重金属螯合剂处理垃圾焚烧飞灰的稳定化技术

引言随着我国社会经济的发展、城市化进程的加快以及人们物质生活的提高,全国城市生活垃圾年产生量已达1.5亿吨以上,并以每年8%～10%的速率增加[1-3]。城市垃圾焚烧是我国垃圾处置的重要手段,在焚烧过程中将产生大量飞灰,飞灰产量与垃圾种类、焚烧条件、焚烧炉型及烟气处理工艺有关,一般约占被焚烧垃圾量的3%～5%。分析表     

垃圾焚烧飞灰重金属药剂稳定化研究进展

生活垃圾焚烧飞灰中存有大量高毒性的重金属物质,若不规范处置容易对土壤、地下水造成严重污染,目前通常采用添加化学药剂的方法来稳定飞灰中的重金属。本文在梳理国内外文献的基础上,归纳评述了飞灰重金属的性质、固化稳定化填埋工艺以及目前已被研究或应用的飞灰重金属稳定药剂,包括硫化钠、磷酸、无定形硅材料、铁化合物等无机药剂以及硫脲、EDTA接聚体、壳聚糖、氨基硫代羧酸盐等有机螯合剂,阐明了药剂作用机制和存在的问题,总结了不同药剂作用下的重金属稳定效果,同时针对新形势下的飞灰重金属稳定化要求进行了探讨,提出今后的研究方向为：选择特征性重金属药剂复配稳定飞灰;以改性、成环方式改良氨基硫代羧酸盐类物质（DTC）物质或以交联接枝等方式开发新型螯合剂。     

Ca(OH)2对污泥焚烧灰渣中Pb含量的影响

将添加有Ca(OH)₂的污泥在管式炉中焚烧，通过原子吸收分光光度计（AAS）测定灰渣中Pb的含量，分析Ca(OH)₂对灰渣中Pb含量的影响。结果表明：在污泥焚烧过程中，Pb的挥发率随焚烧温度呈先上升后下降再上升趋势，结合X射线衍射（XRD）分析发现，这主要是由于硅铝酸盐对Pb的固留作用和挥发动力学的相互影响。添加Ca(OH)₂后，污泥灰渣中Pb的含量有明显的降低，而且随着Ca(OH)₂添加量的增加，污泥灰渣中Pb的含量持续降低，表明Ca(OH)₂的添加，促进Pb的挥发，减少Pb在灰渣中的含量。将灰渣中Pb的形态分为浸出态和残渣态，通过分析X射线衍射（XRD）和灰渣中两种形态Pb的变化规律，得到Ca(OH)₂促进Pb挥发的机理主要是：添加的钙元素与硅铝酸盐反应，降低了硅铝酸盐与Pb反应的概率，从而使Pb转变为挥发形态的可能性增大，因此提高了挥发率。     

水热法稳定垃圾焚烧飞灰中重金属研究进展

随着社会经济的发展和垃圾焚烧的应用,产生了大量属于危险废物的垃圾焚烧飞灰。其无害化处理技术的研发变得日益迫切,而水热处理技术是最具潜力的垃圾焚烧飞灰无害化技术之一。本文综述了水热法处理垃圾焚烧飞灰稳定重金属的研究进展。首先阐述了垃圾焚烧飞灰的理化性质;然后系统介绍了针对垃圾焚烧飞灰的水热处理方法,将其细分为传统水热法、添加剂辅助水热法和微波水热法,并分别总结了各类水热处理方法影响重金属稳定效果的因素,包括反应时间和温度、碱性激发剂及其浓度、液固比等;最后探讨了水热法稳定垃圾焚烧飞灰中重金属技术的优化途径,为后续的研究提供了研究思路,其中探究水热过程中硅铝酸盐矿物的合成及其稳定重金属机理极具发展潜力。     

Potential utilization of oil sludge incineration bottom ash for glass-ceramics: Crystallization kinetics,properties and toxicological evaluation

The bottom ash (OIBA) generated from the incineration of hazardous oil sludge is classified as a hazardous waste. In this work, the OIBA was applied as raw material to prepare SiO₂-Al₂O₃-CaO system glass-ceramics by melt-sintering with the addition of waste glass wool (GW). The effects of basicity (CaO/SiO₂ ratio, 0.52-1.05) and sintering temperature (900–1050 °C) on the crystallization kinetics, properties, microstructure, leaching concentrations of heavy metals and potential toxicity of glass-ceramics were investigated. The results showed that the crystallization pattern was two-dimensional crystallization, and with the decrease of basicity, the main crystalline phase evolved from gehlenite to diopside. And the glass-ceramics with basicity of 0.88 and sintering temperature of 950 °C exhibited the best comprehensive properties, including density (2.72 g/cm³), water absorption (0.06%), compressive strength (452.45 MPa) and chemical corrosion resistance. In addition, the reduction of heavy metal leaching concentration indicates that produced glass-ceramics showed excellent solidification effect on heavy metals, the low toxicity of glass-ceramics leaching solution to the wheat seeds and Artemia suggests the environmental protection characteristics of OIBA-based glass-ceramics. These findings proved that the glass-ceramics produced by OIBA and GW could be a promising method to dispose hazardous waste with preparing high value-added construction materials.     

含油污泥流化悬浮焚烧技术及污染物排放

为了实现含油污泥的低成本、规模化、资源化、无害化处理,胜利油田采用流化-悬浮焚烧锅炉处理含油污泥,使焚烧污染物排放达标。介绍了流化-悬浮焚烧锅炉处理的工艺流程,分析了焚烧技术,焚烧污染物SO2、NOx排放量,二噁英污染物排放量,烟气中粉尘排放量,焚烧余热利用的技术特点。对含油污泥焚烧后的灰渣易燃性和灰渣毒性进行了分析,并对焚烧灰渣再利用进行了论述。含油污泥流化焚烧处理系统实现了环保与资源综合利用的双重效果,项目建成后减少了含油污泥对胜利油田的环保治理压力,累计处理含油污泥26万t,产生了良好的环保效益与社会效益。     

上海城市生活垃圾焚烧飞灰的性质分析

垃圾焚烧飞灰是我国城市垃圾焚烧新技术发展过程中产生的一个新问题,飞灰中有大量有害物质。必须予以安全处置。而飞灰的性质对如何处置以及处置的效果非常重要。飞灰的性质有很大的地域性差异。我们对上海浦东御桥垃圾焚烧厂产生的飞灰的相关性质如化学组成、重金属浸出率、重金属挥发特性等进行了检测。并对结果进行了分析。结果表明：上海市飞灰中SiO2含量较高。有利于进行熔融固化。但飞灰在熔融过程中。重金属的挥发量较大,需要引起注意。     

Properties of water-soluble and insoluble particulate matter emitted from dewatered sewage sludge incineration in a pilot-scale ash melting furnace

Emission of inorganic particulate matter (PM) from the incineration of dewatered sewage sludge has been investigated in a novel ash melting furnace. The sludge containing 79 wt% water was incinerated in an oxygen-enriched atmosphere at the primary temperature of 1400 °C, and its unburned volatile was combusted at 1100 °C in a secondary combustion chamber. A 13-stage low-pressure-impactor and the conventional impinger methods were employed for PM sampling at the outlet of the secondary combustion chamber. The results indicate that, PM is dominated by volatile and semi-volatile elements including Br, Cl, P, S, Na, K, Zn, As, Cu, Mn and Ni. Less refractory elements were found. PM has two major fractions: <0.22 and ?0.22 μm. Their chemical forms as well as water solubility are different between two fractions. The majority of Br, nearly half of Cl, and 40% of S and P are present in the small fraction. They are mostly water-soluble due to the association with alkali elements and heavy metals. The water-insoluble calcium sulfate and calcium/iron phosphate were, however, found in the large fraction of PM. Regarding the cations, the water solubilities of Na, K, Mn and Ni are close to their proportions partitioned into the small fraction of PM, since their water-soluble species were preferentially formed in this fraction. A relatively weak correlation for Al, Ca and As, while no such a correlation were found for Cu, Zn and Fe, due to the complex compounds formed for them.     

Low temperature incineration of mixed wastes using bulk metal oxide catalysts

Volume reduction of low-level mixed wastes from former nuclear weapons facilities is a significant environmental problem. Processing of these materials presents unique scientific and engineering problems due to the presence of minute quantities of radionuclides which must be contained and concentrated for later safe disposal. Low-temperature catalytic incineration is one option that has been utilized at the Rocky Flats facility for this purpose.

This paper presents results of research regarding evaluation of bulk metal oxides as catalysts for low-temperature incineration of carbonaceous residues which are typical by-products of fluidized bed combustion of mixed wastes under oxygen-lean conditions. A series of 14 metal oxides were screened in a thermogravimetric analyzer, using on-line mass spectrometry for speciation of reaction product gases. Catalyst evaluation criteria focused on the thermal—redox activity of the metals using both carbon black and PVC char as surrogate waste materials. Results indicated that metal oxides which were P-type semiconductor materials were suitable as catalysts for this application. Oxides of cobalt, molybdenum, vanadium, and manganese were found to be particularly stable and active catalysts under conditions specific to this process (T < 650°C, low oxygen partial pressures).

Bench-scale evaluation of these metal oxides with respect to stability to chlorine (HCl) attack was carried out at 550°C using a TG/MS system. Cobalt oxide was found to be resistant to metal loss in a HCl/He gaseous environment while metal loss from Mo, Mn, and V-based catalysts was moderate to severe. XRD and SEM/EDX analysis of spent Co catalysts indicated the formation of non-stoichiometric cobalt chlorides. Regeneration of chlorinated cobalt was found to successfully restore the low-temperature combustion activity to that of the fresh metal oxide.     

Development of construction materials using sulfite-rich scrubber sludge and fly ash

Construction materials with characteristics suitable for a variety of applications have been developed using up to 95% of coal combustion by-products comprising of sulfite-rich scrubber sludge and fly ash. These materials can be produced as soil-like mixes that can be prepared at the power plant, transported to the deployment site and compacted using conventional road building equipment without a need for forms. These developed materials provide an early strength of 5.8-8.3 MPa after 7-14 d and are environmentally benign. For a cattle feeding pad application, which is the focus of this paper, the cost is estimated be about 25-30% of the cost of developing a conventional concrete feeding pad. Following mix development and establishment of quality assurance/quality control protocols, a commercial cattle feeding pad has been designed and demonstrated using the developed mix.     

固体废物焚烧灰渣毒性评估及其控制方法研究进展

固体废物焚烧产生的灰渣时环境是一种二次污染物,其中,焚烧飞灰因其含有重金属及有毒有机污染物而被列为危险固体废物,因此在其最终处置前,必须进行稳定化处理.作者介绍了灰渣的污染特性,尤其是飞灰中所含重金属、有毒有机污染物的毒性及其各种评估方法,包括水平震荡法、浸出柱实验法、毒性浸出程序(TCLP),并综述了当前灰渣的控制技术方法和资源化利用手段,如水泥固化法、熔融固化法、化学药剂固化法.     

硅铝调控与晶种诱导对水热稳定飞灰中重金属的协同影响

研究了选取的粉煤灰、膨润土、高岭土、硅藻土作为外源硅铝调理剂添加与雪硅钙石人工晶种诱导对150℃水热法稳定垃圾焚烧飞灰中重金属Pb、Zn、Cu、Cd、Cr的协同影响。飞灰由于富钙而低硅铝的元素特征,导致其在水热条件下无法直接合成沸石类,Pb的浸出浓度仍然超标;当单一或混合添加硅铝调理剂添加量为10%时,其水热产物中有水钙铝榴石或加藤石生成;提高添加量至30%时,均有目标雪硅钙石的生成,这与30%添加量下飞灰中Ca/（Al+Si）元素比接近雪硅钙石的理想元素比值0.67~1.20直接相关。混合添加30%的粉煤灰与硅藻土为最佳选择,水热产物Pb的浸出浓度降低至0.30 mg·L^-1,且在此基础上再添加3%的诱导晶种可加速从第6 h开始即合成雪硅钙石,并使Pb的浸出浓度下降到最低值0.28 mg·L^-1。硅铝调控（30%的复合硅铝调理剂,其中粉煤灰：硅藻土为1：1）与晶种诱导的协同影响下高效生成雪硅钙石,并显著抑制Pb、Zn等在水热过程中向液相的转移、降低其在水热液相中的浓度,使飞灰中的重金属在水热后确实稳定于水热固相产物中而非迁移至水热液相造成污染转移,真正实现了飞灰中重金属的固定化。     

Solidification of electroplating sludge using alkali-activated pulverized fuel ash as cementitious binder

This work investigated the potential for utilization of alkali-activated PFA as solidification binder to treat electroplating sludge. The sludge was solidified using 30 wt.% of lime and 70 wt.% of PFA. Two alkali activators, Na₂SiO₃ and Na₂CO₃, were added at 0, 4, 6, and 8 wt.%. Results showed that early strength development of lime-PFA cements with Na₂SiO₃ and Na₂CO₃ was considerably higher than those without. Addition of electroplating sludge resulted in reduced strength. The strength reduction was greater when 4% Na₂SiO₃ activator was used than when 8% Na₂CO₃ activator was used. A higher pH of Na₂SiO₃ solution (pH=13.5) compared to that of Na₂CO₃ solution (pH=11.9) resulted in resolubilization of metal hydroxides from the electroplating sludge, which competed with calcium ion for soluble silicate. In addition, Pb, Cd, and Cu were not found in the toxicity characteristic leaching procedure (TCLP) leachates. Cr, Zn, and Fe were detected and in some cases Cr exceeded U.S. EPA allowable limits.     

垃圾焚烧飞灰水洗脱氯及重金属浸出特性研究

系统研究了机械炉排炉垃圾焚烧飞灰水洗过程中氯化物和重金属的浸出特性,并采用Visual MINTEQ模拟分析水洗液中重金属的存在形态。结果表明：飞灰中的氯主要以可溶性氯化钠（NaCl）、氯化钾（KCl）、氯化钙（CaCl₂）、碱式氯化钙（CaClOH）的形式存在,飞灰水洗浸出成分97%以上为氯离子（Cl^-）、钠（Na）、钾（K）、钙（Ca）,其中氯离子占比高达60%;重金属及其他成分的浸出量很少,不足1%。水洗对氯离子的去除效果非常明显,可达92%以上,但是重金属的浸出量极低。飞灰单次水洗最佳条件：液固体积质量比为6 mL/g,洗涤时间为10 min。Visual MINTEQ模型分析表明,pH是控制飞灰水洗液中铅（Pb）、铜（Cu）、锌（Zn）、镉（Cd）形态的重要因素,氯离子（Cl^-）对镉的形态分布也有着重要的影响。飞灰水洗液电导率与氯离子质量浓度具有极好的线性相关性,其可作为监测滤液中氯离子质量浓度变化的有效间接指标。     

利用城市垃圾焚烧飞灰煅烧水泥熟料初探

针对垃圾焚烧飞灰化学组成上的特点,进行了利用垃圾焚烧飞灰烧制水泥熟料的探索研究,通过试验研究了其对水泥生料的易烧性、烧制的水泥熟料的力学性能和水化速率等的影响规律。研究结果表明,垃圾焚烧飞灰可以用作水泥原料从而有效地降低其处置成本,减少其对环境造成的二次污染,硬化水泥浆体水化28d时各重金属浸出量低于鉴别标准规定的指标,是一种有待开发的潜在的水泥原料资源。     

模拟酸雨对污泥焚烧灰渣砖中重金属浸出影响

用不同pH的模拟酸雨浸泡掺杂污泥焚烧灰渣自制的混凝土路面砖,探讨了相同浸泡时间时,模拟酸雨pH对自制路面砖中重金属浸出的影响。结果表明,在相同浸泡时间时,铬、锰、铜、铁的浸出浓度都随着模拟酸雨pH的增大而下降。在pH为4.4的模拟酸雨中,浸泡时间大于8小时后,铬、锰、铜、铁浸出浓度的大小关系是铬>锰>铜>铁。而镉、镍、铅的浸出浓度在各种模拟酸雨中都小于0.1 ppb。     

城市污泥中重金属存在形态、去除及稳定化研究进展

城市污水处理厂污泥产生量大,含有丰富的有机质、氮、磷、钾等农作物所需营养物质,但由于受重金属的污染使污泥无法直接农用。本文简述了城市污泥重金属的来源、特点及危害。重点论述了城市污泥中重金属去除和稳定方法,包括化学法（电化学法、化学试剂法）、生物法（微生物法、植物法、低等动物法）、物理法（超临界流体萃取、微波和超声）及联合技术。分析了各种方法处理污泥重金属过程中重金属的形态变化及其对处理效果的影响,对比各种方法的优缺点、影响因素及适用范围。指出污泥中重金属形态分布是影响去除效果的关键因素,污泥中重金属形态分布差异性大,且大部分重金属以稳定或相对稳定的状态存在,导致物理法和生物法去除效率较低,微生物和低等动物处理法相比植物法（备受时空限制）则表现出更好的适应性;电化学法对可氧化、可还原态分布的重金属都能起到较好的转化去除作用,但往往受由污泥向污泥液相中转移过程的控制,电损耗较突出;化学试剂浸提剂是目前效率较高的方法,但强酸环境常导致污泥营养物质流失和酸根离子累积,农用时容易板结而不利于污泥土地利用。因此,以土地利用为前提的条件下,将各种处理技术联合运用以提高污泥重金属去除率有待于进一步研究。     

Integrated utilization of high alumina fly ash for synthesis of foam glass ceramic

Due to the numerous increase of the building energy consumption and huge volume of industrial wastes produced in China, the development of thermal insulation materials is quite needed. Herein, foam glass ceramic, a kind of thermal insulation materials, was fabricated by using solid wastes high alumina fly ash and waste glass as the main raw materials. First, in this study the proportion scheme of this research was designed by using Factsage 7.1 and the foaming agent was CaSO₄. Secondly, the decomposition of calcium sulfate and the influence of process parameters, namely the sintering temperature and the foaming agent additive amount, on the microstructure and mechanical properties of foam glass ceramic were investigated. The experimental results showed that when the proposed foam glass ceramic was sintered at between 1180 and 1220?°C, it exerted excellent macro and micro properties. The optimum parameters were 2% CaSO₄ addition and sintering temperature of 1200?°C, and the corresponding bulk density and compress strength values were 0.98?g/cm³ and 9.84?MPa, respectively. Overall these results indicated that the preparation of foam glass ceramic made up a promising strategy for recycling industrial waste into new kind of building insulation materials.     

含砷石膏渣水泥固化/稳定化：预煅烧影响和砷固化机理

提出了一种预煅烧和水泥固化/稳定化相结合的无害化处置含砷石膏渣方法,研究了预煅烧影响及砷固化机理. 含砷石膏渣中砷含量为8.56%,浸出毒性高达1097.5 mg/L,远高于《危险废物鉴别标准GB5085.3-2007》中危废鉴别值5 mg/L. 预煅烧温度为600和700℃时,石膏渣中亚砷酸盐分解导致总砷量和砷迁移性降低,砷浸出毒性可显著降低至较低水平(41.2和4.2 mg/L). 采用水泥固化可降低砷浸出毒性和控制砷泄露风险,较高温度(600和700℃)预煅烧后的石膏渣经水泥固化后抗压强度分别达4.2和5.2 MPa,砷浸出毒性分别达到0.98和0.22 mg/L,低于GB5085.3-2007危废限值. 砷以Ca2As2O7和AlAsO4形式被包裹或吸附在C?S?H水化产物中,降低了砷迁移性;预煅烧可加速石膏渣水泥固化中砷参与水泥水化和化合反应,导致更多且密实的AlAsO4和Ca2As2O7相形成,强化砷固化效果. 该方法有利于含砷量高和毒性高的含砷石膏渣处置,固化体可直接进入垃圾填埋场.     

Characterization of an alkali activated lagoon ash and its application for heavy metal retention

The wet disposal of ash, from the coal-fired thermal power plants, involves its mixing with water and its impoundment in the ash ponds or lagoons. This causes the interaction of ash and the alkalies present in it with water over a period and the formation of ash zeolites (i.e. zeolitization of the ash) takes place. In order to simulate such ash-water interactions, alkali activation of a typical lagoon ash, from India, has been conducted. Investigations have been conducted to identify the effect of zeolitization of the ash on its physical, chemical and mineralogical characteristics. Such studies are essential to explore the possibility of application of the lagoon ash, and the zeolitized ash, for various environmental applications, viz. retention and removal of heavy metals from the industrial sludge.