Study of the treatment effectiveness of a solidification/stabilization process for waste bearing heavy metals

The sludge from a steel processing unit bearing zinc, lead, iron, and manganese was solidified with ordinary Portland cement. The waste was stabilized in the specimens with a waste/binder ratio range of 0.16–4.0. On the basis of the available leaching and unconfined compressive strength, the performance of the solidified/stabilized waste was compared for different numbers of curing days. It was found that curing up to 28 days resulted in a performance improvement, as shown by less leaching of heavy metals and the increased unconfined compressive strength of the specimen. The treatment effectiveness of the solidification/stabilization process was assessed for the metals Pb, Zn, Fe, and Mn, and was found to be 89%, 95%, 74%, and 90%, respectively, for an optimum ratio of 4.0 after 28 days of curing.     

铬渣水泥固化体稳定性研究

采用水泥固化的方法对铬渣进行处理。在水泥与铬渣、砂、水、硅酸钠的质量比为1：0．6：0．45：0．15：0．1时固化效果较好。固化体经28d的养护后,表面Cr^6 的浸出率为10^-5数量级,即使破碎至5mm以下的粒度,其Cr^6 的浸出质量浓度仍在国家标准以下。模拟酸溶试验和固化体抗压强度测试结果表明,固化体用于填埋是长期安全的。     

强酸性硫化砷废渣的稳定固化

采用污泥、石灰、氧化镁和水泥等药剂稳定固化强酸性硫化砷废渣(简称砷渣)。以浸出液中砷的质量浓度为考核指标,采用正交实验考察了稳定化药剂加入量对废渣浸出毒性的影响。实验结果表明:污泥加入量是影响废渣浸出毒性的最主要因素;在m(污泥):m(砷渣)=2.0、m(石灰):m(砷渣)=1.0、m(氧化镁):m(砷渣)=0.10、m(水泥):m(砷渣)=0.3的最佳实验条件下,砷的浸出质量浓度由1780.00 mg/L降至1.37 mg/L,低于GB 18598—2001《危险废物填埋污染控制标准》中砷浸出质量浓度为2.5 mg/L的填埋限值;处理后废渣中其他金属的浸出质量浓度也低于标准限值。     

Stabilization of chloro-organics using organophilic bentonite in a cement-blast furnace slag matrix.

The application of cement-based stabilisation/solidification treatment to organic-containing wastes is made difficult by the adverse effect of organics on cement hydration. The use of organophilic clays as pre-solidification adsorbents of the organic compounds can reduce this problem because of the high adsorption power of these clays and their compatibility with the cementitious matrix. This work presents an investigation of the effect on hydration kinetics, physico-mechanical properties and leaching behaviour of cement-based solidified waste forms containing 2-chlorophenol and 1-chloronapthalene adsorbed on organophilic bentonites. These were prepared by cation exchange with benzyldimethyloctadecylammonium chloride and trimethyloctadecylammonium chloride. The binder was a 30% pozzolanic cement, 70% granulated blast furnace slag mixture. Several binder-to-bentonite ratios and different concentrations of the organics on the bentonite were used. Kinetics of hydration were studied by measurement of chemically bound water and by means of thermal and calorimetric analyses. Microstructure and other physico-mechanical properties of the solidified forms were studied by means of mercury intrusion porosimetry, scanning electron microscopy and unconfined compressive strength measurement. Leaching was checked by two different leaching tests: one dynamic, on monolithic samples, and the other static, on powdered samples. This study indicates that the incorporation of the organic-loaded bentonite in the binder matrix causes modifications in the hardened samples by altering cement hydration. The effects of the two organic contaminants are differentiated.     

Examination of the influence of dissolved halite (NaCl) on the leaching of lead (Pb) from cement-based solidified wastes

The leaching of lead from cement-based solidified waste forms mixed at different water/cement ratios was studied by conducting equilibrium and semi-dynamic leaching tests using deionized water and sodium chloride solutions. The results suggest that leaching of the primary constituents of the cement (calcium, silicon and sulfate) is controlled by solubility equilibria, with increased leaching into chloride solutions due to ionic strength effects. The original porosity of the waste forms increased with water/cement ratio and chloride solutions further increased it as a result of decalcification. Lead leaching was generally low, and appears to be a transport-controlled process, such that leaching correlates positively with porosity.     

Modelling the effects of waste components on cement hydration

Ordinary Portland Cement (OPC) is often used for the solidification/stabilization (S/S) of waste containing heavy metals and salts. These waste components will precipitate in the form of insoluble compounds on to unreacted cement clinker grains preventing further hydration. In this study the long term effects of the presence of contaminants in solidified waste is examined by numerically simulating cement hydration after precipitation of metal salts on the surface of cement grains. A cement hydration model was extended in order to describe pore water composition and the effects of cement grain coating. Calculations were made and the strength development predicted by the model was found to agree qualitatively with experimental results found in literature. The complete model is useful in predicting the strength and leaching resistance of solidified products and developing solidification recipes based on cement.     

Efficiency of a blast furnace slag cement for immobilizing simulated borate radioactive liquid waste

The efficiency of a blast furnace slag cement (Spanish CEM III/B) for immobilizing simulated radioactive borate liquid waste [containing H3BO3, NaCl, Na2SO4 and Na(OH)] has been evaluated by means of a leaching attack in de-mineralized water at the temperature of 40 degrees C over 180 days. The leaching was carried out according to the ANSI/ANS-16.1-1986 test. Moreover, changes of the matrix microstructure were characterized through porosity and pore-size distribution analysis carried out by mercury intrusion porosimetry (MIP), X-ray diffraction (XRD) and thermal analysis (TG). The results were compared with those obtained from a calcium aluminate cement matrix, previously published.     

Reuse of residues arising from lead batteries recycle: a feasibility study

The performance of products arising from the stabilization/solidification of slags from lead batteries recycle into a Portland cement matrix has been evaluated not only in order to get a stabilized waste to be disposed of according to the current legislation, but also to obtain a recyclable material, with both economic and environmental benefits. Under this respect a detailed characterization of raw slags has been performed and different slag-cement samples have been prepared by varying the slag content. The parameters related to the cementation process have been evaluated and a series of tests on the final waste forms have been carried out, aimed at assessing both mechanical performance and leaching behaviour. In spite of the acceptable values for flexural, compressive and tensile strength, however, the high release of lead from the solidification products seems to be a limiting factor for a reusable material. While explanations of such phenomenon are given (high alkalinity of Portland cement; early "doping" of cementitious components by lead in the amorphous state), the main conclusion of the research work is that further efforts should be addressed to the adoption of a different or a modified incorporation matrix.     

Solidification with water as a treatment method for air pollution control residues

The process of solidification with water was studied on air pollution control (APC) residues from incineration of refuse-derived fuel (RDF) regarding mechanical strength and leaching behaviour of solidified material. Factorial design in two levels was applied to investigate the impact of water addition, time, and temperature to mechanical strength of solidified material. Factors time and temperature, as well as the interaction between the addition of water and time significantly (alpha=0.05) influenced the mechanical strength of solidified material. The diffusion-leaching test NEN 7345 was performed to investigate if the leaching behaviour of elements from solidified material was determined by diffusion. Since it was found that leaching is not diffusion controlled, the long-term leaching behaviour was not assessed. However, the investigation showed that some of the studied components (Al, Hg, Mn, Pb, Si, and Zn) could be considerably demobilised by solidification with water. Concentrations of As, Cd, Co, Cu, Fe, and Ni were either below or not quite above the detection limits to be included in the analysis of leaching behaviour. The elements least demobilised by solidification were Cl, Cr, K, and Na.     

固硫灰固化焦化废水处理外排污泥

采用机械力化学法活化循环流化床燃煤固硫灰,用于固化焦化废水处理外排污泥(CWT污泥)。探讨了固硫灰活化条件,并通过XRD和FTIR分析了固硫灰固化CWT污泥中重金属的机理。实验结果表明:当m(Ca O)∶m(Ca O+固硫灰)为20%、球磨频率为40 Hz、球磨时间为2 h时,养护28 d固硫灰固化体的平均抗压强度达到72.2 MPa;当污泥掺加量为50%(w)时,养护28 d含污泥固化体的抗压强度达到8.5 MPa,固化体浸出液中Pb2+和As5+的质量浓度分别为0.177 mg/L和0.013 mg/L,均远低于GB 5085.3—2007《危险废物鉴别标准浸出毒性鉴别》的规定限值。XRD和FTIR表征结果表明,在固硫灰活化过程中,混合体系水化生成了C—S—H凝胶、斜方钙沸石和钙矾石,可通过物理包裹、吸附及离子交换的形式实现CWT污泥中Pb2+和As5+的固化/稳定化。     

粉煤灰-粉煤灰合成沸石对Cs~+的固化

以电厂废弃物粉煤灰为原料、采用碱熔-水热法制备了粉煤灰合成A型沸石(以下简称沸石),再以沸石对溶液中的Cs+进行分离富集,最后在碱激发剂的作用下以粉煤灰和吸附后的沸石制得地聚合物固化体。对固化体的性能进行了评价,并探讨了固化机理。实验结果表明:在吸附温度25℃、初始Cs+质量浓度100 mg/L、固液比10.0 g/L的条件下,沸石对的Cs+的吸附率达98%,比粉煤灰提高了2倍以上;沸石掺量为20%~30%(w)时,固化体的抗压强度符合GB 14569.1—2011要求,固化体中Cs+的42 d浸出率和累计浸出分数均远优于GB 14569.1—2011限值,表现出优异的抗浸出性能。     

Cement based solidification/stabilization of arsenic-contaminated mine tailings

Cement was used to solidify/stabilize the abandoned mine tailings contaminated primarily with arsenic (up to 88 mg/kg) and lead (up to 35 mg/kg). Solidified/stabilized (s/s) forms with a range of cement contents, 5–30 wt%, were evaluated to determine the optimal binder content. Unconfined compression strength test (UCS), Korean standard leaching tests, toxicity characteristic leaching procedures (TCLP), and synthetic precipitation leaching procedure (SPLP) were used for physical and chemical characterization of the s/s forms. Addition of 5% cement was enough for the s/s forms to satisfy the UCS requirements (0.35 MPa). The addition of 7.5% cement remarkably reduced the leachability of arsenic in tailings. However, that of lead tends to increase slightly with increase of cement content due to its amphoteric nature. The discussions were made for determination of optimal binder content and for results from different evaluation procedures.     

Hybrid cement-assisted dewatering,solidification and stabilization of sewage sludge with high organic content

Sewage sludge with high organic content is particularly difficult to dewater before disposal in landfill. In this study, different hybrid cement binders were investigated to evaluate their ability to dewater the sewage sludge with high organic content. After 7 days of stabilization, the CASC (Mayenite/Sulfoaluminate cement) hybrid binder showed an excellent efficiency on both water content reduction and strength development; the water content and unconfined compressive strength value of solidified sludge reached 52.43 % and 109.55 kPa, respectively, at 8 % binder/sludge mass rate. The horizontal vibration leaching test (HJ 557-2009) indicated that leachability of heavy metals of the CASC-solidified sludge was far lower than that of non-solidified sludge and CAPC-solidified sludge. Furthermore, SEM and XRD analyses suggested that certain hydrates formed in the solidification process might have accelerated the depletion of interstitial water and strength development in the CASC-solidified sludge.     

Solidification/stabilisation of air pollution control residues using Portland cement: Physical properties and chloride leaching

Portland cement (CEMI) was used to solidify air pollution control (APC) residues from an energy-from-waste plant burning municipal solid waste. APC residue/CEMI mixes were prepared with CEMI additions ranging from 0 to 50 weight% (wt%) of total dry mass and water/solids ratios between 0.40 and 0.80. Isothermal conduction calorimetry was used to assess the effect of APC residues on the hydration of CEMI. Although up to 30wt% additions of APC residues accelerated CEMI hydration, the total heat of hydration during the initial 98h was significantly reduced. Higher levels of APC residues severely inhibited CEMI hydration. The consistence, setting time, compressive strength, porosity and chloride leaching characteristics of the solidified products were determined. As might be expected, increasing the CEMI addition and reducing the water content resulted in increased compressive strengths. All mixes achieved compressive strengths greater than 1MPa at 7 and 28days but only 50wt% samples did not show significant strength reduction when tested after immersion in water. Monolithic leaching tests indicated low physical immobilisation of chloride in the CEMI solidified APC residues, with chloride leaching in excess of relevant UK landfill waste acceptance criteria (WAC). The results of this study show that greater than 50% CEMI additions would be required to effectively treat APC residues to meet current WAC limits.     

Reuse of municipal solid wastes incineration fly ashes in concrete mixtures

This study is aimed at assessing the feasibility of concrete production using stabilized m.s.w. (municipal solid waste) incineration fly ashes in addition to natural aggregates. The tested fly ashes were washed and milled, then stabilized by a cement-lime process and finally were reused as a "recycled aggregate" for cement mixture production, in substitution of a natural aggregate (with dosage of 200-400 kg m(-3)). These mixtures, after curing, were characterized with conventional physical-mechanical tests (compression, traction, flexure, modulus of elasticity, shrinkage). In samples containing 200 kg(waste) m(-3)(concrete), a good compressive strength was achieved after 28 days of curing. Furthermore, concrete leaching behavior was evaluated by means of different leaching tests, both on milled and on monolithic samples. Experimental results showed a remarkable reduction of metal leaching in comparison with raw waste. In some cases, similar behavior was observed in "natural" concrete (produced with natural aggregates) and in "waste containing" concrete.     

The effect of accelerated carbonation on the properties of cement-solidified waste forms

Ordinary Portland cement blended with blast furnace slag and pulverised fuel ash was used to solidify two industrial wastes containing large amounts of metals. The solidified mixes were carbonated using an accelerated regime previously established and compared for strength development, leaching characteristics and phase development against their non-carbonated analogues. A significant difference in the immobilisation of metals such as Zn, Ni and As was recorded for samples in which carbonation was optimised. The work has shown that by controlling mix parameters it is possible to improve the immobilisation of specific metals. Electron microanalysis showed that this is partly due to the precipitation of calcite in the solidified waste pore structure. Carbonation was also found to accelerate C₃S hydration in all carbonated samples and to modify the morphology of residual cement grains through the formation of a calcite coating over de-calcified hydration rims. Some metals appear to be incorporated in both of these zones.     

Municipal incineration bottom ash treatment using hydrothermal solidification

Solidification of municipal incineration bottom ash (MIBA) has been carried out using a hydrothermal processing method, in which the MIBA was first compacted in a mold at 5-20 MPa, and then hydrothermally cured in an autoclave under saturated steam pressure at 150-250 degrees C for 10-72 h. Experimental results showed that the tensile strength of the solidified body was greatly influenced by the addition of NaOH solution and fresh cement in the MIBA. The hydrothermal curing temperature and time exerted a significant influence on the development of tensile strength of solidified body. The strength development is speculated to be due primarily to the formation of 1.1 nm tobermorite. Laboratory leaching tests were conducted to determine the amount of heavy metals dissolved from the solidified bodies and the results showed that under the hydrothermal conditions of this study the leaching of heavy metals was very low. As such, the hydrothermal processing method may have a high potential for recycling MIBA.     

The fixation and leaching of cement stabilized arsenic

The solidification/stabilization of sodium arsenite, sodium arsenate, arsenic trioxide and arsenic pentoxide at dosages of approximately 10% has been investigated using sequential batch leaching tests. The leaching of arsenic, which was found to be diffusion based, was clearly least effective for those formulations containing additional iron(II). Calcium was found to influence the leaching of cement immobilized arsenic: those formulations containing the greatest Ca:As mole ratios were generally the most successful. Analysis using both FTIR and SEM revealed substantial changes to the cement matrices of those formulations to which the ferrous sulfate had been added. Ettringite was identified in the cement+ferrous sulfate formulations.     

Solidification and recycling of incinerator bottom ash through the addition of colloidal silica (SiO2) solution

The possibility of using incinerator bottom ash as a substitute for natural aggregates was investigated. Rough, porous surface of bottom ash, which diminishes the strength of solidified products, was improved by colloidal silica solution. As a result, a significant increase of mechanical strength was accomplished by a slight amount of silica (<1 wt% to total). Moreover, pozzolanic reaction was induced in initial cement hydration due to the nano-particle size of about 20 nm in colloidal silica solution. Cylindrical specimens and bricks were prepared from bottom ash added to a colloidal silica (SiO2) solution and cement, and then their compressive strengths were evaluated. Cylindrical specimens showed an increase of approximately 60% in compressive strength when colloidal solution containing 4 wt% silica particles was sprayed onto the bottom ash. The strength of bricks containing colloidal silica was in excess of 20 MPa, which meets the requirement of construction materials. Results of leaching tests based on Toxicity Characteristic Leaching Procedure (TCLP) proved that the solidified bottom ash possessed good chemical stability.