油酸甲酯与ZDDP交互作用对柴油机油抗氧抗磨性能的影响

为更好的研究脂肪酸甲酯与柴油机油添加剂之间的交互作用,迚一步揭示生物柴油对柴油机油性能的影响。采用旋转氧弹法、热重法等手段研究了油酸甲酯与ZDDP的交互作用对柴油机油氧化安定性和热稳定性的影响,通过红外光谱分析了氧化前后柴油机油结构组成的变化,利用抗磨性试验考察并探讨了氧化前后油酸甲酯与ZDDP的交互作用对柴油机油抗磨性能的影响规律。结果表明:油酸甲酯显著劣化柴油机油的氧化安定性;油酸甲酯与ZDDP交互作用降低柴油机油的热稳定性;在给定试验条件下,油酸甲酯一定程度上改善了基础油的抗磨减摩性能,油酸甲酯与ZDDP交互作用会降低柴油机油的抗磨性能。     

油酸甲酯催化加氢制备生物烷烃的热力学分析

采用Benson基团贡献法对油酸甲酯加氢脱氧、加氢脱羰和加氢脱羧制备生物烷烃的热力学进行了分析，计算了613~653 K温度区间内油酸甲酯加氢体系的反应热、反应熵变、反应Gibbs自由能变和标准平衡常数，在此基础上采用PRO/Ⅱ软件中的平衡反应器模型分析了温度对油酸甲酯加氢产物分布的影响并和实验数据进行了对比验证。结果表明，油酸甲酯加氢脱氧、加氢脱羧和加氢脱羰制备生物烷烃的反应均为放热反应，放热量依次递减，各反应在613~653 K范围内均能够自发进行且反应完全。升高温度能够提高平衡产物中油酸甲酯加氢脱羰/羧产物的选择性，降低温度则有利于加氢脱氧产物的选择性，加氢脱氧与脱羰/羧产物选择性的比例随温度从613 K升高到653 K相应从1.92降低到0.56，与实验测得的反应数据变化趋势吻合。     

杂多酸催化油酸甲酯环氧化的研究

研究了以磷钨酸-D1821(磷钨酸双十八烷基季铵盐)作催化剂,二氯甲烷作溶剂,30%过氧化氢存在下油酸甲酯的环氧化反应,考察了反应条件对油酸甲酯环氧反应的影响,得到的优化反应条件为:m(30%过氧化氢)∶m(油酸甲酯)=1∶1,m(二氯甲烷)∶m(油酸甲酯)=1.5∶1,m(催化剂)∶m(油酸甲酯)=25‰。在最优条件下得到的环氧油酸甲酯的碘值在4.3 g I2/100 g左右,环氧值在3.95 g/100 g左右,酸值在0.2 mg KOH/g左右,均达到了一等品的要求。     

Ag~+-树脂络合吸附分离乌桕梓油中α-亚麻酸

建立了乌桕梓油的定性、定量分析方法,用气相色谱GC测定了乌桕梓油的脂肪酸组成,乌桕梓油中2,4-癸二烯酸、棕榈酸、油酸、亚油酸和亚麻酸的质量分数分别为4.0%,7.6%,14.6%,28.2%,38.4%。测定了Ag+-树脂吸附亚麻酸甲酯和亚油酸甲酯的吸附动力学曲线,吸附时间为5 h时吸附达到平衡。考察了Ag+负载量、溶剂种类对亚麻酸甲酯和亚油酸甲酯分离选择性的影响,在实验范围内,Ag+负载量越高,二者的分离度越大。乙醇作为溶剂时,Ag+-树脂能够选择性的吸附亚麻酸甲酯,亚麻酸甲酯和亚油酸甲酯的分离度为13.9;石油醚为溶剂时,Ag+-树脂对亚油酸甲酯和亚麻酸甲酯基本没有吸附。测定了不同流速时亚麻酸甲酯和亚油酸甲酯的穿透曲线,亚麻酸甲酯/亚油酸甲酯的穿透点和饱和点均随着流量的降低而推迟,而流量的增加有利于提高粒外扩散速率,减小传质带宽度。以乙醇为吸附溶剂,石油醚为洗脱溶剂,经过Ag+-树脂固定床吸附,亚麻酸甲酯的纯度从38%提高到65%。     

离子液体［Hnhm］H2PO4 催化合成油酸甲酯

合成并表征了离子液体［Hnhm］H₂PO₄ ,同时考察了该离子液体的溶解性及吸水性。以油酸甲酯的合成为探针反应,考察合成的离子液体对反应的催化活性。结果表明,在［Hnhm］H₂PO₄ 加入量为油酸质量的8%、n(甲醇)∶n(油酸)=3.5∶l、反应温度90 ℃和反应时间9 h条件下,油酸酯化率达63%以上,且［Hnhm］H₂PO₄离子液体与原料及产物的分离容易实现。     

复合溶剂吸收废气中醋酸丁酯的研究

采用散堆填料塔,分别考察了油酸甲酯、油酸乙酯和油酸甲酯-油酸乙酯复合溶剂对废气中醋酸丁酯的吸收性能.分析了醋酸丁酯质量浓度、油酸甲酯体积分数、液气比和空气流量对含醋酸丁酯废气吸收率的影响.结果表明,醋酸丁酯质量浓度ρ =0.535 g/L,复合吸收剂中油酸甲酯体积分数φ=0.5,液气比1.25 L/m3,空气流量v=4 L/min时,废气中醋酸丁酯吸收率可达94.12％.采用普通精馏对含醋酸丁酯的吸收液进行后处理,塔顶回收所得醋酸丁酯质量分数可达99.0％以上,塔釜回收所得油酸甲酯-油酸乙酯复合溶剂对醋酸丁酯废气回收率达91.01％.     

猪瘟疫苗免疫反应低下猪CD3~+CD4~+和CD4~+CD25~+淋巴细胞亚群分析

目的分析猪瘟疫苗免疫反应低下猪CD3+CD4+和CD4+CD25+淋巴细胞亚群的分布。方法将接种过猪瘟疫苗的种母猪经ELISA和血清中和试验检测筛选出猪瘟病毒(CSFV)抗体阴性猪。从中挑选出15头作为研究对象,以15头抗体阳性猪作为对照。采集猪的抗凝血,分离外周血淋巴细胞(PBL),流式细胞术检测30头猪PBL中CD3+CD4+和CD4+CD25+淋巴细胞亚群的分布。结果CSFV抗体阴性猪PBL中CD3+CD4+细胞的比例(24.09%±1.29%)明显低于CSFV抗体阳性猪(37.49%±1.60%);CSFV抗体阴性猪PBL中CD4+CD25+细胞的比例(2.34%±0.20%)明显高于CSFV抗体阳性猪(1.64%±0.13%)。结论PBL中CD3+CD4+淋巴细胞亚群的减少及CD4+CD25+淋巴细胞亚群的增加,可能是导致猪瘟疫苗免疫反应低下的重要原因。     

环氧油酸甲酯合成工艺的研究

研究了以Keggin型磷钨酸季铵盐作催化剂,二氯乙烷作溶剂,30%过氧化氢存在下油酸甲酯的环氧化反应,考察了不同碳链的磷钨酸季铵盐对油酸甲酯环氧化的催化效果。结果表明,磷钨酸-D1821(磷钨酸双十八烷基季铵盐)的催化效果最好。以磷钨酸-D1821作催化剂,油酸甲酯环氧化反应的最佳反应条件为:m(30%过氧化氢)∶m(油酸甲酯)=1.5∶1,m(二氯乙烷)∶m(油酸甲酯)=3∶1,m(催化剂)∶m(油酸甲酯)=0.025∶1,反应温度50℃。在此条件下,得到的产品的碘价为2.64 g I2/100 g,环氧值为3.91 g/100 g,酸值为0.41 mg KOH/g,达到了一等品的要求。     

DBU催化合成油酸甲酯及其机理初探

以1,8-二氮杂二环十一碳-7-烯(DBU)为催化剂,通过甲醇和油酸酯化反应合成了油酸甲酯。考察了n(甲醇)∶n(油酸)、DBU用量、反应时间等因素对油酸转化率的影响,并采用电导法对DBU催化甲醇和油酸反应的机理进行了研究。研究结果表明,当反应温度为60℃、n(甲醇)∶n(油酸)为6∶1、DBU用量为原料总质量的30%、反应时间为3h,油酸的酯化率为93.7%。甲醇+DBU溶液的电导率随DBU的加入呈现先上升、后下降的趋势,表明DBU的加入有助于甲醇失去活泼质子氢形成甲氧基负离子,从而促使酯化反应的进行。     

SDBS/Na_2CO_3改性膨润土及其在钻井液中的应用研究

对钙基膨润土经过钠化改性,其胶结性、悬浮性、分散性均得到提升,在水介质中,触变性较好,凝胶结构稳定,应用于钻井液中表现良好。实验考察了磁力搅拌时间、微波时间及功率、温度、十二烷基苯磺酸钠/碳酸钠(SDBS/Na_2CO_3)比例及50%无水乙醇等因素对膨润土改性的影响。得到制备改性膨润土最佳条件:m(膨润土)∶m(SDBS)∶m(Na_2CO_3)=16∶2∶3,50%无水乙醇40 mL,磁力搅拌时间3 min,微波时间2 min,反应温度40℃,微波功率200 W;将其用于制备钻井液,配方为:5%碳酸钠+4%改性膨润土+0.7%FLA+2%聚乙二醇+3%硅酸钾+0.8%硫酸钡,并对体系的流变性、滤失性、抑制性及抗污染性进行评价。     

Cold flow properties of fuel mixtures containing biodiesel derived from animal fatty waste

The aims of the present study were to evaluate the cold temperature behavior of methyl esters of vegetable and animal origin and of their mixtures with fossil diesel fuel, as well as to investigate the effectiveness of different depressants. Various blends of rapeseed oil methyl esters, linseed oil methyl esters, pork lard methyl esters and fossil diesel fuel were prepared, and both cloud point and cold filter plugging point (CFPP) were analyzed. It was found that mixtures with CFPP values of –5 °C and lower may contain up to 25% of pork lard methyl esters; whereas the ratio of summer fossil diesel fuel and rapeseed oil methyl esters may vary over a wide range, i.e. such mixtures can be used in a diesel engine in the summer. In the transitory periods it is possible to use up to 20% animal and vegetable ester blends (3 : 7) with winter fossil diesel, whereas only up to 5% of esters can be added to the fuel used in winter. In order to improve the cold properties of rapeseed oil, pork lard and linseed oil methyl ester mixtures, various additives were tested. Depressant Viscoplex 10–35 with an optimal dose of 5000 mg/kg was found to be the most effective.     

The production of fatty acid isopropyl esters and their use as a diesel engine fuel

Biodiesel is an alternative fuel for diesel engines that consists of the monoalkyl esters of vegetable oils or animal fats. Currently, most biodiesel consists of methyl esters, which have poor cold-flow properties. Methyl esters of soybean oil will crystallize and plug fuel filters and lines at about 0°C. However, isopropyl esters have better cold-flow properties than methyl esters. This paper describes the production of isopropyl esters and their evaluation in a diesel engine. The effects of the alcohol amount, the catalyst amount, and two different catalysts on producing quality biodiesel were studied. Both sodium isopropoxide and potassium isopropoxide were found to be suitable for use in the transesterification process. A 20∶1 alcohol/TG molar ratio and a catalyst amount equal to 1% by weight (based on the TG amount) of sodium metal was the most cost-effective way to produce biodiesel fuel. The emissions from a diesel engine running on isopropyl esters made from soybean oil and yellow grease were investigated by comparing them with No. 2 diesel fuel and methyl esters. For nitrogen oxide emission, the difference between the biodiesel produced from soybean oil and yellow grease was greater than the difference between the methyl and isopropyl esters of both feedstocks. The other emissions from using isopropyl esters were about 50% lower in hydrocarbons, 10–20% lower in carbon monoxide, and 40% lower in smoke number when compared with No. 2 diesel fuel.     

Palm oil methyl esters as lubricant additive in a small diesel engine

Malaysian crude palm oil has been successfully converted to methyl esters, also known as palm oil diesel (POD), which is readily combustible in diesel engines. This paper presents and discusses the results of current studies on the performance and the effects of POD on the wear characteristics of tribological components of a small, four-stroke diesel engine. Adding POD to commercial lubricating oil has enhanced the performance of such oils. Results obtained from this study show that the power output and brake specific fuel consumption of the engine, lubricated with commercial SAE 40 oil blended with POD, are comparable to those of 100% SAE 40 oil. Wear debris analysis shows that blends of POD and SAE 40 commercial lubricating oil increase the anti-wear characteristics of the engine when compared to 100% SAE 40 lubricating oil.     

Visible light active Cu-doped iron oxide for photocatalytic treatment of methylene blue

In recent work, pure α-Fe₂O₃ (F-1) and series of 5% Cu doped Fe₂O₃ (CF-5) , 10% Cu doped Fe₂O₃ (CF-10) and 15% Cu doped Fe₂O₃ (CF-15) nanoparticles by facile chemical coprecipitation method were synthesized to study the effect of concentration of doping for photocatalytic activity. As prepared F-1, CF-5, CF-10, CF-15 nanoparticles were subjected to X-ray diffraction (XRD) and Fourier transform infra-red (FTIR) techniques to analyse the structural and functional groups features. These characterization techniques confirmed the successful doping of Cu ²⁺ ions in α-Fe₂O₃. The crystallite size of synthesized samples was calculated by Scherrer formula. Gradually decline in crystallite size from 18 to 15 nm was observed for undoped to doped samples. Scanning electron microscopic (SEM) analysis expressed that doping of Cu reduced the aggregation of particles and enhanced the surface area of nanoparticles. UV–Visible spectroscopic analysis of synthesized samples was used to calculate the bandgap energy of F-1, CF-5, CF-10, CF-15 nanoparticles i.e., 2.0, 1.7, 1.5, 1.4eV respectively. Narrowing bandgap energy of doped hematite supported to perform excellent photocatalytic activity. Maximum degradation of methylene blue was recorded via CF-10 within 140 min. Higher degradation rate of methylene blue by optimal concentration of CF-10 is due to effective electron trapping ability of photocatalyst.     

生物柴油脂肪酸甲酯的成分及含量分析

采用GC/MS技术分析了由精棉籽油和棕榈油为原料通过酯交换反应得到的脂肪酸甲酯。结果表明,精棉籽油脂肪酸甲酯主要为棕榈酸甲酯、亚油酸甲酯和油酸甲酯,含量分别为22.23%,53.18%和18.09%。棕榈油脂肪酸甲酯主要为棕榈酸甲酯、油酸甲酯和硬脂酸甲酯,含量分别为40.3%,50.07%和7.02%。     

Study of the performance,emission and combustion characteristics of a diesel engine using poon oil-based fuels

Experiments were conducted to study the performance, emission and combustion characteristics of a DI diesel engine using poon oil-based fuels. In the present work, poon oil and poon oil methyl ester are tested as diesel fuels in Neat and blended forms. The blends were prepared with 20% poon oil and 40% poon oil methyl ester separately with standard diesel on a volume basis. The reductions in smoke, hydrocarbon and CO emissions were observed for poon oil methyl ester and its diesel blend along with increased NO_x emission compared to those of standard diesel. However, a reduction in NO_x emission and an increase in smoke, hydrocarbon and CO emissions were observed for Neat poon oil and its diesel blend compared to those of standard diesel. The 40% poon oil methyl ester blend showed a 2% increase in brake thermal efficiency compared to that of standard diesel, whereas other fuels tested showed a decreasing trend. From the combustion analysis it was found that ignition delay was shorter for all fuels tested compared to that of standard diesel. The combustion characteristics of poon oil methyl ester and its diesel blend closely followed those of standard diesel.     

Biodiesel production from pomace oil and improvement of its properties with synthetic manganese additive

Renewable energy sources are attracting more attention due to lower cost and lower pollution relative to fossil fuels. The aim of this experimental work is the production of renewable and clean methyl ester from pomace oil as an alternative fuel. This oil was obtained from pomace which is the waste of olive oil plants. Optimum producing conditions were determined experimentally. The maximum yield was obtained at 30% of methanol/oil ratio, 60 °C temperature for 60 min with NaOH catalyst. The properties of the biodiesel thus obtained were compared with diesel fuel requirements. An organic based Manganese additive improved the biodiesel properties. Doping the fuel at a ratio of 12 μmol/l oil methyl ester led to a 20.37% decrease in viscosity, 7 °C fall in the flash point and reduced the pour point from 0 °C to −15 °C. This blend of pomace oil methyl ester-diesel fuel with manganese additive was tested in a direct injection diesel engine. The maximum effect of the new fuel blend and diesel fuel on engine performance was obtained at 1400 rpm.     

Nucleophilic addition of hydrogen sulfide to methyl oleate,methyl linoleate,and soybean oil

Hydrogen sulfide was added to methyl oleate, methyl linoleate, and soybean oil at −70 and 25 C in the presence of boron trifluoride. Major reaction compounds were identified by gas liquid chromatography and mass spectrometry. At −70 C with a 200 molar ratio of hydrogen sulfide to ester, the reactions were complete in 4 hr. Primary reaction product from methyl oleate was methyl 9(10)-mercaptostearate. Methyl linoleate gave ca. equal amounts of methyl 9-(2-pentyl-1-thiolan-5-yl) nonanoate and methyl 8-(2-hexyl-1-thiolan-5-yl) octanoate. At 25 C, the reaction of methyl oleate and linoleate with hydrogen sulfide was less complete, and more side reactions were noted. When equimolar amounts of methyl oleate and methyl 9(10)-mercaptostearate were reacted in the presence of boron trifluoride at 25 C, a new compound was formed, bis(methyl n-octadecanoate 9[10]-yl) sulfide. The addition of liquid hydrogen sulfide to soybean oil at −70 C in the presence of boron trifluoride yields a product which, upon saponification, acidification, and methylation analyzes by gas liquid chromatography as ca. 52% thiolan, 27% mercaptostearate, 10% palmitate, 6% stearate, and 5% unidentified compounds.     

Comparative value of fatty acids and resin acids of tall oil in soaps

Summary A study has been made of the detergency and foaming power of soaps made from a typical acid-refined American tall oil. Sodium soap of tall oil, straight tall oil fatty-acid soap, and straight tall oil resin-acid soap were evaluated. The effect of fatty acid-resin acid ratio was determined by using mixtures of those soaps. Sodium rosinate, sodium oleate, and mixtures of these soaps were used as comparison standards. Curves plotted show wash-test data and foaming values as functions of the ratio of fatty soap to resin soap. The data indicate in terms of detergency: a) tall oil soap has a higher value than sodium rosinate; b) sodium oleate is better than tall oil fatty-acid soap, but the latter is approximately equivalent to soaps from various unsaturated vegetable oils; c) both tall oil resin-acid soap and rosin soap have low detergency on cotton; d) the detergency of most mixtures of tall oil fatty-acid and resin-acid soaps at lower concentrations is greater than would be predicted from the individual soaps, indicating a synergistic effect. As a rough approximation, tall oil soap without unsaponifiables is equivalent to a corresponding mixture of sodium oleate and sodium rosinate. The presence of unsaponifiables lowers both detergency and foaming. Tall oil soap is somewhat less sensitive to hard water than sodium oleate. Significant differences between detergencies of soaps, and especially between soap mixtures, are obscured when launderometer tests are run at moderate soap concentrations. These differences are readily detected at lower concentrations. Presented at 113th meeting of the American Chemical Society, Chicago, Ill., April 14–23, 1948.