Isopropyl Alcohol Extraction of De‐hulled Yellow Mustard Flour

Vegetable oils are typically extracted with hexane; however, health and environmental concerns over its use have prompted the search for alternative solvents. Mustard oil was extracted with isopropyl alcohol (IPA) to produce an IPA‐oil miscella suitable for industrial applications. Single‐stage extraction resulted in 87.6 % oil yield at a 10:1 (v/w) IPA/flour ratio. Multiple‐stage extraction resulted in higher extraction efficiency with lower IPA use. Four‐stage cross‐current extraction at an IPA/flour ratio of 2:1 (v/w) per stage resulted in 93.7 % oil yield. At 45 °C, a 91.5 % oil yield was achieved with three‐stage extraction using a 2:1 (v/w) IPA/flour ratio. Any changes to the pH of the mixture resulted in reduced oil yield. Water also reduced the extraction efficiency. The azeotropic IPA solution containing 13 % water extracted ~40 % less oil than did dry IPA in both single and multiple‐stage extractions. Some polar compounds were also extracted, including sugars; however, protein extraction was negligible. The protein left in the extracted meal was not degraded or lost during the extraction. The results suggest that IPA is an excellent solvent for mustard oil, but water content exceeding 5 % in the solvent adversely affects the oil extraction and reuse of the IPA.     

Recovery and Recycling of Isopropyl Alcohol Used in Biodiesel Production From Yellow Mustard Oil

The recovery of solvents used during biodiesel synthesis is an important factor in the economic feasibility and sustainability of the entire process. In this study, we looked at the use of isopropyl alcohol (IPA) for oil extraction and biodiesel production, as well as its potential for recovery and recycling. We found that multistage extraction improved oil recovery, with up to 86% oil yield using four stages of extraction at an IPA:mustard flour (volume:weight) ratio of 1.5:1 at room temperature. Using acid–base‐catalyzed transesterification, 99% of the mustard oil was converted to biodiesel. At the end of this process, IPA was recovered from the azeotrope by salting out using potassium carbonate or sodium carbonate. The solubility behavior of the components was evaluated by means of ternary‐phase diagrams of IPA/water/sodium carbonate and IPA/water/potassium carbonate, which determined their liquid–liquid–solid equilibrium constants at ambient pressure and at room temperature. Using 20% (w:w) potassium carbonate, 95% of the IPA was recovered at 99% purity from a starting mixture of IPA containing 13% water. Azeotropic distillation of the IPA–water azeotrope with 10% potassium carbonate resulted in the recovery of 99% of the IPA at 94% purity. These results suggest that IPA is not only a suitable solvent for mustard‐oil extraction but also for salt‐enhanced azeotropic distillation resulting in near‐complete recovery from aqueous solutions.     

大豆油异丙酯的合成研究

用碱催化酯交换法合成大豆油异丙酯,考察了醇油摩尔比、催化剂用量、反应温度、反应时间对酯交换反应的影响。结果表明,合成大豆油异丙酯的最佳条件如下:醇油摩尔比10∶1,反应时间60 min,反应温度80℃,碱催化剂浓度2.0%。在此条件下,大豆油异丙酯的产率达53.07%。最后对比研究了大豆油甲酯、乙酯、异丙酯的合成,得出不同结构的醇与大豆油进行酯交换反应的规律。色谱表征表明,经酯交换作用,原料油成功转化为生物柴油。     

Transesterification of soybean oil with nano-MgO or not in supercritical and subcritical methanol

Nano-MgO can apparently improve the transesterification reaction of soybean oil with supercritical/subcritical methanol. The variables affecting the yield of methyl ester during the transesterification reaction, such as the catalyst content, reaction temperature and the molar ratio of methanol to soybean oil were investigated and compared with those of non-catalyst. When nano-MgO was added from 0.5 wt% to 3 wt%, the transesterification rate increased evidently, while the catalyst content was further enhanced to 5 wt%, little increased in yield. It was observed that increasing the reaction temperature had a favorable influence on methyl ester yield. In addition, for molar ratios of methanol to soybean oil ranging from 6 to 36, the higher molar ratios of methanol to oil was charged, the faster transesterification rate was obtained. When the temperature was increased to 533 K, the transesterification reaction was essentially completed within 10 min with 3 wt% nano-MgO and the methanol/oil molar rate 36:1. Such high reaction rate with nano-MgO was mainly owing to the lower activation energy (75.94 kJ/mol) and the higher stirring.     

Alum as a heterogeneous catalyst for the transesterification of palm oil

Alum has been taken beyond its traditional roles as a water treatment chemical and a confectionary additive to a new role as a catalytic precursor in biodiesel production. Its catalytic potentials were empirically proved via palm oil transesterification with methanol and application of solid state instrumental characterization techniques. The catalyst was very clean, efficient, simple and cheap to produce, and could be clearly separated from the reaction products. When the reaction was carried out under the conditions of catalyst to oil ratio of 7.09 wt%, reaction time of 12 h and temperature of 170 °C, methanol to oil molar ratio of 18:1 and catalyst preconditioned at 550 °C, the yield of fatty acid methyl ester (FAME) obtained was 92.5 wt%.     

In situ transesterification of coconut oil using mixtures of methanol and tetrahydrofuran

The conventional biodiesel production method requires oil extraction followed by transesterification with methanol. The solubility of vegetable oils in methanol is low which decreases the overall rate of reaction. To eliminate the oil extraction step and improve the overall reaction rate, simultaneous extraction, esterification and transesterification were conducted by directly mixing methanol and tetrahydrofuran (THF) co-solvent and sulfuric acid catalyst with ground, desiccated coconut meat (copra) in a batch process and continuing the reaction until the system reached steady state. After separation of the mixture, yield was obtained by measuring the content of triglycerides, diglycerides and monoglycerides in the biodiesel phase. The yield increases with THF:methanol ratio, methanol:oil molar ratio and temperature. Within the range of conditions tested, the highest yield achieved was 96.7% at 60 °C, THF:methanol volume ratio of 0.4 and methanol:oil molar ratio of 60:1. The methanol:oil molar ratio is necessarily high in order to completely wet the copra mass, but is still lower than in previous studies by other researchers on in situ transesterification. Product assays show that the resulting biodiesel product is similar to conventionally produced coconut biodiesel. The results indicate that the in situ transesterification of copra using methanol/THF mixtures merits further study.     

Conversion of waste cooking oil to biodiesel using ferric sulfate and supercritical methanol processes

In this comparative study, conversion of waste cooking oil to methyl esters was carried out using the ferric sulfate and the supercritical methanol processes. A two-step transesterification process was used to remove the high free fatty acid contents in the waste cooking oil (WCO). This process resulted in a feedstock to biodiesel conversion yield of about 85-96% using a ferric sulfate catalyst. In the supercritical methanol transesterification method, the yield of biodiesel was about 50-65% in only 15 min of reaction time. The test results revealed that supercritical process method is probably a promising alternative method to the traditional two-step transesterification process using a ferric sulfate catalyst for waste cooking oil conversion. The important variables affecting the methyl ester yield during the transesterification reaction are the molar ratio of alcohol to oil, the catalyst amount and the reaction temperature. The analysis of oil properties, fuel properties and process parameter optimization for the waste cooking oil conversion are also presented.     

Continuous production of biodiesel from cottonseed oil and methanol using a column reactor packed with calcined sodium silicate base catalyst☆

Sodium silicate and that calcined at 400 °C for 2 h were used to catalyze the transesterification of cottonseed oil with methanol. Calcined sodium silicate(CSS) catalyst exhibited much higher catalytic activity and stability. A maximum biodiesel yield of 98.9% was achieved at methanol/oil mole ratio of 12:1, reaction temperature65 °C, reaction time 3.0 h, and CSS/oil mass ratio of 2 wt%. After 7 consecutive reactions without any treatment,biodiesel yield reduced to 82.5%. Considering technological and economic feasibility, CSS base catalyst supported on θ rings was prepared for continuous transesterification. The maximum yield was 99.1% under optimum conditions(reaction temperature 55 °C, methanol velocity 1 ml·min-1, oil velocity 3 ml·min-1, and 5 tower sections). These results indicate that this new continuous biodiesel production process and apparatus present a great potential for industrial application in biodiesel.     

Combined Production of Biodiesel and Nontoxic Cottonseed Meal Using Two‐Step Two‐Phase Solvent Extraction

The preparation of biodiesel and nontoxic cottonseed meal from cottonseed by two‐step two‐phase solvent extraction (TS‐TSE) combined with the transesterification reaction was investigated. The TS‐TSE process could significantly reduce the biodiesel production costs when compared with the two‐phase solvent extraction (TSE) process due to the reduction in methanol. A series of experiments was conducted to evaluate the effects of some factors on the fatty acid methyl ester (FAME) yield and free gossypol (FG) content. These conditions resulted in a maximum FAME yield and reduced the FG content in the cottonseed meal far below the Food and Drug Administration standard. The nontoxic cottonseed meal could be used as animal feed protein source.     

STUDIES OF TRANSESTERIFICATION OF KARANJA (Pongamia pinnata) OIL IN A PACKED BED REACTOR

Studies were made to determine the influence of different reaction temperatures and residence times on biodiesel yield by transesterification of karanja oil (Pongamia pinnata) in the presence of methanol using a solid acid heterogeneous catalyst in a continuous process. Recycle runs were conducted by further transesterification of the organic phases (first run mixture of methyl ester and unconverted oil) in the presence of methanol under similar conditions. High-pressure liquid chromatography (HPLC) reveals poor biodiesel yield even with an increase in the reaction temperature and residence time in the first run. Biodiesel yield obtained from the recycle runs, however, was greatly increased over that of the first-run biodiesel yield. Recycle transesterification at a reaction temperature of 240°C and residence time of 50 min gives a maximum yield value of 97.74%. Consequently, irrespective of the presence of high free fatty acids and other impurities in karanja oil, recycling the organic phase of the first run significantly enhances the biodiesel yield.     

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.     

新型固体碱铝酸钙催化剂用于生物柴油的制备研究

采用化学合成法制备了铝酸钙固体催化剂,并将其用于菜籽油与甲醇酯交换反应的研究.考察了酯交换反应的条件,实验结果表明,当醇/油摩尔比为15:1,催化剂质茸分数6%,反应温度65℃,搅拌速率270 r/min,反应时间3 h,甲酯的收率为89.05%.产物和催化剂固液分离简单容易,铝酸钙固体催化剂具有较好的稳定性,连续使用7次,甲酯的收率均在87.00%以上.同时采用Hammett指示剂法、XRD、BET等手段对铝酸钙同体催化剂进行了表征.     

Simplifying the Process of Microalgal Biodiesel Production Through In Situ Transesterification Technology

Crop-based biofuels, including biodiesel, has sparked international concerns during recent years. Microalgae have been strongly advocated as the most promising substitute for oil crops. However, the commercialization of microalgal biodiesel is hindered by the high costs of feedstock and conventional production processes. This paper elucidates a simplified, scalable production process under conditions of least energetic demand, which integrates oil extraction and conversion into one step through in situ transesterification. Introducing a co-solvent is the key to success. Criteria for co-solvents applicable to the microalgal biodiesel industry are proposed. The overall biodiesel yield (OBY) of Spirulina was determined for benchmarking purposes, using the Bligh and Dyer protocol for oil extraction, and transesterification with potassium hydroxide. The performance in in situ transesterification of the selected co-solvents toluene, dichloromethane and diethyl ether, as well as the solvent combinations petroleum ether/toluene, toluene/methanol and dichloromethane/methanol, was evaluated by OBY. Among all the co-solvents tested, the toluene/methanol system, 2:1 by volume ratio, demonstrated the highest efficiency, achieving a biodiesel yield of 76% of the OBY for the first in situ transesterification cycle and 10% for the second in situ transesterification cycle.     

Experimental analysis of lipid extraction and biodiesel production from wastewater sludge

The most promising renewable alternative fuel, biodiesel, is produced from various lipid sources. Primary and secondary sludge of municipal wastewater treatment facilities are potential sources of lipids. In this study, factorial experimental analyses were used to study the influence of different variables on the lipid extraction and biodiesel production from dried municipal primary and secondary sludge (Adelaide Pollution Control Plant, London, ON, Canada). The empirical models were developed for each factorial analysis. The temperature turned out to be the most significant variable for lipid extraction by using methanol and hexane as solvents. Extraction using methanol resulted in a maximum of 14.46 (wt/wt) % and 10.04 (wt/wt) % lipid (on the basis of dry sludge), from the primary and secondary sludge sources respectively. A maximum of 11.16 (wt/wt) % and 3.04 wt/wt% lipid (on the basis of dry sludge) were extracted from the primary and secondary sludge sources, respectively, using hexane as a solvent. The FAME (fatty acid methyl ester) yield of the H₂SO₄ catalyzed esterification–transesterification of the hexane and methanol extracted lipids were 41.25 (wt/wt) % and 38.94(wt/wt) % (on the basis of lipid) for the primary sludge, and 26.89 (wt/wt) % and 30.28 (wt/wt) % (on the basis of lipid) for the secondary sludge. The use of natural zeolite as a dehydrating agent was increased the biodiesel yield by approximately 18 (wt/wt) % (on the basis of lipid). The effect of temperature and time was also investigated for biodiesel production from the lipid of wastewater sludge. The yield and quality of the FAME were determined by gas chromatography.     

生物柴油的制备及其副产物粗甘油分离与精制工艺的研究

研究了生物柴油制备工艺条件的确定及其副产品粗甘油的分离与精制,对甘油精制中溶剂的选择、溶液的pH值和蒸馏温度对甘油得率的影响进行了研究。制备生物柴油的最佳条件为醇油摩尔比6:1,催化剂用量1%,反应温度60℃,反应时间90 m in,得率达到98.1%(以菜籽油质量100 g为基准)。粗甘油精制的最佳工艺为:用甲醇作溶剂,离心溶液的pH值在5~7之间,在此条件下甘油的得率可以达到31.2%(以粗甘油质量为基准,100 g菜籽油得16 g粗甘油),纯度达到97.52%,可以满足于各种化工生产。     

Biodiesel Feedstock from Emulsions Produced by Aqueous Processing of Yellow Mustard

The multi-stage treatment of stable oil-in-water emulsions produced during non-enzymatic aqueous processing of dehulled yellow mustard flour with cyclic ethers [tetrahydrofuran (THF) and 1,4-dioxane] was investigated to produce a single-phase oil-solvent-water miscella suitable for biodiesel production. While the single-stage treatment of yellow mustard emulsion recovered 97 % and 95 % of the oil by using 4:1 THF:oil and 9:1 dioxane:oil weight ratios, respectively, miscella phases containing more than 7 % water formed, which made them unsuitable as biodiesel feedstock. Multi-stage treatments of the emulsion using lower THF:oil and dioxane:oil weight ratios were further developed to produce oil-solvent-water miscella phases with low water content. While three-stage extraction of emulsions using 0.5:1, 1:1, 1.5:1, and 2:1 dioxane:oil weight ratios did not destabilize the emulsion, three-stage extraction using 0.5:1 and 0.75:1 THF:oil weight ratios effectively recovered over 97 % of the oil, resulting in the production of oil-rich miscella phases containing only 1 % and 1.5 % water, respectively. These miscella phases were analyzed for free fatty acid and phosphorus contents and proved to be excellent feedstocks for the preparation of high-purity methyl esters through single-phase base-catalyzed transmethylation.     

Biodiesel Production from Mustard Emulsion by a Combined Destabilization/Adsorption Process

Tetrahydrofuran, added to the oil‐in‐water emulsions formed by the aqueous processing of yellow mustard flour, produced oil/water/THF miscellas containing 1–2 % water. The high water content prevented the direct conversion of the system to fatty acid methyl esters (FAME) through a single‐phase base‐catalyzed transmethylation process. Dehydration of these miscellas by adsorption on 4A molecular sieves at room temperature using either batch or continuous fixed‐bed systems successfully reduced the water content to the quality standards needed for biodiesel feedstock (0.3 %). Equilibrium adsorption studies for the uptake of water from oil/THF/water miscella phases at room temperature allowed quantitative comparison of the water adsorption capacity based on the oil and THF concentrations of the miscellas. Batch contact was used to investigate the dominant parameters affecting the uptake of water including miscella composition, adsorbent dose and contact time. The adsorption of the water was strongly dependent on adsorbent dose and miscella oil concentrations. The regeneration of molecular sieves by heating under nitrogen at reduced pressure for 6 h at 275 °C resulted in incomplete desorption of miscella components. The adsorption breakthrough curves in terms of flow rates, initial water and oil miscella concentrations were determined. The dehydrated miscella phases were reacted with methanol in a single‐phase base‐catalyzed transmethylation process with high yields (99.3 wt%) to FAME. The resulting FAME met the ASTM international standard in terms of total glycerol content and acid number.     

Analysis of parameters and interaction between parameters of the microwave-assisted continuous transesterification process of Jatropha oil using response surface methodology

A simple continuous process was designed for the transesterification of Jatropha curcas (J. curcas) oil to alkyl esters using microwave-assisted method. The product with purity above 96.5% of alkyl ester is called the biodiesel fuel. Using response surface methodology, a series of experiments with three reaction factors at three levels were carried out to investigate the transesterification reaction in a microwave and conversion of alkyl ester from J. curcas oil with NaOH as the catalyst. The results showed that the ratio of methanol to oil, amount of catalyst and flow rate have significant effects on the transesterification and conversion of alkyl ester. Based on the response surface methodology using the selected operating conditions, the optimal ratio of methanol to oil, amount of catalyst and flow rate of transesterification process were 10.74, 1.26 wt% and 1.62 mL/min, respectively. The largest predicted and experimental conversions of alkyl esters (biodiesel) under the optimal conditions are 99.63% and 99.36%, respectively. Our findings confirmed the successful development of a two-step process for the transesterification reaction of Jatropha oil by microwave-assisted heating, which is effective and time-saving for alkyl ester production.     

Optimum process and energy density analysis of canola oil biodiesel synthesis

Biodiesel has been recommended as an environmentally benign alternative fuel because it emits a comparatively small amount of air pollutants. Biodiesel can be processed from canola oil, which has a low liquefaction temperature owing to its high unsaturated fatty acid content, which also limits its engine-clogging effects. In this study, optimum conditions such as the amount of methanol, the alkali catalyst, and the reaction temperature were determined for production of biodiesel from canola oil. A maximum biodiesel yield was shown at an oil/methanol mole ratio of 1:6. The optimum amount of catalyst was 1 wt% of potassium hydroxide. The biodiesel yield and the methyl ester content were high when the reaction temperature was 55 °C. The consolute temperature for determining the maximum biodiesel yield was proposed in consideration of the boiling point of methanol. The energy density was analyzed for the final products of biodiesel in comparison to the raw canola oil and other plant oil based biodiesels.     

Application of a Ternary Phase Diagram to the Phase Separation of Oil-in-Water Emulsions Using Isopropyl Alcohol

The oil-in-water emulsion formed during an aqueous extraction of yellow mustard seed flour was destabilized using isopropyl alcohol (IPA) in a four stage extraction process, with concurrent recovery of oil and water in separate phases. The emulsion was extracted using two different approaches: phase separation extraction (PSE) that used fresh IPA as the extraction solvent at each stage, and phase separation extraction with recycle (PSER) that reused the extracted water-rich phase, containing IPA, as the extraction solvent. Extraction processes by both approaches were modeled by the ternary liquid phase diagram of IPA, canola oil and water to characterize the extraction progress. PSER resulted in improved oil–water separation and IPA usage efficiency than PSE, but achieved only 84.0?% oil recovery, compared to 92.3?% by PSE. The ternary diagram of IPA, canola oil and water offered good approximation of the oil and water separation behavior of PSE and PSER by closely predicting the compositions of the separated phases; however, the weight ratio of the separated phases were not as closely predicted.