基于超临界技术的印刷线路板资源化方法研究

印刷线路板的回收由于其结构和组成材料的复杂性，被认为是电子电器产品回收中的重点和难点之一。提出了将超临界流体技术应用于废弃印刷线路板的回收工艺，研究出了一种环境友好的废弃印刷线路板回收方法。建立了回收模型及回收实验平台，并使用正交实验设计方法对实验进行设计，利用SPSS分析软件对实验数据进行了分析研究并结合实际实验结果得出了最佳工艺参数。通过对反应生成物进行质谱分析，推测出了生成物的主要组分，并据此对反应机理进行了研究。     

超临界CO2回收线路板工艺研究

用正交试验设计进行了超临界CO2回收废弃印刷线路板的实验。以温度、压强、时间和夹带剂为实验因素,通过对实验前后样本在重量、厚度、弯曲强度和断裂强度四方面变化的分析考察了各实验因素对实验效果的影响。实验结果表明,影响超临界CO2法回收印刷线路板的最主要因素为温度、时间和夹带剂,超临界CO2法回收废弃印刷线路板的最佳工艺条件：温度270℃,压强大于7．38MPa,时间3h,夹带剂（水）160mL。实验进一步验证了压强对实验结果的非显著性影响。     

废弃印刷线路板最佳分离参数的实验研究

为研究废弃印刷线路板的热解特性,确定金属和非金属分离的热解最佳参数,用差热-热重联用分析仪对FR-4型印刷线路板进行了热失重分析,并对影响废弃印刷线路板中金属和非金属分离效果的升温速率、颗粒尺寸、热解终温和保温时间等主要因素进行了实验研究。结果表明,FR-4型线路板在320~360℃区间热失重速率达到最大值;升温速率越高,热解起始温度、终止温度和失重峰温也越高,显著失重过程持续的时间越长;当热解终温相同时,升温速率对FR-4型线路板的热失重率影响很小。综合考虑FR-4型废弃印刷线路板中金属和非金属的分离效果、热解装置的设计、热解过程的能耗以及运行过程的控制等因素,最佳热解参数建议设定为升温速率为10℃/min,热解终温为500℃,保温时间取30 min为宜。     

超临界CO2回收线路板工艺研究

采用正交试验设计进行了超临界CO₂回收废弃印刷线路板的实验。以温度、压强、时间和夹带剂为实验因素,通过对实验前后样本在重量、厚度、弯曲强度和断裂强度四方面变化的分析考察了各实验因素对实验效果的影响。实验结果表明,影响超临界CO₂法回收印刷线路板的最主要因素为温度、时间和夹带剂,超临界CO₂法回收废弃印刷线路板的最佳工艺条件：温度270℃,压强大于7.38 MPa,时间3 h,夹带剂(水)160 mL。实验进一步验证了压强对实验结果的非显著性影响。     

罐底含油泥热解动力学参数计算方法的优选

在化学反应设计中反应动力学是较重要的因素。为得到更合理的污泥热解动力学参数计算方法,利用热重分析仪,在氮气气氛下对罐底含油污泥的热解特性进行研究。根据热重实验数据,分别采用Coats-Redfern法、Kissinger法、FWO法和Popescu法计算污泥热解动力学参数,并获取罐底泥热解制油的主要阶段(第2阶段)的反应活化能E、频率因子A并分析各种方法反应机理。通过对比不同计算方法得到动力学参数及拟合曲线与实验曲线的相关性,确定了最佳罐底含油污泥热解动力学参数计算方法。研究表明,Popescu法得到罐底泥的热解过程符合Jander方程,活化能E为101.43 kJ/mol,与FWO法得到的91.20 kJ/mol相近,且预测曲线与实验曲线有较好的相关性(0.9816),说明Popescu法计算罐底泥热解动力学参数更合适。     

半导体存储介质破碎-分选系统的因子优化设计

废弃半导体存储介质一方面载有隐私信息,需要被安全销毁,另一方面富含金属导体、半导体、绝缘体材料,极具回收价值。提出用破碎-风力-高压静电分选系统对其进行安全销毁和物料分选,其中多级破碎部分使信息半导体硅存储材料破碎至0.80 mm以下,而风力-高压静电分选部分能实现半导体、导体、绝缘体的分选。为确定系统工艺参数,实验对风机蝶阀角度(α),风机频率(f),电选电压(U),电选机转辊转速(n)等因素对半导体收集量(M)的影响进行研究,通过因子设计建立了非线性数学模型:M=1.943 8-0.418 7α*+0.306 2f*-0.193 7 f*U*n*+0.181 3α*f*U。进而通过响应优化得出最优工艺参数设置为:α=30°,f=45 Hz,U=30 k V,n=40 r·min-1。在此参数下,金属导体收集率达90.3%,半导体硅收集率达61.0%,实现了半导体存储介质破碎销毁和物料分选。     

废弃印刷线路板碘化法浸金研究

针对碘化法从废弃印刷线路板中提取金的工艺设计,分别考察了碘的质量分数、n(I₂)/n(I^-)比值、固液比、双氧水的质量分数、pH值、浸出时间和浸出温度对金浸出率的影响。结合正交设计优化实验方法,提出了从废弃印刷线路板中碘化法浸取金的最佳工艺条件：碘的质量分数为1.1％,n(I₂)∶n(I^-)=1∶10,双氧水的质量分数为1.5％,浸出时间4 h,固液比为1∶10,浸出温度为常温（25℃）,溶液pH值为中性,此时金浸出率可达97.5％。     

市政污泥干化动力学研究

利用同步热分析仪(TGA/DSC),采用非等温法,开展了市政脱水污泥干化过程的动力学研究。分析了升温速率对污泥干燥过程的影响,确定出污泥干化过程的最概然机理函数G(α)MP,计算了不同升温速率下的表观活化能E和指前因子A。结果表明,污泥非等温干燥过程可以分为缓慢加速、快速加速和减速3个阶段;升温速率的增大会缩短加速段干化时间,但对减速段没有影响;随着升温速率的增加,干化活化能和指前因子先增大后减小,活化能在19.45~28.46 k J/mol之间变化,指前因子变化范围为1.5×105~5.0×106s-1,且在升温速率为15 K/min时两者达到最大值;干燥过程最概然机理函数的积分形式为G(α)MP=1-(1-α)4反应级数为4;污泥干燥过程的活化能和指前因子之间存在动力学补偿效应。     

氧化亚铁硫杆菌浸出废弃挠性PCB中金属的影响因素分析

废弃挠性PCB是资源化价值高的电子废弃物之一,正需环境友好的方法回收其所含的多种有价金属。采用显微镜对破碎后的挠性PCB粉样进行解离情况观察,发现破碎法难以将挠性PCB中的金属与非金属解离。通过设计单因素实验,研究挠性PCB粉末粒度大小、添加量、培养液初始p H、菌接种量、活化时间以及Fe SO4·7H2O添加量6个因素对氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,简称A.f菌)浸出挠性PCB中金属过程的影响。结果表明,A.f菌不能浸出挠性PCB中Au,但Cu、Ni可以有效浸出且最优化条件为:10 g·L-1挠性PCB、粒度0.25~0.42 mm、培养基初始p H 2.5、菌接种量5%、菌活化时间5 d、Fe SO4·7H2O添加量30 g·L-1,金属Cu的浸出率达到90.1%,比未接种处理高出42.4%;金属Ni的浸出率达到了85.9%,比未接种处理高出了32.9%。因此,采用生物法可环境友好地回收挠性PCB中Cu、Ni,有利于废弃挠性PCB的资源化处理。     

印刷线路板废弃物的热解与动力学实验研究

分别应用管式炉反应器和热重分析手段对印刷线路板废弃物的热解行为和热解动力学进行了实验研究.在管式炉中,研究不同的热解温度:700～950℃,对产物分布和气体成分分布的影响.实验结果表明:PCB热解气体的主要成分是H2和CO2,气体的热值较低,仅为2.09～5.41 MJ/m3,PCB不适合以气体产物为目标的能源利用方式.应用Friedman方法对PCB的热解动力学进行了研究,求得PCB的热解动力学参数分别是:表观活化能190.92 kJ/mol,反应级数5.97,指前因子lnA47.14 min-1.     

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.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

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.     

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.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

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.