Role of Acetic Acid Added to the Reaction Media for the Enantio-differentiating Hydrogenation of Methyl Acetoacetate Over a Tartaric Acid-modified Nickel Catalyst

The role of acetic acid added to the reaction media for the enantio-differentiating hydrogenation of methyl acetoacetate over a (R,R)-tartaric acid-in-situ-modified nickel catalyst was studied from the viewpoint of the hydrogenation rate during repeated runs. The hydrogenation of methyl acetoacetate on the “enantio-differentiating sites” of a tartaric acid-modified nickel catalyst was specifically accelerated by the acetic acid added to the reaction media to increase the enantio-differentiating ability of the catalyst. In order to increase the enantio-differentiating ability, the addition of acetic acid to the reaction media was required in each run during the repeated use of the catalyst.     

醋酸生产工艺选择

介绍醋酸生产的几种工艺路线，将巴斯夫工艺、BP／孟山都工艺及UOP/千代田工艺进行比较，寻找适合我厂的醋酸生产工艺。     

对羟基苯甲酸酯的催化剂研究

综述了固体超强酸TiO2/SO42-,磷钨、硅钨杂多酸及固载杂多酸盐TiSiW12O40/TiO2,浓硫酸(微波常压法),Lewis酸(FeCl3·6H2O,Fe2(SO4)3·xH2O)等几种不同催化剂催化合成对羟基苯甲酸酯的实验结果.分析各种固体催化剂对该酯化反应的催化活性、选择性、重复使用性能及使用范围.     

Phase diagrams for oil/methanol/ether mixtures

One-phase transmethylations of vegetable oils with methanol to form methyl esters occur considerably faster than conventional two-phase reactions. Addition of simple ethers is an efficient method for producing a single phase. Ternary phase diagrams have been determined at 23°C for oil/methanol/ether mixtures; these are useful when applying the one-phase method across a wide range of conditions. Soybean, canola, palm, and coconut oils were used in combination with five ethers, namely, tetrahydrofuran (THF), 1,4-dioxane (DO), diethyl ether (DE), diisopropyl ether (DI), andtert-butyl methyl ether (TBM). All five ethers can produce miscibility for all methanol/oil compositions. The ether/methanol volumetric ratios required for miscibility at a methanol/soybean or canola oil volumetric ratio of 0.20 (5.4 molar ratio) at 23°C are: THF, 1.15; DO, 1.60; DE, 1.38 DI, 1.57; and TBM, 1.57. For THF, this results in one-phase mixtures that contain 65 vol% oil. Soybean and canola oil form identical diagrams. Palm oil requires slightly less ether at the lower methanol concentrations, but coconut oil requires considerably less across the whole concentration range. Acid-catalyzed reactions, when performed at the boiling point of the most volatile component, require less ether than predicted from the diagrams.     

Low-temperature properties of triglyceride-based diesel fuels: Transesterified methyl esters and petroleum middle distillate/ester blends

This work examines low-temperature properties of triglyceride-based alternate fuels for direct-injection compression-ignition engines. Methyl esters from transesterified soybean oil were studied as neat fuels and in blends with petroleum middle distillates (No. 1 or No. 2 diesel fuel). Admixed methyl esters composed of 5–30 vol% tallowate methyl esters in soyate methyl esters were also examined. Pour points, cloud points, and kinematic viscosities were measured; viscosities at cooler temperatures were studied to evaluate effects of sustained exposure. Low-temperature filterability studies were conducted in accordance with two standard methodologies. The North American standard was the low-temperature flow test (LTFT), and its European equivalent was the cold-filter plugging point (CFPP). With respect to cold-flow properties, blending methyl esters with middle distillates is limited to relatively low ester contents before the properties become preclusive. Under most conditions, cold-flow properties were not greatly affected by admixing the methyl esters with up to 30 vol% tallowate (before blending). Least squares analysis showed that both LTFT and CFPP of formulations containing at least 10 vol% methyl esters are linear functions of cloud point. In addition, statistical analysis of the LTFT data showed a strong 1:1 correlation between LTFT and CP. This result may prove crucial in efforts to improve low-temperature flow properties of alternate diesel fuels that contain methyl esters derived from triglycerides.     

5-硝基愈长木酚的合成

5-硝基愈创木酚作为高效、低毒植物调节剂,一直倍受关注.它的合成目前主要采用愈创木酚硝化法,以发烟硝酸和冰醋酸混酸做硝化剂.本文由愈创木酚为起始原料,经酚酯化、硝化、水解等步骤合成了5-硝基愈刨木酚.酚酯化采用碱催化法,收率可达96%以上;硝化反应则采用乙酸酐和硝酸混合物为硝化剂.5-硝基愈创木酚最高收率可达到91%.     

脂肪酸甲酯处理含苯胺工业废水

采用正交实验设计研究了用脂肪酸甲酯处理工业苯胺废水的条件。实验表明:在影响苯胺废水萃取效果的诸因素中,影响大小的顺序为pH值、油水相比、溶液初始浓度和温度。在pH值=7,油水相比为2∶1,20℃的最佳萃取条件下,高浓度苯胺废水经萃取剂脂肪酸甲酯三级萃取后,苯胺去除率达99.98%。     

红色基RL的合成工艺改进

详细研究了红色基RL(对硝基邻甲苯胺,简称RL)的合成工艺,对传统的合成工艺进行了改进,通过用乙酐作氨基保护试剂,混酸硝化,酸性水解等分步操作合成了RL。与传统方法相比,采用乙酐作氨基保护试剂,高温酰化,减少了乙酐用量;用混酸硝化,增强了硝化能力,提高了收率。分别研究了乙酐用量、反应时间、反应温度以及混酸配比对RL收率及熔点的影响规律,得到了反应的较佳条件。采用乙酐酰化分步合成法,RL总收率为56·4%(以邻甲苯胺计),氨基值为91·26%。     

Sorption,diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) in water–acetic acid mixtures

Sorption, diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) were investigated for water–acetic acid mixtures by using a gravimetric method at 30, 40, and 50°C. The membranes were characterized by X‐ray diffraction and Fourier transform infrared techniques. Concentration‐independent diffusion coefficients were obtained by applying Fick's relationship before completion of equilibrium sorption. Permeation coefficients were calculated from sorption and diffusion coefficients. Concentration profiles of liquids were computed considering the sheet geometry for the membrane by solving Fick's equation under suitable boundary conditions. Arrhenius activation parameters were computed for the transport processes. Experimental results and calculated quantities were discussed to understand membrane–solvent interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1139–1150, 2004     

取代2-四氢萘酮的一步合成新方法研究

本文介绍了一步法制备取代2-四氢萘酮的新方法,与常规合成方法相比,该法具有明显的优点:不需要先将羧酸转化成酰氯,避免了三氯化铝以及含氯溶剂的应用,并使催化剂得以循环利用。因此,该方法安全、环保,有望取代常规的付-克反应在工业上的应用。