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.     

基于多相流数值模拟的某石油污染场地地下水中VOCs自然衰减过程识别及能力评估

监测自然衰减(monitoring natural attenuation,MNA)技术是目前普遍认可的去除地下水中挥发性有机污染物(volatile organic compounds,VOCs)的技术。但受其修复周期长、监测费用昂贵等因素的影响,实地开展MNA技术修复污染场地具有一定的局限性。基于此,本研究运用多相流数值模拟手段识别了某石油污染场地内典型VOCs污染物(苯、甲苯、萘)在地下水中的自然衰减过程并评估了其自然衰减能力。结果表明:采用TMVOC所建立的多相流数值模拟模型能较好地预测和识别VOCs在地下水中的衰减规律;在研究区中,苯、甲苯和萘由于理化性质差异,在地下水中的污染羽分布特征不同,其自然衰减过程受挥发、吸附和生物降解作用的影响程度也不同;挥发和生物降解作用对VOCs自然衰减的影响程度均为苯>甲苯>萘,而吸附作用对VOCs自然衰减的影响程度为萘>甲苯>苯;在污染源被阻断的前提下,苯、甲苯和萘分别在泄漏发生7.0、6.5和6.0年后通过自然衰减达到理想去除效果。本文研究成果可以为水文地质条件类似的VOCs污染场地MNA修复方案的制定和修复效果评估提供理论支撑。     

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.     

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.     

稳定型与负载型FeS修复Cr(Ⅵ)污染地下水的可行性

纳米硫化亚铁（Nano-FeS）粒径小、比表面积大、反应活性高,但易团聚、易氧化的特点使其在地下水修复中的应用受到限制,通过改性可提高Nano-FeS的分散性和稳定性。本文选用羧甲基纤维素钠（CMC）及羟基铝柱撑膨润土（Alb）两种改性剂,制备了稳定型改性的CMC-FeS和负载型的Alb-FeS。分别从分散性、抗沉降性、抗氧化性、反应性和迁移性考察了两种改性Nano-FeS的性能。结果表明：Alb-FeS与CMC-FeS的分散性均较Nano-FeS得到明显改善;3 d后Nano-FeS完全沉降氧化,CMC-FeS沉降3 cm且开始氧化,而Alb-FeS沉降16 cm却未氧化;在相同的实验条件下,Alb-FeS、Nano-FeS、CMC-FeS对Cr （Ⅵ）的去除能力从强到弱,去除率分别是85.16%、84.90%、82.78%。在粗砂、中砂与细砂介质中,3种FeS的迁移能力从强到弱依次为CMC-FeS、Alb-FeS、Nano-FeS;在3种介质中CMC-FeS的最大迁移距离分别是Nano-FeS的6.1倍、6.4倍和3.4倍,而Alb-FeS与Nano-FeS相比迁移性没有明显提高。综合考虑分散性、抗沉降性、稳定性、反应活性及迁移能力,实际应用中宜优先选择CMC-FeS作为Cr （VI）污染地下水的原位修复材料。     

Protection of biodiesel and oil from degradation by natural antioxidants of Egyptian Jatropha

Residue of methanolic extract of Egyptian Jatropha curcas contains bioactive substances such as phenolic compounds, which succeeded to be used as natural antioxidants for the protection of oils and their corresponding biodiesel against oxidative deterioration. In the present work, the residue of Jatropha roots were extracted with methanol and resulting residues, were investigated regarding their content of total phenolic compounds by folin-Cioalteau assay. Further, the antioxidant activities of the extracts were characterized by the 2,2-diphenyl-1-picrylhydrazyl radical method and proved remarkable results. Oxidation stability of Jatropha oil, used fried oil and olive oil and their corresponding biodiesel obtained by conventional transesterification were tested using thermal oxidation. Natural antioxidants such as (α-trocopherol), synthetic antioxidants as butylated hydroxytoluene and natural Jatropha root extract were used in the present study in comparison to investigate their addition effect on the oxidative stability of oils and their corresponding biodiesel. In the rapied thermal treatment test, results showed that addition of butylated hydroxytoluene 0.25 % was able to stabilize Jatropha oil 6 h, but poorly stabiliz biodiesel. Addition of 0.25 % α-trocopherol to Jatropha oil showed less oxidation stability after 2 h thermal treatment. Crude root extract addition at 0.25% to Jatropha oil showed good stability up to 4 h thermal treatment while addition of root extract at 0.25 % to biodiesel showed better stability up to 6 h thermal treatment. Besides addition of 220 ppm crude root extract to biodiesel was enough sufficient to occure oxidative stabilization. Also Jatropha root residue addition at 400 ppm was effective antioxidant for fresh Jatropha oil.     

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.     

生物炭修复重金属污染土研究进展

随着城市化进程的加快及工业生产的迅速发展,土壤重金属污染日益加剧,对生态环境造成严重的危害。生物炭是缺氧或限氧条件下加热生物质制得的高度芳香化富含碳的固态物质,其在重金属污染土修复方面具有显著效果,受到广泛关注。基于近些年来国内外围绕生物炭修复重金属污染土所取得的研究成果,分别从生物炭的制备及性质、修复效果及其影响因素、修复机理等方面总结了该领域的研究现状及进展,取得如下主要认识:（1）生物炭具有价格低廉,修复效率高,改良土壤、环境友好等优势;（2）生物炭的理化性质主要受原材料和热解温度的影响,采用活化、磁化、氧化和消化等方法能改善生物炭的性质,提高修复效率;（3）生物炭对土壤中重金属迁移性和生物有效性的影响包括两个方面:固定重金属减少生物有效性或者迁移重金属增加生物有效性,后者可通过改性方法来降低重金属的迁移性和生物有效性;（4）生物炭对土体的固化效果一般,但可与其他固化材料共同使用,以改善土体的力学性质;（5）生物炭修复机理固定重金属的效果为:沉淀作用>络合作用>静电作用,离子交换>物理吸附。最后,针对该领域的研究现状,提出了未来的研究重点和方向,主要包括:建立划分生物炭的统一标准;探讨生物炭对多种重金属共同污染的修复效率;阐明生物炭吸附重金属的机理及其贡献率;扩大研究尺度;开展基于生物炭的固化试验及力学性质研究。     

Applying numerical modeling for designing strategies of effective groundwater remediation

Selection of effective groundwater remediation scenarios is a complex issue that requires understanding of contaminants’ transport processes. The effectiveness of cleanup measures may be verified by fate and transport numerical modeling. The goal of this work was to present the usefulness of fate and transport modeling for planning, verification and fulfillment of effective groundwater remediation methods. Selection methodology was developed, which is based on results of numerical flow and transport modeling. A field site located in south-east Poland was selected as a case study, in which groundwater contamination of trichloroethene and tetrachloroethene was detected. The results indicated that “pump and treat” was the most effective among the studied remediation methods, followed by permeable reactive barrier and in situ chemical oxidation. Natural attenuation-based remediation was demonstrated to be the least suitable, as it requires the longest time to reach predefined remediation goals, principally due to low sorption capacity and unfavorable hydrogeochemical conditions for biodegradation. Fate and transport numerical modeling allowed simulating different remediation strategies, and thus the decision-making process was facilitated.     

共存重金属离子对针铁矿活化过硫酸盐去除水中磺胺吡啶的影响

基于硫酸根自由基的高级氧化技术能有效降解水中磺胺类药物残留。由于在自然环境中共存重金属会对环境修复效果产生一定影响,文中重点研究了不同pH环境条件下不同重金属离子对针铁矿活化过硫酸盐(PS)去除水中磺胺吡啶(SPY)的影响。不同类型重金属离子(Cu^2+、Pb^2+、Cd^2+,0.2mmol/L)在反应体系(初始条件:针铁矿,1.0g/L;PS,4mmol/L;SPY,10mg/L;pH=8.2)中对SPY的降解对比研究发现:在无重金属共存的条件下,针铁矿/PS体系降解SPY的去除率为25.2%;Pb^2+和Cd^2+对针铁矿/PS体系的影响较弱,去除率分别为30.8%和34.8%;Cu^2+的促进作用很大,可以使SPY被完全降解(100%)。机理分析认为,在针铁矿/PS体系中Pb^2+和Cd^2+主要通过影响吸附作用导致磺胺吡啶被去除,而Cu^2+主要通过自身活化PS的作用。不同pH条件(3.0,8.0,12.0)实验证实弱碱性条件下,Cu^2+/针铁矿/PS能够发挥较高的活性从而降解SPY。本文结果为采用针铁矿活化过硫酸盐技术修复类似复合污染地下水环境提供了实验依据。     

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.     

某Cr(Ⅵ)污染场地修复的PRB反应材料及结构设计研究

渗透反应格栅(permeable reactive barrier,PRB)在国外被广泛应用于场地尺度的地下水污染修复,因其无须外源动力、不占地面空间、运行成本低等优势在国内受到广泛关注。不同场地水文地质条件、污染物类型、污染羽分布具有差异性,前期场地调查、反应材料的筛选、反应墙尺寸结构的设计对于PRB的有效运行至关重要。本文以PRB修复河南某Cr(Ⅵ)污染场地为例,详细阐述场地调查、材料筛选、材料反应参数确定、PRB结构优化等方面的研究过程及成果,可为后续PRB修复技术的应用提供参考。研究结果表明:PRB修复技术适用于该场地,铸铁与活性炭混合材料为最佳修复材料;反应门长40 m(反应材料厚2 m,上下游分别为2 m厚砾石层),东西两侧隔水墙长为60 m的U型漏斗-门系统型PRB,可有效捕获并修复污染羽,工程成本远低于连续反应墙式PRB,为该场地修复最优PRB结构类型。     

过硫酸钠修复土壤中多环芳烃的准确测定

多环芳烃(PAHs)是一类具有致癌、致突变、致畸的碳氢化合物,具有较高的辛醇-水分配系数,易被土壤颗粒吸附而影响环境和人体健康。过硫酸钠(Na₂S₂O₈)氧化法是近些年来国内外修复PAHs污染土壤较为常用的方法,但现阶段在测定修复后土壤中PAHs含量、进行土壤修复效果评估时亟待解决的问题是：经该方法修复的土壤,若土壤中残留有过硫酸钠,在样品前处理过程中由于提取温度较高,可能会进一步加速多环芳烃的氧化反应,从而影响土壤中PAHs的准确测定。本文建立了一种在修复后土壤中加入还原剂抗坏血酸,与残留的过硫酸钠反应生成脱氢抗坏血酸,采用索氏提取结合气相色谱-质谱法(GC-MS)同时测定土壤中16种PAHs的方法,PAHs加标回收率为76.2%～110.0%。而修复后土壤若不加还原剂直接进行索氏提取,用GC-MS测定,可能会使部分PAHs及替代物的测定不准确,PAHs加标回收率仅为6.0%～72.4%。通过对比分析表明,在样品提取前加入还原剂,可以有效地消除残留过硫酸钠的影响,提高测定修复后土壤中PAHs含量的准确性。     

Performance and environmental impact of a turbojet engine fueled by blends of biodiesels

Depletion of conventional fuels, concerns about environmental pollution and the tightening of exhaust emission legislations are the main reasons for increasing research on alternative fuels produced from agricultural feedstock. In this study, biodiesel fuels produced from cotton and corn vegetable oils are investigated as renewable fuels for a gas turbine engine for aviation. The biodiesel fuels are defined as cotton methyl ester (CTME) and corn methyl ester. The performance characteristics and exhaust emissions of the gas turbine engine are investigated when the engine fueled with three blends of 10%(B10), 20%(B20) and 50%(B50) of biodiesel/JetA-1 by volume. The biodiesel fuels were produced using transesterification process and characterized according to ASTM biodiesel specifications. Chemical and physical properties show a real potential of using biodiesel blends as an alternative for JetA-1. The measured engine performance parameters and exhaust emissions are compared with that of pure JetA-1 over a range of throttle setting. The gas turbine engine used in this study is equipped with pressure, flow, temperature, thrust and speed sensors that connected to data acquisition system and control unit in addition to exhaust gas analyzer. The experimental results show that biodiesel fuels can be used up to blend of 50% with JetA-1 in gas turbine engines with slight enhancement in engine performance and significant improvements in exhaust emissions. The engine static thrust is increased with 2% for B50 at lower and medium engine speeds and decreased with 11% at high engine speed compared to conventional JetA-1 fuel. The thrust-specific fuel consumption for biodiesel blends is lower than that for regular JetA-1 fuel. The gas turbine engine efficiency is increased for biodiesel blends by 14% compared to JetA-1, and this is reported for CTME B50. For oxygen concentration in exhaust gases emissions, the higher the biodiesel blend, the higher the O₂ concentration in the exhaust compared with JetA-1 fuel. The O₂ level increased by 6% for biodiesel blend of B50 compared to JetA-1 fuel. The emissions of CO and HC emissions decreased by 5 and 37%, respectively, compared with conventional JetA-1. Additionally, the biodiesel blends achieve a higher CO₂ and NO_x emissions with 11 and 27%, respectively, compared to JetA-1. The sulfur dioxide SO₂ decreased by 75% compared to the regular JetA-1 fuel.     

杭州市郊来龙山滑坡的治理与监测

滑坡是一种重大的地质灾害,本文结合杭州市郊来龙山的滑坡工程,具体分析了滑坡的成因、稳定计算和最终采取的治理措施,通过监测的具体内容和结果进行分析,表明治理效果比较好,为以后该地区的滑坡治理与加固提供相关参照。     

乙醇对过硫酸盐氧化地下水中苯系物的影响

过硫酸盐已经被广泛用于土壤和地下水有机污染物的原位化学氧化修复。随着乙醇汽油的推广,乙醇汽油引起的地下水污染问题越来越严重,因此有必要去除该类污染物。前人研究乙醇汽油污染修复多数停留在自然修复技术,为了进一步探究去除地下水中乙醇汽油更为有效的技术手段,深入了解乙醇对降解苯系物（BTEX）存在的潜在风险,需要研究使用新的修复方法。文章通过批实验探索了过硫酸盐氧化法对乙醇汽油污染地下水的修复效果,以及Fe2+活化和过硫酸盐添加方式变化对乙醇汽油中苯系物（BTEX）和乙醇的去除影响。结果表明:活化后的过硫酸盐能够有效去除地下水中的BTEX,但会抑制BTEX的生物降解作用;当有乙醇存在时,过硫酸盐能够优先氧化BTEX,其去除速率明显高于乙醇,这与单纯生物降解作用相反。在过硫酸盐投注总量一定时,分批添加更有利于BTEX的去除,但对乙醇去除没有明显促进作用。该研究为过硫酸盐原位化学氧化技术在地下水乙醇汽油污染修复中的应用提供了重要参考。     

表面活性剂强化含水层修复过程的全局灵敏度

针对非水相流体污染含水层的表面活性剂强化修复过程,在多相流数值模拟模型以及径向基函数人工神经网络替代模型的基础上,应用Sobol法对影响修复效果的变量进行全局灵敏度分析。当替代模型的训练集包含12组和22组数据时,替代模型与模拟模型拟合的确定性系数分别为0.977 8和0.981 6,表明随着训练集数据的增多,替代模型与模拟模型的近似精度逐渐增加。灵敏度分析结果表明：对修复效果贡献最大的决策变量为总抽水量(总灵敏度为0.491 2),其次为修复时间(总灵敏度为0.468 5),表面活性剂浓度对修复效果的贡献最小(总灵敏度为0.124 2);各个变量之间存在着相互作用,但相互作用对输出响应的影响不大。     

Use of a resistivity cone for detecting contaminated soil layers

A cone-penetration technique was developed to detect contaminated soil layers with electrolytes and NAPLs. In this study, laboratory and field experiments were performed to apply the technique. In the laboratory, the change in resistivity was quantitatively examined by adding salt or oil to soil samples. The results showed that the resistivity measurement was varied with an order of ppm for the electrolyte concentration in soil. It was found that the resistivity of sand increased with increasing oil concentration. The effect of oil content was stronger for lower water content of sand.

The results obtained from field experiments showed that the resistivity cone can be used for detecting the contaminated layer in soils whose background values are known. Particularly, the instrument can be used effectively for examining the effects of remediation, by measuring the resistivity of the ground before and after remediation, unless the soil fabric changes significantly during remediation procedures.     

Lead contamination of soil along road and its remediation

With a rapid development of road systems and an associated drastic increase in number of automobiles, the traffic has induced more and more obvious environmental pollution such as noise, dust, emission and heavy metal contamination. Lead, as one of the most harmful heavy metal contaminants, can execute a significant impact on soil quality and plant growth, depending on its form, as well as its transport and accumulation in soil. This paper describes the source and characteristics of Pb contaminant in soil along a road, and reviews the results of research on remediation of Pb-contaminated soils, aiming at identifying promising approaches to soil remediation along roads.     

羧甲基纤维素稳定纳米铁去除水中六价铬的研究

零价纳米铁(NZVI)具有较高活性,近年受到人们关注并将其应用于地下水污染原位修复,但在实际应用中NZVI易发生氧化与团聚,容易失活。因此尝试运用环境友好型材料对NZVI进行表面改性,选择羧甲基纤维素(CMC)对纳米铁进行表面包覆获得CNZVI,研究不同CMC含量包覆NZVI的分散稳定性和CNZVI对水中六价铬的去除效果。结果表明：经过改性后的CNZVI分散稳定性要明显优于商用纳米铁RNIP,包覆CMC的比例越高,CNZVI的稳定性越好,在较高的CMC包覆比例下,纳米铁不易失活并具有良好的反应活性,对溶液中六价铬有很好的去除效果。