二价铁催化过氧化氢-过硫酸钠再生活性炭可行性研究

利用二价铁(Fe~(2+))催化过氧化氢(H_2O_2)-过硫酸钠(Na_2S_2O_8)双氧化体系(ICHP)对被三氯乙烯(TCE)吸附饱和的20~40目粒状活性炭(AC)进行再生研究.同时,结合扫描电子显微镜(SEM)、能量散射光谱仪(EDS)、X射线光电子能谱仪(XPS)及氮气吸附-解吸技术等手段对再生前后的AC进行表征,进一步探讨影响再生效率的原因.结果表明,AC对TCE的吸附符合准一级动力学模型,等温吸附符合Freundlich模型.在TCE∶Fe~(2+)∶H_2O_2∶S_2O_2-8=1∶9.20∶59.79∶77.52(物质的量比)的条件下,AC再生效率约为50%.研究表明,AC的炭损失、比表面积、孔隙体积及孔隙面积的减小,是再生AC吸附能力低于原状AC的主要原因.利用ICHP再生的AC可以实现对TCE的有效吸附并达到AC重复使用的目的,具有很好的实用价值.     

大气中过氧化氢的生成、污染特征及其影响因素

过氧化氢(H₂O₂)是自由基的源和汇,是对流层大气中重要的氧化剂. 采用文献研究法对1990年以来H₂O₂的文献进行搜集整理,对其生成途径、污染特征及其影响因素进行了研究. 结果表明:H₂O₂在大气、云水和颗粒物中均有存在,大气中的H₂O₂主要通过O₃和甲醛光解、VOC同OH·/O₃等反应生成. 大气中φ(H₂O₂)一般在nd～8×10-9内波动,晴天φ(H₂O₂)呈早晚低、午后高的日变化特征;φ(H₂O₂)随φ(O₃)、太阳辐射和气温的增加而升高,随φ(NO_x)、φ(VOCs)和相对湿度的升高而降低;H₂O₂氧化SO₂为SO₄2-是液相化学中最重要的反应,可以导致酸沉降以及二次气溶胶浓度的升高. 在气相光化学反应中,H₂O₂/HNO₃(体积分数比)可以指示O₃生成是VOCs控制还是NO_x控制. 今后需对OH·浓度、NO₂和O₃的光解速率等影响H₂O₂关键因素开展监测研究,此外,还需对我国特殊大气环境下H₂O₂对SO₄2-生成的贡献、不同地区H₂O₂/HNO₃指示O₃生成对NO_x或VOCs敏感性等方面开展更多的研究.      

Experimental determination of dust cloud combustion parameters of α-AlH3 powder in its charged and fully discharged states for H2 storage applications

This study discusses results of an experimental program for determination of dust cloud combustion parameters of charged and fully discharged states of metastable alane (aluminum hydride, α-AlH₃ polymorph) powder in air. The measured characterization parameters include: maximum deflagration pressure rise (ΔP_MAX), maximum rate of pressure rise (dP/dt)_MAX, minimum ignition temperature (T_C), minimum explosible concentration (MEC), and minimum ignition energy (MIE). These measured values are used for calculating the associated explosion severity (ES) index, and volume-normalized maximum rate of pressure rise (K_St). The experimental results show values of MEC and T_C of fully discharged alane to be greater than those of the charged alane but measured MIE values are about the same. Moreover, the results show higher reactivity of fully discharged alane dust cloud in air compared to its charged state. For example, ES and K_St of discharged alane dust cloud in air are about 300% and 35% greater, respectively, than ES and K_St of charged alane dust. The higher air reactivity of fully-discharged (primarily Al powder) dust cloud compared to its charged state can be attributed to the higher surface energy (J/m²) of Al compared to that of α-AlH₃. These experimental insights have safety implications in postulated risk scenarios involving light-duty vehicles powered by PEM fuel cells. The core insights and critical data provided by this contribution are useful for supporting development and promulgation of hydrogen safety standards and augmenting property databases of hydrogen storage materials.     

Hydrogen-rich synthesis gas production from waste wood via gasification and reforming technology for fuel cell application

The purpose of this study was to establish a fuel process for an advanced power generation system in which hydrogen-rich synthesis gas, as the fuel for the molten carbonate fuel cell (MCFC), can be extracted from biomass via gasification and reforming technologies. Experiments on waste wood gasification were performed using a bench-scale gasification system. The main factors influencing hydrogen generation in the noncatalytic process and in the catalytic process were investigated, and temperature was identified as the most important factor. At 950°C, without employing a catalyst, hydrogen-rich synthesis gas containing about 54 vol% hydrogen was extracted from feedstock with appropriately designed operation parameters for the steam/carbon ratio and the equivalence ratio. However, by employing a commercial steam reforming catalyst in the reforming process, similar results were obtained at 750°C.     

Fenton反应助催化剂碳基黄铁矿型纳米二硫化钴的合成

以水热与化学气相沉积方法制备了碳基黄铁矿型纳米CoS₂薄膜,对其组成、形貌进行了表征,并对其Fenton反应助催化性能进行了研究。实验结果表明：在罗丹明B模拟废水的Fenton处理过程中,添加CoS₂助催化剂的Fenton体系具有更高的反应活性,20 s内的脱色率达到98%,相比于普通Fenton体系的反应速率提高了近3倍;在类Fenton体系中的反应速率最高增加了约350%。CoS₂的加入显著提高了H₂O₂的利用效率以及催化氧化反应的反应速率。     

Ex-ante environmental assessments of novel technologies - Improved caprolactam catalysis and hydrogen storage

Utrecht University has conducted a pilot sustainability assessment for the executive board of the chemistry program ACTS (Advanced Chemical Technologies for Sustainability) of the Netherlands’ Organization for Scientific Research (NWO). These assessments represent prospective, i.e. ’ex-ante’ studies on the production of caprolactam by an improved catalyst and on different hydrogen storage options (i.e. compressed and liquefied hydrogen, storage in metal hydrides and storage in a metal organic framework). The pilot sustainability assessments followed the principles of environmental life cycle assessment (LCA), thereby focusing on non-renewable energy use (NREU) and climate change (GWP100). It was found that caprolactam with the novel catalyst has lower impacts than petrochemical caprolactam production from benzene but higher impacts than bio-based caprolactam produced via fermentation. Regarding hydrogen storage, it was found that compressed and liquid hydrogen have the highest impacts. The impacts of the metal hydrides and the metal organic frameworks show by far the lowest environmental impacts. The main reason is that these materials can be reused up to 1500 times (refilling of tank), while for compressing and liquefaction of hydrogen energy is needed each time a tank needs to be refilled. The study demonstrates the successful application of ex-ante technology assessment.     

海洋卡盾藻日本株过氧化氢产生的影响因素

对海洋卡盾藻日本株(Chattonella marina Japan,CMJP)在不同盐度、营养盐条件及不同生长期的过氧化氢产生特点进行了研究.结果表明:H2O2浓度峰值出现在CMJP对数生长期(4~8d),以第6d达到最大,为0.97×10-4nmol/cell.在N:P为8:1和16:1的情况下,CMJP生长较快,藻细胞在对数生长末期之前一直保持较高密度.CMJP产生的H2O2量与藻类生长呈现出一定的相反趋势,在藻细胞适宜生长的N:P下,产生的H2O2浓度较小.在N:P为16:1时单个藻细胞的H2O2量最低(0.40×10-4nmol/cell),仅是N:P为32:1时(1.17 ×10-4nmol/cell)的1/3,N:P为8:1时,单个藻细胞的H2O2浓度为0.63 ×10-4nmol/cell. CMJP在盐度为20,25psu时生长较好且藻细胞达到较高密度,在盐度为10,15,30psu时藻密度较低,表明低盐和高盐条件均不利于CMJP的生长.盐度对CMJP过氧化氢的产量有一定的影响,在高盐度下单个藻细胞的H2O2产量增加,盐度为30psu时,H202浓度最高(1.1×10-4nmol/cell).     

CNT/CdS/壳聚糖-H2O2可见光光催化甲基橙脱色研究

利用共沉淀法制备了具有可见光响应的CNT/CdS复合薄膜光催化材料.以氙灯模拟日光光源,并以双氧水辅助氧化,对甲基橙进行光催化降解,探讨了不同工艺、催化剂用量、双氧水用量、甲基橙初始浓度、溶液pH值、无机阴离子对光催化降解脱色的影响以及催化剂的重复使用性.实验结果表明:双氧水对CNT/CdS光催化甲基橙脱色产生协同作用...     

阻抑催化动力学光度法测定水体中的痕量镍

研究了在pH9.2硼砂介质中,镍(II)对过氧化氢氧化溴甲酚紫褪色反应具有阻抑作用,聚乙二醇-200(PEG-200)对此反应体系有活化作用,据此建立了阻抑动力学光度法测定痕量镍(II)的新方法。试验考察了反应介质种类和用量、活化剂种类和用量、反应温度、反应时间、共存组分等因素的影响,确定了最佳试验条件。该方法的测定波长为590nm;活化剂为PEG-200;反应温度为沸水浴;反应时间为14min;线性范围为1.7×10-6g/L～1.4×10-4g/L;检出限为1.7×10-6g/L。所建方法用于环境水体中痕量镍(II)的测定,最大相对标准偏差为3.27%,加标回收率为95.5%～104.5%;所建方法与火焰原子吸收光谱法进行了对比试验,方法相对误差小于6.50%。     

催化极谱法测定降水中微量过氧化氢

在０．６ｍｏｌ／Ｌ磷酸介质中,钒５－Ｂｒ－ＰＡＤＡＰ与Ｈ２Ｏ２形成三元络合物,于０．０５Ｖ处产生一极灵敏的极谱波。过氧化氢浓度在０．０６－１７μｇ／２５ｍＬ范围内,峰电流与其含量呈良好线性关系。