Nonlinear model predictive control of biodiesel production via transesterification of used vegetable oils

The economic performance of an industrial scale semi-batch reactor for biodiesel production via transesterification of used vegetable oils is investigated by simulation using nonlinear model predictive control (NMPC) technology. The objective is to produce biodiesel compliant to the biodiesel standards at the minimum costs. A first-principle model is formulated to describe the dynamics of the reactor mixture temperature and composition. The feed oil and mixture composition are characterized using a pseudo-component approach, and the thermodynamic properties are estimated from group contribution methods. The dynamic model is used by the NMPC framework to predict the optimal control profiles, where a multiple shooting based dynamic optimization problem is solved at every sampling time. Simulation results with the economic performance of an industrial scale semi-batch reactor are presented for control configurations manipulating the methanol feed flow rate and the heat duty.     

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.     

Biodiesel production in a jet flow stirred reactor

The rate of biodiesel formation was assessed in a transesterification reactor stirred with a dual jet flow close loop. A blend of 85% of soybean and 15% of sunflower oil, methanol and NaOH were used to study the rate of conversion from vegetable oil to methyl esters. A 9 l cylindrical reactor with conical bottom discharge connected to two centrifugal pumps for fluid recirculation through dual opposite radial jet flows in its upper part was developed for the experiment. The system did not require a heating supply due that the frictional effect inside the recirculation hoses and nozzles produced self heating of the inlet fluid to the reactor. Four different diameters of ejector corresponding to initial Reynolds Number (Re) ranging between 1300 and 6470 were tested to assess the reactor heating profile along with the kinetics of biodiesel formation. Clear performance differences among ejector diameters and Reynolds Number values were observed showing that higher Re result in low relative conversion times along with higher final temperature in the reactor. For 98% of relative conversion to biodiesel, the ejector with Re = 6470 showed 88% reduction in transesterification time with respect to an ejector delivering a Re = 1300 and without requiring any external heat source.     

Optimization of conversion of waste rapeseed oil with high FFA to biodiesel using response surface methodology

In the present study, waste rapeseed oil with high free fatty acids (FFA) was used as feedstock for producing biodiesel. In the pretreatment step, FFA was reduced by distillation refining method. Then, biodiesel was produced by alkaline-catalyzed transesterification process, which was designed according to the 2⁴ full-factorial central composite design. The response surface methodology (RSM) was used to optimize the conditions for the maximum conversion to biodiesel and understand the significance and interaction of the factors affecting the biodiesel production. The results showed that catalyst concentration and reaction time were the limiting conditions and little variation in their value would alter the conversion. At the same time, there was a significant mutual interaction between catalyst concentration and reaction time.The biodiesel produced in the present experiment was analyzed by gas chromatography/mass spectrometry (GC/MS), which showed that it mainly contained six fatty acid methyl esters. In addition, the diesel indexes analysis showed that most of the fuel properties were in reasonable agreement with the 0# diesel standard of China (GB252-2000) and the biodiesel standard of America (ASTM D6751).     

磁性固体碱催化剂在棕榈油制备生物柴油中的应用研究

采用煅烧法制得磁性固体碱催化剂CaO/Fe3O4，考察了该催化剂催化24℃分提棕榈油与甲醇酯交换反应制备生物柴油的最佳反应条件及催化剂使用寿命。结果表明，最佳反应条件为醇油摩尔比8、催化剂用量4％、反应温度65℃、反应时间2.0 h。在该条件下制得的生物柴油中脂肪酸甲酯含量为98.2%，其性能指标均达到国家标准GB/T-20828-2007的要求。在棕榈油制备生物柴油过程中重复利用催化剂CaO/Fe3O4进行酯交换反应8次，产物中脂肪酸甲酯含量均在96.5％以上。     

Glycerolysis of Fatty Acid Methyl Esters: 1. Investigations in a Batch Reactor

The present work focused on the glycerolysis of fatty acid methyl esters. The aim was to develop and test a kinetic model that could be used to reliably simulate different process alternatives for this reaction. A prerequisite was the identification and characterization of the factors that affect the reaction kinetics. Experiments were carried out in a batch reactor with and without forced removal of methanol, which is one of the reaction products. Concentrations of all components in the two-phase system were measured. It was found that the methanol concentration has a strong effect on the reaction rate and equilibrium conversion. Near-complete conversions were obtained by stripping methanol with an inert gas. The glycerol concentration in the ester phase was found to increase as the reaction proceeds, which also accelerates the reaction. Effects of mass transfer on the reaction rate were not found to control the reaction rate under well-agitated conditions. A semi-empirical model was used to simulate the reaction. The results from the semi-empirical model show good agreement with experimental results.     

无水硅酸钠催化酯交换合成碳酸二甲酯

以廉价的Na2Si O3·9H2O为原料,通过简单的焙烧处理,制备了系列无水硅酸钠,并将其作为固体碱催化剂应用于碳酸乙烯酯(EC)与CH3OH酯交换合成碳酸二甲酯(DMC)的反应。采用TG-DTA、XRD和Hammett指示剂法对无水Na2Si O3进行表征。结果表明,焙烧温度对无水Na2Si O3的碱强度、总碱量及催化活性没有显著影响。当焙烧温度为200℃时,样品(Na2Si O3-200)的碱强度(Ho)为15.0~18.4,总碱量为10.9 mmol/g。以Na2Si O3-200为催化剂,考察了原料配比、温度和时间对酯交换合成DMC反应的影响。当CH3OH与EC的摩尔比为10∶1,在65℃反应2 h后,EC转化率与DMC收率可分别达到89%和88%。即使在室温条件下,Na2Si O3-200也能有效地催化EC与甲醇酯交换反应的进行。此外,经过4次使用后,Na2Si O3-200的催化活性没有出现明显下降的趋势。     

Fast in situ copolymerization of PET/PEN blends by ultrasonically-aided extrusion

An ultrasonically-aided extrusion process was developed for fast in situ compatibilization of immiscible polymer blends. PET, PEN, and their 50/50 blend were ultrasonically extruded at various amplitudes. PET underwent homopolymerization and degradation, respectively, at ultrasonic amplitudes of 7.5 and 10 μm, while PEN underwent degradation at amplitudes of 5, 7.5, and 10 μm. MALDI-TOF mass spectrometry revealed greater amounts of hydroxyl and carboxyl terminated oligomers in ultrasonically treated PET and PEN, indicating their greater reactivity. Ultrasonic treatment at short residence time led to the enhancement of transesterification reaction in the PEN/PET blend, as shown by ¹H NMR and MALDI-TOF, indicating greater randomization with ultrasonic treatment. The latter was also observed through a shift in T_g that closely follows Gibbs-DiMarzio relation and an increase in viscosity of blend with treatment at an amplitude of 10 μm. No crystallinity was observed in the blend due to the already high level of transesterification introduced by extrusion without treatment. Accordingly, crystallinity, mechanical properties, oxygen permeability, and optical clarity of the blend were not influenced by ultrasonic treatment.     

Transesterification of castor oil: Effect of the acid value and neutralization of the oil with glycerol

This paper evaluates the production of methyl esters from castor oil and methanol after neutralization of castor oil with glycerol. The reaction was carried out under atmospheric pressure and ambient temperature in a batch reactor, employing potassium hydroxide as catalyst. Results showed high yield of castor oil into methyl esters after neutralization of castor oil with glycerol. The highest yield observed was of 92.5% after 15 min of reaction. The best operating condition was obtained applying an alcohol to oil molar ratio of 6.0 and 0.5% w/w of catalyst.