水和游离脂肪酸对DBU催化制备生物柴油的影响

以低品质油脂作为生产生物柴油的原料可以有效降低产品的成本。催化剂对原料油中主要杂质游离脂肪酸和水分的耐受程度决定了该工艺对原料油的适应性。本文采用有机碱1,8-二氮杂双环[5,4,0]十一碳-7-烯（DBU）催化酯交换反应制备生物柴油,研究了不同水和游离脂肪酸含量下酯交换反应的转化率、反应后产物两相的组成以及各组分在两相的分配。结果表明,DBU作为催化剂时,对水和游离脂肪酸具有较强的耐受性：水含量小于2%（质量分数,下同）,游离脂肪酸含量小于5%;1.5%左右的水对反应具有促进作用,水含量为1.5%时,酯交换转化率最高可达93.7%。此外,水和游离脂肪酸会降低甲醇、DBU在甲酯相中的分布,这使得甲酯相中甲酯的纯度有所上升。     

Coupling reaction and azeotropic distillation for the synthesis of glycerol carbonate from glycerol and dimethyl carbonate

A new process, coupling reaction and azeotropic distillation was proposed for the synthesis of glycerol carbonate (GC) from glycerol (G) and dimethyl carbonate (DMC). The bench scale experimental investigation was systematically conducted for this new process. With calcium oxide (CaO) as the solid catalyst, the high yield of glycerol carbonate can be obtained at a low molar ratio of dimethyl carbonate to glycerol with the method of coupling reaction and azetropic distillation. The effect of azeotropic agents on glycerol carbonate yield was explored, and indicated that benzene was the most effective azeotropic agent. The effects of the process parameters, tower height, amount of added benzene, final temperature of tower bottom and reflux ratio were investigated. Glycerol carbonate yield can be as high as 98% under the conditions at molar ratio of dimethyl carbonate to glycerol 1:1, final temperature of tower bottom 85 °C, 1.5 mass ratio of added benzene to that in the azeotrope with methanol theoretically produced and reflux ratio 4. By continuously removing methanol from reaction system with the method of coupling reaction and azeotropic distillation, the yield of glycerol carbonate can be retained at high level using the recycled catalyst.     

Glycerol carbonate synthesis from glycerol and dimethyl carbonate using guanidine ionic liquids

A large number of surplus glycerol from the biodiesel production can be used as renewable feedstock to produce glycerol carbonate.In this paper,a series of guanidine-based ionic liquids were synthesized to catalyze the transesterification of glycerol and dimethyl carbonate.The tunable basicity and the anion-cation cooperative effect were responsible for the obtained results.The [TMG][TFE] showed the best activity turnover frequency (TOF) of 1754.0 h-1,glycerol (GL) conversion of 91.8％,glycerol carbonate (GC) selectivity of 95.5％) at 80 ℃ with 0.1 mol％ catalyst for 30 min.The reaction mechanism of the transesterification was also proposed.     

Synthesis of glycerol carbonate from glycerol and dimethyl carbonate by transesterification: Catalyst screening and reaction optimization

The synthesis of glycerol carbonate from glycerol and dimethyl carbonate by transesterification is reported. Firstly, a catalyst screening has been performed by studying the influence of different basic and acid homogeneous and heterogeneous catalysts on reaction results. Catalytic activity is extremely low for acidic catalysts indicating that reaction rate is very slow. On the contrary, high conversions and yields are obtained for basic catalysts. Catalytic activity increases with catalyst basic strength. The best heterogeneous catalyst is CaO. Calcination of CaO increases dramatically its activity due to calcium hydroxide removal from its surface. A reaction optimization study has been carried out with CaO as catalyst by using a factorial design of experiments leading to operation conditions for achieving a 100% conversion and a >95% yield at 1.5 h reaction time: 95 °C, catalyst/glycerol molar ratio = 0.06 and dimethyl carbonate/glycerol molar ratio = 3.5. Carbonate glycerol can be easily isolated by filtering the catalyst out and evaporating the filtrate at vacuum. Leaching of catalyst in reaction medium was lower than 0.34%. Catalyst recycling leads to a quick decrease in both conversions and yields probably due to a combination of catalyst deactivation by CaO exposure to air between catalytic runs, and a decrease in the catalyst surface area available for reaction due to particle agglomeration.     

DBU/甘油/CO2反应过程及动力学

1,8-二氮朵双环[5.4.0]十一碳-7-烯（DBU）-甘油溶液作为一种新型溶剂,具有低热容、高沸点等优点,目前被广泛研究应用于化学合成和产物分离等。本文考察了不同摩尔比的DBU-甘油溶液吸收CO₂效果,测定了不同摩尔比的DBU-甘油溶液吸收CO₂反应过程中体系的黏度变化,研究了DBU-甘油溶液吸收CO₂反应的动力学。结果表明,在反应温度25℃、CO₂气体流速为238mL/min的条件下,DBU与甘油摩尔比为0.49~1的溶液对CO₂的吸收量可在120min的反应时间内达到10.88g/100g溶液;DBU与甘油摩尔比为0.49∶1和1.12∶1的溶液在吸收CO₂后体系的黏度显著增大,而DBU与甘油摩尔比为0.11∶1和3.43∶1的溶液在吸收CO₂后体系的黏度变化较小。25℃、常压下,在消除扩散影响,甘油大大过量时,DBU/甘油/CO₂反应的速率方程为r=0.22C_DBUP_CO2^0.5,反应的活化能为40.44kJ/mol。     

Production of glycerol carbonate via reactive distillation and extractive distillation:An experimental study☆

A process for the production of glycerol carbonate (GC) is proposed with the transesterification of glycerol (GL) and dimethyl carbonate (DMC) with CaO as catalyst by reactive distil ation and extractive distil ation. The perfor-mance of solvents in separating DMC-methanol azeotrope and the effects of operation parameters on the reactive distillation process are investigated experimental y. The results indicate that both the GL conversion and GC yield increase with the DMC/GL molar ratio, reflux ratio, final temperature of tower bottom, and CaO/GL molar ratio and decrease as the recycle number of CaO increases. The calcium concentration in the residual reaction mixture also decreases remarkably as the DMC/GL molar ratio increases. At DMC/GL molar ratio 4.0, reflux ratio 1.0, final temperature of tower bottom 358 K, and CaO/GL molar ratio 0.05, both the GL conversion and GC yield can reach above 99.0%, and the mass concentration of calcium in the product is less than 0.08%.     

A review of ionic liquids as catalysts for transesterification reactions of biodiesel and glycerol carbonate production

Biodiesel production has been rapidly increasing due to the strong governmental policies and incentives provided leading to an oversupply of its by-product, glycerol. Therefore, finding ways of utilizing glycerol is essential to increase the net energy and sustainability of biodiesel. Ionic liquids have been used successfully as catalyst for both the production of biodiesel and the conversion of glycerol to glycerol carbonate. These catalysts are relatively environmentally friendly as they have the potential to enable sustainable processes. Herein, the prospect of using ionic liquids to catalyze transesterification triglycerides for the production of biodiesel and the conversion of glycerol to glycerol carbonate will be discussed. Elucidation of the reaction mechanism is expected to provide an in-depth understanding of the process with respect to the effects of cation and anion based on the reactions of interest.     

Reactive distillation for synthesis of glycerol carbonate via glycerolysis of urea

This study developed a new process for synthesis of glycerol carbonate via glycerolysis of urea by reactive distillation. Missing thermodynamic parameters were estimated by various group contribution methods. The results of Gibbs free energy showed that Gani's method provided the lowest deviation. Equilibrium and kinetic model parameters of the glycerolysis obtained from batch experiments were employed for the simulation of the reactive distillation using Aspen Plus^® software. High conversion of glycerol was achieved by reducing reactant loss in distillate through an increase in the number of stripping and reaction stages and a decrease in the number of rectifying stages. Moreover, glycerol and urea in distillate were recycled to the reactive section by increasing reflux ratio to a reasonable value. The suitable design and operating parameters were achieved at 3 stripping stages, 3 reactive stages, no rectifying stage, reboiler heat duty of 15 kW and reflux ratio of 2. This offered 93.6% conversion of glycerol, and 90.0% yield of glycerol carbonate with 100% purity in the final product. Compared with conventional in vacuo process, reactive distillation promoted glycerol conversion by 29.1% and saved in energy consumption by 37.1%.     

Granulation of sludge under different loads of a glycerol fraction from biodiesel production

The aim of the research was to evaluate the possibility of using the crude glycerol fraction from biodiesel manufacturing processes for granular sludge production. The experiment was carried out simultaneously in four sequencing batch reactors (SBRs) at different carbon loads: 0.2 ± 0.08, 0.6 ± 0.16, 1.1 ± 0.27, and 1.3 ± 0.35 g COD/g TSS per cycle (COD – chemical oxygen demand, TSS – total suspended solids). Granulation did not occur in the reactor with the lowest organic carbon load. In the remaining reactors small granules began to appear after 25 cycles of reactor operation. In all reactors the efficiency of carbon removal remained at ca. 80%. The highest granular sludge production per cycle was 0.31 ± 0.28 g TSS/L; it was obtained at an organic load of 1.1 ± 0.27 g COD/g TSS per cycle. Most of the introduced COD was removed in the reactors during the first 5 h of aeration; the COD removal rate was correlated with the organic load and varied from 123.12 to 472.76 mg COD per litre and hour. Practical applications: With the increasing production of biodiesel fuel a problem arises with the utilization of glycerol that is a by‐product of the process. By‐product glycerol fraction from small agricultural installations is usually contaminated. Its composition varies depending on parameters of the transesterification process and it is unprofitable to purify it. In the present research we investigated one possible way of dealing with the by‐product. The glycerol fraction was successfully used as a carbon source for the production of aerobic granular sludge. The granules obtained can be used as a seed sludge in granule‐based reactors, or can be cofired with coal or directly combusted. Since aerobic granular sludge is one of the most promising technologies investigated during the last few years it appears to possess high utility.     

Optimization of supercritical dimethyl carbonate (SCDMC) technology for the production of biodiesel and value-added glycerol carbonate

In the present study, biodiesel has been successfully produced from triglycerides and dimethyl carbonate, instead of the conventional alcohol. In this non-catalytic supercritical dimethyl carbonate (SCDMC) technology, valuable compound of glycerol carbonate is obtained as side product, rather than the undesirable glycerol. Glycerol carbonate has higher commercial value compared to glycerol and its application in industries is enormous. In this optimization study, the effects of important parameters including reaction temperature, molar ratio of dimethyl carbonate to oil and reaction time were investigated and optimized by employing response surface methodology (RSM) analysis. It was found that the mathematical model developed was statistically significant and adequate to predict the optimum yield. The optimum conditions for SCDMC process was found to be 380 °C for reaction temperature, 39:1 mol/mol of dimethyl carbonate to oil molar ratio and 30 min of reaction time to obtain 91% optimum yield of biodiesel.     

Cleaner gasoline production by using glycerol as fuel extender

Glycerol, a major by-product of biodiesel production, was employed as a fuel extender in this study. The process was originally investigated by etherifying the entire fluidized catalytic cracking (FCC) gasoline with glycerol. The reactions were carried out in a pressurized liquid phase reactor in the presence of three different catalysts (i.e. Amberlyst 16, Amberlyst 15, and β-zeolite) at 70 °C and 2.6 MPa with a volume ratio of FCC gasoline to glycerol ratio of 84:16 for 10 h. The catalytic activity could be ordered as Amberlyst 16 > Amberlyst 15 >> β-zeolite. The properties of FCC and etherified FCC products were determined by the standard analysis of Research Octane Number (RON), blending Reid vapor pressure (bRvp), distillation temperature following the standard methods of ASTM D-2699, ASTM D-5191 and ASTM D-86, respectively. It was found that the olefin content decreased opposing with increasing of octane number due to ethers of glycerol formation and the etherified gasoline product has lower bRvp than that of original FCC gasoline. The process of FCC gasoline etherification with glycerol showed great environmental benefits; in addition, ethers produced renewably from glycerol could extend the gasoline volume.     

The antioxidant and anticorrosive properties of crude glycerol fraction from biodiesel production

BACKGROUND: Raw glycerol fractions as the waste material from biodiesel production were investigated for its antioxidant and anticorrosive properties. For comparison raw glycerol fractions and biodiesel fuels together with different oil feedstocks (as an input material for the transesterification process) were measured by means of electron paramagnetic resonance (EPR) spectroscopy. Additionally glycerol fractions were subjected to corrosivity testing (Herbert method). RESULTS: 1,2,3‐Propanetriol‐containing fractions exhibited high free radical scavenging properties, in comparison with biodiesel and oil material. Additionally, the Herbert test proved the anticorrosive ability of the crude glycerol fractions investigated. Radical scavenging (antioxidant) properties obtained from EPR spectroscopy paralleled the anticorrosive investigations, with samples having the highest quenching abilities giving the best results in the Herbert tests. CONCLUSION: The anticorrosive activity of glycerol fractions examined in this paper generates a new application in lubricant manufacturing. The results show new ways of utilising raw glycerol fraction without very costly and time‐consuming purification. Copyright © 2009 Society of Chemical Industry     

Production of biodiesel with glycerol carbonate by non‐catalytic supercritical dimethyl carbonate

New biodiesel production processes comprising one‐step and two‐step supercritical dimethyl carbonate methods have been pioneered. The use of dimethyl carbonate allows the reaction conditions to be mild and thus avoid unwanted deterioration of substrates during reaction. In this process, without any catalyst applied, supercritical dimethyl carbonate converts triglycerides (rapeseed oil) into fatty acid methyl esters (FAME) along with glycerol carbonate as a value‐added by‐product, instead of glycerol. Free fatty acids could be also converted into FAME so that the total yield of biodiesel for both methods resulted in over 96 wt%. In addition, the produced FAME satisfy the fuel requirements for the international standards of biodiesel specification.     

Efficient synthesis of glycerol carbonate from glycerol and urea with lanthanum oxide as a solid base catalyst

Lanthanum oxide catalyst prepared by precipitation method and calcined at 600 °C exhibited better catalytic activity in the catalytic synthesis of glycerol carbonate from glycerol and urea with TOF up to 1506 mmol/g·h. It was proposed that the lanthanum oxide catalyst with more strong basic sites (T_d > 400 °C) exhibited higher catalytic activity. Accordingly, the catalyst containing appropriate amount of La₂O₂CO₃ phase exhibited higher catalytic activity. Moreover, the recycling experiments demonstrated that the catalytic activity can be essentially preserved during the recycling tests investigated.     

Treatment of industrial glycerol from biodiesel production by adsorption operation: kinetics and thermodynamics analyses

Abstract

Equilibrium, thermodynamic, and kinetic analyses of the pigments adsorption of the industrial glycerol onto activated charcoal were performed. As the pigments concentration was not known, then, a relative adsorption capacity was defined using absorbance values measured in a spectrophotometer at a wavelength of 265?nm. Kinetic study showed that about 60?s were needed to reach equilibrium conditions. Relative adsorption capacity reached 8?g^?1 for 1% of adsorbent amount (w/w). Adsorption enthalpy was of –17.63?kJ mol^?1, while for isosteric heat values were obtained between –7.39 and –18.46?kJ mol^?1. The mathematical methodology used for the parameters determinations proved to be robust and able to express the relationships of kinetics, equilibrium and thermodynamics. Enthalpy values obtained by Van't Hoff method was confirmed by isosteric heat calculation, evidencing that this methodology can be used for systems whose compositions are unknown, but detectable by indirect form.     

生物柴油副产物粗甘油催化氧化脱水制备丙烯酸

用生物柴油副产物粗甘油催化氧化脱水制丙烯酸,该过程耦合了甘油脱水制丙烯醛和丙烯醛选择性氧化制备丙烯酸两步反应。结果表明,在甘油脱水反应中,使用Cs3PW12O40, P-ZSM-5和Co0.5H2PO4/SiO2等固体酸催化剂,可得到较高的丙烯醛收率(最高86.9%)。利用上述催化剂和MoVW基氧化催化剂,在脱水/氧化双催化剂床层构型反应器中,以甘油为原料合成丙烯酸的收率达50%~80%,直接加入粗甘油可获得相似的丙烯酸收率。     

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.     

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.