烧结活化-酸浸法浸出粉煤灰中铝元素

为实现粉煤灰的高效资源化,并控制资源化过程中的能耗,采用NaOH为烧结助剂,利用烧结活化-酸浸法浸出粉煤灰中的铝元素;在探究最佳工艺条件的同时,通过分析烧结产物矿物组成及官能团的变化来探究粉煤灰烧结活化的机理。结果表明,当烧结温度为550 °C、NaOH/CFA 质量比=1.40、硫酸浓度为30%、烧结时间为10 min的条件下,铝元素浸出率可达95.00%以上。在粉煤灰烧结活化过程中,莫来石及非晶态硅铝化合物与NaOH反应,其中的铝氧八面体结构转变为铝氧四面体结构,铝氧四面体与硅氧四面体结构相结合形成以四元环和六元环为基本结构的铝硅酸盐,即八面沸石和霞石。在酸浸过程中,八面沸石和霞石与硫酸发生反应使铝元素以离子形式存在于酸浸液中,其中霞石相更有利于烧结产物的酸浸过程。该研究结果可为烧结活化-酸浸法浸出粉煤灰中铝元素提供参考。     

Time-resolved leaching of cadmium and manganese from lignite and incinerator fly ash

Fly ashes from a lignite fired power plant and a municipal incinerator were leached for 3 hours using 0.1N HC1. Leachate was analyzed for Cd and Mn and plots of concentration versus time for these elements show Cd, a surface adsorbed element in the combustion process, to be rapidly removed from the ash particles in the initial four or five minutes of leaching. Manganese, a fly ash matrix element, is leached at a more constant rate as the ash praticles are dissolved. Total Cd and Mn concentrations in the incinerator fly ash are greater than total concentrations of these elements in the lignite fly ash.     

粉煤灰复合氧化钙去除铬渣渗滤液中的总铬

粉煤灰虽然具有较大的比表面积,但单独做为处理剂处理含铬废水,效果并不理想,具有吸附容量小、溶解损失大、且有毒性浸出等特点.为了解决粉煤灰以上缺陷,提出氧化钙复合粉煤灰去除铬渣渗滤液中总铬的技术,研究表明,在室温25℃条件下,总铬初始浓度在0.30~80.00 mg/L范围内,选择粉煤灰与CaO配比为1:1时,以150 r/min转速充分振荡24 h,总铬去除率均能达到90%以上.通过空白对照实验研究表明,粉煤灰复合CaO使用,对总铬的去除远优于单独使用粉煤灰或CaO做为吸附剂的处理效果.利用SEM,XRD,红外光谱分析3种材料表征方法,对粉煤灰原料、CaO-粉煤灰处理后残渣等进行分析,结果表明,在水介质条件下,粉煤灰与CaO能生成晶体矿物.当溶液中有铬存在时,晶体矿物在形成的过程中能将铬裹入其结构中.通过浸出实验表明,此晶体矿物对铬具有很好的固定作用.     

添加垃圾焚烧飞灰冷固小球的工业烧结实验

将垃圾焚烧飞灰添加进烧结冷固球团配料进行造球,对冷固小球的成分及强度进行分析,结果表明,添加垃圾焚烧飞灰冷固小球化学组成稳定,重金属浸出毒性远低于危险废物鉴别标准,落下强度较基准期略微降低,但符合运输、贮存的要求.并对添加了飞灰的冷固小球对其后续烧结、冶炼工序的影响进行分析,结果表明,用添加飞灰的冷固小球进行烧结所得烧结矿的转鼓强度、落下强度及常规化学成分较基准期没有太大变化,添加飞灰进行造球、烧结,对其后续冶炼工序的顺行几乎没有影响,所带来的额外的环境污染微乎其微.     

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.     

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。     

The role of ammonia on mercury leaching from coal fly ash

The Federal Clean Air Interstate Rule issued in March 2005 will result in many power plants employing ammonia-based technologies to control NO(x) emission. The Clean Air Mercury Rule, issued at the same time, will encourage many power plants to use various technologies to remove mercury from flue gas, generating fly ashes that contain elevated concentrations of mercury. Ammonia forms relatively strong complexes with mercury compared to most other cationic elements and, therefore, may change the leaching characteristics of mercury. Understanding the impact of ammonia on the leaching of mercury from fly ash is critical in predicting the potential environmental impact of future fly ash. Batch methods were used to investigate the ammonia impact on mercury leaching from fly ash under different pH conditions. The results indicated that mercury leaching without external ammonia addition is not significant. However, ammonia addition increased mercury leaching in the alkaline pH range, due to the formation of less adsorbable mercury-ammonia complexes. Washed ash released more mercury than the raw ash if the ammonia concentration is the same, mainly due to the dissolution of some ash components during washing which exposed more mercury on ash surface. Mercury adsorption data indicated that more than 90% of available mercury was adsorbed by fly ash even in the presence of 1000 mg l(-1) ammonia addition.     

Hydrometallurgical recovery of zinc from ashes of automobile tire wastes

Study has been performed on the investigation of metal leaching behavior for fly and bottom ashes from automobile tire wastes using acid and alkaline solutions from both viewpoints of environmental protection and resource utilization. The two ashes were found to contain substantial amounts of zinc and iron along with small quantities of cobalt, manganese, magnesium, copper, titanium and aluminum. The fly ash contained a much larger amount of zinc than the bottom ash, and seems to be a promising secondary source for the metal. Effects of such experimental parameters as temperature, time and solid-liquid ratio on the leaching behavior were investigated. Using three mineral acids and citric acid, selective leaching of zinc was successfully attained; the concentration of zinc in the leach liquors from the fly ash reached as high as 20 g l(-1) while the iron leaching was much suppressed. Selective separation of zinc was also attained in the leaching with alkaline solutions, though the percent leaching was lower than that in the acid leaching. Moreover, solvent extraction and precipitation were applied to the metal-loaded leach liquors as downstream processing to evaluate the feasibility of zinc recovery.     

硫酸亚铁对粉煤灰中不同价态铬元素淋滤特性的影响

粉煤灰中痕量元素的滤出会对灰场下游的生态环境产生重要的影响,因而研究粉煤灰中痕量元素的淋滤特性具有重要的现实意义.针对贵州某电厂灰样,开展铬元素的迁移控制及柱淋滤特性的研究,建立HPLC-ICP-MS对不同价态铬定量分析的方法,结果显示,以EDTA为络合剂,经过高效液相色谱分离, Cr(Ⅲ)与Cr(Ⅵ)的保留时间分别为80 s和120 s左右,实现了基线分离.并选取硫酸亚铁,研究硫酸亚铁的添加对不同价态铬元素在柱淋滤系统内淋滤特性的影响.     

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。     

熔盐法处置高熔点垃圾焚烧飞灰重金属的浸出特性

对熔盐法处置高熔点垃圾焚烧飞灰重金属离子浸出特性进行了实验研究。结果表明,熔盐物料组成、熔盐温度和热处理气氛对重金属离子的热挥发特性具有重要影响。在还原性气氛条件下,热处理温度为900～1 000 ℃,添加质量分数为10%～50%的CaCl2的氯化钠熔盐中处理2 h后,垃圾焚烧飞灰渣中Pb、Cd、Cu和Zn等重金属浸出浓度降低90%以上,可以完全达到生活垃圾填埋场填埋标准。在此过程中,灰渣较原灰可减轻50%,同时转化成具有良好胶凝性能的水泥活性混合材料,XRD测试表明其晶体矿物组成为硅酸二钙、硅酸三钙和阿里尼特以及硫酸钙等。     

Dolomite phosphate rock (DPR) application in acidic sandy soil in reducing leaching of phosphorus and heavy metals—a column leaching study

A column leaching study was designed to investigate the leaching potential of phosphorus (P) and heavy metals from acidic sandy soils applied with dolomite phosphate rock (DPR) fertilizers containing varying amounts of DPR material and N-Viro soils. DPR fertilizers were made from DPR materials mixing with N-Viro soils at the ratios of 30, 40, 50, 60, and 70 %, and applied in acidic sandy soils at the level of 100 mg available P per kilogram soil. A control and a soluble P chemical fertilizer were also included. The amended soils were incubated at room temperature with 70 % field water holding capacity for 21 days before packed into a soil column and subjected to leaching. Seven leaching events were conducted at days 1, 3, 7, 14, 28, 56, and 70, respectively, and 258.9 mL of deionized water was applied at each leaching events. The leachate was collected for the analyses of pH, electrical conductivity (EC), dissolved organic carbon (DOC), major elements, and heavy metals. DPR fertilizer application resulted in elevations up to 1 unit in pH, 7–10 times in EC, and 20–40 times in K and Ca concentrations, but 3–10 times reduction in P concentration in the leachate as compared with the chemical fertilizer or the control. After seven leaching events, DPR fertilizers with adequate DPR materials significantly reduced cumulative leaching losses of Fe, P, Mn, Cu, and Zn by 20, 55, 3.7, 2.7, and 2.5 times than chemical fertilizer or control. Even though higher cumulative losses of Pb, Co, and Ni were observed after DPR fertilizer application, the loss of Pb, Co, and Ni in leachate was <0.10 mg (in total 1,812 mL leachate). Significant correlations of pH (negative) and DOC (positive) with Cu, Pb, and Zn (P?<?0.01) in leachate were observed. The results indicated that DPR fertilizers had a great advantage over the soluble chemical fertilizer in reducing P loss from the acidic sandy soil with minimal likelihood of heavy metal risk to the water environment. pH elevation and high dissolved organic carbon concentration in soils after DPR fertilizer application are two influential factors.     

垃圾焚烧飞灰对染料（亚甲基蓝）的吸附性能

以垃圾焚烧飞灰为吸附剂对亚甲基蓝进行了吸附脱色实验。主要探讨了飞灰粒径、用量、温度、pH值和初始浓度等因素对亚甲基蓝吸附的影响,同时分析了吸附上清液中重金属Pb和Cr的浸出毒性。研究结果表明,在25—45℃、pH值2～12、飞灰用量1～5g范围内,经过180min吸附,亚甲基蓝的脱色率都达75％以上,最高可达99．46％。实验还得出,除重金属Pb外,吸附上清液中重金属的浸出量远远低于《危险废物鉴别标准浸出毒性鉴别》的限定值。因此,若能降低重金属Pb的浸出,飞灰将具有应用于处理染料废水的巨大潜力。     

Adsorption of arsenic(V) onto fly ash: a speciation-based approach

Arsenic (As) poses a significant water quality problem and challenge for the environmental engineers and scientists in the world. The large volume of coal fly ash produced around the world is a potentially significant anthropogenic source of arsenic. Currently the leaching behavior of arsenic from fly ash is not well understood. Batch methods were used in this study to investigate arsenic leaching using a raw ash, and arsenic adsorption using a clean, washed ash. Experimental results indicated that pH had a significant effect on arsenic leaching or adsorption. Between pH 3 and 7, less arsenic was in the dissolved phase. When pH was less than 3 or greater than 7, increasing amounts of arsenic were leached or desorbed from fly ash. The leaching and adsorption behavior of arsenic was interpreted with the speciation of surface sites and arsenic. In a new approach, a speciation-based model was developed to quantify the arsenic adsorption as a function of pH and surface acidity parameters. This work is important in offering insight into the leaching mechanism of arsenic from coal fly ash, and providing a robust model based upon specific, measurable parameters to quantify arsenic adsorption by other solid media in addition to fly ash.     

Modeling batch leaching behavior of arsenic and selenium from bituminous coal fly ashes

Correctly predicting the leaching potential of arsenic (As) and selenium (Se) is critical for assessing the environmental impact of coal fly ash. This study investigated the impacts of several key environmental factors, including pH, leaching time, and ash washing on the batch leaching behavior of As and Se from bituminous coal fly ashes. The experimental results demonstrated that As and Se leaching from fly ash increased beyond the minimal leaching pH ranges. Increasing leaching time increased As leaching but decreased Se leaching in the alkaline pH condition. A speciation-based adsorption model was used to quantify the batch leaching data, and determine the intrinsic leaching parameters including the total batch leachable mass and the adsorption constant of As or Se. The modeling approach was validated by correctly predicting the independent batch leaching data in a broad pH range and a different L/S condition. Experimental and modeling results also demonstrated that ash washing and ash aging (longer leaching time) did not change the adsorption constants of As and Se on the ash surface. However, ash washing could increase the availability of As and Se for leaching.     

水热法外加硅铝添加剂稳定垃圾焚烧飞灰中的重金属

研究了在碱性水热条件下添加粉煤灰、膨润土、高岭土等以提供硅铝元素稳定生活垃圾焚烧飞灰中的重金属。实验结果表明,水热反应中添加粉煤灰、膨润土合成了雪硅钙石和水钙铝榴石,添加高岭土合成了雪硅钙石和加藤石。水热反应中添加粉煤灰、膨润土、高岭土对降低飞灰中Pb、Zn等重金属的浸出毒性均具有显著效果,水热产物中Pb、Zn和Cu的浸出浓度与飞灰相比分别降低了87%~96%、87%~94%和57%~78%。硅铝添加剂还能抑制飞灰中Pb、Zn等在碱性水热条件下向液相的转移,使重金属稳定在固相中。     

Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15-92%, whereas with the Kota fly ash an increase in sorption by 13-38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K(f)/K(d) values, K(FA) values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

酸洗-电沉积联用技术回收垃圾焚烧飞灰中的重金属

垃圾焚烧飞灰中的重金属浸出能力强、毒性大,属于危险废物,若处置不当将会对环境造成严重污染。采用酸洗-电沉积联用技术,考察硝酸浓度、液固比和酸洗时间对重金属去除率的影响,研究电沉积电压和时间对酸洗废液中重金属回收率的影响,同时评估处理后飞灰的浸出毒性。结果表明,在浓度为2 mol·L⁻¹、液固比为25的硝酸中浸渍洗涤60 min条件下,酸洗能成功去除飞灰中95.26%的Zn、83.06%的Pb、72.62%的Cu和97.85%的Cd;在电压为14 V,电沉积4 h的条件下可回收酸洗废液中95.80%的Zn、99.04%的Pb、79.95%的Cu和90.37%的Cd。对Zn、Pb、Cu、Cd的连续提取和浸出毒性测试表明,处理后飞灰易浸出组分占比降低,残余态物质占比提高,重金属浸出质量浓度符合《生活垃圾填埋场污染控制标准》(GB 16889-2008)要求,可直接进行填埋或作为非危废固体进行资源化利用。本研究结果可为飞灰中重金属脱除和回收利用提供参考。     

矿渣高温固化垃圾焚烧飞灰中的重金属

垃圾焚烧飞灰由于含有大量重金属属于危险固体废物,重金属的浸出含量影响其资源化利用。模拟高炉矿渣在熔融状态下固熔部分飞灰,研究固熔体急冷后其重金属的浸出规律,采用SEM-EDS、XRD、FTIR研究固熔体固化重金属的机理。结果表明：重金属浸出量随着熔融温度的升高而减少,随着飞灰掺量的增加而增加,但浸出浓度远低于国家标准;SEM-EDS表明,主要重金属均出现在固熔体中;XRD证实有部分Zn以生成Ca2ZnSi2O7的形式被固化;FTIR的结果也表明固化的重金属影响了Si—O—Si键的周围环境。     

The leachability and chemical speciation of selected trace elements in fly ash from coal combustion and refuse incineration

A laboratory leaching test has been used to predict the potential mobility of As, Se, Pb and Cd in landfilled fly ash produced by coal combustion and refuse incineration. These waste residues also formed the basis of a speciation study in which the valency states of As and Se and the chemical forms of Pb and Cd have been determined. Selenium displayed the greatest leachability in each ash type, despite being present at relatively low concentrations in both materials. Substantial amounts of other trace elements were also leached, particularly Pb and Cd from refuse ash and As from coal ash. Chemical associations of Pb and Cd were examined by a sequential extraction procedure. In coal fly ash, both elements were mostly present in the residual fraction, while in refuse ash these elements were mainly associated with the exchangeable fraction. Water-soluble extracts of coal fly ash contained As exclusively as As(V); high background interference prevented the detection of water-soluble As in refuse ash. Selenium was present largely as Se(IV) in aqueous extracts of both ash types. The value of speciation techniques and leaching tests as predictors of environmental behaviour is discussed in conjunction with results of routine trace element determinations and plant uptake studies.