水泥、粉煤灰及生石灰固化/稳定处理铅锌废渣

以铅锌废渣为研究对象,采用水泥、粉煤灰为固化剂,生石灰为稳定剂,对废渣进行固化/稳定化处理,并通过TCLP和Tessier连续提取法对固化/稳定化效果进行分析和评价.结果表明,单独添加水泥或水泥、粉煤灰混合固化处理废渣时,重金属铅TCLP浸出浓度显著减少,但达不到安全填埋要求;当稳定剂生石灰添加量为4%(废渣),固化剂废渣比为0.4∶1(粉煤灰与水泥比为1∶9)时,固化/稳定化效果最佳.此时,固化体中重金属Pb、Zn的浸出浓度分别为0.16 mg·L-1、0.243 mg·L-1,符合安全填埋要求.经过固化/稳定化处理后,降低了废渣中的重金属Pb、Zn交换态比例,有效地限制了重金属的迁移.XRD和SEM分析表明,废渣固化/稳定化后形成的Ca(OH)2、水化硅酸钙凝胶(C—S—H)及钙矾石等物质将重金属离子包容起来,形成稳定的固化体.     

水泥固化六价铬污染土力学性能及微观结构研究

通过一系列无侧限抗压强度和电阻率试验,研究养护龄期、水泥掺量和六价铬离子含量对固化污染土无侧限抗压强度和电阻率的影响以及无侧限抗压强度和电阻率之间的关系。研究发现:水泥固化铬污染土的无侧限抗压强度和电阻率随着养护龄期的增加而增大,但增长速率有所不同。铬离子含量越高,水泥固化铬污染土的无侧限抗压强度越低,电阻率越低;水泥掺量越多,水泥固化铬污染土的无侧限抗压强度越大,养护龄期越长,后期增长较大;当养护龄期较短时,固化土的电阻率随水泥掺量的增大略有提高。10%水泥掺量下的无侧限抗压强度(p_u)和电阻率(ρ)近似呈线性关系:p_u=0.740ρ+1.853,R~2=0.917。淋滤实验结果表明:随着固化剂掺量和养护龄期的增加,重金属浸出率降低,固化效果较好。核磁共振试验结果发现:水泥掺量越高,其水化产物越多,水化产物嵌入孔隙,孔径范围越小。微观空隙分析表明:水泥掺量越高,试样整体的平整度和密实性越好,强度越高。     

几种固化剂组配修复重金属污染土壤

选取沸石、硅藻土、海泡石、膨润土和石灰石等5种矿物材料,以6 g.kg-1的浓度分别添加到50 g供试土壤中,熟化两周后进行毒性浸出实验,研究各固化剂对土壤重金属的固化效果.实验表明石灰石对土壤重金属均有较好的固化作用,因此再将前4种固化剂与石灰石以不同质量比组配,并以同样方法研究各组配对土壤中重金属的固化效果,以期得到固化效果优于单一固化剂的组配固化剂.结果表明,几种组配中效果最好的是硅藻土与石灰石以质量比1∶2的组配,土壤浸提液中Pb、Cd、Cu、Zn浸出量较对照分别降低54.3%、100%、27.2%、63.8%.显然,1∶2的硅藻土+石灰石对土壤Pb、Cd、Zn均有较好的固化作用.     

制革污泥固化稳定化处理

为有效控制制革污泥中的重金属铬污染并安全填埋,采用石灰、粉煤灰和煤渣作为固化剂对制革污泥进行固化/稳定化处理,考察固化剂对制革污泥中重金属毒性的影响,并探讨了固化/稳定化的最佳工艺条件.结果表明,当石灰、粉煤灰和煤渣的掺量分别为0.12 kg.kg-1、0.02 kg.kg-1和0.08 kg.kg-1,养护天数为6 d时,制革污泥固化块抗压强度达到884 kPa,含水率由固化前的79.60%降低至30.20%,满足《危险废物填埋污染控制标准》（GB 18598—2001）的要求.固化块浸出液中Cu、Pb、Zn、Ni浓度同固化前相比,分别降低了92.1%、96.7%、92.8%、88.9%,Cr、Cd、Mn均未检出.固化块浸出液的铬浓度随着石灰添加量的增加而降低,随粉煤灰添加量的增加则为先降低、然后再升高,当石灰与粉煤灰添加量比为6∶1时,协同固化效果显著.     

硫杆菌浸出废旧MH/Ni电池中重金属研究

生物淋滤法具有对环境友好、反应温和、运行成本低等优点,近年来主要用于回收难浸提矿石中有用金属及城市污泥有毒重金属脱除。应用氧化硫硫杆菌和氧化亚铁硫杆菌对废旧MH/Ni电池电极材料中重金属进行了生物淋滤处理可行性及工艺技术研究,考查了初始pH值、电极材料投加量、温度及底物单质硫添加量对金属Ni、Co浸出率的影响。试验结果表明:硫杆菌可以浸出电极材料中的重金属Ni和Co,初始pH值及温度对生物淋滤过程金属Ni、Co浸出率影响显著。在初始pH值1.0、电极材料质量分数为1.0%、温度30℃、底物单质硫质量浓度为4.0g·L-1条件下,经过20d生物淋滤,废旧MH/Ni电池中金属Ni和Co浸出率分别为95.7%和72.4%。     

城市生活垃圾焚烧发电飞灰中重金属的固定化研究

垃圾焚烧发电飞灰排放是重金属污染的一个重要来源之一。选用实验室合成的含硫有机稳定剂(DT)并优选无机固化剂(DF),组成有机-无机复合固定剂体系,进行飞灰中重金属的固定化实验,研究一种经济、有效的飞灰无害化处理方法,以满足生活垃圾填埋污染控制标准对飞灰填埋的处理要求。以广州市生活垃圾焚烧发电产生的飞灰为研究对象,分别考察了DT和DF单一添加处理以及混合联用处理对飞灰中重金属的固定化效果。浸出数据表明,随着DT和DF的投料量的增加,飞灰固化体的浸出浓度相应降低。当DT和DF投加量质量分数分别为1.0%和2.4%时,飞灰固化体的重金属浸出浓度均低于生活垃圾填埋浓度限值,说明DT和DF可以实现药剂配伍,提高飞灰中重金属固定化效果,同时减少有机药剂的使用量,从而降低处理成本。该研究同时做了药剂固定化试验和水泥固化试验,通过对比发现药剂固定化法具有增容少、养护时间短和稳定化效果好的优点。采用分级提取法对飞灰中重金属的形态进行了分析,结果表明经混合药剂处理后飞灰中的重金属的形态均呈现出由不稳定态向稳定态转化的趋势。采用扫描电子显微镜(SEM)对固定化前后的飞灰进行了分析,结果表明经混合药剂处理后的飞灰颗粒变大,且颗粒表面变得致密,空隙减少,从而减少与浸提剂的接触面积,降低其浸出毒性。     

磷酸镁水泥固化/稳定化重金属性能及作用机理研究进展

磷酸镁水泥(MPC)作为一种新型无机胶凝材料,是由过烧氧化镁和磷酸盐通过酸碱中和反应制备得来,具有早期强度高、结构紧密和体积形变小等优点,在固化/稳定化重金属方面受到广泛关注,但存在放热量大、凝结速度快等缺点.本文归纳了国内外学者对磷酸镁水泥固化/稳定化重金属和重金属污染土的研究,重点讨论重金属离子对磷酸镁水泥抗压强度、凝结时间、酸碱度和水化热的影响,环境对重金属MPC体系稳定性的影响,以及其固化/稳定化重金属离子的作用机理,得出主要固化机理为化学键合、吸附作用和物理包裹,最后指出磷酸镁水泥固化重金属研究的不足和对未来研究的展望,为磷酸镁水泥固化/稳定化重金属的研究提出了新思路.     

污泥厌氧消化过程中重金属稳定性研究进展

污水处理产生的剩余污泥含有大量有机质和营养元素,采用厌氧消化技术产沼气实现污泥的稳定化与资源化已成为这一领域的重要发展方向.与此同时,污泥厌氧消化产生的沼渣还可以用作土壤改性材料,但消化沼渣中所含的重金属因其潜在的生态环境毒性严重阻碍了其资源化利用.本文综述了污泥厌氧消化过程中重金属稳定性研究进展,重点对有机质中的腐殖质、反应条件中的温度和p H缓冲体系、促进剂中的纳米铁和表面活性剂等因素对消化过程中重金属稳定性的影响和作用机制进行了总结归纳.p H缓冲体系和表面活性剂通过促进污泥有机物的分解和重金属的释放,从而影响重金属在消化液中的浸出;腐殖质和纳米铁主要是通过物理化学作用,影响消化沼渣中重金属的形态分布;温度则通过改变絮体结构和增强金属离子的扩散运动,影响重金属在消化液中的浸出以及消化沼渣中的形态分布.最后对厌氧消化工艺中提高重金属稳定性的方法和技术进行了展望.     

浸提剂pH值对污泥中重金属浸出的影响

为了探讨浸提剂的pH对污泥中重金属释放的影响,采集了我国四个典型城市污水厂的剩余污泥,应用固体废物浸出毒性的浸出方法(GB5086.2-1997),以不同pH值的浸提剂对污泥中重金属的浸出特性进行了实验研究.实验结果表明,污泥中的Cr和Fe的最大浸出质量浓度分别出现在6.5～7.0和5.0左右的pH值范围;Mo和Ni的浸出质量浓度则随着浸提剂pH值的升高而升高;而Zn和Mn的浸出质量浓度则随着浸提剂pH的升高而降低.这表明,浸提剂的pH 值对污泥中重金属的浸出具有显著的影响,而且pH 值对污泥中重金属浸出的影响因重金属的不同而存在较大的差异.     

市政污泥与生活垃圾掺烧的重金属排放特征与风险

中国市政污泥年产生量逐年攀升,低热值、高含水率和污染物富集等特征为市政污泥的处理处置带来难度,未能科学处置的市政污泥将带来生态风险,因此高效科学的污泥处理处置手段是打好污染攻防战的重要环节。与生活垃圾协同焚烧是实现市政污泥减量化和提高污泥综合利用率的有效处理方法。为探讨市政污泥与生活垃圾协同焚烧后的重金属排放特征与模式,于2016年5月(湿季)与2017年1月(干季)采集广东省某生活垃圾焚烧设施在掺烧0%、5%、10%和15%市政污泥后排放的烟气、飞灰和炉渣样品,并采用原子吸收分光光度法和原子荧光光度法系统分析各焚烧组的Cu、Pb、Cd、Ni、As和Cr的排放特征。结果表明,在干湿两季,各污泥掺烧比例下烟气中Cu、Pb、Cd、Ni、As和Cr的质量浓度分别为0.001 6、0.009 9、0.000 8、0.002 5、0.002 2和0.125 3 mg·m~(-3),未超过《生活垃圾焚烧污染控制标准》(GB18485—2014)限值,能够达标排放。市政污泥掺烧可能引起烟气中部分重金属质量浓度下降,而对飞灰与炉渣中重金属质量分数的影响较小,可按照生活垃圾焚烧后固体废物的处理方法统一处理。Cd、Cr和Cu等重金属排放分布特征存在明显的季节性差异,其中干季主要分布于飞灰与炉渣(大于98%)中,在湿季则主要分布于炉渣(大于70%)中,重金属分布特征可能受焚烧物料的重金属含量与季节性焚烧条件的影响。综上所述,在低于15%掺烧比例条件下,市政污泥与生活垃圾协同焚烧对重金属排放浓度不产生显著影响,与生活垃圾协同焚烧是市政污泥安全处理处置的重要手段。     

Solidification of arsenic and heavy metal containing tailings using cement and blast furnace slag

The objective of this study is to examine the solidification of toxic elements in tailings by the use of cement and blast furnace slag. Tailings samples were taken at an Au-Ag mine in Korea. To examine the best mixing ratio of tailings and the mixture of ordinary Portland cement (OPC) and blast furnace slag (SG) of 5:5, 6:6, 7:3, and 8:2, the 7:3 ratio of tailings and OPC+SG was adapted. In addition, the mixing ratios of water and OPC + SG were applied to 10, 20, and 30 wt%. After 7, 14, and 28 days' curing, the UCS test was undertaken. A relatively high strength of solidified material (137.2 kg cm?2 in average of 3 samples) at 28 days' curing was found in 20 wt% of water content (WC). This study also examined the leachability of arsenic and heavy metals (Cd, Cu, Pb, and Zn) under the Korean Standard Leaching Test, and it showed that the reductions in leachabilities of As and heavy metals of solidified samples were ranged from 76 to 99%. Thus, all the solidified samples were within the guidelines for special and hazardous waste materials by the Waste Management Act in Korea. In addition, the result of freeze-thaw cycle test of the materials indicated that the durability of the materials was sufficient. In conclusion, solidification using a 7:3 mixing ratio of tailings and a 1:1 mixture of OPC + SG with 20% of WC is one of the best methods for the remediation of arsenic and heavy metals in tailings and other contaminated materials.     

Immobilization of some metals in contaminated sludge by zeolite prepared from local materials

In this study, zeolite was prepared from cheap local Egyptian clay (kaolin) and characterized by X-ray diffraction, X-ray fluorescence spectroscopy, SEM. The prepared zeolite was used as a binder for immobilization of the metals Cd²⁺, Cu²⁺, Ni²⁺, Pb²⁺, and Zn²⁺ in contaminated sewage sludge. Different leaching tests were conducted to determine the efficiency of the prepared zeolite for metal stabilization. The leaching of the metals from stabilized sludge decreased as the zeolite amount increased. It was found that 10% of zeolite is sufficient for the stabilization of all metal ions under investigation. It was suggested that the metal uptake mechanism by zeolite was by an ion-exchange mechanism. Examination of the solidified sample for its compressive strength after curing for 28 days yielded a value of 0.83?MPa, which indicates that the treated sludge was well solidified and safe to be used in a wide variety of applications, for instance as a raw material for pavement blocks.     

Characteristics of the stabilized/solidified municipal solid wastes incineration fly ash and the leaching behavior of Cr and Pb

Fly ash is a hazardous byproduct of municipal solid wastes incineration (MSWI). An alkali activated blast furnace slag-based cementitious material was used to stabilize/solidify the fly ash at experimental level. The characteristics of the stabilized/solidified fly ash, including metal leachability, mineralogical characteristics and the distributions of metals in matrices, were tested by toxic characteristic leaching procedure (TCLP), X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectrometer (SEM-EDS) respectively. Continuous acid extraction was utilized to extract metal ions and characterize their leaching behavior. The stabilization/solidification procedure for MSWI fly ash demonstrates a strong fixing capacity for the metals by the formation of C-S-H phase, hydrated calcium aluminosilicate and ettringite. The stabilized/solidified fly ash shows a dense and homogeneous microstructure. Cr is mainly solidified in hydrated calcium aluminosilicate, C-S-H and ettringite phase through physical encapsulation, precipitation, adsorption or substitution mechanisms, and Pb is mainly solidified in C-S-H phase and absorbed in the Si-O structure.     

Heavy metals fraction and ecological risk evaluation in municipal solid waste gasification slag non-burnt bricks

The heavy metals in non-burnt bricks made from municipal solid waste (MSW) gasification slags with a modified European Bureau Community of Reference procedure were studied. Heavy metals were present in the form of oxidizable and residual fractions, which were stable and not easy to dissolve. The preparation process of non-burnt bricks displayed prominent solidification effect for some heavy metals in the gasification slag. The solidified rate for metals, such as As, Cd, Cr, Ni, and Zn reached 89.82%, 79.57%, 73.64%, 66.73%, and 88.05%, respectively. Moreover, the leaching concentrations of eight heavy metals were all below 8 mg/kg. On the basis of these observations, the risk of exposure to heavy metals in non-burnt bricks was evaluated using the solidification formula and the leaching concentration of heavy metals combined with the assessments of the Hakanson potential ecological risk and pollution ratio of secondary phase and primary phase. Results showed that the preparation of MSW gasification slag non-burnt bricks was not harmful to the environment, but attention is warranted for possible migration of heavy metal cadmium (Cd) in the long term, which may result in an impact on the ecological environment.     

Experiences of Coal Ash Artificial Reefs in Taiwan

A feasibility study for using fly-ash from Taiwan coal-fired power stations for artificial reef production was started in 1983. Various mixtures of fly ash stabilized with lime, cement, or industrial wastes and formed into blocks were tested in the laboratory. the results showed that the development of compressive strength of those blocks immersed in the sea water was much better than those exposed in the air. Heavy metal (Cd, Cr, Cu, Ni, Pb, Zn) content of the blocks has been monitored routinely to determine the leaching rates. the result indicates that solidification of fly-ash could indeed immobilize heavy metals better than the original fly ash. From March 1984 to February 1987, 3,682 coal ash stabilized blocks with total weight of 300 tons were designed, fabricated and installed at both Hsin-ta, south western coast, and Kuei-hou, northern coast of Taiwan, for field trials. After four years' underwater observations on 100 cubic blocks at Wan-Li, northern Taiwan, it was shown that the physical integrity of the ash reef blocks had been maintained. the compressive strength and durability was better than the concrete artificial reefs nearby. the ash reefs could also attract fishes and the colonization by benthic organisms was similar to that on concrete reefs. Eighty-eight species of fishes were observed, of which 27 were commercially important, comprising more than 80% of the total biomass. These results demonstrate a potential use for stabilized coal ash as artificial reefs to replace traditionally used concrete reefs to protect and enhance the coastal fishery resources in Taiwan in the future.     

Investigation and risk assessment modeling of As and other heavy metals contamination around five abandoned metal mines in Korea

Tailings, agricultural soils, vegetables and groundwater samples were collected from abandoned metal mines (Duckum, Dongil, Dongjung, Myoungbong and Songchun mines) in Korea. Total concentrations of arsenic (As) and heavy metals (Cd, Cu, Pb and Zn) were analyzed to investigate the contamination level. Several digestion methods (Toxicity characteristics leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP), 0.1 N/1 N HCl) and sequential extraction analysis for mine tailings were conducted to examine the potential leachability of As and heavy metals from the tailings. The order of urgent remediation for the studied mines based on the risk assessment and remedial goals was suggested. The Songchun mine tailings were most severely contaminated by As and heavy metals. Total concentrations of As and Pb in the tailings were 38,600–58,700 mg/kg (av. 47,400 mg/kg) and 11,800–16,800 mg/kg (av. 14,600 mg/kg), respectively. Agricultural soils having high As concentrations were found at the all mines. Average concentrations of Cd in the vegetables exceeded the normal value at all mines areas, while As only at the Dongjung, Myoungbong, and Songchun mine area. One groundwater sample each from the Dongil and Myoungbong mines, and 4 groundwater samples from the Songchun mine had values above 10 μg/L of As concentration. The TCLP method revealed that only Pb in the Songchun tailings, 6.49 mg/L, exceeded the regulatory level (5 mg/L). Employing the 1-N HCl digestion method, the concentration of As in the Songchun mine tailings, 4,250 mg/kg, was up to 3,000 times higher than its Korean countermeasure standard. Results from the sequential extraction of As in the tailings showed that the easily releasable fraction in the Myoungbong and Songchun mine tailings was more than 30% and the residual fraction was less than 40%. Based on results showing the exposure health risk employing the hazard quotient and cancer risk of As, Cd and Zn, the Dongil mine needs the most urgent remedial action. The concentration reduction factor (CRF) of As in both soil and groundwater follows the order: Songchun>Dongjung>Dongil>Myoungbong>Duckum mine.     

An integrated method for the rapid dewatering and solidification/stabilization of dredged contaminated sediment with a high water content

• An integrated method, called PHDVPSS, was proposed for treating DCS. • The PHDVPSS method showed superior performance compared to conventional method. • Using the method, water content (%) of DCS decreased from 300 to<150 in 3 days. • The 56-day UCS from this method is 12‒17 times higher than conventional method. • Relative to PC, GGBS-MgO binder yielded greater reduction in the leachability. To more efficiently treat the dredged contaminated sediment (DCS) with a high water content, this study proposes an integrated method (called PHDVPSS) that uses the solidifying/stabilizing (S/S) agents and prefabricated horizontal drain (PHD) assisted by vacuum pressure (VP). Using this method, dewatering and solidification/stabilization can be carried out simultaneously such that the treatment time can be significantly shortened and the treatment efficacy can be significantly improved. A series of model tests was conducted to investigate the effectiveness of the proposed method. Experimental results indicated that the proposed PHDVPSS method showed superior performance compared to the conventional S/S method that uses Portland cement (PC) directly without prior dewatering. The 56-day unconfined compressive strength of DCS treated by the proposed method with GGBS-MgO as the binder is 12‒17 times higher than that by the conventional S/S method. DCS treated by the PHDVPSS method exhibited continuous decrease in leaching concentration of Zn with increasing curing age. The reduction of Zn leachability is more obvious when using GGBS-MgO as the binder than when using PC, because GGBS-MgO increased the residual fraction and decreased the acid soluble fraction of Zn. The microstructure analysis reveals the formation of hydrotalcite in GGBS-MgO binder, which resulted in higher mechanical strength and higher Zn stabilization efficiency.     

Assessment of toxicity of heavy metal contaminated soils by the toxicity characteristic leaching procedure

The concentrations of Cu, Zn, Pb and Cd in soils near a lead–zinc mine located in Shangyu, Zhejiang Province, China, were determined and their toxicity was assessed using the toxicity characteristic leaching procedure (TCLP) developed by the United States Environmental Protection Agency. The TCLP method is a currently recognized international method for evaluation of heavy metal pollution in soils. The available levels of Cu, Zn, Pb and Cd were 8.2–36, 23–143, 6.4–1367 and 0.41–2.2 mg kg⁻¹, respectively, while the international standards were 15, 25, 5 and 0.5 mg kg⁻¹, respectively. Soils around the mine were more polluted with Zn and Pb, followed by Cd and Cu. Moreover, the levels of heavy metals in the soils extracted by TCLP indicated that extraction fluid 2 was more effective than extraction fluid 1 in extracting the heavy metals from the polluted soils and there was a positive correlation between fluids 1 and 2. Available heavy metal contents determined by TCLP were correlated with soil total heavy metal contents.     

改性污泥用作填埋场中间覆盖层的适用性探讨

为研究改性污泥作填埋场中间覆盖材料的长期性能,通过无侧限压缩试验和渗透试验,研究温度和渗滤液对污泥强度和渗透性能的影响。结果表明,温度升高,污泥的无侧限抗压强度下降,渗透系数增大;在自来水中浸泡一个月后,二者的渗透系数分别减小了14.3%和53.4%,污泥的无侧限抗压强度下降了14.3%,而在渗滤液中浸泡一个月后,污泥的无侧限抗压强度反而提高了91.1%。该改性污泥的强度和渗透性均满足作填埋场中间覆盖层的要求。