新型生物柴油技术研究进展

综述了生物柴油的特性及生产方法,介绍了酯交换法制备生物柴油的反应机理及生产工艺,对各种工艺的优缺点进行了剖析,指出了生物柴油技术发展现在面临的问题及研究方向。     

壳聚糖硫酸盐催化合成苯甲酸甲酯

以壳聚糖硫酸为催化剂，由苯甲酸和甲醇合成苯甲酸甲酯，考察了催化剂用量，反应时间及醇酸摩尔比等因素对反应的影响，实验结果表明，在催化剂用量为1．0g，反应时间为4h，醇酸摩尔比为5：1的条件下，产品收率为90．56％，且催化剂可重复使用。     

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.     

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.

     

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.     

KOH负载的不同催化剂催化合成生物柴油

采用湿法浸渍法研究了五种KOH负载的催化剂催化合成生物柴油反应,并采用XRD﹑SEM﹑CO2-TPD等方法对其进行结构和性能表征。结果表明,15%(质量分数,下同)KOH负载的CaO催化酯化活性最高,在醇油摩尔比16∶1,反应温度65℃,催化剂加入量为4%条件下,反应1h,脂肪酸甲酯收率达到97.1%。KOH负载的CaO催化剂中出现了K2O的晶相,15%CaO/KOH催化剂有更多的活性位点,有利于生物柴油酯交换反应。     

Pilot plant studies of biodiesel production using Brassica carinata as raw material

In recent years, the development of alternative fuels from renewable resources, like biomass, has received considerable attention. Biodiesel is defined as fatty acid methyl or ethyl esters from vegetable oils, when it is used as fuel in diesel engines and heating systems.

In this context, the cultivation of Brassica carinata as oilseed crop for biodiesel production in the south of Europe (Spain and Italy) and north of Africa has gained special interest, since it allows the use of set-aside lands, giving higher yields per hectare than the traditional Spanish crops.

Methyl or ethyl esters are the product of transesterification of vegetable oils with alcohol (methanol/ethanol) using an alkaline catalyst. In addition, the process yields glycerol, which has large applications in the pharmaceutical, food and plastics industries.

In the present work, the process of biodiesel production for pilot plant using B. Carinata oil as raw materials with methanol and using potassium hydroxide as catalyst has been studied.

The biodiesel quality meets European specifications defined by pr EN 14214:2002 (E). The obtained results have been used for industrial scale up of the process.     

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.     

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。     

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。     

强碱催化棉籽油酯交换制备生物柴油的动力学

脂肪酸甲酯（生物柴油）,通常是由植物油与甲醇在催化剂作用下通过酯交换反应而得到的．生物柴油作为潜在的柴油能源替代品,以其可生物降解、可再生、尾气排放中的有毒气体（SOx等）低等诸多优点,近年来得到越来越多的重视．目前,世界各国都在积极发展生物柴油的生产和开展相应研究．     

棕榈油酯交换制备生物柴油的反应动力学

在甲醇与棕榈油的摩尔比为6∶1和催化剂KOH用量为棕榈油质量1.0%的条件下,研究不同温度下棕榈油制备生物柴油的酯交换反应动力学,采用Origin软件拟合曲线方程,建立棕榈油酯交换反应的宏观动力学模型。研究结果表明:棕榈油制备生物柴油的酯交换反应遵循1.40级动力学方程,反应速率随温度的升高而加快,二者符合Arrhenius方程,该反应的活化能为27.23 kJ/mol,频率因子为1.4×103。文中研究建立的反应动力学模型将对扩大试验研究提供理论依据和基础数据支持。     

Biodiesel production by the transesterification of cottonseed oil by solid acid catalysts

Methyl esters (biodiesel) were produced by the transesterification of cottonseed oil with methanol in the presence of solid acids as heterogeneous catalysts. The solid acids were prepared by mounting H₂SO₄ on TiO₂ · nH₂O and Zr(OH)₄, respectively, followed by calcining at 823K. TiO₂-SO₄ ²⁻ and ZrO₂-SO₄ ²⁻ showed high activity for the transesterification. The yield of methyl esters was over 90% under the conditions of 230°C, methanol/oil mole ratio of 12:1, reaction time 8 h and catalyst amount (catalyst/oil) of 2% (w). The solid acid catalysts showed more better adaptability than solid base catalysts when the oil has high acidity. IR spectral analysis of absorbed pyridine on the samples showed that there were Lewis and Br?nsted acid sites on the catalysts. Translated from The Chinese Journal of Process Engineering, 2006, 6(4): 571–575 [译自: 过程工程学报]     

固体超强酸Zr(SO4)2/TiO2催化合成生物柴油

以固体超强酸Zr(SO4)2/TiO2为催化剂,通过酯交换反应催化工业用棕榈油与甲醇合成了生物柴油,讨论了醇油摩尔比、催化剂用量、反应时间对棕榈油转化率的影响,确定了较佳工艺条件:醇油摩尔比5∶1,催化剂用量为棕榈油质量的8.8%,在78℃~81℃微沸下反应5 h。此时棕榈油的转化率可达89.3%,在此优化条件下进行第二步反应可使转化率达到98.6%。采用GC-MS对产物进行了分析,鉴定为脂肪酸甲酯。     

Mg-Al类水滑石催化大豆油酯交换制备生物柴油

采用共沉淀法制备了不同n(Mg)/n(Al)比的Mg-Al类水滑石,在不同温度下焙烧得到复合氧化物,作为大豆油与甲醇反应制备生物柴油的催化剂。结果表明,未焙烧Mg-Al类水滑石的催化活性较差,而n(Mg)/n(Al)=3的类水滑石在450℃焙烧时具有极高的催化活性。在反应温度65℃,醇/油15,催化剂用量为大豆油质量的2%,反应3 h,生物柴油产率可达97.4%。催化剂回收再用性能良好,重复使用3次,生物柴油收率仍在90%左右。     

生物柴油制备方法的应用研究进展

生物柴油以其优良的环境友好性和可再生性引起广泛关注,但较高的生产成本是其商业化生产和应用的障碍之一。综述了生物柴油的化学转酯化法和以游离脂肪酶、固定化脂肪酶、全细胞为催化剂的生物转酯化法的工业研究进展,同时还指出了采用生物转酯化法制备生物柴油时面临的一些问题。     

Kinetics of hydroxide‐catalyzed methanolysis of crude sunflower oil for the production of fuel‐grade methyl esters

Methyl esters from crude sunflower oil were produced via methanolysis reaction using sodium hydroxide catalyst. Methanolysis was carried out at different agitation speeds (200–600 rpm), temperatures (25–60 °C), catalyst loadings (0.25–1.00% by weight of oil), and methanol:oil mole ratios (6:1–20:1). Mass‐transfer limitation was effectively minimized at agitation speeds of 400–600 rpm with no apparent lag period. Lowering the temperature resulted in a fall in the rate of reaction prolonging the reaction time necessary to achieve maximum production of methyl ester. Using 0.50% hydroxide catalyst was found to be adequate, resulting in 97–98% conversion without compromising recovery due to soap formation. Increasing the methanol:oil mole ratio beyond the usual amount of 6:1 tended to speed up the initial rate of methanolysis and was found to lower the bonded glycerol content, especially the amount of diglyceride in the sample. Kinetic rate constants were derived from experimental results using second‐order rate expressions, and values of activation energy for glyceride methanolysis have been established. Copyright © 2007 Society of Chemical Industry