Effect of the alcohol type used in the production of waste cooking oil biodiesel on diesel performance and emissions

Experimental results were obtained by testing two different alcohol-derived biodiesel fuels: methyl ester and ethyl ester, both obtained from waste cooking oil. These biodiesel fuels were tested pure and blended (30% and 70% biodiesel content, volume basis) with a diesel reference fuel, which was tested too, in a 2.2 l, common-rail injection diesel engine. The operation modes were selected to simulate the European Driving Cycle. Pure biodiesel fuels, compared to the reference fuel, resulted in a slight increase in fuel consumption, in very slight differences in NOx emissions, and in sharp reductions in total hydrocarbon emissions, smoke opacity and particle emissions (both in mass and number), despite the increasing volatile organic fraction of the particulate matter. The type of alcohol used in the production process was found to have a significant effect on the total hydrocarbon emissions and on the particulate matter composition. As the alcohol used was more volatile, both the hydrocarbon emissions and volatile organic fraction of the particulate matter were observed to increase.     

活塞流反应器制备生物柴油

为实现连续、高效、稳定的生物柴油制备,本研究以自行设计的活塞流反应器制备生物柴油。同时利用正交实验的方法对制备过程的影响因素进行了较为系统的研究,得到的优化条件为:催化剂质量为油质量的1.2%,物料在活塞流反应器中滞留时间约17 min,床层温度65℃,油醇摩尔比约1∶6。在此优化条件下所得产品甲酯质量分数达96.33%。经减压蒸馏精制后,甲酯质量分数提高到98.62%,其他燃料特性也与德国现行生物柴油标准相符,同时接近甚至优于我国0#车用柴油标准。为生物柴油的大规模工业化应用奠定了良好的基础。     

Optimization of the reaction parameters for fast pseudo single-phase transesterification of sunflower oil

Transesterification of sunflower oil with methanol was carried out using potassium hydroxide and methoxide as catalysts and MTBE as cosolvent. The aim of this work was to study and optimize the reaction parameters. Chosen parameters were reaction time, catalyst amount and methanol amount (expressed as catalyst-to-oil and methanol-to-oil molar ratios, respectively). The response variables were methyl ester content (ME) and acid value (AV) due to their relationship with the completion and yield reaction, respectively. A factorial plus composite design was developed to carry out the optimization. From this design, several quadratic models have been used to fit the experimental data. All the factors studied had a positive influence on methyl ester content and acid value, except the methanol amount on acid value. For methoxide catalyst, optimum values were 0.235 catalyst to oil molar ratio, 12 methanol to oil molar ratio and 5 min reaching 99 wt.% ME and 0.20 mg KOH/g of AV.     

磷钨酸铈催化合成棕榈酸和硬脂酸混合酸甲酯

采用磷钨酸铈作为催化剂,在反应温度67 ℃合成棕榈酸和硬脂酸混合酸甲酯反应,研究酸醇物质的量比、催化剂用量和反应时间对酯化反应的影响,并在最佳反应条件基础上研究催化剂的循环利用工艺。结果表明,在酸醇物质的量比1∶10、催化剂用量为棕榈酸和硬脂酸混合酸质量的8%、反应时间4 h和催化剂重结晶后循环利用10次条件下,棕榈酸和硬脂酸混合酸转化率均≥96.0%,催化剂反应前后的IR和XRD表征发现,催化剂均为Keggin型结构,未发生变化,表现出良好的催化活性。     

Rapid transesterification of soybean oil with phase transfer catalysts

Biodiesel is a renewable, non-toxic and biodegradable alternative fuel for compression ignition engines. Biodiesel is produced mainly through base-catalyzed transesterification of animal fats or vegetable oils. However, the conventional base-catalyzed transesterification is characterized by slow reaction rates at both initial and final reaction stages limited by mass transfer between polar methanol/glycerol phase and non-polar oil phase.In our study we used phase transfer catalysts (PTCs) to facilitate anion transfer between polar methanol/glycerol phase and non-polar oil phase to speed up transesterification. The benefits of transesterification by PTCs include no need for expensive aprotic solvents, potentially simpler scaleup and higher activity (shorter reaction time). Various PTCs were investigated for base-catalyzed transesterification. Experimental results showed that base-catalyzed transesterification was enhanced with an effective PTC, indicated by the formation of high methyl ester (ME) content within a relatively short time. Individual operating variables such as molar ratios of methanol to oil, total OH⁻ to oil, PTC to base catalyst and agitation including ultrasound were investigated for transesterification with PTC. Product analyses showed that ME content higher than 96.5 wt.% was achieved after only 15 min of rapid transesterification with PTC (tetrabutylammonium hydroxide or tetrabutylammonium acetate as PTC, MeOH/oil molar ratio of 6, total OH⁻/oil molar ratio of 0.22, PTC/KOH molar ratio of 1 and 60 °C). Free and total glycerol contents in the final product from 15 min rapid transesterification with PTC were lower than maximum allowable limits in the standard specification for biodiesel.     

Engine-out characterisation using speed-load mapping and reduced test cycle for a light-duty diesel engine fuelled with biodiesel blends

In this two-phase experimental programme, key effects of different biodiesel fuels and their blends on engine-out responses of a light-duty diesel engine were investigated. Here, coconut methyl ester (CME), palm methyl ester (PME) and soybean methyl ester (SME) were tested to represent the wide spectrum of degree of saturations in the fatty acid composition. Fossil diesel which served as the blending component was used as the baseline fuel for benchmarking purposes. Phase I examined how engine speed and load affect patterns of variation in tailpipe emissions and engine performance parameters for the test fuels. Here, the trends in engine-out responses across the operational speed-load map for all the tested biodiesel fuels were similar and consistent throughout. However, there were marked differences in the levels of equivalence ratio and specific fuel consumption, as well as exhaust concentrations of CO, UHC and smoke opacity. This is mainly due to differences in fuel properties, especially fuel-bound oxygen content, density and impurity level. Phase II appraised the performance of 31 different fuel blend combinations of fossil diesel blended with CME, PME or SME at 10 vol.% interval under a steady-state test cycle. The use of biodiesel fuels with low to moderate degree of unsaturation was found to conclusively reduce regulated emission species of UHC, NO and smoke opacity levels by up to 41.7%, 5.4% and 61.3%, respectively. This is in contrast to the performance of the highly unsaturated SME, where CO, UHC, NO and smoke opacity levels are higher in relation to that of fossil diesel. Simultaneous NO-smoke reduction can be achieved through the introduction of at least 1 vol.% of PME or 50 vol.% of CME into diesel fuel, although minor trade-off in the higher specific fuel consumption is observed.     

Ca and Zn mixed oxide as a heterogeneous base catalyst for transesterification of palm kernel oil

Transesterification of palm kernel oil with methanol over mixed oxides of Ca and Zn has been investigated batchwise at 60 °C and 1 atm. CaO·ZnO catalysts were prepared via a conventional co-precipitation of the corresponding mixed metal nitrate solution in the presence of a soluble carbonate salt at near neutral conditions. The catalysts were characterized by using techniques of X-ray diffraction (XRD), scanning electron microscope (SEM), and thermogravimetric analysis (TGA). The results indicated that the mixed oxides possess relatively small particle sizes and high surface areas, compared to pure CaO and ZnO. Moreover, the combination of Ca and Zn reduced the calcination temperature required for decomposition of metal carbonate precipitates to active oxides. Influences of Ca/Zn atomic ratio in the mixed oxide catalyst, catalyst amount, methanol/oil molar ratio, reaction time, and water amount on the methyl ester (ME) content were studied. Under the suitable transesterification conditions at 60 °C (catalyst amount = 10 wt.%, methanol/oil molar ratio = 30, reaction time = 1 h), the ME content of >94% can be achieved over CaO·ZnO catalyst with the Ca/Zn ratio of 0.25. The mixed oxide can be also applied to transesterification of palm olein, soybean, and sunflower oils. Furthermore, the effects of different regeneration methods on the reusability of CaO·ZnO catalyst were investigated.     

Mechanical Modifications of Paraffin‐based Fuels and the Effects on Combustion Performance

In order to enhance the mechanical properties, 6 kinds of additives of stearic acid, polyethylene wax (A−C®6A), ethylene vinyl acetate copolymer (EVA), low density polyethylene (LDPE), polypropylene (PP) and high density polyethylene (HDPE) were blended in the paraffin fuel. Mechanical properties of paraffin‐based fuels were investigated by mixing 5 % in mass of different additives and increasing the mass percent of A−C®6A and LDPE. In addition, the combustion performance of the so modified paraffin‐based fuels were tested by a 2D‐radial burner at Nanjing University of Science and Technology. The effects of additives on regression rate were analyzed by thermal performance test (melting point and DSC) and viscosity measurement. Overall, all the additives can improve mechanical properties and the mechanical properties are enhanced by increasing mass% of additives. A−C®6A revealed the best for improving compressive strength (64.0 % increase by blending 5 mass %), LDPE revealed the best for improving tensile strength (105.3 % increase by blending 5 mass %). For combustion performance, the regression rates of paraffin‐based fuels blended with stearic acid increased owing to the decreased melting points while the regression rates of the other five formulations decreased due to the increased melted liquid viscosity. The relationship between regression rate and viscosity is a power function which is not affected by additives at high temperature, thereby it is convenient to predict the regression rate by measuring viscosity.     

The preparation and shock tube investigation of comparative ignition delays using blends of diesel fuel with bio-diesel of cottonseed oil

This paper describes an experimental effort for the production of cotton methyl ester (CME), cotton ethyl ester (CEE) and CEE-diesel blends from neat cottonseed oil (CSO) for use as a bio-diesel fuel and the investigation of the ignition delay times of these fuels using the shock tube. The transesterification of the neat CSO with methanol or ethanol has been performed to determine the optimum conditions for the preparation. The optimum parameters were cottonseed oil/alcohol molar ratio, 1:6; NaOH amount, 1% by the weight of the oil and reaction time, 75 min. The physical properties of all the tested fuels are measured. 89% of the neat CSO was converted into CME or CEE and the use of different alcohols (methanol or ethanol) presents few differences with regards to the kinetics of reaction but the final yield of esters remains almost unchanged. The ignition delay times were measured using a piezo-electric pressure transducer, charge amplifier, data acquisition card, IBM computer and LabVIEW program. Effects of equivalence ratio, initial charge temperature and initial charge pressure on the ignition delay times are discussed. The results show that the minimum ignition delay time was observed at an equivalence ratio of 1.05 for all the tested fuels. The ignition delay can be reduced considerably together with an increase of the initial charge temperatures and pressures. Also, the ignition delays of the tested fuels are compared with the diesel fuel.     

Temperature-dependent kinematic viscosity of selected biodiesel fuels and blends with diesel fuel

The kinematic viscosities of four biodiesel fuels—two natural soybean oil methyl esters, one genetically modified soybean oil methyl ester, and one yellow grease methyl ester—and their 75, 50, and 25% blends with No. 2 diesel fuel were measured in the temperature range from 20 to 100°C in steps of 20°C. The measurements indicated that all these fuels had viscosity-temperature relationships similar to No. 2 diesel fuel, which followed the Vogel equation as expected. A weighted semilog blending equation was developed in which the mass-based kinematic viscosity of the individual components was used to compute the mixture viscosity. A weight factor of 1.08 was applied to biodiesel fuel to account for its effect on the mixture viscosity. The average absolute deviation achieved with this method was 2.1%, which was better than the uncorrected mass average blending equation that had an average absolute deviation of 4.5%. The relationship between the viscosity and the specific gravity of biodiesel fuels was studied. A method that could estimate the viscosity from the specific gravity of biodiesel fuel was developed. The average absolute deviation for all the samples using this method was 2.7%. The accuracy of this method was comparable to the weighted mass-based semilog blending equation.     

Transesterification of karanja (Pongamia pinnata) oil by solid basic catalysts

The transesterification of karanja oil with methanol was carried out using solid basic catalysts. Alkali metal‐impregnated calcium oxide catalysts, due to their strong basicity, catalyze the transesterification of triacylglycerols. The alkali metal (Li, Na, K)‐doped calcium oxide catalysts were prepared and used for the transesterification of karanja oil containing 0.48–5.75% of free fatty acids (FFA). The reaction conditions, such as catalyst concentration, reaction temperature and molar ratio of methanol/oil, were optimized with the solid basic Li/CaO catalyst. This catalyst, at a concentration of 2 wt‐%, resulted in 94.9 wt‐% of methyl esters in 8 h at a reaction temperature of 65 °C and a 12 : 1 molar ratio of methanol to oil, during methanolysis of karanja oil having 1.45% FFA. The yield of methyl esters decreased from 94.9 to 90.3 wt‐% when the FFA content of karanja oil was increased from 0.48 to 5.75%. The performance of this catalyst was not significantly affected in the presence of a high FFA content up to 5.75%. The catalytic activities of Na/CaO and K/CaO were also studied at the optimized reaction conditions. In these two cases, the reaction initially proceeds slowly, however, leading to similar yields as in the case of Li/CaO after 8 h of reaction time. The purified karanja methyl esters have an acid value of 0.36 mg KOH/g and an ester content of 98.6 wt‐%, which satisfy the American as well as the European specifications for biodiesel in terms of acid value and ester content.     

Biodiesel production from tall oil with synthesized Mn and Ni based additives: Effects of the additives on fuel consumption and emissions

In this study, biodiesel fuel and fuel additives were produced from crude tall oil that is a by-product in the pulp manufacturing by craft or sulphate pulping process. Fatty acids and resinic acids were obtained from crude tall oil by distillation method. Tall oil methyl ester (biodiesel) was produced from fatty acids. Resinic acids were reacted with NiO and MnO₂ stoichiometrically for production of metallic fuel additives. Each metallic fuel additive was added at the rate of 8 μmol/l and 12 μmol/l to make mixtures of 60% tall oil methyl ester/40% diesel fuel (TE60) for preparing test fuels. Metallic fuel additives improved properties of biodiesel fuels, such as pour point and viscosity values. Biodiesel fuels were tested in an unmodified direct injection diesel engine at full load condition. Specific fuel consumption of biodiesel fuels increased by 6.00%, however, in comparison with TE60, it showed trend of decreasing with adding of additives. Exhaust emission profile of biodiesel fuels improved. CO emissions and smoke opacity decreased up to 64.28% and 30.91% respectively. Low NO_x emission was also observed in general for the biodiesel fuels.     

Enzymatic conversion of waste edible oil to biodiesel fuel in a fixed-bed bioreactor

The conversion of waste edible oil to biodiesel fuel in a fixed-bed bioreactor was investigated. Three-step methanolysis of waste oil was conducted using three columns packed with 3 g of immobilized Candida antarctica lipase. A mixture of waste oil and 1/3 molar equivalent of methanol against total fatty acids in the oil was used as substrate for the first-step reaction, and mixtures of the first- and second-step eluates and 1/3 molar equivalent of methanol were used for the second- and third-step reactions, respectively. Ninety percent of waste oil was converted to the corresponding methyl esters (ME) by feeding substrate mixtures into the first, second, and third reactors at flow rates of 6, 6 and 4 mL/h, respectively. We also attempted one-step methanolysis of waste oil. When a mixture of waste oil and 90% ME-containing eluate (1∶3, wt/wt) and an equimolar amount of methanol against total fatty acids in the waste oil was fed into a reactor packed with 3 g of immobilized C. antarctica lipase at a flow rate of 4 mL/h, the ME content in the eluate reached 90%. The immobilized biocatalyst could be used for 100 d in the two reaction systems without significant decrease in its activity. Waste oil contained 1980 ppm water and 2.5% free fatty acids, but these contaminants had little influence on enzymatic production of biodiesel fuel.     

Study of oxygenated biomass fuel blends on a diesel engine

Vegetable methyl ester was added in ethanol–diesel fuel to prevent separation of ethanol from diesel in this study. The ethanol blend proportion can be increased to 30% in volume by adding the vegetable methyl ester. Engine performance and emissions characteristics of the fuel blends were investigated on a diesel engine and compared with those of diesel fuel. Experimental results show that the torque of the engine is decreased by 6%–7% for every 10% (by volume) ethanol added to the diesel fuel without modification on the engine. Brake specific fuel consumption (BSFC) increases with the addition of oxygen from ethanol but equivalent brake specific fuel consumption (EBSFC) of oxygenated fuels is at the same level of that of diesel. Smoke and particulate matter (PM) emissions decrease significantly with the increase of oxygen content in the fuel. However, PM reduction is less significant than smoke reduction. In addition, PM components are affected by the oxygenated fuel. When blended fuels are used, nitrogen oxides (NO_x) emissions are almost the same as or slightly higher than the NO_x emissions when diesel fuel is used. Hydrocarbon (HC) is apparently decreased when the engine was fueled with ethanol–ester–diesel blends. Fuelling the engine with oxygenated diesel fuels showed increased carbon monoxide (CO) emissions at low and medium loads, but reduced CO emissions at high and full loads, when compared to pure diesel fuel.     

Nanoheterogeneities in PEO/PMMA blends: A modulated differential scanning calorimetry approach

Modulated differential scanning calorimetry has been carried out on melt‐mixed blends of poly(ethylene oxide)/atactic‐poly(methyl methacrylate) (PEO/PMMA). Two PEO molecular weights have been used to prepare blends in the concentration range 10 to 80 wt % of PEO. Two glass transitions temperatures were observed for the fully amorphous blends, in the 10 to 30 wt % PEO range, using the differential of heat capacity with respect to temperature [dC_p/dT] signal. The semicrystalline blends, 40, 60, and 80 wt % PEO, exhibited melting of PEO crystallites and the PEO‐rich phase glass transition at −30 to −50°C. A second glass transition around 30°C was detected for the 40 wt % PEO blend when a cooling run was carried out, because PEO crystallization was avoided under these conditions. Therefore, heterogeneous amorphous phases were observed not only for fully amorphous blends, but also for semicrystalline ones. Further analysis of the dC_p/dT signal, obtained from the MTDSC experiments by fitting with Gaussian curves, showed that there is an interphase that varies in amount between 10 to 50 wt %. Correlation of the MTDSC observations with NMR spectroscopy and SAXS/SANS literature results are discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2034–2043, 2000     

SO3H-功能化季铵盐离子液体催化酯交换制备生物柴油

采用两步合成法制备了4种SO3H-功能化季铵盐离子液体,红外与核磁共振光谱表征结果表明,其结构符合理论结构特点. 热稳定性分析表明,其分解温度都在200℃以上,均可作为制备生物柴油的催化剂. 将这4种离子液体用于催化制备生物柴油,其催化活性主要与其阴离子的结构有关,[n-But3N(CH2)3SO3H][CH3SO3]的催化活性最好. 甲醇:三油酸甘油酯摩尔比为12:1、催化剂用量7%(w)、在65℃下反应24 h时,油酸甲酯产率最高(89.65%). 催化剂重复使用性能良好.     

Transesterification of the crude Jatropha curcas L. oil catalyzed by micro‐NaOH in supercritical and subcritical methanol

Transesterification of the crude Jatropha curcas L. oil catalyzed by micro‐NaOH in supercritical/subcritical methanol was studied. The effects of various reaction variables such as the catalyst content, reaction temperature, reaction pressure and the molar ratio of methanol to oil on the conversion of crude Jatropha curcas L. oil to biodiesel were investigated. The results showed that even micro‐NaOH could noticeably improve this reaction. When NaOH was added from 0.2 to 0.5 to 0.8 wt‐‰ of triacylglycerols, the transesterification rate increased sharply; when the catalyst content was further increased, the reaction rate was just poorly improved. It was observed that increasing the reaction temperature had a favorable influence on the methyl ester yield. For the molar ratio ranging from 18 to 36, the higher the molar ratio of methanol to oil was charged, the faster the transesterification rate seemed. At the fixed stirring rate of 400 rpm, when the catalyst content, reaction temperature, reaction pressure and the molar ratio of methanol to oil were developed at 0.8 wt‐‰ NaOH, 523 K, 7.0 MPa and 24 : 1, respectively, the methyl ester yield could reach 90.5% within 28 min. Further, the kinetics of this reaction was involved and the results showed that it was a pseudo‐first‐order reaction whose apparent activation energy was 84.1 kJ/mol, and the pre‐exponential factor was 2.21×10⁵.     

Nucleophilic addition of hydrogen sulfide to methyl oleate,methyl linoleate,and soybean oil

Hydrogen sulfide was added to methyl oleate, methyl linoleate, and soybean oil at −70 and 25 C in the presence of boron trifluoride. Major reaction compounds were identified by gas liquid chromatography and mass spectrometry. At −70 C with a 200 molar ratio of hydrogen sulfide to ester, the reactions were complete in 4 hr. Primary reaction product from methyl oleate was methyl 9(10)-mercaptostearate. Methyl linoleate gave ca. equal amounts of methyl 9-(2-pentyl-1-thiolan-5-yl) nonanoate and methyl 8-(2-hexyl-1-thiolan-5-yl) octanoate. At 25 C, the reaction of methyl oleate and linoleate with hydrogen sulfide was less complete, and more side reactions were noted. When equimolar amounts of methyl oleate and methyl 9(10)-mercaptostearate were reacted in the presence of boron trifluoride at 25 C, a new compound was formed, bis(methyl n-octadecanoate 9[10]-yl) sulfide. The addition of liquid hydrogen sulfide to soybean oil at −70 C in the presence of boron trifluoride yields a product which, upon saponification, acidification, and methylation analyzes by gas liquid chromatography as ca. 52% thiolan, 27% mercaptostearate, 10% palmitate, 6% stearate, and 5% unidentified compounds.     

邻苯二甲酸酐一缩二乙二醇酯的合成

讨论了邻苯二甲酸酐一缩二乙二醇酯的合成工艺,分别以硫酸和对甲基苯磺酸为催化剂合成邻苯二甲酸酐一缩二乙二醇酯。结果表明,对甲基苯磺酸作催化剂的选择性较好,合成邻苯二甲酸酐一缩二乙二醇酯的最佳反应条件为:以对甲基苯磺酸为催化剂,其加入量为一缩二乙二醇质量的1%,反应温度185 ℃,邻苯二甲酸酐和一缩二乙二醇物质的量比为1∶2,反应时间10 h,产品纯度大于98.0%。     

Separation Behavior of Octadecadienoic Acid Isomers and Identification of cis‐ and trans‐Isomers Using Gas Chromatography

Using a strongly polar cyanopropyl capillary column we have investigated the gas chromatography (GC) separation behaviors of 24 octadecadienoic acid methyl ester (18:2ME) isomers compared against saturated methyl stearate (18:0ME) and arachidic acid methyl ester (20:0ME), and the dependency on the GC column temperature. The 24 isomers were obtained by performing cis‐to trans‐isomerization of six regioisomers: five of the 18:2ME isomers were prepared by the partial reduction of methyl α‐linolenate and methyl γ‐linolenate C18 trienoic acids with different double bond positions, whereas the sixth isomer, 18:2ME (c5, c9), was obtained from a raw constituent fatty acid methyl ester (FAME) sample extracted from Japanese yew seeds. There are no reference standards commercially available for 18:2ME isomers, and in elucidating the elution order of these isomers this study should help the future identification of cis‐ and trans‐type of 18:2ME. We also report the identification method of cis‐ and trans‐type of FAME using equivalent chain lengths and attempt the identification of cis‐ and trans‐type of 18:2ME isomers from partially hydrogenated canola oil.