Continuous production of palm methyl esters

A system for continuous transesterification of palm oil was developed using a continuous stirred-tank reactor (CSTR) and pumps for continuous delivery of oil and catalyst and for continuous removal of product. Potassium hydroxide was used as the catalyst, the methanol-to-oil molar ratio was 6∶1, and reaction temperature was 60°C. The yield of methyl esters increased from 58.8% of theoretical yield at a residence time of 40 min to 97.3% at a residence time of 60 min. However, higher residence times decreased the production rate. During long-term continuous operation, the CSTR displayed steady state conditions in terms of product profile and methyl ester concentration. This process has good potential in the manufacture of biodiesel.     

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.     

Use of dolomite catalyst in biodiesel production via transesterification of waste cooking oil in oscillatory baffled reactor

Biodiesel has recently gained popularity due to its environmental issues and the fact that it is generated from renewable resources. However, the cost of the synthesis of biodiesel is the major impediment to commercialization. The utilization of leftover cooking oils as raw material, the adaptation of a continuous transesterification process, and the use of cheap catalysts are the major possibilities for investigating the cost of biodiesel. In this work, a dolomite catalyst was prepared from natural dolomite rocks and used for the evaluation of continuous transesterification of biodiesel from oleic acid as a model compound of waste cooking oil (WCO). The dolomite catalyst was prepared by activation under vacuum at a surface area of 34.5 m²/g. The characterization tests showed good thermal stability of the catalyst and evolution of the CaO and MgO compounds at high concentrations. A kinetic study was conducted to obtain kinetic parameters of catalytic transesterification of the WCO. The kinetic experiments were carried out at 298–333 K, and residence time up to 80 min. The results presented that the catalytic transesterification is the first-order reaction, and the activation energy was 43 kJ/mol. The oscillatory baffled reactor (OBR) was used to evaluate the dolomite catalyst for the continuous production of biodiesel via transesterification. The evaluation study was conducted at a methanol: oil mole ratio of 6:1 and the effect of different operation variables on oleic acid conversion to biodiesel was studied. These variables were temperature (323, 333, and 343 K), residence times (5–40 min), the amplitude of oscillation (2–8 mm), and frequency of oscillation (1, 2, 3, 4, and 4.3 Hz). The results showed an outstanding performance and stable activity of the dolomite catalyst as a conversion of 96% was obtained at 333 K, 4.3 Hz, 8 mm amplitude, and 40 min residence time.     

Steady-state and transient behavior of a continuous polyethylene terephthalate condensation polymerization process. I. Melt transesterification stage

The steady-state and transient behavior of a continuous stirred-tank reactor for melt transesterification of dimethyl terephthalate with ethylene glycol in the presence of metal acetate catalyst is presented. The kinetic model includes the main transesterification reactions and side reactions leading to diethylene glycol and carboxylic acid end groups. The effect of various reactro operating parameters such as [EG]/[DMT] mole ratio and feed catalyst concentration on the product distribution under steady-state reactor operating conditions is analyzed. The dynamic process model has also been solved and the reactor transients to step changes in various reactor parameters are reported.     

Modeling of poly(ethylene terephthalate) reactors: 4. A continuous esterification process

A mathematical model has been developed for the direct, continuous esterification process. Influence of process and operational variables, including temperature distribution, residence time distribution, bis(hydroxyethyl)terephthalate recycle, pressure, and ethylene glycol (EG) to terephthalic acid ratio on the reactor performance have been investigated in a range as close to industrial practice as possible. The variables influencing the amount of EG reflux (which governs the energy economy) and side products (which govern the product quality) have been discussed. This investigation provides an analysis of a continuous, direct esterification process, and the results indicate strategies for optimizing productivity and product quality.     

Biocatalytical synthesis and monolayer studies of multiple hydroxylated wax esters

The continuous production of aleuritic acid decyl ester has been investigated with Lipozyme^TM as biocatalyst in a fixed-bed reactor. To avoid the limiting effects of mean substrate solubility, the direct synthesis without organic solvents was chosen, whereby a yield of 90% was obtained depending on the residence time. A comparison of different reaction paths to synthesize a centrally dihydroxylated decyl ester indicated a preference for transesterification of the methyl ester. Under external compression, the interfacial behavior of several enzymatically produced hydroxy wax esters was determined with a Langmuir film balance to find a structure/efficiency relationship. Brewster-angle microscopy allowed direct visualization of a wax ester monolayer at the air/water interface.     

Maleic anhydride modification of polyolefin in an internal mixer and a twin‐screw extruder: Experiment and kinetic model

There has been little effort. to quantitatively understand graft copolymerization in batch and continuous mixers. Little information exists on the evolution of grafting reactions with respect to residence time in an internal mixer or along the screw axis in a twin‐screw extruder. In this study, maleic anhydride was grafted onto polypropylene in both an internal mixer and a twin screw extruder. The influence of residence time on degree of grafting in an internal mixer and a twin screw extruder was studied through measuring reaction yields with respect to reaction time in the internal mixer as well as along the screw axis in the extruder. The dependence of the degree of grafting with monomer and peroxide concentration was determined. A free radical kinetic model of the process was developed and compared to experiment. Kinetic parameters were determined.     

TPA和EG连续生产PET的第一酯化反应器操作模拟

对乙二醇(EG)和对苯二甲酸(TPA)连续生产对苯二甲酸乙二酯(PET)的第一酯化反应器进行了数学模拟。数学模型中包括了反应动力学方程、气液平衡和气液传质方程,使模拟结果接近于工厂实践。此外对不同停留时间、不同的反应器操作温度及压力、不同的进料 EG/TPA 的 mol比,进行了模拟计算,得出了反应器出口各种产物的组成随操作参数的变化,并对各操作参数的范围和对反应的影响进行了评述。     

Emulsion polymerization kinetics and reactor design. IV. Continuous-flow operation with recycling

A new mathematical model with a correction for radical capturing efficiency in a continuous emulsion polymerization with recycle flow has been proposed. These performance equations predict the conversion as well as molecular weight distribution of the polymer product during the continuous-flow operation. Experimental results obtained with vigorous mixing associated with a premixer are in best agreement with the theoretical prediction. In certain situations, the recycling provides a means for obtaining a higher degree of back-mixing with a normal flow reactor. However, it is difficult to obtain a high conversion of monomer by a continuous emulsion polymerization operation even with a long residence time. Theoretical and experimental average degrees of polymerization of polymer leaving the reactor are progressively displaced toward smaller values with greater mean residence time. According to the calculations based on our kinetic model the ratio M?_w/M?_n in the continuous emulsion polymerization remains constant regardless of mean residence time.     

Intensified production of biodiesel using a spinning disk reactor

This work achieves continuous transesterification of soybean oil and methanol in a spinning disk reactor. The effects of the methanol-to-oil molar ratio, catalyst type, catalyst concentration, reaction temperature, flow rate, and rotational speed were investigated. Optimal yield of 96.9% was obtained with a residence time of 2–3 s at a molar ratio of 6, potassium hydroxide concentration of 1.5 wt%, temperature of 60 °C, flow rate of 773 mL/min, and rotational speed of 2400 rpm. The production rate of 1.86 mol/min was high compared to that of other reactors for continuous transesterification process, indicating that a spinning disk reactor is a promising alternative method for continuous biodiesel production.     

Continuous production of biodiesel fuel from vegetable oil using supercritical methanol process

A system for continuous transesterification of vegetable oil using supercritical methanol was developed using a tube reactor. Increasing the proportion of methanol, reaction pressure and reaction temperature can enhance the production yield effectively. However, side reactions of unsaturated fatty acid methyl esters (FAME) occur when the reaction temperature is over 300 °C, which lead to much loss of material. There is also a critical value of residence time at high reaction temperature, and the production yield will decrease if the residence time surpasses this value. The optimal reaction condition under constant reaction temperature process is: 40:1 of the molar ratio of alcohol to oil, 25 min of residence time, 35 MPa and 310 °C. However, the maximum production yield can only be 77% in the optimal reaction condition of constant reaction temperature process because of the loss caused by the side reactions of unsaturated FAME at high reaction temperature. To solve this problem, we proposed a new technology: gradual heating that can effectively reduce the loss caused by the side reactions of unsaturated FAME at high reaction temperature. With the new reaction technology, the methyl esters yield can be more than 96%.     

Physical Blowing Agent Residence Conditions Stimulated Morphological Transformations in Extrusion Foaming

In this study, influence of blowing agent residence conditions on foam attributes has been investigated in extrusion foaming process. The blowing agent injection location in the extrusion barrel was found to affect the residence time inside the barrel, which in turn significantly transformed the foam microstructure. The injection location providing higher gas residence time resulted in foams with lower cell size, higher expansion ratio, and enhanced cell density. Further studies were performed to analyze the synergistic influence of residence time variation on foam attributes at different screw rotational speeds, die temperatures, and blowing agent contents.     

Determination of process parameters and modelling of lipase-catalyzed transesterification in a fixed bed reactor

Chemical transesterification is of major importance to the edible oil industry. While alkali catalysts randomize all the fatty acids in a triglyceride mixture, the use of a 1,3 specific lipase causes a more selective exchange of fatty acid residues. Basic process parameters for the development of a continuous solvent-free process in a fixed bed reactor have been determined. The kinetics of the transesterfication reaction and the influence of particle diameter, substrate and water concentration on the effective reaction rate were examined in batchwise experiments. Residence time distribution and parameters of inter- and intraparticle mass transfer were determined by modelling of experiments carried out in a fixed bed reactor under transient conditions. Fixed bed reactors with side stream analysis were used for continuous transesterification. A kinetic model was developed for the enzyme catalyzed reaction, thereby showing the analogy between heterogeneous catalytic and enzyme catalyzed reactions. A one-dimensional heterogeneous reactor model was formulated on the basis of the kinetic equation and different process parameters. For numerical calculations, an exponential enzyme distribution inside the carrier was assumed. The simulation of experimental results indicates that they are well described by the developed model. Water concentration and presence of other substances strongly influence the stability of the immobilized enzyme.     

酯交换法合成碳酸二甲酯研究

通过酯交换法，以甲醇和碳酸丙烯酯（ＰＣ）为原料，反应精馏合成碳酸二甲酯，筛选出最佳催化剂，确定了其用量，考察了原料配比等对反应转化率的影响，研究结果表明，催化剂ＣＨＳ－１和ＣＨＳ－２催化效果较好，其较佳用量为０．４％～０．５％（相对于甲醇的质量）甲醇与ＰＣ的质量比为８～１０，反应停留时间为４０ｍｉｎ～６０ｍｉｎ本文报道的酯交换工艺具有一定的工业应用价值。     

Particle residence times in the continuous spouting of mixtures

A magnetic labelling technique has been used to examine particle residence time distributions in a continuous spouted bed. For a single particle species, the nearly perfect mixing observed found by others is confirmed. For a binary particle system, perfect mixing of each component is found, but the mean residence times are not equal. The ratio of mean residence times is found to be dependent on the fountain height and bed depth; the influence of some of the underlying physical mechanisms in the fountain, free surface and outlet regions can be seen.     

城市垃圾在回转窑内传输过程的冷态实验

研究了城市垃圾 (MSW)在回转窑反应器内的传输特性 .实验表明 :MSW在回转窑内停留时间总体上服从正态分布曲线 ,但与石英砂相比 ,MSW停留时间的分布更偏离出统计规律 ;非均质的MSW比石英砂具有较高的动休止角 ,从而使其在窑内的平均停留时间 (MRT)较长而体积流率 (MVF)较低 ;回转窑转速的提高和倾角的增大都使得MRT减少 ,MVF增大 ;出口挡板对颗粒的MRT具有十分显著的影响 ,而不同纵肋和环肋组合的内构件对MRT的影响主要取决于窑出口处环肋的高度 ;壁面粗糙度通过改变料床床态对MRT和MVF施以影响 .     

Investigation of the effect of impeller rotation rate,powder flow rate,and cohesion on powder flow behavior in a continuous blender using PEPT

In this paper, we examine the movement of particles within a continuous powder mixer using PEPT (Positron Emission Particle Tracking). The benefit of the approach is that the particle movement along the vessel can be measured non-invasively. The effect of impeller rotation rate, powder flow rate, and powder cohesion on the particle trajectory, dispersive axial transport coefficient, and residence time is examined. Increase in the impeller rotation rate decreased the residence time, increased the axial dispersion coefficient, and resulted in longer total path length. Effect of flow rate was different at two different rotation rates. At lower rotation rate, increase in flow rate increased the residence time, decreased the axial dispersion, and resulted in longer total path length. At higher rotation rate, increase in flow rate decreased the residence time, increased the total path length and showed a complex dependence on the axial dispersion coefficient. Increasing cohesion (measured using the flow index, dilation, and the Hausner ratio) did not affect the axial dispersion coefficient significantly, but had significant effects on the total particle path length traveled and the residence time. These results, relevant to pharmaceutical powders, provide better physical understanding of the influence of operating parameters on the flow behavior in the continuous mixer. In addition, one of the main obstacles of modeling continuous mixing of particles is to know the appropriate values for the modeling parameters as well as validate modeling approaches. One example is the dispersion coefficient which leads to an analytical solution for the axial dispersion model of a continuous blending process.     

Simulation of Barium Sulfate Precipitation using CFD and FM‐PDF Modeling in a Continuous Stirred Tank

A mixing‐precipitation model combining computational fluid dynamics (CFD), finite‐mode PDF (probability density function) model, population balance and kinetic modeling has been proposed to simulate the barium sulfate precipitation process in a continuous stirred tank agitated by a Rushton turbine. The effect of various operating conditions such as impeller speed, feed concentration, feed position and mean residence time on the barium sulfate precipitation process is clearly demonstrated. It is shown that the mean crystal size increases by increasing the impeller speed and mean residence time. However, when the feed concentration is increased, the mean crystal size decreases. The predictions are in reasonable agreement with the experimental data in the literature.     

Experimentelle Untersuchung zur Tropfenbildung in kontinuierlich betriebenen Rotor‐Stator‐Maschinen

Rotor‐stator‐machinery is characterized in continuous operation by a homogeneous power input and a defined residence time. The influence of the equipment configuration and process design in the laminar flow regime was considered little till now. In order to fill this knowledge gap, the process behavior of this type of device was systematically investigated experimentally under axial flow conditions, as well as an energetic optimization of the machine configuration was performed.