新型绿色化学反应介质的研究进展

综述了绿色化学在反应介质方面的研究进展。新型的有机合成反应介质主要包括离子液体、超临界流体、水溶剂及微波无溶剂技术。这些新型反应介质不仅可以取代传统的挥发性有毒有害有机溶剂,同时还可提高反应的活性和选择性,加速反应的进行,且有利于催化剂的回收利用及产品的分离。新型绿色化学反应介质是实现有机合成绿色化的重要途径。     

青藏高原北缘P波波形线性度的动态跟踪及其变化的物理机制初探

利用数字化近震Ｐ波波形资料，追踪研究了青藏高原北缘１９９０年２月～１９９５年８月Ｐ波波形时间线性度的变化过程。发现该区较大地震发生前线性度有一定程度的下降现象。分析认为：大震前孕震区应力场的不均匀分布可使通过孕震区及其周缘的地震波产生频散，可能是较大地震前波形时间线性度下降的物理本质     

水环境中铬的存在形态及迁移转化规律

综合评述了水环境中铬的存在形态、污染特征及其迁移转化规律的研究现状.水体中铬主要是三价和六价,存在形态分为溶解态、离子交换态、有机结合态、无机沉淀态、残留态,迁移转化过程主要是水解、沉淀、络合、吸附和氧化还原等.对铬在水体中迁移和转化过程的动力学模型进行了论述.     

室内有毒易爆气体的检测

随着城市生活水平的提高,室内装修装饰日益普及.各种新材料的引入,使得室内的各种有害气体总量日益增加.长期生活在这样的环境下,会对人体健康产生极为不利的影响.居民生活用煤气,在给人们生活带来便利的同时,作为一种可燃性、有毒气体,也具有极强的危害性.因此,研制一种能检测多种有害气体的实用仪器,具有很大的应用价值.本仪器为便携式多功能仪器,采用可充电电池供电,可以检测ppb的挥发性气体,显示气体浓度值,也可检测煤气,并具有声光报警功能.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

土壤重金属钝化修复剂生物炭对镉的吸附特性研究

目前以生物炭为代表的生物质对重金属的吸附表现出良好的应用前景.为确定生物炭对溶液中镉的吸附性能,选用由棉花秸秆制备的生物炭,研究吸附等温线、吸附动力学以及温度、pH和离子强度等对生物炭吸附Cd2+的影响.研究表明,生物炭对Cd2+的吸附可以用Freundlich等温线较好地拟合,在不同温度下其饱和吸附量分别为9.738 mg.g-1(288.15 K)、10.14 mg.g-1(298.15 K)、10.40 mg.g-1(308.15 K)和10.71 mg.g-1(318.15 K),热力学参数表明生物炭吸附Cd2+的过程是自发的吸热过程;吸附动力学过程符合二级动力学模型,在40 min即可达到平衡;pH对生物炭吸附Cd2+的影响较大,在pH2～8范围时,生物炭对Cd2+的吸附量随pH的增加先上升后下降;生物炭对Cd2+的吸附量随着溶液离子强度的增大呈降低趋势.该项研究可为生物炭在土壤重金属污染修复中的应用提供一定的理论基础.     

红枫湖后午沉积物磷形态与生物有效磷的垂向分布及疏浚深度推算

以贵州红枫湖后午重污染沉积物为研究对象,对沉积物柱芯按每2cm分层,研究了沉积物中含水量、孔隙度、磷形态与生物可利用磷的垂向分布规律,并推算出污染沉积物的环保疏浚深度。结果表明,含水量和孔隙度在沉积物上部30cm内递减,30cm往下剧减。沉积物中不同磷形态、生物有效磷的垂向分布规律相似,分别在6～12cm和15～16cm两个层段出现了转折,在底部30cm后趋于稳定。沉积物表层16cm中NaOH-P和有机磷含量的剖面变化,反映了红枫湖近20年来水环境富营养化的演变过程。根据含量拐点法和环保疏浚经济成本的考虑,可将后午区域疏浚层的深度定为30cm。     

Kinetics of selective catalytic reduction of NO by NH3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results show that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3, respectively, at 350-450℃. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.     

咪唑型离子液体对小鼠的急性毒性

采用寇氏改良法研究了咪唑型离子液体对小鼠的急性毒性,并考察了烷基侧链长度对其毒性的影响,同时采用HE染色法观察了其对小鼠肝脏的毒性.结果表明,4种咪唑型离子液体([C10mim]Br、[C12mim]Br、[C14mim]Br和[C18mim]Br)对小鼠肝脏均有损伤,其LD50值在98.91～220.16 mg·kg...     

不同离子对黑土胶体在土壤中运移的影响

黑土样品采自于黑龙江海伦市,提取胶体并对其主要理化性质进行定性定量表征,通过淋滤实验研究胶体在土柱中的运移特征以及不同离子及其强度对胶体运移的影响。结果显示:所提取胶体粒径与理论计算基本吻合,粒径主要分布在2~5μm;当pH由4上升到9时,胶体的zeta电位则由-26.43mV降低到-34.52mV;红外光谱显示胶体颗粒的有机机团主要为-OH、CH-、C=O、多糖;X射线衍射表明其主要矿物组成是石英(56.9%)。不同离子及其强度对胶体的在土壤中的运移有较为明显的影响,当pH由4增加到9时,k值由6.020×10-4降低至3.858×10-4,Ca2+、K+、Na+当离子强度由0.5mmol/L变化到0.001mmol/L时,k值分别由6.087×10-4降低至4.024×10-4、5.518×10-4降低至3.818×10-4、5.401×10-4降低至4.109×10-4。