废弃电路板中环氧树脂真空热解规律的研究

真空条件下,应用程序升温管式电炉对废弃电路板中环氧树脂热解规律进行了研究.考察了不同的热解终温(200～700 ℃)、升温速率(5～30 ℃/min)、真空度(以压力表征,3～30 kPa)及保温时间(10～150 min)对热解产物产率的影响.实验结果表明,热解终温是影响热解油产率最重要的因素;选择适当的热解终温(400～550 ℃)、升温速率(15～20 ℃/min)、真空度(15 kPa)及保温时间(30 min)有利于提高热解油产率.     

初始温度对废轮胎热解的影响

以管式炉热解实验和热重分析为基础,研究了初始温度对废轮胎热解产率及气相产物特性影响。结果表明,初始温度对废轮胎的热解存在重要影响。热重分析结果表明,废轮胎的热解过程存在2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;可通过提高升温速率能够缩短热解反应时间。在初始温度低于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和CH4的含量高于初始温度小于100℃时的含量;分析认为,可以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℃。     

不同升温速率下城市污水污泥热解特性及动力学研究

利用差热-热重分析法和Coats-Redfern积分法,对杭州某污水处理厂污泥在不同升温速率下的热解特性及反应动力学特征进行研究。实验结果表明,热解温度从室温升至900℃时,污泥热解过程可分为4个失重阶段;升温速率对污泥热解转化率、挥发分析出温度以及最大失重率等热解特性参数都有显著影响。升温速率越高污泥最大失重率越大;而较低的升温速率延迟了污泥热解反应时间,导致污泥失重量相对较大。根据Coats-Redfern积分法计算结果,污泥在氮气氛围下的热解反应为二级反应模式。提高升温速率可显著增加污泥热解的表观活化能和频率因子。     

印刷线路板热解过程中溴的迁移实验研究

选取溴化环氧树脂印刷线路板为原料,通过热重红外联用仪和热解-气相色谱/质谱联用仪对其热解过程中溴的迁移规律进行了研究.结果表明,印刷线路板主要热解温度区间在300～380℃,HBr在最大热失重处释放;PCB热解时,含溴化合物主要有溴甲烷、溴苯酚及2-溴,4-异丙基甲苯.     

灰色预测模型及分布活化能模型在废电路板热解中的应用

分别在管式炉反应器和热天平上对废电路板的热解行为进行实验研究。在管式炉反应器上考察了在同一升温速率（20 K/min）下不同热解终温 (400、500、600、700和800℃) 对废电路板热解产物产率的影响。在相关实验数据的基础上尝试用灰色理论及方法建立基于热解终温的废电路板热解灰色产率预测模型GM(1,1),预测结果与实验数据对比表明,该预测模型精度较高,能够较好地对不同热解终温下废电路板热解产物产率进行预测。此外,在热天平上获得的不同升温速率（10、15和20 K/min）下的热失重曲线表明,废电路板的失重速率峰随升温速率的提高逐渐向高温侧移动。采用分布活化能模型对废电路板热失重曲线进行动力学分析,获得废电路板热解活化能的变化曲线。计算结果表明,废电路板热解过程中活化能并不是单一数值,而是随失重率变化的一个函数。所得废电路板热解活化能值在140～250 kJ/mol范围内变化,当失重率在10%～60%之间,活化能值总体呈缓慢上升的趋势,但当失重率＞60%时,活化能值由155.4 kJ/mol迅速增加到244.4 kJ/mol。     

油田采油污泥的热解动力学及其热解效果研究

以新疆克拉玛依油田采油污泥为对象,分别采用热重分析仪和小型流化床热解反应器研究了含油污泥的热解过程及其热解效果。结果表明,油泥热解主要经历了失水、轻质组分挥发、重组分快速热解失重和缓慢失重4个阶段,热解过程基本符合一级动力学方程,提高热解的升温速率,可使油泥的最大失重速率D_max、失重速率峰值温度θ_max、升温终点的最大失重率都随之增加,表现在动力学上,反映出表观活化能和碰撞频率因子的同时升高,即提高油泥热解转化率的同时也影响了热解效率。失水油泥用流化床热解,在热解温度600℃、反应时间3 min时,油泥回收率可达到87%。     

不干胶废弃物热解与燃烧动力学特性

采用热重分析方法对不干胶废弃物(PSAs)进行了热解和燃烧失重分析,并采用Doyle法拟合计算了PSAs热解和燃烧动力学参数。结果表明:当温度低于200℃或高于600℃,PSAs的热解和燃烧失重过程具有性;300~600℃时,PSAs热解过程具有3个失重峰,而其燃烧过程具有2个失重峰。动力学分析结果表明:PSAs的热解是由多阶段复杂的热裂解反应组成,其热解过程可用4个一级反应来描述,随着升温速率的提高热解阶段第1峰区表观活化能降低;而第2、3峰区以及半焦深度裂解阶段的第4峰区活化能逐渐升高;PSAs燃烧过程可用3个一级反应来描述,随着升温速率的提高,PSAs燃烧过程的表观活化能均逐渐降低,并且燃烧表观活化能均低于热解表观活化能。     

不干胶废弃物热解焦燃烧特性

采用非等温热重分析和固定床热解实验研究了不干胶废弃物热解焦生成特性及热解焦燃烧特性,并计算了不同升温速率下热解焦的燃烧动力学参数。结果表明,不干胶废弃物热解焦产率随温度升高而逐渐降低,当热解终温在400~700℃时,热解焦产率在34.64%~22.03%之间;空气气氛下热解焦燃烧过程包括3个阶段:挥发分燃烧阶段(390~600℃)、混合燃烧阶段(390~600℃)和残炭燃烧与矿物分解阶段(650℃);升温速率对热解焦燃烧效果作用明显,升温速率越大,燃烧特性指数越高,燃烧稳定性越好;热解焦燃烧过程可以通过3个一级反应描述,当升温速率为40℃/min时热解焦燃烧各阶段表观活化能明显降低,表明升温速率提高有助于热解焦的燃烧反应活性,更有利于燃烧反应的进行。     

热解条件对硫酸钙/污泥基生物炭中Pb、Ni形态分布及生态风险的影响

以污泥为原料,硫酸钙为添加剂,采用热解法制备了硫酸钙/污泥基生物炭,考察了硫酸钙添加量、热解温度、升温速率及保温时间对生物炭中Pb、Ni形态分布的影响,并利用生态风险评价指数(RAC)对优化热解条件下制备的硫酸钙/污泥基生物炭中的Pb、Ni进行了生态风险评价。结果显示,优化热解条件为:硫酸钙添加量2.5%(质量分数)、热解温度750℃、升温速率2℃/min、保温时间15min。该优化热解条件下制备的硫酸钙/污泥基生物炭中的重金属Pb、Ni的生态风险分别为无风险、低风险,相对于污泥(低风险、中等风险)明显降低。     

市政污泥热解产油影响因素及产物应用特性

利用外热式固定床反应器,研究终温、反应时间、升温速率等因素对市政污泥热解产油率的影响,并对产物特性进行了讨论。结果表明,热解终温及反应时间显著影响焦油产率,500℃是适宜的污泥热解温度,焦油产率达24.74%,温度继续升高则半焦缩聚反应强烈,热解气产率大幅增加,焦油产率基本恒定;在10℃·min~(-1)的升温速率条件下,热解终温500℃,维持20 min,焦油产率可达到平衡;升温速率对焦油产率的影响不显著,热解反应达到平衡时,不同升温速率条件下,焦油产率相似;污泥焦油组分与中低温煤焦油相近,具备提酚、制燃料油和特种油品的潜力;污泥半焦灰分高,固定碳含量低,具有一定热值,比表面积较发达,掺混燃烧、制备吸附剂是其重要的潜在利用方向。     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.     

土壤中砷的化学平衡

本文比较详细地综述了砷的化学特性,环境背景值及来源和循环,土壤中砷的三大化学平衡即沉淀溶解平衡,氧化还原平衡,吸附解吸平衡,以及微生物对砷的转化。     

Elemental uptake by edible herbs and lettuce (Latuca sativa)

The total concentration of toxic elements (aluminum, cadmium, chromium and lead) and selected macro and micro elements (iron, manganese, copper and zinc) are reported in six leafy edible vegetation species, namely lettuce, spinach, cabbage, chards and green and red types of Amaranth herbs. Although spinach and chards had greater than 125 mv of iron, both the amaranthus herbs recorded > than 320 μ g g^{? 1} dry weight. In both the spinach and chard species, the Mn and Zn levels were appreciable recording > 225 μ g g^{? 1} and 150 μ g g^{? 1} dry weight, respectively. Aluminum concentrations were (in μ g g^{? 1} dry weight) lettuce (10), cabbage (11), spinach (167), chards (65), amaranthus green (293) and amaranthus red (233). All the micro and macro elements and the toxic elements (Ni, Cr, Cd and Pb) elements analyzed, were below the recommended maximum permitted levels (RMI) in vegetables. Further the elemental uptake and distribution of the nine elements, at three growth stages of the lettuce plant grown on soil bed under controlled conditions are detailed. In the soil, except for iron (16%), greater than 33% of the other cations were in exchangeable form. Generally in the lettuce plant, roots retained much of the iron (> 224 μ g g^{? 1}) and aluminum (> 360 μ g g^{? 1}), while leaves had less than 200 μ g g^{? 1} of iron and 165 μ g g^{? 1} of Al. Although the concentrations of elements marginally decreased with growth, the lettuce leaves had significant amounts of Mn (30 μ g g^{? 1}), Zn (50 μ g g^{? 1}) and Cu (3.6 μ g g^{? 1}). Some presence of lead in leaves (2.0 μ g g^{? 1}) was noticed, but all the toxic and other elements analyzed were well below the RMI values for the vegetables.     

The dissipation of nonlyphenol in stream and pond water under simulated field conditions

Abstract

The dissipation of 1.0 ppm nonylphenol in stream and pond water, incubated in flasks at 16°C under simulated field conditions up to 44 days indicated that the half‐life was 2.5 days if the flasks were open, and 16 days if they were closed. A transformed product was detected in the closed flasks.

Translocation of nonylphenol in water occurred when treated water samples were incubated in the presence of sediment. After 10 days, nonylphenol was detected only in the sediment, but not in water (detection limit = 10 ppb). About 80% of the nonylphenol was degraded in 71 days, but no degradation occurred if the water and the sediment were autoclaved prior to incubation.