Comparison of CaO’s effect on the fate of heavy metals during thermal treatment of two typical types of MSWI fly ashes in China

Both grate and fluidized bed incinerators are widely used for MSW incineration in China. CaO addition for removing hazardous emissions from MSWI flue gas changes the characteristics of fly ash and affects the thermal behavior of heavy metals when the ash is reheated. In the present work, two types of MSWI fly ashes, sampled from both grate and fluidized bed incinerators respectively, were thermal treated at 1023–1323 K and the fate of heavy metals was observed. The results show that both of the fly ashes were rich in Ca and Ca-compounds were the main alkaline matter which strongly affected the leaching behavior of heavy metals. Ca was mostly in the forms of Ca(OH)₂ and CaCO₃ in the fly ash from grate incinerator in which nascent fly ash particles were covered by Ca-compounds. In contrast, the content of Ca was lower in the fly ash from fluidized bed incinerator and Ca was mostly in the form of CaSO₄. Chemical reactions among Ca-compounds caused particle agglomeration in thermal treated fly ash from grate incinerator, restraining the heavy metals volatilization. In thermal treated fly ash from fluidized bed incinerator, Ca was converted into aluminosilicates especially at 1323 K which enhanced heavy metals immobilization, decreasing their volatile fractions as well as leaching concentrations. Particle agglomeration hardly affected the leaching behavior of heavy metals. However, it suppressed the leachable-CaCrO₄ formation and lowered Cr leaching concentration.     

Hybrid zero valent iron (ZVI)/H2O2 oxidation process for landfill leachate treatment with novel nanosize metallic calcium/iron composite

A novel nanosize metallic calcium/iron dispersed reagent was synthesized and tested as coagulant/catalyst in a hybrid zero valent iron (ZVI)/H₂O₂ oxidation process to treat leachate. Two different types of leachates, one from municipal solid waste (MSW) tipping hall (MSWIL) and second from an MSW landfill site (MSWLL), were collected and characterized. The morphology, elemental composition, and mineral phases of the nano-Ca/CaO and nano-Fe/Ca/CaO were characterized by scanning electron microscopy–electron dispersive spectroscopy (SEM-EDS) and x-ray powder diffraction (XRD) analysis. The coagulation process with 2.5 g L^?1 nano-Ca/CaO attained 64.0, 56.0, and 20.7% removal of color, chemical oxygen demand (COD), and total suspended solids (TSS) in MSWLL. With only 1.0 g L^?1 of nano-Fe/Ca/CaO, relatively high color, COD and TSS removal was achieved in MSWLL at 67.5, 60.2, and 37.7%, respectively. The heavy metal removal efficiency reached 91–99% after treatment with nano-Fe/Ca/CaO in both leachate samples. The coupling process, using 1.0 g L^?1 of nano-Fe/Ca/CaO and 20 mM H₂O₂ doses, achieved enhancement removal of color, COD, and TSS, up to 95%, 96%, and 66%, respectively, without initial pH control. After this treatment, the color, COD, TSS, and heavy metals were significantly decreased, fitting the Korean discharge regulation limit. A hybrid coupled zero valent iron (ZVI)/H₂O₂ oxidation process with novel nanosized metallic calcium/iron dispersed reagent proved to be a suitable treatment for dealing with leachate samples.

Implications: Conventional treatments (biological or physicochemical) are not sufficient anymore to reach the level of purification needed to fully reduce the negative impact of landfill leachates on the environment. This implies that new treatment alternatives species must be proposed. A coupled zero valent iron (ZVI)/H₂O₂ oxidation process proved to be a suitable treatment for dealing with leachate samples. Coagulation with nFe/Ca/CaO allows 91–99% of heavy metals removal. The coupled coagulation–oxidation process by nFe/Ca/CaO reveals excellent ability to treat leachate. After coupled treatment the color, COD, and TSS were also much lower than the discharge regulation limit.     

SGA对垃圾焚烧飞灰中重金属的固化性能研究简

根据EPA 1311、HJ/T 299-2007、HJ/T 300-2007和HJ 557-2009等国内外不同标准，研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性，探讨了六硫代胍基甲酸（sixthio guanidine acid，SGA）、二甲基二硫代氨基甲酸盐（sodium dimethyl dithio carbamate，SDD）和Ca（OH）₂浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明，随着浸提液pH的降低，该厂焚烧飞灰中大部分金属元素的浸出量增大，焚烧飞灰浸出液中的Cd、Ni、Pb和Zn浓度分别超过国家危险废物鉴别标准（GB5085.3-2007）规定值的4.75倍、1.47倍、6.72倍和2.20倍，属于危险废弃物，必须进行稳定化处理。当固化剂SGA加入量为0.1 mol/kg时，稳定化后的重金属浸出浓度已经低于危险废物鉴别标准，且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）₂；当固化剂SGA、SDD和Ca（OH）₂加入量为0.5 mol/kg时，稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB 5085.3-2007）中的规定值。与SDD和Ca（OH）₂相比，SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。     

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。     

Enhanced heavy metal immobilization in soil by grinding with addition of nanometallic Ca/CaO dispersion mixture

This study investigated the use of a nanometallic Ca and CaO dispersion mixture for the immobilization of heavy metals (As, Cd, Cr and Pb) in contaminated soil. Simple grinding achieved 85-90% heavy metal immobilization, but it can be enhanced further to 98-100% by addition of a nanometallic Ca/CaO dispersion mixture produced by grinding. Observations using SEM-EDS elemental maps and semi-quantitative analysis showed that the amounts of As, Cd, Cr, and Pb measurable on the soil particle surface decrease after nanometallic Ca/CaO treatment. The leachable heavy metal concentrations were reduced after nanometallic Ca/CaO treatment to concentrations lower than the Japan soil elution standard regulatory threshold: <0.01 mg L⁻¹ for As, Cd, and Pb; and 0.05 mg L⁻¹ for Cr. Effects of soil moisture and pH on heavy metal immobilization were not strongly influenced. The most probable mechanisms for the enhancement of heavy metal immobilization capacity with nanometallic Ca/CaO treatment might be due to adsorption and entrapment of heavy metals into newly formed aggregates, thereby prompting aggregation of soil particles and enclosure/binding with Ca/CaO-associated immobile salts. Results suggest that the nanometallic Ca/CaO mixture is suitable for use in immobilization of heavy-metal-contaminated soil under normal moisture conditions.     

Silica-Enhanced Sorbents for Dry Injection Removal of SO2 from Flue Gas

Novel silica-enhanced lime sorbents were tested in a bench-scale sand-bed reactor for their potential for SO₂ removal from flue gas. Reactor conditions were 64°C (147°F), relative humidity of 60 percent [corresponding to an approach to saturation temperature of 10°C (18°F)], and inlet SO₂ concentration of 500 or 1000 ppm. The sorbents were prepared by pressure hydration of CaO or Ca(OH)₂ with siliceous materials at 100°C (101 kPa) [212°F (14.7 psi)] to 230°C (2793 kPa) [446°F (405 psi)] for 15 min to 4 h. Pressure hydration fostered the formation of a sorbent reactive with SO₂ from fly ash and Ca(OH)₂ in a much shorter time than did atmospheric hydration. The conversion of Ca(OH)₂ in the sand-bed reactor increased with the increasing weight ratio of fly ash to lime and correlated well with B.E.T. surface area, increasing with increasing surface area. The optimum temperature range for the pressure-hydration of fly ash with Ca(OH)₂ was between 110 and 160°C (230 and 320 °F). The pressure hydration of diatomaceous earth with CaO did not offer significant reactivity advantages over atmospheric hydration; however, the rate of enhancement of Ca(OH)₂ conversions was much faster with pressure hydration. Scanning electron microscope (SEM) and x-ray diffraction studies showed solids of different morphology with different fly ash/lime ratios and changing conditions of pressure hydration.     

The Capture of Heavy Metals from Incineration Using a Spray Dryer Integrated with a Fabric Filter Using Various Additives

ABSTRACT

This study investigated the effects of feedstock additives [polyvinyl chloride (PVC) and NaCl] and spray dryer additives (SiO₂, CaCl₂, NaHCO₃) on heavy metal and fly ash removal efficiencies, and on particle size distribution of heavy metals. A spray dryer with an integrated fabric filter was used as an air pollution control device (APCD). Removal efficiencies for fly ash and heavy metals were greater than 95 and 90%, respectively. When additives of PVC or NaCl were used, the concentration of heavy metals distributed in fly ash apparently varied when the particle diameter was <1 μm. Although the effects of the additives SiO₂, CaCl₂, and NaHCO₃ on the elemental size distribution of Cr were insignificant, these additives did slightly increase concentrations of Cd, Zn, and Pb partitioning in coarser particles (>1μm).     

The Relationship between the Quantity of Heavy Metal and PAHs in Fly Ash

ABSTRACT

Heavy metal and polycyclic aromatic hydrocarbons (PAHs) in flue gas have received considerable attention in recent years due to their mutagenic or carcinogenic properties. The present study is carried out to investigate the influence of the quantity of heavy metals on PAHs formation in fly ash.

A fluidized bed incinerator was used in this experiment to obtain fly ash of chemical similarity by incinerating various compositions of waste. The obtained fly ash, both with and without heavy metal, were used to adsorb the PAHs in the flue gas and to investigate the formation of PAHs in fly ash. The results indicate that carbon and heavy metals most greatly influence the formation of PAHs in the fly ash. Carbon is absorptive; heavy metals encourage not only absorption of PAHs but also catalyze PAHs formation.     

SGA对垃圾焚烧飞灰中重金属的固化性能研究

根据EPA1311、HJ／T299—2007、HJ／T300—2007和HJ557—2009等国内外不同标准，研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性，探讨了六硫代胍基甲酸（sixthioguanidineacid，SGA）、二甲基二硫代氨基甲酸盐（sodiumdimethyldithiocarbamate，SDD）和Ca（OH）2浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明，随着浸提液pH的降低，该厂焚烧飞灰中大部分金属元素的浸出量增大，焚烧飞灰浸出液中的cd、Ni、Ph和zn浓度分别超过国家危险废物鉴别标准（GB5085．3—2007）规定值的4．75倍、1．47倍、6．72倍和2．20倍，属于危险废弃物，必须进行稳定化处理。当固化剂SGA加入量为0．1mol／kg时，稳定化后的重金属浸出浓度已经低于危险废物鉴别标准，且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）2；当固化剂SGA、SDD和Ca（OH）2加入量为0．5mol／kg时，稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB5085．3-2007）中的规定值。与SDD和Ca（OH）：相比，SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。     

脱硫灰与钾矿石复合生产钾钙硅镁硫肥料研究

对脱硫灰与钾矿石复合生产钾钙硅镁硫肥的研究意义、反应原理、生产流程、环境安全性能以及施肥方法等进行了介绍和评估,并对其应用前景进行了展望。研究结果表明:利用脱硫灰与钾矿石复合生产钾钙硅镁硫肥在理论上可行;生产出的产品中硫酸钾的含量达10.34%～12.0%,枸溶氧化钙19.06%～32.28%,枸溶二氧化硅10.98%～14.46%,枸溶氧化镁1.46%～1.82%。产品的pH值从原脱硫灰的10.65下降到9.60。重金属含量低于农用粉煤灰国家标准,生产过程中不会产生SO2等有害气体污染。肥料的生产成本低于350元/t,该肥料不但可以增加土壤中钾、钙、硅、镁和硫等中微量元素的含量,而且可以提高或改善农作物的产量和品质。达到变废为宝,促进循环经济发展之目的。     

Evaluation of three common alkaline agents for immobilization of multi-metals in a field-contaminated acidic soil

We investigated three common alkaline agents (NaOH, CaO, and Mg(OH)₂) for immobilization of four heavy metals (Pb, Zn, Cu, and Cd) in a field-contaminated soil and elucidated the underpinning principles. NaOH caused the highest pH spike in the soil, while CaO and Mg(OH)₂ served as a longer-lasting source of OH^-. Amending the soil with CaO or Mg(OH)₂ at ≥0.1 mol as OH^- (kg·soil)^?1 for 24 h was able to immobilize all four metals, while NaOH failed. NaOH leached up to 3 times more organic carbon than CaO and Mg(OH)₂, resulting in elevated leachability of the metals. Column elution tests showed that amendments by CaO and Mg(OH)₂ lowered the leachable Pb²⁺, Zn²⁺, Cu²⁺, and Cd²⁺ by 52–54%, 71–75%, 69–73%, and 68%, respectively, after 1440 pore volumes of elution. Sequential extraction revealed that the soil amendments converted the exchangeable fraction of the metals to the much less available forms. XRD and FTIR analyses indicated that formation of metal oxide precipitates and complexation with soil organic matter were responsible for the metals immobilization. Taken together the chemical cost, technical effectiveness, and environmental impact, CaO is the most suitable alkaline agent for remediation of soil contaminated with heavy metals.

     

Removal of SO2 and NOX from Stack Gas by Reaction with Calcium Hydroxide Solids

Previous workers have shown that simultaneous SO₂/NO_X removal can be obtained in a dry scrubbing system with Ca(OH)₂ promoted by an additive such as NaOH, and that fly ash and product recycle improve the reactivity of the solids toward SO₂. To test SO₂/NO_X removal with fly ash and product recycle, bench-scale experiments with a packed bed reactor were performed at bag filter conditions. The most reactive solid for NO_X removal was prepared by slurrying Ca(OH)₂ with fly ash, CaSO₃, and NaOH. The best conditions for NO_X removal were the greatest temperature (125°C) and greatest concentrations of SO₂ (1500 ppm) and O₂ (20 percent). At the best conditions, NO_X removed in 1 hour was 3-4 moles per 100 moles Ca(OH)₂, compared to 5-10 moles SO₂ removed per 100 moles Ca(OH)₂. The best SO₂ removal was obtained at the highest relative humidities/lowest temperatures (55% RH/ 65°C) with solids prepared by slurrying Ca(OH)₂ with fly ash and NaOH. At these conditions, SO₂ removed In 1 hour was 60-80 moles per 100 moles Ca(OH)₂, compared to 0.5 to 1 moles NO_X removed per 100 moles Ca(OH)₂.     

CaCl2高温热处理垃圾焚烧飞灰中重金属的挥发特性

以深圳市某垃圾焚烧厂飞灰为原料，采用高温管式电阻炉，研究了在0．6L／minN，气氛下，CaCl2在不同添加量、处理温度及处理时间下对飞灰中重金属Pb、Cd、Zn和Cu挥发特性的影响，并对收集到的二次飞灰进行成分及物相分析。结果显示，X射线衍射仪和EDS分析表明，二次飞灰主要是由NaCl、KCl和部分SiCl4组成，zn主要以K2ZnCl4形式挥发，而Pb则主要以氧化物PbO和Pb3SiO5的形式挥发。最终得到CaCl2热处理飞灰的最佳二次气化条件：以0．6L／minN，为载气，添加14wt％的CaCl2，在1100℃高温下处理2．5h。经CaCl2热处理后的剩余飞灰，其浸出毒性达到了《生活垃圾填埋场污染控制标准》要求。     

Continuous CO2 capture and MSWI fly ash stabilization, utilizing novel dynamic equipment

Novel dynamic equipment with gas in and out continuously was developed to study the capture capacity of CO₂. Municipal solid waste incineration (MSWI) fly ash has a high capture rate of CO₂ in CO₂-rich gas. Fly ash can sequester pure CO₂ rapidly, and its capacity is 16.3 g CO₂/100 g fly ash with no water added and 21.4 g CO₂/100 g fly ash with 20% water added. For simulated incineration gas containing 12% CO₂, the capture rate decreased and the capacity was 13.2 g CO₂/100 g fly ash with no water added and 18.5 g CO₂/100 g fly ash with 20% water added. After accelerated carbonation, the C and O contents increased, indicating CO₂ capture in the fly ash; CO₂ combines with Ca(OH)₂ to form CaCO₃, which increased the CaCO₃ content from 12.5 to 54.3%. The leaching of Pb markedly decreased from 24.48 to 0.111 mg/L.     

Emission characteristics for co-combustion of leather wastes,sewage sludge,and coal in a laboratory-scale entrained flow tube furnace

Four different mixed fuels consisted of leather waste, coal, and sewage sludge were combusted in a lab-scale entrained flow fluidized bed furnace. The influence of blending ratio on emission characteristics of SO₂, NO_x, HCl, particulate matter (PM), heavy metals, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was studied. Results showed that the mixing of coal with sewage sludge had a complex effect on the emission characteristics. On the one hand, with more sewage sludge blending in the mixed fuel, the acid gas pollutant (SO₂, NO_x) decreased a lot, and the recovery of volatile heavy metals (Cd, Pb) increased at the same time. Furthermore, the leaching toxicity of Cr in the fly ash and bottom ash went down below the national standard with the adding of sewage sludge. On the other hand, the mixing of sewage sludge which consisted of more ash content resulted in the increase of the PM emission. Moreover, the high content of Cu and chlorine in the sewage sludge can promote the formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) when the fuel 3 and 4 were combusted. Most importantly, the concentration of toxic PCDD/Fs in the flue gas produced from fuel 3 and fuel 4 was successfully controlled down below 0.20 ng I-TEQ/Nm³ by the active carbon.

     

The capture of heavy metals from incineration using a spray dryer integrated with a fabric filter using various additives

This study investigated the effects of feedstock additives [polyvinyl chloride (PVC) and NaCl] and spray dryer additives (SiO2, CaCl2, NaHCO3) on heavy metal and fly ash removal efficiencies, and on particle size distribution of heavy metals. A spray dryer with an integrated fabric filter was used as an air pollution control device (APCD). Removal efficiencies for fly ash and heavy metals were greater than 95 and 90%, respectively. When additives of PVC or NaCl were used, the concentration of heavy metals distributed in fly ash apparently varied when the particle diameter was <1 microm. Although the effects of the additives SiO2, CaCl2, and NaHCO3 on the elemental size distribution of Cr were insignificant, these additives did slightly increase concentrations of Cd, Zn, and Pb partitioning in coarser particles (>1 microm).     

Leaching characteristics of stabilized/solidified fly ash generated from ash-melting plant

This study was designed to elucidate the leaching characteristics of stabilized/solidified (S/S) fly ash generated by ash-melting. For this study, pH-dependent leaching tests, sequential extraction procedures, and column leaching tests were carried out. The pH-dependent leaching test results for Pb, Cu, and Zn showed that the heavy metal concentrations in the high-pH range were lower than the predicted values for hydroxide and carbonate. During sequential extraction, Cu and Pb were principally distributed in the S/S ashes' organic matter fraction in the chelating agent, suggesting that metals bind to the chelating agent. The percentage of the water-soluble fraction for Pb and Cu was low (<0.2 %). The fly ashes treated with a chelating agent and cement had low leachability potential for metals in the high-pH range. Column tests for S/S fly ashes showed that two leaching stages were distinguishable: one for short time, corresponding to faster metal leaching, and another for the leaching rate. Kinetic speciation was then applied to data obtained from column leaching tests. The first-order reaction/diffusion model showed a better fit for Ca, Pb, and Cu, suggesting that the initial dissolution of soluble compounds, such as metal chloride, was controlled by the first-order reaction (surface wash off). Subsequently, insoluble compounds such as hydroxide or carbonate might penetrate into the porous matrix by diffusion.     

Stabilization of heavy metals in municipal sewage sludge by freeze–thaw treatment with a blend of diatomite,FeSO4, and Ca(OH)2

In this work, the effects of diatomite with 15% FeSO₄?7H₂O and 7.5% Ca(OH)₂ on sludge stabilization were investigated using batch leaching tests. The influence of cell rupture caused by freezing and thawing on stabilization was also evaluated. The results indicated that the optimal diatomite percentage was 2%. Cell rupture by freezing and thawing reduced heavy metal leachability, followed by cell death and decrease of organic groups. The concentration of heavy metals in sludge leachate increased after cell rupture, indicating that the heavy metal leachability was reduced after freezing and thawings. Moreover, the stabilization effects were generally improved after freezing and thawing. As compared with the stabilization of the original sludge, the unstable fractions decreased and the residual fractions of the heavy metals increased in the stabilized sludge after cell rupture.

Implications: This study developed a method to stabilize heavy metals in municipal sewage sludge. Diatomite combined with FeSO₄·7H₂O and Ca(OH)₂ improved the treatment of sewage sludge contaminated by heavy metals. Cell lysis by freeze–thaw treatment reduced the risk of leaching heavy metals caused by cell death and decreased major organic groups in the sludge.     

油页岩循环流化床锅炉底渣和飞灰中重金属元素浸出毒性研究

为了研究我国桦甸油页岩65 t/h循环流化床锅炉的底渣和飞灰中重金属元素Cr、Cu、Pb和Zn的赋存状态及不同酸度条件下的浸出特性,分别进行了逐级提取实验和分批浸出的淋滤实验。逐级提取实验结果表明,这4种元素在底渣和飞灰中具有基本相当的赋存状态。硫化物结合态和稳定的残渣态是各元素的主要赋存状态,元素的潜在浸出能力大小表现为:PbCrCuZn,飞灰中各元素的潜在浸出能力大于底渣中的。浸出实验结果表明,元素的赋存状态决定了其浸提能力,浸提液的pH值对各元素浸出能力的影响不尽相同,各元素的浸出能力随浸提时间的延长都会趋于平衡,Cr和Pb的浸出浓度都高于地表水和饮用水的国家标准。     

粉煤灰协同微波-Fenton氧化法处理活性艳蓝KN-R染料废水

以粉煤灰联合微波-Fenton氧化工艺处理活性艳蓝KN-R生产废水,考察了粉煤灰投加量及吸附时间对处理效果的影响,并通过正交实验对微波-Fenton工艺参数进行了优化。实验结果表明,粉煤灰絮凝吸附与微波-Fenton氧化具有协同效应;在粉煤灰投加量为40 g/L,搅拌吸附时间为20 min,滤液pH值为4,Fe2＋和H2O2投加量分别为3.6 mmol/L和0.15 mol/L,微波功率为200 W,辐射反应时间为4 min的优化条件下,染料废水的处理效果最好,COD和色度的去除率分别达到90.90%和99.98%。