunflower-soyabean and olein were carried out using methanol, and potasium hydroxide as catalyst. The methyl esters of the corresponding oils were separated from the crude glycerol and characterized by physical-chemical methods to evaluate their thermal properties. This methods are determination of densities, cloud points, pour points, flash points, kinematic viscosities, hydrogen/carbon ratios, sulfur contents, ash contents and triglycerides. The physico-chemical characteristic of biodiesel treated with ozone showed improvement of pour point and flash point indicating higher degree of safety for fuel. Methyl esters mixed with their corresponding ozonated oil were subjected to comparison and evaluation for their thermal properties by the thermo gravimetric analysis differential thermal analysis from which the calculated heat of enthalpy and comparison with the heat of conventional diesel. The results showed that the oxygen content of biodiesel samples treated with ozone increased weight % and resulted in more extensive chemical reaction, promoted combustion characteristics and less carbon residue was produced. Gas chromatography appeared more suitable to address the problem of determining/verifying biodiesel methyl ester and showed that methyl ester content was impurity free. Ultra violet-detection was used for rapid quantization of triglycerols. From the analyses performed biodiesel treated with ozone modified the thermal and oxidative stability shown by the high combustion efficiency indicated by the high heat of enthalpy and reducing the emission of particulate matter.     

Biodiesel synthesis from non-edible oils by transesterification using the activated carbon as heterogeneous catalyst

The need for renewable environmentally friendly energy resources is growing every day. Biodiesel is one of the most promising alternatives to the conventional non-renewable energy resources. Heterogeneous catalysts proved a high efficiency in the transesterification of oils to produce biodiesel. In this research, activated carbon was tested as a heterogeneous catalyst in the transesterification of two non-edible oils (waste cooking oil and Jatropha oil) with methanol to produce biodiesel. Activated carbon was characterized using X-ray diffraction, scanning electron microscope and Fourier transformed infrared. The effect of different operating parameters, namely operation time (30, 60, 120 and 180 min), alcohol-to-oil molar ratio (4:1, 6:1, 8:1 and 10:1), catalyst loading [0.5, 1, 2, 3 and 5% (w/w)] and rotational speed (100, 200, 300 and 400 rpm), was investigated. Results showed that increasing the operational time, the alcohol-to-oil molar ratio and the catalyst loading increases the conversion to biodiesel but only to some extent; increasing the stirring rate was found to be beneficial to the process. The optimum conditions were found to be 2 h of heating, 6:1 alcohol-to-oil ratio, 1 wt% catalyst loading and 400 rpm stirring. Under optimum conditions, the conversion to biodiesel reached 93.95 and 93.27% for the waste cooking oil and the Jatropha oil, respectively. The properties of the obtained biodiesel (density, viscosity, flash point, pour point and cloud point) were measured giving promising results.     

Development and evaluation of biodiesel fuel and by-products from jatropha oil

Biodiesel is an environmentally friend renewable diesel fuel alternative. Jatropha seeds can be a feedstock to produce a valuable amount of oil to be converted to biodiesel using transesterification reaction. Jatropha plant has been successfully grown in southern Egypt using primary treated municipal wastewater for its irrigation. Abench scale production of biodiesel from Jatropha oil (using methyl alcohol and sodium hydroxide as catalyst) was developed with methyl esters yield of 98 %. Biodiesel was produced on a pilot scale based on the bench scale experiment results with almost the same methyl esters yield of 98 %. The produced biodiesel was evaluated as a fuel and compared with petroleum diesel according to its physical and chemical parameters such as viscosity, flash point, pour point, cloud point, carbon residue, acid value and calorific value. The experimental techniques and product evaluation results show that such properties of the produced biodiesel are near to that of petroleum diesel. A mass balance representing the transesterification process is presented in this study. Glycerol of 85 % purity was produced and evaluated as a valuable byproduct of the process. Free fatty acids and sodium phosphate salts which have industrial interesting are also produced and evaluated.     

Performance and pollutants analysis on diesel engine using blends of Jatropha Biodiesel and Mineral Turpentine as fuel

Performance and pollutants features of Jatropha–Mineral Turpentine blends along with diesel have been examined in a single-cylinder compression ignition engine. Vegetable oils have higher viscosities than diesel fuel, and it greatly disturbs the performance, durability, burning and discharge features of the compression ignition engine. The tests were performed with different blend combinations of Jatropha–Mineral Turpentine oil as fuel. The experimental outcome indicates that brake thermal efficiency of the blend of 80% Jatropha Biodiesel and 20% of Mineral Turpentine is nearby to diesel fuel at 75% load. Carbon monoxides, hydrocarbons and emission were reduced to the considerable amount, whereas the oxides of nitrogen increase with increase in part load and reduced with 75% and full load operations. The specific fuel consumption of Jatropha–Mineral Turpentine blends found to be slightly upper than diesel fuel. The heat release rate and cylinder pressure of Jatropha–Mineral Turpentine blends were closer to diesel fuel. The test results recommend that Jatropha–Mineral Turpentine blends might stay a decent auxiliary to diesel fuel in the near upcoming and it can be concluded that Jatropha–Mineral Turpentine oil blends could be utilized in a conventional compression ignition engine with no alteration.     

Bioremediation of dry olive-mill residue removes inhibition of growth induced by this waste in tomato plants

The disposal of dry olive-mill residue, the waste product from olive oil production, is a serious environmental issue. Dry olive-mill residue, being rich in organic and inorganic nutrients, could be used as fertilizer; however, it contains phenolic compounds that can inhibit plant growth. In order to clarify whether bioremediation of this waste could be a valuable strategy for its reuse, the effect of aqueous extract of dry olive-mill residue, untreated or bioremediated by the saprobe fungi Coriolopsis rigida and Penicillium chrysogenum-10, has been analyzed in relation to some physiological parameters of tomato plants. The data show that aqueous dry olive-mill residue significantly reduces the biomass of roots and shoots. In particular, it causes a dramatic reduction in root length, area, and volume as well as in the number of root tips. At an early stage, aqueous dry olive-mill residue also reduces the content of chlorophyll a and b and the efficiency of PS II. The inhibition of growth seems to be due to the increase in phenolic compounds that induce oxidative stress. Interestingly, when plants are treated with aqueous dry olive-mill residue bioremediated by saprobe fungi a decrease in phenolic content and an alleviation of oxidative stress occur. In conclusion, the results show that bioremediation of aqueous dry olive-mill residue is a useful tool to remove most of the inhibiting effects of this waste on plant growth.     

Production optimization and quality assessment of biodiesel from waste vegetable oil

Biodiesel production is worthy of continued study and optimization of production procedures because of its environmentally beneficial attributes and its renewable nature. In Egypt, millions L. of oil used for frying foods are discarded each year into sewage systems. Thus, it adds to the cost of treating effluent or pollutes waterways. This study is intended to consider aspects related to the feasibility of the production of biodiesel from waste/recycled oils in an attempt to help reduce the cost of biodiesel and reduce waste and pollution coming from waste oils. The variables affecting the yield and characteristics of the biodiesel produced from used frying oil were studied, the achieved results were analyzed and a set of recommendations was proposed. From the obtained results, the best yield percentage was obtained using a methanol/oil molar ratio of 6:1, potassium hydroxide as catalyst (1%) and 65 °C temperature for one hour. The yield percentage obtained from waste vegetable oil was comparable to that obtained from neat vegetable oil which reached 96.15% under optimum conditions. From the results it was clear that the produced biodiesel fuel, whether from neat vegetable oil or waste vegetable oil, was within the recommended standards of biodiesel fuel.     

Different techniques for the production of biodiesel from waste vegetable oil

The production of biodiesel from waste vegetable oil offers a triple-facet solution: economic, environmental and waste management. The new process technologies developed during the last years made it possible to produce biodiesel from recycled frying oils comparable in quality to that of virgin vegetable oil biodiesel with an added attractive advantage of being lower in price. Thus, biodiesel produced from recycled frying oils has the same possibilities to be utilized. While transesterification is well-established and becoming increasingly important, there remains considerable inefficiencies in existing transesterification processes. There is an imperative need to improve the existing biodiesel production methods from both economic and environmental viewpoints and to investigate alternative and innovative production processes. This study highlights the main changes occurring in the oil during frying in order to identify the characteristics of oil after frying and the anticipated effects of the products formed in the frying process on biodiesel quality and attempts to review the different techniques used in the production of biodiesel from recycled oils, stressing the advantages and limitations of each technique and the optimization conditions for each process. The emerging technologies which can be utilized in this field are also investigated. The quality of biodiesel produced from waste vegetable oil in previous studies is also reviewed and the performance of engines fueled with this biodiesel and the characteristics of the exhaust emissions resulting from it are highlighted. The overarching goal is to stimulate further activities in the field.     

塔北隆起深层海相油藏中原油及族组分碳同位素组成的纵向分布特征及其地质意义

利用MAT252同位素质谱仪分析了塔里木盆地塔北隆起深层海相油藏中原油及族组分的碳同位素组成。研究表明该区深层海相油藏中原油的全油碳同位素组成主要受生源控制,受热力作用影响较小;而在继承生源的碳同位素组成的基础上,热力作用将对原油族组分的碳同位素组成及其逆转和分馏产生重要影响。总的趋势是随着油藏埋藏深度的增大和热力作用的加强,饱和烃组分的碳同位素组成逐渐变重,而沥青质组分的碳同位素组成不断变轻,族组分碳同位素逆转程度和分馏程度有所加强,并出现饱和烃﹥芳烃﹥非烃﹥沥青质的整体逆转现象。塔北隆起深层海相原油族组分的碳同位素组成的纵向变化特征,可以反映出热力作用对原油稳定性的影响。     

The evolution characteristics and fractionation mechanism of carbon isotopes in the process of "multi-stage hydrocarbon generation"

The Jiyang Sag and the Liaohe Basin are the two important areas where immature oil resources are distributed in China. From these two areas immature-low mature to mature oil samples were collected for carbon isotopic analysis. The extracts of source rocks are dominant in the Jiyang Sag while crude oils are dominant in the Liaohe Basin. The maturity index, R., for source rocks varies from 0.25%(immature) to 0.65% (mature). Studies have shown that within this range of R. values the extracts of source rocks and crude oils, as well as their fraction components, have experienced observable carbon isotope fractionation. The carbon isotopic values tend to increase with burial depth, the oils become from immature-low mature to mature, and the rules of evolution of oils show a three-stage evolution pattern, i. e. ,light→heavy→light→heavy oils. Such variation trend seems to be related to the occurrence of two hydrocarbon-generating processes and the main hydrocarbon-forming materials being correspondingly non-hydrocarbons and possessing MAB characteristics, lower thermodynamic effects and other factors. In the process towards the mature stage, with increasing thermodynamic effects, the thermal degradation of kerogens into oil has become the leading factor, and correspondingly the bond-breaking ratio of 12 C-13C also increases,making the relatively 12C-rich materials at the low mature stage evolve again towards 13C enrichment.     

A review of the synthesis and characterisation of pillared clays and related porous materials for cracking of vegetable oils to produce biofuels

This paper presents an overview of the modification of clay minerals by propping apart the clay layers with an inorganic complex. This expanded material is converted into a permanent two-dimensional structure, known as pillared clay or shortly PILC, by thermal treatment. The resulting material exhibits a two-dimensional porous structure with acidic properties comparable to that of zeolites. Synthetic as well as natural smectites serve as precursors for the synthesis of Al, Zr, Ti, Fe, Cr, Ga, V, Si and other pillared clays as well as mixed Fe/Al, Ga/Al, Si/Al, Zr/Al and other mixed metal pillared clays. Biofuels form an interesting renewable energy source, where these porous, catalytically active materials can play an important role in the conversion of vegetable oils, such as canola oil, into biodiesel. Transesterification of vegetable oil is currently the method of choice for conversion to biofuel. The second part of this review focuses on the catalysts and cracking reaction conditions used for the production of biofuel. A distinction has been made in three different vegetable oils as starting materials: canola oil, palm oil and sunflower oil.     

Generation of aliphatic acid anions and carbon dioxide by hydrous pyrolysis of crude oils

Two crude oils with relatively high (0.60 wt%) and low (0.18 wt%) oxygen contents were heated in the presence of water in gold-plated reactors at 300°C for 2348 h. The high-oxygen oil was also heated at 200°C for 5711 h. The compositions of aqueous organic acid anions of the oils and of the headspace gases were monitored inn order to investigate the distribution of organic acids that can be generated from liquid petroleum.The oil with higher oxygen content generated about five times as much organic anions as the other oil. The dominant organic anions produced were acetate, propionate and butyrate. Small amounts of formate, succinate, methyl succinate and oxalate were also produced. The dominant oxygen-containing product was CO₂, as has been observed in similar studies on the hydrous pyrolysis of kerogen. These results indicate that a significant portion (10–30%) of organic acid anions reported i be generated by thermal alteration of oils in reservoir rocks. The bulk of organic acid anions present in formation waters, however, is most likely generated by thermal alteration of kerogen in source rocks. Kerogen is more abundant than oil in sedimentary basins and the relative yields of organic acid anions reported from the hydrous pyrolysis of kerogen are much higher than the yields obtained for the two oils.     

Markers for secondary reactions of migrated crude oil on carbonaceous surfaces

A high abundance of ethyl substituted aromatic hydrocarbons (HCs) relative to their methyl counterparts is an unusual feature of some crude oils. Enhanced stability of ethyl aromatic HCs in the presence of tetralin was observed when individual ethylated compounds were heated with activated carbon in sealed tubes over a range of 170–340 °C. In addition, conversion of the common distribution of alkyl aromatic HCs to an unusual distribution, containing a higher relative abundance of ethyl compounds, was demonstrated by way of closed system heating of the aromatic fraction of a crude oil in the presence of activated carbon. The conditions for this unusual process require the presence of hydrogen donor components, which selectively limit the reaction and depletion of ethylated compounds relative to methylated compounds. The phenomenon has been shown to occur for substituted benzenes, naphthalenes, phenanthrenes and biphenyls. Enhanced abundance of ethyl aromatic HCs relative to their methylated counterparts is therefore proposed as an indicator for secondary reactions of migrated crude oil that has undergone thermal alteration after contact with carbonaceous surfaces in sediments. Application of these principles to selected crude oils and sediment extracts from the Carnarvon and Cooper/Eromanga Basins (Australia) indicates that significant secondary reaction of migrated crude oil has occurred.     

Biodiesel production from three mixes of oils with high free fatty content: quality evaluation and variable analysis

Due to the excessive use of fossil fuels around the world, more environmentally friendly alternatives have been studied. Technologies for the production of ethanol, biogas and biodiesel are focusing on the importance of improving costs and efficiency. Biodiesel can be used in automotive internal combustion, is biodegradable and has no presence of metals, however, it lacks competitiveness versus petrodiesel mainly by the high cost of the pure oils used for its production. The aim of this study was to obtain biodiesel from oil samples with high content of free fatty acids (>1 %) obtained from three fast food restaurants using their molecular weight and acidity index values in order to neutralize the free fatty acids in a one-step reaction and perform a screening for optimal conditions for transesterification. The experimental design consisted of two reaction times (60 and 90 min); four methanol–oil molar ratios—6:1, 10:1, 15:1 and 20:1; and two catalysts (NaOH and KOH) at three concentrations 0.5, 1 and 1.5 % with a constant temperature of 60 °C and 500 rpm. The optimum conditions for the different waste cooking oil feedstocks were established reaching a final yield up to 85.53 % of biodiesel, concluding that there is viability of production through the use of this raw material and free fatty acids neutralization technique, obtaining a biofuel that meets international quality standards.     

Study on clean technology-assisted combustion behavior and NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> emission using thermal imager for alternate fuel blends

The correlation between oxides of nitrogen emission and in-cylinder temperature of diesel engine fueled with various alternative fuels has been investigated in this research paper. Experimentations were performed in engine without any modifications using pure high-speed diesel fuel, used cooking oil biodiesel (UCO20), animal fat residue biodiesel (AFR20) and camphor oil (CMR20) at 20% volume concentration of biodiesel each. From combustion analysis, the heat release rate and peak cylinder pressure of biodiesel blends were about 13.487% lower and 4.819% higher than those of diesel fuel on an average, respectively. Longer combustion duration has been observed for all biodiesel blends at all load conditions. Oxides of nitrogen emission level show 16.405, 10.352 and 7.524% increment for UCO20, AFR20 and CMR20, respectively. Noteworthy NO _x reduction of about 43.8% was recorded for diesel blended with camphor oil when compared to other biodiesel blends. The relationship between in-cylinder temperature and NO _x emission concentration was premeditated through thermal imager. The result depicted that the increase in NO _x concentration depends on augmented in-cylinder temperature for all test fuels.     

Correlation between the chemical structure of biodiesel and its physical properties

Biodiesel is a renewable, biodegradable, environmentally benign, energy efficient, substitution fuel which can fulfill energy security needs without sacrificing engine’s operational performance. Thus it provides a feasible solution to the twin crises of fossil fuel depletion and environmental degradation. The properties of the various individual fatty esters that comprise biodiesel determine the overall properties of the biodiesel fuel. In turn, the properties of the various fatty esters are determined by the structural features of the fatty acid and the alcohol moieties that comprise a fatty ester. Better understanding of the structure-physical property relationships in fatty acid esters is of particular importance when choosing vegetable oils that will give the desired biodiesel quality. By having accurate knowledge of the influence of the molecular structure on the properties determined, the composition of the oils and the alcohol used can both be selected to give the optimal performance. In this paper the relationship between the chemical structure and physical properties of vegetable oil esters is reviewed and engineering fatty acid profiles to optimize biodiesel fuel characteristics is highlighted.     

东营凹陷原油、储层吸附烃全扫描荧光特征与应用

应用全扫描荧光分析(TSF、QGF-E)技术对东营凹陷沙河街组40个原油、15个储层包裹烃、39个储层砂吸附烃的三维荧光特征进行了定性与定量分析。分析表明,原油与包裹烃的TSF指纹特征总体相似,均为单峰型,指示油气成因具有内在的联系。观察到不同原油TSF强度峰宽与最高值有异,低成熟度样品往往具有较高的TSF强度及较宽的峰。进一步分析表明,原油TSF最高强度、TSF定量参数R1[270nm(Em360nm/Em320nm)]、R2[260nm(Em360nm/Em320nm)]与生物标志物成熟度参数C29甾烷ααα20S/(S+R)、Ts/(Tm+Ts)等有较好的线性正相关性,反映TSF荧光指纹特征及其定量参数可作为一种温标用于热成熟度分析。应用TSF技术确认东营凹陷中央隆起带原油成熟度具有自西南向东北逐渐降低的变化规律,其反映了油源与油气充注方面的重要信息。对东营凹陷牛庄洼陷两口井的储层砂的QGF-E分析表明,颗粒样品所在层段的烃类含量普遍较高,反映致密薄层砂、微裂缝等可能为该洼陷岩性油气藏重要的隐蔽型油气运移通道。TSF、QGF-E技术在油气族群、储层含油气性、油气运移路径与油层识别等方面具有广泛的应用前景。     

松辽盆地双城—太平川地区原油地球化学特征及其成熟度差异

松辽盆地北部双城—太平川地区扶杨油层原油地球化学特征相近,正构烷烃分布完整,呈单峰型,主峰碳主要为C23,部分原油具有轻碳优势,奇偶优势不明显。三环萜烷含量较丰富,部分原油伽马蜡烷、孕甾烷和升孕甾烷含量较高,规则甾烷呈"V"型分布,碳同位素值偏轻,生源构成以低等水生生物和菌藻类为主,兼有高等植物生源输入,母源形成环境为微咸水还原—淡水氧化环境。本区原油的总体特征比较接近,具有相似的生源母质和有机相,但其成熟度存在着一定差异。根据生物标志物参数,原油分为三个组群,即低成熟油、低成熟—中等成熟油和中等成熟油,主要为低成熟—中等成熟原油。认为研究区具有形成低成熟油的有利烃源条件,应该加强对低成熟油的勘探开发。同时加强长春岭背斜带及其周缘构造高部位有利圈闭的勘探与评价。     

生排烃过程中正构烷烃单体碳同位素组成的变化特征及其研究意义

通过对生排烃模拟实验产物 (残留油和排出油 )中正构烷烃单体碳同位素组成的测定,揭示出生排烃过程中正构烷烃碳同位素组成的变化特征。研究表明,生烃初期,液态正构烷烃主要来自干酪根的初次裂解,它们的碳同位素组成不论是在排出油中还是在残留油中,随温度的变化都不明显,呈现较相似的分布特征;在生烃高峰期,早期形成的沥青质和非烃等组分的二次裂解以及高碳数正构烷烃可能存在的裂解,使得正构烷烃单体碳同位素组成明显富集13 C,尤其在高碳数部分呈现出较大的差异。另外,实验结果显示排烃作用对液态正烷烃单体碳同位素组成的影响不太显著。     

Performance analysis of Diesel engines fueled by biodiesel blends via thermodynamic simulation of an air-standard Diesel cycle

Because of environmental problems, it becomes necessary to develop alternative fuels that give engine performance at par with diesel. Among the alternative fuels, biodiesel and its blends hold good promises as an eco-friendly and the most promising alternative fuel for Diesel engine. The properties of biodiesel and its blends are found similar to that of diesel. Many researchers have experimentally evaluated the performance characteristics of conventional Diesel engines fueled by biodiesel and its blends. However, experiments require enormous effort, money and time. Hence, via finite-time thermodynamics simulation, an air-standard Diesel cycle model with heat transfer loss and variable specific heats of working fluid is analyzed to predict the performance of Diesel engine. The effect of compression ratio, cut-off ratio and fuel type on output work and thermal efficiency is investigated through the model. The fuels considered for the analysis are conventional diesel, rapeseed oil biodiesel and its blend (20 % biodiesel and 80 % diesel by volume). Numerical simulations showed that the output work and thermal efficiency of the engine decrease with increase of cut-off ratio for all fuels. Also, the model predicts similar performance with diesel and biodiesel blend which means that the biodiesel blend (20 % biodiesel and 80 % diesel by volume) could be a good alternative and eco-friendly fuel for conventional Diesel engines without any need to modify the engine.     

生物降解作用对储层抽提物中多甲基取代萘分布的影响

对辽河盆地冷东油田冷43块沙三段油藏3口取心井岩心抽提物进行了详细的地球化学分析, 族组成和饱和烃生物标志物分布显示油藏遭受了不同程度生物降解作用的影响, 降解程度由油柱顶部向底部增大, 呈良好梯度变化特征.对比不同降解程度原油样品中三甲基萘、四甲基萘和五甲基萘含量和分布可以发现生物降解的明显控制作用, 根据甲基取代萘异构体在生物降解过程中相对含量的变化初步确定了三甲基萘、四甲基萘和五甲基萘单个异构体的生物降解顺序, 结果表明那些热力学稳定性高的异构体容易遭受微生物的攻击, 而热力学稳定性低的异构体却在生物降解过程中相对富集, 表明生物降解作用完全不同于热力学作用过程, 当原油遭受中等程度生物降解作用影响后, 根据热力学稳定性提出的成熟度参数不再能提供有效的成熟度信息, 易降解和难降解异构体间的比值却是衡量原油遭受生物降解作用程度的地球化学新指标.