CuO/AC脱硫剂的还原再生

CuO/AC脱硫剂吸硫后 ,其中的 CuO即转化成 CuSO₄,需对其进行再生 .本文分别考查以 Ar气氛和 H₂ 气氛还原再生后脱硫剂二次脱硫活性的变化 ,并通过 TG、TPR和 XRD等表征再生过程 .结果表明 :Ar气氛再生实际为载体 C对 CuSO₄的还原 ,最佳再生温度为 400℃ ;H₂ 气氛再生时 ,最佳温度为 250℃ ;即使在最佳温度下 ,再生后的脱硫活性仍低于新鲜脱硫剂 ,可能源于还原生成的 Cu微晶在较高温度下发生的明显聚集 .     

MIE determination and thermal degradation study of PA12 polymer powder used for laser sintering

Pulverized materials such as metallic or polymer powders play a considerable role in many industrial processes. Their use requires the introduction of preventive safeguards to control the plant's safety.PA12 polymer powder processing by laser sintering is characteristic of this tendency. The present work concerns PA12 powder (bimodal particle size distribution: 10 μm and 55 μm) and relates to explosion sensitivity and the thermal degradation of this powder, which can occur during laser sintering. Minimum Ignition Energy is determined using a modified Hartmann tube combined with the Langlie method developed in the PRISME Laboratory. This study shows the influence of parameters such as distance between the electrodes, powder concentration and arc power on MIE values. Theses parameters vary in the range of 3–6 A for the current intensity of the spark and the electrode gap in the range of 2.5–4 mm. The MIE is obtained for a spark gap of 3 mm and current intensity of the 4 A spark in our device. It shows that the MIE is less than 40 mJ for concentrations approaching 1000 g/m³. At lower concentrations (under 150 g/m³) the MIE increases but discrepancies in measurements appear, probably because of the static electricity that creates strong irregularities in dust dispersion. The second part of this study concerns the thermal degradation of the PA12 which is performed by thermogravimetric experiments coupled with mass spectrometric (MS) analysis for gas investigation. The mass loss measurement combined with the gas analysis allows the principal stages of degradation to be determined so as to calculate the kinetics parameter PA12. Experiments have been performed for different heating rates between 1 and 30 K min^?1 and the reproducibility of experiments has been verified. The activation energy is determined using two methods: Freidman and KAS. For a reaction rate of between 0.2 and 0.6, the activation energy is nearly constant. The KAS method gives a value of E_a = 250 kJ mol^?1 and the Friedman method gives E_a = 300 kJ mol^?1. The gas analysis by MS shows that oxidation begins at over 350 °C and finishes at under 650 °C with the formation of CO₂ and H₂O. Other major peaks with an m/z ratio of 29, 28 and 30 are noticed in this range of temperature. They show the presence of intermediate species such as C₂H₆, NO or CH₂O. The presence of HCN is also detected (m/z ratio of 27).     

高钙特征焚烧飞灰的加速碳酸化处理及对重金属浸出特性的影响

针对生活垃圾焚烧飞灰的高钙含量特征,在室温下采用CO2对焚烧飞灰在液固比(L∶S)为0.25∶1的条件下进行加速碳酸化处理,考察加速碳酸化处理对焚烧飞灰中重金属(As、Cd、Cu、Zn、Sb、Pb)浸出特性的影响.焚烧飞灰XRD分析表明,加速碳酸化处理后飞灰中的Ca(OH)2和CaClOH衍射峰消失,而CaCO3的衍射峰增多,且强度增加.加速碳酸化处理后飞灰中铅的形态发生了改变,并且能够检测到铜的化合物.TG/DTA分析表明,焚烧飞灰在440℃之前增重达到5.70%,SEM-EDS分析证实了Ca(OH)2(s)+CO2(g)→CaCO3(s)反应的发生.焚烧飞灰加速碳酸化处理后的TCLP浸出实验表明,碳酸化时间在2 h内,重金属的浸出浓度除Cd保持不变外都显著下降;而当碳酸化时间超过50 h后,重金属的浸出浓度除Pb外普遍高于飞灰未经碳酸化处理时的浸出浓度.     

不干胶废弃物热重分析

为了探索不干胶类包装废弃物的热解特性,采用热重分析手段分析了不同升温速率条件下不干胶类废弃物的失重特点,并且采用Ozawa法和KAS法比较分析不同转化率条件下的表观活化能分布.热重分析结果表明,不干胶类废弃物的热解主要分为3个阶段:第1阶段(室温～ 200℃)为不干胶类废弃物的干燥阶段,第2阶段(200 ～ 590℃)为热解的主要阶段,第3阶段(590 ～800℃)为热解半焦的深度热解阶段.升温速率对热解失重率有重要影响,Ozawa法和KAS法计算结果表明,2种方法计算的热解活化能比较接近,Ozawa法得到的活化能为349.9 kJ/mol,KAS法得到的活化能为336.9kJ/mol;并且不干胶类废弃物的热解表观活化能呈现出阶段性分布.     

利用热重分析不同废水污泥的热解和燃烧

用热重分析法,升温速率为10℃min-1,研究了五种不同废水污泥的热解和燃烧曲线。从失重率对温度曲线图上我们发现,对于没有经过厌氧消化的污泥,燃烧曲线和热解曲线在开始阶段基本重合,随后燃烧曲线向下偏离热解曲线,偏离很大;而经过厌氧消化的污泥热解和燃烧曲线基本重合或偏离很小,其燃烧曲线在最后一段由于先前形成的碳的燃烧会有一个加速分解,热解分解也会超过燃烧分解。同时为了研究金属含量对其热分解过程的影响,我们也对酸洗污泥的燃烧和热解曲线进行了分析。     

煤直接液化残渣掺烧的燃烧特性及其苯系物的排放特征

为分析煤直接液化残渣(液化渣)燃烧处置技术的可行性和环境安全性,采用热重分析仪分析了液化渣、煤和掺烧物料的燃烧特性,并且通过管式炉模拟燃烧试验,研究了不同温度下掺烧过程中苯系物的排放特征. 结果表明:煤和液化渣的燃烧特性及二者在燃烧过程中苯系物的排放特征存在较大差异,液化渣主要失重过程的温度区间为560~820 ℃,明显高于煤的主要失重过程温度区间(230~625 ℃). 从燃烧过程苯系物的排放规律上看,液化渣在700 ℃燃烧时苯系物排放量达到最大值,明显高于煤的燃烧温度(500 ℃). 2种物料由于燃烧特性的差异,在掺烧过程中相互影响,使得掺烧过程苯系物的排放规律发生变化. 掺烧物料在500 ℃下燃烧的苯系物排放量为23.5 mg/kg,远小于燃烧理论值;而当温度高于700 ℃,苯系物排放量为172.6 mg/kg,远大于燃烧理论值. 总体上看,液化渣无论是单独燃烧还是掺烧,低温条件下其燃烧过程中苯系物排放量远大于高温(≥850 ℃)条件下,因此液化渣的燃烧处置或燃料化利用应选择高温炉型.      

Evaluation of the fish short term reproduction assay for detecting endocrine disrupters

In a fish testing strategy, positive results of the fish short term reproduction assay (FSTR), often trigger a definitive test like the fish sexual development test (FSDT) or the fish full life cycle test (FFLC), entailing ethical and economic problems. This study analysed 137 studies encompassing 35 chemicals with different modes of actions (MOAs). Variability is quantified for MOA endpoints vitellogenin (VTG) and secondary sex characteristics (SSCs) as well as for apical endpoints. Two MOA endpoints could indicate estrogenic, anti-estrogenic, androgenic, anti-androgenic and steroidogenesis activities. Great variability, however, has been observed for chemicals with anti-androgenic and steroidogenesis activities, suggesting that TG229/230 may not be sensitive enough to detect these types of chemicals and may produce false negatives. Changes in apical endpoints like fecundity are not limited to endocrine disrupting chemicals (EDCs). Non-EDCs could induce the similar effects on these apical endpoints. If elucidating MOA is needed, targeted in vitro MOA tests are suggested. Positive in vitro MOA results trigger a definitive test, which could be used for confirmation of the MOA in vivo and for deriving a no observed effect concentration (NOEC). Based on positive MOA results of TG229, a definitive test such as the FSDT or the FFLC is still needed, because the current TG229 has limitation on the derivation of a NOEC. An extended TG229 with more power to detect reproduction effects, as recently proposed in the OECD test guideline program, would improve the possibility to derive a NOEC and increase its usefulness in risk assessment.     

Serum concentrations of persistent organic pollutants (POPs) in the inhabitants of a Sicilian city

Background

Polychlorinated biphenyls (PCBs) and organochlorine pesticides are common environmental contaminants that have been associated with human health problems.

Objectives

To assess serum concentrations of several organochlorine contaminants in general population living in a city with an ancient agricultural tradition and to identify possible exposure sources in Sicily.

Methods

A cross-sectional study was conducted on 101 individuals. Each participant answered a face-to-face questionnaire submitted by well-trained personnel and provided a serum sample which was analyzed for the concentrations of PCBs, HCB, HCHs and DDTs by using gas-chromatography coupled with mass spectrometry.

Results

HCB, p,p′-DDE, PCB 138, PCB 153 and PCB 180 were detected in more than 80% of the study participants. The ng g⁻¹ lipid median concentrations were: 18.6 for HCB; 175.1 for p,p′-DDE; 22. for PCB 138; 32.5 for PCB 153 and 23.0 for PCB 180. PCB 153 and PCB 138, PCB 138 and PCB 180, PCB 153 and PCB 180, and p,p′-DDE and HCB showed a high correlation each other (p < 0.05). HCB and p,p′-DDE concentrations were significantly higher in subjects >49 years old (adj-p = 0.03 in 50-69 years old and adj-p < 0.001 in >69 years old, respectively) whereas PCB 138, PCB 153 and PCB 180 concentrations were higher in males (adj-p = 0.03), in subjects >69 years old (adj-p = 0.04) and in current smokers (adj-p = 0.04).

Conclusions

The present study shows that serum concentrations of organochlorine compounds detected in subjects living in a small Sicilian city with ancient agricultural tradition are similar to those found in subjects living in urban areas of other countries. However, further investigations are needed to compare data from rural/urban areas in the same country, assessing correlations between serum concentrations of several chemical compounds and potential health effects in general population.     

多环芳烃类有机污染土作为水泥生料的热解析实验

采集首钢焦化车间周边土壤,分别进行了TG曲线、素土热处理及生料热处理实验,结果表明:所取土壤中含有多种PAHs类有机污染物,多环芳烃总含量约156.39 mg/kg。PAHs污染土在低于850℃条件下,失重可分为失水、有机物分解及无机碳酸盐分解三个阶段。随着加热温度的增加,素土中的总PAHs去除率升高。将污染土替代水泥硅质原料配制水泥生料,经300℃处理,污染土中PAHs除了萘、苊、二氢苊及蒽外,其他有机物均有残留,说明水泥生料对污染物有一定的吸附作用。600℃处理后,除少量菲残留外,其余有机物基本没有残留。因此,PAHs进入水泥窑协同处置,尤其要考虑生料磨及二级悬浮预热器的烟气中污染物含量。     

热重数据的平滑和微分

在热分析技术中,经常要采用高质量的数据平滑方法。本文采用3种平滑方法来得到微分热重(DTG)数据,并比较了效果。从应用于实验数据和模拟数据的效果来看,可以认为Vondrak和高斯光滑方法有各自的优点,并且好于平均光滑方法。从原始TC数据计算的动力学参数和从平滑得到的DTC数据计算得到的参数很好的一致。这表明平滑算法是有效的,可以直接地应用于热动力学分析中。