预酯化-酯交换法利用餐饮废油脂制备生物柴油

以高酸值餐饮废油脂和乙醇为原料,采用预酯化-酯交换法制备生物柴油。第一步为预酯化反应,控制反应温度为70℃,最佳条件为:催化剂加入量为4%,反应时间为90min,带水剂加入量为10%,乙醇加入量控制在醇酸摩尔比为6∶1,可使油脂酸值降至4mg KOH·g-1以下,满足酯交换反应要求。第二步为酯交换反应,最佳条件是:醇油摩尔比为8∶1,碱性催化剂加入量为0.8%,反应温度为70℃,反应时间为30min。本方法具有反应时间短、转化率高,反应条件温和,清洁环保等优点。     

Biodiesel production from waste frying oil in sub- and supercritical methanol on a zeolite Y solid acid catalyst

Waste frying oil (WFO) is a very important feedstock for obtaining biodiesel at low cost and using WFO in transesterification reactions to produce biodiesel helps eliminate local environmental problems. In this study biodiesel was produced from WFO in sub- and super-critical methanol on a zeolite Y solid acid catalyst. The procedure was optimized using a design of experiments by varying the methanol to WFO molar ratio, the reaction temperature, and the amount of catalyst. Typical biodiesel yields varied from 83 to nearly 100% with methyl esters content ranging from 1.41–1.66 mol·L^-1 and typical dynamic viscosities of 22.1-8.2 cP. Gas chromatography was used to determine the molecular composition of the biodiesel. The reaction products contained over 82 wt-% methyl esters, 4.2 wt-% free acids, 13.5 wt-% monoglycerides, and 0.3 wt-% diglycerides. The transesterification of WFO with methanol around its critical temperature combined with a zeolite Y as an acid catalyst is an efficient approach for the production of biodiesel with acceptable yields.     

制备活性炭负载K2CO3用于催化餐饮废油合成生物柴油

以K₂CO₃为催化剂,工业碱木质素(KL)为活性炭(AC)前体,在管式电阻炉中经一步共混活化(K₂CO₃/KL质量比为0.6、活化温度800℃、N₂流量100cm³/min、活化时间2h)制备K₂CO₃/AC固体碱催化剂,用于餐饮废油与甲醇的酯交换反应合成生物柴油。对制备的固体碱催化剂进行了X-射线衍射(XRD)、BET表面积及扫描电镜(SEM)表征。考察了反应温度、催化剂用量、反应时间、醇油摩尔比等因素对餐饮废油转化为生物柴油产率的影响。结果表明当反应时间2h、反应温度60℃、醇油摩尔比15:1、催化剂为原料油质量的3.0%时,生物柴油最大产率为87.5%。考查了催化剂的循环利用效果,结果表明催化剂能循环利用3次,第3次利用时生物柴油的产率仍达到80.7%。     

On the use of waste frying oil in the synthesis of sophorolipids

Sophorolipids are surface‐active agents which are synthesised by the yeast Candida bombicola. Here we present the possibility of reducing the economical and ecological cost of producing sophorolipids by using waste frying oil as a substrate for C. bombicola. A comparison is made between two grades of biodiesel, waste frying oil and the methyl ester of coco/palm oil as lipophilic substrates on a shakeflask level. Cultivations in a bioreactor using waste frying oil as a substrate were carried out. A new strategy for product recovery without the use of organic solvent is also proposed. The work presented here investigates whether it is possible to produce sophorolipids on waste frying oil and recover the product without using organic solvents.     

CaO/La2O3固体碱催化剂制备及其催化大豆油酯交换反应性能

采用共沉淀法制备了氧化钙/三氧化二镧（CaO/La2O3）固体碱催化剂,并将其应用于大豆油与甲醇进行的酯交换反应。XRD表征结果表明,活性组分在三氧化二镧上高度分散,且钙与镧之间有较强的协同作用。催化剂适宜的制备条件：钙与镧物质的量比为2∶1,焙烧温度为750 ℃,焙烧时间为3 h。在醇与油物质的量比为13∶1、催化剂质量占大豆油质量的4%、反应时间为4 h条件下,制备的氧化钙/三氧化二镧固体碱催化剂催化大豆油和甲醇进行的酯交换反应制备生物柴油的产率达到90%以上。     

用于生物柴油制备的KF/Al2O3固体碱催化剂的研究

采用浸渍法制备了KF/Al₂O₃固体碱催化剂，并将其应用于大豆油与甲醇酯交换制备生物柴油的反应。通过酯交换反应的转化率对催化剂制备工艺进行了优化，得出最佳制备条件：KF理论负载质量分数为Al₂O₃的45%，浸渍时间6 h，焙烧温度500 ℃，优化条件下制备的催化剂在大豆油与甲醇物质的量比为12∶1、催化剂用量为油质量的2%、反应时间3 h和反应温度(60～65) ℃条件下,酯交换转化率可达97.15%。     

Dual-template synthesis of hierarchical porous carbon and its application in electrical double-layer capacitors

Hierarchical porous carbons (HPCs) with tailored pore structure were fabricated via direct carbonization of a precursor consisting of agar and acetates in an inert atmosphere. The agar served as the carbon source and curing agent, while potassium acetate and calcium acetate were used to create micropores and mesopores, respectively. The morphology and structural features of the HPCs were characterized, and the electrochemical properties were estimated in a three-electrode system with 6 M KOH as the electrolyte. The resulting HPCs possess a developed pore structure and concentrated pore size distribution (focused at 0.4 and 4 nm), and exhibit typical electrical double-layer capacitive behaviour. Specially, the HCP-2 owns a large specific surface area of 1441.65 m²/g and excellent electrochemical properties, including a favourable specific capacitance (235 F/g at 1 A/g), good rate capability (capacitance retention rate of 88.1% at 20 A/g), and impressive long-term cycling stability (90.6% retention of initial capacitance after 3000 cycles).     

微波辅助固体酸催化废弃油脂合成生物柴油工艺的优化

以废弃油脂为原料,采用微波辐射辅助固体酸催化合成生物柴油。考察反应温度、微波功率、微波加热时间、醇油摩尔比及催化剂的用量对生物柴油产率的影响,并采用响应面法建立二次回归模型对合成工艺进行了优化。分析结果显示,在反应温度为82℃、反应时间为93 min、醇油摩尔比7∶1、催化剂的用量为3.2%时,生物柴油的产率可达到94.58%,与在相同工艺条件下未经微波处理的产率提高了32.47%。     

Na2CO3/CF固体碱对菜籽油酯交换反应的催化性能

以Na₂CO₃为活性组分、泡沫炭（CF）为载体,本文借助等体积浸渍法制备了Na₂CO₃/CF非均相固体碱催化剂,通过SEM、SEM-EDS、FTIR、XRD、BET对其结构性能进行分析表征,结果显示：Na₂CO₃/CF的比表面积为182m²/g,负载的Na₂CO₃以细小颗粒的形式均匀分布于CF泡壁表面,平均粒径<350nm。以菜籽油-甲醇体系为对象,分析了Na₂CO₃/CF的催化活性及重复利用性,并对酯交换反应的工艺条件进行优化,结果显示,在Na₂CO₃/CF用量为油重10%、反应时间180min、醇油物质的量比为27∶1、反应温度65℃的条件下,反应转化率高达97.80%,该催化剂重复利用5次,转化率仍可达94.48%。研究结果对开发以强碱弱酸盐为活性中心的碳基固体碱高效催化剂提供了新思路。     

磺化石墨烯固体酸催化剂的制备及活性评价

石墨烯是由碳原子以sp₂杂化连接的单原子层构成的新型二维碳原子晶体,由于含有众多具有反应活性的碳碳双键,石墨烯纳米片表面很容易进行化学修饰键合有机官能团而改变其性质。采用改良Hummers法制备氧化石墨烯,通过磺化反应制备磺化石墨烯固体酸催化剂,通过FT-IR、元素分析和XPS等对其结构进行表征。将制备的氧化石墨烯和磺化石墨烯应用于催化纤维二糖的水解反应,以纤维二糖糖苷键的水解反应为模型考察其酸催化性能。结果表明,氧化石墨烯和磺化石墨烯中含有-COOH、-OH和-SO₃H等官能团,磺酸根密度分别为1.0 mmol·g^-1和2.2 mmol·g^-1,氧化石墨烯和磺化石墨烯具有与H₂SO₄相比拟的酸催化活性,尽管酸性强度和密度较低,但催化活性与H₂SO₄相当。     

磺化碳固体酸催化剂的制备及其催化性能的研究

以微晶纤维素(MCC)为原料制备了碳基磺酸化固体酸催化剂,用该磺化碳固体酸MCC进行糖化水解,考察其催化水解微晶纤维素的最优条件及碳化温度对催化剂催化活性的影响,并对其重复使用性及再生进行了研究。结果表明,反应温度180℃、反应时间6 h、催化剂用量0.15 g为最佳反应条件,最高糖产率为68.71%;400℃为最佳碳化温度。催化剂重复使用后,由于表面磺酸基团的脱落其活性有所下降,可以通过再磺化得到恢复。     

中孔碳负载铂催化剂制备及其催化3,4-二氯硝基苯加氢反应

以糠醇为碳源,在酸性中孔模板剂MSU-S上缩合,合成具有中孔结构碳材料(MC),通过浸渍法合成Pt/MC催化剂。采用XRD、BET、SEM和TEM等手段对MC和Pt/MC进行表征,MC富含中孔,有效分散Pt纳米粒子并在反应过程中稳定Pt。研究Pt/MC对3,4-二氯硝基苯催化加氢反应的催化性能,在3,4-二氯硝基苯 1 mmol、催化剂用量100 mg、乙醇5 mL、反应温度30 ℃、常压氢气和反应时间6 h条件下,3,4-二氯硝基苯转化率达100%,3,4-二氯苯胺选择性达99.7%,Pt/MC重复使用5次,催化性能保持不变。     

锐钛型介孔偏钛酸催化剂的制备及其催化酯化性能

以工业偏钛浆为原料,通过水洗、碱洗、酸洗处理制备了锐钛型介孔偏钛酸催化剂,将催化剂用于α-蒎烯酯化反应中考察其催化性能,采用FT-IR、XRD、SEM、BET手段对催化剂的晶相结构、形貌、表面积、孔径等结构进行了表征。结果表明,最佳制备条件为：温度30 ℃,碱洗pH=8.5,酸洗pH=4.0;处理后的偏钛酸催化剂基本没有SO42?,且晶型没有发生明显变化,均为锐钛矿相,最佳条件下制备的偏钛酸催化剂孔径分布均匀,晶粒团聚较少,比表面积为334.82 m2/g,平均孔径为3.96 nm,催化α-蒎烯酯化生成草酸龙脑酯含量可达48.59 %,皂化后水蒸气蒸馏收集龙脑,m1（正龙脑）∶m2（异龙脑）=59.27∶37.07。     

Microwave assisted in continuous biodiesel production from waste frying palm oil and its performance in a 100 kW diesel generator

A household microwave (800W) was modified as a biodiesel reactor for continuous transethylation of waste frying palm oil. The high free fatty acid oil was simultaneously neutralized and transesterified with sodium hydroxide. With the ethanol to oil molar ratio of 12:1, 3.0% NaOH (in ethanol) and 30s residence time, the continuous conversion of waste frying palm oil to ethyl ester was over 97%. The waste palm oil biodiesel was then tested in a 100 kW diesel generator as a neat fuel (B100) and 50% blend with diesel No. 2 fuel (B50). The engine performance and emission are recorded. At the engine loads varied from 0 kW to 75 kW (at 25 kW intervals) of the maximum electrical rating, the performance of the neat and B50 are slightly lower than diesel No. 2 fuel. Emissions of NO_x, CO and HC from B100 and B50 are lower than those of diesel No. 2 fuel, except that at the 75 kW engine load, where the B100 emits higher levels of NO_x than the diesel No. 2 fuel.     

负载型膨润土固体碱催化剂的制备及在生物柴油合成中的应用

提出了一种负载型膨润土固体碱催化剂的制备方法,并将此催化剂用于生物柴油合成的酯交换反应。该催化剂通过碱性钙基膨润土在半干条件下负载氢氧化钠制得。催化剂制备的单因素实验结果表明：当氢氧化钠与碱性钙基膨润土的质量配比为0.6、负载时间为18 h、温度为60 ℃及碱性钙基膨润土中OH&#8722;含量为1.5 mmol/g时,催化剂中氢氧化钠负载量达到4.10 mmol/g。将该催化剂用于生物柴油酯交换反应,反应转化率可达97.4%,反应完成后生物柴油无需洗涤,避免了三废的大量排放,减少了对环境的污染。     

有序介孔氮化碳的制备及其催化Knoevenagel缩合反应

以四氯化碳和乙二胺为前驱体,介孔氧化硅SBA-15为硬模板剂,采用纳米浇铸法合成系列不同碳氮比的介孔类石墨相氮化碳材料CN-SBA15。通过N2吸附-脱附、XRD、TEM、FT-IR和XPS等对CN-SBA15进行表征,并考察其在苯甲醛和丙二腈Knoevenagel缩合反应中的催化性能。结果表明,CN-SBA15的比表面和孔体积与前驱体的比例有直接关系,很好地反向复制了原SBA-15的有序结构。CN-SBA15含有大量的N杂环结构,在Knoevenagel缩合反应中显示出较高的催化活性、重复使用性和底物普适性。     

碳酸根型镁铝复合氢氧化物的合成和表征及其催化性能

以恒定pH值共沉淀法合成碳酸根型镁铝水滑石,用XRD、IR、TG-DTA和SEM等手段进行表征。XRD衍射表明，Mg与Al物质的量比为1∶1、3∶1、4∶1和6∶1的合成物均有水滑石结构。热重-差热分析(TG-DTA)显示，水滑石有两个吸热峰值:第一吸收峰值在200～250 ℃, 第二吸热峰值在400～450 ℃,最大损失重量在2780%～33.41%。SEM分析可知，样品呈层状、棒状、针状和蜂窝状等结构。并对镁铝复合氢氧化物作为催化剂用于生物柴油制备作了研究。结果表明，Mg与Al物质的量比为3∶1的水滑石可使甲酯收率达到90%左右，且可重复使用。产品达到德国生物柴油质量标准。     

Effect of oil replenishment during deep-fat frying of frozen foods in sunflower oil and high-oleic acid sunflower oil

Frying stability of sunflower oil (SO) with 23% oleic acid and 61% linoleic acid, and of high-oleic acid sunflower oil (HOSO) with 74% oleic acid and 13% linoleic acid was studied during 20 discontinuous deep-fat fryings of various frozen foods, with or without frequent replenishment of the used oil with fresh oil. Alterations of both oils were measured by column, gas-liquid and high-performance size-exclusion chromatography. Total polar content and compounds, related to thermoxidative changes, and diacylglycerides, related to hydrolytic changes, increased in all oils during frying but reached higher levels in SO than in HOSO. Nevertheless, the increased levels of diacylglycerides observed may result from the frozen potatoes prefried in palm oil. Oleic acid in HOSO and linoleic acid in SO significantly decreased, but the fatty acid modifications that occurred during the repeated fryings were not only related to thermoxidative alteration but also to interactions between the bath oil and the fat in the fried products. Data from this study also indicated that HOSO performed more satisfactorily than SO in repeated fryings of frozen foods. Moreover, frequent addition of fresh oil throughout the deep-frying process minimized thermoxidative and hydrolytic changes in the frying oils and extended the frying life of the oils.