Optimization of Process Variables for Biodiesel Production Using the Nanomagnetic Catalyst CaO/NaY‐Fe3O4

Due to decreasing oil resources, alternative fuels such as biodiesel are required. The nanomagnetic catalyst CaO/NaY‐Fe₃O₄ was synthesized and used for biodiesel production from canola oil. The structure of the catalysts was characterized by X‐ray diffraction, field emission scanning electron microscopy, Brunauer‐Emmett‐Teller method, Fourier transform infrared spectroscopy, and vibrating sample magnetometer method. To optimize the influence of the operating variables, such as the methanol/canola oil molar ratio, the amount of catalyst, and the reaction time, on the yield of transesterification reaction, an experimental design was applied based on the Box‐Behnken method. The optimum values of these variables were predicted by the cubic model and were in excellent agreement with the experimental results.     

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.     

Marble slurry derived hydroxyapatite as heterogeneous catalyst for biodiesel production from soybean oil

In this study, utilization of waste marble slurry (MS) as an eco‐friendly and low‐cost heterogeneous catalyst is introduced for biodiesel production from soybean oil. Catalytic transesterification reaction was done to convert biodiesel from soybean oil using Marble slurry (MS) derived calcined marble slurry (CMS), and hydroxyapatite (HAP) as a heterogeneous catalyst. Marble slurry derived catalysts were characterized by XRD, FTIR, SEM, and TGA with elemental analysis. Hammett indicator method and ion exchange method were also used to verify catalytic activities of the catalysts. The HAP provided the better biodiesel yield of 94 ± 1 % with the highest basicity (13.30 mmol/g) and basic strength than CMS under optimized reaction conditions: reaction temperature 65 °C; reaction time 3 h; methanol/oil molar ratio 9:1; and catalyst concentration 6 wt%. Reusability tests provide confirmation about the stability of the catalyst and slight fluctuations in catalytic activity and biodiesel yield when used up to five runs.

     

固体碱催化剂用于油脂甲醇酯交换反应制备生物柴油

固体碱催化剂用于酯交换反应制备生物柴油有易分离、流程简单的优点。通过金属氧化物活性筛选,发现氧化钙具有很好的酯交换反应活性。将乙酸钙溶液等体积浸渍负载于碱性载体MgO上,并煅烧得到了氧化钙负载量为16.5％(质量)的CaO/MgO混合氧化物催化剂,其在油脂甲醇酯交换反应制备生物柴油的过程中具有高的反应活性。在64.5℃、醇油比18∶1 、催化剂用量2%、反应3.5 h条件下,油脂转化率为92%,接近传统的液体强碱NaOH的催化能力。用XRD、AAS、XPS、CO2 -TPD等对制得的系列催化剂进行了表征,发现催化剂的碱强度对酯交换反应有着重要的影响。通过选择合适的载体、含钙前驱体和氧化钙负载量可以增加负载型氧化钙催化剂的强碱性位,提高催化剂的反应活性。     

Transesterification of Canola Oil to Biodiesel Using CaO/Talc Nanopowder as a Mixed Oxide Catalyst

A series of heterogeneous catalysts including different molar ratios of CaO/talc was synthesized to study the transesterification reaction of canola oil and methanol under different reaction conditions. Characterization and kinetic results revealed that the activity of this catalyst was enhanced due to the increase of CaO/talc molar ratio value leading to an improvement in the biodiesel production. Moreover, the effect of various parameters on the activity of the undertaken catalysts was studied in order to determine the optimum process conditions. Leaching measurements and the durability of the CaO/talc catalyst under several reaction cycles were evaluated and proved it to be a stable catalyst.     

Oil transesterification over calcium oxides modified with lanthanum

Investigations were conducted on a series of calcium and lanthanum oxides catalyst for biodiesel production. Mixed oxides catalyst showed a superior transesterification activity over pure calcium or pure lanthanum oxide catalysts. The catalyst activity was correlated with surface basicity and specific surface areas. The effects of water and free fatty acids (FFA) levels in oil feedstock, water and CO₂ in air, mass ratio of catalyst, molar ratio of oil to methanol, and reaction temperature on fatty acid methyl ester (FAME) yield were investigated. Under optimal conditions, FAME yields reached 94.3% within 60 min at 58 °C. Mixed CaO-La₂O₃ catalyst showed a high tolerance to water and FFA, and could be used for converting pure or diluted unrefined/waste oils to biodiesel.     

Biodiesel production using tetramethyl- and benzyltrimethyl ammonium hydroxides as strong base catalysts

In recent years, the acceptance of fatty acid methyl esters (biodiesel) as an alternative fuel has rapidly grown in EU. The most common method for biodiesel production is based on triglyceride transesterification to methyl esters with dissolved sodium hydroxide in methanol as catalyst. In this study, cottonseed oil and used frying oil were subjected to the transesterification reaction with tetramethyl ammonium hydroxide and benzyltrimethyl ammonium hydroxide as strong base catalysts. This work investigates the optimum conditions for biodiesel production using amine-based liquid catalysts. Biodiesel ester content was strongly related with the type of feedstock and the reaction variables, such as those of the catalyst concentration, methanol to oil molar ratio, and reaction time. The overall results suggested that the transesterification of cottonseed oil achieved high conversion rates with both catalysts, while the use of waste oil resulted in lower yields of methyl esters due to the possible formation of amides.     

Heterogeneous Catalyst of Mixed K Compounds/Ca‐Al‐Graphite Oxide for the Transesterification of Soybean Oil to Biodiesel

A novel heterogeneous solid base catalyst was prepared by loading of Ca‐Al‐graphite oxide with mixed potassium salts and applied in the transesterification of soybean oil with methanol to produce biodiesel. The catalysts were characterized by Hammett indicators, X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X‐ray spectrometry, and transmission electron microscopy. The effects of the methanol‐to‐oil molar ratio, catalyst amount, reaction temperature, stirring rate, and reaction time were investigated to optimize the transesterification reaction conditions. Moreover, the prepared catalyst retains its activity after being used for four cycles. In particular, the solid base catalyst can be effectively and easily separated from the reaction system, which may provide significant benefits for the development of an environmentally benign and continuous process for preparing biodiesel.     

Dolomite as a heterogeneous catalyst for transesterification of canola oil

In this study, the catalytic activity of dolomite was evaluated for the transesterification of canola oil with methanol to biodiesel in a heterogeneous system. The influence of the calcination temperature of the catalyst and the reaction variables such as the temperature, catalyst amount, methanol/canola oil molar ratio, and time in biodiesel production were investigated. The maximum activity was obtained with the catalyst calcined at 850 °C. When the reaction was carried out at reflux of methanol, with a 6:1 molar ratio of methanol to canola oil and a catalyst amount of 3 wt.% the highest FAME yield of 91.78% was obtained after 3 h of reaction time.     

Influence of the glycerin content in the preparation of calcium diglyceroxide from eggshell applied in the residual oil transesterification

Currently, biodiesel is pointed out worldwide as the main alternative in the complementation and substitution of petrochemical diesel. However, the current industrial route of synthesis of this biofuel depends on the cost of raw materials (which are also destined for food purposes) and the expense of the production process. Aiming to remedy this obstacle, the use of solid, sustainable, low-cost, efficient, and reusable catalysts in residual raw materials, such as waste cooking oils, has been highlighted as a promising alternative. This work focused on studying the influence of the glycerin content used in the preparation by wet impregnation of catalyst calcium diglyceroxide in the efficiency of transesterification of waste cooking oil. The catalyst was synthesized from CaO from chicken eggshell, raw glycerin co-product from biodiesel, and methanol. The transesterification reactions were performed using 120 g of frying residual oil, methanol: oil molar rate of 6:1, constant shaking, and reaction temperature of 63 ± 1°C for 180 min. The catalyst material synthesized with residual glycerin was active for four reactions (without reactivation of its sites) with high percentages of efficiency of 96.13, 96.85, 95.93, and 91.65, respectively. It was noted that the glycerol purity correlated with changes in the structural morphology of the final compound, as well as changes in the leaching rate, acidity index, water content, and ester content of the blends. It was found that adding 15% water to the lipid material correlated with an increase in ester content (99%) in the synthesized biodiesel.     

Metakaolinite as a catalyst for biodiesel production from waste cooking oil

The use of metakaolinite as a catalyst in the transesterification reaction of waste cooking oil with methanol to obtain fatty acid methyl esters (biodiesel) was studied. Kaolinite was thermally activated by dehydroxylation to obtain the metakaolinite phase. Metakaolinite samples were characterized using X-ray diffraction, N₂ adsorption-desorption, simultaneous thermo-gravimetric analyse/differential scanning calorimetry (TGA/DSC) experiments on the thermal decomposition of kaolinite and Fourier-transform infrared spectrometer (FTIR) analysis. Parameters related to the transesterification reaction, including temperature, time, the amount of catalyst and the molar ratio of waste cooking oil to methanol, were also investigated. The transesterification reaction produced biodiesel in a maximum yield of 95% under the following conditions: metakaolinite, 5 wt-% (relative to oil); molar ratio of oil to methanol, 1∶23; reaction temperature, 160°C; reaction time, 4 h. After eight consecutive reaction cycles, the metakaolinite can be recovered and reused after being washed and dried. The biodiesel thus obtained exhibited a viscosity of 5.4?mm²?s^–1 and a density of 900.1 kg?m^–3. The results showed that metakaolinite is a prominent, inexpensive, reusable and thermally stable catalyst for the transesterification of waste cooking oil.     

氧化锌催化菜籽油制生物柴油

氧化锌被用于菜籽油甲醇酯交换反应催化剂并制备生物柴油,从不同的锌盐得到的氧化锌在170～220 ℃都具有很好的活性。对氧化锌催化剂进行了活性评价和反应条件研究。结果表明,氧化锌催化剂具有很好的抗酸和抗水性能,在水质量分数高达20%和游离脂肪酸高达15%时,仍保持较高的反应转化率,可大幅度简化原料油的预处理和产品的分离纯化过程。     

硝酸镧改性钙镁锌催化剂制备生物柴油

通过掺杂不同比例的硝酸镧实现对钙镁锌三金属氧化物固体碱催化剂的改性,对改性催化剂用于制备生物柴油的工艺条件的了优化,并通过SEM的方法对改性催化剂的表面结构进行表征。结果表明硝酸镧的加入可以降低钙镁锌三金属氧化物固体碱催化剂最适催化温度并减少催化剂用量。添加3%(质量分数)的硝酸镧的改性钙镁锌体系催化剂,在反应温度为50℃时,醇油摩尔比为15∶1,反应时间为1h时,生物柴油产率可达到86.8%。这种改性催化剂更适于工业化应用。     

Production of biodiesel from waste vegetable oil using impregnated diatomite as heterogeneous catalyst

In this study, biodiesel was produced from waste vegetable oil using a heterogeneous base catalyst synthesized by impregnating potassium hydroxide (KOH) onto diatomite. Response surface methodology based on a central composite design was used to optimize four transesterification variables:temperature (30–120 °C), reaction time (2–6 h), methanol to oil mass ratio (10%–50%) and catalyst to oil mass ratio (2.1%–7.9%). A quadratic poly-nomial equation was obtained to correlate biodiesel yield to the transesterification variables. The diatomite–KOH catalyst was characterized using X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FTIR) and a scanning electron microscope (SEM) equipped with an energy dispersive X-ray detector (EDS). A maximum biodiesel yield of 90%(by mass) was obtained. The reaction conditions were as follows:methanol to oil mass ratio 30%, catalyst to oil mass ratio 5%, reaction time 4 h, and reaction temperature 75 °C. The XRD, FTIR and SEM (EDS) results confirm that the addition of KOH modifies the structure of diatomite. During impregnation and calcination of the diatomite catalyst the K2O phase forms in the diatomite structural matrix and the active basicity of this compound facilitates the transesterification process. It is possible to recycle the diatomite–KOH catalyst up to three times. The crucial biodiesel properties from waste vegetable oil are within the American Stan-dard Test Method specifications.     

Calcium/chitosan spheres as catalyst for biodiesel production

Chitosan, an abundant biopolymer extracted from crustacean shells, can be used as a structuring agent by the insertion of calcium oxide and used as a catalyst in transesterification reactions. These calcium‐incorporated chitosan spheres were calcined in order to obtain a porous calcium catalyst without organic material. The materials were characterized using X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared and X‐ray photoelectron spectroscopies, temperature‐programmed desorption of CO₂, scanning electron microscopy and specific surface area analysis. Afterwards the calcined calcium/chitosan spheres were used in the transesterification reaction of sunflower oil with methanol. The conversion of sunflower oil to methyl esters (Y_FAME), under optimized reaction conditions, which were determined by factorial experimental design (X_MR, 1:9; X_CAT, 3 wt%; time, 4 h; temperature, 60 °C; magnetic stirring, 1000 rpm), was 56.12 ± 0.32 wt%. These results show that chitosan can be used as a precursor for the formation of calcium/chitosan spheres, yielding a porous calcium oxide (with higher surface area) that can be used as an alkaline catalyst for biodiesel production. © 2014 Society of Chemical Industry     

Synthesis and Characterization of Amorphous Nano‐Alumina Powders with High Surface Area for Biodiesel Production

Nano‐alumina powders containing yttrium oxide were synthesized via the sol‐gel method using aluminum chloride hexahydrate as catalyst precursor. Fourier transform infrared analysis showed the presence of Al‐O and Al‐O‐Al bands in the powder structure and X‐ray diffraction spectra proved that the alumina was in the amorphous phase. The amorphous nano‐alumina powders were shown to be mesoporous with a high surface area, and both spherical and slit‐shaped particles were found in the calcined powder. A high percentage of conversion of oil to biodiesel was obtained in the transesterification reaction and the synthesized nano‐alumina powders could be easily regenerated for further use. The amorphous nano‐alumina powder can thus be recommended for use as active catalyst in the transesterification reaction for biodiesel production on the industrial scale.     

酸性离子液体［(CH2)4SO3HMIM］［HSO4］催化潲水油制备生物柴油的研究

制备了酸性离子液体[(CH₂)₄SO₃HMIM］［HSO₄］并用于催化潲水油制备生物柴油,研究了反应时间、反应温度、醇油物质的量比和剂油物质的量比等对酯交换反应转化率的影响,确定了较适宜的反应条件。结果表明,在反应时间4 h、反应温度140 ℃、醇油物质的量比12和剂油物质的量比0.08条件下,酯交换反应转化率为92.13%。制备的生物柴油达到了中国柴油机燃料调合用生物柴油(BD100)标准GB/T20828-2007。     

Rapid transesterification of <Emphasis Type="Italic">Jatropha curcas</Emphasis> oil to biodiesel using novel catalyst with a microwave heating system

We used a microwave heating system to increase Jatropha biodiesel yield, and to reduce both reaction time and energy consumption. The feasibility of converting natural and non-edible feedstocks including arcuate mussel shells and dolomitic rocks, into a novel high-performance, reusable, low-cost and heterogeneous catalyst for the synthesis of biodiesel was also explored. Arcuate mussel shells and dolomitic rocks were first ground and calcined at 900 °C for 2 h. After calcination, calcium oxide (CaO) or a mixed oxide of calcium and magnesium (CaO·MgO) was obtained as white powder, which was then chemically activated to improve the physical, chemical and surface properties, and catalytic activities of the catalysts. By heating CaO from waste shells in an excess dehydrated methanol under 65 °C at 8 h with nitrogen (N₂) flow, calcium methoxide (Ca(OCH₃)₂) catalyst was prepared. The CaO from natural rocks was, however, turned into calcium glyceroxide complex, by combining with methanol and glycerol of the by-product. It was determined that calcium glyceroxide (Ca[O(OH)₂C₃H₅]₂) was formed during the transesterification and acted as the most active phase. Catalyst characterization was by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), and Brunauer-Emmett-Teller (BET) surface area and basic strength measurements. The reaction parameters, including reaction time, microwave power, methanol/oil molar ratio, catalyst dosage and catalyst reusability, were studied for fatty acid methyl esters (FAME) yield. The results indicated that Ca(OCH₃)₂ and Ca[O(OH)₂C₃H₅]₂ catalysts derived from waste shells and natural rocks showed good reusability, high energy efficient, environmental-friendly, low cost and facile route for the synthesis of biodiesel.     

Calcium oxide as a solid base catalyst for transesterification of soybean oil and its application to biodiesel production

In order to study solid base catalyst for biodiesel production with environmental benignity, transesterification of edible soybean oil with refluxing methanol was carried out in the presence of calcium oxide (CaO), -hydroxide (Ca(OH)₂), or -carbonate (CaCO₃). At 1 h of reaction time, yield of FAME was 93% for CaO, 12% for Ca(OH)₂, and 0% for CaCO₃. Under the same reacting condition, sodium hydroxide with the homogeneous catalysis brought about the complete conversion into FAME. Also, CaO was used for the further tests transesterifying waste cooking oil (WCO) with acid value of 5.1 mg-KOH/g. The yield of FAME was above 99% at 2 h of reaction time, but a portion of catalyst changed into calcium soap by reacting with free fatty acids included in WCO at initial stage of the transesterification. Owing to the neutralizing reaction of the catalyst, concentration of calcium in FAME increased from 187 ppm to 3065 ppm. By processing WCO at reflux of methanol in the presence of cation-exchange resin, only the free fatty acids could be converted into FAME. The transesterification of the processed WCO with acid value of 0.3 mg-KOH/g resulted in the production of FAME including calcium of 565 ppm.     

Biodiesel production from vegetable oil using heterogenous acid and alkali catalyst

Zanthoxylum bungeanum seed oil (ZSO) with high free fatty acids (FFA) can be used for biodiesel production by ferric sulfate-catalyzed esterification followed by transesterification using calcium oxide (CaO) as an alkaline catalyst. Acid value of ZSO with high FFA can be reduced to less than 2 mg KOH/g by one-step esterification with methanol-to-FFA molar ratio 40.91:1, ferric sulfate 9.75% (based on the weight of FFA), reaction temperature 95 °C and reaction time 2 h, which satisfies transesterification using an alkaline catalyst. The response surface methodology (RSM) was used to optimize the conditions for ZSO biodiesel production using CaO as a catalyst. A quadratic polynomial equation was obtained for biodiesel conversion by multiple regression analysis and verification experiments confirmed the validity of the predicted model. The optimum combination for transesterification was methanol-to-oil molar ratio 11.69:1, catalyst amount 2.52%, and reaction time 2.45 h. At this optimum condition, the conversion to biodiesel reached above 96%. This study provided a practical method to biodiesel production from raw feedstocks with high FFA with high reaction rate, less corrosion, less toxicity, and less environmental problems.