微藻直接离子液体脂肪酶制备生物柴油

采用小球藻、甲醇为原料,脂肪酶为催化剂,离子液体为提取剂和反应介质,直接提取酯交换制备生物柴油。考察不同工艺条件对产率的影响,结果表明:甲醇用量和藻粉质量比为8∶1,离子液体[BMIM][DCA]和藻粉质量比为1∶1,脂肪酶用量为藻粉质量的12%,反应温度为50℃,酯交换反应时间为16 h条件下,生物柴油的转化率可达69.6%。采用微藻直接离子液体脂肪酶制备生物柴油无需从微藻粉中提取油脂,因此降低过程成本、缩短工艺,能实现含油微藻到生物柴油的一步转化。     

Brønsted酸性离子液体合成及催化制备生物柴油

合成4种成功能化酸性离子液体,采用红外光谱、热重分析等分析法进行表征验证,并用其催化菜籽油酯交换制备生物柴油,考察醇/油物质的量之比、反应温度、反应时间、离子液体用量和水含量对转化率的影响。结果表明,4种离子液体都有较强酸性,与浓硫酸酸性相当;带—SO₃H基团的离子液体表现出更好的催化活性,且随着烷基链的增加,催化活性提高;在（n甲醇）∶n（菜籽油）=12∶1,反应温度130 ℃,反应时间3 h,离子液体（[BSO₃HMIM][HSO₄]）用量为菜籽油质量2%（质量分数）条件下,生物柴油转化率可达99%以上。在反应体系中,水会破坏离子液体的结构并导致其失活,而升高反应温度,可缓解水对离子液体的结构破坏,在130 ℃条件下,即使水分含量为5%时,生物柴油转化率仍可保持在约85%。     

磺酸型离子液体合成及催化制备生物柴油工艺研究

研究合成功能化酸性离子液体1-丙基磺酸-3-甲基咪唑硫酸氢盐([PrSO_3HMIm]HSO_4),采用核磁共振、红外光谱、热重分析等分析法进行表征验证,并用其催化菜籽油酯交换反应制备生物柴油,考察醇油物质的量之比、反应温度、反应时间和离子液体用量对酯交换反应的影响及离子液体的稳定性。结果表明:在n甲醇∶n菜籽油=10∶1,反应温度120℃,反应时间8 h,离子液体用量为菜籽油质量7%的条件下,生物柴油收率可达95.56%,且稳定性良好,循环使用5次催化性能未明显降低。     

微藻油脂制备生物柴油的研究

利用正己烷从异养生长的小球藻(脂类化合物含量高达细胞干重的55%,是自养藻细胞(14%)的4倍)细胞中提取获得了大量油脂。这些异养微藻油脂在30℃、醇油物质的量比为56∶1以及浓硫酸催化条件下经酯交换反应4h可形成高质量的生物柴油。微藻生物柴油的密度为0.864kg.L-1、粘度5.2×10-4(40℃)、热值高达41MJ.kg-1。这些特征与传统柴油相当,且微藻生物柴油具有更低的冷滤点(-11℃)及良好的发动机低温启动性能,因此其应用价值更高。     

氨基磺酸非均相催化菜籽油及废油脂制备生物柴油

采用正交试验和单因素试验的方法研究了氨基磺酸催化菜籽油及废油脂与甲醇的酯交换过程,考察了醇油物质的量比、催化剂用量、反应温度和反应时间对反应收率的影响。结果表明:菜籽油酯交换的最佳反应条件为醇油物质的量比6∶1,氨基磺酸用量为原料油质量的1.0%,反应温度60℃,反应时间20 min,此工艺条件下,脂肪酸甲酯的收率达到95.6%;废油脂酯交换的最佳反应条件为醇油物质的量比8∶1,氨基磺酸用量为原料油质量的1.0%、反应温度65℃,反应时间30 min,此工艺条件下,脂肪酸甲酯的收率达到87.5%。利用红外光谱表征了菜籽油和生物柴油的结构,气相色谱分析了生物柴油的组成。     

离子液体对玉米秸秆组分的溶解选择性

为实现生物质原料的组分分离,研究了1-丁基-3-甲基咪唑甲酸盐([BMIM][HCOO])、1-丁基-3-甲基咪唑乙酸盐([BMIM][CH3COO])、1-丁基-3-甲基咪唑丙酸盐([BMIM][CH3CH2COO])、1-丁基-3-甲基咪唑二氰胺盐([BMIM][N(CN)2])4种离子液体在固液比为1∶20、温度为20~140℃下,对玉米秸秆各组分的溶解能力。结果表明:玉米秸秆在离子液体的溶解率随温度的增加而增加;4种离子液体中,[BMIM][CH3CH2COO]对玉米秸秆中纤维素和半纤维素的溶解能力最强,在140℃下溶解率分别达74.04%和79.22%,[BMIM][N(CN)2]对玉米秸秆中的木质素的溶解能力最强,在140℃下溶解率达75.15%;这4种离子液体对纤维素和半纤维素的溶解选择性均较低,[BMIM][N(CN)2]在140℃下对玉米秸秆中的木质素的选择溶解性系数可达2.03,显示出良好的分离性能。     

花椒籽油生物柴油制备工艺研究

以花椒籽油为原料,对KOH催化其与甲醇发生酯交换反应制备生物柴油进行研究。采用物理萃取法降低花椒籽油中游离脂肪酸的含量,三次萃取后酸值达到2 mgKOH/g以下。研究了花椒籽油和甲醇在氢氧化钾催化下的酯交换反应。进行了不同醇油摩尔比、催化剂用量、反应时间、反应温度等反应条件下对产率的影响,得到最佳反应条件为醇油物质的量之比为12∶1,催化剂添加量为油脂质量的1.2%,反应温度为60～65℃,反应时间为45 min。     

花椒籽油生物柴油制备工艺研究

以花椒籽油为原料,对KOH催化其与甲醇发生酯交换反应制备生物柴油进行研究.采用物理萃取法降低花椒籽油中游离脂肪酸的含量,三次萃取后酸值达到2 mgKOH/g以下.研究了花椒籽油和甲醇在氢氧化钾催化下的酯交换反应.进行了不同醇油摩尔比、催化剂用量、反应时间、反应温度等反应条件下对产率的影响,得到最佳反应条件为醇油物质的量之比为12∶1,催化剂添加量为油脂质量的1.2％,反应温度为60 ～65℃,反应时间为45 min.     

固体碱催化猪油制备生物柴油

运用实验研究和理论分析相结合的方法,阐述猪油和甲醇在CaO催化剂作用下进行酯交换反应制取生物柴油的基本原理和操作方法,分光光度法测定甘油含量,计算生物柴油转化率,得出以CaO催化猪油制取生物柴油的适宜反应条件。结果表明:CaO做催化剂时,催化剂用量为2.0%,醇油物质的量比为6∶1,反应时间为150min,温度为60℃进行磁力搅拌,反应产率最高可达93.68%。     

氧化石墨烯固体酸催化湿藻油制生物柴油

主要研究氧化石墨烯(GO)作固体酸催化转化湿藻油脂制生物柴油。气相色谱质谱联用(GC-MS)、傅里叶红外光谱(FTIR)、扫描电镜(SEM)的结果表明:GO表面带有大量羟基(—OH)及羧基(—COOH),羟基能将亲水的湿藻细胞均匀吸附在GO表面,而羧基及GO带有的磺酸基(—SO_3H)作酸性中心与氯仿萃取出的湿藻油脂接触并高效催化酯交换反应。在1 g湿藻中加入质量分数为5%的GO作为固体酸催化剂,再加入4 mL甲醇和3 mL氯仿,微波加热控温在90℃反应40 min后,生物柴油转化率最高达到95.1%。     

Eco-friendly biodiesel production from olive oil waste using solar energy

This study was carried out to produce biodiesel from olive oil waste by transesterification reaction. Several important reaction variables (the weight ratio of oil to methanol, the temperature, and reaction time) were evaluated to obtain a high quality of biodiesel fuel that meets authentic standards. Solar energy was applied for the transesterification reaction and electricity generated by photovoltaic panels was used to power a motor for mixing the reaction solution.     

A bronsted basic ionic liquid as an efficient and environmentally benign catalyst for biodiesel synthesis from soybean oil and methanol

Morpholine basic ionic liquid was synthesized with N-methyl morpholine, N-butyl bromide, and KOH by two-step method and was used to catalyze the transesterification of soybean oil with methanol to biodiesel. The structure of the catalyst were examined by ¹H nuclear magnetic resonance. The effects of the molar ratio of methanol to oil, reaction temperature, and amount of catalyst on the biodiesel yield were investigated. Optimized biodiesel yield of 94.5% was achieved with catalyst amount of 3.0 wt%, and methanol to soybean oil molar ratio of 14:1 at reaction temperature of 60 °C for 6 h. The catalyst has maintained sustained activity after being employed to six cycles. The prepared biodiesel component was analyzed by gas chromatography-mass spectrometry (GC-MS) and the results showed that the biodiesel comprised of hexadecanoic acid methyl ester, 10, 13-octadecadienoic acid methyl ester, 9-octadecenoic acid methyl ester, and octadecanoic acid methyl ester, illustrating that fatty acids of soybean oil were converted completely.     

Two different kinds of processes for biodiesel production from Chinese cottonseed

Alkali-catalyzed and supercritical methanol transesterification were used to produce biodiesel from Chinese cottonseed. Fourier transform infrared and gas chromatography/mass spectrometry were used to identify the compositions of cottonseed oil biodiesel samples. Six major compositions of the biodiesel samples were identified by the retention time and the fragmentation pattern data of GC/MS analysis. The yields of biodiesel samples obtained from alkali-catalyzed reaction and supercritical methanol transesterification were 98.4 and 99%, respectively. In comparison to the alkaline transesterification, the supercritical methanol transesterification combining with two-phase extraction was more suitable for biodiesel production due to shorter reaction time, less purification steps, and lower cost.     

Production of biodiesel from food processing waste using response surface methodology

The optimum conditions for biodiesel production by the transesterification of waste oil form the pork grilling process in the food factory in Udon Thani, Thailand, using NaOH and KOH as catalysts, has been investigated. A Box–Behnken Design (BBD) followed by a Response Surface Methodology (RSM) with 30 runs was used to assess the significance of three factors: the methanol to oil molar ratio, the amount of NaOH and KOH used, and the reaction time required to achieve the optimum percent fatty acid methyl ester (%FAME). The measured %FAME following transesterification using NaOH as a catalyst was an optimum 95.6% with a methanol to oil molar ratio of 12.2:1, a NaOH percentage mass fraction of 0.49% and a reaction time of 63 min. Using KOH as a catalyst, the %FAME was an optimum 93.0% with a methanol to oil molar ratio of 12:1, a KOH percentage mass fraction of 0.61% and a reaction time of 72 min. The coefficient of determination (R²) for regression equations were 98.55% and 93.99%, respectively. The probability value (P<0.05) demonstrated a very good significance for the regression model. The physicochemical properties of the biodiesel obtained from the waste oil met the ASTM 6751 biodiesel standard, illustrating that waste oil from the pork grilling process can be used as a raw material for biodiesel production by transesterification.     

大豆生物柴油制备及其在柴油机上的试验研究

介绍了通过酯交换反应来制取生物柴油的方法和制取流程,采用正交试验方法确定了最佳的反应条件。在增压柴油机上,进行了自制生物柴油和0#柴油的动力性、经济性以及排放的对比试验。结果表明,与0#柴油相比,燃用生物柴油时最大扭矩,最大功率以及外特性烟度均有所降低,有效燃油消耗率有所增加,NO_x、HC以及CO均有所降低。     

Macroalgae: Raw material for biodiesel production

The objective of this paper is to study marine macroalgae as an alternative raw material for the biodiesel production. The obtained results show that biodiesel production from oil extracted from marine algae is feasible by transesterification. Oil extraction can be carried out simultaneously with the transesterification. To investigate the optimum reaction conditions, the reaction was carried out at various methanol to oil molar ratios, catalyst concentrations and reaction temperatures. The process yields 1.6–11.5% depending on the reaction conditions. Moreover, the properties of macroalgae transesterification residue after transesterification were analyzed, concluding that it is a suitable material for fuel pellets manufacturing.     

固定化脂肪酶在离子液体中催化合成生物柴油

通过硅胶载体涂布法对细菌Burkholderia cepacia GX-35所产的脂肪酶进行固定化。比较了自制固定化脂肪酶在4种离子液体中催化合成生物柴油的效果,其中文章研究新设计并合成的一种离子液体溴代1-乙基-2-甲基咪唑[EMIM]Br对催化反应起促进作用。通过对转酯率的测定,研究了固定化脂肪酶在[EMIM]Br中的最适反应条件:最适反应温度为35℃,[EMIM]Br加入量为花生油质量分数的60%,最佳醇类为乙醇,加水量为花生油质量分数的5%,乙醇与花生油之比为9∶1,固定化脂肪酶加入量为花生油的20%,反应时间为6 h。固定化脂肪酶在[EMIM]Br中稳定性好,使用6次之后转酯率下降不明显。试验结果表明,与不加[EMIM]Br相比,加[EMIM]Br能有效提高生物柴油的转化率。     

地沟油制备生物柴油过程中硫化物迁移及脱除研究

采用地沟油等餐饮废弃油脂转化制备生物柴油中会含有一定量的硫化物,针对上述问题,考察传统的酸碱两步法制备生物柴油过程中硫化物的迁移,并以离子液体（[Hnmp]H₂PO₄）为萃取剂和催化剂,H₂O₂为氧化剂,对粗生物柴油进行萃取氧化脱硫,并利用正交实验法对萃取氧化脱硫反应工艺进行优化。结果表明：反应过程使用的试剂和操作条件几乎不会增大生物柴油制备过程中的硫含量以及改变硫化物在反应体系中的存在形态,硫化物含量及存在形式与原料油自身所含硫化物形态有关。S元素在地沟油原料及生物柴油粗成品中的存在形式主要以噻吩、硫醇、硫醚、硫胺素、硫代葡萄糖苷等物质为主,其中噻吩类硫化物约占地沟油原料或生物柴油中总含硫质量分数的93%以上。在粗生物柴油与离子液体体积比为10∶3,粗生物柴油与H₂O₂体积比为10∶1.2,反应温度75 ℃,反应时间70 min条件下,生物柴油脱硫率达94%以上,脱硫后的生物柴油满足最新国Ⅵ柴油排放标准（GB 17930—2016）硫含量≤10 mg/kg要求。