A catalyst-free novel synthesis of diethyl carbonate from ethyl carbamate in supercritical ethanol

Diethyl carbonate has been synthesized via the alcoholysis of ethyl carbamate in supercritical ethanol under catalyst-free conditions.The influences of various parameters such as reaction temperature,reaction time,reaction pressure,ethanol/ethyl molar ratios and reaction loading volume on the yield of DEC were studied systematically.The experimental results indicated that the alcoholysis of ethyl carbamate was greatly improved in supercritical ethanol.The optimal reaction conditions were as follows：a reaction temperature of 573 K,a reaction time of 30 min,a reaction pressure of 13.2 MPa,an ethanol/ethyl carbamate molar ratio of 10 and a reactor loading volume of 285 μL respectively.The optimal yield of DEC was 22.9%.     

苯胺与氨基甲酸甲酯合成苯氨基甲酸甲酯反应研究

以无水氯化锌为催化剂,考察了温度、时间、催化剂含量及原料配比等条件对合成反应的影响,确定了最优化反应条件,并初步探讨了反应机理.最佳反应条件下MPC收率可达89.90%,选择性为99.76%.     

苯基脲与甲醇合成苯氨基甲酸甲酯的研究

采用苯基脲与甲醇反应合成了苯氨基甲酸甲酯,考察了不同催化剂、原料配比及反应工艺条件的影响,确定了适宜的合成条件,并根据产物分布对催化反应机理进行了初步探讨.结果表明,以PbO为催化剂,于140℃反应4h后,苯基脲转化率为95.2%,苯氨基甲酸甲酯收率为80.6%.     

Comparison and optimisation of biodiesel production from <Emphasis Type="Italic">Jatropha curcas</Emphasis> oil using supercritical methyl acetate and methanol

In this study, biodiesel has been successfully produced by transesterification using non-catalytic supercritical methanol and methyl acetate. The variables studied, such as reaction time, reaction temperature and molar ratio of methanol or methyl acetate to oil, were optimised to obtain the optimum yield of fatty acid methyl ester (FAME). Subsequently, the results for both reactions were analysed and compared via Response Surface Methodology (RSM) analysis. The mathematical models for both reactions were found to be adequate to predict the optimum yield of biodiesel. The results from the optimisation studies showed that a yield of 89.4 % was achieved for the reaction with supercritical methanol within the reaction time of 27 min, reaction temperature of 358°C, and methanol-to-oil molar ratio of 44. For the reaction in the presence of supercritical methyl acetate, the optimum conditions were found to be: reaction time of 32 min, reaction temperature of 400°C, and methyl acetate-to-oil molar ratio of 50 to achieve 71.9 % biodiesel yield. The differences in the behaviour of methanol and methyl acetate in the transesterification reaction are largely due to the difference in reactivity and mutual solubility of Jatropha curcas oil and methanol/methyl acetate.     

Preparation of alkaline polymer catalyst by radiation induced grafting for transesterification of triacetin under neural network optimized conditions

A simple and flexible method was used to develop new alkaline polymer catalyst through radiation induced grafting of glycidylmethacrylate (GMA) onto polyethylene/polypropylene (PE/PP) nonwoven sheet followed by amination reaction and alkalisation. The chemical structure and morphology of catalyst was evaluated by Fourier transform-infrared (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermal gravimetric analyzer (TGA). The catalyst was examined for the transesterification of triacetin/methanol mixtures in a batch mode and the obtained methyl ester was detected by GC-MS. In order to optimize the reaction parameters towards getting the higher yield, an artificial neural network (ANN) was used to develop a non-linear model correlating the four independent reaction parameters including catalyst dosage, triacetin/methanol molar ratio, reaction time and temperature. The maximum conversion obtained via the simulated annealing (SA) algorithm was 86.2% at the optimal conditions of 5.01 wt% catalyst dosage, triacetin/methanol 1:12 molar ratio, 8 h reaction time and 62.8°C temperature. Upon using these optimal conditions in the experimental reaction, the conversion of as high as 85% was achieved. These results suggest that the simply modified low cost PE/PP fibrous sheet has a potential to catalyze biodiesel production. Moreover, the combined ANN-SA modelling method is highly effective in predicting the conversion of transesterification reaction and optimizing its parameters.     

基于氯化镁饱和溶液中固定化脂肪酶Lipozyme TL IM催化光皮树油脂合成生物柴油

基于氯化镁饱和溶液反应体系中,对采用固定化脂肪酶Lipozyme TL IM催化光皮树油脂转化为生物柴油的工艺进行了研究。考察了固定化脂肪酶Lipozyme TL IM催化光皮树油转酯化的工艺中甲醇的用量、固定化脂肪酶的添加量、摇床的转速和反应时间对生物柴油产率的影响。实验结果表明,采用氯化镁饱和溶液反应体系,在醇油摩尔比为3∶1,固定化酶Lipozyme TL IM用量为光皮树油质量的20%,摇床转速为150 r/min,反应8 h时,生物柴油产率最高,达到86.5%。与传统的三步甲醇醇解或者有机溶剂反应体系比较,采用的氯化镁饱和溶液体系的酶稳定性更好,反应效率更高,有效地解决了酶在甲醇中失活的问题,生产成本低,可成为生产生物柴油的新工艺。     

Treatment of acidic palm oil for fatty acid methyl esters production

Acidic crude palm oil (ACPO) produced from palm oil mills with an acid value of 18 mg g⁻¹ was considered to be a possible feedstock for biodiesel production. Due to its high acidity, conventional transesterification cannot be applied directly for biodiesel production. Methane sulphonic acid (MSA, CH₃SO₃H) is used to reduce the acidity prior to the alkaline transesterification reaction. The laboratory-scale experiments involved an MSA to ACPO dosage of 0.25–3.5 %, a molar ratio (methanol to ACPO) from 4: 1 to 20: 1, reaction temperature of 40–80°C, reaction time of 3–150 min, and stirrer speed of 100–500 min⁻¹. The optimum esterification reaction conditions were 1 % of catalyst to ACPO, with a molar ratio of methanol to ACPO of 8: 1, a stirring speed of 300 min⁻¹, for 30 min and at 60°C. Under these conditions, the FFA content was reduced from 18 mg g⁻¹ to less than 1 mg g⁻¹ and with a yield of 96 %. The biodiesel produced met the EN14214 standard specifications. MSA was recycled for three times without losing its activity. The biodiesel produced in a two-stage process has a low acid value (0.14 mg g⁻¹).     

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     

Preparation of biodiesel catalysed by KF/CaO with ultrasound

Biodiesel, chemically consists of fatty acid methyl ester (FAME) produced by methanolysis of natural triglycerides, such as animal fats and vegetable oils, is a kind of biomass energy, which is renewable and ecofriendly. In this article, KF/CaO was used as solid base catalyst for transesterification of soya bean oil and methanol, while ultrasound as supplementary means. Compared to mechanical stirring, ultrasound treatment is an effective method to increase the yield of FAME and shorten reaction time. By single-factor method, the optimisation of reaction conditions has been studied. The research showed that the optimum reaction conditions were: w(catalyst)/w(oil): 3%, reaction temperature: 65°C, n(methanol)/n(oil): 12, reaction time: 1?h, sound intensity: 1.01?W?cm(-2), frequency: 20?kHz, the yield of FAME could be 97%.     

废茶油的精制及其合成生物柴油的研究

本文以废茶油为原料,经过脱胶脱酸等预处理后与甲醇进行酯交换反应制取生物柴油.探讨了反应时间、反应温度、醇-油摩尔比和催化剂用量等因素对废茶油-甲醇酯交换反应的影响,并且采用正交实验优化合成条件,确定了反应的最佳操作条件以及影响反应的关键因素.研究结果表明,酯交换反应进行的最佳反应条件为:醇油摩尔比为25:1、催化剂用量为油重的1.0%、反应时间为30min、反应温度为60℃,茶油酸甲酯产率77.34%.     

1-萘胺氧化合成1,4-萘醌

研究了在乙酸中,用H2O2氧化1-萘胺合成1,4-萘醌的新方法。 考察了反应温度、反应时间、1-萘胺与H2O2摩尔比、硫酸和H2O2质量分数等因素对产品收率的影响。 得到较优的反应条件为：1-萘胺与H2O2摩尔比为1∶10、H2O2质量分数为5%、硫酸质量分数为45%、反应温度为80 ℃、反应时间为3 h。 在此条件下,1,4-萘醌的收率为52.2%。 该方法具有操作简单、反应时间短和产物易分离等优点。     

微波促进酸性离子液体催化水杨酸酯化

用自制的硫酸氢1-甲基-3-(3-磺酸基丙基)咪唑([MIMPS]HSO4)酸性离子液体作为水杨酸与醇的酯化反应催化剂,考察了温度、时间、物料配比和离子液体用量等因素对酯化反应的影响,优化的最佳反应条件为: 微波辐射时间20 min,反应温度95 ℃,醇与酸摩尔比3∶1(水杨酸的量为0.02 mol),[MIMPS]HSO4用量10 mmol,水杨酸甲酯的产率和选择性分别为91.9%和99.0%。 离子液体回收循环使用4次,催化效率不变。 与热催化酯化反应相比,微波辐射可缩短反应时间;水杨酸与不同碳链醇的酯化产率随着碳链的增加而降低,同碳链的伯醇酯化率比仲醇高。     

盐酸催化合成α-萘乙酸甲酯

以α-萘乙酸、甲醇为原料,以浓盐酸为催化剂,通过酯化反应合成了植物生长调节剂萘乙酸甲酯。通过正交设计讨论了醇酸摩尔比、催化剂用量、反应时间等因素对酯化产率的影响。在α-萘乙酸50mmol,n(甲醇)：n(α-萘乙酸)=25,催化剂用量为α-萘乙酸质量的17％,反应时间2．0h,酯化温度65℃～69℃的最佳反应工艺条件下,产率97．4％。     

Conversion of phenylacetonitrile in supercritical alcohols within a system containing small volume of water

The reaction of phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water was studied. The effects of various operating conditions, such as reaction temperature, reaction time, the mole ratio of phenylacetonitrile/water/methanol or ethanol on the product yield were systematically investigated. The optimal yield of methyl phenylacetate for phenylacetonitrile in supercritical methanol in a system containing a small volume of water was 70 % at 583 K and 2.5 h. The optimal yield of ethyl phenylacetate for phenylacetonitrile in supercritical ethanol with a small volume of water was 80 % at 583 K and 1.0 h. At the same time, a feasible mechanism was proposed for phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water.     

脂肪酸在超临界甲醇中的酯化反应研究

超临界甲醇中的酯化和酯交换反应是利用植物油、动物油或废油脂制备生物柴油的新工艺.它的最大特点是不需要添加催化剂,超临界甲醇既是反应媒介,又是反应物.     

含钒杂多酸催化发烟硫酸中甲烷液相部分氧化反应

 以H5PV2Mo10O40 为催化剂,在发烟硫酸中进行了甲烷液相部分氧化,考察了催化剂用量、反应温度、反应时间和发烟硫酸浓度等工艺条件对反应收率的影响. 甲烷在反应中首先转化为硫酸甲酯,硫酸甲酯随后水解为甲醇. 对于甲烷液相部分氧化反应,发烟硫酸中游离的SO3是非常重要的影响因素. 在工艺条件为催化剂用量7.0 mmol, 反应温度473 K, 反应压力3.5 MPa, 反应时间3 h和发烟硫酸中SO3含量50%时,甲烷转化率可达48.5%, 目的产物甲醇收率为41.5%.     

Transesterification of palm oil using supercritical methanol with co-solvent HCFC-141b

The transesterification of palm oil in supercritical methanol has been investigated without using any catalyst. HCFC-141b was used as co-solvent to reduce the molar ratio of methanol to palm oil under the milder conditions. The reaction was carried out in a flow-type tubular reactor. The residence time was fixed at 40 min. When the molar ratio of methanol to palm oil was set to 20:1 at 325 °C and 35 MPa, the optimum molar ratio of methanol to co-solvent was found to be 20:1. Addition of HCFC-141b increased FAME production even at the lower molar ratio of methanol to palm oil. In addition, a similar FAME content was obtained under the milder conditions (5 MPa lower pressure) compared with conditions without co-solvent at higher pressure. The role of HCFC-141b in the transesterification reaction under supercritical conditions was investigated.     

采用Pd／树脂催化剂的轻汽油临氢醚化反应研究

研究了催化裂化轻汽油临氢醚化工艺,以降低催化裂化汽油的烯烃含量并提高辛烷值,制备了Pd负载D005阳离子交换树脂催化剂,该催化剂具有同时催化二烯烃选择性加氢和步碳烃与甲醇醚化的功能。考察了遗金属负载量和反应择醚收率的影响,在反应温度343K、压力1．5Mpa,n（甲醇）/ n(叔碳烯烃）比＝1．1、n（氢）／n（二烯）比＝2、液时空速3/h的条件下,醚收率达55．32％。2016h的寿命试验表明,该催化剂活性稳定,可以长周期使用。     

微波-超声复合场辅助水介质砜类化合物合成

发展了一种微波-超声复合场下绿色高效合成砜类化合物的简便方法。 以芳甲基氯和苯亚磺酸钠为原料,以水为反应介质,在微波-超声复合场辅助下合成了一系列芳甲基苯基砜。 通过考察微波功率、超声功率、原料投料比、溶剂体积和反应时间等因素的影响,得出了苄基氯与苯亚磺酸钠之间模型反应的最优反应条件:微波功率为40 W,超声功率为50 W,苄基氯与苯亚磺酸钠的摩尔配比为1:3,反应时间为5 min。 在此条件下合成的苄基苯基砜产率为83%。 相比常规油浴条件,在微波-超声复合场的强化下反应速率提升了约42倍。 该方法具有较好的底物适应性,成功合成了23种砜类化合物。     

两相溶剂萃取黄连木籽油制备生物柴油

以黄连木籽为原料,采用乙醇/异己烷两相不互溶溶剂对其进行萃取处理.考察了乙醇／异己烷体积比、萃取温度和萃取时间对萃取过程的影响.通过实验确定最佳的萃取条件为,黄连木仁粉50 g,乙醇异己烷总体积300 mL,乙醇/异己烷体积比为50∶50,萃取温度40℃,萃取时间30 min.在此条件下,黄连木籽油出油率达到99.5％...