水泥窑协同处置含锌粉尘对水泥熟料性能及环境安全性的影响

利用水泥窑协同处置技术对含锌粉尘进行了处置.通过掺入不同量的含锌粉尘煅烧成水泥熟料,探讨含锌粉尘中重金属离子对水泥熟料性能和环境安全性的影响.结果表明,含锌粉尘中的Zn离子可以被有效固化在水泥熟料中,固化率最高可达98.11％;Zn离子在水泥净浆中的浸出浓度低于工业固体废弃物浸出毒性鉴别标准的规定限值,故水泥熟料固化的...     

废物水泥窑共处置产品中重金属释放模型研究——混凝土路面场景

通过模拟煅烧试验制取水泥熟料,并制得混凝土样品。在混凝土路面场景分析的基础上,参照欧盟固体中无机组分有效量测试方法(EA NEN7371),以pH=3.2的HNO3/H2SO4溶液(质量比为1∶2)为浸取液,在液固比为20 L/kg条件下,对混凝土样品进行模拟浸出实验;参照欧盟块状材料中无机组分的扩散实验方法(EA NEN7375)测定混凝土样品中重金属的有效释放量。模拟浸出实验结果表明,Cr、Ni和Cd在浸出过程中扩散控制是其释放的主要因素。在此基础上建立了重金属在混凝土路面中的释放模型。实验室实测累积释放量(实测值)与模型预测累积释放量(预测值)的拟合检验结果表明,实测值与预测值之间差异不显著,释放模型能较好地预测混凝土路面中重金属的长期累积释放量。     

pH值对烧结砖中重金属释放的影响

采用酸消解实验和NEN 7371浸出实验研究了烧结砖中重金属总量和有效释放量,采用pH-dependence实验研究pH对破碎烧结砖样品中重金属(Cr、Ni、As、Cd和Pb)浸出特性的影响,以及烧结砖样品的酸碱缓冲容量。结果表明,烧结砖中重金属的有效释放量低于总量,释放率从大到小依次为CdAsPbNiCr;烧结砖的酸缓冲容量较小,浸出液pH从7.03降到3.64,消耗了29.33 mmol/kg硝酸,碱缓冲容量较大,pH从7.03升到12.40,共消耗256 mmol/kg氢氧化钠溶液,因此在使用烧结砖的过程中要特别注意环境pH;浸提液的酸碱性是影响烧结砖中重金属浸出的重要参数,在实验研究的pH范围内,不同重金属的浸出规律不同。Cr和As的释放受pH影响较小,而Ni和Cd的浸出量随pH的增大而降低,Pb的浸出量在强酸和强碱条件下均较大,当pH在5.59~9.86的范围内浸出量很低。     

液固比对含重金属水泥熟料制品中重金属释放的影响

通过模拟煅烧试验制取水泥熟料，参照JGJ 55-2000（《普通混凝土配比设计规程》）制取混凝土样品，参考SR003.1和NEN 7375浸出试验，分别研究液固比对粒状及块状混凝土样品中重金属（Cr、Ni和As）释放的影响。结果表明，在不同液固比条件下粒状混凝土中的重金属浸出浓度为Cr>Ni>As，Cr、As浸出浓度基本保持不变，分别为2 500 μg/L左右和5～6 μg/L，Ni在液固比（L∶S）<6时，浸出浓度随着液固比的增加而降低，在L∶S>6时，浸出浓度较稳定，为35.7～41.5 μg/L；浸出量均随着液固比的增加而增大。液固比（L∶S）<10时，块状混凝土中重金属累积释放量及扩散系数均随液固比的增加而增大，当L∶S>10时两者基本保持不变。     

水泥回转窑固化处理废弃重金属元素的实验研究

废弃的重金属化学试剂是一类危险的固体废物.通过在水泥回转窑中添加质量小于水泥质量的重金属化学试剂的实验研究表明(本实验添加质量约为水泥的0.1%):掺加化学试剂重金属元素后,各水泥熟料的XRD图谱相似,水泥熟料主要矿物相没有发生大的改变;重金属化学试剂的添加对水泥的7 d、28 d抗压强度的影响较小,符合国家标准;熟料试样在其水化28 d时各重金属的浸出量都很低,已低于工业固体废物浸出毒性鉴别标准规定的指标,由此表明利用水泥回转窑处理废弃化学试剂方法可行.     

基于生态水泥的再生混凝土中重金属浸出动力学研究

使用生态水泥、再生骨料制备再生混凝土.分别通过快速浸出实验和长期连续浸出实验对混凝土中的重金属进行浸取,并采用原子吸收光谱法检测浸出溶液中的重金属含量,对比研究再生混凝土与普通混凝土重金属浸出性能差异.研究发现,快速浸出实验条件下,再生混凝土浸出液各重金属浸出浓度高于普通混凝土浸出浓度,但仍低于《危险废物鉴别标准浸出毒性鉴别》(GB5085.3-2007)标准规定的限值.快速浸出实验条件下重金属浸出量与重金属总量相关性不显著,说明快速实验方法有局限性.长期连续浸出实验结果表明,再生混凝土各重金属元素的扩散系数高于普通混凝土(除Zn外),这是由再生混凝土独特的显微结构引起的.     

镍渣的重金属浸出特性

在分析镍渣的矿物相组成和重金属元素含量的基础上,鉴定了镍渣样品的浸出毒性,并考察了pH、液固比和浸出时间等条件对镍渣样中铬、铅、铜和锌等重金属浸出特性的影响。结果表明,镍渣中的重金属总量约为渣样的0.9%,且铬、铜和锌的含量较高,需进行安全管理。实验所用镍渣样品为第Ⅰ类一般工业固体废物。在强酸条件下镍渣中重金属浸出浓度较大,pH3后浸出浓度显著降低;液固比40 L/kg时,镍渣中重金属不断溶出,液固比40 L/kg后,浸出达到饱和,浸出浓度趋于平衡;随着浸出时间的增加,重金属离子的浸出浓度先增加后减少,但由于各重金属性质不同,各重金属达到最大浸出浓度的时间不同。     

水泥对垃圾焚烧飞灰的固化处理试验研究

对垃圾焚烧飞灰的化学成分、重金属物质的含量及浸出浓度进行测试分析.结果表明,飞灰中Pb和Cr等重金属物质浸出量超过浸出毒性标准,因而被认为是危险废物,必须进行固化处理.还考察了水泥对焚烧飞灰中重金属物质固化的效果,研究表明当飞灰掺量适当时,重金属物质的固化效果良好.重金属物质通过物理固封、替代,沉淀反应和吸附等形式可固化进水泥水化产物结构中.     

石灰干化污泥对土壤重金属稳定化处理的效果

以采自湖南省嘉禾县重金属复合污染土壤为研究对象,采用城市污水处理石灰干化污泥作为稳定剂,对污染土壤进行稳定化处理,并采用TCLP和BCR连续提取法对稳定化效果进行分析和评价。研究结果表明,单独使用石灰干化污泥,TCLP浸出浓度随着干化污泥质量分数的增加而显著减少,干化污泥的质量分数为40%时,稳定化率最大为Zn-98.92%、Cd-99.06%、Pb-96.84%;但是干化污泥的高pH值导致稳定后土壤中As的浸出增加。为了恢复植物生长功能,经过亚铁盐和磷酸调节pH后,石灰干化污泥稳定过的土壤pH有效降低,同时亚铁盐和磷酸有利于促进Pb和Zn的稳定效果;但是对Cd的稳定有负面影响;另外,亚铁盐的加入同时可以减少As的浸出浓度。经处理后土壤中重金属形态由不稳定态转为稳定态,使重金属的浸出浓度明显降低,减少了土壤重金属的浸出毒性。该研究结果表明,石灰干化污泥可以作为资源回收利用,应用于重金属污染土壤的修复中,并能改善稳定后土壤适宜植物生长的理化性质。     

含重金属污泥制砖毒性的浸出

污泥中的重金属是影响污泥处置利用的重要因素,污泥制砖可以有效固结重金属。采用污水厂污泥与页岩按一定配比混合制备烧结砖,通过毒性浸出实验,研究烧结砖对重金属的固化程度以及重金属浸出稳定性,从而评定烧结制砖的安全性。结果表明,在浸出液为中性和酸性条件下,Cu、Cr、As和Pb的浸出浓度基本保持稳定,浸出时间的影响不大,而Zn的初始浸出浓度相对较大,最终逐渐降低;碱性条件下,Cr、Cu和Pb的浸出浓度随时间变化不大,而Zn和As的浸出浓度则在浸提时间内无明显变化规律;但不同p H浸出液下的重金属浸出浓度均远低于国家限值,污泥制砖重金属固化效果好,安全可靠。     

稳定化/固化废物中重金属的渗漏行为

采用穿透渗漏和常见的环绕流动渗漏（动态渗漏）实验方法,研究和比较了经水泥固化的稳定化／固化有毒有害废物的渗漏行为,所用的合成重废物样吕由Ｐｂ＾２＋、Ｚｎ＾２＋、Ｃｕ＾２＋、Ｎｉ＾２＋和Ｃｒ（ＶＩ）等５种重金属组成,结果表明,在同种渗漏方式中,重金属的渗漏行为不同。发生穿透渗漏时,重金属的渗漏速率较环绕流动渗漏时高。由于穿透渗漏加束渗漏过程,因此用它研究废物渗漏行为可节省实验时间。     

以城市污泥为掺料制备烧结砖

以城市污泥为部分原料制备烧结砖,对不同烧成温度下不同污泥掺量的烧结砖的物理、力学性能进行了详细分析。结果表明,污泥可用于制备烧结砖,当污泥掺量≤12%,烧成温度为1 100℃时,烧结砖物理力学性能均符合烧结砖标准要求。此外,实验以污泥掺量为12%的烧结砖,烧成温度为1 100℃为例,进行了重金属毒性浸出实验,以考察烧制污泥砖对重金属的固化作用,进而评定污泥制砖的安全性。结果表明,经过高温焙烧,大多数重金属浸出毒性都显著降低,且符合规范要求,不会对环境造成危害。其中,重金属固化效果最好的为Zn,最差的为Cr。     

Assessment of the mechanical stability and chemical leachability of immobilized electroplating waste

The effectiveness of cement based treatment technology, in immobilizing chromium laden electroplating sludge was assessed by conducting toxicity characteristic leaching procedure (TCLP). The mechanical stability of the blocks was tested by measuring the compressive strength. Other leaching tests such as NEN 7341 test, ANS 16.1 and multiple TCLP (MTCLP) test conducted on select solidified blocks showed that chromium was immobilized by the binder studied. A linear relationship was obtained between the cumulative fraction of chromium leached (CFL) and square root of time in the solidified samples proving that diffusion is the controlling mechanism for leaching of chromium. The leachability indices (LI) obtained for the solidified materials using cement and cement-fly ash system (EPC6, EPFC6A and EPFC6B) satisfy the guidance value as per US NRC, which clearly indicates that chromium is well retained within the solid matrix. Chromium concentrations in the TCLP leachates of the above mix ratios were well within the regulatory level of United States Environmental Protection Agency (USEPA). Molecular characterization of the solidified material was carried out using Fourier transformation infra red (FTIR) technique.     

Stabilization and Solidification of Metal-Laden Wastes by Compaction and Magnesium Phosphate-Based Binder

ABSTRACT

Bench-scale and full-scale investigations of waste stabilization and volume reduction were conducted using spiked soil and ash wastes containing heavy metals such as Cd, Cr, Pb, Ni, and Hg. The waste streams were stabilized and solidified using chemically bonded phosphate ceramic (CBPC) binder, and then compacted by either uniaxial or harmonic press for volume reduction. The physical properties of the final waste forms were determined by measuring volume reduction, density, porosity, and compressive strength. The leachability of heavy metals in the final waste forms was determined by a toxicity characteristic leaching procedure (TCLP) test and a 90-day immersion test (ANS 16.1). The structural composition and nature of waste forms were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively.

CBPC binder and compaction can achieve 80-wt % waste loading and 39-47% reduction in waste volume. Compressive strength of final waste forms ranged from 1500 to 2000 psi. TCLP testing of waste forms showed that all heavy metals except Hg passed the TCLP limits using the phosphate-based binder. When Na₂S was added to the binder, the waste forms also passed TCLP limits for Hg. Long-term leachability resistance of the final waste forms was achieved for all metals in both soil and ash wastes, and the leachability index was ~14. XRD patterns of waste forms indicated vermiculite in the ash waste was chemically incorporated into the CBPC matrix. SEM showed that waste forms are layered when compacted by uniaxial press and are homogeneous when compacted by harmonic press.     

The effect of earthworms on the fractionation, mobility and bioavailability of Pb, Zn and Cd before and after soil leaching with EDTA

The effect of two ecologically contrasting earthworm species Eisenia fetida (epigeic) and Octolasion tyrtaeum (endogeic) on the fractionation (accessed using sequential extractions), mobility (toxicity characteristic leaching procedure, TCLP) and oral bioavailability (Ruby's physiologically based extraction test, PBET) of Pb, Zn and Cd was studied before and after soil remediation with soil leaching. Twenty-step leaching, with 2.5 mmol kg(-1) EDTA used in each step, removed 58.4%, 25.0% and 68.0% of initial soil Pb, Zn and Cd, respectively, shifted the fractionation of residual heavy metals toward less labile forms, and decreased their mobility by 83.7%, 80.3%, and 90.9%. Pb oral bioavailability was reduced by 3.1-times (in each stomach and intestinal phase). After soil leaching, both earthworm species enriched the carbonate soil fraction in their casts with residual Pb, and increased the Pb bioavailability in the simulated intestinal phase by a factor of 2.4 (E. fetida) and 2.8 (O. tyrtaeum). The concentration of Pb in TCLP leachate from E. fetida casts was 6.2-times higher than in the bulk of the remediated soil. These results indicate that the effect of biotic factors on the availability of heavy metals residual in soil after soil leaching requires consideration.     

Mobility of Pb, Cu, and Zn in the phosphorus-amended contaminated soils under simulated landfill and rainfall conditions

Phosphorus-bearing materials have been widely applied in immobilization of heavy metals in contaminated soils. However, the study on the stability of the initially P-induced immobilized metals in the contaminated soils is far limited. This work was conducted to evaluate the mobility of Pb, Cu, and Zn in two contrasting contaminated soils amended with phosphate rock tailing (PR) and triple superphosphate fertilizer (TSP), and their combination (P?+?T) under simulated landfill and rainfall conditions. The main objective was to determine the stability of heavy metals in the P-treated contaminated soils in response to the changing environment conditions. The soils were amended with the P-bearing materials at a 2:1 molar ratio of P to metals. After equilibrated for 2 weeks, the soils were evaluated with the leaching procedures. The batch-based toxicity characteristic leaching procedure (TCLP) was conducted to determine the leachability of heavy metals from both untreated and P-treated soils under simulated landfill condition. The column-based synthetic precipitation leaching procedure (SPLP) were undertaken to measure the downward migration of metals from untreated and P-treated soils under simulated rainfall condition. Leachability of Pb, Cu, and Zn in the TCLP extract followed the order of Zn?>?Cu?>?Pb in both soils, with the organic-C- and clay-poor soil showing higher metal leachability than the organic-C- and clay-rich soil. All three P treatments reduced leachability of Pb, Cu, and Zn by up to 89.2, 24.4, and 34.3 %, respectively, compared to the untreated soil, and TSP revealed more effectiveness followed by P?+?T and then PR. The column experiments showed that Zn had the highest downward migration upon 10 pore volumes of SPLP leaching, followed by Pb and then Cu in both soils. However, migration of Pb and Zn to subsoil and leachate were inhibited in the P-treated soil, while Cu in the leachate was enhanced by P treatment in the organic-C-rich soil. More than 73 % P in the amendments remained in the upper 0–10 cm soil layers. However, leaching of P from soluble TSP was significant with 24.3 % of P migrated in the leachate in the organic-C-poor soil. The mobility of heavy metals in the P-treated soil varies with nature of P sources, heavy metals, and soils. Caution should be taken on the multi-metal stabilization since the P amendment may immobilize some metals while promoting others’ mobility. Also, attention should be paid to the high leaching of P from soluble P amendments since it may pose the risk of excessive P-induced eutrophication.     

Stabilization and solidification of metal-laden wastes by compaction and magnesium phosphate-based binder

Bench-scale and full-scale investigations of waste stabilization and volume reduction were conducted using spiked soil and ash wastes containing heavy metals such as Cd, Cr, Pb, Ni, and Hg. The waste streams were stabilized and solidified using chemically bonded phosphate ceramic (CBPC) binder, and then compacted by either uniaxial or harmonic press for volume reduction. The physical properties of the final waste forms were determined by measuring volume reduction, density, porosity, and compressive strength. The leachability of heavy metals in the final waste forms was determined by a toxicity characteristic leaching procedure (TCLP) test and a 90-day immersion test (ANS 16.1). The structural composition and nature of waste forms were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. CBPC binder and compaction can achieve 80-wt% waste loading and 39-47% reduction in waste volume. Compressive strength of final waste forms ranged from 1500 to 2000 psi. TCLP testing of waste forms showed that all heavy metals except Hg passed the TCLP limits using the phosphate-based binder. When Na2S was added to the binder, the waste forms also passed TCLP limits for Hg. Long-term leachability resistance of the final waste forms was achieved for all metals in both soil and ash wastes, and the leachability index was approximately 14. XRD patterns of waste forms indicated vermiculite in the ash waste was chemically incorporated into the CBPC matrix. SEM showed that waste forms are layered when compacted by uniaxial press and are homogeneous when compacted by harmonic press.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

Effects of sintering atmosphere on cement clinkers produced from chromium-bearing sludge

The purpose of this study was to investigate the effects of sintering atmosphere (oxidizing and reducing) on the polymorphs of dicalcium silicates (Ca2SiO4, C2S) and on the chromium leaching of the belite-rich clinkers made from a chromium-bearing sludge. This sludge was generated in an electroplating factory, and in addition to chromium, it contained nickel, copper and zinc. In the clinker production, air was used as the oxidizing atmosphere, and carbon monoxide, which was produced by burning graphite with an insufficient amount of oxygen, was employed as the reducing atmosphere. Dicalcium silicates were substantially formed under both kinds of sintering atmosphere, but there was some nonhydraulic gamma-C2S in the clinkers produced under the oxidizing atmosphere. In addition, the amount of gamma-C2S decreased with the chromium-bearing sludge addition, whereas that of beta-C2S increased. The clinkers produced under the reducing atmosphere had less residual chromium, a finding that shows that more chromium was evaporated. However, the reducing atmosphere can decrease the proportion of hexavalent chromium (Cr(VI)) in the resulting clinkers. For other heavy metals, the residual amounts of nickel and copper generally increased with the sludge addition, but zinc was absent in most of the clinkers produced under the reducing atmosphere. This implies that the evaporation of zinc is much more significant than that of the other heavy metals under a reducing atmosphere. In the leaching tests, the concentrations of nickel, copper, and zinc were below the detection limits in all the leachates. In terms of chromium, the total leaching concentration was highly related to Cr(VI). The clinkers produced under the oxidizing atmosphere had high leaching concentrations of chromium, and thus failed to meet the regulatory limit. In contrast, the reducing atmosphere was effective in decreasing the chromium leaching, and it therefore makes the resulting cement clinkers more environmentally sound.