Experimental study on MSW gasification and melting technology

In order to develop municipal solid waste (MSW) gasification and melting technology, two preliminary experiments and a principle integrated experiment were fulfilled respectively. The gasification characteristics of MSW are studied at 500-750℃ when equivalence ratio (ER) was 0.2-0.5 using a fluidized-bed gasifier. When temperature was 550-700℃ and ER was 0.2-0.4, low heat value (LHV) of syngas reaches 4000-12000 kJ/Nm3. The melting characteristics of fly ash were investigated at 1100-1460℃ using a fixed-bed furnace. It was proved that over 99.9% of dioxins could be decomposed and most heavy-metals could be solidified when temperature was 1100-1300℃. The principle integrated experiment was carried out in a fluidized-bed gasification and swirl-melting system. MSW was gasified efficiently at 550-650℃, swirl-melting furnace maintains at 1200-1300℃ stably and over 95% of fly ash could be caught by the swirl-melting furnace. The results provided much practical experience and basic data to develop MSW gasification and melting technology.     

双通道气相色谱法观测本底大气中的CH_4、CO、N_2O和SF_6

在商用Agilent6890N气相色谱仪基础上,通过自组装、集成及调试,在青海瓦里关全球大气本底站建立了双通道气相色谱在线观测系统,以实现同时高精度分析本底大气中的CH4、CO、N2O和SF6.同时,利用保留时间定性,用峰高定量CH4、CO和SF6,用峰面积定量N2O,对体积分数分别为2000.3×10-9、199.8×10-9、320.04×10-9和5.9×10-12的CH4、CO、N2O和SF6混合标气重复进样110次,分析时每隔3个未知样品穿插分析1个标气,以保证分析结果的可靠性.该站试运行期间的数据表明,该系统分析CH4、CO和SF6的稳定性较好,能满足清洁本底大气高精度、高准确度分析要求,分析结果的相对标准偏差(RSD)分别为0.04%、0.50%、0.08%和1.80%.     

医疗垃圾焚烧飞灰的重金属浸出特性及其稳定化处理研究

通过对医疗垃圾飞灰的浸出特性和高温熔融处理实验,研究了浸出时间、液固比、pH值和颗粒尺寸对重金属浸出特性的影响以及飞灰熔融对重金属稳定化处理效果.结果表明,随着浸出时间的增加,飞灰绝大部分重金属的浸出浓度增高,浸出毒性增强;液固比(L/S)增加,大部分重金属的浸出率大大提高,其中重金属Cd的浸出率最大,在液固比为90时,飞灰中的Cd的浸出率达到70%以上;pH为中性左右的时候,医疗垃圾飞灰中的大部分重金属的浸出液浓度最低;颗粒尺寸在较大或者较小时,医疗垃圾飞灰中的大部分重金属浸出浓度较小,大部分重金属在颗粒尺寸250～900μm时,重金属的浸出浓度较高;飞灰高温熔融后,重金属的浸出毒性大大降低,说明熔融对重金属有很好的固化效果.     

某铅锌矿区农田重金属分布特征及其风险评价

为进一步探讨铅锌矿开采和冶炼地区农田重金属污染的分布特征和污染途径,以会泽县者海镇铅锌矿区周边农田土壤为研究对象,共布设496个采样点,测定表层土壤中重金属（Cd、Hg、Pb、Cu、Zn）的含量.利用自然邻点法对表层土壤中重金属含量进行插值拟合,以空间三维模型研究该地区农田土壤重金属污染特征,运用单因子指数、综合污染指数和潜在生态风险指数法对重金属污染程度进行评价,采用相关分析、主成分分析和聚类分析识别污染途径.结果表明：Cd、Hg、Pb、Cu和Zn的含量平均值（mg/kg）分别是云南省背景值的33.05、5.83、12.02、4.89和16.33倍;Cd、Hg、Pb、Zn含量空间分布表现为西北部浓度最高,且中部高于东西两侧,而Cu与此相反;单因子指数评价结果显示99.8%的土样达到Cd重度污染,其次是Cu（82.06%）、Zn（62.50%）;综合污染指数表明,研究区均处于重度污染程度,西北部尤为严重;综合生态风险评价表明,中部风险高两边低,Cd的贡献率最大占61%;相关分析结果显示,Zn、Cd、Pb、Hg之间呈显著正相关性（P < 0.01）,表明其污染途径相近;主成分分析和聚类分析表明,Cd、Hg、Pb、Zn污染途径主要与人类活动有关,Cu主要受自然因素影响,因此对该地区土壤重金属的修复和治理应综合考虑人为因素和自然因素的影响.     

Characterization of products obtained from pyrolysis and steam gasification of wood waste,RDF, and RPF

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products.The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500 °C but the polycyclic aromatic hydrocarbons became the major compounds at 900 °C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700 °C under steam gasification condition.For WBC, both char utilization by pyrolysis at low temperature (500 °C) and syngas recovery by steam gasification at higher temperature (900 °C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500 °C) might be one of viable options. Steam gasification at 900 °C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered.     

Reduction–melting combined with a Na2CO3 flux recycling process for lead recovery from cathode ray tube funnel glass

With large quantity of flux (Na₂CO₃), lead can be recovered from the funnel glass of waste cathode-ray tubes via reduction–melting at 1000 °C. To reduce flux cost, a technique to recover added flux from the generated oxide phase is also important in order to recycle the flux recovered from the reduction–melting process. In this study, the phase separation of sodium and the crystallization of water-soluble sodium silicates were induced after the reduction–melting process to enhance the leachability of sodium in the oxide phase and to extract the sodium from the phase for the recovery of Na₂CO₃ as flux. A reductive atmosphere promoted the phase separation and crystallization, and the leachability of sodium from the oxide phase was enhanced. The optimum temperature and treatment time for increasing the leachability were 700 °C and 2 h, respectively. After treatment, more than 90% of the sodium in the oxide phase was extracted in water. NaHCO₃ can be recovered by carbonization of the solution containing sodium ions using carbon dioxide gas, decomposed to Na₂CO₃ at 50 °C and recycled for use in the reduction–melting process.     

Melting and incineration plants of municipal waste. Chemical and biochemical diagnosis of thermal processing samples (emission,residues)

Control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in emissions and thermal residues from incinerators has been a cause of public concern for more than one decade. Recently, several studies showed that other persistent organic pollutants (POPs) such as coplanar polychlorinated biphenyls (co-PCBs) also have dioxin-like activity and are released from incinerators. Therefore, the present study was aimed at making a risk assessment about dioxin-like activity in extracts of thermal waste residues (e.g. combustion gas; fly ash, slag) from incineration and melting processes in Germany and Japan. For this purpose, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (co-PCBs), polychlorinated naphthalenes (PCNs) and polyaromatic hydrocarbons (PAHs) were analyzed by chemical analysis. Additionally, 2, 3, 7, 8-TCDD equivalents (EROD-TEQs) were determined by in vitro Micro-EROD bioassay using rat H4IIE hepatoma cells. EROD-TEQs could be correlated to I-TEQ values (from PCDD/Fs/co-PCBs) analyzed by chemical analysis resulting in a maximal sixfold higher estimate. Our study indicates minor influences of co-PCBs, PAHs and PCNs to the sum of dioxin-like toxicity in the extracts of thermal waste residues as determined here. Furthermore, we showed that the levels of dioxins and co-PCBs contained in slag from melting processes and bottom ashes from incineration processes were lower by 1-2 orders of magnitude than that in fly ash.     

Brominated flame retardants and heavy metals in automobile shredder residue (ASR) and their behavior in the melting process

The End-of-life Vehicles Recycling Act went into effect on January 1, 2005, in Japan and requires the proper treatment of airbags, chlorofluorocarbons (CFCs), and automobile shredder residue (ASR). The need for optimal treatment and recycling of ASR, in particular, has been increasing year after year because ASR is regarded as being difficult to treat. Dioxin-related compounds, brominated flame retardants (BFRs), heavy metals, chlorine and organotin compounds are all present in high concentrations in ASR. The authors conducted ASR melting treatment tests using a 10-tons/day-scale direct melting system (DMS), which employs shaft-type gasification and melting technology. The results obtained showed that dioxin-related compounds and BFRs were decomposed by this melting treatment. The high-temperature reducing atmosphere in the melting furnace moved volatile heavy metals such as lead and zinc into the fly ash where they were distributed at a rate of more than 90% of the input amount. This treatment was also found to be effective in the decomposition of organotin, with a rate of decomposition higher than 99.996% of the input amount. Via the recovery of heavy metals concentrated in the fly ash, all the products discharged from this treatment system were utilized effectively for the complete realization of an ASR recycling system that requires no final disposal sites.     

Energy-efficient modification of reduction-melting for lead recovery from cathode ray tube funnel glass

Lead can be recovered from funnel glass of waste cathode ray tubes via reduction melting. While low-temperature melting is necessary for reduced energy consumption, previously proposed methods required high melting temperatures (1400 °C) for the reduction melting. In this study, the reduction melting of the funnel glass was performed at 900–1000 °C using a lab-scale reactor with varying concentrations of Na₂CO₃ at different melting temperatures and melting times. The optimum Na₂CO₃ dosage and melting temperature for efficient lead recovery was 0.5 g per 1 g of the funnel glass and 1000 °C respectively. By the reduction melting with the mentioned conditions, 92% of the lead in the funnel glass was recovered in 60 min. However, further lead recovery was difficult because the rate of the lead recovery decreased as with the recovery of increasing quantity of the lead from the glass. Thus, the lead remaining in the glass after the reduction melting was extracted with 1 M HCl, and the lead recovery improved to 98%.     

循环流化床锅炉脱硫灰熔融固化特性研究

为了解决循环流化床锅炉脱硫灰堆存带来的二次污染问题,同时为了将固硫灰能够资源化利用,采用高温熔融技术对脱硫灰进行熔融固化处理,在对熔渣的物相变化、组成变化、密度、重金属、浸出量等特性进行分析的基础上,还研究了冷却方式对熔渣性质的影响。实验结果表明:经熔融处理后,脱硫灰的体积大幅度减小,有害重金属得到了有效固化,同时不同冷却方式能够得到不同性质的熔渣产品。证明熔融固化技术可以实现循环流化床锅炉脱硫灰的减量化、无害化以及资源化利用。