Photochemical behaviour of musk tibetene

BACKGROUND: Synthetic musk compounds are widely used as additives in personal care and household products. The photochemical degradation of musk tibetene in aqueous solutions or in acetonitrile/water mixtures under different conditions was studied in order to assess its environmental fate. METHODS: Musk tibetene dissolved (or suspended) in water and/or acetonitrile/water mixtures was irradiated at different times by UV-light and by solar light. The irradiation mixtures were analyzed by NMR and TLC. The photoproducts formed were identified by GC-MS and NMR data. RESULTS: The experimental results indicated that musk tibetene was photodegradable in water or acetonitrile/water mixtures with half-life reaction times close to 20 minutes. The irradiation mixtures were separated by chromatographic techniques yielding three photoproducts (3,3,5,6,7-pentamethyl-4-nitro-3H-indole, 3,3,5,6,7-pentamethyl-4-nitro-1H-indoline and 3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone) identified by means of spectroscopic analysis. DISCUSSION: The numerical modelling of the photodegradation concentration-time profiles gave (8.13 +/- 0.15) x 10(-2) and (1.34 +/- 0.04) x 10(-2) mol/E for the overall primary quantum yield of direct photolysis for musk tibetene and the major intermediate (3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone), respectively, in the wavelength range 305-366 nm. The half-life times of photodegradation of the both substances varied from 1-1.5 hours at 20 degrees N during the summer season to 6-10 hours for highest latitudes in winter. CONCLUSIONS: Under solar light, musk tibetene was photolabile in acetonitrile and acetonitrile/water 1/1, while it was slowly degraded when suspended in water. In all media, musk tibetene was photodegraded into three photoproducts. By using a kinetic model, the overall primary quantum yields of direct photolysis of musk tibetene and its main photoproduct, in the wavelength range 305-366 nm, were estimated, indicating that the photodegradation rate for musk tibetene is faster than the photolysis rate of the major by-product. RECOMMENDATIONS AND PERSPECTIVES: The results indicate that, in order to assess the environmental impact of musk tibetene on the aquatic ecosystem, great attention should be focused on the major photoproduct which is proved to be more persistent than the parent compound under light irradiation. The predicted half-life times of direct photolysis for both substances ranged from 1-1.5 hours at 20 degrees N during the summer season to about 6-10 hours for highest latitudes in winter, indicating that, from a photochemical point of view, the environmental persistence of these substances increases by increasing the latitudes and during the cold seasons, making more realistic an intake of these xenobiotic molecules into the food chain of aquatic living organisms. Tanabe reports in his Editorial (Tanabe 2005) that "It is necessary to have knowledge of the global picture of synthetic musk pathways. So, it is conceivable that now is the time to study the transport, persistency, distribution, bioaccumulation and toxic potential of this new environmental menace on a global scale, especially in developing countries". Therefore, the future environmental analysis and investigations on the eco-toxicity of nitro musk compounds should take into account not only the presence of the parent compounds but also their photochemical intermediates or end-by-products.     

氟里昂12(CCl2F2)燃烧分解催化剂性能的研究

本文对贵金属、氧化物和复合氧化物体系催化剂上氟里昂_(12)(F_(12))燃烧分解反应进行了活性评价和稳定性研究.结果表明:TiO_2,ZrO_2/TiO_2催化剂对氟里昂_(12)燃烧分解反应具有良好的低温催化活性和较好的稳定性,ZrO_2/TiO_2催化剂具有一定的臭氧-催化氧化活性     

纳米铁催化分解高氯酸盐废水的反应动力学

通过实验考察了酸性条件下纳米铁催化分解高氯酸盐过程中的影响因素,对其分解的动力学进行了研究,并对纳米铁催化剂结构及微观形貌进行SEM、EDS和XRD表征分析。利用阿仑尼乌斯方程和幂指数方程拟合反应动力学方程,获得了高氯酸盐分解动力学方程Ct=C0exp{-0.03773exp(-201.65/T)[H]0.191t},理论的计算值与实验值吻合较好,误差在15%以内。     

Ce(Ⅲ)对UV-B辐射胁迫下大豆幼苗光化学反应的影响

用水培法研究Ce(Ⅲ)对UV-B辐射胁迫下大豆幼苗光化学反应的影响.结果表明, 20 mg·L^-1 CeCl₃使大豆幼苗净光合速率(Pn)、Hill反应、Mg²⁺-ATPase活性与光合磷酸化活力4项指标较对照提高23.2%～14.3%; 有效抑制UV-B辐射(T₁=0.15 W·m^-2和T₂=0.45 W·m^-2)胁迫下4项指标下降, 4项指标降幅［Ce(Ⅲ)+T₁为36.6%～15.9%,Ce(Ⅲ)+T₂为65.6%～33.2%］小于对应的UV-B辐射组(T₁为50.9%～23.3%,T₂为77.3%～51.4%). 动态变化显示, Ce(Ⅲ)减缓了胁迫期4项指标的下降趋势,促进了恢复期4项指标上升幅度. 说明Ce(Ⅲ)通过减轻UV-B辐射对大豆幼苗光化学反应的伤害, 遏制UV-B辐射胁迫下大豆幼苗Pn下降.     

模拟可见光下土壤表面石油的光化学降解研究

在模拟可见光照射下,分析了土壤中的初始含油量、土壤类型和土壤pH值对石油在土壤表面光降解过程的影响,并利用紫外-可见分光光度法(UV-Vis)、气相色谱-氢火焰离子化检测器(GC-FID)和傅立叶红外光谱(FTIR)等方法对石油在光降解过程中的演变规律进行研究.结果表明,石油在土壤表面上的光化学降解行为符合准一级反应动力学,实验测得石油的光解速率常数为0.002 6～0.017 2 h^-1,半衰期为40～267 h.GC-FID分析结果表明,在光降解50 h后,石油的饱和烃组分中高碳数的烷烃相对含量降低,低碳数的烷烃相对含量提高;芳香烃组分的大部分色谱峰有明显地降低或消失.红外光谱分析发现,光照60 h后土壤萃取液中可能产生了羰基类化合物,说明石油在光降解过程中逐渐发生氧化.     

二氧化碳资源化技术研究进展

过量的二氧化碳(CO2)排放可导致温室效应的不断加剧,因此CO2减排受到越来越多的关注,其中将CO2转化为附加值较高的化工产品,即CO2资源化利用技术不仅可实现CO2减排,同时具有一定的经济效益。CO2资源化利用技术主要包括光化学还原法、电化学还原法和催化转移氢化法等。重点介绍并总结了以上3种方法的特点、优势和不足,指出未来需研究解决的关键问题和研究方向,为实现高效的CO2资源化利用提供借鉴和参考。     

整合消费与增加值视角的中国行业碳排放变动分解研究

在研究影响我国CO 2排放因素领域,基于投入产出技术的分解模型已成为主要的分析工具,现有研究多分别基于消费视角或收益视角展开分析。为全面评估各行业收益与消费对其上游、下游行业碳排放的综合影响,整合基于收益与基于消费两个视角,运用2012年与2015年我国投入产出表,构建两层嵌套式结构分解分析模型(SDA),比较分析消费规模效应、收益规模效应、行业流入、流出增加值变动效应、增加值结构变动效应等14个影响各行业碳排放变动的关键因素,并借助对消费者原则碳排放估算公式的重构,更准确地实现从增加值视角对各行业消费者原则碳排放变动的关键影响因素分析。研究发现:①研究期内,我国在总产出增长29.14%的同时碳排放量上升1.46%,各行业碳排放强度下降是主要的减排因素,其中建筑业减排贡献最大。②增排效应方面,影响从大到小依次为消费规模、收益规模、完全投入结构与完全消费结构四项效应,且前两个规模效应的影响是后两个结构效应的2倍以上,尤其建筑业消费规模效应、煤炭采选产品业收益规模效应增排较大。③消费规模扩大导致增排的原因并非行业本身生产规模扩大,而主要在于建筑业、服务业等行业规模扩张时吸收其他行业流入的增加值量增多。④收益规模扩大导致的增排效应方面,细分来说从大到小依次为劳动者报酬、生产税净额、固定资产折旧、营业盈余四项效应,且行业差异显著,如煤炭采选产品业的劳动者报酬效应,石油、炼焦产品和核燃料加工品业的生产税净额效应以及电力、热力生产和供应业的营业盈余效应增排贡献较大,而煤炭采选产品业的营业盈余效应、批发、零售业和住宿、餐饮业的生产税净额效应则减排贡献较大。     

Thermal decomposition mechanism of 65% lysine sulfate powder and its thermal stability based on thermal analysis

Lysine is widely used in the fields of food, medicine and feed, which generally appears in the form of lysine sulfate or lysine hydrochloride dust because of the high instability of the free L-lysine. The L-lysine Sulfate is in high risk of decomposition, spontaneous ignition and even the dust explosion, because the control temperature in its production process is high up to 90 °C. Thus, the thermal behaviors and its thermal stability of 65% lysine sulfate are experimentally explored in Air and Nitrogen using the simultaneous TG-DSC measurements. Results show: (1) the decomposition of 65% lysine sulfate can be divided into three stages both in the atmospheres of air and nitrogen, and most of the weight loss occurred in the first two stages, which are related with the decarboxylation and deamination process. (2) The effects of atmosphere on the decomposition of 65% lysine sulfate mainly occur at the third stage. In this stage, the weight loss in nitrogen is only 14.2%, which is much lower than that in air (34.3%), which is related to the oxidative degradation at high temperature. Besides, the active energy is slightly increased in nitrogen compared to that in air. (3) The initial temperatures of the decomposition of the 65% lysine sulfate are 145 °C and 155 °C, for the air and nitrogen atmosphere, respectively, which are much lower than that (260 °C) of the pure lysine.     

水稻和玉米的热氧化分解特性及几种动力学方法结果的比较

利用热重分析仪在空气气氛、不同的升温速率下对带壳稻谷粉和玉米粒粉进行了热重测试,依据热重实验数据,采用多种热解动力学分析方法计算了水稻和玉米的活化能数值并进行比较,结果表明水稻和玉米的热氧化反应活化能随着转化率出现先增加后降低的趋势,并在转化率为70%左右达到了极大值。     

The inhibitory combustion reaction performance and tail gas analysis of composite ultra-fine dry powder extinguishing agent containing different additives

For lack of an extinguishing agent with high-efficiency, non-toxic and environmentally friendly, a new type of extinguishing agent was fabricated to solve such an urgent problem. In this study, the zinc borate (ZB) and ferrocene (Fe(Cp)₂) were utilized as two additives for extinguishants to suppress combustion reaction and the toxicity of the tail gas was detected. The mass fraction of ZB corresponding to the optimal inhibitory effect was determined to be 0.5–1.5%, by contrast, the optimum interval of Fe(Cp)₂ was detected as 0.5–1.0%. Similarly, with the increasing proportion of the two additives, the homologous inhibitory action was gradually weakened. From the perspective of thermogravimetric analysis (TGA), it was indicated that the ZB accelerated the pyrolysis process of the extinguishant, making its thermal decomposition process more thoroughly. Meanwhile, the differential scanning calorimetry (DSC) demonstrated that the decomposition efficiency was markedly improved when the amount of ZB was maintained at 0.5–1.5%. Besides, the tail gas tests were implemented to assess the extent of toxic and harmful properties. In terms of the carbon monoxide (CO) and carbon dioxide (CO₂) generated, once the mass fraction of ZB and Fe(Cp)₂ was less than 1.5% and 1.0% respectively, the concentration of CO and CO₂ was distinctly lower than that without additives. Moreover, the inhibitory ability on nitrogen oxides (NOx) was enhanced when the mass fraction of the two additives was kept below 1.0%. The results confirmed that a more practical extinguishant was proposed and it can provide guidance for the application and development of extinguishants.