低温下2,5-二甲基呋喃的氧化动力学及产物研究

建立了2,5-二甲基呋喃(DMF)的气相色谱(GC)定量分析方法,跟踪测定DMF在低温下的氧化过程及动力学,用碘量法测定了DMF过氧化物的生成,并测定了DMF的氧化产物。结果表明,DMF与氧气在低温下的氧化呈现表观一级反应,温度为323.15,333.15,343.15,353.15,363.15 K时的反应速率常数分别为:0.004 6,0.006 4,0.008 9,0.011 8,0.015 0 h~(-1),反应表观活化能为29.08 k J/mol。在363.15 K反应10 h,主要氧化产物为5-甲基-2-呋喃甲醇(7.3%),反-3-己烯-2,5-二酮(70.8%),5-甲基-2-呋喃甲醛(13.4%),其他(8.5%)。     

低温下2,5-二甲基呋喃的氧化动力学及产物研究

建立了2,5-二甲基呋喃(DMF)的气相色谱(GC)定量分析方法,跟踪测定DMF在低温下的氧化过程及动力学,用碘量法测定了DMF过氧化物的生成,并测定了DMF的氧化产物。结果表明,DMF与氧气在低温下的氧化呈现表观一级反应,温度为323.15,333.15,343.15,353.15,363.15 K时的反应速率常数分别为:0.004 6,0.006 4,0.008 9,0.011 8,0.015 0 h^(-1),反应表观活化能为29.08 k J/mol。在363.15 K反应10 h,主要氧化产物为5-甲基-2-呋喃甲醇(7.3%),反-3-己烯-2,5-二酮(70.8%),5-甲基-2-呋喃甲醛(13.4%),其他(8.5%)。     

电化学合成2,5-二甲氧基-2,5-二氢呋喃甲醇工艺研究

以糠醇为原料,NaBr为电解质,甲醇为溶剂,利用电化学法合成焦袂康酸中间体2,5-二甲氧基-2,5-二氢呋喃甲醇,考察反应时间、NaBr添加量、反应温度对产率的影响。结果表明,反应时间与反应温度对产率有显著影响,NaBr添加量对产率影响不显著。当加入糠醇3 g(24 mmol),恒压15 V,最优条件为反应时间2.4 h, NaBr添加量为1.76 g,反应温度-10℃时,平均电流0.93 A,2,5-二甲氧基-2,5-二氢呋喃甲醇产率为67.9%。     

2,5-二溴甲基对苯二甲腈的合成

以对二甲苯为原料,分别通过芳环上的溴代、亲核取代及α-位溴代3步反应,合成了2,5-二溴甲基对苯二甲腈。以碘作催化剂,对二甲苯与液溴在二氯甲烷中于12℃严格避光条件下搅拌反应18 h,得到2,5-二溴对二甲苯;2,5-二溴对二甲苯与氰化亚铜在DMF中加热回流48 h得到2,5-二甲基对苯二甲腈;2,5-二甲基对苯二甲腈与N-溴代丁二酰亚胺(NBS)在四氯化碳中被偶氮二异丁腈催化反应16 h得到2,5-二溴甲基对苯二甲腈,各步收率分别为96.3%、87.5%、31.4%。借助正交实验优化了各步的反应条件:溴代n(B r2)∶n(p-xylene)=2.2∶1,c(p-xylene)=3.2 mol/L,反应温度12℃,反应时间18 h;亲核取代n(CuCN)∶n(2,5-二溴对二甲苯)=2.5∶1,c(2,5-二溴对二甲苯)=0.2 mol/L,反应温度155℃,反应时间48 h;α-位溴代n(NBS)∶n(2,5-二氰基对二甲苯)=2.1∶1,c(2,5-二氰基对二甲苯)=0.1 mol/L,反应温度80℃,反应时间16 h。并对各步产品进行了质谱和核磁共振氢谱表征。     

2-甲基-2,5-二甲氧基-2,5-二氢呋喃合成研究

2-甲基-2,5-二甲氧基-2,5=二氢呋喃是合成重要肉香味香料2-甲基-3-呋喃硫醇的原料,本文对其合成方法进行了研究,产率达到77.4％～87.0％。     

2,5-呋喃二甲酸的合成

以糠酸为原料,经过酯化、氯甲基化、水解、氧化得到2,5-呋喃二甲酸,并对各步反应中的工艺参数进行了优化。优化结果:酯化反应时间为10 h,氯甲基化反应温度为35～40℃,水解反应原料摩尔比为n(氢氧化钠)∶n(5-氯甲基-2-呋喃甲酸甲酯)=2.1∶1,氧化反应体系pH=7～8,反应总收率47.5%。按该工艺顺利完成了3次20 L扩试反应,平均收率可达47.3%,产品HPLC纯度大于99.4%。     

毛细管气相色谱法测定2,5-二氢呋喃含量

目的:建立气相色谱法测定2,5-二氢呋喃含量。方法:采用DB-624石英毛细管柱(30 m×0.53 mm×3μm),以乙腈为内标物,检测器:氢火焰离子化检测器,柱温:程序升温,初始温度45℃,保持5 min,以10℃/min升至250℃,保持10 min。进样器温度:220℃;检测器温度280℃;载气:氮气,流速3 mL/min,分流比:30∶1。结果:2,5-二氢呋喃在5.884~29.422 mg·mL~(-1)范围内与峰面积呈良好的线性关系,r=0.999 95;平均回收率(n=5)为100.03%。结论:本法灵敏度高、结果准确、重复性好,可用于2,5-二氢呋喃的质量控制。     

3-芳基-2,5-二甲基吡嗪类化合物的合成

利用Suzuki偶联反应以2,5-二甲基-3-氯吡嗪及取代苯硼酸为起始原料,合成了吡嗪衍生物,其结构经1H NMR、IR、EI-MS分析表征。结果表明:在氮气保护条件下,碱性二氧六环中,使用Pd(PPh3)4催化剂,除邻氰基苯硼酸因位阻效应收率较低外,其他产物的收率可达56%~94%。     

磺化碱熔法制备2,5-二甲基苯酚

通过对二甲苯磺化、碱熔法合成2,5-二甲基苯酚,研究了影响磺化、碱熔产物收率和纯度的因素。磺化时酸性滤液回收套用,可减少三废,降低生产成本。最佳磺化条件:缓慢把硫酸往对二甲苯中滴加,硫酸与对二甲苯摩尔比为1.6∶1,反应温度125℃,反应时间2.0 h,2,5-二甲基苯磺酸钠收率为96.87%,纯度为99.30%。碱熔时,通入水蒸气、添加抗氧剂和硬脂酸钠,增加了物料的流动性,提高了收率和纯度。最佳碱熔条件:将KOH、NaOH、潮品钠盐、抗氧剂1035(2,2'-硫代双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯])和硬脂酸钠混合后投入反应釜,NaOH和KOH质量比3∶2,抗氧剂1035为4 g,硬脂酸钠为9 g,330—340℃保温2.0 h,2,5-二甲基苯酚收率为92.70%,纯度为99.45%。     

酸性树脂催化1,4-丁烯二醇制备2,5-二氢呋喃

提出1,4-丁烯二醇在酸性条件下脱水关环制备2,5-二氢呋喃的反应机理。实验对照了磺酸基树脂D61、D72以及膦酸基树脂LSC-500的催化性能,在5小时的反应过程中,它们的催化活性均逐渐下降,其中D61活性最强,平均每克催化剂1小时转化2.96克1,4-丁烯二醇,D61和D72的收率逐渐下降,LSC-500的收率最高而且比较稳定,保持在80%以上。     

Dynamometer evaluation and engine wear characteristics of palm oil diesel emulsions

Dynamometer engine tests at steady-state conditions and a wear characteristics study were carried out on an indirect-injection diesel engine with palm oil diesel (POD) and its emulsions. The POD fuel was obtained in commercial form, and its emulsions were created by mixing POD fuel to contain 5 and 10% of water by volume. Variations in the engine’s performance characteristics were determined from the results of steady-state tests carried out at fifteen selected torque-speed matrix points of the engine’s performance map. The wear characteristics tests were performed by running the engine at half throttle setting for twenty hours for each fuel system. Then a desk-top comparison study was performed between the base-line fuel system of ordinary diesel (OD), POD, and its emulsions. Promising results have been obtained. Neither the lower cetane number of POD fuel nor its emulsification with water presented obstacles to the operation of the diesel engine during a series of steady-state engine tests and the twenty-hour endurance tests. Engine performance and fuel consumption for POD and its emulsions are comparable with those of OD fuel. Accumulations of wear metal debris in crank-case oil samples were lower with POD and its emulsions than with baseline OD fuel.     

Temperature effect on the viscosities of palm oil and coconut oil blended with diesel oil

One of the major difficulties in using crude vegetable oils as substitute fuels in diesel engines is their relatively high viscosities. Increasing the temperature of the crude vegetable oil, blending it with diesel oil, or the combination of both offers a simple and effective means of controlling and lowering the viscosities of vegetable oils. This work reports viscosity data, determined with a rotational bob-and-cup viscometer, for crude palm oil and cononut oil blended with diesel oil over the temperature range of 20–80°C and for different mixture compositions. All the test oil samples showed a time-independent newtonian type of flow behavior. The reduction of viscosity with increasing liquid temperature followed an exponential relationship, with the two constants of the equation being a function of the volume percentage of the vegetable oil in the mixture. A single empirical equation was developed for predicting the viscosity of these fuel mixtures under varying temperatures and blend compositions.     

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.     

高效缓蚀阻垢剂在小型柴油发电机循环水的应用

新型KA-1缓蚀阻垢剂用于小型柴油发电机组循环冷却水处理,解决了设备的结垢、腐蚀等问题,实际运行效果显著,经济效益和社会效益明显。     

A rapid test to measure performance,emission and wear of a diesel engine fueled with palm oil diesel

Results of performance, emission and tribological evaluations of palm oil methyl ester and its blends with conventional diesel in an automobile diesel engine test bed are presented. Polymerization and carbon deposits on the fuel injector were monitored. CO, CO₂, O₂, combustion efficiency and temperature of exhaust gases were also measured. Palm oil methyl ester and its blends have great potential as alternative diesel fuel. Performance and exhaust gas emission for palm oil methyl ester and its blends with conventional diesel are comparable with those of conventional diesel fuel. Palm oil methyl ester does not pose a severe environmental problem and will not deteriorate engine and bearing components.     

微乳柴油的性能研究

对由柴油、水及乳化剂组成的微乳柴油进行了电导率、粘度、粒径、稳定性及腐蚀性、密度和凝点等性能研究。结果表明:微乳柴油体系为牛顿型流体;温度升高,体系粘度降低;表面活性剂质量分数增大,粘度也逐渐增大;粘度的变化同水量的变化规律基本一致;粒径均在100nm左右;腐蚀性、密度和凝点均符合国家标准;室温时稳定期在6个月以上。     

Biodiesel from safflower oil and its application in a diesel engine

Safflower seed oil was chemically treated by the transesterification reaction in methyl alcohol environment with sodium hydroxide (NaOH) to produce biodiesel. The produced biodiesel was blended with diesel fuel by 5% (B5), 20% (B20) and 50% (B50) volumetrically. Some of important physical and chemical fuel properties of blend fuels, pure biodiesel and diesel fuel were determined. Performance and emission tests were carried out on a single cylinder diesel engine to compare biodiesel blends with petroleum diesel fuel. Average performance reductions were found as 2.2%, 6.3% and 11.2% for B5, B20 and B50 fuels, respectively, in comparison to diesel fuel. These reductions are low and can be compensated by a slight increase in brake specific fuel consumption (Bsfc). For blends, Bsfcs were increased by 2.8%, 3.9% and 7.8% as average for B5, B20 and B50, respectively. Considerable reductions were recorded in PM and smoke emissions with the use of biodiesel. CO emissions also decreased for biodiesel blends while NO_x and HC emissions increased. But the increases in HC emissions can be neglected as they have very low amounts for all test fuels. It can be concluded that the use of safflower oil biodiesel has beneficial effects both in terms of emission reductions and alternative petroleum diesel fuel.     

Performance and emissions of bus engine using blends of diesel fuel with bio-diesel of sunflower or cottonseed oils derived from Greek feedstock

An experimental investigation is conducted to evaluate the use of sunflower and cottonseed oil methyl esters (bio-diesels) of Greek origin as supplements in the diesel fuel at blend ratios of 10/90 and 20/80, in a fully instrumented, six-cylinder, turbocharged and after-cooled, direct injection (DI), Mercedes-Benz, mini-bus diesel engine installed at the authors’ laboratory. The tests are conducted using each of the above fuel blends, with the engine working at two speeds and three loads. Fuel consumption, exhaust smokiness and exhaust regulated gas emissions such as nitrogen oxides, carbon monoxide and total unburned hydrocarbons are measured. The differences in the measured performance and exhaust emissions from the baseline operation of the engine, i.e., when working with neat diesel fuel, and the two bio-diesels are determined and compared. Theoretical aspects of diesel engine combustion with the differing physical and chemical properties of these blends, aid the correct interpretation of the observed engine behavior.     

The formation of deposits from oil under conditions pertinent to diesel engine pistons

The production of deposits from oil on various materials has been studied under conditions pertinent to the ring zone of a diesel engine piston. Deposition is found to occur only as a result of oxidation, and metal catalysed free radical reactions in the liquid phase appear to be responsible for the problem. Metal species removed from the surface are the most active promoters and these may be deactivated by heavy deposition (encapsulation) or by the addition of deactivating complexing agents.     

Performance of a diesel generator fuelled with palm oil

Pure palm oil may be employed in diesel engines as an alternative fuel. Engine performance and emissions were influenced by basic differences between diesel fuel and palm oils such as mass based heating values, viscosity, density and molecular oxygen content. The high viscosity of palm oil resulted in poor atomisation, carbon deposits, clogging of fuel lines and starting difficulties in low temperatures. When heated at 100 °C palm oil presented lower viscosity, better combustion and less deposits. Tests were conducted in a naturally aspirated MWM 229 direct injection four-stroke 70 kW diesel-generator fueslled with 100% palm oil.