废弃油脂原料SRCA生物柴油技术的研发与工业应用示范

针对废弃油脂品质差,酸值高,难于采用传统的碱催化酯交换技术加工生产生物柴油,中国石化石油化工科学研究院开展了超/近临界甲醇介质中油脂溶解和反应的基础研究,相继解决了甲醇与油脂的互溶、降低反应条件,三脂肪酸甘油酯和游离脂肪酸的深度转化,以及产品质量等问题,成功开发了近临界醇解生物柴油技术(以下简称SRCA),于2009年建成了6万吨/年工业化示范装置,以酸化油和餐厨废油为原料,生产连续稳定,产品收率高且满足国家生物柴油质量标准(GB/T20828-2007).     

生物柴油树种油脂脂肪酸组成对燃料特性的影响

以目前中国主要开发或具有开发潜能的10种生物柴油树种为研究对象,分析其果实或种子油脂脂肪酸组成对合成生物柴油燃料特性的影响。结果表明,木本植物生物柴油产品十六烷值、碘值、氧化安定性等燃料特性主要由原料油脂肪酸的不饱和度决定,脂肪酸不饱和度低于133.13,十六烷值(GB/T 20828-2007)和碘值(EN 14214)就可以达标。生物柴油产品冷滤点随着长碳链饱和脂肪酸的增加而升高,脂肪酸饱和碳链长度因子分别小于8.41和2.72时,可以满足冷滤点0℃和-10℃的要求。高品质生物柴油的原料中应该具有较高的单元不饱和脂肪酸含量。通过油脂脂肪酸单不饱和脂肪酸、多不饱和脂肪酸和饱和脂肪酸的组成绘制出生物柴油特性三角预测图,为预测生物柴油产品燃料特性提供参考依据。     

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     

气相色谱法测定生物柴油中脂肪酸甲酯含量

生物柴油是利用动植物油脂等可再生资源通过酯交换技术制造的可以替代石化柴油的新型清洁安全燃料[1-3]它的主要成分是脂肪酸甲酯。由于不同油脂原料所生产的生物柴油的脂肪酸甲脂组成不同因而测定时所需的气相色谱条件与方法也不尽相同[4-6]。本文采用HP-innowax毛细管色谱柱,     

废弃油脂生产生物柴油的研究进展

简单介绍了生物柴油的生产原料,综述了用废弃油脂生产生物柴油的现状和方法。废弃油脂生产生物柴油的方法主要有物理法和化学法,物理法主要有掺和法和微乳法,化学法主要有热裂解法和酯交换法。目前生产中采用化学法的酯交换法、以酸碱两步催化法的工艺为主,而生物酶法和超临界法是研究热点。     

油脂催化转化为绿色燃料的技术进展

油脂是一类非常重要的绿色可再生能源载体.运用催化技术将油脂高效地转化为液态燃料尤其是绿色烃类燃料是当前生物质转化利用中最具有工业化应用潜力的方向,因此备受关注.本文从油脂催化转化技术中的酯交换技术、催化裂化技术、硫化态和还原态金属加氢脱氧技术等方面阐述了国内外科研前沿领域在催化剂、工艺、反应路径及机理等方面的进展.对未来多种油脂原料转化为烃类燃料尤其是生物航煤的技术路线进行了分析与建议.     

微藻的高油脂化技术

温室效应与石化能源紧缺已成为全球问题,生物燃料作为一种可再生且环境友好的替代能源受到人们的普遍关注。不少微藻油含量高,环境适应性强,净碳值几乎为零,被认为是生物质能,尤其生物柴油最重要的原料来源之一。本文综述了油脂微藻的国内外研究现状,并对高油脂微藻藻种筛选、高密度培养,以及提高微藻油脂含量和产油速率的可能方法进行了讨论;阐述了采用基因工程技术调控微藻脂类代谢途径生产高油脂的可能性;最后介绍了以CO2废气为碳源,膜生物反应器强化微藻培养技术,为进一步降低微藻产油成本,提高微藻生物柴油经济性提出了一条极有可能实现工业化的潜在高效生产途径。     

近年生物柴油产业的发展——特色、困境和对策

本文介绍了美国、欧盟、印度生物柴油产业发展的特点、发展生物柴油的新兴原料和生物柴油生产技术的最新进展.分析了造成现在生物柴油产业发展面临困境的原因在于原料植物油的价格高涨.通过对生物柴油产业链的分析,提出生物柴油产业摆脱所面临困境的对策是:从植物育种和栽培开始,到收割、储存和榨油加工的每一步都要降低成本,力求取得低成本的原料油;开发投资少、成本低的清洁生物柴油生产工艺;关键是要从生物柴油(脂肪酸甲酯)和甘油来生产高附加值的化工产品,大幅度提高利润.     

近年生物柴油产业的发展——特色、困境和对策

本文介绍了美国、欧盟、印度生物柴油产业发展的特点、发展生物柴油的新兴原料和生物柴油生产技术的最新进展.分析了造成现在生物柴油产业发展面临困境的原因在于原料植物油的价格高涨.通过对生物柴油产业链的分析,提出生物柴油产业摆脱所面临困境的对策是:从植物育种和栽培开始,到收割、储存和榨油加工的每一步都要降低成本,力求取得低成本的原料油;开发投资少、成本低的清洁生物柴油生产工艺;关键是要从生物柴油(脂肪酸甲酯)和甘油来生产高附加值的化工产品,大幅度提高利润.     

微藻的高油脂化技术研究进展

温室效应与石化能源紧缺已成为全球问题,生物燃料作为一种可再生且环境友好的替代能源受到人们的普遍关注。不少微藻油含量高,环境适应性强,净碳值几乎为零,被认为是生物质能,尤其是生物柴油最重要的原料来源之一。本文综述了油脂微藻的国内外研究现状,并对高油脂微藻藻种筛选、高密度培养,以及提高微藻油脂含量和产油速率的可能方法进行了讨论;阐述了采用基因工程技术调控微藻脂类代谢途径生产高油脂的可能性;最后介绍了以CO2废气为碳源,膜生物反应器强化微藻培养技术,为进一步降低微藻产油成本,提高微藻生物柴油经济性提出了一条极有可能实现工业化的潜在高效生产途径。     

酸、盐处理对Pt/SAPO-11物化及其催化性能的影响

采用不同酸和盐浸渍处理SAPO-11分子筛,然后负载Pt制成改性的Pt/SAPO-11催化剂,用XRF、XRD、N_2吸附-脱附、SEM、NH_3-TPD和Py-IR对催化剂进行表征,分析其物理化学性能。结果表明,酸和盐处理没有破坏SAPO-11的骨架结构,还提高了催化剂的孔容、孔径、比表面积等性质,催化剂的酸性、酸量也明显发生了改变。在固定床反应器中,评价了改性的Pt/SAPO-11催化小桐子油一步加氢制异构烷烃性能;结合催化剂表征数据表明,颗粒粒径、比表面积、孔径、酸性和酸量影响催化剂的活性及产物分布。对比发现,经0.5 mol/L柠檬酸处理的Pt/SAPO-11催化剂孔径大小、酸性、B酸和L酸量分布合适,因此,一步加氢催化处理小桐子油性能优异;其中,生物航油组分(C_(8-16))的收率为32.47%,异构烷烃(C8-16)选择性为53.13%。     

Biodiesel Production from Vegetable Oils and Animal Fat over Solid Acid Double-Metal Cyanide Catalysts

Biodiesel comprises of fatty acid alkyl esters prepared from vegetable oils or animal fat by esterification/transesterification with short-chain alcohols (methanol or ethanol, for example). It is a biodegradable renewable fuel. Its production is growing exponentially due to greater concerns about environmental protection and depletion of fossil fuel resources. Further, its production from non-edible oils and animal fat is more desirable than from edible oils due to lower cost of non-edible feedstocks and elimination of food verses fuel issues. Solid acid catalysts are ideal for conversion of such low-grade oils to biodiesel. Biodiesel from non-edible oils can be produced by two methods: (1) simultaneous esterification of fatty acids and transesterification of fatty acid glycerides and (2) hydrolysis of glycerides followed by esterification. This account reports the catalytic performance of solid, Fe–Zn double-metal cyanide (DMC) complexes and other acid catalysts in these transformations for biodiesel production. The factors influencing the catalytic performance of the solid acid catalysts in biodiesel production are discussed.     

Lipase-Catalyzed Transesterification of Rapeseed Oil for Biodiesel Production with tert-Butanol

Biodiesel is a fatty acid alkyl ester that can be derived from any vegetable oil or animal fat via the process of transesterification. It is a renewable, biodegradable, and nontoxic fuel. In this paper, we have evaluated the efficacy of a transesterification process for rapeseed oil with methanol in the presence of an enzyme and tert-butanol, which is added to ameliorate the negative effects associated with excess methanol. The application of Novozym 435 was determined to catalyze the transesterification process, and a conversion of 76.1% was achieved under selected conditions (reaction temperature 40 °C, methanol/oil molar ratio 3:1, 5% (w/w) Novozym 435 based on the oil weight, water content 1% (w/w), and reaction time of 24h). It has also been determined that rapeseed oil can be converted to fatty acid methyl ester using this system, and the results of this study contribute to the body of basic data relevant to the development of continuous enzymatic processes.     

Analysis of biodiesel conversion using thin layer chromatography and nonlinear calibration curves

Biodiesel (BD) is a fuel produced by the (trans)esterification reaction between the components of vegetable oil (or animal fat) and an alcohol. The presence of several substrates complicates analytical separation of the mixture, yet understanding of the complex reaction kinetics requires acquisition of a large body of data. The two well-established methods of gas chromatography (GC) and HPLC are time consuming and expensive when analyzing multiple samples. Additionally, it is not always possible to record all the reactants on one elution profile. We examined applicability of thin layer chromatography (TLC) for this purpose, where the detection was based on either flame ionization detector (FID) or a modified staining procedure. The suggested staining method gave no background and appeared well suited for quantitative analysis. The relevant calibrations are presented, and the general principles of analysis of nonlinear responses are discussed. Several experimental samples were produced by enzymatic conversion of rapeseed oil to BD. One reaction step resulted in 85-95% conversion (6h). The second step (after removal of glycerol and water) increased the yield to 97-98%. All components of the mixtures were separated and quantified. Relation of the BD contents measured by TLC and GC gave the values of 1.03±0.07 (TLC-staining) and 0.95±0.04 (TLC-FID), indicating applicability of the TLC-methods.     

Study on the Performance of Three Different Capillary Gas Chromatographic Analyses in the Evaluation of Milk Fat Purity

The adulteration of milk fat with foreign fat has been and still is a major concern in the dairy industry. Milk fat purity is currently evaluated by triglyceride analysis by using the Official EU method. The detection limit of the various vegetable and animal fats ranges between 4 and 6%. This research was carried out to verify whether it is possible to decrease the detection limits of beef tallow, which is the most widely used adulterating animal fat. For this purpose, determinations of diglycerides and 3,5-cholestadiene, together with the Official EU method, were applied both to several samples of pure milk fat and to mixtures of milk fat with different percentages of beef tallow. The best results were obtained combining the data deriving from the three determinations by multivariate statistical techniques; in particular, the statistical model obtained by the UNEQ technique seems to be able to decrease the detection limit of beef tallow from 5.2 to 2%. The diglyceride and 3,5-cholestadiene evaluation, combined with the Official EU method for triglycerides, can be usefully applied both to detect small additions of beef tallow and to demonstrate the adulteration of milk fat samples showing results close to the detection limit of the official method.     

Application of Flying Jet Plasma for Production of Biodiesel Fuel from Wasted Vegetable Oil

Biodiesel, a good partial or total substitute for petrodiesel, is a renewable clean burning fuel which can be produced from transesterification of vegetable oils and animal fats with an alcohol in presence of a catalyst. Since the feedstock costs in this process constitutes more than 70 % of the overall cost, use of wasted vegetable oil (i.e. consumed cooking oil) for biodiesel production is a big challenge in terms of cost reduction and environmental impacts. Nonetheless, the content of residues in the wasted vegetable oil, formed during frying, is a major drawback could be faced in this direction. In this research, we applied an unconventional design of flying jet dielectric barrier discharge plasma torch to treat several specimens of wasted cooking oil collected from different resources before transesterification. In other experiments, the jet plasma itself was used to catalyze the reaction process. The examined plasma torch was found more feasible than conventional DBD reactor design in terms of gas and power consumptions. Upon inducting plasma treatment, the transesterification process resulted in higher biodiesel yield, lower reaction time and easier product separation than the conventional path. Upon catalyzing the reaction by the sole jet plasma effect, the biodiesel content of saturated methyl esters was higher than conventional tranesterification. Also, the yield and properties were found within commercial standards.     

超声作用下KF/CaO催化酯交换反应制备生物柴油

等体积浸渍法制备了KF/CaO固体碱催化剂,用于催化大豆油与甲醇酯交换反应制备生物柴油,在反应体系中引入超声作为辅助条件。研究表明,KF/CaO催化活性高。在超声的辅助作用下,酯交换反应速率加快,生物柴油的收率提高。实验考察了反应条件对产品中脂肪酸甲酯含量的影响。醇油摩尔比为12∶1,反应温度65℃,催化剂与大豆油的质量比为3%,反应1 h,超声频率20 kHz,超声声强1.01 W/cm2,在此反应条件下,产品中脂肪酸甲酯的质量分数达到99.6%。     

药渣热解过程NO_x前驱物生成特征及规律研究

以凉茶药渣(HTW)和青霉素菌渣(PMW)为对象,结合热重(TGA)和X射线光电子能谱(XPS)表征,在水平管式反应器上对比研究了热解NO_x前驱物的生成特征,考察了热力因素和燃料理化特性的影响。结果表明,蛋白质N为主要原料N结构,HTW占全部,PMW超过80%,决定了主导NO_x前驱物为NH_3;热力因素不改变此主导性,但会影响前驱物生成路径,改变组分比例及总产率,其强弱顺序为:高温快速高温慢速低温快速≈低温慢速;基于高温快速热解,大粒径和低含水率可分别降低总产率5%-11%和4%-6%;燃料组分影响NH_3产率,低温或慢速下,N结构差别使PMWHTW;高温快速下,灰分元素差异使PMWHTW;半焦N结构及N分布表明,典型热解条件下总产率为20%-45%,与药渣种类无关,可为其清洁利用提供参考。     

微波消解/干灰化-分光光度法测定面制食品中的铝

采用微波消解法和干灰化法对面制品进行前处理,用分光光度法测定面制品中的铝含量,建立了微波消解/干灰化-分光光度法测定铝的方法.实验结果表明,本方法前处理简单,检测结果准确度高,精密度好,在0～10μg/25 mL线性范围内:相关系数r=0.999 5,方法检出限为0.2 μg/25 mL,样品的加标回收率在92.0 %...     

Animal-fat investigation and combustion test

The department was commissioned to investigate the possibilities for animal-fat combustion in industrial steam generators operating originally on fuel–oil or natural gas. There are two main reasons for operating generators on animal fat as a fuel: On one hand, this material is considered as hazardous waste, thus an important goal is its environmentally benign elimination or disposal. On the other hand, fat is an excellent energy source and can be used as combustion fuel. This way fossil fuel usage can be saved while environmental regulations can also be met. The usage of animal fat as a fuel for furnaces required classification according to fuel classification rules, and comparison with the properties of fuel oil. In addition, its pollutant content was determined and the effects on the combustion process and emission were investigated. Finally the savings in fossil fuel energy consumption and related CO₂ emission achieved were determined. The first stage involved the determination of the composition of animal fat. Subsequently other properties such as viscosity and flash point variation were investigated. These data were compared to the properties of fuel oil. The theoretical investigations of animal-fat classification were promising. Initially one steam generator, originally designed for fuel oil combustion, was modified and fitted with a parallel animal fat fuel supply system. The results of the test were encouraging, although there were some problems with power regulation and later with fuel supply. A rotary cup type burner was then fitted to the boiler. Using this system, all the requirements including environmental regulations were met.