溴化环氧树脂在亚临界醋酸体系中的降解特性

该文将废弃线路板中的溴化环氧树脂经过亚临界醋酸处理后,对其降解特性进行研究。考察不同温度、醋酸质量浓度和保温时间对溴化环氧树脂降解效果以及降解产物的影响。在亚临界醋酸环境下,当反应温度为220～260℃,保温时间为1～2 h,醋酸质量浓度为49.90%时,溴化环氧树脂能够完全降解,得到以双酚A、苯酚和异丙基苯酚为主的油相产物。在亚临界醋酸中可以快速溶胀并降解,溶胀现象能够增强醋酸对溴化环氧树脂的催化降解效果。降解产物中溴主要以HBr的形式存在于水相中。剩余固相产物中主要为玻璃纤维和铜箔,二者自动分层便于回收。该研究为废弃印刷线路板的无害化处理以及资源化利用提供了一种新方法。     

废弃印刷线路板热解过程传热特性实验研究

为了改善印刷线路板热解过程中的传热性能、提高废弃印刷线路板热解效率和产率、减少热解过程对环境的二次污染,本文设计并搭建了一套固定床热解实验装置,在高温氮气渗流条件下对3种不同尺寸废弃印刷线路板颗粒料层的热解过程进行了对比实验;测试了颗粒料层热解过程沿轴向和径向的温度分布,分析了线路板颗粒尺寸对物料层温度场和对热解区域迁移速度的影响,阐明了沿热解炉高度方向物料温度参数随时间的变化特征,揭示了热解区域和热解状态对于沿轴向的温升速率和温度梯度的影响规律.结果表明:较大颗粒料层的热解区域纵向迁移速度要快于小颗粒料层,当颗粒尺寸分别为1.5、2.5和3.5 cm时,热解区域的纵向迁移速度分别为0.47、0.50和0.63 m·h~(-1);热解区域和热解状态对于沿轴向的温升速率和温度梯度有显著影响;废弃印刷线路版热解过程的能源利用效率较低,只有29.50%～37.13%,主要损失为热解装置和物料的蓄热损失.研究结果对印刷线路板热解装置的设计和运行具有重要的指导意义.     

印刷线路板及覆铜板热分析实验研究

选取印刷线路板(简称PWBs)和覆铜板(简称CCL)两种典型电子废弃物代表,应用氧弹量热仪和热重分析仪分别对其进行高位定容弹筒发热量测试和热重分析。结果表明:对于PWBs,温度控制在250~520℃时,样品剩余质量随着升温速率的增加而增多,当温度超过520℃后趋势相反;CCL的分界温度在410℃附近。随着升温速率的提高,PWBs和CCL样品的最大失重速率会推迟出现10~20℃,且两种样品的DTG曲线均随着升温速率的提高整体向高温区偏移。反应初始温度、最终温度以及反应最大速率所对应的峰值温度均随着升温速率的增大而升高。当升温速率β增大时,PWBs和CCL样品的DTG峰值温度Tp值均升高;CCL样品的最大热解速率νmax变化趋势与Tp相同,但PWBs样品的νmax随升温速率变化不大。     

印刷线路板热处理过程中HBr析出特性研究

利用热重红外联用和管式炉研究了溴化环氧树脂线路板热处理过程中HBr的析出特性。结果表明:HBr主要在线路板快速失重阶段(300~380℃)析出;加热方式对HBr的析出有很大影响,非等温加热方式下,在380℃以上,反应温度对HBr的析出影响不大。等温加热方式下,反应温度的提高有利于HBr的析出,而且HBr释放量显著高于非等温加热方式;在高温下HBr的析出量随氧分压的增加呈现增大的趋势。     

流化床污泥热解实验及产物性质研究

采用流化床反应器对城市污水污泥在400~600 ℃及800~950 ℃温度区间内进行了热解实验.结果表明,污泥受热升温过程经过干燥脱气、分解解聚和裂解缩聚3个阶段,在此过程中发生复杂的化学反应,生成热解气、焦油和半焦.热解温度为550 ℃时液体产率达到最大值,为50.35%,热解气产率在950 ℃时为51.58%,半焦产率随着热解温度升高而逐渐降低,950 ℃时为36.92%.污泥低温热解焦油含有较高百分含量的脂肪族碳氢化合物和类固醇类化合物,经加工可作为液体燃料利用,高温热解焦油可提取多种化工原料.热解气可作为合成气或燃烧利用.     

铝塑包装废物的热解特性研究

利用热重-差热-傅立叶变换红外光谱联用仪对铝塑包装废物热解特性进行分析,并对物料性质、纸质存在对热解过程的影响进行研究. 结果表明:铝塑包装废物热解主要发生于438～500 ℃,最大失重速率出现在470～475 ℃;产物中主要是—C—C—以及少量的—CC—与芳香烃;反应温度由50 ℃升至850 ℃,铝塑包装废物依次经历聚乙烯熔融软化、热解,铝熔融,铝与焦状物反应等过程;铝塑包装废物中含纸质时,在312.4～363.2 ℃增加了一个失重过程,同时高温时的热解反应更为复杂.      

初温和终温对废轮胎热解产物分布影响

以热重分析和固定床热解实验为基础,研究初温和终温对废轮胎热解产率及气相产物特性影响。实验结果表明:废轮胎的热解过程存在两个主要失重过程,第一失重温度区间为200～500℃,第二失重温度区间为650～800℃;升温速率仅改变了热解的最大失重速率,并未改变废轮胎最终热解失重率。固定床实验表明:初始温度低于100℃时,废轮胎在800℃时热解已基本结束;当终温为800℃,初始温度在100～550℃范围内时,随着初始温度的提高,固、气两相产物产率均提高,而液相产物产率降低;其中气相中H2、CO、CH4的含量高于初始温度小于100℃时的含量;分析认为:可通过调节热解的初始温度调节废轮胎热解在不同热解阶段的时间分配,适当提高热解初始温度有利于提高整个热解过程中的时间利用效率、改变废轮胎热解产物的分布;废轮胎热解气化的最佳温度区间为500～800℃。     

环境升温过程对常温固化环氧树脂热力学性能的影响

目的提高常温固化环氧树脂体系的高温使用性能。方法采用常温固化剂T31、中温固化剂IPDA以及高温固化剂DDM作为混合固化剂,对E-44型和AG-80型混合环氧树脂体系进行常温固化反应,并分析环境升温过程对固化物热力学性能的影响。通过DMA分析、热变形测量、固化度测试,分别评价室温固化环氧树脂在环境升温过程前后的玻璃化转变温度、热变形量及体系内部的固化反应程度变化,并通过吸水率测试和弯曲强度测试对玻璃纤维布增强常温固化环氧树脂基复合材料的耐湿热性能以及高温条件下的力学性能进行分析。结果环氧树脂常温固化物的tg为85.21℃,经1.5℃/min的平均升温速率加热至90℃之后,该环境升温过程使固化物的固化度增大至92%以上,tg增长为132.06℃的同时热变形温度增大。其复合材料耐湿热性能提高,且100℃时弯曲强度的保持率为65%,对于加热至120℃的环境升温过程,固化物的固化度接近96%,tg增长为144.45℃的同时热变形温度进一步提高,其复合材料耐湿热性能改善程度更加明显,且130℃时弯曲强度保持率仍接近60%。结论常温、中温、高温混合固化剂的合理复配有助于环氧树脂体系在环境升温变化的诱导条件下发生梯度式固化反应,使体系内部的交联固化程度迅速升至较高水平,可以有效提高其玻璃化转变温度,显著改善常温固化环氧树脂体系在高温条件下的热力学性能。     

十溴联苯醚的热解及其影响因素研究

在200~300℃的温度范围内研究了十溴联苯醚(BDE-209)的热降解及其影响因素.结果表明,温度、时间以及硝酸铜、三氯化铁、氯化铝和氯化锌等处理线路板过程中产生的金属盐对BDE-209热降解有不同的影响.升高温度或延长热解时间均能促进BDE-209的热解,且温度对BDE-209降解的影响程度大于时间对其降解的影响;硝酸铜、三氯化铁和氯化铝对BDE-209的热解均起促进作用,促进作用的顺序为:硝酸铜 >三氯化铁 >氯化铝;氯化锌对BDE-209的热解有抑制作用;随着温度的升高,氯化铝和氯化锌对BDE-209热降解的影响减弱.该研究结果可为深入探究电子垃圾热处理过程中BDE-209的释放及降解提供科学依据.     

热解条件对废电路板真空热解规律的影响

采用自行设计的间歇式固定床真空热解中试装置对废线路板进行了真空热解试验;研究了物料尺寸、热解终温、升温速率、真空度及恒温时间等热解条件对热解产物产率分布的影响和废线路板真空清洁热解过程的规律.试验结果表明,热解条件决定废线路板的真空热廨规律,热解终温是影响热解产物产率分布的最重要的热解条件,其它热解条件对热解产物产率分布也有一定影响.在物料尺寸为50 mm×50 mm、热解终温为550℃、加热速率为10℃·min-1、热解压力为20 kPa及恒温时间为60 min的热解条件下,有利于降低热解固体产物产率,同时有利于提高热解液体产物产率和减少处理费用.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.