城市垃圾焚烧飞灰重金属药剂配伍稳定化实验研究

以飞灰中富含的Pb和Zn为目标重金属,对飞灰中重金属药剂配伍稳定化效果了实验研究.选用EDTA、Na2S、NaH2PO4等稳定化药剂和pH值控制,首先将试剂单独投加飞灰中测定重金属浸出浓度,分析各试剂的稳定化效果;然后通过系列试验观察现象,确定试剂最优投加顺序;最后,按照试剂性质制定4个配伍方案,按照最优投加顺序投加试剂,测定分析各个配伍方案的稳定化效果.结果表明:pH值保持在弱碱性(10左右),重金属稳定化效果较好.EDTA二钠、NaH2PO4和Na2S重金属稳定化效果明显,而有机试剂EDTA二钠稳定化效果明显优于NaH2PO4和Na2S;稳定化药剂投加顺序以Na2S、EDTA二钠、NaH2PO4顺序投加处理效果为最佳;配伍方案4处理效果明显优于其他方案,可以实现稳定化药剂配伍相合,提高飞灰中重金属稳定化效果,同时减少有机螯合剂的使用量,从而降低处理成本.     

危险废物焚烧飞灰中重金属的稳定化处理

以上海市某危险废物焚烧厂飞灰为研究对象,采用Na2S、FeSO4、Na3PO4、和Na3C3N3S34种不同类型化学稳定药剂对飞灰进行了稳定化处理,并应用XRD、IR、SEM和连续化学提取法等仪器和手段对Na3C3N3S3处理焚烧飞灰的产物进行分析研究。研究结果表明,Na3C3N3S3对飞灰中的重金属Cr、Pb、Zn的稳定效果最好,Na3PO4对Cr无明显稳定效果。稳定后产物表面变得致密化,Na3C3N3S3与重金属离子生成的沉淀物干燥后无明显晶型存在。经稳定处理后飞灰中的重金属形态由弱酸提取态转化为可氧化态,减少了飞灰中重金属的浸出毒性。     

碱性催化剂对农业废物液化产生生物油和气体的影响

采用热化学处理法对农业废物玉米秸秆和苹果渣进行处理,3种碱性物质Na2CO3、K2CO3和KOH作为催化剂,都能不同程度提高液化生物油收率、减少固体残渣收率.但碱性催化剂会降低气体收率,因而不适合作为以获得气体产物为目的的生物质气化试验的催化剂.就增加液化生物油收率方面而言,Na2CO3的催化效果最好,KOH催化效果次之,K2CO3的催化效果最差.     

铬污染土壤的还原稳定化修复

以湖南某工业场地的铬污染土壤为修复对象,投加不同比例的Fe SO4·7H2O、Fe SO4·7H2O和Ca(OH)2混合物及Na HSO3,通过测定土壤及浸出液中六价铬、总铬以及铬的形态,比较3种稳定剂对该污染土壤的还原稳定化作用。结果表明,Fe SO4·7H2O和Na HSO3对铬污染土壤的还原稳定效果都较好,可以有效还原土壤中六价铬并能降低土壤中总铬的浸出浓度。当Fe SO4·7H2O投加量为2%时,土壤六价铬和总铬浸出浓度降幅分别达到99.0%和57.5%;当Na HSO3投加量为0.8%时,六价铬和总铬浸出浓度降幅分别达到97.7%和42.2%,与前二者相比,Fe SO4·7H2O和Ca(OH)2混合物还原稳定化效果较差。投加Fe SO4·7H2O能够将土壤中活性大的可交换态和碳酸盐态铬转化为稳定的有机态和残渣态铬;而Na HSO3主要将可交换态和碳酸盐态铬转化为相对稳定的铁锰氧化态铬,其稳定化效果要差于Fe SO4·7H2O。     

几种硫化物对紫色土汞的稳定化效果及优化稳定条件

以西南地区广泛分布的紫色土-灰棕紫泥为对象,探讨了硫化物种类(S、Na_2S、FeS、Na_2S_2O_3和DTCR(二硫代氨基甲酸盐))、用量对不同水平汞污染土壤的稳定化效果。结果表明5种硫化物对土壤汞均具有显著的稳定化效果。固定S:Hg摩尔比为1:1条件下,在1.5～250 mg·kg~(-1)汞污染土壤中,几种硫化物稳定效率相对大小顺序:DTCRNa_2SNa_2S_2O_3SFeS。Na_2S和DTCR在高浓度汞污染土壤中均表现较高的稳定化效果,在不同汞污染浓度下均能在3d内使土壤浸出汞浓度满足美国固体废弃物毒性浸出程序(TCLP)浸出标准要求(0.2 mg·L~(-1)),Na_2S_2O_3稳定效果相对较差,对250 mg·kg~(-1)的汞污染土壤,稳定化处理时间需要15d才能达到浸出标准要求,当汞污染浓度≥150 mg·kg~(-1)时,S和FeS不能满足浸出标准要求。固定汞污染浓度为150 mg·kg~(-1)稳定化效果取决于硫化物的用量,其中,仍然以DTCR效果最好,S:Hg=1稳定化处理3 d时即可达汞浸出标准。Na_2S和Na_2S_2O_3则均需要在较高的浓度下才能实现汞的稳定化,但是过高的用量会导致土壤中HgS再次溶解,两者的最佳施用量为S:Hg=5。元素S和FeS则需要以S:Hg5稳定化处理7 d以上才能达到浸出标准要求。土壤中汞的浸出活性与其赋存形态有关,交换态(Exc-Hg)和碳酸盐结合态汞(Carb-Hg)与土壤浸出汞浓度呈显著正相关,高效稳定剂显著促进了汞向有机质结合态(OM-Hg)和残渣态(Res-Hg)转化。硫化物稳定化处理9个月内土壤中浸出汞浓度始终维持在极低水平,满足持续稳定化要求。     

燃煤钙基固砷剂的影响因素研究

利用电石渣、CaCO3、CaCO3·Ca(OH)3和Ca(OH)2作为燃煤钙基固砷剂,通过正交试验研究了固砷剂种类、固砷剂用量、燃烧温度及煤粒径对固砷效果的影响.结果表明,燃烧温度是影响燃煤固砷的最显著因素,最佳为1 050℃;钙基固砷剂中CaCO3和电石渣的固砷效果最好,其次是CaCO3·Ca(OH) 2,Ca(OH) 2的固砷效果最差;钙基固砷剂用量按Ca、S摩尔比计量为2.0、煤粒径为160～200目时,钙基固砷剂具有较好的固砷效果,而且具有固砷固硫的双重作用.     

粉煤灰、电石渣及其配合物碳酸化特性

为了促进粉煤灰和电石渣建材化高效利用和协同矿化CO_2减排,研究了粉煤灰、电石渣及其配合物的碳酸化特性。实验采用pH在线测试方法分别对粉煤灰、电石渣以及两者配合物的碳酸化过程的pH进行在线测试,并对原料和产物进行XRD、TGA和SEM表征。结果表明:相同条件下,粉煤灰碳酸化浆液pH降到7.0的平均速度约为电石渣的51倍;与等量电石渣单独碳酸化相比,粉煤灰与电石渣按照4:1(质量比)复配碳酸化pH降低到7.0的速度较纯电石渣提高了近5.6倍,且在相同电石渣配量的条件下,粉煤灰-电石渣复配料比碳酸钙-电石渣复配料的碳酸化反应完成时间缩短了31.6%,说明电石渣与粉煤灰复配后进行碳酸化反应具有明显协同促进作用。TGA分析表明,纯粉煤灰和纯电石渣的固碳率分别约为2%和61.3%,粉煤灰与电石渣复配料的固碳率较等量单一电石渣和粉煤灰的固碳率之和的计算值提高了19.6%。SEM分析表明,粉煤灰与电石渣复配料碳酸化产物碳酸钙颗粒在粉煤灰表面呈现异位分散附着形态,而单一电石渣碳酸化产物碳酸钙则在电石渣颗粒表面呈现原位聚集附着形态。这可能是复配料固碳率提高的主要原因。     

三种混凝剂处理煤泥水的对比试验研究

本文介绍了石灰、电石渣及CaCl2 分别与聚丙烯酰胺联用处理煤泥水的对比试验研究结果。结果表明 ,三种方法对煤泥水均有较好的处理效果 ,其中CaCl2 法效果最好 ,但药剂费也最高 ,石灰法和电石渣法处理效果相差不大 ,但电石渣法药剂费较低。     

粉煤灰和电石渣对聚丙烯塑料裂解的影响研究

研究了粉煤灰和电石渣对聚丙烯塑料裂解的影响,讨论了加入量对裂解速度和裂解产物的影响.结果表明:粉煤灰和电石渣都使裂解产物中的轻质部分(汽油和裂解气)增加、重油降低;粉煤灰比电石渣更能加快反应的进行,而且加入量越多,反应越快,需时越短;粉煤灰比电石渣对聚丙烯塑料的裂解具有明显的催化促进效果.     

三种混凝剂处理煤泥水的对比试验研究

本文介绍了石灰、电石渣及CaCl2分别与聚丙烯酰胺联用处理煤泥水的对比试验研究结果。结果表明：三种方法对煤泥水均有较好的处理效果，其中CaCl2法效果最好，但药剂费也最高，石灰法和电石渣法处理效果相差不大，但电石渣法药剂费较低。     

Hazardous Waste Minimization: Part VI Waste Minimization in the Foundry Industry

The foundry industry is a major consumer of waste materials (scrap). Unfortunately, the recycling of these waste materials can result in the generation of hazardous wastes that must be properly managed at a significant cost. This article focuses on two waste streams in the foundry industry; calcium carbide desulfurization slag and melt emission control residuals. The author presents an overview of how foundries have evaluated different waste management options with the ultimate goal of minimizing the generation of hazardous waste.     

Immobilization of antimony waste slag by applying geopolymerization and stabilization/solidification technologies

During the processing of antimony ore by pyrometallurgical methods, a considerable amount of slag is formed. This antimony waste slag is listed by the European Union as absolutely hazardous waste with a European Waste Catalogue code of 10 08 08. Since the levels of antimony and arsenic in the leachate of the antimony waste slag are generally higher than the landfilling limits, it is necessary to treat the slag before landfilling. In this study, stabilization/solidification and geopolymerization technologies were both applied in order to limit the leaching potential of antimony and arsenic. Different combinations of pastes by using Portland cement, fly ash, clay, gypsum, and blast furnace slag were prepared as stabilization/solidification or geopolymer matrixes. Sodium silicate–sodium hydroxide solution and sodium hydroxide solution at 8 M were used as activators for geopolymer samples. Efficiencies of the combinations were evaluated in terms of leaching and unconfined compressive strength. None of the geopolymer samples prepared with the activators yielded arsenic and antimony leaching below the regulatory limit at the same time, although they yielded high unconfined compressive strength levels. On the other hand, the stabilization/solidification samples prepared by using water showed low leaching results meeting the landfilling criteria. Use of gypsum as an additive was found to be successful in immobilizing the arsenic and antimony.

ImplicationsDespite the wide use of antimony for industrial purposes, disposal options for an antimony waste such as slag from thermal processing of antimony ore were not reported in the existing literature. This study aimed to develop a disposal strategy for the hazardous antimony waste slag. The findings of this study would contribute to understand the immobilization mechanisms of antimony and arsenic and will also be of interest to the owners of the antimony ore processing plants and to researchers investigating the efficiency of stabilization/solidification and geopolymerization technologies.     

改性钢渣吸附氨氮和磷的特性研究

利用钢渣与氢氧化铝以4∶3质量配比混合,在700℃下进行2 h煅烧,得到改性钢渣。通过批次吸附实验,研究了改性钢渣在不同初始pH值、振荡时间和温度下对水溶液中氨氮和磷酸根的吸附情况,进而分析了改性钢渣对氨氮和磷酸根的吸附等温线、热力学和动力学特性。结果表明,改性钢渣脱氮除磷能力比原钢渣显著增强,且最适pH值为4～8。改性沸石对氨氮和磷酸盐的吸附均符合Langmuir等温吸附方程,氨氮(以N计)最大吸附量在10、20和30℃下分别为1.67、2.59和3.24 mg/g,磷酸根(以P计)的最大吸附量在10、20和30℃下分别为1.02、1.19和1.37 mg/g。热力学参数ΔG0、ΔH0和ΔS0表明,该吸附是一个自发、吸热、熵增型反应过程,且磷的吸附是化学吸附为主,氨氮的吸附是以离子交换吸附和物理吸附为主。改性钢渣对磷和氨氮的吸附动力学符合伪二级方程(R2>0.999)。     

危险废物稳定化/固化技术的现状与发展

本文对危险废物稳定化／固化处理技术的历史、现状以及今后的发展方向进行了较为系统的论述，对该技术在处理危险废物时所存在的问题进行了探讨，认为今后药剂稳定化技术在废物处置预处理领域将会占据重要的地位。     

典型危险废物的工程力学特性

掌握填埋废物的工程力学特性是确保危险废物填埋堆体稳定性的重要前提条件,因此,针对6种典型危险废物的工程力学特性开展了调查研究.研究结果表明,污泥类危险废物的含水率和有机质含量远高于非污泥类危险废物,而前者的比重则显著低于后者.污泥类危险废物的渗透系数相对较小,比污染土壤和飞灰炉渣混合物的渗透系数小1个数量级,比滤池填料的渗透系数小2个数量级.不同危险废物的无侧限抗压强度排序为:飞灰炉渣混合物(314.3 kPa)和滤池填料(278.9 kPa)＞污染土壤(124.9 kPa)＞杭州氧气厂污泥(68.6 kPa)、锌铬污泥(71.4 kPa)、油泥(58.4 kPa).不同危险废物的粘聚力排序为:飞灰炉渣混合物(40.8 kPa)、滤池填料(31.1 kPa)＞污染土壤(20.9 kPa)＞杭州氧气厂污泥(1.94kPa)、锌铬污泥(3.10 kPa)、油泥(1.81 kPa).此外,不同危险废物的内摩擦角差异相对较小,其变化范围在18.8°～35.0°之间.综合分析可知,飞灰炉渣混合物和滤池填料的工程力学特性较好,而污泥类危险废物的工程力学特性则较差.     

改良型湿法制备活性白土清洁生产及末端治理实验研究

传统湿法制备活性白土工艺中存在水耗、酸耗大等清洁水平较低的问题,本研究提出了在生产工艺流程中循环使用硫酸酸性废液、并从循环3次的硫酸废液中回收铝盐制备无铁硫酸铝的一种改良型湿法制备活性白土工艺,对末端治理采用电石渣替代石灰作为中和剂进行了探索性实验研究。实验结果表明,改良型湿法制备活性白土工艺对活性白土产品的理化性质无明显影响,产品质量符合行业标准,且酸的利用率从20%提高到约90%,水耗减少量为原工艺的1/3,无铁硫酸铝主要参数符合相关产品技术标准(HG/T2225-2001)。用电石渣作为中和剂处理酸性废液能够实现出水水质稳定达标,处理成本从255万元降低至210万元。本研究的实施使得活性白土的生产工艺清洁生产水平有较大提高。     

Role of sodium ions in the vitrification process: Glass matrix modification,slag structure depolymerization,and influence of metal immobilization

This study investigates the role of Na ions, a common flux, in the vitrification process. Artificial glass systems composed of Al₂O₃, CaO, and SiO₂ with various Na concentrations were melted at 1450 °C. The specimens were cooled by air cooling and water quenching and the metal mobility was evaluated using a sequential extraction procedure. The X-ray diffraction analysis and scanning electron microscopy observations showed that Na ions governed the air-cooled slag’s structure. Na ions initially depolymerized CaSiO₃-linked chains into CaSiO₃ chains, and further cut them into shorter and nonuniform ones, making the slag structure amorphous. With even more Na ions, CaSiO₃ chains were divided into single SiO₄ tetrahedrons and formed Na-related crystals (Na₂Ca₃Si₂O₈ and NaAlSiO₄). The phase distributions of Al, Cr, Cu Mn, and Ni showed that Na has a positive effect on the immobilization of heavy metals at suitable concentrations, but a negative effect when in excess amounts.

Implications:Vitrification has been widely used to treat hazardous materials. The Na-bearing additives were often used as a flux to improve the melting process. This study described the role of Na played in the vitrification process. The Na ions acted as glass modifier and depolymerize the chain structure of slag. With adequate addition amount of Na ions, the immobilization of heavy metals was improved. The results provided much information about the crystalline phase variation, metal mobility, and surface characteristics while Na serves as a flux.     

Evaluation of the leachability of polychlorinated dibenzo-p-dioxins and dibenzofurans in raw and solidified air pollution control residues from municipal waste incinerators

Leachability of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from raw and solidified air pollution control (APC) residues with selected solvents, including acetic acid, simulated acid rain, humic acid, linear alkylbenzene sulfonate (LAS) and n-hexane was investigated. High-chlorinated PCDD/F congeners were observed in all leachates of raw APC residue samples, with the largest total leaching concentration (61.60 ngm(-3); 0.30 ngI-TEQm(-3)) from treatment with humic acid. Low-chlorinated congeners were mainly leached with LAS and n-hexane. Solidification and stabilization (S/S) processes with cement and sulfur-containing chelating agent decreased the leachability of PCDD/Fs by up to 98% with humic acid and LAS as solvents. However, S/S processes enhanced the leachability of both high- and low-chlorinated PCDD/F congeners with n-hexane as the solvent, which largely increased the toxic equivalent quantity of leachates. These results suggest that conventional S/S processes may effectively restrain the release of PCDD/Fs when APC residues are leached with rain water or natural organic compounds (e.g., humic acid), but may have a deteriorated effect when APC residues are leached with nonpolar organic solvents (e.g., n-hexane) coexisting in the landfill sites.     

硝基氧化剂废水处理研究

用钠盐（Na2CO3和NaHCO3）作为和剂去除硝基氧化剂废水中HNO3;用尿素、Na2SO3去除NO2^-、NO3^-;加入适量的沉淀剂、络合剂、絮凝剂、助凝剂去除废水中的F^-和PO4^3-;并对处理pH值、各种药剂浓度及处理时间作了讨论,得出了最佳条件,处理后的出水达到国家污水排放标准。     

Mercury Measurement and Its Control: What We Know,Have Learned,and Need to Further Investigate

Disposal of mercury waste has always provided unique challenges due to its high degree of complexity and volatility. This study evaluated the feasibility of using waste LF slag to form a cementitious matrix capable of providing an effective stabilization/solidification solution for the treatment of mercury wastes. The new matrix was synthesized and simulated through a combination of alkali activation and autoclaving process and doped with mercury nitrate at increasing dosage while monitoring the final form of the mercury and its effects on the mineral stability and structure of the new matrix. Compressive strength of up to 20 N/mm² was achievable for the original matrix. Promising results were obtained in terms of reduced leachability of the mercury when compared to ordinary Portland cement systems at low doping concentration of around 0.5% by weight. A series of precipitation reactions was found to be the main cause responsible for this successful stabilization, especially the metal sulfide precipitation that occurred with the sulfur present in the original waste LF slag.

Implications: Using waste to treat waste as a concept is a new approach that not only solves waste disposal problems but also minimizes the toxicity and the potential hazard of leaching of heavy metals. This study evaluated the feasibility of using waste ladle furnace slag generated from steel-making industries to form a cementitious matrix capable of providing an effective stabilization/solidification solution for the treatment of mercury-containing wastes. Promising results were obtained, and it clearly showed this approach is feasible, which could be a one-stone-kills-two-birds solution for mercury stabilization as well as an industrial waste disposal problem.