GC-R-CF-MS method to determine the 13C abundance of gaseous combustion products in cigarette smoke

To determine the ¹³C abundance of combustion and break down products formed in cigarette smoke, especially CO and CO₂, a simple and fast analytical method is needed. Taking into account the knowledge about the determination of the natural ¹³C abundance in air, an online method—based on gas chromatography-reaction-continuous flow mass spectrometry (GC-R-CF-MS)—has been developed, which enables the determination of the ¹³C abundance of CO and CO₂ in the vapour phase of cigarette smoke with a relative standard deviation of≤0.5% in one analytical run. Additionally, in a second step, the ¹³C abundance of total volatile carbon can be determined.     

火灾烟雾颗粒凝并分形特性研究

火灾烟雾颗粒因布朗运动由初期的主粒子凝并形成大颗粒的凝团结构，其外形呈现出分形特征，根据分形理论对火灾烟雾颗粒凝团结构进行分析研究，采用场发射扫描电镜对多种材料的烟雾颗粒图像进行测试，通过对烟雾凝团图像进行处理，获得了火灾探测中常见的多种材料的分形维数和分形系数，给出了烟雾颗粒的主粒子粒径，并对其影响因素进行了对比分析，为火灾烟雾探测中颗粒凝并分形特性研究提供有益的探索. 关键词： 火灾 烟雾 颗粒 凝并 分形     

Large-Scale Reassessment of In-Vineyard Smoke-Taint Grapevine Protection Strategies and the Development of Predictive Off-Vine Models

Smoke taint in wine is thought to be caused by smoke-derived volatile phenols (VPs) that are absorbed into grape tissues, trapped as conjugates that are imperceptible by smell, and subsequently released into wines as their free odor-active forms via metabolism by yeasts during fermentation. Blocking VP uptake into grapes would, therefore, be an effective way for vineyards to protect ripening grape crops exposed to smoke. Here, we re-evaluated a biofilm that had previously shown promise in pilot studies in reducing levels of smoke-derived VPs. A suite of nine free and acid-labile VPs were quantitated in Pinot Noir grapes that had been exposed to smoke after being coated with the biofilm one, seven or 14 days earlier. In contrast with earlier studies, our results demonstrated that in all cases, the biofilm treatments led to increased concentrations of both free and total VPs in smoke-exposed grapes, with earlier applications elevating concentrations of some VPs more than the later time points. Tracking VP concentrations through the grape ripening process demonstrated that some (phenol, p/m-cresol, and guaiacol) were not entirely sequestered in grapes as acid-labile conjugates, suggesting the presence of VP storage forms beyond simple glycosides. Free VPs in grapes, though a minor portion of the total, most clearly correlated with concentrations present in the resulting wines. Finally, red table grapes, available year round, were observed to replicate the effects of the biofilm treatments and were capable of transforming most VPs into acid-labile conjugates in under 24 h, indicating that they might be an effective model for rapidly assessing smoke-taint prophylactic products in the laboratory.     

Cu/HMOR催化二甲醚羰基化合成乙酸甲酯: 催化剂制备方法的影响 (cited: 2)

采用氨蒸发法、尿素水解法、离子交换法及浸渍法制备HMOR负载的Cu催化剂, 考察其催化二甲醚(DME)羰基化合成乙酸甲酯(MA)性能. 结果表明离子交换法制得Cu/HMOR催化剂在Cu的金属中心和酸性分子筛载体的共同作用下具有较好催化反应活性. 在210 oC、1.5 MPa、空速4883 h^-1,DME转化率为95.3%,MA选择性为94.9%. 对催化剂进行N2物理吸附、X射线衍射、NH₃程序升温脱附和CO程序升温脱附等表征发现,离子交换法制得Cu/HMOR催化剂具有较高比表面、大量弱酸及一定中强酸、适中的CO吸附强度,提高了CO插入DME羰基化反应活性.     

Heterogeneous fixation of N2: Investigation of a novel mechanism for formation of NO

Formation of NO initiated by heterogeneous fixation of N₂ during pyrolysis is investigated experimentally and theoretically. The experiments were conducted with beech wood as well as with the pure biomass components cellulose, xylan, and lignin. The NO formation during char oxidation was recorded as function of pyrolysis atmosphere (N₂ or Ar), pyrolysis temperature (700–1050 °C), and oxidizing atmosphere (O₂ in N₂ or Ar). The results confirm earlier reports that biomass char may be enriched in N during pyrolysis at 900 °C and above. The N-uptake involves re-capture of N-volatiles as well as uptake of N₂. During char oxidation, the captured N is partly oxidized to NO, resulting in increased NO formation. The NO yield from oxidation of beech wood char made in N₂ increases with pyrolysis temperature, and is about a factor of two higher at 1050 °C than the corresponding yield from chars made in Ar. The experiments with pure materials show that the lignin char has the strongest ability to form NO from uptake of N₂, while xylan char forms only small amounts of NO from N₂. Density Functional Theory (DFT) calculations on model chars have revealed a number of chemisorption sites for N₂, many of which are weakly bound and therefore expected to have a short half-life at the higher pyrolysis temperatures. However, the chemisorption of N₂ across a single ring of the armchair surface was found to have an activation energy of 344 ± 30 kJ mol⁻¹ and form a stable, exothermic product with cyano groups. This demonstrates that at least one channel exists for the high-temperature incorporation of N₂ into a char which could give rise to the observed increase in NO release in subsequent char oxidation.     

Pulsed Corona Discharges for Tar Removal from Biomass Derived Fuel Gas

To supply combustion engines or gasturbines with fuel gas obtained from biomass gasification, it is necessary to clean the fuel gas. Also the production of chemicals by processes such as Fisher-Tropsch requires a high gas quality. Especially heavy aromatic hydrocarbons (tars) must be removed. In this work, we give an overview of our investigations on tar removal by pulsed corona discharges as an alternative approach to catalytic or thermal tar cracking. Experimental results (at a gas temperature of 200°C) are reported for the removal of various model tar components in synthetic fuel gas. In order to identify the major reaction pathways, experiments were also done on tars in individual fuel gas components. The results show that tar removal by pulsed corona processing is possible. The process for tar removal is mainly via oxidation. Also termination reactions by CO play an important role.     

火灾烟颗粒的分形结构形状模拟与光散射计算

针对火灾烟颗粒的形状特点，提出并建立火灾烟颗粒分形结构凝团的形状模型，并对烟颗粒扫描电镜(SEM)图像进行分析，获取分形结构模型中的单个凝团中基本颗粒个数、凝团分形维数、基本颗粒半径等参数.利用该模型对火灾烟颗粒的形状进行模拟的结果表明，该模型能够较好反映出烟颗粒的形貌特征.利用形状模型对火灾烟颗粒散射进行初步计算表明，在其他参数相同的情况下，相对于同体积的球形颗粒，分形凝团具有前向散射较弱，后向散射较强的特征.     

火灾烟气危害性气体在狭长通道内水平方向迁移的模拟实验研究

利用狭长通道的小型实验台模拟研究了火灾烟气毒性成分在水平方向上的迁移规律.结果发现,火灾烟气危害性成分水平方向上的演变非常相似,而不同高度水平面上的烟气成分浓度有些差别,这主要是建筑结构中各种开口或者空气流动造成的.数据表明,CO等气体到达浓度峰值的时间随着高度的降低而逐渐增加.其中,O2和CO2到达峰值的时间比较一致,而CO则与前两者不一致,整体滞后80秒左右,这可能因为热烟气在传播过程又新生成了CO.     

Analysis of the product gas from biomass gasification by means of laser spectroscopy

The use of biomass and waste for decentralised combined heat and power production (CHP) requires highly efficient gasification processes. In the Technische Universität München (TUM), an innovative gasification technology has been developed. This allothermal gasifier is producing a hydrogen- rich, high-calorific gas, that can be further used in a microturbine or a fuel cell producing energy. For the operation of such a system, the online analysis of the composition of the product gas is of high importance, since the efficient working of the machines is linked with the gas quality. For this purpose an optical measurement system based on laser spectroscopy has been applied. This system can measure not only the basic components of the product gas (H₂, CH₄, CO, CO₂, H₂O), but it also gives information concerning the content of high hydrocarbons, the so-called tars, in the product gas.     

Investigation,by single photon ionisation (SPI)–time-of-flight mass spectrometry (TOFMS), of the effect of different cigarette-lighting devices on the chemical composition of the first cigarette puff

Soft single-photon ionisation (SPI)–time-of-flight mass spectrometry (TOFMS) has been used to investigate the effect of different cigarette-lighting devices on the chemical composition of the mainstream smoke from the first cigarette puff. Lighting devices examined were a Borgwaldt electric lighter, a propane/butane gas lighter, a match, a candle, and the burning zone of another cigarette. To eliminate the effects of the different masses of tobacco burnt by use of the different lighting methods a normalisation procedure was performed which enabled investigation of changes in the chemical patterns of the resulting smoke. When another cigarette was used as the lighting device, elevated levels of ammonia and other nitrogen-containing substances were observed. These are high in the sidestream smoke of the cigarette used for lighting and would be drawn into the mainstream smoke of the cigarette being lit. In contrast, smoke from the cigarette lit by the electric lighter contained slightly higher normalised amounts of isoprene. Lighting the cigarette by use of a candle resulted in larger amounts of substances, e.g. benzene, which most probably originated from thermal decomposition of wax. The composition of the first puff of smoke obtained by use of the three lighting methods with open flames (gas lighter, match, and candle) was usually similar whereas the composition of the smoke produced by use of the electric lighter and the cigarette as the lighter were more unique. The chemical patterns generated by the different lighting devices could, however, be separated by principal-component analyses. Two additional test series were also studied. In the first the cigarette was lit with an electric lighter, then extinguished, the ash was cut off, and the cigarette was re-lit. In the second the cigarette was heated in an oven to 80 °C for 5 min before being lit. These treatments did not result in changes in the chemical composition compared with cigarettes lit in the ordinary way. Figure Time-of-flight mass spectrometry (TOFMS) has been used to investigate the effect of different cigarette-lighting devices on the chemical composition of the mainstream smoke from the first cigarette puff