燃煤电厂异相凝并飞灰重金属淋滤特性

采集了燃煤电厂的异相凝并后飞灰，分析了其物理化学特性。并通过淋滤实验研究了飞灰中重金属As、Se、Pb的环境稳定性。结果表明，凝并飞灰的粒径峰值为138.04 μm，而粉煤灰为60.26 μm；凝并后细颗粒凝聚成了较大的颗粒；凝并飞灰中重金属As、Se、Pb含量均高于同工况下粉煤灰中的含量，且后序脱硫环节所产生石膏中重金属的含量有所下降；批淋滤实验研究结果表明，凝并飞灰中的重金属浸出能力受淋滤液的pH值影响较大，温和环境和碱性条件抑制了As的浸出，酸性和碱性条件抑制了Se的浸出，而碱性条件抑制了Pb的浸出。柱淋滤实验研究结果表明，在酸性溶液和水溶液中，凝并飞灰的重金属浸出能力均受到了抑制。     

Direct As,Bi, Ge,Hg and Se(IV) cold vapor/hydride generation from coal fly ash slurry samples and determination by electrothermal atomic absorption spectrometry

Direct cold vapor and hydride generation procedures for As, Bi, Ge, Hg and Se(IV) from aqueous slurry of coal fly ash samples have been developed by using a batch mode generation system. Ir-treated graphite tubes have been used as a preconcentration and atomization medium of the vapors generated. A Plackett–Burman experimental design has been used as a strategy for evaluation of the effects of several parameters affecting the vapor generation efficiency from solid particles, vapor trapping and atomization efficiency from Ir-treated graphite tubes. The effects of parameters such as hydrochloric acid and sodium tetrahydroborate, argon flow rate, trapping and atomization temperatures, trapping time, acid solution volume and mean particle size have been investigated. The significant parameters obtained (trapping and atomization temperatures for As and Ge; trapping temperature and trapping time for Bi; argon flow rate and atomization temperature for Se) have been optimized by 2²+star central composite design. For Hg, the trapping temperature has been also significant. Optimum values of the parameters have been selected for the development of direct cold vapor/hydride generation methods from slurry particles. The accuracy of methods have been verified by using NIST-1633a coal fly ash certified reference material. Absolute detection limits of 11.5, 48.0, 600, 55.0 and 11.0 ng l⁻¹ for As, Bi, Ge, Hg and Se have been achieved, respectively. A particle size less than 50 μm has shown to be adequate to obtain total cold vapor/hydride generation of metals content in the aqueous slurry particles.     

Total reflection X-ray fluorescence analysis of fly ash from Bulgarian coal-fired power plants

The contents of Cl, Ca, K, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Rb, Sr, Ba and Pb in raw coal fly ash from five Bulgarian power plants were determined by total reflection X-ray fluorescence (TXRF), using gallium as the internal standard. The samples were analysed as in slurry form in Triton? X-114. The experimental parameters, such as grain size, concentrations of fly ash slurry and excitation time were optimised. For validation of the method, the certified reference material BCR-176R fly ash was used. The precision of the results obtained is characterised by a relative standard deviation of approximately 10%. The resulting data confirm the suitability of TXRF for the simultaneous determination of major, minor and trace elements in coal fly ash samples. Further advantages provided by TXRF are easy sample preparation (no sample dissolution) and the small sample amount required for analysis.     

氧化钙对流化床燃煤飞灰中砷的淋滤特性影响

在实验室小型流化床实验装置上,利用添加氧化钙研究了原煤中钙硫比变化对燃煤过程中砷在飞灰中的富集规律和飞灰中砷的浸出特性的影响。实验结果表明,增加钙硫比能有效促进砷在飞灰中富集,降低砷的排放。砷与氧化钙的反应受制于钙的硫化反应控制。飞灰中砷的浸出与滤液pH值关系显著,碱性飞灰导致滤液pH值增大,能有效抑制飞灰中砷的浸出。碱性飞灰中砷的浸出历程为飞灰中砷在短时间内快速溶出;随着滤液pH值增大,溶出的砷与钙发生二次反应形成钙砷化合物沉淀,降低滤液中砷浓度。     

石嘴山电厂煤中微量元素的迁移释放行为

应用电感耦合等离子体质谱（ICP-MS）和原子荧光光谱（AFS）对中国西北部石嘴山电厂的原煤、底灰和飞灰中Hg、As、Se、Pb、Cr、Cd、Mo、Ni、Co、U和Th 11种微量元素的含量进行了测定。根据底灰和飞灰的产率, 结合微量元素在底灰和飞灰中的含量计算了电厂燃煤过程中微量元素的挥发性。结果表明, Hg、Cd、Se、As四种元素在燃煤过程的挥发率均在50%以上, 最高可达70%。通过对底灰和飞灰在酸性介质下的柱淋滤实验研究了底灰和飞灰中微量元素在60h内的迁移释放行为。Mn、Ni、Co、As四种元素的最大淋出率均超过2.0%, 最高接近10.0%, 并且还未达到淋滤平衡。根据微量元素的挥发和淋滤释放特性建立了电厂煤中有害微量元素在燃烧和淋滤过程中的释放分配模型。结果显示, 燃煤过程中的挥发是微量元素释放的主要形式, 部分元素的淋滤释放也可对周围水环境造成污染。
     

Determination of Ga, Ge, As, Se and Sb in fly ash samples by ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

Ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) has been applied to determine Ga, Ge, As, Se and Sb in fly ash samples. The influences of instrument operating conditions and slurry preparation on the ion signals were reported. Pd and ascorbic acid were used as the mixed modifiers to enhance the ion signals. This method has been applied to determine Ga, Ge, As, Se and Sb in NIST SRM 1633a and 1633b coal fly ash reference materials and a fly ash sample collected locally. Since the sensitivities of the elements studied in slurry solution and aqueous solution were different slightly, analyte addition technique was used for the determination of Ga, Ge, As, Se and Sb in these samples. The As and Se analysis results of the reference materials agreed with the certified values. The results for which no certified value was available were also found to be in good agreement between the ETV-ICP-MS results and the reference values. The reference value was obtained by digesting the samples and analyzing the digested sample solutions by pneumatic nebulization Dynamic Reaction Cell™ (DRC) ICP-MS. The method detection limits estimated from analyte addition curves were about 0.23, 0.13, 0.17, 0.25 and 0.11 μg g⁻¹ for Ga, Ge, As, Se and Sb, respectively, in original fly ash samples.     

Removal of Phenolic and Lignin Compounds from Bleached Kraft Mill Effluent by Fly Ash and Sepiolite

This study aimed to remove phenolic and lignin compounds from paper mill industry (4500 m³/h) wastewaters, which is discharged to sea from a plant located in the western Turkey. As adsorbent, fly ash, raw sepiolite and heat-activated sepiolite were used. The effect of factors such as, particle size, temperature and pH on adsorption process was investigated. From kinetic studies, equilibrium time was found as 1 h for both. The kinetic data supports pseudo-second order model but shows very poor fit for pseudo-first order model. Intraparticle model also shows that there are two separate stages in sorption process, namely, external diffusion and pore diffusion. Adsorption isotherms for fly ash and activated sepiolite were obtained at two different temperatures. From experiments carried out at different pHs, it was observed that pH plays an important role in the adsorption process in removing of both lignin and phenolic compounds, providing both ionizating the compounds and modifying sorbent surfaces. It was also observed that heat-activated sepiolite is more effective than raw sepiolite and fly ash to remove these compounds. Adsorption of lignin and phenolic compounds increases with decreasing particle size. In addition, the efficiency of adsorption decreases with increasing adsorption temperature for both fly ash and untreated sepiolite.     

酸洗污泥与煤共燃烧过程中重金属的迁移分布研究

采用高温管式炉系统进行酸洗污泥与煤共燃烧实验。对共燃烧后As、Cr、Ni、Cd、Cu、Mn、Pb、Zn、Sb、Se重金属元素在烟气、飞灰及炉渣中的分配率进行分析。结果表明,Cd、Se、Zn是易挥发重金属,主要分布在烟气和飞灰中。Cd在烟气中的最大分配率为61%;Se在烟气中的分配率为38.58%~94.612%;Zn在低、高温段分别主要分布在烟气和飞灰中。As、Cu、Pb、Sb是半挥发重金属,Pb在炉渣中的分配率较稳定,分配率为42.67%~64.76%,在烟气和飞灰中的分配率波动较大,其分配率分别是14.176%~45.79%和9.78%~32.55%;Sb在烟气中的最大分配率为37.64%;温度升高反而会抑制As、Cu挥发,这与高温下As、Cu易与矿物质反应生成络合物有关。Ni、Cr、Mn属于难挥发重金属,绝大部分残留在炉渣中,且分配率对温度变化不敏感。赋存于炉渣中的Cr、Ni分别超过95%和97%;随着温度升高,Mn在炉渣中的分配率由71.46%增加到96.89%。     

Hydrothermal solidification of municipal solid waste incineration fly ash

Hydrothermal solidification of municipal solid waste incineration (MSWI) fly ash has been conducted under saturated steam pressure at 200 °C for up to 48 h with quartz addition. To enhance the strength of solidified specimens further, the raw fly ash was pre-treated by water-washing and mixed with NaOH solution (2 M) as reaction solvent. Experimental results showed that curing time and temperature had significant effects on strength development. Strength development was found to be mainly due to tobermorite formation, and addition of quartz and NaOH solution promoted tobermorite formation. The raw fly ash could also be used as an additive to solidify MSWI bottom ash, and with raw fly ash addition (10%) the flexural strength of solidified specimens reached more than 21 MPa, suggesting high potential to recycle 100% MSWI ash (e.g. as 10% fly ash + 90% bottom ash). Leaching tests were conducted to determine amounts of heavy metals dissolved from solidified specimens. The results showed that under the hydrothermal conditions of this study, leaching of heavy metals was very low. As such, the hydrothermal processing method might have high potential for recycling/reusing MSWI fly ash on a large scale.     

城市生活垃圾焚烧飞灰重金属的浸出特性

对用流化床焚烧炉混烧垃圾和煤的布袋飞灰进行了重金属的TCLP(Toxicity Characteristic Leaching Procedure)浸出特性实验，探讨了液固比、初始pH值及浸出时间对飞灰中重金属Pb、Cr、Cd、Ni、Cu、Zn的浸出影响。结果表明，重金属的浸出量都随着液固比的增加而增加，其中Cr、Cu一般呈上升趋势，Cd、Ni、Zn在液固比大于20时曲线变化较平缓，Pb的浸出规律比较特殊，有一个明显的波峰和波谷。重金属在浸取液的pH≤2.90时的浸出浓度远远大于pH≥4.03时的浸出浓度。Pb、Cr、Zn随着浸出时间的增加，浸出浓度下降，而Cd、Ni上升，Cu是先上升后下降。在液固比、初始pH值及浸出时间这三个影响因素中，pH值对重金属的浸出影响较大，重金属在酸性环境下较易浸出。     

Determination of trace elements in fly ash samples by FAAS after applying different digestion procedure

The fly ash samples obtained from Kangal Power Plant were prepared for FAAS analysis by a new approach. The trace elements of the fly ash samples were leached with appropriate solvents under suitable conditions. The leaching method is known as an effective technique for substances dissolving very hard and refractory materials. The leaching effects of solvents and their mixtures were investigated on fly ash samples that are used largely in analysis of soil and sediment samples.The fly ashes mainly consist of glassy aluminosilicates. The major components of the samples are SiO₂, Al₂O₃, CaO and Fe₂O₃. Therefore, decomposition of the silicate lattice of the fly ash is required for liberation of trace elements. The dissolution process can be completed by using a mineral acid such as concentrated HCl. This technique has an advantage that the fly ash can be dissolved without any oxidation at room temperature.Maximum element recoveries were obtained by the procedure of 37% HCl leaching after the samples were treated with 2.0 ml of concentrated HF. It was also observed that maximum mass loss occurred in this procedure. The effect of the four leaching reagents, which are HCl, HNO₃, HClO₄ and HNO₃ + HClO_4, were investigated on fly ash samples that were treated with concentrated HF. An optimum leaching method was determined based on the confidence of analytical results and element recovery rates.     

煤中痕量元素在循环流化床锅炉中的迁移行为与富集特性

对天津市某电厂循环流化床(CFB)锅炉燃用的原煤及燃烧产物底灰、飞灰、细飞灰(≤50 μm)进行痕量元素含量的测定,分析了Be、Zn、Hg、V、Cr、Mn、Co、Ni、Cu、As、Se、Cd、Pb 13种痕量元素在燃烧过程中的迁移行为,揭示了痕量元素在CFB锅炉中的分配、富集特性。结果表明,CFB锅炉中,较低的炉温对于痕量元素的迁移富集产生了较大的影响。由相对富集系数得知,Be、V、Co、Se在底灰中耗散,在飞灰中富集,Zn、Mn倾向于在底灰中富集,元素Cd、Pb、Ni、Cu挥发性较强,在底灰和飞灰中均是耗散。As受钙氧化物影响,挥发性表现并不明显。Hg在底灰和飞灰中相对富集系数均很低,表明Hg在整个燃烧过程中以气态形式排放;Hg、As、Se、V、Cr、Mn、Co、Ni、Cu、Zn、Pb均有向小颗粒物中富集的趋势。根据相对富集系数以及研究的13种元素在低温CFB锅炉中的迁移行为,将这些元素分为三类:A类(E_R<0.1),主要是以气态形式排放元素Hg;B类(0.1R≤0.85),较易挥发元素As、Be、Ni、Cu、Se、Cd、Pb、Co、V;C类(E_R>0.85),主要残留在固体产物中元素Zn、Mn、Cr。     

固体添加剂对垃圾掺烧污泥焚烧飞灰高温过程中重金属挥发特性的影响

在研究垃圾与污泥掺烧后焚烧飞灰中重金属浸出特征的基础上,重点研究了飞灰在1 000 ℃条件下高温处置过程中重金属(Cu、Zn 、Pb、Cd)随不同停留时间的挥发特性及添加剂(CaO、Al₂O₃、SiO₂、高岭土、粉煤灰)对重金属转化与挥发特性的影响。研究结果表明,飞灰中重金属Zn、Pb、Mn含量较高,Ni的含量较低,而毒性较大的Cd达到29.4 mg/kg。浸出液中七种金属都满足危险废物鉴别标准(GB5085.3-1996),并且重金属的浸出浓度受浸取时间及浸取液pH值影响较大。在同样的高温处置条件下,焚烧飞灰中不同重金属的挥发特性有较大的差别。其中,Pb表现出易挥发的特性,其挥发率超过80%,而Cu挥发性较小,其挥发率小于30%。综合来看,飞灰中重金属的挥发性大小依次为Pb>Cd>Zn>Cu。飞灰中添加Al₂O₃和高岭土可以抑制Cd的挥发,添加Al₂O₃后Pb的挥发率有所减少,添加SiO₂、CaO、高岭土、粉煤灰均使Zn的挥发率降低,而对Cu的挥发率没有抑制作用,这与飞灰中高Cl含量及各痕量元素化合物对固体添加剂活性位选择性的竞争吸附有关。     

Neutron activation analysis and natural radioactivity measurements of lignite and ashes from Megalopolis basin,Greece

Elemental concentrations and specific activity values of natural radionuclides were measured in lignite, bottom ash and fly ash samples collected from the Megalopolis power plant A in southern Greece, using nuclear analytical techniques. The results show that the elements As, Br, Mo, Sb, Se, and U were enriched in the lignite samples, the elements Mo, Se and U in bottom ash, while fly ash samples were enriched in As, Mo, Sb, Se and U. Specific activity measurements also show that ²³⁸U (²²⁶Ra) activity values in lignite and both ash samples were high relative to the corresponding data for coal and earth crust given in the literature. As a high quantity of fly ash is produced during the operation of the lignite power plant A, this power plant should be considered as a major source of air particulate pollution and radiation to the population living in the vicinity of lignite burning power plant.     

Determination of inorganic oxyanions of As and Se by HPLC-ICPMS

A liquid chromatographic separation of inorganic oxyanions of As (As(V) and As(III)) and Se (Se(VI) and Se(IV)) using mixed ion-pairing reagents followed by ICPMS detection is described. The separation was accomplished in less than 4 min on Capcell C18 RP column using mixed ion-pairing modifier containing 5 mM of butane sulfonic acid (BSA), 2 mM malonic acid, 0.30 mM hexane sulfonic acid (HSA) and 0.5% methanol of pH 2.5. All four species were resolved with retention times of 2.4, 2.6, 3.0, and 3.1 min for Se(VI), As(V), As(III), and Se(IV), respectively. The detection limits were less than 0.08 and 0.77 μg l⁻¹ for arsenic and selenium species, respectively. The relative standard deviation of the proposed method for arsenic (at 2.5 μg l⁻¹) and selenium (at 10 μg l⁻¹) was less than 3.7 and 4.8%, respectively. The technique was used to determine inorganic oxyanions of As and Se in water samples (tap, well, and river) and extracts of coal fly ash and sediment. Low power microwave digestion was employed for extraction from fly ash and sediment samples.     

Leaching Studies of Inorganic and Organic Compounds from Fly Ash

Fly ash is produced in massive quantities by fossil fuel based power plants and waste incinerators, and contains high levels of potentially toxic chemicals. Various leaching tests exist to determine the available fractions, but the outcome is strongly dependent on the experimental conditions, and these have not yet been harmonised at the international level. In order to test existing protocols for heavy metals, several intercomparisons were organised within the framework of an EU-INCO project "ANALEACH", in which seven institutes from five countries participated. Two existing reference materials were made available for the project and test batches of two new fly ash reference materials were produced. Availability tests, leaching tests and pH-stat tests were studied and critical steps in the procedures were identified. Fly ashes can also contain large amounts of inorganic sulphur and nitrogen compounds, and the determination and leaching behaviour of these compounds were also studied. In one intercomparison for metals, inorganic S and N-compounds were also included. A five-step leaching test was optimised for fly ash in order to link metal fractions to different types of binding. Column leaching experiments were carried out to investigate leaching from fly ash into soil, mimicking the effects of (acid) rain on fly ash deposited on topsoil after atmospheric transport. The major fraction of the leached metal ions was retained by the soil. Also large numbers of organic compounds (including many toxic ones) were identified in fly ash extracts, especially in city waste incinerator ash. Leaching procedures based on ultrasonic extraction were developed for organic compounds and an intercomparison exercise was organised. In a field study at the river Nitra(Slovakia) numerous organic pollutants were found at elevated levels downstream from a major fly ash dump site.     

利用旋风炉玻璃化处理垃圾焚烧飞灰实验研究

在自行设计的旋风炉实验台上对焚烧飞灰进行玻璃化熔融实验,系统研究了焚烧飞灰熔融前后微观形貌、灰渣中重金属特性和浸出特性。实验结果表明,焚烧飞灰旋风熔融后成黑色的脆硬玻璃态熔渣,表层呈浅黄色。在熔渣中N i、Cr的固溶率最高,均超过95%以上;低熔点重金属多数挥发至熔融烟气和熔融烟道飞灰颗粒中,Cd的固溶率仅有21%,Pb和Zn部分固溶于玻璃态熔渣中,两者固溶率可达42%以上。Cu和As的固溶率分别为37%和18%。熔融后的玻璃态熔渣重金属浸出率明显低于熔融前的焚烧飞灰,且均低于美国EPA的标准限值。     

城市污水污泥与固体垃圾混烧过程中重金属迁移特性的研究

通过城市污水污泥与固体垃圾合成样品在小型管式焚烧炉内的混烧实验,采集灰渣样品进行XRF化学成分分析和浸出毒性鉴别测试,结合污水污泥焚烧过程中热力学平衡计算,定量表征了污水污泥中Cu、Pb、Zn、 Mn、Ni在焚烧过程中向底灰、飞灰和烟气迁移的特性及对灰渣的毒性影响。研究结果表明,污水污泥混烧显著提高了飞灰和底灰中重金属含量,其中Zn和Pb增加量最大,而Ni、Mn、Cu依次减少;随着有机氯的加入,飞灰中重金属含量呈现递增趋势,其中Zn表现最明显。毒性测试结果显示,污水污泥的混烧也导致了垃圾焚烧飞灰中Zn和Pb的浸出浓度超过中国对危险废物浸出的控制标准值。同时,重金属迁移的热力学平衡模型预测结果与实验结果差距较大。这表明热力学平衡计算方法还需进一步考虑影响重金属氯化物形成的其他因素,如在焚烧过程中反应动力学、焚烧室内氧气含量变化、与其他元素间的化学反应等。     

Determination of hydride forming elements (As,Sb, Se,Sn) and Hg in environmental reference materials as acid slurries by on-line hydride generation inductively coupled plasma mass spectrometry

A method for the determination of As, Hg, Sb, Se and Sn in environmental and in geological reference materials, as acidified slurries, by flow injection (FI) coupled to a hydride generation system (HG) and detection by inductively coupled plasma mass spectrometry (ICP-MS) is proposed. The HG unit has a gas liquid separator and a drying unit for the generated vapor. The slurries were prepared by two procedures. Approximately 50 mg of the reference material, ground to a particle size ≤50 μm, was mixed with acid solutions in an ultrasonic bath. In Procedure A, the medium was a hydrochloric acid solution while in Procedure B, the medium was aqua regia plus a hydrochloric acid solution. The conditions for the slurry formation and the instrumental parameters were optimized. Harsh conditions were used in the slurry preparation in order to reduce the hydride forming analytes to their lower oxidation states, As (III), Se(IV), Sb(III) and Sn(II), before reacting with sodium tetrahydroborate. To test the accuracy, 10 certified reference materials were analyzed (four sediments, three coals, one coal fly ash and two sewage sludges), with the analyte concentrations mostly in the μg g⁻¹ level. Good agreements with the certified values were obtained for Hg, Sb and Sn in the sediments using Procedure A and calibration against aqueous standard solutions. Using Procedure B, good results were obtained for Hg, Se and Sn in the sediment samples, for Se in the coal and coal fly ash samples and for Hg in the sewage sludge samples, also using external calibration with aqueous standard solutions. For As in sediments, coals and coal fly ash, Procedure B and the analyte addition calibration was required, indicating matrix effects. The relative standard deviations were lower than 5%, demonstrating a good precision for slurry analysis. The limits of quantification (10 times the standard deviation; n=10), in the samples, in ng g⁻¹, were: 20 for As, 60 for Hg, 80 for Sb, 200 for Se and 90 for Sn. The method requires small amounts of reagents and reduces contamination and losses.     

Humic acid adsorption on fly ash and its derived unburned carbon

Fly ash is solid waste from combustion process, containing oxide minerals and unburned carbon. In this investigation, fly ash has been separated into metal oxide mineral section and unburned carbon. The fly ash with different contents of unburned carbon was employed for humic acid adsorption to investigate the influence of unburned carbon on adsorption. It is found that metal oxides and unburned carbon in fly ash exhibit significant difference in humic acid adsorption. The unburned carbon plays the major role in adsorption. Higher content of unburned carbon in fly ash results in higher surface area and thus higher humic acid adsorption. Fly ash and unburned carbon exhibit adsorption capacity of humic acid of 11 and 72 mg/g, respectively, at 30 degrees C, pH 7. Humic acid adsorption is also affected by ion strength, pH, and temperature. The thermodynamic calculations indicate that the adsorption is endothermic nature with DeltaH(0) and DeltaS(0) as 5.79 kJ/mol and 16.0 J/K mol, respectively.