Valorisation of waste fractions from autohydrolysis of selected lignocellulosic materials

Non‐isothermal processing of lignocellulosic materials in aqueous media (autohydrolysis reaction) under mild conditions leads to solutions containing valuable chemicals (oligosaccharides, sugars and acetic acid) and other, undesired, compounds (belonging to the extractive and acid‐soluble lignin fractions) which have to be removed in further purification treatments. Liquors obtained by non‐isothermal autohydrolysis of Eucalyptus globulus wood and corncobs under a variety of operational conditions were extracted with ethyl acetate in order to remove non‐saccharide components, and the suitability of the fraction dissolved in the organic phase was assayed for possible utilisation as an antioxidant. The yield and antioxidant activity of ethyl acetate extracts (measured by the α,α‐diphenyl‐β‐picrylhydrazyl (DPPH) radical scavenging capacity) showed a strong dependence on the autohydrolysis conditions. The antioxidant activity of extracts obtained under selected operational conditions compared well with synthetic antioxidants. © 2003 Society of Chemical Industry     

Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry     

过氧化甲乙酮合成研究

论述了过氧化甲乙酮的合成方法，用阳离子交换树脂催化剂代替传统的无机酸催化剂。考察了离子交换树脂用量、反应温度对反应产率、活性氧含量的影响及溶剂对产品稳定性的影响。     

新型香料苹果酯-B的合成

以硫酸高铈为催化剂,通过乙酰乙酸乙酯和1,2-丙二醇反应合成了苹果酯-B,研究了各有关因素对产品收率的影响。实验表明,硫酸高铈是合成苹果酯-B的良好催化剂,在酯醇物质的量比为1∶1.25、催化剂用量为0.3g/0.1mol乙酰乙酸乙酯、环己烷10mL、反应时间2h的条件下,苹果酯-B的收率可达91.5%。     

An attempt to compare the performance of bioscrubbers and biotrickling filters for degradation of ethyl acetate in gas streams

This study presents a comparison of the efficiency of a bioscrubber and a biotrickling filter (BTF) for the removal of ethyl acetate (EA) vapour from a waste gas stream, under the same operating conditions. The maximum EA elimination capacity achieved in the bioscrubber was 550 g m^?3 h^?1 with removal efficiency higher than 96%. For higher EA loadings the bioscrubber was oxygen limited, which caused incomplete EA biodegradation. When pure oxygen was fed to the bioscrubber at a rate of 0.02 L min^?1, the bioscrubber recovered and could treat higher EA loadings without any oxygen limitation. The BTF achieved EA elimination capacity of 600 g m^?3 h^?1 with removal efficiency higher than 97% and the dissolved oxygen concentration remained substantially higher than in the bioscrubber. However, severe channelling and blockage of the spray nozzle occurred due to the excessive biomass growth. Overall, the bioscrubber system was easier to operate and control than the BTF, while an enhancement of the oxygen mass transfer in the bioscrubber could potentially increase its performance by up to three times. Copyright © 2005 Society of Chemical Industry     

甲基丙烯酸三氟乙酰氧乙酯的聚合

对甲基丙烯酸三氟乙酰氧乙酯(TFAOEMA)的阴离子聚合及原予转移自由基聚合进行了研究。常用的阴离于引发剂如丁基锂、1，1-二苯基已基锂等很难引发TFAOEMA的阴离子聚合，而碱性较弱的引发剂如三乙基铝却容易引发，且产率较高。以氯化亚铜、五甲基二乙基三胺、溴代丙酸乙酯为引发体系的TFAOEMA的本体原子转移自由基聚合符合活性聚合特征。但在四氢呋喃为溶剂的原子转移自由基聚合中却存在活性中心失活现象。以末端含卤素的聚甲基丙烯酸甲酯为大分子引发剂，引发TFAOEMA的原子转移自由基聚合，得到了含氟双嵌段聚合物。     

New HPLC Method to Determine Ethyl Carbamate in Alcoholic Beverages Using Fluorescence Detection

ABSTRACT: A new methodology to the quantification of ethyl carbamate (EC) has been developed. This method allows the analysis by HPLC of ethyl carbamate in samples of wine, fortified wine, and wine brandy, by a pre-column derivatization with 9-xanthydrol, and fluorescence detection. This does not require previous sample extraction or concentration. The method presents an average recovery of 96% among samples studied, a detection limit of 4.2μg/L, and an average intermediate precision of 6.3%. The comparison of the results obtained for EC analysis on the same wine brandy samples by GC/MS and HPLC are statistically indistinguishable with 97.5% probability. The results of the analysis of 42 samples are presented.     

Process conditions for separating fatty acid esters by supercritical CO2

The solubilities of ethyl palmitate, ethyl oleate, ethyl eicosapentaenoate (EPA) and ethyl docosahexaenoate (DHA) in supercritical carbon dioxide were determined by a continuous flow method. The solubilities of fatty acid ethyl esters increased with pressure and decreased as the temperature was increased. An empirical equation, similar to Chrastil's equation, was used to describe the relationship between solute solubility and the density of carbon dioxide. The empirical equation was further used to qualitatively estimate the separation efficiency of isolating EPA and DHA ethyl esters from fatty acid esters. The operating conditions yielding high solubility gave fast extraction rate but resulted in low separation efficiency. Experiments were conducted to separate ethyl EPA and ethyl DHA from a model mixture containing four fatty acid ethyl esters and from esterified squid visceral oil. The experimental data compared closely with the calculated values.     

NMR studies of poly(2-hydroxy ethyl methacrylate-co-2-vinyl pyridine)

Copolymers of 2-hydroxy ethyl methacrylate-2-vinyl pyridine (H/V) of different composition were synthesized by free radical bulk polymerization using azobisisobutyronitrile (AIBN) as an initiator under nitrogen atmosphere. The copolymer compositions were calculated from ¹H NMR spectra. The reactivity ratios for H/V copolymers obtained from a linear Kelen-Tudos method (KT) and nonlinear error-in-variables method (EVM) are r_H = 0.50 ± 0.10, r_V = 1.04 ± 0.08 and r_H = 0.55, r_V = 1.06 respectively. The complete spectral assignment of methine, methylene, methyl, carbonyl, and aromatic carbon regions in term of compositional and configurational sequences of H/V copolymers were done with the help of ¹³C{¹H} NMR, distortionless enhancement by polarization transfer (DEPT), two-dimensional heteronuclear single quantum coherence (HSQC) along with total correlated spectroscopy (TOCSY). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

溶胶-凝胶法制备磷钨酸-硅胶催化合成苹果酯

采用溶胶-凝胶法制备了一系列磷钨酸-硅胶催化剂(PW/SG),考察了该催化剂催化乙酰乙酸乙酯与乙二醇液相缩合制备苹果酯的反应性能。实验结果表明,PW质量分数为40%时的PW/SG催化剂表现出最佳的催化活性;40%PW/SG催化剂制备苹果酯的最佳工艺条件为:n(乙酰乙酸乙酯)∶n(乙二醇)=1∶1.2,催化剂用量占反应物质量的0.36%,带水剂环己烷用量占反应物体积的30%,反应温度383K,反应时间90min;在此条件下,乙酰乙酸乙酯的转化率可达95.5%,苹果酯的选择性大于97%;催化剂稳定性实验表明,经5次重复使用,40%PW/SG催化剂的活性基本保持不变,乙酰乙酸乙酯转化率稳定在95.0%左右。