木质素准液体替代柴油交通运输燃料

自1930 年人类才开始对木质素进行研究,1980 年美国人提出建议将木质素直接与柴油混合替代柴油,但都没有在技术上解决木质素颗粒作为柴油替代燃料时木质素在柴油中的稳定分散和输送问题.也即由于一直没有寻找到合适的分散剂或乳化剂,微细粒状木质素作为含氧易燃高能燃料过去一直不能用作为现代发动机的动力燃料.本项目利用木质素高分散性和流动性的特点,通过新的分散介质和乳化技术,使木质素微细颗粒可以与柴油均匀混合作为一种介于液体和固体之间的准液体燃料,部分地替代柴油.仅按照10% 替代比例,每年可以为我国节约柴油近千万吨;且与燃料乙醇、生物柴油相比较,木质素作为准液体燃料,不消耗粮食、不占用耕地、不需要国家财政补贴.与过去传统的试图将木质素液化后利用木质素作为交通运输燃料的技术方法完全不同,在世界科技界几十年来木质素液化生成交通运输燃料技术一直没有获得成功的背景下,本技术是直接利用固体颗粒状木质素经过新的分散乳化技术均匀分散于柴油中获得一种准液体燃料作为交通运输燃料.委托江苏大学江苏省生物柴油动力机械应用工程中心所进行的测试表明,含9.2%( 质量分数) 木质素准液体柴油燃料降低了柴油机排气温度约40℃,排烟状态无明显区别,混合油中的木质素25.2g 可替代14.3g 柴油,按等效热值计算,25.2g 木质素热值相当于16g 柴油的热值,说明木质素在测试使用条件下在柴油机汽缸内充分燃烧并替代柴油燃烧做功.另外,木质素具有玻璃转化温度,不同于其他生物质粉体或煤粉等没有玻璃转化温度的固体材料,在120 ～ 190℃以上温度时其是柔软的,所以对发动机的磨损作用与液体燃料应无大的区别.     

3种木质素的主要理化性质分析

介绍了木质素、碱木质素和铵化木质素的制备方法,且对这3种木质素的比重、钠元素含量、X射线衍射、热重、溶解度等理化性质进行表征。研究结果表明,铵化木质素不含有碱金属钠,同时具有很好的水溶性,即铵化木质素解决了纯木质素难溶于水的问题,又解决了碱木质素与柴油乳化后对柴油发动机汽缸内的损坏和长期使用会存在积炭的风险。这说明铵化木质素与木质素和碱木质素相比更适于同柴油乳化混合,实现传统化石能源的添加剂,铵化木质素为我国林木废弃生物质资源化利用和替代能源开发提供了一条潜在的途径。     

木质素柴油经济与动力性评价

对符合国家标准GB 252-2000《轻柴油》的木质素柴油的经济动力性进行了深入研究,发动机全负荷速度特性对比试验表明:木质素柴油和0号柴油的实测功率和扭矩基本相当;按照木质素柴油中纯柴油量折算则木质素柴油比0号柴油节油,平均节油率为10%~15%;发动机负荷特性对比试验表明:木质素柴油和0号柴油的在相同扭矩下,按照木质素柴油中纯柴油量折算则木质素柴油比0号柴油节油,平均节油率为10%~15%。发动机自由加速工况下排放对比试验表明:木质素柴油与0号柴油的尾气排放未见统计学差异。本文对木质素柴油的推广应用提供了基础数据。     

维生素E自微乳化给药系统的制备

目的:研究维生素E自微乳的制备工艺.方法:考察了维生素E在不同油、乳化剂、助乳化剂中的溶解情况,筛选油相、乳化剂和助乳化剂.以假三角相图中形成微乳的面积为指标,采用正交设计表对处方进行优化,确定维生素E自乳化给药系统的最佳处方.结果:微乳最佳处方:油酸乙酯:Tween-80:丙二醇的比例为3:4:3.结论:该处方自乳化区域大,自微乳化速率快,所形成的乳剂稳定.     

甲醇毕赤酵母表达木质素过氧化物酶的研究

将含有黄孢原毛平革菌(Phanerochaetechrysosprium)木质素过氧化物酶基因的甲醇毕赤酵母工程菌进行了鉴定和筛选,筛选得到木质素过氧化物酶活力高的菌株PMLIP08。确定了一步法发酵的最优葡萄糖浓度,优化其发酵培养条件,结果表明葡萄糖的添加量为10g/L时,发酵条件为pH3.0,诱导温度24℃,培养时间12h,甲醇添加量1.1%,诱导时间72h后发酵液中酶活可达4888U/L。     

长期施肥下亚热带典型农田(旱地)土壤木质素的积累特性

以广西环江(石灰土)、湖南桃源(红壤)两个亚热带典型农田(旱地)长期定位试验为平台,采用碱性氧化铜-固相萃取-气相色谱法,分析两种长期施肥制度[化肥(NPK)、秸秆还田配施化肥(NPKS)]下土壤中木质素V、S、C等3类单体含量及组成的变化,并阐明影响旱地土壤中木质素积累的主要因子.结果表明:长期施用化肥(NPK)对石灰土木质素总量(SumVSC)无显著影响,而红壤木质素总量显著增加(55±1)%;秸秆还田配施化肥(NPKS)均显著增加了两种土壤木质素总含量(P<0.01),增加比例分别为(328±4)%、(456±9)%.长期施肥处理增加了红壤木质素单体C的比例,石灰土则表现为单体V的比例增加,表明农田土壤中木质素的转化具有单体特异性;长期施肥后木质素单体的酸醛比(Ac/Al)V和(Ac/Al)S均有所降低,其中石灰土高于红壤,说明石灰土的木质素分解矿化程度较红壤高.有机质、全氮与木质素单体含量无显著相关,而对木质素单体V、S、C组成有显著影响;木质素V、S和C类单体含量及组成均与土壤速效养分(碱解氮、速效磷、速效钾)显著相关(P<0.05),由此认为土壤速效养分是木质素积累特性的关键影响因子.     

烃降解菌株T7-2产生的生物乳化剂及其理化性质研究

从石油污染海域海底泥中筛选到的1株低温石油烃降解菌, 经鉴定为红平红球菌(Rhodococcus erythropolis), 命名为T7-2。该菌株能以十六烷为碳源代谢产生一种对柴油等烃类具良好乳化作用的生物乳化剂。研究表明, 该乳化剂主要由糖类、脂类和蛋白质组成, 其比例为55.43:31.24:12.65。进一步研究证实, 该乳化剂糖类的单糖组成为甘露糖和鼠李糖; 脂类由十碳、十二碳、十六碳及十八碳脂肪酸组成; 蛋白质由16种氨基酸构成。本文还对乳化剂的理化性质进行了分析, 发现它是一种性能稳定、乳化效率高、适应范围较为广泛的生物乳化剂, 对海洋污染生物修复及石油开采都具有潜在的应用价值。     

烃降解菌株T7-2产生的生物乳化剂及其理化性质研究

从石油污染海域海底泥中筛选到的1株低温石油烃降解菌,经鉴定为红平红球菌(Rhodococcus erythropolis),命名为T7-2.该菌株能以十六烷为碳源代谢产生一种对柴油等烃类具良好乳化作用的生物乳化剂.研究表明,该乳化剂主要由糖类、脂类和蛋白质组成,其比例为55.43:31.24:12.65.进一步研究证实,该乳化剂糖类的单糖组成为甘露糖和鼠李糖;脂类由十碳、十二碳、十六碳及十八碳脂肪酸组成;蛋白质由16种氨基酸构成.本文还对乳化剂的理化性质进行了分析,发现它是一种性能稳定、乳化效率高、适应范围较为广泛的生物乳化剂,对海洋污染生物修复及石油开采都具有潜在的应用价值.     

pH响应型蔗渣木质素水凝胶的制备及其对蛋白质的控释性能

该研究以蔗渣木质素和甲基丙烯酸为原料合成了pH敏感型蔗渣木质素/聚甲基丙烯酸水凝胶,对其合成条件、pH敏感性、溶胀-退溶胀性能以及对牛血清蛋白的控释等性质进行研究,并采用红外光谱、扫描电镜等对凝胶进行表征。结果表明:(1)对凝胶溶胀比影响的因素由大到小依次为甲基丙烯酸用量、交联剂用量、催化剂用量、反应的温度、木质素用量。当甲基丙烯酸单体浓度为1.75 mol·L~(-1)、木质素浓度为25 g·L~(-1)、交联剂浓度为3.25×10~(-2)mol·L~(-1)、引发剂浓度为1.25×10~(-2)mol·L~(-1)、反应温度为65℃时,所得水凝胶在模拟肠液中的溶胀比最大(28.16 g·g~(-1))。与不加木质素的聚甲基丙烯酸水凝胶相比,蔗渣木质素/聚甲基丙烯酸水凝胶的溶胀比有所下降,但其敏感pH由4~5碱移至6~8。(2)蔗渣木质素/聚甲基丙烯酸水凝胶的溶胀—退溶胀可逆性受组成的影响较大,但相对于聚甲基丙烯酸水凝胶,蔗渣木质素/聚甲基丙烯酸水凝胶对pH值的敏感响应性更强、响应速率更快,同时能在更短时间内达到溶胀平衡。(3)加入木质素可以提高水凝胶对牛血清蛋白的负载量,所试验的蔗渣木质素/聚甲基丙烯酸水凝胶样品对牛血清蛋白的最大负载量可达577 mg·g~(-1)。(4)牛血清蛋白在12 h后基本可达释放平衡;在模拟胃液中,牛血清蛋白的释放率仅10%,而在模拟肠液中释放率达92%。pH响应型蔗渣木质素/聚甲基丙烯酸水凝胶可以作为口服型蛋白类药物的潜在载体。     

高产木质素酶荧光假单胞杆菌L-520的筛选及其发酵工艺优化

利用苯胺蓝鉴别培养基及产酶培养基进行菌种筛选,从甘肃兴隆山分离得到的10株菌株中筛选到一株高产木质素酶活力的菌株L-520,对该菌株进行16S rDNA鉴定,确定该菌为荧光假单胞杆菌(Pseudomonas fluorescens)。分别考察了接种量、装液量,初始pH对L-520发酵产酶的影响,以及碳源、氮源对木质素酶活力的影响。结果得到最佳培养基为:蔗糖1%,NH_4Cl 0.2%,KH_2PO_4 0.1%,MgSO_4?7H_2O 0.05%。优化后的发酵条件为:初始pH 5,接种量3%,装液量50%。经发酵工艺优化后,漆酶(Lac)、木质素过氧化物酶(LiP)、锰过氧化物酶(MnP)三种酶活分别为16.43 U/L,106.32 U/L,95.89U/L,与初始酶活相比分别提高了8.7、14.74、11.09倍。本研究筛选得到的荧光假单胞杆菌有助于染料废水中偶氮染料的降解。     

Production of an extracellular polysaccharide with emulsifier properties by Penicillium citrinum

Penicillium citrinum produced a glycolipid with emulsifier properties during cultivation on mineral medium with 1% (v/v) olive oil as carbon source. The emulsifier production was growth-associated and reached maximal activity at 60 h of cultivation. The production yield (Y _p/s) was 0.54 and the best emulsifying activity was observed for xylene and diesel oil when compared to other carbohydrates tested. The emulsifier was shown to be stable to a wide range of pH and temperature values and was shown to contain D-galactose, D-glucose and D-xylose (8.2:1.0:5.3) with a total carbohydrate content of 43%. The presence of salts stimulated the emulsification activity, suggesting potential for its application in industrial waste or marine remediation.     

Effects of Petroleum Hydrocarbons on Plant Litter Microbiota in an Arctic Lake

The effects of petroleum hydrocarbons on the microbial community associated with decomposing Carex leaf litter colonized in Toolik Lake, Alaska, were examined. Microbial metabolic activity, measured as the rate of acetate incorporation into lipid, did not vary significantly from controls over a 12-h period after exposure of colonized Carex litter to 3.0 ml of Prudhoe Bay crude oil, diesel fuel, or toluene per liter. ATP levels of the microbiota became elevated within 2 h after the exposure of the litter to diesel fuel or toluene, but returned to control levels within 4 to 8 h. ATP levels of samples exposed to Prudhoe Bay crude oil did not vary from control levels. Mineralization of specifically labeled ¹⁴C-[lignin]-lignocellulose and ¹⁴C-[cellulose]-lignocellulose by Toolik Lake sediments, after the addition of 2% (vol/vol) Prudhoe Bay crude oil, motor oil, diesel fuel, gasoline, n-hexane, or toluene, was examined after 21 days of incubation at 10°C. Diesel fuel, motor oil, gasoline, and toluene inhibited ¹⁴C-[lignin]-lignocellulose mineralization by 58, 67, 67, and 86%, respectively. Hexane-treated samples displayed an increase in the rate of ¹⁴C-[lignin]-lignocellulose mineralization of 33%. ¹⁴C-[cellulose]-lignocellulose mineralization was inhibited by the addition of motor oil or toluene by 27 and 64%, respectively, whereas diesel fuel-treated samples showed a 17% increase in mineralization rate. Mineralization of the labeled lignin component of lignocellulose appeared to be more sensitive to hydrocarbon perturbations than was the labeled cellulose component.     

Potential Application of Turnip Oil (Raphanus sativus L.) for Biodiesel Production: Physical–Chemical Properties of Neat Oil, Biofuels and their Blends with Ultra-Low Sulphur Diesel (ULSD)

Turnip oil (TO; Raphanus sativus L.) produces seeds that contain around 26 wt% of inedible base stock that are suitable as a potential feedstock for biodiesel production. A turnip oil methyl ester (TME) was prepared from acid-catalyzed pretreated TO in an effort to evaluate important fuel properties of turnip oil-based biodiesel, such as kinematic viscosity, cloud point, pour point (PP), cold filter plugging point, acid value, oxidative stability and lubricity. A comparison was made with soybean oil methyl esters (SME) as per biodiesel fuel standards such as ASTM D6751 and EN 14214. TME was characterized using FTIR, HPLC and ¹H NMR. Except PP property, SME displays superior fuel properties compared to TME. Blends (B5 and B20) of TME in ultra-low sulphur diesel fuel (ULSD) were also assessed for the aforesaid fuel properties and compared to an analogous set of blends of soybean oil methyl ester in ULSD as per petro diesel fuel standards such as ASTM D975 and D7467. TME B5 blends in ULSD displayed improved PP property in comparison to neat ULSD and blends of SME in ULSD. It was demonstrated that the B5 and B20 blends of TME in ULSD had acceptable fuel properties as per ASTM D975 (for B5 blend) and ASTM D7467 (for B20 blend). In summary, turnip oil has potential as an alternative, non-food feedstock for biodiesel production.     

Preparation and Evaluation of Jojoba Oil Methyl Esters as Biodiesel and as a Blend Component in Ultra-Low Sulfur Diesel Fuel

The jojoba plant (Simmondsia chinensis L.) produces seeds that contain around 50 to 60 wt.% of inedible long-chain wax esters that are suitable as a potential feedstock for biodiesel (BD) production. Jojoba oil methyl esters (JME) were prepared from acid-catalyzed pretreated jojoba oil in order to evaluate important fuel properties of jojoba-based BD, including kinematic viscosity, cloud point (CP), pour point (PP), cold filter plugging point (CFPP), acid value (AV), oxidative stability, and lubricity. A comparison was made with soybean oil methyl esters (SME) and relevant BD fuel standards such as ASTM D6751 and EN 14214. JME was characterized using Fourier transform infrared spectroscopy and ¹H and ¹³C nuclear magnetic resonance. The CP, PP, and CFPP of JME were ?13°C, ?16°C, and ?14°C, respectively, which were superior to SME. The kinematic viscosity (40°C) of JME was 6.67 mm²/s, which was higher than observed for SME. Blends (B5 and B20) of JME in ultra-low sulfur diesel fuel (ULSD) were also evaluated for the aforementioned fuel properties and compared to an analogous set of blends of SME in ULSD and relevant petro diesel fuel standards such as ASTM D975 and D7467. JME blends in ULSD displayed improved low-temperature properties in comparison to neat ULSD and blends of SME in ULSD. In summary, jojoba oil has potential as an alternative, nonfood feedstock for BD production.     

中国如何突破生物柴油产业的原料瓶颈

因应我国日益严峻的能源资源、能源环境和能源安全形势,国家大力倡导发展可再生能源。生物柴油是最重要的液体可再生燃料之一,在能源性质方面可以完全替代化石柴油,而且还具有安全环保等其它优良特性。当前利用动植物油脂生产生物柴油,原料成本偏高,而且稳定、充足的油脂原料供应体系尚未形成。我国是油脂资源短缺国家,近年来植物油进口量逐年增加。同时,我国耕地资源匮乏,粮食供应形势不容乐观,扩大油料作物种植的潜力非常有限。但是,我国宜林地丰富,农林废弃生物质资源量巨大。综合以上因素,我国应重点发展木本油料植物规模化种植和推广,加快微生物油脂发酵技术创新和产业化进程;同时,利用植物遗传育种技术提高油料作物产量以及选择性发展不与粮争地的油料作物。依靠各方面的进步,发展创新的油脂生产技术,保障我国生物柴油产业和油脂化工行业健康发展。     

Moringa oleifera oil: a possible source of biodiesel

Biodiesel is an alternative to petroleum-based conventional diesel fuel and is defined as the mono-alkyl esters of vegetable oils and animal fats. Biodiesel has been prepared from numerous vegetable oils, such as canola (rapeseed), cottonseed, palm, peanut, soybean and sunflower oils as well as a variety of less common oils. In this work, Moringa oleifera oil is evaluated for the first time as potential feedstock for biodiesel. After acid pre-treatment to reduce the acid value of the M. oleifera oil, biodiesel was obtained by a standard transesterification procedure with methanol and an alkali catalyst at 60 degrees C and alcohol/oil ratio of 6:1. M. oleifera oil has a high content of oleic acid (>70%) with saturated fatty acids comprising most of the remaining fatty acid profile. As a result, the methyl esters (biodiesel) obtained from this oil exhibit a high cetane number of approximately 67, one of the highest found for a biodiesel fuel. Other fuel properties of biodiesel derived from M. oleifera such as cloud point, kinematic viscosity and oxidative stability were also determined and are discussed in light of biodiesel standards such as ASTM D6751 and EN 14214. The (1)H NMR spectrum of M. oleifera methyl esters is reported. Overall, M. oleifera oil appears to be an acceptable feedstock for biodiesel.     

Stability of the oil-in-water type triacylglycerol emulsions

Lipid emulsions with saturated triacylglycerols (TAGs) with 4 to 10 carbons in each acyl chain were prepared to study how the oil component alters the stability of the lipid emulsions when phosphatidylcholines were used as emulsifiers. The average droplet size of the emulsions became smaller as the chain length of the TAG increased. For a given oil, emulsion with smaller droplets was formed with an emulsifier having higher HLB value. The influence of HLB values on the droplet size was biggest for the tributyrin (C4) emulsions. For the tricaprylin (C8) emulsions, droplet size was identical at given emulsifier concentrations regardless of HLB values. The HLB value and the concentration of the emulsifiers also affect the droplet size of the emulsions. The emulsions with smaller average droplet size were more stable than with bigger size for 20 days. The oil and water (o/w) interfacial tension is inversely proportional to the initial droplet size of the emulsion.     

Encapsulation of sunflower oil in starch matrices via extrusion: effect of the interfacial properties and processing conditions on the formation of dispersed phase morphologies

In this study, the encapsulation of sunflower oil in a starch matrix via extrusion was investigated. The aim of this study was to get insight into the relations between the processing parameters, the hydrophile–lipophile balance (or the hydrophobic–hydrophilic balance; HLB) value of the emulsifier and the morphology of the dispersed phase. The obtained samples were analysed for their dispersed phase morphology using scanning electron microscopy. It was seen that the HLB value of the emulsifier affected the dispersed phase morphology. The average size of the dispersed oil droplets decreased with increasing HLB value, and was explained by the observed decrease in the interfacial surface tension between the starch melt and the oil phase. Average sizes of oil droplets also decreased with increasing screw speed, increasing melt temperature and decreasing throughput. The screw configurations also affected the average sizes of dispersed oil droplets. Especially dispersive mixing elements and kneading blocks favour the formation of smaller dispersed oil droplets.     

Influence of tall oil biodiesel with Mg and Mo based fuel additives on diesel engine performance and emission

The purpose of this study is to investigate influences of tall oil biodiesel with Mg and Mo based fuel additives on diesel engine performance and emission. Tall oil resinic acids were reacted with MgO and MoO(2) stoichiometrically for the production of metal-based fuel additives (combustion catalysts). The metal-based additives were added into tall oil biodiesel (B60) at the rate of 4 micromol/l, 8 micromol/l and 12 micromol/l for preparing test fuels. In general, both of the metal-based additives improved flash point, pour point and viscosity of the biodiesel fuel, depending on the rate of additives. A single cylinder DI diesel engine was used in the tests. Engine performance values did not change significantly with biodiesel fuels, but exhaust emission profile was improved. CO emissions and smoke opacity decreased by 56.42% and by 30.43%, respectively. In general, low NO(x) and CO(2) emissions were measured with the biodiesel fuels.