Chlorine removal from MSWI fly ash by thermal treatment: Effects of iron/aluminum additives

The high content of alkali chlorides in municipal solid waste incineration(MSWI) fly ash limit its resource reuse due to the potential environmental risks.In this paper, with superheated steam as the gasifying agent and inducer, chlorides in fly ash were removed by thermal treatment within a moderate temperature range.Thermal treatment experiments were performed under different conditions: temperature(500–800℃), steam addition(mass ratio of steam to fly ash = 0.25–1) and residence time(0.5–3 hr).Iron and aluminum powders were added to fly ash to improve the chlorine removal efficiency.Water-soluble chlorides included Na Cl and KCl, and insoluble chlorides mainly included Ca(OH)Cl.The heating process with the addition of water steam was more efficient than that without steam in terms of the removal performance of water-soluble chlorides.The removal efficiency of soluble chlorides reached 75.25% for a mass ratio of 1:1 after 1-hr thermal treatment at 700℃.When the residence time was increased above 1 hr, the total dechlorination efficiency was not increased dramatically.Moreover, adding iron and aluminum powder into the fly ash improved the removal of water-insoluble chlorides, and the total dechlorination efficiency was increased by 11.41%–16.64%.     

Mercury emissions and partitioning from Indian coal-fired power plants

In India coal combustion is the single largest source of emission of mercury which is a wide-spread persistent global toxicant, travelling across international borders through air and water. As a party to the Minamata convention, India aims to monitor and reduce Hg emissions and stricter norms are introduced for mercury emissions from power plants (30 μg/Nm³for flue gas in stack).This paper presents the results obtained during the experimental studies performed on mercury emissions at four coal-fired and one lignite-fired power plants in India. The mercury concentration in the feed coal varied between 0.12–0.27 mg/Kg. In the mercury mass balance, significant proportion of feed coal mercury has been found to be associated with fly ash, whereas bottom ash contained very low mercury. 80%–90% of mercury was released to air through stack gas. However, for circulating fluidised bed boiler burning lignite, about 64.8% of feed mercury was found to get captured in the fly ash and only 32.4% was released to air. The mercury emission factor was found to lie in the range of 4.7–15.7 mg/GJ.     

Arsenic removal from groundwater by acclimated sludge under autohydrogenotrophic conditions

Arsenic in the environment is attracting increasing attention due to its chronic health effects. Although arsenite(As(III)) is generally more mobile and more toxic than arsenate(As(V)), reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation with sulfide or by adsorption or complexation with other metal sulfides. The performance of As(V) bio-reduction under autohydrogenotrophic conditions was investigated with batch experiments. The results showed that As(V) reduction was a biochemical process while both acclimated sludge and hydrogen were essential. Most of the reduced arsenic remained in a soluble form, although 20% was removed with no addition of sulfate, while 82% was removed when sulfate was reduced to sulfide. The results demonstrated that the reduced arsenic was re-sequestered in the precipitates, probably as arsenic sulfides. Kinetic analysis showed that pseudo first-order kinetics described the bio-reduction process better than pseudo second-order. In particular, the influences of pH and temperature on As(V) reduction by acclimated sludge under autohydrogenotrophic conditions and total soluble As removal were examined. The reduction process was highly sensitive to both pH and temperature, with the optimum ranges of pH 6.5–7.0 and 30–40°C respectively. Furthermore, Arrhenius modeling results for the temperature effect indicated that the As(V) reduction trend was systematic. Total soluble As removal was consistent with the trend of As(V) reduction.     

Attenuation of arsenic in a karst subterranean stream and correlation with geochemical factors: A case study at Lihu, South China

Arsenic （As） pollutants generated by human activities in karst areas flow into subterranean streams and contaminate groundwater easily because of the unique hydrogeological characteristics of karst areas. To elucidate the reaction mechanisms of arsenic in karst subterranean streams, physical-chemical analysis was conducted by an inductively coupled plasma mass spectrometer and an X-ray fluorescence spectrometer. The results show that inorganic species account for most of the total arsenic, whereas organic arsenic is not detected or occurs in infinitesimal amounts. As（III） accounts for 51.0% ± 9.9% of the total inorganic arsenic. Arsenic attenuation occurs and the attenuation rates of total As, As（III） and As（V） in the Lihu subterranean stream are 51%, 36% and 59%, respectively. To fully explain the main geochemical factors influencing arsenic attenuation, SPSS 13.0 and CANOCO 4.5 bundled with CanoDraw for Windows were used for simple statistical analysis and redundancy analysis （RDA）. Eight main factors, i.e., sediment iron （SFe）, sediment aluminum （SAI）, sediment calcium （SCa）, sediment organic matter （SOM）, sediment manganese （SMn）, water calcium （WCa^2＋）, water magnesium （WMg^2＋）, and water bicarbonate ion （WILCOX） were extracted from thirteen indicators. Their impacts on arsenic content rank as： SFe〉SCa〉WCa^2＋〉SAl〉wHCO3^-〉SMn〉SOM〉WMg^2＋. Of these factors, SFe, SAl, SCa, SOM, SMn, WMg^2＋ and WCa＆2＋ promote arsenic attenuation, whereas WHCO3^- inhibits it. Further investigation revealed that the redox potential （Eh） and pH are adverse to arsenic removal. The dramatic distinction between karst and non-karst terrain is that calcium and bicarbonate are the primary factors influencing arsenic migration in karst areas due to the high calcium concentration and alkalinity of karst water.     

Comparison study of phosphorus adsorption on different waste solids: Fly ash, red mud and ferric–alum water treatment residues

The adsorption of phosphorus(P) onto three industrial solid wastes(fly ash, red mud and ferric–alum water treatment residual(FAR)) and their modified materials was studied systematically via batch experiments. Compared with two natural adsorbents(zeolite and diatomite), three solid wastes possessed a higher adsorption capacity for P because of the higher Fe, Al and Ca contents. After modification(i.e., the fly ash and red mud modified by FeCl_3 and FARs modified by HCl), the adsorption capacity increased, especially for the modified red mud, where more Fe bonded P was observed. The P adsorption kinetics can be satisfactorily fitted using the pseudo-second-order model. The Langmuir model can describe well the P adsorption on all of the samples in our study. p H and dissolved organic matter(DOM) are two important factors for P adsorption. Under neutral conditions, the maximum adsorption amount on the modified materials was observed. With the deviation from pH 7, the adsorption amount decreased, which resulted from the change of P species in water and surface charges of the adsorbents. The DOM in water can promote P adsorption, which may be due to the promotion effects of humic-Fe(Al) complexes and the pH buffer function exceeds the depression of competitive adsorption.     

Antimony(V) removal from water by hydrated ferric oxides supported by calcite sand and polymeric anion exchanger

We fabricated and characterized two hybrid adsorbents originated from hydrated ferric oxides(HFOs) using a polymeric anion exchanger D201 and calcite as host. The resultant adsorbents(denoted as HFO-201 and IOCCS) were employed for Sb(V) removal from water. Increasing solution pH from 3 to 9 apparently weakened Sb(V) removal by both composites, while increasing temperature from 293 to 313 K only improved Sb(V) uptake by IOCCS. HFO-201 exhibited much higher capacity for Sb(V) than for IOCCS in the absence of other anions in solution. Increasing ionic strength from 0.01 to 0.1 mol/L NaNO3would result in a significant drop of the capacity of HFO-201 in the studied pH ranges; however, negligible effect was observed for IOCCS under similar conditions. Similarly, the competing chloride and sulfate pose more negative effect on Sb(V) adsorption by HFO-201 than by IOCCS, and the presence of silicate greatly decreased their adsorption simultaneously, while calcium ions were found to promote the adsorption of both adsorbents. XPS analysis further demonstrated that preferable Sb(V) adsorption by both hybrids was attributed to the inner sphere complexation of Sb(V) and HFO, and Ca(II) induced adsorption enhancement possibly resulted from the formation of HFO-Ca-Sb complexes. Column adsorption runs proved that Sb(V) in the synthetic water could be effectively removed from 30 μg/L to below 5 μg/L(the drinking water standard regulated by China), and the effective treatable volume of IOCCS was around 6 times as that of HFO-201, implying that HFO coatings onto calcite might be a more effective approach than immobilization inside D201.     

Influence of SO2 in incineration flue gas on the sequestration of CO2 by municipal solid waste incinerator fly ash

The influence of CO2 content and presence of SO2 on the sequestration of CO2 by municipal solid waste incinerator(MSWI) fly ash was studied by investigating the carbonation reaction of MSWI fly ash with different combinations of simulated flue gas.The reaction between fly ash and 100% CO2 was relatively fast;the uptake of CO2 reached 87g CO2/kg ash,and the sequestered CO2 could be entirely released at high temperatures.When CO2 content was reduced to 12%,the reaction rate decreased;the uptake fell to 41g CO2/kg ash,and 70.7% of the sequestered CO2 could be released.With 12% CO2 in the presence of SO2,the reaction rate significantly decreased;the uptake was just 17g CO2/kg ash,and only 52.9% of the sequestered CO2 could be released.SO2 in the simulated gas restricted the ability of fly ash to sequester CO2 because it blocked the pores of the ash.     

Effect of CaO on retention of S, Cl, Br, As, Mn, V, Cr, Ni, Cu, Zn, W and Pb in bottom ashes from fluidized-bed coal combustion power station

This work was conducted to evaluate whether Ca-bearing additives used during coal combustion can also help with the retention of some other elements. This work was focused on the evaluation of bottom ashes collected during four full-scale combustion tests at an operating thermal fluidized-bed power station. Bottom ashes were preferred to fly ashes for the study to avoid interference from condensation processes usually occurring in the post-combustion zone. This work focused on the behaviors of S, Cl, Br, As, Mn, V, Cr, Ni, Cu,Zn, W, and Pb. Strong positive correlations with CaO content in bottom ashes were observed（for all four combustion tests） for S, As, Cl and Br（R = 0.917-0.999）. Strong inverse proportionality was calculated between the contents of Pb, Zn, Ni, Cr and Mn and CaO, so these elements showed association to materials other than Ca-bearing compounds（e.g., to aluminosilicates, organic matter, etc.）. Somewhat unclear behaviors were observed for W, Cu, and V. Their correlation coefficients were evaluated as statistically ＂not significant＂, i.e., these elements were not thought to be significantly associated with CaO. It was also discovered that major enrichment of CaO in the finest bottom ash fractions could be advantageously used for simple separation of elements strongly associated with these fractions, mainly S and As, but also Cl or Br. Removal of5% of the finest ash particles brings about a decrease in As concentration down to 77%-80% of its original bulk ash content, which can be conveniently used e.g., when high As content complicates further ash utilization.     

Mercury removal from coal combustion flue gas by modified fly ash

Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.     

Preparation and evaluation of Zr-β-FeOOH for efficient arsenic removal

A Zr-β-FeOOH adsorbent for both As(V) and As(III) removal was prepared by a chemical co-precipitation method.Compared with β-FeOOH,the addition of Zr enhanced the adsorption capacities for As(V) and As(III),especially As(III).The maximum adsorption capacities for As(III) and As(V) were 120 and 60mg/g respectively at pH 7.0,much higher than for many reported adsorbents.The adsorption data accorded with Freundlich isotherms.At neutral pH,for As(V),adsorption equilibrium was approached after 3 hr,while for As(III),adsorption equilibrium was approached after 5 hr.Kinetic data fitted well to the pseudo second-order reaction model.As(V) elimination was favored at acidic pH,whereas the adsorption of As(III) by Zr-β-FeOOH was found to be effective over a wide pH range of 4-10.Competitive anions hindered the adsorption according to the sequence:phosphate > silicate > bicarbonate > sulfate > nitrate,while Ca2+ and Mg2+ increased the removal of As(III) and As(V) slightly.The high adsorption capability and good performance in other aspects make Zr-β-FeOOH a potentially attractive adsorbent for the removal of both As(III) and As(V) from water.     

Removal of arsenate and arsenite from aqueous solution by waste cast iron

The removal of As(III) and As(V) from aqueous solution was investigated using waste cast iron, which is a byproduct of the iron casting process in foundries. Two types of waste cast iron were used in the experiment: grind precipitate dust (GPD) and cast iron shot (CIS). The X-ray diffraction analysis indicated the presence of Fe0 on GPD and CIS. Batch experiments were performed under different concentrations of As(III) and As(V) and at various initial pH levels. Results showed that waste cast iron was effective in the removal of arsenic. The adsorption isotherm study indicated that the Langmuir isotherm was better than the Freundlich isotherm at describing the experimental result. In the adsorption of both As(III) and As(V), the adsorption capacity of GPD was greater than CIS, mainly due to the fact that GPD had higher surface area and weight percent of Fe than CIS. Results also indicated the removal of As(III) and As(V) by GPD and CIS was influenced by the initial solution pH, generally decreasing with increasing pH from 3.0 to 10.5. In addition, both GPD and CIS were more effective at the removal of As(III) than As(V) under given experimental conditions. This study demonstrates that waste cast iron has potential as a reactive material to treat wastewater and groundwater containing arsenic.     

铝改性粉煤灰漂珠吸附水溶液中砷的性能研究

采用湿法与干法相结合的方法合成铝改性粉煤灰漂珠环境材料,借助静态吸附实验研究吸附剂量、pH值、离子强度、共存离子、反应时间和温度对其吸附水溶液中砷性能的影响,并进行吸附等温线和动力学拟合.结果表明:铝改性粉煤灰漂珠吸附水中As(V)的最佳pH值范围为中性偏酸;混合离子和H2PO4-对As(V)的吸附影响较大,CO32-次之;离子强度对As(V)吸附的影响不明显;在温度298K、吸附剂量2.5g/L和反应时间24h的条件下,最大吸附容量约5000μg/g;吸附等温线符合Langmuir单层吸附模型;动力学过程符合准二级动力学模型.     

改性粉煤灰在处理锑矿选矿废水中的应用

针对锑矿选矿废水中锑和丁基黄原酸钠严重超标的问题,用酸改性粉煤灰对其进行吸附处理.试验结果表明,当改性粉煤灰处理选矿废水的最佳质量体积比(g.mL-1)为1:100,pH值为3,静置时间为4h时,可以将选矿废水中的锑浓度从28.611mg.L-1降到0.05mg.L-1以下,去除率达99.8%以上;废水中的丁基黄原酸钠浓度可从0.373mg.L-1降到0.02mg.L-1以下,去除率达95.0%以上.处理废水后的改性粉煤灰用硫酸-硝酸浸提,浸出液中重金属离子浓度均低于国家浸出毒性标准,表明改性粉煤灰是一种很好的锑矿选矿废水处理剂.     

焚烧飞灰水泥窑煅烧资源化水洗预处理实验研究

以苏州某公司生活垃圾焚烧飞灰为对象,采用水洗和CO2曝气等方法,通过考察飞灰中Cl的去除率、水洗液的pH值和其中重金属的浓度的变化,对飞灰水泥窑煅烧资源化预处理中的工艺参数和处理效果进行了实验研究。结果表明:水灰比是影响氯盐洗脱效果的最主要因素,水洗比应控制在5:1到10:1左右,而CO2通气量是飞灰水洗上清液中重金属去除过程的主要影响因素,通气量在1.4~1.5 L(CO2)/L(HO2)左右可以有效降低上清液pH值及重金属浓度,使出水达到国家污水排放标准。     

煤飞灰中铬铁元素的形态分析研究

用连续提取法将煤飞灰中的铬、铁元素依结合态区分为水溶态,交换态,表面氧化物和碳酸结合态,铁锰氧化物结合态,金属有机物和硫化物结合态,磁性四氧化三铁结合态和硅铝酸盐矿物态,用原子吸收法及X-衍射分析进行测定。并对煤飞灰化学形态分布进行了讨论。     

循环流化床粉煤灰与煤粉炉粉煤灰磁选除铁差异性研究

粉煤灰中氧化铁是其高值化利用过程的主要杂质,高效去除铁杂质对于粉煤灰高值利用具有重要意义。采用湿法磁选方法对循环流化床粉煤灰（CFB灰）、碳热还原循环流化床粉煤灰（R-CFB灰）及煤粉炉粉煤灰（PC灰）进行除铁研究,并对不同类型粉煤灰中铁的存在形式进行对比,最后对粉煤灰中铁的去除和铝的回收进行了考察。结果表明:CFB灰直接磁选铁的去除率仅为17.6%,PC灰直接磁选铁的去除率可达到55.8%,这与CFB中的铁主要以赤铁矿形式存在,而PC灰中的铁主要以磁铁矿形式存在有关;经碳热还原后CFB灰中的铁由赤铁矿转变为磁铁矿,在磁场强度为400 mT,磁选3次,液固比为20:1的条件下,R-CFB灰的除铁率为64.7%,,铁含量从3.4%降低到1.2%,且铝的回收率为78.6%。与PC灰磁选法除铁效果对比,经碳热还原的CFB灰可达到较高的除铁率。     

微生物对煤系固体废弃物淋滤液污染性影响

煤矸石和粉煤灰是煤矿区的两种主要废弃物,它们不仅占用大量的土地,同时也对矿区环境产生了严重污染。分别接种氧化硫硫杆菌和解磷细菌于煤矸石和粉煤灰中,通过柱状淋滤试验研究微生物对两种固体废弃物淋滤液污染性的影响。结果表明:煤矸石中添加氧化硫硫杆菌能显著脱除煤矸石中的硫,同时淋滤液中也生成了大量的H+和铁离子,使淋滤液中硫酸根和磷酸根离子浓度显著增大,超出了GB3838-2002《地表水环境质量标准》的指标。粉煤灰中添加解磷菌能显著提高淋滤液中的磷含量和电导率,但对淋滤液的pH、SO42-和铁离子影响不明显。氧化硫硫杆菌和解磷细菌对煤矸石和粉煤灰混合工艺处理效果较好,粉煤灰在一定程度上降低了硫、磷和铁的污染性。     

不同吸附剂处理废水中磷的对比研究

为了降低富营养化,实验中讨论了粉煤灰、活性炭两种吸附剂对人工配制的含磷废水的去除效果。从投药量、废水pH值以及振荡时间三个方面考察了对吸附作用的影响。实验结果显示：粉煤灰对磷的去除效果远比活性炭的好,而且还可达到以废治废的效果。粉煤灰、活性炭的最佳投药量分别为0．06g／ml、0．05g／ml;最佳pH值均为6;最佳振荡时间分别为5h、7h;在上述条件下,粉煤灰对磷的吸附率可达90．38％,而活性炭则为31．54％。     

粉煤灰改性及其在废水处理中的应用现状研究

粉煤灰是煤高温燃烧后的产物,在形成过程中形成了一定的多孔结构和较大的比表面积,具有一定的吸附能力,可以作为水处理材料。但由于原性粉煤灰吸附性能有限,对水中污染物的去除率较低,不能满足水处理的实际要求。因此,研究热点集中在对粉煤灰进行改性处理,增加粉煤灰中的活性组分,增大粉煤灰的比表面积,提高其性能,从而增强其对废水处理的效果。粉煤灰在废水处理领域的应用,增加了粉煤灰的综合利用途径,同时以废治废,符合节能环保政策。笔者对粉煤灰的改性方法及其在废水处理中的应用现状进行了总结,以期对粉煤灰的在废水处理中的综合利用提供参考。