Cold Flow Properties of Fatty Esters

This article is devoted to the study of cold flow properties of neat esters of branched chain alcohols with fatty acids and blends of these esters with fossil diesel fuel. According to determined CFPP values the influence of alcohol branching on the fuel filterability is negligible. Fossil fuel blending with fatty esters of branched alcohols up to 10 vol % does not substantially change the cold flow properties of fossil fuel. The low-temperature properties of fossil diesel and fatty acid methyl/ethyl ester (FAME/FAEE) blends with low ester content (up to 10 vol %), prepared mainly from oils/fats with higher share of saturated fatty acids namely palm oil, tallow and lard, were also measured. The obtained results show that studied esters do not change low-temperature properties of fossil fuel in the blends with the low esters content of 3–5 vol %, although their own CFPP is over the value permissible by the standard EN 14 214. However, current standard EN 590 specifies to meet all parameters of the standard EN 14 214 also for FAME assigned for blended fuels entirely. The proposal to repeal the CFPP limit for esters assigned for blending is fully justified, without any negative effects on fuel quality.     

直喷式柴油机燃用脂肪酸甲酯的排放特性

脂肪酸甲酯是由生物脂肪经过酯化反应得到的脂肪酸单酯,具有良好的燃料品质和环境友好性,是生物柴油众多种类中的一种.以纯矿物柴油、脂肪酸甲酯、含30%脂肪酸甲酯与70%柴油的混合燃料和含50%脂肪酸甲酯与50%柴油的混合燃料为燃料,在四缸涡轮增压直喷式柴油机上进行的性能对比实验,表明柴油机燃用脂肪酸甲酯能够保持其动力性和燃料经济性,可以显著降低HC和碳烟排放,但会增加CO和NOx排放.脂肪酸甲酯可以作为柴油机的代用燃料进行推广.     

Biodiesel production from waste oil feedstocks by solid acid catalysis

Biodiesel is a non-toxic and biodegradable substitute for petroleum-based diesel. However, it is impractical to use refined edible oils to produce biodiesel due to its high cost and priority for food products, especially in China, while waste oils with high free fatty acids (FFAs) can be considered as the raw materials. In the present work, a solid acid catalyst comprising SO₄²⁻/TiO₂–SiO₂ was prepared, characterized and studied for its activity for the production of biodiesel from several low cost feedstocks with high FFAs. The solid acid catalyst can be recycled, easily removed and can simultaneously catalyze esterification and transesterification. The influence of reaction parameters was studied, and the optimized reaction parameters are reaction temperature 200 °C, molar ratio of methanol to oil 9:1 and catalyst concentration 3 wt.%. The catalyst showed good stability. A continuous process for biodiesel production from cheap raw feedstocks was proposed, and a 10,000-tonnes/year biodiesel production demonstration plant has been built.     

A New Solubility Model to Describe Biodiesel Formation Kinetics

The development of a mathematical model that accurately describes the formation of fatty acid methyl esters (FAMEs) (otherwise known as biodiesel) from rapeseed oil and methanol in the presence of sodium hydroxide catalyst at temperatures in the range of 293–333 K is described. The model accounts for the existence of more than one phase at any given stages of the reaction and for the solubilities of the reacting species in various phases. The latter were obtained experimentally and are presented in the form of ternary phase diagrams. The model appears to give a good fit to the experimental data obtained using both batch and continuous flow reactors.     

Fuel recovery from waste oily sludge using solvent extraction

Solvent extraction was used to recover oil from waste sludge generated from the storage of crude petroleum. Different solvent-to-sludge mass ratios were used for two solvents, methyl ethyl ketone (MEK) and LPG condensate (LPGC). Several parameters were compared, such as oil recovery as a percent of the original sludge mass, and reduction in carbon residue, ash content, and asphaltene content. A 4:1 solvent-to-sludge ratio was found to be optimum for both solvents. The MEK extraction recovered 39% by mass of the sludge as recovered oil. The LPGC recovered 32%. The amount of asphaltenes in the fuel oil was related to the concentration of fuel oil in the solvent phase during the extraction, suggesting that asphaltenes are extracted mainly by the fuel oil components, not the solvent. The physical properties and metal content of the recovered oil were measured. The recovered oil was distilled to provide diesel fuel. This diesel fuel contained high levels of sulfur and carbon residue, as well as a high diesel index, indicating the fuel requires further treatment prior to use as a fuel.     

生物柴油产业链分析

生物柴油是指由植物油、动物油脂等制备得到的单烷烃酯类。它是一种环境友好、清洁排放的燃料,因此是非常理想的石油柴油替代燃料。本文从生物柴油产业链中的原料来源、生产工艺、产品应用以及其效益等方面对这种新型的清洁燃料进行了简单介绍。总之,生物柴油是一种很有发展前景的生物质燃料。     

Experimental Study on the Potential Application of Cottonseed Oil–Diesel Blends as Fuels for Automotive Diesel Engines

This paper presents the results of an experimental study on the direct application of cottonseed oil–diesel blends as fuel for diesel engine vehicles without using additional retrofit mechanical systems. The use of biofuels is one of the main actions promoted by the European Union and member states in an effort to tackle global warming, enhance energy security and contribute to regional development. Here, the possibility to blend cottonseed oil directly with fossil diesel as a fuel for diesel engines is examined. This option has lower cost and larger well-to-wheel greenhouse gas benefits than fatty acid methylesters. The paper presents measurements of important fuel properties, density, viscosity, cetane number and cold flow characteristics. In addition, a common rail Euro 3 compliant diesel car is tested using 10% v/v cottonseed oil–diesel blends in order to examine the effects on performance and emissions of regulated pollutants and CO₂. Furthermore, particle emission characteristics are studied, including total and solid particle number concentrations and particle size distributions over driving cycles and steady state modes. The results indicate that the test fuel presents good operating characteristics and limited effects on regulated emissions and vehicle performance. These results would justify further research on the direct use of vegetable oils as automotive fuels.     

Optimization of biodiesel production by alkali-catalyzed transesterification of used frying oil

Biodiesel as an alternative fuel for fossil diesel has many benefits such as reducing regulated air pollutants emissions, reducing greenhouse gases emissions, being renewable, biodegradable and non-toxic. In this study, used frying oil was applied as a low cost feedstock for biodiesel production by alkali-catalyzed transesterification. The design of experiments was performed using a double 5-level-4-factor central composite design coupled with response surface methodology in order to study the effect of factors on the yield of biodiesel and optimizing the reaction conditions. The factors studied were: reaction temperature, molar ratio of methanol to oil, catalyst concentration, reaction time and catalyst type (NaOH and KOH). A quadratic model was suggested for the prediction of the ester yield. The p-value for the model fell below 0.01 (F-value of 27.55). Also, the R² value of the model was 0.8831 which indicates the acceptable accuracy of the model. The optimum conditions were obtained as follows: reaction temperature of 65 °C, methanol to oil molar ratio of 9, NaOH concentration of 0.72% w/w, reaction time of 45 min and NaOH as the more effective catalyst. In these conditions the predicted and observed ester yields were 93.56% and 92.05%, respectively, which experimentally verified the accuracy of the model. The fuel properties of the biodiesel produced under optimum conditions, including density, kinetic viscosity, flash point, cloud and pour points were measured according to ASTM standard methods and found to be within specifications of EN 14214 and ASTM 6751 biodiesel standards.     

Synthesis of Bio-Diesel and Bio-Lubricant by Transesterification of Vegetable Oil with Lower and Higher Alcohols Over Heteropolyacids Supported by Clay (K-10)

The use of different lower and higher alcohols viz; methanol, ethanol, n-propanol and n-octanol, for the synthesis of methyl, ethyl, propyl and octyl fatty acid esters by transesterification of vegetable oil (triglycerides) with respective alcohols also known as ‘Bio-diesel’ and ‘Bio-lubricants’ was studied in detail. The reactions were carried out in a batch process. The activity with different supports like clay (K-10), activated carbon, ZSM-5, H-beta and TS-1 were compared. The superacids (heteropolyacids, HPA) viz; Dodeca-Tungstophosphoric acid [H₃PO₄·12 WO₃·xH₂O] (TPA) and Dodeca-Molybdo phosphoric acid ammonium salt hydrate [H₁₂Mo₁₂N_3-O₄₀P + aq] (DMAA) was used to increase the acidity and so the activity by loading on the most active support viz; clay (K-10). These HPA loaded on clay as a catalyst was used for the following study: effect of percent HPA loading on clay, effect of different vegetable oils, effect of different alcohols on the triglyceride conversion based on glycerol formation and selectivity based on alkyl esters formation. The data is compared at the best-optimized identical set of operating reaction conditions: 170 °C, 170 rpm, catalyst loading: 5% (w/w of reaction mixture), molar ratio (oil: alcohol): 1:15 and time on stream of 8 h. The generated data is also evaluated based on the reported one.     

Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

温度分层环境下火灾烟气羽流上升高度公式分析

对小尺度空间温度分层环境下柴油有焰火及棉绳阴燃火烟气运动进行了实验和数值模拟.结果表明,在分层环境下,烟气与环境空气温度差造成的浮力在某一高度消失并转为负值,致使烟气停止上升而向横向扩展.Morton积分公式低估了烟气羽流上升的最大高度,且在相同出口条件及分层环境下,柴油烟雾比棉绳烟雾下降趋势快,上升高度小,其原因在于积分公式中自相似卷吸及烟气为空气假设.引入烟气密度修正系数和自相似修正系数,对Morton公式进行了修正和讨论.     

轻柴油储罐火灾过程及安全性评价

从 2 0 0 2年 1月 1日起我国实施新的“轻柴油”产品标准 ,新标准将轻柴油的闪点指标由原来的≥ 65℃改为≥ 5 5℃ ,由此导致轻柴油的火灾危险类别发生变化 ,并进而引发原有轻柴油储罐能否安全储存新标准轻柴油的问题。笔者利用化学流体力学模型和挪威船级社 (DNV)的SAFETI风险评估软件对 65℃闪点和 5 5℃闪点轻柴油的储存火灾危害性进行了评估 ,取得了轻柴油火灾中危害程度的计算机模拟结果     

天然腐殖酸对柴油在寒旱区黄土上吸附特性的影响

选用西北寒旱区黄土为供试土样,通过热力学和动力学吸附试验研究了干旱区低有机质黄土对柴油的吸附行为,以及提取的天然腐殖酸对柴油在黄土上吸附行为的影响。结果表明,无论是否加入腐殖酸,柴油在黄土颗粒上的吸附都符合Freundlich方程,且腐殖酸质量浓度对柴油的吸附量有显著影响。在27℃时,加入10 mL质量浓度为40 mg/L的腐殖酸溶液后,柴油在黄土上的饱和吸附量由12.034mg/g减小为7.407 mg/g,且吸附量随温度的升高而降低,表明吸附为自发的放热过程。描述柴油在黄土上吸附动力学的最优方程为Elovich方程,其次为双常数方程。无论是否加入腐殖酸,黄土对柴油的吸附都在短时间内达到平衡。对吸附影响因素的分析结果表明,柴油在黄土上的吸附随溶液pH值的增大而降低;黄土颗粒粒径越小,柴油在土样上的吸附量越大。     

Optimization of biodiesel production from the waste cooking oil using response surface methodology

In this research, transesterification of the waste cooking oil has been studied. Response surface methodology (RSM) based on Box–Behnken design was used to investigate the effects of the main operating parameters, including the methanol to oil molar ratio, catalyst concentration, and reaction temperature, on the biodiesel yield. The results revealed that the catalyst concentration is the most important parameter. The maximum biodiesel yield under the optimized conditions was 99.38 wt.%. Thermogravimetric analysis (TGA) was used for the determination of biodiesel conversion and the results were compared with that of gas chromatography (GC) analysis, showing a very small difference. Furthermore, an empirical quadratic equation has been presented to show the relation between biodiesel conversion and product viscosity.     

浸油沙层火焰传播速度研究

使用0#柴油和沙层作为燃料和地面模型,通过实验研究了泄漏液体燃料渗透在地面之后的火焰传播现象.详细研究了燃料床中沙粒直径、燃烧盘宽度及一端施加辐射热对火焰传播速度的影响,并使用热电偶测量了沙层表面火焰前沿到达时的温度以及沙层表面能够达到的最高温度.结果表明,燃料渗漏在地面的火焰传播速度明显低于液池火灾的火焰传播速度,且改变沙油质量比、燃烧盘的宽度及外界热辐射直接影响火焰传播速度.     

阻燃抑爆柴油的燃烧性能和排放研究

以-10号军用柴油为基础油配置阻燃抑爆柴油,在WP10.290发动机上进行了台架实验,考察了使用阻燃抑爆柴油时的动力性、经济性和排放性。结果表明:燃用阻燃抑爆柴油相比于燃用-10号军柴会一定程度上降低输出功率和扭矩,动力性能下降2.31%~4.26%;燃用阻燃抑爆柴油时平均质量燃油消耗率较燃用军用柴油时增加了5.74%。体积燃油消耗率与军用柴油相比,平均增加了4.32%;能够降低NO的排放,NO的排放量相较于-10号军柴降低了7%~19%;能够降低排气温度,相比较于-10#军柴,阻燃抑爆柴油的排气温度最大可以降低19.5℃。     

Using fuzzy method to evaluate safety condition of big diesel engine

Big diesel engine is one of the most important equipments in industry, and its safety condition plays a great role in oil production. This paper presents a fuzzy method to monitor the safety state of the big diesel. Six useful diagnostic characteristic parameters have been selected to diagnose safety condition of the big diesel engine. The standard fuzzy vector was obtained by using statistical method, so the status of big diesel's safety condition can be determined by calculating the fuzzy distance between the fuzzy vector and standard fuzzy vector. This fuzzy method has been successfully used on PZ12V190 diesel engine.     

Small scale thin-layer boilover experiments: Physical understanding and modeling of the water sub-layer boiling and the flame enlargement

Boilover is defined as a violent ejection of fuel due to the vaporization of a water sub-layer, resulting in an enormous fire enlargement and formation of fireball and ground fire. This paper focuses on the physical principles behind the thin-layer boilover phenomenon, and on the improvement of the thin-layer boilover modeling. Small scale field and laboratory experiments, with a mixture of diesel and oil, and reservoirs ranging from 0.08 to 0.3 m, have been performed. High-speed visualizations and image processing, in parallel to temperature and mass loss measurements allows to better understand the water boiling, and the consequent flame enlargement. The modeling of the boilover period is done through the calculation of the pre-boilover burnt mass ratio and the boilover intensity based on the mass loss and on the flame enlargement.     

Performance evaluation of biodiesel from used domestic waste oils: A review

Global warming, high-energy demand and availability of new technologies are among the factors catalyzing the search for alternative sources of energy. Currently, there is renewed interest in obtaining energy from wastes hitherto meant for disposal. Increased costs of disposal and their attendant problems of heavy environmental loading are some aspects making the disposal option unattractive. These wastes are sources of energy and among the several sources of generating this energy are the waste-to-energy (WTE) categories with potentials for useable fuel production. The WTE materials are mainly used domestic waste oils (UDWOs), municipal solid waste (MSW), agricultural and industrial wastes. However, the latter wastes are not attractive as they consist of innumerable hazardous contaminants. The UDWOs are arguably a safe and cost effective source of useable fuel. Their conversion offers the merits of a reduction in greenhouse gas emission (GHG), enhancing fuel diversification and a qualitatively comparable energy output to fossil diesel fuels. Thus, UDWOs could significantly contribute towards achieving the 2020 and 2030 goals of substituting approximately 20% and 30% of petro-diesel with biofuels in US and EU, respectively. Moreover, attaining the forecasted annual production rate of 227 billion liters of biofuel by most active stakeholders in the biodiesel industry could be easily achieved.This review aims to analyze the performance of biodiesel fuels obtained from UDWO and to demonstrate the suitability of applying these fuels as substitutes to mineral diesel in various industries. Benefits of UDWO as a biodiesel feedstock were as well highlighted.     

A summary of the available technologies for biodiesel production based on a comparison of different feedstock's properties

Biodiesel production is mainly done by carrying on the transesterification reaction while using refined oil, methanol and a homogeneous base catalyst. When using refined oil, a competition between oil for food and oil for fuel is then presented. Even more, the conventional technology has the disadvantage that the raw material has to be very pure, with no traces of other impurities. Otherwise, undesirable products will be produced decreasing the productivity of the process and making a large amount of waste treatment.Because of this, other technologies appear as possible sources for biodiesel production, mainly from refined oil, but also allowing less pure raw material to be used, such as waste oil, frying oil, soapstocks, and animal fats.In this work, a comparison of all these different raw materials, their physicochemical properties and how they can have an influence, and the magnitude of this phenomenon, in the biodiesel production will be presented and compared. Based on the previous analysis, a short summary of the technological possibilities to produce good quality biodiesel from low price raw material will be discussed with the aim of showing their advantages and disadvantages when using different feedstocks.