废油脂催化转化制取生物柴油的研究

随着世界经济的发展,石化燃料已经不能满足世界经济发展的需要.以天然油脂为原料生产的生物柴油,作为一种可再生的清洁能源,目前已经受到世界各国的普遍关注.但是目前生产生物柴油使用最广泛的原料是纯菜籽油,生产成本较高,不具有与石化柴油竞争的能力.因此,本实验提出了利用餐     

生物柴油简介

介绍了生物柴油作为燃料的性质、制备生物柴油的原料和生产方法。     

纯四方相硫化氧化锆催化剂的制备及其生物柴油合成应用研究

将过硫酸铵浸渍于直接合成的纳米氧化锆晶体表面,经300-500℃高温焙烧处理获得硫化氧化锆催化剂。采用X射线衍射（XRD）、氮气吸附-脱附、氨气程序升温脱附（NH₃-TPD）、傅里叶红外光谱（FT-IR）、扫描电镜（SEM）和能谱仪（EDS）等分析手段对催化剂的结构性能进行了表征。结果表明,所有的催化剂均展现出纯四方相结构和高的结晶度。其中,经500℃热处理获得的催化剂拥有最高的硫含量和酸性位,将其应用于大豆油与甲醇酯交换反应合成生物柴油,获得了脂肪酸甲酯收率高达84.6%的催化效果,进一步表明该催化剂表面存在优越的超强酸位。     

固定化脂肪酶催化高酸废油脂酯交换生产生物柴油

 探讨了固定化脂肪酶Novozym 435催化高酸废油脂与乙酸甲酯酯交换生产生物柴油. Novozym 435能催化高酸废油脂与乙酸甲酯的酯交换反应,反应24 h后甲酯产率为77.5%,但该值大大低于以精制玉米油为原料时的甲酯产率(86.2%). 系统研究了反应体系中的水、游离脂肪酸和乙酸对反应的影响. 当反应体系中的水含量低于0.05%时,水对酶反应速率和甲酯产率影响甚小,而水含量高于0.05%时,酶反应速率和甲酯产率随着水含量的增加而降低. 游离脂肪酸对反应有较大影响,甲酯产率随着游离脂肪酸含量的增加而急剧下降. 乙酸甲酯与游离脂肪酸反应产生的副产物乙酸是导致甲酯产率显著下降的原因. 在反应体系中添加适量(油重的10%)的有机碱三羟甲基氨基甲烷或三乙胺可有效提高酶促高酸废油脂的酯交换反应速率和甲酯产率,使反应12 h后的甲酯产率分别达到85.9%和80.8%; 碱的加入还提高了酶的操作稳定性,添加有机碱三羟甲基氨基甲烷或三乙胺可使反应10批次后Novozym 435的相对酶活力分别由对照值86%提高到97%和93%.     

新型碱性离子液体催化酯交换合成生物柴油

两步法合成了吗啉阴离子型碱性离子液体1-丁基-3-甲基吗啉盐[Hnmm]Im,经1 H-NMR和FT-IR分析确认了离子液体中间体的结构,并通过阴离子交换得到碱性离子液体,对该离子液体在酯交换制备生物柴油反应中的催化性能进行了研究。结果表明,该碱性离子液体[Hnmm]Im具有较高的酯交换催化活性,在60℃、催化剂用量为3%、醇油物质的量比为6.5∶1.0、反应2 h的条件下,产物脂肪酸甲酯(FAME)含量可达95.80%。而且该离子液体的催化稳定性较好,重复使用5次后仍有较高的催化活性。     

大麻籽油合成生物柴油

大麻籽油;甲醇;甲酯化;生物柴油;酯交换     

新型碱性离子液体催化酯交换合成生物柴油

两步法合成了吗啉阴离子型碱性离子液体1-丁基-3-甲基吗啉盐Im,经 ¹H-NMR和FT-IR分析确认了离子液体中间体的结构,并通过阴离子交换得到碱性离子液体,对该离子液体在酯交换制备生物柴油反应中的催化性能进行了研究。结果表明,该碱性离子液体Im具有较高的酯交换催化活性,在60 ℃、催化剂用量为3%、醇油物质的量比为6.5：1.0、反应2 h的条件下,产物脂肪酸甲酯（FAME）含量可达95.80%。而且该离子液体的催化稳定性较好,重复使用5次后仍有较高的催化活性。     

固定化脂肪酶催化合成生物柴油

固定化脂肪酶催化合成生物柴油;转酯反应;固定化脂肪酶;菜籽油;甲醇;生物柴油     

固体碱KF/Sm2O3催化菜籽油制备生物柴油

以菜籽油为原料,研究了负载型固体碱催化剂KF/Sm2O3在酯交换制备生物柴油过程中的催化活性.用气相色谱法对酯交换产物进行分析,并用CO2-TPD,XRD,Ramaa等技术对催化剂进行了表征.当催化剂焙烧温度为873 K,KF负载量为15%,甲醇跟菜籽油的计量比为12:1,催化剂用量为菜籽油质量的3%,反应温度为338 K,反应时间为1 h时,生物柴油产率达到95.1%.     

钙镁负载型固体碱催化剂制备生物柴油

固体碱催化剂;酯交换反应;脂肪酸甲酯;生物柴油     

Utilization of waste seashells and Camelina sativa oil for biodiesel synthesis

The seafood industry produces over 100 million pounds of seashell waste every year. With landfill space diminishing quickly, ways to recycle waste materials are becoming more sought for. Herein, we utilized waste mussel, clam and oyster shells as heterogeneous catalysts for the transesterification of Camelina sativa oil as a feedstock into biodiesel. Camelina sativa oil provides a reliable solution for biodiesel production because it has high tolerance of cold weather, drought, low-fertility soils and contains approximately 40% oil content. The catalysts from waste seashells were characterized by X-ray powder diffraction and Fourier transform infrared (FTIR) spectroscopy. High biodiesel yields were achieved at a 12:1 (alcohol:oil) molar ratio with 1?wt.% waste seashell catalysts in 2?h at 65°C. Biodiesel was analyzed by ¹H NMR and FTIR spectroscopy and the fuel properties of the biodiesel produced from Camelina sativa oil and waste seashells were compared with American Society for Testing and Materials standards.     

柴油溶剂中脂肪酶催化高酸值废油脂酯化制备生物柴油

采用0＃柴油作为反应溶剂,利用固定化脂肪酶催化高酸值废油脂与甲醇酯化反应制备生物柴油。来源于Candida antarctica的固定化脂肪酶Novozym435在0＃柴油溶剂中具有极高的催化活性。以酸价高达157×10-3的废油脂为原料,废油脂质量比10%的Novozym435,甲醇与废油脂初始摩尔比2∶1,0＃柴油与废油脂质量比5∶1,摇床摇速170r/min,50℃下反应2h甲酯化率可达95.10%。0＃柴油作为反应溶剂有效地溶解了高酸值废油脂和甲醇,降低了反应体系的黏度和消除了甲醇对Novozym435的负面影响,提高了Novozym435的稳定性。同时,0＃柴油溶剂对未脱胶废油脂中残留的对脂肪酶有害的磷脂等胶类物质具有一定的稀释作用。该工艺省却了溶剂蒸馏的繁琐工序,直接得到脂肪酸甲酯和石化柴油的混合燃料。     

锂-铝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锂-铝比[n(Li)/n(Al)]的Li-Al类水滑石,经不同温度下焙烧得到复合氧化物;将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,考察了其对大豆油酯交换反应的催化性能.结果表明,n(Li)/n(Al)=13的类水滑石在400℃下焙烧得到的复合氧化物对大豆油酯交换反应具有极高的催化活性....     

Ca/Al固体碱催化菜籽油制备生物柴油

采用共沉淀法制备了Ca/Al复合氧化物固体碱催化剂,考察了沉淀剂种类、Ca/Al摩尔比、沉淀温度、溶液pH值、老化时间和焙烧温度等制备条件对其催化剂活性的影响。采用正交实验方法得到制备Ca/Al复合固体碱催化剂前躯体的最佳制备条件为,沉淀剂NaOH,Ca/Al摩尔比为3,沉淀温度为60 ℃,沉淀过程中pH值保持在10,在90 ℃老化18 h。在该最优条件下制备的催化剂前驱体主要以Ca₄Al₂O₆(NO₃)₂·10H₂O晶相存在,在N₂气保护下300 ℃焙烧2 h后,催化剂形成高分散钙铝复合氧化物,且碱性强度达到26.5以上。在催化菜籽油和甲醇的酯交换反应中,菜籽油的转化率达到95%,脂肪酸甲酯的质量分数为95.9%。     

Thermal and kinetic evaluation of cotton oil biodiesel

The biodiesel obtained by transesterification by reaction between ester and an alcohol in the presence of catalyst. The purpose of this work is to evaluate the thermal and kinetic behavior of the methanol biodiesel derived from cotton oil. The quality analysis was done by gas chromatography and proton nuclear magnetic resonance spectrometry (¹H NMR) in order to examine if the product meets with the requirements of the European Standard EN 1403. The thermogravimetric profile of the cotton biodiesel indicated that the decomposition steps are associated to the volatilization and/or decomposition of the methyl esters. Kinetic data was also obtained by thermal analysis.     

Optimization of alkaline transesterification of soybean oil and castor oil for biodiesel production

This article reports experimental data on the production of fatty acid ethyl esters from refined and degummed soybean oil and castor oil using NaOH as catalyst. The variables investigated were temperature (30–70°C), reaction time (1–3 h), catalyst concentration (0.5–1.5 w/wt%), and oil-to-ethanol molar ratio (1:3–1:9). The effects of process variables on the reaction conversion as well as the optimum experimental conditions are presented. The results show that conversions >95% were achieved for all systems investigated. In general, an increase in reaction temperature, reaction time, and in oil-to-ethanol molar ratio led to an enhancement in reaction conversion, whereas an opposite trend was verified with respect to catalyst concentration.     

Catalysts derived from waste slag for transesterification

MgO-CaO/SiO2 solid catalysts derived from waste slag (WS) of metal magnesium plant were prepared. The catalytic performances were evaluated in the transesterification of rapeseed oil with methanol to biodiesel in a 500 mL three-necked reactor under atmospheric pressure. The basic strengh of the catalyst reached 22.0 measured by indicators accroding to Hammett scale. The results show that the MgO-CaO/SiO2 is an excellent catalyst for transesterification, and the conversion of rapeseed oil reach 98% under the optimum condition.     

CaO@SiO_2纳米固体碱的制备、表征及其大豆油酯交换反应催化性能

采用溶胶-凝胶法合成Ca O@Si O_2固体碱催化剂,以聚苯乙烯有机聚合物为硬模板剂和以P123为软模板剂对Ca O的微观形貌进行调控。并将其应用于大豆油与甲醇的酯交换制备生物柴油的反应体系中。通过对Ca O@Si O_2纳米固体碱催化剂进行X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电镜(TEM)、CO_2-TPD及N_2的吸附-脱附(BET)表征发现,不仅制备得到了形貌归整的纳米固体颗粒,而且得到了Ca O包裹在Si O_2表面的核壳结构。进一步考察了不同的硅钙质量比、反应温度、催化剂的用量以及油醇物质的量比对生物柴油收率的影响,生物柴油的收率最高可以达到95.6%。     

Catalytic biodiesel synthesis under supercritical conditions

Increasing atmospheric pollution with greenhouse gases, a large proportion of which are transport pollutants, is forcing the search for new fuels from renewable sources. Biodiesel is currently produced by transesterification of plant oils over heterogeneous catalysts under gentle conditions. The other recent technology dealing with the transesterification with alcohols under supercritical conditions, i.e., at high temperature and pressure, can be more efficient, the cost of the resulting biodiesel having been lower, and lower quality feedstocks having been used. Supercritical transesterification can be performed catalytically or catalyst-free. This paper provides an overview of the catalytic lipid transesterification under supercritical conditions. The influence of raw material, alcohol and catalyst, as well as process parameters on biodiesel yield is analyzed.     

Brønsted双核碱性离子液体的合成及其在制备生物柴油过程中的催化性能

以N-甲基吗啡啉和1,4-二溴丁烷为原料,通过两步法合成了新型Brønsted碱性双核离子液体.分别采用¹H-NMR、FT-IR和元素分析对合成的离子液体进行结构分析;采用TGA测试离子液体的热稳定性;同时测定了离子液体的溶解性和碱性.此外,考察了双核碱性离子液体在大豆油和甲醇酯交换反应中的催化活性.结果表明,当甲醇:大豆油=14:1(物质的量比)、离子液体用量为大豆油质量的5%、反应时间5 h、反应温度60 ℃时、生物柴油收率为 95.6%(质量分数),且离子液体经回收、真空干燥,重复使用6次后催化活性没有明显降低,仍能达到94%以上.