过氧化氢热爆炸研究进展

过氧化氢作为绿色环保的氧化剂,广泛应用于工业的各个领域,同时也因其热分解爆炸危险性导致了一系列严重的火灾爆炸事故。过氧化氢在高温或与一些不兼容化学物质作用下,将会激发其热危险性,进而引发热失控反应,最终导致爆炸事故的发生。结合近年来国内发生的过氧化氢热爆炸事故,简要概述了其热爆炸事故历程,并从理论研究和实验研究两个方面综述了过氧化氢热爆炸的研究进展。理论研究方面,主要介绍了化学反应失控模型和基于热动力学的研究方法,尤其对基于热失控模型的热风险评估进行了详细的阐述。实验研究方面,分析了高温条件下与杂质催化作用下过氧化氢的热危险性,包括无机杂质和有机杂质。最后就过氧化氢热爆炸的研究提出了进一步的研究方向。     

Kinetic parameter estimation for decomposition of organic peroxides by means of DSC measurements

The thermal stability of organic peroxides (cumene hydroperoxide 80 wt% and dicumyl peroxide) was studied by means of calorimetric measurement (DSC, TA Q1000) in an isotherm mode and a dynamic mode. Analysis of power profiles released in the isothermal mode was combined with the analysis of the decomposed compounds by a gas chromatograph/mass spectrometer (GC/MS) to determine the reaction mechanisms corresponding to each of the two reactions. In this work, a methodology for estimating kinetic parameters was based on the comparison of the power profile (dynamic mode) given by the model to that obtained experimentally by changing the parameters values. Parameter estimation is achieved using the mixed estimation method where a genetic algorithm is combined with a locally convergent method.     

腐殖质及其模型化合物的H2O2光化学生成研究

在模拟太阳光下研究了多种腐殖质及其模型化合物的过氧化氢（H₂O₂）生成动力学,并对其生成机制进行了探讨.结果表明不同来源或不同形式的腐殖质在模拟太阳光照射下均能产生H₂O₂.不同腐殖质生成H₂O₂速率差异不大,范围为6.379~15.784nmol/（L·min）,腐殖酸生成H₂O₂速率略快于富里酸.对于腐殖质模型化合物,邻苯二酚、间苯二酚、对苯二酚、苯醌、邻茴香胺、对茴香胺、水杨酸和2,6-二甲氧基-1,4-苯醌等8种模型化合物没有产生明显的H₂O₂,而藜芦醇、对氨基苯甲酸、3,5-二羟基苯甲酸（DHBA）、2,5-二羟基-1,4-苯醌、苯酚、苯甲酸和苯胺等7种化合物均可检测到H₂O₂产生.但其产生H₂O₂的速率差异较大,相差1~2个数量级,生成H₂O₂速率最快的化合物为2,5-二羟基-1,4-苯醌和DHBA,较慢的为苯酚、苯甲酸和对氨基苯甲酸.基于腐殖质生成H₂O₂机制,推测典型模型化合物DHBA的H₂O₂生成机制可能为光照条件下该化合物跃迁为单重激发态,该激发态发生分子内电子转移,生成还原性自由基中间体,该中间体和O₂反应,生成了超氧负离子（O₂·^-）,随后与水中H⁺反应生成了H₂O₂.     

Enhanced nitrogen removal upon the addition of volatile fatty acids from activated sludge by combining calcium peroxide and low-thermal pretreatments

This study investigated a combined low-thermal and CaO₂ pretreatment to enhance the volatile fatty acid (VFA) production from waste activated sludge (WAS). The fermentative product was added to a sequencing batch reactor (SBR) as an external carbon source to enhance nitrogen removal. The results showed that the combined pretreatment improved WAS solubilization, releasing more biodegradable substrates, such as proteins and polysaccharides, from TB-EPS to LB-EPS and S-EPS. The maximum VFA production of 3529 ± 188 mg COD/L was obtained in the combined pretreatment (0.2 g CaO₂/g VS + 70 °C for 60 min), which was 2.1 and 1.4-fold of that obtained from the sole low-thermal pretreatment and the control test, respectively. Consequently, when the fermentative liquid was added as an external denitrification carbon source, the effluent total nitrogen decreased to Class A of the discharge standard for pollutants in rural wastewater treatment plants in most areas of China.     

Fenton试剂加硫酸处理高浓度含酚废水的研究

研究了硫酸、Fenton试剂对酚的催化降解作用，证实了硫酸与Fenton试剂对酚的催化降解具有协同作用。H_2SO_4－Fenton试剂对高浓度含酚废水的处理结果说明，在Fenton试剂中加入硫酸可大大增加其对酚的降解能力。与单独的Fenton试剂法比较，当H_2O_2∶COD（重量比）＜0．8时，本法对COD≥14000mg／L含酚废水COD去除率可提高40％以上，对高浓度含酚废水具有很好的处理效果。     

High performance of multi-layered alternating Ni–Fe–P and Co–P films for hydrogen evolution

Judiciously engineering the electrocatalysts is attractive and challenging to exploit materials with high electrocatalytic performance for hydrogen evolution reaction. Herein, we successfully perform the interface engineering by alternately depositing Co–P and Ni–Fe–P films on nickel foam, via facile electroless plating and de-alloying process. This work shows that there is a significant effect of de-alloying process on alloy growth. The electronic structure of layered alloys is improved by interface engineering. The multilayer strategy significantly promotes the charge transfer. Importantly, the Co–P/Ni–Fe–P/NF electrode fabricated by interface engineering exhibits excellent electrocatalytic hydrogen evolution activity with an overpotential of 43.4 mV at 10 mA cm-2 and long-term durability for 72 h in alkaline medium (1 mol L-1 KOH). The innovative strategy of this work may aid further development of commercial electrocatalysts.     

催化湿式氧化乐果农药废水及催化剂的研究

通过共沉淀法制备了用于湿式氧化乐果农药废水的Cu/Mn复合氧化物催化剂,研究了沉淀剂种类、沉淀温度、焙烧温度和活性组分配比等因素对Cu/Mn复合氧化物催化剂的活性及稳定性的影响,确定了最佳制备条件,利用BET比表面积测定和XRD对催化剂进行了表征。结果表明:优化条件制备的Cu/Mn复合氧化物催化剂催化湿式过氧化氢氧化处理乐果农药废水时,具有较高的催化活性和稳定性。催化剂用量以6 g/L,反应温度80℃,过氧化氢加入量为12.0 g/L,反应时间60 min,COD去除率为89.5%,活性组分溶出量较小。     

日光/H2O2/草酸铁络合物光解水溶液中的直接耐酸大红

以H2O2/草酸铁络合物作光氧化剂,利用太阳光对水溶液中的直接耐酸大红进行了光氧化降解试验研究。结果表明,在日光照射下,H2O2/草酸铁络合物能使溶液中直接耐酸大红迅速光解,晴天光照15min或阴天光照30-40min,溶液（直接耐酸大红的质量浓度为50mg/L）可褪至无色;溶液的初始pH对染料光解有显著影响;pH为2-4时光解效果最佳;提高H2O2浓度可以提高光解速率,但H2O2的利用率会降低。     

深度氧化技术处理有机废水的研究进展

利用深度氧化技术处理有机废水是目前国内外废水处理的新技术,在美国和欧洲等发达国家,该技术已应用于各种废水和饮用水处理过程。针对我国石油、石化企业在外排废水中所含有毒有害有机物质大多难以降解的特点,经过调研,详细介绍了深度氧化技术处理有机废水的研究进展,并着重探讨了在光催化氧化技术、超声降解技术、超临界水氧化技术、湿式氧化技术等方面所做的工作及深度氧化过程除去水中有机污染物的原理。     

Modelling of stem biomass accumulation in Pinus densiflora seedlings exposed to aqueous-phase OH radicals generating mist

The present study aimed to evaluate the short-term biomass accumulation of forest trees exposed to wet acidic depositions. A hierarchical Bayesian model of tree growth was developed based on the data of a short-term experiment in which 2-year-old Japanese red pine (Pinus densiflora Sieb. et Zucc.) seedlings were exposed to aqueous phase OH radicals generated by an iron-oxalate-H₂O₂ mist (a pseudo-polluted dew) over two growing periods. We conducted a statistical comparison of tree growth between the control and pollution treatment groups by using the growth model incorporated the random effects due to the unknown characteristics of each seedling. The variability among seedlings is expressed in this model by the posterior probabilistic distributions of unobserved dry weight of a stem cohort before exposure treatment. The analysis of the effects of pollution treatment on the stem growth revealed that this treatment decreases the biomass allocation in the current year stems. However, the effects on the relative growth rate of pre-existing stems were unclear. Based on these results, we can speculate that in a polluted environment, the short-term growth of the young stems in the seedlings inhibited by pollution treatment, thereby resulting in the slowdown of long-term biomass accumulation. This can explain the patterns observed in the declining Japanese red pine forests that are subjected to OH-generating dews in the polluted area of western Japan.