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.     

二价铁活化过氧化钙提高剩余活性污泥的脱水性能

采用Fe²⁺活化过氧化钙（Fe²⁺/CaO₂）提高剩余污泥的脱水性能,考察初始pH值、Fe²⁺和CaO₂投加量对污泥脱水性能的影响,并进一步探究了实现污泥深度脱水的内在机制.结果表明,初始pH值为中性,Fe²⁺和CaO₂投加量（以VSS计）分别为3.31 mmol·g^-1和3.68 mmol·g^-1时,污泥的脱水效果最好,污泥比阻（SRF）和含水率（W_C）分别由20.99×10¹² m·kg^-1和86.61%降低至3.91×10¹² m·kg^-1和76.15%.Fe²⁺/CaO₂的氧化使污泥微生物细胞裂解,胞内有机物释放,胞外聚合物（EPS）降解;同时,Fe³⁺促使污泥颗粒再絮凝形成致密、多孔的絮体结构,有利于EPS结合水释放,实现污泥深度脱水.从技术和经济角度来看,Fe²⁺/CaO₂工艺经济实用,在提高剩余污泥脱水能力方面具有一定的应用前景.     

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。     

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。     

超声波-H2O2协同作用处理孔雀绿废水

采用超声波（US）-H2O2协同作用处理含孔雀绿的废水（简称废水）；考察了H2O2加入量、US功率、反应温度、反应时间对废水色度、COD去除率的影响，并对US-H2O2体系降解孔雀绿的机理进行了探讨。实验结果表明：在US作用下，H2O2加入量对废水色度、COD去除率的影响较大；废水色度、COD去除率均随US功率和反应时问的增加而提高；在US～H2O2体系中，低温对处理废水有利，高温反而不利；US—H2O2处理废水具有协同作用。在废水量为100mL、pH为7．3、反应温度为40℃、H2O2加入量为10mL、US功率为240W、反应时间60min的条件下对废水进行处理，废水COD、色度去除率分别为97．5％，98．8％。     

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.